Thorpe's Dictionary of Applied Chemistry Vol.1

lMiV.
01
LIBRARY
A DICTIONARY
OF
APPLIED CHEMISTRY
VOL. I.
A DICTIONARY OF APPLIED CHEMISTRY
SIR EDWARD THORPE, C.B., LL.D., F.R.S.
Assisted by Eminent Contributors
REVISED AND ENLARGED EDITION
5 Vols. Medium 8vo, 2 $s. net per volume.
LONGMANS, GREEN, AND CO

LONDON, NEW YORK, BOMBAY, AND CALCUTFA
DICTIONARY
OF
APPLIED CHEMISTRY
BY
SIR EDWARD THORPE, C.B., LL.D., F.R.S.
PROFESSOR OP GENERAL CHKMISTRT AND DIRECTOR OP THE CHEMICAL LABORATORIES OP THK

IMPERIAL COLLEGK OF SCIENCE AND TECHNOLOGY, SOUTH KENSINGTON, LONDON;
LATE PRINCIPAL OF THE GOVERNMENT LABORATORY, AND A PAST PUK8IDKNT OF THE

CHEMICAL SOCIETY AND OF THE SOCIETY OF CHEMICAL INDUSTRY
ASSISTED BY EMINENT CONTRIBUTORS
IN FIVE VOLUMES
VOL. I.
REVISED AND ENLARGED EDITION
WITH ILLUSTRATIONS
LONGMANS, GREEN, AND CO

PATERNOSTER ROW, LONDON
39
NEW YORK, BOMBAY, AND CALCUTTA
1912
All rights reserved

PBEFACE
DURING the twenty-two years that have elapsed since the volume of this
first
work made its appearance, chemistry has advanced at a rate and to an extent
altogether unprecedented in its history, or, indeed, in the history of any other
science. This extraordinary growth has been accompanied by a no less re-
markable increase in the variety and comprehensiveness of its applications to
the arts and manufactures. Accordingly, in the attempt to make this re-
issue reasonably adequate as a presentation of contemporary knowledge, both as
regards the science and its
applications, has been found absolutely necessary
it
to enlarge greatly the original scope of the book. All the articles in the former
issue have been carefully revised and many have been wholly rewritten. In
addition, of course, a large number of new and important subjects have had
to be dealt with. The result is that this edition of the Dictionary of Applied
Chemistry is practically a new work.

In preparing it the Editor has again been fortunate in securing the co-
operation of eminent authorities, not only in the United Kingdom, but also in
America, Germany, Switzerland, etc., as writers on subjects with which they
are specially qualified to treat. A list of these, with the titles of their contribu-
tions, is prefixed to the several volumes in which these contributions appear.

Their names and standing are a sufficient guarantee that no pains have been
spared to make the work a faithful record of the present relations of chemistry to
the arts and manufactures.
The Editor acknowledgments to the following Demon-
desires to express his
strators, Assistant-Demonstrators, and Assistants in the Chemical Department

of the Imperial College of Science and Technology for help in the revision
and compilation of the subject-matter of many of the articles Dr. W. N. :
Haworth ;
Dr. H. F. Harwood, M.Sc. ;
Dr. P. W. Robertson, M.A., M.Sc. ;
Dr. Arthur Clayton Mr. A. T. King, B.Sc.

;
Mr. H. V. A. Briscoe, B.Sc.
;
;
Mr. E. G. Couzens, B.Sc. Mr. F. P. Dunn, B.Sc.

;
Mr. H. F. V. Little, B.Sc.
;
;
and Mr. J. A. Pickard, B.Sc. Also to Mr. Arthur G. Francis, B.Sc., of the
Government Laboratory; Mr. Lionel M. Jones, B.Sc., of the Birmingham
Technical School Miss Zelda Kahan, B.Sc., and Miss Gertrude Walsh, M.Sc.
;
and
Lastly, he is under great obligations to Dr. M. A. Whiteley, A.R.C.S.,
Mr. F. P. Dunn, B.Sc., A.R.C.S., of the Imperial College, for the care and
attention they have bestowed on the revision of the proof-sheets, and for the
assistance theyhave rendered generally in the production of the work.
ABBREVIATIONS
OF THE TITLES OF JOURNALS AND BOOKS.
Amer. Chem. J. American Chemical Journal.

Amer. J. Pharm. . American Journal of Pharmacy.
Amer. J. Sci. . . American Journal of Science.
Analyst .... The Analyst.
Annalen .... Annalen der Chemie (Justus Liebig).
Ann Chim. anal. . Annales de Chimie analytique applique'e a 1'Industrie, a 1' Agriculture,
a la Pharmacie et & la Biologie.
Ann. Chim. Phys. . Annales de Chimie et de Physique.
Ann. Falsif. . . .
;
Annales des Falsifications.
Ann. Inst. Pasteur. Annales de PInstitut Pasteur.
Arch. Pharm. . . ! Archiv der Pharmazie.
Bentl. a. Trim. . .
j
Bentley and Trimen. Medicinal Plants.
Ber Berichte der Deutschen chemischen Gesellschaft.
Ber. Deut. pliarm.
Ges Berichte der Deutschen pharmazeutischen Gesellschaft.
Bied. Zentr. . . . Biedermann's Zentralblatt fur Agrikulturchemie und rationellen
Landwirtschafts-Betrieb.
Bio- Chem. J. . . The Bio-Chemical Journal.
Biochem. Zeitsch. . Biochemische Zeitschrift.
Brewers J. . . . Brewers Journal.
Bull. Imp. Inst. Bulletin of the Imperial Institute.
Bull. Soc. chim. Bulletin de la Societe chimique de France.
Chem. Ind. . . . Chemische Industrie.
Chem. News . . . Chemical News.
Chem. Soc. Proc. . Journal of the Chemical Society of London. Proceedings.
Chem. Soc. Trans. Journal of the Chemical Society of London. Transactions.
Chem. Zeit. . . .
j
Chemiker Zeitung.
CJiem. Zentr. . .
|
Chemisches Zentralblatt.
Compt. rend. . . .
[
Comptes rendus hebdomadaires des Stances de P Academic des Sciences.
Dingl. poly. J. . . !
Dingler's polytechnisches Journal.
Fa'rber-Zeit. . . . !
Fiirber-Zeitung.
Fluck. a. Hanb. .
Fliickiger and Hanbury. Pharmacographia.
Frdl Friedlander's Fortschritte der Teerfarbenfabrikation.
Gazz. chim. ital. Gazzetta chimica italiana.
Jahrb. Min. . . . Neues Jahrbuch flir Mineralogie, Geologic und Palaeontologie.
J. Amer. Chem. Soc. Journal of the American Chemical Society.
J. Ind. Eng. Chem. Journal of Industrial and Engineering Chemistry.
J. Inst. Brewing . Journal of the Institute of Brewing.
J. Pharm. Chim. . Journal de Pharmacie et de Chimie.
J. Phys. Cliem. . . Journal of Physical Chemistry.
J.pr. CJiem. . . . Journal fur praktische Chemie.
J. Buss. Phys. Chem.
Soc Journal of the Physical and Chemical Society of Russia.
J. Soc. Chem. Ind. Journal of the Society of Chemical Industry.
J. Soc. Dyers. . . Journal of the Society of Dyers and Colourists.
Min. Mag. . . .
Mineralogical Magazine and Journal of the Mineralogical Society.
Monatsh Monatshefte fur Chemie und verwandte Theile anderer Wissen-
schaften.
Pharm. J. . . . Pharmaceutical Journal.
Pharm. Zeit. . . Pharmazeutische Zeitung.
Phil. Mag. . . .
Philosophical Magazine (The London, Edinburgh and Dublin).
Phil. Trans. . . .
Philosophical Transactions of the Royal Society.
Phot. J. . . . .
Photographic Journal.
Proc. Boy. Soc. . .
Proceedings of the Royal Society.
Rec. trav. chim. Receuil des travaux chimiques des Pays-Bas et de la Belgique.
Zeitsch. anal. Chem. Zeitschrift fiir analytische Chemie.
Zeitsch.angew.Chem. Zeitschrift fiir angewandte Chemie.
Zeitsch.anorg.Chem. Zeitschrift fiir anorganische Chemie.
Zeitsch. Nahr.
Genussm. . . . Zeitschrift fiir Untersuchung der Nahrungs-und Genussmittel.
Zeitsch. o/entl.
Chem Zeitschrift fiir offentliche Chemie.
Zeitsch. physikal.
Chem Zeitschrift fiir
physikalische Chemie, Stochiometrie und Verwandt-
schaftslehre/
Zeitsch. physiol.
Chem Hoppe-Seyler's Zeitschrift fiir physiologische Chemie.
LIST OF CONTKIBUTOES
TO VOLUME I.
Dr. E. F. ARMSTRONG (Messrs. Hunttey and Palmers, Reading}. [AMYLANS, BREAD, CARBO-
HYDRATES.]
Dr. G. H. BAILEY (The British Aluminium Company, Kinlochleven, Argyll, N.B.). [ALUMINIUM,
ALUMS, AND ALUMINIUM COMPOUNDS.]
G. S. BLAKE, Esq., A.R.S.M. [BARIUM ; CALCIUM.]
BERTRAM BLOUNT, Esq., F.I.C., Analytical and Consulting Chemist, London. [CEMENT.]
HAROLD BROWN, Esq., The Imperial Institute, London. [BALATA.]
Dr. J. C. CAIN, Editor of the Journal of the Chemical Society, London. [ANILINE ; ANILINE
SALT ; Azo-CoLOURiNG MATTERS BENZENE AND ITS HOMOLOQUES.] ;
W. H. COLEMAN, Esq., Tar Works Chemist (Messrs. Hardman & Holden, Manchester). [CAR-
BOLIC ACID.]
Dr.HAROLD G. COLMAN, F.I.C., Consulting and Analytical Chemist, London. [AMMONIA.]
JAMES CONNAH, Esq., B.A., B.Sc., F.I.C., The Government Laboratory, Custom House, London.
[ABSINTH ; ABSINTHIN ; ABSINTHOL ; ARRACK ; BRANDY ; CHARTREUSE.]
C. F. CROSS, Esq., B.Sc., F.I.C. (Messrs. Cross <5a Bevan, Consulting Chemists, London). [CEL-
LULOSE.]
(The late) Dr. W. DITTMAR, F.R.S., Professor of Chemistry in Anderson's College, Glasgow.
[BALANCE.]
THOMAS FAIRLEY, Esq., F.I.C., Analytical and Consulting Chemist, Leeds. [ASPIRATORS.]
JOHN GOLDING, Esq., F.I.C., The Midland Agricultural and Dairy College, Kingston, Derby.
[CHEESE.]
Dr. A. D. HALL, M.A., F.R.S., Rothamsted Experimental Station, Earpenden, Herts. [CEREALS.]
Dr. W. D. HALLIBURTON, F.R.C.P., M.R.C.S., F.R.S., Professor of Physiology, King's College,
London. [BiLE BLOOD BONE.] ; ;
JOHN HERON, Esq., B.E. (R.U.I.), F.I.C., Consulting Chemist, London. [BREWING.]
Dr. JOHN T. HEWITT, M.A., F.R.S., Professor of Chemistry in the East London College. [AcRi-
DINE DYE STUFFS.]
J. W. HINCHLEY, Esq., A.R.S.M., Lecturer on Chemical Engineering, Imperial College of Science
and Technology, South Kensington. [AUTOCLAVE.]
JOHN HOLMES, Esq., The Government Laboratory, London. [ALCOHOLOMETRY.]
Dr. JULIUS HUBNER, M.Sc., F.I.C., Director of Dyeing and Paper-making Departments, Muni-
cipal School of Technology, Manchester. [BLEACHING.]
H. W. HUTCHIN, Esq. (The Cornish Consolidated Tin Mines, Camborne). [ARSENIC.]
HERBERT INGLE, Esq., B.Sc., F.I.C., late Chief Chemist to the Transvaal Agricultural
Department. [ALMOND APPLE APRICOT ARGININE ARROWROOT ARTICHOKE ASH
; ; ; ; ; ; ;
ASPARAGUS AVOCADO PEAR ; BANANA BARLEY BATATAS BEAN BEET-ROOT

; ; ; ; ; ;
BETAINE BLACKBERRIES BRAN BREAD FRUIT BUCK WHEAT CABBAGE CARROT

; ; ; ; ; ; ;
CASSAVA CASTOR OIL SEEDS

; CAULIFLOWER CELERY CHERRY CHESTNUT.] ; ; ; ;
Dr. RUDOLF LESSING, Consulting Chemist, London. [BROMINE.]

VIVIAN B. LEWES, Esq., F.I.C., Professor of Chemistry in the Royal Naval College, Greenwich,
S.E. [ACETYLENE AS AN ILLUMINANT ; BOILER INCRUSTATIONS AND DEPOSITS.]
Dr. JULIUS LEWKOWITSCH, M.A., F.I.C., Consulting and Analytical Chemist, London.
[ADIPOCERE ANACARDIUM NUT ARACHIS OIL BASSIA OILS BEN OIL BONE FAT
; ; ; ; ; ;
BORNEO TALLOW BRAZIL NUTS CACAO BUTTER CAMELINE OIL CANDLES CANDLE-
; ; ; ; ;
NUT OIL CASTOR OIL ;CHAULMOOGRA OIL GROUP.] ;

viii LIST OF CONTRIBUTORS.
C. A. MITCHELL, Esq. (Messrs. Beaufoy & Co., South Lambeth Road., S.W.). [AERATED OB
MINERAL WATERS.]
Dr. GILBERT T. MORGAN, A.R.C.S., F.I.C., Assistant Professor of Chemistry, Imperial College
of Science and Technology, South Kensington. [ACIDIMETKY AND ALKALIMETRY ; ANALYSIS ;
CESIUM ; CERIUM METALS AND EARTHS.]

L. MYDDLETON NASH, Esq., F.I.C. (Messrs. Carson & Sons, Battersea). [CASEIN.]
B. E. R. NEWLANDS, Esq., F.I.C. (Messrs. Newlands Brothers, Analytical Chemists, London).

[ANIMAL CHARCOAL.]
A. G. PERKIN, Esq., F.R.S., F.I.C., Clothworkers Research Laboratory, University of Leeds.
[ALKANET ANNATTO ARCHIL ASBARG ATRANORIN BARBATIC ACID BRAZIL WOOD
; ; ; ; ; ; ;
BUCKTHORN BUTEA FRONDOSA CATECHU CATELLAGIC ACID CHAY ROOT CHESTNUT

; ; ; ; ;
EXTRACT.]
Dr. F. MOLLWO PERKIN, Consulting Chemist, London. [ELECTROCHEMICAL ANALYSIS.]
Professor W. H. PERKIN, LL.D., F.R.S., and Dr. ROBERT ROBINSON, Chemical Depart-
ment, University of Manchester. [ALIZARIN AND ALLIED COLOURING MATTERS.]
Dr. J. C. PHILIP, M.A., Assistant Professor and Lecturer on Physical Chemistry, Imperial College
of Science and Technology, South Kensington [CHEMICAL AFFINITY.]
J. A. PICKARD, Esq., B.So., A.R.C.S. [ACETINS ALLYL ] ;
Dr. HENRY ROBINSON, M.A. [ANESTHETICS.]

Dr. THOMAS K. ROSE, The Royal Mint, London. [ASSAYING.]
Dr. WALTER ROSENHAIN, The National Physical Laboratory, Teddington. [AMALGAM ;
ANNEALING.]
Dr. F. W. RUDLER, I.S.O., late of the Museum of Economic Geology, Jermyn St., London. [AGATE ;
CAIBNGOBM.]
Dr. ROBERT SCHUPPHAUS, Consulting Chemist, New York. [CELLULOID.]
Dr. ALFRED SENIER, F.I.C., Professor of Chemistry, University College, Qalway. [ALOES ;
ABABOBA POWDER BALSAMS ; ; BLACK HELLEBORE ROOT ; BROOM TOPS ; CALUMBA ;
CAMPHOBS CASCABA SAGBADA; ; CASCAEILLA BARK.]

L. J. SPENCER, Esq., M.A., Mineralogical Department, British Museum, London. [ABRASIVES ;
AGALITE AGALMATOLITE
;
ALUM-SHALE ALUNITE ALUNOGEN ;AMAZON-STONE ; ; ; ;
AMBER AMBLYGONITE
;
AMETHYST ANATASE ANGLESITE APATITE ABAGONITE
; ; ; ; ; ;
ABGENTITE ABGYRODITE ASBESTOS

; ATACAMITE AZUBITE BABYTES
; BAUXITE ; ; ; ; ;
BELLITE BENITOITE
;
BERYL BEBZELIANITE BERZELIITE BISMITE BISMUTHINITE
; ; ; ; ; ;
BISMUTITE BLOODSTONE ;
BLUE IRON-EARTH BOG IBON ORE ; BOLE BORNITE ; ; ; ;
BORONATROCALCITE BOSTONITE BOURNONITE BRAUNITE BROCHANTITE BBOGGEBITE

; ; ; ; ; ;
BRUCITE BUHBSTONE CALCITE

;
CARBONITE CABNOTITE ; CASSITEBITE CELESTITE ; ; ; ; ;
CERARGYRITE CERUSSITE CHALCANTHITE CHALK CHALYBITE.]

; ; ; ;
GEORGE STUBBS, The Government Laboratory, London. [BUTTER.]

Esq., F.I.C.,
EDWARD R. TAYLOR, Penn Tan, N.Y., America.

Esq., Manufacturing Chemist, [MANU-
FACTURE OF CARBON DISULPHIDE BY THE ELECTRIC FURNACE.]
MISS BEATRICE THOMAS, M.A., Girton College, Cambridge. [AMINES.]
Dr. M. A. WHITELEY, A.R.C.S., Demonstrator in Chemistry, Imperial College of Science and
Technology, South Kensington. [ADENINE ; ALANINE ALLANTOIN ALLOXAN ; ALLOX- ; ;
ANTIN ;
ARGINASE ; ARGININE ; ASPARAGINE ; ASPARTIC ACID ; CARNINE ; CARNITINE ;
CABNOSINE.]
GEHEIMRAT PROFESSOR Dr. OTTO N. WITT, Polytechnic, Charlottenburg, Berlin. [AziNES.]
Dr. W. P. WYNNE, F.R.S., F.I.C., A.R.C.S., Firth Professor of Chemistry, University of
Sheffield. [AURIN AND ROSOLIC ACID.]
DICTIONABY
OF
APPLIED CHEMISTRY.
AAL, A'L, ACH, AI'CH. Native names for and was used for removing grease-spots,
the roots of Morinda tinctoria and citrifolia, M .
stains, &c.,
paint-
from clothing. It is a nearly colour-
employed in various parts of India, under the less mobile liquid of powerful aromatic smell,
general trade name of Suranji, as a dyestuff, recalling that of oil of oranges.
more especially for dyeing reds, purples, and Abietene has been shown by Thorpe to consist
chocolates. H
almost entirely of normal heptane, C 7 1(j , mixed
ABACA. A
species of fibre derived from with a small quantity of a resin to which its
Musa textilis (Nee), obtained mainly from the characteristic smell of orange oil is due (Thorpe,
Philippine Islands, and used in the manu- Chem. Soc. Trans. 35, 296 Schorlemmer and
;
facture of mats, cordage, &c. It is also known Thorpe, Phil. Trans. 174, 269 ; v. also Blasdale,
'
under other names, including Manilla hemp,' J. Amer. Chem. Soc. 1901, 162).
' '
'
Menado hemp,' Cebu hemp,' Siam hemp,' Abietene is also the name given to the hydro-
'
and White rope.' Less valuable fibres are carbon which is obtained as an oil
by the reduc-
obtained from other species of Musa, such as tion of abietic acid (q.v.) (Easterfield and
Bagley,
M. sapientum (Linn.), the banana and plantain, Chem. Soc. Trans. 1904, 1238 ; Kraemer and
which yield banana fibre and plantain fibre. Spilker, Ber. 1899, 2953, 3614). Its formula is
ABIES. The generic name of the Silver Firs. C 1g H 2g and it is probably decahydroretene, as,
,
A. alba (Mill.) [A. pectinata (DC.)] furnishes when carefully purified, and reduced with
timber very similar to the white deal of Picea phosphorus and hydriodic acid, it yields a
excelsa, the common spruce. It is the source fluorescent hydrocarbon identical with the do-
of 'Strasburg turpentine,' containing free abienic, decahydroretene of Liebermann and Spiegel
abietric, and a- and fi-abietinolic acids, and an (Ber. 1889, 780).
amorphous substance abietoresen, an ethereal oil ABIETIC ACID. An acid obtained by digesting
of agreeable aromatic odour, a bitter principle colophony with dilute alcohol and recrystallising
and colouring matter (Tschirch und Weigel, Arch. the product from methyl alcohol (Maly, Annalen,
Pharm. 1900, 238, 411). 129, 54; 132, 249); or by saturating an alcoholic
A. Canadensis is the source of Canada balsam, solution of colophony with hydrogen chloride
which contains canadic, canadolic, and o- and 0- and subsequently recrystallising the product
canadinolic acids, an ethereal oil, canadoresen ; (Fliickiger, J. 1867, 727). It can also be
and small quantities of succinic acid and a bitter obtained by distilling colophony under reduced
substance. The acids contain no methoxyl pressure or with superheated steam (Easterfield
groups and give the cholesterol reactions, in- and Bagley, Chem. Soc. Trans. 1904, 1238).
cluding that of Tschugaeff (I.e. 1900, 238, 487). It occurs in resin spirit, from which it may be
ABIETENE. A hydrocarbon obtained by obtained by extraction with ether, shaking with
distilling the terebinthinate exudation of Pinus sodium carbonate solution and then acidifying
sabiniana (Doug.), a coniferous tree indigenous to with acid. It is obtained in a purer condition by
California, and growing on the dry slopes of the recrystallising from acetic acid m.p. 166-167
;
foothills of the Sierra Nevada and on the hills (Tschirch and Wollf, Arch. Pharm. 1907, 1);
along the coast, and known locally as the Nut pine 153-154 (Mach, Monatsh. 1893, 186). Accord-
or Digger pine. To procure the exudation, the tree ing to Easterfield and Bagley and Mach, it
is a derivative of phenanthrene, and has the
during winter is notched and guttered at a con-
venient height from the ground, and the resin on formula C 19 H 28 2 whilst Levy (Ber. 1906, 3043),
,
distillation yields the liquid hydrocarbon. The Koritschoner (J. Soc. Chem. Ind. 1907, 641),
crude oil was met with in San Francisco as an Fahrion (J. Soc. Chem. Ind. 1907, 264), and
'
article of commerce under the names of Abie- Vesterberg (Ber. 1907, 120) represent its com-
tene,'
'
Erasine,'
'
Aurantine,' and
'
Thioline,' position as C 20 H 30 2
.
According to Strecker
VOL. L T.
ABIETIC ACID.
(Annalen, 150, 131), Duvernoy (Annalen, 148 The so'Called crushed steel, made by quenching
143), and Easterfield and Bagley (I.e.), abietic white-hot crucible steel, is used in the stone-
acid is identical with sylvic acid ; it
cutting trade. Tantalum is an extremely hard
not identical with pimaric acid, which yields metal and may in future find some application
abietic acid on distillation under reducec depending on hardness.
pressure. By distilling abietic acid under ordi- Carbides.- Carborundum 1
(q.v.) or silicon
nary pressure, or, better, by treatment uith carbide, CSi (H. =
9J), is prepared artificially in
hydriodic acid, carbon dioxide evolved, the is the electric furnace from petroleum-coke and the
H
hydrocarbon abietene C 18 28 being formet purest quartz-sand, and is produced in large
(E. and B. I.e. Levy, I.e.
;
Kraemer and; quantities (over 3000 tons in 1907) at Niagara
Spilker, Ber. 1899, 3614). Distillation with Falls. It is largely made into sharpening stones
sulphur converts abietic acid into retene, and grinding wheels. In lapidaries' work it has
C 18 H 18(E. and B., I.e. ; Vesterberg, Ber. to a certain extent taken the place of corundum ;
1903, 4200). Oxidation with potassium per- but although harder than corundum, it has the
manganate yields an acid C 10 16 3 m.p. 123 H , disadvantage of being more brittle, and it soon
(Mach, Monatsh. 1894, 627) ; and a method has rubs to flour. Carbide of boron, CB g and silicide ,
been devised by Endemann (D. R. P. 183328 ; of boron, SiB 3 are also remarkable on account
,
Chem. Zentr. 1907, i. 1607) to oxidise resinous of their intense hardness (H. Moissan, Compt.
materials, containing abietic acid, to resin acids rend. 118,556).
and malonic acid. Oxides.- Corundum (q.v.) A1 2 3 is, next
Detection and Estimation. The following to diamond, the hardest of minerals (H. 9).
=
colour reactions may be used for detecting The impure variety, emery (q.v.), is not quite so
abietic acid : (1) 3 vols. of cone, hydro- hard. The crushed and graded material is made
chloric acid and 1 vol. of ferric chloride sol. into corundum wheels and emery paper, and is
give a violet red colouration ; (2) sulphuric acid much used in lapidaries' work. Artificial
'
dissolves abietic acid to a red solution; (3) when corundum, known by the trade-name of alun-
heated with dry chloroform, acetic anhydride dum,' is now manufactured in considerable
and sulphuric acid, a purple red colour is pro- amounts (about 3000 tons in 1907) at Niagara
duced changing through violet and blue to a Falls, by fusing bauxite in an electric furnace.
' '
greenish black (Mach. I.e.). In order to estimate Corubin is also an artificial corundum, formed
abietic acid in resins, &c., 10 grms. of the sub- as a by-product in the Goldschmidt thermite
stance are refluxed with 20-25 c.c. of 10 p.c. process.
alcoholic potash for hour on a water-bath the ; Quartz (q.v.) Si0 2 (H. = 7), and its several
resulting soap is decomposed with dilute hydro- varieties find extensive applications. Millstones
chloric acid, and the separated resin filtered off, and grindstones are made of quartz -rock,
washed with cold water and dried. It is then quartzite, burrstone (or buhrstone), grit, or
powdered and extracted with 50 c.c. of hot sandstone while scythe-stones, oilstones
(q.v.)
;
petroleum ether. From this solution abietic acid (q.v.), and whetstones (q.v.) consist of hornstone,
is precipitated by ammonia, filtered off, dried on lydian-stone and other compact varieties of
the water-bath, and the ammonia expelled by quartz. In the form of sand, quartz is used as a
gentle heating. The residue represents the sand-blast, in scouring-soap, for cutting and
amount of crude abietic acid in the sample (Robs, grinding marble, making sand-paper, &c. Tri-
Chem. Zentr. 1907, i. 997). poli or infusorial earth is a powdery variety of
Abietic acid (or colophony) is used in assisting opal (hydrated silica), and is used for polishing.
the growth of lactic or butyric ferments, as it Silicates. Garnet (q.v.) (H. 6-7) is =
favours the production of that which is present used for making ' emery' paper and cloth and ;
in the quantity and suppresses the

greater felspar (q.v.) (H.=6) is also used to a small
other. It promises to be of great use in the degree. Silicate rocks are employed to a small
e.g. pumice for polishing, and the mill-
fermentation industry in preventing infection extent ;
(Effront, Compt. rend. 136, 1556), (v. COLO- stone lava (leucite-nepheline-tephrite) of Nieder-
PHONY). mendig on the Rhine, for millstones. L. J. S.
ABRASIVES. The various hard substances, ABRASTOL or Asaprol - Etrasol. Trade
chiefly of mineral origin, used for abrasive pur- names for the calcium salt of /3-naphthol-
poses fall naturally into the following groups, in sulphonic acid, Ca(Cj H,OS0 3 ),,3H 2 0, used in
which the hardness is roughly inversely propor- the clarification and preservation of wines. The
tional to the complexity of chemical composition. maximum quantity needed for this purpose is
Elements. Diamond (q.v.) is the hardest of 10 grms. per hectolitre. According to Noelting
all substances (hardness =
10 on Mohs's scale). and Dujardin-Beaumetz and Stackler, the sub-
Inferior material of no use for gems is known as stance is harmless from a hygienic point of view
bo art (or bort), and is crushed to powder and (see Mon. Sci. 1894, 8, 257 J. Soc. Chem. Ind. ;
much used by lapidaries. Diamond powder is 1894, 177, 534). To detect its presence,
the only material with which diamond itself can
Sangle-Ferriere proceeds as follows (Compt.
be ground and polished. Embedded in the edge rend. 1893, 117, 796) 200 c.c. of the wine is
:
of a thin disc of soft iron, diamond powder boiled for an hour in a reflux apparatus with
is largely used for
cutting gem-stones and thin 3 c.c. of hydrochloric acid, when the abrastol
sections of rock Specimens, and also for slicing s hydrolysed to 0-naphthol, which
blocks of the harder ornamental stones.
may be
larger jxtracted with benzene, and the residue left
A black, compact variety 'of diamond known as after distilling the benzene sol. taken up with
'
carbonado (' carbonate or carbon') is em- hloroform. A
fragment of potash is dropped
bedded in the steel crowns of rock-drills.
So named by E. G. Achesou, in 1893, from carbon and
1
Amongst artificial products, steel and some corundum, because before it had been analysed, it was
other hard metals are used for abrasive purposes. thought to be a compound of carbon and alumina.
ABSTNTHIN OR ABSINTHIIN.
into the chloroform solution, which is boiled is
gently heated by steam to a temperature of
for 2 rains., when a blue colouration is pro- 60 in order to extract
chlorophyll. After
duced changing to green and finally becoming cooling, the green liquor is drawn off, and
yellow. 0-1 grm. per litre may thus be detected. strained, if
necessary, through a hair sieve. The
The presence of abrastol in no way vitiates the colouring is sometimes separately prepared and
determination of potassium sulphate (J. Soc. added as required to the colourless distillate.
Chem. Ind. 1894, 177). Sinibaldi (Mon. Sci. 7, Occasionally the latter is sweetened by the addi-
842) has given the following method : 25 c.c. of tion of about 5 p.c. by weight of crushed
the wine are neutralised by ammonia and shaken white sugar. Chlorophyll for imparting the
with 25 c.c. of amyl alcohol. After separation, green colour to absinth (and other liqueurs) is
the amyl alcohol is boiled to expel ammonia, and frequently obtained from nettles, parsley, and
when cold is shaken with 0-25 c.c. ferric chloride spinach, and is free from objection provided the
sol. A
grey-blue colouration denotes abrastol. vegetable matter is sound.
Gabutti (Chem. Zentr. 1904, 2, 370) proceeds On keeping, genuine absinth assumes the
in a similar way, but instead of ferric chloride, yellowish tint appreciated by connoisseurs, and
employs phosphoric acid and formaldehyde its qualities generally are improved by age.
solution, when, in presence of abrastol, a Many objectionable varieties of absinth are,
green fluorescence is produced. (For other however, on the market, made from inferior
methods, Sanna Pintus, J. Soc. Chem. Ind.
v. spirit, to which essences and resins are added, the
1900, 933; Briand, Compt. rend. 1894, 118, former to give a fictitious flavour and the latter
925 ; Carletti, Chem. Zentr. 1909, 2, 72. For to produce the opalescence which occurs in
colour reactions, v. Barral, J. Pharm. C'him. 1903, genuine absinth on the addition of water, owing
18, [5] 206; Salomone, Chem. Zentr. 1907, i. 306.) to the liberation of the essential oils, resinous
(Fora review of the various methods of detec- bodies, and colouring matters derived from the
tion, v. Vitali, Apoth. Zeit. 1908, 23, 507 ; J. Soc. plants and seeds used in its manufacture. Other
Chem. Ind. 1908, 830.) colouring matters than chlorophyll are also
ABRAUM SALTS. (Ger. Abraumsalze 'salts :
employed, as indigo, sulphate of copper, picric
to be removed.') The mixed salts found over- acid and turmeric or other vegetable colour.
laying the rock-salt deposit at Stassfurt, in Gum benzoin, guiacum ' and rosin are also used
Prussia. These consist mainly of rock-salt ; to produce ' milkiness on dilution, and even
Carnallite, a double chloride of potassium and chloride of antimony is said to have been em-
magnesium ; Sylvine, or potassium chloride ; and ployed for this purpose.
Kieserite, or magnesium sulphate, v. POTASSIUM. To detect adulteration it is usually suffi-
ABRIN. A brownish yellow soluble substance cient to determine the essential oils, resins,
obtained from the seeds of Abrus precatorius and colouring matters (vide Hubert, Ann.
(Indian liquorice or Jequirity). Contains a Chim. anal. 409, and Niviere and Hubert,
6,
poisonous proteid, resembling, if not identical Mon. Sci. 1895, 566). According to Hubert,
with, ricin. Lethal dose, according to Robert, is absinth has a specific gravity of 0-8966 to
only 0-00001 grm. per kilo body- weight i.e. 1 :
0-9982, and alcoholic strength of 47 to 72
to 100,000,000. p.c. by volume of absolute alcohol. The
ABSINTH. (Absinthe, Fr. Wermuthex-
; average results of twelve samples expressed as
tract,Ger.) One of the best-known liqueurs or grams per litre were as follows essential oils,
:
cordials (g.v.), is made chiefly at Lyons, Mont- 1-5 to 5-0; extractive, 0-36 to 1-72; acids.
pellierand Pontarlier in France, and until quite 0-024 to 0-288; aldehydes, 0-005 to 0-155; fur-
recently (videinfra) at Neufchatel in Switzerland. furol, 0-0002 to 0-007 ; ethers, 0-005 to 0-123. The
It is a highly intoxicating spirituous liquor strength of absinth as imported into the United
'
flavoured with oil of wormwood (Artemisia Kingdom varies from proof to about 20 over
'
absinthium, nat. ord. Composite) and other proof, and rather more than 3000 gallons are
essential oils as angelica, anise, cinnamon, imported annually.
cloves, fennel, hyssop, peppermint, &c. (v. OILS, Although genuine absinth, taken in modera-
ESSENTIAL). tion, has valuable qualities as a cordial, sto-
There are three distinct processes in the machic, and febrifuge, its characteristic bitter
manufacture of absinth, viz. maceration, dis-
:
principle, absinthiin (q.v.), is an active poison,
tillation, and colouration. The leaves and flower- having a very injurious effect upon the nervous
tops of Artemisia absinthium, together with the system of those addicted to the habitual and
other flavouring ingredients (which vary in kind immoderate consumption of absinth. Legal
and quality according to the requirements of the measures have therefore been taken in various
different manufacturers) are digested with spirit European countries to control, restrict, or even
for periods varying from 12 hours to 10 days, prohibit its sale. In France, liqueurs may not
according to the temperature of the infusion and contain more than 1 gram per litre of oil of
the strength of the spirit used. The French wormwood or other oil of similar toxic nature,
manufacturers, as a rule, digest for short periods whilst in Belgium the manufacture and sale of
at the temperature of an ordinary water bath, absinth have been entirely prohibited. A
and with spirit containing about 85 alcohol, similar prohibition was enforced in 1910 by the
whilst the Swiss maceration process was con- Swiss Government. J. C.
ducted at air temperature with spirit somewhat ABSINTHIN or ABSINTHIIN C 15 2(,0 4 The H .
bitter principle extracted from the dried leaves

'
below British ' proof strength, or about 50
alcohol. of large absinth or wormwood (Artemisia
The infusion is distilled and the distillate trans- absinthium) is an active poison, and it is to
ferred to the colouring vessel containing small its presence in oil of wormwood that the toxic
absinth leaves, balm and hyssop, dried and finely effect of absinth (q.v.) appears to be due.
divided. This vessel is h efip6t4palJy sealed and Various formulae have been assigned to this
B 2
ABSINTHIN OR ABSINTHIIN.
substance, being due to the
the differences ABUTILON INDICUM (Sweet), PETAREE
difficulty of obtaining it in a pure state (Mein, or TUBOCUTY. The bark of this malvaceous
Annalen, 8, 61 ; Luck, Annalen, 78, 87; Kromayer, tree consists of long, thin, tough fibrous strips
Arch. Pharm. [2] 108, 129). (bast fibres), and, according to Dymock (Pharm.
Pure crystallised absinthiin was first isolated J. [3] 8, 383) and others, is \vorthy of attention
by Duquesnel (Bui. de Therapeutique, 107, 438). as a source of fibre.
Senger obtained absinthiin as a pale yellow ABYSSINIAN GOLD. yellow alloy of 90-7 A
amorphous substance melting at 65 and having parts of copper and 8-3 of zinc. The ingot is
the empirical formula C 15 H 20 4 This formula .
plated on one side with gold, and is then rolled
was confirmed later by Bourcet, who found that out into sheets, from which articles of jewellery
the pure substance crystallises in fine white are formed in the usual way, the amount of
prismatic needles melting at 68, the amorphous gold on the finished article varying from 0-03 to
form and lower melting-point found by Senger 1-03 p.c. Known also as Talmi gold. The term
is sometimes applied in trade to Aluminium
being probably due to traces of a resinous
impurity. Bronze.
According to Senger and Bourcet, absinthiin ACACIA CATECHU (Willd) or KHAIR is a
is a glucoside, free from nitrogen, and is decom- tree growing in various parts of India. Its .un-
posed by the action of dilute acids, or even by ripe pods and wood, by decoction, yield a
boiling with water, into dextrose, a volatile oil, catechu (Agricult. Ledger, 1895, No. 1, and
and a solid resinous body of the aromatic series. 1896, No. 35) known by the name of Cutch or
It is soluble in alcohol, ether, chloroform, or Kutch, which must not be confounded with the
benzene ;difficultly soluble in light petroleum, officinal catechu (Catechu pallidum). It is used
water, though more soluble in cold than in in the preparation of some leathers and by dyers.
boiling water. It gives a precipitate with tannic The timber is also used for constructional and
acid and with gold chloride, which is reduced on other purposes.
warming yields volatile fatty acids on oxidation
; ACACIA GUM v. GTTMS.
with nitric acid, and oxalic and picric acids with ACANTHITE. A form of silver sulphide found
potassium chromate and sulphuric acid. With at the Enterprise mine, near Rico, in black
Frohde's reagent it gives a brown colour, chang- crystals of orthorhombic habit (Chester, Zeitsch.
ing to violet, then blue and with sulphuric acid
; Kryst. Min. 1896, 26, 526).
brown, passing through green to blue (Senger, ACAROID RESIN or BOTANY BAY RESIN
Arch. Pharm. 230, 103 ; and Bourcet, Bull. Soc. v. Xanthorrhcea Balsams, art. BALSAMS.
chim. [3] 19, 537). J. C. ACCIPENSERINE. A protamine belonging to
ABSINTHOL C 10 H 16 0. The essential prin- the sturine group found in the testis of Acci-
ciple of oil of wormwood derived from Artemisia penser stellatus. Composition of the sulphate :
absinthium Composites), a plant

(nat. ord. C 35 H 72 9
N 18 ,4H 2 S0 4 (Kuraeeff, Zeitsch. physiol.
indigenous to most European countries and com- Chem. 1901, 32, 197).
paratively recently introduced into the United ACENAPHTHENE C 12 H 10 , i.e. C 10H 6 C 2 H 4
: .
States of America, whence increasing supplies of A crystalline substance found in coal-tar oil
the cheaper qualities of wormwood oil are now (Berthelot, Bull. Soc. Chim. [2] 8, 226). Obtained
obtained. by cooling the fraction of heavy coal-tar oil
Although the oil obtained by the distillation boiling between 260 and 270. On recrystallising
of wormwood has been known for at least four the solid product from alcohol, acenaphthene is
centuries, its chemical composition was first obtained in long needles, m.p. 95 (Behr and
systematically investigated in 1845, when Leblanc Dorp, Annalen, 172, 265), 103 (Schiff, Annalen,
(Compt. rend. 21, 739) showed that its principal 223, 263) b.p. 278; 229-5 (Perkin, Chem. Soc.
;
constituent, boiling at 203, has the formula Trans. 69, 1196).

Cj H
16 0. This was confirmed later by Gladstone For its Absorption Spectrum, v. Baly and
and other investigators (Cheni. Soc. Trans. 17, 1), Tuck (Chem. Soc. Trans. 1908, 1902) Heats of ;
and by Beilstein and Kupffer (Annalen, 170, 290), Solution (Speyers, Amer. Chem. J. 18, 146) ;
who gave to the product the name 'absinthol,' Magnetic Rotation (Perkin, Chem. Soc. Trans.
and identified its dehydration product with 1896, 1088) ; Refraction and Dispersion (Pellini,
cymene. Gazz. chim. ital.31, i. 1) ; Similarity in form to
Semmler (Ber. 25, 3350) proved absinthol to acenaphthylene (Billows, Chem. Zentr. 1903, ii.
be a ketone identical with thujone or tanacetone, 44).
which occurs largely in other essential oils, as oil Is reduced by hydrogen in presence of nickel
of tansy, sage, and Artemisia barelieri. It is a 1
to tetrahydroacenaphthene (Sabatier and Sen-

colourless oUy liquid of pleasant odour, strongly :
derens, Compt. rend. 132, 210, and 566) ; with

dextrorotatory (about +68), boils at 203, ,
Ni0 2 to tetrahydro- and dekahydroacenaphthene
density 0-9126 at 20, and refractive index I
(Ipatjew, Ber. 41, 997).
1-4495. With potassium dichromate and acetic acid
Though isomeric with camphor, it differs from and acenaphthenequinone
yields naphthalic acid
that body in combining with sodium bisulphite 1
(Graebe and Gfeller, Ber. 25, 652 Jaubert, ;

and hi not being converted into camphoric acid Gazz. chim. ital. 25, i.
245).
by means of nitric acid, nor into campho- Derivatives. Oxygenated (Graebe and Gfeller,
carboxylic acid by treatment with carbon Annalen, 276, 1 ; Hodgkinson, Chem. Soc. Proc.
dioxide and sodium. With melted potash it 1896, 110); with sulphur (Dziewonski, Ber. 36,
gives a resin, but no acid. When heated with 962; Rehlander, Ber. 36,1583); styphnate (Gib-
P 2 S S and ZnCl, it yields cymene (Beilstein and son, Chem. Soc. Trans. 1908, 2098).
Kupffer, Ber. "6, 1183; Annalen, 170, 290; ACETAL C 6 H 14 O 2 orCH 3 -CH(OC 2 H 5 ),
,
(D6-
Wright, Chem. Soc. Trans. 27, 1 and 319; bereiner, Gm. 805 Liebig, Annalen, 5, 25 ;
4, :
Semmler, Ber. 25, 3343 and 27, 895). J. C. 1
14, 156 ; Stas, Ann. Chim. Phys. [3] 19, 146 ;

ACETALS.
Wurtz, Ann. Chim. Phys. [3] 48, 70 ; Geuther, contains chiefly aldehyde and
compound ethers,
Annaleu, 126, 63). 120-170 chiefly monochloracetal, 170~185 di-
To prepare acetal by Wurtz's method, 2 parts chloracetal (Lieben, I.e.), and the fraction
boiling
alcohol are added to a mixture of 3 parts man- above 185 contains trichloracetal (Paterno, I.e.).
ganese dioxide, 3 parts sulphuric acid and 2 parts These compounds may then be obtained in the
water, and, after the effervescence first produced pure state by repeated fractionation.
has subsided, the whole is heated at 100 until A better method of obtaining monochloracetal
3 parts have distilled over. The product is is by
passing chlorine through well-cooled 94-99
then fractionally distilled, and two portions, one p.c. alcohol until the chlorinated product has
boiling below 80 and the second boiling at a sp.gr. 1-02-1-03 at 25. Half the
original
80 95, are collected. 1 Each fraction is treated volume of alcohol is added and the mixture
with solution of calcium chloride and the ethereal heated a few hours at 50-60. The free acid
layer which separates is distilled. The product is removed
by calcium carbonate; the oil
contains aldehyde and ethyl acetate in addition washed with water, dried and fractionated.
to acetal ; to remove these it is shaken with con- The proportion of di- and trichloro-derivatives
centrated aqueous potash, the brown liquid formed depends on the amount of chlorine added
separated from the aqueous layer is distilled, (Fritsch, Annalen, 279, 288).
and the distillate shaken with calcium chloride. Monochloracetal CH 2 C1.CH(OC 2 H B ) 2 (Lieben,
It is then heated with twice its volume of con- Annalen, 146, 193 Paterno, Mazzara, Ber. 6,
;
centrated aqueous soda in sealed tubes at 100 1202 Klien, J. 1876, 336 Natterer, Monatsh.
; ;
for 24 hours, separated from the soda, distilled, 3, 444 ; 5, 497 ; Wislioenus, Annalen, 192, 106 ;
the distillate again rectified the fraction 100-

: Frank, Annalen, 206, 341) is a colourless liquid,
105, Avhich constitutes the greater portion, is having an aromatic ethereal odour b.p. 155 ; ;
acetal. sp.gr. 1-0418 at 0, 1-026 at 15 (Klien) 156- :
In addition to its formation as a by-product 158 (Autenrieth, Ber. 24, 159). When heated
in the oxidation of alcohol, acetal can also be with bleaching powder it yields di- and tri-
obtained from a mixture of acetaldehyde (1 vol.) chloracetal, chloroform, and chlorinated acetal-
and absolute alcohol (2 vols.) (1) by heating with dehyde (Goldberg, J. pr. Chem. [2] 24, 107).
acetic acid ( vol.) for 12 hours at 100 (Geuther, Dichloracetal CHC1 2 -CH(OC 2 H 5 ) 2 (Jacobsen,
Annalen, 126, 63) (2) by cooling in a freezing
;
Ber. 4, 217 Pinner, Ber. 5, 148 Annalen, 179,
; ;
mixture, passing dry hydrogen chloride to satu- 34 Krey, I.e.

; Paterno, Annalen, 149, 372
; ;
ration, and decomposing the resulting mono- 150, 134); b.p. 183-184; sp.gr. 1-1383 at 14.
chlorether with sodium ethoxide (Wurtz and When treated with hydrocarbons it forms com-
Frapolli, Compt. rend. 67, 418 ; Annalen, 108, pounds of the type CHX
2 -CC1, (Fritsch, Annalen,
223) ; or (3) by cooling a mixture of equal 279,219; Wicchell, Annalen, "279, 337 Butten- ;
volumes to 21, and passing a current of pure berg, Annalen, 279, 324).
hydrogen phosphide for 24 hours (Engel and Trichloracetal CC1 3 -CH(OC 2 5 ) 2 (Byasson, H
Girard, Compt. rend. 92, 692 J. 1880, 694).
;
Bull. Soc. chim. 32, 304 Wurtz, Frapolli, J.
;
Acetal is a colourless liquid with agreeable 1872, 438); b.p. 197; 204-8 at 758-7 mm.
odour: b.p. 104, and sp. gr. 0-821 at 22-4 Paterno, Pisati J. 1872, 303); sp. gr. 1-2813.
(Stas, Annalen, 64, 322) b.p. 103-7-104-3 at
;
When heated with concentrated sulphuric acid
744-4 mm., and sp. gr. 0-8314 at 20/4 (Briihl, ityields chloral.
Annalen, 203, 25). It is soluble in 18 vols. of H
Trichloracetal C 6 n Cl 3 2 Obtained by the .
water at 25, and the solubility increases as the action of chlorine on alcohol (Lieben, Paterno,
temperature rises. Acetal is miscible in all Krey, I.e.); crystallises in monoclinic needles
proportions with alcohol and ether, does not resembling caffeine ; m.p. 89.
reduce ammoniacal silver solution, and is un- Mondbromacetal (Pinner, Ber. 5, 149 ; Wis-
altered on exposure to air ; platinum black, licenus, Annalen, 192, 112; Fischer a. Lund-
however, oxidises it first to acetaldehyde and steiner, Ber. 25, 2551 ; Freundler a. Ledru,
subsequently to acetic acid. Compt, rend. 1905, 140, 794); b.p. 81-82 at
Acetal does not give the iodoform reaction 27-28 mm. (Freundler). According toF. a. L. a
until shaken with a few drops of hydrochloric cheap method of making monobromacetal is by
acid, whereby the acetal is hydrolysed to alcohol brominating paraldehyde at with constant
and aldehyde. shaking mixing with absolute alcohol, and after
;
Derivatives. Mono-, di-, and trichloracetal standing 12 hours pouring into an ice-cold sol.
are obtained as intermediate products in the of potassium carbonate. The separated oil is
preparation of chloral by passing chlorine through dried and fractionated in vacua.
80 p.c. alcohol (Lieben, Ann. Chim. Phys. [3] Monoiodoacetal, b.p. 100 at 10 mm. ; sp.
52, 313 ; Paternb, Compt. rend. 67, 765). 1-4944 at 15 (Hesse, Ber. 1897, 30, 1438).
According to Krey (J. 1876, 475), a better yield ACETALS (Wurtz, Ann. C him. Phys. [3] 48,
of these derivatives is obtained if a mixture of 370). The acetals are a group of compounds
2 parts absolute alcohol, 3 parts manganese formed by the combination of 1 mol. of an alde-
dioxide, 3 parts sulphuric acid, and 2 parts hyde with 2 mols. of an alcohol, and the elimina-
water is heated until f of the liquid has distilled tion of the elements of 1 mol. of water. They are
over and chlorine is passed through the well- generally obtained as by-products in the pre-
cooled distillate until it shows signs of turbidity. paration of aldehydes by the oxidation of the
In either case the product is washed with corresponding alcohols, the aldehyde at the mo-
water, dried over calcium chloride, and submitted ment of formation uniting with the alcohol,
to fractional distillation. The fraction 0-120 and this tendency to combine is much increased
if acetic acid is present (Geuther, Annalen, 126,
1
Theb.p. is given as in the original paper, but, inas-
much as b:p. of acetal is 104, it seems probable that 95 is 65), or if pure hydrogen phosphide is passed
a misprint for some higher temperature say 105. through the cooled mixture of aldehyde and
8 ACETALS.
alcohol (Girard, Compt. rend. 91, 629 ; J. 1880, 1194 ; l.c. and Compt. rend. 131, 745;
Delepine,
695). Stolle, Ber. 35, 1590 Oddo and Mameli, Gazz.
;
They are formed readily by the interaction of chim. ital. 33, ii. 373 ; Atto, R. Acad. Lincei,
aldehydes with very dilute alcoholic hydrochloric 1905, [v] 14, ii. 587 Freundler, Compt. rend.
;
acid (Fischer and Giebe, Ber. 30, 3053 31, 545).

; 138, 289; Bull. Soc. chim. 1907, [iv] 1, 66;
Ketonic and aldehydic acetals, both aliphatic and Tschitschibabin, J. pr. Chem. 1906, [ii.] 73,
aromatic, are formed by the interaction of 326 Paal and Gember, Arch. Pharm. 246, 306
; ;
nascent orthoformic ester and the necessary Arbusoff, J. Russ. Phys. Chem. Soc. 40, 637 ;
ketone or aldehyde in the presence of hydro- Smiles, Chem. Soc. Trans. 1909, 1000). The
chloric acid (Claisen, Ber. 31, 1010; Annalen, mono- and di-acetal derivatives of catechol (pyro-
237, 269). catechin) are obtained by heating the mono-
The acetals are liquids having aromatic sodium derivative of catechol with monochlor-
odours, and are sparingly soluble in water, acetal (Moreu, Compt. rend. 126, 1656).
from which they can again be separated on ACETALDEHYDE v. ALDEHYDES.
addition of concentrated calcium chloride solu- ACETAMIDE C 2 H 5 NO, or CH 3 .CONH 2.
tion. They are readily soluble in alcohol and (Hof mann, Ber. 15, 980; Schulze, J. pr. Chem.
ether ; their vapours or their solutions in alcohol [2] 27, 512 ; Keller, J. pr. Chem. [2] 31, 364 ;
benzene or acetones slowly harden dry gelatin Aschan, Ber. 31, 2344 Kiindig, Annalen, 105,
;
films (Beckmann and Scharfenberger, Chem. 277; Abel, J. Soc. Chem. Ind. 1899, 515.)
Zentr. 1896, ii.
930). When heated in a closed Acetamide is usually prepared by the dry
tube with glacial acetic acid, the corresponding distillation of ammonium acetate ; a better yield
aldehyde is obtained (Beilstein, Annalen, 112, (91 -7 p.c. ) and a purer product is obtained by
239). According to Bachmann (Annalen, 218, distilling ammonium diacetate in the special
45) the series of acetals can be descended by apparatus described by Fran9ois (J. Pharm.
heating any member of the group with an Chim. 23, 230). Between 135 and 195 acetic
alcohol containing a smaller number of carbon acid and water are evolved, and at 195-
atoms than is present in its alcohol residue ; for 222 some acetamide passes over. When the
example, diethylacetal and methyl alcohol yield temperature remains constant at 222 the dis-
dimethylacetal and ethyl alcohol ; but the tillation is stopped, the residue being pure
reverse change, if it occurs at all, results in the acetamide. A nearly theoretical yield is obtained
production of very small quantities of the higher by saturating a mixture of ethyl acetate and
acetal. Delepine (Compt. rend. 1901, 132, 331. ammonia with dry ammonia gas at 10, and
968) finds, however, that when some acetals are after standing, fractionating in vacuCi (Phelps,
boiled with any alcohol in the presence of a few Amer. J. Sci. 24, 429).
drops of hydrochloric acid, a balanced reaction Acetamide forms white hexagonal crystals
takes place. Thus Avhether methylal is heated which are odourless when pure, and melt at
with amyl alcohol or diamyl formal with methyl 81-82 (Hofmann, Ber. 14, 2729 Mason, Chem. ;
alcohol, the result is the same, the products con- Soc. Trans. 1889, 107 ; Meyer, Ber. 22, 24 ;
sisting of a mixture of methylal, diamyl formal, Forster, Chem. Soc. Trans. 1898, 791; Nicol,
methyl and amyl alcohols and the mixed acetal Zeitsch. anorg. Chem. 15, 397), boils at 222
MeO-CH 2 -OC 5 H 11 the products of higher mole-
,
(cor.) [Kiindig], is readily soluble in water,
cular weight predominating. Mixed acetals and when heated with acids or alkalis is con-
that is, acetals containing two different alcohol verted into acetic acid and ammonia (Coninck,
residues described by Bachmann (I.e.), con- Compt. rend. 121, 893 126, 907 127, 1028
; ; ;
sist of mixtures of molecular proportions of Dunstan a. Dymond, Chem. Soc. Trans. 1894,
two distinct acetals (Riibencamp, Annalen, 225, 220; Guebet, Compt. rend. 129, 61). Chlorine,
271 ; Fritsch and Schumacher, Annalen, 279, led into fused acetamide, yields acetchloramide
308), but Delepine (I.e.) seems to have obtained CHj-CONHCl; and bromine, in the presence of
such acetals and also their chloro- derivatives. dilute aqueous potash or soda yields acetbrom-
The latter have also been obtained by Magnamini amide, which on distillation with concentrated
(Gazz. chim. ital. 16, 330). aqueous soda is converted into methylamine
The following acetals have been prepared : (Hofmann, Ber. 15, 408); Buchner and Papen-
methylal, which is an excellent solvent for many dieck, Eer. 25, 1160; Selivanoff, Ber. 26, 423;
organic compounds (Kane, Annalen, 19, 175 ; Fransois, Compt. rend. 147, 680 ; 148, 173 ;
Briihl, Annalen, 203, 12) ; ethylidene-dimethyl Behrend a. Schreiber, Annalen, 318, 371).
(Arlsberg J. 1864, 485), -dipropyl, and -diiso- Acetamide acts both as a base and an acid
butyl (Girard, J. 1880, 695), and -diisoamyl (Pinner and Klien, Ber. 10, 1896), combining with
ether (Arlsberg, J. 1864, 486) ;
propylidencdi- hydrogen chloride or nitric acid, and forming
propyl ether (Schudel, Monatsh. 5, 247); iso- compounds in which a metal takes the place of
butylidenediethyl ether (Oeconomides, Bull. oneatom of hydrogen, as C 2 H 3 ONHAg (Strecker,
Soc. chim. 35, 500); and Tafel and Enock, Ber. 23,
amylidene-dimethyl, Annalen, 103, 321 ;
-diethyl, and -diisoamyl ether (Arlsberg, I.e.). 1550; Blacher, Ber. 28, 432; Hofmann and
Glycolacetal, a derivative of glycolaldehyde, has Bagge, Ber. 41, 312; Titherley, Chem. Soc.
also been prepared (Pinner, Ber. 5, 150 ; Varlev Trans. 1897,467). According to Forster (Chem.
Chem. Zentr. 1899, ii. 919). Soc. Trans. 1898, 783), mercury acetamide is a
A large number of halogen alkyl and other powerful dehydrogenising agent and owing to its
acetal compounds have been prepared (Fischer tendency to exchange its mercury for hydrogen
Ber. 26, 464; 41, 2860; 42, 1070 ; Fritsch (l.c ) when the latter is attached to nitrogen, particu-
Wolff, Ber. 21, 1481 ; Wohl, Ber. 21, 616 ; 22', when hydroxyl groups are in proximity,"
larly
568, 1353; Wohl and Lange, Ber. 40, 4727; itcan be employed, as a convenient means of
Heller, Lob, Alexander, Ber. 27, 3097, 3093*, detecting primary and secondary hydrazines
3102 ; Fosse nd Etlinger, Compt. rend. 13o] and primary hydroxylamines. It has also a
ACETIC ACID.
marked tendency to form additive compounds colouring matters (De Coninck, Compt. rend.
Ihe 1899, 503). It reacts with zinc chloride at 180
Proc. 1906, 23).
(Morgan, Chem. Soc. with the formation of the yellow dye flavaniline
has also been replaced
hydrogen in theNH, group
Soc. Irans. (Braiitigam, Pharm. Zeit. 44, 75).
by alkyl groups (Titherley, Chem. Acetanilide is present in the urine of cows
1901 396 411,413). Acetamide
forms molecular
CH 3 -CONH 2 ,X, where (Petermann, Ann. Chim. anal. 1901, 165). It is
compounds of the type For methods
X = an organic or inorganic acid or an inorganic largely used in headache powders.
Ann. Chim Phys of estimation v. Puckner, Ph. Rev. 1905,
salt (Titherley, I.e.; Topin,
When acetamide is treated Witt 302, and Seidell, Amer. Chem. J. 1907, 1091.
F71 5 99)
or The following reactions may be used for
formaldehyde, paraldehyde, trioxymethylen^
,H 2 U bromine water
condensation products of the type R-NH- detecting its presence: (1)
of value as added to a solution of acetanilide in acetic acid
are obtained ;
these products are of p-brom-
for uric acid (J. Boo. gives a white crystalline precipitate
antiseptics and as solvents
acetanilide, m.p. 167; (2) evaporation of a
Chem. Ind. 1906, 283). Mono-, di-, and
tri-
solution to dryness with mercurous nitrate gives
chloracetamide (Willm, Annalen, 102,
1
and Fuchs, Ber. a green mass, changing to blood red on addition

Geuther, J. 1864, 317 ; Pinner of a drop of concentrated sulphuric acid (3)
10 1066 ; Malaguti, Annalen, 56,
286 ; Uoez, ;
Annalen 229, 165; ferric chloride gives no blood-red colouration

Annalen, 60, 261; Bauer, from
171 ; Swartz, with acetanilide, thus distinguishing it
Dootson, Chem. Soc. Trans. 1899,
Chem. Zentr. 1899, [L] 588 Clermont, Compt. phenacetin and antipyrine.
Chloracetanilides (Jones and
;
Derivatives.
rend 133 737). Bromo-dialkyl-acetamide (J. Nitro-
Orton, Chem. Soc. Trans. 1909, 1056) ;
Soc/Chem. Ind. 1904, 1238) and other halogen acetanilides and Sluiter, Rec. trav.
derivatives have also been prepared (Seliyanott,
(Holleman
132 Broche, chim. 1906, 208).
J. Russ. Phys. Chem. Soc. 24, ;
Acide Acetique.
Conrad, Ber. 29, 1042; ACETIC ACID. Essigsciure.
J. pr. Chem. [2], 50, 97 ;
Ber. Acidum Aceticum. C 2H 4 2

i.e. CH 3 -COOH, or
Zinke and Kegel, Ber. 23, 230 Willstatter, ;
37 1775 Steinkopf, Ber. 41, 3571 Swartz,

I.e. ;
;
C,H 3 OOH.
226 ; Ratz, Acetic acid occurs in nature in the juices ot
Francesconi, Gazz. chim. ital. 33, either as free acid
Monatsh. 1904, 25, 687; Einhorn
Annalen many plants, especially trees,
or, generally, as the
calcium or potassium salt ;
343, 203; Finger, J. pr. Chem. 1906, [11.]
74, 153).
in the oils
The acetamido 0-naphthaquinones and some and, in the form of organic acetates,
from many seeds. It is stated to be present
in
of their halogen derivatives which may
be used in
Avhen the plants are kept from
and Zimmerli, Matis, and larger quantities
dyeing (Kehrmann the light. It exists in certain animal
fluids ;
and Aebi, Ber
Locker, Ber. 31, 2405 ; Kehrmann states it to be a normal constituent
32 932; Kehrmann and Wolff, Ber. 33, 15^8) Bechamp
of milk. Gmelin and Geiger have found it in
and other acetamide derivatives have been pre-
Ind. 1894, 60 Lumiere, mineral waters, doubtless from the decomposition
pared (J. Soc. Chem.
;
Monatsh. of organic matter.

Bull. Soc. chim. 1903, iii. 30, 966; Ratz, both at the ordinary
26 1487 ; Miolati, Gazz. chim. ital. 23, 190). Being a very stable body a
C4 7 H N0
or NH(C 2 3 0) 2 and H and at high temperatures, it is found as pro-
Diacetamide dis-
duct of the decomposition or destructive
2 ,
127 ;
its derivatives (see Gautier, Z. 1869, substances. Acetic
Ber. 23, tillation of many organic
Hofmann, Ber. 14, 2731; Hentschel, acid was first shown by Lavoisier
to be formed
Amer
2394; Curtius, Ber. 23, 3037; Mathews, Its true composi-
Chem. J. 20, 648 ; Konig, J. pr. Chem. 1904, [n.J by the oxidation of alcohol. and
in 1814,
347 Tnacet- tion was ascertained by Berzelius
69 1 Troeger, J. pr. Chem. 69, ;
it was formed
H H Dobereiner in 1822 proved that
amide C 6 9 NO 3 or N(C 2 3 0) 3 and its deriva-
,
the oxidation of alcohol,
tives (see Wichelhaus, Ber. 3, 847).
together with water, by
acid as had
C6 H -NH-COCH also without the formation of carbonic
ACETANILIDE 5 3,
as Antifebrin, is prepared by heating

been previously supposed.
known Acetic acid is produced by the
glacial acetic
acid and aniline for some Preparation.
and destructive dis-
together oxidation, decomposition,
time. , .
bodies. 1 he greater
acetic acid tillation of many organic
By substituting thioacetic acid for and at a in commerce is obtained by
the reaction proceeds more rapidly part of that used wood.
the destructive distillation of
lower temperature (Pawlewski, Ber. 1898, bbl). into acetic acid
Alcohol may be converted
Acetanilide may also be prepared by heating such as chromic
of dilute acetic by powerful oxidising agents,
1 part of aniline with If parts may be taken
acid! nitric acid,&c. Advantage
acid or of crude pyroligneous acid under pressure or platmui
6220 of the fact that spongy platinum
at 150-160 (Matheson & Co., Eng. Pat. and
black has the property of absorbing oxygen
and D. R. P. 98070 ; J. Soc. Chem. Ind. 1897, It
thus acting as a powerful oxidising agent
559) over a vessel of
The substance melts at 114-2 (Reissert, Ber. spongy plttinum be placed the platinum
and Fresse, alcohol with free access of air,
1890, 2243), at 115-116 (Hantzsch the oxygen and 1
absorbs at the same time
Ber. 1894, 2529), and boils without decomposi- and produce
Ber. alcohol vapour, which combine
tion at 303-8 (corr.) (Pictet and Crepieux,
acetic acid and water :
1888 1111), at 305 (corr.) (Perkin, Chem. Soc.

Trans. 1896, 1216) ;
it is soluble in hot water, CH 3 CH OH+0 =CH
2 2
COOH+OH 3 2
.
Alcohol. Acetic acid.

alcohol, or ether.
Acetanilide is hydrolysed at 100 by caustic
but not by In addition to acetic acid, aldehyde (acetic
potash or by hydrochloric acid, aldehyde) is produced, which
is intermediate
sulphuric acid (Hantzsch

and Fresse, Ber. 11 alcohol and acetic
it is rapidly decomposed by
chromic m composition between
removal of two
2529) ;
and producing acid. It is formed by the

acid, liberating carbon dioxide,
ACETIC ACID.
atoms ofhydrogen from the alcohol without liquor is poured from the crystals and concen-
their replacement by an atom of oxygen : trated with the production of a second crop of
crystals ; this is repeated until about four crops
CH 3 -CH 2 OH+0=CH 3 -CHO+H 2 0.
have been produced. The crystals are dissolved
Alcohol. Aldehyde.
in water, filtered through animal charcoal, mixed
In presence of excess of oxygen aldehyde with about 10 p.c. of calcium chloride,
and
forms acetic acid. Aldehyde is a very volatile recrystallised, The crystals are distilled with
liquid, and is liable to be lost before its conver- a mixture of 1 part sulphuric acid of sp.gr.
sion into acetic acid it is therefore necessary in
; 1-84 and 2 parts water, and the acetic acid
all cases where acetic acid is produced by the concentrated in the usual way. The glacial
oxidation of alcohol to allow free access of air. acid may also be prepared by the distillation
This method produces a very pure acetic of di- or acid-acetate of potash, which, when
acid, but on account of the initial cost of the heated, decomposes into acetic acid and the
platinum (which, however, is not in any way in- normal acetate of potash. If ordinary acetic
jured by use) it is not used on the manufacturing acid be heated with normal potassium acetate,
scale. the acid acetate is formed, and a weaker acid at
Patents have been taken out in England for first distils over ; as the temperature rises, the
the acetification of alcoholic liquors by ozone diacetate begins to decompose, and the distil-
and by nascent oxygen and also for the manufac- late increases in strength until the glacial acid
ture of acetic acid from alkali acetates by passes over. When the temperature reaches
electrolysis(Plater-Syberg, Eng. Pat. 1898, 233). 300 the distillate becomes coloured from the
A French patent (360, 249, 1905) describes the decomposition of the acid (Melsens, Annalen, 52,
preparation of acetic acid from acetylene. 274; Compt. rend. 19, 611).
Acetylene is passed into a solution of a normal Scott and Henderson (Eng. Pat. 1896, 6711)
mercuric salt which precipitates mercury acety- purify the crude acetates by boiling w^th sodium
lide. The liquid is then boiled, when aldehyde hypochlorite until the colour is nearly gone.
is formed and the mercuric salt reformed. The The solution is then cooled and allowed to settle.
aldehyde is then oxidised to acetic acid. The clear liquid is decanted and crystallised. The
Several kinds of ferments are capable of crystals are of great purity. Scott (Eng. Pat.
converting fermented alcoholic liquors into 1897, 12952) has patented a process which
acetic acid. The two chief are the Mycoderma dispenses with lime in the manufacture of acetic
aceti of Pasteur, also known as Mycoderma vini, acid. He distils the crude acid at 100, and
'
'
mother of vinegar and the vinegar plant,'
'
fractionally condenses the vapours. The acid
and the Bacterium xylinum of Brown. Buchner collects mainly in the first portions.
and Meissenheimer have shown that the fer- Crude acetates may be decomposed with
mentation is due to enzymes in the plant-cell. H 2 S0 4
or HC1, and the acetic acid distilled in
They are white gelatinous nitrogenous plants, vacuo (Thompson, J. Soc. Chein. Ind. 1896, 357) ;
requiring for their healthy growth proteid or crude acetic acid may be treated with oxygen
substances and mineral salts, which are always under pressure, filtered through charcoal and
present in wines and other alcoholic liquids. distilled over pure sodium acetate (Schmidt,
In the absence of this food they have no action Eng. Pat. 1896, 25100).
on pure alcohol, but Pasteur has shown that Hochstetter (J. Soc. Chem. Ind. 1902, 1469)
pure alcohol, to which alkaline phosphate and prepares pure acetic acid by heating pure sodium
ammonium phosphate have been added, is slowly acetate with dry HC1 at 120.
acetified by this ferment, the ammonia supply- 'Aromatic vinegar' may be prepared by
ing the nitrogen. distilling crystallised diacetate of copper (dis-
The concentrated or glacial acid is usually tilled verdigris). The acetate is dried at 160
prepared by the distillation of a dry acetate and heated in earthenware retorts, when the
with an equivalent quantity of strong sulphuric glacial acid distils over. The verdigris produces
acid, or acid potassium or sodium sulphate. about half its weight of the acid. The pleasant
Sodium acetate is generally used. The odour of aromatic vinegar is largely due to
anhydrous âlt is fused on sheet-iron pans, 6 feet acetone, which is always produced when acetates
4
by feet, care being taken that no sparks reach of heavy metals are distilled, but camphor and
the dried salt, as it would then ignite and burn essential oils are frequently added to increase
like tinder. The mass is cooled, broken into or modify the smell.
small lumps, and distilled with concentrated Acetic acid for pharmaceutical and medicinal
sulphuric acid. The first portion distilling con- purposes should not decolourise a solution of
tains the water, the later portion is collected and
potassium permanganate. To remove the organic
cooled when crystals have formed the still liquid
; matter which would have that effect, the acid
portion is removed, the crystals are melted and is distilled with potassium permanganate or
redistilled as before, producing the glacial dichromate.
acid. The strongest acid solidifies at
Properties.
When a solution of calcium chloride is mixed 16-7 in tabular or prismatic glistening crystals.
with a solution of calcium acetate, crystals of .The glacial acid may be cooled to 10 with-
calcium aceto-chlorideCaC 2 H 3 2 Cl,5H 2 Ogradu- out solidification, even when agitated, but on
ally separate. These crystals may be produced the addition of a crystal of the acid the whole
in comparative purity even when
impure broun solidifies and the temperature rises to 16-7.
acetate of lime is used. To obtain acetic acid The specific gravity of the crystals at 15/4
ordinary commercial or '
distilled acetate of
'
lime is mixed with the proper proportion of cal-

is 1-0607 (Mendele'eff, J. 1860, 7). They melt to a
mobile colourless liquid of sp.gr. 1*0543 at 16/4
cium chloride, and the solution is concentrated by (Petterson. J. pr. Chem. [2] 24, 301), 1-0495 at
evaporation until it crystallises the mother
;
20/4 (Briihl) which boils at 118-5at 760 mm.
ACETIC ACID. g
(Perkin). The liquiduninflammable, but the

is is evolved and the density increases until 20
vapour burns with a blue flame producing water p.c. of water is present; from this strength to
and carbonic acid. When passed through a red- 23 p.c. of water the density remains stationary.
hot tube only a small portion is decomposed, Further dilution lowers the density, so that
producing carbon, acetone, benzene, &c. The either dilution or concentration from this point
strong acid blackens when heated with concen- will produce an acid of diminished density.
trated sulphuric acid, evolving sulphurous and An acid containing only 43 p.c. of acid has the
carbonic anhydrides. same density as the glacial acid. This, together
Nitric and chromic acids have no action ; for with the slight difference between the density of
this reason acetic acid is frequently used as a acetic acid and water, renders it impossible to
solvent for organic substances such as hydro- determine, with any precision, the percentage of
carbons, which are to be subjected to the action acid by means of the hydrometer.
of chromic acid. Chlorine under the influence No definite hydrates of acetic acid are known
of sunlight replaces a portion of the hydrogen, (De Coppet, Ann. Chim. Phys. [7] 16, 275 Colles,
;
and produces mono-, di- and trichloracetic acids. Chem. Soc. Trans. 1906, 1247).
Similarly, bromine produces dibromacetic acid. The following table shows the density of
On the addition of water to the glacial acid heat aqueous acetic acid at 15 and 20 :
DENSITY OF AQUEOUS ACETIC ACID (OUDEMANS).

JO ACETIC ACID.
appear at the negative pole, and ethane and
carbon dioxide at the positive pole.
ACETIC ACID. 11
process conducted are low-roofed, and the walls

is are extracted three times with water, in a circular
are provided with openings for the admission of mash tun supplied with a central stirrer, the first
air, which can be closed when the temperature extraction with water at 72, the second at a
is not sufficiently high. higher temperature, and the third with boiling
A number of casks of well-seasoned oak, water. The extracts, which together should not
bound with iron hoops, each holding from 50 to exceed 100 gallons, are passed into a large cast-
100 gallons are supported on their sides in rows iron tank 24 feet by 8 feet, cooled by
refrigerators
about 18 inches from the floor, one set being to 24, poured into a large circular vessel,
frequently placed above another, in which case mixed with 3 or 4 gallons of good yeast and
those nearest the roof are found to work most fermented briskly for about forty hours. The
rapidly. Each cask is bored with two holes in extract is filtered, and, where intended for the
the front end, a larger one, the ' eye,' for the manufacture of the best keeping vinegar, is
addition of wine or the removal of vinegar, and stored in casks for some months, whereby the
a small one for the admission of air. extractive matters which would induce putrefac-
When first used the casks are thoroughly tion are deposited.
' '
scalded with boiling water to remove extractive This wash may be treated by the quick '
'
matter, one-third filled with boiling strong vine- vinegar process or acetified in large casks
gar, and allowed to stand for eight days ; from lying on their sides in a room at a temperature
that time wine is added in charges of about 10 of about 24. The bung-holes of the casks
pints every eight days until not more than two- are open, and at each end near the top an open-
thirds full after a further interval of 14 days a
; ing is made for the circulation of air. When
portion, varying from 10 gallons to half the conducted in the open air the process is known
' '
total bulk, is drawn off and the periodical addi- as fielding ; from eight to twenty rows of casks
tion of the wine continued. The temperature constitute a vinegar field. The operation is com-
of the chambers should be about 25, and is menced in the spring and completed in about
kept up when necessary with a stove. In three months.
order to ascertain if the fermentation is com- The fermenting casks are frequently worked
pleted at the end of the usual time, the work- in pairs ; one being completely and the other
man plunges a Avhite spatula into the liquid ; three parts filled, acetification progresses more
if a reddish froth adheres, more wine is added
rapidly in the latter ; every day a portion is
and the temperature raised ; a white froth transferred thereto from the full cask, being re-
indicates the completion of the process. More placed by an equal amount of the more fer-
than eight days sometimes required to com-
is mented liquid, until completed.
which case stronger wine
plete the oxidation, in Before storing, it is necessary to filter the
and a higher temperature may be used. The vinegar from the extractive matter. The filter-
' ' '
sluggishness may, however, be due to the casks ing vessel, rape or fining tun,' is a large
becoming foul, which occurs usually after about cask, usually wider at the base than at the top,
six years' working. The deposit of argol, yeast fitted with a false bottom, above which it is
sediment, &c., is thoroughly removed, the casks filledwith spent tanner's wood, wood shavings,
'
cleansed and recharged with hot vinegar as in or, which is far preferable, with rapes,' the
the case of new casks. Good casks will often pressed cake of residue from the British wine
last twenty-five years. manufacture, consisting of the stalks and skins
When working satisfactorily each cask will of grapes and raisins. Through this the vinegar
produce about twice its capacity of vinegar anis poured, escaping through a tap beneath the
nually. false bottom into a tank from which it is con-

Before storing, the vinegar is usually passed
'
tinuously pumped to the top of the vessel and
' '
again passed through until the last traces of
'
through the rapes where it is brightened
and the acetification completed. alcohol have been oxidised and the vinegar
In other parts of France and in Holland and cleared and brightened. In this way pickling
on the Rhine the following method is used. vinegar is produced.
The wine is placed in two large upright tuns For household vinegar, the malt is acetified
about 9 feet high and 4 feet wide, open to the in upright casks fitted with false perforated
air. Each tun has a perforated false bottom bottoms covered with a layer of rapes after ;
about 12 inches above the true bottom on this is

; twenty-four hours it is transferred to another
placed a quantity of vine cuttings, stalks, &c., so similar cask, remaining there for two or three
as to expose a large surface for the formation of days, and thence to a third and fourth
cask. A
the fungus. One of the vats is half, and the other to the
portion of the liquid is transferred
'
completely, filled. The acetification progresses

'
mothers and the remainder allowed to fer-
more rapidly in the former this, after twenty-
;
ment. A little argol is occasionally added to
four hours, is filled from the full cask, in which produce a flavour of wine vinegar, the liquid
the action then increases. This alternate trans- being clarified with isinglass.
Vinegar casks are made in three sizes,
ference is continued daily until the acetification hold-
is complete. The most favourable temperature ing 25, 50, and 116 gallons.
is about 24. The vinegar is run off into casks Quick vinegar process. Schnellessigbereiiung.
containing chips of birch wood on which the This method, applicable to any alcoholic
in 1720 by
lees settle, and in about fourteen days being liquid, is founded on that proposed
thus clarified is stored in close casks for the Boerhaave, and was first introduced by Schutzen-
market. bach in 1823. It differs from the other processes
Malt vinegar. Malzgetreide Bieressig. Ace- in causing the liquid to expose a very large
tum Britannicum. This is prepared from an surface to the action of the air, one gallon being
infusion of malt which has first been fermented sometimes made to cover a surface of 100
to produce alcohol. Six bushels of crushed malt square yards.
12 ACETIC ACID.
The vat usually from 6 to 12 feet high,
is upper disc and trickles slowly down the twisted
and from 3 4 feet wide. In England it is
to threads, which swell and prevent too rapid
frequently as much as 13 feet high, 14 feet passage. As the liquid flows over the shavings
wide at the top, and 15 feet wide at the base. it becomes oxidised, the action being more rapid
At a distance of 18 inches from the bottom, six or when, after some time in use, the shavings have
more ah- holes are bored 1 inch in diameter, in- become coated Avith the ' mother of vinegar.'
clining downwards towards the inside ; just When the action is satisfactory the temperature
above these a false perforated bottom is fixed. A of the interior rises on account of the oxidation
quantity of beechwood shavings is thoroughly to 37, and creates a constant upward current
washed with hot water, dried and placed on the of air which passes from the openings below the
false bottom, nearly filling the vat. The shav- false bottom, round the shavings and through
ings may be substituted with advantage by- the tubes in the upper disc.
pieces of charcoal about the size of a walnut, When the liquid contains no more than 4 p.c.
from which the saline particles have been re- alcohol, the vinegar which collects is entirely
moved by acid and subsequent washing. The acetified, but where a stronger liquid is used it
acetifying action is assisted by the power of may be necessary to pass it three or four times
absorbing oxygen possessed by the charcoal. through the graduator. When a strong vinegar
Near the fop of the tun is fixed a wooden is required, thaft produced from one of the above-
disc perforated by holes as large as a quill, about mentioned liquids is mixed with a more alcoholic
1 inch apart
through these, twists of cotton
; liquid, and again passed through, and this may
yarn or string are passed, of sufficient length to be repeated until 1 oz. of the liquid will neutral-
touch the shavings they are tied into knots at
: ise sixty grains pure dry potassium carbonate,
the upper end to prevent them from slipping corresponding to about 12 p.c. acetic acid by
through. There are also five or six larger holes weight. Each graduator will contain about 80
through which pass glass draught tubes project- gals, of liquid and will produce daily 15 gals, of
ing on either side of the disc, 1 to 2J inches wide good vinegar. One workman usually attends to
and 4 to 6 inches long, firmly fastened so that ten tuns.
no liquid can pass round them through the hole. By this process, on account of the large
About 1 inch from the true bottom is fixed a surface exposed, a considerable loss of alcohol,
bent tube attached to a tap through which the and hence of acetic acid, is unavoidable, amount-
vinegar is drawn as soon as it rises to a height ing when properly carried out to about 6 p.c. of
of about 15 inches. The vessel is closed with the whole but if the temperature has been
;
a tightly-fitting lid through which a circular allowed to rise too high, the loss is greatly in-
opening is cut for the admission of liquid and creased. At the same time sufficient air must
for the escape of air. be introduced to convert the alcohol directly
Before commencing the fermentation it is into acetic acid, or the loss will be further in-
' '
necessary to sour the shavings for this pur-

;
creased by the formation of the volatile aldehyde.
pose hot vinegar is poured in from the top and By some makers the vapours from the tuna
allowed to soak for at least twenty-four hours. are passed over or through water to absorb the
The composition of the fluid used varies con- alcohol and aldehyde.
For this purpose two
siderably any alcoholic liquid may be used, but
:
floating gasometers are sometimes used one
:
the presence of a trace of tarry matter, such as rises and removes the air which has performed
is present in pyroligneous acid, prevents the itswork, while the other falls, keeping up a con -
action. According to Wagner (Chem. Tech- stant current of air through the generator. As
nology), the following mixture is generally used : each gas-holder falls it discharges the air through
4 gab. (20 litres) brandy of 50Tralle3 (42-5 a cistern of water, which absorbs the volatile
p.c. by weight), 9 gals, vinegar, and 27 gals, products and is used for the preparation of a
water, to which is added a mixture of bran and further quantity of malt extract.
rye to promote the growth of the vinegar fungus. Recent improvements in the quick vinegar
Another standard liquor is 50 gals, brandy process have taken the form of labour-saving
or whisky 52 p.c. by weight, 37 gals, beer or malt contrivances and of devices to avoid loss by
wort with about T iR) part of ferment this is
[J ; evaporation. Leaker has patented a process
mixed with 3 to 4 vols. of soft water before whereby the acetification takes place in closed
passing through the tuns. Molasses or honey in rectangular vessels containing shelves of absorb-
the proportion of 2 Ibt. to 50 gals, is sometimes ent woven material. To the vessel is attached
added,to produce a more finely coloured vinegar. a condensing worm into which the vapours are
'
For wine malt,' 40 Ibs. wheat-meal and 80 drawn by a fan.
Ibs. barley-meal are ground, and mixed together About one-third of the total extractive matter
with 40 gals, warm water (50); after- set- in the malt
is lost or dissipated in the fermenta-
tling, the clear liquid is drawn off, the residues tion and
acetification.
are treated with hotter water (70), settled, In Singer's generator a number of vessels
the liquid removed and the residue again treated, are placed one above another in a shed in which
this time with boiling or nearly boiling water, in a suitable temperature is maintained and from
such quantity that the total washings amount to which draughts aie excluded. The vessels are
about 100 gals. The solution is cooled, mixed connected together by wooden tubes provided
with 15 Ibs. yeast, and allowed to ferment at with longitudinal slits through which air can
27 for five or six days ; it is then known as pass. The liquid slowly drops through the
'
the gyle.' The temperature of the chamber tubes from one vessel to another, and, exposing
being about
' '
38 the liquid which, where the
'
a large surface to the air, becomes acetified.
'
generator or graduator is new, is heated to It is stated that the loss of alcohol usually
50, or, where in use for some time and thus experienced is avoided in this process. In many
in good condition, to 25, is poured over the ' '
vinegar works- the larvae of the vinegar fly
ACETIC ACID. 13
' '
(Drosophila cellaris) and vinegar eels (An- An artificial vinegar is made by mixing
guillula aceti) abound. acetic acid with water and
adding burnt sugar
Vinegar found occasionally to decompose
is (caramel) and acetic ester to produce the proper
when shaken, probably on account of the lees colour, odour, and taste. This vinegar differs from
becoming mixed with the liquid. genuine kinds by the absence in the evaporated
Of late years delicacy and uniformity of residue of phosphoric, tartaric, or malic acid.
flavour in the various kinds of vinegars have Properties. Malt vinegar is a brown liquid
been obtained by the use in acetification of pure of a characteristic odour due to the
presence, in
cultures of the particular bacterium (Henneberg, addition to the acetic acid, of acetic and other
Zeit. fur Spiritusind, 1898, 180, and Cent. Bakt. esters. Acetic ester is frequently added in
1905, 14, 681; Rothenbc,ch, Woch. fur Brau. small quantity to increase this aroma.
15, 445, and Deut. Essiggind, 1905, 9,217, and The vinegar of the B.P. has a sp.gr. of 1-017
Woch. fur Brau. 1906, 23, 260 Mayer, Zeit. ; to 1-019. In commerce it usually occurs in four
fur Spiritusind, 21, 334; Biichner and Gaunt, strengths, numbered 18, 20, 22, and 24. The
' '
Annalen, 1906, 349, 140). last is proof vinegar ; it contains 6 p.c. acetic
In addition to wine and malt, vinegar is pre- acid, and its sp.gr. is 1-019. The numbers
pared from many other substances. Cider denote the fact that one fluid ounce of the
vinegar is of a yellowish colour, sp.gr. 1-013 to liquid will neutralise 18, 20, 22, and 24 grains
1-015. It contains 3J to 6 p.c. acetic acid, and respectively of pure dry sodium carbonate. The
on evaporation leaves a mucilaginous residue, real weight of acetic acid in one ounce of liquid
smelling and tasting of baked apples, and con- may be found by multiplying its number by
taining malic but not tartaric acid. The residue 1-132, and the percentage by weight by multi-
varies from 1-5 to 1-8 p.c. Genuine cider vinegar plying the number by 0-259. Thus No. 24 should
is distinguished from spurious cider vinegar by contain 6-22 p.c. of absolute acetic acid.
the residue, which consists of glycerol, albuminous The addition of 1 part sulphuric acid to
matters, gums, malic and other organic acids 1000 parts vinegar is lawful, and is occasionally
and mineral matters. They have no rotation made, though the idea that it prevents decom-
and little cupric reducing power after the usual position has been shown to be erroneous.
clarification with basic lead acetate solution. Malt vinegar usually contains alcohol, gum,
The ash of a pure cider vinegar amounts to sugar, and extractive matter, acetates, chlorides,
not less than 0-25 p.c., consisting mainly of potash, free and combined sulphuric acid, and on evapo-
with small quantities of alumina, lime, magnesia, ration and ignition leaves a residue containing
sulphate, and phosphate, variable amounts of much phosphate.
carbonate, and complete absence of soda. Wine vinegar varies in colour from pale
Spurious cider vinegars have a molasses-like yellow to red that made from white wine is
;
residue and an ash with a large percentage most esteemed it usually has an alcoholic
;
of lime or soda (Doolittle and Hess. See odour. Its sp.gr. is 1-014 to 1-022 it contains ;
also Smith, J. Amer. Chem. Soc. 1898, 20, 3 ; from 6 to 12 p.c. acetic acid. A litre (1-76 pint)
Leach and Lythgoe, I.e. 1904, 26, 375 ; Van ]
of Orleans vinegar usually saturates 6 or 7
Slyke, New York Agric. Exp. Stn. Bull. 1904, i
grams (92 to 108 grains) of pure dry sodium

258, 439 ; Ladd, N. Dakota Exp. Stn. Bull, i
carbonate. On evaporation the total extract

32, 278). Perry and crab-apple vinegars are !
varies from 1-7 to 2'4 p.c., of which 0-25 p.c. is
used in Wales and Monmouthshire, and possess usually potassium tartrate, a salt peculiar to
characteristic properties. wine vinegar. The residue, with the exception
Ale vinegar is prepared from sour strong of the tartar, should dissolve in alcohol.
pale ale. It usually gives a large residue (5 to 6 The proof vinegars of various countries differ
p.c. ), and is very liable to decomposition. Crystal considerably the minimum of acetic acid al-
;
vinegar is ordinary vinegar decolourised by fil- lowed by the various Pharmacopoeias is France,
tration through animal charcoal. householdA 8 to 9 p.c. England, Germany, and Austria,
;
vinegar is made
in Germany from 7J gals, 6 p.c. Belgium, 5-6 p.c. Russia, 5 p.c. United
; ; ;
soft water, 2 Ibs.honey or brown sugar, 1 gal. States, 4*6 p.c. Genuine vinegar seldom falls
whisky or corn spirit, 2 ozs. cream of tartar. below 5 p.c., and should be condemned as
Glucose or sugar vinegar is prepared by adulterated with water when the amount is as
the conversion of amylaceous substances into low as 3 p.c.
sugar, by the action of dilute acids, followed by
fermentation and acetification. It contains Analysis of Vinegar.
glucose, dextrin, and very often gypsum, with The adulterants to be looked for in vinegar
hardly any proteins. The ash is composed are mineral acids, especially sulphuric acid,
mainly of potassium salts, is rich in sulphates, and more rarely hydrochloric, and still more rarely
in the case of cane-sugar vinegars, readily fusible nitric acid, tartaric acid, and pyroligneous acid ;
(Allen's Comm. Org. Anal. 1909, 498). It is flavouring agents, cayenne, ginger, &c. ; metals
stated to be used for adulterating wine vinegar. usually derived from the vessels used copper,
It can be distinguished from other vinegars by lead, zinc, tin, arsenic (from sulphuric acid).
the addition of 3 or 4 volumes strong alcohol, The presence of free mineral acids may
which produces a slimy precipitate of dextrin. be detected by the addition of Paris violet
Barium chloride usually gives a copious precipi- (methylaniline violet). Prepare a solution of
tate, due to the sulphuric acid used in the manu- this dye by dissolving 1 part in 1000 parts
facture of the glucose. water, and add two or three drops of the solu-
Vinegar is now made from skim milk by tion to about one ounce of the vinegar. In
addition of sugar, neutralisation with chalk, presence of 1 p.c. free mineral acid the colour is
pitching first with yeast and then with Mycoderma green, with 0-5 p.c. bluish-green, and with 0-2
aceti (Barbier Fr. Pat. 1903, 334071). p.c. blue (Hilger, Arch. Pharm. 1876, 193).
14 ACETIC ACID.
mineral acids are added to vinegar in
If to deposit any sulphate of lime still present.
small quantity they liberate an equivalent Sulphate of lime, being slightly soluble in water,
amount of acetic acid from the acetates, until the is contained in the liquid in small quantity, and
acetates are wholly decomposed, and form salts diminishes the brilliancy of the colours produced.
with the base, thus ceasing to exist as free By the substitution of lead acetate for the
acids. As acetates on ignition produce carbon- calcium acetate a better product is obtained.
ates, the presence of an alkaline reaction in the For this purpose 100 Ibs. alum is dissolved in
ash indicates the presence of acetates in the 50 gallons water, and treated with 100 Ibs. finely-
vinegar, and therefore the absence of free mineral powdered lead acetate with constant stirring or, ;
acids, though these may have been added in using the same quantities, 10 Ibs. crystallised
small quantities in the first instance. If, how- carbonate of soda is added before the acetate of
ever, the ash be neutral, the presence of mineral lead ; or, to 100 Ibs. alum in 50 gallons water
acids is indicated. Hydrochloric acid may be 6 Ibs. of carbonate are added in small portions
tested for by adding silver nitrate to the dis- followed by 50 Ibs. of lead acetate. The addition
tillate from the vinegar. of the carbonate is made with a view to the pro-
Heavy metals may be considered absent if no duction of a basic sulphate of alumina as well
darkening is produced on passing sulphuretted as the acetate, and as the sulphate assists
hydrogen for some time through the solution. the mordanting, less acetate is required. The
To determine the acetic acid in vinegar 110 c.c. solutions are allowed to settle and decanted.
may be distilled until 100 c.c. have passed over. They contain the aluminium acetate mixed with
The 100 c.c. will contain four-fifths of the total basic aluminium sulphate and alkaline sulphate.
acid, and may be titrated with standard alkali An aluminium sulpho-acetate appears to act
and phenolphthalei'n, making an allowance for satisfactorily. It is prepared by mixing (1)
the one- fifth left in the retort. 453 Ibs. ammonia alum (or 383 Ibs. aluminium
Formic acid may be estimated by the method sulphate), 379 Ibs. lead acetate, 1132 Ibs. water ;
recommended by Ost and Klein (Chem. Zeit. or (2) 453 Ibs. alum (or 333 Ibs. aluminium sul-
1908, 32, 815). The acid is neutralised with phate) and 158 Ibs. acetate of lime. The mix-
alkaliand titrated with permanganate. Other ture is agitated, settled, and the clear liquid
substances which reduce permanganate must be decanted.
absent. By the use of aluminium sulphate, red liquor
Oxalic acid may be estimated by concen- of the same density contains much more of the
trating the vinegar and then boiling with calcium active alumina than that prepared with alum.
acetate solution. Thus in a sample of the former 1 gallon con-
Potassium hydrogen tartrate is estimated by tained 4 oz. 416 grs. alumina whilst the average
titration against N/2 alkali, and tartaric acid by amount found in three samples prepared from
conversion to potassium hydrogen tartrate and alum was 3 oz. 245 grs. The addition of a little
subsequent titration (Zeitsch. anal. Chem. 1908, ammonia or other alkali to the red liquor pre-
47, 57). pared from aluminium sulphate is advantageous
(For the estimation of methyl alcohol in vine- for certain colours. Red liquor usually contains
gar, seeAnn. Chim. anal. 1901, 6, 127 and 171.) from 3 to 5 p.c. alumina (A1 2 3 ) and 6 to 10 p.c.
Cayenne pepper, ginger, and other flavouring acetic acid ; its density varies from 1-085 to
matters may be discovered by neutralising the 1-120.
vinegar and tasting. Ammonium acetate C 2 H 3 0.jNH 4 .
Chevallier has found fuchsine in French wine The crystalline salt is usually prepared by
vinegars. saturating glacial acetic acid with dry ammonia
gas. In solution it may be prepared more
METALLIC ACETATES.
cheaply by neutralising acetic acid solution with
Aluminium acetates. ammonia. On evaporation, a solution of the
The triacetate or normal acetate A1 2 (C 2 H 3 2 ) 6
salt loses ammonia, and leaves the acid acetate
is not known. A solution corresponding to this or diacetate.
compound, but which appears to be a mixture of Ordinary solid ammonium acetate always has
the diacetate and acetic acid, is the only acetate an odour of acetic acid ; it is very soluble in
It is known as red
'
of commercial importance. water and alcohol.
''
liquor or mordant rouge,' and is largely used Pure ammonium acetate should be entirely
in dyeing and calico-printing, especially for the volatilised on heating. The commercial salt
production of red colours, madder reds and pinks usually contains the same impurities as sodium
(whence its name of red liquor) for the produc-
; acetate.
tion of dense lakes, and for waterproofing woollen Calcium acetate. Diacetate of lime. Pyro-
fabrics. It is prepared by several methods. Ca(C 2 H 3 2 ).4
lignite of lime. .
A solution of alum is added to acetate of This important salt is prepared by neutral-

lime liquor. The lime is precipitated as sul- ising acetic acid, or pyroligneous acid, with lime
phate, its place being taken by the aluminium or chalk.
forming aluminium acetate sulphate of am-
; In the preparation from pyroligneous acid,
monia or potash (according to whether ammonia the crude acid may be used, in which case the
or potash alum has been used) is produced acetate of lime is known as brown acetate ; or the
at the same time. The mixture is agitated distilled liquor may be employed, producing grey
and allowed to settle, and a small quantity of acetate. The acid is placed in large wooden or
the clear fluid removed and tested by the addi- iron pans, and powdered chalk or lime added in
tion of alum ;if a precipitate forms sufficient
slight excess ; the liquor remains at rest at a
alum has not been used and more must be warm temperature until settled, and is then
added. The solution is filtered and concentrated siphoned off into the evaporating pans. It i-r
to a specific gravity of 1-087 to 1-10 and allowed coils of
generally evaporated by pipe through
ACETIC ACID.
which steam passes ; in this case the vessels are This substance consists of a mixture of mono-,
usually wooden, and lined with lead, but some- di-, andtri-basic acetates of copper, which are
times iron pans are used, the evaporation being present in different proportions in different
conducted over a fire. As the 1 iquid evaporates, varieties of verdigris.
tarry impurities rise to the surface, and are re- At Grenoble and Montpellier the following
moved with a skimmer. As the acetate forms, process is used The ' marcs ' or residues from
:
it is withdrawn and drained in wicker baskets \

the wine factories, consisting of the skins and
suspended over the pans. |
stems of grapes, are loosely placed in earthen
The proper drying of the Bait is necessary vessels, about 16 inches high, 14 inches in
to the formation of a good product. In diameter at the widest part, and 12 inches at the
is used, which is mouth, covered and allowed to ferment, until
large works a drying house
usually a wind furnace 7 or 8 feet long, 4 feet on inserting a piece of copper (previously
broad. It is first heated from 75 to 115, and moistened with verdigris and dried), it becomes
the fire slackened; the salt is then spread over the uniformly coated green in 24 hours. The
bottom to the depth of about 2 inches, and when fermentation should not proceed too far, or
somewhat dry an equal quantity is spread above decomposition may ensue.
it, the salt is repeatedly turned, and the heat The copper used is in sheets ^ inch thick, 4
continued for about 24 hours. When apparently to 6 inches long, and 3 to 4 broad, each
weighing
dry, the heat is increased to about 125, and about 4 ox. they are freed from scales, if neces-
;
the last traces of moisture driven off. Care sary, rubbed with a solution of verdigris and
must be taken that the heat is not too high, or dried unless this precaution be adopted, the
;
the salt becomes decomposed. As in the case of first coating produced by the marcs will be
sodium acetate, no sparks must touch the mass, black instead of green. They are heated over a
or it may burn away like tinder. charcoal fire until as hot as the hand can bear,
The product, when prepared from the brown and placed in an earthenware vessel in layers
liquor, is dark-coloured and contains char- with the marcs. 30 to 40 Ibs. of copper are
coal and decomposed tarry matters it may be
; used for each vessel. In from ten to twenty
dissolved in 3 parts hot water, filtered through days, according to the temperature, the covers
animal charcoal, and again evaporated and are removed, when, if the process has pro-
crystallised yielding a nearly colourless product. gressed favourably, the marcs will be whitish
Pure calcium acetate crystallises in silky and the copper covered with fine, glossy, green
needles or prisms containing two molecules of crystals. The plates are then removed and
water. At the ordinary temperature the crystals placed on end one against another. After two
effloresce, and at 100 become anhydrous, form- or three days they are moistened by immersion
ing a white powder of saline taste, very soluble in water or damaged wine, and again placed on
in water. end for about a week. This alternate moisten-
Calcium acetate is used in the preparation of ing and exposure to the air is continued for
other acetates, and of acetic acid, and in calico- about six or eight weeks. The plates thus be-
printing. The pure salt is completely soluble in come covered with increasing coatings of the
water and proof spirit. The commercial article verdigris, which is detached and the plates are
usually contains 62 to 67 p.c. of real acetate, again used until entirely eaten away. The
and 1 to 8 p.c. of matters insoluble in water. verdigris is kneaded with a little water into
The impurities are hydrate, carbonate, and sul- leather bags, pressed into rectangular cakes and
phate of lime and tarry matters formate and
; dried.
other salts of lime with fatty acids also occur. This substance is known as blue verdigris,
Many methods of assay for this substance and consists principally of the basic acetate
are in use, varying considerably in accuracy.
The most trustworthy method is to distil (C 2 H 3 2)2 Cu 2 0.
with pure phosphoric acid and titrate the distil- It should be dry, of a fine bluish colour, and
late as already described under acetic acid (see soluble in dilute acids and ammonia.
Stillwell, J. Soc. Chem. Ind. 1904, 305; Green verdigris contains as a principal consti-
Grosvenor, ibid. 530; Gladding, J. Ind. Eng. tuent the sesquibasic acetate, CuO2Cu(C 2 3 O 2 ) 2 , H
Chem. 1909, 250). and is prepared by placing the copper plates
Calcium aceto-chloride H
CaC 2 3 2 Cl,5H 2 has alternately with cloths moistened every two or
already been described as used in Condy's pro- three days with pyroligneous acid or acetic acid
cess for the preparation of pure acetic acid. until the plates show green crystals. The plates
Copper acetates. are arranged so as to allow free access of air and
The normal copper acetate is prepared by occasionally moistened, for five or six weeks.
dissolving cupric oxide or verdigris in acetic acid ; Large quantities of verdigris are manufactured in
or by the action of copper sulphate on the ace- England by this process from pyroligneous acid.
tates of lead, calcium, or barium. The imports of verdigris are very small.
It crystallises in prisms soluble in 13 parts
;
The various forms of verdigris are used as
cold or 5 parts hot water, and in 14 parts al- oil and water colours. With white lead it is
cohol. In commerce it usually occurs in bunches used in Russia and Holland as an oil paint,
of deep-green coloured opaque crystals known which by double decomposition produces a
as 'grappes.' peculiar green. The paint is considered a good
Copper acetate is used in the manufacture preservative. Verdigris is used in dyeing and
of pigments ; as an oxidising agent in the indigo calico-printing, and for the preparation of
vat ; and, to a slight extent, for the preparation Schweinfurth green and other copper paints.
of acetic acid. Verdigris is frequently adulterated with chalk,
Basic copper acetate. Verdigris. Vert-de-gris. sand, clay, pumice, and sulphates of copper,
Vert de Montpellier. Grilnspan. barium, and calcium. When brass sheets have
16 ACETIC ACID.
been used in the preparation instead of copper, quantity of a weaker acid, 86-5 parts of litharge
zinc will also be present. are added in small quantities, with constant
When warmed with dilute hydrochloric acid stirring, until the liquid is nearly neutral ; it is
the sand, clay, baryta, &c., will remain undis- then heated to boiling and impurities skimmed
solved, and may be weighed. The total residue from the surface, transferred to another vessel
in a good sample will usually amount to 3 p.c., and evaporated to a density of 1-5, and removed
but should not exceed 6 p.c. to the crystallising pans, which are usually of
Aceto-arsenite of copper. Schweinfurth green wood, lined with lead or copper, 4 feet by 2 feet,
(v. ARSENIC). and 6 or 8 inches high. The coarsely crystalline
Ferric acetate Fe 2 (C 2 H 3
2)6
This salt is
. mass thus obtained is drained on wooden racks,
prepared by the addition of calcium or lead and broken into lumps for the market.
acetate to ferric sulphate or iron alum, avoiding A
coarser variety, known as brown acetate, is
excess of the acetate. It is used as a mordant, its prepared by substituting distilled pyroligneous
action corresponding with that of aluminium ace- acid for the purer acid. The muddy liquid pro-
tate. An alcoholic solution is used in medicine. duced is settled in a large tun, and the super-
For many purposes a mixture of ferrous and natant liquid transferred to a large iron pan and
ferric acetates is preferred. It is prepared by heated to boiling. It is again allowed to settle,
repeatedly pouring pyroligneous acid on iron transferred to another pan, evaporated until
turnings until saturated with iron. The liquid
' '
crystallisation commences, and about 3 volumes
is known at pyrolignite of iron,' bouillon noir,' of water added, causing the remaining impurities
'
liqueur de ferraille.' i to rise to the surface. The liquid is skimmed

H
Ferrous acetate Fe(C 2 3 O 2 ) 2
Pyrolignite of
. and diluted if the liquid is not sufficiently clear,
iron ; iron liquor or black liquor. Is prepared i
and again evaporated until a small portion of
on the large scale by the action of crude pyrolig- the liquid crystallises on removing and cooling.
neous acid of sp.gr. 1-035 to 1-040 on iron
I
!
It is then ladled into pans and allowed to
turnings, nails, &c., at a temperature of 65. i
crystallise.
The is frequently agitated and the
solution As a rule,
about 3 parts acetate are produced
tarry matters skimmed from the surface as they from 2 parts litharge.
rise. By another method granulated lead, white
It is found that the purified acid produces a lead residues, &c., are placed in vessels standing
less satisfactory liquor, a fact due, according to obliquely one above another ; the upper vessel is
filled with strong acetic acid, which after the
Moyret ( J. Soc. Dyers, i. 117), to the presence of a
small quantity of pyrocatechol in the crude acid, expiration of half an hour is allowed to run into
which forms a compound with the ferrosoferric the second vessel. Every half-hour it is re-
oxide in the solution, and causes its intense moved to a lower one. After the acid has been
colour and keeping properties. removed, the lead absorbs oxygen rapidly, and
The liquid is intensely black, of sp.gr. 1-085 |
becomes heated. On leaving the last vessel,
to 1-090, and is evaporated until its density rises the acid is again passed through the series, dis-
to 1-120, or sometimes to 1 140. It is then ready solving the acetate which has been formed, and
'
for use, and is known as printer's iron liquor.' !
is evaporated and crystallised.
The liquor of density 1-120 contains about 10 Schmidt (Eng. Pat. 1897, 7192) describes a
p.c. iron. process for preparing the neutral and basic
The density of the liquor used by dyers is | acetates of metals such as lead and copper by
frequently raised by the addition of copperas |
the action of dilute acetic acid and oxygen upon
(ferrous sulphate) ; thus, the addition to 1 gallon j
the metal contained in closed iron cylinders.
of black liquor, sp.gr. 1-085, of \ Ib. copperas, \ Pure lead acetate is a white crystalline salt
would raise its density to 1-111. Tannin also is of sweetish taste and weak acid reaction, con-
sometimes added. taining 3 molecules of water. It dissolves in
Black liquor is also prepared by the action of I 1-5 parts cold water, and in 0-5 hot water. At
ferrous sulphate on acetate of lime ; the liquor |
280 it melts, and when heated more strongly it
produced has an average density of I'll, and forms a basic salt and suddenly solidifies.
always contains sulphate of lime. By the action Lead acetate is largely used in dyeing and
of lead acetate on ferrous carbonate, carbonate j
calico-printing; for the preparation of alum
of lead and
ferrous acetate are produced. mordants, &c. ; in the manufacture of chrome
Black liquor absorbs oxygen from the air, yellow and other pigments, and in medicine.
forming ferric acetate, which is always present Lead forms two well-defined basic acetates
in the liquid. To dimmish this action clean H
the dibasic acetate Pb(C 2 3 O 2 ) 2 PbO,2H 2
metallic iron is frequently added. (Wittstein, Annalen, 52, 253), formed by dis-
It is largely used in calico-printing and in solving litharge in the normal acetate in cal-
dyeing, in the preparation of blue, violet, black, culated proportions and the tribasic acetate
;
brown, and other colours, and for producing a Pb(C 2H 3 2 ) 2 2PbO-aq, prepared by boiling the
black colour on hats, furs, leather, wood, &c. normal acetate with excess of litharge for some
Lead acetate. Normal or di-acetate of lead. time. Solutions of subacetate of lead are used
Sugar of lead. Sel de Saturne. Bleizucker. in medicine as Goulard water and Liquor plumbi
Pb(C 2 H 3 2 ) 2 . subacetatis.
For the preparation of white acetate of lead, Magnesium acetate. A
basic acetate of mag-
leaden vessels are used, or copper pans, on the nesia, prepared by warming the normal acetate
bottom of each of which a piece of metallic lead with magnesia, is stated to be a powerful anti-
is soldered to produce a galvanic action and septic, disinfectant, and deodoriser (W. Kubel,
prevent the copper from being acted upon. In Ber. 15, 684-686). A syrupy solution of the salt
the vessel acetic acid of 45 p.c. or less is placed, containing suspended magnesium hydroxide is
found in commerce under the name of Sinodor.'
'
and to 100 parts of 45 p.c., or a proportionate
ACETIC ACID. 17
Potassium acetate C 2 H 3 O 2 K occurs in the sap isoAmyl acetate, generally known as amvl
of many plants, and of trees. acetate (CH,) 2 CH-CH CH 0-C H
2 2 2 3 O, is a colou?-
Its mode of preparation is similar to that of less liquid of an odour
resembling that of jar-
sodium acetate. It is a deliquescent crystalline gonelle pears. Sp.gr. 0-8762 15/4 (Mendele'eff )
solid, soluble in 0'53 part ice-cold water, and in 0-8562 22/4 (Briihl), b.p. 138-5-139 at 758-6
hot water forms a solution which, boiling at (Schiff).
169?, contains 88 p.c. of the salt. It may be prepared
by distilling a mixture of
When chlorine gas is passed through a solu- 1 part amyl alcohol, 1 part strong sulphuric
tion of potassium acetate, carbonic acid is evolved acid, and 2 parts dried potassium acetate or
by ;
and a powerful, unstable, bleaching fluid id pro- warming a mixture of 1 part amyl alcohol, 1
duced. part acetic acid and 0-5 part strong sulphuric acid
Potassium acetate may contain the same on the water-bath and
pouring the solution when
impurities as the sodium salt. The di- and tri- cold into excess of water. The
upper layer of
acetates are prepared like those of sodium. purified amyl acetate is separated, shaken with
Sodium acetate C 2 H 3 O 2 Na is formed (1) by a strong solution of sodium carbonate,
again
the action of dilute acetic acid on sodium carbo- separated, dried over calcium chloride, and re-
nate, the solution being evaporated and crystal- distilled.
lised ; (2) by neutralisation of pyroligneous acid may be prepared commercially from fusel
It
with soda, and evaporation and fusion of the salt oil, hydrochloric acid, and calcium acetate
to remove tarry matters ; (3) by the addition of (Wilson, Eng. Pat. 4669). The commercial amyl
Glauber's salt to solution of acetate of lime or acetate contains some of the other isomerides.
of lead. The solution is decanted and filtered It is insoluble in water, but dissolves in all
from the precipitated calcium or lead sulphate, proportions in ether, amyl alcohol, and ordinary
evaporated and crystallised, and the crystals alcohol. The latter solution is largely used
dissolved and recrystallised. Methods (2) and under the name of Jargonelle pear essence for
(3) are used on the manufacturing scale. flavouring confectionery.
Sodium acetate forms monoclinic crystals, Camphor, tannin, resins, &c., dissolve readily
containing 3 molecules of water ; has a strong in amyl acetate. A solution of gun-cotton there-
saline taste is soluble in 2'8 parts cold water in is used as a varnish, for
;
lacquering metals,
and in 0-5 boiling water. The crystals melt com- &c., and in the form of a stiff jelly, mixed with
pletely at 75 and lose their water of crystallisa- opaque substances such as china clay, as a sub-
tion at 100. By solution of this salt in ordinary stitute for celluloid.
strong acetic acid and rapid evaporation the di- It is also used in the manufacture of photo-
acetate of soda is formed when glacial acid is
; graphic films and in some smokeless powders.
used the triacetate is produced. It has been recommended for use for the
Sodium acetate is used for the preparation of production of a standard flame in photometry
acetic acid and in medicine ; for the preserva- (J. Soc. Chem. Ind. 1885, 262).
tion of meat and other foods instead of salt. The Hefner standard lamp burns amyl
The saturated solution is occasionally used for acetate as an illuminant.
fillingcarriage foot- warmers. Ethyl acetate. Acetic ether C 2 H 5 (C 2 H 3 2 is
)
The commercial acetate is liable to contain a fragrant limpid liquid of sp.gr. 0-9072 15/15,
sulphates, chlorides and carbonates, and me- b.p. 77-5 (Perkin); sp.gr. 0-92446 0/4, b.p.
tallic salts. Tarry matters are frequently pre- 77-17 at 760 mm. (Young and Forty).
sent from the pyroligneous acid used in its For the preparation of acetic ether 3-6 pts. by
/ manufacture. Acetate of lime, and sulphate weight of commercial absolute alcohol is mixed
and carbonate of potash are occasionally added with 9 pts. sulphuric acid with constant stirring.
as adulterants. After standing twenty-four hours the mixture
For the estimation of acetic acid in com- is poured on 6 pts. of fused sodium acetate (in
mercial acetates the method of Stillwell and small lumps), allowed to stand for twelve hours
Gladding in a modified form is used (v. supra). and distilled. The product is rectified over cal-
cium chloride and carbonate of potash and re-
ALKYL ACETATES. Acetic ethers. distilled. Clark recommends the following pro-
Acetic acid forms numerous acetates with cess : 283(10 oz.) of rectified alcohol (sp.
c.c.
organic radicles. Some of these occur in the oils gr. 0-838) are placed in a flask, and 283 c.c. of
from various seeds. sulphuric acid (B.P.) are added with constant
Amyl acetates C'5H 11 (C 2 H 3 ). !! stirring. The liquid should be cooled externally
The following isomeric amyl acetates are as far as possible, allowed to stand till the tem-
known :
perature has sunk to 15, and 351 grams
1. Normal amyl acetate,
boiling at 147'6 (12| oz.) of dried sodium acetate added gradually
(Gartenmeister) at 148-4 (737 mm.) (Lieben
; with constant stirring and cooling. The liquid
and Rossi). is distilled until 400 c.c. (14 oz.) has passed
2. Isoamyl acetate. over this is digested for three days with
;
3. Methyl propyl carbinyl acetate, boiling at 2 oz. freshly dried potassium carbonate and
133-135 (Wurtz); at 134-137 (Schorlemmer). filtered. The filtrate is distilled on the water-
4. Methyl wopropyl carbinvl acetate, boiling bath until all but 1 oz. has passed over. On the
at 125 (Wurtz). large scale dried sodium acetate may be sub-
5. Diethyl carbinyl acetate, boiling at 132 stituted for the potassium carbonate with ad-
(741 mm.) (Wagner and Saytzeff). vantage (v. further W. I. Clark, Pharm. J. [3]
Tertiary amyl acetate, boiling at 124
6. 1883, 777).
(750 mm.) (Flavitzky). Ethyl acetate is soluble in 8 parts of water
Of these, only the second is of technical in- at 0, and somewhat less soluble in water at
terest. 15. On the other hand, 1 part water dissolves
VOL. I. T.
18 ACETIC ACID.
26 parts of the acetate at and 24 parts The value of the product depends upon the
at 15. extent to which combination has taken place,
Commercial acetic ether usually contains less and this is determined by observing the specific
than 75 p.c. of ethyl acetate, the rest being gravity and estimating the free and combined
acetic acid, alcohol, water, ether, &c. It occurs, acetic acid. The density varies between 1-1608
together with other organic acetates, in vinegar and 1-1896, being lowest when the free acetic
and wines. acid is present in largest amount. The free
Methyl acetate CH H
3 (C 2 3 2 ) is a colourless
and combined acetic acid are determined as
'
fragrant liquid of sp.gr. 0-9398 15/15, boiling follows : 50 grams of ' acetin are diluted with
at 57-5 (760 mm.) (Perkin). It occurs in wood- water to 500 c.c. The free acid in 50 c.c. of this
spirit, and in crude wood-vinegar. solution is determined by titration with normal
Methyl acetate is best prepared by distilling caustic soda, using phenolphthalein as indicator.
a mixture of 1 part methyl alcohol, 1 part potas- 15 c.c. of normal caustic soda are added to 10 c.c.
sium acetate, and 2 parts sulphuric acid. The of the acetin solution, and the combined acetic
product is dried over calcium chloride and quick- acid liberated by hydrolysis by boiling for five
lime and redistilled. w It is soluble in water, minutes. The excess of caustic soda remaining
alcohol, and ether. is a measure of the total acid present ; and the
ACETINS. The acetins are the acetyl deriva- amount of combined acid is found by subtract-
tives of glycerol, or glycerol acetates. Five of ing from the amount of caustic soda used up in
these are theoretically possible, two mono-, two the hydrolysis the quantity accounted for by
di-, and one tri- derivative, according to the the free acid. The following table (Kopp and
number and position of the hydroxyl groups Grandmougin, Bull. Soc. Ind. Mulhouse, 1894,
attacked by the acetic acid. Only three of 112) shows the results of typical analyses:
these compounds have been prepared so far,
one in each class, and the positions which the
acetyl groups take up in the mono- and di- deri- No.
vatives does not appear to be experimentally
proved, though they are probably terminal.
Commercial acetin is a mixture of all three
compounds with other products.
The following method for the preparation of
mono-, di-, and tri-acetin has been described by
A. C. Geitel ( J. pr. Chem. 1897, [ii.] 55, 417) :'
200 grams of dry glycerol are heated with
500 grams of glacial acetic acid for 8 hours, and
the acetic acid and water distilled off under re-
duced pressure. A further quantity of 150 grams
acid is then added, and the heating continued for
16 hours. Triacetin is isolated from the product
by diluting with water and extracting with ether,
and is a colourless liquid, dissolving in water to
the extent of about 7 p.c. at 15. It has a sp.gr. j
1-1605 at 15 and distils without decomposition

at 172-172-50/40 mm. Diacetin is obtained from
the remaining solution by fractionating (after
concentration) under a pressure of 40 mm., when |
'
it comes over between 175-176. It is a soluble

colourless liquid with sp.gr. 1-1769 at 15. In
order to isolate the monoacetin formed in the
reaction the aqueous solution after removal of
the triacetin is extracted for 8 hours with ether
at 34-35 in an extracting apparatus for liquids ;
the later extracts are collected separately, diluted
with an equal volume of water, and, after being
extracted with hot benzene, are concentrated.
The monacetin thus formed is a thick syrup of
sp.gr. 1-2212 at 15. By prolonging the ether
extraction still further monacetyldiglycerol
H H
C 3 5 (OH) 2 -0-C 3 5 (OAc)-OH may be obtained ;
it is a colourless liquid of sp.gr. 1-2323 at 15.
Diacetyldiglycide may also be separated from

the monacetin by fractionation, and triacetyl-
diglycerol is also formed.
Commercial Acetin (' Acdine ') is prepared by
heating in an oil-bath a mixture of 60 parts of
glycerol and 82 parts of glacial acetic acid for
12-15 hours at 120, and gradually raising the
temperature to 160 to expel the excess of acetic
acid. The product is a thick liquid smelling of
acetic acid and varying in colour from light
yellow to dark brown, according to the purity
of the glycerol used.
ACETOACETIC ACID. 19
obtained by the action of sodium iodide on the Ethyl acetoacetate is prepared by the action
corresponding chloro- compound. It is an un- of sodium on ethyl acetate. The following
stable oil having a sp.gr. 1.4584 at 15. details of the method are
given by Conrad
J. A. P. (Annalen, 186, 214) 100 grams of sodium are
:
ACETOACETIC ACID CH 3 -CO-CH 2 -C0 2 H is added to 1000 grams of pure ethyl acetate, and
.a thick acid liquid miscible with water in all after the reaction has moderated
considerably,
It is prepared from its ethyl ester the whole is heated on a water- bath under a
proportions.
oy leaving 4 parts of ester in contact with 2*1 reflux condenser for 2-2J hours until all the
for 24 sodium has disappeared. To the warm mass
parts of potash and 80 parts of water
hours and acidifying with sulphuric acid. It is 550 grams of 50 p.c. acetic acid are added, and
extracted from the solution with ether. after cooling 500 c.c. of water. The whole is
It is very unstable and readily decomposes well shaken, and the upper layer separated,
below 100 into acetone and carbon dioxide. It washed with a little water, and fractionated.
yields a violet colouration with ferric
chloride The fractions 100-130, 130-165, 165-175,
and forms ill- characterised amorphous salts, 175-185, 185-200 are collected separately
BaA 2 ,2H 2 and CuA 2 ,2H 2 O, when treated with and refractionated twice. The yield is 175
the corresponding carbonate. grams of product boiling at 175-185, and from
Acetoacetic acid appears in the urine of the fraction boiling below 100, 350-400 grams
diabetic patients, and indicates defective oxida- of ethyl acetate may be recovered after removing
tion. Its detection and estimation have been 'he alcohol by salting out.
the subject of much controversy and investiga- Ethyl acetoacetate is neutral to litmus, but
tion. Arnold (Chem. Zentr. 1899, ii. 146) makes 'orms salts with sodium, copper, and other
use of a colour reaction with acetophenone, which metals by replacement of hydrogen. Only one
will show 1 part in 10,000, but is affected to atom hydrogen can be replaced by sodium,
of
some extent by the presence of acetone. Riegler but the sodium in the resulting compound is
if
(Chem. Soc. Abstr. 1903, ii. 112) employs the replaced by an alkyl radicle a second hydrogen
colour produced by the addition of sulphuric atom may then be replaced. Ferric chloride pro-
and iodic acids, which he states to be unaffected duces a violet colouration. With sodium bisul-
by the presence of sugars, leucine, tyrosine, or phite a crystalline addition product C 6 Hi 3 ,
acetone. Bondi (Chem. Zentr. 1906, i. 707) NaHS0 3 is formed. On heating for a long time,
recommends the use of a solution of iodine and or leading the vapour through a hot tube, acetone,
the detection of acetoacetic acid by the cha- alcohol, dehydracetic acid, and methane are
racteristic smell of the iodacetone produced ; formed. Sodium amalgam reduces it to /3-hydroxy
but Lindemann (ibid. 717) says that this smell butyric acid CH 3 -CH(OH)-CH 2 -C0 2 H. It con-
is not characteristic of acetoacetic acid. Mayer denses with hydroxylamine, but does not form
adds the urine to a very dilute solution of ferric an oxime, as internal condensation takes place,
chloride in brine, when, in the presence of resulting in the production of methyl iso-
acetoacetic acid, a claret-red ring is formed. oxazolone CH 3 -C-CH 2 -CO which is converted by
When the red colour is only just visible, the N--- 6
liquid may be assumed to contain 0-01 p.c. of
the acid. A blank test performed after boiling
alkalis into salts of -oximinobutyric acid.
the acid for five minutes should give no colour Applications in Synthesis. By means of
ethyl acetoacetate fatty acids, ketones, and many
(Chem. Zentr. 1906, i. 406).
ring compounds may be prepared.
Messinger's process as modified by Huppert
Fatty acids may be obtained by dissolving
(Analyse des Harns, 1898) estimates the total sodium (1 atom) in absolute alcohol, adding
amount of acetone and acetoacetic acid present
with fair accuracy, and the acetone may be ethyl acetoacetate (1 mol.) followed by an
alkyl halogen compound (1 mol.). The resulting
estimated separately with considerable exacti-
tude by the method of Folin (J. Biol. Chem. alkyl derivative is treated with strong alkalis,
when the molecule is hydrolysed with formation
1907, 3, 177), in which it is aspirated out of the
of acetic acid and the desired alkyl acetic acid.
liquid into iodine and potash, and the resulting
iodoform weighed. CH 3 -CO-CH -C0 H -> CH 3 -C(ONa):CH-C0
2 2 2
Et
Methyl acetoacetate CH 3 -COCH 2 -C0 2 Me is -5 CH 3 -CO-CHR-C0 Et -> CH -CO,H 2 3
prepared by heating together methyl acetate and + ECH 2 -C0 2 H.

sodium under a reflux condenser and subse-
the hydrolysis is brought about by dilute
If
quently distilling in a stream of carbon dioxide. concentrated alkalis, the
It is a colourless liquid, easily miscible with water, acids instead of
which boils at 169-170 and has a sp.gr. 1-0917 molecule is differently divided, producing
at 4 ; 1-0809 at 15 ; and 1-0724 at 25. It is ketones.
decomposed on boiling with water into carbon CH 3 -CO-CHR-C0 2 Et ->

dioxide, acetone, and methyl alcohol. With CHCO-CH 2 R EtOH + C0
ferric chloride it yields a deep red colouration.
CH Dialkyl acetic acids and ketones may be pro-
Ethyl acetoacetate (acetoacetic ether) 3 -CO-
CH 2 -C0 2 Et and CH 3 -C(OH) : CH-C0 2 Et, was duced by introducing a second alkyl radicle into
discovered by Geuther in 1863, and independently the molecule by a similar process after the first
by Frankland and Duppa in 1865. It is a has entered, but the two cannot be introduced
colourless, slightly syrupy liquid, with a pleasant together in one operation.
the most important
odour. It boils at 186-6 -i81-2/754 mm. (Briihl) ; Pyfazolones, of which
180-180-3 /754-5 mm. (Schiff) mm. industrially is antipyrine,
are produced by the
; 71/12-5
and 100-2/80mm. (Kahlbaum). It has a specific condensation of ethyl acetoacetate with hydra-
gravity 1-0465 0/4 (Schiff); 1-0282 20/4 zines. Antipyrin (l-phenyl 2 3-dimethyl-5-pyra-
:
zclone) is prepared
from symmetrical methyl
(Schaum). *
C
ACETOACETIC ACID.
T
phenylhydrazine and ethyl acetoacetate (v. also Ethyl propylacetoacetate(JR 3 -(JO-CRP a-CO,&
PYRAZOLE and ANTIPYRINE). boils at 208-209, and has sp.gr. 0-981 at
PhNH OEt-CO 0/4. It is prepared by adding to a solution
of 27 grams of sodium in 270 grams absolute
,,TT
MeNH alcohol, 152-7 grams ethyl acetoacetate, followed
HO-CMe gradually by 206 grams propyl iodide.
PhN-CO CH 3 -COCHPr-
Ethyl isopropylacetoacetate
>CH + EtOH + H 2 0- C0 2 Et boils at 201/758-4, and has sp.gr.
0-9805 at 0.
MeN-CMe CH 3 -CO-CH(CH 2 -
Ethyl isobutylacetoacetate
Quinolines may be prepared by first making CHMe 2 )-C0 2 Et boils at 217-218, and has sp.gr.
the anilide of ethyl acetoacetate by heating 0-951 at 17-5 (Rohn, Annalen, 190, 306 ; Minter,
with aniline at 110, and afterwards heating Ber. 1874, 501).
this product with concentrated hydrochloric CH 3 'COCH(CH 2
Ethyl isoamylacetoacetate
acid. CH -CO-CH -CO-NHPh changes
3 2
into CH 2 -CHMe 2 )C0 2 Et boils at 227-228 (Peters,
CH 3 -C(OH) CH-C(OH) NPh, and readily
: : con- Ber. 1887, 3322).
denses to l-hydroxy-l-methylquinoline
Ethyl amylacetoacetate CH 3 -COCH(C 5 H n )
N N C0 2 Et boils at 242-244 (Ponzio and Prandi,
XCOH Gazz. chem. ital. 28, ii. 280).
Ethyl heptylacetoacetate boils at 271-273, and
CH has sp.gr. 0-9324 at 17-7.
CH Ethyl octylacetoacetate boils at 280-282, and
CMe has sp.gr. 0-9354 at 18-5/17-5.
HO-CMe 2. Di-substituted alkyl derivatives.
Pyridines (v. also BONE OIL) are obtained by- Ethyl dimethylacetoacetate CH
3 -CO'CMe 2
-
C0 Et boils at 184, and has sp.gr. 0-9913 at 16.

condensing ethyl acetoacetate with aldehyde 2
ammonias. Ethyl dihydrocollidine dicarboxyl- Ethyl methylethylacetoacetate CH 3 -COCMeEt

ate is the simplest example :
C0 2 Et boils at 198, and has sp.gr. 0-947
at 22/17-5.
C0 Et-CH HO-CHMe HC-CO ? Et
Ethyl methylpropylacetoacetate CH 3 -COCMe
2
PrCO,Et boils at 214, and has sp.gr. 0-9575 at

CH 3 -C-OH HNH HO-C-CH, 17 /4.
CHMe CH 3 -COCEt
Ethyl diethylacetoacetaie 2 -C0 2 Et
boils at 218, and has sp.gr. 0-9738 at 20.
CO 2 Et-C C-CO,Et
C-
boils at236, and has sp.gr. 0-9585 at 0/4.
Ethyl diisobutylacetoacetate boils at 250-253,
and has sp.gr. 0-947 at 10.
NH Ethyl diheptylacetoacetate boils at 332, and
Pyrones. Dehydracetic acid, a-methyl /3- has sp.gr. 0-891 at 17-5/17-5.
acetylpyrone, is produced on heating ethyl Ethyl dioctylacetoacetate boils at 264 /90 , mm
acetoacetate for a considerable time. 340-342 /760 mm.
Constitution. The constitution of ethyl aceto- ACETOL. Obtained as an ester of salicylic
acetate and its sodium derivatives was for many acid by condensing sodium salicylate with
years a subject of discussion by Frankland and monochloracetone OH-C 6 H4-COO-CH 2 -CO-CH 3 .
Duppa, Geuther, Claisen, Laar, Wislicenus, Forms needles from solution in alcohol, m.p. 71 ;
Briihl, Perkin, and others. The general opinion sparingly soluble in warm water (Fritsch, E. P.
is that ethyl acetoacetate consists of a mixture 3961, 1893; J. Soc. Chem. Ind. 1894, 274).
of the two forms, ketonic CH 3 -CO-CH,-C0 2 Et, ACETOMETER. A hydrometer graduated to
and enolic CH 3 -C(OH) CH-C0 2 Et. : The freshly indicate the strength of commercial acetic acid
prepared substance is practically a pure ketone, according to its density.
but on keeping it changes partially into the H
ACETONE C 3 6 or CH 3 -CO-CH 3 Dimethyl .
enolic form, and when equilibrium is reached ketone. A product of the destructive distillal ion
about 10 p.c. of the latter is present at ordinary of acetates ; obtained by Liebig from lead acetate
temperatures. The sodium compound is a deri- (Annalen, 1, 225) and further examined by
vative of the enolic form. Dumas (Ann. Chim. Phys. [2] 49, 208), who'
Alkyl derivatives of ethyl acetoacetate. first determined its composition. Acetone is
1. Mono-substituted alkyl derivatives. also produced in the drv distillation of wood
Ethyl methylacetoacetate CH 3 -COCHMc-C0 2 Et (Volckel, Annalen, 80, 310 ; J. Soc. Chem. Ind.
boils at 186-8, and has sp.gr. 1-009 at 6. 16, 667, 722 ; 27, 798) ; of citric acid (Robiquet,
Prepared from methyl iodide and sodium B. J. 18, 502) ; of sugar, starch, and gums with
acetoacetate (Geuther, J. 1865, 303). lime (Fremy, Annalen, 15, 279 ; J. Soc. Chem.
Ethyl ethyl acetoacetate CH 3 -CO-CHEt-CO 2 Et Ind. 21, 541, 1096). By oxidation of proteid
boils at 195-196, and has sp.gr. 0-9834 at 16. substances with iron salts (Blumenthal and
It is readily decomposed by baryta or alcoholic Neuberg, Chem. Zentr. 1901, i. 788; Ingler,
potash into alcohol, carbon dioxide and methyl Beitr.Chem. Phys. Path. 1902, i. 583), and
propyl ketone ; and by dry sodium ethoxide into by heating citric acid with potassium per-
acetic and butyric esters (Miller, Annalen, 200, manganate (P6an de St. Gilles, J. 1858, 585;
281 ; Wedel, Annalen, 210, 100 ; Frankland and Sabbatani, Atti Acad. Sci. Torino, 1900, 35, 678);
Duppa, Annalen, 138, 215 Wislicenus, Annalen,
; and by the oxidation of tsovaleric acid (Croseley
186, 187). and Le Sueur, Chem. Soc. Trans. 1899, 165).
ACETONE. 21
Preparation.- Acetone can be obtained

1. J. 53, 317).Acetone is used in perfumery and
by distilling a mixture of 1 part of caustic lime pharmacy; in the manufacture of smokeless
and 2 parts of crystallised lead acetate (Zeise, powders ; of cordite and of celluloid articles
Annalen, 33, 32) ; but is usually prepared by (Marshal, J. Soc. Chem. Ind. 23, 24, 645), also in
the dry distillation of barium acetate at a the preparation of iodoform (Teeple, J. Amer.
moderate heat. Calcium acetate can also be Chem. Soc. 26, 17Q Abbott, J. Phys. Chem. 7,
;
employed, but the temperature required is 83) of chloroform (Squibb, J. Amer. Chem. Soc.
;
greater, and the product is contaminated with 1896, 231 Orndorff and Jessel, Amer. Chem. J.
;
impurities, such as dumasin, an isomeride of 10, 363; Dolt, I.e. 271); and in the presence
mesityl oxide but according to Becker ( J. Soc. of sodium sulphite it can be used as a
;
good
('hem. Ind. 26, 279) a lower temperature is substitute for alkali in photographic developers
required the calcium salts are made quite
if (Lumiere and Segewetz, Bull. Soo. chim. 15^ [3]
neutral and the formation of free lime is pre- 1164; Mon. Sci. 1903, 257, 568; Eichengrun,
vented by the introduction of a stream of dry Zeitsch. angew. Chem. 1902, 1114). When its
carbon dioxide. Magnesium or strontium vapour is passed through a red-hot copper tube,
acetates can also be used. Industrially, ace- a very small proportion of tarry products con-
tone can be prepared by passing the vapour of taining naphthalene is obtained together with
acetic acid into air-tight vessels heated to 500, a large volume of gas having the composition :
containing some porous substances saturated carbon monoxide, 39-23 p.c.; methane, 37'58p.c.;
with lime or baryta (J. Soc. Chem. Ind. 18, hydrogen, 17-54 p.c.; and ethylene, 5-65 p.c. (Bar-
128, 824 ; Bauschlicker, D. R. P. 81914) ; also bier and Roux, Compt. rend. 102, 1559). De-
by passing a continuous current of pyroligneous hydrating agents readily act on acetone and
acid over a heated acetate capable of forming convert it into condensation products thus, ;
acetone (J. Soc. Chem. Ind. 25, 634 26, 1002 ; ;

caustic lime converts acetone into mesityl oxide
27, 277). An improved method is also described H H
C B 10 and phorone C 9 14 when the action is
by Wenghoffer (D. R. P. 144328; compare allowed to continue for a week (Fittig, Annalen,
aiso J. Soc. Chem. Ind. 14, 987 ; 20, 1130 22, ; 110, 32), and, together with smaller proportions
297). of other products, these two compounds are
According to Squibb (J. Soc. Chem. Ind. also formed when it is saturated with hydrogen
1896,^&8T; J. Amer. Chem. Soc.), pure acetone for chloride and allowed to stand for 8 to 14
use in the preparation of smokeless powders can days (Baeyer, Annalen, 140, 297) with zinc :
be obtained by subjecting acetates mixed with chloride terpene condensation products are
an excess of calcium hydroxide to destructive formed ( Raikow, Ber. 30, 905). Distillation with
distillation and to the action of superheated concentrated sulphuric acid converts acetone
steam. into mesitylene, mesityl oxide, phorone and
2. From wood-spirit acetone can be separated /sodureneand other substances (Orndorff and
by distilling over calcium chloride. The product Young, Amer. Chem. J. 15, 249). A similar
obtained by these methods can readily be purified result is obtained when it is heated with boron
by converting the acetone into its crystalline fluoride. The action of nitric acid and nitric
compound with acid sodium (or potassium) oxide on acetone has been studied by Newbury
sulphite, crystallising this, and subsequently and Orndoff (Amer. Chem. J. 12, 517), Behrend
distilling with aqueous sodium carbonate ; the and Schmitz (Annalen, 277, 310), Behrend and
distillate is then treated with concentrated Tryller (Annalen, 283, 209), Apetz and Hell (Ber.
calcium chloride solution and the ethereal layer 27, 933), Traube (Annalen, 300, 81), Mclntosh
rectified over solid chloride. According "to (Amer. Chem. Soc. 27, 1013) of hydrogen per- ;
Conroy (J. Soc. Chem. Ind. 19, 206), it should be oxide by Baeyer and Villiger (Ber. 32, 3625 33, ;
purified by distillation over sulphuric acid (Dott, 174, 858), Pastureau (Compt. rend. 140, 1591),
J. Soc. Chem. Ind. 27, 272), whilst Arnoult Wolffenstein (Ber. 28, 2265); of thionyl chloride
(ibid. 27, 679) recommends treatment with by Loth and Michaels (Ber. 27, 2540) and of ;
oxidising agents. hypophosphorous acid by Marie (Compt. rend.

Acetone has been prepared synthetically from 133, 219).
zinc methyl and acetyl chloride (Freund, Sodium in the presence of water reduces
Annalen, 118, 11). It occurs in the urine, blood, acetone to isopropyl alcohol and pinacone (Fittig,
and brain of calcium diabetic patients. Annalen, 110, 25; 114, 54; Stadeler, Annalen,
Properties. Acetone is a limpid, mobile 111, 277; Friedel, Annalen, 124, 329), but
when
liquid, having an agreeable odour and a pepper- the materials are quite dry and air is excluded,
mint-like taste. It is very inflammable and sodium acetonate is formed (Freer, Amer. Chem.
burns with a white smokeless flame, b.p. 56-3 J. 12, 355 13, 308
; 15, 582 Taylor, Chem.
; ;
(Regnault) sp.gr. 0-8144 at 0, 0-79945 at 13-9

; Soc. Trans. 1906, 1258 Bacon and Freer,
;
(Kopp, Annalen, 64, 214); b.p. 56-53 (corr.) J. Sci. 1907, 2, 67). Red-hot
Philippine
and sp.gr. 0-81858 at 0/4 (Thorpe. Chem. Soc. magnesium acts on acetone, yielding hydrogen
Trans. 37, 219); sp.gr. 0-81378 at 0/4, 0-79705 and allylene, whilst magnesium amalgam forms
decom-
at 15/4, 0-77986 at 30/4 (Saposchnikoff, J. magnesium acetonate which is rapidly
Russ. Phys. Chem. Soc. 28, 229); m.p. 94-9 posed by water, yielding pinacone hydrate
Conturior
(Ladenburg and Kriigel, Ber. 32, 1821 Formenti,
; (Reiser, Amer. Chem. J. 18, 328;
L'Orosi, 1900, 23, 223). Acetone is miscible in and Meunier, Compt. rend. 140, 721). Chlorine,
all proportions with water, alcohol, ether, and bromine, and iodine in the presence of alkalis
many ethereal salts; it can be separated from convert acetone into chloroform, bromoform,
its aqueous solution
by the addition of calcium and iodoform respectively.
chloride, and dissolves many fats and resins. Reactions. When quite pure acetone should
It is also an excellent solvent for acetylene remain perfectly colourless on exposure to light,
and tannins (Trimble and Peacock, Pharm. and should not be attacked by potassium
22 ACETONE.
permanganate in the cold; in the presence of Sabbatani, Chem. Zentr. 1899, ii. 22 ; Riegler,
alkali, however, and on warn: ing, carbonic and Zeitsch. anal. Chem. 40, 94 ; Vournasos, Bull.
oxalic acids are formed (Cochenhausen, J. pr. Soc. chim. 31, [3] 137; Graaff, Pharm. Week-
Chem. 166, 451 ; (Jonroy, J. Soc. Chem. Ind. blad, 1907, 44, 555; Folin, J. Biol. Chem. 1907,
19, 206; Fournier, Bull. Soc. chim. 1908, 3, 3, 177; Monimart. J. Pharm. Chem. 1892, 26,
259). Acetone, when treated with aqueous 392 ; Heikel, I.e. ; Hart, J. Biol. Chem. 1908, 4,
potash and iodine, yields iodoform (Lieben). 477.)
Gunning (Zeitsch. anal. Chem. 24, 147) has modi- Derivatives.Acetone combines directly with
fied this reaction to render it available when a large number of substances yielding well-
alcohol is present by employing ammonia and a characterised additive compounds. 1. Com-
ammonium iodide. Another
solution of iodine in pounds with alkaline sulphites Acetone forms
:
testproposed by Reynolds (ibid. 24, 147) is based definite crystalline compounds when shaken with
on the fact that mercuric oxide is soluble in concentrated solutions of the acid sulphites (bi-
acetone in the presence of potassium hydroxide ; sulphites) of the alkali metals (Precht, Phot.
the suspected liquid is mixed with a solution of Centr. 1902, 8, 301; Kerp, Kaiserl. Gesundh.
mercuric chloride rendered strongly alkaline with 1904, 21, 40; Roth wood, Monatsh. 26, 1545). The
alcoholic potash, and after shaking the mixture H
potassium salt C 3 6 0,KHS0 3 , and the sodium salt
is filtered and the filtrate tested for mercury by C 3 H 6 0,NaHS0 3 , crystallise in nacreous scales
means of ammonium sulphide or stannous (Limpricht, Annalen 93, 238) ; the ammonium
chloride. Deniges (Compt. rend. 126, 1868 ;
salt C 3 H 6 0,NH 4 HS0 3 crystallises in laminae
127, 963 ; Bull. Soc. chim. 13, [3] 543 ; 19, [3] (Stadeler, Annalen, 111, 307). The
barium
754) recommends the use of the additive com- salt has formula 2C 3 H 6 0,Ba(S0 3 H),,H 2 (Fa-
pound formed by acetone with mercury sulphate, gard, J. Pharm. Chim. 1895, 2, 145). These salts
for detecting acetone in methyl and ethyl yield acetone when heated with aqueous potash.
alcohol (Oppenheimer, Ber. 32, 986). Penzoldt 2. Compounds with c.hloroform (Willgerodt,
(Zeitsch. anal. Chen'. 24, 147) adds to the Ber. 14, 2451; 15, 2308; Cameron and Holly,
suspected liquid orthonitrobenzaldehyde, which Chem. Zentr. 1898, ii. 277 ; Jocitsch, ibid. 1899, i.
in presence of caustic alkali combines with ace- 606 ; Willgerodt and Diirr, J. pr. Chem. 148, 283).
tone to form indigo. Another delicate test is to 3. Compounds with hydrogen cyanide (Urech,
add sodium hydroxide, hydroxylamine and Annalen, 164, 255): Acetone yields acetone-
pyridine, then ether and bromine until the cyanhydrol C 4 H 7 NO, b.p. 120, when added to
solution is yellow, hydrogen peroxide is now anhydrous hydrogen cyanide ; and diacetone-
added when, if acetone is present, the solution H
cyanhydrol C 7 13 N0 2 a crystalline substance,
,
becomes blue (Stock) dimethyl p-phenylenedia-

;
when treated with a 25 p.c. solution (aqueous) of
mine produces a red colouration which changes hydrogen cyanide (Tiemann and Friedlander, Ber.
to violet on addition of alkali or acid (Malerba, 14, 1965) with 3'3 p.c. hydrogen cyanide acetone-
;
Zeitsch. anal. Chem. 37, 690). Similar colour re- cyanhydrin is obtained in the dark, but in the
actions are obtained by adding a few drops of light a mixture of products is formed (Silber,
sodium nitroprusside to a mixture of acetone and Ber. 38, 1671). 4. Compounds with ammonia:
a primary aliphatic amine (Rimini, Chem. Zentr. Ammonia unites with acetone in the cold with
1898, 2, 132). Of all these tests Lieben's is perhaps the elimination of the elements of water ; the
the most sensitive. To detect acetone in urine a reaction, however, proceeds more quickly if the
strong solution of sodium nitroprusside is added, temperature is raised to 100, or if dry ammonia
then the mixture made alkaline with potash, gas is passed into boiling acetone. Several
when a red colouration is produced which bases, diacetonamine C 6 H 13 NO, triacetonamine
changes to violet on addition of acetic acid (Legal, C 9 H 17 NO, triacetonediamine C 9 H 20 N 2 O, and
J. Pharm. Chim. 1888, 17, 206; Deniges, Bull. dehyclrotriacetonamineCgHjjN; the last two in
Soc. chim. [3] 15, 1058). According to Egeling very small quantity only, have been obtained by
(Chem. Zentr. 1894, ii. 457), it is best to use these methods, the relative proportions in which
ammonia, when a brilliant violet colour is at they are formed varying with the temperature
once produced this reaction is not given by
: and time employed. These bases and their
aldehyde. For other methods of detecting and derivatives have been examined by Heintz
estimating acetone, compare Arachequesne, (Annalen, 174, 133 175, 252 ; 178, 305, 326
; ;
Compt. rend. 110, 642; Collischonn, Zeitsch. 181, 70; 183, 276; 189, 214; 191, 122; 198,
anal. Chem. 29, 562; Squibb, J. Amer. Chem. 42, 87 ; 201, 90 ; 203, 336) and by Sokolow and
Soc. 18, 1068 Kebler, ibid. 19, 316 Schwicker,
; ; Latschinow (Ber. 7, 1384), Ruhemann and
Chem. Zeit. 15, 914 Strache, Monatsh. 13, 299
; ; Carnegie (Chem. Soc. Trans. 1888, 424), Riighei-
Klar, J. Soc. Chem. Ind. 15,299 Hintz, Zeitsch.
; mer (Ber. 21, 3325; 25, 1562), Harries (An-
anal. Chem. 27, 182; Sternberg, Chem. Zentr. nalen, 296, 328), Franchimont and Friedmann
1901, i. 270; Keppeler, Zeitsch. angew. Chem. (Rec. Trav. Chim. 1907, 223), Gabriel and Colman
18, 464: Vaubel and Schleuer, ibid. 18, 214; (Ber. 35, 3805), Kohn and Lindauer (Monatsh.
Jolles, Ber. 39, 1306; Auld, J. Soc. Chem. Ind. 23, 754), Kohn (Annalen, 351, 134 ; Monatsh.
25, 100 Heikel, Chem. Zeit. 32, 75.
; 24, 765, 773; 25, 135, 817, 850; 28, 429,
(For estimating acetone in wood spirit, see 508, 529, 537, 1040) ; they yield well-crystallised
Arachequesne, I.e.; Vignon, Compt. rend. 110, salts,and can be separated from one another
534 ; 1 12, 873 and in urine, see Huppert,
;
by means of their oxalates. Methylamine also
Zeitsch. anal.Chem. 29, 632; Salkowski, J. gives corresponding compounds with acetone,
Pharm. Chim. 1891, 194; Geelmuyden, Zeitsch. but dimethylamine yields dimethyldiaceton-
anal. Chem. 35, 503; Willen, Chem. Zentr. amine as the sole product (Gottschmann,
1897, i. 134; Martz, ii. 232; Argenson, Bull. Annalen, 197, 27).
Soc, chim. 15, [3] 1055; Studer, Chem. Zentr. Thioacetones have been studied by Bau-
1898, i. 1152; Mallat, J. Pharm. 1897, 6296; mann and Fromm (Ber. 22, 1035, 2592).
ACETONECHLOROFORM. 23
Acetone forms compounds with mercuric sul and Kegel, Ber. 23, 230; Claisen, Ber.
25,
phate (Deniges, I.e. ; Oppenheimer, I.e. ), wit] 3164 ; the azo- (Bulow and Schlotterbeck, Ber.
mercuric oxide (Auld and Hantzsch, Ber 35, 2187) and diazo- derivatives of
acetonyl
38, 2677; Lasserre, J. Pharm. Chim. 1890 acetone, have dyeing properties (Faurel, Compt.
22, 246), with mercuric cyanide (Marsh anc rend. 128, 318).
Struthers, Chem. Soc. Trans. 1905, 1878), with Acetone, with diazobenzene chloride in the
mercuric iodide (Gernez, Compt. rend. 137, 255 presence of alkali, yields a compound C 15 14 ON,. H
Marsh and Struthers, Chem. Soc. Proc. 1908 m.p. 134-135, which has dyeing propertie's
266), and with mercuric nitrate (Hof mann, Ber (Bamberger and Wulz, Ber. 24, 2793). For other
31, 2212). Metallic derivatives of the type condensation products compare Boessneck, Ber.
CH 3 'CO'CH 2
K
are obtained by the electrolysis 21, 1906 Pechmann and Wehsarg, ibid. 2989,
;
of acetone solutions of potassium or sodium 2994; Franke and Kohn, Monatsh. 19, 354-
iodides or of potassium thiocyanate (Levi anc 20, 876; Spier, Ber. 28, 2531; Perkin and
Voghera, Gazz. chim. ital. 35, i. 277). Thorpe, Chem. Soc. Trans. 1896, 14S2 ; Weidel,
Acetone yields substitution derivatives when Monatsh. 17, 401 Micko, ibid. 442 ; Stobbe,
;
acted upon with chlorine or bromine (Bischoff, Ber. 28, 1122; Cornelson and Kostanecki, Ber.
Ber. 5, 863, 963; 8, 1329). The folio wing deriva- 29, 240; Claisen, ibid. 2931; Rohmer, Ber. 31,
tives have been obtained: Monochloracetone 281 ; Pfitzinger, J. pr. Chem. 164, 283 Freer, ;
(Henry, Ber. 5, 190; Mulder, Ber. 5, 1009; Bar- Amer. Chem. J. 17, 1 Barbier and Bouveault,
;
baglia, Ber. 7, 467 ; Linnemann, Annalen, 134, Compt. rend. 118, 198; Haller and March,
171 Koenigs and Wagstaffe, Ber. 26, 554 ;
; Compt. rend. 139, 99 Straus, Ber. 37, 3293 ;
;
Wislicenus, Kircheisen and Sattler, ibid. 26, Harries and Ferrari, Ber. 36, 656 Ulpiani ;
908; Fritsch, ibid. 26, 597; Tcherniac, Ber. and Bernardini, Atti R. Accad. Lincei, 1904,
25, 2629 ; Kling, Bull. Soc. chim. [3] 33, 322) ; 13, 331 ; Pechmann and Sidgwick, Ber. 37,
unsymmetrical dichloracetone (Fittig, Annalen, 3816 ; Duntwitz, Monatsh. 27, 773 ; Knoeve-
110, 40; Borsche and Fittig, Annalen, 133, nagel, Ber. 39, 3451, 3457 Purdie, Chem. Soc.
;
112: Erlenbach, Annalen, 269, 46; Tcherniac, Trans. 1906, 1200 Richard, Compt. rend. 145,
;
I.e.
; Fritsch, I.e. ; Mclntosh, Chem. Soc. Trans. 129. Diacetones and their derivatives have been
1905, 790) symmetrical dichloracetone (Barba-
; studied by Combes (Compt. rend. 108, 1252;
glia, Fritsch, I.e.); trichloracetone (Bischoff,
I.e. ; Behal and Auger, Compt. rend. 109, 970 ;
I.e. ; Kraemer, Ber. 7, 252 ; Perrier and Prost, Claisen and Stylos, Ber. 21, 141); derivatives of
Compt. rend. 140, 146 ; Hantzsch, Ber. 21, 242); triacetone by Weinschenk (Ber. 34, 2185).
tetrachloracetone(Bischoff, Levy, Witte and ACETONECHLOROFORM, aaa-trichlor- 0-hy-
Curchod, Annalen, 252, 330, 254, 83 Levy ; droxy-/3-methylpropane (Chloretone) (CH 3 ) 2 -C(OH)-
and Jedlicka, Ber. 21, 318); and pentachlor- CC1 3 , prepared by slowly adding powdered
acetone (Cloez, Bull. Soc. chim. [2] 39, 638 ; potassium hydroxide (3 parts) to a cooled
Fritsch, Annalen, 279, 310 and I.e. Levy ;
mixture of acetone and chloroform
(5 parts)
and Jedlicka, I.e.). The corresponding bromo- Chem. [2] 37, 361) is
(1 part) (Willgerodt, J. pr.
derivatives, with the exception of tribromace- a white crystalline compound, b.p. 167, melt-
tone, are obtained by the direct action of bromine ing near but above 97 it has a camphor-
;
upon acetone (Mulder, J. 1864, 330 ; Mclntosh, like odour, is soluble in hot, sparingly soluble
I.e.; Lapworth, Chem. Soc. Trans. 1904, 33), in cold water, and crystallises well from ether,
also by other methods (Hjelt and Siven, Ber. alcohol, acetic acid, acetone, or chloroform ; it
21, 3288 Norton and Wistenhoff, Amer. Chem.
; forms no definite hydrate, but the system acetone-
J. 10, 213 Hantzsch, I.e.).;
Other halogen chloroform/water presents a quadruple point
derivatives (J. Soc. Chem. Ind. 16, 933 ;
For the solid, two solutions and the vapour at 75-2
Hantzsch, I.e. and Ber. 22, 1238) and the (Cameron and Holly, J. Phys. Chem. 1898, 2,
compounds of acetone with the halogen acids 322). The acetate (CH 8 ) 2 -C(OAc)-CCl, boils at
(Archibald and Mclntosh, Chem. Soc. Trans. 191. The benzoate (CH 3 ) 2 -C(OBz).CCl 3 boils at
1904, 924) have been described. 282 (Willgerodt and Diirr, J. pr. Chem. [2] 39,
Acetone forms a large number of condensa- 283 ). Acetonechlorof orm is reduced by zinc-dust
tion products and derivatives with other organic and alcohol, forming dichloroisobutylene, iso-
compounds Cyanacetones (Hantzsch, Ber. 23,
:
crotylchloride,andisobutylene (Jocitsch, J. Russ.
1472 ; Tcherniac, Ber. 25, 2607, 2621 ; Kowppa, Phys. Chem. Soc. 1898, 30, 920) ; and is decom-
Ber. 33, 3530). Acetone dioxalic ester obtained posed by water at 180, yielding hydrogen
by the action of sodium ethylate on a mixture chloride and hydroxyisobutyric acid (Willgerodt,
of acetone and oxalic ester is converted when Ber. 1882, 15, 2305). By the action of benzene
treated with sodium ethoxide to a dienolic n presence of aluminium chloride the chlorine
substance forming lemon-yellow needles, m.p. atoms of acetonechloroform are replaced wholly
98, and dyeing wool in alcoholic solution. >r in
part by phenyl residues, and the compounds
It is the first nitrogen free dye-stuff of the fatty diphenykhloromethyl dimethyl carbinol CPh 2 Cl-
series yet obtained (Willstatter and Pummerer, CMe 2 'OH b.p. 239 phenyldichloromethyl dimethyl
;
Ber. 37, 373.3). PseudocycZocitralidene acetone carbinol CPhCl 2 -CMe 2 -OH b.p. 217; and tri-
and its homologues have an odour of violets, jhenylmethyl dimethyl carbinol CPl^-CMe/OH
and are suitable for use in perfumes (J. Soc. ).p. 260, have been prepared, and similar
Chem. Ind. 24, 290). ompounds are obtained using toluene or p-
For acetone dicarboxylic acid and its deriva- :ylene (Willgerodt, J. pr. Chem. [2] 37, 361).
tives, see Ormerod, Chem. Soc. Proc. 1906, 205 ;
Acetonechloroform a powerful germicide, a
is
for
Deniges, Compt. rend. 128, 680 ; Lippmann, atisfactory surgical dressing, and hypnotic
Ber. 41, 3981; for acetonyl acetone and its internal use (Aldrich and Houghton, Amer.
derivatives, see Knorr, Ber. 22, 168, 2100 ;
J. Physiol. 1900, 3, 26); it is used as a
Claisen and Ehrhardt, Ber. 22, 1009 ; Zincke specific for sea-sickness (Merck, Ann, Report,
24 ACETONECHLOROFORM.
1907, and a 1-2 p.c. solution is used under the
1),
which are not diminished
anaesthetic properties,
name of anesin for producing local anaesthesia by condensing with aldehydes containing a
it
phenolic hydroxyl, but are destroyed

when it is
(Cohn, Pharm. Zentr. H. 40, 33).
ACETONEDICARBOXYLIC ACIDi-.KETONES. |
condensed with benzaldehyde, tolualdehyde,
ACETONE OIL is the oily residue remaining j
or cinnamaldehyde (Hildebrandt, Chem. Zentr.
after the separation of acetone from the products !
1905. ii. 502 : Scholz and Huber, Ber. 37, 390 ;
of the dry distillation of calcium acetate. It Schafer, Ber. 39, 2181).
can also be prepared by the dry distillation of Acetophenonephenetidene, m.p. 88, an anti-
the lime salts obtained by neutralising fleece pyretic substance, can be obtained by heating
washings with milk of lime. About 15 litres of molecular proportions of acetophenone and p-
the oil are obtained from a cubic metre of fleece phenetidene in vacuu, then distilling in vacuu at
11B.
It is a slightly-coloured 210-212 (Valentiner, J. Chem. Soc. Ind. 15,
washings of
liquid of 0-835, having a penetrating
sp.gr. 50; 17,602).
smell and acrid burning taste. It consists mainly j8-ACETO-PROPIONIC ACID. Lcevulic acid
of methyl ethyl ketone (A. and P, Buisine,
CH 3 -CO-CH 2 -CH 2
-C0 2 H.
Compt. rend. 126, 351 128, 561).
; According
to Duchemin (Bull. Soc. chim. [3][21, 798) acetone This substance is formed by the action of dilute
oil is of very variable composition, depending acids on a number of carbohydrates e.g. levu-
upon the nature of the pyrolignate from which it lose, inulin, galactose. It is also a product of
is prepa'red. A
French Commission reported that oxidation of the terpene alcohols, but is best
it was effective as a denaturant of alcohol and prepared by heating on the water-bath cane
it was adopted for this purpose by the Swiss sugar with dilute hydrochloric acid (4 vols.
Government in 1895. water, 1 vol. cone, acid) until a brown flocculent
For details of mode of manufacture from wool precipitate is no longer formed. (Compare Tol-
washings, v. Buisine (J. Soc. Chim. Ind. 18, lens, Ber. 17, 668 Wehmer a. Tollens, Annalen,
;
292; 21, 164); P. Baechlin, (Rev. Chim. Ind. 9, 243, 214.) The filtered liquid is then evaporated
112; 15, 240). on the water-bath, extracted several times with
ACETONIC ACID v. HYDROXYBUTYRIC ACID. ether, and after distilling off the ether the
ACETOPHENONE. Phenyl methyl ketone. residue is fractionated in a vacuum.
Hypnone C 6 H 5 -COCH 3 is obtained by acting It can be obtained by the hydrolysis of various
-
with benzoyl chloride on zinc methyl ; by nucleic acids (Kossel and Neumann, Zeitsch.
distilling a mixture of the calcium salts of physiol. Chem.
27, 2215; Inouye, ibid. 42, 117;
benzoic and acetic acids or by boiling together
; Levene, ibid. 43, 119). For other methods of
benzene and acetyl chloride with aluminium preparation, compare Tiemann and Semmler
chloride. It can be isolated from the fraction (Ber. 28, 2129) ; Verley (Bull. Soc. chim. [3]
of heavy oil of coal tar boiling at 160-190 17, 190); Erlenmeyer (j. pr. Chem. 179, 382);
by addition of sulphuric acid, distilling the Blaise (Bull. Soc. chim. [3] 21, 647).
solution in steam and converting the distillate Lsevulic acid crystallises in plates which
into the ^-bromophenylhydrazone derivative melt at 33. It boils at 239, 148-149 /15 mm.
of acetophenone (Weissgerber, Ber. 36, 754). (Michael, J. pr. Chem. 152, 113), and has at
It is best obtained synthetically by adding 15 a sp.gr. 1-135. It is very soluble in water,
small quantities of sublimed ferric chloride alcohol, or ether, and is not attacked by
(7 parts) to a mixture of benzene (5 parts) and bromine in the cold. Nitric acid converts it
acetyl chloride (7 parts) diluted with carbon into carbon dioxide, acetic acid, succinic and
disulphide. The mixture is then warmed on the oxalic acids. Iodine and sodium hydroxide form
water-bath, dried and fractionated (Nencki and iodoform even in the cold. Hydriodic acid and
Stoeber, Ber. 30, 1768). phosphorus at 200 convert it into normal valeric
Acetophenone crystallises in large plates, m.p. acid whereas sodium amalgam forms sodium
;
20-5; b.p. 202. It possesses a persistent 7-hydroxyvalerate acid in an alcoholic solution,

odour of oil of bitter almonds and cherry laurel and normal valeric acid in an acid solution.
water is insoluble in water, but dissolves easily
; When added to boiling iodic acid solution diiodo-
in alcohol,ether, chloroform, or benzene. acetoacrylic acid is formed (Angeli and Chiassi,
It readily oxidised by potassium perman-
is Ber. 25, 2205). When placed over sulphuric
ganate to phenylglyoxylic acid (Gliicksmann, acid in a vacuum it decomposes, leaving a
Monatsh. 11, 246). By the action of ammonia on residue of dihydroxyvaleric acid (Berthelot and
an alcoholic solution of acetophenone, the aceto- Andre, Compt. rend. 123, 341).
phenone ammonia is formed CMePh(N CMePh).,, : The mercury salt Hg(C 5 H 7 3)2, which crystal-
m.p. 115 (Thomae, Arch. Pharm. 244. 643) (v. lises up on treatment
in silvery plates, breaks
KETONES). with sodium hydroxide, forming the two mer-
Acetophenone forms a large number of deriva- curilsevulic acids C 5 H 6 O 3 Hg and C 5 H 4 3 Hg 2 .
tives and condensation products with aldehydes, Laevulic acid condenses with benzll
readily
halogens, acids, mercury salts, &c. (Japp and Murray, Chem. Soc. Proc. 1896, 146),
Acetophenone was discovered by Dujardin- and with aldehydes (Meingast, Monatsh. 26, 265).
Beaumetz and Bardet to possess powerful It forms a semi-carbazone, m.p. 187 (Blaise,
soporific properties (Compt. rend. 101, 960; I.e.).The ethyl ester when treated with ethyl
Karmensky, Liss. Med. Chi. Acad. St. Peters- magnesium bromide yields a lactone, b.p.
burg, 1888-1889, No. 70). In quantities of 0-05 105-106/18 mm. (Grignard, Compt. rend. 135,
to 0-15 gram, it induces a quiet sleep, but is
627). Halogen substitution derivatives of Ise-
said to impart a disagreeable odour to the vulic acid have also been obtained (Wolff, Ber.
breath (Pharm. J. 1886, 582). 26, 2216 Wolff and Riidel, Annalen, 294, 192;
:
Atninoacttophenone (Camps, Arch. Pharm. Conrad and Schmidt, Annalen, 285, 203).
40, 15), b.p. 250-252; 135/17 mm,, has The substance js employed on a manufac-
ACETYLENE GROUP.
turing scale as a mordant instead of acetic acid, acetylene at a red heat yields benzene (Bone
as it possesses the advantage of not being volatile and Coward, Chem. Soc.' Trans. 1908, 1197;
with steam. Bone and Jerdan, Chem. Soc. Proc. 1901, 165;
Italso used in the preparation of the anti-
is Maquenne, Compt. rend. 115, 558); allylene
pyretic untithermin. Phenylhydrazine is dis- H
C 3 4 , by the action of sulphuric acid, gives
solved in dilute acetic acid, and on adding a H
mesitylene C 9 12 (trimethyl benzene) ; and
solution of laevulic acid a yellow precipitate is H
crotonylene C 4 g gives hexamethyl benzene.
formed, which is purified by recrystallisation H
Acetylene C 2 2 i.e. HC CH is produced when
;
from alcohol (Pharm. J. [3] xvii. 801) (v. ANTI- an electric arc is formed between carbon points
THERMIN). in an atmosphere of hydrogen (Bone and Jerdan,
ACETOPURPURINE v. Azo- COLOURING Chem. Soc. Trans. 1897, 54). Further, by passing
MATTERS. the vapours of many carbon compounds (alcohol,
ACETPHENETIDENE v. PHENACETIN. ether, ethylene) through red-hot tubes (Bone and
ACETYLENE GROUP. Hydrocarbons having Coward, I.e.). It is also formed by electrolysing
the general formula CnH,n 4. the sodium or potassium salt of fumario or
The hydrocarbons of this series exist in two maleic acid, and by the action of silver, copper,
isomeric modifications. Representatives of the or zinc-dust on iodoform (Cazeneuve, Compt.
firstgroup are rend. 97, 1871). A steady stream of gas can
CH;CH CH -C;CH 3
be obtained by the action of the copper-zinc
Acetylene. Allylene. couple on bromoform (Cazeneuve, Compt. rend.
And of the second 113, 1054).
CH 2 : C CH,
: CH 2 : CH-CH 2 -CH 2 -CH CH, : By the action of water on the carbides of
Isomeric allylene, Diallyl. barium, calcium, or strontium (Travers, Chem.
The hydrocarbons of the first group thus Soc. Proc. 1893, 15; Maquenne, I.e. Moissan,
;
contain the group = CH united to one carbon Bull. Soc. chim. [3] 11, 1007).
atom, and may be designated true acetylenes. By allowing the flame of a bunsen burner to
strike back, or by the action of alcoholic potash
They form compounds with copper and silver in
which the hydrogen of the group (CH) is re- on ethylene dibromide.
placed by the metal. According to Matthews J. Amer. Chem. Soc.
(
When heated to a high temperature with 22, 106), agood laboratory method is to cover cal-
alcoholic potash in a sealed tube the triple bond cium carbide with absolute alcohol and add water
changes its position thus : drop by drop. The gas is purified by passing
into copper sulphate solution acidulated with
H
C 2 5 -CH,-C :.CH -> C 2 r -C:C-CH 3 H .
C2 5 H -C;CH'-t CH -C:C-CH 3 .
sulphuric acid, then over pumice stone saturated
3
with an acetic or sulphuric acid solution of
The reverse action occurs by boiling with
chromic acid.
metallic sodium.
The following general reactions yield hydro- Commercially acetylene is nearly always pro-
duced from calcium carbide (Lewes, J. Soc.
carbons of this series :
Chem. Ind. 16, 33; Clowes, ibid. 209, 319;
1. By heating the monohalogen derivatives
Wilson, ibid. 15, 103; Liipke, Elektr. Chem.
of the hydrocarbons C n 2n with alcoholic potash H Zeit. 1895, 145 Wyatt, J. Soc. Chem. Ind. 14,
;
CH 3 -CC1 :CH 2 +KOH=CH 3 -C: CH+KC1+H 2 O. 135 ; 796 20, 109

; Bamberger, Zeitsch. angew.
;
2. the action of alcoholic potash on the

By
Chem. 1898, A rapid evolution of
720).
gas is be obtained by treating
also said to
dihalogen derivatives of the ethylene series. In
this case the reaction takes place in two stages. calcium carbide with crystallised sodium car-
bonate previously mixed with powdered rock
I. CH,Br-CH 2 Br+KOH salt (J. Soc. Chem. Ind. Commercial
27, 438).
=CHBr CH +KBr+H :
2 2 0.
II. CHBr CH 2 +KOH=CH CH+KBr+H,0.
:
:
acetylene often contains as impurities ammonia,
:
other hydrocarbons, carbon monoxide, hydrogen,

The bromine derivatives give, as a rule, a
nitrogen, oxygen, arsine, sulphuretted hydrogen,
better yield than the chlorides. and phosphoretted hydrogen, the last of which
3. By electrolysing unsaturated dibasic acids. is the most dangerous. The action of the gas
CH-C0 2 H CH-CO 2 H=CH CH+2C0 2 +H 2
:
: . on copper is due chiefly to these impurities.
Fumaric acid Acetylene The gas can be purified and the impurities
The acetylenes combine with Br 2 or Br 4 ; thus detected by passing it through cooled solutions
acetylene forms C 2 2 Br 2 and C 2 2 Br 4 H H . of sulphuric acid, lime, lead or mercury salts,
Nascent hydrogen converts the acetylenes into and chromic acid in sulphuric or acetic acid
the hydrocarbons C,,H 2n and G n 2n+ ,. H (Clowes, I.e. ; Lunstroem, Chem. Zeit. 23, 180;
The presence of mercuric
acetylenes in Berge and Reychler, Bull. Soc. chim. [3] 17, 218;
bromide combine with water to form aldehydes Gottig, Ber. 32, 1879; Rossel and Landrisset,
and ketones (Kutscheroff, Ber. 14, 1542 17, 28). ; Zeit. angew. Chem. 1901, 77 ; Caro, J. Soc. Chem.
C 2 H 2 +H 2 0=C 2 H 4 O Ind. 22, 17 ; 23, 15 ; Ullmann and Goldberg,
Acetylene. Aldehyde. Chem. Zentr. 1899, ii. 19; Pfeifer, J. f. Gasb. 42,
CH 3 -C CH+H 0=CH 3 -COCH 3
:
2
551 ; Frasuckel, Chem. Zentr. 1908, ii. 643 ;
Allylene. Acetone. Eitner and Keppeler J. f. Gasb. 44, 548 ;
According to Desgrez (Ann. Chim. Phys. Jaubert, J. Soc. Chem. Ind. 24, 116; Willgerodt,
1894,3, 215; Bull. Soc. chim. [3] 11, 362), the Ber. 28, 2107; Hoffmeister, Zeitsch. anorg.
elements of water can be made to combine Chem. 48, 137).
directly with the acetylenes without the presence The best method of freeing acetylene from
phosphine is to pass the cooled gas over
of condensing or other agents. bleach-
By polymerisation of the acetylenes, coming powder, or the compound CaO,CaOCl 2 ,2H 2
pounds of the benzene series are formed. Thus or CaO,CaOCl 2 ,H 2 (Ditz,P. R. P. 1906, 162324),
26 ACETYLENE GROUP.
moistened with just sufficient water to make it magnesium, aluminium, chromium, manganese,
cohere in balls, and finally over lime (Lunge and iron, nickel, cobalt, bismuth, antimony, arsenic,
Cedercreutz, Zeitsch. angew Chem. 1897, 651 : and tin (Makowka, Zeitsch. anal. Chem. 46,
J. Soc. Chem. Ind. 16, 37 24, 1294 ; 27, 798 ;
;
145 ; Erdmann, ibid. 46, 125 ; Soderbaum, Ber.
Wolff, J. f. Gasb. 1898, 41, 683). 30, 760, 814, 902, 3014).
Acetylene is a colourless gas which, when quite Acetylene can be used as a starting-point for
pure, has a distinct and agreeable ethereal odour ;
the production of alcohol (J. Soc. Chem. Ind.
it has no action on metals (Clowes, J. Soc. Chem. 1900, 476; Caro, ibid. 1895, 226), but the
Ind. 16, 109 ; Moissan, Compt. rend. 121, 566), methods are costly and the yield poor. Accord-
and is non- poisonous when inhaled in small ing to Vitali (L'Orosi, 21, 217), acetylene has
quantities, although it may produce asphyxiation considerable antiseptic properties.
when more than 40 p.c. of it is present (Clowes, Troubel (J. f. Gasb. 48, 1069) recommends
I.e. ; Korda, Mon. Sci. 45, 409 Mosso and Otto-
; the use of acetylene for autogenous soldering.
lenghi, Ann. di Chim. e. di. Farmacol. 25, 163 ; When acetylene is burned with compressed
Vitali, Chem. Zentr. 1898, ii. 586 Moissan, I.e. ;
; air or oxygen in a specially adapted glass-blower's
Grehaut, Compt. rend. 121, 564; Berthelot, lamp, a flame can be produced but slightly
ibid. 121, 566; Brociner, ibid. 121, 773; J. luminous, which is either oxidising or quite
Soc. Chem. Ind. 16, 319 ; Rosemann, Chem. neutral, is comparable with the electric arc in
Zentr. 1895, ii. 998). intensity, and whilst capable of melting nickel,
It condenses at 1 and 48 atm. to a colourless gold, and platinum, is free from the reducing
liquid which on rapid exhaustion solidifies ; with I
and carburetting properties of the arc (Nichols,
water, liquid acetylene forms a crystalline J. Soc. Chem. Ind. 20, 29).
H
I
hydrate C ? 2 ,6H 2 O (Villard, Compt. rend. 120, On heating sodium hi acetylene, hydrogen is
1262). With ozone acetylene is violently de- given and the compounds C 2 HNa and C 2 Na 2
off,
composed (Otto, Ann Chim. Phys. 1898, 13, 116). are formed (Matignon, Compt. rend. 124, 775 ;
It explodes more violently than other hydro- Skosarewsky, J. Russ. Phys. Chem. Soc. 36,
carbons with oxygen (Meyer, Ber. 27, 2764 ; 863 ; Moissan, Compt. rend. 126, 302). With the
Chatelier, Compt. rend. 121, 1144; Grehaut, hydrides and ammoniums of the alkali metals
ibid. 122, 832 : Berthelot and Vieille, ibid. 123, and of calcium, compounds of the type C 2 M' 2 .
523; Bone and Cain, Chem. Soc. Proc. 1896, H

C 2 2 are formed (Moissan, Compt. rend. 127,
176 ; Clowes, J. Soc. Chem. Ind. 15, 90, 418, 701, 911 ; 136, 1217, 1522 137, 463 ; Berthelot and
;
891). Delepine, ibid. 129, 361).

Any mixture with 3-82 p.c. of
air containing The compounds with copper and silver corre-
acetylene is explosive (Bunte, Ber. 31,5; Clowes, spond respectively with the formulae C 2 H 2 Cu 2 O
Chem. Soc. Proc. 1896, 143 Berthelot and Vieille,
; and C 2 H 2 Ag 2 O, or C.2 H 2 2Ag 2 0. The former is
Compt. rend. 128, 177), but the explosibility is red, the latter yellowish. Both explode on heat-
reduced by admixture with inert gases. It is ing (Blochmann, Annalen 173, 174; Kuntzmann,
slightly soluble in water, more so in alcohol Bull. Soc. Chem. [3] 6, 422 Alexander, Ber. 32,
;
or ether, and very readily so in acetone, with 238 Isolva, ibid. 2697 ; Phillips, Amer. Chem.
;
the last three of which, according to Mclntosh J. 16, 340 ; Scheiber and Flebbe, Ber. 41, 3816 ;
(J. Phys. Chem. 1907, 306), it forms crystalline Makowka, ibid. 824 Freund and Mai, Chem.
;
compounds. Zentr. 1899, i. 410 ; Berthelot, Compt. rend. 132,

Since acetylene gas, as well as the liquid, is 1525).
highly explosive under pressure, it is best stored It also forms such compounds as C 2 H 2 Cu 2 Cl 2 ,
by solution in acetone (Berthelot and Vieille, C 2 Ag 2 AgN0 3 and more complex

,
ones still, some
Compt. rend. 123, 523 ; 124, 966, 988, 996, 1000 ; of which are very explosive (Chavastalon,
Claude and Hess, ibid. 124, 626 ; 128, 303 ; J. Compt. rend. 124, 1364 125, 245 ; 126, 1810
; ;
Soc. Chem. Ind. 20, 1021, 1196; 22, 288; 24, 127, 68 ; 130, 1634, 1764 131, 48 ; 132, 1489 ;;
191, 1101; 16, 788; Wolff, Zeitsch. angew. Hofmann and Kiispert, Zeitsch. anorg. Chem.
Chem. 1898, 919 ; Caro, J. Soc. Chem. Ind. 25, 15, 204; Soderbaum, Ber. 30, 760, 814;
1138). Willgerodt, Ber. 28, 2107 ; Arth, Compt. rend.
The gas burns in air with a smoky flame, 124, 1534; Berthelot and Delepine, I.e. ; Nieuw-
decomposes when exposed to sunlight, and forms land and Maguire, Amer. Chem. J. 28, 1025 ;
condensation and resinous products when sub- Edwards and Hodgkinson, J. Soc. Chem. Ind.
jected to an electric discharge (Berthelot, Bull. 23, 954 ; 25, 495 ; British Association Reports,
Soc. cbim. [3] 4, 480 ; Jackson and Laurie, 1904; Alexander, Ber. 32, 2381; Gooch and
Chem. Soc. Proc. 1906, 155; Losanitsch, Monatsh. Baldwin, Zeitsch. anorg. Chem. 22, 235 ; Reiser,
29, 753 ; Javitschitsch, ibid. 29, 1 ; Coehn, Zeit. Amer. Chem. J. 14, 285).
f. Elektr. 7, 681 ; Billitzer, Monatsh. 23, 199; Acetylene forms compounds with mercury of
Schutzenberger, Compt. rend. 110, 889). the type C 2 Hg 2 ,H 2 0; 3C 2 Hg,H 2 O; C 2 (HgN0 2 ) 2 ,
Acetylene is now used fairly extensively for many of which are very explosive (Nieuwald
illuminating purposes, and is a safe form of and Maguire, I.e. Plimpton and Travers, Chem.
;
artificial lighting (Liipke, Elektr. Z. 1895, 145 : Soc. Trans. 1894, 264 Keiser, I.e. ; Plimpton,
;
J. Soc. Chem. Ind., 16, 33; 18, 476, 343; Chem. Soc. Proc. 1894, 32 Berge and Reychler, ;
Bullier, Bull. Soc. chim. [3] 17, 646) (v. infra). Bull. Soc. chim. [3] 17, 218 Peratoner, Gazz. ;
It is used in flashing-point tests ( J. Soc. Chem. chim. ital. 24, ii. 36 Gooch, I.e. Alexander, I.e. ;
;
Ind. 1898, 949), and has been recommended by Hofmann, Ber. 31, 2212, 2783 Kothner, 2475 ; ;
Lunstroem for freeing alcohol from water ; Burkard and Travers, Chem. Soc. Trans. 1902,
by Violle (Compt. rend. 122, 79), for use in 1270 ; Bilz and Mumm, Ber. 37, 4417 ; Brame,
photometry ; by Erdmann and Makowka Chem. Soc. Trans. 1905, 427 ; Hofmann and
(Zeitsch. anal. Chem. 46, 128) for the separa- Kirmreucher, Ber. 41, 314).
tion of copper from silver, alkaline earths, It also forms bromo-magnesium compounds,
ACETYLENE GROUP. 27
HC CMgBr
; ; BrMgC j CMgBr (Oddo, Atti R. iodine, two iodides are formed a solid, m.p. 78,
Acad. Lincei, 13, 187 ; Gazz. chim. ital. 38, i.
liquid, b.p. 185 (Paterno and Peratoner, Gazz.
625). chim. ital. 19, 580 ; 20, 670).
With fuming sulphuric acid acetylene yields a Acetylene diiodide C 2 I 2 (C CI 2 Nef ) is :
sulphonic acid, and from the potassium salt intensely poisonous (Loew, Zeit. Biol. 37, 222).
H
(C 2 2 ) 3 (S0 4 KH) 4 phenol can be obtained by According to Schenck and Litzendorff (Ber. 37,
treating with potash and distilling the product 3462),it can be used with benzene in making
(Berthelot, Compt. rend. 127, 908; Schroeter, good photographic paper.
Ber. 31, 2189 ; Muthmann, ibid. 1880). When subjected to the action of heat or light,
With fuming nitric acid, nitroform, certain C2I 2 is changed into C 2 I 4 ;
with nitrous fumes it
neutral and acid compounds and the explosive yields nitro-triiodoethylene CI 2 : CI.N0 2 , m.p.
H N
substance C 4 2 3 4 , m.p. 78, are obtained 107 (Meyer and Pemsel, Ber. 29. 1411 B~ilz and ;
(Tustoni and Mascarelli, Atti Real. Acad. Lincei, Werner, Ber. 30, 1200; 33, 2190; Bilz and
1901, 10, i. 442 ; Baschieri, Gazz. chim. ital. Kiippers, Ber. 37, 4412 Chalmot, Amer. Chem.
;
31, i. 461 ; Mascarelli, ibid. 33, ii. 319). J. 19, 877

Nef, Annalen, 298, 202).
;
With hydrogen peroxide acetylene is oxidised Mixed halogen derivatives have also been
to acetic acid (Cross, Bevan, and Heiberg, Ber. obtained (Lemoult, I.e. Keiser, I.e.). ;
33, 2015). With water and carbon tetrachloride or

Nascent hydrogen converts acetylene into similar halogen compounds at 0, acetylene forms
ethylene and ethane. mixed crystalline hydrates (Forcrand and
When acetylene and hydrogen are passed over Thomas, Compt. rend. 125, 109).
freshly-reduced nickel, cobalt, copper, or iron, or Acetylene black, the soot produced when
platinum black, ethane, ethylene, and liquid acetylene burns with a smoky flame or when
hydrocarbons are formed, in amounts depending it is exploded under two atmospheres pressure,
on the nature of the metal, the relative may be used in the colour industry, calico-
proportions of acetylene and hydrogen, and the printing, and also in production of ink (J. Soc.
temperature of the reaction. When acetylene Chem. Ind. 178, 711 18, 284 20, 955 Depierre,
; ; ;
alone is passed over these metals, ethane, ibid. 20, 890 Frank, Zeitsch. angew. Chem.
;
ethylene, hydrogen, and liquid paraffins, are 1905, 1733).

formed, together with ethylenic and aromatic Allylene or Allene C 3 H 4 exists in two isomeric
hydrocarbons, the proportion of the products modifications.
formed depending on the catalyst and tempera- 1. Methyl acetylene or allylene CH 3 -C J
CH.
ture. In the case of copper a greenish hydro- formed by the action
Is of alcoholic potash
H
carbon cupre ne (C 7 6 ) n is also formed ; a on bromopropylene
similar compound is also obtained with nickel CH :CBr:CH +KOH
3 2
(Sabatier and Senderens, Compt. rend. 128, =CH -C;CH+KBr+H
3
0.
1173; 130, 250, 1559, 1628; 131, 187; Also by acting with sodium on dichloracetone
Moreau, ibid. 122, 1240). chloride
A mixture of nitrogen and acetylene sub-
CH 3 -CCl -CHCl 2 +Na 4 =CH 3 -C CH+4NaCl.
jected to the action of induction sparks yields
2 \
prussic acid C 2 2 :
2
H +N =2HCN
(Beilstein). Or by electrolysing the alkali salts of citraconic
Chlorine and acetylene combine explosively or mesaconic acids, or by action of magnesium
when exposed to daylight, but according to on acetone vapour and treating the solid mass
Monneyrat (Compt. rend. 126, 1805), chlorine thus obtained with water (Keiser, Amer. Chem.
and acetylene in the absence of oxygen combine J. 18, 328; Desgraz, Bull. Soc. Chem. [3] 11,
without explosion forming acetylene tetra- 391 ;Lespieau and Chavanne, Compt. rend.
chloride, which together with the dichloride, can 140, 1035).
23-5 ;
also be produced by the action of acetylene on Allylene is a colourless gas, b.p.
antimony pentachloride (Tompkins, D. R. P. m.p. 110; very similar to acetylene, and, like
196324; J. Soc. Chem. Ind. 24, 150). The it, forming compounds with metals.
The
tetrachloride, which is an excellent solvent for H
mercuric compound (C 3 3 ) 2 Hg is obtained by
fats, oils, and resins, can also be prepared by the passing allylene through water containing
action of acetylene and chlorine on acetylene mercuric oxide in suspension. It crystal-
dichloride when exposed to radium emanations lises from hot alcohol in fine needles. It is
(Lidholm, D. R. P. 1908, 201705). Acetylene soluble in hydrochloric acid with evolution of
also be chlorinated by passing it into a allylene, but does not explode
on heating (Keiser,
mixture of sulphur chloride and a catalyst such I.e. ; Lessen and Dorno, Annalen, 342, 187 ;
as an iron compound (J. Soc. Chem. Tncl. 24, Plimpton and Travers, I.e. ;
Bilz and Mumm, I.e. ;
1255; 27, 643, 344; Nieuwald, Chem. Zentr. Hofmann, Ber. 37, 4459).
1905, i.
1585). The silver compound (C 3 H 3 2 Ag forms micro- )
Bromine added to an alcoholic solution of at about 150.

scopic needles which explode
acetylene, or acetylene passed into bromine According to Berthelot (Compt. rend. 126,
water, forms C 2 H 2 Br 2 but if the gas be passed
|
561, 567, 609, 616) allylene, when subjected

to
,
through bromine the substances C 2 H 2 Br 4 and

!can the silent electric discharge, condenses to a solid
(C 2 HBr 3 3 are obtained (Gray, Chem. Soc. Trans. with
) with a pungent empyreumatic odour ;
1897, 1027 Elbs and Newmann, J. pr. Chem.

; nitrogen the substance C J5 H.,
is formed. N
additive pro-
[2] 58, 245) dibromoacetylene C 2 Br 2
;
b.p. , Allylene forms with bromine
76-77, is obtained by treating an alcoholic H H
ducts, C 3 4 Br 2 and C 3 4 Br 4 , and with halogen
solution of tribromethylene with potash acids compounds of the type CH 3 -CC1 2
-CH 3 .
(Lemoult, Compt. rend. 136, 1333). Concentrated sulphuric acid absorbs allylene
with water,
According to Keiser (Amer. Chem. J. 21, 261) readily and on distilling the solution
when dry acetylene is gently warmed with solid acid
acetone, mesitylene, and allylenesulphonic
28 ACETYLENE GROUP.
C 3 H 3 S0 3 H are formed (Schrohe, Ber. 8, 18 3. Vinyl-eihyleneCH 2 : CH-CH : CH., (Perkin
and 367). With hypochlorous and hypobromous and Simonsen, Chem. Soc. Trans. 1905, 857).
acids, allylene forms dichlor- and dibrom- Prepared by passing the vapours of fusel oil
acetones, and trimethyl allylene yields the through a red-hot tube (Caventou, Annalen,
halogen pinacolins (Wittorf, Chem. Zeit. 23, 695). 127, 348). It is present in compressed coal gas
2. Symmetrical allylene or allene 2 C 2 CH : : CH (Caventou, Ber. 6, 70), and in oil gas (Armstrong
is obtained by the action of sodium on and Miller, Chem. Soc. Trans. 1886, 74). It gives
/3-chlorallylchloride no precipitate with an ammoniacal cuprous
CHC1 CH-CH 2 Cl+2Na=CH 2 C CH 2 +2NaCl.
: : :
chloride solution. When treated with bromine
in chloroform solution cooled to 21, it gives a
Or by the action of zinc-dust on an alcoholic
liquid dibromide, b.p. 74-76 /26 mm., which at
solution of dibrompropylene (Gustavson and
100 is converted to a solid of the same com-
Demjanoff, J. pr. Chem. 1888, 201 Vaubel, ;
53-54, b.p. 92-93 /15 mm. ; with
position, m.p.
Ber. 24, 1685; Lespieau and Chavanne, i.e.). bromine the liquid dibromide yields a tetra-
And by the electrolysis of the alkali salts of
bromide (Griner, Compt. rend. 116, 273; 117,
itaconic acid.
553 Thiele, Annalen, 308, 333).
;
The substance is a gas (b.p. 32 ; m.p. 146), 4. The butine CH 3 -CH C CH 2 is prepared
: :
but from unsymmetrical allylene in giving

differs
no precipitate with an ammoniacal copper or by heating tetrachlorbutane with alcohol and
the zinc-copper couple or from chloral by treat-
;
silver solution (Phillips, Amer. Chem. J. 16, 340).
ment in the cold with zinc ethyl. It is a colour-
With aqueous mercuric chloride allene and its less liquid, b.p. 18-19, yields no precipitate with
homologues yield white precipitates (Vaubel, I.e. ;
ammoniacal copper solutions, but with bromine
Lessen and Dorno, I.e. ). It unites with bromine
yields di- and tetra-bromine derivatives (Norton
to form C 3 H 4 Br 4 b.p. 225~~230, with decom-
,
and Noyes, Amer. Chem. J. 10, 430).
position. The compound CH C-C CH, formed by the
: :
According to Smirnoff ( J. Russ. Phys. Chem. action of cupric chloride on copper acetylene,
Soc. 35, 854 36, 1184), the allene hydrocarbons
is described by Noyes and Tucker (Amer. Chem.
;
can be identified by treatment with hypochlorous

when keto-alcohols of distinctive properties
J. 19. 123) ; pentachlorbutine C 4 HC1 5 by Zincke
acid, and Kuster (Ber. 26, 2104).
are obtained.
Derivatives of the butines, some of which are
Butines C 4 6 H .
used as dye-stuffs, are described by Freund

Four isomerides exist.
1. Ethylacetylene C 2 H 5 -C;CH. Formed by (Ber. 34, 3109).
Pentines. Seven of eight possible pentines
the action of alcoholic potash on C.,H 5 -CC1 2 -C'H 3
are known, of which isoprene obtained in the dry
(Bruylants, Ber. 8, 412). distillation of indiarubber is the most important
By passing acetylene and ethylene through (Ipatieff and
Wittorff, J. pr. Chem. [2] 55, 1 ;
a red-hot tube (Berthelot, Ann. Chim. Phys. [4]
Ipatieff, ibid.
4). It can be obtained synthe-
9, 466).
tically by the action of alcoholic potash on
The compound is a liquid boiling at 18, and
is a true acetylene, since it forms precipitates #-dimethyltrimethylene dibromide. It has b.p.
33 34, unites with hydrogen bromide forming
with ammoniacal copper and silver solutions.
CMe 2 BrCH 2 -CH 2 Br, and has no action on
With ammoniacal silver chloride and alcoholic ammoniacal cuprous chloride or silver nitrate
silver nitrate it forms explosive compounds
(Euler, J. pr. Chem. [2] 57, 131).
(Wislicenus and Schmidt, Annalen, 313, 221) it ;
When saturated with hydrogen chloride at
also yields a sodium derivative (Jociez, Chem.
and then allowed to remain in a sealed tube at
Zentr. 1897, 1012). i.
the ordinary temperature for two or three weeks,
2. Crotonylene or dimethylacetylene
/~ITT .c* * r^.otr
a substance analogous to indiarubber is formed
v^-TL 3 U v> OX1 3 ,
(Bouchardt, J. Soc. Chem. Ind. 21, 56).
Formed by acting with alcoholic potash on &y- Two trimethylene pentines and cycZopentine
dibromobutane CH 3 -CHBr-CHBr-CH 3 ; by the have also been obtained.
action of sodium ethoxide on monobrompseudo- Of the higher terms of the series the hexine
butylene MeCBr CH-CMe (Holz, Annalen, 250,
:
diallyl is of interest. It is formed by the action
230) ; or by the decomposition of the salts of of sodium on allyl iodide
j8-bromoangelic acid (Wislicenus, Talbot, and
Henge, Annalen, 313, 228). It is a liquid,
also by distilling mercuric allyl iodide with
b.p. 27-2-27-6 (Wislicenus and Schmidt, I.e.). potassium cyanide. It probably consists of a
With bromine it forms a liquid C 4 H 6 Br 2 b.p. ,
mixture of two isomerides (Wagner, Ber. 21,
146-147 (Holz, I.e.), and C 4 H 6 Br 4 which 1 ,
3343; 22, 3056; Siderenko, J. Russ. Phys.
solid, m.p. 243 zsocrotonylene dibromide, b.p.
;
Chem. Soc. 36, 898).
149-150, is also known, and is not readily It forms a liquid smelling of horse-radish,
attacked by zinc - dust
(Wislicenus and
boiling at 59, and combines with bromine to
Schmidt, Z.c.). form the tetrabromide C 6 H 10 Br 4 melting at 63. ,
Crotonylic mono- and hydro-bromides, as well If this be boiled with potash a liquid dibromo-
as the iodide and chloride derivatives, have also
diallyl is obtained, which boils at 210, and by
been obtained (Wislicenus, Talbot, and Henge, the action of alcoholic potash yields diproparyyl
Z.c. ; Peratoner, Gazz. chim. ital. 22, ii. 86 ;
C 6 H g a liquid boiling at 85 isomeric with ben-
,
Charon, Ann. Chim. Phys. 1899, 17, 228;
zene, but having the constitution
Favorsky, J. pr. Chem. [2] 42, 143).
On shaking the hydrocarbon with sulphuric CH C-CH 2 -CH 2 -C
:
|
CH.
acid and Avater (3:1), hexamethylbenzene is ACETYLENE AS AN ILLUMINANT. Al-
obtained though acetylene was discovered by Davy aa
3C 4 H 8 =C 12 H 18 =C 6 (CH 3 ) 6
. far back as 1836, its use as an illuminant became
ACETYLENE AS AN ILLUMINANT. 29
' '
practicable only in 1892, when Moissan

in the run carbide is limited only by the size
France, and T. L. Willson at Spray, showed of the carbon electrodes that can be obtained ;
' '
that it was possible to make calcium carbide on with ingot carbide a furnace taking about
a commercial scale in the electric furnace. 200 E.h.p. is the most useful, taking into con-
At temperatures above 3000 a mixture" of sideration efficiency as well as wear and tear.
lime and some form of carbon, such as coke, The most usual current for such a furnace would
soot, anthracite, or charcoal, becomes semi- be about 12 to 15 amperes per square inch of
liquid, and reduction of the calcium oxide electrode surface at a pressure of 55-65 volts.
results with production of carbon monoxide Cheap power is of course the main factor in
and liberation of calciu m, which unites with the the economical production of calcium carbide,
excess of carbon to form calcium carbide : and this has resulted in the carbide industry
2CaO + 3C 2 = 2CO + 2CaC 2 becoming localised in those districts where
Lime. Carbon. Carbon monoxide. Calcium carbide. water power is available, but the important
advances which have of late taken place in the
Water decomposes the carbide with reproduction
of lime and generation of acetylene :
development of power from gaseous fuel will
probably result in the establishment of factories
CaC 2 + H 2
= CaO + C 2H 2 in localities where the necessary material can be
Calcium carbide. Water. Lime. Acetylene.
readily obtained and a local market secured for
In the early days of carbide manufacture the product, since carriage necessarily influences
littleattention was paid to the purity of the the cost of production.
materials, with the result that the compound The cost of production of calcium carbide may
formed contained impurities, some of which be taken as being about 11. per ton under the
were decomposed by water and gave products most advantageous conditions.
contaminating the acetylene. Since the im- Calcium carbide, as made in the electric
portance of purity in the acetylene has been furnace, is a dark crystalline substance with
recognised, everything possible is now done to a metallic lustre, having a density of 2-22. The
reduce such impurities to a minimum. pure compound, however, has been produced by
The lime employed is burnt in special kilns Moissan in thin white semi-transparent plates,
heated by gas, as the ordinary method of lime- the colour of the commercial material being due
burning by means of coal, &c., introduces so to the presence of iron and other impurities.
many impurities into the finished material that The impurities found in commercial carbide
a bad carbide results. The limestone from may be divided into those which can be decom-
which the lime is obtained must be as free from posed by water, and those on which water has
foreign matter as possible for the same reason. no action. Amongst the former are substances
The same restriction applies to the carbonaceous evolving phosphorus compounds on contact with
matter used as the source of the carbon, and it water, aluminium sulphide, organic sulphur com-
is of the utmost importance that the ash, sulphur, pounds and metallic nitrides : whilst the latter
and phosphorus should be as low in quantity class contains such bodies as graphite, carbides
as possible. of boron and silicon, carbides and silicides of
The proportions of the lime and carbon various metals contained in the lime and in the
required by theory are 56 parts of lime to 36 ash of coke, these being left with the lime residue
parts of carbon, but allowance has to be made after the decomposition of the carbide by water,
for impurities and loss in manufacture, so that and in no way influencing the purity of the gas.
the ratio now adopted is 100 of lime to 70 of The purity of commercial acetylene depends
carbon, whilst in some cases, to ensure a more primarily on the purity of the carbide from
fusible product, a rather higher proportion of which it is generated, and as long as it is im-
lime is used, but the carbide so made has a possible to get absolutely pure materials
for the
slightly inferior gas-generating power. manufacture of the carbide, so long will im-
Various types of electric furnace have been purities be found in the gas made from
it. The
devised for the manufacture of calcium carbide, most important of these impurities are :
but they can be divided practically into two (a) Phosphoretted hydrogen,
obtained from
classes (a) those in which the arc is struck in
: the decomposition of calcium phosphide, &c.,
a mass of the mixed lime and carbon placed by water, and, in burning with the acetylene,
round the poles, the upper pole being raised as gives rise to phosphorus pentoxide,
which forms
the carbide is produced, thus gradually building a light haze in the room in which the gas is
' '
up an ingot ; and (6) those in which the being burnt.

mixture is fed continuously between the carbon (b) Sulphuretted hydrogen,
formed by the
poles, the carbide remaining in the furnace in action of water on aluminium sulphide, &c., and
a fused condition, and being tapped from time yielding when burnt sulphur dioxide,
which if
dissolved by condensing moisture will absorb
' '
to time, the product being known as run
carbide. oxygen from the atmosphere, forming traces of
At the present time nearly all the European sulphuric acid.
carbide is made by the latter process, whilst (c) Ammonia, from
the magnesium nitride,
ingot carbide is still largely made in America, which rapidly corrodes brass gas-fittings, and
a rotary furnace of the ' Horry ' type being on burning produces traces of nitrogen acids.
much used, in which the slow revolution of the Siliciuretted hydrogen is also found in small
furnace removes the ingot as it is formed from quantities in crude acetylene.
the direct impact of the arc, and presents a Several processes have been devised for the
fresh portion of the charge to its action. purification of acetylene by
the removal of these
For all practical purposes it may be stated compounds as well as of the hydrocarbon
that 1 E.h.p. per year will yield one ton of vapours formed by the polymerisation of the
carbide. The size x>f the furnace in the case of gas due to high temperature during generation.
ACETYLENE AS AN ILLUMINANT.
The only impurity that offers any real difficulty CaC 2 + H O = CaO +
2 C 2 H,
in removal the phosphoretted hydrogen, and
is Calcium carbide. Water. Lime. Acetylene.
three substances have been suggested and used CaO + H O = Ca(HO)
2 2
.
in practice for this purpose Lime. Calcium hydroxide.

Water.
(a) bleaching
:
powder, (b) acid copper or iron salts, and And so great is the affinity of the carbide for
(c) acid solution of
chromic acid. water that the calcium hydroxide so formed is
The bleaching powder is employed in the form slowly decomposed on standing by any excess
of small lumps, as offering the least resistance of the carbide.
to the flow of the gas when in a slightly mois- The first generator was of the simplest con-
tened state. Its action is purely that of oxi- struction, the carbide being contained in a glazed
dation, the phosphoretted and sulphuretted vessel provided with two side tubulures and a
hydrogen being converted respectively into phos- lid could be clamped down gas-tight.
that
phoric and sulphuric acids, the acetylene being Through one of the tubulures water was
unaffected. To obtain as large a surface as admitted by means of a siphon, whilst the gas
possible the bleaching powder is sometimes evolved was led through the other tubulure to
mixed with an inert bod} such as sawdust or
7
, a holder, but when the commercial possibilities
oxide of iron, but in whatever condition the of the gas had become apparent, inventors at
bleaching powder is used the gas requires an once turned their attention to the multiplication
after-purification for the elimination of chlorine of the forms of generator.
compounds, for which purpose a lime purifier is Although the generation of acetylene by thus
generally employed. bringing calcium carbide in contact with water
Bleaching powder, though an efficient purify- seems so simple, yet in actual practice it was
ing agent when good order, is apt to be un-
in complicated by several difficulties, amongst
certain in its action, and cases have frequently which be mentioned the heat of the
may
occurred of spontaneous firing and explosion reaction, which caused the polymerisation of
when air has been admitted to purifiers con- some of the acetylene, and by the fact that the
taining this material that have been in use for evolution of gas did not cease immediately
some time, so that precautions are necessary the water supply was cut off, this being due to
when using this method of purification. water mechanically held in the residue formed,
An
acid solution of cuprous chloride, or solids to the dehydration of the calcium hydroxide
made by impregnating kieselguhr or similar by the unchanged carbide, as well as to the
porous bodies with the acid copper salt, are moisture condensed from the gas as the tem-
also very effective in removing the various perature of the generator fell.
impurities, the phosphorus and sulphur com- Acetylene generators can be divided into two
pounds being transformed into copper phosphide main classes those in which water is brought
and sulphide. The disadvantages of the process in contact with the carbide, the latter being in
are that a second purification with lime is excess ; and those in which the carbide is thrown
required to remove acid vapours, and that the into water, the water being always in excess.
material being highly acid cannot be used in The first class may be subdivided into those in
ordinary metal containers, whilst if the copper which water is allowed to rise to the carbide,
salt became neutralised by ammonia there might those in which it drips on to the carbide, and those
be danger of the explosive copper acetylide in which a vessel full of carbide is lowered into
being formed. Under suitable conditions 1 kilo- water and then withdrawn as the generation of
gram of the material will purify 20 to 25 cubic the gas becomes excessive.
metres of the gas, the acetylene not being acted Each of these types may be ' automatic ' or
upon, and the action being regular and certain.
'
non-automatic.' In the former are to be
Chromic acid in solution containing sulphuric found devices for regulating and stopping at will
or acetic acid, or kieselguhr charged with this the generation of the gas within limits, whilst
'
mixture, is the third purifying agent, and
'
the non-automatic variety aim at developing
eliminates the phosphoretted and sulphuretted the gas from the carbide with as little loss as
hydrogen and the ammonia. When exhausted possible and storing it in a holder.
the spent material can be regenerated by The points to be aimed at in a good genera-
exposure to the air. tor are :
In practice these three materials seem to give (a) Low temperature of generation.
equally good results, and the passage of the gas (b) Complete decomposition of the carbide.
through the solution or solid scrubs out of it (c) Maximum evolution of gas from carbide
to a great extent the tarry fog and lime dust used.
often mechanically held in the gas when it has (d) Low pressure in every part of the ap-
been generated too rapidly or at too high a paratus.
temperature. (e) Removal of all air from the apparatus
Absolute purification is by no means neces- before collection of the gas.
' '
sary ; for ordinary use all that is required being Generators of the drip type, in which
to reduce the amount of impurity below the limit water is allowed to fall slowly upon a mass of
at which the products of combustion are injurious carbide, possess most of the disadvantages due
to health or- cause haze and with a fairly pure
; to heat of generation, fluctuation of pressure,
specimen of carbide mechanical scrubbing is &c., and this type has been abandoned except
sufficient if a generator of the non-automatic for the smallest forms of portable generator.
type is employed, and the gas is stored in a Those in which water rises to the carbide are
holder before use. most efficient, and overheating can be avoided
When calcium carbide is acted upon by water by ensuring that the water never rises above
the changes that take place may be represented that portion of the carbide which is undergoing
by the equations :
decomposition : in other words, that the gas
leaves the carbide immediately upon its forma- causing a greater insuck of air into the flame,
tion and passes away to the holder with the and ensuring a more complete combustion.
least opportunity for becoming overheated by Some specially small union jet burners were
contact with decomposing carbide. also produced by Bray, and both these
nipples
Generators in which the carbide dips into answered extremely well for a time and deve-
water and is then withdrawn are apt to overheat loped from 30 to 36 candle power per cubic foot
to a dangerous extent, especially if the generator of gas consumed, but they both had the same
be over-driven. weakness, and after a few hundred hours began
Although it might be expected that the to smoke, and evolve copious clouds of soot-
dropping of the carbide into an excess of flakes.
water would produce the coolest and purest gas, This trouble generally began by a filiform
yet this is not the fact, and evidence of over- growth of carbon appearing on the jet of the
heating of the gas is often found in generators burner, which quickly distorted the flame,
of this class, as a coating of lime can form impeding proper combustion and causing the
around the lumps, preventing the free access of formation of quantities of free carbon. If the
water, and allowing the interior of the mass burner was cleaned and relighted, the trouble
from which generation is proceeding to become began again in an hour or two, and the only
heated to redness ; the efficiency also is very remedy was to replace the burner by a new one.
low, as a considerable amount of the gas is The smoking of acetylene burners after they
dissolved in its upward passage through the have been in use for some little time, more
large volume of water. particularly if the gas be turned down, is due
Theoretically 64 parts by weight of carbide indirectly to the property possessed by acetylene,
require only 36 parts by weight of water for in common with many heavy gaseous hydro-
complete decomposition and conversion of the carbon compounds, of polymerising as the tem-
lime into hydroxide, but it is found in practice perature rises ; and also to the pressure at the
that, owing to the heat of the reaction driving burner-tip being insufficient to impart to the
off some of the water as steam, and a further gas the velocity necessary to ensure the admix-
portion mechanically adhering to the slaked ture with sufficient oxygen to effect its complete
lime, double this amount of water is necessary, combustion or, in some cases to the flow of gas
;
and the only safe way to ensure entire decom- through the burner holes being checked by
position of the carbide is to add sufficient water accumulation of foreign matter therein.
to flood the residue. If the steatite jet of a burner in which smoking
When acetylene is burnt in air under such has developed be broken it will be found to be
conditions as to complete its combustion, it is carbonised for some depth into the material,
converted into carbon dioxide and water vapour, showing that a liquid hydrocarbon has soaked
the same compounds that are produced by all into the steatite and has been decomposed by
combustible hydrocarbons, 1 cubic foot of the heat with deposition of carbon. The generally
gas requiring 2 cubic feet of oxygen, or five accepted idea is that the heat of the burner
times that amount of ah*. polymerised some of the acetylene to benzene,
When acetylene was first used for illuminat- and that this scrubbed out by friction at the
ing purposes, Bray union jet burners were nipple led to the carbonisation and choking of
employed, and although a very high duty was the burner. Another theory, however, is that
obtained, the pressures necessitated were too the heat evolved by the reaction between the
high to be desirable, and carbon was rapidly carbide and water in the generation of the gas
deposited on the burner tip, and caused such polymerises some of the acetylene immediately
serious smoking of the flame as to considerably upon its formation, and that a certain quantity
prejudice the use of the new illuminant. The of the liquid hydrocarbon so formed is held in
proper combustion of any hydrocarbon gas, how- suspension and carried by the gas as a vapour
ever rich in carbon, can be effected by supplying to the burner, where it is scrubbed out by
the flame with exactly the amount of air neces- frictional contact and gradually accumulates
sary to prevent smoking, and it is under these thereand is decomposed.
conditions that the highest illuminating effect Although the deposition of carbonaceous
possible with a particular burner is obtained. matter does not take place so readily in burners
The ratio between the air to be supplied and supplied with gas that has been generated
the gas consumed depends upon the thickness slowly and at a low temperature with subsequent
of the flame and the pressure at which the gas washing and purification, yet it is a fact that
issues from the burner. the trouble arises when the gas is in the purest
If acetylene be burnt from a 000 Bray union possible condition. Gas generated below 280
jet burner at ordinary pressure a smoky flame will not so frequently give rise to the trouble of
is obtained, but if the
pressure be increased to carbonising at the burner, but if this temperature
4 inches an intensely brilliant flame results, free be exceeded in generation, no after-treatment
from smoke and giving an illuminating value of of the gas will prevent it.
240 candles per 5 cubic feet of gas consumed. A small percentage of water carried along with
For practical purposes, however, this pressure the gas mechanically, or a little lime dust held
is too high, and the largest burners at first in suspension, is also a source of carbon deposit
adopted, which required the consumption of at the burner.
1 cubic foot of
acetylene per hour, gave on an '
Carbonisation of the burner is aggravated by
of gas
average 32 candles at an inch pressure. turning down,' in which case the flow
These first burners were of the union jet type, is checked and the flame plays about the tip
in which
very fine holes were employed for the of the burner, heating it to a temperature
delivery of the gas, and drilled at a more obtuse favourable to. polymerisation, when carbon is
causes the
angle than ordinarily used for coal gas, thus deposited, and by its catalytic action
32 ACETYLENE AS AN ILLUMINANT.
accumulation of further growths. If, however, 1
though of slightly different construction. It

the gas is burned at full pressure, the flame is ! consisted of a metal base, the upright from
not in actual contact with the burner, and the which forked into two arms, which near their
velocity of the issuing jet of gas induces currents extremities were bent inwards at right angles.
of air around and through it, which prevent the These arms carritfJ. steatite or ' lava ' tips,
temperature of the burner being raised to a bored with a fine hole from the interior to the
degree sufficient to polymerise the gas to any base of the mushroom head, where its diameter
material extent. was more than doubled, whilst four small lateral
For the above reasons it was soon discovered air tubes were bored at regular intervals from
that ordinary gas burners of the union jet the base of the head to the broad aperture of
pattern were unsuitable, although attempts had the nipple, with the result that the flow of
been made in America to use acetylene diluted acetj-lene from the narrow into the wider tube
with a certain proportion of air, which per- sucked air in through the side tubes and sur-
mitted it to be burnt in flat flame burners, but rounded the ascending gas with an envelope
the danger of such admixture being recognised which prevented its contact with the heated
efforts in this directionwere soon abandoned. tip. These burners, which are more generally
In France burners were devised in which jets known as the ' Naphey ' burners, gave very-
of acetylene coming from two tubes spaced some good results, and have been more widely adopted
little distance apart were made to impinge and than the Billwiller burners that preceded them,
splay each other out into a flat flame, whilst partly because they did away with the expense
soon after Bullier introduced the idea of sucking of the platinum, were cheaper to make, and
air into the flame at or just below the burner- were less liable to break.
tip. These tips were very largely manufactured on
No real advance, however, was made in burners the Continent, both the American and English
for acetylene until 1896-97, when Bullier 's supply coming from Nuremberg. The form of
principle of making the tips of the burner jets mounting, however, was considerably varied in
into small bunsens was adopted by Dolan in order to suit the taste of the user or to give the
America, and Billwiller on the Continent. burner a new name. In one very popular
The Billwiller burner has two steatite arms form the arms are made as a portion of a
rising at right angles from a common base circle, this modification doing away with the
from which the acetylene issued at two snialJ friction and check to the flow of gas due to the
orifices exactly opposite each other and giving sharp bend in the original pattern, whilst these
the double jet. Immediately above the gas again are made up in groups of two or three
orifice a small platinum plate was burners where greater illumination is required.
fixed at a distance of about 0-5 The great drawback to all the Naphey tip
mm. from the steatite, with a burners is that the heat from the flame causes
hole in it rather larger than the a slight and gradual warping of the metal
orifice in the steatite just below. mounting, with the result that after a time the
The acetylene issuing from the jets become slightly thrown out of their true
hole in the steatite rushed through position, which at once distorts the flame and
the hole in the platinum above causes it to throw up smoky points. This
FIG. 1.
and drew air in under the plati- trouble is not found with burners having steatite
num plate. The air so drawn in flowed to the or composition arms, as these, being pressed or
confines of the rapidly travelling stream of cut, do not warp with the heat.
acetylene and passed upwards around it, so These burners proved the forerunner of a host
preventing contact between the edge of the of others in all of which the same principle was
hole in the platinum and the acetylene, whilst adopted, one of the simplest and most popular
the metal, being part of a collar of platinum being shown in Fig. 2, whilst Fig. 3 is a section
fixed round each steatite arm, and
being a
good conductor of heat, prevented such heating
as would lead to the deposition of carbon from
the gas.
These burners, made by Schwarz of Nurem-
berg, and sold under the name of the Basle ' '
burner, gave excellent results, as is shown in

the following table :
Number Gas con- Pressure , Total ,

Candles per
of sumed ,
in inches :
light cnb. ft. of

burner (cub. ft.) (water) (candles) !
gas
in gas pressure caused by
turning down the acetylene flat-flame burners under the best
flame do not lead to carbonisation.
conditions, but very widely different results
The same principle is utilised by Schwarz in nave been obtained,
' ' owing to irregularities in
the Suprema burner made at Nuremberg, the pressure or lack of air
which is shown in Fig. 4. regulation, and at
th moment of
Another burner has been brought out by lighting or turning out there is
a ^liability of a small but violent
|
this maker in which the idea of air explosion,

injection has which has disastrous effects
upon the mantle.
been successfully adapted to a slit burner: A further difficulty is caused when
phosphoretted
the gas issues from a series of fine holes hydrogen is present as an impurity, for this
placed below a cap provided with a broad slit leads to the formation of fusible
phosphates of
thorium and cerium, with
consequent destruc-
tion of the mantle.
Apart from these con-
siderations, the mantle appears to be hardened
and strengthened by the intense heat to which
it is
subjected, but it is not yet determined
how the life of the mantle is affected
by the
temperature of the flame.
Under the light yielded by the combustion of
FIG. 4, FIG. 5.
acetylene colours appear practically the same
and side air tubulure, the gas drawing in suffi- as in daylight, and all tints and shades can be
cient air in its passage through the slit to prevent as clearly distinguished from one another as in
smoking or carbonisation of the burner (Fig. 5). sunlight. For this reason the gas has been
From the earliest introduction of acetylene found to be of invaluable utility in
dyeing and
attempts have been made to utilise it with colour printing. The spectrum of acetylene,
incandescent mantles, but under the pressures however, although the same as that of daylight
which are usually obtained from the ordinary for red and yellow, has an increase in the blue
generating apparatus this has not proved success- rays of 0-46, which brings them to about the
ful. Acetylene, when consumed in an atmo- same value as the Northern Light. The violet
spheric burner, gives an excessively hot flame, rays show a slight increase, so that acetylene
not only on account of its composition, but also is even richer than
sunlight in the rays which
from endothermic character. Several diffi-
its are so essential to the chemical action of
light,
culties, however, are met with in trying to burn and yet the red rays which are so detrimental
acetylene mixed with air in sufficient proportion in colour work do not
predominate, as in the
to yield a non-luminous flame, namely : electric arc.
(a) The wide range over which such mixtures In 1896 Claude and Hess, in France, sug-
are explosive. gested the idea of making use of the solubilitv
The low temperature of ignition.
(b) of acetylene in certain liquids as a means of
The high speed at which the explosive
(c) storing this gas, and acetone was tried as the
wave travels through the mixture of gas and air. solvent. But it was found that the simple
In order to make a bunsen burner for acetylene solution of acetylene in acetone, although less
the tube has to be very narrow, and even then liablethan the compressed or liquefied acetylene
flashing back is very liable to occur, whilst a to explosion, could not be said to be sufficiently
high pressure is needed to bring about a satis- free from danger to admit of its general use.
factory mixture of the gas with sufficient air to It was soon discovered by Janet and Fouche
ensure combustion with an absolutely non- that when acetylene is dissolved in acetone
luminous flame. The range of explosibility lies absorbed by porous material of the right kind
between 3 p.c. and 82 p.c. of acetylene in the under 10 atmospheres pressure, it was impossible
mixture, and the propagation of the explosive to produce explosion. The medium employed
wave cannot be stopped by the ordinary device has a porosity of 80 p.c. soaked with 43 p.c. of
of using wire gau/.e, on account of the low the capacity of the cylinder with acetone. In
ignition point of the mixtures. By using a tube this way one cubic foot of cylinder space can
\ mm. in diameter the explosion ceases to be be made to hold 100 cubic feet of acetylene,
propagated at all, but such tubes, on account of which is, to a large extent, given off when the
their small diameter, cannot be utilised
singly. tap of the cylinder is opened.
The difficulty can be surmounted by using a
. Acetone dissolves 24 times its volume of
bundle of small tubes united to form a single acetylene at 15 and under ordinary atmo-
burner, or by employing a large tube having a spheric pressure, the solubility increasing with
constriction at one point of not more than 5 mm. the augmentation of pressure, and the volume
diameter. The diameter of the tube at the of the acetone also increasing very largely.
constriction must be in a definite proportion to Under 12 atmospheres 300 volumes of gas are
the particular mixture of air and acetylene con- dissolved.
sumed, as the more air the greater must be the The oxy-acetylene flame has within the last
constriction in the strangulated portion of the few years become of great service in auto-
tube, owing to the increased velocity of the ex- genous welding. The advantages of such a
plosive wave. flame were well recognised previous to 1901, but
With an acetylene bunsen, and using a considerable difficulty was experienced in pro-
Welsbach No. 2 mantle, as much as 90 candles viding a blowpipe which would consume the
per cubic foot of acetylene has been obtained. acetylene at low pressures, and it was not until
It may be taken that when used with a mantle the introduction of dissolved acetylene that
acetylene will give double the illuminating power success was attained. Blowpipes are now made
per cubic foot as compared with the light in which the oxygen alone is under pressure,
obtained when the gas is burnt in the ordinary the acetylene being under the low pressure au
VOL. 1.T. D
ACETYLENE AS AN 1LLUMINANT.
delivered from a generator. The two systems superior to the arc light or incandescent
are known as the high-pressure and low-pressure mantle. V. B. L.
methods of oxy-acetylene welding. ACHRODEXTRIN v. DEXTRIN.
The temperature of the oxy-acetylene flame !
ACHYRANTHES ASPERA or Aghara. An
is approximately 3000, and from the nature of Indian plant used as a simple and as a remedy
the combustion the flame has a reducing action for toothache.
tending to exclude the possibility of oxidation ACID ALBUMEN v. PROTEINS.
of the metals undergoing treatment. Theoreti- ACID ALIZARIN, -BLUE, -GREEN v. ALI-
cally 2 -5 volumes of oxygen are required for each ZARIN AND ALLIED COLOURING MATTERS.
volume of acetylene, but in practice it is found ACID CERISE v. TRIPHENYLMETHANE
that the proportions are approximately 1-4 to COLOURING MATTERS.
1-0, this low proportion of oxygen ensuring a ACID GREEN v. TRIPHENYLMETHANE
reducing action in the flame. COLOURING MATTERS.
In the high-pressure system the oxygen is ACIDIMETRY and ALKALIMETRY. This
delivered from an ordinary cylinder under branch of quantitative analysis dealing with the
pressure, and the acetylene, dissolved in acetone estimation of acids and alkalis is of great
under pressure, isalso supplied from cylinders. technical importance. In pure aqueous solu-
Both cylinders are fitted with special governors, tions the amount of acid or alkali can usually
as a perfect regulation of the flame is one of the be ascertained with considerable accuracy by
main secrets of success. determining the specific gravity of the liquid
With the low-pressure plant the acetylene is at a definite temperature and referring to a table
made in an ordinary generator, which may be especially drawn up for this purpose.
of the automatic or non-automatic type, the Direct estimations may also be made by
size of the works to a great extent influencing suitable gravimetric methods, but volumetric
the kind of generator used, but, whatever type processes are almost exclusively employed, and
be adopted, it is necessary that the generation are indeed the only methods available for
distinguishing between free and combined
of the gas should not be accompanied by over- acid
heating, as this leads to low temperatures at the or alkali. In these operations the quantity of
burner and other troubles. The gas should be acid or alkali present is calculated from the
purified before use, as the presence of the amount of standard alkali or acid required
phosphoretted and sulphuretted hydrogen would respectively to neutralise it exactly, the precise
tend to spoil the weld, and the purifying agent point of neutralisation being determined by
should be renewed when necessary. After the addition of a small quantity of an indicator,
leaving the purifiers the gas is distributed to the i.e. a substance which by undergoing a marked
various points in the workshops in gas- or change of colour renders evident the transition
steam-barrel piping, and at each point a hy- from acidity to alkalinity, or vice versd.
draulic back-pressure valve is inserted, in order Indicators. Although many natural and
to prevent the oxj'gen through any mischance artificial colouring matters have been recom-
flow ing back through the acetylene service. The mended as indicators, comparatively few are
first successful blowpipe was the Fouche, em-
actually used, those most frequently employed
ployed with the low-pressure system, and this being methyl orange, phenolphthale'in, and litmus.
type has held its own in spite of the competition Artificial indicators are either very weak
of other patterns. After the weld has been organic acids or (more rarely) weak bases, and
made the plate is annealed, this being essential. the prevalent view regarding their behaviour is
Although the results of tests up to the present that in solution their colour in the non-ionised
are not very consistent, it may be taken that, state differs from that which they exhibit in
on the average, the welded joint has a tensile the ionic condition.
strength from 95 to 80 p.c., depending on the In accordance with the ionic theory of solu-
thickness of the plate. tion, a very weak acid HM
exists in solution,
There are many classes of work in which mainly, but not entirely, in the non-ionised state,
oxy-acetylene welding can be advantageously the equilibrium between ions and undissociated
employed. In the motor-car industry, both
in the garage and repair shop, it has proved of molecules HM^H+M being expressed quanti-
great service, it being a comparatively simple tatively by the equation
matter, for instance, to mend a cracked cylinder - +
or gear-box. For the welding of tubes, repairs M X H/HM = constant
to boilers in situ needed by corrosion, &c., in which the symbols denote the molecular con-
for the mending of fractured stems and stern centrations of the ions and molecules, and where
posts, the process has been invaluable. +
Acetylene has been found of great service in
as in the case under discussion M
and H are very
the illumination of small towns and country small in comparison with HM.
villages, and for isolated houses and farms. It +
hag been employed in photography on account Any increase in the value of H, which is
effected by adding a small quantity of a fairly
of its richness in actinic rays. For headlights
on motors, for tram, lighting, for buoys, and strong (ionised) acid to the solution, leads to a
in fact in a number of cases where bright and
corresponding diminution in the value of M.
trustworthy light is required without the com- The reverse change, leading to an increase in
plication of a coal-gas works or the dangers of
oil, acetylene has proved its worth. the value of M, with a corresponding decrease
It has been found that the rays from an
acetylene light possess remarkable penetrative in the value of H, is effected by adding a slight
powers in fog or mist, being in this respect amount of a fairly strong (ionised) alkali hy-
ACIDIMETRY AND ALKALIMETRY. 35
product obtained from the dried female insect
droxide, since the equilibrium H OH =
X constant Coccus cacti (Linn.), is termed carminic acid.
obtains in aqueous solutions, and the alkali added The best '
^trade product,
which is called silver
increases considerably the value of the factor
cochineal,' was first recommended as an indicator
OH. Ifthe acid HM
and the ion Mdiffer in by Luckow (J. pr. Chem. 1861, 84, 424; Zeitsch.
anal.Chem. 1862, 1, 386) ; 3 grams of the sub-
colour, then, in any solution containing this
stance (not pulverised) is extracted with 250 c.c.
acid a change from acidity to alkalinity, i.e. from
of dilute alcohol (1 vol. alcohol 3-4 vols.
:
water),
a state in which H predominates over OH to the and the clear liquid decanted. In alkaline solution
reverse condition, may be indicated by an appre- the colour is violet, in acid This
yellowish-red.
ciable change of colour. The degree of ionic indicator, which is very sensitive to strong acids
dissociation of the indicator HM
must, however, and bases, is extremely useful in
titrating
be considerably smaller than that of either acid ammonia ; it is scarcely affected by carbon
or alkali employed in the titration ; moreover, dioxide. The colour-change is well defined even
another acid HR, having a smaller degree of in artificial light. Cochineal is, however, useless
ionisation than HM, will indicate the transition for titrating organic acids and iron, aluminium
;
with even greater precision, providing that the and copper salts must be absent, since their
solutions remain pink even when
recognition of the\ colour-change is not more acid.
difficult. The quantity of indicator employed Curcumin (Turmeric yellow). The
colouring
must be so small that the amount of alkali matter from the roots of Curcuma longa
required to neutralise it is negligible. (Linn.), is turned yellow by acids and reddish-
For Theory of Indicators, v. Ostwald (Scien- brown by alkalis it is nearly always employed
;
as a test-paper, and is useful in

tific Foundations of Analytical Chemistry, trans- detecting ammonia
lated by McGowan), Kiister (Zeitsch. anorg. and boric acid.
Chem. 1897, 13, 127), Waddell (J. Phys. Chem. Gallein (Alizarin violet, Pyrogallolphtha-
1898, 2, 171), Vaillant (Compt. rend. 1903, 136, le'in). This compound, prepared by heating
1192), Stieglitz (J. Amer. Chem. Soc. 1903, 25, together pyrogallol and phthalic anhydride
1112; Amer. Chem. J. 1908, 39, 651 ; 1909, 42, (Baeyer, Ber. 1871, 4, 457, 555, 663), was pro-
115), McKoy (Amer. Chem. J. 1904, 31, 503), posed as an indicator by Dechan (Pharm. J. 15,
Hewitt (Analyst, 1908, 33, 85), Salm (Zeitsch. i
849). A 0-1 p.c. alcoholic solution is used,

10 drops being added to 100 c.c. of liquid. In
physical. Chem. 1906, 57, 471 ; Zeitsch. Elek. |
Chem. 1907, 13, 125), Salessky (Zeitsch. Elek. alkaline solution the colour is reddish-violet, in
Chem. 1904, 10, 204), Fels (Zeitsch. Elek. Chem. acid pale-broivn. This indicator is scarcely
1904, 10, 208), Schoorl (Chem. Zentr. 1907, affected by carbon dioxide, and can be used in
i. 300, 502, 585), Hantzsch (Ber. 1907, 40, the accurate titration of organic acids.
1556; 1908, 41, 1187), Rohland (Ber. 1907, 40, Iodoeosin ( Tetraiodofluoresce'in, Erythrosin
2172), Acree (Amer. Chem. J. 1908, 39, 528, 649, B.). This substance, prepared by iodating
789), Handa (Ber. 1909, 42, 3179) ; and cf. Noyes fluorescein, is a brick-red powder soluble in
for the physico-chemical theory ( J. Amer. Chem. hot alcohol or in ether, but almost insoluble
Soc. 1910, 32, 815). in water or cold alcohol it was first recom-
;
Indicators may be divided broadly into three mended by Mylius and Forster (Ber. 1891, 24,
classes (i. ) Those insensitive to very weak acids,
: 1482) ; 0-5 gram of the sodium derivative of
such as carbonic, boric, and hydrosulphuric iodoeosin is dissolved in 1 litre of water, 2-5 c.c.
acids; these indicators comprise among others are added to the solution to be titrated together
methyl orange, lacmoid, cochineal, and iodoeosin. with 5 c.c. of chloroform, the mixture being
(ii.) Those somewhat sensitive to weak acids,
shaken in a stoppered bottle during titration.
although as a rule these acids cannot be While alkaline the aqueous layer is rose red,
accurately titrated with their aid ; if weak
when acid the aqueous layer becomes colourless,
volatile acids such as carbonic acid are and the chloroform assumes a yellowish tint
removed by boiling, these indicators act like (Ellms, J. Amer. Chem. Soc. 1899, 21, 359; M.
those of the first class towards fairly strong and F. used ether instead of chloroform). With
acids and bases. Litmus is the chief represen- this indicator, centinormal or even millinormal
tative of this group, ) Those highly sensitive
(iii.
solutions can be titrated ; it is indifferent to car-
even to weak acids. This class contains phenol- bon dioxide, and phosphoric acid can be titrated
phthale in, turmeric, and rosolic acid (v. Glaser,
:
as a monobasic acid with sodium hydroxide
Zeitsch. anal. Chem. 1899, 38, 273 ; Wagner, (Gliicksmann, Chem. Zentr. 1902, (i.) 1131).
Zeitsch. anorg. Chem. 1901, 27, 138). Feeble bases, such as the alkaloids, may also
The more important indicators are de- be titrated, using iodoeosin as indicator.
scribed below in alphabetical order. Lacmoid (Resorcin Blue). This substance
Aurin (Commercial or para-Bosolic acid) is obtained by heating gradually to 110
is a mixture of several substances, a mixture of 100 parts of resorcinol, 5 r
produced
by heating together phenol and oxalic and of sodium nitrite, and 5 parts of water,
sulphuric acids ;
it appears in commerce in the violent reaction moderates, the ma^
yellowish-brown resinous lumps. A 1 p.c. solu- to 115-120 until evolution of air-
tion in 60 p.c. alcohol is employed, 0-5 c.c. being The product is a glistening
added to the solution to be titrated. In acid (Traub and Hock, Ber. 1884,
solution the colour is pale yellow, in alkaline A0-3 p.c. alcoholic solution is empk <*
solution rose-red. This indicator is very sensi- better colour change is produce ^s of :
tive and well adapted for titrating barium naphthol green are dissolved in | of this
hydroxide solutions, but it is affected by carbon solution (Zeitsch. angew. Chem. 189C >, 163). In
dioxide and hydrogen sulphide. alkaline solution the colour is blue ; in acid,
Cochineal. The colouring matter in the red. Although these colour changes resemble
D 2
36 ACIDIMETRY AND ALKALIMETRY.
those of litmus, the indicator is more closely sodium salt) is dissolved in 1 litre of water, and
allied to methyl orange. It is only slightly two drops of this solution are added in each
affected by carbon dioxide, although direct titration ;if, owing to dilution during the
titration of not satisfactory in
carbonates is titration, the colour becomes too faint, another
cold solution ; lacmoid test paper may, how- drop of the indicator is added on no account
;
ever, be used in almost any experiment for should too much indicator be used, since the
which methyl orange is suitable. This indicator colour change, from yellow in alkaline to pink
is useless for organic acids. in acid solution, is not sharp in such circum-
Litmus occurs in commerce in the form of i stances. Methyl orange is exceedingly useful,
small cubical granules mixed with a large pro- since its indications are practically unaffected
portion of calcium carbonate. An aqueous solu- | by the presence of carbonic, hydrosulphuric,
tion of this product not only contains free alkali, boric, and silicic acids ; carbonates and sulphides
but also a variable proportion of colouring may therefore be titrated in cold solution as if
matters which interfere with the delicacy of the !
they were hydroxides. All titrations must be

reaction. Special precautions must therefore be made with this indicator in cold aqueous solution,
taken in preparing the solution for use in and, since methyl orange is not very sensitive as
acidimetry. Various processes have been recom- compared with various other indicators, the acid
mended by Berthelot and De Fleurieu (Ann. or alkali employed should be fairly concentrated.
Chim. Phys. 1865, [4] 5, 189), Wartha (Ber. 1876, It is advisable to employ normal solutions,
9, 217), Mohr (Titrirmethode), Luttke (Zeitsch. though with N/2 or even N/5 solutions it is
anal. Chem. 1892, 31, 692). The following method possible to determine an end-point to within a
gives excellent results The litmus is extracted
:
singledrop. With N/10 solutions, especially
three or four times with boiling methylated when carbonates are being titrated, there is a
alcohol of 85 p.c. in order to remove the injurious distinct brownish transition tint between the
colouring matters, the residue is extracted with yellow and pink, and results may be uncertain
cold water, slightly acidified with sulphuric acid, to the extent of one or two drops (cf. Kiister,
and boiled to expel carbon dioxide. The extract Zeitsch. anorg.Chem. 1897, 13, 140).
is neutralised with
baryta water, a few bubbles The addition of indigo-carmine to methyl
of carbon dioxide passed in to remove excess of orange has been recommended by Luther (Chem.
baryta, and the liquid again boiled and filtered. Zeit. 1907, 31, 1172), who states that the colour
The solution should contain about 20 grams of change very pronounced. Ethyl orange is
is
solid matter per litre, and must be kept in vessels stated by Wieland to be even better than methyl
to which the air has free access. If kept in orange (Ber. 1883, 16, 1989).
closed vessels it undergoes fermentation and is Methyl, red. This substance, prepared by
decolourised. The colour is restored when the diazotising anthranilic acid and coupling the
liquid is exposed to air. The colour of the resulting diazonium salt with dimethylaniline,
solution should be purple ; it turns blue with was introduced as an indicator by Rupp and
alkalis, and red with acids, and is affected by Loose (Ber. 1908, 41, 3905). A 0-2 p.c. alco-
carbon dioxide, sulphur dioxide, and hydrogen holic solution is employed, and two drops of
(For the relative merits of litmus and this are added in each titration. The colour
:
sulphide.
methyl orange, v. Reinitzer, Zeitsch. angew. change is from a pure yellow in alkaline to a
Chem. 1894, 547, 574; Lunge, ibid. "1894, reddish-violet in acid solution, and is very pro-
733.) nounced. This indicator is very sensitive, and
The colour change is rendered more delicate can be used for titrating weak bases in centi-
by conducting the titration in the monochro- normal solution. The precise extent to which
matic light obtained by heating a bead of sodium it is affected by carbon dioxide has not yet been
carbonate in a bunsen flame (L. Henry, Compt. determined but ordinary sodium hydroxide
;
rend. 1873, 76, 222). The red solution seems solutions containing a little carbonate can be
colourless, whilst the blue solution is almost black. accurately titrated in the cold.
Litmus is not well adapted for use by gas- or Phenacetolin, first recommended by Degener
lamp-light. (Zeit. d. Ver. f. d. Riibenzucker Industrie, 1881,
Luteol. The preparation of this substance, a- 357; J. Soc. Chem. Ind. 1882, 1, 85), is prepared
hydroxychlorodiphenylquinoxaline, is described by boiling together for several hours -molecular
by Autenrieth (Arch. Pharm. 1895, 233, 43), and proportions of phenol, acetic anhydride, and
by Glaess and Bernard (Mon. Sci. 1900, 14, 809) ;
sulphuric acid. The product is extracted with
it forms woolly, yellowish needles, m.p. 246.
fine, water to remove excess of acid, dried and dis-
A 0-33 p.c. alcoholic solution is used as an indi- solved in alcohol in the proportion of 1 gram to
cator. In alkaline solution the colour is yellow ; 500 c.c. It is pale yellow with alkalis, red with
in acid it is colourless. This indicator is said to carbonates of the alkalis and alkaline earths,
be remarkably sensitive, excelling Nessler's solu- colourless or pale yellow with acids. It is used
tion as a test for ammonia ; but it is sensitive for estimating both hydroxide and carbonate
to carbon dioxide (Higgins, J. Soc. Chem. Ind. when present in the same solution.
1900, 19, 958). It was especially recommended Phenolphthalein, obtained by heating phenol
by Autenrieth for use in Kjehldahl's process (v. with phthalic anhydride and concentrated sul-
ANALYSIS). phuric acid (Baeyer, Annalen, 1880, 202, 69),
Methyl orange (Helianthin, Poirrier's Orange was proposed as an indicator by Luck (Zeitsch.
III.). This substance, prepared by diazotising anal. Chem. 1877, 16, 322). One or two drops of
sulphanilic acid and coupling the resulting diazo- a 0-5 p.c. alcoholic solution are used in each
nium salt with dimethylanuine, was introduced titration. In alkaline solution the colour is red ;
as an indicator by Lunge (Ber. 1878, 11, 1944 ; the acid solution is colourless. Owing to its very
J. Soc. Chem. Ind. 1882, 1, 16). One gram of weak acid character, phenolphthalein is the
pure methyl orange (either the free acid or its indicator par excellence for organic acids ;
it
is useless, however, in the presenceof am- Compt. rend. 1900, 130, 1128; Gerock, Chem.
monium salts, and since even carbonic and Zentr. 1900, ii. 1294) ; flavescin (Lux, Zeitsch.
hydrosulphuric acids discharge the red colour, anal. Chem. 1880, 19, 457); fluoresce'in
(Kriiger,
it is necessary to work with solutions free from Ber. 1876, 9, 1572 ; Zellner, Chem. Zeit. Rep.
these acids or titrate in boiling solution; 1901, 25,40); hcematoxylin (Wildenstein, Zeitsch.
hence its use is somewhat restricted. A con- anal. Chem. 1863, 2, 9) ; melanil yellow (Linder,
venient method of titrating organic acids with J. Soc. Chem. Ind. 1908, 27, 485); methyl-3-
ordinary sodium hydroxide solutions using phenol
-
aminoquinoline (Stark, Ber. 1907, 40, 3434);
phthalein as indicator, is described by Philip extract of mimosa flowers (Robin, Compt. rend.
(Chem. Soc. Trans. 1905, 87, 991); cf. McCoy 1904, 138, 1046) ; para-nilrophenol (Langbeck,
(Amer. Chem. J. 1904,31, 503); and Schmatolla Chem. News, 1881, 43, 161 ; Spiegel, Ber. 1900,
(Ber. 1902, 35, 3905). 33, 2640; Zeitsch. angew. Chem. 1904, 17, 715;
Turmeric v. CTTKCUMIN. Goldberg and Naumann, Zeitsch. angew. Chem.
Many other indicators have been proposed 1903, 16, 644) ; paranitrobenzeneazo-a-naphthol
from time to time, among others the following :
(Hewitt, Analyst, 1908, 33, 85) ; and Poirrier's
Alizarin (Scha&l, Ber. 1873, 6, 1180); Alizarin-
'
blue C4B (Engel, Compt. rend. 1886, 102, 214).
red 1. W.S. (Knowles, J. Soc. Dyers, 1907, 23, The relative sensitiveness of the more im-
120) ; Congo-red ; cyanine (Schonbein, J. pr. portant indicators and their behaviour under
Chem. 1865, 95, 449) ; cyanogen iodide (Kastle various conditions have been investigated by
and Clark> Amer. Chem. J. 1903, 30, 87); Wieland (Ber. 1883, 16, 1989), andespecially by
diaminazoatoluenesulphonic acid (Troeger and Thomson (Chem. News, 1883,47, 123, 135, 184;
Hille, J. pr. Chem. 1903, 68, 297) ; ferric salicylate 1884, 49, 32, 38, 119; 1885, 52, 18, 29), whose
(Weiske, J. pr. Chem. 1875, 12, 157; Wolff, results are summarised in the following table :
-
concentration of the acid solution is calculated sulphate solution (Hart and Croasdale, Chem.
from each result, and the mean of the concordant News, 1891, 63, 93; Kohn, J. Soc. Chem. Ind.
values adopted as correct. Chemically pure 1900, 19, 962).
sodium carbonate is obtainable in commerce, Hydrochloric acid. In preparing a normal
and should be free from all but traces of chloride solution advantage may be taken of the fact
and sulphate ; it is dried in a platinum crucible that an aqueous solution of hydrogen chloride
with continual stirring for 20-30 minutes at which boils at a constant temperature has a
such a temperature that the crucible bottom is practically constant composition. A
quantity
barely red hot, or the crucible, embedded in of ordinary concentrated acid is distilled from a
sand, may be heated at 300 for half an hour. capacious retort until one-third has passed over.
Pure sodium carbonate may also be prepared The residual liquid will contain 20-2 p.c. of
by heating the bicarbonate at a temperature hydrogen chloride, and 165 c.c. when diluted
not exceeding 300 (Lunge, Zeitsch. angew. |
to 1 litre will form an almost exactly normal
Chem. 1897, 10, 522). Sulphates and chlorides i solution ; it should be standardised by one of
are removed from the bicarbonate by washing j
the following processes.
with cold water. (For the preparation of pure The strong acid is diluted until its specific
sodium bicarbonate, v. Reinitzer (Zeitsch. angew. i
gravity is approximately 1-1, and distilled; after
Chem. 1894, 7, 551), and North and Blakey (J. !
three-fourths of liquid have passed over, the
Soc. Chem. Ind. 1905, 24, 396).) remaining distillate is collected apart, and the
The foregoing method, although extensively barometric height observed. The final quarter
used, has been adversely criticised, the chief of the distillate is of perfectly definite com-
objection being that it is impossible to dehydrate position, and the following table gives the actual
the carbonate or bicarbonate without losing a !
content of hydrogen chloride for a definite baro-
little too much carbon dioxide. It is asserted metric height, together with the weight of
that sodium oxide present even when the
is distillate which contains one gram-equivalent of
temperature of drying has not exceeded 170 ;
hydrogen chloride, i.e. which yields a normal
v. Kissing (Zeitsch. angew. Chem. 1890, 3, 262); solution when diluted to 1 litre :
Higgins (J. Soc. Chem. Ind. 1900, 19, 958); Grams of mixture con-
Sorensen and Andersen (Zeitsch. anal. Chem. Barometer
1905, 44, 156); North and Blakey (J. Soc. 770
Chem. Ind. 1905, 24, 396); Sebelin (Chem.
Zeit. 1905, 29, 638); but cf. Seyda (Chem.
Zentr. 1899, 1164); Lunge (Zeitsch. anal.
(i.)
Chem. 1904, 231 ; 1905, 18, 1520).
17,
A satisfactory method of checking the values
obtained by the carbonate method depends on
the fact that sodium oxalate, when heated, is
converted into sodium carbonate. As this
oxalate can be prepared in a high degree of
purity, the residue of carbonate theoretically
obtainable from a known weight of oxalate can
be calculated, and the presence of any sodium
oxide is immaterial providing that all calcula-
tions are based on the original weight of sodium
oxalate.
The weighed oxalate is carefully heated in
a platinum crucible until all the separated carbon
has been burnt off and the residual carbonate
begins to fuse the cooled residue is dissolved
;
in water and titrated as already described v.;
Sorensen (Zeitsch. anal. Chem. 1897, 36, 639;

1903, 42, 333, 512; 1905, 44, 156), Lunge
(Zeitsch. angew. Chem. 1905, 18, 1520); and
ANALYSIS, (Volumetric section, standardisation
of permanganate).
From time to time many other standards
have been proposed, and among others the
following :
Potassium succinic acid (Phelps

tetroxalale ;
and Hubbard, Chem. 1907, 53,
Zeitsch. anorg.
361 ; Phelps and Weed, ibid. 1908, 59, 114,
120); borax (Rimbach, Ber. 1893, 26, 171);
potassium hydrogen tartrate (Borntrager, Zeitsch.
anal. Chem. 1892, 31, 43); potassium dichromate
(Richter, Zeitsch. anal. Chem. 1882, 21, 205);
potassium iodate (Fessel, Zeitsch. anal. Chem.
1899,- 38, 449); potassium biiodate (Meineke,
Chem. Zeit. 1895, 19, 2); sodium (Hartley,
Chem. Soc. Trans. 1873, 26, 123; Neitzel,
Zeitsch. anal. Chem. 1893, 32, 422; cf. Hopkins,
J. Amer. Chem. Soc. 1901, 23, 727); and
sulphuric acid, prepared by electrolysing copper
ACIDIMETRY AND ALKALIMETRY.
39
convenient method of expressing the result ; of sulphuric acid in the
solution is then obtained
e.g. if the acid is used to estimate an alkali of f rence to ta bles
L giving the values for
equivalent e, then 1 c.c. acid = ^-^ x z grams
i
15715 or 18/18 (v. Sutton's Volumetric
Analysis, 9th ed., or J. Soc. Chem. Ind. 1899, 18,
of alkali. If necessary, the acid solution may 4). The table given in J. Soc. Chem. Ind.
1902,'
be diluted with distilled water so that the ratio 21, 1511, may be employed when the
final volume -f- initial volume z =
it will then;
specific
gravity (15715) has been calculated without
be exactly normal. A simple arithmetical calcu- introducing any vacuum corrections, which
lation is required, and if this process is con- must be allowed for if the other tables are
templated, care should be taken initially to employed. Between the limits of 66 p.c. and
ensure that z shall be slightly greater than 81 p.c. the
following formulae reproduce the
unity. values in the tables with an error not
exceeding
Hydrochloric acid is most accurately stand- 0-04 p.c. :
ardised gravimetrically by precipitating chlorine P = 86 S - 69-00

with excess of silver nitrate and weighing the P = 86S,15 -68-82
8
silver chloride in a Gooch crucible. The solution
may be titrated against pure silver according to where P = percentage of sulphuric acid, and
the Mint process for assaying this metal. The 8j 5 and S 18 = the specific
gravities referred to
method may be modified by adding the silver water at 15 and 18 respectively, calculated
solution in very slight excess, this excess being without allowing for air ' '
displaced (Marshall
determined in the filtrate with N/10-thiocyanate J. Soc. Chem. Ind. 1899, The diluted
18, 4).
Dittmar's acid may be kept in a
(Thorpe's Quantitative Analysis ; stoppered bottle without
Quantitative Analysis Knorr, J. Amer. Chem.
; change, and by weighing out the appropriate
Soc. 1897, 19, 814; Hopkins, ibid. 1901, 23, amount and diluting to a litre, a normal solution
These methods are trustworthy only of sulphuric acid can be
727). rapidly prepared.
when the hydrochloric acid is free from chlorides. Oxalic acid. A normal solution is
prepared
A simple and accurate process of standardisa- by dissolving 63-03 grams of the recrystallised
tion consists in immersing weighed pieces of Ice- hydrated acid 2 C 2 4
H
2H +
in water and
land spar in a measured volume of the acid, and diluting to 1000 c.c. As the" crystallised acid
noting the loss in weight of the spar after the
is somewhat effloresent, especially on slightly
acid is neutralised (Masson, Chem. News, 1900, warming, it may contain less than two molecular
81, 73 ; Green, ibid. 1903, 87, 5 cf. Thiele and
; proportions of water. The solution may be
Richter, Zeitsch. angew. Chem. 1900, 13, 486). checked against a standard alkali,
using phenol-
Small quantities of standard hydrochloric phthalein as indicator, or against an accurately
acid may be prepared by absorbing dry hydrogen standardised permanganate solution (cf. Tread-
chloride in a weighed quantity of water and well-Hall, Analytical Chemistry, vol. 2).
ascertaining the increase in weight (Moody, Oxalic acid solutions do not keep very well.
Chem. Soc. Trans. 1898, 73, 658; Higgins, J. Sodium hydroxide. To prepare a normal
Soc. Chem. Ind. 1900, 19, 958 ; Acree and solution, clear transparent lumps of the best
Brunei, Amer. Chem. J. 1906, 36, 117). white commercial caustic soda are selected, any
Sulphuric acid. An approximately normal opaque portions of their surface scraped off, and
solution is obtained by diluting to 1 litre 28 c.c. 50 grams of the substance weighed out for each
of pure concentrated sulphuric acid (sp.gr. 1-84). litre of solution. The cooled solution is stand-
The solution may be standardised with pure ardised against the standard hydrochloric acid,
sodium carbonate or oxalate (v. HYDROCHLORIC using methyl orange as indicator, and taking
ACID), or a measured quantity treated with a 50 c.c. for each titration.
slight excess of ammonia, evaporated to dryness, For the preparation of sodium hydroxide
and the residual ammonium sulphate heated at solutions free from carbonate, v. Kiister (Zeitsch.
120 and weighed. This method gives trust- anorg. Chem. 1897, 13, 134 1904, 41, 472, and
;
worthy results only when pure redistilled acid Bousfiekl and Lowry, Phil. Trans. 1905, 204, 253).
is employed in preparing the solution
(Weinig> Potassium hydroxide cf. SODIUM HYDROXIDE.
Zeitsch. angew. Chem. 1892, 5, 204; Shiver, Barium hydroxide. An approximately N/10-
J. Amer. Chem. Soc. 1895, 17, 351 Hopkins, ;
solution is best prepared from the crystalline
ibid. 1901, 23, 727 Marboutin and Pecoul,
; hydroxide Ba(OH),, 6H.,O. The powdered sub-
Bull. Soc. chim. 1897, 17, 880). stance is shaken with distilled water, the solu-
Ameasured volume of the acid is added to a tion allowed to settle, the clear liquid siphoned
weighed excess of sodium carbonate in a platinum off and diluted with an equal volume of recently
dish, the solution evaporated, the residue dried boiled-out water. The solution must be kept
at 300 and weighed. The change in weight due permanently in contact with that portion already
to the transformation of sodium carbonate into in the burette, and guard tubes are required
sulphate indicates the amount of acid present in to prevent access of carbon dioxide. The
the solution. This method is much preferable solution is standardised against succinio acid,
to precipitating and weighing the acid as barium phenolphthalein being used as indicator; or a
sulphate (cf. Richardson, J. Soc. Chem. Ind. measured volume may be evaporated to dryness
1907, 26, 78). with a slight excess of pure sulphuric acid, the
Sulphuric acid solutions of definite concentra- residual barium sulphate being gently heated
tion may be prepared by specific gravity measure- and weighed.
ments (Pickering, Chem. Soc. Trans." 1890, 57, The chief use of this solution is in titrating
64). A
quantity of the purest acid is diluted with organic acids, using phenolphthalein as indicator.
half its volume of water, and the specific gravity For this purpose carbon dioxide must be ex-
of the mixture accurately determined at 15 or cluded, and barium hydroxide is consequently
18 in a Sprengel pyknometer. The percentage the most convenient alkali to employ.
Ammonia. This solution is not often em-
ployed ; an approximately semi-normal solution,
readily obtained by diluting 28 c.c. of concen-
trated ammonia solution to 1 litre, is titrated
against hydrochloric acid in the cold, using
methyl orange as indicator ;phenolphthaleiin
cannot be employed.
Schultze has determined the rates of expan-
sion of normal solutions of acids and alkalis
and other solutions employed in volumetric
analysis (Zeitsch. anal. Chem. 1882, 21, 170).
The following are the results for average
temperatures :
burette tip dipping into the liquid to prevent fora method of estimation
entirely different in
escape of carbon dioxide, until the liquid be- principle from the foregoing.)
comes colourless. At this point, which corre- Hydrochloric, Hydrobromic, Hydriodic, Sul-
sponds with the complete conversion of the phuric, and Nitric acids are readily estimated by
normal carbonate into acid carbonate, the volume direct titration with standard alkali,
using methyl
of acid added is read off. The liquid is then orange as indicator.
boiled and acid is added gradually until the Oxalic, Tartarie, Citric, Acetic, and Lactic
solution remains colourless even after long acids can likewise be titrated
accurately with
boiling, and the volume of acid is again read standard alkali if phenolphthaleiin is used as the
off. If x represents the first reading, and y the indicator (Thomson, I.e.). Oxalic acid
may
also
second reading, then 2x = the normal carbonate, be titrated, using litmus as indicator.
and y 2x = the acid carbonate (Warder, Chem. Boric acid gives no very definite reaction
News, 1881, 43, 228). with the majority of indicators, but it is quite
Lunge (J. Soc. Chem. Ind. 1882, 1, 57) neutral to methyl orange, and hence the
quantity
proposes a different method based on the of alkali in akaline borates can be
accurately
reaction : estimated by direct titration with standard acid
aM^GOa -l-i/MHCOa + zNH 3 + (x + j/)BaC! 2 if methyl
orange is used as indicator (Thomson).
=(2x + y)MCl + j/NHiCl + (x + j/)BaCO 3 + (z - The titration of boric acid itself becomes
The solution to be tested is mixed with a mea- possible if the solution contains at least 30 p.c.
sured excess of standard (half -normal) ammonia, of its volume of glycerol. The boric acid then
excess of barium chloride added, and the liquid behaves towards phenolphthaleiin as a monobasic
diluted with recently boiled water to a definite i
acid (Thomson, J. Soc. Chem. Ind. 1893, 12, 432 ;
volume. When the precipitate has settled, an |
Jorgensen, Zeitsch. angew. Chem. 1897, 10, 5 ;
aliquot portion of the clear liquid is withdrawn ;
Honig and Spitz, ibid. 1896, 9, 549 Copaux,

;
and titrated with standard acid in order to as- Compt. rend. 1898, 127, 756). A similar result
certain the excess of ammonia. The difference
J
is effected by saturating the solution with

between the volume of ammonia added and that mannitol. Since phenolphthalein is employed,
remaining after precipitation gives the volume carbon dioxide must not be present in the
corresponding with the quantity of acid carbonate j
solutions to be titrated (Jones, Amer. J. Sci.
in the liquid analysed. i
1898, 7, 147 Stock, Compt. rend. 1900, 130,

;
By adding a definite excess of pure sodium !
516).
hydroxide from carbon dioxide, a mixture
free Sulphurous acid can be titrated directly if
of normal carbonate and hydroxide is obtained I methyl orange, phenolphthalein, or aurin is used
which may be analysed as described above. as indicator (Lunge, Dingl. poly. J. 250, 530).
Ammonia. In order to determine the quan- With methyl orange the hydrogen sulphite
tity of free ammonia in a solution of the gas, an MHS0 3 is the neutral salt, whilst with the other
accurately measured quantity (10 c.c.) of the two indicators the normal salt is neutral. This
liquid transferred to a light tared flask, and
is I difference can be utilised for the determination
weighed. This gives at once the weight taken of the relative proportions of normal and acid
for analysis and the sp.gr. The liquid is then sulphite in the same solution (Blarez, Compt.
titrated with standard acid in the usual way, rend. 1886, 103, 69; Chem. Soc. Abst.
using litmus, lacmoid, or methyl orange as 1886, 50, 918). Caustic soda or potash must
indicator. be used, since ammonia gives inaccurate results.
Ammonia in combination is determined by Phosphoric and Arsenic acids are monobasic
boiling the substance with sodium hydroxide, with methyl orange, and dibasic with phenol-
leading the ammonia into a measured excess of phthalein (Joly, Compt. rend. 1882, 94, 529;
standard acid, and determining the residual acid Chem. Soc. Abst. 1882, 42,692). These acids
with standard alkali. The substance is weighed can be most accurately titrated with barium
into a flask fitted with a cork, through one hole hydroxide, using phenolphthalein as indicator.
in which passes a pipette containing a strong Towards the close of the reaction, time must
solution of sodium hydroxide, whilst through be allowed for the gelatinous tribarium phosphate
another passes a tube leading to a flask or bulb 1
to change into the crystalline dibarium salt

U-tube containing a known volume of standard i
(Joly, Compt. rend. 1886, 102, 316 ;Chem. Soc.
acid. The flask or U-tube is fitted with a cork I
Abst. 1886, 50, 418). Advantage can be taken
'
which carries a calcium chloride tube containing of the different basicity with methyl orange
beads moistened with some of the acid in order ;
and phenolphthalein to estimate phosphoric acid
to ensure complete absorption of the ammonia. !
in presence of monobasic acids such as hydro-
After addition of the sodium hydroxide solution chloric acid (Joly, Compt. rend. 1885, 100, 55 ;
the liquid is gently boiled for half an hour, and |

Chem. Soc. Abst. 1885, 48, 348).
the residual acid determined. From the volume (For another simple and accurate method, v.
of acid which has combined with the ammonia
Segalle, Zeitsch. anal. Chem. 1895, 34, 33.)
1
the quantity of the latter is readily calculated. Carbonic acid in solution is estimated by
The sodium hydroxide may be replaced by milk i
adding excess of ammonia and calcium chloride.

of lime, and the most effectual method of The liquid is then boiled, and the precipitated
1
removing the ammonia is to distil the mixture calcium carbonate collected, well washed, and
in steam. The use of magnesia in place of dissolved in a measured excess of standard hydro-
sodium hydroxide is not advantageous (Kober, chloric acid, the excess of acid being determined
J. Amer. Chem. Soc. 1908, 30, 1279). (For a by means of standard alkali. The volume of
[
different method of distilling off the ammonia, normal acid actually used multiplied by 0-022
v. Kober (J. Amer. Chem. Soc.
1908, 30, 1131). gives the quantity of carbon dioxide.
See also Ronchese (J. Pharm. Chim. 1907, 25, Insoluble carbonates are weighed into a flask
611) and Wilkie (J. Soc. Chem. Ind. 1910, 29, 6) fitted with a cork which carries a bulb and
delivery tube. The bulb contains moderately formed, but as soon as the free acid is neutralised,
strong hydrochloric acid, which is allowed to the ammonia in a fresh quantity of cupram-
drop slowly on the carbonate, and the evolved monium sulphate reacts on the cupric sulphate
gas is led into a flask containing strong ammonia already in the liquid and produces a precipitate
solution. This flask is closed with a cork, of a basic salt, the formation of which indicates
through which passes the delivery tube, which the point of saturation. The precipitate is most
ends just above the surface of the liquid. The readily seen against a black background. In
cork also carries an exit tube filled with glass order to standardise the liquid, 10 c.c. of normal
beads moistened with ammonia to arrest the sulphuric acid are placed in a flask or beaker
last traces of carbon dioxide. When all the gas and Kieffer's solution added until a permanent
has been expelled from the carbonate the am- precipitate is produced, and from the volume
monia is mixed with calcium chloride, boiled, of solution required, its strength in terms of
and the precipitate treated as above cf. Gooch ; normal acid is readily calculated. The strength
and Phelps (Amer. J. Sci. 1895, 50, 101). With of the solution gradually diminishes, and it must
slight modification this process can be adapted be titrated from time to time. In making an
to the estimation of carbon dioxide in aerated actual determination, the Kieffer's solution is
waters. added to the liquid to be tested until a per-
For the direct titration of carbon dioxide in manent precipitate is formed. The method is
solution, v. Seyler (Analyst, 1897, 22, 312) ; not very accurate, owing mainly to the fact that
Ellms and Beneker (J. Amer. Chem. Soc. 1901, the precipitate is not quite insoluble in solutions
23, 405) and Forbes and Pratt J. Amer. Chem.
; (
of ammonium salts, and therefore the end re-
Soc. 1903, 25, 742). action does not take place until the liquid is
Hydrofluoric acid may be accurately titrated saturated with the basic salt. The magnitude
with sodium hydroxide free from carbonate, of the error depends on the concentration
using phenolphthale'in as indicator (Winkler, of the solution. When the liquids to be ti-
Zeitsch. angew. Chem. 1902, 15, 33 cf. Haga ; trated contain barium, strontium, &c., the
and Osaka, Chem. Soc. Trans. 1895, 67, 251 ; Kieffer's solution must be prepared with cupric
and J. Amer. Chem. Soc. 1896, 18, 415; nitrate.
Monatsh. 1897, 18, 749). (For other methods, v. Sims (Chem. News,
Hydrofluosilicic acid may be titrated with 1907, 95, 253) and Ahlum (Chem. Soc. Proc.
sodium or barium hydroxide in the presence of 1906, 22, 63).)
alcohol (an equal volume is added) using phenol- Bibliography. Mohr's Chemisch-Analytische
phthaleiin or lacmoid as indicator the alcohol
; Titrirmethode, 6th ed. 1886 Button's Volu- ;
renders the salt produced insoluble in the solu- metric Analysis, 9th ed. 1904 ; Fresenius'
tion; v. Sahlbom and Hinrichsen (Ber. 1906, Quantitative Chemische Analyse, v. 2, 6th ed. ;
39, 2609) cf. Schucht and Moller (Ber. 1906,

; Tread well- Hall, Analytical Chemistry, v. 2, 2nd
39, 3693) and Honig and Szabadka (Chem.
; ed. 1910 Lunge's Technical Chemist's Hand-
;
Zeit. 1907, 31, 1207). book Cohn's Indicators and Test Papers, 2nd
;
Combined acids in salts may be estimated ed. 1902 Glaser's Indikatoren der Acidimetrie
;
with approximate accuracy by adding to a solu- und Alkalimetrie, 1901. G. T. M.

tion of the salt a measured excess of sodium ACID ALIZARIN, -BLACK, -BROWNS,
hydroxide or carbonate. The liquid is boiled, -PONCEAU, -YELLOWS v. Azo- COLOURING
allowed to cool, and diluted to a definite volume. MATTERS.
When the precipitate has settled, an aliquot ACID MAGENTA v. TRIPHENYLMETHANE
portion of the clear liquid is withdrawn, and the COLOURING MATTERS.
excess of alkali determined by titration. From ACID VIOLET v. TRIPHENYLMETHANE
the volume of alkali used the proportion of acid COLOURING MATTERS.
in the salt is calculated. In order to avoid the ACIDINE BRILLIANT RED v. Azo- COLOUR-
error due to the presence of the precipitate, the ING MATTERS.
liquid may be filtered before diluting to a definite ACME YELLOW v. Azo- COLOURING MATTERS.
volume, but methyl orange or cochineal must be ACOKANTHERA SCHIMPERI. The arrow-
used as indicator in order to avoid any error poisons of East Africa are prepared from the
from carbon dioxide absorbed from the atmo- wood of the genus Acokanthera, which contains a
sphere. Salts of copper, silver, mercury, cobalt, crystalline glucoside, acokantherinin C 30 46 12 , H
nickel, iron, and chromium are precipitated with H 2
H
(Arnaud), C 3i! 50 0, 2 (Faust). Crystallises
sodium hydroxide ; salts of calcium, barium, from water and alcohol insol. in ether or chloro-
;
strontium, magnesium, aluminium, zinc, bismuth, form; sol. neutral and bitter. Strong sulphuric,
and manganese, with sodium carbonate. acid gives a red colour eventually becoming
Kiefler's method is useful for coloured solu- green. On boiling with dilute mineral acids is
tions, or in presence of normal salts with acid hydrolysed with formation of rhamnose. Is
reactions ( Annalen, 1855, 93, 386). Sixty grams optically inactive, softens at 130 and decom-
of crystallised cupric sulphate are dissolved in poses at 220. The pharmacological action of
water, mixed with ammonia until the precipitate the glucoside resembles that of members of the
is almost but not quite dissolved, diluted to
digitalin group (Fraser and Tillie, Proc. Roy.
about 900 c.c., the solution left for some time, Soc. 58, 70; Faust, Chem. Zentr. 1902, 2,
and the clear liquid siphoned off, or filtered [19] 1217).
through glass-wool, and diluted to 1000 c.c. ACONINE, ACONITE, ACONITINE, ACO-
If any further precipitate forms, it must be NITIC ACID v. VEGETO-ALKALOIDS.
siphoned off or collected. If the solution of ACORUS CALAMUS (Linn.). The common
cuprammonium sulphate thus obtained is added sweet flag. The root is used by distillers to
to an acid liquid, so long as the acid is in excess flavour gin, and the essential oil by snuff-makers
an ammonium salt and cupric sulphate are for scenting snuff. It contains a glucoside
ACRIDINE.
termed acorin 36 H 60
6 (Faust,
Bull. Soc. chim. the product is then oxidised with ferric chloride
[2] 9, 392 ; Thorns,
Arch. Pharm. [3] 24, 465) or potassium percarbonate 2 C 2 O g or hydrogen
K
(v. CALAMUS). peroxide, and the resulting metallic salt decom-
ACRIDINE C 13 H 9N. Crude anthracene con- posed with hydrochloric acid (D. R. P. 52324;
tains basic substances, and among them acri- Lymn, J. Soc. Chem. Ind. 1897, 16, 406 ; Ull-
dine, which can be isolated by extracting it with mann and Marie, Ber. 34,4308 Haase, Ber. 36,
;
dilute sulphuric acid and adding potassium di- 589). It forms yellow crystals melting above
chromate to the acid solution. The precipitated 300, soluble in alcohol, acetone and pyridin,
acridine chromate is then recrystallised from and forming a yellow solution in sulphuric acid
water, treated with ammonia, and the base crys- with a green fluorescence. It yields derivatives
tallised hot water (Graebe and Caro,
from which form yellow, orange, brownish-, greenish-,
Annalen, 158, 265 Ber. 13, 99).;
and reddish-yellow dyes, and can be used on
Acridine has also been obtained syntheti- cotton, leather, wool, and silk. The following
cally by passing the vapours of orthotolylaniline are some of the methods of preparation :
and of orthoditolylamine through a tube heated (1) heating with mineral acids under pressure,
to.dull redness (G., Ber. 17, 1370); by severally when it yields aminohydroxy- and dihydroxy-
heating formic acid and diphenylamine (Bernth- dimethyl acridine (D. R. P. 121686; Chem.
sen and Bender, Ber. 16, 767, 1802), chloroform, Zentr. 1901, ii. 78; J. Soc. Chem. Ind. 21,
diphenylamine and zinc oxide (Fischer and 37) (2) heating with monochloracetic acid and
;
Korner, Ber. 17, 101), and aniline and salicylalde- water under pressure (D. R. P. 133788 Chem. ;
hyde (M6bJ.au, Ber. 19, 2451) with zinc chloride; Zentr. 1902, ii. 616 D. R. P. 136729
; Chem. ;
by passing o-amidodiphenyl methane through Zentr. 1902, 1396) (3) heating with formalde-
ii. ;
a layer of lead oxide heated to dull redness hyde and mineral acids under pressure (D. R. P.
(Fischer and Schiitte, Ber. 26, 3085). By dis- 135771 Chem. Zentr. 1902, ii. 1233 J. Soc.
; ;
tillingtetrahy droacridine with litharge (Borsche, Chem. Ind. 21, 112, 544, 402); (4} by treatment
Ber. 41, 2203), and also from acridone (Decker with formaldehyde and aromatic bases (J. Soc.
and Dunant, Ber. 39, 2720; Ullmann, Bader Chem. Ind. 22, 140 D. R. PP. 131365, 132116
; ;
and Labhardt, Ber. 40, 4795). Chem. Zentr. 1902, ii. 172 i. 1288) (5) heating; ;
Properties. Acridine crystallises in small with benzvl chloride in presence of nitrobenzene

colourless needles, or four-sided rhombic prisms, (J. Soc. Chem. Ind. 21, 701, 1530); (6) treating
sublimes at 100, melts at 111, boils above 360 with aqueous formic acid (ibid. 21, 90) ; (7) heat-
without decomposition, and distils with steam. ing with glycerol at 150-180 (D. R. P. 151206) :
It is sparingly soluble in hot water, but readily (8) alkylation (Ullmann and Marie, I.e. D. R. P.
soluble in alcohol, ether, or carbon disulphide, 79703; J. Soc. Chem. Ind. 19, 1010; 24,
yielding solutions showing a blue fluorescence. 840).
When inhaled either as dust or vapour it causes Phenylacridine C, 9 13 H N
is obtained by heat-
violent sneezing, in solution both it and its
and ing diphenylamine with benzoic acid and zinc
salts cause much irritation on the skin. On chloride at 260 (Bernthsen, Ber. 15, 3012 ; 16,
treatment with nitric acid it yields two nitro- 767, 1810), and melts at 181. The hydroxy-
derivatives (m.p. 154 and 214) and a dinitro- phenylncridines which form yellow dyes in
derivative (G. and C. ) ; potassium permanganate mineral acids can be obtained similarly by using
oxidises it to 2 3-quinolinedicarboxylic acid
: the corresponding hydro xy acid (Landauer, Bull.
C 9 H 5 N(CO.,H) 3 and sodium amalgam reduces it
, Soc. chim. 31, 1083).
to hydroacridine C 13 H 1VN (B. and B., Ber. 16, Other acridine dyes can be obtained by
1971 G., Ber. 16, 2831). The salts are yellow and
; heating tetraminoditolylmethane or the leuco-
crystallise well, but are decomposed into their compounds of amino-acridines with mineral acid
constituents on boiling. Heated with hydrogen and alcohol under pressure, the shade depending
and finely divided nickel, it forms 2 : 3-dimethyl on the quantity and nature of alcohol and of
quinoline (Padoa and Fabris, Atti R. Acad. acid used (J. Soc. Chem. Ind. 20, 888; 22,
Lincei, 1907, [v.] 16, i. 921). The halogen addition 1126 23, 932). Also by the interaction of an
;
compounds of acridine and its derivatives are aromatic or aliphatic ?w-diamine with an alde-
formed by the direct action of the halogen on hyde (ibid. 21, 1529; Chem. Zeit. 14, 334;
the acridine (Senier and Austin, Chem. Soc. Trans. J. Soc. Chem. Ind. 17, 573; 22, 1241). By
1904, 1196); orby the action of a mixture of phos- heating the formyl derivatives of m-diamines
phorus oxy chloride and pentachloride on thio- with ammonia salts or salts of organic
acridone (Edinger, Ber. 33, 3770; D. R. P. bases at 150-200 (D. R. PP. 149409,
120586 Edinger and Arnold, J. pr. Chem. [ii.] 64,
; 149410). For other methods of preparing
182, 471 ; D. R. P. 122607); for other methods, acridine derivatives, many of which have dyeing
compare Dunstan and Stubbs (Ber. 39, 2402 ;
properties, compare Bizzarri, Gazz. chim. ita'.
:
D. R. P. 126795), Graebe and Lagodzinski 20, 407 Decker, J. pr. Chem. 153, 161 ; Mohlau
;
(Annalen, 276, 48). Alkyl iodomagnesium com- and Fritzsche, Ber. 26, 1034; Volpi, Gazz. chim.
pounds of acridine have also been obtained ital. 21, ii. 228 ; J. Soc. Chem. Ind. 19, 732 ;
(Senier, Austin, and Clarke, Chem. Soc. Trans. 21,338,701, 911, 1528; Goodwin and Senier,
1905, 1469). When exposed to sunlight acri- Chem. Soc. Trans. 1902, 285 ; J. Soc. Chem. Ind.
dine forms pale-yellow crystals, m.p. 276 (Orn- 22, 23, 90 ; D. R. PP. 133709, 107517; Ullmann,
dorff and Cameron, Amer. Chem. J. 1895, 17, Ber. 36, 1017, 1025 ; D. R. P. 141297, 141356 ;
658),. Biinzley and Decker, Ber. 37, 575;
Fox and
2 :
7-dimethyl- 3 : 6-diaminoacridine or acri- Hewitt, Chem. Soc. Trans. 1904, 529; 1905,
dine yellow NH 2 -C 6 H Me/ C^\C H Me-NH
2 6 2 2
1058; Schopff, Ber. 26, 1121; Ber. 27, 2316;
Duval, Compt. rend. 142, 341 ; Koenigs, Ber. 32,
isobtained by heating under pressure tetramino- 3599; Ullmann andMaag, Ber. 40, 2515; Austin,
djtolylmethane with hydrochloric acid and water, Chem. Soc. Trans. 1908, 1760 ; D. R. PP. 118075,
44 ACRIDINE.
152662; Pope and Howard, Chem. Soc. Trans. NH, (HC1)
97, 83.
Naphthacridine and its derivatives, which
can also be used as dyes, have been prepared ( J.
Soc. Chem. Ind. 18, 826; 19, 237 Ullmann and ;
Naef, Ber. 33, 905, 912, 2470; J. Soc. Chem. Ind.

20, 37, 573 D. R. P. 126444
;
Ullmann and ;
Baezner, Ber. 35, 2670 37, 3077 Ullmann and

; ;
Felzvadjian, ibid. 36, 1027; Ullmann and Farre,

ibid. 37, 2922 Ullmann and Fitzenham, ibid.
;
38, 3787 Baezner and Gardiol, ibid. 39, 2623

; ;
Baezner, ibid. 2650 Senier and Austin, Chem.

;
Soc. Trans. 1907, 1233, 1240 Senier and Comp-;
ton, ibid. 1907, 1927 ; Baezner and Gueorgnieff,

Ber. 39, 2438).
In the case of many of the naphthacridine
derivatives, patents have been taken by Ullmann
(D. R. PP. 104667, 104748, 108273, 117472, The reaction is capable of considerable modi-
119573, 123260, 127586, 128754, 130721, 130943); fication thus from formaldehyde and dimethyl-
;
the further alleviation of some of these, as well
as of other acridine compounds has been patented
m-phenylenediamine, acridine orange is produced
in an analogous manner. It should be noted,
by the A.-G. fur Anilin-Fabrikation (D. R. PP. however, that m-phenylenediamine gives pro-
117065, 129479). ducts which are evidently mixtures, and cannot
ACRIDINE DYESTUFFS. Acridine, though be purified (R. Meyer and R. Gross, Ber. 1899,
colourless, shows absorption bands in the ultra-
32, 2365).
violet. The salts are yellow, and the addition The reaction between an aldehyde and a
products with alkyl halides are also coloured. wi-diamine may be carried out in two stages;
(For absorption spectra, see Dobbie and Tinkler,
Chem. Soc. Trans. 1905, 87, 269.) The salts Meyer and Gross (I.e. p. 2358), for example,
of acridine itself are useless tinctorially, but
prepared a monobenzylidene derivative of vn-
amino- and alkyl-amino- derivatives of acri- toluylenediamine and converted this into
tetraminoditolyl-phenylmethane by Avarming
dine, phenylacridine, &c., are useful dyestuffs, its alcoholic solution with the hydrochloride of
generally producing yellow shades. For the
m-toluylenediamine for three hours at 60-70.
preparation of these substances, synthesis is Acridine itself may be obtained in good yield
generally resorted to, although acridine may be
nitrated (Graebe and Caro, Annalen, 1871, 158,
by heating salicylidene-aniline with phosphorus
and a-nitro-acridine has been reduced pentoxide to 250 (Blaii, Monatsh. 1897, 18, 123).
275), A closely-related synthesis of acridine
to an amino-acridine (Anschiitz, Ber. 1884, derivatives is that of F. Ullmann and E. Naef
17,437).
(Ber. 1900, 33, 905). When dihydroxydi-
One dyestuff of the acridine series, chrys-
is formed as a by-product in the manu- naphthylmethane, the product of the interaction
aniline, of formaldehyde and /3-naphthol, is heated with
facture of magenta (Hofmann, Jahresb. 1862, ^j-toluidine hydrochloride, methylhydronapth-
346). Its constitution
acridine is produced with elimination of #-
naphthol.
CH 2 (C 10
H
6 -OH) 2 + NH 2 -C 6
H 4 -CH 3
was determined by 0. Fischer and G. Korner ; = C 10 H 7
OH + CH <g;|* CH3) >NH
2
probably two molecules of aniline and one of

Rheonine is obtained from m-amino-
7>-toluidine condense when oxidised to opp-
triaminotriphenylmethane, this yielding chrys- phenylauramine or tetramethyldiaminobenzo-
aniline when further oxidised. This view is phenone and m-phenylenediamine at 200, using
zinc chloride as condensing agent.
supported by the fact that when o^-triamino-
triphenylmethane is heated with arsenic acid to
150-180, chrvsaniline is produced (Annalen, <CH,),N/\
1884, 226, 188)."
The processes for preparing amino- deriva- CO
tives of acridine on a technical scale may be
illustrated by the methods of preparing benzo*
flavine, rheonine, and diaminoacridylbenzoic acid.
Symmetrical diamino-acridines are ob-
tained by the condensation of aldehydes with
\/
N(CH 3 ) 2
m-diamines, removal of the elements of ammonia N
from the resulting tetra-amino- compound by
heating with hydrochloric acid, and oxidation
= 2H (CH 3 ) 2 N NH,
of the dihydro-acridine thus produced with 3
ferric chloride. In the case of benzoflavine

benzaldehyde and m-toluylene-diamine are
employed.
NH, NH, =
C 6 H 5 -CHO+2 H2 +
CH.
N(CH 3 )S
ACRIDINE DYESTUFFS. 45
Some derivatives of xanthene, when ener- dimethyl-wi-phenylenediamine and benzaldehyde.
getically treated with ammonia, suffer replace- I
Its reactions and uses are similar to those of
ment pyrone ox3 gen atom by an imino-
of the
-
Mark NO.
group. By the prolonged heating of fluorescein D. R. P. 68908 also mentions the use of
with ammonia under pressure, R. Meyer (Ber. 7n-aminodimethyl-o-toluidine. If the latter base
1888, 21, 3376) obtained an acridine derivative, bo condensed with jo-nitrobenzaldehyde to a
to which one of the three following constitutions triphenylmethane derivative, the nitro- group
is assignable : reduced and condensation and oxidation effected
in the usual way, an acridine
NH N dyestuff possessing
two tertiary and one primary amino- group is
NH 2 /\/ \/\NH 2 obtained (I). R. P. 70065 ; compare D. R. P.
i
71362).
The use of acetaldehyde as a component was
claimed by the Ges. f. Chem. Ind. (D. R. P.
143893, 13 March, 1902).
Acridine Yellow (Farbwerk Mtthlheim,D. R, P.
52324, 27 June, 1889) was, like the two pre-
ceding colours, discovered by Bender. Its
constitution is that of a 3 6-diamino-2 7-
NH :
dimethylacridine hydrochloride; it is produced

:
from formaldehyde and m-toluylenediamine.

It forms a yellow powder soluble in water and
alcohol with yellow colour and green fluore-
C 6H 4 scence; yellow precipitates are obtained
with hydrochloric acid (hydrochloride) and
sodium hydroxide (free base). Silk is dyed a
The salts of the tetra-ethyl derivative of this greenish yellow with green fluorescence, cotton
compound form the dyestuff known as flaveosine. (tannin mordant) is coloured yellow.
Acridine Orange NO (Farbwerk Miihlheim, The salts with aliphatic acids, e.g. formate
H
D. R. P. 59179, 17 Dec. 1889), C 13 7 N[N(CH 3 ) 2 ] ? . and acetate, are more soluble (Farbenfabriken
HCl-ZnCl, was discovered by Bender. It is vorm. F. Bayer, D. R. P. 140848, 13 March,
produced by condensation of dimethyl-ra- 1903). Acridine yellow is converted into an
phenylenediamine with formaldehyde and pro- orange yellow, more easily soluble dyestuff by
ceeding according to the method referred to ;
'
heating with twice its weight of glycerol for
above. It forms an orange powder which 4-6 hours to 170-180 (Badische Anilin und
dissolves in water or alcohol with orange- Soda-Fabrik, D. R. P. 151206, 26 July, 1903).
red colour and greenish fluorescence. The (For the action of aldehyde on aniline yellow,
aqueous solution is reddened by hydro- see D. R. P. 144092.) Compounds, probably of
chloric acid ; sodium hydroxide gives a yellow acridinium type, are obtained from aniline
precipitate. The solution in concentrated sul- yellow by the action of monochloracctic acid
phuric acid is nearly colourless and has a greenish (M. L. B., D. R. PP. 133788, 136729, 152662)
fluorescence, dilution with water produces suc- and other dyestuffs by condensation with
cessively red and orange colouration. The dye |
formaldehyde and m-diamines (D. R. PP. 131365,
gives orange shades, fairly fast to light and soap, 132116, 135771). Either one or both of the
on cotton mordanted with tannin it is also ; amino- groups in acridine yellow and analogous
suitable for printing and leather-dyeing. dyestuffs are replaced by hydroxyl on heating
'
The analogous dyestuff from diethyl-m- with dilute sulphuric acid to 180-220 (D. R. P.
phenylenediamine is described in D. R. P. I
121686), and similar compounds may be obtained
67609, the substances derived from monoalkyl- from formaldehyde by condensation with amino-
phenylenediamines in D. R. P. 70935. |
cresols (D. R. P. 120466).
Another method of preparing acridine orange Dibenzyl aniline yellow is claimed by Bayer
is to heat 12 kilos, of aminodimethylaniline !
& Co. as a useful leather dye (D. R. P. 141297).
either with 10 kilos, of formic acid (sp.gr. 1-2) and Benzoflavine (several marks), 3 6-diamino-
:
10 kilos, of zinc chloride graduaUy to 150-160, 2 7-dimethyl-9-phenylacridine

:
hydrochloride
or with 12 kilos, of dehydrated oxalic acid, 10 C 13 H 4 N(CH 6 )(NH 2 2 (CH 3 ) 2 ,HC1, was discovered
)
kilos, of glycerol and 1 1 kilos, of zinc chloride to by Rudolph in 1887, and introduced commercially
150. Heating and stirring are continued as i byK. Oehler in 1888 (D. R. PP. 43714, 28 July,
long as any darkening of shade can be observed, 1887 ; 43720, 45294, 45298). Its preparation has
ammonia is liberated during the reaction, and beengiven above. The dye, which is usually mixed
formic acid having been employed instead of i
with dextrin, forms an orange powder, difficultly
formaldehyde, the product when worked up soluble in cold water, more easily in hot. Both
yields the dyestuff instead of its leuco- compound aqueous and alcoholic solutions are orange, with
(D. R. P. 67126). strong green fluorescence. Hydrochloric acid
The formyl derivatives of m-diamines may gives an orange precipitate, sodium hydroxide
also be used (D. R. PP. 149049, 161699), or the : liberates the yellowish-white base. The solution
'
methane ' carbon atom may be furnished by 1 in concentrated sulphuric acid is greenish yellow,
various formyl derivatives such as formanilide and shows a very strong green fluorescence. It
(D. R. P. 149410). :
may be used for dyeing both mordanted and

Acridine Orange, R
extra (Farbwerk Miihl- unmordanted cotton. The acetate and lactate
heim, D. R. P. 68908, 7 Feb. 1890). The dye- are more readily soluble (Bayer, D. R. P.
stuff is the hydrochloride of
tetramethyldia- 142453, 19 April, 1902) it behaves like acridine
;
niino-9-phenylacridine, and is obtained from yellow when heated with glycerol.

46 ACRIDINE DYESTUFFS.
The Patent Phosphines of the Ges. f. Chem. obtained by the esterification of the product of
Ind. in Basel are obtained by alkylation of the interaction of ammonia and fluoresceiin
benzoflavine and acridine yellow (D. R. P. (B. A. S. F., D. R. PP. 73334, 75933 ; compare
79703; compare D. R. P. 131289). D. R. P. 141356).
Coriophosphines (Bayer &
Co.). These dye- Rheonine (Badische Anilin und Soda-Fabrik).
stuffs,which are suitable for leather-dyeing, are This dyestuff was discovered by C. L. Miiller
probably unsymmetrically alkylated diamino- (D. R. P. 82989, 16 Dec. 1894). Its method of
acridines obtained by condensation of formalde- preparation has already been given. Rheonine
hyde with one molecule of an asymmetrically forms a brown powder, soluble in water and
dialkylated m-diamine and one molecule of a alcohol, with brownish-yellow colour and green
non-alkylated or monoalkylated m-diamine, with fluorescence. Hydrochloric acid turns the solution
subsequent elimination of ammonia, and oxida- brownish-red, caustic soda gives a bright brown
tion (D. R. P. 133709). precipitate. It is used for obtaining brownish-
H
Chrysaniline C 19 J6 N occurs under many yellow shades on leather or cotton (tannin).
other names commercially, e.g. Leather yellow, Two marks, N (brighter) and A (darker), are
Xanthine, Philadelphia yellow G, Leather brown, in use.
Phosphine (several marks), &c. Reference to The use of diaminobenzophenone and of
its occurrence in the manufacture of magenta Michler's hydrol for condensation with ra-dia-
has already been made. Numerous methods mines have been patented (M. L. B., D. R. P.
for preparing homologues and analogues of this 89660 and B. A. S. F., D. R. P. 85199 re-
substance have been patented (D. R. PP. 65985, spectively).
78377, 79263, 79585, 79877, 81048, 94951, Many acridine and naphthacridine dyestuffs
102072, 106719, 114261, 116353). The method containing only one amino- group have been
adopted for this purpose by Meister, Lucius, and described (D. R, PP. 104667, 107517, 107626,
Briining may be mentioned (D. R. P. 65985, 108273, 118075, 118076, 125697, 130360); and
2 April, 1892). p-Toluidine and its hydro- it has also been observed that dyestuffs can be
chloride are heated with ferric chloride (oxygen- obtained when only one molecular proportion of
carrier), and m-nitroaniline gradually added. a m-diamine is used with formaldehvde (D. R. P.
The resulting dyestuff is the next higher homo- 136617). J. T. H.
logue of chrysaniline, containing a methyl- group ACRODEXTRINS v. DEXTRINS.
in position 7. ACROSE v. CARBOHYDRATES.
According to Friedlander (Fortschritte der ACTINIUM. A radioactive element, dis-
Theerfarbenfabrikation V. 373), the yields pro- covered by Debierne in the precipitate produced
duced by this method are not good, but the by adding ammonia and ammonium sulphide to
reaction between p-aminobenzaldehyde or a the filtrate from the hydrogen sulphide precipi-
derivative and phenyl-ra-phenylene- (or toluyl- tate obtained in the course of analysing pitch-
ene-) diamine proceeds nearly quantitatively : blende (Debierne, Compt. rend. 129, 593 130, ;
+ C H (NH )CHO +
C 6 H B -NH-C 7H 6 -NH 2 6 4 2 906). In fractionating the rare earths thus ob-
tained from pitchblende by means of their double
= 2H + C,H4<T>C 7H6NH
2 a nitrates with magnesium nitrate, actinium accu-
X>C H 4 -NH 6 2 mulates in the more soluble portions together
(B. A. S. F., D. R. PP. 94951, 102072). with neodymium and samarium (Compt. rend.
Chrysaniline forms an orange-yellow powder, 139, 538). The predominating rare earth in
soluble in water and alcohol with reddish-yellow
pitchblende is thorium ; but actinium also
colour and yellowish-green fluorescence. The solu- occurs in uranium minerals containing no
tion is unaltered by hydrochloric acid ; sodium thorium (Szilard, Chem. Soc. Abstr. 1909, ii t
hydroxide gives a bright yellow precipitate. 663).
Chrysaniline is chiefly used in leather dyeing. Actinium has not been obtained pure, but
Corioflavines (Griesheim-Elektron). These it appears to resemble thorium chemically
dyestuffs, which occur commercially as marks (cf. however, Giesel, Ber. 40, 3011). It is pre-
G, GG, R, and RR, are used in leather-dyeing cipitatedby oxalic acid, hydrofluoric acid, and
and calico-printing. They form red or reddish- by ammonia. Actinium preparations are highly
brown powders, which dissolve in concentrated !
radioactive, imparting induced radioactivity

sulphuric acid with yellow or orange colouration I
to surrounding objects (Curie and Debierne,
and green fluorescence ; these solutions turn Compt. rend. 132, 548), and, like radium, they
red or reddish-brown on dilution.
spontaneously give rise to helium (Debierne,
Flaveosine (Meister, Lucius, and Bruning, Compt. rend. 141, 383) ; they are not lumines-
D. R. P. 49850, 11 May, 1889) is a tetraethyl- cent. Their aqueous solutions slowly evolve
diaminoacridylbenzoic acid, which is obtained hydrogen and oxygen in the proportions
by heating m-acetaminodimethylaniline with necessary to form water. Actinium salts also
phthalic anhydride. It has been examined by evolve an emanation, an inert gas having
'
Grandmougin and Lang (Ber. 1909, 42, 4014). a molecular weight of approximately 70,
The hydrochloride crystallises in shining i
according to diffusion experiments (Debierne,

brownish-yellow needles, the sulphate in prisms ,
Compt. rend. 136, 446, 767 138, 411 Bruhat,
; ;
exhibiting a cantharides lustre. The base is j

Comp. rend. 148, 628; Russ, Phil. Mag. 17,
precipitated from the salts by sodium carbonate, !
(vi.) 412), and condensing to a liquid at

and forms golden-yellow shining leaflets. - 120 to - 150 (Kinoshita, Phil. Mag. 16,
Flaveosine dyes silk golden yellow (yellowish- (vi.) 121).
green fluorescence) from a feebly acid bath; wool The spontaneous decomposition of actinium
and cotton (tannin mordant) are coloured appears to give rise to six successive products :
reddish yellow. The colours are fast. radio actinium (Hahn, Ber. 39, 1605 ; Phil. Mag.
Substances closely related to flaveosine are 13, (vi) 165), which is said to resemble the
ADHESIVES. 47
alkaline earths (Giesel, Ber. 40, 3011), and 96927, 24/3, 97 ; Traube, Annalen, 1904, 331,
which changes into actinium X, a substance 64).
soluble inammonia; this transforms into actinium Adenine from dilute aqueous
crystallises
emanation, from which actinium A, actinium B, solution in long rhombic needles that become
and actinium C successively arise (Hahn and anhydrous at 110, and melt with decomposition
Mcitner, Chem. Soc. Abstr. 1908, ii. 920) ; they when rapidly heated at 360-365 (Fischer,
I.e.),
are induced active deposits. Actinium itself is and sublime in microscopic needles without
rayless all the other products except actinium decomposition at 220. Adenine is
;
sparingly
A emit a- particles ; and radio actinium, actinium soluble in cold (1 1086) and
readily soluble in
:
A, and actinium C emit ft- rays (Hahn and hot water (1 40) ; insoluble in ether or chloro-
:
Meitner, Chem. Soc. Abstr. 1908, ii. 1007). form, sparingly so in alcohol. It forms com-
Actinium is identical with the substance pounds with bases, acids, and salts. The nitrate
emanium discovered by Giesel (v. Giesel, Ber. C 5 H 5 N 5 ,HN0 3 4H 2 is crystalline, and the
35, 3608 36, 342 ; 37,
; 1696, 3963 Debierne,
; dry salt dissolves in 110-6
parts of water ; the hy-
Comp. rend. 139, 538 ; Hahn and Sackur, Ber. drochloride H
C 5 5 N S ,HC1,H 2 forms transparent
38, 1943 cf. Marckwald, Ber. 38, 2264). monoclinic prisms a b c 2-0794 1 :
1-8127, : =
=
; : :
ADAMANTINE SPAR CORUNDUM.

v. j8 61 40' the anhydrous salt dissolves iii
ADAMITE. An artificial abrasive made in 41-9 parts of water; the chloracetate C N H r ,
Austria. H
C 2 3 O 2 C1 melts and decomposes at 162-163";
5 5
ADAMITE. Hydrated basic zinc arsenate, HN

the sulphate (C 5 5 5 2 ,H 2 S0 4 ,2H 2 0, the oxalate
)
Zn 3 (As0 4 2 -Zn(OH) 2 crystallising in the ortho-

) ,
H H
C 5 5 N 5 ,C 2 2 4 ,H 2 0, anddichromate (C 5 N ) 2
6 S
H
rhombic system. First found in 1866 as violet H 4 Cr 2 7
are crystalline the picrate C ;N 6
H 5 5,
,
crystals in a silver-mine at Chanarcillo, Chile, C 6 H 3 N 3 O, is stable at 220, and is so sparingly

and subsequently as greenish and yellowish soluble in cold water (1 3500) that it is used :
crystals in considerable abundance in the zinc- as a means of estimating adenine in solution

mines at Cape Garonne in France, and Laurion (Ber. 1890, 23, 225) ; the picrolonate C 5 6 5 HN
in Greece. H N
C 10 S 5 4 crystallises from water and melts at
,
ADANSONIA DIGIT ATA (Linn.), the Baobab 265 (Levene, Biochem. Zeitsch. 1907, 4, 320). The
tree, yields a fibre which has been used in paper- platinichloride (C 5 5 5 ) 2 ,H 2 PtCl 6 HN
crystallises
making. Its bark (Gowik Chentz or Churee from dilute solution in needles, and yields the
Chentz) is said by Duchaissaing to be a useful salt C 5 H 5 N 5 ,HCl,PtCl 4 when a concentrated
substitute for cinchona (Dymock, Pharm. J. solution is boiled. The acetyl derivative
[3] 7, 3).
C 6 H 4 N 5 Ac does not melt at 260, the benzoyl
ADENASE v. ENZYMES. derivative C 6 H 4 N B Bz has m.p. 234-235 (Kossel,
ADENINE, 6-Aminopurine Ber. 1886, 20, 3356). The methyl and benzyl
derivatives have been prepared (Thoiss, Zeitsch.
N:C(NH 2 )-C-NH\X physiol. Chem. 13, 395). Bromadenine C 5 H 4 N 5 Br
CH,3H 2
strongly basic, forms an insoluble picrate,
|
is
CH N : C-N^ and on oxidation with hydrochloric acid and
discovered in the pancreatic gland and spleen potassium chlorate yields alloxan, urea, and
of the ox, occurs in all vegetable and animal oxalic acid (Bruhns, Ber. 1890, 23, 225 ;
Kriiger,
tissues rich in cells (Kossel, Ber. 1885, 18, 79, Zeitsch. physiol. Chem. 1892, 16, 329). Adenine
1928; Zeitsch. physiol. Chem. 1886, 10, 248); is converted into hypoxanthine by the action
thus it has been extracted from tea leaves of nitrous acid (Kossel, Ber. 1885, 18, 1928).
(Kossel, Z.c.), from beet-juice (v. Lippmann, Ber. M. A. W.
1896, 29, 2645),from the young shoots of bamboo ADHESIVES, as distinguished from cements,
(Totani, Zeitsch. physiol. Chem. 1909, 62, 113); may be defined to be substances or preparations
from human excretory products (Kriiger and of a gummy or gelatinous character used for
Schittenhelm, Zeitsch. Physiol. Chem. 1902, 35, the purpose of joining together or effecting the
159), and from herring brine (Isaac, Chem. mutual adhesion of the surfaces of bodies. They
Zentr. 1904, ii. 647 ; from Beitr.chem. phvsiol. are usually substances which (1) soften in water,
Path. 1904, 5, 500) ; it is probably one of the e.g. gum arabic, isinglass, glue, &c. ; (2) gela-
degradation products of nuclein
(Schindler, tinise in water or other menstruum, and harden
Zeitsch. physiol. Chem. 1889, 13, 432), and is either by the evaporation of the solvent or its
found in small quantity when nuclein is heated absorption by the cohering surfaces, e.g. liquid
with dilute sulphuric acid (Kossel, Ber. 1885, glue, gelatine dissolved in acetic acid, rubber
18, 1928). or guttapercha in benzene, &c. or (3) which ;
Adenine is isolated from tea extract after soften on heating and congeal on cooling, e.g.
the removal of caffeine by precipitating the marine glue, shellac, &c. The surfaces of the
H
cuprous compound C 5 3 N 6 Gu 2 by means of articles to be joined should be perfectly clean ;
copper sulphate and sodium bisulphite, and de- they should be brought into intimate contact,
composing the precipitate with ammonium and as little of the adhesive as possible employed.
sulphide; the crude adenine is then isolated In certain cases perfect contact is ensured by
from the filtrate in the form of the sulphate. heating the parts to be joined to a temperature
For the method of separating adenine from such that the adhesive solidifies only when
other purine bases compare Schindler, Zeitsch. union is effected.
physiol. Chem. 1889, 13, 432). The synthesis Solutions of gum arabic, or of dextrin, or
of adenine has been effected
by reducing with British gum, mixed with acetic acid, are fre-
hydriodic acid 2-amino-2 8-dichloropurine ob- :
quently employed in the case of paper. Flour
tained by the action of aqueous ammonia on or starch mixed with water containing a little
trichloropurine (E. Fischer, Ber. 1897, 30, 2226; alum so as to form a thick cream, which is
1898, 31, 104; Bohringer and Sons, D. R. P. then heated to boiling, and when cold mixed
48 ADHESIVES.
with oil of cloves, thymol, phenol, or salicylic distilled, and no anhydride is obtained by tho.
acid so as to preserve it, makes an effective distillation of the acid. It is slightly soluble
adhesive. A transparent paste may be made in water at the ordinary temperature, and has
by the use of rice starch instead of ordinary a great tendency to form supersaturated solu-
flour. Occasionally a small quantity of linseed tions (Dieterle and Hell, Ber. 17, 2221) ; readily
oil or glycerol is added in the case of labels soluble in hot alcohol and ether. It forms salts
exposed to moisture. Or the labels may be with most metals which are generally soluble in
protected from damp by being coated with a water and crystal Usable. There are eight iso-
mixture of 2 pts. shellac, 1 pt. borax dissolved merides of adipic acid, all of which have been
in 16 pts. of boiling water. An alternative prepared.
method is to apply a coating of copal varnish. ADIPOCERE (from adeps, fat and cera, ;
A strong adhesive may be made from wax). A peculiar waxy-looking substance, first
shredded gelatine, swollen in water containing observed by Fourcroy in 1786, when the Cime-
25 p.c. of glacial acetic acid and applied hot. tit>re des Innocents at Paris was cleaned out.
The mixture should be kept in a closely corked A large number of coffins had been piled to-
phial. Another recipe Dissolve 60 pts. borax
:
gether and had remained for many years ; the
in 420 pts. water, add 480 pts. dextrin and 50 corpses in many of these were converted into
pts. glucose, and heat carefully
not above 90 a saponaceous white substance. Fourcroy placed
with constant stirring until the whole is in this substance, together with cholesterol and
solution replace the evaporated water and filter
; spermaceti, in a separate class termed by him
'
through flannel (Hiscox). Adipocere.' Gregory (Annalen, 1847, 61, 362),
Wheat flour rich in proteins is mixed with observed a similar substance in the case of a
concentrated sulphite liquors and evaporated to hog which had died of an illness, and had been
a suitable consistency (Robeson). Dry casein buried on the slope of a mountain-side. The
mixed with half its weight of borax and a substance was completely soluble in alcohol,
sufficiency of water makes an excellent adhesive contained no glycerides, and consisted, according
for broken china or earthenware. Milk casein to Gregory, of about 25 p.c. of stearic acid, and
dissolved in alkali and an alkaline silicate, such about 75 p.c. of palmitic and oleic acids (these
as water-glass, and mixed with a solution of three acids form the chief constituents of lard).
magnesium or calcium chloride, also constitutes The absence of lime was explained by Gregory
an effective adhesive. as due to the solvent action of water saturated
Metallic surfaces after having been rubbed with carbonic acid, which continually ran over
with an alcoholic solution of hydrochloric acid the carcase. Gregory fully recognised that the
may be caused to adhere by means of a mixture fatty acids had been formed by the hydrolysis
of 10 pts. tragacanth mucilage, 10 pts. honey, of the fat, water having washed away all the
and 1 pt. flour (Spon). glycerol simultaneously produced, and he clearly
Amarine glue may be made by dissolving stated his view that from corpses of animals
10 pts. caoutchouc in 120 pts. benzene, and all nitrogenous and earthy constituents could
adding the solution to 20 pts. melted as- be washed away, fatty acids only remaining
phaltum, the mixture being poured into moulds behind. Ebert (Ber. 8, 775) in the main con-
to consolidate. In order to use it the glue is firmed these results in the examination of a
soaked in boiling water and heated over a flame specimen of adipocere. On saponifying with
until liquid. potash, about 1 p.c. ammonia escaped and an
ADIPIC ACID. Butane-a-5-dicarboxylic acid insoluble residue (about 6 p.c.), consisting of
C0 2 H-(CH 2 ) 4 -C0 2 H. Obtained by the action of lime, &c., from tissues, remained. mixture A
nitric acid on sebacic acid, or on tallow, suet, of potassium salts was obtained, which by
and other fatty bodies (Arppe, Z. 1865, 300; fractional precipitation with magnesium acetate
Laurent, Ann. Chim. Phys. [2] 66, 166; yielded mainly palmitic acid. The last fraction,
Bromeis, Annalen, 35, 105 ; Malaguti, Ber. not precipitable by magnesium acetate, but
1879, 572). It is present in beet-juice (Lipp- by lead acetate, j'ielded a hydroxylated acid,
mann, Ber. 1891, 3299), and may be obtained the formula of which is given as C 17 34 3 H .
from Russian petroleum by distilling the fraction This acid, termed by Ebert hydroxymargaric
containing naphthalene hydrocarbons (Aschan, acid, melts at 80, and is most likely 1 10 :
Ber. 1899, 1769). It may be prepared by acid of the melting-point

hydroxystearic
the reduction of mucic acid (Crum-Brown, 81. The occurrence of this acid in the
Annalen, 125, 19), saccharic acid (de la Motte, adipocere examined by Ebert is very likely, as
Ber. 1879, 1572), wosaccharic acid with hydriodic he could not detect any oleic acid ; it would
acid and phosphorus, or of muconic acid with thus appear that in the course of time the oleic
sodium amalgam (Marquardt, Ber. 1869, 385) ; acid had been oxidised to 1 10 hydroxystearic
:
by heating /3-iodopropionic acid with silver acid. More recently Schmelck (Chem. Zeit.
( Wislicenus, Annalen, 149,
221 ); by the electrolysis 1902, 11) found in the examination of three
of the potassium salt of the monoethyl ester of
specimens of adipocere the following results :
succinic acid, whereby the diethyl ester of adipic

acid is produced (Brown and Walker, Annalen, Melting-point . . . 62-5C.
261, 117) by oxidising cyclo-hexanone with
;
Insoluble fatty acids . 83-84 p.c.
potassium permanganate in the presence of Ash 1-7 p.c.
sodium carbonate (Rosenlew, Ber. 1906, 2202 ; (containing 83-5 p.c. CaO)
Mannich and Hancu, Ber. 1908, 575). Unsaponifiable matter 16-7 p.c.
Adipic acid crystallises in monoclinic laminae, Acid value .. .. 197
melts at 149, and sublimes at a still higher Neutralisation value of
temperature (Wirz, Annalen, 104, 257). Cyclopen- the fatty acids . 203
.
tanone is produced when the calcium salt is Iodine value . 14

AERATED OR MINERAL WATERS. 49
Tarugi (Gazz. chim. 34, ii. 469) also

ital. a few drops of adrenaline solution to a little
states that adipocere consists chiefly of palmitic sodium hydroxide (Gunn and Harrison, Pharm. J.
acid. 1907, 78, 718) ; (iii.) a fine red colour is obtained
The formation of adipocere from animal by boiling a solution containing a little potas-
matter had been studied in glass vessels filled sium iodate and a few drops of phosphoric
with water by Kratter. Kratter's opinion that acid with a few c.c. of the adrenaline solution.
adipocere originates from the albuminoids must, Adrenaline may be estimated
colorimetrically
however, be rejected as erroneous, for there can by means of iodine and sodium thiosulphate
be no doubt that the free fatty acids are formed (Abelous, Soulie, and Toujan, Bull. Soc. chim.
by the hydrolysis of the body fat. All the 1905, 23, 624).
decomposition products of the albuminoids and ADSORPTION v. COLLOIDS.
the glycerol would be washed away, and the ADUROL. Trade name for a haloid sub-
fatty acids would naturally form with the lime stitution product of hydroquinone, used as a
of the bones, lime soap, which may or may not photographic developer.
be further hydrolysed by water, to free acid and AERATED or MINERAL WATERS.
lime, according to the conditions obtaining in '
Originally the term mineral water was used
'
the decomposition of -the body. There can be to describe natural spring waters
containing
little doubt that the hydrolysing action of the small quantities of various salts in solution, and
water is greatly assisted by the presence of saturated with carbon dioxide,
frequently
enzymes which act as accelerators in the hydro- hydrogen sulphide, or other gases. When these
lytic action of the water on the body fat. waters were first imitated by the artificial intro-
J. L. duction of carbon dioxide into dilute saline
ADONIN v. GLTTCOSIDES. liquids, they were known as
'
aerated waters,'
ADONITOL v. CARBOHYDRATES. to distinguish them from the natural products.
ADRENALINE. Epinephrine, Suprarenine At the present time the two terms are employed
C 6 H ? (OH) a -CH(OH)-CH ? -NH-CH 3 It may be
.
indiscriminately, and as a rule the whole of the
obtained by extracting finely divided suprarenal products of the manufacturer of aerated waters
are popularly known as mineral waters.'
'
glands with trichloracetic acid, concentrating

the extract under reduced pressure and precipi- Natural Mineral Waters. In every quarter
tating the adrenaline by the addition of ammonia of the globe natural spring waters containing
(Abel, Ber. 1903, 1839 ; 1904, 368). Takamine salts with medicinal properties are common,
(Chem. Soc. Abstr. 1903, i. 376, D. R. P. 131496) though fashion has made some more celebrated
obtains a concentrated aqueous solution of the than others. Some of these waters (e.g. Hunyadi
glands, renders it alkaline and precipitates the Janos) contain magnesium and sodium sulphate,
adrenaline by the addition of an ammonium and have an aperient action, whilst others con-
salt or by passing carbon dioxide through the taining iron (e.g. Tunbridge Wells water) are
solution. The crude product is recrystallised valued as tonics. Others, again, like the waters
from hot water. The constitution of adrenaline of Harrogate, contain sodium sulphide (0-02 p.c.),
has been investigated by Jowett (Chem. Soc. and are used as remedies in various complaints.
Trans. 1904, 192), Bertrand (Compt. rend. 1904, The most widely consumed natural mineral
139, 502), Abderhalden and Bergell (Ber. 1904, waters are those which contain only a small
2022), and Bottcher (Ber. 1909, 253). Adrenaline proportion of salts and a large amount of carbon
has been synthesised from catechol. Catechol dioxide. Typical examples of these are Apol-
is treated with chloracetylchloride, and the linaris water, Selters water, and St. Gaulmier
resulting chloracetylcatechol condensed with (French).
methylamine, whereby monomethylaminoacetyl The table of analyses (p. 50) show the chief
catechol is produced. Reduction of this with constituents of typical natural mineral waters.
aluminium in the presence of mercuric sulphate Small quantities of many other compounds
yields adrenaline (Stolz, Ber. 1904, 37, 4149 ; are also present in all these waters, but the
Farb. Meister, Lucius and Briining, D. R. PP. figures given above represent their main con-
152814, 155632, 157300; Chem. Zentr. 1904, stituents. The composition of all natural
ii. 270, 1487 ;1905, i. 315. Other syntheses, v. mineral waters varies from time to time, but
Barger and Jowett, Chem. Soc. Trans. 1905, they preserve their general characteristics.
967; Farb. Meister, Lucius and Briining, D. R. P. Artificial Mineral Waters. Special mixtures
212206, Chem. Zentr. 1909, ii. 486; Bottcher. of salts approximately corresponding in com-
Ber. 1909, 42, 253; cf. Paulz, Ber. 1909, 42, position to those in many of the well-known
484). An aqueous solution rapidly oxidizes, be- medicinal waters are now sold, with directions
coming pink and finally brown (Takamine, for preparing solutions, which, when aerated,
Amer. J. Pharm. 1901, 73, 523). Fusion with shall produce passable imitations of the natural
potash converts adrenaline into catechol ; products.
potassium permanganate oxidises it to formic Among the purely artificial mineral waters
acid, oxalic acid, and methylamine (Jowett, mention must be made of seltzer water, which is
l.c.). prepared somewhat upon the lines of the natural
Adrenaline is a very strong haemostatic agent Selters water, and contains sodium carbonate,
and an intravenous injection produces an chloride, and sulphate, and sometimes calcium
enormous rise in blood pressure. The following and magnesium chlorides, the proportion of these
reactions serve for its detection (i.) a few drops
:
ingredients being varied to suit
the popular taste
of 1 1000 solution added to a solution containing
: of the district. It is bottled at a pressure of
copper sulphate and potassium cyanide give a about 1201bs., corresponding to about 45-55 Ibs.
characteristic red colour (Knill, Pharm. Zeit. 1907, in the bottle.
25, 115); (ii.) a characteristic odour resembling Other medicinal artificial mineral waters
phosphoretted hydrogen is obtained by adding include soda-water, potash-water, lithia-water,
VOL. I.T.
50 AERATED OR MINERAL WATERS.
PRINCIPAL SALINE CONSTITUENTS OF MINERAL WATERS PARTS PER 10,000,
Source
AERATED OR MINERAL WATERS. 51
PLAN OF A SODA-WATEB MANUFACTORY.

A. Main water supply from well or waterworks. L. Soda-watt r solution tank for mixing mineral waters
B. Water reserve. which require no syrup. When using this tank
C. Filter. the tap M i3 closed.
D. Pipe and branches supplying filtered water to syrup M. Tap to shut off plain filtered water when bottling
boiler, solution tank, and soda-water machine. non-saccharine beverages.
E. Steam-cased pan for boiling syniDS. N. Soda-water machine.
FFF. Mixing and cooling pans for syrups. O. Condenser containing aerated water, to which pipes
GGG. Felt filtering bags, through which syrup is leading to bottling machines are attached.
passed. P. Whiting bin.
HHH. Tank in compartments for storing filtered Q. Whiting shoot to generator.
syrups. R. Vitriol cistern.
III. Syrup junctions and pipes supplying syrup pumps S. Gasometer.
at bottling machines . T. Generator.
JJJ. Bottling machines U. Blow-back prevention acid boy.
K. Solution pan feeding soda-water machine with V. Steam engine.
eitlier plain water from filter C, or soda or other X. Steam pipe to syrup boiler and bottle-washing
solution from tank L. apparatus.
actual pressure in the closed bottle being very thick syrup is made from sugar and saccharin
much less. Thus experiments made by the and water, and this is acidified with citric or
writer have shown that the pressure within tartaric acid and flavoured with an essential
bottles of soda water bottled at a machine oil, which is conveniently added in the form of
pressure of 100-120 Ibs. does not exceed 45-55 an alcoholic solution termed a 'soluble essence.'
Ibs. An excess of pressure above a certain The syrups are filtered through the filter bags
limit does not result in the liquid containing shown at c, C, c, in the diagram, into their
more gas. respective tanks, H, H, H, whence they are
An essential of good bottling is that all air drawn off into the bottling machine. The use
should be expelled from the bottle, since other- of saccharin to replace part of the sugar in the
wise, air being only slightly soluble as compared syrups is almost universal in this country. It
with carbon dioxide, the liquid will rush with has the advantages of reducing the cost and of
almost explosive violence from the bottle, when acting as a preservative, whilst its disadvantages
opened, but will become flat almost immediately. are its cloying taste, which prevents its being
On the other hand, a liquid properly saturated used in more than a certain proportion, and the
with carbon dioxide and free from air will want of fulness on the palate of syrups containing
continue to emit minute bubbles of gas for at it. The latter drawback is sometimes remedied
least five minutes after it leaves the bottle. by the addition of glucose syrup.
Pressure Gauges. The mode of measuring Methods of detecting and identifying sac-
the pressure of the gas varies in different charin are described by Boucher and Boungne,
countries. Thus in England and the United Bull. Soc. Chim. Belg. 1903, 17, 126 ; Analyst,
States the zero mark on the dial of the pressure 1903, 28, 241 von Maler, Farmaz. J. 1904,
;
gauge indicates atmospheric pressure, and the 1089; Analyst, 1904, 29, 374; Villiers, Ann.
succeeding figures represent the number of Ibs. Chim. Anal. 1904, 9, 418 ; Analyst, 1905, 30,
in excess of that pressure. In Germany the dial 21 ; Chace, J. Amer. Chem. Soc. 1904, 26, 1627 ;
is graduated in
atmospheric pressures in excess Jorgensen, Analyst, 1909, 34, 156.
of the normal pressure, which is represented by Addition of Saponin. The popular demand
zero whereas hi France, which adopts the same
; for a liquid which shall retain a frothy head for
mode of expression, the figure 1 represents the some time after it has left the bottle has led
normal pressure, and the figure 2 corresponds to the manufacturers frequently adding an
to 1 on the German scale and to 15 Ibs. on the extract of quillaia bark or other preparation of
and American and so on. saponin, sold under the name of foam heading,'
'
British scales,
Sweetened Aerated Drinks. Lemonade, ginger &c. Such an addition is more necessary in
and similar sweetened mineral waters are liquids containing saccharin than
' '
ale, in all-sugar
prepared in the same way as soda water. A beverages, which froth more with
the carbon
B 2
52 AERATED OR MINERAL WATERS.
dioxide. According to the results of experi- was held, and it was decided to adopt stringent
ments made by Lohmann (Z. offentl. Chem. measures to guard against bacterial contamina-
1903, 9, 320; Analyst, 1903, 28, 361), saponin tion.
has no injurious physiological effects. On the In addition to the obvious precautions of
other hand, according to Bourcet and Chevalier having a pure water supply and observing clean-
(Pharm. J. 1905, 75, 691) commercial saponin liness in every stage of the manufacture, it was
contains neutral saponins of a toxic nature. agreed to discard all wooden tanks and vessels
For the detection of saponin, see Brunner (except for preliminary soaking to remove labels
(Zeit. Untersuch. Nahr. Genussm. 1902, 5, 1197) from old bottles), to rinse the bottles with
and Riihle, ibid. 1908, 16, 165 (J. Chem. Soc. water of assured purity immediately before
Ind. 1908, 27, 954). filling, and to use for this purpose a metal jet
Fermented Beverages.- The products of the of sufficient force. Wherever practicable, rubber
mineral water factory include one or two rings were to be removed from the stoppers, or,
beverages in which the aeration is the result of failing that, were to be immersed in a solution
a limited fermentation. of calcium bisulphite, and afterwards rinsed with
Ginger beer, which is the type of this class, pure water. The plant was also to be inspected
is prepared by adding sugar and citric acid to by a competent authority.
a dilute infusion of ginger root, infecting the There is no doubt that the adoption of such
liquid with a small quantity of a suitable yeast, precautions has had the result of raising the
bottling it, and allowing the bottles to stand standard of purity of soda-water throughout the
at a proper temperature until sufficient fer- country.
mentation has taken place. In considering the bacteriological aspect of
As a rule the fermented liquid contains less the question, several points suggest themselves.
than 1 p.c. of absolute alcohol, but occa- Thus an unfavourable bacterioscopic examina-
sionally in very hot weather the fermentation tion of one or two samples taken casually does
may proceed much further, and the ginger beer not necessarily imply faulty manufacture, for
may then contain as much as 5 or 6 p.c. of it may be the result of accidental contamination
alcohol. The pressure in the bottle of ginger of the stopper by the hands of the worker
beer when ready for consumption averages about against which there is no complete safeguard.
15 Ibs. to the square inch, but in cases of Absolute sterility of the contents of the
abnormal fermentation it may reach 100 Ibs. or bottle should not be demanded, and it is un-
more, and burst the bottle. ;
reasonable to require a greater degree of purity
Occasionally objectionable flavours are pro- than that of the average water supply of London.
duced by infection of the liquid with wild yeasts Given a sufficient degree of purity of the original
or bacteria, just as in the case of ordinary beer. water, which is essential, efficient inspection
Other drinks of this description are hore- of the factory at irregular intervals is a better
hound beer and other herb beers. Certain non- protection than an occasional bacterioscopic
alcoholic ales on the market are prepared by examination. When such examinations are
partial fermentation of an infusion of malt made periodically, they should be made under
and hops, which is then used as a syrup, and comparable conditions, i.e. at the same intervals
bottled with aerated water as in the case of after bottling otherwise the product of the
;
lemonade. cleaner process may show the worse results.

Stoppers of Bottles. The screw stopper of Standards are notoriously difficult to fix,
vulcanite or stoneware with a rubber ring to but making allowance for the various chances
effect a tight joint is now universally employed ; i
of contamination, an average sample of soda
for the glass ball-stopper (which had much to water, examined one day after bottling, should
recommend it) has fallen into popular disfavour, not yield more than 100 organisms per 1 c.c. at
and is now rarely met with, except in out-of-the- |
20, or contain sufficient B. coli to be dis-
way districts. coverable in 10 c.c.
The chief objection to the rubber-clad stopper Preservatives in Mineral Waters. The pre-
is that impurities of various kinds may lodge servatives most likely to be met with in un-
beneath the rubber, and unless strict clean- sweetened mineral waters are sulphites and
liness is observed, may contaminate the con- bisulphites, solutions of which are frequently
tents of the next bottle into which it is used, as in breweries, for cleansing the plant.
introduced. Asmall proportion of salicylic acid is often
Until about two
Bacteriological Conditions. employed to prevent ' fermentation in the so-
or three years ago was commonly believed
it called fruit syrups and other sweetened
that sterilisation was effected by aerating a articles, which might otherwise ferment and be
liquid with carbon dioxide under a high pressure. the subject of an excise prosecution for con-
In 1908, however, bacterioscopic examinations taining alcohol.
were made, at the instigation of the medical Fermentations occurring in Mineral Waters.
officer for the City of London, of a large number Excessive fermentation of ginger beer is not
of bottles of soda-water, and it was found that uncommon in very hot weather, and the writer
about 25 p.c. could be regarded as pure, and has met with samples containing as much as
over 33 p.c. as impure, the remainder being 6 p.c. of absolute alcohol.
' '
fairly pure or ' not pure.' In some of the Occasionally acetic or lactic fermentation
worst samples the numbers of micro-organisms may take place, and spoil a batch of goods, but
per 1 c.c. at 20 were uncountable, and some this seldom happens when thorough cleanliness
yielded sediment from 50 c.c., which when is observed.
cultivated at 37, gave innumerable colonies. A troublesome form of fermentation, commonly
As the result of this investigation a meeting termed the mucoid fermentation,' results in
of representative mineral water manufacturers the conversion of the contents of the bottle into
AGAR-AGAR.
a thick ropy gelatinous mass. This may be quantity of an essential oil, and the residue
caused by several micro-organisms, such as contains a resin, a crystalline
hydrocarbon
B. gelatinosum betce or B. viscosus sacchari, and H
pentatriacontane C 35 72 (m.p. 74) and a crystal-
is more liable to occur when beet sugar is used line alcohol (m.p. 140-141 [a] D =_35-7) :
for the syrup than when cane sugar is used. either isomeric with phytosterol C 26 41 0, H
When occurs in an isolated bottle, insufficient
it or a lower homologue ; d-mannitol,
together
cleansing is a chief factor in its production. with a small quantity of a volatile alkaloid
Metallic Impurities. Mineral waters not in- resembling conine, to which the alleged poisonous
frequently contain traces of metallic impurities, j
character of the herb may be due (Power and
especially iron, tin, and lead, derived from the Tutin, J. Soc. Chem. Ind. 1905, 938).
materials used or from some part of the plant. AFFINITY, CHEMICAL v. CHEMICAL
Iron in soda-water is objectionable from the !
AFFINITY.
fact that, when the beverage is added to a AFRICAN ELEMI v. OLEO-RESINS.
light-coloured liquid, such as whiskey, con- AFRICAN GREEN or EMERALD GREEN v.
taining a trace of tannin, an unpleasant dark PiaMENTS.

colouration is produced. AFRICAN INCENSE OLEO-EESINS. v.
Traces of tin find their way into mineral AGALITE. A name used in the paper-making
waters through the action of acid syrups upon trade for a fibrous variety of the mineral talc,
the tin piping leading to the bottling machines, a hydrated magnesium silicate, H 2 Mg 3 Si 4 Oi 2 .
whilst lead may be derived from solder on the It is white with a tinge of green, and is
readily
pipes. No such soldering should be permitted, reduced to short, fine fibres. It is obtained
and thorough flushing of tin piping with water almost exclusively from the district near
night and morning effectually prevents con- Gouverneur, in St. Lawrence Co., New York,
tamination with tin. A still better safeguard, about 70,000 tons, valued at $10 per ton,
which has been adopted by some factories, is being produced annually. With the exception
to replace the tin pipe by glass tubes with of a small quantity exported to Germany, it is
rubber connections. all used in the American paper trade. It gives
A still more common source of lead is the weight and body, and produces a fine gloss on
citric or tartaric acid, in which it is frequently the surface of the paper. L. J. S.
present as a manufacturing impurity. AGALMATOLITE, or Pagodite. A soft stone
Copper is not a common impurity, and, when much used in the East, especially in China, for
present, is usually due to accidental contact of carving small statues and figures, as signified
the acid syrup with the metal. by these names. At least three mineral species
Arsenic may be derived from glucose used appear to be included under these terms, viz.
in the preparation of the syrups, or from the pyrophyllite, steatite, and pinite but it is to ;
use of preparations of phosphoric acid instead the compact forms of the first of these that they
of citric or tartaric acid for acidifying the are perhaps more generally applied. In addition
syrups. to their compact nature and low degree of
It has been asserted that mineral waters hardness, they have in common a greasy or
take up traces of antimony from the rubber j
'
soapy feel in colour they are white, greyish,
:
rings of the stopper (which contain a large greenish, yellowish, &c., often with mottling.
proportion of antimony sulphide). Experiments Pyrophyllite is a hydrated aluminium silicate,
made by the writer, however, have shown that H 2 Al 2 Si 4 12 steatite, a hydrated magnesium
;
even a boiling 5 p.c. solution of hydrochloric j silicate, H Mg

3 Si 4
2 12 and pinite is an alteration-
;
acid does not dissolve any antimony from red product consisting largely of a finely scaly
rubber, and that there is thus no risk of mineral muscovite-mica, a hydrated potassium alu-
waters being contaminated in this way. minium silicate, H 2 KAl 2 Si 3 Oi 2 - Besides being
(For the detection of traces of metallic im- I
employed as material for carving, these minerals

purities in mineral waters, see Budden and are used for slate-pencils ('pencil-stone') and
Hardy (Detection of Lead, Tin, Copper, and for tailor's chalk (' French chalk' ).
Iron), Analyst, 1894, 19, 169;
Tatlock and : Extensive beds of compact pyrophyllite are
Thomson (Lead in Citric and Tartaric Acid), i
quarried in the Deep River region in North

Analyst, 1908, 33, 173 ; Lander and Winter 1
Carolina, the material being mainly used for
(Poisonous Metals), Analyst, 1908, 33, 450; making slate-pencils. At Fukuye, in Goto
Report of Conjoint Committee on Arsenic Deter- Island, in the south of Japan, a compact mineral
mination, Analyst, 1902, 27, 48 ; Report of allied to pyrophyllite is mined under the name of
;
' '
Royal Commission (Arsenic), Analyst, 1904, 29, greasy stone in Japanese) ;

'
i
roseki' (meaning
60 ; Thorpe (Electrolytic Determination of it is crushed, washed, and prepared very much
Arsenic), Analyst, 1903, 28, 349). C. A. M. like china-clay, and the product used for making
/ERUGO. (Verdigris (?) or basic carbonate fire-bricks, and to a smaller extent in the manu-
'
of copper.) The name given by the Romans to ;

facture of porcelain and paper. This material
the green rust produced on copper and bronze contains Si0 2 53-58, A1 2 3 32-36, 2 7-9 p.c. H
L. J. S.
by the united action of the oxygen and carbon
dioxide of the air. It was considered by them [
AGAR-AGAR. Bengal Isinglass. Dried sea-
to enhance the beauty of their bronze statues. weed obtained from Singapore. It is obtained
The same rust forms on brass, which was, from various red alga?, including Gelidium
however, not used by the Romans. corneum, G. cartilagineum, Eucheuma spinosum,
^SCULIN v. GLUCOSIDES. and Gracilaria lichenoidcs, which grow along the
AETHUSA CYNAPIUM (Linn.). Fool's
'
|
coasts of Eastern Asia and Malaya. The cell-
parsley
'
or the
'
lesser hemlock,' a poisonous walls of these seaweeds, when placed in boiling
umbelliferous herb. When dried and extracted water, change into jelly.
with alcohol, yields on distillation a small It occurs in small transparent strips or as
AGAR-AGAR.
a powder, and dissolves almost entirely in water usually present a pitted surface. On the exterior
' '
to a gelatinous, tasteless, and inodorous jelly. is a green coating or skin of delessite, or of
It is widely used as a nutritive medium for the similar mineral chlorophceite : many of the
the cultivation of bacteria and fungi (v. ALGÊ). larger agates, however, present a rusty coating
AGAROBILLA. The seed-pods of Ccesalpina of ferric hydrate. The earliest-formed siliceous
used in dyeing and tanning.
brevifolia (Baill.), deposits are usually chalcedonic, and the latest
AGATE. (Achat, Ger.) A natural aggregate j
are often crystalline :thus in a hollow agate the
of various forms of crystalline, crypto-crystal- j
interior is generally lined with a crop of quartz
line, and colloidal silica. In most agates these crystals, not unfrequently amethystine,
the
siliceous minerals are arranged in alternating apices of the pyramidal crystals being
directed
layers, which present on section a banded ap- towards the central cavity. This structure shows
pearance, whence the agate is valued, when that the agate has been formed by successive
cut and polished, as an ornamental stone. deposition from without inwards in other words,
:
This zoned structure is usually the result of the growth has been endogenous.' It is notable
the deposition of silica in successive layers .
that in certain agates the first-formed layers have
within the cavities of a vesicular rock. In been concentric with the walls of the original
some cases, however, the deposition has been !
cavity, and the subsequent strata horizontal.

effected in fissures, thus forming siliceous veins, Tubular orifices, lined with siliceous deposits,
as in the brecciated agates of Saxony and i
may be detected in many agates, and these have

Bohemia. In other cases the agates may occur been commonly regarded as inlets of infiltration,
in the cavities of stratified rocks, or occupy the or channels through which the siliceous solution
spaces between the pebbles of a conglomerate :
gained access to the interior. It has, however,
such are the agates of the dolomitic conglomerate been held by many observers that the solution,
and the potato stones of the Triassic marls of
' '
so far from having been introduced through a
Somersetshire. definite aperture, gradually filtered in at all
The artificial deposition of silica, in forms points ; and the internal walls .thus became uni-
closely resembling those of certain agates, has formly coated with a gelatinous layer, which
been effected by I'Anson and Pankhurst (JMin. allowed the further introduction of silica by
Mag. v. 1882, p. 34). A
strong acid is intro- !
osmotic action. Heddle pointed out that if,
duced by means of a jipette into a solution of an by a difference in the density of the siliceous
alkaline silicate, containing a certain proportion solutions within and without the cavity, pressure
of alkaline carbonate ; the bubbles of carbon were exerted outwards against the gelatinous
dioxide set free become coated as they ascend medium, this deposit might give way, and the
with gelatinous silica, which forms a tube and ; so-called inlet would thus be really a point of
by continued deposition a stalactiform agate is egress (Nature, 1884, p. 419). E. Reusch has
produced. If a cavity in a rock were filled with suggested that the agate-bearing cavities were
a solution of an alkaline silicate, and the rock filled periodically with hot siliceous solutions
permeated by an acid, a layer of amorphous by the action of intermittent thermal springs
hydrated silica would be deposited upon the (Pogg. Ann. 1864, p. 94). G. Lange, extending
walls of the cavity, and through this gelatinous this view, supposes that the steam from the
layer further deposition might gradually proceed. solution confined in the cavity might exert suffi-
The rocks in which agates typically occur are cient pressure outwards to pierce the gelatinous
the basic igneous rocks known as basalt, dolerite, deposit, and thus an outlet of escape might be
' '
diabase, and melaphyre. These traps are mistaken for an inlet of infiltration.
essentially plagioclase-augite rocks. In many Agates, when released from their matrix by
cases they present a vesicular texture, and the its natural disintegration, occur as loose nodules,
vesicles may enclose various secondary minerals either in the beds of rivers or scattered over the
' '
resulting from the decomposition of the con- country in pebble-drifts. The Scotch pebbles
stituents of the rock. Among the commonest of are found chiefly near Montrose in Forfarshire,
these alteration-products is the green earthy and at the Hill of Kinnoul in Perthshire. The
mineral known as ddessite, a hydrated silicate agates of the Cheviots are found in the Coquet
of aluminium, iron, and magnesium, probably and other Northumbrian rivers. In India agates
a product of the decomposition of the augite. have for ages been worked by the lapidaries of
Many vesicles are simply lined with this green Cambay, Broach, and Ratanpur, who obtain
substance, but in other cases the delessite be- their supply from the traps of the Deccan and
comes covered by subsequent mineral deposits of the Rajmahal Hills, or from the agate-bearing
until the cavities are more or less completely gravels of Rajpipla, which are systematically
'
filled. The rock thus becomes amygdaloidal,' mined (Man. Geol. India, pt. III. [V. Ball],
a term suggested by the fact that the kernels of 1881, p. 503; pt. IV. [F. R. Mallet], 1887,
mineral are usually of almond-like shape. This p. 70).
shape is due to the cavities, which were origin- The largest and finest agates are the so-
ally gas- or steam-bubbles, having been elon- called Brazilian stones, which come chiefly from
gated by the flow of the lava-like rock Avhen
'
the State of Rio Grande do Sul in Brazil, and
viscous. In many cases the amygdules,' or from the neighbouring country of Uruguay.
contents of the cavities, are kernels of calcite, Here they are mostly found as pebbles in the
but in other cases they are siliceous. If hollow beds of rivers, especially the R. Taquarie,
they form geodes ; and when nearly filled with having been derived from amygdaloidal trap
alternate layers of chalcedony, jasper, quartz, rocks. Some interesting agates have been
and other forms of silica, they constitute true obtained from Uruguay, consisting of a rind
agates. of chalcedony, lined with quartz crystals,
The embedded agates are easily detached and containing liquid, movable within. These
from the enclosing rock, and when removed have been called water-stones, hydroliles, or
AGATE. 55
enhydros. According to C. W. Giimbel, the ,

daries. These stones are also cut, to a limited
liquid is water with a small quantity of Nad, !
extent, at Waldkirch in the Black Forest.
CaCl 2 ,CaSO 4 ,SiO 2 ,C0 2 , &c. (Sitz. B. z. Munchen, For many years the German
agate-workers,
1880, II. p. 241 ; 1881, III. p. 321). Chalcedonic , following the earlier practice of the Italian
waterstones, of polyhedral form, occur at Beech- :
cameo-cutters, have modified the colour of most

of the stones by
worth, Victoria. staining them. The commonest
Moss-agate consists of chalcedony enclosin practice is that of darkening certain layers in a
twisted filaments, usually green but sometimes banded agate, so as to produce an The
onyx.
red or brown, resembling vegetable structures, onyx presents a succession of two or more strata,
Mocha-stones are simply white or brown chalce- alternately light and dark brown, or even white
dony, generally from India, with dendritic or and black. To produce this contrast of colour
trborescent markings due to oxides of iron j
when not naturally present, the agate is first
and manganese. Fortification-agate is a term steeped in honey and water, and gently heated
applied to those stones in which strata of jasper on a stove. In course of time, perhaps two or
and chalcedony have been deposited upon quartz j
three weeks, certain layers of chalcedonv, more
crystals,and hence they present on section j
porous than others, are found to have absorbed
curious zigzag patterns, suggestive of the plan the saccharine matter. No
j
perceptible change
of a fortress. The trivial terms eye-agate, riband- is observed when the
I
agate is removed and

agate, &c., need no explanation. washed ; but on placing it for a short time in
Agate is employed for the knife-edges of sulphuric acid the absorbed matter becomes
balances, for small mortars and pestles, for carbonised, and it is then seen that certain
burnishers and writing styles, for trinket-boxes, layers of chalcedony, originally of a dull grey
umbrella-handles, seals, brooches, beads, and an tint, have assumed a rich brown or even black
endless variety of trivial ornaments. Nearly all colour. In place of the honey, olive oil is some-
the agate used in the arts is worked in Germany. times used. If accidentally coloured too strong,
The industry of cutting and polishing agates i
the excess may be removed, or the colour
'
is centred in the neighbourhood of Oberstein j
drawn,' by the use of nitric acid. The process
on the river Nahe, a tributary to the Rhine at j
of darkening agates is one of
great antiquity,
Bingen. Most of the agate-mills are situated and imperfectly described by Pliny (Hist.
is
near Idar, about two miles north of Oberstein. Nat. xxxvii. c. 75) as having been in his day
Here the Idar Bach, which flows into the Nahe, practised in Arabia. On the history of colouring
furnishes abundant water-power, which for four agates, v. Noggerath, Die Kunst, Onyxe . . .
centuries has been utilised in the local mills. zu farben, Karsten's Archiv. xxii. 1848, p. 262.
The original location of the trade in this district Carnelian a red variety of chalcedony, and
is
was due to the occurrence of agates in the its characteristic tint may be easily developed
amygdaloidal melaphyre of the Galgenberg, near artificially in the chalcedonic bands of certain
Idar, where agates were formerly obtained by j
agates which are, in their natural state, merely
systematic mining operations. For many years, !
grey or yellowish. It has long been the practice
however, these workings have been abandoned, in India to heighten the colour of pale brownish
and the mills have been supplied with South agates by prolonged exposure to solar heat,
American agates, the importation of which was whereby any ferric hydrate in the stone loses
begun about 1827. more or less water. In Germany the agate
Large consignments of South American agates is usually heated and then moistened with sul-
are periodically sold by auction at Oberstein. phuric acid, or is placed in a solution of ferric
The common stones are first roughly dressed with nitrate, prepared by throwing old nails into
hammer and chisel, while the finer stones are dilute aquafortis in either case the stone is ;
carefully wrought into form by means of metal afterwards exposed to a red heat, whereby the
discs fed with emery or with diamond powder. absorbed salt is decomposed and ferric oxide
The grinding is performed on wheels of red formed. Alternating bands of red and white
sandstone, about 5 feet in diameter, set vertically, chalcedony constitute the variety of agate known
and rotating at the rate of about three revolu- as sardonyx, and it is to imitate this stone that
tions per second. Each stone is about 1 foot the red tints are often developed. Prolonged
digestion in warm hydrochloric
in width, and its surface presents channels acid imparts a
corresponding with the form of the objects to yellow tint to the agate, but this colour is not
j
be ground. The stones are usually moved by popular. Green colours, resembling those of
large undershot water-wheels, but the incon- chrysoprase, which is simply a green chalce-
;
venience of their stoppage during the drought dony, are produced by means of salts of either
of summer or the frost of winter has led to the nickel or chromium. Blue tints may be readily
partial introduction of steam-power. When obtained by soaking the stone in a solution of
;
working, the grinder lies almost horizontally ferrous sulphate and afterwards in either ferro-
j
upon a wooden stool, hollowed to the shape of cyanide or ferricyanide of potassium, when
|
his body, and having his arms free. The agate Prussian blue or Turnbull's blue is formed in
is pressed
forcibly against the grindstone, fed the pores of the stone
i or an ammoniacal solu- ;
with water from above, while the Avorkman tion of sulphate of copper may be used. Blue
!
obtains purchase by pressing his feet against a are extensively sold

agates, artificially stained,
,
block fastened to the floor. The polishing is as

lapis-lazuli.
i More recently a dead-white
afterwards effected with rouge and water on effect has been produced in certain stones, which
'
soft metal plates or with tripoli on wooden are thus rendered more valuable for cameo work,
i
cylinders. It is said that this effect is obtained by the use

Not only agates, but rock-crystal, amethyst, of caustic potash and subsequent exposure to a
high temperature. On
false crocidolite, and other hard stones are now the agate industry, v.
extensively cut and polished by the Idar lapi- H. Lange, Die Halbcdelsteine, Kreuznach,
1868 ;
56 AGATE.
Upmann, Gesch. d. Graftsch. Ober-
Beitr. z. ornamental objects, such as vases, lamps, stands
stein, Mainz, 1872; M. Bauer, Edelsteinkunde, of time-pieces, &c., is found at Volterra, in
2nd ed., Leipzig, 1909, and Engl. transl., Tuscany. The harder varieties are worked with
Precious Stones, by L. J. Spencer, London, 1904. the same tools as marble, smoothed with pumice-
F. W. R. stone, polished with a mixture of chalk, soap,
AGAVE. An amaryllidaceous genus including ;
and milk, and finished by friction with a
several species, the leaves of which provide useful flannel.
'
fibres. '
Pite,' or pita hemp,' mainly produced The softer kinds may be turned or fashioned
in Mexico, obtained from A. americana (Linn.)
is with rasping tools, fine chisels, or small files,
and A. mexicana (Lam.). It is also obtained smoothed with dried shave grass, then rubbed
from several other American species of Agave. with a paste of putty powder or finely divided
Sisal hemp' is derived from A. rigida (Mill.), slaked lime, and polished by washing with soap,
which grows in Mexico, Central America, and water, and lime, and finally with powdered elu-
the West Indies. triated French chalk or talc.
AGAVOSE. An inactive sugar C 12 22 O n H , Alabaster may be stained by heating it to
reducing alkaline copper tartrate, and yielding about 90 or 100, and then dipping it into
a laevogyrate sugar on inversion found in ;
the colouring solution, which may be eithei
Agave americana (Linn.), grown in Mexico. The metallic solutions, spirituous tinctures of natural
young flower heads are used in the preparation dyes, or coloured oils (Habild, Wagner's Jahr.
of a fermented intoxicating drink termed 28, 669).
'
pulque
'
(Michaud and Tristan, J. Amer. Chem. A variety of alabaster known as onyx of
Soc. 14, 548). According to Stone and Lot/, Tecali, from Mexico, takes a fine polish its ;
J. Amer. Chem. Soc. 17, 368, this sugar is colour varies from milk-white to pale-yellow and
saccharose. pale-green (J. 29, 1264).
AGONIADA BARK. The bark
Plumiera of ALACREATINE v. CBEATINE.
lancifolia (MuelL), used in Brazil as a remedy ALAMOSITE. A lead silicate PbSiO 3 found
,
for intermittent fever, contains a bitter crystal- ; near Alamos, Sonora, Mexico ; analogous to
line glucoside, agoniadin (Peckolt, Arch. Pharm. wollastonite CaSi0 3 in form, habit, and com-
[2] 142, 40, 1870), identical with the plumieride !
position. It occurs in radiated aggregates of

of Boorsma and Merck, obtained from Plumiera minute colourless transparent fibres, which give
acutifolia (Poir.) it is probably the methyl ester
; a snow-white appearance to the mass (Palache
of plumieridic acid, and has the composition i and Merwin, Amer. J. Sci. 1909, 27, 399 ; J. Soc.
C, H, 6 12 (cf. Franchimont, Rec. trav. chim.
] I
Chem. Ind. 1909, 606).
1898," 18, 334; Proc. K. Akad. Wetensch. ALANGIUM LAMARCKII v. ANKOOL.
Amsterdam, 1900, 3, 35). ALANINE, a-Alanine. a-aminopropionic acid
AGROSTEMMA SAPOTOXIN v. GLUCOSIDES. I
NH 2 -CHMe-C0 2 H, contains an asymmetric car-
AICH METAL. An alloy patented by J. Aich bon atom, and the dextro-, laevo-, and racemic
in 1860 for use as sheathing for ships. Con- isomerides are known. d- Alanine is one of the
tains copper, 60 parts ; zinc, 38-5 parts iron, decomposition products of a large number of pro-
;
1 -5 parts. teids ; together with a glucoproteid C 7 14 4 N 2 H ,
AILANTHUS BARK. The inner bark of A. it forms 51 p.c. of the product obtained by
excelsa (Roxb.) and A. glandulosa (Desf.) ; it the hydrolysis of legumin of peas (Bleunard,
has the odour and taste of cinnamon ; used as Ann. Chim. Phys. [5] 26, 47), and is formed to
j
a tonic in dyspepsia (Dymock, Pharm. J. [3] 7, the extent of 21 p.c. from silk fibroin (Weyl,
309). An Indian name of the former is Ber. 21, 1529 Fischer and Skita, Zeitsch. ;
Maharukh. physiol. Chem. 33, 177). (For the methods of

AIROFORM. Identical with airol (q.v.). separating alanine from the other hydrolytic
AIROGEN. Identical with airol (q.v.). products of the proteid, v. art. PROTEINS.)
AIROL. A basic bismuth-oxyiodide gallate, r- Alanine is prepared synthetically by the action
'
analogous to dermatol,' a basic bismuth- of hydrochloric acid on the aminonitrile

gallate. Is a greyish-green powder without 2 -CHMe-CN, produced by NH
the interaction of
smell or taste, soluble in caustic soda or dilute aldehyde ammonia on hydrogen cyanide
mineral acids. Becomes red on exposure to (Strecker, Annalen, 75, 29) or, together with ;
damp air. Has been used clinically as a sub- o-aminopropionitrile hydro chloride, when am-
stitute for iodoform (v. BISMUTH). monium chloride, potassium cyanide, and acetal-
AKANDA v. AK MUDAE. dehyde interact in equimolecular quantities in
AK MUDAR, AKANDA, AKRA RUI, or aqueous solution (Zelinsky and Stadnikoff, Ber.
ERUKKU ERUKKAM. The bark of Calotropis 41, 2061) or by reducing o-nitrosopropionic ;
gigantea (Ait.) and C. procera (Ait.). An im- acid with tin and hydrochloric acid (Gutknecht,
portant Indian drug (Dymock, Pharm. J. [31 10, Ber. 13, 1116).
122). Alanine crystallises in needles or sharp
AKOLA v. ANKOOL. rhombic prisms, dissolves in 4-6 parts of water
AKRA RUI v. AK MUDAR. at 17, or in 500 parts of 80 p.c. cold alcohol ;
ALABANDITE. Manganese sulphide (MnS) its heat of combustion is 389 Cal. and heat of
(v. MANGANESE). formation 135-2 Cal. (Berthelot and Andre,
ALABASTER. (Albdtre, FT. ; Alabaster, Ger.) Compt. rend. 110, 884). The resolution of racemic
A massive, crystalline, and marble-like variety alanine has been effected through the benzoyl
of the mineral gypsum (CaS0 4 ,2H 2 0). It is derivative, which is separated into d-benzoyl-
found in Glamorganshire ; at Syston in Leices- alanine (m.p. 147-148 [a] D +37-13 in alkaline
tershire at Tutbury, near Burton-on-Trent in
;
solution), and l-benzaylalanine (m.p. 150-151
A (corr. ), [O]D 37 -3 in alkaline solution), by crystal-
|
Staffordshire, and other places in Britain.

snow-white alabaster much used for small lisation of the brucine salt, and these
yield on
ALANINE. 57
hydrolysis the corresponding optically active derivatives, see Curtius and Lambotte, J pr
alanines ; r-alanine decomposes at 264-268 Chem. 1904, [2] 70, 109) phthalylalanine C H.:
;
fi
(Zelinsky and Stadnikoff, I.e.), at 293 (Fischer, (C0) 2 N-CHMe-C0 2 H, m.p. 164, and phthal-
:
Ber. 32, 2451) ; d-alanine has [a] D 9-55 in + oylalanine C0 2 H-C 6 H 4 -CO-NH-CHMe-C0 2 H,
hydrochloric acid solution ; l-alanine decom- H,0, m.p. 129 (Anclrcasch, Monatsh. 1904, 25,
poses at 297 and has [a] D 9-68 in hydrochloric 774) ;
palmityl-a-alanine CH 3 (CH 2 14 -CO-NH-
acid solution. A cultivation of Aspergillus niger CHMe-C0 2 H, m.p. 110, [a] 10 - 5-98 (Aber-
'
)
in an aqueous solution of r-alanine destroys

about 10 p.c. of the dextrorotatory constituent, halden and Funk, Zeitsch. physiol. Chem. 1910,
but Penicillium glaucum does not flourish in a 65, 61) diethyldialaninquinone C 6 2 2 (NH-
; H
2 p.c. alanine solution. CHMe-C0 2 Et) 2 forms red prisms, m.p. 140
In its physiological action, d-alanine causes (corr.) (Fischer and Schrader, Ber. 1910, 43, 525) ;
a rapid rise in the urinary nitrogen, most of the 2 4:-dinitrophenyl-dl-alanine,
m.p. 178 (Abder-
:
extra nitrogen being excreted on the same day ; halden and Blumberg, Zeitsch. physiol. Chem.
Z-alanine is not decomposed quite so rapidly, but 1910, 65, 318).
none of it is excreted unchanged (Abderhalden Among the polypeptides prepared by Fischer,
and Schittenhelm, Chem. 1907,
Zeitsch. physiol. Abderhalden, and others, there are many con-
' '
51, 323 ; compare, however, Sevene and Meyer taining the alanyl group one or more times,
(Amer. J. 1909, 25, 214).
Physiol. After ad- e.g. r-alanylalanine NH 2 -CHMe-CO-NH-CHMe-
ministering 20 grms. of r-alanine, 4-7 grms. of
C0 2 H, m.p. 276 (corr.), the benzoyl derivative
the /3-naphthalenesulphonic derivative of Z-ala- m.p. 203-204, the ethyl ester m.p. 114-116;
nine was recovered from the urine (Schittenhelm dialanylalanine NH-[CHMe-CO-NH] 2 -CHMe-
and Katzenstein, Chem. Zentr. 1906, i. 1279). CO 2 H, m.p. 219 (corr.) (Fischer and Kautzsch,
When rf-alanine is injected in the blood-stream Ber. 1905, 38, 2375) ; l-alanyl-d-alanine, m.p.
it rapidly absorbed, as very little can be
is 269-270 (corr.),
- 68-5 d-alanyl-l-
detected in the blood or urine after a lapse of [af^ ;
20
twenty minutes
(Abderhalden others, and alanine, m.p. 275-276 (corr.), [a] +68-94
Zeitsch. physiol. Chem. 1907, 53,113, 251, 326;
(Fischer and Raske, Ber. 1906, 39, 2893, 3981),
52, 507 ; 53, 148).
&n<lihetetTa,peptideglycyl-tyrosyl-glycyl-d-alanine
The importance of alanine as a final hydro-
decomposing at 225 (corr. ) is probably a mixture
lytic product of many proteid substances, has of stereoisomerides of the tetrapeptide isolated
led to an extensive examination of its derivatives
from silk fibroin (Fischer, Ber. 1908,41, 2860;
in order to facilitate its detection and estimation,
cf. Abderhalden and Hirrizowski, Ber. 1908, 41,
and to determine the part it plays in the building For other polypeptides derived from
2840).
up of the proteid molecule. short accountA alanine, see Fischer (Ber. 37, 2486; 4585;
of the more important of these derivatives is
38, 2375 ; 2914 ; Annalen, 340, 128, 152 ; Ber.
appended. 39, 453 40, 943, 1754, 3717 ; Annalen, 363, 136),
The copper salt (C 3 6
H
2 N) 2 Cu,H 2
forms and Abderhalden
;
(Ber. 41, 2840 2857 42, ; ;

>bluish-violet crystals readily soluble hi water.
3394: Zeitsch. physiol. Chem. 63, 401 65, 417).
H
The nickel salt (C 3 6 2 N) 2 Ni,4H 2 forms blue
3-Alanine, /3-aminopropionic acid 2 N-CH 2
;
H -
crystals, these become anhydrous at 108-110 CH 2 -C0 2 H, prepared by treating -iodopropionic

and dissolve in 132 parts of water (Orloff, Chem. acid with ammonia (Mulder, Ber. 9, 1902) or
Zentr. 1897, ii. 192 ; Bruni and Formara, Atti
with silver nitrite and reducing the resulting
R. Accad. Lincei, 1904, [v] 13, ii. 26). The nitro- compound with tin and hydrochloric acid
ethyl ester has b.p. 48/H mm. and sp.gr. 0-9846
(Lewkowitsch, J. pr. Chem. [2] 20, 159) by ;
at 12-5 r-alqninamide, m.p. 62 (Franchimont
heating ethyl acrylate with alcoholic ammonia
;
and Friedman, Proc. R. Akad. Wetensch. Amster-

in sealed tubes at 110 (Wender, Gazz. chim. ital.
dam, 1905, 8, 475) d-alaninamide has m.p.
;
or by the action of potassium hypo-
19, 437) ;
72 (corr.) and [a]n +6 in 5-2 p.c. aqueous
bromite on an alkaline solution of succinimide
solutionr-alanylchloride hydrochloride
; NH 3 C1-
this is the best method, and gives a yield of
CHMe-COCl melts and decomposes at 110; 60 p.c. of the theoretical (Hoogewerf and van
d-alanylchloride hydrochloride has [a] +7-32 Dorp, Rec. trav. chim. 10, 4; Holm, Arch.
Ber. r-
Pharm. 242, 590).
(Fischer, 1905, 38, 605, 2914) ;
alanineanhydride 0-Alanine forms prisms m.p. 196 (Hoogewerf

(dimethyldiketopiperazine
and van Dorp, I.e. ), does not melt at 220 (Kursda,
NH has m.p. 282, and d- Monatsh. 12, 422), m.p. 206-207 (Lengfeld and
the hydro-
alanineanhydride has m.p. 297 (corr.) and ,
Stieglitz, Amer. Chem. J. 15, 504) ;
D chloride of the methyl ester has m.p. 94-95 and

-28-8 (Fischer, Ber. 1905, 39, 453). of the ethyl ester m.p. 65-5. The copper salt
[o]^
Acetylalanine NHAc-CHMe-C0 2 crystallises in H H
Cu(C 3 6 N0 2 ) 2 ,6H 2 has the properties of an
of a cupram-
rhombic plates a b c =0-7792 1 : 1-0983 m.p.
: : :
; ordinary cop'per salt, and not those
137 (de Jong, RJJC. trav. chim. 19, 259 ; Fischer monium derivative (Callegari, Gazz. chim. ital.
and Otto, Ber. 36,2106); chloracetylalanine ester 1906, 36, ii. 63).
CH Cl-CO-NH-CHMe-C0
2 2
Et has m.p. 48-5-49-5 /3-Alanine does not occur naturally
in the
(corr.) (Fischer and Otto, I.e.) ; the benzene- i
body; when administered with food it causes

sulphonic derivative S0 2 Ph-NH-CHMe-C0 2 has H an increase in the urinary nitrogen, but it is
than
m.p. 126 (Hedin, Ber. 1890, 23, 3197) ; the apparently changed with more difficulty
P-naphthalenesulphonic derivative C 13 14 3 NS H |
o-alanine, as the increased nitrogen
excretion is
melts and decomposes at 220 (Koenigs and not observed until the second day (Abderhalden
Mylo, Ber. 1908, 41, 4427) ; for hippurylalanine and Schittenhelm, Zeitsch. physiol. Chem. 1907,
NHBz-CH 2 -CO-NH-CHMe-CO.,H, m.p. 202, and
|
'
51, 323).
M A - - w -
58 ALANT CAMPHOR.
ALANT CAMPHOR v. CAMPHOR. ceeding 145" it yields ether (C 4 10 0). With H
ALANT ROOT. The root of Inula helenium twice its bulk of sulphuric acid it gives ethyleno
is said to contain antiseptic principles, efficacious (C 2 4 ).HWith excess of dry chlorine gas it pro-
against tuberculosis bacilli. By distilling the duces chloral (C 2 HC1 3 O).
root with water, helenin, alantic acid, and alantol Preparation. Synthetically from its ele-
(alant camphor) are obtained. Alantic acid ments thus :
By passing an electric arc between
H
C 15 22 3 crystallises from alcohol in white carbon poles in an atmosphere of hydrogen,
crystals, m.p. 91 ; and on heating it forms the acetylene (C 2 H 2 ) is produced, which, in the pre-
H
anhydride C 15 20 2 Both acid and anhydride
. sence of nascent hydrogen, becomes ethylene
are insol. in water, sol. in alcohol or fatty oils ; (C.,H 4 ). Ethylene by protracted shaking with
form sol. salts with alkalis. Alantol is an sulphuric acid is converted into sulphovinic
aromatic liquid, b.p. 200 (Marpmann, Pharm. acid, which, being distilled in presence of water,
Zent. 8, 122 J. Soc. Chem. Ind. 1887, 520).
; produces alcohol.
ALBERTITE. A jet-black mineral substance Alcohol is, for practical purposes, prepared
resembling asphalt, discovered in 1849, at Hills- by dehydrating the products of the distillation
borough, Albert co., New Brunswick. Used in of fermented liquids. Up to 1796 the strongest
the United States for the production of oil and spirit known contained not less than 5 p.c.
coke. The yield per ton is said to be 100 gallons of water. Lowitz appears to have been the first
of crude oil, and 14,500 cubic feet of illumina- to prepare it in an approximately anhydrous
ting gas, whilst a residue of good coke remains condition. His process consisted in first increas-
in the retorts. Albertite has been found at ing the strength of rectified spirit by adding to
Strathpeffer, Ross-shire ; it contains 62 p.c. vola- it dry potassium tartrate, and after decanting
tile matter, 37 p.c. fixed carbon, and 0-60 p.c. from this, distilling very slowly in presence of
water. Its ultimate composition is 79-75 p.c. great excess of dry potassium carbonate.
carbon, 8-12 p.c. hydrogen, 1-63 nitrogen, and Richter used, instead of potassium carbonate,
10-30 oxygen (Morrison, Min. Mag. 6, 101 ;Chem. hot calcium chloride (Crell's Ann. 2, 211).
Soc. Abstr. 50, 311). Drinkwater first digested .with dry potassium
ALBITE v. FELSPAE. carbonate for twenty-four hours decanted the
;
ALBUM GR/ECUM. A term formerly used strong spirit thus produced, digested with as
for the excrement of dogs. It was at one time much fresh-burnt quicklime as was sufficient to
supposed to have medicinal properties, but is absorb the whole of the alcohol, and afterwards
now used only for tanning, as skins treated distilled in a water-bath at a temperature of
with it, after the removal of the hair and previous 82-2. The product of this distillation, which
to tanning, preserve their softness. It consists was found to have a specific gravity of 0-7946 at
mainly of phosphate of lime. Fowls' dung is 15-6, was returned to the retort, and a fresh
said by tanners to answer the purpose better. quantity of dry pulverised quicklime added to it,
ALBUMINOIDS and ALBUMINS v. PROTEINS. after which it was allowed to digest for a week
ALCOHOL (Ethylic or Vinous), the active at a temperature of 15-6. It was then again
principle of intoxicating liquors, is, in the dehy- slowly distilled and the specific gravity of the
drated condition, a colourless liquid, having a product found to be 0-7944 at 15-6. this was
specific gravity of 0-791 at 20/20 (Lowitz, digested at a temperature of 54-4 with hot quick-
Crell's Ann. 1796, 1, 1), 0-7938 at 15-6/15-6 lime, and distilled out of contact with the air at
(Fownes, Phil. Trans. 1847, 249), 0-793811 at a temperature of 81-1 to 82-2, and the specific
15-6/15-6 (Drinkwater, Phil. Mag. Feby. 1848), gravity of the product, which was taken as abso-
0-79350 at 15-6/15-6, 0-79367 at 15/4 lute alcohol, found to be 0-793811 at 15-6/15-6.
(Mendeleeff, Pogg. 138, 230), (Squibb, Ephe- Squibb followed the process of Drinkwater,
meris, 1884-5, and Pharm. J. [3] 16, 147-148). distilling in a partial vacuum of 380 to 630 mm.
It boils at 78-4 under a pressure of 760 mm. The alcohol thus prepared had a specific gravity
(Kopp, Annalen. 92, 9), and solidifies at 130-5 of 0-79350. The difference between this specific
(Wroblewski and Olsewski, Compt. rend. 96, gravity and that found by Drinkwater repre-
1140 and 1225). It is inflammable, the com- sents one-tenth p.c. of alcohol. Mendele'eff's
bustion evolving great heat but little light, observations (Pogg. 138, 103, 230) practically
and producing carbon dioxide and water. It confirm those of Drinkwater and Fownes. 1
acts as a caustic irritant in contact with the Analytical Methods. We are dependent upon
tissues of the body, owing probably to the specific gravity for the exact quantitative esti-
energy with which it draws moisture from the mation of alcohol, and perhaps no method could
surface. It possesses a specific heat of 0-6120, be devised so easy of application (v. ALCOHOLO-
at temperatures between 16 and 40-5(Schiiller, METRY). It is, however, open to the objection
P. Erg. 5, 116-192). Its index of refraction for that it assumes water to be the only volatile
H= -3667 (Briihl), and its critical temperature
1 substance with which the spirit is mixed, alde-
234-6 at 48-9 m. At this point 1 gram occupies hyde, fusel oil, and ether when existing as im-
3-5 c.c. (Ramsay and Young, Proc. Roy. Soc. purities being reckoned as alcohol. On the other
38, 329). hand, no chemical method, caj^ble of practical
Alcohol forms ethoxides with sodium and application, has yet been devised for the exact
potassium, and unstable compounds with certain quantitative estimation. Berthelot's process
crystalline salts, e.g. zinc chloride, the latter (Compt. rend. 80, 1039) of measuring the ethylene
called alcoholates. Subjected to the action of Absolutely anhydrous alcohol produces no blue
1
a limited supply of oxygen, it is converted into colouration with dehydrated (white) copper sulphate. It
H
aldehyde (C 2 4 0), which, by further oxidation, should give no cloudiness when mixed with benzene.
H
becomes acetic acid (C 2 4 2 ). Distilled with Absolutely anhydrous alcohol added to a mixture of
chloride of lime, it forms chloroform (CHC1 3 ). anthraquinone (0-001 gr.) with a little sodium amalgam
gives a green colouration if a trace of water be present
;
With sulphuric acid at a temperature not ex- the colour becomes red (Claus, Ber. 10, 927).
ALCOHOL. 59
produced by sulphuric acid and absorbed by bro- yeast, for not only has he to run the risk of
mine from a given quantity of spirit is a valuable acetic and other ferments being introduced into
qualitative test, and within limits most useful the wort, involving loss of alcohol, but to
provide
when applied quantitatively in presence of against the presence of aldehyde, which is
methylic alcohol. The production of iodoform objectionable in the spirit. Kekule attributes
(Hager, Compt. rend. 82, 768) may be employed the presence of aldehyde to the action of nitrates
with advantage as a preliminary test for small derived from the materials. It is found in prac-
quantities of alcohol, but as other bodies produce tice that it is always more
prone to appear in
iodoform in the same circumstances, it cannot hot weather, when the difficulty of keeping the
be regarded as conclusive. For the detection of yeast from decomposition is greatest, and as
alcohol in ether, Allen (Chem. Soc. Trans. 1877, 2, yeast always contains some spirit in a dilute
930) suggests that a little fuchsine be shaken form it is not improbable that the aldehyde is
up with water and ether, and 10 c.c. of the solu- frequently a product of the oxidation of this
tion thus formed agitated with the same quantity spirit.
of the ether submitted for examination ; the The materials used in the manufacture of
intensity of the colour produced would be a alcohol in the United Kingdom are chiefly malt,
measure of the quantity of alcohol present. maize, rice, sago, tapioca, barley, rye. oats, sugar,
For the detection of fusel oil in alcohol, and molasses, but occasionally dates and locust
Jorissen (Bied. Zentr. 1881, 791) recommends beans have been employed. At the present
that 10 c.c. of the spirit should be mixed with time maize constitutes fully 75 p.c. of the grain
10 drops of colourless aniline and 2 or 3 used. In Scotland the smaller distillers use
drops of sulphuric acid. A deep-red colour is malt only, and the spirit they produce under
formed if fusel oil be present, due to the the name of Highland, Campbeltown, or Islay
action of furfuraldehyde, an invariable con- Whiskey, Glenlivet, Lochnagar, &c., has im-
stituent of fusel oil. parted to it a flavour derived partly from the
Alcohol sometimes used as an adulterant
is peat used in drying the malt. The process of
in essential oils. A very ready test is to manufacture consists in distilling the fermented
place a little of the oil in a dry test-tube, wort then called wash in a common still, col-
taking care in pouring it in that none adheres lecting the distillate, which is weak spirit con-
to the side. Rub a little fuchsine on the upper taminated with fusel oil, and is called 'low
inside surface of the test-tube and apply heat, wines,' and redistilling. The spirit which passes
the presence of alcohol will be indicated by red over in the middle of the redistillation is that
stains in the fuchsine. No satisfactory method which is used for consumption. It contains from
has yet been suggested for the estimation of 60-8 to 76-7 p.c. of alcohol by weight (20 over-
aldehyde in alcohol, but the peculiar suffocating proof to 45 overproof), but is generally diluted
odour which accompanies it, and the brown by the addition of water to 55-4 p.c. of alcohol
colour produced by alkalis in the spirit, are by weight (11 overproof) before being sent into
indicative of its presence. A colorimetric method consumption or placed in bond. Irish whiskey
of estimation is generally employed by compari- differs from Scotch chiefly in the absence of peat
son of the sample with a standard solution of flavour. The materials used in its manufacture
aldehyde, using Schiff's reagent. are, with one or two exceptions, a mixture of
Manufacture. The first process in the manu- malt and grain, the proportion of malt being,
facture of spirit is one of brewing, and in general however, greater than in English distilleries. It
principles it does not differ from that employed is generally bonded at 25 overproof (64 p.c. of
in making beer. The brewer, as well as the alcohol by weight).
distiller, endeavours to treat his materials in We have hitherto dealt with the spirit manu-
'
such a way as to extract from them the greatest factured in Common or Pot stills, or in
' ' '
amount of fermentable matters. The brewer of other words by boiling the wash, condensing the
beer, however, does not desire to convert all the steam thus produced, reboiling the product and
matter he extracts into spirit, and he brews at recondensing. But by far the greater quantity
such gravities as his customers require. The of the alcohol of commerce is produced by
distiller desires to convert as much as the Coffey still, in which the alcoholic vapour
possible
of the matter he has extracted from his materials
produced is deprived of water as the process
into spirit ; he therefore produces a wort con- continues until a spirit is formed of much
the
taining more maltose and less dextrinous matter greater purity than that manufactured by
than the brewer of beer. He has also an ad- old method. The annexed illustration represents
vantage over the brewer in being able to choose a Coffey's distilling apparatus, the left-hand
the gravities which he knows by experience will column being called the analyser, the right
produce the best results. It has been found that hand one the rectifier. The first operation is to
for distillers' purposes it is advisable to
keep the fill both columns with steam. This is accom-
specific gravity of the wort when set for fermen- plished by introducing it under pressure
from
tation below 1040. The principle of low tem- the boiler at c, whence it ascends within the
peratures when the diastase is acting in the analyser, passing by the pipe
M into the bottom
mash tun appears to be fully recognised, 60 to of the rectifier. When a proper temperature
63 being generally adopted, and it is understood has been attained, the wash is pumped from
that the higher the temperature at which the the wash charger by a pipe which enters the
worts are set for fermentation, the greater is the top of the rectifier. This pipe is only
shown
amount of fusel oil in the spirit. The distiller sectionally in the sketch after entering
the
has, therefore, to choose the lowest temperature column, but it is continuous, and the wash
at which a
healthy fermentation can be started, passes slowly through it, becoming warmer,
and this is found to range between 23 and 25. owing to the pipe being in contact
with the
He cannot be too careful as to the purity of the steam. When it has reached the bottom of the
60 ALCOHOL.
rectifier it not far from the boiling-point.
is shallow vessel placed on that next beneath. The
It will be seen that the
pipe then ascends, and wash on entering falls on the first plate, but on
finally delivers the wash into the top of the reaching a depth of an inch and a half passes
analyser. The lines across the analyser repre- through the tube to the second one. In the
sent plates of perforated copper, and in connec- mean time the steam produces ebullition in the
tion with each is a tube which projects about an contents of the plates, and carries away with it
inch and a half above the plate, and dips into a the alcoholic vapour through the steam exit
ALCOHOL. ill
pipe, so that by the time the wash has reached therefore can only pass into the
spirit in very
the bottom of the column it has been deprived small proportion.
of its alcohol. The alcoholic vapour passes by We have hitherto only dealt with spirits
the pipe M into the bottom of the rectifier, which manufactured in the United
Kingdom. Of
like the analyser contains plates and metal the more important
foreign spirits, the prin-
tubes, and where a process of gradual cooling i
cipal is brandy, the production of which from

takes place by the action of the pipe carrying I
grape wine is an industry confined almost en-
the cold wash. Fusel oil vapour, condensing at tirely to France. The best brandy is derived
a higher temperature than alcohol, is the first from white wine, but a considerable
quantity of
to assume the liquid form, and contaminated spirit is imported from the Continent under the
with spirit passes into the hot
'
feints
'
re- name of brandy, which has either been mixed
ceiver. The vapour containing alcohol con- with other spirits or
prepared from substances
tinues to ascend, meeting with portions that bearing no relation to wine. The distillation of
have condensed, and are undergoing the process genuine brandy takes place in stills which are
of rectification. It will be seen that the upper practically on the pattern of common or pot
part of the apparatus is marked off in the sketch stills ; the improvements
being chiefly confined
as finished -spirit condenser. It is so called be- to the adoption of means for
carrying on the
cause all that condenses within its area, instead distillations continuously. Illustrations of the
of returning towards the bottom of the apparatus various stills now in use will be found in
to be rectified, passes by the finished -spirit Duplais' treatise on the manufacture and dis-
pipe or feints pipe into the receivers. At the tillation of alcohol.
Brandy is im-
' generally
top of the apparatus is a pipe marked alcoholic ported into this country at a strength a little
steam exit,' which carries away most of the :
below proof (47 to 48 p.c. of alcohol
by weight)
aldehyde as well as spirit vapour which under
1
(v. BRANDY).
special circumstances may not have been con- Rum is the spirit
produced by fermenting
densed before reaching that point. diluted molasses and
distilling the product in an
The English distillers confine themselves ordinary still. Its character is due to the for-
almost exclusively to this apparatus, brewing mation of ethyl butyrate, which, when added to
for the most part from a mixture of grain and other spirits, produces a flavour difficult to
malt. In addition to Goffey's still, various forms distinguish from genuine rum. The strength at
of rectifying stills are in use to meet special which rum is generally imported into this coun-
requirements, e.g. the production of a purer try is about 35 overproof (70 p.c. of alcohol
though not stronger spirit than that obtainable by weight) (v. RUM).
from the Coffey still for the purpose of com- The molasses from the beet-sugar manu-
pounders and certain manufacturing processes, factories in France is now utilised in making
and apparatus having for their object (in con- spirit, being simply neutralised, generally mixed
sequence of the increasing demand for fusel oil) with a little rye flour and malt, fermented and
the recovery of the maximum amount of this distilled. The best qualities of spirits thus pro-
by-product, which indeed is now considerably duced are devoid of taste or any peculiar aroma,
more valuable than the spirit itself. The spirit and are employed in the manufacture of liqueurs,
produced does not to any large extent go into for improving common brandies, and for refining
consumption as whiskey, the want of flavour rectified spirit.
being an objection in regard to the better Geneva or Hollands is a well-known form
qualities. Large quantities are transferred to of gin manufactured in Holland, where the grain
the rectifiers, who redistil them with various spirit is for the most part made from a mixture
flavouring ingredients, producing gin, British of malt and rye. It does not possess any
brandy,. British rum, and the various cordials. characteristic to distinguish it from the same
A portion, after being redistilled from potash or article manufactured by rectifiers in this country,
potassium carbonate, or filtered through charcoal, and its consumption appears to be declining
is used in the arts and in medicine under the (v. GIN). Absinth isa form of gin in which the
names of rectified spirit and spirits of wine. spirit is flavoured with the bitter principle of
The British Pharmacopoeia (1898) requires wormwood, together with extracts of some or all
rectified spirit to be of a specific gravity of 0-834, of the following plants : fennel, hyssop, anise
equal to 85-65 p.c. of alcohol by weight. The coriander, angelica seed, dried veronica, chamo-
Pharmacopoeia of the United States fixes it at mile, and mint (v. ABSINTH). A large quantity
0-820, equal to 91 p.c.,which is about the strength of spirit manufactured in Germany from po-
it comes from Coffey's apparatus. It is from tatoes is imported into this country, coming
this spirit that anhydrous or absolute alcohol into competition with the lowest qualities of
is generally prepared. It varies considerably spirits of wine of the British distilleries.
in flavour, and, according to the United States Reference has already been made to the bond-
Dispensatory, 1883, the purest is produced under ing of whiskey that is, placing it in warehouses
Atwood's patent, in which permanganic acid is under the control of the revenue authorities,
used to destroy the disagreeable organic sub- where it remains maturing for periods varying
stances. It has been suggested that the purity from a few months to several years. The exact
of strong spirit might be considerably increased change which takes place during the maturing
by redistilling in vacua. Reference has already process has not yet been satisfactorily ex-
been made to the occurrence in variable quantity i
plained, although the labours of Pelletan, Dumas
of secondary products on fermentation. Pasteur and Stas, Gaultier, Chancel, Wurtz, Cahours,
(Ann. Chim. Phys. 58, 330) showed that on the I
Balard, Liebig and Pelouze, Pasteur, Fittig, and

fermentation of sugar 3-16 p.c. of glycerol and Kramer and Pinner have added largely to our
0-67 p.c. of succinic acid are produced. These knowledge of the subject. According to the re-
bodies are, however, very slightly volatile, and ! searches of these authorities fusel oil is a complex
62 ALCOHOL.
substance and a necessary accompaniment to The principal restriction on the use of methyl-
fermentation. In grain fermentations amyl ated spirit is that it shall only be kept by
alcohol is the predominant constituent of this authorised persons and in authorised premises.
oil, but propyl and butyl alcohol are also present. In 1891 it was found necessary (owing to the
In wine fermentations it consists principally of possibility of methylated spirit being sufficiently
cenanthyl and caproyl alcohols. It is probable purified to render it fit for potable purposes, and
that these alcohols are converted, in the process the growing practice of drinking even the un-
of maturing the spirit, from a disagreeable- purified methylated spirit by the poorer classes
smelling and highly intoxicating body into com- in some of the larger cities) to again restrict the
pound ethers which are both fragrant and use of methylated spirit made as above described
'
harmless. (i.e. ordinary methylated spirit ') to manu-
In the process of mellowing there is generally facturers only, and, even then, subject to
a loss of alcohol, varying with the length of time revenue restrictions, and to prescribe the
and the condition of the atmosphere of the addition of a further denaturant to methylated
warehouse. The revenue authorities fully recog- spirit intended for general purposes. This
nise this, and make the necessary allowances denaturant consists of mineral naphtha (petro-
' '
in charging the duty. It will therefore be ap- leum), and the mixture, known as mineralised
parent that alcoholic strength based on specific methylated spirit, may be sold by licensed
gravity is not always a measure of the money retailers to the general public for any purpose
value of spirits as beverages. The Food and to which it is applicable, as lighting, heating,
Drugs Amendment Act (42 & 43 Viet. c. 30) has cleansing, or mixing with paints, varnishes,
'
&c.
'
fixed a limit below which spirits shall be assumed It was found, however, that ordinary
to be diluted. This limit is 25 under proof methylated spirit was not universally applicable
(35-8 p.c. of alcohol by weight) for whiskey, to manufacturing processes requiring the use of
j
brandy, and rum ;

and 35 under proof (30-8 alcohol, and accordingly, in 1902, the Com-
p.c. alcohol by weight) for gin. missioners of Inland Revenue, under powers
Uses. In addition to its use as a beverage, :
conferred upon them by the Spirits Act of 1880
employed as a solvent for many of the
spirit is I and the Finance Act of 1902, authorised the use
drugs required in medicine, and diluted to the of duty-free alcohol denatured with substances
standard of British proof that is, to the specific other than wood-naphtha in certain manufactur-
j
gravity of 0-91984 at 15-6, representing 49-24 p.c. ing operations and subject to special conditions.
by weight of Drinkwater and Fownes alcohol As the result of an inquiry by a Depart-
it forms part of a large proportion of the tinc- mental Committee, in 1904-5, the amount of
tures of the Materia Medica. It is also used
'
wood-naphtha to be used as a denaturant for
'
largely as a solvent for essential oils, in pre- ordinary methylated spirit used for industrial
paring perfumes and essences, and ether is purposes was reduced from 10 to 5 ' p.c. of the '
manufactured from it. The alcohol used in all mixture. This is described as industrial
the above preparations pays a duty of 15s. Id. methylated spirit.
per proof gallon, equal to about 27s. per gallon At the present time (1911), there are, there-
of the alcohol of Gay-Lussac, the standard of fore, two descriptions of methylated spirit offici-
France. ally recognised in the United Kingdom, viz. :
Adulteration. Although it has been stated (a) Mineralised methylated spirit as sold by
that spirits, especially gin, were formerly adul- licensed retailers for general use (except for the
terated with capsicum and even sulphuric acid, preparation of beverages or medicine), and con-
in order to increase their fiery character, it is taining not less than 10 p.c. by volumeof approved
satisfactory to find that in the working of wood-naphtha, and, in addition, not less than
the Food and Drugs Act no evidence has been 0-385 p.c. of approved mineral naphtha (petro-
afforded of such practices during late years. leum of specific gravity not less than 0-800).
The report of the Local Government Board (b) Industrial methylated spirit, intended for
(1909) shows that the adulterants detected use in manufacturing processes, and sold only by
during the year consisted of water (the great methylators to persons authorised to receive
majority of cases) ; foreign spirit in 16 samples this kind of spirit. This must contain not less
out of 5217 samples of brandy, rum, and whiskey than 5 p.c. of approved wood-naphtha or other
examined; one case (whiskey) contained an substance or combination of substances approved
admixture of sherry wine. by the Commissioners of Customs and Excise.
Methylated spirit. In 1853 a strong repre- The wood-naphtha must be sufficiently im-
sentation was made to the Government to allow pure to make the methylated spirits so nauseous
j
the use of alcohol duty free in the arts and as to render them incapable of being used as a
j
manufacturing processes in which it was re- beverage or of being mixed with potable spirits
quired, and after careful inquiry the Board of without rendering them unfit for human con-
Inland Revenue in 1855 decided to sanction, sumption. It must contain not less than 72 p.c.
under certain restrictions, a mixture of nine by volume of methyl alcohol, and not more than
parts of spirits of wine and one part of methyl 12 grams per 100 c.c. of aldehydes, acetone, and
alcohol (wood naphtha) free of duty under the higher ketones, estimated as acetone by Mes-
name of methylated spirits. In 1861 the per- singer's iodoform process, nor more than 3 grams
mission was extended to all other purposes except of esters estimated as methyl acetate by hydro-
consumption as a beverage or as a medicine. lysis ; not more than 30 c.c. of naphtha shall
The reasons for selecting wood naphtha were that be required to decolourise an aqueous solution
whilst it would be least likely to interfere in any containing 0-5 gram of bromine, and 5 c.c. at
of the processes for which alcohol was required least of deci-normal acid shall be required to
especially as a solvent it would be very difficult neutralise 25 c.c. of the spirit when methyl
to separate from the alcohol when once mixed. orange is used as indicator.
ALCOHOL. 63
The wood-naphtha which is now used by common and the mixture introduced into
salt,
methylators is fairly uniform in character as a wide tube and heated for some
hours at
regards its content of methyl alcohol, and it is 90 -100. The product is exhausted with
warm
by the recognition of this alcohol that the alcohol and the extract filtered and made
up to
presence of methylated spirits is usually de- a volume of 100 c.c.
tected. Acetone is present in much more varying If the
sample of spirit contained ethyl
quantities, whilst unsaturated alcohols, com- alcohol only, the colour of the
liquid will be
pound ethers, and nitrogenous basic substances red, but in the presence of 1 p.c. of
methyl
are present in too small and varying proportions alcohol it has a distinct violet
shade, whilst in
to afford suitable means for dectectmg methy- the presence of 2 p.c. the violet is
very decided,
lated spirits in mixtures. and becomes more so as the
proportion of
The most satisfactory methods for detecting
methyl alcohol in presence of ethyl alcohol
depend either on differences in the physical pro- Percentage of
methyl alcohol by
perties of the alcohols themselves, or on differ- volume in the mix-
ences in the chemical behaviour of their deriva-
1
ture of alcohols
tives or products of oxidation, but of these, few
are capable of indicating with certainty the
presence of less than 1 p.c. of methyl alcohol.
Of the methods which have hitherto been
devised for this purpose, none can compare, as
regards the certainty of the conclusions which
may be drawn from the results, with that of
Riche and Bardy, which depends on the ultimate
formation of methylaniline violet and its de-
position on merino- wool (Compt. rend. 1875, 1076).
As a preliminary test, and one which may with
advantage be incorporated in the Riche and
Bardy process, the following will be found to be
useful. About 10 c.c. of the strong spirit freed,
if necessary, from essential oils, &c., by the
salt-petroleum method and fractionated from
potassium carbonate (v. ALCOHOLMETRY) are
placed with 30 grams of powdered iodine in a
small round-bottomed flask which can be readily
connected with a condenser. Two grams of
amorphous phosphorus are added and the result-
ing alkyl iodides distilled and collected under
water in a small separator. When from 10 to
12 c.c. have been collected, the iodides are washed
with water, decolourised with dilute potash, and
drawn off from the aqueous layer into a flask
containing a little freshly heated potassium
carbonate. After remaining an hour or so with
occasional shaking, the potassium carbonate is
removed by filtration, and the boiling-point of
the iodides carefully determined. Ordinary
ethyl alcohol yields an iodide which has a con-
stant boiling-point of 72. When methyl
alcohol is present in the spirit, the initial
boiling-point of the iodides is lower and a
portion distils below this temperature. By
noting the temperature at which the first
drop of distilled iodides falls into the condenser
and receiver respectively, the presence of rela-
tively small quantities of methyl alcohol can be
detected. The results (see table in next col.)
obtained with synthetic mixtures indicate the
delicacy of the method.
In doubtful cases, or when the initial boiling-
point is below 70, the first fraction of 3 c.c. of
distilled iodides is
digested with an equal
volume of aniline at a moderate temperature,
and the Riche and Bardy method proceeded
with. After standing one hour, hot water is
added to the crystalline mass, and the mixture
boiled for some minutes, 25 c.c. of
strong potash
solution are then added, and the liberated aniline
oil washed with water 1 c.c. of this oil is inti-
;
mately mixed with 10 grams of a mixture

consisting of 100 grams of dry quartz sand,
3 grams of cupric nitrate, and 2 of
grams
64 ALCOHOL.
embodied in tables associated with the names of
given above for rectified spirits, but in all cases
in which a dye is obtained a proportional excess those entrusted with the investigations.
of carbon dioxide is also obtained. In 1794 Sir Charles Blagden and Mr. Gilpin
In other countries there are, as a rule, classes completed an extensive series of experiments,
of denatured alcohol corresponding more or less undertaken at the request of the British Govern-
with those authorised in the United Kingdom, ment (Phil. Trans. 1790-1794), the results of
i.e. spirit for general use so completely denatured which have since served as the basis of systems of
as to be deemed undrinkable, and spirit not alcoholometry in this and other countries. At
absolutely denatured and intended for use by that time anhydrous alcohol had not been pre-
responsible manufacturers subject to a more or pared, Blagden and Gilpin's tables having refer-
less strict revenue control. ence to spirit of a sp. gr. 0-825 at 15-6/15-6
Wood-naphtha is the denaturant most in (60 /60F.). Tralles, in 1811, conducted a
favour for spirit intended for general use, the like investigation for the Prussian Government
nauseous character of the methylated spirit (Gilb. Ann. 1811), and adopted 0-7946 as the
being sometimes intensified by the addition of specific gravity of alcohol at 15-6/15-6. He
such substances as pyridine bases, benzine, &c. incidentally confirmed the general accuracy of
In France, spirit for general use contains one- the results of Blagden and Gilpin, and constructed
eleventh of its volume of officially approved tables of spirit-strengths which for upwards of
wood-naphtha, with an addition (when used for sixty years formed the basis of German alcoholo-
lighting and heating purposes) of 0-5 p.c. of heavy metry. Similar researches were undertaken by
benzine distilling between 150 and 200 and Gay-Lussac (Paris, 1824),McCulloch(Washington,
'
4 p.c. of gum resin for finish.' 1848), Baumhauer( Amsterdam, 1860), Mendele'eff
In Germany, the official formula is 2 p.c. of (St. Petersburg, 1865), and more recently by
wood naphtha, 0-5 p.c. of pyridine bases, and the Kaiserliche Normal Eichungs Kommission
(optionally) 0-125 p.c. of rosemary oil. Spirit (Berlin, 1889), the several results of which have
intended for motor cars, and internal combustion from time to time been incorporated in the
engines is denatured 1
by adding p.c. of wood- systems of alcoholometry adopted by the respec-
naphtha, O25 p.c. of pyridine bases, 0-25 p.c. of tive Governments. The unofficial investigations
a solution of methyl violet dye, and from 2 to 20 of Fownes (Phil. Trans. 1847), Drinkwater
p.c. of benzol to the pure spirit. (Chem. Soc. Mem. 1848), and Squibb (Ephemeris,
In the United States of America, 10 p.c. of 1884), are likewise entitled to consideration.
approved methyl alcohol and 0-5 p.c. of benzene Drinkwater prepared alcohol of a specific
is prescribed to be added to spirit denatured for gravity 0-79381 at 15-6/15-6 (in air), whilst
general use. Squibb obtained it as low as 0-7935, but this
: Two result lacks confirmation.
Austria- Hungary p.c. of wood-naphtha,
0-5 p.c. of pyridine bases, and a trace of phenol The work of Mendeleeff for the Russian
phthalein are added to spirit intended for general Government admittedly constitutes the most
purposes. comprehensive and exact of the researches
In Belgium and Russia specific denaturants hitherto made in the field of alcoholometry.
are prescribed for each of the principal manu- Mendele'eff obtained alcohol of a specific
facturers, and this practice obtains in certain gravity 0-79425 at 15/15 , which at 15-6/15-6
other countries, as Germany, France, Switzer- is equivalent to 0-79384 in a vacuum, or to
land, and the United Kingdom, when it can be 0-79359 in air, and he assigned to Drinkwater 's
shown that ordinary methylated spirit is un- alcohol an alcoholic content of 99-95 p.c., and to
suitable. In such cases the denaturants are the strong spirit of Blagden and Gilpin 89-06
naturally very varied in character, being specially p.c. by weight. The results of Tralles' andGay-
adapted to the particular necessities of each Lussac's experiments, being based on alcohol
manufacturer. less dehydrated than that of Drinkwater, com-
(Minutes of Evidence and Report of the pare less favourably with those of Mendele'eff.
Departmental Committee on Industrial Alcohol, Mendeleeff was so well satisfied with the
1905 Herrick, Denatured or Industrial Alcohol.)
; work of Blagden and Gilpin, and Drinkwater,
ALCOHOLOMETRY is the term applied to that, for spirituous mixtures of low strength, he
any process for estimating the amount of alcohol included many of their results in his tables of
in a spirituous liquid. In simple mixtures of spirit-densities, and after a critical investigation
alcohol and water a determination of specific and subsequent verification by the Kaiserliche
gravity at a standard temperature affords an Normal Eichungs Kommission, his results have
accurate index of alcoholic content, and it is been substantially adopted as the basis of the
by taking advantage of this fact that the assay present system of German alcoholometry in pJace
of spirit for revenue and commercial purposes of the relatively less accurate data of Tralles.
is usually carried out. The results of the work of these four autho-
When alcohol and water are mixed together rities have been incorporated in the accompany-
the volume of the mixture is invariably less ing table of spirit-densities, which may serve
than the sum of the initial volumes, and the for the pyknometrical determination of the true
degree of contraction varies with the proportion strength of spirits. In the assessment of duty
of alcohol present. In countries in which the and in commercial transactions, the standard of
revenue from spirit is of great importance it has strength is termed
'
proof.' Spirit of proof

therefore been found necessary to ascertain by '
strength is defined as that which at the tem-

experiment the specific gravities of mixtures of perature of 51F. (10-6C.) weighs exactly |2ths
alcohol and water in all proportions and at of an equal measure of distilled water
'
also at
various temperatures. These experiments have 10-6. According to the best available data
in general been carried out at the request of the this mixture of alcohol and water has a specific
Governments interested, and the results are gravity of 0-91976 at 15-6/15-6, and contains
ALCOHOLOMETRY. 65
Specific
gravity iu air
. 15-6
at
lW
ALCOHOLOMETRY.
with water to proof strength, yield 175-35 strength of 73-5 overproof, or 98-24 p.c. of
' '
volumes at that temperature. alcohol, whilst the 10 mark corresponds to
In the table on p. 65 specific gravities of 66-7 overproof, or 92-50 p.c. of alcohol by weight,
' '
aqueous alcoholic mixtures are correlated with the strength proper to the mark on Sikes'
percentages of alcohol by weight and by volume, hydrometer.
and fiscal proof spirit. The specific gravities In the United States of America Tralles'
are reduced to air values and represent the tables are legalised, and, as in England, revenue
ratio of the weight of a given volume of spirit is raised with reference to a mixture of alcohol
'
to the weight of the same volume of water at and water termed proof.' American proof
15-6 under the same atmospheric conditions ; spirit is defined as containing one -half of its
they may be converted to specific gravities in volume of Tralles' alcohol at 15-6. For Excise
vacuum by means of the expression purposes a series of alcoholometers are employed,
each having a limited range, and indicating
S + 0-0012 ' '
percentages of proof spirit representing
1-0012 water,
' '
100 proof spirit and 200 alcohol
' '
Although probable that the density of a

it is and readings at temperatures other than 15-6
spirituous liquid can be determined more accu- are corrected by means of tables to what they
rately by the use of a pyknometer than by other Avould be in the same spirit at that temperature.
means, in practical operations where regard In comparing American with British proof it is
must be had to convenience, it is preferable to necessary to remember that the American gallon
employ one of the many hydrometers or alcoholo- is smaller than the British Imperial gallon,
meters, the stems of which are variously graduated 100 British being equivalent to 120 American
to show densities, percentages of alcohol by gallons. Consequently, 100 British proof gallons
weight or by volume, or again arbitrary indica- are equal to 137 American proof gallons.
tions which can be interpreted by suitable Similarly, in Holland a proof standard is
tables. recognised. Dutch proof contains 50 p.c. by
Since the year 1816, Sikes' hydrometer has volume of anhydrous alcohol at 15. As in
been the legal instrument for ascertaining the the United States, a series of alcoholometers
strength of spirits for revenue purposes in Great are employed, differing only in regard to the
Britain and Ireland, as well as in most of the range of their strength indications. The alco-
British Colonies. It is made of brass, gilded, holometer scale is divided into 28 principal
and consists of a hollow sphere provided at one divisions or degrees, which are equal in length,
pole with a graduated rectangular stem uniform and again subdivided, each principal division
in section, and at the other with a conical representing ^
of the volume of the instru-
spindle terminating in an oval counterpoise to ment below the zero mark. Spirit tables based
give stability to the instrument when floating on the results of Baumhauer's investigations
in a liquid, and also to serve as an attachment accompany the instruments and translate
for various poises. The graduated portion of degrees on the scale into percentages of alcohol
the stem contains ten principal divisions, which at 15 on which the revenue charge is based.
' '
are equal in length, and marked at the In Italy Tralles' alcoholometer is used
' '
upper, and 10 at the lower end, and between officially. This instrument is made of glass,
these points the stem is again subdivided to and at the standard temperature of 15-6
2 tenths of a division. When the instrument is directly indicates the volume of alcohol con-
' '
floating at the mark in spirit at a tempera- tained in 100 volumes of spirit when measured
|
ture of 15-6, it indicates a strength of 66-7 at the same temperature. Indications at other
I
overproof, or 92-50 p.c. of alcohol, whilst the temperatures are corrected by means of tables
' '
!
10 mark corresponds to a strength of 58 to true percentages by volume at 15-6.

overproof, or 86-11 p.c. of alcohol (by weight). In Austria-Hungary an alcoholometer closely
For strengths weaker than these a series of nine resembling Tralles', and indicating percentages
poises or weights are used, numbered consecu- of alcohol by volume at 15 is used. Its in-
tively from 10 to 90. The poises are made of dications are uniformly higher than those of
hammered brass, gilded, and can be attached by Tralles' to the extent of from one or two tenths
means of a slot in the poise to the spindle of
.
per cent. Readings on this instrument are taken
the hydrometer. The series of principal divi- 1
at the highest point of the capillary meniscus,

sions can thus be repeated ten times, reading which extends 1-2 mm. on the stem above the
'
from ' ' to 100,' which latter indication repre- normal surface of the liquid.
sents distilled water. Sikes' hydrometer indica- Tralles' alcoholometer and tables are used
tions refer to readings on the stem at the surface commercially in Russia, but for Revenue purposes
of the liquid in which it is floating, the capillary a metal h3 drometer with nine poises similar in
r
meniscus being disregarded, and are interpreted character to Sikes' hydrometer is official. On
into proof-strengths by means of tables which this instrument, however, Sikes' indications are
' '
are arranged so as to identify a sample of reversed, so that 100 is made to represent
' '
spirits at any temperature between 1 -1 (30F. ) strong spirit, and distilled water. The hydro-
and +37-8' (100F.). meter scale is arbitrary, and indications are inter-
The hydrometer which is used for strong preted into percentages by volume of Tralles'
spirits beyond the range of the ordinary Sikes' alcohol at the standard temperature of 15-6.
instrument is known as the
'
A '
or Light hydro-
'
Previous to the year 1887, Tralles' instrument
meter,' and tables proper to this instrument are was also used in Germany. It has now been
also issued. It is made of brass, gilded, and replaced by a system of weight alcoholometry,
graduated on the stem similarly to' Sikes' hydro- based on Mendeleeff's data, whereby the pro-
meter. When floating at the '
mark in portion by weight of alcohol is determined. The
spirit at a temperature of 15-6, it indicates a official alcoholometers are made of glass, and
ALCOHOLOMETRY. 67
Indication of
Sikes' hydro-
meter at 15- 6
68 ALCOHOLOMETRY.
Indication of
Sikes* hydro-
meter at 15-6
ALDEHYDE. 69
to 30, the percentage by volume of alcohol of the distillate is determined
by the Zeiss
which a liquid contains at 15. Immersion Refractometer. The refractions of
Previous to the adoption of Gay-Lussac's mixtures of ethyl alcohol and water have been
alcoholometer and tables by the French Govern- determined at various temperatures
by Wagner
ment, Cartier's areometer was used as the and Schultze (Zeitsch. anal. Chem. 1907,
508)
Revenue instrument. Its stem is graduated from and others, and a near approximation to the true
10 to 45 in divisions of equal length, and in- alcoholic content of a fusel oil mixture, treated
dicates the concentration of a spirituous liquid as above described, can be obtained
by applying
by arbitrary degrees, which serve as spirit to the apparent percentage by volume of
-
alcohol,
strengths for charging duty. Cartier's areometer as indicated by the density of the
distillate, a
used in Spain and South America.
is still subtractive correction of 0-5 p.c. for each
degree
In Switzerland, Beck's hydrometer is used of difference between the refractometer
reading
for spirit assaying, and, like Cartier's instrument, as found at 15-6, and that
j
required for a
of which it is a modification, floats at the lowest mixture of ethyl alcohol and water
correspond-
indication in distilled water at 12-5 (10R.). | ing to the ascertained density. This method of
By means of the table on p. 67 the indica- j
eliminating foreign matters in spirit assaying,
tions of any one of these instruments at 15-6 from a knowledge of their influence on the specific
can be converted into degrees of any other, and i refractions of aqueous alcoholic mixtures, is
British fiscal strengths compared with those of I
capable of wide application, and has been utilised,

other countries. for instance, by Leach and Lythgoe Amer. Chem.
(
An indispensable step to a correct assay of J. 1905, 964) for

determining the proportion of
spirit is the removal of any foreign matter which methylated in a spirituous liquid (v.
spirits
may be in solution in the alcoholic mixture. In I
REFRACTOMETER). J. H.
the case of potable spirits, wines, liqueurs, &c., ALCORNIN or ALCORNOL. An alcohol,
the spirit is freed from saccharine and other 1
C 22 H 34 0, of the nature of phytosterol found in

dissolved matter by distillation. The distilla- ;
Alcornoco bark (Hartwich and Diinnenberger,

tion of a strong spirituous liquid into its own Arch. Pharm. 1900, 341).
volume so as to obtain an accurate determina- ALCOVINOMETER. An instrument for de-
tion of the amount of alcohol present is im- [
termining the alcoholic content of a wine by
practicable with the apparatus and the methods observing its ascent in a capillary tube.
of distillation commonly used, so that although ALDEHYDE Acetaldehyde C H O 2 4 or
it is possible to distil without loss spirits of CH 3-COH. A product of the oxidation of ordi
underproof strength into the same volume, it is nary (ethylic) alcohol. Aldehyde occurs, together
necessary to dilute overproof spirits and distil with its polymerides metaldehyde and paralde-
' '
into two, three, or four times the original hyde, in the first runnings from the stills in
volume. The amount by which the true alco- the rectification of alcohol which has been
holic strength of brandy or rum differs from the filtered through charcoal (Kramer and Pinner,
apparent strength, as indicated by the hydro- Ber. 2, 403 4, 787
; Johnson, J. Soc. Chem.
;
meter or a density determination, is termed the Ind. 8, 57; Hewitt, ibid. 21, 97); the best
'
obscuration.' yield is obtained from the alcohol manufactured
In the case of medicinal preparations, flavour- from potatoes and from the sugar beet. It
ing essences, &c., which yield distillates con- is also present in crude wood spirit (Kramer
taining essential oils and volatile substances, and Grodzki, Ber. 9, 1921) in crude petroleum ;
special treatment is necessary before a pykno- (Robinson, J. Soc. Chem. Ind. 18, 232) in wine ;
metrical determination of spirit is possible. during the process of ageing (Trillat, Compt. rend.
In these circumstances the sample or dis- 136, 171); and in certain circumstances in
tillate is mixed with water in a separator so the fermentation products of alcohol (Trillat,
that the mixture shall contain not more than Compt. rend. 146, 645 Trillat and Souton, 146,
;
20-25 p.c. by volume of alcohol, and common 996 Kayser and Demolon, 146, 783).
;
salt is added in quantity sufficient to saturate Aldehyde is also formed when calcium formate
the liquid. The mixture is then shaken vigor- is heated with calcium acetate (Limpricht,
ously with 50-100 c.c. of light petroleum, and Annalen, 97, 369), and when lactic acid and the
after remaining a short time, the aqueous layer lactates are distilled with manganese dioxide
is extracted, necessary, a second time with
if and sulphuric acid (Stadeler, Annalen. 69, 333) ;
petroleum (forinstance when- chloroform or it is also one of the products of the dry dis-
(
ether is present), and finally drawn off into a i tillation of sugar (Volckel, Annalen, 87, 303).
flask and distilled. In the case of soap lini- Preparation. Aldehyde is formed by the
ments and similar preparations, dilute sulphuric j
oxidation of alcohol by means of platinum
acid is used instead of salt, and the aliphatic black (Dobereiner, Gm. 8, 274), of manganese
acids and volatile matters removed by petroleum dioxide and sulphuric acid (Liebig, Annalen, 14,
before distilling (Chem. Soc. Trans. 1903, 314). 133), of potassium dichromate and sulphuric acid
Preparations containing iodine are decolourised (Stadeler, J. 1859, 329), of metallic catalysers
with sodium thiosulphate, and excess of caustic (Bouveault, Bull. Soc. chim. 1908, 3, 117;
soda added to prevent decomposition of the tetra- Sabatier and Senderens, Compt. rend. 136, 738),
thionate during distillation. Similarly, volatile or when alcohol is passed through an iron tube
acids must be neutralised, andammoniacal liquids heated to 710-750 (Ipateiff, Ber. 34, 596).
distilled from dilute sulphuric acid solution. According to Lang (J. Soc. Chem. Ind. 22,
For the estimation of ethyl alcohol in fusel 571), the most useful oxidising agents for
oil, or liquids containing fusel oil, the salt- converting alcohol to aldehyde are the manganic
petroleum process may be employed, but as salts. When prepared by Liebig's method,
the higher alcohols cannot be wholly elimi- 2 parts of 80 p.c. alcohol are heated with
nated by this method, the specific refraction 3 parts of manganese dioxide, 3 parts of
70 ALDEHYDE.
sulphuric acid, and 2 parts of water, and sium permanganate, acetic acid is formed, but in
the distillation carried on until the distillate presence of excess of potash, oxalic and carbonic
begins to show an acid reaction ; this point j
acids are also formed (Denis, Amer. Chem. J.
is reached when about three parts have col- 38, 561).
lected in the well-cooled receiver. The dis- When subjected to electrolysis in faintly
tillate containing alcohol, acetal and ethereal alkaline or neutral solution it is decomposed into
salts is then distilled with an equal weight of alcohol and acetic acids (Slaboszewicz, Chem.
calcium chloride, and 1| parts collected this ;
Zentr. 1903, i. 279 ; Law, Chem. Soc. Trans.
is again rectified with an equal weight of calcium 1905, 198 ;
Jackson and Laurie, ibid. 1906,
chloride and J part distilled over. The product 156), whilst when heated alone to high tempera-
so obtained is nearly anhydrous, but still contains tures carbon monoxide and methane are the
alcohol and small quantities of ethereal salts ; chief products (Bone and Smith, Chem. Soc.
to free it from these, it is dissolved in 2 vols. of Trans. 1905, 910).
ether, saturated with ammonia in the cold, and Acetaldehyde and its dimethyl derivative
the aldehyde-ammonia which separates is col- have antiseptic properties (Coblenz, J. Soc.
lected, dissolved in water, distilled with dilute Chem. Ind. 17, 728 Pasqualis, Chem. Zentr.
;
sulphuric acid in a water-bath, and the distillate 1897, ii. 10, is also useful in photo-
12). It
rendered anhydrous by rectification over calcium graphic developing (Seyewetz, Bull. Soc. chim.
chloride at as low a temperature as possible. 19, (3) 134), and the -vapour or solution in
Improved methods and apparatus for oxi- alcohol or benzene slowly hardens drv gelatine
dising alcohol into aldehyde are described by films (Beckmann, Chem. Zentr. 1896, ii. 930).
Boult ( J. Soc. Chern. Ind. 15, 608 ; Fournier, Aldehyde readily polymerises in the presence
ibid. 16, 695). of small quantities of various substances, such
Commercially, aldehyde is obtained from the as sulphuric acid, phosgene, zinc chloride,
of the alcohol stills. A special
' '
first runnings hydrogen chloride, sulphur dioxide, the halogens,
form of still in which the separation of aldehyde particularly iodine, &c., and two compounds
from alcohol is brought about during the recti- are obtained the relative quantities of which
fication of the latter is figured and described by depend upon the temperature ; the chief pro-
Galland (Dingl. poly. J. 259, 225). duct being metaldehyde (C 2 H 4 0) 3 (Hanriot and
Substituted acetaldehydes applicable to per- Oeconomides, Ann. Chem. Phys. [5] 25, 227 ;
fumery can be obtained by condensing a ketone Mclntosh, Chem. Soc. Trans. 1905, 790;
with a halogen or amino substituted acetic ester Zecchini, Gazz. chim. ital. 22, ii. 586), when
in the presence of sodium. The a-hydroxy- the action takes place in a freezing mixture;
acrylic ester thus obtained is saponified and and the isomeric paraldehyde (elaldehyde) when it
decomposed by heat or distillation under reduced occurs at the ordinary temperature (Kekule' and
pressure (J. Soc. Chem. Ind. 23, 455). Zincke, Annalen, 162, 125 Desgrez, Bull. Soc.
;
Properties. Aldehyde is a colourless liquid chim. 1 1, (3) 362 Wachhausen, Chem. Zentr. 1897,
;
b.p. 20-8, m.p. 120-7, and sp.gr. 0-80092 i. 493 ;

Ciamician and Silber, Ber. 35, 1080).
at (Kopp, Annalen, 64, 214) 0-79509 at 10, :
Paraldehyde is a colourless liquid, crystallising
0-79138 at 13, 0-78761 at 16 (Perkin, Chem. below 10 in large transparent prisms b.p. 124 ;
Soc. Trans. 45, 475). It has an extremely at 759-8 mm. and sp.gr. 0-998 at 15 (Kekule
pungent suffocating odour it is very inflam-;
and Zincke) sp.gr. 0-99925 at 15
; (Perkin,
mable, and burns with a feebly luminous flame. i
Chem. Soc. Trans. 45, 479) ; b.p. 123-2-123-5
Itsoluble in all proportions in alcohol,
is
I
at 744 mm. (Briihl, Annalen, 203, 26). When
ether, and water, and is separated from the condensed with hydroxyquinol, it produces
aqueous solution as an ethereal layer on yellow dyes (Liebermann and Lendenbaum,
addition of calcium chloride. When heated Ber. 37, 1171, 2728).
with aqueous soda, potash, or barium hydroxide, Metaldehyde crystallises in needles or tetra-
so-called aldehyde resin is obtained as a brown gonal prisms, sublimes without previous fusion
mass (Liebig, I.e. Weidenbusch, Annalen, 66,
; at 112-115, and when heated in sealed tubes
153 Lederer, Monatsh. 22, 536).
; Sodium at 120 is entirely reconverted into ordinary
amalgam converts aldehyde into ethyl alcohol, aldehyde (Friedel, Bull. Soc. chim. 9, (3) 384).
a small quantity of j8-butyleneglycol, which is According to Troeger (Ber. 25, 3316), after
also formed by the action of magnesium amalgam standing for ten years a sample was converted
(Meunier, Compt. rend. 134, 472 Tistschenko and ; into aldehyde and paraldehyde, but according
Grigoreeff, J. Russ. Phys. Chem. Soc. 38, 540 ; to Hantzsch and OechshV (Ber. 40, 4341),
Voronkoff, ibid. 38, 547), being formed simul- metacetaldehyde is not isomeric with paracet-
taneously (Kekule, Annalen. 162, 310). With aldehyde, and is quite stable when pure.
sodium, acetaldehyde reacts violently, pro- Orndorff and White (Amer. Chem. J. 16, 43)
ducing the compound CH 2 CH-ONa, which : state that when it is allowed to stand for
rapidly polymerises to a brown substance, some time the metaldehyde is converted into
whilst if the reaction takes place in presence tetraldehyde (C 2 4 0) 4 H .
of benzoic chloride in ethereal solution alde- Neither polymeride is resinised by aqueous

hydoaldolbenzoate C 13 H 16 4, m.p. 86-87, is soda or potash, but in other reactions they
formed (Freer, Amer. Chem. J. 18, 552 Annalen, ; behave generally as ordinary aldehyde and yield
293, 326). Phosphorus pentachloride reacts similar products (Kekule and Zincke).
with it, yielding ethylidene dichloride (Geuther, Reactions. -Aldehyde in aqueous solution
Annalen, 105, 323). very readily reduces an ammoniacal solution of
In presence of reduced nickel hydrogen silver nitrate giving a bright metallic mirror.
reduces aldehyde to ethyl alcohol, a good yield Acetaldehyde (and all aldel^'des which are
and pure product being obtained (Sabatier and stable in aqueous soda solution) can be de-
Senderens, Compt. rend. 137, 301). With potas- tected by adding to a solution of the suspected
ALDEHYDE. 71
substance in dilute alkali a fresh solution of Gazz. chim. ital. 31, i. 265 ; Fiquct, Bull. Soc.
1 part of paradiazobenzeiiesulphonic acid in chim. 7, (3) 767); with phenyl hydrazones
00 parts of water rendered alkaline with a little (Fischer, Ber. 29, 793; 30, 1240 ; Pechman, Ber.
soda, and then some sodium amalgam ; if an 31, 2123 ; Bamberger and Pemsel, Ber. 36, 85 ;
aldehyde is present, a reddish-brown colour is Lockmann and Liesche. Annalen, 342, 14 ;

developed after the mixture has stood for 1020 Medvedeff, Ber. 38, 1646, 2283 Maurenbrecher, ;
minutes (Penzoldt and Fischer, Ber. 16, 657). Ber. 39, 3583). Substances capable of use in
A solution of rosaniline decolourised by sul- perfumery can be obtained by condensing alde-
phurous acid (Villiers and Foyolle, Compt. rend. \
hydes with negatively mono- substituted acetic
119, 75), or magenta bleached by sunlight (Blaser, acids in presence of ammonia or a primary or
Chem. Zentr. 1899, ii. 848), regains its original secondary amine (J. Soc. Chem. Ind. 24, 689,
colour on addition of an aldehyde. This re- j
1323). (For compounds of other substances
action is due to the formation of coloured with aldehydes, see Hooker and Carnell, Chem.
compounds by the condensation of the aldehyde |
Soc. Proc. 1893, Fischer, Ber. 27, 165 Claisen, ;
and magenta (Urbain, Bull. Soc. chim. 1896, Annalen, 237, 261 ; Conneler, Chem. Zeit. 20,
iii. 15, 455). With salts of m-diamines alde- 585 Kietreiber, Monatsh. 19, 735
; Bamberger ;
hydes give coloured solutions with intense ;

and Miiller, Ber. 27, 147 Rassow, J. pr. ;
greenish fluorescence (Bitto, Frdl. 36, 369). j

'
Chem. 172, 136, 129 Betti, Gazz. chim. ital. ;
With sodium nitroprusside and alkali acetalde- 30, ii. 310

27 Koenigs, Ber. 34, 4336 ;
; 33, i. ;
hyde gives a cherry-red colouration, whilst if Moureu and Desmots, Compt. rend. 134, 355 ;
tnmethylamine is first added a blue colour is Knoevenagel, Ber. 36, 2136 Hann and Lap- ;
produced (Bitto, Annalen, 267, 372 ; 269, 377 ; worth, Chem. Soc. Trans. 1904, 46 Simon and ;
Deniges, Bull. Soc. chim. 17, (3) 381 ; Simon, Conduche, Compt. rend. 138, 977 ; Darzens,
Compt. rend. 125, 1105 ; Bull. Soc. chim. Compt. rend. 142, 214; Eissler and Pollock,
19, (3) 297). Thiosemicarbazide mixed with an |
Monatsh. 27, 1129; Rolla, Gazz. chim. ital.
aldehyde in acetic, alcoholic, or aqueous solution 37, 623 Senier and Austin, Chem. Soc. Trans.
;
yields characteristic thiosemicarbazones. Acet- ;

1907 1233 Wohl, Ber. 40, 4679 Braun, Ber.
> ; ;
aldehydethiosemicarbazone hasm.p.l46(Freund !
41, 2169 Zeisel and Bitto, Monatsh. 29, 591.)

;
and Schander, Ber. 35, 2602). Additive compounds. Aldehyde not only
Other tests for aldehydes are described by j
shows a strong tendency to yield polymerides
(Ihl,Chem. Zeit. 14, 1571; Doebner, Ber. 27,352, :
and condensation compounds, but unites directly
2020 Lumiere and Seyewetz, Bull. Soc. chim.
; with a large number of substances.
19, (3) 134 Rimini, Atti Real. Acad. Lincei,
;
i
(1) Compounds with alcohols (v. ACETAL).

1901, 10, 355 ; Murco, Compt. rend. 31, 943 ; (2) Compounds with acids Geuther, :
Riegler Frdl. 42, 168 ; Behrens, Chem. Zeit. 26, j

Annalen, 106, 249 ; Lieben, ibid. 106, 336 ; 178,
1125; Sadtler, J. Soc. Chem. Ind. 23, 387 ; 43 Riibencamp, ibid. 225, 279 ; Schiff, Ber. 9,
;
Prud'homme, Bl. Soc. Ind. Mulhouse, 1904, 304; Ponzio, J. pr. Chem. 161, 431 ; Schroeter,
74, 169 ; Leys, J. Pharm. Chim. 1905, 22, 107 ; |
Ber. 31, 2189; Annalen, 303, 114; Dele'pine,
Auld and Hantzsch, Ber. 38, 2677. Compt. rend. 133, 876 Mclntosh, Amer. Chem. ;
Aldehyde readily yields condensation com- J. 28, 588.

pounds ; thus when allowed to remain in the (3) Compounds with alkaline sulphites :
cold with dilute hydrochloric acid, or with Aldehyde forms definite crystalline compounds
aqueous solutions of zinc chloride or of salts when "dissolved in concentrated aqueous solu-
having an alkaline reaction, such as potassium tions of the acid sulphites (bisulphites) of the
carbonate, aldol is obtained, whilst croton- alkali metals. The potassium salt C 2 4 0,KHS0 3 H
aldehyde is formed when
heated with con-it is crystallises in indistinct needles ;
the sodium
centrated hydrochloric acid (Kekule', Annalen, H
salt C 2 4 0,NaHS0 3 2 0, in
The ammonium compound
+H
fine needles or
162, 92 Kling and Roy, Compt. rend. 144, 1111).
; nacreous plates.
Aldehyde has also been condensed with other has the formula C,H 4 (OH)S0 2 -NH 2 These salts .
aldehydes and ketones (Wallach, Chem. Zentr. are almost insoluble in excess of the sulphite,
899, 'ii. 1024; Schmalzhoffer, Monatsh. 211, and separate in the crystalline state ; from them
with a
671 Wogrinz, ibid. 22, 1 ; Weiss, ibid. 25,
; aldehyde can be obtained by distillation
or by alkali
1065^ Schachner, ibid. 26, 65 Salkind, J. Russ. ; stronger acid, an alkaline carbonate,
Phys. Chem. Soc. 37, 484; Rainer, Monatsh. nitrites (Bunte, Annalen, 170, 305 ; Freundler
25, 1035; Ehrenfreund, ibid. 26, 1003); with and Bunel, Compt. rend. 132, 1338, Seye-
amines (Eibner and Peltzer, Ber. 33, 3460 ; wetz and Burdin, Compt. rend. 141, 259; Rosen-
Eibncr, Annalen, 328, 121 Knoevenagel, Ber. ; heim, Ber. 38, 2005; Coppock, Chem. News,
37, 4461); with rhodanic and substituted rho- 1907, 225). With hyposulphites in neutral or
danic acids forming stable dyeing acid solutions aldehyde hyposulphites are
compounds
(Andreasch and Zipser, Monatsh. 24, 499 ; 26, obtained ; 2RCHO,M 2 S 2 4 (J. Soc. Chem. Ind.
1191; Zipser, ibid. 23, 592; Stachetz, ibid. 25, 475) by varying the condition sulphoxylates
;
26, 1209; Bergellini, Atti Real. Acad. Lincei, of type RCH 2 -SO 3 can be formed (D. R. P.M
15, 35, 181 Andreasch, Monatsh. 27, 1211 are obtained
; ; 180529). Crystalline thioaldehydes
by the action of hydrogen sulphide on an
29, 399 acidified
Wagner, ibid. 27, 1233) ; with methyl
;
ketole forming leuco- bases of the dyes of alcoholic solution of aldehyde (Baumann and
rosaniline type (Freund and Lebach, Ber. Fromm, Ber. 22, 2600 Ber. 24, 1419, 1457 ; ;
36, 308; Freund, Ber. 37, 322); with indole Klinger, Ber. 32, 2194 Drugman
and Stockings, ;
dyes, also forming leuco- bases (Loew, Ber. 36, Chem. Soc. Proc. 1904, 116; Vanino, J. pr.
4326); with cyanides and cyanacetic esters Chem. 185, 367).
(Claisen, Ber. 25, 3164 ; Barbier and Bouveault, Compound with ammonia
(4) Aldehyde- :
Compt. rend. 120, 1269; Kohn, Monatsh. 19, ammonia C 2 H 4 O-NH 3 obtained by leading dry ,
519; Wade, Chem. Soc. Proc. 1900, 156 ; Bertini, !

ammonia into aldehyde in ethereal solution
ALDEHYDE.
(Liebig, Annalen, 14, 144 ; Jean, Bull. Soc. primary alcohols. In composition the aldehydes
chira. 13, (3) 474; Trillat, ibid. 13, (3)- 689; differ from the alcohols from which they are
Dele'pine, Compt. rend. 125, 951; 128, 105; derived by containing two atoms of hydrogen
137, 984; 144, 853; Coninck, Compt. rend. fewer in the molecule whilst in their chemical
;
126, 1042; Tschitschibabin, J. Russ. Phys. behaviour they all exhibit the general pro-
Chem. Soc. 37, 1229 ; Duden, Bock and Reid, perties of the typical member of the series,
Ber. 38, 2036 ; Ciamician and Silber, Ber. 38, acetaldehyde.
1671; 39, 3942), crystallises in large rhombo- There are general methods for preparing
hedra, melts at 70-80, boils at 100 without aldehydes (1) By the
: action of organo-
decomposition, and is decomposed into its magnesium compounds on the esters of ortho-
constituents on distillation with dilute acids. formic ester thus :
When hydrogen sulphide is passed through a HC(OR) 3 + R'Mgl = ROMgl + R'HC(OR) 2

mixture of aldehyde ammonia and ether a
R'HC(OR) 2 + H 2 = R'HCO + 2R-OH
crystalline substance SH-CHMe-NH-CHMeOH,
obtained (Chabrie', C. R. Soc. (Tschitschibabin, Ber. 37, 186 ; Gattermann and
m.p. 60-63, is
Biol. 1896, 3, 72).
Maffezzoli, Ber. 36, 4152 ; Williams, Chem. Soc.
Proc. 1906, 22). (2) By decomposing with water
(5) Compounds with hydrocyanic acid :
the products of reaction between di-substituted

(Tiemann, Ber. 14, 1965; Strecker, Annalen, amino- formaldehydes on alkyl, aryl, or hydroxyl
91, 349 ; Erlenmeyer and Passavant, ibid. 200,
120).
magnesium halides ( J. Soc. Chem. Ind. 23, 1237 ;
With Bouveault, Bull. Soc. chim. 31, (3) 1306, 1322).
(6) Compounds with metallic salts :
mercuric sulphate it forms the compound S0 4 : (3) By the action of organo-magnesium com-
pounds on formic acid or alkyl formates (J.
(HgO) 2 HgC;jH 4
:
(Deniges, Compt. rend. 128, Soc. Chem. Ind. 24, 690 ; Chem. Zentr. 29, 667 ;
429) ; with mercuric nitrate, C 2 Hg 2 4 (Hof- N0 H D. R, P. 157573).
mann, Ber. 31, 2212) ; and with mercuric acetate Other methods are described by Stoermer
alkaline solution at 0, CMe-HOHgO (Lasserre,
(Ber. 39, 2288) Blaise (Compt. rend. 138, 697) ;
J. Pharm. 1905, 22, 246). With gold chloride it ;
forms a coloured colloidal solution (Garbowski, Faworsky (J. Russ. Phys. Chem. Soc. 38, 741);
Tiffeneau (Compt. rend. 37, 1260) Behal and
Ber. 36, 1215) ; and with magnesium bromide, ;
Sommelet (D. R. P. 177614, Compt. rend. 138,

the compound MgBr 2 ,3CH 3 CHO
(Menschutkin, Guerbet (Compt. rend. 146, 132) Mossier
Zeitsch. anorg. Chem. 53, 26). 89) ; ;
Substitution-derivatives. The action of (Monatsh. 29, 69) Merling (Ber. 41, 2064, 2217)
;
Aliphatic dialdehydes have been prepared by

chlorine on aldehyde has been studied by Wurtz
Wohl and Schweitzer (Ber. 39, 890) ; Suais (Bl.
(Annalen, 102, 93), Wurtz and Voigt (Bull. Soc. Ind. Mulhouse, 1907, 75).
chim. 17, 402), and by Pinner (Annalen, 179,
21 Coblenz, I.e. Freundler, Bull. Soc. chim.
;
ALDEHYDE GREEN v. TRIPHENYLMETHANE
;
COLOURING MATTERS.
1, (4) 66; Freundler, Compt. rend. 143, 682).
Pinner finds that when chlorine is passed into
ALDEHYDINE v. BONE OIL.
ALDEHYDINES. Compounds formed by the
ordinary aldehyde at 10, metaldehyde and par- condensation of ortho-diamines with aldehydes
aldehyde are first formed, and these subsequently
(Ladenburg, Ber. 10, 1126) (v. AMINES).
yield substitution-derivatives, of which chloral ALDER BARK. (Aune, Fr. ; Erie, Ger.)
is the chief product, butyric chloral and dichlor-
Alnus glutinosa (Gaert.). Used for tanning and
aldehyde being formed in smaller quantity. The
dyeing. The percentage of tannin varies from
following derivatives have been prepared :
CH Cl-CHO+iH 16 to 18 (Eitner, Zeit, f. d. Chem. Grossgew.

Chloraldehyde 2 2 (Natterer,
3, 668 4, 279).
Monatsh. 3, 446); dichloraldehyde, CHCl^CHO ;
The tannin appears to be a methyl tannin

(Grimaux and Adams, Bull. Soc. chim. 34, like that of the oak
29 ; Wohl and Roth, Ber. 40, 212) trichloralde- ;
;
it gives a reddish-blue
precipitate with ferrous acetate, an olive-green
hyde (v. CHLORAL).
The bromine derivatives, and the action of precipitate with ferrous sulphate, and is precipi-
tated by a gum solution.
bromine on aldehyde, have been examined by
Pinner (Ber. 7, 1499, and I.e. Bugarsky, Zeitsch.
;
A
solution of the bark is employed for ob-
taining black, greys, and browns on linen ; in
physikal. Chem. Freundler, Compt. rend.
48, 63 ;
140, 1693 ; Mauguin, Compt. rend. 147, 747). Germany for reds ; and in Kamchatka for
colouring skins a red tint.
Aldehyde blue is obtained by treating para- ALE v. BREWING.
rosaniline with aldehyde or, better, paraldehyde
in aqueous acid solution, and precipitating the ALEMBROTH, SALT OF. A compound of.
mercuric chloride and sal ammoniac
dye with sodium chloride. It is soluble in
alcohol and ether, and when treated with strong 2NH 4Cl,HgCl 2 ,H 2 0.
hydrochloric acid is converted into a reddish formed by mixing the two salts in suitable
yellow base which shows all the properties of a proportions. Also called by the alchemists Salt
rosaniline dye (Gattermann and Wichmann, Ber. of Wisdom.
22, 227). By slightly varying the conditions in ALEURITES CORD ATA (Steud. ).
The seeds
the preparation of aldehyde blue, aldehyde green of this euphorbiaceous plant, which is found
can also be obtained (Miller and Pliichl, Ber. 24, largely in Japan, yield Japanese wood-oil
1700). (q.v.).
ALDEHYDES. The name aldehyde origi- ALEURONE GRAINS. Organised granules
nally assigned to the compound obtained by the deposited in the cells of many seeds of plants,
limited oxidation of ethyl alcohol, has come to generally near the exterior, in which the proteins
possess a wider signification, and is now used are mainly concentrated. They were so named
as a generic term for a class of organic sub- by Hartig, who first described them. In many
stances which are similarly derived from the plants, the aleurone grains possess the shape of
ALGAROBILLA. 73
crystals. Botanists, indeed, regard them as con- A small amount of an albumose is also probably
sisting of two parts :

(1) a crystalloid, crystal- present. The globoids contain a globulin and
like protein body, and (2) one or more rounded mineral matter, especially calcium, magnesium,
globoids mainly composed of mineral matter, in and phosphoric acid they are soluble in con-
;
which phosphoric acid, lime, and magnesia are centrated solutions of ammonium sulphate,
usually the largest constituents. acidified sodium chloride, or potassium dihy-
When the aleurone grains exhibit the form drogen phosphate. The grains with their en-
of crystals, it is generally found that they are closures are reserve-food materials which are
soft and swell up if treated with weak acids or consumed when the seed germinates. They
'
alkalis. The term 'crystalloid,' as used by originate as liquid vacnoles,' in which an in-
botanists in this connection, has reference to creasing amount of protein material is gradually
the appearance of the aleurone grains, and not deposited. The germinating power of seeds
to their property of diffusion when dissolved probably depends upon the solubility of the
through membranes. According to Tschirch and crystalloids in dilute sodium chloride solution.
Kritzler (Chem. Zentr. 1900, ii. 585), the aleurone According to Posternak (Compt. rend. 1905,
grains of a variety of plants consist mainly of 140, 322), aleurone grains often contain anhydro-
globulins. The crystalloids consist of at least oxymethylene diphosphoric acid (phytine). He
two globulins, which are soluble in dilute, but found the following amounts of nitrogen and
insoluble in concentrated saline solutions (e.g. mineral substances in the aleurone grains of
ammonium sulphate, sodium chloride with trace (1) spruce fir, (2) sunflower, (3) hemp, (4) white
of acetic acid, potassium dihydrogen phosphate). lupin :
74 ALGAROBILLA.
adhering loosely to the somewhat open frame- by Martius and Griess, who obtained thus a
work of the fibre. It is one of the strongest substance of the formula C 10 6O 3 which was, H ,
tannin matters known, and contains on the however, not identical with alizarin, and was
average 45 p.c. In character it resembles divi- therefore supposed to be isomeric with it.
divi, and its extract is somewhat prone to Some time after these experiments of Martius
fermentation. It is very suitable for tanning and Griess, Graebe commenced his research on
and also for dyeing purposes. quinones, the working out of which led not only
ALGAROTH, POWDER OF. Pulvis Alga- to results which proved beyond a doubt what the
rothi, English Powder. A crystalline oxy- chemical nature of alizarin really was, but also
chloride of antimony, obtained by pouring anti- eventually resulted in the artificial production of
mony chloride into hot water. Used in the this important colouring matter. In pursuing
preparation of tartar emetic (v. ANTIMONY). this investigation Graebe succeeded in preparing
ALGIN. A nitrogenous body obtained from chloranil C 6 C1 4 O 2 by treating phenol with potas-
,
seaweed, somewhat resembling albumen (v. sium chlorate and hydrochloric acid, and in acting
IODINE). on this with caustic potash he found that two of
ALGODONITE. A copper arsenide of a the atoms of chlorine in this compound became
steel-grey colour. Found in the Lake Superior replaced by (OK), producing the potash salt of
copper-mining district. chloranilic acid C 6 Cl 2 (OK) 2 0.j, a change the/
ALHAGI CAMELORUM (Fischer), JAWASA, knowledge of which proved to be of the utmost
Of JAWANI. A leguminous thorny shrub, importance in his subsequent experiments on
the artificial production of alizarin.
widely spread from Greece to dry parts of India,
where a drug extracted from it is used for Chloroxynaphthalic acid was now considered
rheumatism, and also as a laxative and diuretic by Graebe to be related to naphthalin in much
J. [3] 9, 145). the same way as chloranil was to benzene, i.e. to
(Pharm.
ALIZARIN AND ALLIED COLOURING be a derivative of naphthaquinone.
MATTERS. Madder, Riibia tinctoria, which Soon after this the attention of Graebe and
was for a long time used on a large scale in Liebermann was turned to alizarin, which they
the
' '
two also thought might belong to the quinone series.
Turkey- red industry, contains
In determining the constitution of this
colouring matters, alizarin and purpurin, of
which the former is by far the more important. substance, the first step was to obtain some
Alizarin is not found ready-formed in the information as to the nature of the hydro-
madder-root, but exists there as a glucoside carbon from which alizarin was derived, and
'
this was done in the following way : Alizarin
called ruberythric acid,' which when allowed I
to ferment, or when boiled with dilute acid, |

prepared from madder was mixed with zinc-dust
splits up readily into alizarin and glucose.
i and heated strongly in a furnace, according to
The colouring matter itself was fir.jt isolated !
Baeyer's method of reducing benzenoid com-

from the madder-root in 1827 by Colin and pounds, and in this way a crystalline hydrocarbon
Robiquet, who obtained it by extracting ground
was obtained having the composition C 14 10 H ,
madder with hot water and subliming the puri- which on examination was found to be identical
fied extract carefully in a glass tube. ;
with anthracene, a hydrocarbon previously ob-
This method of sublimation was not con- ;
tained by Dumas and Laurent from coal tar.
sidered sufficient proof of the existence of alizarin Using the information already obtained in the
in madder, and it was not till Schunck suc- ]
research on quinone, Graebe and Liebermann
ceeded in isolating this substance by chemical now assumed that alizarin must be a dihydroxy-
means from the madder extracts used by quinone of anthracene, the relation of these
substances to one another being seen from the
dyers that this important point was definitely !
following formulae
:
settled. :
In assigning the correct formula to alizarin, C 14 H 10 C 14 H 8 2 C 14 H 6 2 (OH) 2

considerable difference of opinion existed at first, :
Anthracene. Anthraquinone. Alizarin.
owing no doubt to some extent to the difficulty Having thus obtained anthracene from ali-
experienced in obtaining alizarin in a condition :
zarin,it was now only necessary to reverse the
pure enough for accurate analysis.
operation and convert anthracene into alizarin,
Schunck proposed the formula Ci 4 in 4 H ,
and the problem of the artificial production of a
whilst Strecker believed it to be C 10 H 6 3 and
related to
' ' vegetable colouring matter would be solved for
chloroxynaphthalic acid (chloro- 1
the first time.

hydroxynaphthaquinone), a derivative of naph- In 1862 Anderson, while investigating anthra-
thalene, since both these substances on oxidation
cene, obtained from it by oxidation a substance
yield phthalic acid. H
of the formula C 14 8 2 which he named ox- ,
Strecker's formula was the more generally anthracene.
accepted by chemists, and chloroxynaphthalic In this substance Graebe and Liebermann
acid was looked upon as being simply chlorinated
recognised the quinone of anthracene (anthra-
alizarin, the two bodies being thus related :
quinone), the first step in the synthesis of alizarin

Ci Hg0 3 C 10H 5C10 S from anthracene, and in order to convert this
Alizarin. Chlorinated alizarin or quinone into alizarin all that was necessary was
Chloroxynaphthalic acid. to replace two atoms of hydrogen in it by
In order to prove the relation supposed to hydroxyl, an operation which is easily done in
exist between these two substances, it was only the following way :
necessary to replace the chlorine atom in Anthraquinone when heated with two mole-
cules of bromine in sealed tubes is converted into
chloroxynaphthalic acid by hydrogen, when
alizarin should result. dibromanthraquinone, thus :
This operation was eventually accomplished C 14 H 8 2 +2Br 2 =C 14 H 8Br 2 2 +2HBr.

ALIZARIN AND ALLIED COLOURING MATTERS. 75
This substance when heated with potash ex- black, and on dissolving this in water a rich
changes each of its bromine atoms for (OK), yield- purple solution was obtained which when acidi-
H
ing the potash salt of alizarin, C 14 6 (OK) 2 O 2 a ,
fied with dilute sulphuric acid
gave a copious
reaction which is precisely similar to the forma- precipitate of alizarin.
tion of chloranilate of potash from chloranil as The great obstacle to the preparation of
described above. The potassium alizarate thus alizarin viz. the use of bromine was thus re-
obtained, when decomposed with hydrochloric moved, and, as the future has proved, a process
acid, yielded alizarin, and thus the problem of had been obtained by which this colouring
the artificial production of alizarin was solved. matter could be manufactured in quantity and
In considering this synthesis, perhaps the at a price so cheap as entirely to supersede the
most remarkable fact, from a chemical point of old method of dyeing with the madder root.
view, is that, in consideration of the number of Another process for the manufacture of arti-
possible isomers of alizarin, just that dibrom- ficial alizarin shortly afterwards discovered
by
anthraquinone prepared by Graebe and Lieber- W. H. Perkin, and largely used by him on a
mann should on treatment with potash have manufacturing scale, is the following :
yielded alizarin. Had

this not been so, the Anthracene is treated with chlorine and
artificial production of alizarin would no doubt thus converted into a beautifully crystalline
have been very much delayed. compound called dichloranthracene C 14 H SC1 2 .
The great importance of alizarin as a dyeing This substance combines with Nordhausen
agent induced Graebe and Liebermann to patent sulphuric acid, forming a bright-green solution,
this process, which proved, however, to be of no which contains a sulphonic acid of dichloran-
commercial value, owing to the great expense thracene. When heated with sulphuric acid
attending the use of bromine, and it was there- this substance undergoes a remarkable
change,
fore desirable to find some new method which hydrochloric acid and sulphurous acid are
would render their discovery important from a evolved, and a disulphonic acid of anthraquinone
manufacturing point of view. formed, thus :
This was first achieved by W. H. Perkin in *
C 14 H 6 C1 2 (S0 3 H) 2 +H 2 S0 4
the following way :
Sulphuric acid, as is well
Dichloranthracene-disulphonic acid.
known, forms with many organic bodies com- =C 14 H 6 2 (S0 3 H) 2 +2HC1+S0 2 .
pounds called sulphonic acids, which in composi- Anthraquinone disulphoiiic acid.

tion simply correspond to the substance acted This anthraquinone disulphonic acid when
on plus sulphuric anhydride. fused with potash yields alizarin.
Thus benzene C 6 H 6 when treated with sul-
phuric acid acid Alizarin and the other colouring matters of
yields benzenesulphonic
C 6 H 5S0 3 H naphthalene C i0H 8 naphthalene-
; ,
this class willnot dye unprepared fabrics ;
sulphonic acid C 10 H 7 S0 3 H. When fused with these must first of all be mordanted.
caustic potash these sulphonic acids are split up The mordants used in this case consist of
into the potassium salt of the corresponding metallic hydroxides e.g. of aluminium, iron,
phenol and potassium sulphite, thus :

and chromium. Chloride of tin (tin crystals) is
also extensively employed.
C 6H BS0 3 H+3KOH=C 6H 6 OK+K 2 S0 3 +2H 2 0.
With alumina mordants alizarin produces
Similarly disulphonic acids when fused with shades of red and pink with iron mordants,
;
potash are converted into dihydric phenols, thus :

shades of black and purple with chromium
;
mordants, a dull purple and with tin crystals a

;
bright yellowish orange. These mordants may

In this second example it will be seen that a also be mixed and thus a large variety of different
body is formed which bears the same relation shades produced. A description of the method
to benzene as alizarin does to anthraquinone, of application of these various mordants and the
and it was therefore probable that if anthraqui-
processes employed in dyeing with alizarin will
none were subjected to a similar series of re- be found in the article DYEING.
actions, alizarin would result. Since the first production of artificial alizarin
The great obstacle to carrying out this on the large scale, the study of this substance
synthesis, in the first instance, was the remark- and of the various colouring matters related to
able stability of anthraquinone in general and it has received a large amount of attention at
particularly towards sulphuric acid, which is so the hands of chemists, the result being that a
great that it dissolves in moderately hot sul- considerable number of derivatives of anthra-
phuric acid without change, and crystallises out quinone have been prepared and examined.
again in needles on cooling. Most of these are either colouring matters
When, however, a mixture of anthraquinone themselves, or easily converted into such,
and sulphuric acid was heated very strongly, several of them being obtained on the large scale
combination did eventually take place, the pro- in the manufacture of alizarin.
duct becoming perfectly soluble in water, the These derivatives may be divided under the
solution now containing mono- and
disulphonic following heads :
acids of anthraquinone.
(1) Sulphonic acids of anthraquinone.
After removing the excess of sulphuric acid
(2) Monohydroxyanthraquinones.
from the new product, it was mixed with caustic
(3) Dihydroxyanthraquinones.
potash, and heated to about 180. (4) Trihydroxyanthraquinones.
During the heating the melt became darker (5) Higher hydroxylated anthraquinones.
and darker in colour, and eventually almost In this article are also included the two
dyeing matters, Gallein and Ccerulein, which
1
It should be mentioned here that wliile these ex-
periments were in progress, Caro, Graebe and Lieber-
mann were investigating although not actually anthracene derivatives, are
the same reaction in Germany. very closely allied to them.
ALIZARIN AND ALLIED COLOURING MATTERS.
Sulphonic acids of anthraquinone. soda (or caustic soda). This causes the difficultly
soluble sodium salt of anthraquinone mono-
Anthraquinone a-sulphonic acid sulphonic acid to separate out, leaving the
C 6H 4 <3xJ>C 6H 3 -S0 3 H. easily soluble salt of the disulphonic acid in
(1) solution.
It is a remarkable instance of the influence The pasty mass obtained on neutralising
of a catalyst that whilst anthraquinone ordi- with soda is thoroughly pressed, washed with a
narily sulphonates in the 2- position, yet in the littlewater, and then if required pure recrystal-
presence of quite small amounts of mercury the lised from this solvent. In this way a beautiful
1- position is exclusively attacked. brilliant white scaly crystalline mass is obtained,
In preparing anthraquinone a-sulphonic acid, which consists of pure sodium anthraquinone
'
monosulphonate, the so-called silver salt
'
100 pts. of anthraquinone are heated for three of
hours at 130 with 110 pts. of sulphuric acid the alizarin manufacturer.
containing 29 p.c. sulphuric anhydride, and The free acid obtained by the addition of an
0-5 part of mercury. acid to the soda salt crystallises in plates. It
The free acid is easily soluble in alcohol and is very easily soluble in cold water and alcohol,
water, its lead, barium, and strontium salts are but almost insoluble in ether.
very insoluble in hot water. The calcium salt When fused with caustic soda, this acid (or
is fairly soluble, but crystallises on heating the rather its soda salt) gives first hydroxyanthra-
solution. The potassium salt occurs in glistening
yellow leaflets. quinone C 6 H 4<^,~,Q^>C 6 H 3 OH, and then
The
further sulphonation of the a acid in
alizarin and, as will be shown later on, alizarin,
presence of mercurj- leads to the formation of
;
when prepared on a manufacturing scale, is in-

1 :
anthraquinone disulphonic acid, mixed
5-
with 8- and 1
1 : 7- acids. :The same mixture variably formed from the monosulphonic acid of
isproduced by the direct sulphonation of anthra- anthraquinone, not from the disulphonic acid
as might be expected. The reason for this is
quinone (100 parts) with 200 parts of sulphuric-
acid containing 40 p.c. sulphur trioxide, in the that on fusing hydroxyanthraquinone with
caustic soda, a continuous process of oxidation
presence of mercury (1 part) at 160 for one
hour. The mixture of acids is converted into and reduction is carried on, the change being
calcium salt and fractionally crystallised. The represented by the following equation :
calcium salt of the 1 8- acid is least soluble,

: C 14 H 7 (ONa)0 2 +NaOH+0
the middle fraction is the largest and consists Sodium monohydroxyanthraquinonate.
of 1 5- whilst the calcium salt of 1:7- is
:
easily soluble.
>
2 +OH 2.
Similarly it has been found that anthra- Sodium alizarate.

quinone ^-sulphonic acid (see below) is changed the ox3 gen being supplied at the expense of a
r
by sulphuric acid in presence of mercury to a part of the hydroxyanthraquinone which is there-

mixture of 2:8- and 2 : 5- anthraquinone disul-
by reduced to anthraquinone. On the large scale
phonic acids (N.B. 2 : 8- is same as 1 7). It :
this reduction is prevented by the use of chlorate
is strange that the direct sulphonation of anthra-
of potash in the fusion.
quinone in the presence of mercuric sulphate also Literature. Graebe and Liebermann (An-
yields the 2 : 8- disulphonic acid. The constitu-
nalen, 160, 131 ; 212, 44 Ber. 7, 805).
;
tion of these sulphonic acids has been demon-
Anthraquinone disulphonic acids
strated by their conversion into the correspond-
^CO-
ing hydroxyanthraquinones by heating under
pressure with milk of lime.
Literature. Iljinsky (Ber. 36, 4194-4200) ;
When anthraquinone is heated to a high tern-
Schmidt (Ber. 37, 66-72). :
perature with 2 or 3 parts of ordinary or better

Anthraquinone- 2 or ,s- sulphonic acid fuming sulphuric acid, a mixture of a- and #-
c^c\ anthraquinone disulphonic acid is obtained,
p jr <c^^^***yC\ H (SO HI which can be separated by fractional crystal-
lisation of the sodium salts.
This acid formed together with a certain
is Preparation. 1. A mixture of 10 kilos, of
amount of anthraquinone disulphonic acid by anthraquinone and 20 to 30 kilos, of fuming sul-
heating anthraquinone with fuming sulphuric phuric acid is heated to a temperature of 160-
acid to 170 or with ordinary sulphuric acid to 170 until a sample taken out is found to clis-
250-260. |
solve completely in water. The product is then
In preparing it a mixture of one part of heated another hour to convert any mono- into
fuming sulphuric acid (containing 4050 p.c. disulphonic acid, poured into water, neutralised
anhydride) and 1-1J parts of anthraquinone is with caustic soda, and evaporated. 2. 10 kilos,
gradually heated to about 170 and kept at this of anthraquinone, 12 kilos, of hydrogen sodium
temperature for eight or ten hours, the whole sulphate, and 40 kilos, of ordinary concentrated
being well stirred during the operation. sulphuric acid are heated in pressure tubes for
The product thus formed consists chiefly of five or six hours to 260, the product treated
the monosulphonic acid together with a little with water, and the acids converted into sodium
disulphonic acid and unchanged anthraquinone. salts as above.
On diluting with water the anthraquinone sepa- In concentrating the solution of the sodium
rates out, and can easily be filtered off, leaving salt obtained by either of the above methods,
the sulphonic acids in solution. In order to sepa- the sodium salt of the a-acid crystallises out
rate the mono- from the disulphonic acid the first, the more readily soluble salt of the /3-acid
clear filtrate is neutralised with carbonate of remaining in the mother-liquors, and thus by
repeated recrystallisation, the two acids are disulphonate with nitric acid. The sodium salt
easily separated from one another. crystallises in yellow prisms, which are sparingly
The free acids obtained by decomposing the soluble in water. On fusing with potash this
salts by an acid are both readily soluble salt yields chrysazin C
14 H
6 (OH),0,, hydroxv-
in alcohol and water, but insoluble in ether H
chrysazm C 14 5 (OH) 3 2 ,m-hydroxybenzoic acid,
and benzene; the a-acid crystallises in small and salicylic acid.
yellow crystals, the j8-acid in beautiful yellow Literature. Liebermann and Dehnst (Ber
plates. 12, 1288).
The salts of the a-acid are sparingly soluble p-Anthraquinone disulphonie acid is obtained
in water and crystallise with difficulty ; those of by oxidising 0-anthracene disulphonic acid. The
the /3-acid are readily soluble and crystallise soda salt crystallises in leather-yellow plates,
with the greatest ease. which are easily soluble in water. On
fusing
Besides these two important acids, two with potash it yields anthrarufin
other disulphonic acids of anthraquinone are
known viz. X' an t nra(lumone disulphonic acid
and p-anthraquinone disulphonic acid. hydroxychrysazin C 14 H 5 (OH) 3 0,, m- and o-
Literature. Schultz (Chemie des Stein- hydroxybenzoic acids.
kohlentheers, 709, 712) Perkin (Chem. Soc.
; Literature. Liebermann and Dehnst (Z.c.).
Trans. 1870, 133) Graebe and Liebermann
; The relation of the various colouring matters
of this group to anthracene,
(Annalen, 160, 134). anthraquinone, and
Y-Anthraquinone disulphonic acid. This its sulphonic acids is
easily understood from the
acid is formed by treating sodium a-anthracene following table (Schultz) :
Anthracene
I
Anthraquinone (a- & -)

Anthracene disulphonic acids
(a- & -) Monosulphonic acid (a- & j8-) Disulphonic acids (x- & p-) honic acids
Disulphonic
o- & j-Hydroxyanthraquinone Anthranavic

iflavic acid Isoanthraflavic acid Chrysazin Anthrarufin
Alizarin Flavopurpurin Isopurpurin Hydroxy- (Hydroxyan-

(Anthrapurpurin) chrysazin thrarufin)
The behaviour of the
anthraquinone disul- 190. When fused with potash it gives alizarin.
phonic acids on fusion with potash is exactly The substance does not dye mordanted fabrics.
similar to that of the monosulphonic acid. Just 1- Acetoxyanthraquinone, prepared by boil-
as this acid on fusion with potash is first coning erythroxyanthraquinone with acetic anhy-
verted into monohydroxyanthraquinone and dride and sodium acetate, crystallises in yellow
then by oxidation into dihydroxyanthraquinone needles from alcohol and melts at 176-179.
(alizarin), so the anthraquinone disulphonic 1- methoxyanthraquinone is obtained by
acids in the first place yield the corresponding the action of boiling methyl alcoholic potash on
dihydroxyanthraquinones, which then by the 1- nitroanthraquinone.
further action of the potash are converted into This is the simplest example of a very general
trihydroxyanthraquinones. reaction in the anthraquinone series. The sub-
stance is yellow, microcrystalline, and melts at
Hydroxyanthraquinones.
140-145.
Literature. Baeyer and Caro (Ber. 7, 969) ;
I. Monohydroxyanthraquinones Pechmann (Ber. 12, 2128); Romer (Ber. 15,
1793), Liebermann and Hagen (Ber. 15, 1804) ;
Hoechste Farbwerke (D. R. P. 97688).

2- hydroxyanthraquinone.
1- hydroxyanthraquinone. Erythroxyanthra- This substance is obtained synthetically (to-
quinone.
This substance is formed together with 2- gether with erthroxyanthraquinone) by heating
a mixture of phenol, phthalic anhydride, and
hydroxyanthraquinone by strongly heating a The mixed hydroxyanthra-
mixture of phenol and phthalic anhydride with sulphuric acid.
quinones can be separated by means of baryta
sulphuric acid
water, since the barium salt of 1- hydroxy-
anthraquinone is insoluble, whilst the 2- hydroxy
compound is easily soluble. It crystallises from
=C H alcohol in yellow plates which melt at 323 and
6 4 <gg>C H (OH) + H 0.
6 3 2
readily sublimes at a higher temperature.
Also by heatingbromanthraquinone with
1- It can be obtained in various ways from
potash to 160 or by acting on 1- amidoanthra- anthraquinone or its derivatives.
quinone with nitrous acid in concentrated An easy preparation consists in melting
sulphuric acid solution. anthraquinone sulphonic acid or 2- bromanthra-
1-
hydroxyanthraquinone crystallises from quinone with potash.
alcohol in orange-red needles which melt at The action of ammonium persulphate on a
78 ALIZARIN AND ALLIED COLOURING MATTERS.
condenses with benzene
solution of anthraquinone in concentrated sul- Hemipinic anhydride
to in the presence of aluminium chloride, yielding
phuric acid containing sulphur trioxide leads
the production of 2- hydroxyanthraquinone, the methyl ether of dihydroxybenzoylbenzoic
alizarin, and purpurin. acid. This latter substance, on treatment with
reduced
to 2- hydroxyanthra- hot sulphuric acid, is converted into alizarin
Alizarin is
quinone by the action of alkaline stannous methyl ether, which is hydrolysed by aluminium
chloride to alizarin. The following formulae
chloride; or alizarin amide, obtained by the
of reactions
represent this series
:
action of ammonia on alizarin, yields this sub-
stance when treated with ethyl nitrite.
A GO
very curious reaction of this hydroxy-
anthraquinone, and one which involves migra-
tion of an oxygen atom, is its conversion to
quinizarin by treatment with nitrous acid in
sulphuric acid solution and in the presence of OH CO
boric acid.
Graebe and Liebermann (An- MeO/X/
Literature.
+ CH 3C1
nalen, 160, 141) Baeyer and Caro (Ber. 7,
;
969) ; Liebermann and Fisher (Ber. 8, 975) ; OOH

Liebermann (Annalen, 183, 208) ; Wacker (J. Pr.
Chem. [2] 54, 89) Bayer & Co. (D. R. P. 86830).
;
OH CO
MeO
+H 2
0.
Dihydroxyanthraquinones.
Alizarin
1 : 2- dihydroxyanthraquinone Alizarin methyl ether.
MANUFACTURE OF ALIZARIN.
1. Anthraquinone process. Anthracene, the
madder as the glucoside
Alizarin occurs in basis of alizarin, is obtained entirely from the
ruberythric acid, and also in Chay root (Olden- coal-tar oils boiling above 300, the so-called
landia umbellata) and some species of rhubarb. '
last runnings of the tar distiller. These
It is obtained from its glucoside by the action heavy oils are redistilled and the anthracene
of dilute acids or of ferments. oils collected as soon as the distillate on cooling
commences to solidify. In this way a semi-
C 2S H 28 14 + 2H 2
= C 14 H 8 4 + 2C H 12
6 6
.
solid greenish-looking mass is obtained, which,
Ruberythric acid. Alizarin. Glucose.
after roughly freeing from excess of oil by treat-
It may be prepared artificially by manv ment in hydraulic presses, is the starting-point
methods. in the alizarin factory. This crude product con-
Thus alizarin is produced by fusing dichlor- tains only about 30-40 p.c. anthracene, the re-
anthraquinone, dibromanthraquinone, anthra- mainder consisting of phenanthrene, naphthal-
quinone, mono- or di-sulphonic acids with ene, carbazol, and small quantities of other
potash. Rufigallic acid yields alizarin when hydrocarbons.
reduced with sodium amalgam. The first operation necessary in the manu-
On the other hand, anthraquinone may be facture of alizarin is that of purifying the crude
directly oxidised to alizarin by the action of anthracene obtained from the tar distillers, in
ammonium persulphate in concentrated sulphuric order to obtain a product fit for the subsequent
acid solution. oxidation to anthraquinone.
Good yields of alizarin are said to be obtained This process of purification varies consider-
by heating anthraquinone with sodium chlorate ably in different countries, but the following
and a mixture of sodium and potassium hy- method may be given as having been used with
droxides in aqueous solution at 200. This much success.
process used for the manufacture of alizarin,
is The crude anthracene is first ground between
but it is not clear that it has entirely displaced edge-runners, and then thoroughly agitated with
the older process shortly to be described. boiling petroleum spirit in large iron vessels
Hystazarin undergoes isomeric change to fitted with stirrers and heated with steam.
alizarin when heated with concentrated About 1500 to 1800 Ibs. of crude anthracene
sulphuric
acid to 200 for two and a half hours. and 300 gallons of petroleum spirit are used in
Alizarin may be synthesised by processes not one operation, the amount of the latter varying
involving the intermediate formation of anthra- slightly according to the quality of the anthra-
quinone. cene employed. After boiling for an hour or
Together with hystazarin it is produced when two, the product is allowed to cool, filtered
a mixture of catechol and phthalic anhydride is through coarse canvas, and the anthracene on the
heated with sulphuric acid at 200. filter washed with a little clean petroleum spirit.
The pasty mass thus obtained is next treated
with steam to remove the excess of petroleum
Phthalic anhydride. Catechol. spirit, and then sublimed. The sublimation pro-
cess is best carried out by melting the anthra-
+H
'
: 2 0. cene in an iron pot, called the subliming pot,'

2
and then blowing in superheated steam. This
Alizarin.
carries the anthracene vapour forward through
Finally the following synthesis of alizarin is a long pipe, where it meets a spray of water,
noteworthy :
which serves to condense both it and the steam.
The anthracene is thus obtained in an extremely is best purified by crystallisation from
liquid
finely divided state, much more sulphur dioxide or ammonia.
suitable for
oxidation than when simply ground under edge- The anthraquinone is now in a condition
runners as it used to be. The next step consists suitable for conversion into the
sulphonic acid.
in converting the anthracene into anthraquinone This operation, which consists in
heating
by oxidation with bichromate of potash (or soda) anthraquinone with fuming sulphuric acid, is
and sulphuric acid an operation which is usually conducted in large iron pots capable of
holding
done in the following way The anthracene is
: from 30 to 40 gallons. The amount of
fuming
placed in lead-lined tanks with about twice sulphuric acid employed depends on the nature
its
weight of the bichromate (dissolved in water), the of the sulphonic acid required. In preparing
requisite amount of dilute sulphuric acid is slowly the monosulphonic acid, 1 part of
fuming acid
added, and the mass kept well boiled and agi- (contained 40-50 p.c. S0 3 ) and 1 to 1 parts of
tated by a steam jet connected with a Korting's anthraquinone are used.
injector. The mixture is gradually heated by means of
The whole is then transferred to settling an oil-bath to 170, or even to 190, and kept at
tanks, the crude yellowish-brown anthraquinone this temperature for eight or ten hours, the
well washed by decantation until free from green stirrer being kept constantly in motion.
chrome liquors, well drained, and freed from The product, which contains, besides anthra-
water as completely as possible by placing it in quinonemonosulphonic acid, a little disulphonic
canvas bags and exposing it to great pressure in acid, and some unacted-on anthraquinone, is
a hydraulic press. The amount of oxidiser re- diluted with water, passed through a filter-press
quired to convert the crude anthracene into an- to remove the anthraquinone, and neutralised
thraquinone is of course regulated by the purity with caustic soda.
of the sample employed, pure anthracene re- In a short time the whole becomes quite
quiring about 1 -66 times its weight of potassium thick owing to the separation of the sparingly
bichromate to convert it into anthraquinone.. soluble soda salt of anthraquinonemonosul-
Instead of potassium bichromate, the sodium phonic acid, the easily soluble salts of the di-
salt is now very often used on account of its sulphonic acids remaining in solution.
cheapness. The crystalline salt is collected in filter-
The anthraquinone thus obtained is still very presses, washed with a little very dilute sul-
impure, and must be carefully purified before it phuric acid, and thus obtained practically pure
can be converted into sulphonic acid. In puri- in beautiful, brilliant, pearly scales.
fying anthraquinone two methods may be In preparing the disulphonic acids of anthra-
employed :
quinone, the operation is similar to the above,
(1) The anthraquinone is sublimed, and then the only difference being that more fuming
recrystallised from high boiling coal-tar naphtha. sulphuric acid is used and the sulphonation
(2) The anthraquinone is treated with con- conducted at a much higher temperature
centrated sulphuric acid. (about 260).
When the first process is employed, the an- The next operation consists in the conversion
thraquinone melted in iron pots and subjected
is of the product just described, and called ' soda
to the action of super-heated steam. The steam salt,' into colouring matter, a change which is
carries the vapour of the anthraquinone with it, accomplished by heating it strongly with caustic
and on condensation a fine, almost impalpable, soda and a little potassium chlorate.
powder is obtained, which, when dried and re- If the potassium chlorate is not added, a
crystallised from high-boiling coal-tar naphtha, considerable loss is incurred owing to the re-
consists of nearly pure anthraquinone. ducing action of a large quantity of nascent
In this country this process has now been hydrogen, always formed during the fusion,
almost abandoned method (2) having entirely
;
which converts the soda salt partially into an-
taken its place. thraquinone and hydroanthraquinone. The
The working of this method is based on the fusion is conducted in large wrought-iron cylin-
fact that crude anthraquinone when treated with ders fitted with stirrers and heated with hot air.
sulphuric acid at 100 dissolves, but is not acted The usual charge is 700 Ibs. caustic soda (70 p.c.)
on. The impurities, however, become converted dissolved in water, 1300 Ibs. of a concentrated
into sulphonic acids, which, being easily soluble, solution of ' soda salt,' and 13 to 15 p.c. of
can be removed by treating the product with potassium chlorate, the amount of this latter
water, when nearly pure anthraquinone is left substance varying slightly with the nature of
behind. the salt used, the monosulphonic salt requiring
In carrying out this operation a mixture of more chlorate than the disulphonic salt.
1 part of crude anthraquinone and 3 parts of The temperature is maintained at about 180
sulphuric acid is placed in large circular lead- for at least twenty-four hours and often much
lined iron pots, and heated by steam for twenty- longer, the progress of the decomposition being
four hours, the whole being continuously agitated controlled from time to time by extracting small
by a stirrer. quantities of the melt and examining them in
The blackish-looking product is then run into the laboratory.
shallow tanks, and exposed to the action of damp The product thus obtained is an intense
air, or a gentle current of steam, until the acid purple fluid, becoming thick on cooling and con-
has become diluted. In a short time anthraqui- taining the colouring matter as sodium salt
none separates out as a light-brown crystalline besides sodium sulphite and an excess of caustic
powder, which, after washing by decantation, soda.
pressing, and thoroughly drying, is found to To separate the colour the melt is run into
contain about 95 p.c. of pure substance. large wooden tanks, diluted with water, and
According to recent patents anthraquinone boiled with dilute sulphuric acid.
This causes the solution to become orange in isaccomplished in iron pots capable of holding
colour owing to the precipitation of artificial about 30 gallons and fitted with iron covers in
alizarin. which there is an opening for the escape of the
After being allowed to settle, the supernatant acid vapours formed during the reaction.
liquor is run off, the alizarin forced into filter- These pots are charged with 350 Ibs. of con-
presses and carefully washed until free from centrated sulphuric acid and heated to 140-160
acid and saline matter. The colouring matter by means of an ordinary fire, the dichloranthra-
is then made up to a definite strength (10 p.c. or cene (70 Ibs.) being shovelled in in small quanti-
20 p.c. paste as required) by transferring it to ties at a time. After all the dichloranthracene
large wooden tubs fitted with powerful stirrers, has been added and the frothing due to the
and thoroughly mixing it with water. evolution of the hydrochloric and sulphurous
Pure alizarin thus prepared produces a blue acids produced during the decomposition has
shade of Turkey-red, and anthrapurpurin (pro- '
subsided, the temperature is gradually raised
duced by fusing sodium anthraquinonedisulpho- to 260 and then maintained at this point until
nate with caustic soda) a red shade, so that by a sample taken out on a glass rod and diluted
varying the amounts of these two constituents
!
with water forms a nearly clear solution devoid

any intermediate shade required by the market of fluorescence.
can be obtained. The product contains now the mono- and
2.Dichloranthracene process. In manufac- disulphonic acids of anthraquinone, the latter of
turing alizarin by this process it is necessary, which greatly predominates.
in the first place, to purify the anthracene used These crude sulphonic acids are next diluted
much more thoroughly than is the case in the with water in a large wooden tank and boiled
anthraquinone process. with slaked lime until neutralised. The neutral
For this purpose the anthracene, after washing product is then forced into filter presses to sepa-
with petroleum spirit as described in the last rate the calcium sulphate, the clear filtrate mixed
process, is submitted to distillation with potash. with the washing of the calcium sulphate, evapo-
This removes the carbazol and the phenolic sub- rated until it contains about 15 p.c. of lime
stances present in the crude anthracene, and as, salts, and then treated with sufficient sodium
besides this, a considerable quantity of the other carbonate to precipitate all the lime as carbonate.
impurities are charred during the distillation, The solution of the sodium salts of the sul-
the anthracene resulting, although still very im- phonic acids is siphoned from the precipitated
pure, is found to be greatly improved in quality. calcium carbonate, concentrated until it contains
In carrying out this operation 100 parts of 30 p.c. of soda salts, and then converted into
washed anthracene, 30 parts of potash, and 6 colouring matter by fusion with caustic soda, as
parts of powdered lime are thoroughly ground described in the last process.
together under edge-runners, the mixture intro- Purification of artificial alizarin. Com-
duced into iron retorts and distilled. The dis- mercial alizarin contains as impurities hydroxy-
tillate, which consists of pale-yellow cakes con- anthraquinone, anthrapurpurin, flavopurpurin,
taming about 50 p.c. of pure anthracene, is now and small quantities of other colouring matters.
sufficiently pure for conversion into dichlor- In order to separate the alizarin from these,
anthracene. the crude commercial product is dissolved in
In chlorinating anthracene, leaden chambers dilute caustic soda, and the solution treated with
are used, technically known as chlorine ovens.' carbonic acid until two-thirds of the colouring
These are 10 ft. long, 4 ft. 6 in. wide, and 1 ft. 6 in. matter has been precipitated as acid sodium salt.
deep, and are used in pairs, connected at one The precipitate is collected, washed with water,
end in order that any chlorine escaping from the decomposed with hydrochloric acid, the crude
first oven may come in contact with a fresh alizarin thus obtained dissolved hi caustic soda,
amount of anthracene and thus prevent loss. and the treatment with carbonic acid repeated
400 Ibs. of anthracene are put into each oven, twice more.
and subjected to the action of a rapid current of The purified product is then boiled with
chlorine for about five or six hours. baryta water to remove hydroxyanthraquinone
The anthracene first fuses and gets dark in and anthraflavic acid (which dissolve), the bariun
colour, hydrochloric acid being evolved in abun- salt of alizarin is collected,
washed, decomposed
dance ; but after a time this fluid product begins by hydrochloric acid, and the alizarin either sub-
to deposit crystals and soon becomes a semi- limed or recrystallised from alcohol.
solid mass. In order to purify this crude pro- Another method of separation is based on
duct, it is first freed from hydrochloric acid by the temperatures at which the various con-,
washing with dilute caustic soda, and then stituents of the mixture sublime. Alizarin itself
pressed between linen cloths in a hydraulic sublimes at 110, flavopurpurin and anthra-
press, by which means a considerable quantity purpurin at 160 and 170 respectively.
of a thick dark oily product, technically known Alizarin crystallises from alcohol in red
'
as chlorine oils,' is got rid of. needles or prisms, which melt at 282. With
The yellow cakes of dichloranthracene thus care alizarin can be sublimed in magnificent
obtained are still not pure enough for use they ;
deep-red prisms, which, if the operation be per-
must next be soaked in coal-tar naphtha for formed on a large scale, may be obtained over
some time and pressed, this operation being re- an inch hi length.
peated until a product is obtained which con- It dissolves in alkalis with a purple colour,
tains 84 p.c. of pure substance. and is completely precipitated from this solution
The next process consists in converting the
by the addition of lime or baryta in the form of
dichloranthracene into the sulpho- acids of a blue precipitate of the calcium or barium salt.
anthraquinone by treating it with ordinary con- Heated with acetic anhydride to 160 alizarin
centrated sulphuric acid. This H
decomposition forms a diacetyl compound C 14 6 2 (C 2 H 3 0) 2 2,
which from alcohol in long yellow

crystallises on the potassium salt of the monomethyl ether
needles, melting at 160. When treated with with methyl iodide.
nitrous acid, alizarin yields anthraquinone. Alizarin diethyl ether
Nitric acid acts violently on alizarin with evolu-
tion of red vapours and formation of phthalic ^k H 6 2
<^Q.gk ^)
and oxalic acids. Distillation with zinc reduces
can, however, be prepared by heating alizarin
alizarin to anthracene.
with potash and potassium ethyl sulphate at
When fused with alkaline hydroxides at a 160 (Habermann, Monatsh. 5, 228).
fairly high temperature, protocatechuic acid and Monobromalizarin
benzoic acid are formed. Concentrated aqueous
ammonia at 200 replaces the hydroxyl in posi-
tion (1) by amidogen. The l-amido-2-hydroxy-
anthraquinone so produced is called alizarin This derivative can be prepared by
heating
amide. alizarin with bromine and carbon
disulphide to
Salts of alizarin. Calcium alizarate 180-190 for four or five hours.
CaC 14 H.0 4 +H,0 It is better prepared, however, sul- by
isprecipitated by adding calcium chloride to an phonating alizarin with fuming sulphuric acid,
ammoniacal solution of alizarin as a purple and subsequently treating the solution with
mass. Barium alizarate BaC 14 H 6 O 4 2 +H
is bromine.
It crystallises from glacial acetic acid in
prepared, like the calcium salt, by mixing an
alkaline solution of alizarin with barium chloride. orange-coloured needles, which, when heated,
first melt to an
It deep-violet when moist, almost black when
is orange- coloured liquid and then
Alum- sublime in orange-red needles.
dry, and very sparingly soluble in water.
H
inium alizarate (C 14 6 2 ) 3 A1 2 6 (?) is obtained As a dyeing agent, monobromalizarin retains
all the properties of
by precipitating an alkaline solution of alizarin combining with mordants
with alum or aluminium hydroxide. It is a very possessed by alizarin, and the colours produced
fine red or rose-red precipitate. Lead alizarate appear to be equally fast. The shade of colour
H
C 14 6 4 Pb is obtained by mixing an alcoholic produced is, however, not the same, the reds
solution of alizarin with an alcoholic solution being less purple, and the purples less blue than
of sugar of lead. those produced by alizarin.
Alizarin can readily be detected by means of Literature. Perkin (Chem. Soc. Trans. 27,
the spectroscope, as it gives in alkaline solution 401).
two sharp absorption bands, one at D and one a-Nitroalizarin. Alizarin brown
near c, as will readily be seen from the accom- /OH (1)
which shows the absorption
panying figure, CÔH (2)
^N0 2. (4)
This substance is obtained by treating diacetyl
alizarin with nitric acid.
It is manufactured by dissolving alizarin in
fuming sulphuric acid and after cooling to
spectrum of a solution of alizarin in alcoholic 5 to 10, treating with the calculated
potash.
Literature. Anderson (J. 1847-48, 749) ; quantity of nitric acid dissolved in sulphuric
acid.
Stenhouse (J. 1864, 543); Rochleder (Ber. 3, a-Nitroalizarin crystallises from alcohol or
295); Perkin (Chem. Soc. Trans. 23, 141);
glacial acetic acid in golden-yellow needles. It
Graebe and Liebermann (Annalen Suppl. 7, 300 ; dissolves in caustic alkali with a blue-violet
Ber. 3, 359) ; Baeyer and Caro (Ber. 7, 972) ;
colour, but if only a minute quantity of alkali
Liebermann (Annalen, 183, 206) ; Liebermann
and Dehnst (Ber. 12, 1293) Schunck (Annalen,
is employed the solution is of a fine crimson
;
colour. The alkaline solution gives two absorp-
66, 187) ; Wolff and Strecker (Annalen, 75, 8) ; tion bands similar to alizarin. Nitroalizarin is
Lagodzinski (Ber. 28, 1428) ; Widman (Ber. 9,
easily reduced in alkaline solution with sodium
856) Liebermann Hohenemser (Ber. 35, 1779)
amalgam or ammonium sulphide and amido-
; ;
D. R. P. 116526; Perkin (Chem. Soc. Trans. alizarin the product.

is
75, 453). On warming with sulphuric acid 1:2:3:4-
Derivatives of alizarin. When treated with
the ordinary re-agents, such as bromine, nitric tetrahydroxyanthraquinone is produced.
a-Amidoalizarin. Alizarin garnet, Alizarin
acid, &c., alizarin forms a variety of valuable
cardinal
substitution products, some of which are used to
a considerable extent as dyeing agents. The
most important of these are the following :
8 ^cp\
4<
^C0^ u/rgg^ *
Alizarin methyl ether

'^NH,. (4)
This valuable dye-stuff is obtained by the
(1) reduction of o-nitroalizarin. It crystallises
.
(2) from alcohol in small needles of a nearly black
The synthesis of this substance from hemipinic colour, but possessing a slight greenish metallic
acid has already been described (p. 78). reflection.
It can also be produced the two absorption
by treating Its alcoholic solution gives
monopotassium salt of alizarin with methyl bands ; the first is a little beyond D and the
iodide or methyl sulphate. second near c. There is also a faint line close
The substance crystallises from alcohol, and to F.
has the melting-point 224-226.
Dyeing Properties of a-Nitro- and a-Amido-
The dimethyl ether is not obtained by acting alizarin. These colouring matters possess the
VOL. I. T. G
by the action of concentrated sulphuric acid on
power of dyeing ordinary madder mordants.
a-Jfttroalizarin gives with alumina mordants
alizarin.
unlike some It yields brilliant scarlet red shades with an
very clear orange-red colours, not
of the colours produced with aurin, and with aluminium mordant, bordeaux red with chro-
iron mordants reddish-purple colours. Amido- mium.
alizarin gives with alumina mordants purple Literature. Graebe and Liebermann (An-
colours, and with iron a bluish or steel-like nalen, 160, 144).
colour. Alizarin Blue
It is used for wool-dyeing and calico-printing. OH
Alizarin Maroon is a mixture of amido-
alizarins and purpurins obtained by the reduc- >OH
tion of the product of nitration of commercial
alizarin in sulphuric acid solution. On alumina N
mordants it produces a garnet red, maroon on il
chrome. CH CH
Literature. Perkin (Chem. Soc. Trans. 30,
678) Brasch (Ber. 24, 1610) Schunck and
; ;
CH.
Romer (Ber. 12,587); D. R. PP. 66811, 74431,
This important colouring matter, discovered
74598.
0-Nitroalizarin, Alizarin Orange by Prud'homme, is obtained by treating /3-nitro-
alizarin with glycerol and sulphuric acid or by
treating 0-amido alizarin with glycerol, nitro-
N0 .
benzene, and sulphuric acid. Its chemical
2 (3) constitution was first demonstrated by Graebe,
/8-Nitroalizarin is prepared by the action of who showed that this substance was related to
nitric acid on alizarin and also by boiling dinitro- alizarin in precisely the same way as quinoline
2-hydroxyanthraquinone with caustic soda of is to benzene, i.e. that alizarin blue is a quinoline
20 p.c. of alizarin.
It is manufactured in large quantities by the 1 part of #-nitroalizarin, 5
Preparation.
action of nitric acid on alizarin dissolved in
parts sulphuric acid, and 1 glycerol (of sp.gr.
sulphuric acid containing boric acid. The in- 1-262) are mixed and gently heated.
fluence of the boric acid on the position attacked At 107 the reaction commences and soon
by the nitric acid is probably due to the forma- becomes very violent, the temperature rising to
tion of a boric ester of alizarin. 200. After the frothing has subsided, the mass
The crude /3-nitroalizarin is purified by is poured into water, the product well boiled,
crystallisation from glacial acetic acid. filtered, and the residue extracted three or four
-Nitroalizarin crystallises in orange-yellow times with acid. The
very dilute sulphuric
needles which melt with decomposition at 244. combined extracts on cooling deposit the crude
When carefully heated it sublimes, with a good alizarin blue sulphate in brown crystals. These
deal of decomposition, in yellow needles. Dis-
are collected, washed with water till neutral,
solved in alkalis it forms a purple solution the ;
mixed with water, and borax added until the
sodium an excess of caustic
salt is insoluble in
solution becomes brownish-violet. The precipi-
soda. The calcium salt is an insoluble violet- tate thus formed is filtered off, washed with
red precipitate, which is not decomposed by
water, and decomposed with a dilute acid, the
carbonic acid (distinction from alizarin). Treated crude alizarin blue thus obtained being purified
with glycerol and sulphuric acid, /3-nitroalizarin
is converted into alizarin blue. by recrystallisation from benzene or glacial
acetic acid.
The
diacetate of j8-nitroalizarin crystallises
Alizarin blue crystallises from benzene in
in yellow needles melting at 218.
brownish-violet needles which melt at 270, and
0-Nitroalizarin is prepared on the large scale, at a higher temperature gives off orange-red
and comes into the market under the name of
Alizarin orange.' In dyeing it is applied to vapours which condense in the form of blue
needles.
the various fibres in the same way as alizarin ;
It is insoluble in water, sparingly soluble in
but although it yields fast colours, it has as yet
alcohol and ether, more readily soluble in hot
found only comparatively limited employment.
benzene. It dissolves in ammonia, potash, or
Applied to wool, it gives the following shades :
soda, forming blue solutions which become green

With an aluminium mordant it yields a very when mixed with an excess of alkali.
good orange ; with stannous chloride mordant, a
Alizarin blue combines with both bases and
reddish or yellowish orange, according to the
acids.
amount of mordant used ; with copper sulphate
The barium salt BaC 17 H 7 N0 4 BaO+H 2 is
mordant, a good reddish-brown is obtained ; with a greenish-blue precipitate. The following salts
ferrous sulphate, a purplish-brown ; and with
of alizarin blue with acids have been prepared :
bichromate of potash, a dull brownish-red.
Literature. Rosenstiehl (Bull. Soc. chim. 26,
H
C 17 9 N0 4 ,HC1 is a red crystalline precipitate
formed by passing dry hydrochloric acid gas
63) ; Schunck and Romer (Ber. 12, 584) ; Simon
(Ber. 15, 692) ; Bayer & Co. D. R. P. 74562.
through a solution of alizarin blue in boiling
benzene. When treated with water it is com-
Alizarin Red S
pletely decomposed into its constituents. The
/OH (1) sulphate crystallises in red needles. The acetate
H H
C 17 9N0 4 ,C 2 4 2 crystallises in blue plates.
3 Na. Alizarin blue also combines with picric acid
forming a compound C 17 H 9NO 4 -C 6 H 3 (N0 2 ) 3 0,
This dyestuff is the sodium salt of the mono-
eulphonic acid of alizarin. It is easily prepared which crystallises from benzene in long orange-
red prisms melting at 245. This compound is This dyestuff is prepared from rc-amidoalizarin
completely decomposed by water. One by treatment with glycerol, nitrobenzene, and
of the
most important compounds of alizarin blue is sulphuric acid. Its production and properties
the sodium bisulphite compound resemble those of alizarin blue. It is employed
C 17 H 9 N0 4 -2NaHS0 3 in printing, and is used with a nickel
. magnesia
manufactured on a large scale mordant.
This product is
Purpuroxanthin. 1
and sold under the name of Alizarin Blue S.' 3-dihydroxyanthraqui-
' :
It dissolves readily in water, with a brownish-red

colour. Alizarin blue is met with in commerce
j
H 2\OH.
in two forms, viz. as a paste containing about (3)
10 p.c. of dry substance, and as a powder. Purpuroxanthin exists in small quantities in
The former is nearly insoluble in water, while madder. It can be prepared by heating purpurin
the latter, which is the bisulphite compound
C 14 H 6 (OH) 3 2 with iodide of phosphorus and
This water, or more readily by boiling purpurin with
(described above), dissolves readily.
kind is now almost entirely used in caustic soda and chloride of tin.
soluble
dyeing. In dyeing cotton with alizarin blue a Preparation. Purpurin is dissolved in a
chromium mordant is used, but in the case of boiling solution of caustic soda (10 p.c.), and
chloride of tin added until the solution loses its
wool, bichromate of potash gives the best results.
Alizarin blue with an alumina or iron mordant deep-red tint and becomes of a yellow colour.
is also used for dyeing silk. Hydrochloric acid is then added, the precipitate
Alizarin blue is used largely as a substitute washed with strong hydrochloric acid, dissolved
for indigo in calico-printing works. It is one of in baryta water, reprecipitated with hydrochloric
the most stable colouring matters, and is even acid and crystallised from alcohol.
said to be faster than indigo itself. Purpuroxanthin crystallises in reddish-yellow
Literature. Prud'homme Soc. chim. needles which melt at 262-263. It dissolves in
(Bull.
Graebe (Annalen, 201, 333); Auerbach alkalis with a reddish colour. If the solution
28, 62);
in caustic potash be boiled in the air, it absorbs
(Chem. Soc. Trans. 35, 800).
Alizarin Green S (B). oxygen, the purpuroxanthin being reconverted
Alizarin blue can be oxidised by means of into purpurin.
It is not a mordant dyestuff.
sulphur trioxide, and the product on treatment
with sulphuric acid gives a dihydroxyalizarin Literature. Schiitzenberger and Schiffert
blue of the probable constitution (Bull. Soc. chim. 4, 12) ; Liebermann (Annalen,
OH m \/\OH
OH 183, 213) ; Schunck and Romer (Ber. 10, 172).
Quinizarin. 1 :
4-dihydroxyanthraquinone
.
(4)
is obtained by heating a mixture of quinol or
p-chlorphenol and phthalic anhydride with
CH CH
v
CH
Alizarin Green S (B) is the bisulphite com-
sulphuric acid.
+ (1)
(4)
(1)
pound of this tetrahydroxyanthraquinone (4)
+ hl 2^ )-
quinoline. It dyes very fast bluish-greens on

Together with alizarin and purpurin, it is
chromed wool. obtained by the action of ammonium persulphate
Alizarin Indigo Blue S on anthraquinone in sulphuric acid solution;
OH OH also on heating anthraquinone in sulphuric acid,
containing boric acid, with nitrous fumes.
2NaHSO Preparation. Equal parts of ^-chlorphenol
and phthalic anhydride are heated to 200-210
OH N for some hours, with ten times as much sul-
phuric acid as chlorphenol used. The product
CH CH is poured into two or three times its volume of
is the bisulphite
V
of the pentahydroxy-
compound
water, and after standing for twenty-four hours,
the precipitate is filtered off, washed and pressed.
The crude product is then boiled with water
to free it from phthalic acid, dissolved in caustic
anthraquinone quinoline, obtained by the further
oxidation of alizarin Green S (B) with concen- soda, precipitated with hydrochloric acid and
trated sulphuric acid at 200. It yields fast recrystallised from alcohol. In order to remove
a small quantity of purpurin, which is nearly
indigo blue shades on chrome mordanted wool.
Alizarin Green S (M) always present, the crude quinizarin is then
washed with cold dilute caustic soda as long as
CO OH the solution is coloured red, and the residue
\/\OH recrystallised from toluene.
Quinizarin crystallises from alcohol in red
needles which melt at 192-193, and sublime at
a high temperature with partial decomposition.
It dissolves readily in benzene. The solutions in
CH ether and sulphuric acid are characterised by a
i
beautiful greenish-yellow fluorescence. Quini-

zarin dissolves in baryta, forming a blue solution
Q 2
it is reprecipitated on passing car- following series of reactions : Phthalic anhydride
from which
bonic acid (distinction from alizarin). condenses with veratrol in carbon disulphide
The tinctorial effects produced by quinizarin !
solution under the influence of aluminium
chloride,
on fabrics mordanted with iron, chromium, or
aluminium are about Ta of those produced by
'
OMe
an equal amount of alizarin.
When fused with potash it isconverted into
hydroxychrysazin C 1 4 8 B
H .
Quinizarin forms a \/OMe
diacetate which melts at 200. Phthalic anhydride. Veratrol.
Baeyer and Caro (Ber. 8, 152) ; xv /COOK

Literature.
Schunck and Romer (Ber. 10, 554) ; Bayer & Co. /\OMe
D. R. P. 81245.
Quinizarin Blue
\XOMe
: 4 : dimethoxybenzoyl-
NH 0,Na.
benzoic acid.
The 3 4-dimethoxybenzoylbenzoic acid
:
thus produced yields 2:3: dimethoxyanthra-

quinone on heating with concentrated sulphuric
x/'\CO/ acid. This is hystazarindimethyl ether and
OH
yields hystazarin on demethylation.
This dyestuff prepared by heating quini-
is
Hystazarin crystallises from acetone in
zarin and aniline in molecular proportions and orange-yellow needles, which do not melt at 260.
sulphonating the product.
From an acid bath It is almost insoluble in benzene, difficultly
it dyes wool a red shade of blue, and gives a soluble in xylene, soluble in hot alcohol, ether,
greenish blue with
chromed wool. glacial acetic acid, and acetone.
Quinizarin Green. It dissolves in alkalis with a blue (corn-
Quinizarin is treated with an excess
of
flower) colour, in ammonia with a violet colour,
aniline and the product sulphonated. The dye- and in concentrated sulphuric acid with a blood -
stuff is the sodium salt of the sulphonic acid, and red colour. The barium salt is a blue precipi-
has the constitution tate, the calcium salt a violet precipitate ; both
are insoluble in water.
NH- 30,Na Hystazarin possesses only very feeble tinc-
torial properties. The faint red colour pro-
duced with an aluminium mordant differs in
shade from the alizarin red. The solution of
.
SO,Na. hystazarin in dilute sodium hydrate absorbs
the yellowish red and violet rays of the spectrum.
Toluidine and other amines may replace the
A very dilute solution shows two lines in the
yellow, A=619-8, A. t =587-4. Distilled over zinc-
aniline. The green shades produced on wool
from an acid- bath are fast to light and milling. dust, hystazarin yields large quantities of
anthracene.
Hystazarin. Hystazarin, 2 : 3-dihydroxyan- H H
Diaeetyl hystazarin C 14 6 2 (OC 2 3 0) 2 crys-
thraquinone tallisesfrom acetic acid in needles, which melt at
(2) 205-207.
.
(3) Literature. Liebermann and Schoeller
This substance is formed, together with alizarin,
(Ber. 21, 2501-2505) ; Lagodzinski and Lore'tan
when a mixture of pyrocatechol and phthalic
(Ber. 28, 118).
anhydride is treated with sulphuric acid 5 Anthraflavlc acid. 2 6-dihydroxyanthra-
:
grams of pyrocatechol, 6-8 grams phthalic quinone

anhydride and 75 grams sulphuric acid are heated
for 4 to 5 hours to 340-150 on a sand-bath.
The resulting product, while still warm, is
(6) HO-C 6H 3 <g>C H -OH. 6 3 (2)
Anthraflavic acid prepared by fusing a-anthra-

is
poured into f litre of water, heated to boiling,
and filtered hot. quinone disulphonic acid with potash, and is
The dark-green precipitate thus obtained is therefore nearly always present in artificial
well washed with hot water, dissolved in dilute alizarin. Synthetically it has been obtained by
potash, and the dark-blue solution precipitated heating wi-hydroxybenzoic acid with sulphuric
acid to 190.
by dilute sulphuric acid. The precipitate is
washed with water, dried on a porous plate, and 20H-C 6 H 4 -COOH
treated with boiling alcohol in an extraction : H 2 0.
apparatus, by which means a considerable por-
tion is dissolved. This mode of formation proves that this sub-
The dark-red solution on evaporation yields stance contains the two hydroxyl groups in
an orange-red mass, which consists of alizarin different benzene rings.
and hystazarin. These two substances are Anthraflavic acid crystallises from alcohol in
readily separated by treatment with boiling yellow needles which melt above 330. The pure
benzene, which dissolves the alizarin and leaves substance when carefully heated sublimes par-
the hystazarin ; the latter may then be further
tially in yellow needles, leaving a considerable
purified by recrystallisation from acetone. quantity of a carbonaceous residue. Anthraflavic
Yield 1 p.c. alizarin and 12 p.c. hystazarin acid does not dye mordanted cloth. It dissolves
of pyrocatechol used. in alkalis forming a yellowish-red solution, and
Hystazarin may be synthesised by the in sulphuric acid forming a green solution, the
absorption spectrum which shows a broad

of Anthrarufin forms a diacetate which melts
band between the blue and the green. Anthra- at 244-245.
flavic acid forms a number of salts, of which the Anthrarufin dimethyl ether is obtained on
sodium salt is the most characteristic. This salt boiling 1:5: dinitroanthraquinone with methyl
is sparingly soluble in water, and is remarkable alcoholic caustic soda. The substance forms
for the ease with which it crystallises ; this dis- deep-red needles of m.p. 230.
tinguishes it from isoanthraflavic acid, and gives Literature. Schunck and Romer (Ber. 11,
a ready means of separating these two substances. 1175) Liebermann and Dehnst (Ber.
; 12, 1289)
When treated with acetic anhydride, anthraflavic Bayer and Co. D. R. P. 101220.
acid forms a diacetate melting at 228-229. Alizarin Saphirol B.
Literature. Perkin (Chem. Soc. Trans. 1871, OH NH,
24, 1109 26, 19) ; Schunck and Romer (Ber. 9,
;
379; 11, 970); Liebermann (Ber. 5, 968); NaS0 3

Rosenstiehl (Bull. Soc. chim. 29, 401-434);
Barth and Senhofer (Ber. 170, 100). ^/~1/"\'
A / S0 3 Na
>/_.
NH 9
CO OH
/soAnthraflavic acid. 2 7-dihydroxyanthra- :
isan important blue acid wool-dye derived from
quinone anthrarufin by successive sulphonation, nitration,
(7) HO-C 6H 3<gg>C 6H 3 -OH (2) and reduction. This dyestuff excels in respect
to its fastness to light.
is formed when-anthraquinone disulphonic acid 1:7-
Metabenzdioxyanthraquinone. dihy-
is fused with potash, and is therefore
always con- droxyanthraquinone
tained in crude alizarin. In preparing it, crude
alizarin is dissolved in dilute caustic soda, the (7) HO-C H 6 3 <^g>C H _OH. 6 3 (1)
solution precipitated with hydrochloric acid, and
the precipitate dissolved in cold baryta water Literature.Schunck and Romer (Ber. 11,
and filtered. (In this way tsoanthraflavic acid, 1176) Liebermann and Dehnst (Ber. 12, 1289).
;
which forms a soluble baryta compound, is easily Metabenzdihydroxyanthraquinone C 14 H 8 4

is formed together with anthrafiavic acid and an-
separated from alizarin, anthrapurpurin, and
anthraflavic acid, which yield insoluble barium thrarufin by heating m-hydroxybenzoic acid with
sulphuric acid (v. supra). It is separated from
compounds.) The filtrate is treated with hydro-
chloric acid, and the precipitate recrystallised these by treatment with benzene and subsequent
from alcohol, /soanthraflavic acid crystallises recrystallisation from dilute alcohol. Meta-
forms
in long yellow needles, containing 1 mol.
2 0,
H benzdihydroxyanthraquinone yellowish
which can be driven off at 150. It melts above needles which melt at 291-293, and sublime at
330 and sublimes at a high temperature in a higher temperature almost without decom-
lustrous yellow needles. position. It dissolves in alkalis with a dark-
It dissolves easily in
alkalis forming a deep-red solution, but it does yellow colour, and in concentrated sulphuric
not dye mordanted cloth. Fused with potash acid, forming a brownish-yellow solution, which
isoanthraflavic acid yields anthrapurpurin. shows no absorption bands.
The diacetate of isoanthraflavic acid melts at The diacetate of metabenzdihydroxyanthra-
195. quinorie melts at 199.
Literature. Schunck and Romer Literature. Schunck and Romer (Ber. 10,
(Ber. 9,
379). 1225) ; Rosenstiehl (Ber. 9, 946).
Anthrarufin. 1 Chrysazin. 1:8- or 1 : 6-dihydroxyanthra-
:
5-dihydroxyanthraquinone
quinone is formed by fusing x-anthraquinone-
(5) HO-C 6H 3 <gg>C H 6 3 -OH. (1) disulphonic acid with potash, or by treating
H
hydrochrysamid C 14 2 (NH 2 ) 4 (OH) 2 with ni- :!
Anthrarufin is formed together with anthraflavic trous acid and alcohol. (N.B. Hydrochrysamid
acid and metabenzdioxyanthraquinone by is obtained by the reduction of chrysammic acid
heating ra-oxybenzoic acid with sulphuric acid. H
C 14 4 (N0 2 ) 4 4 , which is the product of the
(2) OH-C 6H 4 -COOH action of nitric acid on aloes.)
Chrysazin forms reddish-brown needles,
=OH C H ^^tQ^'C H OH
i
6 3 8 3
>
-J- 2H 2 0. which melt at 191. It dissolves in alkalis and

It may also be obtained sulphuric acid, with a red colour. Its diacetate
by fusing o-anthra-
quinone disulphonic acid with potash. melts at 227-232.
The process employed for the manufacture of Crude dinitroanthraquinone contains a com-
anthrarufin depends on the fact that it is the pound which is converted into chrysazin dimethyl
chief product when anthraquinone is oxidized ether on treatment with methyl alcoholic potash.
with sulphur trioxide under the following con- Literature. Liebermann (Annalen, 183, 184).
ditions :
Anthraquinone (50 pts. ) is heated with /soChrysazin. 1 : 6- or 1 :
8-dihydroxy-
fuming sulphuric acid (1000 pts. containing 80 p.c. anthraquinone has been obtained by Lrfschutz,
SO 3 ) and boric acid (20 pts.) for 36 hours at 100 by treating dinitroanthraquinone with concen-
under pressure. trated sulphuric acid. It crystallises from
Anthrarufin crystallises in yellow needles alcohol and ether in deep-red needles, which
which melt at 280 and sublime easily at a higher melt at 175-180. It dissolves in alkalis and in
temperature (distinction from anthraflavic acid). ammonia with a reddish violet colour, and in
colour.
It dissolves with
difficulty in ammonia and soda, sulphuric acid with a reddish yellow
but more readily in potash. When heated it sublimes readily, and at a com-
Anthrarufin dissolves in sulphuric acid, paratively low temperature, in orange-red plates
forming a deep-red solution, the colour of which or needles. It does not dye mordanted cloth.
is so intense that it is still
easily apparent in The diacetyl compound melts at 160-165.
solutions containing only 1 part in 10,000,000. Literature^ LifschUtz (Ber. 17, 897).
Constitution of the dihydroxyanthraquinones. and acidified with hydrochloric acid.
to boiling,
The synthesis of quinizarin from phthalic
The anthrapurpurin thus obtained is purified by
conversion into its difficultly soluble sodium
anhydride and quinol establishes its constitution
as 1 :
4-dihydroxyanthraquinone compound, and from this, by precipitation with
H barium chloride, the barium salt is obtained,
30. which is decomposed with hydrochloric acid.
The precipitate is collected on a filter, well washed
with water and recrystallised from glacial ace-
tic acid.
OH Anthrapurpurin crystallises in orange-
Further alizarin and hystazarin are produced by coloured needles, which melt above 330, and,
the condensation of phthalic anhydride with j
when carefully heated, sublime in long red
catechol. needles. It dissolves in alkalis with a violet
It follows that these colouring matters are colour ; the solution shows the same absorption
represented by the following formulae : spectrum as alizarin.
OH With acetic anhydride anthrapurpurin forms
a triacetate C 14 H 5 (C 2H 3 0) 3 5 which crystallises
x\ /COv\//\
//\Y/C0\Y/v
,
\OH i
H in yellow needles, melting at 220. When heated
with ammonia, anthrapurpurin is converted into
1
'OH H
anthrapurpurinamide C 14 5 (NH 2 )(OH) 2 2 .
I. II. Anthrapurpurin has the same affinity for

mordants as alizarin the colours it produces
;
The synthesis of alizarin from hemipinic acid is are also analogous to some extent, as it produces
conclusive evidence that the formula I. represents reds with alumina, purples and blacks with iron
alizarin, and consequently II. is the structure of mordants. There is, however, a considerable
hystazarin. difference in the shade of colour produced, the
Again, purpurin is produced by the oxidation reds being much purer and less blue than those
of both alizarin and quinizarin, and must there- of alizarin, whilst the purples are bluer and the
fore be 1 : 2 : 4-trihvdroxyanthraquinone
" blacks more intense. When used in Turkey -red
OH dyeing it produces very brilliant colours of a
\OH scarlet shade, which are of remarkable per-
manence.
Perkin (Chem. Soc. Trans. 25,
Literature.
CO OH 659 ; 26, 851) ; Caro (Ber. 9, 682) ;
425 ; 29,
Schunck and Romer (Ber. 9, 679 ; 10, 972, 1823
On reduction it yields neither alizarin nor
Rosenstiehl (Bull. Soc. chim. 29, 405) ;
;
13, 42) ;
quinizarin, but purpuroxanthin, which is

Auerbach (J. 1874, 488).
obviously 2 :
4-dihydroxyanthraquinone (the
Purpurin 1:2: 4-trihydroxyanthraquinone
same position as 1 3). :
Similar arguments can be developed with CO OH

respect to anthraflavic acid, isoanthraflavic acid,
anthrarufin, and metabenzdioxyanthraquinone.
\/\OH
There remains a doubt as to the constitution
of chrysazin and isochrysazin, but it is most j
O]
probable that chrysazin is 1 8-dihydroxyanthra- : !
quinone, in which case the hydroxyl groups in j

Purpurin occurs along with alizarin in
wochrysazin must be in the 1 6 position. :
madder, probably as a glucoside. In order to
The properties of chrysazin are similar to separate it from alizarin, the mixture of the two
those of anthrarufin, and it is much more <
substances is repeatedly recrystallised from a
hot solution of alum, in which purpurin is more
probable that dinitroanthraquinone is a mixture
of 1 8 and 1 5 than of 1 6 and 1 5.
: : : :
soluble than alizarin, or the mixture is dissolved
in caustic soda and the solution saturated with
Trihydroxyanthraquinones : Anthrapurpurin,
carbonic acid. This precipitates the alizarin,
/sopurpurin, Hydroxy/,wanthraflavic acid. 1:2:7-
but not the purpurin.
trihydroxyanthraquinone
OH Purpurin is obtained when alizarin or
nn quinizarin (1 pt.) is heated with pyrolusite
H0 / \/\OH (1 pt.) and concentrated sulphuric acid (8-10 pts.)
II II at 160.
is
The oxidation of alizarin to purpurin
also effected by the action of ammonium
XXX
persulphate in sulphuric acid containing sul-
This important colouring matter is contained phuric anhydride. a-Amidoah'zarin is changed
in crude artificial alizarin. It is formed by fusing to purpurin by the action of nitrous acid in
/3-anthraquinonedisulphonic acid, i'soanthra- sulphuric acid solution.
flavic acid,
metabenzdihydroxyanthraquinone, Purpurin crystallises from dilute alcohol in
or a-dibromanthraquinone with potash.
long orange-coloured needles, which contain
The preparation of this substance is a some- 1 mol. 2 0.
H
The pure substance begins to
what tedious process, dependent on the fact that sublime at 150, and melts at 253. It is
anthrapurpurin differs from alizarin in the slightly soluble in water, forming a deep yellow
behaviour of its alumina lake. The former, on solution ; in alkalis it dissolves with a purple-
treatment with an alkaline carbonate, is dis- red colour ; in alkaline carbonates with a red
solved, whilst the alizarin lake remains un- colour. The solution in alkalis shows two
attacked. The solution containing the anthra- marked absorption bands in the green. Purpurin
purpurin is filtered from the alizarin lake, heated also dissolves readily in ether, carbon disulphide,
benzene, and acetic acid these solutions give
;
xCO
OMe
two absorption bands, one at F and the other
near E the solution in sulphuric acid shows
;
another line in the yellow. When boiled with MeO x

aceticanhydride it yields a triacetate, Anisole. Hemipinic anhydride.
C 14 H 6 (C 2 H 3 0) 3 6, OMe
which crystallises in yellow needles, melting at )Me.
192-193. >
Aqueous ammonia at 150 converts purpurin MeO\ HOCO\ / /
into purpurinamide Trimethoxybenzoylbenzoic acid.
This benzophenone derivative is reduced
by
(OH:OH:NH 2 zinc-dust and concentrated
hydrochloric acid,
= 1:3:4), and the product is 4 5 : :
6-trimethoxydiphenyl-
methanecarboxylic acid, which is changed by
which, when boiled with ethyl nitrite, yields sulphuric acid to 1 2 6-trimethoxyanthrone.
: :
purpuroxanthin, OMe
OMe
(3) MeO HOCO
Purpuroxanthin is also the product when 4:5: 6-trimethoxydiphenylmethanecarboxylic acid.
purpurin is reduced with either alkaline stannous
chloride or sodium amalgam. If, however, ,
PTT 2
OMe
zinc-dust be employed as the reducing agent in
L<xi \ /\
'\/\OMe.
weakly alkaline, neutral, or acid solution, then
the leuco- compound of quinizarin is obtained.
Purpurin is converted into 2-anilino-l 4- :
CO
1:2: 6-triraethoxyan throne.
dihydroxyanthraquinone when heated with a
mixture of aniline and aniline hydrochloride. 1:2: 6-trimethoxyanthrone crystallises from
A certain amount of dianilino-hydroxyanthra- benzene in small needles melting at 170. It is
quinone is produced at the same time. oxidised by chromic acid in glacial acetic acid
Purpurin dyes fabrics much in the same way solution to the trimethyl ether of flavopurpurin,
as alizarin and anthrapurpurin, there being, which consists of yellow needles, crystallises from
however, a difference in the shades. The reds acetic acid, and melts at 225. The trimethyl
produced by purpurin are much yellower, and ether is hydrolysed to flavopurpurin by the action
the browns (with chrome mordant) much more of aluminium chloride at 210.
intense than are produced either by alizarin or Flavopurpurin crystallises from alcohol in
anthrapurpurin. anhydrous yellow needles, sparingly soluble in
The following figure shows the absorption water, but readily soluble in cold alcohol. Its
spectrum of a solution of purpurin in aluminium melting-point lies above 330.
sulphate : It dissolves in caustic alkalis with a purple
colour the solution shows two absorption bands,
;
one in the blue and the other near the red,

but a little further removed than the alizarin
band.
Flavopurpurin dyes mordanted fabrics simi-
larly to alizarin, there being, however, a slight
Flavopurpurin. 1:2:6- trihydroxyanthra- difference shades produced. The red
in the
quinone shade is duller and yellower ; the
somewhat
OH brown shade is also yellower. Flavopurpurin
\ /\ dyes wool mordanted with tin crystals and
\/\OH cream of tartar a bright yellowish orange.
When heated with acetic anhydride, flavo-
\00/ purpurin yields a triacetate C 14 6 (C 2 3 0) 3 5 H H ,
which crystallises from alcohol in golden-yellow

Flavopurpurin occurs in commercial artificial
plates melting at 238.
alizarin, but is with difficulty isolated from this
Alizarin Red 3 W. S. is the sodium salt of the
product, owing to the fact that its chemical
monosulphonic acid of flavopurpurin.
properties agree so closely with those of anthra- Alizarin Orange G. Nitroflavopurpurin
purpurin, which is also nearly always present
in artificial alizarin, that it can
only with diffi-
OH
culty be separated from this substance.
It is prepared by
fusing j8-anthraquinone-
disulphonic acid or anthraflavic acid with HO
potash.
It may be synthesised It
by the following series is similarly constituted to /8-nitroalizarine.
of reactions :
isobtained by the nitration of flavopurpurin with
Hemipinic anhydride condenses with anisole ordinary nitric acid. Fast orange shades can be
the presence of anhydrous aluminium tri-
produced by applying this compound with an
in
chloride, yielding the trimethyl ether of 4 5 : 6- : aluminium mordant.
trihydroxybenzoyl benzoic acid. On treatment with glycerol and sulphuric
ss ALIZARIN AND ALLIED COLOURING MATTERS.
acid a trihydroxyanthraquinone quinoline of strongly heated it sublimes in red needles. It
the constitution dissolves in potash, forming a violet solution,
OH and shows in its reactions great similarity to
purpurin. It differs from this substance in the
xOH fact that its solution in alum gives no absorption
i I
HO
I
spectrum.
-co The solution in sulphuric acid shows, however,
two weak bands. The substance is a mordant
dyestuff.
The triacetate of hydroxyanthrarufin melts
at 192-193.
isproduced, the bisulphite compound of which is
the dyestuff Alizarin Black P. Literature. Liebermann (Annalen, 183, 191) ;

It is used for producing a fast violet grey to Schunck and Romer (Ber. 11, 1179) ; Lieber-
black in cotton-printing. mann and Boeck (Ber. 11, 1617) ; Liebermann
Literature. Caro (Ber. 9, 682) Schunck and ;
and Dehnst (Ber. 12, 1289).
Rorner (Ber. 9. 679 ; 10, 1823 13. 42) Bis- : : Tetrahydroxyanthraquinones.
trzycki and Yssel de Schepper (Ber. 31, 2798). Anthrachrysone. 1:3:5: 7-tetrahydroxy-
Anthragallol. 1:2: 3-trihydroxyanthraqui- anthraquinone
OH
OH HO
\/\OH OH
JOH. OH
The preparation of this body is effected by
Anthragallol does not itself occur in nature, heating 3 5-dihydroxybenzoic acid with 10
:
but its three isomeric dimethyl ethers have been parts of sulphuric acid for 3 to 5 hours.
found in Chay root (Oldenlandia umbellata). The substance consists of silky yellow needles
Anthragallol is formed when a mixture of when crystallised from alcohol, or it can be
gallic acid (1 pt.), benzoic acid (2 pts.), and sublimed with partial decomposition in leaflets.
sulphuric acid (20 pts.) are heated to 125 for It does not melt at 360.
eight hours. Anthrachrysone has a very feeble affinity for
mordants. Its tetraacetate crystallises in
COOH yellow needles from acetic acid, and melts at
253.
OH Various dyestuffs are derived from anthra-
HOCO chrysone.
Benzoic acid. Gallic acid.
Dinitroanthrachrysonedisulphonie acid
CO
N0 2 rf) OH
'\ /^
OH HO \/\S0 H 3
+ 2H 2 0. OH
S
H HSO.
CO
CO OH N(_
Anthragallol. isprepared by sulphonation, followed by nitra-
The product poured into water, well
is
tion of anthrachrysone.
washed, and recrystallised from alcohol. It is a fast brown wool dye.
It is also obtained from 1 3-dinitro-2-hydro- :
On reduction it yields diamidoanthrachry-
xyanthraquinone (the nitration product of 2- sonedisulphonic acid, which dyes wool violet
hydroxyanthraquinone) by reduction in strongly from an acid-bath, or blue on a chromium mor-
alkaline Or 1
solution. 3-diamido-2-hydro-
:
dant.
xyanthraquinone be converted to anthra-
may If, however, the reduction is carried out in
gallol by heating with hydrochloric acid under alkaline solution with sodium sulphide, then the
pressure. dyestuff Acid Alizarin Green B and G results.
Anthragallol crystallises in yellow needles The constitution of this product is
which, when heated to 290, sublime without
It is sparingly soluble in water,
SH n OH
melting. /\ ^J*J\. x\.
chloroform, or carbon disulphide ; readily soluble HO/\/ \/ \S0 Na 3
in alcohol, ether, or glacial acetic acid.
It dissolves in alkalis
Its triacetate C 14 5 (C 2H
forming a green solution.
H3 0) 3 O S melts at 171-
NaS0 \
OH
3
/\/OR
SH
\
173. It dyes chromed wool a fast, pure green.
With an excess of ammonia anthragallol Acid Alizarin Blue BB and GR
reacts, forming anthragallolamide, 1-amido- OH OH
2 :
3-dihydroxyanthraquinone. CO
Seuberlich (Ber. 10, 39).
Literature. HO \/\S0 Na 3
Hydroxyanthrarufln (Hydroxychrysazin).
1:4: 5-trihydroxyanthraquinone. This sub- NaSO !
OH
OH co
stance is formed by fusing chrysazin,
anthrarufin, OH
p- or x- an thraquinonedisulphonic acids with is obtained by boiling diamidoanthrachrysone-
potash. It crystallises in small red needles, disulphonic acid with alkali. A red shade is
which are sparingly soluble in alcohol. When
produced on wool from an acid-bath, which on
obtain which the reaction product is rendered

chroming develops a beautiful blue, exceedingly
fast to light milling, acids or alkalis. alkaline and then boiled with an excess of
Literature. Hohenemer (Ber. 35, 2305) ; hydrochloric acid.
Barth Senhofer (Annalen, 164, 109) ; Noah (Ber. It is found that the oxidation of alizarin
occurs more readily in presence of boric acid.
19, 755).
RuQopin. Alizarin bordeaux can be obtained in deep
This tetrahydroxyanthraquinone is obtained red needles with green metallic reflection.
by heating opianic or hemipinic
acids with On an aluminium mordant it produces
sulphuric acid at 180. bordeaux shades ; violet blue on chromium.
Also by fusing the disulphonic acid of anthra- Thetetraacetate crystallises from chloroform-
rufin with potash. alcohol in micro- needles of m.p. 201.
It forms a reddish yellow crust from ether, Dimethyl ether of alizarin bordeaux.
and can be sublimed in orange needles. This substance is synthesised by heating hemi-
It gives a violet-red solution in dilute alkalis pinic acid and quinol with sulphuric acid to 130.
or in sulphuric acid. A
curious property of The brown-red micro leaflets obtained by
rufiopin is its stability
towards fusion with crystallisation from benzene melt at 225-230.
potash. Literature. Schmidt (J. pr. Chem. [2] 43,
The substance is of no value as a dyestuff, 239) ; Liebermann and Wense (Annalen, 240,
since it gives only dull-brown shades with 299).
mordants. Pentahydroxyanthraquinones.
Literature. Liebermann and Chojnacki Alizarin cyanine R. 1:2:4:5: 8-penta-
(Annalen, 162, 323) ; D. R. P.
103988. hydroxyanthraquinone
a- and /3-hydroxyanthragallol. OH OH
A mixture of these substances is produced
when equimolecular proportions of gallic and OH
m-hydroxybenzoic acids are heated at 150,
with 10 parts of sulphuric acid for twenty hours.
The product is poured into water and the OH
dried precipitate extracted with alcohol. This This valuable substance is obtained by the
extract is evaporated and the residue treated oxidation of alizarin bordeaux with pyrolusite
with hot benzene. The a- compound passes into in sulphuric acid solution. The sulphonic acid
solution, whilst the /3- remains undissolved. ether so produced is hydrolysed by boiling with
o-hydroxyanthragallol crystallises from dilute acid. This oxidation is entirely analogous
alcohol in golden yellow micro- needles. It forms to that by which purpurin is produced from
a green solution in alkalis, whilst that in sul- alizarin. The substance crystallises in bronze-
phuric acid is violet, and shows two absorption coloured leaflets from nitrobenzene. The blue
bands between s and D. With mordants it solution in concentrated sulphuric acid exhibits
behaves similarly to rufigallic acid. red fluorescence.
Its tetraacetyl derivative melts at 207- Alizarin cyanine R. yields a handsome blue
209. chromium lake.
0-hydroxyanthragallol crystallises from Dihydroxyanthragallol. 1:2:3:5: 7-penta-
alcohol and occurs in red needles. Its brown-
hydroxyanthraquinone
red solution in sulphuric acid shows two absorp-
CO
C
H
tion bands between E and H.
The tetra-acetate crystallises from glacial HO/\/ \/\OH
acetic acid in lemon-yellow tablets of m.p. /OH
189. 10
Literature. Noah
(Annalen, 241, 270). OH
1:2:3: 4-tetrahydroxyanthraquinone is
Equimolec.ular amounts of gallic
acid and 3 : 5-
obtained by heating anthragallol with sulphuric to 160 for
dihydroxybenzoic acid are heated
acid in the presence of boric acid at 200-240. ten minutes with ten times their weight of
It consists of green needles soluble in both
sulphuric acid. The product contains dihydroxy-
alkalis and sulphuric acid with red colour. and
anthrachrysone.
anthragallol, rufigallic acid,
The tetraacetyl derivative melts at 205. In order to separate them, advantage is taken of
Literature. Bayer and Co. D. R. P. 86968. the fact that only dihydroxyanthragallol penta-
Alizarin bordeaux (Quinalizarin). 1:2:5:8- acetate is soluble in alcohol. The acetate so
tetrahydroxyanthraquinone obtained is hydrolysed with cold sulphuric acid.
from al-
OH OH Dihydroxyanthragallol crystallises
cohol in small red needles, which do not melt at
360. The substance is similar in tinctorial
acid.
properties to rufigallic
CO The pentaacetate melts at 229.
OH Noah (Annalen, 241, 275).
Literature.
Alizarin bordeaux is by far the most impor- Hexahydroxyanthraquinones. Rufigallol.
Run-
tant of the tetrahydroxyanthraquinones.
gallic acid, 1:2:3:5:6: 7-hexahydroxyanthra-
It has been obtained by the hydrolysis of its
quinone
dimethyl ether (see below) with a solution of
CO
C
H
hydrochloric acid in acetic acid at 200.
It is prepared by heating alizarin (1 pt.) with HO/\/ \/\OH
sulphuric acid (10 pts. containing 80 p.c. S0 3 ) OH
for four days at 25-50. This yields the CO
sulphuric acid ester of alizarin bordeaux, to
when gallic acid acetic anhydride. This is recrystallised several
Rufigallic acid is produced
is heated with concentrated sulphuric acid at times, and decomposed with potash.
140. It may be sublimed in yellow needles. Gallein crystallises from alcohol in small
A violet solution is obtained with alkalis, red greenish crystals. It is insoluble in chloroform
with sulphuric acid. Baryta produces a blue and benzene, sparingly soluble in water and
insoluble precipitate. Alizarin is obtained by ether, readily soluble in alcohol, forming a dark-
the reduction of rufigallic acid with sodium red solution. It dissolves in cold concentrated
amalgam. The substance is a good example of sulphuric acid without change ; on warming the
a polygenetic dyestuff,and yields with aluminium, solution ccerule'in is formed.
iron, and chromium mordants, red, violet, and Gallein dissolves in small quantities of potash
brown respectively. The colours are, however, or soda with a red colour ; excess of alkali pro-
not pure in tone. duces a blue solution. Heated to 150 with
Anthracene Blue. 1:2:4:5:6: 8-hexa- acetic anhydride gallein yields a tetracetate of
hydroxyanthraquinone hydrogallein.
OH
s\ m
/\J\J\
OH
/\
Gallein (often called anthracene violet) is
sold in the form of a reddish -brown powder, or
\/\OH a 10 p.c. paste ; not very soluble in cold water,
I i I
but readily so in hot. With all the usual aliza-
H0\\//\\Tfl/ \/ rin mordants gallein produces purple colours,
OH OH which are fast to light and soap ; those obtained
Anthracene blue is an important dyestuff, and by the use of chromium and iron are bluish, those
can be obtained from erythroxyanthraquinone, with tin reddish, those with aluminium inter-
anthrarufin, or anthrachrysone, by the oxidising mediate in tone.
action of sulphur trioxide in sulphuric acid in Literature. Baeyer (Ber. 4j 457 and 663) ;
the presence of boric acid. Buchka (Annalen, 209, 261); Orndorff and
It is best prepared by the action of 40 p.c. Brewer (Amer. Chem. J. 1901, 97).
sulphuric anhydride on 1 : 5-dinitroanthra- Coarulein C., H 10 6
quinone, and treatment of the product with OH r. OH
ordinary sulphuric acid.
The solution in concentrated sulphuric acid OH
is violet-blue and shows a 'brown fluorescence.
The aluminium lake is violet and the chromium
lake blue.
Its disulphonic acid is Acid alizarin blue B B, CO
mentioned above, and prepared from anthra-
chrysone.
Benzoin Yellow
Ph
Ccerulein is prepared by heating 1 part of
gallein and 20 parts of sulphuric acid to 200,
and precipitating the colouring matter by adding
a large quantity of water. It is thus obtained
OH as a bluish-black mass, which, when rubbed,
OH acquires a metallic appearance. It is almost in-
soluble in water, ether, and alcohol, more readily
!0
soluble in acetic acid.
is prepared by the condensation of benzoin with It dissolves in alkalis with a green colour, in
gallic acid under the influence of sulphuric acids with an olive-brown colour. With bisul-
acid.
phite of soda ccerule'in forms an easily soluble
Itdyes wool on a chromium mordant a fast
compound. With acetic anhydride it forms a
yellow (except to light). triacetate. Coerulein (anthracene green) is sold
Gallein C 20 H 12 7 in two forms, either as a bluish-black paste con-
_ OH' OH taining 10-20 p.c. ccerule'in, or as a black powder.
OH The former is insoluble in water, the latter,
known as coerulein S, is soluble in water, and is
indeed a bisulphite compound of ccerulein.
Coerulein is mostly employed in calico-print-
ing for producing very fast olive-green shades.
Whatever the mordant used, only different
/\co OH shades of olive-green are produced.
Literature. Baeyer (Ber. 4, 556, 663) Orn- ;
dorff and Brewer (Amer. Chem. J. 1901, 97).

Gallein is formed by heating pyrogallol with W. H. P. and R. R.
phthalic anhydride. ALIZARIN (Natural) v. CHAY BOOT and
Preparation. A mixture of 1 part of phthalic MADDER.
anhydride and 2 parts of pyrogallol are heated to ALIZARIN AND METHYL ETHER v. CHAY
190-200", the product dissolved in alcohol, and ROOT.
the colouring matter precipitated by the addi- ALIZARIN BLACK, -BLUE, -BORDEAUX,
tion of water. The crude gallein thus obtained BROWN, -CARDINAL, -CYANINE, -GARNET,
is dissolved in alcohol,
reprecipitated with water, GREENS, -MAROON, -ORANGE, -REDS, -SA-
and, after repeating this operation a few times, PHIROL v. ALIZARIN AND ALLIED COLOURING
converted into the acetate by heating with MATTERS.
ALLANTOIN. 91
ALIZARIN YELLOW v. Azo- COLOURING sweets, &c., and for these purposes it is well
MATTERS. adapted on account of its ready solubility and
ALIZARIN YELLOW A v. KETONES. harmless nature.
ALKALI ALBUMIN v. PROTEINS. Bottger (J. pr. Chem. 107, 146) and Eng
ALKALI BLUE. Nicholson's blue. Sodium (
J. 70, 935) recommend the use of
papers
triphenyl-rosaniline sulphonate (v. TRIPHENYL stained by alkanet as indicators in
alkalimetry.
METHANE COLOURING MATTERS). According to Jolin (Chem. Schriften iiber
ALKALI BROWNS, -YELLOW v. Azo- CO- Alkanna, iv. 84), Thompson (Pharm. J. [3] 1C,
LOURING MATTERS. 860), and Eriksson (I.e.), alkanet root contains
ALKALIMETRY v. ACIDIMETRY. from 5 to 6 p.c. of anchusin. A. G. P.
ALKALI WASTE v. Soda manufacture, art.
'
ALKANNA or AL-KENNA. The powdered

SODIUM. roots and leavesof the Lawsonia alba (Lam.),
ALKANET. The Arabic name Al-henneh, used in the East for dyeing the nails, teeth,
modified to alkanna or al-kenna, was originally hair, and garments. Used in Persia mixed with
applied, to the lythraceous shrub Lawsonia alba lime for dyeing the tails of horses.
(Lam.), the root of which was described as Radix ALKANNIN (ANCHUSIN) v. ALKANET.
Alkannce vera, in contradistinction to the root ALKASAL v. SYNTHETIC DRUGS.
of our alkanna, which is Anchusatinctoria (Lam.), ALLANTOIN. Glyoxyldiureide C 4 H 6O 3 N 4
and which became known as Radix Alkannce
spuria tinctoria. The latter, or False alkanet, /NH-CH-NH-CONHo
is also known as Orcanette, Fr. ; Orkanet, Ger. ; C0<\NH-CO |
Languedoc bugloss or Dyers' bugloss, Radix

Alkannce spuria. A
rough plant with downy /NH-C:N-CO-NH 2
or C0<
spear-shaped leaves, and clusters of purplish or
reddish flowers; belongs to the Boraginacece. \NH-CH-OH
Found in Asia Minor, Greece, Hungary, &c. was found originally in the allantoic liquid of
The roots, which have an astringent taste, occur cows (Vauquelin and Buniva, Ann. Chim. 23,
in commerce, varying from the thickness of a 269; Lassaigne, Ann. Chim. Phys. [2] 17,301)
quill to that of a finger. and in the urine of newly- born calves (Wohler,
Alkanet is one of the more ancient dye- Annalen, 70, 229) it occurs also in the young
;
stuffs, having been employed by the Romans, leaves, buds, and stem of the plane tree (Platanus
but, on the other hand, it does not appear at orientalis) sycamore (Acer pseudoplatanus), and
;
any time to have attained such importance in the bark of

the horse-chestnut (JEsculus
as madder, indigo, or even turmeric. The hippocastanum). Under normal conditions of
colouring matter of alkanet, known as an- growth 0-25 gram allantoi'n may be isolated from
chusin or alkannin, has been examined by 440 grams of fresh young leaves of the plane,
several chemists, but it is doubtful whether this but when the branches are cut in bud and
compound has as yet been obtained in a che- the buds allowed to open in water, the amount
mically pure condition. Its composition is of allantoiin increases to 0-5 or 1 p.c. of the
H
variously given as Ci 7 10 4 (Pelletier, Annalen, dried leaves (Schulze and Barbieri, Ber. 1881,
6, 27) C 3 ,H 20 O g (Bolley and Wydlers, Annalen, 14, 1602; J. pr. Chem. [2] 25, 145; Schulze
H
62, 41), C 15 14 4 (Carnelutti and Nasini, Ber. and Bosshead, Zeitsch. physiol. Chem. 1884,
13, 1514), and C 15 H
14 4 or C 15 H
12 4 (Lieber- 9, 420). It has been found in the nitrogenous
mann and Romer, Ber. 20, 2428). constituents of wheat-germs (Richardson and
Alkannin forms a dark-red amorphous powder Crampton, Ber. 1886, 19, 1180); in tobacco
possessing a beetle-green iridescence, is readily seeds (Scurti and Perciabosco, Gazz. chim. ital.
soluble in most of the usual solvents, and its 1906, 36, ii. 626) and in crude beet juice (v.
;
alkaline solution is coloured deep-blue. On dis- Lippman, Ber. 1896, 29, 2652). Allantoin is a
tillation with zinc-dust it
gives, according to normal constituent of the urine of mammals ; the
Liebermann and Romer, both methylanthracene amount varies in different species, being greatest
and anthracene. in the least in man (Frericho, Stadeler,
dog and
Diacetylalkannin C 15 H 12 4 (C 2 H 3 0) 2 forms a J. 1854, 7, 714 ; Wiechowski, Biochem. Zeitsch.
dull yellow micro-crystalline powder (CC and N.). 1909, 19, 368 ; Schittenhelm, Zeitsch. physiol.
According to Eriksson (Ber. Deut. pharm. Chem. 1909, 63, 248, 269, 283, 289). In the
Ges. 1910, 20, 202), alkannin consists of two red case of the the amount of allantoiin in the
dog
pigments, the one being coloured green and the urine increased after a diet of animal food
is
other blue by the action of alkalis. Red crystals (Salkowski, Ber. 1878, 11, 500), of calf's thymus
have been observed by Tschirch in spaces in the (Cohn, Zeitsch. physiol. Chem. 1898, 25, 507;
cortex of old specimens of alkanet root. As Mendel, Amer. J. Physiol. 6, xiv.-xv. ; M'Lach-
alkannin is insoluble in water, in dyeing with lan, Proc. Roy. Soc. Edin. 1906, 26, 95) ; it is
alkanet an alcoholic extract is usually employed ; also increased after the administration of uric
and with aluminium and iron mordanted fabrics, acid (Salkowski, Ber. 1876, 9, 719; Swain,
violet and grey shades are Amer. J. Physiol. 1910, 6, 38; Wiechowski,
respectively produced.
These colours, however, are not fast to light, and Beitr. Chem. Physiol. Path. 1908, 11, 109;
are somewhat
readily affected by weak alkalis or Biochem. Zeitsch. 1910, 25, 431) or of nucleic
acids. acid (Mendel, I.e. ; Schittenhelm, Zeitsch.
Haussmann of Mulhouse introduced alkanet physiol. Chem. 1910, Wiechowski, I.e.).
66, 53;
into calico-printing, and for a short time it Allantoin is therefore to be regarded as an
case
appears to have played a quite important part, end-product of uric acid metabolism in the
but it is now little if at all employed in Europe of such animals as dogs and rabbits (Wiechow-
for ordinary It is still used I.e. Schittenhelm,
dyeing purposes. ski, ; I.e.).
for artificial wines,
colouring pomades, hair-oils, The method of preparation of aUantoin by
92 ALLANTOIN.
oxidising uric acid with lead peroxide in presence found by Liebig (Annalen, 121, 81) and by
of water is due to Liebig and Wohler (Anna* Lang (Zeitsch. anal. Chem. 6, 294) in certain
len, 1838, 26, 245) ; it has been modified by pathological excretions, is one of the oxidation
Mulder (Annalen, 1871, 159, 349), who effects products of uric acid, and was first prepared by
the oxidation in dilute acetic acid solution and Brugnatelli (Ann. Chim. Phys. 1817, 8, 201 ;
in bright daylight by this method 100 grams
;
from Giornale di Fisica, decade seconde i. 117),
of uric acid yield 30-32 grams of allantoiin. under the name of erythric acid, by oxidising
A quantitative yield of allantoi'n is obtained uric acid by means of nitric acid, chlorine or
when uric acid is oxidised by an alkaline solu- iodine. Liebig and Wohler (Annalen, 1838, 26,
tion of potassium permanganate, and the 256), who systematically studied the oxidation
intermediate compound of uric acid, gave to this product the name of
/NH-CO -C(OH)-NH\ alloxan, regarding it as bearing the same relation

CO/ >CO to allantcfin and oxalic acid that oxaluric acid
\NH C(OH)-NH/ does to oxalic acid and urea. According to
acetic acid (Sundvik, Zeitsch. Liebig and Wohler (I.e.) and to Gregory
decomposed by
physiol. Chem. 1904, 41, 343 ; Behrend, (Mem. Chem. Soc. 1848, iii. 44), alloxan can
be obtained most readily and with a yield of
Annalen, 1904, 333, 141). Allantoin is also
obtained by the action of nitrous acid on 90 p.c. by careful oxidation of uric acid by means
of nitric acid, sp.gr. 1-412.
dialuric acid (Gibbs, Annalen Suppl. 1870, 7,
337). The synthesis of allanto'in has been According to Schlieper (Annalen, 1845, 55,
effected (1) by Grimaux (Compt. rend. 1876, 83, 261), the oxidation of uric acid to alloxan is
more conveniently effected with hydrochloric
62) by heating a mixture of glyoxylic acid (1 part,
and carbamide (2 parts) at 100 for 8-10 hours ; acid and potassium chlorate 4 parts of uric acid
;
are mixed with 8 parts of hydrochloric acid,

(2) by Michael (Amer. Chem. J. 1883, 5, 198) by and 1 part of finely powdered potassium chlorate
heating a mixture of mesoxalic acid and car-
bamide in equal proportions at 110; (3) and added in successive small quantities, avoiding
the liberation of chlorine ; after two or three
by Simon and Chavanne (Compt. rend. 1906,
hours the diasolved alloxan is reduced by means
143, 51) by the action of ammonia or alkali
hydroxides on ethyl allantoate CH(NH-CO.
of sulphuretted hydrogen to the sparingly
NH 2 ) 2 C0 2 Et, obtained by the condensation of soluble alloxantin. This is separated from the
ethyl glyoxylate with carbamide. sulphur by crystallisation from hot water, and
Allantoin is readily soluble in boiling water, oxidised to alloxan by the action of diluted
nitric acid.
sparingly so in cold (1 : 131-5 at 21-8) (Grimaux,
Ann. Chim. Phys. 1877, Alloxan crystallises from warm saturated
389); crystal-
[v] 11,
lises in glassy monoclinic prisms (Dauber, aqueous solution in large triclinic prisms con-
Annalen, 1849, 71, 511) its heat of combustion
;
taining 4H 2 on exposure to the air or on heating
;
at constant pressure is + 413-8 Cal., and heat of at 100 it loses 3H 2 0, and the dried compound
formation + 170-4 Cal. (Matignon, Ann. Chim. has the composition expressed by the formula
Phys. 1893, [vi.] 28, 106).
Allantoin forms a silver salt C 4 5 3 4 Ag H N
(Liebig and Wohler, I.e.) and a potassium
salt C 4 H
5 3 4NK (Mulder, I.e.); it also com- (Lang, Grailich, J. 1858, 308 Hartley, Chem. ;
bines with certain metallic oxides to form spar- Soc. Trans. 1905, 87, 1802) ; also obtainedit is
the mercury, copper, in oblique rhombic prisms, belonging to the

ingly soluble compounds ;
zinc, and cadmium derivatives are de- monoclinic system on evaporating an aqueous
lead,
scribed solution at 65-70. The remaining molecule of
by Limpricht (Annalen, 1853, 88, 94).
water is lost at 150.
(For the method of estimating allantoiin based on
the sparing solubility of the silver and mercury When crystals of alloxan are kept for some
derivatives, see Loewi, Zeitsch. anal. Chem., 1900, years in closed vessels they sometimes undergo
39, 266 ; Poduschka, ibid. 267.) spontaneous decomposition, forming alloxantin,
Allanto'in is oxidised by potassium ferricya- parabanic acid, and carbon dioxide. According
nide in the presence of potassium hydroxide to to Gregory (Annalen, 1853, 87, 126), this is due
to the presence of traces of nitric acid contained
potassium allantoxanate
in the water of crystallisation. Similar pheno-
/NH-CO mena were observed by Baumert (Pogg. Ann.
C0< Heintz Ann.
\NH-C :N-C0 K 2
1860, 110, 93), by (Pogg. 1860, 111,
436), and by Otto (Annalen Suppl. 1865, 4, 256):
(van Embden, Annalen, 1873, 167, 39); the free Cases of spontaneous explosive decomposi-
acid does not exist, but breaks down, when
tion of alloxan are recorded by Wheeler and by
liberated from its salts, into carbon dioxide and
allantoxa'idin Bogert (J. Amer. Chem. Soc. 1910, 32, 809) ;
the products of decomposition being carbon

/NH-CO dioxide, carbamide, oxalic acid, and alloxantin
CO/
(Gortner, J. Amer. Chem. Soc. 1911, 33, 85).
|
\NH-C :NH The molecular heat of combustion of alloxan

(Ponomareff, Ber. 1878, 11, 2156). M. A. W. is 276-5 Cal. (Matignon, Ann. Chem. Phys. 1893,
ALLEMONITE. A native alloy of arsenic [vi.] 28, 300) ;
the dissociation constant is
and antimony, SbAs 3 , found at Allemont in the 2-32 X lO- (Wood, Chem. Soc. Trans. 1906, 89,
7
Dauphine, Przibram in Bohemia ; and Andreas- 1835). In common with the other simple
berg in the Hartz. ureides, alloxan shows no absorption bands in
ALLOXAN. Mesoxalylcarbamide its spectrum (Hartley, Chem. Soc. Trans. 1905,
87, 1815).
Alloxan is readily soluble in alcohol or water ;
ALLOXAN. 93
the solution acid to litmus, stains the skin
is 9, 1092) ; from f-uric acid (Fischer, Ber.
1899,
purple, and imparts to it a curious
and un- 32, 2731) ; from theobromine (Maly, Andreasch
pleasant odour. In its physiological action Monatsh. 1882, 3, 108 ; Fischer and
Clemm, Ber.
alloxan affects the central nervous system, pro- 1897, 30, 3090). It crystallises from water in
ducing first stimulation, then paralysis. When brilliant colourless prisms, becomes
anhydrous
taken internally it is excreted in the urine as at 60 in a vacuum, and
decomposes at 156.
alloxantin and parabanic acid (Lusini, Chem. Dimethylalloxan
Zentr. 1895, ii. 311, 727, 838; Koehne, Chem.
Zentr. 1894, ii. 296).
Alloxan is readily oxidised by warm dilute
nitric forming carbon dioxide and para-
acid, prepared by oxidising caffeine (Fischer, Annalen,
banic acid (oxalylcarbamide) (q.v.) ; is reduced by 1882, 215, 257 ; Maly, Andreasch, Monatsh. 1882,
sulphuretted hydrogen, stannous chloride, zinc, 3, 96), by boiling dichlorodimethylbarbituric
and hydrochloric acid, or by boiling with excess acid with water or silver oxide (Techow, Ber.
of sulphurous acid to alloxantin (q.v.) ; and is 1894, 27, 2083), loses 1H 2 when dried over
readily hydrolysed by alkali carbonates or by the sulphuric acid, decomposes at 100; the an-
hydroxides or chlorides of the alkaline earths, hydrous compound is a pale
yellow powder
forming the corresponding salt of allozanic acid. soluble in alcohol. Diethylalloxan C 8 10 4 2 , H N
The barium and calcium salts are insoluble. prepared by oxidising 1 : 3-diethylbarbituric
acid with nitric acid, containing a little nitrous
/NH-CX CO-NH-CO-NH 2 acid (Sembritzki, Ber. 1897, 30, 1820).
CO +H 2
= CO Methyl-
ethylalloxan, from ethyltheobromine by oxidation
\NH-CO COOH. (Pommerehne, Apoth. Zeit. 1897, 12, 5). Some
derivatives of 1 : 3-diphenylalloxan have been
If, however, excess of alkali is employed or the described by Whiteley (Chem. Soc. Trans. 1907,
solutions are heated, the hydrolysis is carried
91, 1344).
to completion with the formation of mesoxalic Inasmuch as the alloxan molecule contains
acid and carbamide (Schlieper, Annalen, 1845, the mesoxalyl radical
55, 263 56, 1 ). Alloxan gives a deep- blue colour
;
with ferrous salts, but no precipitate is formed (OH)

unless an alkali is present. According to Agres- '<oo.'
tini (Boll.Chim. Farm. 1902, 41, 5-7 ; Chem. it forms a wide series of condensation products
Zentr. 1902, i. 631), the formation of blue colour through the medium of the C(OH) 2 or :CO group
:
is dependent on the presence of a trace of yielding derivatives of the type

ammonia or caustic alkali, and the same deep-
blue colour is also given by pure ferric salts under
similar conditions. Alloxan gives the murexide
RC(OH) >CO or R :
reaction, and Angrestini (I.e.) finds that the \CO-NH

ammonia in the reaction can be replaced by respectively. These compounds will be described
certain acid amides, amino acids, or substituted under the following eight headings.
amines ; Rosenheim's alloxan test for choline 1. Condensation of Alloxan with Bisulphites.
(J. Physiol. 1905, 33, 220), namely, the forma- Alloxan forms condensation products of the
tion of a deep red- violet colour when a drop type C 4 H 2 N;>0 4 ,NaHS0 3 ,lH 2 O with alkali
of a 1 p.c. solution of choline hydrochloride is bisulphites (Limpricht and Wuth, Annalen, 1858,
evaporated on the water- bath with a few drops 108, 41), and with the sulphites of certain organic
of a saturated solution of alloxan, is probably a bases (Pellizzari, Annalen, 1888, 248, 146).
reaction of the same order. Alloxan ethylamine sulphite C 2 H 7 N'S0 3 H 2 '
Other tests for alloxan are (1) the formation C 4 H 2 N 2 4 ,H 2 ; Alloxan aniline sulphite C 6 H 7 N
of a deep violet-blue colour when a solution of S0 3 H 2 ,C 4 H 2 N 2 4 ,2H 2 ;
Alloxan methylaniline
2 ,C 4 H 2 N 2
alloxan is boiled for a few minutes with a drop 4 -2H 2
Alloxan
;
of pyrrole. The colour changes to red on cooling,

becoming green and then intensely blue on the 4H 2 0, are described and the crystallographic
addition of alkali. (2) The blue-green solution constants are given. The benzidine compound
obtained on mixing concentrated sulphuric acid contains 1H 2 ; toluidine, aminobenzoic acid, and
solutions of alloxan (or alloxantin) and pyro- aspartic acid yield similar compounds. Alloxan
catechol, the colour changes to an intense pyridine sulphite is triclinic, and anhydrous
green on dilution (Agrestini, I.e.). Hartley (Chem. crystalline derivatives are afforded by quino.ine,
Soc. Trans. 1905, 87, 1816) finds that hydrated picoline, morphine, and cinchonine ; the strychnine
alloxan, when powdered along with pure calcite. compound has 1H,0, and the brucine compound
acquires a yellowish-pink tinge. After half an 1H 2 0.
hour the colour is decided and it is permanent ; 2. Condensation of Alloxan with Hydroxyl-
on adding water a red solution is obtained. amine. Alloxan condenses with hydroxylamine
When alloxan, dried at 100, is similarly treated, hydrochloride (Ceresole, Ber. 1883, 16, 1133) to
there is no colour developed until water has form the oxime, violuric acid
been added. AUoxanic acid gives no such
colour reaction.
The following homologues of alloxan have
been described :
Methylalloxan (q.v.).
Condensation of Alloxan with Hydrazines.
3.
of alloxan and its homologues can
Hydrazones
be prepared by the condensation of (a) the
prepared from methyl uric acid (Hill, Ber. 1876, alloxan with the hydrazine
94 ALLOXAN.
from alloxan and aminophenylcyanamide, straw-
yellow compound, m.p. 286 (Rolla, Gazz. chim.
ital. 1907, 37, i.
623).
Condensation of Alloxan with Semicarba-
4.
of the corresponding This reaction has been studied by Brom-
(b) the dibromo- derivative
zide.
barbituric acid with the hydrazine berg (Ber. 1897, 30, 131). He describes the
compounds alloxansemicarbazide CsH 9 O g N 5 and
H
dimethylalloxansemicarbazide C 7 11 B 6 but was N ,
not successful in determining their constitution.

: N-NHPh + 2HBr, 5. Condensation of Alloxan with Diamines.
In the condensation of alloxan with o-diamines
(c) the corresponding barbituric acid with the
the ke tonic carbonyl and one of the adjacent
diazonium chloride
carbimido- groups take part, and the product
is an azine ; alloxazine
/N:C-NH-CO
And the following hydrazones have been pre- \N:C<X)-NH
pared by one or more of these methods
Alloxan- :
obtained from o-phenylenediamine, forms yellow

phenylhydrazone
microscopic crystals that decompose above 300 ;
similar derivatives were obtained from 3 4- :
diaminotoluene and a-0-diaminonaphthalene

crystals, melts and decomposes
at
pale-yellow
a
298-300 ; 1 3-Dimethylalloxanphenylhydrazone
:
(Kuhling, Ber. 1891, 24, 2363) ; for the effect of
oxidising and reducing agents on these com-
^ N
W NHph pounds, compare Kuhling, Ber. 1895, 28, 1968 ;
\NMe-OV . .
f( '
1899, 32, 1650).

slender yellow crystals, m.p. 261 the o- and p- The condensation of alloxan with mono-
nitro derivatives are yellow crystalline substances substituted o-diamines results in the formation
and decompose at 310 and 300 respectively of two compounds according as one or more
(Kuhling, Ber. 1891, 24, 4140 ; 1898, 31, 1972) ; alloxan molecules take part in the reaction.
alloxanphenylmethylhydrazone Thus alloxan condenses with orthaminoditolyl-
amine at the ordinary temperature to form
alloxanylorthaminoditolylamine
brick-red hexagonal plates, decomposes at 189-
191 (Whiteley, Chem. Soc. Proc. 1906, 22, 201) ; CO
alloxandiphenylhydrazone
glittering yellow prisms, that melt and decompose
at 252, and dissolve in concentrated sulphuric
bright-yellow powder, melts above 270 (Arm- acid with a deep red colour ; if, however, the
strong and Robertson, Chem. Soc. Trans. 1905, condensation is effected in the presence of fuming
87, 1291) ; 1 3-dipJienylalloxanphenylhydrazone
:
hydrochloric acid and the mixture is boiled,
dialloxanylorthaminoditolylamine
C(OH)-N(C,H 7 )-C 7 H 6 -N:C

bright-yellow needles that decompose at 265, the
p-nitro derivative forms yellow prisms with a OC CO OC CO
purple reflex and melt and decompose at 274 ;
1 :
3-diphenylalloxanphenylmethylhydrazone
HN NH HN NH
decomposes at 175 and crystallises in orange- is formed. It is crystalline, and blackens at

red prisms or bright-yellow needles ; 1:3- 300, dissolves readily in alkali carbonates, and
diphenylallozandiphenylhydrazone gives a deep-blue solution in concentrated
sulphuric acid. Dimethylalloxan gives similar
derivatives (Kuhling, Ber. 1893, 26, 540), and
similar condensation products are obtained
melts and decomposes at 254-255, and forms from alloxan and phenyl-o-phenylenediamine,
yellow crystals yielding an orange-red powder on
trituration 1 o-aminodi-p-tolylamine, and N-methyl-o-pheny-
3-diphenylalloxanphenylbenzylhy-
; :
lenediamine (Kuhling and Kaselitz, Ber. 1906 ;

drazone
39, 1314) and from tetramethyl-m-phenylene-
;
CO <NPh'cO>C N'NPh-CH 2 Ph :
diamine (Sachs and Appenzeller, Ber. 1908, 41,
91).
melts and decomposes at 130, crystallises from 6. Condensation of Alloxan with Aromatic
benzene in bright-yellow needles, and from amines. Alloxan condenses readily with pri-
methyl alcohol in bright-red prisms ; from
toluene a mixture of the red prisms and yellow
mary aromatic amines (Pellizzari, Gazz. chim.
ital. 1895, 17, 419) to form aminoaryl sub-
needles is obtained (Whiteley, Chem. Soc. stituted dialuric acids, yielding on hydrolysis
Trans. 1907, 91, 1344) ; alloxancyanophenyl- with the corresponding tartronic acid
alkali,
hydrazone (q-v.). Thus aniline and alloxan give >-amino-
phenyldialuric acid, and this on hydrolysis
yields ^-aminophenyltartronic acid
ALLOXANTIN. 95
A description of the compounds obtained
from alloxan and the phenolic
compounds, phenol,
m-cresol, p-cresol, guaiacol, pyrocatechol, resor-
cinol, hydroquinone, pyrogaUol, a-naphthol, is
NH + 4KOH given m
D. R. P. 107720,
25/8, 1898; 113722
4- 2
9/7, 1900 ; 114904, 17/9, 1900; and the tartronic
= NH 2 -C 6 H 4 -C(OH)(C0 2 K) 2 +2NH 3 +K 2 C0 3
.
acids derived from them are described in D R P
In view of the importance of these compounds 115817, 8/10, 1900.
as sources of tartronic acids, their preparation 8. Condensation of Alloxan with
Ketones.
forms the subject of a patent, D. R. P. 112174 Alloxan condenses with acetophenone and certain
(Frdl. 1900-1902, 158-159), in which the amino- of its homologues to form
phenacyldialuric acid
aryl- dialuric and tartronic acids obtained from
or its derivatives of which the
following are
the following bases are described : ethylaniline, described by Kuhling (Ber. 1905,
38, 3003),
diethylaniline, benzylaniline, methylbenzylani- Kuhling and Schneider (Ber. 1909, 42, 1285) :
line, ethylbenzylaniline, diphenylamine, o-tolu- phenacyldialuric acid

idine, o-ethyltoluidine, o-anisidine, methyl-o-
anisidine, o-phenetidine, m-chloraniline, m-chlor-
/CO-NH
COPh-CH 2 -C(OH) \CO,H
dimethylaniline, and w-chlordiethylaniline.
2
By careful oxidation with potassium perman- \CO-NIT

ganate of the alkali salts of the tartronic acids, m.p. 212, with decomposition the brotno- ;
or by oxidising the corresponding dialuric acid derivative decomposes at 217;

p-ethoxyphen-
with mercuric oxide in presence of potassium H
acyldialuric acid C, 4 14 6 N 2 m.p. 214; the
,
hydroxide, the corresponding glyoxylic acid (q.v.) bromo- derivative, decompose's at 201
ay-di- ;
can be obtained phenylacetonyldialuric acid

NH 2 -C 6
H 4 -C(OH)(C0 2 H) 2 + /CO-NH
= NH 2 -C 6 H 4 -CO-CO..H + C0 + H O
2 2 CH
and the preparation by these methods of an 2 Ph-CO-CHPh-C(OH) ^>CO
important glyoxylic acids forms the
series of \CO-NH
subject of patents D. R. P. 117021, 26/11, m.p. 233 with decomposition ; p-methylphen-
1900 and
; 117168, 3/12, 1900. acyldialuric acid
Alloxan condenses also with pyrazolone bases /CO-NH
to form derivatives of dialuric acid (tartronyl-
C 6H 4 Me-CO-CH 2 -C(OH) \JQ
carbamide), and these on hydrolysis with cold
caustic alkali yield the corresponding substituted \CO-NH
tartronimides (Pellizzari, Gazz. chim. ital. 1888, m.p. 241-242, with decomposition ; the acelyl
Thus phenylmethylpyrazolonetartronyl- derivative decomposes at 220, the
18, 340). benzoyl at
carbamide 215 p-methoxyphenacyldialuricacidC H. O N a
;
13 lz 6
NPh-CO decomposes at 227, and yields an acetyl deriva-
tive, m.p. 207.
ALLOXANIC ACID v. ALLOXAN.
MAW
forms long yellow needles that decompose at ALLOXANTIN C 8 H 6 8 N 4 ,2H 2 (Ritthausen,
170-178, and Ber. 1896, 29, 892) exists in small quantities
yield phenylmethylpyrazolonetar-
tronimide in crude beet-juice (Lippmann, Ber. 1896, 29,
NPh-CO 2645), and forms 34 to 36 p.c. of the products
when convicin from sow- beans (Vicia faba minor)
N = CM [
or from vetches (Vicia sativa) is
hydrolysed
on hydrolysis ; phenyldimethylpyrazolonetar- | by dilute mineral acids (Ritthausen, I.e.
J. pr. Chem. 1899, [ii.] 59, 487). Alloxan-
tronylcarbamide ;
NPh CO !
'
tin was first prepared by
Liebig and Wohler
(Annalen, 1838, 26, 262) by oxidising uric acid
NMe-CMe with dilute nitric acid ; or by the direct union
melts and decomposes at 261, and of alloxan and dialuric acid, or by
yields reducing a
phenyldimethylpyrazolonelartronimide cold aqueous solution of alloxan with
sulphur-
NPh-CO etted hydrogen or stannous chloride.
According
to Vitali (Chem. Zentr. 1898, i. 665, from Boll.
NMe-CMe<
f
Chim. Farm. 37, 65), the reduction can also be

effected by means of hyclriodic acid.
decomposing at 245-250. Alloxantin
7. Condensation of Alloxan with Phenols. was synthesised by Grimaux (Compt. rend. 1878,
Alloxan condenses in the presence of hydrogen 87, 752) by heating malonic acid, carbamide and
chloride, sulphuric acid, or zinc chloride with J
phosphoryl chloride at 150, and passing
mono- or polyhydroxy- phenols to form sulphuretted hydrogen through a nitric acid
derivatives of dialuric acid (tartronylcarbamide), solution of the crude product or by passing
;
that promise to be of value for pharmaceutical sulphuretted hydrogen through a hot aqueous
purposes, and are readily converted by hydrolysis solution of dibromobarbituric acid (Compt. rend.
into the corresponding tartronic acid .- 1879, 88, 86). Koech (Annalen, 1901, 315, 246)
describes the conversion of j'sodialuric acid into
OH-C.H, alloxantin by heating it with guanidine and
/CO-NH ]
acetic acid the change seems to be due to the
;
transformation of the t'sodialuric acid into

OH-C g H 4 .C(OH) \X) dialuric acid by the action of the base, and the
\CO-NH
j
subsequent oxidation of the dialuric acid to

-> OH-C 6H 4C(OH)(C0 2 H) 2 alloxantin, since, if the reaction is conducted in an
96 ALLOXANTIN.
atmosphere of carbon dioxide, dialuric acid only aqueous solution of the hydrochloride of a
is obtained. primary amine, yielding alloxan, together with
Alloxantin crystallises from aqueous solutions the corresponding dibarbiturylalkylamine. These
in small sharp rhombic prisms, containing 2 mols. are colourless crystalline dibasic acids, hydrolysed
H 2 ; it becomes anhydrous after heating for by boiling with aqueous alkali hydroxides into
1-1 J hours at 150, or for 5 hours at 107-110 ; dialuric acid and the amine. Dibarbiturylme-
it decomposes at 170 into hydurilic acid, thylamine
ammonia, carbon monoxide, carbon dioxide, and
oxalic acid. It is decomposed into barbituric 'c
acid and parabanic acid when heated with

concentrated sulphuric acid at 120, or into decomposes at 280, dibarbiturylethylamine de-
H N
allituric acid C 6 8 4 4 when boiled with excess composes at 235, dibarbiturylphenylamine be-
of hydrochloric acid (Schlieper, Annalen, 1845, comes blue at 240, dibarbituryl-a-naphthylamine
56, 20). Alloxantin is sparingly soluble in cold becomes black at 260, the corresponding j8-
water, yielding an acid solution that reduces compound decomposes at 260, and dibarbituryl-
solutions of silver salts, and gives a characteristic carbamide CO(NH-C 4 H 3 3 N 2 ) 2 decomposes above
violet-blue precipitate with baryta water, 300.
changing on warming into the colourless barium
The following homologues of alloxantin have
alloxanate which undergoes further decomposi- been prepared methylalloxantin C 9 H 8 8 N 4 ,
:
tion into barium mesoxalate and barium car- 3H 2 from methylalloxan and dialuric acid
bonate (Liebig and Wohler, Annalen, 1838, 26, (Andreasch, Monatsh. 1882, 3, 431); sym-
312). Alloxantin has a molecular heat of com- dimethylalloxantin C 10 H 10 8N 4 ,4H 2 O from
bustion = 584-7 Cals. (Matignon, Ann. Chim. methylalloxan (Maly, Andreasch, Monatsh. 1882,
Phys. 1893, [6] 28, 323), and a freshly prepared 3, 109), uusym-dimethylattoxantin C 10 H 10 8 N4 ,
aqueous solution shows a remarkable absorption H from dimethyldialuric acid and alloxan
2
band in the ultra-violet, which disappears upon (Andreasch. Montash. 1882, 3, 428). Tctra-
keeping the solution, owing to the decomposition methylalloxantin, C 12 H 14 O 8N 4 amalic acid (from
of the alloxantin into alloxan and dialuric acid dyua\o's
= soft, so called on account of its
(Hartley, Chem. Soc. Trans. 1905, 87, 1814). feebly acid reaction), prepared (1) by oxidising
For this reason Hartley expresses the constitution caffeine with chlorine or nitric acid ( Rochleder,
of alloxantin by the formula Annalen, 71, 1) ; (2) by reducing dimethylalloxan
/CO-NH X with sulphuretted hydrogen (Fischer, Ber.
/NH-CCK
C0< HO^C-0-Cf-H \CO 1881, 14, 1912) or with stannous chloride
NNH-CO/ XCO-NH/ (Andreasch, Monatsh. 1895, 16, 19) ; (3) from
dimethyldialuric acid and dimethylalloxan
(ibid. 1819). Piloty and Finckh (Annalen, 1900,
(Maly and Andreasch, Monatsh. 1882,3,105);
333, 22) found that alloxantin was resolved into
(4) by the electrolysis of caffeine in sulphuric
alloxan and dimethylamine dialurate, by boiling acid solution (Pommerehne. Arch. Pharm. 235,
with dimethylamine acetate, and suggest the C 16 22 8 4, ob- H N
365). Tetraethylalloxantin
constitutional formula
tained by reducing diethylalloxan, melts and
^/NH-CCK decomposes at '162 (Sembritzki, Ber. 1897,

,^C(OH)-NH-^ 30, 1821). M. A. W.
\XTTT f^/~\ / ^*^*^J\J '
-WJi^
JNH-OU/ ALLOXAZINE v. ALLOXAN.
in which the relationship between alloxantin and ALLOYS v. METALLOGRAPHY.
alloxan is the same as that existing between ALLYL. A univalent radicle C 3 5 H ,
or
quinhydrone and quinone. CH 2 CH-CH :
2 , isomeric with propenyl CH 3 -
Alloxantin is readily converted into murexide CH CH<. :
by the action of ammonia, into alloxan

(q.v.) Allyl acetate CH 3 -C0 2 C 3 H 5 , boils at 103-
by mild oxidising agents, and into dialuric 104/733-9 mm. (Briihl), andhassp.gr. 0-9376 at
acid by reducing agents. In its physiological (Schiff). It is only slightly soluble in water,
action alloxantinresembles alloxan, but is and has a rather sharp smell. It is prepared
especially poisonous to cold-blooded animals, by the action of allyl iodide on silver acetate
the blood showing strong reducing properties ; (Zinin, Annalen, 96, 361 Cahours and Hofmann, ;
when taken internally it appears in the urine as Annalen, 102, 295 ; Briihl, Annalen, 200, 179 ;
parabanic acid, and in smaller quantities as Schiff, Annalen, 220, 109).

dialuric acid, murexide, and alloxantin itself Allyl acetic acid C 3 H 5 -CH 2 -C0 2 H boils at
(Kowalewski, Chem. Zentr. 1887, 1296 Susini, ; 187-189, and has sp.gr. 0-98416 at 15 (Perkin). '
Ann. Chim. Farm. 1895, 21, 241 1896, 22, 341, ; It is slightly soluble in water and its smell
385). resembles that of valerianic acid. It is unaffected
Acetylalloxantin C 10 H 8 9 N 4 ,H 2 0, obtained by reduction with sodium amalgam, but readily
by the interaction of acetyl dialuric acid and unites with two atoms of bromine. It is prepared
alloxan, crystallises in thin leaflets, becomes by hydrolysing allyl acetoacetic acid ethyl ester
anhydrous when kept in a vacuum over sulphuric with dry sodium ethoxide, or by heating allyl
acid, melts and decomposes at 263 265, and malonic acid (Zeidler, Annalen, 187, 39 ; Conrad
is slowly hydrolysed by hot water with the and Bischoff, Annalen, 204, 170 ; Henry, Chem.
formation of alloxantin. Zentr. 1898, ii. 663).
H
Benzoylalloxantin C 15 10 9 4 ,H 2 0, simi- N The chloride C 3
6
H
-CH 2 -COC1 is a thick,
larly formed from benzoyl dialuric acid and pungent-smelling syrup, boiling at 128/765 mm.,
alloxan, crystallises in colourless six-sided plates, and of sp.gr. 1-0739 at 16 (Henry, I.e.).
and melts at 253-255 (Behrend and Friedrich, Allylacetone CH 3 -COCH 2 -C 3 H 6 boils at
Annalen, 1906, 344, 1). 128-130, and has sp.gr. 0-834 at 27. It is
Alloxantin is decomposed when boiled in an an unpleasant-smelling liquid. It forms an
ALLYL. 97
to remove excess of bromine and
amorphous compound with sodium bisulphite, [
cooling. This
and is reduced by sodium amalgam to hexenyl liquid contains dihydroxyacetone, and in the
alcohol. It prepared by hydrolysing allyl
is presence of concentrated sulphuric acid gives a
acetoacetic acid ethyl ester (70 grams) with deep-blue colour wioh codeine, orange-red with
crvstallized baryta (215 grams) and water resorcinol, blood-red with thymol, or green with
(|iif>0 c.c.) (Zeidler, Annalen, 187,35; Merling, green fluorescence with ^-naphthol (Deniges,
Annalen, 264, 323). Treated with hydroxyl- Compt. rend. 148, 172 and 282).
amine it yields allylacetoxime CH 3 -C( NOH)-CH 2 : .
Allylamines.
C 3 H 5 which is a liquid boiling at 188 (corr.),
,
H
Monoallylamine C 3 5 -NH 2 is a liquid boiling
soluble in alcohol, benzene, ether, acids and at 53-3 and of sp.gr. 0-7799 at 4 and 0-7688 at
alkalis. 15 (Perkin, Chem. Soc. Trans. 1889, 697) ;
b.p.
H
Ally! alcohol C 3 6 -OH, i.e. CH
2 :CH-CH 2 -OH,
58 and sp.gr. 0-864 at 15 (Rinne, Annalen,
occurs in raw wood spirit, but only to the extent 168, 262) ; b.p. 56 -56-5 /756-2mm. (Schiff, Ber.
of about 0-2 p.c. (Aronheim, Ber. 1874, 1381 ; 1886, 565). It is
prepared from allyl isocyanate
Groclzki and Kramer, ibid. 1492). It is a and potash, or from allyl iodide and ammonia,
pungent liquid with a burning taste, and mixes or by reduction of allyl mustard oil with zinc
readily with alcohol, water, or ether. It boils and hydrochloric acid (Oeser, Annalen, 134, 8). It
at 96-6 (corr.), and has sp.gr. 0-87063 at and possesses a penetrating smell, which excites tears
0-8573 at 15/15 (Thorpe, Chem. Soc. Trans. and produces sneezing. It is miscible with water
1880, 208). in all proportions,and is a strong base, forming
It is prepared by slowly distilling glycerol |
a crystalline platinichloride (C 3 H 5 -NH.,) 2 PtCl 6 ,
(400 pts.) with crystallized oxalic acid (100 pts.) !
and sulphate (C 3 H 5 -NH,) 2 H.,S0 4 .The" hydro-
and a little ammonium
chloride (1 pt.) to !
chloride melts at lOS^HO" (Delepine, Bull.
convert any potassium oxalate into chloride. Soc. chim. [3] 17, 294) and the picrate at
The receiver is changed at 190 and distillation 140-141 after sintering (Gabriel and Eschen-
continued up to 260. The distillate, containing bach, Ber. 1897, 1125).
aqueous allyl alcohol, allyl formate, acroleiin, H NH
Diallylamine (C 3 5 ) 2 boils at 111 and
and glycerol, is rectified and dried, first with is prepared from allylamine and
allyl bromide
potassium carbonate, then over solid potash and (Ladenburg, Ber. 1881, 1879 ; Liebermann and
distilled. When the last traces of water are Hagen, Ber. 1883, 1641).
removed by quicklime it boils at 96. The H
Triallylamine (C 3 5 ) 3 N is a very unpleasant-
yield is one-sixth of the weight of oxalic acid smelling liquid, boiling at 150-151 (Pinner, Ber.
taken (Tollens and Henninger, Bull. Soc. chim. 1879, 2054) ; 155-156, sp.gr. 0-8094 at 14-3
[2] 9, 394 ; Briihl, Annalen, 200, 174
Linne- ; (Zander, Annalen, 214, 151). It is prepared by
mann, Ber. 1874, 854). Further purification distilling tetrallylammonium bromide with large
may be effected by prolonged heating with excess of recently fused potash (Grosheintz,
sodium bisulphite and, after removal of the , Bull. Soc. chim. [2] 31, 391) or from allyl chloride
bisulphite, redistilling several times from quick- and alcoholic potassium cyanide in the cold
lime (Thorpe). (Pinner, I.e.); or from allyl chloride and am-
,It is oxidised by chromic acid solution to monia (Malbot, Bull. Soc. chim. [2] 50, 90). It is
acrolei'n and formic acid ; and by dilute nitric displaced from its aqueous solution by potash,
acid to formic and oxalic acids whilst potassium;
and forms a crystalline platinichloride and
permanganate produces acrolein, glycerol, and hydrochloride.
formic acid. It combines directly with chlorine H
Tetrallylammonium bromide (C 3 5 ) 4 NBr is a
bromine, iodine chloride, and cyanogen, producing crystalline solid, soluble in alcohol and water,
additive products. It is partially reduced by but only slightly so in ether. It is prepared by
boiling for some hours with zinc and dilute leading a stream of ammonia into an alcoholic
sulphuric acid to w-propyl alcohol. Potassium solution of allyl bromide. The product is puri-
displaces the hydroxylic hydrogen atom and fied by recrystallisation from alcohol containing
forms gelatinous potassium allylate. i
a little ether (Grosheintz, Bull. Soc. chim. [2] 31,
Deniges (Bull. Soc. chim. 1909, 5, 878) !
390). Treated with moist silver oxide it yields

describes the following colour reactions for the tetrallylammonium hydroxide.
detection of allyl alcohol, depending on the Tetrallylammonium iodide (C 3 H S ) 4 NI is the
formation of (1) glyceraldehyde and (2) di- main product of the reaction of allyl iodide on
hydroxyacetone and the condensation of these ammonia at the ordinary temperature (Cahours
products with various reagents. Bromine and Hofmann, Annalen, 102, 305 Malbot, Ann.;
water (0-6 c.c. in 100 c.c. water) is added to Chim. Phys. [6] 13, 488). It is a crystalline
till a slight permanent
0-1 c.c. of allyl alcohol, solid, insoluble in strong potash solution.
colouration produced, and the liquid is
is Allylaniline C 6 H 5 -NHC 3 H, is a yellow oil
then boiled, cooled, and divided into portions produced by the action of ally! iodide on aniline.
of 0-4 c.c. To each of these 0-1 c.c. of a 5 p.c. It boils at 208-209 and has sp.gr. 0-982 at 25
solution codeine, resorcinol, thymol, or
of (Schiff, Annalen Suppl. 3, 364).
-
naphthol added, followed by 2 c.c. of sulphuric

is Diallylaniline CgH 5 -N(C 3 H 5 ) 2 is prepared by
acid (sp.gr. 1-84) and the mixture warmed adding allyl bromide (1 mol.) to aniline (1 mol.)
during 3 or 4 minutes at 100. Codeine and in a flask fitted with reflux condenser, separating
thymol give reddish-violet colourations, resor- the allyl aniline by the addition of potash, and
cinol wine-red, and /S-naphthol yellow with converting it into diallyl aniline by repeating
greenish fluorescence. The second series of the process with more allyl bromide (1 mol.).
colour reactions is obtained by adding to the It boils at 243-5-245, and has sp.gr. 0-9538 at
brominated liquid above described 5 c.c. of 19-8 (Zander, Annalen, 214, 149).
bromine water (0-6 c.c. in
water), 100 c.c. C 6 H,j-CH 2 -CH:CH 2
Allyl benzene is obtained
heating during 20 minutes at 100, then boiling by heating together benzene, allyl iodide and
VOL. I. T.
98 ALLYL.
zinc-dust to 100 (Chojnacki, J. 1873, 559; absorbed by strong sulphuric acid, and acetone
Fittig,Annalen, 172, 132). It boils at 155. is produced on dilution. When dissolved in
The isomeric propenyl benzene (and phenyl absolute ether and heated with sodium to 100,
it changes into the isomeric methyl acetylene.
propylene C 6 H^CH:CH-CH 3 ) is sometimes in-
It readily forms a tetrabromide C 3 H 4 Br 4 by
correctly referrea to as allyl benzene.
Ally! bromide, monobrompropylene 2 :CH. CH addition of bromine.
CH 2 Br, boils at 70-71,
and has sp.gr. 1-4336 Unsymmetrical allylene, methyl acetylene
at 17 (Zander, Annalen, 214, 144). It is formed CH 3 -C CH, results from propylene bromide,
by the action of phosphorus tribromide on monobromopropylene, or monochloropropylene
allyl alcohol, and is prepared by dropping allyl by withdrawal of HC1 or HBr by means of
alcohol into a hot solution of potassium bromide alcoholic potash, and from symmetrical allylene
in sulphuric acid (1 vol. acid to 1 vol. 2 0) H (v. supra). It is an unpleasant-smelling gas,
according to Grosheintz (Bull. Soc. chim. [2] 30,

which is liquefied under a pressure of 34
78) or by saturating allyl alcohol with hydro-
; atmospheres. It burns with a bright sooty
bromide at and subsequently heating to flame. It dissolves readily in ether (30 vols. in 1
oiling for several hours (Jacobi and Merling,
fen ! of ether at 16). Potassium permanganate in
Annalen, 278, 11). |
the cold oxidises it to formic, oxalic, and malonic
Allyl chlorideCH 2 :CH-CH 2 C1 boils at 46, I acids. Explosive compounds are produced by
and has sp.gr. 0-9547 at leading it into ammoniacal solutions of silver
'
(Tollens, Annalen,
156, 154) ; 0-9371 at 19-3 (Zander, Annalen, 214, !
nitrate or cuprous .chloride. Concentrated sul-
142). It is prepared by the action of mercuric phuric acid readily absorbs it, forming on dilution
chloride on allyl iodide, or from allyl oxalate and distillation acetone mesitylene and allylene
calcium chloride and alcohol at 100 (Oppenheim, 1
sulphonic acid C 3 H 3 S0 3 H (Schrohe, Ber. 1875,

Annalen, 140, 205) or, best, by heating allyl
;
18 and 367). The barium salt of the latter is
alcohol and concentrated hydrochloric acid to crystalline, easily soluble, and not decomposed
100 for some hours (Eltekow). It combines on boiling with water.
with hydrogen chloride to form propylene H
Allyl ether C 3 5 -0-C 3 H 5
boils at 94-3 and
chloride C 3 H g Cl 2 and with fuming hydrobromic
,
has sp.gr. 0-8046 at 18. It is prepared from
acid yielding l-chloro-3-bromopropane CH 2 C1- allyl iodide and sodium allyl alcoholate, or from
CH 2 'CH 2 Br. :
allyl iodide and mercuric oxide (Cahours and

Allyl cyanamide, sinamine, C 3 H 5 -NH-CN, is ,
Hofmann, Annalen, 102, 290 ; Berthelot and

produced by warming allyl thiocarbamide with Luca, Ann. Chim. Phys. [3] 48, 291).
lead hydroxide on the water-bath (Will, Annalen, H
Allyl ethyl ether C 3 5 -0-C 2 H S boils at 66-
52, 15). On
standing for some months crystals 67/742-9 mm. (Briihl, Annalen 200, 178). Pre-
pared from allyl iodide and sodium ethoxide.
j
separate from the resulting product. It is pre-

pared by shaking an aqueous solution of allyl Allyl iodide C 3 H 5 1 boils at 102-5-102-8 and
thiocarbamide with mercuric oxide until the has sp.gr. 1-8293 at 23. Berthelot and Luca,
!
solution no longer blackens ammoniacal silver Ann. Chim. Phys. [3] 43, 257) obtained it by
nitrate (Andreasch, Monatsh. 2, 780). It is the action of PI 2 on glycerol. It may be
alkaline in reaction, precipitating metallic oxides prepared by leaving together for 24 hours red
and replacing ammonia in its salts. The crystals phosphorus (20 grams), allyl alcohol (160 grams),
contain JH 2 and melt at 100, giving up then- and iodine (254 grams) (Tollens and Henninger,
water. It forms a difficultly crystallisable salt Annalen, 156, 156) or by the following process ; :
with oxalic acid, but not with other acids, and 100 grams of iodine and 1500 grams of carefully
double compounds with mercuric and platinic dehydrated glycerol are brought together in
chlorides. a large vessel, the air displaced by a current of
Allyl cyanide, crotononitrile, C 3 H 5 -CN, boils at carbon dioxide, and 300 grams of ordinary
119 (corr.), and has sp.gr. 0-8491 at and phosphorus gradually added. The allyl iodide
0-8351 at 15. It is obtained by the action of allyl is distilled off in a stream of carbon dioxide, and
iodide on potassium cyanide, and, together with then contains as impurity some sopropyl iodide.
other products, by allowing allyl mustard oil to To purify it from this it is dissolved in alcohol
remain in contact with water for some weeks, and shaken with mercury, when the compound
and also by the action of acetic anhydride on HgC 3 H 5 I is precipitated. This is recrystallised
crotonaldoxime. It has been prepared by Henry from water and decomposed, regenerating allyl
(Chem. Zentr. 1898, ii, 662) by the action of iodide, by distillation with water and the
phosphorus pentoxide on a- or -hydroxy-bu- theoretical quantity of iodine (Linnemann,
tyronitrile. It is a liquid with an unpleasant, Annalen Suppl. 3, 263). It combines with
onion-like smell. On warming to 50-60 with bromine to form tribromhydrin, and with'
fuming hydrochloric acid for two hours, chloro- hydriodic acid to give diiodopropylene. By
butyric acid is produced. Chromic acid oxidises long heating with about 20 parts of water it is
it to acetic acid, nitric acid to oxalic acid. converted into allyl alcohol and hydriodic acid.
Allylenes. Two allylenes are possible and Allyl mercaptan C 3 H 5 SH boils at 90.
known :
symmetrical allylene CH 2 :C:(JH 2 , With mercuric yields C 3 5 SHgC'l,
chloride it H
and unsymmetrical allylene 3 -C. CH :
CH. which crystallises from alcohol
in plates (Hof-
Symmetrical ally\ene,propadiene, CH C :CH
2 :
2, mann and Cahours, Annalen, 102, 292 ; Gerlich,
is a gas which burns with a sooty luminous Annalen, 178, 88).
flame. It is prepared by dropping o-bromoallyl Allylmethylal isothioeyanate is the name
bromide (10 grams) into a mixture of 20 grams H
given to the compound C 3 5 0-S-CH 2 -CN, pre-
zinc-dust and 25 grams alcohol (70 p.c.) (Gus- pared by passing a current of formaldehyde gas
tavson and Demjanow, J. pr. Chem. [2] 38, 202). through glycerol (1 kilo) and allyl isothiocyanate
It does not precipitate ammoniacal solutions of (5 grams) heated to 190 until the weight of the
silver nitrate or cuprous chloride. It is readily whole is 1400 grams. When cool the product
ALMOND OIL.
and the resulting methylal wothiocya-

is filtered urea 00 in
Allyl crystallizes
nate used as an antiseptic (Piot, Fr. Pat. 330988,
1903). needles, melting at 85 (Cahours and Hofmann,
Allyl mustard oil v. MUSTARD OIL and ESSEN- Annalen, 102, 299 ; Andreasch, Monatsh. 5, 36).
TIAL, OILS. J. A. P.
Allyl nitrite C 3 5 H N0
2 is obtained by
adding ALMASCA. A
soft grey resin soluble in
to ice-cold allyl alcohol and and absolute alcohol. Pro-
glycerol trinitrite chloroform, ether,
ester (Bertoni,
cautiously distilling off the allyl bably derived from the burseraceous Protium
Gazz. chim. ital. 15, 364). It boils at 43-5-
heptaphyttum (March.) [Icica heptaphylla (Aubl.)]
44-5, and has sp.gr. 0-9546 at 0. It is readily (Symes, Pharm. J. [3] 13, 213).
decomposed by shaking with water,
and yields ALMATEIN. Trade name for a condensa-
with ethyl alcohol.
ethyl nitrite on treatment tion product of haematoxylin and formaldehyde.
Used as an antiseptic.
may be ALMIRAO. Indian name for Launcea pinna-
Allyl-phenyl-thiourea
tifida Microrhynchus sarmentosus (DC)
(Cass.)
prepared from aniline
and mustard oil (Zinin, which belongs to the family Compositse and is
Annalen, 84, 348); or from allylamine and phenyl used at Goa as a substitute for taraxacum
mustard (Weith, Ber. 1529). It forms
oil 8,
and (Dymock, Pharm. J. [3] 6, 730).
crystals, melting at 98,
is
monoclinic ALMOND. The kernel of the fruit of Prunus
readily soluble in ether, but not hi
water.
amygdalus or Amygdalus communis.
Allyl pyrrol C 4 4 3 8H NC H
is readily obtained
Two principal varieties exist the sweet and
by the action of allyl bromide on potassium the bitter almond. Both contain amygdalin,
pyrrol in ether (Ciamician
and Dennstedt, Ber. but the latter is much richer in this substance
It is a light-yellow oil, turning
1882, 2581). (2 to 3 p.c.), and contains an enzyme, emulsin,
brown on exposure to air. It boils at 105/48 mm. which, in the presence of water, decomposes the
It is insoluble in water, but dissolves in HC1,
amygdalin, yielding glucose, benzaldehyde, and
producing a red colour. hydrocyanic acid
H
Allyl sulphate C 3 5 -HS0 4 is prepared by C 20H 27N0 11 +2H 2
acid
adding allyl alcohol (1 vol.) to sulphuric =C H S CHO+HCN+2C H 12
6 6 6.
diluted with its own volume of water (1 vol.),
In addition, almonds contain about 50 p.c. of
and leaving at ordinary temperatures for five
their weight of a fixed oil (mainly olein, and
days. Subsequently the mixture is heated to liable to become rancid) and smaller quantities
70 for 12 hours, diluted with water (10 vols.),
of proteins, sugar, starch, gum, fibre, and ash.
and saturated with barium carbonate (Szyman-
ski, Annalen, 230, 44 ; v. also Cahours and Analyses of almonds made at various stages
It forms cha- of growth and ripening, show the percentage of
Hofmann, Annalen, 102. 293).
racteristic salts, a number of which are described amyloses, glucose, and saccharose to steadily
diminish, whilst the proportion of oil increases
by Szymanski (I.e.).
Allyl sulphide, oil of garlic, (Ger. Kndblau-

(Du Sablon, Compt. rend. 1896, 123, 1084).
chol) H
(C 3 5 ) 2 S, occurs in garlic (Allium sativum) According to Valle'e (Compt. rend. 1903, 136,
[2] 114), reducing sugars
in the immature almond
and other plants. It is prepared from mustard
oil and potassium sulphide at 100
decrease as the fatty oil increases ; sucrose
(Wertheim,
increases until oil - formation begins, then
Annalen, 55, 297) ; or from allyl iodide and
decreases during oil-production, and towards the
potassium sulphide (Hofmann and Cahours,
Annalen, 102, 291 ). It is a liquid boiling at 138-6,
end again increases. Ripe almonds contain
and has sp.gr. 0-88765 at 26-8/4. It has a very about 3 p.c. of sucrose. According to Osborne
and Campbell Amer. Chem. Soc. 1896, 18,
strong odour of garlic and is only slightly
(J.
soluble in water. 609), the protein in almonds is amandin and not

conglutin or vitellin.
H. I.
Allyl thiocarbamide, allyl thiourea, thiosina-
ALMOND OIL is obtained from the seeds
of Prunus amygdalus (Stokes) [Amygdalus
mine, 'Rhodallin' is produced
communis, (Linn. )]. The almond tree appears to
,
have been indigenous to Turkestan and Middle

by the prolonged action of aqueous ammonia to
on mustard oil (Dumas and Pelouze, Annalen, Asia, and has been transplanted from there
10, 326). It forms clear six-sided tables, which Greece, Italy, Spain, France, and to Northern
melt at 78-4, after sintering at 71. It is Africa. The mean percentage composition of
the almond is given by Konig as follows :
insoluble in benzene, sparingly soluble in
and readily so in alcohol and ether. It Oil 41-00 p.c.
water,
combines with Water 27-72
directly halogens, cyanogen,
Albuminoids . 16-50
ethyl iodide, acids, &c. Deprived of its sulphur
.
by mercuric oxide, or lead oxide, it yields sina- Extracted matter, free from nitro-
H
mine (allyl cyanamide) C 3 5 -NH-CN. It has been gen . 10-2
used in surgery for the removal of scar tissue, Crude fibre . 2-81
Ash 1-77
being injected as a 10 or 16 p.c. solution in
.
dilute glycerol.
Tribromhydrin C 3 H 5 Br 8
' ' 100-00
Allyl tribromide, ,
was obtained by Wurtz by treating allyl iodide The commercial expressed from
oil is chiefly
with bromine, and by Berthelot and Luca by bitter almonds, the seeds of Prunus amygdalus,
the action of phosphorus tri- and pentabro- var. amara. Bitter almonds contain, besides
mides on glycerol. It is a slightly yellow liquid the oil, amygdalin and emulsin, which give
of sp.gr. 2-430 at 15-5, and boils at 217. It is rise to the formation of benzaldehyde, glucose,
a strong sedative and anodyne. and acid.
hydrocyanic Hence the press-cakes
H 2
100 ALMOND OIL.
from almonds find a profitable outlet in the Jamaica, and St. Helena. It is opaque, lustre-
manufacture of genuine ethereal bitter almond
'
less, and
of a brown colour, with a bitter
oil,' by triturating the meal with water.
nauseous taste and very disagreeable odour
Sweet almonds (from Prunus amygdalus, it gives a powder of a dull-yellow colour.
var. dulcis) are but rarely used alone for the 2. Cape Aloes (A. Perryi, A. lucida ?),
obtained from A. spicata, A. africana, A. ferox,
preparation of almond oil. Mogador bitter
almonds, which are chiefly used in this country and other Cape species. Its odour is stronger
for the manufacture of almond oil, are always ;
and more disagreeable than that of Barbados
more or less mixed with sweet almonds. Sweet aloes it is of a deep greenish-brown colour, is
;
almonds yield from 44-55 p.c. of oil, bitter ;

resinous and shining, and its powder is of a
almonds yield less and may contain as low a greenish-yellow colour, and is almost completely
soluble in boiling water.
proportion of oil as 20 p.c. On an average,
however, bitter almonds yield from 38 to 45 p.c. 3. Hepatic Aloes. Imported from Bombay
of oil. and Madras. It is probably the juice of the
The oil is it has a very pleasant,
pale yellow ;
Socotrine aloe solidified without the aid of arti-
mild taste, and almost free from odour. The
is ficial heat (Pereira, Pharm. J. [3] 11) ; it is of an
specific gravity of the oil varies from 0-917 to opaque liver colour, its powder contains much
0-9195 at 15. The oil solidifies at 15, has matte insoluble in weak alcohol.
the saponification value of the majority of oils 4. Socotrine Aloes. The juice of A. Perry i
which are free from volatile acids, and an iodine (Baker) imported from Bombay and Madras. It
value of 93-100. This points to the presence of is of a garnet-red to golden-red colour, is aro-
linolic acid, of which about 10 p.c. may be matic, and has an intensely bitter taste ; its
contained, on an average, in almond oil, the powder is of a bright golden-yellow colour
remainder being practically oleic acid, since the (Cooley, 1).
oil contains no stearic acid, and is most likely 5. Zanzibar Aloes, from Zanzibar.
also free from palmitic acid. Aloins. By extracting aloes with water the
Almond oil is chiefly used in pharmaceutical
purgative principles, aloiins, can be obtained.
practice. Owing to its high price almond oil is Shenstone (Pharm. J. [3] 13, 461 Chem. Soc. ;
largely adulterated with other oils of the Prunus Trans. 44, 480) divides them into two classes :
with apricot kernel oil, from

family, chiefly 1. Nataloins, which only yield picric and oxalic
Prunus armeniaca (Linn.), and with peach kernel acids with nitric acid, and which are not
oil, from Prunus persica (Sieb. et Zucc.). These reddened by it, even on heating (Fluckiger,
two oils are very similar to almond oil ; they Arch. Pharm. [2] 149, 1.1 ; Tilden, Chem. Soc.
differ from it by their higher iodine values, and Trans. 25, 153). 2. Barbalo'ins, which yield
in having a less pleasant taste than almond oil. aloetic acid C 14 H 4 (N0 2 ) 4 2 chrysammic acid
,
They are used to such an extent as adulterants C 14 H 2 (NO.j) 4 (OH) 2 O2, picric and oxalic acids,
that frequently they completely substitute and are reddened by nitric acid. a- Barbalo'ins,
' '
almond oil indeed foreign
; almond oil, or from Barbados aloes reddened in the cold by
'
'
oil of sweet almonds, French (Oleum amygda- strong nitric acid (Tilden, Pharm. J. [3] 2, 845 ;
larum gallicum), is nothing else than a mixture Chem. Soc. Trans. 25, 488). Barbalo'ins, from
-
of apricot kernel oil and peach kernel oil.

Socotrine, Zanzibar, and Jafferabad aloes,
Genuine almond oil is sold in commerce under coloured only on heating with ordinary, and in
the name almond oil, English.'
'
the cold with fuming, nitric acid (Fluckiger, I.e. ;
The close relationship in which apricot and
Tilden, Chem. Soc. Trans. 28, 1270; Pharm.
peach kernel oils stand to almond oil, renders J. [3] 4, 208).
their detection in almond oil a difficult problem. Barbados aloes, analysed by Tschirch and
For methods of solving it the reader is referred Pedersen (Arch. Pharm. 236, 200), was found to
to Lewkowitsch, Chemical Technology and
contain 12-25 p.c. barbaloin, 12-65 p.c. resin,
Analysis of Oils, &c. ii. 234. J. L. 1-75 p.c. ash, 10-5 p.c. amorphous constituents
ALMONDS, BITTER, Essential oil of (v. BEN- soluble in water, and 0-15 p.c. of an orange
ZALDEHYDB also OlLS, ESSENTIAL).
colouring matter, aloe-emodin C ls H. 10 O b m.p.
;
,
ALOE. A genus of succulent plants, having H

216. Barbaloin C 16 18 0, or C 16 16 O 7 (?) was H
stiff,pointed, fleshy leaves, belonging to the isolated by Smith (Chem. Gaz. 1851, 107), and
Liliacese. (Plants figured, and structure of first examined by Stenhouse. It consists of pale-
leaves described, Pennetier, 560, 579.) Of the
yellow needles, which melt at 147 and readily
85 species 60 are natives of Cape Colony, and the become discoloured when moist. Leger (Compt.
other species are mainly sub-tropical African, rend. 125, 185 ; 127, 234), by recrystallisation.
though a few occur in the tropics ; a number of of partially purified barbaloin from methyl
species have been, however, introduced into the alcohol, has obtained isobarbaloin, isomeric with
West and East Indies. (For a list of the species barbaloin. /sobarbaloin crystallises from methyl
and their distribution, v. Pharm. J. [3] 11, 746.) alcohol in efflorescent crystals with three mols. of
The fibre is used for rope, &c. experiments ;
methyl alcohol, or from water with two mols. of
made in Paris have shown it to be five times as water of crystallisation. On fusion with caustic
strong as hemp. The fibre has also been used potash, barbaloin yields orcin, ^-hydroxybenzoic
for paper-making (Nat. 20, 484). and alorcinic acids (Hlasiwetz, Annalen, 134, 237;
ALOE RESINS v. ALOES OR BITTER ALOES. 136, 31), and on oxidation with chromic acid
ALOES or BITTER ALOES. ( Aloes, Fr. ;
breaks up into carbon dioxide, acetic acid, and
Aloe, Ger.) The inspissated juice or extract of aloexanthin (Tilden, Pharm. J. [3] 8, 231 Chem. ;
the aloe. The principal varieties found in the Soc. Trans. 32, 264, 903). Oesterle and Babel
market are :
(Chem. Zentr. 1904, ii. 340) have shown, how-
Barbados Aloes (aloes in gourds. The
1. ever, that Tilden's aloexanthin is a mixture
juice of A. vera (Linn.) growing in Barbados, of aloe-emodin and rhein, the latter compound
ALPINIA OFFICINARUM. 101
being identical with the rhein isolated from reddish-violet tint (Klunge, Ber. 16, 691 ; Arch.
rhubarb by Hesse (Annalen, 309, 43). Pharm. 1883, 363). This reaction is due to iso-
The resin from Barbados aloes on hydro- barbaloi'n, for barbaloin, recrystallised several
lysis gives cinnamic
acid and a resin alcohol times from methyl alcohol, does not
give the
H
aloresinotannol C 22 2g 6 consisting of a greyish-
,
test (Leger, Compt. rend. 131, 55).
Borntrager
brown powder (Tschirch and Pedersen). By the (Zeitsch. anal. Chem. 19, 165 ; Ber. 13, 1040)
action of alcoholic hydrogen chloride, Oesterle extracts with twice the volume of benzene, and
(Arch. Pharm. 237, 81) obtained a trihydroxy- adds to the clear extract a drop of ammonia,
methylanthraquinone C 15 Hi O s , m.p. 224, when, on warming and shaking, the solution
identical with the aloe-emodin of Tschirch and becomes violet-red; Groves (Pharm. J. [3] 11,
Pedersen; also Leger (Compt. rend. 134, '1111) 1045) finds that this colour is not due to alo'i'n,
has obtained aloe-emodin by treatment of barba- but probably to a tannin-like substance. Accord-
loi'n or t'.?obarbalo'in with sodium peroxide. ing to Tschirch and Pedersen, this test depends
According to Leger (J. Pharm. Chim. iv. 20, on the presence of aloe-emodin. Lenz (Zeitsch.
145; Compt. rend. 150, 983), both barbalo'in anal. Chem. 21, 220) extracts with amyl alcohol,
and wobarbaloin left in contact with alcohol evaporates the extract, treats with nitric acid,
for a long time, give a pentose alo'inose. This and then with potassium cyanide and hydroxide,
sugar has since been shown by Leger (Compt. when a blood-red colouration is obtained.
rend. 150, 1695) to be identical with d-arabinose. Cripps and Dymond (Pharm. J. [3] 15, 633)
The aloiin from Natal aloes has the composi- test for aloi'n by dissolving 1 grain in 16
tion C 24 H 2S 10 with varying amounts of com-
, drops of strong sulphuric acid, then adding
bined water. It softens at 180 and melts 4 drops of nitric acid (1-42) and 1 ounce of
with decomposition at 210. On acetylation a water, when a deep orange or crimson colour
penta-acetyl derivative is formed. Natalo'in is produced, deepened
by ammonia substances ;
differs from barbaloiin by its resistance to alkalis, containing chrysophanic acid behave in a similar
and by containing a methoxyl group (Groenwold, manner, but their aqueous solution turns pink
Arch. Pharm. [3] 28, 115). Leger (Compt. rend. upon the addition of ammonia. Aschan (Arch.
128, 1401) has isolated two aloins from Natal Pharm. 241, 340) gives in tabular form a com-
aloes: natalo'in, the compound more soluble in parison of the reactions of the chief varieties of
methyl alcohol, to which he gives the formula aloes.
C 16 H 18 7 and homonatalo'in C 15 H lg 7 the less
; , For the estimation of aloin in aloes, Schaefer
soluble constituent. Tschirch and Klaveness (Jour. Pharm. [vi.] 5, 296) recommends the
(Arch. Pharm. 239, 231), however, could not following : 50 grams of aloes are dissolved in
detect any substance corresponding with Leger's 300 c.c. of warm water to which a few drops of
homonataloiin. hydrochloric acid have been added. When
The resin from Natal aloes when hydrolysed cold the solution is separated from the resin,
gives H
nataloresinotannol C 22 18 4 (OH) 4 , con- 50 c.c. of 20 p.c. aqueous ammonia and a solution
sisting of a brown powder, and ^-coumaric of 15 grams of calcium chloride in 30 c.c. of
acid. Nataloresinotannol gives a tetra-benzoyl water are added, and the whole rapidly shaken.
derivative it yields oxalic and picric acids
;
At the end of fifteen minutes the precipitate is
when oxidised with nitric acid, and on fusion separated and triturated in a mortar with
with potash gives phloroglucinol and fatty acids. hydrochloric acid. The free aloi'n and the
Natalo'in, heated with sodium peroxide, calcium chloride are dissolved in as little water
yields nataloemodinmethylether, m.p. 238, as possible, filtered if necessary, and the residue
which on heating with concentrated hydrochloric washed with boiling water. The aloi'n separates
acid is converted into nataloemodin, consisting of from the aqueous solution on cooling. A. S.
orange-red needles, melting at 220-5 (Leger). ALOES, ESSENTIAL OIL OF. A pale-yellow
The aloins from Curacao, Cape Socotra, mobile liquid to which the odour of aloes is due.
Uganda, and Jafferabad aloes are probably Sp.gr. 0-863, boils at 266-271. It exists in small
identical with barbalo'in. Zanalo'in from Zanzi- quantities in aloes, and when pure has the taste
bar aloes appears to be different (Leger, J. and odour of peppermint (Pharm. J. [3] 10, 613).
Pharm. 25, [vi.] 513 Tschirch and Hoffbauer,
; ALOES WOOD. A
name applied to the wood
Arch. Pharm. 243, 399). The latter chemists of Aquillaria Agallocha (Roxb.), a leguminous tree
show that Barbados aloes contain but little of Cochin China, and to that of A. malaccensis
j'soaloin, Jafferabad none, whilst that from (Lam.) of tropical Asia. Both are highly
Cura9ao contains a considerable proportion. fragrant and aromatic used in fumigations and
;
Uses. Chiefly in medicine and as a hop- pastilles, and occasionally by

cabinet-makers and
substitute. It has also been used as a source of inlayers.
certain dyeing materials (Ure, 1, 104 Preston,
;
The same name is applied to the resin. Of
Chem. Zentr. 1876, 390; Chem. Soc. Trans. all perfumes this is said to be the most esteemed
32, 378). Kayser (Chem. Tech. Report, 1876-80) by Orientals.
finds aloe colouring matters make certain aniline ALOIN 77. GLUCOSIDES.
dyes faster. ALOO BOKHARA, ALPOGADA, PAZHAM.
Properties and Reactions. Pure aloes is The Bokhara plum (Primus insititia (Linn.) \P.
soluble in ether and almost completely soluble bokhariensis], largely imported into Bombay.
in water, the solution
being coloured dark- brown Used as a laxative. The root is astringent ; the
by alkalis, black by ferric chloride, and grey by gum is used as a substitute for gum arabic under
lead acetate (Fliickiger). By adding a solution the name of Persian gum (Dymock, Pharm. J.
of copper sulphate or chloride to a solution of
[3] 9, 145).
aloes, an intense yellow-coloured solution is ALOUCHI RESIN v. AlucM resin, art. RESIN.
obtained, which, warmed
with potassium ALPHOL v. SYNTHETIC DRUGS.
bromide or chloride, turns to a deep-red and ALPINIA OFFICINARUM v. GALANGA ROOT.
102 ALPINIA OIL.
ALPINIA OIL. An essential oil obtained ALUMINATES v. ALUMINIUM.

from the leaves of Alpinia malaccensis ap.gr. ;
ALUMINIUM. Sym. Al. At. wt. 27-1.
1-02 at 26, rot. power +6-5. Consists mainly Occurrence. Aluminium is the most widely
of methyl cinnamate, together with d-pinene distributed element in nature with the exception
Proc. K. Acad. Wetensch. of oxygen and silicon. It is not found in the
(Van Romburgh,
Amsterdam, 1900, 3, 451). metallic state.
ALPININ v. GALANGA KOOT. As oxide, A1 2 3 aluminium is found in co-
,
ALPOGADA v. ALOO BOKHARA. rundum, or, coloured by metallic oxides, in

ALQUIFON. Black lead ore or Potters' ore. sapphire, ruby, emery, &c. The hydrated
A native lead sulphide, used by potters to glaze oxide A1 2 3 ,H 2 O occurs as diaspore, and, to-
coarse ware. gether with ferric oxide, silica, &c., as the
ALSOL v. SYNTHETIC DRUGS. important mineral bauxite.
ALSTONIA BARK. The bark of Alstonia Aluminium occurs in combination with
constricta (F. Muell.), an
apocynaceous tree oxygen and metals as aluminates, in spinel
It has a bitter taste,
in Australia. Al 2 O 3 -MgO, chrysoberyl Al 2 O 3 -BeO, gahnite
growing
slightly camphorous odour, contains
a neutral Al 2 O 3 -ZnO. As hydrated sulphate it is found in
bitter principle (similar to cailcedrin and aluminite or websterite A1 2 3 S0 3 ,9H 2 0, and as
tulucumin), a volatile oil smelling like alunogen A1 2 3 (S0 3 ) 3 ,18H 2 O ; as the double sul-
camphor, an iron-greening tannin, resin, fat, phate of aluminium and potassium in alumstone
wax, a protein-like substance, oxalic and citric or alunite ; and, as an efflorescence on aluminous
acids (Palm, J. 18G3, 615). minerals in the form of the alums of potassium,
Miiller and Rummel (Chem. Soc. Trans. 35, sodium, ammonium, &c.
31) obtained a yellow substance to which they Aluminium occurs principally, however, as
gave the name alstonine. Oberlin and Schlag- silicate in the various clays ; as silicate contain-
denhauffen (Pharm. J. [3] 10, 1059; Chem. ing silicon fluoride in the topaz and, as double
;
Soc. Abstr. 38, 127) showed that this body with iron, magnesia, lime, &c., in
silicate,
consisted of two compounds alstonine and garnets with potassium, sodium, magnesium,
;
alstonicine, the former being soluble in acids and calcium in immense quantities in the
with fluorescence, the latter without. varieties of felspar.
Hesse subsequently (Ber. 14, 264 ; Annalen, As double fluoride of aluminium and sodium
205, 360) isolated : it is found in cryolite Al 2 F g -6NaF ; as hydrated
Alstonine (chlorogenine) C 20 H 21 N,0 4 a brown ,
phosphate in the turquoise and in wavellite, and
amorphous mass, a strong base, soluble in chloro- as borate in a crystalline mineral occurring in
form, alcohol, and sparingly soluble in ether, and Siberia.
melting when anhydrous at 195 (uncorr.) Although present in such quantities in the
Porphyrine C 21 H 25 N 3 2 a white powder
, soil, aluminium is not usually considered a
melting at 97 (uncorr. ), soluble in alcohol, chlo- constituent of the ash of plants except of cryp-
roform, ether, and acids, with blue fluorescence. togams ; Yoshida, however (Chem. Soc. Trans.
Porphyrosine, soluble in acetic acid, forming 1887, 748), has found it in a number of phanero-
a pink solution. gams in Japan.
Alstonidine, colourless needles, melting at History. The name of this metal is derived
181 (uncorr.), soluble in chloroform, ether, from alumen, a term applied by the Romans to
alcohol,and acetone. all bodies of an astringent taste. Pott, in 1746,
Hesse, however, could not find a trace of stated that the basis of alum is an argillaceous
quinine (Ber. 11, 1546, 1753). earth ; and in 1754 Marggraf pointed out the
ALSTONIA SPECTABILIS. PoeUbark. Con- distinction between alumina and lime, and its
tains alstonatnine (Hesse, Ber. 11, 1548), and presence in combination with silica in clay.
the alkaloids of dita bark. It contains six Davy, in 1807, having isolated the alkali
times as much echitammonium hydroxide as metals by electricity, endeavoured, unsuccess-
dita bark (Hesse, Annalen, 203, 144). fully., to reduce alumina in the same manner.
Its physiological action is like that of curare. Oersted, in 1824, prepared aluminium chloride
ALSTONITE. A
rare mineral consisting of by passing chlorine over a mixture of alumina
barium and calcium carbonate (Ba,Ca)CO 3 , and carbon heated to redness. He appears to
crystallising in the orthorhombic system. The have reduced the chloride to the metallic condi-
small crystals have the form of acute six-sided tion by heating with potassium amalgam :
pyramids, and consist of complex twin inter- (Berzelius, Jahresb. 1827,[6] 118). The amalgam
growths. Found in 1834 in a lead- and zinc- produced oxidised rapidly in the air, and left, on
mine near Alston in Cumberland, and in 1909 volatilising the potassium, a tin-white metal.
in a coal-mine near Durham. L. J. S. Wohler, in 1827 (Annalen, 1828, 37, 66),
ALTI. Indian name for a root used at Goa having failed to procure the metal by Oersted's
as a substitute for Althaea (Dymock, Pharm. J. method, obtained it by the decomposition of the
[3] 8, 101). anhydrous chloride with potassium, as a grey
ALUDEL. The aludels of the earlier chemists powder, which became brilliant under the
were pear-shaped pots generally made of earthen- burnisher.
ware, but sometimes of glass, open at both ends. Bunsen and Deville, in 1854, independently,
Each aludel had a short neck at the top and obtained the metal by electrolysis of the fused
bottom, so that a series of them could be fitted chloride. Deville, in the same year, much sim-
together by means of the necks. The earthen- plified the manufacture by substituting sodium
ware pear-shaped vessels in which the mercurial for the more expensive potassium. In 1854
vapours are condensed at Almaden in Spain are he was installed in the manufactory of Javel
also known as aludels. by the Emperor Napoleon III., and supplied
ALUM v. ALUMINIUM! with the necessary apparatus for experiments
ALUMINIUM. 103
on the large Afterwards his process was

scale. that have been made to prepare the metal
by the
removed to Nanterre and finally to Salindres. action of the usual reducing agents, such as
A description of his method is given in Ann. carbon, hydrogen, or hydrocarbons, have met
Chem. Phys. [3] 43, 5-36, and specimens of the with so little success. The heat of formation
metal produced were shown at the Paris Exhibi- of these compounds is an index to their
stability,
tion of 1855. and may be taken as a measure of the
energy
Shortly after the publication of these results, requisite for the isolation of the aluminium.
Messrs. Dick and Smith, under the direction of The operation is not likely to succeed unless
Dr. Percy, prepared aluminium by the action of the elements which become separated from the
sodium on the then newly discovered mineral aluminium enter into new combinations of still
some of the product being shown by
cryolite, greater stability. The nature of the changes
Faraday at the Royal Institution in March, 1855 that might be expected to take place
may be
(Phil. Mag. 10, 365). expressed in the following equations :
About sixmonths subsequently, Rose, inde- 2A1 2 O 3 + 3C4A1 = 3CO, +

pendently, prepared it in the same manner, and or A1 2 O 3 + 3C2A1 = SCO +
published his results in an extended article in A1 2 3 + 6H =
2A1 + 3H 2
P. 96, 152 (Phil. Mag. 10, 233). A1 2 3 + 6Na =
2A1 -f 3Na 2
Deville at once turned his attention to this A1 2 C1 8 + 6H =
2A1 + 6HC1
process (Ann. Chim. Phys. [3] 46, 451) ; but on A1 2 C1 6 + 6Na =
2A1 + 6NaCl
account of the impurity of the metal produced, A1 2 F 6 + 6Na
2A1 = 6NaF. +
he preferred the double chloride of aluminium In order that there may be a likelihood of
and sodium, using cryolite as a flux only. these reactions occurring, the heat arising from
The first manufactory in England was started the formation of the compounds on the right
at Battersea, London, in 1859, by F. W. Gerherd. hand should exceed the heat concerned in the
Some of his metal was shown at the Society of
decomposition of the aluminium compounds on
Arts Exhibition in 1860. Messrs. Bell, of New- the The show how
left. following table will far
castle, also prepared aluminium and aluminium this is the case :
bronze in 1863, using Netto's process. A mixture

of 200 Ibs. of cryolite and an equal weight of
common salt was brought to fusion, and 40 Ibs.
of sodium gradually added. The charge thus
contained only 5 p.c. of aluminium, but less than
half of this was obtained in the yield.
The manufacture ceased in 1874. In
Grabau's process (J. Soc. Chem. Ind. 1891,
433) aluminium fluoride was subjected, to the
action of metallic sodium. Other modifica-
tions were proposed from time to time, but
the production of aluminium made no notable
advance. Weldon, in 1883, summed up the
position of the industry in the statement that
the only method known for the manufacture
'
of aluminium is Deville's. M. Pechiney has

improved and cheapened the modes of working,
and the appliances for carrying that method into
effect, but this is all the progress which has been
made in the manufacture of aluminium during
the last five and twenty years.'
When the great stability of the available
compounds cdhtaining aluminium is considered,
it is not to be wondered at that the many attempts
104 ALUMINIUM.
be prepared by the method adopted by him integrated under the intense heat. For a non-
in his determination of the atomic weight of conducting furnace lining, fine particles of
that element (Phil. Trans. 171, 1018). Ordinary charcoal are washed in lime-water, exposed to
commercial aluminium is converted into bromide the air and dried. They thus become coated
by the direct action of bromine. On account with lime and are of good insulating power.
of the violence of the action, the metal should At the high temperature produced, ordinary
be immersed only for a short time, at intervals, charcoal becomes converted into graphite and
until dissolved, or should be added in very forms a good conductor. The two electrodes
small pieces. The bromide
so produced is freed being within a few inches of one another, the
from bromine by and fractionally
distillation charge of twenty-five parts of corundum, twelve
distilled, that portion boiling uniformly at parts of carbon, and fifty parts of granulated
2(53 -3 being reserved. This portion is colour- copper is placed around and between them,
less, entirely soluble in water, and consists of covered with small lumps of charcoal, and the
the pure bromide. whole covered with an iron top lined with fire-
It is heated with sodium (which has been brick. The current from a powerful dynamo is
carefully freed from oil and well scraped) in a then passed, and the electrodes moved if
crucible made of a mixture of pure alumina and necessary to produce the requisite resistance.
sodium aluminate. The amount of sodium In about ten minutes, the copper having melted
used should not be sufficient to reduce the between the electrodes, the distance between
whole of the bromide, or the aluminium is them is increased while the current is raised to
liable to contain sodium. The globules of 300 amperes of fifty volts E.M.F. and the
metal are fused together before the blowpipe yield 1 Ib. per E.P.H. hour. As the resistance is
on a bed of alumina, immersed for a short time increased, the temperature rises, the alumina
in hydrochloric acid, washed and dried. Pure is reduced to the metallic condition and
aluminium might also be produced by the elec- alloys with the copper, while its oxygen forms
trolysis of the pure bromide or chloride. carbon monoxide and burns at the openings
The purification from metallic impurities on in the cover with a white flame. After
the large scale involves many difficulties. The about five hours the operation is completed.
only method of obtaining satisfactory metal is The alloy produced is brittle, consisting of
to ensure as high a state of purity as possible copper and 15 p.c. or upwards of aluminium.
in the first instance by making use of selected When boron or silicon oxides have been added,
materials and avoiding contamination in the the bronzes produced contain these elements.
process of manufacture. It is melted, cast into ingots, the percentage of
By the establishment of Deville's process aluminium determined, and sufficient copper
the price of aluminium had been brought down '
added to produce aluminium bronze,' or the
from 181. per Ib. to 11., at which it stood till required alloy.
1887. When other metals, such as iron, nickel,
The double
chloride of sodium and aluminium silver, &c., are substituted for copper, corre-
used contained only 14 p.c. of aluminium, and sponding alloys are produced.
the working of large charges with a small yield The slag produced is hard and compact, but
together with the high cost of sodium and fuel soon falls to a fine alkaline powder ; it contains
stood in the way of any prospect of reduction alumina, calcium aluminate, with traces of
in the price of the metal.
copper, silicon, &c.
The introduction of Castiier's process, by Pure aluminium cannot be produced satis-
which sodium could be produced much more factorily by this method, as it remains, to a great
cheaply, led to the establishment of the Alu- extent, mingled with the carbon.
minium Company's works at Oldbury, and See further, W. P. Thompson (J. Soc. Chem.
some reduction in the price of alu-
effected Ind. 1886, 206) ;Mabery (Amer. J. Sci. 308,
minium. Meanwhile Messrs. Cowles (Patents and Amer. Chem. J. 1887, 11).
Aug. 18, 1885, and Jan. 26, 1886) brought The Electrical Process. A new principle was,
electrical heating into operation, and,
though however, introduced into metallurgy, and the
their process was not adapted to the production
application of electricity for purposes of heating
of aluminium, it was capable of and reduction of metals has made rapid pro-
furnishing alloys
of aluminium with copper and other metals.
gress in recent years. Its full development
These could be made at one-tenth the price had not, however, been reached in the pro-
which had ruled for aluminium, and the valuable cess just described. It had been shown that,
properties of aluminium bronze, Hercules metal, though the fusion of a substance like alumina
and other alloys were soon recognised. More- could not be economically effected owing to its
over, the discovery of the effect of the addition high resistance, the addition of copper and other
of minute amounts of aluminium to iron and metals enabled the furnace charge to conduct
steel gave a further stimulus to the the current. If a suitable solvent could be
production
of aluminium. 0. W. Siemens had already found for alumina then the electrolytic action
described an electric furnace (1881) capable of of the current could be
brought into play.
giving very high temperatures, and the type of When this was accomplished the chemical
furnace patented by Messrs Cowles 5ros. was method of decomposition would give place to
based on similar lines. the electrolytic method, and the isolation of
The furnace is a rectangular box, one foot aluminium become a question of a sufficient
wide, five feet long, and fifteen inches deep, all current at the necessary voltage. This voltage
inside measures. Two carbon electrodes pass can readily be calculated from the heat of forma-
through pipes in the ends ; they are three inches tion of the compound in question by dividing
in diameter and thirty inches this size the number of calories per equivalent by 23,250.
long ;
could not be exceeded, as larger carbons dis- We thus obtain for alumina 2-81 volts, for
ALUMINIUM. 105
aluminium chloride 2-32 volts, for aluminium coal could notcompete with cheap water power
fluoride 4-00 volts, for aluminium sulphide 0-9 in this industry,and rapid expansions of the
volt, industry were made. The price had by 1891
A suitable solvent is found in native cryolite been brought down to one-fifth of that which
3NaF-AlF 3 which may be brought to fusion
,
had ruled under Deville's process, and the
below 1000, and will dissolve 15 to 20 p.c. of production had increased to over 300 tons per
its weight of alumina, and in this condition it is annum. The accompanying statement is the
likely that the voltage is somewhat lower in cost of production at this period, as
given by
the case of alumina about 2-3 volts. A. E. Hunt (Eng. and Mining Journ. 1891, 280).
In the year 1886 the He'roult process was For 1 Ib. of aluminium there was requisite
patented and soon came into use at Neuhausen, 2 Ibs. alumina costing 6 cents
and at the Societe Electrometallurgique at 1 Ib. carbon electrode ,, 2
Froges, near Grenoble. In this process the Chemicals, pots, &c. 1
anodes consisted of carbon and the cathode 22 E.H.P one hour 5
was the carbon lining of the furnace, the distance Labour, interest, repairs ,, 5
between the anode and cathode being capable making 19 cents in all.
of adjustment by raising or lowering the anode. The following firms were at this period
The cryolite was melted in the bath by
first manufacturing either aluminium or its alloys :
utilising the heat generated by the resistance In England

to the electric current, and then alumina was Cowles Syndicate (Cowles process)..
added, and the additions continued from time Reduction Syndicate (Hall process).
to time as the bath became exhausted. The In the United States
metallic aluminium settled at the bottom of the Pittsburg Reduction Company.
bath in the neighbourhood of the cathode, and Cowles Electric Smelting Company.
was tapped every 24 hours. United States Aluminium Metal Co.
The purity of the metal at first was 97-99 On the Continent
p.c. There were at disposal 360 kilowatts at Societe Electrometallurgique at Froges.
Froges, and just over 1000 kilowatts at Neu- Aluminium Industrie Actien-Gesellschaft
hausen (J. Soc. Chem. Ind. 1892, 910) ; the |
at Neuhausen.
yield usually obtained was about 1J Ibs. of Further progress was mainly in the direction
aluminium per kilowatt-day, an efficiency of less of increasing the yield and bringing down the
than 25 p.c. cost of production whilst perfecting the various
The Hall process, brought out in the United details of the process so that a purer product
States about the same time, only differed from could be made.
Heroult's in matters of detail, the anodes being We shall now describe the further development
rods of "carbon 3 inches in diameter, or of larger of the industry and the manufacture as it stands
dimensions in sections banded together, the elec- to-day after over 20 years of experience ; and in
trolyte being alumina dissolved in mixed fluorides doing so it will be well to consider in greater
of calcium and aluminium or AlF 3 -NaF. detail (a) the production of alumina, (b) the
Minet (Compt. rend.. 112, 231) used a bath making of the carbon electrodes, (c) the nature
composed of 62-5 p.c. of common salt and 37-5 and arrangement of plant, including the reduc-
p.c. of cryolite, but his metal seems to have tion furnaces.
contained 2 to 3 p.c. of impurity, which was Development of the Aluminium Industry.
chiefly silicon, owing largely to the impurity of The factory established on electrical lines
first
the alumina used by him. Aluminium so pre- was that started in 1888, at New Kensington,
pared was liable to contain sodium, owing to by the Pittsburg Company, which is now known'
the fact that the voltage necessary for the as the Aluminium Company of America, and
decomposition of aluminium fluoride differed so conducts operations at the Niagara Falls, the
little from that required to decompose sodium Shawingian Falls, and at Massena.
fluoride viz. 4-7 as against 4. Amongst the pioneers of the industry were
There was added to the bath as the operation also (1) Aluminium Industrie Aktien-Gesellschaft,
proceeded, a mixture of hydrated alumina, cry- who control works at Neuhausen, Rheinfelden,
olite, and alumina dissolved in cryqlite. and Lend Gastein (2) the British Aluminium
;
Kleiner invented a furnace for the decomposi- Company, with reduction works operating in
tion of cryolite, and carried on the production 1896 at Foyers and now at Kinlochleven (Argyll-
of aluminium at Tyldesley in Lancashire ; a shire),and branch works at Greenock, Larne,
plant was also operated on the lines of the and Milton (Staffordshire), this company is
Heroult system at Patricroft near Manchester. also associated witli reduction works at Stang-
In this case the dynamos were run by steam fiord(Norway), and projected works at Orsieres
power, and it soon became manifest that this (Switzerland) ; (3) Societe Electrometallurgique
could not compete with advantageous supplies Fran9aise at Froges, La Praz, and St. Michael,
of water power which began to be called into and the Cie. des Produits Chimiques d'Alais et
requisition wherever such power was available. de la Carmargue.
Mention should also be made of the method of There are also works on a smaller scale
Bucherer, D. R. P. 63995 (1892), who prepared under the Aluminium Corporation at Wallsencl,
aluminium by electrolysing the double sulphide with construction going on at Dolgarrog (N.
of aluminium and an alkali or alkaline earth, Wales), the Anglo-Norwegian Company at
the chief obstacle to success being the expense Vigeland Falls (Norway), and developments in
and difficulty attending the production of the Italy at Bussi. The cost of production of the
sulphide. metal to-day is said to be 611. per ton as a
It soon became evident that the Hall and minimum, though at most works it would reach
Heroult process must hold the field, and that 801. (Mining World, June 26, 1909).
106 ALUMINIUM.
The market price of aluminium ingots in a b
1902^4 was 120Z. per ton, but it rose to 2001. in 1893 154. 870 .
1894 250 1491

1906, and has since then fallen to 657. (1909), . . . .
417 1835
though it is now again advancing. Since 1902 1895 . . . .
no trustworthy record has been made of the !

1896 . 591 . .2250 .
world's output of aluminium. It remained, 1897 . 1814 .

. . 5220
however, fairly stationary in the neighbourhood 1898 . 2359 . ..6860
of 8000 tons from 1900 to 1905 inclusive, and 1899 . 2948 .
. 8950 .
since then has grown steadily, and may be The Production of Alumina. The raw
estimated for 1909 at 30,000 tons. In the material from which the alumina is usually
United States Geological Survey publications made is bauxite, deposits of which occur at
(Metallic Products) for 1908 there may be found Beaux and in the Var (S. France), at Feistritz
the estimated consumption of metal in the United (Austria), Wochein (Styria), Irish Hill (Ireland),
States, from which it appears that in 1907 this Georgia, Arkansas, Alabama (United States),
amounted to nearly 7700 tons, and in 1908 to and in New South Wales. The physical condi-
nearly 5000 tons. tion of the bauxite varies considerably, so that
The following is a statement of the produc- some kinds are more readily acted upon for the
tion of aluminium in metric tons from 1889 to production of alumina than others. In the alu-
1899, (a) in the United States, (b) total out- minium industry a low content of iron and silica
put : is desired, especially the latter it is therefore
;
a b
usually found advantageous to employ the red
1889 . 22 . .93 bauxites, the white bauxites being used prefer-
1890 . 28 . .193 ably in the manufacture of sulphate of alumina.
1891 . . 68 . .302 The following table gives the composition of
1892 118 505 typical samples ;
Locality Beaux
A1 2 3
Fe 2 3
Si0 2
H 2
TiCK
ALUMINIUM. 107
condition for use in the reduction furnaces it amount of silicon in the metal will be that
must be calcined at 1100-! 200, so that it contained in 0-8 p.c. of silica, i.e. 0-37
p.c.
shows no tendency to give up moisture when The electrical resistance is in microhms per
used in the furnace or to absorb moisture when cubic inch of
1000
exposed to air.
The alumina of to-day is superior to that of Amorphous carbon (pressed) 1-63 1-45
fifteen years ago, and the cost of production Graphitic carbon . . 0-42 0-25
It constitutes, however,
Electrodes for aluminium 3-00 2-60
less than one-half.
.
about one- fifth of the whole cost of manufacture The resistance per cubic centimetre would be
of aluminium, and many processes have been 2-54 times these values. (For further detail, The
or
brought forward with a view to improve Electric Furnace, Stansfiekl, or the
pamphlet
be men-
cheapen the product. Of these may issued by the Acheson Graphite Co.,
may be
tioned the patents of Penokoff (Erg. Pat. consulted. ) In addition to low resistance to the
Nov. 19, 1895, Mar. 18 and May 13, 1896, &c.). electrical current, it is desirable that electrodes
Endeavours have been made to obtain alumina should be of low conductivity for heat, that they
of sufficient purity from bauxite, clay, felspar, or should be sufficiently hard and resistant to
kaolin by electrically heating them with iron (or superficial oxidation, of low porosity and of even
its oxide), carbon and cryolite, thus separating character throughout their whole mass.
ferrosilicon from alumina ; Moldenhauer ( J, To produce electrodes having these qualities
Soc. Chem. Ind. 1909, 148), Sinding-Larsen the material (oil-coke is largely used) must be
(ibid. 1908, 409), and Tone (Electrochem. and carefully selected, ground, calcined, and sub-
Metallurg. Ind. 1909, 35), Hall (J. Soc. Chem. jected to high pressure with the admixture of
Ind. 1902, 49). Recently Serpek has proposed tar or other material to act as binder.
They are
to prepare alumina by forming the carbide and then baked at a temperature of about 1200.
in a kiln, in principle
acting upon this with producer gas consisting resembling a pottery kiln,
of 77 p.c. nitrogen, 23 p.c. carbon monoxide, the surface of the blocks being protected from
and a little carbon dioxide. He claims that a oxidation by being embedded in carbon. The
tolerably pure nitride of aluminium is formed, permissible current-density for good electrodes
and this decomposed by steam yields alumina of this type is 25 to 60 amperes per square inch
and ammonia (Journal du Four Electrique, of transverse section, though in practice a milch
315, 1 J. Soc. Chem. Ind. 1911, 26
;
Fr. Pat. ; lower current-density is employed. For further
4057 12 and 418059). details and description of Mendheim and other
The Making of Carbon Electrodes. Bitumi- kilns suitable for baking the blocks, reference
nous coal, anthracite, retort carbon, natural or may be made to Die Kiinstlichen Kohlen, by
artificialgraphites, soot and oil-coke are all Julius Zellner. The connection of the carbon
materials which have from time to time been blocks with the anode beam carrying the current
used in the production of carbon electrodes. In may be effected by means of an iron claw let
deciding which of these materials should be into the block or a copper hanger fitted into it
used, account must be taken of : (a) Supply by a screw contact.
and cost of raw material ; (b) ash content ; The Reduction Furnaces. These consist
(c) amount of volatile matter and sulphur; essentially of an iron casing lined with car-
(d) conductivity for electricity and heat. It bon, the general character and arrangement of
must also be understood that electrodes used which is shown in transverse section (p. 108). The
for the production of aluminium differ in electrodes vary in size and form in different
character from those used for lighting or for works, and are not necessarily arranged in two
the production of calcium carbide and many rows as indicated in the figure. Their total
other purposes where graphitisation of the sectional area is, however, always adapted to
carbon is an advantage and the presence of the current to be used and good electrodes will
mineral matter is quite permissible and even act satisfactorily under a current-density of 8
necessary. The graphitisation of amorphous to 10 amperes to the square inch. The lower
carbon indeed effected by exposing it to a
is part of the carbon body serves as the cathode,
high temperature under electrical heating after and a special form of cathode is let into the
admixture with finely divided iron. carbon at the base of the furnace. In starting
It is said that at the temperature employed a furnace it is usual to introduce first the cryolite,
the iron volatilises. Be this as it may, the ash which is brought to a state of fusion by electrical
of such carbon contains a considerable amount heating. Alumina is then fed in gradually at the
of oxide of iron. Aluminium, boron, silicon, surface of the cryolite, and as it dissolves the
and other elements which form carbides can be resistance gradually falls to about 5 or 6 volts,
used as graphitising agents, as also to some and the temperature of the bath will be
extent the oxides of these elements. generally 1000. The electrolytic action brings
It may be taken that, so far as it is capable about a decomposition, which has been usually
of reduction in the aluminium furnace, the taken to result in the formation of carbon
mineral ash contained in the carbon alloys monoxide, according to the equation
A1 2 3 + 3C = 2A1 + 3CO,
itself with the aluminium, as also the foreign
matter present in the alumina. The amount of
alumina used should be about double that of but there doubt that primarily carbon
is little
the aluminium resulting therefrom, and the dioxide is formed, and the change should be
electrode consumption about two-thirds of the
expressed as
aluminium, so that an estimate may be made =
of the impurity as silicon contained in the
2A1 2 3 + 3C 4A1 + 3C0 2 .
metal. Assuming the silica in the alumina and In the former case the carbon used would
in the electrode as 0-3
p.c., in each case, the be two-thirds of the weight of the aluminium
108 ALUMINIUM.
produced, whilst in the latter it would be one- conductivity of aluminium, taking copper as
third. In practice the ratio of carbon to alumi- 100, is as follows 98-5 p.c. purity, 55
: 99 p.c-., ;
nium lies between these extremes. 59 99-5 p.c., 61

;
100 p.c., 66.
;
A
sample of metal produced in1856, having
a lower degree of purity, gave 51-3.
Its elasticity modulus (i.e. load in kilogrammes
per square millimetre, divided by its alteration
in length) is 7462 as compared with 11,350 for
copper, and the torsion moduli of these

metals
are 3350 and 4450 respectively.
The specific gravity of the molten metal
is 2-54, and of the cast metal is about
2-66 ; this may be increased by rolling. Its
expansion coefficient is 0-00002313 at 40
(Fizeau), and 0-0000315 at 600. It expands
on fusion to the extent of 4-8 p.c. (Toepler).
In hardness it resembles silver, and the pure
metal is softer than the impure. It becomes
more elastic and also harder by hammering and
rolling, andcapable of being drawn down to a
is
wire of ^
inch in thickness, or rolled into plate
It can
or beaten into foil to ^^
inch thick.
also be finely granulated for use in explosives, or
prepared in the form of very fine powder, which
'
is largely emplo3 ed as thermite,' or as aluminium
r
paint. The strength of aluminium is

tensile
12 to 13 tons on the square inch, but this varies
with the temper of the metal between 6J and
15| tons on the square inch, the elongation
varying in the inverse manner from 23 p.c. to
1 p.c. Aluminium has been largely used for
overhead electrical transmission and it possesses
many advantages for such purposes owing to3 its
lightness. Its specific gravity being only T B of
that of copper, and conductivity over 60 p.c.,
The production of aluminium is discon-
it follows that an aluminium cable has double the
tinuous, for about 2 hours after the proper
efficiency of a copper cable of the same weight
charge of alumina has been added the voltage as a means of conveying current. The tensile
of the furnace rises rapidly and affords an
indication that more alumina must be added. strength of aluminium is affected, of course, by
its form, method of casting and mechanical
The aluminium collects at the bottom of the treatment. Its ultimate strength in tons per
bath of electrolyte, and is tapped off at stated
square inch is in castings 7 tons, in sheet 11
periods, either every day or at longer intervals. tons, and in wire from 13 to 29 tons.
The reduction of alumina by electrolytic methods
on a laboratory scale is beset with difficulties ; Although corroded in the atmosphere of
some large towns, it is not more so than other
an account of experiences in this direction ia
metals used for cables, and under ordinary
given in papers by Neumann and Olsen (Met. circumstances it merely becomes coated with a
and Chem. Engineering, 1910, 185), and Tucker
thin film of oxide which acts protectively.
(ibid. 1909, 315). There has been great difficulty in finding a
Physical Properties. Commercial aluminium
is a metal with the whiteness of tin. It has wholly satisfactory solder for the metal, and one
that shall resist corrosion. Dagger (J. Chem.
been obtained in crystals resembling octahedra,
Soc. Ind. 1891, 436) quotes as useful for heavy
and is very slightly magnetic.
Its specific heat is, at soldering Al 12 pts. Cu 8 pts. Zn 80 pts., and for
light soldering Al 6 pts. Cu 4 pts. Zn 90 pts.
-100 0-1893 300 0-2434 Joints can, however, be made by autogenous
0-2098 500" 0-2739
welding with an oxyhydrogen or acetylene flame
100 0-2236 650 0-3200 or electrically. Butt and other joints may be,
(Schmitz, Proc. Roy. Soc. 72,177). effected by various mechanical devices with the
The total heat required to bring a kilogramme aid of fusion at the surfaces or by a casting of
of aluminium from to 625 is 239,400 metal around the junctions.
cals., and its latent heat of fusion is 80. It Chemical Properties.- Aluminium absorbs
melts at 654-5 (Heycock and Neville), 657-3 about its own volume of hydrogen, which is,
(Holborn and Day), the melting-point being however, expelled on heating or in vacud. It
dependent (as are other physical properties) on is practically unacted upon by oxygen at or-
its purity. Small amounts of silicon and iron, dinary temperatures, but if finely divided it
which are always present, have a considerable undergoes considerable oxidation at 400, or
effect on its behaviour, both pl^sically and in even, though less rapidly, at lower temperatures.
contact with reagents. Lorenz found its If of sufficient purity, water has no action upon
conductivity for heat at 0-3435, at 100 it, though when sodium is present in the metal
0-3619; whilst Jaeger and Dresselhorst for metal a slight action occurs. This is accentuated if
containing 0-5 p.c. iron and 0-4 p.c. copper, copper, brass, or other metals are in contact
found 0-4923 at 100. Similarly the electrical with it. A recent use to which the metal has
ALUMINIUM. 109
put is for the treatment of hard waters, frosted appearance. This is produced by plung-
which by intimate contact with the metal, are ing the article momentarily into caustic alkali,
said to be softened and become less liable to washing well, and immersing in dilute nitric
form incrustation on the shell of the boiler. acid.
The halogen elements or acids readily act upon Action on metallic solutions. Aluminium,
aluminium, and the chemical activity of the especially in the form of foil, has a considerable
metal is such that a large amount of heat is action on many salts in solution. The action of
generated on combination with these elements. sulphates and nitrates is usually very slow. All
The heat of formation of A1 2 3 is 391,600 cals., chlorides, except those of the alkalis and alka-
AljjSa is 124,400 cals., A1 2 F 6 is 558,000 cals.,
line earths, are readily decomposed, even alu-
AU i g is 323,600 cals., Al 2 Br 6 is 243,900 cals., minium chloride solution dissolves the metal
AL1 6 is 140, 600 cals. with evolution of hydrogen. Bromides and
The very great affinity which aluminium iodides have corresponding effects. The pre-
possesses for oxygen has been made use of in sence of chlorides in solutions of other salts
the application of
'
thermite
'
as a means of much facilitates their action.
ivi hieing oxides. Goldschmidt, D. R. P. 96317 From a neutral or feebly acid solution of
(1895), has thus used the finely divided metal in silver nitrate, silver precipitated slowly ; from
is
the production of iron, manganese, chromium, an ammoniacal solution of the chloride, silver is
nickel, cobalt, titanium, boron, molybdenum, rapidly precipitated as a crystalline powder.
tungsten, vanadium, and other metals. From the nitrate or sulphate of copper, pre-
Reagents which readily part with the cipitation is slow, from the acetate quicker,
halogens, such as SiCl 4 and PC1 3 , also attack it, and from the chloride or other salt in presence
and carbon or the oxides of carbon at high of sodium chloride, rapid and complete.
temperatures convert it into carbide, A1 4 C 3 . Mercurous salts are decomposed with forma-
Concentrated nitric acid has very little action tion of an amalgam. Lead and zinc are readily
upon it unless the metal is impure, but more precipitated (v. also Cossa, Zeitsch. f. Chem.
dilute acid dissolves it appreciably. Sulphuric [2] 6, 380 and 443).
acid only reacts if hot and concentrated, and Action of dry salts and oxides. The action
in these circumstances there is a considerable of aluminium, when heated with certain salts
evolution of sulphur dioxide. Alkalis or the and oxides, is peculiar, and shows, especially at
hydroxides of the alkaline earths, especially high temperatures, the tendency of this metal to
baryta, attack the metal, and hence vessels used form aluminates.
for culinarypurposes will be corroded if brought It is not affected by potassium nitrate except
into contact with soda. Mallet (Chem. Soc. above a red heat it is then rapidly oxidised
;
Trans. 1876, 340) found that molten aluminium with formation of potassium aluminate. With
is acted upon by nitrogen with the formation alkaline carbonates combination takes place at
of nitride. a red heat with separation of carbon, and with
If brought into intimate contact with alkaline sulphate combination takes place sud-
mercury in presence of moisture, aluminium is denly at redness with explosive violence ; in both
readily converted into the hydroxide, and when cases aluminates are formed.
exposed to the vapour of mercury with access When finely divided aluminium is mixed
of air, it undergoes rapid oxidation. with oxide of copper, lead, or iron, combination
The action of organic acids on aluminium is takes place at a white heat only, with such vio-
inconsiderable. In presence, however, of sodium lence as frequently to shatter the crucible. In
chloride these acids have a slight solvent the case of lead and copper oxides, aluminates
action. Under like circumstances, tin and are produced, and with iron an alloy of iron and
copper would be much more affected, with the aluminium (Tissier).
production of injurious salts ; the salts of alu- When heated with silicates or borates, alu-
minium are, however, quite harmless, and are minium liberates silicon or boron, forming an
almost entirely precipitated and rendered in- aluminate with the base. Fused silver chloride
soluble on boiling. is reduced to metal ; zinc is reduced from its
Perspiration, being acid, has no apparent fused chloride, whilst magnesium chloride is
effect ; saliva, on account of
its slight alkalinity, not affected (Flavitzky, Ber. 6, 195). The vapour
acts very slowly. Aluminium tubes have been of mercuric chloride is reduced with such energy
used for insertion in the human by heated aluminium that the metal fuses.
body where
much purulent matter was present, without Detection. Compounds of aluminium, when
perceptible corrosion. heated, moistened with solution of cobalt
Aluminium when fused with potash or soda nitrate, and again strongly heated produce a
is unaffected even at a dull red heat, but the fine sky-blue colour (Thenard's blue, q.v., art.
superficial silicon isremoved ; metal so treated COBALT).
takes a good ' matt.' Aluminium compounds are usually colour-
Dry ammonia gas has no action ; solution of less. Silicates and other compounds insoluble
ammonia has a slight action upon the metal, in acids require to be finely powdered, mixed
converting it into hydrate, whilst a portion with 4 parts of sodium carbonate or fusion mix-
passes into solution. ture, and heated strongly in a platinum crucible.
Pure aluminium is less acted upon by most The aluminium, having thus become converted
reagents than the commercial metal (Mallet). into sodium aluminate, is dissolved out with
For burnishing and engraving aluminium, to
hydrochloric acid, evaporated to dryness
the ordinary media are unsuitable.
According render any dissolved silica insoluble, and treated
to Mourey and others, an emulsion of equal parts with dilute hydrochloric acid. The aluminium
of rum and olive oil is most satisfactory. The is then present as chloride.
finish of manufactured articles is
improved by a Aluminous solutions, on addition of an alkali,
110 ALUMINIUM.
give a white gelatinous precipitate of hydrate, be taken as a measure of the aluminium present.
soluble in excess of the precipitant and in acids. In these circumstances it is customary to
Ammonia produces the same precipitate, which determine the impurities and arrive at the
is only slightly soluble in excess, and is entirely amount of aluminium by difference.
reprecipitated on boiling off the excess of The impurities generally present in quantity
ammonia if sufficient ammonium chloride be are iron, silicon, and sometimes copper. Minute
present, amounts of sodium, carbon, and nitrogen are
Estimation.- Aluminium is always precipi- also contained in the metal, but these should not
tated as the hydrated oxide A1 2 3 ,3H 2 0. greatly affect the result unless when dealing
For this purpose the solution, which, in pre- with specially impure metal. Commercially,
sence of alkalis or alkaline earths, is mixed therefore, iron and silicon alone are usually
with excess of ammonium chloride, is treated estimated. For the iron, the metal is dis-
with a slight excess of ammonia, and the solu- solved in caustic soda, and this solution on
tion boiled until the free ammonia is expelled. acidulation with sulphuric acid yields sulphates
The hydrate, having thus become totally pre- of alumina and iron which redissolve in the acid,
cipitated, is filtered, well washed, dried
and whilst the presence of copper is indicated by the
heated in a platinium crucible, the heat being appearance of a black residue. The amount of
finally raised to bright redness for five minutes iron is finally determined by titration with
over the blowpipe. The weighed residue consists potassium permanganate. For the silicon, the
of anhydrous oxide, A1 2 3 and contains 53 p.c.
,
metal is digested with hydrochloric acid (in
of aluminium. The separation from other presence of nitric acid to avoid volatilisation of
metals is not difficult. The heavy metals may any silicon as chloride) forming a turbid solution
be precipitated from the acid solution by sulphu- owing to the separation of the silica. This is
retted hydrogen, leaving the aluminium in solu- then boiled down with sulphuric acid until white
tion, whilst the precipitation in presence of fumes of this acid appear. The aluminium and
ammonium chloride in excess separates it from iron salts are thus converted into sulphate, and
the alkalis and alkaline earths. From chro- redissolve on digestion with water, the silica
mium and iron the separation is less simple. being left in suspension.
Chromium may be separated as follows : The After nitration and washing, the silica is
precipitated oxides are dried, mixed with 2 strongly heated and weighed. Copper may be
parts potassium nitrate and 4 sodium carbonate estimated as sulphide, or the black residue above
and fused in a platinum crucible. Alkaline mentioned may be dissolved and the copper
chromate and aluminate are thus produced. estimated colorimetrically. If the amount of
The mass is digested with water and a small sodium is to be found, the metal must be dissolved
quantity of potassium chlorate and hydrochloric in nitric acid to which a little hydrochloric acid
acid are then added, and the solution is evapo- is added. The solution is boiled down to
rated to a syrup, with occasional addition of dryness and exposed to a dull red heat so long
potassium chlorate to destroy the excess of as red fumes appear. The residue is extracted
hydrochloric acid and prevent its reducing with water, care being taken finally to remove
action on the chromate. The aluminium in the all alumina or other metals precipitated by the
diluted solution is precipitated as above by ordinary reagents. Ultimately the sodium salt
ammonia, leaving the chromate in solution. remaining may be converted into sulphate and
For the separation from iron, the precipitated weighed as such. For fuller details a paper by
hydrated oxides are dissolved in the minimum Seligman and Willott may be consulted (Journ.
quantity of hydrochloric acid and treated with Inst. Metals, vol. iii. p. 138).
an excess of pure strong potassium hydroxide For general analytical details, the following
solution, boiled for a few minutes, diluted, sources of information may be consulted :
filtered, and well washed. The ferric oxide is Moissan (Compt. rend. 121, 851); Gouthiere
thus precipitated and separated from the soluble (Analyst, 21, 270) ; Jean (Rev. Chim. Indust. 8,
alumina. The solution and washings are acidi- 5). The better qualities of commercial metal
fied with hydrochloric acid and precipitated should not contain more than 0-5 p.c. of iron
by ammonia. On account of its solvent action and silicon together, nor more than 0-03 p.c. of
upon glass, the treatment with potash should sodium.
be performed in a porcelain dish, which is much Alloys. The addition of quite small quanti-
less attacked, or, preferably, in one of silver. ties of aluminium to certain metals (e.g. copper
Commercial Analysis of Aluminium. The and iron) has a profound effect in modifying the
direct determination of aluminium, constituting properties of these metals. Likewise the addi-
as it does usually over 99 p.c. of the metal under tion of small quantities of certain metals (e.g.
examination, presents many difficulties. It has Fe, Mn, Si, &c.) to aluminium effects con-
been proposed to estimate the aluminium by siderable change in the properties of this metal.
ascertaining the volume of hydrogen evolved on The addition of 0-1 p.c. of aluminium to copper
dissolving it in hydrochloric acid or the amount brings down its conductivity 23 p.c. ; the
of chloride formed, but the errors to which such addition of zinc, copper, nickel, iron, or man-
a determination is liable are too great to admit ganese to aluminium is accompanied by con-
of sufficient accuracy moreover, the impurities
; siderable augmentation of the tensile strength.
usually present give rise to corrections which The alloys of aluminium may be classified into
detract from the simplicity of the method and bronzes, casting alloys, and rolling alloys, accord-
complicate the result. The solution in caustic ing to then- properties. The true bronzes
soda is preferable to this, the iron and copper consist of copper and aluminium alone, but there
remaining as a black residue, but the silicon, in are many binary (and ternary) alloys which
part, at least, reacts with caustic soda, so that contain metals other than copper and yet suffi-
even in this case the hydrogen evolved cannot ciently resemble bronze to be classed along with
ALUMINIUM. Ill
it. The bronzes proper chiefly employed are

to 5 p.c. of aluminium
gold bronze, containing 3 ;
steel bronze, with 8-5 p.c. Al and some silicon ;
acid bronze, with 10 p.c. Al. The copper

bronzes, with 90, 92-5, 95 and 97-5 p.c. of copper,
are all good alloys, showing homogeneity and
freedom from crystallisation. They are of great
hardness and high tensile strength.
Such alloys possess very valuable properties,
the ultimate stress of the 90 p.c. alloy being
38 tons to the sq. inch, and they have the
further valuable property of being practically
noncorrodible by sea- water ; this property is
also shown very markedly by bronzes containing
manganese. These bronzes in hardness and
tensile strength compare favourably with the
best steel, and are similarly affected by temper-
ing. The alloys high in aluminium and low in
copper are also of great commercial value ; a
bronze with 4 p.c. copper by rolling and drawing
showed a steady increase in tensile strength
from 9-6 tons to 20 tons to the sq. inch.
A small percentage of manganese renders
these alloys more ductile without reducing their
ultimate stress, but large proportions of man-
ganese increase the strength and lessen the
ductility.
For further information reference may be
made to the eighth report Research
of the Alloys
Committee of the Inst. Mech. Engineers (Car-
penter and Edwards), and to the ninth report
(Rosenhain and Lantsberry), also to The Metal
Industry, 1909, 186 (Hiorns). The composition of
other bronzes used industrially is given in the
following table :
112 ALUMINIUM.
white, brittle, and crystalline. Aluminium con- hydride. The two inetals combine rapidly in
taining 10 p.c. of gold is white and hard. presence of alkalis. The amalgam may also be
The malleability of aluminium is not much produced by electrolysis of mercuric nitrate,
impaired by the addition of gold, silver, or tin, using a negative plate of aluminium dipping in
but the presence of iron, and especially of mercury. When aluminium is rubbed with
silicon, is very injurious. wash leather impregnated with mercury, com-
With aluminium unites in almost all
silicon bination occurs ; the surface rapidly oxidises and
proportions, either directly or by its action on becomes heated, with formation of concretions of
silicious materials ; for this reason the fusion alumina (Jehn and Hinze, Ber. 7, 1498).
or preparation of this metal should not be per- Alloys of bismuth with aluminium are hard
formed in any silicious crucible in presence of a and brittle. With antimony and lead aluminium
flux. The presence of silicon renders aluminium does not unite, although traces of lead are fre-
brittle and much permanent. The alloy
less quently present in commercial aluminium.
containing 10 p.c. silicon is grey and brittle. Sodium unites readily with aluminium. The
Wohler prepared an alloy containing 70 p.c. last traces of sodium are difficult to remove,
silicon, which still appeared metallic. especially, it is said, when the metal has been
With iron the alloys are of especial interest. reduced from cryolite. The alloys are easily
The presence of a small quantity of iron is very attacked by moisture, and burn in the air, with
injurious ; it renders the aluminium crystalline, oxidation both of the aluminium and sodium ;
and raises the melting-point. The alloy con- that containing 2 p.c. of sodium decomposes
taining 5 p.c. of iron is hard and brittle ;
with water with ease. The necessity of avoiding the
8 p.c. the alloy crystallises in needles, and on presence of sodium in the preparation of alu-
heating separates into a more liquid alloy con- minium is therefore obvious.
taining but little iron and a skeleton very rich Aluminium also unites with manganese ; with
in that metal. Michel (Annalen, 115, 102) has platinum it unites easily, forming fusible alloys.
prepared an alloy which crystallises in six-sided With boron aluminium combines in varying pro-
prisms, corresponding to Al 2 Fe. A beautifully portions.
'
'
The so-called adamantine and gra- ' '
crystalline substance having the composition phitic boron appear to be borides of aluminium
Al 4 Fe is often found in the neighbourhood of (Hampe, Annalen, 1876, 75 ; and Deville and
the cathode of a reduction furnace. Wohler, ibid. 1867, 268) (v. BORON).
The valuable properties imparted to iron and Mallet (Chem. Soc. Trans. 1876, ii. 350) has
steel by the presence of a small quantity of prepared a nitride of aluminium in small crystals
aluminium have long been known
'
Faraday
; hard enough to scratch glass.
(Quarterly Journ. Roy. Inst. 1819, 290) found For further information, see J. W. Richards,
from 0-013 to 0-069 p.c. of aluminium in certain Aluminium and its Alloys, London.
samples of Bombay wootz, though it has been Aluminium oxide, Alumina, Al.2 O 3 .
shown by Henry and others that this metal is Aluminium forms only one oxide, A1 2 3 ,
cor-
not always present. About the same time responding to and isomorphous with the ses-
S. B. Rogers showed the presence of aluminium quioxides of iron and chromium.
in some of the best quality of pig-iron made in This oxide occurs native, colourless as
South Wales, and found that a steel to which ;
hyaline, corundum ; or coloured by metallic
0-8 p.c. of aluminium had been added in the form oxides, as ruby, sapphire, oriental topaz, &c. (q.v. ).
of an alloy with iron, was rendered harder and Very impure, dark, and usually associated with
stronger and resembled the best wootz (Rogers, magnetite and haematite, it occurs in large
Metallurgy, 1858, 14). A superior steel was I
boulders in many districts, and is used as a
prepared by Sir Charles Knowles, which was i
grinding and polishing material in the form of

stated to owe its value to the use of kaolin and emery (q.v.). The native oxide crystallises in the
consequent introduction of aluminium into the rhombohedral system in hardness it comes
;
metal in its preparation (Mining Journal, 1859, next to the diamond. The finely coloured
118). specimens are used as gems. It occurs almost
Messrs. Cowles Bros, have exhibited a Sie- pure in considerable quantities in the AUeghanies
mens-Martin basic steel containing 0-2 p.c. j
in Northern Georgia.
aluminium, which welds with iron and shows no It may be prepared by the ignition of alu-
mark at the junction. minium foil in air or oxygen ; the oxide so pro-
The addition of aluminium to iron or steel duced is fused and as hard as corundum.
' '
for the production of mitis castings has been Amorphous alumina may be produced by
patented by P. Ostberg (Engineering, 1886, 360). ignition of the precipitated hydrate, pure alu-
Iron and steel, especially at temperatures far minium sulphate or ammonia alum ; in either'
above the melting-point, absorb considerable case alumina alone is left.
quantities of gas, which impairs the value of the It is white and soft, but becomes hard on
castings. The addition
of 0-05 or 0-1 p.c. of strong ignition. According to H. Rose (Pogg.
aluminium to the fused iron or steel lowers the Ann. 74, 430) the sp.gr. of the oxide after
melting-point, prevents the absorption of gas, heating over a spirit -lamp is 3-725 its density
;
and considerably increases the fluidity. The may be raised to 4, just about that of corundum
metal can then be easily cast. by heating in a porcelain furnace, but it still re-
Nickel and aluminium combine with incan- mains amorphous. It is remarkable that though
descence when heated together. The presence the density of the artificially prepared alumina
of under 3 p.c. of nickel lowers the melting-point is nearly 4, its bulk
density may be less than
and increases the hardness and elasticity. one-fifth of this. With a somewhat lower
Pure aluminium combines with mercury, al- density the bulk density is higher, but is still
though not readily, when the metals are heated such that it occupies a larger bulk than the
together in an inert gas such as carbonic an- same weight of water.
ALUMINIUM. 113
Whenheated by the oxyhydrogen blow-pipe, heated to redness with chalk,
forming sodium
alumina melts and crystallises ; the addition of aluminate and calcium fluoride :
chromium oxide or a chromate imparts a ruby

Al 2 F 6 -6NaF+6CaC0 3 =Al 2 (NaO) +6CaF 2 +6C0 2
colour to the crystals. 6
Fremy and Verneuil (Compt. rend. 1888, The mass produced is lixiviated with water and
566) have prepared artificial rubies by heating fitered. From this aluminate the
hydroxide is
to redness a mixture of barium fluoride and precipitated by carbon dioxide with formation
alumina containing a trace of potassium dichro- of sodium carbonate :
mate. The heat requires careful management.

Fine rubies are thus formed in a friable matrix
which may be separated by agitation with water. The hydroxide is usually made into aluminium
By former methods the matrix was hard and sulphate by solution in sulphuric acid, or it is
difficultto remove (Fremv and converted into alum.
Feil, Compt. An
rend. 1877, 1029, and 1887^, 737). crystals The entirely different process has been intro-
contain no barium, easily scratch the topaz, and duced by Sauerwein. The finely powdered cryolite
isboiled with milk of lime forming aluminate as
possess the form and properties of natural rubies ;
their crystalline form has been determined by before :
Descloiseaux (Compt. rend. 1888, 567). By the Al 2 F 6 -6NaF+6CaO=Al 2 (NaO) 6 +6CaF 2 .
addition of a little cobalt oxide before the fusion, For the conversion of the aluminate into oxide
sapphires may be produced. Sauerwein applies a peculiar property possessed
Alumina is soluble, when strongly heated, in
by that salt, which shows the readiness with
boric acid ; the latter may be driven off at a which alumina loses its acid properties and again
very high temperature, leaving crystalline becomes basic. Sodium aluminate, when mixed
alumina. By the addition of the proper oxide in equivalent proportions with any haloid salt of
the corresponding spinels may be produced,
aluminium, is decomposed the sodium combines
;
coloured by cobalt oxide (blue), chromium oxide with the halogen, while the whole of the alumi-
(red), iron oxide (black), (Ebelmen, Ann. Chim. nium is precipitated as hydroxide. On the large
Phys. 3, 22, 211 and 33, 34). Only two hydroxides scale the haloid salt used is cryolite. The finely
of aluminium are known, viz. : A1 2 3 ,H 2 O and
A1 2 3 ,3H 2 0. By Graham's method an aqueous powdered mineral is stirred into the clear liquid
from the previous operation, and the alumina
solution of the hydroxide may be obtained.
When the hydroxide is freshly precipitated precipitated as hydroxide :
Al 2 (NaO) 6 +Al 2 F 6 -6NaF+6H 2

it dissolves readily in dilute acids, but on
=2Al 2 (OH) 6 +12NaF.
standing, or after filtration, solution is more
difficult, and achieved by a mixture
is best, Sodium aluminate is a white, infusible,
of 8 parts of sulphuric acid and 3 parts of amorphous solid, easily soluble in both cold and
water. When heated, the hydroxide loses its hot water. The concentrated solution rapidly
water, undergoing a contraction of about 30 deposits alumina, leaving in solution a basic
p.c. in bulk as it passes into the form of the aluminate, which on evaporation is obtained as
anhydrous oxide. a fusible and hygroscopic mass. The addition
When boiled with water containing a drop of any acid at once decomposes it with precipita-
of a 1 p.c. solution of alizarin, the
hydroxide tion of alumina. This alumina is pure and free
assumes a bright red colour, not removed by a from alkali, which is never the case when alkaline
weak solution of acetic acid. precipitants have been used. It may be employed
This test easily distinguishes it from gelatin- as a mordant in dyeing and calico-printing, in
ous silica. Aluminium hydroxide possesses a an acid and not, as in the case of alum, an
powerful affinity for many organic substances, alkaline bath. For the production of lakes the
and enters into association with a large number colouring matter is mixed with the aluminate
of colouring matters,
precipitating them entirely solution and precipitated by the addition of sul-
as lakes. On this property depends the use of phuric acid. According to Morin these lakes
alum mordants (red liquor, &c.). They pre- are richer than those obtained from alum and are
cipitate the hydroxide upon the fibre of the produced at about one half the cost.
goods to be dyed, and this constitutes the Potassium aluminate A1 2 ? -3K 2 or Al,(KO) g
mordant or fixing agent which retains the colour. is obtained in hard glistening crystals when
Sodium aluminate Al 2 3 -3Na 2 O or Al 2 (NaO) 6 . alumina is fused with potash, the mass boiled
This salt is now prepared on a large scale, both in water and the solution evaporated in vacud.
to be used as such and as an intermediate
pro- Aluminium chloride A1 2 C1 6 This compound
.
duct in the preparation of the sulphate and other was first prepared in 1824 by Oersted, by passing
salts of aluminium. chlorine over a mixture of alumina and charcoal
Its formation
depends upon the property heated to redness. The method and apparatus
possessed by alumina of acting as an acid in pre- resemble that used in the preparation of the
sence of a powerful base. double chloride, omitting the sodium chloride.
Its preparation from bauxite has been de- According to P. Curie (Chem. News, 28, 307)
scribed on page 106. It may also be produced it may be easily prepared as follows: Anhy-
by passing a current of steam through a heated drous alumina, or, less satisfactorily, clay, is
mixture of bauxite and common salt, and by strongly heated in a tube
and subjected to a
strongly heating a mixture of bauxite, sodium current of hydrochloric acid impregnated with
sulphate, and carbon, but in the latter case its carbon disulphide by bubbling through that
purification from the sodium sulphide simul- liquid. Aluminium sulphide appears to be
taneously produced is difficult. It is also formed formed and at once decomposed by the hydro-
in the
preparation of soda from cryolite. Accord- chloric acid, yielding aluminium chloride and
ing to Thomsen's method, powdered cryolite is sulphuretted hydrogen. The condensed chloride
VOL. L T.
114 ALUMINIUM.
be freed from sulphur by distillation with of being lighter and melting at a lower tem-
may
iron filings. perature (J. Soc. Chem. Ind. 1890, 945). Natural
A solution of the chloride may be obtained cryolite occurs in quantity only in one locality,
in a large vein in the gneiss at Ivigtut in
by dissolving the hydroxide in hydrochloric acid.
The pure anhydrous chloride is a white, waxy, Greenland. Greenland cryolite has the following
crystalline solid ; in presence of a trace
of iron composition Al 13-2, Na 32-7, F 54-2, and small
:
it becomes yellowish. On heating, it volatilises quantities of manganese. The melting-point of

without fusion. If large pieces be quickly heated mixtures of cryolite and alumina is said to be
1000
they fuse and boil at 180 to 185 (Liebig). It Cryolite
With 3 p.c. A1 2 3 . 974
very hygroscopic, and evolves hydrochloric
.
is
acid on exposure to the air ; is easily soluble in 6 p.c. . . 960
water ; soluble in alcohol and ether. When 10 p.c. . . 980
15 p.c. 994
deposited from a solution in hydrochloric acid,
. .
it forms crystals of the formula A1 2 C1 6 ,12H 2 O. 20p.c. . . 1015

It absorbs ammonia and combines with (Chem. Soc. Abst. 1907, '469).
metallic chlorides, forming double chlor- It is a semi-transparent, white, crystalline,
many brittle solid, which melts at the edges in a candle
ides,the most important being that with sodium.
Aluminium chloride has been recommended by flame. Its hardness is 2-5 to 3 its sp.gr. 2-95.
;
Filsinger (Chem. Zentr. 10, 1270) for the preserva-

When impure it is frequently yellowish-red or
tion of wood, and by Saget (Chem. News. 45, 113) even black (v. CRYOLITE).
and others (J. Soc. Chem. Ind. 1882, 185 and Cryolite is used as a flux in the manufacture
of aluminium formerly for making salts of
230) for the production of a discharge on indigo ;
blue. An impure chloride containing calcium sodium and aluminium and for the manufac-
;
and sodium salts is stated to be largely used as a ture of an opaque, porcelain-like glass. It is
disinfectant under the name '
Chloralum.' I
also used for enamelling pans and as a glaze for
Double chloride of aluminium and sodium pots as replacing lead glaze.See further, Benzon,
(
Al.,Cl 6 ,2NaCl. This compound may bepro- (Hoffmann's Ber. Entw. Chem. Ind. [1] 660).)
duced by fusing together the proper proportions
Aluminium sulphide A1 2 S 3 may be "prepared
,
of aluminium and sodium chlorides. It is a by strongly heating a mixture of aluminium

colourless crystalline solid, melting at 185 and sulphur, or by heating alumina to bright
and redness in the vapour of carbon disulphide.
(Deville) volatilising at a red heat. It
is but much less so than It forms a yellow, glassy mass, which fuses
slightly hygroscopic,
aluminium chloride it is also more stable
;
with difficulty, and burns in air with produc-
and more satisfactory in use than that sub- tion of alumina and sulphur dioxide. It is at
stance, and gives up nearly the whole of its once decomposed by water. Houdard (Compt.
aluminium when reduced by sodium. rend. 1907, 801) found that by heating alu-
Aluminium bromide Al 2 Br g is most readily minium turnings and sulphides of manganese iron
prepared by the action of bromine on metallic and chromium in a carbon boat, sulphides related
aluminium. The action is violent, and the metal to the spinels are formed, of which he prepared
should only be added gradually. A lump of MnS,Al 2 S 3 FeS,Al 2 S 3 CrS,Al 2 S 3
, , .
aluminium weighing twenty grams becomes Aluminium carbide A1 4 C 3 may be obtained

strongly heated and even fused on being placed by the action of carbon or the oxides of carbon
in cold bromine (Mallet, Phil. Trans. 171, 1018). on alumina at very high temperatures, and often
It may also be prepared by the action of occurs in small quantity in the neighbourhood
bromine on a strongly heated mixture of alumina of the cathode of aluminium reduction furnaces
and carbon, and, in solution, by dissolving the in the form of a yellow powder ; it is formed
hydroxide in hydrobromic acid. It crystallises in when a mixture of alumina and carbon is sub-
colourless shining laminae, which melt at 93 mitted to a current of 300 amperes at 35 volts.
(Deville and Troost) and boil at 263-3 (at 747 It possesses the remarkable property of being
mm.) (Mallet). stable at high temperatures, and yet undergoing
Like the chloride, it forms a double bromide,
decomposition at a dull red heat. It reacts,
Al 2 Br g) 2KBr.
though somewhat slowly, with water or dilute
Aluminium iodide A1 2 I 6 may be prepared by acids with the production of methane. The
heating aluminium with iodine in a closed tube. i
formation of carbide and ultimately its decom-
It melts at about 185 (Weber) and boils at position has been proposed as a means of pre-
350 (Deville and Troost) ; its vapour is com
paring alumina from clay or other crude materials.
bustible. It dissolves in water, alcohol, and
Pring (Chem. Soc. Trans. 1905, 1530) found
carbon disulphide. -\
that up to 1400C. the carbide acts as a reducing
Aluminium fluoride AJ 2 Fg, may be prepared
agent on metallic oxides,
by the action of gaseous silicon fluoride, or of
+
A1 4 C 3 12MO=2A1 2 3 +3CO 2 +12M,
hydrofluoric acid upon aluminium. It forms but at higher temperatures alloys of aluminium
transparent rhombohedra, volatile at a red heat, and the metal are produced, only carbon being
insoluble in water and unacted upon by acids.
In solution in hydrofluoric acid, it appears to oxidised,
Al 4 C 3 +3CuO=Al 4 Cu 3 +3CO,
form the compound Al.,F g -6HF, the acid cor-
responding to the double fluoride of aluminium owing to the fact that alumina can be reduced
and sodium. by carbon at very high temperatures ; at lower
Cryolite Al 2 F 6 -6NaF.
This important com- temperatures the aluminium is oxidised by
carbonic oxide as observed by Moissan,
pound may be prepared and attempts
artificially,
have been made to produce it as a substitute for 6A1+3CO=:A1 4C 3 +A1 2 3,
the natural cryolite, it being claimed that the reaction being reversed at the higher tem-
the artificial cryolite possesses the advantage peratures.
ALUMINIUM. 115
Aluminium sulphate A1 2 3 (SO 3 3 ,18H 2 or

)
AL(S0 4 3 ,18H 2O. Aluminium sulphate occurs

)
naturally in considerable quantities. As the

hydrated salt of the above composition, it
forms the chief constituent of the mineral
alunogcn, halotrichite, feather alum, or hair salt,
which is found in volcanic districts, at Bilin in
Bohemia, Copiapo in Chili, &c. It also occurs
in pyritic shale. A sample of feather alum from
Friesdorf, Bonn, was found by Rose to contain
A1 2 3 14-9 p.c., S0 3 374 p.c., FeO 2-5 p.c.,
H 2
45-2 p.c., with traces of K, Na, Mg, and
Si0 2 .
Aluminile or webstente, a hydrated basic salt

of the composition A1 2 3 S0 3 ,9H 2 O, has been
found at Auteuil, Halle, Muhlhausen, &c.
In combination with potassium sulphate, the
basic salt occurs also in alunite, alumstone, or
alum rock K 2 S0 4 ,3A1 2 O 3 (S0 3 ),6H 2 O, a mineral
which is found in large quantities at La Tolfa
near Civita Vecchia, in Hungary, at Puy-de-
Sancy and Madriat in Auvergne, and in many
other localities. It usually occurs in fibrous
compact masses in trachyte, of colour varying
from white to red or brown, being produced by
the action of sulphurous gases upon trachytic
rocks rich in felspar.
The alunite from La Tolfa contains from
35 p.c. to 17 '5 p.c. alumina ; the average
composition of the mineral is A1 2 O 3 27-6 p.c.,
S0 3 29-74 p.c., K
2 O 7-55 p.c., Fe 2 3 1-2 p.c.,
Si0 2 22-7 p.c., 2 H 11-2 p.c.
Aluminium sulphate may be produced by
dissolving either the hydrated oxide or the
silicate in sulphuric acid. Of the raw materials
available for its manufacture, the two which
are of the greatest importance at the present
time are china clay (kaolin) and bauxite. China
clay is a very pure variety of clay, resulting
from the natural decomposition of felspar, and
approximating in composition to the formula
Al 2 3 ,2Si0 2 ,2H 2 0. It is of comparatively rare
occurrence, being found chiefly in Devon and
Cornwall in England ; at St. Yrieix near
Limoges, and in the departments of Allier,
Puy-de-Dome, and Brittany, in France ; at
Seilitz in Saxony and at Nassau in Bavaria.
;
Bauxite isan impure aluminium hydroxide

A1.2 3 ,2H 2 0, containing widely varying quan-
tities of silica and ferric oxide. It is found in
Ireland, in the south of France, and in Austria,
Calabria, Senegal, &c. (v. BAUXITE).
The composition of typical commercial grades
of the two minerals is given in the following
table, the analyses having been made on
material dried at'lOO :
Source
116 ALUMINIUM.
clay in the manufacture of aluminium sulphate |
Newlands (Eng. Pat. 1880, 5287) evaporates
a crude solution of the sulphate to a density of
1
was proposed by Lechatelier in 1858, and its

treatment forms the subject-matter of numerous 67Tw. (at 200F.) and cools for twenty -four
patents. Bauxite has the advantage over china hours in leaden tanks.
clay that it is more readily soluble in acid, and
About 60 p.c. of the sulphate thus crystallises
needs no preliminary calcination, the chief out. The liquid is drained off, and the residue
drawback to its use being the presence of a pumped or forced into lead -lined filter presses,
the plates of which are covered with thick felt,
comparatively large amount of iron.
The treatment of bauxite for the preparation and separated by metal rings. Here it is sub-
jected to a pressure of about 200 Ibs. to the
'
of alumino-ferric cake,' as patented by Messrs.
P. and F. M. Spence (1875), is as follows The : square inch. The hard cake so produced
mineral is digested with dilute sulphuric acid contains about 67 p.c. of the total aluminium
with the aid of steam until the acid is neu- sulphate, and 0-05 to 0-1 p.c. of iron. The
tralised ; the insoluble matter allowed to sub- mother liquor, evaporated and similarly treated,
side, and the solution evaporated to 100Tw. yields a second and third crop of crystals
and run into shallow-partitioned lead coolers. containing increasing quantities of iron.
It there solidifies, and 'is removed in blocks Ghadwick and Kynaston have patented a
18 or 20 inches square, each weighing about method for the removal of iron from bauxite
1 cwt. It is yellowish-green in colour, con- before converting the latter into aluminium
tains much alumina, and a small proportion sulphate. The powdered mineral is mixed to a
of iron and free acid. It is used in the prepa- thick cream with water, and treated with 5 to
ration of all but the finest papers, in the pre- 10 p.c. of oxalic acid and sufficient hydrochloric
cipitation of sewage and refuse liquids, and in acid to prevent the 'formation of insoluble
the clarification and decolourisation of water oxalates. After seven to ten days the mass is
supplies. The following analysis shows its washed, and a large proportion of the iron
general composition : A1 2 3 14-26 p.c. (corre- (together with some of the alumina) is thus
sponding to A1 2 3 3S0 3 47-61 p.c. ), Fe 2 3 0-28 p.c., removed as oxalate.
FeO 0-32 p.c. S0 3 (combined) 35-36 p.c., S0 3 Condy, in 1877, proposed the reduction of
(free) 0-45 p.c. Insoluble 0-06 p.c. the iron by reducing agents, or its conversion
The commercial sulphate of alumina which into sulphide by sulphuretted hydrogen, and
' '
is names of concentrated alum
sold under the the removal of the metal or sulphide by dilute
and alferite,' resembles alumino-ferric in com-
'
acid. The proportion of iron may thus be re-
position, and is prepared by a similar process. duced to one-third.
The following details concerning its manu- Weismann suggested the precipitation of
facture will serve to exemplify modern prac- the iron from aluminium sulphate liquors by
tice. means of potassium ferrocyanide. The method
As raw material, it is usual to employ a mix- is by no means satisfactory, as the precipitate
ture of Irish and French bauxites, reduced by contains much alumina and subsides very
means of disintegrators to the state of a coarse slowly.
powder. The powdered mineral is conveyed by Kynaston precipitates the bulk of the iron
means of an elevator to a lead-lined vat contain- as ferric arsenite, removing the last portions
ing sulphuric acid, heated to its boiling-point with calcium ferrocyanide, followed by the
(about 112), and having a strength, at this addition of copper or zinc sulphate.
temperature, of 96Tw. The mixture of acid According to Fahlberg and Semper (Eng.
and bauxite is boiled vigorously for 6 hours, Pat. 1881, 5579), both ferrous and ferric salts
after which it is diluted with weak liquors to may be precipitated from aluminium sulphate
70Tw. (measured at the boiling-point) and by agitation in the cold for about thirty minutes
allowed to settle. The clear liquor is decanted with lead peroxide, ferrous salts being first
and evaporated in lead-lined vessels until its oxidised and then precipitated. No lead passes
density reaches 112Tw. (boiling). It is then into solution unless chlorides be present. The
run into partitioned coolers where it solidifies, composition of the precipitate is not known, but
forming blocks or slabs, containing on an average the peroxide may be regenerated by digestion in
13-8 p.c. alumina, 0-7 p.c. ferric oxide, and 0-1 cold nitric acid. P. and F. M. Spence (Eng. Pat.
p.c. insoluble matter. 1882, 3835) use manganese dioxide for the
If French bauxite be used alone in the above same purpose. In presence of reducing agents
process, great difficulty is experienced in the such as ferrous salts, &c., manganese passes
clarification of the liquor ; with a mixture of into solution, and requires to be reprecipitated
Irish and
French bauxites, however, rapid by addition of chlorine or a hypochlorite.
settling occurs,and a perfectly clear liquor is The use of metantimonic acid and meta-
readily obtained. It is of importance also, in stannic acid (Hood and Salamon) has also been
this connection, that the liquor should retain a proposed for the precipitation of iron. The iron
small amount of free acid, as the fully neutralised is first oxidised by the addition of
bleaching
solution settles very slowly. powder, and the liquid is neutralised with chalk
Sulphate of alumina prepared by any of and agitated with the precipitant. Both sub-
the above processes always contains appreciable stances may be regenerated by digesting the
quantities of iron, and the removal of this precipitate with sulphuric acid.
impurity is a problem of considerable impor- (For further information regarding these pro-
tance, and one which has received the attention cesses, see Beveridge (J. Soc. Chem. Ind.
of many chemists. Numerous processes have 1886, 16-22) B. E. R. Newlands (ibid. 1882,
;
been devised for the purpose, but doubt-
it is
124); Kynaston (Chem. News, 40, 191 and
ful if any of these is satisfactory in works' 202).)
practice. The above-mentioned processes for the
ALUMINIUM. 117
purification
ofaluminium sulphate from iron of aluminium sulphate, facilitates the crystalli-
or no commercial significance at sation of the salt (Persoz).
possess little ' '
the present time. Pure aluminium sulphate

is prepared directly from pure alumina, which is
'
'
obtained from bauxite by the alkali fusion
The bauxite, reduced to a fine powder,
process.
is mixed with soda ash in such proportions that
for every molecule of A1 2 3 (including Fe 2 3 )
of Na,0.
present there are 1 to 1-2 molecules
The mixture is strongly heated in a reverberatory
furnace, with frequent stirring, for a period of
five hours. Carbon dioxide is evolved and the
alumina and ferric oxide are converted into
sodium aluminate and sodium ferrite respec-
tively. The mass is lixiviated by successive
extractions, first with weak liquor from previous
batches, and finally with pure water. The
sodium aluminate dissolves as such, whilst the
sodium ferrite is decomposed, forming insoluble
ferric oxide which remains in the exhausted
residue, and caustic soda which passes into
solution. The clear liquor is run into a boiler
and saturated with carbon dioxide produced by
the combustion of coke or by the decomposition
of limestone. During the passage of the gas
the contents of the boiler are heated to 70 and
kept thoroughly stirred by means of an agitator.
When the precipitation of the alumina is com-
plete, the liquid is allowed to settle and the
clear liquor decanted and concentrated for the
recovery of the dissolved sodium carbonate,
whilst the alumina is drained in a hydro-
extractor.
A cheaper process for obtaining the alumina
from the sodium aluminate has been devised by
Bayer (as described, p. 106).
The alumina prepared by either of the above i
processes yields by treatment with sulphuric

acid, a very pure quality of aluminium sulphate. |
Two grades of the latter are commonly prepared [
for the English market the one, sold in the ;
form of slabs or blocks, contains 14-0 p.c. of j
alumina and 0-0025 p.c. of ferric oxide, the

other, sold in powder, contains 18-0 p.c. of |
alumina and 0-0040 p.c. of ferric oxide.

Aluminium sulphate crystallises with diffi-
culty in thin, six-sided nacreous plates, con- ;
taining 18 molecules of water and having a

density of 1-6913 at 17(Dewar). The following
table of solubilities is given by Poggiale (Ann.
Chim. Phys. [3] 8, 467) for the crystalline and
anhydrous salts :
118 ALUMINIUM.
red in 100 c.c. of boiling water and diluting to a Mursaly, Munkact, and Tokay in Hungary in ;
litre). the islands of Milo, Argentine, and Nipoglio

T. J. I. Chem. Ind. 1911, 184)
Craig (J. Soc. (Grecian Archipelago) at Puy-de-Sancy and
;
proposes to determine the free acid in aluminium Madriat (Auvergne) ; at Samsoun in Asia
sulphate by treating the latter with excess of Minor; and in Australia. An 'alum mountain,'
neutral potassium fluoride, whereby the double composed of this mineral, is reported to exist in
salt A1F 3 -3KF is formed together with potassium China, and is stated to be nearly 1900 feet high
sulphate. As these products, are neutral to and to have a circumference at its base of about
phenolphthalein, the free acid present may be ten miles (U. S. Cons. Report, 1903).
directly titrated with a standard solution of The manufacture of alum is of great an-
potassium hydroxide. tiquity. In the time of Pliny alum was in use
as a mordant for the production of bright
'
Iron, in the ferrous condition, is estimated

by titration with decinormal potassium per- colours, and was even tested by means of the
manganate, and total iron by means of standard tannin in pomegranate juice to ascertain its
titanous or stannous chloride solution. If the purity. It was prepared in the thirteenth cen-
quantity of iron present be very small, it is tury at Smyrna from alum rock, and since the
determined colorimetrically (v. ALUMS). fifteenth century has been largely produced at
Several basic aluminium sulphates have been La Tolfa from the same substance.
prepared. The compound A1 2 3 ,2S0 3 ,12H 2 is Its preparation from pyritic shale has long
obtained by heating a solution of aluminium been known, together with the fact that the
sulphate with zinc, or by dissolving in it the presence of an alkali was necessary to induce
calculated quantity of aluminium hydrate. crystallisation, but, until proved in 1797 by
Spence and Sons, Limited (D. R. P. 1903, Chaptal and Vauquelin, the essential presence
167419), prepare a basic sulphate of similar of alkali in the crystals was not recognised.
composition by heating sulphuric acid under Very pure alum is prepared in small quan-
pressure with 15 to 30 p.c. more alumina than tities at Solfatara. The natural alum found there
is required for the formation of the normal salt. is digested with water in large wooden vats under
The solution is then treated with sufficient chalk cover, and maintained at about 40 by the
or lime to raise the basicity by 20 to 28 p.c. natural heat of the soil. The solution is de-
The strongly basic solution is rapidly filtered and canted and crystallised. A second crystallisation
concentrated in vacu6 until its density reaches produces extremely pure alum.
1'45. On cooling with agitation, a magma of Production of alum from alunite. The pre-
crystals is formed and is separated by suit- paration of alum from alunite is an industry
able means from the mother liquor which con- which dates from very early times. Of Oriental
tains normal aluminium sulphate (compare also origin, it appears to have been introduced into
Eng. Pat. 1902, 25683, and Fr. Pat. 1903, Europe in the thirteenth century, and during
331836). the fifteenth century several alum works were
ALUMINIUM BRONZE v. ALUMINIUM. established. Amongst these may be mentioned
ALUMS. This generic name is given to an the celebrated works at La Tolfa near Civita
important group of double salts of the general Vecchia, a district in which alum manufacture
type R 2 S0 4 ,R',0 3 (S0 3 ) 3 ,24H 2 0, where R is a still ranks as an important industry.
monovalent metal or basic radicle such as The outline of the La Tolfa process given
potassium, sodium, ammonium, &c., and R' 2 3 below is of historical interest. The mineral,
is a sesquioxide such as that of aluminium, iron, broken into lumps of moderate size, is calcined
chromium, or manganese. They are all soluble at a low red heat, either in heaps or in kilns.
in water, and crystallise therefrom with twenty- The operation requires to be carefully performed,
four molecules of water, in forms belonging and is stopped as soon as the mineral begins to
to the regular system, usually octahedra or evolve acid fumes. The calcination occupies
cubes. about six hours and results in a loss in weight
The alums which contain the sesquioxide of amounting to about 33 p.c., chiefly due to the
alumina will alone be considered here, and of expulsion of water at the same time the basic
;
these the most important are the potassium, sulphate is decomposed, yielding alum and in-
sodium, and ammonium compounds. soluble alumina. The roasted mass is trans-
' '
alums
Selenic have been prepared, in ferred to brickwork bins and exposed to the
which sulphuric acid is replaced by selenic acid. air for several months, during which time it
Potassium alum, Potash alum is
occasionally moistened. The resulting sludge
K 2 S0 4 ,A1 2 3 (S0 3 ) 3 ,24H 2 0.
is lixiviated with water at 70, and the clear
decanted liquor concentrated. The crystals of
This salt is found in nature as kalinite, in the alum which separate on cooling are cubic and
form of fibrous crystals or as an efflorescence on have a reddish tinge owing to the presence of
aluminous minerals, and occasionally also in ferric oxide this be removed
suspended ; may
octahedra, at Whitby, Campsie, &c. In the by The amount of soluble iron
recrystallisation.
Solf atara near Naples, and the islands of Volcano stated to be less than 0-005 p.c. The
is
present
and Milo, it occurs in larger quantities, being
product, known as Roman alum, was in former
formed by the action of volcanic gases upon times highly valued on account of its great
felspathic trachyte. purity.
Of greater importance is the mineral alunite In the modern process, employed on the
or alumstone, which is a double salt of
potassium Continent, the alunite is calcined at a higher
sulphate and basic aluminium sulphate, having temperature and the product treated with
the composition K 2 S0 4 ,A1 2 (SO 4 ) 3 ,2A1 2 (OH) 8 ; sulphuric acid, whereby aluminium sulphate is
it isfound at La Tolfa near Civita Vecchia at ; formed from the excess of alumina, and passes
Montioni in the Duchy of Piombino ; at into solution together with the alum. The
ALUMS. 119
latter is either crystallised out, and the more 1-09 to are run into
1-15, settling tanks and
soluble aluminium sulphate recovered as such allowed to deposit calcium sulphate, ferric
oxide,
from the mother liquors, or sufficient potassium and other suspended impurities, and are then
sulphate is added to convert the whole of the removed for concentration. The method adopted
aluminium sulphate into alum. for this purpose varies
according to the nature
According to C. Schwartz (Ber. 17, 2887), of the mineral under treatment. In the case
the best temperature for the roasting is 500, of shales from Hurlet and
Campsie the concen-
and the acid used should have a density between tration is effected by surface
evaporation in a
1-297 and 1-530. L. Geschwind (Manufacture reverberatory furnace.
of Alum and the Sulphates of Alumina and The bed is of stone, coated with well-rammed
Iron, 1901), however, states that in France a clay, 4 or 6 feet wide, 2 or 3 feet deep, 30 or 40
temperature of about 1000 is employed. feet long. It is filled to the brim with
strong
Formerly, the greater portion of the alum liquor, and the flame and hot air from the fire
manufactured in England was prepared from carried over it. As evaporation proceeds, more
alum shale (alum ore), alum schist, and similar liquor is added until the proper concentration
minerals, which occur in large quantities at is reached. It is then run into leaden
pans,
Whitby in Yorkshire, Hurlet and Campsie in concentrated to about 14 sp.gr. and conveyed
Scotland, in Sweden, Norway, Belgium, and in to a precipitating cistern containing the
requisite
several parts of Thuringia, Westphalia, &c. quantity of dry potassium chloride ; the liquid
These minerals are mixtures of aluminium is well agitated and the chloride soon dissolves.
silicate, iron pyrites, and bituminous substances ; In about 5 days the liquor is drained from the
the iron pyrites is principally present in the large crystals, which are washed and recrystal-
aluminous schists as a fine black powder, lised.
disseminated throughout the mass, and not The Whitby shales differ from those at
distinguishable to the eye. The rapid oxidation Hurlet, that they contain a considerable
in
of these minerals under atmospheric influences quantity magnesia which passes into the
of
or heat is due to this state of fine division. extract in the form of magnesium sulphate. In
Aluminous earllis are dark brown, friable, this case surface evaporation is not
satisfactory
porous masses without structure, and contain on account of the formation of a crust of this
less silicathan the schists. They usually occur salt which retards evaporation, The evapora-
in layers with lignite. tion of the liquor is carried out, therefore, in
Production of alum from aluminous shale. leaden vessels, until a sp.gr. of 1-125 to 1-137 is
The more earthy shales are porous, and if piled reached, after which the solution is allowed to
in heaps in the open air and occasionally mois- stand until clear. The concentration is con-
tened undergo spontaneous oxidation, with the tinued up to sp.gr. 1 -25, at which stage a sample
formation of sulphates of iron and aluminium. of the liquor is withdrawn and the percentage
Usually they require roasting, and when not content of aluminium sulphate determined.
sufficiently bituminous for combustion, are first After further evaporation to a density of 1 -4 to
mixed with fuel. 1-5, the hot liquor is run into a precipitating
The coarsely broken shale is built up with tank and mixed with a saturated solution of
alternate layers of coal into heaps, which are the calculated quantity of potassium chloride
ignited. As the mass burns, fresh quantities of or sulphate, the whole being kept in constant
the mineral are added, until a sufficient mass of agitation to induce the formation of small
material has been accumulated. By pumping 7
cr3 stals (alum meal).
water over the surface at intervals the tempera- When much ferric sulphate is present in the
ture is regulated to a degree suitable for rendering solution, the addition of potassium sulphate
the decomposition as complete as possible. Too would produce iron alum, isomorphous with ordi-
high a temperature is to be avoided, as it nary alum, which would crystallise out and con-
results in the loss of sulphur dioxide and the taminate the product. The use of potassium
formation of a slag. During the combustion chloride prevents this, by producing the easily
of the shale the pyrites is soluble ferric chloride, while ferrous salts are
decomposed, giving
up a portion of its sulphur, which is converted converted into the equally soluble ferrous
by burning into sulphur dioxide, and this in chloride, an equivalent amount of potassium
conjunction with atmospheric oxygen attacks sulphate being formed at the same time. Chloride
the clay, forming aluminium sulphate. The of potassium is generally employed in preference
calcined mass is allowed to remain exposed to to the sulphate, whenever sufficient iron sulphate
the air for a considerable period, during which is present to supply the requisite amount of sul-
a further absorption of oxygen takes place, phuric acid for the formation of alum ;
its
resulting in the conversion of the lower sulphide greater solubility is also in its favour. Too much
of iron into ferrous
sulphate and ferric oxide. chloride should be carefully avoided, for after
Lixiviation. This operation is carried out the iron sulphates have been decomposed, the
in large lead-lined boxes with
perforated bottoms, aluminium sulphate is itself attacked, with the
the filtering bed
being formed of timber topped production of the very soluble chloride, which
with brushwood. A layer of the roasted mineral is lost.
about 13 inches deep, is introduced and its The alum meal, consisting of small brownish
extraction is effected, first with the mother crystals, drained and washed twice with cold
is
liquor from the alum crystallising pans, and later water. The adhering mother liquor, containing
with pure water, the liquid in each case
being much iron, is thus removed, and the meal is left
left
overnight in contact with the material. nearly pure. The final purification is effected by
The exhausted mineral still contains a dissolving in a minimum quantity of boiling
considerable amount of alumina and sulphuric water and allowing the solution to stand for
acid. The liquors, which have a density of about eight days in casks furnished with movable
120 ALUMS.
staves. At the end
of this period the staves some days the staves are removed and a hole
are removed, the block of crystals is pierced, j
is bored in the mass of crystals for the removal
the mother liquor drained off and employed for of the liquor. Each block weighs about 3 tons,
dissolving fresh quantities of meal. while the mother liquor contains about 1 ton.
The mother liquor from the alum meal has a i To produce 1 ton of ammonium alum by
sp.gr. of about 1 -4 ; it contains sulphate or I
this method on an average about 16 cwts. of the
chloride of iron, magnesium sulphate, &c., and !
shale is required.
will yield more alum on evaporation. In a final A great advantage of this process is the
evaporation it yields ferrous sulphate in fine speed with which the crude material is con-
green crystals. When iron is present in large verted into marketable alum. By the old pro-
quantity, the liquors are evaporated and the cess twelve months was required for this con-
ferrous sulphate crystallised out before the ad- version, whilst by Spence's process the whole
'
dition of the potassium salt. In this case the j

operation is performed in one month. For this
iron salt is less pure and less soluble, but the process Spence was awarded the medal for
alum subsequently produced contains less iron. I
alum manufacture at the Exhibition of 18C2, at
Formerly, potassium alum was alone pro- which date he manufactured 150 tons of alum
duced. In 1845, however, the potassium sul- weekly, over one-half the total production of
phate was replaced by the ammonium sulphate
'
England (v. Hofmann's Report on Chemical

produced from the then waste liquors from gas Processes at the Exhibition of 1862, p. 62, and
works, yielding ammonium alum. This great j
J. Carter Bell, Chem. News, 12, 221).
improvement was introduced by the late Peter Alum is also produced by the addition of
Spence his method was soon generally adopted
; potassium sulphate to aluminium sulphate, pre-.
both in England and on the Continent. pared by any of the processes already described.
Another great advance was made by Spence It is prepared in great purity from the sulphate
in 1845 in the manufacture, by the treatment produced from cryolite ; 1 ton of cryolite pro-
of the refuse shale underlying the coal-seams duces 3 tons of alum (v. Sodium aluminate).
of South Lancashire. This shale contains from Many other processes have been proposed
5 to 10 p.c. of carbonaceous matter. It is and used for the preparation of alum.
piled upon rows of loosely placed bricks (to Spence, in 1870 (Eng. Pat. 1676), patented a
allow a free passage to the air) in heaps method of preparing alum from mineral phos-
4 or 5 feet high and 20 feet long. The com- phates, especially that from Redonda near
bustion is started with a little fuel, but the shale Antigua, which contains 26-1 p.c. of alumina as
contains sufficient combustible matter to con- phosphate with ferric oxide and silica. It is
tinue burning. The calcination is performed calcined at a red heat to render it porous,
slowly at a heat below redness. In about 10 days powdered, and digested with sulphuric acid of
the roasting is completed, and the material has sp.gr. 1-6 in quantity proportional to the amount
become soft, porous, and light red, whilst the of alumina, in lead-lined vessels, heated by steam.
alumina contained in it has become anhydrous The liquid is concentrated to a density of 1-45,
and soluble in sulphuric acid. Too high a tem- and treated with the requisite amount of potas-
perature, however, partially vitrifies it, in which sium sulphate to convert the whole of the
case it is only slowly attacked by acid. Charges alumina into alum. Phosphate containing 20
of 20 tons are placed in large covered pans 40 p.c. of alumina yields about H
times its weight
feet long, 10 feet wide, and 3 feet deep, lined of alum, from which, however, the last traces
with lead, and are digested for about 48 hours of phosphoric acid are removed with difficulty.
with sulphuric acid (of sp.gr. 1-35) at 110, The phosphoric acid in the mother liquors is
the temperature being maintained by fires be- valuable as a manure.
neath the boilers. Formerly ammonia was forced Methods have frequently been proposed for
into the* liquid from a boiler containing gas the preparation of alum from felspar. Ordinary
liquor ; ammonium sulphate was thus produced, felspar contains both potassium and aluminium
with considerable rise of temperature, and com- combined with silica in larger proportions than
bined with the aluminium sulphate forming am- are contained in alum the problem to be solved
;
monium alum. The solution of alum so pro- is the substitution of sulphuric acid for silica.
duced is run into cisterns 29 feet by 17 feet, and A method adopted by Turner, said to have been
If feet deep, in which it is kept in constant originated by Sprengel, consisted in the ignition
agitation. In about 14 hours the small crystals of a mixture of one part of the powdered mineral
so formed are drained, washed with some with one part of potassium bisulphate until
'
mother liquor from block alum,' and dissolved fused ; one part of sodium carbonate was then
'
by a process known as rocking for the pro- added, and the whole again fused. The mass
duction of pure block alum. For this purpose was boiled with water and the insoluble double
they are introduced into a hopper, at the silicate remaining was decomposed by hot sul-
bottom of which they encounter a current of phuric acid of sp.gr. 1-20, and the alum crystal-
steam at a pressure of 20 Ibs. per sq. inch, both lised out. On account of the high temperature
steam and crystals being supplied in such required, this processwas not successful.
proportions that all the crystals are dissolved, At the present time the bulk of the alum
while no steam is wasted. In this manner 4 manufactured in England is prepared either
tons of crystals may be dissolved in 30 or 40 from shale or from the aluminium sulphate
minutes. The solution is run into a leaden tank, derived from bauxite or china clay.
and, after a time, treated with a small quantity For the more delicate dyes the alum used
of size, which precipitates a quantity of insoluble must be of extreme purity. Samples containing
matter. The clear liquid is next run into tubs even less than 0-001 p.c. of iron may be unsuit-
about 6 feet high and 6 feet wide, tapering able for certain purposes. The percentage of
upwards, Avith movable lead-lined staves. After iron in alum or in aluminium sulphate is usually
ALUMS. 121
determined by means of a solution of ammonium

thiocyanate standardised with iron alum. Many
precautions are necessary in performing the
(v. Tatlock, J. Soc. Chem.
analysis Ind. 1887,
276 G. Lunge, Mon. Sci. 1897, 160).
;
Potassium alum crystallises with 24 molecules

of water, in crystals belonging to the cubic
system, usually in large colourless octahedra of
sp.gr. 1-751 (Retgers,
Zeitsch. physikal. Chem.
3, 289 ; J. B. 1889, 148).
De Boisbaudran has also obtained it crystal-
lised with hemihedral faces of the tetrahedron.
The crystalline form is affected by the presence
of other substances in solution, and by the tem-
perature. When formed at ordinary temperatures
in the presence of basic alum, the crystals are
cubes, frequently dull on the surface from the
presence of the basic salt ; for this reason Roman
alum usually forms cubes. At 40, even in
presence of basic salts, octahedra are produced.
Potassium alum possesses the property of
crystallising with hydrogen peroxide (Will-
statter, Ber. 36, [1903] 1828).
According to Poggiale (Ann. Chim. Phys. [3]
8, 467), the solubility of potassium alum and of
ammonium alum is as follows :
100 parts water dissolve :
c.
122 ALUMS.
3. P. M., D. D., and H. Spence (Eng. is found on the island of Anguilla in the West
Pat. 1900, 5644) prepare a solution of sodium Indies.
sulphate saturated at 40 to 60, which is Aluminium thiocyanate or sulphocyanate
allowed to cool during agitation until a consider- has been proposed as a substitute for aluminium
able proportion of decahydrated crystals have acetate for alizarin, steam reds, &c. the colours
;
separated. The mixtureof liquid and crystals produced are said to be especial^' permanent
is then run into a solution of aluminium sulphate (v. Storch and Strobe], Dingl. poly. J. 241, 464 ;
containing the solid salt in suspension. There and Gottlieb Stein, Dingl. poly. J. 250, 36).
is thus obtained a large crop of Avell-defined Lauber and Haussmann (Dingl. poly. J. 245,
soda alum crystals. Alternatively, the solid 306) recommend the following method of prepara-
aluminium sulphate may be added to a suitable tion 5 kilos, aluminium sulphate are dissolved
:
solution of sodium sulphate or chloride, in which in 5 litres boiling water, 250 grams of chalk are
either salt may be suspended in the solid state. added, followed by 11 -5 litres of crude calcium
Sodium alum is much more soluble at ordi- thiocyanate solution of 30Tw., and the whole
nary temperatures than potassium or ammonium well stirred and allowed to settle. The clear
alum, in consequence of which it is more liquid is ready for use.
difficult to purify from iron. On account of Aluminium permanganate v. MANGANESE.
the lower cost of sodium salts, it would be Aluminium silicates. These compounds are
largely used in place of other and more ex- exceedingly numerous and important. As an
pensive alums, if it could be easily purified by anhydrous silicate, with silicate of iron, calcium,
crystallisation (see Eng. Pat. 1881, 5650). magnesium, &c., aluminium occurs in the
Sodium alum crystallises with 24 molecules varieties of garnet, crystallising in the regular
of water in regular octahedra, having a sp.gr. of system. As silicate of aluminium, calcium, and
1-667 (Soret). At 10-6 100 parts of water sodium it is found in lapis-lazuli, which was
dissolve 107-11 parts of the alum (Wadmore) ; formerly used as ultramarine. It is now re-
according to Ure, the solution saturated at 15-5 placed by artificial ultramarine (v. ULTRAMARINE).
contains 110 parts of the alum in 100 of water, As silicate of aluminium, combined with
and has a density of 1-296. Sodium alum is potassium, iron, and magnesium, it occurs in
insoluble in alcohol. the micas. As double silicate of aluminium,
Ammonium alum potassium, sodium, magnesium, or calcium, it
forms the varieties of felspar which occur in
(NH 4 S0 4 ,A1 2 O 3 (SO 3 ),,24H,O
)2
immense quantities in eruptive rocks. By the
occurs as Tschermigite in Bohemia, and in the decomposition of felspar by the carbonic acid
crater of Mount Etna. in the atmosphere and in rain or spring water,
Its preparation is
analogous to that of the alkaline compounds are removed, leaving
potassium alum, a solution of aluminium sul- clay of more or less purity (v. CLAY), which,
phate, prepared by any of the methods already under pressure, becomes hardened and laminated,
described, being treated with the equivalent forming shale, and finally slate ((J.v.). Many of
quantity of ammonium sulphate, and the alum the silicates of aluminium are of great impor-
separated and purified by crystallisation. tance, and of the widest application. The more
Ammonium alum crystallises with 24 mole- important of them are specially considered under
cules of water in regular octahedra, their applications (v. POTTERY ; PORCELAIN).
having a
conchoidal fracture and a density of 1-631 Aluminium acetate. Red liquor (v. Alumi-
(Soret). At ordinary temperatures it is less nium acetates, art. ACETIC ACID).
soluble in water than potassium alum (v. Table The compounds of aluminium with the higher
of solubilities, under Potassium alum). The fatty acids are used for increasing the viscosity of
saturated solution boils at 110-6, and contains mineral lubricating oils, under the names oil
' '
207-7 parts of the alum to 100 parts of water pulp and fluid gelatin (L. Marquardt, Zeitsch.
'
(Mulder). When heated the crystals swell up anal. Chem. 25, 159).
and form a porous mass, losing water and Aluminium oleate is a soft white, putty-like
sulphuric acid ; at a high temperature alumina substance, of great tenacity, insoluble in water,
alone remains. This serves as a useful method soluble in ether and petroleum. A mixture of
for the production of very pure alumina. oleate, palmitate, and other fatty salts is pro-
In its general properties and uses, ammonium duced from whale, cotton-seed, and similar
alum closely resembles the oils by saponification with soda and addition
corresponding
potassium compound. of the sodium salt so produced to a solution of
'
Aluminium sulphite A] 2 3 (S0 8 ) 3 . alum. The gummy precipitate is known as oil ,
The bisulphite has been used by Becker pulp,' and is dissolved in 4 or 5 parts of mineral
' '
(Dingl. poly. J. 257, 300), Suchomel J. Soc. Chem.
(
oil to form a thickener for addition to the
Ind. 1887, 143) and others, for the purification lubricator. A sample of oil pulp resembling
of beet sugars. Becker prepares for this purpose thick gelatin had a sp.gr. of 0-921, and contained
a solution of sp.gr. 1-167 containing 4-37 p.c. 6 p.c. alumina combined with 30 p.c. fatty acids,
alumina and 13-9 p.c. sulphurous oxide, by dis- together with 15 p.c. lard oil, and 48 p.c. paraffin
solving the hydrated oxide in sulphurous acid. oil (Oil and Colourman's Journ. 4, 403).
Aluminium phosphates. As hydrated phos- Aluminium palmitate is a constituent of oil
phate, aluminium occurs in the turquoise, and pulp. It may be prepared in the same manner
enters into the composition of wavellite, lazu- as the oleate, from palm oil. It forms a resinous,
lite and It is found in considerable
gibbsite. elastic, inodorous, neutral substance, insoluble
quantity mineral phosphates, as in the
in in water, but readily soluble in petroleum and
Redonda phosphates which have been used for turpentine. K. Lieber (Dingl. poly. J. 246, 155)
the preparation of alum and for fertilisers (v. recommends the use of the latter solution as a
ALUMS; MANURES). A massive stony variety varnish. It imparts a glossy appearance 'to
AMALGAM. 123
paper, leather, &c.,

and renders them waterproof fungus, Fortes (Polyporus) igniarius, the false
' '
without affecting their elasticity. G. H. B. tinder-fungus, which grows on the trunks of the
ALUMNOL v. SYNTHETIC DRUGS. oak. but also on alder, willow, and various other
ALUM-SHALE. A kind of shale or slate trees. It must be plucked in the months of
containing disseminated iron pyrites, which, on August and September. It may also be pre-
prolonged exposure to the weather, gives alu- pared from Fames (Polyporus) fomentarius, the
minium sulphate, owing to the action of sul- true tinder-fungus, also indigenous, found
phuric acid (from the decomposition of the especially on the beech, elm, and various fruit
iron pyrites) on the clayey material. The heaps trees. It was formerly used in surgery, and has
of weathered shale are leached with water, and hence been called surgeons' agaric. Amadou is
to the solution of aluminium sulphate and prepared by removing the outer rind and care-
sulphuric acid so obtained potashes are added. fully separating the yellow-brown spongy sub-
The alum obtained by the evaporation of this stance which lies within it. This substance is
solution is purified by recrystallisation. The cut into thin slices, and beaten with a mallet to
alum-shales of Liassic age on the coast of can be easily pulled asunder
soften it, till it
Yorkshire, in the neighbourhood of Whitby, between the

In this state it is useful
fingers.
have been largely worked by this method since in surgery. To convert it into tinder, it is
the time of Queen Elizabeth, but now the boiled in a strong solution of nitre, dried, beaten
industry has become extinct. Alum-shales in anew, and put a second time into the solution.
the coal-measures of the West Riding of York- Sometimes, to render it very inflammable, it is
shire are, however, still worked to a small imbued with gunpowder, whence the distinction
' '
extent (v. Alums, art. ALUMINIUM). L. J. S. of ' black and ' brown amadou.
ALUNDUM. An abrasive manufactured at AMALGAM. An alloy of mercury with some
]
Niagara Falls from fused bauxite (v. ABRASIVES other metal or metals.
and BAUXITE). There are four general methods for preparing
ALUNITE or ALUM -STONE. Hydrated amalgams.
basic sulphate of aluminium and potassium 1. Metallic mercury is brought into contact
KA1 3 (S0 4 ) 2 (OH) 6 usually found as white, with the other metal, either in the solid or in a
,
compact, granular masses, somewhat resembling finely divided state at the ordinary or at a
limestone in appearance. It mostly occurs in higher temperature. In this way amalgams of
connection with volcanic rocks, having been antimony, arsenic, bismuth, cadmium, mag-
formed by the action of solfataric vapours on nesium, potassium, silver, sodium, tellurium,
such rocks. In some cases, however, it may have thorium, tin, zinc, and lead may be obtained.
been formed by the action of decomposing iron- 2. Mercury is brought into contact with a
pyrites on clay. Extensive deposits are met saturated solution of a salt of the metal, when
with at Tolfa near Rome, in Tuscany and part of the mercury goes into solution and the
Hungary, and at Bulladelah in New South remainder combines with the liberated metal ; or
Wales. Alum is obtained from it by repeatedly better still, zinc or sodium amalgam is employed,
roasting and lixiviating, the yield being from 60 when the zinc or sodium displaces the metal in
to 80 p.c. In Hungary the harder and more the solution. By this method amalgams of bis-
compact varieties have been used for millstones. muth, calcium, chromium, iridium, iron, magne-
L. J. S. sium, manganese, osmium, palladium, and stron-
ALUNOGEN. Hydrated aluminium sulphate tium may be prepared by using sodium amalgam,
A1 2 (SO 4 ) 3 ,18H 2 0, occurring as a white, delicately and cobalt and nickel by using zinc amalgam
fibrous efflorescence on shale and other rocks. (Moissan, Compt. rend. 1879 Chem. News, 39, ;
It has been formed by the action on the alu- 84).

minous rock of the products of decomposition 3. The metal to be amalgamated is placed in
of iron pyrites. A trace of iron sulphate is a solution of a mercury salt copper may be ;
often present, imparting a yellowish or reddish amalgamated by this process.

|
colour to the mineral. L. J. S. 4. The metal is placed in contact with

ALVA or ALFA v. ESPARTO this is the method
!
mercury and dilute acid ;
ALVELOS. A
name applied to the Euphorbia usually employed in amalgamating zinc. Iron,
heterodoxa (Muell.), growing in Brazil, the juice aluminium, palladium, nickel, and cobalt may
of which has been used as a cure for cancer be made to combine with mercury by this process
(Pharm. J. [3] 15, 614). if they be placed in contact with a stick of zinc
ALYPIN. Trade name for benzoyltetramethyl- (Casamajor, Chem. News, 34, 36 Arch. Pharm. ;
diaminoethyldimelhylcarbinol hydrochloride. Em- [3] 11, 64; Chem.

Soc. Trans. [2] 34, 474).
ployed as an anaesthetic and as a remedy for Amalgams are also formed when mercury is
vomiting and in the treatment of diseases of used as the cathode in the electrolysis of salt
the upper respiratory passages and of the organ solutions ;
a number of metals can thus be
of hearing. Used also in veterinary practice in obtained as amalgams, although they cannot be
place of cocaine. obtained directly in the tree state by the elec-
It occurs in crystals, m.p. 169, sol. in trolysis of aqueous solutions.
water, forming a neutral solution. Aqueous The combination of sodium with mercury by
solutions may be sterilised without undergoing method I takes place with great energy, heat
decomposition by boiling from 5 to 10 minutes and light being produced. It is best prepared by
(Neustiitter, Pharm. J. 1905, 869). combining a small portion of the mercury with
(For distinctive reactions, v. Lemaire,
Rep. the sodium, and then adding the remainder to
Pharm. 1906, 18, 385.) (v. SYNTHETIC DRUGS.) the amalgam.
AMADOU or GERMAN TINDER. (Amadou, Native amalgams are found in various parts
Fr. ;
Zunderschwamm, Ger.) A spongy com- of the world. The following table contains the
bustible substance, prepared from a species of analyses of a few :
124 AMALGAM.
Ag
AMBER OR SUCCINITE. 125
of trimethylamine ; saturated solutions of the AMBAR LIQUID v. BALSAMS.

hydrochlorides of aniline, coniine, morphine, AMBER or SUCCINITE. (Bernstein, Ger.) A
and quinine give off hydrogen only. fossil resin derived from the
extinct conifer
Electricalamalgam is made by melting to- Pinitessuccinifer (Goppert), andfound as irregular
gether 1part of zinc and 1 part of tin, and then nodules in strata of Tertiary age,
principally on
adding 3 parts of mercury. An amalgam of the Prussian coast of the Baltic. The amber-
cadmium is used in the construction of the bearing stratum lies partly below sea-level, and
cadmium standard cell ; this amalgam and its the amber washed out by the action of the waves
electrical behaviour have been studied by F. E. is picked up on the sea-shore or won
'
by dredging.
Smith Mag. February, 1910).
(Phil. Such ' strand-amber was formerly collected
Silveringamalgams. For metals, 1 part of farther west, as far as the coast of Holland, and
silver to 8 parts of mercury ; for glass, 1 part isolated specimens are picked up on the east
each of lead and tin, 2 parts bismuth, and 4 parts coast of England (Norfolk, Suffolk, and Essex).
mercury. The use of amalgams for silvering has At the present time the bulk of Prussian or
been almost completely superseded by the use in Baltic amber is obtained from pits and mines in
' '
the case of glass of chemically deposited silver, the blue earth in Samland, East Prussia.
and in the case of metals by electro-plating. Here the production in 1907 amounted to
Teeth fillings. 1. Copper precipitated from 404,300 kilos, and in addition about 20,000
copper sulphate solution with zinc, washed with kilos Avas collected on the sea-shore.
sulphuric acid containing a small quantity of Baltic amber differs from other fossil resins
mercuric nitrate, and amalgamated with twice in containing succinic acid, which is
present to
its weight of mercury (Fletcher), has the pro- the extent of 3 to 4 p.c. in perfectly transparent
perty of softening with heat and hardening again specimens, but reaching 8 p.c. in cloudy ('frothy ')
after a few hours. It is a permanent filling, as amber. It is therefore distinguished by the minera-
the copper salts penetrate and preserve the tooth logical name succinite, and in the trade the ten-
dency is to apply the name amber exclusively
'
substance. It has the objection of staining the '
tooth, and is only used in posterior teeth. 2. A to Baltic amber. The composition is somewhat
palladium amalgam is sometimes empkêd, but variable, averaging C, 79 p.c.; 0, 10-5 p.c.;
its rapidity of setting, intense black colour, and H, 10 '6 p.c. ; and corresponding approximately
cost are against its general use. 3. An alloy of H
with the formula C 10 160. Sulphur is also
silver 68-5, tin 25-5, gold 5, and zinc 1 p.c. present (0-26 to 0-42 p.c.), and some ash, usually
(Black); or silver 69-5, tin 25-5, gold 4, and about 0-2 p.c., but increasing in amount if the
zinc 1 p.c. (Tulloch), amalgamated with mer- material encloses foreign matter. Amber is,
cury, is extensively employed, as it has a good however, not a simple resin when heated, it
;
edge strength, and suffers little, if any, shrinkage. gives oil of amber (q.v.) and other products, and
The shrinkage is the greatest difficulty to over- by the action of solvents at least four different
.come in order to render alloys of permanent use kinds of resin can be extracted from it. Accord-
for teeth filling, the object being to secure such ing to 0. Helm, Baltic amber contains 17 to 22
a proportion of metals that the shrinkage of one p.c. of a resin (m.p. 105) soluble in alcohol ;
may be overcome by the expansion of another, 5 to 6 p.c. of a resin (m.p. 145) insoluble in
and so obtain a watertight plug. alcohol, but soluble in ether 7 to 9 p.c. of a
;
AMALIC ACID v. ALLOXANTIN. resin (m.p. 175) insoluble in alcohol and ether,
AMANITA MUSCARIA. Fly agaric. A but dissolving in caustic potash ; and 44 to 60
poisonous fungus, used in Kamtschatka and p.c. of insoluble bitumen.
Siberia as a narcotic and intoxicant, and, when Baltic amber is usually pale yellow, ranging
steeped in milk, as a fly-poison. narcotic A to brown or reddish- brown in colour, and it
organic base, muscarine C S 15 H NO
3 , which is the varies from perfect transparency to opacity.
hydrated aldehyde of betaine, has been isolated The varying degrees of turbidity are due to the
from it (Schmiedeberg and Harnack, J. 1876, 804). presence of vast numbers of microscopic air-
The natural muscarine is like the artificial bubbles. The enclosure of insects and fragments
product in crystalline form, solubility, and of wood and dirt in amber is well known, and
composition of its platino- and auro-chlorides, points at once to the mode of origin of the
and to a large extent in its physiological action, material. According to differences in colour and
but unlike the artificial muscarine it does not transparency, various trade names are applied,
'
induce paralysis of the intermuscular nerve- such as 'clear,' flohmig,' 'cloudy,' 'bastard,'
terminations in the frog, and myosis in the pupils 'osseous' or 'bone,' and 'frothy.' The sp.gr.
of the eyes of birds
(Nothnagel, Ber. 26, 801). ranges from 1-05 to 1-10 (varying with the
porosity) ; and the hardness
It differs both in constitution and is 2|, being rather
properties
from anhydro- and iso-muscarine. higher than that of most other resins, which
A green and red dye of composition latter can be scratched with the finger-nail.
C 29H 2p 10 , andC 19 H 18 8 respectively, have also The material is brittle and breaks with a con-
been isolated from it (Griffiths, Compt. rend. choidal fracture. When cut with a knife,
130, 42). parings are not obtained, but only powder. It
AMARANTH v. Azo- COLOURING MATTERS. can be turned on the lathe and takes a good
AMAZON-STONE. A
bright-green variety of polish, being worked with whiting and water or
the potash-felspar microcline (KAlSi
3 8 ). It is rotten-stone and oil, and finished by friction with
found hi granitic rocks near Lake Ilmen in the a flannel. When heated, amber begins to soften
Ural Mountains, at Pike's Peak in Colorado, and at about 150, giving a characteristic odour ;
recently of very good quality in Madagascar. It it melts at 350-375, that is, at a higher
is used to a limited extent as a
gem-stone, and temperature than other resins, giving dense white
for making various small ornamental
objects fumes with a peculiar aromatic odour, and
(v. FELSPAR). L. J. S. causing violent coughing. When rubbed it
126 AMBER OR SUCCINITE.
becomes negatively electrified (from the ancient Stantienite (E. Pieszczek, 1880), a brown
'
name electron, for amber, the word ' electricity resin occurring with Prussian amber.
is derived) ; and when rubbed vigorously it emits For several papers on amber and amber-like
an aromatic odour, but does not become sticky resins, by O. Helm and by P. Dahms, see Schr.
like other resins. These characters serve to natf. Ges. Danzig, vols. iv.-xii. (1878-1908).
distinguish true amber from the more abundant See also Max Bauer, Edelsteinkunde, 2nd edit.
copal ;
the latter is further usually clearer, 1909, and English transl. (Precious Stones), by
lighter in colour, and more gummy in appear- L. J. Spencer, 1904. L. J. S.
ance. AMBER, OIL OF. When amber is heated
In the trade the material is sorted into many it softens, fuses, and gives off succinic acid, water,
grades suited for various purposes. The larger oil, and a combustible gas. If the residue
pieces of better quality (' work-stone ') are cut (colophony of amber) be more strongly heated,
into beads and other small personal ornaments, a colourless oil passes over. These oils, accord-
and are largely used for making the mouth- ing to Pelletier and Walter (Ann. Chem.
pieces of tobacco-pipes and cigar- and cigarette- Phys. [3] 9, 89), have the composition of
holders. Smaller and impure fragments oil of turpentine. By distilling with water,
(' varnish ') are melted down for the manufac-
a pale-yellow oil, having a strong odour and
ture of amber varnish and lac ; but in recent acrid taste, can be obtained. It blackens and
years such material is largely converted by the thickens on exposure to air and heat, boils
application of heat and hydraulic pressure into at 86, and has a sp.gr. of 0-758 at 24. One
blocks of pressed amber or ' ambroid.' About part of the rectified oil mixed with 24 parts of
35,000 kilos, of pressed amber is now produced alcohol (0-830) and 96 of ammonia, forms eau
annually from three times the amount of rough de luce, a celebrated old perfume.
' '
By mixing
amber ; it is cut for ornaments and smokers' eau de luce with nitric acid, artificial musk is
mouth-pieces. Prices (current in 1908) for made. Its solution in alcohol was formerly
' '
rough work-stone vary from III. to 10s. considered as a specific for whooping-cough (v.
per kilo, and for smaller, inferior material also OILS, ESSENTIAL, and RESINS).
(' varnish ') about 5s. per kilo. Pressed amber AMBER VARNISH v. VARNISH.
fetches 4:1. to 51. per kilo. The production and AMBERGRIS. (Anibregris, FT. ; Ambra, Am-
the trade in amber, as well as the literature of bar, Ger.) (J. Soc. Chem. Ind.1890, 429.) Is found
the subject, is almost exclusively German, in the sea, near the coasts of tropical countries,
though the finished articles are largely made in and in the intestines of the spermaceti whale
Vienna. (Physeter macrocephalus).
Other varieties of fossil resin closely allied Ambergris is generally found in fragments,
to amber, but regarded as distinct from Prussian but a piece has been obtained weighing 225 Ibs.
or Baltic amber (succinite), are the following : Its sp.gr. ranges from 0-780 to 0-926 (0-780 to
Beckerite (E. Pieszczek, 1880), a black resin 0-896 Brande, 0-908 to 0-920 Pereira). If of good
occurring with Prussian amber. quality, it adheres like wax to the edge of a
Burmite, Birmite, or Burmese amber (F. knife with which it is scraped, retains the
Noetling, 1893), a dark reddish-brown, amber- impression of the nails, and emits a tat odori-
which has long been mined in Upper
like resin, ferous liquid on being penetrated with a hot
Burma and used in China. It is found in large needle. It is generally brittle, but on rubbing it
masses, one seen by the writer weighing 33lbs., with the nail it becomes smooth like hard soap.
whilst the largest piece of Prussian amber yet Its colour varies from black to white. Its smell
found weighs only 9-7 kilos. (21 Ibs.). is peculiar, and not
easily counterfeited. It
Chemawinite (B. J. Harrington, 1891), melts at 62-2, at 100 it is volatilised as a
Cedarite (R. Klebs, 1897), or Canadian amber, white vapour ; on a red-hot coal it burns and is
found as pale yellow fragments the size of a pea entirely dissipated. Water has no action on it ;
to that of a walnut on the beach of Cedar Lake, acids, except nitric acid, act feebly upon it ;
near Chemahawin in Saskatchewan. ether and the volatile oils dissolve it ; so do
Gedrite (0. Helm, 1878), a brittle, pale yellow the fixed oils, and also ammonia when assisted
resin found with Prussian amber, but differing by heat ; alcohol dissolves a portion of it.
from this in containing less oxygen and no The principal constituent of ambergris is
succinic acid ; m.p. 140. ambre'in (q.v.) ; its inorganic constituents are car-
Glessite (O. Helm, 1881), also found with bonate and phosphate of calcium, with traces of
Prussian amber ; it contains no succinic ferric oxide and alkaline chlorides.
acid, but probably some formic acid ; m.p. Used by perfumers. The Chinese test its
200. purity by scraping it upon boiling tea, in which'
Roumanite, Romanite, Rumanite, or Rou- it should wholly melt.
manian amber (0. Helm, 1891), a brownish- AMBERITE v. EXPLOSIVES.
yellow to brown resin, found in Tertiary sand- AMBLYGONITE. Fluo-phosphate of alu-
stone at several places in Roumania ; it re- minium and lithium AlP0 4 ,LiF, crystallising
sembles Prussian amber in containing some in the anorthic system. It isusually found as
succinic acid (0 -3-3 -2 p.c. ), and is characterised by whitish cleavage masses much resembling felspar
the relatively large amount of sulphur (1 -15 p.c.) in appearance, from which it is
;
distinguished by
m.p. 300. its higher sp.gr. 3-01-3-09 and chemical cha-
Simetite, or Sicilian amber (0. Helm and H. racters. It occurs in granitic rocks at Montebras
Conwentz, 1886), a clear wine-red to garnet-red in France, Cacares in Spain, Pala in California,
resin, remarkable for its beautiful green or blue &c. At each
of the places named it has been
fluorescence, found in the river Simeto and other mined for the preparation of lithium salts, the
parts of Sicily. It contains only 04
p.c. of phosphate being a by-product. It contains
succinic acid. about 10 p.c. of lithia. L. J. S.
AMINES. 127
AMBREIN, (Arnbreine, Fr. ; Ambarstoff, Ger. ) compounds such as nitrosamines, diazo- com-
Isolated by Pelletier and Caventou, by digesting pounds and others which contain
;
nitrogen linked
to nitrogen or elements other than
ambergris in hot alcohol, sp.gr. 0-827. It is of carbon, as
a brilliant white colour, has an agreeable odour, well as to alkyl- residues. It also includes
is destitute of taste, is insoluble in water, dis- compounds in which the
nitrogen forms part
solves readily in alcohol and ether. Melts at of a ring, as in pyridine, pyrrol, and their
36, and is volatilised above 100 ; is non- derivatives, among which the alkaloids may be
saponifiable ; is converted by nitric acid into
mentioned. The majority of these more
complex
ambreic acid. Ambreiin is probably impure substances are treated of in detail in
special
cholesterol. Pelletier (Annalen, 6, 24) found it arts. Azo- COLOURING MATTERS
articles (see
;
to contain C 83-3, H
13-3, and 3-31 p.c. AZINES VEGETABLE ALKALOIDS
; BONE OIL ; ;
AMBRITE. Abrown translucent resin, QUINOLINE, &c.), and come within the scope of
similar to retinite, found in association with this only in so far .as
they possess the general
New Zealand coal. characteristics of the ammonia bases.
AMENYL. Trade name for the hydrochlo- Amines are classed as primary, secondary, or
ride of methyl hydrastimide. Forms yellowish tertiary, according as one, two, or three of the
needles, m.p. 227. Soluble in hot water or hydrogen atoms of ammonia have been replaced
alcohol. by alkyl groups. Thus the general formula of
AMERICAN COW or MILK TREE WAX the primary amines NH
R, of the secondary
is 2
v. WAX. amines NHRR', and of the tertiary amines
AMERICAN ELEMI v. OLEO-RESINS. NRR'R", where R, R', and R" may be identical
AMETHYST. A purple transparent variety or represent different alkyl groups. The re-
quartz (Si0 2 ), used as a gem-stone.
of crystallised actions of the amines differ to some extent
'
So named, from a/afdvaros, not drunken,' according as the substituting alkyl- groups are
owing to the ancient belief that the stone when (l)all aliphatic ; (2) mixed aliphatic and aromatic,
worn as a charm prevented intoxication (v. with the nitrogen attached to the aliphatic
QUARTZ). L. J. S. residue, as in benzylamine; (3) mixed aliphatic
AMETHYST. Tetramethyl safranine and and aromatic, with the nitrogen attached to a
tetraamyl safranine are found in commerce carbon atom of the benzene ring, as in methyl
under this name (v. AZINES). aniline and (4) pure aromatic amines such as
;
AMETHYST, ORIENTAL, v. CORUNDUM. aniline itself, di- and tri-phenylamine, and their
AMIANTHUS (Amiante, Fr.) Mountain homologues. Substances of groups ( 1 ) and (2) will
flax (v. ASBESTOS). be referred to here as aliphatic and aromatic
AMID ASE v. ENZYMES. amines respectively, and those of groups (3) and
AMIDE POWDER. An explosive similar to (4) as aromatic amino- compounds. Aromatic
ordinary gunpowder, in which, in place of the amino- compounds serve as the starting materials
sulphur, an ammonium salt is employed in in many of the different branches of the dyeing
combination with saltpetre, in such proportions industry, and are prepared artificially in large
that on ignition potassamide, volatile at high quantities (see arts. ANILINE; Azo- COLOURING
temperatures, is formed. This increases the MATTERS ; TRIPHENYLMETHANE COLOURING MAT-
useful effect of the explosive, which burns with- TERS; DlPHENYLAMINE, &C.).
out residue (Gaens. Eng. Pat. 14412, 1885; With the important exception of the vege-
J. Soc. Chem. Ind. 5, 678). table alkaloids, the amines are not widely
AMIDOAZOBENZENE or ANILINE YEL- distributed in nature, though some of the lower
LOW V. AZO- COLOURING MATTERS. members of the fatty series (methylamines)
AMIDOGENE. An
explosive made by dis- occur in plants and in the blood of some animals.
solving 73 parts of potassium nitrate and 1 part They are, however, found as decomposition
magnesium sulphate in one -third their weight of products of animal and vegetable organisms,
boiling water ; 8 parts of ground wood charcoal, and of mineral substances. Thus the methyl-
8 parts of bran, and 10 parts of sulphur are added, amines are found in herring brine and hi decom-
and the whole is digested for two hours at 140 ; posing fish. Others, chiefly diamines, are found
it is then dried at 50 and made into cartridges in certain pathological conditions of the urine,
(Gemperle, J. Soc. Chem. Ind. 3, 191 ; 1, 201 ; and as decomposition products of the animal
Biedermann's Chem. Tech. Jahrb. 7, 146). tissues (ptomaines). The decomposition of
AMIDOGUANIDINE v. HYDRAZINBS. proteins gives rise to large nunibers of amino-
AMIDOL. Trade name for 2 4-diamino- : acids. Aniline was first isolated as a product
phenol hydrochloride, used as a photographic of the distillation of indigo, and it and its
developer. homologues as well as other bases are present
AMIDONAPHTHOLS v. Azo- COLOURING in the distillates from bone oil (Dippel s oil),
MATTERS. and of coal tar. A mixture of fatty amines is
AMIDONAPHTHOPHENAZINE v. AZINES. obtained in the dry distillation of the residues
AMIDOPHENOPHENANTHRAZINE v. hi the beet-sugar industry, and this, under the
AZINES. name of trimethylamine,' of which it contains
'
'
AMINES.Amines or ammonia bases may
'
about 5 p.c., is used in France for the preparation
be regarded as substances derived from am- for industrial purposes of methyl chloride on ;
monia by the substitution of hydrocarbon radicles account of the greater solubility of its hydro-
for hydrogen.
They may also be looked upon as chloride, it has also been used instead of ammonia
derived from hydrocarbons by the replacement in the preparation of potassium carbonate, in a
of one or more
hydrogen atoms by or its NH manner analogous to the Solvay method for the
alkyl substitution products or "NRR'. NHR preparation of sodium carbonate, but the process
The definition of the term would include alkyl does not seem to have been commercially
derivatives of hydrazine and hydrazoic acid, and successful.
128 AMINES.'
General methods of preparation. compounds of the aliphatic and aromatic amines
are only obtained indirectly. Zinin in 1842 pre-
1. By action of ammonia or its alkyl deriva-
tives on substitution products (generally haloid pared aniline from nitrobenzene, by the action
or hydroxyl derivatives) of hydrocarbons.
of alcoholic ammoniun sulphide. On the
The method first described by Hofmann (Phil. commercial scale, as for instance in the pre-
Trans. 1850, 1, 93 ; 1851, 2, 357), of heating alkyl paration of aniline, iron and water with some
halides (preferably bromides or iodides) with am- hydrochloric acid is usually employed as the
reducing agent. Nitro- compounds, however,
monia, is available for the preparation of primary,
as well as nitriles, oximes, and hydrazones, can
secondary, and tertiary amines of the fatty
;
be .reduced to amines by electrolysis in dilute

series, and if aniline is substituted for ammonia, |
alcohol and sulphuric acid, using a nickel

for the preparation of secondary, tertiary, and
aromatic amino compounds. Quaternary am- kathode (Pierron, Bull. Soc. chim. 1899, [3] 21,
monium compounds are also formed in the
i
780). A mixture of aliphatic aldehydes and

ammonia is converted into amines if electrolysed
reactions, which may be represented as follows :
;
in sulphuric acid solution with a lead kathode,

NH 3 + RBr = NH R-HBr.2 the relative proportions of primary, secondary,
NH R + R'Br
2
= NHRR'-HBr. and tertiary amines formed depending on the
NHRR' + R"Br = NRR'R"-HBr. and the relative amounts
NRR'R" + R'"Br = NRR'R"R'"Br. strength of the current,
of aldehyde and ammonia present (Knudsen,
The reaction will take place, though only very Ber. 1909, 42, 3994). Another method for the
slowly, in water solution, more quickly in alco- reduction of nitro compounds, nitriles, oximes,
holic solution, and best on heating in alcoholic and
hydrazones, consists in heating in a stream
solution in sealed tubes at 100. The products of
hydrogen in the presence of finely divided
obtained may contain haloid salts of one or all nickel or
copper (Sabatier and Senderens, Compt.
of the possible amines, and of the quaternary rend. In all these methods
1902, 125, 225).
the temperature must not be allowed to rise too
In the preparation on the large scale of
high, or reduction of the amine to hydrocarbon
secondary and tertiary aromatic amino- com- and ammonia takes place. Other reducing
pounds, e.g. dimethylaniline, the primary amine
agents employed are sodium amalgam and water,
is heated under pressure directly with the
sodium and alcohol, sodium sulphide, zinc-dust
alcohol and hydrochloric or sulphuric acid at and
potash, stannous chloride, &c. Magnesium
180-200. Here the alkyl group is exchanged
alkyl iodide (the Grignard reagent) sometimes
directly for hydrogen without the intermediate acts as a reducing agent, and ethyl aniline has
separation of the alkyl halide. The presence of been obtained by treatment of nitrobenzene,
other negative groups in the benzene molecule with
increases the ease with which the NH 2 group Accad.
magnesium ethyl iodide (Oddo, Atti R.
Lincei, 1904 (v.) 13, 2, 220).
can displace halogen groups. Thus the chlorine Amides and amidines are also converted to
atoms of chlorbenzene can be replaced by NH 2 amines
by reduction with sodium and alcohol
groups by the action of ammonia if the benzene (Guerbet, Compt. rend. 1899, 129, 61).
ring also N0
contains 2 groups.
= RCH-NH., + H O.
Amines may also be obtained by heating RCONH, + 2H 2 2
zinc ammonium chloride with alcohols at 250- RCNH-NH; + 2H 2 = R-CH -NH + NH 2 2 S.
260 and Gasiorowski, Ber. 1884, 17, Condensation products of the action of primary
(Merz
623).
amines and aldehydes of the type R-CH : N-R',
Alcohols or phenols will react with ammonia yield secondary amines on reduction.
or alkyl derivatives on heating in the presence
its R-CH NR'
:
+H = 2 R-CH 2 -NHR'
of zinc chloride, calcium chloride, or other
(Stoermer and v. Lepel, Ber. 1896, 29, 2110;
catalytic agent (Merz and Weith, Ber. 1880, 13, Brand, Ber. 1909, 42, 3460).
1298 ; Merz and Mueller, Ber. 1886, 19, 2901). 3. From amides by the action of bromine
Mixtures of the vapours of alcohol and and potash. (Hofmann, Ber. 1882, 15, 762.)
ammonia or primary amine led through tubes This reaction is mainly applicable to the
containing finely divided thoria or tungsten preparation of primary fatty amines, and gives
oxide, at 360 give amines (Sabatier and good yields only with the lower members of the
Mailhe, Compt. rend. 1908, 148, 898). series. The first product of the reaction is a
Sodamide or its alkyl substitution products bromamide, and this on further treatment with
may be used instead of ammonia in the case of potash gives amine, potassium bromide, and car-
aliphatic amines. bon dioxide, the alkyl group being transferred
NH 2 Na + CH 3 C1
= NH 2 -CH 3 + Nad from the carbon to the nitrogen atom, as in the
'
(Lebeau, Compt. rend. 1905, 140, 1042; Cha- Beckman rearrangement.'

blay, Compt. rend. 1905, 140, 1262). Sodamide CH 3 -CONH 2 +KOH+Br 2
will also react with anhydrous sulphuric esters =CH 8 -CONHBr+KBr+H 0. 2
of the aliphatic series, and with aromatic sul- CH 3 -CONHBr+KOH = CH 3 -NH +C0 2 +KBr. 2
phonic acids to give primary amines (Jackson Azides on boiling with alcohol or water, and sub-
and Wing, Ber. 1886, 19, 902 ; Titherley, Chem.
Soc. Trans. 1901, 79, 399).
sequent treatment with cone. HC1 give amines.
2. By reduction of nitrogen-containing sub- R-CO-N 3 +C 2 H 6 -OH = RNH-COOC H.+N 2 2.
stances. R-NH-COOC 2 H 6 +H 2
This method is chiefly important in the pre- =RNH +C0 +C H OH
2 2 2 S
paration of primary amines, and particularly in (Curtius, Ber. 1894; 27, 779, 1896, 29, 1166).
that of the aromatic ammo- compounds, the nitro- 4. By the action of alkalis on alkyl isocya-
compounds of which are easily obtained by direct nates. (Wurtz, Annalen, 1849, 71, 330; 1850,
nitration of the hydrocarbons, whereas the nitro- 76, 317.)
AMINES. 129
The interest of this method is mainly amines respectively (Titherley, Chem. Soc
historical, since it led to the discovery of the Trans. 1901, 79, 399).
amines by Wurtz in 1848. Primary amines 7. By distillation ofamino- acids with baryta.
are the chief product, but secondary and tertiary
amines are also formed in small quantities.
C 2 H 5NCO+H 2 = C,H -NH a +CO,.
8 8. Aliphatic primary and secondary amines
5. By
hydrolysis of alkyl esters of thio- may be obtained by the action of potash on the
carbamines and isocyanides with concentrated p-nitroso derivatives of secondary and tertiary
acids. aromatic amino- compounds.
C 2 H SNCS+H,0 = C 2 H 6 -NH 2 +COS. NO-N-C 6H 4 (CH 3 + KOH
C 2 H 5 NC+H 2 = C 2 H -NH 2 +HCOOH.
)2
?
= C H -NO-OK + N(CH ).,H.
6 4 3
6. From compounds which certain substances NO-C 6 H -NHCH + KOH
4 3
form with alkyl halides. =C H -NO-OK+NH -CH
6 4 2 3
.
(a) Hexamethylene tetramine, formed by the 9. Tertiary amines can be obtained

action of ammonia on formaldehyde, gives by heat-
ing primary and secondary bases with excess of
addition compounds of the type C 6H 12 N 4 RI <
potassium alkyl sulphate.

with alkyl iodides. These on treatment with
HC1 and alcohol are decomposed, giving primary RR'NH + CH 3 OS0 3 K=
RR'NCH 3 + HOS0 3 K.
amines (Delepine, Compt. rend. 1897, 124, 292 ; General Properties.
Ann. Chim. Phys. 1898, [7] 15, 508). The amines of the aliphatic series are vola-
(b) Phthalimide, on treatment with alcoholic tile inflammable substances, the lower members
potash, gives potassium phthalimide, and this
being gases or liquids with low boiling-points,
gives an alkyl derivative on treatment with very soluble in water and
strongly alkaline
alkyl iodide, which on hydrolysis with fuming to litmus ; the
density of the liquid mem-
HC1 yields a primary amine. bers of the series is about 0-75 that of water,
C 6H 4 (CO) 2 NK+RI = C 6H 4 (CO) 2 NR+KL and increases slightly with increase in the
C 6H 4 (CO) 2 NR+2H 2 0=C 6H 4 (COOH) 2 +NH 2 R molecular weight. Their basicity, measured by
(Gabriel, Ber. 1887, 20, 2224 ; 1891, 24, 3104). the conductivity method, is considerably
(c) Magnesium alkyl iodides form addition greater than that of ammonia, and they will
compounds with phenyl isocyanate ; these, on saponify esters and precipitate oxides from the
treatment with water are converted into salts of many of the heavy metals. They have
anilides, which yield amines on saponification an ammoniacal and fishy odour. The smell,
(Blaise, Compt. rend. 1901, 132, 38, 478, 978). inflammability, boiling-point, and solubility in
(d) Sodium acetamide, if treated with alkyl water become less with increase in the mole-
iodide, gives mono- and di-alkyl derivatives of cular weight, and the highest known members
formula R-CONHR, and R-CONRR', and these are odourless solids at ordinary temperatures.
on saponification yield primary and secondary They react with moist air with formation of
ALIPHATIC AMINES.
Alkyl groups
130 AMINES.
HOMOLOQUES OF ANILINE.
Primary aromatic amino- compounds

AMINES. 131
forms, and a number of these have been isolated.

The quaternary ammonium compounds, unlike C 6H 5 N 2C1+C 6 H 5 N(CH 3 ) 2
their inorganic analogues, are not decomposed =C 6 H 5 N NC 6 H 4N(CH
:
3 ) 2 +HC1
on boiling with potash on heating alone they
;
aromatic
Tertiary such as compounds,
give tertiary amines and alkyl halides. The with nitrous acid to
react
dimethyl aniline,
corresponding bases are obtained from their form j9-nitroso compounds, where the nitroso
halides by treatment with moist silver oxide
nitrogen is attached to the carbon of the benzene
;
they are strongly alkaline to litmus, and the ring in the para- position to the substituted amino-
solutions generally decompose easily on evapora-
group. These are highly coloured substances,
tion, but some of the aliphatic members have and serve as intermediate compounds in the
been obtained crystalline by evaporation in
production of certain colouring matters (methy-
vacud. lene blue, &c.), which are ussd in the colour
The formation of quaternary ammonium On treatment with caustic potash
industry.
compounds by addition of excess of methyl they give secondary amines and salts of nitroso
ioJ.'le to an amine gives a quantitative method
phenol.
for the determination of the number of replace- 2. With chlorides of aromatic sulphonic acids.
able hydrogen atoms in the substance. Analysis Primary and secondary amines in strong
of the original compound and of its quaternary alkaline solution are converted into amides
methyl derivative gives the number of methyl by shaking with chlorides of aromatic sul-
groups which have entered into the molecule. phonic acids of these amides, Ph-S0 2
; and NHR
The chemical behaviour of many substances PhS0 2 NRR' respectively, the first" only are
varies with the different classes of amines, soluble in dilute alkalis with formation of salts.
and separation and purification of the amines
Tertiary amines do not react. The primary and
formed in many of the methods above referred
secondary amines can be regenerated from the
to may be carried out by making use of such amides by boiling with cone. HC1 or H 2 SO 4 at
differences. Primary and secondary amines 120-150 (Hinsberg, Ber. 23, 2963; Annalen,
usually give similar reactions, whilst tertiary 1891, 265, 178).
amines are more stable, in accordance with 3.With acetyl chloride or acetic anhydride.
the general rule for compounds which contain
Primary and secondary amines give, as a
carbon atoms linked to the maximum possible
rule, acetyl derivatives which are insoluble in
number of hydrogen atoms. cold water tertiary amines either do not react,
;
or form soluble acetates and hydrochlorides. The

Reactions.
primary and secondary amines may be regene-
1. With nitrous acid. rated by saponification of the acetyl derivatives.
Primary amines, on boiling with potassium Since the velocity of the formation of the acetyl
or sodium nitrite in acid solution, give alcohols derivative of the primary is much greater than
or phenols with evolution of nitrogen. that of the secondary amine, a method based
RNH +HONO = ROH+N +H
2 2 2
0. on this difference in property has been used to
Secondary amines give nitrosamines, which separate the two (Menschutkin, Chem. Zentr.
on boiling with cone. HC1 are again transformed 1900, 1, 1071 ; Potozki and Gwosdow, ibid.
into the original amines. 1903, ii. 339).
RR'NH+HONO = RR'N-NO+H 2 O. The action of benzoyl chloride is similar to
RR'N-NO+2HC1 = RR'NH-HCl+NOCl. that of acetyl chloride.

4. With oxalic esters.
Tertiary amines do not react. Several of the aliphatic primary and secondary
Primary aromatic amino compounds react amines react with ethyl oxalate, the former
differently if their solutions are kept cooled.
giving solid diamides and the latter liquid
They give diazo- compounds according to the oxamic esters. Tertiary amines do not react.
following equation :
Primary and secondary amines are regenerated

RNH ,HC1+HONO = RN NC1+2H
2 :
2 O.
by boiling with potash (Hofmann, Ber. 1870, 3,
This reaction is of the greatest importance, 109, 776 DuvUlier and Buisine, Ann. Chim.
;
for the diazo- compounds are very unstable, and Phys. [5] 23, 299).
on treatment with various substances either 5. With magnesium methyl iodides.
form substitution products of benzene hydro- Primary amines react, giving two molecules
carbons with evolution of nitrogen, or retain the of methane for every molecule of amine :
nitrogen and form azo- compounds, which are

the parent substances of the azo- dyes. Thus,
RNH +2MeMgI =
2 RN(MgI),+2CH 4 .
if the diazo- compound be boiled with water, Secondary amines react in a similar manner,
but give one molecule of methane for every
alcohol, cuprous chloride, bromide, or cyanide,
molecule of amine :
phenol,, benzene, chlor, brom, or cyan, derivatives

respectively are produced. If the diazo- com- RR'NH+CH 3 MgI = RR'NMgI+CH 4 .
pound is treated with a substance containing a Tertiary amines either do not react or they
phenol or aromatic amino- group, a coloured form addition compounds with the reagent
substance is formed which is capable of fixing (Sudborough and Hibbert, Chem. Soc. Trans.
itself as a dye on a fabric. Compounds derived 1909, 95, 477).
from unsubstituted amines have only a limited 6. With o-xylylene bromide.
application for dyeing purposes, as they are Primary amines react, giving two molecules
generally insoluble in water ; the sulphonic acids of HBr and liquid derivatives of o-xylyleneimine
derived from them are, however, generally (dihydroisoindol).
soluble, and are used extensively (see art. Azo- Secondary amines react, giving crystalline
COLOUBINO MATTERS). The reactions are ex- quaternary ammonium bromides and one mole-
pressed by the following equations : cule of HBr :
K 2
132 AMINES.
DIAMINES.
These may be regarded as derived from
+ 2HBr. hydrocarbons by replacement of two hydrogen
atoms by two amino- groups, or from two
molecules of ammonia by replacement of two
hydrogen atoms one from each molecule by a
, + HBr. hydrocarbon residue. Certain of them occur
^CH, as decomposition products of the animal organ-
Br ism, the chief of these being putrescine (tetra-
methylene diamine), and cadaverine (penta-
Tertiary aliphatic amines give addition pro- Diamino- acids are an
ducts of one molecule of xylylenebromide with methylene diamine).
two of amine. Tertiary aromatic amines and important product of the decomposition of
ammo- compounds do not react (Scholtz, Ber. proteins.
Preparation. The methods are entirely
1898, 31, 1707).
7. With aromatic aldehydes.
analogous to those used in the preparation of
monamines. Aliphatic diamines are obtained
Primary and secondary amines form com-
by the action of aqueous ammonia on dihalogen
pounds with loss of water :
derivatives of hydrocarbons this method is not

C SH BCHO+NH 2 R = C H CHNR+H
6 8 2 0.
;
generally applicable to the preparation of

C6H CHO+2NRR'H=C H
5 6 6 CH(NRR') 2 +H 2 0. aromatic mono- or diamino- compounds, but a
modification of it, which consists in treatment
Tertiary amines do not react (Schiff, Annalen,
of p-chlormonamines with aqueous ammonia in
159, 159).
8. With chloroform and potash. presence of copper salts, is used in the commercial
manufacture of ^-phenylene diamine and its
Primary amines give isocyanides on warming.
RNK +CHC1 +3KOH=RNC+3KC1+3H O homologues (Ger. Pat. 204848, 1908). Aromatic
2
2 3 diamino- compounds are prepared on the com-
(Hofmann, Ber. 3, 767). mercial scale chiefly by the reduction of
Secondary and tertiary amines give no dinitro- compounds ; but practically all the
characteristic reaction. methods for the production of monamines are
9. With carbon disulphide. also available for that of diamines.
Aliphatic primary and secondary amines Properties. The aliphatic diamines are
react as follows :
strongly basic substances, their basicity in-
creasing with the number of methylene groups
(Bredig, Zeitsch. physical. Chem. 1894, 13, 308).
Their boiling-points are much higher than those
of the corresponding monamines. Their hy-
On boiling the product of the action of CS 2 droxides, which are diacid bases, are extremely
on primary amines with metallic salts (HgCl 2 or stable, and are only decomposed on boiling
FeCl 3 ), mustard oils are produced, and primary with caustic alkalis or distillation over metallic
amines partly regenerated. sodium. The list of the chief aliphatic dia-
mines and their physical constants (see p. 133)
= SCNR + H * s + NH R *
-
is taken from Meyer and Jacobsen's Lehrbuch
der Organischer Chemie. The lower members
(Hofmann, Ber. 8, 105, 461; 14, 2754; 15,
of the aromatic diamino compound differ from
1290).
Aromatic amines give substituted thio ureas. the corresponding monamines by being easily
soluble in water. Their solutions in water are
2RNH 2 +CS 2 =H 2 S+(RNH) 2CS. easily oxidised, but the dry bases are stable in
With the alkali metals.
10. air.
Primary and secondary amines dissolve with Reactions. Diamines give the ordinary
evolution of hydrogen and formation of sub- reactions characteristic of the amino- group, but
stances of the type RNHK
or RNK 2 Tertiary .
primary aromatic o-amino- compounds and to
amines do not react. some extent aliphatic diamines, possess in
11. With oxidising agents. addition, the property of forming condensation
Oxidation with potassium permanganate products containing nitrogen rings, m- and p-
decomposes aliphatic amines with formation of diamines do not exhibit this property.
aldehydes and acids. 1. With aldehydes.
With Caro's acid (H Z S0 6 ), primary amines With
aliphatic diamines, cyclic compounds
of the type RCH 2 NH 2 are oxidised to hydroxyl- are formed as well as the ordinary alkylidene
amines and hydroxamic acids, all of which give bases. Thus the action of formaldehyde on cold
a characteristic colouration with ferric chloride. solutions of ethylene diamine results in the
Ketoximes are formed from amines of the type formation of a compound C 8 16 4 , to which H N
RR'CH-NH ,whilstthoseofthetypeRR'R"C-NH 2
2
the formula
give nitroso- and nitro- derivatives (Bamberger, CH 2 N CH N CH
2 g
Ber. 1902, 35, 4293 1903, 36, 710).
;
With hydrogen peroxide aliphatic, secondary,

and tertiary amines give hyclroxylamines and CH,CH
N-oxides of type RR'NOH and RR''R"NO (Dun-
stan and Goulding, Chem. Soc. Trans. 75, CH , X CH 9 N CH '
1104). has been assigned (Bischoff, Ber. 1898, 31, 3254).

Oxidation of aniline and its para compounds Aromatic o-diamino- compounds give alde-
gives quinone. hydines or anhydro bases :
AMINES. 133
ALIPHATIC DIAMINES.
134 AMINES.
the aliphatic series are decomposed on heating water. It gives the typical reactions of m-
with separation of ammonium salt and formation diamino- compounds (see above).
of cyclic compounds. Thus, tetramethylene By the action of a diazobenzene salt on
diamine gives pjTrolidine and pentamethylene m-phenylenediamine, chryso'idine (unsymme-
diamine gives piperidine: tricaldiamidoazobenzene) is produced :
NH (CH 2 ) 4 NH 2 ,HC1=NH 4C1+H 2C, CH, C 6H SN 2 C1 +C H 6 4 (NH 2 )2

2
= HC1 + C H N 6 6
: N-C 6H 3 (NH 2 ) 2 .
H,C\XCH, In the manufacture of phenylene-brown and

NH chrysoidine the solution of crude m-phenylene-
CH, diamine hydrochloride obtained by the reduction
NH 2 (CH 2 6NH 2 ,HC1=NH 4 C1+H 2 C//\CH 2
)
of m-dinitrobenzene is employed, without first
H ,C\ isolating the base. A violet colouring matter is
obtained by heating m-phenylenediamine with
NH d
aniline hydrochloride to 190 -200, and a blue
The higher homologues, however, do not colouring matter by heating it with m-phenylene-
form ring compounds containing a corresponding diamine hydrochloride (Krause, Ber. 9, 835).
number of atoms in the ring. Thus, octomethy- p-Phenylenediamine. C 6H 4 (NH..).j. Obtained
lene diamine hydrochloride, on heating, does not by reducing p-dinitrobenzene (Rinne and Zincke,
give octomethylene imine, which would contain Ber. 7, 871), or ji-mtraniline (Hofmann, Proc.
a ring of nine atoms, but 2-butylpyrrolidine. Roy. Soc. 12, 639), or aminoazobenzene (Martius
Similarly, decamethylene diamine gives 2- and Griess, J. pr. Chem. 97, 263), with tin and
hexylpyrrolidine (Blaise and Houillon, Compt. hydrochloric acid, aniline being formed simul-
rend. 1906, 142, 1541 ; 1906, 143, 361). taneously in the case of aminoazobenzene.
The aromatic diamines are the starting- Along with dia mi nodi phenyla mine by reducing
points for the preparation of a large number of aniline-black with tin and hydrochloric acid or
dyes, and hence are of commercial importance. with hvdriodic acid and amorphous phosphorus
The following are the chief members of the (Nietzki, Ber. 11, 1097). By distilling (1, 2, 5)-
series : diaminobenzoic acid (Griess, Ber. 5, 200). By
o-Pheniile,nediamine C 6 4 (NH 2 ) 2 First ob- H . action of ^-chloraniline on aqueous ammonia in
tained by Griess by the distillation of o-m- and presence of copper salts. Crystals, melting at
m-p- diaminobenzoic acid : 147. Boils at 267. Sublimes in leaflets.
C 6H 3 (COOH)(NH 2 ) 2 =C 6H 4 (NH 2 ) 2 +CO, Readily soluble in water, alcohol, and ether.
(1, 2, 3, or 1, 3, 4) (1, 2) Yields quinone on oxidation. When oxidised in
(J. pr. Chem. [2] 3, 143). By the reduction the presence of primary amines or phenols it
of o-nitraniline C 2 H 4 (N0 2 (NH 2
(1, 2) (Zincke ) ) gives indamines and indophenols, these on heating
and Ber. 6, 123), or of o-dinitroben-
Sintenis, produce safranines. By heating it with sulphur
zene H
C 6 4 (NO 2 ), (1, 2) (Rinne and Zincke, to 150-180, it is converted into diamino-
Ber. 7, 1374), with tin and hydrochloric acid. thiodiphenylamine (leucothionine, Lauth's white)
Crystallises from water in laminae, melting at
102. Boils at 252. Readily soluble in water,
alcohol, and ether. Diaeid base, the sulphate
2[C e H (NH
4 2)2 ,H 2 S0 4 ] 3H 2 O forms nacreous which, when oxidised with ferric chloride, yields
laminae. It gives all the reactions for o-diamino- thionine (Lauth's violet)
compounds referred to above. On oxidation N
with ferric chloride it gives a red compound,
diaminophenazine :
NH, H
+C H6 4 (NH 2 2 +30)
The latter colouring matter may also be obtained
NH 5 by the simultaneous oxidation of p-phenylene-
X diamine and sulphuretted hydrogen by ferric
chloride in aqueous solution (Lauth, Compt. rend.
C 6H 2 (NH 2 82, 1441 Bull. Soc. Chim. 25, 422 ; Bernthsen,

) 2 +3H 2
;
Annalen, 230, 108). If dimethyl-^-phenylene-

diamine C 6H 4 (NMe 2 )(NH 2 ) is substituted for
N
m-Phenylenediamine C 6H 4 (NH 2 ) 2
p-phenylenediamine in the foregoing reaction,
By re- .
tetramethylthionine (methylene blue) is formed

ducing m-dinitrobenzene or m-nitraniline with
iron filings and acetic acid (Hofmann, Proc. (v. Methylene blue).
Roy. Soc. 11, 518; 12, 639), or with tin and Tolylene-diamines (Diaminotoluenes)
hydrochloric acid (Gerdemann, Zeitsch. f. Chem. C,H 3 (CH 3 )(NH 2 ) 2.
1865, 61). By reducing either (1, 2, 4)- or All the six

possible compounds are known.
(1, 2, 6)-dinitrobenzoic acid with tin and Their physical constants are as follows :
hydrochloric acid, the carboxyl group being M.pt. B.pt.

eliminated in the process (Zincke and Sintenis, l-Methyl-2 : 3-diaminobenzene 61 255
~
Ber. 5, 791 Griess, Ber. 7, 1223).
; On a manu- 4 99 283~285
C
facturing scale it is prepared by reducing dinitro- 64 273
benzene with iron turnings and hydrochloric 103
acid. Separates from its solutions as an oil 88 265
which does not readily solidify unless brought 284
in contact with a crystal of the base. Melts Only two of these however, are of technical
at 63, and boils at 287. Readily soluble in importance.
AMINO-ACIDS. 135
H
Tolylenediamine C S 3 (CH 3 )(NH.2 ) 2 (1, 2, 4). tion of o-#-dinitraniline or of chrysoidine. On
Obtained by the reduction of the corresponding oxidation it gives triaminophenazin.
idnitrotoluene. Sparingly soluble in cold, 1.3.5-triaminobenzene is only known in the
readily soluble in boiling water, in alcohol, and form of its salts.
in ether. Forms crystalline salts. As the two 1.2.3.4. and 1.2A.54elraminobenzenes pre-
amino groups in this compound are in the pared by the reduction of oximes and nitro
meta- position to one another, it is an analogue compounds, have been isolated as their sparingly
of r-phenylenediamine, which it resembles in soluble sulphates (Nietzki and Schmidt, Ber.
many of its reactions : thus 2 4-tolylenediamine
:
1889, 22, 1648 Nietzki, Ber. 1887, 20, 2114).
;
may either wholly or in part replace the m- Pentaminobenzene has been obtained as the
phenylenediamine used in the manufacture of hydrochloride with 3 molecules of HC1, by reduc-
phenylene-brown, producing colouring matters tion of triaminodinitrobenzene (from tribrom-
is redder than that of ordinary
the shade of which henzene and ammonia). Pentaminotoluene has
phenylene-brown. been similarly obtained.
Tolylenediamine C SH S (CH 3 )(NH 2 ) 2 (1, 2, 5) Reduction of triaminotrinitrobenzene gives
is obtained by the reduction of the corresponding pentaminobenzene (Palmer and Jackson, Ber.
m-nitro-o-toluidine C SH 3 (CH 3 )(NH 2 )(N0 2 ) (1,2,5) 1888, 21, 1706; Palmer, and Grindley, ibid.
with tin and hydrochloric acid (Beilstein and 1893, 26, 2304). M. "B. T.
Kuhlberg, Annalen, 158, 350 ; Ladenburg, Ber. AMINO-ACIDS. The amino-acids may be
11, 1651). Formed along with o-toluidine when conveniently described under the two headings
the aminoazotoluene prepared from o-toluidine (a) Aliphatic Amino-acids, and (b) Arcmatic
is treated with the same reducing agent : Amino-acids.
Aliphatic Amino-acids. The amino-fatty
acids are of great physiological importance,
CH 3 them occurring in plant and animal
of
JCH,
+2H 2 many
organisms. They are products of proteid de-
gradation, and may be obtained from proteins
CH, by heating with hydrochloric acid or baryta
CH, water. The general methods in use for pre-
NH S paring these acids are :
NH, (i.) By treating the monohalogenated fatty

acids with ammonia :
CH 2C1-COOH - CH (NH }COOH.

2 2
The two bases may be separated by fractional Chloracetic acid. Glycine.
distillation (Nietzki, Ber. 10, 832). This reaction
(ii.) By heating the cyanhydrin
of an alde-
is utilised in preparing the mixture of o-toluidine
and -y-tolylene-diamine which, after the addition hyde or ketone with ammonia and then hydro-
lysing the product, whereby an o-amino-acid
is
of a second molecule of a monamine (either
aniline or o- or ^-toluidine), yields on oxidation
produced :
safranine. On a large scale the aminoazo-

toluene is reduced with iron turnings and hydro- -> CH 3 -CH(NH 2 )C0 2H.
chloric acid. Crystallises in colourless
rosettes
Alanine.
of tabular crystals. Readily soluble in water, acids
alcohol, and ether, sparingly soluble
in benzene. (iii.) By the reduction of the cyanofatty
C 6H 3 (CH 3 )0 2 with nascent hydrogen (Zn and HC1 or by heating
Yields on oxidation toluquinone .
with HI)
Other diamines of this series are
Xylylene diamines :
CN-CO-OH + 2H = CH,(NH
2 2 )C0 2H.
Cyanoformic acid.
1.3-dimethyl, 2.4-diaminobenzene, m.p. 64.
1.3- 4.6 104. The amino-fatty acids are crystalline bodies with
77. usually a sweet taste,
and are readily soluble
1.3- 2.5
feeble
Diaminotrimethylbenzenes : diamino- pseudo- in water. They are amphoteric, i.e.
cumenes: bases and feeble acids. Important members
5. 6-diamino benzene, m.p. 90. are glycine, alanine, phenylalanine, tyrosme,
1.2.4-trimethyl,
1.2.4- 3.6 m.p. 78. leucine, and valine, serine, cystme. trypto-
acid,
Diamino mesitylene : phane, histidine, arginine, lysine, aspartic under
90. and acid, which are described
glutaminic
1.3.5-trimethyl, 2.4-diaminobenzene, m.p. also PROTEINS).
Similar diamines have been prepared from their respective headings (v.
Aromatic Amino-acids. A true aromatic
naphthalene and other hydrocarbons. (b)
amino-acid such as anthranilic acid, contains
united
both the amino and the carboxyl- groups
AND PENTAMINES. Isomeric
TEIAMINES, TETRAMINES, to carbon atoms in the benzene ring.
with these are acids which contain the
ammo
Very few substances are known.
of these introduced
<rroun or the carboxyl- group or both,
Their properties are similar to those of other
Fnto fatty side chains, the last two
classes being
substances containing the amino group. acids.
1.2.3- triaminopropane ; b.p. 190 really substituted fatty
(Curtius,
J. pr.Chem. 1900, 62, 232). The general methods in use for preparing
aromatic amino-acids are :
2.3.5-<riawino7txane(Morelli and Marchetti, nitro-
Atti del Accad. Lin. 1908, [5] 17, 1, 250). (i.) reducing the corresponding
By
The three modifications of triaminobenzene I acids :
are all known. C 6H 4 (N0 2 )COOH(1:2)->0 6

H 4 (NH 2 )COOH(1:2)
Vnitrobenzoic acid. Anthranilic acid,
1.2.3- triaminobenzene m.p. 103; b.p. 336.
;
the halogen esters with
1.2.4- triaminobenzene is formed by reduc- (ii.) By treating
136 AMINO-ACIDS.
the b p. 135-5 (15
mm
The ethyl ester melts at
potassium phtalimide and hydrolysing
)-
pro-
13 and boilsjit 136 -137^ (13 20V -
duct with hydrochloric acid at 200. ^mm.ât
The aromatic amino-acids are used in the 268 (corr.) (Frankel and Spiro, Ber. 1895, 1684).
Aminobenzoic acid alkamine esters (v. jj-amino-
preparation of azo-dyestuffs (q.v.).
o-Aminobenzoic acid. Anthranilic acid benzoic acid).
C 6H 4 (NH 2 )C0 2 H
Anthranil CH
(1:2). /CO
It was obtained by heating indigo with
first
C 6H 4< or C 6H 4\ I
^>0
j
caustic potash (Fritzsche, Annalen, 39, 83). It
may be prepared by the reduction of o-nitrp- j

is the anhydride or lactam of anthranilic acid,
benzoic acid with tin and hydrochloric acid its being still under discussion. It
constitution being
derivative
(Beilstein and Kiihlberg, Annalen, 163, 138),
,
is
prepared by treating the dimercury
or with zinc and sodium bisulphite (Gold- of o-nitrotoluene (obtained by suspending o-
berger, Chem. Zentr. 1900,
ii. 1014; v. also nitrotoluene in water and heating it with freshly
Preuss and Binz, Zeit. angew. Chem. 1900, [16] oxide and caustic soda)
precipitated mercuric
385 and Bad. Anil. u. Soda Fab. Eng. Pat. 18319 ; with concentrated hydrochloric acid and decom-
J. Soc. Chem. Ind. 1900, 774) ; by heating o- posing the product with water (Kalle and Co.
chlorbenzoic acid and ammonia at 125 under Fr Pat. 370522; D. R. P. 194364; J. Soc.
(Fabw. Meister, Lucius und Bruning, Chem. Ind. 1907, 278 1908, 713) ; by heating
;
R. P. 145604; Chem. Soc. Abst. 1904, i.

S-essure
. o-nitrotoluene with caustic soda to 170 (Kalle
50) ; by treating phthalimide with bromine
and and Co. D. R. P. 194811 ; Chem. Soc. Abstr.
caustic potash (Hoogewerff and van Dorp, Ber. 1908, i. 786) ; by the reduction of o-nitrobenz-
Ber.
1891, Ref. 966; Bad. Anil, und Soda Fab. aldehyde with aluminium amalgam (Briihl,
D. R. P. 55988 ; Frdl. ii. 546 ; Amsterdamsche 1903, 3634) and by the oxidation of o-amino-
;
Chininefabrik. Eng. Pat. 18246 ; J. Soc. Chem. benzaklehyde with a neutral solution of Caro's
Ind. 1891, 831) ; by boiling phthalhydroxylamic persulphuric acid (Bamberger
and Demuth, Ber.
acid, formed by treating phthalic anhydride 1903, 829 ; 2042).
with hydroxylamine, with caustic soda or sodium Anthranil is an oil, readily volatile in steam
1 _ //^11~ T> J /~1~.,1 *3'Amlinn Tj\. T>rt4- and boils at 210-
carbonate (Cie. Par. de Coul. d' Aniline, Fr. Pat.
L
j
possesses a peculiar odour,
318050 ; J. Soc. Chem. Ind. 1902, 1392 ; Farbw. 213. It dissolves in alkalis to form salts of
Meister, Lucius und Bruning, Eng. Pat. 1982, anthranilic acid and on treatment with acetic
D. R. P. 136788 ; Easier Chemische Fabw. ; anhydride yields acetylanthranilic acid.
D. R. PP. 130301, 130302) ; by reducing sulph- m- Aminobenzoic acid. Semantic acid
anthanilic acid electrolytically or with sodium C 6 H 4 (NH 2 )C0 2 H (1:3), is prepared by re-
amalgam (Kalle and Co. D.R. P. 129165; Chem. ducing m-nitro benzoic acid with ammonium sul-
Zentr. 1902, i. 1138 ; D. R. P. 146716 Chem. Soc. acid with
;
phide and subsequently precipitating the
Abst. 1904, i. 159) ; by treating o-nitrotoluene tartaric acid (Holleman, Rec. Trav. Chim. 1902,
with concentrated alcoholic or aqueous alkali [ii.] 21, 56;
v. also Gerland, Annalen, 91, 188).
(Bad. Anil, und Soda Fab. D. R. P. 114839; It is a colourless crystalline solid, m.p. 174 ;
Chem. Zentr. 1900, ii. 1892) ; and by heating sparingly soluble in cold, readily so in hot water.
isatoic acid with concentrated hydrochloric acid Reduction with sodium amalgam in hydro-
(Kolbe, J. pr. Chem. [2] 30, 124). chloric acid yields ?n,-aminobenzyl alcohol (Lang-
Anthranilic acid is of great commercial guth, Ber. 1905, 2062). Concentrated hydriodic
importance, as it is one of the intermediate acid transforms it into ammonia and benzoic
products in the manufacture of synthetical acid (Kwisda, Monatsh. 12, 428). m-Amino-
indigo. It crystallises in colourless plates, benzoic acid is used in the preparation of azo-
m.p. 145, and is readily soluble in alcohol or dyestuffs (q.v.) (Bayer and Co., D. R. PP. 58271,
water. It condenses with formaldehyde, form- 59081, 60494, 60500, 63104, 64529, 69445,
ing compounds which are of use in the prepara- 74198, 74516, 78493, 86314; Frdl. iii. 614
tion of indigo (Heller and Fiesselmann, Annalen, et seq., Ill et seq. iv. 793, 795
: Ges. f. Chem. ;
324, 118 Bad. Anil, und Soda Fab. D. R. PP.

; Ind., D. R. P. 76127 Frdl. iii. 746).
;
Amino-
117924, 158090, 158346; J. Soc. Chem. Ind. benzoic acid alkamine esters (v. ^-aminobenzoic
1905, 615). Reduction with sodium amalgam acid).
in hydrochloric acid solution yields o-amino- H
p. Aminobenzoic acid C 6 4 (NH 2 )C0 2 (1 4), H :
benzylalcohol (Langguth, Ber. 1905, 2062). is prepared by the reduction of y-nitrobenzoic

Concentrated hydriodic acid decomposes it at acid with ammonium sulphide (Fischer, Annalen,
200 into ammonia, carbon dioxide, aniline and 127, 142) or with tin and hydrochloric acid
benzoic acid (Kwisda, Monatsh. 12, 427) ; whilst (Beilstein and Wilbrand, Annalen, 128, 164).
nitrous acid converts it in aqueous solution into It is a colourless crystalline solid, m.p. 186-
salicylic acid. Anthranilic acid is employed in 187, readily soluble in water, alcohol, or ether.
the preparation of azo- dyestuffs (q.v.) (v. also Strong hydrochloric acid at 180 converts it
Bayer and Co. D. R. PP. 58271, 60494, 60500, into aniline and carbon dioxide (Weith, Ber. 1879,
86314 ; Frdl. iii. 614, et seq. iv. 795). 105) and hydriodic acid at 200 into ammonia,
The methyl ester of anthranilic acid occurs in carbon dioxide, and benzoic acid (Kwisda,
Neroli oil (oil of orange flowers) (Walbaiim, Monatsh. 12, 428). ^-Aminobenzoic acid is
J. pr. Chem. 1899, 59, [6-71 350). It is prepared used in the preparation of azo- dyestuffs (q.v.)
by heating anthranilic acid with methyl alcohol (Bayer and Co. D. R. PP. 58271, 60494, 60500,
and hydrochloric acid (Erdmann, Ber. 1899, 86314 Frdl. iii. 614 et seq. iv. 795
;
Ges. ; ;
1213; D. R. P. 110386) or from acetylanthra- f. Chem. Ind., D. R. P. 76127 Frdl. iii. 746). ;
nilic acid, methyl alcohol and mineral acids and alkamine esters
Many complicated alkyl-
(Erdmann, D. R. P. 113942; Chem. Zentr. 1900, of the aminobenzoic acids have been prepared
ii. 831). It is a crystalline solid, m.p. 24-5, and they are claimed to be valuable anaesthetics
AMMONIA. 137
(Farbw. Meister, Lucius, and Bruning, D. R. PP. 1878, 583), or by reducing dioxindole with tin
170587, 172301, 172447, 172568, 179627, 180291, and hydrochloric acid, or with sodium amalgam
180292, 194748, Eng. Pat. 17162, Fr. Pat. (Bayer and Knop, Annalen, 140, 29). Crystal-
361734, U. S. Pat. 812554 ; J. Soc. Chem. Ind. lises in colourless
needles m.p. 120. ;
1906, 607 ; 1907, 434 ; Chem. Soc. Abstr. 1906, 3-Amino-a-toluic acid (3-Aminophenylace-
i.845etseq. ; 1907, i. 923 ; 1908, i. 638; Merck, tic acid) NH 2 -C 6 H 4 -CH 2 -C0 2 H (1 :
3). Obtained
D. R. P. 189335; J. Soc. Chem. Ind., 1908, by reducing 3.nitro-o-toluic acid with tin and
471 ; Bayer and Co. D. R. PP. 211801, 218389, hydrochloric acid ; m.p. 148-149 (Gabriel and
Eng. Pat. 4321 ; J. Soc. Chem. Ind. 1909, 854 ; Borgmann, Ber. 1883, 2065).
Chem. Zentr. 1910, i. 782 ; Fritzsche, Eng. Pat. 4-Amino-a-toluic acid (4-Aminophenylacetic
2020, Fr. Pat, 398259, 1). R, P. 213459; acid) NH
2 -C 2 H 4 -CH
2 -C0 2 (1:4). Method of H
J. Soc. Chem. Ind. 1909, 814). preparation as above (Radziozewski, Ber. 1869,
4-Amind-o-toluic acid C 6 H
3 -CH 3 (NH 2 )C0 2 H 209); m.p. 199-200 (Bedson, Chem. Soc.
(1:4:2); m.p. 196. Obtained by the reduction Trans. 1880, 92).
of 4-nitrotoluic acid with tin and hydrochloric
acid (Jacobsen and Wierss, Ber. 1883", 1959). Obtained by heating a-phenylbromacetic acid
5-Amino-o-toluic acid C 6 H 3 -CH 3 (NH Z )C0 2 H with aqueous ammonia at 100-110 (Stockenius,
(1:5:2); m.p. 153, is obtained by the re- Ber. 1878, 2002); m.p. 256 (Tiemann, Ber.
duction of 5-nitrotoluic acid with tin and hydro- 1880, 383). Sublimes without melting at 265
chloric acid (Jacobsen, Ber. 1884, 164). (Elbers, Annalen, 227, 344).
6-Amino-o-toluic acid C 6 3 -CH 3 (NH 2 )C0 2H H a-AMINO CAPROIC ACID v. LEUCINE.
(1:6:2). Method of preparation as above; AMINONAPHTHOPHENAZINE v. AZINES.
m.p. 191 (J. andW. I.e.). AMINOPHENYLACETIC ACID v. AMINO-
H
2-Ar,iino-m-toluic acid C 6 3 -CH 3 (NH 2 )C0 2 H ACIDS (AROMATIC).
(1:2:3). Method of preparation as above ; AMINOPHENOPHENANTHRAZINE v.
m.p. 132 (Jacobsen, Ber. 1881, 2354), 172

(Jurgens, Ber. 1907 4409). a- and 0-AMINOPROPIONIC ACIDS v.
<i-Amino-m-toluic acid (Methylanthranilic ALANINE.
acid) H
C 6 3 -CH 3 (NH 2 )-C0 2 H (1:4: 3).
Obtained a- AMINO-Mo VALERIC ACID v. VALINE.
by reduction of 4.nitro-rn-toluic acid with tin AMLA (Beng.), AMLIKA (Hind.), AMLIKU
and hydrochloric acid (Jacobsen, Ber. 1881, 2354) (Ass.), OWLA (Mechi), NELLI and TOPPINELLI
or by treating p-methylisatoic acid with concen- (Tarn.). A euphorbiaceous Indian tree, Phyllan-
trated hvdrochloric acid (Panaotovic, J. pr. thus emblica (Linn.), the fruits of which (Emblic
Chem. ; m.p. 172
[2] 33, 62) (Ehrlich, Ber. 1901, myrobalans ) are used in a fresh condition as a laxa
-
3366), 175 (Findeklee, Ber. 1905, 3533). tive, and, when dried, as an astringent (Dymock,
H
6-Amino-m-toluic acid C 6 3 -CH 3 (NH 2 )C0 2 H Pharm. J. [3] 10, 382). The fruits are also pickled
(1:6:3); m.p. 167. Obtained by reduction and eaten, and used for tanning and dyeing.
of 6-nitro-m-toluic acid (Beilstein and Kreusler, AMMONAL v. EXPLOSIVES.
Annalen, 144, 147). AMMONIA. Volatile, alkali, alkaline air,
H
2-Amino-p-toluic acid C 6 3 -CH 3 -(NH 2 )-C0 2 H spirit of hartshorn. Solutions of ammonia have
(1:2:4); m.p. 164-165. Method of preparation been known from very early times, but the
as above (Ahrens, Zeitsch. f. Chemie, 1869, 104). substance itself was first clearly recognised by
3-Amino-p-toluic acid (Homo-anthranilic acid) Priestley, who obtained it by heating the aqueous
H
C 8 3 -CH 3 (NH 2 )C0 2 H
(1:3:4); m.p. 177. solution and collecting the gas, which he termed
Method of preparation as above (Niementowski alkaline air, over mercury. Scheele proved that
and Rozanski, Ber. 1888, 1997 ; Noyes, Amer. itcontained nitrogen ; and Berthollet, and more
Chem. J. 10, 479). accurately Austin, demonstrated its real nature,
I'-Amino-o-toluic acid (Benzylamine-o-car- and determined the proportions of its con-
boxylic acid) NH 2 -CH 2 -C SH 4 -C0 2 H (1:2). Ob- stituents.
tained by digesting part of o-cyanobenzyl-
1 Ammonia (or its salts) is found in small
phthalimide with 4 parts of concentrated sulphuric quantities in the air, and in most natural ; water
acid (Gabriel, Ber. 1887, 2231).
Crystalline non- in the juice of plants, in most animal fluids, in
volatile solid.
many soils, and in a few minerals, ochres, clays,
I'-Amino-m-toluic acid
(Benzylamine-m-car- marls, &c. Ammonia can be obtained syntheti-
bnxylic acid NH 2 -CH 2 -C 6H 4 -CO 2 H
(1 3); m.p. :
cally in small quantity by the passage
of elec-
215-218. By heat;ng at 200
a mixture of trical discharges through a mixture of nitrogen
2 grams m-cyanobenzylphthalimide and 10 c.c. and hydrogen (Donkin, Pogg. Ann. 21, 281); or
concentrated hydrochloric acid (Reinglass, Ber. as nitrite by the action of a strong induction
1891, 2419). spark on a mixture of nitrogen
and water
as
l'-Amino-p-toluic acid (Benzylamine-p-car- vapour (The'nard, Compt. rend. 76, 983) or ;
H
boxylic ocjW)NH 2 -CH 2 -C 6 4 -C0 2 H(l 4). Method : chloride by sparking a mixture of hydrogen,
of preparation as above
(Giinther, Ber. 1890, nitrogen, and hydrogen chloride (Deville, Compt.
1060). Crystalline solid. rend. 60, 317) or by the action of heated spongy
;
2-Amino-a-toluic acid (2-Aminophenylace- platinum, pumice, &c., on

a mixture of hydrogen
<tc and) NH2 -C 6
H 4 -CH
2 -C0 2 H(1:2) is not known and nitric acid.
in the free state ; all For laboratory purposes the gas is usually
attempts to prepare it
result in the formation of its oxindole.anhydride, prepared by heating a mixture of
ammonium
Oxindole chloride or sulphate with slaked lime, or by
and
gently warming the concentrated solution,
is
C H *<NH 2
obtained by treating 2-nitro-a-toluic acid

>CO drying the gas over quicklime. (For
the' pre-
see Stas,
paration of the chemically pure gas,
with tin and hydrochloric acid Zeitsch. anal. Chem.
(Bayer, Ber. 6, 423.)
138 AMMONIA.
Ammonia is a colourless gas, having a very becomes nearly complete at 630 under atmo-
pungent characteristic smell, and is poisonous spheric pressure, but the last traces do not dis-
when breathed in quantity, destroying the appear even at 1000. Conversely, in presence
mucous membrane. It has a sp.gr. of 0-5967 of iron as catalyst, Haber and v. Oordt find that
(air
= 1), 1 litre of the gas at and 760 mm. at 1000 traces of ammonia are formed from
weighing 0-7708 gram, and readily liquefies on nitrogen and hydrogen at atmospheric pressure,
compression, the critical temperature being 131, and Nernst and Jost have found that small
and the critical pressure 113 atm. Liquid quantities are formed at the same tempera-
ammonia is colourless and very mobile, and has ture under the greater pressure of 50-70 atm.
a sp.gr. at 0/4 of 0-6385 (Dieterici), 0-6388 Recently, however, Haber has found that at
(Drewes), the coefficient of expansion being very temperatures of 500-550 under 200 atm.
high and increasing rapidly with the temperature. pressure, presence of metallic osmium or
in
It boils under atmospheric pressure at 33-5, uranium, nitrogen and hydrogen combine to a
and freezes to a white crystalline solid at 75 considerable extent (see below).
(Faraday), 77 (Brill), the vapour pressure being Ammonia gas is very soluble in water,
as follows (Regnault, J. 1863, 70) : alcohol, ether, and many saline solutions, the
at 30 1-14 atm. at 4-19 atm. aqueous solution (caustic ammonia or liquor
-20 1-83 10 6-02 ammonia) being of great commercial importance.
One gram of water at and 760 mm. absorbs
-10 2-82 20 8-41
1148 c.c. or 0-875 gram of ammonia, at 10"
Its latent heat of evaporation is, with the excep- -679 gram, at 20 -526 gram, at 30 -403 gram,
tion of that of water, higher than that of any and at 100 0-074 gram (Roscoe and Dittmar,
known liquid, amounting to about 5000 cal. Chem. Soc. Trans. 12, 128 Sims, Chem. Soc.
;
at 15 and 5600 cal. at its boiling-point, and on Trans. 14, 1 see also Perman, Chem. Soc.
;
this account it is produced commercially in Trans. 79, 718; 83, 1168). In the act of
large quantity for employment in freezing solution much heat is evolved, and according to
machines. In many of its physical properties Thomsen, NH 3 +aq. = 8430 cals.
the liquid resembles water, and it acts as a solvent The density of aqueous solutions of ammonia
for a large number of substances. of varying strength, according to the deter-
Ammonia gas burns with difficulty in the minations of Lunge and Wiernik, is given on
air when cold, but inflames more readily on p. 139.
heating, and still more readily in oxygen, The solution is very strongly alkaline, and
giving a greenish-yellow flame of high tempera- unites with acids to form the ammonium salts,
ture. In presence of suitable catalysts, such as and it is frequently supposed that the solution
copper, iron, nickel, and especially platinum, contains ammonium hydroxide NH
4 -OH, corre-
ammonia is oxidised by oxygen at lower tem- sponding to NaOH
and KOH. The evidence
peratures with production of oxides of nitrogen, for this view is not altogether conclusive, and
the manufacture of nitric acid from ammonia by the physical properties of the solution at the
Ostwald's process (Eng. Pat. 698, 1902) being ordinary temperature are in some respects
carried out in this manner. A number of the opposed to the presence of the compound
elements, when heated in ammonia gas, yield NH 4 OH, and in favour
of the supposition that
corresponding nitrides, boron, magnesium ; and the ammonia is dissolved as such. At very low
titanium being especially active in this respect, temperatures, however, Rupert ( J. Amer. Chem.
whilst the alkali metals give rise to amides. Soc. 31, 866; 32, 748) has shown that two
With carbon at temperatures above 750 definite hydrates exist, the freezing-point curve
ammonia is partly dissociated, and partly of mixtures of ammonia and water in varying
converted into hydrocyanic acid, the presence proportions showing two well-defined minima at
of the latter in crude coal gas being largely due 87 and 94 respectively, the composition at
to this reaction. these two points corresponding to the formulae
Manysalts combine Avith ammonia to form NH 3 ,H 2 and 2NH 3 ,H 2 0. The first-named forms
stable compounds at the ordinary temperature, small colourless crystals resembling those of
the ammonia playing the same part as water of sodium and potassium hydroxide ; and the latter,
It is evolved on heating, liquid Whether these
crystallisation. larger needle-shaped crystals.
ammonia having been first obtained by Faraday, are true hydrates or are to be regarded as
in 1 823, by warming the compound with silver ammonium hydroxide NH 4 OH and ammonium
chloride 2AgCl,3NH 3 in a sealed tube.
, oxide (NH 4 2 0, is at present uncertain.
)
The action of heat upon ammonia has been The aqueous solution of ammonia also dis-
investigated by Ramsay and Young (Chem. Soc. solves many metallic oxides and hydroxides,
Trans. 45, 92), Perman (Proc. Roy. Soc. 74, such as Ag 2 0,Cu(OH) 2 , as well as many salts
110; 76A, 167), Haber and v. Oordt (Zeitsch. which are insoluble in water, such as silver
anorg. Chem. 44, 341), and Nernst and Jost chloride and phosphate, and cuprous chloride, and
(Zeitsch. Elek. 13, 521). Under atmospheric also acts as a solvent for many fats and resins.
pressure, decomposition commences at tempera- The solution of cupric hydroxide in ammonia
tures below 500, its extent increasing rapidly is of considerable commercial importance, as
with the temperature, but the speed with which it is a solvent for cellulose, and is used in
equilibrium is attained between undecomposed large quantities in the manufacture of artificial
ammonia and nitrogen and hydrogen varies silk.
greatly according to the nature 'of the surfaces Technical sources of ammonia. 1 Ammonia
I.
with which the gases are in contact. Glass is is formedin nature chiefly during the decay of
very inactive, but porcelain and many metals nitrogenous organic substances, and conse-
and their oxides have a very strong accelerating
For more complete details, see Lunge's Coal- Tar and
effect. In presence of the latter decomposition Ammonia, chaps, xii.-xv. (Uuriiey and Jackson, 1909).
AMMONIA. 139
quently exists in considerable quantity both in with some insoluble matter. Ammonium sul-
the soil and the atmosphere. Whilst this is of phate is contained in the Tuscan soffioni,' and
'
the importance for agriculture, it is is there obtained in considerable quantity as a

greatest
only possiblein very exceptional cases to by-product in the manufacture of boric acid.
utilise thissource for the manufacture of am- Ammonium chloride, together with sulphate, is
monium salts, practically the whole of the sometimes found in the neighbourhood of
world's production being obtained by the volcanoes.
destructive distillation of nitrogenous organic B. Synthetic processes for production of
matter, chiefly coal. ammonia. Very many attempts have been
A. Natural occurrence of ammoniacal com- made to effect the manufacture of ammonia from
pounds in quantity of commercial importance. atmospheric nitrogen, and a large number of
Ammonium carbonate has been found in guano with this object have been patented,
deposits on the West Coast of South America, itherto, however, no method which has been
S'ocesses
and has been imported into Europe, a sample proposed has proved successful on a commercial
imported into Germany in 1848 consisting scale, for although, as stated above, nitrogen and
essentially of ammonium bicarbonate mixed hydrogen combine together to a slight extent to
DENSITY OF AQUEOUS SOLUTIONS OF AMMONIA AT 15 (LUNGE AND WIEKNIK).
Sp.gr.
140 AMMONIA.
about 500, and cooling between each passage of It is stated that sal-ammoniac made from it was
the gas over the metal, Haber has synthesised an article of commerce as early as 1410, and
ammonia at the rate of about 90 grams per hour, that the Jesuit Sicard in 1720 saw the manu-
the ammonia separating out on cooling under facture of it in the Delta of the Nile. In Egypt
these conditions as a liquid. Larger plant is sal-ammoniac was made by burning camels'
now being erected by the Badische Anilin und dung and collecting the sublimate. Putrefied
Sodafabrik. urine (in which the urea has passed into ammo-
Attempts to effect the synthesis by the nium carbonate) has been used for centuries,
passage of the silent discharge and of sparks and to a certain extent is still used by dyers as
through the mixture of nitrogen and hydrogen a source of ammonia for scouring wool and
have also failed to effect a sufficient yield of other purposes. The methodical working up of
ammonia. Patents for this type of process have urine collected in large quantities, or of sewage
been taken out by Young (Eng. Pat. 1700, 1880), for obtaining ammonia therefrom, has been
Muller and Geisenberger (Eng. Pat. 1481, 1879 ;
carried out in the neighbourhood of some large
1592, 1879), the Sociefed' Azote (D. R. P. 17070), towns, e.g. Paris, but only a very small quantity
Nithack (D. R. P. 95532), West-Deutsche of ammonia in comparison with the enormous
Thomasphosphatwerke (D. R. P. 157287 and quantity excreted is actually obtained in this
179300), Gorianoff (Fr. Pat. 368585), Hooper way-
(U.S. Pat. 791194), and Cassel(D. R. P. 175480); Normal urine contains per litre from 20 to
see also Briner and Mettler (Compt. rend. 35 grams urea (carbamide), which after a short
144, 694), and Davies (Zeitsch. physikal. Chem. time is changed into ammonium carbonate
64, 657). A similar lack of commercial success under the influence of a micro-organism. An
has hitherto attended the efforts to produce adult man produces from 22 to 37 grams urea
ammonia by combining atmospheric nitrogen per 24 hours, together with a little uric acid,
with elements which readily form nitrides, such corresponding to 12-5-21 grams NH
3 per day,
as boron, titanium, magnesium, and calcium, or between 9 and 17 Ibs. per annum. If all the
and subsequent conversion of the nitride into ammonia obtainable from London urine were re-
ammonia by the action of steam patents in this
; covered this would amount to 100,000 tons of
respect having been taken out by Bassett (Eng. ammonium sulphate per annum.
Pat. 4338, 1897), Lyons and Broadwell (U.S. Owing to the now almost universal adoption
Pat. 816928), Wilson (Eng. Pat. 21755, 1895), of the removal of sewage by means of water, the
Mehner (Eng. Pat. 12471, 1895 ; 2654, 1897 ; dilution of the ammonia in the combined sewage
28667, 1903), Kaiser (Eng. Pat. 26803, 1905), isso great that its recovery is hardly practicable,
Borchers and Beck (D. R. P. 196323), and Roth but with concentrated pan sewage, recovery of
(D. R. P. 197393). ammonia is carried on in a few places, especially
0. Production from cyanides. It has long in Paris. A large number of patents have been
been known that nitrogen combines at high taken out for the recovery of ammonia both from
temperatures with carbon and alkalis with sewage and also from the more concentrated sludge
production of cyanides, and many attempts deposited in the collecting tanks at the sewage
have been made during the last fifty years to works, among which may be mentioned Duncan
manufacture cyanides in this manner and to (D. R. PP. 27148, 28436), Young (Eng. Pat.
convert these subsequently into ammonia by 3562, 1882), Bolton and Wanklyn (Eng. Pat,
the action of superheated steam. The large 5173, 1880), Gesellschaft fur Wasserabklarung,
demand for cyanides themselves, resulting from Berlin (D. R, P. 161166), Butterfield and
their employment in the extractions of gold Watson (Eng. Pat. 19502, 1905), Taylor and
from the mine tailings, and the fact that at Walker (U.S. Pat. 603668).
present nitrogen, in the form of cyanide, com- j
In Paris there are daily 2200 cubic metres
mands a higher price than in the form of (say tons) of urine and night soil taken out of
ammonia, has made such processes of no value the fosses, and treated by various processes.
for ammonia production under In the Bilange process the sewage is mixed with
existing condi-
tions, and in fact, at the present time, the milk of lime and allowed to settle, the liquid
opposite process of converting ammonia into portion is worked for ammonia, the muddy de-
cyanides is carried on to a large extent. The posit (containing a great many albuminoid
methods proposed, so far as they relate to matters) is heated by steam, passed through
cyanide production, will be discussed under filter-presses and sold as manure. In the
that heading, but one method may be here Kuentz process the muddy deposit is mixed
mentioned, namely, the manufacture of calcium with a reagent prepared by treating a mixture
cyanamide, Ca N'C :
N, according to Frank of bauxite, natural phosphate of lime, and
and Caro's process (j. Soc. Chem. Ind. 1908, hydrated oxide of iron with hydrochloric acid.
1093), by the action of nitrogen on heated The resulting mass is passed through filter-
calcium carbide, this being simultaneously a presses ;
the cakes remaining in these contain
cyanogen and an ammonia derivative (v. Cyan- all the phosphoric acid (10-12 p.c.) as dicalcic
amide, art. NITROGEN, ATMOSPHEEIC, UTILISA- phosphate, precipitated by ammonium car-
TION OF). This substance may readily be con- bonates the iron has absorbed the sulphur
;
verted into ammonia by the action of

super- compounds, and the alumina has modified the
heated steam, but it is for the most part albuminous and slimy matters which would
directly employed on the land as a nitrogenous have impeded the filtration. The percentage of
manure.
nitrogen in these cases is 3-3-5.
D. Ammonia from urine, sewage, and animal
Ketjen (Zeitsch. angew. Chem. 1891, 294)
excreta. Urine is not merely the oldest, but also reports a successful recovery of ammonia
for centuries was the only source for obtaining from concentrated sewage by distillation with
ammonia compounds on a commercial scale. lime at Amsterdam.
AMMONIA. 141
Ammonia from guano, &c. Whilst

E. the limits of 0-9 and 2-0 p.c. thus Tidy (Lunge's
;
ammonia obtainable from excreta is mostly lost Coal Tar and Ammonia, 4th ed. p. 872) found
for immediate recovery, as it quickly passes in Welsh coal 0-91 p.c., in Lancashire coal 1-25
away into the water, the soil, or the air, there p.c., and in Newcastle coal 1-32 p.c., whilst
are a few exceptions to this rule presented by Foster (Inst. Civ. Eng. 77, iii. 23) found in Welsh
the deposits of birds' excrements on some desert anthracite 0-91 p.c., in English coals 1-66-1-75
'
islands, and a few similar cases. In this guano,' p.c., and in Scotch cannel 1-28 p.c. Schilling
ammonia salts exist already preformed, and (J. Gasbel, 1887, 661), using the Kjeldahl
ammonia can be formed from other nitro- method of estimation, obtained from West-
genous substances contained therein by heating phalian coal 1-50 p.c., from Saar coal 1-06 p.c.,
guano with lime (as patented by Young in 1841), from Silesian coal 1-35 p.c., from Bohemian coal
not remunerative, since the 1 -36 p.c., from Saxon coal 1 -20
but this process is p.c., from Boldon
direct manurial value of guano is much superior to (Durham) coal 1-45 p.c., from Pilsener cannel
that of the ammonia salts obtainable therefrom. 1-49 p.c., and from Bohemian lignite 0-52
p.c.
F. Manufacture of ammonia by the destructive McLeod (J. Soc. Chem. Ind. 1907, 137) analysed
distillation of nitrogenous organic matter. The 80 samples of Scotch coals and cannels, and found
total quantity of ammonia commercially pro- percentages of nitrogen varying from 0-91 to
duced by all of the methods described above is 1 -87,and averaging 1 -43.
at present almost negligible, nearly the whole of The Avorld's production of coal in 1909
the world's supply of ammonia and its salts amounted to about 950,000,000 tons, containing
being obtained as a by-product in the course of on the average probably some 1 -3 p.c. of nitrogen,
other manufactures in which nitrogenous organic which, if the whole were recovered as ammonia,
matter is subjected to the process of destructive would represent an output of about 48,000,000
distillation. By far the greatest proportion is tons of ammonium sulphate per annum. In
obtained in the manufacture of illuminating gas, fact, however, the production, as shown by the
power gas, or coke from coal, and in the distilla- above figures, only amounts to about ^ of this
tion of shale for the production of shale oil. A quantity. Fully 90 p.c. of the coal is con-
considerable amount is also recovered from the sumed in such a manner that the recovery of
gases evolved from blast-furnaces where coal is the nitrogen is impracticable, and where the
used as fuel, and smaller quantities from the processes in use are such that ammonia is
distillations of bones, horn, and other animal recovered, only a relatively small proportion of
refuse, and also from the residue obtained from the nitrogen is actually obtained in the form of
beet-root molasses. ammonia, for reasons discussed later in con-
The total production of ammonia in the sidering the different manufactures in which it
United Kingdom, calculated as sulphate, for the is produced.
years 1907-8-9, is shown in the following (a) Production of ammonia in the manufacture
table, the figures for 1889 being also given to of coal gas, and of coke in by-product coke
ovens.
indicate the increase in production during the The carbonisation of coal in retorts for the manu-
past 20 years. The statistics are taken from the facture of illuminating gas for general distribu-
Annual Reports of the Chief Alkali Inspector : tion at present yields the largest contribution of
1889 1907 1908 1909 ammonia, but the output from this source is
Gas works 87,000 165,474 165,218 164,276
.
being rapidly approached by that obtained in
Iron works 5,500 21,024 18,131 20,228
. the analogous process of carbonising the coal in
Shale works 22,000 51,338 53,628 57,048
. ovens for the manufacture of hard metallurgical
Coke ovens .
53,572 64,227 82,886 coke. Formerly the great bulk of such coke was
Producer gas and manufactured in beehive ovens, in which case
other carbon- no by-products were recovered, but these are
ising works . 3,000 21,873 24,024 24,705 now being rapidly replaced by by-product
recovery ovens, the quantity of ammonium
117,500 313,281 325,228 349,143 sulphate obtained from this source in the United
The world's production for 1907 is given in Kingdom having increased from about 10,000
Mineral Industry, 16, 31, as follows :
tons in 1899 to 83,000 tons in 1909.
In both industries, however, only a portion
Great Britain .
331,220 metric tons (2204 Ibs.) of the nitrogen of the coal is recovered in
Germany .
287,000 the form of ammonia, the remainder being
United States .
81,400 distributed in the coke, as nitrogenous com-
Holland and Bel-
pounds in the tar, as cyanide in the gas and
gium . . 55,000 ammoniacal liquor, and as free nitrogen in the
France . .
52,900
gas. The relative proportion of the nitrogen
Other European
obtained in the different forms varies consider-
countries .
88,000
ably, being dependent both on the nature of the
coal and on the conditions of carbonisation ;
895,520 the rate at which the latter proceeds, and es-
Of the German production, only 30,000 tons were pecially the temperature employed have a
produced from gas works, the remainder being marked influence. At low temperatures, such,
derived chiefly from coke ovens. for example, as are employed in the manufacture
' '
Coal always contains nitrogen in greater of coalite (about 450), a very large proportion
proportion than is present in fresh vegetable of the nitrogen remains in the coke, but with
matter, this being probably due to the remains higher temperatures, although more nitrogen
of animals is given off from the coke primarily in the form
inhabiting the coal-forming forests
and swamps. The total percentage of nitrogen of ammonia, this is partly converted into hydro-
found in the coal usually varies between the
cyanic acid by the action of incandescent carbon
142 AMMONIA.
and partly dissociated into itselements, the (b) Production of ammonia in the manufac-
latter being especiall}* the case when the volatile ture of producer gas from coal. In the manufac-
products as well as the residual coke are strongly ture of producer gas from carbonaceous fuel (see
heated. The maximum yield of ammonia, GAS, PRODUCER) by the introduction of limited
when carbonising in horizontal retorts appears amounts of air and steam into the incandescent
to take place at a temperature of about 900- fuel, the whole of the carbon of the latter is
950, but with vertical retorts heated to much gasified together with the nitrogen it contains.
higher temperatures, a greater yield of ammonia Where the quantity of steam added is limited,
is claimed, owing to the fact that the volatile so as to ensure that the gas produced shall only
products are not raised to so high a temperature contain small percentages of carbon dioxide,
before escaping from the retort. the temperature of the producer is such that
The following tables, which give figures almost the whole of the ammonia formed from
obtained over a long period of working in gas- the nitrogen is dissociated into its elements as
works and coke ovens respectively, probably fast as it is produced. If, on the other hand, a
represent a fair average of the distribution of the large excess of steam is employed, the tempera-
nitrogen in the two industries under modern ture of the producer is so much lowered that the
conditions, although doubtless in different works greater part of the ammonia escapes decomposi-
considerable variations from these figures occur. tion, and may then be recovered from the gas
The gas-works figures are given by McLeod evolved. The latter contains much larger
(J. Soc. Chem. Ind. 1907, 137) as the result of percentages of hydrogen and carbon dioxide
working at the Provan Gas Works, Glasgow, than that obtained by the use of smaller quan-
and the coke-oven figures by Short ( J. Soc. Chem. tities of steam, but is still capable of economic
Ind. 1907, 581) for the working of Otto-Hilgen- employment, especially in gas engines. The
stock Coke Ovens, using Newcastle coal. process is therefore now largely adopted for
producers using bituminous fuel, especially in
Gas works Coke ovens
the Mond Gas plant, in which up to about 75 p.c.
Nitrogen in coke . 58-3 . 43-31 p.c. of total
3-9 of the nitrogen in the coal is recovered as am-
in tar . . 2-98
as ammonia 17-1 . 15-16 monia. This is usually obtained direct as
,, as cyanide . 1-2 . 1-43 ,,
sulphate by washing the crude gas with dilute
as free nitro- sulphuric acid, and subsequent evaporation and
gen in the gas 19-5 . 37-12 crystallisation of the solution obtained ; the
sulphate thus produced has, however, generally
McLeod does not appear, however, to include in a yellow or brownish colour, due to the presence
his cyanide figures the hydrocyanic acid removed of small amounts of tarry matter.
from the gas during condensation, allowance for The employment of steam, except in very
which would probably raise the cyanide figure limited quantity, is impracticable in the carboni-
to about 1 -5 p.c. sation of coal in gas works and coke ovens, as
In both gas and coke-oven works the am- the chief products required in those industries
monia is recovered by cooling the gas, when tar are gas of relatively high illuminating power
and aqueous vapour condense, the condensed and calorific power, or good coke, or both ; and
water removing a large portion of the ammonia the addition of steam in such quantity as
and other gaseous impurities from the gas, and materially increases the yield of ammonia, effects
the remainder being recovered by washing the so large a depreciation in the quality of
gas and
cooled gas with water. Recently, also, in coke- coke produced that the loss in these respects far
oven works, processes have been adopted in outweighs any increased revenue obtained from
which the ammonia is directly recovered from the additional quantity of ammonia formed.
the hot gas by washing with sulphuric acid (c) Production of ammonia from shale. In
after removal of the tar. Methods for manu- the distillation of Scotch bituminous shales for
facturing ammonium sulphate direct from the the production of shale oil (see PARAFFIN),
crude gas, in which the sulphuretted hydrogen ammonia is also evolved, and is recovered in a
present is simultaneously oxidised to form the similar manner to that employed in gas works.
necessary sulphuric acid, have been described by In this case also the introduction of steam (and
Feld (Eng. Pat. 3061, 1909) and Burkheiser also of limited quantities of air)
during the
(Eng. Pat. 20920, 1908; 21763, 1908; 17359, distillation has the effect of largely increasing
1910), but the processes are still (1910) in the the percentage of nitrogen recovered as ammonia.
experimental stage. The objections to the method which hold in the
The various apparatus employed and methods case of the gas industry do not
of working are described in the articles on GAS
apply in the-
shale-oil manufacture, as the chief
product, the
(COAL) and COKE. The yield of ammonia in shale oil, is not materially affected
both gas works and coke ovens, calculated as by the use of
steam, and the coke formed is in any case of
sulphate, amounts usually to 20-25 Ibs. per ton. little value. The gas produced, even when
Many attempts have been made to increase steam is used, is sufficiently good for the purpose
the proportion of nitrogen converted into for which it is used, namely, for
heating the
ammonia, but none applicable to these two retorts. The addition of steam for increasing
industries has had any success. Cooper's lime the yield of ammonia was, in fact, first worked
process (Eng. Pat. 5713, 1882), in which lime out to practical success in this industry, chiefly
is added to the coal before
carbonisation, was by Young and Beilby (Eng. Pat. 1587, 1881 ;
tried in many works, and abandoned, as,
although 2164, 1881 ; 4284, 1881 ; 1377, 1882 ; 5084,
a greater yield of ammonia was obtained, the 1882 ; see also Beilby, J. Soc. Chem. Ind. 1884,
gain hi this respect was more than counter- 216), its application in the case of carbonisation
balanced by the loss due to depreciation in the of coal in producers for the same
purpose being
quality of the resulting coke. of rather later date.
AMMONIA. 143
(d) Ammonia from Mast furnaces. Where then passing through hot milk of lime to absorb
coal is used as fuel in blast furnaces for cast-iron the acetic acid, and finally through
sulphuric
waste gases contain considerable acid to recover the ammonia as sulphate.
production, the (It
quantities of ammonia
and tarry matters, which is claimed that not
only is a quantitative yield
are now largely recovered from the gas, the latter, of ammonia obtained from the
nitrogen of the
after purification, being employed in gas engines. peat, but that some ammonia is also formed
In most English districts, the coal available is synthetically from the nitrogen of the ah- used.)
not sufficiently hard for use in the furnaces, and Details of the results on the
manufacturing scale
hard coke is used, the employment of coal being have not yet been published.
confined chiefly to the West of Scotland and to Frank and Caro, in
conjunction with the
North Staffordshire, where coal of sufficient Mond Gas Co. (Zeitsch.angew. Chem. 1906,
hardness can be obtained. The recovery of the 1569), find that peat containing 50 p.c. of water
tar and ammonia is effected by cooling and wash- may be employed in place of coal in the Mond
ing in a similar
manner to that employed in gas Gas plants, with production of gas suitable for
works, the apparatus being suitably modified
to gas engines, and a yield of about 90 Ibs. of am-
allow for the fact that the tar and ammonia are monium sulphate per ton of dry peat.
much more diluted with other gases, and that (/) Ammonia from bones, horn, leather, hair,
large quantities of
dust are mechanically carried skins, and other animal refuse. In the distillation
along with the gas from
the blast furnace. of bones for the manufacture of bone charcoal
'
Processes for the washing of the gas with dilute (animal charcoal, or char '), used especially in
so far to have been sugar refining, large quantities of ammonia are
sulphuric acid do not appear
permanently successful, and the same is
true formed, together with tar rich in pyridines,
of the process of Addie (Eng. Pat. 4758, 1882 ; known as 'Dippel's oil.' The carbonisation is
3246, 1883), in which the gas was mixed with frequently carried out, especially in France and
sulphur dioxide and passed through
a scrubber Germany, by heating the bones in open pots
fed with water, the resulting solution of am- placed in a furnace, in which case the tar and
monium sulphite being oxidised to sulphate by ammonia are so largely diluted with hot furnace
injection of air. gases that their recovery is rendered very diffi-
The yield of ammonium sulphate obtained cult. In this country generally, and to an in-
from blast furnaces is very similar to that creasing extent elsewhere, the carbonisation is
obtained in gas works and from coke ovens, effected in closed retorts, and the tar and am-
namely from 20 to 25 Ibs. per ton of coal. monia recovered in accordance with the usual
Ammonia
(e) from
peat. Vast deposits of gas works practice, the yield of ammonia being
peat exist in many places, especially in Ireland equivalent to about 50-60 Ibs. of sulphate per
and Prussia, and as this contains a good deal of ton of dry bones.
nitrogen, amounting in some cases to
4 p.c. of Other animal refuse, such as wool, hair,
the dry peat, many attempts have been made to skin, waste leather, &c., is sometimes carbonised
recover this nitrogen as ammonia. The great in a similar way, the residue being employed as
difficulty in the way has been
the very large manure, and the ammonia recovered from the
quantity of water contained hi the peat, which gases. Sometimes, however, these materials are
is costly to remove, and hitherto very little simply heated in cylinders in a current of steam,
ammonia has been put on to the market from which renders them friable and capable of ready
this source, Of the earlier attempts that of disintegration, when they are directly employed
Grouven (D. R. PP. 2709, 13718, 18051) is of as manure. A further proposal is to utilise the
interest, inasmuch as this represents one of the nitrogen by heating the dried refuse with con-
attempts to increase the yield of ammonia
first centrated sulphuric acid, whereby the nitrogen
by injectionof steam during distillation, but is converted quantitatively into ammonium
although prolonged experiments were made sulphate, as in the well-known Kjeldahl method
with the process, it was ultimately abandoned. of estimating nitrogen.
Lencauchez suggested the use of peat in gas (g) Ammonia as a by-product in the beet-root
producers with subsequent ammonia recovery, sugar industry. During the evaporation of beet-
and patents relating to the matter were taken root juice, small amounts of ammonia are
out by Ruderer, Loe, and Gumbart (D. R. P. evolved, which Vibrans (D. R. P. 15513) has
53844), Kuntze (Eng. Pat. 9052, 1891), and proposed to collect. Much larger amounts can,
Pieper (Eng. Pat. 28190, 1896). however, be obtained by the distillation of the
'
More recently Woltereck (Eng. Pat. 16504, vinasse,' i.e. the residue left after fermenting
1904 ; 28963, 1906 ; 28964, 1906) has patented the sugar remaining in the molasses, and dis-
a process for recovering ammonia and other tilling off the alcohol produced. This contains
products from peat, and works for carrying out nitrogenous bases, especially betai'ne,
and on
the method have been erected near Carnlough dry distillation yields ammonia and trimethyl-
Harbour, in the North of Ireland. In his amine. Vincent (Chem. News, 39, 107) carried
process, the wet peat is placed in a generator, out the distillation with the primary object of
and burned in a current of air and steam, obtaining trimethylamine and from the latter
regulated so as to keep the temperature of the methyl chloride, but the ammonia was simul-
generator very low and at the same time to taneously recovered as sulphate. The residue
effect almost complete combustion of the peat, from the distillation is rich in potassium salts,
no attempt being made to obtain a combustible and is employed as a manure or worked up into
gas. The products, in addition to the waste pure salts. Other patents dealing with the
gases, are chiefly small quantities of tarry recovery of ammonia by distillation of vinasse
matter of the paraffin series, acetic acid and are those of Ernst (D. R. P. 13871), Lederer
ammonia, the first being removed by treating and Gintl (D. R. P. 17874), and Meyer (Eng. Pat.
the hot gases with high boiling oils, the gas 17347, 1887). Bueb (Eng. Pat. 7175, 1895;
144 AMMONIA.
20259, 1898 ;
sec also Ost, Zeitsch. angew. the cooling, chloride being only present to any
Chem. 19, 609) utilises the vinasse for the pro- extent in the hydraulic main and condenser
duction of both ammonia and cyanides, the liquor, but the total quantity of ammonia
latter being the product especially aimed at. j
present is insufficient to remove the whole of
In his process the vinasse is carbonised in retorts the remaining acid gases, which are separated
in the ordinary manner, and the gases, which later by special purification processes. Other
contain ammonia and trimethylamine, but little ammonium salts are, however, produced in the
hydrocyanic acid, are then passed through a liquor by secondary reactions thus the sulphide ;
highly heated brickwork chamber, the ammonia

is oxidised by the oxygen always present in the
being only slightly affected, whilst the trimethyl-

crude gas, and later by the oxygen of the air to
amine is converted chiefly into hydrocyanic acid. which it is exposed during storage, yielding
The resulting gases, containing about 7 p.c. of polysulphides, thiosulphate, sulphate, and
ammonia and 7 p.c. of hydrocyanic acid, are possibly sulphite. The cyanide reacts with
the polysulphide, forming thiocyanate, and
passed through" sulphuric acid to recover the
ammonia as sulphate, and the gas freed from possibly also with thiosulphate, forming
ammonia employed for the manufacture of thiocyanite and sulphite, so that polysulphide
is rarely if ever found in the liquor. Small
cyanide.
II. Properties and Composition of Ammoniaca 1 quantities of ferrocyanide are also sometimes
Liquor. The ammoniacal liquor obtained by formed by the action of ammonium cyanide
the washing and cooling of the gases produced on the ironwork of the apparatus. In
by destructive distillation, is, after separation I
addition, the liquor always contains small
from tar by settling, a liquid having a colour !
quantities of pyridine, and considerable amounts
from pale yellow to dark brown, and smelling of substances derived from the tar, especially
strongly of ammonia, sulphuretted hydrogen, j
phenols.
and also of phenols. Its specific gravity usually j
From the point of view of the subsequent
varies from 1-01 to 1-03. In the coal-gas working up of the ammoniacal liquor, it is
manufacture, the liquor is usually obtained in i
important to distinguish between the amount of

' ' ' '
and ammonia
j
three stages, viz. (1) the hydraulic main liquor, volatile fixed present. The
formed during the cooling of the gas to tempera- i
former represents the ammonia present as sul-
tures of 50-60, which is usually weak (0-5-1-0 phide, carbonate, and cyanide, and in combina-
p.c. of NH 3 ), owing to the lessened solubility of
tion with the phenols, the term being given
ammonia at that temperature ; (2) the con- because the ammonia in this form is completely
denser liquor, produced in the subsequent dissociated and volatilised by simply boiling the
cooling of the gas to atmospheric temperature, solution ; whereas that present as chloride,
which is more concentrated (23-5 p.c. of NH 3) ; sulphate, thiosulphate, and thiocyanate is not
and (3) the scrubber and washer liquor, formed evolved to any material extent under these
conditions, and is therefore termed
' '
by washing the cooled gas to effect complete fixed

removal of the ammonia, the strength of which ammonia. For its recovery it is necessary to
varies considerably, and depends largely on the add to the liquor a sufficient amount of a stronger
construction of the washing plant, and the alkali to combine with the whole of the above-
supervision of the working. The first two named acids present. The ' fixed ' ammonia in
'
products together form the virgin liquor,' i.e. the average liquor usually amounts to from
solution produced from the water formed by the 20 to 25 p.c. of the whole, but the proportion is
condensation of the steam always present in the much higher in the hydraulic main and con-
crude gas ; but the liquor from all sources is denser liquor.
usually collected together with the tar in a The table on p. 145 gives the results of
common storage well or wells. Frequently the a number of analyses of ammoniacal liquor
weak hydraulic main liquor is used, after cooling, from gas-works, coke-ovens, shale-works, and
in the preliminary washers or scrubbers, thereby iron-works, made by Linder, on behalf of the
effecting a further partial removal of the am- Chief Alkali Inspector, and published in the
monia, and becoming simultaneously concen- annual reports of the latter. In addition an
trated, but for the complete removal of the analysis is also given of the liquor obtained in low-
ammonia the gas must be washed with fresh temperature carbonisation as practised in the
water in the final scrubber. In coke-oven coalite manufacture, and two analyses of German
works the conditions prevailing in these respects gas-works liquor, by Mayer and Hempel (J.
are very similar generally to those in gas works. Gasbel, 1908, 428). (For methods of analysis,
The quantitative composition of the ammo- see Linder (Alkali Inspector's Report, 1909, 15),'
niacal liquor varies considerably, not only in and Mayer and Hempel (I.e.).) In these analyses
that obtained at different stages of the process, the whole of the carbon dioxide and sulphuretted
but also in the average liquor obtained, being hydrogen present is calculated as the normal
dependent on the nature of the coals carbonised, carbonate and sulphide respectively, and in
the conditions of carbonisation, and the con- Linder's analyses the difference between the
struction and working of the condensing and total sulphur and that present as sulphide,
scrubbing plant. The qualitative composition sulphate, and thiocyanate is calculated as
varies but little ; the primary products formed ammonium thiosulphate.
in the liquor are ammonium chloride, sulphides, The existence of free ammonia (or its
carbonates, and cyanide, produced by the hydroxide) a point on which considerable
is
action of the ammonia solution on the acid difference of opinion exists. The above analy-
constituents of the crude gas, viz. hydrochloric tical results appear to show that in the case of
acid, sulphuretted hydrogen, carbon dioxide, average stored liquor, the quantity of acids
and hydrocyanic acid. The strongly acid hydro- present, including phenol, is usually sufficient to
chloric acid is absorbed in the earlier stages of combine with the whole of the ammonia
AMMONIA. 145
but at the same time it is very probable that amount may be considerable. The presence
of
some of the salts, especially the sulphides and cyanide is objectionable, as
it increases the
carbonates, undergo hydrolytic dissociation into amount of hydrocyanic acid in the waste
gasea
acid and free ammonia or its hydroxide in the from the manufacture of ammonium sulphate
solution. With the hydraulic main liquor, (see below).
formed at temperatures mostly above 60, the III. Valuation of Ammoniacal Liquor. In
acids found are insufficient to combine with the this country, for technical
purposes, the strength
whole of the ammonia, some of which must of the ammoniacal liquor is
mostly expressed in
therefore be present in the free state. The terms of
'
ounce-strength,' this figure repre-

existence of free ammonium cyanide in the liquor senting the number of ounces avoirdupois of
has also frequently been denied, but more pure sulphuric acid required to neutralise the
perfect methods of analysis have shown that ammonia contained in 1 gallon of the liquor, and
this is undoubtedly often present in small for statistical purposes or sale, the volumes of
quantity even in stored gas-works liquor, and liquor are usually converted into the equivalent
that in coke-oven liquor, which is usually only volume of liquor of 10-oz. strength. In order to
stored for a short time before working up, the convert these figures into the more
generally
COMPOSITION OF AMMONIACAL LIQUOK.
146 AMMONIA.
the was expelled with the steam. Addition of lime
invariably recovered from the liquor in
first
instance by distillation. Formerly, also, in to drive offthe fixed ammonia was rarely
many cases, only the volatile ammonia was practised with such plants, owing to the forma-
recovered, as this could be obtained without tion of thick deposits of lime salts on the heated
addition of alkali, the fixed ammonia being run boiler plates. These plants have now been
off with the waste liquor; but this procedure is almost entirely superseded by continuous
now becoming exceptional, the fixed ammonia, column stills, constructed on the general
principle of the Coffey still,
the intermittent
except in the case of some small plants, being
also mostly recovered by addition of the system being now employed only in very small
such as the distillation
necessary alkali. On account of its cheapness, works or in special cases,
lime is almost always employed for this purpose, of liquors containing very large quantities of
but in some small plants, caustic soda is used, fixed ammonia, in which case the addition of
for although the cost of the latter is much the necessary amount of lime renders the liquid
makers to be so thick that these must be stirred by mechanical
greater, this is held by some
compensated for in such plants by the fact that agitators to effect complete recovery of the
the stills run much longer without cleaning. ammonia. The annual report of the Chief
The plant employed in the distillation has Alkali Inspector for 1909 shows that in the
been of various types ; at first an intermittent various districts into which the United Kingdom
in externally fired is divided for administration purposes under the
process of distilling the liquor
boilers was adopted, the distillation being con- Alkali Act, the proportion of liquor distilled by
tinued until the whole of the volatile ammonia intermittent stills varies from about 7 p.c. to nil,
FIG. 1.
and probably averages over the whole country ammonia previously prepared from the gas
from 1 to 2 p.c. liquor. Much the largest proportion of the
For the purpose of heating the stills, three liquor is converted into sulphate, the demand
methods have been employed (1) external
: for this salt being greatest, owing to its employ-
firing ; (2) by means of internal coils through ment as a nitrogenous manure. The method of
which steam is passed and (3) by blowing live
; manufacture of this salt will therefore be de-
steam through the stills. The first plan gives scribed first, followed by that of the other
a high fuel consumption, as well as trouble from commercially important ammonia derivatives.
lime deposits on the heated portions of the still ; Ammonium sulphate. A
description of the
and of the other two methods the use of live different forms of intermittent stul formerly
steam is the most economical in fuel consiimption, adopted for obtaining the ammonia in the
and is therefore now almost invariably adopted. liquor, but now seldom used, may be found
The ammonia evolved on distillation is in Lunge's Coal Tar and Ammonia 4th
converted at once either into ammonium sul- ed. Of the continuous stills, those of
phate, concentrated gas liquor, pure aqueous Gruneberg and Blum (D. R. P. 33320) and of
ammonia, or liquefied ammonia. The remaining Feldmann (Eng. Pat. 3643, 1882) will be de-
salts of commercial importance, namely, am- scribed, more recent forms differing from these
monium chloride, carbonate, and nitrate, are now only in detail and not in general principles. In
rarely manufactured directly from the ammonia the manufacture of sulphate, the volatile
as evolved from the stills,but are obtained ammonia is first driven off, lime being then
either from ammonium sulphate or aqueous
1
added to the liquor to liberate the fixed ammonia,

AMMONIA. 147
the combined gases evolved being passed through gas liquor. The economiser j, and the saturator
sulphuric acid. B, with the gas-bell F, require no special explana-
The apparatus of Griineberg and Blum is tion.
shown in Fig. 1, as arranged for the manufacture
of sulphate. A is the still, B the gas-liquor
heater or economiser, c the lime pump, and D
the saturator charged with acid for absorption
of the ammonia. The gas liquor enters the
economiser B by means of pipe a, and is heated
by the hot waste gases from the saturator, and
passes thence by the pipe b to the top of the
column E of the still. This column is divided
into a number of compartments by horizontal
division plates, the liquor flowing downwards
from compartment to compartment by the
overflow pipes, the admitted steam travelling
upwards in the reverse direction through the
central pipes o, covered by hoods having
which compel the steam to bubble
serrated edges,
through the liquor in each compartment, thus
'
driving off the

'
volatile ammonia and also the
volatile acids present, viz. carbon dioxide,
sulphuretted hydrogen, and hydrocyanic acid.
The lime vessel F, into which milk of lime is
pumped by means of pump c and pipe c, serves FIG. 2.
to expel the fixed ammonia, and the boiler G,
with its stepped cone, serves to boil the liquor in In more recent types of still,
only a single
thin sheets, by means of the steam coil d, and column is usually employed, the lime
being
thus to set free the last portions of ammonia. introduced into one of the compartments of
In B the first heating of the liquor takes place by the lower portion of the still, which
may be
means of the hot vapours from the saturator D, made of larger size for this purpose, the hood
which ascend through the bell q, the pipe s, and being also more deeply sealed to effect more
the inner pipes of B, while the liquor, arriving vigorous agitation. The mixture of liquor and
at a, rises up in B. It then enters through 6 into lime then passes through the lower
compartments
the dephlegmating column E, and finds its way of the still, constructed in a similar manner to
downward from chamber to chamber, till it gets those above. A still of this type, manufactured
into the lime vessel F. From here it overflows by the Berlin Anhaltische Maschinen Actien-
by pipe / into the sludge-catcher g, overflows Gesellschaft, is shown in Fig. 3.
here again all round at Mi, and runs over the
cone i downwards from step to step ; from the
pipe k it is discharged continuously and quite
spent to the overflow t. The steam travels in
the opposite way namely, along the steps of
cone i, upwards in pipe m, and through n into
the lime vessel F. From here the mixed steam
and ammonia vapours ascend into the column
E, and traverse this from chamber to chamber,
and ultimately leave it by the pipe 2). This pipe
enters the saturator D, charged with sulphuric
acid. The sulphuretted hydrogen, carbon
dioxide, &c., collecting in the bell q, are led
through the flue s into the economiser B, where
they give up their heat to the gas liquor, and
lose their steam in the shape of condensed water.
Ultimately they are conveyed away by a pipe
not shown in the diagram for treatment to
prevent nuisance, the methods adopted for the
purpose being described below.
In the apparatus of Feldmann ( D. R. P. 2 1 708 ) ,
Fig. 2, the gas liquor, after having passed through
the ordinary rectifying column A, flows into a
FIG. 3.
vessel B, into which milk of lime is pumped by
G in regular intervals, whilst the whole is kept Other modifications relate chiefly to im-
agitated by steam injected into the mixture. provements in mechanical details, and in making
The liquor, after having deposited most of the the parts more accessible for cleaning, especially
lime, flows into a second column c, where the in the portions of the still where lime is present.
ammonia set free by the lime is distilled off : Thus Wilton (Eng. Pat. 24832, 1901) replaces
the spent liquor runs away continuously through the central pipe for the steam and circular hood,
(I, and the gases and vapours pass over by pipe by a narrow opening extending over nearly the
h into the first column BA, which serves both for full diameter of the still, and covers this with
retaining the water and for driving off the vola- an inverted trough having serrated edges,
tile ammonium salts contained in the crude which can readily be removed for cleaning from
L 2
148 AMMONIA.
a small manhole at the side. Scott (Eng. Pat. When sufficiently dry, the product is placed into
3987, 1900 ; 11082, 1901) has patented a process stock, or it may be at once dried by a centrifugal
in wlu'ch the whole of the plant is kept under machine.
'
vacuum, whereby considerable economy of fuel In place of fishing,' the sulphate may be
is claimed. The plant and method of working are periodically or continuously removed from the
described by Ballantyne (J. Gas Light. 82, 8G9). saturator by means of a steam-ejector, whirh
Absorption of the ammonia in sulphuric acid. forces it together with much liquor on to the
The gases from the still, consisting chiefly of drainer, thence into a centrifugal machine, the
ammonia steam, carbon dioxide, sulphuretted mother liquor in either case returning to the
hydrogen, and small quantities of hydrocyanic saturator.
acid, are conveyed to the saturator (D in Fig. 1, With a closed saturator other means of
Kin Fig. 2) charged with sulphuric acid. This is removing the sulphate are adopted, a represen-
constructed either of solid lead throughout, or of tative of this type being the Colson saturator,
wood or iron lined with lead, the gases being con-
ducted in
by means of a perforated leaden pipe
which distributes them over a large area in the
saturator and keeps the liquid thoroughly
agitated. In some oases, dilute sulphuric acid
is used, this being removed and replaced by
fresh acid when nearly neutralised. The solu-
tion, after settling, is concentrated and crystal-
lised, the mother liquor being returned to the
saturator. The dilute solution of ammonium
sulphate obtained by direct washing of the
crude gas with acid, as in the Mond Gas process,
is evaporated and crystallised in a similar way.
In most cases, however, when distilling gas liquor,
a much stronger acid (of about 140Tw.) is used
which soon becomes saturated, after which the
ammonium sulphate crystallises out as formed,
and is removed by various means, fresh acid
being run in to replace that removed as sulphate.
Two types of saturator are employed, (a) partly
open, (6) closed. A common construction of
the former type is shown in Fig. 4, the gases
FIG. 5.
the bottom of which consists of an inverted cone,

to the apex of which is fixed a right-angled bend,
closed by a simple valve, consisting of a copper
disc pressed against the flange of the outlet pipe
by a screw clamp. During working this is
opened to a sufficient extent to allow the sulphate
to fall out almost as soon as it is formed.
The ammonium sulphate thus obtained
usually contains from 24 to 25 p.c. of ammonia,
equivalent to about 9399 p.c. of pure ammonium
sulphate. It usually contains from 0-1 to 0-5 p.c.
of free sulphuric acid, the remainder consisting
of moisture and small quantities of insoluble
matter. The salt produced with modern plant
has mostly a white or greyish-white colour,
discolouration by tarry matter being now of rare
occurrence with continuous stills, if the liquor
'"
is properly separated from tar by settling

previous to distillation. When pyrites sulphuric
FIG. 4. I
acid is employed, the resulting sulphate may be
coloured yellow or brown, by arsenic sulphide,
entering by the pipe b perforated as shown, and which depreciates its value, and makers therefore
bubbling through the acid, the waste gases 1
prefer to use acid obtained from brimstone or

being led off by the pipe c ; the sulphate accumu- spent oxide. In many cases, however, pyrites
lates on the floor of the saturator. The front acid is used, and the arsenic sulphide whieh
of the saturator is open, and separated from the rises as a scum to the surface of the liquid in t he
closed portion by the sealing curtain a, which saturator removed as it forms, or preferably t he
does not reach to the bottom, and enables the acid is previously treated with a portion of the
attendant to remove the sulphate periodically waste gases from the saturator, the sulphuretted
by fishing with a perforated ladle, the crystals hydrogen in which precipitates the arsenic as
being placed on a lead-lined drainer fixed so that '
sulphide, the latter being removed before the
the mother liquid flows back to the saturator. acid enters the saturator.
AMMONIA. 149
In some cases the sulphate assumes a blue substances, and hydrocyanic acid, and is also
colour on standing in the air, owing to the difficult to dispose of. The hot condensate from
formation of traces of Prussian blue. From the the liquor-heater or cconomiser is less
objection-
researches of Forbes Carpenter and Linder able than that obtained in the further
cooling
(Chief Alkali Inspector's Report, 1905, 51), it of the waste gases, which contains much more
appears that this is mostly due to local alkalinity sulphuretted hydrogen; but if the latter is
occurring in some portion of the liquid in the returned to the pipe conveying the hot con-
saturator, in which case hydrocyanic acid is ab- densate and the waste gases from the cconomiser,
sorbed at that point, and, with the traces of iron most of the sulphuretted hydrogen is driven off
a \\ ays present, forms ammonium ferrocyanide ;
I
again into the waste gases, and the combined
the latter, on exposure to the ah", oxidises, form- liquor, after cooling, may be mixed with the
ing Prussian blue. Priming of the still, resulting effluent from the stills without increasing the
in the introduction of ferrocyanides and thio- difficulty of dealing with the latter (Broadberry,
cyauates into the saturator, has a similar effect, J. Gas Light. 69, 345).
but the production of the blue salt often occurs The waste gases, after cooling, consist
in absence of priming. Its formation is best chiefly of carbon dioxide, sulphuretted hydrogen,
avoided by maintaining the liquid hot and of and smaller quantities of hydrocyanic acid, as
sufficient acidity, and arranging that the passage well as strongly smelling empyreumatic vapours
of the gas shall effect a thorough mixing of the derived from the tar. With coke-oven liquors,
liquid in the saturator, so as to prevent the which often contain considerable quantities of
occurrence of local alkalinity. cyanide, the amount of hydrocyanic acid may
Waste products in the manufacture of Am- be considerable, necessitating additional care in
monium Sulphate. Three waste products are dealing with it owing to the poisonous nature of
formed in the process (a) the effluent liquor ; (6)
: the gas. In many cases the gases are burned
the aqueous condensate from the cooling of the under the boiler or other furnaces, and discharged
waste gases ; (c) the waste gases. The effluent with the products of combustion from the
liquor is run into settling tanks, where it deposits chimney ; or the gases may bo burned separately
suspended lime salts, and becomes cooled. The and the resulting sulphur dioxide absorbed by
clarified liquor is sometimes run into the sewers, passing the products through a limestone tower
but as it contains large quantities of lime salts down which water is passing, yielding -a solution
(especially thiocyanate and phenols), this is of calcium bisulphite, or through scrap-iron
frequently not permitted, and its disposal is towers, when a solution of ferrous sulphate is
often a matter of great difficulty. In gas works formed (Wilton, Eng. Pat. 15468, 1901). With
it is sometimes got rid of by employing it to small and medium-sized plants, the sulphuretted
quench the hot coke from the retorts, and in hydrogen and hydrocyanic acid are mostly
some cases it is even evaporated to dryness. removed by oxide of iron, in a similar manner to
Fowler (Alkali Inspector's Report, 1907, 51) that employed for purifying coal gas. In place
allows the liquor, after considerable dilution, to of purifying boxes, conical heaps of oxide of
pass through coke filters inoculated with sewage iron on a concrete floor are now much used, the
bacteria, which, if gradually accustomed to the gas being introduced from the bottom at the
liquor, oxidise the thiocyanates and phenols, centre of the heap ; the spent oxide obtained is
yielding a fairly pure effluent, and this may be saleable for its sulphur content. The sulphur-
employed for dilution of the fresh liquor going etted hydrogen may also be precipitated with
on to the filter. Radcliffe (Eng. Pat. 10075, metallic salts, and where sulphuric acid is also
1905) removes the thiocyanates by precipitate made, the gases are burned and passed into the
ing as cuprous thiocyanate with copper sulphate chambers, thus recovering the sulphur as gul-
in presence of sulphurous acid, the latter being phuric acid. A
considerable proportion of the
obtained by burning a portion of the waste waste gas is converted into sulphur by tho
gases. Grossmann (Eng. Pat. 20387, 1905; Claus process (Eng. Pat. 3606, 1882; 5070,
7932, 1907; J. Soc. Chem. Ind. 1906, 411) has 1883 ; 5958, 1883), also used on tho large scale
also described a process for avoiding the produc- in theChance sulphur-recovery process. By this
tion of waste liquor and recovery of the ferro- method, sufficient air is mixed with the gas to
cyanide and thiocyanates present in it. react with the sulphuretted hydrogen in accord-
The avoidance of the production of waste ance with tho equation 2H 2 S + 2 =2H 2 0+2S,
liquor altogether is an especial object in the and the mixture passed through a kiln containing
process of the Otto-Hilgenstock Coke Oven Co. heated ferric oxide, tho sulphur formed being
(Eng. Pat. 12809, 1908) now being adopted in deposited in cooling chambers, and the residual
some coke-oven works. In this the gas from the gases passed through a small limestone
tower
ovens is treated for the removal of tar at tem- and oxide-of-iron purifier to remove any sulphur
peratures above that at which water condenses, dioxide or sulphuretted hydrogen remaining.
and then passed directly through sulphuric acid ;
Tho sulphur obtained is not very pure, owing to
the aqueous condensate obtained in the subse- tarry matters, &c., present in the gases treated.
quent cooling of the gas is free from ammonia, Manufacture of Caustic Ammonia (Liquor
and only contains small amounts of impurity, Ammoniac) and of Liquefied Ammonia. The
and it is claimed that no difficulty is experienced pure aqueous solution of ammonia was formerly
in
disposing of it. Wilton (Eng. Pat. 16355, manufactured by distilling ammonium sulphate
1909) has patented a somewhat similar process with lime in intermittent stills provided with
with the same object. mechanical arrangements for stirring the some-
The aqueous condensate obtained by cooling what thick cream, but it is now usually made by
the waste gases is a
very noxious-smelling liquid, the direct distillation of gas liquor, with suitable
and is hence termed devil-liquor.' It contains
'
purification of the gas evolved from

the stills,
sulphuretted hydrogen, pyridines, and similar which is then dissolved in water. In addition
150 AMMONIA.
to the pure aqueous solution, a crude solution ensure the removal of the last traces of sulphur-
containing sulphide, and sometimes carbonate, etted hydrogen, ferrous sulphate solution is
is also largely manufactured, this being sometimes added to the last lime washer, the
cheaper and equally applicable to many ferrous hydroxide formed by the action of the
purposes, especially in the manufacture of soda lime retaining the gas as ferrous sulphide, or,
by the ammonia-soda process, and for the according to Pfeiffer (J. Gasbel. 1900, 89), a
preparation of other ammonium salts. This small final washer containing caustic soda
crude product is termed ' concentrated gas solution is added. Solutions of sodium per-
liquor,' two kinds being manufactured, the one manganate or ammonium persulphate may also be
containing from 16 to 18 p.c. of ammonia, with used (Foucar). The gases then pass through a
both sulphide and carbonate present, and the series of scrubbers charged with wood charcoal,
other from 18 to 26 p.c. of ammonia, with some which remove the strongly smelling empyreu-
sulphide but little or no carbonate. matic substances derived from the tar, and in
In the manufacture of the first-named liquor, some cases additional purification in this respect
the gases from the stills, worked as in the is effected by passing the gas through a fatty or
manufacture of the sulphate, pass through a high-boiling mineral oil. The resulting purified
reflux condenser, to remove some of the steam gas is then led into distilled water, and thus con-
present, and then through a direct condenser, verted into solution of any desired strength up to
the gases from which are washed with water. about 36 p.c. The charcoal scrubbers must be
Working in this manner, it is not practicable to renewed as soon as their activity becomes
obtain a greater strength of ammonia than 1618 lessened, the spent material being revivified by
p.c., as with higher concentrations stoppages heating in closed retorts.
occur in the condenser from crystallisation of Technical caustic ammonia is usually clear,
ammonium carbonate. For the preparation of and colourless, and contains only small quantities
the more concentrated gas liquor, the vapours of pyridine and empyreumatic substances. When
from the still, after passing the reflux condenser, these are present in larger quantity, owing to
are led through a washer containing milk of defective action of the charcoal filters, the liquid
lime, which removes practically the whole of assumes a yellowish colour on keeping. Its
the carbon dioxide and some of the sulphuretted strength is ascertained from its specific gravity.
hydrogen, a liquor being then obtained by A table showing the specific gravity of different
condensation usually containing 22-26 p.c. of concentrations is given on p. 139.
ammonia, and a little sulphide, but usually free Liquefied Ammonia. The liquefied gas,
from carbonate. stored in steel cylinders, is nowlargely produced
Pure Caustic Ammonia. In the manufacture and employed for refrigeration purposes. It is
of pure aqueous ammonia from gas liquor, a manufactured from the gas obtained and
sufficient quantity of lime must be employed to purified as described for the manufacture of the
remove the whole of the acid constituents of the pure aqueous solution, but instead of passing
liquor, including the carbon dioxide and sul- it into water, it is well dried, and then com-
phuretted hydrogen. For the complete removal pressed by suitable pumping machinery. The
of the latter the use of a decided excess of lime commercial liquid usually contains small
is necessary, and owing to the amounts of water, pyridine, and lubricating oil,
hydrolysis of
calcium sulphide even excess of lime does not and traces of other substances, but is now
remove the last traces of sulphuretted hydrogen, sold, in many cases, as of guaranteed 99-9 p.c.
which is eliminated by other reagents. The purity.
addition of the large amount of lime required in Ammonium Chloride (Muriate of Ammonia
the stills themselves during the distillation of the or Sal-ammoniac). This salt has been manu-
liquor, gives rise to much trouble from blockage factured in a similar manner to that employed
in the latter, and it is therefore mostly found for the sulphate, by passing the gases from
preferable to effect the removal of those two the stills into hydrochloric acid, but as
gases by passing the still vapours through lime lead is attacked under these conditions, the
washers. Much economy in the use of lime saturator must be constructed of stoneware or
results if the liquor, previous to distillation, is similar material,which has many disadvantages.
subjected to a preliminary heating to 70-80 It is now
usually made by neutralising hydro-
(Hills' process), at which temperature a large chloric acid with concentrated gas liquor, and
proportion of the carbon dioxide and sulphur- evaporating and crystallising the resulting
etted hydrogen are evolved, accompanied by solution, or by evaporating a solution of ammo-
only small amounts of ammonia, the latter being nium sulphate and sodium chloride in equivalent
recovered by washing the evolved gases with proportions ; the sodium sulphate formed
water or weak ammoniacal liquor, or, where the separates out during concentration as the
manufacture of sulphate is carried on simulta- monohydrate, which is removed by '
fishing,'
neously, the gases evolved may be passed direct leaving finally a concentrated solution of ammo-
to the sulphuric-acid saturator, along with the nium which is
chloride, purified by crystallisa-
gases from the stills used in that process. tion.
The preheated liquor is distilled as in the It is also manufactured by neutralising
case of the sulphate process, and the gases "
galvanisers' pickle" (which consists chiefly of
evolved, after traversing a reflux condenser, pass ferrous chloride) with ammonia, and by the
through a set of two or three washers, containing action of ammonium carbonate (or of ammonia
cream of lime, to remove carbon dioxide and and carbon dioxide) on calcium chloride solution,
sulphuretted hydrogen, the partly used lime the latter being obtained in large quantity as a
being run back into the stills to effect the de- by-product in the ammonia-soda manufacture,
composition of the fixed ammonium salts, and and in that of potassium chlorate ; the solutions
recovery of ammonia from the cream. To of ammonium chloride obtained in either case
AMMONIA. 151
are evaporated and crystallised after removal of parts of ammonium sulphate and 720 parts of
the precipitated substances. sodium nitrate (40 p.c. excess) is dissolved in
Ammonium chloride is frequently further 900 parts of water, and the bulk of the sodium
purified by sublimation, the sublimed product sulphate formed separated by evaporation. The
being known as sal-ammoniac. In this country filtered liquor is further concentrated till a
the operation is carried out in large iron pots sample on cooling to 70 deposits ammonium
externally heated and covered with a similar nitrate ; the whole solution is then cooled to
concave iron plate on which the sublimate slightly above 70, and after removal of the
(sal-ammoniac) forms. This is detached at the copious deposit of crystals of sodium nitrate and
end of the operation, the surface adhering to the sulphate, the mother liquor is mixed with
iron, which is always discoloured, being removed sufficient water to prevent the separation of
previous to sale. In France the discolouration sodium salts at 15, 14 parts of water per 100
with iron is avoided by using earthenware pots, of mother liquor being sufficient with the above
but the product is more expensive, owing to quantities. On then cooling to 15, about 40
the fact that the pots are destroyed at each p.c. of the ammonium nitrate separates in the
operation. pure state. The mother liquor from these
The commercial crystallised salt is white or crystals, and the sodium nitrate previously
only slightly discoloured, whilst the sublimed separated, are employed in working up a further
material has a fibrous structure, and frequently amount of ammonium sulphate.
contains small amounts of iron. It is employed The nitrate is also manufactured from the
in pharmacy, soldering, galvanising, dyeing, and calcium nitrate now commercially prepared from
calico-printing, and in small quantities for many the oxides of nitrogen obtained by the oxidation
other purposes. of atmospheric nitrogen, by heating it with a
Ammonium Carbonate (Sal-Volatile). The solution of rather less than an equivalent
commercial product sold under this name quantity of ammonium sulphate. Under proper
consists of a mixture of ammonium bicar- conditions the reaction is said to be almost
bonate NH 4 -HCO 3 with ammonium car- quantitative, the calcium sulphate separating
bamate NH 2 -CO-ONH 4 and contains about 31
, in a readily removable form (Wedekind & Co.
of ammonia and 56 p.c. of carbon dioxide. Eng. Pat. 20907, 1909). Attempts to obtain
J.c.
b is
usually prepared by subliming a mixture the nitrate from the calcium salt by the action
of about 1 part of ammonium sulphate with 1 -5 of ammonia and carbon dioxide have not
to 2 parts of chalk in retorts, the evolved gases hitherto proved successful, owing to the forma-
being passed into leaden chambers, where the tion of double salts.
carbonate is deposited as crusts on the walls, Ammonium phosphate. Monammonium phos-
the exit gases being washed with water or phate (NH4 )H a P0 4 and diammonium phos-
,
sulphuric acid to recover the uncondensed phate (NH 4 ) 2 HP0 4 have become commercial
ammonia. Lunge recommends the passing of products by the process of Lagrange, which
an additional quantity of carbon dioxide through starts from commercial calcium superphosphate.
the chambers to effect a more complete recovery This is lixiviated by water and steam, and a
of the ammonia. As soon as the crust has solution of 42Tw. is obtained, together with a
attained a sufficient thickness it is detached, and residue of calcium sulphate. Some of the
is
usually purified by resublimation. In Kun- latter remains in the solution, and is re-
heim's process, the carbonate is prepared by moved by carefully adding barium carbonate.
passing ammonia obtained by the distillation The filtrate is neutralised by ammonia in slight
of gas liquor direct into chambers, where it excess, whereby all the lime is precipitated as
mixes with carbon dioxide and deposits the basic phosphate, which is washed and used over
carbonate as a crust. (See also Bueb, Eng. again for the manufacture of superphosphate. c
Pat. 9177, 1910.) The marking 32 Tw., contains
filtered solution,
The commercial product forms crystalline monammonium phosphate, and can be worked
crusts, smelling strongly of ammonia, which is for this or for diammonium phosphate. The
partially evolved on exposure to the air, the latter is obtained by gradually mixing the above
mass and leaving a powder consisting
efflorescing solution with liquor ammonice of sp.gr. 0-92, in
of ammonium bicarbonate. It is employed in the proportion of li equivalents of 3 to 1 of NH
wool-scouring, dyeing, and as a constituent of (NH 4 )H 2 (P0 4 ).
The diammonium phosphate at
baking powders. once separates out as a crystalline mass, which,
Ammonium This salt is produced
Nitrate. after cooling, is submitted to hydraulic pressure.
to a considerable extent for use in the The operation is carried out in a closed vessel,
explosive industry and in the preparation to prevent the escape of ammonia. The mother
liquor is employed for the manufacture
of nitrous oxide. It may be obtained by neu- of
tralising caustic ammonia with nitric acid, and ammonia. The diammonium phosphate is prin-
evaporating and crystallising the solution if cipally used in Lagrange's sugar-refining process,
necessary, or by heating a mixture of ammonium Ammonium thiocyanate is manufactured in
sulphate and sodium nitrate in equivalent pro- considerable quantity in the crude state, but
portions, either alone or in solution. When the the product is for the most part simply employed
solution is concentrated, sodium sulphate as an intermediate product in the manufacture of
separates out first for the most part, but the cyanides. It occurs, as has been mentioned, in
ammonium nitrate obtained simply by further considerable amount in gas-liquor, and also in
extracted by
evaporation is far from pure. According to spent oxide, from which it may be
Wedekind and Co. (Eng. Pat. 19465, 1906); water, but in both cases it is mixed with so
a pure salt may be produced
by a modified many other impurities that its recovery is not
system of evaporation, of which the follow- remunerative ;
it may, however, be easily iso-
ing example is given. A mixture of 400 lated as cuprous thiocyanate by precipitation
152 AMMONIA.
with copper sulphate and sulphurous acid. It is of potatoes. Amyl alcohol is a constituent of
prepared synthetically from carbon disulphide the product obtained when ordinary alcohol is
by absorbing the latter in ammonia in presence formed by fermentation. The alcohol is got
' '
of bases such as lime (Albright and Hood, Eng. from the last runnings by shaking the crude
Pat. 14154, 1894), the ammonium thiocarbonate product with hot milk of time, decanting, drying
first produced undergoing conversion into thio- over calcium chloride, and rectifying at a tem-
cyanate. A concentrated solution of ammonium perature of 132. Pure amyl alcohol is ob-
thiocyanate is now prepared in a number of tained by preparing potassium amyl sulphate,
gas works, according to the British Cyanide Co.'s purifying this by solution in alcohol and pre-
process (Eng. Pat. 13653, 1901), by passing the cipitation with ether, and subsequently decom-
crude gas containing ammonia and hydrocyanic posing by heating for five hours with 10 p.c.
acid through a washer containing water and sulphuric acid.
fed with powdered sulphur, the ammonium Properties. Amyl alcohol is a colourless
polysulphide first formed combining with the liquid with a peculiar cough-exciting odour and
hydrocyanic acid to form thiocyanate, solutions a burning taste ; it burns with a white smoky
of 30-50 p.c. strength being readily obtained, flame b.p. 131-6
; (corr.) and sp.gr. 0-8248
which oni}' contain small amounts of other non- atO 0-8113 at 18-7 (Kopp, Annalen, 94, 289);
;
volatile ammonium salts. b.p. 128-9-129-2 at 740-9 mm., and sp.gr.

The pure salt is used in dyeing and calico- 0-8104 at 20/4 (Briihl, Annalen, 203, 23) ; b.p.
printing, and may be obtained from the crude 130-5-131 at 759-2 mm. (Schiff,Annalen, 220,
product by firstconverting it into the barium 102). It is soluble in ethyl alcohol or ether,
salt with baryta- water or the barium salt may
; but is soluble in water only to the extent of 1 in
be produced by the action of barium sulphide 39 at 16-5 (Wittstein, J. 1862, 408), and
on cuprous thiocyanate. After purification by 1 in 50 at 13-14, and the solution becomes
recrystallisation, the barium salt is exactly milky at 50 (Balbiano, Ber. 1876, 1437). Amyl
precipitated with ammonium sulphate, and the alcohol dissolves in all proportions in acetic acid
solution evaporated and crystallised. The white diluted with an equal bulk of water (Bcrthelot
deliquescent salt has frequently a reddish colour, and St. Gilles, J. 1862, 408). When oxidised
duo to the formation of the red ferric thiocyanate, with platinum black, ordinary valeric (iso valeric)
from traces of iron present. acid is formed, whilst distillation with either
Ammonium persulphate. This salt is now manganese dioxide or potassium dichromate
produced on the commercial scale by the and sulphuric acid converts it into isov&ler-
electrolysis of ammonium sulphate, and is aldehyde and isovaleric acid. Sulphuric acid
employed for photographic purposes and as an dissolves it in the cold, forming amyl-sulphuric
oxidising agent. The commercial product usually acid, which, on heating, decomposes into
contains small quantities of lead derived from amylene and its polymerides diamylene and
the electrodes used in its manufacture. tetramylene these hydrocarbons, together with
;
TT
hexylene and the corresponding paraffins, are
f*1 î
AMMONIACUM, AFRICAN, v. GUM RESINS. also obtained when amyl alcohol is distilled with
AMMONIACUM, GUM, v. GUM RESINS. zinc chloride (Wurtz, Annalen, 128, 316) it is
:
AMMONIACUM, PERSIAN, v. GUM BESINS. probable, however, that the latter owe their
AMMONITE v. EXPLOSIVES. formation to impurities in the alcohol. The
AMMONIUM MELEQUETA v. COCCULUS action of chlorine has been studied by Barth
INDICUS. (Annalen, 119, 216), and that of bleaching
AMRAD-GUM. This gum forms white, yellow, powder by Goldberg (J. pr. Chem. [2] 24, 116).
and brown lumps of a sweetish taste and resin- The bromide (Cahours, Annalen, 30, 298 ;
ous smell. An aqueous solution (1 : 2) is viscid Balbiano, J. 1876, 348), chloride (Cahours,
and strongly adhesive. It also gives with oil Annalen, 37, 164 ; Balard, Annalen, 52,
excellent emulsions, which keep very well. The 312 ; Balbiano, I.e.), and iodide (Cahours,
dry substance contains 5-61 p.c. of ash, consist- Annalen, 30, 297) have been prepared by the
ing of carbonic acid, lime, iron, magnesia, traces action of the corresponding phosphorus com-
of phosphoric acid and silica. Has been recom- pounds. Commercial amyl alcohol is generally
mended as a substitute for gum arabic. It was laevorotatory the degree of rotation, however,
;
brought into the market some years ago, and is not constant, but varies in different
specimens,
comes from the Abyssinian highlands is pro- ; and the variation has been shown by Pasteur
bably obtained from Acacia etbaica (Schwein- (Annalen, 96, 255) to be due to the fact that
furth). (H. Unger and Kempf. Pharm. Zeit. 33, ordinary amyl alcohol is a mixture, in varying
218 J. Soc. Chem. Ind. vii. 446.)
;
proportions, of two isomerides, one of which is
AMYGDALASE, AMYGDALIN v. GLUCO- optically inactive, and the other laevorotatory.
SIDES. When ordinary amyl alcohol is treated with
AMYGDONITRILE GLUCOSIDE v. GLUCO- sulphuric acid and the resulting amyl sulphuric
SIDES. acids converted into barium salts by neutralisa-
AMYGDOPHENIN v. SYNTHETIC DRUGS. tion with barium carbonate, a separation of the
AMYL ACETATE v. ACETIC ACID. two isomeric alcohols can be effected, inasmuch
AMYL ALCOHOL C 5 H 12 0. The ordinary as the barium salt of the optically active alcohol
amyl alcohol (fusel oil, fermentation amyl is 2^ times more soluble in water than the corre-
alcohol, or iso&myl alcohol Cl-hydroxy-3-methyl sponding salt of the optically inactive modifica-
butane) is one of the eight alcohols of the formula tion. (For an examination of the properties
C 6 H 1? theoretically possible, and is the chief and physical constants of commercial amyl
constituent of the fusel oil or ' last runnings ' alcohol, see Richmondand O'Shaughnessy, J.
obtained in the rectification of alcohol, particu- Soc. Chem. Ind. 1899, 107.) Marckwald and
larly of the alcohol made by the fermentation McKcnzie have reviewed the previous work of
AMYLANS. 153
Ley, Le Bakhoren, and Chapman. They

Bel, tasting like peppermint. It boils at 93
have succeeded in dividing the commercial (J. Soc. Chem. Ind. 1889, 1003).
alcohol into its constituents by fractional AMYLACETIC ACID (Active) v. HEPTOIC
crystallisation of their nitrophthalic esters,
and ACIDS.
find that active amyl alcohol has [a]n 5-90 at iso-AMYLACETIC ACID v. HEPTOIC ACIDS.
20. The other constituent isobutyl carbinol
is a- and /8-AMYLANS n(C 6 H
10 5 ) ?
After
(Ber. 1901, 485, 479 ; 1909, 1583). extracting cereals with strong
first
Amyl alcohol has been used as a solvent for alcohol, the aqueous extract contains gummy
nitrocellulose in the manufacture of celluloid, as laevorotatory colloidal carbohydrates, which
have also its chlorination products Liebert has are precipitated by strong alcohol. The product
utilised amyl nitrate (I). R. P. 51022) by adding so obtained from barley is a mixture, part being
it to nitroglycerine in order to diminish its soluble in cold water. The insoluble
crumbly
sensitiveness to cold and concussion. residue, amounting to 2 p.c. of the barley, is
In addition to the optically active and in- a-amylan. It has [a] D 21-6, and does not
active modifications obtained from ordinary reduce Fehling's solution ; it is gelatinised in
amyl alcohol, the following isomeric alcohols hot water, and yields viscous solutions even at
have been prepared Normal amyl
: alcohol 1-2 p.c. concentration. O'Sullivan (Chem. Soc.
(Lichen and Rossi, Annalen, 159, 70
Schor- ;
Trans. 1882, 41, 24) found it to be present in
lemmer, Annalen, 161, 268) methyipropyl car-; barley, oats, wheat, and rye, especially in the
binol (Schorlemmer, I.e. Saytzew and Wagner,
;
two first named. The soluble product 0-
Annalen, 175, 351 179, 313 ; Markownikow,
; amylan has [o]p 65; it amounts to 0-3 p.c.,
J. 1883,861) ; methylisopropyl carbinol (Wysch- and is very similar to a-amylan in properties.
negradsky, I.e. ; Munch, Annalen, 180, 339 ; O'Sullivan obtained from -amylan, by
Winagradow, Annalen, 191, 125) diethyl ;
fractional precipitation with alcohol or on boiling
carbinol (Saytzew and Wagner, I.e.); di- with milk of lime, a similar substance [a]n
methykthyl carbinol (Wurtz, Annalen, 125, 114; 129-7. This he regarded as a decomposition
127, 236 ; 129, 365 ; Berthelot, Annalen, 127, 69 ; product, but this is probably not the case.
Flavitzky, Annalen, 179, 348 ; Wyschnegradsky, O'Sullivan states that the amylans yield glucose
I.e.
; Osipoff, Ber. 1875, 1240). alone on hydrolysis. Lintner and Dull (Zeit.
AMYL NITRITES C 6 H n N0 2 . Commercial angew. Chem. 1891, 538) obtained galactose
amyl nitrite is a mixture of the nitrites of isobutyl and xylose from barley gum. Wroblewski
carbinol and active amyl alcohol (Ber. 1893, 30, 2289) obtained arabinose. Lindet
(Berlin Congress, 1903, 3, 498) isolated a dextro-
(CH 3 )2 CH-CH2 -CH 2 -N0 2 +CH 3(C 2 H 6 )CH-CH 2 -N0 2
rotatory gum from barley, in addition to a
It may also contain isobutyl nitrite, and always Isevo-rotatory gum.
contains some unaltered amyl alcohol. Curt- Contrary to O'Sullivan's statement that
mann Soc. Chem. Ind. 1893, 372) gives diastase is without action on amylan, Horace
(J.
examples of specimens containing from 33 p.c.
Brown (Trans. Guinness Research Laboratory,
to 93 p.c. of amyl nitrite. It is prepared by 1906, 317, where there is a full account of amylan)
finds that when barley gum is steeped in malt
passing nitrous fumes into amyl alcohol (Balard,
Ann. Chim. Phys. [3] 12, 318; Williams and extract it swells up and undergoes gradual
Smith, Pharm. J. 1886, 499); by distilling liquefaction and and in a few days
solution,
together the theoretical quantities of amyl
its colloidal nature is lost. This is one of the
alcohol and potassium nitrite with excess of most significant changes which mark the con-
dilute sulphuric acid ; or by version of barley into malt.
passing nitrosyl
chloride into a mixture of equimolecular propor- To prepare ' amylans ' in quantity, Brown
tions of dry pyridine and amyl alcohol (Bouveault boils the finely divided grain with water, treats
and Wahl, Compt. rend. 136, 1563). The last with malt extract at 50-55 for an hour to
isa general method for the preparation of nitrous liquefy the starch, boils again, and filters. The
esters, and gives a yield of 80 p.c. in the case nitrate is concentrated in vacuum tosp.gr. 1-060,
of amyl nitrite. The commercial article is a and three volumes 80 p.c. alcohol (by volume)
yellow liquid with characteristic odour, which added gradually. The crude amylans are
should boil between 97 and 99, and have a precipitated in large white flocks free
from
sp.gr. 0-870 to 0-880. It is of value as a stimu- dextrin and have no cupric reducing power. Cor-
lant in angina pectoris and similar affections. rected for ash and nitrogen they amount on a
Normal amyl nitrite CH 3 -(CH -CH 2 N0 2 is number of dry barleys to about 9-6 p.c., and
2)3
a pale-yellow liquid, have [o] D +62 to +73. This amount practi-
boiling at 104 ; sp.gr. 0-8528
at 20. The nitrite group is readily removed cally accounts for the whole of the missing
by dilute potash (Marcel Pexsters, Chem. Zentr. constituents of the soluble portion of barley
1907, i.
1398). after hydrolysis with malt extract.
Isobutyl carbinol nitrite On hydrolysis about 60 p.c. of glucose is
formed, together with arabinose, xylose, and
an unknown substance of low angle and reducing
power.
from pure isobutyl carbinol, boils at 97, and has The above dextrorotatory amylan repre-
sp.gr. 0-880 (Dunstan and Williams, Pharm. J. sents everything insoluble in 62 p.c. alcohol. By
1889, 487). a variation of the method of preparation a
Tertiary amyl nitrite (CH 3 ) 2 (C 2 5 )C-N0 2 H carbohydrate [o] D 100-34, corresponding
to
(Bertoni's amylonitrous ether) has been used as Wroblewski's araban, was obtained.
' '
a substitute for It is obvious that the
ordinary amyl nitrite, its action amylans require
being stronger in degree and more lasting. It is further investigation. According to O'Sullivan,
a yellow liquid with weak it is probably owing to the presence of amylan
camphoraceous odour,
154 AMYLANS.
that unmalted barley cannot be satisfactorily 13, 45, 129; 14, 136; Kondakoff, J. Russ.
Phys. Chem. Soc. 20, 141 24. 381 ; Ber.
employed in the preparation of beer. Malted :
grain does not contain it. Distillers using raw 24, 929 Hell and Wildermann, ibid. 216)
;
with ;
grain (oats and barley) have at times much

bromine (Wurtz, Ann. Chim. Phys. [3] 55, 458;
Hell and Wildermann, ; Kondakoff, I.e.), and,
difficulty in separating the wort (solution
of I.e.
sugars, &c.) from the grains (undissolved when cautiously mixed with well-cooled sulphuric
portion of the gram employed) in consequence acid, sp.gr. 1-67 (2 vols. H
2 S0 4 to 1 vol. water),
of the presence of amylan in quantity, the in a freezing mixture, is converted into dimethyl-
barleys and oats of some seasons containing ethyl carbinol, b.p. 101-6-102/762-2 mm.,
much more of it than at other times. E. F. A. which has valuable hypnotic properties (J. Soc.
AMYLASE v. DIASTASE also ENZYMES. ;
Chem. Ind. 8, 1002 ; 9, 650, 889), and can be
AMYLENE C 5 H 10 Eight isomeric amylenes
. obtained, after neutralisation with sodium
are theoretically possible, and all have been pre- hydroxide ; on distillation (Flavitzky, 175, 157)
with sulphuric acid, sp.gr. 1-545 (2pts. by weight
pared. These hydrocarbons have been chiefly
studied by Flavitzky (Annalen, 179, 340),Wysch- H 2 S0 4 to
1 pt. water), methyh'sopropyl carbinol
is obtained (Osipoff, Ber. 8/542, 1240). Amy-
negradsky (Annalen, 190, 336), and by Kondakoff
(J. Russ. Phy.. Chem. Soc. 24, 381), and can be
lene forms compounds with metallic salts
obtained by the action of alcoholic potash on (Deniges, Compt. rend. 126, 1146; Kondakoff,
the various amyl iodides or by the action of
;
J. Russ. Phys. Chem. Soc. 25, 35). When
heated to high temperatures, benzene, naphtha-
dehydrating agents such as sulphuric acid or
zinc chloride on amyl alcohol. They can often lene, acetylene, methane, carbon, and hydrogen
be converted into one another by the action of are produced, the products depending on the
hydriodic acid and the subsequent removal of temperature (Haber and Oechelhauser (Chem.
the latter, thus : Zentr. 1897, i. 225). The action of nitrosyl
chloride on amylene has been studied by Tilden
Me 2 CH-CH CH 2 +HI
:
and Sudborough (Chem. Soc. Trans. 1893, 482).

KOH
->Me 2 CH'CHIMe Me 2 C:CHMe. In addition to ordinary amylene, the following
-falcohol isomerides have been obtained : Normal amyl-
The amylene ordinarily met with is tri- em, b.p. 39-40 (Wurtz, Annalen, 123, 205 ; 127,
methylethylene, and is chiefly obtained by the 55; 148, 131; Zeidler, Annalen, 197, 253;
dehydrating action of zinc chloride on fermenta- Kondakoff, J. Russ. Phys. Chem. Soc. 24, 1 13 ;
tion amyl alcohol. Flavitzky and Wyschnegradsky, I.e.) isopropyl- ;
Preparation. To prepare amylene, ferments ethykne, b.p. 21-l-21-3 (Flavitzky and Wys-
-
tion amyl alcohol (1 part) is shaken with coarsely chnegradsky, I.e. ; Kondakoff, i.e. ; Ipatieff, I.e.);
powdered zinc chloride (1J parts), allowed to symmetrical methylethylethylene, b.p. 36 at
remain for twenty-four hours, and then distilled. 740-8 mm. (Wagner and Saytzew, Annalen, 175,
The product consists of a complex mixture of 373 ; 179, 302 ; Kondakoff, I.e. ; Lissier, Bull.
paraffins from C S H 12 to C 10 H 22 with defines Soc. chim. 9, (3) 100); and unsymmetrical
from C 5 H 10 to C 10H 20 (Wurtz, J. 1863, methylethylethylene, b.p. 31-32, sp.gr. 0-67 at
507). These can be isolated by fractional dis- (Wyschnegradsky, I.e. ; Le Bel, Bull. Soc.
tillation (Wurtz), but according to Eltekow (J. chim. 25, 546 ; Kondakoff, I.e. 25, 354) ; Methyl-
Russ. Chem. Soc. 14, 379), amylene is most tetramethylene, b.p. 39-42 (Coleman and Perkin,
readily obtained if the product is well cooled, Chem. Soc. Trans. 1888, 201) ; pentamelhylene,
and shaken with dilute sulphuric acid (2 vols. of b.p. 35 (Gustavson and Demganoff, J. Russ.
acid to 1 vol. of water), the acid layer separated, Phys. Chem. Soc. 21, 344 ; Markownikoff, Ber.
diluted with water, and distilled ; the distillate 30," 975; Young, Chem. Soc. Trans. 1898, 906;
consists of amylene (trimethylethylene) and Wislicenus and Hanschcl, Annalen, 275, 327) ;
tertiary amyl alcohol, and the latter, on dis- and dimethyltrimcthylene (Gustavson and Popper,
tillation with sulphuric acid (1 : 1), yields pure J. pr.Chem. 166, 458).
trimethylethylene. Pure trimethylethylene can The action of hydrogen iodide on the amyl-
be prepared by heating tertiary amyl iodide enes has been investigated by Saytzew (Annalen,
Me 2CIEt with alcoholic potash (J. Russ. Phys. 179, 126) ; whilst Zeidler (Annalen, 186, 245) has
Chem. Soc. 17, 294). It can also be formed by examined the products obtained when various
dropping tertiary amyl alcohol on to oxalic acid amylenes are oxidised with potassium perman-
(D. R. P. 66866). ganate in acid, neutral and alkaline solution,
Other methods for obtaining ordinary amyl- with chromic acid, and with potassium dichrom-
ene have been described by Balard (Ann. ate and sulphuric acid. The halogen derivatives '
Chim. Phys. [3] 12, 320) Bauer (J. 1861, 659),

; of the various amylenes have been investigated
and Linnemann (Annalen, 143, 350) Kondakoff ;
(Lipp, Ber. 22, 2572 Hell and Wildermann,
;
(I.e.); Ipatieff (J. Russ. Phys. Chem. Soc. 30, 292); 23, 3210 Ipatieff, J. pr. Chem. 161, 257
;
Chem. ;
Tornoe (Ber. 21, 1282) ; Blaise and Courlot (Bull. Zentr. 1898, ii. 472 Brochet, Ann. Chim. Phys.
;
Soc. chim. 35, 582). 1897, 10, 381 Wassileef, Chem. Zentr. 1899, i.
;
Properties. Amylene is a colourless liquid, 775 ; Froebe and Hochstetter, Monatsh. 23,
b.p. 36-38 and sp.gr. 0-6783 at (Le Bel, 1075 ;Kukuritschkin, J. Russ. Phys. Chem.
Bull. Soc. chim. 25, 547) ; b.p. 36-8 at 752-7 mm. Soc. 35, 873 Schmidt and Leipprand, Ber. 37,
;
(Schiff, Annalen, 223, 65). It combines directly 532 ; Hamonet, Compt. rend. 138, 1609). Also
with a large number of substances : with nitric the action of oxalic acid on various amylenes
peroxide (Guthrie, Chem. Soc. Trans. 13. 129 :
(Miklosheffsky, J. Russ. Phys. Chem. Soc. 22,
Wallach, Annalen, 241, 291 ; 248, 161 ; Miller, 495), the nitrolamines (Wallach and Wohl,
Chem. Soc. Proc. 3, 108; Demganoff, Chem. Annalen, 262, 324), and the nitrosites and
Zentr. 1899, i. 1064) sulphur chloride and
; nitrosates (Ipatieff, Chem. Zentr. 1899, ii. 178 ;
chlorine (Guthrie, Chem. Soc. Trans. 12, 112; Schmidt, Bcr. 35, 2323, 2336, 3737 : Hantzsch,
ANESTHETICS. 155
2D78, 4120 ; Schmidt and Austin, Ber. 36, done. In spinal anaesthesia, the whole of the
nerves supplying large sections of the
1768). body are
The following polymerides of amylene have paralysed at their exit from the spinal cord by
also been obtained, and can be prepared by applying to the latter a drug which is injected
heating ordinary amyl alcohol or amylene with into the vertebral canal. Thus
spinal anaesthesia
zinc chloride: Diamylene C IO 20 b.p. 157- H , resembles general anaesthesia inasmuch as it
157-5/759 mm.
(Balard. Annalen, 52, 316 ; causes loss of sensation and muscular
power
Schneider, Annalen, 157, 207 ; Bauer, Jahres- together over a wide region, and local anaesthesia
bericht. 1861, 660; Kondakoff, J. pr. Chem. in that consciousness is not lost and the anaesthe-
162, 442 Gasselin, Ann. Chim. Phys. 1894, 3,
;
tic is not diffused in the circulation.
5) ;
H
triamylene C 16 30 (Bauer, I.e. : Gasselin, Local anaesthetics. Very little is known of
I.e.}; and tetramylene C 20 H
40 (Bauer, I.e.). Also the action of these on the tissues with which
derivatives of diamylene (Schindelmeister, Chem. they come in contact. They are all protoplasmic
Zentr. 1896. ii. 354). poisons which have a special preferential action
AMYLOCARBOL. Trade name for a dis- upon nervous structures. Those in common use
infectant, said to consist of carbolic acid 9 pts., are :
cocaine, stovaine, novocain, tropacocaine,
amyl alcohol 160 pts., green soap 150 pts., j8-eucaine, alypin, 0-eucaine lactate, nirvanine,
water 690 pts. holocaine hydrochloride, acoine, orthoform,
AMYLOCOGULASE v. Enzymes, art. FER- anaesthesine. Braun has formulated postulates
MENTATION. for appraising local anaesthetics. one
Omitting
AMYLOFORM. An antiseptic prepared by which has not secured general assent, they are :
the action of formic aldehyde upon starch (1) Low toxicity in proportion to local
(Claassen, Pharm. Zeit. 41, 625) (v. SYNTHETIC anaesthetising power.
DBUGS). (2) Solubility in water to 2 p.c. at least ; and
AMYRIN v. OLEO-RESINS. stability of the solution, which should keep
ANACAHUITA. A wood of unknown botani- without deteriorating and be capable of sterilisa-
cal origin imported from Mexico ; its preparation by boiling.
tions are said to be useful in pulmonary disorders. (3) Non-irritability to the tissues, and
The wood contains a volatile oil, an iron-greening freedom from after-effects when absorbed into
tannin, gallic acid, a yellowish resin, sugar, a the circulation.
tasteless volatile body crystallising in warty (4)Compatibility with adrenalin.
masses, and a bitter substance crystallising in Acoine, holocaine hydrochloride, anaesthesine,
white needles (J. 1861, 771). and orthoform are more or less insoluble.
ANACARDIUM NUT (Cashew Nut, Kajoo) /3-eucaine is about on the 2 p.c. border line. The
is the fruit of Anacardium
occidentale (Linn.), a others are freely soluble and will keep without
tree indigenous to Brazil, Central America, and. deteriorating. Cocaine solutions cannot be
the West Indies. It has been transplanted to, boiled, but stovaine, novocain, /3-eucaine lactate,
and become naturalised in, many parts of India. tropacocaine, alypin, and nirvanine can be thus
The fruit rests on a fleshy edible peduncle, from sterilised, at 115 if necessary.
which a spirit is distilled in Mozambique and in The most powerful anaesthetic action is that
Western India. The nut is edible after it has of stovaine. Next are cocaine, novocain,
been roasted to expel the cardol which it con- tropacocaine, alypin, and /8-eucaine lactate,
tains the cardol thus obtained is used at Goa
;
which are all about equal. The others have
for tarring boats, and as a preservative of wood- inferior actions in this respect. Experiments
work (Dymock, Pharm. J. [3] 7, 730). In on mice and rabbits have resulted in the following
addition to cardol, the nuts contain aracardic table of relative toxicity, cocaine being taken
acid, and an oily matter which, by exposure to as the unit * :
the air, assumes a fine black colour, permanent

Alypin, 1-25 Stovaine, 0-625
against acids, alkalis, chlorine, and hydrocyanic Cocaine, 1-00 Novocain, 0-490
acid. It has been recommended as a marking
Nirvanine, 0-714 /3-eucaine lactate, 0-414
ink, and is used for giving a black colour to
candles (Bottger, Dingl. poly. J. 205, 490).
The irritant action of stovaine, tropacocaine,
From the stem of the plant a gum exudes which and jS-eucaine lactate is greater than that of
is said to be used
cocaine ; that of novocain is less. All these five
by book- binders in South are compatible with adrenalin if the solutions are
America.
fresh mixed for each case. They are extensively
The kernels contain 47-2 p.c. of a fatty oil,
having the following characteristics employed ; but novocain is evidently the best
Saponifi- :
cation value, 187 ; iodine value, 77-83-6 ;

yet discovered for routine use.
refraction in Zeiss' butyro-refractometer at 25,
Local anaesthetics are used dissolved in
58-1-58-8 (TheopolJ, Pharm. Zeit. 1909, 1057). water or in normal saline solution. It is not
essential that they should be injected subcutanc-
J. L.
AN/ESTHETICS. There are three principal ously ; where the surface tissues are delicate, as
on the eye, larynx, tongue, tonsils, simple
types of anaesthesia, or loss of sensation sufficient
to allow of surgical operations without contact with a local anaesthetic in solution or in
pain. In
fine powder will destroy sensation sufficiently
local anaesthesiathe actual tissues to be lacerated
are for many surgical procedures. But elsewhere
with some substance which
infiltrated
the solution is injected with a hypodermic
paralyses the endings of the nerves that convey
painful sensations. In general anaesthesia, total syringe into the tissues which are to be rendered
anaesthetic. If adrenalin be mixed with the
insensibility and loss of muscular power are
anaesthetic solution, contraction of all the
produced by the action of drugs on the brain,
carried there in the circulation ; minute blood-vessels in the locality takes place.
extensive
operations on any part of the body can then be 1
Le Brocq, Pharm. J. 1909, 674.
156 ANESTHETICS.
Thus the drug retained longer in the tissues
is America and on the Continent anaesthol, somno-
about the site of injection, instead of being form, and narcotile are also employed. Anaasthol
rapidly dissipated in the blood -stream. Conse- is a mixture of chloroform, ether, and ethyl
quently a more intense and lasting, because more chloride, in molecular proportions somnoform
;
strictly local, action occurs. is ethyl chloride 60 parts, methyl chloride

Local anaesthesia can also be obtained by 35 parts, ethyl bromide 5 parts ; narcotile has
freezing the superficial tissues. A fine jet of been stated to be a compound, but analysis has
ether or ethyl chloride is directed on to the shown it to be a mixture of methyl chloride,
desired portion of the skin, and when the latter ethyl chloride, and ether. Mixtures of ether
is frozen a cut can be made, as for a whitlow, and chloroform in various proportions are in
boil, or other small abscess, without causing common use everywhere. Morphine, chloral,
pain. cannabis indica, and many other drugs have
Spinal anaesthetics. Some of the same drugs analgesic and anaesthetic properties ; some of
which cause local anaesthesia are available for them, morphine especially, are used to assist
injection into the cerebro-spinal fluid with whicji the action of the volatile ana3sthetics.
the spinal cord is surrounded in the vertebral The effects of a general anaesthetic are pro-
canal. Stovaine and novocain are most used in duced by the circulation in the blood of the
Britain, but tropacocaine also is popular in drug employed. When reaches the brain the
it
Europe. The method was introduced by Bier phenomena of anaesthesia are exhibitedat first :
in Germany in 1899, and since 1907 has been doses more and
slightly, then with increasing
very extensively tried all over the world. The more intensely, until with a sufficient quantity
balance of opinion is that for ordinary cases death results. The phenomena of general
spinal anaesthesia is too dangerous to replace anaesthesia are the same whether absorption
general anaesthesia ; but that for certain cases takes place through the lungs, rectum, skin, or
where the latter entails especial risks, it is of
gastro-inteptinal tract.
Thus alcohol has a
undoubted utility. Barker and McGavin, 2 who
'
marked anaesthetic effect, familiar in the in-
are the most prominent advocates of spinal difference of a drunken man to injury.
anaesthesia in England, use a solution of stovaine The easiest way of introducing into the blood
in 5 p.c. glucose ; 4 to 7 centigrammes of any substance which is a gas or a volatile liquid
stovaine is the dose for an adult. Ryall, follow- is by means of the lungs. The blood thus
ing Jonnesco of Bucharest, adds half to one charged with an anaesthetic, is rapidly delivered
milligramme of strychnine to 4 to 10 centi- to the nervous centres, in .which the essential
3
grammes of novocain. Strychnine is also used changes of general anaesthesia take place.
The
with stovaine, and with tropacocaine ; the object with
absorption of vapours in the lungs varies
is to prevent the anaesthetic from causing death if numerous factors barometric pressure, tem-
:
it should by any chance reach the respiratory

perature of the vapour and of the blood,
rate of
centre near the upper end of the spinal cord. the
respiration, and rate of blood-flow through
Bier has used morphia with scopolamine (hyo- But the process is also
pulmonary svstem.
scine) as a preliminary, injected hypodermi- something more than simple solution by diffusion
cally ; but he seems now to be convinced that of gases through a thin membrane ; there is at
the method which he originated is too risky to least an element which depends on the fact that
4
replace general anaesthesia. the tissiies concerned are living.
General anaesthetics. There are many sub- The lungs are also the chief, but not the
only, medium for the elimination
stances which diminish or abolish the perception of inhaled
of pain ; but only a few of these are freely used anaesthetics. These are but little decomposed
as general anaesthetics. The conditions which during their tour of the circulation,
and the
must be fulfilled to obtain admission to the list after the
greater part is discharged unchanged
are 5 : administration is suspended. What change
(1) To produce absolute insensibility to pain they undergo in the blood is very uncertain.
without causing any great discomfort during Chloroform, which has hitherto received more
induction. attention in this respect than the others, is
(2) To produce loss of all voluntary and many recoverable from the blood in fatal cases of
reflex movements. chloroform anaesthesia, but it is believed that
(3) To be capable of
being readily introduced most of it circulates in the red corpuscles of the
into the system, and rapidly eliminated, after blood in combination with the lecithin and
1
the completion of the operation, without injury cholesterin which they contain. Glycuronic
to the patient. acid not uncommonly appears in the urine after
(4) To act in a regular and constant way, so chloroform anaesthesia. Nitrogen and sulphur
that the effects can be controlled by the adminis- are also excreted in the urine in greater quantity,
trator. indicating a greater destruction of proteid
and ;
The general anaesthetics in use in Great Britain the increase of chlorides is held to show that
are four in number nitrous oxide, ethyl chloride,
: some chloroform is decomposed in the body.
ether, chloroform. Ethyl bromide, ethidene di- The affinity of cholesterin and lecithin for chloro-
chloride (dichlorethane), bichloride of methy- form, chloral, ether, sulphonal, tetronal, trional,
lene, and amylene (pental) are obsolete. In and chloralamide has been suggested as the
1
British Medical Journal, 1908, ii. 453 (and other explanation for the selective action of these
papers). narcotics on the central nervous system, which
contains a larger proportion of cholesterin and
"
Practitioner, August, 1909: British MedicalJournal,
Sept. 17, 1910. lecithin than do the other organs. With regard
3
Clinical Journal, July 17, 1909.
4
Deutsch. Zeitschr. f. Chirurgerie, xcv. 373. to ether, Turnbull states that etherisation
s
R. W. Collum, The Practice of Anaesthetics, 1909,
14.
1
Hale White, Materia Medica, llth ed. 1909, 280.
ANAESTHETICS. 157
produces a marked diminution

of the haemoglobin muscular relaxation necessary. Nitrous oxide
of the blood ; and Reicher finds three times gas is the safest known general anaesthetic, and
'
the normal quantity of fat present in the blood, recovery takes place very rapidly (two or three
increased amount of acetone,
together with an minutes) without unpleasant after-effects.
due to the disintegration of fat and albuminoid Ethyl chloride. The vapour of 3 to 5 c.c. of
bodies. 2 The chemical composition of the blood this substance allowed to volatilise in a closed
is often much modified during anaesthesia, be- chamber, such as a rubber bag, into which an
cause the air supply to the lungs is frequently adult patient exspires and from which he
inspires,
curtailed to a greater or less extent, and the produces anaesthesia very rapidly. If adminis-
elimination of C0 2 hindered. The proportions tration is then suspended,
insensibility lasts
of and C0 2
in the circulating blood may thus from one to two minutes. By administering a
be altered at the expense of the former, and an further dose before recovery takes place from
asphyxial element added to the narcotic effect the first one, anaesthesia can be
prolonged ; it
of the anaesthetic. Some authorities believe is preferable, however, to
give ether or chloro-
that deprivation of oxygen is the method by form or nitrous oxide and oxygen if a longer
which all anaesthetics produce their action on anaesthesia is required. The after-effects of
ethyl
3
the nervous tissues. chloride are intermediate between those of
The chemical changes which may be assumed nitrous oxide and those of ether and chloroform.
to take place in the brain during anaesthesia are Ethyl chloride given by an expert is safer than
unknown, as indeed are those of natural sleep. either of the latter, but not so safe as nitrous
It has been suggested that unstable compounds oxide.
are formed between the anaesthetic and the Ether. About 30 p.c. of air and 70 p.c. of
protoplasm of the nerve cells, and some ob- ethereal vapour will produce and maintain
servers describe changes recognisable micro- general anaesthesia. The vapour is so intensely
scopically in those cells as a result of anaesthesia. irritating to the mucous membrane which lines
Professor Hans Meyer holds that there is a loose the mouth, nose, and air-passages, that it must
physico-chemical combination with the lipoids of first be offered very dilute, and then in a
the cell. This causes inhibition of the normal gradually increasing percentage. Limitation of
metabolism until the loose reversible combina- air supply renders it possible to procure anaesthesia
tion breaks up. A rare sequel of chloroform with a much smaller quantity of ether than when
anaesthesia is known as delayed chloroform fresh air is freely admitted, for a slight con-
poisoning. The symptoms of this condition, current asphyxia helps the action of the ether.
which sometimes fatal, arise about eighteen
is Such asphyxiation has disadvantages of its own
to seventy -two hours after the anaesthesia. They if allowed to exceed a very moderate
degree ;
'
are attributed to acidosis,' that is to diminished it is usually' present during anaesthesia under
'
alkalinity of the blood due to the presence of ether by the closed methods. There is slightly
acetone and aceto-acetic acid, which can be more difficulty in producing anaesthesia by the
detected in the urine and the breath. For the ' '
open method, in which air enters freely ; the
developed condition sodium bicarbonate in large preliminary injection of small doses of morphine
doses is employed ; as a preventive measure (-|-
to J grain) with atropine y
s to T J 5 grain)
is of
feeding on glucose for a day or two before advantage. Ether is much less dangerous to
operation is found to answer best. Very rarely
4
life than chloroform in the operating room ; but
indeed this acidosis has followed the adminis- part of this advantage is counterbalanced by
tration of ether. the occasional development of bronchitis and
Nitrous oxide (Laughing gas). The inhala- broncho-pneumonia afterwards.
tion of from three or four to twenty or thirty Chloroform. Much research has been carried
gallons of this gas without any air produces out to determine the percentage of chloroform
anaesthesia. If the administration is then sus- necessary to produce anaesthesia by inhalation.
pended, insensibility lasts on an average about Vernon Harcourt introduced early this century
thirty to forty-five seconds, during which time a chloroform inhaler capable of regulating this
minor operations such as the extraction of teeth proportion up to 2 p.c. Experience showed that
can be undertaken. A marked asphyxial ele- in occasional cases it is very difficult or impos-
ment is nearly always present, owing to the sible to induce anaesthesia with this amount, and
replacement of oxygen by 2 0. N
If air be a modification of the instrument allows air to be
admitted for brief "periods between successive inspired containing 3 p.c. In practically every
doses of gas, anaesthesia can be maintained case anaesthesia, when fully established, can be
without great difficulty for several minutes. By maintained with a 2 p.c. vapour. Alcock, who
delivering nitrous oxide mixed with pure oxygen has investigated the dosage of chloroform very
for inhalation, anaesthesia can be prolonged for carefully, finds
l
that for an ordinary adult it
any desired period. The proportions of the two suffices to offer a percentage rising gradually
gases are varied to meet the requirements of to 2| in three minutes ; this as a rule produces
individual cases, but roughly the mixture must in eight to ten
complete surgical anaesthesia
contain about 80 p.c. by volume of N 2 0. The minutes. If a higher proportion is necessary,
previous injection of narcotics such as morphine, 3 p.c. may be allowed at the end of five minutes.
with atropine, facilitates the induction of He finds" that within a few minutes after in-
anaesthesia. This method is well suited for duction is and after half an
complete 1-5 p.c.,
operations on the limbs, but for abdominal hour 1 p.c.,
be enough. Several
will usually
operations it is difficult to get the complete physiologists have
estimated the amount of
chloroform in the circulating blood during
1
Laurence Turnbull, Artificial Anaesthesia, 223.
2
Reicher, Lancet, Jan. 25, 1908, 268.
3
B. Gill, The CHC1 3 Problem, 1906. i
N. H. Alcock, British Medical Journal, Feb. [6.
4
Wallace and Gillespie, Lancet, Dec. 5, 1908, 1665 1909, 325.
158 ANESTHETICS.
longer time for their execution.
It is in this
anaesthesia : their results vary from 0-035 to
0-07 p.c. Chloroform is the most dangerous of direction that volumetric analysis has been most
these four anaesthetics, especially in the hands xtensively developed, the general tendency in
of those whose experience as anaesthetists is industrial laboratories being to replace gravi-
small. H. R. metric methods by quicker volumetric processes
with with very little loss in accuracy, provided
ANALGESINE. Identical antipyrine
that certain essential conditions be fulfilled.
(q.v.).
ANALYSIS. Chemical analysis is the separa-
tion of a complex materhl into simpler con- General Operations.
stituents. It is ultimate when these component Sampling. It is of the highest importance
parts are elementary forms of matter,
and that the sample under examination should be
proximate when the subdivision consists only truly representative of the bulk of the substance.
in the separation of the original substance Discrepancies between the results of different
into less complicated compounds. The aim of analysts are usually attributed to faulty
chemical analysis is twofold : the first object, methods or inaccurate work, but in many cases
is to ascertain the nature of the compo- they are really due to imperfect sampling. If
nents of a mixture or complex substance; the substance is a liquid, the contents of the
the second is to determine the proportions in vessel should be thoroughly mixed before the
which these constituents are present. All sample is withdrawn. If the substance is con-
analytical operations may therefore
be classified tained in several vessels, a proportional quantity
under the two main categories of qualitative and should be taken from each, the different portions
quantitative analysis, according
as to whether mixed together, and the final sample taken from
these processes lead to the identification of the the mixture.
proximate or ultimate constituents of a complex In the case of solid products care must be
substance, or to the determination of the relative taken to secure a proper proportion of large and
proportions in which these constituents
are small, hard and soft fragments. If a ship's
present. cargo is to be sampled, portions should be

This article is written primarily from the taken from different parts of the bulk ; if the
technical point of view, and accordingly the substance is contained in railway trucks, por-
descriptions given in the qualitative section
are tions should be taken from the ends and middle
restricted mainly to those elements which find of each truck. When the substance is in bags
application in the arts and industries. Simi- or barrels, a long hollow auger is thrust to the
larly, the estimations and separations bottom of each and then withdrawn, bringing
outlined
in the quantitative section are chiefly those with it a long core of the substance. If the
required in the analysis of technically important material loses or gains moisture, or undergoes
materials. any other change on exposure to air, as in the
The systematic investigation of the individual case of soap or caustic soda, a proper proportion
elements and their typical compounds has of the internal and external portions must be
revealed the existence of many characteristic taken. In all cases the first samples are broken
reactions which are exhibited by certain elements into small pieces, thoroughly mixed, and one-
and compounds under widely varying conditions fourth taken for further treatment. This is
of combination or association. This circum- ground to powder, again thoroughly mixed, and
stance leads to a simplification which is utilised one-fourth taken. The subdivision is repeated,
extensively in both qualitative and quantitative if necessary, and the final sample kept in well-
'
In qualitative work, such charac-
'
analysis. closed bottles. This process of quartering

teristic reactions as are not generally interfered may also be effected by spreading out the finely
with by other substances enable the analyst to powdered material in the form of a flattened
detect the presence of certain elementary or cylinder dividing this radially into four parts,
compound substances without undertaking the taking out the opposite sectors, mixing these
more laborious processes involved in isolating thoroughly, and repeating the subdivision.
these constituents from the other ingredients of If the mixture is soft and friable, pulverisa-
a mixture. tion is readily effected in a porcelain or earthen-
In analysis two essentially
quantitative ware mortar, but harder substances should be
different methods of procedure are em- powdered in a cast-iron or steel
ployed, the more fundamental one being gravi- mortar. When the substance is
metric analysis, in which the elementary or hard, and a very fine powder is
complex constituent of a mixture is isolated required, an agate mortar should
and weighed hi the form of a definite compound. be used for the final operation, so
By utilising quantitatively the above-mentioned that the powder may be completely
distinctive reactions it is frequently possible to sifted through fine muslin. Very
adopt the second procedure known as volumetric hard substances, such as minerals,
analysis, in which the relative amount of a certain are first broken into small pieces
constituent is estimated in the presence of other by wrapping them in paper and
elements and compounds associated with this striking with a hammer, and are
constituent in the mixture under examination. then further crushed in a steel
For the purposes of scientific investigation mortar (Fig. 1) consisting of a strong
the most accurate methods are essential, and base with a circular recess into which
these are, in the main, gravimetric in cha- fits a movable steel
ring or guard,
racter but for technical requirements extreme
; and inside this is a solid steel
accuracy is rarely required, and rapid methods piston which acts as a pestle. A
giving approximately correct results are pre- small quantity of the mineral is placed on the
ferred to more exact processes involving a base of the mortar inside the guard -ring, the
ANALYSIS. 159
latter held firmly down, and the piston is

is of which is close beside the vessel which is being
with a hammer, heated.
placed inside and struck smartly
which drives it down upon the mineral. The If it is desired to keep the
temperature con-
final crushing is done in an agate mortar. stant for a long time, the oven must be
provided
The mechanical ore-grinder described in with a thermoregulator (v.
THERMOREGULATORS).
Hillebrand's Analysis of Silicate and Carbonate Weighing. The balance and the precautions
Rocks, may likewise be employed in reducing to be observed in weighing form the
subject of a
hard minerals to a fine powder. special article (v. BALANCE). As a rule, sub-
Drying. Many substances absorb more or stances taken for analysis should be
weighed
less moisture when exposed to the air, and in from tubes provided with well-fitting stoppers or
order to bring them into a definite condition for corks, or from weighing bottles fitted with glass
analysis, it is desirable that they should be dried, capsule stoppers, the difference between the
this operation being conducted at the ordinary weight of the tube or bottle before and after
or at a higher temperature according to circum- the removal of the substance giving the
weight
stances. Substances which contain water in taken for analysis. The quantity required for
combination are usually dried by exposure to air an analysis will depend upon circumstances.
or by pressure between folds of filter paper. In When constituents present in minute quantity
other cases where a higher temperature would have to be estimated, a relatively large amount
be injurious the substance may be placed under of the substance is required, but for the estima-
a bell-jar which also incloses a dish containing tion of one or two constituents from 1 to 2 grams
sulphuric acid. The operation proceeds more of the substance is usually sufficient. The
quickly if the bell- jar is connected with an air- smaller the quantity of matter operated upon,
pump and thus rendered vacuous. the shorter the time required for filtration,
Substances Avhich do not decompose at 100 washing, &c., but also the greater the demands
are best dried in a copper oven provided with a on the skill and accuracy of the operator.
jacket containing water which is heated to Hygroscopic substances and precipitates must
boiling, the water-level being kept constant by
be kept under a desiccator (q.v.), i.e. a glass dish
means of an overflow a and feeding arrangement containing sulphuric acid or calcium chloride,
fitted with a tray to support a crucible, &c., and
provided with an air-tight glass cover, preferably
bell-shaped. Crucibles containing non-hygro-
scopic precipitates may be allowed to cool with
exposure to air, provided that the empty crucibles
were allowed to cool under the same conditions
before weighing.
Solution. The solution of a substance is
most conveniently effected in flasks or in some-
what deep beakers which are inclined at an
angle in order to prevent possible loss by spurt-
ing. The operation may be accelerated by heat,
and the reagent should be used in the most
concentrated form possible and in the least pos-
sible excess, in order to avoid loss of time in
evaporation, &c. Evaporation to expel excess
of solvent should, where possible, be conducted
in the same vessel.
Evaporation.- The evaporation of a liquid
may be effected over an ordinary bunsen flame,
or over a rose burner, care being taken that the
liquid does not boil. If the operation is con-
ducted in a flask or crucible, the latter should be
inclined in order to prevent loss by ebullition,
and the operation is accelerated in the first case
FIG. 2. by drawing a current of air through the flask, in
the second by inclining the lid of the crucible
at the side. The inside of the oven is fitted (Fig. 3) across the mouth of the vessel and thus
with a perforated shelf which supports dishes, producing a circulation. The rate of evapora-
funnels, &c. (Fig. 2). tion, cceteris paribus, depends on the area of
When the substance is sufficiently stable it surface exposed, and hence the operation is
is advisable to
dry at 115-120, since an increase effected most quickly in shallow dishes, especially
of 10 or 20 often greatly reduces the time re- if a current of air removes the vapour as fast
quired. For this purpose we use a copper oven as it is given off. During the process the
without a jacket, heated by a lamp underneath ; contents of the dish should be protected from
or toluene, boiling at 110, may be used instead dust, &c., and this is really done by supporting
of water in the oven with a jacket; crude at a distance of about six inches above the
xylene will give a higher temperature (129). surface of the dish a triangle of glass rod or
Inside the oven at a little distance from the
tubing on \vhich is stretched a sheet of filter
bottom is a shelf which supports the vessel paper freed from soluble compounds by treat-
containing the substance. At the top of the ment with acid. When evaporation over a
oven are two apertures, one of which serves direct flame impracticable, the dishes, &c.,
is
to promote a current of air should be placed on a water-bath, that is, a
through the oven,
whilst the other carries a thermometer the bulb vessel containing boiling water, in such a way
160 ANALYSIS.
that they are heated by the steam. The top of Filtration. The separation of a precipitate
the water drying-oven already described (Fig. 2) from a liquid usually effected by means of a
is
may be provided with a series of rings of various specially prepared variety of blotting paper,
known as filter paper. The Swedish paper
made by J. Munktell has the oldest reputation,
but that made by Schleicher and Schull, of
Diiren, is of excellent quality, and for many pur-
poses answers better. The latter firm supply
paper which has been treated with hydrochloric
and hydrofluoric acids, and thus freed from
almost all inorganic matter. Filter papers of
similar quality are also supplied by Max Drever-
hoff, and by Baker and Adamson. It is de-
sirable that all paper used in quantitative work
should be free from soluble compounds, and this
end is secured by soaking the ordinary filter
paper for three or four hours in pure hydro-
chloric acid diluted with 1520 times its volume
of water, and then washing thoroughly to remove
all traces of acid and soluble salts. The paper
is conveniently kept in circular pieces of known
radii (2, 4, 5, 6, 8 cm.), and the ash left by each
size should be determined once for all by in-
cinerating six filters of one of the medium sizes
in the manner described under the treatment of
precipitates, and weighing the ash which is left.
This quantity divided by six gives the average
amount of ash left by one filter of that size, and
the amount left by the other sizes is readily
calculated, the quantity of ash being propor-
tional to the area of the paper.
FIG. 3.
Usually the filter paper is supported in a
sizes and thus serves two purposes. Ordinary glass funnel which should have smooth even
tin cans or copper vessels of similar shape will sides and an angle of 60. The stem should be
answer, but in all cases it isdesirable to have somewhat long and not too wide, with the lower
an arrangement for keeping the water at a con- end cut obliquely. A circular filter is folded in
stant level. half, then in a quadrant, and when the quadrant
Precipitation is conducted in beakers, dishes, is opened at one side it forms a hollow cone
or conical flasks, but not in ordinary round which should fit accurately into the funnel.
flasks because of the difficulty of removing the The edge of the filter paper should be about
precipitate. Glass vessels, especially when new, 10 mm. below the edge of the funnel, and the .
are appreciably attacked and dissolved by water, size of the filter should be such that it is not
and still more strongly by alkaline solutions, more than three quarters filled by the preci-
the action increasing with the concentration of pitate. After placing the filter in position it is
the solution and the duration of contact. For moistened with water, and fitted accurately to
quantitative work Jena glass vessels should be the glass, care being taken to remove all air
used, as these are least affected by alkalis. bubbles from between the glass and the paper.
Acid liquids, with the exception of dilute sul- Attention to these points greatly facilitates the
phuric acid, have less solvent action. Porcelain subsequent filtration. The edge of the vessel
vessels, especially after they have been used for containing the liquid to be filtered is slightly
a short time, are not appreciably attacked greased outside, and the liquid is directed into
(Fresenius's Quant. Anal.). All precipitations the filter by means of a glass rod, care being
involving long heating with alkaline liquids taken not to disturb the precipitate until most
should be conducted in porcelain vessels or in of the clear liquid has passed through. It is
platinum, silver, or nickel dishes. Silica-ware advisable to keep the filter well filled with the
vessels can be used with all acid liquids except- liquid, but the latter must not rise higher than
ing those evolving hydrogen fluoride (Zeitsch. 10 mm. below the top of the paper.
anorg. Chem. 1905, 44, 221). In order to accelerate filtration a glass tube
Unless circumstances forbid, the liquid and about 3-4 mm. in diameter and not less than
the reagent should be heated to boiling and 20 cm. long, bent into a loop near its upper end,
mixed gradually with continual agitation, since may be attached to the stem of the funnel by
under these conditions precipitation as a rule is means of indiarubber tube.
more rapid and complete, and the precipitate Greater rapidity of filtration is obtained by
is obtained in a dense and granular form and using one of the numerous water pumps (v.
is readily separated and washed. Usually nitra- FILTER PXJMP). In this case the liquid is filtered
tion may be commenced as soon as the super- into a flask with stout walls, preferably of the
natant liquid is clear, or at any rate after two conical form. The stem of the funnel passes
or three hours. An unnecessary excess of reagent through a cork which fits in the neck of the
should always be avoided, but in all cases com- flask and also carries a tube connected with the
plete precipitation should be proved by adding pump, or the flask may be provided with a side
a small quantity of the reagent to the clear tube for this latter purpose. When it is required
liquid. to filter into a dish or beaker, the latter is placed
ANALYSIS. 161
under a tubulated bell-jar standing on a glass care being taken that the pump is set in action
the funnel, &c., being before any liquid is poured into the crucible.
plate, the cork carrying
fitted into the tubulus of the bell-jar. If the Drying and igniting the precipitate occupies but
reduction of pressure is considerable, it becomes little time. For gelatinous precipitates the
necessary to support the apex of the filter. In crucible may be replaced by a cone, the lower
the case of filters of medium size the necessary part of which is made of platinum gauze and
into the apex the upper part of platinum foil.
toughness is obtained by dropping
of the dry filter, after it has been fitted into the Gooch has proposed (P. Am. A. 1885, 390 ;
funnel, two or three drops of the strongest Zeitsch. anal. Chem. 24, 583) in special cases to
nitric acid. After a minute or two the paper is replace the asbestos by anthracene, which after
washed and is ready for use. Bunsen's original filtration can be dissolved in benzene or other
method is to support the apex of the filter by suitable solvent, leaving the precipitate undis-
means of a cone of platinum solved.
foil, which is made in the Not unfrequently it is necessary to keep the
following way. A circular contents of a funnel hot during filtration. This
piece of thin platinum foil is effected by placing the funnel inside a
copper
34 cm. in diameter is cut jacket filled with water which is heated to boil-
in the manner shown in the ing by means of a side tube. A simpler plan is
diagram (Fig. softened
4), to coil lead pipe round the funnel and blow
d by a flame, and
heating in steam through the pipe (Richter, J. pr. Chem. (ii.)
then placed against a small 28, 309).
metal cone of 60, so that Sometimes it is desirable to avoid contact
the point a coincides with the apex of the cone. with air during filtration. A convenient ap-
The foil is then folded round the metal so that it paratus for this purpose has been described by
also forms a small cone, which is finished by being Klobukow (Zeitsch. anal. Chem. 24, 395 ; J. Soc.
pressed in a hollow conical mould into which Chem. Ind.'4, 756).
the metal cone fits. It is then dropped into All precipitates require to be washed in order
the funnel and the paper fitted in. The metal to remove soluble impurities, the liquid em-
cones and moulds required can be purchased; ployed being water, dilute acid, dilute ammonia,
Bunsen's method of making a cone and mould alcohol, &c., as the case may require. The
of plaster is described in Thorpe's Quantitative object in all cases is to reduce the impurity to
Analysis. the desired minimum in the shortest possible
Carmichael has described a method of reverse time with the least expenditure of liquid, and it
filtration (Zeitsch. anal. Chem. 10, 83). can readily be shown that successive treatments
The Gooch crucible (Chem. News, 37, 181), with small quantities of the liquid are far more
which has a perforated bottom lined with a effectual than the same volume of liquid applied
thin asbestos mat, has now become a recognised all at once (Bunsen, Annalen, 148, 269). When-
means of collecting precipitates. The asbestos ever possible hot liquids should be used, and the
makes an excellent filter, is not affected by precipitate should be washed so far as possible
ordinary acid and alkaline liquids, is readily by decantation, only the washing liquid being
dried, and does not alter in weight when ignited. poured on the filter. The soluble impurity
The quality of the asbestos is of prime import- collects round the top edge of the filter paper
ance, a non-ferruginous amphibole being pre- by reason of capillary action and evaporation,
ferable to the cheaper hydrated varieties of and hence, when washing is effected with the
serpentine which are appreciably soluble in aid of an ordinary wash-bottle with a movable
acids. Silky asbestos is scraped into a short jet, it is important that the liquid should be
fine down, boiled with hydrochloric acid, well directed on to the top edge of the filter. It is
washed, and kept in water. A platinum or silica also important that each quantity of wash-
crucible, preferably of the low wide form, with water should be drained away as completely
the bottom perforated with a large number of as possible before adding a fresh quantity, and
minute holes, is fittedair-tight into an ordinary it is obvious that this takes place most readily
funnel by means of an indiarubber ring placed when a pump is used. In this case the liquid
between the crucible and the wall of the funnel, is poured into the funnel from an open vessel
which is fitted into a filtering flask. The pump to a height of about 10 mm. above the edges
is set in action and water
containing the asbestos of the paper. Care must be taken that the
in suspension is poured into the crucible. A
layer precipitate is not drained so far that channels
of asbestos felt is quickly formed, and when this are formed. It is always advisable to ascertain
isof sufficient thickness it is drained, dried, and whether the washing is complete by testing a
ignited over a lamp, and the crucible is then few drops of the last wash- water.
weighed. It is desirable to have a non-per- Drying and weighing precipitates. Occa-
forated bottom to fit on the crucible during sionally a precipitate must be dried without the
ignition, in order to protect the contents of the application of heat, and this is accomplished in
crucible from the flame gases. A
Soxhlet tube, a desiccator over sulphuric acid, preferably in a
having a perforated porcelain or platinum disc vacuum. In other instances the substance is
covered with an asbestos layer and supported not injured by a temperature of say 120, but
at the constricted part of the tube, is frequently cannot be ignited. In these cases the filter is
used to collect precipitates. Neubauer recom- carefully dried at the particular temperature,
mends a perforated platinum crucible with a enclosed between a pair of watch-glasses, and
felted platinum mat (Zeitsch. anorg. Chem. weighed. It is then placed in the funnel
and
1901, 922; cf. Amer. Chem. J. 1909, 31, 456). the operation proceeded with. After filtration
The weighed crucible is replaced in the funnel, the filter and the precipitate are thoroughly
and filtration is conducted in the ordinary way, dried at the same temperature as before and
VOL. I. r. M
162 ANALYSIS.
again weighed, the increase being the weight of ing vessels at 100. If higher temperatures are
the precipitate. Tared filters can, however, be needed, a saturated solution of calcium chloride,
generally replaced by Gooch crucibles, Soxhlet melted paraffin, or oil may be used. Maumene'
tubes, &c. The majority of the precipitates (Compt. rend. 1883, 97, 45, and 215) has proposed
usually met with can, moreover, be dried by to use fused mixtures of alkaline nitrates for
heating them in a crucible over a lamp. In temperatures between 140 and 250. Brauner
most cases it is not necessary that the precipi- (Chem. Soc. Trans. 1885, 47, 887) has described
tates should previously be dried. The greater a simple arrangement for heating substances in
part of the water is removed by draining in the sulphur vapour.
funnel by means of the pump or by placing the Reagents. The ordinary acids and ammonia
filter and its contents on a porous tile or on a are required in a dilute as well as in a concen-
pad of filter paper. The filter is then intro- trated form. Whenever possible the reagents
duced into a crucible, heated cautiously until should be made in solutions the strengths of
quite dry and then heated more strongly until which are multiples or submultiples of normal
the weight is constant. solutions. A convenient strength for the dilute
When the precipitate is not easily reducible mineral acids is twice normal, and the alkaline
it is not necessary to remove the paper before solutions should be of equivalent strength.
ignition. The wet paper enclosing the precipi-
tate is placed in a platinum crucible, and the QUALITATIVE ANALYSIS.
latter heated with a full flame ; the water The detection of the constituents of a
present assumes the spheroidal state and the mixture or chemical substance is based on the
paper smoulders away without spurting. If fact that almost every metallic or acidic radicle
any slight reduction takes place, for example, will under suitable conditions give rise to a
with barium sulphate, it is easily remedied by reaction which, under these conditions, is
adding a few drops of dilute sulphuric acid and characteristic and thus enables one to distinguish
again heating. In the case of magnesium pyro- this radicle from all others. These tests may be
phosphate strong nitric acid serves a similar applied directly to the solid substance, usually
purpose. If, however, the precipitate is readily at high temperatures, when they are known as
reduced in contact with organic matter, it must dry reactions ; or they may be employed in solu-
be removed from the paper as completely as tion, in which case they are described as wet
possible by gentle friction, and transferred to reactions. The wet and dry reactions of metallic
the crucible, which should stand on a sheet of and acidic radicles are generally, but by no
glazed paper. A carefully trimmed feather or means invariably, independent of the acidic and
a camel's-hair brush is useful to transfer scattered metallic radicles with which they are respec-
particles from the paper to the crucible. The tively combined.
filter paper is then folded with the portion to
which the precipitate had adhered inside, Examination in the Dry Way.
wrapped in platinum wire which forms a sort The indications obtained from the dry re-
of cage, and set on fire. Whilst burning it is actions of a substance frequently afford very
held over the crucible, and when completely suggestive clues to its composition, but as these
burnt out, the ash is heated with the tip of a tests rarely, if ever, indicate the relative pro-
Bunsen flame for a few minutes and then shaken portions in which the constituents exist in the
into the crucible. mixture under examination, they must be re-
Precipitates which contain compounds of garded as being preliminary to the more syste-
silver, lead, zinc, tin, and other easily reducible matic examination of the substance in solution.
metals, should be heated in porcelain crucibles, Moreover, negative results obtained from dry
since platinum vessels are liable to be attacked. tests must not be accepted as final evidence.
Care should also be taken that platinum vessels In all cases, however, a preliminary examina-
' '
are not heated with smoky or roaring flames, tion of the substance should be made in the dry
and do not come in contact with brass crucible way, and if the substance is in solution a portion
tongs or easily fusible metals whilst hot. After should be evaporated to dryness. The reactions
some time the surface of the metal may become of several substances in the dry way are inter-
dull, owing to the partial disaggregation of the fered with and rendered inconclusive by the
platinum, but this defect can be remedied by presence of certain other substances ; but never-
polishing the metal with sea-sand or a burnisher. theless an examination of this kind often gives
Heating appliances. The ordinary bunsen much information in a short time.
burner serves for most operations, but the argand The most convenient source of heat for this
bunsens introduced by Fletcher are more efficient, purpose is the ordinary bunsen burner. This
and the radial slit burner of the same inventor consists of a metal tube at the base of which
is perhaps the most efficient gas-burner for heat- coal gas enters by means of a jet, the lower part
ing purposes that has yet been made. Glass of the tube being pierced with holes through
vessels are more safely heated on a sheet of wire which air is drawn and mixed with the coal gas.
gauze or on a layer of sand in a metal tray. A The mixture of 1 volume of coal gas with about
most useful piece of apparatus in a technical volumes of air, which is thus produced, burns
laboratory is a large iron plate supported on iron at the top of the tube with a non-luminous flame.
legs, and heated by a burner underneath the When the supply of gas is turned low, it is
middle. Vessels placed on the plate near its necessary also to reduce the air supply by
edges are subjected to a very gentle heat, but partially closing the inlet holes by means of a
may be raised to a much higher temperature by regulator. The upper part of the burner is
being moved nearer to the middle. generally fitted with a support carrying a cone
A water-bath provided with a constant feed- to protect the flame from draughts.
ing arrangement is the most useful way of heat- The flame consists essentially of an inner
ANALYSIS. 163
dark zone containing unburnt gas mixed with flattened and cut off obliquely. The flame
air, and an outer zone
or flame mantle in which should be much smaller than when the burner
combustion becomes com- is used in the ordinary way.- Coal
gas usually
plete. If the air holes are contains more or less sulphur, and
consequently
partially closed, a luminous cannot be used when testing for this element.
cone appears at the top of A thick stearin candle answers well but ;
the inner zone. Bunsen has nothing is better than a lamp consisting of a low
shown, however, that several and rather wide cylindrical metal vessel, open
distinct zones exist, each of at the top, with a somewhat broad and flat wick-
which can be utilised for pro- holder attached to the side. The fuel used is
ducing particular reactions. solid paraffin, which is kept in a melted condi-
The most useful of these are tion by the heat of the blowpipe flame, the wick
a, a comparatively cold zone being so arranged that the flame passes over the
at the base of the flame, which top of the paraffin. A metal cover protects the
serves for the volatilisation lamp from dust when not in use.
of salts in order to obtain The nozzle of the blowpipe is introduced a
flame colourations ; the lower short distance into the lamp flame at a short
redwing flame S about one distance above the wick, and when the blast is
quarter of the way up and produced the flame is deflected horizontally,
close to the edge of the dark becomes long and narrow, and is seen to consist
zone ; ij, the upper and more of two parts, viz. an outer or oxidising flame, at
powerful reducing flame at the tip of which there is an excess of oxygen
the top of the dark zone,
obtained by closing the air
holes until the tip of the
inner zone just becomes lu-
minous ; 0, the zone of fusion
or highest temperature, .at
about one-third the height of heated to a high temperature, and an inner or
FIG. 5.
the flame and half-way be- reducing flame, which contains carbonic oxide
tween the inner zone and the flame mantle ; and hydrocarbons heated to a high temperature.
If the blowpipe is held just at the edge of the
7, the lower and hotter oxidising flame at the
flame and a moderate blast is used, a broader
edge just below the zone of fusion ; and e, the
upper oxidising flame at the extreme tip of reducing flame can be obtained, which has a
the flame. luminous tip containing solid particles of carbon.
Instead of the bunsen burner, the flame ob- The following appliances are required a :
tained by means of a blowpipe may be used ; a small pair of forceps with platinum points ; short
mouth blowpipe consists of a metal tube pro- pieces of thin platinum wire ; charcoal from some
vided at one end with a mouthpiece, the other end fine-grained compact wood glass tubes about
;
3 mm. internal diameter, and 60-80 mm. long,

fitting into a small metal box which serves to
condense and retain the moisture of the breath. closed at one end ; and glass tubes of similar
From the side of this box a second shorter diameter 100-120 mm. long, open at both ends
and narrower tube projects at right angles to and bent slightly in the middle. The reagents
the first, and is provided with a nozzle or used are borax, microcosmic salt (NH 4 NaHP0 4 ,
jet of
brass or, better, of platinum. For general work 4H 2 O),
potassium cyanide, sodium carbonate,
the diameter of the bore of the
jet should be
potassium nitrate, cobalt nitrate solution, and
potassium hydrogen sulphate.
The dry tests are conveniently performed in
the following order :
(1) Heating in a dry closed tube, To avoid

soiling the sides of the tube, the substance
should be introduced by means of a roll of stiff
FIG. 6. paper. The following changes may be observed :
(a) Carbonisation with or without evolution

04 mm. In Black's blowpipe the larger tube is of empyreumatic vapours =
organic compounds.
conical, the lower and wider end serving the Condensation of moisture on cold parts
(b)
-;uiiu
purpose as the box in the form just de- of tube neutral reaction
;
=
hydrated salts and
The art of keeping up a continuous hydroxides acid reaction = acids and acid salts
hcribed. ;
;
blast of ah- through the
blowpipe can only be alkaline reaction = ammonium salts.
acquired by practice. The necessary pressure is (c) Fusion without change of colour
= alka-
produced by distending the cheeks, breathing line salts, hydrated salts.
being carried on through the nostrils, whilst (d) Fusion with change of colour
= yellow
communication between the nostrils and the hot, dark yellow cold = bismuth oxide yellow ;
mouth is cut off by the pressure of the tongue hot, red cold = lead oxide. The chro mates of
against the palate. A
convenient form of hand- lead and the alkali metals fuse and darken on
blower for blowpipe work has been devised bv
heating.
Fletcher. No but change of colour dark
(e) fusion, :
A good flame for blowpipe work is obtained yellow hot, pale yellow cold =
stannic oxide ;
by dropping into the tube of an ordinary bunsen yellow hot, white cold =
zinc oxide ; black hot,
burner a brass tube, the lower end of which reddish -brown cold =
ferric oxide; black hot,
descends to the bottom of the burner and cuts
bright red cold =
mercuric oxide ; brown darken-
off the
supply of air, whilst the upper end is ing on heating = cadmium oxide.
M 2
164 ANALYSIS.
(/) Gas evolved: oxygen =oxides, peroxides, carbonate or of a mixture of 2 parts sodium car-
chlorates, bromates,perchlorates, iodates, periodates, bonate and 1 part potassium cyanide, is placed
persulphates, and nitrate* ; carbon dioxide
= in a small shallow hole scooped out in charcoal,
carbonates, bicarbonates, oxalates; carbon mon- and heated in a reducing flame. The metallic
oxide (blue flame) =
formates, oxalates; sulphur bead obtained is examined as to colour, malle-
dioxide =
acid sulphites, sulphates of heavy ability, solubility, &c. Many metals yield films
metals (together with sulphur trioxide) ; cyanogen of oxide, which coat the charcoal at a greater or
= cyanides of heavy metals ; ammonia am- = less distance from the flame, and the colour and
monium salts ; phosphine =
phosphites, hypo- appearance of which are more or less character-
phosphites ; orange-brown vapours nitrates, = istic. These and similar films are best seen
nitrites, bromides ; violet vapours iodides ; = when the charcoal is supported on an aluminium
colourless fuming gas =
hydrated chlorides. plate (Ross). A piece of sheet aluminium 12 cm.
(g) Sublimate : white infusible arsenious = by 5 cm. is bent in right angles at a distance of
oxide (octahedra), antimonious oxide (needles), 2 cm. from one end, thus forming a ledge on
selenium dioxide, ammonium chloride, am- which a small flat piece of charcoal is placed,
monium sulphite (from ammonium sulphate) ; the plate being held so that the surface rises
white fusible =
mercuric chloride, tellurium vertically behind the ledge. Volatile oxides, &c.,
dioxide, organic acids, molybdenum trioxide (at condense on the metallic surface (v. Hutchings,
very high temperatures) ; coloured, black, or Chem. News, 1877, 36, 208, 217).
reddish black =
selenium, mercuric sulphide ; The reduction may also be effected by adding
yellow hot, red cold =
mercuric iodide ; reddish a fragment of sodium to the substance supported
yellow = arsenious sulphide ; yellow sulphur = on charcoal (Parsons, J. Amer. Chem. Soc. 1901,
and sulphides ; black metallic mirror arsenic ; = 23, 159).
grey metallic globules =
mercury. These metal- In order to obtain reduced metals with the
lic sublimates are often obtained nore readily by bunsen flame, a match-stick is smeared with
heating the material with potassium cyanide. ordinary sodium carbonate (washing soda) which
Phosphorus compounds are detected by has been melted by holding it in the flame, and
heating in a closed tube with magnesium ribbon the wood thus prepared is carbonised by beating
and dropping the hot tube into water, when in- it in the flame. A small quantity of the sub-
flammable phosphine is evolved. stance is mixed in the palm of the hand with a
(2) Heating in open tube. The tube being small quantity of the fused washing soda, and
inclined, to promote a current of air through the mixture is carefully placed on the charcoal
it, the changes observed are similar to the splint, which is then heated in the lower or upper
reactions in the closed tube, but sulphides reducing flame. When reduction is complete,
burn evolving sulphur dioxide; arsenic is the match is allowed to cool inside the dark zone,
oxidised to arsenious oxide, and selenium and and is then withdrawn, crushed in a mortar, and
its compounds evolve a pungent odour of horse- the lighter particles of charcoal removed by
radish (dioxide), and give a grey or reddish levigation with water, the heavy metallic
sublimate. particles being left.
(3) Heating on platinum wire. Flame coloura- By means of the bunsen flame reduced metals
tions. The wire being cleaned by repeated dip- and their oxides can be obtained in the form of
ping in hydrochloric acid and heating till it imparts films on a porcelain surface. The substance is
no colour to the flame, a small quantity of the supported on a long slender piece of asbestos,
substance supported on the end of the wire is and heated in the tip of a small oxidising or
introduced into zone a of the bunsen flame. As reducing flame, a small evaporating dish con-
a colouration is produced only if volatile com- taining cold water being held momentarily just
pounds of the metals are present, the substance above the asbestos (v. Bunsen's Flammen-
should be moistened with hydrochloric acid to reactionen, Heidelberg, 1880).
produce the volatile chlorides. This result may Incrustations on charcoal white, very
:
also be attained by mixing the substance on an volatile =

arsenic ; white, less volatile anti- =
asbestos thread with moist silver chloride, a mony ; orange-yellow hot, pale yellow cold =
compound which, while imparting no colour to bismuth pale yellow hot, deep yellow .cold,
;
the flame, slowly yields chlorine, converting other white edge =

lead ; yellow hot, white cold =
metals into chlorides. The wire should be zinc, molybdenum reddish-brown or orange-
;
slowly moved into the hottest part of the blow- yellow cold =
cadmium.
pipe or bunsen flame, so that the colourations Metallic beads or residues on charcoal :
due to less volatile constituents may be suc- white malleable =

silver, tin, lead ; red malle-
cessively developed. able =copper grey brittle
;
=
antimony, bis-
Colourations : yellow =
sodium ; orange red muth ; grey powder, magnetic =
iron, cobalt,
= calcium crimson
;
=
strontium, lithium ; nickel ; non-magnetic =
molybdenum.
lavender =
potassium, rubidium, caesium ; apple (5) Cobalt nitrate reactions. Certain in-
green =
barium ; bright green thallium, = fusible substances, when moistened with cobalt
copper, boric acid ; pale blue =
lead, antimony ; nitrate solution and strongly heated, acquire
deep blue becoming green copper halides ; characteristic colours. These reactions are
deep blue =
selenium. frequently, but not necessarily, carried out on
The pocket spectroscope (direct vision) is a a charcoal support : blue infusible mass =
useful aidin examining flame colourations, aluminium ; blue fusible =
certain phosphates,
particularly in the case of strontium and calcium, silicates, borates ; green =
zinc, titanium, tin ;
which exhibit respectively a characteristic blue pink = magnesium.
and a yellowish -green line. (6) Heating urith borax or microcosmic salt.
(4) Healing on charcoal. The substance A small loop is made at the end of a platinum
mixed with three times its weight of dry sodium wire, to which some borax or microcosmic salt is
ANALYSIS. 165
made and heated in the flame until

to adhere, sium nitrate soluble green mass = manganese ;
:
fused. The bead when cold must be quite trans- yellow mass = chromium.
it must be re- (d) Heating in closed tube with potassium
parent and colourless, otherwise
melted, shaken off, and a fresh bead made. A hydrogen sulphate. Gas evolved carbon dioxide
:
small quantity of the substance is taken on the = carbonates, oxalates ; accompanied bv charring
bead and heated first in the oxidising flame (O.F.) of the residue = tartratcs, citrates, &c. carbon ;
and then, after it has been examined, in the monoxide (blue

flame) formates, oxalates;
inner or reducing flame (I.F.). The colour of sulphur dioxide = sulphites, thiosulphates hydro-
gen sulphide = sulphide* (not all)
;
the bead should be observed both hot and cold. hydrogen

;
If too much substance is taken, the bead becomes chloride (fuming in air) = chlorides (not all);
opaque, and the colour cannot be distinguished. hydrogen fluoride (etching glass) = fluorides ;
These so-called borax and microcosmic beads bromine and hydrogen bromide = bromides
iodine =iodides nitrous fumes = nitrites, nitrates.
;
owe their colour respectively to the formation ;
of certain borates and phosphates of the heavy

Examination in the Wet Way.
metals. Borax glass consists of anhydrous
Na 2 B 4 7 and when heated with a metallic The preparation of the solution requires some
,
oxide or salt the excess of boric oxide present attention. A metallic substance is treated at
unites with the metallic oxide, forming the
once with moderately strong nitric acid. Tin
and antimony form oxides which to a great
corresponding borate :
extent remain undissolved ; arsenic is oxidised

Na 2 B 4 7 +CoO = Na 2 B 2 4 +CoB 2 4 (blue). to soluble arsenic acid other metals (with the
;
Microcosmic salt on ignition yields the exception of gold and the platinum metals, which
sodium metaphosphate, and this
readily fusible are not attacked) are converted into nitrates,
salt combines with metallic oxides to form which dissolve at once or on diluting.
double orthophosphates : If the substance is not a metal, it is first
NaP0 3 +CuO = CuNaP0 4 (green).

treated with hot water, and if anything is dis-
solved (which is ascertained by evaporating a
When a silicate is
introduced into the molten few drops on platinum foil), the substance is
metaphosphate, the latter withdraws the basic boiled two or three times with fresh quantities of
oxide from the former, setting free silica, which water. Any residue which may be left is treated
remains undissolved (' silica skeleton ') :
with dilute hydrochloric acid, and afterwards, if
CaSi0 3 +NaP0 = CaNaP0 4 +Si0
3 2. necessary, with the concentrated acid. Care
Borax beads.
must be taken to observe if any gas is given off
Outer flame e.g. carbon dioxide (effervescence), from carbon-

Inner flame Metal
ates ; sulphur dioxide, from sulphites or thiosul-
Hot Cold Hot Cold
from peroxides or hypo-
phates ; chlorine,
Green Bottle-green Yellow Paler Iron
Green Green Yellow Green Chromium chloriteshydrocyanic acid, from cyanides ;
;
Green Bottle-green Yellow Pale Uranium hydrogen sulphide, from sulphides. Many
yellow chlorides are insoluble in the strong acid, and
Colourless Colourless Amethyst Amethyst Manganese
Blue Blue Blue Blue Cobalt hence the solution must be diluted before filter-
Grey Grey Violet Reddish- Nickel ing. Silver, lead, and univalent mercury will
brown be converted into insoluble chlorides.
Brownish Emerald- Yellow Greenish- Vanadium
Solvent action of the mineral acids (v.
green yellow
Colourless Brown Green Bluish- Copper A. A. Noyes and W. C. Bray, J. Amer. Chem.
green Soc. 1907, 29, 137, 481). In dealing with sub-
Colourless Colourless Orange- Colourless Cerium
stances insoluble in water the following acidic
red
Brown Brown Yellow Colourless Molybdenum solvents may be used hydrochloric, nitric, sul-
:
Brownish- violet Yellow Colourless Titanium phuric, and hydrofluoric acids. Although it
Yellow to brown Yellow Colourless Tungsten is impossible to give a hard-and-fast rule as to
Microcosmic beads. The colours produced the way in which these agents should be applied,
are similar to those in the borax bead, but the the following considerations will indicate the
reducing effects are less pronounced. In the I.F. relative advantages of one or other of these
molybdenum compounds give a green colour, solvents :
and those of tungsten a greenish-blue tint. Hydrochloric acid. (1) Advantages : (i.)
Chlorides and bromides evolve a blue and green Solutions on this acid do not yield a precipitate
flame when heated with a microcosmic bead of sulphur on treatment, with hydrogen sulphide ;
saturated with copper oxide, and iodides give a (ii.) the solvent action of this acid on the
green flame. following oxides : lead peroxide, manganese
(7) Other special dry tests. (a) Heating on dioxide, and the hydrated oxides of tin and
charcoal with potassium (or cuprous) iodide and antimony, is superior to that of nitric acid ;
sulphur crimson incrustation
: bismuth ; lemon = (iii.) hydrated silica is readily precipitated on
yellow incrustation =
lead ; greenish-blue fumes evaporating the hydrochloric acid solution.
= mercury. (2) Disadvantages: (i.) This
acid is com-
(b) Heating on charcoal with (i.) fusion paratively useless for alloys (ii.) evaporation
;
mixture (Na 2C0 3 ,K 2C0 3 ) alone and moistening of the hydrochloric acid solution leads to the
with dilute acid, hydrogen sulphide evolved = volatilisation of arsenic, mercury, tin and
sulphur compounds ; (ii.) fusion mixture and selenium as chlorides.
sulphur, soluble mass giving coloured precipi- Nitric acid. (I) Advantages: (i.)
The best
tate with dilute acid, yellow = tin ; orange = general solvent for the metals
and their alloys ;
antimony. The fused insoluble oxides Sn0 2 (ii.) oxidises and dissolves
insoluble compounds
and Sb 2 can be thus characterised.
4 of arsenic, mercury, and selenium without
(c) Heating with fusion mixture and potas- the formation of volatile compounds of these
1G6 ANALYSIS.
elements ; (iii.) does not cause the precipita- ployed in attacking substances not dissolved
tion of silver or lead oxidises sulphides
; (iv.) by hydrochloric or nitric acid, although it is
not attacked by hydrochloric; and sulphuric acids. of little use for colourless insolubles. It readily
(2) Disadvantages: (i.) This acid alters the dissolves gold and platinum, but is less efficacious
state of combination of many elements, e.g. it in rendering soluble the rarer noble metals (e.g.
oxidises mercurous, arsenious, antimonious, osmium and iridium).
stannous, and ferrous salts ; (ii.) its solution
much Treatment of Insolubles.
deposits sulphur on treatment with
hydrogen sulphide; (iii.) the oxidation of The substances not dissolved by the fore-
sulphides by nitric acid in the presence of going acidic reagents are generally regarded as
barium, strontium, and lead leads to the insolubles, although they are divisible into two
precipitation of these metals as sulphates ; (iv.)
classes : (i. ) pseudo-insolubles, which are dissolved
nitric acid is less efficacious than hydrochloric by certain specific solvents ; (ii.) true insolubles,
acid in rendering hydrated silica insoluble. which are only broken up into soluble com-
The nitric acid solution of an alloy when pounds by the agency of fused alkali carbonates.
evaporated to dryness and heated at 120-130 Pseudo-insolubles. Silver chloride &ndbromide,
soluble in aqueous ammonia. (The three silver
may yield the partially dehydrated hydroxides
of silica, tin, antimony, titanium, and tungsten halides may be completely decomposed by treat-
in an insoluble condition. When phosphorus ment with zinc and dilute sulphuric acid,
or arsenic is present together with tin the so- metallic silver and soluble zinc halide being
called stannic phosphate or arsenate (phospho- produced.) Insoluble fluorides (those of the
stannic or arsenostannic acid) may also be found common and rare earth metals) are decomposed
hi the insoluble residue. by heating with concentrated sulphuric acid.
Sulphuric acid. The dilute acid is of little Lead sulphate, soluble in ammonium acetate
value as a solvent, but the hot concentrated solution ; oxides of antimony, dissolved in hydro-
acid has been found useful in certain cases, chloric and tartaric acids. Anhydrous chromic
(i.) In bringing certain alloys
into solution, e.g. sulphate and basic bismuth sulphate, converted
white metals (r. Low, J. Amer. Chem. Soc. respectively into hydroxide and basic carbonate
1907, 29, 66); (ii.) destruction of organic by boiling with aqueous sodium carbonate ; these
matter ; evaporation of a concentrated sulphuric products are then dissolved in dilute mineral
acid solution of the substance is preferable to acids.
ignition, because the latter process renders cer- True insolubles. These substances are fused
tain compounds insoluble and leads to the loss with a mixture of sodium and potassium car-
by volatilisation of such elements as mercury, bonates in equimolecular proportions (so-
arsenic, selenium, &c. Very stable organic called fusion mixture). In the absence of
substances (e.g. paraffin and cellulose) can be reducible metals (e.g. silver or lead), insoluble
destroyed completely by adding a little strong sulphates (barium and strontium sulphates) and
nitric acid and heating till the solution acquires silicates may be heated with the fusion mixture
a light yellow colour. When diluted con- in a platinum crucible. If any insoluble molyb-
siderably with water (20-30 vols.) this solution denum sulphide is present (indicated by dry
may yield a deposit containing silica and certain tests), a little nitre must be added to oxidise this
refractory silicates and fluosilicates, together sulphide, and thus prevent its corrosive action
with the sulphates of barium, strontium, lead, on the platinum. In the case of an insoluble
calcium, and chromium (an insoluble sulphate silicate the fused mass is treated directly with
formed during the heating), basic sulphates of hydrochloric acid, when the metals present pass
bismuth, antimony, and tin and the ignited into solution as chlorides, and the silica is ren-
oxides of the last two metals with those of dered insoluble by evaporating down the acid
aluminium and titanium, (iii.) Insoluble com- solution. In the case of insoluble sulphates the
pound cyanides are decomposed by hot confused mass is extracted with water to remove
centrated sulphuric acid, but may also be the soluble alkali sulphate, and the residue
attacked by aqueous alkali hydroxides yielding (BaC0 3 ,SrC0 8 ) is subsequently dissolved in
soluble alkali cyanides and insoluble metallic dilute acid.
hydroxides. Silver iodide, bromide, and chloride are
Hydrofluoric acid. The insoluble residues decomposed by fusion mixture,' yielding the
from the preceding acids may be treated with soluble alkali halide ; insoluble lead compounds
a 40 p.c. solution of hydrogen fluoride, which is are similarly decomposed. The strongly heated
now obtainable in glass bottles lined with oxides of aluminium, chromium, titanium, tin, and
paraffin wax. (1) Advantages: (i.) Many antimony rank as insolubles ; they are not readily
insoluble silicates are readily decomposed, the attacked by ' fusion mixture,' but are rendered
silicon being eliminated completely as gaseous soluble by fusion with potassium hydroxide.
silicon fluoride ; (ii. ) the reducible metals and The oxides of titanium and aluminium may be
their compounds may be treated in platinum rendered soluble by fusion with potassium
basins or crucibles providing that the solution hydrogen sulphate ; special methods for treat-
is never evaporated to dryness. ing the insoluble oxides of chromium, tin, and
(2) Disadvantages: (i.) Glass or silica- ware antimony are indicated among the dry tests
vessels cannot be used with hydrofluoric acid ; (7, b and c). The insoluble compounds of the
(ii.) owing to the destructive action of hydrogen easily reducible metals (e.g. Ag, Pb, Sn, Sb, &c.)
fluoride on animal tissues, all operations with can all be decomposed and reduced by fusion
solutions of this gas must be conducted in an with sodium or potassium cyanide.
efficient draught cupboard. When both aqueous and acid solutions have
Aqua regia (concentrated hydrochloric acid been obtained from the same substance, the
3 parts and nitric acid 1 part) may be em analyst, must use his judgment as to whether
ANALYSIS.
they may be mixed should he analysed

or GROUP II.
Reagent hydrogen sulphide in
:
separately. The latter course sometimes acid solution. Thioacetic acid has been recom-
gives information as to the
distribution of the mended as a substitute for hydrogen sulphide
acids and bases in the original substance. If in qualitative analysis (Schiff and Tarugi
the first course is adopted, it must be borne Ber. 1894, 27, 2437). Precipitate : the sulphide*
in mind that the hydrochloric acid solution may of arsenic, antimony, tin,
molybdenum, gold,
precipitate lead and silver, and possibly mercury, platinum (the other platinum metals), bismuth,
from an aqueous or nitric acid solution. lead, mercury, copper, and cadmium, together
with selenium and tellurium, partly free and
partly as sulphides. The solution should be
Systematic Method of Examination in the dilute and not too acid, and it should be treated
Wet Way.
and saturated repeatedly with the group reagent,
The formation of a precipitate at the proper since prolonged treatment is required to
precipi-
stage in the systematic separation is not suffi- tate molybdenum and the platinum metals.
cient proof of the presence of a particular sub- The filtrate from the foregoing sulphides is
stance ; some characteristic confirmatory test boiled to expel hydrogen sulphide, and
any iron
should always be applied. The colour of the present peroxidised by warming with nitric
solutions at different stages in the operation is acid or bromine water. If organic matter is
a valuable indication. Unnecessary excess of present, it is destroyed either by evaporation to
reagents should be avoided, but filtrates should dryness or treatment with hot concentrated sul-
always be tested to make sure that precipitation phuric acid (v. supra). Silica or barium sulphate
is complete. Many tests succeed only when the may be precipitated at this stage. A portion
proper proportion of the reagent is added, and of the oxidised solution should now be tested
it should be a rule always to add the reagents for phosphate with nitric acid and ammonium
very gradually. All precipitates which have molybdate.
to be subjected to the action of reagents should GROUP III. Reagents : ammonium chloride
be carefully washed, but in qualitative analysis and ammonium hydroxide. Precipitate : (a) In
it is not as a rule desirable that all the washings absence of phosphates hydroxides of aluminium,
:
should mix with the filtrate. iron, chromium, glucinum, titanium, zirconium,
The reaction of the original solution towards tantalum, coluinbium, thorium, cerium (and
litmus paper should be noted and a portion other rare earth metals), and uranium as am-
tested for ammonium compounds by heating monium diuranate. Some manganese, zinc,
with sodium hydroxide or by triturating in a and alkaline earth metals may be coprecipi-
mortar with soda-lime (dry sodium and calcium tated. (b) In presence of phosphates the :
hydroxides). phosphates of the preceding metals, together

In systematic qualitative analysis advantage with those of Groups IV., V., and magnesium.
is taken of certain similarities existing between GROUP IV. Reagents ammonium sulphide:
the metallic radicles which enable these radicles or hydrogen sulphide and ammonium hydroxide.
to be divided into a limited number of groups, Precipitate : sulphides of zinc, manganese, cobalt,
the members of which are subsequently either and nickel. The precipitation is carried out in
separated or identified by means of the differences the boiling solution, and the filtrate, if brown,
between the properties of their respective com- is slightly acidified with hydrochloric acid, when
pounds. vanadium and a small portion of the nickel are

The metallic radicles are divided into six precipitated as sulphides.
groups, according to their behaviour with the GROUP V. Reagents ammonium carbonate
:
following reagents, which must be applied in and ammonia. Precipitate barium, strontium, :
the order given. It may be mentioned that and calcium as carbonates.

some chemists prefer a division into five groups, GROUP VI. The filtrate from Group V.
and add the reagents of Groups III. and IV. suc- contains magnesium, sodium, lithium, potassium,
cessively imthout an intervening filtration. This rubidium, and caesium, which are identified by
process is conveniently adopted in the presence special tests.
of the less commonly occurring metals ( J. Amer. In the absence of the rarer metallic radicles,
Chem. Soc. 1908, 30, 481). the group precipitates are examined in the fol-
GROUP I. Reagent : hydrochloric acid in lowing manner. Confirmatory tests are given
moderate excess. Precipitate :
silver, lead, under special reactions.
thallium (thallous), and mercurous chlorides; GROUP I. The precipitate is boiled with
tungslic acid. water the aqueous extract mixed with dilute
;
If the original solution is alkaline, the group sulphuric acid gives a white precipitate (PbS0 4 ),
precipitate may contain sulphides (e.g. As 2 S 3
, indicating lead. The insoluble portion is treated
Sb 2 S , SnS 2 ) which had been dissolved in aqueous with aqueous ammonia a black residue
;
?
alkali sulphide or hydroxide. This yellow or (NH 2 Hg 2Cl or NH
2 HgCl
and Hg) indicates
orange precipitate is examined under Group II. mercury ; the ammoniacal filtrate acidified
The group precipitate may also contain in- with nitric acid gives white silver chloride,
soluble silver salts AgBr, Agl) precipitated
(e.g. indicating silver.
from solution in alkaline cyanides or thio- GROUP II. The precipitate is washed with
sulphates ; thesa are dealt with as insolubles. aqueous hydrogen sulphide and warmed with
The filtrate from the Group I. precipitate or the yellow ammonium sulphide [(NH 4 ) 2 S X ], this
solution itself in the absence of a precipitate, extraction being repeated.
must be evaporated nearly to dryness if nitric (A) The filtrate is acidified with dilute hydro-
acid or nitrates are
present, since these corn- chloric acid, the precipitate boiled with strong
pounds lead to the precipitation of sulphur in aqueous ammonium carbonate, and the solution
Group II. filtered ; the filtrate acidified yields a yellow
168 ANALYSIS.
precipitate (As 2 S 3 ), denoting arsenic. The residue separation (Tower, J. Amer. Chem. Soc. 1910,
is dissolved in concentrated hydrochloric acid, the 32, 953).
solution boiled, diluted, and treated with strips The phosphoric acid mayalso be removed
of platinum and pure zinc ; a black stain on the by evaporating the from Group II. to
filtrate
platinum = antimony. The zinc is dissolved dryness with nitric acid and granulated tin,
in hydrochloric acid and mercuric chloride added ; when an insoluble residue is obtained consisting
a white precipitate (Hg 2Cl 2 ) becoming grey of metastannic and phosphostannic acids.
(Hg) =
tin. GROUP IV. The mixed sulphides, washed
In the separation of arsenic, antimony, and with hydrogen sulphide water, are dissolved
tin by ammonium carbonate, this solvent in aqua regia, or hydrochloric acid and potassium
dissolves an appreciable amount of stannic chlorate. Excess of sodium hydroxide is added
sulphide, which is reprecipitated by acids as to the solution after expelling excess of acid ; the
a white oxysulphide (Schmidt, Ber. 1894, 27, precipitate collected, and the filtrate treated with
2739). hydrogen sulphide ;
white precipitate (ZnS) =
Boiling the mixed sulphides with con- zinc. The
precipitated hydroxides are dissolved
centrated hydrochloric acid effects a separation in hydrochloric acid, excess of ammonium acetate
by dissolving the tin and antimony compounds, added, and the solution saturated with sulphide.
leaving nearly the whole of the arsenious sulphide Any black precipitate is removed and the
undissolved. The mixed sulphides may also filtrate rendered ammoniacal; pink precipitate
be dissolved in aqueous sodium peroxide, which (MnS) = manganese.
produces sodium arsenate, antimonate, and The black precipitate is tested in the borax
stannate. On boiling this solution with excess bead ;a brownish-yellow colour indicates nickel
of ammonium chloride, hydrated stannic oxide present and cobalt absent. If the bead is blue
is precipitated (v. J. Walker, Chem. Soc. Trans. (== cobalt), the precipitate is dissolved in hydro-
1903, 83, 184; cf. Caven, Chem. Soc. Proc. chloric acid, potassium chlorate added, excess of
1910, 26, 176). acid expelled, and the solution nearly neutralised
(B) The precipitate insoluble in ammonium with sodium carbonate ; excess of potassium
sulphide is boiled with nitric acid (1 vol. acid cyanide is then added, and the solution boiled
sp.gr. 1-20 2 vols.
: H
2 0), the
residue dissolved in an open dish. An excess of sodium hypo-
in aqua regia, excess of acid expelled, and stan- chlorite or freshly prepared sodium hypobromite
nous chloride added ; a white precipitate (Hg 2 Cl 2 ) is added to the warm solution; a black pre-
indicates mercury. The nitric acid solution is cipitate (Ni 2 O 3 ,a;H 2 0)
=
nickel the filtrate con-
;
evaporated to a small bulk with sulphuric acid, tains potassium cobalticyanide (K 3 Co(CN) 6 ).
diluted with cold water and filtered ; white A quicker separation of the Group IV.
residue (PbS0 4 ) indicates lead. The filtrate is sulphides may be effected by digesting them
rendered ammoniacal, blue colour copper = with cold dilute hydrochloric acid (1 : 20).
white precipitate (Bi(HO) 3 ) =
bismuth, con- This treatment should bring the zino and
firmed by dissolving in hydrochloric acid and manganese into solution, leaving the sulphides
diluting considerably with water (BiOCl). The of nickel and cobalt undissolved ; but it is gene-
colour of the filtrate discharged by potassium rally found that appreciable quantities of the
cyanide (excess) ; the solution saturated with latter metals are present in the filtrate. Alterna-
hydrogen sulphide, a yellow precipitate (CdS) = tive methods of detecting and separating nickel
cadmium (confirmation is essential, since a yellow and cobalt are given under special reactions.
cyanogen derivative may be precipitated at this GROUP V. Dissolve the washed precipitate
stage). in dilute acetic acid, add aqueous potassium
GROUP III. (phosphates absent). The mixed chromatc; yellow precipitate (BaCr0 4 ) ba- =
hydroxides, suspended in water, are warmed with rium : filtrate boiled with concentrated aqueous
excess of sodium peroxide and filtered. A ammonium sulphate; white precipitate (SrS0 4 )=
residue (Fe 2 3 -a;H 2 0, which may contain some strontium : final filtrate treatedwith ammonium
Mn0 2 ) indicates iron. The filtrate is divided into oxalate; white precipitate (CaC 2 O 4 ,a;HÔ) =
two parts, (i. ) boiled with excess of ammonium calcium. to their close relationship, a
Owing
chloride, white gelatinous precipitate (A1(OH) 3 ) sharp separation of the three metals is extremely
aluminium; (ii.) acidified with dilute acetic difficult. The following alternative process has
acid and lead acetate added, yellow precipitate recently been worked out (v. Bray, J. Amer.
(PbCrO 4 ) = chromium. Chem. Soc. 1909, 31, 611).
GROUP III. (phosphates present). If the The group precipitate, which may contain
original solution was acid, this group precipitate magnesium, is dissolved in 20 c.c. of 30 p.c.,
may contain phosphates insoluble in neutral or acetic acid, solution neutralised with ammonia,
alkaline solutions. The sodium peroxide separa- 3 c.c. of acetic acid added, diluted to 40 c.c., 10
tion is applied to one-third of the precipitate ;
c.c. of 20 p.c. potassium chromate slowly added,
the remainder is dissolved in dilute hydro- solution boiled for 2 minutes ; yellow precipitate
chloric acid, the solution nearly neutralised (BaCrO 4 ). Three c.c. of ammonia added to
with pure sodium carbonate, and treated filtrate, diluted to 60 c.c., 50 c.c. of alcohol
successively with ammonium acetate, acetic (95 p.c.) added ; after 10 minutes yellow pre-
acid, and ferric chloride until no further preci- cipitate (SrCr0 4 ). Without washing this pre-
pitate is produced and the solution is deep red. cipitate, 200 c.c. of water are added to filtrate,
The mixture is boiled and filtered hot the ; the sohition boiled, and 40 c.c. of 4 p.c. ammo-
filtrate is then examined for the metals of nium oxalate added ; after 10 minutes white
Groups IV. and V., and for magnesium. The precipitate (CaC 2 4 ). Magnesium is precipitated
precipitate, which
neglected, con tarns ferric
is in filtrate as a colourless crystalline precipitate
phosphate and basic ferric acetate. Ammonium (Mg(NH 4 )P0 4 ,6H 2 0) by adding ammonia and
formate may be used instead of acetate in this sodium phosphate.
ANALYSIS. 169
GHOUP VI. A
portion of the filtrate from in ammonium sulphide, and digested for 10
V. examined for magnesium (v. supra), the re- minutes with nearly boiling hydrochloric acid
mainder evaporated to dryness and ignited to (sp.gr. 1-20); the solution contains tin and
expel ammonium salts. The residue dissolved antimony, and the residue arsenic and the rarer
in a small bulk of water, the solution filtered elements. The residue is dissolved
by strong
if necessary, examined by flame test and hydrochloric acid and potassium chlorate ; the
divided into two parts, (i.) platinic chloride solution concentrated to the
crystallising point
added; yellow crystalline precipitate (K 2PtCl 6 ) yields a yellow precipitate (K 1PtCl 6 )=platinum.
= potassium; (ii.) potassium pyroantimonate The filtrate, treated successively with ammonia
added; colourless crystalline precipitate and magnesia mixture (MgCl,,2NH 4Cl with
(Na 2 H 2 Sb 2 7 ,6H 2 0) = sodium. NH 4 -OH), yields a colourless crystalline pre-
cipitate (Mg(NH 4 )As0 4 ,6H 2 0) = arsenic. The
GEOUP SEPARATION IN THE PRESENCE OF filtratefrom the double arsenate is evaporated
THE RAKER METALS. to remove ammonia, and then boiled with oxalic
In the presence of the less commonly occur- acid, and the brownish-black precipitate (gold)
ring elements, the ordinary group separations extracted with hydrochloric acid to dissolve
require, in certain instances, to be modified any co-precipitated tellurous acid. The filtrate
very considerably. A
systematic attempt to from the gold concentrated and acidified with
is
deal with this problem has recently been made strong hydrochloric acid, and after removing
by A. A. Noyes and his collaborators, to whose any precipitated potassium chloride, sodium
original memoirs reference should be made for sulphite (in slight excess) is added when a red
the exact working details of the necessarily precipitate =
selenium. The filtrate from se-
somewhat complicated separations, an outline lenium is diluted and treated successively
of which is given below (J. Amer. Chem. Soc. with potassium iodide and solid sodium sulphite
1907, 29, 137 1908, 30, 481
; 1909, 31, 611).
; (excess); the double iodide, K 2TeI 6 becomes ,
be seen that the greater number of

It will reduced, and a black precipitate tellurium. =
the rarer elements are precipitated by the re- The final filtrate is boiled with hydrochloric
agents of Groups II., III., and IV. of the fore- acid to expel sulphur dioxide, and to the cooled
going analytical classification but in the ;
solution 10 p.c. potassium thiocyanate and
scheme devised by Noyes, Groups III. and IV. stannous chloride (or a scrap of zinc) are
are merged into one, and it is chiefly in this successively added, when a red colouration
comprehensive group that the additional com- (Mo(CNS) 4 ) soluble in ether molybdenum.
plications are to be found. GROUPS III. and IV. The filtrate from
GROUP I. The precipitate may contain Group II. is boiled to expel hydrogen sulphide,
thallous chloride and tungstic acid. The former treated with moderately strong ammonia, the
is extracted by hot water, any lead separated colour of the precipitate being noted, and the
as sulphate, when the filtrate treated with potas- ammoniacal mixture heated nearly to boiling
sium iodide gives a yellow precipitate (Til) = and treated with ammonium sulphide, or pre-
thallium. The hydrated tungstic acid, preferably, in the presence of nickel, with hydrogen
cipitated by hydrochloric acid from alkali sulphide to saturation. In the presence of
tungstates, remains in the residue, and may vanadium the filtrate has a reddish colour,
be separated from lead and silver by fusion and on adding hydrochloric acid brown vana-
with sodium carbonate. The aqueous solution dium sulphide is precipitated. The acid filtrate
of alkali tungstate is boiled with zinc and hydro- is boiled to expel hydrogen sulphide, and treated
chloric acid, when the development of a blue with ferric chloride and ammonia to precipitate
colouration = tungsten. last traces of vanadium. The presence of this
GROUP II.
Selenium, tellurium, molybde- metal in the sulphide and ferric hydroxide pre-
num, gold, platinum and its allies, are precipitated cipitates is confirmed by dissolving in nitric
by hydrogen sulphide in acid solution. Ex- acid (sp.gr. 1-20), diluting and adding hydrogen
traction of the group precipitate with yellow peroxide, when an orange-yellow colouration
=
ammonium sulphide carries the greater part vanadium.
of these elements into the tin sub-group, but The group precipitate is dissolved in
the separation is not quite sharp, for small but hydrochloric acid (sp.gr. 1-12), adding, if
appreciable quantities of molybdenum, gold necessary, some nitric acid or bromine water.
and the platinum metals remain in the insoluble The solution is then boiled with hydrochloric
sulphides of the copper sub-group. acid to remove nitric acid, and treated in a
A. Copper sub-group. The precipitate boiled platinum dish with 40 p.c. hydrofluoric acid,
with dilute nitric acid (1 vol. of sp.gr. 1-20 : 2 and evaporated to dryness. An insoluble
.
vols. water) partially dissolves; the solution residue indicates the fluorides of the rare earth
contains lead, copper, cadmium, and bismuth, metals (thorium, cerium, yttrium, erbium, &c.) ;
while the residue contains mercury, gold, the aqueous extract, which contains all the other
platinum, and a trace of tin. The insoluble metals of this analytical group, is evaporated
successively with hydrochloric and
portion is oxidised with bromine water, potas- nitric tvcids.
sium chloride and hydrochloric acid are added The insoluble fluorides are decomposed by hot
and the solution concentrated ; a yellow crystal- sulphuric acid, and the resulting sulphates
of
line precipitate (K 2PtCl ) =
platinum. The the rare earth metals subjected to special tests
excess of acid is expelled from the solution, for these elements.
which is then rendered alkaline and boiled with The nitric acid solution of the other metals
excess of oxalic acid; a brownish-black of the group is treated successively with caustic
pre-
cipitate = gold. soda solution, dry sodium peroxide, and aqueous
B. Tinsub-group. The sulphides are re- sodium carbonate, when a precipitate B and
precipitated by dilute acid from their solution a filtrate A are obtained. This treatment
170 ANALYSIS.
separates these metals into two sub-groups, and water and treated with hydrogen peroxide and
the method is valid even when phosphates are subsequently with sodium phosphate; orange-
present. yellow colouration (TiO 3 ) = titanium white ;
A. The aluminium sub-group (may contain flocculent precipitate (Zr(OH)-P0 4 )

= zirco-
sodium glucinate, zincate, aluminate, vanadate, nium. The final filtrate is reduced with
chromate, and peruranate). The solution is sulphurous acid, when a white flocculent pre-
acidified with nitric acid (sp.gr. 1 -42) and diluted cipitate (Ti(OH)'PO 4 ) confirms titanium.
considerably, solid sodium hydrogen carbonate GROUPS V. and VI. In the presence of
added in moderate excess and the mixture heated lithium it is preferable to precipitate magnesium
in a stoppered bottle. The precipitate (contain- in the calcium group. The filtrate from Groups
ing zinc, glucinum, and aluminium) is dissolved III. and IV. is concentrated to 10 c.c. and treated
in hydrochloric acid, and the solution rendered with 30 c.c. of 20 p.c. ammonium carbonate and
ammoniacal ; the zinc remains in solution, 30 c.c. of 95 p.c. alcohol. After 30 minutes the
while the hydroxides of glucinum and alu- precipitation is complete, the magnesium being
minium are precipitated. These hydroxides are present as the double carbonate (MgC0 3 ,
dissolved in strong hydrochloric acid, ether (NH 4 ) 2 C0 3 ,4H 2 O). The treatment of the group
(1-5 vols.) is added, and the cooled solution precipitate has already been described under
saturated with hydrogen chloride, white crystal- Group V. (v. supra). The filtrate is evaporated
line precipitate (A1C1 3 ,6H 2 0) = aluminium. to dryness and ignited. The residue is taken
The ethereal filtrate is evaporated, treated with up with 10 c.c. of water, and one-third tested
ammonia, any precipitate dissolved in 10 p.c. for lithium by adding 0-5 c.c. of 10 p.c. caustic
sodium hydrogen carbonate, the solution soda and 2 c.c. of 10 p.c. sodium phosphate,
saturated with hydrogen sulphide the filtrate
; heating to boiling and adding 1 c.c. of alcohol,
from any precipitated sulphide is acidified, white precipitate (Li 3 P0 4 ) lithium. =
The fil-
boiled, and rendered ammoniacal, when a white trate from this phosphate is tested for potassium
flocculent precipitate (G1(OH) 2 ) = glucinum. by adding acetic acid and sodium cobaltinitrite.
The filtrate obtained from the first treatment The remaining two-thirds of the solution, con-
with sodium hydrogen carbonate is acidified taining the alkali metals, are tested for sodium
with nitric acid, and just neutralised Avith by potassium pyroantimonate after removing
caustic soda ; 2 of nitric acid (sp.gr. 1 -20)
c.c. the lithium as fluoride by ammonia and am-
and 20 c.c. of 20 p.c. lead nitrate are added ; monium fluoride.
yellow precipitate =
chromium. The lead is
removed with hydrogen sulphide, the excess of Examination for Acids.
gas boiled off, vanadyl salts oxidised to vanadates Although it is not possible to separate the
with bromine, any excess of this reagent being acidic radicles into a limited number of groups,
removed by boiling. The solution, after each having a group reagent, yet the reactions
neutralisation with ammonia, is treated suc- may be divided into (i.) preliminary tests made
cessively with 5 c.c. of 30 p.c. acetic acid, 2 on the original solution or substance ; and (ii.)
grams of ammonium sulphate (or nitrate), and systematic tests made on suitably prepared
2 grams of sodium phosphate; the mixture is solutions. The reactions may be conveniently
heated to boiling, when a white precipitate carried out in the following order :
-
(U0 2 (NH 4 )P0 4 ) =

uranium. The final filtrate I. Preliminary tests (compare dry reactions).
is rendered ammoniacal, saturated with 1. The substance or solution is
hydrogen original
sulphide, acidified with acetic acid, and boiled; warmed with dilute hydrochloric or sulphuric acid.
dark precipitate =
vanadium. A gas is evolved, carbon dioxide, turning lime
B. The iron-manganese sub-group (may con- water milky =
carbonate sulphur dioxide ;
sul- =
tain the hydroxides and phosphates of iron, phite hydrogen sulphide, blackening lead acetate
;
manganese, cobalt, nickel, zinc (traces), titanium, paper = sulphide (not all) nitrous iumea= nitrite ;
;
and zirconium, together with calcium, strontium, hydrogen cyanide, odour of bitter almonds =
barium, and magnesium, as carbonates and cyanide.
phosphates). The precipitated hydroxides, &c., 2. The original substance or solution
are dissolved in hydrochloric acid, the solution warmed slowly with strong solution of sodium
evaporated down with strong nitric acid, and dichromate slightly acidified, carbon dioxide
treated with 0-5 gram of solid potassium evolved, confirms carbonate in presence of
chlorate ;
brownprecipitate = manganese. A sulphite.
portion of the filtrate tested for phosphoric acid, 3.Heating with concentrated sulphuric acid.
when, if present, the remainder is treated with The foregoing gases may be evolved, and in
ammonium hydroxide till nearly alkaline, and addition the following :
boiled with ferric chloride and ammonium (a) Colourless :
acetate. The filtrate contains the ordinary Fuming acid gas etching glass = fluoride ;
metals of Groups III. and IV., together with

fuming acid gas not etching = chloride odour ;
magnesium; the precipitate consists of the of vinegar = acetate carbon monoxide, blue
;
hydroxides, phosphates, and basic acetates of flame = formate, ferrocyanide carbon monoxide ;
iron, zirconium, titanium, and possibly thallium and dioxide = oxalate ; sulphur dioxide and
(tervalent). This precipitate is dissolved in sulphur sublimate = thiosulphate.
hydrochloric acid (sp.gr. 1-12), and the solution (b) Colour.
shaken with an equal volume of ether. The Orange vapour, bromine = bromide violet ;
ethereal extract contains ferric and thallic

vapour and hydrogen sulphide = iodide nitrous ;
chlorides ; the hydrochloric acid solution the fumes = nitrite, nitrate oxides of carbon and
;
zirconium and titanium. The latter is evapo- sulphur with charring = tartrate, citrate, mutate ;
yellow explosive chlorine oxide = chlorate.

rated down with sulphuric acid until the
hydrogen
chloride is expelled, the residue taken and
up with 4. Heating with alcohol concentrated
ANALYSIS. 171
acid, green flame

uric = borate. Before Precipitate sulphide as CdR, PbS, or ZnS by
performing this test chlorates must be decom- adding cadmium carbonate or lead carbonate
posed by igniting the original substance, other- sludge or zinc chloride solution. Add strontium
wise an explosion may result. nitrate and leave for 12 hours ; the
precipitated
5. Heating with concentrated sulphuric acid strontium sulphate and sulphite separated
by
and sand, a colourless gas (SiF 4 ), giving a hydrochloric acid, the filtrate contains the
gelatinous precipitate on moist rod, confirms thiosulphate, decomposed by strong hydro-
chloric acid, giving sulphur and
fluoride. sulphur dioxide
II. Systematic tests. Before testing a solution (Autenrieth and Windaus, Zeitsch. anal. Chem.
for acids, boil with excess of pure sodium 1898, 37, 295).
carbonate to remove heavy metals, filter, and Chloride, bromide, and iodide. (1) Place the
carefully neutralise with nitric acid. substance in a small flask connected with a
1. Barium chloride in neutral solution yields : small bulb U-tube containing a little starch
(a) a white precipitate, insoluble in hydro- paste and placed in a beaker of water. Add
chloric acid =
sulphate, silicofluoride (/8) a ;
water and ferric sulphate solution to the sub-
white precipitate, soluble in hydrochloric acid stance in the flask, and heat to If
boiling.
= sulphite, carbonate, phosphate, oxalate, borate, iodine is present, the starch paste becomes blue.
fluoride, silicate,
tartrate ; (y) a yellow precipi- Remove the cork, boil with fresh additions of
tate = chromate. ferric sulphate till all iodine is
expelled. Now
To a portion of the neutral solution add
2. add a few crystals of potassium permanga-
calcium chloride in excess, allow to stand for nate, connect with a bulb tube containing
some time with occasional shaking, and filter. chloroform, and again boil. If bromine is
A white precipitate () insoluble in acetic acid present, the chloroform is coloured brown. Boil
= oxalate (sulphate in strong solutions) ; (ft) with addition of more permanganate until all
soluble in acetic acid =
phosphate, borate, and bromine is expelled, filter and test filtrate for
other acids precipitated by barium chloride. chlorine (Hart, Amer. Chem. J. 1884, 6, 346).
Calcium tartrate after washing is soluble in (2) After iodine has been detected by means
potash, and is re-precipitated on diluting and of nitrogen oxides in sulphuric acid, evaporate
boiling. part of the solution to dryness with sodium
The from the precipitate in the cold
filtrate carbonate, fuse with ten times its weight of
is boiled for some time and filtered hot a white ; potassium dichromate till all iodine is expelled,
precipitate '= citrate (malate in strong solutions). place in a small dry retort, and heat with strong
The filtrate from this precipitate is allowed to sulphuric acid.Part of the distillate is agitated
cool and then mixed with excess of alcohol ; a with water and carbon disulphide ;
if bromine
white precipitate =
succinate, malate. is present, the latter becomes orange-red. The
3. Silver nitrate in neutral solution yields : remainder of the distillate is neutralised with
(a) A
precipitate soluble in nitric acid. ammonia, and tested for chromic acid by acidi-
(1) White
= oxalate, borate, tartrate, ben- fying with acetic acid and adding lead acetate.
zoate, &c. The presence of chromic acid indicates the pre-
(2) Yellow
= phosphate, arsenite. sence of chlorine in the original substance.
(3) Brick-red = arsenate. (3) A neutral solution of the three halides
(4) Dark-red = chromate. is treated with potassium iodate and dilute
.
(j8) A precipitate insoluble in nitric acid. acetic acid ; as iodine is liberated, more iodate
Soluble in ammonia : White = chloride (hy- is added and the solution boiled until all the
pochlorite), cyanide^ thiocyanate yellowish-white ;

iodine is eliminated. The solution is mixed
= bromide orange-red = ferricyanide
; white with half its volume of 5^V-nitric acid, bromine
;
= ferrocyanide (sparingly soluble). is evolved and the solution boiled colourless. till
Insoluble in ammonia Yellow = iodide A little potassium iodide added to destroy the
:
black = sulphide.
;
iodate in excess, and the solution boiled till

4. Ferric chloride in neutral solutions yields : colourless, then an equal volumeof strong nitric
(o) Acolouration : blood-red acetate, for- = acid and a few drops of silver nitrate are added,
mate (precipitate on boiling), thiocyanate (no when a white precipitate indicates a chloride:
precipitate on boiling) ; violet salicylate,
= The strong nitric acid holds in solution any
thiosulphate (fugitive) ; bluish-black = tannate, trace of silver iodate. If thiocyanic acid is
gallate ; greenish-brown =
ferricyanide (dark- present, the test for iodine must be made in a
blue precipitate on adding stannous chloride). small portion of the original solution, adding
(0) A
precipitate : buff benzoate, carbon- = sodium acetate as well as acetic acid to depress
ate ; reddish-brown =
succinate ; white phos- = the dissociation of the latter (Benedikt and
phate ; black =
sulphide ; bluish- or greenish- Snell, J. Amer. Chem. Soc. 1903, 25, 809).
black =
tannate, gallate. Other acids must be detected by special tests.
Sulphur acids. (1) Detect sulphate by barium Iodine, and ferrocyanides and f erricyanides must
chloride, and sulphide acetate, by lead
&c. be removed before testing for nitrates.
Make part of the solution slightly alkaline with To remove iodine, ferrocyanic, ferricyanic,
potash, add zinc sulphate in considerable ex- and thiocyanic acids, add excess of a mixture of
cess, and filter. Test one part of the filtrate cupric and ferrous sulphates, and filter. To
for thiosulphate by means of
hydrochloric acid ; remove excess of copper and iron (which is not
to the other part add acetic acid till
faintly always necessary) heat to boiling, add slight
acid, sodium nitroprusside in small quantity, excess of pure caustic potash or soda, and filter.
and potassium ferrocyanide ; a pink precipitate To remove bromine and iodine, acidify with
indicates a sulphite. dilute sulphuric acid, and boil with successive
(2) Separation of soluble sulphates, sulphites, additions of potassium permanganate until the
sulphides, and thiosulphates in neutral solution. liquid has a faint permanent pink tinge
filter.;
172 ANALYSIS.
To remove hypochlorous and nitrous acids, white precipitate, becoming yellow, red, and then
acidify with dilute sulphuric acid, and boil. black (HgS) insoluble in ammonium sulphide
; ;
Nitrous acid can also be decomposed by boiling appreciably soluble in alkali sulphides (Hg(SNa ) 2 ),
with a strong solution of ammonium chloride. insoluble in nitric acid ; soluble in aqua regia.
For an alternative classification of the acidic Stannous chloride, white precipitate (Hg 2Cl 2 ),
radicles into analytical groups, compare T. Milo- becoming grey (Hg) with excess of the reagent.
bendski (J. Russ. Phys. Chem. Soc. 1909, 41, Potassium iodide, scarlet precipitate (HgI 2 ),
1301). soluble in excess. Metallic copper, as mercurous
SPECIAL REACTIONS. salts.
Bismuth.
In the following only the most charac
lists
teristic and useful reactions have been given ;
Hydrogen sulphide, brown precipitate (Bi 2 S 3 ),
insoluble in ammonium sulphide soluble in
negative reactions, and others not particularly
;
nitric acid. Ammonia, white

precipitate
characteristic, have, as a rule, been omitted (see
also Dry (Bi(HO) 3 ), soluble in hydrochloric acid. Water
reactions).
in large excess (with previous addition of am-
METALS. monium chloride if chlorides are absent), white
The metalsare arranged in the order of their precipitate (BiOCl), soluble in hydrochloric acid ;
occurrence in the systematic separation. insoluble in tartaric acid. Reducing agents
Silver. (sodium stannite, hypophosphites, hydrosulphites,
Hydrochloric acid, a white precipitate (AgCl), formaldehyde in alkaline solution) reduce bis-
insoluble in hot water and in nitric acid ; soluble muth compounds to elemental bismuth.
in ammonia and reprecipitated by nitric acid in Copper.
excess. Potassium chromale, a dark-red pre- Hydrogen sulphide, black precipitate (CuS),
cipitate (Ag 2 Cr0 4 ) ; soluble in mineral acids insoluble in ammonium sulphide and in dilute
and decomposed by caustic alkalis. Potassium sulphuric acid ; soluble in nitric acid and in
cyanide, white precipitate (AgCN) soluble in potassium cyanide. Ammonia, blue precipitate,
excess to KAg(CN) 2 . soluble hi excess to dark-blue solution. Potas-
Lead. sium ferrocyanide, chocolate- brown precipitate,
Hydrochloric acid, a white precipitate (PbCl 2 ), insoluble in dilute acids ; in very dilute solutions
soluble in hot water, from which it crystallises colouration only ; decomposed by sodium
on cooling ; insoluble in ammonia. Hydrogen hydroxide, yielding blue copper hydroxide.
sulphide, a black precipitate (PbS), insoluble in Cadmium.
ammonium sulphide (in presence of hydrogen Hydrogen sulphide, yellow precipitate (CdS),
halides, intermediate red compounds are pro- insoluble in ammonium sulphide and potassium
duced, e.g. PbS,4PbI 2 , J. Amer. Chem. Soc. cyanide ; soluble in nitric acid and hot dilute
1895, 17, 511 ; 1901, 23, 680) ; soluble in nitric sulphuric acid. Ammonia, white precipitate
acid. Sulphuric acid, a white precipitate (CdH 2 2 ), readily soluble in excess. Caustic
(PbS0 4 ), soluble in hot hydrochloric acid ; in- potash or soda, white precipitate (CdH >().,)
soluble in dilute sulphuric acid ; soluble in insoluble in excess.
ammonium acetate (Noyes and Whitcomb, Tin.
J. Amer. Chem. Soc. 1905, 27, 747). Potassium Stannous compounds. Hydrogen sul-
chromate, yellow precipitate (PbCr0 4 ), in- phide, dark-brown precipitate (SnS), soluble in
soluble in acetic acid ; soluble in potassium yellow but not in colourless ammonium sul-
hydroxide. phide. Mercuric chloride, white precipitate
Thallium. (Hg 2Cl 2 ), becoming grey (Hg).
Hydrochloric white precipitate (T1C1),
acid, Stannic compounds. Hydrogen sulphide,
only slightly soluble in hot water. Potassium yellow precipitate (SnS 2 ), soluble in ammonium
iodide, pale-yellow precipitate (Til), even in sulphide ; appreciably soluble in ammonium
dilute solutions. Sulphuric acid, no precipitate carbonate (Ber. 1894, 27, 2739); soluble in
(diff. from Pb). Sodium cobaltinilrite gives red concentrated hydrochloric acid; dissolves in
crystalline precipitate (Tl 3 Co(N0 2 ) 6 ) (J. Russ. aqueous caustic soda. Stannic chloride, boiled
Phys. Chem. Soc. 1910, 42, 94). with copper becomes stannous chloride. When
Tungsten. zinc and platinum are placed in the solution,
Hydrochloric acid, a yellowish-white pre- no black stain on the platinum crystals of tin
;
cipitate (H 2 W0
4 ), insoluble in excess of the on the zinc.
dilute acid ; soluble in the concentrated acid Antimony.
and in tartaric acid ; fragments of zinc added Hydrogen sulphide, orange precipitate (Sb 2 S 3 ),
to this solution produce a blue colouration. soluble in ammonium sulphide and in concen-
Stannous chloride, a yellow precipitate, which trated hydrochloric acid ; insoluble in ammo-
becomes blue if mixed with hydrochloric acid nium carbonate. Water in excess (with ammo-
and heated. Ammonium sulphide, no precipitate nium chloride if chlorides are absent), white
with sodium tungstate, but on acidifying, light- precipitate (SbOCl), soluble in hydrochloric acid
brown precipitate (WS 3 ), insoluble in hydrochloric and in tartaric acid. Zinc and platinum, a
acids, soluble in ammonium sulphide. black stain on the platinum (Sb), soluble in
Mercury. nitric acid and in ammonium sulphide.
Mercurous compounds. Hydrochloric Arsenic.
acid, white precipitate (Hg 2Cl 2 ), insoluble in Hydrogen sulphide, yellow precipitate, soluble
hot water insoluble in ammonia, but blackened ammonium ammonium
; in sulphide and in car-
(NH 2 Hg 2Cl). Stannous chloride, grey precipi- bonate insoluble in concentrated hydrochloric
;
tate (Hg). Metallic copper, becomes coated with acid. Metallic copper, boiled with the liquid after
mercury, which can be sublimed. acidifying with hydrochloric acid, is covered with
Mercuric compounds. Hydrogen sulphide, a shining grey deposit (As 2Cu 5 ), which, when
ANALYSIS. 173
heated in a tube, yields a sublimate of arsenious oxidises osmium compounds to osmic tetroxide
oxide (Reinsch's test) (Clark, Chem. Soc. Trans. (Os0 4 ),
characteristic odour and yellow solution
1893, 63, 884, 886). Nascent hydrogen produced in caustic soda.
from zinc and dilute sulphuric acid reduces Ruthenium.
arsenic compounds to volatile arsine (AsH 3 ), Hydrogen sulphide, blue solution followed by
which decomposes on gently heating, giving an brown precipitate of ruthenium sulphide.
arsenic deposit soluble in aqueous hypochlorites. Sodium thiosulphate in ammoniacal solution to
Antimony compounds under these conditions dilute solutions of ruthenium, a
purplish-red
also give a black deposit (antimony), insoluble colouration. Zinc reduces RuCl 3
giving a blue
,
in hypochlorites (Marsh's test). Zinc and caustic solution and then precipitating ruthenium.
soda reduce arsenic compounds, liberating arsine, Rhodium.
which produces a yellow-to-brown stain on Hydrogen sulphide, on warming, black pre-
mercuric chloride paper (Gutzeit's test, Chem. cipitate (Rh 2 S 3 ), insoluble in ammonium sulphide;
Soc. Trans. 1901, 79, 715). soluble in boiling nitric acid. Potassium nitrite,
Arsenites. Ammonia-silver nitrate, yellow warmed with sodium rhodium chloride, gives
precipitate (Ag 3 As0 3 ),
soluble in nitric acid and orange-yellow precipitate (K 3 Rh(NO 2 6 ) ).
ammonia. Ammonio-cupric sulphate, bright- Gold.

green precipitate (CuHAs0 3 ), turns red by Hydrogen sulphide, black precipitate (Au 2 S 3 )
boilingwith caustic soda. in cold, brown precipitate (Au 2 S) in hot, solu-
Ar senates. Ammonio-silver nitrate, brick- tion ; soluble in yellow ammonium sulphide.
red precipitate (Ag s As0 4 ), soluble in nitric acid Oxalic acid or ferrous sulphate, brown or purple
and ammonia. Ammonium chloride, ammonia, precipitate, yellow and lustrous when rubbed.
and magnesium sulphate, white crystalline pre- Stannous and stannic chlorides, purplish pre-
cipitate (NH 4 MgAs0 4 ). Ammonio-cupric sul- cipitate, insoluble in hydrochloric acid.
phate, pale-blue precipitate, turned black by Hydrogen peroxide, in very dilute alkaline solu-
boiling with caustic soda. tion, liberates finely divided gold having a
When arsenic acid or arsenates are present, beautiful blue shimmer.
they should be reduced by heating with sul- Molybdenum.
phurous acid or ammonium iodide or hydriodic Hydrogen sulphide, brownish-black precipi-
acid (Bull. Soc. chim. Belg. 1909, 23, 88) before tate (MoS 3 on heating, soluble in ammonium
)
applying hydrogen sulphide or Reinsch's test sulphide. Sodium phosphate, in presence of

(Usher and Travers, Chem. Soc. Trans. 1905, nitric acid, yellow precipitate on heating,
87, 1370). soluble in ammonia and in excess of the alkaline
Platinum. phosphate. Potassium thiocyanate and zinc or
Hydrogen sulphide, brown precipitate (PtS 2 ) stannous chloride, red colouration due to
on heating, soluble in ammonium sulphide. Mo(CNS) 4 soluble in ether. Concentrated sul-
Ammonium chloride or potassium chloride, phuric acid, when strongly heated with moly-
yellow crystalline precipitate (M 2 PtQ 6 ), less bdenum compounds, develops a deep-blue
soluble in presence of alcohol. Potassium iodide, colouration. Phenylhydrazine, in 50 p.c. acetic
in dilute solution red colouration (K 2 PtI g ), acid, red colouration (Ber. 1903, 36, 512).
very delicate test. Stannous chloride, in dilute Selenium.
solution, brownish-red colouration, delicate Hydrogen sulphide, yellow precipitate, be-
test. coming dark on heating, soluble in ammonium
Palladium. sulphide. Sulphurous acid, in presence of hydro-
Hydrogen sulphide, black precipitate (PdS), chloric acid, a red precipitate, which becomes
insoluble in ammonium sulphide soluble in
; grey on heating, and is soluble in potassium
hot hydrochloric acid and in aqua regia. Potas- cyanide. Stannous chloride and other reducing
sium iodide, black precipitate (PdI 2 ), somewhat agents behave in a similar manner. Barium
soluble in excess. Mercuric cyanide, yellowish chloride, (i.) white precipitate (BaSe0 3 ), soluble
white, gelatinous precipitate (PdCy 2 ), readily in dilute hydrochloric acid (ii. ) white precipitate
;
soluble in ammonia. Ammonium chloride, no (BaSe0 4 ),insoluble in dilute hydrochloric acid;

precipitate (diff. from Pt) ; on addition of chlorine soluble in the strong acid, evolving chlorine.
water, orange precipitate ((NH 4 ) 2 PdCl e ). Potas- Concentrated sulphuric acid, green colouration.
sium chloride, precipitate (2KCl-PdCl 2 ) only in Tellurium.
very concentrated solutions. Hydrogen sulphide, brown precipitate (TeS 2 )
Indium. at once from tellurites, but from tellurates only
Hydrogen sulphide, decolourisation f ollowedby after boiling with hydrochloric acid. Potassium
brown precipitate (Ir 2 S 3 ), soluble in ammonium iodide, to tellurite in acid solution, black pre-
sulphide. Caustic potash, a greenish colouration cipitate (TeI 4 ). Reducing agents (SnCl 2 ,Zn),
which, on heating with exposure to air, changes black precipitate (Te). Concentrated sulphuric
slowly to azure blue (diff. from Pt). Ammo- acid, carmine colouration.
nium chloride or potassium chloride, dark-brown Aluminium.
or red precipitate (double chloride), insoluble in Ammonia, white gelatinous precipitate
a saturated solution of the precipitant. Both (A1H 3 3 ), insoluble in excess and in ammonium
salts become olive green with potassium nitrite carbonate ;
soluble in acids. Caustic potash or
and other reducing agents, especially in hot soda, white gelatinous precipitate (A1H 3 3 ),
solutions. Strong sulphuric acid and ammonium soluble in excess ; reprecipitated on adding
nitrate, on heating, blue colouration. ammonium chloride and heating.
Osmium. Chromium.
Hydrogen sulphide, in acid but not in neutral Chromic salts. Ammonia, greenish or
solution, black precipitate (OsS 4 ), insoluble in soluble in acids ;
purplish precipitate (CrH 8 0,),
ammonium sulphide. Nitric acid on boiling insoluble in ammonium carbonate. Caustic
174 ANALYSIS.
potash soda, green precipitate (CrH 3 O 3 ),
or brown precipitate, readily decomposed by
soluble in excess, but reprecipitated on boiling. alkalis, yielding yellow alkali diuranates.
Chromates. Hydrogen sulphide in acid solu- Titanium.
tion, reduction to chromic salt with change of Ammonia, caustic potash, or soda, or ammo niuin
colour to green. Lead acetate, bright yellow sulphide, white precipitate (H 2 Ti0 3 ), insoluble in
precipitate (PbCr0 4 ), insoluble in acetic acid. excess ; soluble in dilute sulphuric and hydro-
Silver nitrate, dark-red precipitate (Ag 2Cr0 4 ), chloric acids. Potassium ferrocyanide, dark-
soluble in nitric acid. brown precipitate. Sodium thiosulphate, com-
Iron. plete precipitation on boiling. Hydrogen per-
Ferrous salts. Ammonium sulphide, black oxide, to a slightly acid solution of titanium
precipitate (FeS), soluble in acids. Ammonia or sulphate orange-red colouration ; weakened by
;
caustic potash or soda, white precipitate, rapidly fluorides. Reducing agents (SnCl 2 or Zn and
becoming green and then brown. Potassium HC1) produce a violet colouration (TiCl 3 ).
ferrocyanide, white precipitate, gradually be- Catechol added to dilute solutions of titanic
coming dark Potassium ferricyanide,
blue. or titanous salts, yellowish-orange colouration,
dark-blue precipitate (Fe 3 (FeCy e ) 2 ). Potassium very delicate test, but interfered with by mineral
thiocyanate, no reaction. acids or alkalis (Ber. 1909, 42, 4341).
Ferric salts. Ammonium sulphide, black Zirconium.
precipitate (2FeS + S, or Fe 2 S 8 ),soluble in Ammonia, ammonium sulphide, caustic soda,
acids. Ammonia or caustic potash or soda, white gelatinous precipitate, dissolving in dilute
reddish-brown precipitate (FeH 3 3 ), soluble in acid, but less readily after boiling ; precipitation
acids. Potassium ferrocyanide, dark-blue pre- prevented by tartaric acid. Oxalic acid, white
cipitate (Fe 4 (FeCy 6 ) 8 ), insoluble in dilute acids. precipitate (Zr(C 2 4 ) 2 ), readily soluble in am-
Potassium ferricyanide, no precipitate ; greenish- monium oxalate or in excess of oxalic acid.
brown colouration. Potassium thiocyanate, Hydrogen peroxide, white milky precipitate
blood-red colouration not affected by boiling
; (Zr,0 s ), evolving chlorine when boiled with
or by hydrochloric acid. hydrochloric acid. Turmeric paper, moistened
Thorium. with acid solution of zirconium salt, becomes
Ammonia, caustic soda, or potash, white reddish- brown on drying.
gelatinous precipitate (Th(OH) 4 ), insoluble in Zinc.
excess. Ammonium or sodium carbonate, white Ammonium sulphide, white precipitate (ZnS),
precipitate, basic carbonate; soluble in excess. soluble in dilute hydrochloric acid ; insoluble in
Oxalic acid, white precipitate (Th(C 2 4 ).,,2H 2 0), acetic acid and in alkalis. Caustic potash or soda,
insoluble in excess and insoluble in mineral acids, white precipitate (ZnH.,0 2 ), soluble in excess.
but soluble in ammonium oxalate. Potassium Potassium ferrocyanide, white precipitate, in-
fluoride or hydrofluoric acid, white precipitate soluble in dilute hydrochloric acid (Zn 2 FeCy 6 ).
(ThF 4 ). Potassium sulphate, white crystalline Manganese.
precipitate (2K 2 S0 4 ,Th(S0 4 ) 2 ,2H 2 0). Ammonium sulphide, pink precipitate (MnS),
Cerium. soluble in dilute hydrochloric acid and in
Ammonia, white precipitate of basic salt, in- acetic acid. Caustic potash or soda, white pre-
soluble in excess. Caustic potash or soda, white cipitate (MnH 2 2 ), insoluble in excess, becoming
precipitate(Ce(OH) 3 ), insoluble in excess ; be- brown on exposure to air. Boiled with dilute
comes yellow when exposed to air. Oxalic acid, nitric acid and lead peroxide (in absence of
white precipitate (Ce 2 (C 2 4 ) 3 ), insoluble in ex- chlorine), a purplish crimson solution of per-
cess, but soluble in a large quantity of hydro- manganic acid.
chloric acid. Potassium sulphate, white pre- Nickel.
cipitate even in somewhat acid solutions Ammonium sulphide, black precipitate (NiS),
(CeK 3 (S0 4 ) 3 ), insoluble in saturated solution somewhat soluble in excess ; insoluble in cold
of potassium sulphate. Hydrogen peroxide, in dilute hydrochloric acid ; soluble in strong acids.
ammoniacal solution, orange-brown precipitate. Caustic potash or soda, pale-green precipitate
Glucinum. ( NiH 2 2 ), insoluble in excess. Potassium cyanide ,
Ammonia, white precipitate (G1H 2 2 ), in- precipitate (NiCy 2 ), soluble in excess, forming
soluble in excess. Caustic potash or soda, the NiCy 2 ,2KCy, which is not altered when boiled
same precipitate, soluble in excess, but repre- with exposure to air. This solution, heated
cipitated on boiling (diff. from Al). Ammonium with excess of sodium hypochlorite solution,
carbonate, white precipitate, easily soluble in or mixed with bromine in the cold, yields a
excess (diff. from Al). precipitate of black nickelic hydroxide (NiH 8 3 >.
Glacial acetic acid dissolves G1(OH) 2 or G1C0 3 , Dimethylglyoxime (CH 3 -C(NOH)-C(NOH)-CH ;J )
and the residue, after evaporating to dryness, is (Tschugaeff, Ber. 1905, 38, 2520), added to am-
the basic acetate (G1 4 0(CH 3 -CO.) 6 ), readily moniacal or acetic acid solution of nickel salts,
soluble in chloroform, ether, acetone, the alcohols, scarlet precipitate (distinction from cobalt).
and other organic media; dissolves unchanged Dicyanodiamidine (H. Grossmann and W.
in glacial acetic acid ; it melts at 283-284 , and Heilborn, Ber. 1908, 41, 1878) added to am-
can be sublimed without decomposition. Sodium moniacal solutions of cobalt and nickel salts
hydrogen carbonate, 10 p.c. dissolves G1(OH) 2 ; containing excess of sucrose, yellow crystalline
dilution to 1 p.c. causes reprecipitation. H
precipitate (Ni(N 4 5 C 2 0) 2 ,2H 2 0), the presence
Uranium. of cobalt indicated by the reddish-violet colour
Ammonia, caustic potash, or soda, yellow pre- of the solution.
cipitate, insoluble in excess, but readily soluble Cobalt.
in ammonium carbonate. Ammonium sulphide, Ammonium sulphide, black precipitate (CoS),
brown precipitate, readily soluble in ammonium insoluble in cold dilute hydrochloric acid ;
carbonate. Potassium ferroc-yanide, chocolate- soluble in strong acids. Caustic potash, pale-blue
ANALYSIS. 175
precipitate (CoH 2 slightly soluble in excess,

2 ), Magnesium.
forming a blue solution. Potassium cyanide, Sodium phosphite, in presence of ammonia
precipitate (CoCy 2 ),
soluble in excess, forming and ammonium chloride, white precipitate,
CoCy 2 ,4KCy, and when this solution is boiled rapidly becoming crystalline (NH 4 MgP0 46H,0).
with exposure to air it is changed to 3 CoCy 6 , K Forms slowly in dilute solutions, formation
which is not precipitated by sodium hypochlorite being accelerated by agitation and by rubbing
or bromine. Potassium nitrite to dilute acetic the sides of the beaker with a glass rod ; soluble
acid solutions, yellow crystalline precipitate in acids.
(K 3 Co(N0 2 ) 6 ). Nitroso-0-naphihol 10 6 -OH NOC H Potassium.

(Ilinski
and Knorre, Ber. 18, 699) dissolved in Chloroplatinic acid H
2 PtC'l 6 , yellow crystalline
dilute acetic acid added to feebly acid solu- precipitate (K 2 PtCl 6 ), somewhat soluble in water;
tions of cobalt and nickel, brick-red precipi- insoluble in alcohol. Sodium hydrogen tarlrate,
H
tate (Co(NOC 10 6 '0) 3 ); solution examined for in neutral or feebly acid solutions, a white crys-
nickel (Chaplin, J. Amer. Chem. Soc. 1907, 29, talline precipitate (KHC 4 H 4
8 ), forming slowly
1029). in dilute solutions. the solution contains free
If
Vanadium. mineral acids, nearly neutralise with soda and
Ammonium sulphide, dark-brown solution, add sodium acetate.
which when acidified yields a brown precipitate Sodium cobaltinilrite in acetic acid solution,
(V 2 S 4 ). Ammonium chloride, white precipitate yellow precipitate (K 2 NaCo(N0 2 6 ). ) Sodium
of ammonium meta-vanadate (NH 4 V0 3 ). Potas- l-amino-P-naphthol-6-sulphonate (eikonogen) in
sium ferrocyanide, in acid solution, a green 5-10 p.c. solutions, crystalline precipitate
precipitate. If a solution of an alkaline vana- (KS0 3 -C 10
5
H (NH 2 )-OH) ; negative results with
date is agitated with hydrogen peroxide and ether, ammonium and magnesium salts (Alvarez,
the solution acquires a deep purplish-red colour, Chem. Soc. Abstr. 1905, ii.
355).
but the ether remains colourless. Mild re- Ammonium.
ducing agents (S0 2 , H 2 S, HBr, alcohol, &c.) Ammonium salts are readily volatile. Heated
reduce vanadates in acid solutions to blue with lime, caustic potash, or soda, ammonia gas
divanadyl salts. Strong reducing agents (zinc is given off, and is recognised by its smell and
and aluminium with acids) produce a series of its action on test paper.
colour changes blue, green, and violet. Chloroplatinic. acid, yellow crystalline pre-
Columbium. cipitate ((NH 4 ) 2 PtCl 6 ), slightly soluble in water;
Hydrogen fluoride and potassium fluoride insoluble in alcohol. Sodium hydrogen tartrale,
produce potassium columbo-fluoride, which white crystalline precipitate (NH 4 HC 4 4 6 ), H
when boiled in aqueous solution yields potassium forming slowly in dilute solutions.
columbium oxyfluoride (K 2 CbOF 5 ,H 2 0) (solu- Nessler's reagent (K 2 HgI 2 and KOH), brown-
bility 1 in 12-5 cold water). Mineral acids, ish-red precipitate or colouration (NHg 2 I,H 2 0),
partial precipitation of columbic acid from very delicate test.
alkali columbates zinc and acid, blue coloura-
: Sodium.
tion, turning brown ; potassium ferrocyanide, Flame colouration, intense yellow.
greyish-green precipitate. Although all sodium salts are more or less
Tantalum. soluble, some dissolve only sparingly, e.g. sodium
Hydrogen fluoride and potassium fluoride oxalate and sodium a-naphthylamine-8-sul-
produce potassium tantalofluoride (K 2 TaF 7 ) phonate.
(solubility 1 in 154 cold water), separating in Potassium pyroantimonate, white crystalline
colourless needles. Mineral acids, white pre- precipitate (Na 2 H.,Sb 2 7 -6H.,0) (J. Amer. Chem.
cipitate of tantalic acid. Potassium ferrocy- Soc. 1909, 31, 634); from "neutral or slightly
anide, reddish-brown precipitate (v. Weiss and alkaline solutions.
Landecker, Zeitsch. anorg. Chem. 1909, 64, 65). Dihydroxytartaric acid, colourless precipitate
Calcium. (CChNa.C(OH) 2 -C(OH) 2 -C0 2 Na) (Fenton, Chem.
Ammonium carbonate, white precipitate Soc." Trans. 1895, 67, 48). Solution of bismuth
(CaC0 3 ), soluble acids. in
Sulphuric acid, nitrate in 50 p.c. potassium nitrite containing
white precipitate only in very concentrated solu- caesium nitrite, yellow crystalline precipitate
tions. Ammonium oxalate, white precipitate (5Bi(N0 2 3 ,9CsN0 2 ,6NaNO,); very delicate test,
)
(CaC 2 4 ), insoluble in acetic and oxalic acids, not interfered with by lithium and metals of
but soluble in hydrochloric acid. alkaline earths (Ball, Chem. Soc. Trans. 1909,
Strontium. 95, 2126). Sodium chloride, obtained by slow
Ammonium carbonate, precipitate, white evaporation of a solution acidified with hydro-
soluble in acids (SrC0 3 ). sulphate,Ammonium chloric acid, crystallises in distinct cubes.
white precipitate, especially on boiling. Am- Lithium.
monium oxalate, white precipitate (SrC 2 4 ), Chloroplatinic acid, no precipitate.
soluble in hydrochloric acid ; insoluble in acetic Sodium phosphate, in alkaline solution ; white
precipitate (Li 3 P0 4 ), soluble in hydrochloric acid,

acid. Sulphuric acid or calcium sulphate, white
precipitate (SrS0 4 ), forming slowly. not reprecipitated by ammonia except on boiling.
Barium. Lithium chloride is soluble in ethyl or amyl
Ammonium carbonate, white precipitate alcohol, and in pyridine. Ammonium hydrogen
(BaC0 3 ), soluble in acids. Ammonium oxalate, fluoride, white precipitate (LiF).
white precipitate (BaC 2 4 ), soluble in hydro- Caesium.
chloric acid ; insoluble in acetic acid. Flame colouration, violet.
Sulphuric
acid or calcium sulphate, an immediate white
Chloroplatinic acid, yellow crystalline pre-
precipitate, insoluble in acids and alkalis. Potas- cipitate (Cs,PtCl 4 ),
insoluble in boiling water.
VJMW chromate, yellow precipitate (BaCr0 4 ), Tartaric acid, crystalline precipitate, some-
insoluble in acetic acid. what soluble in water. Stannic chloride, white
176 ANALYSIS.
precipitate (Cs 2 SnCl.). Lead chloride dissolved Sulphides.
in chlorine water, yellow precipitate (Cs 2 PbCl 6 ). Hydrochloric acid, in most cases evolution of
Caesium carbonate is soluble in alcohol (diff. hydrogen sulphide, especially on heating. Lead
from K, Rb). nitrate or acetate, black precipitate (PbS).
Rubidium. Silver nitrate, black precipitate (Ag 2 S), in-
Flame colouration, violet. soluble in ammonia, sodium thiosulphate, and
Chloroplatinic acid, yellow crystalline pre- potassium cyanide. Sodium nitroprusside, in
cipitate (Rb 2 PtCl 6 ), insoluble in boiling water. alkaline solutions an intense but somewhat
Tartaric acid, white crystalline precipitate, less fugitive violet colouration.
soluble than the caesium compound (Reactions Phosphates.
of Cs and Rb, v. Wells, Amer. J. Sci. [3] 43, 17 Barium chloride, white precipitate Ba s (P0 4 ) 2,
and 46, 18%6, and 265). soluble in dilute acids. Calcium chloride, white
precipitate (Ca 3 (P0 4 ) 2 ), soluble in acetic acid.
ACID RADICLES. Silver nitrate, yellow precipitate (Ag 3 P0 4 ), soluble
The acid radicles are arranged partly in the in nitric acid and in ammonia. Pyrophos-
order of the systematic separation and partly phates and metaphosphates give white
with a view to bring together those acids which precipitates of their silver salts with silver
are commonly associated or which resemble one nitrate, but metaphosphates alone, unlike ortho-
another hi their reactions. In all cases, unless and pyro-phosphates, coagulate albumin. Mag-
otherwise specified, it is important that the nesium sulphate, in presence of ammonium
solution should be neutral. chloride and ammonia, white crystalline pre-
Sulphates. cipitate (NH 4 MgP0 4 6H 2 0), soluble in acids.
Barium chloride, white precipitate (BaS0 4 ), Ammonium molybdate, in nitric acid solution,
insoluble in acids and alkalis. on heating, a yellow precipitate ((NH 4 3 P0 4 )
-
Sulphites. 12Mo0 3 soluble in ammonia, and soluble in

)
Hydrochloric acid, sulphur dioxide evolved, excess of an alkaline phosphate.

but no sulphur piecipitated. Barium chloride, Phosphites.
white precipitate (BaS0 3 ), soluble in hydro- Barium chloride, white precipitate (BaHP0 3 ),
chloric acid. Iodine solution, sulphites are con- soluble in hydrochloric acid. Silver nitrate,
verted into sulphates. Neutralise, then slightly precipitate of metallic silver, especially in pre-
acidify with acetic acid ; add excess of zinc sence of ammonia, and on heating. Mercuric
sulphate,, a small quantity of sodium nilro- chloride,white precipitate (Hg 2 Cl,), becoming
prusside and potassium ferrocyanide. The preci- grey (Hg). Heated with nitric acid, phosphites
pitate of zinc ferrocyanide has a pink colour. are converted into phosphates. Heated alone,
Strontium chloride, white precipitate (SrS0 3 ), phosphites evolve phosphine. Copper sulphate,
different from thiosulphate SrS 2 3 , being much pale blue precipitate.
more soluble. Hypophosphites.
Hyposulphites hydrosulphites,' e.g. Na 2 S 2 4 ,
(' Heated alone, evolve phosphine. Barium
2H 2 0)*owe their technical application to their chloride, white precipitate only in strong solution
reducing action on indigotin and its sulphonic (Ba(H 2 P0 2 ) 2 ). Silver nitrate, metallic silver
acids the colour is discharged (indigo-white). precipitated. Copper sulphate, brown preci-
Silver nitrate, black precipitate (Ag). Mercuric pitate, cuprous hydride (Cu 2 H 2 ).
chloride, black precipitate (Hg). Copper sulphate, Carbonates.
reddish precipitate (Cu and Cu 2 2 ), in very H Hydrochloric acid, effervescence, with evolu-
dilute solution, colloidal copper. tion of carbonic anhydride, which turns lime
Thiosulphates. water turbid. Barium chloride, white pre-
Hydrochloric acid, sulphur dioxide evolved cipitate (BaC0 3 ), soluble in acids with efferves-
and sulphur precipitated. Silver nitrate, white cence. Mercuric chloride, red precipitate (basic
precipitate (Ag 2 S 2 O 3 ), rapidly changing to black carbonate) bicarbonates give only a yellowish
;
(Ag 2 S), soluble hi excess of alkaline thiosul- opalescence. Calcium sulphate, white precipitate,
phate, forming a much more stable solution. immediately with carbonate, but only after
With sodium nitroprusside, zinc sulphate, and standing with bicarbonate (Leys, J. Pharm.
potassium ferrocyanide, the precipitate is white. Chim. 1897, (vi.) 6, 441).
Iodine solution converts soluble thiosulphates Borates.
into tetrathionates, which give no precipitate Barium chloride, white precipitate in not too
with barium chloride. Ferric chloride, transient dilute solutions, soluble in acids. Silver nitrate,
violet colouration (Fe 2 (S 2 3 ) 3 ). in strong solution, white precipitate (AgBQ 2 );
Persulphates (e.g. K 2 S2 8 ). in dilute solution, dark-grey deposit (Ag 2 0).
The dry salts evolve oxygen on heating. Mix the solid substance with concentrated
Barium chloride, no precipitate in the cold, on sulphuric acid in a small crucible, add alcohol,
warming oxygen evolved and BaS0 4 precipitated. and ignite ; the alcohol flame is green, especially
Silver nitrate, black precipitate (silver peroxide). at the edges. Mix the solid substance with three
Other metallic salts (Pb, Mn, Co, and Ni) yield parts potassium hydrogen sulphate and one part
their hydrated peroxides. powdered fluorspar, and heat on platinum wire
Monoper sulphuric acid (Card's acid) in the cold area of the flame; a bright-green
HOS0 2 -OOH, produced by adding a persulphate colouration (due to BF 3 )
is observed. Turmeric
to cold concentrated sulphuric acid, and pouring paper, moistened with acid solution of boric
the mixture on to ice. Aromatic amines (e.g. acid, becomes reddish brown on drying.
H
p-Cl-C 6 4 -NH 2 )give coloured oxidation products Silicates.
with persulphates and nitroso- compounds (e.g, Solutions of silicates heated with acids, am-
H
C1-C 6 4 -NO) with Caro's acid. monium chloride, or ammonium carbonate,
Thionie acids (v. Chem. Soc. Trans. 1880, 608). deposit silicic acid. Dilute solutions must be
ANALYSIS. 177
evaporated to dryness, and on treating the gen oxides in sulphuric acid likewise liberate
residue with dilute hydrochloric acid insoluble iodine, but do not liberate bromine unless
silica is left. added in large excess.
Most silicates are insoluble in water some ; Cyanides.
are decomposed by acids others are only de- Silver nitrate, white precipitate
;
(AgCN), in-
composed fey fusion with about four times their soluble in nitric acid, but soluble in
ammonia,
weight of a mixture of equal parts of sodium sodium thiosulphate, or excess of the alkaline
and potassium carbonates. cyanide.
Silicofluorides. Add ferric chloride and ferrous sulphate ;
Concentrated sulphuric acid, in leaden or make alkaline with caustic potash or soda, and
platinum capsule, hydrogen fluoride and silicon then acidify with hydrochloric acid. A
dark
fluoride are evolved. Barium chloride, colourless blue precipitate of Prussian blue is formed.
crystalline precipitate BaSiF 6 Silicofluorides
.
Evaporate the solution with an excess of
oil heating evolvesilicon fluoride, leaving residues yellow ammonium sulphide to complete dryness
of metallic fluorides. on a water- bath ; dissolve in very dilute hydro-
Oxalates. chloric acid, and add ferric chloride ; a blood-
Barium chloride or calcium chloride, white red colouration is produced.
precipitate, insoluble in acetic acid, but soluble Most cyanides evolve hydrocyanic acid, re-
in hydrochloric acid. cognisable by the smell, when treated with
Acidify with sulphuric acid, and add potas- hydrochloric or sulphuric acid.
sium permanganate ; the colour of the latter is Mercuric cyanide cannot be recognised by
rapidly and completely discharged. these tests. It yields cyanogen when heated in
Heat the solid substance with concentrated a closed tube, and is decomposed when heated
sulphuric acid carbonic anhydride and car-
;
with strong sulphuric acid.
bonic oxide are evolved. The latter burns with Ferrocyanides.
a blue flame. Silver nitrate, white precipitate ( Ag 4 FeCy g ), in-
Fluorides. soluble in nitric acid and sparingly soluble in
Barium, chloride, white precipitate (BaF 2 ), ammonia ; soluble in potassium cyanide. Ferric
soluble in hydrochloric acid. Silver nitrate, no chloride,dark-blue precipitate (Fe 4 (FeCy g ) 3 ).
precipitate with soluble fluorides. Concentrated Ferrous sulphate, white precipitate, rapidly be-
sulphuric acid, especially when heated, produces coming blue. Capper sulphate, chocolate- brown
hydrogen fluoride, which attacks glass. The precipitate (Cu 2 FeCy 6 ), or in very dilute solution
substance and acid are placed in a small leaden a brown colouration.
or platinum crucible, which is covered with a Ferricyanides.
watch-glass protected by a thin coating of wax, Silver nitrate, orange precipitate (Ag 3 FeCy 6 ),
part of which has been scratched away so as to soluble in ammonia ; insoluble in nitric acid. Fer-
expose the glass. rous sulphate, dark-blue precipitate (Fe 3 (FeCy 8 ) 2 ),
Chlorides. insoluble in dilute acids ; decomposed by alkalis.
Silver nitrate, a white precipitate (AgCl), Ferric chloride, a greenish -brown colouration.
insoluble in nitric acid, soluble in ammonia ; Thioeyanates.
darkens when exposed
to light. Manganese di- Silver nitrate, white precipitate (AgCNS),
oxide and sulphuric acid, evolution of chlorine soluble in ammonia ; insoluble in nitric acid.
on heating. Potassium dichromate and strong Ferric chloride, blood-red colouration, not
sulphuric acid, evolution of chromyl chloride affected by boiling nor by hydrochloric acid ; de-
on heating. This forms with ammonia a yellow colourised by mercuric chloride. Copper sul-
solution of ammonium chromate. phate, a black precipitate changing to white
Bromides. (Cu 2 (CNS) 2 ) on standing or addition of a re-
Silver nitrate, white precipitate
yellowish ducing agent. Moderately strong sulphuric acid
(AgBr), insoluble acid ; moderately
in nitric evolves carbon oxysulphide, which burns to car-
soluble in ammonia ; readily soluble in potassium bon dioxide and sulphur dioxide. Cobalt chloride
cyanide or sodium thiosulphate. Manganese and the solution shaken up with ether and amyl
dioxide and sulphuric acid, orange vapours alcohol, azure-blue colouration (K,Co(CNS) 4 ).
<>f
bromine, which turn starch paste orange. Cyanates.
Chlorine water liberates bromine, which dis- Cobalt chloride, in aqueous alcoholic solution,
solves in ether or carbon bisulphite,
forming an blue soluble double salt (K 2 Co(CNO) 4 ), decom-
orange-browji solution. Bromides heated with posed by excess of water.
potassium dichromate and strong sulphuric acid Nitrates.
yield bromine, which forms a colourless solution Sulphuric acid evolves nitric acid on heating ;
with ammonia. if metallic copper is added, red-brown nitrogen

Iodides. oxides are given off.
Silver nitrate, yellow precipitate (Agl), in-
^
The neutral solution is mixed with ferrous
soluble in nitric acid or ammonia ; acid is
soluble sulphate, and concentrated sulphuric
poured down the side of the tube so as to form a
in potassium cyanide or sodium thiosulphate.
M'inganese dioxide and -sulphuric acid yield layer at the bottom a dark-brown ring is formed
;
violetvapours of iodine, which colour starch at the junction of the two liquids. Iodine and
paste blue. Chlorine water, bromine water, or bromine must be removed before applying this
potassium dichromate in presence of hydrochloric test, and the liquid must be cold. Nitrate in
tcid, liberates iodine, which turns starch paste an presence of nitrite: destroy nitrite by boiling
ntense blue. The colour acetic acid solution with urea or hydrazine sul-
disappears on
md reappears on cooling. The liberatedheating,
iodine phate ; then add potassium iodide, starch,
and
nay be agitated with carbon bisulphide or chlo- a fragment of zinc; blue colouration denotes
roform, when it yields a violet solution. Nitro- nitrate.
VOL. I. T. N
178 ANALYSIS.
Nitrites. (Ca 3 (C' 6 H 6 7)2 )
Silver nitrate, a white precipitate in concen- only on boiling. Potassium salts, no precipitate.
trated solutions. Cadmium chloride, gelatinouswhite precipitate
Mix the solution with potassium iodide and (Cd(C 6 H 6 7 ) 2 ), insoluble in hot water ; soluble in
starch and acidify with acetic acid a deep-blue;
acetic acid (diff. from tartrates). Mercuric
colouration produced, owing to the liberation
is sulphate (5 p.c.), following by potassium perman-
of iodine. Nitrites heated with dilute acids white turbidity, mercuric acetone-
evolve nitrogen oxides. Melaphenylenediamine fanate,
icarboxylate (halogens should be absent)
hydrochloride, Bismarck brown colouration. (Deniges).
A dilute solution of a-napthylamine and Malates.
sulphanilic acid acidified with acetic acid ; a red Calcium chloride, no precipitate even on
colouration of azo- compound (cf. Zeitsch. boiling, except in strong solutions ; precipitate
angew. Chem. 1900, 235). in dilute solutions on adding alcohol. Lime
Hypochlorites. water, no precipitate even on boiling. Silver
Silver nitrate, a white precipitate of silver nitrate, white precipitate (Ag 2 C 4 H 4 O B ), which
chloride. Lead nitrate, a white precipitate be- becomes grey on boiling. Lead acetate, white
coming orange-red, finally brown. Manganous precipitate (PbC 4 H 4 B ), which when washed
salts,a brown precipitate (Mn0 2 o;H 2 0). Indigo
,
melts in boiling water.
solution, decolourised even in an alkaline solution. Succinates.
Chlorates. Barium chloride, or calcium chloride, no
Warm a small quantity of the solid with con- precipitate except after addition of alcohol.
centrated sulphuric acid a yellow explosive gas
;
Ferric chloride, reddish-brown precipitate
is produced with detonations. H
(Fe 2 (C 4 4 4 ) 3 ), soluble in acids ; decomposed by
Acidify the solution with sulphuric acid, add ammonia.
indigo solution, and then sulphurous acid or a Benzoates.
sulphite drop by drop ; the colour of the indigo Hydrochloric acid, white crystalline pre-
isdischarged. cipitate of benzoic acid, slightly soluble in
Perchlorates. water. Ferric chloride, a buff precipitate
Concentrated sulphuric acid, no explosive gas. H
(Fe 2 (C 4 7 O 6 ) 6 ), soluble in hydrochloric acid with
Titanous sulphate, perchlorates reduced to liberation of benzoic acid ; decomposed by
chlorides. ammonia. Concentrated sulphuric acid and
Bromates. alcohol on heating produce ethyl benzoate, dis-
Silver white precipitate, AgBr0 3
nitrate, ,
tinctive odour. Soda lime : benzoates heated
decomposed by hot hydrochloric acid with evo- with this reagent are decomposed, evolvin
lution of bromine. Barium chloride, white pre- benzene.
cipitate, Ba(Br0 8 ) 2 Sulphurous acid, bromine
.
Salicylates.
liberated. Ferric chloride, intense purple colour ; noi
lodates. affected by glycerol ; interfered with by alkalis,
Silver nitrate, white curdy precipitate (AgI0 3 ), dilute mineral acids, tartaric, citric, and oxalic
soluble in ammonia ; reduced to yellow silver acids, and certain other substances such as
iodide by sulphurous acid. Barium chloride, borax, sodium phosphate, ammonium and sodium
white precipitate (Ba(I0 3 ) 2 ). Sulphurous acid, acetates. Silver nitrate, white precipitate in
iodine liberated. neutral solutions. Bromine water, white pre-
Periodates. cipitate, which with sodium amalgam yields
Silver nitrate, yellowish-white, red, or brown phenol. Concentrated sulphuric acid and methyl
precipitate depending on the acidity of the alcohol on heating give methyl salicylate (' oil
periodate solution. Barium chloride, white pre- of whiter-green '). Diazotised aniline or sul-
cipitate. Manganous sulphate, red precipitate phanilic acid gives an orange azo- compound.
Mn 2 HI0 6 turning brown. Reducing agents
, Acetates.
(H 2 S0 3 Ti
, 2 (S0 4 ) 3 , Zn, etc.) convert periodates Ferric chloride, a dark-red colouration, dis-
readily into iodides. Mercuric nitrate, orange- charged on boiling, with precipitation of a basic
red precipitate 5HgO,I 2 7 , different from ferric acetate. Also discharged by hydrochloric
iodates, which give white Hg(I0 3 ) a . acid. Heated with strong sulphuric acid, acetic
Tartrates. acid is evolved. If alcohol is added, ethyl
Calcium chloride, in excess, a white pre- acetate is formed and is recognised by the smell.
H
cipitate (CaC 4 4 6 ), soluble in acids and in Formates.
potash solution. Complete precipitation requires Silver nitrate, a white precipitate in cpn-
time, and is promoted by vigorous agitation. centrated solutions ; the solution or precipitate
Potassium acetate, in presence of free acetic rapidly becomes black (Ag), especially on heat-
acid, a white crystalline precipitate 4 (KHC
4 6 ),
H ing. Ferric chloride, a red colour, discharged
forming slowly in dilute solutions. Silver on boiling, with precipitation of basic ferric
nitrate, a white precipitate, soluble in nitric acid formate ; also discharged by hydrochloric acid.
or ammonia. If the washed precipitate is dis- A solid formate mixed with concentrated
solved in the least possible quantity of dilute sulphuric acid gives off carbonic oxide even in
ammonia, and the solution heated, the test-tube the cold, but no carbonic anhydride.
is coated with a mirror of metallic silver. Fer- Gallic acid.
rous sulphate, followed by few drops of hydrogen Ferric chloride, in neutral solutions, a bluish*
peroxide and excess of caustic soda, bluish- violet black precipitate or colouration. Gelatin or
colouration. albumin, no precipitate. Potassium cyanide,
Citrates. red colouration, which disappears on stand-
Calcium chloride, or lime water, in excess in ing, but reappears on agitation in presence of
neutral solution, a white precipitate air. Caustic soda, green colouration gradually
ANALYSIS. 179
darkening, and with excess becoming brownish- as far as possible,

may be removed by repeated
reel. Lime water, bluish-grey precipitate. evaporation with strong hydrochloric acid, but
Tannic acid. this treatment is not admissible if the metals
Ferric chloride, bluish-green or bluish-black present form volatile chlorides ; if present, a
precipitate or colouration.
Gelatin or albumin, much higher degree of dilution is necessary. In
yellowish-white precipitate. Potassium cyanide, most cases precipitation is accelerated and the
no colouration. Caustic soda, reddish- brown precipitate rendered more granular by keeping
colouration gradually darkening. Lime water, the liquid warm. A
current of washed' hydrogen
grey precipitate. sulphide is passed through the solution until it
Phenol. is thoroughly saturated, and the flask is closed
Ferric chloride, violet colouration, destroyed and left in a warm place until the precipitate has
by acids. Bromine water, white precipitate settled. Molybdenum and the metals of the
(tribromophenol and tribromophenol bromide). platinum group are only completely precipi-
Concentrated sulphuric acid and a fragment of tated after prolonged treatment with the
gas.
sodium nitrite, on gently warming, greenish blue The precipitate is protected from air as far as
solution, turned red when poured into water, and possible during filtration, and the liquid used
changed again to blue by caustic alkali. for washing should contain
hydrogen sulphide in
order to prevent oxidation.
Pyrogallpl.
Silver nitrate or Fehling's solution, readily When arsenic is present, the liquid should
reduced. Caustic alkalis, brown solutions, rapidly be heated with pure sulphurous acid to reduce
darkening owing to absorption of oxygen. Form- arsenic acid, and the excess of sulphurous acid
aldehyde and strong hydrochloric acid, white pre- expelled before treatment with hydrogen sul-
cipitate becoming red, and finally purple. phide. In presence of antimony, tartaric acid
Uric acid. should be added to prevent co-precipitation of
Alkali urates reduce silver nitrate, and when basic antimony chloride.
heated with solid caustic soda, ammonia is When copper is precipitated as
sulphide in
evolved, and an alkali cyanide is produced. presence of zinc, the copper sulphide should be
Nitric acid: evaporate solution to dryness on washed once or twice with dilute hydrochloric
water-bath, reddish colouration, rendered violet acid of sp.gr. 1-05 containing hydrogen sulphide,
by ammonia, and turned blue by caustic soda and then with water also containing the gas.
(Murexide test). (j8) With previous precipitation by ammonium
sulphide. Add to the warm solution a consider-

QUANTITATIVE ANALYSIS. able quantity of ammonium chloride, which is
GRAVIMETRIC METHODS. found to promote precipitation and render the
A few metals are separated and weighed in the precipitate more granular, then ammonia to
metallic condition, but the majority of metallic
alkaline reaction, and a slight excess of am-
and acidic radicles are weighed in the form of monium sulphide. Close the flask and allow to
one or other of their compounds. In order stand in a warm place until the precipitate has
that a compound may be available for the deter- settled. Protect from air as far as possible
mination of one of its constituents, it should be during filtration, and wash with water containing
of perfectly definite composition and not highly ammonium chloride and a little ammonium sul-
hygroscopic or otherwise liable to alter ; it must phide or hydrogen sulphide.

be insoluble in the liquid in which it is formed, and The precipitated sulphide is treated in one
of two ways : it is collected on a weighed filter,
insoluble in an excess of the reagent ; it must be
dried at a definite temperature and weighed ; or
easily freed from impurities, and capable of
heated with sulphur in a current of hydrogen,
being brought into the proper condition for
and then weighed.
weighing without tedious and complicated opera-
tions. It is also desirable that the compound
In the first case it is essential to ensure the
should contain only a small proportion of the absence of co-precipitated sulphur, and for this
constituent to be estimated, since the effect of purpose the dried precipitate is treated with
the unavoidable error of experiment is thus pure carbon bisulphide and again dried, or, hi
minimised. An estimation of chlorine in the the case of cadmium, mercury, or bismuth, the
form of silver chloride is more accurate than an moist precipitate is treated with a warm con-
estimation of silver in the same way, since only
centrated solution of sodium sulphite, again
one-fourth of the error of experiment represents washed, and dried.
chlorine, whilst three-fourths represent silver.
When the sulphide is stable at a moderately
A description will first be given of a few high temperature and is not reduced by hydrogen,
Rose's method is employed. The dry precipi-
typical gravimetric methods ; then an alpha-
betical list of metals and acid radicles, with a tate is separated from the filter, which is then
summary of methods available in each case; burnt, and the precipitate and filter ash are in-
troduced into a porcelain crucible and mixed
followed by a series of methods of separation of with pure finely powdered sulphur. The crucible
general applicability. Special methods for the is provided with a perforated lid, through which
analysis of technical products will be found in
the articles passes a porcelain tube connected with a hydro-
dealing with these materials.
gen apparatus. A current of purified and dried
GENERAL METHODS OF ESTIMATION.
hydrogen is passed into the crucible, which
is
I. As excess of
Sulphides. gradually heated to full redness until
(a)With previous precipitation by hydrogen sulphur is expelled, allowed to cool in a current
sulphide. The solution should be moderately of hydrogen, and weighed.
dilute and Non-volatile sulphides may be collected in a
distinctly acidified with HC1, but any
large quantity of this acid must be avoided. wide Soxhlet tube and dried in situ over a ring
Nitric acid and burner at 300, while a current of pure dry
nitrates, which should be absent
N 2
180 ANALYSIS.
carbon dioxide is conducted through the tube. The cyanide is removed by treatment with water,
This treatment removes both moisture and the metal washed, dried, and weighed. Care
co-precipitated sulphur (Cahen and Morgan, should be taken that the metallic button does
Analyst, 1909, 34, 3). not contain small fragments of porcelain result-
II. As Oxide. ing from the corrosion of the crucible.
(a) With previous precipitation as hydroxide. IV. As Sulphate.
The solution is mixed with ammonium chloride, Barium, strontium, and lead are precipitated
heated to boiling, and ammonia added in slight from solutions in the ordinary way, but other
excess. A
large excess of ammonia will partially
metals are converted into sulphate by treatment
redissolve some of the precipitate, and must be with the strong acid, the method being only
expelled by The is washed available when a single metal is present in com-
boiling. precipitate
with hot water. bination with a volatile acid. The highly con-
If ammoniais inadmissible, pure caustic centrated solution, or better, the solid substance,
used as the precipitant. Excess is mixed cautiously with concentrated
potash or soda is sulphuric
of alkali must be avoided, and the precipitat acid in a platinum crucible and then gently
must be very thoroughly washed, since smali heated to expel excess of acid, the crucible being
quantities of alkali are somewhat firmly retained. inclined and the lid placed in a slanting position
In both cases it is better to precipitate in a across its mouth. A large excess of acid should
porcelain or platinum vessel than in glass. be avoided, and care must be taken that the
Non-volatile carbon compounds, such as temperature is sufficient to expel the excess of
free acid but not sufficient to decompose the
sugar, 'glycerol, alkaline, tartrates, and citrates,
&c., more or less completely prevent precipitation sulphate. Sulphates of the alkalis and alkaline
of hydroxides by ammonia or caustic potash, or earths may be heated to redness. Bismuth
soda, and hence must first be removed by calci- sulphate and zinc sulphate decompose if heated
nation. Moderately strong nitric acid attacks above 400 ; magnesium sulphate is not decom-
filter paper, forming soluble products, which posed at 450, nor barium or lead sulphate at
prevent the precipitation of metallic hydroxides. 500 (G. H. Bailey). A temperature of about
(#) With previous precipitation as carbonate. 350 is required to expel the last traces of free
The solution is nearly neutralised, heated to sulphuric acid. With lead or bismuth sulphate
boiling, and mixed with a slight excess of sodium a porcelain vessel must be used.
carbonate, boiling being continued until all
carbon dioxide is expelled. The precipitate is GRAVIMETRIC DETERMINATION OF METALS
washed with hot water. Ammonium carbonate AND ACID RADICLES.
can be used in some cases, and has the advantage Details of operations will be found under
of not introducing a fixed alkali. In these cases General Methods of Estimation (v. p. 179), and
the precipitate should be washed with water electrolytic and volumetric methods will be in-
containing a little ammonia and ammonium dicated under appropriate headings (v. p. 206).
carbonate. Aluminium.
The precipitated hydroxide or carbonate is (a) As with previous precipitation with
oxide,
placed in a crucible (with previous separation ammonium sulphide, ammonium carbonate, or
from the filter paper if the metal is easily re- as basic acetate (v. Methods of separation). The
ducible), and is gradually heated to full redness, aluminium hydroxide is maintained in its in-
care being taken that no reducing gases from the soluble hydrogel form by washing with dilute
name enter the crucible. Oxides of reducible aqueous ammonium nitrate. The hydroxide
metals must be heated in a porcelain crucible, may also be precipitated in a form suitable for
but in other cases a platinum crucible may be filtration by boiling the solution of the aluminium
used with advantage. If carbonates (or oxalates) salt with potassium iodide and potassium iodate
are being converted into oxides, it is important (Stock, Ber. 1900, 33, 548 ; Compt. rend. 1900,
to secure a circulation of ah- in order to remove 130, 175).
carbon monoxide and carbon dioxide as fast as (b) As phosphate. The solution is nearly
they are given off, and thus accelerate decom- neutralised, mixed with sodium acetate and a
position. This is done by inclining the crucible small quantity of acetic acid, heated to boiling,
and placing the lid across the mouth in a slanting sodium phosphate added in excess, and the pre-
position. cipitate washed with hot water, heated, ana and
,
III. As reduced Metals. weighed as aluminium phosphate (A1P0 4 ).

(a) In some cases the metal is precipitated Ammonium.
as oxide, which is then dried and heated in (a) As platinichloride (NH 4 ) 2 PtCl s (v. ôtas-
hydrogen as in Rose's method for sulphides, the sium). The platinic chloride solution should
reduced metal being cooled in hydrogen and be added before the liquid is heated, and evapo-
weighed. This method is especially valuable ration should not quite be carried to complete
when, as in the case of cobalt, the oxide obsti- dryness.
nately retains small quantities of alkali, which, (b) By distillation (v. ACIDIMETRY).
however, can readily be removed from the reduced Antimony.
metal by washing with water. (a) As sulphide Sb 2 S 3 (v. p, 179). The precipi-
(/3) The other method is to mix the oxide, tate is collected (i.) in a weighed Soxhlet tube
carbonate, &c., with five or six times its weight on an asbestos mat, and dried at 280-300 in a
of ordinary potassium cyanide, and heat in a current of carbon dioxide
(Analyst, 1909, 34, 3);
capacious porcelain crucible, at first cautiously or (ii.) in a Gooch crucible and dried in an air-
and afterwards to complete fusion. When re- oven in an atmosphere of carbon dioxide. An
duction is complete, the crucible is allowed to aliquot part is then placed in a porcelain boat,
cool, and is tapped occasionally to promote the and heated in a glass tube in a current of dry
collection of the reduced metal in a single button. carbonic anhydride until it becomes black, and
ANALYSIS. 181
all admixed sulphur is expelled. The loss of bdate Bi(NH 4 ) (Mo0 4 ), (Miller and Cruser, J.
weight is calculated to the whole quantity and Amer. Chem. Soc. 1905, 27, 16).
deducted from the weight at 100. Cadmium.
(b) As oxide Sb 2 4 , \vith previous precipi- (a) As sulphide CdS, which is dried at 100,
tation as sulphide. The sulphide is placed in a or dissolved in hydrochloric acid, and the solu-
porcelain crucible and treated with fuming nitric
tion evaporated to dryness with
sulphuric acid,
acid boiling at 86 until completely oxidised, the the residue gently ignited and weighed as CdSO .
4
excess of acid expelled, and the residue heated (b) As oxide, after precipitating as basic car-
with partial exposure to air until the weight is bonate from boiling solutions by potassium
(not
constant. The sulphide may also be mixed with sodium) carbonate and collecting in a Gooch
30 to 50 times its weight of precipitated mer- crucible (Amer. J. Sci. 1906, 20,
456).
curic oxide and heated cautiously until of con- Calcium.
stant weight. A deep capacious crucible with (a) As
oxide CaO, after precipitation with
a lid having a side tube for the exit of vapours ammonium carbonate or ammonium oxalate
has been devised for this and similar estimations. (v. Utz, Oest. Chem. Zeit. 1904, 7, 510). In the
Arsenic. latter case the solution is made alkaline with am-
(a) As As 2 S 3 (v. p. 179), which is
trisulphide monia, heated to boiling, and mixed with excess
dried 100. The dry precipitate should
at of ammonium oxalate. The precipitate is
volatilise completely when heated. washed with hot water, and strongly heated until
(b) As pentasulphide As 2 S 5 The arsenic is . its weight is constant.
oxidised to arsenic acid by chlorine in alkaline (b) As sulphate CaS0 4 by , igniting the car-
solution,and the precipitation then effected in bonate or oxalate with pure sulphuric acid.
warm acid solution after decomposing all the Chromium (in chromic salts).
chlorate (Brauner and Tomicek, Monatsh. 1887, (a) As oxide Cr 2 3 after precipitation by
,
8, G42 and Neher, Zeitsch. anal. Chem. 1893, 32,

; ammonia, or better, ammonium sulphide ;
or by
45). potassium iodide and iodate (Stock and Massaciu,
(c) Arsenic acid is estimated as magnesium Ber. 1901, 34, 467).
pyroarsenate Mg 2 As 2 7 , in the same way as (b) As phosphate, in the same way as alu-
phosphoric acid (which see). The filter paper is minium.
moistened with a solution of ammonium nitrate Chromium (in chromic acid and chromates).
and dried before burning, in order to prevent (a) As oxide Cr,0 3 . The solution is neutral-
reduction (v. Ducru, Compt. rend. 1900, 131, ised, heated to boiling, and mixed with excess of
886; cf. also Friedheim and Michaelis, Zeitsch. a neutral solution of mercurous nitrate free from
anal. Chem. 1895, 34, 505). nitrous acid. The precipitate is washed with hot
Barium. water containing mercurous nitrate, and heated
(a) As sulphate BaS0 4 by precipitation with
,
to redness in a porcelain crucible until all mer-
sulphuric acid (v. Sulphuric acid). curial vapours are expelled. The mercurous
(b) As carbonate BaCO n , which may be chromate yields chromic oxide.
dried at a temperature below dull redness after (b) As chromate, by precipitation with barium
moistening the filter ash with ammonium car- chloride in acetic acid solution.
bonate (v. General Methods of Estimation). Cobalt.
(c) As silicofluoride (v. Methods of separa- (a) As metallic cobalt, after precipitation as
tion). cobaltic hydroxide by caustic soda or potash with
(d) As bromide (Thorne, Zeitsch. anal. Chem. bromine (v. p. 180). The solution must be free
1905, 43, 308). from ammonium salts, or all ammonia must be
Glucinum. expelled by boiling. The precipitate retains
As oxide G10, with previous precipitation by traces of alkali, and in accurate estimations the
ammonia or ammonium sulphide, but not caustic reduced metal should be washed with water,
soda or potash, or ammonium carbonate. dried, and again heated in hydrogen.
Bismuth. As sulphate CoS0 4 after precipitation as
(b) ,
(a) As oxide Bi 2 3 after precipitation with a

, sulphide, which is treated with nitric acid and
slight excess of ammonium carbonate. In pre- then with sulphuric acid (v. p. 180). If the
sence of chlorides or sulphates the
precipitate heated sulphate is at all black, it must be treated
will contain basic chloride or
sulphate, and in again with sulphuric acid.
this (or in any other) case the bismuth
may be Copper.
precipitated as sulphide, which is oxidised in (a) As cuprous sulphide Cu 2 S, using Rose's
the crucible by
fuming nitric acid boiling at 86, method, with previous precipitation as cupric
and then heated. or sodium thio-
sulphide by hydrogen sulphide
(b) As sulphide Bi 2 S 3 which is dried at 100
, sulphate (Chem. Zeit. 1895, 19, 1591).
and weighed at intervals of 20-30 minutes. The (b) As oxide, after precipitation by caustic
potash or soda in absence of ammonium
salts.
weight first decreases owing to loss of water,
and then increases owing to oxidation ; the (c) As cuprous thiocyanate
CuCNS (Rivot
minimum weight is taken as correct. Compt. rend. 1854, 38, 868 also Amer. J. Sci.
;
(c) As metallic bismuth (v. p. 180). Bismuth is 1902, 13, 20 and 138). The warm solution,
precipitated as metal by adding to slightly acid which must contain no free nitric acid, is slightly
solutions of its salts,
formaldehyde and excess of acidified with hydrochloric acid, and mixed
of a moderately strong
caustic soda, boiling and filtering through a gradually with an excess
Gpoch crucible, the precipitate being washed solution of equal parts of ammonium or potas-
with alcohol and dried at 105
(Vanino and sium thiocyanate and ammonium hydrogen
Treubert, Ber. 1898, 31, 1303). sulphite. When cold, the precipitate is collected
(d) Other methods: phosphate (Stabler and in a weighed Gooch crucible, washed with cold
Scharfenberg, Ber. 1905, 38, 3862), double moly- water anil 20 p.c. alcohol,
and dried at 1 10-120,
182 ANALYSIS.
The precipitate may also be converted into to redness until the weight is constant. If the
cuprous sulphide by Rose's method. Cuprous precipitate is black, owing to partial reduction,
thiocyanate is not quite insoluble, especially in it is moistened with a few drops of strong nitric
presence of much free acid. acid, and again heated until perfectly white.
Gold. (b) As oxide MgO, after precipitation as
As metallic gold. Nitric acid is removed hydroxide by barium hydroxide, or mercuric
by evaporation with hydrochloric acid. The oxide, or as double carbonate MgC0 3 (NH 4 ) 2 C0 3
solution is acidified with hydrochloric acid, (Zeitsch. anorg. Chem. 1908, 58, 427), the pre-
mixed with a large excess of ferrous sulphate cipitate being strongly ignited (v. Zeitsch. anorg.
solution, and heated gently for a few hours ; or Chem. 1901, 26, 347).
it is acidified with sulphuric acid, mixed with (c) As pyroarsenate (v. Pyrophosphate,
oxalic acid, and allowed to stand in a warm place Amer. J. Sci. 1907, 23, 293).
for several hours. Formaldehyde and hydrogen Manganese.
peroxide in alkaline solution can be used as pre- (a) As sulphide MnS, by Rose's method af
cipitants (Ber. 1899, 32, 1968). Nitrous acid is precipitation by ammonium sulphide.
also suggested (Jameson, J. Amer. Chem. Soc. (b) As oxide Mn 3 4 , after precipitation
1905, 27, 1444). The precipitate is collected on sodium carbonate, or ammonium carbonate
a weighed filter, washed and dried. (Tamm, Zeitsch. anal. Chem. 1872, 11, 425). The
Iron. hydrated peroxide precipitated by bromine and
(a) As ferric oxide Fe.jO 3 , after precipitation ammonia, on prolonged ignition yields Mn 3 4 .
by ammonia, caustic potash or soda, potassium (c)As pyrophosphate Mn 2 P 2 7 Ammonium .
iodide and iodato (v. Chromium), or as basic chloride and microcosmic salt are added in con-
carbonate, basic acetate or formate. The oxide siderable excess to the cold manganese solution
is heated to redness until its weight is constant ; followed by a slight excess of ammonia. The
if heated at a higher temperature, it is
partially mixture is then heated
the precipitate be-
till
converted into ferroso-ferric oxide Fe 3 O 4 . comes silky and After cooling for
crystalline.
(b) Ferrous and ferric salts can be separated 30 minutes, the precipitate is collected on the
and estimated gravi metrically by means of Gooch, washed with very dilute ammonia, and
barium carbonate and ammonium chloride, when ignited (Gooch and Austin, Amer. J. Sci. 1898,
the ferric salt is decomposed, precipitating ferric 6, 150).
hydroxide, and the ferrous salt remains in (d) As sulphate (v. p. 180, Gooch and Austin,
solution. Amer. J. Sci. 1898, 5, 209).
Lead. Mercury (in mercurous compounds).
(a) As sulphate PbS0 4 . The solution, which As mercurous chloride Hg 2 Cl 2 . The dilute
should not be dilute, is mixed with dilute sul- cold solution is mixed with a solution of sodium
phuric acid and twice its volume of alcohol, and chloride in slight excess, and the precipitate is
allowed to stand, and the precipitate washed collected on a weighed filter and dried at 100.
with alcohol. If the addition of alcohol is in- Mercury (in mercuric compounds).
admissible, the solution is evaporated with a As sulphide HgS, which is dried at 1(
(a)
large excess of dilute sulphuric acid, till fumes after precipitation by hydrogen sulphide.
are evolved. The residue is taken up with cold (b) As mercurous chloride Hg 2 Cl z The solu- .
water and quickly filtered on a Gooch crucible ; tion is mixed with excess of hydrochloric acid
and the precipitate is washed with dilute sul- and phosphorous acid (made by allowing ptos-
phuric acid and afterwards with alcohol to phorus to oxidise slowly in moist air), and allowed
remove all free acid. to remain in a warm place for twelve hours. The
(b) As sulphide PbS, by hydrogen sulphide precipitate is collected on a weighed filter and
and Rose's method. dried at 100.
(c) As oxide PbO, after precipitation by Molybdenum.
ammonium carbonate, avoiding an excess of (a) As lead molybdate PbMo0 4 . The solu-
ammonium salts. tion is heated to boiling, mixed with excess of
(d) As metal (v. p. 180). lead acetate, and boiled for a few minutes. The
(e)Other methods. As chromate and iodate. precipitate is washed with hot water, dried at
Magnesium. 100, and heated to low redness in a porcelain
(a) As pyrophosphate Mg^PÔ^. The solution crucible.
is mixed with ammonium chloride in sufficient
(b) As the oxide Mo0 3 The solution is
.
quantity to prevent precipitation by ammonia, neutralised with nitric acid, mixed with excess
made strongly alkaline with ammonia, and of a neutral solution of taercurous nitrate, the
then mixed with excess of sodium phosphate, or, precipitate washed with mercurous nitrate solu-
better, ammonium phosphate or microcosmic tion, dried, and heated until the weight is constant.
salt. Care should be taken to avoid rubbing or The metal is precipitated as sulphide either in
scratching the sides of the vessel. The liquid acid solution, or an ammoniacal solution is
is allowed to remain for a few hours, filtered, and saturated with hydrogen sulphide and then
the precipitate washed with a mixture of strong The
acidified. precipitate, collected in a Gooch
ammonia (1 part) and water (5 parts) until the crucible, is roasted to oxide. Molybdenite is
washings give only a faint opalescence with roasted to form trioxide ; this is extracted with
silver nitrate after acidifying with nitric acid. ammonia, and the filtrate evaporated and residue
The precipitation of the double phosphate is ignited (Analyst, 1906, 31, 312).
greatly accelerated and a granular non-adherent Nickel.
product obtained by shaking the mixed solutions (a) As oxide NiO, after precipitation as
in a stoppered cylinder. The precipitate is nickelic hydroxide (Ni(OH) s ) by caustic potash or
dried, cautiously heated in a platinum crucible soda with the addition of bromine in absence
until all ammonia is
expelled, and then heated of ammonium salts ; or after precipitation
ANALYSIS. 183
ammonium sulphide thoroughly saturated

with is evaporated down with excess of dilute per-
nickel sulphide being chloric acid until all the
hydrogen sulphide, the hydrogen chloride is
dissolved in aqua regia and the solution preci- expelled. The residue is taken up with alcohol,
the precipitate collected on a Gooch
pitated by caustic soda or potash. crucible,
As dimetJiylglyoximate washed with alcohol, and dried at 130 (Amer
(b)
J. Sci. 1897, 2, 263).
CH 3 -C NO- Ni-NO C CH 3
: :
Selenium.
As selenium. The solution
CH 3 C NOH -
: NOH : C CH 3 fied with hydrochloric acid, mixed with excess
is
strongly acidi-
(Ni
= 20-31 p.c.). A 1 p.c. alcoholic solution of sulphurous acid or sodium
hydrogen sul-
of climethylglyoxime (J. pr. Chem. 1908, 77, 44) phite, and boiled for about fifteen minutes.
is added to a hot dilute hydrochloric acid solution The precipitate is collected on a weighed filter
of nickel followed by ammonia in slight excess. and dried at a temperature below 100. Solu-
The red precipitate is collected on a Gooch tions of selenium containing hydrochloric acid
crucible, washed with hot water and dried at cannot safely be concentrated by evaporation
110-120 (Briinck, Zeitsch. angew. Chem. 1907, except in presence of a large quantity of alkaline
20, 834). chlorides, which prevent the volatilisation of the
(c) As nickel dicyanodiamidine Ni(N 4 5 C/)) 2
H .
selenium as chloride.
Dicyanodiamidine sulphate and caustic
alkali
Hypophosphorous acid in alkaline solution,
are added to an ammoniacal solution of nickel and potassium iodide in acid solution, have also
salt, the yellow precipitate collected
and dried been recommended as reducing agents (Zeitsch.
at 115. If cobalt is present, hydrogen peroxide anorg. Chem. 41, 448 and Amer. J. Sci. 1896,
;
is first added to the ammoniacal solution. [4] 1, 416). For a review of methods for esti-
Aluminium and iron are kept in solution by mating selenium, see Zeitsch. anorg. Chem. 1904,
means of tartaric acid (Grossmann and Schiick, 41, 291).
Chem. Zeit. 1907, 31, 335, 911). Silver.
Platinum. As chloride AgCl, or bromide AgBr. The
As metal. The
solution of platinic chloride solution is acidified with nitric acid, heated to
free from excess of acid is precipitated by am- boiling, and mixed with a slight excess of sodium
monia, or, better, potassium chloride (v. Potas- chloride or potassium bromide. Estimation as
sium), and the precipitate is filtered by Gooch's bromide is to be recommended, since silver
method or through a plug of thoroughly dried chloride is not quite insoluble in pure water.
asbestos contained in a weighed tube. The The precipitate is washed with hot water, dried,
precipitate is dried, heated to redness in a detached from the paper as far as possible,
current of hydrogen, washed with water to transferred to a porcelain crucible, and dried at
remove alkaline chloride, again dried, and 150, or heated slowly until it shows signs of
weighed. The metal is also precipitated by fusion at the edges, and weighed. The filter is
reducing agents (e.g. formic acid, alcohol in burnt and the ash added to the crucible, which
alkaline solution) ; and by metals such as mag- is again weighed. The increase in weight is
nesium or zinc (Chem. Zeit. 1905, 29, 293). filter ash and metallic silver. The quantity of
Potassium. bromide or chloride corresponding with the
(a) As platinichloride K.PtCl,.. The solu- latter is calculated and added to the weight of
tion, which must contain the potassium in the the precipitate.
form of chloride and be free from acid, is mixed Sodium is weighed in the form of chloride
with excess of platinic chloride and evaporated together with any potassium which may be
to dryness on the water-bath. The crystalline present, and is estimated by difference, or it may
residue is washed with strong alcohol, without be estimated directly as sulphate or chloride if
breaking the crystals, until the washings (which potassium is absent.
at first must be orange, showing the presence of The following reagent precipitates sodium
excess of platinum) are colourless. The pre- even from very dilute solutions, and is not
cipitate is left in the evaporating dish, and the interfered with by the other alkali metals or
washings are poured through a small filter. by magnesium and the metals of the alkaline
When washing is complete, the precipitate is earths. Three grams of bismuth nitrate and
transferred to a weighed porcelain crucible by 30 grams of potassium nitrite are dissolved in
means of a jet of alcohol from a wash-bottle, and water containing sufficient nitric acid to remove
the alcohol is decanted off through the filter. any turbidity, about 1-6 grams of caesium nitrate
The precipitate in the crucible is dried first at are added, and the solution diluted with water
70 till most of the alcohol is expelled, and then to 100 c.c. The precipitation should be carried
at 100 for half an hour. The filter is dried, and out in a stoppered bottle in an inert atmosphere.
any precipitate is detached from the paper as The precipitate, 5Bi(N0 2 3 ,9CsNO>6NaN0 2
) ,
far as possible and added to the contents of the contains 3-675 p.c. sodium (v. Ball, Chem. Soc.
crucible, which is then weighed. The filter is Trans. 1910, 97, 1408).
burnt, and the ash allowed to fall into the Strontium.
crucible, which is again weighed. The increase (a) As sulphate SrS0 4 The solution, which
.
in weight is filter ash and metallic platinum. must contain but little free acid, is mixed with
The amount of platinichloride corresponding excess of dilute sulphuric acid and at least an
with the latter is calculated and added to the equal volume of alcohol, and the precipitate is
weight of the precipitate (v. J. Amer. Chem. Soc. washed with alcohol. If alcohol cannot be used,
1895, 17, 453 ; and Zeitsch. anal. Chem. 1906, a much larger excess of sulphuric acid is added
45, 315 ; Chem. Zeit. 1906, 30, 684). and the precipitate is washed with cold water,
(b) As KC1O 4
perchlorate The solution . but the results are less exact.
containing potassium and sodium as chlorides (b) As carbonate SrC0 3 (which must not be
184 ANALYSIS.
heated too strongly) after precipitation by am- then neutralised with ammonia. The precipitate
monium carbonate. isdissolved in dilute hydrochloric acid, avoiding
Tellurium. any excess. The liquid is then saturated with nil
(a) As tellurium, by reducing solutions of sulphur dioxide and boiled, the precipitate ,ate
tellurous or telluric compounds with sulphur being collected, ignited, and weighed as TiO., (J.
dioxide and hydrazine hydrochloride (Lenher, Soc. Chem. Ind. 1900, 19, 419 ; also J. Ame aer.
J.Amer. Chem. Soc. 1908, 30, 387). Other reduc- Chem. Soc. 1903, 25, 1073 ; and 1910, 32, 957)>.
ing agents have been employed : sulphur dioxide Tungsten.
and potassium iodide, hypophosphorous acid, As tungstic anhydride 3 W0
The solutic
Dion .
and grape sugar in alkaline solution. containing the tungsten as an alkaline tungstate
(b) As dioxide Te0 2 (v. Amer. J. Sci. 1909, is neutralised with nitric acid and precipitat
(iv.) 28, 112). with a neutral solution of mercurous nitrat
Thallium. The precipitate is washed with a solution
(a) As thallous iodide Til. The solution is mercurous nitrate, dried, and heated in a
heated with sulphurous acid to reduce all the celain crucible, when tungstic anhydride is lef
thallium compounds to thallous salts, allowed to Fused lead tungstate, when boiled with strong
cool, and then mixed with excess of potassium hydrochloric acid, gives a precipitate of tungstic
iodide. The precipitate is washed with dilute acid (Brearley, Chem. News, 1899, 79, 64).
alcohol, and dried on a weighed filter at 170 Uranium.
(v. Baubigny, Compt. rend. 1892, 113, 544). (a) As the oxide U 3 8
. The solution, oxi-
(6) As thallous platinichloride. This salt is dised necessary by nitric acid, is heated to
if
very insoluble, but is difficult to filter (Crookes, boiling and mixed with a slight excess of am-
Select Methods, 4th ed. p. 172). monia. The precipitate of acid ammonium
Tin. uranate is washed with ammonium chloride solu-
As oxide SnO 2 which
, is obtained when tin tion, dried, and strongly heated.
or one of its alloys is treated with nitric acid. (6) As thepyropfawÂa<e(UO ? ) 2 P 2 7 ,obtained
The solution is boiled for ten minutes to ensure by precipitating uranyl ammonium phosphate
complete precipitation, and the precipitate is (U0 2 )(NH 4 )P0 4 with ammonium phosphate in
digested for an hour with dilute nitric acid the presence of ammonium acetate and igniting
(1:6) at 100 to remove other metals, washed the precipitate at low redness. For the appli-
with hot water, and ignited. cation of this process to uranium minerals, see
In other cases the tin is precipitated as Low's Technical Methods of Ore Analysis, 3rd
hydrated oxide. If the solution contains stannous ed. p. 223; and J. Amer. Chem. Soc. 1901, 23, 685.
salts, the latter are oxidised by chlorine or by Vanadium.
hydrochloric acid and potassium chlorate, am- (a) Asbariumpyrovanadate2T$&0-VzQ & The .
monia added until a slight precipitate forms, solution is neutralised with ammonia, heated to
and hydrochloric acid until the precipitate just boiling, mixed with excess of barium chloride,
redissolves.The solution is then mixed with a agitated, and cooled quickly out of contact with
moderately large quantity of a strong solution air. The precipitate is washed and heated.
of ammonium nitrate or sodium sulphate, and (b) As manganese pyrovanadale 2MnO-V 2 6 .
boiled for some time. The precipitate is washed The solution is mixed with a slight excess of ammo-
with hot water by decantation and on the filter, nium chloride and ammonia, manganese chloride
dried, and heated. To ascertain if precipitation or sulphate mixed with ammonium chloride is
is complete, a small quantity of the filtrate is added in excess, and the liquid is boiled two or
added to a hot solution of ammonium nitrate or three minutes and allowed to cool out of con-
sodium sulphate. tact with the air. The precipitate, which should
If the tin has been precipitated as stannic be brownish yellow and free from oxidation
sulphide, the latter is washed with a solution of products, is washed with cold water and heated.
sodium chloride, and finally with a solution of (c) As pentoxide 5VO
obtained (i.) by pre-
,
ammonium acetate, dried, and roasted in a cipitating barium or lead vanadate, decomposing
porcelain crucible until the weight is constant. with sulphuric acid, filtering, evaporating the
Decomposition is facilitated by adding a small filtrate,and igniting; (ii.) by precipitating and
quantity of ammonium carbonate. igniting mercury vanadate (iii.) by precipitating
;
In all cases the filter is burnt separately and ammonium vanadate by ammonium chloride
the ash dropped into the crucible. and igniting the precipitate.
Titanium. For other methods of estimating and separat-
As dioxide Ti0 2 after precipitation by
, ing vanadium, v. A. Carnot, Compt. rend. 104 t
ammonia. Usually the substance is dissolved 1803 and 1850; Chem. Soc. Abstr. 1887, 896;
in sulphuric acid, fused with potassium
or is Chem. Zeit. 1905, 29, 392 Amer. J. Sci. 1910,
;
hydrogen sulphate and dissolved in water. The 30, 220.

solution is and boiled for some
diluted largely Zinc.
time, when all titanium is precipitated as hy- (a) As oxide ZnO, with previous precipitation
drated oxide, which is rendered anhydrous by by sodium carbonate in absence of ammonium
ignition. The solution should contain 0-5 p.c. salts.
(6) As sulphide ZnS, by Rose's method after
of free sulphuric acid if less, the
; precipitate is
impure, if more, precipitation is incomplete precipitating with ammonium sulphide.
(Levy). In presence of iron the results are The filtration of the zinc sulphide may be
always somewhat too high. promoted by precipitating in the presence of
Baskerville recommends fusing titaniferous ammonium acetate or thiocyanate, and washing
iron ores with potassium hydrogen sulphate con- with a 5 p.c. solution of either of these salts.
taining some sodium fluoride. The product If mercuric chloride is added to the solution,
is boiled with water
containing nitric acid and the mixed precipitate of mercuric and zinc
ANALYSIS. 185
sulphides filters much better than the latter reduced by hydroxylamine in ammoniacal solu-
alone the former
;
is expelled on ignition. tion (Ber. 1905, 38, 1576).
Formaldehyde in
dilute nitric acid reduces chlorates in 30 minutes
ACID RADICLES. and bromates in 2 hours; iodates are not reduced
Carbonic acid. (Griitzner. Arch. Pharm. 1896, 294, 634 com- ;
The estimation of carbon in carbonates may pare Brunner and Mellet, J. pr. Chem. 1908 77
be made by a loss in weight method. The car- 33).
bonate is weighed into an apparatus fitted with Hydrobromic, hydrochloric, and hydriodic
a stoppered dropping funnel containing acid acids.
to decompose the carbonate, and an exit tube As silver salts (AgBr, AgCl, Agl). The solu-
containing strong sulphuric acid to dry the tion mixed with excess of silver
is
nitrate,
escaping gas. The apparatus is weighed with acidified with nitric acid, and heated to
boiling.
the acids, &c., after the carbonate has been The precipitate is treated exactly as in the esti-
introduced. The acid is then allowed to drop mation of silver.
on the carbonate until the decomposition is Hydrofluoric acid.
complete, and the liquid boiled to expel dis- (a) As calcium fluoride CaF 2 , in the case of
solved carbon dioxide. The apparatus is again soluble fluorides. The solution is mixed with
weighed and the loss of weight gives the a moderate excess of sodium carbonate, heated
amount of carbon dioxide. The apparatus is to boiling, and mixed with excess of calcium
figured in most treatises on quantitative analysis. chloride. The precipitate is washed, dried, and
More accurate results are obtained by weighing heated to redness in a platinum crucible, then
the carbon dioxide directly by absorbing it in treated with excess of acetic acid, evaporated to
weighed tubes containing soda lime or in bulbs dryness, and heated to expel excess of acid. The
containing aqueous caustic potash. For a com- product is now heated with water, and the in-
plete form of apparatus for this estimation, see soluble calcium fluoride filtered off, washed, and
Thorpe's Quantitative Analysis, 9th ed. p. 86, heated.
and Clowes and Cole man's Analysis, 8th ed. (b) Indirectly as silicon fluoride SiF 4 . The
p. 104. finely powdered solid substance is placed in
When carbonates and sulphides occur to- a deep platinum crucible and covered with three
gether, the gases evolved on treatment with or four times its weight of pure precipitated silica,
acid are passed into a solution of copper acetate the weight of which is accurately known. Sul-
acidified with acetic acid and heated to boiling. phuric acid is then added, and the crucible gently
Hydrogen sulphide is absorbed, with formation heated for half an hour. The temperature is
of copper sulphide, and carbon dioxide passes raised to expel most of the sulphuric acid, the
on. residue treated with hydrochloric acid, washed,
For the estimation of carbon dioxide in the dried, and heated. The hydrofluoric acid is
presence of nitrites, sulphides, and sulphites, see calculated from the loss in weight of the silica :
Marie, Chem. Soc. Trans. 1909, 1491 ; and =

4HF Si0 2 The amount of silica in the sub-
.
Wolkowitz, Zeitsch. angew. Chem. 1894, 165. stance must be known, and its weight added to
Chloric acid. that of the admixed silica.
Any chlorine present as chloride is determined, (c) By distillation and weighing as calcium
the chlorate reduced by a zinc-copper couple, fluoride. The fluoride is decomposed by concen-
und the chlorine again determined. The differ- trated sulphuric acid in a platinum apparatus ;
ence is the amount of chlorine existing as chlorate the hydrogen fluoride carried off in a current of
(Thorpe, Chem. Soc. Trans. 1873, 541 ). Thin gra- air and carbon dioxide and absorbed in a solution
nulated zinc is washed with caustic soda solution, of pure caustic soda contained in a platinum
then with dilute sulphuric acid, which is allowed dish. Calcium chloride is added to this solution
to act for a short time, and finally with water. and the precipitate (CaC0 3 and CaF..) washed,
It is then covered with about 100 c.c. of a 3 p.c.
ignited, and treated with dilute acetic acid in
solution of copper sulphate heated to 40-50. moderate excess. After evaporation to expel
When most of the copper has been deposited, this excess of acid, the residue is taken up with
the liquid is carefully poured off, and treatment water and the insoluble calcium fluoride collected,
repeated with a fresh quantity of solution. The washed, and ignited (Jannasch and Rottgen,
zinc-copper couple is now
very carefully washed Zeitsch. anorg. Chem. 1895, 9, 267). The
with distilled water by decantation, not more apparatus employed is figured in Janna?ch's
than 0-5 gram of potassium chlorate, or the equi- Praktischer Leitfaden der Gewichtsanalyse,
valent quantity of any other chlorate, is weighed 2nd ed. 411 (compare also J. Amer. Chem.
out into the beaker and dissolved in about 25 c.c. Soc. 1901, 23, 825; and Chem. News, 1905,
of warm water, which should
just cover the 92, 184).
couple. The liquid is heated gently for half an (d) Directly as silicon fluoride (Fresenius).
hour, then boiled for half an hour, dilute sul- The mineral is finely powdered and intimately
phuric acid added drop by drop until the white mixed with ignited quartz and heated with con-
precipitate of zinc hydroxide and oxychloride centrated sulphuric acid in a dry |J-tube at
just dissolves, filtered, the filtrate neutralised 150-160. A current of dry air free from carbon
with pure calcium carbonate, and the chlorine dioxide is drawn through the decomposition tube
estimated by standard silver nitrate solution and thence through a series of five U'* u^ es -
(Chem. Soc. Trans. 1888, 166). The first of these is empty and cooled by im-
This reduction may also be effected by mersion in cold water the second contains glass-
;
Devarda's alloy (Al 45, Zn 5, Cu 50). Jannasch wool, or, if the substance contains chlorine, half
recommends hydroxylamine sulphate and excess is filled with pumice impregnated with anhydrous
of nitric acid asa suitable reducing agent for copper sulphate, and the other half with pure dry
chlorates while bromates and iodates are best calcium chloride. The third and fourth tubes
186 ANALYSIS.
are weighed and serve to absorb the silicon enters. The dish and the funnel are rinsed with
fluoride ;the third contains pumice moistened very small quantities of acid, the object being
with water, and the fourth contains soda lime to use as little liquid as possible. The contents
and calcium chloride. The fifth tube is a guard of the flask are then rapidly boiled to dryness,
tube containing the same reagents as the fourth. the evolved gas being collected in the tube over
After one or two hours the decomposition of the mercury, and carbon dioxide is driven through
fluoride is complete, and the gain in weight of the the apparatus to expel all nitric oxide. The
absorption tubes represents the amount of silicon mixture of nitric oxide and carbon dioxide is
fluoride generated. This process may be ren- transferred to an apparatus for gas analysis ; the
dered volumetric (v. Volumetric section). latter absorbed by caustic potash, and the former
Hydrogen sulphide (sulphides). mixed with oxygen and absorbed by alkaline
Insoluble sulphides are decomposed by hydro- pyrogallol. Nitrites are converted into nitrates
chloric acid in a flask similar to that used in by addition of hydrogen peroxide during evapo-
the gravimetric estimation of carbonic acid, and ration of the original solution (v. Warington,
the gas evolved is led into two or three bulb Chem. Soc. Trans. 1880, 468, and 1882, 345).
\J -tubes containing a solution of bromine in (c) By standard indigo solution (Warington,
dilute hydrochloric acid, which converts the Chem. News, 35, 45, and Chem. Soc. Trans.
hydrogen sulphide into sulphuric acid. When 1879, 578).
decomposition is complete, the liquid in the flask (d) As 1 : 4-diphenyl-3 5-endanilodihydro-
:
is boiled, and the last traces of the gas are drawn triazole nitrate C 20 H, 6 4 N ,HNO 3 . A
10 p.c. so-
through the bulbs by means of an aspirator. lution of the base 1 :
4-diphenyl-3 : 5-endanilo-
The contents of the bulb tubes are transferred hydrotriazole
'
Nitron,'
to a beaker, heated to expel bromine, and the
sulphuric acid precipitated by barium chloride.
C 6H 6 -N- -N
Sulphides which are not decomposed by hy-
N-C.HJI
I
drochloric acid may be oxidised with aqua regia,

N-C 8H 6
hydrochloric acid and bromine, or hydrochloric
acid and potassium chlorate, the sulphuric acid in 5 p.c. acetic acid produces a voluminous
formed being weighed as barium sulphate. white precipitate in dilute nitric acid or nitrate
Nitric acid. solution. Nitrites interfere by giving a sparingly
(a) Indirectly, as ammonia, by means of the soluble salt with this base ; they are removed
zinc-copper couple (Thorpe). A zinc-copper by hydrazine sulphate. Bromides, iodides,
couple (v. Chloric acid) is made in a flask into chlorates, perchlorates, and chromates, are also
which is weighed a quantity of the nitrate cor- precipitated by nitron, and must be removed.
responding with not more than 0-5 gram of Organic matters do not seriously affect the
potassium nitrate, and sufficient water is added method, which has been tested successfully
to just cover the couple. The flask is attached with solutions containing 0-5 p.c. of gelatine,
to a condenser, the other end of which is con- and 2 p.c. of dextrin (Busch, Ber. 1905, 38,
nected with a U-tube or flask containing hydro- 861). The method gives favourable results for
chloric acid, as in the estimation of ammonia. nitrates in water or fertilisers (Collins, Analyst,
The liquid is gently heated for some time, and 1907, 32, 349).
then distilled nearly to dryness. After cooling, (e) Howard and Chick have shown that
a further quantity of water is added to the couple, cinchonamine gives a very insoluble nitrate and
and distillation repeated. The ammonia in the can be used in estimating nitric acid and its
distillate is estimated as platinichloride, or is salts (J. Soc. Chem. Ind. 1909, 28, 53).
received in a measured volume of standard acid Oxalic acid.
and titrated. The reduction can also be con- As calcium oxalate. The method is already
veniently effected by the use of Devarda's alloy indicated under Calcium.
(v. Chloric acid) in alkaline solution (Analyst, Phosphoric acid.
1910, 35, 307). As magnesium pyrophosphate Mg 2 P 2 7
. The
(b) Schloesing's method. When a solution of operation conducted as in the estimation
is
a nitrate is heated with an acid solution of a of magnesium. If magnesium sulphate is used
ferrous salt, the nitrate is decomposed, the as the precipitant, the precipitate may be con-
whole of the nitrogen being evolved as nitric taminated with basic magnesium sulphate ; it is
oxide, which is measured. The difficulty lies therefore advisable to employ a solution of the
mainly in obtaining the nitric oxide free from chloride, which is made as follows 85 grams of :
air. The apparatus employed consists of a small crystallised magnesium sulphate are dissolved in
distilling flask provided with a side tube which boiling water, acidified with 5 c.c. of hydrochloric
terminates under a gas-collecting tube in a mer- acid, mixed with an aqueous solution of 82
curial trough. The neck of the flask is fitted grams of crystallised barium chloride, boiled, and
with a cork, which carries a tube funnel provided filtered. Afew drops of magnesium sulphate
with a stop-cock and another tube connected solution are added to be sure that there is no
with a carbon-dioxide apparatus. Carbon di- excess of barium, then 165 grams of pure am-
oxide free from air is passed into the apparatus monium chloride, and 260 c.c. of ammonia, and
until all air is expelled and the gas issuing from the solution diluted to 1 litre. After two or
the exit tube is completely absorbed by caustic three days the solution is filtered. In many
potash. The substance containing the nitrate, cases the phosphoric acid is first separated by
which must be in the solid condition, is dissolved ammonium molybdate (v. Methods of separation).
in 2 or 3 c.c. of concentrated ferrous chloride Silicic acid.
solution, mixed with 1 c.c. of strong hydrochloric As Si0 2 Soluble silicates are acidified
silica .
acid, and introduced into the flask by means of with hydrochloric acid and evaporated to com-
the funnel tube, care being taken that no air plete dryness ; moistened with strong hyc *
ANALYSIS. 187
chloric acid, again evaporated to dryness, the All fluosilicates, even
topaz, evolve filicon
residue treated with dilute acid, and the insoluble fluoride on ignition, and water is estimated
by
silicawashed with hot water and ignited. mixing the mineral with lead oxide in a hard
Insoluble silicates are very finely powdered, glass tube, heating the mixture in a current of dry
intimately mixed with about five times their air and passing the gases over a
layer of lead
weight of a dry mixture of sodium and potassium oxide contained in the same tube. The water
carbonates in equal proportions, and heated to is collected and
weighed in calcium chloride tubes.
redness in a platinum crucible for half an hour.
The cooled mass is treated with water, acidified METHODS OF SEPARATION;
with hydrochloric acid, and evaporated as above.
A. The Estimation of the Metals in their Ores
(For the separation of silica when the alkalis
have to be estimated, v. Methods of separation,
and Alloys.
In this section the metals are
Group VI.) arranged in the
Sulphuric acid. order in which they occur in the
qualitative
As barium sulphate BaS0 4> by precipita- groups. Both gravimetric and volumetric me-
tion with barium chloride. The chief difficulty thods are included in this description, the
arises from the tendency of the barium sulphate latter being indicated wherever possible,
owing to
to separate in a finely divided condition and to the greater rapidity with which the
analysis can
carry down impurities, especially in presence of be executed.
nitrates and potassium salts. These sources of GROUP I.
error are avoided by taking care that the solution Silver is separated from all other metals
by
is somewhat dilute, is free from nitrates, and treating its ores and alloys with moderately
contains a moderate but not excessive quantity strong nitric acid, evaporating off excess of
of free hydrochloric acid. The solution and the solvent, diluting with water, and adding to the
barium chloride solution should both be heated filtered solution either hydrochloric acid or
to boiling, and mixed gradually, tvith continual sodium chloride. To remove any lead or thallous
agitation. The liquid may be filtered as soon as chloride which may be present, the precipitate
ithas become clear, and the precipitate is washed is extracted
repeatedly with warm water ; it
with hot water and heated to dull redness. If should, however, be remembered that silver
too little hydrochloric acid is present, the pre- chloride is not absolutely insoluble in hot
cipitate is liable to be impure ; if a very large water. Silver is conveniently estimated volu-
excess of the acid is present, precipitation is not metrically in the above dilute nitric acid solution,
quite complete (compare Allen and Johnston, after boiling off nitrous fumes, by adding ferric
J. Amer. Chem. Soc. 1910, 32, 588). indicator and titrating with standard ammonium
Sulphurous acid. thiocyanate in accordance with Volhard's method
Indirectly as barium sulphate after oxidation (see Volumetric section). The presence of
by bromine water, excess of bromine being ex- other metals having colourless salts does not
pelled by boiling. interfere with this process ; nickel, cobalt, and
Thiosulphuric acid. copper must not be present to any large extent,
Indirectly as barium sulphate after oxidation and mercury should be absent because of the
by bromine water, excess of bromine being ex- insolubility of mercuric thiocyanate. When more
pelled by boiling. than 60 p.c. of copper is present, the silver is
Water
is usually estimated
by difference. If precipitated with excess of alkali thiocyanate.
a direct determination is required, the method The well-washed silver thiocyanate is decomposed
to be adopted will by strong nitric acid, the sulphuric acid produced
depend upon circumstances.
In many cases it is sufficient to heat the substance precipitated by barium nitrate, and the Volhard
on a watch-glass, or in a crucible in a
drying titration effected without filtering off the barium
oven, at a definite temperature, until the weight sulphate (v. Ber. 1905, 38, 566).
is constant.
During weighing the dried sub- The silver in argentiferous galena is estimated
stance must be carefully protected from the by fusing the sulphide with crude potassium
air. Attention must, however, be paid to the hydrogen tartrate (argol), and sodium carbonate
possibility of the volatilisation of substances in an iron crucible, and by heating the lead -silver
other than water. Many hydrated haloid salts, button thus obtained in a porous bone-ash cru-
for
example, lose part of their acid. In such cible (' cupel ') until the lead is removed as
eases the substance is
previously mixed with oxide, partly by volatilisation and partly by
aknown weight of perfectly dry lead monoxide. absorption into the cupel. The residual silver
Ammonia, ammonium salts, and volatile organic is detached from the cold cupel and weighed.
matter may also be given off. If the Gold quartz is assayed for silver by heating
drying is
conducted in a glass tube, the vapours
may be the mineral with lead oxide, and a reducing flux,
led into standard acid and the ammonia deter- when the lead produced extracts both the gold
mined by titration the total loss, minus the
: and silver. This alloy is cupelled, and the silver-
'
ammonia, gives the amount of water. Some ' with strong
gold button is parted by heating
substances increase in
weight in consequence of nitric acid diluted with three parts of water ; the
oxidation. Frequently it is desirable to collect residual gold is collected, ignited, and weighed.
the evolved water and
weigh it directly. The The silver is precipitated by hydrochloric acid
substance is introduced into a
glass tube (plain, from the nitric acid solution. When more than
r with a bulb in the
middle) drawn out and 30 p.c. of gold is present in the button before
bent at right In order to
parting, this metal will retain
at one which silver.
angles end, passes
directly, without any intervening indiarubber prevent this retention, a known weight of silver
ibe, through the cork of a
U'tube containing is added to the fused button. (For further
;her calcium chloride or
pumice moistened details of the separations of gold, silver, and lead
with strong sulphuric acid ORGANIC ANALYSIS). in the dry way, see ASSAYING, pp. 322-327.)
(v.
188 ANALYSIS.
Thallium, in the more stable thallous con- Lead in its ores and alloys is usually separated
dition to which thallic salts are readily reduced, from other metals by dissolving the substance
in hydrochloric or nitric acid, or if necessary in
is separated from the metals of Group II. by
a mixture of the two acids, and evaporating down
precipitating the latter with hydrogen sulphide
in acid solution. Alkali hydroxides separate it the solution with sulphuric acid until white
from all metals, giving insoluble hydroxides, and fumes are evolved. The mixture is then cooled
ammonium sulphide, which precipitates thallous diluted with water, and the lead sulphate quickly
sulphide, separates this metal from the alkalis
collected. If the amount of lead is small, alcohol
and alkaline earths. Gravimetrically, thallium must be added to complete the precipitation.
can be weighed as acid sulphate T1HSO 4 , stable The lead sulphate thus obtained is freed from
at 240, and as sulphate T1 2 SO 4 , stable at low silica, stannic oxide, and other impurities by
red heat ; it can be precipitated and weighed dissolving it in an excess of ammonium or sodium
as iodide Til, platinichloride Tl 2 PtCl 6 and chro-
,
acetate.
mate Tl 2 CrO 4 Volu metrically, it can be esti-
.
When separated as lead sulphate, the lead
mated by the oxidation of thallous salts by per- can be estimated volumetrically by boiling the
manganate or by titrating with thiosulphate the precipitate with ammonium carbonate and then
iodine set free in accordance with the following dissolving the lead carbonate in acetic acid. The
reaction: T1C1 3 3K1 +Til = +
3K01 1, (Chem. + lead is thus converted into lead acetate which is
Soc. Proc. 1908, 24, 75). titrated with standard ferrocyanide using as indi-
GROUP II. cator drops of uranium acetate on a porcelain
Mercury in its ores is generally estimated by plate. The lead may also be reprecipitated as oxa-
distillation with quicklime in a current of coal late from the acetate solution by alkali oxalate,
the washed lead oxalate being then suspended
gas or carbon dioxide. The decomposition of
the mercury compounds is facilitated by mixing in dilute sulphuric acid, and titrated with
standard permanganate. From the solution of
copper strips with the quicklime, and the pre-
sence of this reducing agent is essential in the the sulphate in sodium acetate the lead can be
case of mercuric iodide. The mercury which precipitated as chromate by potassium dichro-
distils over is collected under water, washed, mate. The chromate is dissolved in dilute nitric
dried, and weighed. Ores containing only small acid, and reduced with methyl or ethyl alcohol.
amounts of mercury are decomposed by heating
The solution, rendered ammoniacal, is treated
with oxalic acid, when lead is precipitated and
titrated as above with standard permanganate (v.
Chem. News, 1896, 73, 18 ; J. Amer. Chem. Soc.
1896, 18, 737 ;
Zeitsch. anal. Chem. 1902, 41,
653). Lead may be separated from copper by
electrolysing a solution of the metals in dilute
nitric acid with a weak current (0-5-1 -5 amperes
and 1-4 volts), when the lead is precipitated as
dioxide on the anode (a platinum dish with un-
polished inner surface).
Bismuth is separated from all other metals
FIG. 8.
but those of Group II. by the precipitation of its
with iron filings in a porcelain crucible, a, having sulphide by hydrogen sulphide in acid solution.
a silver lid, /, which is cooled by a water-jacket, The insolubility of the sulphide in ammonium
6, laid upon it. The mercury condenses on the sulphide separates this metal from arsenic, anti-
under surface of the silver plate, /, which is mony, and tin. The further separation of bis-
weighed before and after the experiment (v. muth from mercury, copper, and cadmium pre-
Holloway, Analyst, 1906, 31, 66). sents no particular difficulty, and is effected by
Mercury is separated from all other metals taking advantage of the solubility of bismuth
in the wet way by dissolving the ore or alloy in sulphide in nitric acid (sp.gr. 1-25), and the
nitric acid or aqua regia, diluting considerably, precipitation of bismuth oxychloride on diluting
precipitating the sulphides of Group II. by hydro- considerably an acid solution of bismuth chloride.
gen sulphide, removing the arsenic-tin sub-group The problem of separating bismuth from lead
by means of yellow ammonium sulphide (not is, however, much more troublesome, and the
sodium sulphide or hydroxide), treating the following appear to be most trustworthy methods :
residual sulphides with dilute nitric acid (sp.gr. (i.) the separation of the bismuth
as basic nitrate
1-2-1 -3), and dissolving the final residue in and the solution of lead nitrate in dilute am-
aqua regia and filtering if necessary from sulphur monium nitrate (J. pr. Chem. 1858, 74, 345) ; (ii.)
and lead sulphate. The mercury can be re- the distillation of the mixed sulphides in a cur-
precipitated by almost neutralising the acid rent of bromine, when bismuth bromide is volati-
solution, adding in succession ammonium sul- lised, leaving behind lead bromide (Jannasch,
phide, caustic soda and ammonium nitrate. Praktischer Leitfadender Gewichtsanalyse,lsted.
The caustic soda redissolves the sulphide initially 155); (iii.) the precipitation of bismuth as the
formed as the soluble double sulphide Hg(SNa) 2 , basic formate a repetition of this operation gives
;
and from this the ammonium nitrate reprecipi- a precipitate free from lead, which is dissolved in
tates mercuric sulphide in a form suitable for dilute nitric acid, the solution almost neutralised
collection. The precipitate is washed succes- with sodium carbonate, and the bismuth then
sively with water, alcohol, and carbon disulphide, finally precipitated and weighed as phosphate
dried at 110, and weighed as HgS. (For other BiPO^ (Stabler, Chem. Zeit. 1907, 31, 615). The
methods of separating mercury, see Jannasch, lead in the filtrate from the formate sepa-
Zeitsch. anorg. Chem. 1896, 12, 1.32, and 359 ; ration is precipitated as sulphide, converted into
and Stabler, Chem. Zeit. 1907, 31, 615.) sulphate, and weighed as such. This method
ANALYSIS. 189
of separation gives accurate results (Little and deposited from a cyanide solution (0 -7-1 -2 amperes
Cahen, Analyst, 1910, 35, 301). and 4-8-5 volts) ; the use of a
rotating cathode
Copper is separated from the metals of Groups accelerates the rate of deposition
(compare
III., IV., V., and VI., by precipitation
as sulphide Flora, Amer. J. Sci. 1906, 70, 268 and 392 ; and
by hydrogen sulphide in acid solution. In Avery and Dales, J. Amer. Chem. Soc. 1897, 19.
alloys and ores it is generally separated
from 379).
antimony and tin by rendering these insoluble Tin, antimony, and arsenic are separated
by the action of moderately strong nitric acid. from the remaining metals of Group II. bv
If, however, the sulphides
of these metals and digesting the group precipitate at 80 with con-
arsenic are present, they are extracted from the centrated yellow ammonium sulphide, when the
precipitate with alkali sulphides (not ammonium sulphides of these three metals dissolve, leaving
sulphide). The insoluble residue, containing the
the other sulphides insoluble. Copper
sulphide
sulphides of copper, bismuth, lead, mercury, and appreciably soluble in this solvent, and in the
is
cadmium, is treated with nitric acid (v. Mercury presence of copper it is preferable to use sodium
and Bismuth). Copper is readily separated or potassium sulphide, but in the
presence of
from bismuth by means of ammonium carbonate, mercury these reagents are inadmissible, owing
which precipitates basic bismuth carbonate, to formation of the soluble double
sulphide
leaving copper in solution. The separation from Hg(SK) 2 In the presence of much lead a
.
cadmium may be effected by one of the following small amount of tin is retained in the insoluble
methods (1) Hydrogen
:
sulphide is passed residue. Arsenic rarely occurs in alloys, and
into a boiling solution of the sulphates of copper in these substances antimony and tin are
and cadmium in dilute sulphuric acid (1:4). separated from other metals as insoluble oxy-
The precipitated copper sulphide, which contains acids (metantimonic and metastannic acids) by
some cadmium, is redissolved in nitric acid, and, the use of nitric acid as solvent.
after expelling excess of the solvent, the precipi- Arsenic is separated from antimony and tin
tation is repeated. (2) The copper is preci- by distilling the hydrochloric acid solution of
pitated as cuprous thiocyanate, leaving cadmium the three elements with ferrous chloride; the
in solution. (3) The copper is converted into arsenic is volatilised as arsenious chloride; this
potassium cuprocyanide K 3 Cu(CN) 4 , with a compound is collected in cold water and the
considerable excess of potassium cyanide, and the arsenic precipitated as trisulphide (Fischer,
cadmium precipitated with hydrogen sulphide or Zeitsch. anal. Chem. 1881, 21, 266). Various
ammonium sulphide (compare also Browning, modifications of this method have been intro-
Amer. J. Sci. 1893, [3] 46, 280). duced ; the distillation is carried on in a current
The following volumetric processes for copper of hydrogen chloride and hydrogen sulphide,
are employed in the technical analysis of the the latter serving as the reducing agent
ores of this metal, (i.) The mineral is dissolved instead of ferrous chloride ; the volatilised
in hydrochloric and nitric acids, and the solution arsenious chloride is converted in the cooled
boiled down with sulphuric acid to expel the receiver into the trisulphide (Piloty and Stock,
volatile acids. The copper is precipitated from Ber. 1897, 30, 1649). (For other modifications,
the boiling solution by introducing a sheet of see Gooch and Banner, Amer. J. Sci. 1891, [3]
aluminium and redissolving in nitric acid with 42, 308; Andrews, J. Amer. Chem. Soc. 1895,
the addition of bromine to destroy nitrous 17, 869; Rohmer, Ber. 1901, 34, 33; Morgan,
fumes. The solution is neutralised with am- Chem. Soc. Trans. 1904, 85, 1001.)
monia, acidified with acetic acid, and treated The arsenic may also be separated from tin
with excess of potassium iodide, when the liber- and antimony by dissolving the three sulphides
ated iodine is titrated with standard thiosul- in ammoniacal hydrogen peroxide, neutralising
phate (Low, J. Amer. Chem. Soc. 1902, 24, 1082). the solution with mineral acid, acidifying with
(ii. ) A solution of potassium cyanide is standard- tartaric acid, and precipitating the arsenic
ised against pure copper foil by dissolving the as magnesium ammonium arsenate by the
latter in nitric acid,adding bromine, boiling to addition of ammonia and magnesia mixture
expel nitrous fumes and excess of bromine, adding (see Qualitative analysis).
ammonia till strongly alkaline, and titrating with The following method of separating arsenic
the cyanide solution until the blue tint dis- and antimony in their ores, leads to volumetric
appears. The copper ore is treated as in (i.), the processes for the determination of these elements
copper being precipitated by aluminium, re- (Low, J. Amer. Chem. Soc. 1906, 28, 1715). The
dissolved in nitric acid,and the resulting solution mineral is decomposed by heating with strong
titrated in manner
just described (v. Brearley, sulphuric acid (20 parts) containing potassium
Chem. News, 1897 76, 189). (For other methods hydrogen sulphate (1-4 parts), and 1 part of
of
separating and estimating copper, see also tartaric acid. The cooled product is taken up
Zeitsch. anorg. Chem. 1896, ii. 268 ; Chem. Soc. with 350 c.c. of hot water, 10 c.c. of strong hydro-
Abstr. 1901, ii. 197 ; J. Amer. Chem. Soc. 1905, chloric acid, and 3 grams of tartaric acid, and
27, 1224; Zeitsch. anal. Chem. 1907, 46, 128; the solution saturated with hydrogen sulphide.
J. Amer. Chem. Soc.
1908, 30, 760 Chem. Zeit. ;
The mixed sulphides are dissolved in aqueous
1908, 33, 263; Amer. J. Sci. 1909, (iv.) 27, 448.) potassium sulphide, and the filtrate evaporated
(For electrolytic estimation of copper, see down with 10 c.c. of strong sulphuric acid and
p. 25XM 3 grams of potassium hydrogen sulphate until
Cadmium separated from the other metals
is the sulphur and the greater part of the free aid
of Group II.
by the methods indicated under are expelled. The cooled melt is dissolved in
copper, lead, &c. In the presence of zinc, Fox 50 c.c. of strong hydrochloric acid and 25 c.c.
recommends precipitation in a solution con- of water, and arsenious sulphide precipitated
taining trichloroacetic acid (Chem. Soc. Trans. by hydrogen sulphide. The antimony remaining
1907, 91, 964). Electrolytically, cadmium is in the nitrate is precipitated as sulphide by
190 ANALYSIS.
diluting the solution and passing in more hydro- position of the tin is complete in about one hour
gen sulphide. The antimonious sulphide is again Henz. Zeitsch. anorg. Chem. 1903, 37, 1 ; and
dissolved in potassium sulphide, the solution /ahen and Morgan, Analyst, 1909, 34, 3).
evaporated nearly to dryness with strong sul- In Clark's original process the filtrate from
phuric acid and potassium hydrogen sulphate, the antimony sulphide, which contains stannic
the melt dissolved in dilute hydrochloric acid tin, ismixed with yellow ammonium sulphide
and titrated with standard permanganate. n excess and acidified with acetic acid. After
The arsenious sulphide is dissolved in warm some time the stannic sulphide is collected,
ammonium sulphide, and the solution heated washed with a solution of ammonium nitrate,
strongly with strong sulphuric acid and potassium and converted into stannic oxide by ignition,
[n accurate work the antimony sulphide is
hydrogen sulphate until all the sulphur and
nearly all the acid are expelled. The residue is redissolved, and the oxalic acid separation
boiled with water to expel sulphur dioxide, repeated in order to obtain the last traces of tin
neutralised, and titrated with standard iodine (compare Carnot, Compt. rend, 1886, 103, 258).
solution in the presence of sodium bicarbonate. (For descriptions of other methods of estimating
Arsenic may also be estimated in minerals tin and antimony in their ores and alloys, see
(which do not contain phosphates) by fusing the J. Chem. Ind. 1892, 11, 662; G. W.
Soc.
powdered ore with sodium carbonate and nitre Thompson, J. Soc. Chem. Ind. 1896, 15, 179 ;
or sodium peroxide, extracting the fused mass T. Brown, jun., J. Amer. Chem. Soc. 1899, 21,
with water and precipitating silver arsenate 780; Argenot, Zeitsch. angew. Chem. 1904, 17,
from the neutralised solution. This precipitate 1274; Levy, Analyst, 1905,30,361; Panajotow,
is redissolved in nitric acid, and the amount Ber. 1909, 42, 1296.)
of silver in it determined by standard thio- The following process, due to Pearce, gives a
cyanate; whence the quantity of arsenic pre- rapid volumetric method for estimating tin in
sent can be readily calculated. (For other its ores. The mineral is fused in a nickel crucible
processes for the estimation of arsenic in with about 20 parts of sodium hydroxide with
technically important materials, v. Clark, Chem. the addition of a little powdered charcoal ; the
Soc. Trans. 1892, 61, 424 ; Friedheim, Zeitsch. fused mass is dissolved (excepting silica) in
anal. Chem. 1905, 44, 665; Heath, Zeitsch. hydrochloric acid, and the solution reduced by
anorg. Chem. 1908, 59, 87 ; Gooch and Phelps, the addition of iron rods or sheet nickel. The
Amer. J. Sci. 1906, (iv.) 22, 488 ; McGowan and stannous chloride thus produced is titrated with
Floris, J. Soc, Chern. Ind. 1905, 24, 265 ; Sanger standard iodine solution in presence of suffi-
and Black, ibid. 26, 1115.) (For the detection cient hydrochloric acid (1 4) to prevent the
:
and estimation of minute quantities of arsenic, oxidation of any arsenic or antimony which may
v.ARSENIC.) be present.
Separation of tin and antimony. In the Gold and platinum are separated chiefly in the
absence of any large amount of lead or other analytical subgroup containing arsenic, anti-
metal giving a sulphide insoluble in am- mony, and tin. Fusion of the sulphides with
monium sulphide, tin and antimony can be sodium carbonate and nitre, followed by extrac-
separated from these metals by means of this tion with water, removes the arsenic. The residue,
reagent, but if lead is present in considerable treated with zinc and hydrochloric acid, reduces
amount the tin is never completely extracted, tin and antimony to the metallic state ; the former
a portion always remaining in the insoluble is dissolved boiling hydrochloric acid, and the
by
residue. In this case it is preferable to separate latter by and tartaric acids, whilst gold and
nitric
out the tin and antimony by oxidising them to platinum are left. Treatment of the mixed
their insoluble hydrated oxides by means of metals with chlorine water removes gold, and
nitric acid. These oxides when fused with dilute aqua regia then dissolves platinum, palla-
caustic soda in a silver crucible yield sodium dium, and rhodium. From this solution platinum
stannate and antimonate; the latter of these is precipitated by ammonium chloride and alcohol,
salts is practically insoluble in dilute alcohol and from the nitrate, after neutralisation with
(1 vol. alcohol, 2 vols. water), whilst the former sodium carbonate, palladium is precipitated as
is readily dissolved. A repetition of this process cyanide by mercuric cyanide.
with the insoluble antimonate leads to a com- The residue from the aqua regia treatment ia
plete separation. roasted hi the air ; osmium volatilises as the
When present as sulphides, these metals are tetroxide, ruthenium sublimes as the dioxide,
conveniently dealt with by Henz's modification whilst iridiumis left (v. Leidie", Compt. rend. 1900,
of Clark's method. The sulphides are dissolved 131, 888 and PLATINUM METALS).
;
in excess of aqueous caustic potash containing Molybdenum is precipitated as sulphide pre-

potassium tartrate ; the solution is gradually ferably from a sulphuric acid solution by treat-
heated to boiling with excess of 30 p.c. hydrogen ment with hydrogen sulphide under pressure.
peroxide. When the oxidation of the sulphides From the sulphides of the copper-lead subgroup,
is complete, excess of oxalic acid is added (15 separated by digestion with sodium sulphide
it is
grams for 1 gram of mixed metal), the liquid under pressure, when the molybdenum passes
boiled to destroy excess of hydrogen peroxide, into solution and is reprecipitated as sulphide
and hydrogen sulphide passed for some time by dilute sulphuric acid. Molybdenum sul-
through the hot solution. The precipitated phide is separated from the sulphides of anti-
antimony sulphide is dealt with as described mony and tin by dissolving the latter in hydro-
under gravimetric estimations (p. 180). The chloric acid. The sulphides of arsenic and
filtrate is treated with sulphuric acid, concen- molybdenum are dissolved in hydrochloric acid
trated to a small bulk (150 c.c.), and electrolysed and potassium chlorate, the arsenic precipitated
at 60 with a current of 0-2-0-3 ampere, and from the filtrate after adding ammonia and
2-3 volts, using a rotating anode, when the de- magnesia mixture as magnesium ammonium
ANALYSIS. 191
The final filtrate is acidified, and the sodium or ammonium carbonate. In
presence
of iron the liquid. becomes
molybdenum reprecipitated as sulphide. Moly- deep red, but no
bdenum is separated from phosphorus in a precipitate must be formed. Sodium, or, better,
similar manner. From tungsten it is best ammonium acetate, is added in sufficient but
separated' by heating the mixed trioxides or not excessive quantity, and the
liquid is boiled
their alkali salts at 250-270 in a current of until the precipitate becomes
granular and
hydrogen chloride, when the molybdenum
is settles rapidly.
Prolonged boiling makes the
completely volatilised as the additive com- precipitate slimy. The liquid is filtered whilst
pound Mo0 3 ,2HCl, while the tungsten remains lot, and the precipitate is washed with hot
in the non-volatile residue (Debray, Compt. water ; if the liquid is allowed to cool the
pre-
rend. 1858, 46, 1101 and Pechard, ibid. 1892,
:
cipitate is partially redissolved. The precipi-
114, 173). tate is converted into ferric and aluminium
Selenium and tellurium fall into the analy- oxides by ignition ; the other metals are in the
ticalsub-group containing arsenic, and after this filtrate. It is advisable, and in
presence of
element has been removed as magnesium am- nickel essential, to redissolve the
precipitate
monium arsenate (v. Molybdenum), the selenium and repeat the process. This method is not
and tellurium are precipitated by reducing agents available for the separation of chromium.
such as sulphur dioxide, hydrazine, &c. (i.) Sul- The same result can be obtained with
phur, selenium, and tellurium are separated by ammonium formate or succinate.
fusion with potassium cyanide in a stream of Aluminium and chromium from iron, zinc,
hydrogen. On dissolving the mass in water and manganese, nickel, and cobalt. Mix the solution
passing air through the solution, the potassium with a moderate quantity of pure normal potas-
telluride present is decomposed, and tellurium sium tartrate, then with pure caustic potash or
is precipitated. When the filtrate is acidified, soda until the precipitate redissolves, add am-
the potassium selenocyanate (KCNSe) is decom- monium sulphide in slight excess and allow to
posed, yielding selenium, (ii.) The mixed di- stand. Wash the precipitate with water con tam-
oxides of selenium and tellurium are dissolved ingammonium sulphide. Aluminium and chro-
in aqueous caustic potash ; the solution, faintly mium are in the filtrate, the other metals in the
acidified with hydrochloric acid, is diluted to precipitate. and chromium are absent,
If iron
at least 200 with boiling water, rendered
c.c. it is sufficient to add the alkaline tartrate,
just ammoniacal and rcacidified with acetic excess of ammonia, ammonium chloride and
acid. After 30 minutes the tellurium dioxide ammonium sulphide.
is collected, washed with cold water, and gently Separation of iron and aluminium. The fol-
ignited (Browning and Flint, Zeitseh. anorg. lowing methods have also been employed for
Chem. 1909, 64, 104). this important separation, (i.) Potassium hy-
Gold from all other metals : reduction of an droxide dissolves aluminium hydroxide, but not
acid solution by oxalic acid or sulphurous acid. ferric hydroxide ; the former is reprecipitated
Selenium from the metals : reduction with sul- from the filtrate by boiling with ammonium
phurous acid in hydrochloric acid solution. chloride or adding successively nitric acid and
GEOUP III. The metals of Group Ilia, are ammonia ; the iron precipitate is dissolved in
separated from those of the succeeding groxips acid and reprecipitated by ammonia, (ii.) The
by precipitation with ammonia in presence of two metals are precipitated with ammonia and
ammonium chloride the metals of Group III6.
;
the weight of the combined oxides determined.
are separated from those of the succeeding The mixture is then digested with strong hydro-
groups by means of ammonium sulphide (v. chloric acid (10 concentrated solution 1 water)
:
General methods of estimation). until all the iron has dissolved ; the presence of
Iron, aluminium, chromium, uranium, free chlorine or hydriodic acid assists the solution
glucinum, and cerium, from zinc, manganese, of the ferric oxide. If alumina predominates, it
nickel, cobalt. The solution, which must contain may be necessary to fuse the mixed oxides with
iron and uranium as ferric and uranic salts, is potassium pyrosulphate. The solution is satu-
nearly neutralised, mixed with excess of finely rated with hydrogen sulphide to reduce the iron
divided and recently precipitated barium car- to the ferrous condition ; the excess of this sul-
bonate, and allowed to remain hi a closed vessel phide expelled by carbon dioxide, and the
is
at the ordinary temperature for some hours liquid titrated with standard permanganate.
with occasional agitation. In presence of nickel The proportion of aluminium is determined by
and cobalt, ammonium chloride should be added difference, (iii.)
Iron and aluminium may also
to prevent precipitation of traces of these metals. be separated by treating the mixed chlorides
Filter and wash with cold water. The
precipitate with strong hydrochloric acid and ether (equal
may contain ferric,chromic, aluminium, glucinum, vols.) ; the aluminium chloride is precipitated,
eerie and uranic hydroxides, mixed with barium collected, washed with ethereal hydrochloric
carbonate ; the filtrate contains the other metals, acid and ignited with mercuric oxide (Gooch and
together with some barium. In both cases the Havens, Amer. J. Sci. 1896, 2, 416). (iv.) The
barium can be removed by means of sulphuric separation of small quantities of
aluminium
acid, but as the barium sulphate carries down from excess of iron has been successfully effected
by the use of phenylhydrazine. The iron
small amounts of the other metals, it is preis
ferable to separate the metals of Groups III. first reduced to the ferrous condition by adding
hydrochloric acid and ammonium bisulphite,

and IV. by a double precipitation with am-
monium sulphide (Treadwell). and the solution almost neutralised with am-
Iron and aluminium from zinc, manganese, is
monia, a slight excess of phenylhydrazine
nickel, cobalt, uranium, and metals of the suc- then added, and after one hour the aluminium
with a solu-
ceeding groups. The solution, which must con- hydroxide is collected and washed
tain iron as a ferric salt, is tion of phenylhydrazine sulphite. In this way
nearly neutralised by
192 ANALYSIS.
aluminium can be separated from iron, man- with dilute sulphuric acid (1:6) at 170 in an
ganese, calcium, and magnesium (Hess and inert atmosphere (carbon dioxide) ; the solu-
Campbell, J. Amer. Chem. Soc. 1899, 21, 776). tion which contains uranyl sulphate (2 mols.)
Separation of iron, aluminium, and phos- and uranous sulphate (1 mol.), is titrated with
phoric acid. When the total amount of these standard permanganate solution.
substances is small, the precipitate obtained by
ammonia is ignited and weighed (A=Fe;,O 3
c.c.^KMn0 4 =0-03593U.
1
+A1 2 3 -|-P 2 5 ). The precipitate is then fused
with sodium carbonate and silica, and the mass Uranium ores are treated in the follow!
extracted with water containing a little am- way. The mineral (0-6-1 -0 gram) is dissolv
monium carbonate. The residue containing iron in nitric acid or aqua regia, silica removed
by
and aluminium is evaporated down with sul- evaporation, the soluble residue extracted with
phuric acid to dissolve the iron ; the solution is hydrochloric acid, and the metals of the copper
reduced with hydrogen sulphide as in the pre- group precipitated by hydrogen sulphide. The
ceding separation, and titrated with permanga- filtrate is oxidised with potassium chlorate, and
nate solution. The solution, which contains all treated successively with ammonium phosphate,
the phosphoric acid, is evaporated down with ammonia (till nearly neutral), and sodium
hydrochloric acid to remove silica ; the residue carbonate in excess. The mixture is boiled and
taken up with water, and the phosphoric acid sufficient ammonium chloride added to decom-
precipitated from the filtrate as magnesium pose excess of sodium carbonate. The preci-
ammonium phosphate. From the weight of pitate, which contains the iron, vanadium, &c.,
is washed with aqueous ammonium carbonate.
magnesium pyrophosphate obtained the amount
of P 2 Qk is determined, and the A1 2 3 is obtained This salt is removed from the filtrate by boiling
by difference. If the total amount of these alone and with nitric acid. The solution is
three substances is large, the original solution almost neutralised with ammonia, and to the
may be divided into three aliquot portions, in one boiling liquid are added successively micro-
of which the phosphoric acid is precipitated as cosmic salt, sodium thiosulphate, acetic acid,
ammonium phosphomolybdate, in the second and finally ammonium acetate. The precipitate,
part the iron is determined volu metrically, and uranyl ammonium phosphate, is collected, ignited,
from the third the total precipitate (Fe 2 O 3 . moistened with nitric acid, again ignited and
A1 2 3 ,P 2 S ) is obtained (compare Cooksev, weighed as (UO 2 ) 2 P a O 7 .
Analyst, 1908, 33, 437). Uranium is separated from thorium (and

Chromium is readily separated from many iron) by means of hydroxylamine hydrochloride,
metals, e.g. aluminium, by conversion into which in ammoniacal solution precipitates
chromate, which is not precipitated by alkalis. thorium and ferric hydroxides, leaving the
This can be done in one of the following ways, uranium in solution (Jannasch and Schilling,
(a) Make the solution alkaline with caustic potash Chem. Zeit. 1905, 29, 248).
or soda, saturate with chlorine, and then heat to Cerium is separated from other metals by
expel excess of gas, and decompose hypochlorites saturating the solution with sodium sulphate, this
by heating with ammonia, (b) Ammonium salt being added in fine powder. A crystalline
persulphate is added to a solution containing double sulphate of cerium and sodium separates,
chromium, iron, and aluminium. On boiling, and is washed with a saturated solution of
the chromium is oxidised to chromate, the acid sodium sulphate.
set free during oxidation being sufficient to keep Glucinum is precipitated with aluminium in
the iron and aluminium in solution (G. v. Knorre. Group III., and separated from aluminium and
Zeitsch. anorg. Chem. 1903, 16, 1097). (For the the other metals of the group by one of the
(i.) A
estimation of chromium in chromite and chrome following methods : saturated solution
steel, see Volumetric section.) of sodium hydrogen carbonate dissolves out
Aluminium from chromium. After chro- glucinum hydroxide from a precipitate con-
mium has been converted into chromic acid, the taining aluminium and ferric hydroxides, leaving
aluminium may be precipitated as hydroxide the latter unaffected (Parsons and Barnes,
or as phosphate (v. Determination of metals). J. Amer. Chem. Soc. 1906, 28, 1589). (ii.) Alu-
The filtrate is acidified, heated to boiling, and minium and glucinum chlorides are separated
sodium thiosulphate added until the chromium by saturating their solutions with hydrogen
is completely reduced it can then be estimated
;
chloride in the presence of ether ; the former is
as phosphate in the same way as aluminium. precipitated, the latter remaining dissolved
Uranium is separated from the other metals (Amer. J. Sci. [4] 11, 416). (iii.) The acetates
of this group by the solubility of its hydroxide, may be separated by the use of hot glacial
sulphide, and acid uranates, in ammonium car- acetic acid, from which solvent basic glucinum
bonate. acetate G1 4 0(C0 2 -CH 3 ) 6 separates on cooling
Uranium from iron and aluminium. An acid (Parsons and Robinson ; cf. also Glassmarn,
solution containing ammonium salts is mixed Ber. 1906, 39, 3366; and J. Amer. Chem. Soc.
with excess of ammonium carbonate and am- 1895, 17, 688).
monium sulphide in a closed flask. The pre- Barium carbonate decomposes glucinum
cipitate contains ferrous sulphide and aluminium chloride, thus separating this metal from those
hydroxide ; the uranium remains dissolved as of Group III6.
the doublecarbonate U0 2 -C0 3 ,2(NH 4 ) 2 Cp ? . Vanoilium separated from the majority of
is
The concentrated considerably, acidi-
filtrate is metallic elements by fusion with sodium car-
fied with hydrochloric acid, boiled, and the bonate and potassium nitrate ; the vanadium
uranium precipitated as ammonium diuranate dissolves in water as sodium vanadate. Chro-
with ammonia. The precipitate is ignited and mium and manganese would also be found in
weighed as U 3 8 Or this oxide is heated
. the aqueous extract, but from these metals
ANALYSIS. 193
vanadium separated by the addition of am-

is Columbium and tantalum are extracted
monium sulphide in excess, when chromium from columbite or tantalite by fusing the
and manganese are precipitated respectively as mineral with potassium hydrogen sulphate and
hydroxide and sulphide lea vine; vanadium in extracting the fused mass with hot water and
solution as a thiovanadate (cf. Zeitsch. anorg. hydrochloric acid. The residue is treated with
Chem. 5, 381 ; Compt. rend. 1904, 138, 810 ; ammonium sulphide to remove tin, tungsten,
and Hillebrand, Amer. J. Sci. [4] 6, 209). From and again extracted with hot hydrochloric acid.
arsenic, vanadium may be separated either by The final residue is then dissolved in hydro-
reducing with sulphur dioxide and precipitating fluoric acid, the filtered solution is treated with
arsenious sulphide with hydrogen sulphide or by potassium carbonate potassium tantalofluoride
:
heating the mixed sulphides in hydrogen chloride separates in acicular crystals and the mother
at 150, when the arsenic is volatilised (Field liquor furnishes potassium columbium oxy-
and Smith, J. Amer. Chem. Soc. 1896, 18, 1051). fluoride, crystallising in plates (compare Weiss
Vanadium is separated from phosphoric acid and Landecker, Zeitsch. anorg. Chem. 1909,
by reducing vanadjc acid to a hypovanadic salt 64, 65 and Chesneau, Compt. rend. 1909, 149,
;
with sulphur dioxide, and precipitating the 1132).

phosphorus as phosphomolybdate. Titanium. In addition to the process given
Vanadium and molybdenum are separated under the estimation of titanium, this element
by the action ov hydrogen sulphide on vanadic may be separated from iron by the following
and molybdic acids under pressure, moly- methods (i.) By adding ammonium sulphide to
:
bdenum sulphide being precipitated, or am- an alkaline tartrate solution of the two elements,
monium metavanadate may be precipitated by when ferrous sulphide is precipitated (Gooch,
the action excess of ammonium chloride
of Amer. Chem. J. 1885, 7, 283). (ii.) By precipitat-
(Gibbs, Amer. Chem. J. 1883, 5, 371) ; the latter ing titanic acid with phenylhydrazine (J. Amer.
method serves to separate vanadium from Chem. Soc. 1895, 25, 42 1 ). Titanium is separated
tungsten. from aluminium by boiling with an alkali acetate
(For methods of estimating vanadium in iron and dilute acetic acid, when basic titanium
and steel, see Brearley and Ibbotson, The acetate is precipitated.
Analysis of Steel Works Materials; and Blair, Titanium and zirconium are separated by
The Chemical Analysis of Iron.) the following methods : (i.) A
solution of the
Tungsten is separated from the majority of elements in dilute sulphuric and acetic acids is
other elements by fusion with alkali carbonate boiled for some time, when titanic acid is preci-
and extraction of the alkali tungstate with pitated (J. pr. Chem. 1869, 108, 75; Zeitsch.
water. This extract, when acidified with nitric anal. Chem. 9, 388). (ii.) The acid solution is
acid and evaporated to dryness, yields tungstic boiled with zinc till the titanium is reduced to
acid as a residue insoluble in water. From titanous salt, the zirconium is then precipitated
arsenic and phosphoric acids tungstic acid is by the addition of potassium sulphate (Compt.
separated by the addition of magnesia mixture, rend. 1863, 57, 298). (iii.) A
neutral solution
which precipitates the arsenic and phosphorus, of the nitrates is added drop by drop to a boiling
leaving the tungstate in solution (Gooch, Amer. concentrated solution of ammonium salicylate
Chem. J. 1871, 1, 412; and Gibbs, ibid. 1885, (1 : 5H 2 0), the solution boiled for one hour,
7, 337). concentrated, and the precipitated zirconium
The tungsten in wolframite may be estimated salicylate collected washed with am-
and
by fusing the finely powdered ore (0-5 gram) monium salicylate solution. Titanium sali-
with 6 parts of fusion mixture in a platinum cylate is soluble in hot water and remains in
crucible for half an hour. The fused mass is the filtrate (Dittrich and Freund, Zeitsch. anorg.
extracted with boiling water when alkali tung- Chem. 1907, 56, 337, 348).
state passes into solution together with silicate Cerium is precipitated in the aluminium
and stannate. The insoluble residue contains group (IILa), and, together with the other metals
iron, manganese, calcium, and magnesium with of the rare earths, is separated from iron and
small amounts of columbic and tantalic acids. aluminium by means of oxalic acid or am-
The filtrate is evaporated to dryness with excess monium oxalate. From lanthanum, praseo-
of nitric acid, and the residue, after heating at dymium, and neodymium it may be separated
120, is extracted with dilute ammonium nitrate by suspending the hydroxides in aqueous
solution the residue, which consists of tungstic
;
caustic potash and passing in chlorine until the
oxide with silica and stannic oxide, is weighed liquid is no longer alkaline. The cerium remains
and then treated with hydrofluoric acid and precipitated as the yellow hydrated dioxide,
weighed again. This second residue consists of whilst the other hydroxides are dissolved
tungstic oxide and stannic oxide, and the latter (Mosander). Various methods have been pro-
is volatilised
by heating repeatedly with am- posed similarly based on the oxidation of cerous
monium chloride until the weight of the final compounds to the eerie condition (v. Ann. Chem.
residue (W0 3 )
is constant. Pharm. 131, 359; Monatsh. 1884, 5, 508; Ber.
To remove tin the mixed oxides may be 35, 672).
ignited with zinc powder, and the residue, after Thorium, together with the rare earths, is
extraction with hydrochloric acid, is tungsten separated from the other elements by oxalic
trioxide (Angenot, Zeitsch. angew. Chem. 19, acid. The further separation is effected by the
140). following methods :
(For other separations of tungsten from is heated with

Monazite sand concern
(i.)
its usual associates, see J. Amer. Chem. Soc. trated sulphuric acid at 180-200 for 2 to 3
1900, 22, 772 ; Zeitsch. anorg. Chem. 1905, 45, hours, and the product taken up with water, and
396 ; Zeitsch. anal. Chem. 1908, 47, 37 ; Bull. the rare earths precipitated by the addition of
Soc. Chim. 1908, 13, 892.) oxalic acid. The precipitated oxalates, after
VOL. I.T.
194 ANALYSIS.
washing tillfrom phosphoric acid, are
free 209; Zeitsch. anal. Chem. 1904, 43, 382;
ignited, and the
resulting oxides dissolved in Jannasch and Riihl, J. pr. Chem. 1905, 72, 1 ;
hydrochloric acid. The excess of acid is ex- Moore and Miller, J. Amer. Chem. Soc. 1908,
pelled by evaporation at 100, the residue dis- 30, 593).
solved in water and treated with sodium Nickel from cobalt. The solution, which
thiosulphate. After 12 hours the solution is should contain but little free acid, is mixed with
boiled for 10 minutes and filtered. The pre- excess of pure potassium cyanide free from
cipitate contains thorium, but contaminated cyanate (the ordinary cyanide is fused with char-
with cerium it is therefore redissolved and
; coal, dissolved in water, filtered, and evaporated
the precipitation repeated until the filtrate gives in a silver dish), heated to boiling, and mixed
no precipitate on boiling with ammonia. At with a solution of mercuric oxide in mercuric
this stage the precipitate is ignited, fused with cyanide. The precipitate, Avhen washed, dried,
sodium hydrogen sulphate, the product dis- a.nd ignited, leaves a residue of nickel oxide
solved in water, and the thorium finally preci- NiO, which is weighed. Cobalt is usually deter-
pitated with oxalic acid, the precipitate being mined by difference ; but if direct estimation
ignited and weighed as Th0 2 (Fresenius and is required, the filtrate from the nickel is eva-
Hintz, Zeitsch. anal. Chem. 35, 543). porated to dryness, heated for some time
(ii.) The mixed oxalates obtained as before
with strong sulphuric acid, and the cobalt
from the monazite sand are decomposed, and estimated in the solution.
the metals converted into nitrates by repeated Nickel can be separated from cobalt and all
evaporation with nitric acid. The neutral solu- the other metals of Groups III. and IV. by pre-
tion of the nitrates is diluted with aqueous cipitation in ammoniacal or dilute acetic acid
ammonium nitrate (10 p.c.) warmed to 80, solution with dimethylglyoxime (see Estimation
and the thorium precipitated as peroxide by the of nickel). If ferric salts are present, they should
addition of pure hydrogen peroxide solution. be reduced to the ferrous condition, or tartaric
The precipitate, which contains a trace of acid is added before rendering the solution alka-
cerium peroxide, is filtered, washed with aqueous line ; the organic acid prevents the co-precipita-
ammonium nitrate, ignited and weighed as tion of iron, chromium, and aluminium (Brunck,
ThO, (Benz, Zeitsch. angew. Chem. 1902, 15, Zeitsch. angew. Chem. 1907, 20, 1845).
297 ;" compare Chem. Zeit. 1908, 32, 509). Cobalt from nickel, (i. ) In acetic acid solution,
(iii. ) Precipitation by organic acids, (a) Fumaric nitroso-)3-naphthol precipitates the cobalt as
acid precipitates thorium fumarate in 40 p.c. cobaltic nitroso-/3-naphthoxide (Ilinski and
alcohol, leaving the other rare earths in solution Knorre, Ber. 18, 699). (ii.) Cobaltic hydroxide is
(Metzger, J. Amer. Chem. Soc. 1902, 24, 901). precipitated from a neutral solution of the two
() m-Nitrobenzoic acid in aqueous solution metals by barium carbonate and bromine water
precipitates its thorium salt, the separation (Taylor, Proc. Manchester Phil. Soc. 1902, 46,
being complete in the presence of aniline. (ii.) 1). (iii.) Small quantities of cobalt can be
Under these conditions, cerium, praseodymium, detected and estimated in the presence of nickel
neodymium, and lanthanum remain in solu- by adding to a neutral solution concentrated
tion (Kolb and Akele, Zeitsch. angew. Chem. aqueous ammonium thiocyanate. On shaking
1905, 18, 92). with amyl alcohol and ether, these organic
(iv.) Boiling with potassium azide in neutral solvents extract the double salt (NH 4 ) 2 Co(CNS) 4
solution leads to the precipitation of thorium (blue solution), leaving the nickel in the aqueous
hydroxide, the salts of the other rare earth solution (Ber. 1901, 34, 2050 and 3913). Zinc
metals being unaffected (Dennis, J. Amer. Chem. is removed with the cobalt.
also
Soc. 1896, 18,
947). Fusion with potassium Cobalt is precipitated as double nitrite on
hydrogen fluoride separates thorium and cerium adding potassium nitrite to an acetic acid solu-
from zirconium, for on extraction with water tion of the two metals ; the nickel is left in solu-
containing a little hydrogen fluoride, potassium tion (Fischer, Pogg. Ann. 72, 477 ; and Funk,
zirconofluoride dissolves, leaving behind the Zeitsch. anal. Chem. 1907, 46, 1).
fluorides of thorium and cerium (Chem. News, Separation of zinc, manganese, nickel, and
1897, 75, 230). cobalt. The slightly acid solution of the four
Manganese and iron are separated in their metals is treated with sodium carbonate till a
alloys (ferromanganese, &c.) by dissolving the permanent precipitate is formed, which is redis-
alloy in hydrochloric acid with a little nitric solved by a few drops of hydrochloric acid ;
acid. After boiling off nitrous fumes, the solu- then for every 100 c.c. of liquid 16 drops of the
tion is filtered and diluted with boiling water same acid are added, followed by 10 c.c. of 20 p.c.
to 600 c.c. Ammonia is added till a faint ammonium thiocyanate ; the solution heated to
turbidity remains, excess of neutral ammonium 70 is then saturated with hydrogen sulphide;
acetate is then quickly added, and the solution the zinc in the precipitate is determined either
boiled. The basic ferric acetate thus precipi- as sulphide or oxide. Manganese is separated
tated contains some manganese ; it is therefore from nickel and cobalt by passing hydrogen
redissolved and the separation repeated. The sulphide into a solution of their salts in acetic
united filtrates are treated with excess of acid containing excess of ammonium acetate,
bromine followed by strong ammonia also in when nickel and cobalt are precipitated as
excess ; the liquid is vigorously agitated during sulphides; the filtrate may, however, still con-
the addition of these reagents, and then heated tain small amounts of these metals. The solu-
slowly to boiling. The precipitate is collected, tion is concentrated, treated with ammonium
washed with boiling water, ignited and weighed sulphide, and then with acetic acid. A further
as Mn 3 O (compare Riggs, Amer. J. Sci. 43, 135
,
; precipitate of nickel and cobalt sulphides is
Gooch, Zeitsch. anorg. Chem. 1898, 17, 268 ; thus obtained (v. Treadwell and Kramers,
Brearley and Ibbotson, Chem. News, 1902, 82, Zeitsch. anorg. Chem. 1901, 26, 184 ; com
ANALYSIS. 195
J. Soc. Chem. Ind. 1905, 24, 228; Bull. Soc. In solutions free from ammonium
salts, the
Chim. 1908, (iv.) 3, 114). magnesium can be precipitated as magnesium
Zinc from nickel and cobalt. Add excess of hydroxide by the addition of aqueous barium
pure potassium cyanide and precipitate the zinc hydroxide. The excess of barium is removed
with sodium sulphide. by ammonium carbonate and the alkalis are
GROUP IV. The metals of this group are determined in the filtrate. Magnesium chloride
separated from those of the following group is also separated from the alkali
chlorides by
by precipitation with ammonium carbonate (v. ignition with mercuric oxide, when mercuric
General methods of estimation). The liquid chloride and the excess of oxide volatilise,
leaving
is first made alkaline with ammonia and after- magnesia, from which the soluble alkali chlorides
wards heated to boiling to ensure complete pre- are readily separated.
cipitation. Alkalis from magnesium, (a) The solution
Barium from calcium and strontium. The is made distinctly alkaline with
pure milk of
dilute neutral or feebly acid solution is mixed lime (calcium hydroxide suspended in
water)
with excess of freshly prepared hydrofluosilicic and boiled for some time, care being taken that
acid and one-third its volume of 95 p.c. alcohol it remains alkaline. The liquid is filtered, made
allowed to stand twelve hours, collected on a alkaline with ammonia, and the calcium pre-
weighed filter, washed with a mixture of equal cipitated by adding ammonium carbonate and
parts of water and alcohol, and dried at 100. a small quantity of ammonium oxalate. The
Calcium and strontium are not precipitated. filtrate is acidified with hydrochloric acid and
Barium from strontium. Ammonium bichro- evaporated in a weighed platinum dish, heated
mate and ammonium acetate are added alter- to expel ammonium salts, and the alkaline
nately to a solution of barium and strontium chlorides weighed. They should dissolve com-
salts containing ammonium acetate. After pletely in water and should give no precipitate
three hours the precipitate, BaCr0 4 , is washed when mixed with ammonium carbonate and
with ammonium acetate solution, dried at 180-, allowed to stand for some time. If any calcium
and weighed (Kahan, Analyst, 1908, 33, 12; is present, it must be removed by
repeating the
v. Zeitsch. anal. Chem. 1905, 44, 742 ; J. Amer. treatment with ammonium carbonate and
Chem. Soc. 1908, 30, 1827). oxalate.
Barium and strontium from calcium. The (b) The solution, which must contain only
solution is mixed with a concentrated solution potassium, sodium, and magnesium, is mixed
of ammonium sulphate, using 50 parts of the with excess of oxalic acid, evaporated to dryness,
latter salt for one part of the mixed salts, and the oxalic acid expelled by heating carefully
heated to boiling with addition of a small quan- over a lamp until white fumes cease to come off.
tity of ammonia, and the precipitate washed The residue is treated with water, when potas-
with water containing ammonium sulphate. The sium and sodium dissolve as carbonates, whilst
filtrate contains the calcium, which can be magnesium oxide remains undissolved.
precipitated by ammonium oxalate. Alkalis from silicates, (a) The finely pow-
Calcium from strontium. Convert the metals dered silicate (1 gram) is mixed intimately with
into nitrates, evaporate to dryness, and extract an equal weight of ammonium chloride and
with a mixture of equal volumes of alcohol and eight parts of dense granular calcium carbonate,
ether, which dissolves calcium nitrate but not and heated to redness for half an hour. The
strontium nitrate. product is boiled with water in a platinum or
Calcium from strontium and barium. The silver dish for two hours, care being taken to
nitrates are dried at 140 and extracted with make up the loss by evaporation, the liquid
amyl alcohol, which dissolves out the calcium is filtered and the residue well washed with hot
salt, leaving the other two undissolved (Brown- water. The filtrate, which contains calcium and
ing, Amer. J. Sci. 43, 50, 314). the alkalis, is treated in the manner just de-
Calcium from magnesium. The calcium is scribed. In this method of decomposition,
precipitated by ammonium oxalate (v. Determi- which is due to J. Lawrence Smith, the silicate
nation of metals), adding sufficient of this salt is decomposed by the calcium oxide, which is
to convert both metals into oxalates, since dissolved by the fused calcium chloride formed
calcium oxalate appreciably soluble in a solu-
is by the action of the ammonium chloride on the
tion of magnesiumchloride. In very accurate calcium carbonate.
separations the precipitate should be filtered off, (6) The silicate is
treated in a platinum dish
redissolved in hydrochloric acid, and reprecipi- with excess of sulphuric and hydrofluoric acids,
tated by adding excess of ammonia and a small and the mixture evaporated on the water-bath
quantity of ammonium oxalate (cf. Richards, until the mineral is entirely decomposed. The
Zeitsch. anorg. Chem. 1901, 28, 71 Zeitsch.
; temperature is then raised to drive off the
angew. Chem. 1908, 21, 592 ; J. Amer. Chem. greater part of the sulphuric acid,
and the
Soc. 1909, 31, 917). cooled residue extracted with water. The sul-
GROUP V. Magnesium from alkalis. The phates are converted into chlorides by
barium
magnesium precipitated with ammonium
is chloride, the metals of Groups III. and IV. pre-
phosphate in the usual way, the filtrate evapo- cipitatedby ammonia and ammonium carbonate,
rated to dryness, heated to expel ammonium the magnesium removed by barium hydroxide,
salts, the residue evaporated two or three times and the excess of this reagent eliminated by
with strong nitric acid to remove hydrochloric ammonia and ammonium carbonate. The alkali
acid, and the phosphoric acid removed by stannic chlorides remaining in the final filtrate are
oxide (v. Phosphoric acid from metals ; v. Gibbs, estimated as indicated in the following section.
Amer. J.
Sci. [3] 5, 114; Neubauer, Zeitsch. Certain native silicates of the andalusite group
angew. Chem. 1896, 9, 439; Gooch, Zeitsch. are not decomposed completely by this treat-
anorg. Chem. 1899, 20, 121). ment with hydrofluoric acid ; these minerals
o 2
196 ANALYSIS.
may, however, be broken up by ignition with Chem. Soc. 1908, 30, 1104). (For the separation
ammonium fluoride. of lithium as phosphate and fluoride, see Ann.
(c) The alkali and other metals contained in Chim. Phys. 98, 193; Frdl. 29, 332, and
a refractory silicate may be separated by heat- Analyst, 16, 209.)
ing the mineral with lead carbonate. The pro- Rubidium and caesium are separated from
duct is extracted with nitric acid ; the lead each other and from potassium by taking advan-
removed as chloride and sulphide, and the tage of the difference in the solubility of their
metals in solution dealt with in the customary Rubidium hydrogen tartrate is
platinichlorides.
manner (Jannasch, Zeitsch. anorg. Chem. 1895, more than nine times less soluble than the
8, 364). caesium salt. Caesium carbonate alone of the
(d) Silicates of different types are decomposed alkali carbonates is soluble in alcohol. Caesium
by fusion with boric anhydride followed by gives rise to a series of sparingly soluble per-
extraction with methyl alcoholic hydrogen halides and yields double chlorides with lead and
chloride and evaporation to remove the boric antimony chlorides (v. Wells, Amer. J. Sci. 43,
acid as volatile methyl borate (Ber. 1895, 28, [3] 17; and Amer. Chem. J. 1901, 26, 265).
2822 ; Zeitsch. anorg/Chem. 1896, 12, 208). Ammonium can be removed from a
salts
Potassium from sodium. The metals are solution in two ways: (1) By evaporating to
converted into chlorides, which are evaporated dryness and carefully heating over a lamp until
to dryness and weighed together after drying at all fumes cease to come off. (2) By concen-
150. The salts are dissolved in water, mixed trating the solution and heating for some time
with platinic chloride in sufficient quantity to with excess of strong nitric acid. When evolu-
convert both into platinichlorides, and evapo- tion of oxides of nitrogen ceases, the liquid is
rated nearly but not quite to dryness. The evaporated to complete dryness and the nitrates
residue is then treated with alcohol, which dis- converted into chlorides by repeated treatment
solves the sodium but not the potassium salt with hydrochloric acid if necessary.
(v. Potassium). If the mixture is evaporated to
B. The Estimation of Acid Radicles.
complete dryness and heated so that the sodium
platinichloride becomes anhydrous, it dissolves Bromine from chlorine, (a) The two ele-
with difficulty in alcohol. Under some condi- ments are precipitated by excess of silver nitrate
tions reversion takes place and sodium chloride and weighed together. The filter ash is removed,
separates in white crystals insoluble in alcohol. the precipitate cautiously heated to fusion, and
In this case the alcohol is very carefully evapo- a portion poured into a weighed porcelain boat.
rated and the residue again treated with platinic The boat is again weighed, heated to fusion in
chloride. a current of dry chlorine in a glass tube until
In order to separate small quantities of po- all bromine is expelled, and the silver chloride
tassium from large quantities of sodium, advan- formed is weighed. It is advisable to heat in
tage may be taken of the fact that potassium chlorine for a further period of ten minutes and
chloride is more soluble than sodium chloride weigh again. The loss of weight multiplied by
in strong hydrochloric acid (Zeitsch. analyt. 4-223 gives the amount of silver bromide in the
Chem. 1880, 156). The dry mixed chlorides are weight of precipitate treated with chlorine, from
thoroughly moistened with concentrated hydro- which the quantity in the whole precipitate is
chloric acid 2 c.c. of the acid is then added,
:
readily calculated (v. Indirect methods of de-
and the salt thoroughly crushed and stirred with termination).
a glass rod. After standing for a few minutes This method gives accurate results if the
the acid is poured off into a small dish. Ten proportion of bromine is not too small. When
repetitions of this treatment, using 2 c.c. of a small quantity of bromine is mixed with a
acid each time, will suffice to remove all potas- large quantity of chlorine, the former may be
sium, whilst the greater part of the sodium concentrated by taking advantage of the fact
chloride is not dissolved. The acid solution is that if a limited quantity of silver nitrate is
evaporated to dryness and the potassium deter- added, the precipitate will contain all the bro-
mined as platinichloride (Chem. Soc. Trans. 39, mine, but only a portion of the chlorine. In one
506). By adopting this plan much less platinic portion of the substance the two elements are
chloride is required, and the separation is much determined together by complete precipitation.
more accurate. Another portion in somewhat dilute solution is
Lithium from sodium and potassium. When mixed with a quantity of silver nitrate insuffi-
a lithia-containing silicate (e.g. lepidolite) is cient for complete precipitation, and allowed to
broken up by one of the preceding processes stand in the cold for some time with repeated
the precipitable metals of Groups I. -IV. are agitation. The precipitate is collected, washed,'
first removed and the alkali metals converted and weighed, and the proportion of bromine
into chlorides. The combined chlorides are determined in the manner already described.
dried and weighed ; potassium is estimated in The quantity of silver nitrate which should be
one portion, and in a second portion the lithium used depends upon the relative proportions of
is estimated by extracting the chlorides with chlorine and bromine. If one part of bromine
amyl alcohol or with ether-alcohol saturated ispresent for every 1000 parts of chlorine, one-
with hydrogen chloride. Anhydrous lithium fifthor one-sixth of the silver necessary for com-
chloride is soluble in these media, whereas plete precipitation should be used ; if one part
sodium and potassium chlorides are practically to 10,000, only one-tenth ; if one part to 100,000,
insoluble therein. Lithium chloride has also only one-six'tieth (Fehling).
been separated from the chlorides of the other (ft) The solution of the two halides heated
alkali metals and barium by dissolving it in at 70-80 is treated with ammonium persul-
boiling pyridine, in which the others are in- phate, and the liberated bromine volatilised in a
soluble (Kahlenberg and Rrauskopf, J. Amer. current of air, collected in sulphurous acid, an" "
ANALYSIS. 197
estimated as silver bromide (Engel, Compt. rend. The calculation of the relative proportions of
1894, 118, 1263). these constituents becomes possible when one
Iodine is separated from chlorine in exactly the can obtain as many independent relationships
same way as bromine from chlorine. The loss of as there are radicles to be determined. The
estimation of chlorine and bromine (a) is a case
weight on treating with chlorine, multiplied by
2-569, gives the weight of silver iodide in the in point. The loss of weight due to the replace-
portion of precipitate taken.
ment of Br.(79-92) by Cl(35-46) is proportional
Iodine from chlorine or bromine. The solu- to the amount of bromine present. Let w
tion is slightly acidified with hydrochloric acid, loss of weight. Now
mixed with palladious chloride until precipi- Cl
= 35-46 and henCC Br - 35-46 Br D =w
tation is complete, and allowed to stand in a Br 79*2 79-92
>
warm place for twenty -four or forty-eight hours. or Br = 1-797 w i.e. the loss of
:
weight multi-
The precipitate of palladious iodide PdI 2 is
plied by 1-797 gives the quantity of bromine
collected on a weighed filter, washed with warm
present.
water, and dried at 100, or is reduced by heating
Similarly, the halogens in a mixture of
in hydrogen and the metal weighed.
soluble chloride, bromide, and iodide can be
Iodine can also be liberated by nitrous acid calculated from the following data : (i.) the
and estimated volumetrically (v. Volumetric amount of iodine present, set free by nitrous
methods). acid or hydrogen peroxide and acetic acid ;
Bromine, chlmine, and iodine from one
(ii.) the total weight of mixed silver halides
another, (a) The three elements are precipi- obtained from a known amount of mixture ;
tated and weighed together in one part of the
(iii.) the silver required for the complete pre-
solution. In another part the iodine is separated
cipitation of the three halogens this is obtained
;
as palladious iodide by palladious chloride, or
volumetrically. The indirect method can also
better, nitrate ; the excess of palladium is be applied to the estimation of sodium and
removed by hydrogen sulphide and excess of
potassium contained in the mixed chlorides
the latter by sulphate ; and the chlorine
ferric
from a silicate analysis (v. supra). The data
and bromine in the are precipitated com-
filtrate
required are (i.) the
:
weight A of mixed
pletely or fractionally and the bromine deter- chlorides the weight B of chlorine therein
; (ii.)
mined in the manner previously described. The
contained, this amount being determined either
chlorine is estimated by difference.
gravimetrically or volumetrically. Let x and y
(b) A direct method of estimating the three be the amounts of potassium and sodium
halogens in a mixture of their soluble salts has respectively, then these quantities are readily
been investigated by Jannasch and his colla-
calculated from the following equations, where
borators. The process in its present stage of
Cl, K, and Na represent the atomic weights of
development gives a sharp separation of chlorine these elements.
and iodine, but the results for bromine are
rather low. The mixture dissolved in 25 c.c. x+y=A-V
Cl Cl
B
=B
K* + Sa*
of water is heated to boiling with acetic acid ,
and hydrogen peroxide, and the liberated iodine

expelled by a current of carbon dioxide. The These indirect methods give useful results
bromine is then liberated by adding excess of only when the atomic or molecular weights of
hydrogen peroxide and moderately strong sul- the two radicles differ considerably, and when
phuric acid (5 :
3). The iodine is collected in the quantities present are approximately equal.
an ammoniacal solution of hydrazine sulphate Moreover, the results are affected to a consider-
and the bromine in alkaline hydrazine sulphate. able extent by comparatively small experi-
After acidifying with nitric acid, the iodine and mental errors.
bromine are precipitated as silver salts, and the Cyanide from chloride. Silver nitrate is
chlorine left in the distilling flask is similarly added in excess to an approximately 2 p.c.
precipitated (Ber. 1906, 39, 196, 3655 ; J. pr. solution of soluble cyanide and chloride. An
Chem. 1908, 78, 29; Zeitsch. anorg. Chem. 1, excess of normal nitric acid is now added, and
144 and 245). (For other processes for sepa- the mixture containing the freshly precipitated
rating the halogens, see Volumetric section ; and silver salts is distilled, when hydrocyanic acid is
estimated in the
Monatsh. 13, 1 ; Chem. Soc. Trans. 1893, 63, expelled quantitatively and
with
1051 ;
Compt. rend. 1898, 126, 187 ; Ber. 1899, distillate byprecipitation as silver cyanide
32, 3615.) acidified silver nitrate, drying this precipitate
Several indirect methods of estimating these at 110, and weighing in a Gooch crucible or on
paper (Plimmer, Chem. Soc.
three elements in a mixture have been pro- a tared filter Trans.
posed. They are based on the methods given, 1904, 85, 12 ; compare also Richards and
together with the fact that the radicles may be Singer, Amer. Chem. J. 1902, 27, 205).
precipitated exactly by a standard solution of Phosphoric acid from metals, (a)
The nitric
silver nitrate and the
precipitate weighed, the acid solution, as free as possible from hydro-
proportion of silver and halides in the precipi- chloric acid, and free from silicic and arsenic
tate being thus determined Fresenius, acids, is mixed with excess of
a solution of am-
(v.
Quantitative Analysis, sect. monium molybdate in nitric acid, heated gently
5).
for a few minutes, and filtered after standing for
Indirect Methods of Determination. This a short time. The precipitate is washed with
estimation of two or three halogens in a dilute nitric acid, dissolved in ammonia, and the
mixture furnishes a good example of indirect phosphoric acid precipitated by magnesia
methods of analysis, which are adopted in those mixture. This method is more especially ap-
of phosphoric acid
plicable when the quantity
cases where the separation of two or more
constituents is either impossible or inconvenient. is relatively small.
To prepare ammonium
198 ANALYSIS.
molybdate solution, 25 grams of the salt is dis- expelled by boiling. A small portion of the
solved in 100 c.c. of dilute ammonia, and the solu- ferrous iron is now reoxidised with a few drops
tion poured gradually with constant and vigorous of bromine water. Ammonia is added care-
agitation into 500 c.c. of a mixture of 3 vols. fully till a brown precipitate is formed which
strong nitric acid and 1 vol. water. TheJUquid becomes green on Acetic acid is added
stirring.
is heated at 50 for some time and the clear till the precipitate either dissolves or becomes
solution drawn off. whiter, and the solution then heated to boiling.
(b) By stannic oxide. The nitric acid solu- The precipitate, which contains all the phos-
tion is concentrated, mixed with fuming nitric phorus as ferric phosphate mixed with basic
acid boiling at 86, heated gently, and granulated ferric acetate, is dissolved in hydrochloric acid,
tin added gradually hi quantity not less than the solution evaporated nearly to dryness, excess
four times the amount of phosphoric acid pre- of citric acid added, and then magnesia mixture
sent. The stannic oxide produced' forms an in- and ammonia. The magnesium ammonium
soluble compound with the phosphoric acid. phosphate redissolved in hydrochloric acid
is
This is filtered off, washed with hot water, dis- and reprecipitated in the presence of citric acid
solved in caustic potash, the solution saturated to remove a small amount of iron, and ignited
with hydrogen sulphide, acidified with acetic and weighed as Mg 2 P 2 7 .
acid, and the stannic sulphide removed. The fil- (b) The filtrate from the silica is evaporated
trate is concentrated, any stannic sulphide which to dryness, the residue dissolved in dilute nitric
separates subsequently is removed, and the acid, ammonium nitrate added, and the solution
phosphoric acid is estimated in the usual way. heating to boiling. A
boiling solution of am-
The original filtrate from the stannic oxide con- monium molybdate is then added to phosphate
tains the metals previously combined with the solution, when ammonium phosphomolybdate is
phosphoric acid. precipitated quantitatively. This precipitate is

(c) The nearly neutral solution is mixed redissolved in ammonia to which ammonium
with silver nitrate and digested for some time nitrate and ammonium molybdate are added,
with excess of silver carbonate. The phos- and reprecipitated by adding hot nitric acid to
phoric acid separates as silver phosphate, the the boiling solution. The compound is now
metals remain in solution with the excess of pure, and is collected, washed with water con-
silver nitrate. The silver is removed by hydro- taining ammonium nitrate and nitric acid, and
chloric acid. either dried at 160-180 or gently ignited. In
(d) When the phosphoric acid is combined the former case it is weighed as (NH 4 ) 3 P0 4 ,
with metals which form phosphates insoluble hi 12Mo0 3 (containing 3-782 p.c. P 2 5 ) or in the
water but soluble in acetic acid, the solution latter as P 2 6 ,24Mo0 3 (containing 3-946 p.c.
is nearly neutralised, mixed with sodium or P 2 5 ) (v. Ber. 1878,11,1640; Zeitsch. anorg.
ammonium acetate, and a slight excess of ferric Chem. 1893, 32, 144 ; Amer. Chem. J. 34, 204 ;
chloride containing a known weight of iron Analyst, 1909, 34, 392 ; Chem. Zeit. 21, 442).
added. The liquid is heated to boiling, the Separation of phosphoric and titanic acids (v.
mixture of ferric phosphate and basic acetate J. Soc. Chem. Ind. 1895, 14, 443). Estimation
washed with hot water, dried, and heated in a of phosphorus in phosphor-bronze (v. J. Amer.
platinum crucible until the weight is constant. Chem. Soc.1897, 19, 396) in phosphor-tin
The weight of the precipitate minus the known (J. Soc. Chem. Ind. 1908, 27, 427).
weight of the ferric oxide gives the phosphoric Silicic acid from titanic acid. The silica
anhydride P 2 5 The precipitate may be mois-
. and titanium dioxide are weighed together, the
tened with nitric acid before the final ignition. mixture fused with a somewhat large quantity
Phosphoric acid in silicates. In the analysis of potassium hydrogen sulphate, and the cooled
of silicates (v. supra) the phosphoric acid is mass extracted with water. Silica is left un-
found together with iron and aluminium in the dissolved, titanic oxide dissolves, and can be
precipitate produced by ammonia in the filtrate precipitated from the filtrate by ebullition (v.
from the silica. This mixture is analysed in Titanium).
accordance with the method indicated under the Sulphides. If the sulphides are decom-
separations of metals (Group III.). posable by hydrochloric acid, the hydrogen
Phosphorus and silicon in iron and steel. The sulphide is absorbed in hydrochloric acid con-
iron or steel borings are dissolved in nitric acid taming bromine (v. Determination of metals).
(1HN0 3 sp.gr. 1-4:1H 2 0); the solution eva- Insoluble sulphides are decomposed by gently
porated to dryness, and the residue ignited heating with aqua regia or with hydrochloric
carefully until all the ferric nitrate is converted acid and bromine, and the sulphuric acid
into ferric oxide. The ignited residue is dis- estimated in the solution. The latter method
solved in concentrated hydrochloric acid heated gives the total sulphur.
nearly to boiling, when the ferric oxide and Sulphur in coal and coke. The finely pow-
phosphate pass into solution, leaving insoluble dered material(1 gram) is mixed intimately with
silica. The solution is evaporated to dryness, 1gram of calcined magnesia and 0-5 gram of
moistened with strong hydrochloric acid, and sodium carbonate, and ignited to dull redness
taken up with water ; the silica is collected, in an open platinum crucible for 1 hour, the
ignited, and weighed, its purity being tested by mixture being stirred every five minutes with
treatment with hydrofluoric and sulphuric acids. a platinum wire. The mixture is then heated
The phosphoric acid in the nitrate is estimated strongly for 10 minutes with 1 gram of am-
by either of the following methods. monium nitrate. The residue is extracted with
(a) The ferric solution, diluted and almost water and the sulphate determined in the usual
neutralised with ammonia, is reduced with sul- way (Eschka). The sulphur may also be deter-
phurous acid or sodium sulphite. Hydrochloric mined by heating the coal with sodium or potas-
acid is added and the excess of sulphur dioxide sium carbonate (4 parts) alone, and extracting
ANALYSIS. 199
the residue with hydrochloric acid and a few of known strength is added gradually until
drops of bromine (Nakamura). (Compare also the yellow colour of the methyl
orange just
Zeitsch. angew. Chem. 1905, 18, 1560 ; Chem. changes to red, thus indicating the point of
Zeit. 1908, 32, 349 ; J. Russ. Chem. Soc. 1902, neutralisation. The volume of acid required is
34, 457.) noted ; the weight of sulphuric acid which it
Sulphur in pyrites. The pyrites is oxidised contains, and hence the weight of soda which
either by fusion with sodium peroxide and it will neutralise, is known, and thus the
pro-
sodium carbonate or by oxidation with nitric portion of soda in the substance is determined.
acid and bromine. These processes convert the In order that a reaction may serve as the
sulphur to sulphate, which is estimated in the basis of a volumetric process, it must be
rapid,
usual way (v. J. pr. Chem. 1892, [2] 45, 103 ; simple, and definite, and not complicated by
Zeitsch. anorg. Chem. 6, 303, I.e. 1896, 12, secondary reactions. It should remain constant
129; J. Soc. Chem. Ind. 1905, 24, 7; Chem. through considerable variations in conditions,
News, 1906, 93, 213). and should not, for example, be materially
Sulphuric acid, from all other acids except affected by the degree of concentration of the
hydrofluosilicic by precipitation with barium solution. A final reaction should be rapid, per-
chloride in presence of hydrochloric acid. fectly decisive, and should only require a slight
Sulphuric acid from hydrofluosilicic acid. excess of the reagent for its production. In
is mixed with excess of potassium
The solution many cases a third substance is employed to
chloride and an equal volume of strong alcohol, indicate the completion of the reaction, and is
filtered through a weighed filter, and the precipi- termed an indicator. It is an internal indicator
tate of potassium silicofluoride (K 2 SiF 6 ), washed if it is added to the bulk of the liquid, an external
with a mixture of equal volumes of alcohol and indicator if drops of the liquid are removed and
water, and dried at 100". The sulphuric acid in brought in contact with it.
the filtrate is estimated in the usual way after The execution of volumetric processes in-
evaporation of the alcohol. volves the possession of accurately graduated
Titanic acid from silicic acid (v. Silicic acid instruments of three kinds, viz. flasks, pipettes,
from titanic acid). and burettes. The flasks should be fitted with
Boric acid. The borates of the alkali and well-ground stoppers, and should have some-
alkaline earth metals, when heated with pure what long necks, the graduation being not higher
methyl alcohol (free from acetone) and acetic than the middle of the neck, in order that there
acid, evolve all the boron present in the form of may be sufficient empty space for efficient agita-
methyl borate (b.p. 65). This liquid, when tion. Flasks holding respectively 1000 c.c., 500
added to moist lime, is completely hydrolysed c.c., 250 c.c., and 100 c.c., are used. Each flask
and the boric acid set free combines with the should have two graduation marks, viz. the
calcium oxide forming calcium borate. The containing mark, indicating the point to which
decomposition is effected in a small retort fitted the flask must be filled in order that it may
with a tap funnel for introducing further quan- then contain the particular volume of liquid, and
tities of methyl alcohol. The retort is connected the delivery mark or point to which the flask
with a water condenser and a conical flask must be filled in order that it may deliver the
a amount given volume of liquid when emptied by
containing weighed of quicklime. This drain-
lime is carefully slaked before the distillation,
ing. A pipette is usually a cylindrical bulb
and the methyl borate dropping into the conical a tube, the lower
terminating at each end in
flask is decomposed and the boric acid taken
up of which is drawn out to a jet, whilst the end
by the lime. The contents of the receiver are of the upper tube is slightly contracted so that
rinsed into a platinum dish, and the
methyl it may be readily closed by the forefinger and
alcohol evaporated at as low a
temperature as the flow of liquid regulated or stopped altogether.
The residue is cautiously ignited to a delivery mark, but
possible. Usually a pipette has only
destroy calcium acetate, and the increase in their
occasionally they are graduated throughout
weight of the lime represents the amount of whole length, and then take the form of a some-
boric anhydride B 2 3 obtained from the borate. what wide tube contracted to a jet at the bottom
Instead of lime, aqueous ammonium carbonate and terminating in a narrower tube at the top.
may be used in the receiver, and the liquid Pipettesof .100 c.c., 50 c.c., 25 c.c., 10 c.c., and 5
poured on to slaked lime (from a known weight useful. A burette
c.c. capacity are most generally
of quicklime) contained in a is a long tube of uniform bore,
12 to 15 mm. in
platinum dish
centimetres and
(Zeitsch. anal. Chem. 1887, 26, 18, 364). diameter, graduated in cubic
tenths or fifths. A convenient capacity is 50 c.c.
VOLUMETRIC METHODS. It is open at the top and contracted at the
In volumetric analysis the proportion of a lower end, to which a glass jet is attached by
substance is ascertained, not by separation and means of a piece of narrow indiarubbcr tubing.
weighing, but by determining the exact volume This tubing is nipped by a spring pinchcock,
of a
reagent solution of known concentration which is opened by the pressure of the fingers,
required to produce some particular reaction, the flow of liquid being thus
such as neutralisation, oxidation, or
precipita- regulated. A better plan is JH* S?~\
\^J
|
tion. The termination of the reaction is indi- to insert in the indiarubber {

cated by some end-reaction, which is a short of
usually a tubing piece glass
2
production, destruction, or change of colour, rod the diameter of which is 1
the formation of a to the
permanent precipitate or just sufficient prevent FIG. 9.
the cessation of the formation of a flow of liquid when the tub-
precipitate.
In If, however, the tubing
determining the strength of caustic soda, for ing remains circular.
example, it is coloured yellow with methyl
'
is "squeezed out laterally by the pressure

of
orange, and a dilute solution of sulphuric acid the thumb and fore finger (Fig. 9), a channel
200 ANALYSIS.
is made through which the liquid can pass, liquid may be covered with a 1 ayer of rectified
and by increasing or reducing the pressure, the paraffin of moderately high boiling-point, or the
flow of liquid can be regulated to a nicety. neck of the bottle may be provided with a cork
Certain reagents act upon indiarubber, and for carrying a tube containing caustic potash, or
these a burette with a glass stopcock should be alkaline pyrogallate, through which all air enter-
used. This form is, in fact, the most convenient ing the bottle has to pass. Astill better plan
for all purposes. The stopcock may be preis to fill the upper part of the stock bottle
vented from sticking by a little vaseline or with carbon dioxide, or, if the nature of the
paraffin, and from slipping out by a small india- solution permits, with coal gas, and connect it
rubber ring passed over the tap and round the by means of a cork and tube with a self-acting
burette tube. Sometimes the tube carrying the carbon dioxide apparatus or the ordinary gas
stopcock is not in the same line with the burette, supply. When solution is withdrawn, carbon
but is bent twice at right angles, so that the dioxide or coal gas enters. The burette should
burette jet, although still vertical, is one or two be kept permanently attached to the reservoir as
inches in advance of the burette itself. This just described, and the top end of the burette also
form is useful when titrating hot liquids, since put into communication with the inert gas supply.
the risk of heating the burette and its contents Graduation of the instruments. Accurate
is reduced. An alternative method is to have calibration of the measuring vessels is of course
the top of an ordinary burette funnel-shaped, necessary if correct results are to be obtained,
which admits of the burette being slung in a and it is never advisable to trust the makers'
stand by the funnel without other support, so graduations. All the instruments should be
that it can be tilted from the vertical when checked before being taken into use. Although
titrating hot solutions. it is sufficient for most purposes if the relative
When a burette is in use, it is important that volumes of the vessels are correct, they should
it should be supported in a vertical position. nevertheless be graduated in true cubic centi-
This can be done by means of a clamp attached metres. W T
ith gas-volumetiic apparatus this
to a stand similar to a retort stand. A
useful procedure is essential. If the calibration is per-
and easily constructed burette stand is described formed at a temperature of 18-20, variations
in J.Amer. Chem. Soc. 1905, 27, 1442. from the true volume resulting from the ex-
When several different solutions are being used pansion of the glass are so small for the intervals
continually, it is convenient to have the series of temperature through which the laboratory is
of burettes attached to a revolving stand, so likely to vary, that they may be neglected.
that each may be brought round to the front The vessels are checked by ascertaining the
when required. Short test-tubes inverted over weight of distilled water at a known temperature
the tops of burettes serve to keep out dust. which they will contain or deliver as the case
Standard solutions should be kept in well- may be. A large beaker of distilled water is
stoppered bottles in a cool place protected from placed in the balance room, and left for some
bright light. When many determinations of hours till its temperature has become constant.
the same kind have to be made, it is convenient The vessels to be calibrated are thoroughly
to keep the reservoir of standard solution at- cleansed by successive treatments with concen-
tached to the burette to facilitate the filling of trated caustic potash, distilled water, and a warm
the latter. A glass T-piece is introduced be- solution of chromic acid in concentrated sul-
tween the graduated part of the burette and the phuric acid, and then rinsed well with distilled
stopcock or pinchcock, and is attached by means water. The flasks are then dried. A narrow
of an indiarubber tube to a tubulus at the bottom strip of paper is attached vertically to the^ neck
of the bottle which contains the standard solution of the litre flask near the mark, the flask placed
and stands on a shelf above the burette. If this on one pan of a large balance capable of re-
bottle has no tubulus, a glass tube bent twice at sponding to 0-05 gram, and counterpoised.
right angles,with one limb reaching to the bottom Weights corresponding with the weight of water
of the bottle and the other connected with the which at the temperature of the supply in use
burette, is fitted into the neck of the bottle by will occupy 1000 c.c., are then placed in the pan ;
means of a cork, and is kept always full, so that the flask is filled nearly to the mark with water,
it acts as a siphon. There must, of course, be and water is gradually added until flask and
an entrance for air as the liquid flows from the weights are in equilibrium. Any water ad-
bottle. The flow of hering to the inside of the neck of the flask
liquid into the burette is regu-
lated by a pinchcock on the indiarubber tube. above the mark must be removed by means of
If the standard solution acts upon indiarubber, filter paper. If the mark on the neck of the
all these connections must be constructed of flask is thus found to be in error, a pencil mark
glass tubing. Burettes may now be obtained is made on the strip of paper at the point corre-
fitted with Greinerand Friedrich's three- way taps sponding with the lower edge of the meniscus,
(compare Fig. 12): these are readily connected to the glass above and below is evenly coated with
reservoirs and filled from the bottom. Filling a thin film of wax, and a horizontal ring is
the burette from the bottom avoids the forma- scratched through by means of a needle pre-
tion of air-bubbles, but it can also be filled cisely on a level with the pencil mark. The
from the top if the tube from the stock bottle ring is covered with a small piece of filter paper,
is bent slightly so that the liquid flows down which is moistened with hydrofluoric acid, care
the side of the burette. A convenient form of being taken to remove air-bubbles. After a
apparatus for this method, which is the only one few minutes the acid is washed off and the wax
available with an ordinary tap burette without removed, when a new mark will be found etched
a side-tube attachment, is described in Chem. into the glass.
News, 1906, 93, 71. When the standard solu- In calibrating volumes by determining
tion alters if exposed to air, the surface of the weights of water, it is necessary to reduce the
ANALYSIS. 201
and then divide

weight to vacuum standard,
theresult by the density of the water in order
to obtain accurately the volume in true cubic
centimetres. This calculation can be avoided
table
by making use of the following
:
t
202 ANALYSIS.
weighed, using the precautions that would
all of oxidising 0-005630 grams of iron, then since
be observed in an actual titration. From the the corresponding figure for a decinormal solu-
e OQA
table already given the true volume of this
0-005585, the permanganate
'
tion is is or
water is calculated Suppose this to be 4944 c.c.
.
-^ 5
Then the volume of the calibrating pipette must 1-008 times decinormal, and when using it to
_ estimate a substance of equivalent x, each c.s.
be
49^4
2.QQQ c.c. The differences between
the successive burette readings and the suc-
of permanganate will oxidise
^QQ X 1-008
cessive numbers 2-06, 4-12, 6-18 grams of substance. When only one or two
give at once
. . .
the burette errors at these inter- j

litres of a standard solution are required, and
the pure reagent is at hand, the exact quantity
vals, due regard being paid to the
J
sign of the difference. In the ex-

may be weighed out and diluted to the appro-
priate volume e.g. solutions of silver nitrate and
ample quoted, the correction to
;
be applied for 50 c.c. is obviously potassium dichromate may be thus prepared.

0-05 c.c. (see J. Amer. Chem. Measurements. In measuring out solutions,
Soc. 1900, 22, 149; and for a &c., the vessels must be perfectly dry, which is
modification of above, J. Amer. inconvenient, or must be well drained and then
Chem. Soc. 1901, 23, 484). rinsed out with a small quantity of the solu-
A
better design for a calibration to be measured, which is allowed to run
ting pipette is shown in Fig. 12, away.
which also illustrates the Greiner To read correctly the level of the liquid in a
and Friedrich three-way tap burette or pipette requires certain precautions.
(Morse and Blalock, Amer. Chem. In the first place, the instrument must be held in
J. 1894, 16, 479). a vertical position. Ordinary liquids form a
The gas burettes described concave surface, or meniscus, and the reading
under Gas analysis may be cali- should always be taken from the lowest point of
brated in much the same wayâs this curve, except in the case of very dark-
an ordinary burette, by filling coloured solutions, when the upper line of the
with water or mercury, drawing surface must be taken. The meniscus must be
off aliquot portions and weighing properly illuminated, and on a level with the
them, the temperature of the i
eye, in order to avoid parallax. The best

liquid being noted and the appro- method of avoiding this error is by the use of
priate correction made for expan- a burette having the graduation marks carried
sion. Any error thus detected :
half-way round the tube. In default of such
must be used as a correction in a burette, use may be made according to Mohr
subsequent readings. of a piece of card one-half of which is black
Standard solutions. These and the other half white. This is attached to
form the basis of all volumetric the burette by an indiarubber ring, and is ad-
FIG. 12. work, and great care should be justed so that the horizontal edge of the black
exercised in their preparation. half, which is lowest, is 2 to 3 mm., but not
When a solution is used only for the estimation more, below the meniscus. The lower edge of
of one substance, it may be convenient to the curve then appears black against the white
adjust its strength so that each c.c. is equiva- background. If the card is too low, the reading
lent to some simple and definite quantity of will be slightly too high. The little clamp and
the substance, say 0-01 gram; but for general screen designed by Gockel are based on the
purposes the so-called normal solutions should same principle. Some burettes are provided at
be employed. Anormal solution contains in the back with a dark vertical line on a milk
1000 c.c. the equivalent hi grams of the glass background. When the eye is on a level
active substance. A
solution of one-tenth this with the bottom of the meniscus, the dark line
strength is termed a decinormal solution, and appears to be drawn out to two fine points
one of a hundredth a centinormal solution. which just touch one another. By means of
Thus a normal solution of sulphuric acid con- these devices accurate readings can easily be
tains 49-04 grams of real acid per litre, a deci- taken even without using a burette float.
normal solution of iodine contains 12-69 grams In addition to the errors incident to all
of iodine per litre, and each litre of a decinormal in
analytical processes, another error arises
solution of potassium permanganate contains volumetric analysis, owing to variations in the
0-8 gram of active oxygen. concentrations of the solutions due to changes
Standard solutions are usually made up ap- of temperature. In the case of .tf/10-solutions
proximately normal or decinormal as the case this affects the results to the extent of 0-1 p.c.
may be, and afterwards accurately standardised for each 5 variation in temperature. With
by titration against a weighed amount of some concentrated solutions, especially those of the
pure compound. If the solution has been pur- acids and alkalis, the error is greater. The
posely made rather too concentrated, it may coefficients of expansion of certain standard
then be suitably diluted until exactly normal solutions have been determined by A. Schulze
or decinormal. Since accurate adjustment by Chem.
(Zeitsch. anal. 21, 167).
dilution is difficult to effect, and in certain cases Errors due to changes of temperature may be
inadvisable, it is usually better to avoid the eliminated by weighing the solutions instead of
process and determine a factor by which readings a
measuring them. The liquid is contained in
must be multiplied in order to convert them into light glass bottle, with a long jet-like neck,
and
equivalent readings of a normal or decinormal a tubulus at the shoulder which can be closed
solution. For example, if 1 c.c. of potassium by the finger, and the flow of liquid thus regu-
permanganate solution is found to be capable lated. The bottle is weighed, the solution
ANALYSIS. 203
of distilled water in a mortar and
poured gradually from it until the reaction is decanting the
complete, and the bottle again weighed. The solution into the stock bottle. After a day or
difference between the two weighings gives the two, the solution is filtered through
asbestos,
quantity of solution used. Convenient weight and standardised. If kept away from direct
burettes are described in Chem. News, 1877, sunlight, reducing gases and dust, it retains its
35, 98 J. Amer. Chem. Soc. 1908, 30, 31.
;
titre for a long time ;spontaneous decom-
its
Volumetric methods may be broadly classi- position is largely augmented by the presence
fied as I. Methods of Saturation ; II. Methods of solid dioxide, which explains the
necessity
of Oxidation and Reduction ; III. Methods of for the filtration through asbestos (Amer. Chem.
Precipitation ; and examples of the two latter J. 1896, 18, 401).
types of processes are indicated below. (For The solution is best standardised against
methods of saturation, v. ACIDIMETRY AND electrolytic iron, anhydrous sodium oxalate, or
ALKALIMETRY. ) by the iodimetric method of Volhard, using a
In the following section the methods for thiosulphate solution which has been recently
preparing and standardising the more com- titrated against pure iodine. (For the latter
monly employed solutions are first described, method, see Thiosulphate solution, and for the
followed by details of the various volumetric first, which requires a somewhat complicated
estimations for which these solutions may be apparatus, consult Treadwell-Hall, vol. 2, 81.)
conveniently employed, alphabetically arranged Titration by sodium oxalate. This method
under the names of the elements that are was proposed by Sorensen, and its accuracy
determined. has been fully established by various other
chemists (Zeitsch. angew. Chem. 1902, 15,
PREPARATION OF STANDARD SOLUTIONS. 1244 ; 1904, 17, 230 and 269 1905, 18, 1520).
;
The pure oxalate, prepared by Kahlbaum accord-

Potassium permanganate.
ing to Sorensen's directions, should be dried at
Employed as an oxidising agent, usually in 100 for a few hours before use.
acid solution, when the per-
dilute sulphuric Three or four portions of the oxalate, each
manganate decomposes according to the equa- weighing about 0-25-0-30 grams, are dissolved
tion :
in an excess of dilute sulphuric acid the solu- ;
2KMn0 4 +3H 2 S0 4 tions are warmed to 60-80, and titrated with

=K 2 S0 4 +2MnS0 4 +3H 2 0+50. the permanganate solution until a faint, per-
The oxidation of ferrous sulphate, for ex- manent pink colouration is obtained. From
manner the relation 2Na 2 C 2 4 2
= the value of the
,
ample, is represented in the following :
2KMn0 4 + lOFeSO 4 + 8H 2 SO 4 permanganate solution is calculated for each

titration, and the mean of the concordant
= K S0 4 +2MnS0 4 +5Fe 2 (S0 4 3 +8H 2
2 ) results adopted as the true value.
and of oxalic acid thus :
Many other methods for standardising per-
2KMn0 4 +5H 2 C,0 4 +3H 2 S0 4 manganate have been proposed, e.g. titration
= K 2 S0 4 +2MnS0 4 +8H 2 + 10C0 2. against crystalline oxalic acid H^CaO^HaO,
In order to facilitate calculation, these oxida- ammonium oxalate (NH 4 ) 2 C 2 4 ,H 2 0, ferrous
tions are conveniently expressed as a trans- sulphate FeS0 4 ,7H 0, Mohr's salt FeS0 4 .
ference of oxygen from one oxide to another, e.g. : (NH 4 ) 2 S0 4 ,6H 2 0, &c., which although at times
convenient, are less accurate than the methods
10FeO+Mn 2 7 = 5Fe 2 3 +2MnO. Standardisation against iron wire is not
given.
The utility of permanganate solution de- to be recommended, since the small quantities
pends upon the facts that such oxidation proof oxidisable impurities present consume more
their
cesses are usually quite easy to effect, the end- permanganate than would be required by
point being readily indicated by the solution own weight of iron, and the error is augmented
acquiring a faint permanent pink tinge, due to iron content
by making allowance for the actual
the presence of a
slight excess of permanganate, of the wire (Zeitsch. anal. Chem. 1903, 42, 359 ;
which thus acts as its own indicator. Oxida- Zeitsch. angew. Chem. 1901, 14, 1233; also
tion usually proceeds
rapidly at -the ordinary Treadwell-Hall, I.e.).
ot a
temperature, but solutions of oxalic acid must It is usual to express the concentration
be heated to 60-80. of the amount
It is most essential that permanganate solution in terms
a considerable excess of of iron it can oxidise; thus 1 c.c. of tf/10-
sulphuric acid should
be present (about 5 c.c. of concentrated acid
per KMn0 4 = 0-005585 gram Fe.
00 c.c. of solution), since otherwise the solution
becomes turbid owing to the separation of Potassium dichromate.
,
manganese dioxide, and the determination is A solution of this reagent may replace
The presence of hydrochloric acid in of ferrous salts,
spoilt. permanganate in the titration in the
the solution should be
avoided, if possible, since with the advantage that it can be used
it reacts with the or sulphuric acid.
permanganate under certain presence of either hydrochloric
circumstances, particularly in the presence of An excess of free acid is essential, the oxidation
iron salts. The error that thus arises can be of ferrous chloride, for example, proceeding
reduced to a
negligible amount by adding according to the equation
:
manganese sulphate to the solution, and titrating

very slowly (see Iron, p. 211).
Preparation and titration of the solution. A
decinormal solution which
containing 3-16 grams of is :
essentially
the salt per litre of solution is most convenient
for general use 2Cr0 3 +6FeO = Cr 2 3 +3Fe 2 3.
it is most
;
readily prepared by
grinding the solid repeatedly with small amounts A decinormal solution obtained by dissolving
204 ANALYSIS.
~ of oil of cassia to a litre of starch liquor is also
2
cn"
?
= 4-903 grams of the pure dry re-
recommended as a preservative.
crystallised salt in distilled water and diluting Sensitiveness of the iodine-starch reaction.
the solution to 1 litre, requires no further This depends upon several circumstances. It
standardisation. A
stock solution of approxi- is necessary to work with cold solutions,
pre-
mate strength may be standardised against ferably neutral or slightly acid ; the presence
several weighed amounts (1-0-1 -4 grams) of of mineral acid in high concentration greatly
pure ferrous ammonium sulphate by a similar impairs the sensitiveness of the reaction, since
it hydrolyses the starch.
procedure to that described under the standardi- It is essential that
sation of permanganate by sodium oxalate. The a soluble iodide should be present (usually this
titrations, however, are made in cold solution, is potassium iodide) in moderate amount ; the
and the dilute sulphuric acid used should be best concentration of potassium iodide to
gently boiled for half an hour to expel dis- employ is about N/15Q, since the sensitiveness of
solved air, and cooled rapidly just before use. the reaction then reaches a maximum (see Zeitsch.
Since the green colour of the chromic salt pre- anal. Chem. 1902, 41, 485; Amer. J. Sci. 1900,
vents the excess of dichromate from being seen, [iv.] 10, 151 ; J. Amer. Chem. Soc. 1909, 31,
an external indicator is necessary. Drops of a 1038).
dilute solution of potassium ferricyanide, free Good starch solution first yields a pink
from ferrocyanide, are placed on a white plate, colouration with iodine, which more iodine
and from time to time the end of a glass rod, develops into the blue colour ; starch which
previously dipped in the titrating flask, is produces green tints should be rejected ( J. Amer.
brought into contact with a drop of the ferri- Chem. Soc. 1908, 30, 31). It frequently happens
cyanide. As long as any ferrous salt remains a in titrating arsenious and antimonious oxides
blue precipitate is produced ; the approach of with iodine that various tints of red make their
the end is indicated by the decrease in intensity appearance instead of the usual blue coloura-
of the blue colouration, and when very near tion. This is due to impurity in the starch in :
the end about thirty seconds should be allowed such a case one or two grams of potassium iodide
for the colour to develop. The end-point is are added, the end-point being ascertained from
reached when the blue colour ceases to appear. the development of the yellow colour of the iodine,
The ferricyanide solution should be prepared and then confirmed by the starch (Amer. J. Sci.
only when required by dissolving in water a 1902, [4] 13, 379).
crystal of the salt which has been rinsed to remove For the iodine solution 25 grams of potassium
superficial ferrocyanide : the yellow colour of iodide are dissolved in a little water, 12-7 grams
the drops on the white plate should be barely of commercial iodine added, and the mixture
visible ; if the ferricyanide is too concentrated, shaken till the iodine has dissolved ; the solu-
the blue colouration changes through various tion is then filtered through asbestos and
shades of green into a brown tint. diluted to 1 litre. It should be kept in the
dark, and protected from dust. For the thio-
Iodine, Sodium thiosulphate, and Sodium arsenite.
sulphate solution the crystalline salt Na 2 S 2 3 ,
Decinormal solutions of these reagents are 5H 2 O is dissolved in distilled water, using
25 grams per litre, and the solution kept away
frequently used in conjunction with one another.
The reaction between iodine and sodium thio- from direct sunlight for two weeks before it is
is standardised. It then retains its titre for
sulphate essentially :
= months. For the sodium arsenite, 4-948 grams of

2Na 2 S 2 O 3 +I 2 Na 2 S 4 O 6 +2NaI
resublimed arsenious oxide are dissolved in a
although under certain circumstances oxidation little warm sodium hydroxide free from iron,
to sulphate proceeds to a small extent, even at
the solution rinsed into a litre flask, and made
the ordinary temperature (Pickering). When
just acid to phenolphthalem with dilute sul-
using decinormal solutions the end-point is phuric acid. A
filtered solution of 20 grams of
readily indicated by the appearance or dis- sodium bicarbonate in 500 c.c. of water is added,
appearance of the yellow colour of the iodine, and if the mixture reacts alkaline to the phenol-
provided the solution undergoing titration is phthalein, sulphuric acid added till the pink
not unduly diluted and is otherwise colourless. colour disappears. This solution, when diluted
The production of a blue colour when free to 1 litre and thoroughly mixed, is strictly deci-
iodine and starch solution are brought together
normal, and keeps indefinitely. A measured
is, however, much more sensitive, and is the
method usually employed quantity of the N/10 -arsenite solution is delivered
in ascertaining the into an Erlenmeyer flask, and the iodine solu-
end-point. tion run in from the burette until present in
Preparation of starch solution. About 1 gram
slight excess, starch paste being added nearly
of powdered starch is rubbed into a paste with
at the finish of the titration (see remarks on
a little cold water, and slowly added to 200 c.c. of
starch above). The reaction
boiling water, the boiling is continued for two
or three minutes, the solution cooled, and after
As 2 O 3 +2I,+2H 2 ^ As 2 O 5 -f4HI
some hours the clear liquid is decanted. The proceeds to completion in the sense of the upper
solution will only keep for one or two days, arrow in neutral solution, a condition secured
unless sterilised, when it is conveniently pre- by the presence of the bicarbonate, which
served in small bottles, completely filled and neutralises the hydriodic acid produced. Since
closed by soft rubber stoppers ; it will then the solution should be saturated with carbon
keep indefinitely. Starch paste prepared from dioxide, it is advisable to stopper the flask
Gastine's formula (5 grams starch, 0-01 gram except when actually introducing the iodine
mercuric iodide, and 1 litre water) retains its (J. Amer. Chem. Soc.' 1908, 30, 31).
sensitiveness for a long time. Addition of 1 c.c. The iodine being standardised, the thio-
ANALYSIS. 205
sulphate can be directly titrated against it, former case 35 grams of pure ferrous ammonium
the iodine into a measured sulphate are dissolved in dilute sulphuric acid
preferably by running
volume of thiosulphate. and the solution diluted to 1 litre 25 c.c. are ;
Many alternative methods have been pro- then exactly oxidised with dilute
permanganate,
posed for standardising iodine
and thiosulphate and the resulting ferric sulphate titrated with
solutions. The latter may be titrated against the titanous chloride until a
drop of the solution
0-5 gram of pure iodine and 0-1 gram no longer gives a red colour with potassium
pure iodine :
potassium iodide are powdered and mixed

'
of thiocyanate. Instead of using this spot-out '
together in
a porcelain dish, and heated on a method, 10-20 c.c. of 10 p.c. potassium thio-
sand-bath till vapour is copiously evolved ; the cyanate may be added to the ferric solution.
dish is then covered with a dry watch-glass, and If the standardisation be effected with
potas-
the greater part of the iodine sublimed on to it. sium dichromate, addition of the indicator to
The watch-glass is covered with a second accu- the solution itself is inadmissible.
Nearly all
rately fitting glass and the whole weighed, the the titanous chloride necessary, may, however,
height of the glasses having been previously be added at once, since the colour
changes,
found. The whole is gently placed in a solution through orange to green and then violet, afford
of 1 gram of potassium iodide in lOc.c. of water, an indication of the end-point. Drops of solu-
and after a few seconds the solution is diluted tion are removed for testing when the
green
to 100 c.c. and titrated with the thiosulphate. colour has just disappeared (J. Soc. Chem. Ind.
The thiosulphate may also be standardised 1908, 27, 673).
against permanganate, itself verified by reference Pure ferric alum, the preparation of which
to sodium oxalate. One or two grams of potas- is described by De Koninck (Bull. Soc. chim. Belg.
sium iodide are dissolved in water, acidified with 1909, 23, 222), might also be employed for this
5 c.c. of hydrochloric acid (1:5) and 25 c.c. of standardisation.
standard permanganate added. The iodine, For a number of estimations it is necessary
which is quantitatively liberated : to employ titanous sulphate instead of the
Mn 2 O 7 + 10HI = 2MnO + 5H 0+5I 2 2
chloride.
is then titrated with the thiosulphate, after Stannous chloride.
This reagent has long been employed as a
diluting the solution to 100 c.c. By the reverse
process of calculation, a permanganate solution reducing agent, but the closely allied and more
may be standardised against a thiosulphate powerfully reducing titanous salts appear to be
solution that has been verified by either of the displacing it. Ferric salts are easily reduced
in hot acid solution
preceding methods (see Standardisation of per-
:
manganate; cf. Annalen, 1897, 198, 333 Zeitsch. ; 2FeCl 3 + SnCl 2 = SnCl + 4 2FeCl 2 .
angew. Chem. 1904, 17, 815 ; Ann. Chim. Anal. Iodine cold
in acid solution oxidises it
1904, 9, 365 ; Zeitsch. anorg. Chem. 1906, 49,
277).
quantitatively :
(For the use of potassium dichromate in this 2SnCl 2 + 21, = SnI 4 + SnCl 4 .
connection, see Volumetric estimation of Ten grams of pure tin in thin pieces are
chromium ; Zeitsch. anorg. Chem. 1899, 19, heated with 200 c.c. of concentrated hydro-
427; 1906, 49, 277. See also Copper under chloric acid in a platinum dish until dissolved :
Volumetric estimations. For a gravimetric or a glass flask may be used with a piece of
method for standardising iodine solution, consult
Amer. J. Sci. 1909, (iv.) 28, 33.)
platinum foil touching the tin to promote its
speedy solution. The solution is diluted to
1 litre, and preserved out of contact with the
Titanous chloride.
air.
This reagent, introduced into volumetric
The solution is best standardised by that
analysis by Knecht (J. Soc. Dyers and Colourists,
process for which it is afterwards to be employed,
19, No. 6; Ber. 1907, 40, 3819), is a powerful
e.g. if required for iron estimations, by titration
reducing agent. For example, a hydrochloric
acid solution of ferric chloride is quickly and
against a known amount of ferric chloride.
The latter may be obtained by dissolving
quantitatively reduced hi the cold, according to 10-03 grams of bright iron wire (99-7 p.c. iron)
the equation :
in hydrochloric acid, oxidising with potassium
FeCl 3 TiCl 3+ =
FeCl 2 -f TiCl 4 chlorate, expelling the excess of chlorine by
and the end-point is reached when a drop of boiling, and diluting the solution to 1 litre ;
the liquid ceases to
produce a red colouration 25 c.c. are conveniently used for titrating the
with potassium thiocyanate. Chromic acid and above solution.
?upric salts may be similarly estimated, and Several methods have been proposed for
ilso a
large number of organic dyes. determining the end-point. The iron solution
Fifty c.c. of the commercial 20 p.c. containing 2040 c.c. of concentrated hydro-
solution of titanous chloride, which usually con- chloric acid in a volume of 125 c.c. may be
;ains a little iron, are mixed with an equal titrated nearly at the boiling-point, 15 c.c. of
rolume of concentrated hydrochloric acid, boiled indicator solution (34 grams HgCl 2 +0'05 gram
'or several minutes, and diluted to 1 litre with Pt as chloride per litre) being added. The
lir-free water. The solution must be kept pro- end-point is reached when a dark-cloud of
ected from the air a convenient method is finely divided mercury and platinum
is pro-
;
igured in Button's Volumetric Analysis (9th ed.), duced (Amer. Chem. J. 1893, 15, 360). Or a
drop of the solution may be mixed with am-
The concentration of the solution is fixed monium molybdate on a white plate ; the
known quantity salt causes a blue
>y titrating against a of either slightest trace of stannous
erric salt or potassium dichromate. In the colouration. An alternative is to add a slight
206 ANALYSIS.
excess of stannous chloride, and titrate back VOLUMETRIC ESTIMATIONS.
the cold solution with iodine.
Aluminium. lodimctrically. The neutral
(For the standardisation by means of iodine solution is boiled with excess of potassium iodide
see. Volumetric estimation of
tin.) and potassium iodate for twenty minutes in a
Silver nitrate, Sodium and Am- stream of hydrogen the iodine evolved, and
;
chloride,
monium collected in potassium iodide,
thiocyanate. together with that
which remains in the distilling flask, is titrated
These precipitation reagents, which are con-
with .ZV/lO-thiosulphate (Amer. J. Sci. 1905,
veniently made of decinormal strength, are oi 181 ; Zeitsch. anorg. Chem. 1907, 52,
20,
286) :
great service for the volumetric estimation oi
silver, copper, mercury, the halogen acids, A1.(S0 4 ) 3 +5KI+KIO,+3H 2
cyanides, and thiocyanates. = 2A1(OH) 3 +3K.,S0 4 +3T 2 .
Silver nitrate is used either in neutral or in

nitric acid solution. In the first case potassium Antimony. ANTIMONIOTJS SOLUTIONS, (a) lodi-
chromate is employed as indicator when halogens metrically. One or two grams of Rochelle salt
are being estimated (Mohr's method). Silver are added, the solution made alkaline with
chromate is decomposed by solutions of halogen sodium bicarbonate, and titrated with N/IQ-
salts forming silver halide and metallic chromate ; iodine. = I2 Sb (v. AESENIC).
consequently, silver chromate cannot permanently (6) By oxidation. The hot hydrochloric acid
exist in the solution until all the halogen has solution (above 60) is titrated with
^/lO-potas-
been precipitated. The first drop of silver sium bromate, which has been standardised
nitrate in excess then produces a permanent against a known amount of pure antimony
precipitate of silver chromate, which gives 3SbCl 3 +KBr0 3 +6HCl=3SbCl s +KBr+3H 2 0.
faint red tint to the previously pale-yellow
liquid. This colour change is more readily The end-point is indicated by the bleaching of
observed in monochromatic light (from a power- a few drops of methyl orange added to the hot
ful sodium flame). One or two drops of a solution (Chem. Zeit. 1903, 27, 749; J. Soc.
10 p.c. solution of potassium chromate are Chem. Ind. 1906, 25, 1181 ; Chem. News, 1907,
added to the solution, which should not be 95, 49).
unduly diluted. chromate is soluble in
Silver (c) By oxidation. The cold solution, freely
mineral acids or ammonia hence the necessity
;
acidified with hydrochloric acid, is titrated with
for working in neutral solution. An alkaline AT/10-permanganate (Zeitsch. angew. Chem. 1901,
solution may be acidified with dilute nitric acid, 14, 1179 ; J. Amer. Chem. Soc. 1907, 29, 66).
and then neutralised with powdered calcium ANTIMONIC SOLUTIONS, (a) By reduction to
carbonate. Barium must be absent from the the tervalent state, and estimation by one of
solution, since it precipitates the indicator ; it the foregoing processes. Reduction may be
may be removed with sodium sulphate. accomplished : (i.) by boiling the hydrochloric
In the presence of nitric acid, silver nitrate acid solution with sodium sulphite or sulphurous
and ammonium thiocyanate solutions are used acid (Zeitsch. angew. Chem. 1888, 155) accord- ;
in conjunction (Volhard's method, Annalen, ing to Rohmer, the reduction is not quanti-
1878, 190, 47). The addition of thiocyanate to tative unless a gram of potassium bromide is
a nitric acid solution containing silver causes added (Ber. 1901, 34, 1565); (ii.) by boiling
the precipitation of white silver thiocyanate, the sulphuric acid solution (100 c.c. containing
and the end-point is indicated by the red 5 c.c. of concentrated acid and 4 grams of Rochelle
colouration produced by the interaction of the salt) with 1-0-1 -5 grams of potassium iodide till
first drop of thiocyanate in excess with a ferric nearly all the iodine is expelled, exactly bleach-
salt previously introduced into the solution. ing the remainder with dilute sulphurous acid,
The thiocyanate should always be added to the diluting, rapidly cooling, and neutralising. The
silver solution. The ferric indicator is prepared solution is then titrated in bicarbonate solution
by adding nitric acid (4 1 boiled to expel: with -ZV/10-iodine (Amer. J. Sci. 1892, 42, 213).
nitrous acid) to a saturated solution of iron (b) lodimetrically. The cold solution con-
alum until colourless ; 5-10 c.c. are used in the taining 20-25 c.c. of hydrochloric acid in a
titration. volume of 100 c.c., is mixed with 0-5-1-0 gram
Standard sodium chloride solution is used of potassium iodide and the liberated iodine ti-
for the estimation of silver by the very exact rated with ./V/10-thiosulphate. I 2 Sb (Zeitsch. =
method originally due to Gay-Lussac. (For a anorg. Chem. 1908, 58, 202 ;
cf. ibid. 1903, 37,
description of the method, v. ASSAYING. ) 337).
Decinormal silver nitrate is obtained by dis- Arsenic. AKSENIOUS SOLUTIONS. lodimetri-
solving 16-99 grams of the pure dry recrystal- cally. The solution, containing sodium bicarbo-
lised silver nitrate in water and diluting the aate in excess, is titrated with ^/10-iodine as
solution to 1 litre. If it is to be used in con- described under the standardisation of iodine
junction with the thiocyanate, this solution iolution. The bicarbonate may with advantage
may also be prepared by dissolving 10-788 grams )e replaced by disodium hydrogen phosphate
of piire silver in a slight excess of nitric acid, J. Amer. Chem. Soc. 1908, 30, 31).
boiling till nitrous acid is expelled, and diluting ARSENIC SOLUTIONS, (a) By reduction with
to 1 litre. lydriodic acid as described under Antimony, and
The thiocyanate is prepared approximately subsequent titration with iodine ; no Rochelle
decinormal by dissolving the salt in distilled salt is necessary (Amer. J. Sci. 1900, 10, 151).
water (8 grams per litre), and is standardised deduction may also be effected by heating the
against the silver nitrate solution, 25 c.c. of sulphuric acid solution with sulphurous acid
which are diluted to 100 c.c. and titrated as n a stoppered bottle for an hour, diluting and
described above. soiling down to half the volume to expel excess
ANALYSIS. 207
of sulphurous acid (Zeitsch. anal. Chem. 1883, tilla permanent turbiditv is produced
(Liebig
22, 378 ; Chcm. News, 1886, 53, 221). Annalen, 1851, 77, 102)." This marks the end
(b) By precipitation.
The neutral or acetic of the reaction :
acid solution is precipitated with excess of silver 2KCN+Ag N0 =KN0 3 +KAg (CN)
3 2.
nitrate, and the precipitatedsilver arsenate The end-point best observed by
is
adding 5-10
collected, washed, dissolved in nitric acid, and the drops of 20 p.c. potassium iodide as an indicator.
silver titrated with N/ 10-thiocyanate. 3 Ag As. = A permanent yellow turbidity, due to silver
anal. Chem. 1906,
(c) lodimelrically (Zeitsch. iodide, is produced as soon as the above reaction
45, 596 ; compare
Amer. J. Sci. 1900, 10, 151). is completed (Ann. Chira. Phvs.
1895, (vii.1 6
(See also Zeitsch. anorg.
Chem. 1909, 62, 123, 381).
for a method suitable for small quantities of (b) See Ferrocyanides (b).
arsenic.) FERRICYANIDES. (a) The salt is reduced to
Barium. lodimelrically. Excess of potas-
ferrocyanide by boiling with sodium hydroxide
sium iodate added to the faintly ammoniacal
is and ferrous sulphate and the filtered solution
solution, the precipitated iodate washed with strongly acidified with sulphuric acid and titrated
ammonia and then with alcohol, dissolved in with -ZVyiO-permanganate (v. Ferrocyanides).
hydrochloric acid
and potassium iodide, and the Reduction may also be effected by boiling with
iodine titrated with JV/10-thiosulphate. 6I 2 =Ba sodium peroxide (Arch. Pharm. 232, 226).
(J. Amer. Chem. Soc. 1909, 31, 43). (b) lodimetrically. The neutral solution (50
Bismuth, (a) lodimetrically. The solution, c.c.) is mixed with 3 grams of potassium iodide
as free as possible from mineral acids, is mixed and 1 -5 grams of zinc sulphate, the mixture well
with excess of JV/2-potassium chromate, shaken shaken, and the iodine titrated with N/10-thio-
for 10 minutes, diluted to a known volume, and sulphate. 2K 3 Fe(CN) 6 =I 2 (Zeitsch. anorg. Chem.
the chromate in an aliquot part of the filtrate 1910, 67, 418 ; compare ibid. 67, 322).
from the .bismuthyl chromate Bi 2 3 '2CrO 3 is FERROCYANIDES. The
(a) By oxidation. solu-
titrated iodimetrically (Zeitsch. anorg. Chem. tion strongly acidified with sulphuric acid
is
1902, 32, 362 ; Zeitsch. anal. Chem. 1907, 46, and titrated with iV/lO-permanganate till the
223). colour changes from yellowish-green to yellowish-
(b) As bismuth ammonium molybdate (J. Amer. red. If any difficulty is experienced in deter-
Chem. Soc. 1903, 25, 907).
mining the end-point, a drop of the solution
ACIDIMETEY AND ALKALI-
Boron, (a) v.
may be mixed with dilute ferric chloride. A
METRY. blue colour will develop whilst any ferrocyanido
(b) lodimetrically. The reaction remains (de Haen, Annalen, 1854, 90, 160 ;
Zeitsch. anorg. Chem. 1910, 67, 418).

5KI+KIO 3 +6HB0 2 =3I 2 +3H 2 O+6KBO 2 compare
An
excess of permanganate may also be
is quantitative in a solution saturated with added,the excess being determined iodimetricully.
mannitol (v. Amer. J. Sci. 1899, 8, 127).
(For details, consult Zeitsch. anorg. Chem. 1910,
Bromine v. Halogens.
67, 322.)
Calcium. By oxidation. The oxalate, preci- The
(b) By conversion into hydrocyanic acid.
pitated from a hot slightly ammoniacal solution
ferrocyanide solution is boiled for five minutes
(see Gravimetric methods), is washed with warm with 10 c.c. of IV-sodium hydroxide and 15 c.c.
water till free from ammonium oxalate, decom- of 3IV-magnesium chloride, 100 c.c. of boiling
posed with hot dilute sulphuric acid, and the
oxalic acid titrated with JV/10-permanganate.
N/10-mercuric chloride are then added, and the
boiling continued for ten minutes. The mercuric
The precipitate may also be dissolved in dilute
cyanide produced is distilled for thirty minutes
hydrochloric acid, 0-5 gram of manganese sul- with 30 c.c. of 3.ZV-sulphuric acid, the prussic
phate added, and the solution titrated with acid collected in 25 c.c. of N-sodium hydroxide,
permanganate (v. Amer. Chem. J. 1905, 33, 500).
a little potassium iodide added, and the cyanide
Carbon. CARBON DIOXIDE, v. ACIDIMETRY titrated with -ZV/lO-silver nitrate (Feld, Chem.
and ALKALIMETRY, and Gas analysis.
Zentr. 1903, ii. 1398 ; Analyst, 1908, 33, 261 ;
CYANOGEN ACIDS. CYANATES. The cold, dilute
1910, 35, 295).
solution is exactly neutralised with .ZV/10-hydro- THIOCYANATES. (a) By precipitation. As in
chloric acid (using methyl orange or congo red
as indicator), excess of acid is added, the solution
standardising ammonium thiocyanate solution;
the thiocyanate must be added to the silver
boiled for ten minutes, cooled and titrated back
nitrate, and not vice versd, since nitric acid
iV/10-sodium hydroxide. Excess of ^/lO-sodium
decomposes thiocyanates.
hydroxide is then added, the solution boiled to The thiocyanate is ti-
(b) By oxidation.
expel ammonia, and titrated back with N/10- trated in concentrated hydrochloric acid solu-
hydrochloric acid. From these data two values tion with potassium iodate, in a stoppered
for the cyanate can be calculated, which serve The end-point
bottle, with vigorous shaking.
to check one another (Chem. News, 1906, 93,
is reached when 5 c.c. of chloroform previously
5 ; compare Zeitsch. angew. Chem. 1901, 24, introduced are no longer coloured by iodine
585 J. Soc. Chem. Ind. 1904, 23, 244).
;
(J. Amer. Chem. Soc. 1908, 30, 760); e.g.
KCNO+2HC1+H 2 = KCl+NH 4 Cl+CO a .

4CuCNS+7KIO,+14HCl
CYANIDES, (a) By precipitation, (i.) Excess = 4CuS6 4 +7KCl+7ICl+4HCl+6H 2 0.
D
2VyiO-silver nitrate is added to the neutral Oxidation in dilute sulphuric acid solution with
Cyanide solution, and then a little nitric acid, permanganate is untrustworthy.
il'he excess of silver is titrated with ^/10-thio- Cerium, (a) lodimetrically. Ceric oxide is
isyanate after filtering off the silver cyanide. warmed with concentrated hydrochloric acid
iii.) The slightly alkaline solution is titrated and potassium iodide in a stoppered bottle till
vith A^/lO-silver nitrate with constant
stirring complete solution is effected. The liberated
208 ANALYSIS.
iodine is then titrated with jV/10-thiosulphate excess of peroxide(v. J. Soc. Chem. Ind. 1896,
(Bunsen, Annalen, 1858, 105, 49; also Amer. 15, 155, 436; Chem. Zeit. 1897, 21, 3; Bull.
J. Sci. 1899, 8, 451). Soc. Chim. 1909, 5, 1133; Chem. News, 1896,
73,
2Ce0 2 +8HCl+2KI==2CeCl 3 +2KCl+I 2 +4H 2 1).
The solution is
Cobalt, (a) lodimetrically.
(b) By oxidation. The washed oxalate is mixed with hydrogen peroxide, and then with
suspended in hot dilute sulphuric acid and sodium hydroxide, when the cobalt is preci-
titrated with IV/lO-permanganate (v. Calcium; pitated as sesquioxide Co 2 3 whilst nickel is ,
Zeitsch. anal. Chem. 1880, 19, 194; Amer. J. simply precipitated as green hydroxide. After
Sci. 1899, 8, 457). boiling for a minute, the black ppt. is dissolved in
(c) By reduction. The cerium is oxidised with hydrochloric acid and potassium iodide, and the
sodium bismuthate sulphuric acid
in boiling iodine titrated with .ZV/10-thiosulphate (Chem.
solution to eerie sulphate and the filtered solu- News, 1900, 82, 66, 73 1903, 88, 184).;
tion reduced by a slight excess of ferrous (b) By precipitation with ferrocyanide, as

sulphate, the excess being titrated with N/10- described under Nickel (b).
permanganate. Other rare earth metals do not Columbium. By reduction and subsequent,
interfere (J. Amer. Chem. Soc. 1909, 31, 523; oxidation (v. Zeitsch. anorg. Chem. 1909, 62, 383).
1910, 32, 642 ; compare Compt. rend. 1899, Copper, (a) lodimetrically. The solution of
128, 101 ; Ber. 1900, 33, 1924 ; Ber. 1903, 36, cupric salt preferably neutral or containing
282). acetic acid, is diluted to 100 c.c., 5 grams of
(d) Other methods (Zeitsch. anorg. Chem. potassium iodide are added, and the liberated
1907, 54, 104 ; 1908, 59, 71). iodine titrated with N/ 10 -thiosulphate, using
Chlorine v. Halogens. starch paste as indicator. If more than 25 c.c.
Chromium. The chromium should be in the of thiosulphate are required, 2-3 grams more
form of chromate. potassium iodide should be added (Amer. J. Sci.
(a) lodimetrically. The chromate solution is 1907, 24, 65 ; compare J. Amer. Chem. Soc.
acidified with hydrochloric acid (5 c.c. of concen- 1902, 24, 1082; 1905, 27, 1224; see also
trated acid per 100 c.c. solution), 1 or 2 grams of Methods of separation).
potassium iodide added, and the covered solu- 2CuS0 4 +4KI = 2K 2 S0 4 +I 2 +Cu 2 I 2 .
tion allowed to stand for 15 to 20 minutes. It

is then diluted to 400-500 c.c. and the liberated
By titration with potassium cyan
(b)
(Steinbeck's process). The ammoniacal copper
iodine titrated with .ZV/10-thiosulphate. 3I 2 =2Cr.
solution is titrated with potassium cyanide
A known dichromate solution can in this way be until colourless (v. Chem. News, 1897, 76, 189;
used to standardise sodium thiosulphate (J. pr. Methods of separation ; and the article COPPER).
Chem. 1868, 103, 362; Zeitsch. anorg. Chem.
(c) precipitation as thiocyanate and esti-
By
1899, 19, 427 ; 1906, 49, 277 ;
Zeitsch. angew.
mation of the precipitate by potassium ioclate
Chem. 1900, 1147). in hvdrochloric acid solution (v. Thiocyanates ;
(b) By reduction (i.)
with ferrous ammonium
and J. Amer. Chem. Soc. 1908, 30, 760).
sulphate, of which a slight excess is added
to
(d) By oxidation. The oxalate is precipi-
the chromate solution containing sulphuric or tated in a nitric acid solution by adding excess
hydrochloric acid, the excess of ferrous salt being of ammonium oxalate, washed and titrated
then titrated with 2^/10-dichromate ; (ii.) with with JVYlO-permanganate (Amer. J. Sci. 1909, 27,
titanous chloride (v. Preparation of standard
448).
solutions ; J. Soc. Chem. Ind. 1908, 27, 673) ; To the
(e) By reduction to cuprous salt.
(iii.) with
arsenious oxide (Amer. J. Sci. 1896,
sulphuric or hydrochloric acid solution, 10-20 c.c.
1, 35). of 10 p.c. potassium thiocyanate and a little
Chromium in chrome steel. Three grams of ferrous salt are added, when a deep red coloura-
alloy are dissolved in 35 c.c. of concentrated tion is produced, since ferrous salts in acid
hydrochloric acid, and the excess evaporated ;
solution are partly oxidised by cupric salts.
150 c.c. of strong nitric acid are added, the The cold solution is titrated with titanous
boiling continued till no more brown
fumes are
chloride until the red colouration is destroyed
evolved, when all chlorine has been expelled.
(Chem. Soc. Trans. 1906, 89, 1491). Or a slight
The chromium is then oxidised by adding excess of titanous chloride may be added, and
10 grams of potassium chlorate, and the solution titrated back with standard ferric alum.
boiled down to 40 c.c. to decompose excess of The fluoride is
Fluorine. Acidimetrically.
chlorate 100 c.c. of water are added, and one
;
mixed with ten times its weight of finely
or two drops of hydrochloric acid, to dissolve
powdered and ignited quartz, and decomposed
separated manganese dioxide. The chromate by warming with concentrated sulphuric acid ;
solution is boiled to expel chlorine, cooled and the silicon fluoride evolved passes through a
titrated according to method (b) (i.) above. (For
dry U-tube filled with glass beads and immersed
other methods, see J. Amer. Chem. Soc. 1905, in cold water, in order to remove sulphuric acid,
27, 1550; 1908, 30, 1116; J. Soc. Chem. Ind. and is then absorbed in 50 p.c. alcoholic potas-
1907, 26, 1010; Chem. News, 1904, 90, 320; sium chloride, which precipitates silicic acid
91, 3 ; also Manganese and Vanadium (v. and potassium silicofluoride, leaving hydro-
infra). ) chloric acid in the solution :
Chromium in chromite. The valuation of
the only important ore of chromium, is
3SiF 4 +2H 2 O = 2H SiF +SiO,
2 6
this,
a volumetric method ; the H 2 SiF 6 +2KCl = K SiF +2HCl. 6
usually effected by
2
finely powdered ore is fused

with sodium per- The hydrochloric acid is titrated with N/5-
oxide in a nickel crucible, and the chromate in sodium hydroxide, using lacmoid as indicator.
the aqueous extract estimated as described 2HC1 = 3F 2 .
(For full
experimental details,
above, after boiling for ten minutes to decompose which are absolutely essential in order to obtain
ANALYSIS. 209
accurate results, consult Chem. News, 1879, 39, indiarubber derived from
stoppers, &c., is avoided
179; Amer. J. Sci. 1906, 22, 329; or Low's by fitting the condenser and the
Technical Methods of Ore Analysis.)
dropping
Gold. lodimetrically. The auric solution is
treated with potassium iodide in more than
sufficient quantity to dissolve the aurous iodide
first precipitated, and the iodine liberated is
estimated with standard thiosulphate (Amer.
J. Sci. 1899, 8, 261 ; compare Zeitsch. anorg.
Chem. 1899, 19, 63).
Halogens. This term is restricted in this
connection to chlorine, bromine, and iodine,
fluorine being treated separately, since its
analytical reactions are quite different.
ESTIMATION OF HALOGENS. Iodine is esti-
mated by solution in potassium iodide and titra-

tion with .ZV/10-thiosulphate, using starch paste
as indicator (v. Preparation of standard solutions,
p. 205). Bromine and chlorine are absorbed in
potassium iodide solution, setting free an equi-
valent quantity of iodine, which is titrated with
JV/10-thiosulphate.
A large number of substances, e.g. peroxides,
chlorates, chromates, &c., may be readily deter-
mined indirectly by distillation with concen-
trated hydrochloric acid, the available oxygen
of the compound setting free its equivalent of
chlorine, which is absorbed in potassium iodide,
and the liberated iodine titrated with JV/10-thio-
sulphate. It is very desirable to exclude air
in the process of distillation, since it liberates
iodine from the hydrogen iodide set free in the FIG. 14.
receiver, by the hydrogen chloride distilling
funnel to the distilling flask by ground-glass
over during the experiment. The apparatus
devised by Bunsen, the originator of this joints.
shown in Fig. 13, b. The ESTIMATION OF HALOGENS IN HALIDE SALTS.
analytical method, is
By precipitation, (i.) Mohr's method. The neu-
tral solution is titrated with .ZV/10-silver nitrate
in the presence of a few drops of potassium
chromate as indicator (v. Preparation of standard
solutions, p. 206). It is advisable to perform
a blank experiment under identical conditions,
to allow for the silver nitrate necessary to bring
out the reddish colouration, (ii.) Volhard's
method. The nitric acid solution of the halide
is precipitated by adding a
slight excess of iV/10-
silver nitrate, the excess being then titrated with
AyiO-ammonium thiocyanate. Silver chloride
must be filtered off before the latter titration is
performed, since it reacts with the thiocyanate
FIG. 13.
(J. Amer. Chem, Soc. 1907, 29, 269 compare ;
small flask (50 c.c.) and the delivery tube are Zeitsch. anorg. Chem. 1909, 63, 330); but
ground at their junction to fit, and the joint silver bromide and iodide do not interfere. It
made with caoutchouc tubing ;
a ground-glass is advisable to titrate iodide in a stoppered
joint is better, a spring holding the two parts bottle with vigorous shaking when adding both
tightly together. The mixture is
rapidly boiled, the silver solution and the thiocyanate, to
the chlorine
passing into potassium iodide con- minimise error due to occlusion. It is more
tained in the retort, the size of which must be accurate to weigh out a very slight excess of
suitably chosen to prevent overflowing. A pure silver, dissolve it in nitric acid (carefully
different receiving vessel is shown in Fig. 13, a. expelling nitrous acid, which interferes
with
t is
very convenient to perform such dis- the indicator), and add to the halide solution
tillations in a current of carbon dioxide or than to measure out jY/10-silver nitrate. After
vigorous shaking, the excess of silver is then
other inert gas, and various
designs of apparatus
lor such a titrated with a dilute thiocyanate solution
purpose are given in Amer. J. Sci.
1898, 6, 168; Chem. News, 1899, 79, 85; (1 c.c.
=
1 milligram Ag).
Jhem. Soc. Trans. 1892, 61, 87 ; Zeitsch. angew. IODIDES. lodimetrically. (i.) A slight excess
Jhem. 1890, 477. of potassium iodate is added, and the solution
The apparatus shown in Fig. 14 (Analyst, acidified with dilute sulphuric acid. The
"US, 33, 117) admits of the gradual introduction liberated iodine is extracted with chloroform,
'f a
liquid reagent during distillation in carbon carbon disulphide or toluene, and titrated with
lioxide, steam, or any other gas or vapour, jV/10-thiosulphate. A weaker acid than sul-
.'ontamination of the reagents with cork or phuric acid may be employed, e.g. acetic or
VOL. LT. r
210 ANALYSIS.
tartaric acid. Five-sixths of the iodine found Bromates. The substance is digested at 100
was originally present as iodide (Chem. Zeit. 1904, with potassium iodide and concentrated hydro-
28, 1191 ; Amer. J. Sci. 1897, 3, 293 ; J. pharm. chloric acid in a stoppered bottle, and the
Chim. 1902, 16, 207; J. Amer. Chem. Soc. liberated iodine titrated with thiosulphate.
1903, 25, 1138). This method is available in Br0 3 = 3I 2 (compare Zeitsch. anorg. Chem. 1899,
the presence of bromide and chloride, if acetic 19, 427).
acid be employed, (ii.) The solution, contain- lodates. These are simply added to a slight
ing the iodide, 2 grams of pure potassium arsenate, excess of potassium iodide solution, acidified
and 10 c.c. of concentrated sulphuric acid, is with sulphuric or hydrochloric acid, and the
boiled down from a volume of 100 c.c. to liberated iodine titrated. I0 3 3I 2 = .
35-40 c.c.,when the iodine is expelled. The

all
arsenious salt in solution is then titrated with ESTIMATIONS INVOLVING MIXTURES OP THE
FOREGOING HALIDE SALTS.
AyiO-iodine (Amer. J. Sci. 1890, 39, 188). As
=I 2 In the presence of chloride the results
.
Chloride, Hypochlorite and Chlorate. The
are a little low ; bromide causes them to be solution is titrated with N/1Q- sodium arsenite
slightly high, (iii.) (v, Chem. Soc. Trans. 1885, by Penot's method for the hypochlorite ; the
47, 471.) chlorate is then estimated in the solution, after
ESTIMATIONS OF HALOGENS IN OXYHALOGEN acidifying with sulphuric acid, by reduction with
COMPOUNDS, (a) By reduction to a halide salt standard ferrous sulphate, and the total chlorine
and determination of the latter. lodates are then titrated by Volhard's method (Compt. rend.
reduced by adding sulphurous acid to the 1896, 122, 449; cf. J. Amer. Chem. Soc. 1909,
sulphuric acid solution of the iodate till the 31, 525, 1273).
separated iodine is redissolved ; an excess of Chloride, Chlorate and Perchlorate. Chloride
^/10-silver nitrate is added to precipitate the is titrated in one portion of the solution by
iodide, the mixture boiled with excess of Volhard's method, and in another portion after
nitric acid, and finally the excess of silver reducing the chlorate with ferrous sulphate.
titrated with .ZVyiO-thiocyanate. Bromates and For perchlorate the dry substance, mixed with
chlorates are reduced by adding an excess of five times its weight of pure quartz sand and
iron filings to the sulphuric acid solution ; after covered with a layer of the same 2 cm. deep,
an hour, excess of A^/10-silver nitrate is added, is fused in a platinum crucible for half an hour,
the mixture boiled with nitric acid to oxidise the cooled, extracted with water, and the total
ferrous salt, and the excess of silver titrated chloride estimated (Compt. rend. 1896, 122,
(Amer. Chem. J. 1904, 32, 242). 452).
(b) By reduction to a halide salt and estima- Chloride and Iodide. The total halogen is
tion of the reducing agent used up in the process. titrated by a suitable method in one portion of
With chlorates and bromates, the sulphuric acid solution, and the chlorine in another portion
solution is boiled for ten minutes with excess of after removing iodine by one of the following
standard ferrous sulphate in an atmosphere of methods (Amer. J. Sci. 1890, 39, 293). (i.) To
carbon dioxide, the solution cooled, manganese the neutral solution (400 c.c.) is added 10 c.c.
sulphate added and the unchanged ferrous salt sulphuric acid (1:1), 2 grams ferric sulphate,
titrated with #/10-KMn0 4 6Fe . =
C10 3 or Br0 3 and 3 c.c. nitric acid, and the whole boiled till
(Zeitsch. anorg. Chem. 1904, 38, 110). Bromates all iodine is expelled 1 c.c. nitric acid is again
;
may also be reduced with arsenious oxide (Amer. added, and the solution again boiled, (ii.) The
J. Sci. 1902, 14, 285). Chlorates are reduced by ferric sulphate and nitric acid of method (i.) are
adding an excess of .ZV/10-titanous sulphate, and replaced by 2 grams of pure sodium nitrite (or,
after three minutes, titrating back with ferric failing this, by passing into the solution the
alum (J. Soc. Chem. Ind. 1908, 27, 434). vapours generated from the slightly im
(c) lodimetrically. Chlorates, (i.) By dis- nitrite and dilute sulphuric acid).
tillation with concentrated hydrochloric acid. Bromide and Iodide (v. supra, Iodides).
C10 3 =
3I 2 (Bunsen's method ; v. Estimation Bromide and Chloride. The solution is aci
of halogens ; Chem. Soc. Trans. 1892, 61, 87). fied so as to contain 25 c.c. of concentrated ni
(ii.) By reduction with concentrated hydro- acid in a total volume of 100 c.c., heated to
chloric acid and potassium bromide (Chem. Zeit. boiling and boiled for one minute, the source
1901, 25, 727), or with potassium iodide and of heat removed and air sucked through the
dilute sulphuric acid in presence of vanadyl solution until it is perfectly colourless (and for
sulphate (Zeitsch. anal. Chem. 1907, 46, 521). one minute longer). The bromine is then com-
(For other methods, see Amer. J. Sci. 1891, 42, pletely expelled ; the residual chloride is titrated
220; J. Amer. Chem. Soc. 1903, 25, 756; by Volhard's method. The total halogens are
Zeitsch. anal. Chem. 1907, 46, 308.) titrated in another portion of solution (J. Soc.
Hypochlorites. A slight excess of .ZV/ 10-sodium Chem. Ind. 1909, 28, 505).
arsenite is added and the excess titrated with (For a very accurate but more elaborate
T
JV/10-iodine, or the hypochlorite is directly ti- method, v. J. Amer. Chem. Soc. 1907, 29, 275 ;
trated with the arsenite till a drop of the solution also Zeitsch. anorg. Chem. 1895, 10, 387 ; Zeitsch.
ceases to colour starch-potassium iodide paper anal. Chem. 1900, 39, 81.)
blue. As = CIO (Penot's method ; compare Chloride, Bromide, and Iodide, (a) The iodide
Chem. Zeit. 1904, 28, 59). is decomposed with potassium iodate and acetic
Perchlorates. The concentrated solution is acid, the iodide extracted with chloroform and
boiled with a large excess of titanous sulphate, titrated. The bromide is destroyed by boiling
the excess oxidised with permanganate, and the with 5^-nitric acid, any iodate remaining is
chloride produced is titrated as usual (Zeitsch. decomposed with a slight excess of potassium
anorg. Chem. 1909, 62, 108 ; Chem. Zeit. 1909, iodide, which excess is readily decomposed by
33,759). boiling with nitric acid, and the residual chloride
ANALYSIS. 211
titrated. The
total halogens are titrated in
(Analyst, 1909, 34, Seduction by
306). (v.)
another portion of solution (J. Amer. Chem.
palladium-hydrogen in boiling acid solution;
Soc. 1903, 25, 1138). this introduces no
foreign substance into the
(b) The iodide is destroyed by boiling with
ferric sulphate and sulphuric acid, and the
amount of ferric salt reduced is determined with
AyiO-dichromate. The
halogens are deter-
total
mined by Volhard's method, and, in another
portion of solution, the iodide is removed by
adding hydrogen peroxide and acetic acid and
distilling in steam, the bromine separated as
described under Bromide and Chloride and the
residual chloride titrated (J. Soc. Chem. Ind.
1909, 28, 505).
Iron. FERROUS SALTS. By oxidation, (a)
The cold solution is strongly acidified with dilute
sulphuric acid and titrated with JV/10-perman-
ganate. This simple and accurate method
requires modification when hydrochloric acid is
present, since it reacts with permanganate.
This side-reaction can be practically prevented
by adding a moderate quantity of manganese
sulphate to the solution and titrating very
slowly. A
solution is prepared as follows :
67 grams of crystalline manganese sulphate are
dissolved in water, 138 c.c. of phosphoric acid
(sp.gr. 1-7), and 130 c.c. concentrated sulphuric
acid (sp.gr. 1-82) are added, and the mixture
diluted to 1 litre. Of this solution, 25 c.c. are
added to the ferrous solution to be titrated.
The phosphoric acid keeps the ferric solution
colourless, and thus facilitates the observation FIG. 15.
of the end-point (Zeitsch. anal. Chem. 1863, 1,
329 ; Chem. Zeit. 1889, 13, Amer. Chem.
323 ;
solution (Zeitsch. angew. Chem. 1902, 15 398
J. 1905, 34, 109; Analyst, 1908, 33, 43, and 424 ; Analyst, 1904, 29, 346). (vi.) Reduction
1909, 34, 306). with titanous sulphate (Amer. J. Sci. 1908, 25
(b) The acid solution is oxidised by N/10- 343).
dichromate as described under Preparation of (6) direct titration with a
By reducing agent.
standard solutions. (i.) Tilanouschloride. The sulphuric or hydro-
FERRIC SALTS, (a) By reduction to ferrous chloric acid solution of the ferric salt is titrated
salt and titration with permanganate or di- as described under Preparation of standard
chromate. Reduction may be effected in any solutions, p. 205. (ii.) Stannous chloride. The
of the following ways : (i.)The sulphuric acid nearly boiling hydrochloric acid solution is
solution is heated to boiling and hydrogen titrated as described under Preparation of
sulphide passed through it until the solution standard solutions, p. 205, using either the
is
completely colourless ; the excess of hydrogen mercuric chloride indicator (Amer. Chem. J.
sulphide is expelled from the boiling solution 1893, 15, 360) or titrating back with iodine.
by a current of carbon dioxide, (ii.) The nearly FERROUS IRON IN MINERALS AND BOCKS. The
neutral solution is boiled with sulphurous only satisfactory method consists in decom-
acid or ammonium sulphite, excess posing the coarsely powdered substance with
being re-
moved by continued boiling, preferably in a sulphuric and hydrofluoric acids in an atmo-
current of carbon dioxide, (iii.) Eight or ten sphere of carbon dioxide, and titrating the
grams of granulated zinc are added to the
i
ferrous salt produced (Cooke's Method; Amer.

!warm sulphuric acid solution, and the action J. Sci. 1867, 44, 347 ; see also Amer. J. Sci.
allowed to continue until a drop of the solution
i
1894, 48, 149). The old method of heating with

jno longer gives
a colouration with potassium dilute sulphuric acid in a sealed tube (Mitscher-
thiocyanate. The solution is cooled, filtered lich) is worthless in the presence of sulphur or
through glass wool, and titrated. The use of sulphides (J. Amer. Chem. Soc. 1900, 22, 625).
the zinc-copper
couple is preferable (Analyst, (For an exhaustive discussion of this problem,
>01, 26, 225 ; compare Chem. News, 1908, 97, v. Hillebrand's Analysis of Silicate and Carbonate
50). Reduction may be rapidly effected by Rocks.)
pouring the liquid through a long column of Iron and Aluminium. After weighing the
'.iuc
(The Jones' Reductor (Fig. 15); Chem. ignited sesquioxides, they are brought into solu-
N'uws, 1889, 60, 93 ; Blair's Chemical Analysis of tion by fusion with potassium hydrogen sulphate
Iron, 6th ed. 94). (iv.) The hydrochloric acid or acid potassium fluoride (followed by evapora-
-olution is heated nearly to
boiling, and stannous tion with sulphuric acid), and the iron reduced
phloride (25 p.c. solution) added drop by drop and titrated (Zeitsch. angew. Chem. 1905, 18,
nitil the solution is colourless 10 c.c. of
; 815).
saturated mercuric chloride are added to Iron and Titanium. Ferric salts can be
destroy
texcess of stannous chloride, the solution reduced with sulphurous acid or hydrogen
diluted,
aanganese sulphate added (v. supra), and the sulphide without reducing titanic salts ; or
crrous salt titrated with reduction of both may be effected with zinc and
^/10-pernianganate
P 2
212 ANALYSIS.
sulphuric acid, the titanous salt oxidised with 3MnO+Mn O = 5Mn0
2 7 2
a slight excess of bismuth oxide, and the ferrous (Zeitsch. anal. Chem. 1909, 48, 751 ; Little and
salt titrated in the filtered solution. To estimate Cahen, Analyst, 1911, 36, 52).
both elements present, one of the preceding (b) By precipitation as dioxide and estimation
methods may be combined with the reduction of the available oxygen. Precipitation may be
process for titanium, described later, which effected in one of the following ways (i.) By :
Avould give the total iron and titanium (v. also adding bleaching-powder solution and calcium
J. Soc. Chem. Ind. 1909, 28, 189; Analyst, carbonate to a hot neutral solution of the
1910, 35, 198). manganese salt containing ferric and zinc
Iron and Vanadium. Reduction with sul- chlorides (Chem. Soc. Trans. 1879, 35, 365;
phur dioxide proceeds with the vanadium as J. Soc. Chem. Ind. 1891, 10, 333). (ii.) By
far as to the oxide 2 V
4 ; reduction with zinc boiling the solution in concentrated nitric acid
carries it as far as 2 2 ; V
hence two such (quite free from any hydrochloric acid) with
reductions and titrations with permanganate potassium (or preferably sodium) chlorate,
furnish data for calculating both iron and (iii.) By boiling the dilute sulphuric acid solu-
vanadium (Amer. J. Sci. 1908, 26, 79). tion with ammonium persulphate (Zeitsch.
Lead. precipitation (i.) As molybdate.
By angew. Chem. 1901, 14, 1149 ; 1903, 16, 905 ;
The boiling acetic acid solution is titrated with Compt. rend. 1902, 135, 965 ; 1903, 136, 449).
standard ammonium molybdate (4-75 grams per The washed precipitate in either case is dis-
litre, titrated against pure lead) until a drop solved in a sulphuric acid solution of standard
of solution gives a brown or yellow colour with ferrous sulphate or oxalic acid, and the excess
a drop of dilute tannic acid solution. The of reagent titrated. The precipitate obtained
' '
indicator not being very sensitive, a blank by method (ii.) is deficient hi available oxygen
experiment should be made and the necessary (Amer. J. Sci. 1898, 5, 260), and the standard
correction allowed for both in an assay and in solution employed in the final titration must
standardising the solution, (ii.) As ferrocyanide. therefore be standardised on a known amount
The cold acetic acid solution is titrated with of manganese treated in a similar fashion.
potassium ferrocyanide (10 grams per litre (c) By conversion into permanganic acid.
titrated against pure lead) until a drop of the (i.) The cold solution free from hydrochloric
solution produces a brown colouration with a acid, and containing one quarter its volume of
drop of saturated uranium acetate solution ; nitric acid (specific gravity 1-42), is oxidised by
'
a blank experiment should also be made shaking with 2-4 grams of sodium bismuthate
(J. Amer. Chem. Soc. 15, 550 ; Chem. News, for three minutes, diluted with half its volume
1896, 73, 18). In determining lead in ores, &c., of 3 p.c. nitric acid, the solid residue allowed
it is usually separated as sulphate and dissolved to settle, and the permanganic acid solution
in ammonium acetate previous to titration. filtered into a slight excess of ferrous sulphate ;
(For a comprehensive review of methods for lead, excess of the latter is then titrated with N/10-
v. Chem. News, 1903, 87, 40 ; Gaz. chim. ital. permanganate (Dingl. polv. J. 269, 224 ; Chem.
1896, 26, i. 327 ;
see also Methods of separation ; Soc. Trans. 1895, 67, 268"; Chem. News, 1901,
and J. Amer. Chem. Soc. 1903, 25, 632 ; 1904, 84, 209, 247; J. Amer. Chem. Soc. 1904, 26,
26, 1135.) 793). (ii.) The oxidation of small quantities of
Magnesium, (a) Acidimetrically. The mag- manganese may be effected by boiling the nitric
nesium is precipitated as the double ammonium acid solution with lead peroxide, or by heating
phosphate, the precipitate washed with dilute with ammonium persulphate in the presence of
ammonia, and then with aqueous alcohol till free a little silver nitrate (Chem. News, 1901, 84,
from extraneous ammonia, dissolved in a 239).
measured excess of ^/10-hydrochloric acid, and Manganese in Ferromanganese and Steels. The
the excess titrated with JV/10-sodium hydroxide, foregoing methods a, b, and c (i.) have all been
using methyl orange for indicator :
employed for this purpose ; method c (i. ) is the
= MgCl +H simplest and probably the most accurate. In
Mg(NH 4 )P0 4 +2HCl 2 2 (NH 4 )P0 4 method c it is necessary to remove iron from
(Chem. Zentr. 1876, 727 a method which
; for the solution ; this is conveniently performed by
obviates the use of alcohol, v. J. Amer. Chem. adding a slight excess of zinc oxide to the
Soc. 1900, 22, 31 ; see also Phosphorus). solution (v references given above ; also J. Amer.
.
(b) lodimetrically. The magnesium is pre- Chem. Soc. 1902, 24, 243 ; Ann. Chim. anal. 1906,
cipitated as double ammonium arsenate, dis- 11, 124).
solved in hydrochloric acid and potassium iodide, Manganese and Chromium occurring together
and the iodine titrated (J. Amer. Chem. Soc. in steels may be estimated by oxidising with
1899, 21, 746; Zeitsch. anal. Chem. 1907, 46, ammonium persulphate in sulphuric acid solu-
714). tion in the presence of silver nitrate ; one
Manganese, (a) By oxidation with perman- portion of solution is titrated for total perman-
ganate. (Volhard's method, modified.) The neutral ganate and chromate with ferrous sulphate, and
chloride or sulphate solution containing 10 grams another for permanganate alone by means of
of zinc sulphate is heated to boiling, 1 gram of arsenious oxide (J. Amer. Chem. Soc. 1905, 27,
freshly ignited zinc oxide added, and the liquid 1550; v. alsoCnem. News, 1901,83,25; 1905,
titrated with ^/lO-permanganate, boiling and 91, 3 ; Chem. Zeit. 1905, 29, 987 Chem. ;
Zeit,
shaking frequently until the supernatant liquid Rep. 1905, 29, 380).
is red ; 1 c.c. pure glacial acetic acid is added, The foregoing bismuthate method c (i.) may
and the titration slowly finished with perman- be applied in the presence of molybdenum, tung-
ganate in the hot but not boiling liquid. The sten, titanium, and vanadium also, with certain
;
manganese can be accurately calculated from precautions, in the presence of chromium (Chem.
the equation :
News, 1901, 84, 247). (For estimating manganese
ANALYSIS. 213
in tungsten steels, v. also J. Soc. Chem. Ind. 1907, is madefeebly ammoniacal and titrated slowly,
26, 345.) stirring constantly, with standard potassium
Mercury, (a) By precipitation. Mercuric ni ferrocyanicle (20 grams per litre, titrated against
trate readily titrated with .ZV/lO-thiocyanate
is pure nickel), until a drop of the solution when
using ferric nitrate as indicator, provided
tha acidified with dilute acetic acid
develops a green
nitric acid is present in fairly high concen colour in five minutes ( J. Amer. Chem. Soc. 1910
tration (Ber. 1901, 34, 3502 ; 1902, 35, 2015) 32, 757 ; Bull. Soc. chim. 1907, 4, 1163).
Chloride must be absent ; if necessary, the Nickel in Steel. Method (b) can be
directly
mercury is precipitated as oxide with sodiun applied ; method (a) can also be employed with-
hydroxide, and the washed precipitate out removing iron, molybdenum, or
dissolvec
chromium,
in nitric acid. if a sufficient excess of ammonium citrate
or
(b)
The mercuric solution
lodimetrically. sodium pyrophosphate is added to the solution ;
1 gram of potassium
containing or a moderate amount (2-3
(25-50 c.c.) grams) of each
iodide is made sodium hydroxide
alkaline with of these reagents
may be added (J. Amer.
2-3 c.c. of 40 p.c. formaldehyde added, and the Chem. Soc. 1907,29, 1201 1908,30, 1116; 1899,
;
whole shaken vigorously for two minutes. The 21, 854; Chem. Zeit. 1908, 32, 1223). (For
solution is acidified with acetic acid, and the modifications in presence of other metals,
reduced mercury is dissolved by adding an v. Chem. News, 1898, 78, 177, 190.)
excess of .ZVyiO-iodine. After shaking, the excess Nitrogen. AMMONIA
(v. ACIDIMETRY AND
of iodine above that required to form mercuric ALKALIMETRY).
iodide is titrated with 2VyiO-thiosulphate (Ber. HYDRAZINE. lodimetrically. A moderate
1906, 39, 3702; 1907, 40, 3276; Bull. Soc. excess of sodium bicarbonate or sodium acetate is
chim. 1907, [iv.] 1, 1169). Mercurous salts added to the solution of a hydrazine salt, which
require a preliminary oxidation. is then titrated with ^/lO-iodine. NH 2 4 =21
(For other methods, v. Compt. rend. 1863, (J. pr. Chem. 1902, 66, 332; 1903, 67, 140;
56, 63; Chem. Soc. Trans. 1892, 61, 364; v. also Gazz. chim. ital. 1899, 29, 265).
Arch. Pharm. 241, 444.) HYDROXYLAMINE. (a) By oxidation. The
Molybdenum, (a) By reduction and subse- solution of a hydroxylamine salt is slowly added
quent oxidation. The sulphuric acid solution to excess of boiling and well stirred Fehling's
is reduced by passingit through a long column solution, the precipitated cuprous oxide washed,
of amalgamated zinc to a condition represented dissolved in acid ferric alum, and the ferrous
by the formula Mo 2 3 the liquid is caught
; salt titrated with permanganate. 2 2
NH OH=Cu
directly in ferric sulphate solution, which re- (Chem. Soc. Trans. 1903, 83, 1394; compare
oxidises the molybdenum salt, and the ferrous Ber. 1877, 10, 1940).
sulphate produced is titrated with .ZV/10-perman- (b) By reduction. An excess of titanium
ganate (Amer. J. Sci. 1907, 24, 313 ; compare sesquisulphate is added to the acid solution,
Ber. 1905, 38, 604 ; Analyst, 1907, 32, 250). and the ammonium salt produced is estimated
(b) lodimetrically. The solution in concen- by distillation with sodium hydroxide (Ber.
trated hydrochloric acid is boiled with a slight 1909, 42, 2695J.
excess of potassium iodide till the volume is NITRATES, (a) By reduction. The solution
reduced to 25 c.c., when complete reduction to is made strongly alkaline with sodium hydroxide,
the condition Mo 2 s is effected. The solution 5 c.c. of alcohol and 2-5-3 grams of powdered
is cooled, diluted to 125 c.c., 0-5
gram of man- Devarda's alloy added, and the flask connected
ganese sulphate added, and then a slight excess with a distilling apparatus, the receiver of which
of $yiO-permanganate ; JV/10-arsenious acid contains excess of Ar /2-hydrochloric acid. After
isnext added, and after the addition of tartaric standing for half an hour, the liquid is steam-
acid and sodium bicarbonate, the excess is distilled for an equal length of time, when all
titrated with 2VyiO-iodine. The permanganate the nitrate has been converted into ammonia
plus iodine and minus the arsenious acid measure and driven over into the acid the excess of the
;
the Mo 2
present (Amer. J. Sci. 1901, 12, 449 ;
s latter is then titrated (Zeitsch. anal. Chem.
compare 156 ; 1898, 6, 168).
ibid. 1896, 2, 1894, 33, 113; Analyst, 1910, 35, 307; v. also
Molybdenum in Steels and Alloys (v. J. Amer. the Gravimetric section).
<'hem. Soc. 1904, 26, 675). (b) lodimetrically (v. Zeitsch. angew.
Chem.
Nickel, (a) By double cyanide formation. A 1890, 3, 477; Chem. Soc. Trans. 1891, 59,
few drops of 10 p.c. potassium iodide are added 530 ; Amer. J. Sci. 1892, 44, 117).
to the cold,
slightly ammoniacal nickel solution, NITRITES, (a) By oxidation. The nitrite solu-
and then a small measured volume of silver tion is slowly added to a measured quantity of
nitrate (3 of silver per litre).
grams Standard .ZV/10-permanganate, which is acidified with sul-
potassium cyanide (25 grams per litre) is then phuric acid, diluted to 400 c.c.,
and warmed to
run in with stirring till the precipitate of silver 40, until the colour is just discharged.
iodide just disappears ; more silver nitrate ia 2HN0 2 =
2 Otherwise, the cold dilute nitrite
.
added till a very faint turbidity is produced, solution is slowly titrated with IVyiO-permanga-
which is then dissolved by the least possible nate to a red colouration; a few drops of sul-
excess of cyanide. The relative values of the jhuric acid are then added, followed by an excess
silver nitrate and cyanide solutions are deter- of permanganate. The liquid is then strongly
mined by a preliminary experiment, and the acidified with sulphuric acid, heated nearly to
cyanide standardised against a known amount wiling, and the excess of permanganate titrated
of pure nickel (or
pure silver, and calculated to vith AyiO-oxalic acid (Amer. Chem. J. 1883, 5,
nickel). The method is rapid and accurate 388).
(Chem. News, 1895, 72, 92). (b) lodimetrically. Several methods have
(b) By precipitation. The hot nickel solu- een based on the reaction.
tion
containing ferric chloride and citric acid 2HI+2HN0 2 = Is +2NO+2HjO.
214 ANALYSIS.
It is necessary to perform the experiment in an calcium phosphate in acetic acid, standardised
atmosphere free from oxygen ; the iodine may gravimetrically by the method of Woy (Chem.
be determined by thiosulphate or arsenite. (For Zeit. 1897, 21,*442), must be used if the uranium
details, v. Pharm. J. 19, 741 ; Chem. News, acetate is to be used for estimating phosphates
1904, 90, 114; cf. Organic analysis, Aromatic of the alkaline earths (J. Soc. Chem. Ind. lv.
amines.) 11, 328). It is essential that titrations should
Osmium. lodimetricatty (v. Chem. Zentr. be made under conditions closely approximating
1898, ii.
65). those which obtained when the uranium solution
Oxygen. PEROXIDES, (a) lodimeiricaUy. Such was standardised.
peroxides as those of manganese and lead PHOSPHOBTJS rs mox AND STEKL. Th.
may be estimated by distillation with concen- usually separated as ammonium phospho-
trated hydrochloric acid, and collecting the molybdate ; it may then be titrated accord intr
chlorine evolved in potassium iodide (Bunsen's to 6 above, or the precipitate is washed with
(ii.)
method). Finely divided peroxides of manganese dilute ammonium sulphate, dissolved in am-
react quantitatively with cold dilute hydro- monia, the solution strongly acidified with
chloric acid and potassium iodide (Chem. Soc. sulphuric acid, reduced with zinc, and the
Trans. 1880, 37, 128), a method of estimation MojO 3 solution collected directly in ferric alum,
that is available with the peroxides of the alkali the ferrous salt being then titrated as described
and alkali earth metals, which do not give under Molybdenum (Amer. J. ScL 1907. 24.
satisfactory results bv the distillation method 313 ; compare Blair's Analysis of Iron).
(Arch. Pharm. 1902, 240, 437). Hydrogen per- Potassium. By oxidation. The acetic acid
oxide may be determined in this manner solution, free from ammonium salts, is evapo-
(Analyst, 1888, 13, 62). rated on the water-bath tillpasty with sodium
(6) By reduction. Hydrogen peroxide, or cobaltinitrite solution in rather large excess,
peroxides of the alkal and alkaline-earth metals, cooled and stirred with 50-100 c.c. of cold water.
may be dissolved in cold dilute acid and titrated
T
The dipotassium sodium cobaltinitrite is collected,
with A /10-permanganate, which loses as much on asbestos, washed with cold water, and then
oxygen as is lost (v. also Gas-
by the peroxide immersed in an excess of nearly boiling per-
Volumetric methods). manganate solution. After 5 minutes the solu-
(For critical reviews of methods, &c., v. tion is acidified with sulphuric acid, excess of
Arch. Pharm. 228, 432 ; Amer. Chem. J. 1906, ^T/10-oxalic acid added, and the clear solution
36, 117 ; Zeitsch. angew. Chem. 1901, 14, 828 ; titrated with permanganate. The perman-
1908, 21, 589; Chem. Zeit. 1906, 30. 1275; ganate is best standardised against a pure
1907, 31, 1257 ; Zeitsch. anal. Chem. 1908, 47, potassium salt. The oxidation of 2 molecular
465.) proportions of KNaCo(NO 2 ) e by permanganate
Phosphorus. PHOSPHOBIC ACID (OBTHO-). requires 11 atomic proportions of oxygen or
(a) (V. ACIDMETRY AND Al.KAT.TMKTBY).
=
4K 22H (Amer. J. Sci. 1907, 24, 433 ; com-
(6) AcidimetricaUy, with previous precipita- pare Chem. Soc. Trans. 1900, 77, 1076). (For
tion. (i.) The precipitated magnesium am- another method, v. Chem. Zeit. 1895, 19, 301.)
monium phosphate (v. Gravimetric section) is Selenium. SELESIOUS ACID. By oxidation.
washed and titrated as described under Mag- To the cold solution containing 5 p.c. by volume
nesium, p. 212 (Zeitsch. anaL Chem. 1898, 37, of concentrated sulphuric acid is added an ex-
217; Zeitsch. angew. Chem. 1905, 18, 655; cess of A'/lO-permanganate ; a moderate excess
compare Zeitech. anal. Chem. 34, 33). (ii.) The of AyiO-oxaUc acid is then added, and the
precipitate of ammonium phosphomolybdate (v. titration finished at 50-60 with permanganate.
Gravimetric section) after washing is dissolved 2SeO. =
O z (Amer. J. ScL 1895, 50, 51).
in a slight excess of standard potassium hy- (For an entirely different method, v. Amer.
droxide free from carbonate, and the excess Chem. J. 1896, 18, 703 ; Amer. J. Sci. 1899, 7,
titrated with standard nitric acid using phenol- 287.)
phthalein as indicator. One molecular propor- SELEKIC ACID. lodimetricatty. (L) The acid
tion of S P
5 present as (NH 4 ),PO 4 ,12MoO 3 , is boiled with hydrochloric acid (25 c.c. concen-
requires 23" molecules of KjO in pure aqueous trated acid in a total volume of 75 c.c.) for
caustic potash. P ZO S Z =23K O
(J. Amer. Chem. 10 minutes in a Bunsen distilling apparatus or
Soc. 1895, 17, 950 ; 1897, 19, 703 ; J. Soc. Chem. one of its various modifications, and the chlorine
Ind. 1904, 23, 1186). evolved is collected in potassium iodide (r.
(e) By precipitation. To the solution, feebly supra, Volumetric estimation of halogens, p. 209)
acid with acetic acid, 10 c.c. of 10 p.c. am- SeO, =
Cl z (Amer. J. Sci. 1895, 50,
monium acetate are added and standard uranium (ii.) The solution (60 c.c.) containing
20 c.c. of
acetate solution (35 grams per litre) run in from sulphuric acid (1:1) and 1 gram of potassium
a burette until a drop of the solution gives a bromide is distilled and the liberated bromine
brown colouration with potassium ferrocyanide collected in potassium iodide. SeO, Br* =
upon a white tile. The solution is heated to (Amer. J. Sci. 1895, 50, 402).
boiling, when the latter reaction will no longer SELESITM ix EITHER STATE OF OXIDAI
take place, and more uranium acetate added lodimetricatty. This is effected by a
until the brown colouration is obtained once distillation,the solution (60 c.c.) containing
more, e,g. : 5 c.c. of concentrated hydrochloric acid and
z4Izs2s41ii
= KC H,0 +2HC,H,0 +UO NH PO
Z 4 4
1-3 grams of potassium iodide. The selenium
compound is reduced to the element itself, and
an equivalent of iodine is distilled into potassium
In analysing alkali phosphates, the uranium iodide and titrated. SeO, = 2I 2
and SeO s =3I.
solution is standardised against pure potassium (Amer. J. Sci. 1895, 50, 249 ; for a simpler method
dihydrogen phosphate, while a solution of v. Amer. J. Sci. 1896, 1, 31).
ANALYSIS. 215
Silver. By precipitation, (i.) The nitric acid barium chloride, and determining the excess
by
solution is titrated with standard sodium chloride adding sodium acetate, acetic acid, and am-
until no further precipitation is observed. (For monium dichromate, and titrating an aliquot
details of this very exact method, v. the article part of the filtrate with 2^/20-ferrous sulphate
on ASSAYING. ) numberA of devices have been (Chem. Soc. Trans. 1909, 95, 2198). (iii.) The
described for rapidly filtering a portion of the sulphate is precipitated from dilute solution
liquid in order to test it for further precipita- with excess of benzidine hydrochloride solution
tion (Chem. Soc. Trans. 1908, 93, 1037 ; Gazz. as benzidine sulphate, and the
precipitate
chim. 1909, 39, ii. 240).
ital. modified A titrated with WyiO-sodium hydroxide,
using
method consists in adding a slight deficit of methyl orange as indicator (v. Zeitsch. angew.
sodium chloride, filtering and titrating the Chem. 1907, 20, 9, for details, corrections, &c.).
remaining silver with dilute ammonium thio- THIOSULPHURIC ACID. lodimetrically. Thio-
cyanate (J. Amer. Chem. Soc. 1897, 19, 814; sulphates are titrated with iodine as in stan-
v. also Chem. Soc. Trans. 1900, 77, 232 ; Zeitsch. dardising thiosulphate solution (v. supra, p. 205) ;
angew. Chem. 1904, 17, 647). (ii.) Titration may sparingly soluble salts are suspended in water
be effected with ^/10-thiocyanate as described and titrated, shaking vigorously in a stoppered
under Preparation of standard solutions. bottle all the time.
Sodium (v. Chem. Soc. Trans. 1898, 73, 167). PERSULPHURIC ACID, (a) By oxidation. The
Sulphur, Acids of. HYDROGEN SULPHIDE. solution is acidified with sulphuric acid, a con-
lodimetrically. The gas or a measured volume of siderable excess of standard ferrous sulphate is
solution is absorbed in an excess of 2VyiO-iodine, added, and then 100 c.c. of hot distilled water
the excess being afterwards titrated with N/10- (70-80). Excess of ferrous salt is then quickly
thiosulphate. 2S
H
I2 =
Direct titration with
. titrated with jV/10-permanganate. 2S 2O g
=: H
iodine leads to low results (Zeitsch. anal. Chem. 2FeO (Chem. Soc. Abst. 1900, ii. 45).
1906, 45, 541). (For other methods, v. Chem. Zentr. 1900,
HYDROSULPHUROUS ACID. By oxidation. The 435 Amer. J. Sci. 1901, 12, 367 ; Gazz. chim.
;
sodium salt, used hi indigo-dyeing, can be ital. 1902, 32, ii. 383; Bull. Soc. chim. 1903,
estimated by dissolving it in air-free water in 30, 930.)
an atmosphere of carbon dioxide, adding a Tellurium. TELLUROUS COMPOUNDS, (a) By
drop of ferrous sulphate, and running in standard oxidation. The solution is rendered alkaline
potassium ferricyanide solution until a blue with sodium hydroxide, an excess of N/lQ-pcr-
colour appears, air being rigjdly excluded manganate is added, and the excess estimated
(Zeitsch. angew. Chem. 1905, 18, 168) :
by acidifying with sulphuric acid, adding N/1Q-
and finishing the titration
'oxalic acid in excess,
Na t S,O i +2K,Fe(CN).==2S0 2 +2K,NaFe(CN).. 2Te0 2 =0 2 (Chem. Soc.
with permanganate.
If necessary, a little acetic acid is added to Trans. 1891, 59, 238; Amer. J. Sci. 1899, 8,
ensure that the liquid shall be acid.
122).
SULPHUROUS ACID. lodimetrically. An (b) By precipitation as tetraiodide in mo-
aqueous solution of sulphur dioxide is estimated derately concentrated sulphuric acid solution
by running it into an excess of standard iodine (Amer. J. Sci. 1896, 2, 271).
solution with constant stirring, and not vice Amer. Chem. J. 1898,
(c) lodimetrically (v.
versa, since that method causes a separation of 20, 278).
sulphur due to the side-reaction : TELLURIC COMPOUNDS. lodimetrically. The
S0 2 +4HI=S+2H 2 0+2I 2 tellurate is distilled with concentrated hydro-
chloric acid in Bunsen's apparatus, the chlorine
(Annalen, 1887, 242, 94). Sulphites may be accu- absorbed in potassium iodide and the iodine set
rately determined by adding the powdered salt free is titrated with ^/10-thiosulphate. Telluric
to excess of JV/10-iodine, and after the decom-
anhydride must be previously dissolved in con-
position is complete, titrating back with N/IQ- centrated potassium (not sodium) hydroxide,
thiosulphate (J. Soc. Chem. Ind. 1884, 3, 197 ;
since scarcely attacked by hydrochloric
it is
1885, 4, 303) acid. The reduction, which proceeds to tel-
SO S +I 2 +2H 2 =H 2 SO 4 +2HI. lurous acid, may be also effected by distilling
SULPHURIC ACID, (a) lodimetrically. The with bromide and dilute sulphuric
potassium
feebly acid boiling dilute sulphate solution is acid (Zeitsch. anorg. Chem. 1894, 7, 132).
Thallium. The dilute solu-
precipitated with an excess of a solution of lodimetrically.
mixed with excess of
j
barium chromate in hydrochloric acid (3^4 grams j

tion of thallic salt is
iodine liberated
potassium iodide, and the
is ti-
'
BaCr0 4 30 c.c. cone. HC1, diluted to 1 litre).

,
Barium sulphate is thus precipitated, and an trated with AyiO-thiosulphate. Tl =I 2 (Compt.

equivalent of chromic acid liberated. The rend. 1902, 134, 655).
boiling solution is neutralised with powdered Tin. STANNOUS SALTS. lodimetncally. Ine
chalk to remove excess of barium chromate, cold hydrochloric acidT solution of the stannous
and the chromic acid in the cold nitrate titrated salt is titrated with /10-iodine. A Sn =I 2 (J.
Amer. Chem. Soc. 1897, 19, 809). Free exposure
iodimetrically. CrO 3 =SO., (Amer. Chem. J. 1889,
11, 567 Chem. Zeit. 1898, 22, 357).
;
of the solution to air must be avoided, since
(b) By precipitation, (i.) The boiling sul- stannous salts readily undergo oxidation it is ;
phate solution, slightly acid with hydrochloric preferableto work in an atmosphere of carbon
acid, is titrated with standard barium chloride dioxide.
until no more precipitate is produced. Ba=S0 4 STANNIC SALTS must be reduced before
be accomplished may
(Chem. News, 1889, 59, 41). A device for titration with iodine ;
this
acid solution with
readily observing the end-point is described in by heating the hydrochloric
iron, or sheet nickel, or
with finely powdered
(ii.) Method
('hem. Soc. Trans. 1907, 91, 1370.
(i.) may be modified by adding an excess of antimony (Chem. News, 1901, 84, 167).
216 ANALYSIS.
Titanium.By reduction and subsequent diluted and titrated with N/lO-permanganate .
oxidation. It is difficult to obtain accurate Ber. 1903, 36, 3164).

results with quantities of titanium dioxide (b) By reduction. The vanadate solution,
lot or cold, and containing hydrochloric or
exceeding 0-15 gram. The warm, dilute sul-
phuric acid solution of titanic salt is reduced
to sulphuric acid, is titrated with standard (2 p.c.)
the tervalent condition by means of zinc, stannous chloride (titrated against iodine) until
a drop of the solution gives a blue colouration
aluminium-magnesium alloy, or zinc-aluminium
with ammonium molybdate. Reduction pro-
alloy (Zn, 90 p.c. Al 10 p.c., cast in sticks),
cooled* and rapidly filtered into ferric sulphate eeds as far as the tetroxide V2 4 (Bull. Soc.
solution the equivalent quantity of ferrous
;
him. 1908, 3, 626).
sulphate produced is titrated with .ZV/lO-perman- (c) lodimetrically. (i.) About 0-3-0-5 gram
ganate. Ti =
Fe (Chem. Zeit. 1907, 31, 399 ; of vanadate is distilled with 1-5-2-0 grams of
Amer. J. Sci. 1908, 25, 130 ; Analyst, 1910, 35, jotassium bromide and 30 c.c. of concentrated
198 ;compare J. Amer. Chem. Soc. 1895, 17, lydrochloric acid, the liberated bromine ab-
878).
sorbed in potassium iodide, and the iodine
Titanium and Iron (v. Iron).
titrated with 2V/10-thiosulphate V 2 5 = Br 2
; ,
reduction and subsequent ;he reduction proceeding to the tetroxide (Chem.

Tungsten. By
oxidation. The solution is reduced by zinc and Zentr. 1890, i. 977 for other iodimetric methods,
;
v. Amer. J. Sci. 1896, 2, 185, 355;

hydrochloric acid to a condition corresponding 1902, 14,
to the oxide 2 , filteredW0and titrated with a 369).
standard ferric solution. The end-point is per- Vanadium and Chromium (v. Bull. Soc. chim.
ceived by the disappearance of the intense blue 1904, 31, 962).
colour of the intermediate compound correspond- Vanadium and Uranium (v. J. Amer. Chem.
ing to W
2O5,
the reaction Soc. 1906, 28, 1443).
Fe 2 3 +WO = W0
2 3 +2FeO Vanadium and Iron (v. Iron ; and J. Amer.
Chem. Soc. 1908, 30, 1229, 1233).
being quantitative (Chem. Soc. Proc. 1909, 25, Zinc, (a) By precipitation. The chloride
227). solution, containing 3 c.c. of concentrated hydro-
Uranium, (a) By redaction and subsequent
chloric acid hi a volume of 250 c.c., is heated
oxidation. The solution, containing 20 c.c. of
nearly to boiling, and titrated with standard
concentrated sulphuric acid in a volume of
125 c.c., is poured upon 100 grams of pure potassium ferrocyanide solution (21-5 grams
per litre, titrated against pure zinc) until one
zinc (in sticks 2 cm. long), heated nearly to
or two drops of the solution produce a brown
boiling for 15 minutes, filtered into a large colouration with uranium nitrate (J. Amer.
porcelain dish, and the zinc washed with cold Chem. Soc. 1900, 22, 198 ; 1904, 26, 4 ; 1908,
dilute sulphuric acid (1 10 by volume) till the :
30, 225 ; Zeitsch. anal. Chem. 1906, 44, 174).

total volume of solution is 300 c.c. The solution
The uranium nitrate indicator may be replaced
of uranous sulphate, which should be sea-green in
by ammonium molybdate (Chem. Zeit. 1905, 29,
colour, is then titrated with iV/lO-permanganate. It has been recommended to add excess
951).
The solution can also be reduced by passage of ferrocyanide, and titrate back with standard
through a long column of amalgamated zinc ;
zinc chloride (Zeitsch. anal. Chem. 1896, 35,
in either case the reduction proceeds a little
460).
too far, but oxidation to the uranous state is
(For the application of this method to ores
accomplished during the filtration and washing. and alloys, v. J. Amer. Chem. Soc. 1907, 29,
High results are obtained by carrying out the 265 ; Chem. Zeit. 1905, 29, 951 ; J. Soc. Chem.
experiment in an atmosphere of carbon dioxide. Ind. 1905, 24, 228, 1278.)
5U(S0 4 ) 2 = 2KMn0 = 4 10FeS0 4 or ,
U= 2Fe (b) Acidimetrically. As for Magnesium, v.
(J. Amer. Chem. Soc., 1909, 31, 367 ; compare supra, p. 212; and J. Amer. Chem. Soc. 1901,
ibid. 1901, 23, 685 ; 1906, 28, 1541 ; Amer. J. 23, 468.
Sci. 1903, 16, 229). (c) lodimetrically. As for Magnesium, v.
(b) lodimetrically (v. Ber. 1904, 37, 189). supra, p. 212 ; and J. Amer. Chem. Soc. 1900,
Uranium and Vanadium (v. J. Amer. Chem. 22, 353.
Soc. 1906, 28, 1443).
Vanadium, reduction and subsequent
(a) By COLOEIMETBIC METHODS.
oxidation, The vanadic
solution containing
(i.) These methods are especially valuable for
sulphuric acid is boiled with sulphur dioxide the estimation of very small quantities of sub-
until the colour is a pure blue, and the excess stances, and are capable of giving very accurate
of sulphur dioxide then expelled with carbon results. The depth of tint produced by some
dioxide the solution, containing vanadium
; characteristic colour reagent in a given volume
salt corresponding to the oxide 2 4 , is then V of the solution is compared with the tint pro-
titrated hot with IVy 10-permanganate. (ii. ) The duced by the same reagent in an equal volume
sulphuric acid solution is passed through a Ion; of a solution containing a known quantity of
column of amalgamated zinc, and the reducei the substance to be determined. The tint in
solution collected and. titrated as describee the comparison tube can be varied by varying the
under Molybdenum (v. supra, p. 213). In thi proportion of the substance which it contains,
ease reduction proceeds as far-as the oxide V 2 2 and when the tints are equal the quantities of
(Amer. J. Sci. 1908, 25, 332; compare ibid. the substance in each tube are also equal. The
1903, 15, 389). (iii.) The solution is evaporatec quantity in one tube is known, and hence that
nearly to dryness three times with concentrated in the other is determined. It is important that
hydrochloric acid, when vanadyl chloride VOC1 2 the comparison be made under comparable con-
is formed ; hydrochloric acid is removed by ditions with respect to degree of acidity or
alkalinity, proportion of the reagent, and
evaporation with sulphuric acid, the solution the
ANALYSIS. 217
like. It is also important that the depth of tint does not interfere (Tauber, Ber. 1899, 32, 3150).
should not be materially affected by the presence A mixture of potassium carbonate (138 parts)
of other saline substances in the solution under and magnesium powder (72 parts) has been re-
examination. commended for general use in detecting nitrogen
The following substances may be determined even in the case of diazo- derivatives and stable
by these methods :
pyrrole compounds (v. Ber. 1902, 35, 2523 ;
Lead, with hydrogen sulphide. Gazz. chim. ital. 1904, 34, [2] 359). This
Copper, with hydrogen sulphide or potassium mixture is, however, found to take up nitrogen
ferrocyanide (Carnelley, Chem. News, 32, 308). from the atmosphere (Ellis, Chem. News, 1910,
Iron, with potassium ferrocyanide (Carnelley, 102, 187).
Chem. News, 30, 257). Halogens are detected by heating the sub-
Iron, with potassium thiocyanate (Thomson, stance with pure lime or pure soda-lime, extract-
Chem. Soc. Trans. 1885, 493). ing with water, slightly acidifying with nitric
Vanadium, with hydrogen peroxide. acid, and testing with silver nitrate. Highly
Titanium, with hydrogen peroxide (Weller, nitrogenous compounds, when heated with lime,
Ber. 1882, 15, 2593). are apt to yield calcium C3 anide ; hence the
r
Ammonia, by Nessler's solution (v. WATER). supposed precipitate of silver halide should
Iodine, in solution in carbon disulphide, or always be tested for cyanide (v. Separation
with starch. of cyanide and chloride), unless nitrogen is
Nitrates, by phenolsulphonic acid test known to be absent. With soda-lime no
(v. WATER). cyanide is formed. The substance may also be
Nitrites, by (i.) m-phenylenediamine ; (ii.) heated with sodium or potassium as in testing
sulphanilic acid and a-naphthylamine (v. WATER). for nitrogen iodine and bromine are detected
;
The principle may likewise be applied to the by acidifying, adding chlorine water, and shaking
comparison of colouring matters, provided that up with chloroform, which becomes purple or
the solutions are sufficiently diluted (v. COLORI- brown. The supposed silver chloride should,
METER). however, always be tested for cyanide.
Sulphur and phosphorus in non- volatile sub-
ULTIMATE ANALYSIS OF CARBON COMPOUNDS. stances are detected by fusing with caustic soda
The majority of carbon compounds contain or potash mixed with about one-fifth its weight
carbon, hydrogen, and oxygen, or carbon, hydro- of potassium nitrate, or by heating with sodium
gen, oxygen, and nitrogen a smaller number
; peroxide diluted with sodium carbonate in ;
contain one or more of the halogens, or either case the product is tested for sulphuric
sulphur. There are a still smaller number of or phosphoric acid. Volatile or non-volatile
organic derivatives of phosphorus, arsenic, substances may be oxidised by heating in a
antimony, silicon, and other metalloidal and sealed tube at 150-300, according to cir-
metallic elements, and the metals also occur in cumstances, with fuming nitric acid of sp.gr. 1 -5.
the salts of organic acids. Sulphur and are oxidised to sul-
phosphorus
phuric and phosphoric acid respectively.
Qualitative Examination. Sulphur is also detected by heating the sub-
Carbon is converted into carbon dioxide stance with sodium, extracting with water, and
adding sodium nitroprusside, when
when the substance is heated with cupric oxide. a brilliant
Hydrogen. The substance is heated to a violet colouration indicates the presence of
temperature below that at which decomposition alkaline sulphide.
begins, until all water existing as such is ex- Arsenic and antimony are detected by fusing
pelled, and is then heated with finely divided the substance with equal weights of sodium
and recently ignited cupric oxide ; the hydrogen carbonate and sodium peroxide, extracting with
is evolved as water. water, acidifying, and passing in hydrogen sul-
Nitrogen. Many carbon compounds contain- phide. Other appropriate tests for these two
ing nitrogen evolve this element in the form of elements may be applied.
ammonia when heated with caustic soda or soda-
lime, but this test is not applicable to nitro-, Quantitative Determinations.
nitroso-, azo-, and diazo- derivatives. Carbon and hydrogen in absence of nitrogen,
Many nitro-, nitroso-, and diazo- derivatives halogens, &c.
evolve oxides of nitrogen, with or without ex- The simplest and most convenient method
plosion, when heated. for general purposes is to burn the compound in
Nitrogen in all classes of carbon compounds, a glass tube in a current of oxygen, assisted by
with the exception of the diazo- compounds, cupric oxide the carbon is converted into car-
;
may be detected by heating the substance with bon dioxide, which is absorbed by caustic
into water,
metallic sodium or potassium, together with potash the hydrogen is converted
;
some sodium carbonate if the substance is which is absorbed by calcium chloride or con-
explosive. The nitrogen is converted into centrated sulphuric acid.
alkali cyanide, and the cooled mass is extracted Erlenmeyer's modification of
Von Babo s
with water and the cyanogen detected by the furnace is frequently -employed. The heat is
Prussian-blue test, which consists in adding supplied by a row of 20-25
Bunsen burners,
ferrous sulphate to the alkaline solution aftei each of which is "provided with a tap and a per-
filtration, warming gently and then acidifying. forated collar for regulating the supply of air.
Nitrogenous carbon compounds containing The flames strike the under side of a semicircular
sulphur yield, when heated .with sodium, a or gutter in which
fireclay or sheet-iron trough
thiocyanate, and the Prussian-blue test cannot the combustion tube rests on a layer of magnesia
be used. A large excess of or asbestos. Inclined at an angle over this
potassium is recom-
mended in this case, when it is stated that sulphur a row of fireclay tiles
gutter on either side
is
218 ANALYSIS.
by which the flame is reverberated upon th The furnace can be built up in shorter lengths
upper part of the glass tube, which is thu by using fewer of the furnace blocks, of which
heated all round. Each tile can be pulled baa two are represented in Fig. 16.
and rested against an iron rail which runs down To avoid the necessity for using
an india-
each side of the furnace, and thus any part o rubber stopper between the combustion tube
the tube can be readily examined, and more and the water-absorption apparatus, Marek
over the tiles can be made to assist in regulatin; suggests a mercury joint made by drawing out
the temperature. the combustion tube to a conical end, and
In Hofmann's furnace the tube is heated bj fixing round
a knee tube by means of
this
two double rows of perforated cylindrical fire asbestos and fused silver chloride.
The knee
clay burners placed over ordinary fish-tai joint, which is loosely filled with silver ribbon,
burners. The tube rests upon the top of fits iinto a bell-shaped tube dipping under
central row of much shorter burners. Th mercury (J. pr. Chem. 1907, [2] 76, 180).
burners are inclosed by flat vertical tiles, anc The combustion tube should consist of in-
flat tiles are laid horizontally on the top. fusible potash or Bohemian glass 1-5-2 mm.
In the Glaser furnace the heat is provided bjthick, with an internal diameter of 12-15 mm.
a row of Bunsen burners. The tube is supportec It should be of such a length that it projects
a
by series of semicircular perforated iron plates about 2 cm. from each end of the gutter or
placed close together. The flames strike the trough. Pieces of copper wire gauze about 2 cm.
bottom of these plates, and then pass through th broad, heated in a flame to remove grease, are
perforations and strike against the fireclay rolled up into plugs which fit moderately tightly
covers, by which they are reverberated on the in the tube, and one of these plugs is pushed
tube, so that the latter is heated from the top into the tube to a distance of about 25 cm. from
and sides as well as from the bottom. The tube one end. The tube is then filled with freshly
is usually
wrapped round with wire gauze. This ignited granular cupric oxide to within 5 or 6 cm.
furnace will give higher temperatures than the of the other end, and a second plug is inserted.
Erlenmeyer furnace, but consumes more gas. The granules of cupric oxide should be fairly
A more modern type of combustion furnace regular in size, and 1-5-2 mm. cube. Another
which gives very high temperatures with a smal] plug about 10 cm. long is made by rolling a piece
consumption of gas has been introduced by of copper gauze round a stout copper wire 12 cm.
Fletcher. The furnace itself consists of six se- long, and bending the projecting end of the
parate hollow fireclay blocks 6 inches in length latter into a loop by means of which it can be
and of the same height, which are placed end withdrawn from the tube. This plug is placed
to end, so as to give a total length of 3 feet. in the other end of the tube behind the boat.
The combustion tube is supported on a fireclay The end of the tube nearest to the copper oxide
trough placed along the top of the row of furnace is fitted with a dry caoutchouc stopper perforated
blocks which are each pierced along one side to receive the tube of the absorption apparatus ;
with five holes leading to a hollow space im- the other end is closed by a similar stopper, which
mediately below the trough. The main gas- carries a piece of tubing of very narrow bore,
supply pipe is a brass tube of square section which is connected with the apparatus for drying
which is raised about 1 k inch above the stone the oxygen.
The substance to be analysed is contained in
a platinum or porcelain boat about 70 mm. long
and 8 mm. deep, of such diameter that it slides
easily in the combustion tube. It may con-
veniently be inclosed in a small well-corked tube
while being weighed.
The water is absorbed by granulated anhy-
drous calcium chloride, which is treated with a
FIG. 16.
bench by terminal brass supports ; it carries

thirty burners projecting at right angles from
it in a
slanting direction, so that their nozzles
reach upwards to the perforations in the furnace
blocks, the centres of these holes being about FIG.
3 inches above the bench. Each furnace block
current of dry carbon dioxide, and then wit
is therefore heated
by five burners, and rever- current of dry air to convert any calcium oxicf
beration is ensured by small semicircular fire-
present into carbonate, and thus prevent tl
clay arches, three of which fit loosely on each
of the furnace blocks. ibsorption of carbonic dioxide.
Owing to their oblique The calcium chloride is contained in a U-tuh
position, the burners are readily kept clean, the )rovided with a small side bulb for condensir
brass heating
arrangement is quite separate he water, the tube from this bulb fitting direct!
from the earthenware furnace, and the
taps and nto the cork in the combustion tube, whilst tli
lower parts of the burners are
protected from ther limb of the U-tube is closed by a caoutchouc
the heat of the furnace a brass shield running
by ork carrying a narrow tube bent at a right angle
along the whole length of the main gas pipe. nd connected with the potash bulbs (Figs. 18
ANALYSIS. 219
and 19). In the absence of the side bulb, each The tube containing the soda-lime is con-
limb of the tube is closed by a caoutchouc cork nected with a U-tube filled with calcium
chloride,
carrying a narrow tube bent at a right angle, to protect the absorption apparatus from mois-
one of these tubes fitting directly into the cork ture ;this is especially needful when the air is
of the combustion tube, and the other being drawn through the apparatus by means of an
connected with the potash bulbs. A small test- aspirator.
tube, 2-3 cm. long, placed in the upper part of The oxygen or air used in the combustion is
the first limb of the U-tube, collects the greater freed from carbon dioxide by
passing through a
part of the water, and thus protects the calcium strong solution of caustic potash. If compressed
chloride (No. 1, Fig. 17). (For other forms of oxygen is employed, it is advisable to pass it first
calcium chloride tubes, v. Chem. Soc. Proc. 1906, through a short length of heated combustion tube
22, 87 ; Chem. Zeit. 1907, 31, 342.) containing cupric oxide, in order to burn out
A U-tube containing pumice moistened with any carbonaceous impurity. The air or oxygen
strong sulphuric acid may also be used to collect is then dried
by passing through dry calcium
the water, but bulbs filled with the acid must chloride or through pumice moistened with
not be used, since it dissolves an appreciable concentrated sulphuric acid, the same desic-
quantity of carbon dioxide. cating agent must be used to dry the gas as is
The carbon dioxide is absorbed in a strong employed to collect the water produced during
solution of potassium hydroxide made by dis- the combustion.
The oxygen is dried by passing it through
two long U -tubes containing calcium chloride.
Instead of the U -tubes we may use a tall
cylinder with the lower half filled with soda-lime
and the upper with calcium chloride.
The oxygen required for combustions in the
open tube may be prepared from potassium
chlorate and magnanese dioxide and stored over
water in gasholders of moderate capacity. The
FIG. 18.
gas may also be generated as required by the
solving this substance in an equal quantity of following method, which furnishes the gas under
water. The solution is contained in ' potash sufficient pressure for use in combustions. A
bulbs,' of which there are many forms. Geissier's solution of 25 grams of potassium permanganate
form is the most convenient, since it will stand in 500 c.c. of water, and 50 c.c. of sulphuric acid
is introduced drop
on its own base (No. 2, Fig. 18). Liebig's original by drop into a litre flask
form (No. 1) is still used, but the more recent containing 500 c.c. of hydrogen peroxide (10
vols.). The gas contains chlorine and ozone,
which are removed during its passage through
the purifiers (Bull. Soc. Chim. 1907, [4] 1, 501).
The operation. The tube is placed in the
furnace and connected at one end with the dry-
ing apparatus and at the other with the calcium
chloride guard tube, but not with the absorption
apparatus. It is gradually heated to redness,
a current of dry oxygen is passed through for
half an hour to remove all moisture and organic
matter, and the tube is allowed to cool. When-
a combustion tube is being used for the first
time or after a long interval, it is advisable to
carry out a blank experiment by putting on the
FIG. 19. absorption apparatus and heating the tube for
some time in a stream of dry oxygen. If the
form devised by Bender (Fig. 19) secures efficient tube is ready for the analysis, the weight of the
absorption, and is convenient for weighing, as absorption tube and apparatus should be
it stands either on its own base or on an alu- constant. The solid or non-volatile liquid sub-
minium foot. stance is now weighed into the platinum boat,
The Geissler or Liebig bulbs must contain which is introduced into the tube by removing
such a quantity of caustic potash solution that the long copper plug at the back, and the latter
it washes The front end of the tube is
up to a certain extent in the last is then replaced.
bulb, but yet is not sufficient to fill the large then connected with the absorption apparatus,
first bulb in case a vacuum is and the other end is connected with the drying
produced by rapid
absorption of the gas. In addition to the potash tubes and the oxygen reservoir. The burners
bulbs, a U-tube filled with granulated soda-lime, under the front part of the tube are now lighted
with a layer of calcium chloride 2 cm. and the temperature gradually raised until the
deep in the
upper part of each limb, is used to absorb the tube is at a dull-red heat to within 12 cm. of the
last traces of the The tube in contact with the stopper at
gas and any small quantity of boat.
moisture that may be given off from the caustic the front end should be so hot that it can only
potash solution. Two such soda-lime tubes may just be touched by the finger,
and this tempera-
be used in place of ture should be maintained throughout the
potash bulbs. ( For other forms
of carbon dioxide
absorption tubes, v. Chem. Zeit. operation by regulating the first
two burners, in
1905, 29, 569; 1907, 31, 342; 1908, 32, 77; order to prevent condensation of moisture with-
Amer. Chem. J. 1906, 35, 309 : Ann. Chim. anal. out decomposing the stopper. If any water
1907, 12, 318 ; Chem. Soc. Proc. 1908, 24, 182.) should condense, it may be volatilised by bringing
220 ANALYSIS.
one of the hot over the tube. The last
tiles close passage, and the narrow diameter of the entrance
two or three burners under the long copper plug tube assists in a similar manner, but in all cases
at the back are now lighted and the temperature of the analysis of a volatile substance a slow
gradually raised to dull redness, whilst at the current of air should be passed almost from the
same time the copper oxide is heated to within beginning. Later, oxygen should be passed, but
5-6 cm. of the boat, and a current of oxygen is not too soon, otherwise an explosive mixture
passed through the tube at the rate of a bubble may be formed. The open tube, in fact, does not
every two seconds. One of the burners under yield such satisfactory results with volatile
the "boat is then lighted and the boat very liquids as with other substances, and in such
gradually heated, combustion being regulated cases combustion should be made by the follow-
so that the bubbles passing into the potash bulbs ing method.
can easily be counted. When the substance is Liebig's original method aa modified by
completely carbonised, the temperature of the Bunsen. Granular cupric oxide and some of the
boat is raised and the current of oxygen increased finely divided oxide are heated strongly, and
to a bubble per second. Towards the close of while still hot are placed in flasks with long necks
the operation the boat is heated to redness and
a somewhat more rapid current of gas is passed.
It is not necessary to heat the tube above red-
ness, and a higher temperature produces distor-
tion. When combustion is complete, the current
of oxygen is continued for a short time to drive
out all carbon dioxide and reoxidise any reduced
copper. When the oxygen bubbles through
the potash bulbs at the same rate as through
the drying apparatus, the oxygen reservoir
is disconnected and a current of air is drawn
FIG. 20.
through the whole apparatus to expel the oxygen.
At the same time the tube is gradually cooled which are then tightly corked. The combustion
and is ready for a second operation. If the tube is drawn out at one end in the manner
tube is carefully heated and cooled, it may be shown in the figure, and sealed at the point a.
used for a very large number of analyses. The A layer of granular cupric oxide
absorption apparatus is disconnected and about 10 cm. long is first intro-
weighed. All the weighings should be made duced by placing the combustion
without the plugs of caoutchouc tubing and tube in the neck of the flask (Fig. 21)
glass rod which are used to protect the contents
When containing it, and then 23 cm. of
of the tubes and bulbs from the air.
the finely divided oxide. The sub-
several analyses are being made of substances
stance (about 0-5 gram) is now intro-
which burn only with difficulty, the entire heat- duced from a long narrow weighing
ing may with advantage be carried out in a tube which can be inserted into the
current of oxygen, and some saving of time is mouth of the combustion tube, and
effected by weighing the absorption apparatus
5-6 cm. of the finely divided oxide
filled with oxygen.
is added and intimately mixed with
Volatile liquids are inclosed in a small thin
the substance by means of a 'long
cylindrical glass bulb 3 cm. long, with a capillary
copper wire, the lower end of which
neck, readily made by drawing out a piece of has two twists like a corkscrew (Fig.
wider tubing. The bulb is weighed, heated, and
22). The wire and sides of the tube
the capillary tube immersed beneath the liquid.
are rinsed with some of the oxide, and p IGt 21.
As the tube cools a small quantity of the liquid the tube is filled with the granular
enters. This is heated to boiling, and when the
oxide to within 5-6 cm. of the top, and a plug of
air is expelled the end of the tube is again
cupric gauze inserted. Every care must be taken
placed in the liquid, and when the vapour con- to prevent absorption of moisture by the cupric
denses the bulb is completely filled. If the
liquid is very volatile, the capillary end may be
sealed before weighing the tube, but usually this
is not necessary. The bulb is placed in the FIG. 22.
boat with the capillary end open and directed
towards the copper oxide. Combustion is con- oxide. The remainder of the operation is con-
ducted as already described, but much greater ducted as described above, and when combustion
care is required, especially if the liquid is very is complete the drawn-out end of the tube is con-
volatile. The front part of the copper oxide nected with a drying apparatus, the tip broken
must be quite red-hot before the liquid begins off inside the caoutchouc tube, and a current of
to volatilise, and it is advisable that the bulb oxygen and afterwards of air passed through
be empty before the copper oxide near the the apparatus.
boat is heated. With an iron gutter sufficient In whichever way the combustion is made it
heat is conducted to vapourise volatile liquids, is found that the percentage of hydrogen is
but in other cases a very low flame may be always about 0-1-O15 too high, a result attri-
used, or one of the hot tiles may be held over buted to the difficulty of perfectly drying the
the boat. In all cases it is difficult to prevent cupric oxide, &c. It is frequently stated that an
diffusion of vapour into the back of the tube and open tube rarely gives correct results the first
even into the drying apparatus. The long time it is used; but this is solely due to neglect
copper plug at the back increases the speed of of the precaution of first heating in a current of
the current by decreasing the diameter of the oxygen (p. 219).
ANALYSIS. 221
Combustion wiih lead chromate. Sub- furnace may be obviated by bringing a mixture
stances such as graphite, resins, &c. which are of oxygen and the vapour of the
organic sub-
oxidised with great difficulty, should be burnt stance heated to a suitable temperature, into
with lead chromate, or in extreme cases with contact with some active material, such as
lead chromate containing 10 p.c. of potassium platinum, platinised quartz, platinised asbestos,
bichromate these oxidising agents can be em-
; palladium, or even finely divided copper oxide.
ployed in either open or closed combustion tubes. This process, which has been applied successfully
The chromate is precipitated by adding potas- by Dennstedt and his collaborators to a varied
sium bichromate to a solution of lead nitrate, series of organic substances, is carried out in a
washed, dried, fused, and then granulated. It hard-glass or quartz combustion tube, about
is heated immediately before being used, and 86 cm. in length and 16-18 mm. in diameter,
the tube is filled in the same manner as with the contact material being placed about the
copper oxide in B. The efficiency of the lead middle of the tube. Platinised quartz is pre-
chromate depends mainly on the fact that at a pared by soaking thoroughly clean and dry
high temperature it fuses. After being used it quartz fragments in an alcoholic solution of
is heated with nitric acid in order to remove the pyridine platinichloride and igniting them over
reduced oxides, and is washed, dried, and the blow-pipe. A layer of about 3 cm. of this
again ignited. material can be used in the combustion, or
Carbon and hydrogen in presence of nitrogen, platinum foil or wire may be employed, one of
halogens, &e. When nitrogen is present it is the most efficient forms of this metal being a
partly converted into nitrogen oxides, which six-rayed star of platinum foil, about 10 cm. in
are absorbed by the caustic potash. In order length. The combustion is most conveniently
to avoid this source of error, the front of the effected in a double supply of oxygen. The
tube contains plugs of copper wire gauze or a boat containing the substance is placed in the
layer of granulated metallic copper 12-15 cm. hard-glass inner tube (18 cm. in length) shown
in length reduced in carbonic oxide. The copper in Fig. 23, which is open at one end and at the
is heated to redness throughout the operation,
and the nitrogen oxides are decomposed with
absorption of oxygen and liberation of nitrogen.
A silver gauze plug is preferable to the copper,
because if the latter is reduced in hydrogen, it
is apt to retain water, and if in methyl alcohol,
it may also contain carbon
(Zeitsch. anal. Chem.
1906, 14, 741).
Perkin (Chem. Soc. Proc. 1880, 37, 457)
FIG. 23.
employs precipitated manganic oxide made into
a paste with a saturated solution of potassium other terminated by a wide capillary tube,
chromate containing 10 p.c. of dichromate, dried through which a current of dry oxygen can be
and granulated. A layer of this mixture 15 cm. introduced. This inner tube has a diameter of
long is placed in the front of the tube and heated about 14 mm., and oxygen can be passed through
to 200 d-250 C. All nitrogen oxides are ab- the annular space by means of the T-tube fitting
sorbed, but if the mixture is heated too strongly over the capillary tube as shown in the figure.
they are partially expelled. After each analysis By means of this apparatus the supply of
the manganic oxide is heated more strongly oxygen required for vaporising and burning the
whilst a current of air is passed through the tube, substance can be carefully regulated. When
and the nitrogen oxides are more or less com- the organic compound contains nitrogen, sul-
pletely driven off. phur, or halogens, a large boat containing lead
The halogens, when present, form halide peroxide is placed in the combustion tube and
coppersalts, which are somewhat volatile and heated to 300-320. The sulphur is absorbed
are liable to be carried into the absorption in the form of lead sulphate, and may be esti-
apparatus. In such cases the front layer of mated by extracting the lead peroxide with
copper may be replaced by silver foil or gauze, 5 p.c. sodium carbonate solution, and estimating
which decomposes the nitrogen oxides and also the sulphate in the filtrate. The estimation of
absorbs the halogens. Compounds of this kind chlorine and bromine may be similarly effected.
may also be burnt by means of lead chromate, Iodine is not entirely absorbed by lead peroxide,
'
and, accordingly, molecular silver must be

'
(v. supra), or a mixture of the substance with
lead chromate may bo placed in a porcelain employed to take up this element (Dennstedt,
boat and burnt in a current of oxygen in the Zeitsch. angew. Chem. 1905, 18, 1134; 19, 517 ;
usual way (cf. Amer. Chem. J. 1906, 35, 531). Chem. Zeit. 1905, 29, 52; 1909, 33, 769;
Sulphur forms sulphur dioxide, which is ab- Analyst, 1905, 135 ; Ber. 1908, 41,
600 ; Bau-
sorbed by caustic potash. Compounds contain- mert, Ber. 1907, 40, 3475). Walker and Black-
ing this element may be burnt with lead chro- adder recommend a furnace 60 cm. long, with
in the
mate, care being taken that the front of the tube granular copper oxide partly placed
is not too hot or the front of the tube may
; combustion tube and partly mixed with the
weighed substance. The combustion
contain a somewhat longer layer of manganic is carried
oxide and potassium chromate, the front half out in about 30 minutes, and the tube can be
being kept at 200-250 to absorb nitrogen heated with Bunsen burners on an ordinary
4
oxides, whilst the rear half is heated to dull working bench (Chem. News, 1909, 99, cf.
;
redness and absorbs the sulphur dioxide Marek J. pr. Chem. 1906, 73, 359).
(Perkin, I.e.). Electrical method. In this process the
Combustion in presence of a contact electric current is used as the source of heat, and
substance. The use of a special combustion platinum as the catalyst. A Dennstedt inner
222 ANALYSIS.
tube is employed to contain the boat z with the DKJOP, and the absorption apparatus is fitted
weighed substance, and the spiral of platinum- on to the outer end of the nickel tube DE. A
iridium wire NJ is wound round a porcelain or divided stream of oxygen is employed as in the
quartz tube held in position in the combustion Dennstedt process, and the time required for
tube by a nickel tube DE, passing through the complete combustion varies from 15 to 40
indiarubber stopper c. The coil is heated to minutes.
redness by the passage of the current through The consumption of electrical energy in
FIG. 24.
this method of carrying out combustions is rentrapp, or of an ordinary bulb U-tube.

small, amounting to about 3-6 amperes at Winkler has devised a combination of bulb
54 volts (194-4 watts) during the time when and flask which is especially convenient for
the highest temperature is obtained (Breteau estimations by titration, since the liquid need
and Lerona, Bull. Soc. chim. 1908, [4] 3, 15 ; not be transferred. Ordinary dilute hydro-
cf. B. Blount, Analyst, 1905, 30, 29 ; Morse and chloric acid or a definite volume of standard
Taylor, Amer. Chem. J. 1905, 33, 591 ; Morse acid is placed in the bulb. The tube is gradually
and Gray, Amer. Chem. J. 1906, 35, 451 ; heated to redness, beginning at the end near
Carrasco and Plancher, Gazz. chim. ital.
1906, the U-tube, and when decomposition is com-
36, 492 ; Lippmann, Chem. Zeit. 1905, 29, 487, plete the oxalic acid at the back is heated, and
174; Tucker, J. Amer. Chem. Soc. 1907, 29, the ammonia in the tube is driven out by
1442). the current of carbonic oxide and carbon
Nitrogen. This element is determined in dioxide. The excess of acid is then determined
the form of ammonia and Varrentrapp,
(Will by standard alkali or the liquid is evaporated
;
Ruffle, Kjeldahl), or in the form of nitrogen gas, with platinic chloride as in an ordinary estima-
which is collected and measured, the weight tion of ammonia, and the precipitate is washed
being calculated from the volume (Dumas, Max- with ether containing a small quantity of alcohol,
well Simpson). dried, heated in a crucible till completely decom-
A. Will and Varrentrapp's method. The sub- posed, and the nitrogen calculated from the
stance is heated with soda-lime and the nitrogen weight of the residual platinum. Pt=N 2 The .
is evolved as ammonia, which is absorbed in nitrogen frequently forms volatile bases other
hydrochloric acid and precipitated as ammo- than ammonia, and hence the platinum pre-
nium platinichloride or estimated volumetri- cipitate cannot be weighed as such. The ratio
cally. This method is not applicable to azo-, of platinum to nitrogen is, however, the same in
diazo-, nitro-, and nitroso- derivatives, and to all cases. The precipitate is washed with ether,
certain albuminoid substances. because if such bases are present, it may be
Soda-lime is prepared by slaking 2 parts of soluble in alcohol.
good quicklime with a strong solution of 1 part It is important that the front part of the tube
of sodium hydroxide free from nitrates or sul- be heated sufficiently to secure complete decom-
phates. The mixture is dried by heating in an position, but the temperature must not be too
iron vessel, granulated, and preserved in well- high, otherwise part of the ammonia itself is
closed bottles. A mixture of equal parts of decomposed, and the results are too low. Sub-
calcium hydroxide and anhydrous sodium car- stances rich in nitrogen should be mixed with
bonate may also be used. some pure sugar in order to dilute the ammonia
A glass tube about 50 cm. long and 12 mm. and prevent too rapid absorption.
diameter, sealed at one end, is filled to a depth Various modifications of Will and Varren-
of about 5 cm. with a mixture of anhydrous trapp's method have been introduced in order
oxalic acid and granular soda-lime, and a short to make it more generally applicable, but these
plug of recently ignited asbestos is inserted. processes have been superseded by Kjeldahl's
The substance is intimately mixed with sufficient method (cf. Ruffle, Chem. Soc. Trans. 1881, 39
finely powdered soda-lime to form a layer about 87 ; Arnold, Ber. 1885, 18, 806).
15 cm. long, and is quickly introduced into B. Dumas' method. In this process the hydro-
the tube. The mortar is rinsed with a small gen and carbon are burnt by means of cupric
quantity of soda-lime, which is also put in the oxide and the liberated nitrogen collected
tube, and the latter is then filled with granular and measured. A glass tube 80 cm. long, 12 to
soda-lime to within 5 cm. from the end and a 15 mm. diameter, sealed like a test-tube at one
loose asbestos plug inserted. The tube is tapped end, is filled to a length of 12-15 cm. with dry
to form a channel over the powdered soda-lime sodium hydrogen carbonate, 4 cm. of cupric
for the escape of the gases, and is placed in a oxide is added, and then an intimate mixture
furnace, which may be considerably shorter than of the substance (0-3-0-6 gram) with cupric
that used in the estimation of hydrogen and oxide, then the cupric oxide used to clean the
oxygen. The combustion tube is attached by mortar, a layer of granular cupric oxide, and
means of a perforated cork to an apparatus for finally a layer of reduced granulated copper or
absorbing the ammonia. This may consist of copper- wire gauze not less than 15 cm. in length.
the bulbs originally devised by Will and Var- The tube is connected by means of a cork and
ANALYSIS. 223
bent tube with an apparatus for collecting the attached to the jet of the burette
by means of
The sodium hydrogen carbonate is caoutchouc tubing. By closing the lower
nitrogen.
first heated until all air is expelled and the tubulus, raising the potash reservoir, and opening
absorbed by potash the stopcock, the gas is driven over into a
issuing gas is completely gradu-
solution. The copper is then heated to redness, ated tube standing over water, and is measured.
the heat being gradually applied to the whole The error due to the unknown vapour tension of
tube as far as the carbonate. When combustion the potash solution is thus avoided, but the
has ceased, the carbonate is again heated until vapour tension of the water at the particular
all the nitrogen has been expelled. temperature must of course be taken into
The most convenient form of apparatus for account. Other forms of apparatus are de-
is that devised by H. scribed by Zulkowsky (Annalen, 1876, 182, 296 ;
collecting the nitrogen
Schiff (Zeitsch. anal. Roscoe and Schorlemmer's Chemistry, 3, pt. 1,
Chem. 7, 430), or a simi- 74) and Schwarz (Ber. 1880, 13, 771).
C. Maxwell Simpson's modification
lar form described by of DumaJ
Groves (Chem. Soc. method (Chem. Soc. Trans. 1853, 6, 290 ; Annalen,
Trans. 1880, 37, 500). 1855, 95, 74). In order to avoid the formation
The former consists of a of carbonic oxide and nitric oxide, the substance
burette, A, fitted with a is burnt with a mixture of
cupric oxide and
heavy foot and provided mercuric oxide. Into a tube similar to that
with a stop-cock, c, at used in Dumas' method is introduced about
the top. Close to the 12 grams of manganese carbonate or granulated
bottom is a tubulus, &, magnesite mixed with 2 grams of precipitated
an angle of
inclined at mercuric oxide, followed by a plug of asbestos.
about 45, and on the Another gram of mercuric oxide is introduced,
other side is another and then an intimate mixture of 0-5 gram of the
tubulus, a, connected by substance with 45 parts of a previously prepared
means of a caoutchouc and thoroughly dry mixture of 4 parts of ignited
tube previously soaked cupric oxide and 5 parts of precipitated mercuric
in paraffin with a globu- oxide. The mortar and the sides of the tube are
lar reservoir, B, which is rinsed with a similar mixture and another as-
attached to the burette bestos plug is introduced. A layer of granular
by a clip, and the height cupric oxide about 9 cm. in length and a layer of
of which
is readily ad- not less than 20 cm. granulated copper, kept in
justed. Mercury is position by another asbestos plug, fill the re-
poured into the burette mainder of the tube. After the air has been
through the lower tubu- expelled by heating the manganese carbonate or
lus to a height of 2 or magnesite, the tube is gradually heated to red-
3 mm. above the lower ness, beginning from the front. The metallic
opening, and the reser- copper not only decomposes nitrogen oxides, but
FIG. 25. voir is then filled with a also absorbs the excess of oxygen. The gas is
solution of caustic pot- collected as in Dumas' method, the magnesite
ash in its own weight of water, the lower or manganese carbonate providing the carbon
tubulus being closed with a cork. The stop- dioxide.
cock is opened and the reservoir raised until the Certain organic compounds (e.g. hydroaroma-
burette is completely filled with the alkaline tic series), when analysed for nitrogen, evolve a
solution. The stopcock is then closed and the portion of their carbon as methane, which, being
reservoir lowered to the bottom of the burette. burnt only imperfectly, adds to the volume of
The tubulus may now be opened without the the nitrogen. In these cases lead chromate is
mercury or alkaline solution being forced out. recommended as the oxidising agent, or the
When the air has been expelled from the com- substance may be mixed with cuprous chloride
bustion tube the end of the delivery tube is and copper oxide (Haas, Chem. Soc. Proc. 1906,
inserted through the tubulus and the 22, 81).
nitrogen
collected. At the close of the operation the Various modifications of Dumas' process have
temperature of the gas is allowed to become con- been proposed. Thudichum and Wanklyn use a
stant, the reservoir is raised so that the level of mixture 5 parts of normal sodium carbonate and
the liquid is the same as in the burette, and the 13 parts of fused potassium bichromate in place
volume of the nitrogen is read off, together with of sodium hydrogen carbonate. Groves (I.e.),
the temperature and the with a view to using the same tube repeatedly,
height of the baro-
meter. The weight of the places the mixture of carbonate and bichromate
nitrogen, P, is then
calculated from the volume by means of the in a small tube connected with the combustion
formula tube by an indiarubber joint. The portion
of the cupric oxide mixed with the substance is
p _V(B-/)0-00125I separated from the layer remaining always in the
(1 +
0-00366)760' tube by means of a tight plug of asbestos and
where V the observed volume, B the height
is
copper gauze, the latter keeping a free passage
of the barometer,
/ the tension of aqueous for the gas.
vapour at the temperature t, and 0-001251 the The combustion tube may be open at both
weight of 1 c.c. of nitrogen at and 760 mm. ends, the rear being connected with an apparatus
Gatterman (Zeitsch. anal. Chem. 24, 57) for generating carbon dioxide, but special pre-
collects the an apparatus similar to cautions must be taken to obtain this gas free
nitrogen in
but not graduated. A bent tube of
Schiff's, from air (v. Warington, Chem. Soc. Trans. 1882,
small diameter completely tilled with water is 41, 346).
224 ANALYSIS.
The carbon dioxide required for this modifica- need be used. The copper oxide keeps the ex-
tion ofDumas' process may be generated in a hausted tube from collapsing when heated.
In many cases, especially with nitro- deriva-
Kipp's apparatus by the action of hydrochloric
acid on marble or calcite. These minerals tives, the gas generated in the exhausted tube
should, however, be boiled with water before is a mixture of nitrogen with nitric oxide, the
latter being sometimes present in considerable
being used, in order to free them from air. The
dioxide may also be generated by dropping a quantity. It is advisable, therefore, to de-
concentrated solution of potassium carbonate compose the oxide by using either a
nitric
(sp.gr. 1-5) into a mixture of water and con- layer of reduced copper or a long plug of silver
centrated sulphuric acid. A convenient ap- gauze placed between the copper oxide and the
paratus in which to effect this operation is shown exit, and by keeping this material heated
in the accompanying figure (Young and Caud- throughout the combustion.
Liquids in which nitrogen is to be determined
may be enclosed in bulbs which are dropped into
the combustion tubes as in the determination of
hydrogen and oxygen.
The copper oxide used in nitrogen deter-
minations should be prepared by heating metallic
copper in air and never by ignition of the nitrate,
since in the latter case it is apt to contain basic
nitrates which evolve nitrogen on heating.
The copper used in nitrogen determinations,
&c., should not be reduced in hydrogen, since it
is liable to occlude this gas. It may be reduced
in the mixture of carbon monoxide and carbon
dioxide obtained by heating oxalic acid with
strong sulphuric acid. Plugs of copper gauze
may also bereduced by heating them to redness
and dropping them into a test-tube containing a
few drops of formic acid or methyl alcohol. The
FIG. 26.
reduced copper is carefully dried at 100-110.
The
When no carbonate is used and the gas is
well, J. Soc. Chem. Tnd. 1907, 26, 184).
carbonate solution flows from the dropping simply pumped out of the tube and collected
over mercury, it consists of a mixture of car-
funnel into the mercury trap and out into the
bon dioxide and nitrogen. If the former is
Woulff's bottle through the small hole a. The estimated by absorption with caustic potash, a
rate of evolution is regulated by the exit tap,
determination of the carbon may be combined
and s is a safety tube. with that of nitrogen.
In both Dumas' method and Simpson's
Jannasch and Meyer have described a method
modification the combustion tube may be drawn
for the simultaneous estimation of carbon, hydro-
out at the front end and connected with a
gen, and nitrogen (Ber. 1886, 19, 949 ; Annalen,
Sprengel mercury pump by glass tubing joined 1886, 233, 375 Zeitsch. anal. Chem. 1887, 26,
;
by short pieces of caoutchouc tubing, the joints 86; cf. Bull. Soc. chim. 1905, 33, 951).
being surrounded by short wide tubes filled D. KjeldahVs method (Zeitsch. anal. Chem.
with water or glycerol. A bulb is blown on the
1883, 22, 366). The substance is heated with
concentrated sulphuric acid to a temperature
approaching the boiling-point of the latter, and
when decomposition is complete, an excess of
solid potassium permanganate is added. The
nitrogen is thus converted into ammonium
sulphate, which is then distilled with excess of
alkaliand the ammonia collected and estimated.
This method is economical, requires no com-
bustion furnace or special apparatus, is rapid,
and requires comparatively little attention, so
that a large number of determinations can be
carried on at the same time. The substance need
not be in a very fine state of division, and the
method is especially suitable for liquid and pasty
substances such as extracts.
It is important that the sulphuric acid em-
FIG. 27. ployed for these determinations should be pro-
tected from ammonia, and the caustic soda solu-
horizontal part of the glass tube at the end near tion should be well boiled in order to expel any
the combustion tube, and this bulb is kept cool ammonia which it may contain. The purity of
during the operation, and serves to condense the the reagents is best ascertained by making an
water which is formed. The combustion tube is
experiment with pure sugar. If a small quantity
made vacuous, and when no more air issues of ammonia is present, the same quantity of the
from the end of the pump, the combustion is
reagents should be used in each experiment, and
conducted in the ordinary way, the gas which is a correction made for the ammonia which they
evolved being pumped out by the Sprengel pump contain.
and collected in a suitable tube. No magnesite In order to prevent bumping during distillation,
ANALYSIS. 225
a small piece of zinc may be placed in the in the case of substances rich in fat.
They
flask, but it is essential that
the soda should be regard the use of phosphoric oxide as unneces-
free from nitrates and nitrites, which would be sary, and the use of fuming sulphuric acid as
reduced and yield ammonia. undesirable on account of its liability to contain
The time required for the operation may be nitrogen oxides.
considerably shortened by using sulphuric acid Jodlbauer (Chem. Zentr. [3] 17, 433) uses
containing sulphuric anhydride or phosphoric phenolsulphonic acid in place of benzoic acid,
anhydride. and reduces with zinc dust. He thus obtains
The method as thus carried out is applicable ood results even with nitrates. Reitmair and
to substances which can be analysed by Will
all tutzer (Rep. Anal. Chem. 7, 4) find that the
and Varrentrapp's process, and to many others. nitrate must be somewhat finely divided ; 0-5
Heffter, Hollrung, and Morgen (Zeitsch. f. to 1-0 gram of the substance is mixed with
Chom. 8, 432) treat 1-0-1-5 grams of substance 50 c.c. of sulphuric acid containing 20 grams of
with 20 c.c. of a mixture of 4 vols. ordinary phenol per litre, allowed to stand for a short
1 vol. of fuming acid, and time with occasional agitation, mixed with 2-3
sulphuric acid and
2 grams of phosphorus pentoxide. Kreusler grams of dry zinc powder and 1 or 2 drops of
metallic mercury, and heated in the usual way.
(Zeitsch. anal. Chem. 1885, 24, 453)
uses sul-
phuric acid containing 200 grams
of phosphorus Conversion into ammonium sulphate requires
pentoxide per litre. one and a half hours.
Wilfarth (Chem. Zentr. [3] 16, 17, 113) finds A most important improvement in the
that the oxidation of the organic matter Kjeldahl process due to Gunning (Zeitsch. anal.
takes place much more rapidly in presence of Chem. 28, 188), consists in the addition of
certain metallic oxides. Mercuric oxide is the potassium sulphate to the concentrated sul-
most efficient, but cupric oxide answers almost phuric acid. The solution of potassium hydro-
equally well. The former produces mercuri- gen sulphate in concentrated sulphuric acid
ammonium derivatives, which are not readily boils at a temperature considerably above the
decomposed by caustic soda, and hence the boiling-point of the strong acid and the oxidation
alkaline liquid must be mixed with some potas- of the organic matter is thereby greatly facili-
sium sulphide to decompose the mercury com- tated. Various oxidising and catalytic agents
pounds. The mercuric sulphide formed makes may be
employed in conjunction with this
the liquid boil regularly without the addition mixture, and the following are among the
of zinc. Ulsch recommends the use of ferrous many which have been suggested in addi-
sulphate instead of potassium sulphide ; it may tion to those already mentioned platinic
:
be added before the caustic soda. chloride, ferric chloride, manganese dioxide,
Warington (Chem. News, 1885, 52, 162) magnesia, and sodium phosphate. The use of
removes nitrites and nitrates by boiling with potassium permanganate has now been aban-
ferrous sulphate and hydrochloric acid. doned, and, in the case of refractory substances,
With a view to secure the reduction of nitro- oxidation is now generally induced by the
derivatives, &c., and thus make the process catalytic action of mercury or its oxide. The
generally applicable, Asboth (Chem. Zentr. [3] following process is described by Dyer (Chem.
17, 161) mixes 0-5 gram of the substance with Soc. Trans. 1895, 67, 811). The substance
1 gram of pure sugar in the case of readily (0-5-5 grams) is introduced into a round-
oxidisable compounds, and with 2 grams of bottomed Jena flask, and heated gently with
benzoic acid in the case of nitrates and similar 20 c.c. of concentrated sulphuric acid containing
derivatives. Most probably the benzoic acid a small globule of mercury. After the initial
first forms nitro- derivatives, which are after- action has subsided, the temperature is raised to
wards reduced. He adds Rochelle salt with the boiling, and in 15 minutes 10 grams of potassium
caustic soda in order to prevent precipitation of sulphate are added, and the boiling continued
manganese, &c., and thus avoids bumping till the solution is clear and colourless. The
during distillation. With these modifications flask is closed with a loosely fitting bulb stopper,
the method is applicable to all nitrogen com- from the internal projection of which the con-
pounds except those of the pyridine and quino- densed sulphuric acid drops back into the flask.
line series. E. Arnold (ib. p. 337) uses 0-5 gram There is, therefore, little loss of acid except
of anhydrous cupric sulphate and 1 gram of through reduction to sulphurous acid. The pro-
metallic mercury in place of the oxides as duct is rinsed into a capacious Jena distilling
recommended by Wilfarth, and heats 1 gram of flask, rendered strongly alkaline with sodium
the substance with these and 20 c.c of sulphuric hydroxide, with the addition of a small quantity
acid containing 20-25 p.c. of phosphoric of sodium sulphide, and the liquid distilled in
oxide. a current of steam, the ammonia being collected
C. Arnold (Arch. Pharm. [3] 24, 785) confirms and estimated in the usual way.
Asboth's statements, but finds that in addition to When nitrates are present, Jodlbauer's
pyridine and quinoline compounds, azo- deriva- modification is employed, but the phenol may
tives and nitrites yield unsatisfactory results. conveniently bo replaced by salicylic
acid.
He heats 0-5 gram of substance with 0-5 gram When the solution of this substance in concen-
of anhydrous cupric sulphate, 1 gram of metallic trated sulphuric acid is poured quickly on to
mercury, 2 grams of phosphoric oxide, 1 gram the weighed material, the loss due to the forma-
of sugar, and in case of nitrates, &c., 2
grams of tion of loAver oxides of nitrogen is avoided, and
benzole acid, and 20 c.c. of sulphuric acid. satisfactory results are obtained
even when
Reitmair and Stutzer (Rep. Anal. Chem. 5, ammonium nitrate is present. This circum-
232 Zeitsch. anal. Chem. 1886, 25, 582) use
; stance is of great importance in connection with
about 0-7 gram of mercuric oxide and 20 c.c of the analysis of compound fertilisers containing
sulphuric acid, with a small fragment of paraffin both ammonium salts and alkali nitrates. The
VOL. I. T.
226 ANALYSTS.
zinc and mercury are added while the solution 4 grams of nitric acid for each 50 c.c. of its volume.
is still cold, and the former metal allowed to If the operation is prolonged, it is desirable to
dissolve before the mixture is heated. Otherreduce the pressure in the tube by opening it
reducing agents, such as sugar and sodium from time to time by heating the capillary end
thiosulphate, may be used either alone or in of the previously cooled tube in a flame until
it softens, when the gas forces its way out.
conjunction with zinc. By the aid of this
modified process satisfactory results are obtained The weighed substance is enclosed in a
in the analysis of organic nitro-,azo-,artd hydrazo-narrow tube of thin glass of such length that
derivatives. It has not been found possible to its mouth projects above the nitric acid in the
obtain correct estimations of nitrogen in sodium tube, and the acid does not come in contact
nitroprusside, phenylhydrazine and its deriva- with the substance until the tube is sealed.
tives, and in mixtures containing large propor- The tubes used should be about 15 mm. in
tions of chlorides and nitrates (cf. J. Amer. diameter and 1-5-2 mm. thick in the glass.
Chem. Soc. 17, 567 Analyst, 1905, 314 ; Ber. After introduction of the substance they are
;
1905. 38, 559 ; Chem. Soc. Proc. 1901, 25, 351 ; drawn out to a capillary tube with thick walls,
1903, 27, 988). which is then sealed. The sealed tubes are
The literature of nitrogen determinations is heated in a pressure tube furnace tilted at one
extremely voluminous. Summaries of contribu- end so that the capillary ends of the tubes do
tions to this subject will be found in Zeitsch. not come into contact with the liquid. After
anal. Chem. 1884, 23, 551 ; 24, 439 25,
;
424 and being heated, the tubes should on no account
571 26,
;
249 and ;
Chem. News, 1888, 57, 62, be removed from the protecting iron or steel
et seq. In addition to the references already tube until they have been opened. For this
papers relating to Kjeldahl's process may purpose the tubes are held in position by means
e found in Zeitsch. anal. Chem. 24, 199, 388, of a cork collar through which the capillary
fiven,
and 393 25, 149 and 155 ; 26, 92 ; 27, 222 and ends project out of the furnace. The capillary
;
398. end is first gently warmed to volatilise any con-

and iodine.
Chlorine, bromine, densed acid, and then heated more strongly
By lime. A tube about 40 cm. long and until the gases under pressure blow a hole
7 mm. diameter, sealed at one end like a test- through the softened tip of the sealed capillary.
tube, is filled to a depth of 5 cm. with pure In this operation the pressure of the imprisoned
granulated quicklime. The substance is weighed gases is very great, and it is extremely dangerous
into the tube and mixed with finely powdered to attempt to open the tube with a file. The
lime by means of a copper wire twisted at the end tube furnace should only be used for this pur-
like a corkscrew. The wire and tube are rinsed pose within a well-protected enclosure (Fig. 28),
with lime, the tube is filled to within 5 cm. of so as to minimise the personal risks arising from
the open end with granulated lime. The tube explosions of the heated tubes.
is gradually heated to redness from the front.
When cold the contents of the tube are dissolved
in water slightly acidified with nitric acid,
filtered, and the halogen precipitated by silver
nitrate.
In the case of iodine the substance is dissolved
in water, filtered, mixed with silver nitrate, and
finally acidified, in order to avoid liberation of
iodine. A
further precaution consists in adding
a little sodium sulphite before each addition o
nitric acid.
When the substance contains nitrogen, cyan-
ides may be formed ; but this is avoided by
If the
using pure soda-lime in place of lime.
lime contains sulphates, some sulphide is liable
to be produced. (On the preparation of pure -JJ
lime, see Zeitsch. anal. Chem. 4, 51 and 15, 5.) FIG. 28.
Liquids are contained in small bulbs with
capillary openings, which are dropped into The silver salt formed is rinsed out of the
the tube before filling up with lime. The tube
must be very gradually heated, and should be opened tube and treated in the usual way.
For the estimation of iodine in organic com-
longer than usual.
Carius's method (Annalen, 1860, 116, 1 ; 1865, pounds this method is to be preferred to the
The substance lime process, but as the silver nitrate and silver
136, 129 ; Ber. 1870, 3, 697).
iodide frequently form a fused yellow mass,
is oxidised by heating with nitric acid in sealed
the mixture must be extracted thoroughly with
tubes in presence of silver nitrate. In many
hot water in order to remove the former salt.
cases acid of sp.gr. 1-2 and a temperature of
The silver halide obtained by the Carius method
120-200 will suffice ; but substances which
is collected in a tared Gooch crucible, washed
are more difficult to oxidise require acid of
cases with some successively with water and alcohol, dried at
sp.gr. 1-42, mixed in special
100, and weighed.
potassium dichromate, or the fuming acid of
If necessary the tubes Stepanow's method. The substance is boiled
sp.gr. 1-5 may be used. with alcohol (2040 c.c.) and sodium is added
may be heated as high as 300. The quantity at such a rate that a vigorous reaction is main-
of acid used should not be more than twice
that theoretically required for complete oxida-
tained. A large excess of the metal is essential
tion, and the tube must not contain more than XCl+2Na+C 2 H 6 -OH=XH+NaCl+C 2 H 6 -ONa.
ANALYSIS. 227
When allthe sodium has dissolved, 20-40 c.c. of acid or phosphoric acid estimated in the usual
water are added, and the alcohol removed by way.
distillation. The aqueous solution is acidified Many non-volatile substances may be oxi-
with nitric acid, and the halogen estimated dised by heating with pure concentrated caustic
gravimetrically, or volumetricallv by Volhard's potash solution, diluting with twice the volume
method (Ber. 1900, 39, 4056;* cf. Bacon, J. of water, and treating with a current of chlorine.
Amer. Chem. Soc. 1909, 31, 49). By using the After complete oxidation the solution is
acidified,
latter method and weighing the mixed silver heated to expel chlorine, and the
sulphuric or
halides, the two halogens can be estimated phosphoric acid determined.
indirectly in the same compound. Arsenic. The estimation of this element in
Pringsheim's method consists in burning the organic compounds has recently acquired in-
organic substance with sodium peroxide. Com- creased importance owing to the
application of
pounds containing more than 75 p.c. of carbon these substances in therapeutics. One of the
are mixed with 18 parts of this oxidising agent, earliest methods, due to La Coste and Michaelis
and those with 5075 p.c. of carbon with 16 (Annalen, 1880, 201, 224), consisted in mixing
parts. Substances containing less than 25 p.c. the substance with soda-lime, and
heating the
of carbon are mixed with sugar or naphthalene, mixture in a stream of air or oxygen. The
and treated with 1618 parts of the peroxide. residue was dissolved in nitric or hydrochloric
The mixture is placed in a steel crucible sur- acid, the arsenic precipitated as sulphide, and
rounded by water and having a perforated lid afterwards converted into magnesium pyro-
through which a glowing iron wire is thrust to arsenate. Monthoule recommends destroying
cause ignition. The product is extracted with the organic matter with nitric acid
containing
water, acidified with nitric acid, and the halogen magnesium nitrate, when a final ignition leads
estimated in the usual way (Ber. 1903, 36, 4244 ;
to the formation of magnesium arsenate (Ann.
1904, 37, 324 :1905, 38, 2459 ; Amer. Chem. J. Chim. anal. 1904, 9, 308).
1904, 31, 386; cf. Moir, Chem. Soc. Proc. 1907, Pringsheim oxidises the organic arsenic
23, 233 Baubigny, Bull. Soc. chim. 1908, (iv.)
;
derivative with sodium peroxide, and estimates
3, 630). the arsenic as magnesium pyroarsenate (Amer.
Sulphur and phosphorus. Chem. J., 1904, 31, 386).
Non-volatile substances. Pure caustic potash The following procedure has been shown
is fused in a silver dish with about one-sixth its to be applicable to the organic arsenical
weight of potassium nitrate and a little water. drugs now on the market. The substance
When cold the substance is weighed into the (0-2-0-3 gram) is mixed with 10-15 grams
dish, which is again heated, the substance being of sodium peroxide and sodium carbonate in
mixed with the alkali by means of a silver equal proportions, the mixture heated gently
spatula. When oxidation is complete, the mass in a nickel crucible for 15 minutes, and the
is allowed to cool, and is then dissolved in water temperature then raised to dull redness for
acidified with hydrochloric acid, and the sul- 5 minutes. The product is extracted with water,
phuric or phosphoric acid estimated in the usual 25-31 c.c. of sulphuric acid (1:1) added, and
way. the solution concentrated to 100 c.c.,when 1 gram
Carius's method is carried out exactly as in of potassium iodide is added and the liquid
the estimation of the halogens. Sulphur is boiled down to 40 c.c. After destroying any
oxidised to sulphuric acid and phosphorus to trace of iodine with a few drops of sulphurous
phosphoric acid. It is advisable to remove the acid, the solution is diluted considerably with
greater part of the nitric acid before precipita- hot water, and the arsenic precipitated as sul-
ting barium sulphate or magnesium ammonium phide. The precipitate, after washing three times
phosphate. with hot water, is dissolved with 20 c.c. of
Another method applicable to volatile and .Af/2-sodium hydroxide, and the filtered solution
non-volatile substances is as follows :Into a treated with 30 c.c. of hydrogen peroxide (20
combustion tube 40 cm. long, sealed at one end, vols. ), the excess of this reagent being destroyed
is introduced 2-3
grams of pure mercuric oxide, by heating on the water- bath. A few drops
then a mixture of the substance with equal proof phenolphthaleiin are added followed succes-
portions of mercuric oxide and pure anhydrous sively by 11 c.c. of sulphuric acid (1:1) and one
sodium carbonate, and the remainder of the gram of potassium iodide the solution is
;
tube is filled with sodium carbonate mixed with evaporated down to 40 c.c. and the pale-yellow
a small quantity of mercuric oxide. The open colour removed by sulphurous acid. Cold water
end of the tube is closed by a cork carrying a is then added, and the diluted solution neutralised
glass tube dipping under water, in which the with 22V-sodium hydroxide, and just acidified
mercury is condensed. The tube is carefully with sulphuric acid. The arsenite solution is
heated so that the front layer of sodium car- now titrated Avith standard iodine solution and
bonate is red hot before the substance begins to starch in the presence of sodium hydrogen
volatilise. The substance is then rapidly heated, carbonate or sodium phosphate (Little, Cahen,
so that decomposition is complete in about and Morgan, Chem. Soc. Trans. 1909, 95, 1477).
fifteen minutes, and finally the mercuric oxide Antimony. When present in organic com-
at the rear end of the tube is heated until pounds, this element may be estimated by acidi-
fying the product of the sodium peroxide
oxygen issues from the end of the delivery- fusion
tube (Russell, Chem. Soc. Trans. 1854, 7, 212 ; (v. Arsenic, supra), and precipitating
as sulphide,
J. pr. Chem. 1855, 64, 230). The contents of this precipitate being collected, washed, and
the cooled tube are dissolved in water, a small weighed in the manner indicated under Gravi-
quantity of bromine water added to oxidise any metric determinations.
sulphide, the solution acidified with hydrochloric Oxygen. No satisfactory method has yet
acid, boiled to expel bromine, and the sulphuric been devised for the direct determination of this
Q 2
228 ANALYSIS.
element, and it is usually estimated by difference Fractional solution. The most useful and
(v. Baumhauer, Annalen, 90, 228
v. Zeitsch.
; most generally applicable method of proximate
anal. Chem. 5, 141 Stromeyer, Annalen, 117,
; analysis is based upon the different solubilities
247 Mitscherlich, Zeitsch. anal. Chem. 6, 136
; ; of various substances in different menstrua.
7, 272; 13, 74, and 15, 371; Ladenburg, The mixture is treated successively with various
Annalen, 135, 1 ;Maumene, Compt. rend. 55, solvents, each of which dissolves some of the
432 and Cretin, Zeitsch. anal. Chem. 13, 1).
; constituents, but leaves the others undissolved.
Proximate analysis of carbon compounds. Advantage may also be taken of the fact that the
The methods to be adopted for the separation solubilities are in many cases modified by a rise
of the constituents of any particular mixture of temperature. Further, if two substances differ
will depend entirely upon the nature of the considerably in their solubility in one and the
mixture. It is only possible to describe the same liquid, they may be separated by treatment
general methods which are found to be most with successive small quantities of the liquid,
useful in organic analysis. To a certain limited which removes the more soluble compound but
extent these operations are applicable to the leaves the greater part of the other undissolved.
proximate analysis of complex inorganic mix- The following is a list of the solvents commonly
tures. employed, with indications as to their general
Fractional distillation is available for the properties :
separation of liquids which differ considerably Water dissolves many salts and acids in- ;
in their boiling points (v. DISTILLATION). organic and organic alkalis and their salts ;
Distillation in a current of steam is fre- carbohydrates, gums, certain alcohols, poly-

quently employed as a method of proximate hydric phenols, and other highly oxidised
analysis. In this way volatile organic acids carbon compounds whih are not readily solu-
can be separated from volatile bases by steam- ble in alcohol, ether, &c. On the other hand, it
distilling the mixture in the presence of mineral does not dissolve the carbonates, phosphates,
acids. On the other hand, volatile bases are oxalates, and certain other salts of the heavier
separated from organic acids by distilling metals. Very many organic substances are in-
in steam the mixture of these substances soluble in this liquid. It decomposes the halogen
rendered alkaline by sodium or potassium compounds of the acid radicles and certain other
hydroxide. compounds, and converts many normal metallic
Fractional precipitation may be employed salts into basic salts, part of the acid passing into
for the separation of substances, some of which solution in the free state.
are precipitated by a given reagent, whilst the Dilute acids will dissolve many salts, and
others are not ; or for the separation of sub- also some organic substances which are insoluble
stances which differ in the order of their preci- in water.
pitation. If, for example, silver nitrate is added Alcohol dissolves many salts, caustic alkalis,
in successive small quantities to a solution con- hydrocarbons, fatty acids, resins, and a very
taining an iodide, bromide, and chloride, the large number of carbon compounds. It reacts
first portion of the precipitate contains the with many haloid substitution derivatives, and
greater part of the iodine ; the middle portion hence is not a suitable solvent for this class of
contains the greater part of the bromine ; and compounds.
the last portion the greater part of the chlorine. Ether dissolves a few salts, and is an excel-
In a similar manner organic acids can, not un- lent solvent for hydrocarbons, fats, resins, alka-
frequently, be separated by taking advantage loids, and almost organic compounds which
all
of differences in the order of then* precipitation are insoluble in water. It reacts with very few
by silver nitrate or lead acetate. In these cases substances, and boils at a low temperature, so
the separated precipitates can be suspended in that it can readily be distilled off and the dis-
water and decomposed by hydrogen sulphide, solved substance recovered.
when the acids are again liberated. Benzene dissolves iodine, sulphur, phos-
Fractional crystallisation may be adopted in phorus, oils, fats, wax, camphor, resins, caout-
the case of substances which differ in their solu- chouc, gutta-percha, &c., and is especially useful
bility in one and the same solvent. The solution as a solvent for haloid derivatives, on which it
is concentrated somewhat, and the crystals which has no action. In certain instances this hydro-
separate are removed ; the mother liquor is still carbon maybe replaced by its homologues,
further concentrated, and the second crop of toluene, and the xylenes.
crystals is removed, this process being repeated Carbon disulphide shares with ether the
as often as the case demands. The least soluble advantage of being readily volatile. It should
compound is mainly in the first crop of crystals ; always be purified from dissolved sulphur before
the most soluble is in the last mother liquor. being used. The best plan is to mix it with a
Fractional saturation is an analogous pro- small quantity of white wax, and then distil off
cess,but is of more limited application. It was the disulphide on a water-bath. It dissolves
employed by Liebig for the separation of volatile sulphur, phosphorus, iodine, fats, essential oils,
organic acids. The mixture of acids is mixed with resins, caoutchouc, &c. ; but its solvent powers
a quantity of caustic soda or potash insufficient are comparatively limited, and almost all salts
for complete saturation, and is then distilled. and very many carbon compounds are insoluble
The acids of higher molecular weight are first in it.
neutralised and converted into salts, which of Light petroleum consists of the more volatile
course remain in the retort, whilst the acids hydrocarbons of the paraffin series. It occurss
of lower molecular weight are found in the free in commerce in several varieties under different
state in the distillate. Anything like complete names: Petroleum ether boils at 50-60 petro- ;
separation is only to be obtained by many repe- leum benzene, at 70-90 ligroln, at 90-120.
;
titions of this process. They are excellent solvents for oils and fats, but
!
ANALYSIS. 229
dissolve very few other compounds. Three bend of the siphon, the latter draws off the clear
grades of light petroleum are now obtainable solution into the flask, and the liquid is
again
for use as solvents, boiling respectively at 40-60, volatilised whilst the dissolved matter remains
60-80, and 80-100. inthe flask. The process goes on
automatically,
Chloroform readily dissolves oils, fats, and and the substance can be extracted many times
similar substances, and is especially useful as a with a small quantity of liquid. When extrac-
solvent for alkaloids. tion is complete, the flask is connected with an
The chloro- derivatives of ethane and ordinary condenser, the liquid is distilled off,
ethylene have been introduced as useful non- and the residue dried and weighed if necessary.
inflammable solvents for oils, fats, or resins ; A convenient apparatus for treatment with
these liquids give a wide range of boiling-points solvents in dishes has been described by A. W.
and solvent action (Koller, 7th Congress Applied Blyth (Chem. Soc. Trans. 1880, 37, 140).
Chemistry, 1909). A large number of other In many cases substances in solution can be
solvents are applied in certain special cases, and removed and separated by agitating the liquid
among those more commonly employed may be with some non-miscible solvent. The alkaloids
mentioned, acetone, ethyl acetate, amyl alcohol, and many amines can be removed from aqueous
pyridine, aniline, and nitrobenzene. solutions by means of ether, whilst metallic salts
The treatment of a solid with a volatile are left ; fatty substances can be removed from
solvent must be conducted in a special apparatus, liquids by means of light petroleum, and so on.
especially if the liquid is to be heated. Various Extractions of this kind are best made in a
forms of apparatus have been devised for this separator consisting of a somewhat wide tube
purpose, but there is none more efficient than contracted at one end, which is fitted with a cork
that of Soxhlet (Dingl. poly. J. 232, 461). It or stopper, whilst the other end is drawn out
consists of a short wide test tube (E), open at into a narrow tube provided either with a stop-
the top but closed at the bottom, to which is cock or an indiarubber tube and a pinch-cock
sealed a narrower tube (N) which can be fitted (Fig. 30). The liquid and the solvent can be
completely mixed by agitation, and after they
A have separated the lower layer can be drawn
off. If it is required to remove the supernatant
liquid in this or any similar case, a somewhat
narrow tube is bent twice at right angles, and
one limb is fitted by means of a cork into a dis-
tilling or other flask, which is connected with
an aspirator, whilst the other limb of the tube
is placed in the liquid. When the aspirator is
set hi action, the liquid is drawn over into the
flask, from which it can be distilled. With care
a very accurate separation can be made, and
the tube is readily rinsed by drawing some of
the fresh solvent through it. This method may
be rendered approximately quantitative by cali-
brating the above cylindrical separator (Fig. 30).
The microscope is of the greatest service in
ascertaining whether a substance is a single
compound or a mixture, and a microscopic
examination of the various products obtained
FIG. 29. FIG. 30. in the course of a proximate analysis affords
valuable information as to the extent to which
into a small weighed by means of a cork.
flask separation has been effected.
Communication between the two tubes is made by
means of (1) a narrow side tube (s) which opens ESTIMATION OF RADICLES COMMONLY OCCUB-
into the bottom of the wider upper tube, forms BING IN ORGANIC COMPOUNDS.
a siphon, and descends through the lower tube In this section it is only possible to indicate
nearly to the bottom of the flask and (2) a
; a few of the most general methods by
briefly
wider side tube (t) which enters the upper tube which certain typical radicles present in organic
near the top and the lower tube near the junction
compounds can be estimated.
(Fig. 29). A weighed quantity of the substance Hydroxyl. A known weight of the hydroxylic
to be treated is placed in a cylinder of filter
compound is treated with excess of magnesium
paper open at the top, and introduced into the methyl iodide (Grignard's reagent), and the
upper tube, or the bottom of the tube is packed amount of methane evolved is measured in a
with purified cotton wool, and the substance is
gas burette (Fig. 31).
placed upon this. A quantity of the solvent
rather more than sufficient to fill the upper tube R-OH+CH 3 -MgI=R-OMgI+CH 4 .
to the level of the bend in the siphon, is placed The organic magnesium compound is dis-
in the flask and heated to boiling by means solved in dry amyl ether or phenetole, and if the
in either of
of a water-bath. The upper tube is attached hydroxylic compound is too insoluble
to a reflux condenser, care being taken that the it may be dissolved indry pyridine.
these solvents,
(Hibbert and Sudborough, Chom. Soc.
Trans.
condensed liquid falls directly into the cylinder
containing the substance. The vapour passes 1904, 85, 933 and Zerevvitinoff, Ber. 1907, 40,
;
up the wide side tube, is condensed, falls upon 2023.)

the substance, and filters through the paper or This process has been extended to the
cotton wool. As soon as the liquid rises to the estimation of sulphydryl- (SH), imino-, and
230 ANALYSIS.
amino- groups, and for all active hydrogen heated in a glycerine bath at 130*-140, a current
of carbon dioxide being passed through the mix-
atoms (c/. Ber. 1908, 41, 2233 and 3025).
ture of substance and concentrated hydriodic
acid. The heating is continued for one hour,
and the temperature finally raised, so that the
hydriodic acid .boils gently, but without dis-
tilling into the side tube of the distilling flask.
The methyl iodide is collected in two flasks, B,
containing alcoholic silver nitrate. The precipi-
tated silver iodide is treated with nitric acid,
the alcohol evaporated, and the precipitate col-
lected and weighed in the usual manner.
Zeisel's method and its modifications are
applicable to the estimation of ethoxyl, but the
results obtained are generally less accurate.
Methyl.
A further modification of Zeisel's method
renders it available for the estimation of methyl
groups attached to nitrogen. The substance is
heated with concentrated hydriodic acid and
dry ammonium iodide, and the methyl iodide
evolved dealt with in the manner indicated
above (Herzig and H. Mever, Ber. 1894, 37,
319 ; Monatsh. 1894, 15, 613 1895, 16, 599
; ;
Fia. 31. 1897, 18, 379 Kirpal, Ber. 1908, 41, 820).
;
Methoxyl. Acetyl.
The estimation of methoxyl, a radicle It is only possible in comparatively few cases
present in many naturally occurring organic to determine with certainty by ultimate analysis
compounds, is generally accomplished by the number of acetyl groups existing in organic
Zeisel's method, which consists in heating the compounds. For example, the mono-, di-, and
substance with concentrated hydriodic acid or triacetyl derivatives of the trihydroxybenzenes
with a mixture of this acid and acetic anhydride. have approximately the same percentage com-
Methyl iodide is evolved and absorbed in alco- position. These and other similar acetyl deri-
holic silver nitrate, with the result that silver vates are hydrolysable by standard caustic
iodide is precipitated, each molecular propor- alkalis employed in alcoholic solutions, even
tion of this substance being equivalent to one when they are not readily attacked in aqueous
solutions (Benedikt and Ulzer, Monatsh. 1887,
8, 41 Van Romburgh, Rec. trav. chim. 1882,
;
1, 48 R. Meyer and Hartmann, Ber. 1905, 38,

;
3956). Acid hydrolysis may be employed in a

large number of cases and the volatile acetic
acid distilled into standard alkali, the excess
of which is determined by alkalimetry. Accord-
ing to Wenzel's process, the acetyl derivative
is first hydrolysed by moderately strong sul-
phuric acid (1 2H 2 0), and the mixture treated

:
with monosodium phosphate and boiled down

to dryness ; the sulphuric acid is fixed as
sodium sulphate, and the acetic acid is distilled
into a known excess of standard alkali, the
distillation being carried out under reduced
pressure (Monatsh. 1893, 14, 478; 1897, 18,
659).
The destructive action of strong sulphuric
acid on organic compounds may be avoided by
the use of the aromatic sulphonic acids as hydro-
lytic agents. The acetyl compound is distilled
in steam in a 10 p.c. solution of benzenesul-
phonic acid or one of the naphthalenesulphonic
acids the distillate, which contains all the
;
FIG. 32. acetic acid furnished

by the hydrolysis, is titrated
with standard barium hydroxide (Sudborough
methoxyl group. Zeisel's original apparatus and Thomas, Chem. Soc. Trans. 1905, 87,
(Monatsh. 1885, 6, 989 1886, 7, 406) has been
; 1752).
modified subsequently by several investigators A. G. Perkin hydrolyses the acetyl compound
(M. Bamberger, Monatsh. 1894, 15, 904 Perkin, ; with alcoholic sulphuric acid, adding fresh alcohol
Chem Soc. Trans. 1903, 83, 1367 Hesse, Ber. ; from time to time. The ethyl acetate obtained
1906, 39, 1142; Decher, Ber. 1903, 36, 2895; in the distillate is then hydrolysed with a known
Hewitt and Moore, Chem. Soc. Trans. 1902, 81, amount of standard caustic alkali, and the
318). Of these modifications Perkin's (Fig. 32) excess of the latter ascertained with standard
is probably the simplest it consists of a distil-
; acid (Chem. Soc. Trans. 1904, 85, 1462 ; 1905,
ling flask, A, with a very long neck (20-25 cm.) 87, 107 ; 1907, 91, 1230).
ANALYSIS. 231
Carboxyl. The weighed substance is digested for 12 hours

In many cases the number of carboxyl with an aqueous solution of pure potassium
(C0 2 H) groups in an organic compound can be iodide and iodate in a stoppered vessel. The
determined by the analysis of its neutral salts. mixture containing the liberated iodine ia
For this purpose the silver salts are generally rinsed unto the generating vessel of a gas
selected, as they are usually anhydrous, and volumeter and treated with alkaline
hydrogen
indicate the normal basicity of the organic acid. peroxide, when the oxygen evolved
The aromatic hydroxy-carboxylic acids (e.g. 1 6- : I2 +2KOH+H 2 2 ==2KI+2H,0+0 2
dinitro-p-hydroxybenzoic acid) take up two is a measure of the carboxyl groups
atoms of silver, one replacing the carboxylic, originally
present (6C0 2 HEE30 2 ) (Baumann-Kux, Zeitsch.
and the other the phenolic hydrogen. Some anal. Chem. 1893, 32, 129 ; Annalen, 1904, 335,
silver salts organic acids are sensitive to
of
4; cf. Groger, Zeitsch. angew. Chem. 1890, 3,
light, and others are very explosive. The more 353, 385). It should be noticed that acidic
stable ones can be analysed by direct ignition substances not containing carboxyl groups (e.g.
and Aveighing the residual silver. In other cases
picric acid) liberate iodine from the iodide-
the organic matter must be destroyed with iodate mixture.
nitric acid, and the silver estimated as chloride
Carbonyl.
in the acid liquid. The carbonyl group, whether present in
Other metallic salts are frequently employed
aldehydes R-COH or ketones R'COR', can be
in determining the basicity of carboxylic acids, detected by means of the following colour-
and it is advisable before arriving at a final
reaction. An aqueous or alcoholic solution
conclusion to estimate the metals in a series of of the substance is treated with a 0-5 to 1 p.c.
these compounds. solution of the hydrochloride of an aromatic
If the molecular weight of a carboxjdic acid
meta-diamine (meta-phenylenediamine or its
is known, the basicity can often be determined
homologues), when in a few minutes an intense
by titration with aqueous or alcoholic sodium, green fluorescence is developed, which attains
potassium, or barium hydroxide ; the indicators its maximum intensity after two hours. All
generally employed are phenolphthalein, methyl aldehydes give this reaction, but the mixed
orange, and lacmoid. ketones and ketonic acids do not (Windisch,
The following indirect method has been Zeitsch. anal. Chem. 1888, 27, 514).
recommended (P. C. Mcllhiney, Amer. Chem. J.
Practically all aldehydes restore the colour
1894, 408) for the estimation of carboxyl
16, to the following solution (Schiff's reagent). A
groups. The substance (1 gram) is dissolved litre of 0-10 p.c. magenta solution is decolourised
in excess of alcoholic potash, the alcohol
at least 93 p.c.
being
The solution is saturated with by adding 20 c.c. of sodium bisulphite solution
(30Be'.) followed after one hour by 10 c.c. of
carbon, dioxide until the excess of alkali is concentrated hydrochloric acid. (For the ex-
precipitated as carbonate or bicarbonate. The
ceptions, cf. Bitto, Zeitsch. anal. Chem. 1897,
precipitate is collected and washed with alcohol, 36, 375.) The reaction has also been utilised
the nitrate is distilled to remove the solvent,
and the residue containing the potassium salt quantitatively (McKay Chase, J. Amer. Chem.
Soc. 1906, 28, 1472; Schimmel & Co., Ber.
of the organic acid is distilled with 10
p.c. 1907, 123).
aqueous ammonium chloride, the ammonia
evolved being estimated in the usual way. Phenylhydrazine condenses with aldehydes
and ketones, yielding phenylhydrazones. When
Each molecular proportion of ammonia corre- the mixture is treated with Fehling's solution
sponds with one carboxyl group. This method
is applicable to the weaker
(70 grams CuS0 4 ,5H 2 0, 350 grams Rochello
fatty acids. salt, and 260 grams KOH, in 2 litres), the excess
Carboxyl can be estimated by a method of phenylhydrazine is decomposed, evolving
based on the following reaction :
nitrogen :
6R-C0 2 H+5KI+KI0 3 =6R-C0 2 K+3I 2 +3H 2 C 6 H 5 -NH-NH 3 +0=C 6 H 6 +H 0+N ;! ,
FIG. 33.
while the phenylhydrazone remains unchanged, known volume of Fehling's solution is introduced
The estimation is carried out in a flask, B, connect- and covered with a layer petroleum to prevent
of
ed with a carbon dioxide generator, A (Fig. 33). A the caustic potash from absorbing the carbon
232 ANALYSIS.
dioxide. A blank experiment is first made and traces of oxides of nitrogen by passing the
with the standard solution of phenylhydrazine mixed gases through alkaline permanganate
'
hydrochloride and aqueous sodium acetate, the solution. Half the nitrogen measured in the
nitrogen evolved on heating the solutions gas burette corresponds with that originally
together being collected in a Schiff's nitrometer, present in the ammo-acid.
F. The experiment is then repeated with the In the case of the aromatic primary amines,
same solutions of phenylhydrazine and sodium the acid solution of the base is carefully diazo-
acetate plus the carbonyl compound ; the tised at with standard sodium nitrite the ;
difference between the two volumes of nitrogen end-point is reached when a drop of the solution
collected is a measure of the carbonyl present gives a blue colour on starch-iodide paper.
in the compound (Strache, Monatsh. 1891, 12, The sodium nitrite solution may be standardised
524; 1892, 13, 299; 1893, 14, 270; Watson with either potassium permanganate, sodium
Smith, Chem. News, 1906, 93, 83). H
sulphanilate (NH 2 -C 6 4 -S0 3 Na,2H 2 0) or para-
When the carbonyl compound (e.g. pyruvic toluidine (cf. Green and Rideal, Chem. News,
acid) condenses readily with phenylhydrazine 1884, 49, 173 ; Kinnicutt and Nef, Amer. Chem.
or its hydrochloride in aqueous solution, the J. 1886, 5, 388 ; Zeitsch. anal. Chem. 1886, 25,
excess of this base can be estimated by adding 223).
excess of A//10-iodine solution, and titrating Estimation of imino-groups in secondary
the remaining iodine with standard sulphurous amines. A weighed quantity of the substance
acid or thiosulphate, using starch as indicator. is mixed with a known excess of acetic anhydride,
This estimation is based on the following either alone or diluted with dry xylene or
reaction :
dimethylaniline (Bull. Soc. chim. 1892, [3]
H
C B 6 -NH-NH 2 +2I 2 =3HI+C 6 5 I+N 2H 7, 142 ; Chem. Zeit. 1893, 17, 27, 465).
. After
The phenylhydrazone is not affected by the one hour, water is added and the mixture warmed
iodine solution (E. v. Meyer, J. pr. Chem. 1887, under a reflux apparatus, so that no anhydride
Ber. is lost by evaporation. The solution is then
[2] 36, 115; cf. Petrenko-Kritschenko,
1901, 34, 1699; and Annalen, 1905, 341, titrated with standard barium hydroxide and
phenolphthalei'n indicator. The amount of
15, 150).
acetic acid present indicates the excess of acetic
Organic amines.
The organic amines are divisible into three anhydride left over from the acetylation of the
classes, primary, secondary, and tertiary, secondary base.
The amines and the quaternary
containing their nitrogen atoms combined tertiary
ammonium salts do not give the reactions of the
respectively with one, two, and three organic
groups. These groups may be either aliphatic primary and secondary amines, but the total
or aromatic, and the reactions of each of the amount of basic nitrogen present in an organic
three classes of amines depend very largely on amine can frequently be ascertained by the
the nature of the organic groups to which the analysis of the characteristic salts of the base.
basic nitrogen atom is attached. The aurichlorides and platinichlorides may
Primary amines. The primary amino- frequently be employed for this purpose, as
NH these double salts on ignition leave a residue
group C 2 may be detected by the carbyl-
-
amine reaction (Hofmann, Ber. 1870, 3, 767), of the metal, each atomic proportion of gold
irrespective of the nature of the organic group, corresponding to one basic nitrogen atom,
which may be either aliphatic, aromatic, or while a similar quantity of platinum corresponds
Monatsh. with two basic nitrogen atoms. In the majority
hydroaromatic (cf. 1896, 17, 397).
The of cases these double salts have respectivelv the
warming the substance in
test consists in
alcoholic solution with chloroform and caustic general formula;, RHCl,AuCl 3 and (RHCl) 2 PtCl 4 ,
and are obtained in the anhydrous con-
potash, when a carbylamine (iso-nitrile) is
dition ; yet, in certain instances, hydrated
produced, which has a pungent disagreeable
odour :
forms are known and sometimes the salts them-
selves have an anomalous composition not
R-HN 2 +CHC1 3 +3KOH=R-NC+3KC1+3H 2 0. with the general formulae.
corresponding
The primary amines all interact with nitrous Evidence obtained in this way should, if possible,
acid, but the aliphatic bases are immediately be supplemented by the analysis of other salts,
converted into hydroxyl derivatives (alcohols), and for this purpose the ferrichlorides, chromates,
whereas the aromatic bases furnish diazo- oxalates, thiocyanates, ferrocyanides, picrates,
derivatives from which the nitrogen is evolved and picrolonates have been employed, as well
rapidly on warming or slowly at the ordinary as the commoner nitrates, sulphates, and
temperature. halide salts.
In the case of the aliphatic primary amines,
this nitrogen can be collected, and the amount Gas analysis.
indicates the proportion of amino- groups The experiments of Gay-Lussac established
present. As nitrous acid itself decomposes long ago the value, from a scientific point of
readily, evolving oxides of nitrogen, Stanck view, of the determination of the volumetric
recommends the use of nitrosyl chloride, obtained composition of gases and the products formed
by adding fuming hydrochloric acid to 40 p.c. by their interaction ; but it is only within recent
aqueous sodium nitrite (Zeitsch. physiol. Chem. times that the methods of gas analysis have been
1905, 46, 263). This reagent can be mixed with applied to any great extent for technical pur-
saturated salt solution without undergoing poses. The value of such determinations is now
decomposition ; the aliphatic amino -car boxylic generally recognised on account of the informa-
acids (glycine, &c.) can be readily decomposed tion which they give respecting the efficiency of
"
by it in a current of carbon dioxide, and the combustion, the progress of operations in which
nitrogen evolved is freed from the former gas gases are consumed or produced, and the like.
ANALYSIS. 233
With few exceptions the volumetric aud not convenient form of instrument for the purpose,
the gravimetric composition of the gas is and should stand on the table close to the gas
required, and the measurements are essentially apparatus. In case the level of the mercury or
measurements of volumes. The gas to be ex- water in the measuring tube is higher than that
amined is confined over mercury or water in a in the trough or the attached tube, the true pres-
suitable measuring apparatus, and its composi- sure upon the gas is given by the height of the
tion is determined (I) by treatment with ap- barometer minus the difference between the
propriate absorbing reagents and measurement of mercury level inside and outside the tube. If
the contraction produced (2) by exploding with
; water is used, the height of the water column
oxygen or hydrogen and measuring the contrac- divided by 13-6 gives the height of the corre-
tion (3) by exploding with oxygen or hydrogen, sponding column of mercury with sufficient ac-
;
measuring the contraction, and then treating curacy. It is better to eliminate this correction
with absorbing reagents, and measuring the by adjusting the liquid so that it is at the same
second contraction. Sulphur dioxide and some level both inside and outside the tube, which is
other gases soluble in water are estimated by easily done.
titration, a definite volume of the gas being The gas must be either perfectly dry or
drawn through a measured quantity of a standard saturated with moisture. If an indefinite
solution, the excess of which is afterwards de- quantity of water vapour is present, accurate
termined. measurements are impossible. It is more con-
The highly refined and accurate methods of venient to measure the gas when moist, and
gas analysis employed for purposes of research hence if the gas is confined over mercury a few
are of little value for technical purposes on drops of water are introduced when the tube is
account of the length of time required for their filled with the mercury and this water is taken
execution. Information respecting these methods up by the gas. Under these conditions the sur-
may be found in Bunsen's Gasometrische rounding pressure is balanced partly by the gas
Methoden, 2nd ed. 1887 ; Button's Volumetric and partly by the aqueous vapour which it con-
Analysis, 9th ed. 1904 ; Dittmar's Exercises in tains, and in order to ascertain the pressure
Quantitative Analysis, 1887 Hempel's Gas-
; which the gas itself is under, the tension of
analytische Methoden, 3rd ed. 1900 ; Travers' aqueous vapour at the particular temperature
Experimental Study of Gases, 1901 v. also
; must be subtracted from the height of the
Thomas (Chem. Soc. Trans. 1879, 35, 213), and barometer. The formula for reducing the
Meyer and Seubert (Chem. Soc. Trans. 18S4, volume of gas to the standard temperature and
45, 581). In this article only those methods pressure (0 and 760 mm.) is :
will be described which are available for technical

V+ x (B - /) or V X (B - /)
purposes.
273
+ 1) X 760
Vn =
(273 (1+0-0036WX760)
Measurements. The volume which a given
mass of gas occupies depends on the tempera- in whichV is the actual reading ; t, the tempera-
ture, the pressure, and the proportion of moisture ;
the tension of aqueous vapour at the
/,
ture which it contains. The temperature is as- temperature, t ; and B, the height of the baro-
certained by means of a thermometer attached meter. The reduction of the height of the
to or suspended near to the measuring vessel. barometer to is necessary for accurate calcula-
Measurements are usually made under atmo- tion, but may usually be omitted. The following
spheric pressure, and this is determined by means table, abbreviated from Bunsen's Gasometrische
of a barometer placed in the room in which the Methoden, gives the value of 1+0-00366* for the
analysis is made. The siphon barometer is a ordinary range of temperature :
t
234 ANALYSIS.
and pressure should occupy under the conditions The stock solution is made by dissolving
200 grams of cuprous chloride and 250 grams of
described, is calculated from the expression :
ammonium chloride in 750 c.c. of water ; it is

v _ (760- 4-5)100X(273+< )
(760-4-5)100Xl+0-Q0366<)
kept in stoppered bottles, and, when required,
273(B-/) B-/ mixed with one-third its volume of ammonia
and air is carefully introduced into the tube until, solution (sp.gr. 0-91).
when the mercury is at the same level inside Hydrogen obtained by the action of dilute
is
and outside the tube, it stands exactly at the sulphxiric acid on pure zinc. The granulated
calculated volume. The tube now contains a zinc may be "placed in a small bottle fitted with
quantity of gas saturated with moisture, which, a capillary delivery tube, which can be closed by
under standard conditions, would occupy 100 c.c., a tap or pinch-cock. The bottle has a tubulus at
but its actual volume varies in the same ratio as the bottom, and is connected by a caoutchouc
the volume of gas to be measured. The two tube with a similar bottle containing dilute sul-
tubes are allowed to stand side by side, and
phuric acid. The latter bottle is raised so that
when the levels have been properly adjusted in the acid runs on the zinc, and the action is
each case the volume of the gas to be measured allowed to proceed until the air is completely
and the volume of the air in the comparison tube expelled from the first bottle. The tap is then
are read off. The volume (under standard closed, and the acid is driven back into the second
conditions) of the gas under examination is bottle by the pressure of the hydrogen. It is
obtained by the proportion advisable to keep the second bottle at a slightly
Vv Vv. V
.. v x
'
. Vv '
, higher level than the first, to avoid any chance

in which V is the actual volume of air in the of air leaking in. One of Hempel's tubulated
comparison-tube V its volume under standard
; , absorption bulbs answers admirably (Fig. 41).
conditions, which is always 100 ; V/, the The zinc is attached to a cork, which is inserted
observed volume of the gas to be measured ;
in the tubulus of the first bulb, and the acid is
and V ', its volume under standard conditions. introduced. When all air is expelled, the capil-
During the operations the temperature lary tube is closed, and the acid is driven up into
should be kept as constant as possible, and the the second bulb, so that the pipette is always
readings should be taken rapidly, otherwise the charged with hydrogen under pressure.
proximity of the body will cause variations in Oxygen is obtained in a pure state by heating
the temperature of the gas. It is an ad vantage potassium chloride without manganese dioxide.
to have the measuring tube surrounded by a The powdered chlorate is contained in a glass
wider tube which is filled with water. The most bulb, the neck of which is drawn out to form a
accurate method is to take the readings through narrow delivery tube.
a carefully levelled telescope (a cathetometer) at Phosphorus is employed in the form of narrow
a distance of about five or six feet. This also sticks, which are made by melting it under warm
avoids parallax. The measuring tube must be water and drawing it up into narrow glass tubes.
kept vertical, and when water is the confining The upper ends of the tubes are closed by the
liquid, sufficient time must be given for the finger, and they are plunged into cold water,
liquid to run down the sides of the tube. Not when the phosphorus solidifies. It may also
unfrequently this requires several minutes. be used in a granular form, obtained by shaking
the phosphorus vigorously with warm water in a
Reagents. well-closed flask until it solidifies.
All liquid reagents should be saturated with Caustic potash (or soda) for Orsat's apparatus
the gases which they do not absorb chemically. is dissolved in three parts of water, and the solu-
It is desirable that the tensions of these gases tion kept in well-stoppered bottles. Hempel
in the liquids should be approximately equal to uses a solution of caustic potash in two parts of
their tensions in the gases which are to be water, which will absorb forty times its volume
analysed, in order to avoid exchanges between of carbon dioxide. It may, however, be used
the gas and the absorbing liquid. This is best somewhat more dilute, and is then less liable to
secured by going through the process two or attack the glass.
three times without making measurements, Pyrogallol is kept in the solid state, and only
whenever the pipettes have been freshly filled. dissolved immediately before being used. Orsat
Liquids used for the analysis of, say, flue gases, recommends a solution of 25 grams of pyrogallol
should not be used for gases of a different chain a small quantity of hot water, mixed with
racter, i.e. which contain the constituents in 150 c.c. of a solution of 1 part of caustic soda in
very different proportions. 3 parts of water. Hempel uses a mixture of
Bromine water is used for absorbing defines. 25 c.c. of a 20 p.c. solution of pyrogallol with
It should be well saturated with bromine and 75 c.c. of 33-3 p.c. caustic potash solution.
kept in the dark. This quantity will absorb 200 c.c. of oxygen.
Cuprous chloride is made by dissolving 50 Sulphuric acid of sp.gr. 1-84 is used as a
grams of cupric oxide in hydrochloric acid, add- drying agent and for the absorption of nitrogen
ing 50 grams of copper, and boiling for some oxides. Acid of the same strength mixed with
time with as little exposure to air as possible. so much sulphuric anhydride that it remains
The solution is then diluted to 1000 c.c. with liquid at the ordinary temperature but solidifies
hydrochloric acid of sp.gr. 1*12, and allowed to if cooled, is used for absorbing ethylene and
remain in contact with metallic copper in a closed other hydrocarbons.
vessel until the solution becomes colourless. Water, which is very largely used for con-
This solution attacks mercury rapidly. fining the gases, should be well saturated
with
Cuproso-ammonium chloride, obtained by air, but should not contain carbon dioxide.
dissolving cuprous chloride in ammonia, does Distilled water is preferable, but any potable
not attack mercury. water of good quality may be used.
ANALYSIS. 235
Standard solutions used in the estimation of Jean, 1902, 135, 746 ; J. Amer. Chem. Soc.
ibid.
gases by titration are known as normal gas 1900, 22, 14 ; 1907, 29, 1589 ; Ann. Chim. anal.
solutions when they are of such strength that 1910, 15, 1).
1 c.c. of the solution is equivalent to 1 c.c. of Hydrogen is converted into water by combus-
the gas under standard conditions. A normal tion with air or oxygen, and the volume of the
gas solution of iodine for the estimation
of hydrogen is represented
by two-thirds of the con-
traction consequent upon combustion.
sulphur dioxide would contain 11-333 grams of If the
iodine per litre, and the thiosulphate solution gas is confined over mercury, an excess of pure
used in conjunction with it would be of equiva- oxygen is introduced, the volume read off, and
lent strength. the pressure on the gas reduced
considerably
In many cases it is the weight of the absorbed below atmospheric pressure by lowering the
constituent per cubic metre or cubic foot of gas mercury in the level tube. The lower end of the
that is required, and the ordinary standard explosion tube is closed, and combination is
solutions may be used. initiated by passing a spark from a coil between
the platinum wires which are fused into the tube.
Methods of estimation. The pressure is restored to the normal, and when
Ammonia, by titration. the gas has cooled the volume is again read off.
Benzene, by absorption in fuming nitric acid When the gas is confined over water it is
almost impossible to obtain satisfactory com-
boiling at 86, the nitrogen oxides being then
removed by caustic potash. Fuming nitric acid bustion, and it is much more convenient to pass
also absorbs carbon dioxide and carbon mon- the combustible mixture over gently heated
oxide. Like the olefines, benzene is absorbed spongy palladium. This is prepared by dis-
by fuming sulphuric acid and by bromine water, solving about two grams of palladium chloride
and in fact no absorption method is at present in a small quantity of water, adding a small
known by means of which benzene and the quantity of a saturated solution of sodium
olefinescan be separated (Ber. 1888, 21, 3131). formate and sodium carbonate until the re-
Carbon dioxide, by absorption in potassium action is alkaline. About 1 gram of long
or sodium hydroxide. and very soft asbestos fibres is introduced, and
Carbon monoxide, by absorption in a satur- the pasty mass is dried at a gentle heat. In this
ated solution of cuprous chloride in hydrochloric way the asbestos is obtained covered with very
acid or ammonia. It seems (Ber. 1887, 20, finely divided palladium. After being completely
dried at 100, it is carefully washed with water
2754) that these solutions are liable to give off
part of the dissolved carbon monoxide, especially
to remove soluble salts and again dried. Some
after they have been used repeatedly. The of the fibres are moistened and twisted into a
error is less with the ammoniacal solution, and is thread about 1 cm. long, which is then intro-
reduced if the solution remains in contact with duced into the middle of a stout capillary tube, E,
the gas for some time. The cuprous chloride about 15 cm. long and 1 mm. internal diameter,
solution should always be tolerably fresh, and
should be saturated with hydrogen, nitrogen,
and the other gases which usually occur with
carbonic oxide (Ber. 1888, 21, 898). If the
amount of carbon monoxide is small, it should
be converted by combustion (v. Hydrogen) into
carbon dioxide, which is afterwards absorbed
by caustic potash. If the amount of carbon
monoxide is large, the greater part may be ab-
sorbed by cuprous chloride, and the remainder
removed by combustion and absorption.
The estimation of small quantities of carbon
monoxide in air or other comparatively inert
gases can be effected by passing the dried gas
over solid iodine pentoxide. At temperatures
varying from 40-150 the following reaction
occurs: I2 5 +5CO=5C0 2 -|-I 2 . Either of the
volatile products can be estimated the iodine
:
volumetrically by standard thiosulphate, or

gravimetrically by absorption in a weighed tube
containing copper powder the carbon dioxide
;
may be absorbed in standard barium hydroxide,

and the excess of the latter titrated with oxalic FIG. 34.
acid. If carbon dioxide is
present in the gas
under examination, it is first removed by and this tube is bent at a right angle at each end.
potassium or barium hydroxide. Below 60 no or in any other way convenient for its attach-
hydrocarbon except acetylene reduces iodic ment to the measuring apparatus containing the
anhydride. At higher temperatures several gas. One end of the capillary is in communica-
unsaturated hydrocarbons have an appreciable tion with the graduated tube, A, and the other
action. Ethylene hinders the oxidation of with a bulb pipette, c, filled completely with
carbon monoxide by the iodine pentoxide. The water, into which the gas is passed.
A small gas
process is applicable to air containing one part or spirit-lamp flame is arranged to heat that part
of carbon monoxide in 30,000, and is used for of the capillary which contains the asbestos.
estimating the monoxide occluded in steel When the other gases have been estimated, the
(Gautier, Compt. rend. 1898, 126, 871, 1299 ;
mixture of hydrogen and nitrogen which remains
236 ANALYSIS.
is mixed with air by lowering the level-vessel admixture with oxygen, and the peroxide is
until the pressure absorbed by caustic potash, the excess of oxygen
is sufficiently reduced, and
then putting the measuring tube in com- being afterwards absorbed by alkaline pyrogatiate.
munication with the air. The stop-cock is then Nitric oxide may also be absorbed by a con-
closed, the asbestos very gently heated, and the centrated solution of ferrous sulphate, but
.
gas passed slowly through the capillary into the this method does not give such satisfactory
bulb and back again three or four times. When results.
combustion is complete, the volume of the Nitrogen peroxide and nitrous anhydride, by
residual gas is measured. titration ; by absorption with sulphuric acid of
This method may be employed in estimating sp.gr. 1 -84 ; or, in absence of carbon dioxide
hydrogen in the presence of methane, since the and other absorbable gases, by absorption with
latter is not burnt under these conditions, caustic potash.
pro-
viding that the temperature does not exceed Olefines, by absorption with fuming sulphuric
500 (J. Soc. Chem. Ind. 1903, 22, 925 ; 1905, acid, acid vapours being removed by caustic
24, 1202 ; Zeitsch. angew. Chem. 1903, 16, 695). potash ; or by absorption in bromine water,
The palladinised asbestos can be used in bromine vapours being afterwards removed by
promoting the combustion of carbon monoxide. caustic potash.
Drehschmidt (Ber. 1888, 21, 3245) prefers a Oxygen, by absorption with alkaline pyro-
platinum tube 20 cm. long and 2 mm. thick, with gallate. If the oxygen is present in greater pro-
a bore 0-7 mm. diameter. The bore is almost portion than 20 p.c. a small quantity of carbon
closed by the insertion of a palladium wire ex- monoxide is evolved from the pyrogallol during
tending through the whole length of the tube. absorption, and hence the results are slightly too
The tube is attached to a burette and an absorp- low. After treatment with pyrogallol the gas
tion pipette in the same manner as the may be passed into the cuprous chloride bulbs
glass
tube ; 5 to 6 cm. are heated to redness by means in order to remove any carbon monoxide that
of a gas flame, and the
gas is passed backwards may have been formed. Usually, however, this
and forwards until there is no further alteration error has no material influence on the results.
of volume. No explosions occur even with Oxygen may also be absorbed by phosphorus,
mixtures of hydrogen and oxygen containing and this has the advantage that the presence of
only a slight excess of the latter. carbon dioxide is without influence on the result.
Hempel has applied the well-known absorp- The temperature, however, must not be below
tion of hydrogen by palladium to the estimation 18, and the absorption is prevented by the
of this gas. Pure palladium is indifferent presence of ammonia, defines, and other hydro-
towards hydrogen in the presence of methane carbons, alcohol, &c.
and nitrogen, but when it contains a little palla- Sodium hydrosulphite has been recommended
dious oxide combustion of some of the as an absorbent for oxygen, the reaction
hydrogen
occurs, and the heat generated ensures the
absorption of the remainder. Palladium sponge
Na 2 S 2 4 +H O+0=2NaHS0
2 3
is heated and allowed to cool

slowly so that it taking place readily at low or high temperatures.
becomes superficially oxidised. A U-tube of The solution contains 50 grams of the salt and
4 mm. internal diameter and 20 cm. total 40 c.c. of sodium hydroxide (5 7) in 250 c.c. of
:
length
is
charged with 4 grams of this oxidised sponge water, and is used in a pipette filled with rolls of
and maintained at 90-100 by immersion in a iron-wire gauze (Ber. 1906, 39, 2069).
beaker of hot water ; this tube is interposed Oxygen may also be estimated by combustion
between the gas burette and a pipette filled with with hydrogen, either explosively by the spark
water. The absorption is effected by siphoning or over palladium-asbestos. The hydrogen
' '
the gas backwards and forwards should be evolved from commercial pure zinc
through the
palladium sponge. and pure dilute sulphuric acid, or in special cases
Hydrogen chloride, by titration. from magnesium and sulphuric acid. One-third
Hydrogen sulphide, by titration. of the contraction consequent upon combustion
Hydrocarbons other than defines are esti- gives the volume of the oxygen.
mated by combustion, preferably with oxygen Sulphur dioxide, by titration.
over mercury under reduced pressure. Acety- In the ordinary gases from flues, generators,
lene and benzene may be burnt over palladium, &c., the constituents are estimated in the follow-
but require a somewhat high temperature. ing order Carbon dioxide, defines and benzene,
:
Methane cannot be burnt in this way even in oxygen, carbon monoxide, hydrogen, methane,
presence of hydrogen. The combustion of this nitrogen (as residue or by difference).
gas is effected by mixing it with a considerable If acid vapours are present together with one
quantity of air and aspirating the mixture or more of the above gases, the order of absorp-
through a short tube containing cupric oxide tion, &c., must be determined by circumstances.
heated to redness in a small combustion furnace,
the carbon dioxide which is produced Apparatus and manipulation.
being
absorbed in standard baryta solution, which Collecting samples. The gas to be analysed
is afterwards titrated with standard oxalic is usually drawn from the flue, chamber, &c., by
acid.
aspirating it through glass tubes, which may be
Drehschmidt finds (Ber. 1888, 21, 3249) that termed conducting tubes. When the tempera-
a mixture of methane and oxygen can readily be ture is high, porcelain tubes may be used or if
;
burnt in a platinum tube, as above, if the latter the gas has no acid properties, iron tubes can be
is heated to
bright redness. The contraction employed. When samples are constantly taken
is observed, and the carbon dioxide formed is from the same flue, &c., it is convenient to have
removed and the volume again measured. a short piece of porcelain or iron pipe cemented
Nitric oxide is converted into peroxide by into the wall and closed at the outer end with a
ANALYSIS. 237
plug, which is readily removed when the sample this volume for temperature,
&c., in the usual
is taken. In cases where the gases are originally way (v. ASPIRATOR).
at a high temperature and possibly in a state of When
aspiration is to be continued for a long
partial dissociation, it is important to draw the time, one of the various forms of water
pump
sample slowly through a somewhat long tube in may be used. The volume of air aspirated in a
order that the gas may cool slowly, since rapid given time with a given pressure of water may
cooling of the gases may leave them in a partially be determined once for all
by direct measure-
dissociated condition and thus lead to erroneous ment, or a small gas meter maybe placed between
results. the pump and the vessel into which the
gas is
The sample may be conveniently collected in passed.
the measuring apparatus itself ; but where this the gas has to be kept for some time before
If
is not possible, a cylindrical glass tube A, drawn analysis, or if it has to be
transported from one
out at the upper end and connected with a stop-
1
place to another, it may be collected in glass

, cock and capillary tube, and tubes which have previously been drawn out at
fi" A drawn out at the lower end and each end. As soon as the tubes are
full, the ends
connected by caoutchouc tubing are closed by stoppers of indiarubber
tubing and
with a similar tube B, open at glass rod, or are hermetically sealed by fusion.
the top, makes a convenient If the quantity of
gas is
large, cylindrical zinc
sampler. The collecting tube vessels with conical ends closed
by indiarubber
may with advantage be pro- corks answer very well.
vided with a stop-cock at the (For other forms of gas-samplers, v. J. Soc.
bottom. The vessel A is com- Chem. Ind. 1889, 8, 176 ; 1903, 22, 190.)
pletely filled with water or mer- Estimations by titration. A measured
quan-
cury by raising B to a higher tity of the appropriate standard solution is
level, and the upper stop-cock placed in a flask or a Woulffs bottle fitted with
is closed. The capillary tube is two tubes, one of which dips into the liquid and
connected with the conducting is connected with the tube
placed in the flue,
tube, and the vessel B is lowered &c., whilst the other ends just below the cork
so that when the stop-cock is and is connected with an aspirator. After
slowly opened the gas is drawn aspiration has been continued for a sufficient
into A, and the water or mercury length of time, the excess of reagent is deter-
collects in B. When A is filled the mined by titration. The volume of gas aspirated
FIG. 35.
stop-cocks are closed. The gas is determined
by the volume of water which has
is readily transferred from A to the measuring run from the aspirator or by means of a gauge
vessel by raising B and carefully opening the attached to the aspirator. This volume of
stop-cock. water, however, represents a volume of gas
In all cases the air in the conducting tube saturated with moisture and at a temperature
must be expelled, and this is done by placing a and pressure which must be determined by
T-tube between the end of the tube and the means of a thermometer attached to the aspirator
collecting vessel. This T-piece is connected and a barometer in close proximity ; the volume
with an aspirator, and the tube is filledwith the under standard conditions is calculated in the
gas before the stop-cock of the collecting vessel is usual way. In calculating the percentage com-
opened. When the collecting vessel is provided position of the gas, it must be borne in mind that
with a three-way cock, the aspirator may be the original volume of the gas was the sum of the
connected directly with the latter. Various volumes of the absorbed constituent and the
forms of aspirator may be used. When the volume which has passed into the aspirator.
volume of gas to be aspirated is small (e.g. in If F! is the volume of the absorbed gas, and
removing air from the conducting tube), a small V z the volume which has passed into the aspira-
globular indiarubber aspirating pump is very tor, both under standard conditions, then
convenient. For larger quantities of gas, glass 100 X V.
7
=
per cent, or Kj by volume.
'
1 ~T~ 2
This method may be applied in the estimation
of
Ammonia, by absorption in sulphuric acid
and titration with alkali.
Carbon dioxide (in small quantities), by
absorption in standard baryta solution and
titration with oxalic acid.
Chlorine, by absorption in a standard solu-
tion of arsenious oxide in sodium carbonate,
and subsequent titration with iodine after
FIG. 36. FIG. 37. saturating with carbon dioxide.
When hydrochloric acid and chlorine occur
a tubulus or stop-cock at the bottom together, the latter is determined separately
bottles with in
and a tube or stop-cock at the top, or similar one quantity, and a second quantity is absorbed
vessels of sheet zinc, may be used (Figs. 36 and 37). in the solution of arsenious oxide hi sodium
They are filled with water, the upper tube being carbonate free from chlorine, and the total
connected with the tube which passes into the chlorine is determined by titration with silver
flue, and tne water is allowed to flow from the tap nitrate, using Volhard's thiocyanate method.
at the bottom. The volume of gas aspirated is In calculating the percentage composition, it is
important to remember that 1 vol.
determined by measuring the volume of water of chlorine
which flows from the aspirator, and correcting produces 2 vols. of hydrochloric acid.
238 ANALYSIS.
in sodium somewhat large cylindrical bulbs communicating
Hydrochloric acid, by absorption
carbonate and titration with silver nitrate, or, at the bottom by a curved tube. The bulbs
in absence of carbon dioxide and other acids,
or
by absorption in standard caustic potash
soda, and subsequent titration with an acid.
Hydrogen sulphide, by absorption in standard
iodine and titration with thiosulphate ; or by
absorption in bromine water and gravimetric
estimation as barium sulphate.
acidified
Nitrogen oxides, by absorption in
the
permanganate solution of definite strength,
is just de-
gas being passed until the solution
colourised. This method gives the amount of
nitrogen oxides in terms of
their reducing
poAver.
Sulphur dioxide, by absorption in standard
iodine solution and titration with thiosulphate,
or by absorption in bromine water and gravi-
metric estimation as barium sulphate. The
latter may be adopted when the proportion
plan
of sulphur dioxide is very small and a large
volume of gas must be aspirated.
Measuring and absorption apparatus. Only
those forms which have come into general use
and are of wide applicability will be described
Descriptions of the numerous
here. other
modifications will be found in Winkler's Chem.
Unters. der Industrie-Case ; Winkler and FIG. 39.
Lunge's Technical Gas Analysis ; and
in Zeitsch.
nearest the capillary tubes are fitted with short
anal. Chem.
lengths of glass tubing so that a large surface of
Anextremely convenient device which is the reagent may be exposed, and the other bulbs
applied to almost all the forms
of apparatus is
receive the liquids when they are driven out
the three-way stop-cock. This has the usual from the first bulbs by the gas. Any number
of bulbs can, of course, be attached to the main
51 capillary, and at the end of it there is a three-

way tap communicating with the aspirating tube
or with the air.
The three absorption pipettes indicated in
Fig. 39 are generally filled respectively with
solutions of caustic potash, alkaline pyrogallate,
and cuprous chloride, and serve for the estima-
tion of carbon dioxide, oxygen, and carbon
FIG. 38. monoxide.
The burette is filled with water by placing
transverse bore, but the plug itself is elongated the liquid in the level-bottle and raising the
in the form of a tube, the bore of which is con- latter, and the stopcocks are then closed. The
tinued in a curved direction through the plug absorption bulbs are rather more than half filled
and opens at the side in the same plane, but with the liquid reagents, and by opening the
in a direction at right angles to the transverse stop-cocks and placing the level-bottle below the
bore. By means of this tap two tubes can be apparatus the liquids are drawn up so as to fill
made to communicate with one another, or completely the bulbs connected with the capil-
either of them separately can be put in com- laries. The stop-cocks are then closed.
munication with a third tube or with the air. The burette is filled with water up to the
Orsat's apparatus. The measuring tube or capillary tube by raising the level-bottle, and the
burette consists of a cylindrical bulb terminating far end of the capillary tube is connected with
at one end in a capillary tube and at the other the tube along which the gas is to be conducted.
in a narrow tube of uniform bore graduated in The lower end of the three-way tap is connected
tenths of a cubic centimetre. The total capacity with an indiarubber aspirator, and the air is
of the tube from the zero to the capillary is 100 removed from the conducting tube by aspirating
c.c., and the lower end of the tube is connected the gas through it. The level-bottle is then
'
by caoutchouc tubing with a level-bottle,' the lowered, the tap is turned through 90, and
height of which can readily be adjusted. The the gas is drawn into the burette. When a
burette is enclosed in a cylinder which is filled sufficient volume has entered, the tap is closed,
with water at a constant temperature. The the levels inside and outside the burette are
capillary from the upper end of the measuring adjusted by raising the level-bottle, and the
tube is carried horizontally along a wooden volume of the gas is read off as soon as the
support. Other capillary tubes provided with temperature is constant. If it is desired to
stop-cocks are fused into it at right angles and operate upon exactly 100 c.c., the gas is drawn in
communicate by means of very short lengths until the water is a little below the zero, the tap
of stout indiarubber tubing with the absorption is closed and the level-bottle is raised so that the
pipettes, each of which consists of a pair of gas is slightly compressed and the
water rises
ANALYSIS. 239
above the zero (time having been given for the Before an analysis the whole of the
apparatus,
liquid to run down from the sides of the burette), including the connections, is filled with mercury,
and the indiarubber tube is closed by a pinch-
cock. The level-bottle is again lowered, and by
cautiously opening the pinch-cock the water is
allowed to descend exactly to the zero, and the
pinch-cock is closed. The tap at the end of the
main capillary is opened for an instant, so that
the excess of gas may escape and the 100 c.c.
remaining in the burette may be at atmospheric
pressure.
In order to bring the gas into any one of the
absorption bulbs, the le.vel-bottle is raised and
the tap of the particular bulb is opened. The
gas passes into the bulb, and by alternately
raising and lowering the level-bottle the gas can
be passed backwards and forwards several times,
care being taken that the absorbing liquid does
not pass through the stop-cock. The gas is
finally drawn off so that the absorbing liquid
just reaches the stop -cock, the latter is closed,
and, after readjusting the levels, the volume of
gas is again read off. After making the neces-
sary corrections, the decrease in volume is, of
course, the volume of the gas which has been
absorbed. The order in which the absorbing
liquids should be applied has already been
given (p. 236).
Lunge has added to this apparatus a capil-
lary tube with
palladium asbestos, for the
estimation of hydrogen, connected with a bulb
similar to the absorption bulbs, but containing
water only. The apparatus also contains a
small spirit-lamp carried by a movable rod for
heating the palladium asbestos (Dingl. poly. J.
1882, 245, 512).
Sodeau has introduced a modification of
Orsat's apparatus suitable for the analysis of
mixtures containing only small proportions of
combustible gases (e.g. chimney gases). In
this modification the cuprous chloride pipette
and the palladium combustion tube are replaced
by a combustion pipette, the only absorption
pipettes present being those containing caustic FIG. 40.
potash and alkaline pyrogallate. The carbon
dioxide is first estimated by means of the former, and the gas may be introduced either from the
and the combustible gases burnt by passing an sampling tube, K, or from the absorption
electric current (5 amperes) for 8, short time vessel, F.
through a platinum spiral in the combustion The Regnault-Frankland principle of mea-
pipette. The contraction is noted, and the surement employed, namely, the measurement
is
carbon dioxide produced is estimated by of the pressure of the gas (in mm. of mercury)
absorption in the caustic potash. These data at constant volume. The measuring tube A
give the proportions of carbon monoxide and has a series of constant-volume marks coinciding
hydrogen originally present in the gaseous with the 0. 100, 200, &c., mm. marks on the
mixture. The residual oxygen may now be pressure tube B. These two tubes are moistened
estimated by absorption in the alkaline pyro- with dilute sulphuric acid (1 20) as a precaution
:
gallate (Chem. News, 1904, 89, 61). against the accidental introduction of alkali
Bone and Wheeler's apparatus is a simple into the measuring tube. The tap closing the
form of gas apparatus capable of upper end of the pressure tube is connected to
giving accurate
results with almost all gaseous mixtures it by stout indiarubber pressure tubing ; this
ordinarily
met with in technical practice. The working gives a tight but elastic joint, and obviates
liquid is
mercury, and the apparatus consists of risks of fracture. By means of this tap the
the following parts (1) : A
water- jacketed com- pressure tube can be rendered vacuous, and, in
bination of measuring and pressure tubes, A and this way, the measurements are rendered inde-
B, communicating through the glass tap c with pendent of the barometric pressure, and it
the mercury reservoir D ; becomes possible to analyse smaller volumes of
(2) an absorption
vessel, F, standing over mercury in a mahogany gas. The length of the pressure
tube provides for
trough ;(3) an explosion tube, E, fitted with the requisite dilution of the explosive mixtures
firing wires, and having a separate mercury in analyses by explosion. All the absorptions
reservoir, H (4) a sampling tube, K.
; The con- are carried out in the same vessel, F, a com-
nections between A, E, and F are of
capillary paratively small amount of freshly prepared
bore throughout, with suitable
glass taps. reagent being used in each operation. The
240 ANALYSIS.
absorption vessel is rinsed out by means of the the other (Fig. 34). The upper part of the lower
three-way tap, the lower parallel limb of which bulb terminates in a straight capillary tube,
is joined to a large bottle connected up with the which extends to a slightly greater height than
water pump. In this way a series of absorptions the higher bulb, and serves to connect the pipette
can be carried out without disturbing a single with the burette. In the tubulated pipette the
connection in the apparatus. An analysis of pro- bottom of the lower bulb is provided with a
ducer gas is easily completed in 45 minutes, and tubulus, which can be closed with a caoutchouc
one of coal gas requires about an hour (J. Soc. stopper, and through which solid reagents such
Chem. Ind. 1908, 27, 10). (For other forms of
technical gas apparatus, v. F. Fischer, Zeitsch.
angew. Chem. 1890, 3, 591 ; Sodeau, J. Soc.
Chem. Ind. 1903, 22, 187. See also Chem. Soc.
Trans. 1894, 65, 43 ; 1899, 75, 82 ; Ber. 1902,
35, 3485, 3493 ; 1907, 40, 4956 ; J. Soc. Chem.
Ind. 1908, 27, 483, 491 ; Chem. Zeit. 1903, 845 ;
1904, 686 ; Zeitsch. angew. Chem. 1907, 20, 22.)

HempeVs apparatus. The measuring appa-
ratus consists of a burette, and a plain tube
of the same length and diameter, which serves
as a level-tube. The burette holds 100 c.c.
from the zero to the capillary, is graduated in
fifths of a c.c., and terminates at the top in a
capillary tube to which is fitted a short piece of
stout-walled caoutchouc tubing closed by a FIG. 42.
pinch-cock. Both the burette and the level- tube
are fixed at the bottom into heavy circular as phosphorus or zinc can be introduced. A
stands, and each has a side tubulus near' the composite absorption pipette consists of two
bottom over which is slipped the caoutchouc similar pairs of bulbs, the second pair containing
tube by which they are connected. It is water or some other liquid which protects the
advisable to make all the joints secure with reagent in the first from the action of the air.
copper wire. In order to make the measure- Composite pipettes are used with alkaline pyro-
ments more accurate, the burette may be gallate, cuprous chloride solution, bromine water,
surrounded by a wider tube filled with cold and similar reagents (Fig. 42).
water (Winkler). In making the absorptions the pipettes,
The pinch-cock is opened and both tubes are which are attached to wooden stands, are placed
rather more than half filled with water. The on a table stand of such height that the top of the
burette is completely filled with water by raising capillary of the pipette is level with the top of
the level-tube until the water runs out of the the capillary of the burette. The burette and
indiarubber tube at the top, and the pinch-cock pipette are joined by means of short pieces of
is then closed. By means of the indiarubber caoutchouc tubing and a short piece of capillary
tube the burette is attached to the conducting tube bent twice at right angles. The volume of
tube, which has already been filled with the gas, air contained in this capillary is so small that it
the level-tube is lowered, and the pinch-cock does not introduce any appreciable error. Care
is taken that the capillary of the absorption
opened. When sufficient gas has been drawn in
the pinch-cock is closed, the levels adjusted, and pipette is filled just up to the top with the re-
the volume read off in the usual manner. If it agent. The connections being made, the level-
is desired to admit exactly 100 c.c., proceed tube, which should be full of water, is placed on
in the same way as described under Orsat's the table stand and the pinch-cock is opened.
apparatus. The gas passes into the pipette, and by raising
The reagents are contained in absorption and lowering the level-tube the whole of the gas
pipettes. Simple absorption pipettes consist of can be passed backwards and forwards two or
three times ; or the gas may be allowed to re-
main in contact with the liquid in the pipette.
When absorption is complete, the level-tube is
lowered until the reagent is drawn just up to the
top of the capillary of the pipette, the pinch-cock
is closed, and a second reading is taken.
When combustions of hydrogen or carbon
monoxide have to be made, the capillary tube
containing palladium asbestos is inserted
between the burette and a simple absorption
pipette containing water only. With gases
:ontaining both methane and hydrogen, the
:ombustion is conveniently effected in an ex-
plosion of spherical form, in which
pipette
mercury is used as the working liquid. The
two bulbs of the pipette are connected by
thick-walled indiarubber tubing, and the ex-
FIG. 41. plosion bulb can be closed by two stop-cocks.

When gases very soluble in water have to be
two bulbs which communicate at the bottom by measured, a burette is used, provided at the top
a bent tube, one bulb being at a higher level than with an ordinary stop-cock and at the bottom
ANALYSIS. 241
with a three-way stop-cock, the volume between Stead's apparatus consists (Fig. 44) of a
them being exactly 100 c.c. The burette must graduated tube A, in which all measurements
be perfectly dry before being filled, an end are made, fitted with taps B and c,
leading
which is most quickly effected by rinsing the respectively to the absorption vessel and the
burette with water, then with alcohol, and sampling tube. The lower end of A is joined
finally with ether, and passing
a current of warm by means of a T- piece to the mercury reservoir E,
and to the tube D, which is open to the atmo-
\C
sphere at H. The readings are taken under
atmospheric pressure. The gas sample is
collected either directly in the laboratory
vessel a or in Stead's sampling apparatus
(Fig. 45). From either of these reservoirs a
portion of the gas is introduced into the ap-
paratus at c, and thence by opening B into the
laboratory vessel G, which contains caustic
potash solution standing over mercury. If the
gas consists practically of carbon dioxide,
carbon monoxide, and hydrogen, it is then
FIG. 43.
air through it. The lower end of the burette is

connected with the conducting tube by means of
the three-way tap d, the other end is connected
with an aspirator, and a current of the gas is
drawn through the burette until the air is com-
pletely expelled. The stop-cocks are then closed,
care being taken that the gas in the tube is at
FIG. 46.
mixed with a known volume of oxygen, and the

mixture sparked by means of platinum ter-
minals fused into the upper part of the graduated
tube A.
The contraction is ascertained and the
carbon dioxide produced isestimated, and from
these data the amounts
of carbon monoxide and
hydrogen are determined.
When other absorb-
able gases are present,
then six absorption ves-
sels are employed, and
these are carried on a
turn-table, so that each
in turn can be brought
into contact with the
measuring tube (Fig. 46).
In this modified form of
the apparatus the eudio-
meter tube and each of
the absorption vessels are
fitted with a perfectly flat
piece of plate glass per-
forated in the centre.
These plates are lightly
smeared with oil, and
when communication is
to be made between the & An
eudiometer and the ab-
FIG. 44. sorption vessel, these face
plates are held together by a spring clip
atmospheric pressure..- The absorptions, &c., use of

are made in the same way as with the ordinary A further improvement consists in the shown
vessel
burette. the modified form of absorption
VOL. L T.
242 ANALYSIS.
in Fig. 48, in which the reagent is contained removing the gas, the latter method is only ap-
in a glass bottle closed by an indiarubber bung plicable when the reagents do not interfere with
each other e.g. for the absorption of carbon
dioxide by caustic potash, followed by the absorp-
tion of oxygen by alkaline pyrogallate.
The estimation of nitrogen oxides in solution
in sulphuric acid is conducted in the following
manner. The apparatus is filled with mercury,
so thatwhen the tap is open between the burette
and the cup, and the level-tube is raised, the
mercury just passes through the tap and stands
at a height of about 2 inches in the level-tube.
The tap is then closed and 2-5 c.c. of the sul-
phuric acid, according to the quantity of

nitrogen oxides which it contains, is placed in
the cup, the level-tube is lowered and the tap is
turned so that the acid is nearly all drawn into
the burette without any air being admitted. To
avoid measuring out small quantities (0-5-1 c.c.)
of highly nitrated acid, this liquid should be
diluted with a known volume of pure concen-
trated sulphuric acid, and 5 c.c. of this solution
taken for analysis. The cup is rinsed with two
FIG. 48.
successive quantities of 2-3 c.c. of pure acid,
carrying a small glass stopper and a pipette which is drawn into the cup with the same
furnished with a tap. precaution as before. The tap being closed,
By means of these additions Stead's appara- the burette is taken out of the clamp and
tus can be used for the complete analysis of agitated in such a manner that the liquid is
furnace and producer gases and other technically brought thoroughly into contact with the first
important gaseous mixtures (J. Soc. Chem. Ind. 10 cm. or so of the mercury, which is broken
1889, 8, 178). up into bubbles. Nitric oxide is formed and
The nitrometer, originally devised by Lunge collects in the upper part of the tube. When
(Ber. 1878, 11, 43fi) for the estimation of nitrogen no more gas is given off, the levels are adjusted
oxides in oil of vitriol, is capable of being applied and the volume read off after the froth has
to gas analysis and a large number of other subsided. In adjusting the levels the difference
determinations. It consists (Fig. 49) of a between 'the specific gravity of the acid and the
burette, fitted at the top with a three-Avay tap mercury is allowed for by taking 6'5 mm. of
and a cup-shaped funnel, and communicating at acid = 1 mm. of mercury. A small quantity of
acid is placed in the cup and the tap opened : if
the acid is drawn in the pressure in the burette
was too low if gas escapes, the pressure was too
;
high. It is better to err on the side of too low

pressure, which is readily corrected by allowing
acid to run in from the cup and taking another
reading.
In agitating, care should be taken that the
drop of acid which collects in the top of the
burette just below the tap does not escape con-
tact with the mercury, otherwise the results will
be too low.
To prepare for another estimation, the level-
tube israised and the tap is opened so that all
the acid and some of the mercury is driven into
the cup, and the tap is then turned so that the
acid runs out at the side.
The nitrometer may be used for the valuation
of nitrites and nitrates, which are introduced in
FIG. 49. FIG. 50.
the form of a concentrated aqueous solution,
the bottom by means of caoutchouc tubing with care being taken that the proportion of water to
a plain tube of the same diameter, which serves acid does not exceed 2 parts of aqueous solution
as a level-tube. When large quantities of gas to 3 parts of the strongest acid. It may also be
have to be measured, the upper part of the used for the estimation of nitrates and nitrites
burette is expanded into a bulb, and there is a in potable waters, and in fact for almost any
similar bulb on the level-tube (Fig. 50). determinations in which a definite volume of
This apparatus is used with mercury, and
gas is given off. For example, the estimation of
is thus suitable for the analysis of gases soluble carbonic acid ; of urea by hypobromite (the
in water. It can be used in the same way
reading being increased by 9 p.c. to correct for
as Hempel's burette, and for all purposes to
solubility of the gas and incomplete decom-
'
which the latter is applicable. It may also be position) ; hydrogen peroxide by an acidified
used without absorption pipettes, the reagent solution of potassium permanganate, or, vice
being introduced by means of the cup, but versa, the value of a permanganate solution by
since the reagents cannot be removed without means of hydrogen peroxide, &c. (See Lunge,
ANALYSIS. 243
Ber. 1878, 11, 436; J. Soc. Chem. Ind. 1885, temperature and under the same pressure, and
4, 447, and 1886, 5,
82 ; Zeitsch. anal. Chem. since the gas in B occupies the same volume as
and the translation of Winkler's it would at and 760 mm. pressure, it follows
25, 309 ;
Technical Gas Analysis (1885); also Allen, that the gas in A also occupies the same volume
J. Soc. Chem. Ind. 1885, 4, 178.) as it would under the standard conditions. In
The gas-volumeter. Several of the estima- this way, by the use of the
gas-volumeter, all
to the preceding paragraph are thermometric and barometric
tions referred in
readings and all
more conveniently carried out in the gas- reductions by calculations or special tables are
volumeter devised by Lunge, as in this apparatus avoided ; for the volume of gas is read off
the decomposi- directly under conditions corresponding to the
tion can be ef- normal pressure and temperature. It is, how-
S ? fected in a sepa- ever, essential that the reduction tube should
rate vessel. The be arranged for dry or moist gases
according to
measuring tube A the nature of the analytical operation involved
and the reservoir (v. Lunge, Ber. 1890, 23, 440; 1891, 24, 729;
c are converted 1892, 25, 3157 ; Zeitsch. angew. Chem. 1890, 3,
by means of the 129 ; 1891, 4, 197, 410 ; 1892, 5, 677 ; J. Soc.
T-piece D, with Chem. Ind. 1890, 9, 547. Of. Gruskicwicz,
'
the so-called re- Zeitsch. anal. Chem. 1904, 43, 85).
'
duction tube B. In addition to the hypobromite and hydrogen
At the outset peroxide decompositions, Lunge and Mareh-
the temperature lewski have adapted the gas-volumeter to the
g and pressure are estimation of carbon dioxide in natural car-
5 observed, and the bonates, Portland cement, and other mineral
volume occupied substances, and also to the determination of
under these con- carbon in iron and steel (Zeitsch. angew. Chem.
ditions by 100 c.c. 1891, 4, 229 1893, 6, 395 ; J. Soc. Chem. Ind.
;
of dry (or moist) 1891, 10, 658). G. T. M.

air measured at
and 760 mm. ELECTROCHEMICAL ANALYSIS.
is The
calculated. The suggestion to apply the electric
first
reduction tube is current to the deposition of metals was made
filled with air to by Cruickshank in 1801 (Nicholson's Journal of
this volume, and Nat. Phil. 1801, 4, 254). He noticed that metals
the tap of the were deposited from acid or alkaline solutions
tube closed, or of their salts at the negative pole, and that the
the end of the metal went into solution at the positive pole.
reduction tube He therefore suggested that the electric current
FIG. 51. may be termi- might thus be used as an aid to analysis, par-
nated by a capil- ticularly for depositing lead, copper, and silver,
lary and sealed off after the volume has been In 1812 Fischer suggested its use for detecting
correctly adjusted. A
special tap for the redac- small quantities of arsenic (Gilbert's Annalen,
tion tube has been devised by GiJckel (Zeitsch. 42, 92). In 1840 Cozzi (Arch, delle Science
angew. Chem. 1900, 13, 961, 1238). If moist med. fis 50, ii. 208) employed the galvanic
gases are to be measured, a small drop of water current (produced by plates of gold and zinc
is introduced into the reduction tube ; if dry connected together by a wire) to ascertain
gases are under examination, a drop of concen- whether organic fluids, such as milk, contained
trated sulphuric acid must be introduced into metallic impurities. Gaultier de Claubry (J.
the reduction tube. The formulae for calculating Pharm. Chim. iii. 17, 125) applied it to detect
the volume of gas in the reduction tube are as small quantities of arsenic in animal fluids. In
follows :
1861, Bloxam (Quart. Journ. Chem. Soc. 13,
12, 338) described an electrolytic method for
detecting arsenic and antimony. Becquerel
(Ann. Chim. Phys. 1830, 43, 380) found that
V, (moist
manganese and lead were readily oxidised, and
where V, = volume of gas required ; appeared as oxides on the anode.
V =normal volume (e.g. 100 c.c.) ; All these workers appear to have merely
= observed temperature
t ; used the electric current as an aid to qualitative
=
B observed barometric pressure ; analysis. Wolcott Gibbs (Zeitsch. Anal. Chem.
3, 334), in 1864, showed
water vapour at observed
/ =* tension of that copper, nickel,
temperature. zinc, lead, and manganese might be quantita-
When a decomposition by sodium hypo- tively determined by
means of the electric
bromite or hydrogen peroxide has been carried current. Lucknow (Dingl. Poly. J. 1865, 177,
out in the auxiliary generating bottle, the gas 231, and 178, 42), from 1860, had employed
evolved passes into the measuring tube A. The electrolytic methods for the quantitative
mercury in A and c are then adjusted to the analysis copper salts and for commercial
of
same level, and the tap o closed, the gas being copper. this time forward many workers
From
then at the atmosphere pressure. The three entered the field, and about 1880 Edgar Smith
tubes are now adjusted so that the mercury in in America, and Classen in Germany, very
A and B are at the same level when the mercury much advanced the subject of electro-analysis,
in the latter tube stands at the 100 c.c.
gradua- and to-day it is one of the most useful helps to
tion. The gases in A and B are at the same the analytical chemist.
B 2
244 ANALYSIS.
Before dealing with the methods of deposition the analysis. The loop near the top of the
and separation of the metals, it will be well to serves to hang the electrode on the balance.
describe the apparatus used ; but only the The anode is
apparatus most generally employed will be made of plati-
dealt with. num wire, and
Classen first suggested the employment of a is bent upon
platinum basin as cathode and a platinum disc itself in such a
as anode. A convenient stand for holding the way that when
basin, and a method of connecting with the it is placed in
source of current, are shown in Fig. 52. The basin position for
should hold from electrolysis, as
150 to 180 c.c. of illustrated in
solution. The Fig. 55, an even
inner surface of density is ob-
the basin should tained on all
be roughened by parts of the
the sand blast, as cathode.
this causes better It has been
adherence of the found that the
deposit, especi- rate of deposi-
ally in the case tion of metals
Fio. 54.
of peroxides such from theirsolu-
as lead and man- tions is very much increased and higher current
ganese. The base densities can be employed when either the
of the stand is of anode or cathode is rapidly rotated. Frary
slate or marble,
and the brass rod
which conveys
the current is
hollow ; through
this brass rod an
insulated wire for
carrying the +
current passes,
and is connected
at the top of the
~- ~~
rod by means of
IIG. 52. a piece of ebonite.
The ring which supports the basin has three little
platinum points at equal intervals on its circum-
ference ; on these the basin rests, thus ensuring
good contact. The posi-
tive pole of the source
of current is connected
with the binding-screw
fixed to the slate base,
and the negative pole
with the binding screw
-
marked .
Another useful form of

electrode is illustrated in
Fig. 53. The anode is a

stout spiral of platinum and FIG. 55.
the cathode a cylinder
is
of platinum gauze. This (Zeit. f. Elektrochem. 1907, 308) has also showri
form of electrode can be that excellent results can be obtained by electro-
employed either for station- lysing with
ary work or for rapid depo- stationary elec-
sition work when the anode trodes, but
is rotated. The vessel in causing agita-
which the electrolysis takes tion of the
place may either be a electrolyte by
beaker, or, better, a funnel placing the
FIG. 53. with a tap such as is illus- whole appara-
trated in Fig. 67. tus in the field 0~
For stationary work the Flag electrode of of a powerful
F. Moll wo Perkin (Fig. 54) gives very satisfactory
electro-magnet.
results. The cathode consists of a small sheet The forms of
of stout platinum gauze, autogenously fastened the apparatus
on to a rigid platinum-iridium frame, both frame are depicted in YiQ 56
and gauze being roughened by the sand blast. Fig. 56. From
The wire holds the electrode in position during the figure it is seen that the solution is contained
ANALYSIS. 245
in a beaker B, in which is a cylindrical pla- Fig. 58 represents the the
arrangement of
tinum gauze cathode c and a heavy platinum apparatus when fitted together.
wire as anode A. The beaker is placed in the
centre of a spool made from insulated copper
wire E. By passing an electric current through
the copper wire of the spool, a powerful
magnetic field is produced, in the centre of
which the beaker stands. If now a current
be passed through the electrolyte by means of
the electrodes, the electric lines of force are cut
at right angles by the magnetic lines of force,
and this produces a tendency for the solution to
rotate, owing to the vertical magnetic field and
radial current lines. The speed of rotation
depends upon the ratio between the electric
current and the magnetic current. With an
electrolysing current of from 6 to 7 amperes,
Frary was able to deposit 0-850 gram copper
in 15 minutes. The other form, illustrated in
Fig. 57, is for electrolysing with a mercury
cathode, the
use and appli-
cations of
which will be
described later.
The electrolys-
ing vessel is
ring-shaped, so
that it may fit
into a hole cut
into the pole D
of the magnet. FIG. 58.
An iron rod
passes from the F. Mollwo Perkin and W. E. Hughes (Trans.
other pole up Faraday Soc. 1910, 14) use an electrode of sheet
into the centre platinum spun up so as to form a narrow thimble
of the electro- (Fig. 59), the upper end being open and
lysing vessel. having a stout iridio-platinum wire fused
A the anode
is on to it by means of three short wire
and c the ca- supports. This electrode is fixed into
thode. Ex- a small chuck and rapidly rotated by
FIG. 57. tremely rapid means of an electromotor, the speed of
rotation is thus rotation usually being from 750 to 950
produced, because the iron core very much revolutions per minute. When in use,
facilitates the passage of the about two-thirds of the length of the
magnetic current,
there being a radial field with vertical current thimble is dipped into the electrolyte,
lines. the active surface being about 16-3 sq.
The advantages claimed for this method cm. If dipped too deeply into the solu-
are rapidity of deposition, and, as there are tion, there is a tendency for the liquid
:
no mechanical parts which require lubrication, to splash into the interior of the cylinder,
there is no chance of contamination from oil and this would, of course, lead to erro-
or grease into the solu- neous results. The anode consists of a
accidentally falling
tion. As a matter of however, rapid
fact, platinum cylinder of fine mesh. It is, pIQ 59
methods electrolysis are more frequently
of however, frequently more satisfactory to
carried out by means of a
rotating anode or employ a rotating anode and a stationary
cathode. cathode, and for this purpose the gauze anode
Gooch and Medway (Amer. J. Sci. 15, 320) is employed as cathode, and the anode consists
use a rotating cathode. It is made from a of a spiral of stout iridio-platinum wire. The
platinum crucible of about 20 c.c. capacity. simplest arrangement is illustrated in Fig.
53.
The crucible is attached to the shaft of the The electrolysing vessel consists of a tap funnel
electromotor, which is used to rotate it at which, when the electrodes are covered, holds
a speed of from 600 to 800 revolutions about 60 to 70 c.c. of solution. The advantage
per
minute by fitting it over a rubber form of electrolysing vessel the ease
stopper with of this is
a central bore, into which the end of the with which the electrolyte can be removed on
shaft fits tightly. In order to make electrical the completion of the electrolysis and the
connection between the crucible and the shaft electrodes washed. The method of procedure
is to place a beaker beneath the tap and draw
of the motor, a narrow
strip of sheet platinum
off the solution until about half of it has run in.
is soldered to the shaft
and bent upwards along
the sides of the This connects the Distilled water is then run up to the original
stopper.
shaft with the inside of the crucible when the mark and the solution drawn off as before.
latter is pressed over the stopper. The anode The operation is repeated until the ammeter
consists of a half needle sinks to zero. The remaining water is
cylinder of sheet platinum.
246 ANALYSIS.
run off, the tap closed, and the funnel filled with then a mercury cup is fastened on to the top of
pure methylated spirit. This is run off, and, the spindle so that the current passes directly to
the spindle.
The apparatus of H. J. Sand (Trans.
Chem. Soc. 1907, xvi. i.373) is rather more
complicated, but gives equally satisfactory
results.
The special object in the design of this
electrode Avas to produce an apparatus which
could be satisfactorily employed for the
separation of metals by graded potentials.
It consists of a pair of platinum gauze
FIG. 60.
after a final washing with absolute alcohol,

carried out in the same manner, the electrodes
are removed and the cathode dried in the steam
oven.
Another form of rotating cathode devised by
Perkin is illustrated in Fig. 60. The cathode
consists of a cylinder of platinum gauze. The
anode is in the
form of a double
circle of stout
platinum wire,
and has four small
baffle plates so
placed as to pre-
vent it from ro-
tating with the FIG. 62.
cathode.
In order to electrodes (Fig. an
inner rotating el
61), .-
The
rotate the anode trode A, and an outer
electrode B.
(or cathode), it is two are kept in position relatively to each
fixed into a small other by means of a glass tube, Avhich is
chuck fastened on slipped through the collar and the ring of the
to the end of the outer electrode B. It is gripped firmly by
spindle of a bi- the former, but passes loosely through the
cycle hub. The latter. The hollow iridio-platinum stem A
barrel of the hub of the inner electrode is passed through the
has an arm fast- glass tube, in which it rotates freely. The mesh
ened into it which of the gauze is 14 2 per sq. cm. The gauze
can be clamped of the outer electrode almost completely stops
to any suitable the rotation of the liquid. The electrolyte is,
support. The therefore, ejected rapidly from the centre of
upper end of the the inner electrode by centrifugal force, and is
spindle has a sheaf continually replaced by liquid drawn in from
FIG. 61. of pulleys fast- the top and the bottom. So great is the suction
ened to it, so that thus produced, that when the electrode is moving
it can be rotated by means of a belt from a rapidly, chips of wood or paper placed in the
motor and different speeds be obtained. It is solution are drawn down to the top of the
found that the current passes very well through outer electrode. The circulation is practically
the barrel of the hub and the balls, which independent of the size of the beaker employed.
are lubricated with oil and graphite, to the As the outer electrode surrounds the inner
spindle, and so to the electrode. When it is completely, the lines of flow of the current are
desired to obviate all drop in potential, e.g. if the contained between the two, and even when
apparatus is to be used for graded potentials, strong currents are employed, the potential
ANALYSIS. 247
of the electrolyte anywhere outside the outer rotated by means of an electromotor or water
electrode is practically the same as that of the turbine.
layer of liquid in immediate contact with it. The chief difficulty in
using the mercury
62 shows the apparatus with stand and cathode is the trouble
Fig. experienced in washing
motor in work- and drying it. The solution left at the end of
ing order. Be- the electrolysis is siphoned off, and at the same
fore the method time water is run in until the needle of
distilled
adopted for elec- the ammeter drops to zero. Then, and not till
trolysing by then, the current is switched off. The inside of
means of graded the beaker and the
amalgam are rinsed with
potential is dis- alcohol three times, and finally with dry ether.
cussed, the mer- It is advantageous, in order to drive out
cury cathode de- thoroughly the last traces of ether, to blow dry
vised by Smith air into the beaker for a few minutes. After
and Howard will standing for half an hour, the apparatus is ready
be described. for weighing. F. M. Perkin (Trans. Faraday
WolcottGibbs, Soc. 1910, 14) uses a small quartz beaker as
in 1880, first sug- containing vessel, Avith an iridium wire fused
gested the use of into it to make contact with the
mercury. The
metallic mercury advantage of iridium is that it does not amalga-
as cathode, a mate with the mercury. An advantage of the
definite amount quartz vessel is that it can be heated to redness
being weighed for purposes of cleansing. The apparatus is
into a beaker, illustrated in Fig. 64. It will be noticed that a
where it was con- siphon tube is fused
nected by means into, one side of the
of platinum wire beaker. The layer of
with the nega- mercury must not be
tive pole of a sufficient in quantity
battery. Various to close the side tube.
metallic salt A spiral iridio-plati-
solutions were num anode is em-
experimented ployed. When the (ft
upon, and, in electrolysis is finished,
1883 (Amer. a piece of rubber tube
Chem. J. 13, 571), is fastened to the
FIG. 63.
Gibbs stated bent end of the siphon.
'
that was found possible to separate iron,
It Distilled water is
cobalt, nickel, zinc, cadmium, and copper so added so that the

completely from solutions of the respective solution begins to
sulphates that no trace of metal could be siphon over into a
detected in the respective liquids.' Gibbs had beaker placed below
in view not only the determination of the the rubber tube. In jr IG 64. .
metals, but also of the anion left in the solution order to work with
by titration. as small a quantity of water as possible and in
In 1886 Luckow (Chem. Zeit. 9, 338, and cases where the solution is required again, e.g.
Zeitsch. anal. Chem. 25, 113) suggested the addi- in metal separations, the solution is allowed
tion of a known weight of a solution of a mercury to run out until its level drops almost to the
salt to a solution of zinc
sulphate, and so to end of the anode. Fresh water is then run in,
deposit zinc and mercury simultaneously. and the operation repeated until the ammeter
In 1891 Vortman (Ber. 24, 2749) suggested a needle points to zero. For purposes of steadi-
similar method, and employed it in the deter- ness the vessel is held between clips on a copper
mination of several metals. Drown and plate.
MoKenna (Amer. Chem. J. 5, 627) further worked By means of the mercury cathode not only
at the subject,
using an apparatus somewhat can the cations be rapidly and accurately deter-
similar to Wolcott Gibbs, that is to say, an mined, but also the anions remaining in the
actual mercury cathode, but the process was solution.
first
successfully worked out by Edgar Smith Method of Graded Potential.
and his collaborators (J. Amer. Chem. Soc.
25, 885). The apparatus employed consists Each metal has a particular potential at
of a small tube or beaker of about 50 c.c. which it begins to be deposited; below this
capacity, close to the bottom of which a potential it is not possible to deposit the metal.
thin p\atinum wire is introduced It follows, therefore, that when dealing with a
by means of
which the current is supplied to the mercury solution containing the salts of two or more
cathode (Fig. 63). metals it will be possible, provided the deposition
The external part of the platinum wire potentials of the metals do not lie too near
touches a disc of sheet copper on which the
together, to deposit separately the metals, by
beaker rests, and which is connected with the first working with the lowest potential at which
negative source of the current. one of the metals will be deposited. When this
The anode is either a perforated disc of metal has been deposited the next one in the
platinum or a stout spiral of platinum wire. potential series will be deposited if the potential
During the electrolysis the anode is rapidly is raised.
248 ANALYSIS.
This method of analysis was suggested by
Kiliani in 1883, and was further elaborated by
FIG. 65.
Freudenberg working in Ostwald's laboratory

(Zcit. physikal. Chem. 12, 97).
But it was
I
ANALYSIS. 249
of the metal will fall
again, the concentration nese, chromium, molybdenum, uranium. Some
to under 0-1 p.c., so that the deposition can be of them can, however, be
satisfactorily deposited
considered finished. as an amalgam on a
mercury cathode.
In cases where side-reactions occur, the GEOUP V. The metals of this groupare the
current does not fall to zero, but it generally most strongly electropositive, and can only be
attains a constant value which allows it to be deposited by using a cathode of mercury but
;
seen when all the metal has been removed. In even then it is not possible in all cases to obtain
certain cases this can be tested for chemically, a quantitative separation. The metals of this
and by continuing the experiment for about group are aluminium, glucinum, calcium,
half as long again as this reaction demands, the strontiiim, barium, magnesium, potassium,
metal may be safely assumed to have been sodium, lithium, rubidium, caesium.
deposited completely. This method may
be GEOUP VI. These are all anions, and their
adopted, for example, in the separation of lead estimation has been rendered possible mainly
from cadmium, the former being roughly tested through the work of Edgar Smith, who com-
for by sulphuric acid. If none of these methods pletely deposits the metals by means of a mercury
is available, the metal must be deposited to cathode and estimates the anions by titration or
constant weight, or else the separation must be other appropriate method. The most important
carried out under very carefully defined con- anions analysed by this method are F', 01', Br',
ditions for a length of time proved by previous I', S0 4 ", C0 3 ", Fe(CN),"", Fe(CN),"' f P0 4 '",
experiment to be more than sufficient. NO,'.
Sand has simplified the apparatus necessary It has not been found possible to analyse
for the potential measurements by fitting all the organic anions by electrolytic methods, because
apparatus required for the measurement of the they are either decomposed or various reactions
electrode potential into a single box. Full par- more or less complicated take place. Thus,
ticulars will be found in Trans. Faraday Soc. for example, when the acetate anion is given up
1909, 162. at the anode, ethane is produced, which, of
F. M. Perkin uses the apparatus depicted on course, is given off in the form of a gas.
p. 248 for working with graded potentials. The
vessel containing the electrolyte has a tube Nature of Deposit.
fused into the side. Into this side tube the Sand (Trans. Chem. Soc. 1907, 383) has
capillary end of the auxiliary electrode is theoretically and practically worked out the
inserted (Fig. 67). conditions necessar}' for obtaining adherent metal
deposits.
CLASSIFICATION OP THE METALS FOE ELECTEO- The production of a uniform deposit over
ANALYTICAL PUEPOSES. the electrode depends entirely upon the relation
Most metals can be deposited satisfactorily at between polarisation and the E.M.F. required
the cathode, particularly since the introduction according to Ohm's law to force the current from
of the mercury cathode and of the graded poten- one part of the solution to the other (Zeitsch.
tial methods. Theoretically, by grading the Elektrochem. 1904, 452). The case of metals
potential, it should be possible to separate any such as cadmium and zinc, which require a
one metal from another. Indeed, in many higher potential for then precipitation from
1
cases, this can be done, but there are cases in most of then* solutions than hydrogen, is a
which the potential differences at which two question of supertension. The metals can
metals can be deposited, that is to say, the only be deposited by virtue of the super-
minimum potential at which they will both be tension which is required to liberate hydrogen
deposited, lie so close together that it is not as a gas. This supertension varies with the
possible to so adjust the conditions that a material of the electrode, and may even vary
separation can be effected. at different parts of the same electrode, owing
GROUP I. Copper, silver, mercury, gold, to different states "of its surface. Consequently,
palladium, rhodium, platinum, indium, bismuth, it may happen that the metal is deposited
antimony, tin, (arsenic), tellurium. These on a portion of the electrode which has a high
metals are more electronegative than the supertension, and will continue to grow there ;
hydrogen electrode, and, consequently, can but at rougher parts of the electrode, where
theoretically be deposited quantitatively from the supertension is lower, hydrogen alone
acid solutions. will be evolved. This is, for example, particu-
GBOUP II. Cadmium, zinc, and indium. larly noticeable in the case
of zinc, which,
These metals aremore electropositive than instead of being evenly deposited over tho
hydrogen, but, owing to the supertension of surface of an electrode, apparently perfectly
the hydrogen evolution in acid solution, it is smooth and even, often comes out in patches,
free from
actually possible to deposit them from weak parts of the electrode being absolutely
acid solutions. deposit. Some solutions also of
the same metal
GROUP in
III. Iron, nickel, cobalt. These appear to be more sensitive to variations
metals are more electropositive than hydrogen, the quality and character of the electrode than
but, as the supertension of hydrogen is very others. Thus with ordinary electrodes when
low, these metals cannot be deposited completely the potential is not graded, it is a matter of the
from acid solutions. They can, however, be greatest difficulty to obtain an
adherent deposit
deposited from acid solutions if a mercury of copper when the electrolyte is sulphuric acid.
cathode is
employed. On the other hand, with electrolytes of potas-
GROUP IV. The metals of this group can sium cyanide or nitric acid, an even deposit is
either be deposited as oxides at the anode, or
readily produced.
as oxides at the cathode. The group comprises The nature of the deposit. Electrolytic de-
the following metals or
:
lead, thallium, manga- posits may be spongy, coarsely crystalline,
250 ANALYSIS.
finely crystalline. The last is the only form dipped into a beaker of absohite alcohol. It
in which metals may be deposited in order to is then dried in the steam oven, and, after cooling
yield satisfactory quantitative results. Sand for 20 minutes, weighed. When the gauze
considers (I.e.) that spongy deposits are most cylindrical electrode is used, a stoppered funnel
probably due to the metal being deposited in as illustrated in Fig. 67 is very convenient.
the form of an unstable hydride, which gradually The solution is drawn off until only about one
decomposes with evolution of gas. quarter of the electrode is immersed. Distilled
The difficulty of hydride formation is got water is then run in, and the operations repeated
over by keeping the potential of the electrode until the ammeter shows zero. By operating
under control. Vigorous stirring of the elec- rapidly, the cathode may be removed, and, if
trolyte, small current density, and the presence dipped at once into a beaker of water and then
of some oxidising agent, tend to keep the washed under the tap or in several change
potential low. But, by using an auxiliary of water and then in alcohol, absolutely accurate
electrode and rapid rotation, it is possible to results can be obtained.
obtain metals from solutions from which, under The deposit obtained from nitric acid is
ordinary circumstances, they cannot be de- bright red, and generally has a more or less
posited. crystalline appearance. If the C.D. has been
'
Copper. too high, it may be burnt,' and have a brown-

Copper may readily be deposited from solu- ish appearance, and may be powdery and non-
tions which contain considerable quantities of adherent. When it is desired to electrolyse
nitric or sulphuric acid. But good deposits can over-night and this is often found very con-
also be obtained from cyanide solutions, and it venienta C.D. of from 0-2 to 0-3 of an ampere
is possible to employ solutions containing an is used. It is generally advisable in this case
excess of ammonia. to add more nitric acid, because, owing to the
The solutions which give the best results are reducing action of the hydrogen liberated at the
those containing nitric acid or potassium cyanide. cathode, the nitric acid becomes converted into
Indeed, it is a matter of considerable difficulty ammonia. This formation of ammonia causes
to obtain satisfactory results in presence of free the deposit to be spongy and of a bad colour,
sulphuric excepting when a mercury
acid, when it is difficult to wash and weigh. For run-
cathode isemployed. For stationary work, ning over-night about 2 c.c. extra of nitric acid
either the gauze flag electrode or the cylindrical should be added for every 100 c.c. of solution.
gauze electrode is to be recommended. The deposits obtained with sulphuric acid
Nitric acid. About 1 gram of the copper are generally not satisfactory, but of all the
salt is dissolved in about 140 c.c. of water, and copper deposits that obtained from solutions
5-10 c.c. of nitric acid (sp.gr. 1-42) added to containing potassium cyanide is the most
the solution ; that is, from 8 to 10 p.c. of the beautiful.
acid. If the flag electrode is employed, usually Potassium cyanide. The colour of the
about 120 c.c. of water is sufficient, in which deposited metal is pinkish red, and perfectly
case proportionately less nitric acid must be smooth. But, from other points of view, the
used. The solution may either be electrolysed deposition from cyanide solutions has no
at ordinary atmospheric temperature, or heated advantage over the deposits obtained from
from 45-50 ; in the latter case the time solutions containing nitric acid. The copper
required for the complete deposition of the salt is dissolved in about 30 or 40 c.c. of dis-
metal is considerably lessened. The best C.D. tilled water, and then a freshly prepared solution
to employ is from 0-8 to 1-2 amperes, when the of potassium cyanide added, until the precipi-
E.M.F. will be from 1 to 2-8 volts. A bright tate first produced is dissolved. Slightly mor
red film will be seen to flash across the cathode potassium cyanide than is necessary to
almost immediately the circuit is completed. solve the precipitate should be used, but any
In cold solutions, from 2 to 3 hours will be considerable excess must be avoided. Generally
required to completely deposit the metal with ; speaking, from 1 to 1-5 grams of potassiur
hot solutions the rate of deposition is consider- cyanide should be used for every gram of copper
ably accelerated. To ascertain when the whole salt taken.
of the copper has been deposited, withdraw The C.D. employed should be from 0-8
about 1 c.c. of the solution by means of a pipette, 1-2 amperes. The "E.M.F. required in col
transfer to a test-tube, make alkaline with solutions will be found to be about 5-6 volts :
ammonia, then acid with acetic acid, and add in warm solutions, from 4 to 5 volts. The whole
a few drops of potassium ferrocyanide ; the of the copper is deposited in 2 to 2 hours.
formation of a brown precipitate or colouration Rapid methods. By employing rotating
shows that there is still some copper left in the electrodes, either rotating anode or cathode,
solution, in which
case, of course, it is necessary copper may be completely deposited in a fe\
to continue the electrolysis until, on further minutes. Thus Sand, by using his apparatus,
testing with the reagent, no colouration is was able to completely deposit the copper from
produced. 0-25 gram copper sulphate in 6 minutes, the
Washing the deposit. As the electrolyte con- number of revolutions of the anode per minute
tains an excess of free nitric acid in which the being about 800 ; in. that of Fischer the copper
copper deposit is readily soluble, the washing from 0-3 gram copper sulphate was deposited
has to be carried out with caution. Some in 10 minutes, the speed of revolution being
workers prefer to siphon off the electrolyte with- 1000 to 1200. In the one case a rotating anode
out breaking the circuit, and to run in water at was employed and in the other the cathode was
the same time, until the ammeter points to zero. rotated. The electrolyte in both cases contained
The current is then cut off and the cathode free nitric acid. Cyanide solutions give, however,
removed, finally washed with distilled water and equally satisfactory results.
ANALYSIS. 251
Edgar Smith, by employing a rotating anode The mercury can be removed from the
and mercury cathode, has deposited quantita- electrode by heating in the Bunsen flame, but
tively 0-789 gram of copper in 10 minutes, and as owing to the tendency for electrolytically
much as 0-3945 gram per 4 minutes, the solutions deposited mercury to alloy with platinum, the
containing sulphuric acid. The advantage of electrode is almost invariably marked with
the mercury cathode is that almost any electro- black stains, and a slight loss in weight takes
lyte can be employed equally satisfactorily. place. For this reason some workers prefer to
Indeed, the pure salt of the metal may be plate the electrode with copper or silver before
dissolved in water and electrolysed without the using. These difficulties are, however, entirely
addition of any acid or other electrolyte. When eliminated by using a mercury cathode in fact,
;
the whole of the metal has been deposited, the it is

strongly recommended to employ always a
solution is run off, and may then be titrated in mercury cathode when dealing with mercury.
"
order to determine the anion, e.g. SO 4 (p. 247). Many electrolytes have been suggested, and
Silver. all give more or less
satisfactory results. Thus,
Silver can best be deposited from solutions the mercury salt may be dissolved in water
containing potassium cyanide. From solutions and electrolysed in presence of a small quantity
containing other electrolytes it is apt to be de- of sulphuric, hydrochloric, or nitric acid. With
posited in a crystalline feathery form, and conse- sulphuric acid, from 1 to 2 c.c. of the concen-
quently does not adhere well to the cathode. trated acid are added to each 100 c.c. of
There is, however, a tendency for the results solution, and electrolysis conducted with a
to be slightly too low when cyanide solutions C.D. of 0-3-0-8 ampere per square decimeter,
are employed. It is very important that only which is finally increased to 1 ampere towards the
the purest potassium cyanide be used in making
j
end of the operation. With rotating electrodes,
up the solutions. For 0-5 gram of a silver salt j
ciirrents of from 4 to 6 amperes per square deci-
about 3-4 grams of potassium cyanide will , meter may be employed. The temperature of the
usually be found sufficient. With a C.D. of 0-5 electrolytemay be 50-60, but not higher.
to 1-0 ampere, and a temperature of 50-60, [
Sometimes, owing to the reducing action of the
the silver will be deposited in from 1 to 2 hours.
[
hydrogen given off at the cathode, mercurous
Using a cold solution and with a C.D. of from j
salts are precipitated. The addition of small
0-2 to 0-35 ampere, the time required is from quantities of ammonium persulphate will cause
4 to 4-5 hours. The deposit should either be them to go into solution again. The con-
washed by siphoning, or the electrode must be ditions with the other acids mentioned are
very rapidly removed from the electrolyte and very similar to those required for sulplmric
dipped into water, in order to avoid loss by the acid. Potassium cyanide is not to be recom-
solvent action of the potassium cyanide. mended, owing to slight solution of the anode
With rotating electrodes the silver can be taking place.
deposited within a few minutes. By using an Sodium sulphide gives very satisfactory
auxiliary electrode androtating anode
the results, but care must be taken to employ a
vigorously, Sand was able to deposit silver from very pure solution of salt. From 25 to 30 c.c.
ammoniacal solutions in 7 to 8 minutes. of the concentrated solution of sodium sulphide
Smith, by using a mercury cathode and are required for every 100 c.c. of solution. The
rapidly rotating anode deposited 0-2240 gram of solution should be heated to about 65, and for
silver from silver nitrate in 4 minutes. At the stationary electrodes a C.D. of 0-15-0-25 ampere
commencement of the operation an anodic per square decimeter used. With rotating
deposit of silver peroxide was obtained, but electrodes from 3 to 6 amperes per square
after a minute or two this disappeared. decimeter may be used.
Mercury. With mercury electrodes rotating anodes are
Many methods have been devised for pre- almost invariably used, and high-current densities
cipitating mercury on platinum cathodes, and can be safely employed. The whole of the mer-
some of them give quite satisfactory results. cury can be deposited in from 15 to 25 minutes.
When mercury is deposited on a platinum dish, Cinnabar may be dissolved in aqua regia,
or on a wire gauze electrode, it spreads
evenly the solution evaporated to dryness. The
over the surface as a thin metallic film, which, residue is then taken up with water, filtered from
however, is inclined to run together as the gangue, and then directly electrolysed after the
amount of mercury on the electrode increases addition of a small quantity of nitric acid.
in quantity. After the mercury has been Gold.
deposited, the electrode is washed with Avater Gold may be deposited from its -solution
in the usual way, then in absolute alcohol, and in cyanide or in sodium or potassium sulphide,
finally in absolute ether. The last traces of or in ammonium thiocyanate. The drawback
ether may be removed by
blowing dry air on to using potassium cyanide is the tendency for
to the electrode. the anode to go into solution. But with low-
On no account may the mercury-coated current densities, this only takes place to a
electrode be heated. If the electrode is washed small extent. The solution is made up by
once in 90 p.c. alcohol, and then placed in a adding rather more than the quantity necessary
beaker of anhydrous acetone for a minute, it of potassium cyanide to bring the gold salt into
may then be dried without using ether. It is a clear solution. With stationary electrodes
always advisable, before weighing, to place the a C.D. of 0-6-0-8 ampere is employed at a
de-
electrode in a desiccator for 20 minutes. The temperature of 50-60, the metal being
desiccator should have a dish in it posited in the course of 2 to 3
hours. With
containing a
3 amperes
little metallic
mercury, because even at ordinary rotating electrodes a current of about
temperatures mercury volatilises to a small may be employed, when the metal will be
but appreciable extent. deposited in about 30 minutes.
252 ANALYSIS.
Sodium sulphide. From 20 to 25 c.c. of a Elektrochem. 1904, 386, 853, and Annaien,
saturated solution of sodium sulphide are used 1905, 235), necessary that the potential should
for every 100 c.c. of solution. With a C.D. of not exceed 1-25 volts. With stationary elec-
from 0-1 to 0-3 ampere the metal will be de- trodes the process is very slow, and polarisation
posited in from 4-5 to 5-5 hours. With rotating at the anode takes place, owing to the formation
electrodes and high-current densities, the results of oxy- compounds. On the other hand, by
are too high, owing to deposition of sulphur using a rotating electrode and solutions of
along with the gold. palladium ammonium chloride with 30 p.c. by
Ammonium thiocyanate. 5 to 7 grams of weight of sulphuric acid and a C.D. of from 0-23
ammonium thioycanate are dissolved in about to 0-50 ampere, as much as 0-3-0-9 gram may
80-90 c.c. of water at 70 to 80, and the gold be deposited in from 3-5 to 5 hours.
solution run slowly in with constant stirring. Julia Langness, by using currents of from
The clear solution is electrolysed at a temperature 15 to 17 amperes, and an ammoniacal solution,
of 40-50 with a C.D. of 0-2-0-55 ampere, the has obtained quantitative deposits in from 3 to
metal being deposited in from 1-5 to 2 hours. 5 minutes.
This method has not been tried with rotating Antimony.
electrodes. The precipitation of small quantities This metal may be deposited from its thio-
of yellow canarine in the electrolyte during salts, particularly sodium thioantimonite, a
electrolysis does not interfere with the reaction. method originally suggested by Classen. During
E. F. Smith obtains good results by electro- the electrolysis there is, however, a danger,
lysing a gold chloride solution, using a mercury owing to the deposition of sulphur at the anode,
cathode. In order to prevent the chlorine for sodium thioantimoniate to be formed, and
evolved attacking the anode, from 10 to 12 c.c. this prevents the quantitative deposition of
of toluene are added. The time required to the metal. A. Fischer (Ber. 1903, 2474) recom-
deposit 0-15-0-2 gram of gold is about 5 to mends the addition of potassium cyanide to the
7 minutes. electrolyte, which prevents the formation of the
Most solvents for gold will also attack the thioantimoniate, thus :
platinum cathode. Aqua regia, for example, N 2 S 4 +3KCN=3KCNS+Na 2 S.

cannot be used to dissolve the gold from the
platinum. F. M. Perkin recommends a dilute There is one difficulty when sodium sulphide
solution of potassium cyanide to which is added is used the results obtained are usually slightly
4-5 c.c. of hydrogen peroxide, or from 2 to 3 grams too high. This is due to the occlusion of small
of an alkali persulphate. On gentle warming quantities of sulphur along with the metal.
the deposit is removed in a few seconds. For this reason large quantities of metal should
not be deposited by this method. The antimony
2Au+4KCN+H 2 O 2 =2KAu(CN) 2 +2KOH. salt is dissolved in 60-80 c.c. water made just
Platinum. alkaline with sodium hydroxide, any precipitate
Like gold, platinum can be deposited from being ignored, then 20-25 c.c. of a fresh saturated
solutions containing free mineral acids, but solution of sodium sulphide added, and 2-5-3
unlike gold, which from these solutions is grams of potassium cyanide. The solution is
deposited in a non-adherent form, it may be then electrolysed at from 30-40. With
deposited with very feeble currents in a hard stationary electrodes the metal is deposited in
and reguline condition. With high currents and from 4-5 to 6 hours ; when rotating electrodes
with stationary electrodes the metal is always are used, in 30 to 45 minutes.
deposited as platinum black. With a current F. M. Perkin and H. D. Law (Trans. Faraday
of from 0-01 to 0-05 at a temperature of 50-60, Soc. i. 262) recommend neutral tartrate solu-
about 0-1 gram of platinum can be deposited in tions. The antimony salt is dissolved in water,
4-5 to 6 hours. Julia Langness (J. Amer. and from 8 to 10 grams of ammonium tartrate
Chem. Soc. 1907, 459), by using a rotating added if necessary, the solution is neutralised
;
cathode, deposited 0-2 gram of platinum from a with dilute ammonia. At a temperature of
solution of K 2 PtCl 6 in 5 minutes. But the from 70 to 80, and a C.D. of 0-25-0-55 the metal
current, 17 amperes, must be looked upon as can be deposited with stationary electrodes in
excessive for analytical purposes. from 2-5 to 3 hours.
Before depositing platinum it is advisable to Sand (Chem. Soc. Trans. 1908, 1572) dis-
coat the cathode with silver. solves the metal in 20 c.c. of hot cone, sulphuric
Rhodium. acid, and dilutes the cold solution to 80 c.c.
This metal may be deposited on to a silver- The solution becomes turbid owing to hydro-
coated electrode from solutions acidified with lysis, but this disappears during the electrolysis,
phosphoric acid. A current of 0-18 ampere and does not affect the result. The auxiliary
is used. As the process continues, the purple electrode potential is kept at from 0-55 to 0-65,
colour of the solution gradually disappears and but may be increased to 0-75 toward the end
becomes colourless, when the deposition is of the process. The time required to deposit
finished. With a rotating anode the metal 0-35-0-45 gram of metal is from 20 to 35 minutes
may be deposited from solutions weakly acidu- with an anodic rotation of about 800 revolutions
lated with sulphuric acid in about 15 minutes
per minute. Small quantities of hydrazine
with a current of 8 amperes, and with a current sulphate (0-5-0-6 gram) are added to reduce
of 14 amperes in 5 minutes. The deposited any antimonial salts which may be formed.
'
metal has a black colour, but is quite adherent. Bismuth.

Palladium. Until the advent of rotating electrodes, and
In order to obtain a dense and firmly
particularly of the method of graded potential,
adhering deposit of this metal from acid solu- bismuth was one of the most difficult metals
tions, it is, according to Amberg (Zeit. f. to deposit, since it almost invariably came
ANALYSIS. 253
down in a powdery and non-adherent form. 0-1 ampere. Time
of deposition, 4 to 5 hours.
These remarks do not apply to the mercury When a rotating electrode is employed, the time
cathode. According to Kollock and Smith of deposition is much accelerated.
(J. Amer. Chem. Soc. 27, 1539)
to a solution GROUP II. Zinc.
containing about 0-2 gram of the metal as nitrate, Zinc is rather a difficult metal to
deposit
the volume of which should not exceed 12 c.c., satisfactorily and quantitatively, and a very
0-5 c.c. of strong nitric acid is added. A current large number of methods have been suggested
of about 4 amperes is passed, and the whole by different workers. Although it is +0-77
of the bismuth will be precipitated in from 12 volt more positive than
hydrogen, it can be
to 15 minutes. The anode should be very deposited from slightly acid solutions, owing to
rapidly rotated, so that the mercury may take the high supertension of
hydrogen evolution
up the bismuth as it separates, otherwise it from the surface of zinc, the supertension of
mav collect in a black mass beneath the anode. hydrogen being 0-70 volt.
Sand (Chem. Soc. Trans. 1907, 373) uses a With zinc it is advisable always to employ
solution containing tartaric acid any excess of
; rotating electrodes. The electrodes need not,
nitric acid, which may be in the original solution, however, be made of platinum ; nickel, par-
is removed by the addition of sodium tartrate. ticularly in the form of gauze, answers equally
By means of the auxiliary electrode, the cathode well.
potential is maintained between 0-63 and 0-9 Price and Judge (Trans. Faraday Soc. 1907,
volt. The anode is rotated at 800 revolutions 88) use an electrolyte containing sulphuric
per minute. In one case the amount of metal in acid which must not be more than^-W and sodium
the solution was 0-2 gram, 2-5 c.c. of nitric acid sulphate.
(1:4) was added, and 8 grams of sodium tartrate. It is, in fact, better to keep the
normality
With a current varying from 0-2 to 3 amperes the of the acid rather lower than one-sixth.
By
metal was deposited in 9 minutes. starting with a C.D. of 0-25 ampere and increasing
A. Fischer uses an electrolyte containing to 2-0 amperes about 0-2 gram of metal can be
for each 0-5 gram metal, 10 grams of potassium deposited in 40 minutes.
oxalate, and 5 grams of Rochelle salt. By Owing to acetic acid being much less dis-
means of an auxiliary electrode, the cathode sociated than sulphuric acid, solutions
containing
potential is kept at 0-8 volt. Temperature of considerable quantities of this acid may be used.
solution, 75; time required, 11 to 15 minutes. Thus, Exner (J. Amer. Chem. Soc. 1903, 896)
Tin. deposited 0-25 gram zinc with a current of 4
Tin can be satisfactorily deposited from an amperes in 15 minutes. The electrolyte con-
ammonium sulphide solution. Sodium sulphide tained 3 grams sodium acetate and 0-30 p.c.
isnot satisfactory ; indeed, tin is not thrown acetic acid. A. Fischer (Chem. Zeit. 1907, 25)
out from strong solutions at all. Hence, we takes 1 c.c. cone, sulphuric acid, 3-5 c.c. cone,
have here a method of separation of antimony ammonia, 1-5 c.c. acetic acid, and 2-5 grams
and tin. If the tin solution is acid, it is first ammonium acetate. A. Classen (Quant. Analyse
neutralised with ammonia, and then sufficient d. Elektrochem. 1897, 156) uses a solution of
yellow ammonium sulphide is added to dissolve potassium oxalate, the zinc solution is added
the precipitate and form a clear solution. With to a solution of from 4 to 5 grams of potassium
stationary electrodes and a current of 1-0-1 -8 oxalate. As soon as the electrolysis has started,
amperes, the tin will be deposited in from 3 to it is advisable to add a few c.c. of a 1 p.c.
4 hours. solution of oxalic acid. Ammonium salts must
With rotating electrodes the metal can be be absent.
deposited in from 15 to 35 minutes, depending Kollock and Smith use a mercury cathode,
upon the current employed, and the temperature and a solution of zinc sulphate or zinc sulphate
of the electrolyte. Currents of from 1-8 to 8 acidified with sulphuric acid.
amperes have been successfully employed. Zinc adheres somewhat firmly to platinum
A mercury cathode also gives very good electrodes, and, if left on for some time, seems
results. The tin salt is dissolved in dilute to alloy with the electrodes. If, however, it
sulphuric acid, and electrolysed with a current is removed shortly after the electrolysis, no ill
of from 2 to 5 amperes. From 0-5 to 0-8 gram effect is produced. The best method to remove
can be deposited in from 8 to 12 minutes. the deposit is to warm the electrode in a strong
When platinum electrodes are employed, solution of sodium hydroxide.
considerable difficulty may be experienced in Cadmium.
removing the deposit. The simplest method Although cadmium is electropositive to
isto make the electrode on which is the deposit, hydrogen by as much as 0-42 volt, yet, owing to
the cathode in dilute sulphuric acid, a piece of the high supertension of hydrogen with this
copper wire serving as cathode. Some workers metal, it is possible to deposit it from acid
prefer to coat the electrode with copper, and then solutions. Owing, however, to the depolarising
the copper with tin, the tin being deposited from action of nitric acid, nitrates should not be
an ammonium oxalate solution ; this proceeding, present ; on the other hand, small amounts
however, is tedious. of chlorides do not seem to matter.
Tellurium. Cadmium may be deposited from solutions
Finely powdered tellurium is dissolved in a containing small quantities of free sulphuric
few c.c. of cone, sulphuric acid. The white acid. It is usually advisable to add, after the
anhydride so obtained is washed with a little bulk of the cadmium has been deposited, the
freshly boiled water into the electrolysing vessel, equivalent amount of sodium hydroxide to
and then 80 c.c. of a 10 p.c. solution of pyrophos- neutralise the sulphuric acid which has been
phoric acid or sodium pyrophosphate added. set free through the deposition of the metal.
The solution is then electrolysed with a C.D. of In 100 c.c. of solution, 1 c.c. of concentrated
254 ANALYSIS.
sulphuric acid may be added before commencing noticed that a small quantity of ferric hydroxide
the electrolysis. With stationary electrodes and separates. This is due to the solution becoming
a current of 0-1 to 0-35 ampere, the metal is slightly alkaline, owing to the decomposition of
deposited in from 3 to 4 hours ; with a rotating the oxalate by the current. Should the hydrox-
electrode and a current of 4 to 5 amperes, the ide be thrown out, small quantities of oxalic acid
deposition is complete in 20 minutes. The must be added.
deposition from cyanide solutions is the simplest With rotating electrodes the time of electro-
and most easy to carry out. A solution of lysis is from 14 to 20 minutes.
potassium cyanide is added to the cadmium With tartrate solutions the results are equally
solution until the precipitate first produced is good. The method of procedure is similar to
dissolved, and then about half the quantity that described for oxalates, ammonium tartrate
already added is run in. It is advisable also to being used in place of the oxalate. The
add about 2 c.c. of a normal solution of sodium advantage of the tartrate method is that
hydroxide. With stationarj' electrodes and a ferric hydroxide is never deposited ; consequently,
current of 0-15-0-35 ampere at a temperature it is not necessary to add tartaric acid, and thus
of 50, the deposit is complete in from 4-5 to less attention is required.
5-5 hours; with rotating electrode and a Nickel.
current of from 5 to 8 amperes, in from 15 to Nickel and cobalt are difficult to determine
30 minutes. by general analytical methods, but they can
GROUP III. Iron. both be readily and accurately analysed by
It is not often that the analyst requires to electrochemical means.
deposit iron electrolytically, owing to the very Although many methods have been suggested
satisfactory methods of titration and precipita- for the deposition of nickel, few of these are
tion. Iron cannot be deposited from acid or of practical importance. Most of them depend
even from neutral salt solution upon a platinum upon the use of the salts of organic acids. In
electrode, owing to its being so much more such cases there is a tendency for traces of
electropositive than hydrogen 0-34 volt, while carbon to be deposited with the metal. The
the supertension of hydrogen is only 0-08 volt. most useful and generally applicable method
Kollock and Smith (Proc. Amer. Phil. Soc. 44, for depositing nickel is that of Fresenius and
149, and 45, 261) have, however, succeeded in Bergmann (Zeit. f. Anal. Chem. 33, 9), in which
depositing iron from weak acid solutions by the double salts of potassium and nickel or
means of a mercury cathode, the iron as it is ammonium sulphate together with excess of
depositedamalgamating with the mercury. ammonia are used.
The method described by these authors is as The nickel salt is dissolved in water and
follows : mixed with an aqueous solution of from 4 to 5
Five c.c. contained 0-2075 gram of iron. grams of ammonium sulphate, and from 30 to
Three drops (40 drops =1 c.c.) of concentrated 35 c.c. of strong ammonia. If more than 1 gram
sulphuric acid were added to it, when it was of the nickel salt is employed, larger quantities
electrolysed with a current of 3 to 4 amperes of ammonia should be added. As, however,
and 7 volts. The anode made from 500 to 900 large quantities of strong ammonia are apt to
revolutions per minute. The iron was com- contaminate the atmosphere, it is better to
pletely deposited in 7 minutes. The water work with smaller quantities of nickel. Nitrates
was then siphoned off and the amalgam washed, should be absent, as their presence considerably
as in all previous cases, with alcohol and water. retards the rate of deposition. With a current
From its oxalate, tartrate, or citrate solutions, of 1-1-5 ampere per sq. dcm., the metal will
iron may be satisfactorily deposited, but in all be deposited in from 2 to 2-5 hours; at a
cases traces of carbon are deposited along with temperature of 50-60, the time will be from
the metal. By employing low-current densities, 1-5 to 2 hours; with rotating electrodes, in
the amount of carbon deposited from oxalate from 15 to 30 minutes, depending upon the
and tartrate solutions is negligible, but from conditions and the form of apparatus. The
citrates the results are almost always consider- metal is usually deposited as a brilliant plating
ably too high. on the electrode. The deposit is at times some-
Ammonium oxalate. This method was first what difficult to remove, and, owing to its
suggested by Classen (Zeit. f. Elektrochem. i. appearance being rather like polished platinum,
288), and is the one most generally employed. it is not always easy to ascertain whether it has ,
The iron solution, which should be free from been completely dissolved off. The best method
chlorides and nitrates, must be poured into the of removing the metal is to warm the electrode
solution of ammonium oxalate, if it is in a in moderately strong sulphuric or nitric acid.
ferrous condition, otherwise a precipitate of Other methods employed are the double
ferrous oxalate may be formed which is difficult oxalate method of Classen and Von Reiss
to dissolve. With ferric salts the order of (Ber. 14, 1622) ; ammonia and ammonium
adding does not matter. borate, by F. M. Perkin and W. C. Prebble
Dissolve 5-7 grams of ammonium oxalate (Trans. Faraday Soc. 1904, 103). Kollock and
or acid ammonium oxalate in a small quantity Smith (Proc. Amer. Phil. Soc. 45, 262) have
of hot water, and to this add the iron salt also used a mercury cathode successfully, the time
dissolved in a little water. The solution is of deposition being from 7 to 20 minutes. An
then made up to the required bulk, and electro- amalgam of 40 grams mercury and 1 gram
lysed with a C.D. of from 0-6 to 1-2 amperes. nickel has the consistency of soft dough, and is
Time of deposit from cold solutions and with bright in appearance.
stationary electrodes, 4 to 5 hours from
; Cobalt.
solutions at 50-60, in 2 to 2-5 hours. As the Cobalt may be deposited from an ammonium
electrolysis proceeds, it will sometimes be sulphate, ammonium hydroxide solution similar
ANALYSIS. 255
to that used in the case of nickel. But as a of nitric acid and water to which 4-5
grams of
rule the results obtained are too low, owing to glucose has been added.
the tendency for peroxide to be formed on the Lead does not give satisfactory results with
anode. a mercury cathode.
F. M. Perkin and W. C. Prebble (Trans. Manganese.
Faraday Soc. 1905, 103) use a solution con- Manganese can only be deposited as oxide
taining dihydrogen sodium phosphate and at the anode. It is, however, much more
phosphoric acid. The solution is made up by difficult to deal with than lead, as the deposit
adding 2 c.c. of a 5 p.c. solution of phosphoric is apt not to adhere well. It is absolutely
acid to the solution of the cobalt salt in 70-80 c.c. essential to employ roughened electrodes.
water and then 20-25 c.c. of a 10 p.c. solution Mineral acids cannot be employed. The most
of dihydrogen sodium phosphate. The elec- satisfactory electrolyte is one containing am-
trolysis should be commenced cold with a monium acetate, and Engels (Zeit. Elektrochem.
current density of G'2-0-3 ampere per sq. dcm. ; ii. 413) has shown that the addition of small
after about 50 minutes the solution is warmed quantities of chrome alum helps to cause the
to 50 or 60, and the current increased to 1-2 deposit to adhere more firmly, probably owing
ampere. If. as often happens, some peroxide is to a depolarising effect. The manganese salt
deposited on the anode, it can be removed by is dissolved in 40-50 c.c. of water, 8-10
grams
the addition of 0-2-0-3 gram of hydroxylamine of ammonium acetate added, and the solution
sulphate. After the solution has become electrolysed at a temperature of 75-80, with
colourless, about 1 c.c. of .ZV/1-ammonia should a current of 0-6 to 1 ampere. The deposition
be added. The time necessary with stationary will be complete in from 1-5 to 2 hours.
electrodes is from 4 to 5 hours. The deposit With rotating electrodes the time will be
is extremely bright, resembling polished about 30 minutes. In this case it is as well to
platinum. add 10 c.c. alcohol to prevent frothing (J. Koster,
The only methods which have been tried Zeit. f. Elektrochem. 10, 553).
with rotating electrodes are solutions containing The best way to ascertain if all the manganese
ammonium acetate and solutions with sodium has been deposited, is to employ the per-
formate. With currents of 8 amperes, L. Kol- manganate test. Withdraw 1 or 2 c.c. of the
lock and E. F. Smith (J. Amer. Chem. Soc. solution, add 3 c.c. cone, nitric acid, and about
29, 797) succeeded in depositing 0-3 gram of 1 gram of red lead. Boil for a minute or two
cobalt in from 30 to 40 minutes. and dilute. A pink colouration indicates that
GROUP IV. Lead. the whole of the manganese has not been
Owing to its ready oxidisability, it is difficult to removed.
deposit lead satisfactorily on the cathode. Except When all the manganese has been deposited,
in cases of separation from other metals, indeed, the electrode is washed as usual, and then
it is of no advantage to deposit it at the cathode. strongly heated in order to convert the hydrated
Sand has, however, found it a convenient method manganese peroxide into trimanganese tetroxide
to separate lead from cadmium and bismuth Mn 3 4 It is necessary to heat until the black
.
(Chem. Soc. Proc. 22, 43) deposit becomes a dull orange red. The weight
From dilute solutions of nitric acid lead is of the deposit multiplied by 0-72 gives the
partially deposited as metal on the cathode, weight of metallic manganese.
and partially as peroxide at the anode. It is Chromium.
therefore necessary to have about 20 c.c. of cannot be deposited on the
This metal
nitric acid (1 : 4) to every 100 c.c. of electrolyte. anode as peroxide ; neither under ordinary
is it possible to obtain a cathode
Arsenic, manganese, selenium, and bismuth conditions
should be absent, and according to Vortmann deposit. Kollock and Smith (Trans. Amer.
(Annalen, 351, 283), antimony, silver, mercury, Chem. Soc. 27, 1905, 1255) have succeeded in
zinc, iron, cobalt, aluminium, and the alkali depositing it in the form of an amalgam by
metals also cause the results to be high. Chromic employing a mercury cathode. The electrolyte
acid should also be absent, and phosphoric acid consisted of dilute sulphuric acid. With a
retards the deposition. The lead salt is dis- current of 1-3 amperes 0-12 gram was deposited
solved in water, and from 25 to 30 c.c. of strong in 20 minutes. This method is useful for
nitric acid added. The electrodes used, whether separating chromium from aluminium, which
stationary or rotating, should be roughened by latter metal is not deposited as an amalgam.
the sand blast. With stationary electrodes Classen (Ber. xxvii. 2060) oxidises
and a current of from 1-3 to 1-8 ampere at a chromic chromates in an ammonium
salts to
temperature of 60-70, the deposition will be oxalate solution. This method is useful for
nickel and
complete in from 1 to 1-5 hours. At the com- separating chromium from iron,
mencement of the electrolysis a yellowish cobalt, and in the analysis of chromium steels
deposit is obtained which becomes orange or and of chrome iron ore. The chromic acid pro-
red, and finally dark-brown or black. duced can be estimated iodometrically or by
With rotating electrodes, the time of deposi- or barium chromate.
precipitation as lead
tion is from 10 to 25 minutes. The solution containing the iron and
At the end of the electrolysis the electrode chromium salt has excess of ammonium oxalate
is well washed
by placing it in hot water, then added to it, and if free mineral acid is present is
washed with alcohol and ether, and heated to neutralised with ammonia. It is then electro-
220 in the air-bath for an hour. It must be at the cathode
lysed, when the iron is deposited
cooled in a desiccator ; the weight of the and the chromium oxidised to chromate. The
of chromium
deposit is multiplied by the factor 0-866. iron, when deposited in presence
The best method to remove the deposit from salts, is usually very brilliant like polished
the electrode is to warm it with When all the iron is deposited, the
equal volumes platinum.
256 ANALYSIS.
solution is removed, the iron deposit dried and lising dish, 11 cm. in diameter and about 5 cm.
weighed, and the chromium determined. If deep ; a beaker 6 cm. in diameter and 4-5 cm.
the whole of the chromic salt has not been high, with the bottom
oxidised during the deposition of the iron, the cut off, is placed in-
solution is again electrolysed. By using a side, and
rests on a
rotating anode it is possible to completely triangle of glass rod
oxidise 0-15 gram of a chromic salt, such as placed on the bottom
Cr 2 (S0 4 ) 3 or Cr^Cl,, in 90 minutes, the volume of the crystallising
of the solution being 120 c.c. and the amount dish. The beaker is
of ammonium oxalate 15 grams. The electro- kept in position in
lyte should be heated to 80, and a current of the middle of the
from 5 to 5-5 amperes employed (Elektron- dish by means of
alytische Schnellmethoden, p. 180). three rubber stoppers
Uranium. fitted radially be-
Uranium is deposited at the cathode as tween it and the
oxide from solutions containing acetic acid or outer dish. Two com-
ammonium carbonate. The deposit consists partments are thus
of U3 4 ,3H 2 O. At the end of the operation formed, which are
this is heated strongly to convert it into U 3 8 . sealed off by means
Wherry and Smith (Trans. Amer. Chem. Soc. of mercury.
29, 806), by using a rotating cathode and an In the outer
electrolyte containing in 125 c.c. 2-5-5-5 gram c ompart-
sodium acetate, deposited 0-25 gram of uranium ment there
in from 15 to 30 minutes, the current employed is a ring con-
being 3-5 amperes, the electrolyte being either sisting of
cold or heated to 50. six turns of
Molybdenum. stout nickel
From solutions containing dilute sulphuric wire, pro-
acid, molybdenum can be deposited as peroxide vided with
at the cathode, but the deposit cannot be three legs .
weighed as such. Wherry and Smith (Trans. dipping into

Amer. Chem. Soc. 29, 806), therefore, oxidise it the mercury
by means of nitric acid and weigh as Mo0 3 . and serving
Thallium. to maintain
Many methods have been suggested for the the lowest FIG. 68.
electrolytic analysis of thallium, but only one can winding of
be considered satisfactory, and that is, by using the nickel about 1 cm. above the surface of
a mercury cathode. depositing the metal
By the mercury, when sufficient is placed in the
into pure mercury, it found that portions are
is dish to seal off the two compartments. By
lost on weighing but if the mercury contains a
; means of a platinum wire passing through a
small quantity of zinc, this is not the case. glass tube the mercury is made the cathode.
Smith recommends to deposit the zinc and The anode consists of two discs of platinum
mercury simultaneously. In order to do this gauze heavily plated with silver.
a definite volume of zinc sulphate solution of Pure mercury must be used, and the cell
known strength is added to the solution before must be kept scrupulously clean. Before
electrolysis. The electrolyte consists of dilute starting the cell, mercury is poured in so that its
sulphuric acid. The amount of zinc necessary to level is about 3 mm. above the lower edge of
protect the thallium is very small, and need not the inside beaker. The solution to be electro-
be more than 0-001 gram. With a current of lysed is then put into the inner compartment.
5 amperes it is possible to deposit as much as In the outer one enough distilled water to cover
0-2 gram in about 10 minutes. It is, however, the nickel wire is placed, and to this 1 c.c. of
advisable to electrolyse for a longer time. a saturated solution of common salt. By this
GROTTP V. Sodium. arrangement the amalgam formed in the inner
E. F. Smith (Trans. Amer. Chem. Soc. 25, compartment is immediately decomposed in
1903, 890) was the first to show that the the outer one. The sodium chloride serves
metals of the alkali group could be analysed merely to make the liquid a conductor, so that
elecfcrolytically. The method is based on the the action may proceed more rapidly at the
removal of the halogen anion of the metal by commencement. Unless this is done, the
causing it to unite with silver, the alkali metal amalgam is not entirely decomposed in
remaining in the solution as hydroxide is deter- the outer compartment, because pure water
mined by titration ; by ascertaining the in- does not attack it rapidly enough to prevent the
crease in weight of the silver anode, the halogen partial decomposition in the inside cell. After
can be also determined. the electrolysis is complete, the entire contents
An ingenious apparatus has been devised by of the cell are poured into a beaker, the cell
Hildebrand (Trans. Amer. Chem. Soc. 29, 1907, rinsed, and the alkali titrated. After titration
447) for the analysis of the cations of the alkali the mercury is washed, the water decanted, and
metals, and of barium and strontium ; and at the metal poured into a large separating funnel
the same time of various anions. In principle from which it can be drawn off clean and dry.
the cell resembles that of the Castner-Kellner The table on p. 257 give the results which
process employed in the manufacture of sodium were obtained by Hildebrand.
hydroxide. The weighed gauze anode is clamped to the
The outer cell (Fig. 68) consists of a crystal- shaft. The latter is lowered into the cell till
ANALYSIS. 257
the lower gauze is about 5 mm. from the surface
of the mercury. The most convenient speed
for the motor is about 300 revolutions per
minute. The anode does not require washing,
as the water after electrolysis is pure. It may
be at once dried in the steam oven.
Time :
Mins.
258 ANALYSIS.
produces a flame of about 3 mm. in eize. As solutions containing nitric acid as peroxide on
soon as all the air has been driven out, which the anode, whilst copper is deposited as metal at
usually occupies about 10 minutes, the issuing the cathode, it might be supposed that there
hydrogen is ignited and the Bunsen burner would be no difficulty in depositing both metals
lighted. If after about 15 minutes no brown concurrently. It must, however, be remembered
ring makes its appearance, the reagents may be that unless there is a considerable concentration
considered free from arsenic. At the end of of nitric acid, a portion of the lead will be de-
30 minutes the capillary tube is sealed off, posited as metal at the anode. On the other
and the open end also fused together. The hand, in presence of copper, the tendency to
mirror is then compared with the standard reduction of the lead and its appearance at the
mirrors as above described. cathode is decreased that is to say, in presence
;
Preparation of standard mirrors. Pure re- of copper a lower concentration of nitric acid
sublimed arsenious oxide is ground in an agate is required. It has, therefore, been found
mortar and dried at 100. Then 0-1 gram is possible to separate the two metals. The
carefully weighed and washed into a 1 -litre volume of solution employed was 85 c.c., and
flask, the flask being filled to the mark with dis- contained 1 c.c. HN0 3 (1 :4). With a rotating
tilled water. Each 1 c.c. of this solution con- anode and a current of 2 amperes, the whole of
tains 0-0001 arsenious oxide ; 100 c.c. of this the lead was deposited in 5 minutes. The
solution are diluted to 1 litre. This second current was then increased to 10 amperes, when
solution contains 0-00001 gram of arsenious acid the last traces of copper were removed. The
in each 1 c.c., or 0-01 mg. Standard tubes washing and drying of the anode deposit requires
containing 0-004. 0-006, 0-008, 0-010, &c., mg. care, since the peroxide when deposited from
can then be prepared. weak acid solutions does not adhere so well as
When foodstuffs are being examined for from stronger solutions (Sand).
arsenic, Thorpe considers itadvisable to take a Copper and arsenic. McCay finds the
portion of the foodstuff arsenic free and following conditions give a satisfactory deposit
mix with the known quantity of arsenic before
it of copper in presence of arsenic. The arsenic
proceeding to electrolyse it. The standard remaining in the solution cannot, however, be
mirrors are thus prepared under the same con- estimated electrolytically, unless present in very
ditions as those under which the suspected food- small quantities.
stuff is tested. To the solution 20 c.c. ammonium hydroxide
S. R. Trotman (J. Soc. Chem. Ind. 23, 177) (sp. gr. 0-91) and 2-5 gram ammonium nitrate are
recommends the adoption of a parchment added, the volume of solution being 125 c.c.
membrane in place of the porous Pukal cell, The solution is then electrolysed at a temperature
as he considers this decreases the resistance, of 50-60, with 0-5 ampere per 100 sq. deem,
and thus makes the apparatus more sensitive. of electrode surface. As much as 0-22 gram
It however, not so convenient to use.
is, of copper will be deposited in 3 hours. With
Sand and J. E. Hackford (Chem. Soc. Trans. a rotating anode about 15 minutes are
85, 1018) use the parchment membrane, but required. In this solution the arsenic should
they also employ a heavy lead cathode and a be present as arsenate. Copper and arsenic
lead anode. Their apparatus is thereby much may also be separated electrolytically from
cheaper than that used by Thorpe, and is said solutions containing potassium cyanide. If
to be equally accurate. acid, the solution is neutralised, and then
sufficient potassium cyanide added to just
Metallic Separations. redissolve the precipitate first produced. With
Alarge number of separations of metals by a current 0-25-0-27 ampere, the whole of the
electrolytic methods have been worked out, copper is deposited in about three hours.
but in many cases a purely chemical procedure Antimony from tin. Tin can be quantita-
or a combination of electrolytic and chemical from solutions containing
tively deposited
methods is easier. There are, however, cases excess of ammonium sulphide. It cannot,
in which satisfactory and rapid electrolytic however, be deposited from solutions contain-
separations can be carried out. A few of the ing excess of sodium sulphide. Antimony, on
more important are given below. the other hand, can be deposited from solutions
Copper from nickel. By employing a containing excess of sodium sulphide. It is
rotating anode with an auxiliary electrode, therefore possible to separate antimony from
and maintaining the cathode potential -at tin by adding excess of sodium sulphide to a
0-7-0-75 volt, copper can be deposited from solution containing the two metals. If the
solutions containing sulphuric acid. The solu- solution is acid, it is first made slightly alkaline
tion is then made alkaline with ammonia, when with sodium hydroxide before the sodium
the nickel can be deposited. If the cathode
sulphide is added. It is, however, better to
potential is not regulated, small quantities of first precipitate the two metals as sulphides, and
the nickel are deposited along with the copper. then dissolve them in a concentrated solution of
Exner (J. Amer. Chem. Soc. 25, 896) finds sodium sulphide. The tin should be in the
that by employing a solution containing nitric stannic state. The solution is electrolysed at a
acid and ammonium nitrate (volume of solution
temperature of 50-60 with a current of from
125 c.c. ; HNO 3 , 0.25 c.c. ; 3 gram 4
NH N0
3) 0-2 to 0-9 ampere per sq. dcm. of electrode
and using a rotating anode, it is possible to surface. In trom 2 to 4 hours the whole of the
deposit as much as 0-25 gram copper in 15- antimony is deposited. It is, however, almost
20 minutes ; the nickel, which may be of equal always contaminated with small quantities of tin.
weight, remains in solution, and can be after- In order to deposit the tin, the sodium
wards deposited. sulphide must be decomposed. This is done by
Copper from lead. Since lead is deposited from adding about 25 grams of ammonium sulphate,
ANDA-ASSU, OIL OF. 259
and boiling until no more hydrogen sulphide is ampere, and maintain the potential at 1-1-1-6
now deposited by electro-
j
evolved. The tin is volt. The silver will be completely deposited

lysing with a current density of from 0-3 to 0-5 in from 4 to 5 hours. After the silver has been
amperes. weighed, the electrode is replaced, the current
The best method of separating antimony and voltage increased, when the copper will be
and tinthat of Sand, by means of graded
is deposited.
potential and a rapidly rotating anode (Chem. Silver may also be separated from
copper in
Soc. Trans, xciii. (2) 1908, 1572). From solu- ammoniacal solutions by using an auxiliary elec-
tions containing strong sulphuric acid (1:1) trode, and keeping the potential below 0-5 volt.
antimony is deposited at an auxiliary potential Iron from other metals. Iron can readily be
of 0-65 volt when the temperature is kept above separated from aluminium, vanadium, glucinum,
100, and a small quantity of hydrazine sulphate uranium, thorium, and many other metals with
is added. Tin, on the other hand, under which it may be alloyed by dissolving in sul-
similar conditions, is not deposited below 0-8 phuric acid, filtering from any residue, nearly
volt. The method of procedure when dealing neutralising with ammonia, and electrolysing
with alloys of antimony and tin is as follows : with a mercury cathode.
The alloy is dissolved in a mixture of Cadmium from zinc. These metals can be
40 c.c. cone, sulphuric acid, 5 c.c. water, and separated by means of graded potential. The
2 c.c. nitric acid (1 42) on heating to 180-200
: ; solution is made up by adding first 2 c.c. of
solution rapidly takes place. It is necessary cone, sulphuric acid, then 3-33 grams of sodium
to remove the nitric acid because it causes the hydroxide, and 1 c.c. of glacial acetic acid. The
formation of antimonic acid, which is only auxiliary electrode is kept at a potential of 1-15
slowly reduced to the metallic state electro- -1-20 volts, and the solution electrolysed at a
lytically. In order to decompose the nitric temperature of 30. The whole of the cadmium
acid (nitrosulphonic acid), a current of 5 amperes will be deposited in 11-14 minutes. The
is passed, and the liquid heated to 250-270. potential is afterwards raised, when the zinc can
After the current has been passed for 5 to 10 be deposited in about 30 minutes.
minutes at the high temperature, it is stopped. Bibliography. Electroanalysis, by Edgar
The solution is cooled to 100, and 0-5 gram of Smith (P. Blakiston's Son & Co., Philadelphia) ;
hydrazine sulphate added. (N.B. The amount Practical Methods of Electrochemistry, by F.
of hydrazine sulphate added should be equal to Mollwo Perkin (Longmans, Green, & Co., London);
the weight of metal taken. ) Elektroanalytische Schnellmethoden, by A.
The temperature is then raised to 300. It Fischer (Ferdinand Enke, Stuttgart) ; Quantita-
is again cooled to 100, when from 30 to 40 c.c. tive Analyse durch Elektrolyse, by A. Classen
of water and another 0-5 gram of hydrazine (Julius Springer, Berlin) ; Analyse des Metaux
sulphate are added. par Electrolyse, by A. Holland et L. Bertiaus
The anode l is then rotated to ensure mixing (H. Dunod et E. Pinat, Paris). F. M. P.
of the solution, the temperature of which rises ANAMIRTA COCCULUS or A. PANICULATA
to about 120. The analysis is now begun, the (Colebr.). The former is the superseded name,
auxiliary potential having first been adjusted and the latter the true name, of the Indian
to 0-53-0-65 volt. The current will vary Menispermaceous liane, whose dried fruits
between 34
amperes, and, at the end of the (Grains of Paradise) are supplied under the name
electrolysis, will drop to 0-4-0-5 volt. Time of of Cocculus indicus (v. COCCULUS INDICUS).
electrolysis from 20 to 30 minutes. ANANAS, OIL or ESSENCE OF. A solution
Thetin is determined as follows : The of ethyl butyrate in 8 to 10 times its weight of
solution after the antimony has been deposited alcohol. It possesses the odour of the pine-
is mixed with about 4 grams of oxalic acid, and
apple (Ananas sativus (Schult.)), and is employed
is neutralised with strong ammonia. In order in confectionery and perfumery also to imitate
;
to prevent loss by spurting the electrodes are the flavour of rum (Hofmann, Annalen, 81, 87).
placed in position, the rotating stem being ANANDONIS GREEN, Hydrated chromium
passed through a hole drilled in a clock glass. sesquioxide (v. CHKOMIUM).
The ammonia poured on the clock glass and
is ANASPALIN. Trade name for a form of
runs down the stem of the electrode into the wool-fat.
solution, the anode or inner electrode being at ANATASE or Odahedrite. One of the tri-
the same time rotated. Considerable ebullition morphous forms (TiO 2 ) met
of titanium dioxide
ensues, but none of the liquid is spurted out. with as crystallised minerals the others being
;
Exact neutralisation is ascertained by the use of rutile and brookite. It is found as small,
methyl orange as indicator. Litmus cannot be isolated crystals of a steel-blue or honey-
nature hinders the in
employed, since its colloidal
yellow colour, in schistose rocks, particularly
deposition of the tin. After neutralisation, the Alps. L- J- S.
0-5-0-75 c.c. of sulphuric acid are added for ANCHIETA BARK. The root bark of An-
every gram of oxalic acid previously added. chietea salutaris (A. St. Mil.), one of the Violacese,
The solution is electrolysed at a temperature a bushy shrub growing at Rio de Janeiro. It
of 70 with a current of 3-4 amperes. Time of contains anchietine, a substance crystallising in
deposit, 60-80 minutes. straw-coloured needles, having a nauseous taste.
Silver and copper. (Smith and Frankel, Used for syphilisand quinsy (Peckolt, Arch.
Amer. Chem. J. 12, 104.) To a neutral solution Pharm. [2] 97, 271).
of the silver and copper salt, add 2-3 grams of ANCHUSIN (Alkanniri) v. ALKANNET.
pure potassium cyanide. Electrolyse at a tem- ANDA-ASSU, OIL OF. An oil obtained from
perature of 65 with a current of 0-03-0-05 the seeds ofJoannesia Princeps (Veil.), belonging
to the Euphorbiaceae, growing in Brazil. It is
1
After the metal has dissolved, the subsequent opera- ,
with a taste
tions are carried out with the electrodes in position. ;
clear, slightly yellowish, odourless,
s 2
260 ANDA-ASSU, OIL OF.
at first nauseating and then sweet. It solidifies ANGELICA OIL v. OILS, ESSENTIAL.
at 8, its sp.gr. at 18 is 0-9176 (Pharm. J. [3] ANGICO RESIN. A Brazilian gum obtained
12, 380). from Piptadenia rigida (Benth.) [Acacia Angico] ;
ANDAQUIES WAX v. WAXES. soluble in water and proof spirit. Used in chest
ANDROGRAPHIS PANICULATA (Nees) or complaints (Symes, Pharm. J. [3] 13, 213).
Kuryat. An Indian plant is used as a tonic,
; Angico wood is that of another Brazilian legu-
and similar to quassia in its action.
is minous plant, Enterolobium ellipticum (Benth).
ANDROPOGON OILS v. OILS, ESSENTIAL. ANGLESITE. Native lead sulphate (PbS0 4 ),
ANDROSIN GLUCOSIDES.
v. forming brilliant, colourless, orthorhombic crys-
ANESIN An aqueous solution of
(Aneson). tals, isomorphous with barytes (BaS0 4 and )
acetonechloroform, having marked anaesthetic celestite (SrS0 4 ). It occurs in the upper

and hypnotic properties (Apoth. Zeit. 1897, 12, oxidised zones of veins of lead ore, having
608) (v. ACETONECHLOROFORM). resulted by the alteration of galena (PbS). It
ANETHOL v. OILS, ESSENTIAL. ie less common than cerussite (PbC0 3 ), with
FIG. 1. ANILINE OIL PLANT.

A, Aniline pan. F, Feed hopper for borings. L, Gutter. Q, Cold-water inlet.
B, Agitating blades. G, Charging dish. M, Receiving pan. B, Receiver.
C, Side lining plates. H, Vapour pipe to condenser. N, Pipe from N.B. tank. S, Steam pump.
D, Bottom do. Pure-steam pipe.
J, O, Condenser. T, Settling tubes.
E, Wood plug for hopper. K, Aniline-steam do. P, Overflow. U, Air pressure egg.
which it has sometimes been mined as an ore of tar in 1834, and by Fritzsche in 1840, among
lead. Good crystals have been found at many the products obtained by distilling indigo with
localities, perhaps most abundantly at Broken alkali hydroxides. Prepared by Zinin in 1840,
Hill, in New South Wales. The mineral takes by the reduction of Mitscherlich's nitrobenzene
its name from the Isle of Anglesey, where with hydrogen sulphide. Unverdorben called his
crystals were found by W. Withering, in 1783, product krystallin ; Runge, Tcyanol Fritzsche,
;
in the Parys copper-mine. L. J. S. anilin ; Zinin, benzidam.

ANGOSTURA BARK or ANGUSTURA In 1843 Hofmann showed that nitrobenzene
BARK CUSPARIA BARK.
V. could be reduced by a metal such as zinc in the
ANHYDRITE v. CALCIUM. presence of a dilute acid, and also that krystallin,
ANIL. The name of the American species kyanol, anilin, and benzidam were identical with
of the indigo plant, Indigofera anil (Linn.). each other. Shortly afterwards Be'champ stated
ANILINE. that nitrobenzene could be reduced by ferrous
History. First observed by Unverdorben in acetate in the presence of water, but that the
1826 among the products of the
destructive oxalate, sulphate, &c., had no effect.
distillation of indigo. Detected by Runge in coal In the year 1856 Perkin's discovery of mauve
ANILINE. 261
gave rise toa commercial demand for aniline, simple method of 'feeding' the iron
borings
and the manufacture was commenced by Messrs. has proved better than many of the mechanical
Simpson & Maule. feeding devices that have been tried. Distilla-
Preparation. Benzene, then only obtained tion proceeds, and the distillate
passes through
in small quantities and with much difficulty, as the condenser and runs back into the
dish,
the treatment of tar scarcely existed, was intro- together with the nitrobenzene which is carried
'
duced into glass balloons (known as bolt over. The iron borings and nitrobenzene are
heads ') of 1 gallon capacity, and the calculated added only in sufficient quantities to maintain
quantity of nitric acid, mixed with about an a constant level in the dish. If the reaction
equal volume of sulphuric acid, was gradually proceeds too violently, loss is caused by the
added, the mixture swung round and well formation of benzene. When the level of the
agitated, and then allowed to stand. It was liquid in the dish begins to lower, the supply of
usual to have about twenty balloons in a row, nitrobenzene and iron borings is increased. This
and to add acid in turn until the reaction was process is continued until the whole charge of
complete. nitrobenzene is run in, which takes about 10
The nitrobenzene was separated, washed, and hours. The total weight of iron borings re-
reduced with iron borings and acetic acid, at quired is 9 cwt. A sample caught as it runs
first in a copper still, later in an iron cylinder. from the condenser should then be quite free
The aniline was freed from water, rectified, and from nitrobenzene, and the machine will contain
was then ready for use. The selling price was only aniline oil, water, and oxide of iron. The
about a guinea a pound. .
supply of steam is then increased, so as to
Somewhat later cast-iron C3rlinders of con- distil over the aniline oil and water, 1 and the
siderable size were used for the reduction, acetic distillate is diverted into the tank beneath
acid being still used and neutralised with soda or the condenser. The steam used for this dis-
lime at the end of the reaction, and the aniline tillation is not pure steam, but is generated from
was in some factories distilled off over a naked the aniline water mentioned below, in a separate
fire, in others steam was blown into the mixture, boiler. The aniline water is that which separates
and the aniline and water condensed and from the oil in the separating tubes, and con-
separated. Acetic acid continued to be used tains about 2 p.c. of aniline oil in solution. The
until about 1866. Since that time the apparatus aniline and water in the tank below the con-
has undergone little change, the treatment condenser are pumped into the settling tubes, and
sisting in reduction mainly by the use of iron allowed to settle for 48 hours. The distillation
and water, hydrochloric acid being employed to of the oil and water from the machine takes
start the reaction. about 7 hours, and during the last hour pure
The aniline machine shown in Fig. 1 is the steam is again used, so that when the operation
type that gives the best results.
1
A careful is finished, the condensed water left in the
comparison between this design and the hori- machine will be free from aniline, and can be
zontal machine has proved unmistakably that used for flushing out the oxide of iron into the
the vertical machine is more economical and gutter which runs to the settling tanks outside.
better in every respect. This is particularly The oxide, after the water is drained off, is
the case with regard to repairs and maintenance. dried and ground, and disposed of for the
The machine is of cast-iron, If inches thick, with purification of coal gas from sulphur. Large
driving gear, agitating shaft, and blades, as quantities ai;e also now being used in the manu-
shown in the sketch. An important feature is facture of cheap black paints, and the con-
the renewable cast-iron lining plates at the sumption in this direction is increasing. The
sides and bottom, which protect the machine aniline oil which has settled to the bottom of
from the friction caused by the revolving mass the settling tubes is run off into the air-pressure
of iron borings. It is 6 feet 6 inches deep, and egg below;, and blown into the crude aniline-oil,
4 feet 6 inches in diameter, having a total capa- store tanks, ready for the final purification by
city of 650 gallons. Steam is admitted through distillation in the vacuum still. The upper
the vertical shaft, which is hollow, and passes layer of water left in the settling tubes, and
through the extremities of the horizontal which contains about 2 p.c. of aniline in solution,
is, as already explained, used for feeding
agitating blades. Twenty-one of these machines the
are required to produce 150 tons of aniline oil aniline steam boiler. The average yield of
per month. 2
A charge of 1000 Ibs. of nitrobenzene I crude 'aniline oil from each machine, with a
is run into the
receiving pan above the machine. charge of 1000 Ibs. of nitrobenzene, is 765
Ibs.
To start the reaction, 1 cwt. of clean cast-iron The yield of pure aniline oil from nitrobenzene
borings, 10 gallons of hydrochloric acid, and j
is given further on.
ft
gallons of water are run in through the funnel- i
The final purification of the crude aniline oil
shaped hopper, and simultaneously steam is \
is done in a vacuum .still. The sketch (Fig. 2)
turned on and the nitrobenzene run in a thin i
shows one of these stills of recent design. The
stream into the dish on the top of the machine. body of the still is wrought-iron, 15 feet long,
The wooden plug in the hopper is driven in tight, and 7 feet 6 inches in diameter, having a total
and the space between it and the hopper is kept capacity of 4000 gallons, and capable
of dis-
full of iron
borings. By dexterously manipulat- tilling 35,000 Ibs.
in one charge. The steam is
ing the wood plug, the borings can be added supplied from a boiler having a working pressure
Without allowing any vapour to escape. This of 100 Ibs. per sq. inch, at which pressure
1
See Chem. Trade J. 1906, 38, 59. The writer ia the steam possesses a temperature of 170.
indebted to Messrs. Davis Bros, for permission to repro-
duce the two figures. 1
In some works this distillation is not done, but
2
Larger machines, on the same principle, in which the contents of the reduction apparatus are passed im-
several tons of nitrobenzene can be reduced, are used by mediately through a filter press, the filtrate then running
some manufacturers. directly or being pumped into the settling tanks.
262 ANILINE.
The internal steam tubes are wrought-iron, condenser is 432 feet. The two receivers permit
2 inches in diameter. In place of the usual continuous working, so that when the first is
straight tubes which used to be expanded into full, as indicated by the gauge-glass tube, it is
both end plates, bent tubes are employed, shut off, and the second brought into use. The
which enter and return to the same end of the contents of the first can then be drawn off while
' '
still. This prevents the tearing of the tubes the second is being filled, and the vacuum is
owing to expansion and contraction, and the thus maintained throughout.
' ' '
breathing of the end plates. The column

'
The still is charged with 35,000 Ibs. of crude
is of cast iron, 18 feet
high and 9 inches in aniline oil from the store tank, and steam is
diameter. The condensing coils consist of three turned on. The first fraction, about 7 p.c. of
vertical flat copper coils, 2 inches in diameter, the distillate, consists of aniline oil and water,
arranged side by side in a wrought-iron tank, which is added to the crude oil and water in the
'
the distillate entering all the three coils simultane- separating tubes. The next fraction is light
ously from the still head by means of branch aniline,' and consists of aniline oil with a small
pipes. The total length of copper pipe in the quantity of benzene. If the reduction of the
FIG. 2. VACUUM STILL FOR ANILINE OIL.

A, Vacuum still. J, Condenser. R, Inlet from condenser.
B, Internal hollow stay. K, Cold-water inlet. S, Air-admission tap.
C, Steam tubes. L, Overflow for water. T, Do. do.
D, Do. do. M, Receiver for distilled oil. U, Run-off tap for distilled oil.
E, Steam inlet. N, Do. do. do. V, Do. do. do.
F, Do. outlet. O, Connection from vacuum pump. W, Connection from vacuum pump.
G, Vapour pipe to condenser. P, Do. do. do.
H, Pressure gauge. Q, Inlet from condenser.
nitrobenzene has been carefully performed, this The process of reduction and rectification as
fraction is only about 4 p.c. of the distillate. described applies also to toluidine, and modifica-
It is collected and redistilled, giving pure tions of the process are also in use for the pro-
aniline and benzene, the latter being returned to duction of xylidine and alphanaphthylamiae.
the nitrobenzene department, to be renitrified. and of the reduction portion for the manufacture
The next fraction is pure aniline oil of market- of metaphenylene- and metatolylene-diaminc
able quality, clear and water-white. The tail from the respective dinitro- compounds.
'
end, called last runnings,' forms about 5 p.c.
of the distillate, and, on redistillation, yields Valuation of Commercial Aniline Oil.
80 p.c. of pure marketable aniline oil. The Aniline oil, as it occurs in commerce, may
total yield of pure aniline oil obtained from contain as impurities water, traces of insoluble
nitrobenzene is 7 If p.c. As the pure benzene- hydrocarbons and of orthotoluidine, sometimes
yields 154i p.c. of nitrobenzene, and the latter traces of hydrogen sulphide, and, if carelessly
7l- p.c. of pure aniline oil, the total yield of made, of nitrobenzene, benzene, and ammonia.
pure aniline oil from pure benzene is 110-85 p.c. Besides these, which should be carefully tested
Compared with theory, there is little room for for, there is possibly a certain amount of amino-
improvement. thiophen, which has no deleterious action for
ANIMAL CHARCOAL. 263
most, if not of the purposes for which aniline

all, Toluidine liquid should boil at 197-198,
is used, and which, moreover, for the present at show a sp.gr. of about 1-000, and contain
least, cannot readily be got rid of. 30-40 p.c. para-, the rest orthotoluidine.
The method of 'testing usually adopted is to Orthotoluidine. The sp.gr. of commercial
determine the boiling-point of the sample. For orthotoluidine should be about 1-0037 ; b.p.
this purpose 100 c.c. are introduced into a small about 197-198; should not solidify on
boiling flask with side tube,
and distilled through cooling to 4. Lunge (Chem. Ind. 1885, 8, 74)
a short condenser into a graduated 100 c.c. has published a table showing the specific
cylinder. Readings of the thermometer are gravities of mixtures of o- and jj-toluidine.
taken as each 10 c.c. of the cylinder fills, and the For the estimation of small amounts of ^-tolui-
last when 95 c.c. are filled. An alternative dine in o-toluidine, Schoen's method is perhaps
method is to take readings of the cylinder at each the best. A standard oil is prepared, containing
fifth of a degree rise of the thermometer. It is 8 p.c. of p-toluidine and 92 p.c. of o-toluidine,
also usual to note the temperature when the first 1 c.c. of which is dissolved with 2 c.c. of pure
drop has fallen from the condenser. The ther- hydrochloric acid in 50 c.c. of water, and oxidised
mometer readings should be corrected for cold by adding 1 c.c. of a saturated solution of
barometer and immersion of mercurial column potassium dichromate. After standing for two
in the vapour of the liquid, and of course for the hours, the product is filtered, the precipitate
errors peculiar to the thermometer in use. being washed with water, and the filtrate and
A few fragments of platinum wire, fire-brick, washings made up to 100 c.c. The toluidine to
or wrought iron, should be placed on the bottom be tested is treated in the same manner, and
of the flask, and great care used to adjust the compared colorimetrically with the above
size of the flame and rate of boiling. The flask solution. J. C. C.
also should be held by the neck in a good clip ANILINE BLACK v. DYEING.
over the naked flame, gauze being apt to cause ANILINE BLUE v. TRIPHENVLMETHANE
currents of heated gas to flow up round the neck COLOURING MATTERS.
of the flask and superheat the vapour. ANILINE BROWN V. AZO- COLOURING
The specific gravity of the sample may also MATTERS.
be taken (pure aniline has a specific gravity of ANILINE SALT. The commercial name of
1-0265-1-0267 at 15), although this indication aniline hydrochloride C 6 H 5 -NH,,HC1.
is not of great moment if the boiling-points It is prepared in large quantities for the use
are good. of calico-printers, who employ it in the produc-
A recent example of the determination of the tion of aniline black. The process consists in
boiling-point is the following (Walter, Chem. mixing the calculated quantities of pure aniline
Zeit. 1910, 34, 702) : and hydrochloric acid in lead-lined or nickel -
Temperature P.c. over Temperature P.c. over lined tanks, and allowing the salt to crystallise,
182-4 3 183-2 20 freeing it from mother liquors in a centrifugal
182-6 4 183-4 97 machine, and drying at a low temperature. The
182-8 5-5 183-6 98 hydrochloric acid used should be of good quality,
183-0 11 183-8 free from iron and even from traces of copper,
Pure aniline may be tested for insoluble oils or the salt will rapidly blacken.
by dissolving 10 c.c. in 40 c.c. of hydrochloric The mother liquors may be neutralised with
acid and 50 c.c. of water. The solution should lime or soda, and the aniline recovered, or they
be quite clear. may be boiled down and used in making magenta
If, in carrying out the boiling test, the by the nitrobenzene process, &c.
'
Aniline salt
'
occurs in commerce in
temperature rises considerably at the end, the
presence of toluidine may be suspected. This large, white, nacreous and much-contorted
can be detected when a considerable quantity plates.
of commercial pure aniline is made into acet- The great desiderata for the calico-printer
anilide. On
recrystallising this and working
are that the salt should be made from pure
up the mother liquors, a small quantity of im- aniline and should be dry and normal, contain-
of hydro-
pure acetyl compound of low melting-point will ing 93 parts of aniline to 36-5 parts
always be found in the most soluble portion, or chloric acid ; it should be free from sand and
first mother grit, which injure
the printing machines.
liquors.
J. C. C.
Nitrobenzene shows itself with the insoluble
hydrocarbons. A very delicate test for it is to ANILINE YELLOW v. Azo- COLOURING
shake the sample of aniline violently for a few MATTERS.
minutes, and then to notice the colour of the ANIMAL CHARCOAL. (Nair rf'os, Fr. ;
froth. The merest trace of nitrobenzene colours Knochenschwarz, Ger.) This substance, also
it a
very distinct yellow. known by the name of Bone Black or techni-
as Char,' is formed by carbonising bones
'
The presence of water may be detected by cally
distilling the sample (100 c.c.) as for a boiling- at a high temperature in vessels from which
point determination, and collecting the first air is excluded. Animal charcoal possesses
10 c.c. in a narrow graduated cylinder of 15 c.c. the property of absorbing organic colouring
capacity, shaking with 1 c.c. of saturated matters from solutions brought in contact with
sodium chloride solution, and reading off the it ; thus a solution of brown sugar passed
will be found to have
volume of the latter. The method will not through animal charcoal
show the presence of less than 0-3 p.c. of water, its colour more or less removed. This property
is also possessed, though to a far smaller degree,
consequently, 0-3 c.c. must always be added to
LSwitz
the amount of salt solution observed. It is not by wood charcoal, as was first noticed by
usual for aniline, sold as pure, to contain more about the year 1800. In fact, from that date
than 0-5 p.c. of water. to 1811, wood charcoal was much employed for
264 ANIMAL CHARCOAL.
decolourising syrups, but it was then demon- than when the contact is prolonged. The
strated by Figuier that bone black was far more difference due to time of contact, however,
effectual and energetic in its action. ceases when the contact has lasted some hours.
In 1812 Louis Constant took out a patent Various explanations have been offered to
for improving wood charcoal by washing and account for the peculiar action of charcoal. It
grinding, and using this prepared charcoal in was attributed by Bussy to the highly divided
sugar-refining. state of the carbon contained in it. From the
In 1815 Messrs. P. & J. Martineau patented similarity of the action of charcoal upon diverse
bodies, and the general nature of its operation,
'
the use of animal charcoal, that is to say,
animal substances properly burnt, charred, or it would appear to be due to some
physical or
calcined,' for refining and clarifying sugar and ;
mechanical cause. Charcoal seems, indeed, to
in 1817 De Cavaillon in a patent, states that he exert merely a surface action, withdrawing the
had found that animal charcoal, after it has been colour from the liquid passed through it, but
used and again calcined, answers for the purpose not in any way destroying the same, and Kohl-
of bleaching and clarifying sugar in a manner
'
rausch has shown by experiment that by means
superior to new charcoal, and the operation may be of a solution of ammonia it is possible to practi-
repeated any number of times with equal effect.' cally dissolve out all the colour which has been
In 1830 Charles Derosne described the use absorbed by charcoal through which molasses
of animal charcoal reduced to the size of fine
'
has been previously passed.
placed on a cloth in a layer to the In connection with the action of animal
eight of 16 inches, and covered with a perforated
funpowder,' charcoal, it is stated by P. Degener and J. Lack
diaphragm, as a filter for sugar solutions. (D. R. P. 31358, 1884) that the freshly ignited
Although the effect of animal charcoal is charcoal, moistened with as much water as it
most conspicuous in removing organic colouring can take up, and exposed to light and ah-, pro-
matters from solution, it is also capable of absorb- duces, even in a few minutes, a perceptible
ing many other organic and also mineral sub- quantity of hydrogen peroxide, and is thus ren-
stances. It was proved by Graham that various dered more active than the untreated material.
mineral substances were removed from solution They also state that exposure for 48 hours
by animal charcoal thus the lime is taken up
; in layers of 3 inches thick, the charcoal being
from lime water, and metallic salts are absorbed frequently sprinkled with water and turned over
from their solutions in water. According to gives good results, and that if milk of lime
Chevallier, lead nitrate and acetate are com- is sprinkled over bone black, calcium peroxide is
pletely removed by animal charcoal. Weppen produced, and in the same way other alkaline
has shown that this action extends to a great earths and alkalis can be converted into peroxides.
variety of metallic salts, including cupric, zinc, It was first observed by Tilliot that more
chromic and ferrous sulphates, nickel, cobalt, organic matter is absorbed by charcoal from
silver, mercurous and mercuric nitrates, tartar solutions at a high temperature than in the cold,
emetic, stannous chloride, and ferric acetate. this result being only partially due to the
As the result of a number of experiments on increased circulation caused by heating.
the absorption of different salts by animal Manufacture of animal charcoal. The bones
charcoal, Bodenbender (The Sugar Cane, ii. 316) employed should be carefully selected, hard,
arrived at the following conclusions : and free from extraneous matter. Whale and
1. The power which it fish bones are not of a suitable character,
possesses of absorbing
salts is for the most part a physical property. as they yield a soft char. Bones which have
2. A given weight absorbs a larger proportion been exposed to atmospheric action for a long
of salts from a concentrated than from a diluted time, or which have been buried in the ground,
solution ; on the other hand, the proportion cannot be successfully employed, as, owing to
absorbed from a constant quantity of salts is the alteration in their composition, they produce
more considerable when this quantity is in a a char deficient in carbon.
dilute, than when it is in a concentrated, solution. Before proceeding to carbonise the bones,
3. The presence of sugar has only a the fat is removed by boiling, or by means of a
slight
influence on the absorption of salts. suitable solvent such as benzene. By the first-
4. The salts of potassium are retained in named treatment from 4 to 5 p.c. of fat is ex-
smaller proportion than those of sodium. tracted, and by the second from 8 to 12 p.c. In
5. Among the salts experimented with, the the process of extracting fat from bones by
amount taken up is in the following order, means of a solvent, difficulties arise from the
beginning with that least absorbed potassium
:
presence of water, and F. Seltsam (Eng. Pat.
chloride, sodium chloride, potassium nitrate, 10208, 1855) has proposed to overcome these by
sodium nitrate, potassium acetate, sodium using a solvent (such as a hydrocarbon from
acetate, potassium sulphate, sodium sulphate, petroleum) having a higher boiling-point than
magnesium sulphate, potassium carbonate, that of water, the temperature during extraction
sodium carbonate, sodium phosphate. being raised to above 100C. He states that by
6. A chemical action of charcoal has been this means the water is expelled from the bones
observed with respect to some carbonates, oxa- and the extraction of fat is rendered more
lates, and other salts, being brought about by complete. Lorcnz says that bones after treat-
the presence of calcium sulphate and phosphate ment with benzene contain 1 -2-2-5 p.c. of fat,
in the charcoal. which can be extracted by a further treatment
7. Charcoal saturated with one salt is with benzene, and 0-48-0-8 p.c. of fat remov-
capable, within certain limits, of withdrawing able by ether, or in all, 1-68-3-3 p.c., which is
another salt from solution. lost in the process. This mode of extracting fat is
8. There is less
absorption by charcoal of a employed in many factories on the Continent, and
salt when in contact with it for a short time, until recently was used in the United Kingdom,
ANIMAL CHARCOAL. 265
but it is objectionable on the ground that The carbon always contains a certain pro-
the advantage gained in the increased amount portion of nitrogen amounting to about one-
of fat recovered is more than counterbalanced tenth of its weight ; there is also a minute
by the decreased value of the resulting animal proportion of hydrogen present. The nitrogen
charcoal. continually becomes less and less whilst the
The apparatus employed in making bone bone charcoal is being used for sugar-refining.
charcoal similar to that used in a gasworks.
is When char is repeatedly reburned, it becomes
The bones are carbonised, after being roughly less porous and shrinks in volume, so that a ton
crushed, in vertical or horizontal iron retorts of of char, which, when new, measures 48 to 54
a round, oval, or D
section, the latter by pre- cubic feet, may be reduced to as low as 28 cubic
ference. The length of the horizontal retort is feet after being reburned many times, or, in
usually from 8 to 10 feet, the long diameter being other words, its apparent density may be
nearly
18 inches and the short diameter of the oval re- doubled.
tort 12 inches. There are usually five or seven Wallace has, however, shown that the real
retorts in each bed. The retorts are connected sp.gr. varies but little ; thus, a new char occu-
in the same way as gas retorts, with a hydraulic pying 50-6 cubic feet per ton, or having an
main, and this again with condensers or scrubbers apparent sp.gr. of 0-71, had a real sp.gr. of
with coke in which the bone oil separates and
filled 2-822, whilst a moderately old sample, occupying
from which the gases are exhausted. The gases are 35 cubic feet per ton, or having an apparent
then forced through a series of washers contain- sp.gr. of 1-03, had a real sp.gr. of 2-857, or only
ing water to remove the ammonia, the residual a trifle over that of the new.
gases, which are employed for heating and light- Another proof that char loses its porosity to
ing purposes, finally passing into a gas-holder. a considerable extent by long-continued use 'and
Charges of about 2J cwt. of bones are carbonised reburning is afforded by the fact, pointed out
in vertical, and 5 cwt. in horizontal retorts, the by Wallace, that dry new char will absorb from
operation taking about 6 to 8 hours with 80 to 100 p.c. of its weight of water, whereas
the former and 8 to 10 hours with the latter. old char will only retain from 30 to 45 p.c.
The bone oil collected in the condenser amounts New charcoal of good quality should, in the
to from 3 to 5 p.c. on the bones carbonised, and dry state, contain not less than 9 and not more
the ammonia in the ammoniacal liquor is equal than 11-5 p.c. of carbon. The silica should not
to about 8 p.c. of ammonium sulphate, into exceed 0-5 p.c., the oxide of iron 0-15 p.c., the
which it is converted in the usual way. When calcium sulphate 0-2 p.c., and the moisture
the bones are completely carbonised the char- 8 p.c. Its weight should not exceed 52 Ibs. per
coal is removed from the retorts and cooled in cubic foot. It should be of a dull black colour,
strong sheet-iron canisters, which are at once and, when incinerated, leave an ash of a uniform
covered with closely fitting lids and luted round white or cream colour the presence of grey or
;
the edges, either with charcoal paste or a water reddish particles indicates that the sample has
lute. The char when quite cold is crushed in been mixed with old charcoal. When brought
a suitable mill (on its way to which any iron it in contact with the tongue, it should adhere to
may contain is removed by passing over the it somewhatstrongly. The size of grain which
poles of an electromagnet), ami then sifted into desirable to have in new charcoal depends
it is
various sizes to suit the requirements of the upon the use to which it is to be applied. Large-
sugar-refiner. It is usualty moistened before grain charcoal is preferable for strong liquors,
grinding to keep down the dust. Good bones such as the liquor used for washing loaf sugar.
yield about 65 p.c. of char, but from 20 to 30 p.c. Refiners, as a rule, prefer small grain if, how-
;
of this is dust, which fetches a lower price than ever, it be very small, it impedes the passage
the larger grist. of liquor and also gives considerable trouble in
The following analysis gives approximately washing. Char may be used over and over again
the composition of a good sample of new bone and sometimes lasts several years, being revivi-
charcoal : fied each time after use by reburning in special
Carbon 10-51 kilns (see SUGAR). When, by continued use, it has
Calcium and magnesium phos- practically lost its power of removing colour, it
is known as spent char, and is then used as a
phates, calcium fluoride, &c. 81-21
Calcium carbonate . ..7-30 manure, either as it is, or more generally after
Calcium sulphate
Ferric oxide
Silica
.... . . 0-17 .
0-12
0-34
treatment with sulphuric acid, so as to form
superphosphate of lime.
Animal charcoal dust is employed as a pig-
ment after being finely ground either in a dry
Alkaline salts . . . .0-35
or wet state; it is also used in the manufacture
100-00 of blacking (q.v.).
Moisture originally present 8-00 . Ivory black consists of char in an exceedingly
fine state of division.
Space occupied by one ton, 48 cubic feet.
Sizes left on sieves of various
degrees of Although the chief use for animal charcoal is
fineness :
in refining sugar, it is also employed for the
Above 10 holes to linear inch purification of water, vegetable or mineral oils,

.
paraffin, glycerol, and various other organic

10 to 20 , 28
substances.
20 to 30 32
sometimes found necessary to use a
.
,
It is
30 to 40 . 27
40 to 50
,
more powerful decolourising agent than ordinary
. 11
,
bone charcoal, and this is prepared by treating
Through 50 , or
dust_2 new animal charcoal with dilute hydrochloric
100 acid to dissolve out the inorganic constituents,
266 ANIMAL CHARCOAL.
leaving the carbon behind. This, when care- Indian plant belonging to the Labiatae and
fully washed and dried, forms a most valuable containing a volatile oil. Used in quinsy.
decolourising agent. N. BROS. ANISOLE. Anisoil ; Methylphenyl ether
ANIMAL OILS and FATS v. OILS AND FATS. C 6 H S -0-CH 3 .
ANIME and ANIMI v. OLEO-RESINS. Preparation. Anisole can be obtained by dis-

ANISEED. (Anis, Fr., Ger.) The fruit of the tilling anisic acid or o-methoxybenzoic acid with
Pimpinella Anisum (Linn. ), cultivated in Malta, baryta, or by heating potassium phenate with
Spain, and Germany. Used for the preparation methyl iodide at 120 (Cahours, Ann. Chim. Phys.
of anise oil and cordials. Alcohol extracts 36-24 [3] 2, 274 10, 353
; 27, 439).
;
It is prepared
p.c. of this spice (Biechele, Pharm. J. [3] 10, by passing a current of methyl chloride over dry
878). sodium phenate heated at 190-200 (Vincent,
ANISE CAMPHOR v. CAMPHOKS. Bull. Soc. Chim. 40, 106), and by heating phenol
ANISE OIL. The essential oil of aniseed, with methyl alcohol and potassium bisulphate
obtained by with water. According
distilling it at 150-160 (Act. Ges. fiir Anil.-Fabrik. D. R. P.
;
to Landolph (Compt. rend. 81, 97 ; 82, 226), it 23775). It has been synthesised by fusing
contains 90 p.c. of anethole, boiling at 226. sodium benzene sulphonate with sodium
Anethole, according to Perkin (Chem. Soc. methoxide (Moureu, J. Pharm. Chim. 8, v. 211).
Trans. 32, 668), is p-allylanisole C 6 H 4 (OMe)CH :
Properties. It is a colourless ethereal liquid,
CH'CH 3 ; he obtained it by heating ;p-methoxy- which boils at 155-155-5at 762-3 mm. (Schiff,
phenylcrotonic acid. Annalen, 220, 105) at 153-9 (corr.) (Perkin,
Anise oil is sometimes adulterated with Chem. Soc. Trans. 69, 1240) ; melts at - 37-8
fennel oil this can be detected by heating the
; (Von Schneider, Zeit. Phys. Chem. 19, 997)
oil, when the fennel odour becomes perceptible. and has a specific gravity 0-991 at 15 (v.
Star anise oil has a similar colour and OILS, ESSENTIAL).
taste, but it does not solidify at 2 (v. OILS, ANISOMELES MALABARICA (R. Br.). A
ESSENTIAL). much-esteemed Indian plant belonging to the
ANISIDINE. 2 -C 6NH
4 -OMe. H
Orthanisi- Labiatse ; an infusion of the leaves is used in
dine. Obtained by the reduction of orthonitrani- intermittent fevers, and the essential oil is
sole with tin and hydrochloric acid or iron and applied externally in rheumatism.
hydrochloric acid (Meister, Lucius, and Bruning, ANKOOL, AKOLA, DHERA BARK. The
D. R. P. 7217 of Dec. 3, 1878), is a colourless root bark of Alangium Lamarckii (Thw.), one of
oil, which boils at 226-5 at 734 mm. pressure the Cornaceae, used in leprosy and skin-diseases
(Muhlhaiiser, Annalen, 207, 239); at 225 at (Dymock, Pharm. J. [3] 9, 1017).
760 mm. (Perkin, Chem. Soc. Trans. 69, 1210), "ANNATTO isderived from the fruit of the
and has a sp.gr. 1-108 at 26. When diazotised Bixa oreUana (Linn.), a shrub found native in
and treated with -naphtholdisulphonic acid Central America, and cultivated in Brazil,
(R-acid), it yields anisole-red (v. Azo- COLOURING Guiana, Mexico, the Antilles, and India.
MATTERS). A mixture of orthanisidine (2 mols.) To prepare the dyestuff, the seeds and pulp
and paraphenylenediamine (1 mol.) is converted, are removed from the mature fruit, macerated
on oxidation with potassium dichromate, into a with water, and the mixture is left to ferment.
reddish colouring matter formerly employed The product is strained through a sieve, and the
under the name safranisole (Kalle & Co., D. R. P. colouring matter which settles out is collected,
24229 of Oct. 27, 1882 expired March, 1885).
; partially evaporated by heat, then placed in
Paranisidine, obtained from paranitranisole boxes, and finally dried in the sun.
by reduction with tin and hydrochloric acid, Annatto comes into the market in the form
crystallises in prisms which melt at 55-5-56-5 of cakes, and among the different varietie
(Lessen, Annalen, 175, 324) and boil at 245- Cayenne annatto is the most esteemed, and is
246 (Salkowski, Ber. 7, 1009) ; 243 at 760 mm. considered to be the richest in colouring matter.
(Perkin, Chem. Soc. Trans. 69, 1210) ; p-anisidine, It should contain from 10 to 12 p.c. of the pure
o-sulphonic acid, prepared by boiling the hydro- dye, and not more than 5 p.c. of ash, whereas
gen sulphate of 2>- ani s idine, when diazotised the amount of colouring matter in the Bengal
and coupled with -naphthol, yields an azo- product is frequently lower than 6 p.c.
compound forming red lakes with baryta, In 1848 Dumontal devised a new method for
alumina, &c. (Aktiengesellschaft fiir Anilin- the preparation of annatto, in which fermenta-
Fabrikation, D. R. P. 14665). tion is avoided, and the pulp is simply washed out
Chloranisidine, when diazotised and coupled from the capsules and off the seeds. The
with /9-naphthol, yields a red compound in- product known as bixin is said to be five to six
soluble in water (Julius, Ludwigshafen and times more valuable than ordinary annatto
Jahrmaht, U.S. Pat. 695812) ; p- and m-nitro- (Crookes, Dyeing and Calico-Printing).
anisidine, when diazotised and coupled with The colouring matters of this dyestuff were
/8-naphthol, yield red and pink dyestuffs (Imray, first investigated by Chevreul (Legons de chimie
Eng. Pat. 25756 ; J. Soc. Chem. Ind. 1898, 1039 ; appliquee & la Teinture), who isolated two
and Freyss, J. Soc. Chem. Ind. 1901, 356) ; substances, one yellow, which was called orrclline,
o-iodo-^)-anisidine, when diazotised and treated soluble in water, and a second, bixin, which is
with naphthol sulphonic acid, yields a red dye, red and very sparingly soluble.
similar to that obtained from p-anisidine Bixin, the useful colouring matter, was subse-
(Reverdin, Ber. 29, 997). quently examined by numerous chemists, who
Anisidine condenses with orthoformic ester, were only successful in preparing it as an
and the resulting compound is used as an amorphous powder, and its isolation in a
anesthetic (Goldchsmidt, Eng. Pat. 9792 ; J. Soc. crystalline condition was first achieved by Etti
Chem. Ind. 1899, 606). (Ber. 7,446; 11, 864).
ANISOCHILUS CARNOSUS (Wall.). An Etti digested 1-5 kilos of purified annatto
ANNEALING. 267
with a solution of 150 grams of calcined soda ash country. As the orange-red colour which it
in 2-5 kilos, of 80 p.c. alcohol on the water-bath yields is extremely
fugitive to light it has at no
at 80. The mixture was filtered and the time been very extensively used. On the other
residue pressed between warm plates, and again hand, it resists the action of soap and dilute acids
extracted with 1-5 kilos, of warm 60 p.c. alcohol. very well.
The alcoholic filtrate was diluted with half In order to dye cotton, the annatto is first
its volume of water, concentrated sodium carbon- dissolved in a boiling solution of carbonate of
ate solution added, and the crystalline precipi- soda, and the goods are then entered and left
tate of sodium bixin was collected after several in the bath for a quarter of an hour.
They are
daj's, and pressed. The product purified by solu- subsequently pressed out, and washed in slightly
tion in 60 p.c. alcohol at 70-80, and reprecipi- acidulated water or alum solution.
tation with sodium carbonate was finally made For silk, the bath is made up with equal
into a cream with alcohol, and this, when neu- parts of annatto and sodium carbonate ; soap
tralised with hydrochloric acid yielded crystal- is also usually added, and the
dyeing is con-
line bixin. tinued at 50 for about an hour, according to the
A simpler method has been more recently shade required. The colour produced can be
devised by Zwick (Ber. 30, 1972). Well-dried rendered somewhat more yellow by passing
annatto is extracted for 24 hours with boil- the fabric through a weak solution of tartaric
ing chloroform, the extract evaporated, and acid.
the residue thoroughly exhausted with ligroin. Wool is dyed at 80-100, without any
"
The product is crystallised from chloroform, addition to the bath. A. G. P.
and after washing with ligroin, is repeatedly ANNEALING. (Le recuit, Fr. ; das Anlassen,
recrystallised from the former solvent. Ger.) A
process which is applied princi-
Bixin C 28 H 34 5 (Etti, I.e. Marchlewski
; pally to glass and metals for the purpose of
and Matejko, Chem. Zentr. 1906, ii. 1265) rendering them softer or less brittle. The
consists of brown-red or deep-red rhombic process itself always consists in the application
crystals, which, when slowly heated, melt at of heat for a period of time, which may vary
191-5, and when rapidly heated, at 198. It is from a few minutes to many hours, and which
sparingly soluble in the usual solvents, and of may be followed by very slow cooling ; the
these it is most readily dissolved by chloroform object of the process is to permit the material
or alcohol. Concentrated sulphuric acid dis- to attain approximate equilibrium in regard
solves bixin with a cornflower-blue colouration, to its internal structure. This state of normal
and this reaction is characteristic, and is given internal equilibrium may be disturbed either
by minute traces of the substance. by the effects of rapid cooling or by the applica-
Monosodium bixin C 28 33 O 5 H 2 Na+2H
is tion of mechanical deformation. The former
best prepared by dissolving 10 grams of bixin is most frequently met with in glass, and in
in a solution of 1-2 grams of sodium carbonate large metal castings, while the latter is found in
' '
in 300 c.c. of 12 p.c. alcohol at 70 (Etti, Zwick). wrought metal of all kinds.
It is deposited on cooling in dark-red iridescent In the case of substances which are poor
crystals, and can be obtained in the anhydrous conductors of heat, such as glass, and also in
condition by recrystallisation from 70 p.c. masses of metal which are so large that thermal
alcohol (M. and M.). conductivity cannot produce reasonable uni-
Disodium bixin C 28 32 OsNa 2 H 2 +2H
is formity of temperature, relatively rapid cooling
obtained when 20 grams of bixin is dissolved In sets up severe stresses, owing to the fact that
a solution of 10 grams sodium carbonate in the outer or most rapidly cooled layers solidify
600 c.c. of boiling 12 p.c. alcohol. It consists first subsequently the internal portions of the
;
of a dark-red amorphous powder (Etti). Mono- mass endeavour to contract in solidifying, and in
potassium bixin C 28 33 O 2 H K+2H
2 and dipo- cooling, but find themselves constrained by
their
tassium bixin, C 28 32 5 2 H K +2H
2 have also attachment to a relatively rigid external envelope ;
been prepared. the tendency to thermal contraction is there-
Bixin contains one inethoxyl group. Dis- fore overcome by severe tensional stresses.
tilled with zinc-dust, bixin yields,
according to A body in this condition, while it may present
'
Etti, metaxylene, metaethylxylene, and a hydro- the phenomenal strength of a Rupert's drop,'
H
carbon C M 14 b.p. 270-280.
,
is liable to sudden fracture, particularly if
According to Zwick, bixin is readily reduced the surface is cut or broken. In such sub-
by sodium amalgam, and a compound, C 23 40 7 , H stances, effective annealing implies heating
is thus
produced. Marchlewski and Matejko. to a point where the mass becomes sufficiently
on the other hand, studied the action of zinc- soft to release all internal stresses, followed by
at
dust and acetic acid, and obtained in this very slow cooling down to the temperature
manner an orange-coloured crystalline substance which the body is completely solid. In the
which possessed a strong metallic lustre. When case of fine optical glass, the rate of cooling is
slowly heated, it melts at 200-5, but if the retarded so that a fall of 100 occupies one
operation is carried out rapidly, at 208-210. week. For metals such excessively slow cooling
This compound is evidently of an unstable is undesirable, and is never intentionally used.
' '
nature, for whereas when freshly prepared it Metals in the cast or other normal con-
gives C=75-4, H=7-7 p.c., on standing for some dition consist of aggregates of minute crystals
days in the air it becomes colourless and then of approximately equal dimensions in all direc-
gives 0=58-6, H=5-8
per cent. At 100 this tions ; when metal is mechanically deformed,
change occurs more rapidly. as by hammering, rolling, or other working
the cold, these minute
Dyeing properties. Annatto is still employed process carried on in
to a fair extent for in the same general sense
colouring oils and butter, crystals are elongated
but is almost extinct as a dyostuff in this as the mass of which they form part, and this
268 ANNEALING.
deformation of the crystals is accompanied by matter of the flowers of the yellow toadflax
the well-known hardening of the metal under (Linaria vulgaris). Formerly used as a dyeing
cold work. This is due in part to the internal material, but the colour is not permanent.
rearrangement which each crystal undergoes, ANTHOKYAN. The expressed juice of the
and in part to the partial and local destruction sweet or purple violet (Viola odorata), gently
of the crystalline arrangement itself, accom- heated to 89, then skimmei, cooled, and
panied by the formation of a hard amorphous
' '
filtered. A little rectified spirit is then added,
phase (Ewing and Rosenhain, Phil. Trans. and the following day the whole is again filtered.
1899, ser. A, cxiii. 353-375; Beilby, Used to make syrup of violets, and to colour and
Phil. Mag. 1894). When the metal is subse- flavour liqueurs.
quently annealed, i.e. heated to a suitable ANTHOPHACIN. A term given by Mobius
'
temperature, the metal recrystallises,' the (Chem. Zentr. 1901, i.

190) to the brown colouring
crystals rearrange themselves, and the original matter of flowers.
condition is approximately restored. In some ANTHRACENE C 14 H, . Discovered by Dumas
metals the molecular mobility is such that and Laurent in the highest boiling portion of
recrystallisation takes place slowly even at the coal tar, and termed by them paranaphthalene
ordinarv temperature (lead Ewing and Rosen-
:
(Annalen, 5, 10) further examined by Laurent,
;
hain, Phil. Trans. 1900, cxcv. 279-301 ; brass : who re-named it anthracene (Annalen, 34, 287) ;
Cohen, Rev. general des Sciences, April 30, first obtained pure, and its composition deter-
1910) but in the greater number of cases a

; mined, by Fritzsche (Annalen, 109, 249), and
high temperature is required. In the great more exactly studied by Anderson (Annalen,
majority of pure metals, and in some alloys, 122, 294 ;Chem. Soc. Trans. 15, 44).
the rate of subsequent cooling is immaterial Occurrence. -Anthracene is one of the pro-
so far as the softening effect is concerned ; but ducts of the destructive distillation of coal, and
in certain metals and in a large number of is found in the tar ; the average yield of the
alloys either allotropic or other changes take pure hydrocarbon is about 0-3 p.c. of the tar
place during gradual cooling, and these trans- obtained.
formations are more or less inhibited by rapid A new source of anthracene has been an-
cooling in such metals the rate of cooling
; nounced (Dingl. poly. J. 246, 429) in the tar
' '
through the critical temperatures at which obtained when the residue, left after the illumi-
these changes occur is of material importance. nating oils have been distilled from Baku petro-
The most striking example is found in carbon leum, is allowed to fall on pumice in red-hot iron
steels, which are moderately soft if cooled slowly retorts. 1000 kilos of naphtha residue under
down to a temperature of 650, but become these conditions yield 500 c.m. of gas, used to
exceedingly hard if suddenly cooled from a heat the retorts, and 300 kilos, of tar, containing
temperature above 700. In the case of about 0-2 p.c. of pure anthracene. The supply
hardened tool steel, the process of annealing of the naphtha residue is, however, too limited
consists in raising the steel to such a temperature to render anthracene from this source a serious
(above 700) that the changes which were competitor with that from coal tar.
suppressed when the steel was hardened by According to Elliott (Amer. Chem. J. 6,
quenching are allowed to take place during the 248), the tar obtained in the manufacture of
heating and cooling process. gas by the destructive distillation of light
In many metals the annealing process is petroleum naphtha boiling below 150 contains
liable to be complicated by the effects of 2-63-2-90 p.c. of anthracene. A remarkable
chemical actions between the metal and its production of anthracene, during the distillation
solid or gaseous surroundings, as well as by the of the higher-boiling portions of crude phenol,
effects of the growth of the constituent crystals has been observed by Kohler (Ber. 18, 859).
of the metal ; at high temperatures these Anthracene is obtained by the distillation
crystals tend to increase in size, and the resulting of rhein with zinc-dust (Oesterle and Tesza,
coarsening of the grain of the metal leads to Arch. Pharm. 1908, 432), but this production
a deterioration in mechanical properties. is of no commercial value.
Annealing at an unduly high temperature or '

Preparation (Auerbach, Das Anthracen und
for too long a time thus becomes over-heating,' seine Derivate ; Kopp, J. 1878, 1187 Per kin, ;
and .is injurious to almost all metals and alloys, Journ. Soc. Arts, 27, 572 Lunge, Coal Tar and
;
notably to steel and brass. W. R. Ammonia). Anthracene is obtained from the

' '
ANODYNINE. Identical with antipyrine green grease which forms the last portion of
' ' ' '
(q.v.). the heavy oil or dead oil of the tar distiller :
ANON A MURICATA (Linn.). A decoction this at first is a brown liquid with a greer
of the root is used as an antidote for fish-poison- fluorescence, but soon becomes semi-solid on
ing, and the bark serves as an astringent. The standing, owing to the separation of solid sub-
leaves are useful in softening abscesses, and from stances. When no further separation occurs,
the seeds a wine can be prepared which is said the mass subjected to filtration, cither in
is
to be beneficial in cases of diarrhoea (Chem. centrifugal machine or a filter press, first in
Zeit. 10, 433 ; J. Soc. Chem. Ind. 5, 332). the cold and finally at 40 (Gessert, Dingl.
ANORTHITE v. FELSPAR. poly. J. 196, 543) ; or is filtered through strong
ANOZOL. Trade name for a preparation linen bags, and afterwards submitted to hydraulic
of iodoform deodorised by 10-20 p.c. of thymol. pressure in a press so arranged that the plates can
ANTHEMOL v.CAMPHORS. be heated with steam and the cake hot-pressed.
ANTHIONE. Trade name for a solution of A notable quantity of anthracene remains dis-
potassium persulphate. Employed as a photo- solved in the expressed oil, and especially in
graphic reagent. the portions separated when the temperature is
ANTHOKIRRIN. The yellow crystalline raised, and is recovered by redistilling and
ANTHRACENE. 269
working up the product as just described. The of different origins to a similar

condition of
hard yellowish-green cake obtained, containing purity ; even pitch anthracene obtained by
25-40 p.c. of pure anthracene, is ground to a the distillation of gas-tar
pitch in iron retorts
fine powder in mills and heated with coal-tar with the aid of super-heated steam, and
generally
naphtha (b.p. 80-100), solvent naphtha (b.p. unsuitable for purification to the
owing difficulty
120-190), creosote oil, or petroleum spirit of removing higher hydrocarbons associated
(b.p. 70-100), in large
iron vessels provided with it works perfectly well after it has been
with stirrers. Petroleum spirit is to be pre- subjected to this process.
ferred (Perkin), since it dissolves less anthracene Many modifications in the method of puri-
whilst the impurities are sufficiently soluble fying crude anthracene have been introduced.
in it to be removed if the quantity of solvent A method based on the far greater solubility
employed is 23times as great as that of the of the impurities in mixtures of
aniline, pyridine,
anthracene to be purified. Solvent naphtha, or quinoline bases, has been patented
by the
consisting esentially of xylenes, pseudo-cumene Chemische Fabriks-Actiengesellschaft in Ham-
and mesitylene, is extensively employed, as burg (D. R. P. 42053 of April 15, 1887). The
phenanthrene is much more soluble than anthra- crude anthracene is dissolved at 100 in
l|-2
acene in this solvent. When creosote oil is times its weight of a dehydrated and rectified
used, it must be free from naphthalene ; the mixture of tar bases (pyridines) separated from
advantage of using creosote oil is that it dis- the light oil obtained in tar distillation
(compare
solves out the methyl anthracene, the anthracene D. R. P. 34947 and 36372), and the solution,
being practically insoluble therein. The residue on cooling, yields a crystalline separation of
contains from 45-50 p.c. of the hydrocarbon, anthracene almost free from carbazole and its
but inasmuch as it is not readily reduced to homologues. The patentees state that a 33 p.c.
powder, and unless finely divided is only slowly anthracene dissolved in 1-75 times its weight
attacked by oxidising agents, it is sublimed by of pyridine bases yields on crystallisation an
passing steam, heated at 220-240, over the 82-5 p.c. anthracene, whilst when dissolved
melted product, and condensing the vapours in in twice its weight of a mixture of equal
parts
a chamber by jets of water. The anthracene of pyridine bases and benzene, it yields an
thus obtained is in leafy masses, containing 80 p.c. anthracene, and in twice its weight of a
from 50-60 p.c. of the hydrocarbon, the chief mixture of equal parts of benzene and aniline a
impurities consisting of carbazole (10-12 75 p.c. anthracene. The recovery of the an-
p.c.), phenanthrene, pyrene, chrysene, and other thracene contained in the mother liquors offers
hydrocarbons, together with small quantities of no special difficulty.
phenols of high boiling-point, and of acridine ; Remy and Erhart (D. R. P. 38417 of Jan. 19,
it can readily be
ground to a paste, and is now 1886) have proposed crystallisation from oleic
sufficiently pure for conversion into anthra- acid as a means of purification of crude anthra-
quinone by oxidation. If, however, dichloran- cene. The difficulty of recovering the anthra-
thracene is required, further purification is cene contained in the mother liquors would seem,
necessary ; this can be effected by distillation however, to deprive this method of technical
with caustic potash, whereby impurities such as importance.
carbazole and bodies of a phenolic character are Graham (Chem. News, 33, 99, 168) has
retained, and anthracene, together with phenan- devised a method for recovering anthracene
threne, distils over with no greater loss than from the filtered oils used in its purification.
occurs if the 60 p.c. product is distilled alone ; The Farbenfabriken vorm. Friedr. Baeyer &
caustic soda cannot be substituted for the potash, Co. (D. R. P. 68474 Eng. Pat. 5539
; j. Soc. ;
since it produces no purification of any conse- Chem. Ind. 1893, 439) employ liquid sulphur
quence. Instead of distilling washed anthracene dioxide, which dissolves the impurities of crude
(100 parts) with caustic potash, Perkin employs anthracene, but very little anthracene itself.
a mixture of Montreal potash (30 parts), which 600 kilos, crude anthracene is mixed in a wrought
usually contains potassium hydroxide in con- iron agitator with 2400 kilos, liquid sulphur
siderable quantities, and caustic lime (6 parts). dioxide, first exhausting the air and then allowing
Unless lime is used, the residue in the retorts the sulphur dioxide to enter. The reaction
its own
forms a hard cake, which can be removed only [laving ceased, the mass is forced by
with difficulty. Hydrogen is evolved during the vapour pressure into an iron steam-jacketed,
distillation. The distillate is freed from phen- filtering tower, where anthracene
of 7080 p.c.
anthrene by washing with coal-tar naphtha, and remains behind. The mother liquor is distilled,
the residue is a very pure anthracene. This the sulphur dioxide being collected and recon-
production of phenanthrene, even from anthra- densed by means of an air-compressor.
cene which has been freed from this impurity by Another patent of the same firm (D. R. P.
extraction with solvents previous to distillation 78861 Eng. Pat. 7862
;
J. Soc. Chem. Ind.
;
with caustic potash, is noteworthy and points to 1895, 361) recommends the use of acetone or
the probable existence of molecular compounds other fatty ketones as a purifying agent.
of phenanthrene with other of the 560 crude anthracene is stirred in a steam-
impurities of kilos,
the washed anthracene, which are destroyed jacketed cylinder with 750 kilos, acetone for an
during the distillation with caustic potash. This iour. After cooling the separated anthracene
process of Perkin has been subjected to con- '.afiltered and washed with 375 kilos, acetone.
liquor is used over again, and
siderable criticism. The second the
According to Auerbach, a
loss of anthracene to the extent of 10 iirst to recover the acetone.
is distilled From
p.c. occurs,
and this, added to the cost of fuel employed, crude stuff containing 34 or 35 p.c. anthracene,
renders it the most costly method of purification an article of 82 p.c. is easily made, and only a few
yet devised. The great advantage of the ser cent, anthracene remain in the residue after
method, however, is that it brings anthracenes distilling off the acetone.
The acetone may be
270 ANTHRACENE.
' ' '
used in the form of raw acetone or acetone Vesely and Votocek (Eng. Pat. 27596;
oils.' J. Soc. Chem. Ind. 1905, 191) find that concen-
Welton (Eng. Pat. 27559 D. R. P. 113291 ; ; trated sulphuric acid extracts the whole of the
J. Chem. Ind. 1900, 139) purifies crude
Soc. basic impurities of anthracene from a solution
anthracene by means of liquid (anhydrous) of crude anthracene in a solvent immiscible
ammonia, which dissolves out most of the with sulphuric acid. The most suitable solvents
impurities, but not the anthracene itself. are mineral and coal-tar oils, but carbon clisul-
Luyten and Blumer Pat. 14892;
(Eng. phide and chloroform may be used 100 parts
;
D. R. P. 141186 ; J. Soc. Chem. Ind. 1901, 796) of crude anthracene (35 p.c.) are dissolved in
state that when anthracene is purified by 300 parts of solvent naphtha, 100 parts of
solvents such as naphtha, acetone, &c., the concentrated sulphuric acid are added, and the
presence of tar oil in the crude anthracene is mixture is heated and at the same time vigo-
beneficial. 25 parts of drained crude anthra- rously agitated for a few minutes. The sulphuric
cene are heated with 35 parts of naphtha until acid having been drawn off, the solution is
the temperature is near that of the solvent. freed from acid by agitation with calcium
On cooling, the anthracene crystallises out and carbonate, filtered, and then allowed to crystal-
is filtered and washed with a little of the solvent. lise. By this process it is stated to be possible
It is dried by heating to fusion, and distilling to obtain an 85-90 p.c. anthracene, perfectly
off the solvent ; 80 p.c. anthracene is obtained free from carbazole.
by method.
this Atroublesome impurity in anthracene is
The Aktien Gesellschaft fur Theer und Erdol a peculiar paraffin, which has a high melting-
Industrie (D. R. P. 111359; Eng. Pat. 7868; point, and is only sparingly soluble either in
J. Soc. Chem. Ind. 1899, 750) heat crude light petroleum or coal-tar naphtha ; it is dis-
anthracene to fusion, and allow it to cool until solved to a certain extent by these solvents
50 p.c. has crystallised, when the mother liquor when hot, but on cooling is almost entirely
is run off and again allowed to crystallise. The deposited again. A small quantity left in the
second crop can be raised to the value of the anthracene frequently impedes succeeding opera-
first (45-50 p.c.) by another fusion. This tions, and, owing to its stability, passes through
product is again fused and treated with caustic most of the processes without change.
potash lye (50 p.c.) in quantity sufficient to Syntheses. From orthotolylketone, by heating
react with the carbazole present. When the with zinc-dust (Behr and Van Dorp, Ber. 7,
reaction is complete, the mass separates into two 17) from orthobenzylbromide, by the action of
;
layers, the lower part being potassium carbazole. sodium (Jackson and White, Ber. 12, 1965) ;
The upper anthracene layer is run into its own from a mixture of benzene, acetylene tetra-
volume of 90's benzol, which dissolves any bromide, and aluminium chloride (Anschiitz,
phenanthrene. The anthracene is pressed or Annalen, 235, 156) ; from benzene and alu-
centrifuged, and again washed with the same minium chloride under the influence of nickel
solvent, and isobtained as a pale-brown powder. carbonyl at 100 (Dewar and Jones, Chem. Soc.
By this means 30 p.c. anthracene is raised to Trans. 1904, 213) ; and by treating pentachlor-
90 p.c. (v. also Scholvien, Fr. Pat. 335013 ; ethane in benzene with aluminium chloride,
J. Soc. Chem. Ind. 1904, 113). when anthracene is formed through the inter-
The AktienGesellschaft fur Anilinfabrik mediate formation of perchlorethylene (Mouney-
(D. R. P. 178764; J Soc. Chem. Ind. 1907, rat, Bull. Soc. chim. 19, [3] 557). An interest-
1193) add potassium hydroxide to the melted ing synthesis resulting in the production of
crude anthracene, which is then distilled in methyl anthracene (m.p. 200) is that of Kraemer
vacud, the anthracene distilling over being and Spilker (Ber. 1890, 3174). By the interac-
passed into some solvent in which it is soluble tion of xylene and cinnamene, phenyltolyl-
at the temperature of the reaction, and from pentane is formed, which when passed through
which it crystallises on cooling. It is stated that a red-hot tube forms methyl anthracene (m.p.
9596 p.c. of the anthracene is recovered as a 207), hydrogen and methane being evolved.
product containing 95-98 p.c. of pure This synthetical production of methyl anthracene
is of importance in its relation to the present
Wirth (Eng. Pat. 14462 ; J. Soc. Chem. Ind. theories of the mode of formation of anthracene
1901, 464) separates the carbazole by means of in coal tar.
its easily soluble nitroso- compound. Crude Properties. Anthracene crystallises in glis-
anthracene is mixed in a vessel provided with a tening white scales. It melts at 216-5 (Reis-
stirrer with light coal-tar oil and sodium nitrite. sert, Ber. 1890, 2245), and boils at 382
Dilute sulphuric acid is added gradually, and the (Schweitzer, Annalen, 264, 193). When pure,
sodium sulphate which is formed is dissolved in it shows a bluish-violet fluorescence, but this
water and separated from the light-oil layer. is concealed small quantities of yellow im-
if
The anthracene is filtered from the light coal- purities (Fritzsche's chrysogen) are present.
tar oil, washed with benzene, and dried. It Yellow- coloured anthracene, on exposure to
contains 75-95 p.c. anthracene, according to sunlight, is bleached, and becomes fluorescent,
quality of the crude material. but under these conditions the hydrocarbon
Catchpole (Eng. Pat. 16641; D. R. P. undergoes conversion into paranthracene
164508; J. Soc. Chem. Ind. 1903, 1190) places H
(C 14 10 ) 2 a peculiar modification, which is
the crude product in the form of blocks or slabs much less soluble than anthracene, is unattacked
on a perforated or channelled surface in a by bromine and nitric acid at 100, and does
chamber suitably heated to a temperature not not combine with picric acid it melts at 244,
;
exceeding 200, whereby the impurities are and is thereby converted into ordinary anthra-
'
sweated
'
out. A slight washing with acid cene (Fritzsche, J. pr. Chem. 101, 333; Graebe
and distillation complete the process. and Liebermann, Annalen, Suppl. 7, 264 ;
ANTHRACENE. 271
Schmidt, J.Chem. [2] 9, 248). The fluor-

pr. 54B., and about 60 p.c. of the anthracene
escence of anthracene and certain of its deriva- employed is thus converted. If sulphuric acid
tives has been referred by Liebermann to a of 66B. is used, two isomeric
disulphonic acids
particular molecular grouping (Ber. 13, 913). are obtained, and these, on oxidation,
yield two
Meyer (Zeitsch. physikal. Chem. 1897, 468) anthraquinonedisulphonic acids, which are
attributes fluorescence to the presence of what isomeric with the two acids obtained
by the
are known as fluorphoric groups, which must direct sulphonation of anthraquinone. The
be situated between two heavy atomic groups, j8-anthracene disulphonic acid, after oxidation
usually benzene nuclei. The solubility of with chromic or nitric acids, and subsequent
anthracene in 100 parts of various solvents fusion with alkali, yields alizarin (q.v.), and the
has been determined by Versmann (Jahresbericht. monosulphonic acid similarly treated yields
1874, 423), Perkin (Journ. Soc. Arts, 27, 598 : anthrapurpurin (q.v.) (La Socie"te Anonomye des
v. Becchi, Ber. 12, 1978), Findlay (Chem. Soc. Matieres Colorantes et Produits Chemiques de
Trans. 1902, 1221) with the following results : St. Denis, Eng. Pat. 1280 ; J. Soc. Chem. Ind.
Parts of anthracene 1894, 32).

Alcohol (absolute) at 16 dissolves 0-076
The same acids are obtained by heating
(B.).
0-830 anthracene with alkali bisulphate to 140-150
b.p. (B.).
(D. R. P. 77311). Anthracene is readily attacked
sp.gr. =0-800 at 15 0-591 (V.).
=0-825 0-574 , (V.).
by chlorine and bromine, and yields with each
=0-830 0-491
element a series of additive and substitution
, (V.).
derivatives ; additive compounds, apparently,
=0-835 0-475 , (V.).
=0-840 0-460 are the first products of the action, and these
, (V.).
either decompose during the reaction or can be
=0-850 0-423 , (V.).
Ether . , 1-175
.
(V.).
decomposed by boiling with alcoholic potash
into the corresponding substitution derivatives,
Chloroform 1-736
. , (V.).
Carbon disulphide 1-478
which also form additive compounds by the
, (V.).
0-444 further action of the halogens. The chloranthra-
Acetic acid . , (V.).
cenes are now prepared on a large scale (Clayton
Light petroleum 0-394
. , (V.).
70-100 Aniline Co., Eng. Pat. 8744 ; J. Soc. Chem. Ind.
.
b.p.
at 15 disso ves 0-115 (P.). 1906, 64). Dry chlorine reacts with anthracene
in the presence of lead peroxide at a high
Benzene . . 1-296 (F.).
b.p. 80-100 0-976 (P.). temperature. Fifty parts by weight of anthracene
Toluene . . at 16-5 0-920 (B.).
and 10 parts of dry powdered lead peroxide are
treated with dry chlorine at 220 until the
. at b.p. 12-940 (B.).
weight has increased to 120 parts. The tempera-
When introduced into an alcoholic solution ture, however, may be varied between 180 and
of picric acid saturated at 30-40, anthracene 260, and the composition of the product varies
H
forms a picrate C 14 10 ,C 6 3 (N0 2 ) 3 0, crystal- H with the temperature employed and the amount of
lising in glistening red needles which melt at chlorine absorbed. The product consists mainly
138 it is decomposed into its constituents by
; of -tetrachloranthracene (m.p. 152), which
alcohol, water, and dilute alkalis, even in the is readily soluble in benzene and crystallises out
cold. The formation of the picrate is best in yellow needles, and another part much Jess
obtained by warming molecular quantities of soluble in benzene and more highly chlorinated.
anthracene and picric acid on the water-bath in This latter consists of two products hexachlor-
:
chloroform solution. On oxidation with po- anthracene (m.p. 277), which crystallises from
tassium dichromate or manganese dioxide and nitrobenzene, and heptachloranthracene (m.p.
sulphuric acid, anthracene is converted into 232), which is more soluble in benzene than
anthraquinone, whilst strong nitric acid oxidises the former. Oxidation converts these com-
itto anthraquinone and dinitroanthraquinone ; pounds into chloranthraquinones, containing
nitro- derivatives of anthracene can, however, 2 atoms of chlorine less than the original com-
be prepared by the action of strong nitric acid pound. Treatment with a mixture of nitric
on the hydrocarbon, if care is taken to decompose and sulphuric acids results in the formation of
any nitrous acid which may be formed during chlornitroanthraquinones which yield dyestuffs
the reaction (Perkin, Chem. Soc. Proc. 1889, 13). on treatment with fuming sulphuric acid. The
Electrolytic oxidation in acetone yields anthra- chloranthraquinones on treatment with fuming
quinone (Fontana and Perkin, Chem. Zentr. sulphuric acid in the presence or absence of boric
1904, ii. 708) the same product results by the
; acid, yield hydroxy- compounds ; e.g. 1 4 :
electrolytic oxidation of a suspension of anthra- dichloranthraquinone yields quinizarin (q.v.)

cene in a 2 p.c. solution of cerium sulphate in (Farb. vorm. F. Baeyer & Co., FT. Pat. 385358 ;
20 p.c. sulphuric acid at 80-90 (Farb. vorm. J. Soc. Chem. Ind. 1908, 557). Reducing agents,
Meister, Lucius and Bruning, D. R. P. 152063 ; such as sodium amalgam or phosphorus and
Chem. Zentr. 1904, ii. 71) or by the oxidation ; hydrogen iodide, convert anthracene into the
of anthracene by cerium oxide in sulphuric acid dihydride (Graebe and Liebermann, I.e. ; Lieber-
(Farb. M. L. & B. D. R. P. 158609 Chem.
; ; mann and Topf., Annalen, 212, 5); hydrogen
Zentr. 1905, i. 840) or by heating anthracene
; and nickel oxide at 260-270 and 100-125
with charcoal at 150-300 (Dennstedt and atmos. convert anthracene first into tetrahydro-,
Hassler, D. R. P. 203848 Chem. Zentr. 1908, ; then decahydro-, and finally perhydroanthracene
Ber. 1908,
ii. 1750). (Ipatieff, Jokowleff, and'Rakitin,
Concentrated sulphuric acid converts anthra- 996).
cene into sulphonic acids. Anthracene mono- Estimation. Luck (Ber. 6, 1347) ; Meister,
sulphonic acid is obtained by the direct sulphona- Lucius, and Bruning (Dingl. poly. J. 224, 559) ;
tion of anthracene with sulphuric acid of 53 or Nicol (Chem. Soc. Trans. 1876, 2, 553) ; Bassett
272 ANTHRACENE.
(Chem. News, 73, 178; 79, 157). The per- ANTHRACENE GREEN. Carulem and Cceru
centage of anthracene in a sample of the com- lein S. ALIZARIN AND ALLIED COLOURING
(v.
mercial product is determined by oxidising it MATTERS also XANTHINE COLOURING MATTERS).
;
to anthraquinone with chromic acid, dissolving ANTHRACENE VIOLET. Gallein(v. ALIZARIN

the product in sulphuric acid, and precipitating AND ALLIED COLOURING MATTERS ; also XANTHINE
with water, since the associated impurities are COLOURING MATTERS).
either destroyed during the oxidation or are
converted into sulphonic acids soluble in water.
ANTHRACHRYSONE v. ALIZARIN AND ALLIED
CGLOURING MATTERS.
The details of the process are as follows 1 gram
:
of anthracene is introduced with 45 c.c. of acetic ANTHRACITE v. FUEL.

acid into a flask connected with a reversed ANTHRACITE BLACK r. Azo- COLOURING
condenser, and heated to boiling ;
a solution of
15 grams of chromic acid in 10 c.c. of acetic ANTHRACOXENE v. RESINS.
acid and 10 c.c. of water is then added, drop by ANTHRACYL CHROME GREEN ?;. Azo-
drop, to the boiling solution during a period of COLOURING MATTERS.
2 hours and the product is boiled for 2
;
hours longer, allowed to stand for 12 hours,

ANTHRAFLAVIC ACID v. ALIZARIN AND
ALLIED COLOURING MATTERS.
then poured into 400 c.c. of water, and, after
ANTHRAGALLOL v. ALIZARIN AND ALLIED
standing for 3 hours longer, is filtered. The COLOURING MATTERS.
anthraquinone on the filter is washed with
water, with hot dilute alkali, and then with hot ANTHRAGALLOL DIMETHYL ETHERS
water ; afterwards it is placed in a small dish v. CHAY ROOT.
dried at 100, and digested for 10 minutes with ANTHRANIL, ANTHRANILIC ACID (o-
10 times its weight of pure concentrated sulphuric aminobenzoic acid) v. AMINOBENZOIC ACID AND
acid at 100. The solution of anthraquinone HOMOLOGUES.
is sulphuric acid is then allowed to remain for ANTHRANOL. 9-Hydroxyanlhracene
19 hours in a moist atmosphere, mixed with
200 c.c. of water, and the precipitated anthra- X>(OH)N
quinone filtered off and washed first with water,
then with dilute alkali, and finally with water ;
it is then dried at 100 in a dish, weighed, ignited, is prepared by the reduction of anthraquinone
and the ash deducted from the first weighing. with hydriodic acid and phosphorus (Liebermann
The difference gives the weight of anthraquinone and Topf, Annalen, 212, 6 ; Ber. 1876, 1201),
or with tin and acetic acid (Liebermann and
corresponding to the amount of anthracene
present in the sample. Gimbel, Ber. 1887, 1854). Another method is
Impurities. Paraffin is usually present in to add copper or aluminium powder to anthra-
crude anthracene, and is estimated by treating quinone dissolved in concentrated sulphuric
the material with fuming nitric acid, keeping acid at 30*-40, and pour the product into water.
the mass cold. When all the acid has been The crude substance is recrystallised from
added, the mixture is kept at the ordinary glacial acetic acid containing a trace of aluminium
temperature until the anthracene has dissolved, and a little hydrochloric acid
(Baeyer & Co.,
and then heated until the paraffin has melted. D. R. P. 201542 Chem. Zentr. 1908, ii. 1218 ;
;
The solution is filtered and the precipitate washed Bezdzik and Friedlander, Monatsh. 30, 871).
with fuming nitric acid until the filtrate dis- Anthranol has been synthesised by heating
solves in water without turbidity, and then with 1 part of o-benzylbenzoic acid with. 2
parts of
water until neutral. Finally, the paraffin is sulphuric acid at 100 (Fischer and Schmidt,
washed with alcohol, dissolved in warm ether Ber. 1894, 2789). It crystallises in colourless
and the filtrates collected in a weighed porcelain needles, m.p. 165, with decomposition. It
dish ;
the filtrates are evaporated and the dissolves in alkalis, and then behaves as its
paraffin dried at 105-110 for half an hour tautomeride anthrol (q.v.); e.g. it condenses with
(Heusler and Herde, J. Soc. Chem. Ind. 1895, benzaldehyde to form benzilidine anthrol
828). The detection of carbazole and phen- (Haller and Padova, Compt. rend. 141, 857, v.
also Bad. Anil, und Soda Fab.,D. R. P. 172930 ;
j
anthrene in the purified product is carried out j
as follows : Chem. Zentr. 1906, ii. 834). By heating the

Carbazole. Sample is extracted in cold alkaline solution of anthranol for some time, it
with ethyl acetate, solution allowed to evaporate, |
becomes oxidised to anthraquinone; hydroxyl-
and residue transferred by a few drops of same amine hydrochloride converts it into anthra-
solvent to a watch-glass. On evaporation, quinonedioxime (Nietzki and Kehrmann, Ber.
carbazole is left behind ; when treated with a 1887, 613). Anthranol yields a benzoyl deri-
drop of nitrobenzene and phenanthraquinone, vative (m.p. 164) with benzoyl chloride in
it yields characteristic small copper coloured pyridine (Padova, Compt. rend. 143, 121 ; Ann.
plates. Chim. Phys. [8] 19, 353), and a diiodide with
Phenanthrene. Sample is extracted with iodine in benzene solution (Liebermann, Glawc
benzene, and the evaporation residue treated and Lindenbaum, Ber. 1904, 3337).
with a-dinitrophenanthraquinone in nitroben- H
Dianthranol C 28 18 2 is formed, together
zene. In this case mixed crystals are obtained with a little anthraquinone, when anthranol
having the form and colour of the brown i dissolved in benzene is exposed to sunlight for
needles of the phenanthrene compound, but some weeks, or when the benzene solution is
containing a large quantity of anthracene. boiled for some hours. Colourless tabular crystals
ANTHRACENE ACID BROWN, -CHROME (m.p. 250) (Orndorff and Bliss, Amer. Chem. J.
BLACK, -RED, -YELLOW v. Azo- COLOURING 1896, 453 Orndorff and Cameron. Amer. Chera.
;
MATTERS. ,
J. 1895, 658).
ANTHRAQUINONE. 273
ANTHRAPURPURINv. ALIZARIN AND ALLIED Chem. Ind. 1909, 360, 1310). Darmstadter
COLOURING MATTERS. (Chem. Zentr. 1900, ii. 151 ; D. R. P. 109012)
C 6H 4<^J ) ^>C 6 H 4 prepares anthraquinone by the electrolytic
ANTHRAQUINONE .
oxidation of anthracene in a chromic-acid bath.

Obtained by the oxidation of anthracene with Various processes have been patented for
chromic acid (Kopp, Jahresbericht. 1878, 1188 ; purifying the crude anthraquinone thus pro-
Laurent, Ann.' Chim. Phys. [2] 60, 220 ; 72, 415 ; duced. Bronner (J. Soc. Chem. Ind. 1882,
Annalen, 34, 287 ; Anderson, Annalen, 122, 499; 1883,410; Eng. Pat. 759 ; D. R. P. 21681)
301 : Graebe and Liebermann, Annalen, Spl. 7, dissolves out the impurities on a
specially con-
285) by;
the distillation of calcium benzoate structed circular shelf. The method depends
(Kekule' and Franchimont, Ber. 1872, 908); on the continuous extraction of the impure
by the distillation of benzoic acid with product with an amount of solvent insufficient
phosphorus pentoxide ; by the distillation of to keep in solution the whole of the anthra-
o-benzoylbenzoic acid with phosphorus pentoxide, quinone and the easily soluble impurities.
or by heating it alone (UUmann, Annalen, 291, Bayer & Co. (D. R. P. 68474 ; Eng. Pat, 5539 ;
24 ;
Behr and Dorp, Ber. 1874, 578 ;
Lieber- J. Soc. Chem. Ind. 1893, 439) dissolve out the
mann, Ber. 1874, 805; Perkin, Chem. Soc. impurities with liquid sulphur dioxide ; Sadler &
Trans. 1891, 1012) ; by the dry distillation of Co. Ltd. and Driedger (Eng. Pat. 17635 ; J. Soc.
calcium phthalate (Panaotovits, Ber. 1884, 13). Chem. Ind. 1902, 1072) recrystallise the crude
Heller (Zeitsch. angew. Chem. 1906, 19, 669) anthraquinone from hot aniline.
heats 1 part of phthalic anhydride with 3-5 parts Properties. Anthraquinone, as usually pre-
of benzene and 1-8 parts of aluminium chloride pared, forms a felted mass of crystals of a pale-
in a lead vessel at 70 until the evolution of yellow or buff colour ; by sublimation it can be
hydrogen chloride ceases. After cooling, water obtained in the form of lemon-yellow needles or
is added and the excess of benzene removed by golden-yellow prisms m.p. 277 ; b.p. 379-
;
steam distillation. The solution is made 381 (corr.) (Recklinghausen, Ber. 1893, 1515);
alkaline and boiled, and then on addition of sp.gr. 1-438-1-419 (Schroeder, ibid. 1880, 1071).
*
acid benzoyl benzoic acid is precipitated. On Sparingly soluble in alcohol and ether, some-
heating this for one hour at 150, anthraquinone what more soluble in hot benzene. It is
is obtained (cf. Piccard, Ber. 1874, 1785 ; neutral in its reactions, and is insoluble in
Friedel and Crafts, Ann. Chim. Phys. [6] 1, 523 ; dilute acids or alkalis. Anthraquinone is
Miiller, J. 1863, 393). Phenyl-o-tolylketone very stable ; it is not affected by hot hydro-
gives anthraquinone on heating with lead oxide chloric acid, or by boiling with caustic potash or
or on oxidation with manganese dioxide and calcium hydroxide solutions ; it dissolves in hot
sulphuric acid (Behr and Dorp, Ber. 1873, 754 ; nitric acid (sp.gr. 1-4), and is deposited in crystals
1874, 16 ; Thorner and Zincke, Ber. 1877, 1479). on cooling or on dilution ; it dissolves unchanged
Industrial preparation. Crude anthracene hi concentrated sulphuric acid at 100, and is
(55-60 p.c.) is slowly added to a hot solution precipitated in fine crystals on pouring into
of potassium dichromate in a large wood vat water. Strongly heated with sulphuric acid,
lined with lead. The solution is kept well it is converted into mono- and di-sulphonic acids
stirred and heated with steam all the
until (v. ALIZARIN). Anthraquinone is of great com-
anthracene has been added. The steam is mercial importance, as it is used in the prepara-
then cut off and sulphuric acid is run into the tion of alizarin, quinizarin, purpurin, &c. (v.
mixture in the form of a fine spray ; the heat ALIZARIN). Fusion with zinc or treatment with
generated by the reaction keeps the solution sodium methoxide converts it into anthracene
boiling. The crude anthraquinone is then (Haller and Minguin, Compt. rend. 120, 1105) ;
separated by filtration and dried. It is dis- fusion with caustic soda converts it into sodium
solved in sulphuric acid without applying any benzoate (Graebe and Liebermann, Annalen,
heat, and, when solution is complete, transferred 160, 129), and by distilling it over lime benzene
to a large vat lined with lead and boiled with is formed reduction with zinc and caustic
;
water. The precipitated anthraquinone is at soda, or with sodium amalgam yields oxanthranol
once separated by means of filter presses Ci 4 Hi 2 and
dianthranol (Diels and Rhodius,
from the soluble compounds ; the pressed cakes Ber. 1909, 1076 Meyer, Ber. 1909, 143) ; zinc
;
are boiled with a solution of soda, and then and amyl alcohol converts it into dianthrol
again filtered, pressed, dried, and finally sub- (Meyer, Monatsh. 30, 165). Phosphorus penta-
limed (Levinstein, J. Soc. Chem. Ind. 1883, chloride and phosphorus oxychloride convert
219 ; Kopp. l.c.). Poirrier and Rosenstiehl it into trichloranthracene and other chlorinated
(Eng. Pat. 8431; J. Soc. Chem. Ind. 1887, products (Radulescu, Chem. Zentr. 1908, ii.
595) oxidise anthracene in a closed lead-lined 1032). A delicate test for anthraquinone
vessel by means of ferric sulphate. The vessel consists in reducing it with sodium amalgam in
is heated to 120-150
during 72 hours, com- dry ether. On adding a drop of water, a red
pressed air being injected into the vessel. By colouration is produced ; if alcohol is used
this means the anthracene is virtually oxidised instead of ether, addition of water gives a green
by the air, the ferric sulphate acting as a carrier colouration (Claus, Ber. 1877, 927).
for oxygen. Another process consists in the Condensation products. With phenols :
absorption of nitric oxides diluted with air, by Scharwin and Kusnezof, Ber. 1903, 2020 ; 1904,
zinc oxide, copper oxide, or a similar oxide 3616; Deichler, D. R. P. 109344; Chem. Zentr.
of low basicity. Anthracene is mixed with 1900, ii. 360. With amines Bayer & Co.
:
this,and a stream of air or oxygen is passed D. R. P. 86150, 107730, 136777, 136788, 148079 ;
through the mixture at 250-350, anthraquinone Chem. Zentr. 1902, ii. 1272 Chem. Soc. Abst.
;
being produced (Ch. Fabr. Griinau, Landshoff 1904, i. 326. Aryl ethers, aryl- and alkyl-
& Meyer, D. R. P. 207170, 215335; J. Soc. amino- derivatives Bayer & Co. D. R. P.
:
VOL. l.T. T
274 ANTHRAQUINONE.
158531; Fr. Pat. 354717, 362140; J. Soc. treatment with sodium carbonate to neutralise
Chem. Ind. 1905, 885, 1105; 1906, 752. Thio- any free acid ammonia, and sodium
; nitrii
cyanates: Bayer & Co. D. E. P. 206054 ; J. Soc. have also been recommended.
Chem. Ind. 1909, 239. Mercaptans : ibid. 469. ANTIDIABETINE. Trade name for a
1.2- and 1.4-anthraquinones have been preparation said to be composed of saccharin
pared from a-anthrol and 1.2 -anthraquinone mannite.
from -anthrol (v. Dienel, Ber. 1906, 926; ANTI-FEBRIN. A trade name for
Liebermann, Ber. 1906, 2089 Harlinger, Ber.
;
anilide H
or phenylacetamide C 6 6 'NH'COCH
1906, 3537 ; Lagodzinski, Ber. 1894, 1483 ; Discovered by Gerhardt in 1853, and investiga
1895, 1422 ; 1906, 1717). as an antipyretic by Kussmaul in 1886
ANTHRAQUINONE RED v. ALIZARIN AND ACETANILIDE).
ALLIED COLOURING MATTERS. ANTIFORMIN. Trade name for the alkaline
ANTHRARUFIN v. ALIZARIN AND ALLIED liquid prepared by adding caustic soda to a
COLOURING MATTERS. solution of sodium hypochlorite. Used as a
ANTHROL disinfectant, the active ingredient being the
CH chlorine, of which 4 p.c. is liberated on treatment
with hydrochloric acid. Solutions of sodium
hypochlorite are prepared in Germany by the
Two isomeric anthrols are known, a- or 1- electrolysis of 5 p.c. salt solution. A current
hydroxyanthracene and 0- or 2-hydroxy- of 110 volts and 100 amperes furnishes nearly
anthracene. 6000 litres daily of a disinfecting or bleaching
a-Anthrol is prepared by fusing 1-anthracene- solution containing 1 p.c. of available chlorine.
sulphonic acid with 5 parts of caustic potash at According to H. Will (Zeitsch. Ges. Brauw.
250, dissolving the mass in water, and filtering 1903, 865 ; J. Soc. Chem. Ind. 1904, 125), it is
off the yellow flocks which separate out. The one of the best disinfectants for brewery work.
crude product is recrystallised from acetic acid It rapidly softens organic impurities and facili-
and water. It forms yellow plates, m.p. 152. tates then- removal by scouring, in addition to
a-Anthrol dissolves in the ordinary solvents with its oxidising action, and it also dissolves incrusta-
a blue fluorescence, and is more soluble than tion. Its germicidal power is high, and a 5 p.c.
0-anthrol (Schmidt, Ber. 1904, 66; Dienel. solution is sufficient for most purposes. It is
Ber. 1905, 2862 ; v. also Linke, J. pr. Chem. [2] used cold, and may be safely applied to varnished
11, 227). surfaces with a brush, provided care is taken to
fi-Anthrol is prepared by fusing 2-anthracene- prevent prolonged contact.
sulphonic acid with potash and recrystallising ANTIFUNGIN. Trade name for magnesium
the crude product from acetone (Liebermann borate,employed as a fungicide.
and Hermann, Ber. 1879, 589 ; Linke, J. pr. ANTIGERMIN. Trade name for a prepara-
Chem. [2] 11, 222). It can also be obtained by tion of a copper salt of a weak organic acid,
reducing hydroxyanthraquinone with hydriodic mixed with lime. It is used as a fungicide.
acid and phosphorus (Liebermann and Simon, ANTIHYPO. A
solution of potassium per-
Ber. 1881, 123). It forms yellow plates melting carbonate, used for destroying sodium thio-
with decomposition at 200, and is soluble in sulphate in photographic negatives and prints.
the common organic solvents with a violet ANTIMONIN. Trade name for antimony
fluorescence. By reduction with sodium in calcium lactate, used as a tannin-fixing mordant.
alcoholic solution, dihydroanthrol is obtained ANTIMONITE. Native antimony sulphide
(Bamberger and Hoffmann, Ber. 1893, 3069), (v. ANTIMONY).
and by heating with acetamide at 280 anthramin ANTIMONY. (Antimoine, Fr. ; Antimon,
is obtained.Azo- dyestuffs have been obtained Ger.) Stibium. Sym. Sb. At. wt. 120-2.
from 0-anthrol (Act. Ges. f. Anilinf. D. R. P. Occurrence. Antimony occurs native in
21178; Frdl. i. 538). small quantities, occasionally in rhombohedral
ANTIAR RESIN or UPAS ANTIAR. A crystals, at Andreasberg in the Hartz, Przibram
green resin which exudes from the upas tree in Bohemia, Sala in Sweden, Allemont in France,
(Antiaris toxicaria (Lesch.), order Maracese). in the United States, New South Wales, and
Light petroleum and benzene extract from it a Quebec. It occurs in large masses in Sarawak,
substance analogous to caoutchouc, a fatty Borneo.
matter, and two resinous substances ; alcohol Combined with oxygen as the sesquioxide
extracts from the residue a very poisonous Sb 2 3 it occurs in antimony bloom, white anti-
,
glucoside, antiarin (De Vrij and Ludwig, J. pr. mony, or valentinite, and in senarmontite, being
Chem. 103, 253). found hi workable quantities in the Algerian
ANTIARIN v. GLUCOSIDES. province of Constantine. In antimony ochre
ANTI-CHLOR. Linen and cotton fibres and or cervantite, and in stibiconite and volgerite, it
paper pulp are apt to retain some free chlorine occurs as antimonite of antimony Sb 2 4 .
from the hypochlorite used in bleaching, and Combined with sulphur, it occurs as stibiiiie,
as this causes the material to rot slowly, the antimonite, or grey antimony ore Sb 2 S 3 In
.
manufacturers use certain reagents known as union with sulphur and oxygen together, it
' '
anti-chlors to remove the last traces of forms red antimony, antimony blende or ker-
chlorine. The first substances employed were mesite Sb.,O 3 2Sb,S 3 .
the neutral and acid sulphites of soda (sodium With arsenic, antimony is found in atte-
sulphite and bisulphite) ; these were superseded montite or arsenical antimony. With sillier,
in 1853 by sodium hyposulphite, which is now in discrasite.
very largely employed. Calcium sulphide, made With sulphur and metals, antimony forms a
by boiling milk of lime with sulphur stanuous ; number of sulphantimonites, among which may
chloride hi hydrochloric acid with subsequent be mentioned zinkenite, jamesonite, boulanyerite,
ANTIMONY. 275
and feather ore, containing antimony, sulphur, The method of liquation in
reverberatory
and lead miargyrite, pyrargyrite, and stephan-
;
furnaces is used in some places where ore can
ite, containing silver ; berthierite, containing be mined cheaply but fuel is dear. The con-
iron, and antimonial copper glance. Antimony sumption of fuel per unit of sulphide liquated is
is found in certain ferruginous waters. least with this type of furnace, but there is a
The antimony minerals of commercial im- considerable loss of antimony by volatilisation.
portance as ores are stibnite, and the decomposi- This loss, however, can be prevented by the
tion products which are usually associated with use of suitable condensing apparatus such as
it and sometimes entirely replace it, viz. kerme- Herrenschmidt's (v.i.).
site, valentinite, senarmontite, and cervantite. In any process of liquation the temperature
ores occur in workable quantities
Antimony must be carefully regulated, as too low a tempera-
in Mexico, California, North America, Canada, ture results in a low yield of sulphide, the
Australia, Japan, Borneo, Cape of Good Hope, residues containing too much antimony, while too
New Zealand, Asia Minor, Algiers, Italy, Spam, high a temperature increases the loss by volatili-
Portugal, Corsica, and Sardinia. Small deposits sation.
of antimony sulphide have been discovered in Ores of class (6) are either roasted to the
Cornwall, Cumberland, and Scotland. non- volatile tetroxide, or to the volatile trioxide,
The veins in which stibnite is found are or are subjected to one of the direct reduction
usually 4-6 inches in width, but in some rich processes.
mines, as in Nevada, they are several feet across. The oxidation of the sulphide to tetroxide
The gangue materials are quartz, with some takes place at temperatures between 350 and
brown-spar and heavy spar, and from these 400 in presence of excess of air. If the ore is
the sulphide can only be separated by hand- impure, antimonates of the metallic impurities
picking or liquation. It is occasionally found are formed at the same time. During the roasting
in pockets, when it is usually very pure. there is a great tendency for the ore to frit, and
By far the most general ore of antimony is this necessitates the constant rabbling of the
the sulphide, but in some cases, as in Algeria, the charge. The presence of gangue renders the
oxide is found in workable quantities, and in other ore less liable to fuse, so that the process is most
cases both oxide and sulphide occur together. easily carried out with poor ores, e.g. ore-dust,
Extraction. Metallic antimony and its com- for the treatment of which it is largely used.
pounds are nearly always extracted from the The furnaces employed are of two classes :
ores by dry methods. According to their (a)Rabble furnaces, having an egg-shaped

suitability for the several methods of treatment, flat bed, with a furnace on either side and a
the ores fall into two broad classes :
working door at the front. With these the
(a) Sulphide ores containing over 40 p.c. process is intermittent.
"
stibnite. (b) Fortschaufelungsofen," in which the
(b) Sulphide ores containing less than 40 p.c. roasting is carried on continuously. These fur-
of the sulphide, and oxide ores of any grade. naces are 40-45 feet long, by 8 feet high, by 2 feet
In this class also may be included liquation wide, and have 10 working doors on each side.
residues and flue deposits, &c. The ore is charged in at one end, and is then
Preliminary treatment of ores. Ores of gradually worked along the bed during about
used for the production of the metal
class (a) are 40 hours, and finally discharged at the other
by the English process. If the content of end. Fresh ore is continually charged into the
sulphide is over 90 p.c., the ore requires no furnace at the rate of 6 cwts. every 8 hours.
preliminary treatment, but less pure ore is The oxidation of the sulphide to volatile
subjected to a process of liquation, in which the trioxide takes place at about 400 with a
sulphide is melted and allowed to run away carefully regulated amount of air. This pro-
from the gangue. cess, provided suitable condensation apparatus
The following method of liquation was is installed, presents marked advantages, and is
formerly used where fuel is plentiful, as at finding an increasing application, especially in
Malbosc, in the Department of Ardeche, Wolfs- dealing with poor ores. It may be noted that
berg in the Hartz, and in Hungary. The ore was arsenic is completely separated as the more
placed in small lumps in a number of conical volatile trioxide, that any gold or silver present
pots of 45 kilos, capacity, each perforated below is left hi the residues and can afterwards be
and standing on a perforated plate over a sunken extracted, that there is no loss of antimony,
receiver. The pots were surrounded by fuel and that the consumption of fuel is low. Many
which continued to burn for 10 hours, the melted different forms of plant have been used for
sulphide collecting in the receivers. this process, but in most the roasting takes
At La Lincouln, Wolfsberg, and Haute Loire, place in a cupola or reverberatory furnace.
the pots were contained in a reverberator} 7
The earlier forms of condensing apparatus are
furnace. AtSchmollnitz, in Hungary, the of two classes :
melted sulphide ran through channels into (a)In which the vapours are passed through
receivers outside the furnace. a series of flues and chambers and finally through
At
Malbosc, the pots are replaced by cylin- water-tanks in which the last traces of oxide are
drical tubes, perforated below and
standing on deposited.
similarly perforated plates above the receivers. (b) In which the furnace gases
are cooled
Each cylinder has a capacity of 500 Ibs. of ore, below 100 in flues and then filtered through
four being heated in one furnace. Each has a canvas or other coarse fabric (v. Chatillon, FT.
hole at the side, Pat. 189974, 1888; and 382504, 1907; Wool-
through which the residues are
removed, these holes being closed during the ford, Fr. Pat. 200245, 1889 Plews, U.S. Pat.
;
heating. The receivers are of clay, or of iron 704367, 1902). Herrenschmidt has patented a
coated with clay.
complete plant for this process (Fr. Pat. 33330G,
T 2
276 ANTIMONY.
1903, and 386107, 1908), which differs materially charcoal and 0-5 part of potash, or part
from any earlier apparatus. charcoal saturated with a concentrated solution
The roasting furnace is partly of brick and of sodium carbonate, and fused in a covered
partly cast metal, and is provided with a hopper crucible at a low red heat, and poured into a
through which the ore, mixed with 4-5 p.c. of hot mould. 100 parts of sulphide yield 44 parts
gas-coke or 6-7 p.c. charcoal, is introduced. of antimony. The slag which rises above the
The gases pass from the furnace into a chamber, metal consists of alkaline carbonate mixed with
and then through a series of cast-iron tubes double sulphide of antimony and potassium or
placed nearly vertical and air-cooled, in which sodium with charcoal, and is known as crocus
the main portion of the trioxide is deposited. of antimony. The action of the charcoal in
The last traces are removed by forcing the gases this reduction consists in the removal of the
up a tower filled with coke over which water oxygen from the antimony oxide, producing
flows. The draught is maintained by two metallic antimony, and in the reduction of a
centrifugal fans, working tandem. It is stated part of the alkali. The alkaline metal thus set
that 6 tons of ore, containing 10-1 5 p.c. antimony, free combines with the sulphur of a part of
can be treated in 24 hours, with a yield of over the antimonious sulphide, freeing an equivalent
90 p.c., and that the cost of producing 1 ton of quantity of the antimony and forming a double
oxide is 70 francs. sulphide of antimony and potassium with a
Smelting of the metal. Antimony is prepared further quantity of the sulphide.
from crude antimony ' or high-grade stibnite
'
The sulphide may also be reduced by fusing
' ' ' '
ores by the English or precipitation method. 8 parts of sulphide Avith 6 parts of cream of
The ore, of which the composition has been tartar in a crucible heated nearly to redness,
determined by analysis, is ground under edge- then adding 2 or 3 parts of potassium nitrate,
runners to the size of a hazel-nut, or smaller, and fusing until perfectly liquid ; or 8 parts of
and is subjected to three operations :
sulphide are mixed with 6 parts of cream of
Singling. This process is carried out in tartar and 3 parts of nitre, and are thrown in
crucibles of which about forty are arranged in a portions into a red-hot crucible and heated until
double row on the hearth of a long reverberatory perfectly fluid. By quietly fusing, with frequent
furnace having a grate at each end, and a flue, stirring to prevent frothing, a mixture of 8 parts
leading to condensing chambers, in the middle. sulphide, 1 part sodium carbonate, and 1 part
The about 20 inches high and 11
crucibles are charcoal, 66 p.c. of metal is said to be obtained
inches across, and are made of a mixture of from the sulphide.
6 parts fire-clay and 1 part plumbago. The It is possible also to reduce the sulphide on
charge for each pot is 42 Ibs. ore, 16 Ibs. iron the hearth of a reverberatory furnace. The
(of which about 2 Ibs. is in the form of turnings, partially roasted ore, which contains the sulphide
and 14 Ibs. as tin-plate cuttings beaten into a and oxides of antimony, is mixed and fused with
' '
ball), 4 and 1 Ib. slag from doubling
Ibs. salt, 8-13 p.c. of coal and 9-11 p.c. of soda, fre-
(v.i.). These materials are introduced into the quently with the addition of iron, in which case
red-hot crucible, and kept in a state of fusion for the slag produced is much less fusible and does
2-3 hours, at the end of which time the contents not entirely cover the bath of metal ; the anti-
are poured into moulds, and the antimony is mony produced also contains much iron (Dingl.
removed from beneath the slag. The product, poly. J. 162, 449). Where carbonate of soda is
known as singles, usually contains about 91 p.c. used for the fusion the mass froths considerably
antimony. and attacks the furnace hearth. .
Doubling is carried out in crucibles arranged The metal is prepared from either of the
in a furnace as previously described. The oxides by one of the numerous reduction pro-
charge for each pot is 84 Ibs. broken singles, cesses now in use.
78 Ibs. liquated sulphide, and 4 Ibs. salt, and (a) Reduction in reverberatory furnaces is
the fusion, which takes about \\ hours, is carried out at Bouc, Septemes, New Brunswick,
closely watched, the Avorkmen judging from the &c. The furnace-bed is egg-shaped, deep in
nature of the slag when the operation is complete. proportion to its width, and is provided with a
The slag is then removed with an iron ladle, tap-hole at the lowest point. The furnace gases
and the metal run into moulds. This product are passed through a long series of condensing
is called bowl metal or star bowls. chambers. First 90-110 Ibs. flux (chiefly salt,
Frenching, or melting for star metal (t>.i. under with some soda and sodium sulphate) and
Refining). 220-230 Ibs. of slag from a previous operation
In the English process the loss due to are melted on the hearth, and then 400-500 Ibs.
slagging and volatilisation is small, being of roasted ore and 67-75 Ibs. of charcoal are added,
only 2-5 p.c. and the whole kept in a state of fusion till
The sulphide may be mixed with half its reduction is complete. At New Brunswick the
weight of charcoal to prevent caking, and roasted reduction and refining are carried out conse-
at a gentle heat, the heat being gradually in- secutively in the same operation.
creased, but not to melting, Avhereby large (b) Some French smelters reduce an oxidised
quantities of sulphurous acid, arsenious oxide ore containing 3040 p.c. of antimony in a
and antimonious oxide are evolved, the two latter 3-tuyered shaft furnace at the rate of 2-2 tons
being collected in flues. 20 p.c. of the antimony per 24 hours, with the consumption of about
is stated to pass off in this
operation, the greyish half that weight of coke. The regulus contains
or red mass which remains consisting of anti- 92-95 p.c. of antimony, and is subsequently
mony tetroxide containing about one-sixth of refined.
its weight of the trioxide and some sulphide. At Banya, Hungary, antimony ores are
This residue, known as antimony ash, is mixed mixed with sih'cious material and smelted in a
with 0-5 part of cream of tartar, or 1 part blast-furnace for impure regulus, which is then
ANTIMONY. 277
refined in a reverberatory furnace. The blast- All these impurities, except lead, can be
furnace used is a round stack 6 m. high and 1 -4 m. removed by slagging with oxidising, sulphurising,
diameter at the throat. The hearth, which is or chlorinating agents. The usual fluxes are :
1 m. across, is fitted with five water-jacketed Glauber salt and charcoal, which remove copper
tuyeres, and has two outlets for slag and metal and iron as sulphides, and arsenic as sodium
respectively ; a third opening is used for blowing arsenate ; and antimony glass (antimony
out. A
blast of 15 c.m. per minute is used, and oxysulphide) which eliminates sulphur. Chlor-
the gases are collected by a tube at the throat ides, such as salt or carnallite, must be used
and passed through a condensing apparatus. with caution, or great loss by volatilisation may
Such a furnace will run for 3 weeks continuously, result.
smelting about 20 tons of material daily (Berg. Refining in crucibles finds its chief application
u. Hiitt. Zeit. 1886, p. 102). in the English process. The ' star bowls (v.s. )
'
(c) Reduction in crucibles is only used when are cleaned from slag by chipping with sharp
rich ore or the trioxide is available. The hammers, and the metal is then broken small
reducing agent is carbon (charcoal or anthracite), and melted with 2-3 p.c. of antimony flux, pre-
and sodium sulphate and carbonate are added to pared by melting together American potashes
form a slag. and powdered stibnite in varying proportions
Considerable quantities of antimony ore are (approximately 3 parts potashes and 2 parts
now treated directly for the production of the stibnite) until, by experiment, the correct com-
metal. One such process which has been success- position is found. The refining is carried out
fully used for some time depends on the reduction in the pots nearest the grates, and takes 30
of the sulphide in a bath of molten ferrous sul- minutes to 1 hour, the charge for each crucible
phide containing iron (v. T. C. Sanderson, U.S. being 84 Ibs. The finished product is run into
Pat. 714040, 1902 ; Cookson, Fr. Pat. 324864 8-lb. ingots, which are carefully surrounded with
1902 and Herrenschmidt, Fr. Pat. 296200, 1900).
; slag and allowed to cool without disturbance.
Another method consists in the reduction of The coal consumption is large, but is com-
the sulphide with carbon in water- jacketed pensated by a much smaller loss by volatilisation
blast-furnaces. This has been used by Bering than occurs in other processes.
for the treatment of liquation residues. Refining in reverberatory furnaces is used at
Germot (Revue des Produits Chemiques, Milleschau. Banya, Siena, and Oakland. It is
Dec. 15, 1907) and Herrenschmidt (Fr. Pat. imperative that the bed of the furnace should
333340, 1903) have used converters for the be tight and able to withstand the action of the
smelting of sulphide ores. alkali flux, and this is best attained by making
Methods of treating antimony ores have also it of one solid piece of soft, weathered granite.
been proposed by which the antimony is con- A fairly good substitute for the granite is a
verted into the volatile chloride, as in Lyte's mixture of burnt and raw clay well rammed into
process of roasting the ore with salt. The ore an iron box. An example of such a process is
may also be subjected to the action of hydro- that recommended by Helmhacker and used at
chloric acid gas in a reverberatory or muffle Milleschau (Berg. u. Hiitt. Zeit. 1883, 191 ; and
furnace, the volatilised chloride being condensed Dingl. poly. J. 250, 123).
in a solution of hydrochloric acid (Dingl. poly. J. A glass of antimony is prepared by fusing
'
'
250, 79-88, and 123-133). a mixture of the crystalline antimony oxide

Among processes allied to the smelting of which collects on the hotter portions of the flues
antimony there need only be mentioned that of with sulphide of antimony, until it forms a
this is mixed
Herrenschmidt for the extraction of gold from glassy dark grey or brown mass ;
antimony (Fr. Pat. 350013, 1904). This de- with the carbonate for the purification of the
pends on the fact that when a small quantity metal, and is occasionally used alone where the
of antimony is melted with or reduced from metal is but slightly impure
auriferous stibnite, all the gold present in the The bed of the furnace is heated to a cherry
sulphide passes into the metal. red and 600 to 700 kilos, of crude antimony
Many proposals have been made for the ex- placed on it a quantity of oxide
;
and some
traction of antimony by wet or electrolytic arsenic escape, and in from 30 to 60 minutes the
methods, but they have not been a success metal has run down. From 3 to 7 p.c. (according
commercially. Reference may be made to to the purity of the metal) of carbonate of soda,
Hering (Dingl. poly. J. 230, 253), and Borchers sometimes mixed with coal or coke, is then added.
(Electrolytische Gewinnung des Ant. Chem. Zeit. The metal is thus covered and fumes less, small
xi. 1883, 1023). jets of flame appearing occasionally
on its sur-
face ; the temperature is raised, the metal
3 hours
Refining of Antimony. remaining under the slag for from 1 to
then
Unrefined antimony contains sulphur, iron, (determined by the workman), the slag
arsenic, and sometimes copper and lead. The becomes thick, and is removed by drawing it
through the door with a long-handled
flat
following analyses show the composition of
typical samples, I. and II. being metal made transverse iron.
with scrap iron, the arsenic and gold
being due Three p.c. of antimony sulphide and 1J p.c.
to admixed pyrites; III. and IV. metal from of oxide are then thrown on the surface of the
of
roasted ore smelted in a blast furnace: metal, and when melted 4 p.c. carbonate
carbonate of potash
I. II. III. IV. potash, or of a mixture of
Antimony . 94-5 84-0 97-2 95-0 and soda, are added. By this means the iron
Iron . . 3-0 10-0 2-5 4-0 and last traces of are removed; in
sulphur
Sulphur . 2-0 5-0 0-2 0-75 less is complete, and
than 15 minutes the refining
Arsenic . 0-25 1-0 0-1 0-25 the operation of ladling
critical is performed.
Gold . . traces A cast-iron hemispherical ladle, holding 15-20
278 ANTIMONY.
riveted to a chain hanging from the
kilos., is with 1st, potassium carbonate
; 2nd, potassium
roof exactly in front of the working door, before nitrate ; 3rd, antimonic oxide
; 4th, potassium
which the cast-iron moulds for receiving the carbonate (Th. Martins, Kastn. Arch. 24, 253),
metal are arranged on a stone table. The work- or by fusing three times with fresh
portions of
man dips his ladle obliquely, removing some slag sodium or potassium nitrate.
with the metal ; part of this is first poured Duflos (Kastn. Arch. 19, 56) recommends a
into the mould to prevent the metal from process in which the arsenic is driven off as
actually touching the mould, and the metal is fluorideby means of sulphuric acid and fluorspar.
well covered with the slag and left at rest. (See further Schw. 42, 501 ; also Buchner and
'
Unless this be done the ' starring will be im- Herberger, Repert. 38, 381, 256.)
perfect, and, as this is considered a test of purity, Pure antimony may be obtained by heating
its value will be lowered in the market. The tartar emetic to low redness and digesting the
slag may generally be used again. The oxide resultant mass in water to remove the potassium.
condensing in the flues is removed as seldom as The powder thus obtained may then be dried
possible, as this operation, as well as the furnace and fused into a button.
work, is very injurious to the workers.
The cost of refining 100 kilos, of regulus is Tests for Impurities in Antimony.
from 4 to 5 shillings. Sulphur. The powdered metal evolves sul-
Star antimony usually contains small phuretted hydrogen gas (which blackens lead
amounts of iron, lead, sulphur, and arsenic, but paper) on heating with strong hydrochloric
can be further purified by Liebig's method, acid.
which consists in fusing the metal successively Potassium or sodium. The metal is greyish
with 12 p.c. sodium carbonate and 6 p.c. anti- and loses its lustre on exposure to air ; it has an
mony sulphide, and again with sodium carbonate alkaline taste and reaction, and evolves hydrogen
to which a little nitre has been added. on immersion in water.
Unlike many other metals, antimony carries Arsenic. If deflagrated with J its weight
When
'
on its face its own character for purity. of sodium nitrate, boiled with water and filtered,
' ' '
pure,' a beautiful fern leaf or star appears the arsenic enters into solution, leaving the
upon its surface, ' and 'according to the length antimony behind the solution is saturated with
;
and form of this star on the ingot its quality sulphuretted hydrogen (if an orange precipitate,
is determined. The presence of a relatively consisting of antimony sulphide, falls, this must
small percentage of impurities in the metal will be filtered quickly ; it is due to the presence of
'
prevent it from starring.' It is this peculiar a trace of antimony in the solution). The
characteristic of pure antimony to crystallise on arsenic is deposited as the lemon-yellow sulphide
the ingot in the fern-leaf or star form when on standing.
'
cooling, which originates the trade term of star Lead and copper. The metal is powdered
'
antimony for good quality of antimony. and treated with dilute nitric acid, evaporated
For pharmaceutical purposes it is important nearly to dryness, taken up with water and
to prepare antimony quite free from arsenic. filtered the addition of sulphuric acid precipi-
;
This may be accomplished by Wohler's method. tates white lead sulphate, and the addition to
A mixture of 4 parts powdered commercial the filtrate of potassium ferrocyanide gives a
antimony, 5 parts sodium nitrate, and 2 parts brown precipitate in presence of copper.
sodium carbonate (to prevent the formation sulphur as well as lead be present in the
If
of insoluble antimony arsenate) is thrown into antimony, the lead is converted at once into
a red-hot crucible. Combustion takes place sulphate by the action of nitric acid, the residue
quietly, the mass is pressed together and more on evaporation is digested with yellow am-
strongly heated for half an hour, so as to become monium sulphide, which dissolves the antimonic
pasty without fusion, being pressed down as it oxide and leaves black lead sulphide.
risesfrom evolution of gas. While still hot Iron. The powdered metal is ignited with
and soft, it is removed, reduced to powder, and three parts nitre and washed with boiling water,
boiled with frequent stirring in water, the finer the residue is boiled with hot dilute hydrochloric
powder is poured off with the water, and the acid ; on the addition of potassium ferrocyanide
residue again treated, the washings being mixed a blue precipitate is produced.
with that first obtained. The water, which con- When antimony containing arsenic and iror
tains the whole of the arsenic but no antimony is heated on charcoal, it
gives a garlic odour an
(Meyer), is removed from the insoluble portion becomes coated with oxide of iron ; it ceases
by subsidence, decantation, and filtration. The burn on removal of the flame, and yields a di
residue of sodium antimonate should be white, surface and yellow oxide (Liebig). The pi;
but the presence of lead imparts a yellow colour. metal under such circumstances burns brilliant
It is dried and fused with half its weight of cream and becomes coated on cooling with whit
of tartar at a moderate heat, cooled, broken into crystals of the oxide.
small lumps, and the potassium and sodium Detection of antimony. When fused on cha
removed by digestion in water. The powdered coal with potassium cyanide or sodium carbonat
metal is then fused into a button. or a mixture of the two, antimonial compounc
This method may be used quantitatively for produce a brittle white bead of metallic antimonj
the separation of antimony from arsenic. If the with white fumes and a white incrustation on
sodium nitrate be replaced by potassium nitrate, the charcoal ; the bead leaves a white reside
a portion of the antimony will enter into solu- on treatment with nitric acid, which is soluble
tion with the arsenic as potassium antimonate in cream of tartar or tartaric acid. Sulphide
(v. C. Meyer, Annalen, 46, 236 Chem. Zentr.
; antimony melts readily in the candle flame.
1348, 828). Arsenic may also be completely A delicate confirmatory test, given bj
removed by fusing the antimony in succession Crookes, is to add to the white incrustation or
ANTIMONY. 279
the charcoal one drop of ammonium sulphide, mony trioxide or any antimonious
compound
when the formation of the orange sulphide is is dissolved in a solution of tartaric acid, neutra-
conclusive evidence of the presence of antimony. lised with sodium carbonate, treated with a
Estimation of antimony. -Fire assay. In cold saturated solution of sodium bicarbonate
valuing ores containing the sulphide the ore is in the proportion of 10'c.c. to each 0-1
gram
broken into pieces about to 1 inch diameter, SbjOg, and quickly titrated with JV/10-iodine
and from 2000 to 7000 grains of the lumps solution, using starch as indicator.
(avoiding dust), according to the probable rich- (c) Electrolytic. Classen and others havo
ness of the ore, are selected. A Hessian crucible shown that if
antimony sulphide (v.s.) is dis-
with a hole at the bottom covered with a piece solved in the minimum amount of concen-
of charcoal, is placed within another crucible trated solution of sodium sulphide, and treated
of such size that the upper one enters about 1 with excess of sodium sulphite, or, better,
inch. The ore, mixed with charcoal of about potassium cyanide solution (to destroy poly-
equal quantity and size, is placed in the upper sulphides), the liquid can be successfully electro-
crucible, covered with a layer of charcoal and lysed in the cold with a current of 0-25-0-5 amp.,
luted down. Heat is then applied, the lower using a platinum dish as cathode. The process
crucible being below the furnace bars and sur- takes about 12 hours, and gives a good coherent
rounded by ashes to keep it cool. The heat deposit of metal which can be washed with
should be maintained at a cherry red, but not water, alcohol, and ether, and finally dried and
higher, for from 1 to 1 hours. On cooling, the weighed.
regulus is removed from the lower crucible and
weighed. It should be well fused, bluish-grey, Properties of Antimony.
and of bright fibrous crystalline fracture, the Antimony is a lustrous, bluish-white metal,
residue in the upper crucible should be examined which has a coarsely laminated or granular
to see if it is free from visible sulphide. As the structure, according as it has been slowly or
sulphide contains 71-8 p.c. of antimony, the quickly cooled. By partial solidification it
percentage of available antimony in the ore may can be obtained in obtuse rhombohedra,
be roughly calculated. approximating to cubes.
The fire assay of an ore for metallic antimony The sp.gr. of the metal is 6-72-6-86. It
is carried out as follows : If the ore contains melts at 630 -5C. (Heycock and Neville, Chem.
sulphide, it is roasted to oxide at the lowest Soc. Trans. 1895, 186), and boils at about 1350
possible temperature in a scarifier. Oxide ores in a current of hydrogen. Antimony has a
need no preliminary treatment. The charge is hardness of 3-3-5, and is so brittle that it can
made up of ore, 10 grams ; sodium bicarb., 25 readily be powdered. It is a bad conductor of
grams ; argol, 5 grams ; salt to cover ; and is heat and electricity.
heated carefully in a clay crucible for the shortest The most important physical property of
time and at the lowest temperature that will antimony is that of expanding on solidification,
ensure complete reduction. The resulting me- a property possessed also by its alloys. At
tallic button is cleaned by washing, and weighed. the ordinary temperature it is not acted on by
Wet assay. (a) Gravimetric. The antimony the air, but oxidises quickly on melting, and
is obtained in solution as antimonate or anti- burns at a red heat, producing white fumes of
monite, and hydrogen sulphide is passed into the the trioxide. It is oxidised by nitric acid of
cold liquid for 20 minutes. Then, without various strengths, dilute acid producing princi-
stopping the current of gas, the solution is heated pally the trioxide, and the concentrated acid
to boiling, and the gas allowed to pass for another producing the pentoxide (H. Rose, Analyt.
15 minutes. The resulting precipitate of sul- Chem. 1, 258). Dilute sulphuric and hydro-
phide may then be subjected to one of two chloric acids are without action on it, but the
methods of treatment. It may be collected strong acids produce the sulphate and chloride
on a Gooch crucible, washed with hot dilute respectively. When fused with borax or other
acetic acid saturated with hydrogen sulphide vitrifying material, it imparts to them a yellow
and heated to constant weight at 230 in a colour.
current of carbon dioxide. Or the precipitate Antimony combines directly with the halo-
may be collected on a filter, washed successively gens Avith evolution of light and heat, and also,
with hot water, alcohol, equal parts alcohol at a higher temperature, with the elements of
and carbon disulphide, alcohol, and, finally, the sulphur group, and with phosphorus and
ether, and then dried. The greater part of the arsenic. The element occurs in three modifica-
precipitate is transferred to a watch-glass, and tions :
(1) the crystalline or ordinary form
that still adhering to the paper is dissolved in a described above (2) an amorphous yellow
;
little hot ammonium sulphide, and the solution modification, soluble in carbon disulphide, which
allowed to run into a weighed porcelain cru- is produced by the action of oxygen on liquid
cible. This is then evaporated to dryness, the stibine at 90; and (3) the amorphous ex-
main portion of the precipitate added, and the the
plosive antimony, which is best prepared by
whole treated with fuming nitric acid and action of a weak constant electric current on a
warmed, the crucible being covered with a I
concentrated acid solution of antimony tri
watch-glass. When the violent action has sub- chloride, the strength of current bearing a con-
sided, the contents of the crucible are evaporated stant relation to the surface of deposition, not
to dryness, again treated with nitric acid, and less than inch
grain being deposited per sq.
finally evaporated to dryness and heated to per hour. Thus produced, it is bright
and steel -
redness till the weight is constant. The anti- like in appearance, with an amorphous frac-
mony is then weighed as tetroxide. ture, and sp.gr. 5-78. When heated to 200,
(b) Volumetric. The most important volu- or struck or scratched, it rapidly changes into
metric method is that of Mohr, in which anti- the crystalline form, increasing in density, with
280 ANTIMONY.
the production of .great heat. Antimony tri- mony, is also used, under the name of hard lea
chloride is always contained in the metal to the in lead pipes, for making pumps and taps fc
extent of 4-8-7-9 p.c., and is given off when raising acid in alkali works, in the manufacture
the form changes. It is probable that this of cannon-balls and shot, and for the emery
substance is a solid solution of an antimony wheels and tools of the lapidary.
Tin forms numerous useful alloys with anti-
halogen compound in an allotropic form of
antimony, and that the explosion consists in the mony, especially with the addition of other
rapid transformation of the latter into the stable
metals. Common Britannia metal consists
form. The change is accompanied by an evolu- of tin 140, copper 3, antimony 9. Britannia
tion of heat amounting to 20 cals. per gram. metal for castings : tin 210, copper 4, antimony
Cohen and others (Zeit. physikal. Cheni. 1904, 12 ; ditto for lamps : tin 300, copper 4, antimony
47, 1 ;1905, 50, 291 ; 52,' 129) have shown
15. The best Britannia metal contains tin 90,
that this change goes on slowly when explosive antimony 10, lead and bismuth being carefully
excluded. Copper also is never added except
antimony is preserved.
Antimony is precipitated as a fine powder by
for the production of colour. The exact pro-
the action of zinc on an acid solution of an portion of antimony used depends on the quality
of the tin, and is always ascertained experi-
antimony salt. In this form it is sold as iron
'
'
'
black for producing an appearance of polished mentally. Increasing the proportion of anti-
steel on papier mache, plaster of Paris, and zinc mony raises the m.p., increases the hardne
ornaments. and decreases the malleability of the alloy.
Brass can be covered with a fine lustrous Good alloys take a brilliant polish, and show
fine-grained, jagged fracture. The presence
coating of antimony by dipping in a hot mixture
of 1 part tartar emetic, 1 part tartaric acid, 3 or arsenic in the antimony diminishes the ductilitj
4 parts powdered antimony, 3 or 4 parts hydro- of the product (v. BKITANNIA METAL). Superic
chloric acid, and 3 parts water. pewter is made by fusing together tin 12, copi
It may be deposited electrolytically on brass 1, antimony 1.
or copper by using a bath of the double chloride Metal argentum contains tin 85-5, antimor
of antimony and ammonia acidulated with 14-5.
hydrochloric acid. Ashljury metal : tin 77-8, zinc 2-8, antimor

19-4. Ships' nails, tin 3, lead 2, antimony 1.
Alloys of Antimony. Minofer is tin 68-5, antimony 18-2, copj
Antimony alloys with most of the heavy 3-3, and zinc 10.
metals and with the alkaline metals. It Bearing or anti-friction metal usually contaii
generally increases the fusibility, brittleness, and antimony, tin, and copper, but the compositic
hardness of the metals with which it is com- is very variable, and some cheap varieties cor
bined, and imparts the valuable property of sist chiefly of iron or zinc. Occasionally le
expanding on solidification, thus producing very and tin or lead and
zinc are alloyed with anti-
fine impressions. The alloys of silver, gold, and mony to form bearing metals. As the nar
lead with antimony have a greater density than indicates, it is used for machinery
bearings, beir
the mean of the constituents, while those of especially suitable for light loads at high speec
iron, tin, and zinc are of less density. The As examples of these alloys the following maj
sharpest impressions are produced when any of be given :
these alloys are cast at a low temperature ( J . Antimony Tin Copper

Soc. Chem. Ind. 1, 982). The castings are Babbit's metal . 8-3 83-3 8-3
usually made in brass moulds coated with Very hard bearings . 5 2 -5 Iron 7C
lampblack and turpentine. Cheap bearings . . 1-7 7 Zinc i
With lead, antimony mixes readily in all U. S. Rly. Babbit metal 7-4 88-9 3-7
proportions. By the addition of antimony to German Rly. Babbit
red-hot lead, alloys which crystallise in rhom- metal . 11-1 . . 88-3 5-6
bohedra have been obtained by F. de Jussieu Copper. The presence of 0-15 p.c. of anti-
(Oompt. rend. 38, 1321-1322). An alloy of mony renders copper both cold and hot short.
equal parts of lead and antimony is very brittle, With varying proportions of the two metals,
and rings when struck. Nasmyth has recom- shades from pure copper-red to rose-red, crimson,
mended the addition of 5 p.c. antimony to lead and violet may be obtained, the last when
for use instead of bronze in taking casts of equality is reached. Two definite compounds of
works of art (Athenaeum, No. 1176, 511). copper and antimony appear to exist, viz. SbCu,,
Type metal is essentially an alloy of lead and a violet alloy known as Regulus of Venus,' and
'
antimony, frequently with addition of tin and SbCu 4 (Kamensky, Phil.

Mag. [5] 17, 270; v.
containing less frequently bismuth or copper. also Ball, Chem. Soc. Trans. 1888, 167).
A few examples of common type-metals are :
Antimony is frequently added to brass to
Bis- heighten its colour. These alloys are harder and
Lead Antimony Tin Copper muth finer in texture than copper or brass, and take a
Type metal .55 30 15 better polish. Antimony is sometimes added
. 70 18 10 2 for this reason to the material for concave
. 50 28 22 mirrors. It is also added occasionally to bell
85-7 14-3
Stereotype plate metal, as it is believed to add to the intensity
. 70 15 15 and clearness of the sound. Many celebrated
Linotype metal 84-5 13-5 2 old bells contain antimony, e.g. ' Old Tom o"
'
Wetterstedt's patent ship sheathing consists Lincoln, which contains about 0-03 p.c.
of 100 lead to about 3 antimony, but does not Zinc. Antimony forms definite crystalline
appear to have been used to any extent. The compounds with zinc, which, however, differ
alloy, containing varying proportions of anti- widely in composition while retaining the same
ANTIMONY. 281
form. They decompose water rapidly at the pellets for cartridges, in pyrotechny and in
boiling temperature, and this action is promoted veterinary surgery.
by the presence of traces of platinic chloride. Kermes mineral. Brown-red antimony sul-
Cooke has suggested the suitability of this phide. Pulvis Carthusianorum. Sulph. stibia-
reaction for the preparation of pure hydrogen. turn rulirum.
Iron containing less than J p.c. of antimony Kermes mineral usually consists of a mixture
is both hot and cold short. A mixture of 7 parts of the trisulphideand trioxide containing alkali.
antimony and- 3 parts iron heated to whiteness Berzelius and Rose state that some samples
with charcoal forms a hard white alloy which examined by them consisted of a true double
strikes sparks with steel. sulphide of potash and antimony.
Alloys of antimony and aluminium have been Preparation. Fuchs asserts that if antimony
described by Pecheux (Compt. rend. 138, sulphide is heated and suddenly cooled in water
1606), which vary in composition from SbAl 30 it yields an orange-red, less dense powder of
to SbAl 40 having a density of 2-73-2-60, and
. kermes. A. Ditte (Compt. rend. 102, 212) does
m.p. 760-730. These alloys expand on not confirm this statement.
solidifying, and are hard, but fairly malleable. (1) Four parts pure potassium carbonate and
They are unaltered by air or water at ordinary 11 parts pure antimony sulphide are heated to
temperatures, and this property, combined with fusion in a covered crucible, cooled, boiled with
their lightness and malleability, should render water, and filtered. The solution on exposure
them useful in the building of light structures to the air deposits kermes, the residue from the
such as aeroplanes. first boiling is heated with the mother liquor
Melted gold absorbs the vapour of antimony, from some previously deposited kermes, and
but gives it up almost entirely on further heating. yields a further quantity ; this operation is re-
Gold loses its malleability when jj, of antimony peated until an insoluble residue of trisulphide
is present. An alloy of 9 gold and 1 antimony and trioxide is left. Each successive deposit of
is white and very brittle, with an amorphous the kermes contains a larger amount of the oxide.
porcelain -like fracture. Silver antimonide occurs (2) Fuse together 2 parts antimony, 1 sulphur,
as the mineral discrasite. and 3 sodium carbonate or, 1 antimony
;
sulphide and 3 or 4 tartaric acid, until fumes

COMPOUNDS OF ANTIMONY. cease to be evolved and treat
;
the product as
The principal compounds of antimony are in(l).
formed by combination with oxygen, sulphur, (3) Theslags from the reduction of antimony
and chlorine ; some compounds contain two of ore with cream of tartar slowly precipitate
these negative elements, of which the oxychloride kermes when treated with water this is sold to ;
'
or powder of Algarotk, and the oxysulphide or veterinar y surgeons as kermes by the dry way.
'
glass of antimony are examples. When antimony sulphide is boiled with potash
The most important of these are the tri- and precipitated with an acid, the kermes pro-
chloride, trisulphide, and trioxide. duced contains no oxide (Liebig). The kermes
Antimony trisulphide Sb 2 S 3
.
produced by the action of dilute alkaline car-
Crude antimony, antimony ore, sesquisul- bonate on antimony sulphide also contains no
phide of antimony ; Schwefelspiessglanz ; Grau- oxide (Rose). The oxide may be removed from
Spiessglanzerz ; Stibium sulphuratum nigrum ; ordinary kermes by digestion with tartaric acid.
lupus metallorum. A solution containing so much alkali as to give
This substance, as it occurs r aturally, or after no precipitate on cooling gives, when treated
liquation, is usually too impure to be employed with carbonic acid gas, a highly sulphurated
for other purposes than the preparation of the kermes containing antimony pentasulphide.
metal. Kermes is a brown-red, loosely coherent
The ordinary sulphide may be prepared by powder, with a brown streak, containing water,
the following methods : which is given off below 100". It is lighter
(1) Thirteen parts pure antimony are mixed than the ordinary sulphide. The kermes con-
with 5 parts flowers of sulphur, and projected in taining antimony oxide, when fused
and solidi-
while
portions into a red-hot crucible ; when com- fied, is destitute of crystalline structure,
pletely fused, it is poured out and any free metal that free from oxide produces a highly crystalline
detached. solid.
Sulphuretted hydrogen precipitates it as
(2) Antimony pentasulphide Sb 2 S 5 Golden sul- .
auralum.
an orange precipitate from a solution of an phide of antimony ; sulphur antimonii
with potash
antimony salt. Prepared by boiling the trisulphide
(3) Digest for two hours in a closed vessel and ground sulphur, filtering and precipitating
1 part crude
antimony sulphide, 1 part pearl with acid. Redwood recommends 4 parts black
ash, 1 parts lime, and 15 parts water, and add antimony sulphide, 8 lime, and 80 water,
with hydro-
sulphuric acid ; the alkaline sulpho- salt first digested, filtered, and precipitated
or, 2 sulphide, 4 potassium
formed is decomposed by the acid with the pre- chloric acid car-
;
bonate, and 1 sulphur, to be fused, treated

with
cipitation of the pure sulphide. Antimony sul-
phide is soluble in alkaline sulphides and in
f
20 parts water, filtered, and the solution pre-

When finely powdered excess of sulphuric acid.
acid potassium sulphate. cipitated with a large
and rubbed to a paste at 20 or 30 with strong On treating the mother liquor from kermes
sodium sulphide solution, a coppery metallic mineral with an acid, the pentasulphide is pre-
mass is produced, and the liquor, on addition of cipitated with evolution
of sulphuretted hydro-
more sodium sulphide, yMds Schlippe's salt. gen. The mother liquor from Schlippe's salt
The sulphide is used to some extent in re- also yields this substance on the addition of an
fining gold from silver and copper, and in the acid (R. Bartley, Chem. Soc. Trans. 1876, 1,
preparation of safety matches and percussion 748). It generally contains free sulphur.
282 ANTIMONY.
Antimony pentasulphide is of some import- 64 parts nitre, is thrown little by little into
ance commercially, as it is used in the process of a heated crucible, fused, powdered, washed, and
vulcanising rubber. dried. In this way bismuth antimonate is pro-j-
Antimony pentasulphide combines with alka- duced. Of this 1 part is mixed with 8 parts bs
line sulphides, forming sulphantimonates, which ammonium and 128 parts litharge, an>.d
chloride
as well as the sulphantimonites (which contain fused as before. The time occupied and the
less sulphur) are known as livers of antimony.'
'
temperature used cause considerable variations
Of these the sodium sulphantimonate, or in the colour. Merimee's yellow is a fine per-I
salt, is the most important. manent colour of good body. It is only used A
Schlippe's
A
mixture of 11 parts finely powdered anti- for the finest painting.
mony trisulphide, 13 crystallised sodium car- Naples yellow is essentially an antimonate
bonate, 1 flowers of sulphur, 5 recently slaked of lead containing excess of lead oxide, but
lime, and 20 water, is digested at the ordinary mixtures of carbonate and chromate of lead are
temperature for 24 hours with frequent also sold under the name. Many processes may
stirring, in a vessel which can be closed. It is be used for its preparation. According to
then strained and washed several times with Brunner, a mixture of 1 part tartar emetic, 2
water, the solution and washings are evaporated parts lead nitrate, and 4 parts sodium chloride is
in a porcelain or clean iron dish until a sample heated, just to fusion, for 2 hours. The cooled
yields crystals on cooling ; the solution is then mass is placed in water and soon falls to pieces.
cooled, and the resultant crystals washed with According to Guimet, it may be produced by
cold water and dried in the open air or in a heating a mixture of 1 part potassium antimo-
desiccator at the ordinary temperature. The nate and 2 parts red lead. It is a fine very
salt ismore rapidly formed when the mixture is permanent orange or yellow pigment, used in
heated (Liebig, Handworter. d. Chem. 2te Aufl. oil-painting, and, mixed usually with a lead glass,
2, 139 ; also Gm. 4, 384). for glass and porcelain staining.
Oxysulphides of antimony are formed by the Antimony trichloride (Butter of antimony).
combination of the sulphides and oxides or by Prepared by dissolving the sulphide hi strong
the partial oxidation of the sulphides. hydrochloric acid with a small quantity of nitric
Antimony crocus or saffron. Fuse together acid and evaporating to dryness.
3 parts of antimony trioxide and 1 part trisul- To prepare the pure chloride, the acid solu-
phide, or fuse the oxide with the calculated tion is evaporated until it just crystallises on
standing in a cool place ; then transferred
'
quantity of sulphur. it is
The scoria from the fusion of the sulphide to a retort and distilled until a drop of the dis-
with carbon and alkaline carbonate in the pre- on a cold surface ; the receiver
tillate solidifies
paration of the metal is known as crocus of is then changed, and the further distillate is
antimony. pure.
Crocus of antimony is a brownish-yellow It is a white, buttery, semivitreous, delique-
body. scent solid. When pure, it is crystalline, and
Glass of antimony. Vitrum antimonii. When melts sharply at 73-2, and boils at 223-5
antimony sulphide is fused until the necessary (Beckmann, Zeitsch. anorg. Chem. 1906, 51, 96).
amount of sulphide has been converted into It is used as a caustic in medicine, for the pre-
oxide, the whole forms a glassy mass of this paration ' of tartar emetic, and as a bronzing
'
compound. The best method of preparation is solution for gun-barrels, &c. For this pur-
to roast the sulphide completely into oxide and pose a saturated solution is mixed with olive oil,
fuse the product with ^ part of sulphur. Its rubbed over the warmed metal and exposed to
colour varies with the proportion of sulphur the air until the proper colour is produced.
present from yellowish-red to hyacinth red. The When bronzed, the metal is polished with a
best quality is of a fine red colour, and con- burnisher or with wax. or coated with a varnish
tains 8 antimonious oxide and 1 antimonious of 2 oz. shellac, 3 drachms dragon's blood, dis-
sulphide. solved in 2 quarts of methylated spirit.
Antimony cinnabar is an oxysulphide of a Antimony oxychloride. Basic chloride,
fine vermilion colour, soft and velvety, and un- powder of Algaroth ; pulvis Algarothi ; 8.
altered by air or light ; it is used in the prepara- Argelicus ; mercurius vitce, dec.
tion of oil and water colours, and in calico-print- Water is added to a solution of the trichlor-
ing. It is prepared by dissolving antimony ide untilit is distinctly turbid, when it is filtered
oxide in hydrochloric acid, and placing the solu- (the precipitate carries down any traces of sul-
tion in a large wooden tub which is f filled
i
phuretted hydrogen which may be present, and

with calcium hyposulphite. The mixture is which ifleft would soon turn the substance
stirred and heated with steam to 70, the pre- yellow). Five to ten volumes of water are added,
cipitate soon subsides as a yellowish sediment and the precipitate is washed with cold water
which changes to a bright orange-red, and is and filtered. Its composition varies with the
thoroughly washed, and dried below 50. N. temperature at which it is produced and the
Teck (Chem. Zentr. 26, 1880) prepared it from amount of water used, varying between SbOCl
4 parts tartar emetic, 3 tartaric acid, 18 water and, where a very large amount of water has
mixed at 60 with hyposulphite of soda and been used, Sb 2 3 It is a white powder, and is
.
heated to 90 (Wagner), or 4 volumes antimonious principally used for the preparation of pure
chloride of sp.gr. 1-19 mixed with 10 vols. water antimonious oxide and tartar emetic.
and 10 vols. hyposulphite of 1-19 sp.gr., and Antimonious oxide Sb 4 6 Trioxide of anti-
.
heated gradually to 55 (Mattieu Blessy). mony. If antimony is powdered and heated in

Antimony yellow (Merimee's yellow). Accord- a shallow dish, it eventually forms antimony
ing to the method of Merimee, a mixture of 3 tetroxide Sb 2 4 this, together with the un-
;
parts bismuth, 24 parts antimony sulphide, and changed metal, is fused in a crucible, when
APATITE. 283
the tetroxide and antimony react, forming anti- a process for using trichloride with sufficient
monious oxide, the excess of antimony sinking common salt to prevent the precipitation of the
to the bottom of the crucible. oxychloride (G. Watson, J. Soc. Chem. Ind.
For pharmaceutical purposes 20 parts of finely 1886, 5, 591 ; B. W. Gerland, J. Soc. Chem. Ind.
powdered antimony sulphide are gradually added 1884, 4, 643 and Kopp and Bruere, J. Soc.
;
to 100 parts hydrochloric acid containing 1 part Chem. Ind. 1888, 566). A
double salt of anti-
nitric acid, and heated, gently at first, and mony fluoride and ammonium sulphate SbF 3
(NH 4 2 S0 4 known as antimony salts,' is also
'
then more strongly, until sulphuretted hydrogen ) ,
ceases to be evolved. It is then boiled for an used in dyeing, but as it attacks glass as well as
hour, enough water is added to produce a slight metal, it should be stored and worked in wooden
precipitate, which removes the last traces of sul- vessels. A good bath is 100 litres water, 400
phuretted hydrogen, and filtered into a vessel grams antimony salts, 200 grams soda crystals,
containing 1 gallon of water, precipitating the at a temperature of 50 (Frey, Bull. Soc. Md.
oxychloride, which is filtered and washed until Mulhouse, 1888, 301).
it ceases to have an acid reaction ; it has then Tartar emetic as a mordant has, at the
become converted into the trioxide. present time, been largely superseded by the
It is a white fusible solid, slightly soluble double oxalate of potassium and antimony, as
in water, volatile at a red heat. It becomes it is cheaper than the tartrate, and
equally
further oxidised to the tetroxide Sb 2 4 on efficient, although it contains less antimony.
heating in air, and is then non- volatile. Recently F. During has recommended the
In presence of alkalis it absorbs oxygen ; use of the double lactate of antimony and cal-
for this reason it has been proposed to use it for cium, which can readily be obtained by mixing,
reducing nitrobenzene to aniline, and in the in the dry state or in solution, alkali lactates
'
preparation of aniline red. with antimony salts,' or other antimonious
It is used for the preparation of tartar emetic. compounds (Farber, Zeit. [20] 319). He states
When ground with linseed oil it is sometimes that at least 80 p.c. of the antimony in the
used as a substitute for white lead, being less solution will actually go into the cloth as
injurious to the workmen and less acted upon by mordant.
'
sulphur gases ; it has, however, less body and

'
ANTIMONY SALTS. A compound of anti-
is more expensive. mony fluoride with ammonium sulphate used as
Tartar emetic. Potassium antimony tartrate. a mordant (v. ANTIMONY).
Tartarus stibiatus. Brechweinstein ; spiessglanz- ANTINONIN. Trade name for a solution
weinstein. H
2C 4 4 K(SbO)0 6 ,H 2 0. Three parts of potassium o-dinitrocresol used as a fungicide.
antimonious oxide and 4 cream of tartar are ANTIPYRINE. Phenyldimelhylpyrazolone (v.
made into a thin paste with water and digested PYKAZOLE).
for about half an hour, keeping the water at ANTIRRHINIC ACID v. DIGITALIS.
constant volume ; 8 parts of water are then ANTISEPTICS v. DISINFECTANTS.
added, boiled, and filtered whilst hot. The ANTISEPTINE. Said to be a mixture of
oxychloride or oxysulphide may be substituted zinc iodide, zinc sulphate, boric acid, and thymol.
for the oxide, but not so satisfactorily. ANTISEPTOL. Cinchonidine iodosulpJiate,
Tartar emetic forms octahedral crystals, used as a substitute for iodofprm.
which give off a part of their water on exposure ANTITHERMIN. Phenylhydrazone of Icevulic
to the air. They dissolve in 14-5 parts cold and acid CH 3 -C(N 2 H-C 3 H S )-CHVCH 2 -CO,H is ob-
in 1-9 parts boiling water. They show an acid tained by dissolving phenylhydrazine in dilute
reaction with litmus, and have a nauseous acetic acid, adding an aqueous solution of the
metallic taste, 5-10 centigrams causing vomiting, equivalent quantity of laevulic (acetopropionic)
and larger quantities being very poisonous. acid, and crystallising the resulting yellow pre-
It is used in medicine and in the preparation cipitate from alcohol (Farbw.
vorm. Meister,
of pomades, &c., and also
largely as a mordant Lucius & BrUning in Hochst a. M., Ger. Pat.
in dyeing and calico-printing. Mixtures of 37727).
tartar emetic for mordanting are sold containing It forms colourless, inodorous, and tasteless
as much as 3359 p.c. zinc sulphate at a lower scales, melts at 98-99, is sparingly soluble
in
price, under the names tartar emetic powder, cold water, soluble in alcohol, ether, or dilute
tartar emetic substitute, antimony mordant, &c. acids. It has been employed as an antipyretic
It is known that zinc acetate Chem. Zentr. 1887, 415) but, according
may partly replace (Nicot, ;
the tartar emetic with advantage, but the to Stark (Chem. and Drug, 32, 651), its use in
sulphate appears to be a simple adulterant (H. medicine is now almost abandoned. Inasmuch
Smid, Chem. Zeit. 1882, 949). as decomposed by alkalis, its physiological
it is
Several other compounds of antimony have activity is probably due to phenylhydrazine
been proposed for mordants instead of tartar (Gehe & Co., Chem. Zentr. 1888, 49).
emetic. E. Jacquet (Dingl. poly. J. 257, 168) ANTWERP BROWN v. PIGMENTS.
advised the use of a mixture of basic antimony ANVULA v. AMLAKI.
oxalate with twice its weight of ammonium AOOD-I-BALSAM. Balsaam of Mecca (v.
oxalate. Nolting recommended the double OLEORESINS).
oxalate of potash or of ammonia and antimony APATITE. A crystallised mineral,
consist-
in combination with
(Dingl. poly. J. [3] 255, 122). It is stated that ing of calcium phosphate
the latter compounds have or carbonic acid,
long been used under fluorine, chlorine, hydroxyl,
other names. the formula being (CaF)Ca 4 (P0 4 ) 3 or 3Ca 3 (P0 4 ) 2
The use of the fluoride (which is not pre- + CaF 2 , where F may be replaced by Cl, OH, or
cipitated with excess of water) and the double C0 3 There are thus several chemical varieties,
.
fluorides ofantimony and the alkalis has been namely, fluor-apatite, chlor-apatite, hydro-
patented by S. M'Lean. Watson, jun., patented and carb-apatite ; the last being also
apatite,
284 APATITE.
called podolite (W. Tschirwinsky, 1907). Simi- APOLLO RED v. Azo- COLOURING MATTERS.
larity, by partial replacement of the calcium, APOMORPHINE v. VEGETO-ALKALOIDS.
there are the chemical varieties mangan-apatite, APOPHYLLITE v. CALCIUM.
cupro-apatite, and talc-apatite. In addition to APOREINE. A poisonous alkaloid found in11
these, some other trivial names are applied to ,he juice of Papaver dubium. Gives crystal-
varieties of crystallised apatite ; for example, ine salts. H
The hydrochloride C 1? 1B NO2,HC1,
asparagus-stone, from Murica in Spain ; moro- 'orms silvery nacreous scales, subliming without
xite, from Arendal in Norway and francolite,
; decomposition in dry carbon dioxide between
from Wheal Franco, near Tavistock in Devon- 220 and 240.
shire. The distinction between fluor-apatite APORETIN v. RHUBARB.
and chlor-apatite is, however, the only one of APOTURMERIC ACID v. TURMERIC.
any importance. (For the varieties of massive APPLE. The fruit of Pyrus mains. Many
apatite, v. PHOSPHORITE.) varieties are known*, differing greatly in size,
Apatite is often found as well-developed shape, colour, and flavour.
crystals. These belong to the hexagonal The solid matter of apples consists largely of
system, and are usually bounded by a six-sided sugars glucose and sucrose ; their acidity is due
prism and pyramid with the basal plane, though H
to malic acid C 2 4 0(COOH) 2 .In unripe apples
sometimes numerous other brilliant facets are starch is present sometimes to the extent of
present. The colour
is commonly greenish or 4 or 5 p.c., but the fully ripened fruit is devoid
brownish, but sometimes sky-blue, violet, or of starch. Cellulose forms about 1 p.c. of the
colourless. The crystals may be transparent or weight of the ripe fruit, pentosans about 0-5 p.c.,
opaque, and they have a vitreous to sub-resinous and pectose matters also about 0-5 p.c. Mineral
lustre. Sp.gr. 3-2 hardness 5 (the mineral can
;
matter is usually between 0*2 and 0-3 p.c., and
be scratched with a knife). Owing to its about half of this is potash.
variable appearance, apatite is frequently mis- The following analyses of American Baldwin
taken for other minerals, and it well deserves apples show the changes which occur during
its name, from a-ira.rav, ' to deceive.' In ripening :
determining the mineral, it is always well to test

for phosphoric acid.
As microscopic crystals, apatite is present as
an accessory constituent of igneous rocks of all
kinds. It also occurs in metamorphic rocks and
in metalliferous veins. Fine specimens are
found at many localities, but only in two
regions in Norway and Canada is crystallised
apatite mined for commercial purposes. In
southern Norway, in the neighbourhood of
Kragero and Bamle, extensive deposits of chlor-
apatite occur in connection with gabbro (a
pyroxene-felspar rock of igneous origin). Large
deposits of fluor-apatite are mined in Ottawa Co.,
Quebec, and in Renfrew Co., Ontario ; here the
mineral forms beds in Laurentian gneiss, usually
in association with crystalline limestone.
L. J. S.
APERITOL. A
mixture of equal parts of
valerianyl and acetylphenolphthale'in, used as a
laxative.
APHTHITE. An alloy containing 800 parts
of copper, 25 of platinum, 10 of tungsten, and
170 of gold (Zeits. f. d. C. Grossgew. 4, 313).
APIGENIN v. FLAVONE.
APIIN. A glucoside contained in parsley and
celery, forming on hydrolysis apigenin and a
disaccharide, made up of a-glucose and a pentose,
apiose (Vongerichten, Annalen, 1901, 121), (v.
FLAVONE and GLUCOSVDES).
APIOL v. OILS, ESSENTIAL.
APIOSE v. CARBOHYDRATES.
APIOS TUBEROSA (Moench.), Glycine
apios (Linn.). A leguminous plant from
North America, the roots of which have been
proposed as a substitute for the potato, and the
young seeds for peas. Payen (Compt. rend. 28,
189) gives the following analysis of the root :
Nitrogenous matters, 4-5; fatty matters, 0-8;

starch, sugar, &c., 33-55; cellulose, &c., 1-3;
inorganic, 2-25; water, 57-8 (cf. Brighetti, Chem.
Zentr. 1900, i. 914).
APIUM v. OILS, ESSENTIAL.
APIUM PETROSELINUM (Carum petro-
selinum) v. FLAVONE.
AQUA REGIA. 285
in American apples, while the figures for phos- Seeds (stone) . 4-30 3-22
phorus pentoxide and chlorine are higher. Skin and cellulose 0-97 0-94
Hotter (Chem. Zentr. 1900, ii. 484) gives the Pectose . . 0-15 1-00
following analysis of apple ash : Ash . . .
I (0-07) (0-10)
CaO MgO Fe 2 3 SiO 2 S0 3 Total insoluble matter, ex-") r < K in-
51-58
Certain
4-22
varieties
3-71
of
1-18 1-08
apples particularly
those used for cider-making are rich in tannin,
2-49 10-42
cluding ash
Water .... . .
'
84-96 82-12
100-00 100-00
and, when the cells are broken, e.g. by cutting
the apple or by a bruise, so as to admit air, a In Californian-grown apricots, Colby (Exp.
browning takes place probably by the action Stat. Record, 1893, 4, 918) found, in the whole,
of an oxydase upon the tannin. 'resh fruit, water, 85-16 ; dry matter, 14-84 ;
Otto (Bied. Zentr. 1901, ii. 553 ; and 1902, ontaining nitrogen, 0-194; sugar, 11-10; ash,
31, 107) found that the percentage of water 0-49.
increases during ripening on the tree, but di- The ash was found to contain :
minishes on storing, that the starch diminishes K2O Na 2 O CaO MgO MnO 2 P 2 5 SO 3 SiO 2
and finally disappears, while the cellulose 59-36 10-26 3-17 3-68 0-37 13-09 3-63 5-23
remains constant. The nitrogen increases during Cl Fe 2 O 3
0-45 1-68
ripening on the tree, but afterwards diminishes.
The acidity diminishes during ripening, both Californian apricots appear to contain more
before and after gathering.
nitrogen than the European fruit. As many
Under normal conditions, the starch present other analyses agree in giving about 11 p.c. of
hi unripe apples is converted, during ripening,
sugar, it is probable that some error has been
into sugar by the diastase present, but if the made in Fresenius' figures, though they have
unripe apples be bruised, this change is incom- been widely quoted.
plete in the bruised portion, and starch may be The sugar is chiefly sucrose, with a little
found in the browned tissues. According to dextrose, and invert sugar, which becomes less
Warcollier (Compt. rend. 1905, 141, 405), this when the fruit ripens (Desmouliere Ann. Chim.
is due to the paralysing effect upon the diastase anal. 1902, 7, 323). The colouring matter is
of the tannin which escapes from the bruised
probably related to carrotene.
cells (and which, by the action of an oxydase, The acidity of apricots is due to malic
chiefly
gives rise to the browning), thus preventing the and citric acids.
saccharification of the starch, upon which The kernels of apricot
'
pits,' or stones, like

normal ripening depends. those of the other members of the Prunus
Apples are now dried by artificial heat (with family, contain amygdalin and about 40 p.c. of
or without the use of sulphur dioxide, which a fatty oil resembling almond oil. This oil
improves the colour), and sold, either as whole
'
has a sp.gr. of 0-9204 at 15 -5, a pale-yellow colour,
fruit or as apple rings.' Fresh apples yield and a slight odour of almonds (Maben, Pharm. J.
about one-seventh of their weight of the dried Trans. [3] 16, 797). More recent determinations
product. Zinc is frequently found in dried give the following (Dieterich, Chem. Zentr. 1902,
apples, probably from contact with zinc trays 2 [15], 943) sp.gr. at 15C. 0-915-0-921,
: at 90,
during the drying process. As much as 0-58 0-9010-0-9015; solidifying point, 14 to 20;
gram Zn per kilogram has been found in Ameri- saponification value, 193-1-215-1
iodine value ;
can dried apples. American analyses give as refractometer value at 25,

(Hiibl), 100-108-7 ;
the average components of dried apples 36 p.c. :

65-6-67-0 at 40, 58-0 at 50, 52-25. It can be
; ;
water, 1-4 p.c. protein, 3-0 p.c. ether extract, distinguished from almond oil by Biber's reagent
57-6 p.c. carbohydrates, and 1-8 p.c. ash. The
(fuming nitric acid, sulphuric acid and water),
flavour, and particularly the odour, of apples with which it gives a red colour, while almond
can be imitated by iso-amyl-iso-valerate dissolved oil only yields a faint yellow.
'
in spirits of wine. This constitutes the essence The flavour of apricots can be imitated by
'
of apples used in confectionery and perfumery. a mixture of isoamyl butyrate and iso&myl
alcohol.
APPLES, ESSENCE OF, . APPLES. Dried apricots are prepared either by sun-
APPLE TREE. (Pyrus malus, L. ; Pomrne, drving or by artificial heat, sulphur
dioxide
Fr. Apfel, Ger.) The wood is much used in
;
being often employed in the
latter case, in order
turnery, and that of the crab tree is used by to prevent darkening in colour. They are largely
millwrights for the teeth of mortice wheels. used in America and in some of the colonies.
The bark contains a tannin identical with that American analyses show them to contain about
contained in horse-chestnut bark. 32 p.c. of water, 63 p.c. of carbohydrates, 2-9 p.c.
APRICOT. The fruit of Prunm armeniaca of nitrogenousmatter, and 1-4 p.c. of ash.
II. I.
(Linn.).
Thefollowing analyses were made by APRICOT, ESSENCE OF. A mixture of
Fresenius :
woamyl butyrate and zsoamyl alcohol.
Medium
I. II.
Large
APRICOT KERNEL OIL v. ALMOND OIL.
size wt. 60 grams AQUA FORTIS v. NITRIC ACID.
Sugars . . .1-14 1-53 AQUA REGIA. Nitromurialic acid ; KiJnigs-
acid 0-90. . 0-77 wasser. A name given by the alchemists to
0-39 a mixture of nitric and hydrochloric acids,
Nitrogenous matter. 0-83
sal ammoniac
Ash
(Free
Total soluble matter
...
Pectins, gum, &c. 5-93
0-82
9-62
. 9-28
0-75
12 -75
originally prepared by dissolving
in strong nitric acid, and used by them as
solvent for gold, sulphur, &c.
a
Usually made
286 AQUA REGIA.
by mixing 1 vol. of nitric acid with 4 vols. of kidney beans ; it is used as salad oil, and sold
hydrochloric acid. The mixture is at first under the name ' huile surfine.' The oil
colourless, but gradually especially on heating obtained by the next expression also serves for
acquires a deep orange-yellow colour, due to edible purposes, in the sardine and margarine
the formation of nitrosyl chloride and free industries, or for burning ; the lowest quality,
chlorine 3 3HC1
: HN0 +
NOC1 C1 2 2H 2 0. = + + which has been expressed at the highest tempera-
The solvent action of aqua regia appears to be ture, is chiefly used for soap-making.
mainly due to the free chlorine. The arachis cakes serve as an excellent
AQUA VIT>E. An alchemistic name used to cattle food, for they contain the highest amount
denote common alcohol as obtained by distilling of proteids of all known oil cakes ; moreover,
a liquid which has undergone vinous fermentation. these proteids are more easily digested than those
ARABIC GUM v. GUMS. of other cakes.
ARABINOSE v. CARBOHYDRATES. On standing a few degrees above freezing-
ARACHIDIC ACID CH 3 (CH 2 18 COOH ' '
)
is point, stearine deposits from arachis oil.
found partly free and partly as a glyceride in This stearine contains arachin which does not
earth-nut oU (from Arachis hypogcea (Linn.)); in settle out as a crystalline mass, so that it cannot
butter, and in the fruit of Nephelium lappaceum be removed in the usual manner by expression.
(Heintz. Pogg. 90, 146 ; Grossmann, Annalen, 89, Hence it is necessary, in order to '
demargari-
'
1 ; Oudemahs, Zeits. f. Chem. 1867, 256). It nate arachis oil, to allow it to stand for a
'
has been prepared by treating behenolic acid prolonged ' time in the cold, when margarine
H
C 22 40O 2 with fuming nitric acid (Grossmann, d'arachide settles out, so that the supernatant
Ber. 1893, 644), and synthetically from aceto- clear oil can be drawn off.
acetic ester and octodecyl iodide (Schweizer, Amongst the solid fatty acids of arachis oil,
Arch. Pharm. 1884, 753) ; m.p. 77 (Baczewski, arachidic acid and lignoceric acid have been
Monatsh. 17, 530). identified. These two acids are characteristic
ARACHIS OIL is obtained from the seeds of of arachis oil, and as their proportion can be
Arachis hypogcea (Linn. ), which are known in com- determined quantitatively, the separation and
merce as earth nuts or monkey nuts. The
' '
determination of crude arachidic acid (i.e.
cultivation of the arachis plant dates back so a mixture of arachidic and lignoceric acids)
far in history that its origin is unknown. It is furnishes an excellent means of identifj'ing
frequently assumed that the home arachis oil, and determining its proportion in
of the
arachis nut is Brazil. The plant is chiefly mixtures with other oils. Amongst the liquid
cultivated in the East Indies, Indo-China, Java, fatty acids of arachis oil, oleic acid undoubtedly
Japan, the West Coast of Africa, Mozambique, predominates ; in addition to it there has also
the United been proved the presence of hypogseic and
Madagascar, Egypt, Spain, Sicily,
States of America, the Argentine, and in the linolic acids.
West Indian Islands. The East Indian and Arachis oil has a sp.gr. 0-917-0-919 at 15 ;
West African nuts represent two distinct itsiodine value fluctuates between 87 and 100.
varieties. In commerce a distinction is made As the iodine value of arachis oil lies so near
between decorticated and non-decorticated nuts. that of olive oil, adulteration of olive oil with
The Indian and Mozambique nuts are usually arachis oil takes place on the largest scale ;
decorticated before they are shipped to Europe ; indeed, very frequently arachis oil is entirely
as they undergo some detrimental changes on substituted for olive oil (as in the preparation
the voyage, they cannot be used for the produc- of tinned sardines).
tion of best edible oil, and are mostly worked Arachis oil is chiefly expressed in the South
up for soap oil. The nuts coming from West of Europe (Marseilles and Trieste); therefore
Africa mostly arrive non-decorticated, and are the lower qualities of this oil enter largely into
therefore suitable for the preparation of best the composition of the soaps of South Europe.
edible oil, the lower qualities only, derived from Thus, one of the most characteristic components
a second and third expression (see below) being of the Marseilles white soap is arachis oil. The
used for technical purposes. The approximate quantity of arachis nuts imported into France
composition of arachis nut, taking
the average during the year 1907 was arachis nuts in shells,
:
of nuts from various places of origin, is as 163,241 tons ; decorticated arachis nuts,
follows oil, 38-50 p.c. ; water,
:
4-6-12-8 p.c. ; 117,404 tons. The total quantity of arachis
albuminoids, 26-31 p.c. ; carbohydrates, 5-19 nuts produced in the world may be taken to
p.c. ; fibre, 1-1-4-1 p.c. ; ash, 1-6-3-0 p.c. amount to about 350,000 tons. Next to France,
The undecorticated nuts are shelled by special arachis nuts are largely imported into Trieste,
machinery and the inner red skua which sur- Delft, and in smaller quantities to Germany
rounds the kernel is removed as completely as (about 25,000 tons), and to the United States of
possible by a blast of
air. The separated and America. The latter country produces about
cleaned kernels are then ground in the usual 50,000 tons per annum. J. L.
manner and subjected to hydraulic pressure. ARAGONITE. The orthorhombic form of cal-
As the kernels contain so high a proportion of cium carbonate (CaC0 3 ), differing from the more
oil, the expression
of the oil is carried out in common dimorphous form calcite (q.v.) in its
two stages frequently the
;
meal is even greater density (sp.gr. 2-93), greater hardness
expressed three times. The (H. 3), and in the absence of cleavage. It
first expression
takes place at the ordinary temperature, and crystallises, together with calcite, from aqueous
'
'
cold-drawn oil ; the second ex- solutions containing carbon dioxide at tempera-
yields the
pression is carried out at
a temperature of 30- tures above 18, and the presence of various salts
32 and the third expression at 50-55.
;
in the solution favours its growth. In nature
'
The ' cold-drawn oil is nearly colourless, it isdeposited by thermal springs, for instance,
and has a pleasant taste, recalling that of those of Carlsbad in Bohemia, in the form of
ARCHIL OR ORCHIL. 287
pea-like concretions, this variety of the mineral drop of

fuming nitric acid gives a red solution,
being known as pisolite. Another variety, which when spread in a thin layer and treated
called flos-ferri (flower of iron), is found as with ammonia strikes a violet colour (Pharm.
snow-white coralloidal forms in the iron-mines Germ.).
of Styria. Crystals were first found embedded Dichrysarobin consists of orange crystals,
in red clay and gypsum in Aragon, Spain ; and decomposing at about 250. It is distinguished
divergent groups of spear-lJke crystals have been from chrysarobin by being insoluble in benzene ;
found in an iron (haematite) mine in west it also appears to be more

readily oxidised,
Cumberland. L. J. S. yielding, similar to chrysarobin, chrysophanic
ARALIA BARK or False Prickly Ash Bark, acid. A
hexa-acetyl derivative, C 30 18 7 Ac 6 , H
the bark of Aralia 'spinosa (Linn.), contains a m.p. 178-181, has been obtained, and on
volatile oil, an amorphous bitter substance, distillation with zinc-dust j3-methyl anthracene
(tannin), a grey acrid resin, and a glucoside to is formed.
which the name aralem has been given (Lilly, Though sometimes administered internally
Pharm. J. [3] 13, 305). By boiling aralein with as a purgative, araroba powder is used in
dilute hydrochloric acid, araliretin is obtained medicine almost exclusively as an external
(Holden, Pharm. J. [3] 11, 210; Chem. Soc. remedy in the form of ointment, in the treatment
Trans. 40, 105). if certain skin diseases. A. S.
ARAROBA POWDER. Goa Powder Chrys- ; ARASINA GURGI. An impure gamboge
arobin. A powder varying in colour from a pale from Camara, obtained probably from a species
primrose yellow to bronze and purple, which of Garcinia (Dymock, Pharm. J. [3] 7, 451).
collects, possibly as the result of oxidation ARBOL-A-BREA RESIN is obtained from
of the resin, in the cavities of the stems and Canarium luzonicum (Miq.), a tree belonging to
branches of the Andira Arardba (Aguiar) (ord. the Burseracese, growing in the Philippines.
Leguminosce), a tree inhabiting the forests of The resin is greyish-yellow, soft, glutinous,
Bahia in Brazil (Aguiar, Pharm. J. [3] 10, 42 ; and has a strong agreeable odour. It contains
cf. Greenish, ibid. [3] 10, 814). 61-29 parts of resin very soluble in alcohol ;
Crude araroba was examined by Attfield in 25-00 parts of resin sparingly soluble in alcohol ;
1875 (Pharm. J. [3] 5, 721), and found to contain 6-25 essential oil ; 0-52 free acid ; 0-52 bitter
moisture, 1 p.c. ; glucoside, bitter constituent and extractive matter ; 6-42 woody and earthy
arabin, 1 p.c. ; yellow crystalline substance ex- impurities (Bonastre, Jour. Pharm. 10, 129).
tracted with benzol, supposed to be chrysophanic Baup has isolated four crystalline substances,
acid, 80-84 p.c. ; resins, 2 p.c. ; ivoody fibre, 5-5 Amyrin, Bre'idin, Bre'in, and Brymdine (Ann.
p.c. On incineration, 0*5 p.c. of ash was obtained. Chim. Phys. [3] 31, 108).
The yellow crystalline compound which ARBUTIN v. GLUCOSIDES.
constitutes the chief part of Goa powder and ARCHIL or ORCHIL (Orseille, Fr. ; Orseilk,
to which its activity is probably due, was Ger. ; appears in commerce in three
Oricello, It.)
subsequently examined by Liebermann and forms (1) as a pasty matter called archil
:
(2) ;
Seidler (Ber. 11, 1603; Annalen, 212, 29). It as a mass of a drier character, named persis ;
was shown to be chrysarobin, independent of, and (3) as a reddish powder called cudbear.
but closely related to, chrysophanic acid, and It is obtained from various lichens of the genus
into which it is readily converted by the oxidising Roccella, growing on the rocky coasts of the
action of the air. This is most expeditiously Azores, the Canaries and Cape de Verd Isles,
effected by leading a current of air through also of the Cape of Good Hope, Madeira, Corsica,
Goa powder dissolved in aqueous potash. Sardinia, &c., and from Ochrolechia tartar ea,
Hesse (Annalen, 309, 32) finds that araroba growing in Sweden and Norway. None of
powder contains no chrysophanic acid, but is these contains the colouring matters
lichens
a mixture of chrysarobin C 1S 12 H 3, with a ready formed, but they contain certain colour-
substance yielding methyl iodide by Zeisel's less acids of the type of lecanoric acid, deriva-
method, which was assumed by Hesse to be tives of orcin, into which they can be readily
chrysarobin methyl ether. converted. Thus, lecanoric acid (1) gives first
Araroba powder has been fully investigated orsellenic acid ; (2) and subsequently orcin (3)
by Jowett and Potter (Chem. Soc. Trans. 81, according to the following scheme. (See under
1575), who have isolated the following substances : LECANOEIC ACID.)
H
chrysarobin C 15 12 3 ; dichrysarobin C 30 24 7 ; H CH
dichrysarobin methyl ether C 3 iH 2i 7 , melting
CH
H
at 160; and a substance, C 17 14 4 , m.p. 181. COOH/ /co/\
Pure chrysarobin prepared from the com- (1)
OH OH\ ;OH
mercial product by extraction with light
petroleum, distilling, and recrystallising the CH 3 CH
residue repeatedly from a large quantity of
ethyl acetate, consists of lemon-yellow scales
COOK/' (3)
(2)
melting at 202 (corr.) insoluble in aqueous OH\ /OH OH\ /OH
sodium carbonate, but soluble in caustic alkalis,
giving a yellow solution which becomes red in Orcin itself, when acted upon by air and
the air. It dissolves in concentrated sulphuric ammonia, changes into a purple substance called
acid with a yellow colour. On distillation with orcein, which is the name applied to the colouring
zinc, /8-methyl anthracene is obtained. When matters of archil (Robiquet, Ann. Chim. Phys.
acetylated, chrysarobin yields a diacetyl com- [2] 47, 238).
H
pound, Ci 5 10 3 Ac 2 m.p. 193,
,
and a triacetyl Finely powdered orcin is placed in
a thin
H
compound, C 15 9 3Ac 3 m.p. 238. A minute
, layer under a bell jar, together with
a beaker
quantity (1 nig.) of chrysarobin sprinkled on a containing strong ammonia solution.
As soon
288 ARCHIL OR ORCHIL.
as the substance has become brown-coloured, !
of the arc or oxygen is entrapped, and exerts
it is removed and exposed to air for some time. therefore a more powerful oxidising effect.
It is then dissolved in very dilute ammonia Orchil liquor isprepared by extracting the
solution, reprecipitated with acetic acid, and lichens with boiling water, concentrating the
dried. According to Gerhardt and Laurent, extract to from 8 to 10Tw., and submitting this
orcin has the composition C 14 7 N0 6 (Ann. H to the action of air and ammonia; whereas
Chim. Phys. [3] 24, 315), but more recent orchil extract is produced by the extraction of
researches indicate that it is a mixture of orchil paste itself.
substances. instance (Ber.
Liebermann, for In former times archil and cudbear were
7, 247 ; 8, 1649), considers that by this re- frequently adulterated with magenta, certain azo-
!
action three colouring matters are produced, colours, extracts of logwood, brazilwood, &c. ;
H N0
|
having respectively the formulae (a) C 14 13 4 ; ! but as the importance of these dyestuffs has
(b) C; H 12 N
4 2 3 ; and (c) C 14 H 12 N 2 3
.
|
now very greatly diminished, such a contamina-
Zulkowski and Peters (Monatsh, 11, 227) I
tion is at the present time of rare occurrence.

allowed orcin to remain in contact with ammonia Archil and its preparations are substantive
for two months, and from the product isolated colouring matters, which dye well in a neutral
three substances: !
bath, but have the useful property of behaving

(a) Bed orcein C 28 H 24N 2
the main pro- 7, i
nearly as well under slightly acid or alightly
duct, which appears to be formed according to j
alkaline conditions. Even colours of con-
the following equation :
|
siderable intensity are produced from it without
4C 7 H 8 2 +2NH 3 +60=C 28H 24N 2 7 +7H 2 0. difficulty, but unfortunately these are not fast
1
to light. Wool is dyed hi a neutral bath, or

It is a brown crystalline powder, soluble in
with addition of a trace of sulphuric acid, and
alcohol with a red colour, and in alkaline solu-
silk is dyed in the presence of soap solution,
tions with a blue-violet tint.
acetic acid being sometimes added. Archil is
H 19 N0
'
Acrystalline yellow compound,C 21

(b) 5,
not applied to cotton.
which is accounted for as follows :
Archil was at one time employed to a large
3C 7 H 8 2 +NH +30=C H 19 N0 +4H
3 21 5 2 0. i
' '
extent for bottoming indigo, that is to say,
(c) An amorphous
product similar to litmus. i
the fabric was first dyed with archil and subse-
These substances can be prepared much more i quently with indigo. The reverse process,
rapidly by the addition of hydrogen peroxide i
known as * topping,' has again been considerably
to an ammoniacal solution of orcin. i in vogue. Cudbear and archil are also used
There can be no doubt that this reaction to a limited extent in conjunction with other
'
proceeds in several stages, and that the cha- dyestuffs for the production of compound
racter of the product varies according to the |
shades. White wines are sometimes coloured
duration of the process. This is well known |
with archil, but its presence can be detected
to manufacturers, who can prepare at will a i
by precipitating with lead acetate and extracting

blue or a red orchil. The constitution of these i with amyl alcohol, when a red colour indicates
colouring matters has not yet been determined, the presence of archil or magenta. The addition
'
but in view of the circumstances by which they i

of a little hydrochloric acid changes the colour
are produced, it is most probable that they to yellow if magenta be present, but does not
are members either of the oxazine or oxazone alter it if archil is the adulterant (Haas, Zeitsch.
groups. anal. Chem. 20, 869 ; J. Soc. Chem. Ind. 1, 119).
Orchil was originally prepared from the A. G. P.
lichensby means of stale urine, which supplied ARCHIL REDS v. Azo- COLOURING MATTEES.
the necessary ammonia, but ammonia solution ARCHIL SUBSTITUTES v. Azo- COLOURING
is now exclusively employed. The older MATTERS.
methods have, however, been greatly improved, ARECA. A genus of palms containing the
and in the place of barrels the operation is important species Areca Catechu (Linn.) (betel
carried out in large horizontal or vertical nut or areca nut), the fruit of which is used as a
cylinders with stirrers, and suitable
fitted masticatory in the East Indies. It contains an
openings for the admission of air. inferior catechu, tannic and gallic acids, am-
In such an apparatus the weed is digested monium acetate, fats, oils, gum, nitrogenous
with about three times its weight of ammonia substances, and a dye (areca red). The charcoal
solution at 60 for from three days to one week, of the nut used as a tooth powder, and the
is
the admission of air being regulated according ground nut is employed as a remedy for tape-
to the judgment of the manufacturer. The worm.
first product of the reaction has a blue colour, AREOMETER v. HYDROMETER.
and if the process be stopped at this point, ARGAL v. ARGOL.
there is formed the dyeware known as blue ARGAN OIL. An oil obtained from the
orchil. On the other hand, if the action of the kernels of Argania Sideroxylon (Roem. et Schult)
air and ammonia is allowed to proceed further, (ord. Sapotacece), growing in Morocco. The
red orchil is obtained. These orchil pastes kernels are first roasted, ground to powder and
when dried and finely ground, constitute the mixed with water, when the oil separates (Pharm.
product known as cudbear. J. [3] 10, 127).
Bedford (Ger. Pat. 57612, 1889) blows air ARGENT AN. Aluminium bronze (v. ALU-
or oxygen through the ammoniacal mixture, MINIUM).
which, especially in the latter case, materially ARGENTINE. A name given by R. Kirwan
shortens the process. The apparatus employed in 1794 to a variety of calcite (CaC0 3 ) occurring
is erected vertically, and by an ingenious as small scales with a pearly white or silvery
arrangement of projecting shelves, the edges of lustre.
which are turned down, a considerable quantity ARGENTINE. Finely divided spongy tin,
ARGININE. 289
made by reducing a weak solution of tin salt casein, 0-25 p.c. (Hedin, Zeitsch. physiol.
(120 in 60 litres of water) by zinc.
grams The :
Chem. 1894, 20, 186), whilst the protamines
tin is collected in a sieve, washed with water, !
salmine, sturine, Clupeine, Scombrine, Cyclopte-

and dried at a gentle heat. Used for tin-plating rine, and Crenilabrine yield arginine as the
and also for printing upon fabrics and paper chief product of hydrolysis (Kossel, Zeitsch.
(Deut. Ind. Zeit. 23, 255; J. Soc. Chem. Ind. physiol. Chem. 1896, 22, 176; 1898, 25, 165-
7, 504). 1899, 26, 588; 1904, 40, 565; 1910, 69, 138).
ARGENTITE. A mineral consisting of silver In cases of phosphorus-poisoning
arginine is
Ag 2 S, and occurring as cubic crystals found in the urine (Wohlgemuth, Zeitsch.
sulphide
or as compact masses. It is blackish lead-grey physiol.Chem. 1905, 44, 74), whilst the
in colour, and perfectly sectile ; surfaces cut amount obtained from the liver is diminished
with a knife are bright and shining. Containing (Wakeman, Zeitsch. physiol. Chem. 1908, 44
87 ! p.c. of silver, it is a valuable ore of the 335).
metal when met with in quantity, as in the When arginine is heated with barium
Comstock lode in Nevada and in Mexico. hydroxide, it is decomposed into ammonia,
L. J. S. carbamide, and ornithine (q.v.) (ati-diaminovaleric
ARGENTOL. A acid); cyanamide reacts with ornithine at the
synthetic antiseptic, con-
of silver, with quinosol, ordinary temperature to form arginine (Schulze
sisting of a compound and Winterstein, Zeitsch. physiol. Chem. 1898,
of the formula C 9 6 N(OH)SOyAg. H Forms a
Ber. 1899, 32, 3191 f, or with a-ben-
26, 1
yellowish powder, of a faint smell, sparingly
;
soluble in water and alcohol (Pharm. Zeit. 1897, zoylornithine to form the benzoyl derivative
of arginine, and this is readily hydrolysed to
42, 243).
arginine, which is thus proved to be a-amino-
ARGENTORAT. Trade name for a flash- S-guanino-n-valeric acid (Sorensen, Ber. 1910,
powder consisting of a mixture of potassium 43, 643).
perchlorate and aluminium, used in photo-
Arginine crystallises in brilliant monoclinic
graphy gives very little smoke (v. FLASH-
:
plates (Haushofer, Zeitsch. physiol. Chem.
POWDERS). 1887, 11, 53); m.p. 207-207-5 (Gulewitz,
ARGINASE. An enzyme occurring in the Zeitsch. physiol. Chem. 1899, 27, 178); it also
present in the kidney, the intestinal
liver, also crystallises with 1H 2 in rhombohedra (Hedin,
mucous membrane, thymus, and other organs Zeitsch. physiol. Chem. 1895, 21, 160); it dis-
(Kossel and Dakin, Zeitsch. physiol. Chem. solves readily in water, and is sparingly soluble
1904, 41, 321), and found by Shiga (Zeitsch. in alcohol. Arginine contains an asymmetric
physiol. Chem. 1904, 42, 502) among the carbon atom, and the dextrorotatory form is
enzymes obtained from yeast ; it can be the natural product, the hydrochloride has
extracted from the liver by water or dilute ro]D + 12'5 in aqueous or +25-5 in hydrochloric
acetic acid, precipitated from solution
and is
acid solution.
Arginine is strongly alkaline,
by alcohol, ammonium sulphate.
ether, or and solution absorbs carbon dioxide from
its
Arginase is a specific enzyme for the exclusive the air ; it forms well defined crystalline salts
hydrolysis of d-arginine or of substances con- with acids, and compounds with certain metallic
taining the d-arginine grouping, which it converts salts (Gulewitz, I.e.).
The nitrate C 6 Hj.,O 2 N 4 ,
almost quantitatively into carbamide and d- HN0 ,H,0 has the dinitrate
3 m.p. 126;
ornithine. Creatine and other guanidine deri- C H 14 N" ,2HN0 3 has m.p. 151;
6 2 4
the hydro-
vatives structurally similar to arginine, or
chloride C H 14 N 6 2 4 ,HC1,H 2 melts and decom-
itself, are incapable of hydrolysis at 209 when anhydrous the silver
poses ;
y this enzyme (Dakin, J. Biol. Chem. 1907, 3,

fuanidine
nitrate compounds C 6 H 14 2 N 4 ,AgNO,,^H 2
M. A. W.
435).
decomposes at 164, and C 6 H 14 2 N 4 ,AgN0 3 ,
ARGININE C 6 H 14 2 N 4, a-amino-S-guanino- HN0 3 melts and decomposes at 180 the ;
n-valericacidNH :
C(NH 2 )-NH-(CH 2 3 -CH(NH ) 2 )- cupric nitrate compound 2C 6 H, 4 2 N 4 ,Cu(N0 3 ) 2 ,
CO..H, first isolated by Schulze and Steiger 3H 2 melts at 112-114 or decomposes at

(Ber. 1886, 19, 1177) from the etiolated germi- 232-234 when anhydrous the copper sulphate ;
nated cotyledons of Lupinus, the most widely is compound melts at 110 or decomposes when
distributed dissociation product of proteid anhydrous at 235-238 the picrate C 6 H 14 2 N 4
;
.
matter, and can be obtained by hydrolysis of C 6 H 3 7N 3 ,2H 2 0, m.p. 205, dissolves in 204-1
the proteid matter of seeds of Lupinus luteus, parts of water at 16; thepicrolonate C 6 14 2 4
H N ,
Cucurbita pepo, Picea excelsa, to the extent of H N

C 10 8 5 4 ,H 2 0, m.p. 231, dissolves in 1124
of alcohol at the
10 p.c., Abies pectinata, Pinus sylvestris, and other parts of water, or 2885 parts
conifers (Schulze, Ber. 1891, 24, 276 ; Zeitsch. ordinary temperature (Schulze and Steiger,
physiol. Chem. 1896, 22, 411, 435; 1897, 24, Ber. 1886, 19. 1177 Hedin, Zeitsch. physiol.
;
276). According to Suzuki (Chem. Zeit. 1899, Chem. 1894, 20. 186 Gulewitz, ibid. 1899, 27, ;
23, 658) the arginine obtained from the seeds 178 ; Steudel, ibid. 1903, 37, 219 ; Reisser, ibid.
of conifers exists
already formed, but in loose 1906, 49, 210).
combination with the proteid material, and is Certain acyl derivatives and esters of arginine
also produced synthetically in the plant from have also been prepared, the dibenzoyl derivative
ammonium salts and nitrates, either in full or H N
C 6 12 2 4 Bz 2 crystallises in rhombic needles
diffused daylight (Bull. CoU. Agr. Tokyo Imp. or prisms, m.p. 2i7-5-218 (Gulewitz, I.e.), the
Univ. 1900, 4, 25). Arginine is also one of the P-naphihalenesulphonic derivative
C g H 13 O 2 Nj-
constituents of the product of hydrolysis of SOyC 10H 7 is a colourless powder, m.p. 88-89
is isolated
proteids of animal origin, thus, horn yields (Reisser, diarginylarginine
I.e.) ;
2-25 p.c. ; glue, 2-60 p.c. ; conglutin, 2-75 p.c. ; N

as the ^WcmfeC t8 38 4 1 ,(C g 3 7
N 3 ) 2 ,2H 2 0,
H H
obtained by hydro-
albumen from yolk of egg, 2-3 p.c. ; from white m.p. 207, from the product
of egg, 0-8 p.c. ; blood serum. 0-7 with hydrogen fluoride;
p.c. ; and lysing pepsin extract
VOL. I. T.
290 ARGININE.
arginylarginine picrate Ci 2 H 26 3 N 8 ,C 6 H 3 7
N 3, 33 hours (Reisser, Zeitsch. physiol. Chem. 1906,
2H 2 0, 213, is similarly obtained from
m.p. 49, 210) ; it decomposes at 210 (Cathcart, Proc.
gelatin (Hugouenq and Morel, Compt. rend. Physiol. Soc. 1905, 39) ; the nitrate C 6 14 O.,X 4 H ,
1909, 148, 236) ; arginine methyl ester hydro- HN0 3 has m.p. 216 the dinitrate C 6 H 14 2 N 4
, ; ,
chloride has m.p. 195 (corr.) with decomposition, 2HN0 3 m.p. 151 the cupric nitrate derivative
, ;
the picrate forms lemon-yellow crystals, which H

2C 6 14 2 N 4 ,Cu(N0 3 ) 2 ,3H 2 0, m.p. 228-229 ;
melt and decompose at 218 (corr.); and the the silver nitrate derivative (C 6 14 2 N 4 ,HN0 3 2 H ) ,
nitrate melts at 189 (corr.) (Fischer and AgN0 3 m.p. 170-172; theîcra<eC 6 H 14 2 N
, 4 ,
Suzuki, Sitzungber. K. Akad. Wiss. Berlin . C 6 H 3 O 7 N 3 m.p. 200-201, is sparingly soluble

,
1904, 1333). 100 parts of water at 16 dissolve 0-22 parts ;

The presence of arginine assists the tryptic the picrolonate C 6 14 O 2 4 ,C 10 8 5 4 m.p. H N H N ,
digestion of proteid matter and aids the emulsifi- 248, 100 c.c. of water at 16 dissolve 0-03
cation of fats this appears to be connected with
:
grams of salt the p-naphtJialene sulphonate
;
its alkalinity, as sodium carbonate acts similarly C 6 H 13 2 N4 -

S0 2 -C 10H 7 ,|H 2 0, has m.p. 85-90
(Lawroff, Zeitsch. physiol. Chem. 1899, 28, (Reisser, I.e.).
303). When arginine (hydrochloride or car- ^-Arginine is formed by treating t^-arginine
bonate) is administered as a food, it suffers carbonate with the expressed juice of calf's
complete decomposition, and 3777 p.c. of the liver, the ferment arginase present in the extract
nitrogen so given reappears as urea (Thompson, destroys the d-arginine, and does not attack the
Zeitsch. physiol. Chem. 1905, 33, 106), and the Isevo- isomeride. With the exception of the
amount of arginine in the various organs shows difference in optical activity, the salts of l-
no increase (Orglmeister, Beitr. Chem. Physiol.
arginine are identical with those of the dextro-
Path. 1905, 7, 27).
isomeride, l-arginine hydrochloride has
Arginine is readily oxidised by hot calcium [a]
or barium permanganate yielding guanidine, -20'51 (Reisser, I.e.). M. A. W.
7-guaninobutyric acid and succinicacid(Benech, ARGININE. This name has also been given
Kutscher, Zeitsch. physiol. Chem. 1901, 32, to an alkaloid discovered J. Pharm.
by Quiroga (
278, 413), and the estimation of the number of Chim. 1896, 16, 293) in a species of laurel (known
arginine groups in proteids is based on this by the natives as viraro-mi), growing in the east
reaction (Orglmeister, I.e. ; Kutscher and of the Argentine and west of Brazil. It forms
Zickgraf, Sitzungsber. K. Akad. Wiss. Berlin, prismatic crystals, soluble in chloroform or
1903, 28, 624), the guanidine thus obtained
benzene, slightly soluble in ether, petroleum
being isolated in the form of its sparingly soluble spirit, or water. Its aqueous solutions,
picrate, and either weighed as such, or the acidified with hydrochloric acid, give a white
nitrogen estimated in the usual way. Another ppt. with bromine water and a white ppt.
method of isolating and estimating arginine with alkali soluble in excess. The bark and
is based on Siegfried's carbamino- reaction of
cambium contain 1-5-1 -6 p.c., the wood 0-04-
amino- acids (Zeitsch. physiol. Chem. 1905, 44, 0-05 p.c. of the alkaloid. H. I.
85 ; 46, 402 ; 1907, 50, 171 ; Ber. 1906, 39, 397),
ARGOL or ARGAL. (Tartre brut, Fr. ;
whereby the barium, strontium, or calcium salt
of the corresponding carbamic acid is formed Weinstein, Ger.) Crude potassium bitartrate,
when carbon dioxide is passed into a solution known as red argol (Cremore di Vinaccia), or
white argol (Cremore di St. Artimo), according
of the amino- acid containing excess of alkali
to whether it is deposited from the red or the
earth hydroxide until the solution is neutral
to phenolphthalem white grape (v. TARTARIC ACID).
ARGON. Sym. A or Ar. At. wt. and
RCH-NH, molec. wt. long ago as 1785,
39-88. As
Cavendish (Phil. Trans. 75, 372) made experi-
I +Ca(OH) 2 +C0 2
C0 2 H ments in order to determine whether the inert
residue left after withdrawing oxygen, water,
R-CH-NH-COj
=
>Ca+H 2 0. and carbon dioxide from air was homogeneous.
I
CO, He sparked a mixture of air and oxygen

in presence of potash for the absorption of the
The barium and strontium salts of these com- acid produced, and removed the excess of
plex carbamic acids are much less readily oxygen by a solution of liver of sulphur. Only
soluble than the corresponding amino- acid, and a small bubble of gas remained unabsorbed,
afford a means of isolating the compounds and this did not diminish in volume on further
(D. R. P. 188005, 1906). In order to estimate sparking with oxygen. Cavendish concluded
' '
the amino- acid, the filtrate containing the
'
that if there is any part of the nitrogen of our
calcium salt of the carbamic acid is decomposed atmosphere which differs from the rest, and
cannot be reduced to nitrous acid, we may safely
by heating with boiled-out water into calcium
carbonate, and the amino acid the ratio C0 2 ;
: N conclude that it is not more than -^ part of
is determined by weighing the calcium carbonate the whole.'
thus precipitated, and estimating the nitrogen Cavendish's work was overlooked for more
in the filtrate by Kjeldahl's method (Zeitsch. than a century, and attention was only directed
physiol. Chem. 1908, 54, 423). to it after the discovery, in 1894, by Lord
cH-Arginine is readily produced by the Rayleigh (Roy. Soc. Proc. 55, 340), that the
' '
tryptic fermentation of fibrin, or by heating density of atmospheric nitrogen was one-

d-arginine nitrate at 210-220 for 15-20 half per cent, higher than 'that of nitrogen
minutes (Kutscher, Zeitsch. physiol. Chem. prepared by chemical means. This result gave
1901, 32, 476) or by heating d-arginine in 50 p.c. fresh indication of the existence of some hitherto
sulphuric acid in sealed tubes at 160-180 for undiscovered gas in the atmosphere, and further
ARGON. 291
investigations, carried out jointly by Rayleigh

mixture having previously been heated under
and Ramsay (Phil. Trans. 186, 187), led to the diminished pressure to drive off any volatile
isolation of a new gaseous element. The gas, matter. Both oxygen and nitrogen are absorbed
which has a density of approximately 20, and by the mixture. The issuing gas is led over hot
which constitutes nearly 1 p.c. by volume of the copper oxide to burn any hydrogen, hydro-
atmosphere, was called argon, owing to its carbons, and carbon monoxide present, and the
remarkable chemical inertness, in virtue of which water vapour and carbon dioxide removed.
it can be readily separated from the accom- Using 7 kilos, of carbide, 11 litres of argon may
panying nitrogen. be obtained in two days (Fischer and Rinee
Ber. 41, 2017).
Argon occurs in the atmosphere to the
extent of 1'3 p.c. by weight (Leduc, Compt. The gas prepared by the above methods
rend. 123, 805) and 0-933 p.c. by volume contains traces of the other inert gases neon,
(Schloesing, Compt. rend. 121, 604 Moissan,
; krypton, and xenon, from which it is separated
Compt. rend. 137, 600). It also occurs in a by fractional condensation and evaporation
large number of mineral waters and thermal (Ramsay and Travers, Roy. Soc. Proc. 67, 329 ;
springs (Bouchard, Compt. rend. 121, 392 ; Liveing and Dewar, Roy.' Soc. Proc. 68, 389).
Troost and Ouvrard, ibid. 121, 798 ; Moissan, The total quantity of these gases present is,
ibid. 135,1278; Moureu, ibid. 135, 1335; 142, however, only 0-25 p.c., and 85 p.c. of this
1155), and in the volcanic gases of Mt. Pele'e impurity is neon.
(Moissan, Compt. rend. 135, 1085); it is found, Argon is a colourless gas, condensing to a
moreover, in fire damp and in coal (Schloesing, colourless liquid, boiling at 86-9 abs. ( 186-1),
Compt. rend. 123, 233). Argon has also been at which temperature its density is 1-4046
observed, together with helium, in the gas (Baly and Don nan, Chem. Soc." Trans. 81,
evolved on heating numerous minerals. 914). Its m.p. is 83-4 abs. ( 189-6), its
critical temperature is 155-6 abs. (
Preparation. (i.) By sparking air with 117-4),
and its critical pressure is 52-9 atmos. (Ramsay
oxygen, the method originally employed by
Cavendish (v. supra). The gas is preferably and Travers, Roy. Soc. Proc. 67, 329).
confined over mercury, and a small quantity Argon is more soluble in water than nitrogen,
of potash introduced through a curved pipette. the absorption coefficient being 0-02561, at 1,
The sparks are passed between the ends of and falling regularly to 0-02567 at 50
stout platinum wires, fused through the ends (Estreicher, Zeitsch. phys. Chem. 31, 176) these ;
of U-shaped glass tubes. These tubes are filled figures may, however, be in error by 5 p.c. (v.
with mercury, and serve to establish elec- Fox, Chem. News, 99, 250). The refractive
tricalconnection with the secondary terminals index of the gas for sodium light at N.T.P. is
of a Ruhmkorff coil capable of giving a 6-inch 1-0002837 (Burton, Roy. Soc. Proc. 1908, 80,
spark through air when worked by four lead 390) ; its thermal conductivity is 0-00003894
accumulators. The sparking is usually con- (Schwaize, Pogg. Ann. 11, (iv.) 303); and its
tinued for several hours after contraction has molecular specific heat at constant volume is
ceased ; the excess of oxygen is then absorbed 2-977 cals. (Pier, Z. Elek. 15, 536). Its
by phosphorus (Rayleigh and Ramsay, I.e. ; coefficient of expansion is 0-003668 (Kuenen
Rayleigh, Chem. Soc. Proc. 13, 181; Becker, i
and Randall, Roy. Soc. Proc. 59, 60). Argon
Z. Elek. 9, 600). To save time, it is customary passes through rubber more quickly than
;
to prepare by method (ii.) a gas consisting nitrogen (Rayleigh, Phil. Mag. 49, (v.) 220) or
mainly of argon, and to employ the method carbon dioxide (Kistiakowski, J. Russ. Chem.
of sparking only to remove the last traces of Soc. 30, 576), and does not pass through heated
platinum or palladium ; it is diamagnetic
(ii.) From
'
atmospheric nitrogen,' the nitrogen (Tanzler, Pogg. Ann. 24, (iv.) 931). (For its
rate of effusion, v. Donnan (Phil. Mag. 49, (v.)
being absorbed by a metal. In their original
investigation, Rayleigh and Ramsay separated ;
423).)
iargon from nitrogen by continuously circulating The density of argon has been determined
sthemixture over red-hot magnesium shavings, by several observers, with the following results :
whereby the nitrogen was absorbed, forming (O = 16); 19-940 (Rayleigh, Roy. Soc. Proc.
magnesium nitride (c/. Ramsay
and Travers, }
59, 201), 19-941 (Ramsay, Phil Trans. 186, 238) ;
Roy. Soc. Proc. 64, 183). This method is no 19-945 (Fischer and Hahnel, Ber. 43, 1435).
longer used ; a dry mixture of pure lime (5 parts) Argon is a member of the group of inert gases,
id magnesium dust (3
1 1
parts), introduced by
and up to the present all attempts to combine
Maquenne, is employed instead, which, when , it with other elements have failed (Rayleigh and
heated to redness, produces metallic calcium Ramsay, I.e. ; but c/. Cooke, Zeitsch. physik&l.
vnd absorbs nitrogen with great rapidity. By Chem. 55, 537).
lassing atmospheric nitrogen over this red-hot Atomic and molecular weight. The molecular
nixture, and leading the residual gas over weight, 39-88, follows from the density determina-
netallic calcium heated to dull redness, complete i
tions just cited but the atomic weight cannot
;
ibsorption of the nitrogen is readily effected !

be determined in the usual manner, since argon
Moissan and Rigaut, Compt. rend. 137, 773). forms no compounds with other elements. The
Metallic lithium has also been employed for ratio of the specific heat at constant pressure
he same purpose (Guntz, Compt. rend. 120, to the specific heat at constant volume is 1-644
(Rayleigh and Ramsay, I.e.), and
77 ; 123, 995). this result,
The readiest means of preparing argon
(iii.) from analogy with the case of mercury vapour
i
quantity consists in leading air slowly over and by comparison with the ratio 1 -666 theoreti-
mixture of calcium carbide (90 p.c.) and cally required for a monatomic gas according
alcium chloride (10 p.c.) heated to 800, the to the kinetic theory, is regarded as proof that
292 ARGON.
argon is monatomic. Its atomic weight is molasses or a mixture of these is added to the
therefore 39-88. rice. The whole is allowed to ferment, and the
This is mixture is then distilled.
Spectrum. extremely characteristic,
and has been carefully examined by Crookes This method, which is said to produce the
(Phil. Trans. 186, 243), Kayser (Chem. News, best quality of arrack, obtains at Batavia and
72, 99), Eder and Valenta (Monatsh. 16, 893 17, ; in Jamaica, but in India arrack is
frequently
50), and by Trowbridge and Richards (Phil. made from toddy alone.
Mag. 43, (5) 77). The most prominent lines The best qualities of arrack are agreeable
are two in the red, having wave lengths of to the taste and wholesome, which cannot be
6965-6 and 7056-4, a yellow line (6038-4), two said of the commoner kind made from rice
green lines (5610 and 4702), and a violet line alone, in some parts of India and China. This
(4200). has a somewhat nauseous odour and taste,
ARGYRODITE. A sulpho-germaniate of due to a volatile oil which distils from the rice,
silver, being the mineral in which the element and is narcotic and very unwholesome. Its
germanium was discovered in 1886. It had, intoxicating effect is frequently increased by
however, been mentioned by A. Breithaupt in the addition of hemp leaves, poppy heads,
1823, under the name Plusinglanz. These stramonium juice, &c.
occurrences in the Himmelsfiirst silver-mine A large amount of revenue is obtained from
at Freiberg, Saxony, show only botryoidal the manufacture of arrack in Siam and Ceylon,
crusts with a minutely crystallised surface. and the latter exports a considerable quantity to
Later, the mineral was found as distinct, though the United Kingdom, where it is used as a
small, cubic crystals in Bolivia, analysis of valuable ingredient in making punch.
which proved the formula to be Ag 8 GeS 6 (S. L. An imitation arrack is sometimes made by
Penfield, 1893 and 1894). More recently, cubic rum with flowers of benjamin or ben-
flavouring
crystals of larger size (3-5 cm. across) from zoic acid. J. C.
Colquechaca, Bolivia, have been described and
ARROPE. Sherry boiled to a syrup, used for
analysed (V. M. Goldschmidt, 1908). At this
colouring other wines.
locality the mineral appears to be not uncommon,
and no doubt large quantities of have been it ARROWROOT. The starch obtained from the
smelted for silver. In external appearance it rhizomes of Maranta arundinacea, grown in the
is not unlike argentite, but is less sectile than West Indies. The starch prepared from other
this. roots is often known locally as arrowroot;
In the Bolivian mineral the germanium may e.g. in Queensland, where the tubers of Canna
edulis supply such a product.
be replaced isomorphously by tin, giving the
The composition of the roots of true arrow-
species canfieldite Ag 8SnS g (Penfield, 1894).
Intermediate members of this series, or stanni- root grown in Jamaica is :
ferous argyrodite, also occur (Prior and Spencer, Dextrin Crude Ether
L. J. S. Water Starch and sugar fibre extract Proteid Ash
1898).
63-4 27-8 2-1 3-9 0-2 1-6 0-9
ARIBINE v. VEGETO-ALKALOIDS.
ARICINE v. VEGETO-ALKALOIDS. (Leuscher, Zeit. offentl. Chem. 1902, 8, 23.)
ARISTOCHIN. Trade name for Commercial arrowroot contains from 83-5 to
di-quinine
carbonate CO(0-C 20 H 23 N 2 0) 2 .
86-9 p.c. starch, 11-0 to 15 p.c. water, proteins
from 0-4 to 1-4 p.c., with small quantities
ARISTOL. Dithymol di-iodide used as an
(circa 0-3 p.c.) of ash, cellulose, and fat.
iodoform substitute.
a series of of arrowroots
ARJUN WAX v. WAXES. (For
from various sources,
analyses
see Ballard, Jour. Pharm.
ARMENIAN BOLE v. PIGMENTS. 1903, 17, [10] 476.) H. I.
ARNATTO v. ANNATTO. ARSACETIN. The sodium salt of acetyl-
ARNICA v. RESINS. p-aminophenyl arsenic acid
ARNICA YELLOW v. Azo- COLOURING /OH
MATTERS. CH 3 -CO-NH-C H 4 -As^=O
6
ARNOTTO v. ANNATTO. \ONa

AROMATIC VINEGAR v. ACETIC ACID. (v. ARSENIC, Organic compounds of).
ARRACK. (Aracka,ndRack,T?T. Arrack :Reis- ;
ARSENIC. (Arsenic, Fr. ; Arsenic, Arsen,
' ' '
brauntwein, Ger. ) The term araq or arak was
'
Ger. ) Schwerbenkobalt, Fliegengift, Napfchenkobalt
applied by the Arabs to distilled spirits generally, Arsenicum. Regulus Arsenici. Symbol, As ; at.
but it is now usually restricted to the spirituous wt. 74-9.
liquor obtained by distillation of the fermented Occurrence. Arsenic, in small quantities, is
juice of the coco-nut palm (toddy or palm wine), one of the most widely distributed elements ;
or from rice, or from a mixture of both. Arrack it is found in mineral and other waters, and in
is also made from the succulent flowers of the coal smoke, in most pyretic minerals, and in a
Bassia genus of trees and from other vegetable large number of ores.
products, and is manufactured not only in the In England it occurs principally with tin ore,
East, but also in the West Indies. and on the Continent in mispickel. Arsenic
Whererice is used, it is steeped in water occurs native (usually associated with iron,
in large vatsand agitated cautiously (so as not to cobalt, nickel, antimony, and silver) in crystal-
damage the grains, which would interfere with line rocks and hi the older schists, generally in
the subsequent fermentation) until about half reniform and stalactitic masses, often mammil-
the rice has begun to germinate. The water lated ; it also occurs occasionally in rhombo-
is then run off from below, and toddy or hedral crystals. At Zimeoff in Siberia, large
ARSENIC. 293
masses are found it occurs in the silver-mines

; good conductor of electricity, and is odourless
of Freiberg, Annaberg, Marienberg, and Schnee- and tasteless.
berg in Saxony ; at Joachimsthal in Bohemia, It is volatile at temperatures above 100, and

Andreasberg in the Hartz, Kapnik in Transyl- is rapidly vaporised at a dull-red heat. At the
vania, Orawitza in the Banat, Kongsberg in ordinary pressure it volatilises without previous
Norway, St. Marie-aux-Mines in Alsace, in fusion, the vapour being yellow and of a garlic
Borneo, and in the United States. smell, but when heated under pressure it melts
As arsenide it occurs combined with iron in at 500 (Landolt). Joubert states that above
two forms FeAs 2 and Fe 2 As 4 with nickel as
; 200 its vapour is phosphorescent (Compt. rend.
Kupfernickel NiAs and NiAs 2 with cobalt as
; 78, 1853).
tin white cobalt, CoAs 2 With antimony it
.
When the vapour is condensed at a tempera-
occurs as arsenical antimony, at Przibram in ture but little below the volatilising point, i.e.
Bohemia with blende, antimony and spathic
; when condensed in an atmosphere of arsenic, a
iron, at Allemont, at Schladming in Styria and nearly white compact mass of strongly metallic
Andreasberg in the Hartz. lustre is produced which scarcely oxidises in the
Arsenic is generally present in native sulphur. air even when heated to 80.
T
W
hen it is de-
Combined with sulphur it occurs as realgar or posited on a colder surface or in an atmosphere
ruby sulphur As 2 S.> in Hungary, Saxony, other than arsenic, it forms less dense, dark-grey
Switzerland, and China and as orpiment As 2 S 3
;
crystals which readily oxidise in the air even in
in Hungary and the Hartz. the cold, and especially on heating.
With sulphur and iron it occurs as mispickel, Ludwig Pharm. [2] 97, 23) has
(Arch.
arsenical pyrites, or white mundic FeS 2 FeAs 2 ; with obtained arsenic with a perfectly bright sur-
(?)
sulphur and cobalt in cobalt glance CoS 2 CoAs 2 :
face resembling freshly granulated zinc, and of
in nickel glance NiS 2 NiAs 2 , and in a number the low density 5 -395, by distilling in a tube with
of other ores, being obtained as a secondary a small quantity of iodine.
product in the roasting of tin and copper When heated in air it absorbs oxygen, burn-
ores, copper nickel, arsenical fahl ores, smaltine, ing with a bluish flame and forming arsenious
cobalt and nickel glance, &c. oxide. In pure water it is unaltered, but when
With oxygen, arsenic occurs as arsenolite or exposed to air it forms a grey powder supposed
arsenite As 4 8 usually as a crust on other
, by some to be a suboxide, but probably a mixture
arsenical minerals, being formed by their de- of metallic arsenic and arsenious oxide this ;
composition. With oxygen and cobalt, it forms fly-powder.' When powdered

'
powder is sold as
cobaltbloom or arsenate of cobalt ; it also occurs and thrown into chlorine, it ignites, forming the
as arsenates of iron, copper, and lead. trichloride ; with the aid of heat it combines with
Preparation. Metallic arsenic is used only bromine, iodine, and sulphur. Hydrochloric
to a small extent in commerce. It is usually acid has but little action on arsenic, but it is
prepared from native arsenic, arsenical iron, or rapidly dissolved by nitric acid, aqua regia, or
mispickel, the latter being the only mineral by a mixture of hydrochloric acid and potassium
used to any extent in England. The mineral chlorate.
used is heated in earthenware retorts or tubes When deflagrated with nitre it forms potas-
laid horizontally in a long furnace. Great care sium arsenate.
is required in manufacturing the retorts ; a Bettendorf (Annalen, 144, 110) has obtained
mixture of 1 part fresh clay and 2 parts bricks a specular, amorphous, vitreous arsenic of sp.gr.
or old retorts powdered, is made into the proper 4-69-^t-716 by subliming arsenic in a stream of
form, coated with a mixture of blood, loam, hydrogen and condensing it at'210-220.
At
forge-scales and alum to produce the glaze, and 360 it is converted into the crystalline form
burned. They are very strong and heat-resist- with the evolution of considerable heat, and
ing, and quite impervious to the vapour of when heated suddenly it hisses and gives off
arsenic. A piece of thin iron sheet is rolled and vapour whilst transforming.
inserted into the mouth of the retort, and an Arsenic is a constituent of many alloys it ;
earthen receiver luted on. On distilling, most is used for bronzing brass and for the manufac-
of the arsenic condenses in the iron as a nearly ture of opal glass.
white, coherent, internally crystalline mass, and commercial
(For the distribution of arsenic in
is detached on
cooling by unrolling the iron.
If required, the arsenic is products, v. Arsenious oxide.)
purified by redistilla- when
tion. Detection. Arsenical compounds,
heated on charcoal, give off the characteristic
At Altenberg in Silesia, arsenious oxide is white fumes of the oxide, with
heated with charcoal iia an earthen crucible garlic odour and
a white incrustation on the charcoal some dis-
covered with an inverted crucible or conical iron
tance from the assay. Metallic arsenic, and
cap. This method is more economical and pro- when
ductive than the one above described, but the many arsenical minerals, such as mispickel,
heated in a tube closed at one end, form a
metal is grey and pulverulent, and always con- on the cooler
tains arsenious acid.
blackish, shining metallic ring
if heated in a tube open
portion of the tube ;
at both ends, the arsenic is oxidised, and
con-
It may also be prepared by heating the
sulphides with charcoal and sodium carbonate denses in a ring of white octahedral crystals,
or potassium cyanide. their shape being plainly visible under a lens.
Properties. Arsenic is a very brittle steel- On cutting off the closed end of the tube con-
and heating, it is
grey metalline mass of sp.gr. 5-62 to 5-96, of taining the metallic mirror,
brilliant lustre, crystallising in rhombohedra, also converted into the white ring higher up
isomorphous with metallic antimony. It is a the tube. The white crystals dissolve in boiling
294 ARSENIC.
water, and the solution shows the usual tests performed in the same manner to ensure the
for arsenic. Antimony under like circumstances purity of the zinc and acid. It is essential not
would produce a white ring, which, however, is only to obtain zinc and acid which are free from
not crystalline, and is not soluble in water. traces of arsenic, but also to see that the zinc
Oxides of arsenic require to be mixed with used is ' sensitive,' and will permit all the arsenic
charcoal before they produce the black mirror. in the solution to be evolved as arseniuretted
Sulphides require the addition of alkaline car- hydrogen. The presence hi the solution of
bonate or potassium cyanide, or they may be certain metals notably iron is liable to retard,
heated with baryta alone (Brame). or entirely prevent, the evolution of arseniuretted
White arsenic when heated with about 3 hydrogen. (On the presence of arsenic hi glass
as a source of error in the detection of arsenic,
parts of sodium acetate, gives the offensive smell
v. W. Fresenius, Zeitsch. anal. Chem.
of kakodyl. 22, 397 ;
Ber. 17, 2938.) Instead of heating the tube, the
In solution the reactions of the two series of
gas may be ignited at the mouth of the tube, and
compounds, the arsenious and the arsenic, differ
the flame caused to impinge on a cold surface of
considerably generally speaking, arsenic com-
;
porcelain, or preferably of platinum foil. The
pounds may be converted into the arsenious arsenic film may be distinguished
form by heating with sulphurous acid or with from that
a sulphite. produced by antimony as follows :
Reinsch's test. Ifa piece of clean metallic (1) The arsenic film is quickly evaporated,
while that of antimony only slowly disappears.
copper is immersed in a solution of arsenious
acid or an arsenious Helling (Das Microscop in der Toxicologie) re-
compound acidulated with commends that small spots be heated and the
pure hydrochloric acid, it is coated with a grey
vapour received on a slip of glass, when, under
film, which is probably an arsenide of copper.
the microscope, the octahedral crystals due
The action proceeds better at the boiling tem-
arsenic are visible.
perature. The acid must first be tested in the
same manner to ensure the absence of arsenic, (2) The arsenic film quickly dissolves in a
which is always present in the commercial acid. solution of sodium hypochlorite ; the antimony
The metal is washed, dried gently and heated film is
very slowly soluble.
in a tube, when the arsenic becomes oxidised (3) The antimony film dissolves quickly in
and forms a crystalline ring on the colder part yellow ammonium sulphide, leaving an orange-
of the tube. A film due to antimony, as men- yellow residue on evaporation ; the arsenic film
tioned before, would not produce a crystalline dissolves very slowly.
ring. Magnesium may also be employed in place of
This method is used in testing for and re- zinc, and E. Davy and Al. Jandousch use an
moving arsenic from hydrochloric acid, and in amalgam of 1 part sodium in 8 parts mercury,
toxicology by it 1 part of arsenic can be
; with or without acid.
detected in 250,000 parts of solution. The presence of nitrates or nitric acid inter-
It is not so delicate as Marsh's or the electro- feres with this and the acids used should
test,
lytic method. be dilute.
When
hydrogen is generated in a liquid con- (For the detection and estimation of arsenic
taining an arsenious compound, the arsenic by electrolytical methods, v. Arsenic in art.
combines with it and passes off as the gaseous ANALYSIS, ELECTRO-CHEMICAL.)
man} very delicate tests are based on
7
hydride ; Estimation. Arsenic is usually estimated
this reaction. as (I) magnesium pyro-arsenate ; (2) as arsenic
(1) Fleitmann's test. The solution is mixed sulphide ; (3) as metallic arsenic.
with excess of caustic potash, a piece of pure (1) For this method it is necessary that
zinc, or of magnesium, or aluminium foil in- the substance should be present as an arsenic
serted, and the solution heated. A piece of filter compound. The conversion from the arse-
paper moistened with silver nitrate is held over nious to the arsenic condition may be effected
the mouth of the tube. In presence of arsenic, by heating with nitric acid (v. Estimation as
arseniuretted hydrogen is produced and reduces sulphide) or hydrochloric acid and potassium
the silver on the paper forming a greyish or chlorate.
purplish colour. Antimony is not evolved in The acid solution, which should occupy only
this test. Fleitmann's test is therefore a ready '
a small bulk, is mixed with magnesia mixture
'
means of finding arsenic in presence of antimony ; and rendered strongly alkaline with ammonia.
it is not, however, so delicate as
Reinsch's, After standing for 24 hours, the solution is
Marsh's, or the electrolytic method. filtered, the last portions of the precipitate,
(2) Marsh's teft. This or Reinsch's test is which consists of ammonium magnesium arsen-
usually used in toxicology. The solution is ate, being washed entirely on to the filter paper
acidulated with pure hydrochloric acid and in- with a little of the filtrate (the volume of this
troduced into an apparatus in which hydrogen is filtrate should be noted roughly). The preci-
generated by means of pure sulphuric acid and pitate then washed with a mixture of 1 part
is
zinc. Arsenic hydride is formed and is passed strong ammonia and 3 parts water, until only a
through a narrow glass tube, Avhich is heated at slight opalescence is produced on the addition
one spot by a lamp ; the arseniuretted hydrogen of nitric acid and silver nitrate to a few drops
as it passes over the heated portion is decom- of the washings. It is then dried, detached as
posed with the precipitation of arsenic as a black much as possible from the filter paper, and
ring. In testing for very small quantities of transferred to a weighed porcelain crucible,
arsenic, the action should be continued for about moistened with nitric acid, dried, and ignited, at
an hour. A blank experiment should always be first gently, and finally to bright redness.
The
ARSENIC. 295
paper moistened with nitric acid, dried, and

is The latter should
produce no opalescence. If a
crucible and its
ignited on the lid, and the precipitate is produced, a further quantity of
contents weighed. The ignited residue consists tartaric acid or ammonium chloride must be
of magnesium pyro-arsenate Mg 2 As 2 7 , and added. The solution is then precipitated by
'
contains 48-27 p.c. of arsenic. magnesia mixture,' and the estimation made
On account of the solubility ot the ammonium as before described.
magnesium arsenate, an addition should be From tin. A solution of oxalic acid is
made to the weight obtained of 0-001 gram for added to the solution in the proportion of 20
each 16 c.c. of filtrate obtained, not counting the grams of oxalic acid for each gram of tin sup-
washings. posed to be present. The solution should be
(2) The arsenic for this method should be sufficiently strong for the acid to crystallise out
in the arsenious form. If arsenic compounds on cooling. The liquid is heated to boiling and
are present, they are preferably reduced by sulphuretted hydrogen passed through for 20
passing a current of sulphurous acid through the minutes, The liquid is allowed to stand for
liquid, the excess of that gas being driven off by about 30 minutes, and the arsenious sulphide
subsequent heating. Sulphuretted hydrogen is filtered off. It is quite free from tin.
then passed through the liquid until thoroughly Arsenious chloride in small quantities may be
saturated, the liquid left to stand for some time, separated from other metals by distillation of the
the excess of sulphuretted hydrogen driven off hydrochloric solution (Thorpe, Chem. Soc. Trans.
by heating, and the precipitated arsenious sul- 83, 971) ; in certain metals and alloys by
phide containing sulphur filtered off. The sul- distillation of the finely divided material with a
phide is dissolved in ammoftia, filtered if neces- suitable solution of ferric and calcium chlorides,
sary, and the arsenic estimated in the solution acidified with hydrochloric acid (the materials
by one of the three following methods : used should be tested for arsenic). With a
(a) The solution is evaporated to dryness in solution of zinc and cupric chlorides in hydro-
a porcelain dish, then covered with an inverted chloric acid boiling at 108 both arsenic and
funnel, and fuming nitric acid added. After the antimony may be separated from other metals ;
first violent action has ceased, the liquid is the arsenic is in the distillate from 108 to 115,
heated on a water-bath until the whole of the the antimony in the distillate from 115 to 160
sulphur has disappeared, and only a small bulk (Gibb, J. Soc. Chem. Ind. xx. 3).
' '
of liquid remains ; magnesia mixture is then For the estimation of arsenic in ores, Parnell
added, followed by excess of ammonia, and the recommends the following method A weighed
:
process followed as already described. quantity of the finely powdered ore is heated to
(6) The ammoniacal solution is evaporated about 200 in a slow current of chlorine gas,
to dryness in a porcelain dish, and heated on a the volatilised arsenious chloride being absorbed
sand-bath to drive off the whole of the free in a solution of chlorine water. After evapora-
sulphur and carboniseany organic matter tion of the excess of chlorine, the arsenic may
(which is present in toxicological
frequently be estimated by any ordinary method. Anti-
analysis) without volatilising any of the arsenious mony, if present in the ore, would also volatilise
sulphide. The residue is again dissolved in with the arsenic.
ammonia, filtered if necessary, evaporated to For technical purposes the following methods
dryness, and gently heated in a weighed porce- are largely used :
lain dish, and weighed as arsenious sulphide A weighed portion is partially decomposed
As 2 S 3 (Mohr, Chem. Toxicologie, 56). with a minimum quantity of strong nitric acid,
(c) The arsenic in the solution may be dried and fused with sodium peroxide or a mix-
estimated by means of standard iodine solution ture of sodium carbonate and nitre. The fused
(Champion and Pellet, Bull. Soc. chim. [2] 26, mass is extracted with water and filtered. The
541). solution of alkaline arsenate is acidified with
(3) For this method the arsenical mirror nitric acid and boiled to effect decomposition of
obtained by the Marsh- Berzelius method or the either peroxide or nitrite ; it is next carefully
electrolytic method may be estimated by com- neutralised and then acidified with acetic acid,
parison with standard mirrors obtained under and the arsenic determined by titration with a
similar conditions to the estimation. Experience standard solution of uranium acetate. Pearce
has shown that when hi the preparation of stand- recommends separation as silver arsenate from
ard mirrors, the quantities of arsenic used differ the aqueous extract after fusion ;
the silver
by amounts such as 0-002 milligram, a series of and estimated
salt is dissolved in dilute nitric acid
mirrors can be obtained showing differences in by Volhard's method. With very poor ores to
intensity which are sufficiently distinct and the solution in nitric acid a sufficient quantity of
constant to be utilised for comparison. tartaric acid is added, and the arsenic separated
Separation from other metals. Certain heavy as magnesium ammonium arsenate. For the
metals, if present, would be precipitated with estimation of arsenic in organic salts ignite with
the arsenious sulphide by means of sulphuretted sodium peroxide, reduce with hydriodic acid
hydrogen. From the sulphides of lead, bismuth, and titrate with iodine and starch in presence
&c., the arsenious sulphide can be dissolved by of disodium hydrogen phosphate (Morgan, Cheni.
digestion in ammonium sulphide. The solution Soc. Trans. 1909, 95, 1477).
would also contain antimony and tin, if present. Alloys of arsenic.
The separation of arsenic from these two metals Arsenic combines with most metals, in many
may be performed as follows : cases in atomic proportions, the alloys being
From antimony. The mixed sulphides are then known as arsenides. Many natural
oxidised with aqua regia, as already described, arsenides occur as minerals.
and tartaric acid solution added, followed by The alloys may be prepared (1) by fusing
excess of ammonium chloride and ammonia. the metals under a layer of borax, or in an
296 ARSENIC.
atmosphere of some inert gas (2) by reducing the
; With potassium and sodium arsenic forms
arsenite or arsenate of the metal with potassium j
alloys which evolve arseniuretted hydrogen when
cyanide ; and (3) in some cases as with gold, placed in water. With platinum it forms a
silver, and copper by placing arsenic in a fusible alloy, and was formerly used to facilitate
solution of a metallic salt. W. Spring (Ber. 16, the working of that metal.
324) has obtained crystalline alloys of arsenic Arsenic trihydride. Arse.ne.tted or arse
with other metals by repeatedly compressing a uretted hydrogen. Arsine. AsH 3 . This gas
mixture of the constituents at 6500 atmo- formed whenever hydrogen is liberated in
spheres. solution containing arsenious acid or an arseni
When heated out of contact with air, arsenical as when zinc is introduced into an acid soluti
alloys usually lose a portion of their arsenic ; of the substance. It is a colourless, nentr
heated in air the arsenic is oxidised, a portion disagreeably smelling gas, slightly soluble
volatilising, and the remainder forming an water, and highly poisonous, even when mu
arsenite or arsenate of the metal. When heated diluted. At a red heat it decomposes in
with nitre, arsenates are produced. (For a list arsenic and hydrogen.
of alloys of arsenic in atomic proportions, It is evolved in the bronzing of brass wi
probably existing as arsenides, v. A. Descamps. arsenic, in tinning sheet iron and frequently
Compt. rend. 686, 1022 and 1065. ) Some ancient the desilverisation of lead with zinc and sub;
copper from Cyprus contained
spear-heads quent heating of the argentiferous zinc wi
1-348 p.c. and a bronze figure of
arsenic, acid. It is also occasionally present in the
the Ptolemaic period from Egypt contained of rooms of which the wall-paper is colou:
1-479 p.c. with arsenical pigments (v. Schiveinfurth green).
The presence of arsenic generally renders It is a very powerful reducing agent, precipi-
an alloy more brittle, more fusible, and brighter. tating silver, gold, and other metals from their
In Pattinson's process it tends to render the solutions. Methods for the quantitative estima-
crystals smaller, and thus lengthens the time tion of arsenic are based on this property.
required for draining. Its alloys with iron, zinc, Asolid hydride of arsenic appears to exist.
and tin are brittle ; with gold and silver, brittle, Arsenious oxide. Arsenious acid. White
and grey ; and with lead and antimony, hard, arsenic. Flowers of arsenic ; commonly known
biittle, and fusible.
'
The addition of from 3 to 6 as arsenic.' As 4 6
.
parts arsenic to 1000 lead (with occasionally a Preparation. In Cornwall, Devon, and at
little copper) causes the small shot in falling Swansea, arsenious oxide is principally prepared
down the tower to form spheres, instead of by roasting mispickel, which occurs mixed with
elongating, as they have otherwise a tendency iron and copper pyrites, tin ore, wolfram, blende,
to do. The arsenic is frequently added in the galena, &c. These ores, if present in sufficient
proper proportions in the form of an alloy of quantity, are separated as far as possible before
lead and arsenic known as
' '
temper ; this is roasting ; tinstone by washing the finely

prepared by fusing together arsenious oxide and powdered ore, and the other minerals by hand.
lead. By heating a mixture of lead and arsenic Arsenious oxide is also largely prepared by
to whiteness, Berthier obtained an alloy of roasting arsenical silver at Andreasberg, a:
the formula Pb 4 As, any excess of arsenic beyond from arsenical ores of nickel and cobalt.
that corresponding to this formula being vola- In ores from which arsenic is produced as"
tilised at that temperature. With copper it principal product, the arsenical pyrites generj
forms white, malleable, dense, and fusible alloys. occur to the amount of about 12 p.c.
White copper contains about 10 p.c. arsenic. The ores are usually roasted in a reverbe:
Arsenic is also used in speculum metal, and tory furnace. In a common form, the fum
bed is flat, 12-15 feet long and 7-9 feet wide
in the middle ; the arch is about 2 feet above
the bed, and sinks gradually towards the flue,
at which end there is an iron door, through
which the ore is raked (Fig. 1).
From 3-15 cwt. of the stamped dried ore is
introduced through a hopper over the centre of
the fire-bridge and spread over the furnace bed.
The heat is raised to dull redness and the ore
1
is frequently stirred to ensure thorough oxida-
tion of the arsenic and sulphur. In about 10

hours these have been expelled as oxides, and
the arsenious oxide together with some of the
sulphur collects in the flues. The spent ore
is removed through an aperture in the bed,
which is closed with an iron door during calci-
nation.
Two such furnaces are sometimes built side
by separated by a wall, and with their flues
side,
uniting. The furnace beds slope gently towards
a narrow fireplace. In the first instance the ore
is introduced through a number of doors on
FIG. 1. each side of the furnace. As the ore is worked
downwards its place is constantly supplied by
is frequently present in common Britannia fresh ore through an opening in the roof.
metal. Brunton's Calciner is much used in Cornv
ARSENIC. 297
It is practically a reverberatory furnace with a passing through a series of chambers before
revolving bed. The bed is of firebrick resting escaping into the air. At the Devon Great
on a cast-iron table, and is higher at the centre
than at the periphery. It is usually 8 or 10 feet
in diameter ; it revolves three or four times in
an hour by steam or water power, about half-
horse power being required. There are two
furnaces on opposite sides of the bed.
The dried and finely stamped ore is intro-
duced through a hopper over the centre of the
bed. Above the bed are fixed radially three cast-
iron frames hi which are fastened a number of
equidistant iron scrapers shaped like the coulter
of a plough and placed obliquely, so that, as the
bed revolves, they turn the ore over and outwards
towards the periphery of the bed. It is thus
thoroughly roasted, and, on reaching the edge,
falls into the chamber beneath.
Oxland and Hacking's Patent Calciner
(English 'Pat. 1868, 2950) is largely used, espe-
'
cially for rank ores (Figs. 2 and 3). It consists

of a wrought-iron cylinder, which, if 32 feet in
length, is lined with sufficient firebrick to leave
4 feet clear internal diameter. Four longi-
tudinal ribs of firebrick occur within the furnace,
leaving sufficient space at the upper end for the
continuous supply of the ore. The cylinder is
generally mounted in an inclined position, the
slope being usually \ to 1 inch per foot, and is
turned by means of a turbine or water-wheel
once in 8 or 10 minutes upon friction-wheels.
The dried, finely powdered ore is introduced
through an archimedean screw, or from a hopper
at the upper end, and in the revolution of the
tube becomes lifted to a certain height by the
ribs of firebrick, and falls in a fine stream
through the hot blast. In a few revolutions the
ore is completely oxidised, the arsenic burning
off first, and finally reaches the lower end of the
tube, where it falls through a chamber beneath.
A calciner of the above size will roast 6 to 7
tons of ore in 24 hours. In this furnace the
amount of air required is minimised, thus render-
ing the condensation less difficult. The amount
of fuel used is also small (v. further, Henderson,
Proc. Roy. Inst. Mech. Engineers, 1873).
A
modification of this furnace was patented
by R. & C. Oxland (Eng. Pat. 7285, 1885). It
is so
arranged that the products pass into the
condensing chambers unmixed with other gases.
At the lower end of the rotating tube is a cast-
iror prolongation,heated externally by a grate
and a system of flues surrounding it. At the
end of the prolongation is a door for removing
the calcined products and a regulator for ad-
mitting the required amount of air.
Roasting in muffle furnaces. This process
is used at
Altenberg (Figs. 4, 5, and 6) and at
Reichenstein in Silesia (Figs. 7 and 8), where
wood is cheap.
The ore, reduced to a moderate size and
known as schleich, is introduced through an
opening in the top in charges of about 10 cwt.
and spread 2 or 3 inches thick on the floor of
the muffle: It is first heated to redness, and
then more gently, with the muffle door open, to
oxidise the mass thoroughly before sublimation.
The operation is completed in 11 or 12 hours.
Condensation of the oxide. The vapours
Consols and other large works, the
chambers
passing off in the roasting are carried through
chambers so arranged that the gases come in are made of thin brickwork covered
with iron
contact with a very large condensing surface platesto assist the cooling of the gaseous oxide.
298 ARSENIC.
The ores, before calcination, are dried over iron compounds when so mixed it is of a dark-
;
plates or the condensers. colour and requires to be resublimed.

These chambers are cleared at intervals, The condensing chambers connected wit
the muffles are in a lofty build
in Silesia
'
called the poison tower (Giftthiirme).
gases traverse, by a sinuous course, a series
chambers, depositing the finest product in tl
lower ones, that in the upper chambers contair
ing sulphur. The chambers are cleared aboi;
every 2 months, and contain about 25
of white arsenic (' poison flour,' or Giftmehl)
Being comparatively pure, it does not usualh
require refining, but may be at once conver
into arsenical glass. The workmen engaged
clearing the chambers are clothed in leather
garments with glazed apertures for the eye
and wear wet cloths over their mouths
noses to absorb the irritating fumes. It
'
stated at Salzburg that only arsenic-eaters
can perform this work continuously.
Refining or resublimaiion. For this pi
a reverberatory furnace is used, which is usually
much shorter than that in which the calcination
is performed. The arsenical soot is charged
from the top and paddled down through
at the side, more being added as it sublime
The fuel used is smokeless, usually a mixture
FIG. 4. VERTICAL SECTION of anthraciteand coke.
TOWEK.' The sublimate is collected in chaml
similar to those already described. It is whit
some every fortnight, those at Silesia once in
glistening, and minutely crystalline. It
two months. Two sets of chambers are fre-
ground between millstones, and is thence fe
quently used, so that one set may be working into kegs from a hopper through a leatl:
while the other is being cleared. hose which fastens to the top of the cask
|
prevents any escape of the powder.

Arsenic glass, or vitreous white arsenic,
j
prepared by volatilisation of the powder unde
i
slight pressure. For this purpose, at Swanse
j
a cast-iron pan is used 2 feet in diameter
I
surmounted by a bell 2 feet 6 inches high,
pan is heated to a cherry red, and about J
of refined white arsenic introduced through
opening in the top of the bell, which is the
closed with a plug. In about 2 hours the whol<
has evaporated and condensed on the bell as
transparent glass ; more white arsenic is the
j
introduced and condensed, until after 24 hoi;
! the glass has reached a thickness of abov
1 inch. The later charges, owing to the
j
den sing surface being hotter, require about frv
as long to condense as the first.
At Silesia the subliming pots are deej
and of greater capacity ; they are surmount
by iron drums and conical caps, which conde
the glass ' and open into condensing chamber
'
The temperature is carefully regulated,
FIG. 5. GROUND PLAN OF FURNACE. arsenic glass produced amounts to about 92 p.i
' '
of the flowers used.
The oxide produced by all processes except
'
that of the muffle is known as arsenical soot,' Analyses of Arsenic Powder and Arsenic
and is impure, containing carbon and sulphur (1) Powder from Altenberg, from the
denser of a
roasting furnac
near the furna
end (Lampadius).
(2) Do. froi
further end of con-
denser (Lamp*
dius).
(3) Do. froi
Transverse Section. Longitudinal Section. Oberschlema (I
FIG. 6. SUBLIMING FURNACE. padius).
ARSENIC. 299
(4) Arsenic glass from Andreasberg (Streng). of an ordinary piece is therefore doubtful,
depend-
(1) (2) (3) (4) ing on the amount of change it has undergone.
95-85 It is very soluble in glycerol, and is stated
Arsenious oxide 90-1 94-31 98-2 by
Arsenious sulphide 2-05 0-32 1-03 Jackson to form glyc.eryl arsenite (Chem. News
Bismuth .
.
_. _ 0-25 49, 258).

0-73 0-71 0-50 On making a strong solution of the vitreous
Sulphur .
form in dilute hydrochloric acid by

Ore-dust 5-51 2-05 3-05 dissolving
3 parts in a mixture of 12 hydrochloric acid
Antimonious oxide . 1-68
and 4 water, and slowly cooling, it is deposited
Properties and uses of arsenious oxide. in the octahedral form, each crystal as it falls
White arsenic occurs in the amorphous or glassy
producing a flash of light (H. Rose). If these
crystals be redissolved or if the opaque form
be used, no light is produced on crystallising,
that phenomenon appearing to depend on the
change of the amorphous into the crystalline
form at the moment of crystallisation.
At about 193 arsenious oxide softens and
sublimes without fusion ; it fuses under pres-
sure ; its vapour is colourless and odourless.
It is acid to test papers, but does not appear to
form true arsenious acid on solution in water.
Arsenious oxide is a powerful febrifuge, being
sometimes efficacious when quinine has failed.
It is highly poisonous, 2 or 3 grains being a
very dangerous dose. When used habitually,
however, comparatively large quantities may be
taken with impunity. The inhabitants of Styria
eat it under the name of hydrach,' to increase
'
their endurance. Many authentic cases are

recorded of 6 grains and upwards being taken
I
without ill effect. Arsenic-eaters are stated to
be fresh complexioned, with a tendency to
stoutness, to be long-lived, but to die suddenly.
The workmen engaged in the manufacture of
dyes where arsenic acid is used have been ob-
served to have this tendency to stoutness (v.
j
Roscoe, Mem. of Lit. Phil. Soc. Manchester,
I
1860). In cases of death from poisoning, the

greater part of the arsenic appears to be con-
FIG. 7. tained in the liver and intestines of the bones,
;
those of the pelvis and neighbourhood vertebrae

form, and in two crystalline modifications :
appear to contain most.
(1) the octahedral or common form, and (2) in In manufactures, arsenious oxide is used ;
trimetric prisms, occasionally found in sub- in glass-making, to remove the colour produced
limates ; this form is converted into the octahe- by the lower oxides of iron ; in enamelling ;
dral variety when heated or boiled in water. in calico-printing as a constituent of white
;
The amorphous form is transparent when fire in pyrotechny; for the prevention of boiler
first
prepared, but becomes opaque when exposed incrustations (40 parts white arsenic to 9 so-
to the air, especially when damp, diminishing dium carbonate) ; in the manufacture of arsenic
acid ;
of fly and rat poisons ; and in the
and
manufacture of a large number of pigments,
arsenic being found in green, blue, pink, white,
brown, and other colours. As a preservative
it is thrown into the holds of ships, to prevent
as a wash for walls
vegetable decomposition ;
inIndia, to prevent insect ravages to prevent

;
smut in wheat and with sodium carbonate as

;
a wash for sheep and in arsenical soap, for

;
preserving skins.
Arsenious oxide is employed in the fixation of
aniline colours, especially of aniline blue. It is

FIG. 8. REICHENSTEIN FURNACES. used principally for preparing steam colours,
either as a solution in glycerol containing 4 Ibs.
slightly in specific gravity and forming the of the oxide to 1 gallon of glycerol, under
'
the
crystalline oxide. The
action commences at name ' arsenic and glycerine standard ; or as
the outside, so that even after a considerable sodium arsenite, dissolved in sodium carbonate
time a piece is frequently found with a trans- or borate.
parent nucleus. The vitreous form may be kept In medicine it is used as Fowlers solution,
in a sealed
glass tube for
unchanged years. which contains 4 grains of the oxide (in the
The vitreous form, according to Buchner, is form of sodium arsenite) in each ounce of fluid.
soluble in 108 parts of cold water, whilst the In India it has been used as a cure for hydro-
opaque form requires 355 parts In veterinary
; the solubility phobia and serpent poisoning.
300 ARSENIC.
surgery largely used as a tonic, to eradicate
it is
precipitate is thrown upon a filter cloth, washed
worms, and for improving the coats of horses. with warm water, and dried gently with the
It occurs, either as an impurity or as an production of about 1 Ibs. of the pigment.
adulterant, in a large number of commercial Seheele's green is a pulverulent, fine light-
products. Besides the ordinary commercial green colour, formerly largely used in calico-
compounds in which arsenic is expected to be printing and for wall-papers. It is, however,
present, it has been found in caustic soda, much less used at the present time. It dissolves
potassium chlorate, commercial glucose (Cloue't entirely in excess of alkali or in acids.
and Hitter), and in wine free from artificial Schweinfurth green. Imperial green. Eme-
colouring matter (traced to sulphuric acid used rald green. Mitis green. Aceto-arsenite of copper
in purifying the casks). Dr. Tidy found about
' '
(when mixed with gyspum or heavy spar, known
38 p.c. of arsenious oxide in some violet powder also as Mountain or Neuwieder green).
which had caused the death of at least two 3CuOAs 2 3 -Cu-(C 2 H 3 2 ) 2.
children (Lancet, Aug. 21, 1878).
Five parts of verdigris (basic copper acetate)
In the year 1900 occurred a serious epidemic are made into a thin paste with water and adde
"
of arsenic -poisoning due to contamination of

to a boiling solution of rather more than 4 parts
beer through the use of brewing sugars, glucose,
'
arsenious oxide hi 50 parts water ; the solution
sugar containing arsenic. The
'
or invert If a yellow-
is kept boiling during the mixture.
arsenic was introduced by the use of highly
arsenical sulphuric acid in the production of green precipitate falls, a little acetic acid is added
and the solution boiled a few minutes longer ; tl
the sugars. The total number of persons who
suffered in consequence of the epidemic was cer- precipitate becomes crystalline and soon acqu
the characteristic green colour.
tainly 6000, and probably considerably greater. A very fine product is prepared by the follow-
At least 70 deaths. were attributed to the epidemic.
Coal or coke used for malt drying always ing method :
Boiling, concentrated solutions
arsenious oxide and copper acetate are mixed ir
contains arsenic ; with an ordinary malt kiln
such proportions that equal weights of the two
part of the arsenic volatilises and may deposit substances are present when a bulky olive-greer
on the malt. Various methods have been tried an equal bulk of cold wat
precipitate falls ;
and adopted in which it has been found that is then added and the mixture placed in a
access of arsenic to malt may be obviated or
flask which it fills to the neck, thus preventing
diminished (Royal Commission: Arsenical Poison-
any pellicle which may form on the surface from
ing, 1903).
falling through the liquid and causing a prema
(For a statement of the amount of arsenic in ture crystallisation. The colour under the
the varieties of pyrites, and of its distribution
circumstances takes two or three days to perfect,
in the preparation of sulphuric acid and alkali,
the beauty of the product being much incre
v. H. Smith, Phil. Mag. [4] 44, 370 Chem. News,
by slow formation. The workmen engaged in
;
26, 176; and C. Hjelt, Dingl. poly. J. 226, the preparation of this pigment do not appear
174-181.) be injured by it. In contact with organic matt
Fresenius finds that the arsenic in many
it is, however, liable to change. Bischof
chemical glasses is removed by alkaline, but not
(Zeitsch. anal. Chem. 23, 117) states that micr
by acid liquids ; the bearing of this on judicial
is
organisms and fungi act on compounds of arsenic
important.
producing arseniuretted hydrogen; and Fleck
investigations
The commercial article is frequently adul-
Sonnenschein, and others have conclusively
terated with gypsum, chalk, &c., these may
shown that this gas is frequently present
easily be detected by heating a little on a knife, the air of rooms with arsenical wall-paper.
when they will remain after the oxide has the action of damp and mould on paper coloi
volatilised.
with this pigment a peculiar odour is frequentl}
Sodium arsenite. Acid sodium arsenile
produced, which appears to be due to the forma
Na 2 0-2As 2 O 3 -2H 2 tion of diethylarsine (v. ARSENIC MOULD).
is prepared by dissolving arsenious oxide in a Arsenic oxide. Arsenic acid, Arsenic peri
solution of caustic soda or sodium carbonate, oxide, Acide arsenique, Arsensaure, Acidur
and evaporating the solution. The neutral salt, arsenicum. As 2 6
.
Na 2 OAs 2 formed by boiling this compound

3 , is Produced when arsenious oxide is acted uj
for some time with sodium carbonate, and by an oxidising agent.
washing the residual salt with alcohol (Pasteur). On the large scale 4 parts white arsenic
Potassium arsenite is prepared in a similar gradually added to 3 parts nitric acid of not le
manner. than 1-35 sp.gr. in a vat capable of hold'
Sodium arsenite is used as a substitute for from 65 to 70 kilos, of white arsenic. Gi
dung in dyeing, but is not so reliable as the heat is produced and the evolved fumes
arsenate. It enters anto the composition of all passed over coke moistened with water, whereby'
preparations in which arsenious oxide is dissolved about twTo-thirds of the nitric acid is recovere
with sodium carbonate. In 24 hours a syrupy liquid is formed, contaii
An arsenite of chromium and iron is used as a small quantity of arsenious oxide, which maj
a green pigment in wall-papers. be oxidised with a little more nitric acid.
Seheele's green. Arsenite of copper. Hydro- Kestner performs the oxidation in large glass
cupric arsenite. CuHAs0 3 .
flasks, the nitrous fumes being passed through
According to Seheele's method, 11 oz. ar- lead pipes and condensed in leaden chambers.
senious oxide are gradually added to a solution Arsenic oxide has also been prepared by
of 2 Ibs. potassium carbonate in 10 Ibs. boiling a
suspending arsenious oxide in water, passing
water ; this is filtered and poured into a solu- current of chlorine through the liquid, and
tion of 2 Ibs. copper sulphate in 30 Ibs. water, evaporating the solution thus produced.
so long as a grass-green precipitate falls. The It is a deliquescent solid fusing at a dull-red
ARSENIC. 301
heat, of acid metallic taste and acid reaction. through a solution of arsenious acid in hydro-
It dissolves in 6 parts cold and in 2 parts hot chloric acid.
water. A
cold, strong solution blisters the skin. Schultze (J. pr. Chem. 25, 431) considers that
Arsenic oxide and its
poisonous salts are less another form of the trisulphide exists which is
than the corresponding arsenious compounds. soluble in water (v.
COLLOIDS).
Sodium arsenate. Hydric disodic arsenate ; On the large scale it is prepared by subliming
'
Dung salt.' Na 2 HAsO 4 .
sulphur with arsenious oxide, 2 parts of arsenious
It prepared by saturating arsenious oxide
is oxide and 1 part sulphur
being a common pro-
with crude soda ash, drying, and deflagrating portion the
; colour of the product is lighter when
with sodium nitrate in a reverberatory furnace. less sulphur is used.
Arsenate of soda is largely used in calico- According to R. Wagner, a very fine colour
printing as a substitute for dung, its feebly may be produced as follows 2 parts finely :
alkaline properties rendering it useful for that ground barium sulphate are calcined with 1 part
purpose. powdered charcoal or other carbonaceous matter,
Arsenate of iron is an amorphous green and the product is pulverised, mixed with 1 part
powder containing 33-6 p.c. arsenic. ground orpiment, boiled in water and filtered.
Arsenic sulphides. Arsenic forms three The solution, containing a sulpharsenite of
well-defined sulphides, As,S 2 , As 2 S 3 and As 2 S 5 , , barium, is precipitated by the addition of sul-
the two former occurring naturally. large A phuric acid. By the addition of a suitable
number of other sulphides of indefinite com- amount of barium chloride before precipitation,
position also exist. the pigment may be correspondingly lightened in
Realgar. DisulpMde of arsenic. Ruly sul- colour.
phur. Rothes rauschgelb. Rothes Schivefel. Orpiment is insoluble in water but very
Sulphur^ rouge. Orpin rouge. Eisigallo. soluble in alkaline sulphides. It was formerly
Sandaraca. As 2 S 2 . much used as a pigment under the name of
Prepared by fusing together arsenic and King's Yellow, but now
is largely replaced
by
sulphur or orpiment in the proper proportions. chrome yellow. The
lighter varieties contain
On the large scale it is obtained by distilling a as much as 80 to 90 p.c. of arsenious oxide,
mixture of arsenical ores, such as arsenical and and are consequently very poisonous. The
iron pyrites, with sulphur or with the sulphide darker varieties contain from 1 p.c. to 15 p.c. of
of arsenic precipitated in the purification of the oxide and from 0-2 to 3 p.c. non-volatile
sulphuric acid. matter. It is used in pyrotechny, and the finer
The mixture should contain about 15 p.c. kind, especially the mineral, is made into
arsenic and 26-28 p.c. sulphur it is placed in ; pigment for artists.
flask-shaped earthenware retorts, holding about It was formerly used as a deoxidising agent
60 Ibs. when two-thirds full, which are connected in the reduction of indigo blue, and in ammonia-
with similar receivers. The retorts are gradually cal solution in silk-dyeing. A mixture of 9
heated to redness and kept so for 8-12 hours. orpiment and 1 quicklime made into a paste
with water is used under the name of Rusma
' '
The crude realgar should be compact, dark,
and rich in arsenic ; if sulphur be in excess it for removing hair from skins, but is now generally
is friable and light red. It is re-melted rapidly replaced by the solution of sulphide of lime
in cast-ironpans with the requisite amount of prepared from the spent lime of gasworks.
sulphur or arsenic, or with realgar of poorer Arsenic pentasulphide As 2 S 5 Berzelius in .
quality. The mass is cleared of slag and heated 1826 stated that this compound was formed when
until quite fluid, and until a small quantity sulphuretted hydrogen is passed through a
shows the proper appearance on cooling. It moderately concentrated solution of arsenic acid,
is then poured into conical sheet-iron moulds. but the precipitate was generally considered to
Greater care is necessary in the preparation be a mixture of the trisulphide and sulphur.
of realgar than of orpiment, and an assay is Bunsen in 1878 showed that it was produced on
frequently made to ascertain the exact propor- passing a rapid current of sulphuretted hydrogen
tions required before the final melting. through a hot hydrochloric acid solution of an
It is hard and brittle, gererally opaque, with alkaline arsenate, and his results were confirmed
vitreous conchoidal fracture, orange or hyacinth by McCay in 1887 (cf. Brauner and Tomicek,
red in mass and orange-red in powder. Its Chem. Soc. Trans. 1888, 147).
sp.gr. 3-4-3-6, and its usual composition
is Arsenic pentasulphide is totally insoluble in
is arsenic 75, sulphur 25. It volatilises water, alcohol, or disulphide of carbon. The
easily before the blowpipe with a smell of garlic dry substance, on rubbing in a mortar, becomes
and burning sulphur, is insoluble in water or strongly electrical.
hydrochloric acid, but soluble in alkaline Arsenic chloride. Butter of arsenic. Caustic
sulphides. oil arsenic AsCl 3 is produced by the action
of
Realgar is a constituent of blue fire and of of chlorine on arsenic by distilling arsenic
;
with mercuric chloride and by distilling arsen-

'
white Bengal fire,' which is used as a signal ;
and consists of ious oxide with strong hydrochloric acid. It is

light, realgar 2, sulphur 7,
potassium nitrate 24. a colourless, oily liquid, of sp.gr. 2-205 0/4
The variety, especially that which
finest boiling at 130-2 (Thorpe).
occurs native, is used as a pigment by artists. The chloride and iodide are used to a slight
Orpiment. Gelbes Rauschgelb. extent hi medicine. H. W. H.
Operment.
Risigallum. Auripigmentum (of which its usual
name is a Yellow
ORGANIC COMPOUNDS OF ARSENIC.
corruption). Sulphide of
Arsenic. As 2 S 3 oxide (Dimethyl arsine oxide)
. Cacodyl
This sulphide is formed as a yellow pre- [As(CH 3 ) 2] 2
O is formed by the dry distillation of
cipitate when sulphuretted hydrogen is passed a mixture of equal parts of potassium acetate
302 ARSENIC.
and arsenic trioxide. As thus obtained, it is
expressed by the formula NH 2 -C 6 H 4 -AsO(OH) 2 .
spontaneously inflammable owing to the presence It is weakly basic, and forms salts with acids
of free cacodyl. When pure, it is an oily which are at once hydrolysed by water.
liquid, b.p. 150, insoluble in water, and of a Sodium p-aminophenylarsihate, known as
powerful and nauseous odour. It is extremely
'
aloxyl
'
(arsamin, soamin) NH 2 -C 6 H 4 -AsO

poisonous. With acids it forms salts, such as (OH)ONa, is obtained by neutralising the above
cacodyl chloride As(CH 3 ) 2 -Cl this, on heating
; acid with soda. It is a white salt, crystallising
with metallic zinc, in abser.ce of air, yields with an amount of water variously stated to be
catodyl As 2 (CH 3 ) 4 as a colourless, liquid, which
, between 2 and 6 molecules, and effloresces on
takes fire on exposure to air. This compound exposure to air (Moore, Nierenstein and Todd,
also has an intensely disagreeable smell, and is Biochem. Jour. 1907, 300 v. also Ehrlich and
;
very poisonous. Bertheim). The anhydrous salt is soluble in

Cacodylic acid (CH 3 2 -AsO-OH
)
is obtained methj'l alcohol, but almost insoluble in ether,
by the oxidation of cacodyl oxide by means of acetone, benzol, or chloroform. (For its thera-
mercuric oxide. It is a crystalline, odourless peutic action, see Pharm. Chem. Jour. 1907,
substance, and is not poisonous (Bunsen ; 528.) It is at present the compound of arsenic
Marshall and Greene, Amer. Chem. J. 8, 128). most largely used in combating trypanosomes.
The salts of cacodylic acid, especially the sodium, Atoxyl solutions should be made with cold,
magnesium, and strychnine salts, have been boiled water and kept in the dark. They must
used in medicine, but have fallen into disfavour not be allowed to become alkaline, and should
on account of their lack of arsenical effect, and be boiled for two minutes (not more) before use.
of certain unpleasant effects attendant upon (For a method of estimating either arrhenal
their use. or atoxyl, v. Bougault, J. Pharm. Chim. 1907,
Disodium methylarsenate, 'arrhenal' ('New 13.)
cacodyl') CH3 -AsO(ONa) 2
is prepared by the Mercury y-aminophenylarsinate (Asyphil)
interaction of methyl iodide and sodium arsenate has been suggested as a substitute for atoxyl.
in the presence of excess of alkali. It is a white It may, in common with many other insoluble
crystalline compound, easily soluble in water, organic compounds of arsenic, be dissolved in
but only slightly soluble in alcohol. It may be glycerol, and this solution, strong or diluted,
distinguished from sodium cacodylate by means used for injection. It is said that such a solution
of mercuric chloride, which gives a reddish- has a stronger action on trypanosomes than has
yellow precipitate with arrhenal, but a white atoxyl (P. Wolff, Ger. Pat. 213394, 1908).
precipitate with the cacodylate (Martindale, Acetyl-^-aminophenylarsinic acid (Acetyl-
J. Chem. Soc. Ind. 1907, 907). arsanilic acid) CH 3 -CO-NH-C 6 H 4 -As(OH) 2 is
The compounds of arsenic with aromatic prepared by acetylating 31 parts of atoxyl with
radicles, especially atoxyl and its congeners, have 55 parts of acetic anhydride, and then adding
'
attained importance hi the treatment of sleeping 300 parts of water and 52 parts hydrochloric
sickness,' Gambia fever, &c., which are due to the acid (Ber. 40, 3292). By neutralising the acid
presence of specific trypanosomata in the blood with soda,
(v. Plimmer and Thomson, Proc. Roy. Soc.
B. Sodium acetyl-^-aminophenylarsinate (' Ar-
1907, 505). sacetin,' acetyl-atoxyl) CH 3 -CO NH-C 6 H 4
< -
Diphenylarsinic acid (Phenyl cacodylic acid) AsO(OH)-ONa is obtained as a white crystalline

H
(C 6 6 ) 2 : AsO-OH is prepared as follows : powder, soluble in water (1 10). This com-
:
Diphenyl-arsenious chloride, one of the products pound is stated to be less toxic than atoxyl (v.
of the interaction of mercury diphenyl and Extra Pharmacopoeia, xiii. 168), and its solutions
arsenious chloride (Michaelis, Ber. 8, 1316 ; 9 can be sterilised by heat and stored without
1566), is mixed with water and treated with a alteration. It has been successfully exhibited
rapid stream of chlorine at a temperature of in cases of syphilis, and is very active in com-
60-70. bating trypanosomes.
Diphenylarsinic chloride (C 6H 5 ) 2 AsCl 3 is Phenylglycine-p-arsinic acid
thus formed the solution is evaporated to
:
C0 2 H-CH 2 -NH-C 6 H 4 AsO(OH) a
dryness on the water- bath, and the residue taken is prepared either by mixing sodium p-amino-
up with water, from which the acid can be arsinate (' atoxyl ') and chloroacetic acid in hot
crystallised in long needles ; m.p. 174 (Mi- water, or by hydrolysing with alkalis the nitrile
chaelis, Annalen, 201, 231 ; 321, 151). Martin-
CN-CH 2 -NH-C 6 H 4 AsO(OH), produced by warm-
dale recommends the use of ether as a solvent.
ing together in aqueous solution, p-aminophenyl-
(For an alternative method of preparation, see arsinic acid, potassium cyanide and 40 p.c.
Sachs and Kantorowiez, Ber. 41, 2767.)
H formaldehyde (D. R. P. 204664).
p-Tolylarsinie acid CH 3;C 6 4 -AsO(OH) 2 is
Arsenophenylglycine (' 418 ')
prepared by passing chlorine into a mixture As 2 (C 6 H 4 -NH-CH 3 -C0 2 H) 2
of 1 part >-tolyl-arsenious chloride and 5 parts ,
water at 60-70. The solution is evaporated a reddish-brown powder, soluble in aqueous

to dryness and the residue boiled with water, sodium carbonate, but insoluble in dilute mineral
from which the acid crystallises (Martindale). acids, and the ordinary organic media, is pre-
The acid has been found efficacious in destroying pared by reducing the preceding compound with
alkaline sodium hyposulphite (D. R. P. 206057 ;
trypanosomes (Plimmer and Thomson, ibid.).
p-Aminophenylarsinie acid (Arsanilic acid) U.S. Pat. 888321). This substance has given
was first prepared by Be'champ in 1863 (Compt. promising results in sleeping sickness. Ehrlich
rend. 56, 1172), by heating aniline arsenate at supposes that it acts on that part of the trypano-
190-200. He supposed it to be an anilide of some concerned with multiplication. The
arsenic acid. Ehrlich and Bertheim have shown sodium salt is a readily soluble yellow powder,
(Ber. 40, 3292) that the acid has the composition which, however, can be preserved only in sealed
ARTOCARPUS INTEGRIFOLIA. 303
tubes ;
has found employment in a 5
it p.c. 1900, 1187) ; Galli-Valerio and Strzyzowski
ii.
ointment in eye affections and eczema. |

(ibid. 1901, i. 63).
/i-Hydroxyphenylarsinic acid PenicilUum brevicaule also gives
garlic or
HO-C 6 H 4 -AsO(OH) 2 , mercaptan-like odours with compounds of
selenium and tellurium (Maassen, Chem. Zentr.
yellow prisms m.p. 173-174, is obtainable
;
I
.'''_, 1. _ 1 * > .
either directly by heating phenol and crystallised

, I
/
arsenic acid at 150 for 4 hours, or by decompos-

ARSENOGENE. Trade name for an albu-
minous preparation of arsenic and iron obtained
ing with hot water the diazonium derivative of
|
by heating peptonised casein with arsenic acid

p-aminophenylarsinic acid. and ferric ammonium sulphate. Used in medi-
2-Nitrophenol-p-arsinic acid cine (Salkowski, Apoth. Zeit. 1908, 23, 114).
HO-C R H 3 (N0 2 )-AsO(OH) 2 ,
ARSENOPYRITE v. MISPICKEL.
isprepared by dissolving the sodium salt of the ARSINE. Arsenic trihydride (v. ARSENIC).
preceding acid in cold concentrated sulphuric ARTEMISIN. An alkaloid isolated by Merck
acid and adding to the solution at the calcu- from the mother liquors obtained in the prepara-
lated amount of nitric acid (sp.gr. 1-4) mixed tion of santonin from the seeds of Artemisia
with an equal volume of sulphuric acid. maritima. Forms colourless crystals ; m.p. 200 ;
4 4'-Dihydroxy-3 3'-diaminoarsenobenzene
: :
sparingly soluble in water, more soluble in
hydrochloride As 2 [C 6 H 3 (OH).NHJ 3 ,2HCl (Sal- alcohol; [] 84-3. With hot soda solution
' D
varsan, 606 ') is produced by reducing the a
gives carmine red solution, colourless on
preceding compound with sodium sulphide, when cooling. Gives an oxime with hydroxylamine,
the free base separates as a yellow crystalline and a hydrazone with phenylhydrazine (Bertolo,
precipitate, soluble in dilute hydrochloric acid Pharm. J. 1902, 489 Freund and Mai, Ber, 1901, ;
or aqueous alkalis, and reprecipitated from the
3717 cf. Wedekind and Koch, Ber. 1905, 1845).
;
latter by acetic acid. This compound appears ARTICHOKE. Three vegetables are known
to have a specific action on trypanosomes and
by this name: (1) the Globe artichoke the
spirochetes with a minimum evil after-effect on flower head of Cynara scolymus (2) the Jeru- ;
the host of these parasitic organisms. Very salem artichoke the tuber of Helianthus
remarkable curative results have been obtained tuberosus ; (3) the Japanese or Chinese artichoke
in syphilis, relapsing fever, frambcesia, and fowl
called also Chorogi the tuber of Stachys
spirillosis. The drug has also been exhibited
tuberifera.
with some success in malaria and leprosy ; it is
The following are analyses of the tubers of
applied in the form of injections, which may be the two latter :
either subcutaneous, intramuscular, or intra- Carbo-
venous. Water Protein Fat hydrates Ash
When a sufficient dose is administered it is Jerusalem arti-
frequently found that complete disappearance of choke 79-5 2-6 0-2
. 16-7 1-0 .
the specific organism is effected after a single Stachys tuberifera 78-05 4-32 0-16 14-63 1-21
injection (v. Ehrlich and Hata, Die experimen-
(Strohmer and Stift, Bied. Zentr. 21, 820.)
telle Chemotherapie der Spirillosen (Syphilis, ' '
Theprotein of the Jerusalem artichoke
Riickfallfieber, Hiihner Spirillose, Framboesie) ; includes much material other than true proteid ;
J. Bresler, Die Syphilisbehandlung mit dem
the carbohydrates consist largely of inulin and
Ehrlich- Hata'schen Mittel ; Martindale and levulin.
Westcott, Salvarsan or '606,' 1911). (For organic
According to Tanret (Compt. rend. 1893, 117,
arsenic compounds containing two or thre 50), two other carbohydrates helianthenin m.p.
aromatic or hydroaromatic groups, v. Chem. Soc.
176, 12C 6 H 10 B +3H 2 0, and synanthrin, m.p.
170, 8C 6 H 10 5
Trans. 1908, 93, 1180, 1893, 2144; 1909, 95, 2
are also present, and the +H
1473; Ber. 1908, 41, 931, 1672; 1910, 43, levulin or synanthrose described by other
924.) observers as occurring in artichokes, is a mixture
Arsenogene is an indefinite compound of of saccharose and synanthrin.
peptonised casern and arsenic, recommended for of Stachys tuberifera contain many
The tubers
medicinal use by Salkowski (Apoth. Zeit. 1908,
nitrogenous substances of an amide
nature
114).
The preparation glutamine, tyrosine, arginine, choline, trigonelline,
of albuminoid compounds of
and the characteristic body, stachydrine
arsenic hasbeen patented by Klopfer (D. R. P.
214717, 1908) and Gnezda (D. R. P. 201370, /CHo CH C0\
CH < >0
-N(CH 3 /
1906). 2
(For the determination of arsenic in organic

\CH 2 )2
compounds, see Little, Cahen and Morgan, Trans. The amount of the last-named is estimated al
Chem. Soc. 1909, 1477.) 0-18 p.c. of (Schulze and
the dry substance
ARSENICAL PYRITES or Arsenical mundic. Trier, Zeitsch. physiol. Chem. 1910, 67, 59).
Names commonly used by miners for the mineral The characteristic carbohydrate is stachyose
mispickel (q.v.) or arsenopyrite (FeAsS), which is C 18H 32 16 ,3H,0 (q.v.).
H. I.
the principal ore of arsenic. ARTOCARPUS BARK. The inner bark

ARSENIC MOULD. tree [A. incisa (Linn.)]
PenicilUum brevicaule. (bast) of the bread-fruit
This organism, first obtained by Gosio, in is used the South Sea Islanders for making
by
presence of an arsenic compound, forms diethyl- ropes and
clothing. According to Moeller
arsine AsH(C 2 H
6 ) 2 , to which the poisonous gas (Dingl. poly. J. 231, 463),
this fibre would pro-
It can be obtained
developed by wall-papers containing arsenic is bably be a very useful one.
probably due. The formation of diethylarsine in large quantities.
by the action of this mould has been used as a ARTOCARPUS INTEGRIFOLIA (Lmn. f.).
test for arsenic
by Markmann (Chem. Zentr. (Jack Tree) v. JACKWOOD ; DYES, NATURAL.
304 ARUM MACULATUM.
ARUM MACULATUM (Linn.
' '
). The common
arum, wake robin,' or lords and ladies,'cows
'
and calves,' formerly known

as abron janus,
' '
' '
ramp,' starch wort,' contains a starch which

was made into a kind of arrowroot in the Isle
of Portland, and was the active ingredient of
' The dyeing properties of isorhamnetin are
Portland powder,' a so-called specific for gout.
similar in character to those
Occasionally sold in Paris as a cosmetic, under given by hsempferol
the name of poudre de Cypre.
zsoRhamnetin is also present in yellow wall-
flowers (Cheiranthus cheiri) (Perkin and Hum-
Amorphophallus campanulatus (Blume) is
used in India as a vegetable and also in medicine, mel); in red clover flowers, Trifolium pratense
as are other of the Arums. (Power and Salway, Chem. Soc. Trans. 1910, 97,
Many of the Aroidese A
act as poisons, their toxic action being due 245). description of the more soluble colouring
matters quercetin (quercitron bark) and hsemp-
apparently to the irritation induced by the ferol (Delphinium consolida) are
raphides contained in the cells (Pedler and given elsewhere.
In dyeing properties asbarg closely resembles
Warden, Jour. Asiatic Soc. of Bengal, 57, 2,
106 ; Stahl ; Pflanzen und Schnecken, Zeitsch. quercitron bark, but yields with aluminium
Nat. 11. Med. Jena, xxii. N. F. xv. 1888). mordant, a purer or less orange-yellow. It is,
ASAFCETIDA v. GUM RESINS. however, a much weaker dyestuff, having but
35 p.c. the dyeing power of quercitron bark.
ASAPROL v. ABRASTOL.
The colouring matter of the flowers, minus the
AS ARUM CANADENSE (Linn.). A plant
North America, where it is known flowering stalks, is present to the extent of
indigenous to 3-47 p.c.
' ' A. G. P.
by the names of Wild Ginger,' or Canada
Snake-root.' The rhizome yields on distillation ASBESTOS, from fofco-ros, 'unquenched.'
an essential oil used in perfumery, containing a
Both in ancient and modern times various
phenol C 9 H 12 2 d- and I- pinene, d-linalobl,
,
silicate minerals, closely
resembling one another
in their finely fibrous texture and
Z-borneol, Z-terpineol, geraniol, eugenol methyl flexibility,
have been and are still confused under this
H
ether, a lactone C 14 20 2 , a mixture of fatty
name. The same is true also of the name
acids, including palmitic and acetic, and a blue ' ' '
oil of undetermined composition,

amianthus or aminatos '
(O/UOI/TOS,
'
un-
consisting of because not injured by
defiled,' They are,
oxygenated substances of alcoholic nature names
fire).
therefore, collective of no more definite
(Power and Seed, Chem. Soc. Trans. 1902,
significationthan the adjective ' asbestiform.'
81, 59).
ASBARG. consists of the dried Mineralogists are, however, agreed in limiting
Asbarg the name asbestos to the fibrous forms of horn-
flowers and flowering stems of the Delphinium
blende, but this limitation is not generally
zalil, which is found in great quantity in Afghani-
observed. Any ambiguity may be avoided by
stan. The dyestuff is collected and taken to
Multan and other Punjab towns, from which it using the terms amphibole-asbestos (or horn-
blende-asbestos), serpentine-asbestos, &c., for
isconveyed all over India. It is much used in these asbestiform minerals. The finely fibrous
silk-dyeing for the production
'
of a sulphur-
texture is, of course, an accidental character of
yellow colour known as gandkaki,' and, together the mineral species, depending on the enormous
with Datisca cannabina, to obtain a similar
shade on alum-mordanted silk ; it is also used elongation in one direction of the individual
in calico-printing. The flowers, which are bitter, crystals which form the aggregate. Such a
character might, indeed, be assumed by many
are likewise employed medicinally as a febri-
kinds of minerals ; but it is only the following
.fuge.
that are of any importance in this connection
The colouring matters of asbarg are present :
entirely as glucosides, and are best isolated in the Tremolite, CaMg 3 (Si0 3 ) 4.
crude condition by digesting the boiling aqueous Actinolite, Ca(Mg,Fe) 3 (Si0 3 ) 4 .
extract with a sulphuric acid (Perkin and

little Crocidolite, NaFe'"(Si0 3 ) 2 -Fe"Si0 3 .
Pilgrim. Chem. Soc. Trans. 1898, 268). A Anthophyllite, (Mg,Fe)Si0 3 .
brownish-yellow powder thus separates, which Serpentine, H

4 Mg 3 Si 2 9 .
contains three substances isorhamnetin, quer- : Palygorskite group) JraH 8 Mg 2 Si 3 O l2

cetin, and hcempferol. (pilolite, &c.), / \mH 2
Al 2 Si 4 12 ,5H 2 0.
H
Isorhamnetin C 16 12 7 the sparingly soluble ,
The first two of these only in the
differ
constituent, forms yellow needles resembling relative proportions of the mutually replaceable
rhamnetin in appearance. With lead acetate in magnesium and ferrous iron (and consequently
alcoholic solution, an orange-red precipitate is also in their colours, which are white and green
formed, whilst ferric chloride gives a greenish- respectively), and they are merely varieties of
black colouration. Fused with alkali, phloro- the species amphibole or hornblende. Croci-
glucinol and protocatechuic acid are produced, dolite is another species of the amphibole
and when air is aspirated through its alkaline group of minerals, crystallising in the mono-
solution, phloroglucinol and vanillic acid are clinic system, and also with an angle of 56
obtained. between its
prismatic cleavages. It is known
With acetic anhydride isorhamnetin gives a in the trade as
'
blue asbestos,' and it gives
tetra-acetyl, derivative C 16 R O 7 (C 2 H
3 0) 4 , colour- H the name to the Asbestos Mountains in South
less needles, m.p. 195-196 ; and with Africa, where it is found. Whilst hornblende
methyl
iodide a trimethyl ether, which is identical with is more frequently found as stout crystals
quercetin tetramethyl ether. As, moreover, by and compact masses, crocidolite, on the other
the action of hydriodic acid isorhamnetin yields hand, is as yet known only in the finely fibrous
quercetin, its constitution can only be repre- form. Anthophyllite also belongs to the
sented as follows :
amphibole group, but is orthorhombic in
ASEPTOL. 305
crystallisation. Some of the asbestos mined in differences, the two varieties are put to the same
the United States is of this kind. Serpentine uses, but serpentine asbestos is employed in
occurs in nature as large rock-masses, and the far larger quantities. Spun asbestos is largely
compact rock is frequently traversed by veins used for steam packings, fireproof curtains ; and
of fibrous material of the same composition; as cloth, twine, and rope it finds a
variety of
t he latter is known to mineralogists as chrysotile, applications. As an insulating material, as-
' ' '
and in the trade as asbestos or Canadian bestos fibre is used for coating steam and hot-
asbestos.' In the minerals of the palygorskite water pipes and cold-storage plants ; and as a
group (A. Fersmann, Bull. Acad. Sci. St. Peters- lining in safes, stoves, and furnaces. For use
burg, 1908, 637) the fibres rarely
ii. 255, as a constructional fireproof material, it is made
show a arrangement, but are more
parallel into bricks, boards, millboards, plasters, and
usually matted and interwoven, giving felted
'
paints, being often mixed with other materials,
masses known as mountain-leather,' moun- '
The so-called ' asbestic,' largely used for wall
'
tain-cork,' and mountain-wood.' It is, how- plaster, is prepared by grinding the poorer
ever, to be remembered that these trivial names material and waste, which consists of narrow
may also be applied to similar aggregates of veins of asbestos still enclosed in the serpentine-
fibrous amphibole. rock. In the laboratory, asbestos is used for
From a practical point of view, the most filtering (a pure white tremolite-asbestos being
important of these are tremolite-asbestos and best for this purpose), for stoppings in com-
serpentine-asbestos, which in the trade are known
' ' '
bustion tubes, and in the form of card for
as
'
and Canadian asbestos
Italian asbestos supports. Asbestos paper or twine, soaked in
respectively. former is met with as
The sodium silicate and afterwards treated with
aggregates or bundles of white or greyish fibres, calcium chloride solution, can be used for
sometimes several feet in length, usually arranged repairing glass apparatus.
parallel to the surfaces of crevices in the meta- The production of Canadian asbestos in 1908
morphic and crystalline rocks of mountainous amounted to 65,534 short tons (of 2000 Ibs.),
districts. It is mined in the Alps, Urals, and valued at about 510,OOOZ. ; and, in addition,
'
Appalachians. The supply is limited and un- 25,239 tons of asbestic,' valued at about 5000Z.
certain, and the hardness of the enclosing rocks The prices per short ton vary from $150 to $350
makes mining difficult. The principal mines (about 30Z.-70Z. ) for the better qualities (' crude'),
are those in the north of Italy, in the Susa and descending to $10 for the smaller material
'
Aosta valleys in Piedmont, and the Valtellina ('
fibre and ' paper stock ').
in Lombardy. References. F. Cirkel, Asbestos, its Occur-
Serpentine-asbestos, or chrysotile, occurs in rence, Exploitation, and Uses (Mines Branch,
small veins forming an irregular network in Ottawa, 1905) ; R. H. Jones, Asbestos
serpentine-rock. It has in the closely com- (London, 1890), and Asbestos and Asbestic
pacted mass an oil-yellow or greenish colour (London, 1897) G. P. Merrill, Asbestos and
;
with a pronounced silky lustre and a certain other Asbestiform Minerals (Proc. U. S. Nat.
'
degree of translucency. When rubbed or Museum, ' 1895, xviii. 281), and Non-metallic
crushed, it readily separates into white cottony Minerals (New York, 1910) ; Production and
fibres (pierre a coton of the French-Canadians). Uses of Asbestos (Bull. Imp. Inst. 1905, iii,
The fibres are arranged perpendicularly to the 277) ; The Technical Preparation of Asbestos,
walls of the vein, and are usually only an inch (ibid. 1908, vi. 393); J. S. Diller, Mineral
or two in length, never exceeding 6 inches. Resources of the United States, for 1908, 1909,
The mineral usually contains 2-3 p.c. FeO ii, 697; H. F. Olds, Blue Asbestos [Crocido-
isomorphously magnesia. Although
replacing lite in South Africa] (Trans. Inst. Mining and
chrysolite is the localities where
found at all Metall. 1899, vii. 122). L. J. S.
serpentine-rock occurs (e.g. the Lizard district ASDUANA v. BRIDELIA BARK.
in Cornwall), it is only in Canada that it is mined ASEPTIN. Trade name for .a mixture of
to any large extent, and there only since 1878.
hydrogen peroxide, boric acid, and salicylic acid,
The mining districts are near the villages of used as an antiseptic.
Thetford, Black Lake, East Broughton, and ASEPTOL. Trade name originally given to
Danville in Quebec. The asbestos quarried by a solution of o-phenolsulphonic acid C 6 H 4 (OH)
the ancients at Karystos, in Eubcea (Kary- S0 3 H. It is a thick reddish fluid, of 1-45 sp.gr.,
stian stone), and in Cyprus, was also a ser-
having a faint odour like phenol, occasionally
pentine-asbestos (J. W. Evans, Mineral. Mag., called sozolic acid. It is an antiseptic, but does
1906, xiv. 143). It was used for wicks in not possess the poisonous action peculiar to
the perpetually
burning lamps of the temples ; phenol, and is therefore recommended for
and was woven into napkins, which could be surgical and ophthalmic operations (Chem-
cleansed by fire, and into cremation shrouds. Zentr. 1884, 720).
These two kinds of asbestos the hornblende- The aseptol of Merck is p-phenol sulphonic
asbestos and the serpentine-asbestos differ acid mixed with about 6 p.c. of the o-acid
somewhat in their resistance to acids and heat, (Obermiller, Chem. Zentr. 1907, 1615).
'lirysotile is decomposed by hydrochloric and The name is also given to a preparation con-
mlphuric acids ; at a red heat (but not below) taining from 0-25 to 10 parts potassium oxy-
and the dissolved
loses water, can be fused in the quinoline sulphate, 0-5 to 10 parts soap,
it
fibres
mnsen-flame. Tremolite-asbestos is not at- in 1000 parts of water, mixed with terpineol or
acked by acids, and it is more difficultly other aromatic substances, and occasionally
usible. to a black,
(Crocidolite fuses readily glycerol (Pharm. Zeit. 1897, 770).
to an ill-defined
nagnetic glass.) On the other hand, the fibres Aseptol is also the name given
)f
chrysotile are more flexible and more suitable mixture of phenyl ethers and sulphonated
or action of sulphuric
phenols, obtained by the
textile purposes. Notwithstanding these
VOL. I. T
7
.
X
306 ASEPTOL.
acid on phenol in presence of alcohol (Trillat, A convenient method of minimising the loss
J. Soc. Chem. Ind. 1892, 1028). of chlorides by volatilisation is to char the
ASFRAX or Trayamana. An Indian drug, substance thoroughly at a moderate temperature,
consisting of the flowers, flower-stalks, and im- then cool and extract the black residue with
mature fruit of a species of Delphinium. Used water, filter off the soluble matter, and complete
in Bombay as a medicine, and as a yellow dye the incineration of the residue after drying.
for silk (Dymock, Pharm. J. [3] 8, 161). When all black particles have disappeared, the
ASH. This term is sometimes used to denote residue is allowed to cool, the aqueous extract
the inorganic or mineral matter contained in any added, evaporated to dryness, and then
substance, but more generally refers to the moderately heated. Addition of ammonium
residue left on completely burning or incinerating nitrate to the black char hastens the combustion
it. The two meanings are not necessarily the of the carbon.
same, since in any animal or vegetable substance Ash of animals. The proportion of ash con-
the inorganic constituents are usually present in stituents present in the whole body of an animal
very different states of combination to those in depends largely upon its condition, being greater
which they occur in the residue left when the in lean than in fat animals. According to the
substance is completely oxidised. Eothamsted experiments, the following table
To ascertain the exact amount and com- gives the average proportions of ash and of its
position of the inorganic matter present in any main constituents in the whole bodies of various
organic substance is often a matter of con- farm animals in a fatted condition :
siderable difficulty, and, in many cases, is

impracticable. ' '
The term ash should be used, therefore,
only in the second sense given above.
Most animal and vegetable substances leave,
on combustion, a residue containing the follow-
ing constituents in varying proportions :
Acidic Basic
Chlorine Sodium
Carbon dioxide Potassium
Sulphur trioxide Calcium
Sulphur Magnesium
Phosphorus pentoxide Iron
Silica Manganese
Other constituents, generally in small quantities,
are also often present.
In the original substance the greater portions
of the basic constituents in the above list are
probably present in combination with organic
acids, and, consequently, are left in the ash as
carbonates (often largely the case with potash
and soda) or as oxides (e.g. portions of the lime,
magnesia, oxides of iron, and manganese) ; while
the carbonates, sulphates, and phosphates are,
in many cases, derived from organic combina-
tions of carbon, sulphur, and phosphorus exist-
ing in the original substance. The determina-
tion of the amount and composition of the ash
of animal and vegetable substances, though,
perhaps, inadequate to ascertain the exact
nature of the inorganic constituents of the
organised bodies, affords valuable information
as to their fitness as foodstuffs, and as to the
needs of animals or plants.
In the process of incineration, there is great
danger of loss of chlorides of potassium and
sodium by volatilisation, also of reduction of
phosphates and sulphates by the reducing action
of the hot carbon. Berthelot proposed to over-
come these difficulties by heating in a current
of oxygen, the substance to be incinerated being
previously mixed with a known weight of
sodium carbonate (Compt. rend. 128, 23).
Shuttleworth (Chem. Zentr. 1899, ii. 144) has
suggested the addition of calcium acetate in
order to prevent the sintering which is so often
an obstacle to complete incineration, and has
devised a special platinum vessel in order to
prevent loss of chlorides by volatilisation, and to
hasten incineration. A modified form of this
apparatus is described by Tucker (Ber. 32, 2583).
ASH. 307
The following table, compiled chiefly from Wolff's analyses, gives the average proportions
of ash and of its chief components in various fresh or air-dried agricultural products.
100 parts of the substance contain :
Substance
308 ASH.
Substance
ASPARAGINE. 309
Lithium, rubidium, zinc, copper, barium, The cereals contain a large excess of phos-
and arsenic have also been detected in the ash phoric acid over lime, and the use of an exclusively
of certain plants grown in soils containing these cereal diet may lead to imperfect bone nutrition
constituents (Passerini, Chem. Soc. Abstr. 1893, (I.e. also Illustrated Poultry Record, 1910).
;
ii. 225 ; Homberger, ibid. 1899, A, ii. 506 ;

The
necessity of an adequate supply of
Macdougal, ibid. 1900, A, ii. 235). chlorides in the diet is well recognised, and in
Even chromium, molybdenum, and vanadium many countries the ordinary food supplies of
have been detected in the ash of fir, oak, vine, domestic animals have to be supplemented by
and poplar (Demarcay, ibid. 1900, 235). common salt to ensure healthy existence.
Indeed, the composition of the soil has a Whenever the rations are restricted to one
great influence upon the amount and composi- or two items, there is considerable probability
tion of the ash of the crop grown upon it, though that certain mineral constituents will be lacking
this influence is much more marked upon the or supplied in improper proportions.
foliage, stem, &c., than upon the seed. It is too often the practice, in discussing
Certain plants, originating from plants of the feeding of animals, to devote much con-
the seashore, e.g. asparagus, beet, and carrot, sideration to the organic portions of their food,
generally leave an ash containing unusually high but beyond requiring that sufficient mineral
matter or bone -forming ' material be present,
'
amounts of chlorine and sodium, and applica-
tion of common salt as manure to such crops to pay little or no attention to its composition.
is usually stated to be beneficial, although on Thus bran is widely regarded as a food
no very sufficient evidence. particularly rich in mineral matter, and therefore
Plants like salt-worts (Salsola) and samphire valuable for bone nutrition; but the ratio of
(Salicornia) growing on the coast, contain phosphorus pentoxide to lime in this food is
relatively enormous quantities of soda in the about 11 to 1, and the practice of feeding
former 6 times, in the latter 14 times, as much animals largely upon bran is known to produce
'
soda as of potash. a disease of the bones ' bran rachitis in
The ash of the club-moss (Lycopodium) horses.
contains from 20 to 50 p.c. of alumina. Kellner (Scientific Feeding of Animals,
As already stated, some of the phosphates 1909) estimates that for oxen, 50 grams of
and sulphates found in the ash of plants result phosphorus pentoxide and 100 grams of
from the oxidation of phosphorus and sulphur lime per 1000 kilos, body weight per day, are
organic compounds present in the original required in the food, while for full-grown sheep,
plant. 1 gram of the former and 11 grams of lime
Posternak (Compt. rend. 137, 1903) detected suffice.
the existence in peas, beans, potatoes, and the In England, fortunately, hay either meadow
seeds of the red fir, pumpkin, white and yellow or clover forms a large part of the rations of
lupines of anhydro-oxymethylene diphosphoric farm animals, and this contains a large excess
acid of lime over phosphoric acid, and thus neutralises
, OPO(OH) 2 the opposite preponderance in the grain or cake
2 OPO(OH) 2 used with it.
Patten and Hart (Bull. 250 (1904), N. York Agric.
But in South Africa and perhaps some other
countries, meadow or clover hay is but little
Expt. Station) have shown that about 86 p.c.
of the total phosphorus in bran, 81 used, and many horses are fed entirely upon
p.c. in malt oat hay or oat hay and maize. In either case
sprouts, and 50 p.c. in oats, is soluble in 0-2 p.c.
there is a large preponderance of phosphoric
sol. of hydrochloric acid; and that the
greater acid over lime, and to this fact the prevalence
portion of this is present in the bran as calcium,
of certain bone diseases is almost certainly due.
magnesium and potassium salts of anhydro- Similar considerations apply to other animals
oxymethylene diphosphoric acid.
kept in confinement, especially to poultry when
deprived of a grass run, and to pigs. H. I.
Importance of the Ash Constituents of Foods. ASPARAGINE. Aminosuccinamic acid
The influence of the mineral matter in the C 2 H 3 -NH 2 (C0 2 H)(CO-NH 2 occurs
) in two
food of animals upon their health and well- optically active forms, differing in direction of
being is probably much greater than is generally rotatory power and in taste. Lcevo-asparaqine,
recognised. Not only is it essential that all discovered by Vauquelin and Robiquet (Ann.
the inorganic constituents required for Chim. anal. 1805, 57, 88) in the young shoots of
building
up the tissues and producing the various digestive asparagus (Asparagus officinalis, Linn. ), is widely
and other secretions be supplied in sufficient distributed in the vegetable kingdom, occurring
quantities, but it is important, at least with in most plants at the time of budding and during
certain pairs of constituents, that they be the flowering period, and, with glutamine, forms
supplied in appropriate ratios to each other. the chief non-proteid compounds present in
A
preponderance of phosphoric acid over the juice of ripening oranges (Scurti and de
lime and magnesia in the diet is Chem. Zentr. 1908,
probably the Plato, ii. 16, 1370). Miyacha
cause or a predisposing cause of certain diseases (Bull. Coll. Agric. Imp. Univ. Tokyo, 1897, 2,
of the bones of shown that in the cases of Pceonia
horses, mules, and donkeys 458) has
(Ingle, Jour. Comp. Pathology and Therapeutics, albiflora and Thea chinensis, even old leaves,
1907 ; Jour. Agric. Science, 1908, iii. 22 ; Jour. showing incipient decay, can produce asparagine.
Roy. Inst. Public Health, 1909); Avhile the It occurs to a larger extent in leguminous plants
ratio of potash to soda in the food has an than in any other natural order, and is most
important bearing upon health, and especially abundant at the time of germination, the
upon the susceptibility to certain diseases, quantity being greater in etiolated than in
e.g. scurvy. normal plants (Borodin, Bied. Zentr. 1879,357),
310 ASPARAGINE.
Sachsse (Landsw. Versuchs. Stat. 1874, 17, 88) !
34, 36) the molecular heat of combustion is
;
found that the amount of asparagine in germi- j

448-4 Gals., and the heat of formation 205-1
nating peas increased from 0-67 to 6-94 p.c. during j
Cals. (Berthelot and Andre, Compt. rend. Ifc90,
24 days' growth; and Schulze and Umlauft ;
120, 884) ; it is sparingly soluble in cold, readily

(ibid. 1875, 18, 1) found 17-9 p.c. of asparagine | so in hot water 1 part dissolves in 82 parts
in the dried shoots of Lupinus luteus seedlings of water at 10, in 47 parts at 20 (Becker, Ber.
j
germinated in the dark in distilled water (com- 1881, 14, 1028), in 58 parts at 13, and 1-89
pare also Mercadante, Gazz. ital. chim. 1875, 5, parts at 100 (Guareschi, Gazz. chim. ital. 1876, 6,
'
187 ; Schulze, Landsw. Versuchs. Stat. 1895, I
370 compare Bresler, Zeitsch. physikal. Chem.

;
46, 383 ; Stoklasa, Landw. Jahrb. 1895, 24, ]
1904, 47, 611). The aqueous solution is weakly

827 ; Bourquelot and Herissey, J. Pharm. 1898, acid, has an insipid and disagreeable taste, and
(vi.) 8, 385 ; Bre'al, Ann. Agron. 1900, 26, 5 ; is laevo-rotatory [o] 5 4' (Piutti, Compt.
|
D
Schulze and Barbieri, Landsw. Versuchs. Stat. rend. 1886, 103, 134); the rotatory power of
21, 63 ; Kinoshita, Bull. Coll. Agric. Imp. Univ. the solution is increased by the addition of
Tokyo, 1895, 2, 203) ; Schulze and Bosshard, alkalis, inverted by mineral acids, and destroyed
Zeitsch. phvsiol. Chem. 1885, 9, 420; Bungener,
acetic acid (Champion and Pellet, Compt.
i
Bied. Zentr. 1885, 861 ; Behrens, Bot. Zentr. by

rend. 1876, 82, 819; Becker, Ber. 1881, 14,
1894, 178). Asparagine is one of the decom- !
1028). Advantage is taken of this last fact to

position products of proteid matter (Schulze, [
eliminate the error due to the presence of
Bied. Zentr. 1901, 30, 106 ; Chem. Zentr. 1901,
asparagine in saccharimetric determinations of
!
i. 1108; Ber. Deut. Bot. Ges. 1907, 25, 213), and

sugar liquors from beets and canes. Asparagine
j
its accumulation in the plant during the periods

is partially hydrolysed by boiling with water,
of germination and budding, particularly when acid
forming aspartic (aminosuccinic acid)
the development occurs in the dark is attributed
H
C 2 3 -NH 2 (C0 2 H) 2 and ammonia; the change
by Borodin (Bied. Zentr. 1879, 357) and Schulze
!
is rapid and complete when excess of barium

and Barbieri (J. pr. Chem. 1882, [2] 25, 145), to
the absence of carbohydrates which under hydroxide or dilute hydrochloric or sulphuric
j
acid is employed (Schulze, Landsw. Versuchs.
conditions of normal assimilation effect the j
Stat. 29, 233) ; by the action of potassium

reincorporation of amides into proteid mole-
cules ; and this view is confirmed by Monteverde
j
permanganate, asparagine is oxidised to car-

j
bamide and ammonia ; and when used in 5 p.c.

(Ann. Agron. 17, 376), who found that branches
of lilac plunged in distilled water or 4 p.c.
aqueous solution for the culture of Bacillus
pyrocyanicus, it is converted into aspartic
!
glycerol solution and kept in the dark, contained acid after 60 hours, and completely decomposed
abundance of asparagine at the end of 15 days, j
after 72 hours (Arnaud and Charrin, Compt.
but neither starch nor mannitol. When, how- ;
rend. 1891, 112, 755; Adeney, Proc. Roy.

ever, branches of the same plant were kept in Irish Acad. 1905, 25, 6). Under the action of
solutions of glucose, sucrose, or mannitol, they
enzymes, asparagine yields a mixture of formic,
|
formed no asparagine in a month, but contained and

much mannitol and starch. Another source i
propionic, and succinic acids (Neuberg
of asparagine in the plant is its synthetic
Cappezzuoli, Biochem. Zeitsch. 1909, 18, 424),
and a similar change is effected by brewer's
formation from ammonium salts, urea, or
nitrates supplied by the soil. This synthetic yeast (Effront, Mon. Sci. 1909, (iv.) 23, i.
145).
production is only possible in the presence of
The estimationof asparagine is based upon
sugar, and under conditions that exclude the
formation of proteids (Suzuki, Bull. Coll. Agric. its quantitative conversion into aspartic acid
and ammonia by the action of hydrochloric
Imp. Univ. Tokyo, 1895, 2, 196). The function
of the asparagine in the plant economy is the acid, the aspartic acid may be removed in
the form of its sparingly soluble copper salt
production of proteid matter ; hence the
addition of leguminous seeds after steaming (Engel, Compt. rend. 1888, 106, 1734) and the
to the mash in brewing is recommended by ammonia determined by Sachsse's method (J.
Birner (J. Soc. Chem. Ind. 1882, 333), as the pr. Chem. 1872, [2] 6, 118) or by one of the
modifications of Schloessing's method described
asparagine they yield forms excellent nutriment
for the yeast cell ; and Kinoshita (Bull. Coll. by Meunier (Ann. Agron. 6, 275), by Schulze
(J. pr. Chem. 1885, [2] 31, 233), or by Brown
Agric. Imp. Univ. Tohyo, 1895, 2, 196) found
that young shoots of soja bean that showed an and Millar (Jour. Soc. Chem. Ind. 1904,
increase in asparagine, from 21-5 to 28-7 p.c. after 135).
four weeks' natural growth, became poorer in has feeble basic and acidic
Asparagine
asparagine (18-9-13-7 p.c.) if grown for the and forms salts with acids and bases
properties,
same period in methyl alcohol and glycerol (Chautard and Dessaigne, Annalen, 1848, 68,
solution, but contained reserve proteid matter. 349; Dessaigne, Annalen, 1852, 82, 237;
Asparagine can be extracted from the juice Smolka, Monatsh. 1887, 6, 915) ; it also forms
expressed from young vetch seedlings that double compounds with certain salts of the
have germinated in the dark, 10 kilos, of vetch heavy metals, the sparing solubility of the
yielding 150 grams of pure asparagine (Piria, compound with mercuric nitrate is made use
Annalen, 1848, 68, 343). of in isolating small quantities of asparagine
Asparagine crystallises from aqueous solution from solutions containing carbohydrates
in large rhombic laevo- hemihedral prisms, (Schulze, Ber. 1882, 15, 2855); the alum
a :6 c: 0-4752 1 0-8294 (Freundler, Compt.
: : : : H
(C4 tO^Nt ) tHJ30 4^l t(SO4) w24H,9 forms
rend. 1897, 125, 657). containing 1H 2 O, which octahedral crystals. Asparagine is converted
it loses at 100, and then melts at 234-235 into Z-chlorosuccinic acid and fumaric acid by
(Michael, Ber. 1895, 28, 1629) ; it has a sp.gr. the action of nitrosyl chloride in hydrochloric
1-5434 at 14-8/4 (Piutti, Gazz. ital. chim. 1904, acid solution (Tilden and Forster, Chem. Soc.
ASPARAGINE. 311
Trans. 1895, 67, 489) ; it yields the amide of the racemisation of the Z-asparagine during the
uratnidosuccinic anhydride process of evaporation of the solutions. The
CO-NH,-CH 2 -CH-NH-CO-NH author states that after boiling Z-asparagine
in tf/10 hydrochloric acid solu-
[0]|+36-19 ,
CO tion] for 12 hours, with water, and subsequent

when fused with carbamide (Guareschi, Gazz- fractional crystallisation, he obtained a fraction
chim. 1876, 6, 370), and is converted into
ital. that had [o]| 15-3 in acid
N/1Q hydrochloric
amidosuccinuric acid
solution, and therefore contained d-asparagine.
^^NH-CO-NH., In addition to the two asparagines already
described, there is a third form known as
m.p. 137-138, by the action of potassium
it does not occur naturally is
Ber. o-asparagine ; ;
cyanate (Guareschi, 1877, 10, 1747).

optically inactive, crystallises in the triclinic
Certain condensation products of asparagine
system, a b : c= 1-5957 1 0-5668 ; a=9119' ;
: : :
with other amino- acids are described by Fischer =

j8 113/12', 7 =83 48' (Brugnatelli) ; and has
(Ber. 1904, 37, 4585; 1907, 40, 2048), chloro- a sp.gr. 1-454 at 14-8/4 (Piutti, Gazz. chim.
acetylasparagine, m.p. 148-149 (corr.); glycyl- ital. 1904, 34, ii. 36), and is not structurally
asparagine, m.p. 216, [a] D -6-4 at 20; identical with the optically active or /3-aspara-
anhydroglycylasparagine, decomposing at 274 ; gines. The three asparagines have been syn-
d-lencyl-l-asparagine, decomposing at 230 (corr. ), thesised by Piutti (Gazz. chim. ital. 1887, 17,
[a]
53-6 at 20 ; l-leucyl-d-asparagine, m.p. 126 ; 1888, 18, 457) by the following methods,
that leave no doubt as to the constitution of
228 (corr.), [a] +17 '8; asparagylaspartic
the compounds. By the reduction of the oxime
acid, decomposing at 120. Sasaki (Beitr. Chem. of oxalacetic ester C0 2 Et-CH,,-C(NOH)-C0 2 Et
Physiol. Path. 1907, 10, 120) describes a benzoyl- with sodium amalgam and partial saponification
polypeptide of asparagine C 19 24 8 e , decom- H N of the product, Piutti obtained two different
posing at 210, and giving the biuret reation. ethyl hydrogen aspartates, melting at 165 and
As regards the alimentary value of asparagine, 200 respectively. The ester melting at 165
it has been found that in the case of herbivorous is identical with the compound obtained by
mammals and geese, asparagine has a proteid- reducing Ebert's (Annalen, 1885, 229, 45) mono-
action, and under appropriate con-
sparing ethyl ester of oximinosuccinic acid, which has
ditions prevents waste and causes the formation the formula C0 2 H-CH 2 -C(NOH)-C0 2 Et, since
of proteid matter (Weiske, Bied. Zentr. 1879, on heating it loses C0 2 and forms oximino-
744 1882, 312 ; Zeit. fur Biol. 15, 261 ; 20,
;
propionic ester CH 3 -C(NOH)-C0 2
Et. It follows,
276; Landws. Versuchs. Stat. 1888, 34, 303; therefore, that the ethyl hydrogen aspartate
Rosenfeld, Zeit. Ver. Deutsch. Zucker. Ind. melting at 165 is the monoethyl a-aspartate
1900, [539] 1055, from Jour. Soc. Chem. Ind. C0 2 H-CH 2 -CH(NH 2 )-C0 2 Et, and the ester melt-
1901, 271). According to Zuntz and Miiller ing at 200 must be the monoethyl /S-aspartate
(Pfliiger's Archiv. 1906, 112, 245), the proteid- C0 2 H-CH(NH 2 )CH 2 -C0 2 Et. When these esters
sparing action of asparagine is the result of are treated with alcoholic ammonia, they are
a kind of symbiosis, the bacteria in the paunch converted into the corresponding asparagines ;
of the ruminants decomposing the asparagine the ester m.p. 165 gives inactive a-asparayine
in preference to the protein in the food. In C0 2 H-CH 2 -CH(NH 2 )-CONH 2 and the ester ,
the case of omnivora and carnivora, asparagine

m.p. 200 yields a mixture of d- and I- /8-aspara-
exerts only a diuretic action (Murck and Voit, C0 2 H-CH(NH 2 )-CH 2 -CONH 2 From .
gines
Bied. Zentr. 1884, 749 ; Politis, Zeit. Biol. 1893, silver ethyl 7-oximinosuccinate
27, 492; Mauthner, ibid. 507; Gabriel and /CH-COoEt
Voit, ibid. 29, 115, 125; Levena and Kohn,
Amer. Jour. Physiol. 1909, 23, 324).
OH-N< |
\CH-CO 2 Ag
Dextro-asparagine was discovered by Piutti Piutti (Gazz. chim. 1890, 20, 402) obtained a
ital.
(Ber. 1886, 19, 1691) in the young shoots of the mixture of the three asparagines, the a-aspara-
vetch (Vicia saliva, Linn.) 6500 kilos, of vetch
gine readily gave up its water of crystallisation
in
buds yielded 20 kilos, of crude asparagine, from
a vacuum, and fell to powder and the d- and I- /8-
;
which 100 grams of pure dextro-asparagine
was isolated it is slightly more soluble than asparagines could then be separated by hand
:
the Isevo- compound the solution has an intensely sorting. A mixture of the three asparagines
;
was also obtained by the action of alcoholic
sweet taste, is dextro-rotatory in neutral ammonia on the ethyl hydrogen ester of inactive
or alkaline solution [a] +5-41 (Piutti, Compt.
aspartic acid (Piutti, Gazz. ital. chim. 1887,
rend. 1886, 103, 134), and Isevo-rotatory in 17, 126 ; 1888, 18, 457). Korner and Menozzi
acid solution ; it forms large rhombic dextro- (Gazz. ital. chim. 1887, 17, 171, 226) effected
hemihedral crystals, a b : c : 0-4741 1 0-8310
: : : : the synthesis of the d- and I- 0-asparagines
(Freundler, Compt. rend. 1897, 125, 657). A from ethyl bromosuccinate, from ethyl fumarato
solution of equal parts of the two optically or ethyl maleate, by the action of alcoholic
active asparagines is optically inactive, but ammonia ;
and similar results were obtained
the two varieties separate on crystallisation, by Piutti (Ber. 1896, 29, 2069) with Z-bromo-
twining frequently taking place between the succinamic acid or maleic anhydride.
left and right crystals (Piutti, Compt. rend.
' P-Ethylasparagine C0 2 H-CH(NH 2 )-CH 2 -
1886, 103, 134). CO-NHEt, m.p. 258-260 with decomposition,

According to Pringsheim (Zeitsch. physiol. and 0-allylasparagine C0 2 H-CH(NH 2 )-CH a -
Chem. 1910, 65, 89), the d-asparagine found by CO-NH-C 3 H 4 , melting and decomposing at 258~
Piutti is the mother liquors from which the 261, prepared by the action of the cor-
Z-asparagine had been isolated, was formed by responding alkylamine on 0-ethylaspartic acid,
312 ASPARAGINE.
yield optically inactive solutions (Piutti, Gazz. I
is one of the acid constituents of Kiihne's
chim. ital. 1888, 18, 478). M. A. W. '
antipeptone
'
(Kutscher, Zeitsch. physiol.
ASPARAGUS. The shoots of this plant Chem. 1898, 25, 195 26, 110). :
(Asparagus officinalis) are used as a table The naturally occurring aspartic acid is
vegetable. laevo-rotatory and the same l-aspartic acid is
Carbo- obtained by hydrolysis of fovo-asparagine
Water Protein Fat hydrates Ash Ber. it in
(Schiff, 1884, 17, 2929); crystallises
Average composition 94-0 1-8 0-2 3-3 0-7
rhombic prisms, m.p. 270-271 (Michael, Ber.
The nitrogenous matter of asparagus consists 1895, 28, 1629), is sparingly soluble in water,
largely of amino-succinamic acid CO(NH 2 )-CH 2
-
100 grams of water dissolve y mg. of the acid
CH(NH 2 )-COOH, a substance known (from its at t, where
discovery, in 1805, in asparagus shoots) as 2
y=372+14-l-0-18124< +0-0053<
3
asparagine (q.v.). (Engel. Compt. rend. 1888, 106, 1734). A

Coniferin and vanillin have also been found solution containing 1-873 p.c. of acid is feebly
I
in the sap and cellular tissue (Lippmann, Ber.

dextro-rotatory below 75, but laevo-rotatory
1886, 18, 3355); Tanret (Compt. rend. 1909, i
above that temperature ; in alkaline solutions
149, 48) describes two new carbohydrates as the substance is strongly laevo-, and in acids
occurring in approximately equal quantities in
j
strongly dextro-, rotatory (Becker, Ber. 1881,

H
asparagus roots asparagose (C 6 10 5 ),,-H 2 O, The heat of combustion is 387-2 Gals.,
=
where n 15 or 16, crystallising in microscopic :
14, 1028).
the heat of formation 231-9Cals. (Berthelot and
needles, soluble in water, insoluble in absolute Andre', Compt. rend. 1890, 110, 884) ; the heat
alcohol, m.p. 198-200, gives no colouration i
of dissolution at 16 is 7-25 Gals., heat of
with iodine, and does not reduce Fchling's neutralisation by sodium hydroxide +3-0 Gals.
solution ; and ty-asparagose, a white, hygroscopic for the first, and +3-5 Gals, for the second
substance more soluble than asparagose. Both
i
equivalent (Berthelot, Compt. rend. 1891, 112,

substances are hydrolysed by invertase, yielding
i
829). Aspartic acid is readily soluble in aqueous
dextrose and Isevulose. i
solutions of certain mineral salts ; for this reason
The seeds of asparagus were examined by Schiff (Ber. 1886, 17, 2929) recommends that
Peters (Arch. Pharm. 1902, 240, 53), and were in its preparation from asparagine by boiling
found to contain water 11-5, woody fibre 8-2, with hydrochloric acid, the minimum quantity
nitrogen 3-0, and oil 15-3 p.c. Starch was not (2 mols.) of acid be employed, and the excess
present, but a reserve cellulose (mannan), afterwards neutralised by ammonia (1 mol.);
capable of yielding d-mannose on boiling with by adopting this precaution, a yield of 90 p.c.
dilute hydrochloric acid, occurred ; 37-5 p.c. of of the theoretical is obtained.
the weight of the seeds, of mannose was obtained.
Aspartic acid forms salts with acid and bases,
The oil was reddish yellow, had a sp.gr. of 0-928 , H
the copper salt C 4 5 4 NCu,4H 2 0, forms pale-
at 15, and an iodine number of 137-1. H. I. blue needles almost insoluble in cold water (Engel,
ASPARTIC ACID. Aminosuccinic acid
I.e.). Aspartic acid is oxidised by hydrogen per-
CO 2 H-CH 2 -CH(NH 2 )-C0 2 H, found in young oxide to the semi-aldehyde of malonic acid which
sugar cane and in molasses of sugar beet breaks up into acetaldehyde and carbon dioxide
(Scheibler, J. 1886, 399), and in young shoots of
(Dakin, Jour. Biol. Chem. 1909, 5, 409); it
the gourd (Schulze and Barbieri, Ber. 1878,
is capable of furnishing the nitrogeen required
710), has been observed in diseased liver
j
11, for the development of B-coli communis in

(Taylor, Zeitsch. physiol. Chem. 1901, 34, 580),
I
presence of mannitol and glucose, becoming

and occurs in certain glands of Tritonium j
reduced to ammonium succinate (Harden, Chem.

nodosum, the posterior portion of the gland Soc. Trans. 1901, 623), and by enzyme action
wrhen stimulated secretes an acid fluid from which
!
it is decomposed into formic, propionic, and

acid immediately crystallises. As
|
aspartic succinic acids (Neuberg and Cappezzuoli,

aspartic acid is soluble in sea-water, it is probably
[
Biochem. Zeitsch. 1909, 18, 424 ; Borchardt,

employed by the animal in destroying the Zeitsch. physiol. Chem. 1909, 59, 96). When
calcareous shells of the other shellfish that j
aspartic acid is heated at 190-200 for 20 hours,

form its food (Henze, Ber. 1901, 34, 348).
and the product boiled with water, two sparingly
Aspartic acid is prepared by hydrolysing soluble anhydrides, octoaspartide
asparagine by means of hydrochloric or sul-
|
phuric acid, lime, baryta, lead oxide or potash

NH
(Plisson, Ann. Chim. Phys. [2] 35, 175; 37,
HO(CO-C-CH 2 -CO) 8H
81 ; 40, 303 ; Schulze, Landsw. Versuchs. Stat.
29, 233) ; it is one of the degradation products and tetrasparlide
of proteid matter, and is obtained when casein
or proteid is heated with (1) dilute sulphuric
NH .
acid (Kreussler, J. pr. Chem. 1869, 107, 239; .

HO(CO-C-CH 2 -CO) 4H
Ritthausen, ibid. 218 ; Fischer, Zeitsch. |
physiol. Chem. 1901, 33, 151 ; 1902, 35, 70 ; are obtained, the more soluble octoaspartic
36, 462); (2) bromine or with stannous chloride
(Hlasiwetz and Habermann, Annalen, 1871, NH 2
159, 325; 1873, 169, 162). Aspartic acid is HO(CO-C-CH 2 -CO 2H) 8H
produced by the oxidation of conglutin with I
potassium permanganate (Pott, J. pr. Chem. and letraspartic acid

1873, [2] 6, 91), by the pancreatic digestion
of fresh blood fibrin at 40-50 (Radziezewski
NH 2
and Salkowski, Ber. 1874, 7, 1050), or of gluten HO(CO-C-CH 8 -C0 2H) 4H

(Rnicriem, Zeitsch. f. Biol 1876, 11, 198); and
ASPHALT. 313
can be isolated from the filtrate (Schiff, Ber. the sodium salt of ethyl oximino-oxalacetate
1897, 30, 2449). The following alkyl esters (Piutti, Chem. Zentr. 1888, 68). (d l)- +
of aspartic acid are described Monoethyl :
Aspartic acid forms small monoclinic prisms;
199 ; diethyl and 100 grams of water dissolve y mg. of the acid at
asparate hydrochloride, m.p.
dimethyl aspartate hydrochlorides, deliquescent t, where
t/=517+21-693<-0-165< 2 +0-0079<
3
solids (Curtius and Koch, Ber. 1885, 18, 1293 ;
Weescheiden and Frankl.Monatsh. 1906, 27, 487), (Engel, Compt. rend. 1888, 106, 1734). The
ethyl 0-aspartate C0 2 H-CH(NH 2 )-CH 2 -C0 2 Et, copper salt CuC 4 H 5 4 N,4JH 2 O is dark-blue
m.p. 200; ethyl a-aspartate CO 2 H-CH 2 -CH(NH 2 )
(Engel. I.e.). The benzoyl derivative has
C0 2 Et, m.p. 165 (Piutti, Chem. Zentr. 1888, m.p. 164-165 and can be resolved into
(corr.),
1459). The methyl, ethyl, allyl, propyl, iso- its active components by crystallising the
propyl, butyl, wobu.tyl, and i'soamyl hydrogen brucine salt (Fischer, Ber. 1899, 32, 2451).
esters are dextro-rotatory at ordinary and M. A. W.
laevo-rotatory at higher temperatures, and ASPHALT. Compact bitumen, Mineral pitch,
form sparingly soluble copper salts (Piutti and Jews' pitch, Bitumen of Judcea. (Judenpech,
Maghi, Gazz. chim. ital. 1906, 36, ii. 738). Erdpech, Bergpech, Ger. Goudron mineral, Fr.)
;
Z-Diethylaspartate has b.p. 126-5/ll mm. A name givento the solid varieties of bitumen.
== 9-46 In its purest form asphalt presents the appear-
pressure; sp.gr. 1-089 at 17 and [a]p
ance of a black or brownish-black solid substance,
(Fischer, Sitzungber, Akad. Wiss. Berlin, 1900,
48, 1062), or b.p. 126 -127/10mm., i50-152/25 possessing a bright conchoidal fracture. It
melts at 100, burning with a brilliant flame and
mm. pressure, and forms a yellow picrolonate
C 8H 16 4 N,C 10 H 8 6 N 4 m.p. 290 emitting a bituminous odour. Sp.gr. 1-0-1-68.
,
(Schmidt and Asphalt is insoluble in alcohol and water, soluble
Widman, Ber. 1909, 42, 497). in about five times its weight of naphtha, and
Of the acyl derivatives of aspartic acid, the in benzol. It is dissolved by alkalis and alkaline
benzenesulphonyl derivative S0 2 Ph-NH-C 2 H, carbonates.
(C0 2 H) 2 melts at 170 (Hedin, Ber. 1891, "23, By dry distillation a yellow oil, Asphalt
3196) ; the hippuryl derivative NHBz-CH 2 -CO. oil, is obtained. It consists of hydrocarbons
H
NH-C 2 3 (C0 2 H) 2 , m.p. 191 (Curtius and mixed with a small quantity of oxidised matter.
Curtius, J. pr. Chem. 1904; (ii.) 70, 158); It begins to boil at 90, but the boiling-point
benzoyl l-aspartic acid, m.p. 184-185 (corr.)-
20 gradually rises to 250. The portion boiling
has [O] D +37-4, leucyl aspartic acid CH 2 PAa below 200 has the sp.gr. 0-817 at 15; that
above 200 has a sp.gr/ of 0-868 at 15. Both
CH(NH )-CO-NH-C 2 H 3 (C0 2 H) 2 ,H 2
2 decom-
poses at 180-182 (corr.) (Fischer and Koenigs, portions gave by analysis about 87-5 p.c. carbon,
Ber. 1904, 37, 4585) 11-6 p.c. hydrogen, and 0-9 p.c. oxygen, which
and the picryl derivative
;
H N4 has m.p. 137; aspartic diamide

isnearly the composition of oil of amber ( Volckel,
Ci 8 10
C 2 H 3 (NH 2 )(CONH 2 Annalen, 88, 139). Nitric acid converts it into
)2 m.p. 131, has [] D ~7,
,
a resin, having the odour of musk and the taste
and gives the biuret reaction (Fischer and of bitter almonds.
Koenigs, Ber. 1904, 37, 4585). Aspartic acid Boussingault obtained from the asphalt of
resembles asparagine in its Bechelbrunn a pale-yellow oil, petrolene, having
physiological action
(Salkowski, Zeitsch. physiol. Chem. 1904, 42, a faint taste and bituminous odour, of sp.gr. 0-891
1207 ; Andrh'k and Velich, Zeitsch. Zuckerind. at 21, and boiling at 280.
Bohn, 1908, 32, 313). Byheating asphalt to 250 for 48 hours, the
d-Aspartic acid, obtained by hydrolysis of volatile oils are driven off a black solid sub-
;
rf-asparagine (Piutti, Ber. stance, asphaltene, is obtained. It becomes soft

1886, 19, 1694), or
from J-bromosuccinic acid and aqueous ammonia and elastic about 300.
at 40, a Walden rearrangement taking place The purest asphalt is found on the shores of
(Fischer and Raske, Ber. 1907, 40, 1051); is the Dead Sea and in the pitch lakes of Trinidad
also obtained from a solution of the racemic and Mexico. Rocks more or less impregnated
acid [(d+l)
aspartic acid] which has been with bitumen, to which the name earthy or
innoculated with a mould grown on
Z-aspartic
crude asphalt is given, are found at the Poldice
acid (Engel, mines, Cornwall near Matlock, Derbyshire ;
Compt. rend. 1887, 106, 1734). ;
Benzoyl d-aspartic acid, obtained by Fischer at Haughmond Hill, Shropshire ; at the Hot-
(Ber. 1899, 32, 2451), by the resolution of the wells, near Bristol in the limestone near
;
racemic compound,
through the brucine salts, Glasgow ; the freestone near Edinburgh and ;
has 181-182, _37. 6 generally throughout the Orkneys. Large

m.p. [ a ]2 in alkaline
deposits occur also at Seyssel, Dept. de 1'Ain ;
solution. at Bechelbrunn and Lobsann, Lower Rhine ; at
Inactive, (d+l)-aspartic acid, prepared by the Bastennes and Dax, in the De'pt. des Landes ;
action of in the Val de Travers, Neuchatel and other
boiling hydrochloric or nitric acid on
the product obtained the ammonium
by heating places.
salts of malic, fumaric acids (Dessaigne,
male'fc, or Asphalt is separated from the minerals with
Compt. rend. 1850, 30, 324); by heating an which it is associated either by melting the
aqueous solution of the hydrochloride of mass, allowing the earthy matters to subside
J-aspartic acid at 170-180 for some hours and removing the bitumen or by boiling with
;
(Michael and Wing, Ber. 1884, [1] 2984) ; by water, which causes the bitumen to run out in
d- or
heating J-aspartic acid with 2 mols. HC1 the melted state or by the action of hydro-
;
(sp.gr. 1-107) at 170-180, or from an aqueous chloric acid, which dissolves the calcium car-
solution of equal parts of the d- and I- acids bonate and leaves the asphalt ; or with oil of
;
the racemic acid
crystallises out (Piutti, Ber. turpentine, which dissolves out the bitumen.
1880, 19, 1694) ; by reducing and Murrie (J. Soc. Chem. Ind. 3, 182) describes the
hydrolysing
314 ASPHALT.
methods used in Italy for the extraction of and other species of the same genus, contain a
bitumen from crude asphalt. fermentable substance from which alcohol may
The Val de Travers asphalt contains about j
be prepared (cf. Riviere and Bailhache, Compt.
20 p.c. of bitumen, and it only requires the [
rend. 1895, 121, 659). By drying and coarsely
addition of 6 to 8 p.c. of mineral or coal tar to j
grinding the tubers, Landerer obtained a powder
convert it into a plastic, workable mastic of good which, mixed with water, formed a strong glue.
quality for pavements and hydraulic works. Badoil and Lienders obtain tannin from the
The modern method of laying down asphalt pulp left after the extraction of the alcohol.
pavement is to first prepare a foundation of con- ASPIDIN v. FILIX-MAS.
crete the surface of which is carefully flattened. ASPIDOSAMINE and ASPIDOSPERMINE
On this even surface, when thoroughly dry, the v. VEGETO-ALKALOIDS.
melted asphalt is spread with a wooden trowel, ASPIRATORS. Aspirators are used to draw
and the surface is smoothed over. The
finally air or other gases
through any apparatus con-
liquid Val de Travers, Limmer'?, and Barnett's nected with them, and were probably first
asphalts used for this purpose are all mixed employed by Brunner in his analyses of air,
with grit or sand, and so present rougher surfaces 1830-1840 (Pogg. Ann. 20, 274; 24, 569;
than those pavings which consist of asphalt 31, 1). The process of aspiration or inhaling
alone. Brande (D. R. P. 4993, 1878) mixes ground of air is, however, most common, being necessary
slag with the asphalt instead of sand. to the life of animals and to the ventilation
Another method of paving is to break up the of buildings, mines, &c., to change the air so
bituminous ore, and heat the fragments till that it may support life. In other analyses
they crumble to powder. A layer of this hot of airby Dumas and Boussingault, an exhausted
powder, from 16 to 20 inches thick, is laid on globe or jar was used as an aspirator (1841,
the dry concrete and compressed by stamping Ann. Chim. Phys. [3] iii. 257). When a vessel
with hot irons. isemptied of liquid, air must enter to take its
Artificial asphalt, or gas-tar asphalt, is a place, and the common aspirator, in its various
mixture of chalk:, sand, or limestone with the forms, is a vessel with two openings, the lower
thick, pitchy residue obtained by evaporating to serve as outlet for the water or liquid, and
the more volatile portions of gas tar. The the upper as inlet for the air or gas to be aspirated.
mineral substance must be heated to expel With suitable fittings a siphon may be used
moisture and adhering air, and then added to instead of the lower opening, or the apparatus
the strongly heated pitch. may be modified into a bell-jar standing over a
In addition to the use of asphalt for pave- basin or large jar, the air being drawn in through
ments, water-tight tanks, and coatings for iron the neck of the bell-jar. This is Mohr's aspirator,
tubes used for conveying gas or water, &c., it is which is sometimes poised like a gasholder to
used in photography, in photo-lithography, and facilitate filling and emptying of the bell-jar
photo-engraving, owing to the asphalt becom- (Mohr, Lehrbuch der Titrirmethode, 1855,
ing insoluble in turpentine after exposure to Brunswick).
light. In the latter case copper plates are From their introduction, aspirators were used
covered with a thin coating of pure asphaltum, not only to draw in gases through apparatus and
or bitumen of Judaea, dissolved in benzene or reagents employed, at a regulated rate, but
also
chloroform. When dry, the plate is exposed to measure the gases so manipulated by simply
behind a film to bright sunlight for half an measuring or weighing the liquid run out of the
hour, and then developed by first softening the aspirator. For approximate readings aspirators
soluble portion of the asphaltum with olive oil, of glass may be graduated, and those of metal
to which subsequently a little turpentine is may be provided with gauge glasses.
added. As soon as the lines are bare the turpen- Numerous forms of the simple aspirator have
tine and oil must be washed away by the action been invented by Brunner, Regnault, Mohr, and
of water. others. Fig. 1 is perhaps the form in most fre-
Methods for preparing asphalt for paving
and other purposes are described by Dagusan
(D. R. P. 4999, 1878 ; Dingl. poly. J. 232, 547) ;
Kalilbetzer (D. R. P. 5646, 1878) ; Zadig and
Neuberg (D. R. P. 5678, 1878 ; Dingl. poly. J.
233, 490) ; Clark (Em*. Pat. 8036, 1884 : J. Soc.
Chem. Ind. 5, 183) ; Kettmann (Eng. Pat. 12425,
1884; J. Soc. Chem. Ind. 4, 675); Richter
(Siefenseid Zeit. 23, 272 ; J. Soc. Chem. Ind.
2, 474).
Native asphalt can be distinguished from
artificial asphalt by extracting with carbon di-
sulphide, filtering, evaporating to dryness, and FIG. 1. FIG. 2.
heating the residue till it can be ground to a

fine powder ; 0-1 gram is treated with 5 c.c. of quent use, and is generally of glass, plain or
fuming sulphuric acid for 24 hours, and is then graduated. Fig. 2 is a- very convenient form,
mixed, with continuous stirring, with 10 c.c. of described by Clemens Winkler (Industrie-Case,
water. If pitch or coal tar be present, the solu- 1877, 39-41) constructed of zinc plate
and
tion will be of a dark-brown or blackish tint ; if supported on a wooden tripod. The second tap
the
not, the solution will be of a light-yellow colour below, on the side tube, is useful in filling
(v. PITCH). aspirator with water. Fig. 3 is the form often
ASPHODEL. The tuberous roots of Aspho- used in testing the gases from chemical works.
It is simply a'cubical or rectangular box made
d&le de Sardaigne, of Asphoddus ramosus (Linn.),
ASPIRATORS. 315
of sheet lead, with a graduated gauge glass, and tubulure to D at the side of the bottle is secured
can be opened at A to fill it with water. by pushing an indiarubber tube through the
Double aspirators. In short operations the tubulure and fixing it in the proper position
simple aspirator requires no refilling nor special before the wax is run in, and after the wax is
attention after the taps are adjusted. To obviate quite solid this tube is drawn out. The passage
the inconvenience of stopping to change or refill should be curved, so that on emptying the bottle
that would be necessary in longer operations, of water the water runs out to the mark at D.
Brunner, Boisgiraud, Dancer, Muencke, and The bottles are then adjusted by weighing their
others have contrived double aspirators so con- content of water between the marks and adding
nected that each vessel is alternately above and or removing paraffin till at the standard
below, and one or other always ready for use. temperature and pressure they hold the exact
The aspirating bottles may be mounted on a quantity of water corresponding to the volume
common axis as in Dancer's swivel aspirator, required. In successive weighings of bottles so
adjusted the differences should not exceed
0-1 gram. To avoid loosening of the wax from
direct contact with the glass, the bottles should
be preserved from changes of temperature and
from mechanical vibration, &c.
Constant or automatic aspirators. Instru-
ments of this class have been invented by
Guthrie (Phil. Mag. [4] 15, 64) and by Bonny
(Winkler's Technical Gas Analysis, trans, by
Lunge, 17). In each of them a pipe from the
water supply leads a constant stream of water
into a vessel, which, when full, is emptied by a
siphon, whose tube is of larger size than the
supply pipe. The arrangement thus acts on
the principle of the intermittent siphon, and
the vessel is filled and emptied at regular
FIG. 3. FIG. 4.
intervals. In Bonny's instrument these are
Fig. 4(Chem. News, 1864, 10, 295). These swivel registered by a simple mechanism, and the total
aspirators arc very convenient, but the difference
volume passed is known on measuring the
of water-level in the two bottles is not under the volume passed in one operation.
control of tho operator and varies between the The Sprengel and injector pumps may be
height of one bottle and a very small minimum.
used as constant aspirators (v. FILTER PUMPS).
Figs. 5 and 6 show an arrangement devised By means of a collecting box attached below the
pumps to allow the gas and water to escape at
different levels, the gas may be measured by
passing it through a small gas meter (Davis,
J. Soc. Chem. Ind. 211).
J. Grossman (Winkler's Industrie-Case,
218) has invented a small mercurial aspirator,
on the principle of the Geissler pump, with two
reservoirs, which are alternately raised and
lowered. It is fitted with registering apparatus.
In testing air and gases from confined places,
works, &c., Angus Smith, Davis, and others
have used small pear-shaped aspirators of india-
rubber. These are emptied by simply squeezing
in the hand. The air escapes by a valve, of
which the simplest is a small slit in the rubber
connecting tube, opening outwards like a
FIG. 5. FIG. 6.
Bunsen's valve. The rubber recovering its form
draws a certain volume of gas through the test-
by the author, which has certain advantages. ing apparatus, and it is easy to ascertain approxi-
The bottles A and B are connected as shown, mately the total volume of gas corresponding
being raised and lowered alternately. The four- to any given number of times the aspirator
way tap c (shown larger in Fig. 6) has its index has been filled. Another larger aspirator of this
I turned towards the
upper bottle in aspirating class is of bellows form, like a concertina, the
and towards the lower bottle in blowing. It is folding part being of indiarubber.
This aspi-
made from a good gas tap by boring up the rator is frequently used for filling by displace-
centre of the plug at F, leading out the hole at ment jars or bottles with gas to be tested. The
o. A small piece of metal H is then fitted and common single-barrel air pump or apparatus,
soldered diagonally where the holes cross, a on the same principle, is also applied in this
piece of tubing K soldered on to the socket of manner as an aspirator.
the tap, and an index i above the plug. At the British Association Belfast meeting,
Paraffin wax is used to adjiist the bottles for 1874, the late Prof. Andrews showed how an
exact measurement, and to obtain a fine adjust- ordinary wet gas meter could be converted into
ment below at D, as well as above, by a mark on an aspirator by applying motive power to the
the neck of the bottle. The proper quantity of hollow axis of the drum, thereby causing it to
melted wax is run through a wide tube into" the suck in air at the inlet side and at the same time
warm bottle slightly tilted. A passage from the to measure the air on the meter index. Using
ASPIRATORS.
mercury as liquid in a cast-iron meter, a similar I may be set aside as a sample, or the whole heap
arrangement forms the basis of the Barr and '.
may be made into a perfect cone, which is

Stroud air pump applied in the evacuation of flattened and divided into four quarters along
bulbs for electric lighting lamps (J. Soc. Chem. j
two diameters. Two opposite quarters are
'
Ind. 1896, 640 ; Eng. Pat. 13188, July, 1895).
j
removed and mixed, and the process of coning
'
T. F. and quartering repeated as often as necessary.
ASPIRIN. Trade name for acetyl salicylic A heap or vat of ore or tailings, which must
acid C 6 H 4 (COOH)0-CO-CH 3 used as an anti-
,
j
be sampled without being moved, is pierced at
rheumatic. j regularly spaced intervals by a sampling tube
'
ASSAYING. Assaying, the trial of metals,' i
which resembles a cheese-taster, and withdraws
a term originally applied only to the testing of a cylindrical sample extending to the bottom
gold and silver, is now usually extended to the of the vat or heap.
determination of the quantity of the valuable In automatic sampling machines, which
metal in an ore or metallurgical product. It is are much used in Western America, the crushed
also sometimes taken to include the estimation ore is made to slide down an inclined plane or
of any element which may prejudicially affect rotating cone, and a portion of the stream of
the value of the ore, but it is more usual to ore is deflected and set aside as a sample. Those
discuss this together with such work as the machines are preferred which momentarily
complete analysis of ores, slags, furnace materials, i
take the whole stream of ore at regular intervals
'
fuel, &c., under the heading of metallurgical of time. Further reduction in the laboratory
analysis.' A brief account of some of these i is effected by coning and quartering or by a
sections is given below. [
machine such as the riffle or sampling tin,
The art of assaying is of great antiquity. which consists of a series of metal troughs
The use of the touchstone for testing gold in arranged side by side and fastened at equal
India was referred to by Mathuranatha (Hist, distances from each other. A stream of ore
i
of Hindu Chemistry, by Ray, ii. 231), and was let fall on it is in part retained by the troughs
I
probably known in the Greek world at least and in part passes through. j
as early as B.C. 700, when the first electrum or The final grinding of the ore is effected by
gold-silver coins were manufactured. At any means of an iron pestle and mortar, or of a large
rate the touchstone found its way into Greek hammer with a curved face sliding on an iron
mythology. The testing of gold alloys by plate (or buckboard), or by some form of rolling
cementation was described by Pliny, by Strabo, i
or grinding mill. The crushed ore is passed
and in the eighth century A.D. by the AraMan !
through a sieve, the fineness of which varies

Geber, who Avas also familiar with the method ;
according to the ore and the method of assay.
of cupellation, and is reputed to have discovered ! If a panning test is required, a 20-mesh sieve
nitric acid. The parting assay of gold with the '
(i.e.one with 20 holes to the linear inch) suffices.

aid of this acid is referred to in a decree of For most fusions, e.g. dry lead assay, a 60-mesh
Philippe de Valois in the year 1343, confirming i
sieve is used. Gold ores are crushed through
its use in the French Mint. Alloys of silver |
an 80- or 100-mesh sieve, and in the case of
with copper were tested by observing the degree i telluride ores of gold, the best results are
of blackening caused by heat in the Roman ! obtained by using 120-mesh sieves. Before it
Mint under the Republic (Rochon, Essais sur can be passed through a fine sieve, the ore
j
les Monnoies, 17, 1792). j

must be dried, so that the moisture, is determined
It is probable that ores were not valued i
on coarsely crushed ore by drying at 100 on
except by inspection until the Middle Ages. I
a water-bath, or, if the dry material is not likely
The clear references to ore-assaying are
first
j
to be affected in any way by a somewhat higher
to be found in the writings of Biringuccio, temperature, it is heated on a sand-bath. In
Agricola, and Ercker in the sixteenth century, crushing rich gold and silver ores, mint sweep-
but the art was evidently regarded by these ings, &c., pieces of metal are found which
authors as already ancient at the time at which become flattened out and are caught on the
' '
they wrote. Ercker, writing at Frankfort in sieve. These metallics are treated separately,
1580, describes the fire-assays not only of and the value calculated on the weight of ore
several different kinds of gold and silver ores, from which they were derived.
but also of the ores of copper, lead, tin, antimony, The dried and crushed sample is thoroughly
iron, mercury, and bismuth. Assaying by mixed by means of a spatula in a basin, or on
'
means of wet methods,' volumetric, gravi- rubber-cloth, before the portion required for
metric, and electrolytic, is of comparatively recent assay is weighed out. If stored in a bottle or
introduction (excepting the parting assay of tin, the movement of the vessel causes the heavy
gold), but has now in great part superseded the particles to settle, so that the material at the
ancient processes involving the use of furnaces. bottom becomes richer than that at the top.
Sampling. Whether the material to be Ingots of metal are sampled by cuts taken
assayed is a portion of a vein underground, a from the corners or edges, as in the case of
heap of broken ore, pigs of metal, or a delicate refined gold and silver, or by drillings from a
piece of jewellery, in every case a representative number of different spots, as is sometimes done
sample must be obtained. In the case of ore in the case of iron and steel. Pigs of argenti-
in situ underground, pieces are taken from a ferous lead are sometimes sampled by drillings
number of different points and either mixed or or saw cuts. Base gold and silver ingots, and
examined separately. Ore which can be moved in many cases ingots of steel and pigs of lead,
is reduced in bulk either by hand or by machinery, are melted and stirred, and a portion dipped
and is generally crushed finer between each out and granulated by pouring into water, or
successive reduction in bulk. Every second, cast into a little ingot. Coins are sampled in
fifth, tenth, or twentieth shovelful or car-load various ways, silver coins being seldom uniform
ASSAYING. 317
in composition. The simplest method applicable The muffle furnace consists of a small oven or
to all is to roll them out and cut them into a muffle of refractory fireclay open at the front,
large number of little pieces, so that all parts and having an arched top. It is heated by
of the coin may be represented in the portion coal, coke, oil, gas, or electricity. Muffles
taken for assay. This method is adopted in the vary in size according to the amount of work
Philadelphia Mint, but is not in general use, to be done, but those used at the Royal Mint may
other more complicated methods being preferred. be considered full size. Sectional views of one
Gold and silver wares are usually pickled, and are of these furnaces are shown in Figs. 1 and 2.
richer on the surface than in the interior. In The muffle A is 14t inches long, 8J inches wide,
sampling them, it is accordingly necessary to and 5 inches high, inside measurements, with
remove the outside by scraping and then to scrape walls about f inch thick. The mouth is closed
off a portion of metal for assay. by the firebrick B and by a sliding plate. Air
The preliminary examination of ores includes enters through holes in the sliding plate and
careful inspection, which is all the more useful passes out at the back through the tube c,
if some comparatively large pieces are included
in the sample. The proximate constituents,
such as quartz, pyrites, magnetite, galena, &c.,
are thus observed, and the proportions in which
they are present roughly estimated, this informa-
tion being required inmaking-up furnace charges.
Frequently a concentration test is made in a
miner's pan (a flat-bottomed sheet-iron pan
about 20 inches in diameter, and 3 or 4 inches
deep, with sloping slides) or a vanning shovel, or
in any basin, pan, or even clock-glass available.
For this purpose a portion of 25 grams or more
is weighed out, stirred and shaken with water
by a circular motion on the shovel, and the

lighter particles rinsed away and caught in a
basin. Finally by a combination of the circular
motion, and a series of jerks, the denser particles
are thrown up and the lighter ones washed
down the shovel. The concentrates are ex-
amined with a lens or separated, dried, and
weighed, or treated with acid, or examined
by means of the blowpipe, or in other ways, in
order to determine the presence or absence of
elements likely to interfere with the method
of assay chosen. The vanning shovel is used which has a sliding damper and leads into
particularly with tin ores, but may be applied the mam flue. The fuel is ordinary gas, supplied
others. are of bunsen burners D, and complete
to any Panning tests especially by a row
useful in the examination of gold ores, but are combustion of the gas may. be aided by clay fire-
also required to determine the nature of the balls surrounding the muffle. The flues B E carry
' '
mineral or compounds of the heavy metals off the waste gases. The furnace walls consist
in almost all ores. The test may be applied of firebrick bound with iron and covered with a
to half a gram of ore in a watch-glass, if no more thick layer of magnesia and asbestos to check
can be spared. radiation. No chimney stack or forced draught
The furnaces used by assayers are the muffle isrequired for this furnace.
furnace, and the melting or wind-furnace. A melting furnace adapted for the use of
coke as fuel and suitable to make fusions in
assay operations, is shown in section in Fig. 3,
in which A is the fireplace, B the flue, c the
ashpit, D the damper, and E the firedoor. The
most useful size of
the fireplace is
about 9 inches
square, and about
10 niches in depth
from the firebars
to the flue. The
furnace is built of
brick and lined
with firebrick. It
is bound with
angle iron or
covered with iron
plates bolted
together and fur-
nished with tie
rods. Gas-melting
furnaces with
natural draught FIG. 3.
318 ASSAYING.
or using a blast of air are less The

common. cupel tongs, scorifier tongs, and button tongs,
of fireclay or with various scrapers, pokers, &c. Iron slag-
fluxing crucibles (a, Fig. 4) consist
a mixture of plumbago and fireclay, or, in the moulds (b, Fig. 4) are required for casting the
are of results of scorifications and of fusion assays,
assay of galena, of wrought iron. They
different sizes and shapes, the best-known
and hammers, anvils, slag hoops, and other
and implements are also required. The charging
being the Battersea (round, Cornish,
triangle), French, Hessian,
and Colorado cru- scoop (c, Fig. 4) is required for charging metal,
&c., into red-hot crucibles.
The reagents used in fire assay may be
classed as fluxes, agents for reducing, oxidising,
sulphurising, and desulphurising, and covers to
protect the contents of the crucible from the
action of the air, furnace gases, &c. Generally
speaking, an ore consists of compounds of a
heavy metal or metals (the mineral), together
with a quantity of earthy materials, such as
quartz, silicates, &c. (the gangue). It is re-
quired to reduce the valuable constituent to
metallic form, and to incorporate the remainder
FIG. 4.
of the ore in a fusible slag, through which the
cibles, the last-named being used for making particles of metal may settle to the bottom,
fusions in the muffle, a common practice in
where they collect in the form of a button.
America. Most crucibles require careful anneal- Sometimes a regulus or matte (sulphide of a
ing before being used. Roasting
dishes made heavy metal) or a speise (arsenide of a heavy
of fireclay (a, Fig. 5) are for the roasting of ores ; metal) forms a separate layer between the metal
scorifiers (c) are used in the process of scorifica-
and the slag, and a cover, say, of common salt,
may be provided which is lighter than silicate
slags and floats on the top. On breaking open
a cold crucible in which a fusion has been made,
there are, therefore, frequently four layers.
The principal fluxes used are sodium car-
bonate, which forms fusible mixtures with acid
(siliceous) ores, and also acts as a desulphuriser,
converting pyrites into a mixture of sulphides of
iron and sodium which does not form a regulus,
but is dispersed through the slag. Carbonate
of soda is generally used in the form of powdered
bicarbonate, which gives up half its carbonic
FIG. 5. acid without fusion. Soda crystals give up their
water of crystallisation with ebullition, and are
tion ; cupels of various shapes and sizes (d, e)
not suitable unless previously dried. Basic
are made of compressed bone-ash or magnesia,
ores require borax, which forms fusible mixtures
and are required in the assay of the precious with oxides of iron, lime, &c. ; and increases the
metals. The bone-ash cupels may be made by
fluidity of most charges. Crystallised borax
the assayer, and must be carefully dried before
powder on heating swells up enormously, gives
use. Magnesia cupels are usually bought
A flask is shown in up its water and fuses into a glass. The swelling
ready-made. parting
may occasion loss in the assay if the crucible is
too full. To avoid this, borax glass may be
used, which is equivalent to about double its
weight of ordinary borax. Litharge is a useful
flux, especially for oxides of iron, copper, &c.,
but attacks and corrodes the crucibles. Fluor-
spar is sometimes used, especially for phosphates.
Sand is often required to protect the crucible
from attack by basic ores.
The reducing agents are carbon (charcoal
powder or lampblack), flour, tartar or argol
(crude hydrogen potassium tartrate), and
occasionally potassium cyanide. One part of
charcoal is about equal to two parts of flour
or five of tartar, but tartar also acts as a flux,
being converted by heat into carbon and
potassium carbonate. Black flux is a reducing
mixture made by deflagrating one part of nitre
with two and a half parts of argol.
o
FIG. 6.
The chief oxidising agents, which are also
desulphurisers, are hot air, litharge or red lead,
and nitre. Iron is often used as a desulphurising
agent. The ordinary materials used as covers
6, Fig. 5. The furnace implements (Fig. 6) are borax and common salt.
consist of basket or circular tongs for lifting The balances and weights do not differ, as a
crucibles out of the furnace, pouring tongs, rule, from those used in ordinary chemical
ASSAYING. 319
analysis, the most notable exception being

in In all methods of assaying, wet or
dry,
the case of those used in the assay of gold and time must be considered as well as
accuracy.
silver. The proportion of these metals present It is sometimes important to arrive at a result
in ores is reported in troy ounces, pennyweights, in the course of an hour or less, and some of
and grains per ton, or sometimes in ounces and : the methods described are intended for such
decimals or in pennyweights and decimals. emergencies, when extreme accuracy must be
The weight of ore taken for assay accordingly !
sacrificed. It is also necessary to observe
contains as many milligrams as there are ounces that assay methods are intended to be com-
troy in a ton (29,166 in a ton of 2000 Ibs., and parative, and wherever it is possible check assays
32,666 in a ton of 2240 Ibs.). This weight of on similar materials of known composition
29-166 grams is called an assay-ton (or A.T.), should be made side by side with the assays of
and boxes of weights made up of assay-tons and ores or other bodies requiring examination, and
decimals are used by many assayers. Then a correction applied to the results. In the
the gold extracted from the sample of ore is following pages, only methods in common use
weighed in milligrams, and can be reported in assay offices are described. The methods
without calculation. In the assay of gold of ordinary analysis are generally omitted or
bullion the weights commonly range from made the subject of brief reference.
'1000' downwards, where 1000=0-5 gram or Aluminium. There are no special methods
some other unit such as 5 grains. Much of assaying the ores of this metal. The silicates
tedious calculation is avoided by thus mark- are broken up, and the silica removed as usual
ing the weights so that their face-value (see p. 329), and the acid solution of the bases
gives at once the result of the assay. Again, is treated so as to separate the metals contained
in assaying silver by precipitation as chloride in it. Aluminium is precipitated and weighed

(India Mint method, see p. 327), since 18-815 as phosphate A1P0 4 or oxide A1 2 3
, It is .
grains of pure silver are contained in 25 grains sometimes weighed as oxide together with oxide
of chloride, it follows that if 18-815 grains of of iron Fe 23, and also P2 5, if these con-
an alloy be always taken for assay, and the stituents are present in the ore. The last
resulting chloride be weighed out with a series mentioned constituent is of course combined
of weights the largest of which is marked 1000, as phosphate. The phosphorus and iron are
and is equal to 25 grains, and the others are then determined, aluminium being estimated
marked correspondingly, then the subsidiary by difference (Low's Technical Methods of Ore
weights of this series will indicate the result of Analysis, 1st ed. 22).
the assay without calculation. A similar series Antimony. The antimony in ores may be
can, of course, be arranged for any special purpose. determined by fusion with cyanide of potassium
The balances used for weighing gold and silver or with iron (avoiding excess) and black flux,
in bullion assays are light and delicate, taking but the results are unsatisfactory. The sulphide
about 2 grams as their maximum of weight, of antimony in an ore may also be approxi-
and turning to one hundredth of a milligram. mately determined by charging 500 grams of
Usually, one division of the ivory scale is made ore broken to nut-size into a clay crucible with
equal to 0-05 mg. Balances for weighing a perforated bottom. This crucible is fitted into
the parted gold in ore assays are still more another of about the same size, and the joint
delicate. The maximum weight which they carefully luted. A cover is also luted on, and
can carry is only 1 gram or even less, and they the whole is slowly raised to a red heat. The
turn with one-hundredth or in some cases only sulphide of antimony fuses and liquates into
one five-hundredth of a milligram. Milligram the lower crucible, from which it can be detached
and half-milligram riders are used, but the when cold, and weighed. The fused sulphide
final reading is always based on the deflection of antimony, if pure, contains 71-7 p.c. of the
from the zero position of the pointer, measured metal. The valuation of antimony sulphide
by the number of divisions on the ivory scale ores is usually effected, according to Bedford
covered by the swing. At the present day short McNeill (Berenger's Assaying, llth ed. 226),
beams of 6 inches, 4 inches, and even 8 cm. in by having recourse to the ordinary smelting
length, are in use, so that the balances are very operation, which is to be used in treating the
rapid in action in spite of then- sensitiveness. ore on the large scale. Charges of about 20 kilos,
In quantitative blowpipe work on gold and of ore are used for the valuation.
silver, it has been found possible to dispense The wet methods of estimation of antimony
altogether with a delicate balance, and to use in ore are far more accurate than those referred
an ivory scale (Plattner's scale), by which the to above. The ore is fused with sulphur and
diameter of the bead of metal is accurately sodium carbonate, and then digested with
measured. The principle has been extended water. A solution of an alkaline sulpho-
in the assay of poor materials, and beads of compound of antimony is thus obtained, from
microscopic dimensions are placed on the stage which a mixture of antimony and arsenic sul-
of a microscope and measured by means of a phides and free sulphur is precipitated by the
micrometer eyepiece. In this way L. Wagoner addition of dilute hydrochloric acid. After
(Trans. Am. Inst. Mining Eng. xxxi. 1901, the arsenic has been separated, the antimony
798) obtained a close approximation to the sulphide is weighed or is oxidised by fuming
weight of beads of silver of 0-02 mm. in diameter, nitric acid, and weighed as Sb 2 4 Ores may .
which weighed about 0-00004 mg". also be attacked by hydrochloric acid. The
The above summary has special reference to antimony in the separated sulphide may be
the requirements of a laboratory for making estimated volumetrically, dissolving the sul-
dry or fire assays. For wet assays, the apparatus phides in hydrochloric acid and chlorate of
and reagents are those of the ordinary analytical potash, warming to expel the chlorine, adding
laboratory (v. ANALYSIS). an excess of potassium iodide, and titrating
320 ASSAYING.
with thiosulphate of soda (J. Soc. Chem. Ind. mercial standard copper, refined copper, and
xv. 255). the alloys of copper require to be assayed.
Arsenic. The determination of arsenic in The chief methods in use are as follows :
ores and metallurgical products is usually made (1) Dry or Cornish assay, long used in con-
by Pearce's method, which consists in fusing nection with the sale of copper ores, but
about 0-5 gram of the ore with 5 grams of a applicable chiefly to mattes and rich sulphide
mixture of equal parts of sodium carbonate ores.
It is especially unsatisfactory when
and nitre, dissolving out the soluble arsenates of dealing with poor ores, but gives low results in
the alkalis and precipitating the arsenic in a all cases, the loss,
according to Beringer, ranging
neutral solution by means of silver nitrate. from 2 p.c. of the copper present in the richest
The precipitated brick-red silver arsenate materials to 33 p.c. of the copper in 2 p.c. ore.
Ag 3 AsO 4 is filtered off, dissolved in nitric acid, It consists in fusing the calcined
regulus for
and the silver in it determined by Volhard's metallic copper and refining the copper. Rich
thiocyanate method. The amount of arsenic oxidised ores are fused for metal at once. The
present can then be calculated (Low's Ore Ana- amount of ore taken for assay is 400 grains,
lysis, 41). Small quantities of arsenic in metals but with rich material only 200 grains or even
and minerals may be separated by distillation 100 grains are taken. The" fluxes vary with the
with ferric chloride and calcium chloride in a nature of the ore, in which there may be too
hydrochloric acid solution, the distilled arsenious much sulphur and iron, as in copper pyrites, &c. ,
chloride being condensed in a vessel of cold water or too little, as in grey copper. The following
(Berenger's Assaying, 384). (For arsenic in steel, are examples of the charges :
see p. 325.)
A. Copper pyrites B. Grey copper ore
Bismuth, an ore in the metallic
if
present in Ore 200 grains
. 100 grains
state, may be determined by liquation, the Nitre 50
method of procedure being similar to that used
Lime 200 200
in liquating sulphide of antimony (q.v.). The 200
Fluorspar 200
bismuth in an ore may also be determined by Glass 150 150
fusing with fusion mixture, common salt, and
it
Borax 150 150
cyanide of potassium. These methods are Haematite 15-20
inexact, and bismuth is usually determined by 25-30
Sulphur
being weighed as BiO 3 after precipitation as 30
Argol
carbonate, or as BiOCl on a weighed filter or a ' '
Gooch crucible after being dried at 100. _The charge is fused in a large copper crucible
Bismuth metallic lead is precipitated and
in at a low red heat, which is gradually raised.
weighed as BiOCl, and in metallic copper it After about 15 minutes the charge is poured into
is detected by the colour given to lead iodide. a conical mould, and, as soon as the slag is
(For estimation of bismuth in copper, see solid, it is taken up by tongs, dipped into water,
p. 322.)
and allowed to dry. When treated in this way,
Chromium occurs in chrome-iron ore and the slag breaks up readily. The regulus is
sometimes in other iron ores, in pig-iron and detached by a hammer and crushed to powder
in steel. Small quantities of chromium in iron in an iron mortar. It should be reddish-brown
ores, after separation from other metals and in colour and contain about 50 p.c. of copper
earths, are precipitated by lead acetate in an and 20 p.c. of iron. It is roasted in a Cornish
acetic acid solution, and weighed as PbCr0 4 ,
crucible in the melting furnace or in a roasting
or, in the alternative, reduced by sulphurous dish in the muffle, at a low but increasing
acid and the chromium precipitated from the temperature, with continuous stirring at first.
green solution by means of ammonia and When sweet,' i.e. not smelling of sulphur, at
'
weighed as Cr 2 O 3 Chrome-iron ore is assayed

. a full red heat, it is mixed with a little charcoal
by a volumetric method based on the oxidation powder, and re-roasted to decompose sulphates.
of ferrous iron by chromium in the form of It is then crushed again, if necessary, and fused
chromate. The chromium is oxidised by per- in the same crucible with argol, borax, and
oxide of sodium ( J. Iron and Steel Inst. xlviii. sodium carbonate. A high temperature is
153). The ferrous iron is added in the form of required, and the charge is poured in about
a weighed amount of ferrous ammonium sulphate 15 minutes. The slag is detached and cleaned
or of a weighed amount of metallic iron dissolved by a second fusion with more argol and sodium
' '
in sulphuric acid. The excess of ferrous iron carbonate. The coarse copper obtained in this,
present in the solution containing the chromium way is refined by being charged into a very hot
is titrated with permanganate. Chromium in crucible and melted. The impurities are
and weighed as chromium
steel is precipitated oxidisedby the air and form a ring of oxides
phosphate (Chem. News, Ivii. 1888, 153), or as round an eye of copper. Then refining flux,
chromic oxide Cr 2 3.
which consists of a deflagrated mixture of nitre,
Cobalt. (See Nickel, p. 326.) argol, and common salt, is added, and 2 minutes
Copper. The principal ores of copper are later the copper is poured, and if it is found
'
(a) native copper ; (&) sulphide ores, copper to be at tough pitch,' it is weighed. The slag
pyrites or yellow ore, erubescite or purple ore, contains copper, and must be cleaned. (For
grey copper ore, &c. ; (c) oxidised ores, malachite, full details of the method, see Percy's Metallurgy,
silicate of copper, &c. The treatment of copper i. 1861, 454-478.)
ores results in the production of copper matte (2) Electrolytic assay of copper. The weight
or regulus containing from 30 to 50 p.c. of copper, of ore taken for assay depends on its richness,
and cement copper *ôr copper precipitate, con- convenient amount of metallic copper for
taining 70 p.c. or more of metallic copper. electro-deposition being from O'l to 0-5 gram.
In addition to these materials, ordinary com- When using this method or any of the other
ASSAYING. 321
wet methods, the copper must first be brought straw-yellow colour. The results are affected
into solution and usually separated from other by time, temperature, degree of dilution, and
metals. Oxidised ores may require merely to by the amounts of ammonia and of ammonium
be treated with hydrochloric acid. Sulphide salts. The conditions of the check assays on
ores, mattes, copper precipitate, &c., are at- pure copper and those on ores, &c., must
tacked by nitric acid, evaporated to dryness, therefore be identical, and ferric hydrate, for
and taken up by hydrochloric acid. Copper example, must be present either in both or in
slags are fused with sodium and potassium neither. The standard cyanide solution, which
carbonate (fusion mixture), and a little nitre, decomposes somewhat rapidly, contains about
and are then digested with water and hydro- 42 grams KCy to the litre, and 100 c.c. of this
chloric acid. The copper is precipitated from is equivalent to 1 gram of copper. The reaction,
its hydrochloric acid solution by means of according to Beringer, is represented by the
sulphuretted hydrogen or (after evaporation equation :
with sulphuric acid) by sodium thiosulphate, CuSO 4 +4KCy=2KCy.CuCy 2 +K 2 S0 4 .
and the sulphides are filtered off and redissolved

For the electrolytic assay, the The quantityof copper usually present in an
in nitric acid.
solution obtained in this way is diluted, warmed, assay is about 0-5 gram. At the finish the effect
of an addition of 0-5 c.c. of cyanide is readily
and filtered into a 200 c.c. flask, and made up to
observable. Zinc, silver, nickel, and cobalt
about 100 c.c., of which from 2-5 to 5 p.c.
interfere with the assay, and must be removed
should be nitric acid. Platinum electrodes
before titration.
(spiral and weighed cone or cylinder) are then In the iodide method, the alloy or the sul-
placed in position, and a current from two
Daniell cells in series is passed through for phide of copper separated from the ore is
dissolved in nitric acid, evaporated almost to
16 or 17 hours. The cylinder is removed from
the colourless solution, washed with water and dryness in order to expel nitrous fumes, and
diluted. The solution is then filtered if necessary,
afterwards with alcohol, dried in a water-oven,
and weighed. The copper precipitate should
and carefully neutralised with sodium carbonate,
be salmon-red in colour. The solution still avoiding excess. One c.c. of acetic acid is then
contains a little copper, which is estimated added, which should be enough to redissolve the
colori metrically, ammonia being added, and the precipitated copper. Next, after cooling the
flask, an amount of about 5 grams of potas-
colour, after filtration, compared with those of
standard solutions containing known amounts
sium iodide crystals is added (or not less than
ten times the weight of the copper present) ;
of copper. Silver, mercury, bismuth, arsenic, the solution is diluted to a fixed amount, say
and antimony interfere with the process, being
50 c.c. ; and the liberated iodine is at once
deposited with the copper. Mercury, however, titrated with a solution containing 39-18 grams
is separated on dissolving the sulphides in nitric
acid. Bismuth turns the copper dark grey, but sodium thiosulphate (equivalent to 10 grams of
is not deposited until most of the copper has copper) to the litre. The reactions are repre-
been thrown down. Arsenic and antimony sented by the equations :
darken the copper deposit, but may be driven 2CuS0 4 +4KI=Cu 2 I,+2I+2K 2 S0 4 .
off by heating to dull redness. Lead makes its 2Na 2 S 2 3 +2I=2Nal"+Na 2 S 4 6 .
appearance at the anode. The electrolytic When the yellow colour is almost discharged,
assay is suitable for all materials containing 2 c.c. of fresh starch solution is added, and the
copper (cf. ELECTROLYTIC ANALYSIS).
addition of the thiosulphate continued drop
Byrapidly rotating the cathode a coherent by drop until the blue colour disappears and
deposit can be obtained even when a strong does not return within 2 or 3 minutes. The
current of 10 to 12 amperes per 100 sq. cms. of effect of one drop or 0-05 c.c. of standard solu-
cathodic area instead of the usual current of tion, equivalent to 0-5 mg. copper, is observable.
0-5 to 1 -0 ampere is used. The time required for The solution is standardised with, pure electro-
the deposition of the copper may thus be lytic copper. Ferric acetate, arsenic, lead, and
shortened to a few minutes (Amer. J. Sci. 1903, large quantities of sodium acetate may interfere
xvii. 320, xviii. 56; J. Amer. Chem. Soc. xxv. with the titration. According to J. W. West-
896; Chem. Soc. Trans, xci. 373). moreland (Beringer's Assaying, 441), sodium
(3) The volumetric assay of copper. There acetate counteracts the interference of arsenic
are two main processes the potassium cyanide and bismuth, and the bad effect of large quanti-
and the iodide methods. Both are in wide ties of sodium acetate is removed by doubling
use in the assay of ores, alloys, &c. In pre- the amount of potassium iodide added. Iron, if
paring to use these methods, the copper is present, is precipitated by ammonium phosphate
brought into solution, and may be separated (
J. Soc. Chem. Ind. v. 48). Instead of neutralising
from other metals, &c., as already described, with sodium carbonate and acidifying with acetic
with any further precautions necessary to acid, an addition of 20 c.c. of a saturated solution
remove special impurities. With ordinary of zinc acetate may be made (A. H. Low).
pyritic ores, however, containing no zinc, silver, The colorimetric method of assaying copper
nickel, or cobalt, it is sufficient, in preparing is sometimes used in the case of very poor ores,
for the cyanide process, to heat the ore gently or generally whenever the quantity of copper
with concentrated nitric acid to which a little present is small. Reference has been made to
sulphuric acid has been added. It is then it above.
diluted, an excess of ammonia or of Na 2 C0 3 Examination of commercial copper. Electro-
added, the bulk made up to some convenient lyticand Lake copper are generally nearly pure,
amount such as 300 c.c., and the solution titrated but some of the metal sold contains as much as
with potassium cyanide. The blue solution is 2 or 3 p.c. of impurities. The most im-
decolourised, and when overdone changes to a portant of these are arsenic, nickel, oxygen, and
VOL. l.T. v
322 ASSAYING.
phosphorus; but antimony, bismuth, cobalt
gold, iron, selenium, silver, sulphur, and tellurium
may also be present. The impurities to b
looked for in copper which has passed a hig
conductivity test are mainly bismuth, selenium
and tellurium. Arsenic and phosphorus ar
separated as iron arsenate and phosphat
mixed with acetate. Gold and antimony ar
separated by dissolving the copper in nitri
acid, and silver is precipitated as chloride o
bromide from a nitric acid solution. It ^
be collected in a precipitate of lead sulphate
Nickel is left in solution by precipitating coppe
electrolytically, or by sulphuretted hydrogen
in an acid solution. Lead is detected by th
blackening af the anode in the electrolyti
assay, and is estimated as sulphate or chromate
Oxygen is usually taken by difference, bu
is sometimes estimated by colorimetric deter
mination of the quantity of the insoluble basic
salt of copper formed by the reaction of silver
nitrate with cuprous oxide (Hampe's method
Zeitsch. anal. Chem. xiii. 188). The equation
representing the reaction is as follows :
3Cu 2 0+6AgN0 3 +3H 2
= 2Cu 2 H 3 3 N0 3 +2Cu(N0 3 ) 2 +6Ag
The metallic copper is completely dissolved by
the silver nitrate with separation of metallic
silver. Bismuth is separated, according to
Beringer, by precipitation by sodium bicar-
bonate. After redissolving in sulphuric acid,
it is boiled with sulphurous acid and
potassium
iodide, and the bismuth in the yellow solution
estimated colorimetrically. Tellurium and se-
lenium (J. Amer. Chem. Soc. xvii. 280) are
precipitated as iron tellurite and selenite by
additions of iron nitrate and ammonia. The
precipitate is redissolved in HC1, tartaric acid
and potash added, and a current of sulphuretted
hydrogen passed. The selenium and tellurium
are subsequently precipitated by a current of
sulphurous acid in a hydrochloric solution, and
parted by boiling with potassium cyanide.
Gold. Gold is generally in the metallic
state in its ores, either in the form of grains,
scales, pellets, &c., in loose alluvial gravels, or
in various forms embedded in quartz or other
gangue in veins. It is frequently associated
with iron pyrites, blende, &c., but the only
native compounds are the tellurides. Besides
these, the auriferous materials to be assayed
comprise tailings or residues of ores after treat-
ment, copper bottoms, pig lead, unrefined
bullion, which contains silver, copper, and other
metals, fine (i.e. refined) gold, and the commercial
alloys used for coinage, plate, &c. The assay
of gold ores and alloys is made with greater
exactness than other assays, owing to the high
value of the metal.
Apanning assay, or concentration test is
carried out as described on p. 317. The con-
'
centrates consist of black sand ' or oxides of
iron, titanium, &c., sulphides and arsenides,
and sometimes grains of platinum. Free gold
is sometimes visible, and is collected by
grinding
in a mortar with mercury, panning out the
amalgam, and recovering the gold by distilling
off the mercury or dissolving it in nitric acid.
In either case the gold must be parted from the
silver as described on p. 323. The panning
assay of alluvial gold deposits is usually reported
in grains of fine gold per cubic yard, which
ASSAYING. 323
then be in the lead button. In the case of ores As oxidation proceeds, the litharge encroaches
' '
containing much copper, this is a disadvantage, on the eye of metal, and at length covers it
entailing loss of gold in cupellation, and the over. A pinch of charcoal powder is then added
in tissue paper, and when the fusion is
copper may be removed from the ore by treat- again
ment with acid before fusion (with some loss of tranquil, the charge is poured into a mould, and
silver) or large quantities of litharge (6 A.T. of the slag detached. The lead is cupelled, and
PbO to 1 A.T. of ore) may be added, and only the assay finished as before.
a small part of it reduced. In the latter case In cupellation some gold and silver is carried
the slag contains gold and silver, and is cleaned into the cupel with the litharge, especially if
by a second fusion, with the reduction of f more tellurium, selenium, copper, &c., are present.
lead. Asimilar method of fluxing is used for The gold and silver are usually recovered by
telluride ores, an excess of litharge in the slag fusing the crushed cupel with litharge, charcoal,
preventing tellurium from entering the lead sodium carbonate, borax, and fluorspar, and
button. Antimonial and arsenical gold ores cupelling the button of lead (see Lodge's Notes
are sometimes roasted with coal-dust in a re- on Assaying, 112-169).
ducing atmosphere, in order to remove the Assay of gold 'bullion and alloys. A piece of
antimony or arsenic as a sulphide before fusion. the metal to be examined is adjusted by
cutting
An alternative method is to fuse with much and filing to correspond in weight with a standard
'
litharge and enough nitre to oxidise the antimony weight marked 1000,' which varies with differ-
with the formation of antimoniates. Sulphides ent assayers between 5 and 10 grains, but is
may be roasted in air before fusion. usually 0-5 gram. To the assay piece is added a
The lead button, rounded by hammering, is piece of silver (free from gold) equal in weight to
placed on a hot cupel in the muffle (see p. 317), 2 times (at the Royal Mint 2-1 times) that of
which is kept at a full red heat. The lead melts the gold estimated to be present in the alloy,
and oxidises, and the litharge and other oxides which, if not already known, can be ascertained
are absorbed by the cupel, the gold and silver by a rough preliminary assay or by the touch-
'
being left as a bead (or prill ') on the surface. stone (see p. 324). The whole is' wrapped in
If the bead is large and contains much silver, it sheet lead, the weight of which depends mainly
must be cooled gradually to prevent it from on the amount of copper to be removed, and
' '
spitting on solidification, by which part of the varies from 8 to 32 times the weight of metal
metals might be lost. The bead is cleaned, taken for assay. The lead packets are then
weighed, flattened, and parted by dissolution in transferred by means of tongs to cupels already
boiling nitric acid in a porcelain crucible or test- raised to a bright red heat in the muffle, the
tube. If less than two parts of silver are present current of air through the muffle is carefully
to one of gold, the metals are not parted com- regulated and the heat maintained. In from
pletely, silver being left in the gold, and it is 10 to 20 minutes, a rapid passage of brilliant
convenient to have a greater proportion of silver iridescent bands of colour over the surface of
present. It is, therefore, often necessary to the button is observed to take place, and the
melt the bead with more silver, the proportion buttons then appear to become colder, no longer
varying with the size of the bead, as follows :
glowing brightly with the oxidation of the lead.
Weight of gold Silver required for parting A few minutes later the muffle is closed to allow
10 milligrams 40 milligrams the buttons to set without loss by spitting. If
1 6 copper is present in the assay pieces, however,
0-2 or less 2 this is not to be feared, and the charge can be
A little extra silver is permissible, but if too drawn while the buttons are still molten. At
much silver is present, there is a tendency for the Royal Mint a charge consists of 72 assay
the gold to break up into very fine particles, pieces, which are charged in simultaneously by
which are difficult to wash without loss. The means of a divided metal tray with a sliding
separation of these minute particles is avoided bottom and withdrawn simultaneously
while
by dropping the bead into boiling acid, sp.gr. 1-2, still molten by means of a tray made of a
when the parting will be completed in a few mixture of graphite and clay, on whic'h the
seconds. The parted gold is washed free from cupels are placed. The buttons are cleaned by
silver nitrate, &c., and is made firm and co- brushing, flattened on an anvil, annealed in the
herent for weighing by being annealed at a red muffle or before a blowpipe, and reduced to a
heat. (For weights, balances, &c., see p. 318.) thickness of about 0-2
mm. by passage through
' '
The silver is estimated by difference. The a small pair of flatting rolls. The fillets are
'
litharge, fluxes, &c., must be tested for silver again annealed

and coiled into a spiral or cornet'
and gold by running blank charges without ore. by the finger and thimb.
In scarification about 0-1 or 0-2 A.T. of ore is The parting in nitric acid is effected either
mixed with 30 or 40 grams of granulated lead, and in glass parting flasks or in a platinum boiling
transferred to a dry scorifier (see Fig. 6). The apparatus. If parting flasks are used, an
charge is covered by a similar amount of granu- amount of about 2 oz. of nitric acid of sp.gr. 1-2
lated lead, and from 0-5 to 1 gram of borax is is heated in the flask almost to boiling, and the
sprinkled on last. The scorifying dish is then cornet is then dropped in and boiled until 2 or 3
charged into a muffle, which has been raised to minutes after the red fumes have disappeared.
a temperature of 1000-! 100, or
considerably The acid is then poured off, and the gold, after
above that required for cupellation, and the being washed twice with boiling water, is boiled
muffle is closed. As soon as the charge is melted for a further 15 minutes with nitric acid of
down, the muffle is opened. The lead now sp.gr. 1-2 or stronger. The acid must be free
oxidises, and the litharge, forming a ring ofl?lag from silver, chlorine, &c.
;
round the scorifier, oxidises the sulphides, &c., The gold is again washed, and is then trans-
and slags off the earthy materials in the ore. ferred to a porous crucible or annealing cup ' '
324 ASSAYING.
by filling the flask with water, placing the cup 'resare oxides, carbonates, &c., and the iron in
over its mouth, and inverting it. The gold falls hem is easily dissolved by
hydrochloric acid.
into the cup, and the flask is removed without Titaniferous ores are fused with acid potas-
agitating the water in the cup. The gold is ium sulphate and dissolved in water and
then dried, annealed by heating to redness, and lydrochloric acid. If nitric acid is present in
weighed. If no more than three parts of silver 'he acid solution, it is destroyed by evaporating
are present to one of gold, the cornet does not iO dryness with
hydrochloric acid and taking
break up; and if
enough is known previously ip with hydrochloric acid and water, and the
of the composition of the bullion to make sure ron is then reduced by zinc, which gives a
of this in the cupelled button, a platinum tray, stream of hydrogen or (if titanium is present) by
containing a number of little platinum cups may crystals of sodium sulphite in a neutral or slightly
be used. A
cornet is placed in each cup, and acid solution. As soon as the solution is colour-
the whole tray is immersed in nitric acid, and ess, the excess of zinc is removed, or the sodium
subsequently washed by dipping in and out of sulphite decomposed by boiling with hydro-
hot water. Less acid is used per assay piece chloric acid, and titration is carried out in a
by this method, and the boiling is more pro- porcelain basin by means of a solution prepared
longed, 30 minutes in each of two acids of sp.gr. by weighing out 4-39 grams of potassium bichro-
1-23 being used at the Royal Mint. mate to the litre, equivalent to 5 grams of iron
In each batch of assays, two or more check according to the equation :
assays
'
on pure gold are made to determine the 6FeCl 2 +K Cr,0
2 7 +14HCl
surcharge or net sum of the losses of gold and
'
~=3Fe 2 Cl 6 +Cr 2 Cl 6 +2KCl-ir7H 2 0.
the gain in weight due to the retention of silver.
Potassium ferricyanide (0-1 p.c. solution,
With alloys boiled separately in flasks, check
freshly prepared) is used as an indicator, a drop
assays are of comparatively little value (see from the assay solution being mixed with a drop
Rose's Metallurgy of Gold, 5th ed. 470-498).
of the test solution on a white glazed tile, from
Alloys of gold and silver If the alloy con- time to time. The end-point is reached when a
tains enough silver to be parted by nitric acid,
colour is no longer produced. The solution of
no difficulty arises. The silver is dissolved, bichromate is standardised by means of piano
precipitated by hydrochloric acid, and weighed wire, which contains about 0'4 p.c. of impurities.
either as chloride or as metal. If the silver is
The permanganate method is carried out in
deficient in quantity, the alloy is melted with
a sulphuric acid solution, the equation being :
of cadmium under
two and a half times its weight
a cover of potassium cyanide and parted with 10FeS0 4 +K 2 Mn 2 8 +8H S0 4
2
nitric acid. The silver is precipitated and =5Fe 2 (S0 4 3 +2MnS0 4 +K 2 S0 4 +8H
) 2 0.
weighed as chloride. The gold residue is an- The standard solution is prepared by weighing
nealed and weighed. Sometimes the silver i out 2 82 grams of potassium permanganate per
-
determined by difference, the alloys bein litre, which is equivalent to 5 grams of iron.
cupelled and weighed, and subsequently cupelle The end reaction, the appearance of a pinkish
again with the addition of silver, and parted. tinge in the solution in the flask, is very sharp.
(For alloys containing gold and platinum, see When the amount of ferrous iron only in the
p. 327.) ore is reqiiired, the ore is dissolved in hydro-
Assay by the touchstone. This ancient chloric or sulphuric acid with exclusion of air.
method comparing the colour of the
consists in The ferric iron may be determined by difference,
streak produced by a sample of gold of unknown or, as a check, the stannous chloride method
composition on a black surface with those from may be used, in which the yellow solution of
a series of known compositions, after all have ferric iron hi hydrochloric acid is decolourised.
been treated alike with nitric acid. Any The standard solution (20 grams of commercial
abrading surface on which the acid is without stannous chloride per litre, acidulated with
action can be employed for this purpose. hydrochloric acid) is run into a boiling-hot
Iridium occurs alloyed with platinum, and solution of iron, and is standardised by means
finds its way into gold bullion. In the latter of a solution of ferric chloride free from nitric
case, it is found with the gold cornet obtained acid.
in the bullion assay, adhering in the form oi Analysis of iron and steel. The elements
black scales or powder to that side of the golc requiring estimation are carbon (graphite, com-
which was originally nearest to the cupel. II bined carbon and total carbon), silicon, man-
can be estimated by dissolving the gold in aqua ganese, sulphur, phosphorus, arsenic, and, in
rcgia, the iridium remaining undissolved. special steels, chromium, nickel, tungsten,
Iron. The dry assay of iron, made by molybdenum, vanadium, &c. The total carbon
fusing ores with fluxes in carbon-lined (brasqued is estimated by combustion, usually after
crucibles, obsolete, and need not be described
is removal of the iron by a cupric salt. The
The wet methods are volumetric, based on the graphite is estimated by combustion of the
oxidation of iron from the ferrous to the ferric residue after dissolving the iron in hydrochloric
state or on the converse reduction. Either th< acid, by which the combined carbon is removed
bichromate or the permanganate method i in combination with the hydrogen evolved,
generally used to determine the total amoun or more advantageously in nitric acid, by which
of iron in ores or the amount of iron present in the combined carbon is oxidised and retained in
the ferrous condition. The stannous chloride solution. The combined carbon is determined by
method is used for measuring the amount o the colour of a nitric acid solution compared with
iron present in the ferric state in an ore. the colour of certain standard solutions con-
For the determination of the total amoun taining known amounts of carbon. Silicon is
of iron, the ore is passed through an 80-mesl weighed as silica after dissolution of the iron
sieve, and attacked by acids as usual. Mos by acids or iodine. Sulphur is weighed as
ASSAYING. 325
barium sulphate, after the iron has been dis- method gives results with pure ores which are
solved in aqua regia, or it is evolved as sul- about 1 or 2 p.c. too low. When the ore
phuretted hydrogen, which is absorbed by contains antimony, bismuth, copper, &c., these
caustic soda, and decomposed by a standard metals are in part reduced with the lead, and
solution of iodine. The excess of iodine is are weighed with it. If the lead button is
estimated by sodium thiosulphate. hard, it is necessary to estimate the lead in it
Manganese is separated by precipitation with by weighing it as lead sulphate or otherwise, or
bromine in an ammoniacal solution after removal to adopt wet methods of assaying the ore.
of the iron as basic acetate. The precipitated (For details of the dry assay of lead, see
hydrated peroxide is heated strongly in a muffle Percy's Metallurgy of Lead, 103-119.)
and weighed as Mn 3 4 There is also a colori-
. In the wet methods, oxidised ores are
metric estimation, the steel being dissolved in attacked by hydrochloric acid, followed by
nitric acid and the solution boiled with lead nitric acid, if necessary. Sulphide ores are
peroxide. The colour of the permanganate treated direct with nitric acid. The lead is
produced is compared with those of standard determined either as sulphate or volumetrically,
solutions. Phosphorus is precipitated by ammo- by means of ammonium molybdate (Alexander's
nium molybdate or magnesia mixture. Arsenic method). In the latter method (Eng. and Mng.
is separated by precipitation as sulphide in an J. April 1, 1893, 298), the mixture of nitric
acid solution, converted into arsenic acid and acid and ore is evaporated with sulphuric acid,
determined by precipitation by magnesia mixture. diluted, boiled, and filtered. The lead sulphate
(For determination of the metals in
the in the residue is dissolved in hot ammonium
special steels, see under the headings Chromium, acetate, acidified with acetic acid, raised to
Nickel, &c. For full details of the analysis of boiling, and titrated with a standard solution of
iron and steel and also of the complete analysis ammonium molybdate, containing, according to
of iron ores, see Blair's Chemical Analysis of Low, 4-25 grams per litre. The solution is
Iron, Campredon's Guide Pratique du Chimiste standardised with pure lead foil. Tannin is
Metallurgiste et de 1'Essayeur, 438-634, and used as an indicator, giving a yellow colour to
Brearley and Ibbotson's Analysis of Steel Works a drop of the solution ou a white glazed tile
Materials. ) when the ammonium molybdate is in excess.
Lead. Both dry and wet methods of assay If iron and calcium are present, it is better to
are used. The dry assay is only applicable to separate the lead as sulphide and redissolve
rich ores and to concentrates, and even with before titration (Low's Ore Analysis, 113).
these is less accurate than the wet methods. Lead may also be determined in a feebly
The ore is crushed through a 60-mesh sieve, acid solution by adding an excess of potassium
mixed with sodium carbonate and argol, and chromate and estimating the amount of excess
fused in a wrought-iron crucible or in a clay pot by means of a standard solution of ferrous
with hoop-iron. Galena is reduced by the iron, chloride. The reaction is the same as in the
and any oxides, sulphates, &c., of lead arc bichromate assay of iron, but in this case the
reduced by the argol. Borax is sometimes end is marked by the appearance of a green
added as a cover. The following are examples colour in the test drops on the plate (Beringer's
of the charges recommended by Percy :
Assaying, 214).
2. Any Manganese occurs as Mn0 2 in pyrolusite,
1. Rich galena, esp. Phos-
3. 4. Cerus- when the value of the ore usually depends on
galena poor ores phate ore site its property of liberating chlorine when heated
Ore . . 500 grs. 500 grs. 300 grs. 500 grs. with hydrochloric acid, and not on the pro-
Sodium car-
portion of metal contained in it. Nevertheless,
bonate . 500 ,, 350 350 500 the percentage of manganese in ores is some-
Argol (tartar) 50 100 100 100 times required, and spiegeleisen, ferroman-
Borax 150 30 30
ganese, and steel are also assayed for manganese.
. .
The iron crucible is made red hot, cleaned, and Either the ferrous sulphate assay or Volhard's
allowed to cool. The charge is then transferred volumetric process is generally used. In the
to it, care being taken to avoid loss by dusting, latter method, the manganese is precipitated by
neutral
and the borax, or, if none is used, part of the potassium permanganate in a boiling
sodium carbonate is added as a cover. A clay solution. The precipitate, as far as numbers
lid is also placed on the crucible. The charge are concerned, is represented by the equation :
is slowly heated for about 20 minutes, and is K 2 Mn,0 8 +3MnS0 4 +2H.,O

then poured into a mould, provided that all =K 2 S0 4 +5Mn0 2 +2H a S0 4 .
About one gram of the ore or spiegeleisen

signs of effervescence have disappeared, and the
mixture is seen to be in a state of tranquil dissolved in hydrochloric and nitric acids,
is
fusion. The lead is found at the bottom. It heated with sulphuric acid, and neutralised by
is detached from the
slag with a hammer, and is the addition of an emulsion of zinc oxide in
cleaned and weighed. The slag is examined for slight excess. All the iron is precipitated, and,
lead beads before being thrown away. Clay after violently shaking the mixture, it is made
crucibles are used for phosphate and carbonate up to 500 c.c., allowed to settle, and 100 c.c. of
ores. the clear supernatant liquid" is drawn off, heated
When the ore contains arsenic, a speise is to boiling, and titrated. The end point is
formed which is found adhering to the upper marked by the appearance of a pinkish tinge.
surface of the lead, below the slag. It must (For the estimation of manganese in steel, see
be removed with great care to avoid loss of lead. above. )
The lead should be soft and malleable. The Mercury. The wet methods of assay are not
silver and gold in the ore are determined by satisfactory, and one of the distillation
methods
cupellation and (seeparting
p. 323). The is usually employed. When a large percentage
326 ASSAYING.
of mercury ispresent, a combustion tube of copper. Gold is added to the speise after tl
18-20 inches long is used. It is sealed at one elimination of cobalt if copper is present,
end and magiiesite powder placed in it first, to speise is weighed after each metal has
a depth of 3 or 4 inches. Next a layer of 2 removed. The slag must be frequently ex-
inches of unslaked lime is added and then 5 or 10 amined and renewed, and great care and ex-
grams of ore well mixed in a mortar with 10 grams perience are needed to attain even approximate
of lime. The mortar is cleaned with more lime results.
and the rinsings added to the tube and covered The method is easier to carry out if copper
with clean lime to a depth of 3 or 4 inches. is absent, and this metal is sometimes removed
Finally, a loosely fitting plug of asbestos ie by precipitation with sulphuretted hydrogen in
inserted and the unoccupied portion of the tube an acid solution before the speise is formed. If
is drawn out almost to a point and bent over cobalt is absent, a weighed amount may be added,
at right angles, care being taken that no hollow as otherwise it is difficult to observe the point at
in the glass is formed which might collect some which nickel begins to pass into the slag after the
of the mercury. The tube is placed in position removal of the iron. The arsenides in the
in a combustion furnace and tapped until the speise have the formulae Fe 2 As, Co 2 As, Ni.2 As,
mixture settles and leaves a free passage for and Cu 3 As (Rhead & Sexton's Assaying, 187).
gases throughout its length. The narrow open- In the wet methods it is usual to roast the
ing is made to dip into a beaker of water, and ore as a preliminary in order to remove the
the tube is heated, beginning with the asbestos arsenic, sulphur, &c., and then to separate
plug and finishing with the magnesite, which the nickel and cobalt from the iron, manganese,
yields enough carbon dioxide to sweep out the zinc, &c., by suitable methods. The nickel is
vapours of mercury. The time required for precipitated as hydrate and weighed as NiO.
heating is about 30 minutes. While the tube Cobalt is often included in the nickel, but is
is still red hot throughout its length, its end is separated if present in large quantities. A
cut off and dropped into the beaker. The volumetric method depends on the interference
mercury collects in the water, and is dried by by nickel in the titration of cyanide with a
blotting-paper and then in a desiccator and standard solution of silver nitrate. An alkaline
weighed in a porcelain crucible. solution containing caustic soda is used, and a
When only small quantities of mercury are little potassium iodide added as an indicator.
present, Eschka's method is used (Dingl. poly. An excess of a standard solution of potassium
J. cciv. 74), in which the mercury is condensed cyanide is added to a solution of nickel sulphate
on a weighed piece of gold. This is in the made alkaline (and precipitated) by caustic
form of a basin made of thin sheet gold, soda. The excess of cyanide is titrated by a
used as the cover of a porcelain crucible and standard solution of silver nitrate (Beringer's
filled with water to keep it cool. The basin Assaying, 255). The reactions are represented
projects beyond the rim of the crucible, and by the equations :
usually weighs about 10 grams. From 0-2 to 2-0

4KCy+NiS0 4 =K
n NiCy 4 +K S0 4 .
i!
grams of ore is mixed with iHt grams of iron 2KCy+AgNO,=KAg Cy 2 +KN0 3 .
filings, and heated in the crucible for 10 or 20 Nickel and cobalt are also sometimes ea
minutes, the flame being kept from heating the mated by electrolysis, and for this purpose mi
upper part. This may be done by fitting the be separated from zinc and other metals,
crucible into a hole in a piece of sheet asbestos.
solved in nitric acid, and precipitated in
The gold basin is then dried without the agency ammoniacal solution.
of heat, and weighed, the increase of weight
For the separation of nickel from cobal
representing the mercury. see J. Soc. Chem. Ind. ix. 375.
Molybdenum in ores is estimated by pre- Nickel in steel is precipitated by bromii
cipitation as mercurous molybdate in a very water and caustic soda, after removal of
slightly alkaline or neutral solution by means of iron as basic acetate. It is weighed as NiO.
mercurous nitrate. The precipitate is ignited Platinum in alluvial deposits is concentrat
in a porcelain crucible, either alone or with as in the case of auriferous sane
by panning,
litharge, until the mercury is expelled. The In all cases platinum can be collected in le
increase in the weight of the crucible is taken the same methods as those described unde
by
as Mo0 3 but if chromium, vanadium, tungsten,
, the assay of gold ores. The lead buttons
phosphorus, or arsenic is present in the ore, the sometimes cupelled at a very high temperatur
ignited Mo0 3 must be purified by further treat- but it is difficult to remove the whole of the lea
ment or separated before precipitation. Moly-
' '
in this way, as the prill freezes on the cuj
bdenum in steel is precipitated as ammonium when only part of the lead has been oxidised.
phospho-molybdate. Cupellation may be finished hi the oxygen-ga
Nickel and cobalt occur together in ores, the blowpipe flame, but the loss of platinum is thet
former more commonly and in greater proportion large. It is more usual to dissolve the le
than the latter. They are usually assayed button in dilute nitric acid and to filter off tl
together. In the fire assay, the ore is roasted platinum and gold residue, which is parted bj
sweet and then fused with arsenic to form a dissolving in aqua regia, and precipitating the
speise. This is heated in air on a little clay dish gold with oxalic acid. The platinum is estimated
in the muffle, and the metals oxidised succes-
by difference or by precipitation as (NH 4 ),PtCl 6 .
sively, iron passing into the slag first, cobalt Platinum in alloys or in rich alluvial con-
next, and then nickel, copper being left until centrates may be estimated by melting with
last. The changes in colour of the borax slag six parts of pure lead, and grinding in a mortar
j
show the progress of the assay. The slag is the brittle alloy freed from slag. Portions of
coloured brown while iron is passing into it, blue the alloy are scorified with fresh lead and
by cobalt, sherry-brown by nickel, and blue by dissolved in nitric acid.
ASSAYING. 327
Alloys containing gold, silver, and platinum taining about 1-003 gram of silver is
weighed
are difficult to assay, as they are insoluble in and dissolved and 100 c.c. of the
in nitric acid,
aqua regia. The method adopted is first to salt solution added to from a pipette. The
it
cupel the alloy to remove copper, &c., these chloride is agglomerated by a shaking in a
motals being estimated by difference. The stoppered bottle, and the clear supernatant
' '
alloythen inquarted by cupellation with twice

is liquid is tested by decinormal
solutions of
its weight of silver and parted by boiling in common salt necessary, of
and, if silver
sulphuric acid. The residue contains the gold nitrate. The appearance of the cloud of silver
and platinum. These may be parted by again chloride shows the amount of silver left in so-
inquarting with silver and dissolving in nitric lution. Further shakings are resorted to if
acid, provided that the amount of gold present required, and the final reading is taken after
is at least ten times that of the platinum. If waiting for about 5 or 10 minutes. Check
the proportion of gold present is less than this, assays on fine silver are used with every batch
part of the platinum remains undissolved, and to test the strength of the solution, which varies
it is therefore necessary to add gold in many with the temperature, &c. Mercury interferes
cases. The parted gold is weighed and the with the method, and is detected by the colour
6me
platinum estimated by difference (6 Rapport of the precipitated silver chloride, which does
des Monnaies, 1901, p. xxix. ; Rose's Precious not darken if mercury is present. Acetate of
Metals, 272). soda corrects the error if the quantity of mercury
Silver. The
ores of silver are assayed in the present is small. The Gay Lussac method can
same way as those of gold of a similar kind, be used only in cases where the approximate
the scorification method being used far more assay is already known (Percy's Silver and Gold,
frequently than in the case of gold ores. The 282 ; Riche et 'Forest, L'Art de FEssayeur, 183).
slags and cupels must be examined usually, as In the India Mint method, the silver alloy
silver ismore readily lost than gold. The tem- is dissolved in nitric acid and precipitated by
perature of cupellation is kept as low as possible, a slight excess of hydrochloric acid. The silver
to check the loss of silver by volatilisation (see ;
chloride is then collected by shaking in a stop-
Lodge's Notes on Assaying, 37-111). I pered bottle, and, after being washed, is trans-
Silver bullion and alloys are assayed by ferred to a porous cup, dried, and weighed while
cupellation, by the Gay Lussac or the Volhard I
warm. The chloride is washed by decantation,
volumetric processes, or by weighing the chloride but the drying tedious, and is expedited by
is
(India Mint method). In cupellation, the breaking up the crust with a glass rod. Any
' '
base or oxidisable metals are removed in the gold that may be present is weighed as silver
muffle, and the silver prill is cleaned and weighed. chloride. This is the best method for alloys con-
The weight of silver taken is usually 10 grains. taining less than 70 p.c. of silver (Trans. Inst.
The amount of lead required varies from six Mng. & Met. xvii. 334).
times the weight of the silver for alloys of high The Volhard method is largely used in this
standard to twelve times for silver 700 fine. country. The nitric acid solution of the silver
The method
is not suitable for alloys containing is freed from nitrous acid by boiling, and is then
less than 70 p.c. of silver. The muffle is kept diluted and titrated with a solution containing
at a lower temperature than that required for 7 -04 grams of ammonium thiocyanate per litre.
gold cupellation, but must be raised to above the As this salt is deliquescent, it is usual to weigh
melting-point of pure silver (962) at the finish, out about 7-3 grams per litre. Iron alum is
to prevent the metal from setting in the furnace used as an indicator, giving a red colour when
before all the lead has been removed. When all the silver has been precipitated. Time is
the cupellation is complete, the mouth of the saved and the accuracy of the method increased
furnace is closed with great care to exclude by taking for assay an amount of alloy contain-
draughts, and the furnace is allowed to cool ing about 1-003 gram of silver, and running in
slowly to prevent loss of silver by spitting. The 100 c.c. of the standard solution of thiocyanate
solidified prills are cleaned and weighed. The from a pipette. After shaking the liquid in a
loss of silver in cupellation varies from 5 to 15 !
flask, the titration is finished by adding the
parts per 1000, and check assays on pure silver thiocyanate a drop or two at a time. Check
are placed in all parts of the furnace to measure assays on fine silver are used (Trans. Inst. Mng.
this loss. Any gold that may be present is & Met. xvi. 154).
weighed as silver. The process is very ancient, Tin. Tin ore is concentrated on a vanning
' '
and clear reference is made to it in connection shovel with the production of black tin in
'
with a trial of the Pyx in the Black Book of the order to determine what yield may be expected
Exchequer, written in the reign of Henry II. when the ore is treated on the dressing floors.
In the Gay Lussac process, the volume is The ore is crushed and sampled, and about
measured of a standard solution of common 30 grams are thoroughly mixed with 30 or 40 c.c.
salt or sodium bromide required for the
pre- of water on the vanning shovel with the fingers,
'
cipitation of a little more than a gram of silver to prevent, as far as possible, the loss of float
in solution as nitrate. No indicator is used, and tin.' The ore is then collected by a vigorous
the end of the operation is judged from the circular motion of the water, and the slimes
appearance of a faint cloud of chloride in a are poured off, a process which is repeated until
solution from which almost all the silver has the water remains clear after being left to settle
been precipitated. It is the most accurate for a few seconds. By means of a circular
method of assaying silver bullion. The standard motion of the shovel, combined with a series
solution of common salt (usually called the ;
of jerks, the tin oxide is now separated from the
'
normal solution lighter material, which is carried down by
') contains about 5-416 grams the
of Nad per litre, so that 100 c.c. will precipitate ;
descending wave. The tailings are saved and

1
gram of silver. A weight of silver bullion con- ,
washed over again until they yield no more fciu,
328 ASSAYING.
and are then crushed by rubbing with a hammer by means of prolonged boiling with sulphurous
and again washed. The concentrates are dried acid. The residue left by the attack on the
and roasted and dressed once more. Sometimes original ore with acids is similarly treated, after
they are washed quite clean from worthless the silica has been removed by heating with
material, and sometimes left impure with oxide sulphuric and hydrofluoric acids (Beringer's
of iron, &c., according to the nature of the ore Assaying, 293).
and the custom of the operator. Sometimes Tungsten in wolfram, steel, &c., is estimated
they are purified by boiling in hydrochloric acid by weighing as tungstic acid W0
3 The ore is
.
or aqua regia, which, according to J. H. Collins, boiled with hydrochloric acid or aqua regia, when
causes a loss of tin. The residue is usually the tungstenseparates as insoluble yellow
reported in pounds of black tin to the long ton tungstic acid. After thorough washing, this
of ore, or alternatively in parts per 200, so that ammonia, filtered, and recovered
is dissolved in-
a produce of ' 9A ' would be equivalent to 4-75 by evaporating the solution to dryness, and
p.c. (Beringer'sAssaying, 276). gently igniting the residue to decompose the
The black
tin obtained by vanning is assayed ammonium tungstate. Nearly pure tungstic
for metallic tin by reduction with anthracite acid remains. Any silica that may be present
(Cornish method) or
potassium cyanide. In may be removed by hydrofluoric acid.
the Cornish method 100 grams of tinstone are Uranium. The mineral is evaporated with
heated with 20 grams of anthracite in a plumbago nitric acid and taken up with HC1. After
crucible at a white heat for 15 or 20 minutes. separation of the other metals as sulphides and
The charge is then stirred with a stick and again carbonates, the uranium is precipitated by
heated for a few minutes before pouring. The ammonia and weighed as U 3 O g , or it is pre-
excess of anthracite contains beads of tin, which cipitated by microcosmic salt in the presence
are separated by vanning. In the cyanide of acetic acid and ammonium acetate. The
process, 10 grams of tinstone are fused with 40 precipitate consists of ammonium uranyl
grams of
impure cyanide (containing potassium phosphate U0 2 NH 4 P0 4
which is washed,
carbonate), and poured at a red heat. The ignited gently and weighed or converted into
German process consists in reducing a mixture uranyl pyrophosphate (U0 2 ) 2 P 2 7 for greater
,
of 5 grams each of tinstone and cupric oxide accuracy (Low's Technical Ore Analysis, 201).
with 15 grams of black flux (a mixture of carbon This precipitation is also the basis of a volu-
and potassium carbonate, obtained by heating metric method, a boiling solution of uranium
tartar) and 1-25 grams of borax with a cover of being titrated with a standard solution of
common salt. The reduced metal is compared phosphate, until ferrocyanide no longer gives a
in weight with that of the copper reduced from brown colour.
cupric oxide alone. The most trustworthy of Vanadium in steel is estimated by titratir
these methods is the fusion with cyanide. The with potassium permanganate. The steel
reduced tin, however obtained, is usually impure dissolved in HC1 and evaporated to dryness with
(Beringer's Assaying and KerPs Metallurgische a little nitric acid. The residue is fused with
Probirkunst). nitre and fusion mixture, boiled in water and
A good wet method for the estimation of filtered, and the filtrate evaporated with H 2 S0 4 ,
tin inores without previous concentration is reduced by sulphur dioxide and titrated. One
described by G. L. Mackenzie (Trans. Inst. atom of iron is equivalent to one of vanadium
Mng. and Met. xiii. 1904, 87). It consists in the titration (Rhead and Sexton's Assaying,
in cleaning a sample of from 1 to 5 grams 270).
of the ore with aqua regia (and removing the Zinc.The old dry methods of assay of or
tungstic acid, if it is present, by means of am- and alloys based on the loss of weight due
monia), reducing the stannic oxide to tin by the volatilisation of zinc at a white heat
ignition in a current of coal gas, dissolving the obsolete. Zinc is usually weighed as oxide after
metallic tin with hydrochloric acid and potas- precipitation as carbonate, or it is titrated with
sium permanganate, precipitating with sul- sodium sulphide or potassium ferrocyanide. Ar
phuretted hydrogen, and igniting the tin sul- amount of 1 or 2 grams of ore is weighed out
phide. The tin is weighed as stannic oxide. and dissolved in hydrochloric acid or aqua regia.
Tin is also estimated volumetrically. A The silica and metals other than zinc are re-
satisfactory method
described by Beringer moved as usual. All the precipitates will
(Text-Book of Assaying, llth ed. 285) is to contain zinc if they are bulky, and must be
reduce the solution of stannic chloride to stan- redissolved and reprecipitated. The alkaline
nous chloride by means of nickel foil, and to filtrate may be diluted to 200 c.c. and used for
titrate with a standard solution of iodine in an the sodium sulphide titration, which is carried
atmosphere of carbonic acid gas. Starch is used out at 50-60. A flake or two of freshly pre-
as an indicator. In all wet methods, tin oxide cipitated ferric hydrate is used as an indicator,
must be reduced to metallic tin before it can be turning from red to black as soon as sodium
dissolved. sulphide is in excess. One c.c. of the standard
Titanium in ores is generally in the form of solution of sodium sulphide should be equal to
titanic oxide, which is insoluble in acids. Tita- 0-01 gram zinc. Instead of ferric hydrate,
nates, however, are somewhat soluble, so that sodium nitroprusside may be used as an indicator
on attacking ores with acid, titanium will be on a white tile. This gives a purple colour with
found partly in the residue and partly in the sodium sulphide.
solution. The metals of the iron group with For titration with potassium ferrocyanide,
titanium are precipitated from the solution as the pure ammoniacal solution of zinc obtained
basic acetates, which are fused with potassium as above is acidified with hydrochloric acid,
bisulphate and extracted Avith water. The boiled and titrated hot. The standard solution
titanic acid is precipitated from the solution of ferrocyanide is made up by dissolving 41-2
ASSAYING. 329
grams of the pure salt in a litre of water. The the weight of water that could be evaporated at
test solution consists of 0-5 gram of uranium 100 and 760 mm. pressure by a unit weight of
acetate dissolved in 20 c.c. of water. drop A the fuel (v. FUEL).
of this solution gives a brown colour on a white In gold mills, these
Cyanide solutions.
tile with a drop of the zinc solution as soon as solutions are in wide use, and require frequent
the ferrocyanide is in excess. It is advisable analysis. Free cyanide is estimated by means
to confirm the end reaction by adding 5 c.c. of of a solution of silver nitrate prepared by dis-
a standard solution of zinc in hydrochloric acid, solving 13-04 grams of crystallised AgN0 3 in a
containing 10 grams of zinc per litre, and again litre of water. One c.c. of this solution is
titrating (Chem. News, Ixxvi. 6). equivalent to 0-01 gram of KCy, the end of the
The assay of zinc-dust for metallic zinc is titration being denoted by the solution becoming
made by acting on the sample with dilute sul- milky from the precipitation of AgCy. The
phuric acid, and collecting and measuring the reaction
is represented
by the equation :
hydrogen which is evolved.

Commercial metallic zinc contains lead, AgN0 3 +2KCy=KAgCy 2 +KN0 3 .
cadmium, and iron, and may also contain The amount ofcyanide solution taken for
arsenic, copper, antimony, tin, &c. By dis- assay may be from 10 c.c. to 100 c.c., according
solving in dilute sulphuric acid, the lead and the to its strength. Alkalis and other compounds
greater part of the copper, tin, cadmium, &c., which may be present dissolve silver cyanide,
are left undissolved. The residue is attacked and accordingly it is usual to add potassium
by nitric acid, and the metals separated as iodide as an indicator. Turbid cyanide solution
usual. Iron in zinc is titrated in the sulphuric must be filtered before titration. If soluble
acid solution without being separated. Arsenic sulphides are present, they prevent the assay
and antimony are passed with the hydrogen from being carried out. They are removed by
evolved by sulphuric acid into a solution of agitating the solution with freshly precipitated
silver nitrate (Campredon, Guide Pratique, 760 ; lead carbonate. If zinc is present in the
Eliot and Storer, Amer. Acad. Arts & Sciences, solution, part of the cyanide contained in the
viii. 57).
'
K
double cyanide 2 ZnCy 4 is estimated as free KCy.
'
Coal. The assay
of coal usually comprises The total alkali in a cyanide solution is
the determination of moisture, total ash, sulphur, estimated (J. E. Clennell, Chemistry of Cyanide
coking properties, and calorific power. The Solutions, 62) by titration with a standard
coal is broken down and sampled as in the case solution of sulphuric acid, using methyl orange
' '
of ores (see p. 316), and the sample is passed as an indicator. Protective alkali (op. cit.
through an 80-mesh sieve. 63) is determined by adding a slight excess
The moisture is determined by drying 1 of silver nitrate together with a little phenol-
gram in a water-oven for 30 minutes and weigh- phthalei'n solution, and titrating with sulphuric
ing. The coal is then again warmed for 15 acid until the pink colour disappears. The
' '
minutes and reweighed, and the process is con- reducing power of cyanide solutions is deter-
tinued until the weight is constant or begins to mined by acidification and subsequent titration
increase. with potassium permanganate, until the pink
For sulphur, 2 grams of coal are mixed tint becomes permanent, or by adding an excess
with 3 grams of a mixture of two parts of of permanganate followed by an excess of
calcined magnesia and one part of potassium car- potassium iodide and estimating the amount
bonate, and heated to dull redness for an hour of iodine liberated (op. cit. 71).
in a porcelain or platinum crucible, with occa- Gold and silver in cyanide solutions are
sional stirring. After cooling, the charge is determined by evaporation on lead foil, which
transferred to a beaker and digested with water is afterwards cupelled, or by evaporation with
and 1 c.c. of bromine. It is then acidulated litharge, which is fused for lead. A more rapid
with hydrochloric acid, the bromine boiled off, ;
method is to precipitate the gold and silver with
and the sulphur, now in the form of sulphate, zinc-dust and sulphuric acid, filter, and scorify
precipitatedby barium chloride. The sulphur or fuse- the residue. The latter method is espe-
may also be oxidised by heating the coal with I
cially suitable for treating large samples of
a mixture of nitre and common salt. Phos- I
poor solutions containing very little gold and
phorus in coal, if determined at all, is estimated i
silver. In all these methods, a button of lead is

in the ash, which may require complete analysis. I
obtained which is cupelled and the gold and
The coking qualities of coal are examined by |
silver parted as usual.
heating 50 grams of coarsely crushed coal in a Silica. The silica in ores is partly free and
' '
large copper crucible covered with a closely partly combined. The white sandy residue left
fitting lid. The evolution of gases is completed after careful extraction with acids is sometimes
after 15 or 20 minutes at a full red heat. After nearly
'
pure silica, and is often reported as
cooling, the coke is turned out and weighed, the i
silica and silicates insoluble in acids.' It may

loss of weight giving the amount of volatile be tested with sulphuric and hydrofluoric acids.
I
matter. The usual method with ores, slags, &c., is to

The calorific power of coal isdetermined by i
fuse 1 gram with 5 grams of fusion mixture
igniting 2 grams of the finely powdered sample and a little nitre in a platinum crucible or dish.
with 20 grams of a mixture of six parts of po- It is extracted with warm water and a little
tassium chlorate and one part of nitre. The coal hydrochloric acid and evaporated to dryness on a
and deflagrating mixture are ground together water-bath. The bases are dissolved out with
in a mortar and ignited in a Thompson calori- hydrochloric acid, and the silica filtered off.
meter. The error due to loss of heat by escaping The filtrate is again taken to dryness and dis-
gases, &c., always taken as one-tenth of the
is solved in hydrochloric acid to separate the
total evolved. The calorific power reported is remainder of the silica. If the ore contains a
330 ASSAYING.
large percentage of sulphides, oxides, &c., crystals of a bright-green colour and with
which are soluble in acids, these are removed brilliant faces are not uncommon. Sp.gr. 3-76.
before the fusion. In this case the acid solution Before the days of blotting-paper, it was used,
may contain silica, removed by evapo-
which is under the name of arsenillo, as a -writing sand
rating to dryness, taking up with hydrochloric for absorbing ink (v. COPPER). L. J. S.
acid and filtering. The purity of the silica is ATELESTITE. A
bismuth arsenate con-
tested by evaporating two or three times with taming iron phosphate found at Schneeberg in
water, sulphuric acid and hydrofluoric acid. The Saxony : Bi 2 3 , 57-15 ; Fe 2 P 2 O g , 12-50 ; As.,0 3 ,
silica is volatilised (J. Amer. Chem. Soc. xxiv. 30-35 (Freuzel, J. M. 1873, 785).
1902, 362). ATHAR or ATTAR. Indian name for
Sulphur. A rapid method of determining volatile oil of roses (v. OILS, ESSENTIAL).
the sulphur in ores given by Furman (Manual ATLAS DYNAMITE v. EXPLOSIVES.
of Practical Assaying, 5th ed. 91) is to fuse ATLAS POWDER v. EXPLOSIVES.
5 grams of the ore with 15 grams of borax, 3 ATLAS SCARLET 'v. Azo- COLOURING
grams of charcoal, and one or two nails in a MATTERS.
hot fire. The time required for fusion is about ATMOSPHERE. The gaseous envelope sur-
15 minutes. The nails are then withdrawn and rounding any liquid or solid body more parti- ;
the charge poured. As soon as the slag is cool, cularly the gaseous envelope which surrounds
the matte detached from it with a hammer
is the earth, and which is commonly known as ah*.
and weighed. If the matte were pure FeS, it The thickness of this aerial envelope is not
would contain 36-3 p.c. of sulphur. By analysis, known even approximately, but it is quite certain
Furman finds that the nearest approximation is that it exceeds 45 miles measured from the
to take the sulphur as 30 p.c. of the matte. The earth's surface, which was the limit assigned to
method, though inaccurate, is sometimes useful, it by Wollaston. Secchi calculated that air
as it can be completed in less than half an hour. exists even at a height of 300 kilometres above
The more accurate methods consist in the earth's surface. From the ratio of decrease
oxidising the sulphur by aqua regia or nitric of density with elevation, the atmosphere at
acid and potassium chlorate, or by fusion with a height of 50 miles cannot exert any measurable
a mixture of nitre and sodium carbonate, and pressure. The mass of the atmosphere forms,
weighing it as barium sulphate. A good method like the earth itself, an oblate spheroid, the polar
for ores and slags consists in fusion with axis of which is much shorter than the equatorial
caustic alkali, extracting with water, and oxidis- axis, the ratio of the two axes being, according
ing with bromine. After separation of the silica, to Laplace, as 2 to 3.
the sulphur is precipitated by barium chloride The pressure of the atmosphere at any par-
(Chem. News, i. 1884, 194). If lead is present, ticular spot may be measured in terms of the
the solution is boiled with ammonium car- height of a column of mercury which it is capable
bonate. T. K. R. of sustaining. It follows from the law of
ASTATKI. A Russian term, signifying Boyle that the density of the air rapidly dimi-
nishes with the height. For air of constant
'
dregs,' applied to the residue left in the dis-

tillation of Baku petroleum after the volatilisa- temperature, its density, or, what comes to the
tion of the kerosene, and now largely used as same thing, the height of the mercurial column,
fuel in the Caspian region (v. PETROLEUM). should diminish in geometric progression, whilst
ASTERIA (Star Sapphire) v. CORUNDUM. the distance from the earth increases in arith-
ASTRALINE. Russian petroleum oil, used metic progression. The pressure, even at the
for burning (v. PETROLEUM). same place, is continually varying from a
ASTRALITE. A glass resembling aven- variety of causes, and hence the height of the
turine, but containing crystals of a cupreous barometer, as the mercurial column was first
compound which by reflected light exhibit a termed by Boyle, is practically never absolutely
dichroic iridescence of dark red and greenish constant. The average height at any one spot
blue. Made by fusing and allowing to cool at the sea-level is mainly dependent upon the
slowly a mixture of 80 pts. silica, 120 lead oxide, great movements of air which result from the
72 sodium carbonate, 18 borax, with either effect of the earth's motion upon the gaseous
24 pts. scale oxide of copper, and 1 pt. scale envelope, combined with variations in the
oxide of iron, or with 5 pts. lime, 26 copper density of the aerial mass due to solar action.
oxide, and 2 iron oxide. According to Regnault, 1 litre of dry air, free
ASTROLIN. Trade name for antipyrine- from carbonic acid and ammonia, measured at
methyl-ethyl glycollate H
C 6 10 3 ,C 11 1? ON 2 H , and 0-76 mm. pressure, at Paris (lat. 48 50')
m.p. 64-65-5. A colourless powder, with a and at a height of 60 metres above the sea-level,
slight smell and pleasant taste, readily soluble weighs 1 -293187 grams. Lasch found that 1 litre
in water and alcohol. of pure air at standard temperature and pressure
ASUROL. Sodium-mercuri-amido-oxy.so- weighs at Berlin (lat. 52 36') 1-293635 grams.
butyrosalicylate. The Bureau Internat. des Poids et Mesures
ASYPHIL. Trade name for a mercury salt adopts for the weight of 1 litre of dry air, con-
of p-aminophenylarsinic acid taining 0-04 p.c. carbonic acid, at the normal
H
(NH,C 6 4 AsO(OH)0) 2 Hg. temperature, and under the normal barometric
pressure at lat. 45 and sea-level,
(v. ARSENIC, ORGANIC COMPOUNDS OF ; cf. p. 337).
ATACAMITE. Hydrated oxychloride of ***
~ 1 1-293052
+ 0-00367 X
i
760
copper CuCl 2 -3Cu(OH) 2 occurring in
, the
Atacama region of Chile, sometimes in sufficient on the assumption that 0-00367 is the expansion
amounts for use as a copper ore (Cu 59-4 p.c.). coefficient ofat constant pressure for a
air
Large quantities have also been mined at normal degree. For purposes of ordinary
Wallaroo in South Australia. Orthorhombic chemical calculation it may be assumed with
ATMOSPHERE. 331
sufficient accuracy that 1 gram of air measures The

refractive indices of dry air at standard
at standard temperature and pressure 773 c.c. temperature and pressure for the Fraunhofer
The total weight of the atmosphere is about lines A, B, C, D, E, F, G, H, are, according to
11 trillions of pounds, or about 5 trillion kilo- Kettler (Pogg. Ann. 124-401), as follows :
grams and the relative amounts of the chief n A = 1-00029286 wE= 1-00029584
constituents may be assumed to be B = 1 -00029345 nF = 1 -00029685
kgm.
Trillions C= 1-00029383 G= 1-00029873
Carbonic acid
....
Nitrogen (argon, &c.)
Oxygen
. .
.
.
4-041200
1-218040
0-003156
wD = 1-00029470
The emission spectrum of
by Huggins (Phil. Trans.
wH= 1-00030026
air has been mapped
154, 139) and Ang-
strom (Pogg. Ann. 94, 141), and the spectrum
5-262396 of lightning by Kundt (Pogg. Ann. 135, 315),
Herschel calculated that, allowing for the who has shown that forked lightning gives a
space occupied by the land above the sea, the line spectrum, whereas sheet lightning gives a
mass of the atmosphere is about 75^505 P ar* f band spectrum. The absorption spectrum of
that of the earth. air was first mapped by Brewster and Gladstone,
The unit of pressure adopted by engineers and has been further examined by Janssen,
and others, and styled an atmosphere, is an Cornu, and Chappuis (Compt. rend. 91, 988).
amount equal to the average pressure of the Air, owing to the oxygen it contains, is a
atmosphere at the sea's level. In British magnetic substance. The diurnal variation in
measure an atmosphere is the pressure equivalent magnetic declination has been alleged to bo
to 29-905 inches of mercury at 32F. at London, due to the varying magnetic potential of the
and is about 14-73 Ibs. on the sq. inch. In oxygen owing to alterations in temperature.
the metric system it is the pressure of 760 mm. Air is a mixture of nitrogen, oxygen, aqueous
(29-922 inches) at 0C. at Paris, and is equal to vapour, argon, carbon dioxide, with minute
1-033 kilos, on a sq. centimetre. Hence the quantities of ozone, hydrogen peroxide, am-
' '
English atmosphere is 0-99968 that of the monia, nitrous and nitric acids, hydrocarbons,
metric system. helium, neon, krypton, xenon, hydrogen, &c.
The specific heat of air at constant pressure That the air is not a chemical compound
is0-2374 (Regnault). Its coefficient of thermal of itscomponent gases is proved by the facts :
expansion between -30 and 200 is 0-003665 (1) that these gases are not present in any
for 1. constant ratio (2) that air can be made by
;
By the application of sufficient cold and simply mixing its constituents in the proportion
pressure, air may be liquefied. indicated by the analysis of air, without con-
Comparatively little of the sun's heat is traction or any thermal disturbance resulting ;
absorbed in its direct passage through the air. (3) that on treating air with water and expelling
According to Tyndall, a column of air 1 metre the dissolved air by boiling, the proportion of
long absorbs 0-088 p.c. of the heat which passes the oxygen to the nitrogen is found to be in-
through it. According to Violle, and also Lecher creased, and in amount corresponding with
and Pernter, the amount is not greater than the law of partial pressures ; (4) that the
0-0070 p.c. This absorption is mainly due to constituents of the air can be mechanically
aqueous vapour, and, in a lower degree, to car- separated by processes of diffusion and (5) that
;
bonic acid and suspended organic matter. The the refractive power of the air is equal to the
air mainly gets its heat by conduction from the mean of the refractive powers of its constituents,
earth, and hence, as a rule, it is hottest near the whereas in compound gases the refractive power
ground. The law of the decrement in tempera- is either greater or less than the refractive power
ture corresponding to height is not accurately of the elements in a state of mixture.
known it is usually stated to be about 0-56
; The amount of oxygen in air may be ascer-
per 100 metres, but the rate is liable to very tained by measuring the diminution in volume
great variations. which a known bulk experiences when in contact
Air is not perfectly transparent. Its particles with some substance capable of absorbing or
reflect and scatter light in sufficient quantity to
combining with oxygen gas. Among the sub-
obscure the light from the stars. The blue colour stances which may be conveniently used for this
of the sky is due to the fact that the most re-
purpose are :
frangible rays are most widely scattered. In the 1. Phosphorus. A fragment of phosphorus
higher regions of the atmosphere, where the on the end of a platinum or copper wire is
amount of reflected light becomes less and less, exposed to a measured volume of
air standing
owing to the decreased density of the air, the sky over water or mercury until no further decrease
appears to grow gradually darker. Brewster first of volume is observed (Berthollet). Lindemann
proved that the blue light from the sky, as well (Zeitsch. anal. Chem. 1879, 18, 158) employs
thin
as the white light from the clouds, was due to sticks of phosphorus for the same purpose in
by the fact that it was polarised.
reflected light, the Orsat apparatus (v. GAS ANALYSIS). At
Suspended matter, dust, smoke, aqueous a temperature below 7 the oxidation of the
vapour in a state of partial precipitation, &c., phosphorus ceases.
greatly diminish the transparency of air. Wild 2. Pyrogallol in Alkaline solution. Chevreul,
gives the following numbers as representing the in 1820, first suggested the use of this reagent.
transparency coefficient of 1 metre of air :
The absorption is apt to be accompanied by the
Dry air (free from dust) . . . 0-99718 formation of notable quantities of carbon
Air of a room (diy, but containing monoxide if the amount of oxygen is large or
dust) .
. . . . . 0-99520 the alkaline solution very concentrated. Accord-
Air free from dust, but saturated with the best pro-
ing to Hempel (Ber. 20, 1865),
dissolved in 15 c.c.
aqueous vapour . . . 0-99328 portions are 5 grams pyrogallol
332 ATMOSPHERE.
water mixed with 120 grams caustic potash dis- the oxygen was 702-56 mm., and after the ab-
solved in 80 cm. of water. Practically, no straction was 555-70 mm., then 1 volume of the
carbon monoxide is formed with this solution.
The absorption is very rapid (Hempel, Ber. 18,
air would be reduced to
=|^= 0-79096 vol.,
267 and 1800). or, expressed centesimally, the composition of

3. Metallic Copper. A spiral of copper wire
the air would be :
is heated to redness in dry from carbonic

air free
acid and of known pressure until the whole
of the oxygen has combined with the metal
to form cupric oxide. The pressure of the
Oxygen ....
Nitrogen (argon, &c.) . . 79-096
20-904
100-000
residual gas is then determined, whereby the
Kreusler has shown that unless the air be care-
amount of nitrogen is ascertained, and hence
the amount of oxygen. An apparatus on this fully dried before being heated with the copper
spiral, the proportion of oxygen will be apparently
principle was suggested by Jolly W. N. S. 6538)
( ;
too low.
it is seen in Fig. 1.
The glass vessel A, of about 100 c.c. capacity,

Dumas and Boussingault (Ann. Chim. Phys.
[3] 3257), as far back as 1841, made use of the
is exhausted by the mercurial pump, and is
fact that heated metallic copper combines with
replenished with the air under investigation.
oxygen, in order to determine the gravimetric
This is then cooled to by surrounding A
composition of air. Air deprived of moisture
and carbonic acid was passed through a weighed
tube containing metallic copper heated to red-
ness, whereby all the oxygen was absorbed, the
nitrogen being collected in a vacuous glass globe
also previously weighed. At the conclusion
of the experiment the tube containing the
metallic copper was again weighed ; the increas_
in its weight gave the amount of absorbed
oxygen, together with the weight of the nitrogen
which it also contained. The nitrogen was then
removed by the air pump and the tube agair
weighed ; the difference between the first and
third weighings of the tube containing the copper
gave the weight of absorbed oxygen, and the
weight of nitrogen was obtained by adding the
difference between the second and third weighings
of the tube to the increase in the weight of the
glass globe. As the mean of a large number
of experiments made by this method, the
precentage composition by weight of air fr
from water and carbonic acid was found to be
Oxygen . 23-00
Nitrogen (with argon, &c.) 77-00
100-00
Leduc has shown that this proportion of
oxygen is too low, as an average the amount ;
is about 23-2 p.c. by weight as calculated from

FIG. 1.
the known density of air and of its constituent
with the metallic cylinder B, which is filled gases (Compt. rend. 1896, 12, 1805 ; 1898, 126,
with melting ice. The tension of the confined 413).
air is measured by the height of mercury in the 4. Explosion with hydrogen. A measi
glass tubes g and d, which are connected to- volume of air is mixed with a known volume
gether by caoutchouc tubing. The tube g is hydrogen in excess, and the mixture is exploded
movable in the clamp /, the position of d being by the electric spark, when the oxygen combim
fixed with reference to A. By turning the three- with the hydrogen in the proportion of 1 vol.
way stop-cock b, A and d may be alone brought of the former to 2 of the latter to form water.
into connection, or both may be made to connect One-third of the contraction resulting from thi
with the outer atmosphere. The cock is now explosion represents, therefore, the amount
so turned that A and d are alone in connection ; oxygen in the air under examination. This
the tube g is now raised until the level of the method, first suggested by Volta, was perfected
mercury in d just touches the point m, when by Bunsen. Modifications of the method have
the tension of the air is read off on the graduated been made by Regnault and Reiset, Williamson
scale behind g. The copper spiral in A is next and Russell, Frankland and Ward, and others.
heated to redness by an electric current, whereby These methods are extremely accurate, and
the heated metal rapidly combines with the have afforded us all the exact knowledge we
oxygen. The cylinder B is once more placed have respecting the variations in the amount of
round A, the residual nitrogen cooled down to oxygen in atmospheric air. Thus Bunsen, in a
by means of melting ice, and its tension measured series of analyses made in the winter of 1846,
by adjusting the level of the mercury to m, and found that the percentage amount varied from
reading off the height of the mercury in g. 20-97 to 20-84. Regnault made a large number
If, for example, the pressure before abstracting of analyses of air collected from all parts of the
ATMOSPHERE. 333
world. In 100 analyses of air collected in Paris paper blue. Thallium turned brown
salts are
the minimum amount of oxygen was 20-913, the by the action of ozone, and hence papers soaked
maximum 20 '999. Air collected in various parts in solution of these salts have been used for the
of Europe, from above the Atlantic Ocean, from recognition of ozone. Paper soaked in a very
tin- summits of the Andes and from the South dilute solution of neutral gold chloride is turned
Polar Sea, contained an amount of oxygen vary- a deep violet colour by ozone (Bottger, Chim.
ing from 20-86 co 21 p.c. Many hundreds of Zentr. 1880, 719).
analyses were made by Angus Smith, of air Attempts have been made to estimate ozone
collected in various towns in England and by aspirating large volumes of air through
Scotland, and also of air collected in the country. dilute solutions of hydriodic acid and determin-
The oxygen in London air varied from 20-857 to ing the amount of the liberated iodine by iodo-
20-95, less oxygen as a rule being found in the metric analysis. Also by leading the air through
air of streets than in that of the parks and open a mixed solution of potassium arsenite and
spaces. A series of 30 analyses of Glasgow air potassium iodide, whereby the liberated iodine
showed variations from 20-887 in the closer converts the arsenite to arsenate. The liquid
parts to 20-929 in the more open spaces. Even through which the air had passed was then
wider extremes were found by Leeds in the air mixed with a few drops of ammonium carbonate
of New York, viz. from 20-821 to 21-029 p.c. solution and starch paste, and a standard solution
According to E. W. Morley, the diminished of iodine (1 1000) added until the blue colour
:
proportion of oxygen be caused by the

may was permanent. A precisely similar experiment
down-rush of air from the higher regions of the was made on equal amounts of distilled water,
atmosphere, which probably contain a less iodine, arsenite, &c., used, and from the
relative amount of oxygen. Regnault's experi- difference in the amount of iodine solution
ments afford some evidence for the belief that needed the amount of oxidised arsenite and
the air of the tropics contains slightly less hence the quantity of ozone was determined.
oxygen than that in northern latitudes (v. also It appears that the amount of ozone varies
Jolly, W. N. F. 61, 520). A similar conclusion with the seasons : it is greatest in winter, be-
has been drawn by Hempel (Ber. 20, 1884) from comes gradually less during spring and autumn,
the analysis of a large number of analyses of and is least in summer. Ozone is more fre-
air collected simultaneously at Tromso, Dresden, quently observed on rainy days than in fine
and Paris. The mean results were : weather ; thunderstorms, gales, and hurricanes
Oxygen are frequently accompanied by relatively strong
Tromso . . . .20-92 manifestations of it (cf. Thierry, Compt. rend.
Dresden
Paris ....
. . . .20-90
From the results of 203 analyses of air col-

20-89
1897, 124, 460).
It is highly probable that many so-called
ozone manifestations are due to hydrogen per-
lected at five different spots and analysed by oxide, the existence of which in the air was
three independent methods, it follows that the first demonstrated by Meissner in 1863. Unfor-
most probable mean percentage amount of tunately, there is no ready mode of discriminating
oxygen is 20-93. Numerous determinations between ozone and hydrogen peroxide. It is
by Pettersson and Hogland of the air of Stock- probable that the amount of hydrogen peroxide
holm during October, November, and December, in the air is as a rule greater than that of ozone.
1889. gave 0=20-94 (Ber. 22, 3324; Hempel, Schone found from observations made at
Ber. 20, 1864 ; Kreusler, Ber. 20, 991). Moscow, that it was invariably present in rain,
Ozone is always present in minute quantity dew, and snow, and was less in winter than in
in normal air. Air over marshes contains little summer and more in southerly winds than in
;
or no ozone. No ozone can be detected in the those from the north. The amounts in all cases
air of large towns or hi inhabited houses. were, however, very minute, the maximum
Atmospheric ozone is probably formed by the being 1-4 c.c., and the mean 0-38 c.c. hydrogen
action of electricity on air and on the water peroxide vapour in 1000 c.c. air.
contained in it, and by the evaporation of water.
The quantity of aqueous vapour in the air
No accurate quantitative method is known for varies with the temperature thus 1 cm. of air
:
the estimation of ozone ; all the information we when saturated with water contains :
at present possess has been obtained by the use At 102-284 grams At +20 17-157 grams
of so-called ozone papers. Of these the best 4-871 25 22-843
known is Schonbein's, which is based on the fact + 5 6-795 30 30-095
that ozone liberates iodine from potassium 10 9-362 35 39-252
iodide, and thereby renders starch blue. To 15 12-746
prepare them, unsized paper is immersed in a The most accurate method of determining
solution of 15 parts starch and 1 part potassium amount
the aqueous vapour in the air consists
of
iodide in 200 parts of water and dried in the in aspirating a given volume of the air through
dark. To make a determination of ozone the
weighed tubes filled with some hygroscopic sub-
paper is freely exposed to the air for some hours stance, such as phosphoric oxide or pumice
and moistened with water, and the depth of soaked in oil of vitriol and reweighing the tubes,
tint produced compared with a standard scale when the increase of weight gives the quantity of
of colour. The method has no pretensions to moisture present.
scientific accuracy. Houzeau (Ann. Chim. Usually, however, the humidity of the air is
Phys. 4, 27, 5) determines the relative amount estimated by means of hygrometers, the best-
of ozone by
exposing red litmus paper previously known form of which is the psychrometer or
dipped in 1 p.c. sol. of potassium iodide and wet-and-dry-bulb thermometer of August. The
dried, to the action of the air. The ozone absolute humidity of the air is the weight of
liberates iodinu and the free alkali turns the
aqueous vapour contained in 1 con. The relative
334 ATMOSPHERE.
humidity denotes the relation between the
weight actually present and that which could
be theoretically present if the air were saturated ;
it is usually expressed in per cent, of the maxi-

mum humidity. The air is seldom absolutely
saturated with aqueous vapour, although in our
moist climate saturation is occasionally very
nearly attained. With us the most humid
month is December, and the driest is July.
The presence of carbonic acid in the atmo-
sphere was first indicated by Black hi 1752.
The quantity in normal air is about 0-03 p.c. ;
in that of large towns it is slightly greater.
Angus Smith gives the following summary of
results obtained in London in 1864 and 1869
(Airand Rain, 53-58) :
Over River Thames . 0-0343 p.c.

8 expts.
In the Park . . 5 0-0301
.,
In the streets . .10 0-0380

Any circumstance which interferes with the
ready
"
diffusion of the products of respiration
and of the combustion of fuel will tend
to increase the relative amount of carbonic
acid in the ah- of a town hence during fogs
:
the amount may be as great as 0-1 p.c.

The amount of carbonic acid in the air of
the country at night is usually greater than in
the day, as the following comparison shows :
Air in the day-time.
Observer
ATMOSPHERE. 335
found that the upper strata of air contain much number of estimations of the micro-organisms
less ammonia than air near the ground. Levy contained in the air of towns and in the country
(Compt. rend. 91, 94) found that the rain water and in inhabited buildings. By simultaneously
and snow of Paris contain in mean 1-17 mgm. exposing small circular glass dishes partially
of ammoniacal nitrogen per litre of water. The filled with the nutrient gelatine to the action
amount of ammonia in this meteoric water is of the air, a rough estimate was obtained not
least in winter and greatest during the warmer only of the number of micro-organisms hi a
periods of the year. Gilbert and Lawes found given volume of the air, but also of the number
that 1,000,000 pts. of rain water collected in the which fell during a given time on a definite
country contained 0-927 to 1-142 pts. of am- horizontal area. As the mean of a series of
monia. Rain water collected in towns always observations made on the roof of the South
contains largequantities of ammonia. Thus Kensington Museum between January and June,
Angus Smith found that rain water collected in 1886, it was found that there were 35 organisms
the sparsely populated districts in Scotland con- in 10 litres of air, whilst 279 was the average
tained 0-53 pt. per million, whereas the rain number which fell on 1 sq. ft. in 1 minute.
water of London contained 3-45, that of Liver- Similar experiments made near Reigate and in
pool 5-38, that of Manchester 6-47, and that of the vicinity of Norwich showed an average of
Glasgow 9-1 per million. The increased amount 14 organisms in 10 litres of ah*, while 79 fell
in the towns is doubtless due to the influence of per sq. ft. per minute. Experiments made in
animal life and to the constant presence in Kensington Gardens, Hyde Park, and on Prim-
greater proportion than in the country of readily rose Hill, gave an average of 24 organisms in
decomposable nitrogenous organic matter in the 10 litres, and a deposition of 85 per sq. ft. per
air (cf.Heinrich, Chem. Soc. Abst. 1898, ii. 114). minute. At St. Paul's Cathedral, 56 organisms
The quantities of nitrous and nitric acids hi were found at the base, 29 in the Stone Gallery,
the air are even smaller than that of ammonia. and 11 in the Golden Gallery, in 10 litres of air.
Angus Smith (Air and Rain, 287) has given At Norwich Cathedral, 18 at the base, 9 at a height
the following results showing the amount con- of 180 ft. and 7 at 300 ft. In inhabited build-
tamed in a million pts. of rain water :
ings great variations were observed ; as a rule,
the number of micro-organisms was less than
Scotland, inland country places . 0-305
Ireland . 0-370 was found in the open air when the air of the
Scotland, country places . . 0-424 room was undisturbed, but rose rapidly when the
towns . . . 1-164 ah- was set in motion by draughts or by the
.,
England, inland country places . 0-749 presence of many people (P. F. Frankland, Rov.
towns . . . 0-863 Soc. Proc. 40, 509).
Experiments made at the Montsouris Obser-
Occasionally, and more especially in the air of
vatory have shown that far fewer organisms are
towns, minute quantities of hydrocarbons,
present in the air during winter than during
sulphuretted hydrogen, carbonic oxide,
spring and summer. The number also seems to
sulphurous acid, common salt, alkaline be greatly increased after rain. Whilst in the
sulphates, are met with. Boracic acid and warm months the number of spores in 1 litre of
sal ammoniac have been observed in air in
air was 28, after heavy rain it rose to 95 and
the neighbourhood of active volcanos.
120.
The percentage amount by volume of the
Atmospheric dust is made up of both in-
Argon ....
inert gases in the air may be stated as follows
0-93000 p.c.
:
organic and organic matter. Tissandier found

that 1 c.m of the air of Paris contained on the
Krypton
Xenon
Neon
....
.
....
. . 0-00995
0-00114
0-00123
average 7-5 mgms. of dust ; after a period of
dry weather (8 days), 23-0 mgms., and after
heavy rain, only 6 mgms. It consisted of
-
Helium . . . 0-00040 from 27 to 34 p.c. volatile matter, and from

(Moissan, Compt. rend. 137, 600 ; Ramsay, 66 to 75 p.c. mineral matter, viz. sulphates
Roy Soc. Proc. 1908, 80 A, 599.) and chlorides of the alkalis and alkaline earths,
Organic matter in greater or less quantity oxides of iron, earthy carbonates and phos-
is
always present hi the air. Much of this is phates, &c. (cf. J. Aitken, Trans. Roy. Soc.
nitrogenous, and apparently readily susceptible Edin. 35, 37, 39).
to putrefaction, giving rise to products which are
alternately transformed into ammonia, nitrous
RADIOACTIVE CONSTITUENTS OF THE ATMO-
and nitric acids. This form of organic matter SPHERE.
reduces silver nitrate and potassium perman- A charged electroscope slowly loses its charge
ganate solutions. A
portion of the organic in ah*, and it has been shown that this is not due
matter consists of micro-organisms which to moisture, but that, on the contrary, the
are rapidly deposited in the absence of strong leakage is greater in dry than in wet weather.
aerial currents. Hesse quantitatively estimates The conductivity of air is lessened by passage
of a
the relative proportions of micro-organisms con- through a metal tube or by the presence
tained in air by aspirating a given volume of weak electric field. These facts indicate that
the air through glass tubes coated internally the conductivity of air is due to the presence
with gelatine peptone, which is then kept at a of charged ions (Townsend, Proc. Roy. Soc.
temperature of about 25 for some days, when 1899, 65, 192; Geitel, Naturw. Rundsch. 21,
the various monad bacilli and micrococci which 221). The rate of leakage of electricity from
are arrested and which are capable of growing a charged conductor in dust-free air is the same
in the gelatine
peptone are recognised by the for positive and negative charges, but varies
colonies which they form. By means of this with the pressure. The loss of charge per second
method Percy F. Frankland has made a corresponds to the production of aoout 20 ions
336
ATRANORIN. 337
of either sign in each cubic centimetre of air the contained air. Ashman (Amer. J. Sci.
(Wilson, Proc. Ro.y. Soc. 68, 151). 1908, 26, 119) has thus found in Chicago air
Elster and Geitel have shown (Wied. Ann. an amount of emanation per cubic metre equal
that ions are produced during to that which would be in equilibrium with
[2] 39, 321)
the formation of ozone by contact of air with about 1-0 XlO~ 10 gram of radium. By absorb-
flames or by the slow oxidation of phosphorus, ing the emanations in charcoal and then
&c., but the mere presence of ozone does
not volatilising them into an electroscope, Eve
impart conductivity to air ( Jorissen and Ringer, has obtained results of the same order
Ber. 1906, 39, 2090). Langevin (Compt. rend. 0-8 X 10~ 10
gram for the radium equivalent of
1905, 140, 232) states that in air, in addition to the emanation in the air of Montreal (Phil. Mag.
of a 1907, 14, 724), and has shown by numerous
ordinary ions carrying charges equal to that
ions
hydrogen ion in solution, there exist other observations that the value is not affected by
having a much smaller mobility, but carrying temperature, but that a deep cyclone with rain
charges fifty times as great. causes an increase, whilst anti-cyclonic conditions
Nordmann has described (Compt. rend. 140, cause a decrease in the amount of emanation
430) an apparatus for continuously recording the (Phil., Mag. 1908, 16, 622). These results have
state of ionisation of the air. Air is caused to been confirmed by Satterly (Phil. Mag. 16, 584).
circulate between the plates of a cylindrical All investigators are agreed that these
condenser, and the charge given up by the ions emanations are the chief cause of the ionisation
is removed by dropping water. The condenser of air, but Wilson, by experiments on the effect
' '
is connected with an electroscope, the deviations of pressure on natural ionisation of air enclosed
of which are recorded photographically, and are in a metal cylinder, has shown (Phil. Mag. 1909,
proportional to the number of ions present 17, 216) that it is partly due to some pene-
in
unit volume of air. Another apparatus for the trating radiation the source of which is not
same purpose is that of Langevin and Moulin in the soil (Pacini, Atti R. Acad. Lincei, 1909,
(Compt. rend. 140, 305). 18, 123). Both Pacini and Wulf (Physikal.
No satisfactory explanation of the ionisation Zeitsch. 1909, 10, 152) have detected a double
of air was found until EJster and Geitel showed diurnal periodicity in the state of ionisation of
(Physikal. Zeitsch. 1901,76, 590) that a negatively the air.
charged wire suspended in the open air became (See also Harvey (Physikal. Zeitsch. 1909,
coated with radioactive matter, the presence of 10, 46) and Runge (Chem. Soc. Abstr. 1908, ii.
which could be proved by its action upon a 80).)
charged electroscope, although the quantity ATOXYL. Trade name for the mono-sodium
present was altogether too small to respond
to salt ofp-aminophenylarsinic acid (Ehrlich
any chemical test. Rutherford and Allan and Bertheim). Forms a white crystalline taste-
confirmed this observation, and measured the less, odourless powder. So named from its
rate of decay of the deposit (Phil. Mag. 1902, relatively low toxic action (v. ARSENIC, ORGANIC
vi. 4, 704). Later, Allan showed that the COMPOUNDS OF).
radioactive matter could be removed from the ATRAMENTUM STONE. (Atrameniumslein,
wire by rubbing it with a piece of felt or by Ger.) A product of the partial oxidation
solution in ammonia, and that the ashes of the of iron pyrites, consisting of a mixture of ferrous
felt or the residue from the evaporation of the and ferric sulphates with free ferric oxide. Used
solution showed radioactivity having a period in the manufacture of ink.
of decay equal to that of the deposit on the ATRANORIN C l? H 188
is present in the
wire (Phil. Mag. 1904, vi. 7, 140). lichens Evernia vulpina, E. prunastri, E. fur-
These phenomena are due to the presence furacea, Lecanora atra, L. sordida,
Parmelia
in the atmosphere of the gaseous emanations perlata, P. physode-s, Physcia stdlaris,
Xanthoria
of radioactive elements, probably those of parietina, Cladonia rangiformis,
and Stereocaulan
radium and thorium (Bumstead, Amer. J. Sci. vesuvianum. It forms colourless prisms ; m.p.
1904, 18, 1). The amount of active matter 195-197 (Zopf), 187-188 (Hesse); easily
is not constant, but increases with increased soluble in hot chloroform, soluble in alkalis with
circulation of the air, and is therefore probably a yellow colour.
water
due to the presence of radium in the soil (Simp- According to Paterno, by heating with
son, Phil. Trans. 1905, A, 205, 61). Balloon to 150, atranorin gives physciol (methyl-phloro-
observations made by Flemming (Zeitsch. glucinol),and atraric acid (betorcinol carboxylic
physikal. Chem. 1908, 9, 801) show that radium acid methyl ester), and these substances are also
emanation is present even at a height of 3000 obtained when atranorin is heated with acetic
metres. Thorium emanation exists principally acid in 3 sealed tube (Hesse).
in air taken from the soil or the lower layers
Physciol forms colourless needles, m.p.
104-
of the atmosphere (Gockel and Wulf, Physikal. 105, gives with ferric chloride a blue-green
Zeitsch. 1908, 9, 907). That it is not widely colouration, and possesses, according to Hesse,
disseminated in the air is probably due to its the constitution of a methylphloroglucinol
rapid rate of decay (Blanc, Physikal. Zeitsch. CH 3
1908, 9, 294). The experiments of Dadourian
(Physikal. Zeitsch. 1908, 9, 333) and of Wilson OH |OH
(Phil. Mag. 1909, 17, 321) indicate that air
normally contains about 3700 times as much
radium emanation as thorium emanation.
OH
Betorcinol acid methyl ether
By passing air through a copper spiral cooled carboxylic
140-141
in liquid air, the emanations are condensed, and CioHujO^ crystallises 'in leaflets, m.p. ;
and gives with calcium hypochlorite solution a

may then be volatilised into an electroscope and
the amount estimated by their effect in ionising blood-red colouration. Digested with boiling
VOL. I. T.
338 ATRANOR1N.
hydriodic acid, it is converted into f)-orcin ATTAR OF ROSES v. OILS, ESSENTIAL.
(Stenhouse and Groves) C 8 10 2 , according to H AUCUBIN v. GLUCOSIDES.
the equation : AURAMINE. Iminotetramethyldiparamino-di-
C1 H 11 4 +HI=CH,I+CO +0 H I0 O r t 8 phenylmf-thane hydrochloride, C 17 H 21 N 3 ,HC],H 2 0;
_
fi-Orcin (see also Barbatic acid) is 1-4-di-

NMe 2 -C 6 H 4C(NH)-C 6 H 4 -NMe 2 ,HC],H 2 0(Graebe),
or Me 2 N-C 6 H 4 -C(NH 2 C 6 H 4 NMe 2 Cl,H 2
) : :
methylresorcin.
The constitution assigned to betorcinol (Stock; Dimroth and Zoeppritz). According
to Stock (J. pr. Chem. 47, 401 ; Ber. 1900,
carboxylic acid methyl ether is :
33, 318), and Dimroth and Zoeppritz (Ber. 1902,

CH 3 35, 984), the base has the constitution assigned
to it by Graebe (Ber. 1899, 32, 1678 ; 1902, 35,
OH>OH 2615), but the hydrochloride and the other salts
have the quinonoid structure Me 2N-C 6 4 C(NH,): H <
CH 3 H
C 8 4 : NMe 2 Cl, and are to be regarded as
Heated with alcohol in a sealed tube, atranorin I
derivatives of triphenylmethane in which an
gives, according to Paterno, Hcematommic acid
! amino- group has replaced one of the benzene
and Hcematomminic acid ; but the researches |
residues.
of Hesse indicate that these compounds in Auramine, the first member of a series of
reality consist of hcematommic acid methyl i
yellow, orange-yellow, or brown dyes, is the

ether and betorcinol carboxylic acid methyl ether. hydrochloride of a colourless base obtained by
Hcematommic acid methyl ether C 10 10 5 H the action of ammonia on tetramethyldiamino-
forms colourless needles, m.p. 147, soluble in benzophenone, and comes into the market either
alkaline solutions with a yellow colour. With in the nearly pure form as Auramine 0, or mixed
a purple-red or purple-
ferric chloride it gives with dextrin as Auramine I. and //. (Graebe,
brown colouration. The ethyl ether, C 11 12 5 , H Ber. 20, 3264). Fehrmann (Ber. 20, 2847) pro-
gives colourless needles, melts at 111-112 posed to restrict the name auramine to the
(Hesse); 113-114 (Zopf). It is represented by colourless base, but such a change would inevit-
the formula :
O - CH,
ably lead to confusion ; and Graebe (I.e.) has
consequently adopted the
for the base itself, using the
name auramine-base
term auramine in
its usual signification.
CH 3
Preparation. (
1) Auramine was originally pre-
pared from
tetramethyldiaminobenzophenone
HO O
by dissolving it in some indifferent solvent such
COOC 2H 5 as chloroform, carbon disulphide, hydrocarbons,
&c., treating it with half its weight of phos-
When a solution of atranorin in dilute acetic
phorus trichloride or oxychloride, and adding
acid is gently evaporated, atranorinic acid excess of concentrated ammonia to the chlori-
(Hesse) is produced. This compound is also nated compound thus obtained (B. A. S. F.,
present in the Cladonia rangiformis (Hesse) when D. R. P. 27789).
gathered in December, but is absent from this (2) Auramine can be prepared more econo-
lichen in summer.
mically by heating tetramethyldiaminobenzo-
Atranorinic acid C lg 18 H 9 ,H 2 forms
phenone with suitable ammonium salts, such
colourless crystals, which are anhydrous at as the chloride, acetate, tartrate, thiocyanate,
100, and then melt at 157. With ferric &c., in the presence of zinc chloride at 200
chloride it gives a dark brownish-red colouration. Acetamide
(B. A. S. F., D. R. P. 29060).
Heated with hydriodic acid it gives 0-orcin, or
with alcohol yields carbon dioxide, physciol
may be employed instead of ammonium salts
(B. A. S. F., D. R. P. 38433), or the dye may
and fl-orcin. The constitutors assigned to be obtained by heating aniline hydrochloride
atranorinic acid (I.) and atranorin itself (II.) are with zinc chloride and carbamide, phenylcar-
as follows
bamide, diphenylcarbamide, or carbanil (Ewer
:
CH 3 CH S and Pick, D. R. P. 31936); but these alterna-

tive methods have no practical importance.
/\_COOH COOCH, At the present day, auramine is pre-
HO O CH 2 CH, (3)
pared by a method due to Sandmeyer (Eng.
c Pat. 12549, 1889; 16666, 1890) and Walker'
(J. Soc. Chem. Ind. 1901, 34), which consists
in heating a mixture of tetramethyldiamino-
CH 3j
CH. diphenylmethane, sulphur, ammonium chloride,
OH OH OH\ > and sodium chloride in a current of dry ammonia.
COOH A modification of this method is described by
J. Y. Johnson (B. A. S. F., D. R. P. 71320 ;
CO
[ Eng. Pat. 6249, March 23, 1893), in which the
1. II.
tetramethyldiaminodiphenylmethane is replaced
References. Paterno and Oglialaro (Gazz. by dimethyl - tetramethyldiaminodiphenylme-
chim. ital. 7, 289), Paterno (ibid. 10, 157 and 12, thane obtained by condensing acetone and
257) Zopf (Annalen, 288, 38); Hesse (J. pr. Chem.
; dimethylaniline (Ber. 1878, 12, 813). About 14
57. 280) ; Liidecke (Annalen, 288, 42) ; Hesse kilos, ofdimethyl-tetramethyldiaminodiphenyl-
(Annalen, 119, 365) ; Stenhouse and Groves methane are mixed with 120 kilos, of salt, 6
(Annalen, 203, 302). A. G. P. kilos, of sulphur, and 7 kilos, of ammonium
ATROLACTINIC ACID v. LACTIC ACID. chloride, and a stream of ammonia gas is passed
ATROPINE v. VEGETO-ALKALOIDS. through the mixture for eight hours at 175.
AURAMINE. 339
The mass is first washed with cold water to dis- ducing colours which are pure yellow and
fairly
solve away the salt and ammonium chloride, fast to light and soap. Cotton, for which the
it is then dissolved in water at 70, filtered, is
dye chiefly used, requires to be first mordanted
and the dye salted out, pressed, and dried. with tannin and tartar emetic, and on this
Auramine is also prepared by heating dimethyl- account auramine is useful for producing com-
aminobenzamide and dimethylaniline with zinc pound shades with other basic colouring matters,
chloride at 160-200 (D. R. P. 77329). such as safranine, benzaldehyde-green, &c.,
(4) Guyot (Compt. rend. 1907, 144, 1219; which are fixed by the same mordant. (For
J. Soc. Chem. Ind. 1908, 679) has synthesised further information v. Kochlin, Wagner's Jahr.
auramines by means of the oxalic esters. 1884, 1139.) ;
Tetraalkyldiaminodiphenylglycollic esters J. Soc. ( Salts. Auramine hydrochloride C 17 H 21 N 3 ,
Chem. Ind. 1907, 603) form neutral salts with HC1, is sparingly soluble in water, and has p.y>
acids, the indigo-blue aqueous solutions of which 90-4 at 25
: the palmitate C 17H 21 N 3 ,C 16 H 32 2
;
,
react with ammonia even when dilute to furnish has m.p. 57, the stearate has m.p. 68 (Gnehm,
tetraalkyldiaminodiphenylamino acetic esters, Roteli
j
Zeit. Angew. Chem. 1898, 487); the methyl
according to the equation :
sulphate obtained by the action of dimethyl
I
(R 2 N-C S H 4 ) 2 CC1-CO 2 R'+2NH 3

1
sulphate on auramine, has m.p. 225 (Zohlen, J.

=NH 4C1+(R 2 N-C 6 H 4 ) 2 C(NH 2 )CO 2 R'. pr. Chem. 1902, 66, [20] 387).
'
Substituted Auramines. In addition to

These new compounds are earo-carboxylic deriva-
tives of the leucauramines, and possess all the auramine, substituted auramines have also been
prepared. Auramine G, obtained by treating a
properties of the latter. They dissolve in hot
;
mixture of sym-dimethyldiamino-di-o-tolyl-
'
glacial acetic acid with an intense blue coloura- methane (from methyl o-toluidine and formal-
tion, and condense with aromatic tertiary amines
|
to form triphenylmethane derivatives. Thus dehyde) sulphur, ammonium chloride and salt
with dry ammonia gas (Gnehm and Wright, U.S.
ethylhexamethyltriaminotriphenyl acetate is
!
Pat. 488430), has m.p. 120, the picrate has m.p.

produced by heating an equimolecular mixture ;
of and 234, the sulphate m.p. 182, the oxalate m.p.

dimethylaniline ethyltetramethyl- 210. Leucauramine G has
m.p. 208.
diaminodiphenylaminoacetate in glacial acetic
acid on the water-bath for some minutes :
Metaxylylauramine can be obtained by heat-
ing an intimate mixture of 10 kilos, of tetra-
(Me 2 N-C 6 H 4 2 C(C0 2 Et)-NH 2 +C 6H 5 -NMe 2
)
methyldiaminobenzophenone and 23 kilos, of
=(Me 2 N-C 6 H 4 ) 2 C(CO 2 Et)C 6 H 4NMe 2 +NH 3 metaxylidine hydrochloride for about 4 hours
.
When a dilute alkaline solution of the amino- at 200 in an enamelled vessel provided with a
acetic ester is oxidised with dilute potassium ;
mechanical stirrer. Fusion takes place slowly,
ferricyanide solution in the cold, a quantitative i
and the mass becomes reddish yellow in colour,
yield of the corresponding auramine is produced. assuming finally a greenish metallic lustre towards
Properties. Auramine crystallises from the close of the reaction, which is complete when
water in yellow scales, which seem to consist of a test specimen is almost entirely soluble in
six-sided tables, and from alcohol in golden- water. The cooled mass is extracted with hot
yellow scales, melts at 267 (Graebe), carbonises water, and the dye precipitated in orange-yellow
at 265-280 without previous fusion (Fehrmann), flocks -by addition of sodium nitrate to the
and is sparingly soluble in cold but readily filtered solution.
soluble in hot water ; the temperature of the Methylauramine MeN C(C 6 H 4 -NMe 2 ) 2 m.p.
:
,
aqueous solution, however, must not exceed 60- 133 (Zohlen, J. pr. Chem. 1902, 66, 387), the
70, otherwise decomposition ensues, with the hydrochloride C 18 H., 4 N 3 C1, has m.p. 225, the pla-
formation of ammonia and tetramethyldiamino- tinichloride (C 18 24 H N 3 Cl) 2 PtC] 6 ,
m.p. 190-200,
benzophenone. On treatment with mineral acids, the hydrobromide C 18 H 24 N 3 Br,
m.p. 260, the
the aqueous solution undergoes a similar decom- H N
hydriodide C 18 24 3 I, m.p. 259, forms a series
position either slowly in the cold or very rapidly of unstable
'
polyiodides the trichr ornate

:
on heating. Spectroscopically, auramine be- H N

(C 18 24 3 ) 2 Cr 3 10 , m.p. 70, the thiocyanate
haves like most yellow dyes ; a hot concentrated H N
C 18 24 3 CNS, m.p. 213-214, and the picrate
aqueous solution, however, shows two bands, C 18 H 23 N 3 ,C 6 H 3
7 N 3) m.p.
225.
one in the red and one in the green, which Ethylauramine EtN C(C 6 4 -NMe 2 ) 2 , from
: H
become broader on dilution and finally coalesce, i
auramine ethyl iodide and zinc oxide (D. R. P.
forming a bright broad band extending from the i 136616), m.p.' 130-131, dyes mordanted cotton
middle of the red to the commencement of the a pure yellow.
green (Graebe). On treatment in the cold with Phenylauramine PhN C(C 6 H 4 -NMe a ) 2 pre-
:
,
ammonia, auramine (crystallised from alcohol) pared by heating tetramethyldiaminodiphenyl-

is converted into the colourless base C
17 21 3 H N , methane with aniline and sulphur at 200 (Feer,
which melts at 136, and is characterised by D. R. P. 53614) ; or by heating dimethylamino-
yielding with acids intensely yellow, and for the benzanilide with dimethylaniline and phosphorus
most part crystalline salts, which dissolve in oxychloride (D. R. P. 44077) ; has m.p. 172 ;
water and alcohol without fluorescence. Alka- H
the hydriodide C 23 25 N 3 ,HI, has m.p. 242 ; the
line
reducing agents, such as sodium amalgam, H
methiodide C 23 25 N 3 ,MeI, has m.p. 214.
slowly decolourise the alcoholic solution of Paraminophehylauramine 2 C6 4N NH H :
auramine, forming leucauramine C 17 23 3 , a H N C(C 6 H 4 -NMe 2 ), (Finckh and Schwimmer, J. pr.

colourless crystalline reduction compound melt- Chem. 1894, 50, 401), has m.p. 221-222 the ;
ing at 135, which dissolves in acetic acid with hydrochloride, m.p. 224 ; the picrate, m.p. 185-
an intense blue colour owing to its decompo- 186 (corr.) the diacetyl derivative has m.p. 194-
;
sition into ammonia and tetramethyldiamino- 195 ; the triacetyl derivative has m.p. 257-
benzhydrol. 258* ; monobenzoyl derivative has m.p. 117 and ;
C
Auramine dyes wool and silk direct, pro- the dibenzoyl derivative has m.p. 180-181 ;
340 AURAMINE.
paraphenylenediauramine H
C 6 4 [N C(C 6 4 : H -
Ber. 11, 845). Aurantia is used chiefly as a dye
NMe,) 2] 2 has m.p. 311-312.
,
for leather (W. J. 1877, 1002). Like hexanitro-
Orthaminophenylauramine, m.p. 199-200, diphenylamine, it is very explosive, but any
forms a picrate, m.p. 220-221, and a benzoyl danger may be avoided by moistening it with
derivative, m.p. 236-237 ; orthophenylene- glycerol (W. J. 1876, 996). According to
diauramine has m.p. 305. Gnehm (Ber. 9, 1246, 1557) and Bayer & Co.
/'-Tolylauraniine, obtained by heating te- (W. J. 1877, 879), aurantia produces skin
tramethyldiaminodiphenylmethane with p- eruptions ; Martius, however, contends that
toluidine and sulphur (D. R. P. 53614), or from this effect is due to idiosyncrasy, and quotes the
-
dimethylaminobenzo p toluidine,
-
dimethyl- opinions of Salkowski and Ziureck in support
aniline, and phosphorus oxychloride (D. R. P. of his statement (Ber. 9, 1247), and the question
44077), has m.p. 178. o-Tolylauramine similarly appears to have received a solution in this sense
prepared to the p- compound has m.p. 173-174, in Germany, since the ministerial order of
a - naphthylauramine (Me 2 N-C 6 H 4 ) 2 C NC 10 H 7 : November 8, 1877, prohibiting its manufacture,
(D. R. P. 44077), has m.p. 225. 0-naphthyl- was cancelled in June, 1880.
H
auramine (Me 2 N-C 6 4 ) 2 C N-C 10 7 (D. R. P.
: H AURIN and ROSOLIC ACID.
44077), m.p. 179 - 180. Benzylauramine History. Rosolic acid was first discovered
: H
C 6 H 5 -CH 2 -N C(C 6 4 -NMe 2 ) 2 (D. R. P. 136616) and its tinctorial properties described by Runge
from auramine benzylchloride and magnesia, (P. 31, 65), who obtained it from coal-tar oil by
has m.p. 116. Benzoylauramine (Finckh and dissolving the residue from the distillation of
Schwimmer, -J. pr. Chem. 1894, 50. 401) NBz :
phenol in alcohol, adding milk of lime, filtering
C(C 6 H 4 -NMe.,).,, has m.p. 179 (corr.). off the brown precipitate of calcium brunolate
Methylphenylauramine hydrochloride, de- and precipitating the red solution of calcium
phenylauramine, and pentamethyleneauramine rosolate with acetic acid. Later, Tschelnitz (J.
have been described by Stock (Ber. 1900, 33, 318 ; pr. Chem. 71, 416) and Miiller (Chem. Soc. Trans.
J. pr. Chem. 47, 401^13). The following com- 11, 1) found that the yield was greater if the
pounds, closely related to the naphthylauramines, product after addition of the lime was heated in
form the subject of a patent (D. R. P. 44077) : the air for some time, whilst Smith ( J. 1857, 448)
letraethyidiaminodiphenylmethylene naphthyl-- a - and Jourdin (J. 1861, 943) showed that crude
H
amine (Et 2 N-C 8 4 ),C N-C 10 7 , m.p. 157-
: H phenol was converted into rosolic acid by heating
158 ; dimethyldiethyldiaminodiphenylmethylene- it with soda and
manganese dioxide or mercuric
H
a-naphthylamine (Me 2 N-C 6 4 ) (Et 2 N'C 6 4 )C : N- H oxide. Kolbe and Schmitt (Annalen, 119, 169)
H
C 10 7 , m.p. 177-178 ; tetraethyldiaminodi- and, simultaneously, Persoz (Fr. Pat. 54910, July
21, 1861) obtained it by heating phenol and
H
N'C 10 7 , m.p. 155 ; dimethyldiethyldiaminodi- oxalic acid with sulphuric acid, and this method
phenylmethylene-/3-naphthylamine (Me 2 N'C 6 4 ) H was adopted for preparing the acid on the large
H : H
(Et 2 N-C 6 4 )C N-C 10 7 , m.p. 163-164. scale by Wurtz (Schmidt, Dingl. poly. J. 166,
The substituted auramines dye silk and 318) who termed it (yellow) corallin (known
wool, and also cotton after mordanting with commercially as aurin in England), and by
tannin. The shades produced on cotton are, Guinon, Marnas and Bonnet (Dingl. poly. J.
however, distinctly reddish or brownish-yellow 167, 390), who converted it into pseonin or red
compared with the pure yellow produced by corallin by digestion with aqueous ammonia at
auramine itself ; for example, the auramines 150. The reaction was further investigated by
from orthotoluidine, metaxylidine and cuini- Fresenius ( J. pr. Chem. [2] 5, 184), by Prud'homme
dine hydrochlorides dye cotton golden-yellow ; (Zeitsch. angew. Chem. [2] 19, 359), and by
those from aniline and paratoluidine dye orange- Comaille (Compt. rend. 77, 678), the last of
red, that from metaphenylenediamine dyes whom found that the proportion of oxalic acid
orange-brown, and those from a- and 0-naphthyl- used was too large. By diazotising rosaniline,Caro
amine dye brownish-yellow shades (B. A. S. F., and Wanklyn (Chem. News, 14, 37 ; Proc. Roy.
D. R. P. 29060 Fehrmann, Ber. 20, 2852).
;
Soc. 15, 210) obtained rosolic acid C 20 16 3 , H
AURANTIA (Kaisergelb) is the commercial which, however, was not identical with the pro-
name of the ammonium salt of hexanitro- duct from phenol. Caro (Phil. Mag. [4] 32, 126),
diphenylamine. moreover, showed that the formation of rosolic
Hexanitrodiphenylamine NH[C 6 2 (N0 2 ) 3 ] 2 isH acid from phenol is dependent on the presence
obtained by treating diphenylamine or methyldi- of cresol or of some simple (methane) derivative
phenylamine with nitric acid, and, after the first of the fatty series of organic compounds (com-
vigorous action has subsided, heating to compare Guareschi, Ber. 5, 1055 Zulkowsky, Anna-
;
plete the reaction. The product is then ex- len, 194, 122). The nature and composition of
tracted with water to remove any resin or picric the products obtained in Kolbe and Schmitt's
acid associated with it, and finally crystallised reaction were not, however, accurately known
from acetic acid. until 1878, when the researches of Dale and
It forms bright-yellow prisms, melts at 238 Schorlemmer (Annalen, 166, 279; 196, 75),
with decomposition, but can be sublimed in Caro and Graebe (Annalen, 179, 184; Ber. 11,
yellow needles by careful heating, and is almost 1116, 1348), E. and 0. Fischer (Ber. 11, 473)
insoluble in water, more soluble in alcohol, and and Zulkowsky (Annalen, 194, 122; 202, 179)
easily soluble in ether. It readily yields salts, established the fact that the action of oxidising
and the ammonium salt (aurantia) crystallises agents on a mixture of phenol and cresol, or of
in lustrous brown-red needles, although com- oxalic acid on phenol, results in the formation of
mercially it is obtained as a brick-red powder a mixture of red colouring matters (corallin) con-
which dissolves in water and dyes silk and wool taining two well-characterised substances termed
a beautiful orange colour (Gnehm, Ber. 7, 1399 ; aurin C 19 H 143 , and methylaurin C 20H 16 3
.
9, 1245 ; c/. Townsend, Ber. 7, 1249 ; Mertens, Aurin is the lower homologue of Caro and
AURIN AND ROSOLIC ACID. 341
Wanklyn's rosolic acid, and sometimes known

is Rudolph (Zeitsch. angew. Chem. 19, 384) heats
as pararosolic acid, since it can be obtained by paracresol (108 grams) and phenol (188 grams)
diazotising pararosaniline (E. and 0. Fischer, dissolved in 32 p.c. caustic soda solution (400
Annalen, 194, 268). grams) with sodium dichromate (300 grams)
Corallin.This name is applied to the red also dissolved in 32 p.c. caustic soda solution
colouring matter obtained by heating phenol (250 grams) for some hours at 180 under
and oxalic acid with sulphuric acid. According pressure. The aurin is purified by conversion
to Zulkowsky (Annalen, 194, 122; 202, 134; into the compound with sodium bisulphite.
Monatsh. 16, 363), a mixture of pure phenol Another process is that described by N. Caro
(10 parts) and sulphuric acid of 66B. (5 parts) (Ber. 25, 948), in which a mixture of dihydroxy-
is heated with anhydrous oxalic acid (6 parts) diphenylmethane and phenol in mol. prop, is
added in three equal quantities, at 120-130 oxidised by a cold solution of sodium nitrite in
until the mass becomes viscid and the evolution concentrated sulphuric acid.
of gas (a mixture of and C0 2 in equal volumes)
CO To obtain aurin from the commercial product,
slight. This stage is reached in about 24 hours, Dale and Schorlemmer (Annalen, 166, 280) treat
and the product is then poured into so much a concentrated alcoholic solution of corallin
water that the further addition of water does not with gaseous ammonia until crystals of the
produce a precipitate. The corallin is thus compound of aurin with ammonia cease to
separated from phenolsulphonic acid and un- form the precipitate is then heated with hydro-
;
attacked phenol, and the yield by this process chloric acid or acetic acid to remove ammonia,
amounts to 60-70 p.c. Corallin has been shown and the product repeatedly crystallised from
to be a mixture of pseudo -rosolic acid or corallin - alcohol. Asecond method, in which the com-
phthalin (70 p.c.), to which it owes its resinous mercial product is washed with cold alcohol and
consistency, with aurin, methylaurin, and, the residue repeatedly crystallised from alcohol,
according to Zulkowsky, with several other has also been described (D. and S. Annalen, 196,
products, of which very little is known. 77). A third method, due to Zulkowsky (Anna-
Properties. a brittle resinous substance
It is len, 202, 185), in which a solution of corallin in
with a green metallic lustre, and yields a red dilute soda ley is saturated with sulphur dioxide,
powder. It has been employed as a dye for silk and the resinous pseudo-rosolic acid or corallin-
and wool (Schroder, Dingl. poly. J. 204, 397), and phthalin precipitated by water, has been de-
used for printing on cotton, silk, and wool. In scribed. The separation of the aurin from the
printing with corallin, any acids with which it methylaurm, and leucorosolic acid left in solu-
may come in contact during the process must be tion, is effected by the aid of sulphur dioxide,
neutralised, otherwise a yellow instead of a !
with which aurin forms a crystalline compound.
turkey-red colour is the result. Kielmeyer ;
The process can be varied by dissolving corallin
recommends magnesia for this purpose (Wagner's in a 1-25 p.c. solution of caustic soda, precipi-
Jahr. 1872, 709). tating the clear solution by carbon dioxide,
The following substances have been isolated suspending the precipitate in water acidified
from corallin : with acetic acid, and washing finally with
it
(1) Aurin (pararosolic acid) C 19 H 14 3 or water. The precipitate (

1 then dissolved
part) is
C(C 6 H 4 -OH) 2
: C
6 4 : 0. H
The formation of the in boiling alcohol (20 parts), and the aurin sepa-
aurin present in corallin has been attributed to rated by adding to the solution one -fourth its
the reaction : volume of boiling water (Monatsh. 16, 363). The
3C 6H 6 =C 19H 14 +H CO +2H O yield of aurin by any of these methods amounts
0+H 2 C2 4 3 2 :! 2
to less than 10 p.c.
(D. and S. Annalen, 196, 79 ; compare, how- Properties. Aurin crystallises in garnet-red
ever, Zulkowsky, Annalen, 202, 184 ; E. and 0. rhombic forms, which appear rose-red by trans-
Fischer, Ber. 11, 201 ; Gukassianz, Ber. 11, mitted, and show a sky-blue lustre by reflected,
1179 ; Z. Ber. 11, 1431 ; Nencki and Schmid, light ; it does not melt at 220. In alcohol and
J. pr. Chem. [2] 25, 273) Z. Monatsh. 5, 108
; ; acetic acid it dissolves, forming yellow-red, and
Staub and Smith, Ber. 17, 1740). in alkalis and ammonia carmine, solutions. Aurin
Preparation. Aurin can be obtained by combines with sulphur dioxide, forming the
diazotising pararosaniline (E. and 0. Fischer, I.e. ; compound H 2 S0 3 + (C 19 H 14 3 ) 2 +4H 2 0, wh.^h
compare ROSOLIC ACID), but the process has no crystallises in red cubes and cubic octahedra,
practical value. It can be obtained pure and showing a green metallic lustre (D. andS. Annalen,
in good yield (95 p.c. when zinc chloride is used) 166, 1 84 ; Z. Annalen, 202, 200) ; it also combines
by heating phenol (14 parts) with carbon tetra- with alkaline bisulphites (D. and S.). Acetic
chloride (8 parts) and zinc chloride (30 parts), anhydride converts it into two triacetyl- com-
or aluminium chloride (10 parts), or stannic or H H
pounds, C 19 13 O 4 (C.2 3 0) 3 m.p. 171-172 and
,
ferric chloride (20-30 parts) at 140-160 in an 146-149, from each of which aurin can be
autoclave during 4 hours with occasional stirring. regenerated by hydrolysis (Herzig and Smolu-
The product, when cold, is purified by driving off chowski, Monatsh. 15, 73 ; Herzig, ibid. 17, 191).
unattacked phenol with steam, and removing Bromine reacts with it in acetic acid solution to
soluble impurities by extraction with water form tetrabromaurin Ci 9 Hj 3 Br 4 which yields
,
(Heumann, D. R. P. 68976 of April 3, 1892, violet solutions with alkalis, and in acid solution
expired Aug. 1893 ; compare Friedel, Bull. Soc. is a dark- violet dye for silk and wool (D. and S.
chim. 50, 2). Elbs substitutes chloropicrin Annalen, 196, 81 ; compare Z. Monatsh. 3, 465;
for carbon tetrachloride,
heating the mixture Ackermann,Ber. 17, 1624). With iodine in alkaline
for one to two days in a steam-bath, but does solution, or electrolytically with potassium iodide
not state the yield (Ber. 16, 1275). and an alkali, aurin yields a triiodo- derivative
Reference has been made to Smith's and H
C 19 n 3 l 3 . for which some pharmaceutical
Jourdin's methods of oxidising crude phenol. value is claimed (Classen, D. R. P. 85929, of
342 AURIN AND ROSOLIC ACID.
May 27, 1894). Fe<rant>oawn'nC 19Hi 3 (N0 2 ) 4, ;
of the formula H
C 19 14 O 4 , are contained in the
m.p. 140, and several ethyl ethers have been pre- j precipitation with carbon dioxide,
filtrate, after
pared by Ackermann (I.e. ; for aurindimethyl ether and recovered from it by neutralisation with
H
\
C 19 12 0(OCH 3 ) 2 , see Herzig, Monatsh. 29, 653). |

hydrochloric acid ; they are termed a- and
When an alcoholic solution of aurin is saturated j P-aurin oxides. The nature of these four
with ammonia, aurin-ammonia C 19 14 3 ,(NH 3 ) 3 H substances is unknown.
is obtained ; this crystallises in dark-red needles, !
(5) In addition to the foregoing, phenyl

and rapidly loses ammonia on exposure to air. H
ortho-oxalate C 14 14 O 6 sublimes during the pre-
If, however, aurin is heated Avith aqueous or paration of aurin, and is found on the lids of
alcoholic ammonia at 180-200 for 20 hours, it I
the aurin pots in the form of colourless needles,
yields paraleucaniline (D. and S. Annalen, 196, melting at 128. It plays no part, however, in
75) and similar treatment with methylamine and
;
the formation of aurin, but is produced by the
aniline results hi the formation of trimethyl- :
action of phenol vapour on anhydrous oxalic
and triphenyl- rosaniline respectively. Reduc- acid (Claparede and Smith, Chem. Soc. Trans.
ing agents, and zinc-dust with acetic acid in 1883, 358 ; Staub and Smith, Ber. 17, 1740).
particular, convert it
parahucaurin into Paeonin (red corallin or aurin R.) is pre-
CH(C 6 H 4 -OH) 3 which ,
from alcohol
crystallises j pared by heating 2 parts of (yellow) corallin
in colourless lustrous needles, does not melt at and 1 part of aqueous ammonia (sp.gr. =0-91)
130, yields a triacetyl- derivative, melting at j
in an autoclave at 125 -140 until a test shows ,
138-139, and on oxidation with permanganate j

the desired shade the product is then poured
;
or ferricyanide of potassium, does not yield into water acidified with sulphuric acid.
aurin, but an undetermined red product (Dale and Pseonin is a dark-red amorphous mass,
Schorlemmer; Zulkowski; Caro and Graebe, I.e.). with a green metallic lustre, and is a mixed pro-
The following hydroxyaurins have been I
duct containing among other compounds some
prepared by Nencki (J. pr. Chem. [2] 25, 275) :
pararosaniline. It is insoluble in water, but
cresolaurin C 22 H 20 3 resaurin C 19 H 14 6
; ; and alkalis, yielding purple-red
soluble in alcohol
and orcinolaurin, C 22 H 18 6
j
. do not affect the colour of its

solutions ; acids
Other hydroxyaurins, and several aurin- !
solutions. With wool and silk it gives shades
carboxylic acids have been made by N. Caro's |
intermediate between those of magenta and
process Ber. 25, 2671 ;
(I.e., J. R. Geigy j
cochineal.
and D. R. P. 49970; E. P. 3333 of
Co., i
Closely related to aurin is benzaurin (pher

For example, aurintricarboxylic
1889).
H C 19H 14
acid C[C 6 3 (OH)C0 2 H] 2 C 6 H 3 (OH) O can
j
: :
benzetn) 2
,
be obtained (a) by dissolving salicylic acid |

obtained by gently heating 1 mol. of benzotri-
(2 parts) in concentrated sulphuric acid (15 j
chloride with 2 mols. of anhydrous phenol, re-
parts) and methyl alcohol (4 parts), warming moving excess of phenol by steam distillation,
the solution to 60-70 and adding solid sodium extracting the residue with sodium bisulphite,
nitrite (1-5 parts); (b) by adding salicylic acid ! and precipitating the filtrate with hydrochloric
(2 parts) to a solution of sodium nitrite (1 part) acid (Doebner, Ber. 12, 1462 ; compare Homolka,
in concentrated sulphuric acid (10 parts), and i Ber. 18, 988). It crystallises in brick-red crystals,
adding, with constant stirring, either formalin melts at about 100, is insoluble in water, but
(0-5 part) or methylal (0-4 part) The product, soluble in alcohol, ether, and acetic acid. Alkalis
a red powder, forms lakes with metallic oxides, j
dissolve it, yielding violet solutions. The
of which that with chromic oxide is the most i
acetyl- derivative melts at 119. On reduction

valuable, being fast to soap. The ammonium , with zinc and hydrochloric acid, benzaurin
salt has found employment in calico-printing converted into dihydroxytriphenylmethane
under the name chrome violet. Ci9H 16 O 2 .
(2) Methylaurin C 20H 16 3 crystallisesin I

H
Resorcinolbenzein C 38 30 9 (Doebner, Ber.
small brick-red crystals with a green metallic 13, 610; Annalen, 217. 234; Aktieng. f. Ani-
lustre. Bromine in acetic acid converts it linfab. in Berlin, D. R. P. 4322; E. P. 72
H
into the compound C 20 12 Br 4 3 ,HBr+2H 2 0, of 1878) is obtained by heating 1 mol. of benzc
which on boiling with water yields tetrabromo- trichloride and 2 mols. of resorcinol at 180-190.
methylaurin ; this dissolves in alcohol with a It crystallises in large violet-red prisms, appear-
violet-red, and in alkalis with a magenta, colour. ing yellow by transmitted light, is insoluble
On reduction with zinc-dust and acetic acid, I in water, ether, and benzene, has a yellowish-
methylaurin yields the leuco- base C 20 18 3 , H j green fluorescence in dilute alcoholic solutior
crystallising in colourless rhombic needles (Z. ;
and yields a bromo- derivative which is sparingly
I.e. ; Monatsh. 3, 471). soluble in all ordinary solvents, and dyes woo
(3) Pseudorosolie acid (corattinphthalin or i
and silk in shades similar to those produced bj
H
phenokorallin) C 20 16 4 , is, together with other eosin.
amorphous substances, the chief constituent ;
ROSOLIC ACID (rosaurin) C 20H 16 3
TT
of corallin. In colour it is red, with a green
metallic lustre, and on oxidation with potassium
permanganate yields corallinphthalein. tising rosaniline' (Caro and Wanklyn, Cher
(4) Zulkowski (Monatsh. 16, 363) states that ;
News, 14, 37 ; compare Zulkowsky, Monatst
corallin, when prepared from pure phenol, 16, 395).
contains, in addition to aurin, two colouring Preparation. 500 grams of rosaniline ar
matters of the formulae C 20H 16 4 2O and +H dissolved in 1 \ litres of concentrated hydrochloric
C 20H 16 B +H
2 O, of which the former
is precipi- acid diluted with 1 litres of water, and the
tated from solution in alkali by carbon dioxide, filtered brownish-yellow solution diluted witi
and the latter is not. Further, two isomeric ! 150 litres of water is treated with a dilute solu-
substances, destitute of tinctorial properties, [
tion of sodium nitrite until the rosaniline has
AUTOCLAVE. 343
almost but not quite disappeared. The whole is by quenching a steel containing 0-93 p.c. carbon
then heated gradually to boiling, and filtered and 1-67 p.c. manganese from 1050 in ice-
after the evolution of nitrogen has ceased. On water (Maurer, Metallurgie, 1909, 6, 33). Steels
cooling, rosolic acid separates in lustrous containing 13 p.c. of manganese or 25 p.c. of
brownish-green crystals, and is purified by dis- nickel contain only austenite, and are soft and
solving in soda ley, saturating the solution with non- magnetic.
sulphur dioxide, filtering and precipitating the Under the microscope austenite is recognised
compound by addition of a mineral acid to the by its softness as compared with 'martensite,' with
nearly colourless filtrate (Caro and Graebe, which it is usually associated; by its structureless
Annalen, 179, 192). appearance and by the brightness of an etched,
Properties. Rosolic acid crystallises from polished section (Le Chatelier, Revue de Me'tal-
ruby -red crystals, or in greenish
dilute alcohol in lurgie, 1904).
scales with a metallic lustre, does not melt at AUTAN. A mixture of solid (polymerised)
270, and is insoluble in benzene and carbon formaldehyde and the dioxides of barium or
bisulphide, very sparingly soluble in water, strontium, used in the disinfection of living-
soluble in ether and acetic acid, and readily rooms. On mixing the powder with water, a
soluble in alcohol. In alkalis it dissolves with a rapid disengagement of formaldehyde vapour,
red colour, which in very thin layers is bluish- mixed with ox3rgen, occurs.
red, and in thick layers is yellowish-red. In AUSTRALENE v. TURPENTINE.
dilute solution the colour change from pale AUSTRIAN CINNABAR. Basic lead chro-
yellow to red on the addition of alkali is suffi- mate (v. CHROMIUM).
ciently sensitive to admit of the use of the AUTOCLAVE. An apparatus constructed on
acid as an indicator (Thomson, Chem. News, the principle of Papin's digester, for heating
47, 184). It is a feeble acid, and yields an un- liquids at temperatures above their boiling-
stable ammonium salt, crystallising in steel-blue points. Autoclaves are usually made of cast-
needles. Bromine in acetic acid solution con- iron or steel, occasionally of copper, and in some
H
verts it into telrdbromorosolic acid C 20 12 Br 4 3 , cases of sheet-iron or steel. Cast-iron auto-
which crystallises in lustrous green scales, dis- claves are sometimes
solves in alkalis with a violet colour, and strapped with steel rings
with reducing agents yields the leuco- com- for greater security.
pound. When heated with acetic anhydride They are often enamel-
at 150-200, it forms, among other compounds, led or lined with sheet-
triacetylleucorosolic acid (m.p. 148-149) ; tin, lead, copper, or zinc.
H
leucorosolic acid C 20 18 O 3 itself being obtained Metallic linings are now
by reducing rosoMc acid either with sodium soldered rigidly to the
amalgam or with zinc-dust and soda ley (Caro surface of the autoclave.
and Graebe, I.e.). They are fitted with a
A
colour reaction for rosolic acid has been pressure gauge and
described by Alvarez (Ann. Chim. anal. 12, 9). safety valve, and tubes
To obtain it, 0-05-0-1 gram, with 0-2-0-3 for the insertion of ther-
FIG. 1.
gram of sodium peroxide, is mixed with 5 c.c. of mometers, and are
alcohol, and after 4-6 minutes, 15 c.c. of water usually closed by a
are added, when an intense purple colouration is screw or flanged cover, working against a
obtained which is not destroyed by water. leaden washer, and are heated either by the
'
Azulin or Azurin. Blue colouring matters circulation of hot oil or in a bath of molten
to which these names have been given are ob- lead. As they have frequently to sustain
tained by heating (j'ellow) corallin with aniline pressures of from 20 to 30 atmos., they
(D.and S. Annalen, 166, 294 Guinon, Mamas
; are tested before use by hydraulic pressure.
and Bonnet, I.e.) or rosolic acid with aniline Occasionally they are provided with agitators
or various diamines. By substituting phenyl-
hydrazine or other hydrazines for aniline, red
dyes known as rhodazines are obtained (Ville,
D. R. P. 98436; Eng. Pat. 16039, 27775 of
1896 ; D. R. P. 100555 of 1896), and analogous
bluish-red dyes are formed when aurintricar-
boxylic acid (v. supra) or aurincarboxylic acid
(Vidal, Eng. Pat. 5535, 5689, of 1897) are substi-
tuted for corallin or aurin.
The hexamethoxy- derivatives of aurin and
rosolic acid are described under EUPITTONIC
ACID (q.v.). W. P. W.
AURUM MUSIVUM or MOSAICUM. Mosaic
gold. Made by an amalgam of 2
triturating
parts tin and 1 of mercury with 1 part sal
ammoniac and 1 of sulphur, and subsequently
subliming. Used as a bronzing powder for FIG. 2. FIG. 3.
plaster figures (v. BRONZE POWDERS).
AUSTENITE. A
solid solution of carbon in working through stuffing boxes,
in order to
iron, of
variable composition; is a constant ensure thorough mixing of the contents when
constituent of steels containing 1-1 p.c. of carbon heated.
or more when cooled 4 shows a method of
rapidly from a temperature Fig. withdrawing
of 1100-1500 . or
It be obtained
may pure portions of the contents of an autoclave,
344 AUTOCLAVE.
adding liquid without removing the cover, mineral consisting of hydrated phosphate of
when the apparatus is in use. The three-way uranium and calcium Ca(U0 2 ) 2
P 2 O g -8H 2 0, which
valve A is adjusted so as to prevent passage within recent years has been somewhat ex-
through the pipe e. In order to withdraw a tensively mined as an ore of uranium and radium.
sample, the three-way cock B is made to communi- It is a member of the isomorphous group of
'
cate with b and d, and the valve A turned with minerals known as the uranium micas,' which
a jerk so as to connect e with b ; the sample is crystallise in square, tetragonal (or
very nearly
then withdrawn at d. To completely remove square, orthorhombic) plates with a perfect
the charge the valve A is left open for some time. micaceous and pearly cleavage parallel to their
In working without pressure the air-cock c is surface. In the orthorhombic autunite the
opened, and communication established between colour is characteristically sulphur-yellow, or
sometimes with a greenish tinge, so that this
mineral is readily distinguished from the
emerald-green torbernite or cupro-uranite. Sp.gr.
3-1 ; H. 2-2. It occurs as an alteration
product of pitchblende, and is often found as
a scaly encrustation on the joint-planes of
weathered granite or gneiss. The more im-
portant localities are St. Symphorien, near
Autun in France (hence the name autunite) ;
St. Just, Redruth, and Grampound Road in
Cornwall Johanngeorgenstadt and Falken-
;
stein in Saxony ; Black Hills in South Dakota ;
and Sabugal, near Guarda in Portugal. At

the last-named locality several mines have
recently been opened up ; the crude ore is here
leached with sulphuric acid, and the extracts
sent to Paris for further treatment. L. J. S.
AVA or Kava-kava. The root of Piper
methysticum (Forst, f.), growing in the islands
of the Pacific. It is taken as an intoxicant by
the natives, and is used as a drug on the Con-
tinent. It is often adulterated with matico
and annatto (Pharm. J. [3] 7, 149).
AVENTURINEorAVANTURINE. A variety
of quartzfound at Capa de Gata, Spain, spangled
throughout with minute yellow scales of mica,
FIG. 4. is known as aventurine quartz. An aventurine
felspar or sunstone is found at Tvedestrand,
b and c and a' and b ; b and c are then filled with
Norway. It is used for ornaments.
liquor identical in constitution with that con- Artificial aventurine, or glass, or gold flux,
tained in the apparatus obtained from a previous was manufactured for a long period at the glass-
operation. The contents of the vessel are then works of Murano, near Venice. It may be pre-
removed by restoring the communication between pared by adding to 100 parts of a not too re-
e and b and b and d. To introduce liquor into the
fractory glass, 8 to 10 parts of a mixture of equal
apparatus without removing the cover, the air- parts of ferrous and cuprous oxides, and allowing
cock c is opened, and the funnel a' made to com- the mixture to cool very slowly so as to facilitate
municate with, the pipe e by regulating the valve A. the formation of crystals.
Sometimes it is more convenient, as shown in Aventurine glaze for porcelain, invented by
Fig. 2, to provide a loose container for the Wohler (Annalen, 70, 57), is prepared by finely
substance under treatment. J. W. H.
grinding 31 parts Halle kaolin, 43 quartz sand,
AUTOLYSIS. A physiological term signifying 14 gypsum, and 12 porcelain fragments ; making
self-destruction, and used to indicate the de- the whole into a paste with 300 parts water, and
structive changes (apart from putrefaction due
adding successively 19 parts potassium dichro-
to micro-organisms) which occur in cells after mate, 47 lead acetate, 100 ferrous sulphate, and
death or removal from the living body. These sufficient ammonia to
precipitate the whole of
changes are due to the action of intra-cellular the iron. After the soluble potash and am-
enzymes, and are analagous to those which monium salts have been washed out, the glazing
occur in digestion ; indeed the term auto-diges- is ready for use.
tion is sometimes employed. The study of such AVIGNON GRAINS. The seeds of Ehamnus
changes is important because it is believed that infectorius, employed in dyeing for the produc-
the change after death, when the cells are still tion of
'
yellow colours (v. Rhamnin, art. XAN-
surviving for a time, are identical with those THORHAMNIN).
'
which occur during life and result in the forma- AVOCADO PEAR or ALLIGATOR PEAI
tion of waste substances, the products of vital The fruit of Persea gratissima, a tropical product
activity. During life, however, the destructive The fruit, which usually weighs from 4 to
changes are counterbalanced by changes in the oz., consists of rind (about 8 p.c.), fles
opposite direction by which the cells build them- (67 p.c.), and a large stone
'
or
''
pit
'
(abot
selves up from food materials to repair their 25
p.c.). According to Prinsen-Geerlings (Cher
wear and tear. Assimilation of this kind is Zeit. 1897, 21, 715), the flesh contains :
obviously impossible after death. Glucose Fructose Saccharose Total sugar

AUTUNITE or CALCO - URANITE. A 0-40 0-46 0-86 1-72
AZINES. 345
Theflesh, which has a nut-like flavour, is (Miller and Tschitschkin, Chem. Zentr. 1899,
usually eaten with pepper and salt. An analysis, ii.
181); Harris and Tank (Ber. 1907, 4555)
made by Jamieson (Chem. News, 1910, 102, 61), have shown that a complex mixture of cyclo-
gave : ketones is obtained by distilling the calcium
Water Ether extract Protein Sugar Fibre Ash salt of azelaic acid. Azelaic anhydride is
66-9 10-6 5-7 1-1 4-0 2-0 obtained by heating azelaic acid with 7-8 pts.
The ether extract was green, and contained of acetyl chloride. It melts at 56-57 (fitaix,
about 4 p.c. of resins. After their removal, an Ann. Chim. Phys. [7] 9, 399).
oil, resembling that of bergamot, was obtained, AZELAONE v. AZELAIC ACID.
which had an iodine value of 29-9, and saponi- AZIDINE BLACK, -BLUE, -BORDEAUX,
fication value of 207. H. I. -BROWN, -FAST RED, -FAST SCARLET,
AVOCADO PEAR, pIL OF. An oil obtained -GREEN, -ORANGE, -PURPURINE, -YELLOW,
from the oleaginous fruit of the Persea gralissima. -VIOLET, -WOOL BLUE v. Azo- COLOURING
Hofmann stated that for the purposes of the MATTERS.
soapmaker this oil would be as valuable as AZIMINOBENZENE v. DIAZO COMPOUNDS.
palm oil. AZIMINONAPHTHALENES v. DIAZO COM-
AWAL or Tarwar. An Indian drug, the POUNDS.
bark of Cassia auriculata (Linn.) (Dymock, AZINES (Quinoxalines). Azonium bases,
Pharm. J. [3] 7, 977). and colouring matters derived from them.
AWLA v. AMLAKI. Definition.- -The term 'azines' has been
AXIN. A waxy secretion of a Mexican given to a group of organic bases, which contain
rhynchotrous insect Llaveia axinus which feeds in their molecule as an intrinsic part of their
on Spondias lutea, Xanthoxylum Clava-herculis, constitution a heterocyclic hexagonal ring, built
and X. pentanome : has the consistence of butter, up of four carbon and two nitrogen atoms,
the smell of rancid fat, and a yellow colour.
arranged in such a manner that the nitrogen
Melts at 38, and is soluble in hot alcohol and atoms stand in para-position to each other,
ether. Rapidly absorbs oxygen from the air, whilst the four carbon atoms are disposed in
becoming brown, hard and insoluble in two pairs between them, thus :
alcohol and ether. Is readily saponified, yield-

ing axinic acid and glycerol. It resembles
Japan lac and forms an excellent kcquer for
wood, metals, and pottery (Bocquillon, J. Pharm. c
Chim. 1910, 2, 406; J. Soc. Chem. Ind. 29, c
X
1320).
'
AZADIRACHTA, Margosa, or Nim. The The term azine,' first proposed by Merz, is
bark of the nim tree, Melia indica (Brandis) not happily chosen, and is even misleading, as
[M. Azadirachta], is commonly used in India as it enters into the names of other nitrogen
a tonic and febrifuge. It contains a bitter resin. compounds of a different constitution, such as
An oil, used in medicine and for burning is the hydrazines.
' '
expressed from the seeds, which on saponifica- The name quinoxaline was given by
tion yielded 35 p.c. of fatty acid melting at 30, Hinsberg to compounds which also correspond
and 65 p.c. melting at 44. with the above definition. It was, therefore, con-
AZELAIC ACID. Lepargylic acid. C0 2 H' sidered for some time as synonymous with the
(CH 2 7 'C0 2 H. It is obtained by oxidising
)
word ' azine,' which latter was, however, more
Chinese wax (Buckton, J. 1857, 303), cocoanut frequently used. In later years it has become
oil(Wirz, Annalen, 104, 261), or castor oil (Arppe, customary to distinguish between the two terms,
Annalen, 124, 86) with nitric acid by the ;
and to use them for the two tautomeric forms
oxidation of oleic acid with potassium perman- in which these bases occur (see Theory).
' '
ganate and caustic potash (Ehmed, Chem. Soc. The name azonium bases has been given
Trans. 1898, 627), and by the oxidation of keratin by Witt to a class of organic bases, derived from
(horn shavings) with permanganate (Lissizin, the azines by the linking of ar organic radicle to
Zeitsch. physiol. Chem. 1909, 226). It is formed one of the nitrogen atoms, whereby this atom
together with other products when fats or oleic passes from the trivalent into the pentavalent
acid become rancid (Scala, Chem. Zentr. 1898, state, a process which results in a very marked
i.
439). It has been synthesised from penta- change of the properties of the substance.
methylene bromide and sodium acetoacetate Both the azines and azonium bases possess
(Haworth and Perkin, Chem. Soc. Trans. 1894, the nature of powerful chromogens, the hetero-
86), and has been obtained by decomposing the cyclic ringabove mentioned being endowed with
ozonide of oleic acid (Molinari and Soncini, strong chromophoric properties. Being highly
Ber. 1906, Harries and Thiome, ibid.
2735; basic and capable of assuming a quinonoid struc-
1906, 2844 Molinari and Fenaroli, ibid. 1908,
; ture (see Theory), they, and especially the
2789). It is best prepared by
oxidising with azonium bases, possess to some extent the
potassium permanganate an alkaline solution nature of dyestuffs, which is, however, much
of rieinoleic acid obtained more strongly developed by the introduction of
by the hydrolysis of
castor oil (Maquenne, Bull.' Soc. chim. 1899,
separate auxochromic groups. very large A
(iii.) 21, 106 ; Hazura and Griissner, Monatsh. number of powerful colouring matters of great
9, 475). Azelaic acid crystallises in colourless intensity, variation, and purity of shade may
plates, m.p. 106-2 (Massol, Bull. Soc. chim. thus be obtained, some of which have acquired
[3] 19, 301), and is readily soluble in alcohol, considerable practical importance. According
less soluble in water or ether. to their constitution, which is in almost all cases
By heating
completely cleared up, they have been classified
azelaic acid with soda lime, azelaone (cy,lo-
?ionanone)C 8 H 14 0,b.p. 205 (circa), is obtained into groups, which have received the names
AZINES.
eurhodincs, eurhodols, safranines, sa- element or radicle. The simplest possible com-
franols, aposafranines, indulines, and pound of the kind would thus have the formula
fluorindines. NH
C 4 2 4 . It seems natural to suppose that it
The investigation of the azines and their would be the prototype of all the azines.
derivatives, which was accomplished by a num- i
Such a compound exists and is well kno\
her of chemists during the last 20 years of It has received the name pyrazine. Mar
the nineteenth century, has been of considerable derivatives of it, formed by the substitution of it
importance in the development of our present hydrogen atoms by monovalent organic radicle
views on the constitution of colouring matters, are also known ; they form the large and wel
and especially in the adoption of the modern investigated class of the ketine or aldine ba
quinonoid structural formulae for the great But neither pyrazine itself (which in its propertie
majority of them. resembles pyridine, to which it stands in the
History. The two simplest and most same relation as pyridine stands to benzene) nor
typical members of the azine group, diphenazine the ketines show any resemblance to the typical
and dinaphtazine, have been known for many j
azines. They exhibit no colourations, nor do
' '
years as azophenylene (Glaus and Rasenack,
'
they form any derivatives which have the nature
'
1873; Annalen, 168, 1) and naphtase j
of dyestuffs. For this reason pyrazine and the
(Laurent, 1835 ; Ann. Chim. Phys. 59, 384), ketines are no longer considered as belonging to
but their constitution was not properly under- <
the azine group.

stood and then: importance not recognised. The characteristic properties of the azines
Merz (1886, Ber. 19, 725) finally proved the !
only appear in compounds in which at least

constitution of tht> former, which had been in- one other ring system is linked to the pyrazine
sufficiently substantiated by Glaus, and pro- ring, in such manner that one of the C 2 -groups
posed for it the name diphenazine ; Witt (1886, of the latter becomes part of an aromatic
Ber. 19, 2791) determined the true nature of radicle. The process may be repeated. Thus
'
naphtase.' In 1884 Hinsberg (Ber. 17, 319) the simplest representatives of the azine group
described a general method for preparing his would be compounds of the following type :
quinoxalines, which proved most fruitful in the !
N\ /H
further development of the subject. Other ,
cr
general methods were discovered by Witt, Merz,
Japp, Ullmann, and others. UV a
/C\ X U\ U /ON
The first eurhodines were prepared by Witt
in 1879 and 1885. He recognised that they \/ \\W/
VyAAv N//Ox\H \/
Phenazine.
^S, /<-
\Nx
Diphenazine.
formed a new class of dyestuffs, and also
The nomenclature of the true azines has
that they were related to the safranines. He chosen accordingly. The aromatic radicle or
determined their constitution in 1886 (Ber. 19, '
radicles linked to the central (or meso -') ring
441) by showing that they are the amino- deriva- are prefixed to the syllables -azine.
tives of the azines or quinoxalines. At the The azines are members of the aromatic
same time he discovered the first eurhodol. The series. If we consider them as such, we recognise
natural consequence of this discovery was the
at once a strong analogy to other substances
clearing up of the nature of the safranines, which contain heterocyclic rings linked to
which were recognised in the same year simul-
aromatic radicles, such as :
taneously and independently by Witt, Nietzki,
and Bernthsen as diamino- derivatives of the
(then hypothetical) azonium bases. The first
representative of this new class of bases was
prepared in 1887 by Witt (Ber. 20, 1183).
The subject was now taken up and rapidly
advanced by many chemists, amongst whom
Nietzki and his collaborators, Kehrmann,
Ullmann, and their collaborators, may be cited.
Otto Fischer and Hepp also did a considerable Anthraquinone.
amount of work in this domain, and especially /CK
in the investigation of the indulines and apo-
safranines.
The typical indulines and safranines have
been discovered by purely empirical methods
in the early days of the colour industry. The H H
simplest representative of the group, pheno- Oxazine. Thiazine.
safranine, was prepared by Witt in 1877. Its all of which are chromogens,
like the azines.
phenylated derivative is mauve'ine, the first arti- If we
consider the manner in which the six
ficialdyestuff prepared by W. H. Perkinin 1856. atomicities of the two nitrogen atoms contained
Theory. It has been already stated that in the meso- ring of an azine may be disposed, we
the essential part of the molecule of an azine is recognise two possibilities which are repre-
the heterocyclic ring consisting of two atoms sented in the following structural formulas of
of nitrogen and four of carbon. Each of these diphenazine :
six atoms has three atomicities engaged in the

formation of the ring ; the nitrogen atoms have, C
therefore, no free atomicities left (so long as they
remain in the trivalent condition), whilst each
of the carbon atoms has one atomicity free to be
saturated by hydrogen or another monovalent
AZINES. 347
C=0 HN2 Her^N

=2H,0 +
c
\/c \N/%/c C=0 HN2 HC
II.
Glyoxal. o-Phenylenediamine. Phenazine
Formula I. is the one first proposed by Claus (quiuoxaline).
azophenylene,' and by Merz for his
'
for his works most cases so
It in well, that it has been
azines ; II., the one suggested by Hinsbergfor his recommended by its author (Annalen, 273, 343,
quinoxalines. Practically, there is no difference method of identifying either an
371) as the best
between azines and quinoxalines; they form orthodiamine or an orthodiketone. Very small
one group ; but it has been for a long time
quantities of the ingredients are necessary, and
a matter of opinion which of the above the azine formed is easily recognised by its
formulas was more adapted to the properties of
Formula its
melting-point and sulphuric acid reaction.
these substances. I. explains by reaction be extended to
the extreme stability of the Hinsberg's may
perfect symmetry nitroso-/3-naphthol, which is in reality the
azines, the fact that they may all be distilled oxime of ortho-naphthaquinone. Ullmann and
without the slightest decomposition at extremely Heisler obtained (Ber. 42, 4263) naphthaphen-
high temperatures. Formula II., on the other
azine by heating ortho-phenylenediamine hydro-
hand, is distinctly (ortho-) quinonoid, and con- chloride with nitroso-#-naphthol
-0-napl :
sequently suggestive of chromogenic proper-

ties.
H,N
Theexisting difference of opinion as to the NOH
constitution of the azines has been finally dis- + HC1
posed of by the admission that the azines are
undoubtedly tautomeric, capable of assuming
either of the constitutions I. and II., accord-
In their free state, in Nitroso-/3-naphthol. Orthophenylene diamine.
ing to circumstances.
which they are volatile and almost colourless,
they possess the symmetrical (azine-) constitu-
tion I., whereas in their intensely coloured salts +H 2 + NH 2 OH-HC1.
they have more probably the asymmetrical, Hydroxylamine
quinonoid (qumoxaline-) constitution II. In the hydrochloride.
colouring matters derived from the azines, the
Naphthaphenazine .
case is frequently complicated by the fact that

the auxochromic groups participate in the 4. The method of Merz (Ber. 19, 725) is of
formation of the quinonoid constitution, which, less general application. It consists in the
derivatives upon
by that means, may become para- as well as action of orthodihydroxyl-
orffeo-quinoid. Sometimes it is difficult to orthodiamines : the hydro- derivatives of the
decide between the existing possibilities. azines are formed, and these are oxidised by
Synthetical methods for the production of
the oxygen of the air into the azines :
i
azines, and their derivatives and description of

some typical representatives of the group. +
Azines.
I. (a) Synthetical methods. (These
will be referred to in the description of typical
Pyrocatechol. Orthophenylene diamine.
representatives by their number.)
1.
By heating o-nitronaphthalene with
powdered quicklime, Laurent (Ann. Chim. Phys. = 3H0
59, 384) obtained dinaphthazine, which he
called naphthase. Doer (Ber. 3, 291) and
Klobukowski (Ber. 10, 573) modified the method Diphenazine.
by replacing the quicklime by zinc-dust. Schi- 5.Early investigators had studied the re-
chuzky ( J. R. 6, 2464) used lead oxide. action of ammonia under pressure upon benzoin
Wohl and Aue (Ber. 34, 2443) observed (1901) (Erdmann, Annalen, 135, 181) and phenanthra-
that nitrobenzene gives considerable quantities quinone (Sommaruga, Monatsh. 1, 146). Japp
of diphenazine on being heated with strong and Burton showed that the free ammonia
caustic soda, a reaction which is practically may be advantageously replaced by ammonium ' '
identical with the one discovered by Laurent. acetate, and proved that the ditolane azotide '
2. Claus and Rasenack
(Annalen, 168, 1) I
and
'
phenanthrene azotide obtained were

'
obtained azophenylene ' (diphenazine) by the i
tetraphenylketine and diphenanthrazine. They
dry distillation of orthoazobenzoic acid in the generalised the method
and applied it to j8-
shape of its calcium or potassium salt. Claus naphthaquinone, from which they obtained
proposed the azine formula for his product, but ;
dinaphthazine (Chem. Soc. Trans. 1887, 98).
failed to afford
convincing proofs for it. 6. Another mode of formation of the azines
3. A
general method of great applicability j
consists in the joint oxidation of a phenol, hi
was indicated by Hinsberg (Ber. 17, 319 ; 18, which the para- position is no longer open to
1228), who showed that whenever an alpha- or substitution, and aromatic orthodiamines. This
j
w</to-diketone reacts on an aromatic ortho- method was discovered by Witt (Ber. 19, 917),
diamine, two molecules of water are given off who used it for the production of a new isomeride
and an azine is formed. The method was first of tolunaphthazine by oxidising a mixture of
applied to the production of phenazine : l8-naphthol and orthotolylene
diamine :
348 AZINES.
mon. As a rule, they are solid, well-crystallised
compounds of white, pale yellow, or even orange
colour, possessing a high melting-point, and
+ 20 boiling under atmospheric pressure at very high
CH 3 temperatures (in some cases approaching red
Orthotolylene diamine.
heat) practically without decomposition. They
sublime at temperatures below their boiling-
point, and their vapours condense into volu-
minous aggregates of crystals.
All the azines are bases which form salts
with acids. The mono-acid salts, with the
+ 3H 2 0.
stronger mineral acids, may generally be obtained
in a crystallised condition ; but they are stable
only in the presence of an excess of acid or in
N/ the absence of water, which easily decomposes
Tolunaphthazine. them into their constituents. These salts are
7. An modification of the above intensely coloured, a fact which justifies the
elegant
method was devised inference that they contain the base in the
in 1905 by Ullmann and
quinonoid (quinoxaline) form. The hydrolytio
Ankersmit (Ber. 1811), who heated 0-
38,
action of the water is therefore accompanied by
naphthol with orthoaminoazotoluene. The
the tautomeric' change into the symmetrical
latter takes up the
hydrogen liberated in the These salts, some of which have
reaction, yielding at the same time the necessary (azine) form.
been analysed, invariably contain one equivalent
orthodiamine.
of acid for one molecule of the base. The di-acid
C 7H 7 salts cannot be isolated, but evidence of their
existence is given by the intense red, violet, or
N blue colourations exhibited by the solutions of
azines in a great excess of strong acid, preferably
N sulphuric acid. If water be added to these
/x J-OH solutions, a change takes place ; the di-acid
/3-Naphthol. -XTTT _ salt is decomposed, the yellow or orange mono-
acid salt is formed, and, on further addition of
>-CH 3 a large excess of water, the free azine itself
Orthoaminoazotuluene. separates out in flakes. These striking colour
reactions are highly characteristic, and form the
best means of identifying the azines.
Notwithstanding these intense colourations,
the azines are not applicable as dyestuffs. They
are only to be considered as chromogens and
+H 2 0.
suitable to produce colouring matters by the
introduction of auxochromic groups into their
CH 3
molecules. They are thus strictly analogous
to the other heterocyclic chromogens such as
Tolunaphthazine.
anthraquinone, acridine, oxazine, and thiazine.
8. A
very peculiar mode of formation of There is, however, one group of azines to
these substances was discovered by Witt (Ber. which all the rules and general characteristics
20, 571), who showed that the orthoazo- deriva- given above cannot very well be applied. These
'
tives of secondary amines, and more especially are the Indanthrenes,' certain azines of the
of such amines containing the j8-naphthyl- group, anthracene group, which, owing to their large
are decomposed by being heated with acids into molecule and very complicated constitution,
the corresponding azine and amino- compound, possess properties quite different from all the
thus : other azines. They are intensely coloured and
extremely valuable as dyestuffs if applied to the
' '
textile fibre by the
vat process like indigo.
This peculiar mode
of application brings them
N into close relationship with indigo, and they will
II C 6H 5 therefore be treated in this work under INDIGO
N =
I
+ N AND INDIGOID DYESTTJFFS
NH 2 X (c)
(q.V.).
Description of some typical representatives
Aniline.
of the azine group.
Diphenazine
Benzene-azo-phenyl- Naphthaphenazine.
0-naphthylamine. C 12 H 8N 2 =
The reaction simple and easy, and gives,
is
as a rule, excellent yields. It is in reality a
condensation of the secondary amine into the (Glaus, Annalen, 168, 1 ; Benithsen, Ber. 19,
corresponding azine by the dehydrogenating 3256 ; Ris, Ber. 19, 2206 ; Wohl, Ber. 34, 2443)
influence of the azo- group temporarily intro- j
has been obtained by the methods 1, 2, and 4.
duced for the purpose. It forms pale-yellow needles, of the m.p. 170-
(b) Generic characters of the azine group. All 171, soluble in alcohol and most other solvents.
azines have certain peculiar properties in com- It distils without decomposition. It dissolves
AZINES. 349
in strong acids, forming unstable salts of yellow The third

tolunaphthazine, discovered by
and red colour. Hinsberg (Annalen, 237, 343a, 371) (method 3),
Toluphenazine has been proved to consist of a molecular com-
bination of the two preceding ones ; its melting-
C1 point is 139-142.
Several other tolunaphthazines are theore-
tically possible. They have not, however,
hitherto been prepared.
has been prepared by Merz (Ber. 19, 725) by the
action of pyrocatechol on orthotolylenediamine Dinaphthazines C 20 12 2 H N
It has already .
been stated that Laurent's mysterious naph-

(method 4). It is very similar to diphenazine.
thase,' prepared by method 1, finally proved to
Its in.p. is 117, its b.p. 350.
be dinaphthazine. It is probable that Laurent's
Naphthaphenazine
product was a molecular combination of two of
the four isomeric dinaphthazines foreseen by
theory. A similar mixture may be obtained
by reacting with a-naphthylenediamine upon
-naphthaquinone (method 2). This method
was used by Witt in his identification of
' '
Laurent's naphthase
(Ber. 19, 2791). For
preparing the constituents of this mixture in a
pure state the synthetical method 8 should be
resorted to ; it consists in the decomposition of
has been prepared by Witt (Ber. 20, 571). The
the azo- derivatives of the two isomeric (a, fi, and
best mode of obtaining it is by the decomposi-
tion, by acid, of the azo- compounds derived from
)-dinaphthylamines (Matthes, Ber. 23, 1329
and 1333). The compounds thus obtained
phenyl-/3-naphthylamine, but it has also been have the following constitutions and melting-
prepared by the action of ^-naphthaquinone on
and by simultaneous points :
orthophenylenediamine
oxidation of the latter and -naphthol. It forms
yellow needles, melting at 142 '5, distilling at a
high temperature without decomposition, and
dissolving in sulphuric acid with a reddish-brown
colouration. On dilution, two sulphates crystal-
lise from this solution. It is supposed that the
formation of two series of monacid salts of this
base is due to either of the two nitrogen atoms
o, a, j3, /3. m.p. 283-284. a, /3, /3, a. m.p. 242-243
becoming pentavalent and saturated with the
acid. The two other possible isomerides :
Tolunaphthazines H N
C 17 12 2 Three sub- . NX
stances of this formula are known, the isomerism
of which has been discussed by Witt (Ber. 20,
577). One of these, melting at 179-8 has been
prepared by the simultaneous oxidation (Ber.
19, 917) of orthotolylenediamine and j8-naph-
thol (methods 6 and 7). Its constitution is
expressed by the formula
m.p. 240
may be obtained from /3-naphthylenediamine
by the reaction of the two orthonaphthaquinones
(method 2), but, so far, only the asymmetrical
one has been prepared by Otto Fischer and
Albert (Ber. 29, 2087).
It dissolves in
sulphuric acid with a violet colour- Azines of the Phenanthrene group. Owing
ation. The other is formed by the decomposition to the extreme facility and precision with which
by acids of the azo- derivatives of paratolyl-
phenanthraquinone acts upon all orthodiamines,
fl-naphthylamine (Ber. 20, 577) (method 8). these azines are most easily prepared, and
Its constitution is
represented by the formula phenanthraquinone is commonly used for
CH, deciding the question whether any given
aromatic diamine is an ortho- compound. A
large number of azines has thus become known,
of which only a few may be described as typical
representatives of the group.
N Phenanthraphenazine C 20Hi 2 N 2 (isomeric
with dinaphthazine) may be obtained by acting
on orthophenylenediamine with either phen-
anthraquinone in an acetic acid solution (Hins-
berg, Annalen, 237, 340), or with phenanthra-
Its
melting-point is 169; its sulphuric acid quinone sodium bisulphite in an aqueous solu-
reaction is similar to that of naphthaphenazine. tion (method It crystallises in pale-yellow
2).
350 AZINES.
needles, melting at 217, and dissolves in sul- A large number of other less important azines
phuric acid with a beautiful red colouration. have been prepared in experiments made with a
Its constitution is view to showing that certain compounds
obtained by the authors were either orthodike-
tones or orthodiamines.
II. Colouring matters derived from azines
(eurhodines and eurhodols).
It has already been said that by the intro-
duction of an auxochromic group, NH
2 or OH,
into the molecule of an azine, the latter is trans-
formed into a colouring matter. The amino-
A be obtained from derivatives of azines containing either one or
similar substance may several amino- groups, are embraced by the
orthotolylenediamine. It melts at 212-213.
H
Phenanthranaphthazine C 24 14 N 2 is easily generic name of eurhodines, whilst the name of
eurhodols has been given to the phenolic (OH)
obtained (Lawson, Ber. 18, 2426) from ortho-
derivatives of the azines. The following is an
naphthylenediamine and phenanthraquinone enumeration of the various methods by which
(method 2). It gives a violet colouration with
The eurhodines and eurhodols have been obtained
M.p. 273.
:
sulphuric acid. sulphonic
acid derivatives of this substance, C 24 H 13 N,- A. EUBHODINES.
S0 3H, are obtained (Witt, Ber. 19, 1719";
21, 3485 seq.) by acting with an aqueous
1. By heating together any orthamino-azo-'
solution of phenanthraquinone sodium bisul- compound and the hydrochloride of certain
aromatic monoamines, such as, for instance,
phite upon the solutions of the various naphthyl-
enediamine sulphonic acids in sodium acetate a-naphthylamine or o-aminoquiDoline, preferably
in a phenol solution, monoamino-azines (the
solution, acidulated with acetic acid. These
eurhodines proper) are obtained. It was by this
sodium salts are soluble in pure water ; very
small quantities of alkaline salts are sufficient process that the first eurhodine was discovered
to precipitate them from these solutions. by Witt in 1883 (Ber. 18, 1119; 19, 441) by
H N
Chrysotoluazine C 25 16 2 and Chrysonaphth- heating orthaminoazotoluene with naphthyl-
H N amine hydrochloride. In this reaction an ortho-
azine C 28 J6 2 have been prepared by Lieber-
mann and Witt (Ber. 20, 2442) from chryso- diamine is formed by the reduction of the amino-
azo compound, which combines with a-naph-
quinone and the corresponding orthodiamines
The same authors obtained azine thylamine, hydrogen being eliminated and
(method 2).
absorbed by the amino-azo- compound still till
derivatives from the quinone of picene.
H N
Tolustilbazine C 21 16 2 was discovered by present.
Hinsberg, who described it under the somewhat C 7 H 10N 2 + C 10H N = 6H + C 17 H 13 N 3

9 .
Orthotolylene-
misleading name
' '
a-Naphthyl- Typical
Diphenyltoluquinoxaline diamine. amine. eurhodine.
(Annalen, 237, 339). It is typical of the many
azines which may be obtained by the action of 2. Another method of much greater appliica-
benzil upon aromatic orthodiamines. with o-diketones upon
bility consists in reacting
It separates in silvery leaflets from an aromatic triamines, which contain two amino-
alcoholic solution of benzil mixed with a solution groups in the ortho- position. Two molecules
of orthotolylenediamine (method 2). It melts of water are eliminated for every molecule of
at 111, and dissolves with a crimson shade in eurhodine formed. Thus, for instance, a eurho-
Its constitution is expressed by dine was obtained from triaminobenzene and
sulphuric acid.
the formula phenanthraquinone (Witt, Ber. 19, 445) :
NH
CH,
NH NH
The corresponding derivative of orthonaph-

thylenediamine was prepared by Lawson (Ber.
18, 2426).
Toluindazine C^H^N,,, the azine derivative
of isatine, has been prepared by Hinsberg + 2H 3 0.
(Annalen, 237, 344) from orthotolylenediamine
and isatin, by melting together the ingredients H,N
(method 2) and crystallising the product obtained
from a mixture of alcohol and acetic acid. It
3. Another method of considerable applica-
forms yellow needles, melting at 290, and dis-
bility consists in heating together nitroso-amines
solving in acids with a brownish-red colouration.
Its constitution is (Witt, Ber. 21, 719) or quinonedichlorimides
expressed by the formula (Nietzki a. Otto, Ber. 21, 1598) with aromatic
H amines in which the para- position to the amino-
group occupied by some radicle. Thus, for
is
instance, a eurhodine is formed by heating
CH. together nitrosodimethylaniline hydrochloride
N' and 0-naphthylamine, in an acetic acid soluti""
AZINES. 351
HC1
N(CH 3 )2
HN2
+C 6 H 5 NH +H 2 2
Aniline.
0rNaphthylamine.
NO
K itrosodimethylaniline
hydrochloride.
HC1
NH 2
HC1
(GH 3 ) 2 N (CH 3 )2
N
Eurhodine.
6. Diaminoazines are formed
by the de-
composition of certain indamines when their
solutions are boiled for a certain time.
+ 3H + Thus
2
tolylene blue, the indamine produced the by
2 N action of nitrosodimethylaniline hvdrochloride
upon metatolylenediamine, is decomposed if
NH 2 its solution be boiled for some
time, dimethyldi-
Parapheny lenedi me - aminotoluphenazine (tolyleno red) being the
Dimethylaminonaphthaphen- principalproduct of this reaction (Witt, Ber.
azine hydrochloride.. 1 1, 931 ) i
and an analogous, ^~
though somewhat different Xp-^3
N
reaction takes place
if the
nitrosodimethylaniline CR,
be substituted by
dichloroquinonimide.
Cl C 6H 4
N N NH
NH,
NH 2
NH,
CH,'
CH a
NH
Tolylene blue. Leuco tolylene blue. Tolylene red_
(dimethyldiamino-
toluphenazine) .
Dichloroquinonimide
Di- and polyamino- azines may also be pre-
7.
HN 2
pared by the oxidation of orthodiamines and of
polyamines containing two amino- groups in the
ortho- position. Thus 0. Fischer and E. Hepp
+ 2HC1. proved (Ber. 22, 355) that the red substance
which is formed by the oxidation of orthophenyl-
enediamine and which has been observed by
many investigators (Griess, Ber. 5, 202 Sal- ;
kowski, Annalen, 173, 68 Rudolph, Ber. 12,

;
2211 Wiesinger, Annalen, 224, 353), is nothing

;
Aminonaphthaphenazine. else And Nietzki and
than diaminophenazine.
4. Eurhodines Miiller obtained (Ber. 22, 447) by oxidising
proper may also be obtained
by the reduction (with ammonium sulphide) of tetra-aminobenzene with a current of air tetra-
nitro-azines. Thus, for instance, nitropheno- aminophenazine. Aminooxyphenazines may
phenaathrazine may be reduced into the eurho- sometimes be found as by-products in this
dine aminophenophenanthrazine (Heim, Ber. 21, reaction (Ullmann and Mauthner, Ber. 35,
2306). 4302 and ibid. 36, 4026).
5. If certain azo- colours, such as
chrysoiidine,
be heated with 0-naphthol, an eurhodine is B. EUBHODOLS.
formed : (Ullmann and Ankersmit, Ber. 38, 1812) :
These may likewise be prepared by various
methods.
1. The
sulphonic acids of azines, fused with
potash, readily yield the corresponding oxyazines
or eurhodols (Witt, Ber. 19, 2791 ). For instance :
Q 24 H 13 N 2 S0 3 Na+2NaOH
Sodium naphthaphenanthirazinesulphonate.
+ II =C 24 Hi N ONa+Na
3 2 2 S0 8 .
NH,
\/ Phenanthranaphthaeurhodol
Several eurhodines (amino-azines) yield
2.
.
/3-Naphthol. the corresponding eurhodol on being heated

under pressure with strong acids, a hydrolysis
taking place in the circumstances (Witt, Ber.
19, 444) :
NH a H N
C 17 n 2 -NH 2 +H 0=NH
3 +C 17 n 2 -OH. H N
2
Chrysoidine. Typical eurhodine. Eurhodol.
352 AZINES.
3. Diazo-azines, on being boiled with water, of a crimson colour. Its solution in sulphuric
yield the corresponding eurhodols ; on being acid changes by the addition of water from red-
boiled with alcohol they yield the alkyl ethers dish-brown through green into red. It forms a
of these eurhodols (Witt/Ber. 19, 444) : diazo- compound which, when boiled with alco-
hol, yields .the ordinary naphthaphenazine, of
Diazoeurhodine chloride. the melting-point 142-5. The following com-
H
=HC1+N 2 +C 17 11 N 2 OH. pound is its dimethyl derivative :
Eurhodol. Dimethylamlnonaphthaphenazine C 18 H 15 N 3
H : H
C 17 n N a -N N-C1+C 2 5 OH (Witt, Ber. 21, 719). This eurhodine, the formal
H H
=HCl+N 2 +C 17 n N 2 OC 2 6 tion of which has been described under Section A,
.
Ethyleurhodol. 3, may easily be prepared in quantity by heating

The following is an enumeration of those of together 20 parts nitrosodimethylaniline hydro-
the eurhodines and eurhodols which have been chloride and 10 parts -naphthylamine with
more closely investigated, the properties of 50 glacial acetic acid ; the reaction sets in
which are typical for the whole class of colouring below 100, and is apt to become violent. The
matters :
product changes to a fine violet colour. It is
Typical eurhodine C 17 H 13 N 3 (Witt, Ber. 19, dissolved in water acidified with hydrochloric
445). The mode of formation of this substance acid, and the filtered solution is precipitated by
has already been given (Section A, 1). It is best the addition of sodium acetate. The crude eurho-
prepared by heating to 130 equal molecules of dine which is thus precipitated may be purified
orthoaminoazotoluene, of the melting-point by dissolving it in alcohol acidified with hydro-
118-5, and o-naphthylamine hydrochloride, dis- chloric acid. From this solution the normal
solved in phenol until the colour of the mix- eurhodine hydrochloride crystallises in bronze-
ture, which is at first of an emerald green, has coloured needles. From these ammonia liberates
changed into a brilliant scarlet. The mixture is the free eurhodine base in the form of a scarlet
now treated with a large quantity of toluene, crystalline powder. It may be recrystallised
when the hydrochloride of the new dyestuff is from boiling xylene ; it is thus obtained in
precipitated in a crystalline state. By recrystal- magnificent crystals resembling magnesium-
lisation from water acidified with hydrochloric platinocyanide, melting at 205.
acid, it may be obtained in a pure state. From The change of colour of a sulphuric acid
the pure hydrochloride the free eurhodine base solution of this eurhodine is not very marked,
is precipitated by alkalis or ammonia in the
going from violet through black and green into
form of a yellow powder, which may be re- violet. The ethereal solution of the free base
crystallised from aniline. Thus prepared, it exhibits the brilliant fluorescence characteristic
forms glistening yellow prisms and needles of a of all eurhodines.
dark-brown colour. It dissolves in ether with Aminophenaphenanthrazine C 20 H 13 N 3 This
.
a yellow colour and a magnificent green fluores- eurhodine was prepared by Witt (Ber. 19. 445)
cence, which is characteristic of all the members and by Heim (Ber. 21, 2306) by the methods
of this group of dyestuffs. Eurhodine forms given under Section A, 2 and 4. It crystallises
three series of salts, of which, however, only from toluene in short, thick, yellow prisms,
those with one molecule of acid are fairly stable, melting at 279.
whilst those containing more acid are decom- Dimethyldiaminotoluphenazine Tolylene red
;
posed by the addition of water. It is to the C 15 H 16 N 4 . The formation of this compound by

formation of these various salts that the peculiar the spontaneous decomposition of tolylene blue
change of colour is due wh'ch is observed on has been described under Section A, 5. This
adding water to a solution of eurhodine in con- eurhodine forms, in a pure state, orange crystals,
centrated sulphuric acid. This solution is of a which contain 4 mols. of water of crystallisation ;
cherry-red colour. On adding a small quantity at 150 this is given off and the anhydrous base
of water the colour changes to a fine emerald remains as a dark-red powder. The hydrated
green, whilst still more water produces the base is soluble in ether with a pink colour and a
scarlet shade of the normal sulphate. This beautiful orange fluorescence. The solution in
change of colour, which is observed with all the concentrated sulphuric acid is green on being
;
eurhodines, links them to their parent-sub- diluted with water it changes through sky-blue
stances, the azines, which exhibit similar into red. The normal (monacid) salts are
curious phenomena, and also to the safranines. perfectly stable and soluble in water with a
The normal salts of eurhodine are well pink colour. This solution dyes unmordanted
crystallised and of a bronzed copper colour when or mordanted cotton and other fibres a pink
solid. In solution they exhibit a bright scarlet which in darker shades deepens into a coppery
tint which they communicate to the fibre. red.
These normal salts are, however, partially de- The production of this dyestuff has been
composed by an excess of water, the free eurho- patented (Otto N. Witt, D. R. P. 15272).
dine base being regenerated. The same takes The commercial product, which contains a
place if fibres dyed red with eurhodine be washed. certain amount of impurities, is sold under
'
The scarlet shade is gradually replaced by the the name of neutral red.' It is chiefly used
yellow shade of the free eurhodine base. For in calico-printing, and gives very fast and useful
this reason eurhodine has not found an applica- shades.
tion in the industry of artificial dyestuffs. A similar product is prepared from the in-
Aminonaphthaphenazine C 16 H 11 N 3 has been damine which is formed by reacting with nitroso-
obtained by Nietzki and Otto (Ber. 21, 1598) dimethylamine hydrochloride upon metaphenyl-
from -naphthylamine and dichloroquinonimide enediamine. It is embraced by the same patent
'
(Ullmann and Ankersmit, Ber. 38, 1811). It and sold under the name of neutral violet.'
crystallises in dark-yellow needles. Its salts are Typical eurhodol C^H^N.OH (Witt, Ber.
AZINES. 353
19, 444). This substance, the formation of divalent organic radicles, and 1 aX monovalent
which takes place according to the equation acid radicle. The azonium bases are
compounds
*given under Section B, 2, forms small leaflets of which possess strong basic properties, and which,
a yellow or red colour which dissolve in con- by the tenacity with which they retain their
centrated sulphuric acid with a red colouration, acid radicle, strongly resemble the ammonium
and are reprecipitated from this solution by the bases. It is probable that the free azonium
addition of water. Caustic soda solution dis- bases contain, like the ammonium bases, the
solves it with an orange shade. Thus it is shown hydroxyl group in the position X* of the above
that this eurhodol (like all compounds of the eneral formula. The azonium bases and the
same class) exhibits both acid and basic pro- lyestuffs derived from them are also capable
perties, the latter being
due to the azine group of tautomeric changes, which lead to their
contained in their molecule. assuming quinonoid structures. The nature of
H N
Eurhodol C 24 14 2 OH. o-Hydroxynaphtha- these changes is in many cases doubtful and too
phenanthrazine has been obtained (Witt, complicated to be fully discussed in this article.
Ber. 19, 2791) by the method described under The azonium bases are strongly coloured
Section B, 1, by the fusion of naphthaphen- substances, but their dyeing properties are
anthrazine-o-sulphonic acid with caustic alkalis. developed and brought to perfection by the in-
Its solution in sulphuric acid is of a fine and troduction of amino- groups into their molecule.
intense indigo-blue ; it changes very suddenly As the azonium bases theoretically possible are
into red on the addition of water, the sulphate
very numerous, and each of them is capable of
This substance is a yellow
being precipitated. producing very numerous isomeric mono- and
colouring matter which may be fixed on cotton polyamino- derivatives, the number of possible
with alum-mordant, like alizarin. Owing, how- safranines is exceedingly
large, and the number
ever, to its costliness, it has not been brought of those which have already been prepared is
into commerce. A
large number of isomerid.es insignificant in comparison with that fore-
may be prepared by starting from the numerous shadowed by theory.
Bulpho- derivatives of orthonaphthylenediamine, Of the safranines which have hitherto been
transforming them into azinesulphonates by prepared, only a few are monoamino- derivatives
condensation with phenanthraquinone and into of azonium bases. A few more are of doubtful
eurhodols by subsequent fusion with caustic or unknown constitution. The majority are
alkalis.
asymmetric diamino- derivatives of azonium
III. Azonium and safranines. The
bases bases, containing one amino- group in one of
azonium bases are a class of compounds of which the diatomic organic radicles (R 11, whilst the
our knowledge is very restricted, very few
other is attached to the monoatomic radicle (R 1 ).
representatives of the class being at present The true constitution of phenosafranine
known, and that rather imperfectly. They are,
and itscongeners has been recognised by Witt,
however, of importance, as it is now established
who, after pointing out the analogy between the
beyond doubt that they are the parent sub- eurhodines and safranines (Ber. 18, 1119) and
stances of the very important class of dyestuffs
clearing up the constitution of the former (Ber.
known as Although the first
safranines.
19, 446), proved the latter to be asymmetric
artificial mauveine, was a true safra-
dyestuff, diaminoazonium bases (Ber. 19, 3121). Bernth-
nine, and although this group of compounds
sen had proposed (Ber. 19, 2690) somewhat
has been frequently under investigation, a
earlier a symmetrical formula for the safranines
correct view of their constitution had not been
based upon Witt's eurhodine researches. His
obtained until quite recently. According to
the theory now universally adopted, all safra-
view was subsequently adopted by some chemists,
but the author of this article fails to see the force
nines are amino- derivatives of azonium bases,
of the arguments adduced in support of it.
to which they stand in the same relation as the .
A. Azonium bases. 1. The typical compound

eurhodines to the azines. Hydroxy- derivatives was obtained by Witt (Ber. 20, 1183) by the
of azonium bases have also been prepared and
described under the name of safranols.
reaction of phenanthraquinone on phenj'lortho
They
are, however, of no importance as colouring
naphthylenediamine. By heating these ingre-
dients in an acetic acid solution an inter-
matters.
The azonium bases themselves, none of mediate product is obtained, which on treat-
which has so far been obtained in a state ment with a mineral acid is transformed into
fit for analysis, stand in the same relation to the
the salt of the azonium base :
azines as the ammonium bases to the amines.
They are azines in which one of the nitrogen
atoms has become pentavalent by being satu-
rated with three organic radicles and one acid
radicle, the connection with the second nitrogen
atom being still preserved by the fifth valency
of the pentavalent nitrogen atom. Thua the
characteristic constitution of the azonium com- /\ NO,
pounds may be expressed by the general formula
Rn If nitric acid is used, the nitrate is deposited

in very fine crystals. It is sparingly soluble in
water, soluble in spirit with a fine
readily
orange-red colouration. The hydrochloride dis-
solves in sulphuric acid with a violet tint, which
in which Ri and R 11 represent mono- and changes into red on dilution with water.
VOL. I T. 2 A
354 AZINES.
2. If in this reaction the phenylorthonaphthyl-
enediamine be replaced by phenylortho-
phenylenediamine, the resulting compound is
a yellow dyestuff of considerable strength. It
manufactured and sold under the name
is
'
Flavinduline
' = HC1 +
(1893).
3. A
very similar compound \vas obtained
by Otto N. Witt and Christoph Schmidt in
1892 (Ber. 25, 1017), by the reaction of benzil
upon ethoxyphenylorthonaphthylendiaraine. It
was called ethoxyphenylnaphthostilbazonium New dyestuff.
chloride and has the constitution :
4. In a similar manner nitrosodimethyl-

any other nitroso-amine) reacts with
aniline (or
phenyl--naphthylamine (Witt, Ber. 21, 719):
HC1
N(CH 3 ) 2
+3
NO Phenyl-jS-naphthylami
Nitrosodimethylaniline
hydrochloride.
It is a beautiful yellow dyestuff, but too N
on a manufacturing (CH 3 ) 2
expensive to be prepared
HC1-N(CH S ) 2
B. Safranines. The various colouring mat-
ters belonging to this group have mostly been
prepared by different synthetical methods,
which =2 +3H 2 +
mav be classed in the following manner :
1. Reduction of the nitro- derivatives of

azonium bases. By reacting with mononitro- NH
phenanthraquinone or dinitrophenanthra- New dyestuff. Dimethylparaphenyl-
enediamine mono-
quinone on phenylorthonaphthylenediamine, hydrochloride.
nitro- and dinitro- derivatives of the above
azonium base are obtained, which on reduction The safranines proper (asymmetric di-
5.
with ammonium sulphide yield reddish-violet aminoazonium bases) are formed by the joint
to the safranine oxidation of one molecule of diamine and two
colouring matters belonging
group (Witt, unpublished observations). molecules of an aromatic monoamine. In this
2. If the stilbazonium base obtained by reaction fugitive indamines are formed as inter-
Witt and Schmidt, or any of its congeners mediate products the process thus becomes
;
prepared from ethylated arylorthonaphthyl- strictly analogous to the formation of toluylene

cnediamines be heated with ammonia, the red and its congeners.
amino- group
ethoxy group is replaced by the This is the process which is generally used
and the corresponding safranines are formed. in the manufacture of safranines, and it will
This is quite a general reaction (Witt and therefore be fully explained.
Schmidt, Ber. 25, 2003 ; Witt and v. Helmolt, By the joint oxidation of an aromatic para-
Ber. 27, 2355 ; Witt and Buntrock, Ber. 27, diamine with one molecule of an aromatic
2362). monoamine, an indamine is hi variably formed
3. the action of dichloroquinommides
By (v. INDAMINES). these indamines be oxidised
If
in which the
upon secondary aromatic amines, in the presence of another molecule of an
para- position to the
amino- group is occupied, aromatic monoamine, a safranine is formed :
monoamino-azonium bases are formed (Nietzki
and Otto, Ber. 21, 1598). The reaction, for in- First Stage.
between dichloroquinonimide and phenyl-
stance,
may be represented by the NH S
/3-naphthylamine
equation :
Cl
NH, NH 2
N \/
+0 = N +2H
2 2 0.
Aniline.
NH 2
Paraphenyl-
Phenyl-/3-nphthylamine. enediamine.
NH
Indamine.
AZINES. 355
Second Stage. NH 2
NH, NH, NH 2
'\
HC1 I I
NH,HC1
NH,
NH +30=3H 2 0+
N + +20=2H 0+
2
Cl
Aniline
Aniline i i
hydrochloride.
hydrochloride.
NH.
Dipara-amino-
NH NH 2
diphenylamine.
Indamiue. Phenosafranine.
Of course, any other paradiamine may be This the oldest process for the manufacture
is
substituted for paraphenylenediamine, and any of safranines. The mechanism of this reaction
other monoamine for aniline. As, however, the is simple. Part of the aminoazo- compound
formation of an indamine only takes place if the being reduced, a mixture of a paradiamine and a
para- position to the ammo- group be still free, primary monoamine in molecular proportions is
it results, that at least one of the two molecules formed, which with the monoamine added in the
of monoamines must fulfil this condition. Thus shape of hydrochloride, is transformed into
the formation of a safranine from paraphenyl- safranine by the dehydrogenating action of the
enediamine takes place on oxidation of one remaining part of the aminoazo- compound. It
molecule of the diamine with is evident that the yield must be small in this
(1) Two molecules of aniline. process of manufacture, and such is actually

the case.
(2) Two molecules of orthotoluidine.
(3) One of aniline and one of orthotoluidine. 8. An' asymmetrical safranine has been
(4) One of aniline and one of paratoluidine. obtainedby the reduction of picryl- ortho -
(5) One of orthotoluidine and one of paraphenylenediamine (Kehrmann, Ber. 33, 3074).
9. Certain compounds belonging to the
toluidine; but it does not take place with one
molecule of paraphenylenediamine and two of safranine group (mauvei'ne, &c.) are formed in
a very complicated reaction by the oxidation of
paratoluidine (Witt, J. Soc. Chem. Ind. 1882,
heavy aniline alone on continued oxidation ;
256).
mauveJne is converted into a safranine (Perkin,
Onthe other hand, the other of the two
molecules of monoamines must have a free ortho - Roy. Soc. Proc. 35, 717).
The following is an account of the more
position in order to be capable of entering the
reaction. Thus the indamine of the above important and more thoroughly investigated
safranines :
formula forms safranines with all the primary
aromatic monoamines of the benzene series, with A. MONAMINO- DERIVATIVES OF AZONIUM
the exception of one xylidine and of mesidine, BASES.
of the respective formulae
1. Aposafranine, Monoaminophenylphenazo-
NH, NH, nium chloride, has been obtained by Nietzki
CH,
and
CH/ \CH S
and Otto (Ber. 21,
and 33, 3078) from
and Ber.
1736 ; see also Annalen,
286, 188, 30, 2624,
phenosafranine (see below) by diazotising one
NH a of its amino- groups, and eliminating it by
because these two have no free ortho- position to means of alcohol. It is a red dyestuff of no
be used for the formation of the azonium
group practical importance, but very interesting as
(Nietzki, Ber. 19, 3017 and 3136). prototype of the induline group (see under
It also necessary that this second molecule
is INDITLINES).
of monoamine be a primary 2. Red dyestuff C 22 H 16 N 3 C1. Obtained by
base, whilst the one
the action of dichloroquinonimide on phenyl-
necessary for the formation of the indamine may
be either primary,
secondary, or tertiary, pro- j8-naphthylamine, was prepared by Nietzki and
vided always that it possesses a free Otto (Ber. 21, 1598) by heating the ingredients in
para-
position. ,
molecular proportion in alcoholic solution on
the water-bath. The nitrate forms green needles
6. It is evident that the
general process de- or prisms which are soluble in water with a
scribed under 4 may be modified; thus, for
the dipara-amino- derivatives magenta-red colour. The hydrochlorido dis-
instance, of solves in sulphuric acid with a red colouration,
secondary bases (being the leuco- compounds of which on dilution changes through green into
indamines) may be oxidised together with one red.
molecule of a primary aromatic monoamine,
when a safranine is the result (see top of 3. Violet colouring matter C 24 H, N 3 C1. Pre-
page,
second column) :
pared by Witt (Ber. 21, 719) by acting with 3
molecules of nitrosodimethylaniline hydro-
7. Another modification chloride in an acetic acid solution on 2 molecules
(Witt, Ber. 10, 873)
consists in
heating aminoazo- compounds with of phenyl--naphthylamine. This is the di-
the hydrochlorides of aromatic monoamines.
methyl- derivative of the preceding substance.
356 AZINES.
The hydrochloride forms large black needles impurities, and the liquid is filtered. By adding
soluble in water, with a fine violet colour. The a small amount of nitric acid and some sodium
H N
free base, C 24 20 3 'OH, is liberated from the nitrate to the filtered solution, the nitrate of the
salts by caustic alkalis only. It is insoluble hi safranine crystallises out ; or the chloride may
water, soluble in alcohol, with a red colour anc be prepared by adding common salt to the solu-
a fine orange fluorescence. It is sold as ' neutra tion after acidifying it with hydrochloric acid.
blue.' By repeated recrystallisation from water or
H
4. Violet colouring matter C 25 22 N 3 C1. Pre alcohol, the phenosafranine is obtained in a
pared by Witt (Ber. 21, 719) from paratolyl state of purity, in the form of magnificent green
-naphthylamine hi exactly the same manner as needles. The sulphate forms blue needles. The
the preceding substance, of which this is the H
platinum salt (C 18 1B N 4 Cl) 2 PtCl 4 forms in-
next homologue. Violet soft needles, resem- soluble shining leaflets. Phenosafranine forms a
bling in their colour and reactions the phenyl- diacetyl- derivative on boiling with acetic an-
derivative. hydride in the presence of dry sodium acetate.
The above substances have been patented It forms two diazo-derivatives, of which the
(Otto N. Witt, D. R. P. 19224, dated Feb. 18, first
1882). C 18H 13 N3C1

Basle blue C 32 H 29N 4 C1
a fine blue
5.
dyestuff prepared (T. Annaheim, Ber.
is
20,
^N : N-C1
1371 ; Durand and Huguenin, Ger. Pat. 40886) israther stable and soluble in water, with blue
by the reaction of nitrosodimethylaniline colouration. The other diazo- compound
hydrochloride on the paratolylnaphthylene-
diamine which is formed by heating Ebert /N : N-C1
and Merz's dihydroxynaphthalene with para-
toluidine hydrochloride. It forms a brown
N : N-C1
crystalline powder, soluble in water with a
bluish-violet shade. In concentrated sulphuric isvery unstable and of a green colour.
acid dissolves with a greenish-brown shade,
it Phenosafranine dyes wool, silk, and cotton a
which changes through green into violet on magnificent pink. Its aqueous solutions are red
dilution. and show no fluorescence, whilst alcoholic solu-
6. Aztae green C 30 H N
25 4 C1 is formed by tions show a marked greenish-yellow fluor-
the reaction of nitrosodimethylaniline hydro- escence. Phenosafranine dissolves in con-
chloride upon 2-6-diphenylnaphthylenediamine. centrated sulphuric acid with a green colouration
7. Induline scarlet H N
C 19 18 3 C1, a very which changes through blue into red on dilution,
beautiful red dyestuff discovered by Schraube thus indicating the actual existence of the three
(D. R. P. 77226), and manufactured by the series of salts foreshadowed by theory.
Badische Aniline and Soda-Fabrik, is really If phenosafranine or its homologues be
not an induline, but a safranine. It is prepared diazotised and then combined with /3-naphthol,
by melting together the hydrochloride of beautiful basic blue dyestuffs are obtained,
anilinazoethylparatoluidine and a-naphthyl- which are largely prepared and used for cotton-
amine. The reaction is strictly analogous to dyeing and calico-printing under the name of
'
the formation of the typical eurhodine. Indoine blue.'
The alkyl- derivatives of phenosafranine are
B. DIAMIKO- DERIVATIVES OF AZONIUM BASES.
interesting colouring matters, some of which
1. Phenosafranine C 18H 1?N 4 C1. Discovered have found an industrial application. They
by Witt (exhibited in Paris hi 1878 ; and men- liave not been prepared by introducing alkyl-
tioned in the catalogue of Messrs. Williams, *roups into ready-formed safranine, but rather
Thomas & Dower, closely investigated by by direct synthesis from suitable raw materials.
Nietzki (Ber. 16, 464) and by Bindschedler Each of them exists in two isomeric modifica-
(Ber. 13, 207 ; 16, 865). ;ions, according to the amino- group into which
It was with this compound that the mode of ;he alkyl- group has been introduced. The two
formation of the safranines and their chemical amino- groups of phenosafranine being asym-
properties were definitely ascertained, chiefly by metric, and therefore not equivalent to one
R. Nietzki, whose brilliant researches on this another, must of necessity produce different pro-
subject did much to clear up the chemistry of ducts on being alkylated.
this group. H N
o-Dimethylsafranine C 20 19 4 C1 is produced
Phenosafranine is prepared by the joint )y the simultaneous oxidation of one molecule
oxidation of paraphenylenediamine and aniline. of paraphenylenedimethyldiamine with two
The mechanism of this process has already been molecules of aniline.
discussed. A dilute aqueous solution of the It is a dyestuff of a magenta-red shade. Its
normal hydrochlorides of these bases is used, and nitrate crystallises hi green needles (Bindschedler,
then- oxidation is accomplished by adding Ber. 16, 869).
potassium or sodium bichromate or manganese /3-DimethyIsafranine is obtained by oxidising
dioxide in the necessary proportion to the hot a mixture of one molecule of paraphenylene-
solution. The blue colour of the indamine diamine with one molecule of aniline and one
which appears at first is immediately replaced molecule of dimethylaniline. Its shade ia
by the red colour of the safranine formed. A imilar to that of the preceding one ; its nitrate
certain quantity of insoluble dark by-products orms brown leaflets (Nietzki, Ber. 19, 3017 and
is always formed, but by careful work the yield J136).
of pure safranine may be raised to 70 p.c. of the The two diethylsafranines are obtained in
theory. When the oxidation is finished, soda solu- a similar manner. Their chlorides form green
tion or chalk is added in order to precipitate the needles which dissolve in water with a violet
AZINES 357
shade (Nietzki, Ber. 16, 464). These sub it has been unable to compete with the eosin
stances, and especially the a- derivatives, are colours, which are perhaps still more brilliant
manufactured under the name of Fuchsia. in shade.
Tetramethylsafranine (Bindschedler, I.e.) and 5. Magdala red C 30 H
21 N 4 C1. This old and
tetraethylsafranine (Nietzki, I.e.) may be pre- very beautiful colouring matter is the safranino
pared by the joint oxidation of one molecule of of the naphthalene series. It was discovered
by
paraphenylenedimethyl- (or diethyl-) diamine Schiendl and first investigated by Hofmann
with one molecule of aniline and one molecule (Ber. 2, 374), who, however, owing to the great
of dimethyl- or diethylaniline. These substances difficulties of its analysis, assigned to it the
have been sold under the name of Amethyst. erroneous formula C 30 H 21 N 3 -HC1.After a
Their shade is a magnificent violet, with a fine revision of the analytical data by Julius (Ber.
crimson fluorescence. Unfortunately, they are 19, 1365), its true composition was established.
very fugitive. This substance cannot be prepared by the
2. Tolusafranines (Hofmann and Geyger, usual oxidation process from paranaphthylene-
Ber. 5, 526, and very numerous other publi- diamine and naphthylamine because "para-
H N
cations) C 21 21 4 C1. A mixture of the iso- naphthylenediamine is at once transformed into
merides of this formula is the safranine of a-naphthaquinone even by the feeblest oxidising
commerce. It is prepared by the oxidation of agents. Magdala red has therefore to be pre-
a mixture of paratolylenediamine with the two pared by the old process of heating o-amino-
toluidines. This mixture is obtained by treat- azonaphthalene with a-naphthylamine acetate.
ing three molecules of the orthotoluidine of The chief product of this reaction is rhodindine,
commerce (which contains from 6 to 10 p.c. of the induline of the naphthalene series (v. INDTJ-
paratoluidine) with two molecules of hydro- LINES) ; but a small proportion (6-8 p.c.) of
chloric acid and one molecule of sodium nitrite Magdala red is formed at the same time. This
dissolved in as little water as possible. Athick is extracted from the melt by repeated treat-
heavy oil is the result, which is merely a solution ment with boiling water, in which it is sparingly
of amino-azotoluene in the excess of toluidine soluble. On cooling, this solution deposits
present. By dissolving this oil in hydrochloric the dyestuff in the shape of gelatinous flakes,
acid, and reducing it with either zinc-dust or It is purified by repeated crystallisations from
iron borings, the amino-azo- compound is split water. When pure, it forms a dark crystal-
up into paratolylenediamine and orthoto- line powder, which dissolves in alcohol with a
luidine ; consequently, the aqueous liquid pro- pink colour and a magnificent orange fluores-
duced contains the bases hi the necessary cence. It is used for dyeing light pinks on silk,
proportions the production of safranine.
for but is now rapidly being replaced by rhodamine
The rest of the treatment is exactly similar to (v. TRIPHENYLMETHANE COLOURING MATTERS). If
the one described for pheno-safranine. The ready -formed paranaphthylenediamine be added
safranine is precipitated from the liquid by the to the magenta-melt, the proportion of Magdala
addition of salt. By redissolving it in water, red formed is considerably increased (Otto N.
boiling with a small quantity of potassium Witt, D. R. P. 40868). It is thus shown that
bichromate, treating it afresh with milk of lime Magdala red is, after all, only a product of the
or chalk, and joint oxidation of paranaphthylenediamine and
reprecipitating the filtered liquid
with clean salt, the safranine is purified so as a-naphthylamine.
to give the brightest shades on
dyeing. Safra- The pure salts of Magdala red, when re-
nine prepared with a toluidine rich in para- crystallised from spirit, form green needles with
toluidine is very insoluble in cold water, and a metallic lustre. The chloride, sulphate, pi-
therefore generally disliked by the dyer. The crate, and platinum double chloride have been
presence of aniline has not the same disagree- prepared and analysed. These salts dissolve in
able effect :some manufacturers therefore use concentrated sulphuric acid with a blue- black
the first runnings of the colour which changes into red on dilution.
magenta process, which
consist of aniline and orthotoluidine, and con- Mixed Magdala reds have been prepared
tain no paratoluidine, as a suitable raw
product either by heating amino-azonaphthalene with
for the manufacture of safranine. The safra- aromatic monoamines of the benzene series (M.
nine of commerce forms a brown
powder which T. Lecco, Ber. 7, 1290), or by heating aminoazo-
dissolves readily in hot water. It dyes a bluish- compounds of the benzene series with para-
pink on textile fibres, and was chiefly used for naphthylenediamine hydrochloride and aniline,
dyeing cotton. The introduction of the so- toluidine, or even phenol (Otto N. Witt, D. R. P.
called substantive azo- colours, derived from 40868). These dyestuffs resemble Magdala red
benzidine and its congeners, has much diminished hi their properties.
the use of safranine. 6. Indazine is the commercial name of a
3. Girofle. A
dimethylphenoxylosafranine safranine dye, which is obtained by heating
has been produced by heating nitrosodimethyl- the symmetrical diphenylmetaphenylenediamine
[prepared by heating resorcin with
aniline hydrochloride with xylidine, and sold aniline
under the above name as a violet colouring hydrochloride in the presence of zinc chloride)
matter of a pleasing shade. with nitrosodimethylaniline hydrochloride. Its
4. Safranisol C
18 H N
13 (OCH 3 ) 2 4 -C1 is a sub- constitution may be inferred from its analogy
stance which has been obtained
by Nietzki by to the violet dyestuff prepared from nitrosodi-
It
the joint oxidation of one molecule of
para- methylaniline and phenyl-j8-naphthylamine.
phenylenediamine with two molecules of ortho- is a serviceable blue, of considerable intensity,
anisidine. It dyes a very beautiful yellowish- but little brilliancy of shade.
pink with a yellow fluorescence. This product Mauveme C 27 H 25 N
4 C1.
This subtance, the
has been patented (Kalle & Co.,D. R. P. oldest of all the artificial colouring matters, is
24229),
but owing to the high
price of its production still manufactured in a small wav, and sold under
358 AZ1NES.
the name of rosolane. It was discovered and vorm. Fried. Bayer & Co., 1). R. P. 21080<i ;
examined by W. H. Perkin (Roy. Soc. Proc. Chem. Zentr. 1909, 2, 163); by treating phenyi-
35, 717), who also described the mode of its hydrazine with bleaching powder solution (Brun-
production. It
prepared by oxidising heavy
is ner and Pelet, Ber. 1897, 284). Azobenzene
aniline with potassium dichromate, and extract- can be prepared by the electrolytic reduction
ing the mauveine formed with water or spirit of nitrobenzene in the presence of alkali (Elbs
from the black insoluble mass which is the chief and Kopp, J. Soc. Chem. Ind. 1898, 1137 ; Lob,
product of the reaction. A dyestuff resembling Ber. 1900, 2329 ; Farb. vorm. Fried. Bayer &
mauveine in all its properties may be prepared Co., D. R. PP. 121899 and 121900; Chem.
by the reaction of nitrosodiphenylamine on Zentr. 1901, 2, 153 : Farb. vorm. Meister,
aniline (Otto Fischer and Hepp, Ber. 21, 2617) Lucius and Briining; D. R. P. 141535; Chem.
or by the joint oxidation of diphenylmetaphenyl- Zentr. 1903, (i.) 1283 and Farb. vorm. Weiler-
;
enediamine and paraphenylenediamine or meta- ter-Meer, D. R, P. 138496; Chem. Zentr. 1903.

aminodiphenylamine and para-aminodiphenyl- (i.) 372).
amine. These syntheses are a clue to the Properties. Azobenzene crystallises in large
constitution of mauveine, which has been a yellowish-red crystals belonging to the mono-
mystery for nearly half a century it stands clinic system (Boeris, R. Accad. Lincei, [5] 8, i.
revealed as phenylphenosafranine. The above 575), and to the rhombic system (Alexejeff, Chem.
synthetical methods have been adopted for the Soc. Abstr. 42, 965) ; melts at 68, boils at 293,
industrial preparation of mauveine, as they give and is readily soluble in alcohol and ether, in-
better yields than Perkin's old process of soluble in water. From benzene it crystallises
oxidation. Mauveine is generally sold in the with benzene of crystallisation in rhombic prism?,
shape of a violet paste. It is insoluble in cold, which lose benzene on exposure to the ah-.
sparingly soluble in hot water, easily soluble Weak reducing agents, such as ammonium sul-
with a purple shade in spirit. Concentrated
fine
phide or zinc-dust in alkaline solution (Alexejeff,
sulphuric acid dissolves it with an olive-green Annalen, 207, 327) or phenylhydrazine (Walther,
colouration, which on dilution with water J. pr. Chem. 1896, 54, 433), convert azobenzene
changes through green and blue into purple. into hydrazobenzene, but benzidine is obtained
Mauveine still holds its own against the cheaper when stronger reducing agents such as sul-
new violets on account of its great fastness to phurous acid or hydrogen iodide are employed
light and other influences. It is used for shading (Bordenstein, D. R, P. 172569; J. Soc. Chem.
the white in bleached silks, and also for printing Ind. 1907, 272), or the alcoholic solution is
on paper. treated in the cold with stannous chloride and
Mauveine yields on oxidation a pink dyestuff a little sulphuric acid (Schultz, Ber. 17, 464 ;
which is supposed to be identical with ordinary Mentha and Heumann, Ber. 19, 2970). Azo-
phenosafranine. In our opinion this statement benzene can also be electrolytically reduced to
requires confirmation. 0. N. W. benzidine (Lob, Ber. 1900, 2329 ; when heated
AZOBENZENE C 12 H, 2 . N A
product of the with ammonium hydrogen sulphite and alcohol
partial reduction of nitrobenzene, obtained by under pressure, it is converted into benzidine-
Mitscherlich (Annalen, 12, 311) by boiling an sulphamic acid (Spiegel, Ber. 18, 1481). When
alcoholic solution of nitrobenzene with potash melted with ^-phenylenediamine in the
and distilling the product. presence of ammonium chloride, it yields a
Preparation. Azobenzene is obtained by soluble induline dye (Farb. vorm. Fried. Bayer
acting with sodium amalgam (4-5 p.c. of & Co., D. R, P. 53198 ; Ber. 1891, Ref. 137). Azo-
sodium) on nitrobenzene dissolved in ether con- benzene yields a mixture of mono-, di-, and tri-
taining water (Werigo, Annalen, 135, 176 ; Alexe- nitroazobenzenes when treated with fuming
jeff, J. 1864, 525 ; Rasenack, Ber. 5, 367) ; the nitric acid (Gerhardt and Laurent, Annalen, 75,
product, according to Alexejeff (J. 1867, 503) is 73; Janovsky and Erb, Ber. 18, 1133; 19,
azobenzene or azoxybenzene, according as the 2157; Janovsky, Monatsh. 7, 124 ;
T
erner and W
sodium amalgam or nitrobenzene is in excess. 'Stiasny, Ber. 1*899, 3256): ordinary sulphuric
On the large scale azobenzene is prepared by the acid dissolves it without alteration, whilst
reduction of nitrobenzene in alcoholic solution the fuming acid at 130 converts it into
v.ith zinc-dust and aqueous soda. In this re- azobenzenemonosulphonic acid (Griess, Annalen,
action the reduction tends to go further, and 154, 208; Janovsky, Monatsh. 2, 219);
some hydrazobenzene is also obtained ; this, chromic acid oxidises it to carbon dioxide
however, is readily oxidised to azobenzene if and nitrogen (De Coninck, Compt. rend. 1899,
nitrous fumes are passed into the alcoholic solu- 128, 682). The bromine derivatives of azo-
tion of the product (Alexejeff, J. 1867, 503). benzene have been examined by Werigo (Anna-
Azobenzene can also be prepared by distilling len, 165, 189), Janovsky (l.c.), and Mills (Chem.
azoxybenzene (1 part) with iron filings (3 parts) Soc. Trans. 1894, 51).
(Schmidt and Schultz, Ber. 12, 484) by heating ; AZOBENZENE RED v. Azo- COLOURING
nitrobenzene on a water-bath with the calculated MATTEBS.
quantity (2 mols.) of stannous chloride dissolved AZO-BLACK or NAPHTHOL BLACK v. Azo-
in excess of aqueous caustic soda (Witt, Ber. COLOURING MATTERS.
18, 2912) by reducing nitrobenzene in alcoholic
; AZO-BLUE v. Azo- COLOURING MATTERS.
solution with magnesium amalgam (yield 95 p.c.) AZO-COCCINE v. Azo- COLOURING MATTERS.
(Evans and Fetsch, J. Amer. Chem. Soc. 1904, AZO- COLOURING MATTERS.
1158); by reducing nitrobenzene with alkali History. The colouring matters of this
sulphide in the presence of alkali (Farb. vorm. class contain one or more azo- groups N N :
Meister, Lucius, and Briining, D. R. P. 216246, linking together aromatic radicles. The typical
J. Soc. Chem. Ind. 1909, 1310); by
heating parent substance from which these compounds
nitrobenzene with charcoal and alkali (Farb. may be regarded as being derived is azobenzene
AZO- COLOURING MATTERS. 359
C 6 H 5 -N N'C 6 H 5 which has been known

: ,
since of these acid azo- colours may be regarded as
the year 1834 (Mitscherlich, Annalen, 12, 311). H H
hydroxyazobenzene, C 6 5 -N 2 -C 6 4 -OH, which
The basic and acid derivatives of azobenzene was first prepared by Griess in 1864 (Phil. Trans.
are all colouring matters, the amino- derivative, 153, 679). The general method by which the
aminoazobenzene, having been the first of azo- colours are now prepared is an application of
these compounds which was prepared and intro- the reaction between diazo- salts and phenols
duced into commerce on anything approaching in alkaline solution, first made known by Kekule
a large scale by the firm of Simpson, Maule, and and Hidegh (Ber. 1870, 3, 233), the first colouring
Nicholson in 1863. This substance was pre- matters of this class having been introduced by
'
pared by the action of nitrous gases on aniline Witt under the name of Tropaeoliiies ' (Chem.
dissolved in alcohol, and was known in the Soc. Trans. 1879, 35, 179), and simultaneously by
market by the name of aniline yellow,' the
'
Poirrier, of St. Denis, under the designation of
' '
true constitution of the colour being at the time Orange of various brands. Since the first
unknown. The introduction of the first azo- appearance of the acid azo- colours immense
colour into commerce is thus due to the firm numbers of these compounds have been sent
above mentioned, although the production of into commerce under various designations, the
the colour itself appears to have been previously first patent having been taken out by Griess in
observed by Mene (Compt, rend. 1861, 52, 311), 1877 (E. P. 3698), and being quickly followed
Luthringer (Brevet d'invention, Aug. 30, 1861), by others, which will be referred to in due order.
and Griess (Annalen, 1862, 121, 262, note). Of the acid azo- colours described in the earlier
The first researches on the diazo- compounds specifications, the most successful from an
(as distinguished from azo- compounds) were industrial point of view were those manufactured
'
published'in 1858 by Griess (Annalen, 106, 123), by the Badische Anilin- und Soda-Fabrik '
who in 1862 discovered a compound produced (Ber. 1879, 12, 1364), and by Meister, Lucius,
by the action of nitrous acid on aniline, to which'
'
und Briining, of Hochst (ibid. 144).
he gave the name of diazoamidobenzol The next step of importance in the industrial
(Annalen, 131, 257). The latter was, however, history of the azo- colours was the introduction
a true diazo- compound, and on comparing it of disazo- compounds, containing two azo- groups.
' '
with the aniline yellow of commerce it was The typical compound of this class is benzeneazo-
found that the two substances were isomeric, H H H
benzeneazophenol C 6 5 -N 2 -C 6 4 -N 2 -C 6 4 -OH,
a discovery which led to the establishment of the discovered in 1877 by Caro and Schraube (Ber.
'
true formula of aminoazobenzene by Martius 10, 2230). In 1879 appeared the Biebrich
'
and Griess in 1866 (Zeitsch. Chem. N. F. 2, 132). scarlet of Nietzki (Ber. 1880, 13, 800, 1838),
In this same year a brown dye was sent into the which was introduced by the firm of Kalle &
market by the firm of Roberts, Dale, and Co., Co. of Biebrich. This dyestuff is prepared by
of Manchester, and this colouring matter (known combining diazotised aminoazobenzenedisul-
as Manchester Brown, Vesuvine, Phenylene phonio acid with j8-naphthol, and was the first
Brown, or, more generally, Bismarck Brown) of the secondary disazo- compounds. The first
'
was investigated by Caro and Griess, and primary disazo- colouring matter, Rescrcin
identified as an azo- compound in 1867 (Zeitsch. brown,' was discovered in 1881 by Wallach,
Chem. N. F. 3, 278). These chemists regarded who combined two molecules of a diazo- com-
it as triaminoazobenzene, but G. Schultz pound (m-xylidine and sulphanilic acid) with one
(Chemie des Steinkohlentheers, 2nd ed. 2, 193) molecule of a phenol (resorcinol). In 1884 a
showed that it is benzene-1 3-disazophenyl- :
very important discovery in the history of azo-
enediamine. This compound still occupies an colouring matters was made by P. Bottiger, who
important place in the tinctorial industries, found that the disazo- compound obtained by
whilst the earlier known aminoazobenzene combining the tetrazo- salt prepared from
(aniline yellow) has been completely abandoned benzidine with naphthionic acid possessed the
on account of its fugitive character. It is, how- valuable property of dyeing cotton direct, with-
ever, used in the preparation of other azo- out the use of a mordant. This colouring
colouring matters and indulines. In 1876 a matter was put on the market by the Aktienge-
beautifully crystalline orange colouring matter sellschaft f iir Anilinfabrikation, under the name
made its appearance as a commercial product of
'
Congo red.' This discovery has given rise
under the name of ' chrysoidine,' its composi- to the production of a very large number of
tion and constitution
having been established similarly constituted colouring matters, which
by Hofmann (Ber. 1877, 10, 213), who showed appear on the market under the names of benzo-,
it was cliaminoazobenzene.
that This colouring Congo-, diamine-, and other dyestuffs. In the
matter was discovered almost simultaneously by following year another important development
Caro and Witt, independently, in 1876, but* was was announced by the introduction of the first
satisfactory black azo- colouring matter (naph-
first introduced into commerce
by the latter,
the manufacture
having been carried out by thol black) for wool. This was discovered by
the firm of Williams, Thomas, and Dower, of Hoffmann and Weinberg, and placed on the
Brentford and Fulham. market by L. Cassella & Co. In 1887 A. G.
The manufacture of chrysoidine w as the r
Green found that primuline, which he had dis-
firstindustrial application of Griess's discovery covered, dyed cotton direct, and that the yellow
colouring matter when thus dyed on
of the diazo- the fibre,
compounds, the colouring matter in
question being prepared by the action of a diazo- could be diazotised and combined (developed)
*alt (diazobenzene chloride) on m-phenylene- with j3-naphthol, ?n-phcnylenediamine, and
diamine, and this similar developers,' thus giving rise to a scries
'
manufacture was soon
followed by the appearance of acid azo- com- of new azo- dyestuffs (Ingrain colours). This
pounds prepared by the action of diazosulphonic discovery led to the manufacture of many azo-
acids on phenols. The typical parent substance colouring matters which were capable
of being
360 AZO- COLOURING MATTERS.
similarly diazotised and developed on the fibre old mixture for several hours. Special meth
(e.g. diamine black), as also to the production of xave to be employed to diazotise amines con-
azo- colouring matters on the fibre by treating aining several negative groups ; the operation
the fibre already dyed with an azo- colour with may often be effected by carrying it out in the
a diazo- compound (e.g. benzonitrol colours). presence of excess of 50 p.c. sulphuric acid,
ciu,
In both cases darker and faster dyeings are and Witt has shown (Ber. 1909, 42, 2953 )53)
obtained. ;hat diazotisation is easily brought about
The first direct cotton black (diamine black, ;hese cases by employing strong nitric acii
RO) was discovered in 1889 by Gans (Cassella Other substances which are difficult to diazotise
& Co.), and in 1891 Hoffmann and Daimler satisfactorily are those which are readily
prepared the first green colouring matter of this oxidised by the nitrous
acid, such as the 1 2- :
kind (diamine green). andthe2 : 1-aminonaphthols and their sulphonic

A modified method of the process introduced acids. In this case the diazotisation may be
in 1880 by Read Holliday and Sons, of producing done in the presence of zinc or copper salts
insoluble azo- colouring matters directly on the (compare E. P. 10235 of 1904 ; D. R. P.
fibre, has been largely developed of late years. 171024, 172446; E. P. 353786) or by means of
The first example of this, viz. the combination zinc nitrite. Another method is to diazotise in
of diazotised ^-nitroaniline with j8-naphthol presence of an excess of acetic or oxalic acid
(' paranitraniline red ') still holds the place of (compare D. R. P. 155083, 175593, also E. P. 2946
greatest importance. of 1896).
Manufacture.- The general method of pre- Difficulties are often encountered in en-
paring the azo- colours on a large scale depends deavouring to diazotise certain diamines.
upon the reaction between a diazo- salt, usually o-Phenylene- and tolylene-diamines cannot be
the chloride, and a phenol or phenolsulphonic diazotised, as they yield the azimino- derivatives,
acid in presence of an alkali, as typified by the and, under the usual conditions, the meta-
following example : diamines furnish Bismarck brown ; but if the
C.H B -N t Cl+C.H 5 -ONa diamine run into a mixture of nitrite and acid
is
D'azobenzene Sodium the tetrazo-compound may be obtained (Griess,
chloride. phenoxide. Ber. 1886, 19, 317 ; Tauber and Walder, Ber.
=C 6 H H
5 -N 2 -C 6 4 -OH+NaCl. 1897, 30, 2901; E. P. 1593 of 1888; D. R. P.
Benzeneazophenol. 103685). In the case of p-phenylenediamine
Aminosulphonic acids or aminocarboxylic and certain diamines of the naphthalene series
acids when diazotised react in a similar manner : diazotisation is brought about indirectly, as the
direct action of nitrous acid often leads to a
mixture of the mono- with the bis-diazo- (or
Sodium tetrazo-) compound. Either the corresponding
Diazosulphanilic
acid. phenoxide. nitroamine the monoacetylated diamine
or
=S0 3 Na-C 6 H
4 -N 2 -C 6 H
4 -OH. is employed. This is diazotised and combined
Sulphobenzeneazophenol (sodium salt). with a component in the usual way (see below),
Preparation of the diazo- salts. The amine and then the nitro- group is reduced or the acetyl
to be diazotised is usually dissolved in about group hydrolysed when the free amino- group
10 parts of water and one equivalent of hydro- can then readily be diazotised. Some diamines,
chloric (more rarely sulphuric) acid. For indeed, can only be diazotised as regards one
diamines twice this amount of acid is taken. amino- group, the other being quite unattacked.
The solution l is now cooled by adding ice until In such cases (e.g. o-nitro-p-phenylenediamine,
the temperature is, in the case of aniline, the 1 : 4-naphthylenediamine-2-sulphonic acid- the
toluidined, the xylidines, &c., 0-2, or, in the latter being diazotisable only in acetic or oxalic
case of the naphthylamines, the nitroanilines acid solution) the monodiazo-salt is combined
and diamines such as benzidine, tolidine, with a component and then the remaining
dianisidine, &c., 5-10. This is done by adding amino- group, which before resisted all attempts
ice to the solution. More acid (1^-2 equiva at diazotisation, is easily diazotised (compare
lents) is now added (or 3-4 in the case of Billow, Ber. 1896 29, 2285; E. P. 2946 of 1896).
diamines), and a solution of the calculated (For further information on this subject, see
quantity of sodium nitrite is run in, sufficient Cam, The Chemistry of the Diazo- Compounds,
being used to give a reaction with starch-iodide Arnold, 1908.)
paper after the whole has been mixed for two Combination (coupling) of the diazo- compound
or three minutes. (For velocity of diazotisation, with a component (phenol or amine) to form art
see Hantzsch and Schumann, Ber. 1899, 32, azo- dyestuff. Before the diazo- solution is pre-
1691; Schumann, ibid. 1900, 33, 527.) In pared a solution of a phenol or amine is made
certain cases ready so that no delay may occur before coupling
(e.g. a-naphthylamine, p-miio-
aniline, &c.) add
it is better to the nitrite al] takes place. As a general rule, phenols are
at once in order to avoid the formation of the combined in alkaline and amines in acid (acetic)
diazoamino- compound. In diazotising such com- solution. In the case of phenols or naphthols
pounds as give an insoluble diazo- derivative, the substance is first dissolved in the calculated
as, for example, p-sulphobenzeneazo-o-naphthyl- amount of sodium hydroxide, the solution diluted
amine or p-acetylaminobenzeneazo-a-naphthyl- with water, and sodium carbonate added in
amine, and which themselves are insoluble in sufficient quantity to ensure an alkaline reaction
acids (under the above conditions) it is advisable being obtained at the end of the combination
to use an excess of nitrite and to stir the ice- (i.e. a little more than one
molecule of sodium
carbonate to each molecule of hydrochloric
Some of the diazosulphonic acids, such as diazo
1
naphthionic acid, are insoluble in water, and are there acid, so that sodium hydrogen carbonate may
lore employed in a state of suspension. be formed). When phenoSc sulphonic acids
are the components, they may be dissolved in position 1 (in the ortho- position with respect
sodium carbonate instead of hydroxide. The to the amino- or hydroxy- group). If the
phenolic solution, having been cooled to about 1- position in /3-naphthol is occupied
by a carb-
10, is now ready, and the diazo- solution is oxy- group, this is displaced (compare also
run in gradually with constant stirring. Com- Scharwin and Kaljanoff, Ber. 1908, 41, 2056
bination takes place at once,i and when and article on DISAZO- and TETKAZO- COLOUR-
all the diazo- solution has been added, the ING MATTERS).
mixture must be tested to ensure an alkaline Differing capacity for combination. As will
reaction, and the presence of a slight excess nave been gathered from the preceding para-
of the phenol (about 2-5 p.c. excess of the graph, the azo- group never enters the meta-
theoretical amount is usually taken). The position with respect to an amino- or hydroxy-
next day the colouring matter is filtered through group. Further, a component in which the para-
filter presses. If it has separated out, no further position is occupied by a substituent group is
treatment is necessary, but if it is still partly not so readily attacked (in the ortho- position)
'
or wholly in solution, it is ' salted out (hot or as one that is not substituted (when the azo-
cold) by adding common salt until a spot on group enters the para- position). Moreover, the
filter paper shows only a faintly coloured rim. capacity for combination depends also on the
In rare cases the precipitation is effected by kind of diazo- compound employed, thus 2-
acidifying. The filtration is best effected by naphthol-8-sulphonic acid and 2-naphthol-
the aid of compressed air and the press cake 6 8-disulphonic acid in dilute solution do not
:
is spread on trays and dried. The dry lumps combine at all with diazotised xylidine or
'
are then ground in a mill, adjusted to ' type naphthylamine, whilst diazotised aniline, amino -
by means of common salt, sodium
' '
cr standard azobenzene, aminoazobenzenesulphonic acid and
sulphate, &c., and the product is then ready for naphthylaminesulphonic acids couple easily
the market. In cases where the possibility of with them. The combination with diazotised
the formation of a disazo- dyestuff is present xylidine and naphthylamine can, however, be
(dihydroxy- compounds, o-naphthol, &c.), the made to take place in concentrated solution.
coupling may advantageously be carried out in The compound of ^p-nitroaniline, in most
diazo-
acetic acid solution. cases, combines with extreme ease. Finally,
The procedure adopted in the case of amines 2-naphthylamine-6 8-disulphonic
: acid does
is very similar to the above. The amine is not combine Avith any diazo- compound. (For
first dissolved in the
appropriate amount of measurement of the rate of formation of dye-
hydrochloric acid, the solution diluted and stuffs, Goldschmidt, Ber. 1897, 30, 670,
see
sufficient sodium acetate added to ensure that 2075; 1899, 32, 355; 1900, 33, 893; 1902, 35,
no free mineral acid remains at the end of the 3534; Veley, Trans. Chem. Soc. 1909, 95,
combination (in rare cases coupling is effected 1186.)
in mineral acid or alkaline solution). When Considering now the formation of azo-
the combination is complete, the dyestuff is dyestuffs from tetrazotised diamineS;, should it
filtered off either as it is or after
having been be noted that diamines of the type of benzidine
rendered alkaline. furnish tetrazo- compounds which can either le
Many disazo- dyestuffs are prepared by com- combined with two molecules of one component
bining two molecules of the same or different (phenol or amine) or with one molecule each of
diazo- with an aminonaphthol-
compounds two components, and the reaction can thus be
sulphonic In this case combination is
acid. divided into two stages. This holds good even
effected first in acid solution and then the when one component on!}' is used ; thus tetrazo-
monoazo- dyestuff thus formed is rendered tised benzidine combines almost at once with
alkaline, and the second molecule of diazo- one molecule of naphthionic acid, forming a
compound added. so-called intermediate product ; but the second
Position assumed by the azo- group in the molecule of naphthionic acid combines with this
formation of azo- colouring matters. (a) Benzene only slowly. Here also a difference in combining
series When the para- position with respect to
:
power is to be noted, thus tetrazotised benzidine
the amino- or hydroxy- combines more readily than does the correspond-
group is occupied by a
hydrogen atom, and no group, such as NO.,, ing compound from tolidinc.
S0 3 H, or NR 3 C1, is in the meta- position, the General properties. (1) Action of alkali>.
azo- group enters the
para- position in place of Hydroxyazo- dyes containing a sulphonic or
the hydrogen atom, (b) Naphthalene series :
carboxylic group usually form differently
In corresponding compounds of the coloured salts, and consequently the addition
naphthalene
series (a-naphthylamine,
o-naphthol) the enter- of sodium hydroxide to their solutions produces
ing azo- group also takes up the para- position, a modification in the shade (compare Hewitt
but when, in a-naphthol, a
sulphonic group is and Mitchell, Trans. 1907, 91, 1251). The
in the 3- or
5-position with respect to the isomeric colouring matters prepared from
hydroxy- group, or a nitro- or NR 3 C1- group is a- and 0-naphthol show a characteristic differ-
in the 3- position, the azo-
group enters the 2- ence in that only those derived from the former
position. are changed by sodium hydroxide (e.g. beuzo-
When the para- position is substituted, the azurine, &c.).
azo- group enters the acids.
ortho-(2)- position, but if (2) Action of cold dilute Dyestuffs
the para- substituent is a amino- groups
carboxy- group, this containing amino- or substituted
is
usually displaced by the azo- group. generally undergo a change when treated with
^\ lion diazo- compounds act on /3-naphthyl- dilute acid (compare Fox and Hewitt, Trans.
amine or j8-naphthol, the azo- enters 1908, 93, 333 ; Hewitt and Thomas, ibid.
group
1
For the formation cf diazo-oxy- compounds, see a 1909, 95, 1292 Hewitt and Thole, ibid. 1909,
;
paper by Dimroth and Hartmann, Ber. 1908, 41, 4012. 95, 1393 ; 1910, 97, 511). In the case of Congo
red and methyl orange this change is so pro- taining an amino- or hydroxy- group in the
found that these colouring matters can be used para- position with respect to the azo- group),
as indicators. with the production of the diazo- compound
(3) Action of cold concentrated sulphuric from which the dye is prepared and the nitro-
acid. Nearly all azo- colouring matters give derivative of the other component ; thus,
characteristic colour changes with this reagent, orange II yields diazotised sulphanilic acid, and
and it is often used as an aid in the detection a nitro- derivative of 3-naphthol and methyl
of dyes. Mixtures of dyes, when covered with orange gives ojj-dinitrodimethylaniline, tetra-
sulphuric acid, often reveal themselves by the nitrodimethylaniline and diazotised sulphauilic
various colours produced by the particles as acid (0. Schmidt, Ber. 1905, 38, 3201).
they become dissolved. There are certain re- Finally, warm nitric acid usually decomposes
lationships between the colour of the solution azo- dyestuffs, with the production of nitro-
of azo- dyes in sulphuric acid, and therefore of phenols or bases.
their absorption spectra and their chemical (7) Action of chlorine and bromine. All azo-
constitution. Thus the dyestuff from amino- colouring matters are readily attacked by
azobenzenesulphonic acid and j8-naphthol gives chlorine or bromine. Fission generally takes
a green colour, those from the same (diazotised) place at the azo- group with the production of
amine and j8-naphtholsulphonic acids, a blue, halogenated phenols, but some dyestuffs are
and those from aminoazobenzene and its converted into substitution products (compare
homologues combined with #-naphtholsulphonic Ber. 1884, 17, 272).
acids a red violet (compare Ber. 1880, 13, 1840 ; (8) Action of reducing agents. Reducing
Vogel, Sitzungsber. K. Akad. Berlin, 1887, 34, agents, such as zinc-dust and water, zinc-dust
715; Ber. 1889, 22, 634, 2062; Schiitze, and ammonia, or sodium hydroxide, zinc-dust
Zeitsch. physikal. Chem. 1892, 9, 2; Grebe, and dilute acids, tin and hydrochloric acid,
Diss. Leipzig, 1892). stannous chloride and sodium hyposulphite
(technically known as hydrosulphite ') (Grand-
'
(4) Action of hot hydrochloric acid. Certain

azo- colouring matters, such as, for example, mougin, Ber. 1906, 39, 2494, 3561, 3929;
aminoazobenzene, are decomposed when boiled compare also Chem. 1907, (ii.).76, 124;
3. pr.
with concentrated hydrochloric acid ; reduction Franzen and Stieldorf, J. pr. Chem. 1907, (ii.)
and oxidation take place accompanied by 76, 467 : O. Fischer, Fritzen and Eilles, J. pr.
chlorination. In the instance quoted phenyl- Chem. 1909, (ii.) 79, 562) attack the azo-
enediamine, aniline, and benzoquinone or its group and convert it into two amino- groups ;
chloro- derivatives are produced (Wallach and thus :
Kolliker, Ber. 1884, 17, 395). NH 2 -C 6 H 4 -N : N-C 6 H 5 +2H 2

(5) Action of hot sulphuric acid (Witt, Ber. =NH 2 -C 6 H 4 -NH 2 +C 6 H 6 -NH 2 .
1887, 20, 571). Azo- colouring matters which The base which was used to provide the diazo-
are derived from phenyl- or tolyl-#-naphthyl-
compound is thus regenerated, whilst the other
amine by the action of diazo- compounds on
component is converted into its amino- derivative.
these bases, when boiled with moderately reduction with zinc-dust, dyestuffs
dilute sulphuric acid, yield the bases, or their
By careful
obtained by the combination of diazotised
sulphonic acids, from which the diazo- compound aminoazobenzenesulphonic acid with phenols
was prepared, together with naphthazines.
yield the aminoazosulphonic acid without the
Thus the dyestuff obtained by combining latter undergoing reduction. Further, nitro-
diazotised sulphanilic acid with phenyl-- azo- dyestuffs can be reduced to the correspond-
naphthylamine, is decomposed into sulphanilic ing aminoazo- dyestuffs with sodium sulphide.
acid and phenonaphthazine :
The reduction of azo- dyestuffs is a useful
S0 3 H-C 6 H 4 -N 2 -C 10 H 6 -NH-C 6H 5 means of attacking the problem of their con-
/ N\ stitution, although the operation requires
considerable care (compare Witt, Ber. 1886,
'\N> 19, 1719; 1888, 21, 3468, and especially the
(6) Action of nitric acid. Azo- colouring references quoted in connection with reduction
matters are readily attacked by nitric acid, by hydrosulphite).
and the course of the reaction depends largely Azo- dyestuffs are also readily reduced by
on the conditions of temperature and concentra- titanous chloride, and a process for their estima-
tion. By the moderate action of nitric acid, tion by titration with this reagent has been
the dyestuff may simply be nitrated, thus worked out by Knecht (J. Soc. Dyers, 1903,
diphenylamine orange yields curcumeme and, 19, 169; Ber. 1903, 36, 166, 1549; 1907, 40,
by further action, azo- acid yellow, the dyestuffs 3819). A detailed account of the method of
in both cases, however, being accompanied by carrying out this and other methods of reduction
some nitrodiphenylamine produced by the will be found in Hans Meyer's Analyse und
fission of the azo- group. Also when flavazol Konstitutionsermittelung organische Verbin-
(diazotised toluidine combined with salicylic dungen, 2te aufl. 1909, p. 870.
acid) is nitrated, it yields Persian yellow (o-nitro- (9) Identification of azo- colouring matters
tolueneazosalicylic acid) (compare Ber. 1906, 40. on the fibre. This is carried out by observing
4207). the action on the dyed fabric of various reagents,
Methyl orange is decomposed even by cold forwhich various tables have been constructed
dilute nitric acid ; a methyl group is eliminated (compare Cain and Thorpe, The Synthetic
in the process, and dinitromonomethylaniline Dyestuffs, 1905 ; Lunge, Chemisch-technische
isproduced. The presence of a diazo- compound Untersuchungensmethoden, Eng. trans., edited
can also be detected (Fox, Ber. 1908, 41, 1989). by Keane, 1911).
Cold fuming nitric acid decomposes many Direct formation of azo- colours in the fibre.
azo- colouring matters (particularly those con- The production of an insoluble azo- dyestuff in
the fibrewas first achieved by T. and R. Holliday Nitrophenetidine Rose or Blue-red. Here
(E. P. 2757 of 1880), who impregnated the fibre o-nitro-^J-phenetidine is used as the diazotised
with a- or 0-naphthol, passed it then through base. A substitute for this is Azophor Rose A,
'
a diazo- solution, and finally developed the
'
which is a mixture of a stable diazo- compound
colour by treatment with alkali. An improve- with /3-naphthol. Other rose shades are
ment on this process was introduced by the produced by the use of p-nitro-o-anisidine.
Farbwerke vormals Meister, Lucius und Naphthylamine Bordeaux. Prepared on the.
' '
Briining, in 1889, which consisted in padding fibre from diazotised a-naphthylamine and
the fibre (generally cotton) with the sodium salt /3-naphthol. The dyestuff is used also as a
of a phenol (usually /3-naphthol), and passing pigment colour under the names Carminaph
the cloth through a diazo- solution, the free Garnet (D. H. 1 ) and Cerotine Scarlet 2 R (C. J.).
mineral acid of which has been neutralised by Azo Turkey Red is produced by treating cloth
adding sodium acetate. This process is very padded with /3-naphthol with diazotised 0-
largely used at the present day, and is applied naphthylamine. It is a bright scarlet, which,
to the greatest extent to the production of the however, is not very fast.
' '
so-called para-red (the azo- colour obtained Fast Azo Garnet. Prepared from diazotised
by combining diazotised ^-nitroaniline with o-aminoazotoluene and /3-naphthol. It is also
/3-naphthol). The colouring matters produced manufactured in substance and is used for
in this way will now be described. colouring oils and varnishes under the names
Paranitraniline Red. The colouring matter Oil Scarlet (M) (K) (W), Red B, Oil soluble,
was first prepared in substance byMeldoia (Chem. extra cone. (Remy), Cerotine Ponceau 3 B
Soc. Trans. 1885, 47, 657) by combining diazo- (C. J.), and Fat Ponceau R (K).
tised p-nitroaniline with /3-naphthol in alkaline Benzidine and Tolidine Puce. Obtained from
solution. As stated above, it is now almost tetrazotised benzidine or tolidine and ^-naphthol.
entirely produced on the fibre. The goods are Dark garnet to brown shades are produced which,
soaked in a bath containing sodium -naphth- however, are not fast to light. Rather yellower
oxide and Turkey -red oil, or thickening materials, shades result by using tetrazotised diaminocar-
squeezed out and dried at 65-80. They are bazole instead of these diamines; when treated
then passed through the diazo- solution, washed with copper salts the tints are very fast to light.
and soaped. In order to avoid preparing the Dianisidine Blue. Tetrazotised dianisidine
diazo- solution in the dye-house, various preis combined on the fibre with /8-naphthol in
parations may be used. Thus, Paranitraniline presence of copper salts. The tetrazo-compound
extra N paste is a mixture of ^-nitroaniline isalso put on the market as Azophor Blue D,
with the calculated amount of sodium nitrite, a mixture of the tetrazo- compound and alu-
and needs only to be stirred slowly into the minium sulphate which has been dried in a
necessary quantity of hydrochloric or sulphuric vacuum at 45. The colour is very fast to
acid, ice, and water, to produce the diazo- light, soap, and rubbing.
solution. A similar product is Benzonitrol The production of black insoluble colours
paste. Other preparations contain the diazo- in the fibre was first by the Farbwerke
effected
compound in a suitable form for keeping. vorm. Meister, Lucius und Briining. The
Thus, Nitrosamine Red is the sodium salt of cloth is padded with #-naphthol and tragacanth,
p-nitroaw<idiazobenzene (which is very stable) and treated with a mixture of the tetrazo-
and furnishes the true diazo- solution when compounds of dianisidine and certain other
mixed with dilute acid. Azophor Red, Azogen bases. The mixture of bases sold for this
Red and Nitrazol C. are mixtures of the diazo- purpose is known as Azo Black Base 0,
and the
sulphate with sodium sulphate (whereby sodium diazo- compounds are put on the market under
hydrogen sulphate is produced) they are dis-
; the name of Azophor Black S. Cassclla & Co.
solved in water, the solution filtered, if necessary, have introduced a black obtained by padding
and neutralised before use with sodium acetate the cloth with 1 : 6- or 1 :
7-aminonaphtho],
or hydroxide. Paranitraniline red is used as a and then passing it through diazotised ^-nitro-
substitute for the red Congo dyestuffs and for aniline so as to form the disazo- colouring matter.
Turkey red. It is extracted from the fibre when The aminonaphthol is put on the market as
treated with organic solvents, and when the Amidonaphthol BD and 3 B, and both brands
tiliro is heated to 180-200 the dyestuff partly are mixtures of the two aminonaphthols men-
sublimes. (For the formation of paranitraniline tioned. Full black colours are obtained which
red, see Pomeranz, Zeitsch. Farben. Ind. 1906, are fast to soap and chlorine, but they are not
5, 184; Erban and Mebus, Chem. Zeit. 1907, very easily applied in printing. black, also A
31, 663, 678, 687; Lichtenstein, Zeitsch. introduced by the same firm, is produced from
Elcktrochem. 1908, 14, 586 ; Prud'homme and Azotol C, which is an asymmetric dialkylated
Colin, Rev. Gen. Mat. Col. 1909, 13, 1, 66; identical with
di-p-diaminoazobenzene (it is
Bull . Soc. chim. 1909, (iv.) 5, 779 ; Bucherer, Kinzlberger's Ice Black).
The base is diazo-
and Wolff, Zeitsch. angew. Chem. 1909,22, 731 ; tised and combined with /3-naphthol on the
Justin-Mueller, Bull. Soc. chim. 1910, (iv.) 7, 60.) fibre in the usual way. The latter firm also
Metanitraniline Orange and Nitro-o-toluidine has introduced the use of the diazo- compound
Orange. Prepared as above from diazotised of aminochrysoidine, and of the tetrazo- com-
wi-nitroaniline or nitro-o-toluidine and #- for the
pound of ^-diaminodiphenylamine
naphthol. The former gives yellowish and the colours. Other tetrazo-
production of black
latter reddish shades of
orange. Their use is compounds recommended are these of amjno-
benzene-azo-a-naphthylainine (By.) and
not very extensive, as diamino-
they are not fast to rubbing,
and the colours sublime on keeping. An orange
dimethylcarbazole (M. ).
free from these
disadvantages can, however, See p. 364 for the full names of firms of which thes*
1
be obtained by letters are a contraction.

using m-nitro-^>-phenetidine.
Another process of producing azo- colour- (M.) = Farbwerke vorm. Meister, Luci
ing matters on the fibre is by the use of und Bruning, Hochst a/Main
primuline (q.v.). When cotton dyed with this (N. I.)
= Farbwerk Griesheim. Notzel,
dyestuff is treated with a solution containing Istel & Co., Griesheim a/Main.
hydrochloric acid and sodium nitrite, the dye- (0.)

= Chemische Fabrik Griesheim-
stuff is diazotised. The cloth is now passed Elektron, Werk Oehler (for-
merly K. Oehler), Griesheim.
'
through a bath containing the developer,'
consisting of a solution of an amine or a phenol. (P.) = Societe Anonyme des Matieres
0-naphthol is mostly used in giving Ingrain- or Colorantes & Produits Chi-
Primuline Red. An orange colour is obtained miques de St. Denis, Paris.
with resorcinol (Ingrain Orange), and a brown = Pick, & Co., Amsterdam.
with m-phenylenediamine (Ingrain Brown).
(P. L.)
(Sch.)
= The Lange
Schollkopf Aniline and
Many direct-dyeing cotton colours which contain Chemical Company, Buffalo,
a diazotisable amino- group (for example, U.S.A.
diamine black BH) acquire a faster, deeper, (T. M.) = Chemische Fabriken vorm. Wei-
and modified shade when similarly diazotised ler ter Meer, Uerdingen a/
on the fibre and developed with -naphthol Rhein.
or m-phenylenediamine. (W.) = Williams Bros. & Co., Hounslow,
In the succeeding portion of this article it is Middlesex.
E. P. = English Patent D. R. P. =
'
proposed to give an account of the most impor- Also ;
tant azo- colours which are at present in com- German Patent F. P. = French Patent A. P.
; ;
merce. 1 Each colour will be treated of under = American Patent.

its commercial name its chemical formula
;
I. BASIC Azo- COMPOUNDS.
given, and the mode of preparation and general
properties briefly described. Aniline Yellow Aminoazobenzene
;
Unless otherwise stated, it may be assumed C 6 H 6 -N 2 -C 6 H 4 -NH 2 .
that colouring matters containing a sulphonic [1] [4]

or carboxylic group are placed on the market This compound, discovered by Mene in 1861
in the form of their sodium salts. (Jahresber. p. 496), and introduced into com-
The following abbreviations are used for the merce by Simpson, Maule, and Nicholson in
names of firms :
1863, is interesting as being the first azo- colour
(A.) =Aktiengesellschaft fiir Anilinfa- made on a manufacturing scale. It was formerly
brikation, Berlin. prepared by passing nitrous acid gas into an
(B.) = Badische Anilin- und Soda- alcoholic solution of aniline. As a colouring
Fabrik, Ludwigshafen a/Rhein. matter it is now of no importance, but is largely
(Bl.) = The Basle Chemical Company. used as the starting-point in the manufacture of
(By.) = Farbenfabriken vorm. FT. Bayer other azo- colours and of iixdulines. In practice
& Co., Elberfeld. this compound cannot be prepared directly by
(C.)
= Leopold Cassella & Co., Frank- the action of one molecule of nitrous acid on
furt a/Main. two molecules of aniline, 'since diazoaminoben-
(C. J.) = Carl Jager, G. m. b. H., Dussel- zene is always the first product of this reaction :
dorf-Derendorf. 2C 6 H 5 -NH 2 ,HCl+NaN0 2
(Cl. Co.) = The Clayton Aniline Co., Ltd., =C 6 H 5 -N 2 -NH-C 6 H 6 +NaCl+HCl+2H 2 0.
Clayton, Manchester. The diazo- compound is slowly converted into
(Glaus & Co.) = Glaus & Co., Clayton, Man- the isomeric aniline yellow on being kept for
chester.
some time in contact with aniline and an
CD.) = Dahl & Co., Barmen. aniline salt
CD. H. ) = Dye Works, formerly L. Durand, :
& Co., Basle. C 6 H 6 -N 2 -NH-C 6 H 6 =C 6H 5 -N z -C,H4 -NHt ,
(F.) = A. Huguenin,
Fischesser & Co., Lutterbach. The manufacture carried out as follows :
is
(G.) = Aniline Colour- and Extract- 100 kilos, of aniline are mixed with 36 kilos, of
John R. concentrated hydrochloric acid, the mixture
Works, formerly
cooled (from outside) to about 18, and a solution
Geigy, Basle.
Read Holliday and Sons, Ltd., of 15-5 kilos, of sodium
nitrite in 18 kilos, of
(H.)
Huddersfield. water and 18 saturated sodium chloride
kilos, of
(I. )
= Societe pour 1'Industrie Chimique, solution added at first fairly rapidly, so that
und the temperature rises to 25, and then more
(formerly Bindschedler 28
Busch), Basle. slowly, the temperature being kept below
(K.) = Kalle & Co., Biebrich a/Rhein. by outside cooling. This operation takes about
(K. S.) = Sandoz & Co. (formerly Kern 7-8 hours. After 24 hours the change of
and Sandoz), Basle. diazoaminobenzene into aminoazobenzene i
(L.)
= Farbwerk Miilheim (formerly A. complete. The salt solution is now drawn off,
Leonhardt & Co.), Miilheim, the residue stirred with 96 kilos, of hydrochloric
near Frankfurt. acid and 64 kilos, of water, and the aminoazo-
= Levinstein, Ltd., Man- benzene hydrochloride is filtered off, washed with
(Lev.) Blackley,
chester. 2 p.c. hydrochloric acid, centrifuged and dried
at 60. The yield is 41 kilos, of dry aminoazo-
1
Wool Scarlet Crocelne 3 B (Sch.), and
R (Sch.),
benzene hydrochloride. The old aniline yellow
Diamine Red NO are no longer manufactured,
(C.)
according to information received by the writer from was the oxalate of the base. The free base
the manufacturers indicated. Since the firm Brooke, crystallises in yellow rhombic prisms. M.p.
Simpson, and Spiller, Ltd., ceased to exist, some of the 127-4; b.p. above 300. The hydrochloride
colouring matters made by them are now manufactured needles. Base slightly
by Messrs. Claus and Co., of Manchester. crystallises in steel-blue
AZO- COLOURING MATTERS.
365
soluble in hot water, readily soluble in alcohol. diamine. a brown paste
It is
giving a dark
Yellow solution coloured red by hydrochloric acid. orange-red solution in hot water. It yields a
Literature. Mene, 1861 (see above) ; Dale red solution with
strong sulphuric acid
and Caro, E. P. 3307 of 1863 ; Martius und Literature. E. P. 22886 of 1899 D. R. P.
;
Griess, Zeitsch. f. Chem. 1866, 2, 132 Kekule' ; 1 I L.S 1 .1.
ibid. 2, 689; Witt and Thomas, Chem. Soc. Chrome Brown P (P.); Di n itro Phenolazo-m-
Trans. 1883, 43, 112 ; Friswell and Green, ibid. amino PhenolOH-C 6 H 2 (N0 2 -N -C H
3 2 e 3 (OH)-NH . )
1885, 47, 917; and 1886, 49, 746; Stadel and Prepared from picramic acid and m-aminophenol
Bauer, Ber. 1886, 19, 1953. Introduced in 1903.
Butter Yellow ; Oil Yellow (W.) ; Dimethyl- Literature.!). P. 169579 F. P. 336559
aminoazobenzene, C 6 H 5 'N 2 'C 8 H 4 -N(CH 3
;
),j.
Pre- Diazine Green (K.); Janus Green B
(M.)
the action of diazobenzene chloride
pared by N
on dimethylaniline. Substance forms yellow C 2 H 5 -N-C,H 3 <|>C 6 H 3 -N 2 -C 6 H 4 -N(CH
3 ) 2.
leaflets of m.p. 115; soluble in dilute hydro-
chloric acid with a red colour ; precipitated by
Soluble in strong sulphuric acid with
alkali.
Cl C 6H 5
a yellow colour, becoming red on dilution.
Literature. Griess, Ber. 1877, 10, 528.
Prepared from diazotised diethylsafranine and
Y dimethylaniline. The commercial product is a
Chryso'idine (most firms) ; Chryso'idine
brown or dark-green powder
(H.) (W.); Chrysoidine JEE (C. J.); Chrysoidine giving an olive-
1
Small green solution with strong sulphuric acid. Janus
Crystals; Chrysoidine Crystals (T. M.) Green G is a dyestuff of
Diaminoazobenzene C 6 H 5 -N 2 'C 6 H 3 (NH,) 2 ,
analogous constitution.
[1] [2 :
4]
Literature. E. P. 7337 of 1897 F P
265438 ; D. R. P. 95668.
This colouring matter is prepared by mixing
a solution of diazobenzene chloride with a II. ACID Azo- COMPOUNDS.
solution of m-phenylenediamine. In practice A. Sulphonic Acids of Aminoazo- Compounds.
a known weight of aniline is dissolved in
Acid Yellow (A.); Fast Yellow (B.)
dilute hydrochloric acid and diazotised, the Fast Yellow G New Yellow L (K.)
(By.)-
solution being diluted so as to contain about 2-3
; Yellow SS ;
This and a dilute solution of (P.); Fast Yellow extra (By.). This colouring
p.c. of diazo- salt. matter is a mixture of the sodium salts of mono-
phenylenediamine hydrochloride are run simul- and disulphonic acids of aminoazobenzene
taneously into a sodium chloride solution, and
the colouring matter is filtered off through a HS0 3 -C 6 4 -N 2 -C 6 H 1 -NH, and H
filter press. The press cake is then dissolved HS0 3 -C 6 4 -N 2 -C 6 3 (HS0 3 H2
H >NH .
in hot dilute hydrochloric acid, the hot solution Prepared by the action of fuming sulphuric acid
filtered, and hydrochloric acid added to the on aniline yellow (3-5 parts acid to one of
filtrate. The chrysoidine separates in small aminoazobenzene). Solution not precipitated
needles, which are filtered off, centrifuged, and by alkali
colour dissolves in strong sulphuric
;
dried at 50. The free base forms yellow acid with a brownish-yellow colour
becoming
needles; m.p. 117-5. Slightly soluble in redder on dilution. Solution gives a precipitate
water, readily in alcohol ; solutions orange. with barium chloride, but not with calcium
The commercial product is the hydrochloride chloride. The corresponding colouring matter
C 12 H 12 N 4 ,HC1, which forms beautiful blackish- from aminoazotoluene is somewhat more orange
green prisms with a metallic lustre. The strong in shade, and is known as Fast Yellow
(B.) ;
solution of the salt solidifies on rapid cooling to Yellow (By.) WFast Yellow R (K.). ;
a red jelly. Dissolves in strong sulphuric acid Literature. Grassier, E. P. 43 of 1879 ;

with a brownish-yellow colour. A. P. 253598 D. R. P. 4186, 7094; Chem. Ind.
;
Literature. Hofmann, Ber. 1877, 10, 213 ; 1879, 2, 48, 346; Griess, Ber. 1882, 15, 2187;
Witt, ibid. 350 and 654 Griess, ibid.
; 389. Eger. Ber. 1889, 22, 847.
Chrysoidine R (H.) (W.) (G.) (L); Chrysoidine Methyl Orange Helianthin Orange III. ;
; ;
REE (P.); Cerotine Orange (C. J.); Gold Orange Gold Orange , p-Sulphobenzeneazodimethyl-
for Cotton (T. M.) (D. H.); Benzeneazo-m-tolyl- aniline HS0 3 -C 6 H 4 -N 2 -C 6 H 4 -N(CH,),. Pre-
H H
enediamine C 6 5 -N.2 -C 6 2 (CH 3 )(NH 2 ) 2 . Pre- [4] [1] [4]
pared from aniline and m-tolylenediamine as pared by the action of diazotised sulphanilic
in the preceding case. The free base melts ncid on dimethylaniline. Solution of colouring
1
at 165-166. The commercial product is the matter orange, and not precipitated by alkali ;
dilute acids produce a crystalline precipitate,
hydrochloride, which forms yellowish-brown
the crystals having a violet reflexion (the free
lumps. Dissolves in strong sulphuric acid with
a greenish-yellow colour. sulphonic acid). The substance dissolves in
Chrysoidine R (D. H.); Tolueneazo-m- strong sulphuric acid with a yellow colour
H
tolylenediammeCH 3 -C 6 4 -N 2 -C 6 2 (CH 3 )(NH 2 ) 2 H . becoming red on dilution.
Prepared as above from o-toluidine and ra- Literature. Griess, Ber. 1877, 10, 528.
tolylenediamine. The commercial product is Tropseoline 00 (C.); Orange IV. (P.); Di-
the hydrochloride. It is a crystalline violet phenylamine Orange; Acid Yellow D (A.);
powder which gives a brown colour in strong Orange N (B.) New Yellow (By.) Orange M
; ;
sulphuric acid. (I.) ; p-Sulphobenzeneazodiphenylamine

Meta Chrome Brown B (A.) :
Dinitrophenol- HS0 3 -C 6 H 4 -N 2 -C 6 H 4 -NH-C 6 H 5 .
azo-/n,-tolylenediamine
OH-C,H a (NO a ) JN J -C< H a (CH 8 )(NH 2 ) 2 .
1
For detailed information on the manufacture of
Prepared from picramio acid and m-tolylene- sulphanilic acid and its homologues see MUhlhauser,
1
Chrysoidine Crystals also contain the homologues Dingl. poly. J. 1887, 264, 181 and 238 ; Paul, Zeitsch .
from o- and p-toluidine. angew. Chem. 1896, 9, 686.
Produced by the action of diazotised sulphanihc Literature. Roussin and Poirrier, E. P.
acid on diphenylamine dissolved in alcohol or 4490 of 1878; D. R. P. 6715; F. P. 127221 Chem. ;
crude carbolic acid. The product is thrown on an Ind. 1879, 2, 292.

open filter, the paste dissolved in concentrated Archil Substitute 3 VN (P.); Archil Sub-
aqueous potassium carbonate and precipitated stitute V (A.); p-Nitrobenzeneazo-a-naphthyl-
by adding sodium hydroxide. The colouring aminesulphonic acid
matter is not very readily soluble in water ;
N0 2 -C 6 4 -N 2 -C 10 H H (NH 2 )-S0 3 H.
yellow, and when strong deposits
the solution is 6
crystals on
cooling. Substance dissolves in Prepared by the action of diazotised p-nitro-
aniline on a-naphthylamine-5-sulphonic acid.
strong sulphuric acid with a violet colour,
Forms a brown powder giving a red solution in
becoming redder and giving a greyish precipitate
of the free sulphonic acid on dilution. The water or strong sulphuric acid.
Literature. E. P. 12692 of 1887; D. R. P.
aqueous solution of the substance is coloured red
dilute acids. 45787 ; F. P. 185908.
by
When nitrated this colour furnishes a mono- Palatine Chrome Brown W (B.) ; ^
nitro- derivative together with a mixture of hydroxybenzeneazo-m-phenylenediamine
mono-, di-, and tri- nitrodiphenylamine : S0 3 H-C 6H 3 (OH)-N 2 -C 6 H 3 (NH 2 ) 2.
moderate nitration yields a yellow colouring from diazotised
matter which is found in commerce under the Prepared o-aminophenol-p-
names of Citronine (0.); Curcumeine (A.); sulphonic acid and m-phenylenediamine. A
black- brown powder dissolving in hot water
Azoflavine 3 R ex. cone. (T. M.) ; Citronine NE
with an orange-brown colour, and in strong
(P.). More energetic nitration of Orange IV.
sulphuric acid to give a dark orange -brown
furnishesAZO Acid Yellow (A.) AZO Yellow (M ; ) ;
solution.
Azo Yellow 3 G, ex. cone. (T. M.); Citronine 2 AEJ Literature.A. P. 628814 ; F. P. 284741.
(P.); Azoflavine (B.); Indian Yellow (By.).
Anthracyl Chrome Green (D.); Dinitro-
Both dyestuffs are ochre-yellow powders and
phenolazo-a-naphthylamine-4-sulphonic acid
give with strong sulphuric acid reddish- violet H
OH-C 6 2 (N0 2 ) 2 -N 2 -Ci B (S0 3 H)-NH 2 H .
and magenta-red solutions respectively.
Metanil Yellow (0.), (B.), (A.), (C. J.); Prepared by the action of diazotised picramic
Orange MN Tropaeoline G (C.); Yellow
(I.); M acid on naphthionic acid. Solution in water
(P.); Yellow GR extra (T. M.).; m-
Metani! is reddish-brown, and in strong sulphuric acid
bluish fiery red.
Sulphobenzeneazodiphenylamine
H
HS0 3 -C 6 4 -N 2 -C 6 4 -NH-C 6 H 6 H .
D. P. 142153.
Literature.
[3] [i]
Alkali Brown (D.) ; Benzo Brown 5 R (B}'.) ;
[4] Alkali Brown (L. P.) ; Cotton Brown R (B.) ;
R
Prepared in the same manrer as the preceding Terra Cotta (G.); Primulineazo-wi-phenylene-
from m-diazobenzenesulphonic acid l and di- diamine P l
N 2
g
C 6H 3 (NH 2 ) 2
.
Prepared from
phenylamine. Aqueous solution orange, giving diazotised primuline or dehydrothio-jp-toluidine-
no precipitate with alkalis, becoming red and sulphonic acid on m-phenylenediamine. Solution
precipitating with dilute acids. Dissolves in brownish-red, precipitated by acids or alkalis.
strong sulphuric acid with a dull violet colour, Gives a bluish-violet solution with strong
becoming magenta-red on dilution. sulphuric acid.
Metanil Yellow S Acid Yellow 2 G, is pro-
; Apollo Red (G.) ; Archil Substitute extra (C.);
duced by sulphonating the preceding colouring p - Nitrobenzeneazo-a-naphthylaminedisulphonic
matter. acid, N0 2 -C 6 H 4 -N 2 -C 10 H 4 (NH 2 )(S0 3 H) 2 Pre- .
Literature. E. P. 1226 of 1879 ; 4966 of pared from diazotised p-nitroaniline and a-

1880 ; Paul, Zeitsch. angew. Chem. 1896, 9. 686. naphthylamine-4 6- or 4 7-disulphonic acid- : :
Fast Yellow N Jaune Solide N; Cur-

(P.); Gives a brownish-red solution in water and a
cumeine ; Sulphotolueneazodiphenylamine magenta-red in strong sulphuric acid.
HS0 3 -C H 7 6
-N 2 -C 6 H 4 -NH-C H 5 6
Literature. E. P. 9468 of 1887; A. P.
~~ 376392 F. P. 184638.
;
W~~ Brilliant Archil C (C.) ; Brilliant Wool Scarlet

This colouring matter is homologous with the (K) ; Azimide of p-nitrobenzeneazo-1 :
8-naph-
two preceding, which it resembles in its general thylenediaminedisulphonic acid
properties.
Literature. Roussin and Poirrier, E. P. N0 H H 4 (S0
2 -C 6 4 -N 2 -C 10 3 H)
4491 of 1878.
Archil Substitute V; ^-Nitrobenzeneazo-
Prepared by the action of nitrous acid on the
o-naphthylamine-p-sulphonic acid
product from diazotised jj-nitroaniline and
H
N0 2 -C 8 4 -N 2 -C 10 8 (NH 2 )-HS0 3 H .
1 8-naphthylenediamine-3 6-disulphonic acid.
: :
Prepared by the action of diazotised p-nitro- A brownish-red powder dissolving in water with
2
aniline on naphthionic acid in weakly acid a red, and in strong sulphonic acid with a blue,
solution. Solution precipitated by acids and solution.
alkalis. Strong sulphuric acid gives a magenta- Literature. E. P. 24714 of 1893 ;
D. R. P.
red solution, becoming brownish and precipitating 77425 ; F. P. 234837.
on dilution. Wool Violet S (B.) ;
Dinitrobenzeneazo-
1
m-Aminobenzenesulphonic acid is prepared by diethylmetanilic acid
sulphonating nitrobenzene and reducing the wi-nitro-
benzenesulphonic acid thus formed.
(N0 2 2 C 6 H 3 -N 2 -C 6 H 3 (S0 3 H)-N(C 2 H 5
) ) 2.
2
Naphthionic acid is manufactured on a large scale Prepared from diazotised 2 : 4-dinitroaniline
by heating a-naphthylamine with 3-4 parts of strong and diethylmetanilic acid. A black powder
sulphuric acid or by heating dry naphthylamine sulphate
a
to 180 -200. P = the residue of primuline.
1
giving a reddish- violet solution in water and a ibid. 1887, 20, 904 ; Will and Pukall, ibid. 1120 ;
scarlet-red in strong sulphuric acid. Pukall, ibid. 1147; Fischer and Wimmer, ibid
Literature. E. P. 6197 of 1894; D. R. P. 1578; Will, ibid. 1888, 21, 604; Kostanecki
86071 F. P. 239096
; A. P. 525656. ; ibid. 3119.
Salmon Red (A.); Methylbenzenylamino- Sudan I (A.) (F.) (Ib.) (K.) (W.) ; Carminaph
thioxylenolazo-#-naphthylamine-3 :
6-disulpho- (D. H.) ; Cerotine Orange G (C. J.); Benzene-
nic acid H
azo-0-naphthol C 6 5 -N 2 -C 10 H 6 -OH. Prepared
from diazobenzene chloride and
jS-naphthol.
(CH 3 2C 6H ) K>C 6 H 3 -N 2 -C 10H 4 (S0 3H) 2 A brick-red powder insoluble in water. Used
for colouring oils, &c.
CH 3 NH 2 Literature. Liebermann, Ber. 1883, 16, 2860;
Prepared from diazotised dehydrothio-ra-xyli- Denare, Gazz. chim. ital. 1885, 15, 406 ; Zincke
dine and -naphthylamme-3 6-disulphonic acid :
and Bindewald, Ber. 1884, 17, 3031 ; Zincke and
R. Aqueous solution is orange red. Gives Rathgen, ibid. 1886, 19, 2484 ; Fischer and Wim-
violet solution in strong sulphuric acid. mer, ibid. 1887, 20, 1579 ; Weinberg, ibid. 3172 ;
Literature. Paul, Zeitsch. angew. Chem. Jacobson, ibid. 1888, 21, 415 ; Meldola and East,
1896, 9, 680. Trans. Chem. Soc. 1888, 53, 460 ; Meldola and
Brilliant Yellow S (B.) (T. M.) ; Yellow WR Morgan, ibid. 1889, 55, 603 ; Goldschmidt and
(I.); Curcumine (G.); j>-Sulphobenzeneazodi- Resell, Ber. 1890, 23, 496; Goldschmidt and
pheuylaminesulphonic acid. Prepared by sul- Brubacher, ibid. 1891, 24, 2306; McPherson
Solution in water is Ber. 1895, 28, 2418; Farmer and Hantzsch,
phonating orange IV.
vellow and in strong sulphuric acid bluish-red. ibid. 1899, 32, 3100; Mohlau and Strohbach,
Literature. D. R. P. 21903. ibid. 1900, 33, 805 ; Goldschmidt and
Keppeler,
Lanacyl Violet B (C.); Disulphohydroxy- ibid. 894 ; Mohlau and Kegel, ibid. 2873 ;
naphthaleneazoethyl-a-naphthylamine Betti, Gazz. chim. ital. 1900, 30, ii. 164.
(HS0 3 )2 C 10H 4 (OH)-N 2 -C 10

H 6 -NH-C 2
H5 .
Sudan II (A.) (K.); Red B (B.) (Fi.) ; Cerotine
Scarlet G (C. J.) ; Xyleneazo-6-naphthol
Prepared from diazotised 1 :
8-aminonaphthol-
3 : 6-disulphonic acid and ethyl-a-naphthyl- C 6 H 3 (CH 3 )2 -N 2 -C 10 H 6 -OH.
amine. Solution in water is reddish-violet, and Prepared from diazotised xylidine and #-
in strong sulphuric acid is greenish-blue. naphthol.
Literature. E. P. 12556 of 1896 ; D. R. P. Carminaph Garnet (D. H.); Cerotine Scarlet
94288 ; F. P. 257136. 2 R (C. J.); a-Naphthaleneazo-0-naphthol
B. Carboxylic Acids of Aminoazo- Compounds. C 10 7 -N 2 -C H
a -OH.
1?
H
Yellow fast-to-soap (P.); MG Prepared from diazotised 'o-naphthylamine and
Orange (P.); An insoluble paste used in print-
j8-naphthol.
m-Carboxybenzeneazodiphenylamine ing. (See also Naphthylamine Bordeaux, p. 363.)
H
C0 2 H-C 6 4 -N 2 -C 6 4 -NH-C 6 6 H H .
Azophosphine GO (M.) ; Chloride of m-
Prepared by the action of m-diazobenzoic acid trimethylaminobenzeneazoresorcinol
on diphenylamine. Used in wool-dyeing and C1N(CH 3 ) 3 -C 6 H 4 -N 2 -C 6 H 3 (OH) 2 .
especially calico-printing ; the shades are very from

diazotised m-aminophenyltri-
A Prepared
fast to soap. brown paste, difficultly soluble
in water. Solution becomes reddish-violet methylammonium chloride and resorcinol. Solu-
tion in water is yellowish-red, and in strong
with acids. Dissolves with a violet colour in
sulphuric acid brownish-red.
strong sulphuric acid, becoming red on dilution. Literature. E. P. 14494 of 1895 ; D. R. P.
Literature. E. P. 4621 of 1883 ; D. R. P.
87257 ; F. P. 249227.
29991 ; F. P. 157755 ; A. P. 297852.
New Phosphine G (C.); w-Dimethylamino-
C.
Hydroxyazo- Compounds. tolueneazoresorcinol,
Sudan Brown (A.); Pigment Brown (B.); N(CH 3 ) 2 -CH 2 -C 6 H 4 -N 2 .C 6 H 3 (OH) 2 .
o-Naphthaleneazo-a-naphthol Prepared from diazotised ^-aminobenzyldi-

C 10H 7 -N 2 -C 10H 6 -OH. methylamine and resorcinol. Gives a yellowish-
brown solution in water and strong sulphuric acid.
Prepared by the action of diazotised a-naphthyl- Literature. E. P. 22572 of 1892 D. R. P.
amine on a-naphthol in alkaline solution. ;
70678 F. P. 225968 ; A. P. 515100.

Literature. E. P. 786 of 1878; D. R. P. ;
5411 F. P. 123148 A. P. 204799 ; Frankland,

Tannin Orange R (C.); w-Dimethylamino-
; ;
Trans. Chem. Soc. 1880, 37, 752. tolueneazo-^-naphthol

Sudan G (A.) (F.) (Ib.) (W.) Carminaph J ;
N(CH 3 2 -CH 2 -C 6 H 4 -N 2 .C 10 H,-OH.
)
(D. H.) Cerasine Orange G (C.); Cerotine

; Prepared from diazotised ^>-aminobenzyldi-
Yellow R (C. J.) ; Chrysoiin insoluble (P.); methylamine and /3-naphthol. A brown
H
Benzeneazoresorcinol C 6 S -N 2 -C 6 3 (OH) 2 . Pre- H powder or a 50 p.c. paste. Sparingly soluble
pared by the action of diazobenzene chloride in water, with a browncolour. Gives a yellowish-
on resorcinol in alkaline solution. Solution brown solution in strong sulphuric acid.
of colouring matter
yellow, giving a brown pre- Literature. As for the preceding colour.
cipitate with acids. Dissolves in strong sul- Azochromine (G.); Tetrahydroxyazoben-
phuric acid with a yellowish-brown colour. zene OH-C e H 4 -N 2 -C 6 H 2 (OH) 3 Prepared from
.
Literature. Baeyer and Jager, Ber. 1875, 8, diazotised ^-aminophenol and pyrogallol. Com-
151 ; Typke, ibid. 1877, 10, 1576 ; Wallach, mercial product is a 30 p.c. paste, giving a
ibid. 1881, 14, 24 ; WaUach and Fischer, ibid.
dark-yellow solution in boiling water. With
1882, 15, 2814 ; Meyer and Kreis, ibid. 1883, strong sulphuric acid it gives a brown solution.
16, 1329 ; Liebermann and Kostanecki, ibid. Literature. E. P. 11902 of 1893; D. R. P.
1884, 17, 880 ; Heumann and Oeconomides, 81109; F. P. 230937; A. P. 548460.
Black (K.)
Diazine Janus Grey B (M.);
; Azofuchsine B (By); Tolueneazo-1 8-dihy. :
Safranineazophenol. Prepared from one of droxynaphthalenesulphonic acid

the varieties of safranine and phenol. Its H
CH 3 -C 6 4 -N 2 -C 10 4 (OH) 2 -S0 3 H.H
solution in water is
blackish-green blue, and in
Prepared by the action of. diazotised commei
strong sulphuric acid green. cial toluidine on 1 8-dihydroxynaphthalene-4-
:
Literature. Mon. Sci. 1886, (iii.) 16, 984.
sulphonic acid. Solution in water is bluish -
Indoine Blue R Janus Blue (M.) ;
(B.) (G.) ;
red, and in strong sulphuric acid violet.
Naphthindone (C.); Bengaline (K.); Vac Blue Literature. E. P. 18517 of 1889 D. R. P.
(H.) Fast Cotton Blue R (0.) Indole Blue R :
; ;
54116 F. P. 203744 ; A. P. 466841, 468142.
(A.) ; Diazine Blue (K.) Madras Blue P (P.); ;
;
Ponceau 4 GB (A.) (Lev.); Croceine Orange
Safranineazo-j8-naphthol. Prepared from va-
rious safranines and /3-naphthol. It gives a (By.)(C.); Brilliant Orange G (M.)(C.J.); prange
violet solution in water, and a greenish-brown GRX(B.); Benzeneazo-jS-naphtholsulphonic acid
in strong sulphuric acid.
H H
C 6 5 -N 2 -Ci 5 (S0 3 H)-OH(/3).
Literature. E. P. 4543 of 1891, 18769 of Prepared by the action of diazobenzene chloride
1893, 3488 of 1895, 23985 of 1898 ; D. R. P.
on 0-naphthol-6-sulphonic acid (Schaffer's acid)
in alkaline solution. Solutions in water or
61692, 85690, 85932, 91721, 92015, 105433,
108497; F. P. 212276, 245239, 250239, 283013, strong sulphuric acid are orange-yellow.
P. 524251, 524254; Walter, Aus Literature. Griess, Ber. 1878, 11, 2197.
285360; A.
der Praxis der Anilinfarbenfabrikation, 1903, Orange GT (By.) ; Orange RN (C.) ; Orange
306 (where the preparation is described in (M.) Tolueneazo-0-naphthol-sulphonic acid
;
detail).
C 7H 7 -N 2 -C 10
H
5 (S0 3 H)-OH(j8). Prepared by
diazotising commercial toluidine and combining
D. Sulphonic Acids of Hydroxyazo- Compounds. with Schaffer's -naphtholmonosulphonic acid
1. MONOSTTLPHONIC ACIDS. in alkaline solution.
Orange aqueous solution
Tropaeoline (C.); Resorcin Yellow (A.); gives an oily precipitate with acids. Dissolves
in strong sulphuric acid with a magenta-red
Chrysoin (B.) Chryseoline ; Gold Yellow (By.)
; ;
Yellow T (L); Acme Yellow (L.); ^-Sulpho- colour, giving an oily deposit on dilution.
H
benzeneazoresorcinol HS0 3 'C 6 4 -N 2 'C g 3 (OH) 2 H .
Scarlet (A.) GR
Scarlet R (By.) ; Brilliant
;
Produced by the action of diazotised sulphanilic Orange R; Orange L (Lev.)

(M.) (C. J.) (P.).
acid on resorcinol in alkaline solution. Solution Homologous with the last prepared from ; dia-
zotised xylidine and Schaffer's acid. Dissolves
of colouring matter orange ; substance dissolves
in strong sulphuric acid with a red colour, becom-
in strong sulphuric acid with a yellow colour.
Literature. Griess, Ber. 1878, 11, 2195; ing brown and precipitating on dilution.
Witt, Trans. Chem. Soc. 1879, 35, 183.
Literature. Levinstein, Ber. 1880, 13, 586.
II (most firms); Tropaeoline 000,
Azococcine 2 R (A.) ; Double Scarlet (Lev.); R
Orange
No. 2 Betanaphthol Orange ; Mandarin G Extra Xyleneazo-a-naphtholsulphonic acid
;
(A.); Gold Orange (By.); Orange Extra (C.) ;

H H
(CH 3 ) 2 C8 3 -N 2 -C10 5 (S0 3 H)-OH(a).
Orange A (L.) ; Gold Orange extra cone. (T.M.); Prepared by the action of diazoxylene chloride
p-Sulphobenzeneazo--naphthol (commercial xylidine diazotised) on a-naphthol-
HS0 3 -C 6 H 4 -N 2 -C 10 H S -OH. 4-sulphonic acid in alkaline solution. Aqueous
solution not precipitated by alkalis ; when hot
Prepared from diazotised sulphanilic acid and and concentrated deposits bronzy crystals on
-naphthol. Solution orange, becoming red on Dissolves in strong sulphuric acid with
addition of sodium hydroxide. Solution in cooling.
a reddish- violet colour, becoming brown and pre-
strong sulphuric acid red, becoming orange on
dilution. cipitating free acid on dilution.
Literature. Hofmann, Ber. 1877, 10, 1378; 26012.
Griess, ibid. 1878, 11, 2198 ; Witt, ibid. 1879, 12,
259 ; Miller, ibid. 1880, 13, 268 ; Witt, Chem. Azo Grenadine L (By.); Acetylaminoben-
Zeit. 1880, 4, 437 ; Muhlhauser, Dingl. Poly. J. zeneazo-o-naphthol-4-sulphonic acid
.1887, 264, 181, 238 ; Paul, Zeitsch. angew. Chem.
CH 3 -CO-NH-C 6 H 4 -N 2 -C 10
H 8 (S0 3 H)-OH.
1896, 9, 686 (the last two papers give details of Prepared from diazotised p-aminoacetanilide
the manufacture). and o-naphthol-4-sulphonic acid. Magenta-red
Orange R (L); Orange T (K.); Kermesin aqueous solution becomes orange-red with
Orange (L.); Mandarin GR (A.); Sulpho-o-to-
sodium hydroxide. Solution in strong sulphuric
acid is red.
Iueneazo-j8-naphthol
HS0 3 -C H<-N 2 -C 10H 6 -OH(0). Azoeosine (By.) (Lev.) ; Azoeosine G (K.)111
7
Anisoleazo-o-naphthol-4-sulphonic acid
Homologous with the preceding, the diazotised H
CH 3 -0-C 6 S -N 2 -C 10 5 (S0 3 H)-OH. H
sulphonic acid of o-toluidine being used instead
of sulphanilic acid. Prepared from diazotised o-anisidine and
Orange 2 R (I.); Orange R (B.); Sulphoxylene- naphthol-4-sulphonic acid. Gives a red solution
in water and a carmine-red in strong sulphuric
azo- -
naphthol HS0 3 -C 8H 8 -N 8 -C 10 H 6 -OH(j8).
acid.
Prepared in the same manner as the preceding
from the sulphonic acid of commercial xylidine Literature. E. P. 2237 of 1883.
and /}-naphthol. Aqueous solution gives a Benzoyl Pink; Rose de Benzoyl(P.); Benz-
reddish-brown precipitate with dilute acids. oylaminoditolylazo-a-naphthol-4-sulphonic acid
Dissolves with a red colour in strong sulphuric H H
C 6 5 -CO-NH-C6 4 -C 8 4 -Nj-C10 s -OH H H
acid, giving a brown precipitate on dilution.
Literature. The manufacture of the two CH 3 CH 3 SO H
3
last colouring matters is described in the paper Prepared from diazotised monobenzoyl-o-tolt
by Muhlhauser already referred to. dine and a-naphthol-4-sulphonic acid. A brie
red paste, giving a cherry -red solution in water, chloric acid, and, with sodium hydroxide,
and a bluish-red solution in strong sulphuric becomes first deep- blue and then re'd. Tho
acid. solution in strong sulphuric acid is blackish-blue,
Literature. D. R. P. 60332. giving a brown precipitate on dilution.
Fast Red BT
(By.) (Lev.) (D.H.) ; a-Naphtha- Literature. E. P. 15982 of 1904 ; D. R. P.
leneazo-0-naphthol-6-sulphonic acid 169683 ; F. P. 350071 ; Ital. P. 73531 Aust. P. ;
C 10H 7 -N 2 -C 10H 5 (S0 3 H)-OH. 27191.

Brilliant Double Scarlet G (A.) (Lev.)
Prepared from diazotised a-naphthylamine and Scarlet for silk (M.); Ponceau for silk (P.).
(K.) ;
Gives Pre-
8-naphthol-6-sulphonic acid (Schaffer).
a red solution in water and a violet in strong pared from /8-naphthylamine-6-sulphonic acid
and $-naphthol. Aqueous solution gives brown
sulphuric acid.
Literature. 786 of 1878; D. R. P.
E. P. precipitate with dilute acids. Dissolves in strong
5411 F. P. 123148 ; A. P. 204799.
;
sulphuric acid with a red colour, giving a brown
Fast Brown N (By.) Acid Brown ; (M.) ; precipitate on dilution.
Literature as under Fast Red B.
Naphthylamine Brown ; 2>-Sulphonaphthalene-
HS0 -C H -N -C H -OH. Pre- Fast Fast Red A (B.) (C. J.) (Lev.); Roc-
Red ;
azo-a-naphthol 3 10 6 2 10 6
H.) ; Rauracienne ; Rubidine ; Sulpho-
celline (D.
pared by the action of diazotised o-naphthyl-
amine-4-sulphonic acid (naphthionic acid) on naphthaleneazo-j8-naphthol
a-naphthol in alkaline solution. Colouring
matter gives a reddish-brown solution, not Prepared by the action of diazotised naphthionic
changed by acids or alkalis. Dissolves in strong acid on /8-naphthol in alkaline solution. Sub-
sulphuric acid with a reddish- violet colour. stance dissolves in hot water with a reddish-
Literature. E. P. 786 of 1878; D. R. P. brown colour ; concentrated solution when
5411 ; F. P. 123148 ; A. P. 204799. rapidly cooled solidifying to a brown gelatinous
Fast Brown 3 B (A.); Sulphonaphthalene-2- mass. Soluble in strong sulphuric acid with a
H
azo-o-naphthol HS0 3 -C 10 ? -N 2 -C 10 e -OH. Pre- H violet colour, becoming brown and giving a
pared by the action of diazotised /3-naphthyl- precipitate of the free acid on dilution. The
amine-6-sulphonic acid on a-naphthol in alkaline corresponding colouring matter from o-naphthyl-
solution. amine-5-sulphonic acid is called Brilliant Fast
Aqueous solution brownish-red, becoming RedG(B.).
violet with dilute acids and red with alkalis. E. P. 786 of 1878; D. R. P.
Literature.
Solution in strong sulphuric acid blue, giving 5411 F. P. 123148 ; A. P. 204799 ; Griess, Ber.
;
reddish- violet precipitate on dilution. 1878, 11, 2199 ; 1879, 12, 1364.
Literature. E. P. 3724 of 1882; D. R. P. Acid Ponceau (D. H.); Fast Acid Scarlet;
22547 ; F. P. 150503 ; A. P. 332829. Ponceau S for silk (I.) ; Ponceau G for Silk (K.) ;
Chrome Fast Cyanine G (I.), introduced into Sulpho-/3-naphthaleneazo-^-naphthol

commerce in 1907, is prepared by the action of H
HS0 3 -C 10 6 -N 2 -C 10 6 -OH. H
diazotised l-amino-2-naphtholsulphonic acid on
Prepared by sulphonating j8-naphthylamine,
a-naphthol. diazotising the mixed isomeric sulphonic acids,
Eriochrome Blue Black B (G.); Sulpho- and combining with -naphthol in alkaline
naphtholazo-a-naphthol solution. Aqueous solution gives a brown pre-
HS0 3 -C 10 H 6 (OH)-N 2 -C 10 H 6 -OH. cipitate with dilute acids. Dissolves in strong
Prepared by the action of diazotised 1-amino- sulphuric acid with a red colour, becoming brown
/3-naphthol-4-sulphonic acid on a-naphthol.
1 and precipitating on dilution.
The blackish- violet aqueous solution on addition Lithol Red B (B.); Sulphonaphthaleneazo-
of hydrochloric acid becomes first reddish- 0-naphthol HS0
3 -C 10 H
g -N 2 -C 10 6 -OH.
Pre- H
brown, and then gives a brownish- black prepared by the action of diazotised /8-naphthyl-
cipitate. With sodium hydroxide the solution amine-1 -sulphonic acid on /8-naphthol. The
becomes first blue and, on adding excess, finally commercial product is a paste which is only
red. The solution in strong sulphuric acid is very sparingly soluble even in hot water. It
is used exclusively in the manufacture of lakes.
blue, giving a violet-black precipitate on dilution.
Literature. E. P. 15025 of 1904 ; D. R. P. Literature. E. P. 25511 of 1899 D. R. P. ;
181326 F. P. 350055 ; Ital. P. 73530 ; Aust.

;
112833 ; F. P. 297330 A. P. 650757.
;
P. 30630. Clayton Cloth Red (Cl. Co.); Stanley Red

Eriochrome Black T (Cl. Co. ) ; Sulphobenzenylaminothiocresolazo-
(G.); Nitrosulpho-
naphtholazo-o-naphthol 0-naphthol
N0 2 -C 10 H 4 (S0 3 H)-N 2 -C 10 H 6 -OH. \C-C H (S0 H)-N
Prepared by the action of diazotised 8-nitro- 6 4 3 2 -C 10 H 6 -OH.
amino--naphthol-4-sulphonic acid on a-naph-

thol. The reddish-brown aqueous solution Prepared by the action of diazotised dehydro-
p-toluidinesulphonic acid on 0-naphthol. The
gives a violet-brown precipitate with hydro-
commercial product is the ammonium salt.
In the constitutional formula of this colouring
1
Forms a reddish-browr solution in water, and a
matter, kindly communicated along with other informa-
tion to the writer
violet-red with strong sulphuric acid.
by the manufacturers, the azo- group D. R. P.
sshown attached to the 2- position of the a-naphthol, Literature. E. P. 18901 of 1889 ;
although the 4- position is unoccupied. The combina- 51331.

Acid Alizarine Black R (M.); Nitrosulpho-
tion is probably effected in presence of very concentrated
alkali hydroxide. Other examples of this ortho- com-
bination are known, both in the benzene and naphtha- phenolazo-3-naphthol
lene series. (Compare Michel and Grandmougin, Ber. H
OH-C 6 2 (N0 2 )(S0 3 H)-N 2 -C 10 6 -OH. H
1893, 26, 2353 Bamberger, Md. 1900, 33, 3188 Bam-
Prepared from diazotised 6-nitro-2-aminophenol-
; ;
berger and Meimberg, ibid. 1895, 28, 1889 ; Bamberger,

ibid. 848 D. P. 14443.)
;
4-sulphonic acid and #-naphthol. Aqueous
VOL. I. T. SB
solution is brownish- violet, and solution in strong Milling Yellow (Lev.) (D.) ; Chrome Yellow D
sulphuric acid is reddish- violet. (By.); Anthracene Yellow BN (C.) ; Mordant
Literature. E. P. 2772 of 1900; D. R. P. Yellow (B. ) (M.) ; Chrome Fast Yellow (A.);
143892 A. P. 667935.
; Salicin Yellow D (K.); Sulphonaphthaleneazo-
Anthracene Chrome Black (('.); Sulpho- salicylic acid
naphtholazo-j8-naphthol H
HS0 3 -C 10 6 -N 2 -C 6 H 3 (C0 2 H)-OH.
HS0 3 -C 10 H 6 (OH)-N
-OH. 2 -C 10 H ? Prepared by the action of diazotised /3-naphthyl-
Prepared by the action of diazotised 3-amino- amine-5-(or 6)-sulphonic acid on salicylic acid.
y3-naphthol-7-sulphonic acid (R.) on /8-naphthol. Solution in water is yellow, and in strong sul-
Aqueous solution is red ; hydrochloric acid gives a phuric acid yellowish-red.
reddish- violet precipitate, and sodium hydroxide Oriol Yellow (G.); Cotton Yellow R (B.) ;
turns it bluish-violet. Solution in strong sul- Alkali Yellow (D.); Primulineazosalicylic acid
phuric acid is bluish-green, giving a reddish- H
P 1 -N 2 -C 6 3 (CO ? H)-OH. Prepared by the action
violet precipitate on dilution. of diazotised primuline on salicylic acid. Gives
Literature. E. P. 28107 of 1897 ; D. R. P. an orange-yellow solution in water, and a
109932 F. P. 272620, 272621.
; scarlet-red with strong sulphuric acid.
Palatine Chrome Blue (B.) ; Eriochrome Blue Literature.!). R. P. 48465 ; F. P. 192628 ;
Black R (G.). Isomeric with the preceding. A. P. 398990.
Prepared from diazotised l-ammo-j8-naphthol- Eriochrome Phosphine R (G.); Nitrosulpho-
4-sulphonic acid and -naphthol. .Blue aqueous benzeneazosalicylic acid
solution gives yellowish-brown precipitate with
N0 2 -C 6
H 3 (S0 3 H)-N 2 -C 6 H 3 (C0 2 H)-OH.
hydrochloric acid, and turns first blue and then
red with sodium hydroxide. Solution in strong Prepared by the action of diazotised ^p-nitro-
aniline-o-sulphonic acid on salicylic acid.
sulphuric acid is dark blue, giving a blackish-
brown precipitate on dilution. Yellowish-orange aqueous solution becomes pale
Literature. E. P. 15025 of 1904; F. P. orange with hydrochloric acid, and blue-red with
350055 ; Ital. P. 73530 Aust. P. 30630. sodium hydroxide. Solution in strong sulphuric
;
acid is yellowish orange giving a pale-yellow
Salicin Black U (K.) is the zinc sodium salt
of the above, and is prepared by diazotising precipitate on dilution.
l-amino-0-naphthol-4-sulphonic acid with zinc

Literature.!). R. P. appl. A 17781 of 1909.
nitrite and combining the diazo-compound with Eriochrome Red B (G.): Sulphonaphthol-
j3-naphthol in concentrated alkaline solution. azophenylmethylpyrazolone
Literature. E. P. 23034 of 1905; D. R. P. /C(CE 3 )
: N
175593, 195228; F. P. 353786; A. P. 807422. HSO. C 10 H 5 (OH)-N 2 <\
Eriochrome Black A (G.); Nitrosulpho- V)(OH) N-C 6 H 6 .
naphtholazo-0-naphthol Prepared by the action of diazotised l-amino-/8-

N0 2 -C 10 H 4 (S0 3 H)(OH)-N 2 -C 10H 6 -OH. naphthol-4-sulphonic acid on phenylmethylpyra-
zolone. Yellowish-red aqueous solution gives a
Prepared from
diazotised 8-nitro-l-amino-)3-
acid and /3-naphthol. bright scarlet-red precipitate with hydrochloric
naphthol-4-sulphonic
Dark-blue aqueous solution gives a reddish- acid, and becomes orange-yellow with sodium
brown precipitate with hydrochloric acid, and hydroxide. Solution in strong sulphuric acid
becomes cherry-red with sodium hydroxide.
is magenta-red,
giving a scarlet-red precipitate
Solution in strong sulphuric acid is dark-violet
on dilution.
Literature.E. P. 17274 of 1904 ; D. R. P.
blue, giving a brown precipitate on dilution.
165743 F. P. 350161 ; A. P. 808919.
Literature. E. P. 15982 of 1904 ; D. R. P. ;
169683 ; F. P. 350071 ; A. P. 790363 ; Ital. P. Dianil Yellow (M.). R

Prepared by the
action of diazotised primuline (sulphonic acid)
73531 ; Aust. P. 27191.
Diamond Black PV (By.); Sulphophenolazo- on l-phenyl-3-methylpyrazolone. The orange-
1 yellow aqueous solution gives an orange-yellow
5-dihydroxynaphthalene
:
OH-C 6 H 3 (S0 3 H)-N 2 -C 10 6 (OH) 2 H .

precipitate with hydrochloric acid and a reddish-
yellow one with sodium hydroxide. Solution in
Prepared from diazotised o-aminophenolsul- strong sulphuric acid is dark orange, giving an
phonic acid and 1 5-dihydroxynaphthalene.
:
orange-yellow precipitate on dilution.

Bluish-red aqueous solution gives a dark red Literature. E. P. 10127 of 1897; D. R. P.
precipitate with hydrochloric acid. Solution in 117575.
strong sulphuric acid is blackish-green, giving a Dianil Yellow 3 G (M. ). Prepared from diazo-
reddish precipitate on dilution. tised dehydrothio-2>-toluidinesulphonic acid and
Literature. E. P. 18139 of 1902.
ethyl acetoacetate. Greenish-yellow aqueous
Roxamine (D. H.); Sulphonaphthaleneazo- solution gives a yellow precipitate with hydro-
2 :
7-dihydroxynaphthalene chloric acid, and becomes orange with sodium
H
HS0 3 -0, 6 -N 2 -C 10 H 5 (OH) 2 .
hydroxide. Solution in strong sulphuric acid
Prepared by the action of diazotised naphthionic is brownish-yellow, giving a yellow precipitate
acid on 2 7-dihydroxynaphthalene.
: Aqueous on dilution.
solution is scarlet. Dissolves in strong sulphuric Literature. E. P. 17328 of 1897 D. R, P- ;
acid with a violet colour. 98761 ; F. P. 256647, 269001 A. P. 66256. ;
Azo Acid Blue 4 R (By.). Is probably pre-

pared by the action of diazotised ^-nitroaniline 2. DISULPHOKIC ACIDS.
on 1 8-dihydroxynaphthalene-4-sulphonic acid
:
Phenoflavine (O.); m-Sulphobenze
and subsequently reducing the nitro- group. It
aminophenolsulphonic acid.
gives a blue-violet solution in water and a reddish-
violet in strong sulphuric acid.
HS0 3 -C 6 H 4 -N 2 -<J 6 H 2 (S0 3 H)(NH 2 )-OH.
Literature. Chem. Ind. 1896, 19, 549. 1
P= residue of primuline.
Prepared by the action of diazotised metanilic Produced by the action of diazocumene chloride
acid on 3-aminophenol-5-sulphonic acid (III.). (from ^-cumidine) on R-salt. Properties as
Gives a yellow solution in water or strong sul- above ; colour of a redder shade than the last.
phuric acid. Literature. See above.
D. R. P. 71229.
Literature. Ponceau 3 R (M.); Dimethylethylbenzene-
Chrome Brown RR (G.); Disulphophenol- azo-^-naphthol-3 :
6-disulphonic acid
azopyrogallol C 2 H 6 -C G H 2 (CH 3 ) 2 -N 2 -C 10 H 4 (S0 3 H) 2 -OH( 3).
OH-C 6 H 2 (S0 3 H) 2 -N 2 -C 6 H 2 (OH) 3
J
Prepared by the action of diazotised ethylxyli-

.
Prepared by the action of diazotised p-amino- dine on R-salt.

phenol-2 6-disulphonic: acid on pyrogallol. Literature. See above.
Solution in water is yellow, and in strong sul- Bordeaux B (H.) (A.) (M.) Fast Red B ;
phuric acid brown. (B.); Bordeaux BL(C.) Bordeaux R extra (M. );

;
Literature. E. P. 11902 of 1893; D. R. P. Cerasine (P.).; Archilline 2B(Lev.); o-Naphtha-

81109; F. P. 230937; A. P. 548460. leneazo-0-naphthol-3 6-disulphonic acid :
Orange G (A.) (M.) (B.) (P.) (C. J.) ; Orange H

C 10 7 -N 2 -C 10 4 (S0 3 H) 2 -OH. H
GG (C. Benzeneazo-i8-naphtholdisulphonic
) ;
Prepared from diazotised a-naphthylamine and
H
acid C 6 H S -N 2 -C 10 4 (S0 3 H) 2 -OH(0). Produced R-salt. Solution in water is magenta-red, and
by the action of diazobenzene chloride on in strong sulphuric acid blue becoming
magenta-
j8-naphthol-6 8-disulphonic acid
:
(G-salt) in red on dilution.
alkaline solution. Solution not precipitated by Literature. E. P. 1715 of 1878; D. R. P.
alkali dissolves in strong sulphuric acid Avith an
;
3229 ; JF. P. 124811 ; A. P. 251164.
orange colour, undergoing no change on dilution. Sorbine Red (B.); Azogrenadine S (By.):
Literature. E. P. 1715 of 1878 ; D. R. P. Lanafuchsine SB (C). ; ^-Acetylaminobenz-
3229; F. P. 124811.
eneazo-a-naphthol-3 :
6-disulphonic acid
Crystal Scarlet 6 R (C.) (M.) Crystal Ponceau CH 3 -CO-NH-C 6 H 4 -N
2 -C 10 H 4 (S0 3 H) 2 -OH.
;
(A.)(K.)(B.); o-Naphthaleneazo-0-naphthol-6 8- :
disulphonic acid (G-acid). Produced by the Prepared by the action of diazotised acetyl-j)-
action of diazotised phenylenediamine on o-naphthol-3 6-disulphonic :
a-naphthylamine upon acid.

0-naphthol-6 acid in alkaline Aqueous solution is currant-red, and, in
:
8-disulphonic
solution. strong sulphuric acid fiery red. Lanafuchsine
SG is a closely related dyestuff.
Palatine Scarlet (B.") ; Cochineal Scarlet PS
36491 ;
A. P. 332528.
Ponceau 2 G (A.) (B.) (M.) (C.) Orange R (By.); m-Xyleneazo-a-naphthol-3 6-disulphonic :
(H.). Isomeric with Orange G. Prepared by

;
acid H H
C 8 9 -N 2 -C 10 4 (SO 3 H) 2 -OH. Prepared
the action of diazobenzene chloride upon
from diazotised m-xylidine and o-naphthol-
3 6-disulphonic acid.
: Solution in water is
j8-naphthol-3 6-disulphonic acid (R-salt).
: Pro-
scarlet-red and in strong sulphuric acid bluish-
perties similar to those of the preceding com-
pound ; colour slightly redder in shade.
red. Closely related dyestuffs are Palatine
Literature as for Orange G.
Scarlet 3 R and 4 R (B.) ; Brilliant Cochineal 2
Azocoralline
R and 4 R (C.).
(D.); p-Acetylaminobenzene- XL Carmoisine 6 B (H.). ; m-Xyleneazodi-
azo-j8-naphthol-3 :
6-disulphonic acid acid
CH 3 -CO-NH-C 6 H 4 -N 2 -C 10 H 4 (S0 3 H) 2 -OH. hydroxynaphthalene-3 6-disulphonic
:
C 8 H 9 -N 2 -C 10 H 3 (S0 3 H) 2 (OH),. Prepared by the

Prepared by the action of diazotised acetyl-^J- action of diazotised m- xylidine on 1 :
8-dihy-
phenylenediamine on 0-naphthol-3 6-disul- :
acid
droxynaphthalene-3 :
6-disulphonic (chro-
phonic acid (R-salt). Solution in water is orange-
matrope acid).
red, and in strong sulphuric acid yellowish-red.
Eosamine B (A.); Methoxytolueneazo-o-
Literature. Nietzki, Ber. 1884, 17, 344.
naphthol-3 6-disulphonic acid
:
Ponceau R, 2 R, G and GR l
(A.) (B.) (M.) H
CH 3 -0-C 7 6 -N 2 -C 1 oH 4 (S0 3 H) 2 -OH.
Lev.) (H.) (C.) (C. J.) ; Brilliant Ponceau R
Prepared from diazotised m-amino-^-cresol
!(T. Xylidine Red; Xy-
M.); Xylidine Scarlet;
lcneazo-j8-naphthol-3 : 6-disulphonic acid methyl ether and a-naphthol-3 6-disulphonic :
acid. Solution in water is bluish-red, and in

H
C 8 9 -N 2 -C 10 4 (HS0 3 ) 2 -OH(0).H
Produced by the action of diazotised xylidine strong sulphuric acid violet-blue.
Literature. Chem. Ind. 1896, 19, 8.
chiefly meta-) on 0-naphthol-3 6-disulphonic :
Palatine Red (B.) ; Naphthorubin (By.);
icid
Properties similar to those of
(R-salt).
6-disulphonic
a-Naphthaleneazo-a-naphthol-3 :
Orange G. Colour a distinct scarlet ; aqueous acid H H

C 10 7 -N 2 -C 10 4 (S0 3 H) 2 -OH. Prepared
solution not precipitated by alkali an amor- ;
from diazotised a-naphthylamine and o-naphthol-
phous precipitate by calcium or barium chloride. acid. Bluish-red solution in
3 6-disulphonic
:
Soluble with a red colour in
strong sulphuric water, and blue in strong sulphuric acid. A
ic id,
becoming brown and precipitating on similar colouring matter is Azo Red A (C.).
dilution.
Literature. E. P. 1715 of 1878 ;
D. R. P. 3229;
F. P. 124811 ; A. P. 210233.
38281.
Direct Rose G (K. S.) :
Ponceau 3 R
(A.) (B.) (M.) (C. J.) (K.) ;
Ponceau 4 R2
(A.) ; Cumidine Red (M.) ; Cume-
'
ieazo-/3-naphthol-3 : 6-disulphonic acid

C 9 H U -N 2 -C 10H 4 (S0 3 H) 2 -OH(|8).
Prepared from diazotised dehydrothio-^-tolui-
G and GR are made from crude xylidine and crude
1
dine and o-naphthol-3 8-disulphonic acid (e- :
t-salt, R from crude xylidine and 2 R from m-xylidine a

nd pure R-salt. acid). Cherry-red aqueous solution gives
-
3 R is made from crude cumidine and 4 R from pure scarlet-red precipitate with hydrochloric acid,
'-cumidine. and a bluish-red one with sodium hydroxide.
Solution in strong sulphuric acid is dark-bluish phenylenediamine on 1 :
8-dihydroxynaphthal-
red, giving a scarlet-red precipitate on dilution. ene-3 6-disulphonic acid.
: Solution in water
Erika B (A.); Methylbenzenylaminothio- is violet-red, and in strong sulphuric acid ruby-
xylenolazo-a-naphthol-3 : 6-disulphonic acid red
Literature.!). R. P. 75738.
Chromotrope 10 B (M.); Naphthaleneazo-
1 :
8-dihydroxynaphthalene-3 6-disulphonic acid :
n H
C 10 7 -N 2 -C 10 3 (S0 3 H) 2 (OH) 2H .
Prepared from diazotised dehydrothio-m-xyli- Prepared from diazotised a-naphthylamine and

dine and o-naphthol-3 6-disulphonic acid : the above acid. Violet solution in water, and
Solution in water or strong sulphuric acid is red. greenish-blue in strong sulphuric acid.
The various brands of Geranine (By.) and As under Chromotrope 2 R.
Literature.
Brilliant Geranine (By.) are analogously con- Chromazone Red A (G.) Benzaldehydea: ;
stituted. 1 8-dihydroxynaphthalene-3 : 6-disulphonic

:
Literature. E. P. 17333 of 1888 ; D. R> P. H

acid CHO-C 6 4 -N 2 -C 10 3 (S0 3 H) 2 (OH) 2 Pro- H .
63951 ; F. P. 194406 ; A. P. 418657 ; Schultz, duced from diazotised p-aminobenzaldehyde

Ber. 1889, 22, 583. and 1 8-dihydroxynaphthalene-3 6-disulphonic
: :
Azo Bordeaux (By.) 1

; Naphthaleneazo-o- acid. Solution in water is red, and in strong
naphthol-4 :
8-disulphonic acid sulphuric acid blue.
C 10H 7 -N 2 -C 10H 4 (S0 3 H) 2 -OH. Literature.!). R. P. 85233 ; F. P. 248519.
Chromazone Blue R (G.) ; Phenylethylhy-
Prepared by the action of diazotised o-naphthyl-
amine on a-naphthol-4 8-disulphonic acid. :
drazone of the preceding colouring matter
C 6 H 5 (C 2 H 5 )N'N CH-C 6 H4 -N 2 -C 10H 3(SO 3H) 2 (OH) 2
Magenta-red aqueous solution is not changed by
: .
acids or alkalis. Solution in strong sulphuric Prepared either by condensing chromazone red
acid is blue, becoming magenta-red on dilution. with os-phenylethylhydrazone or by the action
Literature. E. P. 15775 and 15781 of 1885 ; of diazotised 2>-aminobenzylidenephenylethylhy-
D. R. P. 40571, 42304 ; A. P. 333035. drazone on 1 : 8-dihydroxy-3 : 6-disulphonic acid.
Azocochineal (By.); Anisoleazo-a-naphthol- Solution in water is blue- violet, and in strong
4 8-disulphonic acid
:
sulphuric acid blue-red.
CH 3 -0-C 8 4 -N 2 -C 10 4 (S0 3 H) 2 -OH. H H Literature as above.
Diamine Rose (C.) Diamine Pink (C.);
Similarly prepared from diazotised o-anisidine.
;
Solution in water and strong sulphuric acid is red. Benzenylaminothiophenolazochloronaphtholdi

Literature. E. P. 15775 of 1885 ; D. R. P. sulphonic acid
40571.
Chromo trope 2 R (M.) ; Biebrich Acid Red 4 B CH 3 -C 6 H/ \C-C6 H 4 -N 2 -C 10 H 4 C1(S0 3 H) 2
-OH
(K.); XL Carmoisine R (H.); Benzeneazo-
1 8-dihydroxynaphthalene-3
:
6-disulphonic : Prepared from diazotised dehydrothio-p-tolui-
acid C H
-N 2 -C 10 3 (S0 3 H) 2 (OH) 2 H
Produced .
dine and 8-chloro-o-naphthol-3
6-disulphonic :
5 ?
from diazotised aniline and 1 8-dihydroxy-
:
acid. Magenta-redwater, and solution in
acid. Gives in reddish-violet in strong sulphuric acid.
naphthalene-3 6-disulphonic :
water a magenta-red, and in strong sulphuric Literature. E. P. 1920 of 1894 ; D. R. P.

acid a ruby -red solution. 79055, 82285, 96768, 99227 ; F. P. 235271 ; A. P.
Literature. E. P. 9258 of 1890 ; D. R. P. 535037.
69095 F. P. 206439 ; A. P. 458283.
;
Fast Acid Fuehsine B (By.); Benzem
Chromotrope 2 B (M.); p-Nitrobenzeneazo-
1 :
8-aminonaphthol-3 6-disulphonic acid :
1:8- dihvdroxynaphthalene -3:6- disulphonic H H

C 6 6 -N 2 -C 10 3 -(S0 3 H),(OH)-NH 2 .
H
acid N0 2 -C 6 4 -N 2 -C 10 3 (S0 3 H) 2 (OH) 2 Pre- H .
Prepared from diazotised aniline and
pared by the action of diazotised jj-nitroani- aminonaphthol-3 6-disulphonic acid (H-acid) :
line on
8-dihydroxynaphthalene-3 6-disul-
1 : :
in alkaline solution. Solution in water or strong
Solution in water is yellowish-red,
acid.
phonic sulphuric acid magenta-red. is
and in strong sulphuric acid dark violet. 13343 of 1890 ; D. R. P. 62368,
Literature.
Literature. As under Chromotrope 2R. 70031 ; F. P. 210033.
Victoria Violet 4 BS (M.); y-Aminobenz- Tolane Red B (K.); Benzeneazo- 1 8-amino- :
eneazo-1 6-disul-
8-dihydroxynaphthalene-3 naphthol-4 6-disulphonic acid. Isomeric with
: :
:
phonic acid NH^HyNjj-C^H^SOjHyOH).,. the preceding. Prepared from diazotised aniline

Prepared by the alkaline reduction of chromo- and 1 8-aminonaphthol-4 : 6-disulphonic acid
:
trope 2 B or by eliminating the acetyl group (K-acid). Solution in water or strong sulphuric
from Chromotrope 6 B (see below). It gives a acid is magenta-red.
dark-violet solution in water, and a bluish-red E. P. 515 of 1894; D. R. P.
Literature.
in strong sulphuric acid. Similar colouring 99164 A. P. 563383. ;
matters are Victoria Violet 8 BS (M.) and Azo Fast Sulphone Violet 5 BS (K. S.) is prepared
Acid Blue B (M.). by combining a diazo- compound with 1 8- :
E. P. 8270 of 1892 D. R. P.
Literature. ;
aminonaphthol-3 6- or -4 6-disulphonic acid : :
70885, 73321 F. P. 221363. ; in alkaline solution, and treating the product

Chromotrope 6 B (M.); XL Fuehsine 6 B with p-toluenesulphonyl chloride, whereby the
(H.) jj-Acetylaminobenzeneazo-1 8-dihydroxy-
;
:
amino- group is transformed into the p-toluene-
naphthalene-3 6-disulphonic acid :
sulphonylamino- group. Other dyestuffs of the
CH 3 -CO-NH-C 6 4 -N 2 -C 10 3 (S0 3 H) 2 (OH) 2 H H . same kind are Brilliant Sulphone Red B (K. S.
Prepared by the action of diazotised acetyl^p- and Fast Sulphone Violet 4 R (K. S.).
Literature. E. P. 22886 of 1899 ;
D. R. P-
1
No longer manufactured under the name 'Buffalo
'
Rubin by the Schollkopf Co. 120081.
Azorubine S (A.); Azorubine A (C.); Azo thylamine-6 8-disulphonic acid on salicylic acid.
:
Acid Rubine (C. J.) (D.) Azo Acid Rubine R ; Solution in water is yellow, and in
strong sulphuric
(K.); Nacarat (P.); Fast Red C (B.); Car- acid, orange-red.
moisine (By.); Carmoisine AS (Lev.) Sulpho-o- Literature. E. P. 12145 of 1894 ; D. R. P.
naphthaleneazo-o-naphtholsulphonic acid 87483.
H H
HS0 3 -C 10 6 -N 2 -C 10 6 (S0 3 H)-OH. Lanacyl Blue BB (C.); Disulphohydroxy-
Prepared by the action of diazotised naphthionic naphthaleneazoaminonaphthol
acid on a-naphthol-4-sulphonic acid in presence H
C 10 4 (S0 3 H) 2 (OH)-N,-C 10 H 5 (OH)-NH 2 .
of alkali. Solution gives a red crystalline pre- Prepared from diazotised 1 8-aminonaphthol- :
cipitate with calcium chloride substance dis-; 3 6-disulphonic acid (H-acid) and 1 5-amino-
:
:
solves in strong sulphuric acid with a bluish- violet naphthol in acetic acid solution (the azo- group
colour, becoming red on dilution. When used attacks the ortho- position relative to the
for after-chroming on wool the dyestuff is known hydroxy- group). Solution in water is reddish
as Azochrome Blue R (K.). or bluish -violet, and in strong sulphuric acid blue.
E. P. 2237 and 4237 of 1883; To
Literature.
group belong also Lanacyl Blue R and
this
D. R. P. 26012. Lanacyl Navy Blue B and 3 B (C.).
Azochrome Blue B (K.); isomeric with the Literature. E. P. 24134 of 1896 D. R. P. ;
preceding. Prepared from diazotised naphthi- 95190 F. P. 260848.

;
onic acid and

o-naphthol-5 sulphonic acid. Rosophenine 10 B (Cl. Co.) Rosophenine ;
Aqueous solution is bluish-red and gives a Pink (Cl. Co.) Direct Scarlet B (K.); Sulpho-
;
reddish-brown precipitate with hydrochloric benzenylaminothiocresolazo - a - naphthol-4 - sul-

acid. Substance dissolves in strong sulphuric phonic acid
acid with reddish-blue colour.
Fast Red E (B.) (K.); Fast Red (Lev.) (A.)
C 6H 3 / \C-C 6 H 4 -N a -C 10H 5 -OH
Sulpho-a-naphthaleneazo--naphtholsul-
(C.J.)
CH 3 S0 3H S0 3H
;
H
phonic acid HS0 3 -C 10 6 -N 2 -C 10 5 (S0 3 H)-OH. H
Isomeric with the preceding prepared from ;
Prepared from diazotised dehydrothio-^-tolui-
diazotised naphthionic acid and Schaffer's dinesulphonic acid and a-naphthol-4-sulphonic
Aqueous solution acid. Solution in water is crimson-red, and in
)8-naphthol-6-sulphonic acid.
claret-red ; not precipitated by acids, dissolves strong sulphuric acid violet -red.
in strong sulphuric acid with a violet colour, The corresponding colour from diazotised
becoming red on dilution. primuline is called Rosophenine SG (Cl. Co.);
Literature. E. P. 786 of 1878 D. R. P. 5411.
;
Thiazine Red R (B.) (D. R. P. 48465; F. P.
Croceine Scarlet 3 BX (By.) (K.)Coccine 2 B ;
192628, 196988 A. P. 398990). ;
(A.) ; Scarlet 000 (H.). Isomeric with the last ;

Thiazine Red G (B.). Prepared from diazo-
prepared from diazotised naphthionic acid and
tised primuline (sulphonic acid) and /3-naphthol-
Bayer's /8-naphthol-8-sulphonic acid. Hot solu- 6-sulphonic acid. Orange-red aqueous solution
tion (concentrated) gives a crystalline magnesium gives an orange-red precipitate with hydrochloric
salt on adding magnesium sulphate and allowing acid, and becomes dark with sodium hydroxide.
to cool ; solution in strong sulphuric acid reddish- Solution in strong sulphuric acid is blood-red,
violet becoming yellowish-red on dilution. giving an orange precipitate on dilution.
Literature. E. P. 2031 of 1881 ; D. R. P. References as for thiazine red R.
20402 ; A. P. 256376. Dianil Yellow 2 R (M.). Prepared by the
Double Scarlet Extra S (A.) (Lev.) Double ;
action of diazotised primuline (sulphonic acid)
Brilliant Scarlet 3 R (By.); Double Brilliant on l-2>-sulphophenyl-3-methyl-5-pyrazolone.
Scarlet S (K.); Brilliant Ponceau 4 R (By.); Reactions and references as for dianil
Scarlet PR (P.). Isomeric with the last pre- ; yellow R.
pared from diazotised j8-naphthylamine-6-sul- Chrome Fast Yellow G (A.); Di-(and tri-)-
acid
phonic acid (Bronner's), and o-naphthol-4- sulphodiphenylphenotriazineazosalicylic
sulphonic acid
HS0 3 -Ci H 6 -N 2 -C 10H 5 (S0 3 H)-OH.
C 6H 5 -N N/\
Aqueous solution gives yellowish-brown pre- C 6H 5 -CH-N N 2 -C H6 3 (OH)-C0 2
H
cipitatewith dilute acids. Dissolves in strong
sulphuric acid with a red colour, becoming
\/ (di- and tri-sulphonic acids).
Produced from the di-(or tri-)sulphonic acids of

yellower on dilution.
the triazine from chrysoldine and benzaldehyde
22547. by diazotisation and combination with salicylic
acid. The aqueous solution is orange-yellow,
Azofuchsine G (By.); p-Sulphobenzeneazo- the
and the solution in strong sulphuric acid is
dihydroxvnaphthalene-4-sulphonic acid same.
H H
HS0 3 -C 6 4 -N 2 -C 10 4 (OH) 2 -S0 3 H. Literature. D. R. P. 79425 (compare also
Prepared from diazotised sulphanilic acid and D. R. P. 76491 and 78006); Noelting and
1:
8-dihydroxynaphthalene-4-sulphonic acid. So- Wegelin, Ber. 1897, 30, 2595.
lution in water is bluish-red, and in strong
3. TRISXJLPHONIC ACIDS.
sulphuric acid violet. Analogous colours are
Azofuchsine S and GN extra (C.). New
Coccine (A.) (Lev.) Brilliant Scarlet ;
Literature. E. P. 18517 of 1889 D. R. P. ; (C.); Croceine Scarlet 4 BX (K.); Victoria

54116 F. P. 203744 ; A. P. 466841, 468142.
;
Scarlet 4 R (T. M.) ; Special Ponceau (P.) ; Co-
Crumpsall Yellow (Lev.); Disulphonaphtha- chineal Red A (B.) ; Sulpho-a-naphthaleneazo-
acid
leneazosalicylic acid iS-naphthol-6 8-disulphonic:
C, H G (S0 3 H) 2 -N 2 -C 6H 3 (OH)-C0 2 H. H
HS0 3 -C 10 6 -N 2 -C 10 4 -(S0 3 H) i -OH.H
Produced by the action of diazotised j8-naph- Prepared by the action of diazotised naphthionic
acid on j8-naphthol-6 8-disulphonic acid (G- : ihuric acid. The sodium salt is put on the
salt). Aqueous solution red, not precipitated by market in the dry state as Alizarine Yellow GGW
acids. Dissolves in strong sulphuric acid with M.).
a red colour, becoming yellowish-red on dilution. Literature. E. P. 17583 of 1887 ; D. R. P.
Literature. E. P. 816 of 1884; D. R. P. 44170 ; F. P. 187821 ; A. P. 424019.
36491 A. P. 314938.
;
Alizarine Yellow 1
R
(M.) (C. R.) (By.);
Fast Red D (B.) Azo Acid Rubine 2 B (D.) ; ; Terracotta (G.); Chrome Orange (P.) ; Xantho-
Fast Red EB (B.) Cloth Red (T. M.) Bordeaux
; ; chromine. Isomeric with the last. Prepared
S (A.) (Lev.); Amaranth (M.) (C.). Isomeric rom diazotised p-nitroaniline and salicylic acid.
with the preceding. Prepared from diazotised 2omes on the market as a brown paste insoluble
naphthionic acid and R-salt. n water and giving an orange-yellow solution
Literature. D. R. P. 3229. with strong sulphuric acid. This consists of the
Chromotrope 8 B (M. ). p-Sulphonaphthalene- ~ree acid ; the sodium salt (soluble in water with
azodihydroxynaphthalene-3 6-disulphonic acid : an orange colour) is called Alizarine Yellow RW
H
HS0 3 -C 10 6 -N 2 -C 10 3 (S0 3 H) 2 (OH) 2 H . M.).
Literature. Meldola, Chem. Soc. Trans. 1885,
Prepared by the action of diazotised naphthionic
on 47, 666; Bull. Mulhouse, 1892, 198; J. Soc.
acid 8-dihydroxynaphthalene-3 6-disul-
1 : :
Ihem. Ind. 1890, 9, 53 ; 1892, 11, 599 ; J. Soc.

phonic acid. Solution in water is violet-red, and
in strong sulphuric acid indigo-blue. In Dyers, 1889, 5, 106 ; E. P. 13920 of 1888.
addition to this and the other chromotrope
' ' Persian Yellow (G.); o-Nitrotolueneazosali-
colours mentioned above, the marks S. SB, SR,
icacid N0 H
2 -C 7 g -N 2 -C 6 H
3 (C0 2 H);OH.
Pre-
7 B, F B, and F 4 B also appear on the market, but pared by nitrating p-tolueneazosalicylic acid (for-
their constitution has not yet been published. merly in commerce under the name Flavazol)
Literature. E. P. 9258 of 1890; D. R. P. The commercial product is a 20 p.c. paste soluble
in water to a yellow solution, and giving an
69095 F. P. 206439 ; A. P. 458283.
;
orange-yellow solution with strong sulphuric

4. TETEASTJLPHONIC ACIDS. acid.
Literature. E. P. 13920 of 1888; F. P.
Ponceau 6 R (M.)
p-Sulphonaphthalene- (B.) ;
193190 A. P. 431297 ; Ber. 1907, 40, 4207.
;
azo--naphtholtrisulphonic acid Chrome Fast Yellow GG (A.) ; o-Anisoleazo-
H
HS0 3 -C 10 6 -N,-C 10 3 (S0 3 H) 3 -OH. H H
salicylic acid CH3-0-C 6 4 -No-C 6 ? (C0 2 H)-OH. H
Prepared by the action of diazotised naphthionic Prepared from diazotised o-anisidine and sali-
acid on -naphthol-3 6 8-trisulphonic acid. : :
cylic acid. In commerce as a bright-yellow
Solution in water is magenta-red, and in strong paste or a yellow powder. Solution in hot water
sulphuric acid violet. is greenish-yellow, and in strong sulphuric acid
Literature. E. P. 2544 of 1882 ; D. R. P. yellowish-brown.
22038 ; F. P. 137109 ; A. P. 268506. Azoalizarine Yellow 6 G (D. H.); Alizarine
Heliopurpurine 4 BL (By.) ; Disulphonaph- Yellow 5 G (M.); Tartraehromine GG (I.)-;
thaleneazo-a-naphthol-3 6-disulphonic acid :
2>-phenetoleazosalicylic acid
C 10H 6 (S0 3 H) 2 -N 2 -C 10H 4 (S0 3 H) 2 -OH. H H H
C 2 6 -0-C 8 4 -N 2 -C 6 3 (C0 2 H)-OH.
Prepared from diazotised j8-naphthylamine- Prepared from diazotised jj-phenetidine and
3 6-disulphonic
: acid and a-naphthol-3 6- :
salicylic acid. Solution in water is yellowish-
disulphonic acid. Used exclusively in the brown, and in strong sulphuric acid brown-red.
manufacture of lakes. Diamond Flavine G (By.); ^-Hydroxydi-
Farber-Zeit. 1904, 15, 95.
Literature. phenylazosalicylic acid
BL (By.) Isomeric with
Heliopurpurine 7 OH-C 12 H 8 -N 2 -C 6 H 3 (C0 2 H)-OH.
the preceding. Prepared by the action of
diazotised
Prepared by boiling the intermediate product
/3-naphthylamine-l : 6-disulphonic from tetrazotised benzidine and one molecule of
acid on 0-naphthol-3 6-disulphonic acid (R- :
In commerce as a yellowish-
salicylic acid.
salt). Used only for lakes.
brown paste or powder which dissolves ha water
Literature as above.
only after the addition of sodium acetate.
5. PENTASTJLPHOKIC ACIDS. Solution in strong sulphuric acid is blood-red.
Heliopurpurine GL (By.) ; Disulphonaphtha- 60373; F. P. 214756.
6 8-trisulphonic acid
leneazo-j8-naphthol-3 : :
Diamond Yellow G (By.) ; m-Carboxyben-
C 10H 5 (S0 3 H) 2 -N 2 -C 10H 3 (S0 3 H) 3 -OH. zeneazosalicylic acid
Prepared diazotised from
-naphthylamine- H H
C0 2 H-C 6 4 -N 2 -C 6 3 (C0 2 H)-OH.
3 6-disulphonic acid and /3-naphthol-3 : 6 : 8- acid
Prepared from diazotised m-aminobenzoic
:
trisulphonic acid.
and salicylic A greyish-yellow paste
acid.
Use and literature as above. soluble hi(with addition of sodium
water
E. Carboxylic Acids of Hydroxyazo- Compounds. acetateor carbonate) with a yellow colour.
Alizarine Yellow GG (M.); Chrome Yellow Gives a reddish-yellow solution with strong
R(P.); m-Nitrobenzeneazosalicylic acid sulphuric acid.
H E. P. 8299 of 1889 ; D. R.
N0 2 -C 6 4 -N 2 -C 6 3 (C0 2 H)-OH. H Literature.
F. P. 198521 (addition) ; A. P. 502368,
58271
Prepared from diazotised w-nitroaniline and ;
502369.
salicylic The commercial product (th<
acid.
Diamond Yellow R Isomeric with th
(By.).
free acid) a yellow paste, insoluble in water
is acid
and giving an orange solution with strong sul preceding. Prepared from o-aminobenzoic
and salicylic acid. A
brown paste soluble in
Carboxylic acids containing also sulphonic acid
1
Meta Chrome Orange R double (A.) is probably

groups are described under the corresponding sulphoni
or disulphonic) acids. identical with this.
water (in presence with a yellow of alkalis), strong sulphuric acid is bright red, precipitating
colour. Solution in strong sulphuric acid is on dilution.
reddish-yellow.
Literature as for the preceding colour. 76118; F. P. 231694; A. P. 524261.
Resorcin Brown (A.) (K.) :
'
F. Unclassified Monoazo- Colouring Matters. HS0 3-C H
-N 2 -C8 H 2 (OH) 2 -N 2 -C 8 H 6
8 4 .
Tartrazine (B.) Hydrazine Yellow

(I.) (H.); Diazoxylene chloride is combined with resorcin
(0.) ; Benzeneazopyrazolonecarboxydisulphonic yellow (p. 368). Aqueous solution gives a
acid brown precipitate with acids. Dissolves in
/N=OC0 2H strong sulphuric acid with a brown colour.
S0 3H-C 6 H -N< 4 Literature D. R. P. 18862 ; A. P. 269359.
\CO CH-N 2 -C H 6 4 -S0 3H. Fast Brown G (T. M.) ; Acid Brown (D.) (P.).
Prepared (1) by the
action of phenylhydrazine-
acid ; or
sulphonic acid on dihydroxytartaric Prepared by the action of diazotised sulphanilic
(2) by the
action of phenylhydrazinesulphonic acid (2 mols.) on a-naphthol (1 mol.). Aqueous
acid on oxalacetic ester, coupling the product solution red-brown ; violet precipitate with
with diazotised sulphanilic acid and hydrolysing. dilute acid. Strong sulphuric acid solution
Solution in water or strong sulphuric acid is
violet, becoming yellowish-brown on dilution.
yellow. Literature. Krohn, Ber. 1888, 21, 3241.
Literature. E. P. 9858 of 1885 5693 of ;
Fast Brown (By.):
1893; 765 of 1897; D. R. P. 34294; F. P. 169964;
A. P. 324630 ; Ziegler and Locher, Ber. 1887; (HS0 3 -C 10H -N 2 ) 2 C 6 H 2 (OH) 2 .
20, 834 ; Anschiitz, Annalen, 1897, 294, 219 ; Prepared by the action of diazotised naphthionic
acid (2 mols.) on resorcinol (1 mol.). Brown
1899, 306, 1 ; Gnehm and Benda, Annalen, 1898,
299, 100 ; Bernthsen, Chem. Zeit. 1898, 22, 456. aqueous solution gives a readily soluble pre-
cipitate with hydrochloric acid, and becomes
Hydrazine Yellow SO (0.) is probably a
nitrotartrazine (D. P. 109914). cherry red with sodium hydroxide. Solution in
strong sulphuric acid is currant-red.
III. DlSAZO- COMPOUNDS. 1 Literature. D. R. P. 18862.
A. Primary Disazo- Colouring Matters.
2 Palatine Black (B.) ; Wool Black 4 B and
6 B (A.) :
Leather Brown (0.).:
H H H 4 -NH HS0 3 -C 6 H
4 -N 2 -C 10 H
3 (S0 3 H)(OH)(NH 2 )-N 2 -C 10
H7
NH 2 -C 6 4 -N 2 -C 6 2 (NH 2 ) 2
-N 2 -C 6 2.
Prepared by the action of diazotised sulphanilic
Prepared by combining 2 mols. of p-diazoacet- acid (1 mol.) on 1 8-aminonaphthol-4-sul-
:
anilide with 1 mol. of m-phenylenediamine, phonic acid in acid solution, and treating the
and heating the product with strong hydro- in alkaline solution with diazotised
product
chloric acid. Commercial product is the mono-
o-naphthylamine (1 mol.) in alkaline solution.
hydrochloride or the zinc chloride double salt. Dark-blue aqueous solution becomes bluish-green
The brown aqueous solution becomes yellower Avith hydrochloric acid and pure blue with
on adding hydrochloric acid, and gives a brown sodium hydroxide. The solution in strong
precipitate with sodium hydroxide. The sub- acid is blue, giving a dark-blue pre-
sulphuric
stance gives a brown solution in strong sulphuric
cipitate on dilution.
acid, which becomes yellowish-brown on Literature. E. P. 7713 of 1891 ; D. R. P.
dilution. 91855 ; F. P. 213232 ; A. P. 590088.
Literature. E. P. 11218 of 1891 D. R. P.
;
Naphthol Blue Black (C.); Naphthol Black
67429 A. P. 462414.
;
12 B (C.) ; Wool Black 6 G extra cone. (T. M.) ;
Naphthalene Black 10 B (P.) Blue Black NB

Terra CottaF(G.): ;
P 'N 2 -C 6 H 2 (NH 2 ) 2 -N 2 -C 10
H 6 -S0 3
H. (K.); Coomassie Blue Black (Lev.) :
Prepared by combining first diazotised naphthi- H H

N0 2 -C 6 4 -N 2 -C 10 2 (S0 3 H) 2 (OH)(NH 2 )-N 2 -C 6 5 H
onic acid and secondly diazotised primuline
Prepared by the action of diazotised p-nitro-
with m-phenylenediamine. Solution in water aniline (1 mol.) on 1 8-aminonaphthol-3 6- : :
is brown,
giving a brown precipitate with hydro- disulphonic acid (H-acid) in acid solution,
and
chloric acid. Strong sulphuric acid dissolves treating the product in alkaline
solution with
colour to a reddish-violet solution, giving a diazotised aniline. The dark-blue aqueous
brown precipitate on dilution. solution gives a blue precipitate with hydro-
Literature. E. P. 1888 of 1890; F. P. chloric acid. The solution in strong sulphuric
203439 ; A. P. 440288. acid is green, giving a blue precipitate on
Cotton Orange R (B.): dilution.
P'-N 2 -C 6 (NH 2 2 (S0 3 H) 2 -N 2 -C 6 H 4 -S0 3 H.<
) Literature. E. P. 6972 of 1891 D. R. P. ;
Prepared by combining first diazotised primuline 65651 ; F. P. fourth addition to 201770 A. P. ;
and secondly diazotised metanilic acid with 480326.

m-phenylenediaminedisulphonic acid. The Chrome Patent Green NC (K.)
orange-red aqueous solution gives a reddish H
(N0 2 ) 2 C H 2 -N 2 -C 10 a (S0 3H) 2 (NH 2 yOH
precipitate with hydrochloric acid. Solution in
1
See also DISAZO- AND TETRAZO- COLOURING MATTERS. OH N 2 -C 6
H 5
-
It will be sufficient to give the chemical formulae of diazotised aniline
these disazo-compounds without giving their names in Prepared by the action of
full. (1 mol.) and diazotised picramic acid (1 mol.)
3
P = residue
of primuline or dehydrothiotoluidine on 1 8-aminonaphthol-4 6-disulphonic acid.
:
:
refers to sulphonic acid.

4
Literature. D. R. P. 110711; F. P. 291316.
According to Heumann (Die Anilinfarben und ihre Blue Black N (K.)
Fabrikation) the formula is
P'N 2 -C 8 H(NH 2 )(S0 H) 2 -NH-N 2 -C 6
3
H4 -S0 3H. H
(N0 2 -C 6 H 4 -N 2 ) aC 10 2 (S0 3H) 2 (OH)-NH 2 .
Prepared by the action of diazotised >-nitro- Literature. E. P. 15775 and 15782 of 1885 ;
aniline (2 mols.) on 1 8-aminonaphthol-4 6- : : D. R. P. 40571 ; A. P. 333037.

disulphonic acid. Brilliant Croceine M
(C.) (By.) (M.) BrilU; ;
Literature. V. R. P. 108266; F. P. 271070; Croceine (K.); Brilliant Croceine, extra co

A. P. 613639. (T. M.); Cotton Scarlet (B.); Ponceau BO ex
Supramine Black BR (By.). The special (A.) ; Croceine 3 B (P.) :
base used in the preparation of this colouring H H

C 6 6 -N 2 -C 6 4 -N 2 -C 10 d (S0 3 H) 2 -OH. H
matter is yaminophenyl ether. Two mols (or
Prepared by the action of diazotised aminoaz
one of this and one of another base) are diazobenzene on /3-naphthol-6 8-disulphonic aci :
tised and combined with 1 8-aminonaphthol- :

Dissolves in strong sulphuric acid with a reddii
4:6- or 3 6-disulphonic acid.
:
violet, becoming first bluer and then red on
Literature. F. P. 402546; A. P. 958830. tion.
Janus Yellow R (M.) :
Literature. E. P. 816 of 1884; D. R.
H H
N(CH 3 ) 3 C1-C 6 4 -N 2 -C 6 2 (OH) 2 -N 2 -C 6 4 -N0 2 H .
36491 F. P. 159998 ; A. P. 314939.
;
Prepared by combining diazotised m-amino- Oil Scarlet (M.) (W.) ; Red B, Oil solubli
phenyltrimethylammonium chloride with m- extra cone. (Remy.) : Cerotine Ponceau 3 B
nitrobenzeneazoresorcinol. Yellowish - brown (C. J.); Fat Ponceau R (K.). (See also Fast
aqueous solution gives a yellowish-brown pre- Azo Garnet, p. 363.)
cipitate. Solution in strong sulphuric acid is
7
-N 2 -C.H 6 -N 2 -C 10 H 6 -OH.
C 7
H
magenta-red, becoming yellow on dilution. Prepared from diazotised o-aminoazotoluene
Azidine Fast Scarlet G, 4 BS, 8 BS, 12 BS and j8-naphthol. Insoluble in water, but soluble
(C. J.). These dyes are prepared by the action in alcohol or benzene with a bluish-red colour.
of 2 mols. of a diazo- compound, for example,
Strong sulphuric acid gives a blue solution,
that from /3-naphthylamine on the substance
which yields a red precipitate on dilution.
HS0 3 -C 10H 5 (OH)-NH-CO-NH-C 6 H 2 (CH 3 )-S0 3 H Cloth Red B (By.) (D.):
C 7 H 7 -N 2 -C 7 H 6 -N 2 -C 10 H B (S0 3H)-OH.
OH-C 10 H 5 (S0 3 H)-NH-CO-NH
Literature. D. P. (appl.) J. 11718; F. P. Prepared by the action of diazotised o-amin
azotoluene on a-naphthol-4-sulphonic ac"
412138 ; A. P. (appl.) 541843.
The red aqueous solution gives a red precipitate
Benzo Fast Scarlet GS, 4 BS and 8 BS (By.).
with hydrochloric acid, and on adding sodium
These dyes are obtained by the action of 2 mols.
of a diazo- compound on the urea produced by the hydroxide to the solution it becomes violet.
The solution in strong sulphuric acid is blackish-
action of carbonyl chloride on 2 mols. of 5-
blue.
amino-a-naphthol-3-sulphonic acid (J-acid) : i.e.
Literature. E. P. 5003 of 1879 ; D. R.
HS0 3 -C 10 H 5 (OH)-NH-CO-NH-C IO H 5 (OH)-S0 3 H. 16482.
Literature. E. P. 3615 of 1900; D. R. P. Cloth Red G Cloth Red G extra (By.)
(0.) ;
:
122904, 126133, 126801, 128195, 129464, 132511 ; C H -N 2 -C 7 H 6 -N 2 -C 10 H 5 (S0 3 H)-OH()8).

7 7
F. P. 297367; A. P. 653498, 662122, 675629,
Produced by the action of diazotised amin<
675632.
azotoluene on j8-naphthol-6-sulphonic ac:
B. Secondary Disazo- Colouring Matters. Dissolves in water with a n
(Schaffer's).
Sudan III (A.) (Ib.) (Fi.) ; Cerasine Red (C.) ; brown colour giving a similarly coloured p:
Cerotine Scarlet R (C. J.); Fat Ponceau G (K.). :
cipitate on addition of acid. Dissolves with
H
C 6 5 -N 2 -C 6 4 -N 2 -C, H
B -OH(/3).
H blue colour in strong sulphuric acid, giving a
Prepared by the action of diazotised aminoazo- brownish-red precipitate on dilution.
benzene on j8-naphtho]. Insoluble in water ; Literature. E. P. 5003 of 1879; D. R.
dissolves in strong sulphuric acid with a green 16482.
colour, becoming blue, and finally red and pre- Cloth Red B (0.) (K.) ; Cloth Red (M.
cipitating on dilution. Cloth Red BA (A.); Fast Bordeaux (M.
Literature. Nietzki, Ber. 1880, 13, 1838; Fast Milling Red B (Lev.) :
D. R. P. 16483.
Ponceau 5 R (M.) (K.) ; Erythrine X (B.) :
Prepared by the action of diazotised aminoazc
H
C 6 H 5 -N 2 -C 6 4 -N 2 -C 10 3 (S0 3 H) 3 -OH. H toluene on /S-naphthol-3 6-disulphonic acid (R- :
Prepared by the action of diazotised aminoazo- salt). Aqueous solution red, becoming brownish
benzene on /S-naphthol-3 6 8-trisulphonic acid : : on addition of hydrochloric acid. Dissolves in
in alkaline solution. strong sulphuric acid with a blue colour, giving
Literature. E. P. 2544 of 1882 ; D. R. P. a brownish-red precipitate on dilution.
22038 ; F. P. 137109 A. P 268507. ; Literature as under preceding colour.
Cloth Red G (By.) ; Cloth Red R (D.), Cloth Red 3 G extra (By.) Cloth Red 3 GA ;
H H
C 6 5 -N 2 -C 6 4 -N 2 -C 10 5 (S0 3 H)-OH. H (A.) C 7 H 7 -N 2 -C 7 H 6 -N 2 -C 10 H 6 (Sq 3 H)-NH 2 Pre-
:
.
Prepared by the action of diazotised aminoazo- pared by the action of diazotised aminoazo-
benzene on o-naphthol-4-sulphonic acid in toluene on #-naphthylamine-6-sulphonic acid
alkaline solution. Dissolves in strong sulphuric (Bronner's acid). The red aqueous solution
acid with a violet colour, giving a brownish-red gives with hydrochloric acid a dark reddish-
brown The solution in strong
precipitate on dilution. precipitate.
Literature. E. P. 2237 of 1883; D. R, P. sulphuric acid dark greenish-blue, and gives
is
26012. a brownish-red precipitate on dilution.

Croceine B (Sch.). The disulphonic acid Bordeaux BX (By.) :
corresponding with the preceding produced : C 8 H 9 -N 2 -C 8 H 8 -N a -C 10 H 5 (S0 3H)-OH.

by the action of diazotised aminoazobenzene Prepared by the action of diazotised aminp-
on a-naphthol-4 on acid
:
8-disulphonic acid. azoxylene 0-naphthol-6-sulphonic
(Schiiffer's). Solution in water is brownish-red, Prepared from diazotised aminoazobenzene-

and gives a brownish-red precipitate with hydro- disulphonic acid and -naphthol. Solution not
chloric acid or sodium hydroxide. Strong precipitated by alkali ; a brown flocculent
sulphuric acid dissolves colour to a brown precipitate by dilute acids. Dissolves in strong
solution, which gives a reddish-brown precipitate sulphuric acid with a green colour, becoming
on dilution. first blue and finally brown and precipitating on
Literature. E. P. 5003 of 1879; D. R,.P. dilution.
16482. Literature. E. P. 5003 of 1879, 529 of 18PO ;
Archil Red A (B.) Union Fast Claret (Lev.)

;
: D. R. P. 16482, 16483 ; A. P. 224927, 224928 :
C 8 H 9 -N 2 -C 8 H 8 -N 2 -C 10 H 4 (S0 3 H) 2 -OH(0). Nietzki, Ber. 1880, 13, 800, 1838 ; Miller, ibid.
542, 803, 980.
Prepared by the action of diazotised aminoazo- Croceine Scarlet extra (K.) :
xylene on /S-naphtholdisulphonic acid (B-salt).

Soluble in water with a Bordeaux-red colour ;
reddish-brown flocculent precipitate on adding Prepared by the action of diazotised aminoazo-
dilute acid. Solution in strong sulphuric acid benzenedisulphonic acid on #-naphthol-8-sul-
phonic acid. The yellowish- red aqueous
dark blue, giving reddish- brown precipitate on
solution gives a violet coloration with hydro-
dilution.
chloric acid or sodium hydroxide. The solution
Literature. E. P. 5003 and 5021 of 1879;
in strong sulphuric acid is blue, becoming
536 of 1880; D. R. P. 22010; A. P. 210233,246221.
Croeeine Scarlet 3 B Ponceau yellowish- red on dilution.
(By.) (C. J.) ;
Fast Ponceau 2 B (B.) :
4RB(A.):. HS0 3-C 6 H 4 -N2 -C 6 H 3 (S0 3H)'N2 .C 10 H 4 (S0 3 H) 2 .OH

HS0 3 -C 6 H 4 -N 2 -C 6 H 4 -N 2 -C 10 H 5 (S0 3 H)-OH.
Produced by the action of diazotised aminoazo- Prepared by the action of diazotised aminoazo-
on j8-naphthol-8-sul- benzenedisulphonic acid on ^-naphthol-3 6- :
benzenesulphonic acid
disulphonic acid (R-salt). Dissolves in strong
phonic acid (Bayer's). Solution not precipi- sulphuric acid with a blue colour, becoming
tated by alkali ; a red precipitate produced by
barium chloride, becoming dark- violet and orange-red on dilution.
Literature. Miller, Ber. 1880, 13, 542, 803 ;
crystalline on boiling. Dissolves in strong

Nietzki, ibid. 980, 1838.
sulphuric acid with a deep-blue colour, becoming Wool Black (A.) (B.) :
violet and then red on dilution.

Literature. E. P. 1225 and 2030 of 1881.
HS0 3 -C H 4 -N
6 (S0 3 H)-N 2 -C 10 H 6 -NH-C 7 H 7
2 -C 6
H 3
.
2411 of 1883, 8390 of 1884 ; D. R. P. 18027 ;

Prepared by the action of diazotised aminoazo-
F. P. 142024 A. P. 256380.
:
benzenedisulphonic acid on j>-tolyl--naphthyl-
Fast Scarlet B (K.) :
amine. 1 Aqueous solution gives a violet
precipitate with acids. Dissolves with a blue
HS0 3 -C 8 H 4 -N 2 -C 6 H 4 -N 2 -Ci H (S0 3 H)-OH. colour in str6ng sulphuric acid, giving a brown
Prepared by the action of diazotised aminoazo- precipitate on dilution, and decomposing on
benzenemonosulphonic acid on j8-naphthol-
boiling with the formation of Acid Yellow and
6-sulphonic acid (Schiiffer's). Red solution
tolunaphthazine.
in water, giving brown precipitate with hydro- Literature. E. P. 9754 of 1886; D. R, P.
chloric acid and a red-violet coloration with 38425 : A. P. 354746.
sodium hydroxide. Solution in strong sul- Croceine Scarlet 7 B ; Ponceau 6 RB (A.) ;
phuric acid is blue, and becomes red on dilution. Croeeine Scarlet 8 B (K.) (By.) :
Literature.!). R. P. 16482. -N 2 -C 10 H 5 (S0 3 H)-OH(,8).

Cloth Scarlet G (K.):
HS0 3 -C H 8 -N 2 -C H
7 7 6
Prepared by the action of diazotised aminoazo-

HSO,-G8H 4 -N ? -C6 H 4-N a -C 1 oH 6 -OH. toluenesulphonic acid on -naphthol-8-sulphonic
Prepared by the action of diazotised aminoazo- acid (Bayer's) in presence of alkali. Resembles
benzenemonosulphonic acid on #-naphthol. croce'ine scarlet 3 B in general properties ; gives
The scarlet solution in water gives a brown a crystalline magnesium salt on adding magne-
precipitate with sodium hydroxide, and becomes sium sulphate to hot concentrated solution and
yellower on addition of hydrochloric acid when allowing to cool. Dissolves with a blue
colour in
dilute, but in concentrated solutions a light- strong sulphuric acid, becoming red on
dilution.
red precipitate is produced. The solution in Literature as for croce'ine scarlet 3 B and ;
strong sulphuric acid is green, becoming red on A P 256375.

dilution. Orseilline 2 B (By.). Prepared by the action
Literature. E. P. 5003 of 1879; D. R. P. of diazotised aminoazotoluenesulphonic acid
16482. on o-naphthol-4-sulphonic acid. Dissolves with
Milling Orange (D.) :
a blue colour in strong sulphuric acid, becoming
HS0 3 C 6 H 4 -N 2 -C 6 H 4 -N 2 -C 6 H 3(C0 2H)-OH. red on dilution.
Literature. E. P. 2237 and 4237 of 1883 :
Prepared by the action of diazotised aminoazo- '
D. R. P. 26012.
benzenemonosulphonic acid on salicylic acid.
Orange-red solution in water, giving greyish -
Bordeaux G (By.). Prepared by the action
of diazotised aminoazotoluenemonosulphonic
yellow precipitate with hydrochloric acid, and
a dark-red solution and acid on 0-naphthol-6-sulphonic acid (SchafEer's).
precipitate with sodium P. 5003 of 1879.
The Literature. E.
hydroxide. solution in strong sulphuric
acid Bordeaux BX (By.).
is violet,
giving a greyish-yellow precipitate
on dilution. HS0 8 -C H 8 8 -N2 -C 8
H 7 (S0 3H)-N a -C 10 H 5 (S0 3H)-OH
Biebrich Scarlet ; Ponceau 3 RB (A.); New Prepared by heating
1
/3-naphthol with paratoluidine
Red L (K.) Ponceau B and dry calcium chloride :
; Imperial Scarlet (By.) ;
(M.) ; Fast Ponceau B (B.) ; Double Scarlet (K.) :
HS0 3 -C 6 H 4 -N 2 -C 6 H 3 (S0 3 H)-N 2 -C 10 H 6 -OH. '
(Friedlander, Ber. 1883, 16, 2078).

Prepared by the action of diazotised aminoazo- component being j8-naphthol-3 6-disulphonic :
xylenedisulphonic acid on /8-naphthol-6-sul- acid (R-salt). The blue-black aqueous solution

phonic acid (Schaffer's). Red aqueous solution becomes redder with hydrochloric acid. The
giving reddish-brown precipitate with hydro- solution in strong sulphuric acid is green,
chloric acid and becoming browner with sodium becoming red on dilution.
hydroxide. Strong sulphuric acid gives a dark- Literature. E. P. 24980 of 1899 ; D. R. P.
green solution which turns blue and finally 122457 ; A. P. (appl.) 1763 of 1900.
gives a brownish-red precipitate on dilution. Granite Black (A.) :
Literature. E. P. 5003 of 1879. OH-C 6 H 2 (N0 2 2 -N 2 .C in H 5 (S0 3 H)-N 2 -C 10 H 8 -OH.

)
Eriochrome Verdone A (G.): Picramic acid is diazotised and combined with
HS0 3 -C 6 H 4 -N 2 -C 7 H 5 (OH)-N 2 -C 10 H 6 -OH. a-naphthylamine-6-(or 7)-sulphuric acid, and
the product is diazotised and combined with
Sulphanilic acid is diazotised and combined with
m-amino-p-cresol and the product is diazotised j3-naphthol. The dark-violet blue aqueous
and combined with The violet solution gives a dark greenish-blue precipitate
-naphthol.
with sodium hydroxide, and a dark violet-blue
aqueous solution becomes claret-red with
hydrochloric acid, and blue-green with sodium precipitate with hydrochloric acid. The solution
in strong sulphuric acid is blackish-violet.
hydroxide. The solution in strong sulphuric
acid is green, giving a brown-red precipitate on Literature. E. P. 21437 of 1896 ; D. R. P.
dilution. Wool is dyed in claret-red shades 113241 ; F. P. 260056 ; A. P. 583439.
from an acid-bath and on chroming becomes Diaminogen Black (C.) :
blue-green.
NH 2 -C 10 H B (S0 3 H)-N 2 -C 10 Hg-N 2 -Ci H 5 (S0 3 H)-OH.
Literature. E. P. 13904 of 1909 ; D. R. P. Monoacetyl-1 4-naphthylenediamine-7 sulpho-
:
201377 ; F. P. 404536. nic acid is and combined with

diazotised
Janus Red (M.) : o-naphthylamme, the intermediate product
and combined with 7-amino-o-
H
N(CH 3 ) 3 C1-C 6 H 4 -N 2 -C 6 3 (CH 3 )-N 2 -C ]0 H 6 -OH.
diazotised
naphthol-3-sulphonic acid (y-acid), and the
Prepared by diazotising ra-aminophenyltri- product saponified. When diazotised and de-
methylammonium chloride, combining with veloped on the fibre a fast black is produced.
m-toluidine, diazotising the product and com- Literature. E. P. 15443 of 1893 D. R. P. ;
bining with j8-naphthol. The red aqueous 78831 ; F. P. 232299 A. P. 533463.

:
solution gives a brownish-red precipitate with
Diaminogen Blue BB (C.). Prepared as the
hydrochloric acid and a bluish- violet precipitate
with sodium hydroxide. The solution in strong preceding, but the end component is -naphthol-
6-sulphonic acid (Schaffer's).
sulphuric acid is green, and gives a red precipitate Literature as above.
on dilution.
Literature. D. R. P. 93499. Diaminogen Blue G (C.). Prepared as above,
the end-component being jS-naphthol-3 6- :
Nyanza Black B (A.):

disulphonic acid (R-salt).
NH 2 -C 6 H 4 -N 2 -C 10 H 6
-N 2 -C 10
4 (S0 3 H)(NH 2 )-OH. H Literature as above.
Prepared by the action of diazotised p-amino- Diazo Indigo Blue is an analogous product.
benzeneazo-a-naphthylamine (only one amino- Zambesi Sky Blue 4 B (A.). Prepared from
group is diazotised)
l
on 7-amino-a-naphthol- diazotised monoacetyl-3 6-diaminocresyl methyl
:
3-sulphonic acid (7-acid). Solution is dark- ether combined with o-naphthylamine, the 1
violet and gives violet precipitates with hydro- intermediate product being diazotised and
chloric acid and sodium hydroxide. The combined with j8-naphthol-6-sulphonic acid
solution in strong sulphuric acid is blue, and and the end-product saponified. The reddish-
gives a violet precipitate on dilution. The violet aqueous solution becomes redder with
colouring matter itself produces only indifferent hydrochloric acid and bluer with sodium
shades, but when diazotised and developed on the hydroxide. The solution in strong sulphuric
fibre fast shades are obtained. When developed acid is blue and becomes violet-red on dilution.
with m-tolylenediamine, a brown-black is Literature. E. P. 2188 of 1901 ; D. R, P.
obtained, and with /8-naphthol a navy-blue. 126172.
Literature. E. P. 277 and 6630 of 1892; Victoria Black B (By.):
D. R. P. 72394 ; F. P. 221378 ; A. P. 491410, HS0 3-C H 4-N 3 -C 10 H ? -N 2 -C 10 H 4 (S0 3 H)-OH.
6
511688, 512167.
Prepared by the action of diazotised p-sul-
Coomassie Wool Black R (Lev.)
phobenzeneazo-a-naphthylamine on 1 8-dihy-
:
:
NH 2 -C 6
H
H 4 -N 2 -C 10 6 -N 2 -C 10 5 (S0 3 H)-OH. H droxynaphthalene-4-sulphonic acid. The dark
reddish - violet aqueous solution gives with
Prepared by the action of diazotised p-acetyl-
aminobenzeneazo-a-naphthylamine on /3-naph- hydrochloric acid a Bordeaux-red precipitate,
thol-6-sulphonic acid (Schaffer's), and hydrolys-
and with sodium hydroxide becomes dark-
blue violet. The solution in strong sulphuric
ing the product. The dark-violet solution
acid is moss-green, changing on dilution to
gives a precipitate with hydrochloric acid. The
solution in strong sulphuric acid is green, be- sea-green and then to bluish-red.
coming red on dilution. ;
Literature. E. P. 24980 of 1899 ; D. R. P. 61707, 62945 ; F. P. 200520 ; A. P. 466202.

122457 : A. P. (appl.) 1764 of 1900. Jet Black R (By.):
Coomassie Wool Black S (Lev.) :
(HS0 3 2 C 6 H 3 -N 2 -C 10 H 6 -N 2 -C 10 H 6 -NH-C 6 H
) !)
.
NH 2 -C 6
H 4 -N 2 -C 10 H 6 -N 2 -C 10 H 4 (S0 3 H) 2 -OH. Prepared by the action of diazotised disulpho-
benzeneazo-a-naphthylamine on phenyl-a-
Prepared as the preceding dyestuff, the final
The bluish - violet aqueous
All the authorities give the above constitution for
1 naphthylamine.
this colouring matter, but it is generally understood that 1
According to Buntrock (Zsitsch. Farben-Ind. 1902
a benzenoid amino- group is diazotised preferably to a 1, 224). The patents quoted give the 6- or 7-sulphonic
naphthalenoid amino- group. acid as intermediate component.
solution gives a bluish-black precipitate with Literature. As for Diamond Black F; and
hydrochloric acid, and a soluble violet precipitate D. R. P. 62003.
with sodium hydroxide. Strong sulphuric acid Naphthylamine Black D (C.) (K.) Deep Black ;
dissolves the colouring matter to a blue D, cone. (T. M.); Naphthalene Black A (P.);
solution, which gives a greenish-blue precipitate Coomassie Wool Black D (Lev.):
on dilution.
(HS0 3 2 C 10 H 5 -N 2 -C 10 H 6 -N 2 -C 10 H 6 -NH 2
) .

48924 ; F. P. 193430 ; A. P. 425885. a-Naphthylamine-4 :
7-disulphonic acid is diazo-
tised and combined with a-naphthylamine,
Diamond Black F 1 (By.): Chrome Fast and the intermediate product diazotised and
Black B (I.) ; Chrome Deep Black D, extra cone. combined with a-naphthylamine. The violet-
(T. M.); Salicin Black D (K.): black aqueous solution gives a black precipitate
C0 2 H-CS H 3 (OH)-N 2 -C 10 H 6 'N 2 -C 10 H B (S0 3H)-OH. with hydrochloric acid. The solution in strong
Aminosalicylic acid is diazotised and combined sulphuric acid is bluish-black and on dilution
with o-naphthylamine, and the product diazo- becomes green, and finally gives a black
tised and combined with o-naphthol-4-sulphonic precipitate.
acid. Bluish-violet solution gives violet pre- Literature. E. P. 18425 of 1888 ; D. R. P.
cipitate with hydrochloric acid, and becomes 50907 ; F. P. 170342 A. P. 412440. ;
blue with sodium hydroxide. Solution in Naphthylamine Black 4 B (C.) is a mixture of

strong sulphuric acid is greenish, giving a violet Naphthol blue black and the preceding colouring
precipitate on dilution. Similar dyestuffs are matter.
Era Blacks J, F, NG, B and R (Lev.). Naphthyl Blue Black N (C.). Disulpho-
Literature. E. P. 8299 of 1899; D. R. P. naphthaleneazo-a-naphthylamine ethyl ether is
51504 ; F. P. 198521 ; A. P. 438438. diazotised and combined with o-naphthylamine.
Chrome Black I (H.): The dark -violet aqueous solution turns blue
C0 2 H-C 6 H 2 (OH)-N 2 -C 10 H 6 -N 2 -C 10 H 5 -OH and gives a blackish-blue precipitate with hydro-
I I
chloric acid, and becomes blue and precipitates
SO 3H SO 3 H with sodium hydroxide. The solution in strong
Prepared as above, except that the starting sulphuric acid is dark blue, which on dilution
material is the sulphonic acid of aminosalicylic becomes blue, and finally bluish-violet.
acid. red-violet aqueous solution becomes
The Literature. Chem. Ind. 1896, 19, 548.
crimson with hydrochloric acid, and blue with Anthracite Black B (C.) ; Phenylene Black
sodium hydroxide. The solution in strong (P.):
sulphuric acid is bluish-green, becoming violet (HSO a a C lo H s .N,-C IO H e -N,-C 8 H 8 (NH-C,H 6
) )
.
on dilution. 7-in the case of the

o-Naphthylamine-3 :
6-(4 :
Literature.E. P. 2468 of 1899; D. R. P. latter dye) -disulphonic acid is diazotised and

123115; F. P. 293923. combined with a-naphthylamine, and the product
Nerol B (A.) :
diazotised and combined with diphenyl-m-
C4 H B -NH-C 6 H 3 -N 2 -C 10 H 6 -N 2 -C 10 H 4 -OH phenylenediamine. The dull- violet aqueous
I solution gives a violet precipitate with hydro-
SO 3H
I
S0 3 H chloric acid. The solution in strong sulphuric

p-Aminodiphenylamine-o-sulphonic acid is dia- acid is black, giving a greenish-black pre-
zotised and combined with a-naphthylamine, cipitate on dilution.
and the intermediate product is diazotised and Literature. E. P. 4825 and 7977 of 1889;
combined with ^-naphthol-3 6-disulphonic acid : D. R. P. 52616, 61202 ; F. P. 196793, 197963 ;
(R-salt). Dark violet-blue solution in water A. P. 502912.
gives a blue precipitate with hydrochloric acid. Naphthol Black B (C.) ; Brilliant Black B (B.) ;
The solution in strong sulphuric acid is dark-blue Naphthol Black OPAS (Lev.).
violet, giving a blue -violet precipitate on dilution. (HS0 3 2 C 10 H,-N 2 -C 10 H 6 -N 2 -C 10 H 4 (S0 3H) 2 -OH.
)
-Naphthylamine-6 :
8-disulphonic acid is dia-
101274 ; F. P. 271609. and combined with a-naphthylamine,
zotised
Nerol 2 B (A.). Prepared as the preceding, and the product diazotised and combined with
except that the last component is a-naphthol-4- :
6-disulphonic acid (R-salt). The
/3-naphthol-3
sulphonic acid. violet aqueous solution gives with hydrochloric
Properties and literature as above. acid a reddish- violet and with sodium hydroxide
Diamond Green (By.) -.
a blue precipitate. The solution in strong

H H
C6 3 (OH)-N 2 -C IO 6 -N 2 'C ]0 4 (S0 3H)(OH) 2 H .
sulphuric acid is green, becoming
bluer on
dilution, and then giving a reddish-violet
C0 2 H- precipitate.
Prepared by diazotising aminosalicylic acid Literature. E. P. 9214 of 1885 ; D. R. P.
and combining with a-naphthylamine, the 39029 ; F. P. 170342 ; A. P. 345901.
Naphthol Black 2 B (Lev.) is prepared
intermediate product being diazotised and as
combined with 1 8-dihydroxynaphthalene-4- :
the preceding, but starting with a-naphthyl-
sulphonic acid. The blackish- violet aqueous amine-3 6-disulphonic acid.
:
solution gives a dark reddish-violet precipitate Blue Black B (B.) ; Azo Black (M.) :
S0 3 H-C 10 6 -N 2 -C 10 H g .N 2 -C 10 H 4 (S0 3 H)-OH.
with hydrochloric acid, and becomes dark blue
with sodium hydroxide. The solution in strong
H
acid is diazotised
sulphuric acid is
bluish-green, becoming greenish-
j8-naphthylamine-8-sulphonic
and and combined with a-naphthylamine, and the
blue, finally giving a blackish-violet pre- and combined with 0-
cipitate on dilution. product diazotised
1
The yearly production of naphtholdisulphonic acid (R-salt). Aqueous
this important colouring
matter is about 2,000,000 kilos.
solution gives a bluish precipitate with acids
and sodium hydroxide. Solution in strong sul- zotised and combined with aniline, the product
phuric acid bluish-green, becoming blue, and being diazotised and combined with a mixture
finally precipitating on dilution. of 0-naphthol-3 6- and 6 8-disulphonic acids.
: :
Naphthol Black 6 B (C.) (D.) (K.); Acid The bluish-red aqueous solution becomes darker
Black 6 B (H.) Brilliant Black BL and BD (B.)
; ; and bluer with hydrochloric acid, and brownish
Naphthalene Black 5 B (P.) is prepared by the with sodium hydroxide. The solution in strong
action of diazotised disulphonaphthaleneazo-a- sulphuric acid is blue, changing to bluish-red on
naphthylamine on -naphtholdisulphonic acid dilution.
(R-salt). solution dark violet, becom-
Aqueous
C. Tetrazo- Colouring Matters.
ing dark blue with acid or alkali ; dissolves in
strong sulphuric acid with a dark-green colour, Anthracene Yellow C (C.) ;
becoming blue on dilution.
^C
6 H 4 -N 2 -C 8
H
3 (C0 2 H)-OH
E. P. 9214 of 1885; D. R. P.
Literature.
39029; F. P. 1 70342 ; A. P. 345901.
\C H
6 4 -N 2 -C 6
H 3 (C0 2 H)-OH.
Prepared from tetrazotised thioaniline an
Biebrich Patent Black BO (K.) :
acid (2 mols.). The light yellowish

(HS0 3 2 C 10 H 5 -N 2 -C 10 H 5 -N 2 -C 10 H 4 (S0 3 H) 2 -OH. salicylic
brown aqueous solution gives a greenish-broi
)
precipitate with hydrochloric acid. The soluti

S0 3 H
I
in strong sulphuric acid is dark reddish-viol

o-Naphthylaminedisulphonic acid is diazotised giving a yellowish-grey precipitate on dilutio
and combined with a-naphthylamine-6-(or 7)-
Milling Red G (C.) :
sulphonic acid, the product diazotised and com- H
bined with -naphthol-3 6-disulphonic acid :
/-C H
6 4 ,N 2 -C 10 5 (S0 3 H)-OH
(R-salt). The dark reddish- violet aqueous \C H 6 4 -N 2 -C 10 H 5 (S0 3 H)-OH.

Similarly prepared from tetrazotised
solution is turned slightly blue with hydrochloric thioanili
acid and pure blue with sodium hydroxide. and /3-naphthol-6-sulphonic acid (Schaffer's)
Solution in strong sulphuric acid is dark The orange-red aqueous solution gives a bro\
greenish-blue, becoming dark violet on dilution. precipitate with hydrochloric
acid. The soluti
Literature. E. P. 2718 of 1892; D. R. P. in strong sulphuric acid is reddish- violet, givi
73901, 83572, 84460; F. P. 219224; A. P. a brown precipitate on dilution.
476070, 546068, 546069. Cotton Yellow G (B.) :
Biebrich Patent Black 4 AN (K.) : ^NH-C H 6

H 3 (C0 2H)-OH
4 -N 2 -C 6
-N 2 -C 10 H
HS0 3 -C 10 H 6
H 6 -NH 2S (S0 3 H)-N 2
-C 10 .
\NH-C H -N 2 -C 6 H 3 (C0 2 H)-OH.
6 4
Prepared from diazotised naphthionic acid and p-Aminoacetanilide is diazotised

and combin
a-naphthylamine-6-(or 7)-sulphonic acid, the with salicylic acid, the product hydrolysed and
product being diazotised and combined with treated with carbonyl chloride. The yellow
o-naphthylamine. The violet aqueous solution aqueous solution gives a brown precipitate
gives a bluish-black precipitate with hydro- with hydrochloric acid, and becomes rather
chloric acid, and becomes blue with sodium more orange with sodium hydroxide. The
hydroxide. Solution in strong sulphuric acid solution in strong sulphuric acid is orange-red, ;d,
isbluish-green, giving a bluish-black precipitate giving a bluish -violet precipitate
on dilution.
on dilution. Similar dyestuffs bear the brands Literature. E. P. 15258 of 1888; D. R.
6 AN, 4 BN, and 6 BN. 46737, 47902 : A. P. 430535.
References as above. Salmon Red (B.):
Anthracene Acid Black (C.) :
n .^NH-C 6 H 4 -N 2 -C 10
(S0 3H)-NH 2 H 5
OH-C e H 3 -N 2 -C 10 H 5 -N 2 -C 10 H 4 (S0 3H) 2 -OH \NH-C H 4 -N 2 -C 10 H
(S0 3H)-NH 2 .
C0 2 H S0 3 H
6
Prepared as the preceding, but naphthion

5
:
acid is used instead of salicylic acid. The
Aminosalicylic acid is diazotised and combined a bluish-
with o-naphthylamine-6-(or 7)-sulphonic acid, orange- yellow aqueous solution gives
violet precipitate with hydrochloric acid. The
and the product diazotised and combined with
solution in strong sulphuric acid is magenta-
#-naphthol-3 6-disulphonic acid (R-salt).
:
red giving a bluish-violet precipitate on dilution.
Naphthalene Acid Black (By.) :

6 (S0 3 H)-N 2 -C 10 H 6 -NH 2
HS0 3-C H 4 -N 2 -C 10 H 5
.
50852 ; A. P. 430534.
Metanilic acid is diazotised and combined with Heligoland Yellow (N. I.) :
the same acid as in the preceding, and the ^XNH-C 6 H 4 -N 2 -C 6 H 4 -OH

product diazotised and combined with a-naph- \NH-C H 4 -N 2 -C H 4 -OH.
6 6
thylamine. Aqueous solution is violet, becoming
blue with hydrochloric acid, and redder with Prepared by the action of tetrazotised di-p-
sodium hydroxide. Solution in strong sulphuric aminodiphenylcarbamide on phenol (2 mols.)
acid is blue, becoming violet on dilution. The yellow aqueous solution gives a brown
and becomes
Sulphoncyanines are prepared from diazo- precipitate with hydrochloric acid,
tised metanilic acid, which is combined with redder with sodium hydroxide. The solution
o-naphthylamine, the product being diazotised
in strong sulphuric acid is orange- red, giving
and combined with phenyl- and tolyl-a-naph- a brown precipitate on dilution.
Literature. D, R. P. 58204, 60152.
thylamine-8-sulphonic acid. Dyestuffs of this
class are also known as Coomassie Navy Blues Salmon Red (N. I.) :
2 RNX, GNX, G and 3 R (Lev.).

NH-C 6 H 4 -N 2 -C 10 H 5 (S0 3H)-NH 2
cs<
Brilliant Croceine 9 B (C.) : -NH-C6 H 4 -N 2 -C, H 5 (S0 3H)-NH 2 .
(HS0 3)2 C 10 H 5 -N 2 -C B H 4 -N 2 -C 10 H 4 (S0 3 H) 2 -OH. Prepared from the same tetrazo- compound
as
8-Naphthylamine-6 :
8-disulphonic acid is dia- the preceding, and naphthionic acid (2 mols.).
The orange-red aqueous solution gives a bluish- (Cleve's acid), the product saponified, diazotised
violet precipitate with hydrochloric acid. The and combined with 1 mol. of
7-amino-o-naphthol-
solution in strong sulphuric acid is magenta-red, 3-sulphonic acid (y-acid).
giving a bluish-violet precipitate on dilution. Acid Alizarine Black SE (M.) ; Palatine
Literature. As above. Chrome Black F(B.) :
Benzo Fast Pink 2 BL (By.) :

HS0 3 -C 6H 2 (OH)(N 2 -C 10H 6 -OH) 2
^C H (S0 H)-N -C
6 3 3 2 10 H 4 (S0 3 H)(OH)-NH 2 Prepared from tetrazotised 2
.
^C H (S0 H)-N
6 3 3 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 .
4-sulphonic acid and
6-diaminophenol-
-naphthol (2 mols.).
:
Prepared from tetrazotised di-p-aminodiphenyl- Dark-blue aqueous solution

gives a red pre-
carbamidedisulphonic acid and 7 - amino- a - j
cipitate with hydrochloric acid and a greenish-
naphthol-3-sulphonic acid (7-acid ; 2 mols. ). blue precipitate with sodium
j
hydroxide. The
The red aqueous solution becomes reddish- solution in strong sulphuric acid is
violet, giving
violet with hydrochloric acid and yellower ;
a red precipitate on dilution.
'
Literature.. D. R. P. 147880.
sulphuric acid is blue, giving an almost black Manchester Brown EE (C.) Bismarck Brown ;
precipitate on dilution. R (H.) (W.) (I.); Bismarck Brown 2 R, extra

Literature. D. R. P. 129388, 131513 ; Zeitsch. cone. (T. M.) ; Vesuvine B (B) Brown N
(P.) ; :
Farben.-Ind. 1902, 1, 192; Chem. Zeit. 1902, (NH 2 2 C ) 7

H 6
.N 2 -C 7 H 6 -N 2 -C 7 H 6 (NH 2 ) 2.
26, 485.
in the same manner as Bismarck
Bismarck Brown (most firms) Manchester Preparedbut
;
brown, m-tolylenediamine is used instead
Brown Phenylene Brown ; Vesuvine Leather of
; ;
m-phenylenediamine. The reddish-brown
Brown; Cinnamon Brown; English Brown;
Brown A (P.): aqueous solution becomes yellowish-brown with
hydrochloric acid, and gives a light-brown
(NH 2 2 C 6 H 3 -N 2 -C 6 H 4 -N 2 -C 6 H 3 (NH 2 2
)
precipitate with sodium
)
.
The solu- hydroxide.
Prepared by adding a solution of 42-5 kilos, of tion in strong sulphuric acid is dark brown,
sodium nitrite and 127-5 kilos, of hydrochloric becoming first red and then brown on dilution.
acid to a solution of
w-phenylenediamine Literature. Griess, Ber. 1878, 11, 627.
prepared by reducing 250 kilos, of m-dinitro- Toluylene Brown G (0.) (By.):
benzene. The commercial product is the
hydrochloride. The aqueous solution gives a
brown precipitate with sodium hydroxide.
The solution in strong sulphuric acid is brown, Prepared by the action of tetrazotised tolylene-
diaminesulphonic acid (CH 3 NH 2 S0 3 H NH 2 : : :
becoming red on dilution. = 1 2 4 6) on 1 mol. of m-phenylenediamine.

: : :
Literature. E. P. 3307 of 1863 ; Zeitsch. f.

Solution in water is brown, and in strong sul-
Chem. 1867, 3, 287 ; Ber. 1897, 30, 2111, 2203,
2899.
phuric acid brownish-red.
Azo- Alizarine Bordeaux (D. H.) W :
65853 A. P. 516380.
;
H
C0 2 H-C 6 H 3 (OH)-N 2 -C 6 4 -N 2 -C 10 5 (S0 3H)-OH. H Toluylene Yellow (0.). Prepared from the
p-Aminoacetanilide is diazotised and combined same tetrazo- compound as the preceding, and
with salicylic acid, the product hydrolysed 2 mols. of 6-nitro-ra-phenylenediamine in hy-
and diazotised and combined with a-naphthol- drochloric acid solution. The yellowish-brown
4-sulphonic acid. The aqueous solution is red, aqueous solution gives brown precipitates with
and that in strong sulphuric acid is blue. hydrochloric acid and sodium hydroxide.
Literature. E. P. 1033 of 1899; F. P. The solution in strong sulphuric acid is brown.
284775 ; A. P. 631089. Literature. E. P. 1331 of 1896 ; D. R. P.
Azo- Alizarine Black (D. H.). Prepared as 86940.
the preceding, except that the end- component Toluylene Orange RR (O.). Prepared from
is 1
8-dihydroxynaphthalene-3 6-di-(or
: 4- : the same tetrazo- compound as before, and
mono)-sulphonic acid. The aqueous solution is 2 mols. of 0-naphthylamine. The yellowish-
violet, and that in strong sulphuric acid blue. red aqueous solution gives a brownish-red
Literature. E. P. 1033 of 1899; F. P. precipitate with hydrochloric acid, and a
284775 ; A. P. 640010, 628721. yellowish-red precipitate with sodium hydroxide.
Violet Black (B.): The solution in strong sulphuric acid is bluish-
NH 2 -C 10 6 -N 2 -C 6
H H
4 -N 2 -C 10 6 (S0 3 H)'OH.
H grey.
p-Aminoacetanilide is diazotised and combined
with 1 mol. of o-naphthol-4-sulphonic acid. 70147 ; A. P. 497032.
The acetyl- group is then removed by heating DiamineGold(C.):
with acid or alkali, and the amino- compound is C 2 H 6 -0-C 6 H 4 -N 2 -C 10 H 4 (S0 3 H) 2 -N 2 -C 6 H 4 -OH.
diazotised and combined with 1 mol. of a-naph- Prepared from tetrazotised 1 5-naphthylene- :
thylamine. Aqueous solution brownish-red, diamine-3 7-disulphonic acid and phenol (2

:
giving violet precipitate with mineral acids mols.), the product then being ethylated. The
and reddish-violet coloration with acetic acid yellow aqueous solution gives a brownish-
or with sodium hydroxide; blue solution in yellow precipitate with hydrochloric acid and
strong sulphuric acid giving violet precipitate on a yellow precipitate with sodium hydroxide.
dilution. The solution in strong sulphuric acid is reddish-
Literature. D. R. P. 42814. becoming green and then yellow on dilution.
violet,
Ingrain Black C (H.): Literature.. P. 15346 of 1890 D. R. P. ;
HS0 3 -C 10H 5 (N-H 2 )-N2 -C 6 H4 -C 10 H4 (S0 3 H)(OH)-NH2 . 61174; F. P. 182063 A. P. 472121. ;
p-Aminoacetanilide is diazotised and combined Naphthylene Violet (C.):

with a-naphthylamine-6-(or 7)-sulphonic acid NH 2 -C 10
H 6 -N 2 -C 10H 4 (S0 3 H) 2 -N 2 -C 10H 6 -NHj.
Prepared from the preceding tetrazo- compound solution in strong sulphuric acid is blue, becoming
and a-naphthylamine (2 mols.). The Bordeaux- reddish- violet on dilution, and finally giving a
red aqueous solution gives a blue precipitate brown precipitate. The corresponding colouring
with hydrochloric acid, and a red precipitate matter from tolidine is Congo Orange R (A.).
with sodium hydroxide. The solution in strong Literature. E. P. 17957 of 1889 ;
D. R. P.
sulphuric acid is blue, and gives a violet pre- 52328.
cipitate on dilution. The colouring matter Pyramidol Brown BG (P. L.):
is usually diazotised and developed on the fibre
C,H 4 -N 2 -C6 3 (OH) 2 H
or treated on the fibre with nitrous acid, the
latter colour being known as Diamine Cuteh, C 6 H 4 -N 2 -C H
6 3 (OH) 2 .
which is a fast brown shade. from tetrazotised benzidine and

Prepared
Literature. E. P. 15346 of 1890 ; D. R. P. resorcinol (2 mols.). The orange-brown aqueous
62075 ; F. P. 208526 ; A. P. 464566. solution gives a brown precipitate with hydro-
Coomassie Navy Blue (Lev.). chloric acid, and becomes Bordeaux-red with
sodium hydroxide. The solution in strong
1
Prepared by 4-naphthylene- sulphuric acid is reddish-violet, giving a brown
:
diazotising
one amino-
acid
diamine-2-sulphonic (only precipitate on dilution. Cotton dyed red with
group can be diazotised), combining with j8- this colouring matter is converted into a deep
naphthol-3 6-disulphonic acid, diazotising the
:
brown when treated with a diazo- compound
product (the second Umino- group can now be on the fibre.
diazotised), and combining with j8-naphthol. Chrysamine G (By.) (A.) (Lev.) (H.) ; Azidine
Dark-blue aqueous solution becomes violet with Yellow G (C. J.):
sodium hydroxide. Solution in strong sulphuric C 6 H 4 -N 2 -C 6 H 3 (OH)-C0 2 H
acid is blue -green, becoming dark blue on
dilution.
C 6 H 4 -N 2 -C 6 H 3 (OH)-C0 2 H.
Literature.E. P. 2946 of 1896 ; D. E. P.
102160 F. P. 256862
;
A. P.619194, 639748.
;
Prepared by the action of tetrazotised benzidine
1 on salicylic acid (2 mols.) in alkaline solution.
Diphenyl Fast Black (G.): Used for dyeing cotton goods yellow directly
^C H
7 6 -N 2 -C 10
H
4 (OH)(NH 2 )-S0 3
H from a soap-bath. Aqueous solution orange,
becoming redder on addition of sodium hy-
Prepared from tetrazotised ^-diaminoditolyl- droxide ; orange flocculent precipitate, with
amine and 1 mol. of 7-amino-o-naphthol-3- dilute sulphuric acid. Soluble in strong sul-
sulphonic acid (-y-acid) and 1 mol. of m-tolylene- phuric acid, with a magenta-red colour, becoming
diamine. The violet-black aqueous solution orange and precipitating on dilution. The
gives with hydrochloric acid a bluish-black homologue from tetrazoditolyl is Chrysamine R.
precipitate, and with sodium hydroxide a black Literature. E. P. 9162 and 9606 of 1884;
precipitate. The solution in strong sulphuric D. R. P. 31658 ; A. P. 329638.
acid is dark blue, and gives a black precipitate Cresotine Yellow G (A.) (By.) (0.):
on dilution. C 5 H 4 -N 2 -C 7 H 6 (C0 2 H)-OH
258521 ; A. P. 575904. C 6 H 4 -N 2 -C 7 H 5 (C0 2 H)-OH.
Dianthine (Glaus & Co.) ; St. Denis Red (P.)
Prepared from tetrazotised benzidine and
;
Rosophenine 4 B (Cl. Co.) ; Rosanol 4 B (K.) :
hydroxytoluic acid (OH CH 3 C0 2 H 1 : : :

=
xN-C 7 H 6 -N 2 -C 10 6 (S0 3 H)-OH H 2:6). Yellow aqueous solution gives a
o H
\N-C 7 6 -N 2 -C 10 6 (S0 3 H)-OH. H brownish-yellow precipitate with hydrochloric
acid and becomes yellowish-red with sodium
Prepared from tetrazotised diaminoazoxytoluene hydroxide. Solution in strong sulphuric acid
and o-naphthol-4-sulphonic acid (2 mols.). is reddish-violet,precipitating on dilution.
The red aqueous solution gives red precipitates The corresponding colouring matter fror
with hydrochloric acid and sodium hydroxide. tolidine is Cresotine Yellow R (A.) (By.) (0.) ;
The solution in strong sulphuric acid is red, Azidine Yellow R (C. J.).
and gives a red precipitate on dilution. Literature. E. P. 7997 of 1888; A. P.
Literature. E. P. 9315 of 1887, 5736 of 1890; 394841.
D. R. P. 44045 ;
F. P. 184549 ; Compt. rend. Cloth Orange (By.):
1901, 132, 985. C 8 H 4 -N 2 -C 6 H 3 (C0 2H)-OH
Congo Orange G (A.):
C H -N
6 4 2 -C H -0-C H 6
6 4 2 H H
C 6 4 -N 2 -C 6 3 (OH) 2 .
C H 4 -N -C 10 H (S0 H) Prepared from diazotised benzidine and 1 mol

2 -NH 2
.
6 2 4 3 each of salicylic acid and resorcinol. Yellowish-
z
Prepared from tetrazotised benzidine and 1
brown solution gives brown precipitate wit
mol. of )8-naphthylamine-3 6-disulphonic acid,
hydrochloric acid, and becomes red with sodiurr
:
and 1 mol. of phenol, the product being ethylated.

The orange-yellow aqueous solution gives a is reddish-violet, giving a brown precipitate on
brown precipitate with hydrochloric acid. The dilution.
1
Diamine Deep Black (C.) is derived from p-diaminodi- Literature. E. P. 2213 of 1886 and 6687
phenylamine Pluto Black (By.) also belongs to the same
;
1887 ; D. R. P. 44797.
class.
=
Benzidine or p-diaminodiphenylis prepared by reduc- Cloth Brown R (By.) :
ing nitrobenzene with zinc-dust and alkali to hydrazo- C 6 H 4 -N 2 -C 6 H 3 (C0 2 H)-OH

benzene and converting this by means of acids into
benzidine. The homologues of benzidine are prepared
in a similar manner.
Prepared from tetrazotised benzidine, and 1 mol. brown aqueous solution gives a brown
precipitate
each of salicylic acid and a-naphthol-4-sulphonic with hydrochloric acid and a reddish-brown
acid. Reddish-brown aqueous solution gives precipitate with sodium hydroxide. The solu-
a brown precipitate with hydrochloric acid. tion in strong sulphuric acid is
violet, changing
Solution in strong sulphuric acid is bluish- to brown on dilution.
violet, giving a reddish-brown precipitate on Literature. D. R. P. 57857 ; F. P. 201770
dilution. Diphenyl Brown BN (G.) :
Literature. As for the preceding. H H

C 6 4 -N 2 -C G 3 (C0 8 H)-OH
Cloth Brown G (By.):
C 6 H 4 -N 2 -C 6 H 3 (C0 3H)-OH H H
C 6 4 -N 2 -C 10 4 (S0 3 H)(OH)-N(CH 3 ) 8 .
Prepared from tetrazotised benzidine and I mol.

C 6 H 4 -N 2 -C 10H 5 (OH) 2 . each of salicylic acid and
7-dimethylamino-o-
Prepared from tetrazotised benzidine and 1 mol. naphthol-3-sulphonic acid. [The corresponding
and 1 mol. of 2 7-dihydroxy-
of salicylic acid :
colouring matter from the monomethylamino-
naphthalene (the latter combined in weak compound is Diphenyl Brown RN (G.).] The
acetic acid solution). The brown aqueous dark- brown solution gives a red
precipitate with
solution gives a brown precipitate with hydro- hydrochloric acid. The solution in strong
chloric acid, and becomes reddish-brown with sulphuric acid is bluish-violet, giving a red
sodium hydroxide. The solution in strong precipitate on dilution. When tolidine is
sulphuric acid is reddish-violet, giving a brown used instead of benzidine, Diphenyl Brown 3 GN
precipitate on dilution. obtained.
is
Literature. As for Cloth Brown R. Literature. E. P. 2771 of 1896 ; D. R P
Benzo Orange R (By.): '
103149 ; F. P. 250697 ; A. P. 567413.
C e H 4 -N 2 -C 6 H 3 (C0 2 H)-OH Diamine Brown B (C.):
C 6 H 4 -N 2 -C 6 H 3 (C0 2 H)-OH
H H
C 6 4 -N 2 -C 10 5 (S0 3 H)-NH 2 .
Prepared from tetrazotised benzidine and 1 mol.

H H
C 6 4 -N 2 -C 10 4 (S0 3 H)(OH)-NH-C 6 H 5 .
each of salicylic acid and naphthionic acid. Prepared from tetrazotised benzidine and 1 mol.
The orange - yellow aqueous solution becomes each of salicylic acid and 7-phenylamino-o-
reddish-violet with hydrochloric acid, and gives naphthol-3-sulphonic acid. The dark-brown
a reddish-yellow precipitate with sodium aqueous solution gives a Bordeaux-red pre-
hydroxide. Solution in strong sulphuric acid cipitate with hydrochloric acid, and becomes
is violet-blue, giving a greyish-violet precipitate redder with sodium hydroxide. The solution
on dilution. in strong sulphuric acid is violet, giving a brown
E. P. 2213 of 1886; D. R. P.
Literature. precipitate on dilution.
44797 A. P. 447303.
;
Oxamine Maroon (B.):
Diamine Fast Red F (C.); Dianol Fast C 6 H 4 -N 2 -C 6 H 3 (C0 2 H)-OH
Red F (Lev.) Azidine Fast Red F (C. J.);
Oxamine Fast Red F (B.); Naphthamine Red C 6 H 4 -N 2 -Ci H 4 (S0 3 H)(OH) -NH 2 .
H(K.): Prepared by combining tetrazotised benzidine

C 6 H 4 -N 2 -C 10H 4 (S0 3H)(OH)-NH 2 with 1 mol. of 5-amino-o-naphthol-3-sulphonic
acid in alkaline solution, and adding 1 mol. of
C 6 H 4 -N 2 -C 6 H 3 (C0 2 H)-OH. salicylic acid to the product. The ruby-red
Prepared from tetrazotised benzidine and 1 mol. aqueous solution does not change with acids or
of alkalis. The solution in strong sulphuric acid
7-amino-o-naphthol-3-sulphonic acid (y-acid)
combined in acid solution, and 1 mol. of salicylic is dark violet, changing to wine-red on dilution.
Red aqueous Literature. E. P. 2370 of 1893; D. R. P.

acid. solution gives a brown
precipitate with hydrochloric acid. The solution 82572 ; F. P. 229263.
in strong sulphuric acid is and Oxamine Red (B.). Isomeric with the
reddish-blue,
gives a brown precipitate on dilution. preceding. 6-Amino-o-naphthol-3-sulphonic acid
Literature. E. P. 16699 of 1889 D. R. P. is used instead of the 5-amino- acid. The red
57857 ; F. P. 201770. aqueous solution is not changed by hydrochloric
Crumpsall Direct Fast Red R (Lev.) :
acid, but becomes slightly more violet with
H sodium hydroxide. The solution in strong
H
C 6 4 -N 2 -C 10 4 (S0 3H) 2 -OH
blue, changing to wine-red on
sulphuric acid is
dilution.
C 6H 4 -N 2 -C H (C0
6 3 2 H)-OH. Literature. E. P. 2622614 of 1893 ; D. R. P.
Prepared from tetrazotised benzidine and 1 mol. 93276 ; F. P. 227892 ; A. P. 555359.
each of fl-naphthol-S
6-disulphonicacid(R-salt)
:
Wool Red G (B.):
and salicylic acid.
C 6 H 4 -N 2 -C 6 H 3 (S0 3 H)-OH
Diamine Brown M
(C.) ; Chlorazol Brown M
(H.) ; Renol Brown MB, cone. (T. M.)
Brown M
Azidine ;
H H
C 6 4 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 .
(C. J.) Naphthamine Brown (K.) ;

;
Crumpsall Direct Fast Brown B (Lev.) :

each of phenol-o-sulphonic acid and 7-amino-a-
H H
C a 4 -N 2 -C 6 3 (C0 2 H)-OH
naphthol-3-sulphonic acid (y-acid) the latter
C 6 H 4 -N a -C 10H 4 (S0 3 H)(OH)-NH 2 being combined in acid solution. The red
aqueous solution gives a brown precipitate with
.
Prepared from tetrazotised benzidine and 1 mol. hydrochloric acid, and becomes dark red with
each of salicylic acid and sodium hydroxide. Solution in strong sulphuric
7-amino-o-naphthol-3-
sulphonic acid (y-acid) the latter being
; acid is violet, giving a brown precipitate on
combined in alkaline solution. The reddish- dilution.
Literature.!). R. P. appl. 29649 of 1901 Congo Rubine
;
(A.) (Lev).; Azidine Bordeaux
F. P. 313533.
Diamine Scarlet B (C.) ; Dianil Ponceau G C 6 H 4 -N 2 -C 10H 6 (S0 3 H)-NH 2
(M.)':
C 6 H 4 -N 2 -C 6 H 4 -0-C 2 H 5 H
C 6 4 -N 2 -C 1(,H 5 (S0 3 H)-OH.
C 6 H 4 -N 2 -Ci H 4 (S0 3 H) 2 -OH. each of o-naphthol-8-sulphonic acid and
naph-
Tetrazotised benzidine is combined first with 1 thionic acid. The cherry-red aqueous
solution
mol. of 0-naphthylamine-6 : 8-disulphonic acid, gives a blue precipitate with hydrochloric acid
then with 1 mol. of phenol and the product is and a violet-red one with sodium
hydroxide.
ethylated. The red aqueous solution becomes The solution in strong sulphuric acid is blue,
brownish-red with hydrochloric acid. The giving a blue precipitate on dilution.
solution in strong sulphuric acid is violet, Literature.!). R. P. 62659.
becoming brown on dilution. Congo Corinth G (A.) (By.) ; Cotton Corinth G
Literature. E. P. 12560 of 1889 D. R. P. ; (B.) ; Dianil Bordeaux G (M.) :
54084 ; F. P. 200152 ; A. P. 426345. C 6 H 4 -N 2 -C ]0H 5 (S0 3 H)-OH
Pyramine Orange 2 R (B.):
C 6 H 4 -N 2 -C 10 H 4 (S0 3 H) 2 -NH 2 H H
C 6 4 -N 2 -C 10 5 (S0 3 H)-NH 2 .
Prepared from tetrazotised benzidine, a-naph-

H H
C 6 4 -N 2 -C S 2 (NH 2 ) 2 -N0 2 .
thylamine-4-sulphonic acid and a-naphthol-4-
Prepared from tetrazotised benzidine and 1 mol. sulphonic acid. Aqueous solution red ; violet
each of -naphthylamine-3 6-disulphonic acid :
precipitate with hydrochloric acid and coloration
and p-nitro-ra-phenylenediamine. The yellow with acetic acid. Solution hi
strong sulphuric
aqueous solution is not changed by acids or acid blue, giving violet precipitate on dilution.
alkalis. The solution in strong sulphuric acid Literature. E. P. 15296 of 1885 2213 and ;
is blue, becoming yellowish-red on dilution. 6687 of 1886 ; D. R. P. 39096 ; F. P. 160722,

Literature. E. P. 6827 of 1899 ; D. R. P. 163172 ; A. P. 344971, 358865.
107731 ; F. P. 280914 ; A. P. 631611. Brilliant Congo G (A.) (By.) :
Pyramine Orange 3 G (B.) :

C 6 H 4 -N 2 -C 10H 4 (S0 3 H) 2 -NH 2
C 6 H 4 -N 2 -C 6 H 2 (NH 2 ) 2 -N0 2
C 8 H 4 -N 2 -C 10H 6 (S0 3 H)-NH 2
C 6 H 4 -N 2 -C 6 H(S0 3 H).,(NH 2
.
) 2. From tetrazotised benzidine, -naphthylamine-

Prepared from tetrazotised benzidine and 1 mol. 3 : 6-disulphonic acid and
0-naphthylamine-6-
each of m-phenylenediamine-4
6-disulphonic sulphonic acid (Bronner's). Aqueous solution
:
acid andp-nitro-m-phenylenediamine. The gives a brownish-violet precipitate with hydro-

yellowish-red aqueous solution is not changed chloric acid. Solution in strong sulphuric acid
by or alkalis. The solution
acids in strong blue, giving violet precipitate on dilution.
sulphuric acid is yellowish - red, becoming Literature. E. P. 6687 of 1887: D. R.
brownish- yellow on dilution. 41095 ; F. P. 160722.
Literature. E. P. 18506 of 1898 D. R. P. ;
2 B (A.) (By.) (L.):
Heliotrope
105349 F. P. 280914 A. P. 631610.
; ;
C 6H 4 -N 2 -C 10H B (S0 3 H)-OH
Congo Red (Lev.) (A.) (By.); Congo Red R
Cosmos Red (B.); Cotton Red cone.
(H.);
(T. M.); Cotton Red G (P.); Cotton Red B H
C 6 4 -N 2 -C 10 H 4 (S0 3 H) 2 -OH.
(K): Prepared from tetrazotised benzidine and 1
C 8 H 4 -N 2 -C 10H 6 (S0 3 H)-NH 2 each of a-naphthol-4 8-disulphonic acid and
:
-
naphthol - 8 - sulphonic acid. Reddish- violet
H H
C 6 4 -N 2 -C 10 6 (S0 3 H)-NH 2 . aqueous solution gives a bluish- violet precipitate
with hydrochloric acid, and becomes redder
Prepared by the action of tetrazotised benzidine with sodium hydroxide. Solution in strong
on naphthionic acid (2 mols). It can also be
obtained by oxidising benzeneazonaphthionic sulphuric acid is blue, becoming reddish-violet
on dilution, and finally giving a violet precipitate.
acid with manganese dioxide in sulphuric acid
solution (E. P. 6697 of 1895; D. P. 84893; F. P.
45342.
248210). The red aqueous solution becomes blue
on addition of dilute acids ; substance dissolves Trisulphone Violet B (K. S.); Trisulphone
Blue R (K. S.) ; Trisulphone Blue B (K. S.):
in strong sulphuric acid with a slaty blue, giving
a bluish precipitate on dilution. H H
C 6 4 -N 2 -C 10 3 (S0 3 H) 3 -OH
28753; Ber. 1886, 19, 1719. C6 H 4 -N 2 -C 10 H
8 -OH.
;
Diazo Black B (By.). Isomeric with the The first-named (for which the formula is given)
preceding. Prepared from tetrazotised benzi- is prepared from tetrazotised benzidine and
dine and 1 mol. each of a-naphthol-3 6 : 8-trisulphonio
a-naphthylamine-5-sulphonic acid :
(L-acid; 2 mols.). The violet aqueous solution acid and -naphthol. The second and last
becomes blue with hydrochloric acid, and gives colouring matters are prepared from tetrazotised
a blue precipitate with sodium hydroxide. tolidine and dianisidine respectively instead of
The solution in strong sulphuric acid is blue, benzidine. The solutions in water are violet
remaining blue on dilution. The colouring to blue, and give bluish- violet to blue precipitates
matter is generally diazotised and developed with hydrochloric acid. With sodium hydroxide
on the fibre. the aqueous solutions become reddish- violet. The
solutions in strong sulphuric acid are greenish-
1
Diamine Scarlet 3 B (C.); Dianil Ponceau 2 R (M.)
belongs to the same group, but is bluer. blue, giving violet precipitates on dilution.
Literature. E. P. 1897 4703 of ;
F. P. acid (K- acid), and 7-amino-o-naphthol-3-sul-
264279 ; A. P. 584981. phonic acid (y-acid).
Chicago Blue 4 R (A.) Benzo Blue 4 R (By.) ; ; Literature. R. P. 515 of 1894; D. R. P.
Columbia Blue R (A.) ; Benzo Red Blue R (By.). 99164 A. P. 563383.
;
The first two and the last two respectively are Diamine Brown V (C.):
probably identical. These colouring matters C 6 H 4 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2
are produced from benzidine, and 1 mol. each of
aminonaphthol-sulphonic acid (1:8:4) or -di- C 6 H 4 -N 2 -C 6 H 3 (NH 2 ) 2.
sulphonic acid (1:8:2:4) and a naphthol-
sulphonic acid. Chicago blue 4 B gives a each of 7-amino-o-naphthol-3-sulphonic acid
violet- blue and Columbia blue R a pure blue
(y-acid) and m-phenylenediamine. Brown-red
aqueous solution. Both solutions give a blue
with hydrochloric acid. With aqueous solution gives a chocolate-brown pre-
precipitate
sodium hydroxide the former becomes reddish- cipitate with hydrochloric acid, and purplish-
brown precipitate with sodium hydroxide.
violet, and the latter blue. The solutions in
Solution in strong sulphuric acid is bluish-
strong sulphuric acid are cornflower blue,
violet, giving a purplish-brown precipitate on
giving precipitates on dilution.
dilution.
Diamine Violet N (('.); Chlorazol Violet B
(H.) Dianol Violet N (Lev.) ; Azidine Violet DV
;
;
57857 F. P. 201770.
(C. J.); Naphthamine Violet N (K.)
;
:
Diamine Black BH (C.); Dianol Blue BH

C 6 H 4 -N 2 -C 10H 4 (S0 3 H)(OH)-NH 2
(Lev.); Diazo Black BHN (By.) Renolamine ;
Black BH (T. M.) Azidine Black BHN (C. J.) In-

C 6 H 4 -N 2 .C 10H 4 (S0 3 H)(OH)-NH 2 .
Black
; ;
grain 2 B(H.) ; Naphthamine Black CE(K.):

Prepared by the action of tetrazotised benzidine H
C 6 4 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2
on 2 mols. of 7-amino-o-naphthol-3-sulphonic
acid (y-acid) acid solution.
in The reddish- C6 H 4 -N 2 -C 10
H 3 (S0 3 H) 2 (OH)-NH 2 .
violet aqueous solution gives a violet-black

precipitate with hydrochloric acid. The solution Prepared from tetrazotised benzidine and 1 mol.
in strong sulphuric acid is
each of 7-amino-a-naphthol-3-sulphonic acid
greenish-blue, giving and 8-amino-o-naphthol-3 6-disulphonic acid :
a reddish- violet precipitate on dilution.
Literature. E. P. 16699 of 1889 ; D. R. P. (H- acid). The reddish-blue aqueous solution
55648 ; F. P. 201770. becomes violet with hydrochloric acid and
Diamine Black RO reddish-violet with sodium hydroxide. The
(('.); Naphthamine Black solution in strong sulphuric acid is blue, giving
BVE Isomeric with the preceding. The
(K.).
combination effected in alkaline solution where-
is
a violet precipitate on dilution.
the azo- Literature. E. P. 1742 of 1891 ; D. R. P.
by group enters the 2- position with 68462 ; F. P. 233032.
respect to the hydroxy- group, whereas in the
Oxamine Violet (B.) : Chlorazol Violet R (H.) ;
preceding case the azo- group enters the 8- position
(ortho to the amino- group). The violet-black Naphthamine Violet BE (K.) :
aqueous solution gives a blue precipitate with C 6 H 4 -N 2 -C 10H 4 (S0 3 H)(OH)-NH 2
hydrochloric acid, and becomes violet with sodium
hydroxide. The solution in strtong sulphuric H H
C 6 4 -N 2 -C 10 4 (S0 3 H)(OH)-NH 2 .
acid is blue, giving a reddish-blue precipitate on Prepared from tetrazotised benzidine and 6-
dilution. amino-a-naphthol-3-sulphonic acidmols.). (2
Literature. As above. The combination is effected in alkaline solution.
Naphthamine Black RE (K.): The. reddish-violet aqueous solution gives a
C 6 H 4 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH, violet precipitate with acids or alkalis. The
solution in strong sulphuric acid is blue, giving
C 6 H 4 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 .
Literature. -E. P. 2614 of 1893 ; D. R. P.
Prepared from tetrazotised benzidine and 2
mols. of 1
75469 ; F. P. 227892 ; A. P. 521096.
8-aminonaphthol-6-sulphonic acid.
:
Diamine Blue BB (C.) Benzo Blue BB (By.)

Literature.!). R. P. appl. 11223. K Congo Blue 2 BX (A.)
;
Direct Blue V
Benzo Violet R (By.):
(Lev.) ; ;
(P.) ; Azidine Blue 2 B (C. J.) Chlorazol Blue :
C 8 H 4 -N 2 -C 10 H 6 (S0 3 H)-OH RB (H.) ; Naphthamine Blue 2 BX (K.) :
C 6 H 4 -N H C 6 H 4 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH
!!
-C 10 4 (S0 3 H) -OH.
!!
Prepared from tetrazotised benzidine and 1 mol. C 6 H 4 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH 2 .
each of a-naphthol-4-sulphonic acid and a-naph-

thol-3 The reddish- violet Prepared by combining tetrazotised benzidine
:
6-disulphonic acid. in alkaline solution with 8-amino-a-naphthol-
aqueous solution gives a soluble violet precipitate 3 6-disulphonic acid (H-acid ; 2 mols.). The
:
with hydrochloric acid, and becomes red with
reddish-blue aqueous solution is unchanged by
sodium hydroxide. The solution in strong
acids or alkalis. The solution in strong sulphuric
sulphuric acid is violet, giving a violet precipitate
on dilution. acid is blue, becoming violet on dilution.
Literature. E. P. 13443 of 1890; 1742 of
Naphthylamine Diazo Black (K.): 1891 ; D. R. P. 74593 ; F. P. 210033 ; A. P.
H H
C 6 4 -N 2 -C 10 4 (S0 3 H)(OH)-NH 2 464135.
Naphthamine Blues 2B, 3B and 5B (K.).
C 6 H 4 -N 2 -C 10H 3 (S0 3 H) 2 (OH)-NH 2 .
These are derived form tetrazotised benzidine,
5-disul-
Prepared from tetrazotised benzidine and 1 mol. tolidine, etc., and 8-amino-o-naphthol-3
:
phonic acid (K-acid). The blue aqueous

each of solution
8-amino-a-naphthol-3 5-disulphonic :
VOL. 1.T. 2 c
gives a blue precipitate with hydrochloric acid tetrazotised nitrobenzidine and salicylic acid
and turns reddish- violet with sodium hydroxide. (2 mols.), the product being sulphonated. The
The solution in strong sulphuric acid is bluish- orange aqueous solution is precipitated with
green. hydrochloric acid and becomes reddish-brown
Literature. V. P. 515 of 1894; D. R. P. with sodium hydroxide. The solution in strong
99164; A. P. 563385, 563386. wn
sulphuric acid is orange-yellow, and gives a brown
Direct Gray R (I.): precipitate on dilution.
C,H 4 -N 2 -C 10 H 3 (OH) 2 (C0 2 H)-S0 3 H Literature. As above, and Chem. Ind. 18'
19 552
C 6H 4 -N 2 -C 10 H 3 (OH) 2 (C0 2 H)-S0 3 H. 'sulphone Azurine (By.) (A.) (L.) (Lev.):
H H H
Prepared from tetrazotised benzidine and
1: 7-dihydroxy -6 - carboxynaphthalene-3-sul- SO // C (S0 H)-N -C 10 -NH-C
I
6 2 3 2 6 6 6
phonic acid (2 mols.). The violet aqueous \C H (S0 H)-N -C 10H -NH-C H
6 2 3 2 6 6 5.
solution gives a bluish-grey precipitate with Prepared from tetrazotised benzidinesulphone-
hj'drochloric acid and becomes dull violet-red disulphonic acid and phenyl-jS-naphthylamiiie
with sodium hydroxide. The solution in strong (2 mols.). The blue aqueous solution gives blue
sulphuric acid is blue, giving a bluish-grey precipitates with hydrochloric acid and sodium
precipitate on dilution. The corresponding hydroxide. The solution in strong sulphuric
colour from tolidine is Direct Gray B. acid is violet, giving a blackish- violet precipitate
Literature. E. P. 14253 of 1892 D. R. P. ; on dilution.
75258 F. P. 220468 ; A. P. 493564.
; Literature. E. P. 1099 of 1884 ; D. R, P.
Dianol Red 2 B (Lev.); Azidine Purpurine 27954, 33088; A. P. 432989; Ber. 1889, ",
22,
10 B (C. J.): 2459.
H
C 6 H 3 C1-N 2 -C 10 B (S0 3 H)-NH 2 Pyramine Orange R (B.) :
S0 3 H-C 6 H 3 -N 2 -C 6 H 2 (NH 2 ) 2 -NO a

C6 H a-N -C 10H
3 2 6 (S0 3 H)-NH 2 .
Prepared from dichlorobenzidine

tetrazotised H
S0 3 H-C 6 3 -N 2 -C g 2 (NH 2 2 H yN0 .
(NH 2 : Cl=4 : 3), and naphthionic acid (2 mols.). Prepared from tetrazotised benzidinedisulphonic
The red aqueous solution becomes violet with acid and 6-nitro-w-phenylenediamine (2 mols.).
hydrochloric acid. The solution in strong The orange-red aqueous solution gives a yellow-
sulphuric acid is blue, changing to violet on ish-red precipitate with hydrochloric acid
dilution.
or sodium hydroxide. The solution in strong
sulphuric acid is yellow, giving a yellowish-red
265135 A. P. 640743.
precipitate on dilution.
;
Dianol Brilliant Red (Lev.) Toluylene Red ;

(0.); Chlorantine Red 8 B (I.) Acetopurpurine ;
80973 ; F. P. 238340 ; A. P. 545333.
(A.) ;Diphenyl Red 8 B (G.) ; Azidine Brilliant Carbazole Yellow (B.) :
Red8B(C.
/ C 6 H 3 -N 2 -C 6 H 3 (C0 2 H)-OH
J.):
C6 H 3 C1-N 2 -C 10 H 4 (S0 3 H) 2 -NH 2
NH<\C H -N
2 -C 6 H 3 (C0 2 H)-OH.
|
C6 H 3 C1-N 2 -C 10 H 4 (S0 3 H) 2 -NH 2 .

3
6
from tetrazotised diaminocarbazolesole
Prepared
Prepared from tetrazotised dichlorobenzidine
and acid The brownish-
and acid. salicylic (2 mols.).
6-disulphonic
j3-naphthylamine-3 :
yellow aqueous solution gives a brown pre-

The bluish-red aqueous solution becomes
darker with acid. The cipitate with hydrochloric acid, and becomes
slightly hydrochloric The
solution in strong sulphuric acid is blue, becoming orange-yellow with sodium hydroxide.
solution in strong sulphuric acid is violet-blue,
red on dilution.
Literature. E. P. 25725 of 1896 ; D. R. P. giving a brown precipitate on dilution.
Literature. E. P. 14478 and 14479 of 1888 ;
94410, 97101 F. P. 265135 ; A. P. 625174.
;
D. R. P. 46438 F. P. 193212 ; A. P. 401634.
Anthracene Red (I.) (By.) :
;
H (C0 H)-OH Pyramidol Brown T (P. L.):

N0 2 -C 6 H 3 -N 2 -C 6 3 2
H
C 7 6 -N 2 -C 6 3 (OH) 2 H
C 6 H 4 -N 2 -C 10 H (S0 H)-OH.
6 3
H
C 7 6 -N 2 -C 6 3 (OH) 2. H
Prepared by combining tetrazotised nitro-
benzidine first with 1 mol. of salicylic acid and Prepared from tetrazotised tolidine and
then with 1 mol. of a-naphthol-4-sulphonic acid. sorcinol (2 mols.). The reddish-brown aqueous
(The same colour is not produced by inverting solution gives a brown precipitate with hydro-
the order of combination.) The red aqueous chloric acid, and becomes brownish-rod with
solution gives a red precipitate with hydrochloric sodium hydroxide. The solution in strong
acid. The solution in strong sulphuric acid is sulphuric acid is violet, giving a blackish-brown
carmine-red, giving a brownish-red precipitate precipitate on dilution. When the fibre i
on dilution. treated with diazo- solutions a deep brown is
Literature. E. P. 13475 of 1892 ; D. R. P. obtained.

72867 ; F. P. 223176 ; A. P. 493583. Toluylene Orange G (0.) (By.) (A.) ;
Kantho-
Salicine Red G (K.). sine J Azidine Orange G (C. J.)
Prepared from tetra-
:
;
zotised nitrobenzidine and 1 mol. each of salicylic H H

C 7 6 -N 2 -C 7 5 (C0 2 H)-OH
acid and /3-naphthol, the product being sul-
phonated. H
C 7 H.-N 2 -C 7 4 (NH 2 ) 2 -S0 3 H.
Prepared from tetrazotised tolidine and 1
Literature. E. P. 9454 of 1895 D. R. P. mol.
each of hydroxytoluic acid (CH 3 OH C0 2 H
;
87484. : :
Salicine Yellow G (K.). Prepared from = 1:2:3) and m-tolylenediaminesulphonic acid

(CH 3 2 : : NH NH
2 : S0 3 H=1 : 2 4 : 5). The :
Prepared from tetrazoditolyl and 1 mol. of
brownish - yellow aqueous solution gives a crude -naphthylamine-8-sulphonic acid and
with 1 mol. of the 6-sulphonic acid.
yellowish-brown precipitate hydrochloric Owing to the
acid, and becomes reddish-orange with sodium 8-acid being a mixture of isomerides (the 2 7- :
hydroxide. The solution in strong sulphuric and 2 6-acids), the colouring matter contains
:
acid is magenta-red, giving a brown precipitate also benzopurpurine B and deltapurpurine 7 B

on dilution. (see below). Aqueous solution orange, giving
Literature. E. P. 7997 of 1888 ; D. R. P. a brown coloration with acetic acid, and a
47235 ;
A. P. 396634. brown precipitate with hydrochloric acid. Red
Toluylene Orange R (().); Kanthosine R ; precipitate with sodium hydroxide. Solution
Azidine Orange R (C. J.): in strong sulphuric acid blue, giving a brown
C 7 H 6 -N 2 -C 7 H 4 (NH 2 2 -S0 3 H
)
precipitate on dilution.
Literature.E. P. 5846 of 1886; D. R. P.
C 7 H 6 -N 2 -C 7 H 4 (NH 2 )2 -S0 3 H. 42021 Ber. 1887, 20, 1430, 2910, 3160, 3353.
;
Diamine Red 3 B (C.) ; Deltapurpurine 7 B

Prepared from tetrazotised tolidine and toly- m (By.) (A.). Isomeric with the preceding. Pre-
lenediaminesulphonic acid (2 mols. ). The orange
pared from diazotised tolidine and j8-naphthyl-
aqueous solution gives a bluish-red precipitate amine-7-sulphonic acid. The colouring matter
with hydrochloric acid. The solution in strong
is precipitated from its aqueous solution by
sulphuric acid is brown, giving a reddish pre- acetic acid, and forms an insoluble calcium
cipitate on dilution. salt. Red precipitate with sodium hydroxide.
Solution hi strong sulphuric acid blue, giving
40905.
brown precipitate on dilution.
Benzopurpurine B (By.) (A.) : E. P. 4846 and 12908 of 1886 ;
Literature.
H
C 7 6 -N 2 -C 10 B (S0 3 H)-NH 2 H D. R. P. 41201, 48074 ; Ber. 1887, 20, 2910, 3160.
Brilliant Purpurine R (A.) (By.) :
C7 H8 -N a -C 10 H 5 (S0 3 H)-NH 2 .
C 7H 6 -N 2 -C 10H 4 (S0 3 H) 2 -NH 2
Prepared by the action of diazotised tolidine
on -naphthylamine-6-sulphonic acid (2 mols.) H
C 7 6 -N 2 -C 10 8 (S0 3 H)-NH 2H .
in presence of alkali. Aqueous solution, orange-

Prepared from tetrazotised tolidine and 1 mol.
red unchanged by sodium hydroxide
; a ; each of j8-naphthylamine-3 6-disulphonic acid :
brownish-red precipitate by dilute sulphuric acid. and naphthionic acid. The red aqueous solution
Dissolves in strong sulphuric acid with a blue
gives a black precipitate with hydrochloric acid,
colour, giving a brown precipitate on dilution. and a red one with sodium hydroxide. The
References as for the next colouring matter. solution in strong sulphuric acid is blue, giving
Benzopurpurine 4 B (By.) (A.) (Lev.) (T. M.) ; a blue-black precipitate on dilution.
Cotton Red 4 B (B.) (K.) (0.) ; Cotton Red BP Literature. E. P. 6687 of 1887 ; D. R. P.
(P.); Sultan Red 4 B (H.) ; Diamine Red 4 B 41095 ; F. P. 160722.
(C.) ; Dianil Red 4 B (M.): Azo- Blue (By.) (A.):
C 7H 8 -N 2 .C 10 H 6 (S0 3 H)-NH 2 H
C 7 6 -N 2 -C 10 H 6 (S0 3 H)-OH
C 7 H i -N,-0 10 H 5 (SO,H)-NH r C 7 6 -N 2 H -C 10H
6 (S0 3 H)-OH.
Prepared by the action of diazotised tolidine Prepared by the action of diazotised tolidine
on naphthionic acid (2 mols.). About twice on a-naphthol-4-sulphonic
the theoretical amount of naphthionic acid is
acid. Aqueous solu-
tion of colouring matter violet, becoming crimson
used, the excess being regained from the filtrate on addition of sodium hydroxide ; restored to
after separating the colour. The alternative violet by dilute sulphuric acid. Dissolves in
method of preparation by oxidising toluene-
strong sulphuric acid with a pure blue colour,
azonaphthionic acid (cp. Congo Red) is not
used technically. Homologous with Congo Red, giving violet precipitate on dilution.
and isomeric with the last. Aqueous solution 35341 F. P. 171133 A. P. 366078.
; ;
orange-red, giving a red precipitate with excess Congo Corinth B (By.) (A.) Dianil Bordeaux ;
of sodium hydroxide ; blue precipitate with
hydrochloric acid ; dissolves in strong sulphuric
acid with a pure blue colour. C 7 H 6 -N 2 -C 10H 5 (S0 3 H)-NH 2
Literature. E. P. 3803 of 1885, 6697 of 1895 ;
D. R. P. 35615, 84893 ; F. P. 167876, 248210 ; C 7H 8 -N 2 -C 10H 8 (S0 3 H)-OH.
A. P. 329632. From diazotised tolidine, naphthionic acid, and
Benzopurpurine 6B
(Lev.) (By.) (A.). Pre- a-naphthol-4-sulphonic acid. Aqueous solution
pared as above from tetrazoditolyl and Laurent's magenta - red,, giving violet precipitate with
a-naphthylamino-5-sulphonic acid. mineral acids. Blue solution in strong sulphuric
Colouring
matter very similar in properties to the pre- acid ; violet precipitate on dilution.
References as above. The same con- Literature. E. P. 15296 of 1885 ; 2213 and
ceding.
stitution is assigned to Diazo Brilliant Black B 6687 of 1886 : D. R. P. 39096 ; A. P. 358865.
(By.), which gives blues or blacks when diazo- Congo Red 4 R :
tised and developed on the fibre. C 7 H 6 -N 2 -C 8 H 3 (OH) 2

Deltapurpurine 5 B (By.) (A.) (K.) ; Diamine
Red B (A.) (By.) (L.): <J 7 H 8 -N 2 -C 10 H 5 (S0 3 H)-NH 2 .
C 7H 6 -N 2 -C 10 H 6 (S0 3H)-NH 2 From diazotised tolidine, resorcinol, and naph-

thionic acid. Aqueous solution brownish-red,
C 7H 9 -N 2 -C 10 H 6 (S0 3 H)-NH 2 . violet precipitate with mineral acids, brown
precipitate with acetic acid. Solution in strong These colouring matters are produced from
sulphuric acid blue, giving violet precipitate on tetrazotised tolidine and 1 mol. each of 8-amino-
dilution. a-naphthol-5-sulphonic acid (S-acid) and a
Literature. E. P. 15296 of 1885; 2213 of naphtholsulphonic acid. Columbia blue G
1886 ; D. R P. 39096. gives a blue solution, which is precipitated with
Brilliant Congo R (A.) (By.) ; Azidine Scarlet hydrochloric acid, and turned reddish-violet
B(C. J.): with sodium hydroxide. Its solution in
strong
C 7 H,-N 2 -C 10 H 4 (S0 3 H) 2 -NH 2 sulphuric acid is greenish-blue,
giving a reddish-
violet precipitate on dilution.
Chicago blue 2 R
C 7 H 6 -N 2 -C 10 H 6 (S0 3 H)-NH 2 .
forms a violet-blue solution, becoming pure blue
with hydrochloric acid, and reddish- violet with
Prom diazotised tolidine, |8-naphthylamine-3 6- :
sodium hydroxide. Its solution in strong sul-
disulphonic acid and -naphthylamine-6-sul-
phuric acid is cornflower blue, giving a blue
phonic acid (Bronner's). Aqueous solution
brownish-red, giving a similarly coloured pre- precipitate on dilution.
Chicago Blue R (A.):
cipitate with mineral acids. Solution becomes
bluer with acetic acid. Orange precipitate with H
C,H 6 -N 2 -C 10 4 (S0 3 H)(OH)-NH 2
sodium hydroxide. Blue solution in strong
sulphuric acid, giving dark-brown precipitate C 7 H 6 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 .
on dilution. Prepared from tetrazotised tolidine and 8-amino-

Literature. E. P. 6687 of 1887 D. R. P. 41095. ; o-naphthol-5-sulphonic acid (2 mols.). The
Azo- Black Blue (0.) Azo- Navy Blue (0.)
; : violet-blue solution gives a dark- violet precipi-
H H
C 7 6 -N 2 -C 6 3 (OH)(NH 2 )-NH-C 6 6 H tate with hydrochloric acid. The solution in
strong sulphuric acid is cornflower blue, giving
C 7 6 -N 2 H -C 10H
3 (S0 3 H) 2 (OH)-NH . a bluish-violet precipitate on dilution. The
Prepared from tetrazotised tolidine and 1 mol. corresponding colour from dianisidine is Chicago
each of m-hydroxydiphenylamine and 8-amino- Blue B (A.).
Literature. A. P. 506284.
o-naphthol-3 : 6-disulphonic acid (H-acid). Solu-
tion in water is brownish- violet and in strong Dianil Blue B (M.):
sulphuric acid blue, giving a bluish-violet pre- C 7 H 8 -N 2 -C 10H 3 (S0 3 H) 2 (OH) 2

Literature. E. P. 10861 of 1891 ; D. R. P. H
C 7 H 6 -N 2 -C 10 3 (S0 3 H) 2 (OH) 2 .
70201 ; A. P. 402415.
Prepared from tetrazotised tolidine and 2 mols.
Azo- Mauve (0.): of 1 8-dihydroxynaphthalene-3 6-disulphonic
: :
H H
C 7 6 -N 2 -C 10 3 (S0 3 H) 2 (OH)-NH 2 acid (chromotrope acid). The blue aqueous
solution is not changed with hydrochloric acid
H
C 7 6 -N 2 -C 10 H 6 -NH 2 . or sodium hydroxide. The solution in strong
Prepared from tetrazotised tolidine and 1 mol. sulphuric acid is deep-blue, becoming bluish-
each of 8-amino--naphthol-3 6-disulphonic :
violet on dilution.
acid (H-acid) and o-naphthylamine. Violet The corresponding colour from benzidine is
aqueous solution gives a violet precipitate with Dianil Blue R,and from dianisidine Dianil Blue G.
hydrochloric acid, and becomes rather bluer with Diamine Blue 3 B (C.) Benzo Blue 3 B (By.)
; ;
dilute acetic acid. Solution in strong sulphuric Congo Blue 3 B (A.) (Lev.) Azidine Blue 3 B ;
acid is blue, becoming violet on dilution. (C. J.) Chlorazol Blue3B(H.); Naphthamine
;
Literature. As above. Blue 3 BX (K.) :
Azidine Wool Blue R (C. J.). C 7H 6 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH 2

C 7H 6 -N 2 -C 10H 6 (S0 3 H)-OH
C 7 H 6 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH 2 .
C 7 H,-N 2 -C 10H 4 (S0 3 H)(OH)-NH 2 .

Prepared from tetrazotised tolidine and 8-aniino-
Prepared from tetrazotised tolidine and 1 mol. o-naphthol-3 :
6-disulphonic acid (H-acid ;
2
each of 8-naphthol-8-sulphonic acid and 8- mols.). The aqueous solution becomes
violet
amino-o-naphthol-5-sulphonic acid. The corre- bluer with hydrochloric acid, and gives a pre-
sponding colour from dianisidine is Azidine cipitate with excess. The solution in strong
Wool Blue B (C. J.). sulphuric acid is blue, giving a violet precipitate
on dilution.
203535, 209269 F. P. 383747 ; A. P. 888036.
;
Literature. E. P. 13443 of 1890; 1742 of
Oxamine Blue 3 R (B.) ; Azidine Blue 3 RN 1891 ; D. R. P. 74593 F. P. 210033.
;
(C. J.) ; Naphthamine Blue 3 RE (K.) : Diamine Blue BX (C. ) Benzo Blue BX (By. ; ) ;
C 7H 6 -N 2 -C 10 H 5 (S0 3 H)-OH Congo Blue BX (A.) (Lev.); Azidine Blue BX

(C. J.); Naphthamine Blue BXR (K.):
C 7 H 6 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 . C 7 H 6 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH 2
Prepared from tetrazotised tolidine and 1 mol.
each of 6-amino-o-naphthol-3-sulphonic acid and C 7 H 6 -N 2 -C 10 H 6 (S0 3 H)-OH.
o-naphthol-4-sulphonic acid. Violet aqueous Prepared from tetrazotised tolidine and 1 mol.
solution is precipitated with hydrochloric acid each of o-naphthol-4-sulphonic. acid and J
or sodium hydroxide. Solution in strong sul- amino-a-naphthol-3 6-disulphonic :acid (H-
phuric acid is blue, giving a violet precipitate acid). The bluish-violet aqueous solution gives
on dilution. a violet precipitate with hydrochloric acid, and
E. P. 2614 of 1893 ; D. R. P.
Literature. becomes bluish-red with sodium hydroxide. The
93276 ; F. P. 227892 ; A. P. 521095. solution in strong sulphuric acid is blue, giving a
Columbia Blue G (A.) Chicago Blue 2 R (A.).
;
violet precipitate on dilution.
Literature. E. P. 1742 of 1891 ; D. R. P. 1 mol. each of 0-naphthol-3 7-disulphonic acid :
74593. and a-naphthol-4-sulphonic acid. The blue

Direct Blue R (I.) :
aqueous solution gives a blue precipitate with
C 7 H 8 -N 3 -C 10 H3(CO a H)(OH) 2 -S0 3 H hydrochloric acid, and becomes reddish-blue
H H
C 7 6 -N 2 -C 10 5 (S0 3 H)-OH. sulphuric acid is blue, giving a blue precipitate
on dilution.
Prepared from tetrazotised tolidine and 1 mol. Literature. As above.
each of 1 7-dihydroxy-6-carboxynaphthalene-
:
Diamine Blue Black E (('.):
3-sulphonic acid and o-naphthol-4-sulphonic
acid. The violet aqueous solution gives a violet C 2 H5 -0-C a H 3 -N 2 -C 10 H 4 (S0 3 H) -OH i!
precipitation with hydrochloric acid, and

becomes violet-red with sodium hydroxide. The H
C 6 H 4 -N 2 -C 10 4 (S0 3 H)(OH)-NH 2 .
solution in strong sulphuric acid is blue. The Prepared as the preceding, except that 7-amino-
corresponding colour from dianisidine is Direct o-naphthol-3-sulphonic acid is used instead of
Blue B (I.). a-naphthol-4-sulphonic acid. The combination
Literature. E. P. 14253 of 1892 ; D. R. P. is effected 'in alkaline solution. The blackish-
75258 ;
F. P. 220468 A. P. 493563, 493564.
; blue aqueous solution gives a blue precipitate
Indazurine BM(Bl.). Isomeric with the with hydrochloric acid, and is not changed with
preceding. A different naphthoic acid, viz. : sodium hydroxide. The solution in strong
7-dihydroxy-2 carboxynaphthalene 4 sul- sulphuric acid is blackish-blue, giving a blue
- - -
1 :
phonic acid is used, the other constituents being precipitate on dilution.

the same. The violet-blue aqueous solution Literature. V. P. 16699 of 1889 ;
D. R. P.
becomes bluer with hydrochloric acid and red 57857.
with sodium hydroxide. The solution in strong DiazurineB(By.):
sulphuric acid is blue, giving a violet precipitate CH 3 -0-C 6 H 3 -N 2 -C 10 H 5 (S0 3 H)-NH 2
on dilution. The corresponding colour from
dianisidine is Indazurine G. M. (Bl.). CH 3 -0-C 6 H 3 -N 2
-C 10 H 5 (S0 3 H)-NH 2 .
Indazurine TS (Bl.): Prepared from tetrazotised dianisidine and a-
H H
C 7 8 -N 2 -C 10 3 (C0 2 H)(OH) 2 -S0 3 H naphthylamine-5-sulphonic acid (Laurent's acid)
(2 mols.). The brownish-red aqueous solution
H H
C 7 8 -N 2 -C 10 4 (S0 3H)(OH)-NH 2 .
gives a blue precipitate with hydrochloric acid
and a soluble red one with sodium hydroxide.
Prepared as the preceding, except that 7-amino- The solution in strong sulphuric acid is blue,
a-naphthol-3-sulphonic acid is used instead of giving a blue precipitate on dilution.
The violet- blue
a-naphthol-4-sulphonic acid. Benzopurpurine 10 B (By.) (Lev.) (K.);
aqueous solution becomes redder with acids or Sultan 10 B (H.). Isomeric with the preceding.
The solution in strong sulphuric acid
Prepared from tetrazotised dianisidine and 2 mols.
alkalis.
is blue, giving a violet precipitate on dilution. The carmine-red aqueous
of naphthionic acid.
Literature. As above. solution gives a blue precipitate with hydro-
Diamine Yellow N (C.): chloric acid and a red one with sodium hydroxide.
H H H
C 2 5 -0 -C 6 3 -N 2 -C 6 3 (C0 2 H) -OH The solution in strong sulphuric acid is blue,
giving a blue precipitate on dilution.
C.H^-C.HÔ-C^. Literature. E. P. 14424 of 1885 ; D. R. P.
Prepared by combining tetrazotised ethoxyben- 38802 ; F. P. 173042 ; A. P. 481954.
zidine first with salicylic acid (1 mol.) and then Azo- Violet (By.):
with phenol (1 mol.) and ethylating the product. OH 3 -0-C 6 H 3 -N 2 -C 10 H 5 (S0 3 H)-NH 2
The yellow aqueous solution gives a greenish
precipitate with hydrochloric acid and a reddish- CH 3 -0-i 6 H 3 -N 2
-C 10 H 5 (S0 3 H)-OH.
yellow with sodium hydroxide. The solution in Tetrazotised dianisidine (1 mol.) is combined
strong sulphuric acid is violet, giving a greenish- with 1 mol. of naphthionic acid, and then with
brown precipitate on dilution.
1 mol. of a-naphthol-4-sulphonic acid. Aqueous
solution reddish-violet, giving blue precipitate
46134 F. P. 186566, 186567 ; A. P. 380067.
;
with mineral acids and bluish-violet coloration
Diamine Blue 3 R(C.): with acetic acid. Solution turned magenta
C 2 H 5 -0-C 8 H 3 -N 2 -C 10 H 6 (S0 3 H)-OH by sodium hydrox de. Dissolves Avith a
blue colour in strong sulphuric acid, giving a
C 8 H 4 -N 2 -C 10H 6 (S0 3 H)-OH. blue precipitate on dilution.
Prepared from tetrazotised ethoxybenzidine and Literature. E. P. 14424 of 1885 ; 7283 of
a-naphthol-4-sulphonio acid (2" mols.). The 1886 ; D. R. P. 40247 ; F. P. 173042 ; A. P.
reddish-blue aqueous solution is not changed
j j WOAO
with hydrochloric acid, but becomes reddish- BenzoazurineG(By.) (A.) (L.) (Lev.) (K.);
violet with sodium hydroxide. The solution in Bengal Blue G (0.); Oxamine Blue
A (B.);
strong sulphuric acid is dark blue, giving a Azidine Blue BA (C. J.):
violet precipitate on dilution. CH 3 -0-C 6 H 3 -N 2 -C 10 H 6 (S0 3 H)-OH
Literature. As above.
Diamine Blue B(C.): CH 3 -0-C 8 H3-N 2 'C 10 H 5 (S0 3 H)-OH.
C 2H 5 -0-C 6 H 3 -N 2 -C 10 H 4 (S0 3 H) 2 -OH Prepared by the action
of tetrazotised dianisi-
dine on a-naphthol-4-sulphonic acid. Aqueous
i 6 H 4 -N 2 -C 10 H 5 (S0 3 H)-OH. solution bluish-violet, becoming red on
addition
dark-violet precipitate
Prepared from tetrazotised ethoxybenzidine and of sodium hydroxide;
with dilute
hydrochloric in acid. Dissolves in strong sulphuric acid is bluish-green, becomi
strong sulphuric acid with a blue colour, giving pure blue on dilution.
violet precipitate on dilution. Benzoazurine R Diamine Sky Blue (C.) ; Benzo Sky Blue (By.)
is a mixture of benzoazurine G and azo blue. Congo Sky Blue (A.); Dianol Sky Blue (Lev.)
Literature. E. P. 14424 of 1885 ; I). R. P. Renol Pure Blue (T. M.) Azidine Sky Bl ;
38802 F. P. 173042
; A. P. 357273.
; (C. J.) ; Chlorazol Blue6G(H.) ; Naphtham
Benzoazurine 3 G (By.) (A.) (L.) (Lev.) (K.). Blue 7 B(K.). Isomeric with the pre<
Jsomeric with the above. a-Naphthol-5-sul- Two mols. of 8-amino-o-naphthol-3 : 6-dis
phonic acid (Laurent's acid) is used instead of phonic acid (H-acid) are used as componen
the 4-sulphonic acid. Aqueous solution bluish- Blue aqueous solution is not changed with hyi
violet, giving bluish-violet precipitate with chloric acid, but becomes redder with sodium
hydrochloric acid and becoming violet-red with j
sodium hydroxide. Solution in strong sulphuric i
is bluish-green, becoming pure blue on dilution.
acid is blue, giving violet precipitate on dilution, j
Literature. As above. 74593 ; F. P. 201770 ; A. P. 464135.
Chlorazol Blue R and 3 G (H.) : Indazurine B (Bl.):
CH 3 -0-C 6 H 3 -N 2 -C 10 H 4C1(SO 3 H)-OH CH 3 -0-C6 H 3 -N 2 -C10 H 4 (S0 3 H) 2 -OH
CH 3 -0-C 6 H 3 -N 2 -C 10 H 4C1(S0 3H)-OH. H
CH 3 -0-C6 3 -N 2 -C 10 4 (S0 3 H)(OH) 2 H .
Prepared from tetrazotised dianisidine and ,

Prepared from tetrazotised dianisidine and 1 mol.
2 mols. of chloro-o-naphthol-4- or 5-sulphonic each of 1 7-dihydroxynaphthalene-4-sulphonic
:
acid. The violet aqueous solution undergoes acid and j8-naphthol-3 :

6-disulphonic acid.
little change with hydrochloric acid, but turns Blue aqueous solution turns bluer with hydro-
crimson with sodium hydroxide. The solution chloric acid and red with sodium hydroxide.
in strong sulphuric acid is greenish-blue (R) or Solution in strong sulphuric acid is blue, giving
green (3 G). a reddish -blue precipitate on dilution.
Literature. -E. P. 12085 of 1898. Literature.!). R. P. 524069.
Diamine Brilliant Blue G (C.) : Brilliant Azurine 5 G (By.):
GH i 0<3iH,-NI 18H,Ca(SO,H) t -OH H
CH 3 -0-C 6 3 -N 2 -C 10 4 (S0 3 H)(OH) 2 H
H
CH 3 -0-C 6 3 -N 2 -C 10 3 C1(S0 3H),-OH.H CH 3 -0-C 8 H 3 -N 2 -C 10 H 4 (S0 3 H)(OH) 2 .
Prepared from tetrazotised dianisidine and 2 Prepared by combining tetrazotised dianisi

mols. of 8-chloro-o-naphthol-3 6-disulphonic : with 2 mols. of 1 8-dihydroxynaphthalene-4-
:
acid. Bluish-violet aqueous solution gives a sulphonic acid in acetic acid solution. Aqueous
soluble violet precipitate with hydrochloric acid, solution is bluish-violet ; with hydrochloric acid
and becomes cherry-red with sodium hydroxide. a blue precipitate, and with sodium
Solution in strong sulphuric acid is greenish-blue, ydroxide becomes red.
fives Solution in strong
turning violet on dilution. sulphuric acid is greenish-blue, giving a dark
Literature. E. P. 1920 of 1894 ; D. R. P. reddish-blue precipitate on dilution.
79055, 82285; F. P. 235271; A. P, 532125, Literature. E. P. 13665 of 1889 ; D. R.
535037. 57166 F. P. 173042 ; A. P. 417294.
;
Oxamine Blue B(B.) = Indazurine BB (BL):

CH 3 -0-C 6 H 3 -N 2 -C 10 H 5 (S0 3 H)-OH CH 3 -0-C& H 3 -N,-C 10 H 3 (C0 2H)(S0 3H)(OH) t
CH 3 -0-C 6 H 3 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH )-C 6 H 3 -N 2 -C 10 H 4 (S0 3 H) 2 -OH.
CH 3 -0-C -(
2.
Prepared from tetrazotised dianisidine and 1 mol. Prepared from tetrazotised dianisidine and 1 m<
each of 5-amino-a-naphthol-3-sulphonic acid and each of 1 7-dihydroxy-2-carboxynaphthalene-
:
a-naphthol-4-sulphonic acid. Dark- blue aque- 4-sulphonic acid and /3-naphthol-3 : 6-disulphonic
ous solution turns reddish-violet with sodium acid (R-salt). Blue aqueous solution becomes
hydroxide, and pale violet with hydrochloric slightly bluer with hydrochloric acid, and redder
acid. The solution in strong sulphuric acid is with sodium hydroxide. Solution in strong
bluish-green, becoming violet on dilution. sulphuric acid is greenish-blue, giving a blue
Literature. E. P. 2370 of 1893; D. R. P. precipitate on dilution.
82572 F. P. 229263
;
A. P. 558344.
;
Chicago Blue 6 B (A.)
l
Benzo Brilliant Blue
;
Indazurine 5 GM(B1.):
6 B (By.) Diamine Sky Blue FF (C.) Azidine
; ; CH,-0-C.H 8 -N,-C 10 H,(CO H)(S0 8H)(OH) 8
Sky Blue FF (C. J.) Chlorazol Sky Blue FF (H.)
; ;
Dianol Brilliant Blue 6 B (Lev.) : CH 3 -0-C 6 H 3 -N 2 -C 10 H 3 (S0 3H) 2 (OH)-NH 2 .
CH 3 -0-C 6 H 3 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH i Prepared as the preceding, except that 8-amino-

o-naphthol-3 : 6-disulphonic acid (H-acid) is
H H
CH 3 -0-C 8 3 'N 2 -C 10 3 (S0 3 H) 2 (OH)-NH 2 . used instead of R-salt. The pure blue aqueous
solution is not changed with hydrochloric acid,
Prepared from tetrazotised dianisidine and 2 but becomes redder with sodium hydroxide.
mols. of 8-amino-o-naphthol-5 7-disulphonic :
acid (S-acid). The combination is effected in The solution in strong sulphuric acid is bluish-
alkaline solution. Blue aqueous solution is not green, becoming bluish-violet on dilution.
Literature. As above.
changed with hydrochloric acid, but becomes
bluish-violet with sodium hydroxide. Solution Hessian Yellow (L.) (A.) (By.) :
CH-C6 H 8 (S0 3H)-N 2 -C6 H 3 (C0 2 H)-OH

1
Chicago Blue 4 B and RW
and Dianol Blue RW
(Lev.) are mixed azo- dyestuffs from dianisidine, S-acid,
and another component. CH-C6 H 3 (S0 3 H)-N 2 -C 6 H 3 (C0 2 H)-OH.
Prepared from tetrazotised diaminostilbenedi- precipitate with mineral acids. Dissolves with
sulphonic acid ' and salicylic acid. Aqueous a reddish-violet colour in strong sulphuric acid,
solution ochreous, giving blackish precipitate giving blue precipitate on dilution.
with mineral acids. Solution reddened by Literature. E. P. 3994 of 1887 ; D. R P.
sodium hydroxide. Reddish-violet solution in 42466 ; Ber. 1894, 27, 3357.
strong sulphuric acid, giving blackish precipitate Hessian Violet (L.) (A.) (By.) :
on dilution. CH-C6 H 3 (S0 3 H)-N 2 -C 10 H 6 -NH 2

E. P. 4387 of 1886; D. R.
Literature. P.
38735 A. P. 350229, 350230.
;
CH-C 6 H 3 (S0 3 H)-N 2 -C 10 H 6 -OH.
Hessian Purple,N4 (L.) (A.) (By.) :
Prepared by combining 1 mol. of tetrazotised

CH-C H (S0 H)-N -C H -NH
6 3 3 2 10 6 2
diaminostilbenedisulphonic acid with 1 mol. of
II
and then with 1 mol. of
CH-C H (S0 H)-N -C H -NH a-naphthylamine, -
6 3 3 a 10 6 2.
naphthol. Aqueous solution reddish-violet, be-
From tetrazotised
diaminostilbenedisulphonic coming bluer with acetic acid, and giving a blue
acid and /3-naphthylamine. Aqueous solution precipitate with mineral acids. Solution in
red, giving bluish-black precipitate with mineral strong sulphuric acid blue, giving a violet pre-
acids, and violet-black precipitate with
acetic
acid. Red
coloration or precipitate with sodium Literature. E. P. 4387 of 1886; D. R. P.
hydroxide. Blue solution in strong sulphuric 38735, 40575.
acid, giving bluish-black precipitate on dilution. Brilliant Hessian Purple (L.) (A.) (By.) :
References as in preceding.
Hessian Purple B CH-C 6 H 3 (S0 3 H)-N 2 -C 10 H 5 (S0 3 H)-NH 2
(L.) (A.) (By.):
CH-C 6 H 3 (S0 3 H)-N 2 -C 10 H 5 (S0 3 H)-NH 2 CH-C6 H 3 (S0 3 H)-N 2 -C 10 H5 (S0 3 H)-NH 2 .
II
CH-C 8 H,(SO,H)-N,-C 10 H 5 (SO,H)-NH 1 . Prepared from tetrazotised diaminostilbenedi-

sulphonic acid, and 2 mols. of /8-naphthylamino-
Prepared by the action of tetrazostilbenedisul-
6-sulphonic acid. Purple- red aqueous solution
phonic acid (1 mol.) on 2 mols. of crude -naph-
gives bluish- black precipitate with hydrochloric
thylamine-5-sulphonic acid (a mixture of the acid and carmine-red precipitate with sodium
2 6- and 2 7- acids). Aqueous solution red,
: :

giving brownish-black precipitate with mineral
acids. Reddish-violet precipitate with sodium blue, giving a bluish-black precipitate on
dilution.
hydroxide. Violet solution in strong sulphuric
acid giving brown precipitate on dilution.
References as for Hessian Yellow.
References as in preceding, and D. R. P.
Stilbene Colouring Matters.
40575.
Hessian Purple D. Isomeric with the pre- The colouring matters which have hitherto
been under this head are produced by
classified
ceding. Prepared from the above tetrazo-disul-
acid and Dahl's alkaline condensation and oxidation of p-nitro
phonic -naphthylamine-5-
sulphonic acid. Aqueous solution orange, giving toluenesulphonic acid under various conditions.
brown precipitate with mineral acids, and They have generally been considered to be
redder with sodium nitroso- or azoxy- stilbene derivatives, but the
becoming hydroxide.
Violet solution in strong sulphuric acid recent researches of A. G. Green and his colla-
becoming
brown on dilution. borators have shown that all the colouring
References as in preceding. matters of this group must be regarded as azo-
Brilliant Yellow (L.) (A.) (By.): dyes (Chem. Soc. Trans. 1904. 85, 1424, 1432 ;
J. Soc. Dyers, 1907, 23, 162). The first action

CH-C 6 H 3 (S0 3 H)-N 2 -C 6 H 4 -OH
of alkali hydroxide on p-nitrotoluenesulphonic
acid leads to the formation of a dinitrosostilbene-
II
CH-C 6 H 3 (S0 3 H)-N a -C 6 H 4 -OH.

From the same disulphonic acid, one molecule of which is oxi-
tetrazo-disulphonic acid and dised at the expense of a second molecule, and the
phenol. Aqueous solution orange, giving violet
remaining two nitrogen atoms of two molecules
precipitate with mineral acids. Dissolves with combine to form an azo- group in a distilbene
a reddish-violet in strong sulphuric acid, giving
molecule :

References as in preceding.
CH-C 6 H 3 (S0 3 H)-NO
2
-
II
Chrysophenine (L.) (A.) (By.) Chrysobarine

G extra cone. (T. M.) ; Phenine Yellow (P.);
;
CH-C H
(S0 3 H)-NO
ft 3
CH-C,H 3 (S0 3 H)-N -N-C 6 H 3 (S0 3 H)-CH
Azidine Yellow CP (C. J.) :
CH-C 6 H 3 (S0 3 H)-N 2 -C 6 H 4 -OH

II
II
CH-C 6 H 3 (S0 3 H)-N0 2 N0 2 -C 6 H 3 (S0 3 H)-CH.

II
CH-C 6 H 3 (S0 3H)-N 2 -C 6 H 4 -0-C 2 H 5 the formation of the The equation represents
.
greenest yellow of the series (stilbene yellow

Prepared by ethylating the preceding colouring 8G see
matter. below). The redder yellows and oranges :
Aqueous solution orange, giving brown be regarded as formed therefrom by the

1
may
Diaminostilbenedisulphonic acid reduction of the two nitro- groups, first to an
OH = CH azoxy- and finally to an azo- group.
SO 3 H S0 3 H Sun Yellow (G.) Afghan Yellow (H.);
;
Curcumine S (L.) Naphthamine Yellow (K.) ;

;
Direct Yellow J (P.); Azidine Fast Yellow G

_ NH 2 (C. J.) ; Direct Yellow RT (Cl. Co.). Prepared
is prepared by boiling p-nitrotoluene-o-sulphonic acid
with sodium hydroxide and
reducing the product with by heating p-nitrotoluenesulphonic acid with
zinc-dust. aqueous sodium hydroxide. Direct yellow RT,
which was analysed by Green (I.e.), is considered Literature. E. P. 18990, 21399, 21553
to have the constitution :
1897; D. R. P. 100613, 113514; F. P. 26946(
CH-C 6 H 3 (S0 3 H)-N=N-C 6 H 3 (S0 3H)-CH 273018.
II II
Mikado Brown B, 3 GO, M (L.). Prepar.
CH-C 6 H 3 (S0 3 H)-N N-C 6 H 3 (S0 3 H)-CH. by the action of alkalis on p-nitrotoluenesu.
phonic acid in presence of oxidisable substances.
O Brown aqueous solution gives a brown pre-
(the colouring matter being, of course, the cipitate with hydrochloric acid. Solution i
sodium salt). strong sulphuric acid is violet- black,

giving
brownish- yellow. brown precipitate on dilution.
Aqueous solution is Solu-
tion in strong sulphuric acid is violet, Literature. E. P. 2664 of 1888; D. R.
becoming
46252, 48528 ; A. P. 395115, 396527.
yellow on dilution.
Literature. E. P. 4387 of 1886 ; D. R. P. Mikado Orange G to 4 R (L.) ; Naphthamine
38735; F. P. 175630; A. P. 360553; Bull. Orange 2 R (K.) ; Direct Orange G (G.). Pre-
Mulhouse, 1887, 99, Ber. 1886, 19, 3234. pared by the same reaction as the preceding,
and by the action of alkaline reducing agents
Naphthamine Yellow G (K.) ; Direct Yellow
R (By.) ; Renol Yellow R (T. M.). Prepared as on direct yellow. Orange- yellow aqueous solu-
tion gives a dark- brown precipitate with hydro-
above, but the temperature of the reaction
60-85. chloric acid, and an orange one with sodium
is Reddish-yellow aqueous solution
gives brown
precipitate with excess of hydro- hydroxide. Solution in strong sulphuric acid
is violet to blue, giving a brown
chloric acid and a yellow precipitate with precipitate on
sodium hydroxide. Solution in strong sulphuric dilution.
acid is cherry- red, becoming yellow on dilution. Mikado Orange 3 RO (L.) has the constitution :
Literature. E. P. 23672 of 1892 ; D. R. P. CH-C 6 H 3 (S0 3 H)-N N-C 6 H 3 (S0 3 H)-CH

:
79241; F. P. 226635; Ber. 1893, 26, 2233; II
CH-C 6 H 3 (S0 3 H)-N N-C 8 H 3 (SO 3H)-CH.

II
1895, 28, 2281. :
Mikado Yellow (L.) Milkado Gold Yellow 2 G,

; Brands 4 RO and 5 RO are redder shades.
4 G, 6 G, 8 G (L.) Naphthamine Yellow 2 G, 3
; Literature. E. P. 2664 of 1888 ; D. R. P.
G (L.). Prepared by treating the products of 46252, 48528, 46929; F. P. 189697; A. P.
condensation of p-nitrotoluenesulphonic acid 395115, 396527 ; Ber. 1893, 26, 2233 ; 1895, 28,
and sodium hydroxide with oxidising agents. 2281.
Yellow aqueous solution gives a brownish-yellow Polychromine R (G.) Fast Cotton Brown R
;
precipitate with hydrochloric acid, and yellow (G.); Direct Brown R (G.). Prepared by
solution or precipitate with sodium hydroxide. boiling equal molecules of p-nitrotoluenesul-
Solution in strong sulphuric acid is orange to phonic acid and p-phenylenediamine with
red, becoming yellow on dilution. sodium hydroxide. Orange - brown aqueous
solution gives a blue-black precipitate with
42466: F. P. 226635; Ber. 1893, 26, 2234; hydrochloric acid. Solution in strong sulphuric
1897, 30, 2618, 3097 ; 1898, 31, 354, 1078. acid is reddish-violet, giving a bluish - black
Stilbene Yellow G, 4 G, 6 G, 8 G (Cl. Co.). precipitate on dilution.
The constitution of the last brand has already Literature. E. P. 15671 of 1890 ; D. R. P.
been given. The colouring matters are alkaline 59290 F. P. 208626 ; A. P. 455952.
;
condensation products of dinitrodibenzyldisul- Diphenyl Orange RR (G.) ; Azidine Orange D

phonic acid, and dinitrostilbenedisulphonic acid. 2 R (C. J.). Prepared by condensing 2 mols. of
Solution in strong sulphuric acid is orange to p-nitrotoluenesulphonic acid with 2 mols. of
yellowish-red, becoming yellow on dilution. p-phenylenediamine in presence of concentrated
Literature. E. P. 5351, 21553. 21399, of aqueous sodium hydroxide. Orange - yellow
1897 3393 of 1898 ; D. R. P. 113513, 113514 ;
; aqueous solution gives a bluish-black precipitate
F. P. 272384, 273018, 273037; Ber. 1897, 30, with hydrochloric acid, and an orange one with
3097 1898, 31, 1078.
; sodium hydroxide. Solution in strong sulphuric
Diphenylcitronine G (G.). Prepared by con-
acid is red. giving a bluish-black precipitate on
densing dinitrodibenzyldisulphonic acid with dilution.

aniline in presence of sodium hydroxide or by Literature. E. P. 6651 of 1899; D. R. P.
condensing similarly dinitrostilbenedisulphonic appl. G 13069 ; F. P. 286620 ; A. P. 636065.
acid. Yellow aqueous solution gives a brownish- Chicago Orange RR
(G.). Prepared by con-
yellow precipitate with hydrochloric acid, and densing p-nitrotoluenesulphonic acid with benzi-
an orange- yellow one with sodium hydroxide. dine in presence of sodium hydroxide. Orange-
. Solution in strong sulphuric acid is orange, giving yellow aqueous solution gives a brown precipi-
a brownish-yellow precipitate on dilution. tate with hydrochloric acid, and an orange- brown
Literature. E. P. 18990, 21399, 21553 of one with sodium hydroxide. Solution in strong
1897 ; D. R. P. 101760, 113514; F. P. 269466. sulphuric acid is violet, giving a brown pre-
273018; A. P. 613911. cipitate on dilution.
Diphenyl Fast Yellow (G.). Prepared by Literature. E. P. 788 of 1893 ; D. R. P.
condensing dinitrodibenzyldisulphonic acid or 75326 ; F. P. 227271.
dinitrostilbenedisulphonic acid with primuline Arnica Yellow (G.). Prepared by condensing
or dehydrothio-p-toluidinesulphonic acid in p-nitrotoluenesulphonic acid with p-amino-
presence of sodium hydroxide. Yellow aqueous phenol in presence of boiling aqueous sodium
solution gives a brownish-orange yellow precipi- hydroxide. Brownish-yellow aqueous solution
tate with hydrochloric acid, and an orange- gives a brownish- black precipitate with hydro-
yellow one with sodium hydroxide. Solution chloric acid. Solution in strong sulphuric acid
in strong sulphuric acid is red, giving a brownish- is violet, giving a dark-brown precipitate on
yellow precipitate on dilution. dilution.

Literature. F. P. 222554. Janus Brown R (M.) is prepared from diazo-

Diphenyl Chrysoine G (G.). Prepared by tised p-aminobenzyldiethylamine and a-naph-
ethylating the preceding. Golden-yellow aque- thylamine, the product being diazotised and
ous solution gives a blackish- brown precipitate combined with chrysoi'dine, resorcinol, or ra-
with hydrochloric acid, and an orange one with phenylenediamine. Reactions are similar to
sodium hydroxide. Solution in strong sulphuric those given by the preceding colour.
acid is violet - red, giving a blackish-brown Literature. E,. P. 19976 of 1896 ; D. R. P.
precipitate on dilution. 99127 ; F. P. 256156 ; A. P. 610345.

Literature.E. P. 6651 of 1899; D. R. P. Melogene Blue BH (K. S.) ; Diamine Beta
(appl. G.) 13069; F. P. 286620; A. P. 636065. Black (C.) :
Diphenyl Chrysolne RR (G.). Prepared by

diazotising the condensation product of dini-
N </C H -N -C 10 H (S0 3 H) (OH)-NH 2
8 s a 3 2
trodibenzyldisulphonic acid and aniline in ^C 12 H -N -C 10 H 3 (S0 3 H) (OH)-NH

3
Tetrazotised benzidine is combined with 1 mol.
2 2 2.
alkaline combining
solution, the diazo- com-
of p-xylidine, the product diazotised and com-
pound with phenol and ethylating the product. bined with 2 mols. of 8-amino-a-naphthol-3 6-
Reddish orange aqueous solution gives a
- :
blackish-brown precipitate with hydrochloric disulphonic acid (H-acid). The violet-blue

acid, and a reddish - brown one with sodium
aqueous solution gives a violet precipitate with
hydrochloric acid, and becomes violet with
hydroxide. Solution in strong sulphuric acid sodium hydroxide. The solution in strong
is pure blue, giving a brownish-black precipitate
on dilution. sulphuric acid is blue, giving a bluish-violet
Literature.E. P. 6651 of 1899; D. R. P. precipitate on dilution.
-E. P. 28810 of 1896;
Literature. F. P.
117729 ; F. P. 286620 A. P. 644462.
;
262109 A. P. 691616.
Diphenyl Fast Brown G (G.). Prepared as
;
Direct Black V and RR (P.) are analogous

the preceding, but the diazo- compound is com-
colours derived from benzidine, 8-amino-a-
bined with 7-phenylamine-a-naphthol-3-sul-
naphtholsulphonic acid, a primary amine, and a
phonic acid. The dark yellowish-brown aque- m-diamine.
t
ous solution gives a blackish-brown precipitate
with hydrochloric acid, and a dark- brown one
Benzo Gray (By.):
with sodium hydroxide. Solution in strong N ^C
10 H 6 -N 2 -C 10 H 5 (S0 3 H)-OH
sulphuric acid is dark blue, giving a blackish- \C, 2 H 8 -N 2 -C 6 H 3 (C0 2 H)-OH.

brown precipitate on dilution. The colouring matter from tetrazotised benzidine
References as above. and 1 mol. each of salicylic acid and o-naphthyl-
Diphenyl Catechine G (G.). Prepared as amine is diazotised and combined with a-naph-
above, but the diazo- compound is combined thol-4-sulphonic acid. The Bordeaux- brown
with 7 dimethylamino a naphthol-3-sulphonic
- - -
aqueous solution gives a black precipitate with
Yellowish- brown aqueous solution gives
hydrochloric acid. The solution in strong sul-
acid.
a dark-brown precipitate with hydrochloric acid,
phuric acid is blue, giving a black precipitate on
and a brown one with sodium hydroxide. dilution.
Solution in strong sulphuric acid is blackish Literature. E. P. 13235 of 1890 ; D. R. P.
violet- blue, giving a blackish-brown precipitate 57331 F. P. 187365.
;
on dilution. Benzo Olive (By.) :
References as above. H -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH a
Curcuphenine (Cl. Co.). Prepared by con- N ^C
^C
10
H
6
-N 2 -C 6 H 3(C0 2 H)-OH.
12
densing p-nitrotoluenesulphonic acid with de- 8
hydrothio-p-toluidinesulphonic acid in presence Prepared as the preceding, except that 8-amino-

of very dilute aqueous sodium hydroxide. a-naphthol-3 :
6-disulphonic acid (H-acid) is
Yellow aqueous solution gives a brown precipi- used as the end component. The dark moss-
tate with hydrochloric acid. The solution in green aqueous solution gives a blackish-grey
strong sulphuric acid is red, giving a brownish- precipitate with hydrochloric acid, and becomes
yellow precipitate on dilution. dark brown with sodium hydroxide. Solution
Literature. E. P. 12922 of 1896 ; D. R. P. in strong sulphuric acid is violet, giving a
99575 ; F. P. 264755. greenish- black precipitate on dilution.
E. P. 3439 of 1891 ; D. R. P.
Chlorophenine Orange RR and RO (Cl. Co.) Literature.
are reduction products of the preceding. 65480 ; F. P. 187365.
IV. TRISAZO- COLOURING MATTERS. 1 Congo Fast Blue R (A.):
These colours, as their name implies, contain N ^C
10 H 6 -N 2 -C 10 4 (S0 3 H) 2 -OH H
three azo- groups. \C
14 H 12 -N 2 -C 10 H 4 (S0 3 H) 2 -OH.
Janus Brown B (M.) :
Tolidine is' tetrazotised and combined with
1 mol. of a-naphthylamine, the product diazo-
Prepared by combining diazotised m-amino- tised and combined with 2 mols. of o-naphthol-
phenyltrimethylammonium chloride with a- 3 8-disulphonic acid (e-acid).
:
The blue aque-
naphthylamine, diazotising the product and ous solution is precipitated with acids or alkalis.
combining with chrysoi'dine. Aqueous solution The solution in strong sulphuric acid is blue,
is brown,
giving a soluble brown precipitate with giving a blue precipitate on dilution.
'
hydrochloric acid or sodium hydroxide. Solu- Literature. E. P. 6932 of 1890; D. R. P.

tion in strong sulphuric acid is dark
green, be- 60921.
coming brown on dilution. Benzo Black Blue R (By.) :
Literature. E. P. 9343 of 1896; D. R. P. -N 2 -C ]0 H 5 (S0 3 H)-OH

H
95530.. K ^C
w 10 6
'
Chrome patent green A (K.), which belongs to
2
\C 14 H, 2 -N 2
-C IO H 5 (S0 8 H)-OH.
this series, is no longer in commerce. Tolidine is tetrazotised and combined with
1 mol. of
a-naphthylamine and the intermediate 7-amino-o-naphthol-3-sulphonic acid (7-acid)
product diazotised and combined with 2 mols. used instead of Cleve's acid. Blue-black aqueo
of a-naphthol-4-sulphonic acid. Bluish-violet solution gives a black-violet precipitate with
aqueous solution gives a violet precipitate with hydrochloric acid, and a red-violet one witli
hydrochloric acid. Solution in strong sulphuric sodium hydroxide. Solution in strong sulphuric
acid is blue, giving a bluish-violet precipitate on acid is greenish -blue, giving a violet-black pre-
dilution. cipitate on dilution.
E. P. 16484 of 1887; F.
Literature. P. Literature. A.. P. 526763.
187365 A. P. 440639.
; Isodiphenyl Black (G.):
Benzo Indigo Blue (By.) :
H
-C 10 6 -N 2 -C 10 4 (S0 3 H)(OH) 2 H N
N,
-C, 4 H t 2 -N 2 -C 10 H 4 (S0 8 H)(OH) 8 .
Prepared as Columbia black FB, except that
The same intermediate tetrazo- compound as is used instead of Cleve s acid.
resorcinol Violet-
;
above is combined with 2 mols. of 1 8-dihydroxy- :

black aqueous solution gives a black precipitate
naphthalene-4-sulphonic acid (S-acid). The with acids or alkalis. Solution in strong sul-
violet aqueous solution gives a bluish-violet pre-
phuric acid is blackish-blue, giving a black
cipitate with hydrochloric acid, and becomes precipitate on dilution.
reddish-violet with sodium hydroxide. Solution Literature. E. P. 20278 of F. P.
1897;
in strong sulphuric acid is greenish-blue, giving 270151 ; A. P. 615497.
a violet- blue precipitate on dilution. Direct Black V (K. S.) :
E. P. 3397 of 1890; D. R. P.
Literature.
57912 F. P. 200520 A. P. 501118. N ^C 10 H 3 (S0 3H) 2 (OH)-N 2 -C 10 H 8 -NH 8
;
Congo Fast Blue B (A.)

:
:
2
^C ]2 H 3
-N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 .
N /-C 10 H-N 2 -C 10 H 4 (S0 3 H) 2 -OH 7-Amino-a-naphthol-3 6-disulphonic acid (2

:
6
acid) is diazotised and combined with 1 mol.
\C, 4 H 12 2 -N 2 -C IO H 4 (S0 3 H) 2 -OH.
Dianisidine is tetrazotised and combined with a-naphthylamine in acid solution. The monc
azo- dyestuff is then dissolved by adding sodiur
1 mol. of a-naphthylamine and the intermediate
hydroxide and tetrazotised benzidine added, the
product diazotised and combined with 2 mols. combination being effected in presence of sodiur
of a-naphthol-3 8 disulphonic acid (e-acid). carbonate. To this intermediate product is the
:
Blue aqueous solution gives a blue precipitate added 1 mol. of 7-amino-a-naphthol-3-sulphonic

with acids or alkalis. Solution in strong sul- acid (7-acid). Violet- black aqueous solution
phuric acid is cornflower blue, giving a blue
gives a blue-black precipitate with hydrochloric
precipitate on dilution. acid, and becomes reddish- violet with sodium
Literature. E. P. 6932 of 1890; D. R. P.57444.
hydroxide. Solution in strong sulphuric acid is
Columbia Black FB and FF extra (A.):
blue, giving a blue-black precipitate on dilution.
Azidine Black FF (C. J.) Titan Blacks (H.) ; :
literature.. P. 15294 of 1896 ; D. R. P.
X.
-C 6 H 4 -N 2 -C 10 5 (S0 3 H)-NH 2 H 109161 ; F. P. 256950 ; A. P. 601033.
^C H 10 4 (S0 3 H)(OH)-N 2 -C G H 3 (NH 2 ) 2 . Direct Indone Blue R (K. S.) :
p-Aminoacetanilide is diazotised and combined N /-C 10 H 3 (S0 3 H) 2 (OH)-N 2 -C to H 6 -NH 2
with 7-amino-a-naphthol-3-sulphonic acid (7- ^C 12 H 8 -N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH 2 .
acid), the product saponified with sodium hydro-

Prepared as the preceding, except that 8-aminc
xide, the resulting diamino -compound tetrazo-
a-naphthol-3 6-disulphonic acid (H-acid)
:
tised and combined first with 1 mol. of o-naph- used as the end-component. Blue-black aque
thylamine-6- (or 7)-sulphonic acid (Cleve's acids) ous solution gives a dark-blue precipitate with
and then with 1 mol. of wi-phenylenediamine.
hydrochloric acid, and becomes violet with
The aqueous solution is violet-black, and is
precipitated by acids or alkalis. Solution in acid is blue, giving a dark- blue precipitate on
strong sulphuric acid is blue, giving a precipitate dilution.
on dilution.
References as above.
Diamine Bronze G (C.):
131986, 131987 ; A. P. 679221.
Direct Black BMP (P.) has the same or a very ^C H
(S0 3 H) 2 (OH)-N 2 -C 6 H 3 (NH 2 ) 2
10 3
similar constitution, and dyestuffs belonging to 2 ^M^ H

8 -N 2 -C 6
H 3 (C0 2 H) -OH.
the same cliss are Carbon Blacks AW, CW, The dyestuff from tetrazotised benzidine and
CDW, Naphthamine Direct Blacks FF, B, FG 1 mol. each of salicylic acid and 8-amino-a-
and 6S (K.) and Dianol Blacks FF and FB (Lev.). naphthol-3 :
6-disulphonic acid (H-acid) is diazo-
Titan Black J (H.): tisedand combined with 1 mol. of m-phenylene-
^-No-C^H^SOjHJ-NHa diamine. The chocolate-brown aqueous solu-
4 (S"0 3 H)(OH)-N 2 -C 6 H 3 (NH 2 ) 2
: .
tion gives a purple-brown precipitate with hydro-
chloric acid, and becomes yellower with sodium
ja-Aminoacetanilide is diazotised and combined
with acid hydroxide. Solution in strong sulphuric acid
6-amino-a-naphthol-3-sulphonic (J- is bluish- violet, giving a black precipitate on
acid), theproduct saponified, tetrazotised, and dilution.
combined with 1 mol. each of a-naphthylamine-
6-(or 7)-sulphonic acid (Cleve's acids) and m-
75762 ; F. P. 201770.
phenylenediamine.
Trisulphone Browns B, G and 2 G (K. S.).
Oxydiamine Black N(G): These are constituted similarly to the preceding,
N ^C 6 H
4 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2 except that a non-specified diamine is used and
^C 10H 4 (S0 3 H)(OH)-N 2 -C 6 H 3 (NH 2 ),. 7-amino-a-naphthol-3 :
6-disulphonic acid (2
Prepared like Columbia black FB, except that acid) is employed instead of H-acid. (The
diamines used arc probably bcnzidine, tolidino, Benzidine is tetrazotised and combined with
and dianisidine.) Mark B gives a brown solu- 1 mol. of salicylic acid, and the intermediate
tion in water, which yields a blackish-brown product is combined in alkaline solution with
precipitate with hydrochloric acid, and becomes the product of the action of diazotised sul-
red with sodium hydroxide. The solution in phanilic acid on 8-aniiuo-a-naphthol-5-sulphonic
strong sulphuric acid is bluish-violet, giving a acid (S-acid) in acid solution. The green
dark- brown precipitate on dilution. aqueous solution gives a green precipitate with
Literature. E. P. 5746 of 1898 ; D. R. P. hydrochloric acid, and becomes greenish-black
114638 ; F. P. 275733 ; A. P. 608024. with sodium hydroxide. The solution in strong
Chlorazol Deep Brown B (H.) : sulphuric acid is blue- violet,
giving a green pre-
^C H (S0 H) (OH)-N -C H
10 3 3 2 2 7 5 (NH 2 )2 cipitate on dilution.
^C 12 H -N -C H (C0 H)-OH. Diamine Green B (G.); Dianol Green B
8 2 6 3 2
(Lev.); Renol Green B (T. M.); Direct Green
Benzidine is tetrazotised and combined with BN Azidine Green 2 B
(P.) ; (C. J.) :
1 mol. each of salicylic acid and 7-amino-o-naph-

thol-3 6-disulphonic acid (2 R-acid), the pro-
:
N 2 -C 12 H 8 -N 2 -C 6 H 4 -OH
duct being diazotised and combined with m-
C 10 H,(S0 3H) 2 (OH)-NH 2
tolylenediamine.
Columbia Black R (A.) :
H
l!r 2 -C 6 -N0 2
^C 10H (S0 3H) (OH)-N
3 2 2 -C 7 H (NH
6 2)2
4 .
^C Prepared in a similar manner as the preceding.

14 H 12 -N -C H (NH
2 7 5 2 ) 2.
Tetrazotised benzidine is combined with 1 mol.
Tolidine is tetrazotised and combined with 1 mol.
of phenol and the product is combined with the
each of
7-amino-a-naphthol-3 6-disulphonic :
azo- colour from diazotised p-nitroanilino and
acid (2 R-acid) and m-tolylenediamine, and the
8-amino-o-naphthol-3 6-disulphonic acid (H- :
product is diazotised and combined with m- acid). Dull-green aqueous solution gives a
tolylenediamine. Brown-black aqueous solu- bluish-black precipitate with hydrochloric acid,
tion gives a mack precipitate with hydrochloric
and becomes yellower with sodium hydroxide.
acid, and becomes brown with sodium hy- Solution in strong sulphuric acid is violet, giving
droxide. Solution in strong sulphuric acid is pure a black precipitate on dilution.
blue, giving a violet-black precipitate on dilution. Literature. E. P. 15725 of 1891 ; D. R. P.
66351 ; F. P. 201770 ; A. P. 514599.
108215.
Diamine Green G (C.); Chlorazol Green G
Columbia Black B (A.) ; Titan Black ill.).
M (H.); Dianol Green G (Lev.); Azidine Green
Prepared as the preceding, except that diani- 2 G (C. J.). Prepared as the preceding, except
sidine is used instead of benzidine. The violet- that salicylic acid is used instead of phenol.
black aqueous solution gives a dark flocculcnt
Reactions and literature as above.
precipitate with hydrochloric acid, and becomes
reddish- violet with sodium hydroxide.
Diphenyl Green G (G.). Prepared like
Solution diamine green B (above), except that o-chloro-
in strong sulphuric acid is blue-black, giving a p-nitroaniline is used instead of p-nitroanilinc.
violet- black precipitate on dilution.
The reactions are also similar to those given by
this colour.
111744. A. P. 710693.
Literature.
Columbia Blacks 2 BX and 2 BW (A.) belong Diphenyl Green 3 G (G.). Prepared like
to the same class.
diamine green G, o-chloro-p-nitroaniline being
Benzo Black Blue G (By.) :
used instead of p-nitroaniline. The green
-C 10 H e -N 2 -C 10 5 (S0 3 H)-OH H aqueous solution gives a green precipitate with
N,
12\C H
6 (S0 3 H) 2 -N.2 -C 10 5 (S0 3 H)-OH.
H hydrochloric acid, and becomes duller with
Benzidinedisulphonic acid is tetrazotised and
combined with 1 mol. of o-naphthylamine, the acid is reddish-violet, giving a green precipitate
product diazotised and combined with 2 mols. on dilution.
of a-naphthol-4-sulphonic acid. The blue-black Reference as the preceding.
aqueous solution gives a black-blue precipitate Chloramine Green B (K. S.). Benzidine is
with hydrochloric acid, and becomes blue with tetrazotised and combined with 1 mol. of either
com-
.sodium hydroxide. The solution in strong phenol or salicylic acid, and the product
sulphuric acid is blackish-green, giving a blackish- bined in alkaline solution with the azo- colour
blue precipitate on dilution. from diazotised dichloroaniline and 8-amino-a-
Literature. E. P. 16484 of 1887. naphthol-3 6-disulphonic acid (H-acid) (com-
:
Benzo Black Blue 5 G (By.). As the pre- bined in acid solution). The green aqueous
ceding, except that 1 : 8-dihydroxynaphthalene- solution gives a violet-black precipitate with
4-sulphonic acid is used instead of a-naphthol- hydrochloric acid, and becomes black-green
4-sulphonic acid. The blackish-blue aqueous with sodium hydroxide. Solution in strong
a violet-black
solution gives a dark greenish-blue precipitate sulphuric acid is violet, giving
with hydrochloric acid. The solution in strong precipitate on dilution.
sulphuric acid is black-green, giving a dark
greenish-blue precipitate on dilution.
112820 ; F. P. 287971 ; A. P. 627679.
Columbia Green (A.) ; Direct Green CO (L.) : Chloramine Blue (K. S.): HW
N 2 -C 12 H 8 -N a -C 6 H 3 (C0 2 H)-OH 2 -C 12 H 8
N -N a -C 10 H 4 (S0 3H)(OH)-NH,
C 1U H 3 (S0 8 H)(OH)-NH 2 C 10H 2 (S0 3H) 2 (OH)-NH 2
N,-C 8 H 4 -S0 3 H. N 2
-C 6 H 3 C1 2
.
Prepared as the preceding, except that 8-amino- N 2 -C 12 H 8 -N 2 -C 8 H 3 (CO,H)-OH

a-naphthol-5-sulphonic acid (S-acid) is used
instead of phenol or salicylic acid. C 8 H,(OH) 2
Chloramine Blue 3 G (K. S.):
N 2 -C 12 H 8
-N 2 -C 10 H 3 (S0 3 H) 2 (OH)-NH 2
N 2 -C 10 8 -S0 3H. H
Prepared as the preceding, except that a-naph-
H 2 (S0 3 H) 2 (OH)-NH 2 thylamine-5-sulphonic acid (Laurent's acid) i
used instead of sulphanilic acid. Reactions ant
N 2 -C 8 H 3 C1 2 .
references as the preceding.
Azo Corinth (O.):
Tetrazotised benzidine 1 mol. is combined with
of 8-amino-o-naphthol-3 6-disulphonic acid (H- :
N 2 -C 14 H 12 -N 2 -C 6 H 2 (S0 3 H)(OH)-NH 2
acid) and then with 1 mol. of H-acid to which
has been added 1 mol. of diazotised dichloro- C 8 H 2 (OH) 2
aniline in acid solution.
References for the last two colours as for N 2 -C 10
H 8 -S0 3 H.
chloramine green B. Tetrazotised tolidine is combined with 1 me
Diamine Black (('.); HW
Ingrain Black G of 3-aminophenol-6-sulphonic acid (acid III.)
(II.); Naphthamine Black H (K.): and 1 mol. of resorcinol, and the colouring matter
so obtained is treated with 1 mol. of diazotised
N 2 -C 12H 8 -N 2 -C 10 H 4 (S0 3 H)(OH)-NH 2
naphthionic acid. Reddish-brown aqueous solu-
tion gives a reddish- brown precipitate with
C 10H 2 (S0 3 H) 2 (OH)-NH 2
hydrochloric acid, and is turned bluish-red wit
]JT 2 -C 8 H 4 -N0 2 .
acid is bluish-violet, giving a reddish-bro\
Prepared like B (above), except
diamine green precipitate on dilution.
that 7-amino-a-naphthol-3-sulphonic acid (7- Literature. E. P. 13402 of 1893 ; D. R.
acid) is used instead of phenol. Blackish-blue 71182; A. P. 516381.
aqueous solution gives a blue precipitate with
hydrochloric acid. Solution in strong sulphuric V. TBTRAKISAZO- COLOURING MATTERS.
acid is blue, giving a blue precipitate on dilution. These contain four azo- groups.
Benzo Brown G (By.):
66351,70399; F. P. 201770 ; A. P. 514599.
2 -C 8 H 2 (NH 2 ) 2 -N 2 -C 8 H 4 -S0 3 H
Dianil Black R(M.): u 4 ^N
\N
H 2 -C 8 H 2 (NH 2 ) 2 -N 2 -C 8 H 4 -S0 3 H.
N 2 -C 12 H 8 -N 2 -C 8 3 (NH 2 )2
Prepared by the action of diazotised sulphanil

C 10 H 2 (S0 3H) 2 (OH) 2 acid (2 mols.) on Bismarck brown (1 mol.)
Reddish-brown aqueous solution gives a bro\
N 2 -C 10
H 8 -S0 3 H. precipitate with acids and alkalis. Solution
combined with 1 mol. strong sulphuric acid is violet-brown, giving

Tetrazotised benzidine is
brown on
dilution.
and then with 1 mol. of precipitate
of wi-phenylenediamine E. P. 16493 of
Literature. 1887 D. R.
1:8- dihydroxynaphthalene-3 : 6 disulphonic
-
46804 A. P. 384315.
;
;
acid (chromotrope acid), to which has been added

Benzo Brown B (By.) :
1 mol. of diazotised naphthionic acid. The

reddish-violet aqueous solution gives a precipi- ^N 2 -C 8 H (NH2 2)2 -N 2 -C 10 H 8 -S0 3
H
tate with hydrochloric acid, and becomes blue
6 4
^N 2 -C 6 H (NH2 2)2 -N 2 -C 10 H 6 -S0 3 H.
with sodium hydroxide. Solution in strong Prepared as the preceding, except that naj
sulphuric acid is dark blue, giving a reddish- thionic acid is used instead of sulphanilic ack
violet precipitate on dilution. Reactions and references as above.
Literature. D. R. P. 89285. Toluylene Brown R (0.) (By.); Azid
Congo Brown G (A.); Naphthamine Brown BrownT2R(C. J.):
4G H (NH H -S0 3 H
TTSO 3 P 'K 5^-N a
(K.) :
-C 8 2 2)2 -N 2 -C 10 6
N 2 -C 12 H 8 -N 2 -C 8 H 3 (C0 2 H)-OH ^-N 2 -C 6 H.2 (NH 2 )2 -N 2 -C 10 H 8 -S0 3 H.
Prepared by treating the colour from tetrazc
3,H,(OH), tised 2 :
6-tolylenediamine-4-sulphonic acid an
2 mols. of m-phenylenediamine with 2 mols.
C 6 H 4 -S0 3 H. diazotised naphthionic acid. Brown aqueoi
The dyestuff from tetrazotised benzidine, solution gives a brown precipitate with hyd
salicylic acid and resorcinol is treated with chloric acid. Solution in strong sulphuric ack
diazotised sulphanilic acid or the intermediate isdull reddish-violet.
product from tetrazotised benzidine and 1 mol. Literature. E. P. 11000 of 1889; D. R.
of salicylic acid is combined with 1 mol. of 58657 ; A. P. 465116.
resorcinol to which 1 mol. of diazotised sulphan- Hessian Brown BB (L. ) :
ilic acid has been added. The red aqueous /N 2 -C 6 H 2 (OH) 2 -N 2 -C 8 H 4 -S0 3 H
solution gives a brown precipitate with hydro-
chloric acid. Solution in strong sulphuric acid
is reddish- violet, giving a reddish- brown pre- Prepared by the action of tetrazotised benzidine
cipitate on dilution. on 2 mols. of the monoazo- dyestuff from diazo-
Literature. E. P. 10653 of 1888 ; D. R. P. tised sulphanilic acid and resorcinol. Aqueous
46328, 46501 ; F. P. 192331 ; A. P. 399581. solution is brown, giving a brown precipitate
CongoBrownR(A.) : with hydrochloric acid, and becoming red with
AZOXYBENZENE. 397
sodium hydroxide. Solution in strong sulphuric AZOPHENYLENE v. AZINES.
acid is violet-black, giving a brown precipitate AZOPHOR -BLACK, -BLUE, -RED, -ROSE v.
on dilution. AZO- COLOURING MATTERS.
Hessian Brown MM (L.). Prepared as the AZOPHOSPHINES v. Azo- COLOURING
preceding, tolidine being used instead of benzi- MATTERS.
dine. AZO-REDS, AZORUBINES v. Azo- COLOURING
Reactions as above. MATTERS.
Mekong Yellow G (D. H.) : AZOTE. A name given to nitrogen by
C 8 H 4 -N 2 -C 6 H 3 (C0 2 H)-OH Lavoisier, and hence commonly used in French
literature to designate that element.
C 6 H 4 -N 2 -C 6 H 3 (OH AZOTINE. An explosive made in Austria-
Hungary (J. Soc. Chem. Ind. 4, 366).
AZOTOL v. Azo- COLOURING MATTERS.
C 6 H 4 -N 2 -C 6 H 3 (C0 2 H)-OH. AZOTOMETER. A term applied by W. Knop
toan apparatus designed to measure the nitrogen
Tetrazotised benzidine (2 mols.) is combined
evolved by the action of sodium hypochlorite or
with salicylic acid (2 mols.) and the intermediate
hypobromite on ammonium salts and certain
product is combined with dihydroxydiphenylme-
thane (1 mol.). Yellowish- brown aqueous solu- organic substances.
tion gives a brown precipitate with hydrochloric
AZO- TURKEY RED v. Azo- COLOURING
MATTERS.
acid, and becomes reddish-brown with sodium
AZO-VIOLET v. Azo- COLOURING MATTERS.
l^droxide. Solution in strong sulphuric acid AZOXINE COLOURING
is violet, giving a brown precipitate on dilution.
MATTERS v.

OXAZINE COLOURING MATTERS.
AZOXYBENZENE C 12 H 10 N 2 0. A product
80816; F. P. 228593 A. P. 519523. ;
of the partial reduction of nitrobenzene with
Mekong Yellow R (D. H.). Prepared as the alcoholic potash (Zinin, J. pr. Chem. 36, 93 ;
preceding, but tolidine is used instead of benzi- Schmidt and Schultz, Annalen, 207, 325 ; Ber.
dine.
12, 484); or with sodium amalgam containing
Reactions and literature as above.
3-8 p.c. of sodium (Alexejeff, J. 1864, 525;
Cuba Black (Petersen) ; Dianil Black (M.) :
Moltschanowsky, Ber. 15, 1575).

Preparation. Azoxybenzene is best prepared
by dissolving 1 part of sodium in 25 parts of
Benzidinesulphonic acid is tetrazotised and com- methyl alcohol, adding 3 parts of nitrobenzene
bined with 2 mols. of 7-amino-a-naphthol-3- and heating for 5 or 6 hours on a water-bath in
sulphonic acid (y-acid) in alkaline solution, and a flask provided with a reversed condenser. The
the product is tetrazotised and combined with
methyl alcohol is then distilled off and the residue
2 mols. of m-phenylenediamine. Black aqueous treated with water, which dissolves the sodium
solution is precipitated with hydrochloric acid formate formed in the reaction, and leaves the
or sodium hydroxide. Solution in strong
azoxy benzene as a yellow oil; this soon solidi-
sulphuric acid is dark-blue, giving a black pre- fies, and is obtained pure by one crystallisation
cipitate on dilution. from alcohol (Klinger, Ber. 15, 866; Molt-
Literature. E. P.
13743 of 1896; F. P.
schanowsky, I.e. and Ber. 16, 81 ; Klinger,
257245 A. P. 578580.
; Ber. 16, 941, footnote).
Anthracene Acid Brown B (C.): Azoxybenzene is also prepared by the
reduction of nitrobenzene with arsenious oxide
and caustic soda (Loesner, Eng. Pat. 1555,
J. Soc. Chem. Ind. 1895, 31) ; by the reduction
Nitroaminosalicylic acid is diazotised and com- of nitrobenzene with alkali sulphides in alkali
bined with a-naphthylamine. Two mols. of this hydroxide, the products being mainly azoxy-
are diazotised and combined with 1 mol. of m- benzene and azobenzene, in proportions varying
phenylenediamine. Brown aqueous solution with the amount of sulphide and the time of
gives a violet precipitate with hydrochloric acid. reduction (Farb. vorm. Meister, Lucius, and
Solution in strong sulphuric acid is greyish- violet, Bruning, D. R. P. 216246, J. Soc. Chem. Ind.
giving a brown- violet precipitate on dilution. 1909, 1310) ; by boiling nitrobenzene with
Literature. E. P. 2446 of 1896; D. R. P. 60 p.c. aqueous sodium hydroxide and iron
92655. J. C. C. pyrites, or other heavy sulphides, 90 p.c. of the
AZO- ACID YELLOW, -ALIZARIN product being azoxybenzene (Farbenfab. vorm.
YELLOW, -BLACK BASE 0, -BORDEAUX, Fried. Bayer & Co., D. R. P. 204653, Chem. Soc.
-CHROMINE, -COCCINE, -COCHINEAL, Abst. 1909, i. 272) ; by heating nitrobenzene
-CORALLINE, -EOSINE, -FLAVINE, -FUCH- with charcoal and alkali (Farbenfab. vorm.
SINES Azo- COLOURING MATTERS).
(v. Fried. Bayer & Co., D. R. P. 210806 ; Chem.
AZOERYTHRIN v. ARCHIL. Zentr. 1909, ii. 163) ; and by the electrolytic
AZOFLAVIN v. Azo- COLOURING MATTERS. reduction of nitrobenzene in the presence of
AZOGEN RED v. Azo- COLOURING MATTERS. and Bruning,
alkali (Farb. vorm. Meister, Lucius,
AZOGRENADINES v. Azo- COLOURING D. R. P. 127727 ; Chem. Zentr. 1902, i. 446,
MATTERS. and Farb. vorm. Weiler-ter-Meer, D. R. P.
AZOIMIDES, AROMATIC v. DIAZO COM- 138496 Chem. Zentr. 1903, i. 372).
:
POUNDS. Azoxybenzene or its homologues can be

AZOLITMIN. A substance assumed by obtained by heating nitrobenzene or the corre-
Kane to exist in litmus (Annalen, 39, 25). sponding nitro- compound with an equal weight
AZOMETHANE v. DIAZO COMPOUNDS. of zinc- dust and of an aqueous solution of cal-
AZOORSEILLIN v. Azo- COLOURING MATTERS. cium chloride boiling at 130 ; aqueous solutions
398 AZOXYBENZENE.
' '
of other salts be employed, and the reaction
may sun yellow is perhaps the best known, ha\
ensues at the boiling-point of the aqueous solu- been shown to be azo- dyes (q.v.).
tion (v. Dechend, D. R. P. 43230. AZO- YELLOWS v. Azo- COLOURING MATTEI
Properties. Azoxybenzene crystallises in AZULIN. Blue colouring matter, containe
pale yellow rhombic needles, melts at 36, and in certain essential oils ; e.g. chamomile,
is soluble in alcohol or ether, insoluble in water. folium, and wormwood.
When heated with non-volatile substances, such AZULIN or AZURIN v. AURIN.
as iron filings, it decomposes into aniline and AZURE v. PIGMENT.
azobenzene. Weak reducing agents, such as AZURIN C 3 .-H 32 NO
4 S. Obtained by heati
sodium amalgam in alcohob'c solution, convert it salicylic aldehyde with o-tolylenediamii
into hydrazobenzene (Alexejeff, J. 1867, 503) ; Colourless tables, giving blue fluorescent soh
but more powerful agents, such as zinc chloride tions (Ladenberg, Ber. 11, 596).
in acid solution, reduce it chiefly to aniline, a AZURITE v. LAZTJLITE and COPPER.
small quantity of hydrazobenzene and bases AZURITE or Chessylite. Hydrated basic
derived from it by molecular changes being copper carbonate, 2CuCO 3 -Cu(OH) 2 , forming
also formed (Schmidt and Schultz). Azoxy- monoclinic crystals of an azure-blue colour.
benzene yields two isomeric nitroazoxybenzenes Finely crystallised specimens have been found
when heated with concentrated nitric acid in abundance in an old copper mine at Chessy,
(Linin, Annalen, 114, 217), and when heated with near Lyon in the south of France, and on this
concentrated sulphuric acid to a moderate account the mineral is often known as chessylite
temperature is converted into the isomeric (Brooke and Miller, 1852) ; the name azurite
hydroxyazobenzene (Wallach and Kiepenheuer, (F. S. Beudant, 1824) refers to the characteristic
Ber. 14, 2617). colour. Sp.gr. 3-8 ; hardness 3|-4. It occurs
In addition to azoxybenzene other azoxy- as an alteration product of copper-pyrites and
compounds have been prepared by reducing the other sulphide ores of copper in the upper
corresponding nitro- derivatives either with oxidised zones of mineral veins ; and it is itself
sodium amalgam in methyl alcohol solution or often altered to malachite, the green carbonate
with zinc-dust and soda (cf. Limpricht, Ber. 18, (CuCCyCu(OH) 2 ). Fine crystals are found at
1405; Klinger and Pitschke, Ber. 18, 2553; Broken Hill in New South Wales and at Bisbee
Janovsky and Reimann, Ber. 22, 41 ; v. Dechend, in Arizona ; at the latter place it occurs, to-
I.e.). The azoxy- compounds derived from gether with malachite, in sufficient abundance
metanitraniline, the nitrotoluidines melting at to be mined as an ore of copper. It was also
78 and 107, and the nitroxylidine melting at i
formerly mined at Burra-Burra, in South
123 yield, when diazotised and combined with Australia. From Arizona come pretty
phenols, amines or their sulphonic acids, a class specimens, with azurite and malachite banded
of yellow, orange or red azo- dyes, which can be together, which are polished for use in cheap
employed for cotton and wool (Poirrier and jewellery. Powdered azurite was formerly
'
Rosenstiehl, D. R. P. 44045, 44554). used as a pigment under the name mountain
AZOXY- CpLOURING MATTERS. The dyes blue,' but this is now replaced by an artificia
formerly classified under this heading, of which product. L. J. S.
B
BABBIT'S METAL. An alloy of 25 parts Mgle. Marmelos (Correa), from Malabar
tin, 2 and 0-5 part copper, used
parts antimony, |
Coromandel ; is used in diarrhoea and dysente
as an an ti- attrition metal (v. ANTIMONY).
'
and the fresh pulp is sometimes employed as

BABLAH or NEB-NEB. Commercial names laxative.
for fruits of several species of acacia ; used in the BAGASSE, BEGASS, or MEGASS. Ter
East, in combination with alumina and iron i
applied to the refuse sugar-cane after crushing

mordants, to produce various shades of drab and BAKING POWDERS are any powders used
fawn colour in calico-printing. East Indian as substitutes for yeast. The bread or cake
bablah largely obtained from Acacia arabica
is
|
is rendered spongy by the carbon dioxide'
(Willd.) (A. indica (Benth.)); Senegal and !
generated in the dough ; this is effected by the

Egyptian bablah largely from Acacia arabica :
action of an acid, such as tartaric acid, on sodium
(A. nilotica (Delil.)). The aqueous extracts bicarbonate, and some farinaceous substance is
contain a red colouring matter together with added to act as diluent. To permit the use of
considerable quantities of gallic and tannic acids. discoloured flour, alum was frequently employed,
BAPTISINGLUCOSIDES.
v. this renders the bread white, but at the same
BABUL BARK. The bark from Acacia ara- time indigestible. In 1899 such articles as
bica (Willd.) which occurs in India, Arabia, and baking powder were included in the Sale of
tropical Africa its Indian

: vernacular name is Food and Drugs Acts, and therefore the
'
babul.' Used in India as a tanning material. of alum or any injurious matter was prohibit '
BABUL GUM. An inferior kind of gum All articles are perfectly dried before
arabic from Acacia arabica (Willd.). Known also passed through a tine sieve, and kept in ail
as Bengal gum or Gond babul.'
' ' '
tight packages in a dry place. To every pound

BACTERIA, CHEMICAL ACTION OF, v. of flour, 1 teaspoonf ul of baking powder is added
FERMENTATION. for bread, and 2 teaspoonf uls for cakes. General
BAEL FRUIT. The dried half-ripe fruit of preparations are :
BALANCE. 399
(1) 6 ozs. tartaric acid, 2 ozs. sodium bi-

carbonate, and 1-5 ozs. of farina.
(2) 16 ozs. sodium bicarbonate, 14 ozs.
tartaric acid, and 6 ozs. magnesium carbonate,
and 12 ozs. farina (Workshop Receipts, 1909).
(3) 2J Ibs. cream of tartar, 2 Ibs. sodium
bicarbonate, 1 Ib. acid calcium phosphate, and
4 lb.=. cornflour (Pharm. Formulae, 1908, p. 322).
(4) 3 Ibs. acid potassium sulphate, 1 Ib.
sodium bicarbonate, and 1 Ib. of cornflour
(Pharm. Formulae, 1908, p. 322).
(5) 5 ozs. tartaric acid, 15 ozs. cream of
tartar, 20 ozs. sodium carbonate, and 40 ozs.
rice flour (Workshop Receipts, 1909, p. 90).
(6)20 parts acid sodium phosphate, 20 parts
acid calcium phosphate, 25 parts sodium
bicarbonate, and 35 parts starch (Hiscox, 1907,
102).
Grampian's powder 2 parts cream of tartar,
:
part sodium bicarbonate, and 1 part corn

1 Speci-
men of
starch. oil
Humford's powder (approx.) 7 ozs. sodium
:
bicarbonate, 14J ozs. sodium phosphate, and

3 ozs. starch.
Royal powder : 60 ozs. cream of tartar,
28 ozs. sodium bicarbonate, 1 oz. ammonium
carbonate, and 16 ozs. cornflour.
Goodall's powder is a mixture of 2 parts rice
flour with 1 part tartaric acid and 1 part
bicarbonate of soda.
Green's powder : 35 Ibs. tartaric acid, 56 Ibs.
of sodium carbonate, and 1 cwt. of potato flour.
Horsford's powder consists of 2 packets (1) :
acid calcium and magnesium phosphates, made

up with a certain quantity of flour (2) bicarbo-
;
nate of soda with a little potassium chloride.

Berwick's powder is an artificial fermentation
powder compounded with coarse maize.
Self-raising flour may be prepared by mixing
8 ozs. sodium bicarbonate, and 18 ozs. cream of
tartar with 1 cwt. of flour.
Milk in the solid form, concentrated in a
vacuum at 50-60, was used by Hooker, to
replace inert f arinaceous matter. It is claimed
to have a better nutriment value and increased
leavening power : 20 parts tartaric acid,
54 parts milk powder, and 1 part moisture.
The soda is added before the milk is completely
dry, then the whole dried and ground finely in
a mortar (J. Soc. Chem. Ind. 27, 1908). Cream
of tartar is soluble in hot water, but only slightly
so in cold, whilst tartaric acid dissolves readily.
Therefore a powder containing cream of tartar
evolves carbon dioxide much more slowly than
one compounded with tartaric acid. This is
advantageous, as a dough containing it can be
kept for some time before baking, also it does not
darken the bread ; on the other hand, it forms
Rochelle salt which has a very slight saline
taste. The best powders are made from a
mixture of tartaric acid and cream of tartar.
Good substitutes for tartaric acid are acid
ammonium phosphate, and acid potassium
sulphate, acid potassium and calcium phosphates,
but they have a tendency to darken the bread.
Ammonium carbonate is used in very light
pastries, but it requires expert handling, and
so is very rarely present in the made-up pre-
parations.
BAKUIN. Russian mineral machine oils ;
recommended for lubricating heavy machinery

on account of their high viscosity and great
400 BALANCE.
machine. An absolutely rigid beam, so sus- obliquely, so that the edge terminates in two
pended that whilst it can rotate freely about a points, and closing the bearing at each end by
certain axis (which goes across it somewhere a steel plate, so that the knife has just room be-
above its centre of gravity, and of which every tween without jamming. In suspended balances
point holds a fixed position in reference to the the central bearing is fixed at the lower end of a
stand) it is not capable of any other motion. light framework, terminating above in a hinged-
From two points, a and 5, which lie in the same on ring for suspending the instrument from a
plane as the axis of rotation one near the left, fixed hook or the thumb of the operator.
the other near the right end of the beam the In all precision balances the central bearing
pans are suspended by means of absolutely is attached to a fixed pillar, and is plane ; in the
flexible linear strings, a and 6 are equidistant best balances the bearing is made of one piece,
from the axis of rotation. So far all balances and the central knife-edge rests upon it in its
are alike. In now passing to the actual instru- entire length. A plane bearing necessarily in-
ment, we shall confine ourselves in the main to volves an arrestment so constructed that, besides
the class of balances known as precision balances. doing its primary dutj', it assigns to each point
Of the difficulties involved in the construc- of the central knife-edge a fixed position on its
tion of such balances, that of producing a suffi- bearing. In former times hard steel was used
ciently light and yet practically inflexible beam exclusively for both knives and bearings ; sub-
seems to have rested most heavily on the minds sequently agate bearings came to be combined
of the earlier makers ; but there can be no with steel knives. Robinson of London was
doubt that many of their efforts in this direction, the first to make both knives and bearings of
which occasionally resulted in what we should agate. The agate knife adds nothing to the pre-
now call fantastical beam-forms (hollow ellip- cision of a newly- made balance, but it always
soids, monstrous skeleton -forms, &c.), must be remains clean, while a steel knife, in a chemical
traced back to their inability to reach a sufficient laboratory more especially, is apt to rust. Steel
degree of precision in the geometric adjustment knife-edges are generally ground to an angle of
of the three pivots, and to their charging against 60 (or 90 for very heavy charges). In agate
the flexibility of the beam what was really owing knives, as made by Oertling, only the body of
to these defects in the adjustment. As these the agate prism is groin d to 60, while the edge
difficulties were overcome, beams assumed less is formed by two narrow facets, inclined to each
fantastic forms. Sacre' of Brussels, we believe, other at a far more obtuse angle. Such an
never uses any but plain rod-shaped beams (only obtuse edge stands many years' constant use
perforated hi the middle to insert the bearing without wearing out. American makers have
of the central knife). Most balance makers, introduced the artificially made osmium -iridium,
however, prefer the form of a largely perforated which is used for the tipping of stylograph pens,
rhombus or isosceles triangle (cut out, virtually, as a material for both knives and bearings.
of a plate of metal), and thus attain all that is For the realisation of the two point-pivots A
needful without offending the eye by unduly and B, a great many combinations have been
stretching the middle section, and without using invented. A now obsolete construction of
anything more intrinsically rigid than hammered Weber's (Bib. 2) adapts itself very closely to our
brass or some kind of bronze. In reference to ideal conception. He provides the beam at its
ordinary chemical balances (for charges up to two ends with knife-edges turned sideways and
say 100 grams), it would be no great exag- suspends the pans by means of threads of unspun
geration to say that any reasonably made beam silk which are fixed somewhere in the back of the
is sufficiently rigid ; only in the case of balances beam and hang over the edge. The axis of
intended for very high charges, such as 5-10 rotation is realised similarly. In ordinary
kilogrammes, is it at all worth while to employ balances, as a rule, a vertical slit is cut into each
refinedly designed beam-forms, or to look out for end of the beam, and this is traversed by a short
a material of exceptionally high rigidity. For prismatic knife, the edge of which is a circular
these particular balances hard steel would be arc of small radius which stands perpendicular to
the best material ; but, unfortunately, steel the line AB. From each such knife the pan is
beams are apt to become magnetic. With small suspended by means of an 8 or 2-shaped steel
assay-balances intended for charges up to, say, hook. This construction, if well executed, may
5 grams, on the other hand, the question of afford high precision, but the suspender-hook
rigidity is practically out of court, and the use is apt to rub against the sides of the slit in the
of an exceptionally light material such as beam. Hence, wherever the hook-and-eye'
aluminium, or, better, that alloy of 95 parts of arrangement is adopted for precision balances,
aluminium and 5 of silver (which Sartorius of it ismodified in this sense, that the knife-edge
Gottingen uses for small balances generally) is forms a circle of relatively large radius which lies
indicated. 1 In all balances the axis of rotation entkely outside the body of the beam. This
is realised in a straight knife-edge ground to a system, compared with those considered in the
prism of hard material, which is firmly fixed to sequel, offers the advantage of easy adjustment.
the beam, traversing it crosswise and resting on It used to be very popular with balance makers,
a hard bearing. In ordinary balances the middle and many excellent instruments have been pro-
knife is simply driven through the beam, and duced with it especially by Deleuil of Paris. For
only its two ends are supported in cylindrical, small assay-balances it is indeed probably as
or, what is better, roof-shaped bearings, which good as any other that could be named for
;
form secures to the edge a sufficient fixity of balances intended for higher charges it does not
position, forward and back sliding being pre-
the
possess sufficient durability, although, as
vented by cutting off the ends of the knife writer is able to say from his own experience, if
well made, it lasts better than is generally sup-
1
Tor a fuller discussion of this subject, v. the
writer's Memoir (Bib. 6, 322). In modern balances it is rarely seen
BALANCE. 401
in these, as a rule, the pans are suspended from the central
If
long straight knife-edges, similar to the centra bearing forms part of a sus-
pended frame, an arrestment is
one, by means of broad bearings which, of course easily devised in
the ways illustrated
must be arranged so that they neither twist nor 1 by Figs. and 2.
A explains itself; in Fig. 2

slide. very efficient and easily made arrange- the balance is
ment is to give the bearing the form of a rooJ hinged
on to the bent-down
cut and of one side of a prismatic block of stee]
end of a flat bar which
or agate, and to fix it to the
upper end of a slides up and down
stirrup-shaped or "7-shaped holder which ter- in guides fixed to the
minates below in an eye, from which the
pan pillar between two beds
is suspended by a suitable hook. The eye stands
at right angles to the
of rollers 2x2 in the
knife-edge ; its' working guides on the front side
point, when the instrument is in use, lies verti- of the bar, and one
cally below the centre of the respective end-edge, which is pressed against
and the effect is the same as if the whole of the itsback by a spring.
load were concentrated in that one
centre-point, At its lower end the
although the pressure of the bearing on the knife bar has a small wheel
is equally distributed over the whole of its work-
which rests on the
ing length. This hook-and-eye arrangement is shorter end of the
absolutely indispensable if the pans are suspended
hinged lever by means
by stiff stirrups, because, if these were rigidly of which the balance is ,-,
connected with their bearings, the virtual flQ. 1.
point
of application of the load would shift forwards
raised or lowered. A
small vertical
and backwards on the edge, and the least want adjusting screw below the shorter
end of the lever defines the lowest
of parallelism between it and the axis of rotation position of the
bar at which the
would cause the balance to give inconstant pans just touch the table
without slackening
readings. the chains. In
These roof-shaped bearings were
formerly either case it is an
used almost exclusively by German
makers, improvement to
although an undoubtedly superior system had a heavy
been introduced successfully suspend
by Robinson of block of metal at
London many years ago. In it the pans the lower end of the
are suspended by plane
bearings which a frame, to compel it
suitable extension of the arrestment
keeps in to hang plumb, and
their right positions. Robinson's balances to hinder it from
were justly famous in Great Britain a few
of them are still oscillating. The
working to this day yet, specific advantage
after Robinson's death,
Oertling was almost the of suspended bal- <
only balance maker who followed him in this ances is that they
respect. The general plea against the system need no horizontal
was that flat end-bearings were liable to twist
; table or levelling
and some, after having adopted Robinson's
' ' plan,' screws at the board
improved upon it by cutting out a central on which they may
portion of each end-knife, so that it worked FIG. 2.
with its two ends
only be erected. But
proving thereby that they
;
pillar-balances are on the whole more con-
did not understand their
business, because a venient. In the case of these (supposing
really plane bearing, as a matter of fact, does
not twist on a really plane bearings to be absent) a good system
straight knife-edge, even if
the pan oscillates The
strongly. principal
advantage of the Robinson system is that it
enables one to do what the roof-shaped bearing
prohibits, namely, to satisfy himself that the
knives and bearings are
geometrically perfect.
But here, as in all analogous cases, we must not
forget that the excellence of an instrument
supposing it to be based on a reasonable system-
depends far more on the skill of the maker than
on the theoretical perfection of the
design.
From the bare realisation of ttie ideal
machine, we now pass to the accessories which
a balance needs in order to
become a convenient
instrument, and we will consider these in the
order of their importance.
The arrestment is a mechanical contrivance
to enable the beam to be arrested
at any point of
bs
angular motion, and to bring it to permanent
in its normal '
t;
Fia. 3.
position, in which the plane
three axes stands horizontal.
If the three s to fix the central bearing to the top of
aivots are
self-adjusting, there is, strictly speak- a rod which slides up and down within the
ng, no need of an arrestment ; still for the
execution of precise
rapid jillar properly guided to prevent shaking and
weighingsit is almost rotatory motion and, with its lower end, rests
indispensable. on an eccentric concealed in the sole and governed
VOL. LT. 2D
402 BALANCE.
by a lever- or disc -shaped handle. The eccentric whose length is so adjusted that the pans just
must be so adjusted that when it is at one of its touch the table when the balance is fully arrested.
extreme positions, the pans just touch the board Stirrup-shaped pan -suspenders (as represented
and no more, while, when it is in its other extreme in the figure) are more convenient than chains
position, the beam is at its maximum angle of in many respects, but, for the
purpose under
free play. In the excellent Tarirwaagen of consideration, they do not work with plane end-
Messrs. Becker's Sons, Rotterdam, this system of bearings. The ratchet-wheel visible in the figure
arrestment is realised to perfection. was intended to enable the eccentric to he
The system needs only be slightly modified to arrested at intermediate positions (in taring with
adapt itself to the case of a plane central bearing, garnets and similar operations) but was found
but we prefer to at once pass to the case of three not to work satisfactorily it is simpler and
;
plane bearings, and in doing so cannot do better better to have a block of wood so adjusted that
than describe a balance (for charges up to 5 when put under the handle it just raises the
kilos. ) which Mr. Oertling made for us some years
ago. As shown by Fig. 3, the instrument rests
on three pillars standing on a hollow square
block of iron which conceals the eccentric.
Firmly fixed to the top ends of the pillars is a
substantial brass frame which terminates at its
two ends in V-shaped supports for the end-
bearings. These latter are agate plates cemented
each to the horizontal bar of a kind of stirrup,
the bar terminating on each side in a cylindrical
steel pin which, when the balance is at rest, lies
in the corresponding V of the frame. The
central pillar conceals a movable steel rod, pro-
vided at its lower end with a wheel which rests AGATE. BEARING
on the eccentric. Its upper end carries a sub- PLAN
stantial brass block Avhich divides into two short
piers above, whilst it expands below into a
horizontal plate, pierced by a circular perforation
near each end. These perforations fit exactly
around two cylindrical steel pins, r, r, fixed to the
top plate of the pillars, so that the rod, when
moving up or down, cannot turn or shake in the
slightest degree. The space between the two
piers is bridged over by the central bearing, a
plane agate plate fixed to a prismatic piece of
brass, which is dovetailed into the tops of the
piers, so that, while perfectly steady when in its
place, it can without much effort be slid out or in
(Fig. 4). It is inserted while the beam is being
held in its intended position and passes through
a large perforation in the beam into which the
middle knife projects. The beam terminates at
its left end in one, at its right end in two, horizon-
tal steel pins whose shoulders are continuous but
rapidly expanding surfaces of rotation, and these
pins fit, the single one into a notch, the couple
into a fork, forming part of the fixed arrestment
frame. In the arrested balance each bearing
is almost in contact with its knife ; if the
eccentric be now turned, the central bearing
rises and lifts the whole, beams and end-bearings,
to a greater or less height, and ultimately into FIG. 4.
that maximum height at which the eccentric
stands still without being held in its position. beam sufficiently to enable one to see which side
If the eccentric be now turned the other way, goes down.
both the beam and the end-bearings fall back, Instead of fixing the arrestment frame to the
ultimately, into their prescribed positions of pillar and making the central bearing movable,
rest, even if they should have twisted, which, we may of course do the reverse, and this latter
however, they never do in the instrument system, indeed, is generally preferred for pre-
under description. For a balance intended for cision balances of a higher order.
quick work, and more especially for one used The kindness of Messrs. C. Staudinger's
occasionally for the weighing out of predeter- Nachfolger, of Giessen, Germany, enables us to
mined quantities of solids or liquids, this system give a detailed description and drawing of the
of arrestment is the best that we know of, be- kind of movable frame arrestment which they
cause it enables the instrument to be handled are in the habit of applying to their best instru-
pretty much like an ordinary pair of scales only,
; ments.
to be able to do so to the best advantage, and As shown by Fig. 5 (I. to IV.) the pillar is
without spoiling the terminal pivots, the pans hollow and accommodates a round bronze rod F.
must be suspended by flexible short-linked chains This rod itself, however, conceals a co-axial
BALANCE. 403
round rod L of nickelled steel. The bronze rod and has a spring j, Fig. II., about its lower
F, at its lower end, is guided by perforated blocks, end to assist its natural tendency to sink. The
e, e, Fig. I., while at its upper end it terminates two rods F and L carry two independent arrest-
ment-bars ; L the bar T, for the end-bearings, F
the bar TJ for the beam.
A square pillar K (Figs. III. and IV.), which
rises from a prolongation of the head of the stand
pillar s, by passing through perforations in the
two bars T l and T.,, prevents any motion of
these about the axis of their rods. As shown by
Fig. IV., an adjusting screw, passing through the
bar, and a flat spring t on one side of the square
perforation of the bar (T X or T 2 ), enforce steadi-
ness of motion.
The upright pins g g (I.), which are tipped
with sharp agate cones, arrest the end-bearings
by rising into corresponding conical hollows in
the latter. (Fig. 6, though taken from an
Oertling balance, will give
an idea of the way in which ^
~
these pins work.) The two
slanting lines (Fig. I.)
are meant to indicate
two supports, which pass
through slots in the pillar s
and the bronze rod F, and FIG. 6.
are fixed to the inner rod L,
to lend additional rigidity and steadiness of
motion to the end-bearings arrestment.
The arrestment of the beam is effected by two
adjustable piers z rising from the bar T t of the
bronze rod. The tops of these piers carry roof-
shaped agate bearings, in which the arrested
beam lies with its lower (bevelled) edge. This
would be sufficient to keep the beam from turn-
ing. To hinder it from moving progressively,
there is a horizontal frame L (Figs. III. and IV. )
united with bar T 1 by two little pillars G, G, and
carrying two agate bearings, a roof-shaped one
at the hinder end and a plane one at the front end
of the middle (agate) knife. The roof-shaped
bearing receives that end of the middle knife
as the roof-shaped bearing of an ordinary
balance would (so that by it, and the two beam-
supports, three points of the arrested beam are
fixed in prescribed positions) ; the plane bearing
in front only supports the knife as it rises up to
it on arresting. This plane bearing is adjustable
by means of a screw, so that the arrested central
knife-edge can be made rigorously parallel to
the fixed central bearing of the working in-
strument.
There are three eccentrics, all attached to
the same axis and governed by the same handle
(Fig. II.), one, A, for the bronze rod F,
a second,
B, for the inner steel rod L, and a third, c, for
a pan-arrestment, whose mode of acting will
readily be seen by a glance at Fig. I. When the
handle stands so that line p (Fig. I.) is vertical,
the beam is arrested ; after this point has been
the same
passed, the beam-supports remain at
altitude, but, on turning the handle further,
bar T 2 is raised to lift the terminal bearings as
III. Section
soon as line q stands vertical. The last third of
through pillar and middle knife
IV. Horizontal projection.
;
the motion of the handle arrests the pans.
FIG. 6.
The principal feature in Messrs. Staudinger's
is the rela-
Nachfolger's arrestment obviously
in a thinner surrounded by a gently tive independence of the beam-arrestment and
cylinder
acting spiral spring n. The head of the pillar is of the end-bearings arrestment. In most
perforated and guides the attenuated end of F in other movable frame systems there is only one
its
up-and-down motion. The inner (steel) rod, frame for both, and things are arranged so
L, is guided similarly within the bronze rod F that the middle edge is held fast after the end-
404 BALANCE.
bearings have been lifted by a hair's breadth, linear, and let this project over the scale and
and that the upward motion comes to an end as almost touch it.
soon as the middle knife is just visible above its The rider. Small weights are difficult to
bearing. A refinement upon this construction is handle and easily lost. To avoid this incon-
to merely effect the three contacts, and then, by venience, Berzelius conceived the happy idea of
means of a special eccentric, to let the middle dividing the right side of the beam, or rather the
bearing drop through a distance of 0-1 or 0-2 mm. horizontal lever arm corresponding to it, into ten
Whilst all the several points of a rigid though equal parts, and substituting one rider weighing
movable arrestment-bar move up and down in ten centigrams for all the centigram and milli-
vertical straight lines, the end-edges of the vibra- gram pieces of the set of weights. Obviously the
ting beam describe circular arcs. Hence when- rider, when suspended at the first, second, &c.
ever the bar is raised against the slanting beam, mark from the centre, acts like 1, 2, &c. centi-
the end-bearings tend to slide over their knives grams placed in the pan, and it is equally obvious
and to spoil them. To preclude the possibility that every tenth of a division on the beam corre-
of this, Becker & Sons, in their finest balances, sponds to one milligram of additional weight.
make the bar for the end bearings arrestment of This system was universally adopted and is still
two halves which are hinged on to the pillar in in use, only with this qualification, that we now
or very near the axis of rotation. Sartorius apply it to the counting of the milligrams by
adopted this system and brought it into a slightly means of a rider weighing ten milligrams. The
different form, regarding which we refer to Bibl. reason for the change is obvious. In most
4, where it is illustrated by a drawing. balances the points and 10 of the rider-scale
In a balance which has only plane bearings, are inaccessible. Becker & Sons avoid this
no kind of arrestment, of course, will give satis- inconvenience by dividing the arm into twelve
faction, unless its several parts, and also the parts, and supplying a rider weighing twelve
pillar and the sole, are sufficiently substantial to milligrams. Other makers, for instance, Messrs.
ensure absolute constancy of configuration and Verbeek & Peckholdt, of Dresden, make the top
absolute steadiness of motion even after long- bar of their beams exactly horizontal, and,
continued use. The old masters used to pay great besides
keeping it clear of impediments, make it
attention to this important point, but it is sadly project beyond the terminal edges. One of the
neglected by the majority of their present suc- advantages of this system is that, in the case of
cessors. a short beam, it enables us to double the degrees
In a balance of which the end-pivots are self- of the rider scale, by dividing each arm into only
adjusting, the movable arrestment frame five (integer) parts, numbering these from the
assumes a very simple form. All that is needed left knife onwards and using a rider weighing
is a small frame bearing V-shaped notches for five milligrams. Only, if we do so, the rider
arresting the middle knife in a prescribed suspended at the zero must be counted part and
position, and fixed to a horizontal bar with two parcel of the instrument. Bunge provides a
projecting pins, in order, at the same time, to special rider-bar so contrived that the path of
support, the beam in a horizontal position. As the rider lies in the plane of the three axes. This,
these pins have no other function, the bar may theoretically, is the most perfect arrangement.
be very light, and the whole system need not A rider arrangement, to be complete, must be
have that absolute steadiness of motion which supplemented by a mechanical contrivance en-
is indispensable in the case of plane end- abling one to shift the rider while the balance
bearings. case is closed, and to do so with greater rapidity,
The needle and fcale serve to define the ease, and certainty than would be afforded by a
angular position of the beam. In all modern forceps, supposing the case to be open. Rider-
precision balances the needle points downwards, guides fulfilling this latter condition are scarce ;
and is meant to embody a straight line passing even with the best the rider drops down occasion-
through the axis of rotation and standing per- ally, and has to be searched for.
pendicular on the line connecting the two point To avoid this source of annoyance Hempel does
pivots A and B. The scale is attached to the away with the rider and substitutes for it a vane
pillar ; its zero, if the stand is properly levelled, with a limb graduated into milligrams (v. infra).
lies vertically below the axis of rotation. To The gravity bob a small button or disc of
enable the stand to be levelled, there must be metal so attached to a wire standing vertically
either a plumb line or two spirit levels faced to on the top of the beam exactly above the axis of
the pillar, and so adjusted that when they point rotation that it can be screwed up and down
to their zeros, the line connecting the zero of along the whole range of the wire. It enables
the scale with its projection on the middle one to raise or lower the centre of gravity of the
edge is vertical. The scale should be so gradu- beam, and thus to establish any desirable degree
ated that the needle-line, if produced, would of sensibility.
cut, not the circle described by the needle's A bob thus constructed meets all the require-
reference point, but the horizontal tangent to ments of the balance maker, but for the chemist
this circle, into pieces of equal length (v. infra). who uses the balance it is desirable to have an
In most practical cases, however, this comes to
'
arrangement which enables him at a moment's
the same as saying into pieces of equal angular notice to establish any predetermined degree of
value.' In balances provided with a fixed arrest- sensibility. Such an arrangement was invented
ment frame the scale should be made to move up by the writer some years ago (Bibl. 8 and 5). It
and down with the beam, so that its position in consists of a small bob fixed by mere friction
reference to the needle remains constant. In to the upper end of the needle, which at that
most balances the end-point of the needle is part, has the form of a triangular prism,
and
just clear of the upper circular edge of the scale, is provided with a graduation. The mode
but it is better to make its lowest portion almost of standardising the scale is explained below.
BALANCE. 405
Some arrangement for establishing perfect weight A on, say, the right pan ; the position of
equilibrium in the unloaded instrument is re- potential rest will shift, and the beam, to reach
quired. A small bob screwing along a horizontal it,must turn (downwards on the right side)
wire fixed to some convenient part of the beam through a certain angle o, which depends only
answers best. Less convenient is a
'
vane,' on A and on the weight W
of the empty beam,
meaning a movable horizontal lever at-
little which latter we may assume to be concentrated
tached to the lowest point of the wire, which in its centre of gravity c, the force 2P being
carries theordinary gravity-bob, or to the obviously out of consideration. But the two
upper part of the needle. To understand the weights, A at 6 and W
at c, are equivalent to a
working of the vane and at the same time that point weighing W+A and lying on the straight
of Hempel's invention above referred to sub- line c6 at a point c', not far from c. The new
stitute for the vane an equivalent rigid line position of rest is gained as soon as c' lies verti-
(Fig. 7). If the vane-line stands in the position cally below the axis of rotation, or, to put it
in other words, the right side of the beam goes
down until the leverage of A is so far reduced
and that of Whas so far increased, that the two
momenta statica are equal to each other.
Imagine now the axis of rotation were shifted
vertically upwards through a small height h, but
remained parallel to itself. The imaginary point
weighing 2P now, as soon as the beam turns,
has a lever and helps the weight W the beam
;
will turn through a less angle a to gain its new

position of rest, and, supposing 2P to increase,
a' becomes less as 2P increases.
Imagine now the axis of rotation to be

shifted downwards towards the centre of gravity.
The heav37 point weighing 2P grams now helps
A, and the angle which separates the two
positions of rest will become greater than the
original angle ; the greater 2P the greater will
be the actual angle o". But the two weights, W
concentrated in c, and 2P concentrated in the
FIG. 7. centre of the line ab, taken jointly, are equi-
valent to one point c' weighing W+2P grams,
00 parallel to the middle knife
i.e., if it is it and situated on the straight line connecting the
adds no weight to either side, if turned through two points ; and supposing 2P to increase
90 into position (10), it virtually adds, let gradually from nil onwards, c', in the second
us say, 10 milligrams to the charge of the right
case, will rise and rise, and at a certain value of
pan. Divide the line (10) into ten equal parts, 2P fall into the axis of rotation. The balance
erect an ordinate in each point, and you find the then has no definite position of rest ; and if c'
points 0, 1,2, 3, &c., of the circular path of the rises still higher, the balance upsets. However
end-point of the vane, to which the vane-line small an overweight A may be put on either side,
must point, if the virtual addition to the right the beam would have to turn upside down to
pan is to be equal to 0, 1, 2 10 milligrams. A reach its one (theoretical) position of stable
glance at the figure shows one weak point in the equilibrium.
vane contrivance. There is, however, no need The balance maker of course takes care so
of our dividing the circular limb exactly in the to adjust his instrument that even if the sensi-
way of our figure. We
may, for instance, place bility is at the highest value
which the balance
the zero at the 7 and the ten at the +7 of our is meant to afford, and the two-sided charge
figure, divide the interval between the projec- 2P at its maximum likewise, the centre of
tions on line (10) (10) of +7 and 7 into ten gravity of the whole system lies on the safe side
equal parts, and so adjust the mass of the vane of the axis of rotation.
and its distribution that, by turning it from the Assuming this condition to be fulfilled, the
new zero (at 7) to the new
' '
10 (at +7), we balance to be exactly equal armed and to be
virtually add 10 milligrams to the right charge. charged with a pan weighing p grams
and a
The degrees, corresponding each to 1 milligram, load of p grams on each side, the angle a of
then become so nearly equal to one another that deviation is governed by the equation
the subdivision of each into ten
parts of equal Al ,,.
angular value is permissible. '
THE THEORY OF THE BALANCE. where I stands for the arm-length, * for the
For a approximation imagine a balance
first distance of the centre of gravity of the empty
which is ideally perfect, and assume it to be beam from the axis of rotation, and h for the
charged with P grams from the left and with distance of the axis of rotation from the plane
P grams from the
right point pivot. The of the two end-edges, the axis being assumed to
balance, when free to vibrate, can remain at rest lie above the plane. In the opposite case h must
in only its normal
position, and if brought out be assumed to be negative, or the plus sign
of it will vibrate about it as a
pendulum, because before the second term in the denominator be
the two
charges are equivalent statically to replaced by a minus sign.
But tga is the ratio
one heavy particle
weighing 2P, situated in of the absolute length of scale (measured tan-
the central
knife-edge. Now, put a small over- v. supra) corresponding to angle o to
gentially,
406 BALANCE.
the distance I of the tangent-zero from the axis Y-axis passes through the same centre, we have
of rotation. Hence we have for the position of the resultant point the
AZI equations
x( W +p) = Ikp ; and ?/( W+ p) = Ws - pR
where, supposing I to be measured in tangential
scale degrees, n may be read as
meaning the
number of degrees through which the needle We see that if H be constant i.e. if the rider-
turns in consequence of the addition of A. The
path be parallel to the plane of the three axes
product condensed into
'
'
E ' we will call the tga is proportional to the overweight kp virtu-
sensibility.' ally added to the charge of the right pan but ;
The reciprocal of E, i.e. the number E" 1
it is as well to notice that the tga of our equation
the weight- value of is different from the (tga) which is brought

=p is 1 degree of the scale
about if, instead of hanging the rider on the
the particular A which makes n
i.e. 1. = th
(I0) mark, we actually put kp units into the
With a precision balance the milligram is a right pan. Obviously
convenient unit for A.
For a balance provided with the writer's (tga)
= and less than tga .
(5)
auxiliary bob, eq. (2) may conveniently be
brought into the form With a rider weighing only 10 milligrams, and,
+ y) .
say, a hectogram balance, the term >H in the
denominator comes to very little, but with a
rider of ten times the weight it (as a rule) can
where b is the weight of the bob and yo+y the no longer be neglected ; such a rider cannot
distance of its centre of gravity from the axis of
conveniently be used unless H
is constant and
rotation y , being that distance which prevails the rider must always hang at the balance (at
when the bob is at its highest (zero) position. its zero, over, say, the central knife when it is
In a well-made balance the influence of P on E not used as a weight), or else the sensibility
is small ; we may therefore assume the P of the
has one value with the heavy rider on and
equation to be some average value, and, con- another with the rider off. Another requisite is
tracting constants, say, the weight-value of one that notches cut into the beam be substituted
is
degree for mere marks, and that the rider have a sharp
E-' = A + By (3) .
edge to give sufficient constancy of position to
.
where A and B are constants A obviously being

; its point of application.
that value which E- 1 assumes when y=0. B From what we have said so far, it would
is easily determined by one trial at y=to its appear that in a balance provided with a gravity-
maximum, and the scale thus standardised. bob we can give the sensibility any value we
The theory of the rider might be allowed to may fancy. And so we can, but it does not
take care of itself if it were a general practice follow that we can command any desired degree
to place the rider's path exactly into the plane of precision. Because the three edges and
of the three axes. But such is not the case ; bearings are not what they ought to be, and,
this path, as a rule, lies above the plane, and as a little reflection shows, the effect of their
each mark at its own altitude H. Let us there- defects is the same as if, say, the length of the
fore assume that, after the balance had been right arm, instead of being at the
constant
charged with P on each side, a rider weighing value I, oscillated irregularly between I A and
p had been suspended at a point of the beam l-\-\, where A is a very small length,
which
corresponding to the fraction kl of the arm- increases when W
and P increase, but is inde-
length (at the 10&)" mark counting from the pendent of I. And this again is the same as
1
centre). If the beam stand horizontal, and a if A were nil, but the charge of, say, the right
weight kp be placed in the opposite pan, the side, instead of being at a constant value P,
beam will remain in equilibrium, because we varied irregularly from P e to P+e. In a
have l(pk)=p(kl) whatever H
may be the rider ;
given balance charged with a given P at
each
where it is and the charge kp (virtually) in the side e is constant, but the corresponding angle
left knife-edge are conjointly equivalent to a of deviation $ varies when the sensibility varies.
fixed point weighing kp-\-p, and situated on the Within this angle j3 the balance is, so to say, in
straight line joining the left edge and the point a state of indifferent equilibrium. By going a
(10k) where the rider is. And this equivalence little more deeply into the matter, we easily
holds for the slanting beam as well, and is inde- satisfy ourselves that, even allowing
for the fact
pendent of P. But the sensibility of the beam that we cannot substitute a longer for a shorter
with the rider on is evidently greater than it beam without increasing the beam-weight, e will
was with the rider off. Statically speaking, increase when I becomes less. In a balance
the weight of the beam and the two charges P meant to afford a certain degree of precision,
and P are equivalent to a fixed point C weigh- we cannot allow the arm-length to fall below a
ing W'=W+2P, and situated vertically below certain (very uncertain) value 1 .
the axis of rotation at a distance S and this , A glance at eq. (2) would show, if it were
particle, conjointly with the one embodied in not clear without it, that, if the three axes lie in
exactly the same plane i.e. if h=Q
the rider, is equivalent to a point weighing the sensi-
W+2P+p, and situated on the straight line bility becomes independent of
the charge
between C and the point where the rider sits. which is a great convenience. But h obviously
hence ii
Referring to a system of rectangular co-ordinates cannot be equal to nil at all charges ;
whose X-axis passes through the centre of the the case of the best instruments it is regulatec
central edge and is parallel to AB, and whose so that it has a small negative value when only
BALANCE. 407
the pans are suspended, and, by the unavoidable tion, the greater, as is easily shown from eq. (2),
deflection of the beam, becomes nil at some the relative independence of the
sensibility from
suitably selected medium charge, so that, from the charge, and last, not least, the less the time
this charge upwards, it has small positive values. of vibration. The time of vibration can of
That such a degree of precision cannot be course not be allowed to fall below a certain
attained by purely constructive methods goes minimum, or else the centres of gravity of the
without saying ; indeed, any precision balance charges will not be able to follow the oscillations
' '
requires to be adjusted before it is fit to be of the beam with sufficient promptitude. But
used. For this purpose the value of the h corre- this clause, with larger balances
wrought at high
sponding to the medium charge and the ratio precision, usually takes care of itself. The
of the actual arm-lengths I' I" must be deter-
: exact relation in a balance between the time of
vibration t (in seconds) and the sensibility E is
mined and the errors h and ?77
1 corrected.
given by equation :
For the direct geometric measurement of h

special apparatus have been constructed, which,
in their present form, we believe, afford a suffi- where R is the length of the mathematical
cient degree of precision but the final test
;
pendulum beating seconds at the place of obser-
is (or at least was until lately) at a suit-
always vation, P the total charge on one side, and k
able position of the bob, to determine the weight- a numerical factor, kWl being the momentum
2
value E~ l of one degree of deviation for a series inertice of the empty beam. With the customary
of charges, say, p=0, 50, 100 grams, &c., up perforated rhombus or triangle, k is very nearly
to the maximum charge which the balance is equal to J. From the equation we clearly see that
intended to measure ;and to at least virtually '
with a bob of sufficient range we can choose
'
calculate the corresponding values h by means our own time of vibration or our own sensibility,
of eq. (2). Whether h is positive or negative, but we cannot choose both, in a ready-made
is of course seen from the values E
-1 without
balance. It stands differently with a balance to
calculation. Supposing now h has a greater be constructed. To avoid indefiniteness, let us
value than can be tolerated, one of the knives assume that we wished to design a balance for
must be lowered or raised until at a certain
weighing quantities up to 100 grams with a
medium charge the three edges are as exactly toleration of 0-1 mgr. Let us assume also that
as possible in one plane. Most mechanicians we had made up our minds regarding the mate-
provide adjusting screws for this purpose which rial and the general form for the beam, and that
enable one to work in a systematic manner. we had defined the latter so that the relation
Some, however (for instance, Becker & Sons, between arm-length I, and weight W, were in
following the example of Deleuil), prefer to fix accordance with an equation of the form
all the knives definitely and to alter the form
of the beam itself by means of the hammer. If

W = C + BJ . . .
(7)
the central edge has to be lowered, the lower where W includes the empty pans, C designates
bar of the beam is struck (on both sides) ; if it the conjoint weight of all that which is inde-
is to be raised, the upper bar is struck, until the pendent of I ; and B stands for the weight of the
correction is presumably almost but not quite rest if the arm-length 1=}. Our equation now
effected. The values E -1 are then assumes this form
completely
again determined, and if they are not suffi-
ciently near one another, the hammering is
renewed until the adjustment is perfect. In a where p stands for the charge in each pan.
similar manner (or by means of adjusting This equation affords some guidance in the
screws) the two arms are made equal to each selection of I. Assuming for E a value which
other. The test here is very simple. The renders the decimilligram just visible, and
balance, after having been brought to the taking p=0, we substitute for t the smallest
highest degree of sensibility which it will stand admissible value and solve our equation in
at the highest charge P, is* charged with exactly regard to I. Of course cannot be allowed to fall
P grams on each side. The longer arm goes below that minimum 1 (v. supra) at which the
down, and by determining the small over- inherent error would rise to anything like 0-1 mgr.
weight which must be added to the other side to Where does this limit value 1 lie ? Staudinger
establish equilibrium, we can easily determine the used to draw the line at 200, Oertling at 180
ratio I' : I" numerically. All these adjustments millimetres, and similar values were adopted by
are effected by the mechanician, and when once other makers, until Bunge, some twenty-five
effected are final. Some mechanicians for in- years ago, showed in the most direct
manner
stance, the Beckers of constancy
fix even the centre of possible that a sufficient degree
gravity, but this is a mistake. A balance, to be can be attained with an arm-length of as little as
*
60 millimetres. Thanks to the general excellence
'
complete, must have a movable bob to enable
the operator to give the sensibility that value of Bunge's work his short beams soon became
which suits him best. What degree of sensi- very popular with chemists, and the fact that
bility should we choose ? Answer : In general, almost all other German makers have since come
the lowest degree which suffices for the
purpose to adopt the Bunge system shows that the
in hand.
Supposing, for instance, we can neglect additional perfection in the pivots which the
the half-milligram, it is of no use to screw up the short beam undoubtedly demands is not so
bob any higher than necessary for rendering difficult to realise as an outsider might be in-
the angle of deviation clined to think. Assuming this difficulty to be
corresponding to 0-5 mil-
overcome, it cannot be denied that the short
ligram conveniently visible and no more, because in
opposition to the long beam

the less the
sensibility, the greater the range of
does offer certain
weights determinable by the method of vibra- 1st. It is relatively light, and hence
advantages.
408 BALANCE.
the working of the arrestment is a less effort. if
capillary perforations is stretched out between
2nd. It is less liable to irregularities through a and b ; the hair is parallel to the face of the
one-sided elevation of temperature. Perhaps cale, and only some 0-2 to 0'5 mm. removed
we may add that, 3rd, it is easier in its case than rom it. Ashort terrestrial telescope, fixed in
in that of the long beam to make a smooth- he central (fixed) part of the front- pane of the
working arrestment, and on this account chiefly :ase, serves for the readings. The object glass
it enables one to weigh more quickly. 4th, and serves only to produce an image of the scale and
least in our opinion, it vibrates more quickly. lair within the tube, which the eye-piece (a
Not that we value this last advantage at nothing. Compound microscope) magnifies as far as neces-
The writer's auxiliary bob indeed was invented sary. As the telescope need not be perfectly
with the very object of remed3'ing the corre- steady, it can be fixed at a relatively low cost.
sponding defect in the older form of the instru- We have used this arrangement in connection
ment, being originally intended to be used thus. with one of our balances for over two years, and
In the outset, place the bob far down, say to the :ound it to be almost as good as the one first
mark Avhere 1 of deviation corresponds to 2 described.
mgrs. or some other value securing great rapidity
of vibration, and establish equilibrium as far as ON THE SETTING TIP AND TESTING OF A
thus possible. Then raise the bob to the mark PRECISION BALANCE.
at which 1=0-1 mgr., allow to vibrate, shift the A real precision balance, to be able to do
rider correspondingly, and verify your result. justice to itself, must stand on a very steady
The writer, however, soon came to find this support, in a room where it is not exposed to
method less convenient than he had expected, one-sided changes of temperature. The light
and adopted another very obvious expedient. should fall in from the back of the observer.
It is easy in any beam to bring down the time The best support, of course, is a pillar of masonry,
of vibration to the least value one could reason- standing directly on the earth. Next after it
ably wish for by screwing do^Ti the bob to the (in a substantially built building) comes a shelf
corresponding place. This, of course, may fixed to the wall by strong brackets. A
good
render the decimilligram invisible to the naked heavy table, however, suffices in practice. In
eye. But why not help the eye by optical a large city the street traffic becomes very in-
means ? An ordinary lens magnifying six times convenient in weighing. Its effect can be
linearly affords more than there is any occasion minimised by putting small pieces of thick
for ; only it magnifies the parallactic error as vulcanised-rubber plate between the legs of the
well, and the effort to avoid this error strains the case and the table. In the examination of a
eye very unpleasantly. This experience led the newly set-up balance we naturally begin by
writer to the following combination, which he seeing that the arrestment, the rider-shifting
found to give perfect satisfaction. A narrow apparatus, &c., are in good order, we then level
ivory scale divided into degrees of about O'l mm. the case, and next leave the balance to itself
is fixed slantingly to the needle pretty far down, for some four hours at least, to enable it to
yet far enough up for not obscuring the ordinary acquire the temperature of the room. After
scale which does duty as usual ; on the other these preliminaries we proceed to the following
hand, a compound microscope of feeble power, determinations.
which passes through the central fixed portion of Determination of the inherent error e. For
the front pane of the case, is fixed slantingly to this purpose we charge the balance equally
the pillar. The microscope has one vertical on both sides with the highest weight which it
'
'
wire in its focus which acts as a needle. As is intended to measure (a hectogram balance, for
the microscope inverts its images, the apparent instance, with a hundred-gram piece on each
motion of the wire in reference to the scale side), and after having established approximate
(which one easily persuades himself is fixed) is equilibrium at the highest degree of sensibility
the same hi sense as the real motion of the which the balance will stand at this charge with-
needle in reference to the ordinary scale, so out giving obviously inconstant readings, deter-
that mistakes in regard to the +and are mine the exact position of rest, first with the
avoided. The ordinary scale is graduated after two hectograms in the centres of then* pans,
the micro-scale so that each of its degrees is and then, in a series of successive experiments,
equal in angular value to 10 of the latter. with one or other of the hectograms placed
The writer some five years ago caused Mr. at some point of the edge of its pan so as to
Oertling to apply this arrangement to two give any non-parallelism in the axes or any
his balances, and he has found it to work very other defect in the terminal pivots a good
satisfactorily. Although it was originally in- chance of influencing the result, taking care to
tended chiefly for special occasions the adjust interpolate occasionally an experiment with the
ing of weights, &c. it is used even for our every- two weights centrally placed in order to see
if
day work, as it was found that the microscope the balance still gives the same readings as it did
puts a less strain on the eye than the naked-eye at first. If it does not, this is probably owing to
reading of the ordinary scale. The micro- external causes, such as unequal heating of the
scopic arrangement described adds about 31. to two arms. To be able to translate degrees of
the cost of the balance. A cheaper arrangement deviation into differences of weight, we must at
is the following. A micro-scale, divided con- some stage make two successive determinations
veniently into fifth- millimetres, is fixed slantingly of the position of rest, one with P' in the left
to the pillar, the needle at the corresponding and P" in the right pan (P' and P" stand for the
two hectogram-pieces) and another with, say,
one milligram added to P". For the precise
part is shaped thus, and a hair bv means of rest, we cause the
determination of a position
balance to vibrate moderately, and (neglecting
BALANCE. 409
the reading as being in general liable to

first 50, 25, grams, and to calculate the corre-
irregularities), record 3, 5, 7 ... successive sponding values h. In a good balance h is so
turning-points of the needle, applying a to + small that (supposing our rule regarding the
scale-points lying to the left, and a to scale- adjustment of the bob to be followed) the sensi-
points lying to the right of the zero (or vice bility remains almost constant from p=0 to
versa) ; an odd number in any case in order to p =100 grams. Hence, practically, it suffices
correct for the retarding effect of the resistance to adjust the bob so that at a convenient average
' '
of the air, &c. ; those influences, in other words, charge (where average refers to the most
through which the needle, supposing it to start frequently occurring values of p) one demi-
from 4, at the end of a double vibration, does degree corresponds to say or J of a milligram
not come back to exactly 4, but perhaps to exactly, and then to see what it is at other
3 '7. The algebraic sum of any two succes- charges. If there is no sufficient constancy we
sive readings gives the point a of the scale at enter the values E 1 found on a system of rect-
which the needle would come to rest, in half- angular co-ordinates in function of the charges
degrees, and there is no reason why the half- p, and draw the nearest curve to the points.
degree should not be adopted as a convenient This curve (if h were absolutely constant) would
unit for the purpose in hand. Supposing the be a straight line. In any case it supplies the
readings to be data for a table of values for E- 1 This table, .
al aJ a3 a4 S
however, must not be relied on in standard
weighings, because the value h is subject to
(Example) +3-7 -2-7 +3-5 -2-4 +3-5 changes, for this reason amongst others, that the
we have for a the values e^ 2 1 -0 ; tto
: <*
3 + =+ +
of the knives has a different coefficient
= +0-8; a 3 a 4 + = + M;
a 4 +o 5 l-l Mean agate =+
of expansion from the metal of the beam.
=+ 1-0.
The arm-lengths. For the determination of
The mean value of the four results is put the ratio of the arm-lengths, the orthodox
down as the value of a. Supposing a, through method (for a hectogram balance) is to adjust two
the addition of A milligrams to the right hectogram-pieces to exact equality, and, after
charge to increase by n demi-degrees, then having established equilibrium, to put one into
the left and the other into the right pan, &c.
E= (=2 'E' in the sense of our equation But in practice the following method is better.
(2) ) is the sensibility in demi-degrees ;
and its Take any two fairly well adjusted hectograms
A/ = 1 and viewing them, one as a standard representing
reciprocal E- 1 = -I ^ . . . of equation (2)
\
100,000, the other as an object weighing x milli-
n\ 1 I'i
/
the weight-value of the demi-degree in milligrams, go through the ordinary operation of
grams. Supposing the values for a obtained weighing once with the object in the left pan and
with abnormal positions of the charges to be the standard in the right, and once the other way.
ctj, a.2 , a 3 &c., instead of the mean value a , Supposing (using S as a symbol for 100,000
we
....
,
milligrams) find
corresponding to the centrally placed charges,
then (a a 1 )E- 1 =w 1 , (a a s )E =i; 2 , &c., give !
xl' + 8,)Z"
=(S I
each a value for the inconstancy of the balance xl" = (S + 9 )V S . . . .II
in milligrams (or rather fractions of a milli- (where any 8 may be negative), we have by divi-
gram, it is to be hoped). According to a rule sion of I by II, and subsequent multiplication
deduced from the law of frequency of error, the with I" :
I',
computation
0-845 S + 8'
v n(n ,
1)
where all the u's must be taken as positive,
' '
whence, as a sufficient approximation,
gives the probable weight- value of the devia-
tion of any one a from a meaning that value of ,
a)E- which, in a very large number of

J
(a
determinations, is as often exceeded as not No maker who has a name to lose would
reached. But in practice the number of deter- care to send out a precision balance in which
minations made is never sufficiently great to
1 more than 0-00005 at the outside,
bring out anything like a close approximation ^
{
is
to the law, and it suffices to take r as being equal

to 0-845 times the mean of all the values v, and although for purpose a considerably
any scientific
'
greater error could be tolerated. The corre-
adopt it as sufficiently near to the theoretical e.'
The probability l sponding adjustment indeed, while of the first
that, in a given case, (a a)E~
exceeds importance in commercial balances, in precision
balances is in a sense irrelevant.
2r 3r 4r 5r
is 0-18 0-04 0-007 0-0007 UNEQUAL-ARMED LEVER BALANCES.
respectively. The steelyard or Roman balance. In it
(1)
bears a
In these determinations, if the balance lacks only the shorter arm (of the length I)
a microscopic reading arrangement, it is as well pan the longer arm, by notches cut into its
;
to read from a distance with a telescope, to avoid back, is divided into parts of equal length, I
or lines of
the parallactic error which we have no
right to being the unit. The working points
charge against the balance. the notches should lie in the plane of the two
Determination of h.- All that is necessary is for the knife-edge
edges, being so many bearings
to P
to determine the weight value of one degree in forming part of a sliding weight adjusted
the sense of equation (2) for, say, #=100, 75, units. The unloaded balance is in its position
410 BALANCE.
of rest when the beam stands horizontal. To represented in our figure. F and / (and F' and
weigh a body, it is placed in the pan and the /' in the other parallelogram) are fixed pivots,
sliding weight shifted forwards from notch to A, B, a and 6 (A', B', a', b', behind) are movable
notch until (when the weight hangs at the joints. On each side a horizontal bridge con-
distance nl from the axis of rotation) the beam nects a point D on the vertical side Aa (and a
isagain at rest in its horizontal position. We similar point on B&) with a corresponding point
then have for the weight sought D' on the back parallelogram (so that, for in-
xl=nlP or x=nP. stance, AO, A'a', DD' form one piece) and,
from the centres of these bridges, vertical rods
As fully explained above, the principle of the
are arising which support the pans. Supposing
steelyard is discounted in the modern precision each pan to be charged with P pounds, the centre
balance for the determination of small differ-
of gravity of either of these two equal
ences of weight. In theory there is no objection charges
to its extension to the determination of weights may lie in any of a great many positions about
the respective pan, yet the statical effect is the
generally, but the technical difficulties to be
overcome are great. On an equal-armed same as if it were concentrated, one in the centre
of the one bridge, and the other in the centre of
balance, whose beam is divided into 100 equal
the other ; the two charges will balance each
parts (from end to end), all wefghts from 0-0001
to 100 grams might be determined with three Other, because, if the centre of gravity of one
riders weighing half of (100, 1, and 0-01) gram
descends by h mm. that of the other rises by
h mm., so that the work Ph is the same on both
respectively, but the realisation of 101 exact
sides. An over-weight added to one of the
pivots is no small matter. Where relatively
high precision is aimed at, it is better to provide charges will bring down that side. The bars
AB and A'B' are relatively heavy beams, the
only a small number of notches (say 10) and
have a set of riders, weighing say 10, 1, 0-1, lower bars ab and a'b' are light. Hence it
0-01 grams respectively. The specific gravity depends chiefly on the distribution of the mass
in the beams AB and A'B' whether the balance
balances of Westphal of Celle, are made on this
(if nearly equally charged) has a definite posi-
principle. It strikes us that the steelyard
tion of rest but even if it has, it will never
:
principle might be discounted for the decimal
subdivision of weights, thus : vibrate like an ordinary balance, on laccount of
the great friction in the numerous pivots. If it
Imagine a precision balance whose tvro arms could only be cured of this defect, the Roberval
measure 101 and HZ units. 10 grams placed
in the pan of the longer arm are balanced by
would be the ideal balance for the counter or
10+1 grams placed in that of the shorter ; hence ordinary weighings in the laboratory. This
a 1-gram piece may be adjusted after two exact problem has been to some extent solved in the
torsion balance of Springer, in which the axes
10-gram pieces, &c.
The tangent balance has only one short arm, are realised in stretched out horizontal bands
from which the pan is suspended ; its centre of of 'elastic steel, which act, so to say, as knives
and bearings in one.
gravity lies low, so that the momentum staticum
is made
' '
W* of the beam assumes a high value, and even The torsion balance in a great
l
a considerable weight placed in the pan produces variety of forms, but the principle of construction
a moderate angle of deviation. The needle is the same in all. The following description is
only
moves along a circular limb divided so that
the readings are proportional to the tangents of
the respective angles of deviation, and give the
corresponding weights directly. The equation
A=- ,
(see equation (1), above) holds theo-
retically any value A, but the angular
for
deviation corresponding to 1 gram of additional
charge becomes less and less as the charge in-
creases. The tangent balance, though useful for
the rough weighing of letters, parcels, &c., is not
available for exact gravimetric work.
COMPOUND LEVER BALANCES.

In these, practical convenience and rapid
all
working are gamed at the expense of precision. In

b the Roberval balance
^ ""f the
pans are above
the system of levers
(which as a rule is FIG.
^ concealed in a box),
so that there is room based upon the examination of what was sold as
for bodies of even a high-class pah- of counter-scales for loads up
to 20 Ibs. As shown by Fig. 9, the balance con-
sists of two parallel beams united into a flexible
FIG. 8. tended to explain only parallelogram by means of three vertical frames,
the principle of the machine, which in practice the bond of union in the case of each frame con-
sisting of two horizontal bands
assumes an endless variety of forms. of elastic steel,
The beam consists of two parallel vertical 1
By the Torsion Balance and Scale Company, 92 Reade
parallelograms of which only the front one is Street, New York.
BALANCE. 411
'
which bridge over certain gaps of the frames, identical with the ideally perfect Roberval,'
the middle portion of each band being firmly and, if the centres of gravity of the beams
united with the respective beam end at its lower are in their axes of rotation, the parallelogram
side by means of a screwed-on block of metal. will be in a state of indifferent equilibrium at
In this instrument the beams measure 290 mm. any shape which it may assume. To give it a
from end pivot to end pivot, the steel bands are definite position of rest, we must
either shift (let
5 -6 mm. broad and 49 mm. thick the length
-
; us say one of) the centres of gravity vertically
of the working part of a band is 58 mm., 29 on downwards, or else we must endow our ideal
each side of the beam. The middle band lies wires with torsional elasticity, which, of course,
below the plane of the two end bands by about brings us back to the actual instrument. But
2 mm. The central frame, which does service as the torsional elasticity of the steel bands is very
a pillar, is fixed to the sole of the instrument, considerably more than we want ; its effect on
the end frames are fixed only to their respective the sensibility is the same as if (supposing the
beam ends. Fig. 10, which is drawn to scale, upper beam is suspended at its centre of gravity)
that of the lower lay at a very considerable depth
below its axis of rotation. To give the balance
a sufficient degree of sensibility, we must raise
the centre of gravity of say, the lower beam,
until the stability of the position of rest is reduced
to a sufficiently small value. In the actual in-
strument this is effected by means of the heavy
gravity bob above referred to.
The principal advantage claimed for the
torsion-balance, in contradistinction to the
Roberval balance, is its freedom from friction ;
and this advantage it undoubtedly possesses, but
it is compensated for to a
large extent by the
unavoidable viscosity in the elastic bands. The
instrument described above, when equally
charged on both sides, and with the bob suffi-
ciently far down, vibrates like a precision balance
of a high order ; the position of rest as calculated
from a series of couples of successive deviations
of the needle, is remarkably constant up to at
FIG. 10. least a charge of 5 kilos, on each side ; but once,
when we determined the sensibility at first with
represents one of the end frames. The two steel no charge, then at a charge of 2 kilos., and lastly
bands of each frame, though independent of each for a charge of 5 kilos., and then redetermined
other in their action, are really parts of one the sensibility of the unloaded instrument, we
continuous band which is wound tightly round found that it was out of equilibrium to the extent
the edge of the frame, the ends meeting in of more than a decigram. also found that We
B or B', where they are, we presume, riveted on. the reading of the balance is not quite indepen-
To give them the requisite degree of high tension, dent of the position of the loads on the pans.
the frame, of which part of the right side is The ordinary decimal balance, as used for weigh -
movable, is stretched laterally (by means of pegs ing heavy loads, is a combination of levers as
fixed to the two sides of a vice and slipped shown in Fig. 11. a, b, c, d, e, f, g, h, are all joints
through the two holes of the frame) and the gap or pivots a ; / -,
which is thus produced between the two halves and h rest _/&_
of the right side of the frame is made permanent on the fixed
by means of metal plates wedged into it. The framework of
central frame is somewhat differently shaped the machine
from the lateral ones ; the upper ring, r, is and conse- c r
1
omitted, to enable the upper beam to pass freely quently in-
'
through between the legs of a stool fixed to the directly on ^ 11.
lower and terminating into a vertical peg which ,1
the
i 1 i(jr.
ground,
serves as a needle and carries a globular gravity c rests on the lever ab. In the actual machine
bob. The bob, which in the case of the balance cd supports the bridge which accommodates
under consideration weighs 458 grams, i.e. more the load, while a pan suspended at / receives
than a pound, can be raised or lowered to enable the weights. The pan is so adjusted that it
the sensibility of the instrument to be varied. the load
counterpoises the bridge. Suppose
The system of beams is inclosed within a case amounts to P units and its centre of gravity
lies vertically above i ; a portion P c presses
of plate-glass the top plate supports an arch
;
on
made of a metal tube from which an ivory scale the knife-edge at c and the rest P d P P c pulls =
graduated on both sides is suspended vertically at d and with the same force at g. Now P c pull-
so that its lower edge runs through a notch in to a less force bP c pulling at
ing at c is equivalent
the upper sharpened end of the needle to enable "
the vibrations to be read from either side. b, and bP c ab P c ac, whence bP c = PC & But
.
= .
-
To explain the working of the instrument,

is equivalent to a greater
let us for a moment substitute for the steel bands h P c pulling at 6 or e
force 6 P C pulling at g and g P c gh \f c - eh; -
=
so many linear wires, which, though unbendable,
eh eh ac
offer no resistance to torsional disfigurement. hence Pc Pc .
PC-
b
The torsion balance thus modified is in theory
g
===^- =^- a6
412 BALANCE.
The dimensions = be determined by experiments with known

are so adjusted that -r Sartorius of Gottingen used to apply
gh ac weights.
the Ritchie arrangement to his precision balances
whence -r-~r=l; hence the joint effect of for the determination of differences of weight
ab gn
P c and P d from 10 mgrs. downwards (Bibl. 5), but he has
the same as if they both, i.e.
at g is
P, were suspended at g ; and if, for instance, gh long since given up the notion at any rate it is
:
is of hf, I'j P units in the pan will balance

no longer to be seen in his price 'list. A Ritchie
y'jj
balance might perhaps do well for the adjusting
the P units lying on the bridge. In many
of small weights, but a small precision steelyard
balances of this kind the long arm hf is divided
so that lesser weights can be determined by
would work infinitely better.
Sartorius' combination, if provided with a
means of a rider.
relatively strong wire, might make a handy
ELASTICITY BALANCES. instrument for the rapid (approximate) deter-
mination of weights without the use of any
Imagine an elastic solid body beam, wire,
spiral, &c. to be held fast in one or more standard mass less than 1 gram.
fixed points, and suppose some one other point
a to be used as a pivot for the suspension THE HYDROSTATIC BALANCE
of a load of P
Point a will sink until,
units. isa hydrometer provided with a relatively large
at a certain the strain developed by
depth h, body and a narrow neck, and so adjusted that it-
the deformation of the working body balances weighs considerably less than its own volume of
that weight P. As long as the working body is I water. The top end of the neck bears a hori-
not stretched beyond its limit of perfect elas- zontal table, which serves as a pan, or, what is
ticity, the length h, if not proportional to, is at better, is provided with a horizontal system of
least a fixed function of P ; hence the path of cross-bars, from whose ends a pan is suspended
a can be graduated, at least empirically, so that by means of wires or chains, below the shelf
each point of the scale corresponds to a fixed supporting the vessel containing the floating
number of units of weight. This is the general hydrometer. Acertain weight P, placed in the
principle of the multitude of spring balances. pan, brings down the hydrometer so far that the
Sometimes a relatively strong spring is used to surface of the water touches a certain mark on
effect only a small displacement of a even with the stem. If an unknown weight x requires to
the highest charge, but this displacement is be supplemented by standard weights equal to p
then multiplied by a system of levers, so that units, to produce the same effect, x-\-p=P, or
the least difference of weight which the balance x=P p. Even for P=
let us say 2 kilos., the
is meant to show becomes visible. In a very neck need not be thicker than an ordinary
neat kind of spring-balance, which has become knitting needle, so that the milligram, as a differ-
popular, the displacement of a is, by means of ence of weight, becomes perceptible. Wherever
levers and a toothed wheel, translated into the a precision balance has to be extemporised
circular motion of a needle which moves along a this instrument is useful ; but it has no other
divided circular limb like the hands of a clock raison d'etre. Indeed of all the multitude
on their dial. of machines which the science of mechanics
Jolly constructed a <?asi-precision spring- places at our disposal for the measurement of
balance for sp.gr. determinations thus : long A weights, the equal-armed lever-pendulum is the
spiral of wire is suspended vertically in front only one which, so far, has worked satisfactorily
of a vertical millimetre-scale, etched on a strip for precise gravimetric determinations.
of plate glass which is silvered behind, so as to A balance based on dynamical principles has
avoid the error of parallax. From the lower end been proposed. Imagine a pendulum provided
of the spiral a light pan is suspended ; the index with a shiftable bob above the fulcrum, and
is close above the pan at a convenient
point. carrying a pan attached to the bottom end of the
The instrument has never come into general rod by a hook-and-eye. In a given instrument
use, because any second-class precision balance the time of vibration is a function of the distance
beats it in every sense. A similar remark of the bob from the fulcrum, and of the weight x
applies to an ingenious little instrument invented of the object in the pan, and consequently the
by Ritchie for the determination of minute weight a; is a function of the other variables.
weights. Bibliography. (1) Leonhard Euler :First
Ritchie's balance consists of a very light Development of the Theory of the Balance ;
beam whose axis of rotation passes through its Trans, of the Petersburg Academy.
centre of gravity, and which is firmly united (2) Wilhelm Weber : Balance Gottmgen
:
with a thin horizontal wire which lies in the gelehrte Anzeigen for 1837, 287. Description
axis of rotation. The bind end of the wire is and Drawing in Carl's Reportorium fur physi-
absolutely fixed to the stand ; the front end kalische Technik, 1, 18.
forms the continuation of the axis of a circular (3) Lowenherz :
Report on Metrological
pin revolvable within a circular bearing. A Instruments in Bericht uber die wissenschaft-
needle fixed radially to the pin points to a lichen Apparate auf der Londoner Ausstellung in
divided circular limb. The empty balance is so 1876 ; Braunschweig, 1881. Vacuum Balances,
arranged before use that the beam when hori- 223-232. Balance Beams, 232-237. The
zontal is at rest. To determine a small weight Pivots : Modes of Fixing the Knives, 237-245 ;
(x mgr.), it is placed in, say, the right pan, and Bearings, 246-247 ; Arrestments, 248-253.
the wire turned from the right to the left by (4) Lowenherz : Zeitschrift fur Instrumen-
turning the pin until after the needle has passed tenkunde for 1881, 125 ; Report on Sartorius'
through a degrees (where a may be more than Hinged Arrestment Frame.
360) the beam is again at rest when horizontal.
;
(5) Lowenherz ;
same Journal, year 1881,
We then have a;=const. a. The constant must 184. A Report on Apparatus for Measuring
BALSAMS. 413
Small Weights by the Torsion of Wires : Hooke, has coagulated spontaneously ;

a sheet of balata
Ritchie, Sartorius. Full drawing of Sartorius' is thus formed, which, when
sufficiently hard, is
contrivance on p. 188. removed from the vessel and hung up to dry.
(6) Dittmar ; Waage des Chemikers ; same The coagulation of the latex may also be brought
Journal, year 1881, 313-326. about by boiling, in which case the balata is
(7) Dittmar ; same Journal, year 1882, 63 ;
'
obtained in the form of block.' Formerly it
Mikroscopische Ablesungsvorrichtung fur feine was the custom to fell the trees and then to cut
Waagen. rings in the bark in order to obtain the latex,
(8) Dittmar; R. Soc. Ed. Proc. for 1876; but this practice, which involves the destruction
Chem. News, 33, 157. W. D. of the trees, is now prevented as far as possible.
BALANOPHONE WAX v. WAXES. The latex of balata trees usually flows freely,
BALATA is the product obtained by coagu- and, in favourable circumstances, the yield from
lating the latex of Mimusops globosa, Gaertn., a tree 15-20 inches in diameter, tapped to a
a large forest tree, belonging to the natural order height of 8 feet, is about 3 pints, representing
Sapotacese, which is a native of British, Dutch, from 1^ to 2 Ib. of dry balata.
and French Guiana, Venezuela, Trinidad, Commercial balata may be either grey,
Jamaica, and probably Brazil north of the pinkish or brown. When immersed in hot
Amazon. In British Guiana and the West water it behaves like guttapercha, becoming
'
Indies the tree is known as the
'
bullet or soft and plastic, and, on cooling, it slowly
' '
bully tree. hardens again without becoming brittle.

In physical properties and chemical composi- Balata is also similar to guttapercha (q.v. ) in
tion, balata resembles true guttapercha, for chemical composition, consisting essentially of
which it is the best natural substitute, and it is a hydrocarbon (gutta), of empirical formula
of interest in this connection that the tree H
C 10 16 associated with resins the commercial
, ;
yielding it belongs to the same order as the trees product also includes varying amounts of
(Palaquium spp.) which furnish guttapercha. insoluble matter (dirt) and moisture. Balata
The balata trees are tapped by making a contains a much higher proportion of resins
series of incisions in the bark, so arranged that than good guttapercha, and is therefore inferior
the latex can run down to the base of the trunk, in quality to the latter ; when compared with
where it is collected in a calabash. The latex guttapercha containing a similar amount of
is afterwards poured into shallow wooden vessels, resin, it is found to be a little softer and more
which are usually greased or rubbed with soap flexible.
to prevent the balata from adhering to them, The composition of balata is shown by the
and allowed to stand exposed to the air until it following typical analyses :
414 BALSAMS.
mastic is an instance of a resin. The class of concentration of the calcium benzoate solution
gum-resins may be represented by myrrh. thus obtained, precipitating the benzoic acid
Now, amongst these resins and oleo-resins by hydrochloric acid. Liidy (Arch. Pharm.
there is a group the members of which are marked 231, 43) has shown that the a-, $-, and 7- resins
by possessing a peculiar fragrant odour and of the earlier investigators are mixtures of the
agreeable pungent taste, which is due to the partially hydrolysed cinnamates of the resin
presence of free or combined cinnamic or ben- alcohols present, the a-resin being the least and
zoic acid. These are the balsams, and it is the 7- the most hydrolysed. He also finds that
convenient to consider them as a class by them- benzoin from Sumatra contains benzoic acid,
selves. The word balsam,' it is true, has some- cinnamene, traces of benzaldehyde and benzene,
'
times been used in a wider sense indeed, it was 1 p.c. of vanillin, 1 p.c. of phenylpropyl cinna-
originally employed for an oleo-resin resem- mate, 2-3 p.c. of cinnamyl cinnamate, and a
bling the so-called Canada balsam but it is mixture of a little benzoresinol cinnamate with
;
more convenient to restrict the term to resins or much resinotannol cinnamate, this mixture
oleo-resins which contain cinnamic or benzoic forming the main constituent of the balsam.
acid. The balsams have long been familiar to In addition, woody impurities occur to the
writers on materia medica, some of them being extent of 14-17 p.c., also free cinnamic acid, but
known to Pliny, and even earlier to the Greek to a less extent than free benzoio acid. By
physicians. They are favourite constituents of hydrolysis of the mixture of benzoresinol and
the incense used in the Greek and Roman resinotannol cinnamates the two alcohols are
churches, and while they cannot be said to have obtained, benzoresinol C 16 H 26 O 2 consisting of ,
an important therapeutic value, they are reputed white crystals, and resinotannol C 18 H 4,
mild tonics and stimulants and are a common a brown amorphous powder.
flavouring agent in expectorant medicines. The Siamese benzoin also examined by Liidj
following are the more important :
(Arch. Pharm. 231, 461) differs from Sumatra
Benzoin. Gum Benjamin :Benzo'inum. benzoin by containing no cinnamic acid eithe
(Benzoin, Fr. Benzo'e'harz, Ger.)
; The benzoin free or combined, the main constituent being
of Java and Sumatra is derived from the thick- mixture of a little benzoresinol benzoate with
stemmed trees of Styrax Benztfin (Dryander, Phil. much siaresinotannol benzoate. The alcohols
Trans. 1787, 303; Bentl. a. Trim. 169). while obtained by the hydrolysis of the resin are
the more highly prized Siam benzoin is probably present in the proportion of about 1 : 11. The
obtained, according to Royle, from the Styrax benzoresinol is identical with that obtained fror
Finlaysoniana (Wall). The source of Siam Sumatra benzoin and crystallises in whit
benzoin is, however, still uncertain (Holmes, prisms; m.j>. 272. Siaresinotannol C J2 14 3 H
Pharm. J. [3] 1 4, 354). The first European writer is a brown powder very similar to resinotannol
to mention benzoin is Batuta, who travelled in the obtained from benzoin of Sumatra.
East early in the fourteenth century, and from Benzoin, with the exception of woody frag-
that time to the present day the drug has been ments always present in the cake variety, should"
an established article of materia medica. It is dissolve in five times its weight of alcohol, ar
largely used for incense and in the preparation this solution should give with water a milt
of fumigating pastilles, and enters into the emulsion having an acid reaction. Whe
well-known Friar's Balsam or compound tincture benzoin is boiled with, milk of lime, the he
of benzoin, a favourite dressing for wounds. filtrate should not give off the odour of oil
The juice exudes from the trees as the result bitter almonds on the addition of a solutior
of incisions, and it is allowed to harden before of potassium permanganate. This latter tes
it is removed. During the first three years guards against the addition of cinnamic acid (cf.
of the life of a tree the balsam dries in the form U.S. and Ger. Pharm.).
of tears. This is called head benzoin, and is Peru. Balsamum Peruvianum. (Baume
the most highly reputed. A less esteemed Perou, Fr. ; Pervbalsam. Ger.)
variety is obtained during the following seven or A dark molasses-like liquid obtained in tl
eight years, which is browner in colour and is State of Salvador in Central America from tr
called betty benzoin. Lastly, the trees are split, of Myroxylon Pereira (Klotzsch). Description
and the commoner foot benzoin is scraped off v. Bentl. a. Trim. 83. Balsam of Peru was pro-
(cf. Fliick. a. Hanb. 405). bably introduced into Europe soon after the
Benzoin consists essentially of a mixture of Spanish conquest of Guatemala in 1524 (Fliick. a."
resins together with uncombined benzoic and Hanb. 206). The bark is bruised and scorche
sometimes cinnamic acids. The resins are late hi the autumn, and the exudation excited
entirely soluble in solution of potash and in by this means is collected (Fliick. a. Hanb. 207 ;
alcohol, but by their behaviour toward other Dorat, Amer. J. Pharm. [3] 8, 302 ; Hanbury,
solvents they have been distinguished as a-resin, Pharm. J. [3] 5, 241, 315).
fi-resin, &c. (Unverdorben, Pogg. Ann. 8, Balsam of Peru sinks in water, in which it
397; Kopp, Compt. rend. 19, 1269; Van der is It has a sp. gr. of 1 -135 to 1 -150.
insoluble.
Vliet, Annalen, 34, 177). The yield of benzoic It is soluble in absolute alcohol, chloroform,
acid varies from 12 to 20 p.c., being on an acetone, and glacial acetic acid. Examined by
average about 14 p.c. Two methods are adopted Kraut (Annalen, 152, 129) and Kachler (Ber.
for its extraction. the first the benzoin is
By 2, 512), the chief constituent of Peru balsam was
mixed with sand and heated in a suitable vessel, supposed to be cinname'in, benzyl cinnamate
over which is placed a paper or other receiver : H
C G H 5 -CH CH-COOC 7 7 Kacbler's analysis of
.
to collect the vapours of benzoic acid, which Peru balsam is :cinnamie acid 46 p c.
condense in beautiful tufts of acicular crystals. benz}'l alcohol 20 p.c., resin 32 p.c. Cf. Attfield
The second method consists in boiling the (J. 1863, 557); Delafontaine (Z. 1869, 156)
benzoin with milk of lime, filtering, and after finds in addition to benzyl cinnamate, cinnamyl
BALSAMS. 415
cinnamate or styracin. Trog (Arch. Pharm. the taste aromatic and
pungent. Examined
232, 70) by suitable treatment has divided Peru with a microscope crystals may be detected
balsam into two constituents, an oil and a resin. which have been identified, the feathery spicular
The liquid portion known as cinnamein to the crystals as styracin, and the rectangular tables
earlier investigators consists of benzyl benzoate and short prisms as cinnamic acid.
with a small quantity of benzyl cinnamate ; Storax contains 10 p.c. to 20 p.c. of water, KJ
cinnamic acid and vanillin are found to be p.c. to 18 p.c. of woody and inorganic impurities,
present in very small proportions. The resin leaving 56 p.c. to 72 p.c. of matter soluble in
when hydrolysed yields cinnamic acid and a alcohol, which consists of
chiefly styrolene,
small proportion of benzoic acid and peruresino- metastyrolene, cinnamic acid, styracin, and a
tannol, a resin alcohol of the formula C 18 20 6 H large proportion of resin (Fliick. a. Hanb. 275).
The balsam has also been examined by Thorns H
Styrolene or phenylethylene C 6 5 -CH:CH., is
(Arch. Pharm. 237, 271). obtained as a colourless mobile liquid by distill-
Balsam of Peru has been much adulterated. ing storax with water (Bonastre, J. Pharm. Chim.
Alcohol, fixed oils, copaiba, Canada turpentine, 16, 88 ; Simon, Annalen, 31, 267). The solid
colophony, &c., have been used for this purpose. polymeride of styrolene, metastyrolene, is also said
To ascertain its purity many methods have to exist in storax. Cinnamic acid to the extent
been devised. The specific gravity is impor- of 6 p.c. to 12 p.c. is obtained by
boiling the
tant ; this at once indicates alcohol if present. balsam with sodium carbonate solution, which
Alcohol may also be washed out by water and extracts it as a sodium salt from which the free
the reduction in volume noted. The U.S. acid is liberated by mineral acids.
Pharm. directs 10 drops of the balsam to be Styracin or cinnamyl cinnamate
triturated with 20 drops of sulphuric acid, when
a tough homogeneous cherry-red mixture should C 6 H 5 -CH CH-COOC 9H 9
:
result. be washed after a few minutes

If this was originally discovered in storax by Bonastre.
with cold water it should be converted into a It may be obtained, after removal of the
styro-
resinous mass, which is brittle when cold. This lene and cinnamic acid by treatment of the
test indicates the absence of fixed oils and oleo- residue with ether, alcohol, or light petroleum
resins. (For other modes of testing, v. Hirschsohn in the form of a liquid, which with
difficulty
(Pharm. Zeit. 16, 81): Fliickiger (Pharm. J. [3] assumes a solid crystalline form, the crystals
12, 45) ; Schlickum (Arch. Pharm. [3] 20, 498) ; melting at 44 (Simon, Annalen, 31, 273; Toe],
MacEwan (Pharm. J. [3] 15, 236) Andre'e (Arch.
; Annalen, 70, 1 ;Miller, Annalen, 188, 200).
Pharm. [3] 22, 561); Denner (J.Pharm. Chim. Styracin is readily converted by alkali into
[5] 18, 259). balsams, resins, and
Testing of styrone or cinnamyl alcohol and cinnamate.
gum-resins: Pharm. J. [3] 17, 547.) Benzyl alcohol has been detected as a constituent
A White Peru Balsam is sometimes pre- of storax by Laubenheimer (Annalen, 164, 289).
pared in Salvador by expression from the fruit A good bibliography will be found in W. von
of the Myroxylon Pereira. It is a golden yellow Miller's memoir on the Chemical Compounds
semi-fluid granular crystalline mass containing contained in Liquid Storax (Annalen, 188, 184),
a crystalline resin, myroxocarpin C 2 4H 34 3 , in which the author describes as present, in
together with styrolene, styracin, and cinnamic addition to the constituents already mentioned,
acid (Stenhouse, Annalen, 77, 306 ; Pereira, phenylpropyl cinnamate, ethyl cinnamate, ethyl
Annalen, 77, 309 ; Scharling, Annalen, 97, 70 ; vanillin, large quantities of two alcoholic com-
Harrison a. Malsch, J. 1875, 856). (For more pounds, a- and fi-storesin, and their cinnamic
recent investigations, see Germann (Arch. Pharm. esters, a sodium compound of storesin and a resin.
234, 641) ; Biltz (Chem. Zeit. 26, 436) ; Thorns a. According to v. Itallie (Chem. Zentr. 1901, ii.
Biltz (Chem. Zentr. 1904, ii. 1047) ; Hellstrom 856), a good specimen of storax contains about
(Arch. Pharm. 243, 218). For other varieties 2 '4 p.c. of substances insoluble in ether, 23-1 p.c.
of Peru balsam, v. Fliick. a. Hanb. 210.) of free cinnamic acid, 14 p.c. of water, 22-5 p.c.
Storax. Liquid Storax ; Balsamum Styracis. of aromatic esters, 2 p.c. of styrene and vanillin,
(Styrax Liquide, Fr. ; Flilssiger Storax, Ger.) and 36 p.c. of resin. The total proportion of
Storax balsam is derived from trees of cinnamic acid is about 43 p.c. ; the combined
Liquidambar orientalis (Miller), which are acid occurring partly in the resin and partly in
natives of Asia Minor (cf. Bentl. a. Trim. 107). the aromatic esters.
This liquid storax is nearly related to another Storax is sometimes adulterated with turpen-
harder resin the exudation of the Styrax tine. To detect this Hager dissolves the balsam
officinale (Linn.). Both have been known in a little warm alcohol, and shakes this solution
since the later Greek period, but the latter is with light petroleum. The light petroleum on
now no longer an article of commerce. To evaporation leaves a residue in which the tere-
obtain the storax the outer bark of the tree is binthinous odour is concentrated, and may be
removed, and the inner bark is collected and readily detected. Further, the residue so ob-
boiled in water. The balsam melts and rises tained, in the case of genuine storax, is colourless
to the surface and is skimmed off. with a bluish opalescence, and represents 45-55
Liquid storax is heavier than water, about p.c. of the original balsam ;
but if turpentine be
the consistence of honey, and of a greyish-brown present the percentage is larger, and the residue
colour. It always contains a little water, which has a yellowish colour (Ph. Centh. 15, 163).
imparts to it a greyish opacity. When this is Closely allied to liquid storax are the exuda-
removed, by long standing or by heat, the resin tions from the Styrax officinale (Linn.), Liquid-
becomes quite transparent. Dried in this way-it ambar styraciflua (Linn.), a native of North
is soluble in
alcohol, ether, carbon disulphide, America, the balsam of which was examined
and volatile oils ; but not in light petroleum. by Fliickiger and v. Miller (Arch. Pharm.
The odour of storax is agreeably balsamic and [3] 20, 646 a. 648). It is obtained in the
416 BALSAMS.
form of a sticky grey mass containing white samic resins are obtained from the xanthorrhceas
crystalline portions mixed with fragments of or grass trees of Australia. Seven species of
wood and bark. Its composition does not these, the arborea, ausiralis, Hastile, media,
differ essentially from that of Asiatic Storax minor, bracteata, and Pumilio were described as
(v. Itallie). Liquidambar formosana (Hance) ; early as 1810 by Brown (Prodromus Novse
and Altingia excelsa (Noronha) (cf. Fliick. a. Hollandise). The first two are arborescent trees,
Hanb. 276 ; Tschirch a. v. Itallie, Arch. Pharm. the third and fourth have short stems, and the
239, 541). last three are stemless. Hirschsohn (Pharm.
Tolu. Balsamum tolulanum. (Baume de Zeit. 16, 81) distinguishes three xanthorrhoea
tolu, Fr. ; Tolubalsam, Ger.) balsamic exudates ; but of these only two are
Monardes, in his book published in 1574, important, the yellow or acaroid balsam and the
describing the products of the West Indies, is red balsam (Pereira, Mat. Med. 3rd ed. 1099).
the first to mention balsam of tolu. Soon after- Acaroid Balsam, Acaroid Resin, Eesina
wards it was introduced into England. Tolu is Acaroides, Resin of Botany Bay. This balsam
the product of the trees of Myroxylon Toluifera was first mentioned by Governor Phillips in
(H. B. a. K.), natives of Venezuela and New 1789 (Voyage to Botany Bay). It exudes spon-
Granada, and probably also of Ecuador and taneously from the Xanthorrhcea Hastile and,
Brazil. (For botanical characters, v. Bentl. a. according to some writers, from the X. arborea.
Trim. 84. ) V-shaped incisions are made, and the It has a yellow colour resembling gamboge,
concreted juice from time to time collected. This but sometimes has a deep red tint, and when
draining of the trees goes on for eight months of heated evolves a balsamic odour. It is used
the year (Weir, Joum. R. Hort. Soc., May, 1864). in the preparation of sealing-wax and lacquers
Balsam of tolu is a viscid resin, which on and japanner's gold-size. Among those who
exposure hardens to a vitreous mass. It has have investigated acaroid balsam are Lichsten-
an agreeable odour suggestive of vanilla, and stein (Crell'sAnn. 2, 242); Schrader (Tromms-
has a decided aromatic taste. Crystals of dorff's Ann. 5, 96) ; Laugier (Ann. Chim. Phys.
cinnamic acid may be seen in tolu when thin 76, 265) Widmann (Buchner's Repert. 22, 198) ;
;
layers are examined. It is soluble in alcohol, and Stenhouse (C. S. Mem. 3, 10 ; Annalen, 57, 84).
glacial acetic acid, acetone and chloroform, also Its chief constituents are resin, a trace of vola-
in caustic potash. In benzene it is insoluble, and tile oil, and cinnamic, benzoic, and para-coumaric
nearly so in carbon disulphide, volatile oils, and acids,&]so para-hydroxybenzaldehyde&nd probably

ether. Balsam of tolu consists for the most vanillin (Bamberger, Monatsh. 14, 333). The
part of an amorphous resin similar to that left resin consists of xanthoresinotannol C 43 46 10 , H O
by carbon disulphide in the case of Peru balsam. chiefly in form of para-coumarate (Hildebrand,
This resin on hydrolysis yields toluresinotannol (Arch. Pharm, 234, 698). (For properties of
H
C 17 18 O 5 a lower homologue of peruresino-
,
xanthorrhcea resin oil, .see Schimmel and Co.
tannol, a dark brown powder decomposing at (Chem. Zentr. 1898, i. 258); Haensel (Chem.
100 without melting. It gives colour reactions Zeit, 1908, i.
1837).) By distilling acaroid
with ferric chloride and potassium dichromate, balsam, Stenhouse obtained a light neutral oil
and precipitates with lead acetate and gelatin containing benzene and cinnamene, and by treat-
(Oberlander, Arch. Pharm. 232, 559). Treatment ment with nitric acid the same observer finds
with water extracts from balsam of tolu cin- acaroid balsam to give so large a yield of picric
namic acid (Carles, J. Pharm. Chim. 19, 112), and acid that he recommends it as a convenient
according to Busse (Ber. contains also
9, 830) it source of that compound. As much as 13 p.c.
benzoic acid, and both benzyl benzoate and cinna- of parahydroxybenzoic acid is formed when
mate. Distilled with water, small quantities of acaroid balsam is fused with potash. Amongst
a peculiar hydrocarbon pass over which has been the other products of this reaction, are resorci-
called tolene. The yield, according to Deville, is 2 nol, pyrocatechol, and a double compound of
p.c. (Ann. Chim. Phys. [3] 3, 152). Tolene has para-hydroxybenzoic and protocatechuic acids
the formula C 10 16 H Its sp. gr. at 10
. is H
Cj 4 12 7 ,2H 2 0, which has been likewise ob-
0-858 (Kopp), and it boils at 170, according to tained from benzoin (Hlasiwetz and Barth, J.
Deville and Scharling, or at 154-160 (Kopp). 1866, 630).
Deville found tolene to have a vapour density Red Balsam of Xanthorrhoea. Black-boy
of 5-1. This hydrocarbon does hot appear to Oum. A red balsamic resin resembling dragon's
have been further studied or to be known in blood. When heated it evolves a balsamic
any other chemical relation. odour. This resin does not contain cinnamic
Turpentine present as an adulteration in or benzoic acid, it contains a small quantity of
tolu may be detected by treatment with carbon para-hydroxybenzaldehyde, and consists mainly
disulphide, which has scarcely any solvent action of eri/throresinotannol C 40H 40 chiefly as para-
10 ,
on the genuine balsam or by sulphuric acid,
; coumarate (Bamberger, Hildebrand). A. S.
which imparts to tolu a cherry-red colour, BAMBARA FAT v. BASSIA OILS.
whereas when turpentine is present the mixture BAMBOO. The ash of the shoots of these
turns black. A specimen of spurious tolu grasses (Bambusa arundinacea (Willd), Gigan-
examined by Naylor was completely soluble in tochloa verticillata (Munro), &c.) contains from
carbon disulphide (Pharm. J. [3] 8, 624). To test 30 to 40 p.c. of potash (K 2 0), and constitutes a
for added colophony, the sample is agitated with good source of potash. The fibres of the shoots
4 to 5 times its weight of light petroleum and supply an excellent paper-making material,
the filtrate shaken with its own volume of copper and have been used for this purpose by the
acetate solution (1 1000) when no green colour
: Chinese from time immemorial (Romanis,
should be seen in the petroleum layer (Hirsch- Chem. News, 45, 158 ; 46, 51 Nature 18, 50).
;
sohn, Chem. Zentr. 1895, ii. 694). BAMBOOI FAT or BAMBUK BUTTER r.
Xanthorrhcea Balsams. A number of bal- BASSIA OILS.

BARIUM. 417
BANANA. The fruit of Musa sapientium, ing, and evaporating the filtrate to crystallisa-
a plant growing freely in tropical countries. tion. Berberine crystallises in fine yellow
When ripe the pulp is rich in sucrose and invert prisms, very soluble in hot water and alcohol,
sugar, but in the unripe condition contains much but insoluble in ether. It begins to sublime at
starch, and is extensively used for the prepara- 200. The salts of berberine are sparingly
tion of banana flour in the Indian Archipelago, soluble. The hydrochloride and phosphate are
Brazil, the west coast of Africa, and the Pacific used medicinally.
Islands. Berberine is also found in the root, wood, or
Analyses by Leuscher (Zeitsch. offentl. bark of the following plants Berberis aristata,
:
Chem. 1902, 125) of (1) green husks, (2) ripe

8, Berberis cetnensis, ZantJioxylum Clava-Herculis
husks, (3) unripe fruit (pulp), (4) ripe fruit (pulp), (Linn.), Hydrastis canadensis (Linn.), Coscinium
and (5) banana-meal, are as follows : fenestratum (Colebr.), Jateorhiza Columba
(1) (2) (3) (4) (5)
(Miers.), Xylopia polycarpa (Oliver), Podo-
Water . .70-0 70-0 70-5 67-1 15-0 phyllum peltatum (Linn.), Xanthorissa apiifolia,
Crude protein . 2-0 2-9 3-9 5-0 7-0 Coptis Teeta (Wall.), Soddalia aculeata, Evodia
Crude fat . . 4-5 4-1 0-1 0-2 0-3 melicefolia.
Crude fibre . 9-9 8-6 0-4 0-3 5-9 1
The root, root-bark, and especially their con-
N-free extract . 8-3 10-4 70-0 centrated liquid extracts, are used to a small
Starch . . 19-1
extent for dyeing silk and leather yellow. It
is the only natural basic
Dextrin . . 2-61-0 colouring matter at
Tannin . . 2-2 0-1 present employed. Wool and silk are dyed in
Sucrose . . 15-8 a neutral bath, or with a slight addition of alum
to the dyebath. It gives somewhat clear yellow
Invert sugar . 9-7
Ash . . . 5-3 3-9 1-1 0-9 1-8 shades, not remarkable, however, for any special
quality either of fastness or purity of colour.
Only the quite green fruit, containing mere traces Literature. Buchner, Annalen, 24, 228;
of sugar, can be used for preparing the meal.
Fleitmann, ibid. 59, 160; Bcedeker, ibid. 66,
Ripe bananas contain invertase (Mirran, 384; 69, 40; Dyson Perrins, ibid. Suppl. 2,
Chem. Zeit. 1894, 17, 1283). American analyses
171, and 83, 276; Stenhouse, ibid. 95, 108.
show much less protein in ripe bananas than is
Repert. chim. appl. 4, 459 ; Repert. chim. pure,
given in Leuscher's figures, the average being 3, 105; 4, 367; 5, 423; Annalen, 115, 132;
only 1-3 p.c. (Bulletin 28, U.S. Dept. of 122, 256 ; Suppl. 1863, 2, 191 Journ. chim. ;
Agriculture, 1899). H. I. med. 1826, 2, 314; Chem. Soc. Trans. 15, 339.
BAPTISIN GLUCOSIDES.
v.
Bull. Soc. Chim. 1863, 423 Chem. Soc. Abstr.
;
BARBALOIN v. GLUCOSIDES. 1885,675; 1886, 633, 1041; 1887, 174, 383,

BARBATIC ACID. Barbatic acid C 19 H ao O. 505, 1057 Chem. Soc. Trans. 1889, 63 Arch.
; ;
was first isolated from the lichen Usnea barbata Pharm. [3] 26, 329; 25, 164; Amer. J. Sci.
by Stenhouse and Groves (Chem. Soc. Trans. 1880, [2] 33, 43 Annalen, 24, 228 Annalen, Suppl.
; :
37, 405) in which it occurs in conjunction with 2, 197 Perkin and Hummel, Chem. Soc. Trans.
;
usnic acid. Zopf (Annalen, 1897, 297, 271) 67, 415; Perkin, ibid. 71, 1195).
found barbatic acid in the Usnea longissima, in BARBITURIC ACID v MALONYL CARBAMIDE.
.
the Electora ochroleuca (ibid. 1899, 306, 282), BARILLA or BARILLOR. (Fr. Barille.)
and in the Usnea dasypoga (ibid. 1902, 324, 39) ; Commercial name of an impure soda obtained
Hesse (J. pr. Chem. 1898 ii. 57, 232) describes from the ashes of the Salsola Soda (Linn.),
its presence in the Usnea longissima, Usnea
formerly grown specially in Spain, Sicily,
and Usnea ceralina. Hesse
barbata, (I.e.) Sardinia, the Canary Islands, and the Levant.
originally considered that barbatic acid had the The seed was sown at the end of the year, and the
composition C 22 H 24 8 , and described potassium
plants were ready for cutting in September of the
barium and copper salts and an ethyl ester
following year ; they were usually burnt during
m.p. 132, which apparently established this October. A hole capable of holding one or two
formula, but in a later paper ( J. pr. Chem. 1903, tons of soda was dug in the ground and covered
ii. 68, 1) he confirms Stenhouse and Groves' over with an iron grating ; the dried plants,
formula, C 19 H 20 0,. The sodium salt C J9 H 19 7
-
mixed with canes, were heaped on this and set
Na,2H 2 crystallises in straight-sided leaflets on fire. The heat was sufficient to melt the ash,
(compare also Zopf, 1902, 789). The action of which ran down and collected in the hole. More
acetic anhydride on barbatic acid leads to the
material was supplied to the fire till the hole was
formation of what is probably the Ltctone of full of fused soda it was then covered with
;
acetylbarbatic acid this melts at 250 and on

;
earth and left to cool, after which the porous
recrystallisation from acetic anhydride yields mass was broken out and was ready for shipment.
acetyl barbatic acid C 19 19 (C 2 H H
3 0)0 7 , m.p. 172. Contained about 20 p.c. alkali, together with
The hydrolysis of barbatic acid with aqueous chlorides and sulphates of sodium, calcium and
alkalis yields betorcinol and rhizoninic acid. aluminium and very little sulphur. Formerly
Barbatic acid crystallises in colourless needles,
much used for making soda soap little, if at ;
m.p. 184 (Hesse, J. pr. Chem. 1906 [2], 73, 113). all, used now.
A. G. P.
Kelp is sometimes called British Barilla.
BARBERRY ROOT. The root of Berberis BARIUM. Symbol, Ba. At. wt. 137-37.
vulgaris, a wild shrub common to Europe and ' '
The name barote (from fiapvs, heavy) was
Asia. The active principle which it contains is
given to the earth contained in heavy-spar
the alkaloid berberine C ?0 Hi 7N0 4 ,5H,0, which (terra ponderosa) by Guyton de Morveau in
may be prepared by boiling the root with water '
1779, and was afterwards altered to baryta by
'
containing a slight excess of lead acetate, filter- Lavoisier the name itself, therefore, is indica-
;
1
Including tannin aud colouring matter. tive of the great density of its compounds.
VOL l.T. 2i
418 BARIUM.
Barium occurs principally as
sulphate, the about 65 barium, has a coarsely faceted
p.c.
barytes or heavy-spar BaS0 4 , and is generally crystalline and quickly oxidises in
structure,
found associated with metallic ores containing air. For the last operation it is placed in a
sulphur. Dieulafait (Ann. Chim. Phys. [5] 15, nickel boat contained in a porcelain tube lined
530) has shown that all primary rocks contain with nickel foil. The latter is necessary as
barium in sufficient quantity to be easily when the barium distils towards the end of the
detected. Barium also occurs in nature as operation its corrosive action on the glass
witherite BaC0 8 , barylocelestite (BaSrCa)S0 4 ,
causes rupture. The tube is maintained at
barytocakite (BaCa)C0 3 , alstonite (BaCa)C0 3 , 900 for two or three hours under diminished
and in certain varieties of the ores of manganese ; pressure, keeping the ends of the tube suitably
also in certain silicates, as brewsterite 4 (SrBa) H cooled ; then at 950 for one hour
during which
ALSi 6 18 ,3H 2 0, harmotome H 2 (K 2 Ba)Al 2 Si 6 16
-
time there is a considerable loss of barium.
4H 2 0, and hyalophane or baryta-felspar K 2 Ba' The barium so obtained is kept in an atmosphere
2Al 2 Si g and frequently in mineral waters.
2 4,
of dry carbon dioxide. A sample obtained by
Barium also frequently found in calcium and
is distilling half the barium had the composition
strontium minerals, replacing a portion of those Ba 98-35, Hg 0-83, Fe 0-40. In repeated experi-
elements with which it is isomorphous. ments Guntz failed to obtain barium much
It is never found native. Its oxide, baryta purer than 98 p.c. He, however, found in his
BaO, was first recognised as a peculiar earth later experiments that by preparation of the
distinct from lime by Scheele in 1774. hydride a much purer metal could be obtained
Preparation. D&vy (Phil. Trans. 1808, 354) (Compt. rend. 141, 1240). The method is a
electrolysed a moist paste of a barium salt, modification of the earlier experiment. After
using a cathode of mercury. He thereby the preparation of the metal in the above way
obtained a poor amalgam which on distillation pure dry hydrogen is allowed to enter the
yielded a silver -white solid that he believed to be tube, maintained at 900. It is then heated
metallic barium, but which in reality was only to 1200, just below the fusion point of the
a rich amalgam as shown by Donath (Ber. hydride ; by this means every trace of mercury
12, 745). can be removed. The hydride contained in a
Bunsen (Pogg. Ann.91, 619) slightly modified nickel boat is then placed in the nickel-lined
Davy's process, heating the amalgam in a tube, heated in a vacuum at 1200, whereby
charcoal boat in a current of hydrogen, obtaining the hydride is completely decomposed and the
a tumefied mass which was probably a mixture volatilised barium is condensed on a polished
of hydride and carbide. Guntz has also shown steel tube cooled by circulating water placed
that Kern's method (Chem. News, 31, 243) of inside where the vapours are being liberated.
heating the iodide with sodium yields a sub- The metal so obtained assayed 99-5 p.c. barium
iodide which decomposes water. and was free from hydrogen.
Clarke (Ann. Phil. 17, 419) exposed baryta A very convenient laboratory method for
to the action of the oxy-hydrogen blow-pipe preparing small quantities of barium, also due
flame on charcoal and obtained metallic-looking to Guntz, is to heat barium oxide with one-tenth
its weight of metallic aluminium at 1200 in a
globules probably of barium carbide.
Matthiessen (Annalen, 93, 277) electrolysed vacuum. The metal condenses in the cooli
the fused chloride and obtained metallic- part of the tube and assays as much as 98-8
looking globules which were probably sub- barium.
chloride. The preparation of the metal by electrolysis
Maquenne (Bull. Soc. chim. (3) 7, 368) of the fused oxide or chloride does not appear to
heated the amalgam in vacua, but owing to be attended with success ; sub-salts are form
decrepitation of the substance and rupture of and the current passes without further acti
the tube he was unable to obtain satisfactory (Z. Electroch. 9, 291.)
results. Properties. Barium when absolutely p
Guntz (Bull. Soc. chim. [3] 29, 483), by is a silver white metal with a density of 3
studying the same process, was finally able to It is slightly harder than lead. It melts
distil off all the mercury without decrepitation about 850 and commences to volatilise at 9.
or bursting of the tube. After many experi- Barium oxidises rapidly in air yielding prin
ments, he finally adopted the following method : pally the monoxide ; the powder easSy ta[
An amalgam containing 3 p.c. of barium was fire spontaneously. Guntz states that niol
prepared according to Davy's original process, barium attacked all the metals he tried, iron
and 5 to 6 kilos of it were distilled in an atmo- and nickel being the most resistant. Barium in
sphere of hydrogen under reduced pressure to decomposes water and alcohol in the cold, yiel"
such a point as to obtain an amalgam having a ing in the latter case barium ethoxide.
close grain and not readily oxidisable, containing Oxides of barium. Three oxides of bariu :
about 10 p.c. barium. About half a kilo, of are known barium suboxide Ba 2 0, barium
it was then placed in an iron boat contained in a oxide or baryta BaO, and barium peroxide Ba0 2 .
large porcelain tube. Over the boat was placed Barium suboxide Ba 2 is obtained, according
a nickel spiral to prevent spurting and loss. to Guntz (Compt. rend. 143, 339), by heating
The tube was then heated very slowly by an the protoxide with magnesium or barium to a
e
electric current circuit so as to arrive at a dull temperature of 1 100 It is a black mass which
.
red heat in about four hours, a vacuum being decomposes water.

maintained in the tube. The amalgam slowly Barium oxide, protoxide, monoxide, or
loses mercury without change of form, and baryta, BaO, is the oxide formed when the metal
towards 900 it suddenly liquefies, when the burns in air. It is more readily obtained by
current is turned off to avoid ebullition and heating (1) the nitrate or (2) the carbonate of
loss. The amalgam so obtained, containing barium.
BARIUM. 419
(1) Barium heated progressively,

nitrate heat in a stream of oxygen or of air freed from
fuses, then decomposes with the liberation of carbonic acid. Barium hydroxide may be similarly
nitric fumes and much frothing leaving a porous converted into the peroxide, but less readily, as
mass of barium oxide. it fuses below the temperature of
absorption of
(2) The carbonate may also
be converted into oxygen but the absorption may be rendered
;
barium oxide by exposing it to the strongest heat rapid by mixing the hydroxide with lime or
of a forge fire ; but the last traces of carbonic magnesia which prevents fusion and keeps the
acid are only expelled with difficulty. However, mass porous. Peroxide of barium may also be
at an ordinary white heat, this may be accom- obtained by sprinkling red-hot baryta with four
plished by mixing the carbonate
with one-tenth times its weight of powdered potassium chlorate
of itsweight of lampblack or charcoal and in successive small portions the potassium
;
making into a thick paste with oil or tar, carbonic chloride simultaneously formed may be washed
oxide being evolved, thus : out with water, leaving the peroxide in the form
BaC0 3 +C=BaO+2CO. of a hydrate.
The mixture should be heated in an earthen

The peroxide obtained by these means is not
crucible lined with lampblack and fitted with pure, being contaminated with a little uncon-
verted barium oxide, iron, silica, and other sub-
a tight cover on the large scale witherite is
;
stances derived from the preparing vessels. In
thus converted into baryta for use in separating
order to purify it the finely powdered crude pro-
crystallised sugar from molasses. In a second
duct is gradually added to an excess of dilute
baryta-manufacturing process a mixture of the
carbonates of barium and calcium is ignited hi hydrochloric acid, avoiding any considerable rise
of temperature the crude substance dissolves,
a current of aqueous vapour. ;
(3) On the small scale, baryta may be easily

forming barium chloride and peroxide of hydro-
obtained by heating barium iodate, which readily gen. The solution is filtered from insoluble
matters and treated with baryta water until the
gives up all its iodine, together with five-sixths
silica and ferric oxide, together with a little
of its oxygen, without fusing or frothing :
hydrated barium peroxide, regenerated by action

Ba(I0 3 ) 2 =BaO+I 2 6
.
of the peroxide of hydrogen upon the barium
Barium oxide as prepared by the above
hydroxide, are precipitated. The liquid is again
methods is a greyish-white friable
generally filtered and then supersaturated with baryta.
mass of specific gravity 4-7-5-5.
Briigelmann By this means the whole of the peroxide of
(Annalen, [2] 4, 277), by heating barium nitrate hi hydrogen regenerates barium peroxide, which is
a porcelain flask, obtained minute crystals of
precipitated in minute prisms or laminse of the
BaO belonging to the regular system, of sp.gr. hydrate BaOjjSHjO, in which condition the per-
5-722. He found later that by heating the oxide is best preserved, and is a suitable form for
oxide in a clay or graphite crucible he obtained use in the preparation of peroxide of hydrogen.
needles belonging to the hexagonal system On drying at 130 or at ordinary temperatures in
sp.gr. 5-32, but if heated in a platinum crucible vacua it is converted into pure anhydrous barium
the oxide is obtained in cubic forms, sp.gr.
peroxide.
5-74. It is therefore dimorphous (Zeitsch. Barium peroxide is a grey, impalpable powder,
anal.Chem. 29, 127). It is only just melted more fusible than the monoxide. The
slightly
even by the heat of the oxyhydrogen blow-
temperature of dissociation depends upon the
but in the electric furnace it may be
pipe ;
pressure. According to Le Chatelier (Compt.
readily liquefied and volatilised. The liquid rend. 115, 654), the figures are as follows :
on cooling yields a crystalline mass (Moissan,

Temp. C. 520 555 650 670 720 735 750 775 785 790
Ann. Chim. Phys. [7] 4, 139) it is a non- ; Press, mm. 20 25 65 80 210 260 340 510 620 670
conductor of electricity, but in presence of These pressures vary according to the degree of
mercury may be electrolysed into barium and decomposition being highest at the commence-
oxygen. BaO
is strongly alkaline, caustic, and
ment of the Brin's method of
operation.
poisonous. Fluorine attacks it in the cold,
preparing oxygen depends upon the above
liberating oxygen, the mass becoming incandes-
physical factors. The spongy protoxide of
cent. Dry chlorine has little or no action on the barium prepared as indicated above is placed in
perfectly anhydrous baryta. It is deoxidised
thin beds in iron retorts heated by special
by potassium at a red heat, and slakes with furnaces. The temperature is maintained as
water, forming barium hydrate Ba(OH) 2 with constant as possible between 500 and 600.
such energy that the whole mass becomes
Air which has been freed from moisture and
incandescent provided the amount of water carbon dioxide by passing first over quicklime
be not too large. It rapidly absorbs moisture
and then over caustic soda is forced by pumps
from the air. It unites with methyl and ethyl
the
through the retorts whereby the BaO is con-
alcohols, forming compounds BaO,2CH 4 verted to Ba0 2 The residual nitrogen ia
.
and BaO,2C 2
?
0. H
Heated in the vapour of allowed to escape into the atmosphere. When
carbon disulphide, it forms barium carbonate
the peroxidation is complete a set of valves
and barium sulphide :
with the exhaust
places the retorts in connection
3BaO+CS 2 =BaC0 3 +2BaS. pumps, the reduction of pressure causing libera-
!
It dissolves
readily in dilute nitric and hydro
- tion of oxygen. The first portions are allowed
chloric acids, but with most other acids forms to escape until the pressure measures 65 cm.
1
insoluble salts. When vapour of sulphuric an- mercury, another set of valves then comes into
hydride is passed over it, heated to low redness play and automatically connects the retorts
in a glass tube, formation of barium
sulphate with the gasometer. The oxygen obtained is
BaS0 4 occurs with incandescence. 97 to 98 p.c. pure. Barium peroxide is used
Barium peroxide or dioxide Ba0 2 is formed in the preparation of hydrogen peroxide or
when anhydrous baryta is heated to a dull red dissolved in acidulated water as a bleaching agent.
420 BARIUM.
Peroxide of barium is decomposed by sul- bonic acid ; hence it is frequently used in the
phuretted hydrogen at ordinary temperatures, determination of the amount of carbonic acid
and when heated in a current of carbonic oxide contained in the air. On exposure to air the
it becomes white hot. It becomes incandescent crystals fall to a white powder, with loss of
when heated in sulphur dioxide. When treated seven molecules of water. De Forcrand (Compt.
with strong sulphuric acid at a temperature rend. 103, 59) isolated the hydrate Ba(OH) 2 ,II 2
exceeding 70, oxygen is given off ; at lower by allowing the compound BaO,2CH 3 0+2H.:
temperatures the oxygen is mixed with ozone. to evaporate over sulphuric acid in vacua.
When the peroxide is mixed with acidulated H. Lescceur (Compt. rend. 96, 1578) shoAvs that
water in presence of oxide of silver, peroxide at 100 Ba(OH) 2 ,H 2 has a tension of dissocia-
of manganese, or peroxide of lead, oxygen tion of 45 mm., and that this hydrate is com-
isevolved both from the peroxide of barium and pletely converted to Ba(OH) 2 when heated to
from the other oxide. A small quantity of a 100 in vacua. Lescceur also proves that the
silver compound is capable of decomposing a dissociation tension of Ba(OH) 2 ,8H 2 is 213
large quantity of barium peroxide, but iodine mm. at 75, so that at this temperature all three
decomposes an exactly equivalent quantity :
hydrates of BaO may exist simultaneously.
Ba0 2 +I 2 =BaI 2 +0 2. Ba(OH) 2 when heated
, alone, is only reduced
to baryta above a red heat ; if not heated above
The amount of active oxygen in Ba0 2 may
be determined by adding a known quantity of redness, it re-forms, on cooling, a crystalline
the peroxide to pure hydrochloric acid, then mass of Ba(OH) 2 , but when heated in a current
of air it takes up oxygen and is converted into
potassium iodide free from iodate together with
excess of bicarbonate of soda, and titrating the peroxide of barium with loss of water ; when
liberated iodine with a standard solution of
heated in a current of carbonic acid it also loses
sodium thiosulphate. It may also be estimated water and is converted into barium carbonate :
by titrating an acidulated solution with standard Ba(OH) 2 +0=Ba0 2 +H 2 0.

potassium permanganate (Bertrand, Bull. Soc. Ba(OH) 2 +CO 2 =BaC0 3 +H 2 0.
chim. [2] 33, 148). Baryta has until recently been used in the
Barium hydroxide, Hydrate of Baryta, or processes of sugar-refining, inasmuch as it forms
Caustic Baryta Ba(OH) 2 orBaOH 2 0, is formed, H
the compound C 12 !!2 11 BaO with cane-sugar,
with great evolution of heat, when water is which, when treated with carbonic acid gas, is
added to anhydrous baryta (barium oxide) : decomposed into insoluble barium carbonate and
BaO+H 0=Ba(OH) 2 2. sugar, hence affording a means of separating the
Ahot concentrated solution of equivalent pure sugar from the molasses ; but as strontium
quantities of barium nitrate and sodium or po-
hydrate acts in a similar manner, and is not
tassium hydroxide deposits, on cooling, crystals poisonous, it has been substituted for baryta in
of barium hydroxide. Soda is usually employed, sugar-refining.
of sp.gr. 1-1 0-1 -15, and the crystals obtained are Hydrated barium peroxide. Schdne has
freed from mother liquor by draining, or better,
shown (Ber. 13, 803) that only one hydrate of
BaO 2 exists, containing 8 molecules of water,
by means of a centrifugal machine. Ba0 2 ,8H 2 0.This hydrate is precipitated in
Commercial caustic baryta is prepared or
the large scale by igniting the native sulphate crystalline scaleswhen peroxide of hydrogen is
added to concentrated solutions of barium
or heavy spar with coal or charcoal, whereby an
hydroxide. It is slightly soluble in cold water, but
impure barium sulphide is obtained, and heating
this is earthenware retorts into which a current decomposes in boiling water, forming Ba(OH)o
of moist carbonic acid is passed, thus converting
and evolving oxygen.
it into carbonate :
Barium subehloride BaCl is obtained (Guntz,
Bull. Soc. chim. [3] 29, 490) when equal amounts
BaS+CO 2 +H 2 0=BaC0 3 +H 2 S.
of BaCl 2 and Ba are heated together in vacua at
Superheated steam is then passed over the 850. The fragments of BaCl 2 absorb the
heated carbonate, when the following decom- molten barium without change, and are micro-
position takes place :
crystalline. The material so obtained is not
BaC0 3 +H 2 0=Ba(OH) 2 +CO,. pure. It decomposes water. By using Na,
According to R. Heintz (Chem. Zeit. 1901, a definite compound NaClBaCl can be obtained.
199), only the carbonate is used to any extent. BaCl appears to be formed when electrolysing
The calcination is conducted in specially confused BaCl 2 .
structed furnaces lined with basic material Barium chloride BaCl 2 Crystallised (terra.
and heated with producer gas. The product ponderosa salita) BaCl 2 ,2H 2 0. Barium chloride
contains 95 p.c. BaO. The same author reviews may be prepared either from witherite, the
the methods that have been suggested for the native carbonate, or from heavy-spar, the native
manufacture of baryta from barytes, and con- sulphate. The witherite is dissolved in dilute
siders them too costly for the production of a hydrochloric acid and the solution allowed to
cheap commercial oxide. stand some time in contact with excess of the
Caustic baryta crystallises from water in carbonate, which is added to precipitate iron and
large, transparent, colourless, quadratic prisms
other foreioî metals present in the mineral ;
capped by pyramids. The crystals Ba(OH) 2 , the rapidity of precipitation is much increased
The
8H 2 are isoinorphous with the corresponding by the addition of a little baryta water.
strontium compound. They dissolve in 20 parts filtered liquid is then neutralised with hydro-
of water at 15, and in 2 parts of boiling water. chloric acid, and the salt out and
crystallised
The aqueous solution known as baryta water is purified by recrystallisation.
From the native sulphate barium chloride
highly caustic and of strong alkaline reaction,
rapidly becoming covered with a film of car- may be prepared in two ways :
bonate owing to absorption of atmospheric car- (1) By heating the sulphate in a crucible with
BARIUM. 421
powdered coal and decomposing a filtered solu- ably. Hot absolute alcohol dissolves only ^
tion in water of the barium sulphide formed with part of the crystals ; but according to Fresenius,
hydrochloric acid : BaS+2HCl=BaCl 2 4-H 2 S.
1 part of the salt dissolves in 8108
parts of
Excess of hydrochloric acid is added, and alcohol of 99-3 p.c. at 14, and in 4857
parts of
the liquid boiled till free from sulphuretted the same alcohol at its boiling point.
hydrogen ; it is then filtered, cooled, and evapo- The crystals are not efflorescent, but give up
rated to the crystallising point. the whole of their water at 100,
leaving a
(2) By heating a mixture of 100 parts finely
white mass of the anhydrous salt, which melts
powdered heavy-spar, 40 parts of charcoal, 20 at a red heat, forming a translucent mass on
parts of limestone, and 50 parts of
calcium cooling. Specific gravity of the anhydrous
chloride to a red heat in a reverberatory furnace, chloride is given by various observers as 3 -70 to
by which barium chloride and calcium sulphide 4-15. When heated in a current of steam it
are formed. The mass is lixiviated with water, evolves hydrochloric acid below its fusing point.
when the barium chloride is dissolved out, A concentrated solution of barium chloride is
leaving an insoluble calcium oxysulphide formed decomposed by sodium or potassium nitrate
by the union of the sulphide with the oxide of forming barium nitrate and a chloride of the
calcium produced by ignition of the limestone. alkali-metal. With glycocol CH (NH )-COOH
2 2
In this process the manganese chloride left itforms a crystalline compound, and also acts
as a by-product of the chlorine manufacture upon blood as a preventive of putrefaction and
may be used in place of calcium chloride, a little coagulation.
sand being added along with the limestone or Barium chloride is extensively used as a re-
chalk, and heated on a cast-iron plate. Wacken- agent, especially for the detection and estimation
roder (Dingl. poly. J. 253, 440) has proposed to of sulphuric acid. It is also used for the prepa-
'
prepare barium chloride by adding an equivalent ration of artificial sulphate or permanent white,'
of calcium chloride to a solution of barium and for preventing the incrustation of steam
sulphide, and passing a stream of carbonic acid boilers by decomposing the gypsum of hard
gas into the mixture, whereby calcium carbonate waters.
is precipitated. Barium oxychloride. Andre' (Compt. rend.
Commercial barium chloride generally con- 93, 58) obtained an oxychloride of barium by
tains small quantities of strontium and calcium adding 60 grams of Ba(OH) 2 to 200 grams of
chlorides, together with traces of the chlorides crystallised barium chloride, and boUing the
of iron, aluminium, copper, and lead. Washing mixture with 500 grams of water, filtering, and
the crystals with alcohol removes both the allowing to cool, when nacreous lamellae, to
strontium and calcium chlorides, whilst calcium which he ascribed the formula BaCl 2 -BaO,5H 2 0,
chloride may also be removed by digesting with separated out (Compt. rend. 98, 572). Beck-
barium carbonate suspended in water, when the mann (J. pr. Chem. [2] 27, 126) also obtained
calcium chloride becomes converted to car- nacreous plates by similar means to which he
bonate, or more rapidly by adding baryta water gave the formula BaCl(OH),2H,0. These plates
and passing carbonic acid gas into the liquid. lose ;jths of their water at 120 and the remaining
Digestion with barium carbonate also precipi- fifth at the fusing-point by prolonged heating
tates the sesquioxides of iron and alumina. in a stream of hydrogen. This oxychloride is
Lead and copper may best be removed by the readily decomposed by water or alcohol.
addition of a little barium sulphide. Barium chlorate Ba(C10 3 ) 2 .
Dry Ba(OH) 2
Barium chloride may be recovered from does not absorb chlorine, but in presence of
mixtures of chlorides of the alkalis and alkaline water it rapidly takes it up, forming first hypo-
earths by treating the concentrated liquor with chlorite and chloride, the former of which breaks
a hot saturated solution of salt, when on cooling up into chlorate and chloride
a mixture of barium and sodium chlorides
6BaO+6Cl 2 =5BaCl 2 +Ba(C10 3 )2
crystallises out ; by treating a cold saturated
solution of this mixture with twice its volume of (Konigel-Weisberg, Ber. 12, 346).
As it is difficult to separate from the chloride,
hydrochloric acid, barium chloride is precipitated
the chlorate is best prepared by neutralising a
(Dingl. poly. J. 250, 91).
solution of chloric acid with barium carbonate
Barium chloride crystallises from aqueous
solution with two molecules of water BaCl 2 ,2H 2
and evaporating to the crystallising point. It
crystallises in colourless monoclinio prisms
with
in transparent, colourless, rhombic tables;
1 molecule of water, soluble in 4 parts of cold and
sp.gr. 2 -66-3 -05. The crystals decrepitate
when heated. lessthan 1 part of boiling water.
They have an unpleasant, bitter, Barium chlorate is also slightly soluble in
sharply saline taste, exciting nausea, and are
alcohol, and the alcoholic solution burns with a
very poisonous.
One hundred parts of water at dissolve green flame.
32-62 parts of anhydrous barium chloride, and If strongly heated fused barium chlorate be
0-2711 part for every degree above 0; 100 plunged into a jar of coal gas, a brilliant com-
bustion of the carbon and hydrogen contained in
parts of water at 15-6 dissolves 43-5, and at
the coal gas occurs at the expense of the oxygen
105-5 78 parts of the crystallised chloride. One
of the chlorate.
part of crystallised barium chloride at 18-1 dis-
solves in 2-257 parts of water to form a solution Barium perehlorate Ba(C10 4 ) 2 ,4H 2 is readily
of sp.gr. 1-28251 A
solution satu-
formed by neutralising perchloric acid with
(Karsten).
rated at 8 has a barium hydrate or carbonate. It crystallises
sp.gr. of 1-270 (Anthon).
Barium chloride is almost insoluble in strong from the solution in long deliquescent prisms
hydrochloric acid, so that it is precipitated from very soluble in water.
Barium bromide BaBr 2 .
Crystallised
its solutions
by hydrochloric acid, and a few
drops of the acid reduces the solubility consider- BaBr 2 ,2H 2 O.
422 BARIUM.
This salt is prepared by saturating baryta periodate is formed when barium iodate is
water or barium carbonate or sulphide with heated to a high temperature :
hydrobromic acid or by ; decomposing the 6Ba(I0 3 ) 2 =Ba 6 I 2 12 +4I 2 +90 2

sulphide with free bromine, sulphur being pre- or on heating barium iodide in a current of air
cipitated. until no more iodine is given off :
The most convenient method is to bring to-
5BaI 2 +6O 2 =Ba 6 I 2 12 +4I 2
gether under water 12-5 parts of bromine and
.
1 part of amorphous phosphorus, by which a Hence Sugiura and Cross (J. Chem. Soc. 1879 ;
solution of hydrobromic and phosphoric acids 118) conclude that Ba 6 I 2 12 is the most stab
is formed, which is neutralised with barium car- combination of barium, iodine, and oxygen.
bonate rendered alkaline by baryta water. The Barium fluoride BaF 2 is obtained by neutral-
insoluble barium phosphate may then be filtered
ising hydrofluoric acid with barium hydroxide 01
off and the bromide obtained by evaporation and recently precipitated carbonate ; or by precipita-
crystallisation. ting a solution of barium nitrate with sodium or
Barium bromide is very soluble in water, and potassium fluoride. It forms a white, granular,
crystallises with difficulty ; it is isomorphous crystalline powder, sparingly soluble in water,
with the chloride, but unlike the latter salt is but readily soluble in nitric, hydrochloric,
soluble in strong alcohol. Ic loses one molecule hydrofluoric acids.
of water at 75, and the second at 120 (Beck- It combines with fluorides of silicon an<
mann, J. pr. Chem. [2] 27, 126). boron, forming compounds BaF 2 -SiF,
the
Barium oxybromides. Two oxybromides barium and BaF 2 -2BF 3 T"
silicofluoride .
have been prepared by Beckmann (I.e.). former is precipitated by adding hydrofluosilici

BaBr(OH),2H 2 O resembles the corresponding acid to soluble barium salts as a crystalli
oxychloride. BaBr(OH),3H 2 O was obtained by precipitate totally insoluble in alcohol, an
adding alcohol to mixed solutions of BaBr, and serves as a means of separating barium fro
Ba(OH) 2 . strontium and calcium, which are not precipi
Barium iodide BaI 2 Crystallised BaI 2 ,7H,O.
. tated by hydrofluosilicic acid.
Barium iodide is formed when hydriodic acid gas Barium fluoride forms a crystalline compoum
is passed over baryta at a red heat, a violent with the chloride of barium BaCl 2 -BaF 2 when
action occurring attended with incandescence. solution of barium chloride is mixed with one
It is generally prepared by mixing barium monosodium or potassium fluoride ; this double com
sulphide with a saturated solution of iodine in pound is more stable than the fluoride itself, am
alcohol as long as sulphur is precipitated the ; remains as a granular mass on evaporation
filtrate is then boiled rapidly to near dryness, the solution.
redissolved in a little water and again evaporated, Barium carbide BaC, was first obtained by
this time to dryness, preventing the access of air Maquenne (Ann. Chim. "Phys. (6) 28, 259) b;
as much as possible by performing the operation heating a mixture of the carbonate and carbo
in a glass bolt-head. On redissolving the mass with magnesium or by the action of carbon O
in hot water and allowing to cool, slender needles the amalgam in an atmosphere of hydrogen
separate out of the composition BaI 2 ,7H,,0 a red heat. Moissan (Compt. rend. 118, 683
(Croft, Gazz. chim. ital. 1856, 125; Thomsen, obtained it in a pure crystalline condition t
Ber. 10, 1343). heating a mixture of the carbonate or the oxide
These crystals are very deliquescent and with carbon in an electric furnace. Its specific
readily soluble in alcohol. They lose 6 molecules gravity is 3-75, and it possesses properties
of water at 125, and the remainder at 150 similar to CaC 2 but , is more fusible.
(Beckmann, pr. J. Chem. They
[2] 27, 126). Barium carbonate BaC0 3 The native car- .
decompose slowly at ordinary temperatures, and bonate was first noticed to occur at Leadhills in
quickly when warmed, giving off violet vapours Scotland, in 1783, by Withering, and hence
of iodine. received the name witherite. It is found in
The double iodide of barium and mercury many places in England, specially fine crystals
has a sp.gr. of 3 -588 higher than that of Thoulet's being met with at Fallowfield in Northumber-
solution, and may be of use for petrographical land : it is also found in Silesia, Hungary,
purposes (Rohrbach, Jahrb. Min. 1883, 2, Styria, Russia, South America. Witherite
Mem. 186). crystallises in the rhombic system isomorphous
Barium oxyiodide. Beckmann (J. pr. Chem. with aragonite. It occurs also in globular,
[2] 27, 126) prepared an oxyiodide of barium tuberose, and botryoidal forms ; more frequently
of the formula BaI(OH),4H 2 O which crystallises massive. Sp.gr. 4-29-4-35; hardness 3-3-75.
in short thick needles. Knop (Landw. Versuchs-Stat. 17, 65) found
Barium iodate Ba(I0 3 ) 2 is largely used for 0-02 p.c. of barium carbonate in Nile mud
the preparation of iodic acid, and is obtained as from Minich and Achinin and Dworzack ;
a white granular precipitate by adding potassium (Landw. Versuchs-Stat. 17, 65) found baryta in
iodate to barium chloride. the ash of the wheat grown thereon. Alstonite
It is soluble in 3000 parts of cold and 600 (BaCa)C0 3 contains barium and calcium in
parts of boiling water. It dissolves in hot nitric varying proportions, and is isomorphous with
acid, and crystallises out on cooling in bright, witherite. Baryto-calcite BaC0 3 +CaC0 3 crys-
glittering, monoclinic prisms isomorphous with tallises inthe monoclinic system.
the chlorate. Hydrochloric acid dissolves it Barium carbonate is rapidly formed when
to
with evolution of chlorine. baryta, hydrated or anhydrous, is exposed
Barium periodate. By passing iodine vapour the atmosphere. When BaO is heated in C0 a
in a current of dry ah* over heated oxide of it absorbs the gas, becoming incandescent ; the
barium a basic periodate of the formula Ba 5 I 2 O 12 basic carbonate being formed (Raoult, Compt.
or Ba(IO^) 2 4BaO is formed. The same basic rend. 92, 1, 110).
BARIUM. 423
It of colourless octahedra,
is
readily prepared by precipitating occasionally twinned
aqueous solutions of the nitrate or chloride with like spinelle (Groth, Jahrb. Min. 1883, 1, Ref. 14).
ammonium carbonate, filtering, and washing Barium nitrate is prepared on the large scale
with hot vpater or by igniting a mixture of 10
; either by dissolving the native carbonate
parts powdered heavy-spar, 2 parts charcoal, and (witherite) or the crude sulphide in dilute nitric
5 parts pearl ash (potassium carbonate). Potas- acid, or by mixing hot saturated solutions of
sium sulphide and barium carbonate are obtained barium chloride and sodium nitrate. On cool-
and may be separated by water. The impure ing, the larger portion of the barium nitrate
carbonate thus produced may be used to prepare crystallises out, and the evaporation of the
other salts of barium, but these salts will contain mother liquors yields the remaining portion.
iron. Barium nitrate crystallises in lustrous, colour-
Artificial barium carbonate is a dense soft less, regular octahedra, frequently modified
white powder, poisonous, and hence used for by faces of the cube, of sp.gr. 3-2. The
destroying rats. It is very sparingly soluble in crystals are permanent in the air, decrepitating
water, slightly soluble in water containing when heated, and melting at 597 (Carnelley).
carbonic acid, owing to the formation of an acid At a red heat the palt decomposes, evolving
carbonate which is stable only in solution. It oxygen, nitrogen, and nitrogen peroxide, and
dissolves readily in ammonium chloride, nitrate, leaving a residue of pure baryta. It detonates
and succinate, and when boiled with ammonium slightly with combustible bodies, and decomposes
chloride is totally decomposed, forming ammo- with a yellowish light when thrown upon the
nium carbonate and barium chloride. fire. It is largely used in pyrotechny for
giving
It is not decomposed at a strong red heat, green-coloured lights, especially fo.r the prepara-
but at the heat of a forge fire it fuses with loss tion of green fire ; and for the manufacture of saxi-
of carbon dioxide ; the tension of C0 2 emitted fraain, an explosive mixture of 76 parts of barium
at 1100 is 20 mm. ; at 1600 dissociation is nitrate, 2 parts of nitre, and 22 parts of charcoal.
complete. The decomposition is much more It dissolves in water, producing a slight
easily effected in presence of carbon, being depression of temperature ; 100 parts of water
complete at 1450. It is decomposed by steam dissolve 5-2 parts of barium nitrate at 0, 9-2 at
at a red heat, and very easily if mixed with 20, 17-1 at 50, and 32-2 at 100. It is less
an equal weight of chalk" or slaked lime. soluble in dilute nitric acid ; hence a second
The artificial carbonate is of considerable crop of crystals may be obtained from cooled
use in chemical analysis. saturated solutions on addition of a little nitric
Barium nitride Ba 3 N 2 .
Maquenne (Bull. Soc. acid. It is quite insoluble in concentrated nitric
chim. [3]368) obtained this compound by
7, acid and in alcohol.
passing nitrogen into a tube containing a 25 p.c. Hirzel (Zeitsch. f. Pharm. 1854, 49) obtained
amalgam at a red heat. Guntz and Mentrel a hydrate Ba(N0 3 ).,,2H 2 from a solution cooled
581) obtained it by heating barium
(ibid. (3) 29, below 12. Berry"(Chem. News, 44, 190), by
ammonium at 430. So obtained it is a light saturating the same water with barium and
porous material of a canary-yellow colour. It strontium nitrates, introducing a crystal of
decomposes water in the cold, giving ammonia Sr(N0 3 ) 2 ,4H 2 0, and evaporating over sulphuric
and Ba(OH),. acid in vacuo, obtained crystals containing 17 p.c.
Barium ammonium is formed by the action of a hydrated barium nitrate isomorphous with
of ammonia gas on barium or barium
amalgam the strontium compound.
below 28 but it is best prepared by dissolving
;
Barium monosulphide BaS is obtained in a
barium in dry liquid ammonia at 50, when pure state by passing sulphuretted hydrogen
it forms a dark-blue oily liquid immiscible \vith over heated baryta as long as water is formed.
the liquid ammonia. The compound is some- Veley (Chem. Soc. Trans. 1886, 369) prepared
what but a body having the formula
indefinite, pure crystals of the hydrate of barium hydroxide
Ba(NH 3 appears to exist.
) 6 Ba(OH),,8H 2 0, and heated them at 80 in a
Barium amide Ba(NH 2 ) 2 is obtained by current of hydrogen until they attained the
heating barium ammonium to 60 or by passing constant composition Ba(OH) 2 ,H.,0, when a,
ammonia over barium at 280*0. stream of sulphuretted hydrogen was passed
Barium nitrite Ba(N0 2 ) 2 ,H,0 is prepared over them, yielding pure BaS and water :
by heating the nitrate, dissolving in water, and Ba(OH) 2 ,H 2 0+H 2 S=BaS+3H 3 0.

precipitating any baryta formed by passing a It may also bo prepared by passing carbon
stream of carbonic gas through the solution, disulphide over red-hot baryta, or by reducing
adding alcohol to the filtrate to precipitate powdered barium sulphate in a stream of
the unreduced nitrate, and
evaporating to hydrogen.
the crystallising point. Or
by passing nitrous On the manufacturing scale it is prepared by
roasting 100 parts of heavy-spar with 20 parts
vapours into baryta water, evaporating to of
dryness, digesting in a small quantity of water coal flack or charcoal. If charcoal is used, a
the
(not sufficient to dissolve the nitrate) and crystal- thorough mixture must be effected, as
lising. It is most
readily prepared pure by reaction is otherwise very imperfect, owing to the
adding barium chloride to a boiling solution of non -fusibility of the mass. If the' slack of
silver nitrite,
filtering off the silver chloride, and bituminous coal is used, the ' caking supplies a
evaporating. carbonaceous material which readily permeates
It is permanent in the air,
readily soluble in the mass and ensures complete reduction. The
water or alcohol, and crystallises in colourless admixture of resin, oil, or sawdust is also advan-
prisms, either needle-shaped or, according to tageous, and the asphalt of gas
works is a
con-
Fischer, thick short prisms of 71|. capital reducing material, as the hydrogen
Barium nitrate Ba(N0 3 ) 2 native barium . A tained in it prevents the formation of poly-
nitrate has been discovered in Chili in the form
sulphides of barium. The mass thus
obtained
424 BARIUM.
contains excess of carbon and some undecom- which becomes white on cooling. It is insoluble
posed sulphate, but the barium sulphide may be in alcohol.
extracted by treating with hot water. Veley (Chem. Soc. Trans. 1886, 369) finds that
Another method is to heat a mixture of 100 the composition of crystals of barium sulphydrate
parts heavy-spar, 200 of common salt, and 15 is Ba(SH) 2 ,4H 2 O.
parts charcoal powder in a reverberatory furnace, Barium trisulphide BaS 3 is formed as a

the salt being added to assist fusion. greenish-yellow mass when 2 parts of barium
Barium sulphide forms a white mass of sulphide are fused with 1 part of sulphur, the ex-
hepatic odour and alkaline taste, soluble in water, cess of sulphur being distilled off below 360. It
forming a mixture of hydrate and sulphydrate : melts at 400 with loss of sulphur and formation
of a black liquid. On boiling for some time with
2BaS+2H 2 0=Ba(SH) 2 +Ba(OH),. water it dissolves to a red liquid which deposits
When exposed to the air it becomes converted on cooling crystals of the hydrated mono- and
into carbonate with evolution of sulphuretted tetrasulphades of barium.
hydrogen, owing to absorption of moisture and Barium tetrasulphide BaS 4 When 7 parts of
.
carbonic acid. When heated to redness in pre- barium sulphide are boiled in water with 4 parts
sence of aqueous vapour, it is converted into of sulphur, pale-red rhombic prisms are deposited,
barium sulphate with elimination of hydrogen. soluble in water to a red-coloured liquid from
It is decomposed by hydrochloric and nitric which alcohol precipitates it as an orange-
acids with formation of the chloride and nitrate coloured crystalline powder.
and elimination of sulphuretted hydrogen. Veley (Chem. Soc. Trans. 1886, 369) obtains it
Chlorine, bromine, and iodine decompose it with by dissolving sulphur in a warm saturated solu-
formation of chloride, bromide, and iodide, and tion of barium hydrosulphide the crystals which
;
deposition of sulphur. separate out have the composition BaS 4 ,2H 2 0.

The phosphorescent material known as Barium pentasulphide BaS 6 is obtained in
' '
Bolognian phosphorus is a sulphide of barium solution by boiling an aqueous solution of the
obtained by heating 5 parts of precipitated monosulphide with sulphur. On evaporation of
barium sulphate with 1 part of powdered char- the caustic alkaline yellow solution, crystals of
coal over a gas flame for half an hour, and then barium tetrasulphide and sulphur are obtained :
heating for ten minutes over the blowpipe ; it BaS 5 =BaS 4 +S.
must be sealed up while still hot in glass tubes. Barium sulphocarbonate BaCS 3 is deposited
After exposure to the sun's rays, or to any light as a canary-yellow crystalline powder when a
rich in ultra-violet rays such as that emitted by solution of barium stilphide is added to carbon
burning magnesium wire or the electric arc, it disulphide (Thenard, Compt. rend. 79, 673). On
phosphoresces in the dark with a brilliant the large scale 90 p.c. yield may be obtained,
orange-coloured light. Sulphides of barium, and Dumas suggested its use against the
strontium, and calcium are now manufactured phylloxera in wine districts. Thenard was of
for the preparation of luminous paints Avhich are opinion that this barium salt would be injurious
used for coating clock-faces, match-boxes, &c. to the soil, and proposed to convert it into the
Their surfaces are protected from moisture by a potassium salt by adding potassium sulphate to
thin coating of varnish. Barium sulphide is its solution.
now largely used in the manufacture of litho- Barium sulphite BaS0 3 is obtained as a white
phone by adding it dissolved in water to a crystalline precipitate by adding potassium or
solution of zinc sulphate. Mutual precipitation sodium sulphite to a soluble barium salt. Is
takes place, and the white powder formed, con- soluble in a warm solution of sulphurous acid,
sisting of zinc sulphide and barium sulphate, is and crystallises out on cooling in six-sided prisms.
used as a rubber filler. When heated in closed vessels it is converted
When a solution of 5 parts of barium sul- into a mixture of sulphide and sulphate, but
phide is boiled with 1 part of sulphur, and the heated in air the sulphate is the sole product.
solution evaporated over sulphuric acid in Birnbaum and Wittich (Ber. 13, 651) state that
vacuo, colourless six-sided transparent tables of BaO unites slowly with S0 2 at 200, but more
BaS,6H 2 are deposited, which are decomposed rapidly at 230, forming BaS0 3 .
by a small quantity of water, forming barium Barium sulphate BaS0 4 occurs in nature as
hydrosulphide which dissolves, and barium barytes, or heavy-spar, forming fine tabular
hydroxide which remains behind. crystals belonging to the rhombic system. It
Barium hydrosulphide Ba(SH) 2 is formed by is a very common mineral in metalliferous veins,
saturating a warm solution of barium hydroxide and is more particularly associated with lead,
or sulphide with sulphuretted hydrogen, evapo- silver, and cobalt ores. Clowes (Chem. News,
rating apart from the air and cooling, when 52, 194) states that the beds of the new red
crystals of baryta and yellow prisms separate sandstone near Nottingham are permeated by
out. The mother liquor is mixed with alcohol, minute crystals of heavy-spar, which acts as a
filtered from the sulphur and barium thio-
cementing material.
sulphate formed, and cooled to 10, when Crystals of artificial barytes, identical in form
colourless transparent four-sided prisms are and properties with native heavy-spar, may be
obtained. The crystals contain water, which obtained by fusing certain metallic chlorides,
they lose on heating, becoming white. Exposure such as those of manganese, sodium, potassium,
to air decomposes the crystals, with efflorescence, or even barium itself, gradually dissolving
into barium thiosulphate and sulphate. Heated barium sulphate in the fused mass, very slowly
in a retort, they lose their water of crystallisation
cooling, and afterwards extracting the
soluble
without fusing, evolving sulphuretted hydrogen chlorides with water. By this means Gorgeu
as the temperature approaches redness, and (Compt. rend. 96, 1734) prepared crystals much
leaving a yellow mass of barium monosulphide, larger than those obtained by the older process
BARIUM. 425
of fusing potassium sulphate with barium The crystals are soluble in 4 parts of water
chloride. The sp.gr. of the mineral and of the at 18 and in 1-1 parts at 100. When the
artificial crystals varies from 4-3 to 4-7. dry salt is heated, it breaks
up into sulphur
Barium sulphate has been formed by Spring dioxide and barium sulphate. The same de-
(Bull. Soc. chim. 46, 299) by subjecting an composition occurs on boiling with hydrochloric
intimate mixture of molecular proportions of acid, but the solution of the dithionate itself in
sodium sulphate and barium carbonate to great water may be boiled without decomposition.
pressure. It is precipitated as a heavy white A tetrahydrate BaS 2 O g ,4H 2 may also be
amorphous powder of sp.gr. 4 0-4 5 i when obtained by spontaneous evaporation in distinct
> i
sulphuric acid or a soluble sulphate is shining monoclinic crystals, which effloresce on

added to the solution of a barium salt ; this exposure to air.
precipitate is insoluble in water, very slightlv Barium thiosulphate

soluble in dilute acids, more so in strong acid?. BaS 2 3 ,H 2 O orBaH 2 (S0 2 ) 2
Concentrated sulphuric acid does not attack
is obtained as a white crystalline precipitate
anhydrous baryta, but pyrosulphuric acid when the sodium salt Na 2 S,6 3 is added to barium
attacks it so violently that the mass becomes
acetate it loses its water of crystallisation at
incandescent, and forms barium sulphate. ;
When freshly precipitated, it is readily soluble 215. The anhydrous salt, when heated to red-
in concentrated sulphuric acid at 100, the ness, gives off sulphur and leaves a residue of
barium sulphide, sulphite, and sulphate
solution depositing on cooling lustrous prisms :
of the acid barium sulphate BaH 2 (S0 4 ),,. If the 6BaS 2 3 =BaS+2BaS0 3 +3BaS0 4 +6S.
acid solution be exposed to the air, moisture is Barium selenide BaSe is formed by heating
taken up, and silky needles of a salt having the barium selenite to redness in a stream of hydro-
composition BaH 2 (SO 4 ) 2 ,2H 2 are deposited.
gen. It is decomposed by water into barium
Both these acid salts are decomposed by water,
hydroxide and a higher selenide, which is decom-
yielding sulphuric acid and the neutral salt. posed by acids with evolution of H^Se and
Barium sulphate is also soluble to a per-
precipitation of selenium.
ceptible extent in ammonium nitrate. Hydro- Barium selenate BaSe0 4 resembles the sul-
bromic acid solution containing 40 p.c. HBr
phate in being insoluble in water, but differs
dissolves it to the extent of 1 in 2500 parts acid from it in being decomposed by hydrochloric
(Haslam, Chem. News, 53, 87). acid into selenite, which dissolves in the hydro-
Barium sulphate is partially decomposed by chloric acid.
boiling with a concentrated solution of a fixed Barium chromate BaCr0 4 is precipitated as
alkaline carbonate into alkaline sulphate and a yellow crystalline powder when potassium
barium carbonate, but the reaction is much more chromate or bichromate is added to the solution
complete when the sulphate and alkaline car- of a barium salt. The salt may be obtained in
bonate are fused together. It is reduced to
green rhombic crystals isomorphous with BaS0 4
sulphide by ignition with charcoal or organic by heating two equivalents of BaCL with one
matter, also by ignition in a stream of coal gas
equivalent of potassium chromate and one of
or of hydrogen mixed with vapour of carbon
sodium chromate, and allowing the mixture to
disulphide. cool the chlorides may be boiled out with water,
;
Powdered heavy-spar is used to adulterate
leaving the right rhombic prisms of BaCr0 4 of ,
white lead, but has not sufficient body to form
a pigment by itself the amorphous sulphate is sp.gr. 4-6. They are insoluble in water, but
;
are easily soluble in hydrochloric and nitric
prepared on the large scale by precipitation of a acids, and are decomposed by sulphuric acid into
solution of barium chloride of sp.gr. 1-19 by one
BaS0 4 and Cr0 3 (Bourgeois, Compt. rend. 88,
of sulphuric acid of sp.gr. 1 -245, and is used as a
382).
pigment under the name of permanent white
' '
'
The precipitated chromate is used as a pig-
or blanc fixe.' ' '
ment under the name of lemon yellow or
Barium sodium sulphate BaNa 2 (S0 4 ) 2 is
yellow ultramarine.' When strong sulphuric
'
formed as an opaque hard mass of pearly lustre acid is added to the dry pigment, great heat is
by fusing together equivalent quantities of the developed, and it is coloured deep red from
sulphates of sodium and barium (Berthier). liberation of Cr0 3 If it be now ground in a
.
Barium disulphate BaS,0 7 If precipitated,

.
mortar and heated to bright redness, the
barium sulphate be dissolved in fuming sul- chromic acid is reduced to chromic oxide, and a
phuric acid, and the solution heated to 150, on fine green pigment is obtained (Douglas, Chem.
cooling a glistening deposit of granular crystals News, 40, 59).
of the disulpbate is obtained.
Decomposition of Barium dichromate BaCr 2 7 is obtained by
these crystals occurs at a low red heat without concentrated
dissolving barium chromate in hot
previous fusion. chromic acid. On cooling, red crystals of the
Barium dithionate BaS 2 6 ,2H,0. Prepared
composition BaCr.2 7 ,2H 2 are deposited, which
by adding barium sulphide to the manganese salt lose their water at 100, and are decomposed by
formed on passing sulphur dioxide water into the normal chromate and chromic
through finely
divided manganese dioxide suspended in water :
anhydride (Preis and Rayman, Ber. 13, 340).
MnS 2 6 +BaS=MnS+BaS 8 1!
.
Barium manganate BaMn0 4 is formed when
On allowing the solution to evaporate in a manganese dioxide is heated with barium car-
warm place, glittering monoclinic crystals of the bonate or nitrate as an emerald-green powder
salt are deposited of or
the composition BaS..j0 6 , consisting of microscopic four-sided prisms
2H 2 0. According Se'narmont and Ram-
to six-sided plates, insoluble in water but decom-
melsberg, the crystals are rhombic. According posed by acids. This salt is now used in place
to V. Lang (Sitz. B. of the poisonous Scheele's green.
[2] 45, 27), they are mono~-
clinic. Barium permanganate BaMngOg is
prepared
426 BARIUM.
by passing carbonic acid gas through water prepared by evaporating a solution of the di- or
containing barium manganate in suspension ; tri-barium salt in aqueous phosphoric acid. It
after filtering off the barium carbonate the red forms colourless crystals triclinic according to
solution is rapidly evaporated. Or it may be Erlenmeyer, with acid reaction ; soluble without
obtained by the action of barium chloride on decomposition in a small quantity of water, but
silver permanganate. decomposed by excess of water into free phc
Or potassium permanganate may be decom- phoric acid and the neutral salt.
posed by slight excess of hydrofluosilicic acid, Joly (Compt. rend. 98, 1274) states that
the mixture kept cool, and, after separation of the total weight of salt brought in contact witt
the precipitated potassium silicofluoride, the the same quantity of water increases in arithme
supernatant solution decanted and saturated in tical progression, the weight which is dissolve
the cold with barium hydroxide. After separation without decomposition decreases hi geometric
of the insoluble barium silicofluoride, the solution progression ; but as soon as half the original salt"
is evaporated until the barium permanganate has been decomposed a diacid salt is forme
separates out on cooling (Rousseau and Bruneau, BaO-2P 2 O 5 +arH 2 0, the proportion of whicl
Compt. rend. 98, 229). increases as the acidity of the liquid increase
It forms large orthorhombic octahedra, deep- and eventually exists alone in solution.
red and almost black, with a violet reflection. Dibarium orthophosphate Ba 2 H 2 (P0 4 )2
It is used for the preparation of permanganic BaHP0 4 is obtained as a white, scaly, crystal
acid and of the ammonium salt. precipitate when hydrogen disodium phosphat
Rousseau and Saglier (Compt. rend. 99, 139) is added to a neutral solution of a barium salt
find that on heating two grams of barium man- It is soluble in 20,570 parts of water at 20
ganate with ten grams of barium chloride for somewhat more soluble in water contair
four hours to 1500, and extracting with water barium or sodium chloride or ammoniacal salt
and dilute acid, a residue of small opaque From the solution in, nitric or hydrochloric acic
bluish-black crystals of 'barium manganite excess of ammonia precipitates the tribariui
BaMn0 3 remains; sp.gr. 5-85; readily soluble in salt or a salt intermediate between the two
hydrochloric acid with evolution of chlorine. Thus, according to Wackenrodcr, a solution of
The manganite is also formed when mixtures of BaHP0 4 in nitric acid yields, on addition
manganese chloride and barium oxychloride are ammonia, a precipitate of barium phosphat
heated below 1000 or above 1100. Between nitrate 4BaHP0 4 -Ba(N0 3 ) 2 , which leaves, or
these temperatures the product is barium di- heating, a mixture of di- and tri-barium phc
manganite BaO-2Mn0 2 which crystallises in
, phates.
brilliant black lamellae. At 1500 the manganite By precipitating a solution of dibarium phc
is reconverted to manganate. phate with alcohol, a salt intermediate betwe
Barium phosphide Ba 3 P 2 When vapour of
. the mono- and di-salts is obtained :
phosphorus is passed over red-hot baryta, a BaH 4 (P0 4 2 -2BaHP0 4 ,3H 2 0.

)
brownish-red mixture of barium phosphide and If a mixture of potassium silicate and bar
phosphate is obtained commonly known as
'
water boiled, and afterwards mixed with a
is
phosphuret of baryta.' It is decomposed by solution of potassium silicate containing a quan-
water, forming a solution of hypophosphite of
tity of potassium phosphate, on cooling, cubical
barium and evolving a mixture of free hydrogen BaKP0
crystals of the composition 4 ,10H 2
and spontaneously 'inflammable phosphoretted
separate out. BaNaP0 4 ,10H 2 O
was similarly
hydrogen. obtained in regular tetrahedrons (De Schulten,
Jaboin (Compt. rend. 129, 762) prepared the
Compt. rend. 96, 706).
phosphide by heating 100 parts of barium Tribarium orthophosphate, or neutral phos-
phosphate with 16 parts of lamp black in an phate of barium, Ba 3 (P0 4 ) 2 -H 2 is prepared by
electric furnace. The product so obtained has
adding hydrogen disodium phosphate to a solu-
a crystalline structure. It decomposes water, tion of barium chloride rendered strongly alkaline
yieldingPH 3 and Ba(OH) 2 .
by ammonia, and separates as a heavy granular

Barium monometaphosphate is obtained as
powder. It parts with a portion only of its
a white powder by evaporating a solution of water at 200.
barium carbonate in excess of metaphosphoric If a saturated solution of tribarium phos-
acid and heating the residue to 316. Its
phate in hj'drochloric acid is evaporated, on'
formula not known with certainty.
is
cooling, crystals of barium chloride are de-
Barium dimetaphosphate Ba(PO 3 ) 2 ,2H 2 is posited, more and more monobarium phosphate
formed as a crystalline sparingly soluble precipi- being left in solution, and if more hydrochloric
tate when barium chloride is added to a solution acid is added, all the barium may be crystallised
of the corresponding ammonium or sodium salt. out as barium chloride, and pure phosphoric
Barium trimetaphosphate Ba 3 P 6 18 ,6H 2 0, acid remains.
apparently a polymeric form of the last salt, is If the solution of tribarium phosphate in
produced when a solution of 1 part of the corre- hydrochloric acid is boiled, shining needles form
sponding sodium salt in 10 to 15 parts of water in the liquid, and on adding sufficient water to
is mixed with a nearly saturated solution of redissolve them, well-defined crystals of a phos-
3 parts barium chloride. On standing, the phato-chloride 4BaH 4 (P0 4 2 -BaCL are deposited
)
salt separates in monoclinic prisms, which give on standing (Erlenmeyer, J. 1857, 147).
off two-thirds of their water at 100, and the According to Ludwig, a solution of dibarium
rest at a higher temperature. phosphate in hydrochloric acid also yields, on
Barium hexametaphosphate is obtained as addition of ammonia, a phosphato-chloride con-
a gelatinous precipitate by precipitating the cor- taining 3Ba 5 H 2 P 4 q i6 -BaCl 2 -3H 2 O.
responding sodium salt with barium chloride. A salt intermediate between the di- and tri-
Monobarium orthophosphate BaH 4 (P0 4 ) z is phosphates, containing Ba 3 (P0 4 3 -2BaHP0 4
)
or
BARIUM. 427
Ba 6 H 2 P 4 O 16
formed when a solution of the
, is The hydrate, sulphide, chloride, bromide,
dibarium phosphate in hydrochloric acid is iodide, nitrate, and many organic salts of barium
mixed with a quantity of ammonia just sufficient are soluble in water, and all are poisonous. The
to precipitate it. majority of the remaining salts are soluble in
Barium pyrophosphate Ba 2 P a 7 Pyro- .
hydrochloric and nitric acids, whilst the sulphate
phosphoric acid does not precipitate barium and silicofluoride are insoluble in all acids.
salts, but with baryta water gives a precipitate Alkaline carbonates precipitate white barium
of barium pyrophosphate. Barium salts, how- carbonate, soluble in most acids, hence ammo-
ever, give with sodium pyrophosphate a white nium carbonate is used to precipitate it
(along
amorphous barium pyrophosphate,
precipitate of with the carbonates of strontium and calcium)
soluble in aqueous pyrophosphoric and sulphur- in qualitative analysis.
ous acids more soluble in hydrochloric or nitric
; Potassium and sodium hydroxides, free from
acid, but not perceptibly soluble in water con- carbonates and sulphates, give a voluminous
taining ammonium chloride or in acetic acid. precipitate of barium hydroxide Ba(OH) 2 with
Monobarium arsenate BaH 4 (AsO 4 ) 2 is ob- concentrated solutions soluble in more water.
tained by adding baryta water to aqueous arsenic Ammonia gives no precipitate.
acid until a precipitate begins to form, or by dis- Sulphuric acid, as well as all soluble sul-
solving the dibarium salt in aqueous arsenic phates, throws down barium sulphate from all
acid and leaving the solution to crystallise. solutions of barium salts. Pickering (Chem.
Dibarium arsenate News, 4G, 223) states that the smallest quantity
2BaHAs0 4 ,H 2 or BaHAs0 4 ,H 2 of barium which can be detected is 1 part in
833,000 parts of water. The presence of an
according to Berzelius, is obtained when a solu- alkaline citrate greatly interferes with the
tion of the disodium salt is added to excess of
precipitation. Strontium sulphate (which is
barium chloride. It gives up its water at a red
more soluble) forms a delicate test for barium.
heat, and in contact with water is decomposed
into the tribarium salt, which is precipitated, Phosphate, arsenate, borate, and iodate of
sodium also give precipitates soluble in acids.
and the monobarium salt, which dissolves.
Ammonium oxalate gives, from moderately
Tribarium arsenate Ba 3 (As0 4 ) is obtained as
dilute solutions, a white pulverulent precipitate
a white sparingly soluble powder by precipitating
of barium oxalate.
aqueous arsenic acid with baryta water, or bette^ Potassium chromate precipitates bright
by gradually dropping trisodium arsenate into
barium chloride, lemon-yellow barium chromate, soluble in nitric,
Barium silicate. Solutions of baryta, when hydrochloric, or chromic acid.
Hydrofluosilicic acid gives a colourless crys-
kept in glass bottles for any length of time, talline precipitate of barium silicofluoride ; this
deposit transparent rhombic crystals of the reaction will detect 1 part of the chloride in
composition BaSiO 3 ,7H.,0. These crystals lose 3800 parts water. The precipitate is nearly in-
their water a little above 100, and become more
soluble in nitric and hydrochloric acids,
turquoise-blue : they are decomposed by boiling insoluble in alcohol.
water (Le Chatelier, Compt. rend. 92, 931);
Barium is readily distinguished from lead
Cossa and Lavalle (Zeitsch. f. Chem. 11, 399).
(which also forms a sulphate insoluble in water) by
According to Le Chatelier, they may be readily the fact that sulphuretted hydrogen gives a black
obtained in a few dajs. by suspending calcined
lead salts.
silica in baryta water, when the sides become precipitate of lead sulphide with soluble
Soluble barium salts are at once distinguished
covered with crystals.
from those of strontium and calcium by the fact
Barium titanate. When equivalent quan- that they are immediately precipitated by a
tities of titanic
anhydride and barium carbonate solution of calcium sulphate, which only gives
are fused at a bright red heat for an hour with
a precipitate with strontium salts on standing.
excess of barium chloride, and the product
The acid reaction is also of
extracted with very dilute hydrochloric acid, a hydrofluosilicic
use hi separating barium from the other
residue of yellow microscopic crystals resembling
two metals. Barium chloride is insoluble in
cubes and octahedra of tbe composition
alcohol, whilst the chlorides of strontium and
2BaO-3TIO, calcium are soluble, and the nitrates of barium
and of sp.gr. 5-91 remains undissolved. These and strontium are insoluble, in alcohol, whilst
crystals are found on examination by polarised calcium nitrate is soluble. From these facts a
light to consist of aggregations of rhombic scheme of separation is readily derived, the pre-
and
lamellae. cipitated carbonates of barium, strontium,
Reactions of the compounds of barium. calcium being converted into chlorides, and the
When heated on a thin platinum wire in the chlorides of strontium and calcium dissolved out
of
inner blowpipe flame, or when brought into any by alcohol, leaving a residue of chloride
non-luminous flame, barium compounds impart a barium. The strontium and calcium may then
yellowish-green colour to the outer flame. When be separated by converting their reprecipitated
viewed through the spectroscope two green lines carbonates to nitrates and dissolving out the
Baa and Ba/3 come out most intensely Ba7, ;
calcium nitrate (v. ANALYSIS).
though not so marked, is also a characteristic Estimation of barium. When no other
line.^
Besides these, there are numerous lines alkaline metal is present, barium may be esti-
in the red and
yellow and one broad indis- mated as sulphate. A solution of the chlorides
acid is best.
slightly acidified with hydrochloric
tinct line in the blue, close to Fraunhofer's F.
Bunsen found that
salt may be detected
^
of a milligram of barium
spectroscopically. Silicates
Sulphuric acid is added cautiously
solution in slight excess.
to the hot
The precipitate is
of barium
give this reaction on moistening with allowed to settle in a warm place for some hours
strong hydrochloric acid.
!
before filtering.
428 BARIUM.
In its organic salts barium may bo estimated
as carbonate by heating in a platinum crucible
and subsequent moistening of the residue with
a concentrated solution of ammonium car-
bonate, evaporation, gentle ignition, and weigh-
ing.
Where strontium and calcium are present,
after the separation of the other elements, the
alkaline earths are precipitated by ammonia and
ammonium carbonate. This precipitate is then
dissolved in acetic acid, and the barium twice
precipitated as chromate, in which form it may
be weighed or dissolved in hydrochloric acid,
then precipitated, and weighed as sulphate.
G. S. B.
BARK BREAD. A kind of bread which was
formerlymade by the peasants in various parts
of Norway from the inner bark of Pinua sylvestris
(Linn.).
BARKLYITE v. CORUNDUM.
BARLEY. Two species are in common
cultivation Hordeum distichum, two-rowed,
and H. vulgare, six-rowed. Many varieties are
known, differing in size and shape of ear and
grain. The two-rowed varieties are chiefly
grown as spring-sown crops, while the six-rowed
varieties are often sown in the autumn.
The grain resembles in composition that of
other cereals, but contains less gluten than
wheat ; moreover, the gluten of barley is not
so tenacious as that of wheat ; consequently,
barley meal does not yield a satisfactory bread.
Barley is chiefly grown for cattle-feeding and
for malt production. For the latter purpose, a
grain containing but little nitrogenous matter is
preferred, so that too lavish nitrogenous manur-
ing must be avoided in the production of malting
barley.
The following are analyses of typical average
barley as given by 1, Warington ; 2-5, Kellner
(German) ; 6, Wiley (of American barley).
The tablerepresents the composition of
barley' expressed in the usual manner. The
'
item nitrogenous substances is simply the
total nitrogen X 6-25. Of the total nitrogen, a
email portion probably about -fa is present in
non-albuminoid form.
BASSIA OR MAHWA FLOWERS. 429
Barley Straw is much more affected in com- distinguished from calcite by its heaviness
position than the grain by
the richness or poverty (sp.gr. 4-5), and from both calcite and witherite
of the soil, and by the conditions under which it by not effervescing with acid. The massive
is grown. If the ripening of the grain has been material is often white and opaque but crystals ;
robbed of its nitro- are sometimes transparent and colourless, or with

fully completed, the straw is
genous matter and phosphates to a much greater brownish, greenish, or bluish shades of colour.
extent than when the seed has not been fully Barytes is usually met with in veins, often
matured. Thus the straw of a crop cut before it in association with ores of lead. Some of the
is fully ripe possesses much higher feeding value old lead-mines of the north of England and
than usual. Shropshire are now being reworked for barytes.
According to Kellner, the following repre- A remarkable vein of barytes, consisting of pure
sents the average composition of barley straw : white massive material with a thickness varying
Soluble from a few inches to 16 feet, is extensively
Ether carbohy- worked in the coal-measures at New Brancepeth
Water Protein extract drates Fibre Ash near Durham
Colliery, (L. J. Spencer, Mineralog.
Summer barley 14 -3 3-5 1-4 35-9 39-5 5-4
1-4 33-5 42-0 Mag. 1910, xv. 302). Beautiful crystallised
5-6
Winter barley 14-3 3-2
specimens are abundant in the haematite-mines
The ash of barley straw (Wolff) contains : of west Cumberland, but, owing to the brown
K-iO Na 2 O CaO MgO Fe 2 Os P 2 Os SOs SiO 2 Cl or yellow colour of this material, it is of no
23~-3 3-5 7*2 2-6 1-1 4-2 3-9 51-0 3-2 commercial value.
Barley straw consists largely of cellulose, and Barytes is mainly used ha the manufacture
pentosans and lignose. The amount of pento- of paints, not only of white paint, but as an
sans has been estimated at about 25 p.c. The inert body in coloured paints. It is often sug-
'
given in the above table is gested that barytes is used for adulterating
'
crude protein
probably nearly all true albuminoids, since direct various articles. Barium sulphide and carbonate
experiments showed about 91 p.c. of the total are also prepared from barytes by roasting it
nitrogen to be present as albuminoids. The with coal, and from the product, barium chloride
lowest portions of the stems are least nutritious, is largely obtained. In preparing the crude
while the uppermost leaves and top of the stem barytes for the market, it is coarsely crushed
are the most digestible and richest in protein. and hand-picked; or when mixed with rock and
When barley precedes clover, as is often the dirt, these are separated by agitation (jigging)
case in England, the barley straw is enriched by in water. Coloured impurities are sometimes
including a portion of young clover plants. extracted by steam -boiling with sulphuric acid.
Under such circumstances, the product is of The purified material is kiln-dried and reduced
much higher feeding value, and contains more to very fine white powder in a ball- mill provided
protein (up to 6 or 7 p.c.), and soluble carbo- with screens, or between millstones. The
hydrates (38 or 39 p.c.), and less crude fibre. barytes flour so prepared still consists of minute
crystalline (cleavage) particles, and it is this
BARUS CAMPHOR v. CAMPHOBS.
' '
that gives the tooth or adhesive properties
BARUTIN. Trade name for the double salt to the coarser barytes paints. The finer
of theobromine barium and sodium salicylate; qualities are prepared from precipitated barium
a white amorphous powder of sweetish taste and sulphate ; and this is also used for dressing cloth
alkaline reaction, sparingly soluble in water. and leather, and for producing the smooth
' '
Used in the treatment of renal disease. V. SYN- coating on art papers. L. J. S.
THETIC DRUGS. BARYTIC WHITE or PERMANENT WHITE
BARWOOD v. SANDEBSWOOD. or BLANC FIXE v BARIUM ; also PIGMENTS.
.
BARYTA, GREEN, v. BARIUM. BARYTO CjELESTITE v. BARIUM.

BARYTES. Barite, or heavy-spar (from BASE OILS v. OILS and FATS.
0apus, heavy) a common mineral consisting of
; BASIC BESSEMER STEEL v. IRON.
barium sulphate (BaSOJ, and crystallising in BASILICON. Eesin cerate. A mixture of
the orthorhombic system. The name barytes oil, wax, and resin.
is, however, sometimes loosely, but incorrectly, BASIL OIL v. OILS, ESSENTIAL.
applied to include both this species and the BASLE BLUE v. AZINES.
mineral witherite (BaC0 3 , q.v.), or these are
' '
BASSIA or MAHWA FLOWERS. The
occasionally referred to as sulphate of barytes flowers of B. (illipt) latifolia (Roxb.) or Mahwa,
' '
and carbonate of barytes respectively. The a tree growing to the height of 60 feet, very
reason for this confusion is that the two minerals abundant in Central India, are very succulent,
are often mined together, although they are not and fall from the tree in large quantities every
night, a single tree affording from 200
always put to the same uses. to 400 Ibs.
Barytes is frequently to be found as well- of flowers in a season, which lasts during March
developed crystals, which vary considerably in and April. They are used as an article of food,
their appearance and habit. They possess a both cooked and raw. By fermentation and dis-
perfect cleavage parallel to the base, and per- tillation they yield upwards of 6 gallons of proof
pendicular to this are two prismatic cleavages spirit per cwt.
of superior quality, and
It is
parallel to the faces of the primitive rhombic when the operations have been carefully per-
prism, and thus inclined to one another at an formed, is very much like good Irish whisky,
angle of 78 22'. With these three directions having a strong smoky and rather foetid flavour,
of perfect
cleavage, massive barytes sometimes which disappears with age.
presents a certain resemblance to calcite, and They have also been used as a cattle food
its hardness is also about the same
(H.=3). with success. It is said that the flesh of pigs and
The angles between the cleavages are, however, other animals is much improved, acquiring a
different and, further, barytes may be readily
; delicate flavour.
430 BASSIA OR MAHWA FLOWERS.
The dried flawers have been recommended bitter principle (saponin) contained in the cakes,
as a source of sugar. Negri found in them they are unfit as food for cattle. Nevertheless,
57-9 p.c. of glucose, yielding 26-74 p.c. of alcohol the cake is frequently added as an adulterant to
'
on Chim. Med. Pharm.
distillation (Rev. 2, 384 ; the so-called native linseed cake,' which, under
cf. von Lippmann, Ber. 1902, 35, 1448). this misleading name, has latterly found ex-
BASSIA OILS. Under this name are com- tensive sales on the Continent. The seeds and
prised a number of oils belonging to the the oil have recently become an important
genus Bassia. The most important oils (or fats) article of commerce. They are imported to
derived from Bassia species are Mowrah Seed :
Europe in irregular quantities, and are chieflj
Oil, lUipe' Butter, Shea Butter, Njave Oil, and used in the soap and candle industries. En-
Phulwara Butter. deavours have also been made to convert the
Mowrah Seed Oil is the fat obtained from the fat into an edible fat. In India, Mowrah seed
seeds of Bassia latifolia (Roxb.) (Illipe latifolia, oil is largely used as an edible fat under the
Roxb. or Engler: Bassia villosa, Wall.), a tree name Dolia oil,' and as a medicinal oil in the
'
'
widely distributed in the northern provinces of treatment of skin diseases under the name Me
India, and especially in Bengal. The tree is oil.'
frequently cultivated in East India, and forms Illipe Butter is obtained from the seeds of
small plantations but even under the incentive
;
Bassia longifolia (Linn. ), a tree indigenous to the
of modern demand for a solid fat, the cultivation southern part of India a variety of this Bassia
;
of the Mowrah Seed tree for the production of species is known as Illipe malabarica (Konig), in
fat is not likely to be taken in hand in the near the Western Ghats from Kanara to Travancor
future. The tree gradually disappears towards and the Anamalais, where the tree is found at
Calcutta, and is only sparingly met with in the an altitude of about 4000 feet. The seeds be
Madras presidency, where its place is taken by a close resemblance to those of B. latifolia,
Bassia longifolia (see below). but are mostly 3-4 cm. long, and less rounded
The kernels are 1-2 cm. long, and are enclosed than the seeds of B. latifolia. The averag
in a light-brown shiny husk. The seeds are very weight of one seed is 1-4 grms. The kernel
similar in appearance to those of Bassia longi- form 75 p.c. of the seeds, and contain 50-55 p.c.
folia, with which they are frequently con- of a white to light-yellow coloured fat. The fat
founded, much as the fat obtained from both closely resembles Mowrah seed oil, but diffe
species is frequently confounded in commerce. from it by its lower solidifying and meltii
This is partly due to the fact that the two kinds points ; in correspondence therewith the iodine
of fats are mixed together when exported to value of the fat is 58-64, i.e. higher than that
Europe, a practice which is greatly favoured of B. latifolia. The fat contains from 12
by the fact that both species are known to the 20 p.c. of stearic acid ; arachidic acid is absent
natives under such similarly sounding names (Menon).
as Illipi, Elupa, Katillipi. Illipe seeds are imported into France anc
The kernels dried at 100 contain, according England (mostly admixed with Mowrah seeds)
to Valenta : where the fat is expressed for use in candle
Fat extracted (by petroleum ether) . 51 -14 making. The proposal to employ the fat as a
chocolate fat appears to be due to the confound-
soluble in absolute alcohol . .7-83
Tannin 2-12 ing of true Illipe seeds with seeds from the
Bitter principle, soluble in water . .0-60 Malayan States, erroneously described in the
' '
French market as Illipe nuts.
Starch 0-07
Shea Butter is the fat obtained from the
Vegetable mucilage . .1-65
. .
seeds of Bassia Parkii, De C. (Hassk.), Buty
Albuminous substances soluble in water 3-60
spermum Parkii, [G. Don] (Kotschy), a
Extractive substances soluble in water 15-59 .
belonging to the Sapotacece. The tree

Insoluble proteids . . . .4-40 first described by Mungo Park, who found it ir
Total ash 2-71
the kingdom of Bambara. Hence the fat wa
Fibre and loss 10-29
known as Bambara fat and also Bambooi fat
In its fresh state the fat is yellow on ex- ; Other native names are Galam Butter, Bambt
posure to the air the colouring matter is bleached. Butter, and, in French West Africa, Karite' Oil
The oil can also be bleached chemically, as has The Shea Butter tree, or Karite tree, resemble
been done by the author, on a large scale. in appearance the American oak, grows to
The fat has the sp.gr. of 0-9175 at 15, melts height of about 40 feet, and occurs in enormon
at about 25-3-30, and solidifies at 18-5-22. quantities on the West Coast of Africa, anc
The fat has a bitter aromatic taste and a through the centre of Africa in the French anc
peculiar odour. The iodine value of the fat is English Soudan. It is especially abundant ir
50, thus indicating a considerable amount of the middle basin of the Niger, and is as ch
oleic acid. The chief constituent of the solid racteristic of the region of the middle Niger as is
fatty acid "is arachidic acid is
palmitic acid ;
the palm tree of the lower reaches of the river
absent ;
found to occur
stearic acid has been and of the coast line. The Shea nut has the
in specimens examined recently in the author's size and shape of an ordinary plum ;
the out
laboratory by Menon, to the extent of from shell of some specimens is covered with fine
13 to 25 p.c. The saponification value of the fibres, whereas the shell of nuts coming froi
commercial fats is slightly lower than that of the middle Niger district has a polished surfa
fats having the constitution due to the fatty Owing to the wide distribution of the tree, the
acids named, owing to a somewhat high pro- different specimens of nuts and fats exported
portion of unsaponifiable matter, viz. 2-34 p.c. to Europe show characteristic differences. A
The fat is prepared in India in a crude manner, special variety appears to be represented by
and the cakes are used as manure. Owing to a the specimen known as Bassia niloticum (Kot-
BAST FIBRES. 431
sohy et Chevalier). (For a table stating the an extremely poisonous saponin, contained in
different yields of fat from different specimens, the fresh seeds, is completely removed, so that
and some of their characteristics, see Lewko- the fat can be used for edible purposes. In
witsch, Chemical Technology, &c., ii. 433.) case the seeds should be expressed on a large
The natives extract the fat by pounding the scale the press cakes would retain the poisonous
kernels and boiling the paste with water. The substance, and hence be valueless as a feeding
fat rises to the surface and is skimmed off into cake (Der Tropenpflanzer, 1910, 29), unless the
large calabashes, in which
it is carried to the saponin be removed completely by boiling out
river for shipment. Since little care is taken with water. But even if this process were
in the preparation of the exported oil, most feasible, a considerable amount of nutritive
of the shea butter that came until recently substances would be removed thereby. The
to Europe had a dark-grey colour, which was economic prospects of the seeds are, there-
considered to be characteristic of shea butter. fore, still doubtful nevertheless, the exports
;
The fat used by the natives for their own pur- from the German Cameroons have increased
poses is, however, prepared in a more careful from 3 tons in 1906 to 183 tons in 1908.
manner, made into cakes and wrapped round Phulwara Butter is the fat expressed from
with leaves, so that the fat may keep. This the kernels of Bassia (Illipe) butyracea (Roxb.),
'
fat is of a white colour, and keeps well for several the Indian butter tree,' which is indigenous to
months. the Himalayas. The seeds are smaller and
Shea butter plays a very important part thinner than those of B. latifolia and longifolia.
in the economy of the natives as an edible fat, The average weight of one seed is one gram.
and also as a burning oil, and for cosmetic The kernels form 67-5 p.c. of the total seed -,
purposes. Attempts have been frequently they contain 50-65 p.c. of a white fat, having
made to ship the fat and the nuts in bulk to the consistence of lard. Phulwara Butter is
Europe. Owing partly to the careless prepara- one of the most important foodstuffs amongst
tion, and partly to a resinous substance dissolved the natives of the North-West Provinces, on
by the fat, shea butter contains considerable account of its pleasant odour and agreeable
amounts of unsaponifiable matter which imparts taste. The butter is also highly valued by the
to the fat an indiarubber-like taste. This large natives as an ointment when properly perfumed.
amount of unsaponifiable matter precludes the The melting-point of the fat is 39, and its
employment of the fat for soap-making pur- iodine value 42. Stearic acid is absent (Menon).
poses ; it is, however, used in candle-making. Less -known Bassia Oils are Payena Oil or
:
The specific gravity of the fat is 0-9177 ; its Kansive Oil, from Payena oleifera (Chemical
melting-point varies from 25 to 28. Owing Technology and Analysis of Oils, Fats, and
to the considerable amount of unsaponifiable Waxes, ii. 800), and Ratio Oil, from an undeter-
matter, the saponification value varies from 171 mined species of Bassia (Brooks, Analyst, 1909,
to 192. The iodine value varies from 56 to 63, 207). J. L.
so that the proportion of oleic acid in the fat BASSWOOD OIL. An
from Tilia ameri-
oil
may be taken to reach about 60 p.c. The cana, resembling cotton-seed oil, and consisting
author found in a number of shea butters from of glycerides rich in butyric acid (Wiechmann,
33 to 37 p.c. of stearic acid. The remainder Amer. Chem. J. 1895, 17, 305).
of the fatty acid appears to consist of lauric BAST FIBRES. Elongated narrow plant-
acid (Southcombe, J. Soc. Chem. Ind. 1909, 499). cells that form strengthening tissue in stems and
Njave Oil, Njave Butter, Nari Oil, Noumgou leaves, especially in connection with the fibro-
Oil, Adjab Oil, is the oil obtained from the seeds vascular bundles, but not belonging to the wood.
*
of Mimusops Njave (De Lanessan), syn. Bassia The raw material, bast or bast -like fibre, used for
Djave (De Lanessan); Bassia toxisperma (Raoul) textile purposes or for the manufacture of paper,
Tieghemella africana (Pierre); Baillonella toxi- ropes, and the like, is of varied nature and
sperma (Pierre) ; Baillonella Djave (Pierre) ; source, but is always characterised by the
Tieghemella Jollyana (Pierre), a tree belonging abundance in it of bast fibres. It may be
to the family of the Sapotacece. The wood of composed of a number of fibro-vascular bundles,
this tree is known in commerce as ' Cameroon or one such bundle (e.g. coco-nut fibre), or part
mahogany.' The tree is indigenous to West of fibro-vascular bundle (e.g. fibre from leaves of
Africa, the Cameroons, Gaboon, Nigeria, and monocotyledons), or merely a bundle of true
furnishes, like most trees belonging to the bast fibres (from the fibro-vascular bundles or
Sapotacece, guttapercha. The fruits are bark of dicotyledonous stems).
known in commerce as ' Mahogany nuts ' ; in the A typical bast fibre has a thick wall, with
Gold Coast Colony they are known as ' Abeku ' slit-like oblique pits, and a relatively small
'
and Bako '
nuts. The weight of the nuts lumen. The ends usually taper to fine points,
varies between 10 and 21 -6 grams., one-third of but may be blunt or even branched. The cell-
which is made up by the shell. The kernels wall varies in thickness in different species, from
contain 43-64 p.c. of a white fat, which the comparatively thin to extremely thick,
and may
vary in the same fibre, so that the lumen
natives (the Jaundes and the Ngumbas) prepare is alter-
nately wider and narrower. When

by drying the seeds over fire and breaking the the wall is very
shell with stones. The kernels are then pounded thick the lumen is reduced to a line, and may
in a mortar or comminuted be locally evanescent. There are similar differ-
" rubbing between
by
stones. The mass is next boiled out with ences in the width, length, and strength of the
water, the fat is skimmed off
by hand, and raw material and individual bast fibre. The
freed from the bulk of water
by squeezing colour varies from the usual whitish-grey or
between the hands, and then subjecting it to a green or yellow, through yellow and
brown to
somewhat stronger pressure in baskets, by black.
Heaping stones on the mass. By this process The cell- wall is mainly composed of celluloses
432 BAST FIBRES.
and in certain species (flax, Calotropis gigantea, BAUXITE. A clay -like aluminium hydroxide
and others) is entirely soluble in ammoniacal first noticed by P. Berthier in 1821 (alumine
cupric oxide, and gives the colour reactions for hydratee des Beaux), and named beauxite b,\
celluloses ; but the bast fibres of certain other A. Dufrenoy in 1847, and bauxite by H. Sainte
species (jute, hemp, esparto, and others) show Claire Deville in 1861 ; this name being fror
lignification, and give corresponding colour the village Les Beaux, or Les Baux, near Aries
reactions. dep. Bouches-du-Rhone, in the south of Franc
Bast fibres in commercial use are mainly where the material was found. This materia
obtained from comparatively few alliances and came to be regarded as a mineral species wit
families of dicotyledons, and genera of mono- the composition A1 2 3 ,2H. or A1(OH) 2 , cor
!
cotyledons, namely, Malvales (Malvaceae), spending with A1 2 3 , 73-9 ; and H

2 0, 26-1 p.c.
Tiliacese, Sterculiacese, Urticales
(Moracese, that is, intermediate between the definit
Urticaceae, Ulmaceae), Leguminosse, Linacese, crystallised species diaspore (A] 2 3 ,H 2 0) ant
Apocynaceae, and Asclepiadacese, Boraginacese ; hydrargillite or gibbsite (A1 2 3 ,3H,0). It
Agave and Fourcroya, Aloe', Bromelia, Sanseviera, however, varies widely in composition, owii
Musa, Stipa, Pandanus, and several palms to intermixture with quartz -sand, clay, anc
(See articles on any of these, and JUTE and iron hydroxide, and it passes insensibly int
HEMP. For a full authoritative account of clays, iron-ores, and laterite. The variations
vegetable fibres, see Wiesner, Die Rohstoffe des shown by different analyses are : A1 2 O 3 , 30-
Pflanzenreichs, 1903, Bd. ii. 167-463.) -76-9; H 2 O, 8-6-31-1; Fe.,0 3 , l~48-8;
;
BATATAS, or Sweet Potatoes, the tubers of Si0 2 , 1-1-^1-5; Ti0 2 , 1 -6-4-0 "(from table
Ipsomcea batatas or Batata edulis, a convolvulus- analyses quoted by G. P. Merrill, The Non-
like plant, usually with purple flowers, growing metallic Minerals, New York, 1904). (Fc
freely in tropical and sub-tropical countries. The other analyses of French bauxite, j
tubers are sometimes of great size up to 12 Ibs. Arsandaux, Compt. rend. 1909, 148, 936, 1115.)
or more in weight. The material never shows any indicatior
It can be propagated by cuttings or by the of crystalline structure, being always com-
tubers, and, once established, often yields several pact or earthy, or often with a concretionar
crops in succession. An average crop is about (pisolitic or oolitic) structure. In colour
5 tons per acre. Light friable soils are most ranges from white, through creamy and yellow,
suitable. to brown and deep red. Under the microscoT
Average composition of sweet potatoes and it shows only optically isotropic, floccule
their vines :
grains. Bauxite is thus no doubt a mixtu
Soluble of colloidal aluminium hydroxides (for whit
carbohy- the mineralogical name kliachite has
Water Protein Fat d rates Fibre Ash
Tubers . 71-1 1-5 0-4 24-7 1-3 1-0 proposed by F. Cornu, 1909) with various iror
Vines . 41-6 7-6 2-1 29-3 13-6 5-8 hydroxides, clays, &c., and possibly also tt
crystalloids diaspore and hydrargillite ; and
A more detailed analysis of the tubers as grown is thus rather of the nature of a rock than'
in Monte Video, is given by Sacc (Bied. Zentr.
simple mineral.
1883, 337) :
In its mode of occurrence, and no doubt ,
Pectic in its mode of origin, it also shows wide differ

Water Protein Glucose Mucilage acid Starch Fibre Ash ences. The extensive deposits in the south
67-0 0-56 0-3 M5 1-27 13 10 1-0
France have the form of beds interstratified wit
to to to to to limestones of Cretaceous age, or of irregul
68-2 0-64 4-0 15 17-8
pockets in the limestone. Those of Co. Antrir
The sweet potatoes are largely used as food, and of the Vogelsberg and Westerwald ir
and also in the manufacture of alcohol. Germany, are associated with laterite, and
According to Stone (Ber. 1890, 23, 1406), they interbedded with basaltic lava-flows. In
contain from 1-5 to 2-0 p.c. of cane sugar, and kansas the bauxite deposits occur only
baking converts the starch into the soluble form Tertiary areas in the neighbourhood of eruptiv
and hydrolyses the cane sugar. The tops of syenites, while in Alabama and Georgia thej
sweet potatoes are greedily eaten by farm overlie ancient sedimentary rocks. The fr
animals, but should be used with care, since quent presence of pisolitic structures in tl
they sometimes contain a poisonous cyanogetic material and its association with limestones,
glucoside. Amounts of hydrocyanic acid, varying led to the suggestion that bauxite has
from 0-014 to 0-019 p.c. of the green material, have deposited by hot springs containing aluminiur
been found. Sweet potato vines have often salts in solution (probably aluminium sulphat
proved fatal to pigs in Queensland. H. I. from the decomposition of pyritous shales)
BATH BRICK. A brick made from deposits where these have come into contact with lime
of silicious and calcareous earth at Bridgewater, dtone rocks. On the other hand, the materia
Highbridge, and elsewhere, and used for polish- associated with laterite and basalt has, nc
ing metals. doubt, been produced by the weathering unde
BATH-METAL. An alloy of copper and special conditions (the agency of bacteria ha
zinc, containing a larger proportion of copper been suggested) of basalt or of other igneou
than ordinary brass, viz. 83 p.c. copper to 17 p.c. and crystalline rocks. (For papers on the cor
zinc; sp.gr. 8-451; fracture crystalline, and stitution of bauxite and laterite ; see e.g.
colour yellowish-red. Bauer, Jahrb. Min. 1898, ii. 163; and T.
BATIST. A
material consisting of cotton HoUand, Geol. Mag. 1903, 59.)
impregnated with caoutchouc on one or both The alum-clay or bauxite mined in
sides, largely used in the French army for Antrim is all sent to the aluminium works
compresses and antiseptic dressings. Foyers and Kinlochleven in Scotland.
BEAN. 433
France the present source of supply is mainly The most important species of beans are :
in dep. Var ;
and in America the production (1) Adzuki beans (Phaseolus radiatus).
is confined to the states of Alabama, Georgia, (2) Field or horse beans, of which the broad
and Arkansas. The French bauxite is roughly bean is a variety ( Vicia faba).
divided into three classes : (1) white bauxite, (3) French or kidney bean (Phnscolus
with 60 p.c. alumina, not more than 4 p.c. iron, vulgaris).
and no silica, this being used for the manu- (4) Java or Lima bean (Phaseolus lunatus).
facture of aluminium salts and alum ; (2) red (5) Soy or Soja bean (Glycine hispida or
bauxite, with 60 p.c. alumina and 3 p.c. silica, Soja hispida).
used for the manufacture of aluminium ; (3) a (6) Velvet bean (Mucuna utilis).
special kind of white bauxite, with 45 p.c. (7) Carob or locust bean (Ceratonia siliqua).
alumina, a trace of iron, and much silica, used In chemical composition beans are remark-
for making refractory bauxite bricks. The able for the large proportion of albuminoid
greater part of the material is used in the matter which they contain. They thus possess
manufacture of aluminium, but in America high nutritive value as foods.
large quantities are fused in the electric furnace In some cases the seed only is eaten, either
to produce artificial corundum, which, under the green as in broad beans, or dried as in haricot
name of alundum, is largely used as an abrasive beans, which are a variety of Phaseolus vulgaris.
agent. L. J. S. In others, e.g. in the kidney bean, the whole
BAYBERRY TALLOW v. WAXES. pod, in the unripe condition, is eaten ; whilst in
BAY-LEAF OIL v. OILS, ESSENTIAL. the case of the carob bean, the dried pod rather
BAY-SALT v. SODIUM CHLORIDE. than the seeds is the valued product. The
BDELLIUM v. GUM RESINS. velvet bean is usually grown for its foliage,
BDELLIUM RESIN v. RESINS. either for making into hay for cattle or for green
BEAN. The name given to many seeds which manuring.
resemble in size and shape the ordinary kidney In the following table are given analyses
bean. Thus the seeds of coffee, cocoa, castor, &c., of various beans, as far as possible of the
' '
are often known as beans. Usually, however, the products as they are usually consumed as
term is restricted to seeds of various leguminosce. food :
434 BEAN.
and Henry (Proc. Roy. Soc. 1903, 72, 285) found dioxide, 7 of carbon monoxide, 0-5 of marsh
a glucoside which they named phaseolunatin gas, 0-05 of hydrogen, and 0-45 of water (Dingl.
H
C 10 17 6 N, yielding dextrose, prussic acid, and poly. J. 238, 55).
acetone on hydrolysis. The wild plant contains The tar contains phenol, cresol, phlorol,
it in much larger quantity than the cultivated guaiacol, and creosol, the dimethyl ether of
one. From haricot beans Tatlock and Thomson propyl pyrogallol, the dimethyl ether of pyro-
(Analyst, 1906, 31, 249) obtained from 0-001- gallol, which on oxidation yield coerulignone or
0-009 p.c. of hydrocyanic acid. Most of the cediret, pittacal, and picamar.
cyanogen compound, and the whole of the According to Gratzel (J. Pharm. [5] 6, 520),
enzyme which hydrolyses it, are destroyed by ferric chloride colours beech tar creosote a blue
boiling. passing to brown.
The carob or locust bean is remarkable for (For a history of the investigations made upon
the large amount of sugar (cane sugar 23 p.c., wood Schorlemmer, J. Soc. Chem. Ind.
tars, v.
glucose 11 p.c.) contained in the pod, while 4, 152, where also will be found a bibliography
the seed contains a carbohydrate, caroubin, of the subject ; v. also CREOSOTE, and WOOD,
a white, spongy, friable substance, of the same DESTRUCTIVE DISTILLATION OF.)
composition as cellulose (Effront, Compt. rend. BEESWAX v. WAXES.
1897, 125, 38), which yields hi contact with BEET-ROOT. The root of Beta vulgaris
water a very syrupy liquid or jelly, 3 or 4 grams (Linn.). Many varieties are known, differing in
of the substance being sufficient to convert a colour, shape, and size. Mangel-wurzel, or
litre of water into a thick syrup. Caroubin mangold, as it is often called, is a variety (of
might be used with advantage in the prepara- which there are many sub-varieties), largely
tion of nutrient media for bacteriological work. grown as winter food for cattle garden beet -root,
;
It has been introduced under the name of employed as salad or vegetable, is often under-
' ' '
'
tragasol as a,
gum for sizing, colour printing stood when the term beet-root is used. The
and dyeing (J. Soc. Chem. Ind. 1894, 410, and most important variety, however, is the sugar
1896, 112). beet, of which many sub-varieties are known.
Effront (Compt. rend. 1897, 125, 309) These have been obtained by careful selection
states that by hydrolysis, either by dilute with a view to obtaining the highest proportion
acids or the enzyme caroubinase, present in the of cane sugar.
seeds, caroubin yields a sugar, which he calls The presence of sugar hi the juice of beet-root
caroubinose, resembling dextrose, but with lower was observed in 1747 by Marggraf, who suggested
rotatory power. its extraction on a commercial scale. The
Van Ekenstein (Compt. rend. 1897, 125, 719), early attempts, however, proved failures, as
however, finds this sugar to be identical with the process could not compete with the cane-
d-mannose. So, too, Bourquelot and Herissey sugar industry. This is not surprising when it is
find that the action of dilute acid upon the remembered that the beets then grown only
carob seed yields a mixture of mannose and yielded about 2 p.c. of sugar.
galactose so that caroubin apparently consists Careful selection of seed, and improved
of mannans and galactans (Compt. rend. 1899, cultivation and methods of extraction, aided
129, 228 and 391). For analyses of commercial by a system of bounties by continental Govern-
carobs v. Balland, J. Pharm. chim. 1904, 19, 569. ments, have resulted in beet sugar almost
All species of beans, like other leguminosae, entirely replacing cane sugar in the principal
serve as hosts for the tubercle-forming, nitrogen- markets of Europe (v. SUGAR).
fixing organisms (Bacillus radicocola), and thus, Beet-root contains water, nitrogenous mat-
under suitable conditions, are independent ters (including true albuminoids and the bases
of supplies of combined nitrogen in the soil. glutamine, betaine, and choline), pectins, sugars
Beans are therefore sometimes used for enriching (of which cane sugar and raffinose are the chief),
soils incombined nitrogen, being employed for colouring matter of an unstable character
green manuring, though the root debris of a crop (Formanek, J. pr. Chem. 1900, ii. 62, 310),
of beans, even after the removal of the seed and and It will be well to consider, in turn, the
ash.
haulms, often effects this object to a considerable composition of average specimens of the three
extent. H. I.
principal varieties of beet-root mentioned
BEAN OIL. See SOYA BEAN OIL. above.
BEBEERU BARK. The dried bark of (a) Mangel-wurzel, or Mangold*, called some-
Nectandra Eodicei (Hook.), the greenheart tree, times field beets. Many varieties, differing in
obtained from British Guiana, contains bebeer- colour, size, and shape, are in cultivation. They
ine or bebirine may be classified into long, tankard, and globe
C 18H 21 N0 3 , or OH-C 16 H, 4 O(OMe) :
NMe, forms.
to which its strong persistent bitter taste is Mangolds grow best in deep, somewhat
due. Occasionally used as a tonic and anti- clayeysoils, and in warm, fairly dry climates.
periodic. They demand abundant supplies of plant food,

Bebeerine is a tertiary amine, m.p. 214, and and, under favourable conditions, yield very
forms crystalline salts. Is optically active : heavy crops, from 20 to 30 tons per acre being
usually obtained. They are better as food for
1 -6 p.c. sol. in alcohol, has a rotation [a] = 298 cattle and sheep after they have been stored
(Scholtz, Ber. 1896, 29, 2054). for some Aveeks.
BEECH NUT OIL v. OILS and FATS. As in almost all root crops, large mangolds
BEECH TAR. According to Fisher, 100 are distinctly more watery than small ones.
parts of beech wood yield on dry distillation 45 The following is the average composition
parts of acetic acid, 23 parts of charcoal, 4 of of mangolds, according to (1) Warington, (2)
oil, and 28 of gas. consisting of 20 parts carbon KeUner ;
BENGAL LIGHTS. 435
436 BENGAL LIGHTS.
An improvement in the manufacture of zoic aldehyde, Benzoyl hydride. Ethereal, or
Bengal lights has been suggested by Chertier volatile, or essential oil of bitter almonds. Essence
(Wagner's Jahr. 24, 464), who obtains a smokeless of bitter almonds. (Aldehyde benzo'ique, Fr. ;
and odourless fire by melting shellac and adding, BittermandelSl, Ger.) Mortres showed, in 1803,
with continuous stirring, the nitrate. The pro- that, hi addition to the fatty oil, a volatile
portions given are for red fires, one part of shellac
: 011 could be obtained from bitter almonds ; but
to five of strontium nitrate; for green, one of pure benzaldehyde was first isolated, its compo-
shellac to five of barium nitrate; and for yellow, sition determined, and its reactions studied, by
one of shellac to three of sodium nitrate. They Liebig and Wohler in 1837 (Annalen, 22, 1).
burn slowly, and are well adapted for theatres, &c. Benzaldehyde not contained, as such, in bitter
is
C. Schmidt has patented (D. E. P. 34020, almonds it :
produced by the action of a
is
1885) the following process. From 1 to 10 soluble ferment, emulsin (also termed synaptase),
grams of magnesium dust are added to 100 present in the almond, on amygdalin C SO H 27 NO U .
grams of collodion, and 3 grams of barium or In this fermentation, which occurs when the
strontium chloride are added. On evaporation bruised almonds are mixed with cold water, the
of the ether, thin plates are obtained which burn amygdalin is hydrolysed, yielding benzaldehyde,
with great brilliancy. together with hydrocyanic acid and glucose :
Another formula recommended by a German = C^ O+HGN+2C.H ls O.

C 20 H 27NO U +2H 2 i
firm is, for white fires, to fuse one part shellac
with six barium nitrate, grind and mix with 2-5 If boiling water is used, the ferment is destroyed
parts magnesium powder. For red fires, five and the reaction does not take place. Peach
parts strontium nitrate is used instead of the kernels and kernels of other stone fruits contain-
barium nitrate. These mixtures can be made ing amygdalin also yield benzaldehyde. It.
into ribbons or charged into thin zinc tubes so as occurs, ready formed, in the leaves of the cherry
to make torches (Dingl. poly. J. 256, 518). (See laurel (Prunus laurocerasus), of the bird cherry
also FLASH LIGHTS PYROTECHNY.
; ) (Prunus padus), and of the peach (Amygdalus
BENITOITE. This interesting mineral is persica).
an acid titano-silicate of barium BaTiSi 3 9 , 1. From bitter almonds.
Preparation. The
and forms beautiful sapphire-blue, transparent bitter almonds (or more rarely, peach kernels)
crystals suitable for cutting as gems. The are ground and then cold-pressed, to extract the
crystals afford the only known example (except fatty oil. The press cake is made into a thin
Ag 2 HP0 4 (H. Dufet, 1886)) of the ditrigonal- cream with cold water, introduced into a still,
bipyramidal class. Sp.gr. 3 -64-3 -67 ; H. 6. allowed to stand for 24 hours, and then distilled
The dichroism is intense, the ordinary ray being either by blowing in superheated steam, or,
colourless, and the extraordinary ray greenish- less advantageously, over a fire, in which case
blue to indigo-blue. The mineral was first found mechanical stirring must be employed to prevent
(and described by G. D. Louderback) hi 1907, the charring of the vegetable matter. The
near the source of the San Benito river in San distillation is continued as long as the distillate
Benito Co., California, the crystals occurring appears milky. Most of the crude benzaldehyde
embedded in natrolite veins traversing schistose separates as an oily layer under the aqueous
rocks. L. J. S. distillate ; some, however, remains in solution
BENJAMIN, GUM, v. BALSAMS. and may be recovered by distilling the aqueous
BEN OIL, Behen Oil, is obtained from the liquid, when the benzaldehyde passes over with
of the Ben nut, from Moringa pterygo- the earlier portions.
sperma (ole'ifera) and Moringa aptera (Gart.). Michael Pettenkofer (Annalen, 122, 77)
The Moringa trees are indigenous to India, modifies the foregoing process as follows :
Arabia, and Syria, and were introduced to 12 parts of the coarsely powdered press cake are
Jamaica from the East Indies in 1784. Moringa added to 100-120 parts of boiling water, stirring
pterygosperma has also been found in Northern during the process, and the mixture is kept
Nigeria and Dahomey.
Ben oil has a
slightly boiling for about half an hour. In this way all
yellowish colour, is odourless, and has a sweetish the amygdalin is obtained in solution. The
taste. The oil consists of the glycerides of liquid is then allowed to cool ; 1 part of ground
oleic, palmitic, and stearic acids ; it also bitter almonds, suspended in 6-7 parts of cold
contains a solid acid of high melting -point, which, water, is added, and after standing for 12 hours
according to Volcker (Annalen, 64, 342), is the whole is slowly distilled. According to
identical with behenic acid, of the melting point Pettenkofer, the maximum yield of benzaldehyde
76 ; possibly the solid acid is identical with is thus obtained, no amygdalin remaining unde-
arachidic acid. In the East, ben oil is used for composed. Pelz, however, states (J. 1864, 654)
cosmetic purposes; it is also employed in the that the yield of benzaldehyde in this process
' '
maceration process for extracting perfumes is no greater than is obtained by macerating
from flowers. In the West Indies the oil is merely the above-mentioned 1 part of ground
used for edible purposes. The statement bitter almonds with cold water and then
contained in the older literature, that ben oil distilling.
does not turn rancid, and that it is for that The oil prepared by either of these methods
reason the best lubricating oil, is erroneous (see contains hydrocyanic acid, from which it may
Chemical Technology and Analysis of Oils, &c., be freed by fractional distillation, the hydro-
ii. 307). J. L. cyanic acid coming over with the first part of
BENZACETIN v. SYNTHETIC DRUGS. the distillate. The hydrocyanic acid may also
BENZAL CHLORIDE. Benzylidene chloride, be removed without distillation by shaking the
Benzidene chloride (v. TOLUENE, CHLORINE DE- oil with a mixture of milk of lime and ferrous
RIVATIVES OF). sulphate (Liebig and Wohler). The purest ben-
BENZALDEHYDE C H 6 7
or C 6 H 8 -CHO. Ben- zaldehyde is obtained by shaking the crude
BENZALDEHYDE. 437
product with 3-4 times its volume of a concen- few hours potassium or sodium bichromate,
:
trated solution of sodium bisulphite, washing 50 kilos. ; water, 200 litres, acidulated with
the crystals of the double compound hydrochloric acid (20B.), 165 kilos., or its
(C,H 6 0,NaHS0 3 ) 2 H 2 equivalent of sulphuric acid ; distillation ensues,
them from water, water and benzaldehyde coming over. The
with alcohol, recrystallising
and them with a solution of sodium nitrobenzaldehydes may be obtained by sub-
distilling
carbonate Annalen, 85, 183 ; stituting the corresponding nitrobenzylaniline.
(Bertagnini, Another method consists in oxidising the salt
Muller and Limpricht, ibid. Ill, 136).
of the benzylaniline sulphonic acid to the
2. From toluene. At the present day benz-
is generally prepared artificially from benzylidene compound, and then treating it with
aldehyde the salt of an aromatic base, followed by hydro-
chlorinated derivatives of toluene. The follow-
chloric acid. The aldehyde is formed, and the
ing are the chief processes that have been pro- aromatic base can be recovered and used for
posed :
another operation (Farb. vorm. Meister, Lucius

Lauth and Grimaux (Bull. Soc. chim. [2] 7,
H and Bruning, Eng. Pat. 10689 and 30118;
105) boil 1 part of benzyl chloride C 6 5 -CH 2 C1,
D. R. P. 110173; J. Soc. Chem. Ind. 1897,
1 parts of lead nitrate (or copper nitrate), and
10 parts of water with a reflux condenser for 558, and 1899, 36). It has been prepared by
several hours, passing a current of carbon passing a current of air charged with the vapour
of toluene through a chamber containing a
dioxide through the apparatus to prevent
oxidation. Half the liquid is then distilled off, catalyser such as oxide of iron, and heated
and the which separates in the between 150 and 300. By substituting porous
oil, distillate, is
carbon for oxide of iron and using a higher
rectified. The product, which consists mainly
of benzaldehyde, may be further purified by temperature, benzoic acid may be obtained
converting it into the bisulphite compound.
(Chavy, Delage, and Woog, Fr. Pat. 379715;
H. Schmidt (D. R. P. 20909 ; J. Soc. Cbem. J. Soc.Chem. Ind. 1907, 1254; Ipatieff, Ber.
Ind. 1883, 274) chlorinates boiling toluene until 1908, 993).
it attains a
It has also been prepared by the oxidation of
sp.gr. of 1 -175, Avhen it consists
essentially of a mixture of 2 mols. of benzyl
benzyl aniline, or benzyl toluidine with chromic
acid mixture or with potassium permanganate
chloride with 1 mol. of benzal chloride. This
solution in acetone (D. R. PP. 91503, 92084 ;
;
product is boiled with six times its volume of

water and a quantity of powdered black oxide Frdl. iv. 129, 131).
;
It has also been prepared from phenyl

\
of manganese containing two atoms of available
magnesium bromide and orthoformic ester
i
oxygen to the above molecular proportion. vorm. Fried. Bayer & Co. D. R. P.
i The reaction is supposed to take place according (Farb.
to the equation 157573 ; Chem. Zentr. 1905, i. 309). By using
15 grams of magnesium, 100 grams of bromo-
2C 6 H 5 -CH 2 Cl+C 6 H 5 -CHCl 2 +2Mn0 2
benzene, and 60 grams of orthoformic ester, a
=3C a H 6 -CHO+2MnCl i! +H 2 0.
90 p.c. yield can be obtained (Bodroux, Compt.
The product is steam-distilled, and the aldehyde rend. 1904, i. 92). It has been prepared by the
purified in the usual way. A mixture of benzyl oxidation of toluene with manganese dioxide and
bromide and benzal bromide may be substituted
sulphuric acid (Soc. Chim. des Usines du Rhone,
\
;for the chlorine compounds. D. R. PP. 101221 and 107722; Chem. Zentr.
Another method now generally employed 1899, i. 959; 1900, i. 1113), or by heating
consists in heating benzal chloride with milk of
J
toluene with nickel oxide (Bad. Anilin u. Sod.
|lime under pressure. Fab. D. R. P. 127338; Chem. Zentr. 1902,
2 = C b H 5 -CHO + CaCl 2 + H 2 O. i. 150).
According to Espenschied (I). R. P. 47187), the It has been prepared by heating benzal
reaction takes place under ordinary pressures if chloride with water at 90-95 in the presence
insoluble substances such as chalk or barium of small quantities of iron or salts of iron
sulphate are added along with the milk of lime, (Schultze, D. R. PP. 82927, 85493 ; Frdl. iv. 143,
so as to produce an emulsion of the benzal 145) ; by passing a stream of carbon monoxide and
chloride. a cooled mix-
hydrochloric acid gas (2:1) through
E. Jacobsen (D. R. P. 11494 and 13127 ; ture consisting of equal weights of aluminium
Ber. 13, 2013, and 14, 1425) heats benzal chloride bromide and benzene, and T their weight of
|j
with an organic acid (or an ethereal salt of an copper chloride, a solid mass is obtained
: this
organic acid) and a metallic chloride, oxide, or is decomposed by ice water, extracted with
ulphide. Thus benzal chloride, when heated ether, and fractionated. The yield is 85-90 p.c.
on the water-bath with acetic acid and a little (Reformatsky, D. R. P. 126421 Chem. Zentr.
;
zinc chloride, yields benzaldehyde, acetyl 1901, i. 1226 ii. 1372).

;
chloride, and hydrochloric acid Benzaldehyde has also been prepared by the
-eHs-CHCh+CHs'COjjH = CeH 5 -CHO+CH 3 -COCl+HCl. electrolytic reduction of benzoic
acid or its salts.
The acetyl chloride, owing to its much lower An electrode of finely divided graphite and
boiling-point, may be readily removed from the benzoic acid is employed as the cathode of the
benzaldehyde by distillation. cell, the anode being of lead or platinum.
The
Benzaldehyde can be prepared by oxidising solution in the cell is 20 p.c. sulphuric acid,
Benzyl aniline to benzyh'dene aniline, which, saturated with benzoic acid, the current used
on addition of acids, splits into benzaldehyde is 1-5 amp. per sq. dcm., and 12-15 volts
jmd aniline. For this purpose 100 kilos, of (Mithack, D. R. P. 123554 ; Chem. Soc. Abstr.
benzyl aniline, and from 500-1000 litres of 1902, i. 291). Mettler (Ber. 1908, 4148) uses a
>vater are placed in a large retort fitted with an
" sodium-amalgam electrode ; and Moest (D. R. P,
igitator ; during agitation and boiling the 138442 Chem. Zentr. 1903, i. 370) electrolyses
;
ollowing mixture is gradually run in during a a solution of sodium phenylacetate.

438 BENZALDEHYDE.
A methodhas been described for purifying Withpyrogallol benzaldehyde forms dye-
acid stuffs ofthe triphenylmethane series (Hofmann,
benzaldehyde by dissolving it in sulphurous
and precipitating the bisulphite compound by Ber. 1893, 1139), and with chloracetopyrogallol
a golden -yellow dyestuff (Kusselkaul and
adding potassium chloride (Chem. Fab.
Grei-
sheim-Elektron, D. R. P. 154499 Chem. Zentr. ;
Kostanecki, Ber. 1896, 1886). By heating
1904, ii. 965). benzaldehyde with a little sulphur in a sealed
Other modes of formation. Benzaldehyde is tube, stilbene and benzoic acid are formed
also formed in the following reactions, which, (Barbaglia and Marquardt, Ber. 1891, 1881).
Derivatives. The most important derivatives
however, are not of practical importance. By
a mixture of calcium benzoate and cal- are the sulphonic acids, which are the parent
distilling
cium formate (Piria, Annalen, 100, 105) by the ;
substances of various dyestuffs (Gnehm and
oxidation of benzyl alcohol (Cannizzaro, Ann. Schule, Annalen, 299, 347). Benzaldehyde o-
Chim. Phys. [3] 40, 234); of cinnamic acid sulphonic acid (Kafa, Ber. 1891, 791 ; Wallach
(Dumas and Peligot, Annalen, 14, 50 Harries, ;
and Wuster, Ber. 1893, 150; Gnehm and
Ber. 1903, 1296) or of stilbene (Harries, I.e.);
;
Schule, Annalen, 1898, 24; D. R. P. 88952),
by the reduction of benzoic acid, either with Benzaldehyde jj-sulphonic acid (Farb. vorm.
sodium amalgam in acid solution (Kolbe, Sandoz, D. R. P. 154528 ; Chem. Zentr. 1904,
Annalen, 118, 122), or by passing its vapour 1269).
over heated zinc-dust (Baeyer, Annalen, 140, Impurities and adulterations. Benzaldehyde
296) by treating toluene with chromyl chloride
; very frequently contains hydrocyanic acid,
sither originally present or subsequently added
and then with water (Etard, Ann. Chim. Phys.
v. supra), and benzoic acid, formed by spon-
[6] 22, 225) by treating 1 molecule of btnzal
;
chloride with slightly more than 2 molecules of taneous oxidation. The artificial product gene-
acetic acid (Benal, Compt. rend. 148, 179) ; rally contains chlorinated benzaldehydes. Alco-
lol, ethereal oils, and nitrobenzene are some-
by acting on benzophenoneoxime with phos-
limes fraudulently added the latter substance
phorus pentasulphide, and decomposing the
;
thiobenzanilide thus formed wieh boiling alkali resembles benzaldehyde in smell.

and zinc-dust (Cuisa, Chem. Zentr. 1907, i. 28). In order to test the purity of a sample of
Properties. Benzaldehyde is a colourless, benzaldehyde, the sp.gr. and boiling-point should
first be determined, as both of these are altered
strongly refractive liquid with a pleasant aro-
matic odour, boiling at 179-180, and solidi- by the presence of impurities. The substance
should also dissolve without residue in a solution
fying at 13-6 (Pictet, Compt. rend. 119,
955 ; Altschul and Schneider, Zeitsch. physical. of sodium bisulphite.
Chem. 1895,24); spgr.l 0504 15/4(Mcndeleeff, Of the impurities above mentioned, hydro-
J. I860, 7). It is soluble in 300 parts of water, cyanic acid may be detected by distilling the
and miscible in all proportions with alcohol oil and then testing the first portions of the
and ether. It is non-poisonous, the poisonous distillate by the Prussian-blue test ; chlorine
properties of ordinary oil of bitter almonds compounds, by heating the oil with metallic
being due to the presence of hydrocyanic acid. sodium, when sodium chloride will be formed,
Its magnetic rotatory power has been studied in which the chlorine can be detected by silver
nitrate, taking care, however, to distinguish
by Perkin (J. Chem. Soc. 1896, 1064).
Reactions. between silver chloride and silver cyanide, as
Benzaldehyde readily undergoes
oxidation ; thus it absorbs oxygen from the air, this latter will be formed if hydrocyanic acid or
nitrobenzene is present ; alcohol, by the iodo-
forming benzoic acid. The presence of hydro-
form test ; and ethereal oils or nitrobenzene, by
cyanic acid protects it from oxidation ; accord-
ing to Dusart (Bull. Soc. chim. 8, 459), it is dissolving the sample in sodium bisulphite,
therefore usual to add hydrocyanic acid to when these admixtures remain behind. Bour-
artificialbenzaldehyde. Taken internally, goin (Ber. 5, 293) tests for nitrobenzene in
benzaldehyde is oxidised in the organism, re- benzaldehyde by mixing the sample with twice
its volume of caustic potash : if nitrobenzene is
appearing in the urine as hippuric acid and
benzamide. Aqueous caustic potash converts it present, the mixture turns green, and on adding
into benzoic acid and benzyl alcohol water the liquid forms two layers, of which the
under layer is yellow and the upper green,
2C.H i -CHO+KOH=C 6 H 5 -C0 2 K+C,H 5 -CH,OH this latter turning red on standing for some
It forms crystalline compounds with the bisul-
hours.
phites of the alkali metals thus
; ;
Estimation. The reagent employed consists
(C 7 H O,NaHS0 H
6 3 ) 2 2 0. of 1 c.c. of freshly redistilled phenylhydrazine,
Under the influence of dehydrating agents, it 0-5 c.c. glacial acetic acid dissolved in 100 c.c.
readily undergoes condensation with various distilled water. The liquid containing the
other substances ; thus when heated with acetic benzaldehyde is heated on the water-bath for
anhydride and dry sodium acetate it yields cinna- half an hour, set aside for 12 hours, and filtered
mic acid through a Gooch crucible, dried over cone,
C 8 H 5 -CHO+CH 3 -CO 2 H=C 2 H 5 -CH CH-CO 2 H+H 2 O :
sulphuric acid, and weighed. Weight of phenyl
(Perkin, J. Chem. Soc. 31, 389) ; cinnamic acid is hydrazone X 0-5481 gives the amount of
also obtained from ethyl acetate and benzaldehyde benzaldehyde present. Small quantities may
(Claisen, Ber. 1890, 976 ; Farb. vorm. Meister, be satisfactorily estimated by this method
Lucius and Br lining, D. R. P. 53671 ; Ber. (He"rissey, J. Pharm. 1906, 60 Dennis and
;
1891, Ref. 180). With dimethylaniline in presence Dunbar, J. Soc. Chem. Ind. 1099, 488). Another
of zinc chloride it forms the compound C 6 H method consists in estimating benzaldehyde
H
CH(C 4 4 'NMe..) 2 , the leuco- base of benzaldehyde coloriinetrically with fuchsin decolourised with
green which, by oxidation is converted into thai sulphurous acid (Woodman and Lyford, J.
colouring matter (0. Fischer,, Ber. 11, 950). Amer. Chem. Soc. 1908, 1607).
BENZENE AND ITS HOMOLOGUES. 439
dioxide and sulphuric acid (Gillard, Monnet et
SUBSTITUTION DERIVATIVES OF BENZALDEHYDE. Cartier, D. R. P. 101221 ; Chem. Zentr. 1899, i.
o-Nitrobenzaldehyde. It may be preparec 960), by extraction from the products of the
In- the oxidation of the dimercury derivative ol incomplete chlorination of o-nitrotoluene (Kalle
^toluene (Reissert, D. R. P. 186881 ; Chem. & Co., D. R. PP. 110010, 115516 ; Chem. Zentr.
Soc. Abstr. 1907, i. 1046 Kalle & Co., D. R. P.
; 1900, ii. 460, 1168).
11(9147 ; Chem. Soc. Abstr. 1909, i. 76); by Properties. It is a liquid boiling at 213-
the oxidation of o-nitrotoluene with manganese 214 ; sp.gr. 1 -29 at 8. By heating with sulphite
dioxide or by passing the vapour of the hydro- it converted into benzaldehyde o-sulphonic
is
carbon over manganese dioxide heated to 210- acid (Geigy & Co., D. R. P. 88952 ; Frdl. iv.
250 (Gilliard, Monnet and Cartier, D. R. P. 113). It is easily condensed with aromatic
J01221 ; Chem. Zentr. 1899, i. 960 ; Bad. Anil, secondary and tertiary amines to yield dyestuffs
u. Sod. Fab., Eng. Pat. 21947 ; J. Soc. Chem. of the triphenylme thane group (Geigy & Co.,
Ind. 1900, 892) ; by the oxidation of o-nitro- D. R. P. 94126; Chem. Zentr. 1898, i. 296).
toluene with nickel oxide, nickel chloride, and By sulphonation, 1:3: 6-chlor benzaldehyde sul-
hypochlorite (Bad. Anil. u. Sod. Fab., D. R. P. phonic acid is produced, Avhich when condensed
127388; Chem. Zentr. 1902, i. 150); by the with secondary or tertiary amines and then
oxidation of o-nitrobenzylaniline (q.v. benzalde- oxidised yields greenish-blue or blue dyestuffs
hyde) by the oxidation of o-nitrobenzylalcohol
; (Soc. Chem. Ind. of Basle, Eng. Pat. 25128 ;
and its esters (Eug. Fischer, D. R. P. 48722 ; J. Soc. Chem. Ind. 1897, 137 ; Gnehm and
Krdl. ii. 98 Kalle & Co., D. R. PP. 104360,
; Schiile, Annalen, 299, 347).
\
106712; Chem. Zentr. 1899, ii. 950; 1900, ra-Chlorbenzaldehyde. It is obtained from
885) ; by the hydrolysis of o-nitrobenzaldehyde m-nitrobenzaldehyde by replacing the nitro-
diacetate, which is obtained by the oxidation of group by chlorine (Erdmann and Schwechten,
o-nitrotoluene with a mixture of acetic anhydride, Annalen, 260, 259 ; Eichengriin and Einhorn,
acetic acid, and sulphuric acid ( Thiele and Winter, ibid. 262, 135). It crystallises in prisms, m.p.
Annalen, 311, 356 ; Fried. Bayer & Co., D. R. P. 17, and boils at 21 3.
121788 ; Chem. Zentr. 1901, ii. 70). p-Chlorbenzaldehyde. It is associated with
Properties. Large yellow needles, m.p. the ortho- compound in most preparations, and
43-5^44-5. When treated with acetone and may be obtained from the mixture by sulpho-
caustic soda it yields indigotin (Baeyer, Ber. nating the ortho- compound by treatment with
15, 2856). With methyl- and ethyl -aniline or fuming sulphuric acid (Gesel. f. Chem. Ind.,
their sulphonic acids it condenses to form leuco- D. R. P. 98229 Chem. Zentr. 1898. ii. 743) ; by
;
bases of blue-green triphenyl methane dyestuffs nitrating the ortho- compound with nitric and
(Clayton Aniline Co., D. R. P. 108317; Chem. sulphuric acids, and steam-distilling the para-
Zentr. 1900, i. 1081). compound (Gesel. f. Chem. Ind., D. R. P.
m-Nitrobenzaldehyde. It may be prepared 102745 ; Chem. Zentr. 1899, ii. 408) ; by frac-
by dissolving 1 volume of benzaldehyde in a tional distillation (Farb. vorm. Meister, Lucius
mixture of 5 volumes of fuming nitric acid, and and Bruning, D. R, P. 207157 ; J. Chem. Soc.
1(1 volumes of
sulphuric acid, precipitating by Abst. 1909, i. 307). It is a crystalline solid,
addition of water and recrystallising from melting at 47-5 and boiling at 2]3-214.
dilute alcohol (Widmann, Ber. 13, 678 ;
Bertag- Of the dichlorbenzaldehydes the 2 5- and :
nini, Annalen, 79, 260). 2 6-dichlor- compounds are the parent sub-
:
Properties. Pale-yellow needles, m.p. 58. stances of manv dyestuffs. 2 ."-dichlorhenzalde-

:
It condenses with the hyde (Gnehm "and Biinziger, Ber. 1896, 875
i
sulphonic acids of the ;
tertiary aniline bases to yield dyestuffs (Kalle & Schule, Annalen, 299, 34). 2 6-dichlorbenzalde-
:
Co., D. R. P. 73147, Frdl; iii. 85). hyde (Anil. Fabw. und Ext. Fabrik., D. R. P.
|>-Nitrobenzaldehyde. It is prepared by 199943; Chem. Soc. Abstr. 1908, i. 986).
similar methods to those by which the ortho- Hydroxybenzaldehydes (q.v.) Salicylaldehyde.
compound obtained (D. R. PP. 91503, 92084,
is BENZALDEHYDE GREEN v. TRIPHENYL-
93539; iv. Frdl.
129); by heating p-nitro- METHANE COLOURING MATTERS.
benzylalcohol with copper oxide or other BENZAMIC ACID v. AMINO- ACIDS (aromatic).
metallic oxides (Schmidt, D. R. P. 15881 ; BENZAURIN v. AURIN.
Frdl. i.
60). BENZENE AND ITS HOMOLOGUES.
Properties. Colourless prisms, m.p. 106. Benzene. (Benzol, Benzole, Fr. ; Benzol,
condenses with benzene and its homologues Ger.) The name of this substance was derived
It
by addition of sulphuric acid to form ^-nitro- in its original form from that of gum benzoin,
triphenylmethane (Stolz, D. R. P. 40340 ; Frdl. probably as benzo'in oleum, hence benzole, which
i.
58) with secondary and tertiary amines to form
; latter form is still in use amongst nearly all
alkyl- and aryl- derivatives of j>-nitrodiamino- distillers and users of it both in this country and
triphenylmethane (0. Fischer, D. R. PP. 16766, the Continent. In more strictly scientific
16707 ; Frdl. i. 54) ; and with the sulphonic literature,however, the name benzene has now
(Kalle & Co., become generally accepted, and the systematic
acids of tertiary aniline bases
D. R. P. 73147 ; Frdl. iii. 86). The sulphonic termination -em is employed in the names of
acid of its various homologues, as toluene, x.ylene, cy-
p-nitrobenzaldehyde is prepared by tho
oxidation of y-nitrotoluene
o-sulphonic acid, and mene, etc.
from it blue and bluish-red Pure benzene is a limpid, colourless, highly
dyestuffs of the
triphenylmethane series are easily obtainable refracting liquid at ordinary temperatures. Its
(Green and Wahl, Eng. Pat. 21825; J. Soc. sp.gr. at is 0-8991 (Koppj, 0-90023 (Adrieenz),
Chem. Ind. 1898, 915). and at 15 0-8841 (Mendeleeff).
o-Chlorbenzaldehyde. It is prepared by the Its refraction index for the D
line at 15-2 is
oxidation of o-chlortoluenc with 1-4957 (Adrieenz); at 9, 1-4593 for A, 1-5050 for
manganese
440 BENZENE AND ITS HOMOLOGUES.
D, 1-5037 for H (Gladstone); at 8-5, 1-50381 densation and decomposition go on together,
for Ha (Perkin, Chem. Soc. Trans. 1900, 77, acetylene, diphenyl, diphenylbenzene, etc.,
273). being formed with evolution of hydrogen and
When surrounded by ice it becomes solid, deposition of carbon.
and There can be little doubt that toluene and
crystallisation is allowed to take place
if
slowly, rhombic crystals are produced, the xylenes can also be produced in this way, and
axes of which, a, 6, c, are 0-891, 1, 0-799 (Groth). since Berthelot has shown that toluene and
The solid melts at 5-4. xylene when passed through strongly heated
It contracts on solidification, the difference tubes can produce anthracene and naphthalene,
in the specific volume of the liquid and solid and since he also obtained anthracene by so
v v=*o is between 0-1219 and 0-1304 at 5-35 treating a mixture of benzene and ethylene, we
f
(Heydweiller, Ann. Phys. Chem. 1897, (iii.) 61, may assume that if benzene is not the mother
substance of the whole series of hydrocarbons
527).
obtained from coal tar, it is yet capable, under
It exhibits no absorption lines or bands in
the visible portion of the spectrum. Beyond proper conditions, of generating all the others.
show a series of
When chlorine acts on pure benzene in
H, however, photographs benzene hexachloride C 6 H 6 C1 6
sunshine, is
four bands covering the region lying between
W. L. 3171 and 2190 tenth-metres. The methyl- formed. Thesubstitution of chlorine for
ated benzenes, toluene, and the three xylenes hydrogen in the nucleus or benzene ring is a
very slow operation if chlorine alone is used, but
exhibit a similar absorption, requiring, indeed,
if in every litre of benzene about 10 grams of
very careful measurement to distinguish one iodine are dissolved, and the liquid kept boiling
from the other (Hartley. Chem. Soc. Trans.
while a brisk current of chlorine is passed into
1885, 47, 685; Proc. Roy. Soc. 1908, 80, A,
it, substitution readily takes place and chlorinated
162 ; Hartley and Dobbie, Chem. Soc. Trans.
benzenes are produced. The reaction may be
1898, 73, 695 ; Baly and Collie, ibid. 1905, 87,
continued until the whole of the hydrogen is
1332 ; Friederichs, Zeitsch. photochem. 1905,
3, 154; Grebe, ibid. 376; Mies, ibid. 1909, 7,
replaced with production of hexachloroben-
357 ; 1910, 8, 287).
zene C 6 C1 6 Corresponding bromine and iodine
.
Benzene is an excellent solvent, easily dis- compounds, and mono- and ^-di-fluoro- deri-
vatives are known.
solving caoutchouc and asphaltum, if they have
not been exposed to light, though the protective When subjected to the action of strong nitric
effect ofthe light on the asphaltum is but slight, acid or a mixture of nitric and sulphuric acids,
and prolonged treatment with benzene causes substitution of hydrogen by NO
2 takes place with
it to dissolve. Nearly all the gum resins, sul- great ease. If the mixture is kept cool only
phur, phosphorus, fats, oils, most of the natural
mononitrobenzene is formed, but if heated,
alkaloids, and many other organic compounds,
dinitrobenzenes are produced, the
the three
are soluble in it. It has also, in common with metadinitro- product (m.p. 89) always greatly
carbon disulphide, the property of dissolving predominating. The ortho- and para- com-
iodine with production of a violet solution. pounds can only be produced in quantity by
Benzene is itself soluble to a very slight extent indirect methods.' Trinitrobenzenes can only
in water, considerably more so in alcohol, whilst be obtained by the action of a great excess of a
ether, glacial acetic acid, and carbon disul-
mixture of nitric acid and fuming sulphuric
acid.
phide, dissolve it readily.
Benzene boils under normal pressure at All the nitro- compounds on reduction with
80-36 (Regnault). For benzene from coal tar, appropriate reagents, such as iron, zinc, or tin,
Adrieenz found 80-53 to 80-62 ; and for that in the presence of acid, preferably hydrochloric
obtained from benzoic acid prepared from gum and water, yield amino- compounds correspond-
benzoin, 80-60 to 80-67. Its specific heat at ing with the nitro- compound reduced. Such
temperatures between 185 and +20 is 0-176 H
are aniline C 6 5 -NH.,, the three diamino-
(Nordmeyer and Bernouilli, Ber. Deut. physikal. benzenes or phenylenediamines
Ges. 1907, 5, 175) and at 94 is 0-4814 (Schlamp, C 6 H 4 (NH 2 ) 2, etc.
Ann. Phys. Chem. 1896, 58, 759).
(iii.) The The amino- compounds, by the action of
latent heat of vaporisation is 94-37 (Griffiths nitrous acid or nitrites in the presence of an
and Marshall, Phil. Mag. 1896, (v.) 41, 1) or excess of acid, preferably hydrochloric, are
94-93 (Campbell Brown, Chem. Soc. Trans. 1905, converted into diazo- compounds. If a diazo-
87, 265). H
benzene salt, e.g. C 6 5 -N 2 C1, is dissolved in
The vapour when inhaled produces giddiness absolute alcohol, and the solution heated, the
and ultimately insensibility. nitrogen is evolved as gas whilst benzene is
Benzene forms with picric acid the molecular regenerated. If a diazo- salt is dissolved in
compound C 6 H ? (N0 2 3 OH,C 6 H 6

) which melts,
water and boiled in the presence of an acid,
with decomposition at 90. nitrogen is also evolved and the corresponding
Oxidising agents, such as potassium per- phenol is produced.
manganate or manganese dioxide and sulphuric The diazo- compounds react with certain
acid, convert it into formic, propionic, and oxalic amino- compounds or phenols, giving rise to the
acids, together with small quantities of benzoic almost innumerable series of colouring matters
and phthalic acids, the latter substances being known as azo- dyes (q.v.). Solutions cooled
produced by the simultaneous oxidation of with ice should be employed, and all rise
formic acid and benzene, the process of condensa- of temperature must be carefully avoided.
tion resembling that occurring in the conversion Under proper conditions some diazo- compounds,
of dimethylaniline into methyl violet. When however, attack the amino- group of ammo-
strongly heated in- sealed tubes or when passed compounds, forming diazoamino- compounds
slowly through strongly heated open tubes, con- such as diazoaminobenzene C 6 H 6 -N: N-NH-C 6 H 5 .
These can be made to undergo an isomeric

change resulting in the formation of what are
known as aminoazo- compounds, of which
H
aminoazobenzene C8 5 -N N'C 6 H 4 -NH 2 is a :
typical example. Such substances, when treated benzene, the six angles representing the six
with a reducing agent, split up into an amine
groups of CH at any of which substitution is
and a paradiamine, while diazo- compounds
supposed to take place. Since only one mono-
yield hydrazines only, and diazoamino- com- substitution compound of a given kind (i.e. con-
pounds a mixture of a hydrazine and anamine. taining a given substituting group) is known, all
If the nitro- compounds are submitted to the the six CH- groups in benzene are supposed to be
action of alkaline reducing agents in alcoholic of equal value. The fact that disubstitution
solution, such as a mixture of zinc-dust and
compounds exist in three distinct isomeric modi-
alcoholic soda, the reaction takes a different fications (compare the above-mentioned
xylenes),
course altogether. The action of alcoholic soda is explained in this scheme
and heat alone will convert mononitrobenzene by the following
suppositions as to the relative positions occupied
into azoxybenzene C.HyN N-C 6 H S ; this, by
by the substituting groups. First, substitution
Ô/ is supposed to take place at two adjacent
angles,
nascent hydrogen, is converted into azobenzene
e.g. 1 and 2, 2 and 3, 4 and 5, &c., in which
H : H
Cg 5 'N N'C 6 S which under the action of the
,
case the word ortho- is prefixed to the name of
same reagent is still further reduced to hydrazo- the substance, as orthodimethylbenzene (com-
H
benzene CS 6 -NH-NH-C 6 5 H
The latter, when .
monly called orthoxylene), or orthodichloro-,

boiled with an acid, is converted into a salt of
orthodibromo-, or orthodiamino- benzene, etc.
benzidine (paradiaminodiphenyl) Or the substitution is supposed to take place at
NH 2 -C 6
H 4 -C 6
H 4 -NH 2 two angles not adjacent, but with one inter-
which is strongly basic compound isomeric posing, as at 1 and 3, 2 and 4, or 1 and 5, etc.
with hydrazobenzene. In this case the product is indicated by the prefix
When heated with concentrated sulphuric meta-, as metadimethylbenz,ene (commonly
acid or treated in the cold with solutions of called metaxylene, &c. Lastly, the substitution
is supposed to take place at opposite
sulphur trioxide in sulphuric acid, sulphonic angles, such
acids are produced by substitution of 3 for HS0 as 1 and 4, 2 and 5, 3 and C, etc. In such a case
hydrogen. These are either mono-, di-, or poly- the substance is known as a para- compound, as
sulphonic acids, according to the treatment paradimethylbenzene, or paraxylene, paradinitro-
adopted. They are all powerful acids, and benzene, etc.
form well-defined and generally well-crystallised This theory is due to Kekule, and satisfac-
salts with sodium, potassium, and ammonium, torily agrees with most of the phenomena.
and equally definite, less easily crj^stal-
though Toluene and xylene generally react under
lised salts with calcium, barium, copper, iron, similar conditions in the same way as benzene,
etc. These, especially the sodium or potassium producing a similar series of compounds. Since,
fused with caustic potash or soda, or
salts, if however, toluene itself is a mono- substituted
heated under great pressure (40 atmospheres) benzene, mono- substituted toluenes are really
with aqueous soda or potash, are decomposed di- derivatives of benzene. For instance, there is
with production of a sulphite of the alkali metal, but one mononitrobenzene, but there are three
and conversion of the benzene residue into mononitrotoluenes. There are three dinitro-
the corresponding hydroxy- or phenolic com- and three diamino- benzenes, but there are six
pound. dinitrotoluenes and six diaminotoluenes, and
Only the methyl homologues of benzene will so on.
be considered here, as these are the chief ones It is to be borne in mind that in all substi-
which occur in coal-tar. tution derivatives higher than the disubstitution
The monomethyl derivative is known as series, the number of possible modifications is
toluene, and under all treatments behaves as a greater when the substituting groups are dis-
completely homogeneous substance. similar than when they are all alike ; thus,
The dimethyl derivative is known as xylene, although there are only three isomeric tri- substi-
the substance of that name occurring in coal tution compounds of the formula C 8 3 X' 3 orH
tar, which occurs as three isomeric compounds :
H
C 6 3 Y' 3 , there are six such compounds of the
Orihoxylene, boiling at 341-142, which, when H
formula C 6 3 X' 2 Y'.
gently oxidised with weak nitric acid, gives a It follows that the xylenes being di- deriva-
toluic acid melting at 102 ; metaxylene,
boiling tives, their mono- are tri- derivatives of benzene,
at 139, which gives a toluic acid melting at and consequently correspond in number with
106 : paraxylene, melting at 15, and boiling the di- derivatives of toluene.
at 138, giving a toluic acid melting at 178. The introduction of the methyl group, more-
Each of these different xylenes is, however, over, permits of another kind of substitution
absolutely identical in percentage composition, which gives rise to a totally different class of
and this isomerism is considered to be due to compounds from those described above as con-
the configuration of the molecule, or, in other figurational isomerides, in which substitution
words, to the positions in space occupied rela- takes place not in the benzene nucleus, but in the
tively to each other, and to the benzene residue, methyl group itself. Such substitution is said to
by the two substituting molecules. be extra-nuclear.
This method of regarding the constitution of Thus, as mentioned above, there are three
benzene and its innumerable series of deriva- H
substances having the formula C 8 10 known as
tives usually, for purposes of discussion, in-
is ortho-, meta-, or para-xylene. These isomerides
vestigation, or explanation, represented by are represented as dimethylbenzenes of the
drawing a hexagon to represent the molecule of following configurations :
CH, CH 3 CH a both boil at about 113, sp.gr. 1-0194. The very
minute quantity in which these substances occur
CH, renders them of no industrial importance, even
CH 3 as impurities.
Benzene was first isolated by Faraday in
.
H
but there is another C 8 10 only known to occur 1825, in the liquid separating from condensed oil
in one form, and always behaving as a mono- gas.
derivative of benzene thisisethylbenzene
;
It unnecessary here to describe the pro-
is
CH'CH.> cesses by which

Mitscherlich, D'Arcet, Kopp,
and many others obtained benzene, as the first
practically industrial process was that of Mans-
field, founded entirely at first on Faraday's, and
Just as in this case a methyl group has been dealing with a similar product as the source,
introduced into the methyl instead of into the namelv, coal tar (Mansfield, Quart. Jour. Chem.
Soc. 1848, 1, 244). Mansfield took the lower
nucleus, so chlorine, bromine, etc., may be in-
troduced, and in this manner such compounds boiling portion of coal tar, which was then used
H
as benzyl chloride C 6 5 -CH 2 C], the di- or tri-
under the name of naphtha for lighting purposes,
and distilled it over a flame in a still provided
chloride, benzaldehyde, and many others are
with a jacketed head and a simple form of
formed.
The physical properties of toluene greatly dephlegmator made by connecting the upper
resemble those of benzene. As solvents, there part of the condensing worm with the still body
is little or no difference in their powers, and by an inclined tube. The water in the jacket
round the long egg-shaped head partially con-
though the boiling-point of toluene is so much densed the vapours rising from the boiling fluid
higher than that of benzene, yet in a current of until it reached a temperature of 100, when those
air at ordinary temperatures it evaporates nearly
as quickly. vapours condensable at that temperature were
Toluene is a colourless limpid liquid which alone affected and returned to the still, those
requiring a lower temperature passing on to the
solidifiesat 94-2 (Ladenburg and Krtigel,
Ber. 1899, 32, 1818) or -97 to -99 (Archibald worm, and being condensed and collected. Much
of the spray carried upward by the vapours was
and Mclntosh, J. Amer. Chem. Soc. 1904, 26,
305). Its specific gravity is less than that of stopped in the head, and what passed it and was
condensed in the connecting tube between the
benzene, being at 0-882, at 15 0-872, its
still head and the worm flowed into the inclined
index of refraction at 25-5 is for A 1-4709,
D 1-4794, H
1-5090 (Gladstone and Dale), at 8-5 tube, and found its way back to the body of the
for Ha 1-49891 (Perkin).
still. Finally, when nothing more could pass
Toluene boils constantly at 111 ; the vapour the boiling water in the jacketed head, this in-
has much the same physiological effects as that clined tube, on a cock being fully opened, which
of benzene, but its odour is decidedly less plea- during the first part of the process was partially
sant. If ingested into the stomach, it is closed, could be made use of to distil over the
eliminated in the urine as hippuric acid. higher boiling portions.
Of the three xylenes the meta- is chiefly used Such an apparatus could, of course, only effect
' '
a rough separation of the oil into a benzol
in commerce. Orthoxylene boils at 141-142. '
Metaxylene boils at 139, and its specific mainly distilling below 100 and a naphtha,'
0-8668 at 19. most of which would not distil below 100.
gravity is Paraxylene boils at
138, and at 19 its gravity is 0-8621. The two If,however, the water of the water jacket
former are liquid at all temperatures down to round the head were carefully kept at a stated
at least 20, but paraxylene becomes solid temperature, say 80-82, a much purer product
when exposed to a freezing mixture, and when could be obtained. For some years the process
once frozen it only melts at 15. was only carried out with the object of getting
The xylenes are distinctly less volatile than oils for the Read Holliday lamp, and for the use
toluene and benzene in an air current. The of rubber manufacturers.

smell of the vapours is unpleasant and pungent, The early demands for ' benzol for use in
'
and they possess the power of producing un- the aniline colour industry were confined to
consciousness when inhaled. what were known as 30 p.c., 50 p.c., and 90 p.c.
Both benzene and toluene when prepared benzols, which terms were understood to mean
from coal tar are accompanied by sulphur com- that 30, 50, or 90 p.c. by measure of the sample
boiled below 100. Of these the 30 p.c. was
pounds known as thiophens. That derived from
benzene, no doubt by the action of sulphur from mainly used for the production of aniline for red,
the pyrites of coal at a high temperature during and the 90 p.c. for aniline for blue. Mansfield
distillation in the gas retort, is represented bv had, however, subjected his distillates to a care-
ful but most laborious fractionation in glass
/S\
the formula C4H 4S or ( \ retorts, finally obtaining perfectly pure benzene
by recourse to freezing and pressure, and ho
It was by V. Meyer, who
isolated in 1882 '
pointed out that it is evident that any of the
obtained by constant and repeated agitation summary processes of rectification which are
with sulphuric acid about 2 kilos, from 2000 practised distillers in the manufacture of
by
kilos, of commercial benzene. It is a colourless alcoholic spirits are applicable to the separa-
liquid, boiling constantly at 84 ; sp.gr. at 15 tion of benzole from the less volatile fluids of the
1-100. In many of its reactions it behaves naphtha
'
(Reports of the Royal College of

exactly like benzene. Chemistry, 1849, 257).
Two thiotolens corresponding with toluene, Mansfield, in fact, in the remarkable paper
i.e.
being methylthiophen, are known. They just quoted, laid the foundations of the whole
FIG. 1.
A, Still body. B,Analysing column, c, Cooler kept at tempeiature of distillate wanted. D, Condenser for
pure distillate. E, Vase into which distill&te flows, r, Automatic regulator.
benzene industry, and his processes with holes, and one larger, into which is fitted a short
scarcely a change are in use to this day. The wide overflow tube, the end of which stands up
departures from them have been one by one about 2 inches above the level of the plate. On
abandoned in favour of his method of absolute the opposite side of the plate is a small depression
separation of the light oils into their consti- about 2 inches deep and 4 inches in diameter, into
tuents, and it is not too much to say that had it which the overflow tube from the plate above
not been for his terrible death l in February, dips, its own tube dipping in the same way into
1855, we should have had the pure hydrocarbons a depression in the plate below. The condensed
in the market many years ago. fluid acts to each overflow tube as a trap (Fig. 2),
The introduction of the aniline black printing and prevents the ascent of vapour through it.
processes and other improvements in the dye The rising vapour condenses rapidly on these
industry, however, slowly save rise to a demand plates, and the fluid thus produced, unable to
for a purer benzene, while later on a demand for penetrate the small holes through which the
toluene and xylene stimulated the improvement hot vapour is rushing, rises to the brim of the
of the distillation process. overflow tube, and then pours down from plate
The movement was naturally, as Mansfield to plate into the still body. The non-con-
had suggested, towards the use of such a still densed vapour rises through the perforations
as had been introduced by Mr. Coffey in his of the next plate, where it undergoes a similar
patent of 1832 and subsequently carried to great operation, and so on to the top, the vapour
efficiency by succeeding generations of spirit passing away from which has thus been succes-
distillers. Coupler of Paris appears first to have sively washed by bubbling through some thirty
worked on a large scale in this direction about layers of fluid, each slightly cooler than the one
1863. He modified the original Mansfield appa- beneath. Finally, the vapour passes through a
ratus in the way mentioned above, and showed surface or multitubular condenser, c, which is
that at one operation he could separate ordinary provided with a water supply so regulated that
50 p.c. commercial benzol as follows : its temperature is about that of the boiling-
100 litres yielded : point of the liquid required. The liquid here
44 litres between 80 and 82 Pure benzol condensed flows back into the column at a suit-
(' ')
6 82 110 (Crude toluol) able point, while the now purified vapour passes
17 110 112 ('Pure toluol') on to the second condenser, D, and is finally com-
5 112 137 (Crude xylol) pletely condensed into the liquid form. Thence
it flows into the glass vase E, which is fitted on
9 137 140 (' Pure xylol ')
13-14 140 150 last runnings. to a stand-pipe communicating with the dis-
tributing-pipes which convey it to the store
In addition there were about 6 litres between tanks. The fractions taken should now boil as
62 and 80, consisting of various impurities follows: Benzene, 80; toluene, 110; xylene,
such as carbon disulphide, acetonitrile, etc. 140.
Vedle', Savalle of Paris, and others followed If pure products are required, each fraction
with various improvements in the same direc- is washed with concentrated sulphuric acid,
tion, Savalle being most generally considered to and a washing with soda solution follows.
have produced the best still, though it had The fraction is introduced into a cast-iron
two great drawbacks, viz. it was manufactured vessel provided with a lid with manhole and
of copper, which made it very costly, and it was
inlet pipe. Through the centre passes a vertical
hampered, as far as its condensation arrange- shaft rotated by mitre geared wheels. The shaft
ments were concerned, by an expensive and use- is provided with arms so
less attempt to use air from a fan driven
arranged that the con-
steam as a means of cooling the condensers.
by tents can be thoroughly churned up. A good
form of apparatus is seen in Fig. 3. The details
The latter attempt was soon given up. In need no description except to point out that the
Fig. 1 (p. 443) is seen the apparatus in its screws used to force the fluids through the two
form as made
latest
vomiting tubes A and A' should be set on the
by the Metallwerke shaft with their helices reversed right and left,
vormals T. Aders, of so that the lower one causes the lower fluid to
Magdeburg-Neustadt. rush up, and the upper one the upper fluid
The still being to rush down ; they thus cause the two currents
charged with the to meettogether violently and thoroughly
proper quantity of mingle. The centre shaft may also consist of
naphtha or crude ben- an Archimedean screw or of a truncated hollow
zol, which has under- cone. Air agitation is not advisable on account
gone the necessary of the loss of benzol which it is apt to cause.
washings with sul- If the fraction is of fairly good quality and
phuric acid and sodium has been properly separated from the crude
hydroxide, steam is ad- benzol or light oils, the amount of acid required
FIG. 2. mitted into the coils, need not be more than one-twentieth of its
where it circulates, the
condensed water escaping through another tube in weight. In some cases, however, where the
the usual fashion. As soon as the liquid impurities are difficult to remove, more must
begins be used, and the operation repeated. After
to boil, the vapour ascends into the head a and
the acid has been run off, a washing with enough
passes through the curved tube a' into the bottom soda solution to neutralise excess of acid and
of the column B. This contains 25 to 30 flat remove traces of phenols follows, and the frac-
diaphragms, each pierced with a number of small tion is then ready for a second rectification.
1
Mansfield was burned to death If crude naphtha has been used to charge
by the boiling over
of a benzene still. the still, it will have yielded, inter alia, 50 p.c. or
90 p.c. benzol according to requirements. On crystalline precipitate on standing with a few
redistillation, 100 parts of the former should drops of phenylhydrazine (test for carbon
yield 45-48 parts of pure benzene, and from disulphide). When shaken with concentrated
100 parts of the latter 70 parts of pure benzene sulphuric acid the latter should be only slightly
should be obtained. darkened (thiophen or aliphatic hydrocarbons).
When re-rectified, the benzene and toluene On shaking with sulphuric acid and a trace of
isatin, no blue coloration should be produced
(thiophen). On
treatment with a mixture of
nitric and sulphuricacids, and subsequent dis-
tillation hi a current of steam, no unnitrated
hydrocarbons should be obtained (aliphatic
hydrocarbons). Lastly, it should solidify when
cooled below 0.
Pure toluene of commerce should not impart
any coloration to sulphuric acid when shaken
with it. On shaking 90 c.c. of toluene with
10 c.c. of nitric acid (sp.gr. 1 -44) in a stoppered
bottle, the acid should assume only a red colour,
and 'remain quite clear and bright, not turning
greenish or blackish. (For much information as
'
to the commercial valuation of benzols," see
Lunge, Coal Tar and Ammonia, 4th ed. 1909.)
Nitration of benzene, toluene, etc. Nitro-
benzene first made its appearance in the arts
under the name of essence de myrbane, manu-
factured in France by Collas. It was used to
scent soap and as a bitter -almond
flavouring.
Mansfield had taken out a patent for its manu-
facture in 1847 from coal-tar benzene. The
history of its manufacture is interesting, as
the difficulties to be encountered were
very
consider i '
le.
FIG. 3. The first really large quantity produced was

made by Messrs. Simpson, Maule, & Nicholson,
should each distil constantly within 0-5 and at Kennington, in 1856. They worked at first
1 -0respectively, and the xylene within 2. entirely in glass. Along a bench a row of some
The treatment for obtaining toluene is exactly twenty bolt-heads, each of about 1 gallon
the same as that described for benzene, the capacity, was ranged, with a convenient water
toluene following the benzene from the crude trough at hand. Into each flask from 1 to 2 Ibs.
benzol still and being subsequently re-rectified. of benzene was introduced, and the calculated
Toluene is also accompanied by the correspond- quantity of the mixed acid, divided up into cor-
ing thiophen (thiotolen), and requires very responding portions, stood beside each in a
careful and thorough washing with sulphuric stoneware jug. Commencing with the first
acid, or it cannot be properly nitrated. flask, a workman next proceeded to add a small
After the separation of the toluene, more or quantity of the acid and thoroughly swing round
less crude xylene is obtained, and the residue and agitate it with the benzene. As soon as he
in the still is then cooled and run out. When judged it to be safe to leave this flask, he treated
good crude benzol has been worked, the residue the next in rotation, and so on till the whole
contains a very large quantity of naphthalene, series had received its first portion. He now
which separates from it when cold, and is known returned to No. 1, and added a second quantity
'
in the works as naphthalene salts.' As it has of acid, and this was continued until all were
all been brought off from the tar at a low tem- finished. It need scarcely be said that the pro-
perature, it extremely free from higher boiling
is cess was considered a dangerous one, and that
substances, and very pure naphthalene can be any attempt to increase the scale of manufacture
obtained from it with little trouble. Of the was a very serious undertaking. The attempt,
rest, some 20-30 p.c. consists of phenol, to however, was made in cast-iron vessels, furnished
which the same remarks apply. The remaining with mechanical stirrers, and the size of the
third consists of a mixture of hydrocarbons apparatus was rapidly increased until it attained
from which some more xylene could no doubt dimensions at which it was capable of dealing
'
be recovered, but the bulk of this dead oil,' as with several hundred pounds weight of benzene.
it is often called, is used for
burning. Meta- The usual arrangement now adopted (see
xylene can be prepared from the purified mixed
'
Fig. 4) is as follows :
xylenes by agitation with sulphuric acid, as The nitratingpan has a total capacity of
described for benzene and toluene, to remove the 1600 gallons, and is capable of treating 500
thiophens, when a subsequent treatment with gallons or 4420 Ibs. of benzol in one charge.
its own weight of It is of cast iron, 1J inches thick, the sides, from
sulphuric acid converts the
metaxylene into a sulphonic acid, which after the lid down to a depth of 3 feet, being J inch
separation from the insoluble portion is hydro- thicker. The vertical agitating shaft is sus-
lysed, and metaxylene of great purity obtained. pended from the lid on ball bearings, and carries
'
Valuation of commercial pure benzol.' As
stated above, the whole should boil within 0-5
1
See Chem. Trade Jour. 1906, 38, 59. The writer is
indebted to Messrs. Davis Bros, for permission to
of the correct boiling-point. It should give no reproduce the sketch of the apparatus.
two propeller agitators. The internal cooling perforations at the bottom to admit the descend-
pipes consist of two separate coils of thin
lead ing liquid. This serves also as a support for
the grates and coils. Five hundred gallons of
pipe 2 inches diameter, each coil being about
150 feet long. They are supported on circular pure benzol are first run by gravity into the
cast-iron grates or tables, as shown. The coils machine. The acid-mixing tank, which stands
are spaced out so as to allow free passage of above, is charged with 5000 Ibs. of nitric acid,
the liquid between them. To direct the upward 1-43 sp.gr. or 86Tw., and 6600 Ibs. of sulphuric
flow of the liquid, the lower propeller agitator is acid of 96 p.c., and these are thoroughly mixed by
surrounded by a cast-iron with large air agitation. In some factories the acids are
cylinder
^-
41 elTTTnf li if
-
ffi
FIG. 4.
A, Mixed-acid pan. G, Thermometer. N, Cooling-water inlet. T Nitrobenzene pipe.

B, Compressed-air pipe. H, Propeller agitator. O, Do. do. Ao. U, Compressed-air pipe.
C, Sulphuric acid inlet. J, Lead
cooling-coils. P, Compressed-air pipe. V, Waste-acid pipe.
D, Nitric acid inlet. K, Supporting grids. Q, Water inlet. W, Pipe to N. B. tank.
E, Acid-vapour pipe. L, Cooling-water outlet. B, Nitrobenzene washpan. X, Air-pressure egg.
F, Nitrobenzene pan. M, do. do. do. S, Pipe from egg.
mixed in the above proportions in large stock a good supply of cooling water passing through
tanks. The mixed acid is run in a thin stream the coils, very little attention is required, and
into the benzol, while the agitators are revolving the process, which a few years ago was attended
at a speed of about 60 revs, per minute. The with danger and frequent loss, is now carried
heat of the reaction is indicated on a long on almost automatically. This is principally
thermometer suspended in a metal tube, which owing to the purity of the benzol employed, and
passes through the lid and dips into the liquid. the use of internal cooling coils in place of the
The temperature is kept below 60 by checking outside water-jacket.
the flow of acids if the temperature rises. With It is important that the coils should be of
BENZIDENE PUCE 447
pure chemical lead, without flaw,

and before that article being cheaper and yielding a some-
being used, they should be examined minutely. what more fragrant myrbane than benzene alone.
Some of these coils have been known to work The treatment adopted with toluene and
nearly 4 years continuously. The vertical xylene is in all essential particulars the same as
portions, connecting
the coils with the exterior, with benzene. In the former case, however, if
should be protected, as these are quickly the nitrotoluene is not employed direct, the
'
threading them
'
attacked. This is done by product is separated into p- and o-nitrotoluene
through lead pipes of slightly larger diameter, by fractional distillation under diminished pres-
and filling up the intervening space with any sure through a Savalle column. The distillation
is stopped when 40 p.c. has distilled, and the
acid-proof cement. After the full charge of
mixed acids has been run into the machine, distillate on redistillation gives nearly pure
the agitation is continued for about 4 hours, o-nitrotoluene (b.p. 233). The residue on
and the benzol will then be completely trans- cooling deposits crystals of
p-nitrotoluene
formed into nitrobenzol. If a sample is then (b.p. 238; m.p. 54), which are freed from
taken while the agitators are running, and oil by centrifugating.
allowed to settle, the weak sulphuric (called (For the estimation of o- and p-nitrotoluene,
waste acid) will contain less than 1 p.c. of nitric see Reverdin and De la
Harpe, Bull. Soc. chim.
acid, and the upper layer of nitrobenzol will 1888, (ii.) 50, 44; Glasmann, Ber. 1903, 36, 4260 ;
have a sp.gr. of 1-235. The agitation is then Chem. Zeit. 1904, 28, 187 ; HoUeman, Proc. K.
stopped, and the contents of the machine Akad. Amsterdam, 1904, 7, 395 ; Rec. trav.
'
allowed to settle for 5 hours. The waste chim. 1908,27,458.)
acid,' having settled to the bottom, is run off Dinitrobenzene and dinitrotoluene are obtained
into the air-pressure egg below, and blown to by treating a charge of the hydrocarbon with
the sulphuric acid concentrating department to double the proportion of the mixed acids, the
be rectified. The nitrobenzol is next run off operation being carried out in two stages, and
into the air-pressure egg and blown into the the second charge of acids run in directly after
washing pan above, where it is washed by the first. The cooling water is shut off and the
violent air agitation with an equal volume of temperature allowed to rise rapidly. Or nitro-
water containing sufficient sodium hydroxide benzol already manufactured may be taken
to neutralise any trace of acid left in it. After and again treated with the necessary acid.
settling a few hours the nitrobenzol settles to The product of the reaction is separated from
the bottom, and is run down into the air-pressure the acid as usual, and then thoroughly washed
egg, and forced from there into a large store tank, with cold, and lastly with hot, water. As
which is set at a high level, so that the contents dinitrobenzene is sensibly soluble in the latter,
can run by gravity to the aniline machine. the hot wash-water had better always be pre-
The wash-water, which contains a little nitro- served and used for first washing a subsequent
benzol in suspension, is run into a series of batch. Finally, it is allowed to settle, and,
settling tanks, and the oil recovered. Although while still warm, run out into iron trays, in
it is possible to work a charge of benzol in each which it solidifies in masses 2 to 4 inches thick.
machine daily, it is customary to have a duplicate The principal product of the reaction is meta-
set of machines, and to work each machine on dinitrobenzene, m.p. 89-8, but orthodi-
alternate days. For an output of 150 tons of nitrobenzene, m.p. 118, and paradinitro-
pure aniline oil per month, six nitrobenzol benzene, m.p. 172, are also produced, the m.p.
machines are required, with their corresponding of the commercial product being about 85-87.
adjuncts, as shown in the figure. The yield of It should not contain any nitrobenzene, and
nitrobenzol from the pure benzol employed is should be well crystallised, hard, and almost
154 p.c. by weight, and this approaches so odourless, and should not render paper greasy.
near the theoretical yield, viz. 157-6 p.c., that Dinitrotoluene is prepared by a process
there is little room for improvement. It is similar to the above, and, since ortho- and
possible to increase this yield by
slightly para-nitrotoluene yield, when nitrated at a high
settling the waste acid for 48 hours in a series temperature, most of the 2 4-dinitrotoluene,
:
of tanks, and skimming off the nitrobenzol, it is better to proceed straight on from the
but in practice it has not been found to pay toluene.
for the trouble, especially if the previous separa- The subsequent treatment is the same as
tion be carefully watched. 1 when dinitrobenzene is manufactured. Com-
When the nitrobenzol is to be sold as mercial dinitrotoluene consists mainly of the
myrbane,' it is distilled under diminished last-named and the 2 6- modifications, but
:
pressure in order to obtain a perfectly clear and always contains small quantities of the other
transparent liquid such as the users of myrbane isomerides. The 2 6- only occurs in small pro-
:
demand. It is customary to use toluene im- portion, and mainly in the oily drainings from
perfectly freed from benzene for this purpose, the crude product. The nitration of the pure
metaxylene does not differ from the processes
1
Benzene may also be nitrated by using sodium
nitrate instead of nitric acid. A recent recipe is the
already described. J. C. C.
following: 35 kilos, of benzene and 115 kilos, of sodium

BENZENE DIAZONIUM SALTS v. DIAZO
nitrate are mixed at 60-80, and 150 kilos, of 90-96 p.c. COMPOUNDS.
sulphuric acid added slowly. The temperature rises to BENZIDI N E and BENZI DINE REARRANGE-
about 100, when 65 kilos, of benzene are added, and
when the nitration is complete the lower layer of MENT V. DlPHENYL.
bisulphate is drawn off. The yield is stated to be BENZIDINE AZO- DYES v. Azo- COLOURING
150-154 kilos, of washed nitrobenzene, sp.gr. 1-18 at MATTERS, and DISAZO- and TETRAZO- COLOURING
15 , or 148 kilos, of the pure substance boiling at 96
under a pressure of 18 mm. (Saccharin-fabrik. Akt.-Ges.
MATTERS.
vorm. Fahlberg, List & Co. D. R. P. 221787, July 21, BENZIDINE PUCE v. Azo- COLOURING
MATTERS.
448 BENZTL.
BENZIL v. KETONES. heated in a closed vessel and the vapour of the
BENZINE, Light petroleum (v. PETROLEUM) subliming acid flows over into a side chamber
BENZO-AURINE, -BLACK BLUE, -BLUE and condenses at a point below the source of
-BROWNS, -FAST PINK, -FAST SCARLETS heat, thus obviating all risk of fusing the sub-
-INDIGO BLUE, -GREY, -OLIVE, -ORANGE limate. The gum benzoin is introduced by
-PURPURINS, -RED BLUE, -VIOLET v. Azo- means of a metal drawer, which is heated from
COLOTTRING MATTERS. beneath by gas jets ; whilst the sublimed acid
BENZOFLAVINE v. ACRIDINE DYESTUFFS. collects in a second drawer, and can thus be
BENZOIC ACID C 7 H.0 2 orC 8 H 6 -C0 2 H. (Acide removed at the end of the operation (comp.
benzo'ique,FT. ; Benzoesaure, Ger.) Acidum Starting, Arch. Pharm. 231, 342). By other
benzoicum. Blaise de Vigenere, in his Traite du methods the yield from gum benzoin may bo
feu et du sel, published in 1608, described the increased to 25 p.c.
preparation of benzoic acid by sublimation from
Wohler's method (Annalen, 49, 245) consists
benzoin. Lemery, in 1675, called attention in dissolving the powdered gum in an equal
gum
to its acid properties ; and Scheele showed, in volume of alcohol of 90-95 p.c., adding fuming
1775, that it could be extracted from gum hydrochloric acid to the hot solution until a
benzoin by boiling the gum with lime, concen- precipitate begins to be formed, and distilling the
trating the solution, and decomposing the salt
mixture. The distillate contains ethyl benzoate,
with hydrochloric acid. Scheele also, in 1785, alcohol, and hydrochloric acid. The residue is
obtained benzoic acid from cow's urine ; but it again distilled with water as long as ethyl ben-
was not until 1829 that Liebig showed that the zoate passes over, and the united distillates are
substance contained in the urine, by the decom boiled with caustic potash to decompose the
position of which benzoic acid is formed, is ethyl benzoate. From the solution the benzoic
acid is precipitated with hydrochloric acid. It
hippuric acid.
Occurrence. Benzoie acid occurs in gum smells like the sublimed product.
benzoin, tolu balsam, storax, dragon's blood, Scheele's method of extracting the benzoic
and various other natural resins ; in oil of ber- acid from the gum with slaked lime and water
gamot and oil cinnamon ; in vanilla, calamus
of (v. supra), may also be employed.
root, and the ripe fruit of the clove tree ; in 2. From urine. The urine of the cow or
various sweet-smelling flowers thus in the horse is allowed to putrefy, so as to induce a
flowers of Unona odoratissima, from which the hydrolytic decomposition of the hippuric acid
perfume ylang-ylang is prepared ; as hippuric into benzoic acid and glycocoll. Milk of lime is
acid (and sometimes even, it is asserted, as then added, the filtered solution is evaporated to
free benzoic acid) hi the urine of herbivora ; and a small bulk, and the benzoic acid precipitated
in castoreum, a viscid, foatid secretion, found in with hydrochloric acid. In order to avoid the
pouches situated in the perinseum of the beaver. evaporation and the attendant disagreeable
Formation. By the oxidation of all com- smell, the excess of lime may be removed by
pounds which contain the phenyl group united carbon dioxide, the benzoic acid precipitated by
to a single lateral chain, such as toluene, benzyl the addition of ferric chloride, and the ferric
chloride, benzyl alcohol, benzaldehyde, cinnamic benzoate, after separating it by filtration, de-
H
acid, &c. By heating benzotrichlorideC 6 5 'CCl 3 composed by hydrochloric acid. The acid thus
with water. By heating benzonitrile C 6 5 -CN H prepared smells of urine, and must not be used
with acids or alkalis. By boiling hippuric in medicine. The smell may, however, be
acid with hydrochloric acid removed or concealed by mixing the acid
H
(C 7 6 0)NH-CH 2 -C0 2 H+H2
with a small quantity of gum benzoin and
=C 7 H 6 O Z +NH2 -CH 2 -C0 2 H. subliming it.
dioxide into benzene con-
The fresh urine may also be evaporated to
By passing carbon one-third of its bulk, filtered, mixed with hydro-
tain ing aluminium chloride
chloric acid, and allowed to cool. Hippuric acid
C6 H 6 +C0 2 =C 4 H5 -C0 2 H.
crystallises out, which, by boiling with concen-
Preparation. 1. From gum benzoin. In trated hydrochloric acid, is decomposed into
order to obtain the acid from gum benzoin by glycocoll hydrochloride and benzoic acid.
sublimation, the gum, broken up into small Benzoic acid may also be prepared by the action
pieces, is introduced into a flat iron vessel, over of ammonia and zinc-dust on gallic acid and
the mouth of which filter paper is then pasted. A catechu-tannic acid (Guignet, Compt. rend. 113,
large conical cap of strong paper, exactly fitting 200).
the iron vessel, is placed over the filter paper, 3. From toluene. Most of the benzoic acid
tied round the rim, and the whole is gently mployed at the present day, and certainly all
heated over a sand-bath at a temperature of that is employed in the coal-tar colour industry,
about 170. The benzoic acid sublimes through is manufactured from toluene (v. infra). Toluene
the filter paper and collects in colourless crystals by oxidation with nitric acid, may be directly
inside the paper cone, from which it is removed at converted into benzoic acid ; but it is better
the end of the operation (Mohr, Annalen, 29, 177). to chlorinate it first to benzyl chloride, which is
The yield is about 4 p.c. of the gum employed, more readily attacked by the oxidising agent.
and from three to four hours are required for Lunge and Petri (Ber. 10, 1275) boil benzyl
the sublimation of a pound of benzoic acid. Achloride (1 part) and dilute nitric acid (3 parts of
trace of an aromatic oil from the gum adheres acid of 35Baume with 2 parts of water) in
to the crystals, imparting to them a pleasant a reflux apparatus until the smell of
benzyl
odour of vanilla, and enhancing then value as a chloride and benzaldehyde is no longer per-
1
pharmaceutical preparation. On a manufactur- 3eptible. A. v. Rad (Dingl. poly. J. 231, 538),

ing scale a modification of the foregoing labora- lowever, states that this method is unsuited for
tory process is employed, in which the gum is >reparing the acid on a manufacturing scale, and
BENZOIC ACID. 449
prefers to decompose benzotrichloride by heating from unchanged naphthol. The filtrate is

it with water under pressure :
decomposed with sulphuric acid and evapo-
C6 H5 -Ca 3 +2H 2 0==C 6 H 5 -C0 2 H+3HCl ;
rated, the precipitated acids being purified by
distillation.
but it is to prepare pure benzotri-
difficult
6. By the electrolytic oxidation of phenanthrene.
chloride, and the benzoic acid manufactured by Farbwerke vorm. Meister, Lucius and Briining,
this process is always contaminated with chloro-
Chem. Zentr. 1904, ii. 71 ; D. R. P. 152063.
benzoic acids formed from chlorinated benzo-
Properties. It crystallises in lustrous leaflets
trichlorides.
or flat needles of sp.gr. 1-2659 15/4, melting at
Espenschied R. P. 47187) boils the
(D. 121-4. It boils at 249, but is volatile even at
benzotrichloride with milk of lime, or with a
100, so that it may readily be sublimed ; the
solution of caustic soda mixed with whiting or
other insoluble matter, the presence of which vapour excites coughing. It may be distilled
with steam ; 2 litres of aqueous distillate con-
aids the reaction by preventing the benzotri-
tain 1 gram of benzoic acid. 1000 parts of water
chloride from forming a separate layer and also
dissolve at
by promoting local superheating.
E. Jacobsen (D. R. P. 11494 and 13127) Ou 20 40 60 80 100
heats benzotrichloride with acetic acid to which 1-70 2-90 5-55 11-55 27-15 58-75
a little zinc chloride has been added :
(Bourgoin, Arch. Pharm. [5] 15, 168) ; it is
C 6 H 5 -CCl 3 +2CH3-CO 2 H=C HVCO2H:+2CH3-COCl+E:ci
fi soluble in about twice its weight of ether and in
The acetyl chloride is distilled off, the residue about its own weight of absolute alcohol at
extracted with sodium carbonate, and the ordinary temperatures.
benzoic acid precipitated with hydrochloric acid. Traces of impurity lower the melting-point
The benzoic acid required in the coal-tar of benzoic acid very considerably. The impure
colour industry is obtained as a by-product in the acid is also deposited from its solutions in
manufacture of benzaldehyde by heating benzal smaller crystals than the pure.
chloride with milk of lime (v, BENZALDEHYDE), (For absorption spectra, see Hartley and
a portion of the benzaldehyde being converted Headley, Chem. Soc. Trans. 1907, 319.)
into calcium benzoate in this process. Reactions. When heated with lime, benzoic
4. From coal-tar oil.
Aktiengesellschaft fur acid yields benzene and calcium carbonate
Theer und Erdol Industrie, Eng. Pat. 7867; (Mitscherlich). It is very stable towards oxi-
D. R. P. 109122 ; J. Soc. Chem. Ind. 1899, 785. dising agents ; dilute chromic acid is without
The carbolic or creosote oil fraction, obtained action on it, but by warming it with manganese
from coal tar, and boiling between 160 and. dioxide and sulphuric acid it is converted into
240, contains benzonitrile. The fraction from formic acid, carbon dioxide, and phthalic acid
which phenol is obtained is washed with dilute the latter being formed by the simultaneous
soda lye (sp.gr. 1-1) to remove the phenol and oxidation of formic and benzoic acids (Carius,
cresol, and the remaining oil placed in a jacketed Annalen, 148, 72). Sodium amalgam reduces
vessel, provided with an agitator and connected benzoic acid in boiling alcoholic solution to
with a condenser and receiver. Caustic soda benzyl alcohol, benzaldehyde, and tetrahydro-
lye (sp.gr. 1-4) is added in about twice the benzoic acid (Aschan, Ber. 24, 1864, and Annalen,
quantity corresponding to the benzonitrile 271, 231). By electrolytic reduction, benzalde-
present. The mixture is agitated, and wet hyde is obtained (Mettler, Ber. 41, 4148), and by
steam passed in for some hours, as long as reduction with hydrogen and platinum, hexa-
ammonia is evolved in considerable quantity. hydrobenzoic acid is the chief product (Will-
The receiver then contains the lower boiling statter and Mayer, Ber. 41, 1479). When dis-
constituents of the oil, together with a somewhat tilled over heated zinc-dust it yields benzalde-
concentrated ammonia solution, whilst the hyde (Baeyer, Annalen, 140, 296). Calcium
contents of the still consist of a lower alkaline benzoate yields on distillation benzophenone
H H
layer and an upper oily one. The former is C 6 6 -COC 6 S , together with a small quantity of
neutralised with carbonic acid or a mineral acid, benzene and anthraquinone C 14 8 2 (Kekule H
separated from traces of phenol or resinous and Franchimont, Ber. 5, 908). Taken inter-
matters, and the resulting solution of sodium nally, benzoic acid is excreted in the urine as
benzoate decomposed whilst hot by adding an liippuric acid (Wohler).
excess of acid. On cooling, pure benzoic acid When a solution of ferric chloride which
separates in white crystals. tias been mixed with sufficient ammonia to turn
5. From the naphthols and other naphthalene it dark-red is added to a solution of a benzoate,
derivatives. Basle Chemical Works, J. Soc. a flesh-coloured precipitate of basic ferric ben-
H
Chem. Ind. 1901, 1139 ; D. R. P. 136410 ; Fr. zoate (C 7 6 2 ) 3 Fe,Fe(OH) 3 is formed. This re-
Pat. 313187; Eng. Pat. 15527; U.S. Pat. action is used in the separation of benzoic acid,
702171. (See also Chem. Zentr. 1903, i. 546, 857, and also in separating iron from manganese.
1106; D. R. PP. 138790,139956,140999.) By Uses. Benzoic acid is used in medicine ;
heating the naphthols or other naphthalene but for this purpose only the natural product,
derivatives to about 250, in presence of alkali obtained from gum benzoin by sublimation, is
with metallic oxides or peroxides such as copper suitable. Adulteration with the artificial acid
or iron oxide, barium, lead or manganese per- s detected by heating a portion of the acid on
oxide, they yield phthalic and benzoic acids, and ilatinum wire and holding a porcelain dish
a few intermediate products. The excess of noistened with pbloroglucolvanillin over the
alkali is removed by Hxiviation with a little lame ; the production of a red colour, due to
water ; the acids are then dissolved in water and ihe presence of hydrochloric acid, indicates the
decanted from the reduced oxide. This solution jresence of the artificial acid. Artificial benzoic
is saturated with carbon dioxide and filtered icid is employed in the manufacture of aniline
VOL. I. T. 2
450 BENZ01C ACID.
blue. It has been used as a mordant in calico- entirely of benzyl cinnamate. Benzyl benzoate
printing. Benzoic acid, dissolved in a mixture is a colourless oil, boiling at 173 under 9 mm.
of 1 part of ether and 20 parts of alcohol, has pressure, whilst the benzyl cinnamate is crys-
been recommended for the preservation of talline, melting at 37, and boiling at 213-
anatomical preparations. It is said to be used |
214 under 9 mm. pressure. It is stated that
in giving an aroma to tobacco. !
benzyl benzoate is as efficacious, therapeutically,

As an antiseptic it is injurious to health, as the ester obtained direct from Peru balsam,
j
producing serious disturbance of the metabolic whilst it has the advantages that it is free from
j
functions, attended with injury to the digestion !

colour and smell, is constant in composition,
(Wiley, U.S. Dept. of Agric., J. Soc. Chem. Ind. and does not cause the irritation sometimes
1908, 914). |
occasioned by Peru balsam owing to the free
Detection in foodstuffs. By the production acids present (E. Erdmann, Pharm. J. 65,
of diaminobenzoic acid (Mohler, Bull. Soc. chim. 387).
3, 414) ; by the action of the acid on rosaniline H
BENZOIC ANHYDRIDE (C 6 S -CO) 2 O. First
hydrochloride dissolved in aniline oil, when prepared by Gerhardt (Ann. Chim. Phys. [3] 37,
aniline blue is formed (De Brevans, J. Pharm. 299) by the action of benzoyl chloride on sodium
Chim. 14,438); by con verting the acid into salicy- benzoate or on sodium oxalate, or of phosphorus
licacid with hydrogen peroxide, and then adding i
oxychloride on sodium benzoate :

ferric chloride (Jonescu, J. Pharm. Chim. 29, H
C 6 5 -C0 2 Na+C6 H 6 -COCl=(CjH 6 -CO) 2 0+NaCl;
523). In butter: By the formation of ammonium 2C 6 H 5 -COCl+Na 2 C 2 4
diaminobenzoate, which gives a brownish-red =(C6 H 5 -CO) 2 0+2NaCl+CO+C0 2 ;
colouration in alkaline solution (Halphen, 4C s H 8 -C0 2 Na+POCl 3
Pharm. J. 28, 201 Robin, Ann. Chim. anal.
;
=2(C 6 H 5 -CO). 0+NaP0 3 +3NaCl.
i!
14, 53). In fermented beverages and milk : As Pour 100 grams of phosphorus
Preparation.-
in butter (Robin, Ann. Chim. anal. 14, 53 ;
oxychloride over 500 grams of dry sodium ben-
Breustedt, Arch. Pharm. 237, 170). In meats zoate contained in a flask ; complete the re-
and fats (Fischer and Gruenert, J. Soc. Chem. action by heating at 150 ; remove sodium salts
Ind. 28, 849).
by washing the cooled mass with dilute sodium
Examination of the commercial product.
carbonate, and pur,ify the anhydride by dis-
The benzoic acid of commerce is almost
artificial tillation.
always contaminated with chlorobenzoic acids Anschiitz (Annalen, 226, 15) heats benzoyl
(v. supra), the presence of which in any con- chloride with anhydrous oxalic acid. This
siderable quantity is stated to be detrimental in avoids the formation of metallic salts altogether.
the aniline blue manufacture. The chlorine It may also be prepared by heating benzoyl
may be detected by heating the acid with chloride with fused and powdered sodium nitrite
metallic sodium, extracting the residue with water for 12 hours ; the product is extracted with
and testing the solution with silver nitrate. ether and freed from traces of benzoic acid by
The acid should have the proper melting-point,
rapidly washing with a very dilute solution of
and should dissolve without residue in boiling sodium carbonate, and finally with distilled water ;
water.
yield 70 p.c. (Minunni and Caberti, Gazz. chim.
Salts and esters of benzoic acids. Benzoic
acid is monobasic. Most of the benzoates are
ital.20, 655). By mixing together benzoyl
chloride and pyridine and adding water after half
soluble both in water and in alcohol. Potassium an hour, pure benzoic anhydride is precipitated ;
H
benzoate C 7 S 2 K,3H._,0 : efflorescent laminae.
yield 80 p.c. (Minunni, Gazz. chim. ital. 22, ii.
H
Sodium benzoate C 7 5 2 Na,H 2 : efflorescent
213). By treating benzoyl chloride with sodium
needles, used for inhalation in tuberculosis. carbonate and pyridine ; yield quantitative
Ammonium benzoate C,H 6 2 (NH 4 ), rhombic (Deninger, J. pr. Chem. 50, ii. 479). By treating
crystals, also used in medicine. Calcium ben-
benzoyl chloride with sodium hyposulphite in
H
zoate (C 7 6 2 )Ca,2H 2 0, lustrous needles, used the presence or absence of pyridine (Binz and
in the preparation of benzophenone. Basic
Marx, Ber. 40, 3855) ; by treating benzene-
ferric benzoate (C } i
H 2 ) 3 Fe,Fe(OH) 3 (v. supra).
sulphonic chloride with sodium benzoate (Chem.
Mercuric benzoate small white odourless taste- Fab. von Heyden, D. R. P. 123052; Chem.
less crystals; powerful antiseptic ; successfully Zentr. 1902, 2, 618 ); by treating benzoic acid
employed in syphilitic and similar diseases or sodium benzoate with methylchlorsulphate
(Merck's Bull. 1890, [5] 33 ; [6] 49 ; [7] 73). (Bad. Anil, and Sod. Fabrik, D. R. P. 146690 ;
The esters of benzoic acid are obtained either Chem. Zentr. 1904, i. 65) ; by treating benzoic
by distilling benzoic acid with the alcohol and acid with acetic anhydride in the presence of an
sulphuric acid, or better, by saturating a solu- indifferent solvent such as benzene or xylene
tion of benzoic acid in the alcohol with (Kaufmann and Luterbacher, Ber. 42, 3483) ;
hydrogen chloride, digesting the mixture on the from benzotricbloride and acetic acid (Behal,
water- bath for some hours, precipitating the Compt. rend. 148, 648).
ester with water, and purifying by distillation. Properties. Rhombic prisms, sp.gr. 1-1989
H
Methyl benzoate C 7 5 O 2 -CH 3 is a liquid boiling 15/4, melting at 42, and boiling at 360 (corr.)
at 198-6 (Perkin, Chem. Soc. Trans. 69, 1025). (Lumsden, Chem. Soc. Trans. 1905, 93). Insoluble
H H
Ethyl benzoate C 7 6 2 -C 2 5 , boils at 211-8 in water ; readily soluble in alcohol and ether.
(Perkin, I.e.). Propyl benzoate C,H 6 2 -C 3 7 , H Reactions. Water decomposes it very slowly
boils at 230-7 (Perkin,- i.e.). in the cold, more rapidly on boiling, with forma-
Benzyl benzoate. This ester forms the tion of benzoic acid. Towards ammonia, amino-
therapeutically active portion of Peru balsam, and imino- compounds, alcohols and phenols, it
and also the larger fraction of the product behaves like benzoyl chloride, replacing by a
formerly known by the name of cinnamein, and benzoyl- group a hydrogen atom attached to
generally described as consisting chiefly or nitrogen or oxygen. For this reason it is, like
BERYL. 451
bcnzoyl chloride (q.v.), used as a reagent for manner itreacts with compounds containing
amino-, imino-, and hydroxyl- groups, and it has hydroxyl-, amino-, or imino- groups, introducing
the advantage over the latter reagent that no benzoyl in place of hydrogen, and is therefore
hydrochloric acid, a substance which has a very employed in organic chemistry as a test for the
prejudicial effect on many organic compounds, presence of these groups in a compound. Thus
is liberated during its action. with alcohol it yields ethyl benzoate ; with
BENZOIN GUM v. BALSAMS. aniline, benzanilide and dibenzanilide.
BENZOIN YELLOW. This compound is
BENZOYL GLYCOCOLL v. HJPPURIC ACID.
obtained by condensing benzoin with gallic acid.
BENZOYL PINK v. Azo- COLOURING MATTERS.
Benzoin is added to a solution of gallic acid in
BENZOYL SULPHONIC IMIDE and BEN-
ZOIC SULPHINIDE v. SACCHARIN.
sulphuric acid, kept at a temperature of 0-5,
and, after being stirred during 24 hours, the
BENZYLAMINE CARBOXYLIC ACIDS v.
mixture is poured into water, the dye being

AMINO- ACIDS (aromatic).
It crystallises from a mixture of BENZYL BLUE. A dye made by the
pfecipitated.
acetic acid and alcohol in yellow needles. Its Aktiengesellschaft fur Anilinfabrikation, Berlin,
constitution is given as by substituting three atoms of hydrogen in
rosaniline by three benzyl- groups. It is easily
C.H 4 -C =-C-Ph
soluble, in water; dyes silks, wools, and cotton
Ô [0:(OH) t :CO=l:2:3:4] (Reimann's Farber-Zeit, 1879, 251 ; Industrie-
CO C,H(OH) a / Blatter, 39, 360).
(Bad. Anil. Sod. Fab. D. R. P. 95739 ; Chem.
BENZYL CHLORIDE v. TOLUENE, CHLOR-
Zentr. 1898, i. 870, and Graebe, Ber. 31, 2975) INE DERIVATIVES OF.
(v. ALIZARIN AND ALLIED COLOURING MATTERS). BENZYLDIPHENYLAMINE v. DIPHENYL-
BENZONAPHTHOL v. SYNTHETIC DRUGS. AMINE.
BENZOPHENONE (Diphenyl Ketone) (v. BENZYLPHENYLHYDRAZONES v. HYDRA-
ZONES.
KETONES).
BENZOSALIN. Trade name for benzoyl- BERBERINE v. BARBERRY ROOT and VEGETO-
ALKALOIDS.
salicylic-acid- methyl ester, used in the treatment
of articular and muscular rheumatism, neuritis, BERENGELITE. A bituminous resinous
mineral from St. Juan de Berengela, Peru,
neuralgia, and sciatica. V. SYNTHETIC DRUGS.
BENZOSOL v. SYNTHETIC DRUGS. melting at 100, soluble in alcohol and ether.
BENZOTRICHLORIDE v. TOLUENE, CHLOR- According to Dietrich, specimens from Trinidad
INE DERIVATIVES OF. and Arien, Peru, contained 71-84 C, 9-95 H, and
BENZOYL CHLORIDE C ? H6 -COC1. First 18-21 of O (Chem. Zentr. 80, 559). Used for
obtained by Liebig and Wohler, by passing caulking ships.
chlorine into benzaldehyde (Annalen, 3, 262). BERGAMOT v. OILS, ESSENTIAL.
By the action of phosphorus pentachloride on BERGMANN'S POWDER. An explosive
benzoic acid (Cahours, Ann. Chim. Phys. [3] 23, composed of 50 parts potassium chlorate, 5 of
334). pyrolusite, and 45 of bran, sawdust, or tan (J.

Preparation. Benzoic acid is heated with 37, 1748).
slightly more than the molecular proportion of BERLIN BLACK. A black varnish drying
with a dead surface, used for coating iron-
phosphorus pentachloride
work.
C 6 H 5 -COOH+PC1 5 =C 6 H 6 -COC1+POC1 3 +HC1.
BERLIN BLUE or PRUSSIAN BLUE v.
The resulting benzoyl chloride is freed from the CYANIDES.
phosphorus oxychloride by fractional distillation. BERNTHSEN'S VIOLET. Isothionine. 0-
Commercial benzoyl chloride is usually con- Formed by reduc-
Amidothiodiphenylimide,
taminated with chlorbenzoylchloride and fre-
ng 0-dmitrodiphenylaminesulphoxide and oxi-
quently with small quantities of benzaldehyde The
dising the leuco- base with ferric chloride.
(V. Meyer, Ber. 24, 4251, and 25, 209). in needles.
From hydrochloride crystallises Dyes
oxalyl chloride, benzene, and alu- reddish-violet. Isomeric with Lauth's violet
minium chloride (Staudinger, Ber. 1908, 3566).
From benzoic acid or sodium benzoate and (Bernthsen, Annalen, 230, 133).
BERRY WAX v. WAXES.
methylchlorosulphate (Bad. Anil, and Sod. BERTHIERITE. Iron sulphantimonite (v.
Fabrik, D. R. P. 146690 ; Chem. Zentr. 1904,
ANTIMONY).
i.
65).
From salts of benzoic acid. By treatment
BERYL. A
mineral consisting of glucinum
aluminium silicate Be 3 Al 2 Si 6 18 , crystallising
with sulphur dioxide and chlorine (Farb. vorm.
in the hexagonal system. The ancient name,
Meister, Lucius and Bruning, D. R. P. 210805 ;
/S^puAAoy, included also some other gem-stones
Chem. Zentr. 1909, 279). of a greenish colour. The crystals are usually
Properties. Colourless liquid, with a pungent
quite simple in form, with only the hexagonal
odour, boiling at 199 (Lumsden, Chem. Soc.
Trans. 1905, 94); 197-2 (corr.) (Perkin, Chem. prism and the basal plane ; the habit being
Soc. Trans. 69, 1244). Its vapour attacks the
commonly prismatic and the prism faces striated
vertically. They are usually cloudy or opaque,
eyes, causing a flow of tears. Sp.gr. 1-2122 with a pale-greenish or yellowish colour and are
20/4 Annalen, 235, 11).
(Briihl, often of considerable size, crystals weighing as
Benzoyl chloride reacts with
Reactions.
much as one or two tons having been found at
water, slowly in the cold, rapidly on heating, Acworth inNew Hampshire. The sp.gr. is
with formation of benzoic and hydrochloric acids.
2-63-2-80, and the hardness 7^-8. The material
With ammonia it forms benzamide is not attacked by acids, except hydrofluoric ;
C 8 H f -CONH 2 and before the blowpipe is fusible only with

together with ammonium chloride. In like difficulty on the edges.
BERYL.
Crystals of a different type are found in asso- hydrogen, and the hydrochloride obtained from
ciation with lithia minerals (lepidolite and rubel- the solution by evaporation. If choline is also
lite) in certain pegmatites. These are tabular present, it can be removed from the mixed
in habit and rose-red or colourless. Further, hydrochlorides by extraction with cold alcohol,
they differ chemically in containing small leaving the betaine hydrochloride (Schulze,
amounts of alkalis (Cs 2 3-1, Li 2 1-4 p.c.). O Zeitsch, physiol. Chem. 1909, 60, 155).
V. Vernadsky (1908) expresses the composition Betaine crystallises from alcohol in large
by the formula arBeAl 2 Si 4 O lv -y A, where A crystals containing one molecule of water. It
is BeH 2 Si0 4 BeSi0 3 (?), Cs 2 Si6 3 , LioSi0 3 or
, ,
is deliquescent in air, and loses its water when
Na 2 Si0 3 ; and for the caesium-bearing variety dried over sulphuric acid. Strong sulphuric
he proposes the name vorobyevite. acid has but little action upon it, even at 120
Being by far the most abundant of glucinum (Stanek, Zeit. Zuckerind, Bohm, 1902, 26, 287).
minerals, beryl is employed for the preparation It is neutral to litmus, and has a sweet taste.
of the little-used salts of glucinum. It finds It melts and decomposes at 293 (Willstattcr,
more extensive application in jewellery. The Ber. 1902, 35, 584), giving off the smell of tri-
clear grass-green variety is the emerald, one of methylamine and of burnt sugar. The auri-
the most valuable of gems on account of the chloride CBH 11 N0 2 -HCl-AuCl 4 forms plates or
,
rarity of flawless material. Gem-stones of a needles which melt at 209 (Willstatter), or. ac-
greenish, bluish, or sea-green colour are known cording to Fischer (Ber. 1902, 35, 1593), at 250.
as aquamarine, while others are golden-yellow or H
The platinichloride PtCl 4 2(C 5 11 N0 2 ,HCl)-4H 2
rose-pink. L. J. S. forms large plates ; after losing its water it melts
BERYLLIUM v. GLUCINUM. and decomposes at 242 (Willstatter).
BERZELIANITE. Native copper selenide H
C 5 11 N0 2 -HC1 is very soluble hi water,
Cu 2 Se, occurring in a black powdery form in slightly soluble in cold alcohol. H
C 5 J1 N0 2 -HI
calcite at Skrikerum in Sweden and at Lehrbach is soluble in water or boiling alcohol, and melts
in the Harz. Named after the Swedish chemist at 188-190. A compound with KI crystallises
J. J. Berzelius (1779-1848), who first analysed it. as (C 5 Hi 1 N0 2 ) 2 -KI,2H 2 0, m.p. 139 (Kornerand
L. J. S. Menozzi, Gazz. chim. ital. 13, 351), or, if anhy-
BERZELIITE. Arsenate of calcium, manga- drous, at228-229 (Willstatter).
nese, and magnesium (Ca,Mn,Mg) 3 As 2 8 occur- , The term betaine is now used
'
'
generally for
ring as small yellow cubic crystals, and as com- substances containing the group
pact masses, with ores of iron and manganese
at Ltlngban in Wermland, Sweden. Also CO
named after J. J. Berzelius. Other forms of the with other alkyl- groups than methyl, or other
same name, berzeline and berzelite, have been
acyl- groups than acetyl.
applied to these, as well as to some other minerals. Thus, dimethylethylaeetylbetaine or (since
L. J. S.
acetyl is to be understood if no acyl- group is
BESSEMER STEEL v. IRON. mentioned) dimethylethylbetaine
BETAINE (CH 3 3N<^
H be
j^CO ) may
regarded as the internal anhydride of the
acid (CH 3 3 N(OH)-CHyCOOH
) derived from crystallises from alcohol in four-sided plates,
acetic acidby the replacement of one atom of melting and decomposing at 229-231 (Will-
hydrogen by trimethyl hydroxyammonium. statter), while trimethylbutyrobetaine
It occurs in beets and mangolds (especially
unripe roots), in cotton seed, in the shoots of
barley, in wormseed (Artemisia gallica) and in with 3H 2
crystallises in colourless plates in ;
many other plants, often in association with the anhydrous state it softens at 130 and
choline, from which it may readily be obtained decomposes at 222 (Willstatter).
by oxidation. The betaines are isomeric with the esters
Betaine can be synthesised by the inter- of amino- acids ; thus, ordinary betaine is
action of chloracetic acid and trimethylamine isomeric with methyldimethylaminoacetate
(Liebreich, Ber. 1869, 2, 13). (CH 3 ) 2 N-CH 2 -CO-OCH 3 a , volatile oily liquid,
It can be extracted from beet-root molasses b.p. 135, while trimethylbutyrobetaine is iso-
by dilution with water, boiling with baryta, meric with methyl--y-dimethylaminobutyrate

8
filtering, precipitating the excess of BaH 2 2 (CH 3 ) 2 :N-CH 2 -CH 2 -CH 2 -COO-CH 3 , b.p. 171 -
with CO 2 , evaporating the liquid to small volume, 173.
and extracting with alcohol. The alcoholic (For betaines of the pyridine series, see
solution is treated with alcoholic zinc chloride, Kirpal, Monatsh. 1908, 29, 471.)
the ppt. recrystallised from water and decom- According to Schulze and Trier (Zeitsch.
posed by baryta water. The barium is then physiol. Chem. 1910, 67, 46), the three betaines
exactly removed from the filtrate by H 2 S0 4 and , which have been isolated from plant tissues are :
betaine hydrochloride crystallises on evaporation betaine, trigonelline [found in fenugreek by
(Liebreich, Ber. 3, 161 ; Friihling and Schulz, Jahns (Ber. 1886, 18, 2518) associated with
Ber. 10, 1070). choline], and stachydrine, found in the tubers
A general method of obtaining betaine from of Stachys tuberifera and in the leaves of Citrus
plant extracts is to precipitate with lead acetate, aurantium (v. TRIGONELLINE and STACHYDRINK).
filter, remove the lead by sulphuretted hydrogen, H.I.
filter, evaporate to dryness, extract residue with BETEL. A
mixture of the leaf of the betel-
alcohol, and precipitate with alcoholic mercuric pepper, Piper Betle (Linn.) with the fruit of
chloride. The mercuric double salt is then Areca catechu (Linn.) or betel nut and chunam
recrystallised, decomposed by sulphuretted (lime obtained by calcining shells), universally
BIDRY. 453
used by the people of Central and Tropical Asia Muell.), Mercurialis perennis (Linn.), and M.
as a masticatory. tomentosa (Linn.). The juice exists in all these
BETEL-NUT. The fruit of Areca catechu slants in the colourless state, and turns blue only
(Linn.).
on exposure to the air (Handw. d. Chem. 2, [1]
BETH-A-BARRA WOOD. A wood imported 1030 ; Gerh. Traite', 3, 820).
from the West Coast of Africa, much valued for BEZOAR. This name, which is derived from
its toughness and capability of receiving a high a Persian word signifying an antidote to poison,
polish. The interstices of the fibres are filled was given to a concretion found in the stomach
with a yellow crystalline substance which can be or intestines of an animal of the goat kind,
extracted from the sawdust by heating with dis- 'apra aegragus, which was once very highly
tilled water containing a little sodium carbonate, valued for this imaginary quality, and has thence
and precipitating the resulting claret-coloured been extended to all concretions found in
solution with acetic acid. It is purified by animals.
repeated crystallisations from 80 p.c. alcohol. According to Taylor (Phi!. Mag. No. 186, 36,
By precipitating the red solution with hydro- and No. 186, 192), bezoars may be divided
chloric acid and washing the resulting precipitate into nine varieties 1. Phosphate of calcium,
:
with ether, Greene and Hooker (Amer. Chem. J. A'hich forms concretions in the intestines of many
11, 267) found the crystals to be identical in mammalia. 2. Phosphate of magnesium ;
all respects with lapachic acid. semi-transparent and yellowish, and of sp.gr.
If differs from chrysophanic acid by melting 2-160. 3. Phosphate of ammonium and mag-
at 135 and in not forming a compound with nesium ; a concretion of a grey or brown colour,
alum (Sadtler a. Rowland, Amer Chem. J. omposed of radiations from a centre. 4.
1881, 22). (For tables showing the difference in Oxalate of calcium. 5. Vegetable fibres. 6.
the reactions of brasilin, hsematoxylin, santalin, Animal hair. 7. Ambergris. 8. Lithofellic
and beth-a-barra-, v, Amer. Chem. J. 11, 49, and acid. 9. Ellagic or bezoardic acid.
Wagner's Jahr. 28, 537.) Of true bezoars there are three kinds : Oriental,
BETOL SYNTHETIC DRUGS.
v. Occidental, and German. The true Oriental
BETORCIN or 0-ORCIN C 8 Hi 2 . A sub- bezoars found in the Capra cegragus, the gazelle
stance obtained by the decomposition of bar- (Gazella dorcas), and other ruminant animals,
batic acid, found in the lichen Usneabarbata. It are spherical or oval masses, varying from the
is lesssoluble hi water than orcin, and gives a size of a pea to that of the fist, and composed of
deeper crimson colour with hypochlorites. Kos- concentric layers of resinous matter with a
tanecki has obtained it by the action of nitrous nucleus of some foreign substance, such as pieces
acid on m-amino-p-xylenol, thus showing that it of bark or other hard vegetable matter which
is a dihydroxy-xylene (dimethylresorcinol) having the animal has swallowed. They have a shining
the substituting groups in the positions 3, CH resinous fracture, are destitute of taste and odour,
CH 3 OH, OH=1,
, 4, 3, 5 (Stenhouse a.
Groves, nearly insoluble in water and aqueous hydro-
Chem. Soc. Trans. 37, 396 ; Lampartie, Annalen, chloric acid, but soluble for the greater part in
134, 248; Menschutkin, Bull. Soc. chim. 2, potash lye. These characters suffice to distin-
428; Kostanecki, Ber. 19, 2321). guish the Oriental bezoars from those varieties
BETULA RESIN v. RESINS. which contain a considerable quantity of in-
BEZETTA. Tournesol en drapeaux. Schmink- organic matter. There are two kinds of them,
lappchen. Bezetta rubra et ccerulea. A dye or the one consisting of ellagic, the other of litho-
pigment prepared by dipping linen rags in solu- fellic acid. The latter have a more waxy lustre
tions of certain colouring matters. Red bezetta is and greener colour than the former, and are also
coloured with cochineal, and is used as a cosmetic. distinguished by their lower sp.gr., viz. 1-1,
Blue bezetta (Tournesol en drapeaux), which whilst that of the ellagic acid stones is 1-6. They
is chiefly used for colouring the rind of Dutch contain, besides lithofellic acid, a substance
cheeses, is prepared at Gallargues, near Mmes, resembling the colouring matter of bile, and are
in the department of Gard, from a euphorbi- perhaps biliary calculi. Oriental bezoars are
aceous plant, Chrozophora tinctoria (A. Juss.) greatly prized in Persia and other countries of
[Croton tinctorius]. The fruits and the tops of the East for their supposed medical properties.
the plants are gathered, and, the juice being The Shah of Persia sent one in 1808 as a present
expressed, rags of coarse cloth are dipped into it, to Napoleon. The Occidental bezoars are found
then dried, and afterwards exposed to the fumes in the lama (Auchenia glama) and in A. vicugna.
of mules' or horses' dung. This last operation They resemble the Oriental in external appear-
is called aluminadou. The cloths are turned ance, but differ totally in their chemical cha-
from time to time, to ensure uniform colouration inasmuch as they consist chiefly of cal-
racters,
and prevent any part from being exposed too cium phosphate, with but little organic matter.
long to the fumes of the dung, which would German bezoars, which are chiefly obtained
turn them yellow. They are then dried a from the chamois or gemsbock (Bupicapra
second time, again soaked in the juice, mixed tragus), consist chiefly of interlaced vegetable
this time with urine, and lastly exposed for some fibres or animal hairs bound together by a
time to the action of the sun and wind. The leathery coating.
quantity thus manufactured amounts to about BICUHYBA FAT. See MYEISTICA FAT
50 tons yearly. The blue of bezetta is reddened GROUP.
by acids like litmus, though not so quickly, but BIDRY. An Indian alloy of zinc, copper,
differs from the latter in not being restored by and lead, and occasionally tin. Articles of this
alkalis. According to Joly, the sams dye may alloy, after being turned in a lathe and engraved,
be obtained from other euphorbiaceoua plants, are blackened by immersion in a solution of sal
Chrozorphora oblongata [obliqua (A. Juss.) ?] ammoniac, nitre, common salt, and copper sul-
C. plicata (A. Juss.), Argithamnia tricuspidata phate. Known also as Vidry.
454 BIEBRICH ACID RED, PATENT BLACKS, SCARLET PONCEAU.
BIEBRICH ACID RED, PATENT BLACKS, The colouring matter of the juice can be
SCARLET PONCEAU v. Azo- COLOURING MAT- extracted by neutralising it with caustic soda and
TERS. then treating it with hide powder. After two days
BILBERRY. Vaccinium Myrtillus (Linn.). the hide powder containing the colouring matter
Konig gives as the average composition of the is filtered off, washed with water, and treated
fruit : with dilute hydrochloric acid, after which it is
Free Other carbo- Crude precipitated with dilute soda. The colouring
Water Protein acid Sugar hydrates fibre Ash H
substance, probably C 10 12 O 3 is, soluble in
78-4 0-8 1-7 5-0 0-9 12-3 1-0
mineral and organic acids, but insoluble in water,
According to Otto (Bied. Zentr. 1899, 28, alcohol, ether, chloroform, or benzene. It
284), Silesian bilberries contain from 3-5 to 7-0 reduces Fehling's solution, and is decomposed by
p.c. of sugar and acid corresponding io from hot cone, sulphuric acid, a compound C 14 14 7 H
0-9 to 1-5 p.c. of tartaric acid. He found being thrown down when water is added to the
that fermentation of the juice with ordinary red solution thus obtained. The colouring
yeast was very slow unless some nitrogenous matter is oxidised by nitric acid to oxalic and
matter (e.g. ammonium chloride or, better, It slowly decomposes on stand-
picric acids.
asparagine (about 0-6 gram per litre) ) were ing, evolving carbon dioxide, and its solution
added. Bilberries contain a small quantity of a when treated with copper sulphate or zinc
wax melting at 71 (Seifert, Landw. Versuchs- chloride, turns violet; with lead acetate it turns
Stat. 1894, 45, 29).
blue, and with ferric chloride dark - brown
The juice of bilberries contains from 4 to
(Nachen, Chem. Zentr. 1895, 66, 1084).
9-5 p.c. of total solids, 0-25 to 0-31 p.c. ash, and Considerable quantities of citric and malic
acidity corresponding to from 15-5 to 19-6 c.c. acids are present in the juice, which also contains
N/l alkali. The juice contains some substance
hydrocarbons, glucoses, pentoses, and inosotol
which gives a blue colouration when heated with
(Nachen, I.e.). Ammonia turns bilberry juice
hydrochloric acid. This colouration is ap- a brownish-green nitric acid in the cold blue,
;
parently not connected with the red colouring changing to red and becoming orange on boiling ;
matter of the berries and appears to be cha- lead acetate gives a blue precipitate, copper
racteristic of the Vacciniacece for cranberries,
sulphate a violet colour, sodium carbonate a
Vaccinium vitis Idcea also yield the same blue- black, and borax an amaranth red
reaction (Plahl, Zeitsch. Nahr. Genussm. 1907,
(Griessmayer, Chem. Zentr. 8, 381).
13, 1). When chlorine is passed into the juice, a
The sugar in bilberries is entirely invert
bright-grey amorphous precipitate is obtained
sugar (Windisch and Boehm, Zeitsch Nahr. (Nachen, I.e.).
Genussm. 1908, 8, 347). The ash contains
(For quantitative analysis of the juice, com-
:
K 2 O Na 2 O CaO MgO Fe 2 O 3 Mn 3 O 4 P 2 O 5 S0 3 Si0 2 pare Mathes, Muller, and Ramstedt (Chem.

57-1 5-2 8-0 6-1 1-1 2-1 17-4 3-1 0-9 Zentr. 1905, i. 407); Liihring, Bohrisch, and
Hepner 1907, ii. 1755) ; Shamm and
(Borggreve and Homberger, Bied. Zentr. 1886,
(ibid.
Jegin 1907, i. 983); Behre, Grosse, and
(ibid.
487).
Bilberries contain a red-brown dye, insoluble
Schmidt (ibid. 1909, i. 456).)
in acidified water and a soluble dye which, when
When the juice is fermented, the products
boiled with acid, yields sugar and the insoluble
include aldehyde, and capric, propionic, valeric,
and butyric acids (Nachen, I.e.).
colouring matter (Weigert, Bied. Zentr. 1896,
Wine has been prepared from bilberry juice
25, 58).
Thejuice of this berry (Ger. Heidelbcere)
by allowing it to ferment spontaneously when
is used for colouring wines. The colouring mixed with a third its weight of honey. The
matters of grapes and of bilberries behave in wine thus prepared bears prolonged storage, is
an almost identical way with most reagents rich in alcohol and tannin, is of a rich clear
colour, and has an agreeable flavour (Graftien,
(Andre'e, Arch. Pharm. [3] 13, 90; Ber. 13,
Bl. Assoc. Beige des chim. 12, [3] 107 ; Otto,
582 ; Plahl, Chem. Zentr. 1907, i. 837).
Bied. Zentr. 1899, 28, 284).
To detect bilberry juice in wine, 50 c.c. of
the wine is made faintly alkaline with sodium When bilberries are extracted with chloro-
form, the solution evaporated, and the residue
hydroxide, and evaporated to half its volume.
After cooling it is made up to the original volume extracted with light petroleum, the soluble portion
and precipitated with lead acetate. The filtrate yields a wax, m.p. 71,andacrysta!lineconipound,
is then precipitated with sodium sulphate and probably vitin, m.p. 255-260 [a] +60-72
after filtration the solution is acidified with Landw. Versuchs-Stat. 45, 29).
(Seifert,
hydrochloric acid. If any vegetable colouring BILE. Bile is the secretion of, the liver which
matter is still the solution at once
present, is poured into the duodenum (the first part of
becomes red, but the blue colour given by the small intestine). It can be collected in
bilberry only appears on heating the solution in animals by means of a biliary fistula ; the same
a boiling water-bath. In this way 2 p.c. of operation has occasionally been performed in
bilberry juice can be detected (Plahl, Chem. human beings. After death, the gall bladder
Zentr. 1908, i. 1482). yields a good supply of bile, which is more
According to Vogel (Ber. 21, 1746), the concentrated than that obtained from -a fistula.
colouring matter of grapes and of bilberries can The amount of bile secreted is differently
be readily distinguished by their absorption estimated by different observers ; in man it
spectra, providing the wine is not too concen- probably varies from 500 to 1000 c.c. per diem.
trated, and after adding a trace of alum solution, Its constituents are the bile salts proper
it is carefully neutralised with ammonia. After (sodium glycocholate and taurocholate), the bile
long keeping, however, the colouring matters pigments (bilirubin and biliverdin), a mucinoid
cannot be distinguished in this way. substance, small quantities of fats, soap,
BILE. 455
and mineral salts,
cholesterol, lecithin, urea, of action of and acids, and also in
dilute alkalis
which sodium chloride and the phosphates of the intestine, hydrolysed and split into glycine
calcium and iron are the most important. (amino-acetic acid), and cholalic (cholic) acid
Bile is a yellowish, reddish-brown, or green C 26 H 43 N0 6 +H 2 0=C 2 H 5 N0 2 +C 24 H, S .
fluid, according to the relative preponderance Its sodium salt has the formula C!. H oNaNO .
4
of its two chief pigments. It has a musk-like 6 i!6
Taurocholic acid (C 2(,H 45 N() 7 S) similarly splits
odour, a bitter-sweet taste, and is alkaline to into taurine (aniinoisethionic acid) and cholalic
litmus. The specific gravity of human bile is acid
1-026 to 1-032 from the gall bladder, and about
1-011 when derived from a fistula. The greater C 26 H 4J NO ? S+H 0=C H N0 S+C 24 H 40
2 2 7 3 5
.
concentration of gall-bladder bile is partly Itssodium salt has the formula C 26 H 44 NaN0 7 S.
explained by the addition to it from the wall of These substances usually are detected by
that cavity of the mucinoid material it secretes. Pettenkofer's reaction ; small quantities of
The following table will, however, show that cane sugar and sulphuric acid added to the bile
the low percentage of solids in fistula bile is due produce a brilliant purple colour. This is due
mainly to paucity of bile salts. This is accounted to the interaction of furfuraldehyde (produced
for in the way first suggested by Schiff that from the sugar and sulphuric acid) and cholalic
there is normally a bile circulation going on in acid.
the body, a large quantity of the bile salts that Throughout the animal kingdom considerable
pass into the intestine being first split up, then variations are found in the bUe salts. Thus in
re-absorbed and again synthesised and secreted. many fishes potassium instead of sodium salts
This would obviously be impossible in cases are present. There are also variations in the
where all the bile is discharged to the exterior bile acids themselves ; for instance, in the
pig
through a fistula. The following is the table in hyoglycocholic acid (C 27 43 8) takes the H N0
question, the results being the mean of several place of ordinary glycocholic acid, and in the
analyses of human bile :- goose' chenotaurocholic acid (C 29 49 NS0 6 ) of H
Fistula Gall-bladder ordinary taurocholic acid.
Constituents bile bile A good deal of work has been expended
Bile salts . . . 0-42 9-14 on the constitution of cholalic acid, but much
Cholesterol, lecithin, fat . 0-07 1-18
yet remains to be done. According to Mylius, it
Mucinoid material . . 0-17 \ n no is a monobasic alcohol acid with a
secondary
Pigment . 0-07 J
and two primary alcohol groups. Its formula
Ash 0-66 0-78
therefore be written
(CHOH
C 20 H 3 J(CH 2 OH).,. On
may
Total solids . . .1-39 14-08
ICOOH.
'
Water (by difference) 98-61 85-92 oxidation yields other acids, which have
.
it
The Fel bovinum purification of the pharma- been named dehydrocholalic acid (C 24 3 ,O K ), H
copoeia is made by mixing ox bile with twice its H
bilianic acid ( C 2 4 34 8 ), cilianic acid (C 20 2 8 8 H ) ;
volume of rectified spirit this is set aside for

: on reduction desoxycholalic acid (C 24 40 O 4 ) H
12 hours until the sediment subsides; the clear is obtained.
solution is decanted and evaporated on the Choleic acid is another cholalic acid, Avith the
water - bath until it acquires a consistence H
formula C 24 40 4 found in small quantities in
,
suitable for forming pills. The material so the bile of ox and man. It is probably identical
obtained consists mainly of bile salts, cholesterol, with desoxycholalic acid. Fellic acid (C 23 40 4 ) H
fats, salts, and a certain amount of the mucinoid is still another acid obtainable from human bile
material. Its yellowish-green colour is due to along with the ordinary acid. The principal
bile pigment. It is given in doses of 5 to 10 cholalic acid in bear's bile is termed ursocholeic
grains, usually as pills coated with keratin to H H
acid (C 18 28 O 4 or C 19 30 4 ) by Hammarsten.
obviate its deleterious action on gastric digestion. The same investigator finds in the walrus that
It is given mainly in cases where the natural the principal bile acids are o-phocsetaurocholic
secretion is absent or scanty, as in jaundice. acid, the cholalic acid from which has the
But for a full description of its medicinal uses, formula C 22 H 30 O & ; and #-phocaetaurocholic
and also for a description of the action of drugs acid, the cholalic acid from which differs in
(cholagogues) which stimulate the liver either certain particulars from ordinary cholalic acid,
to secrete more bile or to cause a discharge of although it has the same empirical formula ;
bile already formed, the reader is referred to any he terms it isocholalic acid.
standard text-book on Pharmacology. The bile pigments. Bilirubin has the
Plattner's crystallised bile. The bile salts formula C 16 H 18 N 2 O 3 , and biliverdin contains
are soluble in water and in alcohol, but not in an atom more of oxygen (Ci S Hj 8 N 2 4 ) in bile ;
ether. Their solution in alcohol is therefore exposed to the air, bilirubin is fairly rapidly
precipitated by ether, and this precipitate gives, oxidised to biliverdin. It has been proved
with proper precautions in technique, rosettes by physiological experiment that the bile
or balls of fine needles, or 4-6 sided prisms pigment is an iron-free derivative of the blood
composed of the bile salts. This preparation is pigment it is, in fact, identical with the sub-
;
known as Plattner's crystallised bile ; it is stance termed hsematoidin, which occurs usually
usually made from ox bile, in which case the in crystalline form in extravasations of blood
main constituent is sodium glycocholate. in the body, as in a bruise. The bile pigment
The bile salts. The sodium salts of glyco- shows no absorption bands with the spectroscope,
cholic and taurocholic acids are those most fre- and is detected by various colour reactions, of
quently found. The former is more abundant in which the most familiar is Gmelin's test this ;
the bile of man and herbivora, the latter in car- consists in the play of colours green, blue, red,
nivora. Glycocholic acid (C 24 H 43 NO 8 ) is by the and finally yellow produced by the oxidising
456 BILE.
action of fuming nitric acid. The end or yellow peutic agent, to which allusion has already been
product is called choletelin (C 16 H 18N 2 6 ). made, bile has but little commercial importance.
By reduction outside the bod} a product called
7
,
It however, employed for cleansing woollen
is,
H N
hydrobilirubin (C 32 40 4 O 7 ) is obtained. A goods, and, as housekeepers know, is specially
similar but not identical reduction product con- useful in cleaning carpets. This is probably
taining less nitrogen than hydrobilirubin is connected with its power of lowering surface
formed in the intestine, and constitutes ster- tension. Bile is also used by artists to ensure
cobilin, the pigment of the faces. Some of this the uniform spreading of water colours on paper.
is absorbed and ultimately leaves the body in No attempt has been made in the foregoing
the urine, where it is termed urobilin. A small article to allude to the very extensive literature
quantity of urobilin is sometimes found pre- of bile. This relates almost exclusively to the
formed in the bile. physiology and pathology of bile, and the
Bile mucin. The viscous material in the important references can be best obtained from
bile of some animals (e.g. man) is true mucin ; some standard work on Physiological Chemistry,
in other (e.g. the ox) it is a nucleoprotein. such as Hammarsten's. W. D. H.
Cholesterol. Of the other constituents of BIRCH BARK. Betula. (Birke, Ger. ;
the bile, cholesterol or cholesterin is the most Bouleau, Fr.) The inner bark is used in India
interesting ; although normally present in traces as a substitute for paper and for lining the roofs
only, it may occur in excess and form the con- of houses (Dymock, Pharm. J. [3] 10, 661).
cretions known as gall stones, which are usually It contains good tanning materials, yielding
more or less tinged with bile pigment. It is a bright-yellow leather (Wagner's Jahr. 30, 1206 ;
monatomic unsaturated alcohol, with the Trotman and Hackford, J. Soc. Chem. Ind. 1905,
empirical formula C.27 H 45 -OH. Windaus and 1096 Bogh, Chem. Zentr. 1906, i. 1915).
;
others have shown that it is a member of the The dry distillation of birch bark yields a
terpene series, which had hitherto only been tar and an acid aqueous solution (Kuriloff,
found as excretory products of plant life. J. Russ. Phys. Chem. Soc. 23, 98). The chief
The physiological uses of bile. Bile is doubt- constituents of birchwood tar creosote are
less to some extent an excretion. Some state guaiacol and 1:3: 4-creosol, together with traces
that it has a slight lipolytic action ; and in of phenol, cresol, and 1:3: 4-xylenol (Pfreager,
some animals it certainly has a feeble diastatic Arch. Pharin. 228, 713). According to Hirschsohn
power. Its main action, however, is to assist (Pharm. Centr. H, 1903, 44, 845) birch tar is
pancreatic digestion ; this it does not only often adulterated with crude naphtha or
because its alkalinity is useful in helping to naphtha residues, but the adulterated can be
neutralise the acid mixture which leaves the distinguished from the pure product by the
stomach (chyme), but it also acts as a coadjutor fact that the former is only partially soluble in
to the enzymes of pancreatic juice. This is acetone, whereas the latter is wholly soluble.
true for the proteolytic enzyme (trypsin), and When warm birch tar is treated with air,
the amylolytic enzyme (amylopsin), but is oxygen, or ozonised air, a pleasant-smelling solid
especially so in the case of pancreatic lipase ; product is obtained, soluble in alkalis, but almost
some go so far as to speak of the bile salts as the insoluble in alcohol, benzene, and ether. It and
co-enzyme of this ferment. its salts can be employed in medicine, pharmacy,
In virtue of the properties which the bile and technically. At the same time, readily
salts possess of lowering surface tension, the condensible liquid products distil over, which
products of fat -cleavage pass more rapidly can also be used medicinally and technically,
through membranes moistened with bile than as antiseptics and in perfumery (Friedlander's
through these which are not. There is a good Fortschr. der Teerfabr. 1905-7, 930).
deal of evidence that the same holds infra vitam, Acolouring substance employed in pharma-
and thus the presence of bile aids the absorption ceutical and cosmetic preparations is obtained
of fats by the mucous membrane which lines when the bark of young birch trees is soaked in
the intestinal wall. Bile also is a solvent of water containing about ^ of its weight of
fatty acids. bicarbonate of soda or other carbonate. It is
When the bile meets the chyme, the turbidity then boiled and filtered. Hydrochloric acid is
of the latter is increased owing to the precipita- added to the red-brown filtrate until a pre-
tion of unpeptonised protein. This action of the cipitate is formed which is filtered, washed, and
bile salts is probably useful, as it converts the dried at a gentle heat. It should be kept in well :
chyme into a more viscid mass, and somewhat stoppered vessels (Friedlander's Fortschr. der
hinders itsprogress along the first part of the Teerfabr. 1897-00, 661).
intestine, so allowing digestion and absorption The bark contains a crystalline substance
to occur there. H
termed betulin C 33 60 3 m.p. 257-8, sublimes
,
Bile is said to be a natural antiseptic, but it in a current of air, readily yields an anhydride at
is very doubtful if it is
really efficient in reducing 130, and is tasteless and odourless. It does not
the putrefactive processes in the bowel. The combine with acids or alkalis, is insoluble in
bile salts are in vitro very feeble germicides, water, sparingly soluble in alcohol, readily in
and the bile itself is readily putrescible ; any ether and turpentine.
power it may have
in lessening putrescence in It is prepared by mixing the powdered
the intestine is due
chiefly to the fact that by epidermis of Betula alba with 1-8 p.c. of potas-
increasing absorption it lessens the amount of sium nitrate, pressing the mixture into small
putrescible material in the intestinal tract. It tablets, and burning them in closed chambers
is stated also that bile increases the
peristaltic without flame, and with the introduction of a
action of the large intestine. regulated supply of air. The betulin so formed
Industrial and commercial uses of bile. is used as films for certain substances in which
Apart from a somewhat limited use as a thera- it acts as an antiseptic, as a protection against
BISMARCK BROWN. 457
damp or against corrosive acids (Wheeler, (Chem. Zentr. 1909, ii. 2156) had sp.gr. 0-9730
Pharm. J. 1899, 494). at 15 and aD -5 34'.
The films can be deposited direct on various It contains a paraffin, m.p. 50, an ester,
substances by allowing the vapours to play upon and a sesquitorpene alcohol, betulol, probably
them. By a slight modification the films can C 15 H 23 OH, which is very much like amyrol
ho made to have a greater or less degree of (obtained from sandahvood oil),
has a bitter
transparency and porosity (Wheeler, Chein. taste, an odour like incense, b.p. 284-288/743
Zentr. 1900, ii. 798). mm., 138-140/4 mm. sp.gr. 0-975; [a] D -35
;
According to Wheeler (J. Soc. Chem. Ind. (von Soden and Elze, Ber. 38,
1636 Haensel, ;
1899, 606), when birch bark or materials made Chem. Zentr. 1909, ii. 1156. Compare also
from the latter, containing betulin are heated Pharm. Zeit. 47, 818 ; Schimmel, Chem. Zentr.
in a closed chamber and in a current of air,
1905, i. 1340).
substances termed pyrobetulin and pyrobetulin The leaves of Betula alba yield an olive-green
anhydride are produced in forms other than
films.
which is solid at ordinary temperature, but
H
Gaultherine C 14 18 S ,H 2 O, a glucoside, is
oil,
fluid at 35, has sp.gr. 0-9074 at 35, and is
obtained by extracting the bark of Betula knta Chem. Zentr. 1904,
optically inactive (Haensel,
with alcoholic lead acetate, precipitating by
and from alcohol. The
ether, recrystallising Haensel (Chem. Zentr. 1908, i. 1837) has
aqueous solution has a bitter flavour, is laevo- isolated a crystalline paraffin, m.p. 49-5-50,
rotatory, and reduces Fehling's solution
when
from the oil of birch leaves.
boiled. It is hydrolysed by mineral acids,
According to Grasser and
Purkert (Chem.
baryta, and by water when heated to 130-140, Zentr. 1910,i. 489), products C 4 iH 70 7 ,C 3? 68 0;,, H
giving a sugar and methyl salicylate (Schaugans readily soluble in water,
and of which the
and Geroch, Arch. Pharm. 232, 437).
H potassium salt C 41 S7 3 H K
7
can be used thera-
A gum of probable formula C 4 6 O 3 has been can be obtained by
peutically as a diuretic,
isolated from American birch wood (Betula with alcohol, treating
Amer. Chem. J. 1896, 214). extracting birch leaves
alba) (Johnson, the warm extract with potassium hydroxide,
Birchbark oil is obtained by distilling birch and then saturating the solution with dry
bark (Betula alba) in steam. It is brown, and carbon dioxide. Water is now added and the
has a similar odour to birch bud oil. On cooling, The filtrate is
insoluble products filtered off.
crystals separate. It contains palmitic acid
concentrated, the soluble products precipitated
(Haensel, Chem. Zentr. 1907, ii. 1620 ; Ziegel- with a mineral acid, and separated from one
mann, Pharm. Review, 1905, 23, 83). another by conversion into their di- and tri-
The birch bark oil prepared from the bark of alkali derivatives.
Betula alba by Haensel (Chem. Zentr. 1908, ii.
- Birch juice obtained from birch trees contains
1436), had sp.gr. 0-9003 at 20 and [a] D 12-08; a large quantity of malates, and.
Isevulose,
a colourless monocyclic sesquiterpene was basic constituents. When fermented with '
isolated from it, having b.p. 256-256/744 mm., dextrose and milk of almonds, it forms birch
sp.gr. 0-8844 at 20, and [a] D 0-5. The wine' (Lenz, Ber. Deut. Pharm. Ges. 19, 332).
terpene yields a hydrochloride, sp.gr. 0-9753 at BIRD-LIME. (Glu, Fr. ; Vogelleim, Ger.)
20, and a hydrocarbon, b.p. 258-260/747 mm., Bird-lime, from Ilex aquifolium (Linn.), was
and sp.gr. 0-8898 at 20. found by Personne to consist, in addition to
of calcium oxalate,
Birch oil, or the wintergreen oil of commerce, vegetable debris and water,
is obtained from the twigs of North American caoutchouc, and ethereal salts of a solid crystal-
birches, especially the Betula lenta, but the pure
H
line substance, Hide alcohol C 25 44 0, m.p. 175,
genuine oil is prepared from Oaultheria pro- with undetermined fatty acids.
cumbens (J. Soc. Chem. Ind. Abstr. 1893, 174). According to Divers and Kawakita, Japanese
ethereal
It consists of methylsalicylate, a hydrocarbon bird-lime, made from /. Integra, contains
C 18 H 24 , and small quantities of benzoic acid and salts of palmitic acid, and in very small quantity
ethyl alcohol (Schroeter, Amer. J. Pharm. a semi-solid acid, the calcium salt of which is
Aug. 1889 Trimble and Schroeter, Pharm. J.
; soluble in ether and in alcohol. Japanese bird-
20,166; Ziegelmann, Z.c.). lime also yields two very similar alcohols by
from ilicic
Oil of Gaultheria procumbens contains 99 p.c. hydrolysis, one differing only slightly
methylsalicylate, together with some paraffin alcohol, and termed ilicylic alcohol
C 22 38 0, H
C 30 H(, 2 probably triacontane ; an aldehyde m.p. 172, and another
named mochylic alcohol
or ketone ; a secondary alcohol C 8 16 0, and H H
C 26 46 0, m.p. 234, from mochi, the Japanese
an H
ester C 14 24 2 , and is laevo-rotatory, sp.gr. wordfor bird-lime.
1-180 ; that obtained from the birch contains is also present in Japanese bird-
Caoutchouc
99-8 p.c. methylsalicylate, together with the lime to the extent of about 6 p.c., but only
above constituents except the alcohol C S H 16 0, minute quantities of oxalates. By distillation,
which is absent. It is optically inactive ; sp.gr. bird-lime yields much palmitic acid and a thick
hydrocarbon C 26 H 44 (Divers
1-187 (Pharm. J. 1895, 307, 328). and Kawakita,
oily
Birch bud oil is obtained by the distillation Chem. Soc. Trans. 1888, 268).
of birch buds with steam. It is yellow, and has BIREEZ. Persian name for gum galbanum
a pleasant aromatic odour. Crystals separate (Dymock, Pharm. J. [3] 9, 1016).
out at ordinary temperatures, and it becomes BISDIAZONIUM SALTS v. DIAZO COM-
wholly crystalline at 45 (J. Soc. Chem. Ind. POUNDS.
1903, 228). It is soluble hi alcohol and in ether, BISMAL. Bismuth methylene digallate (v.
but not in alkalis, carbon disulphide, or glacial BISMUTH, Organic compounds of ; also SYN-
acetic acid. It is Isevo-rotatory, its rotation THETIC DRUGS).
and specific gravity varying with different BISMARCK BROWN v. Azo- COLOURING
preparations. That obtained by Schimmel MATTERS.
458 BISMITE.
BISMITE. Native bismuth oxide Bi,O 3 , is broken into pieces as large as a hazel nut, and
occurring as a yellow earthy powder, or as minute placed in inclined iron tubes in charges of about
rhombohedral scales. L. J. S. 12 cwts., sufficient space being left in the tube for
BISMON v. SYNTHETIC DRUGS. stirring the ore from the upper end (Figs. 1, 2, 3).
BISMUTH. (Etain de glace, Fr. ;
Bismuth. The tubes are closed at the upper ends by plates
Wismuth, Ger.) At. wt. 208-0.
Symbol Bi. of iron, and at the lower ends by similar plates
Occurrence. Metallic bismuth occurs in containing circular apertures through which the
small quantities in widely distributed localities, molten metal may run. The ends of the tubes
usually with other ores, such as those of cobalt, project slightly beyond the walls of the furnace,
nickel, copper, silver, lead, and tin. It is found the upper over a tank and the lower ends over
massive, granulated, reticulated or arborescent, iron crucibles which contain powdered charcoal,
associated with arsenic and silver, and occasion- and which are gently heated from below by a
ally iron. small charcoal furnace. The tubes are heated
The principal districts are Adelaide in South so as to cause the metal to flow easily, and in
Australia, Altenberg, Schneeberg, Annaberg, about 10 minutes the bismuth commences to
Marienberg, Joachimsthal, Johanngeorgenstadt, pass out into the crucibles, being there covered
Lolling in Carinthia, Fahlun, Sweden, and New by the charcoal and thus protected from oxida-
South Wales. In small quantities it occurs at tion. The ore is occasionally stirred with an
Huel Sparnon, Cornwall, Carrick Fells, Alva, iron rod from the upper end, and in from 30
Stirlingshire, and in Bolivia. Alloyed with 64 to 60 minutes the operation is completed.
p.c. gold it occurs at Maldon, Victoria. Alloyed The residues, graupen or bismuth barley, are
with tellurium it occurs as tetradymite in Cum- raked from the upper end into the tank, and at
berland. An alloy of bismuth with 3 p.c. arsenic once replaced by fresh ore. In this manner only
occurs at Palmbaum near Marienberg. about two-thirds of the bismuth is extracted.
Bismuth sulphide is widely distributed in 20 cwts. of ore require 63 cubic feet of wood.
small quantities, being found in Saxony, Sweden, The contents of the pots are removed by ladles
South Australia, America, and Cumberland. A to moulds and cast into ingots of 25 to 50 Ibs.
sulphide of bismuth, copper, and lead occurs as weight.
needle ore, aciculite, or patrinite. Sulphurous ores are usually roasted to re-
As oxide, or bismuth ochre, it is found as a move sulphur, and then smelted with iron
yellow substance, frequently as a coating on (to remove the last traces of sulphur), carbon,
other minerals, associated with iron and other slag, sodium carbonate, limestone, and some-
impurities, at Schneeberg, Joachimsthal, Beresof times fluor-spar. The regulus of bismuth thus
in Siberia, and in New South Wales. The prin- obtained is fused
cipal ore in Bolivia, which is stated by Domeyko on an inclined iron
to be the richest country in bismuth, is a compact plate and run down,
earthy hydrated oxide. leaving a dross con-
Bismuth occurs as carbonate or bismuthite, taming much of the
usually containing carbonates of iron and copper, impurity. Bismuth
at Meymac, with antimony, arsenic, lead, iron, ores are sent from
and lime in Mexico, whence it is imported to
; Joachimsthal, and
this country in North Carolina, and other
; worked by this pro-
localities. Of late years considerable deposits cess at Schneeberg.
of bismuth ores have been found in many places The following
in America, but they have been very little analyses of two
worked. The supply of bismuth ore would typical samples
much exceed the demand were it not for an show the composi-
agreement between the smelters and the mining tion of commercial
companies by which the supply is restricted and bismuth : From FIG. 1.
the price of the metal maintained at a remunera- Saxony Bismuth,
tive figure. 99-77 p.c. ; copper, 0-08 ; silver, 0-05 ; sulphur,
Bismuth is stated to occur in most sulphurous 0*10; iron, trace. From Joachimsthal Bismuth,
copper ores in about the same proportions as 99-32 p.c. ; lead, 0-30 ; silver, 0-38 ; iron and
silver in galena, in other copper ores except copper, traces ; sulphur, none. About 10,000
the carbonate, and in most samples of commer- Ibs. of bismuth are annually produced at
cial copper and copper coins (Field and Abel,
Schneeberg.
Chem. Soc. Trans. 16, 304; and Field, Chem. At Joachimsthal a method devised by R.
News, 36, 261).
Extraction. At Schneeberg in Saxony the
ore worked is principally metallic bismuth occur-
ing in ores which contain silver, lead, tin, and
arsenic in gneiss and clay-slate. GOO
.'MI njM.mivjiiiwiia-
The ore, which contains from 7 to 12 p.c.
bismuth, is sorted by hand as far as possible from
the gangue before treatment. The old method
' '
of liquation or sweating is still used, but has FIG. 2.
now been largely superseded by smelting pro-
cesses, in which the metal is much more perfectly Vogel is used (Dingl. poly. J. 167, 187) for extract-
extracted. bismuth from ores free from lead. The
ing
Liquation. In this process the metal is ores, which usually contain from 10 to 30 p.c.
separated as far as possible from the gangue by bismuth, are mixed, according to their richness,
melting at a low temperature. The picked ore with 23 to 30 p.c. iron turnings, 15 to 50 p.c.
BISMUTH. 459
sodium carbonate (according to the amount of oxidises much more rapidly than the bismuth,
gangue present), 5 p.c. lime, and 5 p.c. fluor- and at the close of the cupeilation a blackish
spar. The mixture is introduced in charges of litharge rich in bismuth is obtained, from which
about 1 cwt. into clay crucibles, 23 inches high that metal be extracted by reduction and
may
and 16 inches wide at the mouth, covered and In this manner bismuth
cupeilation ( J. 12, 71 1 ).
heated in a wind furnace to tranquil fusion, and becomes concentrated in the blicksilber in the
poured into conical moulds. The liquid sepa- refinement of silver ores at Freiberg, and passes
rates into three into the hearth bottoms, as much as 25 p.c.
layers, the upper being sometimes so absorbed. When the hearths
consisting of slag, the contain sufficient bismuth to be profitably
second of a speiss extracted, they are finely ground and treated
containing the arse- with hydrochloric acid, with the formation of
nic, sulphur, nickel, bismuth chloride. Water is added to the
cobalt, and iron, and solution to precipitate the metal as oxychloride,
most of the other and the precipitate is collected, washed, dried,
impurities, with and reduced to metal by fusion with charcoal,
FIG. 3. about 2 p.c. of bis- sodium carbonate, and powdered glass (v.
muth, and the lower Phillips's Metallurgy).
consisting of a regulus of nearly pure bismuth. Several proposals have been made for the
The metal is again fused and remoulded (see extraction of bismuth by wet methods. Becker
Kerl, Handb. der Met. Hiittenkunde). (Fr. Pat. 366439, 1906) suggests the treatment
A similar process has been adopted by Patera of sulphide ores with a solution of an alkali or
( J. 1862, 646) for the extraction of bismuth from alkaline earth hyposulphite. The solution thus
refinery residues. obtained is treated with alkali sulphides, and
In France the carbonate of bismuth imported the resulting precipitate of bismuth sulphide is
from Meymac is dissolved in the minimum dried and smelted as described above.
quantity of hydrochloric acid and pieces of iron Both Becker (ibid.) and Ranald (Eng. Pat.
inserted in the slightly acid liquid. The bismuth 16622, 1898) have patented the use of a solution
is thus precipitated as a black powder, which is of ferric chloride as a solvent for bismuth
well washed and fused in a plumbago crucible sulphide and the subsequent precipitation of
under a layer of charcoal at as low a tempera- metallic bismuth from the solution by means
ture as possible (Ad. Carnofc, Ann. Chem. Phys. of iron or zinc, or by electrolysis.
[5] 1, 405; and Bull. Soc. chim. 21, 114). Eulert (Rev. Prod. Chim. 4, 164) employs a
For the extraction of bismuth for pharma- mixture of sulphuric acid, water, common salt,
ceutical purposes from sulphurous ores, Valen- and potassium nitrate as the extracting liquor,
ciennes roasts the ore on the level bed of a and the process can be made continuous. The
reverberatory furnace for 24 hours with the bismuth is finally obtained as the oxychloride,
occasional addition of charcoal and frequent which can be sold or smelted for the metal.
stirring with an iron rabble. When the sulphur On the extraction of bismuth from its ores, v.
has thus been evolved, the ore is mixed with about also Winckler (Ber. Entwick. Chem. Ind. 1, 953).
30 p.c. charcoal, and a mixture of chalk, salt, Purification. The crude bismuth produced
and fluor-spar, and again fused in a rever- by the above methods contains a variety of
beratory furnace. From 5 to 8 p.c. of the bis- impurities, from which it is important in many
muth is lost by this process, but this is compen- cases to separate it. These impurities are sul-
sated by the extra purity of the product. By phur, arsenic, antimony, copper, nickel, cobalt,
subsequent fusion with nitre, the antimony, silver, lead,and a trace of iron.
arsenic, and sulphur are removed, and by the Sulphur and arsenic may be removed by
ordinary wet methods the lead, copper, and silver fusion with T B of its weight of potassium nitrate,
'
are eliminated (M. A. Valenciennes, Ann. Chim. with constant stirring at a temperature slightly
Phys. [5] 1, 397). Ores of bismuth averaging above the temperature of fusion ; the nitre
60 p.c. bismuth are imported into England to soon oxidises the impurities and a little of the
the extent of about 40 tons annually, principally bismuth, forming with them a slag which rises
from Adelaide, South Australia, and from and solidifies at the surface. For the complete
Mexico. They are usually fused in black-lead removal of these impurities a second fusion is
pots with borax, sodium carbonate, and a little frequently necessary.
crude tartar. C. Mehu (Pharm. J. [3] 4, 341) recommends the
H. Tamm (Chem. News, 25, 85) states that following process for the removal of sulphur and
bismuth can be separated from ores containing arsenic. The metal is heated considerably above
much copper by fusion with an alkaline flux the melting-point in a vessel so as to expose a
containing free sulphur, in which case the copper large surface, and the oxide is removed to the
remains unreduced. He recommends a mixture sides as fast as it forms until about one-fourth of
of 5 parts sodium carbonate, 2 salt, 1 the metal has become oxidised ; the greater part
sulphur, 1
carbon, to be mixed in about equal proportions of the sulphur and arsenic will then have passed
with the ore. The bismuth produced is stated off as oxides. The mass is cooled, pulverised,
to be much more free than usual from arsenic, and mixed with charcoal, dried soap, and potas-
antimony, and lead, but about 8 p.c. of the total sium carbonate (free from sulphate), about one-
bismuth is lost. The bismuth present in small fourth of the original weight of the metal, in a
quantities in lead, copper, and silver ores fre- crucible, covered with charcoal, and heated to
quently becomes concentrated in the secondary redness for one hour. It is thence removed and
products of the metallurgical processes and may again fused in contact with air to remove the
then be profitably extracted. In the oxidation potassium which it contains, and which sepa-
of silver-lead containing bismuth, the lead rates as a white film on the surface. Arsenic
460 BISMUTH.
may also be mostly removed by fusion for a con- bismuth sulphide in the above operation (E.
siderable time under a layer of charcoal. Arsenic, Matthey, Proc. Roy. Soc. 49, 78).
sulphur, and most of the antimony may be Lead may be separated from the fused metal
eliminated by fusion at a bright-red heat under by repeated crystallisations, the alloy of bismuth
borax, stirring with a rod of iron until the action and lead melting at lower temperatures than the
ceases. The iron combines with the impurities purer bismuth. E. Matthey has thus by four
and rises as a difficultly fusible slag to the surface crystallisations reduced the percentage of lead
from beneath which the still liquid metal may from 12 to 0-4 p.c. (Proc. Roy. Soc. 42, 93).
be poured after partial cooling. For the separation of gold and silver, E.
For the complete removal of antimony, 2 or Matthey (Proc. Roy. Soc. 42, 89, 94) recommends
3 parts of bismuth oxide for each part of anti- the addition of 2 p.c. zinc to the molten metal.
mony supposed present are fused with the The mass is gradually cooled and the surface crust
metal. The oxide of bismuth then gives up its removed. This operation is repeated, whereby
oxygen to the antimony, becoming itself reduced the whole of the precious metals are concen-
and the antimonious oxide floats on the surface. trated in the skimmings. On fusing these in a
Hugo Tamm (Chem. News, 25, 85) recom- crucible with borax, the gold and silver are freed
mends for the removal of copper the fusion of from impurities by the action of the oxide of
the metal at a low temperature under 1 part of a bismuth, and sink to the bottom. To separate
mixture of 8 potassium cyanide and 3 sulphur. the last traces of these metals from the slag, it is
When the action has ceased the mass is stirred again fused with bismuth.
with a clay (not iron) rod, cooled until the flux A. Mohr states (Elektrochem. u. Met. Ind.
has set, and the metal poured out from beneath. 1907, 5, 314) that an electrolytic method has
If impure cyanide is used, a relatively larger been used with success for the purification of a
quantity is required. Mexican lead-bismuth alloy containing 81-1 p.c.
Iron may be completely removed, according lead and 14-5 p.c. bismuth, together with small
to H. Tiirach (J. pr. Chem. [2] 14,309), by fusion amounts of antimony, iron, zinc, arsenic, silver,
under a layer of potassium chlorate containing and gold. First the metal is made the anode
from 2 to 5 p.c. sodium carbonate. in an electrolyte containing 6 p.c. lead fluo-
From silver bismuth may be separated by silicate and 14 p.c. hydrofluosilicic acid. The
cupellation and subsequent reduction of the lead is deposited on this cathode of pure lead,
bismuth oxide so produced, or the metal may be and contains only 0-01 p.c. bismuth. The anode
dissolved in nitric acid, the silver precipitated slimes are fused with sodium hydroxide and
with hydrochloric acid, the solution filtered, and carbonate, and the metal, containing 94 p.c.
the basic salt of bismuth precipitated by excess bismuth, cast into anodes, which are then used
of water, and reduced to metal. in a second electrolysis, using a solution of bis-
Silver can be partially removed from bismuth muth chloride (about 10 p.c.) and free hydro-
by a process resembling Pattinson's process for chloric acid (about 10 p.c.). The cathodes are of
lead (Schneider, J. pr. Chem. [2] 23, 75). Acheson graphite, and are placed on the floor of
Lead may be precipitated from a nitric acid the cell. The current used is 20 amp. per sq. ft.
solution of the metal by the addition of sulphuric at the cathode, and 60 amp. per sq. ft. at the
acid, and the bismuth recovered as already anode, with a P. D. at the terminals of 1-2 volts.
described. A method commonly used is to The resulting bismuth is 99-8 p.c. pure, the
fuse the impure metal with bismuth oxy chloride, remaining 0-2 p.c. consisting chiefly of silver.
from which the lead liberates bismuth, itself (See also Zahorski, Hurter and Brock, Eng.
becoming combined with oxygen and chlorine. Pat. 22251, 1895.)
A number of investigations on the refining Chemically pure bismuth is best prepared by
of bismuth have been conducted by E. Matthey, dissolving the commercial metal in nitric acid,
and the methods he proposes are given separately decanting from any residue, and adding excess
below, inasmuch as they possess the merit of of water, whereby the bismuth is precipitated as
simplicity and have been thoroughly tested on a basic nitrate, leaving the impurities in solution.
large scale. The precipitate is well washed by decantation,
Arsenic is removed completely by maintain- dried, mixed with black flux or other reducing
ing molten bismuth at a temperature of 510- agent which produces a readily fusible flux, and
520 for some time. There is only a very reduced at a gentle heat in a crucible.
slight loss due to oxidation (E. Matthey, Chem. Properties. Bismuth is a greyish white -
News, 67, 63). crystalline metal of distinctly red tinge when

Antimony is separated by melting the metal compared with whiter metals such as zinc or
and maintaining the temperature at 350. antimony. It is very brittle and easily pow-
An alloy of bismuth and antimony, containing dered, and a bad conductor of heat and elec-
over 30 p.c. of the latter, rises to the surface of tricity. Its tenacity is very small, a rod 2 mm.
' '
the metal, giving it an oily appearance, and in diameter will just support a weight of 14-19
can be skimmed off. A complete removal of kilos. (Muschenbroeck). It forms fine obtuse
the antimony is thus effected (E. Matthey, I.e.). rhombohedral crystals, which approach very
Copper. For the separation of copper from closely to the form of cubes. It has also been
bismuth which has been previously freed from obtained in the form of acicular needles, which
arsenic, antimony, lead, &c., E. Matthey are really elongated hexagonal prisms (Heberdey,
(Roy. Soc. Proc. 43, 172) recommends its fusion Ber. Akad. Wien. 104, i. 254). Bismuth melts
with bismuth sulphide. The pure metal ob- at 264 (Roscoe and Schorlemmer), and boils
tained amounts to 90 p.c. of the crude material, at a temperature between the melting-point,
while the remaining bismuth sulphide, containing of copper and nickel, i.e. between 1090 and
copper sulphide, may be resmelted. 1450 (Carnelley and Carlton Williams), con-
Alkali sulphides may be substituted for the densing in laminae. The vapour density at
BISMUTH. 461
temperatures between 1600 and 1700 is 11, blackens with sulphuretted hydrogen (distinction
which corresponds to that calculated for a from antimony).
mixture of monatomic and diatomic molecules Metallic iron', copper, lead, and tin precipitate
(Meyer, Ber. 1889, 22, 726). Its sp.gr. at 12 metallic bismuth from solutions.
is 9-823. Scheerer and Marchand have stated A qualitative test for bismuth proposed by
that, on exposure to great pressure, the density Reichard (Chem. Zeit. 28, 1024) is the addition
of bismuth is lowered. W. Spring, however, of a brucine salt, or, better, brucine itself to the
has shown that the density is thereby increased. solution. In presence of bismuth a deep-red
By exposure of bismuth of density 9-804 to a colour is produced which is distinguished from
pressure of 20,000 atmospheres, the density was that given by nitric acid by the fact that it
raised to 9-856 a second compression still
;
becomes deeper on heating, whereas the colour
further increased the density to 9-863 (Ber. 16, given by nitric acid turns to yellow.
2724). It is stated that by careful hammering Estimation. Bismuth may be separated from
its density may be raised to 9-88. copper, cadmium, mercury, and silver, lead
Bismuth expands in cooling. Tribe (Chem. having been removed previously by precipita-
Soc. Trans. ) has shown that this expansion does tion as sulphate, by the following method, due
not take place until after solidification. to Stabler and Scharfenberg (Ber. 38, 3862).
Exposed to dry air, bismuth remains un- The solution, which may contain hydrochloric
altered at the ordinary temperature, but moist m acid, and should contain about 0-1-0-2 gram
air or in contact with water it becomes coated of bismuth, is diluted to 300-400 c.c., and
any
with oxide. When heated in air it burns with a precipitate redissolved by the cautious addition
bluish flame, evolving yellowish fumes of oxide. of nitric acid. This solution is heated to boiling,
At high temperatures it decomposes water. and treated with a boiling 10 p.c. solution of
Cold sulphuric acid has no action, but the trisodium phosphate Na 3 P0 4 (obtained by
hot concentrated acid dissolves bismuth. Hydro- mixing equivalent amounts of sodium hydrogen
chloric acid acts but slowly, and Ditte and phosphate and caustic soda). In presence of
Metzner have shown (Compt. rend. 115, 1303) much hydrochloric acid, a considerable excess of
that this action can only take place in presence of the phosphate must be used, but, should the
oxygen. Nitric acid, dilute or strong, dissolves solution become alkaline, nitric acid must be
it readily, with the formation of nitrate. Pow- added. After boiling the whole for some time,
dered bismuth thrown into chlorine gas ignites the precipitate is allowed to settle, and the
with the formation of trichloride. It also unites supernatant liquid is tested with sodium phos-
directly with bromine, iodine, and sulphur. phate. If precipitation is complete, the pre-
When comparatively pure, bismuth crystal- cipitate is collected hot on a Gooch crucible,
lises readily. To obtain it in the form of fine washed with 1 p.c. nitric acid, containing
crystals it is melted and allowed to cool until a ammonium nitrate, dried at 120, and finally
crust has formed ; the crust is pierced on heated over a bunsen burner, and weighed as
bismuth phosphate BiP0 4
opposite sides with a hot iron, and the still liquid The precipitate
.
portion poured through one of the openings. is very hygroscopic suitable precautions must
:
On careful removal of the crust the sides of the therefore be taken in weighing it.
vessel are found covered with crystals, frequently A modification of this method, which renders
resembling hollow pyramidal cubes like those of it suitable for the separation of bismuth from
salt, but which are in reality obtuse rhombohedra.considerable amounts of mercury, has been
Their iridescent lustre is due to a very thin described by Stabler (Chem. Zeit. 31, 615).
film of oxide which shows the colour character- A volumetric method for the estimation of
istic of thin plates. bismuth, for which considerable accuracy is
Bismuth can be obtained in the colloidal claimed, is the chromate method of Lowe as
state by reducing a solution of the nitrate with modified by Rupp and Schaumann ( J. Soc. Chem.
stannous chloride, or by the action of hypo- Ind. 1902, 1558).
phosphorus acid on bismuth oxychloride( Gut bier H. W. Rowell has published a method ( J. Soc.
and Hofmeyer, Zeitsch. anorg. Chem. 44, 225). Chem. Ind. 1908, 102) for the estimation of
Bismuth is the most diamagnetic substance small quantities of bismuth in ores, &c. The
known, a bar of the metal placing itself equa- method is colorimetric, depending on the
torially between the poles of a magnet, i.e. at yellow colour produced when potassium iodide
right angles to the position taken up by a bar of is added to a solution of the bismuth compound
iron. Bismuth also occupies an extreme place in sulphuric acid (see also Eng. and Mining
in the thermo-electric series, being used with Jour. 1901, 459).
antimony in the preparation of the most delicate An account of other methods used for the
thermopiles. estimation of bismuth will be found in the
Analysis. All compounds of bismuth, when articleon ANALYSIS.
mixed with carbon or other reducing agent and For the dry assay of bismuth ores the fluxes
fused before the blowpipe, give a brittle white used must depend on the composition of the
bead of metal and a yellow incrustation on the ore. Thus with ores containing metallic bismuth
charcoal, darker than that of oxide of lead. or that metal as oxide, sulphide, carbonate, &c.,
A very good dry test for bismuth is that due a flux consisting of a mixture of 2 parts potassium
to von Kobell. The substance is heated on or sodium carbonate, 1 part sodium chloride, and
charcoal with a mixture of potassium iodide and a proper quantity of argol or potassium cyanide
sulphur, when, if bismuth is present, a brilliant or charcoal powder, will be useful (Tamm) ; with
scarlet incrustation is obtained. the addition, where much earthy matter is
Salts of bismuth in solution give, on addition present, of borax. Where much copper is
of excess of water, a white precipitate of basic
present, Tamm advises the use of one part of the
salt, which is insoluble in tartaric acid, and ore mixed with one part or less of a mixture of
462 BISMUTH.
sodium carbonate 1, salt 2, sulphur 2, charcoal Tin and Lead. The alloys of bismuth with
powder 1 part. The exact proportions in which these two metals are of special interest. They
these fluxes are most useful must be learned by are extremely fusible, and on account of their
experience. expansion on cooling they take a very fine impres-
Alloys of Bismuth. sion, being largely used for electrotype moulds, &c
.
Bismuth unites readily with most metals, An alloy of 1 bismuth, 2 tin, 1 lead is used as
forming alloys which are usually of great hard- a soft solder by pewterers, and for the cake
ness, brittleness, and fusibility, and most of moulds for toilet soap. An expensive but effec-
which expand on solidifying. tive alloy for stereotype cliche's and metallic
Lead containing very little bismuth, is writing pencils contains 5 bismuth, 2 tin, 3 lead ;
toughened without becoming more brittle. The it melts at 91-66.
addition of bismuth to lead increases its hard- For special work solder containing bismuth is
ness and tenacity ; the alloy of 3 lead and 2 employed. It can be used under boiling water
bismuth has ten times the hardness and twenty if a little hydrochloric acid is added.
times the tenacity of lead. The alloy of 66 A thorough physico-chemical investigation

lead and 34 bismuth is very ductile, melting of these ternary alloys has been made by
at 166 ; it corresponds to BiPb 2 . An alloy Charpy (Compt. rend. 126, 1569), whose memoir
containing equal weights of the two metals is should be consulted for details. He finds that
brittle, of foliated texture, and of the colour of the eutectic mixture contains 32 p.c. lead, 16 p.c.
bismuth. Its density is 10-709, i.e. greater than tin, and 52 p.c. bismuth, and has m.p. 96.
the meandensity of the constituents. Such alloys are used to a considerable extent hi
Tin. The addition of bismuth to tin in small safety plugs for boilers and for automatic
quantities renders it more elastic and sonorous. sprinklers.
An alloy of 54 tin, 46 bismuth is crystalline and The varieties of fusible metal contain these
brittle ; it melts at 133 (Guthrie, Phil. Trans. three metals, with the addition sometimes of
[5] 17, 464). The alloy of 24 tin, 1 bismuth is cadmium, which still further lowers the melting-
somewhat malleable, but a further addition of point. A
table of the most important of these
bismuth renders it brittle. alloys is given below :
Name of alloy
BISMUTH. 463
liquid ammonia on bismuth. The compound is alkali to a

bismuthous salt, such as the nitrate ;
of a blue-black colour and takes fire in the air. but Thibault (J. Pharm. Chim. 12, 559) has
A. H. Gallatin (Phil. Mag. [4] 38, 57) has pre- shown that under these conditions the product
pared an alloy of bismuth with ammonium (1). contains appreciable quantities of oxy- acid salts.
He scattered ammonium chloride over bismuth By precipitating the hydroxide from an alkaline
sodium alloy, and added water. The alloy solution by the addition of acid, a pure
product
swelled and again contracted. On plunging is obtained which on
drying yields the pure
in water or heating, a mixture of hydrogen and oxide. It dissolves
in alkali in presence of
ammonia was evolved. After drying in vacu6 glycerol. On
addition of sugar to the solution,
over sulphuric acid, it evolved 27 volumes of metallic bismuth is precipitated, whilst
arsenic,
gas on heating. if present, remains in solution. Lowe (Zeitsch.
Bismuth combines very imperfectly with anal.Chem. 22, 498-505) recommends this
iron, forming alloys of diminished density. With method for the preparation of pure bismuth for
platinum, palladium, gold, and tellurium it also pharmaceutical purposes.
forms alloys. Compounds with the two latter Bismuth nitrate Bi(N0 3 3 ,5H 2 Oisprepared by
)
metals occur in nature. It is remarkable that dissolving bismuth or its oxide or carbonate in
the addition to bismuth of as little as 0-05 p.c. moderately strong nitric acid. The concen-
of tellurium completely changes the appearance trated solution is filtered, if
necessary, through
of the metal, which then has a minutely crystal- asbestos, and deposits on cooling large deliques-
line structure. cent crystals, which are caustic and melt in
their water of crystallisation when gently heated.
COMPOUNDS OF BISMUTH. When the bismuth used for the preparation
Bismuth forms two well-defined classes of contains arsenic, excess of nitric acid should be
compounds, in which it is a diad and a triad used for the solution ; the arsenic is then oxidised
respectively. There are indications of the to arsenic acid, and combines with its equivalent
existence of some more highly oxidised com-
'
of bismuth, being precipitated as arsenate of bis-

pounds, but, assuming their existence to be muth. R. Schneider (J. pr. Chem. 20, 418-434)
proved, their constitution can be more easily recommends the following proportions : 2 kilos,
explained by the assumption of a higher valency bismuth, 10 kilos, hot nitric acid (75 to 90) ;
for oxygen than by assuming bismuth to- be a when the action is finished the liquid is de-
pentad. canted from the sediment, which contains all
Oxides. Only two oxides of bismuth, the the arsenic. On addition of water to the solu-
dioxide and the trioxide, are definitely known. tion a white precipitate of basic nitrate falls, the
The statements of Deichler, Hauser, and Vanino constitution of which varies with the amount
and Treubert, that bismuthic acid and tetroxide of water used. This was formerly known as
exist, have been controverted by Gutbier and magistery of bismuth, and is now called flake or
Bunz (Zeitsch. anorg. Chem. 48, 162 49, 432
; ; pearl white, the latter name being also applied
60, 210 ;52, 124) ;Moser (Zeitsch. anorg. to the oxychloride of bismuth.
Chem. 50, 33) states that the addition of hydro- For pharmaceutical purposes the subnitrate
gen peroxide to a bismuth salt precipitates only is prepared as follows : Dissolve 2 parts of bis-
bismuth trioxide. Hollard (Compt. rend. 136, muth in 4 parts nitric acid of sp.gr. 1-42, diluted
229) says that a peroxide of the formula Bi 2 O 7 with 3 parts water, pour from deposit, if any,
is formed
during the electrolysis of a solution of evaporate to one-third the bulk, and pour into
bismuth sulphate, but this observation has not 80 parts of water, filter, wash and dry the pre-
been confirmed. cipitate at a temperature not above 55.
The trioxide and the compounds derived from It is a pearly-white powder consisting of
it are the
only ones of commercial importance. minute crystalline scales. It is employed as a
Bismuth trioxide Bi 2 3 occurs in nature flux for certain enamels, augmenting their
as bismuth ochre. It is best prepared by fusibility without imparting any colour, and on
heating the subnitrate of bismuth until red this account is used as a vehicle for metallic
fumes cease to be evolved. It may also be oxides. For the colourless iridescent glaze on
prepared by exposing the metal to a red- white porcelain the basic nitrate is rubbed with resin
heat in a muffle. The metal then burns and and gently heated with lavender oil by the ;
forms the oxide, which condenses as a yellow addition of coloured oxides, yellow and other
powder. Bismuth oxide thus obtained is a colours are produced. It is also used like the
pale-yellow amorphous substance, which melts oxide and in the same proportions for gilding
at a red heat to a glass without change of weight. porcelain, and to some extent as a cosmetic
Its sp.gr. is 8-21 it contains 89-66 p.c. bismuth.
; under the names blanc de fard and blanc
The oxide can be obtained crystalline, and d'Espagne. It is largely used in medicine.
has been shown to be isodimorphous with When prepared from impure metal it is liable
antimony trioxide (Muir and Hutchinson, Chem. to contain arsenic, lead, and silver ; tellurium
Soc. Trans. 1889, 143). has also been suspected (Pharm. J. 3, No. 287). To
It is used for glass and porcelain test for arsenic, heat a little of the nitrate in a
staining;
as an addition to certain fluxes to

prevent the tube until brown fumes cease to be evolved.
production of colour and in gilding porcelain, Add a small crystal of potassium acetate, and
;
being mixed in the proportion of 1 part oxide to again heat ; in presence of a trace of arsenic the
15 parts of the gold. odour of kakodyl is observed (A. Glenard, J. de
The darkening of the commercial substance Pharm. [4] 1, 217).
on exposure to light is due to the presence of a Bismuth chloride BiCl 3 This compound
.
trace of silver. is produced when finely powdered bismuth is

A hydrated bismuth.oxide Bi.2 3 ,H 2 O is pre- thrown into chlorine gas or when chlorine is
cipitated as a whitepowder on addition of caustic passed over the heated metal. It is also formed
464 BISMUTH,
by the solution of bismuth in aqua regia and allowed to crystallise. The product is dissolved
evaporation of the liquid; or by distilling a in 980 grams glacial acetic acid, diluted with
solution of the oxide in hydrochloric acid, 8 litres of water, and then mixed with a solution
changing the receiver when all the water has of 188 grams crystallised gallic acid in 8 litres of
distilled over. water. The precipitate of bismuth gallate thus
It is a white, easily fusible solid, which produced is washed five or six times with water,
absorbs moisture from the air, forming a crystal- pressed, and dried (Hartz, Pharm. Rundsch.
line hydrate. By the addition of water a white 12, 182).
precipitate of basic chloride or oxychloride is Another method consists hi treating a solu-
produced corresponding to BiOCl, though it; tion of bismuth nitrate in nitric acid with a
composition varies considerably. solution of gallic acid in 70 p.c. alcohol, nearly
The oxychloride of bismuth is, however, neutralising with sodium hydroxide or sodium
usually prepared by pouring a solution of the carbonate, and finally adding considerable
normal nitrate into a dilute solution of common quantities of sodium acetate or diluting largely
salt, forming oxychloride of bismuth and sodium with water. The compound is thus obtained as
nitrate. a yellow precipitate, which is collected and dried
It is a white pearly powder known as pearl (Eng. Pat. 6234, 1891).
white, and is used as a pigment, and in the pre- The empirical formula of the substance is
paration of a very fine yellow pigment known as H
BiC 7 7 O 7 , and Thibault (J. Pharm. Chim. 14,
Merimee's antimony yellow (v. ANTIMONY). 487) considers that it is really bismuthogallic
Bismuth chromate v. under CHROMIUM. acid, adducing in favour of this view the fact
Bismuth sulphite, produced by the action of that with alkalis it forms salts of which potassium
sulphurous acid on bismuth carbonate, or by bismuthogallate K
s BiC 7 6
H7 is a type.
double decomposition between a bismuth salt A general method for the preparation of
and an alkali sulphite, is a white crystalline bismuth salts of organic acids is the solution
powder, and is used in medical practice to check of freshly precipitated bismuth hydroxide in
intestinal fermentation, and in cases of worms. a solution of the acid (Fischer and Griitzner,
The organic compounds of bismuth have found Arch. Pharm. 1894, 232, 460; v. also Telle,
many applications in medicine and surgery. ibid. 1908, 246, 484, for the preparation of bismuth
Bimsuth salicylate is prepared, according to lactate by this method).
Causse (Compt. rend. 112, 1220), by adding a Basic bismuth
dibromohydroxynaphthoate,
solution of a neutral salicylate to a solution of which has been suggested as a substitute for
bismuth nitrate in a minimum amount of iodoform in surgical dressings (G. Richter,
hydrochloric acid. Considerable quantities of Apoth. Zeit. 1908, 23, 600), is obtained by a
ammonium chloride are added to the solutions similar method. -hydroxynaphthoic acid is
before they are mixed. Hydrated bismuth brominated in acetic acid solution, and the
H
salicylate Bi(C 7 5 3 ) 3 ,4H 2 is thus obtained recrystallised product heated with bismuth
as a white crystalline powder, insoluble in cold hydroxide. The salt is a finely crystalline,
water. yellow, odourless, insoluble powder, which is
A better method of preparation, due to unaffected by heating to 110.
Thibault (Bull. Soc. chim. 25, 794), consists Bismuth chrysophanate (' Dermal ')
in treating the bismuth oxide obtained by H
Bi(C 13 9 4 ) 3 -Bi 2 3 ? )
precipitation from 15 parts of bismuth nitrate yellowish-brown powder, is, according to
with a solution of 10 parts of salicylic acid in Merck, a mixture of
impure chryBarobin and
200 parts of water and heating on the water- bismuth hydrate.
bath till the action is complete. The product Compounds of bismuth with phenols are
is decanted, washed with cold alcohol, and dried obtained by double decomposition between an
at 100. It is thus obtained in rose-grey alkaline salt of the
phenol and a salt of bismuth,
crystals, which are soluble without decomposition such as the nitrate. Among those that have
in cold alcohol, ether, or in a saturated aqueous been made commercially may be mentioned :
solution of salicylic acid.
orphol (the j8-naphthol compound)
Martinotti and Cornelio (Bull. Chim. Pharm.
40, 141) point out that commercial preparations
C 10 H,OBi(OH) 2 +Bi 2 3 +H 2 ;
of the salt vary very much in composition, the xeroform (the tribromophenol compound)
amount of acid ranging from 5 to 67 p.c., and
H
(C 6 2 Br 3 0) 2 Bi-OH+Bi 2 3 ;
that of bismuth oxide from 37 to 79 p.c. helcosol (the pyrogallate)
Kebler, however, has shown (Pharm. J. 64, [C 6 H 3 (OH) 2 0] 2 -Bi-OH.

591) that the alcoholic test of the British An important pathological application of bis-
Pharmacopoeia is too stringent, as hot alcohol muth salts their administration internally
is
decomposes the salt. A more trustworthy in order to outline parts of the body in Rontgen
method of testing of bismuth salicylate for free ray work.
acid consists in extracting it with 90 p.c. benzene Bismuth oxyiodosubgallate C6 H 2 (OH) 3 -C0 2 -
'
and filtering the extract into dilute ferric Bil(OH), airol,' is prepared by heating together
chloride solution (1 in 3000), when a violet ring in 50 parts of water 35 parts bismuth oxyiodide,
is produced at the junction of the two liquids and 18-8 parts gallic acid until the product is a
if free acid is present.
greyish-green powder. It is used as a substitute
Basic bismuth gallate, known commercially for iodoform.
'
as dermatol,' is prepared as follows : 306 grams Other compounds of bismuth to which
of basic bismuth nitrate is dissolved in 328 grams names have been given are :
nitric acid of strength 38B., diluted with 200 Bismal, bismuth methylenedigallate, ot
grams water. The solution is filtered through tamed by the general method from the hydroxide
glass-wool, evaporated down to 600 grams, and and methylenedigallic acid.
BLACKING. 405
Markasol, bismuth borophenate. Rubus fruticosus, Konig gives, as the average

Thioform, bismuth dithiosalicylate, used as composition :
a substitute foriodoform (v. SYNTHETIC DRUGS). Free Other carbo-

BISMUTHINITE or BISMUTH-GLANCE. Water Protein acid Sugar hydrates Fibre Ash
86-4 0-5 1-2 4-4 1-8 5-2 0-5
Native bismuth sulphide Bi 2 S 3 , occurring in
acicular or bladed orthorhombic crystals or The seeds contain about 12-6 p.c. of a drying
lamellar masses, very like stibnite (Sb 2 S 3 ) in oil, sp.gr. at 15 0-9256, iodine number 147-8,
appearance. In Queensland and Bolivia it is the liquid fatty acids about 91 p.c. of the oil,
found in sufficient abundance to be used as an contain about 80 p.c. of linolic acid, 17 p.c. of
ore of bismuth. L. J. S. oleic acid, and 3 p.c. of linolenic acid, whilst the
BISMUTITE. Basic bismuth carbonate, con- solid acids, chiefly palmitic acid, amount to
taining about 90 p.c. Bi.2 3 formula perhaps
;
about 4-7 p.c. ; volatile acids are not present in
Bi 2 3 -C0 2 -H 2 0. It is a yellowish earthy the oil. A
small quantity of phytosterol is
material, and presenting such an appearance is present (Krzizan, Chem. Rev. Fett u. Harz, Ind.
surprisingly heavy (sp.gr. variously given as 1908, 15, 7). H. I.
6-9 and 7-6). It occurs as an alteration product BLACK HELLEBORE ROOT. Radix Helle-
of native bismuth, and in Bolivia is an important bori nigri. (
Racine d'Ellebore noir, Fr. ; Schwarze
ore of this metal. L. J. S. Nieswurzel, Ger.)
BISMUTOSE v. SYNTHETIC DRUGS. The root of the Helleborus niger (Linn.) or
BISSA-BOL v. GUM RESINS. Christmas Rose (Woodville, Med. Bot. 169;
BISTRE v. PIGMENTS. Bentl. a. Trim. 2). Black hellebore and
BISULPHIDE OF CARBON v. Carbon the nearly related green hellebore, Helleborus
CARBON.
disulphide, art. viridis (Linn.), are seldom employed in England
BITTER ALMOND OIL v. BENZALDEHYDE, except in veterinary medicine. They are both
and OILS, ESSENTIAL. powerful intestinal irritants.
BITTER APPLE v. COLOCYNTH. Vauquelin (Ann. de Museum, 8, 87), Sou-
BITTER SWEET v. DULCAMARA. beiran (N. Traite de Pharm. 1), and Feneulle
BITTER WOOD v. QUASSIA. and Capron (J. Pharm. Chim. 8, 503) examined
BITTERN. The mother
liquor which re- hellebore, but no definite constituent of physio-
mains after the crystallisation of common salt logical importance was announced till the dis-
from sea-water, or the water from salt springs. covery of helleborin by Bastick in 1852 (Pharm.
It contains soluble magnesium salts, bromides, J. 12, 174). Our knowledge of the chemistry of
and iodides. hellebore is, however, chiefly due to Husemann
The same term also applied to a mixture
is and Marme' (Annalen, 133, 55), who show that
of equal parts of quassia extract and sulphate of besides helleborin, which is a glucoside, there
iron, 2 parts extract of Cocculus indicus, 4 parts exists in both the black and green hellebore
Spanish liquorice, and 8 parts treacle, used to another glucoside, hellebore'in. Helleborein exists
sophisticate beers. in greatest proportion in the niger, but it is also
BITUMEN. This term includes a consider- the chief of the two constituents in the viridis.
able number inflammable mineral substances
of Hellebore'm, when purified, consists of groups
consisting mainly of hydrocarbons. They are of of microscopic needles which crumble in the air
various consistence, from thin fluid to solid, but to a yellowish- white hygroscopic powder. It has
the solid bitumens are for the most part lique- a sweet taste and darkens at 220-230. Water
fiable at a moderate heat. The purest kind bf and alcohol dissolve it, but it is insoluble in
fluid bitumen, called naphtha or rock oil, is a ether. Sulphuric acid forms with it a brownish-
colourless liquid of sp.gr. 0-7-0-84, and with a red solution, which changes to violet. By the
bituminous odour. It often occurs in nature action of dilute acids it hydrolyês into glucose,
with asphalt and other solid bitumens. Petro- and a grey-green amorphous precipitate of hellebo-
leum is a dark-coloured fluid variety containing retin. Helleboretin gives with concentrated nitric
much naphtha. Maltha or mineral tar is a more acid a violet solution, which deposits violet flakes
viscid variety. The solid bitumens are asphalt on pouring into water. Helleborein gives no such
(q.v.) ; mineral tallow or hatchet in ; elastic colouration (Thaeter, Arch. Pharm. 235, 414).
bitumen, mineral caoutchouc or elaterite ; ozo- Helleborin likewise assumes the form of white
kerite, &c. shining needles, and melts with decomposition at
An abundance of bitumen is found in the 150. It is insoluble in cold water, slightly
island of Trinidad at the Pitch Lakes, and in soluble in ether, but dissolves easily in boiling
Mexico. It is supposed to be a product of the alcohol or chloroform. It gives a characteristic
decomposition of vegetable matter, and consists and delicate colour reaction with sulphuric acid.
chiefly of hydrocarbons with variable quantities The crystals become deep-red, and dissolve in
of oxygen and nitrogen (v. PITCH). the acid to a deep-red solution. The taste
BITUMINOUS COAL v. FUEL. of helleborin is acrid and burning. Dilute
BIXEIN, BIXIN. Colouring matters of acids hydrolyse it into glucose and a resinous
annatto (v. ANNATTO). substance, helleboresin. Helleboresin is in-
BLACK BAND IRONSTONE v. IRON, ORES OF. soluble in water, slightly soluble in ether, but
BLACK BOY GUM v. BALSAMS. is readily dissolved by boiling alcohol. A. S.
BLACK CHALK. A kind of clay containing BLACKING. Blacking for shoes is mentioned
carbon, found in Carnarvonshire and in the Isle as early as 1598, but it was not introduced into
of Islay.
England until the reign of Charles II. It con-
BLACK COPPER v. COPPER. sists of (1) black bone charcoal (free from
BLACK EARTHY COBALT v. COBALT. calcium phosphate, otherwise it is subsequently
BLACK FLUX v. ASSAYING. treated with dilute sulphuric acid) and black
BLACKBERRIES. The fruit of the bramble, colouring matter ; (2) a mixture of sugar and
VOL. I.T. 2n
466 BLACKING.
oil, which, on rubbing, imparts the gloss and ;
water are mixed with constant stirring and
(3) fatty matter for preservation purposes. 153 parts rock candy (powdered), 61 parts gum
A liquid blacking can be prepared from 120 arabic, and 1000 parts ivory black are added
parts of ivory black, 90 parts brown sugar, 15 with constant stirring.
parts olive oil, and 500 parts stale beer. The Boot polish. 5 oz. ozokerite, 2 Ibs. cerasin,
ivory black, sugar, and olive oil are mixed into 5 oz. carnauba wax, If oz. beeswax, 4 pints
a smooth paste, and the beer added under turpentine, 2 Ibs. lampblack, 20 grams black
constant stirring (Hiscox, 1907). aniline dye, and perfume added if desired (Pharm.
AGerman recipe is as follows : 25 parts J. 1908, 506).
Marseilles soap are dissolved in 375 parts of Self-shining blacking. Dissolve 4 oz. gum
warm spirit (25 p.c.) and 40 parts of glycerol arabic, 1 oz. coarse sugar, pint good black
added ; this is shaken and added to a solution ink, and 1 oz. sweet oil, rub in a mortar, add
of 200 parts of shellac dissolved in 1000 parts 2 oz. strong vinegar, and add lastly 1 oz. rectified
of spirit (95 p.c.) and 5 parts nigrosine in 125 spirits (Scientific Amer. 1903, 39).
parts of spirit added. The mixture is well French shoe dressing. 32 oz. vinegar, 8 oz.
shaken in a closed vessel and left for a fort- logwood, and J oz. potassium dichromate are
night. boiled and strained whilst hot into a mixture of
Liquid polish. 4 oz. asphaltum, 8 fl. oz. 4 oz. gelatine, 4 oz. tragacanth, 4 oz. glycerol
turpentine, 3 fl. oz. of gold size, J oz. nigrosine, and 15 oz. water. The mixtureallowed to is
and 3 fl. oz. linseed oil. The mixture is heated stand for some hours: 2 oz. indigo are then
until uniform and thinned down to desired con- added, and the whole triturated in a mortar
sistence with oil of turpentine (Phot. J. Dec. (Pharm. Form. 1908)
1908, 738). Boot-top liquid. 1 oz. oxalic acid, 1 oz. zinc
Day and Martin's chief blacking is obtained sulphate, dissolved hi 30 oz. water. Apply
by mixing ground animal charcoal, sperm oil, with a sponge to the leather, which has been
raw sugar or treacle, and a small portion of previously washed with water, then wash off
vinegar. Dilute sulphuric acid is then added with water, and dry (Workshop Receipts, 1909.
to the mass until intumescence ceases, and 123).
the product is thinned by the addition of For kid shoes. 2 oz. gum shellac, 1 oz.
vinâr. aqueous ammonia, 8 oz. water, and aniline black
Bryant and James's indiarubber blacking is enough to colour. The first two ingredients
prepared by triturating thoroughly 18 oz. very are heated almost to boiling, and water is
fine shreds of indiarubber, 9 Ibs. hot rapeseed added to make the whole measure 16 oz.
oil, 60 Ibs. finely powdered animal charcoal, (Scien. Amer. 1903, 39).
45 Ibs.
treacle, 1 Ib. arabic previously
gum Waterproof blacking. 6 oz. caoutchouc and
dissolved in 20 gall, vinegar. The whole is 3 Ibs. hot rape oil are added to 20 Ibs. ivory black,
placed in a wooden vessel, and 12 Ibs. 15 Ibs. molasses, and 6 or 7 gall, vinegar in which
sulphuric acid added in small quantities at 6 oz. ground gum arabic has been dissolved;
a time, and stirred for J hour daily for 14 then add 4 Ibs. sulphuric acid and stir con-
days, 3 Ibs. of finely ground gum arabic added, stantly. Allow to stand for 2 weeks, then add
and stirring continued for 14 days. If required 1 Ib. fine gum arabic. Stir daily during 2
in the paste form, only 12 gall, vinegar added and weeks, and bottle (Workshop Receipts, 1909,
6 or 7 days' stirring is sufficient. 124).
Brunner makes a blacking by stirring 10 For dress boots. 8 oz. gum arabic and 2 oz.
parts of bone black with 100 parts of glucose molasses dissolved in 2 oz. ink and pt.
syrup, and 5 parts sulphuric acid added with vinegar. This is strained, and 2 oz. spirits of
rapid stirring until the mass is homogeneous. wine added.
2 parts of soda are dissolved in 4 parts water, BLACK JACK. A miner's term for blende,
and 20 parts train oil added and boiled with or zinc sulphide (v. ZINC).
constant stirring until a thick liquid is formed : BLACK LEAD. The common name of
the other mixture is then added with repeated plumbago or graphite (v. CARBON).
stirring. BLACKLEY BLUE v. INDULINES.
Acheap and good shoe blacking may be pre- BLACK LIQUOR. Ferrous acetate (v. ACETIC
pared by mixing 1 Ib. of ivory black, 1 Ib. ACID).
molasses, 8 tablespoonfuls sweet oil, and 1 oz. BLACK MUSTARD SEED OIL v. RAPE OIL :
of gum arabic, dissolved hi 2 quarts of vinegar OILS and FATS.

and J Ib. of oil of vitriol. BLACK TELLURIUM v. TELLURIUM.
Paste blacking. Mix 16 oz. ivory black, BLACK TIN v. TIN.
16 oz. lampblack, 6 oz. treacle, 5 oz. vinegar, BLACK VARNISH or BLACK JAPAN v.
and 4 oz. sperm oil. Mix and add gradually VARNISH.

4 oz. sulphuric acid. When intumescence BLACK WAD v. MANGANESE.
ceases, add oz. of iron sulphate, 6 oz. gum BLACK, WOOL, v. Azo- COLOURING MATTERS.
arabic, and 5 oz. water (Pharm. Formulae, BLANC FIXE. Trade name for ground
1908, 378). barium sulphate, used as a pigment (v.
Sticks of blacking of plastic consistence are BARYTES).
made from the following : 5 oz. stearin, 5 oz. BLANQUETTE. A
kind of crude soda, less
paraffin wax, 2 oz. carnauba wax, 2| oz. caustic than barilla, obtained at Aigues-Mortes
lustrous pitch, and 7 oz. turpentine (Pharm. J. by the incineration of Salsola kali.
Pat. 2564, 1908). BLAST FURNACE GAS v. FUEL.
Hiscox describes the following paste : 122 BLASTING GELATINE AND POWDER v.
parts Marseilles soap, 61 parts potassium car- EXPLOSIVES.

bonate, 500 parts beeswax, and 2000 parts BLAU or BLUE GAS. A mixture of volatile
BLEACHING. 467
'
hydrocarbons, e.g. propane, butane, the pentanes, or kiers,' a representation of which is shown
&c., containing hydrogen and methane, &c., in Fig. 1.
in solution under pressure. The pressure solu- The boiler A has a
central puffer pipe, B, fur-
tion is filled into steel cylinders, and is thus nished with a bonnet or spreader, M, at the top ;
available for transport. Used for illuminating
heating, and power purposes (Hallock, J. Soc.
Chem. Ind. 1908, 550).
BLEACHING. This term signifies the art
of destroying the natural colour of vegetable
and animal products in such a manner as to
leave them unimpaired with as white an appear-
ance as possible. The removal of certain other
natural or artificial impurities usually accom-
panies the bleaching proper. The art acquires
its greatest importance in connection with the
textile fibres, cotton, linen, wool, and silk ; hence
special reference will be made to the modern
methods of bleaching these materials.
Cotton bleaching. Cotton is usually bleached
J
in the form of yarn, thread, and calico, seldom
as loose cotton-wool. The natural impurities
occurring in raw cotton amount to about
5 p.c., and consist chiefly of pectic matters ;
other substances present are brown colouring
matter and very minute quantities of a fatty
acid, cotton wax, and albuminous matter. The
soiled grey appearance of raw cotton- wool, yarn,
and thread is almost entirely due to the presence
of these natural impurities. Cotton cloth or
calico, however, is still further contaminated
with flour or starch, fatty matter, China clay, FIG. 1.
and other mineral substances, all of which, to
the amount of 30-50 p.c., have been introduced c a perforated false bottom
is D is the lid
;
during the sizing of the warp. hinged at E and capable of being readily lifted
Cotton yarn and thread bleaching. If the by means of a chain and counterweight F is ;
cotton yarn is in the form of ' warps,' these are an air valve, L a steam pressure gauge ; H and
I are the steam and liquor pipes connected by
loosely plaited by hand or machine in order to
reduce their inconvenient length ; if in the form the two-way valve K with the pipe j, which
'
of hanks,' these are bleached separately or enters the kier immediately below the puffer
linked together in chain form ; weft yarn is pipe G is the let-off valve.
;
sometimes bleached -in the form of 'cops,' i.e. When such a kier has been charged with
ready for the spool of the weaver's shuttle. yarn and caustic soda solution, the lid is fastened
The several operations of the bleaching down and steam is admitted. The liquor below
process for 1500 kilos, yarn, employing low the false bottom soon begins to boil, and as the
pressure kiers, are as follows :
pressure of steam increases, a portion of the boil-
1. Ley-boil. 300 caustic soda (sp.gr.
litres ing liquor is forcibly ejected up the puffer pipe
1-16), 2000litres water, boil 6 hours ; and spread over the yarn. The liqucr drains
wash in kier 1 hour. through the yarn, soon to be ejected as before.
2. Chemicking. Bleaching-powder solution In this intermittent manner the circulation of
(sp.gr. 1-005), steep under sieve 2 hours ; the boiling liquor is maintained.
wash under sieve half an hour. The apparatus for chemicking, souring, wash-
3. Souring. Sulphuric acid (sp.gr. 1-005), ing under sieve, soaping and blueing, shown in
steep under sieve half an hour ; wash Fig. 2, consists of a stone tank, E, with per-
under sieve half an hour and afterwards forated false bottom F, and communicating by
in washing machine. the valve G with the stone tank D below. The
4. Soaping and blueing. Soap solution chain of yarn is drawn from the kier and led
about 6 grams per litre, with addition into the tank E by means of the winch A.
of small quantity of indigo-purple (indi- When E is suitably filled with yarn, the liquor
gotin monosulphonate of soda), steep in tank D is raised by the pump c to the sieve
2 hours under sieve. F', whence it drains through the yarn into the
5. Dumping. Pass through dumping ma- Avell below, again to be pumped up as before ;
chine containing soap solution and B is the eccentric wheel on revolving shaft by
indigo-purple, as in operation No. 4 ; which the pump is worked.
'
wash, squeeze or hydro-extract, and The dumping machine referred to consists
'
dry. of a pair of heavy wooden rollers placed over a

The first, second, and third operations are large wooden tank containing the soap solution.
repeated in the case of thread because of its The upper roller is covered with cotton rope
closer texture. For the second ley-boil, 30 litres and rests loosely on the lower one. The yarn is
caustic soda (sp.gr. 1-16) and 15 kilos, soap are first passed through the soap solution and then
used the chemicking and souring are exact
; between the squeezing rollers the irregularities
;
repetitions. caused by the linking or plaiting impart to the

The ley-boil takes place in large iron boilers upper roller a constant jumping motion, which
468 BLEACHING.
thus effectually cleanses the yarn and presses process the preliminary operations of stamping,
the soap and blue into the fibres. stitching,and singeing have to be performed.
When hank yarn is not linked to form a '
To recognise each piece of cloth and to trace
chain, but treated as separate hanks, wash damages, the ends are stamped with numbers
'
stocks in which the yarn is subjected to the and letters, usually with thick gas tar, occasion-
beating action of heavy wooden hammers, ally with aniline black. The pieces are then
replace the dumping machine. ' '
stitched together by machine.
Bleaching of yarn in the form of cops or The singeing operation is for the purpose of
'
cross- wound spools
'
(' cheeses '). The cops burning off the loose fibres on the surface of the
may be packed in wicker baskets or in linen calico, since they interfere with the production
bags and boiled in an ordinary kier, or they are of fine impressions, and are apt to
give rise to
treated in special cop-dyeing apparatus. It is certain defects during the
printing process. It
preferable to use a solution of sodium hypo- is performed by
rapidly passing the cloth in the
open width over red-hot
copper plates or cylinders,
or over a row of Bunsen gas
flames. We
may distinguish,
therefore, between plate singe-
ing and gas singeing, the
former being generally pre-
ferred for thick heavy cloth,
the latter for light thin cloth,
muslins, &c.
In plate singeing it is im-
portant that the plates be kept
at a uniform strong red heat
sufficiently high to overcome
the cooling action of the rapidly
moving cloth. The best results
are obtained by means of the
'
singeing roller,' which con-

sists of a slowly revolving
copper cylinder through which
a furnace flame is conducted.
In this case the cloth presses
continually against a different
portion of the red-hot surface
of the roller ; the cooling action
is thus reduced to a minimum,
and a regular even singe is the
result.
All singeing machines are
provided with lever arrange-
ments for immediately re-
moving the cloth from the
hot plate, or the gas flame
from the cloth, in case of
necessity ; further danger from
fire is avoided by causing the
singed cloth to pass at once

between a pair of rollers
moistened with water, or
through a small steam cham-
ber, in order to extinguish
sparks adhering to the cloth.
The above preliminary
FIG. 2. operations are now succeeded
by those of the bleaching
chlorite in place of a bleaching-powder solution. proper. The following is an outline of the
Cotton-cloth or calico bleaching. Accord- process at present in use for 24,000 kilos, cloth,
ing to the purpose for which the bleached employing low-pressure kiers :
material is intended, we may distinguish between 1. Wash after singeing.
the madder bleach, the market bleach,- and the 2. Lime-boil. 1000 kilos, lime, water about
Turkey-red bleach. 37,000 litres ;
boil 12 hours ;
wash.
The madder bleach. This, the most thorough 3. Lime sour or grey-sour. Pass through
kind of calico bleaching, is in general use with hydrochloric acid (sp.gr. 1-01) : wash.
calico-printers. aims at entirely removing
It 4. Ley-boils. 1st. 340 kilos, soda ash, water
every impurity which will attract colouring about 37,000 litres ; boil 3 hours.
matter in the madder or other dye-bath, so 2nd. 860 kilos, soda ash, 380
that the finished print may have a pure white kilos, resin,190 kilos, caustic soda
ground. (solid), water 37,000 litres; boil 12
Before proceeding to the actual bleaching hours.
BLEACHING. 469
3rd. 380 kilos, soda ash, water sized, much of the adventitious matter is also
37,000 litres boil 3 hours
; wash. ;
removed at this stage.
5. Chemicking. Pass through bleaching- The form of washing machine generally
powder solution (sp.gr. 1-0025) ; pile employed is shown in Figs. 3 and 4. It con-
2-12 hours wash. sists of a water trough, B, above which a
; pair
6. White-sour. Pass through hydrochloric of heavy wooden squeezing rollers, A, A, are sup-
or sulphuric acid (sp.gr. 1-01); pile ported. Two strands of cloth are washed simul-
1-3 hours. taneously they enter the machine at the ends,
;
7. Wash, squeeze, open out, and dry. pass between the squeezing rollers, then round
1. Wash
after singeing. From
the singeing the roller R in the water trough, again between
house the cloth is passed through the washing the rollers A, A, and thus travel spirally towards
machine in rope form, then plaited down on the centre of the machine, whence they are
'
the floor and allowed to lie in pile' for some drawn out by a winch and piled on the floor.
hours to soften. By this operation the cloth is A constant stream of water from the main
well soaked with water, and is thus better pre- G enters at the centre of the trough by the
pared to absorb the liquors used in the sub- tap E, the dirty water flowing out at both ends ;
sequent operations. Should the cloth be heavily c, c are wooden guide pegs to separate the several
strands of cloth ; s, s are strong brass rings or After adding the necessary amount of water,
' '
pot eyes through which the cloth enters the boiling and circulation of the liquor takes
the machine, and which can be set at place as already described in the case of the
any angle
to regulate its tension ; K and w
are the screws, ley-boil of cotton-yarn bleaching.
levers, and weights for regulating the pressure of The lime-boil has for its object the decom-
the squeezing rollers
against each other. The position of the fatty, waxy, and resinous im-
action of this machine is such that the cloth is Though not
purities present in the cloth.
continuously being soaked with water and then removed, but adhering still to the fabric in the
squeezed, thus causing a vigorous stream of form of lime-soaps, their altered condition facili-
water to flow down the tates their removal by the subsequent processes.
upward-moving strands
of cloth. The starch of the size is removed, and the
Lime-boil (lime-bowk, bucking, bowking). colouring matter of the fibre is modified. Lime
2.
The pieces are run through milk of lime supplied is preferred to caustic soda because it is cheaper,
to a and much more effective in saponifying neutral
washing machine'
of small dimensions
generally termed the liming machine
'
and are fatty matter than the caustic or carbonated
at once drawn alkalis ; indeed, with the exception of barium
by winches into the lime kiers,
carrying with them the lime they have absorbed. hydroxide, it seems to be the most energetic
The cloth is plaited in regular folds and well
saponifying agent which could bo used in cotton
tramped down by boys, who enter the kiers. bleaching.
470 BLEACHING.
It very essential to have a sufficiency of
is the lime-boil, and to dissolve and remove the
water in the kier, so that it stands at least about lime, also any iron or other metallic oxides
2 feet above the false bottom ; otherwise the present. Experiments by A. Scheurer show also
cloth, either at the top or bottom of the kier, is that the use of the lime-sour makes it less
very apt to be tendered, probably because it essential that complete saponification of the
becomes oxidised by the action of the steam fatty matter should take place during the lime-
upon the cloth in its limed condition. On the boil than would be the case if it were omitted.
other hand, an excess of water in the kier is to This is so because the free fatty acid liberated
be avoided, since then the cloth is apt to float during the lime-sour greatly facilitates the
and become entangled, or damaged by rubbing saponification of any undecomposed neutral fat
against the sides of the kier during the boiling. during the succeeding ley- boil, since the soap
When closed high-pressure kiers and live steam which the fatty acid then forms emulsifies the
are employed, the increase in volume of liquor neutral fat and exposes it to the action of
by the condensation of the steam must be taken the alkali employed. Hence the adoption of
into account, and, if necessary, a little liquor the lime-sour is equivalent to shortening the
must be allowed to escape. time of the lime-boil. A continual flow of fresh
Of the several varieties of kier which have dilute acid into the machine must be maintained,
from time to time been introduced in practice, and, since it is rapidly neutralised by the lime, it
mention may be made of 'Barlow's kiers.' is well to ensure a constant slight acidity of the
These are always worked in pairs, and so liquor by occasionally making acidimetrical tests.
arranged that the top of one kier is connected by Hydrochloric acid is preferred to sulphuric acid,
a pipe with the bottom of the other ; the pipes because it gives the more soluble calcium
which enter at the top and centre of each kier are chloride. The soured cloth should never be
' '
continued as perforated pipes or distributors permitted to remain long exposed to ah",
to a little above the false bottom, and then to especially air currents, otherwise the acid is apt
the bottom of the kier as a stay. Both kiers to concentrate in the exposed portions and thus
having been charged with cloth, the necessary tender the fibre.
amount of water is run into one kier only ; high- 4. Ley-boil. This operation takes place in
pressure steam is then admitted at the top, and the same kind of kiers as are used for the lime-
the liquor forced out below enters the distributor boil. The fatty acids resulting from the decom-
of the other kier at the top and permeates the position of the lime-soaps during the grey-sour,
cloth. When all the liquor has been thus also the brown colouring matters, are removed
transferred, the taps are reversed so that the during this operation. Its special feature is
steam forces the liquor in a similar manner back the use of resin -soap, which greatly facilitates
into the first kier. This alternating process and the removal of fatty matter by exercising a
circulation of the liquor is continued for about purely mechanical emulsive action, the alkali
seven hours. present being then able more readily to saponify
Pendlebury's arrangement of kiers is pre- the emulsified fats, particularly those neutral
cisely similar to that of Barlow, the only differ- fats which perchance have escaped the action of
ence being that one kier is smaller and serves the lime-boil. Ordinary soft-soap acts in a
only to hold the liquor each time it is forced similar manner, but resin-soap is cheaper and
through the cloth contained in the larger kier. better. A. Scheurer finds by experiment that,
The arrangement is cheaper, more economical after caustic lime, the most rapid saponification
as regards space required, and is suitable for of a neutral fat spotted on a piece of calico is
small requirements. effected when boiling under pressure at 120,
In the vacuum kier of Mason and others, by a solution containing 10 grams anhydrous
the circulation of the liquors is effected by means caustic soda and 2 grams resin per litre. In-
of a pump. After filling the kier with cloth, creasing the amount of resin does not hasten
the air is pumped out and the boiling liquor is saponification, though this is done by increasing
then admitted ; in this manner a more perfect the velocity of the circulation of the solution.
penetration of the material by the liquor is Indeed, with circulation even a more rapid sa-
obtained. ponification is effected with caustic soda and
The injector kier of Mather and Platt is resin than with lime.
shown in Fig. 5. A is the kier filled with cloth ; The preliminary short boiling with soda ash,
B, B are the steam pipes c is the injector and
; ;
which is sometimes replaced by merely soaking
D the circulating pipe F is the liquor pipe by
; the cloth in a weak solution of soda (' sweet-
which water or other liquor is admitted E, E is
; ening prevents tendering of the cloth by
'),
the draw-off valve and waste pipe. When the neutralising any traces of acid left in by reason
kier has been suitably filled with cloth and liquor, washing after souring. The boil-
of insufficient
steam is turned on, and, by the action of the ing with soda-ash after the resin-boil is for the
injector c, the liquid is withdrawn from the kier purpose of completing the removal of fatty
below, forced up the pipe D, and spread over matters and any undissolved resin, which other-
the cloth at G. Temporarily collecting at H, wise give rise to brown stains. Immediate re-
the liquor is gradually drawn through the cloth, moval of the cloth from the kier and washing
and in this manner a continual circulation of is necessary to prevent the production of iron
liquor is maintained. stains.

3. Lime-sour (grey-sour). After the lime- 5. Chemicking. The application of the
boil the pieces are washed, then passed through bleaching-powder solution takes place in wash-
a washing machine fed with dilute hydrochloric ing machines of the ordinary kind, but provided
acid, and, if convenient, at once washed. with stone instead of wooden troughs, because
The object of the lime-sour is to decompose of their greater durability. The bleaching action
the insoluble lime-soaps fixed on the cloth during takes place essentially during the lying-in-pile
BLEACHING. 471
or exposure to air of the cloth saturated with the 2. Lime-sour. Hydrochloric acid (sp.gr.
solution of bleaching powder ; the carbonic acid 1-01); steep 2-4 hours ; wash.
of the air liberates hypochlorous acid, and this, 3. First ley-boil or grey-boil. 240 kilos.
in the presence of the fibre, at once decomposes, caustic soda (solid), about 37,000 litres
yielding hydrochloric acid
and oxygen : in the water ; boil 12 hours ; wash.
moment of its production the oxygen oxidises 4. Chemicking. Bleaching-powder solution
and destroys the traces of colouring matter (sp.gr. 1-005) ; steep 2-4 hours ; wash.
it the highest Second ley-boil or white-boil. 240 kilos.
present in the fibre, thus giving 5.
degree of whiteness. soda ash, about 37,000 litres water ;

It is necessary to avoid the use of strong j
'
boil 12 hours ; wash.
solutions of bleaching powder, otherwise the 6. White-sour. Sulphuric acid (sp.gr. 1-01) ;
fibre itself is attacked, oxycellulose being pro- steep 2-4 hours; wash.
duced ; and even if the cotton is not tendered 7. Tint with blue squeeze
;
thereby it is still apt to acquire brown

stains
dry.
the More elaborate
during subsequent operations employed by or less
calico-printer, e.g. steaming, or to produce finishing operations follow
uneven shades in dyeing. e.g. starching, calendering,
6. White-sour. This operation is similar to beetling, stentering, &c. Some
the lime-sour already described, except that bleachers introduce a white-
instead of
sulphuric acid is usually employed
of its lower
hydrochloric acid, chiefly because
cost. Its object is to decompose and remove
traces of undecomposed bleaching powder,
lime, iron, and the oxidised colouring
matter.
7. The final washing must be as
thorough as possible in order to

ensure the removal of all traces of
acid, which, if left in the
cloth, would inevitably
tender portions of it during
the drying process. After
washing, the cloth is speci-
ally squeezed by passing
through a pair of heavy
wooden rollers, or through
the modern grooved brass
roller and disc machine of
W. Birch. The chain of
cloth then passes in a hori-
zontal, loosely
hanging position,
between a pah* of
rapidly revolving,
double - armed
winches or scutchers, which
effectually shake out the
twist from the strand. Thus
opened out to the full width,
the cloth is dried by passing
over steam-heated copper
cylinders, and folded. The
time usually required to
complete the madder bleach
is four to five days.
The market bleach. In
market bleaching the object
is simply to give a brilliant FIG. 5.
white appearance to the
calico or other similar material, to fit them for sour between operations 4 and 5, and
a second
immediate sale in the market as finished white chemicking between operations 5 and 6.
in the ley-boila is
goods. It is not necessary to have the calico The absence of resin-soap
' '
well bottomed i.e. cleansed from all colour- characteristic.
attracting impurities, since no subsequent dye- The Turkey-red bleach. This is merely a
ing or printing is intended. The operations curtailment of the foregoing processes, and is
are for the most part identical with those of the specially intended for yarn or cloth to be sub-
madder bleaching process. The modifications sequently dyed plain alizarin-red or Turkey-red.
introduced are shown in the following outline In it the operation of singeing and the application
of the process, intended for 24,000 kilos, cloth, of bleaching powder are omitted, since they
employing open or low-pressure kiers : diminish the fulness and brilliancy of the
1. Lime-boil. 1440 kilos, lime, water about Turkey-red dye ; the use of the latter is to be
37,000 litres boil 12 hours ; wash.
; avoided, because it gives rise to the production
472 BLEACHING.
of oxycellulose. The use of resin-soap is un- In 1883 Thompson patented a bleaching
necessary, and the process is limited to the process in which the goods contained in an
following operations :
air-tight kier are submitted to the action of
1. Wash. bleaching-powder solution and of carbonic acid
2. Boil in water 2 hours ; wash. alternately.
3. Ley-boils. In 1884 W. Mather, of the firm of Mather &
1st. 90 litres caustic soda (sp.gr. Platt, Manchester, devised an improved arrange-
1-35), about 3000 litres water; ment in which the calico could be passed con-
boil 10 hours wash.
; tinuously through chambers or tanks contain ing
2nd. 70 litres caustic soda (sp. gr. : the two necessary agents mentioned.
1-35); ditto, ditto. The so-called Mather-Thompson process
4. Sour. Sulphuric acid (sp.gr. 1-01) ; steep results from a combination of the two processes
2 hours. here indicated. With regard to the principles
5. Wash well and dry. of the process there is nothing new, for tae
The above quantities of materials are in- application of carbonic acid in connection with
tended for 2000 kilos, cloth, with low-pressure bleaching-powder solution was patented by
kier. P. F. Didot in 1855, while the steaming of goods
The steamer-kier bleaching process. The impregnated with alkali was patented as iar
bleaching processes previously described have back as 1800 by J. TurnbulL
been in vogue with little change during the The novelty consists essentially in the ma-
last forty years minor modifications have
; chinery employed, by which the duration of the
certainly been introduced, but the chief im- bleaching process is very much shortened, and
provements have always been in respect of the other material advantages are gained.
mechanical appliances employed. In the following year Mather introduced the
FIG. 6. FIG. 7.
so-called steamer-kier, in goods, which the in the steamer-kier is a noteworthy and most
previously impregnated with dilute caustic soda, important feature, since it greatly facilitates the
were submitted to the action of low-pressure saponification of the fatty matters on the cotton.
steam. After steaming, the liquor is run off, the kier
The steamer-kier consists of a strong wrought- is almost filled with hot water, and this is cir-
iron horizontal boiler, one end of which can culated through the cloth by means of the centri-
be closed by a specially constructed sliding door. fugal pump for one hour. A
similar washing with
At the side of the kier stands a centrifugal :
fresh hot water takes place during another hour.

pump connected with the top and bottom of Each kier is provided with two pairs of
the kier, and also with liquor tanks beneath, waggons, so that while the goods in one pair are
so that either boiling water or dilute caustic being steamed, the other pair can be emptied
alkali solution can be sprinkled on and cir- and refilled with cloth ready to be steamed. In
'
culated through the goods. Figs. 6 and 7 show this manner the operation of steaming is ren-
the general disposition of the steamer-kier. dered as continuous as possible and a very great
Two waggons of cloth having been run into ;
saving of time is effected.
the kier, and the door closed, steam is admitted The following details have been furnished by
till the pressure reaches a maximum of 4-5 Ibs. H. Koechlin, of the Loerrach Printworks :
|
During the steaming or boiling process, a To effect the madder bleach by the steamer-
continual sprinkling of the cloth with dilute kier process, the continuous bleach with the
caustic soda (sp.gr. 1-01-1-02) is maintained, application of carbonic acid, &c., is omitted, the
in order to keep the cloth well saturated with older method of chemicking and souring being
liquid, and thus prevent oxidation and conse- preferred. Those who consider the lime-boil as
quent tendering of the fibre by the action of th'e essential may apply it equally well by means of
steam. The excellent circulation of the liquors the steamer-kier.
BLEACHING. 473
The operations in this case are as follows : water wash 4 times (-1 hour each
;
1. Lime-boil (or steam). Run through milk time) with boiling water, and once
grams per litre, and pile in
of lime, 50 with cold water in kier.
steamer-waggon boil in steamer-kier 5
;
4. Chemicking. As above.
hours at 10 Ibs. pressure, circulating 5. Sour. As above wash and dry.
;
2000 litres water. Wash in kier with With the exception of the employment of
hot water. the steamer-kier and the use of bisulphite of
2. Sour. Sour as usual with dilute HC1 soda, this process is essentially the same as that
(sp.gr. 1-015) ; pile 2-3 hours, and employed for many years with success by Messrs.
wash. Guillaume Freres of St. Denis.
3. Ley-prepare. Pass through NaOH solu- The preliminary souring process effects the
tion (sp.gr. 1-005-1-01), heated to 70, decomposition of any insoluble fatty acid com-
and pile in steamer-waggon. pounds present in the grey cloth ; it removes
4. Ley-boil steam).
(or Boil 6 hours in calcareous or other mineral matter soluble in
steamer-kier at 10 Ibs. pressure, with acids, and modifies any starchy matter present,
circulation of resin-soap liquor 40 :
probably rendering it more soluble. The addi-
kilos, soda ash, 20 kilos, resin, 1000 tion of the small proportion of the reducing agent
litres water. Wash four times (-1 bisulphite of soda, along with the caustic soda
hour each time) with boiling water, and in the preparing process, is intended to prevent
finally Avith cold water, in kier. any oxidation and consequent tendering of the
6. Chemicking. Pass as usual through di- cotton during the steaming process. The use of
lute bleaching-powder solution (sp.gr. resin-soap along with the caustic soda, combined
1-0025); wash. with the perfect circulation of the liquor, is
6. Sour. Pass as usual through dilute sul- very material to the success of this method of
phuric acid (sp.gr. 1-01) ; wash and madder bleaching, for reasons already stated.
dry. According to H. Koechlin, this method gives
a perfectly satisfactory bleach. The white is
not permanently stained in an alizarin dye-bath,
and does not become yellow on steaming.
A noteworthy invention of Dr. G. Lunge is
the application of acetic acid in connection
with bleaching powder, in place of mineral
acids or carbonic acid. It can be applied im-
mediately before or after, or even along with,
the solution of bleaching powder. It liberates
hypochlorous acid with formation of soluble
calcium acetate. When the hypochlorous acid
exercises its bleaching power, it gives up oxygen
FIG. 8. FIG. 9.
Perfectly satisfactory results, however, are and produces hydrochloric acid, which immedi-
obtained by even omitting the lime-boil and ately acts upon the calcium acetate. In this
proceeding as follows : manner the acetic acid is reproduced, and is thus
1. Sour. Pass as usual
through dilute 2 S0 4
H ready to decompose fresh portions of calcium
(sp.gr. 1-015); pile 2-3 hours; wash hypochlorite.
and squeeze. Hadfield and Sumner patented a process in
2. Ley - prepare. Pass through following which the cloth, after having been impregnated
solution at 70 : 20 litres bisulphite with a solution of bleaching powder, is passed
of soda (sp.gr. 1-3), 20 kilos. NaOH through a box containing acetic acid vapour.
(solid 72 p.c.), 1800 litres water pile in ; A solution of sulphurous acid has been used
steamer- waggons. by some bleachers for the final souring process
3. Ley-boil (or steam). Boil in steamer- in place of sulphuric acid, over which it possesses
kier 6-8 hours at 10 Ibs. pressure, with the advantage of being an antichlor, in conse-
circulation of resin-soap liquor 20 :
quence of its reducing action.
kilos. NaOH (solid 72 p.c.), 40 kilos, The Walsh kier. In this kier, shown in Figs.
soda ash, 20 kilos, resin, 2000 litres 8 and 9, which is very largely used, the boiling
474 BLEACHING.
liquor is circulated by means of a centrifugal platinum - iridium are used, and the other in
pump, and it is heated in a special heating which carbon electrodes (highly compressed
arrangement outside the boiling kier. graphite) are employed.
In the Bentz-Edmeston and in the Tagliani- In the Kellner electrolyser, which belongs to
Rigamonti kiers the boiling operation is a con- the former kind, a centrifugal pump is employed
tinuous process. Low pressure is usually by means of which the salt solution is repeatedly
employed, and the impregnation of the pieces passed through the apparatus until it contains
with the boiling liquor in the lower part of the from 3 to 5 grams of active chlorine per litre.
kiers is followed by
steaming in the upper part. In the Haas and Oettel electrolyser, which
After the boiling is completed the pieces are belongs to the latter kind, the salt solution is
plaited into wooden boxes, in which they are electrolysed until it contains from 10 to 15
allowed to lie for some hours. grams of active chlorine per litre.
Piece goods, such as heavy twills, &c., Powerful circulation of the salt solution is
which are frequently damaged (creased) in or- obtained by means of the hydrogen gas evolved
dinary bleaching in the rope form, are treated during electrolysing.
in the open width. Special kiers have been Bleaching by means of electrolytically pre-
constructed for this purpose, the principal one pared hypochlorite solution, although employed
being the Jackson-Hunt kier (Fig. 10). with advantage in special cases, such as the
bleaching of cops, is not commonly practised,
because it is more expensive in its application
than bleaching powder.
The statement that an electrolytically pre-
pared bleaching solution is more effective than
a solution of bleaching powder containing the
same amount of active chlorine, cannot be
confirmed in practice.
Permanganate, of potash, sodium peroxide,
and hydrogen peroxide give excellent results in
bleaching. Their price, as compared with
bleaching powder, is, however, in most instances,
prohibitive.
The history of cotton bleaching may be
briefly said to comprise the following noteworthy
improvements :
The use of chlorine gas by Berthollet in

1.
FIG. 10.
1787, and of hypochlorite of lime in 1799 by
Previous to boiling in this kier the cloth is Tennant.
2. The boiling with carbonate of soda instead
impregnated with caustic soda ley which has of caustic soda, after the lime- boil, introduced
been used in a former boiling. For this purpose
from America about 1837. A
more effectual
it is passed
through a special batching machine
containing the caustic soda ley, in which the
decomposition of the lime-soaps was thus
obtained.
cloth travels over a perforated drum. The
3. The adoption of the lime-sour, as proposed
caustic soda ley is forced through the cloth by
means of steam, which is blown against it by A. Scheurer-Rott in 1837.
4. The use of resin-soap in the ley-T)oils
whilst it travels over the drum. Ultimately,
the cloth is wound tightly and evenly into a
about the same period.
5. The introduction of high-pressure boiling
batch.
This batch now kiers about 1844.
is placed on a waggon, 6.The use of caustic alkali and resin-soap
which is transferred to the horizontal boiling
kier.
in conjunction with the steamer-kier, to the
exclusion of the lime-boil, in 1883-84.
Special driving gear is provided, by means
of which the cloth is wound off the batch on to Linen bleaching. Since the retted flax fibre
contains a much larger proportion of natural
another batching roller, passing over a heavy
perforated drum which rests on both batches. impurities than cotton, e.g. 25-30 p.c. of pectic
The caustic soda liquor is circulated by means acid, beside fatty matter, &c., linen is not so
readily bleached as cotton. In the main, how-
of a centrifugal pump, and is showered over the 1
cloth during its passage over the perforated drum. ever, the methods adopted for the two fibres are
the same. Linen is bleached hi the form of yarn,
In this kier the cloth is usually boiled under
thread, or cloth.
high pressure (about 45 Ibs.).
In the preparation of sodium hypochlorite Linen-yarn bleaching. Very frequently linen
solution, by electrolysing a solution of common yarn is only partially bleached, the process being
salt two types of processes are employed, one in completed, it necessary, when the yarn has been
which the products of electrolysis, viz. sodium woven into cloth.
and chlorine, are not allowed to combine, and The following operations are employed in
'
order to obtain half- white' or cream, with 1500
the other in which they are allowed to combine
to form sodium hypochlorite kilos, yarn, using low-pressure kiers :
1. "Ley -boil. Boil 3-4 hours in a solution of

2NaOH+Cl 2 =NaOCl+NaCl+H 2 O. 150 kilos, soda ash ; wash and squeeze.
The comes chiefly into considera-
latter process 2. Chemick (reel). Reel 1 hour in bleaching-
tion as regards the bleaching of textile materials.
powder solution, sp.gr. 1-0025 ; wash.
The apparatus used may be divided into two 3. Sour. Steep 1 hour in dilute sulphuric
classes, the one in which electrodes made of acid, sp.gr. 1-005 ; wash.
BLEACHING. 475
4. Ley-boil (scald). hour in a solution

Boil 1 At this stage the cloth is examined ; those
of 30-75 kilos, soda ash ; wash. pieces which are sufficiently bleached are soured
5. Chemick. Reel in a dilute solution of and washed, the rest are further treated as
bleaching powder, sp.gr. 1-0025 ; wash. follows :
6. Sour. Steep 1 hour in dilute sulphuric 10. Sub with rubbing boards and a solution
acid, sp.gr. 1 and dry.
-005 ;
wash well of soft soap.
If the yarn should be bleached more com- 11. Expose infield 2-4 days.
pletely, then operations 4, 5, and 6 are repeated 12. Chemick. Steep 2-4 hours in dilute
two or three times, as may be found necessary, bleaching-powder solution, sp.gr.
with this difference, that between 4 and 5 the 1-0006; wash.
'
yarn is grassed,' i.e. exposed in the field to the 13. Sour. Steep 2-3 hours in dilute sul-
action of the air, light, and moisture, for several phuric acid, sp.gr. 1-005.
days. By introducing this very gentle method 14. Wash, squeeze, and dry.
of bleaching, the full strength of the fibre is the linen is not brown, but made of yarn
If
better maintained. already partly bleached, the above process is
The various operations are conducted hi much curtailed, and weaker liquors are employed.
apparatus precisely similar to that employed in The kiers, chemicking and souring machines
the bleaching of cotton yarn, except in the opera- are the same as those used in cotton-cloth bleach-
tion of chemicking. Although steeping under the ing. The washing is done in the so-called wash-
sieve in dilute bleaching-powder solution might stocks or by slack- washing machines. The latter
well be employed, it is usual to suspend the are very similar to the cotton-washing machines,
hanks of linen yarn on reels in such a manner that the chief difference being that the water tank is
they are only partially immersed in the solution divided into compartments, each of which holds
contained in a shallow tank. As the reels revolve a few yards of slack cloth forming each strand,
the yarn becomes thus alternately impregnated before it passes through the squeezing rollers.
'
with the solution and exposed to the air. The The rubbing referred to is for the purpose
'
liberation of hypochlorous acid by the carbonic of removing mechanically any remaining brown
acid of the air is advantageous, and the bleach particles of ligneous matter termed 'sprits.' It
ismore effective and regular. consists in passing the chain of cloth through a
The application of acetic acid, as proposed solution of soap, and then immediately between
by Lunge, instead of this exposure to air, may a pair of horizontal, corrugated, heavy boards ;
here be strongly recommended, since then no in- the upper board rests loosely upon the lower
soluble lime salt is fixed on the fibre, and the sub- one, and moves lengthwise to and fro, while the
sequent souring is reduced to a minimum. pieces pass between them at right angles.
'
To avoid the presence of caustic lime, some The operation of turn-hanking consists in '
bleachers use hypochlorite of magnesia, as pro- disentangling the pieces after they have been
posed by Hodge, instead of bleaching powder. washed in the stocks, and then refolding them
Linen-cloth bleaching. The old method of for a further wash, thus ensuring a thorough
bleaching linen cloth consisted in alternately cleansing of every portion of the cloth. When
boiling the fabric with solutions of sodium car- slack-washing machines are employed, the
bonate and exposing on the grass, succeeded by operation is of course not necessary.
souring, and rubbing with solutions of soap. The chemistry of linen bleaching is essenti-
The modern method, adapted from that em- ally the same as that of bleaching cotton. The
ployed for calico, is given in the following pectic acid, fatty matters, &c., are rendered
resume. It is intended for 1500 kilos, brown soluble by the alkaline boilings, and the colour-
linen, using low-pressure kiers. ing matters still remaining are oxidised and
1. Lime-boil. Boil 14 hours with 125 kilos. destroyed by hypochlorites. The repetition
lime, 2000 litres water ; wash. of these operations is considered necessary by
2. Sour. Steep 2-6 hours in dilute hydro- reason of the large percentage of impurities
chloric acid, sp.gr. 1-0025 ; wash in present ; but it is very probable that good
stocks, turn-hank, wash. results would be obtained by adopting the more
3. Ley-boils. First, boil 8-10 hours with rational plan of first removing the whole of the
2000 litres water containing resin-soap ; pectic and fatty matters before applying the
30 kilos, caustic soda (solid), 30 kilos, hypochlorites.
resin, previously boiled together with Aprocess of boiling linen goods preparatory
water ; secondly, boil 6-7 hours with to the bleaching has been patented by Cross and
2000 litres water, 15 kilos, caustic soda Parkes. The pieces are first impregnated with
(solid), previously dissolved ; wash. a solution of soap, silicate of soda, caustic soda,
4. Expose in field 27 days according to the and mineral oil. They are then wound on a
weather. batching roller in a chamber containing steam,
5. Chemick. Steep 4-6 hours in dilute and afterwards steamed for some hours. This
is followed by boiling with a solution of silicate
bleaching-powder solution, sp.gr.
1-0025; wash. of soda or of soda ash. The goods are finally
6. Sour. Steep 2-3 hours in dilute sulphuric washed ; they are now ready for the first ' dip.'
acid, sp.gr. 1 -005 ; wash. Wool scouring and bleaching. The bleaching
7. Ley-boil (scald). Boil 4-5 hours with of wool never forms a separate industry, as in the
2000 litres water, 8-13 kilos, caustic case of cotton and linen, and, although in itself
soda (solid) wash. ;
of minor importance, it is necessarily preceded
'
8. Expose in field 2-4 days. by the operation of scouring,' which is of
9. Chemick. Steep 3-5 hours in dilute fundamental importance both to the woollen
bleaching-powder solution, sp.gr. manufacturer and the dyer.
1-0013; wash. In its natural condition the wool fibre is
476 BLEACHING.
contaminated with 15-80 p.c. of foreign matter, 2. Scour 15-30 minutes with dilute alkaline
consisting partly of dirt, &c., derived from solutions (soap, sodium carbonate, &c. )
without, but mainly of certain fatty matters at about 50.
'
designated as yolk,' secreted by the animal 3. Wash with water.

from which it is derived. This secretion is The
steeping is performed in a series of large
'
separable into two parts the one, wool-perspi- iron tanks, in which the wool is systematically
ration,' is soluble in water, and consists essenti- washed or rather steeped in water heated to
ally of the potassium compounds of oleic and 45, until it is deprived of soluble matter. As
stearic acids (potash soaps), &c. ; the other a rule, two or three steeps with fresh water are
'
portion, termed wool-fat,' is insoluble in water, found sufficient ; but it is customary to pass the
and composed of cholesterol and iso-choleste-
is wash- water through several lots of wool until it
rol, which exists partly in the free state, but becomes well saturated with ' wool-perspiration.'
chiefly in combination with oleic acid and other It is particularly advantageous in the case of
fatty acids. wools rich in yolk (e.g. Buenos Ayres wool, &c. ),
Loose-wool scouring. The object of scouring since it prevents too rapid soiling of the scouring
wool is to remove from it the yolk, &c., and thus bath and consequent staining of the wool, and
render it more
suitable for spinning, dyeing, or thus it tends to ensure more complete scouring.
bleaching. Two methods
of effecting it may be By evaporating the waste steeping liquors to
employed. The one generally adopted is to treat dryness, and calcining the residue, a good quality
the wool with dilute alkaline solutions capable of potassium carbonate, containing very little
of forming emulsions with the yolk ; the other sodium salts and suitable for glass manufac-
mode is to submit the wool to the successive turers, is obtained.
action of fat solvents, carbon disulphide, &c., The scouring and washing of the wool in
' '
and of water. order to remove the remaining wool-fat is best
Scouring with alkaline solutions. When performed by the aid of so-called wool-scouring
carried out in the most complete manner, this machines, one of which (J. & W. McNaught's)
method comprises the following operations : is shown in Fig. 11.
1. Steep several hours in tepid water. It consists of a large rectangular trough, A,
FIG. 11.
with a light frame, B, suspended over it by chains by having the rakes fixed in a second frame, oo,
and carrying a series of transverse, fixed, vertical which receives a slight backward-and-forward
rakes or combs, c. movement by means of the rod o and the cam K
The wool, either in its raw condition or after during the inward movement of the main frame
steeping, is spread evenly on the moving endless BB, to which it is attached. By this means the
apron or feeder D ; it is thus continuously wool is slightly opened out and agitated, and the
introduced at one end of the trough. sand and dirt fall through the perforated grating
By suitable mechanism the frame is lowered, LL. When the scouring liquor becomes too
and the wool is at once pressed beneath the sur- soiled for further use, the steam injectors MM
face of the scouring liquor by the perforated tray are brought into action in order to stir up all
or sieve E. When the frame is sufficiently sediment, and the dirty liquor is run off by the
lowered, it moves forward, the rakes gently carry- plug-hole N.
ing the wool towards the other end of the trough. For a complete arrangement there should be
When the forward stroke is completed, the frame at least three such machines placed in line, so
is lifted up, the rakes rise vertically out of the that the wool passes automatically from one
liquid, and the frame returns to its original to the other. The first contains more or less
position. By these successive movements the soiled scouring liquid which has been previously
wool is slowly passed through the scouring liquor. used in the second trough ; the second contains
At the delivery end it is carried up the inclined fresh scouring liquid and the third a continual
;
plane F by the rakes fixed on the small frame G, flow of clean, cold, or preferably tepid water.
which is hinged to the larger one. Having been The choice of scouring agents depends upon
pushed over the ridge, the wool slips down the character and quality of the wool. For
between the squeezing rollers H, H, ready to be fine lustrous wools and such as are poor in
passed through a second similar machine. yolk, a mild scouring agent should be selected, e.g.
The working of the machine as above de- soap, ammonia, ammonium carbonate, 'lant,
scribed, is suitable for Botany and other fine &c., that is to say, agents which are capable of
classes of wool. When washing low Cape. River removing the yolk with the least injury to the
Plate, and similar wools, which contain much fibre. The best soaps to use are those which
dirt and sand, an additional movement is given are most soluble and least likely to contain any
to the rakes while in the liquor. This is effected trace of caustic or carbonated potash or soda.
BLEACHING. 477
Should these injurious constituents be present, between the wire gauze bands, then passes
the soap solution may be de-alkalised by the between hot rollers in a steam-heated drying
addition of a small quantity of boracic acid or chamber and emerges in a scoured, washed, and
ammonium chloride, thus yielding the less in- dried condition. Arrangements for automati-
jurious alkali borates and ammonia, respectively. cally collecting the dirt which settles from the
Potash soaps, being very apt to contain excess carbon disulphide, for separating the latter from
of alkali, should be critically examined. An the water, distilling and returning it to the
excellent and very soluble soap may be readily scouring tanks with the least possible loss, are
made from oleic acid and caustic soda. all provided for by ingenious devices, and the
Although a perfectly neutral soap does not general arrangement seems eminently typical of
always effect a rapid and complete removal of the method of scouring wool to be adopted in the
yolk, still it is better to adopt it, since
one can future. It is said to have been worked with
always add the proper quantity of other agents, success in Australia.
e.g. sodium carbonate, ammonia, &c., when The object of scour-
Woollen-yarn scouring.
necessary. ing Avoollen yarn remove the oU with whicli
is to
For low-class wools containing a large pro- wool has been impregnated by the spinner.
portion of yolk, and when cheapness is
a desi- Precisely the same agents are used as for loose
deratum, sufficiently satisfactory results are wool, but the machinery employed is necessarily
obtained by the proper use of sodium carbonate different.
free from caustic soda or other injurious im- Those yarns which have a tendency to curl
purity. Suitable sodium carbonates are sold up because they have been highly twisted are
under such commercial names as refined soda submitted to the preliminary operation of
' '
ash, Solvay soda, concentrated crystal soda stretching ; it also prevents them from shrink-
(Brunner, Mond, & Co.), crystal carbonate ing during the subsequent scouring process.
(Gaskell, Deacon, & Co.), &c. The hanks of yarn are suspended on the
It is impossible to give precise data with arms of a strong iron frame and tightly stretched
respect to the concentration and temperature of by means of screws. Thus charged, the frame is
the scouring solution to be employed, since immersed in boiling water for a few minutes.
these vary somewhat according to the character After changing the position of the hanks on the
of the wool operated upon. If the best results arms, the operation is repeated, the yarn is
are to be obtained, the solutions must always be allowed to cool in the stretched condition, and
applied as dilute and at as low a temperature is then removed ready for scouring.
(not above 50) as is consistent with the complete The scouring of yarn is effected either by
removal of the yolk. hand or by machine. In the first case the
The waste scouring liquors are collected in hanks of yarn are suspended on wooden rods
large tanks and neutralised with sulphuric acid ; placed across a rectangular steam-heated tank
the liberated fatty acids are sold to oil refiners, containing the scouring liquor. During a period
who by distillation obtain purer products, of 15 to 20 minutes the rods are swayed to and
suitable for making soap. fro by hand, one by one, each hank being
Scouring with volatile liquids. This method frequently turned in order to expose every por-
is stillonly in an experimental stage. Mechani- tion to the action of the liquor. The yarn is
cal difficulties, the fear of fire and explosions, the washed in another tank in the same manner.
first cost of the scouring agent, &c., seem to have Yarn-scouring machines are to be met with
prevented the general adoption of this process. in several forms. A very effective one consists
Its advantages are that the wool-fat is more of a rectangular tank, c, having several rollers
completely removed than by the emulsion above and below, and a pair of squeezing rollers,
method, and the wool itself is not injured. A A, B, situated at one end. The hanks of yarn,
certain degree of success has been obtained by linked together by means of string loops, are
the method proposed by T. J. Mullings, and passed continuously through the scouring liquor,
tried on a large scale. It consists in submitting
the wool to the action of carbon disulphide a:
hi a closed centrifugal machine until the whole
of the wool-fat is dissolved, then expelling the
solvent by means of water, and not as heretofore
by heat or steam, which always leaves the wool
with a yellow colour. The wool must afterwards
be washed in warm water to remove wool-
perspiration and other impurities. The wool
cleansed in this manner is said to be stronger,
capable of spinning finer yarn and with less FIG. 12.
waste and at less cost than if scoured by the
and are then washed in a similar machine
ordinary method with soap.
The same principle is adopted in the process (see Fig. 12).
of Singer & Judell of Adelaide, who employ, Woollen-cloth scouring. Woollen cloth is
however, a more elaborate and more perfect also scoured for the purpose of removing the oil
apparatus, whereby the scouring is made con- with which the yarn is impregnated by the
tinuous. The raw wool is placed on a feeding spinner. The operation consists in passing the
apron and carried along between two broad cloth as an endless band, either in the strand form
endless bands of wire gauze, first through a or in the open width, through the scouring liquor
succession of fourteen tanks containing carbon and then through a pair of squeezing rollers.
disulphide and then through five containing For thick woollen cloths, flannels, &c., scour-
water, all suitably enclosed. The wool, still held ing in tho^strahd is preferred, since a certain
478 BLEACHING.
amount of felting takes place and the cloth chamber one or more times. 14 gives
Fig. i
acquires a better handle. For worsted goods sectional view of the sulphur stove for th<
and such as are liable to crease, scouring in the continuous bleaching of cloth.
open width is preferable. In liquid-bleaching the woollen materia
Fig. 13 shows a section of E. Kempe's is immersed and moved about for several hour
machine for this purpose. It consists of two in a solution of sulphurous acid, or in one con
taining sodium bisulphite, and acidified witl
sulphuric acid. One may also steep the wool
first in a solution of sodium
bisulphite and thei
in dilute sulphuric acid, and
repeat the opera
tions as often as may be necessary. The liquid
bleaching process has not met with that genera
acceptance to which it seems entitled.
After bleaching, the materials are well washec
and tinted blue or bluish- violet, e.g. with refinec
indigo, indigo-extract, aniline-blue, methy
violet, &c., in order to counteract the yellowisl
tint whichis so liable to return.
The bleaching action of sulphurous acid ii
most probably due to its reducing
properties
According to this view, the sulphurous acid takei
up oxygen from the water present, while th<
liberated hydrogen combines with the
colouring
matter of the wool to form a colourless leuca
FIG. 13.
compound. Another explanation, however, i
squeezing rollers, A and B, placed above the that a colourless sulphurous acid compound ii
wooden trough c containing the scouring liquor. formed. Frequent washing of the wool witl
The roller D serves to draw the cloth from the alkaline solutions restores the yellow colour
squeezing rollers, and causes it to fall in regular It seems evident, however, that the
yellowing
folds upon the inclined plane EE. This is influence of alkalis is largely due to their furthei
covered with corrugated zinc, the grooves of action upon the wool substance itself since thej
which run longitudinally, in order to reduce the cause the wool eventually to become yellowei
friction of the cloth, and to prevent the latter than it was before bleaching.
from moving to either side. The upper part of Bleaching with hydrogen peroxide is effectec
the inclined plane is hinged at F, so that the by steeping the wool for several hours in more oi
inclination of this part can be regulated to suit less dilute solutions of this liquid, made slightly
different qualities of cloth, and to ensure that it alkaline by the addition of ammonia.
Th<
always slips down in regular folds without any simultaneous action of light accelerates anc
tendency to fall over or become blocked. The improves the bleaching. The white is very gooc
perforated water-pipes G, G are for" the purpose of and permanent, probably because, in this case
washing the cloth after scouring. the colouring matter is destroyed by oxidation
Bleaching of wool. After scouring, the wool Excessive bleaching by this method gives th<
still possesses a faint yellow tint, to remove which wool a harsh feel. Lunge recommends a slighl
is the object of the bleaching proper. The agent treatment with hydrogen peroxide of sulphur-
almost universally employed is sulphur dioxide, bleached wool in order to oxidise and thui
either in the form of gas (gas-bleaching) or in render innocuous traces of sulphurous acid no1
solution (liquid-bleaching). With hydrogen per- removed by washing. A very dilute solution oi
oxide a more permanent white is obtained, but sodium hypochlorite and exposure to air wil
it is still too expensive to admit of extended effect the same purpose.
application, but it serves as an excellent bleach- Bleaching of wool with hydrosulphite of soda
ing agent for certain fine materials. has been suggested by F. V. Kallab. It if
Gas-bleaching, stoving, or sulphuring, consists prepared by adding zinc powder to a solutior
in exposing the scoured and washed woollen of bisulphite of soda. The zinc is precipitated
material, while still wet, to the action of sulphur by adding milk of lime.
dioxide in a brick chamber. Yarn or thick Silk scouring and bleaching. The raw sill
cloth is suspended on poles, the sulphur (6-8 fibre consists essentially of two substances,
p.c.on the weight of wool) contained in an iron fibroine and sericine. The former constitutes
pot is ignited, the chamber door is closed, and the central portion of the fibre, and may be re-
the material is then left exposed to the action garded as the fibre proper, while the latter resides
of the gas for six or eight hours, or even over- principally in the external part and is readily
night. Thin cloth is generally passed in a con- removed by water and especially alkaline
tinuous manner through a similar chamber pro- solutions.
vided with rollers above and below. The cloth Raw silk is harsh, stiff, lustreless, and more
in the open width enters through a narrow slit or less unsuitable for dyeing, but when the ex-
at one end of the chamber ; it passes in a zig- ternal sericine or silk-glue is removed it becomes
zag course under and over the rollers to the soft and lustrous, and acquires an increased
further end, then returns and passes out by the affinity for colouring matters.
same slit. The sulphur dioxide is prepared in The object then of scouring is to remove the
the stove itself, or it is produced in a separate from the raw silk. It is effected by the
silk-glue
' ' '
furnace and led beneath the perforated floor of two operations, stripping and boiling -off.'
the chamber. According to the appearance of Stripping or ungumming. In order to
the fabric, it is passed through the bleaching move calcareous or other mineral matter solul
BLEU DE LYON, BLEU DE NUIT, BLEU DE PARIS. 479
in dilute acids, it is well first to rinse the silk in oxide, rendered slightly alkaline with ammonia
a tepid bath of dilute hydrochloric acid, and or with silicate of soda or borax, until it is
then wash. The hanks of silk are then hung on sufficiently bleached. A
more rapid and
smooth wooden rods and worked, as in woollen- effective method is to steep the silk in a some-
yarn scouring, in a soap-bath heated to

about what stronger solution, then wring out the
90-95 for about 20 minutes. A second and excess of liquid, and steam. The operations may
even a third bath may be used with advan- be repeated until the silk is sufficiently bleached.
tage. Long working in one bath is not good, Tinting Of Silk. Bleached silk is finally tinted
since the or dyed in delicate shades of blue, purplish-blue,
especially for silk intended to be white,
silk (fibroine) is apt to attract some of the colour- cream colour, &c. For pure white it is usual to
ing matter at first removed along dye the silk in a very dilute solution of a suitable
with the silk-
is afterwards very difficult to remove. coal-tar colour. After tinting, the silk is slightly
glue, and it
With yellow silk this point must be carefully rinsed in water and dried in a moderately warm
attended to. and darkened stove. J. Hii.
During the stripping operation the sericine BLEACHING POWDER v. CHLORINE.

at first swells up and makes the silk somewhat
it dissolves off and leaves the
glutinous, but soon
fibre soft and lustrous. The waste soapy liquors,
strongly impregnated with sericine, are care-
fully preserved and find an important use in silk-'
dyeing under the name of
'
boiled-off liquor.
When applying the coal-tar colours, it serves
to retard their attraction by the silk, and
thus ensures the production of even or level
colours.
After stripping the silk is rinsed in water
containing a small proportion of soap and
sodium carbonate.
Boiling-off. The object of this operation
is to complete _
the removal of
the silk-glue and
thus give the silk
all the lustre and
brilliancy of
which it is cap-
able. The hanks
of silk are tied
up in coarse bags
of cotton or r
. . _
hemp, '
generaUy
called pockets.' *<
and these are

boiled for one to
three hours in
open copper
boilers. The silk is then well rinsed in a weak BLENDE, from Blenden, Ger., to dazzle.
tepid solution of carbonate of soda, and finally Native zinc sulphide. It usually contains iron
in cold water. sulphide which gives it a black colour, whence
During the operations above described, the name Black Jack applied to it. An im-
Japanese and Chinese silks lose 18-22 p.c. in portant ore of zinc. The sulphur it contains is
weight, European silks lose 25-30 p.c. occasionally utilised in the manufacture of sul-
Bleaching of silk. The actual bleaching of phuric acid. (For descriptions of burners for
silk is effected by exposing the scoured silk, while this purpose, v. J. Soc. Chem. Ind. 3, 631 4,54.) ;
still in the wet state, to the action of sulphur BLEU DIRECT or DIPHENYLAMINE BLUE
dioxide gas. The operation is precisely similar v. TRIPHENYLMETHANE COLOURING MATTERS.
to the stoving of wool. BLEU FLUORESCENT C, 8
H 3 Br 6 N 2 5 (NH 4 ).
In certain cases, e.g. with so-calledsouple

' '
A colouring matter obtained by Weselsky and
silk, the stoving is preceded by a preliminary Benedikt in 1880 by treating diazoresorufin
bleaching in aqua regia, diluted to sp.gr. 1-02 dissolved in potassium carbonate with bromine
and heated to 20-35. The silk is rinsed in and precipitating by an acid. Soluble in boiling
this solution for 8-15 minutes until it acquires water with a red- violet colour, giving a fluor-
a greenish-grey colour, and then at once washed escent green solution. Dyes silk and wool blue
well in cold water. A dilute solution of the with brownish fluorescence (Weselsky and Bene-
dikt, Monatsh. 5, 605
'
so-called
'
of the sulphuric Ber. 1885, 18 ; Ref. 76).
chamber-crystals ;
acid manufacture may replace the aqua regia. BLEU DE GARANCE. Artificial ultra-
The bleaching of silk with hydrogen peroxide marine (v. ULTRAMARINE; PIGMENTS).
is
gradually being more and more adopted, BLEU LUMIERE v. TRIPHENYLMETHANE
especially for Tussur silk and other wild silks. COLOURING MATTERS.
Indeed, for these silks no other method of BLEU DE LYON, BLEU DE NUIT, BLEU
bleaching is so satisfactory. The silk is steeped DE PARIS v. TRIPHENYLMETHANE COLOURING
and worked in a dilute solution of hydrogen per- MATTERS.
480 BLEU MARIN.
BLEU MARIN v. TRIPHENYLMETHANE cubic millimetre, or 400-500 red to each white
COLOURING MATTERS. corpuscle. It is these which give the red colour
BLEU DE SAXE v. COBALT. to the blood. They vary in size and structure
BLEU SOLUBLE v. TRIPHENYLMETHANE in different groups of the vertebrates. In
COLOURING MATTERS. mammals they are biconcave (except in the
BLIND-COAL. A Scotch term for anthra- camel where they are biconvex) non-
tribe,
cite. iiucleated discs, in man ^^
inch in diameter ;
BLISTER STEEL v. IRON. during foetal life nucleated red corpuscles are,
BLOCK FUEL v. FUEL also ;
PITCH. however, found. In birds, reptiles, amphibia,
BLOCK TIN v. TIN. and fishes, they are biconvex oval discs with a
BLOOD is a richly albuminous fluid which nucleus they are largest among the amphi-
;
holds in suspension large numbers of corpuscles. bians. Their most important and abundant
The fluid medium in which the corpuscles float constituent is the pigment haemoglobin. In
is called the plasma, or liquor sanguinis. In invertebrates this respiratory pigment is usually
round figures, the plasma contains about 10 p.c. absent, and when present is, with few exceptions,
of solids, of which proteins comprise 8, extrac- in solution in the plasma and not in special
tives 1, and inorganic salts (the principal one corpuscles. In other invertebrates its place is
being sodium chloride) the remaining 1. The taken by other respiratory pigments, for
proteins are all coagulable by heat, and are instance, by the green pigment which contains
named serum albumin, serum globulin, and iron and is called chlorocruorin (hi certain worms),
fibrinogen. The last-named is the least abun- or by the blue pigment which contains copper
dant (0-4 p.c.), but confers upon the blood its and is termed hsemocyanin (in certain crus-
characteristic power to clot or coagulate when taceans and molluscs). The vast majority of
it is shed. When shed, the blood rapidly invertebrates have colourless blood containing
becomes viscous, and then sets into a jelly the ; only colourless corpuscles. Haemoglobin con-
jelly contracts and squeezes out of the clot a tains 0-4 p.c. of iron ; it and certain of its
straw-coloured fluid called serum, in which the derivatives give characteristic absorption spectra
shrunken clot then floats. The formation of which form one of the best tests for blood. It
threads of a solid protein called fibrin from is termed a conjugated protein,
consisting of a
fibrinogen is the essential act in coagulation ; protein (globin) in combination with the iron
this with the corpuscles it entangles constitutes containing material termed ha3matin
the clot, and serum is plasma minus the fibrin (C 32 H 30 N ? Fe0 3)
which it yields. The following scheme shows Haemoglobin is crystallisable, but haematin
the relationships of the constituents of the has not yet been obtained in crystalline form.
blood at a glance :
By boiling dried blood with a little sodium
serum chloride and glacialacetic acid, the character-
,l<
.
istic brown crystalsof haematin hydrochloride
corpuscles / or haemin are readily obtained, and this is the
In round figures, the blood contains 60-65 p.c. best chemical test for blood ; it can be performed
of plasma, and 35-40 p.c. of corpuscles. The quite readily on a microscope slide. By treat-
corpuscles are of three kinds, the red corpuscles ment with acid, an iron-free derivative of hae-
or erythrocytes, the white or colourless cor- matin is obtained called haematoporphyrin, and
puscles or leucocytes, and some very small in the body certain iron-free derivatives some-
particles also colourless, which are called the what similar to haematoporphyrin are formed ;
blood-platelets. these constitute the pigments of the bile. By
The subject of blood clotting has been the the reduction of haematoporphyrin, metliyl-
battlefield of numerous opposing theories, but propylpyrrol is obtained, and the same sub-
the view now generally held is that the conversion stance is obtained also from phylloporphyrin, a
of fibrinogen into fibrin is due to the action of derivative of chlorophyll this is an interesting
;
an enzyme called thrombin or fibrin-ferment. fact, as it indicates a near relationship between

This agent takes origin from the platelets and the principal pigments of the animal and
white corpuscles ; it is first shed out from them vegetable worlds.
in an inactive form called thrombogen throm- ; During life the blood in constant move-
is
bogen is converted into the active enzyme ment (circulation), and

owing to this cir-
it is
thrombin by the combined action of the calcium cumstance that it supplies the tissues with both
salts of the plasma and of an activating agent nutriment and oxygen. The products of pro-
termed thrombokinase, which originates from tein and carbohydrate digestion pass directly
the cells of the blood itself and of the other from the alimentary canal into the blood-vessels ;
tissues of the body. the fat reaches the blood indirectly by the
The white or colourless corpuscles are typical lymph-stream. The blood, however, does not,
nucleated animal cells which have been differ- except in the spleen, actually bathe the tissue
entiated into varieties by their staining re- elements ; the middle-man between blood and
actions, the number of their nuclei, and their tissues is a fluid called lymph, which exudes from
seat of origin (lymphoid tissue, and red bone the blood through the thin walls of the capillary
marrow). Their most important property is blood-vessels. The lymph thus supplies the
their power of amoeboid movement, by which tissues with material for their repair or for
they ingest and subsequently digest foreign storage ; it also removes from the tissues the
particles. They act in this way as scavengers waste products of then- activity ; it is collected
(phagocytes), and thus confer protection against by lymphatic vessels, which converge to the
pathogenic organisms (bacteria, &c.). maui lymphatic channel called the thoracic duct.
The red corpuscles are much more numerous This opens into the large veins near to their
than the white, averaging in man 5,000,000 per entrance into the heart, and thus the lymph is
BLOOD. 481
returned to the blood, and the waste products (For details, see Konig, I.e. 496 ; Merck's Waren-
Lexicon, 5th ed. art. Blut.')
'
are then conveyed to the various organs (lungs,
kidneys, skin) by which they are discharged (3) As a clarifying agent. Blood is employed
from the body. hi the same way as milk, gelatin, and albumin
The function of blood as an oxygen carrier are, as a clarifying agent for wines, syrups, and
is dependent on the presence of haemoglobin. similar liquids, in the proportion of 150-200 c.c.
Oxygen passes by diffusion into the blood of of blood per litre. The clearing action is due to
the lungs, and is then seized by the pigment, the proteins present, but used in this way there
with which it forms a loose compound called is considerable danger of infection, as also is the
oxyhaemoglobin ; this bright - red arterial or case for milk. Dried blood or the dried blood-
oxygenated blood passes to the heart, and is albumin is therefore preferable. Blood-albumin
thence propelled by the arteries all over the is prepared from the serum drained off from the
body ; in the tissues, where the oxygen tension clot ; the product is really dried serum, as the
is very low, oxyhaemoglobin is dissociated, and mixed with the other constituents
proteins are
the oxygen passes into the plasma, and again and the word albumin is used as
of that fluid,
'
synonymous with protein,' and not in the correct

'
reaches the actual tissue elements via the lymph.
The reduction of oxyhsemoglobin changes the chemical sense. It has the advantage of being
colour of the blood to the darker tint which it considerably cheaper than egg-albumin, for the
has in the veins, by which vessels it is carried total blood of an ox will yield 750-800 grams
back to the heart and sent to the lungs for a of the dried product, a good-sized calf will yield
fresh supply of oxygen. The venous blood is 340-400 grams, and a sheep about 200 grams
also rich in carbonic acid, which finds an exit (seeMerck, I.e. art. 'Blutalbumin').
from the blood in the lungs into the expired (4) The therapeutic uses of blood and serum.
air. It should be noted that haemoglobin is The high nutritive value of blood makes it a
not the carrier of carbon dioxide that gas is
;
valuable drug in the treatment of anaemia, and
carried mainly as carbonates in the blood- certain patent medicines sold under the name
plasma. of haematogen consist very largely of blood
The amount of respiratory oxygen carried by mixed with suitable flavouring and preservative
the blood pigment is 1-34 c.c. oxygen per agents. A still larger practical use of blood
gram of haemoglobin. This can be replaced products (serum therapy) has been the outcome
by equivalent amounts of such gases as carbon of work on immunity, in which the names of
monoxide or nitric oxide. These compounds Richet, Ehrlich, Behring, and Roux may be
are more stable than oxyhaemoglobin, and the mentioned as those of pioneers. Those inte-
gas is not removable by the tissues ; hence in rested in problems of immunity should consult
coal-gas poisoning the colour of the blood is current handbooks of pathology. The following
equally bright in arteries and veins, and the does not pretend to do more than give a sketch
cause of death is oxygen starvation. of the main facts, and the example selected of
The foregoing outline of the composition and the usefulness of the method is that in which
uses of the blood from the physiological point serum therapy has been the most successful,
of view can be amplified by the study of any namely, the treatment of diphtheria. The
standard textbook of physiology or physiological animal body is protected against its foes by a
chemistry. variety of mechanisms, and against our micro-
Passing now to the technical and commercial scopic (bacterial) enemies the most potent of
aspect of the case, the uses of the blood come these is the action of colourless blood corpuscles
mainly under four headings ( 1 ) as food ; (2) as
:
(phagocytosis). This, however, is assisted in
manure ; (3) as a clarifying agent ; and (4) as a certain cases by the presence in the fluid part
drug. of the blood of chemical substances which have
'
(1) As food. Blood as such is only used as received a variety of names; for instance, bacte-
'
food by savages, and attempts have been made riolysins are substances which actually kill
' '
to utilise dried defibrinated blood as a com- bacteria ; agglutinins are substances which
mercial food product without any great success. clump the bacteria together and render them
' '
It, however, forms an important constituent of immobile ; opsonins are substances which
certain articles of diet, of which Black pudding render bacteria an easy prey to leucocytes, either
and the German Blutwurst (Blood sausage) are by adding something to them to make them
the best known. In the preparation of these tasty or removing something from them which
' '
pig's blood is most commonly employed, and makes them distasteful ; and antitoxins are
they are of high nutritive value. (For the substances which neutralise the poisons or toxins
composition of various kinds of Blutwurst, see which are produced by the bacteria. There is
Konig, Chemie d. menschl, Nahrungs und very little accurate chemical knowledge of the
Genussmittel, Berlin, 1904, 525 Pott. Handb.
; composition of these various materials ; they
d.
Tier-Ernahrung, iii. 513, 1909 E. Schmidt,
; are, however, as a rule, destroyed by a high
Lehrb. d. pharm. Chem. ii. 2, 1833, 1901.) temperature, and are probably protein-like in
(2}
As manure. Dried blood, the so-called nature. The amount of these substances in the
Blood-meal (Blutmehl), is extensively used as blood may be increased by certain stimuli, much
manure, and may be placed directly on the land, in the same way as the epidermis becomes thick-
or, more frequently, is mixed with superphos- ened as the result of manual labour. The
phates. It is a brown powder with a glue-like administration, for instance, of small doses of
smell, and must be kept in dry places to avoid the toxin will produce an excessive production
putrefaction. It is valuable on account of its of the antitoxin which specifically neutralises
high percentage of nitrogen (11-8) and of the poison. Substances which in this way
phosphorus (1-2 p.c.). Numerous patent ma- stimulate the production of these natural anti-
nures contain a certain proportion of blood. dotes are spoken of in general terms as antigens.
VOL. I. T. 2 i
482 BLOOD.
If the bacilli which produce diphtheria are apes), and with the blood of no other species of
grown in a suitable medium, they produce animal. The test is extraordinarily delicate,
the diphtheria toxin much in the same way as and will detect human
blood that has been dried
yeast will produce alcohol when grown in a for months, and even when it is mixed with the
solution of sugar. If a certain small dose of blood of other animals. W. D. H.
this poison is injected into an animal, it will BLOODSTONE. A popular name for the
produce death, and that is called the lethal mineral heliotrope, a variety of chalcedony
dose. But if the animal receives a smaller dose, (Si0 2 ), showing bright-red spots on a dark-green
it will recover ; a few days later it will stand a ground. It is much used for the engraving of
larger dose and recover more quickly ; this is ring-stones and seals.
continued until after many successively increas- The same name has also been used for
ing doses, it will finally withstand without ill haematite (Fe 2 being a translation of
3 ),
an amount equal to many lethal doses.
effects ot/ioTiTTjs, so called because the colour of the
The animal is now immune against diphtheria, powdered mineral is like that of dried blood.
for the administration of the toxin (or antigen) L. J. S.
has called forth an excessive production of BLOOM. A term given to a mass of
antitoxin, and the blood remains rich in anti- iron after it leaves the puddling furnace (v.
toxin for a considerable but variable time ; the IKON).
serum obtained from the blood of the immunised BLOOMERY. An old term for an iron
animal is then employed for injecting into other furnace.
animals or human beings suffering from diph- BLOWN OILS v. OILS and FATS.
theria, and rapidly cures thedisease. The horse BLOWPIPE v. ANALYSIS.
is the animal selected for the preparation of BLUBBER OILS v. OILS and FATS.
antitoxin, and the success of the new treatment BLUE, ACETIN, Coupler's Hue (v. INDU-
in reducing the death-rate from what used to LINES).
be considered a terrible disease is one of the BLUE, ALIZARIN. This name is given to
wonders of modern medicine. dioxyanthraquinone-quinoline C 17 H 9 N0 4 and
,
its
(5) Miscellaneous uses of blood. Blood is, or sodium bisulphite compound

has been, employed in a number of industrial
C]7 H n N0 10 S 2 Na 2
processes, but it will be sufficient here just to
enumerate a few of them thus it has been used
: ALIZABIN AND ALLIED COLOURING MATTERS).
(v.
as a medium for paints (Johnson, Eng. Pat. 82, BLUE, ALKALI, NICHOLSON'S BLUE or
1883), in the preparation of adhesive cements, as SOLUBLE BLUE v. TRIPHENYLMETHANE COLOUR-
a precipitant of sewage in the alum, blood, and ING MATTERS.
clay process, and in the manufacture of pure BLUE, ANILINE. GENTIAN BLUE, OPAL
animal charcoal. BLUE, NIGHT BLUE, LIGHT BLUE, or FINE
Tests for blood. It is often necessary, in BLUE v. TRIPHENYLMETHANE COLOURING MAT-
medico-legal practice, to be able to identify TERS ;
also ANILINE BLUE.
blood-stains on garments and instruments. If BLUE, ANTWERP, v. PIGMENTS.
the blood is fresh, a microscopic investigation BLUE, AZO-, v. Azo- COLOURING MATTERS.
reveals the presence of corpuscles, and an BLUE, AZODIPHENYL, ACETIN BLUE,
aqueous extract will show the typical absorption COUPIER'S BLUE, INDULIN, FAST BLUE R.
bands of haemoglobin with the spectroscope. C18 H 16 N 3 C1 (v. INDULINES).
The best chemical test is the formation of BLUE, BASLE. Tolyldimethylaminopheno-
hsemin crystals already described, and is given tolyliminonaphthazonium chloride C 32 H 29 N 4 C1
by quite small quantities of blood, even if it is (V. AZINES AND COLOURING MATTERS DERIVED
old and dry. When the blood is dry, and small FBOM THEM).
quantities only are present, the most delicate BLUE, BAVARIAN, v. TRIPHENYLMETHANE
spectroscopic test consists in dissolving it in COLOURING MATTERS.
dilute potash with the aid of heat, and then BLUE, BENZIDINE, v. Azo- COLOURING
adding a drop of a reducing agent such as MATTERS.
ammonium sulphide ; the two absorption BLUE BLACK v. Azo- COLOURING MATTERS.
bands of hsemochromogen are then seen, one BLUE, BLACKLEY, v. INDULINES.
about half-way between the D and E lines, BLUE, BRILLIANT COTTON, METHYL
and the other just on the blue side of the E BLUE, METHYL WATER BLUE. Soda salt
line. of triphenyl-P-rosanilinetrisulphonic acid (v.
Human blood can only be distinguished with TRIPHENYLMETHANE COLOURING MATTERS.
certainty from the blood of other animals by BLUE, CERULEAN, v. PIGMENTS.
the so-called 'biological reaction.' The injection BLUE, CHINA, WATER BLUE 6 B
in successive doses of blood of another species EXTRA, OPAL BLUE, COTTON BLUE,
into an animal acts as an antigen, and causes the MARINE BLUE, v. TRIPHENYLMETHANE COLOUR-
development in the blood' of the injected animal, ING MATTERS.
'
of a specific precipitin ; the addition of the BLUE, CHINESE, or PRUSSIAN BLUE v.
blood to the serum of the animal which furnished CYANIDES : also PIGMENTS.
the injected blood causes a precipitate and; BLUE, COBALT, v. COBALT also PIGMENTS. ;
such a precipitate does not form except between BLUE, COTTON, v. TRIPHENYLMETHANB
the blood of the two species of animal used in COLOURING MATTERS.
the experiment. This has been applied to the BLUE, COUPIER'S, v. INDULINES.
case of human blood, by taking a rabbit and BLUE, CYANINE, v. PIGMENTS.
injecting human blood into it. The serum of BLUE, DIPHENYLAMINE, BLEU DIRECT
this rabbit will then give a precipitate with the TRI-
Triphenyl-p-rosaniline hydrochloride (v.
blood of man (and to a less extent of the higher PHENYLMETHANE COLOURING MATTERS).
BOILER INCRUSTATIONS AND DEPOSITS. 483
BLUE-ETHYLENE v. THIONINE COLOURING potassium nitrate, 62-65 pts. ; charcoal, 17-19J
MATTEBS. pts. ; sulphur, l-2 pts., copper sulphate and
BLUE, FAST, MELDOLA S BLUE, NEW ammonium sulphate, 1317 pts.
BLUE, NAPHTHYLENE BLUE. Chloride of BOG BUTTER. A substance resembling adi-
ditnethylphenyl-ammonium-fi-naphthoxazine (v. pocere occasionally found in peat in Ireland
(q.v. ),
OXAZINE COLOURING MATTEBS). and elsewhere. ( For list of chemical and physical
BLUE, FLUORESCENT, v. BLEU FLUORES- constants of a sample of bog-butter found in
CENT. Tyrone, v. Radcliffe and Haddocks, J. Soc. Chem.
BLUE, GENTIAN, SPIRIT BLUE 0, OPAL Ind. 1907, 3.)
BLUE, BLEU DE NUIT, BLEU LUMIERE, BOGHEAD COAL v. PARAFFIN.
FINE BLUE, v. TRIPHENYLMETHANE COLOUR- BOGHEAD NAPHTHA v. PARAFFIN.
ING MATTERS. BOG-IRON-ORE. An impure iron hydroxide
of recent formation in bogs and marshes. It is
BLUE, INDIAN, v. PIGMENTS.
referable to the mineral species limonite (2Fe 2 3 ,
BLUE, INTENSE, v. PIGMENTS.
BLUE IRON-EARTH. An earthy blue 3H 2 O), and, in fact, this name (from \ei/j.il>v, a
variety of the mineral vivianite, a hydrated meadow) was at first applied to this material,
ferrous phosphate Fe 3 P 2 O g ,8H 2 0, often found which ia known in German as Raseneisenstein
as a blue powder encrusting vegetable remains or Wiesenerz (meadow-ore). It is sometimes
in bog-iron ore, peat, and clays. L. J. S. placed under the species limnite (from A/JUI/TJ, a
BLUE, LEITCH'S, v. PIGMENTS. marsh), to which the formula Fe 2 3 ,3H 2 is
It contains 20-78 p.c. Fe.,0 3 some
BLUE, LIGHT, BLEU LUMIERE, LYONS assigned.
silica and organic matter, and often
,
BLUE, OPAL BLUE, BLEU DE NUIT v. TRI- phosphates

PHENYLMETHANE COLOURING MATTERS. in considerable amount. The material has
been deposited by the oxidation, through the
BLUE, METHYLDIPHENYLAMINE
agency of algse and bacteria, of chalybeate
C 39 H 34N 3 C1 waters. It is dug in shallow pits in the
peat-
obtained in 1874 by Girard by the action of bogs of Ireland, the production amounting to
oxalic acid upon methyldiphenylamine. Or by a few thousand tons per annum, and is mainly
the action of copper nitrate (Bardy and Dusart). used for the purification of coal-gas. The
Or with chloranil (Geigy). No longer made. Swedish lake-ores (sjomalm) are of the same
BLUE, METHYLENE, v. THIONINE COLOUR- nature. L. J. S.
ING MATTERS. BOG MANGANESE, wad, or earthy manga-
BLUE, NEUTRAL, AZINES AND COLOUR-
v. nese (v. MANGANESE).
ING MATTERS DERIVED FROM THEM. BOHEMIAN BOLE. A yellow variety of
BLUE, NILE, v. OXAZINE COLOURING MAT- bole (q.v.).
TERS. BOILED OIL. Linseed oil (v. LINSEED
BLUE, PARIS, v. TRIPHENYLMETHANE OIL).
COLOURING MATTERS. BOILER INCRUSTATIONS AND DEPOSITS.
BLUE, PRUSSIAN, v. CYANIDES; also PIG- The use of certain kinds of feed water in boilers
MENTS. leads to the formation of a deposit which,
BLUE, QUINOLINE, v. TRIPHENYLMETHANE settling on the bottoms, tubes, and furnace
COLOURING MATTERS. crowns, hardens there and gives rise to an in-
BLUE RED v. Azo- COLOURING MATTERS. crustation, which, by checking the transmission
BLUE, RESORCIN, or LACMOID C 12 H 9 N0 4 ? of heat to the water, causes waste of fuel and
N |C 6 H 3 (OH) 2 damage to the plates.

probably |C 6 H 3 /OH, a colouring matter ob- No such thing exists as an absolutely pure
natural water, the nearest approach to it being
_ _ rain water collected from a clean country water-
tained by Weselsky and Benedikt in 1880, by shed. Such water is the best natural kind that
the action of sodium nitrite on resorcin. Blue can be used in generating steam, its only draw-
violet powder soluble in water. Soluble in back being that it exerts a solvent action upon
alcohol with blue colour and dark-green fluores- metal fittings.
cence. Used as an indicator in alkalimetry Temporary hardness. Rain water in falling
(gjft through the atmosphere dissolves only gaseous
BLUE, SAXON, v. COBALT. matter, which is again driven out on heating,
BLUE, VICTORIA, v. TRIPHENYLMETHANE and the collection of impurities by the water
COLOURING MATTERS. from an engineering point of view commences
BLUE COPPERAS, BLUE STONE, or BLUE only when the rain comes in contact with the
VITRIOL. Copper sulphate COPPER).
(v. soil. The rain water falling on the ground
BLUE GUM TREE. The Eucalyptus glo- penetrates the top and subsoil, which contain
bulus (Labdll.), a tree common in Tasmania and decaying vegetation, giving rise to carbon
South-Eastern Australia. dioxide. The water, as it slowly filters through
BLUE JOHN. Avariety of fluor-spar found the soil, becomes saturated with the gas, and,
in Derbyshire, and valued for
making ornamental bearing it in solution, penetrates the earth
articles (v. CALCIUM). below. Here it meets with such substances as
BLUE LEAD. A term applied to galena by common salt (sodium chloride), compounds of
miners to distinguish it from white-lead ore, or magnesium, and calcium sulphate, small quantities
carbonate. of which the water dissolves partly by its own
BLUE PIGMENTS v. PIGMENTS. solvent powers, and partly by the agency of the
BOBBINITE v. EXPLOSIVES. dissolved carbonic acid. The chief substance
BODY VARNISH v. VARNISH. dissolved by the aqueous solution of carbon
BOFFINITE. An explosive consisting of dioxide is chalk or calcium carbonate, and to
484 BOILER INCRUSTATIONS AND DEPOSITS.
a extent the carbonates of magnesium and
less 100 parts of pure water
at a temperature of
iron. These are converted into soluble bicar-
bonates, which readily dissolve in water, and
endow the water with the property known as
'
temporary hardness.'
The characteristics of hard water are too well
known to need description. The hardness due
to dissolved bicarbonate of lime is said to be
temporary, because anything Avhich will break
up this salt and take away the carbon dioxide
which enables it to remain in the soluble form,
will throw down insoluble calcium carbonate
rendering the water far softer. On boiling a
hard water, the bicarbonate is decomposed, the
hot water no longer holds the carbon dioxide in
solution, and the calcium carbonate deposits and
' '
forms the fur in the kitchen kettle or the far
more serious boiler deposit, which is one of
the greatest troubles with which the steam user
has to contend, and which increases and thickens
until at length a thorough clean out of the boiler
has to take place.
Permanent hardness. When the temporary
hardness has been removed from water by
boiling or other means, it is found that there is
another kind of hardness which still remains,
'
and-this is called permanent hardness,' because
it cannot be got rid of by those processes which
' '
serve to soften water rendered hard by bicar-
bonate of lime. Permanent hardness in water
is due to calcium sulphate (sulphate of lime or
gypsum) and to the chloride and sulphate of

magnesium, substances which are dissolved by
the solvent power of the water itself, and these
can be removed only by distillation or by the
use of some qhemical means, which will convert
these soluble salts into insoluble bodies.
The hardness of a water is expressed in
degrees, one degree of hardness representing the
soap-destroying power imparted to one gallon
of it by the presence in solution of one grain of
chalk, so that a water is said to be of ten degrees
of hardness when it contains 10 grains of chalk
per gallon of water, or its equivalent in other
lime and magnesium salts.
Formation of deposit. The scale forming
-
constituents in natural waters are calcium

bicarbonate, magnesium bicarbonate, calcium
sulphate, and silica ; whilst waters which con-
tain sulphates, chlorides, and nitrates of magne-
sium also aid in the production of scale by de-
composition amongst themselves. In tracing
the formation of scale it will be well to consider
the actions which lead to the deposition in the
case of each ingredient.
Calcium carbonate, which is generally the
most abundant constituent of fresh- water scale,
is formed, as pointed out above, by the decom-
position of soluble calcium bicarbonate with

escape of carbon dioxide and deposition of
practically insoluble calcium carbonate, whilst
calcium sulphate, which is the most important
factor in the hardening of scale, is deposited
from water containing it by a totally different
set of actions. Calcium sulphate is dissolved
by the solvent power of the water itself, and not
by the agency of carbon dioxide, and therefore
the mere act of boiling water at ordinary
pressures does not suffice to cause its deposition.
The solubility of calcium sulphate varies very
considerably with the temperature, as is shown
by the following figures :
isreduced to a mere trace, whilst common salt calcium sulphate, for that salt separates out in
has become the most important constituent. a fine needle-shaped crystalline form, which,
('alcium and magnesium sulphates, together aided by the magnesium hydroxide, binds the
with magnesium chloride, are also present in deposit into a hard mass. On the other hand,
large quantities. a deposit consisting of calcium carbonate
The following analyses will give an idea of without any sulphate forms a soft powder,
the wide differences existing between fresh and which remains suspended in the water for some
salt water : time, and which, as it settles in the form of a
mud, admits of easy removal by the use of the
SALTS IN SOLUTION IN RIVER AND SEA WATER :
GRAINS PER GALLON. sludge cock ; but if calcium sulphate is present,

the hardness of the scale is so great as to
River water Sea water necessitate the use of a chisel and hammer to
Calcium carbonate 10-80 3-9
detach it from the plates and tubes, tending to
Calcium sulphate . 3-00 93-1
124-8 injure the boiler and shorten its life.
Magnesium sulphate .
On concentrating sea water, three stages of
Magnesium chloride .
;}o-25{ 220-5 deposition may be traced :
Magnesium carbonate . 1-25 trace

1. Deposition of basic magnesium carbonate ;
Silica . 0-56 8-4
2. Deposition of calcium carbonate with
Sodium chloride . 1-80 1850-1
Oxides of iron and alumina . 0-27 trace remaining traces of the basic magnesium car-
bonate and finally,
;
Organic matter . 2-36 trace

3. Deposition of the calcium sulphate.
When marine boilers were worked at com- The following table gives the variation in the
paratively low pressures, sea water was nearly saline constituents in the remaining liquid :
always employed, but on the introduction of Density 1-029

. 1-05 1-09
. 1-225
high-pressure tubular boilers, the quantity of Sodium chloride 2-6521 4-4201 7-9563 23-8689
deposit formed was so serious and the amount Calcium sulphate 0-1305 0-2175 0-3915 nil
of labour required to remove the incrustation Calcium car-
from between the tubes so considerable that it bonate . 0-0103 0-0171 nil nil
became imperative to discontinue the use of car-
Magnesium
sea water, and to use distilled water for the bonate . 0-0065 0-0032 nil nil
boilers, condensing the steam after use and chlo-
Magnesium
returning it to the boiler, and making up any ride . . 0-2320 0-3865 0-6960 2-0880
loss with fresh water. sul-
Magnesium
Distilled water is free from dissolved solids, 0-1890 0-3150 0-5670 1-7610
phate . .
but the condenser water always contains some

Ifthe sea water be concentrated above a density
of the lubricants from the engine cylinders.
of 1-225, the sodium chloride commences to
When animal and vegetable oils were used for
crystallise out.
lubricating, this condenser water, added to the Two causes affect the deposition of the
usual boiler feed, caused a large amount of
calcium sulphate during the concentration of the
damage to the boiler plates, on account of the sea water first, although it is more soluble in a di-
:
superheated steam decomposing the oils with lute solution of salt than in fresh water, it reaches
liberation of fatty acids but with the mineral
;
its maximum solubility at a density of 1-033,
oils employed for lubricating at the present
and after this point concentration of the saline
day, this trouble is to a great extent obviated. solution diminishes the amount held in solution.
Nature of river and sea water deposits.
The calcium sulphate is insoluble in saturated
Owing to the great difference between river and brine. The second cause affecting the deposition
sea water, variations are found in the nature of
is due to the density increasing as the tempera-
the deposits from them, as is shown by the fol-
ture rises the higher the temperature, the
;
lowing analyses of incrustations in boilers using smaller is the amount of calcium sulphate which
river, brackish, and sea water respectively : the water can hold in solution, so that when a
River Brackish Sea of 284-302F. (140-150C.) is
Calcium carbonate 43-65 0-97
temperature
75-85 becomes insoluble both in sea and
attained, it
Calcium sulphate 3-68 34-78 85-53
fresh water.
Magnesium hydroxide 2-56 4-34 3-39
Under ordinary conditions
it is quite possible
Sodium chloride . 0-45 0-56 2-79 to sea water without the deposition of
boil
Silica . 7-66 7-52 1-10
calcium sulphate, if care be taken that its
Oxides of iron and alu
mina 2-96 3-44 0-32 density does not rise above 1-09, but in a boiler,
pressure and consequent raising of the boiling-
Organic matter . 3-64 1-55 trace
Moisture 3-20 4-16 5-90 point come into play, and act upon the calcium
sulphate in solution in exactly the same way as
concentration and increased temperature, so
100-00 100-00 100-00
that even in the old form of low-pressure boiler
These may be takenas typical deposits, and most of the sulphate was deposited, whilst in
show that the incrustation from fresh water may the high-pressure boilers now in use, every trace
be looked upon as impure calcium carbonate of the sulphate will be precipitated and hence, ;
with small quantities of other compounds ; that owing to the impracticability of getting at the
with a mixture of fresh and salt water, the tubes in such boilers, it is impossible to use sea
deposit consists of nearly equal parts of calcium water in them, so that they require to be fed
carbonate and sulphate, whilst sea water gives with fresh water. Even the fact of diluting the
practically impure calcium sulphate. sea water with distilled water to reduce its
The condition and physical properties of the density does not overcome this difficulty, so
deposit are largely affected by the presence of that when through a break-down in the distilling
'
486 BOILER INCRUSTATIONS AND DEPOSITS.
plant, sea water has to be used, a slight scale is With the removal of the calcium sulphate the
sure to be formed. When a saline solution calcium carbonate is precipitated in a soft and
containing calcium sulphate is heated under powdery condition, and is easily blown-off by
pressure or concentrated until calcium sulphate the sludge cock.
begins to deposit, the separation will continue Other alkalis and alkaline salts are also
even after the solution has cooled down or the employed, amongst which may be mentioned
pressure removed, and calcium sulphate when ammonium chloride, which decomposes the
it has been deposited under pressure or high calcium carbonate in the boiler, forming soluble
temperature from sea water, even if the density calcium chloride, whilst the ammonium car-
of the water is normal, redissolves only at a rate bonate volatilises with the steam.
so extremely slow that it may be looked upon Although acid mixtures have been recom-
as practically insoluble. mended, yet it is evident that, even if they are
This result is due to the mode in which the effective in removing the scale, they must have
sulphate separates from sea water under a detrimental effect on the boiler plates.
pressure. Calcium sulphate occurs naturally Feed-water heaters act to a certain extent in
as gypsum CaS0 4 ,2H 2 0. When calcium sul- softening the water supplied to a boiler, and thus
phate is deposited from sea water in a boiler, aid in reducing incrustation ; as much as 50
p.c.
it comes down in small crystals of the composi- of the calcium carbonate in the water will often
tion 2CaS0 4 ,H 2 O, whilst after deposition in the be found deposited as mud in the superheater.
boiler and in contact with the heated plates and In the anti-incrustators which have merely
tubes, it loses all the water, changes its crystal- a mechanical action, some act by
offering
line form to long needle-shaped crystals, and surfaces on which the deposits will form in
becomes anhydrite CaS0 4 , and in this form it preference to depositing on the plates, as in
binds deposits into a hard mass. the case of fibre brushes or bundles suspended
Means of preventing incrustation. The in the boiler, and which can be easily with-
importance of getting rid of boiler deposits and drawn ; whilst the bulk of them consist of
of keeping the plates as clean as possible has finely divided organic matter of an insoluble
led to innumerable methods being tried for the character, which, by settling with the deposit,
prevention and removal of incrustations. prevents the crystallisation of the calcium
With a very hard water or one containing sulphate binding the mass into a hard crust,
ingredients which cause deposits in the boilers, and so allows the sludge cock to get rid of the
it isimpossible to do much good in the boiler loose deposit. Spent tan is a good example of
and the best way is to treat the water
itself, this class of anti-incrustator as not only does
before it is put into the boiler by some such it prevent binding of the
deposit, but it also
rapid method of precipitation and filtration blackens any scale that exists by the formation
as the Porter Clarke process, but for any such of tannate of iron, so making the boiler look clean.
process to be effective, care must be taken not to Deposits caused by lubricants entering boiler.
overdo the softening by adding too much of the As before mentioned, many of the inconveniences
precipitants, as an excess of calcium hydroxide arising from the use of animal and vegetable
in the water gives rise to as much trouble in oils can be avoided by the
employment of
the boilers as if the ordinary lime salts had mineral oils as lubricants, but with the intro-
been present. duction of high-pressure steam even mineral
It is quite possible to so treat even sea lubricants used in the cylinders have become a
water as to make it available for boilers, and source of trouble, as, when used too freely or
experiment has shown that, using sea water when they are not of good quality, they may
so treated, a boiler which had been kept steaming give rise to a dangerous form of deposit, and
continuously for a month, when opened, was with high-speed engines give a great amount of
found to be in perfect working order, but in this trouble in the boilers.
case also the sea water cannot be treated in the In 1878 the furnaces of the s.s. Ban Righ
boilers themselves, otherwise very heavy deposits and the screw tug Ich Dien collapsed without
would be formed. apparent reason. The only clue to the cause
In fresh- water boilers incrustation can to a was a certain amount of oily deposit which had
certain extent be prevented, or at any rate formed on the tops of the furnaces, and the
diminished, by the addition of substances which result of experiments made by Mr. Dunlop, of
will prevent the calcium sulphate binding the Port Glasgow, showed that this oil, which had
calcium carbonate into a hard mass, and these found its way into the boiler from the cylinders,
so-called anti-incrustators may be divided into was so bad a conductor of heat that its formation
two classes : on the plates allowed them to get overheated ;
1. Those which have some definite chemical they were thus unable to withstand the pressure
action. of steam in the boiler, and collapsed.
2. Those which are purely mechanical in Instances of collapse from similar causes
their action. became increasingly frequent, no less than thirty
In saline anti-incrustators
sodium carbonate occurring within a few years. The causes which
in one form or another generally plays the occasioned them were not at first sight apparent ;
principal part. Its action is to convert the the scale upon the furnace tops where the
calcium sulphate and magnesium chloride into collapse had taken place was not only free from
carbonate, and at the same time to keep the oil,but perfectly harmless both in quantity and
water in an alkaline condition so as to prevent quality. On closer investigation, it was evident
any damage from acids. that this scale was not in the condition in
Calcium Sodium Calcium Sodium which it was formed originally, as the deposits
sulphate carbonate carbonate sulphate from the bottom of the boiler tubes, from the
CaSO + Na 2 C0 3 = CaCO 3 = Na 2 S0 4 bottom of the furnaces and from the shell of
the boiler, were rich in oily matter, and it was crown of the furnaces at one spot, the result
' '
impossible that the furnace tops could have being the formation of a pocket by the local
escaped being coated during this deposition. bulging of the plate.
Experiment soon pointed out the reason for In these oily deposits copper is sometimes
this anomaly, and revealed the actions which found in considerable quantity, due to the slight
had taken place. solvent action of the mineral oils upon copper
In a case which was thoroughly investigated, and its alloys, used in the fittings of the cylinders
the pressure at which the boilers were worked and condenser.
was 80 Ibs. per square inch, corresponding to a Experiments with such deposits have shown
temperature of 311F. (111C.), which was so that even if they are only one-sixteenth of an
far below the boiling-point of the lubricant that inch in thickness, the furnace crown can be
it was evident that it had not distilled in the heated to redness, whilst with an oxy-hydrogen
usual way. Experiment showed that the fact flame the metal can be burnt through in a thin
that a lubricant had a higher boiling-point than wrought-iron plate.
the temperature of the steam, is no guarantee that Experiments upon the power of plates to
no oil will enter the boiler, as under the influence transmit heat bring out the effect of oily deposits
of steam, heat, and pressure the hydrocarbons in an extraordinary way, as it has been shown
of high boiling-point break up into simpler ones that merely wiping the surface of a plate with
boiling at lower temperatures. Having thus a greasy rag hinders the transmission of heat to
found its way into the boiler, the particles of a very considerable extent, and that a thin film
oil coalesce and form a scum on the surface of of oil is as prejudicial as a couple of inches of
the water, with no tendency to sink, since the boiler scale.
specific gravity is about 0-889. Small particles In connection with the question of deposits
of calcium sulphate, which is nearly always caused by lubricants entering the boiler, it may
present owing to small leakages of sea water be stated that the chief essentials of a good
in the condensers, adhere to this scum, and, lubricating oil are that it shall be a pure mineral
becoming coated with oil, stick to one another oil, and that its distilling point in steam shall
and to any surface with which they come in be higher than that of the steam in the cylinder.
contact. The particles thus coated with oil Such oils can be readily obtained, but as the
have the same specific gravity as the water, process of extracting the low boiling-point oils
and rise and fall with the convection currents, is expensive, their price is necessarily high.
sticking to any surface against which they strike, Any lubricant which requires animal or vegetable
and in this way depositing themselves, not, as oils to givebody should be rejected.
it
in common incrustations, on the upper surfaces, Mineral oils are not fats, but hydrocarbons
but also on the under sides of the tubes. The compounds of carbon and hydrogen differing
deposit so formed is a bad conductor of heat, widely from animal and vegetable oils, which
and nature tends to prevent intimate
its oily are liable to be decomposed with liberation of
contact between the water and itself. When fatty acids. The fatty acids are set free by the
this occurs on the crown of the furnaces, over- action of high-pressure steam, and attack iron,
heating of the plates is the consequence, and the copper, and copper alloys with great readiness,
deposit begins to decompose by heat, the lower forming metallic soaps, and thus cause serious
layer next the plates giving off gases which damage to both boilers and fittings. Another
blow up the greasy layer and render it porous, objection to animal and vegetable oils is their
thus making it a still worse conductor of heat. tendency to oxidise, forming a gummy resinous
The plate then becomes heated to redness, and substance.
being unable to withstand the pressure of steam, The prevention of oily deposits. The general
collapses. During the last stages of the overheat- methods adopted to prevent the condenser
ing the oily matter has decomposed thoroughly water introducing oily matter to the boiler are :
and burns away, or rather is distilled off, leaving 1. Cleansing the steam in an exhaust steam
behind, as an apparently harmless deposit, the separator.
solid particles round which it had originally 2. Passing the condenser water through a
formed. feed-water filter.
This oily deposit will more likely be produced The great advantage of the former method
with fresh or distilled water, owing to the low is that most of the oily matter is abstracted
density enabling the deposit to settle more before the condensers are reached, and greasing
quickly ; it is evident also that when this oily of the condenser tubes is prevented, and as the
scum has been formed in the boiler it is dangerous action of the grease is to prevent proper contact
to blow off without first
using the scum cocks, between the water and the metal surface, the
as, whilst the water is sinking, the scum clings loss of condensing power due to a small quantity
to the surfaces of the furnaces, &c., and on of oil is very great, and may cause a loss of from
filling with fresh water, remains there, causing 8 to 15 p.c. in efficiency after a few hours'
rapid collapse. A remarkable instance of this steaming.
occurred in the case of a large vessel in the In these exhaust steam separators the rate
Eastern trade, in the boilers of which an oily of flow of the steam is reduced by leading it into
scum had formed. The ship stopped at Gib- an enlarged chamber, and causing it to impinge
raltar, and the engineer blew out his boilers, on surfaces to which the oily particles adhere.
filling up with fresh water, with the result that There are several types made, and the results
before the ship had been at sea ten are satisfactory, but they do not always ensure
days most
of the furnaces had come down. freedom from traces of oil.
Under some conditions the oily scum Feed-water filters may be either mechanical
coagulates with the solid particles into a thin scrubbers, in which coke, charcoal, sawdust,
cake, which sinks and forms a patch on the crushed quartz, or other inert material exposing
BOILER INCRUSTATIONS AND DEPOSITS.
a large surface, may be used, or they may be BOLOGNIAN STONE. A native variety of
surface filters, in which the water passes through barium sulphate found as nodular masses
cloths fixed on frames, and these filters may be mbedded in clay near Bologna ; when partially
fixed between the feed pump and boiler, in which reduced to sulphide by calcination with charcoal,
case they are under heavy pressure or they ;
it exhibits phosphorescence (v. BARIUM).
may be used as gravity filters before the feed BOLORETIN v. RESINS.

pump is reached, in which case filtration is BOMBICESTOROL v. STEROLS.
carried on more slowly and the separation is BONE. Bony tissue may be either compact
far more satisfactory, the drawback, however, as in the shafts of the long bones, or spongy or
being that they occupy more space. It has been cancellated as in the flat bones of the skull and
found that to ensure complete separation of in the extremities of the long bones ; here an
the oily particles, it is highly advantageous to external compact layer encloses a mass of
add small quantities of aluminium sulphate to spongy bone or diploe. From the embryological
the condenser water in a treatment tank before point of view, bones may be divided into
filtration, as this causes coagulation of the fine cartilage bones and membrane bones. The
particles of oil emulsified in the water, and leads cartilage bones are those which in embryonic
to their easy separation in the filter. V. B. L. life are preceded by cartilaginous prefigure-
BOIS-PIQUANT BARK. The bark of Zan- ments ; these comprise the majority of the bones
ihoxylum caribceum (Lam.), and Z. Perrottetii in the body, and include all the long bones except
(D.C.). Used in France as a febrifuge (Heckel a. the clavicle. In the case of membrane bones
Schlagdenhaffen, Compt. rend. 98, 996). (for instance, the flat bones of the cranium), there
BOLDO. A shrub, Peumus boldus (Molina), is no such preliminary cartilaginous prefigure-
belonging to the Monimiacece, growing in the ment. It must not, however, be supposed that
Chilian Andes. The bark is used in tanning, the in the cartilage bones the cartilage is converted
wood makes a good charcoal, and the bark and into bone for here, as in the cases where there is
;
H
leaves contain a glucoside C 30 52 8 useful as a , no cartilage present, the true bony tissue is
hypnotic and cholagogue (Chapoteau, ,Compt. laid down by the agency of certain cells termed
rend. 98, 1052). osteoblasts in the connective tissue sheath
BOLE. (Bol, Ger.) A
ferruginous clay -like (periosteum) of the bone, and the cartilage
substance, of red, brown, or yellowish colour. It when present, after undergoing a certain amount
is not plastic, and when thrown into water of calcification, is then entirely eaten away by
falls to pieces with emission of streams of certain large cells called osteoclasts. In the
minute air-bubbles. It has an unctuous feel, cartilaginous, as distinguished from the bony
and some varieties adhere to the tongue. When or teleostean, fishes, the replacement of the
cut it presents a shining streak. Before the cartilage by true bone does not occur.
blowpipe it fuses to a yellowish or white enamel. Bone is deposited in concentric laminae, the
Its composition is very variable, but its usual majority of the layers encinmng the channels
limits are from 41 to 47 p.c. Si0 2 , 18 to 25 p.c. called Haversian canals, in which the blood-
A1 2 3 and 24 to 25 *p.c. H 2 0, with a proportion
,
vessels lie. The living elements in bone, the
of Fe 2 3 which may reach 12 p.c. It will be bone cells, lie in spaces between the laminae,
noticed that the percentage of water is higher and these spaces (lacunas) intercommunicate
than in clays. The Fettbol of Freiberg in by minute canals, in which lymph flows and
Saxony occurs in mineral veins, and contains maintains their nutrition.
only about 3 p.c. of A1 2 3 The bole of Stolpen
. The chemical materials present are organic
in Saxony is a j'ellowish substance containing and inorganic. The organic materials are
only a trace of Fe 2 3 Rammelsberg's analysis
.
proteins and nuclei'n derived from the bone
yielded Si0 2 45-92 ; A1 2 3 22-14 ; Cap, 3-9
, , ; cells, a small quantity of an elastin-like sub-
H 2 0, 25-86. In the bole of Sinope (sinopite)
' '
stance which forms a lining to the Haversian
from Asia Minor the Si0 2 falls as low as 32 p.c. canals, and a mucoid or glucoprotein ; but the
The ancients obtained this material from principal organic material, sometimes misnamed
Cappadocia, and used it as a red pigment. It bone cartilage, is better termed ossei'n. Osse'in
was also employed in medicine as an astringent is identical with the collagen of connective tissues,
(v. LEMNIAN EARTH). and like it yields gelatin on boiling with water.
is an analysis of bole, occurring
The following If the inorganic salts are dissolved out by
in granite,at Steinkirchen, Bohemia Dried : mineral acids, the ossei'n remains as an elastic
at 100 it yielded Si0 2 , 46-73 ; Al,0 8 26-17 ; , mass which preserves the original shape of the
Fe..0 3 12-34; CaO, 1-64; MgO, 1-31;
, 2 O, K bone.
0-98 ; MnO, 0-28 ; loss on ignition, 10-53 The inorganic constituents remain as the
(G. Starkl, Verh. k. k. Geolog. Reichs. Vienna, so-called bone earth after the bone is completely
1880, 279). calcined ; it consists chiefly of calcium phosphate,
Bole is frequently found as a product of the but also contains calcium carbonate, and small
decomposition of basaltic rocks. Thus the amounts of magnesium, chlorine, and fluorine.
sheets of basalt in N.E. Ireland, representing Gabriel (Zeitsch. physiol. Chem. 18) states
Tertiary lava-flows, are separated by partings of that potassium and sodium also occur. Traces
bole, associated with lithomarge, bauxite, of iron come from the blood in the bone, and of
pisolitio iron-ore, and seams of lignite. The sulphate from chondroitin-sulphuric acid (Morner,
Antrim bole described as a poor variety of
is ibid. 23).
aluminous iron-ore (Tate and Holden, Quart. Investigators differ as to the manner
in
Jour. Geol. Soc. 26, 1870, 155 ; G. H. Kinahan, which the inorganic substances are combined.
Jour. R. Geol. Soc. Ireland, 16, 1886, 306; Chlorine and fluorine are present in the same
P. Argall, ibid. 98). L. J. S. form as in apatite (CaFL-3Ca 3 P 2 O s ), and
BOLOGNIAN PHOSPHORUS v. BARIUM. according to Gabriel, the remaining mineral
BONE FAT. 489
constituents form the combination 3(Ca 3 P 2 8 )

CaC0 3 .He gives as the simplest expression
for the composition of the ash of bones and
teeth the HP
formula Ca 3 (P0 4 ) 2 +Ca 5 3 O 13 +H,:0,
in which 2-3 p.c. of the Hme is replaced by
magnesia, potash, and soda, and 4-6 p.c. of
the phosphoric acid by carbon dioxide, chlorine,
and fluorine.
Zalesky's analyses (Hoppe-Seyler's Med.
Chem. Untersuch. 19) show how
closely bone
earth agrees in composition in different animals.
The figures represent parts per 1000.
490 BONE PAT.
on the top and be skimmed off. In the case of by prolonged steaming. Hitherto, this kind of
fresh bones, the recovered bone fat had a white fat has not been treated successfully, and even
to yellowish colour, a faint odour and taste, when some immediate improvement was ob-
and the consistence of butter. When putrid tained, the colour and also the unpleasant smell
bones were employed, the bone fat passed, 'reverted' after a short time. patent by A
according to age and state of decomposition Volland (D. R. P. 222669) claims, however, to
of the organic matter in the bones, through all bleach extracted bone fat by means of barium
gradations from a white fat to a dark rancid peroxide.
fat of a very disagreeable smell. The boiling- The bone fat obtained by the boiling-out
out process allows only about one-half of the or steaming-out process can be used for soap
fat to be recovered. The small yield, and the making ; the fat obtained by the extracting
nuisance connected with the preparation of process is utterly unsuitable for that purpose in
the bone fat forced the manufacturers to treat this country, on account of its rank smell.
the bones with steam under pressure. The On the continent, however, such
. benzin-
broken bones were placed in a cage fixed inside extracted fat is used up for soap in small quanti-
an autoclave, and were heated therein with ties, especially when the price of fatty materials
open steam, under a pressure of 2 to 3 atmo- is high. The bulk of bone fat is, however, used
spheres. The bone fat so obtained was of the in candle works, where it is hydrolysed in an
same quality as that prepared by the former autoclave and subsequently subjected to the
process. The best bone fat obtainable in the usual acidifying and distilling processes.
market is at present prepared by this process, Bone fat is an important article of commerce.
especially in the large packing houses of the The chemical composition of bone fat lies
United States and South America, where the midway between that of marrow fat and tallow.
bones are worked up in the fresh state. They On account of the large amount of fatty acid
'
are first washed in bone-washing machines.' contained in bone fat, this fat must be examined
These are cylinders usually 10 feet long and by special methods, for which the reader is
3 feet to 4 feet in diameter, built up from iron referred to Lewkowitsch, Chemical Technology
bars, 1 inch apart, fixed into two cast-iron and Analysis of Oils, &c., ii. 623.
heads. They are driven by chain and sprocket, Bone oil, fatty bone oil (not to be confounded
and rotate slowly, making about ten revolutions with Dippel's oil), is the liquid portion of bone
per minute. Through the entire length of the fat which sometimes prepared in the same
is
drum there is a hinged door made of bars, manner as tallow oil is obtained from tallow.
which allows the filling and emptying of the Bone oil is used as a lubricant, and in the
cylinder. The machines are usually set at an leather industries replaces neat's foot oil in
' '
angle to facilitate the washing and emptying the preparation of fat liquor and other
operations. Some manufacturers even resort emulsions. If such bone oil is free from fatty
to steeping the bones in a solution of sulphurous acids, it represents one of the best lubricating
'
acid in order to obtain a whiter fat (as also a oils on account of its very low cold test.'
better glue) than unbleached bones afford. J. L.
The yield of bone fat in the steaming-out process BONE MEAL v. FERTILISEBS.
under pressure is considerably higher (by about BONE OIL. Animal oil Dippel's ; oil ; Oil
50 p.c.) than in the boiling-out process in open of hartshorn Oleum animate empyreumaticum
; ;
vessels, so that from bones containing 12 p.c. of Oleum cornu cervi Oleum Dippelii. (Knock-
;
fat, 8 to 9 p.c. can be recovered. enol, Thierol, Ger.) The product obtained by
Bone fats of this quality can be bleached, distillingbones hi the preparation of bone black
but only the best kinds are likely to yield a or animal charcoal.
good product. The higher the percentage of The bones are first boiled in a large quantity
free fatty acids, the greater is the difficulty in of water, which removes the greater part of the
bleaching. In fact, products containing more fatty matters ; they are then roughly dried and
that 50 p.c. of free fatty acids could hitherto are subjected to dry distillation in iron retorts,
not be bleached successfully. similar to those used in the manufacture of coal
The highest yield of bone fat is obtained by gas. Bone black or animal charcoal remains
treating the bones with an organic solvent, behind and bone oil distils. The products of
whereby the animal tissue remains unimpaired, distillation are conducted through long iron
so that the whole of the glue-yielding organic tubes, which act as condensers and lead into
substances can be converted into glue aftei the receivers, where the crude bone oil collects, '
fat has been removed. The solvent used in bone- together with water. The gases are then passed
extracting works is almost exclusively petroleum into a separator containing sulphuric acid to
ether or Scotch shale oil, boiling between 100 and retain ammonia, and can afterwards be used for
130. Proposals have been made to use carbon heating purposes, or, if passed through purifiers,
tetrachloride or chloro- compounds of ethylene for The crude oil
illumination. is separated
and ethane. Experiments with carbon tetra- from the aqueous distillate and is subjected to
chloride have, however, been abandoned as redistillation. The aqueous liquid consists of a
'
unremunerative. Extraction with benzin or
'
solution of ammonium sulphide, ammonium thio-
and
shale oil takes place in iron digesters under cyanate and cyanide, ammonium carbonate,
pressure or in open apparatus. The fat obtained small quantities of very volatile organic bases.
by the extracting process is dark-brown, and This is treated with sulphuric acid and afterwards
has a very penetrating, unpleasant smell. In distilled with slaked lime. The distillate, on
addition to a considerable amount of free fatty treating with solid potash, yields large quantities
acids, it contains lime-soap, calcium lactate, ofammonia, whilst some oUy bases separate out,
calcium butyrate, and hydrocarbons from the and are afterwards worked up with the bases
' '
benzin which cannot be fully removed even contained in the crude oil. This latter is a
BONE OIL.
dark-brown, nearly black liquid, having a fcetid, By the action of iodine on potassium
pyrrol,
most offensive smell, and a sp.gr. 0-970. tetriodopyrrol is formed, which
crystallises in
On subjecting it to redistillation it begins to yellowish-brown prisms and decomposes at
boil at 80, when quantities of ammonia come about 140. It acts like iodoform as an anti-
over together with an oil. The temperature septic, and is known as iodol. It has the
rises very gradually to about 250. From advantage over iodoform of being free from
180 upwards large quantities of ammonium smell.
cyanide and ammonium carbonate sublime over, Pyrrol has been synthesised by passing
and care has to be taken to prevent the con- acetylene and ammonia through red-hot tubes :
denser being stopped up. A black resinous 2C 2 H 2 +NH 3 =C 4 H 4 NH+H 2 ;
tar remains, which is employed in making
Brunswick black.
also by distilling the ammonium salts of mucic
and saccharic acids.
Succinimide, on heatins
following substances have been isolated
The with zinc-dust containing zinc hydrate, also
from bone oil by fractional distillation com-
bined with treatment with acids to separate yields pyrrol
basic from non-basic constituents : CH, CO CH=CH
Chief constituents Subsidiary constituents >NH+2H = 2 >NH+2H,0.
Butyro-nitrile Methylamine
Valero-nitrile Ethylamine
CH,. CO CH=CH
Hexo-nitrile Aniline Potassium dissolves in pyrrol with the forma-
Isohexo-nitrile Pyridine H
tion of potassium pyrrol C 4 4 NK, a substance
Deco-nitrile Methyl-pyridine insoluble in ether and decomposed by water into
Palinito-nitrile Dimethyl-pyridine pyrrol and potassium hydroxide. This sub-
Stearo-nitrile Quinoline stance reacts with alkali iodides to form substi-
Pyrrol Phenol tuted pyrrols e.g. ;
:
Methyl-pyrrol Propionitrile N-Methylpyrrol, C 4 H 4 N-CH 3 : boils at 113 ;
Dimethyl -pyrrol Valeramide sp.gr. 0-9203.

(C
H 14 9 Toluene N-Ethylpyrrol C 4 H 4N-C 2 H6 : boils at 131 ;
H
Hydrocarbons] C 10 16 Ethyl-benzene sp.gr. 0-9042.
(CU H 18 Naphthalene N-Phenylpyrrol C 4 H 4 N-C6 H 5 , obtained by
(Weidel and Ciamician, Ber. 13, 65). distilling the anilides of mucic and saccharic
As to the formation of the various compounds acids, melts at 62. The homologues of pyrrol
in bone oil, the nitriles are formed by the action contained in bone oil are, however, all substi-
of ammonia on the fatty acids, pyrrol and the tuted in the group C 4 4 . H
Bythe action of benzalchloride on pyrrol in
pyrrols are the products of decomposition of the
gelatinous substances, and pyridine and its presence of sodium a phenylpyridine is obtained
derivatives are condensation products of acrole'in, in which the phenyl is in the meta- position to
from the dry distillation of the fats, with the nitrogen (Ciamician and Silber, Ber. 20, 191).
ammonia, methylamine, &c. By reducing pyrrol with zinc and acetic acid
Pyrrol. That portion of the non-basic part A3 pyroline is produced (Ber. 1901, 3952).
of bone oil boiling at 98-150 contains pyrrol Electrolytic reduction to the same substance
and its homologues. That above 150 contains may be effected by suspending pyrrol in dilute
dimethylpyrrol. The fraction 140-150 consists sulphuric acid in the cathode cell of an electro-
of a mixture of homopyrrols i.e. methylpyrrols. lytic apparatus, the cathode being lead, and
To separate the a- and 0- derivatives, the mixture passing a current of density 1 amp. per sq. cm.
is converted into the potassium compound Homologues may be similarly reduced (D. R. P.
by fusion with potash, and heated in a current 127086, 1902).
of carbon dioxide to 200. Two isomeric homo- Nascent hydrogen converts pyrrol into pyro-
pyrrol carboxylic acids are formed, which differ line C 4 H 6 NH, a liquid boiling
at 91 which dis-
in the solubility of their lead salts. a-Homo- solves easily in water. It yields, with nitrous
H
pyrrol carboxylic acid melts at 169-5, and its acid, a nitrosoamine C 4 6 N-NO, m.p. 37,
lead salt is very soluble in water, differing from and on heating with methyl iodide gives
the 0-acid, which melts at 142-1, and forms a methylpyrroline (Ber. 16, 1536).
slightly soluble lead salt. The acids obtained Pyrrol is readily oxidised to maleimide
respectively yield on distillation with lime the C 4 H 3 O 2 N, which
forms faintly yellow crystals,
corresponding methylpyrrols. a-Homopyrrol melting at 93, and readily yields a dibromide,
boils at 148 under 750 mm. pressure, and melting at 226 under the influence of light and
0-homopyrrol at 143 at 743 mm. bromine water R. 1904, (v.) i. 489).
(Atti.
The The action of formaldehyde and methylene
constitution of pyrrol is represented as
follows : chloride on pyrrol is described by Pictet and
CH=CH, Rilliet (Ber. 1907, 1166).
By the action of chloroform in absolute ether
CH=CH / on the potassium. derivative of pyrrol, chloro-
pyridine is obtained.
the positions 2 and 5 and 3 and 4 being known
Pyrrol derivatives condense with aldehydes
as the a- and - positions respectively. It boils under the following conditions : (1) When the
at 130-131, and its sp.gr. is 0-9752 at 12. derivatives contain at least one hydrogen atom
=
Refractive index ;U D 1-5074 (Gladstone, Chem. combined with a carbon atom of the nucleus,
Soc. Trans. 1884, 246). It is slightly soluble in either in the a- or j8- position ; (2) when both
water, readily soluble in alcohol and ether. It a- and /3- positions are occupied by substituents,
is a weak base, and is no combination occurs even if the iminic hydrogen
only slowly dissolved by
dilute acids in the cold. is present ; (3) pyrrol derivatives containing
492 BONE OIL.
more than one CH
group in the ring may com- monia on diacetosuccinic ether, the ether of
bine with aldehydes in molecular proportions dimethylpyrrol dicarboxylic acid is obtained.
(Ber. 1902, 1647). This, on saponification, yields the acid, and, on
Indole C 6 H 4<^\TTT .^CH is obtained by dis- heating, carbon dioxide is split off, leaving di-
methylpyrrol. It has the composition
solving pyrrol in 10 p.c. sulphuric acid, allow- CH=OCH 3
ing the mixture to stand 1-2 hours, and then
distilling in steam after adding excess of sodium
hydroxide. Diethyl indole prepared by this CH=C-CH 3
process is a viscid ill-smelling oil, boiling at
270-310 (D. R. P. 125489). and is an almost colourless
oil boiling at 165.
It is very volatile with steam, colours a pine
Pyrrol may also be converted into indole
splint an intense red, and yields on boiling with
by dissolving in dilute hydrochloric acid, acids a pyrrol-red similar to other pyrrol homo-
adding slight excess of ammonia, filtering,
logues.
extracting the filtrate twice with ether, and
Pyrrolearboxylie -acids C 4 (NH)H 3 C0 2 H. The
heating the tripyrroline obtained in the extract
to above 300, when indole and pyrrol result o-acid is obtained from a-homopyrrol by fusion
with potash or by the action of tetrachloride
(Ber. 1894, 476).
of carbon and alcoholic potash on pyrrol. It
Pyrrol may be converted into tetramethylene
diamine as follows. On treatment with hydroxyl- melts at 191, and differs from the /8- acid in
amine, a solid compound, probably the dioxime forming a soluble lead salt. On heating with
acetic anhydride, the substance pyrocoll
of succinaldehyde, is formed, and this, by
reduction with sodium and absolute alcohol, C 4H 3 =N CO
yields tetramethylene diamine.
Pyrrol derivatives of the constitution ^0 N=C H 4 3
Et0 2 OC=CMe is formed, which is a product obtained by dig-

tilling gelatine (Ber. 17, 103).
\N-C 6 H 4 N0 2 -Pvrrolearboxylie acid is formed by fusing
HC=CPh 0-methylpyrrol with potash. It crystallises in
have been synthesised from the three nitro- fine needles, melting at 162, and forms an in-
anilines by the action of ethylphenacyl acetate soluble lead salt.
(Ber. 1907, 1343).
H
N-Acetylpyrrol C 4 4 N-C 2 3 0, obtained by H
In addition, a large number of pyrrol deriva- the action of acetyl chloride on potassium pyrrol,
tives has been synthesised bv Paal and Braikoff is an oil boiling at 178. It is decomposed by
(Ber. 1890, 1086, and also Ber. 1886, 558, 3156). alkalis into pvrrol and acetic acid (Ber. 16, 2352).
Thephysiological action of pyrrol and its
H H
C-Aeetylpyrrol C 4 3 (C 2 S 0)(NH) is formed,
derivatives is characterised by their paralysing together with the foregoing, by acting on pyrrol
action on the peripheral nerves connected with with acetic anhydride. It melts at 90 and
the mechanism of the heart. By the introduction boils at 220, but is not decomposed by alkalis.
of a side group, such as, for instance, the in- Pyridine C 6 6 HN
is contained in that fraction
active pyridine ring, the physiological effect is of the basic oils of bone oil which boils below
greatly intensified. The action of 1- methyl 120, but is also found in smaller quantities in
the higher fractions. It can be separated in these
pyrroh'dine resembles that of nicotine, atropine,
or cocaine, as might be anticipated from their by means of its picrate C5H 5 N,C 6 H 2 (N0 2 3 OH, )
which melts at 162. It is not easily acted on

similarity of constitution (Chem, Zentr. 1902,
ii.
390). by oxidising agents, and can be separated by
this means from the other components of the
Chlorp- and Bromo- Pyrrols. Sulphuryl
fraction.
chloride in excess acting on an ethereal solution
of pyrrol at It is formed from all pyridinecarboxylic
produces pentachloropyrrol in
nearly theoretical yield ; b.p. 209 or 142/15 mm.
acidsby distilling with lime.
If two molecules only of sulphuryl chloride are The following are some of the synthetic
used, followed by bromine (2 mols.), chloro- methods for preparing pyridine and its homo-
tribromopyrrol C 4 NHBr 3 Cl is obtained, which logues :
1. Acrole'm ammonia, on heating, gives off

separates from light petroleum in large prismatic
masses of a pink colour. water yielding methylpyridine
Sulphuryl chloride (3 mols.) followed by C6 H 9 NO=CS H 4 (CH 3 )N+H 2 0.
bromine (1 mol.) gives dichlorodibromopyrrol 2.The same compound is formed by heating
C 4 HNCl 2 Br;, which crystallises in large shining
allyl tribromide with alcoholic ammonia at 250 :
scales decomposing just above 100 (Gazz. chim.

ital.
2C 3 H 5 Br 3 +NH 3 =C 5 H 4 (CH 3 )N+6HBr.
1902, 313).
3. Glycerol and acetamide, on heating with
CClrCCL
Trichloromonobromopyrrol \NH phosphorus pentoxide, yield methylpyridine
CBirCCK (Ber. 15, 528).
4. Potassium pyrrol, on heating with chloro-
may be obtained by the action of sulphuryl
chloride and bromine on ethereal solution of form, yields chloropyridine.
5. Ethyl acetoacetate, heated with aldehyde
pyrrol at 0. It crystallises in monoclinic prisms
with yellowish-red reflex, turning brown at 105, ammonia, gives dihydrocollidine dicarboxylic
and melting and decomposing at 115 (Gazz. ester
chim. 1902, 313 ; 1904, ii. 178).
ital.
The dimethylpyrrol contained in the fraction
of bone oil
boiling above 150 has been obtained =C 6 H N(CH 3
2 )3 (CO,C 2 H 5 ) 2 +3H 2
synthetically as follows : By the action of am- (Ber. 17, 1521).
BONE OIL. 493
By heating a mixture of glycerol and condenser with excess of a bisulphite solution,

ammonium phosphate, a mixture of a large are useful in the preparation of dyestuffs, and
number of pyridine bases is formed. 0-methyl, are also used as medicaments (D. R. P. 208638).
j3-ethyl, probably -propyl, pyridine, besides On heating pyridine with concentrated sul-
pyridine itself and homologues of the diazine phuric acid to 300, 0-pyridine-sulphonic acid is
C 4 H 4 N 2 have been
, recognised (Stoehr. J. pr. obtained. The sodium salt of this acid, distilled
Chem. 1892, 20). with potassium cyanide, yields ;8-pyridyl
Pyridine is a liquid with a pungent smell, cyanide, which on hydrolysis forms nicotinic
miscible with water ; sp.gr. 0-9855 at 15, and acid.
0-9944 at and boils at 115-2/760 mm. It
4; Pyridine may be estimated in aqueous
H
forms a hydrochloride C 5 5 N,HC1, and a platini- solution by heating with excess of gold chloride
H
chloride (C 6 5 NHCl) 2 PtCl 4 Sodium amalgam
. and dilute HC1, evaporating to dryness and
yields p i p e r i d i n e, i. e. hexahydropyridine, which heating the ppt. after repeated washing with
is reconverted into pyridine on oxidation. It pure dry ether. The ppt. has the composition
forms an ammonium iodide with alkyl iodides, C 5 H 5 N-HCl-AuCl 3 (Compt. rend. 1903, 324).
and with chloracetic acid a pyridine-betai'ne Pyridine can be represented as a benzene
ring in which one CH group is replaced by nitro-
/PTT \
C6 H 5 the action of sodium on
N<^Q^>CO. By gen according to the following scheme :
pyridine a dipyridine C 10 H 10 N 2 is obtained, an 4

oil boiling at 280-281/744 mm., which on oxi-
dation with permanganate yields isonicotinic 5C'
ff
acid. Together with dipyridine, a body p-di-
pyridyl is formed NC 5 H 4 -C 5 H 4 N, which melts .C 2
at 114 and distils at 304. It also yields isonico-
tinic acid on oxidation, and on reduction with
tin and hydrochloric acid forms isonicotine, The positions 2, 6, and 8, 5 are known as
which melts at 78 (Ber. 16, 423). ortho- and meta-, and 4 as the para- position.
The isomeric m-dipyridyl is obtained from Hence three mono- derivatives of pyridine are
wi-dipyridyldicarboxylic acid (by oxidising phen- possible. The position of the substituting groups
anthroline). It boils at293, and yields on in these isomerides has been proved by means
reduction with tin and hydrochloric acid of the phenylpyridines obtained from the naph-
nicotidine C 10 H 14N 2 which
, boils at 288 (Ber. thaquinolines (Monatsh. 4, 437 ;
Ber. 17, 1518).
16, 2521). HYDKOXY- DERIVATIVES OF PYRIDINE.
Pyridine, when passed together with hydro- The three are
possible hydroxypyridines
gen over reduced nickel at 160-180, yields known :
amylamine, not piperidine, and this in poor a-Hydroxypyridine, a-pyridone, by distilling

yield. At higher temperatures ammonia, pentane the silver salt of hydroxyquinolinic acid ; melts
and lower hydrocarbons are obtained (Sabatier
and Mailhe, Compt. rend. 1907,
at 107, and is coloured red by ferric chloride.
784).
j8-Hydroxypyridine is formed from the -sul-
Pyridine may advantageously be employed phonic acid by fusing with potash. It melts at
as a halogen carrier in halogenation of aromatic
123, and is also coloured red by ferric chloride.
compounds (Cross and Cohen, Chem. Soc. Proc.
7-Hydroxypyridine or y-pyridone (which is
1908, 15).
The compound of pyridine with methyl probably not a hydroxyl- but a carbonyl- com-
pound) is obtained from hydroxypicolinic acid
iodide, when added to a solution of the neces- with evolution of CO.,. It melts at 148 or at
sary amount of iodine in alcohol, is converted 62 in the hydrated form, and is coloured yejlow
into pyridine methylpentiodide C 5 N(MeI)I 4 H ,
by ferric chloride (Ber. 17, Ref. 169).
melting at 47-5. Various other periodides
are described by Prescott and Trowbridge PYRIDINE MONOCARBOXYLIC ACIDS
(J. Amer. Chem. Soc. 1895, 859). C 5 NH 4 (C0 2 H).
Double compounds with zinc bromide, a-Pyridineearboxylie acid (2- or ortho-),
nickel bromide, copper bromide, and silver picolinic acid was first obtained by oxidising
iodide, are formed, but are rather unstable a-picoline. It is easily soluble in water, crystal-
(Compt. rend. 1891, 622). lises in white needles, melts at 137, and sub-
The physiological action of pyridine is similar limes. By the action of sodium amalgam,
to that of piperidine, but more Both ammonia is given off with the formation of an
energetic.
produce paralysis of the motor nerves, by their acid H
C 8 8 3 (oxysorbinic acid).
effect on the motor centres. There are also acid (3- or meta-), called
j8-Pyridinecarboxylic
destructive changes in the blood corpuscles, and nicotinic acid from the fact of being first
paralysis of the heart, especially in pyridine obtained by oxidising nicotine, is also obtained
poisoning (Chem. Soc. Abstr. 1891, 603). from -methyl- or ethyl-pyridine, from /3-pyridyl
It excreted as methylpyridylammonium cyanide, and from three dicarboxylic acids
is
hydroxide (Chem. Soc. Abstr. 1893, ii. 544). of pyridine (quinolinic acid, cinchomeronic
The double compound of pyridine with silver acid, and zsocmchomeronic acid), which on
nitrateAgN0 3 -2C 5 H 6 N has been recommended heating give off carbon dioxide. It crystallises
by Witt as a ripening agent for photographic in needles and melts at 232.
emulsions (J. Soc. Chem. Ind. 1904, 235). acid (4- or para-), iso-
y-Pyridineearboxylic
Liippe-Cramer,however, denies that it has nicotinic acid obtained from cinchomeronic
is
any advantages over the ordinary ammonia acid and 2 4-pyridinedicarboxylic acid on heat-
:
ripening (ibid. 1906, 197). ing. It melts at 299-5 with sublimation or at

Sulphurous acid esters of pyridine, which 315 in a closed tube, and crystallises from hot
may be obtained by heating under a reflux water in fine needles.
494 BONE OIL.
ACIDS. ondensation of isobutylaldehyde with ethyl
Several of these acids have been prepared cetoacetate and ammonia (Hantzsch and Weiss,
either synthetically, e.g. by heating komanic Jer. 19, 284).
H
acid C 6 4 4 with ammonia, or from the dicar- The acid obtained by oxidising collidine-
boxyh'c acids by splitting off 1 mol. of carbon monocarboxylic acid crystallises with 2 mole-
dioxide (Ber. 17, 589). ules of water and melts at 110. The dried
Komenaminie acid C6 NH 2 (OH) 2 COOH,2H 2 cid melts at 155 (Annalen, 225, 133).
is obtained by boiling komenic acid C S 4 O 6 H Pyridine-pentacarboxylic acid C S N(C0 2 H) 5
with ammonia. It decomposes at 270 into rom trimethylpyridine-dicarboxylic acid. Crys-
carbon dioxide and dihydroxypyridine. allises from water with 3H,O. Decomposes
vithout melting about 200.
PYRIDINE-DICARBOXYLIC ACIDS C6 NH 3 (C0 2 H) 2 .
HALOGEN DERIVATIVES OF PYRIDINE.

Quinolinic acid (aft- or 2 3-) is formed by :
It decomposes and softens a-Chloropyridine results from the action of

oxidising quinoline.
?C1 S on a-hydroxypyridine-; is an oil boiling at
at 190-195, solidifies at 200, and melts again
at 231. It decomposes on heating into carbon 66/714 mm. (Ber. 1891, 3150).
dioxide and nicotinic acid. P-Chloropyridine. By the action of chloro-
'orm or carbon tetrachloride on potassium
Cinchomeronic acid (fry- or 3 4-) is formed by :
the oxidation of the quinine alkaloids with nitric pyrrol (Ber. 14, 1 153) is an oil ; b.p. 148/743 mm.
Dichloro- and trichloro-pyridine are known.
acid, or from j87-methylpyridinecarboxylic acid
on oxidation with permanganate. It melts at A dibromopyridine (&&') has been obtained
into carbon dioxide, 7-pyri- )y acting on collidine-dicarboxyh'c acid with
259, decomposing
jromine and afterwards removing the carboxyl-
dinecarboxyh'c acid, and some nicotinic acid.
Lutidinic acid (07- or 2 : 4-) is obtained, to- groups (Pfeiffer, Ber. 20, 1349). It is identical
with some isocinchomeronic acid, by h that obtained by acting on pyridine with
gether
It melts at 239-240
sromine (Hofmann, Ber. 12, 988).
oxidising lutidine.
(Voigt, Annalen, 228, 54), 235 (Ladenburg, HOMOLOGUES OP PYRIDINE.
Annalen, 247, 27), decomposing into carbon Picoline (a-methylpyridine) C 6 NH
4 (CH 3 ). This
dioxide and 7-pyridinecarboxylic acid. base is separated from that portion of bone
/soeinehomeronie acid (a'-) melts at 236, oil which boils between 130 and 145. On
decomposing into carbon dioxide and nicotinic subjecting this to redistillation, the greater
acid (Werdel and Herzig, Wiener Akad. B. 1879, part of the oil comes over between 133 and
825). 139. It is not possible to effect a separation
Dicarboxylic acid ('-) or Dinicotinic acid. of the bases by means of fractional distil-
By heating to 150 s-pyridine tetracarboxylic lation, but a difference in the solubility of the
acid obtained by oxidising the lutidincarboxylic platinum salts of the two bases furnishes a
acid, prepared by the condensation of isobutalde- means of separating them. According to
hyde ethylacetoacetate and ammonia. The Ladenburg (Ber. 1885, 47), commercial picoline
acid does not melt at 285 (Hantzsch and Weiss, consists of three bases :
a-methylpyridine, a
Ber. 1886, 19, 284. little 0-methylpyridine, and probably ao'-di-
Dicarboxylic acid ('-) or Dipicolinic acid. methylpyridine. The same observer (Ber.
Obtained by oxidising 2 6-dimethylpyridine.:
1885, 51) has also noticed the presence of
It melts at 243 (Epstein, Annalen, 231, 32). pyridine in this fraction. It can be separated by
HYDROXYPYRIDINE-DICARBOXYLIC ACIDS means of its picrate, which melts at 162.
Picoline boils at 128-8/760 mm. ; is an
CB NH,(OH)(C0 2 H) B .
= optically inactive oil, and on oxidation yields

Hydroxyquinolinie acid [OH (C0 2 H) 2 :
picolinic acid (v. supra).

(a' : a : )]. By fusing quinolinic acid with 0-Methylpyridine boils at 143-5, and on
potash. It blackens without melting at 254 oxidation yields nicotinic acid. It also differs
(Ber. 16, 2158). Heated with water to 195 i
from the o-derivative in being slightly laevo-
decomposes into carbon dioxide and hydroxy
rotatory. Landolt shows this effect to be due to
pyridinecarboxylic acid. Its silver salt on errors in manipulation (Ber. 1886, 157).
heating yields a-hydroxypyridine (Ber. 17, 590)
Ammonioehelidonic acid is obtained by heat 7-Methylpyridine does not appear to bo
contained in bone oil. It has been obtained
ing chelidonic acid with ammonia.
synthetically by the action of heat on acrolein-
PYRIDINE-TRICARBOXYLIC ACIDS C5 NH 2 (C0 2 H) 3 ammonia, and also from allyl tribromide; b.p. ,
o/S-y-Triearboxylie acid, Carboeinchomeroni 143-1/760 mm.

acid, is formed by completely oxidising the PlCOLDfE-MONOCARBOXYLIC ACIDS
quinine alkaloids, also from 7-methylquinolin C5 NH 3 (CH 3 )C0 2 H.
and from 7-quinolinecarboxylic acid. It lose
Pieolinecarboxylic acid (pyridine-a-methyl-y-
1|H 2 O (of at 115-120, anc
crystallisation)
carboxylic acid) is formed from uvitonic acid,
melts, if quickly heated, at 250 (Annalen the product of condensation of pyruvic acid
204, 308). and ammonia. It sublimes without melting,
a/3'-Tricarboxylic acid, carbodinicotini
and yields on oxidation a : 7-pyridinedicar-
acid, is obtained from 0-quinolinecarboxyli
It melts at 323 (Annalen, 241, 11).
boxylic acid.
acid.
^y-Methylpyridine carboxylic acid
The tricarboxylic acids theoretical!
six
H=
(OH 3 : C0 2 7 : ft) is obtained by heating
possible are known and characterised.
methylquinolinic acid to 180-185. It melts
PYRIDINE-TETRACARBOXYLIC ACIDS at 212 (Ann. Chim. Phys. [5] 27, 493), and
C 6 NH(CO,H) 4 .
yields on oxidation cinchomeronic acid.
a/3a''-Tetracarboxylic acid. By oxidisin Six of the ten possible picoline uionocar-
the lutidinedicarboxylic acid formed by th boxylic acids are known and characterised.
BONE OIL. 495
PlCOLINE-DICAKBOXYLIC AdDS chloric acid of the bases boiling at 1 58-l 60. The
salt hasthe composition C 7 H 9
C 5 NH 2 (CH 3 )(C0 2 H) 2 . N,HCl,2HgCl 2 ,
and melts at 127. On distilling with potash, the
Methylquinolinic acid ((C0 2 H) 2 : 3 =*i3y).CH salt is decomposed, and the base, after
drying,
By oxidising 7-methylquinoline with perman- boils at 157. Its sp.gr. is 0-9493iat0
/4 . It yields
ganate. It melts at 186, giving carbon dioxide a pyridine-dicarboxylic acid on oxidation with
and 7-methyl--pyridine-carboxylic acid.
permanganate, and the acid melts at 235. This
Uvitonie acid [(CO Z H) 2 CH 3 =a7a'] is the
:
is known as o-lutidinic acid or oy-pyridine-
condensation product obtained, from pyruvic
dicarboxylic acid, since on heating carbon dioxide
acid and alcoholic ammonia. It melts at 274, is given off and zsonicotinic acid is formed.
splitting up into carbon dioxide and picoline- Hence -lutidine has the composition
carboxylic acid. CH 3
Picoline-dicarboxylic acid, from aldehydine,
the condensation product of ethylidene chloride
and aldehyde ammonia. It sublimes easily
without melting.
Three other isomerides are known.
A picoline-tetracarboxylic acid is also (Ladeiiburg and Roth, Ber. 18, 913).
Collidines (y-collidine, trimethylpyridine )
obtainable from the dicarboxylic acid of collidine
by oxidation of the methyl- groups with perman-
C6 NH 2 (CH 3 )3
ganate. Lutidine-tricarboxylic acid is formed may be prepared by distilling collidine

as an intermediate product. dicarboxylic ester (obtained by oxidising
Lutidine (dimethylpyridine). The bases hav- the condensation product of aldehyde ammonia
ing this constitution are mainly contained and ethyl acetoacetate) with lime. It boils at
in that portion of the basic oil boiling 171-172, and has the constitution
between 150-170. After redistilling, it is OH,
separated into the two fractions 150-160
and 160-170. The position of the methyl
groups in these two fractions is determined CH,l >CH 3 .
by means of the oxidation products formed. N

The first fraction yields on oxidation isocin.-
chomeronic acid, which melts at 236. On H
A base, C 8 U N, has been isolated from
the fraction of bone oil boiling between 170
heating, carbon dioxide is split off and nicotinic
acid is formed. From this is inferred that the and 180, but this has been shown by Weidel and
Pick to be a 2-methyl-4-ethylpyridine from the
position of the two methyl groups is a'8. The
fact of its giving on oxidation lutidinic acid melt-
higher fraction yields lutidinic acid on oxidation,
and this, on heating, gives isonicotinic acid, from ing at 219. The base is more soluble in cold
which it follows that the methyl- groups have the than in hot water. Its sp.gr. is 0-9286 at 16-8 ;
it boils at 177-8/758 mm. (Weidel and Pick,
positions ay. All the acids give pyridine on
distillation with lime. According to the re- Monatsh. 5, 656). These authors are of opinion
searches of Ladenburg and Roth (Ber. 18, 49), that Anderson's collidine (Phil. Mag. 4, 9, 145,
the fraction 139-142 also contains a lutidine, 214) was impure. The base does not form any
which was separated by means of the mercuric crystallised salts, and is not identical with any
chloride salt, melting at 186. This was de- synthetical collidine.
composed with potash, and distilled, when, Aldehydine (2-methyl-5-ethylpyridine). Formed
after drying, an oil was obtained which boiled by the condensation of ethylidene chloride
at 142-143, and yielded on oxidation with per- with ammonia (Diirkopf, Ber. 18, 921). It boils
at 176, and has sp.gr. 0-9389 at 0/4.
manganate a dibasic acid which is identical
with that obtained from synthetical lutidine Collidine dicarboxylic acid is obtained by
prepared by condensing cinnamic aldehyde, oxidising hydrocollidine-dicarboxylic acid with

nitrous acid. The ether of the latter acid is the pro-
ethyl acetoacetate, and ammonia (Epstein,
duct of condensation of ethyl acetoacetate with
Annalen, 231, 1). Its sp.gr. is 0-9545, and b.p.
143. aldehyde ammonia. It yields on heating with
The constitution of the 0-lutidine
lime oa'7-trimethylpyriduie. The acid yields by
is
successive oxidation of the methyl- groups by per-
CH manganate the following carboxylic acids :
Lutidine-tricarboxylic acid
C5 N(CH 3 2 (C0 2 H) 3
) ,
(Ladenburg and Roth). Picoline-tetracarboxylic acid

Lutidine-monocarboxylie acid (aa -dimethyl-
C8 N(CH 3 )(C0 2 H) 4 ,
nicotinic acid). Obtained by distilling lutidine- Pyridine-pentacarboxylic acid C 5 N(C0 2 H) 6 .
dicarboxylic acid (Weiss, Ber. 19, 1308). It If one carboxyl- group be removed from the
crystallises in fine needles melting at 160. original acid and then it be oxidised, the following
Lutidine-diearboxylic acid. Obtained by the acids are successively obtained:
condensation of isobutylaldehyde, ethyl- aceto- From collidine-monocarboxylic acid
acetate, and ammonia (Engelmann, Annalen, H
C6 NH(CH 3 ) 3 C0 2 the acids lutidine-dicarboxylic
231, 51 ; Hantzsch and Weiss, Ber. 19, 284). . acid C 5 NH(CH 3 ) 2 (CO Z H) 2 , picoline-tricarboxylic
Lutidine-tricarboxylie acid is formed by the acid C5 NH(CH.,)(CO 2 H) 3 ,pyridine-tetracar-
oxidation of boxylic acid C 5 NH(C0 2 H) 4
collidine-dicarboxylic acid with per- .
manganate. Piperidine, hexahydro-pyridine, is obtained

a-Lutidine (2 <i-dimethylpyridine). Separated
: in small quantity by the reduction of pyridine
by adding mercuric chloride to a solution in hydro- with tin and hydrochloric acid (Konigs, Ber.
496 BONE OIL.
1881, 14, 1856). A better yield is obtained by When mixtures of pyridine (1 mol.) and
with aromatic amines (2 mols.) are acted upon by
operating in absolute alcoholic solution
sodium. It may be prepared from pyridine cyanogen chloride or bromide dyestuffs are
in 95 p.c. yield by electrolytic reduction formed practically quantitatively and very pure,
(E. Merck, D. R, P. 90308; Pip, Eng. Pat.
with the elimination 1 mol. of cyanamide.
21471). It may also be prepared by heating They crystallise and vary from yellow,
well,
piperine, obtained from pepper, with

soda lime. through orange and red, to violet, and dye silk
It is a liquid smelling like pepper and ammonia, in shades showing fine fluorescence and some ;
show marked affinity for unmordanted cotton.

boiling at 105-7, sp.gr. 0-8810 at 0. Miscible
in all proportions with water. It combines They are soluble hi water with difficulty, more
with quinones to form dyes. readily in acetic acid and alcohol, and in pyridine
combination with hydroquinone, pyro-
Its (W. Konig, J. pr. Chem. 1904, 105).
and several other phenols, has been 3. From Piperidine. The quinones (benzo-,
catechin,
patented by Joseph Turner & Co., Ltd. (D. R. P. tolu-, naphtha-, phenanthra-quinones) interact
with piperidine, yielding colouring matters which
98465).
An account of the physiological action of and alkalis. The
are readily changed by acids
piperidine and allied compounds is given by compound with benzoquinone C6 H 2 2 (NC B H, a )
Wolffenstein (Ber. 34, 2410). Its chemical forms reddish-violet prisms with blue
thick,
reactions have been the subject of special study reflex, melting at 178. Neutral or alkaline
solutions are blood-red, acid solutions carmine
by Oechsner (Bull. Soc. chim. 43, 177).
Piperidine guaiacolate prepared by the (Lachowicz, Monatsh. 1888, 505).
action of piperidine on guaiacol dissolved in Isatin blue is derived from piperidine as
benzene or petroleum melts at 79-8. It is follows : Dipiperidyl isatin is prepared by
used in the treatment of phthisis (Pharm J. heating an alcoholic solution of isatin ( 1 mol. ) with
1897, 81), and is important as combining the (2 mols.) piperidine on the water-bath for an
properties of a strong vascular and

nervine hour, and crystallising from alcohol. Isatin
blue results from heating this compound to
tonic piperidine with an antiseptic guaiacol
(Tunnicliffe, Chem. Soc. Trans. 1898, 145).
125-160 in a current of air, or by agitating
Various derivatives of piperidine have been with acetic anhydride at 60 for some time and
pouring into water. It forms indigo-blue
synthesised by Ahrens (Ber. 1898, 2278).
solutions in alcohol, ether, or acetic acid, and
Quinoline. See QUINOLINE.
is -insoluble in benzene or chloroform. It
COLOURING MATTERS DERIVED FROM BONE-OIL may be heated without change to 160, but is
BASES.
completely decomposed at 230 (Schotten,
1. From
Pyrrol. A
red dye may be obtained Ber. 1891, 1366).
from pyrrol by treating cotton cloth, after jj-Aminophenyl piperidine, which may be
dipping in a weak alcoholic solution of bitter compared with y-aminodimethyl aniline,
almond oil (benzaldehyde), with alcoholic reacts inmany cases in a similar way to this
pyrrol solution, hydrochloric acid, ferric chloride, compound. When oxidised with a primary,
and gently warming. A black colour is obtained secondary, or tertiary amine, indamines, varying
by substituting cinnamon oil (cinnamic aldehyde) from blue to green are produced. Oxidised
(Chem. Zeit. 1890, 348). in the presence of meta-diamines, compounds
Pine wood may be dyed red by moistening may be precipitated by means of zinc chloride
with hydrochloric acid, and treating with the which dye cotton blue.
vapour of pyrrol. With phenol, when oxidised with the theo-
Pyrrol blue may be obtained in two varieties : retical quantity of potassium ferricyanide, a
(a) by mixing pyrrol and isatin (1 mol. of each) blue indophenol is obtained. With naphthols
in sulphuric acid, yielding the
'
A
variety ;
'
violet colours result. Other colours are also
and (b) by operating in acetic acid under described by Lellmann and Geller (Ber. 1888,
specified conditions, when pyrrol blue B ' is '
2287).
obtained with a certain amount of A. Pyrrol Anderson, Trans. Roy. Soc. Edin.
Literature.
blue B has a metallic lustre, and is much less 16, 463 20, 247 ; 21, 219 ;
; 21, 571 Annalen, ;
soluble than pyrrol blue A. Pyrrol blue A 70, 32 ; 84, 44 ; 94, 358 ;105, 335 ; Weiclel,
cannot be acetylated, but on treating pyridine Sitz. Ber. 79, 837 ; 80, 443 80, 821 ; 81, 512
; ;
solution with acetic anhydride a small amount of 90, 972; Ciamician, Ber. 1904, 4200-4255;
the pyrrol blue B derivative is obtained. This Bamberger, Ber. 1891, 1758 and in general the
;
acetyl derivative dissolves in sulphuric acid papers of the following Ciamician, Dennstedt,
:
to a magenta solution, which rapidly changes Hoogewerff and van Dorp, Liebermann, Oechsner
to a cornflower blue, owing to the formation of de Coninck, and Weidel.
a disulphonic acid. This acid is very soluble BONE PHOSPHATES v. FERTILISERS.
in water and dyes silk blue (Liebermann and BOOKUM or SAPPAN WpOD. An Indian
Hase, Ber. 1905, 2847 see also Ber. 17, 1034).
; wood, the product of Ccesalpinia Sappan (Linn.).
2. From Pyridine. Pyridine dyestuffs may Used in dyeing reds.
be obtained by diazotising aminobenzyl- BOOMAH NUTS. The fruit of Pycnocoma
pyridine, and combining with the usual com- macrophylla (Benth.), belonging to the Euphor-
ponents. Aminobenzylpyridine is obtained by biacese. Used in tanning (Holmes, Pharm.
reducing the nitro- compound produced by the [3] 8, 363).
condensation of nitrobenzyl chloride and pyri- BORACIC or BORIC ACID v. BORON.
dine bases. These products dye tannin- mor- BORACITE v. BORON.
danted cotton, or wool and cotton from an BORAL v. SYNTHETIC DRUGS.
acid-bath (Farb. vorm. Meister, Lucius and BORATES v. BORON.
Briining, Eng. Pat. 4545). BORAX. As a mineral, borax (Na.,B 4 7
BORON. 497
10Hj,0) isfound as an efflorescence and as mono- of stearic acid. The fat melts at35-36 and
clinic crystals, sometimes of considerable size, liquefies completely at 42. The insoluble
on the shores of the salt lakes of Tibet and fatty acids have a high melting-point, viz. 53-
California. In San Bernardino and Lake 54, and seem to consist of 66 p.c. of stearic
counties in California there are several places acid and 34 p.c. of oleic acid.
known as
'
Borax Lake ' ; but most of the The fats from Shorea Ohysbertiana and
borates commercially mined in this region from Isoptera bornensis have been described
belong to other species (ulexite, colemanite, &c. ). recently as Enkabang fat and Teglam fat
The Tibetan deposits extend from the lake- respectively (Brookes, Analyst, 1909, 206).
plain of Pugha in the west to the lakes of J. L.
Tengri Nur in the east, and formerly, since very BORNESIT v. GLTJCOSIDES.
early times, much crude material was exported BORNITE. A
sulphide of copper and iron,
under the name of tincal. ( v. BORON. ) L. J. S. of importance as an ore of copper (Cu 45-71 p.c. ).
BORDEAUX Azo- COLOURING MATTERS.
v. On a freshly fractured surface the colour is
Lambert (Zeitsch. anal. Chem. 22, 46) detects dark bronze, but this quickly tarnishes to purple
this dye in wines by precipitating with basic or deep reddish hence the names purple
;
lead acetate, and extracting the precipitate copper-ore, variegated copper-ore, erubescite,
with alcohol ; the red solution thus obtained and the Cornish miner's name horse-flesh-ore.
isturned yellow by alkalis. Wool heated with Further alteration produces a black sooty
the wine withdraws its colouring matters. coating. The massive ore is always much
Bellier (J. Pharm. Chim. [5] 14, 7) describes intermingled with copper-pyrites, and even the
a method of determining quantitatively the rarely occurring cubic crystals usually contain
amount of this dye in wines. a nucleus of copper-pyrites. The exact com-
BORDEAUX 'MIXTURE v. PLANT SPRAYS. position of the mineral has therefore long been
BORNEO CAMPHOR v. CAMPHORS. doubtful; analyses by B. J. Harrington (1903)
BORNEOL v. CAMPHORS ;
TERPENES. of carefully selected material gave the formula
BORNEO TALLOW is a generic term for Cu 5 FeS 4 This is the bornite of W. Haidinger
.
a large variety of fats obtained from the kernels (1845): bornite of F. S. Beudant (1832) is an
of a number of plants belonging to the Diptero- obsolete synonym of tetradymite or telluric
carpus family, such as Shorea stenopiera (Burck.), bismuth. L. J. S.
Shorea aptera (Burck.), Hopea aspera (de Vriese), BORNYVAL. Pharmaceutical name for the
Pentacme siamensis (Kurz), all of which are t'so valerian ic ester of borneol C
10 H
17 O.C S 9 0,
H
indigenous to the Sunda Islands, Indo-China, a limpid fluid smelling like valerian, insoluble
and the Malay States. All the fats derived in water, freely soluble in alcohol or ether ;
from these trees are also in commerce known b.p. 255-260 sp.gr. 0-951 at 20,[D] 2a =27 40'.
;
under the native name of Minjak Tangkawang BORO-GLYCERINE. An antiseptic, patented

(Tangkawang Fat). Minjak Tangkawang repre- by Barff (D. R. P. 18108 ; Eng. Pat. 5906,
sents a mixture of at least six fats, obtained from 1884) ; prepared by heating 92 parts glycerol
six varieties of trees known to the natives as with 62 parts of boric acid at 200. It is a
Tangkawang toengkoel, T. rambei, T. lagar yellowish, transparent substance, soluble in
(these trees have a diameter of more than 3 ft. ), alcohol and in 40 parts of water. Used as a
T. goentjang (growing in swampy regions, and preservative for fruits and wines (J. Soc. Chem.
reaching a height of 22 ft., whilst the diameter of Ind. 1, 244 4, 362).
;
the trunk rarely exceeds 6 inches), T. madjan, BORON. B. At. wt. 11-0. An element
T. terindak. usually reckoned among the metalloids, although
The fat is prepared by the natives in a it presents analogies to the metals, and has been
'
very crude manner. In the ' wet process the placed by Etard (Compt. rend. 91, 627) at the
fruits are placed hi baskets, immersed in water, head of the vanadium group, intermediate
and left therein for from 30 to 40 days. After between the places of phosphorus and carbon ;
that time the shells are removed, the kernels is a triad in most of its known combinations,
are split into four parts, and these spread on but is also capable of acting as a pentad (Michaelis
boards, exposed to the sun to dry. The dried and Becker, Ber. 13, 58). Never occurs free;
fruit is then pounded, boiled with water, and usually as boric acid, and in several minerals, as
the liquid fat skimmed off and moulded in the borax or tincal, boracite, hydroboracite, rhodizite,
internodes of bamboo stems hence the com-
; sassolin, borocalcite, boronatrocalcite, and botryo-
mercial samples ' have a shape.
cylindrical lite, and in small quantities in schorl, datolite,
The dry process consists in cutting the kernels tourmaline, apyrite, and axinite.
into discs immediately after the fruit has been The element was first isolated by Gay-Lussac
collected, drying the discs by exposure to the sun, and Th6nard in 1808, by heating boric oxide
jand subsequently pressing. The fat obtained

with potassium. According to Wohler and
by the dry process yields the best product, Deville (Ann. Chim. Phys. [3] 52, 63), it may be
which is largely used for edible purposes in the obtained by mixing 60 grams of sodium in small
East. The Shorea fruit (erroneously also pieces with 100 grams of powdered boric oxide
described in the Straits Settlements as Illipe in an iron crucible, covering the mixture with
Nut) has been occasionally shipped to Europe a layer of 30 grams ignited sodium chloride in
iand endeavours have been made to convert fine powder, and heating the whole to redness.
'
it into a chocolate fat,' but as the harvest is After the completion of the reaction, which is
very violent, the mixture is stirred with an iron
a remunerative one
only in intervals of several
years, this manufacture has been abandoned. rod, until the sodium and sodium chloride are
Borneo tallow contains considerable quantities fused, and carefully poured into dilute hydro-
of stearic acid. Samples examined in the chloric acid, and the residue washed with water
writer's
laboratory contained as much as 66 p.c. containing ammonium chloride (which salt
VOL. L T. 2 K
498 BORON.
issubsequently removed by alcohol) and dried. without apparent volatilisation (British Thorn-
Boron can also be obtained by heating potassium son-Houston Co., Eng. Pat. 1197, 1907).
borofluoride with potassium (Berzelius), or Pure boron is a chestnut-coloured powder
magnesium (Wohler and Deville) ; by the which can be compressed into a fairly con-
electrolysis of fused boric oxide (Davy) ; by sistent solid. It has a density of 2-45, and is
reducing boron trichloride by hydrogen (Dumas) ; infusible at the temperature of the electric arc
by fusing borax with amorphous phosphorus (Moissan) ; it is tasteless, odourless, staining
(Dragendorff) ; by heating boric oxide with the fingers strongly ; becomes denser on being
magnesium and treating the residue with dilute heated in a vacuum or in gases which have no
hydrochloric acid. action upon it ; not oxidised at ordinary
Wohler and Deville's method gives a temperatures in either ah- or oxygen ; heated
product containing, in addition to boron, in air, it burns with a reddish light, forming B.,0 a
compounds of boron with sodium, iron, and and BN ; burns with dazzling brightness in
hydrogen, and boron nitride. The best method j
oxygen, forming Bj,0 3 Boiling water has no
.
is that of Moissan. Pure and dry boric oxide ! action on it, but it is readily oxidised by strong
is intimately mixed with as much magnesium nitric acid in the cold, and by sulphuric acid
filings as will suffice to reduce one-third of it. , when heated. When heated to redness with the
The mixture is placed in an earthenware crucible alkaline salts of oxyacids, yields an alkaline
in a furnace at a bright-red heat, when the borate, the formation being frequently attended
reaction proceeds at once rather violently. with incandescence, and in the case of nitre with
Heating is continued for ten minutes and the explosion. Heated with potash it forms po-
mass allowed to cool. The middle portion of the tassium borate with liberation of hydrogen, and
mass, which is of a reddish colour, is mechanically reduces the chlorides of lead, gold, mercury, and
separated from the surrounding black portion silver, and sulphide of lead, chloride or sulphide
as completely as possible, and boiled with a of boron being formed (Wohler and Devilie, I.e. ;
large excess of dilute hydrochloric acid which and Annalen, 105, 72). Heated in nitrogen, it
removes the boric acid and borides of magnesium. ,
forms white boron nitride. It decomposes nitric
The magnesium borate is removed by repeated oxide at a red heat, burning brilliantly and form-
boiling with strong hydrochloric acid and the
; ing boric oxide and nitride, but apparently has
silica (resulting from the disintegration of the no action on nitrous oxide.
crucible) by heating the residue in a platinum Crystalline boron. This variety has never
vessel with hydrofluoric acid. The residue is been obtained in a state of purity, but always
washed by decantation with water and dried. contains a small proportion of carbon or alu-
It is then approximately pure, but still contains minium or both. It may be obtained by placing
a small quantity of a magnesium boride which 8 parts of aluminium with 10 parts of fused boric
cannot be got rid of except by fusing the product acid in a gas-carbon crucible filled up with
with about fifty times its weight of boric oxide, ignited charcoal and placed inside another
and repeating the above operations. crucible of graphite which is heated to 1500,
Boron has been produced by Weston and for five hours. The aluminium is removed from
Ellis (Trans. Faraday Soc. 1907, 170) by the the resulting mass by means of fairly strong
action of aluminium powder on boric oxide. soda, and the residue is then boiled out with
If 2 mols. of boric oxide to 2 atoms of
i
hydrochloric and hydrofluoric acids. The re-
aluminium are used, the chief product is boron, sidue contains some alumina which is separated
but with a smaller proportion of boric oxide ;
mechanically as far as possible, and completely

aluminium boride is produced to a large by glacial phosphoric acid. Crystals may also
extent. be obtained by heating 2 parts of fused and
Boron may be prepared electrolytically as powdered borax with 1 part of magnesium.
follows : A
fused metallic borate is electrolysed A commercial process has been patented by
between carbon poles separated so as to prevent Kiihn (Chem. Zentr. 1904, i. 64). Boron com-
the boron floating to the cathode. By the pounds are mixed with sulphur and aluminium,
use of a high-current density at the anode and the mixture, which burns, ignited. Crystal
sufficient heat is generated to effect the reduction of boron are found in the resulting mass, and are
of the boric oxide which collects there (U. S. Pat. separated from it by extraction with water,
785962). which decomposes the aluminium sulphide,
Commercial boron is purified by grinding forming aluminium hydroxide and
"
H
2 S, and
the product obtained by heating boric oxide leaving the crystals of boron.
and magnesium with hydrochloric acid, and The hardest variety of crystalline boron
quickly pouring off the upper liquid. This contains 2-4 p.c. of carbon (Wohler and Deville,
contains matter in suspension which holds Joly). It consists of metallic-looking leaves
a higher proportion of impurities than does which are black and opaque, or red in very thin
the residue at the bottom. This process of sections. It is only oxidised with very great
" '
fractional decantation is repeated several difficulty in oxygen, and in air no change takes
times. The residual boron, which may still place even at 2000. Molten potash or lead
contain boron hydride, magnesium boride, chromate oxidises it with incandescence, but
boric oxide, and a borate, is compressed into a fused potassium nitrate does not affect it.
thick stick or cake, and heated to 1200 in a '
Boron diamonds ' of the composition B 4 gCjAl,
vacuum electric furnace, which either volatilises are colourless, transparent prisms (Hampe) ol
or dissociates all these impurities. The pure the tetragonal systBm, and a still more highh
boron is then melted down in the arc in a refracting variety was prepared by Wohler an<i
current of inert gas, preferably hydrogen. The Deville.
resulting boron is a dense solid substance which Boron may be introduced into steel, and thf
conducts electricity and is completely fusible properties of the boron steel so obtained havi
BORON. 499
been studied by Osmond (Compt. rend. 110, carbon, embedding this in powdered carbide, and
242, and by Moissan and Charpy (ibid.
346), firing in an electric furnace (Boiling, Eng. Pat.
120, 130), and by L. Guillet (ibid. 144, 1049). 6693, 1905). Modifications of this process have
Boron steels are obtained either by heating also been patented (Additions
(2) Sept. 30.
amorphous boron with reduced iron in a current 1904, to Fr. Pat. 353017).
of hydrogen, or by adding crystalline boron to Boron nitride is a white, BN
amorphous,
the molten metal. On hardening by heating bulky powder. It is infusible, insoluble in
to a known temperature and quenching, boron water,and generally somewhat inert to reagents,
steel behaves like a high grade hard but Stock and Blix (Ber. 1901, 3039) have de-
carbon steel as regards increase in tensile scribed another modification which is
chemically
strength, whilst the diminution in extension is much more active. It may be obtained mixed with
not so great. The hardness of boron steel is Ba by burning boron in air or by the action
3 ;
not much affected by heating and quenching. of nitrogen on a mixture of boric anhydride
The special effect of boron appears to be to and carbon heated to redness (Wohler and
communicate to the steel a high tensile strength Deville, Ann. Chem. Phys. [3] 52, 84). It is
rather than actual hardness when the metal is best prepared by the action of ammonium
heated and quenched. chloride vapour on a porous mass of calcium
Boron rapidly reduces manganese oxides in phosphate and borax or boric oxide heated to
the electric furnace. With excess of oxide bright redness, afterwards extracting the cold
products containing up to 97 p.c. manganese mass with hydrochloric acid and water, and
may be obtained which are soft enough to be drying the residue of BN in a vacuum desiccator
filed. With excess of boron, harder, granular (Moeser and Eidmann, Ber. 1902, 535) ; or by
substances result, containing up to 20 p.c. boron. allowing boron bromide to drop into liquid
From these a definite boride MnB may be ammonia, and heating the precipitated mixture
isolated. It is a crystalline metallic powder of boramide and borimide to 750 in a current
attacked by halogens and oxygen at high of ammonia gas (Stock and Holle, Ber. 1908,
temperatures, and by alkali hydroxides and 2095).
carbonates at a red heat. Water or steam Boron sulphide N.jS 3 forms fine white needles
slowly decomposes it with evolution of hydrogen of density about 1-55, which melt at 310. It
(Binet du Jassonneix, Compt. rend. 139, 1209). is volatile in hydrogen without
decomposition.
The same author has obtained very similar results It has been carefully studied by Moissan
with molybdenum dioxide and boron (Compt.
(Compt. rend. 115, 203). It may be prepared
rend. 143, 169) ; and has also prepared two by heating together sulphur and amorphous
definite borides of chromium Cr 3 B 2 and CrB, boron (Wohler and Deville); or, better, by
by fusing together chromium and boron. They heating ferroboron in a stream of dry hydrogen
are very stable towards reagents, especially sulphide at 400, and purifying the resulting
the former, but are decomposed by fused product by dissolving out the sulphur with
alkalis, and by chlorine at a red heat. They carbon disulphide (Hofmann, Zeit. angew.
are soluble in hydrofluoric, hydrochloric, and Chem. 1906, 1362). The latter process is much
concentrated sulphuric acids (Compt. rend. than the other.
cheaper
143, 1149). The same author has also prepared Boron trichloride BC1 3 is a colourless, very
Ni 2 B, NiB 2 , Co 2 B, and CoB 2 (Compt. rend. 145,
mobile, refractive liquid which fumes in the
240) ; and borides of zirconium, chromium, air. Sp.gr. 1-4338 at ; b.p. 18-23 (Regnault).
tungsten,and molybdenum have been prepared It decomposed by water with formation of
is
by Tucker and Moody (Chem. Soc. Proc. 1901, hydrochloric and boric acids. It is prepared by
129).
passing dry chlorine over amorphous boron, and
COMPOUNDS OF BORON WITH NON-METALLIC collecting the vapours in a U-tube immersed in
a freezing mixture. The product is purified by
ELEMENTS.
shaking with mercury to remove chlorine, and
Boramide B(NH 2 )3 is formed together with by fractionation.
ammonium chloride by the action of ammonia Boron tribrpmide
BBr 3 resembles the
on boron trichloride at a low temperature chloride in physical properties. It is prepared
(Joannis, Compt. rend. 135, 1106). in the same way, substituting bromine for
Borimide B 2 (NH) 3 is a spongy white mass chlorine, or by treating a red-hot mixture
insoluble in most solvents. On heating it begins of carbon and boric oxide with bromine
to give off ammonia at 125-130, and is com- vapour.
pletely transformed into boron nitride at Boric oxide B 2 3 may be obtained by burning
slightly higher temperatures. It is prepared by boron in oxygen, or, more easily, by strongly
heating the compound of boron trisulphide and heating boric acid, when it melts at 577 to a
B
ammonia 2 S 3 ,6NH 3 for some time at 115-120 viscid mass, cooling to a colourless brittle glass
in a current of Non- volatile, and hence capable
hydrogen or dry ammonia (Stock of sp.gr. 1-83.
and Blix, Ber. 1901, 3039 ; and Joannis, Compt. of expelling carbonic, nitric, and sulphuric acids
rend. 135, 1106). from their salts at a red heat. Soluble in water,
Boron carbide B 6 C forms exceedingly hard forming boric acid.
shining black crystals, which are capable of A blue glass, boron-ultramarine,' of colour
'
polishing diamonds. It may be obtained varying with the duration and intensity of
massive by fusing together boric oxide and
, heating, and with the proportions of the
carbon in an electric resistance furnace and |
ingredients, is made from sodium sulphide and
cooling fairly rapidly (E. A. Sperry, U.S. Pat. boric anhydride. It is stable in air and only
869114). slightly soluble in water (J. Hoffmann, Zeitsch.
Shaped blocks of boron carbide are obtained angew. Chem. 1906, 1089).
by preparing the body of the block in pure Boric or Boracic acid. Sal sedativum
500 BORON.
Hombergii, Sal narcoticum vitrioli. Boric oxide to the north of Copiapo, are the places which
forms three hydrates : have proved most successful commercially.
Orthoboric acid B 2 3 -3H 2 3 BO 3 0=H .
The crude material, known as liza, occurs in
Metaboric acid B 2 O 3 -H 2 2B 2O 4 0=H .
both places in lagoons or troughs ; these, instead
Pyroboric acid 2B 2 3 -H 2 2B 4O 7 0=H .
of being entirely filled with common salt, as is
Boric acid appears to be a dibasic acid, and usually the case in the desert, contain zones or
most of its salts may be regarded as derived from layers of boronatrocalcite, alternating with
metaboric or pyroboric acid. Both these are so- layers of salt and salty earth. The lagoons of
' '
called weak acids. Their salts, when soluble, Maricunga are estimated to cover 3,000,000
have usually an alkaline reaction, even when sq. metres. The raw material contains on the
containing excess of boric acid, and are decom- average about 25 p.c. of boric acid, but by
posed even by carbonic acid. washing and calcination it may be raised to
Boric acid is found free in nature in many 55 or 60 p.c. The roughly purified boronatro-
calcite is shipped to England and
volcanic districts. In Central Italy it is pro- Germany.
duced on a large scale in the territories of A borate of lime (rhodizite) is imported from
the West Coast of Africa.
four communes Pomerance, Massa Marittima,
:
Castel Nuovo di Val di Cecina, Montieri, all

Pure boric acid is easily obtained by treating
a solution of 3 parts borax in 12 parts hot water
in the province of Tuscany, the nearest ship-
with 1 part sulphuric acid. On cooling, boric
ping point being Leghorn, to which place it is acid separates out ; it is recrystallised from hot
brought by railroad from Volterra. It also
occurs in the extinct crater of a volcano on water, dried and fused to expel traces of sulphuric
one of the Lipari Islands, and in the crater acid, and again recrystallised from water. It
of Stromboli, an active volcano on another forms white, translucent, monoclinic laminae
island of the same group, near Sicily. Volcanic (Kenngott), which have a mother-of-pearl
.
lustre and are unctuous to the touch.

emanations containing boric acid occur in Sp.gr.
1-434 at 15.
Nevada, in California, and Nova Scotia. It exists
in solution in the mineral waters of Wiesbaden, Boric acid evaporates freely in a current
of steam. The loss sustained by evaporating
Aachen, and Krankenlied, in Germany in the ;
mud volcanoes of the Colorado Desert, in San an aqueous solution is 0-28 p.c. of the water
Diego county, California in the water of several
;
evaporated, equal to 2-8 Ibs. for every 100 gallons.
mineral springs in Tehama county, California. The solubility of boric acid in water has
In smaller quantities it exists in sea water and been determined by Ditte (Compt. rend. 85,
in the ash of many plants. 1069), but his results are probably low. Herz
and Knoch find considerably higher values at
Sassolin, or Tuscan boric acid, is never
produced in the pure state, but is always asso- 13, 20, 25, and 26. The figures of Brandes
ciated with impurities, both soluble and in- and Firnhaber (Arch. Pharm. 7, 50) also differ.
soluble. It differs considerably in quality, some
The results obtained by Nasini and Ageno
parcels containing 89 p.c. of crystallised acid, (Zeitsch. physikal. Chem. 1909, 69, 482) are
while others yield only 75 p.c. The following quoted below :
analyses show its general composition :
Grams of H 8B0 3 Grams of H 3B0 3

Tempe-
Analyses of crude Tuscan boric acid. solution
rature per 100-gram
solution
Boric acid B 2 3 47-95 44-04
VTT , ( combined . 37-00 33-98
Br 2-59 60 12-90
hygroscopic
\ 0-73 2-80
e c
sulphate (NH 4 ) 2 SO 4
Ammonium 5-67 10-62 12-2 3-69 69-5 15-58
21 4-90 80 19-11
Sulphate of alumina and iron 0-13 0-20
Calcium sulphate trace 1-20 31 6-44 90 23-30
6-91 4-03 40 8-02 99-5 28-10
Magnesium sulphate
Sodium sulphate 0-07 1-10 50 10-35
Sodium
Sand
Sulphur
.....
chloride
....
0-23
0-42
0-32
0-80
trace
The
lessened
solubility of boric acid in water is
(not, as stated in various place's.
Organic matter 0-89 0-91 increased) by the presence of hydrochloric acid
(Herz, Chem. Zentr. 1903, i. 31 2) and of sulphuric,
100-00 100-00 nitric, and acetic acids ; but tartaric acid has
the opposite effect (ibid. 755). Boric acid is
An
analysis of an average sample taken from soluble in alcohol and volatile oils. A cold
5000 tons shows it to be composed as follows :
saturated solution colours litmus a wine-red a ;
Crystallised boric acid B 2 O 3 ,2H O2 . 83-5 hot saturated solution gives a bright-red colour.
Hygroscopic water
Ammonium
Magnesium sulphate
sulphate ....
.
.
.
.
.
.
.1-4
5-3
.7-5
Crystallised boric acid, heated to 100, is
converted into
71), and into H
2B 4
2B 2 H
4 (Schaffgotsch, J. 1859,
at 160 (Merz, J. pr. Chem.
Iron and alumina . . . .0-3 7
99, 179; Ebelmen and Bouquet, Ann. Chiin.

Sand, organic matter, &c. . . . 2-0
Phys. [3] 17, 63). At a stronger heat the acid
froths up, parting with its water and forming
100-0 boric anhydride as a fused viscid mass, solidifying
Boric acid occurs on the West Coast of South to a fissured glass on cooling.
America, principally in the form of boronatro- Boric acid is extensively used in medicine
calcite (ulexite, or hayesine), and is found as an antiseptic and as a food preservative it
;
throughout the province of Atacama and in is also very widely employed. It is also em-
portions of Chili. Ascotan and Maricunga, ployed for glazing porcelain, in the preparation
BORON. 501
of glass and certain pigments, and for soaking The temperature gradually increases, being
the wicks of stearin candles. in the first pans about 60 to 70, in the
following
The effect of boric acid in glazes is to increase pans about 75, and in the last as high as 80.
their hardness and their fusibility, and to In all these pans a precipitation of gypsum
modify the coefficient of expansion. A small takes place, which requires to be removed from
amount of boric acid lowers the expansion time to time. When the solution in the last
whilst a large quantity produces an increase. pans has attained a density of 1-07, it is run
This effect is explained by Grenet (Compt. rend. through funnels into the crystallising vats, con-
123, 891) to be due to the fact that when the sisting of wooden tubs lined with lead. After
proportion of bases to boric acid is high, devitri twenty-four hours the crystallisation is complete,
fication occurs, whilst when the boric acid is the the mother liquor is then decanted off and
more important constituent, the coefficient of added to the evaporating pans a few hours
expansion tends to approximate to that of before the completion of the concentration. The
boric acid itself, which is higher than that of crystals are drained in baskets placed under the
any glass. crystallising vats for twenty-four hours, and are
It has also been proposed to use boric acid spread out on the bottom of a large drying oven,
in the preparation of nitric acid from Chili which is likewise heated by the vapour from
saltpetre, so as to obtain borax as a by-product. the soffioni. The layer of crystals, which is two
Industrial extraction of boric acid. The or three inches thick, is stirred at intervals to
occurrence of the sal sedativum of Homberg in assist the drying. This is complete in twenty-
the water of the Tuscan lagoons appears to four hours. An improved form of evaporating
have been first noticed in 1777 by Hofer, a apparatus consists in decanting the solution in
Florentine apothecary, and its extraction was the reservoirs from which the suspended matter
begun about 1815, and to-day a large part of has deposited into a pan, and thence running it
the boric acid of commerce is derived from into a slightly inclined trough made of sheet
the lagoons near Monte Rotondo, Lago Zolforeo, lead with the edges turned upwards. The
Sasso, and Larderello, in the Maremma of trough has an undulatory form, is supported on
Tuscany, inclosing both natural and artificial wooden sleepers, and heated by the soffioni
vents. The soffioni or jets of steam, which vapours. The solution of boric acid, after
often rise in thick columns to a considerable passing through this heated trough, becomes so
height, contain only traces of boric acid, but when concentrated as to be ready for crystallisation.
these are condensed in the water of the lagoons Artificial soffioni have been bored to a depth
this becomes gradually charged with the acid of 200 feet in the vicinity of the Monte Rotondo.
which is obtained from the solution by evapora- The chief works are at Monte Cerboli, Larderello,
tion. San Federigo, Castel Nuovo, Sasso, Monte
To obtain the boric acid, the soffioni are Rotondo, Lustignano, Serranzano, Lago, and
surrounded by basins of rough masonry, several San Eduardo, each of which has from 8 to 35
of which are arranged in steps, one above the lagoni, 100 to 200 feet in diameter (Payen,
other, in such manner that the contents of each Ind. Chem. transl. by Paul).
basin can be led by gravitation into the basin The boric acid thus obtained is far from
below. Fresh water from a neighbouring spring pure. Analyses of different samples by Payen,
is conducted into the uppermost basin, whilst Vohl, and Wittstein show that it contains from
the gases and vapours of the fumaroles rise 74 to 80 p.c. crystallised boric acid, from 4-5 to 7
through the water from beneath, occasionally p.c. of hygroscopic water, ammonium and mag-
with such violence as to eject the water to a nesium sulphates 8-14 p.c., together with
height of several feet. After twenty-four hours gypsum, clay, sand, sulphur, organic matter,
the water in the first basin, which is generally and free acids and ammonia.
muddy, is allowed to pass into the second basin, The origin of the boric acid in the soffioni
the first being recharged Avith fresh water. After is not understood. Dumas suggested that it ia
another twenty-four hours the second basin is formed by the decomposition by means of water
discharged into the third and the first into the of a bed of boron sulphide formed at some
second, the second and following basins being depth below the surface. Bolley (Annalen,
also built round soffioni. After having passed 68, 122) supposed that it is produced by the
through four or five of these basins, the solution action of a hot solution of ammonium chloride
is passed into
rectangular reservoirs in which upon the borates contained in the earth. Accord-
the suspended matter is deposited on standing. ing to Warington (Chem. Gazette, 1854, 419),
From these it passes into a series of leaden Wohler and Deville (Annalen, 105, 69), and
evaporating pans, placed in couples one above Popp (Annalen, Suppl. 8, 1), its formation is
the other in the form of a terrace. These pans probably due to the action of water upon boron
are heated by the gases and vapours of soffioni nitride.
which, on account of their situation, are other- Dieulafait has found boric acid in regions
wise useless by a method first adopted by where there are no visible manifestations of
Count Lardarel in 1815. The evaporating pans volcanic action,and concludes that it is of
are square, about 1 foot deep and 9 feet square, aqueous and derived from the waters
origin,
and are supported on wooden beams. The solu- of ancient seas (Compt. rend. 100, 1017, and
tion is heated in these for twenty-four hours 1240).
until it has attained a density of 1-017, when it Of late years the importation of boracite
is decanted into a second series of
pans, where, from South America and colemanite from
after another twenty-four hours, it attains a California, and also some Persian ores, has had
density of 1-034, and is finally decanted into the a considerable effect on the Italian industry.
last four pans, where it is evaporated to a specific Besides the obvious method of separating the
gravity of 1-07. boric acid from these ores by acidification and
502 BORON.
crystallisation, other processes are used for its METALLIC BOBATES.
extraction.
Borates are obtained by the action of boric
One process consists in grinding the borate acid on metallic oxides or their salts, in either
of lime or ulexite to an impalpable poAA'der and
he dry or wet way.
treating it with sulphurous acid. In solution boric acid is a very weak acid,
A
large Avrought-iron tank, circular in shape >eing expelled by almost all acids from its com-
and egg-ended, is lined with stout sheet lead ; it
)inations, partially so even by carbonic and
is provided with a cover and still head, mechani-
lydrosulphuric acids. A boiling concentrated
cal agitator, and steam pipes. It is first of
solution, however, decomposes carbonates and
all charged about half full with water or weak soluble sulphides and manganese sulphide.
liquor from a previous operation. The liquor is In the dry way, at high temperatures, it is
then boiled, and the powdered borate fed in by
:apable of decomposing the salts of all more
means of an Archimedean screAV.
volatile acids.
Sulphur is then burnt in an adjoining furnace, Alkaline borates are soluble in water, but
and the sulphurous gas is injected by means of
a peculiarly constructed lead injector into the
are precipitated by alcohol. The remaining
jorates are insoluble, or very sparingly soluble
boiling liquor. A special type of sulphur burner in water. The soluble borates produce precipi-
for this process is patented by the American
tates in solutions of salts of calcium, barium,
Borax Co. (U.S. Pat. 809550, 1906). The gas and
strontium, nickel, cobalt, and of ferric
is \vholly absorbed by the calcium
borate,
salts, which are readily soluble in ammonium
which itself is slightly soluble in Avater, boric shloride.
acid and calcium sulphite being formed. The
steam arising from the operation, containing Anhydrous borates are produced by fusing
together, in a special furnace at 1350-1400
boric acid vapours, passes from the still head '
three hours, boric oxide with the necessary
through a condenser in order to prevent any quantity of oxide, carbonate, or nitrate of the
loss that would occur. When the operation is metal. With large excess of boric acid, lithium,
complete, the steam and gas are shut off, and Dotassium, sodium, rubidium, caesium, thallium,
the contents of the pan allowed to settle, Avhich
ind silver produce clear fusions which either
occupies about ten hours. The clear boric
crystallise or leave clear glasses on cooling.
acid liquor is then run either into vats made
from Avhite sugar pine, or of ordinary Avood Ouprous oxide, and oxides of lead, bismuth,
antimony, arsenic, titanium, molybdenum, and
lead-lined, where the boric acid crystallises
out. The mother liquors are then draAvn off, tungsten produce clear fusions at the high
to be used over again if not too highly impreg-
temperatures which form emulsions on cooling.
The oxides of calcium, strontium, barium,
nated with foreign salts, or still further treated
for the recovery of the calcium sulphite and the magnesium, zinc, cadmium, manganese, iron,
cobalt, and nickel, do not give homogeneous
slight percentage of boric acid they contain.
fusions, but separate into two layers (W. Guertler,
Bigot (J. Soc. Chem. Ind. 1899, 830) obtains J. Soc. Chem. Ind. 1908, 158).
it by heating together borate of calcium and
Borates have also been prepared electrolyti-
ammonium sulphate in a closed vessel. The
cally by Levi and Castellani by electrolysing
ammonia driven off is condensed and collected, boric acid and an alkaline earth chloride in a
and the boric acid obtained by extraction of
special type of divided cell (J. Soc. Chem. Ind.
the residue.
1909, 248).
Another method is to treat boracite with
Ammonium borates. Laderelliie
sodium bisulphate, a by-product in nitric acid
manufacture. The two are dissolved in theo- (NH 4 2 B 10 ) 14 ,5H 2
retical quantities hi Avater to a density of 15B. occurs in the Tuscan lagoons in small crystal-
at 100. The solution is filtered and concen- line rhomboidal plates (D'Achiardi, Chem. Soc.
trated to On cooling, the boric acid
30B. Abstr. 1900, 600). Atterberg (Zeitsch. anorg.
out and very pure sodium sulphate Chem. 1906, 48, 367) distinguishes a diborate
crystallises
is obtained by concentration of the mother (NH 4 ) 2 B 4 7 ,5H 2 0, crystallising in tetragonal
liquors (Heidlberg, Chem. Zeit. 1907, 31, pyramids, besides the pentaborate
Rep. 48). (NH 4 ) 2 O,5B 2 3) 3H 2 0,
Chenal Douilhet & Co. (D. R. P. 110421, crystallising in rhombic double pyramids pre-
1899) produce boric acid by taking advantage viously prepared by Rammelsberg.
of the fact that when a borate is boiled with Calcium borates Ca 2 B 6 O u There are three
.
ammonium chloride, ammonia and boric acic varieties of calcium borate, which correspond to
are produced. If the concentration is too high the three varieties of calcium carbonate, calc
there is a tendency to recombination ; the spar, marble, and chalk viz. boracite or pander-
boric acid is therefore removed frequently by mite, colemanite, and pricite each found in
crystallisation from portions of the liquid, the different parts of the world in large quantities,
mother liquors being returned to the main volume and of a well-defined and constant composition.
1C
By this process it is claimed that 98-99 p.c. o Meyerhoffer and van 't Hoff (Annalen, 351,
the boric acid in combination is recovered. in attempting to prepare compounds of similai
several
In another process chlorine is passed into composition artificially, have obtained
water at 70 containing finely powdered calcium other calcium borates. These authors assign
borate hi suspension. Calcium chloride and chlo different compositions to colemanite and panda
rate and boric acid are produced. The boric acic mite. Boracite, in outward appearance, closely
is removed by cooling, and the mother liquors resembles a snow-white, fine-grained marblf
used again until sufficiently concentrated fo: colemanite is of a crystalline nature like calc spar,
convenient extraction of the chlorate (G. C or Iceland spar, and has been termed
white,
Moore, Eng. Pat. 20384, 1899). spar ; pricite, or bechilite, is a very fine,
BORON, 503
soft, chalkj* mineral of a cohesive nature, easily calcium borates, differing only in their composi-
rubbed to powder, and resembling chalk, j
tion in respect to the water of combination,
Chemically speaking, they are all hydrated i
their composition being given in table below.
504 BORON.
acid, or acetic acid, yielding boric acid. The boric acid in any proportions greater thi
following analysis from bulk shows its composi- 0-0725 equivalent of PbO to 1 equivalent B2
tion : but below this limit an emulsion is formed
Boric acid
Lime CaO
Water H 2 O
B2O3
....
....
. . . 44-24
30-91
23-00
cooling.
Magnesium borates. Stassfurtite (Szaibdyte
This mineral occurs crystalline and massiv
Magnesia MgO . . . 0-65 colour white, streak white, fracture conchoi
Silica SiO,, 1-20 uneven, subtransparent, translucent, lu
vitreous inclining to adamantine, hardness 7,
100-00 sp.gr. 2-83, pyro-electric, soluble in acids. It
Bechilite is a calcium borate found in the is found at Stassfurt, Prussia, embedded in the
kainite beds, the composition being
lagoons in Tuscany. :
Its composition is represented by the formula Boric acid B2 3 . . . 62-33

CaB 4 0,,5H 2 0.
Boronatrocalcite.
B
Ulexile,
B
Jiayesine Ca 2 6 11 Na 2 4 7 ,16H 2 O, is a soft,
tiza, cottoriballs,
Magnesia
Chlorine
Magnesium
a
MgO
Mg
.... .
.
.
.
.
.
27-03
7-91
2-73
fibrous, silky mineral of a brilliant white when
pure, generally found in nodules of a yellowish- 100-00
white colour, varying in size from that of a
Brazil nut to a potato. This curious mineral was found in nodules in grey limestone
It is also
first found in the nitre beds of Peru in small at Werksthal, Hungary, and at Danbury, Con-
quantities, and was examined by Ulex hi 1836. necticut, United States.
It was discovered in Tarapaca, 30 miles from Sussexite is a hydrated borate of manganese
Iquique, under the crust that covers the nitrate and magnesia found in Sussex county, New
of soda beds. It has since been discovered in Jersey, United States. Tourmaline, found in
Chile, Bolivia, California, Nevada, Nova Scotia, different parts of the world in different colours,
and Persia. also contains a small percentage of boric acid.
Its composition is constant, containing, when Potassium borates. Atterberg distinguishes
five different potassium borates : a monoborate
pure :
K K
Boric acid
Lime CaO
Soda Na 2 O
B2 3
.
.
....7-7
.
.
.
.
. 43-1
13-8
2 0,B 2 3 ,3H 2 ; three diborates 2 0,2B 2
crystallising with 4, 5, and 6 molecules of

water respectively and Laurent's pentaborate
;
3
Water H 2 35-4 K,0,5B 2 3) 8H.jO (Zeitsch. anorg. Chem. 1

367).
Sodium borates. The only commercial^
100-0
are sodium diborate
The nodules are frequently found mcrusted important compounds
and the perborate (v. Perborates).
with a coating of sodium sulphate and salt, (v. Borax)
from which cause the
The metaborate NaBO 2 ,4H 2 O is readily obtained
percentage of boric acid
in large parcels varies considerably, the average by fusing together the necessary proportions of
boric acid and sodium carbonate, and crystal-
being from 18 to 25 p.c.
Chile has hitherto been the principal source lising.
Sodium diborate, or Borax. Borax occurs in
of supply of this borax material. Ulexite, when
the crude state hi what are termed borax
in a state of fine division, is difficultly soluble in
marshes, which are generally the bottoms of
boiling water.
Calcium borosilicaie. Dotolite dried-up lakes, or, where tincal is found, lakes
(Howlite).
that are nearly dried. The crude borax in the
A siliceous borate of lime, colour white, streak
former instances is found lying on the surface
white, opaque, of a chalky nature, found at
of the plain, of a peculiar greyish-yellow
Calico, San Bernardino county, California, and
at Brookville, Nova Scotia. colour, having a depth of from 1 inch to 18
Composition : inches. It is generally associated with other
Boric acid B 2 3
Lime CaO
Silica Si0 2
. .
....
....
. 44-22
28-69
15-25
substances, both soluble and insoluble, as the
table of analyses (p. 505) shows.
At Jagadhri in Northern India, 37 miles
Water ELO 11-84 S.E. of Umballa, there is a borax refinery, the
product of which is shipped to Calcutta. The
100-00
quantity of tincal and borax obtained from
Copper borate is readily obtained by treating the districts of the Himalayan Mountains
a soluble borate in solution with copper chloride amounts to about 2000 tons per annum. The
or sulphate. It is blue, and used in certain tincal deposits are of very ancient origin. In
oil paints and also in the colouring of porcelain. North America there are no less than ten
Iron borate. A hydrated borate of iron, deposits, five of them being in the State
of
lagonite Fe 2 3 ,3B 2 3 ,3H 2 0, is found in the California at Saline Valley, Furnace Creek, and
Tuscan lagoons. Armagora (in Inyo county), Slate Range (in San
Lead borates. By mixing concentrated Bernardino county), and Lower Lake (in Lake
solutions of lead nitrate and borax, the meta- county) the remaining five are in the State of
;
borate Pb(B0 2 ) 2 ,H 2 is precipitated, and by Nevada at Rhodes, Teels Marsh, Columbus,

the use of solutions of smaller concentrations and Fish Lake (in Esmeralda county), and Salt
Rose obtained many basic salts. They all melt Wells (Carson Lake, Churchill county).
on strong heating to colourless or light-yellow, Borax was first accidentally discovered in
highly refractive glasses, the hardness increas- California, in 1856, by Dr. John A. Veatch, since
ing with the boron content. Glasses may which time the different deposits mentioned
be obtained by fusing together lead oxide and have been developed, and the available supply
BORON. 505
COMPOSITION OF CETJDE BORAX FROM THE MARSHES.

506 BORON.
2. borax Na 2 B 4 O 7 ,5H 2
Octahedral is ob- After the saturator has received its charge of
tained by allowing a saturated solution of borax soda ash and acid, the liquor is thoroughly boiled
to cool down to about 60 in a warm place and for five hours and allowed to settle, in order that
removing the crystals. the solid impurities may subside. This gene-
The crystals are regular, transparent octa- rally occupies from eight to ten hours, after
hedra, harder than the ordinary borax. They which the liquor is run into large wrought-
have a conchoidal fracture and a sp.gr. of 1-8. iron vats 12 feet long, 6 feet wide, 4 feet deep,
They do not change in dry ah-, but absorb into which the wires made of iron, technically
'
moisture very readily and become prismatic. called straps,' are suspended over bars of wood
They fuse more readily than the prismatic laid across the top of the vat. The liquor on
crystals, and with less intumescence, and with- cooling crystallises on the wires, sides, and
out splitting. Octahedral borax is therefore bottom of the vat, and when the temperature has
better adapted for soldering and as a flux than fallen to 26 (80F.), the liquor is siphoned off
common borax, and the smaller quantity of from the vats, and men get in, and, by the aid of
water (a difference of 17 p.c.) diminishes the cost iron bars terminating in a chiselled end, first
of transport. The prismatic variety is, how- remove the crystallised borax from the straps,
ever, generally preferred, probably because it is then cut up the borax crystallising on the bottom
cheaper weight for weight. of the vat, and lastly knock down the sides.
The commonest impurities in borax are This borax is not of sufficient purity for the
sodium carbonate and small quantities of market, and is, therefore, subjected to a second
chlorides and sulphates of sodium, calcium, and refining, and, if necessary, bleaching. For this
magnesium. It is occasionally adulterated with purpose a series of pans, called refining pans, are
earthy matters, alum, and sodium chloride. It employed ; they are also of wrought iron,
should dissolve in two parts of boiling water and circular, 9 feet diameter, egg-ended, 8 feet deep,
should not effervesce with acids. The aqueous open at the top and provided with 'cradles of
solution should not be rendered turbid when wrought iron perforated with holes, suspended
treated with an alkali, or with barium chloride by iron chains from a patent block overhead in
or silver nitrate in presence of nitric acid. such a manner as to be raised or lowered in the
pans as required. The pans are boiled with
The manufacture of borax from boric acid. steam issuing from a perforated pipe in the
This industry chiefly associated with the
is bottom. They are first half filled with water, or
production from the Tuscan lagoons. The crude some of the clearest liquor from a previous
acid, packed in large casks weighing about 13 operation, and when the liquor is boiling crude
cwts., on arrival at the borax works is first of all borax is thrown into the cradle and allowed to
manipulated in the casks themselves. For this dissolve. The right amount of borax is tested
purpose, the cask is placed on what is termed a by means of the Twaddell hydrometer, which
stillage, the head taken off, the acid loosened should read 30 when the liquor is of the required
with a spade and treated with small quantities strength. About 5 cwts. of sodium carbonate is
of water for the purpose of washing out the sul- added, and a little chloride of lime, and the
phates of ammonia and magnesia, which, on whole thoroughly boiled. The saturated liquor
account of their greater solubility, easily sepa- is then allowed to settle in the pans for ten hours,
rate from the less soluble boric acid, the wash- covers being placed on them to prevent the
ings being used for the recovery of the ammonia liquor chilling ; the pans are run off into vats of
and magnesia they contain, whilst the acid, similar size and shape to those employed in the
which formerly contained 83-46 p.c. B 2 3 3Aq. first process, and the borax allowed to crystallise,
or equivalent to 128-5 p.c. borax, is brought up which takes six days. Upon the expiration of
to a strength of 96-67 p.c. B.,0 3 3Aq. or equivalent that time, the liquor is siphoned off to a well,
to 148-87 p.c. borax. The acid, after draining made by sinking a wrought-iron tank in the
for twenty-four hours, is then placed in wicker ground below the level of the vats, and, if impure,
baskets and transferred to the saturators. These is pumped up to the refining pans to be used over
are made of wrought-iron f plates, having a again, and if sufficiently pure is pumped to boil-
diameter of 10 feet, egg-ended, height 9 feet 6 ing-down pans, to be concentrated to such a
inches, provided with hopper and swivel dis- degree as to yield a further crop of borax.
charge, still head, inspection glasses, run-off The liquors from the first vats are also
stop-cocks, and connected by steam pipes with a pumped to the boiling-down pans, where they
perforated iron coil in the bottom of the pan for likewise undergo a process of concentration.
the purpose of boiling the borax liquor with These boiling-down pans are made of wrought'
injected steam. There is also a manhole with iron, and are capable of holding about 4000
movable cover. When the saturator is ready gallons. They are provided with dry-steam coils,
for charging, liquor is pumped in to the height and are superior to other means of concentra-
of 4 feet, or 2300 gallons, which is then boiled tion from the fact that they are completely
with steam and soda ash. Anhydrous sodium under control, and the evaporation of the liquor
carbonate is then added, about 23 cwts. being can be regulated as fast or as slow as may be
generally required to 60 cwts. of acid. When necessary. The liquors in these pans are concen-
the soda ash is all dissolved, the manhole lid is trated until they reach a sp.gr. of 1-300, or 6(
placed on, and the boric acid is put in by Tw., when they are run off into vats to yield first
degrees through a hopper, half a hundredweight a crop of borax, and then upon reaching a tem-
at a time. At each addition of acid a brisk perature of 80F. they are siphoned off into
ebullition of carbonic acid takes place, which other vats, where they yield a crop of Glauber
passes along the still head, and after being de- salts, or sodium sulphate, after which the liquors,
prived of its ammonia may be utilised for making being rich in sodium carbonate, are used again
bicarbonate of soda. in the saturators for making up a fresh batch of
BORON. 607
borax with acid and soda ash. The mother After boiling five hours the steam and
liquors, strong in common salt and weak in agitators
are stopped, and the muddy liquor
sodium carbonate, are further concentrated in allowed to settle for ten hours, after which time
jacketed pans, where, on continued boiling, the the clear supernatant liquor is run off to vats to
salt falls to the bottom, is collected by means with
crystallise, and the residue is again washed
of rakes, and fished out with perforated scoops weaker liquor from the saturator previously
provided with long wooden handles, and the salt washed, the operation being repeated of boiling
is ladled into iron baskets set over the pans and and washing with the gradually weaker liquors
allowed to drain. By this means all the salts from the other saturators in rotation. By the
contained in the soda ash and boric acid are time the mud has received eight washings, the
saved, and nothing is run to waste. last being with water, the whole of the borax
The washings from the boric acid in the will have been removed, and the chalk which is
first process, containing the ammonium sul- [eft is then pumped through an iron filter press,
phate and magnesium sulphate, are collected which completely presses out the remaining
together, and placed in a wrought-iron still pro- weak liquor and leaves the chalk in a solid cake,
vided with a dry-steam coil. The requisite which is generally thrown to one side, being too
amount of sodium carbonate is then added, and impure for any purpose. The first liquor run to
the ammonium carbonate is distilled off, yield- the vats contains the biborate and borate of
ing a highly concentrated and very pure carbon- soda, together with carbonate and sulphate of
ate of ammonia liquor, which is either sold in soda in solution. The biborate of soda or borax
that state or utilised for making the purest crystallises out after cooling in
the vats for
volcanic ammonia salts. about six days, leaving the borate of soda in
The borax from the refined vats, consisting solution. The liquor is then siphoned off into
of the straps and sides, is carried to the packing the well and pumped to the boiling-down pans,
room, there to be picked, selected, and packed where it undergoes the process of concentration
in casks, whilst the borax bottoms, not being in until it reaches a sp.gr. of 1-350 to 1-400 (70
the form of merchantable borax, are refined again. to 80Tw.), when it is run off into vats and
allowed to throw a further crop of borax. The
Manufacture of borax from borate of lime. mother liquor is now of a syrupy consistence,
The mineral is first crushed in a stone and is pumped into a decomposing tank, where
breaker, the size of jaws being 8 inches and carbon dioxide is blown through it. The folio whig
known as No. 4, easily capable of crushing decomposition takes place :
12 tons in twenty -four hours. As the mineral

4NaB0 2 +C0 2 =Na 2 B 4 7 +Na 2 C0 3 .
passes through it is taken up by an elevator and to the bottom of the tank in

run through millstones, 30 inches in diameter, The borax falls
and placed by the side of the crusher. There a finely divided state, whilst the sodium car-
are two pairs, one grinding fresh ore and the
bonate remains in solution, and can be used over
other grinding the tailings. The millstones again in the saturators for the first operation.
deliver the powdered ore into another elevator, The refining of the borax from the first process is
which passes it through a bolting or sifting
the same as that employed in the boric acid
process, and therefore
need not be further
machine, 10 feet long and 30 inches in diameter,
described. The only precaution necessary is the
having octagonal sides, the bolting cloth being
of silk known as No. 8. As considerable fine addition of a little bicarbonate of soda in the
and impalpable dust arises from the sifting, it is pans to decompose any borate of soda that might
be associated with the borax. Three tons of
kept down by means of an exhaust fan blowing
the dust into a dust room. The fine mineral is borate of lime produce 2 tons of borax and 1 ton
of borax in the state of metaborate of soda. Meta-
conveyed by means of an Archimedean screw
and elevator into bins, each holding a certain borate of soda may be formed by mixing the con-
centrated solutions of borax and caustic soda
quantity and placed over the saturators. These and
are wrought-iron tanks capable of holding a together in then- equivalent quantities,
charge of 2500 gallons, and provided with suit- evaporating to 70Tw. :
able agitators and either dry or wet steam coils, Na 2 B 4 7 +2NaHO=4NaBO a +H 2
the bottom of the saturators being connected from which the metaborate of soda crystallises
by 3-inch wrought-iron valves and pipes to a in needle-shaped crystals having the formula
powerful pump for the purpose of removing the NaB0 2 ,4H 2 O.
contents of the saturator when desired. The 100 parts of metaborate of soda, when de-
saturators are grouped together in sets of four composed by carbonic acid, produce 65-6 parts
for facilitating the lixiviation of the contents by of borax and 34-4 parts of sodium carbonate ;
means of repeated washings, after the first de about 30 cwts. of borate of soda thus produce
composition of the mineral. The saturators, 20 cwts. of borax.
as in the case of the manufacture' of borax from The following process is used by Masson,
boric acid, are first charged with liquor and Gembloux, and Brussels.
Tilliere, An am-
brought to the boil ;
a charge of soda ash, monium salt is treated with lime in a distilling
usually about 30 cwts., being put in, which is column and the ammonia set free is passed into
sufficient to decompose three tons of the borate water contained in a digester, and the digester is
of -lime which is gradually added after the soda then charged with carbonic or sulphurous acid.
ash is all dissolved. The soda ash gradually but The digester is gently heated and pandermite is
completely decomposes the sesquiborate forming introduced. It is then closed and more strongly
calcium carbonate, borate of soda, and biborate heated for several hours, whilst the contents are
of soda : mechanically agitated and are transferred, when
the action is complete, to filter presses, whence
=2CaC0 3 +Na 2 B 4 7 +2NaBO. the liquor passes to a reaction chamber where it
508 BORON.
is agitated with sodium chloride and, after ing hills consist of granite, marble, dolomite,
addition of a little ammonia, is discharged into black lava, and felspar. The composition of the
crystallisers. After removal of the borax which crude material varies in strength from 10 p.c. of
crystallises out, the mother liquor is used instead borax up to 90 p.c., whilst in some places on tho
of water in the succeeding operation. After marsh under a crust composed of sodium sul-
several operations, the mother liquor requires a phate, sodium carbonate, and common salt beds
special treatment. of tincal, or large crystals of borax, some two
In this process, an ammonium biborate is feet in thickness, are found ; whilst below the
first obtained by the ammonium carbonate tincal there is a strong saturated yellowish
treatment of calcium borate, and from this am- liquor containing 1 Ib. of borax to the gallon.
monium salt borax is obtained by double de- All the manipulation that is required is to
composition with sodium chloride. Boronatro- shovel off the surface of the marsh to a depth
calcite may be used instead of pandermite if the of 18 inches and cart the material to long
process is slightly modified. hemispherical wrought-iron pans set on arches
of stone, fired beneath with wood fuel obtained
Manufacture of borax from ulexite.
Borax is manufactured from this mineral at in the neighbourhood. The pans are charged
the various deposits, and also in England,
with water, and the crude material thrown in
and vigorously stirred with
long poles, until,
France, and Germany, to which places it is ex-
with the aid of heat, the soluble salts are
all
ported from Chile and California, selected and dissolved. The fires are then withdrawn, and
packed in sacks. the contents of the pans allowed to settle for ten
The first operation consists in reducing the
material to a state of fine division, and for this hours, when the liquor is drawn off into vats,
where the borax crystallises out. The mother
purpose a mill is used so constructed as to tear
the borate to pieces instead of grinding it, which, liquor after six days is drawn off, and the borax
is taken out and packed into sacks for
owing to its fibrous silky nature, is found pre- shipment.
1.1
terable.
Borax and boric acid are applied in the
The borate manufacturing industries as follows
is then mixed with its proper
:
Brick and tile makers. Glazed surfaces.

proportion of soda ash and bicarbonate of soda, Candle makers. Preparation of wicks.
or soda ash and boric acid, having regard to
the fact that, if associated with much gypsum, a Cement. Making the finest kinds, which take a
polish.
proportionate additional allowance of soda ash China and earthenware. In preparing a frit
must be made, as the gypsum decomposes the
sodium carbonate, forming sodium sulphate used for glazing what is technically termed
' '
biscuit ware in pottery of all descriptions.
and chalk. The composition of ulexite being
Ca 2 B 6 11 Na 2 B 4 7 it requires one equivalent of
- Colour makers. In preparing Guignet's green
,
bicarbonate of soda and one equivalent of car-

and borate of manganese (a drier).
bonate of soda to decompose it :
Coppersmiths. In brazing.
Na 2 B 4 Druggists. Pharmaceutical preparations.
2(Ca 2 B 6 11 )+2NaHC0 3 +2Na 2 C0 3
7
Enamelled iron. An enamelled coating to
=5Na 2 B 4 7 +4CaC0 3 +H 2 0. and wrought iron.
These ingredients are all mixed together in the Glass. Making pastes and as an ingredient.
dry state. The process adopted is similar to the Hat makers. Dissolving shellac for a stiffener.
processes already described namely, that of Ironsmiths. In welding.
first boiling the liquor in the saturator, then
Jewellers. (Ancient name for
In soldering.
gradually adding the crude material, boiling, ' 1
borax, chrysocolla, gold-glue.)
settling, lixiviating. Laundresses. As a starch-glaze for linen.
100 parts of the ulexite, testing 43 p.c. boric
Paper makers. Superfine note and highly glazed
acid, require 10 parts of bicarbonate of soda
paper and cards.
and 12 parts of carbonate of soda, for its con- Pork packers. Curing and preserving hams and
version into 117 parts of borax. bacon.
Manufacture of borax from crude borax. Safe makers. Lining safes to resist fire.
This branch of the industry is generally Soap makers. As an emollient.
carried on at the borax marsh. It may be Tanners. Dressing leather.
desirable to give a description- of the Saline Textile manufacturers. Solvent-bleach ; mor-
Valley, Inyo county, California, where the most dant ; fireproofer.
extensive deposit of natural borax exists in Timber merchants. In preparation of hard from
North America, before entering into the details soft wood.
of refining. Perborates are salts of the acid HB0 3 which
The valley, situated on the eastern slope of has not been prepared in the free state on account
the Sierra Nevada Mountains, 11 miles from the of its instability. The alkali and alkaline earth
Carson and Colorado railroad, is 18 miles long and salts are soluble in water and have an alkaline
12 miles wide, surrounded with mountainous hills reaction. They behave in solution like mixtures
which afford no outlet, and therefore the valley of borates with hydrogen peroxide ; the active
may be said to be the bottom of a dried-up lake. oxygen being liberated by heat, by acidifying
At the point of deepest depression an area of over the solution, or by large dilution. Oxyclases,
1000 acres is covered with crude borax from 6 to reductases, and manganese dioxide cause them
18 inches in depth. The colour of the crude to give up the whole of then- reactive oxygen.
material as it lies upon the level plain is a peculiar They convert chromic acid and molybdates into
grey yellow. The borax in Saline Valley is perchromic acid and yellow permolybdates.
mixed with sand, which is volcanic ash and de- They readily oxidise protoxides and their salts
composed lime rock, sodium sulphate, sodium into higher oxides, but do not always form
carbonate, and sodium chloride. The surround- perborates with them. Ferrous, mercurous,
BORON. 509
Borcitrates are valuable as remedies in cases

manganous, and lead salts yield higher oxides ;
the salts of other metals yield perborates of an of kidney disease and urinary calculi. Their
indefinite or basic composition. Perborates solvent power for urates and phosphates is
of the alkali metals may be obtained by careful greater than that of lithium benzoate. The
precipitation of solutions of alkali borates with
diborocitrates are best adapted for the purpose.
alcohol in the presence of hydrogen peroxide. The following are known :
Ammonium perborate NH
4 B0 3 ,H 2 O is the
Magnesium triborocitrate(C6 H 6 7) 2 Mg 3 (B 3 H 3 4 ) 2
best characterised of the several perborates diborocitrate (CgHÔjaMg^B.jH.jOja
resulting from the action of ammonia and monoborocitrate (C 6 H 5 O r) 2 Mg(BH0 2 )
hydrogen peroxide on ammonium borate. It
contains 16-84 p.c. of active oxygen. Lithium, potassium, sodium, and ammonium,
Potassium O is KB mono-, di-, and tri-borocitrates of similar con-
biperborate 2 5 ,2H 2
obtained by the action of hydrogen peroxide stitution have been prepared. Iron salts have
on potassium borate. also been obtained containing respectively 8 and
Sodium NaBO 3 ,4H 2 0. When 16 p.c. of iron by acting on sodium di- and
perborate
248 grams of boric acid are mixed with 78 grams mono-borocitrate with ferric hydrate (Scheile,
of sodium peroxide and added gradually to
Pharm. J. [3] 11, 389).
2 litres of cold water, the mixture dissolves at The magnesium compounds possess strong
first, but later a crystalline substance separates antiseptic properties.
out which may be filtered off and dried. This
substance, which has a composition Na 2 B 4 8 ,
DETECTION AND ESTIMATION OF BORON.
'
10H 2 0, is perborax,' and is soluble in
called Boron almost always occurs in the form of
water to the extent of 42 grams per litre at 11. boric acid. When the acid is in the free state
When one-half of its sodium is displaced by a itcan readily be recognised by the green colour
mineral acid, a crystalline precipitate of sodium which it gives to the flame, and by its action
perborate NaB0 3 ,4H 2 O separates out. This upon turmeric.
is a very stable substance, and can be preserved Turmeric paper, when moistened with a solu-
indefinitely at ordinary temperatures. It dis- tion of boric acid and dried, acquires a cherry-red
solves readily with slight decomposition in colour, which is changed to olive-green on moisten-
water at 50-60, and a vigorous ebullition of ing with an alkali. Acid solutions of zirconic,
oxygen takes place at 100. The cold aqueous tantalic, niobic, and molybdic acids also colour
solution possesses all the properties of hydrogen turmeric brown. Cassal and Gerrans (Chem.
peroxide. When powdered sodium perborate is News, 1903, 27) find that the sensitiveness is
added gradually to 50 p.c. sulphuric acid, and greatly increased by the addition of oxalic acid,
the solution filtered through guncotton a very and base a colorimetric method of estimation
strong (150-200 vols.) solution of hydrogen of boric acid on this reaction.
peroxide is obtained. The green colour imparted to flame is a very
Patents for the manufacture of zinc and delicate test for boron (according to Merz, J. pr.
magnesium perborates have been taken out by Chem. 80, 487, 1 may be detected by
part in 1400
G. W. Johnson (Eng. Pat. 26790, 1904). means of it). Ithowever, to be noted that
is,
salts of copper likewise colour flame green,
ORGANIC DERIVATIVES OF BORIC ACID. as well as certain compounds of chlorine and
Aniline borate, and compounds of piperidine, barium and thallium. When the boric acid is
coniine, tetrahydroquinoline, and tetramethyl- combined with a base the compound in the state
ammonium hydroxide, have been prepared by of powder is decomposed by means of sulphuric
L. & T. Spiegel (J. Soc. Chem. Ind. 1905, 103). acid, and the boric acid extracted by alcohol.
The menthyl and bornyl esters are readily Compounds not decomposed by sulphuric acid
prepared by heating menthol and borneol with are fused with potash and digested with alcohol
boric acid, xylene being used as a medium in and sulphuric acid.
the latter case (Verein Chininfabriken, Zimmer The presence of boron in minerals may
& Co., Eng. Pat. 11574, 1906). be detected by mixing the mineral in powder
Ethyl borosalicylate, or 'boryl,' is prepared by with a flux containing 1 part fluor-spar to 4
parts hydrogen potassium sulphate, made
boiling together 62 grams of boric acid and
into a
138 grams of salicylic acid with 200 c.c. of water. paste with water, and heating the
mixture in
The resulting borosalicylic acid is esterified by the inner blowpipe flame, when boron chloride is
or by
adding 60 grams of 95 p.c. alcohol and heating given off which tinges the flame green ;
with 40 grams of sulphuric acid. It forms needle- mixing the suspected substance with fluor-spar
shaped crystals which are more convenient than moistening with concentrated sulphuri9 acid,
oil of
winter-green for many medicinal purposes. and passing the escaping gas through a tube
'
Zinc boropicrate, or chrysyl,' is the product drawn to a fine point into the non-luminous
obtained by boiling together boric and picric bunsen flame, which it colours green.
acids, and saturating the mixture with zinc The spectrum of boron shows three bright
oxide. It is a yellow powder used as a medicinal lines in the green and one in the blue. Hartley
antiseptic (Monteil, J. Soc. Chem. Ind. 1908, finds in the spectra of boric acid and borax the
354). lines A.3450-3, A2497, and \2496-3, which he
Phenyl borate B(OPh) 3 , diphenylboric acid considers characteristic of boron (Roy. Soc.
B(OH)(OPh) 2 , m-tolyl borate B(OC6 H 4 Me) 3 and
, Proc. 35, 301). (For the measurement of the
&-naphthyl borate B(Ci H,0) 3 , together with intensity of these bands, v. Lecoq
de Bois-
several other aryl halogen boron compounds and baudran, Compt. rend. 76, 883.)
p-borobenzoic acid H
C0 2 H-C 6 4 -B(OH).,, have The quantitative estimation of boron is
been prepared by Michaelis (Annalen, 315, difficult, as all borates are soluble
to some
19-43). extent in water and alcohol, and boric acid
510 BORON.
cannot be heated without loss in contact with red. Borax may thus be titrated by the stronger
water. acids (A. Joly, Compt. rend. 100, 103).
One method of direct determination is to (For the estimation of boric acid in mineral
precipitate the boron as potassium borofluoride, waters, v. Fresenius, Zeitsch. anal. Chem. 25,
which is quite insoluble in alcohol (Berzelius, 202.)
Lehrbuch, 3 ed. 10, 84 ; Stromeyer, Annalen, To
detect boric acid in milk, baryta is added
100, 82 ; Thaddeeff, J. Soc. Chem. Ind. 1898, to 100 c.c. of milk till alkaline. After incinera-
953). This method has been adversely criticised tion, the ash is dissolved in a little strong hydro-
by Gooch and others, and has been almost chloric acid, evaporated to dryness, and a solu-
entirely superseded. tion of turmeric with a drop of dilute hydro-
The most trustworthy method of estimating chloric acid added, and the solution evaporated
boron is due to Gooch. the boron is not
If on a water-bath. 0-001 p.c. boric acid gives
present as boric acid, it is brought into that a distinct colour to turmeric in this manner
state by heating for some hours in a sealed tube (J. Soc. Chem. Ind. 1887, 563).
with nitric acid. The resulting solution is Boric acid may be rapidly determined in
repeatedly distilled with methyl alcohol, the butter by stirring a weighed quantity with a
boric acid passing over in the vapour. The known volume of warm standard sulphuric acid
distillate is then treated with an exactly weighed till melted, allowing to settle, and titrating a
excess of pure lime, transferred to a platinum portion of the aqueous part with caustic soda,
crucible, evaporated to dryness on the water- using phenolphthaleln. The pink colour appears
bath and strongly heated. The increase in when the sulphuric acid has been neutralised ;
weight represents the boric anhydride. glycerol is then added and caustic soda run in
Volumetrically, boric acid may be estimated till the colour reappears. The second titration
accurately by titration with caustic soda, using represents the boric acid( Richmond and Harrison,
phenolphthale'in as indicator, if about one-third Analyst, 1902, 179).
of the bulk of the solution of glycerol is added BORON ATROCALCITE. An early name (G. L.
(Thomson, J. Soc. Chem. Ind. 1894, 432 v. also ; Ulex, 1849) for the mineral ulexite, a hydrated
ANALYSIS). borate of sodium and calcium NaCaB 5 9 ,8H 2 0.
Boron may be estimated indirectly by digest- Most of the natural borates exported from South
ing a weighed quantity of the finely divided America (Chili, Bolivia, and Argentina) are of
compound in a platinum vessel with hydrofluoric this species : it is also abundant in the borate
acid, and then with concentrated sulphuric acid. deposits of California and Nevada. L. J. S.
On warming gently, the boron present is expelled BOROVERTIN
v. SYNTHETIC DRUGS.
as fluoride, and after driving off the excess of Trade name for ethyl boroisail-
BORYL.
sulphuric acid, the quantity of bases in the cylate. Prepared by boiling together solutions
residue is determined. Their weight, deducted of boric acid and salicylic acid and esterifying
from the weight of the original substance, gives by the addition of alcohol and sulphuric acid.
the quantity of boric anhydride. Needle-shaped crystals. Used in medicine as a
When combined with potash or soda, boric substitute for ethyl salicylate (Monteil, J.
acid may be determined by evaporating the Soc. Chem. Ind. 1908, 354).
solution of the previously weighed salt with BOSCH. An inferior butter prepared in
hydrochloric acid, and determining the chlorine Holland. The term is sometimes used as
in the dry residue (Schweizer, Pharm. Centr. synonymous with margarine (q.v.).
1850, 372 ; J. 1850, 590). BOSTONITE. A trade-name formerly in
use
Crude boric acid (Italian) is usually valued by for the Canadian asbestos
serpentine -
(v.
determining the water and the substances ASBESTOS). L. J. S.

insoluble in alcohol, and taking the rest as being BOSWELLIA SERRATA (Roxb.) or GUGAL.
boric acid. According to Zschimmer (Chem. The gum of this plant (ord. Burseracece) is used
Zentr. 1901, [5] 44, and [7] 67), the results are as an incense. It is often confounded with
inaccurate, on account of the water not being bdellium and olibanum (Dymock, Pharm. J. [3] 7,
completely driven off under the conditions used 190).

(2 hours drying at 45 and 2 hours in desiccator). BOTANY BAY RESIN v. BALSAMS.
Boron is best estimated in the presence of BOTRYOLITE v. CALCIUM.
silicates e.g. in tourmaline, by the method of
;
BOTTLE-NOSE OIL. An oil obtained
G. W. Sargent, who has submitted all the the bottle-nosed whale, closely resembling spe:
processes published to examination and criticism oil its sp.gr. varies from 0-876 to 0-880 (Allen,
;
(J. Amer. Chem. Soc. 1899, 858-888). The J. Soc. Chem. Ind. 2, 53).
mineral is fused with alkali carbonates, and, BOUILLON NOIR. Ferric acetate (v. ACETIC
after lixiviating and acidifying, the boric acid is ACID).
volatilised from the solution as the methyl BOU-NEFA. The root bark of Thapsia gar-
ester. A convenient form of apparatus for ganica (Linn.), an umbelliferous plant growing in
performing this operation is described. The the South of Europe and Algeria. It contains a
boric ester is subsequently hydrolysed by a resin used as a medicine in France.
weighed quantity of pure lime, and estimated by BOURNEENE or VALERENE. A liquid
Gooch's process. hydrocarbon isomeric with oil of turpentine,
A method estimation in insoluble
for its secreted by the Drycbalanops aromatica (Gaertr. ),
silicates is also given by Wherry and Chapin and holding in solution borneol or Borneo cam-
(J. Amer. Chem. Soc. 1908, 1687-1701). phor. According to Wallach (Annalen, 230,
A solution of boric acid produces no change 225 ; Chem. Soc. Trans. [2] 50, 70), it is a mixture
of colour in solutions of helianthin, tropaeolin, of the decomposition products of camphene.
and methyl orange, but a drop of hydrochloric BOURNONITE. Sulphantimonate of copper
acid immediately changes the yellow colour into and lead CuPbSbS 3 , crystallising in tabular
BRAN. 511
orthorhombic crystals ; these are frequently ;

BRAM'S POWDER. An explosive consisting
twinned and show re-entrant angles at the edges, ;
of 60 parts of a mixture of potassium chlorate,
' ' '
hence the names cogwheel-ore and wheel- !
potassium nitrate, wood charcoal, and oak saw-

ore.' It is found in Cornwall, Harz, &c. and
; dust saturated with 40 parts of trinitroglycerine
in Bolivia. It sometimes occurs in sufficient (Wagner's Jahr. 22, 476).
abundance* to be used as an ore of copper and BRAN. The name given to the coarser frag-
lead. L. J. S. ments, consisting- mainly of the outer layers,
BOVEY COAL v. FUEL. which are produced in the grinding or milling of
BRAGA. An alcoholic beverage used in cereal or other seeds. When the term is used
Roumania, prepared by the fermentation of without any descriptive adjective, the product
millet. The seed is boiled with about 12 times from wheat is usually understood but maize,
;
its weight of water for 14 hours, the resulting barley, buckwheat, rye, oats, even peas and
viscous mass cooled, stirred with water and earth nuts, when milled, yield products which
'
allowed to ferment. The liquid is filtered and are described as bran.'
mixed with water, when it is ready for sale. The following analyses, compiled chiefly
It is somewhat sweet, and contains about 1-3 p.c. from German and American sources, show the
' '
of alcohol by weight. general average composition of various brans :
Water
512 BRAN.
1897, 19, 291). He found the following average York Agric. Expt. Station, 1904) about 68 p.c.
percentages in wheat bran : of the total phosphorus is extracted
by 0-2 p.c.
Total soluble carbohydrates calcu- hydrochloric acid solution, and of this, nearly
lated as dextrin . . . 7-2 p. c. the whole exists as anhydro-oxymethylene di-
Starch 17-7 H
phosphoric acid C 2 8 P 2 O 9
True pentosans . . .17-5 =(OH) 2OPO-CH 2 -0-CH 2 -OPO(OH) 2
Lignin and allied substances . 11-6 a substance first isolated by Posternak (Revue
Cellulose . . 8-5
General de Botanique, 1900, 12, 5 and 65 Compt.
;
rend. 1903, 137, 439). In bran, this acid exists

Total carbohydrates . . 62-5 in combination with
magnesium, calcium, and
Other investigators Tollens, C'halmot, potassium.
Giinther and Stone
have found from 22 to The free acid, when heated with strong
25 p.c. of pentosans in wheat bran, while maize mineral acids, is hydrolysed, yielding inositol and
bran contains about 40 p.c. phosphoric acid
Girard (Compt. rend. 1897, 124, 926) gives 3C 2 H 8 P 2 9 +3H 2 0=C 6 H 12 6 +6H 3 P0 4
.
the results of the examination of by-products

Bran is largely used as a food for farm
from wheat presumably shorts and bran by
a method different from the conventional one. animals, but has a weakening effect upon
In estimating the amount of water-soluble digestion if used in large quantities. It is
more suitable as a food for fattening than
matter in products from seeds, he points out the
for working animals. Owing probably to its
necessity of using ice-cold water, otherwise the mechanical action on the bowels, it has & purga-
enzymes present may act upon the constituents tive effect. If used largely for milch cows, it
of the seed, and greatly increase the amount of
tends to make the butter soft. Similarly,
matter soluble in water. large
The mean quantities of bran given to fattening animals
following are the figures calculated tend to lower the melting-point of the body-fat.
from analyses of the by-products from four
This is an advantage in the production of mutton
French wheats :
or beef, but a disadvantage with bacon.
Water Soluble in water Insoluble in water Bran is also largely used in tanning leather.
14-72 10-63 74-65
(For a description of the process and of the
The matter soluble in water consisted of
changes occurring in the fermentation of bran
proteids 2-70, carbohydrates
6-16, inorganic so employed, see Wood and Wilcox, J. Soc.
matter 1-77. The matter
insoluble in water Chem. Ind. 1893, 422, and 1897, 510.) H. I.
consisted of gluten 4-55, starch 28-08, nitro- BRANDY. (Eau-de-vie, Fr. ; Branntwein,
genous woody matter 5-70, fats 3-17, cellulose Ger. ) The term ' brandy is an abbreviation
'
30-22, inorganic matter 1-94, loss and undeter- ' '

of brandy- wine the original English form of
mined 0-99. the word, which occurs also in all the Teutonic
The mineral matter in bran is very high as
languages of Northern Europe, and signifies
compared with that in the rest of the seed, being burnt or distilled wine. The latter term (wine)
usually between 5 and 6 p.c., whilst that in flour in its widest sense includes the product obtained
isusually less than 0-5 p.c. by fermentation of all natural fruit juices or
The ash of bran is particularly rich in phos- extracts from grain, and not fermented grape
phoric acid, but poor in lime. The following juice only. Old English Acts of Parliament
analysis by Wolff gives its usual composition :
refer to
' ' '
brandy and aqua vitse made from
'
K 2 O Na 2 MgO CaO P 2 6 Si0 2 malted corn, whilst the German word brannt-
24-0 0-6 16-8 4-7 51-8 1-1 wein is applied to strong potable spirits
There is a widespread belief that bran is generally without implying that such spirit is
particularly well fitted, because of its richness necessarily derived from wine. At the present
' '
in mineral matter, to supply the needs of time, however, the brandy of commerce is
animals with reference to the development and almost universally understood to be a spirit
nutrition of bone. But from a study of a bone derived exclusively from the grape.
disease among horses and mules in South Africa, Besides alcohol and water, the principal
it has been deduced that for normal bone nutri- constituents of brandy are acetic, butyric,
tion it is necessary that animals be supplied, in oenanthic, and valerianic esters, acetic acid, a
their rations, with phosphoric oxide and lime in small quantity of a volatile oil, and a little
approximately equal proportions by weight fixed acid, tannin, and colouring matter. When
(Ingle, Jour. Comp. Path, and Therapeutics, new, brandy is colourless, but gradually acquires
1907, March, also Jour. Agric. Science, 1908, a yellowish- brown colour by storage in oak casks.
3, 22). From this point of view, bran is The required colour for particular brands is,
particularly ill suited to aid bone development, however, usually obtained by the addition of a
since it contains an overwhelming preponderance solution of caramel or burnt sugar. Genuine
of phosphoric acid over lime, being in the ratio brandy of good quality has a sweet mellow
of 100 to 9 in the above analysis, while in some ethereal flavour, without any suspicion of the
' '
earthy taste common to inferior

' '
samples it is as high as 100 : 5-5. That bran fiery or

has an injurious action upon bone nutrition or fictitious brandies.
when used in large quantities, is shown by the The bouquet of brandy depends upon (a) the
occurrence of a peculiar bone disease in horses nature and quality of the wine from which it
known as bran rachitis or ' millers' horse has been produced ; (6) the conditions under
' '
rickets,' observed in animals fed largely on bran. which the wine has been fermented ; (c) the
The phosphoric acid in bran, however, does method of distillation employed and (d) the age ;
not exist entirely as metallic phosphates. Ac- of the brandy. The characteristic flavour of
cording to Patten and Hart (Bull. 250, New brandy is said to be due chiefly to oananthic
BRANDY. 513
ostor (ethyl pelargonate), but it varies with the efrigerator. The spirit produced in this way
total amount and relative proportions of other s not considered so fine as that obtained by the
volatile constituents present. According to x)t still, but it is of higher strength and more
Ordonneau, the peculiar fragrant odour of uitable for the manufacture of liqueurs.
brandy is due to a very small quantity of a The quality of the spirit depends greatly on
terpene which boils at 178, and which, on he care with which the distillation process is
oxidation, gives the characteristic flavour to old arried out. The stills should be worked slowly
brandy. and regularly, the normal time for the complete
Over 90 p.c. of the brandy imported into the Listillation of a charge being about ten hours.
United Kingdom comes from France, the finest The quantity of wine used in the process of
grades being Cognac and Armagnac, so named manufacture is relatively very great, the amount
from the French towns in which they were if
brandy produced from a given measure being
originally distilled. But little brandy is now 5nly from 10 to 15 p.c. The strength of the
distilled in Cognac itself, the greater part being wine varies from 4-5 to 9 p.c. by weight of pure
produced on the brandy farms of the surrounding alcohol, or approximately from 10 to 20 p.c. of
districts. Other brandies of less value commer- xroof spirit, the average being 6-5 p.c. of alcohol,
cially are those of the Midi and the districts ot r 14 p.c. of proof spirit. The finished spirit as
Aude, Gard, He'rault, and Pyrenees Occidentales, run from the still contains about 64 p.c by weight
'
commonly known as the Trois-six de Mont- if
alcohol, equivalent to a strength of about
pellier.' Marc brandies are distilled from the 25 over-proof. The brandy, as received from
' '
fermented marc or refuse of the wine-press as he farmers, is blended and diluted in vats,
well asfrom the lees of the wine-casks. sweetened with cane sugar, slightly coloured
' '
Whilst the term Cognac has by custom with caramel, and filtered (if necessary) into
come to be used almost as a generic term for storage vats in which it is matured.
'
brandy,' it is, strictly speaking, applicable only The French Government has by various laws
to spirits made from wine grown in the Cognac and decrees of the years 1905 to 1909 prohibited
' '
region, which comprises a certain part of the che description Cognac to be applied to any
two departments of Charente and Charente mixture of Cognac or other wine spirit, with grain
Inferieure, also Dordogne and Les Deux-Sevres. or beet spirit, and has further provided that
A strict delimitation of the Cognac area has labels, marks, &c., bearing the word
'
Cognac
'
been made by the French Government by should signify that the spirit in question is
decree dated 1st May, 1909, and the region is solely the product of the Cognac region (vide
locally subdivided into the Grande or Fine supra).
Champagne, the Petite Champagne, the Borderies The simple pot stills and the modified stills
'
and the Bois, according to the quality of the known as a premier jet,' above referred to, as
wine produced. being used in the Charente districts, are not
The the district is mainly calcareous,
soil of suitable for wines having a strong earthy flavour
and the grape is a small white berry with very ('terroir') or other undesirable qualities. In
acid juice, producing a wine of inferior quality such cases, as in the brandies of the Midi, the
for drinking purposes. (For the extraction and Rochelle district, and the marc brandies of
fermentation of the grape juice, see WINE. ) Burgundy, stills of a more complicated nature
As the reputation of the brandies of the are employed, owing to the necessity for a greater
Cognac and Armagnac districts depends so much degree of rectification. In these the distillation
upon their bouquet, they are submitted to slight is continuous, and in the Rochelle district and
rectification only, and distillation is therefore the islands of the N.W. coast, a pot still with
'
a rectifying head, known as the Alembic des
' '
usually conducted in a simple pot still by the

professional distiller as well as by the farmer. lies,' is employed, whilst in the south the
The still, which varies in content from about distilling column consists of a series of compart-
'
150 to 200 gallons, is usually enclosed in brick- ments separated by plates or plateaux,' con-
work, with only a small bulbous head exposed, nected with taps by means of which it is possible
and is generally heated by means of a furnace to take off the spirit at a higher or lower strength
wood being considered the best fuel. In a few as desired. These stills are generally heated by
distilleries the stills are heated by steam. Occa direct fire.
sionally, a subsidiary vessel, filled with wine anc Immense quantities of wine are produced in
'
called a chauffe-vin,' is attached to the still the Midi for conversion into brandy, the grapes
and through it the pipe conveying the spiril of this region being unsuitable for making good
vapour to the refrigerator passes, heating the wine. This is attributed to the effects of the
wine so that the latter is quickly raised to Phylloxera, which devastated the whole of the
boiling-point when subsequently passed into th Charente district in the years 1875-1878. Before
still, thereby effecting a saving of fuel. Two this time, most of the brandy exported to the
' '
distillations are made, termed brouillis anc United Kingdom was genuine Cognac, but the
'
bonne-chauffe,' corresponding respectively witl destruction of the Charente vineyards stimulated
'
the low wines ' and ' spirits ' of the whiskej the production of brandy in other parts of France
distiller. as well as in other countries. The vineyards of
In some distilleries the finished spirit i the Cognac district were replanted with American
produced at one continuous distillation by mean stocks, on which Charente vines were grafted,
of a still described as ' a In this and the result has been highly successful but
premier jet.' ;
form of still, a vessel is attached to and above in the south of France the vineyards ravaged by
the head of the still, and through it the spirit o the phylloxera were replanted with vines which
the first distillation is conveyed. This spirit i were not appropriate to the soil, and which
again vapourised by the heat of the spirit vapou yielded wine in great quantity but at the sacrifice
rising from the still itself on its way to th of good quality. Hence the use of the rectifying
VOL. I. T. 2L
514 BRANDY.
the Midi and the large quantity of brandy
stills in 1-75 litres ; syrup of raisins, 2-0 litres ; and
produced. Most of this is consumed in France. infusion of walnut hulls, 0-75 litre. Low wines
The spirit derived from diseased or unsound wines which have been kept for some months in casks
ishighly rectified and used for industrial pur- containing clear rain water preserved by the
poses. The cheapness of wine, therefore, affords addition of 10 or 12 p.c. of strong brandy (85)
littleor no inducement to the distillers of the are also used for a similar purpose.
Midi to use beet or grain as the raw material for Whilst there is a legitimate use of colouring
the production of their brandies. which has become practically an essential
The relative values of the spirits above character of the brandy of commerce, the colour
mentioned may be gathered from the average acquired by old brandies owing to long storage
prices per proof gallon in 1909, which were from in casks is often simulated in order to give to
6s. for brandy of the best Cognac district new brandies a fictitious appearance of age by
(Champagne) to 2s. 6d. for Bois brandy, the means of a tincture of oak extract obtained
cheapest in the Cognac district, whilst Midi from chips, shavings, or sawdust of the white
brandy was Is. 9d., and gram and beet spirit oak used at Cognac for making brandy casks.
Is. 2d. and Is. Id. per proof gallon respectively. Brandy is described in the British Pharmaco-
'
Marc brandies or eaux-de-vie de marc are, poeia, as Spiritus Vini Gallici,' thus implying
as the name implies, derived from the marc or the French origin of the spirit, and is defined as
'
refuse of the grapes after the juice has been a spirituous liquid distilled from wine and
extracted. They have a strong earthy flavour, matured by age, and containing not less than
and usually are very rich in secondary products. 36J p.c. by weight, or 43J p.c. by volume of
'
They are therefore often added to other wine ethyl hydroxide (approximately 76 p.c. of
spirits to impart the brandy character, or proof spirit).
admixed with neutral spirit from grain, beet, This definition, however, takes no cognisance
&c., in the preparation of fictitious brandies. of the nature, quantity, or relative proportions
Algerian brandy is of high quality, resembling of the secondary products to which the peculiar
Cognac, and is generally sent to France, whence medicinal properties of brandy are attributed,
considerable quantities are reshipped from the and in view of the variations in these con-
Charente district to the United Kingdom. stituents even in the brandies of commerce
Brandies are produced in most other wine- known to be genuine, and the difficulty of
growing countries, especially when, owing to arriving at any satisfactory standard, it has
over-production of wine, or some defect in its been proposed by the British Medical Association
' '
quality, it becomes more profitable ' to convert it to eliminate brandy at the next revision of
into spirit than to dispose of it as wine.' The the Pharmacopoeia.
most important commercially are from Spain, The following standards of purity are pre-
Egypt, Germany, South Africa, and Australia, scribed by the United States Pharmacopoeia.
but the quantities of these exported to the Brandy should be at least 4 years old ; its
United Kingdom are small as compared with alcoholic content from 39 to 47 p.c. by weight
French brandies. (81-96 p.c. British proof spirit) ; specific gravity
The Spanish brandies are similar in character not exceeding 0-941 nor less than 0-925; the
to the French, and command a high price. residue should not, on the volatilisation of the
Genuine Egyptian brandy is made from fresh last traces of alcohol, evolve a marked disagree-
grapes, although the wine grape is not cultivated able odour of fusel oil, and should not exceed
in Egypt. The grapes are imported into 1-5 p.c. ; also the residue from 100 c.c. should
Alexandria from Southern Turkey, Greece, dissolve readily in 10 c.c. of cold water, and
Cyprus, and Asia Minor, and there made into should be free from more than traces of tannin
wine from which the brandy is distilled. They (i.e. should not give more than a pale-green
have a strong characteristic flavour, much colouration on the addition of a dilute solution
appreciated by consumers of the cheaper brandies. of ferric chloride) and the acidity should
;
Spurious brandies of doubtful origin, but

'
require not more than 1 c.c. of decinormal alkali
described as Egyptian,' are also on the market. for neutralisation using phenolphthaleln as an
They are probably made from the currant grape indicator.
grown in Greece and Asia Minor, and have no
'
Under the Sale of Food and Drugs Act, no
right to the title of Egyptian,' beyond the fact standard for brandy is fixed beyond the limita-
that they are exported vid Alexandria. Increas- tion of strength (in common with whiskey and
ing quantities of brandy of fair quality are being rum) to a minimum of 25 p.o. under proof, below
produced 'in South Africa and Australia. The which it may not legally be sold without the,
'
so-called dop brandy of South Africa is' '
fact of dilution being declared. The strength of
produced in the same way as the French marc brandy as imported into the United Kingdom
brandies, and has similar characteristics. varies considerably, but the average is about
The natural improvement observed in 5 below proof, or 46-5 p.c. of alcohol by weight.
' '
genuine brandies by ageing is always accom- Ordonneau (Compt. rend. 102, 217) subjected
panied by a rise in the quantity of the secondary 100 litres of 25-year-old brandy to fractional (
constituents due to the formation of oxidation distillation, and obtained the following substances
products (aldehydes and acids) and esters, as estimated in grams per hectolitre :
well as to concentration due to loss of alcohol Aldehyde 3-0

and water. The higher alcohols also tend to Normal propyl alcohol . . . 40-0
increase, and furfural to diminish, with age. Normal butyl alcohol . . . 218-6
According to Duplais, the mellowness due to age
may be imparted to new brandy, making it fit
for immediate use, by adding the following to
Amyl alcohol
Hexyl alcohol
Heptyl alcohol
.....1-5
.
.
.
.
.
.
.83-8
0-6
every 100 litres old rum, 2-0 litres ; old kirsch,

: Acetic ester 35-0
BRANDY. 515
Propionic, butyric, and caproic esters standard coefficient suggested by Girard and
3-0
CEnanthic ester (about) . Cuniasse for genuine brandy is 300, of which not
. 4-0
Acetal and amines traces
. . less than 80 should be esters.
. In calculating the
Morin (Compt. rend. 105, 1019) distilled 92 proportion of neutral spirit in a mixture, allow-
litres of pure cognac in Claudin and Morin's ance should be made for the small amount of
in neutral spirit.
apparatus. The first portion of the distillate secondary products present
contained the more volatile bodies the second The average coefficient for industrial alcohol, as
;
consisted of tolerably pure ethyl alcohol the shown by the analyses of Girard and Cuniasse,
;
third, the higher-boiling alcohols, &c. The is 17 and the esters 8.

residue, chiefly water, was tested for free acids, (For a detailed description of the methods of
analysis employed, see Thorpe, Minutes of
isobutylglycol and glycerol.
The first three portions were then fraction- Evidence taken by the Royal Commission on
ated, 5 litres of light alcohol, 55 litres of pure Whiskey
and other Potable Spirits, ii. Appen-
dix Q, xii. 1909.)
ethyl alcohol, and 3-5 litres of higher-boiling
compounds being obtained. The latter fraction The causes which affect the characteristic
smelt strongly of fusel oil, and possessed a bouquet of the wine naturally influence the '
as well as the character of the

burning taste. The water remaining behind was proportion ' '
added to that already obtained. The fractions volatile matters included in the coefficient of
were then redistilled in Le Bel and Henninger's the brandy. Thus the proportion of acids and
esters is considerably augmented if the wine
apparatus. The fusel oil portion, which after
dehydration by potassium carbonate weighed
becomes sour, and, speaking generally, the
352 grams, gave : aldehydes are higher in white than in red wines.
grams Also in regard to distillation, the aldehyde and
Water 7 more volatile esters are found mainly in the
Ethyl alcohol . ..130 . first runnings (' produits de tete '), whilst the
Normal propyl alcohol
/sobutyl alcohol
Amyl alcohol
...
..175
25
6
.
higher alcohols and furfural occur in largest
.
quantity in the tailings (' produits de queue ').

In the brandies of Charente and Armagnac
.....
. .
Furfural 2 the coefficient is usually rather high, but

Wine oils 7 ordinarily, in cognacs and fine champagne, it
The water contained a little acetic and butyric ranges between 275 and 450, although occasion-
it falls considerably beyond these limits.
acids, and a small quantity of a viscous liquid ally
which distilled undecomposed under diminished Brandies obtained from wines of the Midi and
from Algeria show much wider variations,
pressure, and appeared to consist of isobutyl
alcohol and glycerol. The residue contained ranging from 25 (indicating strong rectification)
tannin, together with substances extracted from to 500. Marc brandies have almost invariably
the wood. a very high coefficient, ranging from 500 to nearly
In the following table 1 shows the com-
: 1500, and in these, aldehydes often form a large
pounds contained in 100 litres of the cognac proportion. ;
2 shows the same obtained by the fermentation Attempts have been made to fix minimum
of 100 kilos, of sugar :
and maximum values for the coefficient, but
1 2 without much success, the former with a view
grams grams to the detection of the admixture of neutral
trace trace
Aldehyde spirit, and the latter to restrict the amount of
. .
Ethyl alcohol 50,837-00

. 50,615-0 secondary products for hygienic reasons. The
Norm, propyl alcohol 27-17 2-0 effect of such limits would be to condemn many
/sobutyl alcohol .6-52 1-5 brandies that are undoubtedly genuine and even
Amyl alcohol 190-21
. 51-0 of high commercial value.
Furfural bases .2-19 From the hygienic point of view, the esters,
Wine oil . .7-61 2-0
furfural, and especially the aldehydes, have a
Acetic acid . trace
.
much more deleterious action on the human
Butyric acid trace
.
system than the higher alcohols, whilst the
2-19
/aobutyl glycol acids, particularly acetic, which frequently forms
.
Glycerol . .4-38 a large proportion of the coefficient, cannot be

Butyl alcohol was absent ; furfural was said to have any detrimental influence.
detected directly by the addition of aniline to The French Government, in 1904, instituted
the cognac, a red colouration being produced an inquiry by the Technical Committee of
in the presence of acetic acid. It will be observed (Enology into the possibility of fixing standards
that isobutyl alcohol is present only in small for the total amount of secondary products
quantity, whilst in Ordonneau's results it is (' coefficient non-alcohol ') of genuine brandy,
absent altogether. but the conclusion arrived at was that neither a
The analytical data usually relied upon for minimum nor a maximum limit could be recom-
discriminating between genuine brandies and mended owing to the extremely variable character
those blended with neutral spirit are (a) volatile of brandy, not only with respect to the co-
acids ; (6) aldehydes ; (c) esters (d ) higher efficient as a whole, but also in regard to the
;
alcohols ; and (e) furfural. results are The proportions of the volatile constituents relatively
calculated in parts per 100,000 of absolute to each other. Chemical analysis should not
alcohol, e.g. in milligrams per 100 c.c., or grams be relied upon alone, but should be supplemented
per hectolitre. The total amount of the and its results confirmed by expert tasting
secondary products expressed in this manner (' degustation ').
brandy is usually made from grain

'
is termed the coefficient of impurities,' or British
'
preferably the coefficient non-alcohol.' The spirit distilled with certain flavouring materials,
516 BRANDY.
or by adding flavouring ingredients to the spirits. which is obtained by treating behenolic acid with
It is frequently mixed with foreign brandy, and hydrogen bromide (Hasse and Stutzer, Ber.
is largely used for cooking purposes. 1903, 3601). Brassidic acid crystallises from
The following is Ure's recipe for British alcohol in plates, m.p. 65-66 (Savtzew, I.e.),
'
brandy Dilute the pure alcohol to proof pitch

:
b.p. 282 (30 mm.), 265 (15 mm.), 256 (10 mm.),
and add to every 100 pounds weight of it from 180 (0 mm.), (Krafft and Weilandt, Ber. 1896,
half a pound to a pound of argol crude tartar- 1325); sp.gr. 0-8585 at 57-l/4; is less soluble
dissolved in water, some bruised French plums, than erucic acid in alcohol and ether. (For
and a quart of good cognac. Distil this mixture relationship to erucic acid and comparison of their
over a gentle fire in an alembic provided with behaviour towards various reagents, v. Alb.,zky,
an agitator. The addition of brandy and argol J. Russ. Phys. Chem. Soc. 31, 76; 34, 788;
introduces oenanthic ether, and if a little acetic J. pr. Chem. 61, [2-3] 65.) By fusing brassic
ether be added to the distillate, the whole imparts acid with potash, arachidic acid C 20 40 2 is H
the peculiar taste of genuine Cognac brandy. obtained (Goldschmidt, Jahrb. Chem. 1877, 728) :
Colour with burnt sugar, if necessary, and add oxidation with potassium permanganate yields
a little tannic acid to impart astringency.' a dihydroxybehenic acid (Jukovsky, J. Russ.
Amongst the flavouring ingredients used in Phys. Chem. Soc. 24, 499 Albitzky, I.e.).
;
the manufacture of artificial brandies (including Treatment with hydriodic acid in glacial acetic
British brandy) may be mentioned the following : acid yields iodobehenic acid (Bayer and Co.,
opnanthic ester, tincture of catechu, balsam of D. R. P. 180087 Chem. Soc. Ab-t. 1907, i. 380).
;
tolu, acetic ester, argol, cognac oil, essence of BRASSIL. A local name for iron pyrites.
cognac, infusions of bitter almond shells, tea, BRASSYLIC ACID C 13 H 24
4 Obtained,.
and walnut hulls, liquorice root, prune juice, together with other products, by acting on
rum, syrup
'
of raisins, vanilla, &c.
'
So-called H
behenolic acid C 22 40 O 2 , with fuming nitric
cognac essences mixtures of the
contain acid (Haussknecht, Annalen, 143, 45 ; Gross-
aromatic compounds just mentioned, whilst mann, Ber. 1893, 644). May be prepared by
cognac oil is made by the distillation of a
'
'
the action of nitric acid on erucic acid (Filed and
mixture of alcohol, coco-nut oil, and sulphuric Ponzio, Gazz. chim. ital. 23, ii. 393), and from
acid, cenanthic ester being one of the products. j/c-undecenoic acid (Krafft and Seldis, Ber. 1900,
As a simple formula for artificial brandy of 3571). Flat needles; m.p. 113-114; readily
the cheapest grade, Meischmann gives the soluble in alcohol and ether, sparingly soluble in
following :
spirits, 45 gallons ; caramel, 6 ozs. ; water.
cognac oil, oz. BRAUNITE. A manganese mineral classed
Cider brandy is manufactured in the United with the oxides, but containing an appreciable
States and Canada from cider and perry. amount of silica (8-10 p.c.), the formula being
Danzig brandy is made from rye ground with 3Mn 2 O 3 -MnSiO 3 or 4Mn 2 O 3 -MnSi0 3 . The man-
the root of Calamus aromaticus. ganese is usually isomorphously replaced by small
Guernsey brandy is the spirit of beet root amounts of iron, calcium, barium, &c. It is
flavoured to imitate true brandy. generally found incompact masses, but sometimes
Hamburg brandy is said to consist of potato as tetragonal pyramids, the angles of which are
or beet-root spirit as a basis, flavoured with very near to those of the regular octahedron.
essences or by the addition of inferior brandy, The crystals possess a perfect pyramidal cleavage.
and coloured to represent genuine brandy. The colour is black with a sub-metallic to metallic
Similar imitation brandies appear to be made in lustre. Sp.gr. 4-8 H. 6-6. The mineral is
;
the north of France, in Belgium, and in other found in the manganese-mines in Sweden and, ;
foreign countries. (Girard and Cuniasse, Man. with the exception of psilomelane, it is the most
pratique de 1' Analyse des Alcools et des Spi- abundant of the manganese ores in India (v.
ritueux Schidrowitz Analyst, June, 1905, and
; : L. L. Fermor, Mem. Geol. Survey, India, 1909,
June, 1906; Thorpe, Nature, 3 Nov. 1904; xxvii). L. J. S.
and Report of Royal Commission on Whiskey BRAZIL NUTS are the fruits of Bertholletia
and other Potable Spirits, 1908-9.) J. C. excelsa (Humb. and Bonp.). They yield 73 p.c.
BRASS v. ZINC. of a fatty oil of pale yellow colour, of a taste
BRASSIC ACID v. BRASSIDIC ACID. similar to that of the nuts themselves. The
BRASSIDIC ACID (Brassic acid) oil is expressed from mouldy nuts only, as the
H sound nuts have too high a value for edible

H^c
C 8H 17^^ purposes to be used for the manufacture of a
iatty oil. J. L.
is isomeric with erucic acid (q.v.), from which it BRAZILETTO. An inferior kind of Brazil-
may be obtained by the action of nitrous acid wood obtained from Ccesalpinia braziliensis
(Haussknecht, Annalen, 143, 54 ; Reimer and (Linn.), growing in the West Indies.
Will, Ber. 1886, 3321 ; Websky, Jahrb. Chem. BRAZILWOOD. Under the name of Brazil-' '
1853, 444 Fitz, Ber. 1871, 444) ; by treatment

;
wood certain varieties of the so-called soluble
' '
with hydrogen bromide in acetic acid solution, red woods are known, the term soluble being
monobrombehenic acid C 22 H 43 2 Br, being also employed to distinguish them from the dye-
formed (Ponzio, Gazz. chim. ital. 35, ii. 394) and ;
stuffs of the barwood class, which only with
by heating with concentrated sulphurous acid difficulty yield their colouring matters to boiling
at 200 (M. K. and A. Saytzew, J. Russ. Phys. water. These soluble red woods give with
Chem. Soc. 24, 482 ; J. pr. Chem. 50, [2] 78). aluminium mordanted fabrics, a bright-red shade,
It may also be obtained by heating behenolic which in each case is derived from one and the
acid with zinc and acetic acid, and a few drops same colouring matter, and all are botanically
of hydrochloric acid (Holt. Ber. 1982, 962), and allied, in that they consist of the wood of various
by the reduction of monobrombrassidic acid, species of Ccesalpinia. About nine varieties
BRAZILWOOD. 517
have been employed as dyestuffs, of which the soda solution with a beautiful carmine-red
following are the best known : colour.
Fernambuco or Pernambiico wood is considered Tetraacetylbrazilin C 16 H 10
H 3 0) 4 colour- 5 (C 2 ,
to be the richest in colouring matter, and is the less needles, m.p. 149-151
(Liebermann and
product of the Ccesalpinia crista, a tree which is Burg); triacetylbrazilin C i6 H 1 ,0 5 (C2H 3 0) 3 ,
abundant in Jamaica and Brazil. needles, m.p. 105-106 (Buchka and Erck, Ber.
The true Brazilwood is derived from the 18, 1139); brombrazilin C 16 H 13 Br0 5 , brown-red
Ccesalpinia braziliensis, and is said to contain leaflets (B. and E.) : dibrombrazilinC l6 l2 BT z 5 , H
only one-half the colouring matter which is leaflets (Schall and Dralle, Ber. 23, 1550) ; tetra-
present in the Fernambuco variety. It is acetylbrombrazilin C16 H 9 Br0 5 (C 2 H 3 0) 4 needles, ,
obtained exclusively from Brazil. m.p. 203-204 (Buchka, Annalen, 17,685) tetra- ;
Sappanwood is obtained from the Ccesalpinia acetyldibrombrazilin C 16 H 8 Br 2 5 (C 2 H 3 O) 4 m.p. ,
sappan, a tree which is common to the warmer 185 (S. and D.) tribrombrazilin G 16 RÊr 3 O s (S.
;
regions of Asia. The so-called Limawood is a and D.) dichlorbrazilin C 16 H 12 C1 2 5 (L. and
;
variety of sappan, and the dyewood imported B.) and tetrabrombrazilin C 16 H to Br 4 5 fine red
; ,
from the Philippine Islands is an inferior quality needles (B. and E.) have been prepared.
of this product. When brazilin is methylated with methyl
Peachwood is the product of the Ccesalpinia iodide in the usual manner, it gives brazilin
echinata, which occurs in Central America and trimethyl ether (S. and D. Ber. 20, 3365 ; Herzig,
the northern parts of South America. Monatsh. 14, 56: and Schall, Ber. 27, 525)
These woods, which are very hard, and of a C 16 H 11 O 2 (OCH 3 )3, prisms, m.p. 138-139 ;
and
deep-red colour, come into the market in the on acetylation yields acetylbrazilin trimethyl ether
form of billets varying in weight from a few C 16 H 10 O 2 (OCH 3 ) 3 (C 2 H 3 0), m.p. 171-173 (Her-
pounds up to a hundredweight. If freshly cut, zig, Monatsh. 15, 140 ; Schall, Ber. 27, 326).
the internal colour of the wood is seen to be According to Gilbody, Perkin, and Yates
light-yellow, but this soon changes to deep-red (Chem. Soc. Trans. 79, 1403), large quantities of
in contact with air. the trimethyl ether are conveniently prepared
Some
varieties of these woods were employed as follows 143 grams of brazilin dissolved in
:
for dyeing purposes hi India long before the the smallest possible quantity of methyl alcohol,
discovery of America, and it is stated that when are treated with 35 grams of sodium in methyl-
South America was discovered by the Spaniards, alcohol and methyl iodide (250 grams), and the
in 1500, the northerly portion of the country mixture is heated 50 hours to 60-55 in absence
was named Brazil (from braza, fiery red), because of air. A second method employed also by
this red dyewood was found there in such im- Kostanecki and Lampe (Ber. 35, 1669) consists
mense quantities. in methylating brazilin with excess of di-
Owing to the fugitive character of the methylsulphate and alkali.
colours yielded by Brazilwood, it is now only The difficulty experienced in fully methylat-
employed to a somewhat limited extent. ing brazilin is evidence of the presence of an
H
Brazilin C 16 14 5 the colouring principle of
,
alcoholic group ; but the tetramethyl ether
Brazilwood, was first isolated in a crystalline CiH 10 0(OCH 3 ) 4 , m.p. 137-139, has been pre-
condition by Chevreul (Ann. Chim. Phys. [1] pared by Schall by treating the sodium com-
66, 225) ; but was not further examined until pound of the trimethyl- derivative suspended
1864, when Bolley (Schweiz. poly. Zeitsch. ix. in benzene with methyl iodide at 120 (compare
267) assigned to it the formula C 22 20 O 7 . H also Herzig, I.e.). From this substance the follow-
Subsequently Kopp (Ber. 6, 446) proposed" the ing derivatives have been prepared :
H
formula C 22 18 7 , but it was left to Liebermann Brombrazilin C, 8 9 BrO-
tetramethyl ether H
and Burg (Ber. 9, 1883) to determine the exact (OCH 3 prisms, m.p. 180-181 (S. and D. Ber.
)4,
composition of this substance, and their formula, 21, 3014) ; and dibrombrazilin tetramethyl ether
H
C 1S 14 5 , is in use at the present time. To H
C 18 8 Br 2 0-(OCH 3 ) 4 , m.p. 215 (S. and D. Ber.
prepare brazilin from the wood itself, it is best 23, 1432).
to employ the commercial extract. This is When brazilin is submitted to dry distillation,
stirred up with a considerable quantity of sand, it gives resorcin (Kopp, I.e.), and by fusing it
the product extracted with cold ether, the with potassium hydroxide, Liebermann and Burg
ethereal liquid evaporated to a small bulk, obtained resorcin, and Herzig (Monatsh. 27,
treated with a little water, and allowed to stand 739) also protocatechuic acid. With nitric acid
for some days. Crystals slowly separate, and brazilin yieldstrinitroresorcinol (Reim, Ber. 4, 334).
these are purified by crystallisation from a little When brazilin, the colouring principle, is
water. oxidised under suitable conditions, it is converted
This method is, however, tedious, and the into brazilein, the true colouring matter
usual source of brazilin consists of the crude C 16 H 14 5 +0=C 16 H 12 +H 5 2
crystalline crusts of this substance which are and for this purpose the action of air on an
frequently deposited from Brazilwood liquor, alkaline brazilin solution, alcoholic iodine
an intermediate product in the manufacture of (Liebermann and Burg), potassium nitrite, and
Brazilwood extract. The crude substance is best acetic acid (Schall and Dralle), nitric acid in
purified by two or three crystallisations from the presence of ether (Buchka and Erck), and
water, to which a little sulphurous acid has been sodium iodate (Mayer, Centralb. 1904, i. 228)
added (Gilbody and W. H. Perkin, and Yates, have been employed. It can, however, bo more
Chem. Soc. Trans. 1901, 79, 1396). Brazilin economically prepared from Brazilwood extract
crystallises in two forms, either as colourless in the following manner (Hummel and Perkin,
needles containing 1JH 2 0, or as colourless Chem. Soc. Trans. 1882, 41, 367).
prisms with IH.,0. It "is
readily soluble in To an aqueous solution of the extract, an
alcohol and water, and dissolves in dilute excess of ammonia is added, and air is aspirated
518
through the liquid. A precipitate of the since it showed that brazilin contains a catechol
impure ammonium salt of brazilein gradually nucleus and two orthohydroxyls, as a result
separates, and this is collected, dissolved in of which no doubt in part its tinctorial
pro-
hot water, and treated with dilute acetic acid perties are due.
(sp.gr. 1-04). A brown viscous precipitate of 2.
2-Carboxy-5-methoxyphenoxyacetic acid
the crude colouring matter is thus obtained, and
this is extracted with hot dilute acetic acid, CH a Oi
and the extract evaporated on the water-bath.
Crystals of brazilein separate, which are collected On fusion with alkali, this compound yields
and washed with acetic acid. resorcinol, and on heating with water to 200
Brazilein consists of minute plates possessing is converted into methoxyphenoxyacetic acid
a strong metallic lustre, and by transmitted
light a reddish-brown colour.
It is very spar- CH 3 0/\0-CH -COOH 2
ingly soluble the usual solvents, and

in all
cannot be recrystallised in the ordinary manner.
This can be synthesised by the interaction of
It is in reality the colouring matter of Brazil-
ethylbromacetate and the sodium compound
wood, and possesses strong tinctorial property.
Alkaline solutions dissolve it with a deep-red
of resorcinol monomethyl ether and subsequent
colouration, which on standing in air passes hydrolysis.
3. Brazilic acid
gradually to brown. A
study of this oxidation
was carried out by Schall and Dralle, with
2-7 grams of brazilin dis-
results.
interesting C(OH)-CH 2 -COOH
solved in 150 of water was treated with 10
c.c.
c.c. of sodium hydroxide solution (sp.gr. 1.37), when fused with alkali, gives resorcin, and on
and air aspirated through the liquid for 36 hours.
warming with sulphuric acid is converted into
Ether extracted from the acidified solution
anhydrobrazilic acid
P-resorcylic acid, and a substance C 9 6 4 , H
crystallising in brownish-yellow needles, m.p.
which a
<v
/ CH
271, gave diacetyl compound, m.p.
148-149, and a dimethyl ether, m.p. 169-170.
When the latter was oxidised in acetic acid solu- C-CH 2 -COOH
CO'
tion, withpotassium permanganate fi-resorcylic
acid monomethyl ether was produced :
Boiling baryta water hydrolyses anhydrobrazilic
acid, with production of formic acid and
CH 3 OH 6-hydroxy-4:-methoxybenzoylpropionic acid
COOH CH,0 OH
and Dralle considered that this com-
Schall CO CH 2 CH -COOH
2
pound was probably a pheno-^-pyrone derivative, On methylation converted into the

this is
and Feuerstein and Kostanecki (Ber. 32, 1024)
dimethyl ether, and the latter can be produced
proved that this was in reality the case, and by the interaction of dimethyl resorcinol and
assigned to it the following constitution :
the half-chloride of succinic acid monoethyl
ester, and subsequent hydrolysis. It is also
formed when resorcinol dimethyl ether and
<:.'. ____ 3j succinic acid are treated with aluminium chloride
COH. without employing a solvent. N
Finally, when the methyl ester of this
Thus the dimethyl ether, when hydrolysed hydroxymethoxybenzoylpropionic acid is dis-
with alcoholic potash, gave fisetol dimethyl ether solved in ethyl formate and treated with sodium,
the methyl ester of anhydrobrazilic acid is pro-
duced. This interesting synthesis may be repre-
COCH 2 -OCH 3 sented as follows :
a substance which had already been obtained CH,0/N OH

in a similar manner by Herzig from fisetin tetra- CO CH,-CH,-COOCH 3
methyl ether Young
Fustic).
(see
Our chief knowledge of the constitution of CH,0 OH CH-OH
brazilin is due to the elaborate investigations of II
W. H. Perkin and his pupils, who obtained most _CO C CH 2 -COO CH 3

important results by the oxidation of brazilin
trimethyl ether with potassium permanganate, CH,0 CH
and also with chromic acid. II
Gilbody, Perkin and

Yates (Chem. Soc. C CH -COOCH 3
2 .
Trans. 1901, 79, 1465) found that when brazilin

trimethyl ether is oxidised with permanganate, it Dimethoxycarboxybenzyl formic acid (1), and
gives, in addition to oxalic, acetic, and formic dimethoxycarboxybenzoyl formic acid (2).
acids, the following compounds :
COOH OCH 3 COOH

1. m-Hemipinic acid (1)
COOH-CH
(2)
OCH, CO OH -CO UOCH.
OCH.
CH0 COOH
,'COOH. represent intermediate stages in the formation
of w-hemipinic acid from brazilin trimethyl
The isolation of this substance was important, ether, whereas the acid
BRAZILWOOD. 519
CH,0 CH 2 -CH(OH)COOH CtLO CH.,-COOH

COOH IHOH "COOH
(3)
also isolated,is, no doubt, that product
of the
oxidation which is anterior to the formation of
car boxy methoxyphenoxyacetic acid (see above). CH 3 OCH 3 .
The earlier work suggested the following "

Dihydrobrazilinic acid itself is
accordingly
probable constitution for brazilin :
represented by formula (3).

OH -CH- The following constitution :
O
-CH(OH)-CH-CH 2- OH
OH // \/ V'H 2
but this, as a result of the full investigation and
synthesis of brazilinic acid, a very important sub-
stance, also produced by the oxidation of brazilin >CH,
trimethyl ether, was subsequently discarded.
Brazilinic acid. The constitution of this acid
has been conclusively demonstrated by its synthe-
sis,which has been effected by the interaction of
HO OH.
m-hemipinic anhydride with ethyl methoxyphen- has, as a result of this work, been assigned to
brazilin bv Perkin and Robinson (Chem. Soc.
oxyacetate in the presence of aluminium chloride.
This is illustrated by the following equation :
Trans. 1908, 93, 496), and is in complete har-
mony with the facts above enumerated.
CH S 0/V- CH -COOEt Oxidation of trimethylbrazilin with chromic acid.
O
When trimethylbrazilin is oxidised with
chromic acid it is converted into trimethyl-
brazilone (Gilbody and Perkin, v. infra).
(CH,0),C 1 .H I1 2 +20 = (CH,OVC 16 H,0,+H,0

and this apparently simple reaction has proved
CH -COOH
2 to be of an extremely puzzling character.
.
C0\ /COOH When trimethyl brazilone is oxidised with
permanganate, it gives m-hemipinic acid, 2-
carboxy - 5 - methoxyphenoxyacetic acid, brazilic
OCH OCH 3 .
acid, dimethoxycarboxybenzoylformic acid, dime-
3
Brazilinic acid. thoxycarboxybenzylformic acid, methoxycarboxy-
phenoxylactic acid, and brazilinic acid.
When brazilinic acid is reduced with sodium In an earlier paper, Gilbody and Perkin
amalgam, quantitatively converted into
it is
(Chem. Soc. Trans. 1902, 81, 1040) suggested for
H
dihydrobrazilinic acid C 19 20 9 , which at once
trimethylbrazilone a constitution based upon
loses water with the formation of the lactone
their first formula for brazilin (see above), but it
C 19 H 18 O 8 .
has now been shown that the reaction proceeds
To synthesise thelatter compound, w-hemi-
in the following manner (ibid. 1908, 93, 498).
pinic anhydride is condensed with resorcinol di-
By the oxidation of trimethylbrazilin (1) with
methyl ether to form 2'-hydroxy-<i.5A'-trimethoxy- chromic acid a disruption of the central linkage
benzoyl benzoic acid occurs, with the formation of an unstable dike-
and this subsequently undergoes
CH,0/ X OCH OCH, tone (2),
aldol condensation, and trimethylbrazilone is
produced (3).
CH 3 O/N OH COOH OCH, N O n

- CO OCH'
CH 3 0/ V" \CH 2
1
CHaO/Xx-" ^CH,
-
When
reduced with sodium amalgam, this C(OH) s CO
acid 2-m-meconyl-5-methoxyphenol (1),
gives
\/\CO I
and this by the action of chloracetic acid and 2 (2) CH a
potassium hydroxide is converted into the

lactone of dihydrobrazilinic acid (2) /
CH 3 OH ,0, CH 8 OCH g OCH; OCH,

CH/ CO
CH,0 CH-CO
(1)
CH S
CH 3
OC O H (3)
C(OH)
-COOH
CH OCH 3 OCH 3
(2)
This formula represents trimethylbrazilone
/ as a derivative of tetrahydronaphthalene, and
affords a ready explanation of the decomposition
OCH 3 OCH 3 products of this compound.
520 BRAZILWOOD.
An important point in favour of this con- which was based upon the production of di-
stitution is afforded by the behaviour of trimethyl hydroxypheno-7-pyrone (Schall and Dralle), by
brazilone with alkalis or acetic anhydride and its alkaline oxidation and of protocatechuic
other dehydrating agents, for it is thus converted acid by fusion with alkali (Herzig).
with loss of one molecule of water into anhydro- It was, however, pointed out oy Perkin that
trimethylbrazilone (GH 3 0) 3 C 16 7 0.,. H
There can this formula does not account for the presence
be little doubt that the formation of this sub- of m-hemipinic acid among the oxidation
stance is due to the elimination of water from products of trimethylbrazilin, and Herzig and
the aldol grouping in trimethylbrazilone, and Pollak (Monatsh. 1901, 22, 207) advanced a
that it possesses the following formula : similar criticism. On the other hand, it was
(
suggested by Kostanecki and Lampe (Ber. 1902,
35, 1667) that m-hemipinic acid was not to be
C C-OH
regarded as an oxidation product of trimethyl-
\CH brazilin itself, but that it arose from the
formation during the oxidation of a phenanthrene-
\ or indene- derivative, which by the further
action of the permanganate gives this acid.
Such an indene- condensation is illustrated by the
CH 3 OCHj following scheme, which, according to these
Anhydrotrimethylbrazilone thus a deriva-
is
authors, probably occurred during the formation
tive of f)-naphthol, and it possesses many of the of trimethylbrazilone from trimethylbrazilin.
properties of this substance. It is soluble in dilute The first product of the oxidation with chromic
alkali, and this solution gives with diazobenzene acid will possess the formula I., and this is
chloride a red azo- dyestuff. Diazonaphthalene converted by the following stages into trimethyl-
chloride behaves similarly, and the dye thus brazilone III.
produced dissolves in sulphuric acid with a blue
colour.
When trimethylbrazilone is boiled in acetic CH,0
acid solution with phenylhydrazine, deoxytri-
methylbrazilone C 16 H 9 3 (GH 3 0) 3 is obtained,
and this probably a dihydronaphthalene
is
derivative of the formula
OH
011 s
OGH a
V CH-CH
CH 3
OCH,
OCH 3 OCH 3
II.
The most striking reaction of trimethyl-
brazilone is its behaviour with nitric acid, when OH-C OCH 3
it yields nitrohydroxydihydrotrimethylbrazilone
G 16 H 93 (CH 3 0) 3 3 +HN0 = H
C ]6 10 8 N(CH 3 0) 3 OCH 3
This substance dissolves in alkali with a

purple colour, but on standing the colour rapidly
fades, o-nitrohomoveretrol separates, and the
solution contains p-methoxysalicylic oid. Oxi-
dation with permanganate gives 2-carboxy-5-
methoxyphenoxyacetic acid, and these decom-
III.
positions point clearly to the formula
HOC
OCH 3 I
HO-HC
G(OH) CHA /OGH 3
GO-0 This constitution accounts in a simple manner

as representing the constitution of the nitro- for the formation of the anhydrotrimethyl-
'
compound. (See also Perkin and Robinson, brazilone I., and the nitrohydroxydihydrotrime-
ibid. 1909, 95, 381.) thylbrazilone II. of Perkin, which can be
Feuerstein and Kostanecki (Ber. 32, 1024) represented as follows :
assigned the following constitution to brazilin :
CH 3 O
OCH 3
GH HO-G OGH 3
BRAZILWOOD. 521
brazilone and anhydrotrimethylbrazilone given

CH 8O above by these authors.
Herzig and Pollak (Ber. 1903, 36, 398)
suggested the following constitution for brazilin,
IL HO C NO,/\OCH trimethylbrazilone, and anhydrotrimethylbrazi-
lone :
HO CH OCH,
When anhydrotrimethylbrazilone is digested /OH
with hydriodic acid, anhydrobrazilone C 16 H 10 6 _/\OH
C/-
-f H 2 is produced, but when trimethylbrazi-
lone itself is treated in a similar manner, the OH
result is of a peculiar nature. The compound \/
C 1S H S O(OH) 4 so obtained does not consist of Brasilin.
brazilone, but possesses the formula (I.) or (II.),
and on distillation with zinc-dust gives brazan CH 3 CH,
(III.) (Kostanecki and Lloyd Ber. 1903, 36 /OH ,
2193). C/ /\OCH,
.OCH,
I. OH
Trimethylbrazilon e.
II. OH OCH. X CH
C OCH 3
III. OCH,
x
co
Anhydrotrimethylbrazilone .
In 1899 Liebermann (Ber. 32, 924) obtained

anhydro-a-naphthoquinone resorcin by the con- Somewhat observed that (Ber.
later Herzig
densation of 2-3-dichlor-a-naphthoquinone with 1904, 37, 631) that trimethylbrazilone undergoes
resorcin isomeric change when it is dissolved in sulphuric
O acid, and yield-y-trimethylbrazilone 16 6 C H 3
(OCH 3 ) 3, m.p. 170-173, to which the formula

HO ;
C~/\)CH 3
and this,according to Kostanecki and Lampe HC /OCH 3

k
(Ber. 1908,41, 2373), is 3-hydroxybrazanquinone. OHCO

By reduction with hydriodic acid, this gives Monatsh.
was (Herzig and Pollak,
assigned
hvdroxybrazan Perkin and Robinson (I.e.)
1906, 27, 743).
find that on oxidation with permanganate this
compound gives large quantities of 2-carboxy-
(CH 3 0) a -C g H 2
-
4:-5-dimethoxyphenylacetic acid
can be
(COOH)-CH 2 -COOH, and that there
and from this latter or from the quinone itself, little doubt that its true constitution is repre-
brazan, identical with that obtained from sented by one of the f ormulae
trimethylbrazilone, is produced. Brazan crys-
tallises in leaflets, and melts at 202.
Kostanecki and Lampe (Ber. 1902, 35, 1674) CH a O CH COOH-CH 2 , OCH 8
have considered it probable that, after all, OCH 3
trimethyl brazilin does contain, as found by
Perkin, a nucleus which on oxidation yields
hemipinic acid, and appear to have adopted the
following ns their final formula for brazilin : CH S CH COOH OCH 3
OCH 3
HO /\/\
(
v XCH, CH
CH Finally, Herzig and Pollak (Monatsh. 1906,

27, 743) have considered it necessary to modify
their first formula for brazilin, and have arrived
CH OH at the conclusion that that latterly proposed by
Kostanecki and Lampe correctly represents this
I
HOCH OH
colouring principle. The more recent work of
This constitution, it is evident, will still Perkin and Robinson detailed above shows, how-
harmonise with the formulae of triniethyl- ever, that this constitution cannot be correct,
522 BRAZILWOOD.
because does nut account for the production
it
of brazilinic acid by the oxidation of triinethyl-
brazilin
0-CH 2 -COOH
OCH s f
C0\ _ ^
COOH C CH,
:> <:
OH
_/
OH
the
and there every reason to consider that
is
It was found, for instance, that when brazilein
formula suggested by the latter authors is the
correct representation of the constitution (c/. trimethyl ether (3) is treated with sulphuric acid,
it is converted with loss of methyl alcohol into
also Perkin and Robinson, Chem. Soc. Trans.
the dimethyl ether of isobrazilein sulphate (4)
1909, 95, 381) of brazilin.
Brazilein yields a triacetyl derivative HSO 4
H H
C 16 9 5 (C 2 3 0) 3 , yellow leaflets, m.p. 203-207 Ox
(Schall and Dralle, Ber. 23, 1434),
and a trimethyl CH,0
/
Y NTH, CH S 0'
H
ether C 16 9 (OCH 3 ) 3 2 , which crystallises in two
modifications, melting at 160 and 178 respec- C-OCH 3 C
tively (Engels and Perkin, Chem. Soc.
22, 132).
Proc. 1906,
Brazilein trimethyl ether combines C CH 2
\/\C CH
(3) (4) 2
with formic acid, yielding a formic acid derivative
which crystallises in garnet-coloured prisms, and
is decomposed into its components by treatment
with alcohoL 3CH7 OH
OCH,
Theconstitution assigned to brazilein by CH 3 O
Perkin is as follows :
These authors assign an orthoquinonoid
structure to this and similar oxonium salts..
The commercial preparations of Brazilwood
OH CH 2 known as Brazilwood extract and Brazilwood
liquor, are prepared by boiling
the ground fresh
C(OH) wood with water, and evaporating the decoction
thus obtained to various degrees of consistency
CH ;
without access of air, or as rapidly and at as low
a temperature as possible, e.g, in vacuum pans.
Dyeing Properties. Before dyeing, the logs
as imported are rasped to a coarse powder, and
OH Q
-
this is then usually moistened with water and

allowed to ferment for some weeks. This
When brazilein dissolved in sulphuric acid,
is
operation is performed in order to increase the
and the solution is diluted with acetic acid, colouring power of the wood, and there can be
minute orange-red prisms of isobrazilein sulphate little doubt that a considerable quantity of the
H
C 16 U 4 -S0 4 H
separate (Hummel and A. G. brazilin present is thereby oxidised to the
Perkin, Chem. Soc. Trans. 1882, 41, 367), and this, colouring matter brazilein. It has been con-
on treatment with alcohol, gives the basic sulphate sidered by some that the fresh wood contains in
H H
C 18 12 5 (C 16 1 iO i -S0 4 H)2, which crystallises in reality a glucoside of brazilin, which, under the
red needles. Hydrochloric and hydrobromic influence of fermentation, is hydrolysed, but no
acids at 100 give isobrazileinchlorhydrin evidence has been forthcoming in support of
C 16 H U 4 -C1, and isobrazileinbromhydrin this suggestion.
C, 6 H 11 4 Br, and both compounds consist of
Although still used in calico-printing and in
orange-coloured prisms, which are somewhat wool-dyeing, Brazilwood and its allies have lost
readily soluble in water, forming a solution much of their importance, chiefly because of the
which contains free haloid acid. These interest- fugitive character of the colours they yield.
In
ing substances dye mordanted fabrics colours calico-printing, sappan liquor is employed for
which are entirely different from those yielded by producing steam-reds and pinks, the mordant
brazilein, and the shades which are produced used being aluminium acetate or stannic oxalate,
especially on calico somewhat resemble those separately or combined, together with some
oxi-
given by alizarin. From these haloid salts by dising agent, e.g. potassium chlorate or a copper
digestion with silver oxide a substance is pro- salt. It also enters into the composition
duced known as isobrazilein, which has the of steam-chocolates and certain steam colours
formula C 16 H 12 6, but is totally distinct from in conjunction with other dyewood extracts.
brazilein. These woods have also been much used in
According to Engels, Perkin, and Robinson the past along with garancine in dyeing the
(Chem. Soc. Trans. 1908, 93, 1140), whose reds, chocolates, and other colours of cheap
paper must be consulted for the detailed prints.
account of brazilein and its derivatives, these In wool-dyeing these woods have been ap-
isobrazilein salts are derived from 4-3-indeno- plied for the purpose of dyeing reds and various
benzopyranol (1), and the sulphate which is shades of claret and brown, the wool being pre-
trihydroxy- 4 3 -indenobenzopyranolanhydrohydro- viously mordanted with alum and cream of
- tar-
<jen sulphate (2), may be represented thus : tar or oxalic acid, or with potassium dichromate,
BREAD. 523
in which case other dyewoods, e.g. logwood exactly the right point, it cannot be carried out
and old fustic, are applied in addition. The under precisely the same conditions with hard
colours produced by this method are now only as with soft water.
used to a limited extent. Chemistry of bread making. The chief con-
In cotton-dyeing, peachwood-red was for- stituents of flour, so far as bread making is con-
merly obtained by first preparing the cotton with cerned, are (1) the carbohydrates, (2) the
tannin matter, then mordanting with a stannic proteins. The former include sugars and starch,
salt, and finally dyeing with peach wood, sappan- the proteins consist of a small proportion of
wood, &c. Browns were obtained by the use of soluble protein and a large proportion of in-
logwood in addition, with or without a final soluble gluten.
passage through a ferric salt solution (nitrate of The gas formed during panary fermentation
iron). These colours are now replaced by others is produced by the action of the yeast organism
obtained from coal tar. A. G. P. on dextrose. Flour contains about 1 p.c. of
BR AZILEINand BRAZILIN v. BRAZILWOOD. sucrose and a little raffinose : before fermenta-
BRAZILIAN ANIME OLEO-RESINS.
t>. tion, both these sugars are converted into
BREAD may be defined as the dough made dextrose by the enzyme invertase present in
by the mixture of the flour of grain with water, yeast. This amount of sugar would not suffice
charged in some way with gas so as to distend it, to give the necessary amount of gas, but it is
and afterwards baked. The resulting loaf has supplemented by the maltose produced from the
a delicate spongy structure which causes it to starch of the flour, maltose being itself converted
be the most readily and easily digested of all into fermentable dextrose by another enzyme
wheat foods. The simplest and most primitive maltose contained in yeast.
form of bread making consisted merely in mixing The formation of maltose is effected by the
flour with water and baking the dough, and it agency of a diastatic enzyme present in flour ;
survives still in the Passover cakes of the Jews it begins directly the flour is wetted and continues
and in the damper ' of the Australian settler.
'
throughout fermentation until the loaf is baked.

The charging with carbonic gas is commonly Yeast contains no diastatic enzyme, but it is
effected by fermentation with leaven or yeast ; possible that its action on the proteins of flour
alternative methods involve the use of baking facilitates the production of diastase.
powders (q.v.) or the direct injection of the gas. Gas escapes from the dough throughout the
In addition to producing gas, fermentation has a process of making a loaf, and the supply available
profound effect on the constituents of flour, and must be sufficient to distend the loaf and main-
improves the flavour and digestibility of the tain fully distended until it is fixed in the oven.
it
loaf. Flours which have relatively little diastatic
The mechanical result of aeration is the enzyme will produce insufficient gas, and this
creation of innumerable vesicles or cells within fact explains perhaps the beneficial results
the dough, which are subsequently distended by sometimes obtained on adding malt extract,
heat, the whole mass being encased in the baking which is rich in diastase, to dough. This ques-
within the crust, of dextrin formed by the action tion is in reality somewhat more complicated in
of heat upon the starch. The making of bread that diastase consists of two enzymes a liquefy-
from wheaten flour is only possible because the ing enzyme which renders the starch soluble, anil
latter contains gluten. Gluten is a mixture of a hydrolysing enzyme which converts it into
proteins which becomes viscid when mixed with maltose. It is the former rather than the latter
water, and, when blown up with gas, has suffi- enzyme which is sometimes lacking in flour.
cient coherence to remain in the form of a honey- Gluten is the characteristic and the most
comb instead of collapsing and allowing the gas important constituent of flour (v. GLUTEN). It
to escape. is the agent which principally determines how
Leavening (Lat. levo, to rise) has been much water a dough will take ; what length of
practised from time immemorial in the East ; time it requires to be fermented ; what will be
from the Egyptians it passed to the Greeks and the size of the loaves, and their colour, flavour,
thence to the Romans, whose conquests and and general appearance. The baker requires
colonies extended the art. It consisted in the quality rather than quantity the relation
:
first instance probably in a natural fermentation between chemical constitution and quality is
of the dough by leaving it to become sour ; but not yet fully understood (see British Association
to hasten the process it became usual to add to Report on Wheat, Winnipeg, 1909). During
new dough a portion of old fermented paste or fermentation, gluten becomes softer and at first
'
leaven.' More recently, yeasts were substi- more elastic, subsequently it softens still further,
tuted for the piece of leaven. These were of loses elasticity, and begins to break down.
various origin, that from tho distillery being the Baker's yeast always contains lactic acid
most suitable. To-day, ' pressed or German
'
organisms, and the conditions in a long sponge

yeast, which consists of yeast grown in a special are favourable for the formation of this acid,
way, purified by repeated washing and com- which has a marked solvent and disintegrating
pressed into cakes, is the most generally used. action on gluten. Accordingly, in a long
This keeps well, is uniform in quality, and enables sponge, the gluten is considerably disintegrated.
the baker to exercise a close control over the The baker's art consists in taking the sponge"
regularity of the process. when sufficiently mellow. If under-fermented,
Dough consists roughly by weight of two- a foxy crust is obtained ; if over-ripe, the gluten
thirds flour and one-third water, the quality of becomes too much disintegrated and the loaf is
the water being a matter of some importance. less bulky, inclined to crumble, and in extreme
The softer the water the quicker is the fermenta- cases becomes sour.
tion, and since the quality of the bread depends Common salt is very generally added to
on fermentation being allowed to proceed to bread. This is done firstly to give the necessary
524 BREAD.
flavour, as owing largely to the action of salt in I
growth and reproduction and get the yeast in a
stimulating the palate, minute quantities of particularly active state. Flour is added to
j
other substances can be recognised in its pre- !

make a sponge, and this, some hours later, made
sence. Secondly, salt has a toughening and into dough. The longest system of fermenta-
binding effect on gluten, though it has a solvent j
tion is that practised hi Scotland. An eighth or
effect on some of the proteins of flour. In view tenth of the flour is made into a fairly tight
of the modern theory that the properties of dough with a little yeast and allowed to lie 14 to
gluten are due to small quantities of associated |
18 hours, during which time the gluten becomes
salts, the effect of the added sodium chloride almost entirely soluble, and the dough acquires
must be taken also into account. Salt also a distinctly vinous smell and taste. It is then
checks diastatic action and fermentation to broken up with flour and the remainder of the
some extent. Use is made of this property by liquor to a thin sponge, which lies about 1 hours
the baker in dealing with sponges which are till it shows signs of turning and is then made up
over-ripe :a little more salt than usual is used into a rather soft dough. The long systems
in making the dough, and the subsequent fer- formerly in use, were partly the result of custom
mentation is retarded and the disintegrated and partly due to the slow working yeasts used.
gluten somewhat toughened. To-day, particularly in large bakeries, the
To make a large, well-aerated, shapely loaf tendency is in the direction of the straight
of good colour and flavour, it is necessary to use dough, though the sponge-and-dough method is
a large proportion of flour from strong wheats. very largely practised. It has been claimed that
Such a flour usually contains more nitrogenous j
the longer processes require less yeast, make
compounds than a weak flour. Commercially, bulkier bread, and bread of better flavour.
a demand has arisen for strong flours, which When the dough is ready it is scaled off and
accordingly realise a higher price than weak kneaded into shape. This presses out nearly all
flours. The strongest flours come from parts of the gas and toughens the gluten ;if it is not
the United States and Western Canada, also thoroughly done the loaf is likely to contain
from Hungary. English wheats give, as a rule ; holes. The loaves are next put aside in a warm
weak flours, which by themselves are unsuited place to prove, during which the gluten relaxes
for modern bread making. and the yeast expands the dough evenly. Too
It is the object of the large millers to produce much proof must be avoided, as on putting the
a brand of flour suited for bread making which is bread in the oven the excessive expansion is
a blend of several wheats, and to maintain this frequently followed by the collapse and flatten-
brand of flour of uniform quality throughout the ing of the loaves. The loaves are then baked at
year. The preparation of sample loaves, made 450-500F., a 2-lb. loaf requiring about 40-50
under carefully standardised scientific conditions, minutes. During baking, the gases are at first
still remains the most
satisfactory test of quality, expanded and the dough swells, the yeast is
and many flour mills maintain a laboratory for killed, someof the starch cells burst, the heat
this purpose. sets the gluten and the starch, and finally the
According to Humphries, the starch of flours crust is converted into dextrin and in part
made from wheat grown in hot, dry climates is caramelised.
very stable and resists disintegration. Such It is the baker's object to get the maximum
flours require special treatment, the addition of number of loaves from a sack of flour. Accord-
malt extract being a very common process. ingly, that flour is selected which has the
This addition generally causes an improvement power to take up and retain moisture,
in flavour, due, it is supposed, to the production uch flours are often termed strong.
freatest A
sack
of dextrinous products, which further have the
(280 Ibs.) of good flour yields about 96
effect of making the bread more moist.
quartern loaves.
There is a loss of weight during panary Vienna bread is a term applied to rolls
fermentation, due to the conversion of carbo- and light fancy bread baked in an atmosphere
hydrates into alcohol and carbon dioxide. Jago entirely charged with steam, to obtain which a
estimates this loss at 1-3 p.c. ; other authorities
special oven construction is adopted. The
give somewhat higher values. Experiments starch of the flour is burst by heat and changed
made at Pittsburg indicate that over two-thirds into dextrin by the aid of moisture, so that a rich
of the total fat present in flour is lost
during golden-brown highly glazed crust is obtained.
baking. Leavened bread. In France and elsewhere
The manufacture of bread. To-day, in on the Continent, bread is made from leaven, but
large towns, bread is usually made in bakeries on
'
in the more important towns this mode of bread

a manufacturing scale, and machinery is em-
making has been given up for the Viennese and
ployed for the mixing of the dough, weighing English processes. The practice in the prepara-
and moulding of the loaves, whilst the tion of the leaven consisted in a series of stages
baking is
carried out in large draw-plate ovens.
('levain de chef, levain de premiere, levain de
There are various systems of bread seconde, levain de tout point'), by which, starting
making
depending on whether the dough is made right with a piece of dough put away from a previous
off in one operation, or whether a
portion of the baking and adding at intervals more and more
flour, the yeast and the water, are first made up flour and water, the required quantity is leavened.
into a loose paste the sponge and the rest of From
this is taken a half, which when baked yields
the flour added some hours later. A third a dark, sour bread ; the remainder, being again
system involves the preparation of a ferment mixed with a quantity of flour and some yeast,
most commonly consisting of potatoes, boiled
produces a whiter and less sour dough, a portion
and mashed with water to which a little raw of which is baked and the residue once more
flour is added. The yeast is introduced into added to fresh flour. This subdivision is re-
this and fermentation carried out so as to favour
peated three times, the bread improving at each
BREAD. 525
stage. A characteristic example of leavened which is readily broken up by heat ; or, alter-
bread is seen in the rye bread (Schwarzbrod) of natively, thatit is due to the
shrinkage of the
Germany. fibreswhich form the walls of its visible pores.
Next to wheat, rye is the chief bread-making The adulteratior of bread with alum, zinc,
grain throughout the world, and in particular it and copper sulphates, lime, &c., is now entirely
is largely used in Northern Europe. Rye bread a thing of the past. These were added to
is moister, closer, and darker in colour than prevent the injurious effects of an excess of
ordinary household bread. There are several diastase on the starch during panary fermenta-
qualities, differing in the proportion '
of bran tion when inferior flour was employed. The
contained, the so-called pumpernickel being an cheapening of flour and the critical demands of
'
extreme example. Fine rye bread is as diges- the public for a well-risen white loaf, as well as
tible as wheaten bread, but in the case of improvements in the miller's technique, have
pumpernickel a very large proportion is un- necessitated the use of the best flours in bread.
absorbed (Romberg, Archiv. f. Hygiene, 1897, The question of colour, meaning brightness
28, 244). of appearance in crumb and crust, is an im-
Baking Poivders. Carbon dioxide may also portant one ; at the moment, the demand is for
be generated within dough by the action of a white loaf. Colour is largely a question of
baking powders, which are usually mixtures of optics ; a weak but very white flour may make
sodium carbonate and some acid or acid salt, poor dingy-looking loaves, whilst a darker,
and evolve gas when moistened or heated. stronger flour will make loaves which are better
Owing possibly to the difficulties of distributing aerated and hence appear much whiter.
fresh yeast, baking powders were formerly A modern development is the artificial
widely employed in America. They are not bleaching of flour, usually with nitrous fumes
used much in this country for white bread. produced by some electrical process. There is
They are usually classified according to the acid no proof that bread made with bleached flour is
constituent, as tartrate, phosphate, or alum deleterious to health, but its use has been for-
powders (v. BAKING POWDERS). The so-called bidden in America under the Pure Food Laws.
self-raising flour contains baking powder already It is a matter of controversy whether bleaching
mixed with it. by nitrogen peroxide is due to oxidation or to
ASrated bread is made by injecting carbon nitration. Bleaching does not change a low-
dioxide into dough by mechanical means. The grade flour into a higher one, and bleached flour
process was originated by Dr. Dauglish in 1859, should therefore be declared as such.
and at one time enjoyed considerable popularity, The souring of bread is one of the baker's
but it has not met with universal favour on problems. It is the result of a combination of
account of the raw and insipid taste of the bread, bacterial fermentations, the bacteria being
due to the absence of the products which yeast introduced by the yeast, by the flour, or, as
produces during fermentation. The carbon should not occur, by the use of dirty vessels.
dioxide is produced separately and forced into The flavour of fermented bread improves
water under pressure this water is mixed with
:
gradually as the process proceeds until a maxi-
the flour in a specially constructed vessel, in mum is reached, after which, if fermentation is
which the pressure is maintained. On opening continued, it begins to deteriorate. At this
the vessel, the dough rises and can be imme- stage the alcoholic ferment is exhausted and the
diately baked. The advantages claimed for the acid fermentation begins to predominate. The
system are uniformity of result, and the avoidance sourness is mainly due to lactic and acetic acids,
of the losses in weight which occur during fer- the odour to acetic and sometimes butyric acids.
mentation. A later development consisted in Such bread-diseases as ropiness (compare
mixing a little wort, made from malt and flour E. J. Watkins, Ropiness in Flour and Bread,
and fermented till sour, with the water to be J. Soc. Chem. Ind. 1906, 350) are due to specific
aerated, so as to improve the flavour. The bacteria.
process is eminently suited for the manufacture In a modern bakehouse, bacterial diseases
of whole-meal bread, as the preparation of a should not occur ; they may often be traced to
batch of dough can be effected in thirty minutes. the use of unsound flour.
Composition of Bread. The general composi- Whole-meal Breads. The majority of the
''
tion of bread is very variable. About two-thirds patent breads belong to the brow-n variety,
of the volume is made up of gas. By weight it and contain more of the wheat grain than the
contains 40-50 p.c. of water and 6-5 p.c. of white flour. In some, the finely ground bran is
protein, the balance being mainly carbohydrate. introduced, in others the germ, whilst a third
Hutchison gives the following mean figures for a class claim to contain the complete wheat grain.
number of breads analysed by him : Bran is very rich in diastatic enzyme, here
Carbo- termed cerealin, and its introduction causes a
Water Protein Fat hydrates Cellulose Ash
very rapid conversion of the starch into dextrin
White 40 . 6-5 1-0 51-2 0-3 1-0
and sugar. This causes the dough to become
Wholemeal. 45 6-3 1-2 44-8 1-5 1-2 softand clammy and to bake brown in addition,
:
On keeping, a loaf gradually loses moisture to itbecomes very prone to souring. The use of
the extent of 8 p.c. in 48 hours, 14 p.c. in 72 sodium bicarbonate and hydrochloric acid for
hours (Goodfellow) or 14 p.c. in 1 week (v. Bibra). aerating whole-meal bread is common. When
At the same time, the bread becomes stale, but the fermentation process is used, the bran is not
this change is not attributed to loss of moisture, introduced until the dough stage. Whole-meal
as much of the freshness is restored on heating, bread has a great tendency to become sodden ;
during which considerably more water is lost. it has to be baked for a considerable time, and
It is suggested that staleness is due to a gradual consequently often has a thick crust. Germ
combination of water with the starch or gluten has a very injurious effect on flour, owing to its
526 BREAD.
diastatic character, and the tendency to become obtained, or the unripe fruit is dried, powdered,
rancid. Every effort is therefore made to and sifted, yielding a flour which has the
remove it as completely as possible. When following composition :
subjected to the action of superheated steam, Water Protein Fat Starch Fibre Ash
the germ is cooked, the diastatic properties are 14-3 1-0 0-2 83-8 0-2 0-4
destroyed, and it acquires a pleasant malt-like,
(Balland, J. Pharm. Chim. 1903, 17, [10] 476).
nutty flavour and aroma. This process was The leaves and wood of Artocarpus incisa are
patented by R. Smith of Macclesfield, and a devoid of matter
mixture of one part of treated germ and three colouring (A. G. Perkin,
Chem. Soc. Trans. 1898, 73, A
parts of white flour constitutes Ho vis flour, from
1019). closely
related tree (Artocarpus integrifolia) bears a still
which Hovis bread is made. '
The relative nutritive values of white and larger fruit, jak fruit,' weighing about 25 Ibs.,
of which about 26 p.c. is flesh, the remainder
whole-meal bread is a highly controversial
It is claimed that whole- meal bread is being rind 66 p.c., and seed 8 p.c. The flesh,
subject. when ripe, contains about 5 p.c. of sugar, mainly
richer in protein and so more valuable, but this
cane sugar (Prinsen Geerligs, Chem. Zeit. 1897
is far from being generally true. A
second con-
tention is the larger amount of mineral matter,
21, [72] 719). H. I.
in the brown bread.

BREAN v. OLEO-RESINS.
especially phosphoric acid, BREEZES. (Braise, Fr.) The dust of coke
This is certainly true, but experience has shown
or charcoal. The coke burner applies this term
that the mineral matter is not all absorbed from
to the small residual coke obtained in coke
white bread, whilst in whole-meal bread the
burning. ' The sifted ashes removed from houses
quantity absorbed is so much less that it is is called breeze,' and sold under that name to
probable the blood obtains much the same brickmakers and others. An arrangement for
amount from both (Hutchison). Whole-meal
burning breeze is described in J. Soc. Chem. Ind.
bread is defectively absorbed, owing to the 425.
5,
cellulose which it contains preventing the gastric
juices from gaining access to the neighbouring
BREIDIN, BREIN v. OLEO-RESINS.
nutritive ingredients, and for the same reason BREMEN BLUE and BREMEN GREEN.
it interferes somewhat with the absorption of Pigments containing a basic copper carbonate
other foods. When the unsatisfactory nature with alumina and calcium carbonate.
of the whole-meal bread itself and the pre- BREWING. 1. Introduction. Beer (Fr. Here ;
cautions necessary in its manufacture are taken Ger. bier) may be defined as a spirituous liquor
into consideration, it is to be deplored that a made from any farinaceous grain, but preferably
section of the public should demand bread in from barley, which is first caused to germinate,
this form. With bread containing added germ then ground and mashed with hot water, whereby
the case the bran is absent and the
is different, its fermentable substance is extracted. This
food value, both as regards protein and phos- wort, as it is then termed, is next boiled up with
phate, larger than of white bread.
is hops, which, besides imparting an agreeable
The use of flour containing the untreated bitterness to it, precipitates certain albuminous
original germ of the wheat berry for bread is bodies. The liquor drained off from the hops is
disadvantageous, since the flour easily becomes cooled down, yeast added, and fermentation set
rancid and the germ enzymes commence to act up. After the liquor has ceased fermenting it is
on the gluten from the moment the flour is freed from the yeast, run off into casks and sent
made, causing the loaf to be of poor colour and away for consumption. It may be of different
to be less finely vesiculated and digestible. degrees of strength and colour, according to the
These factors more than outweigh the advantages quantity and nature of the ingredients employed
of the very small additional amounts of protein in its manufacture ; thus we may have mUd ale,
and phosphate introduced and the slightly strong ale, light dinner ale, pale ale, bitter beer,
sweeter flavour of germ bread. porter, and stout.
The desire for more phosphates can be met 2. The ingredients used in the manufacture
by the addition of phosphoric acid to the flour, of English beer are water, barley malt, malt
as is indeed being done at the present moment adjuncts such as maize, rice, sugar, glucose,
during the milling process in order to improve saccharum, &c., hops, and yeast.
the quality of flour (compare Humphries, 3. Water. The principal seat of the brewing
Eng. Pat. 13135 and 17279 of 1908; Chitty trade in Great Britain is Burton-on-Trent, which
and Jago, Eng. Pat. 22434 of 1909; Levin, owes its great commercial prosperity in this
Eng. Pat. 3673 of 1910). branch of chemical industry to a certain chemical
Authorities. Jago, Science and Art of property possessed by the waters of this locality,
Breadmaking, London, 1911 ; Hutchison, Food which render them pre-eminently suitable for
and the Principles of Dietetics, London, 1911; brewing purposes. This property is nothing
Wheat: Brit. Ass. Report, Winnipeg, 1909- more or less than the presence of calcium sul-
Hamill, Local Govt. Board, No. 114, 1911. phate in large quantities in these waters, derived
E. F. A. from the deposits of gypsum contained in the
BREAD FRUIT. The fruit of Artocarpus Keuper marls of the district.
incisa (Linn.). The tree grows freely in tropical 4. The waters supplying the Burton breweries
islands, and yields fruit continuously for 9 months are derived from two sources (1) from the
:
in the year. The fruit is nearly spherical, and valley gravels (shallow wells), and (2) from the
sometimes weighs 5 or 6 Ibs. It is usually gathered red marls and water stones of the new red sand-
while yet unripe, i.e. before its starch has stone formation, obtained by artesian borings.
changed into sugar ; sometimes the unripe fruit The following analyses of these waters may
is peeled, wrapped in leaves and cooked whole, be regarded as typical. No. 1 sample, from a
when a product resembling ordinary bread is well sunk to the depth of 29 feet in the valley
BREWING. 527
the composition of
gravels, very fairly represents
the mineral constituents of the older and shallow
wells of the district, in which the sulphates of
lime and magnesia are partially replaced by car-
bonates of the same'metals due to the percolation
of rain water charged with carbonic acid gas
TABLE I.
528 BREWING.
mineral constituents of the water must first be will,according to varying circumstances, contain
made, and then sulphates of lime, magnesia, different quantities of calcium sulphate, but
and potash, and sodium chloride added in such always less than is really required. After the
proportions as to bring the mineral constituents whole of the water required for mashing and
up to the required standard, either to that shown sparging has run through the gypsum tank into
in column 8 if intended for mild ales, or to that the hot liquor back, then the other salts are
of column 9 if intended for pale ales. added. This may be most conveniently accom-
In the case of neutral waters, the necessary plished by the use of kainite and common salt in
mineral salts are simply added to the water in such proportions as chemical analysis may point
the given proportions, but if the water be alka- out to be necessary. 1 For instance, let us take
line, the alkaline carbonates must first be water No. 4 ; here it was found that by passing
destroyed before further treatment. An essen- the natural water through about a ton of gypsum
tial condition in hardening a water with calcium at a speed of three barrels per minute, 20
sulphate is that the process shall be regular, and grains per gallon of calcium sulphate were taken
the best method of getting the gypsum into into solution ; kainite at the rate of 2 oz. per
solution is decidedly by passing the water as it barrel and common salt 1 oz. per barrel were
issues from the supply tap or storage cistern next added ; the mineral constituents of this
through a tank filled to three quarters its depth water had then the composition shown in
with gypsum stones about the size of a hen's egg. column II.
The method of procedure is shown below : On referring to our table of typical analyses,
A is a wooden round, having a perforated false it will be seen that this water is of the mild ale
bottom B, on which the gypsum stones rest; type. To render it suitable for brewing pale ales,
c, water inlet from main or cistern D, in- ; the water must be run at less speed through the
dicating valve ; E, waste-pipe having a fall of gypsum tank so as to increase the calcium sulphate,
30 feet for washing out ; and further quantities of kainite and common
p: F, wash-out valve G, ; salt must be added as shown in column III.
overflow pipe to liquor
tank. The valve D being
opened to the requisite
degree, and F closed, the
water enters at c, perco-
lates through the gypsum
in A, and flows over
through the pipe G into
a liquor tank. The rate
of flow of the water
which determines the
amount of gypsum to
be taken up is regulated
by the valve D. The
gypsum tank and
size of
the speed at which the
water passes through will
determine the quantity
taken up. As a rule, a
tank capable of holding
about a ton of gypsum
FIG. 1. and with a water of the
composition of No. 2
flowing through it at the rate of three barrels
per minute, takes up about 20 grams per
gallon of calcium
sulphate. Fresh gypsum
must be added daily so as to keep the depth
of layer of gypsum as regular as possible.
To prevent an accumulation of slimy deposit
which always takes place to a greater or less
extent, the gypsum in the tank should be
thoroughly well washed every other week this ;
may be done by closing D and opening F, then

turning water on at the top of B, this passing
through such a length of pipe as B causes a certain
amount of suction which produces the desired
cleansing effect. Some brewers recommend the
addition of the gypsum in a state of fine powder
either to the hot liquor tank before, during, or
after the heating of the water preparatory to
mashing, others sprinkle it over the grist as it
runs into the mash tun, whilst others again add
it to the wort as it is boiling up in the copper.
None of these methods can be recommended, as
in no one case will the whole of the gypsum be
taken into solution, hence the brewing liquor
BREWING. 529
be equivalent to the quantity of alkaline car- nearly three times the quantity of alkaline car-
bonates present, then only about three-fourths bonates originally present do we find that the
of the calcium sulphate is converted into cal- last traces of these substances
finally disappear.
cium carbonate, and an equivalent quantity, These are the results of numerous experiments
that is to say, three-fourths of the alkaline carried out by the author both in the
laboratory
carbonates present, is converted into alkaline and on the large scale in breweries where the
sulphates. As we increase the calcium sulphate, deep-well water supply was highly alkaline in
the alkaline carbonates decrease, until when character, and it was found that the results
we add double the equivalent of calcium sul- obtained on the large scale fully confirmed those
phate nearly the whole of the alkaline carbonates arrived at in the laboratory.
is converted into alkaline sulphates. The following analyses of an alkaline water
(c) The last portions
of the alkaline carbo- before and after treatment with
gypsum will
nates seem to be very persistent, for not until we make this more clear :
increase the quantity of calcium sulphate to
ANALYSES OF AN ALKALINE WATER BEFORE AND AFTER TREATMENT.

530 BREWING.
such a speed as to take up this quantity of The most frequently occurring substance in
CaS0 4 As soon as the requisite amount has run
. solution in natural waters is calcium carbonate,
through, the total hardness of the treated water associated to a greater or less extent with
mag-
is determined. The amount of calcium sul- nesium carbonate. These carbonates are held in
phate in the water is next ascertained by chemi- solution by the carbonic acid which is
always
cal analysis, and the figures thus obtained taken present in natural waters ; they probably exist
as standards of comparison for all subsequent in solution as bicarbonates. On boiling, this ex-
determinations. Thus an alkaline water con- cess of carbonic acid is driven off, and the cal-
taining 16-19 grains per gallon of alkaline carbo- cium and magnesium carbonates are precipitated.
nates, after hardening was found to have taken There is no doubt that these carbonates plav a
up 55-42 grains per gallon of calcium sulphate. very important part in the brewing economy.
Of this 17-92 grains were required to convert the Although a large portion of these salts is
alkaline carbonates into sulphates, leaving 37-5 thrown out of solution during the heating of
grains of available CaS0 4 . the water preparatory to mashing, yet the
The total hardness of this water was 43-75. greater part of the precipitated carbonates re-
Hence 43-75 of hardness correspond to 37-6 maining in suspension finds its way into the
grains CaS0 4 Another determination of total
. mash tun, and there combines with certain
hardness of this water after gypsuming was organic acids, principally lactic acid, always pre-
made some weeks later ; this was found to be sent in malt, forming soluble salts. This neu-
45-5. Therefore tralisation of at least a portion of these
organic
acids must exert an important influence on the
=39 grains of available CaS0 4 .
various processes which take place subsequently.
The amount of calcium and magnesium car-
This does not give such accurate results as in bonates varies considerably, but 12-15 grains
the case of neutral waters, but is quite near
per gallon may be taken as a fair average. It
enough for all practical purposes.
is usual in those breweries where the waters
Treatment of water for brewing black beers, contain very little or none of these salts to
stout and porter. It is a well-known fact that the
sprinkle calcium carbonate or chalk through the
best stout and porter are brewed in London
grist as it goes into the mash tun at the rate
and Dublin. Dublin waters are exceedingly soft, of 4 oz. per quarter of malt (about 10
whilst London water is strongly alkaline, i.e. it grains
per gallon of water).
contains alkaline carbonates, and although con-
Calcium sulphate occurs less frequently than
taining as much as from 40 to 50 grains per the carbonate, but, with the exception of sodium
gallon upon the average of total solids, these
London deep- well waters are yet comparatively chloride, exercises a more important influence
on the mashing and boiling processes than any
soft, showing only 5 of hardness with the soap of the other salts present in natural waters.
test. From this it will be seen that one of the
necessary conditions for the successful produc-
A very interesting on this subject by
article
tion of black beers is, primd facie, a soft water. Southby appeared in the
Country Brewer's
Hence, a brewer whose water supply contains Gazette for 1879, in which he proves very con-
large quantities of magnesium and calcium sul- clusively that, contrary to the opinion prevalent
phates, i.e. a hard water like the Burton waters, among brewers, calcium and magnesium sul-
cannot expect successfully to brew black beers, phates, even when present in the brewing water
but must fall back upon the town supply if that in very large proportions, have no appreciable
is of only a moderate degree of hardness. In the effect on the solubility of the nitrogenous matters
case of naturally soft waters, such as a London of malt ; their principal effect hi the earliest
or Dublin water, no further treatment is neces- stage of brewing operations is to greatly facilitate
the ultimate fining of the beer by causing those
sary, but in the case of a non-alkaline water, such
a water should first 'be well boiled so as to matters which are rendered insoluble by boiling
to separate in a flocculent form instead of in
precipitate the CaC0 3 , then, whilst still boiling,
Na 2 C0 3 at the rate of 10 grains per gallon and that minute state of division which results
30 grains of Nad per gallon should be added to in the beer remaining obstinately cloudy, as so
the brewing liquor, the whole well mixed up many brewers find to then: cost. In addition to
and then allowed to stand until the CaC0 3 has this, calcium sulphate possesses a decided anti-
completely subsided, and the mash proceeded septic action, as worts brewed with a sulphated
with as usual. water resist the action of the fermentative
8. Having glanced briefly at the composition germs when exposed to the atmosphere bettej-
of various types of water and the advantages than those brewed with a softer water. The
or disadvantages they possess from the point of presence of calcium sulphates in a wort also
view of the brewer, we now proceed to consider prevents the solution of the coarser bitter prin-
the relative effects produced on the malt wort by ciples of the hop, hence a brewer employing a
the several mineral constituents usually found to sulphated water can use a much larger propor-
occur in water. tion of hops, if necessary, without rendering his
As has been seen from the tables of analysis ales excessively bitter. The same applies to
on page 527, the quantity and character of the magnesium sulphate. Valuable as the above
various mineral substances found in natural sulphates are in the production of pale and mild
waters vary considerably, and depend on the ales, they are absolutely injurious in the brewing
nature of the rocks through which the water of porter and stout if present to the extent of
percolates. An interesting series of analyses of

more than 3 grains per gallon.
water from the different geological formations of These results have been confirmed by
England was made by Sir Edward Frankland, Moritz and Hartley (Brewer's J. 1883, 92) ; they
and published by him in his work on Water find, however, that these sulphates extract more
Analysis, to which the reader is referred. nitrogenous matter from malt than any other
BREWING 531
of the mineral constituents of water do, and present in water. Nevertheless, the fact remains
Matthews (B. T. R. 1887, 295) is of opinion that that in several breweries where nitrated waters
these nitrogenous substances are of the nature are used for brewing, the yeast keeps clean and
of coagulable albuminoids. We
must at the vigorous and the ales are all that can be desired ;
same time not forget that, by using a water but it is only fair to state that in such breweries
containing appreciable quantities of calcium sugar to the extent of at least one-fifth the quan-
sulphate in solution, a large proportion, if not tity of malt is also used.
all, of the phosphoric acid existing hi the malt, Iron in any shape or form is most injurious,
probably as potassium phosphate, is by double but as it exists mostly in natural waters in the
decomposition converted into acid calcium phos- form of carbonate, it can be converted by oxida-
phate. It is well known that this substance tion into the insoluble peroxide and removed by
exercises a powerful influence on certain albu- subsidence or filtration.
minoid substances, especially at high tempera- The organic matter in water may be of two
tures. Hence the precipitation in flocks of these kinds, vegetable and animal ; the vegetable
bodies, when the wort is boiled in the copper, is organic matter is mostly of peaty origin, and as
no doubt due in great measure to the action of such cannot form suitable pabulum for bacteria,
this salt. and first-class mild and light ales have been
Water containing alkaline carbonates must brewed from peaty waters after treatment with
undoubtedly be" condemned as unsuitable for gypsum and kainite but on the other hand,
;
brewing mild or pale ales. It is well known where the organic matter is of animal origin,
that certain nitrogenous matters, whose presence derived from sewage contamination containing
in malt wort would have a most injurious effect, such matter in solution, as it necessarily must
are freely soluble in slightly alkaline waters ; be, the water, on biological examination, will in
these remain unchanged during the process all probability be found to be highly contami-
of fermentation, and render the finished beet nated with disease germs and although all of
;
persistently cloudy, besides forming a suitable these germs as well as their spores are most un-
nidus for the development of various forms questionably killed during the boiling of the wort
of bacteria. A large amount of colouring in the copper, still such a water must be regarded
matter is also extracted from the malt by alka- as a dangerous one to use for brewing purposes as
line waters, whilstthe diastatic action is con- indicating the presence of matter in solution
siderably impeded ; in the copper also certain which neither boiling nor filtration can destroy
resinous matters are extracted from the hops, or modify, and which at the first moment that
which impart a bitter and rank flavour to the favourable circumstances present themselves
finished beer. will serve to nourish and promote the growth of
Alkaline sulphates if present in excess (more such germs of disease as may find their way
than 10 grains per gallon) have the same action, subsequently into the beer or wort brewed from
though in a very much diminished degree, as such a water.
alkaline carbonates, more especially sodium sul- 9. Barley. The grain which for centuries has
phate. Potassium sulphate, on the other hand, been most generally acknowledged to be best
if present to the extent of not more than 6 to 10 adapted for brewing purposes is barley. Of this
grains per gallon, has a decidedly beneficial cereal as many as 100 varieties have been culti-
effect, acting much in the same manner as mag- vated in this country at one time or another, but
nesium sulphate. the one most generally preferred by brewers is
Calcium chloride gives to the beer a harsh, the narrow-eared, two-rowed type generally
' '
coarse flavour. known as the Chevalier (Hordeum distichum).
Magnesium chloride, if present in small Several varieties of Chevalier barley are grown in
quantity, 2 to 4 grains per gallon, is supposed some parts of the country, and give good results,
'
to be beneficial to fermentation. e.g. Archer Stiff Straw.' There is also another
With regard to the beneficial influence of type of the two-rowed barley known as Gold-
sodium chloride in a brewing water, there can be thorpe, which has been malted in increasing
no question whatsoever. Some of the finest ales quantity for some years, and often gives excellent
in the United Kingdom are brewed in districts results. This barley, having a stouter straw than
where sodium chloride occurs in the natural well Chevalier, is able to withstand bad- weather con-
waters to a larger extent than is allowed by ditions better.
excise regulations to be present in the finished The various species of cultivated barley are
beer. distinguished as two-rowed, four-rowed, and six-
Alkaline chlorides add considerably to the rowed, according to the number of fertile spikelets
palatefulness of the finished beer, exercise con- on the ear. The first and last of these species
siderable antiseptic properties during fermenta- are the most characteristic, the first including
tion, and contribute to a general mellowness and the finest varieties of English barley.
roundness of flavour which without them is The different varieties have been classified
absent in the best brewed ales, mild or pale. by E. S. Beaven as follows (J. Inst. Brewing,
The question of nitrates is still a mixed one ; 1902, 8, 547) :
the balance of evidence seems to be that where Hordeum distichum. Commonly known as
they are not derived from recent sewage con- six-rowed barley, ear wide, short distance
tamination their presence in small quantities acts between the corns. Grown in England as a
as a stimulus to fermentation, but a water con- winter sort. Found in Chilian brewing barley.
taining more than 4 grains per gallon of potas- Hordeum vulgare. Known as four-rowed,
sium nitrate ought to be looked upon with grave ear narrow, long distance between the corns.
suspicion, if not altogether condemned for brew- The ' bere ' or ' bigg ' of Scotland is of this
'
ing purposes, more especially as it is impossible variety as well as most Light Foreign.'
to get rid of nitrates once they are found to be Hordeum zeocriton. Two-rowed barley, ear
532 BREWING.
wide, comparatively short distance between the almost invariably cause such defects in barley
corns. The Goldthorpe barleys are of this type. that the production of really good malt is im-
Hordeum distichum. Two-rowed barleys, ear possible. The difference in price may not be
narrow, comparatively long distance between very great, if viewed from the standpoint of first
the corns. The Chevalier barleys are of this cost, but the deficiency of extract and the in-
type, as well as many long, thin-grained Eastern ferior quality of the wort produced add largely
barleys such as Ouchak. to the actual loss of the brewer.
Originally in the United Kingdom, malt for For the production of sound light beers quick
brewing was made from home grown barley only ; in brightening, it is imperative to secure a barley
of late years, however, very considerable quanti- of high vegetative capacity. With our varying
ties areimported from other countries as France, climate and high farming, English barleys are
Germany, Denmark, California, Russia, Egypt, less suited for this purpose than those imported
Algeria, Chili, and New Zealand and Beaven
;
from other countries, and the superiority of
also classifies these as follows :
foreign barleys over English is, no doubt, to
Chevalier Califomian, Chevalier Chilian, Tri- be attributed to the more suitable condition of
poli (Ouchak type), and Ouchak are the narrow- climate under which they have been grown and
eared two-rowed type, Hordeum distichum. harvested.
Brewing Californian, Mexican, Argentine, North 10. Characteristics of barley. For malting
African, Gaza, Smyrna, Black Sea, Danubian, purposes Stopes groups the qualities of barley
Cyprus and Spanish are mostly of the four- as under four essentials : vitality, condition,
rowed type, Hordeum vulgare. Brewing Chilian, maturity, odour; and six desirable non-
Persian, and Beyrout are of the six-rowed type, essentials: size, weight, uniformity,
Hordeum hexastichum. Mixtures of two-rowed colour, appearanceof skin, age.
and six-rowed barleys are, however, common in Upon the vitality of barley depends the
a good many foreign barleys. growth, hence it is most important that the
Some of these barleys are much superior to barley should contain as few non-germinating
the English in appearance, whilst others, al- grains as possible. The most trustworthy test
though presenting anything but a favourable for this is that of enforced growth, and for this
appearance, are nevertheless not to be despised, purpose Coldewe's
fulfilling, as they do, a useful purpose when apparatus (Fig. 2)
judiciously mixed with our own. This we shall is very effective.
see later on. This consists of
The quality of barley, as one would naturally a receptacle for
suppose, depends to a large extent on the nature water, a germina-
of the soil, climate, manure, &c. tion tray, usually a
Cold clay land, which is stiff or tenacious, no porcelain plate pro-
matter how well drained it may be, can rarely vided with 100 per-
grow really good malting barley (Stopes on Malt forations,and a felt
and Malting). cover fitted with a
Barley requires a warm, friable soil such thermometer as
as the calcareous loams, &c., of Norfolk and the shown in the figure.
districts having a chalk subsoil, which are the The corns to be
best natural soils. Rich, loamy, or well-manured tested are inserted
sandy, and other dry soils are also capable of in the perforations
producing fine barleys when the season favours with the germ
them, especially if lime be present in fair quan- downwards, and a
tities. small quantity of
Barley flourishes best in the farmer's interest moist sand placed
upon land well tilled and heavily manured, for it round them. They
grows strongly and produces heavily. Such receive the neces-
barley, however, is not the best for the brewer, sary moisture for
for it has a higher percentage of certain nitro- germination with
genous matters which are decidedly injurious to perfect equality
the keeping properties of the finished beer. from the recep-
Hence the direct manuring of the soil for barley tacle underneath,
with nitrogenous manures (stable manure, salts whence the water
of ammonia, and nitrates) must be avoided, such evaporates without
manures also produce a rank growth of the stalk causing them to
and of the leaves ; the barley is easily beaten be exposed to an
down, and produces from this cause weak grains excess of moisture.
poor in starch. The consequence is
Accordingly, Professor Farmer recommends that corns of even

that barley should follow wheat which in its quality not only
turn followed roots. This seems to be reasonable, grow as fast as FIG. 2.
for it is now acknowledged that highly nitro- they possibly can,
genous manures are decidedly prejudicial to the but also perfectly alike, thus showing pre-
production of good malting barley. For malting cisely the even or uneven germinating capacity
purposes, the fine, full, well-developed bright of the gram, and as the tray is constructed to
grain is the best. hold exactly 100 corns, the percentage is at once
Climate exercises a more important influence seen.
on barley than soil or manure. Indirectly, a bad Other forms of apparatus in use for the same
' '
summer, and especially a bad harvest time, will purpose are the Aubry and Blaber,' which
'
BREWING. 533
consist of warm chambers or
cupboards, in but narrow furrow may be observed running
which the corns are germinated in a moist down the whole length of one side the general
;
atmosphere. These appear to give better appearance of this side is very convex, both
results than the Coldewe, and their capacity is laterally and longi-
greater, so that several barleys can be tested tudinally, hence it
at the same time. is known as the
This test should show at the utmost only ventral side, and is
4 p.c. of non-germinating grains. The above the side which faces
qualities may be briefly summed up : inwards when the
The corns should not contain more than grain is still attached
4 p.c. of non-germinating grains. to the ear. The
When cut through, the cut surface should be outer or dorsal side
white, friable, and mealy looking ; if it is fatty, of the grain is much
glassy, or spotted, it is not to be recommended flatterthan the ven-
for use. tral. If next we cut
Barley ought to smell fresh and clean, not through a grain of
p
musty or mouldy. barley lengthwise
The corns should be as nearly as possible of with the furrow, so
one size, plump and heavy, and free from other as to split it in two,
seeds. A good heavy barley should weigh from three principal parts E
50 Ibs. to 56 Ibs. per bushel ; all under 50 Ibs. may can be distinguished
be deemed light. The grains should have an in it (Fig. 3) :
even light-yellow colour, with a thin wrinkled (1) The hull, oro
skin. 1 Barley improves in vitality for the first skin. (2) The endo-
few months after harvesting, and then declines, sperm, or starch
so that it is not safe to malt barleys more than substance. (3) The
two seasons old. The actual judging of particular embryo, or germ.
samples with regard to quality and comparative The hull (P) or
value is a matter requiring great practical outer coat of the
experience and skill, especially as often the bulk grain consists of the
is bought from a mere cursory examination of palece or valves,
the sample in market. Grain very hard to bite, formed of three rows
can never be converted into good malt. It has of differently formed
been found that light passes readily through cells. The hull can
vitreous corns, but not through mealy ones, be easily peeled off FIG. 3.
and this fact has been taken advantage of to the barley grain
distinguish between the two. The apparatus after steeping, and under this is a shell tightly
invented by Vogel is used for this purpose. enclosing the grain ; this is the pericarp of the
Barley should be neither over- nor under-ripe. fruit, and beneath this and closely grown
Under-ripe corns have a bad colour, and feel cold together with it lies the integument of the seed.
to the hand. It is difficult to detect over-ripe The starch substance, or endosperm (E), forms
grains. Mature dry grains slip through the by far the larger, bulk of the barley grain.
fingers more readily than immature or damp ones. The embryo, or germ, constitutes about
One of the great difficulties of the present day, of the corn, and lies on the lower end of the
in addition to those resulting from bad harvest- grain, and its point or apex inclines towards
ing and maturing of the grain, is the prevalence the smooth or unfurrowed side. The lobe of
of damaged and broken corns. It is more the seed proper in the shape of a flat shield, GO,
difficult than ever to procure samples that are the scutellum, forms the boundary between the
perfect in this respect, owing to the carelessness endosperm and the embryo ; which, lying as it
so prevalent during the threshing of the barley does in close contact with the endosperm, serves
by modern methods, for we may have not only as a special organ of absorption, through which,
broken corns which are easily detected, but other during germination, the nutritive matter stored
corns, apparently sound and good, that show on in the endosperm must pass on its way to the
closer inspection slight abrasions of the skin growing portions of the embryo. A line of cells
occasioned during threshing by the too close forming a well-marked epithelium separates the
setting of the machinery. This is a source of much embryo from the endosperm. This also has
trouble to the maltster, giving rise to mould on the function of absorption of nutriment for the
floors as well as to a large proportion of non- growing germ, but it is markedly differentiated
germinating corns. from the other tissues by its specialised secretory

Attention has been drawn to the ill effects functions.
of this close dressing by several authorities, and Immediately below the scutellum and in
quite recently Montagu Baird and C. H. Babing- intimate organic connection with it, are the
ton have been instrumental in inducing the main organs of the axis, the plumule and radicle.
Board of Agriculture to publish a circular The former consists of four rudimentary leaves
drawing the farmer's attention to this matter, enclosed ha the plumule sheaths, whilst the
and recommending more careful methods of primary radicle with its root cap is completely
threshing. imbedded in the root sheaths. The endosperm
11. Structure of barley. When a grain of is principally filled with a mass of thin-walled
barley is examined with the naked eye, a deep cells, closely packed with starch granules,
embedded in a very fine network of proteid
Faulty grains are frequently sulphured, but cau be
1
easily detected by an experienced person, on account of

material, and arranged with their larger dimen-
their unusually bright colour. sions parallel with the axis of the grain. The
534 BREWING.
starch-containing cells are surrounded by a Fatty acids . . . 13-62 p.c.
triple layer of thick-walled rectangular cells the Neutral fat . . . 77-78
so-called aleurone cells, the cell contents of Lecithin . . . 4-24
which consist mainly of closely packed aleurone Cholesterol . . . 6-08
grains and fat, embedded in a protoplasmic Resins. The outer
coatings of most cereals
matrix with well-defined nucleus. This layer develop in ripening a certain amount of resinous
does not, however, enter the embryo at any matter, which by its comparative insolubility
point, but is only in close contact with it. protects the interior from premature access of
Lying between the starch-containing portions water.
of the endosperm and the embryo, is a com- In addition to fat and resin, a number of
paratively thick layer of empty and compressed other substances free from nitrogen and which
cells belonging to the endosperm. These cells are generally classed with the resins are also re-
are emptied of their contents during the later
presented in the grain of barley. Very little is
stage of the growth of the grain. The develop- known of them, but although present in minute
ment of the embryo takes place at the expense quantity they play an important part in con-
of the endosperm, emptying its cells of their
tributing to the flavour and general appearance
starch and protoplasm. The cell walls do not of each individual grain of corn.
share the fate of the cell contents, but remain III. The nitrogenous or proteid bodies found
in the ripe grain, pressed tightly together by the in grain are much more complex in chemical com-
growing embryo. position than the carbohydrates ; they all con-
The changes which take place during germina- tain carbon, oxygen, hydrogen, nitrogen, and
tion are brought about by certain catalytic some of them sulphur as well.
agents termed enzymes, and are threefold. Several investigators have turned their
In the first place, there is the dissolution of attention to the nature of these bodies, and we
the walls of the starch-containing cells by one of are indebted to T. B. Osborne for much valuable
these enzymes, which action proceeds progres- information on this subject. This worker finds
sively from the proximal to the distal regions that barley contains the following proportions
of the endosperm in the second place, the
; of proteid bodies :
dissolution of the starch granules thus set free,

Leucosin (albumin) . . 0-30 p.c.
by a second enzyme, and the transference of
the soluble products of the action to the growing
points of the embryo ; and finally, the breaking
down of the complex nitrogenous or albuminoid
Hordein ....
Proteose, edestin (globulin)
Insoluble proteid . .
.
.
1-95
4-00
4-50
bodies, which form the material of the endosperm

10-75
cells, into simpler ones by a third enzyme,
thereby rendering them available as food for Of these the albumin soluble in water, but
is
the young plant. coagulated by heat, globulin is insoluble in
Chemical composition of barley. Those
12. water, but soluble in dilute saline solutions,
substances which go to compose the barley protease is soluble in water, and horde'in only
grain, as well as the other cereals used in brew- slightly so, but readily soluble in 70 p.c. alcohol.
ing, may be classified as follows : In common with all other seeds and living
I. Carbohydrates. II. Resins and fats. III. vegetable as well as animal organisms, barley
Nitrogenous substances. IV. Ash. contains several of a remarkable series of bodies,
The proportions of these several constituents which are considered to be closely allied to the
vary with different kinds of barley, according to albuminoid bodies, and which are termed
circumstances of growth, manuring, harvesting, enzymes. Up to the present no evidence has
climate, &c. been brought forward to determine whether
I. The carbohydrates contain the three ele- these bodies have a definite composition, for in
ments, carbon, oxygen, hydrogen, and are so spite of many investigations it has not been
called because they may be supposed to be de- found possible to determine the constitution of
rived from the union of a certain number of a single one.
molecules of water with an equivalent number These bodies are termed unorganised fer-
of atoms of carbon. ments, and they effect fermentative processes.
The principal members of this group are (a) Effront defines them as active organic
cellulose, starch, dextrin ; (b) maltose, cane sugar substances, secreted by cells which have the
or sucrose, rajfinose ; (c) dextrose, levulose. property under certain conditions of facilitat-
As the chemistry of the carbohydrates is fully ing chemical reactions between certain bodies,
treated of elsewhere, there is no occasion to without entering into the composition of the
refer further to this subject here. definite products which result. The ferments
II. Fats. Only small quantities of fat are act specifically, that is to say, each one exercises
found in grain, and the amount contained in its activity exclusively on substances of well-
barley is about 2-5 p.c. It can be readily defined structural and stereo-chemical composi-
obtained from the ground corn by treatment tion. Of the means by which these ferments
with ether, which on evaporation leaves the fat develop their activity nothing is known. Their
as a thin yellow-coloured fluid of an agreeable reactions must at present be simply regarded
odour, which is, however, soon replaced by an as special phenomena of the catalytic processes,
offensive one if the oil is allowed to remain in catalytic reaction being a somewhat vague term
contact with air. which we apply to those reactions which cannot
The composition of this fat has
been without further knowledge be explained by
investigated by many observers, and
the simple chemical theories. The enzymes have
folio whig is its composition according to A. been divided into the following seven groups,
Stellwag :
according to their respective specific reactions
BREWING. 535
(W. J.
Sykes, Principles and Practice of Brewing, already mentioned, the embryo of the barley corn
1907, 117): is in close contact with the starchy part of the
Group I. Diastatic enzymes. grain, the endosperm, which is the storehouse

Diastase of secretion of all the nutriment required by the young plant
H y drolyse starch
until such time as it can lead an independent
(malt) into
\ maltose, existence and acquire necessary food from the
Translocation diastase
I
glucose , and
(barley) air and soil. The enzymes during this period
maltodextrins.
Ptyalin (saliva) convert the insoluble starch and nitrogenous
j Hydrolyses starch matter into soluble bodies, which can easily
Glucase (maize) finally into glu- travel to the growing germ.
]
(
cose. Ungerminated barley contains an enzyme or
Group II. Cyto-hydrolytic enzymes. amylo-hydrolyst, usually known as translocation
Cytase (malt) ^Transform
cellu- diastase, which differs from the amylo-hydrolyst
Enzymes of seeds in I lose into sugars or diastase, which is present in germinated
which the reserve ma- such as man- grain, in its inability to liquefy starch paste ;
j 1
terial is cellulose J nose, xy lose, &c. the latter having extremely active liquefying
Group III. Pectin enzymes. I and saccharifying powers.
Enzymes which convert pectinous sub- a cold-water extract of barley be added
If
stances into vegetable jelly. ;
to starch paste, it is found to have no action
Group IV. Inverting enzymes. ;

whatever. If, however, this starch paste be
Con vert cane1 first treated with cold-water malt extract, at a
Invertase yeast)
Invertase (malt)
into ^ [ temperature of about 75C. for a few minutes, so
f vert sugar. as to bring it into the form of soluble starch or
Maltase (yeast)
J
Transform mal- erythro-dextrin, then cooled to a temperature of
Enzymes of the small I tose into glu- 50C., and some cold-water barley extract
intestine )
cose. added, the conversion of the soluble starch or
Enzymes of yeast which degrade the higher dextrins into reducible sugars proceeds
dextrins to maltose ; these are especially with great facility.
present in those yeasts which bring Translocation diastase is unable to corrode
about the secondary fermentation and starch granules, Brown and Morris stating that
condition of beer. this power and that of liquefying gelatinised
("Inverts milk starch appear to go hand in hand.
Enzyme of kephir
\ sugar. Lintner and Eckhardt found that the action of
Probable enzyme of (Converts maltose barley and malt diastases differed considerably at
germinating barley \ into cane sugar. various temperatures (Zeitsch. fiir Brauw. 1889),
Group V. Proteolytic enzymes. and J. L. Baker has shown (J. Chem. Soc. 1902)
Enzymes of malt and \~ that the products of reaction on a solution of
other vegetables, Covert proteids soluble starch by barley diastase are very different
which are mto P^ôses from those of malt diastase.
among f
peptones, and As soon as the barleycorn begins to germinate,
peptaseandtryptase
Trypsin (pancreas) the more active amylo-hydrolyst, termed by
, Converts proteids Brown and Morris secretion diastase, to dis-
I into
proteoses tinguish it from the diastase already present in
Pepsin (stomach) j
and
peptones, the grain, makes its appearance, and accord-
but not into ing to these authors, is principally due to a
amides. secretion" by the columnar epithelium of the
Peptonising ferments secreted by many growing embryo. There is a steady accumula-
bacteria. tion of this diastase in the endosperm, which in
Group VI. Glucosidal enzymes. the course of time permeates its whole tissue,
,
Splits up amyg- the ready passage of the enzyme through the
contents of the grain having been enormously
al-
facilitated by the previous destruction of the
^
hydrocyanic cell walls by the cyto-hydrolyst.
and water. acid, When thisis accomplished, the malt acquires
Many other enzymes which have the power the so-called mealy condition which the maltster
of hydrolysing glucosides. endeavours to bring about to its fullest extent.
Group VII. Zymase of yeast. Secretion diastase was first investigated by
Splits up sugar into alcohol and carbon Payen and Persoz, in 1883, who gave it the
dioxide. name diastase from Sidcrracris (separation), on
'
Ferments,' as applied to these bbdies, is account of its supposed property of separating
hardly a very satisfactory name, and it has the interior of the starch granules from their
been suggested, and the suggestion has been outer envelope. Under the action of this
adopted to a large extent, that those enzymes diastase, starch which has been first gelatinised
that bring about the hydrolysis of substances by boiling water undergoes a series of hydrations
should be termed hydrolysts, and by combining and successive decompositions, resulting in the
'
the word hydrolyst with the name of the production of maltose and dextrin. The action,
susbtance acted upon, we get a distinctive name which is capable of taking place at 0C., attains
for each class. Thus an enzyme capable of it maximum between 60 and 65(J., and ceases
inducing the hydrolysis of starch is termed an altogether at 80C.
amylo-hydrolyst ; one which affects proteids, a It appears, then, that malt contains at least
proteo-hydrolyst, &c. two amylo-hydrolysts or diastases, one of which,
Hole of enzymes during germination. As formed during the growth of the barley, has not
636 BREWING.
the power of transforming a saccharifying starch nitrogen wanders through the scutellum into the
paste until it has been first converted into young plant.
soluble starch ; the other, formed during germi- Brown estimates that about 35-40 p.c. of
nation on the malting floors, possesses the power the nitrogenous reserves of the endosperm pass
to a very marked degree of saccharifying starch into the young plant, and it is probable during
paste even at as high a temperature as 80C. the ordinary malting period that at least
Brown and Heron (Chem. Soc. Trans. 1879, 60-70 p.c. of the proteids have been altered,
596) formed an opinion that these bodies were while only 16-17 p.c. of the reserve starch has
not simple chemical compounds of constant been attacked in the same time.
definite composition, but must be considered as The nitrogenous bodies found in malt are
a mixture of several bodies differing from each due to two quite different" but complementary
other in chemical and physical properties. They processes going on simultaneously, viz. the
ascertained that when cold-water extracts of breaking down of these substances into less com-
barley and malt are heated up to different plex bodies, which goes on in the endosperm, and
temperatures, for each increase of temperature the building up of these simpler bodies into new
there is a distinct and definite amount of coagu- complexes, which goes on in the growing embryo
lation of soluble albuminous substances, and a down-grade and an up-grade process. About
at the same time a diminution in the diastatic one-half of the nitrogenous bodies of malt are
energy of the solution, from which they conclude up-grade products of the processes of germina-
'
that the diastatic power of malt is a function tion. This appears to be the explanation of the
of the coagulable albuminoids themselves, and fact that the conditions which tend to force the
is not due to the presence of a distinctive trans- growth of the vegetative parts of the grain are
forming agent.' There can be no doubt that just those which tend to increase the proportion
during the kilndrying of malt a similar reaction of the permanently soluble nitrogenous con-
takes place, especially in the earlier stages of stituents of a malt.
drying ; a small proportion of the more easily H. T. Brown (The Nitrogen Question in
coagulable albuminoids being rendered insoluble, Brewing, J. Inst. Brewing, 1907, 5) has investi-
the diastatic power, which had attained its gated the nature of the nitrogenous bodies
maximum at the withering stage, at the same time soluble in water and not coagulated on boiling,
being diminished to a considerable extent. present in the finished malt, and was able to
Indeed, it is a well-established fact, that a high- determine about 66 p.c. of the total.
dried malt will produce in the brewing a more Taking the nitrogen of a previously boiled
highly dextrinous beer than one which has not extract of malt as 100, he found its distribution
been dried at so high a temperature on the kiln. amongst the various classes of constituents
Another set of enzymes which are secreted came out approximately as follows :
during germination are those that act upon the Ammonia .3-5
nitrogen . .
proteids, the proteo-hydrolysts. It was not

Malt albumose nitrogen . . . 20-0
until quite recently that the presence of these Malt peptone nitrogen . . .31-0
enzymes were definitely decided in the affirma- Amide and amino nitrogen . . 8-5
tive, although it has long been known that the
Nitrogen due to organic bases . . 4-0
nitrogenous bodies of barley undergo considerable Balance of N still unaccounted for . 33-0
modifications during germination, and Weiss
(Zeitsch. f. physiol. Chem. 31, 78-79 ; and 100-0
Zeitsch. ges. Brauw. 1903, 19, 301) has proved
This gives a synopsis of the various classes
fairly conclusively that the two enzymes, peptase
into which they are divided. It was found that
and tryptase, are present. Peptase degrades the
the albumoses consist of at least three distinct
proteids down to albumoses, having a maximum
bodies, albumoses I., II., and III.; whilst the
activity at 51C., and tryplase degrades the
albumins down to amides, &c., the optimum peptones can be differentiated into two malt
temperature lying between 45C. and 50C. The peptones, I. and II. The 8-5 p.c. of nitrogen
action of both enzymes ceases at 70C. attributed to amides and amino-acids includes
The embryo of the barley corn during asparagine, tyrosin, and leucine, and allantoin
is also included. The 4 p.c. of nitrogen corre-
development requires nitrogen to build up new
protoplasm, in addition to the carbohydrates sponding to organic bases mainly represents
betaine and choline.
supplied to it with the help of the diastase, and
the mineral salts. There is therefore a con- The following table, deduced by R. Warington,
tinuous draft on the nitrogenous as well as the from a compilation of all accessible analyses,
carbohydrate reserves of the endosperm. These numbering 56 in all, may be taken as showing
a fair average composition of barley grain :
nitrogenous reserves reside for the most part in

the fine network of the material in which the 1. Carbohydrates .
. . 63-66
2. Fibre 7-09
solid starch grains are embedded, and consist of . . . .
a complex mixture ofproteids with very

3. Fat 2-05
different properties. Some are soluble in water 4. Albuminoids . . . 10-58
(1516 p.c. of the whole), whilst others require 5. Ash 2-57
reagents to bring them into solution. These 6. Water . 14-05
proteids require previous preparation before they
can be absorbed by the embryo. Total 100-00
. .
This preparation is brought about by the Barley grain contains on an average less
enzymes above described, the peptase reducing nitrogen than either wheat or oats ; the propor-
the proteids to albumoses, and the tryptase tion least in fine malting barley, amounting to
is
further reducing the albumoses to the amino- only 8 or 9 p.c. of albuminoids.
acids, &c., and it is mainly in this form that the IV. The ash of barley grain, as calculated
BREWING. 537
from 50 analyses by E. Wolff, has the following Cleaning, grading, kilndrying or sweating.
The dust which is generally found adhering to
average composition :
Potash . . . K 2 21-35 jarley consists to a large extent of spores of

Soda . . . Na 2 O 2-25 numerous ferments and fungoid organisms, many
Lime . . . CaO 2-74 of which find their way into the fermenting
'
8-66 round ; seeds of weeds and other foreign grains

Magnesia ; .
MgO also be present.
Ferric oxide . Fe,0 3 0-91 may
C. G. Matthews (J. R. Microsc. S. 1883)
35-91 bund that various kinds of barley, English as
well as Saale, French, Chilian, and Californian,
Phosphoric anhydride P2 5 35-19
yield, when steeped for a short time in water, an
Sulphuric anhydride . S0 3 1-72 abundance of mould spores, bacteria, and infu-
Silica . . . Si0 2 26-10 soria of various species, and from many experi-
Chlorine . . .01 0-88
ments made by him he concludes that in the
irst stage of malting, when the barley is put in
63-89
steep the spores of various moulds and other
The bulk
of these phosphoric acid compounds micro-organisms are present in quantity in the
in barley ash exist as a calcium-magnesium- steep water, being introduced into the cistern
potassium salt of oxymethylenediphosphoric with the barley, and although the greater portion
acid, while about 5 p.c. are present as lecithin- may be removed on withdrawal of the steep
phosphoric acid. water, yet there would in all probability be left
It has already been stated that land which sufficient to cause a mould growth, on injured or
has been highly manured with mineral salts weakly corns whilst on the malting floor. Now,
.t is a well-known fact that
containing a high percentage of nitrogen, such, good, healthy, grow-
for instance, as sodium nitrate or ammonium ing, perfect corns are never found to develop
sulphate, will produce a heavy crop of barley. growths of any kind of mould the corns which
;
This, of course, from a farmer's point of view, is appear to be favourable to such are always those
decidely an advantage, but such barley is always which from various causes are incapable of
found to be exceedingly rich in albuminoids, and carrying on a strong and healthy growth, having
consequently low in the percentage of starch. been injured by heating in stack, or sprouting,
Hence for brewing purposes it is extremely un- or, as is more generally the case nowadays, been
advisable to use such a barley, for not only will split, crushed, or otherwise damaged during
the wort resulting from the malt made from this threshing, a slight abrasion of the skin in some
barley be poor in saccharine matter, but these instances being sufficient to give rise to develop-
nitrogenous substances, when present in too large ment of mould. Hence it will be seen how very
proportions in the wort, exercise a very injurious important it is that the barley should be cleaned
influence on it, and cause the finished beer to and freed as much as possible from dust, broken
become thick and cloudy and prevent its keep- corns, and all other matters which may in any
ing sound for any length of time (L. Marx, Rev. way encourage the growth of mould on the
Univ. de la Brasserie). malting that if a maltster wishes for
floors, so
Therefore, from a brewing point of view, a clean floors he must first thoroughly clean his
barley rich in albuminoids must be regarded as barley of such objectionable bodies by proper
of poor quality, while a low content of albu- and careful screening. A form of screen which
minoids in general is an expression of high
quality. Hence Maercker (Bied. Zentr. 1885,
696) concludes that the weight per bushel which
is generally regarded as a fair criterion of the
value of a barley, can hardly be looked upon
alone as a safe guide with regard to quality, bul
that the chief characteristics of a first quality
barley are (1) its consistency; (2) its colour
(3)percentage of moisture ; and (4) its percentage
ofalbuminoids ; these in first-class barleys shoul<
not exceed 8-6 p.c. He also finds that a grain
possessing a fine, thin husk is found to yield th
largest amount of starch the kernels in this
;
case should be thin and rounded, the percentag<

of husk being a minimum. This is the viev
adopted by Prof. Brewer, of the Brewer's
Experimental Station, New York, as well as by
C. Lintner, Dingl. poly. J. 247, 350), who gives
10-5 p.c. of albuminoids as a limit for first-class
barley.
Preparation of barley for malting. Very
13. FIG. 4. SELF-ACTING MALT-SCREEN.
littlebarley is in a fit condition for undergoing
the process of malting when it is delivered at the seems well adapted for this purpose is shown in
brewery or malthouse by the farmer, as it gene- Fig. 4.

rally contains several varieties of foreign seeds Grading grain is, if possible, still more impor-
fragments of pebbles, &c., mixed up with it, as tant than cleaning it, as it is most desirable that
well as light and damaged corn. The following for malting purposes all the corns should as
preparatory stages are considered by Stopes to far as possible be of uniform size. The next
is the
be generally needed :
process, and one of extreme importance,
538 BREWING.
kilndrying of barley, or sweating, as it is tech- growth of the plumule takes place between the
nically termed. With cold and damp seasons, testa and pericarp, and in very close proximity
and with the modern fashion of threshing by to the reserve materials of the endosperm, until
steam either when carting or almost immediately it finally issues at the end of the grain the
after stacking, so that the grain has had no farthest removed from the embryo.
chance of sweating in stack, it is highly desirable 15. The water used for wetting or steeping
that this should be done on the kiln, but, like should be of such purity that it may pass as
every other operation in malting, it requires drinking water. Waters containing much
discrimination and the exercise of judgment. organic matter, especially that derived from
Broadly speaking, almost every sample that has animal sewage, frequently contain salts of phos-
not been influenced by damp is decidedly the phorus, which, coming in contact with the
better for a few hours upon the kiln prior to numerous spores of bacteria and mould on the
storing or steeping. If the acrospire has moved, surface of the barley, afford a most favourable
then drying does more harm than good. medium for their development and growth. Cer-
The moisture percentage should be deter- tainly the water in which barley has been steeped
mined on each parcel, and those parcels which affords itself very suitable nourishment for these
contain a larger percentage than 12 should be micro-organisms, and where the water helps in
dried (or sweated) to expel any excess over this the same direction the result is self-evident.
figure. Of the mineral matter in water iron in any
Great improvement in germinating power is form is most objectionable, as it gives rise not
brought about by this sweating, which is as- only to the insoluble phosphate of iron, but it
cribed to the following causes (1) the removal
: also forms with the tannin in the husks of the
of dirt from the skin of the corn and consequent grain, the black insoluble tannate of iron which
freeing of the pores ; (2) the removal of moisture remains in the husk and discolours the gram.
from the endosperm cells causes them to draw Chlorides cf the alkalis, if present in large
together slightly and so gives rise to pores and quantity, remove a considerable proportion of
passages through which the steep water may mineral as well as organic matter, whilst they
reach the centre of the grain,-excess of original retard germination to a considerable degree
moisture causes these cells toswell and become (Michel and Handwerck, Bied. Zentr. 1882, 486).
tightly pressed together ; (3) the expulsion of The presence of calcium chloride hinders the
moisture considerably increases the secretory extractive action of sodium chloride to a certain
function of the embryo as regards the amylo- extent (ibid.).
hydrolytic and cyto-hydrolytic enzymes. Hitherto it has been generally accepted that
Sweating is best carried on at a low uniform when barley is steeped in the cistern, the steep
temperature, rarely exceeding 105F. Schon- water extracts matter not only from the husks,
field states that excellent results are obtained by but also from the interior of the gram and
;
gradually raising the temperature of the barley differing views have been advanced regarding
to 133F., and maintaining this temperature the influence which hard and soft waters exert
with a liberal supply of ah" until sufficiently dry. on the extraction of organic matter and phos-
When dried it is advisable to store the barley in phates from the ulterior of the grain. Ullick
bins for at least a fortnight prior to steeping, in found that calcium and magnesium carbonates
order that it may have time to mellow. The and sulphates are generally supposed to fix the
grain is now in a suitable condition for under- phosphoric acid in the grain, the potash and
going the various processes of malting ; these magnesia being extracted by the hard water,
are steeping, couching, flooring, withering, whilst the lime enters into combination with the
drying. phosphoric acid, forming an insoluble phosphate
14. The chief distinctive difference between m the grain (Ullick, Bied. Zentr. 1882, 40^2) ;
malt and corn is growth ; no matter what pro- but Mills and Pettigrew found that the more of
cesses they may have been subjected to, any these mineral salts there are in steep water the
grams of the corn which have not grown more mineral matter there is extracted from the
remain as barley, wheat, &c., and are not malt. barley (Chem. Soc. Trans. 1882,38). They were
When a seed is placed under suitable conditions confirmed in their results by Michel and Hand-
with regard to heat, light, air, and moisture, it werck (Dingl. poly. J. 247, 82, 168, and 214). From
begins to germinate or grow. When it begins to a series of experiments made by the author on
grow the first sign of a change taking place is the steeping of barley, where (1) distilled water
the protrusion in a downward direction of the alone, (2) a water containing 13-8 grains of
1
rootlets or radicle through the integument ; at calcium carbonate per gallon (v. Analysis
the same time, the plumule or acrospire begins No. 2, p. 352), and (3) the same with 30 grains
to start growing in an upward direction until it of gypsum added, were employed, the following
bursts through the integument and gives rise results were arrived at :that the total matter
to the first leafy organs of the growing plant. extracted by water No. 1 was in all cases the
When wheat commences to germinate, the greatest, that by water No. 3 least ; that this
plumule of the embryo on bursting through its applied to the mineral as well as the organic
envelope finds itself in immediate contact with matter, but whereas No. 1 dissolved out the
the inner surface of the pericarp, which in this most mineral matter, No. 3 extracted the most
case not being sufficiently strong is ruptured, phosphoric acid.
the plumule continuing its growth outside the Mills and Pettigrew conclude that nitrates
grain. have a highly stimulating action on the germi-
In barley the pericarp is of sufficient strength nation of malt, and recommend the addition of
(even hi the so-called naked barley, where the a small quantity of calcium nitrate (about 3
palea, as in wheat, is not adherent) to retain grains per gallon) to those waters which are de-
the plumule within it. In consequence of this the tent in nitrates.
BREWING. 539
A. J. Brown, however, has proved (J. Inst. is first steeped in the same manner as in the
Brewing, 1907, 13, 658) that when undamaged English floor system. It is then transferred to
barley corns are steeped in either hard or soft the interior of a metal cylinder or drum, which
waters the salts dissolved only penetrate the is rotated slowly in order to keep the growing
outer thick coverings of the grain, and the first barley on the move, whilst moist air is blown
thin skin, or pericarp, but are arrested by the through the grain from a central duct ; by this
second thin skin, or testa, which immediately means absolute control of temperature and
surrounds the germ and endosperm, only pure humidity is obtained, and the necessity for
water entering the grain. Hence the action of sprinkling is obviated when the piece (as
;
steep water is limited to the external envelopes of the drum load of growing barley is termed)
the grain, and the matter extracted during steeping has grown to the desired extent it is
(varying from 0-5 to 1-5 p.c.) must be considered either transferred to an ordinary kiln or dried
to be derived in its entirety from the skins of in the same drum, hot air being blown through
the barley corn. Working on these lines, H. instead of cool moist air until the piece is suffici-
Seyffert (Zeitsch. ges. Brauw. 1907, 30) finds that ently cured.
the carbonates of the alkali earths (sodium, The simplest form of malthouse possessing
magnesium, and calcium) act on the tannin and any capacity for work is a plain two-story build-
bitter principles of the husks (the effect being ing having attached to it a kiln or drying-
to remove them or render them harmless), house, and consisting of a ground-floor of clunch,
giving the malt an aroma and greater sweetness. a brick steeping cistern, and a first floor of
This author considers very soft waters unsuitable timber with or without partitions for separating
for steeping, and only give good results with the stored grain or malt ; but a good malt-
very fine thin-skinned barleys, for the greater house of fair size most conveniently and
is
the carbonate content of the water, the less favourably worked if consists of one main
it
stress need be placed on the quality of the building of three stories two kilns and a corn
barley. Moufang and L. Vetter confirm the or malt store.
views of Seyffert, and also add that calcium The growing floor may be composed of a
sulphate and sulphuric acid in steep water variety of materials, but that which is most to
cause the husk constituents to adhere more be preferred is either cement concrete worked to
firmly to the fibre of the husk, so that these a perfectly smooth face, or plain unglazed red
substances can only be removed by subsequent tiles, well set in cement.
treatment with alkaline water. Matter in The cistern should always be at the end
solution in the steep water, however, enters opposite to the kiln in a single-floor house, and
damaged corns, and loss of extract from the so arranged that entire control of the tempera-
interior of the grain takes place in any type of ture of the steep liquor can be secured, and that
water, which fact strengthens the objection to the grain can be readily screened into them
the damages of close threshing. when filled with water to enable the thin corn
It will be seen, then, that, contrary to previous and refuse to float off.
views, the most favourable water for steeping The water supply should be so arranged
is one containing alkaline carbonates. that it can be run in from below and overflow
The temperature of the steep water con- at top prior to a charge of steep liquor, and a
siderably effects the rate at which the grain number of inlet and outlet pipes, all fitted with
absorbs water, and also the speed of germination strainers, should be fixed. There should be
on the floors. The warmer the water, the more in addition a series of perforated pipes, by means
rapid is the absorption, and the quicker the of which water can be sprayed or sparged from
start of germination. The temperature usually above over the grain like a shower. The cis-
adopted in England is 50-55F., and care terns are emptied of the steeped grain either by
should be taken to see that this is kept constant, shovelling on to the floor, if on the same level,
in order to preserve regularity of water content or by running down through shoots in the
and growth. bottom to the floor below.
The use of lime water in the steep has been Cisterns 'are generally built of concrete, brick,
recommended by Windisch to improve germina- or iron. An excellent form of construction is
tion and to avoid mould formation on the floors. afforded by the use of the
This has been found to give good results, the Hygeian Rock cement, as
lime water being used in the first change only. shown in Fig. 5. This
16. Malting. At present three systems of method gives a wall only
making malt are practised : 9 inches thick, but quite
(1) English system. strong enough for all prac-
(2) Continental. tical purposes ; the outside

(3) Pneumatic. wall of the cistern is gene-
The English system
briefly consists in steep- rally coated with cement,
ing the grain in water in large iron or stone whilst the interior of the
cisterns, draining the water off, spreading the cistern is preferably lined
moistened grain in thin layers upon exposed with white glazed or
floors and drying upon an enamelled bricks well set in
open fire kiln at a FIG. 5.
period of from 9 to 21 days from time of steeping. cement. Brick or concrete
The continental system differs materially in cisterns should have a wide central channel
of the channel
allthe above details. running their full length. The top
Pneumatic malting provides for absolute must be framed to receive perforated iron plates
control over the admission of air supplied to the or tiles to serve as strainers. Iron cisterns are
germinating grain. best made square in shape, with a conical bottom
Briefly the system is as follows : The grain with a valve at the apex to discharge the wet
540 BREWING.
grain, the draw-off cock for the steep water at the sides of the furnace are used as coal or
being fixed as close to the valve as possible, and fuel stores. The drying floor c is built at all
being covered with a perforated plate to prevent heights, ranging from 5 to 29 ft. above the
the barley corns being drawn off with the water. furnace, and is generally made of earthenware
Such cisterns are usually fixed above the growing
floor, and the grain is discharged directly on to
it. The capacity of these cisterns should be ample
enough to steep the utmost quantity of corn the
floor can possibly grow in the coldest weather ;
not less than 14 cubic feet per quarter should

be allowed when calculating their dimensions.
The kiln should be a lofty and roomy struc-
ture, preferably of brick, with a high roof
surmounted by a cowl. The area of the drying
floors should never exceed one-fourth or be less
than one-sixth of the growing floors, nor should
the combined air inlets and discharges bear a
ratio to each other exceeding that of 4 to 5.
In practice it is found that the more closely
a kiln resembles a chimney in construction, the
greater is its effective capacity, consequently
the tendency has been constantly to increase the
height of the kilns. Kilns may be of various
forms, but a square one is undoubtedly the best.
In Fig. 6 is shown a type of kiln at one time very
common in Great Britain.
FIG. 6.
In every portion of the plant connected with

malting, great diversities of size and style occur,
and kiln furnaces offer no exception to the rule.
Generally malt-kiln furnaces either permit the
products of combustion to pass through the FIG. 7.
malt whilst drying, or they do not do so. The
form of furnace, perhaps, most in vogue in this perforated tiles resting on light iron bars, whicl
type of kiln is known as the fire-basket. This in their turn are supported by larger joists.
is a large open cast-iron basket of from 3 to 6 ft. The construction of the roof D is of great
square, with legs or supports carrying a frame importance, as very much depends on it ; if the
fitted with ordinary fire-bars and thick sloping pitch is not at the proper angle, the drying of
sides. These baskets are sometimes placed the malt is affected to a certain extent ; cross
merely upon the bottom floor of the kiln with timbers are objectionable, and should be avoided
no protection of any kind, others are built over as far as possible; lath and plaster forms the
with a brick arch left full of holes for the escape best lining to the slate roof, as well as for the
of heat on all sides. A in Fig. 6 shows the form sides of the drying chamber.
of fire-basket usually employed, the spaces BB The cowl B is the usual form of outlet to
BREWING. 541
this type of kiln. In 1881 the first kiln in hours, it being the most impure ; the succeeding
England with two floors, and known as Stopes's steep water should be changed every twelve to
system (Fig. 7), was erected by Messrs. Taplin & twenty-four hours, according to temperature and
Sons, at Brighton, which gave very satisfactory season of year.
results, and is used by many breweries in this Sufficient time must be allowed between run-
country. It is claimed that two-floor kilns pos- ning off the old and running on the fresh water
sess several advantages, of which, probably, the to allow the barley to become well aerated. In
chief are the regularity of temperature upon some maltings air is pumped into the barley
both floors and the economy of fuel and labour. whilst it is steeping in the water.
The modern type of kiln is illustrated in The first steep water should be run off from
Fig. 8. With this type the furnace A consists above, and the second water run in from under-
of a square chamber lined with fire-brick, and neath ;
this upward filtration serves very effec-
furnished with ordinary fire-bars. The tem- tually to cleanse the grain from any adhering im-
perature of the upward draught is regulated purities. Some maltsters sparge on the steep
by iron plates which control the air inlets water through sparge arms fixed above the
cistern, thereby aiding aeration considerably.
The grain is allowed to remain in steep for a
period of forty to seventy hours, depending upon
surroundings but the maltster would naturally
;
be guided by the temperature of the atmosphere,

the quality, condition, and age of the barley,
high temperature necessitating more frequent
changes of steep water and shorter time in
steep. Then, again, coarse, thick-skinned, or
heavy barleys would naturally require longer
steeping than the lighter and thinner kinds ;the
older the barley, the longer it requires to be
steeped, as new barley germinates more quickly
than old, the chief object of steeping being to
impart to the grain about to be malted a suffi-
ciency of moisture to ensure perfect and regular
germination.
18. Couching. Before the repeal of the malt
tax the barley, when taken out of steep, was
placed in what was known as the couch. This
might be regarded as a dry cistern where the
grain had to lie a certain number of hours, or until
it was gauged by the excise officer and the duty
levied. Since this has been done away with, the
couch is no longer needed, though even yet
many maltsters pile up the barley when taken
out of steep in a heap for twenty to twenty-four
hours, indeed, until the growing point of the
rootlet begins to show. This is a great mis-
take. In the first place, a greater amount of
heat will be developed in the interior of the
heap than on the outside by the germinating
grain, hence these corns will grow more rapidly
' '
than the others, so that very uneven pieces
on the floors will be the result. It has also
been proved that heat in couch tends directly
to produce acidity in the finished malt. After
the gram comes out of steep it requires all the
FIG. 8. oxygen it can get, as well as the removal of the
carbonic acid gas which becomes disengaged
oa above the fire. The hot air and products of by the process of germination ; this necessarily
combustion pass up the shaft, and are distributed involves free contact with air, and therefore it is
evenly over the drying floor c by the brick and advisable that couching be done away with
concrete baffle B, supported on short brick altogether.
pillars. The drying floor c is composed of steel 19. Flooring. Where it is still practised, as
wire. The cowl is replaced by a shaft D, pro- soon as germination is observed to have com-
vided with louvre boards, and a fan E to control menced, the couch is broken down and the grain
the force of the upward draught is fixed at the spread out on the floor, the depth at first vary-
base of this shaft. The spaces FF are used as ing from 12 inches to about 3 or 4 according
a malt stores. to season and temperature; it is then left for
17. Steeping. The cistern should be filled from twenty to twenty-four hours, when it is
with the steep water, then the barley slowly run turned by means of a wooden spade. For the
through a shoot into the cistern by this means
; succeeding two or three days it is either
the dirt and dust, small and light corns, and ' '
ploughed or turned about twice daily ;of
other matters find their way readily to the sur- course this entirely depends on the judgment
face and may be skimmed off. This first steep and experience of the maltster, his main object
water should be run off within the first six being to obtain a good bushy root and a regular
542 BREWING.
development ofthe acrospire. This requires and the temperature carefully noted from time
very careful and close attention on the part of
' '
to time ; indeed, the question of temperature is
the maltster, for during flooring he has not just as important a factor in malting as it is in
only to control the development or growth of mashing.
the germinating grain, but the very nature of 20. Drying. By the time the germinated
that growth. He has to give air and secure barley is ready to go on the kiln, it really is in
ventilation, to regulate heat and humidity, to effect no longer barley but malt, or more pro-
foster the development of the acrospire, and perly green malt, and has attained at this stage
check the root growth, or vice versd as the case its highest diastatic energy, so that if the object
may be all this can only be attained by long

;
were merely the production of diastase the malt
experience and an intelligent appreciation of might now be dried off at ordinary tempera-
scientific facts. tures but for the purposes of the brewer and
;
As a rule, English maltsters allow germina- distiller it is absolutely necessary that this
tion to proceed until the acrospire has extended green malt be subjected to the influence of heat,
to about three-fourths the length of the grain, not only for the purpose of drying it completely
the rootlets being at the same time about twice and arresting germination, but in order that
the length of the grain, but this is varied con- certain changes may take place in the chemical
siderably according to the ideas of each in- composition of its various constituents which
dividual maltster. Germination is accordingly are necessary to impart flavour and other
carried on until this stage is reached. properties to the liquor brewed from it and
About the fifth day from the time of taking which we term beer. In addition to this, the
out of steep the grain is sprinkled at intervals malt also becomes capable of lengthened storage,
with water from a watering-can ; this is con- and when well dried is best adapted for grinding
tinued until the sixth day. The quantity of and for transport ; also all mould and fungoid
water used for this purpose varies from three to growths are completely arrested and their
six gallons per quarter of barley, but of course vitality suspended.
will naturally depend upon the state of the The temperature employed in finishing off
atmosphere as well as on the condition of the the malt on the kiln will determine its quality,
piece. On the days of sprinkling the grain is thus we may have pale malts, medium, and high-
turned four times each day after the sixth day
;
dried.
it is turned two or three times daily. As soon For pale malt only the better qualities of
as the germination has proceeded to such a barley should be used, and great attention
degree as may be desirable, it is subjected to should be paid whilst on the growing floor to
the process of withering, the object being to prevent the development of mould also the ;
arrest germination, to increase the temperature withering off should be carefully attended to,
of the piece so that as large an amount of the principal object of the maltster being to
moisture as possible may be got rid of prepara- obtain a good healthy growth in the earlier
tory to kilndrying. In many malthouses a stages, and that the green malt should be as
proper withering floor is provided, generally of dry as possible at the time of going to kiln.
wood. During this stage the sootlets wither, be- To dry pale malt well, Stopes says three
coming shrivelled and dry. As soon as this things are necessary :
takes place, many maltsters throw the green (1) It should be loaded in the condition just
mait, as it is now called, into a heap, and allow described as sound green malt upon a floor at a
it to heat spontaneously, the object being to thickness rarely, if ever, exceeding 7 to 8 inches.
make it tender. (2) It must remain unturned at a low tem-
A piece which was sprinkled on the fifth and perature until nearly all moisture is removed.
sixth days under ordinary conditions should be (3) Heat must then be applied steadily and
ready to go on kiln on the tenth or eleventh freely, and be maintained for a considerable time
day. at a nearly uniform temperature, ranging from
Some
maltsters allow the piece to become 160 to as high as 230 in some cases.
almost dry, not sprinkling until the eighth or Constant forking of the kiln at this period is
even ninth day, but this cannot be recom- necessary, otherwise mould is specially liable to
mended. The grain at time of going to kiln is at take place, and this should be persevered in
most only imperfectly withered, contains an until the malt is sufficiently dry to be turned.
excess of moisture necessitating very frequent On no account should turning be resorted to
turning as well as encouraging the growth of until the malt is fairly dry to the touch. To,
mould on kiln, and finally imparting a degree of ensure the carrying out of these points with
hardness or steelinrss to the finished malt greater accuracy and less risk than is possible
which occasions diminished extract and pos- on an ordinary kiln, the employment of a fan
sibly starchy worts. is requisite to create a motion of air through
If the barley whilst on the floors shows the malt, by which means the moisture can be
much, or in fact any signs of mouldiness, both extracted at much lower temperatures than would
the cistern and floors must be thoroughly well be possible under ordinary circumstances, and
scrubbed with water to which 10 p.c. of good without fear of putrefaction, whilst for unifor-
strong calcium bisulphite has been added. mity of temperature it is unequalled.
When dealingwith low-class, ill-conditioned, As long as an appreciable amount of mois-
or damaged gram, it is always well to add a ture remains in the malt, it is most important
suitable quantity of bisulphite, both to the that the temperature on kiln should not exceed
steep water as well as to the water used for 120, while special attention must be paid to
sprinkling. ventilation. When we consider that from 90
It is also essential that thermometers should to 120 is the most favourable range of tempera-
be placed at frequent intervals on the floors, ture for the development of the numerous
BREWING. 543
spores of various micro-organisms which, de- 6 hours without undergoing any

darkening in
spite all our efforts to the contrary, are to be colour whatever.
found adhering to the moist corns, and that with Much the same method is pursued in the
their development ensue chemical changes, such drying of the malt on double-floor kilns as on
as the production of various organic acids, which single. The malt is first loaded on to the top
most seriously affect the character of the malt, floor, where it is kept at a temperature not ex-
it would seem that the shorter time the malt ceeding 120 until about 90 p.c. of the moisture
is exposed to this
temperature the better ; there- is driven off. It is then dropped through doors or
fore it is advisable that the layer of malt should holes to the lower floor, where it is finally dried
off at a temperature of from 180 to 190 or more,
certainly not exceed 8 inches, and it would
be better still if it were only 6. But it is not and the same heat and air that effect this are
simply a question of drying the malt quickly at in fact the very best possible to drive off the
a low temperature ; certain changes irrespective moisture from the upper floor, which in the
of those produced by micro-organisms are mean time will have been loaded with a fresh
brought about in the nitrogenous as well as in piece.
the other constituents of the malt whilst sub- It is hardly necessary to say that in the
mitted to these conditions of temperature and process of kilndrying, where the temperature is
moisture. the important factor, several thermometers
As soon as the malt begins to present a dry placed on each floor are absolutely indispensable.
appearance, the temperature may be gradually The malt, after it is finished drj'ing, has yet
raised up to the final temperature at which it is to be freed from the radicles or ' combes.' This
to be finished off. It is impossible to give a used to be accomplished in the old maltings by
fixed limit for this, as a great deal will depend its being well trodden by men furnished with
upon circumstances, but, as a general rule, for heavy-soled boots ; the radicles being thus
pale malt the final temperature may be taken at detached from the corns, and by passing the
200F. From the time of raising the tempera- malt over a ' water-fall ' malt screen it was
ture until the end of the process, the malt should completely freed from these as well as from
be turned at intervals. some of the adhering dust. In modern maltings,
In drying the malt the great point to be as soon as the malt is thrown off the kiln, it is
observed is the maintenance of a perfectly even !
passed through a brushing machine, each kernel

'
temperature, so that the whole of the malt being brushed free from combes' and adhering
drying should be at any given moment of the dust. In some maltings, previous to being
same uniform temperature. brushed, the malt is heaped up in the centre of
In the old type of kiln the process of drying, the floor and remains so overnight with the fire
from time of going on to coming off kiln, usually well banked up.
occupies about four days, and is distributed as We may get a very fair idea of the tempera-
follows : ture at which the malt has been dried by observ-
the colour of the combes. The higher the
1st day not below 80 or above 100F. ing
2nd 90 110 temperature, the more highly coloured they be-
3rd 120 130 come ; indeed, where it is almost impossible to
4th 140 180-185 observe any difference in the colour of two malts
dried at different temperatures, an examina-
For the first two days the malt should on no tion of the combes from these malts shows it at
account be turned, but the surface forked over once.
needed. After the second day the
lightly, if After freeing from the combes
21. Storing.
malt should be turned at frequent intervals.
In the modern type of kiln the drying process
by screening, malt is usually stored away in bins
for some weeks previous to use in the brewery.
from the time of going on to coming off kiln The floor, sides, and top of these bins should be
usually occupies three days, and is distributed as
made of good seasoned wood and lined with
follows :
sheet sine. These bins are usually built in the
1st day not below 80 or above 100F driest part of the malthouse ; this would natu-
2nd 100 130
rally be in the neighbourhood of the kiln, and
3rd 130 200 it should be protected as much as possible from
The malt is not turned until the second draughts.
day. As soon as the green malt is loaded on During this storage of the malt previous to
the kiln, the fan is started rapidly, and by this use some change certainly takes place in its
means a strong upward draught is induced nitrogenous constituents ; in technical language,
'
which draws the moisture rapidly from the malt ;
the fire is taken out of it and the malt becomes
as the latter becomes dry, the temperature is mellow,' but, whatever these changes are, nothing
increased, and the speed of the fan is reduced. is known about them up to the present. All that
Medium and high-dried malts are finished off can be said is that it has been found decidedly
at much higher temperatures, ranging from unadvisable to use any malt for brewing purposes
200 to 230 and upwards. until it has been stored for at least six weeks
As soon as the temperature gets up to the from the time of coming off the kiln.
final point, this heat is in a great many maltings 22. Characteristics of malt. The following
maintained only for one or two hours. This is are the characteristics of a good malt, as given
a great mistake there can be no doubt that the
; by Slopes :
longer the malt is erposed to a high heat, the (1) Growth. The malt should be evenly
sounder and better keeping will be the resulting grown, the acrospire showing between two-thirds
beer. The final heat might certainly be attained to three-fourths up the back ; any malt which
in a shorter time than it usually is, and the contains many corns showing the acrospire pro-
malt might be exposed to this heat for at least truding should be rejected. On the other hand,
544 BREWING.
itshould also not contain more than 4 p.c. of 23. Malt adjuncts. These may be divided
ungerminated corns. into two classes. from
First, those substances
Slackness or moisture. This will vary to
(2) which the extract has to be obtained by the
a slight extent -with the age of the malt, but on mashing process and second, those in which the
;
the average, malt should not contain more than extract is already formed.
3 p.c. of moisture. Class I. Several grains of cereals other than
(3) Age. Malt is
at its best from six weeks to barley have been prepared for brewing purposes,
four months ; after that time, under ordinary either by malting or subjecting to the action of
conditions of storage, it gradually absorbs mois- heat in some way or other. The principal of
ture and becomes more or less slack. these which are at present used as substitutes
(4) Odour. Good
malt should have a pleasant, for malt, either in a prepared form or in the raw
well-known aroma peculiar to itself. state, are maize malt, germless maize, gelatinised
(5) Condition.
This will depend a good deal maize, gelatinised rice, torrefied grain or white
upon the quality of the barley. Good barley malt, and in the raw state barley, rice, and
badly managed may produce a bad malt, but a maize. When using any of these substances for
bad barley will never produce a good malt. brewing purposes, certain proportions of them
Good malt should be tender and friable when are either mixed with the malt in the mash tun,
broken, and should bite crisp and crumble or else the starch contained in them is first gela-
readily under the teeth. tinised in a separate vessel and rendered soluble
(6) Cleanliness.
Malt should be compara- by the addition of a little malt, and afterwards
tively free from mould and dust as well added to or sparged over the goods in the mash
as root-
letsand inorganic refuse. tun.
Flavour.
7. The flavour of malt is derived Class II.Under this head are included ordi-
from influences of growth and of drying ; it nary cane sugar, invert sugar, glucose or starch
should possess a pleasant, mellow, sweetish sugar, and dextrin-maltose.
taste, free from rawness on the one hand, and Raw cane sugar cannot be recommended as a
bitterness on the other. brewing material, owing to the large quantities
Such are the characteristics of a good malt of impurities of a dangerous character which are
so far as can be determined by the eye, but always present.
these should always be supplemented by a com- Refined cane sugar is used to a certain extent,
plete chemical analysis. 1 By this means we but before it can undergo fermentation it has
obtain the following information : first to be hydrated or inverted by a peculiar
I. Actual composition : unorganised ferment contained in the yeast and
a. Starch products, as dextrin and maltose. termed invertase, and as this reaction tends to
b. Cane sugar. weaken the yeast to a certain extent as well as
c. Other sugars. favour the production of lactic acid, it has been
d. Total albuminoids soluble after boiling. found more advantageous to use cane sugar
e. Ash. which has been previously inverted. This is
/. Moisture. done by means of sulphuric acid, which is after-
Insoluble matters or grains.
g. wards neutralised with calcium carbonate, and
Relative diastatic capacit}\
II. the inverted sugar freed from the calcium sul-
III. Specific rotatory power. phate by filtration is further purified by being
A
brewer ought to have a fair idea of the passed over animal charcoal, and then boiled
constituents of his malt before commencing to down under diminished pressure to a thick
mash with it, for from such an analysis as given syrup, in which state it is sent out by the
above he will be in a position to predicate very manufacturer.
fairly what kind of wort and 24. Hops. The hop plant belongs to the nettle
beer his malt is
going to produce, and so be enabled to control family, and is a perennial climbing or rather
not only his mashing process, but all subsequent twining plant. It is found hi the wild state all
operations. over Europe, and is propagated not by seed but
Other descriptions of malt, in addition to the by sets or suckers thrown up from the root,
kind we have hitherto been considering, are which is perennial, the stems dying down at
made and used. These are : the approach of whiter, and fresh ones coming
Brown or porter malt. up each spring, and often attaining a height of
Amber malt. 30 feet or even more. The hop plant bears
Black, roasted, chocolate, or patent malt. two distinct kinds of flowers, male and female,
Brown and amber malt are prepared prac- and these flowers again are produced on distinct
tically in the same way as ordinary malt until plants ; of these only the plant bearing fe-
they go on kiln. Here they are dried at a much male flowers is cultivated, the male plant being
higher temperature, and wood is largely used for rigidly excluded from most hop plantations.
the purpose instead of coal or coke. The flowers, which are the only parts of the
Black malt is simply ordinary malt which is plant of any use to the brewer, occur in the
roasted in exactly the same way as coffee berries form of peduncles or cones, consisting of a series
are.
'
A
sample of properly roasted malt is of scales or carpels lying above each other so as
uniform in colour, of a chocolate hue, not black, to form a cone. On the inner side and on the
and each com clear and clean. If it is black, lower edge the carpel is turned over and encloses
with the corns burst, and especially if matted or at first the female flower and afterwards the
run together, it is of a most inferior kind, and fruit developed from the flower. The fruits of
neither good flavour nor permanent colouring the hop are round hard granules or little nuts;
can be expected from it.' these fruits and the inner sides of the scales are
For full details of latestmethpds of analyses of malt,
1 thickly covered with a fine yellow dust the so-
worts, and beer, v. Sugar, Saccharimetry. called lupulin. Under the microscope this dust
BREWING. 545
is seen to consist of numberless granules, these parasitic diseases have made their appearance,
granules being composed of glands, which are sulphuring is decidedly injurious as well as en-
formed by the union of several simple cells. courages fraud. On the other hand, it seems
These glands are hollow, and this hollow space to be a pretty general custom
nowadays to
is filled with hop oil, resin, bitter principle, &c. sprinkle the hop plants whilst growing with
As a rule, the value of the hop may roughly flowers of sulphur, to prevent or
destroy certain
be determined by the quantity of lupulin it diseases which attack the plants at various
contains. stages of their growth such as mildew and
In practice the quantity of the hop flour blight but it is evident that very little of this
'
the condition,' as it is called is is to be found on the hop cones after
present picking ;
roughly estimated by rubbing the hops between but even if any should remain adherent,
being
the hands, the amount of stickiness left forming present as free sulphur, it can have little or no
an index as to the quantity of lupulin present effect on the constituent principles of the
hop.
in the hops. In order to estimate the value of hops with-
Hops are principally cultivated in the coun- out having recourse to analysis, the following
ties of Kent, Surrey, Sussex, and Worcester. physical features may be taken into considera-
The Kent hops are in much repute, and more tion : the fineness of the aroma, the proportion
especially that variety known as Golding, being of lupulin which the cones contain, the pro-
rich and delicate in flavour ; the Sussex hops portion of stalk, seeds, and impurities which
are somewhat coarser in flavour than Kent, and accompany the hops, and the geaeral appearance
perhaps do not present such a pleasing appear- of the cones themselves.
ance to the eye, but nevertheless are good useful The
following experiments (J. Inst. Brewing,
hops for running beers or for mixing with Kents xii. 301) were undertaken some years ago by
for higher-class ales. the writer, with a view to getting some definite
Worcester hops are milder than the above, idea of the action of the various salts occurring
and in some breweries much preferred to any in brewing waters upon hops. Both as regards
other. Of late years bad seasons and the attack the extractive properties of these salts as well as
of the hop aphis have done much to deteriorate the flavour and colour of the extract so obtained,
the quality of English hops, so that at present several experiments were made, of which the
large quantities are imported from Germany and mean value is given in the annexed table. The
America ; but foreign hops lack that delicate method of experiment was as follows : The dry
aroma and flavour peculiar to English growth, salts were added to distilled water at the rate
and are as a rule only used for the lower quality of 21 grains per gallon, or 0-3 gram per litre ;
beers. Hops, in order to be kept for any appre- 10 grams of hops were then digested with 900
ciable time, require to be thoroughly dried ; the c.c. of each solution in a boiling water- bath, for
hop cones, after they are picked, are spread out one hour, cooled down to ordinary temperature,
on the floor of a kiln, where they are dried by and made up to 1005 c.c. (10 grams of hops being
artificial heat. Sulphur is often sprinkled on found to be equivalent in bulk to 5 c.c. of water),
the kiln fires, and the sulphurous acid gas thus shaken well up and filtered as bright as possible ;
produced passing through the hops bleaches 100 c.c. contained the extract of 1 gram of hops.
them, so that hops naturally dark in colour or This quantity was evaporated to dryness, dried
unsightly in appearance are rendered more in water - oven and weighed until constant,
pleasing to the eye and fetch a higher price. then ignited and weighed again the latter ;
Thausing claims that it is decidedly beneficial weight subtracted from the former gave the
to subject hops to the sulphuring process on weight of organic matter extracted from 1 gram
the kiln ; but, unless where the mildew and other of hops (J. Inst. Brewing, xii. 300).
546 BREWING.
separated by decantation. During the boiling f. Gerammt Brauwerein, 1897, 168) confirms
d.
of the hops with the wort in the copper the thisview to a certain extent. He finds that all
if not all, of this oil becomes good hops contain high percentages of tannin.
greater portion,
volatilised and lost to the brewer ; hence a pro- Diastase of hops. Hops, like all other plants,
cess has been recently introduced for extracting contain diastase, but this point appears to have
this oil from the hops previous to boiling, and been overlooked until attention was called to the
afterwards adding it either to the wort oefore fact by Brown and Morris (Trans. Inst. Brewing,
ordinary fermentation or to the finished beer. 1893, 94).
When obtained from fresh hops, the oil has The tannic acid which occurs in hops is a
a light-yellow colour, hot burning taste, and fawn-coloured powder, easily soluble in water
agreeable aromatic smell. It is only slightly and weak alcohol, but insoluble in ether. In
soluble in water, but freely so in alcohol, ether, aqueous solution it gives a dark-green coloura-
and light petroleum. Not only is the hop oil tion with ferric chloride, and possesses the pro-
volatilised at temperature of boiling water, but perty of precipitating in flocks the albuminous
also slowly at ordinary temperatures and by ex- bodies of malt wort. It is therefore an eminently
posure to air is easily oxidised into volatile acids, useful substance in the manufacture of beer.
especially valerianic acid, to the presence of From the foregoing it would appear that the
which the peculiar odour found in old hops is only substances in hops of any use to the
due. brewer are the soft resins and tannic acid.
A. C. Chapman has investigated the com- These soft resins are readily oxidised into the
position of hop oil and has found it to consist hard and insoluble variety, whilst tannic acid
principally of myrcene and a sesquitespene which is capable of
being converted in like manner
he has termed humulene, together with small into gallic acid, a substance possessing very
quantities of linolool and linatyl isononoate. few of the properties of tannic acid. It is
This hop oil is generally found intimately not, then, a matter of surprise that old hops
mixed with resin, which it seems to be capable are of little or no value, for considering the
of dissolving to a certain extent. It seems very loose manner hi which they are housed in most
probable that the resins of the hop (three of breweries, subject to every variation of tempera-
which have been determined) are the results of ture and freely exposed to the air, changes in
the oxidation on the one hand of the hop oil, and the composition of the active principles must of
on the other of an organic acid. Bungener (Bull. necessity take place in a more or less rapid time,
Soc. chim. 45, 9), who has isolated it from hops rendering them eventually of little or no value
and studied its properties, has termed it lupidinic to the brewer.
acid. Hayduck (Wochenschrift fur Brauerei, Briant and Meacham (Jour. Fed. Inst.
1887, 347) has detected three different resins in Brewing, 1897, 3, 487) have described numerous
hops one a soft resin, precipitable by lead experiments which they had conducted to dis-
acetate and soluble in petroleum ether ; a second, cover the best method of storing hops. They
also soft resin, soluble in petroleum ether, but recommend the use of a cold chamber at a
not precipitable by lead acetate ; and a third temperature of 36 to 40F.
one, hard and solid, not soluble in petroleum ether This method of storing has been proved to
and not precipitable by lead acetate. Experi- give excellent results, and has been very
ments made by Hayduck show that the second generally adopted throughout the trade.
of these resins is identical with the soft resin 26. Yeast and fermentation. Before the
formed by the oxidation of Bungener's lupidinic classical researches of Pasteur, various theories
acid, whilst the third resin is due to the oxidation were advanced to account for the phenomena
of hop oil. Hayduck also shows that the soft connected with fermentation, but he was the
resins possess highly antiseptic properties, whilst first chemist who proved that the process of
the hard one checks to a certain extent the fermentation was due, not to a peculiar proto-
rapidity of fermentation. It was found that plasmic substance secreted by the yeast fungus,
when these resins were repeatedly extracted but that the presence of the plant itself in the
with water the aqueous solution gradually de- saccharine liquid is essential to alcoholic fer-
creased in antiseptic power ; this tends to show mentation, and that the yeast cells have the
that it is inadvisable to boil hops more than power, in the absence of the oxygen of the air,
once, since the first boiling would probably of splitting up sugar into alcohol and carbonic
extract the greater portion of the soft and more acid, and deriving the oxygen necessary for their
soluble resin. support and nourishment by that means.
Although it is possible to estimate with a Pasteur has shown that easily fermented
fair degree of precision the various constituents saccharine solutions can remain for years with-
of hops, it has not been so far found possible to out decomposing, even when the air has access
establish any very definite relation between the to them, provided that the living germs which
value of the hops and the amount of essential oil, were originally present in those solutions be first
resins, and tannin which they contain. Conse- destroyed by heat, and that care be taken not to
quently, up to the present time, chemistry has let any but absolutely pure, that is, germ-free
not afforded much assistance in this direction. air enter those solutions afterwards. But the
Briant and Meacham (Jour. Fed. Inst. Brewing, moment impure air was allowed to enter the
1897, 2, 233) have proposed a method for the liquid, or the minutest portion of living yeast,
valuation of the preservative power of hops fermentation was rapidly set up.
which consists in estimating the amount of soft Pasteur has also shown that associated with
resin they contain. Heron proposed to estimate
ordinary yeast are to be found in most fermenta-
the value of hops by the amount of tannin they tions and beers a great number of organisms of
contain. He considers that the larger this quite a different appearance and character
to
amount is the better the sample. Barth (Zeit. yeast cells, and which may all be classed
under
BREWING. 547
the general term of bacteria, and he proved most wort, but for some time after the yeast cell con-
conclusively that these organisms are capable of tinues to produce any buds, and even after the
and do give rise to the various diseases to which rupture takes place between the parent cells and
beer is subject. Or in other words, that, in the resulting daughter cells, the former still
addition to the healthy fermentation of saccha- continue to absorb various substances from the
rine solutions carried on by sound yeast, these liquid. This may be looked upon as a kind of
other organisms, if present, are also capable fattening process, and is due to the assimilation
under certain conditions of carrying on fer- by the yeast of certain nitrogenous matters con-
mentations which give rise to products other tamed in the worts. Hence the process of fer-
than alcohol and carbonic acid. Hence these mentation of malt worts may be regarded as
bacteria or false ferments have been classified first an absorption of carbohydrate substance by
and named according to the functions they fulfil the yeast cell, the transformation of this sub-
or the products they give rise to. stance into alcohol and carbonic acid, whilst at
Those organisms which induce alcoholic the same time the oxygen derived from this
fermentations in a saccharine solution are known decomposition enables the yeast cell to thrive
under the general name of saccharomyces, and and grow and to put forth buds.
since under normal conditions they reproduce When this period of growth is accomplished, a
themselves by gemmation or budding, they have fattening of the cells takes place at the expense
been assigned to that division of the great fungus of the nitrogenous bodies readily assimilable by
group known as budding fungi. In brewing yeast and which consist principally of amido-
technology they are known under the general and amino- acids (asparagin, trypsin and leucine) ;
'
term yeast. Yeast cells are either single or occur if no assimilable nitrogen be present this fatten-
'
in groups or strings each cell consists of a thin-

.
ing does not take place, and the yeast becomes
walled sac or bag containing a semi-fluid matter, starved, as it were, and perishes ; if, on the other
in the centre of which there is often a space full hand, there be a large excess of these nitro-
of a more clear and watery fluid than the rest, genous matters in the worts, the yeast cells
which is termed a vacuole. The sac is com- become overfed, and their capacity for repro-
paratively tough, but it may easily be burst, duction considerably diminished, for it has been
when it gives exit to its contents, which readily found that the power of multiplication and the
diffuse themselves through the surrounding formation of new cells decreases with the increase
fluid. The whole structure is called a cell, the of nitrogen in the yeast.
sac being the cell wall and the contents the proto- It is essential, therefore, that the brewer
plasm. Under a high magnifying power each obtains a wort which is both constant in quality
cell is seen to be round or oval, and on the and definite in composition, and which exactly
average about Û inch in diameter. An agglo- suits the type of yeast he employs. For a type
meration of such cells is technically termed is produced by environment, and varies as the
'
and to the naked eye appears as a thick,
yeast,' composition of the wort varies.
slimy cream-coloured fluid, from which all the A wort produced entirely from malt contains
moisture can be pressed, and the residue dried a large excess of assimilable nitrogenous sub-
at. a low temperature to a
powdery mass without stances, and is hardly an ideal medium for yeast
losing its vitality ; but if heated in the moist production and vitality.
' '
It is found advan-
state to the temperature of boiling water, its tageous to dilute these nitrogenous bodies
fermentative power is completely destroyed. with a certain proportion of material devoid of
Fermentation which has already commenced in yeast nutriment. Raw or gelatinised grain,
a saccharine liquid can be stopped by boiling it. invert sugar, glucose or other similar brewing
When a minute quantity of yeast is added to sugars are used for this purpose. A very satis-
some malt wort which has previously been factory grist is composed of the following pro-
filtered bright, and is then kept in a glass flask portions: 60-65 p.c. malt, 18-22 p.c. brewing
at a temperature of about 70F., after a few sugar and 13-18 p.c. unmalted cereal.
hours bubbles of gas will be seen to rise to the Among the factors which exert a considerable
surface of the liquid, which gradually becomes influence on the progress of fermentation,
more and more turbid, and later on a sediment besides that of the chemical composition of the
will be observed at the bottom of the flask or a liquid, temperature and the amount of oxygen
scum may collect at the surface, carbonic acid present in the liquid may be mentioned. This
gas being copiously evolved. If the yeast cells much is known of the effect of oxygen on the
be carefully examined under the microscope from progress of brewing in practice, that hi order to
time to time whilst this is going on, it will be get a good result it is a necessity to aerate the
noticed that at first the vacuoles which were wort, i.e. to let it take up oxygen from the air.
present in every cell gradually disappear, each Pasteur's researches on this subject led him to
cell becoming full and rounded in appearance state that fermentation is life without air,
owing to the absorption through its cell wall of and that yeast can only decompose sugar by
certain nourishing substances from the wort. taking the necessary oxygen from the sugar
Soon minute little buds will be noticed jutting molecule. His theory has, however, proved to
i
out from the sides of the cells ; these buds be wrong. A deeper insight into the influence
rapidly grow and soon assume the size of the of aeration on fermentation in breweries could
parent cell, from which they finally become de- !
only be obtained by the study of pure culture

t ached, but not before
they in their turn have !
species and races, for, as Hansen's investigations

developed other buds, and these yet others, thus j
in brewing practice have shown, they behave
giving rise to those groups or strings of cells which differently with respect to oxygen. Hansen
are sometimes seen under the microscope. This found further that when the yeast cells have free
cell reproduction and access to the oxygen of the air they can yet
growth is due, then, to the
nourishment which the yeast derives from the produce an active fermentation, an observation
548 BREWING.
which contradicted the theory of Pasteur. bottom of the vats or casks, in contradistinction
Adrian J. Brown observed that a plentiful supply to the English method of fermentation termed
of oxygen increases the fermentative activity of high fermentation, and the yeast, top yeast,
the single cell, even when the cells are in such because here the process is conducted at a high
circumstances as prevent multiplication (Chem. temperature commencing at about 60F. and
Soc. Trans. 1892, 1894). running up to 70F. or more, so that the fer-
Not only has Pasteur established the fact mentation is much more rapid and the yeast
that fermentation is due to the development and thus produced rises to the surface and works out
growth of yeast in saccharine solutions, but he of the bungholes of the casks or is skimmed off
has also shown that there are seVeral distinct the surface of the fermenting tuns.
species of yeast, each one differing from the A great deal of practical work has been done
other in functions and properties, and of the in the way of pure yeast cultivation on the
several species which are capable of inducing large scale in English breweries with varying
alcoholic fermentation he identified the following results. H. T. Brown and G. H. Morris carried
as being present in malt worts, in addition to that through a series of experiments between the
species known as Saccharomyces cerevisice, the years 1885-94 in a large Burton brewery, but
true beer ferment, Saccharomyces pastorianus, found that although the beers produced were
S. ellipsoideus, S. exiguus, and S. apiculatus. sound, they hardly ever came into condition, and
These he found were always present in the atmo- no secondary fermentation occurred, unless after
sphere as well as on the surface of all fruits, so the addition of malt extract or sugar priming.
that if some sweet wort be freely exposed to the Later investigators have found that for many
air, it will in the course of a few hours manifest ales the system can be adopted with very satis-
all the signs of alcoholic fermentation ; but, in factory results, as they have found that in this
addition to these various species of yeast, spores type of beer, fermented with a single-cell yeast,
of bacteria and moulds will also manifest them- a continuation of the primary fermentation
selves and develop, so that after a few days, if occurs after racking and lasts for about a fort-
left to itself, this wort becomes quite turbid, is night. It is conclusively proved that the true
covered with a thin film, emits a disagreeable secondary fermentation, such as occurs in the
smell, and soon putrefies. Hence the necessity case of stock ales when stored for a considerable
for boiling the wort before fermentation ; by period, is not brought about by primary yeast,
this means all the spores which may have been and hence the failure of Hanson's system in the
present, derived in great part from the surface of English breweries.
barley or malt, are killed and the wort rendered N. H. Claussen has studied the yeasts which
free from all foreign germs, and ready to undergo bring about the secondary fermentation hi
a true yeast fermentation. English beers (J. Inst. Brewing, 1904, 10, 308),
But although Pasteur directed attention to and has discovered a non-sporulating budding
the presence of these other forms of saccharo- fungus belonging to the Torula group which
myces or wild yeasts, as they are now termed, in possesses the special property of setting up
fermenting worts and beer, he did not tell us secondary fermentation, and even creates in
how to introduce into the liquid about to be fer- Continental beers that flavour and condition
mented a seed yeast which is really free from typical of English beers. He gives the name of
all such forms of wild yeast. This work was Brettanomyces to this organism, and holds the
reserved for Hansen, and was brought to a most belief that it is a constituent of the pitching
successful issue by him. He started with the yeast.
idea of cultivating a crop of yeast from a single Sufficient has been done to prove that in
selected yeast cell, and pure yeast thus procured ordinary brewery yeast the English brewers
was first used for brewing purposes at old Carls- also possess a mixture from which, by Hansen's
berg Brewery, near Copenhagen, in 1883 (Med- method, several varieties of S. cerevisice can be
delelser fra Carlsberg Laboratoriet, 1881). In separated, which cannot microscopically be dis-
that year he brought forward his doctrine that tinguished from each other, but which, when used
some of the most dangerous and most common upon a practical scale, give entirely different
diseases of low fermentation beer were caused,
.
results, both as to flavour, brightening, attenu-
not by bacteria, but by certain species of ation, and mode of separation of the yeast.
Saccharomyces, and that each of the names em- Experiments have also shown that these charac-
ployed by Rees S. cerevisice, S. pastorianus, teristics can be maintained unimpaired through-
S. ellopsoideus represented not one but several out a very great many successive fermentations
kinds or races. He showed that varieties which in the brewery (Morris, J. Soc. Chem. Ind. 188T,
had been until then incorrectly grouped under 113).
the name of Saccharomyces cerevisice gave in Great differences have been found to exist in
the brewery products having quite different the fermentative capabilities with regard to
characters. Since then, carefully selected types different sugars. Most yeasts ferment glucose
of yeast from pure cultures on this method have and fructose, but there are several types which
been introduced into all the leading breweries of are unable to ferment such sugars as maltose,
Denmark, Norway, and Bavaria, with the most cane sugar, and milk sugar. This difference is
marked success. So far, all the work that has evidently dependent upon the enzyme which the
been done with pure yeast relates to that parti- yeast is able to secrete. It has long been known
cular variety which is employed on the Continent that cultivated yeast secretes an enzyme called
and known as bottom yeast, or low fermentation invertase, which hydrolyses cane sugar, con-
yeast, so called because the fermentation is there verting it into the more readily fermentable
carried on at a low temperature (47F. or even It has more
sugars dextrose and laevulose.
lower), and is a slow process extending over some recently been found that these yeasts secrete
weeks, during which the yeast sinks to the another enzyme, maltose, which converts mal'
BREWING. 549
into glucose, previous to its fermentation. As tries, hasbeen patented by the writer. It
long ago as 1858, Traube brought forward a simply consists of the admixture of ordinary
theory relating to fermentation, which, however, pressed yeast with solid glucose. The glucose
received little credence at the time. According to is first melted by heat and allowed to cool, when
this theory, fermentation is explained as an effect it does not immediately set, but remains
liquid.
due to the various enzymes contained in yeast, The brewer's yeast is first pressed and than in-
and not to the yeast cell itself. This theory has corporated with it, when the whole mass sets
been practically confirmed by the discoveries hard in the course of a few hours ; the yeast is
of Emil Fischer (Ber. 27, 1894 and 28, 1895) thus, so to speak, imprisoned in the crystallised
and Ed. Buchner. Fischer's investigations on glucose, yet without being completely dried up,
enzymes have not only brought to light new and retains its fermentative power with but
but have also pointed to quite new views
facts, slight diminution for a very long period.
as to the nature of the processes concerned. In Aa we have seen, the microscope deea not
1897, Buchner, by submitting yeast to high enable us in some instances to differentiate one
pressure, succeeded in obtaining an extract form of yeast from another, and in order
capable of producing fermentation in solutions to be able to do this some other method must
of sugar. He concluded from his experiments be resorted to. It has long been noticed by
that the active element in the expressed juice many observers, more especially by Rees, Engel,
was an enzyme which he called zymase. Its and Brefeld, that under certain conditions the
fermentative power he found to be several yeast cell, instead of throwing out a bud, multi-
hundred times less than that of living yeast, and plies itself in another way : its protoplasm divides
it loses its activity on keeping. itself into four masses termed ascospores, each
This activity is not influenced by yeast cells of which surrounds itself with a cell wall, and
nor this activity,
is when lost, restored by the the whole are set free by the dissolution 01 the
action of living cells. cell wall of the parent.
A
very large amount of work has been done Hansen found that the ordinary bottom-fer-
since 1897, as the direct result of the new series mentation yeast only formed spores at 25(J.
of investigations provided by Buchner's re- after some days, whilst the wild forms are
searches, both in England and abroad. A capable of forming ascospores at this tempera-
valuable resum6 of these researches will be ture in a few hours, and upon these results
found in two papers read before the Institute Holm and Poulsen (Meddelelser fra Carlsberg
of Brewing by Dr. Arthur Harden Inst. (J. Laboratoriet, 1886) have based a method for the
Brew. 1905, 11, 2-15, and 1910, 7, 663-634) practical analysis of brewer's yeast. The method
(v. FERMENTATION). of procedure is as follows : A
small quantity
Hansen found that particular formsof disease of the yeast to be examined is spread on a small
which manifest themselves in beer after it has sterilised block of plaster of Pans ; this block is
been stored in cask are due to the presence of then placed in a flat covered glass dish and
species of wild yeast (Meddelelser fra Carlsberg kept moist by water previously poured into the
Laboratoriet, 1883), and notably to certain varie- dish. This is then placed in the thermostat or
ties of S. pastorianus, but he has also shown forcing chamber, and kept at a temperature of
that if these wild types are present to the extent 25C. for forty hours. At the end of that time
of not more than 2-5 p.c. on the total it is carefully examined under the microscope,
quantity
of yeast, they do not develop their particular when the spores, if any wild yeast be present,
form of disease. Brown and Morris (Non-crys- will be seen as round bodies within the cell wall.
tallisable Products of the Action of Diastase Grove Johnson and S. Hare (J. Inst. Brew-
upon Starch, Chem. Soc. Trans. 1885, 569) have ing, xi. 467), in the course of some bacterio-
'
found that some of these wild types of yeast,' logical experiments, accidentally discovered a
8. pastorianus and 8. ellipticus, which with other new yeast, to which they gave the name of
species constitute the secondary ferments of our Saccharomyces thermantitonum, owing to its
high-fermentation beers, are capable of first power of resisting high temperatures. It proved
hydrolysing the dextrin to maltose and then to be a true yeast, forming spores at definite
fermenting it, and these results have been fully temperatures and capable of setting up a
confirmed by the author on the large scale in vigorous alcoholic fermentation in a saccharine
the brewery. It is perfectly certain that the solution at a temperature of 110-130F. Prof.
' '
sick frets and other diseases which
prevail in Lindner states that this new yeast differs from
summer-time amongst certain kinds of beer, are Logos yeast in that it precipitates in a much
due to the presence in large quantity of these more compact mass. He further states that at
wild yeast types in the beer. 109F. the fermentation proceeds quickly and
There are also present among the secondary normally, and the yeast retains its ability to
ferments of our top-fermentation beers several isolate itself in large lumps, thereby causing a
types of the Torula group, one type of which has spontaneous clarification of the wort.
been investigated by Claussen, as already men- Yeast has always been classified as belonging
tioned. By Torula, Hansen understands yeast to the fungoid group of plants, but those other
cells which are similar to
Saccharomyces, but do organisms which also have the power of in-
not form endospores nor develop ducing fermentation other than alcoholic in
typical mould
growths. As regards the production of alcohol, saccharine solutions, have been regarded by the
they may exhibit this in all degrees. Com- older observers as belonging rather to the animal
paratively little is known as yet with regard to than to the vegetable kingdom, chiefly on ac-
these yeasts, but no doubt in the near future count of their motility and in the absence of the
they will be more fully investigated. basis required for a more exact comparison, but
A method for the preservation of yeast later investigators see no reason for separating
whereby it can be transported to foreign coun- them from the vegetable kingdom, although all
550 BREWING.
that can yet be said of them is that they may be municating with the measuring apparatus is
'
classed as bacteria, and are a group of simple connected, to the other a stout piece of india-
plants of a low order.' rubber tube which can be closed by an ordinary
Of these the species best known to us as burette clip. The measuring apparatus con-
occurring in beer are Saccharobacillus pas- sists of a U-shaped tube, one limb which is con-
torianus, Bacillus amylobacter, Bacterium termo, siderably wider than the other, is constructed to
Bacterium aceti, Bacterium lactis, and Sarcina. hold 500 c.c. and is graduated into 10 c.c. divisions.
There are other species of which little is known, The extremity of the narrower tube carries a
but which are often met with in old beer, such funnel-like expansion, and is provided at its
as the ropy ferment, colour bacterium, certain lower end with a tap ; the upper extremity of
forms of vibrio, spirillum, &c. the wider limb carries a narrow tube bent at a
These constitute what are known as the right angle, and also a tap.
disease germs of beer, and generally develop When a determination is made, 10 grams of
under favourable conditions in the finished beer yeast under examination are intimately mixed
after it has been some time in cask or bottle. with 400 c.c. of a 10 p.c. solution of cane sugar,
Bacterium aceti has the power of converting and introduced into the flask. This is then
the alcohol of the beer into acetic acid ; B. lactis placed in the water-bath, which has been pre-
attacks the saccharine matter, converting it into viously heated to and is now constantly main-
lactic acid ; whilst butyric acid is supposed to be tained at a temperature of 86F. and is allowed
derived from the further fermentation of lactic to remain uncorked for an hour ; in the mean
acid by means of Bacillus amylobacter, or from time the measuring apparatus is made read)'.
sugar along with butyl alcohol by means of the Five c.c. of paraffin oil are first poured into the
same organism. These three forms of bacteria funnel, and afterwards water. This latter drives
are perhaps those most commonly occurring in the oil before it, and this, when it enters the
beer. measuring chamber, floats on the surface of the
A few forms of mould are sometimes met water and prevents the absorption of carbonic
with, such as Mucor racemosus, Penicillium dioxide. Sufficient water is then introduced to
glaucum, Aspergillus niger; but space will not bring the surface of the paraffin layer to the zero
permit to treat further of this subject. mark on the scale. After the flask has stood for
Energy of fermentation. Leaving out of con- an hour in the water-bath, the apparatus is
sideration the different physiological conditions connected up, the tube c being left open while
of the yeast, the various races show marked this is being done. This is now closed with the
differences in their fermentative activity. This clip, the tap D opened, and the time noted as
can be estimated by observing the amount of fermentation proceeds. The disengaged gas
gas evolved in a given time. The apparatus gradually displaces the liquid in the wider limit,
shown in Fig. 9 is used for the purpose, and and the tap E is opened just sufficiently to allow
the water to escape at the same rate as the gas
enters. At the expiration of half an hour, the
taps D and E are closed, the clip c is removed, and
with the assistance of the pointer the level of the
liquid in the two limbs adjusted to the same
height, either by pouring water into the funnel
or drawing it off by the tap A, and the quantity of
collected gas read off.
27. Having very briefly glanced at the dif-
ferent materials used in brewing, we proceed
next to consider the various processes involved
in the manufacture of beer.
Preparation of malt for mashing. As soon
as the malt is delivered at the brewery it is
further cleaned by screening from adherent dust,
mould spores, and small corns. It is then de-
livered into a small hopper, from which it passes
to the malt mill. This consists of a pair of
smooth steel rollers, or, preferably, of two pairs
!
of such rollers, one pair of rollers being set to a
wider gauge than the other. When passing
I
through such a set of rollers the larger corns are
1
crushed by that pair which is set so as to crush
them sufficiently but not too much, whilst the
j
smaller corns pass on to the other pair, which
are set at a narrower gauge so as to ensure the
FIG. 9. complete crushing of every individual corn. By
this means a comparatively even grist is ob-
consists of a flask, A, containing the yeast and tained. As the malt is ground it passes to the
a solution of cane sugar. It is placed in a water- which is generally placed
grist case (c, Fig. 10)
bath provided with a perforated false bottom, over or has command of the mash tun.
the contents of the bath being kept at a constant The case should be made of well-
grist
temperature of 86F. The flask A is furnished seasoned pine or deal, planed smooth and well
with an indiarubber cork having two perfora- or
jointed, and should be lined with sheet zinc,
tions, into each of which short pieces of glass tube it may be constructed of galvanised iron. The
are inserted. To one of these the tube com- bottom of the grist case must be of sufficient
BREWING. 551
slope to allow of the grist falling easily and when used, are constructed of staves of best
readily into the mashing machine, and is pro- English oak, with a bottom of Dantzic fir. The
vided at the bottom with a sliding valve. staves should not be less than two and a half
28. Mashing process. From the grist case inches thick for small tuns, which must be in-
the crushed malt passes on to the outside creased for larger tuns in proportion to their
mashing machine, where it meets with the size. The mash tun is provided with a false
mashing liquor at a temperature varying, ac- bottom, an internal mashing machine, and a
cording to circumstances, from 160F. to 170F. pipe, termed an underlet, for introducing hot
The malt and water are here thoroughly mixed liquor from the main into the mash tun when de-
before running into the mash tun. The best sired. The capacity of the tun should be such as
form of machine for this purpose, and the one to allow three and a half barrels for every quarter
most generally em- of malt to be mashed ; to this must be added an
ELEVATOR
L
ployed, is Steel's masher, allowance of 3 inches to the depth of the tun.

of which a section is The false bottom, of such a thickness as to
shown at Fig. 10, D. This leave a space of 2 inches in depth between it
consists of a horizontal and the real bottom of the tun, consists of a
cylinder closed at one series of well-fitting stout sheet-copper plates
end and open at the perforated with small holes or slots one-eighth
other, from 3 to 6 feet of an inch in size and about 1 inch apart, and
in length and from 8 to supported by wooden bearers. The internal
22 inches in diameter. mashing machinery consists of a horizontal shaft
It is fixed horizontally rotating at a level of about half the depth of the
above the level of the tun round a central vertical shaft as well as on
upper edge of the mash its own axis, and fitted with light iron bars
tun, and is usually fur- placed at regular intervals along the length of
nished with a shoot the shaft, which by their motion more effectually
whereby the mash may mix up the grist in the tun. 2
be conducted into one One or more pipes, termed underlets, by
or more
tuns. For in- means of which hot water can be introduced
stance, where two mash i into the tun under the false bottom for the pur-
tuns are employed, the pose of raising the temperature of the mash
steel mash- when required, should be affixed to every mash
er is fixed tun. This heating is termed piecing up, and the
between hot water run in for the purpose, piece liquor.
the two The relative proportions of a mash tun are
tuns in such a matter of some importance. Table V., given
E a way that
j
by Southby for the form of mash tun we are
it can be describing, shows these proportions.
used for j
For the purpose of drawing off the aqueous
either one I extract of the malt, or in technical language
sweet wort, the bottom of the
mash tun is provided with a suit-
able number of pipes, which should
be attached at regular intervals to
the bottom of the tun so as to
at pleasure. Inside the ensure an equal draught from
cylinder and every portion. Of course, the
running its
whole length is a shaft number of such draw-off pipes must
provided with spokes at vary with
short and regular the size of
intervals,
and of such a length that the tun. A
they just revolve 25 - quarter
freely
inside the cylinder as mash tun
shown in section. should have
The shaft is driven by at least six
a pulley, and the grist is dr a w- off
fed intothe upper side pipes.
through the uprightT-piece, FIG. 10. l
The mash
the water from the hot
liquor back meeting
the grist at this point. TABLE V.
A accurately adjusted by means of a
slide,
screw, regulates the fall of the malt, whilst a Quarters
of malt
screw tap allows of the admission of the mashed
proper
quantity of water.
The process of mashing is carried on in a
vessel called a mash
tun, B. This may be made
of wood, wood lined with
copper, or of iron, but
the material most is iron,
generally employed
as it is found to last much longer than wood
very
and is more
easily cleaned. Wood mash tuns,
'For the drawings of brewery plant, the author is
aebted to Mr. J. Oxley, brewers' engineer, Frome.
552 BREWING.
tun in all instances is provided with a cover. rapidly replaced by copper covers, generally
This should be carefully made and should 'fit hood-shaped, hung on chains, and worked by
well ; it prevents the cooling of the mash and pulleys and weights so that the hood can be
protects the surface of it from dust. readily lowered or raised as desired.
This cover may be of two forms, square top The draw-off pipes to which taps are affixed
and conical, but the one to be most preferred is are carried separately from the mash tun to a
'
undoubtedly the conical. The square top, which small receiving vessel termed the underbade,'
is of the same diameter all the way up as the into which the wort from each tap flows, and is
mash tun, and is from two to two and a half feet conveyed from this to the copper.
in height, is provided with doors or sliding Figs. 11 and 12 give a general view of all the
shutters. The great objection to this form is mashing arrangements described above.
the large amount of space left above the mash, As we have said, the malt as it leaves the
and the facility afforded by the flat top for the grist case meets in Steel's mashing machine
collection of dust. with the hot liquor, and both, thoroughly inter-
The conical cover is made in irregular sections, mixed, are run into the mash tun. As soon as
all of which are removable, whilst the objections all the grist is run in, a few gallons of
mashing
to the square top are reduced to a minimum. liquor are run through the Steel's masher, and
Both these types of covers, however, are being then the rakes are set going, two turns round
FIG. 11. MASHIKG ROOM IN MESSES. WORTHINGTON & Co.'s BREWERY, BURTON-ON-TRENT.'
the tun being considered sufficient. The tem- which becomes rapidly converted into dextrin
perature of the mash is then taken ; this may and maltose ; the proteo-hydrolyst or proteo-
vary from 140F. to 150F. according to the !
lyticenzymes act upon the nitrogenous or al-

practice of the brewery. If this initial tempera- ! buminoid bodies, converting them into less
ture is not up to the proper point, then some I
complex and more soluble compounds, some of

more hot liquor is introduced through the under- which are hi a form readily assimilable by yeast.
|
let until the The other carbohydrates, such as dextrose, cane

right temperature is attained the ; i
covers are shut up and the mash allowed to i

sugar, and Isevulose (known as the ready-formed
stand, generally for one and a half to two hours. sugars of malt), also enter into solution.
29. The chemical changes which occur
j
during The action of the proteolytic enzymes

mashing. When ground malt is brought into peptase and tryptase is practically a continua-
contact with water at the j
tion of the action taking place on the growing

mashing temperature,
the starch which it contains becomes floors during the process of malting, but is some-
gelatinised
and the several enzymes present in the malt are what restricted, owing to the temperature of the
enabled to perform their several functions. The mash being above the maximum of activity of
amylo-hydrolyst or diastase acts upon the starch, these ferments. The action consists, as already
1
This, with Fig. 15, are taken from Noted Breweries of pointed out earlier in this article, in the pro-
Great Britain, by kind permission of Sir J. Causton & Sons. duction of albumoses, peptones, and amides and
BREWING. 553
ammo -acids, the latter, the lowest type of nitro- 66C. (150-8F.), the conversion of starch into
genous bodies formed, being those most readily dextrin and maltose, and the subsequent hydra-
assimilated by yeast. tions of the higher dextrins into the lower seem
Recent researches have proved most con- to be almost completed by the end of the first
clusively that when gelatinised starch is acted 15 minutes, and even for the transformation
upon by diastase it is split up into dextrin and at 66C. there is a fall of angle of only 10 from
maltose, and, under certain conditions, into 15 to 60 minutes, whilst for the first 15 minutes
maltodextrin as well, and that this change is a the fall is three times as much.
molecular one, and does not take place according
to one equation, but to several, depending upon
j
TABLE VII.
the temperature at which such a transformation
is effected, and that the conversion afterwards
of the dextrins first formed into maltose is a
slow and gradual act of hydration. In all proba-
bility the molecular transformations of starch
may be represented by at least eight possible
equations, depending upon the temperature at
which such transformations are effected.
The following table gives the respective pro-
portions of maltose and dextrin corresponding
to these eight equations, as well as the cupric-
oxide reducing power K and specific rotatory
power [o] D (3-86 divisor), for the joint products
of each of these transformations :
TABLE VI.
No. of
transfor-
mation
554 BREWING.
exists between them, the nature of the curves solved out and transformed by the diastase still
being almost exactly the same in both cases, a remaining into dextrin and maltose. If the
comparatively rapid fall occurring during the sparging be applied at too high a temperature,
first 30 minutes, slow and regular hydration this starch becomes gelatinised, but, in great
proceeding afterwards, but only to a slight ex- part unconverted, owing to the destruction of the
tent, the difference in specific rotatory
power diastase at these temperatures, passes on into the
between 30 minutes and 120 being only about wort, and although this starch of itself exercises
7 in each case, so that it may be taken for very little if any injurious influence on the
granted that the dextrin maltose ratio that is finished beer, it nevertheless serves as an index
to obtain in the resulting wort is practically of other dangers, for the high sparging tempera-
decided during the first 30 minutes. On com- tures which bring into solution some of the pre-
paring the curve at 66 in Table VII. with viously unacted upon starch, also cause some of
those at higher and lower temperatures, it would those nitrogenous bodies which at the ordinary
appear, curiously enough, as if this temperature mashing temperature are quite insoluble, to be-
for mashing were just on the boundary line as it come partly soluble, especially in the presence
were, a few degrees either higher or lower giving of the saccharine matter of the wort ; and these,
worts highly dextrinous and poor in maltose, or finding then- way in a state of semi-solution into
else the very opposite. the finished beer, cause a persistent cloudiness,
Seeing, then, what a very great influence a which neither finings nor storage can remove,
few degrees of temperature would appear to besides offering encouragement to the develop-
exert upon the composition of the wort, too ment of hurtful germs always present to a greater
much stress cannot be laid upon the necessity or less extent in freshly racked beer.
of attending carefully to the initial temperature As soon as the mashing process is considered
of the mash, and there can be little doubt that to be complete, which is generally about 2 hours
the polarisation of samples of wort taken, after starting, the taps leading from the various
say, at 15, 30, and 45 minutes from the underlets are opened, gently at first and after- .
time of finishing mashing, would give an inwards more quickly, till the liquor runs half-bore
telligent brewer much valuable information as and the wort is allowed to flow into the under-
to the relative diastatic capacities of the several back. The first few barrels that come over are
malts he may have to deal with, enabling him to generally cloudy, owing to the presence of small
form a pretty accurate idea as to the most suit- particles of the mash which have passed through
able temperatures for future mashings, and the perforations in the false bottom, and partly
giving him a more perfect control over the subse- from a reduction of temperature of the wort
quent operations of sparging, pitching, attenuat- through coming in contact with the cold pipe.
ing, &c. This cloudy wort is returned to the mash tun.
By an intelligent restriction of the diastase As soon as the taps begin to run fairly bright the
in the mash tun by means of careful manipula- wort is allowed to flow from the underback into
tion of the initial temperatures, therefore, a brewer the copper.
is able to regulate approximately the carbo- When the mash is completed and the wort is
hydrate matter which will exist in the finished running into the copper, the temperature of the
beers. liquor, or tap heat, as it flows from the taps is
Thus for stock ales a comparatively high per- taken. This is generally done about half an
centage of carbohydrates, unfermentable by hour from time of first setting taps.
primary yeast, is necessary in the beer at time of 30. Sparging. After a certain number of
racking, consequently rather high mashing heats barrels of wort have been drawn off, a further
are employed. Using an average pale ale malt, quantity of mashing liquor is sprinkled over the
an initial temperature of from 68 to 70C. goods by means of a sparger, for the purpose of
(155-158F.) is usually obtained with underlet washing out as completely as possible the wort
at 77C. (170F.). For mild ales where a low still adhering to the insoluble matter or grains in
percentage of unfermentable carbohydrates is the mash tun. The sparger (Fig. 10, E) consists of
desirable in the beer at racking, comparatively two or more hollow arms perforated along one
low heats are necessary, and an initial tempera- side and extending to the sides of the mash tun.
ture of 62-64C. (143-148F.) is usually ob- The older forms are connected with a central
tained with underlet at 82C. (180F.). In the basin through which the upright shaft of the
case of black beers, where high-dried malts are mashing machine passes, and the basin runs on
used which have rather low diastatic activity, low wheels fixed to a carriage on the upright shaft.,
mashing heats are essential to encourage dia- The mash liquor flows into the central basin,
static action. An initial temperature of 61-63C. thence along the arms and through the perfora-
(142-147F.) is usual with underlet at 82-87C. tion, causing the arms to revolve ;by this means
(185-190F.), so as to raise the mash to 66C. the whole of the goods are exposed to a washing
(152F.) after 20 minutes' stand. Of course, the the
operation, whereby the greater part of
mashing temperatures vary with the quality of residuary wort matter adhering to the grist
is
the malts, but the above are within the range of abstracted.
temperature employed. The initial tempera- Great improvements have been made in
ture is determined either by inserting a thermo- spargers, with a view to increasing the
extract
meter specially made for the purpose into the obtained from the goods. In the latest forms
mash in the tun, or by fixing a thermometer in the perforations along the arms are made very
the shoot leading from the outside masher into in a
fine, thereby causing the liquor to issue
the mash tun. fine spray, which is thoroughly and evenly
During the operations of sparging, some of distributed over the whole surface of the goods.
the harder portions of the starch which had The liquor passes through the central sha
hitherto escaped saccharification become dis- straight into the arms, which, being hung on ball
BREWING. 555
bearings, ensure a steady revolution at any copper is made up. If higher temperatures
than these are used, a risk is incurred of dissolv-
Most brewers begin sparging shortly after ing out some of the unaltered starch, of which
setting taps, and keep the sparges going con- there is always to be found a small portion
tinuously until the whole of the wort matter has remaining in the grams, and which has not been
been got away from the grains ; others do not acted on by the diastase on the malt.
commence to sparge until one-fourth, one-half, It was at one time the custom to shut off the
or even three-fourths of the strong liquor has taps when the gravity of the wort had fallen to
been drawn off. It is preferable to start sparging about sp.gr. 1005, as wort below that point was
when the first ten barrels of wort are in copper, thought to contain matters detrimental to the
at the rate of one-half to three-quarters of a production of sound beers. In the writer's
barrel per quarter of malt, at a temperature of opinion this is quite a mistaken idea, and there is
170F., and until the upper layers of the mash, no reason why the wort should not be run to as
which have begun to cool somewhat, are again low a gravity as possible. This course has been
at the normal temperature ; the sparging liquor adopted in most up-to-date breweries at the
is then cooled to 160F. and the sparging carried present time.
on continuously at this temperatire until the 31. Boiling. As soon as the wort- leaves the
FIG. 12. MASHING ROOM, ANGLO-BAVARIAN BREWERY, SHEPTON MALLET.

mash tun it is, as we have already seen, either run the wort as it flows into the copper at a tem-
directly into the copper or collected first in an perature not exceeding 165 during the time the
intermediate vessel called the underback, but it copper is being filled. This process is called
is advisable that it should remain only a short stewing the worts, and is said to be often very
time in this vessel, so as to prevent any appreci- advantageous, especially when the malts are
able loss of heat. As soon as the first ten deficient in diastatic power. No advantage can
barrels are in the copper the fire may be got up, possibly accrue from such a process, but, on the
and the temperature of the wort raised to about contrary, much harm may result therefrom to the
180F. or 190F. At the same time, a certain finished beer. With regard to the period at
proportion of the hops may be added a little which it is most advisable to add the hops, much
at a time until all the wort is run into the difference of opinion exists, some brewers not
copper or the copper is made up. As soon as adding any until the copper is nearly or entirely
this is effected the fire is increased and the wort made up, others adding the whole of the hops
brought to the boiling-point as quickly as before the copper is half full. Both methods are
possible. This is carried on usually for one and very objectionable ; the addition of the hops to
a half to two hours. the copper ought to run pari passu with the in-
In some breweries it is the custom to keep flowing wort. By this means we get a more
556 BREWING.
regular precipitation and coagulation of certain ing process, so that the wort at this stage affords
albuminous substances from the wort, and a a very good index as to the dextrin percentage
more even extraction of the bitter and resinous of the resulting beer, and hence a systematic
principles of the hop, the result being a well- polarimetric examination of wort from the cop-
broken, regular wort and superior-flavoured beer. per will be found to be extremely useful. It
The usual plan in many breweries, and one may be taken as a general rule that the specific
which for several reasons is to be strongly re- rotatory power of a wort should not fall below
commended, is to divide the total quantity of 105 [a] or rise higher than 122 [o] , the
D D
hops for each copper into three portions. The former indicating an abnormally low percentage
first portion is added as the wort is running in,
of dextrin and large excess of soluble nitrogen-
a relative proportion for every 10 barrels of wort
ous matters, the latter a very high percentage of
as it runs into the copper until made up ; the
dextrin resulting probably in extremely high
second portion is added after one hour's boiling,
attenuations and cloudy beers, fining only with
and the third portion half an hour before the
difficulty.
copper is turned out.
When the boiling process is completed, the
It is the general custom to use a blend of
wort with the hops is run out of the copper
several varieties and qualities of hops, and in
into the hopback. This is a vessel of somewhat
this case the most inferior are added in the first
similar construction to the mash tun ; the sides
portion, the second portion consists of superior
may be square or circular in shape, preferably
hops to the first, and the last portion are choice the latter, and is furnished with a perforated
hops selected to impart to the beer its special
copper false bottom. Here the wort is drained
character. By this method most of the from the hops and run into a small wooden
volatile oils and resins of the last portion of
underback, whence it is pumped up on to
hops will remain in the beer, imparting to it a the coolers, but as the hops in the hopback
characteristic delicate aroma of flavour.
retain a certain proportion of the wort adhering
We have assumed that the whole of the to their surface, boiling water is sparged over
wort from one brewing is boiled at once in them, and these spargings are added to the wort
one copper, and, where practicable, this is by and serve to reduce it to the required gravity.
far the best plan; but more often the wort Where brewing sugar of any description, whether
from one brewing is divided between two cane sugar, invert, or glucose, is used in the
coppers, the stronger wort being boiled in the brewing, it is best to add the requisite quantity
first copper with the whole or greater part of the
previously dissolved in boiling water to the
hops, whilst the last half and weaker portion of wort in copper about 15 minutes before turn-
the worts is run into the second copper and boiled
ing out ; the usual proportions are from one-
with the already exhausted hops which are re- third to one-fifth of the quantity of malt used,
turned from the first copper. This is a very 2 cwts. of sugar being reckoned to be equivalent
objectionable as well as dangerous method of to the extract yielded by 1 quarter of malt. The
procedure. The first copper wort will contain quantity of hops used will, of course, vary with
proportionately much more saccharine than the gravity as well as quality of the wort. In
nitrogenous matter, the latter being in excess in Burton as much as 20 Ibs. of hops per quarter of
the second copper ; again, all the tannin and malt have been used for export pale ales, but for
the largest proportion of the soluble matters are
ordinary pale ales from 10 Ibs. to 15 Ibs. is the
extracted from the hops by boiling them in the usual proportion, less being required where malt
first copper, so that when these hops, which are substitutes such as invert sugar or glucose are
practically exhausted of all their useful pro- used.
perties, are added to the second copper of wort The main effects of boiling the wort with hops
containing relatively more aJObuminpus matter in the copper are :
evaporation ; sterilisation,
than the first, comparativelyTittle precipitation i.e. destruction by heat of all bacteria and disease
or coagulation is produced by the matter ex- obtained from the malt and from the
organisms
tracted from the hops, whilst a coarse, bitter air destruction of all diastatic and proteolytic
;
flavour is imparted to the wort, so that the
action, and fixation of the starch products ;
resulting beer contains an excess of nitrogenous precipitation of a large proportion of the hitherto
matter, thereby being rendered more liable to soluble albuminoids ; and the addition of hop
disease, and brightening only with difficulty. extract consisting of the bitter principles and
Where it is necessary to divide the wort between tannin.
two coppers, the stronger wort may be run into Two systems are in general use, viz. boiling
one and the weaker into the other, but to both
by fire and boiling by steam. It is essential that
coppers fresh hops should be added in quantities the stability of a beer should be fixed by a
proportionate to the gravities of the respective thorough cooking of the wort, and this is readily
worts. achieved in a suitably deep fire-heated copper,
During the boiling of the wort with hops 'in but it is rather doubtful whether the same result
the copper, all diastatic action is completely is obtained in a copper heated by steam.
destroyed, and the starch products become fixed, In the case of a fire copper, we have on one
a large proportion of the hitherto soluble albu- side of the plates intense heat and on the other
minoids are precipitated, whilst a small quantity side cool wort. The circulation of the wort is
of hop extract is added ; at the same time, a excellent and a vigorous boil results. There is
slight alteration occurs in the carbohydrates also a continuous exposure of a layer of wort to
other than those derived from the starch, being a very high temperature on the bottom of the
probably due to a slight inversion of a part of the copper, which receives the thorough cooking
unacted-on cane sugar by the acid of the boiling which is so essential. In the case of steam
wort, but practically, the actual composition of coppers, the contact temperature is very much
the starch products is unaltered during the boil- lower, for although a tumultuous boil is secured
BREWING. 557
by the aid of coils and heaters of various design, run the tube is filled with liquor, the float
off,
the temperature obtained is high and the placed over the tube, and the outlet tap opened ;
evaporation rapid. Still the wort does not

' '
the wort or liquid at once begins to run over the
receive the same cooking that it does in a fire top of the tube and continues doing so until tho
copper and upon which the final stability of the whole is run off from the cooler or vessel.
beers so much depends. The supply of liquor always being taken from
32. Cooling. Coolers may be described as the top, the brightest and coolest wort is run
large shallow tanks about 18 inches deep, of down first, so that the whole or greater part of
such capacity as to contain the whole contents the sediment is left on the cooler.
of the copper at one time ; they are generally It likewise gets a bright wort down over the
constructed of wood, wood lined with sheet refrigerator into the fermenting tuns, for while
copper or iron. Those made of wood are rapidly the bright wort is running off from the top, the
being discarded, as they are so liable to retain grounds and thick sediment sink to the bottom,
contamination in the way of spores of bacteria and remain on the coolers.
or mould. The wort is usually delivered on to the cooler
The principal object in running the wort on through a perforated pipe in the form of a spray
to the coolers is undoubtedly to lower the tem- for the purpose of aeration, and during the
' '
perature or to take the fire heat out of it ; but summer months in some breweries in order to
at the same time, another action is going on, the prevent bacterial contamination on the coolers,
importance of which has only been clearly these are replaced by deep tanks, the spraying
understood during the last few years, and that of the wort being found sufficient to absorb the
is the aeration of the wort or the absorption by necessary oxygen, the whole of the cooling in
the wort of the oxygen of the air, either by way this case being effected over the refrigerators.
of solution or of combination, for not only does After leaving the coolers, the wort, which is
the atmospheric oxygen become dissolved in the not yet by any means cold, is passed over a re-
wort in a manner similar to carbonic acid in frigerator, where it takes up in its passage a still
water, but it actually enters into direct chemical further quantity of oxygen. There are several
combination with certain nitrogenous consti- forms of refrigerators the vertical one such as
;
tuents of the wort, rendering them thereby in- shown in Fig. 14 is generally considered the best
soluble and causing such substances to be
deposited on the coolers. Aeration has also a
considerable influence on fermentation, indeed,
in the ordinary process of brewing normal fer-
mentation would be almost impossible, and in
every case most defective, if the wort, before
being run into the fermenting vessels were not
aerated by its passage over the coolers, where
the aeration is more or less effective according
to the depth of liquid on the coolers.' It is
evident, then, that it is decidedly advantageous
to allow the wort to remain a certain time on
coolers before passing it on to the fermenting
rounds, and also that the surface liquid should
be drawn off first. This has been effected in a
very ingenious manner by the arrangement
shown in Fig. 13, which is the invention of Mr.
S. Briggs, of Burton-on-Trent.
FIG. 14.
These refrigerators are made from seamless

copper tubes, with a rib or feather on bottom and
groove or channel on top side, running full length
of tube. The rib or feather of one tube is
securely fastened into the groove or channel of
the next tube, thus giving great solidity, and
presenting an even surface to prevent any lia-
bility of dirt accumulating, the brewer being able
at a glance to see if the machine is perfectly
clean.
The ends are fitted with gun-metal boxes
with movable caps, giving easy access for brush-
ing out the tubes, and are especially adapted for
pumping, the tubes having no divisions to
impede the water passage.
They are fitted with adjustable feet for regu-
lating the flow of wort, and a perfect capillary
FIG. 13. attraction is obtained, a great desideratum in
vertical refrigerators. The inlet trough is di-
This apparatus simply consists of a vertical vided to secure an equal flow of wort down both
> tube made of metal, fixed over the outlet of the sides of the machine. .
cooler or vessel. But all the time that the wort is on the
When the wort or other liquid is ready to be coolers and refrigerator it is exposed to danger
558 BREWING.
of contamination with germs of disease such as summer may be taken as safe temperatures
bacteria and wild types of yeast, which are to be for cooling the wort to, previous to adding the
found always floating about in the air. Also be- yeast.
yond a certain limit aeration is injurious to the It has long been recognised that most of the
palate characteristics and aroma of the finished disease organisms that find their way into the
beer, hence it is advisable that, consistently with beer are introduced by the air, and as soon as
sufficient aeration, the wort should be cooled as the wort on the coolers and refrigerators drops
quickly as possible, especially when it reaches below 170F., wild yeasts and acid-forming
a temperature of 170 and lower. Coolers and bacteria are no longer killed. It is advisable,
refrigerators should therefore be of sufficient therefore, unless the air playing on the wort is
capacity to cool the whole of one brewing or gyle sterilised,that the temperature should not drop
down to the required temperature, 58-60F., lower than 170 while the wort is on the coolers.
in at least six hours, counting from the time the In the case of the refrigerators, however, the
first of the wort is pumped on to the coolers conditions are different. Here aeration is
until the last of it is in the fermenting vessel. essential as well as the cooling of the wort to
This temperature will vary slightly with the temperatures favourable to the growth of
quality of the wort and the temperature of the disease germs. There is an extended film of
atmosphere ; but for beer of medium strength, liquid in contact with the ah-, and the organisms
and where the atmospheric temperature is about hi the air coming in contact with the film are
the average, 58-60F. in winter and 58F. in attracted by it, and, being of a viscous nature,
the wort retains a large number of them. It
seems very essential, therefore, to conduct the
process of refrigeration in a sterile atmosphere.
This idea, in fact, is being adopted in a great
number of breweries at the present time. The
FIG. 15.
refrigerators are enclosed in an air-tight room, menting tun (Fig. 15, a). This is usually con-
the walls and ceiling of which are made of structed of wood, and may be square or round,
material which is easily cleansed and which is
preferably the latter, as being more easily
supplied with an inlet and outlet for the sterile cleansed. The wood generally preferred is
air. During the time the wort is running down, Dantzic deal, but care must be taken before
previously purified air is blown through the using vessels made with this wood to first remove _
room at a sufficient rate to renew the atmosphere its resinous flavour from it before running in
at least twenty times in order to ensure efficient the wort. The surfaces of wooden vessels
aeration and also to remove the reek. should present a perfectly smooth interior
There are several air purifiers in use at the surface, otherwise they becomevery readily
present time, but the principle is the same in all contaminated. On this account, copper in thin
cases, and consists in blowing air by means of a sheets has been very extensively employed for
fan over an adhesive or viscous liquid containing lining these vessels. This is undoubtedly the
a germicide. This liquid absorbs all the micro- finest material that can be employed, as it is so
organisms from the air, which issues from the very readily cleansed, is not liable to con-
outlet in a perfectly sterile condition. tamination, and is extremely durable. The
Of course, it is essential that the ceiling, walls, fermenting round is furnished with an attem-
and floor of the refrigerator room should be perator or coil of pipe through which either hot
perfectly clean, as it would be useless to inject or cold water may be transmitted for the purpose
pure air into a room in an unclean condition. of regulating the temperature of the fermenting
33. Fermenting. From the refrigerator the wort. As soon as the first ten barrels of wort
wort is conveyed by copper pipes to the fer- are in the fermenting tun the requisite quantity
BREWING. 559
'
of yeast may be added ; this is called pitching.' at time of pitching will now show an apparent
The quantity of yeast to be added will of course specific gravity or attenuation of about 1023.
vary according to the strength of the wort, the This is about the highest point the tempera-
quantity of hops used, quality of yeast, and ture is allowed to rise to. When, therefore, this
season. For light ales and running beers about point is reached, the separation of the yeast
J Ib. to 1 \ Ibs. per barrel of wort are used, whilst from the beer, or the cleansing process, is com-
for the stronger ales from \\ to 3 or even 4 Ibs. menced.
in some cases are used. Up to this stage from the time of pitching,
In general appearance the yeast should be of the fermentation is very closely watched by the
a rich cream colour, possessing a sweet clean brewer, and the temperature and attenuation
smell. Under the microscope the cells should taken at intervals of about five hours. If the
be uniform in size, full and plump-looking, and fermentation goes on too rapidly, it is easily
transparent, containing feAv, if any, vacuoles or controlled by running more water through the
granulations ; the cell walls should be thick and attemperator.
free from pittings, and stand well out against When the yeast is first added to the wort it
the field. No signs of budding should be ap- lays hold of the free oxygen which has been
parent, and no dead or shrivelled cells should be dissolved by the passage of such wort over the
present. The presence of any dead cells may refrigerators, and not until the greater portion
easily be determined by running on to the slide of that oxygen is used up do the yeast cells
a drop of methylene-blue solution, which in- begin to attack the sugars of the wort and split
stantly stains all dead matter, but has no effect them up into carbonic acid and alcohol. It has
on living cells. In a really good pitching yeast been found in practice that the fermentation
no bacteria or other germs of disease ought to proceeds more satisfactorily if a certain amount
be present, but most yeasts generally contain a of aeration is carried on during the process. This
few. As a rule, any sample of yeast that contains can be done by pumping air into the tun of
more than 20 short bacteria (rods) in 10 fields fermenting wort, but yeast not only requires a
ought to be condemned for pitching purposes ; limited amount of air, but also a vigorous
the presence of any of the longer forms of motion from time to time, in order to enable it
bacteria, whether straight or bent, is sufficient to to do its work effectually as well as to render
at once condemn the yeast as being a highly it capable of being eliminated from the beer.
dangerous one to use. Hence a thorough rousing by means of long

As has already been mentioned, it is almost paddles or oars worked with hand, or by some
impossible to determine by ordinary micro- form of the various machines introduced for this
scopical examination the presence or absence purpose, is necessary at stated intervals, more
of wild types of yeast ; these must be looked especially where the fermentation is inclined to
for by Hansen's method of ascospore forma- be at all sluggish.
tion. During late years, owing to the general use
As soon as the wort has been cooled to the of malt and substitutes devoid of yeast nutriment
proper temperature, and ready to undergo the in brewing, the more highly dried character of
process of fermentation, it is, according to the malt in use, defects of much modern malt
the Inland Revenue Act of 1880, run into a attributable to variation and inferiority of barleys
vessel called the collecting vessel, where it must wetted, and reduction in gravities of collected
remain for a period not less than 12 hours, worts, several forms of nutriment for the yeast
or until such time as the Excise officer can deter- have been introduced. These consist chiefly of
mine its gravity and bulk for the purpose of peptones and amides which have been proved
levying the required duty. In most breweries to be the best nitrogenous nutrients of yeast.
these collecting vessels are the fermenting tuns 34. Cleansing. The separation of the yeast
themselves. from the beer may be accomplished in many
After all the wort has been run into the tun ways. The three principal systems are known
and the yeast thoroughly roused up with it, the as :
process of fermentation commences ; bubbles of The cleansing system, as practised in some

gas rise to the surface until, after a while, the London breweries, and also in Burton, but on a
whole of the surface becomes covered with a very much improved method.
creamy froth. As the fermentation progresses The skimming system, as generally adopted
and the decomposition of the sugar becomes throughout the South and West, as well as
more rapid, the greater is the amount of car- many other parts of England ; and
bonic acid which is liberated, and the froth stone square system, which is almost
The
swells up to such an extent that at last, not being exclusively confined to Yorkshire.
able to resist any further tension, it topples over,
.
In London, and indeed in many country
' '
giving rise to that rocky appearance which is breweries, the cleansing is effected by running
seen on the surface of healthy fermentations the beer from the fermenting tun by means of
during the earlier stages. At the same time, the a hose into ordinary 36-gallon casks, arranged
temperature of the liquid will be noticed to rise in rows side by side on a wooden trough or
steadily. If this goes on too fast it must be stillion, about 2 feet from the ground. The
checked to a slight extent by running some cold beer remains in these casks for some days, the
water through the attemperator. Under normal bunghole being left open, and through it the
conditions a rise of 1 ought to take place in 6 yeast works out and falls into the stillion. As
hours, so that at the end of about 60 hours the yeast works over, more beer is added to each
the temperature of the fermenting wort would cask, so that by the time the beer is freed
have risen to 70F. ; the beer will at the same entirely from the yeast, each cask is full and
time have attenuated to about one-half. Thus ready to be bunged up, and sent away for con-
a beer wort which had a specific gravity of 1050
sumption, for London beer fermented upon this
560 BREWING.
system is generally drunk within a week. This through a tap at the bottom of the tank. The
method of cleansing however, being rapidly
is, yeast is either pressed and sent away, or used
replaced by the skimming system ; this in prin- for pitching fresh wort.
ciple simply consists in skimming off the yeast After the first skimming, the yeast still con-
from the surface of the liquid from time to time tinues to throw up a cleaner and whiter-looking
as it rises to the top, and may be effected either head, so that in about 3 or 4 hours' time
in the fermenting tun itself, or, which is much a second skimming is made, and so on every
preferable, in the cleanser. The beer, when it has 3 or 4 hours until all of the yeast has sepa-
attained the proper degree of attenuation and rated from the beer. It is generally found
temperature, is run down from the fermenting that from four to five skimmings are necessary
tun along with the yeast into a large square to effect this. After the last skimming a thin
wooden tank called the skimming back or settler but tough film of yeast forms on the surface ;
(Fig. 15, b). This is fitted with attemperators this is allowed to remain, and serves as a covering
which run round the sides ; at one end are fixed to protect the beer from aerial contamination
two parachutes, which are simply large flat and from oxidation, as well as to prevent the
funnels of copper having pipes 4 inches in escape of carbonic acid. A
general view of
diameter attached to them, the whole being these skimming backs is shown in Fig. 16.
tinned over, and capable of being raised or It usually remains from two to three days
lowered at pleasure by means of a screw and in the settlers after the last skimming, so as to
winch handle. allow all matters in suspension to settle out.
When the liquor is run into the settler, At the end of that time the beer, which is now
owing to the thorough aeration which it receives very nearly if not quite bright, is run down into
in so doing, a vigorous fermentation takes place, a large tank, termed a racking square, where,
and unless carefully watched the temperature after remaining a few* hours, it is racked off into
trade casks, either to be
sent away for consump-
tion or to be stored for
some time to mature.
The Burton Union
system, as the Burton
system of cleansing is
called, may be regarded

as the scientific develop-
ment of the old London
system of cask cleansing
on stillions. In this
system a number of casks
or unions (Fig. 17) capable
of holding four barrels of
beer, are placed side by
side in two rows ; these
are hung in sets of twelve
or more on a substantial
frame, so as to admit of a
free revolution of each
cask on its axis, so that
FIG. 16. TUN ROOM AT ANGLO -BAVARIAN BREWERY, SHEPTON MALLET. when *he casks are to be
washed they can be filled
is apt to rise. At must with boiling water, bunged up, and rapidly
this point attemperation
be attended to, but the fermentation must not revolved. Supported on the same frame, and
receive too severe a check. Soon a film of yeast immediately above and running parallel with
mixed with carbonic acid gas appears on the these rows of casks, is a long shallow trough
surface of the liquid, which gradually gets called the yeast trough, and at one end and at
thicker, so that about 6 hours after tunning or right angles to it is another trough called the
running into the cleansing tank, the first head
of yeast is ready to be skimmed off. This is done
by means of a plank as long as the tank is wide,
furnished with handles, and held vertically by
two men at the end opposite to the parachutes,
in such a position that one end of the plank
just touches the surface of the liquid imme-
FIG. 17.
diately beneath the head of the yeast. This
plank is then gradually moved along the length feeding trough. From this trough a pipe,
of the tank, pushing the yeast before it. The 2 inches in diameter, runs along the whole
parachutes are fixed so that they will just receive length of the series of casks on either side,
the yeast which overflows into them, which is and is connected with each cask by T-pieces
then conveyed into slate tanks placed imme- and screw unions. At the highest part of
diately beneath (see Fig. 15, c). Here it is each cask is fixed a ground-brass socket, into
allowed to remain for some hours, being roused which is fitted a peculiarly shaped pipe of tinned
occasionally so as to drive off the carbonic acid copper, termed a swan-neck, which is arranged
gas as well as to enable the beer which has come to bend over the yeast trough, and serves to
over with it to settle out, and which is drawn off convey the yeast thrown off during cleansing to
BREWING. 561
this trough. In order to keep the casks full a has subsided, and no more yeast is observed to
certain quantity of wort is placed in the feeding come over, the swan-necks are removed, the
trough, which is allowed to run into the casks casks bunged up, and the contents allowed to
from time to time to replace the yeast (and beer remain at rest for a few days longer for the
carried over with the yeast) which has worked purpose of allowing any yeast or other matters
over into the yeast trough. After a time the that may have remained in suspension to settle
beer carried over with the yeast separates out down to the bottoms of the casks. The clear ale
and is allowed to flow into the feeding trough is then drawn off by means of a screw
tap fixed
through a series of holes in the end of the yeast at the lower part of each cask. The tap projects
trough nearest to the feeding trough, of which it 6 inches upward into the cask, so as to
prevent
forms one of the sides ; these holes are closed the sediment or grounds from being drawn off
with corks, and the man in charge ascertains by at the same time as the clear liquor. From these
trial at which holes the beer will run off free taps the finished beer is delivered by means of a
from yeast, and accordingly opens these in turn trough running underneath them into a large
so that the casks are always kept more or less settling back or racking vessel, where it is
full of beer. This feeding or sparging is done allowed to settle for a short time before
being
at intervals of 3 hours until the active fer- drawn or racked off into trade casks.
mentation has ceased. After the fermentation Where the Union system is employed, no
FIG. 18. UNION ROOM AT MESSES. WORTHINGTOK & Co.'s BREWERY, BURTON -ON-TRENT.
attemperators whatever are used in the fer- high and also a smaller hole provided with a
menting tuns, the time for the beer to be tunned valve, on the under side of which a tube, called
being regulated entirely by the temperature. the organ pipe, is connected, which extends to
As soon as 70 is attained, the beer is imme- within a few inches of the bottom of the square.
diately run into the unions. Neither are any The lower vessel is a little more than filled so
attemperators used in these casks in winter, but that the wort lies some 2 or 3 inches deep in the
during the summer months free recourse is had upper one or yeast-back. About 36 hours after
to attemperating. Fig. 18 gives a very good pitching, pumping is started and carried on at
idea of the Union system of cleansing. regular intervals until attenuation is nearly over,
Where the Stone Square system is used, the wort being pumped into the top-back, well
squares are constructed of stone or slate, and roused and mixed with the yeast that has risen
have a capacity of about 30 to 50 barrels. The there, and allowed to flow back into the lower
organ pipe.' The whole
'
vessels consist of two parts the lower one,
: vessel through the
which has double sides and a space between for crop of yeast is eventually left in the upper back.
attemperating liquor ; and the upper one, which This system is productive of an excellent
is placed so that its bottom forms a
top or cover yeast crop and bright racking beers and of very
to the one below. In this roof or cover, there is brisk, well-conditioned beers with good palate
a man-hole with a raised collar about 6 inches fulness. Owing to the trouble of effectually
VOL. I. T. 2 o
562 BREWING.
cleansing these vessels, and several other diffi- tion it is usual, in order to enable it to become
culties met with, they are gradually going out bright rapidly, to add a solution of isinglass, or
' '
of use. finings at the rate of 1 to 4 pints per barrel of
Space not permit us to enter into a
will beer.
detailed description of the various other systems The isinglass chemically with the
unites
of fermentation carried on in this country, and tannic acid which is
nearly always present in
\ve must now pass on to treat very briefly of the beer, forming a gelatinous flocculent precipitate
German system of beer-brewing. of tannate of gelatin ; this very soon sinks to
The German or decoction method of mashing the bottom of the cask, carrying all matter in
is generally carried out as follows : suspension with it, and leaving the beer clear
Ground malt is run into the mash tun, in and brilliant.
which are two-thirds of the required water at Finings are generally made by dissolving
the ordinary temperature of the air ; here it re- isinglass in sour beer. This is a crude and dan-
mains for 2 hours. In the mean time the gerous method. In the first place, the isinglass
remainder of the water is heated to boiling in takes several weeks to dissolve, and secondly, by
the copper, and then run slowly into the mash means of this sour or turned beer a great risk is
tun, the rakes at the same time kept revolving run of introducing into the sound fresh beer all
at a good speed. By this means the temperature kinds of disease germs, but more particularly
of the mash is raised to 95-100F. The S. pastorianus, as well as the ropy and lactic
first thick mash (about one-third of the whole) ferments.
is now drawn off into the copper and boiled for The best and purest finings are undoubtedly
30 minutes, and then returned to the mash made by dissolving good isinglass in dilute solu-
tun, the temperature of which is thus raised to tion sulphurous acid, and on no account
of
116F., the rakes being kept going during the should any other kind of finings be used in the
addition of the first boiled mash. A second brewery.
thick mash is now drawn off into the copper Beer which is not required for immediate use
and heated to boiling-point, and kept boiling is stored in cellars at a temperature of 54F.,
for 15 minutes, and then run back again to either in vats or in the casks in which it is to be
the mash tun, the temperature being now raised sent out. Such beers are generally not fined,
to 149F. After this the clear part of the mash and each cask is furnished with a porous spile
is run off and boiled in the copper for 15 or vent peg to allow of the escape of a portion of
minutes and run back again to the mash tun ; the carbonic acid produced, owing to a secondary
the temperature of the mash is now 167F. The fermentation which always sets up in casks when
mash is now covered up, and allowed to lie for beers are stored for any time.
one to one and a half hours ; the taps are then Chemical analysis of a beer should be made
set, and the clear wort boiled for 2 hours shortly after racking, and before the secondary
with hops at the rate of about 2J Ibs. of hops to fermentation in cask has commenced. Such an
every 100 Ibs. of malt used. The wort is then analysis, calculated on the solid extract of the
drawn off and run over coolers and refrigerator, original unfermented wort, should show :
where it is cooled down to 40F., and thence to o. Matter fermented.
fermenting tuns, which are generally placed b. Maltose unfermented.

under ground in order that they may be kept c. Dextrin unfermented.
cool by ice ; and for that purpose small ferment- d. Albuminoids, ash, &c.
ing vessels of about twenty barrels' capacity are As the character and keeping properties of a
used. These are filled nearly full with the beer depend to a very large extent on the per-
wort, and bottom yeast in the proportion of centage of unfermented dextrin which it contains,
about 1 Ib. to every five barrels of wort added ; it would appear very desirable that an analysis
the yeast, previous to being added to the wort, is of those beers required for stock or export
first mixed with some wort of the former day's should occasionally be made, so that an idea
brewing, and thoroughly aerated by repeated may be obtained as to the constancy or other-
pouring from one vessel to the other, and then wise of their composition, and hence their
put aside in a warm place for some hours, so suitability for the purpose for which they were
that by the time the wort is ready to be pitched intended.
a lot of new and vigorous yeast cells have Generally, at time of racking, and indeed in
already formed and the fermentation is well some cases at different stages of the brewing pro-
started. During the earlier stages of fermenta- cess, some form or other of antiseptic is added
tion a slight head rises to the surface ; later on to the beer for the purpose of protecting it
the yeast deposits on the bottom of the ferment- against the germs of disease to which from one
ing vessels. During this primary fermentation, cause or another it is so subject. The substances
which lasts about 12 days or more, the most generally employed for this purpose are
temperature of the fermenting wort is kept at calcium bisulphite, salicylic acid, or a particular
about 44F. When the primary fermentation form of potassium sulphite, known as kalium
is finished, the attenuation has run down to The antiseptic, whatever it may
metasulphite.
about one-half the original gravity of the wort, be, is addedeither to the beer whilst in the rack-
and the beer is run off, as free as possible from ing square, or to the beer in cask just after
sediment, into casks, ranged in tiers on either racking, if calcium bisulphite at the rate
of
side of large cellars, which are kept cold by ice. i to J pint per barrel, or salicylic at the rate of
Here they are allowed to remain for some months, J oz. or less per barrel.
during which time a secondary fermentation goes Experience shows that calcium bisulphite is
slowly on, and the beer gradually clears itself much to be preferred to salicylic acid, but the
until it becomes brilliant and fit for use. chief objection appears to be the smell which it
Where beer is required for quick consump- sometimes imparts to the beer, especially when
BREWING. 563
used in any quantity. This may be got over by saturated with carbonic acid gas before bottling,
using kalium metasulphite, which is claimed by so it is racked into casks and stored in a cellar
the discoverers to be much more powerful in its at a temperature of 50-55F. When it is
action than bisulphite, whilst it imparts no conditioned, it is fined if necessary, and bottled
smell to the finished beer. by means of a siphon machine into perfectly dry
Absolute cleanliness in every part of the clean bottles, and immediately corked. The
brewery and in every portion of the plant is necessary bottle condition is then brought
necessary, for unless due regard be paid to this about by storing at a temperature of about
point, no matter how good the materials or how 65F. for some time before consumption.
perfect the process of manufacture, the quality of 2. When a brewer cannot afford to let his
the finished article will be sadly defective in its bottled beers lie for so long a period as is neces-
most vital characteristic, viz. keeping properties ; sary in the old-fashioned system, he generally
'
false ferments and micro-organisms of all kinds has recourse to the second method, called forced
will be taken up by the beer at all stages of its bottling.' The same type of beer is brewed as
manufacture, rendering it after a time sour, in the previous method, and the same care
unpalatable, and unfit for consumption. In exercised in the choice of materials, &c. ; but
order to obviate this, every portion of the plant, early fermentation is encouraged in cask, and
when not in use, should be thoroughly well the time of storage greatly curtailed. This is
cleansed and disinfected with suitable agents, accomplished by adding priming to the beer at
such as chloride of lime, calcium bisulphite, the time of racking, while early clarification is
caustic potash, &c. Cf. A. Hartley, Trans, of brought about by the addition of finings. When
the Laboratory Club, 1, 42. the beer is absolutely brilliant and has been
sufficiently flattened in cask, it is bottled and
BOTTLED BEERS. stored at a temperature of 60-70F. It is
The adoption of lower gravities by the brewer, sent out immediately it is sufficientlyconditioned,
owing to increased expenses and the rapid advance and, provided it is not kept too long, it will turn
into popular favour of light bitter beers, has led out quite satisfactorily.
to the almost general production of a beer of light Naturally conditioned beers, brewed and
gravity, distinctly though not strongly hopped, bottled under the most favourable conditions,
which will fine quickly and carry a good condition present to the palate a peculiar pungent flavour
within a very short time of racking. The desire and an invigorating freshness which cannot
for good condition as well as for a convenient easily be obtained with carbonated beer. There
package has gradually created a large demand is one great drawback, however, to all such
for bottled beer, and the bottling trade has now beers, they must inevitably be accompanied
become an integral part of almost every brewery. by a deposit which in many cases is more or
The various methods of bottling at present less heavy. It was to obviate this defect that
carried out in this country are as follows : the carbonating system was first introduced,
1. Natural method of
bottling. and the many and various improvements which
2. Forced bottling. have been made since its first introduction have
3. Simple carbonation. made it possible to produce a beer in many
4. Quick shilling and filtering process. respects equal to that produced by the natural
5. Prolonged chilling and filtering process. method.
1. The old-fashioned or natural method of 3. To produce a first-class carbonated beer,
bottling can only be successfully carried out if the same amount of care in selection of materials
the beers to be bottled have been specially is hardly necessary, very high-class malts not
brewed for the purpose. There are many other being absolutely essential, and a certain pro-
influences besides the materials used, such as portion of invert sugar being a desirable con-
the conditions of plant, aeration, yeast, &c., which stituent. The beer, however, must be specially
have their action upon the flavour, quality, and brewed for this purpose, as it is absolutely
type of the beers ; and it will be necessary for necessary that the finished beer should possess
the brewer to regulate these matters before he as little fermentable matter as possible, and a
is able to produce a satisfactory article. The very low attenuation. After racking, the beers
water used for mashing should be suitably should be fined and remain in the cellar for three
hardened by the addition of gypsum and alkaline weeks. It is then efficiently filtered through a
chlorides the gypsum conducing to bright and pulp filter, from which it passes into an auto-
more stable worts, whilst at the same time matic carbonating machine, where it is thoroughly
preventing the extraction of an excessive amount impregnated with gas at a pressure of 30-40 Ibs.,
of bitter principles from the hops, and the and at the same time prevented from coming in
alkaline chlorides contributing to palate fulness. contact with any air. The whole secret of gpod
Great care must be exercised in the selection carbonation lies in properly impregnating the
of materials, and only the best malt prepared beer with gas. The gas used should be pure,
from those barleys which are free from an excess the natural gas, collected from fermenting wort,
of nitrogenous constituents should be used. A being preferred by some brewers, as it is said to
blend of good English and foreign malt with a give better results and impart a better flavour to
proportion of some prepared grain will give the the beer. The beer passes from the carbonator to
best results. It is also advisable to use a good a suitable bottling machine which fills into bottles
quality hop with a proportion of foreign hops, and stoppers without waste or loss of gas. This
on account of then* greater preservative power, beer can be sent out as soon as bottled, but can
and only the choicest English should be used for also be kept without throwing a deposit for
dry hopping. It is necessary that all secondary some time. The greatest defect attaching to
fermentation changes should be allowed to carbonated beers is that their brilliancy is
complete themselves, and that the beer should be |
influenced by the temperature at which they are
564 BREWING.
stored, as they are inclined to develop haziness brce the beer rapidly into a vigorous after-
in very hot or cold weather. This has been êrmentation. Kraiisen consists of beer in the
overcome by chilling the beer before filtering irst stage of fermentation, 2444 hours after
and bottling. iltering. The kraiisen should be taken from a
the usual
It is necessary to recognise that seer of the same type and original gravity as
system of brewing and fermenting must be ;he beer to be conditioned. When the beer is
modified to meet the altered conditions involved in high condition, which usually takes six or
for producing chilledand filtered beers, and the seven days, it is slowly chilled by the most
remarks made above with regard to the low suitable means. If glass-enamelled tanks are
attenuations necessary for carbonated beer used, these should be fitted with coils through
applies equally well for this type of beer. which refrigerated brine is passed. In this way
By the process of chilling beer or the cooling the complete process of conditioning, chilling,
of it down to 30F. the yeast and other organisms, and clarification can be worked in the same
with certain of the hop resins and substances of tanks. If the storage plant does not lend itself
a proteid nature which become insoluble at low to chilling in bulk, the vessels are either placed
temperature are coagulated and thrown out of in a coldcellar and aDowed to cool gradually
solution. When these matters are separated at to the required temperature or the beer is
the same low temperature by filtration, the beer passed through a counter-current chiller in which
is rendered insensitive to changes of temperature, the beer can be chilled to any temperature
and freed, or practically freed, from fermentative without loss of gas or waste of beer. After
organisms, and will therefore remain brilliant cooling, the beer is stored for another few days
for a very considerable period. at a uniform temperature of 30F. to allow it to
4. The quick-chilling process consists in rapidly clarify to a considerable extent. It is then
cooling the beer down to 30 F., thoroughly im- filtered through a pulp filter and bottled in a
pregnating with carbonic acid gas, filtering at suitable machine.

the low temperature, and bottling. The com- Beer produced by this method requires no
plete plant consists of a refrigerating machine to carbonation, as the maturing and conditioning
cool a sufficient quantity of brine to about 20F., process itself furnishes quite sufficient gas for
brine-circulating pump, one or more beer-cooling beer condition either in cask or bottle. It will
cylinders, beer filter, and bottle-filling machine. also retain its brilliancy for a very long period
The refrigerating machines in general use are at any temperature.
either the ammonia-compression or the carbonic Great care should always be taken to
acid-compression system. The cooling cylinders thoroughly cleanse the pulp used in the filter,
are horizontal cylindrical vessels, either sur- and there are several machines available which
rounded by an outer jacket or shell around can be used for this purpose. Scrupulous
which refrigerated brine is caused to circulate, cleanliness of the whole plant as well as the
or fitted inside with a coil of pipe through which bottles is most important.
the cold brine passes, the coil being mounted on Certain improvements have been designed of
a shaft which allows it to revolve. late years in the brewing industry, and are
The beer is usually matured over hops in known as follows 1. The Schneifle-Hill Patent
:
cask for about two weeks. The cask of beer is brewing system. The claims of this process are
then transferred into one of the cylinders, which that neither tropical nor arctic temperatures
is at once subjected to the influence of cold by exert any after - influence on the stability,
the passage of cold brine, and at the same time brightness, and palate flavour of the beers pro-
the beer is charged with carbonic acid gas. The duced under this process. Among some of the
temperature of the beer is quickly brought down improvements in this system may be noted the
to 30 F., when it is allowed to rest a short time. retention of the natural gases of fermentation
It is then filtered through an efficient pulp filter in the beer, together with those exquisite
and bottled by means of a bottling machine. flavours of the ethers and other volatile
The beers produced by this method leave very products (which are always wasted by the
much to be desired both as regards flavour and ordinary methods of brewing) to the ultimate
palatefulness, but the process has found favour benefit to the beer in palatefulness, and con-
with many brewers, as it is very easy to manage dition. The fermentations, however, are con-
and requires no storage or lengthening matura- ducted precisely in the same manner as the
tion. ordinary top-fermentation system.
5. The balance of opinion, however, is in favour The albuminoids, also a most frequent cause
of the slow as against the quick-chilling system, of trouble, are dealt with by a most unique but
for undoubtedly the nearest approach to a well- simple clarifying system, whereby these undesir-
matured beer is one which by natural generation able constituents of malt worts are totally
of its own carbonic acid gas in cask or other eliminated. It has been found by practice that
vessel is afterwards allowed to cool down from two to six days are required to bring
slowly, and thus redissolve the free carbonic about these results, by which time the beer is
acid gas and at the same time precipitate thoroughly matured, and ready for filling into
troublesome resins and proteid matters. the trade casks. In conjunction with the above
The system consists in conditioning the beer advantages of always being able to supply the
in cask or other suitable vessel with the aid oi same and uniform beer throughout the year,
kraiisen or priming, gradually chilling and must be added the great advantage of the re-
filtering. duced cost of production. It is a point which
The beer is racked into either butts, hogs- must appeal to all brewers in these days of
heads, or glass-enamelled tanks, which wil severe competition and high prices of materials.
stand a good pressure, and 10 p.c. of kraiisen or Beers produced by this process can be brewed
sugar priming is added, the object being to with 2 Ibs. less original gravity, and still retain
BROMAL. 5C5
the same palatefulness. Less hops can also be BRIQUETTES v. FUEL ; also PITCH.
used at the rate of 1 J Ibs. to 2 Ibs. per quarter. BRITANNIA METAL. Is an alloy of vari-
There is no waste or returns from the tenants. able composition, usually containing only tin
Finings are dispensed with, no cellar room is and antimony, although brass and bismuth are
required in the brewery, as the beer is loaded on sometimes added.
to the drays immediately after racking. There An alloy consisting of 9 parts of tin and 1
is a great saving of time and labour over the part of antimony is attacked slightly by solu-
older system, with its drawing-off, topping-up, ;ions of common salt, potassium, ammonium,
and general care and attention on the floors. and magnesium chlorides, potassium sulphate,
2. The choice of an appropriate name for an potassium nitrate, and sodium carbonate. Caustic
entirely new article of manufacture is always at- soda has a more marked action (Dingl. poly. J.
tended with difficulty, for although the adoption 221, 259).
of a name of some kind or other is an easy This alloy is used in the manufacture of
matter, imperative that the name selected
it is teapots, spoons, and dish-covers.
be a compendious one, capable of affording some Articles made from it may be coloured by
indication of the nature of the product. This is aeating them for 15 to 30 minutes in a bath
more especially the case when the article is one made by mixing 2 Ibs. of water, \\ oz. of cream
designed for human consumption. Within the of tartar, \ oz. of tartar emetic, 2 oz. of hydro-
last few years there has been introduced into the hloric acid, \ Ib. of pulverised zinc, and 1 oz. of
brewing world an article termed concentrated
'
powdered antimony. This gives them a bril-
beer.' The article is a semi-solid one, for the liant lustre.
reason that the concentrated beer is the product By heating in a bath composed of 1 part
of the brewer's art, and is a finished product, tartar emetic, 1 part cream of tartar, 3-4 of
which needs only the addition of water to hydrochloric acid, and 34
of ground antimony,
convert it into a beverage. the following tints be obtained : golden,
may
Innumerable attempts to concentrate finished copper-red, violet, and blue-grey.
beer have been made, but these have always A
metallic ring can be given to articles made
ended in failure, as in the nature of things they of Britannia metal by heating them in an oil-
must end, for the reason that the concentration bath to 220 and then cautiously raising
of beer involves both the initial expense of the temperature to below 3 above the fusing
producing a completely finished article, which is point of the alloy. Small articles must be kept
subsequently partially destroyed, as well as the at this temperature for from 15 to 30 minutes,
cost of separating by evaporation 95 p.c. of the large articles for one hour ; the bath is then
liquid, causing loss of aroma, and the destruction allowed to cool. The rapidity of the cooling
'
of the palate' or flavour of the beer. The seems to have no appreciable effect (D. Ind. Ztg.
converse is the case in producing the concentrated 1867, 507) (v. ANTIMONY).
beer, for all the aroma is retained, the palate BRITISH GUM v.DEXTRIN.
improved, and the beer made from the con- BROCHANTITE. A hydrated basic copper
centrate rendered more wholesome than ordi- sulphate, CuS0 4 -3Cu(OH) 2 forming bright-green
,
nary beer. orthorhombic crystals, found in Cornwall, Urals,

To make one barrel of beer from the concen- &c. It is largely present in some of the Chilian
trate, a tin of the concentrated wort is dissolved copper ores. L. J. S.
in boiling water, and introduced into a 36- BROGGERITE. A crystallised variety of
gallon cask, or, if more convenient, a covered the mineral pitchblende or uraninite, found as
vat of about the same capacity. The wort is now
small, isolated octahedra and cubo-octahedra
cooled down to 60F., and about 1 Ib. of pressed in the felspar quarries near Moss in Norway. It
yeast is added. At the end of a few hours contains about 80 p.c. uranium oxide, together
fermentation takes place, which is finished at with thorium, lead, &c. Cleveite is a very
the end of a week. The beer is now ready for similar, or identical, mineral found in the felspar
drinking, and may be drawn off by means of quarries near Arendal in Norway. L. J. S.
a tap into clean bottles for storage if desired. BROMAL. Tribromaeetaldehyde CBr 3 CHO.
The 36-gallon cask will 24 dozen pint bottles. a
Prepared by passing bromine into solution of
fill
J. H.
paraldehyde in ethylacetate (Pinner, Annalen,
BRIDELIA BARK or ASDUANA. The bark 179, 68), or by passing bromine into absolute
of Brideliamontana is a useful Indian astringent alcohol, fractionally distilling the product, and
(Dymock, Pharm. J. [3] 7, 309). treating the fraction boiling at 165-180 with
"BRILLIANT ARCHIL, -AZURINE, -BLACKS water. The bromalhydrate thus formed is
V. AZO- COLOURING MATTERS. decomposed on distillation into bromal and
BRILLIANT CONGO, -CROCEIN, -DOUBLE water (Schaffer, Ber. 1871, 366 ; Lowig, Annalen,
SCARLET, -GERANINE v. Azo- COLOURING 3, 288). Bromal is an oily liquid boiling at
MATTERS. 174 (760 mm.) sp.gr. 3-34. Alkalis decompose
;
BRILLIANT COTTON BLUE TRIPHENYL- t>.

it on heating into bromoform and a formate.
METHANE COLOURING MATTERS. Bromalhydrate CBr 3 CH(OH) 2 Crystallises .
BRILLIANT GREEN v. TRIPHENYLMETHANE from water in colourless monoclinic prisms con-

COLOURING MATTERS. taining one molecule of water of crystallisation,
BRILLIANT ORANGE, -PQNCEAU, -PUR- m.p. 53-5. It is less soluble than choralhydrate
PURINE, -SCARLET v. Azo COLOURING - (Pope, Chem. Soc. Trans. 1899, 460).
MATTERS. Bromal alcoholates. Bromalethylalcoholate
BRILLIANT YELLOW v. Azo- COLOURING is a crystalline solid, m.p. 44 ; readily soluble
MATTERS. in alcohol, sparingly soluble in water (Schaffer,

BRIMSTONE v. SULPHUR. i.e.). Etard (Compt. rend. 114, 753) has de-
BRINDONIA INDICA v. GARCINIA INDICA. scribed the action of bromine on various alcohols
566 BROMAL.
with the formation of different bromal alcoho- salts, the bromide accumulates in the mother
lates. liquors, and can be recovered from these. Thus
The following condensation products ol Balard discovered bromine in the mother
bromal have been prepared : Bromalammonia liquors obtained on making common salt from
(Schiff and Tassinari, Ber. 1877, 1786); com- sea-water, and for many years it was prepared
pound with hexamethylenetriamine (Lederer, from the mother liquors of the saltworks at
Eng. Pat. 17693 ; J. Soc. Chem. Ind. 1897, Kreuznach, Schonebeck, Neusalzwerk, and other
1039) ; compounds with formaldehyde (Pinner, places in Germany. It was also found in 1846,
Ber. 1900, 1432); bromaldiacetate (Grabutti, by Alter, in similar mother liquors in America,
Gazz. chim. ital. 1900, 30, ii. 191) ; bromal- especially in those at Natrona and Tarentum,
glycolate (Gabutti, Chem. Soc. Abst. 1902, i. later on at Pittsburg, Syracuse, Pomeroy (Ohio),
261) ; and bromalchloralcarbamide (Kalle and and in the Kanawha region in West Virginia
Co., Chem. Soc. Abstr. 1902, i. 429). (Mason City, Parkersville, &c.).
BROMALIN. Trade name for a combina- Until about 1860 the little bromine that was
tion of hexamethylenetetramine with ethyl- made was nearly all used for scientific purposes.
bromide used in the treatment of neurasthenia Then, however, medicine and photography began
and epilepsy (v. SYNTHETIC DBTJQS). to demand a greater supply of bromides, and later
BROMBENZENE v. PHEKYL. on the manufacture of coal-tar dyes raised an
o-BROMCARMINE and 0-BROMCARMINE even more extended demand for bromine. It
v. COCHINEAL. now became remunerative to recover it in the
BROMCHINAL, BROMETONE, BROMEI working up of kelp for iodine, but this yielded
GON v. SYNTHETIC DEuas. only little and impure bromine, and was not
BROMINE. Sym. Br. At. wt. 79-92. An long continued. An idea was conceived of
element belonging to the class of the halogens ; recovering it from the water of the Dead Sea,
discovered by Balard in 1826. Name from but the project, hardly practicable in itself, was
Pp&fj.os,
& stench. Never found free ;chiefly in abandoned when Frank had shown that an ample
combination with alkalis and alkaline earths. supply of bromine could be obtained from the
As AgBr, in Mexico and Chili, in some Silesian mother liquors of the Stassf urt potash industry (v.
zinc ores, and in Chili saltpetre. In sea-water POTASSIUM CHLORIDE). He commenced his prac-
(in the ratio of 340 mgms. Br to 100 grams Cl) tical operations in 1865, when he manufactured
probably as magnesium bromide; in many about 750 kgs. of bromine in 1867 the output ;
marine plants and animals, and in many saline had already increased to 1\ tons, and in 1885
springs. Bromine, as bromindigo, has been the Stassfurt production of bromine was
found to be secreted by certain species of Murex, estimated at 260 tons per annum, the price
and is an essential constituent of the Tyrian having gone down from 50 or 60 (sometimes aa
purple of the ancients. Traces of it are occa- much as 90) marks per kilogram to 0-70 mark.
sionally to be met with in coal, and hence in This lowering of the price was principally due
gas liquors. to the fact that since 1868 the Americans had
At ordinary temperatures is a dark brown- come into the market with bromine made from
red liquid of most irritating smell, very volatile ; the above-named saltworks ; their liquors
vapour yellowish-red, and becoming less trans- contained it in such quantity that they are
parent when heated. able to sell much below Stassfurt prices.
Boils at 63 and solidifies at 7-3 to a brown- Few substances have so rapidly diminished
red crystalline mass of semi-metallic lustre and in price. Originally costing from 90 to 95 marks
conchoidal fracture. per kg., the price fell in 1867 to 40-45 marks,
Vapour acts on mucous membrane and then to 12 marks, later to 2-30 marks, 1-25
occasions great irritation. Sp.gr. of liquid and 0-70 mark. It is now about 1-60 marks.
3-18828, 0/4 (Thorpe). The world's production is now practically
A solution of bromine hi water, bromine controlled by the
'
'
Associated American Pro-
water, contains when saturated 3-169 p.c. at ducers,' and the German Bromine Conven-
ordinary temperature, and has a sp.gr. of tion,' in Stassfurt Leopoldshall.
1 -02367 ; it deposits when cooled bromine-hydrate Chemical Processes. The raw material worked
Br 2 10H 2 in hyacinth-red octahedral crystals. at Stassfurt, crude carnallite (v. POTASSIUM
The solution is frequently used in analysis as an CHLOBIDE), contains bromine to the extent of from
oxidising agent. Very soluble in alcohol, ether, 0-15 to 0-25 p.c. in the shape of brom-carnallite
carbon disulphide, chloroform, and cone, MgBr 2 -KBr,6H 2 0, isomorphous with carnallite.
hydrochloric acid ; sulphuric acid dissolves In the manufacture of potassium chloride, the
traces only. magnesium bromide accumulates together with
Bromine acts violently on hydrogen, sulphur, magnesium chloride in the mother liquors, which
phosphorus, arsenic, antimony, tin, the heavy contain usually from 0-2 to 0-3 p.c. bromide.
metals, and potassium ; but it does not react As it is impossible to separate the magnesium
with sodium, even on heating to 200. Acts as bromide by fractional crystallisation, the
a bleacher and disinfectant. bromine is always extracted chemicalty, being
Extraction and Manufacture. Bromine occurs replaced by a current of chlorine, according to
in nature principally, and so far as its industrial the equation :
preparation is concerned, exclusively in the MgBr 2 +Cl 2 =MgCl 2 +Br 2 .
shape of bromides, accompanying in small The chlorine is either generated within the
quantities the chlorides of sodium, calcium, and liquors by means of hydrochloric acid and
magnesium. Its quantity is never large enough manganese ore, or it is prepared outside and
to admit of its being prepared directly from the passed into the solutions, cheap compressed *
raw material, but where the latter is in the first hlorine in steel cylinders being nowa
instance worked for sodium chloride and other available for that purpose.
BROMINE. 567
In the early days of the bromine industry, various continuous processes, the first of which
the extraction was always done by intermittent was patented by Frank in 1878.
working. One of the first apparatus employed He employed a series of decomposing vessels
was devised by Frank, and is shown in Fig. 1. at different levels, allowing the heated liquor
It consisted of a square vessel or still, A, made of to run from the highest into the next lower one,
sandstone or slate properly jointed together, of and so on, passing at the same time chlorine gas
about 3 cubic metres capacity, which was generated outside and steam into the lowest
charged with a definite quantity of mother liquor vessel, and in counter-current to the higher ones.
previously heated to 60 in tank B by steam coil He thus obtained a steady stream of bromine
i; about 200 kgs. of manganese ore, sufficient for on the one hand, and a solution of magnesium
several operations, were spread on the false chloride practically freed from bromine and
bottom a. After closing the man-hole /, the uncontaminated with manganese salts, on the
required quantity of sulphuric acid of sp.gr. 1-7 other. After a time, chlorine was passed into
was run in through pipe g, which was subse- the second lowest vessel, and steam only into
quently stopped up with clay, and live steam the lowest, to free its contents from chlorine
was passed into the liquor through pipe k. The before running off. However, the high pressure
chlorine evolved on boiling acted upon the mag- required to force the chlorine gas through
nesium bromide present and liberated bromine. several successive layers of the liquor presented
This came over pure at first, but above 75 a great difficulties in the design and working of
mixture of bromine, chlorine, and water vapour this plant. These were overcome by the applica-
passed through the lead pipe h and the stone- tion of the scrubber principle in the apparatus,
ware condensing coil c into the glass bottle D, patented in 1882 by the Leopoldshall Chemical
Works (Ger. Pat. 19780). and shown in
Fig. 2. *- :
The heated mother liquor flows through
the water-sealed pipe a into
column A constructed of stone-
ware or acid-resisting stone,
where it is evenly distributed
by pipe b. The column is fitted
with stoneware balls c, c resting
on a grating which effects
a good contact of the liquor
with the
chlorine
gas as-
cen ding
through
pipe z.
This pipe
is wide
enough
to serve
also as
outlet
for the
liquor
Fm.
which
runs into
holding about 8 litres. The distillation was the steaming vessel B, provided with a number
carried on until the pale colour of the vapours of superimposed flagstone shelves compelling
in the glass adapter n showed that no more the liquor to flow in a zigzag course, and
bromine was coming over. The condensate finally issues through pipe i. Steam is forced
separated into a lower layer of bromine and an into this vessel by means of a stone pipe g
upper layer of bromine and chlorine water and is distributed through perforations in its
which could be siphoned off through o into base. The contents
of B, which is always
vessel E,and was added to a subsequent charge. full, arekept boiling, and the steam rises
Uncondensed vapours passed into vessel F filled principally through holes in the flagstones,
with iron turnings and water, and fitted with a thereby freeing the liquor from chlorine and
collar, p, to allow for frothing, with a run-off bromine. The vapours meet the current of
into jar o. Each operation, lasting an hour to fresh chlorine arriving through pipe I (shown in
an hour and a half, was terminated by knocking dotted lines), which is conveyed through pipe
out plug I, and running off the liquor through the z into the tower A, decomposing the magnesium
covered culvert m connected to the factory bromide. The bromine is taken off on top, and
chimney. passed by pipe o through the stoneware con-
The efficiency of this process was very small, denser p into the receiver q. The uncondensed
each operation yielding 2 to 2-5 kgs. bromine, the vapours are led through x, into receptacle n,
average yield amounting to not more than 0-1 and arrested in the smaller scrubber d suspended
p.c. of the mother liquor. The intermittent by rod t, and fitted with iron borings, kept
method entailed several drawbacks loss of time moist by a stream of water from tube /. The
and material, besides the contamination of the iron bromide collected in n is siphoned off
atmosphere. These disadvantages gave rise to through v into jar w. The regularity of the
568 BROMINE.
current of chlorine arriving from m
is controlled
by the amount of water condensing in the bend

of the glass tube h. If too much water has
accumulated, it is blown through the rubber
tube u into the chlorine washer D. By filling
the bend of h with water, the current of gas
may be interrupted. Of late years chlorine
electrolytically prepared and compressed in steel
cylinders has been used, whereby the regularity
of the current is under complete control.
The apparatus patented by Wiinsche-Sauer-
brey (Ger. Pat. 158715) is based on the same
principle as the foregoing. It is, however, tech-
nically more perfect and consequently much
superior in efficiency.
It consists of a decomposing vessel, a steam-
ing vessel, a condenser, and an auxiliary con-
denser. The four units are built up of cast-iron
elements of hexagonal cross- section, lined with
stoneware plates and
filled with a very large
number, several thou-
sands, of specially de-
signed contact bodies
ffiWXXWOG which rest on gratings
of the same material.
The four units are so
in height
that a perfect counter-
is obtained,
and in both the decom-
BROMINE. 569
not more than about 70 p.c. in any other method. distils over and condensed in a stoneware
is
This low yield is largely due to the extremely coil, separated from water and then contains
small percentage of bromine in the
liquors and | only from 0-05 to 0-10 p.c. chlorine.
the consequently large bulk to be dealt with, and Recent processes attempt the purification by
to the formation of bromates and rectifying without the aid of chemical agents.
chlorates. The formation of solid Kubierschky (Ger. Pat. 174848) employs in con-
magnesia is another drawback. nection with his separating apparatus a refining
I In nearly all the electrolytic tower ; the crude bromine flows downwards
methods proposed, the bromine re- into a vessel charged with bromine and kept at
mains dissolved in the solution and boiling temperature. The chlorine rises in the
must be recovered by tower, and the boiling bromine, freed from
the processes described chlorine, is continually siphoned off and cooled.
above. The German Solvay Works (Ger. Pat. 205448)
Purification have found that in raising the temperature of
of Bromine. crude bromine very slowly and keeping it just
Crude bromine, under its boiling-point, it is possible to free it
as obtained by entirely from its chlorine. The time factor is of
most of the great importance for the successful carrying out
processes de- of their process.
scribed, con- On heating a charge to 59 for 36 to 40 hours,
tains very small it is remove practically all the chlorine
possible to
quantities of with not much more bromine than corresponds
iodine, cy- to the composition of bromide of chlorine.
anogen, Bromine is sold in strong, white, stoppered
bottles, holding 1 litre, and containing 2J or 3
kilos. The glass stoppers must be well ground ;
they are secured by pouring some shellac on to
the joint, covering them with clay putty, and
tying wet parchment paper over all. From four
to twelve such bottles are placed in a wooden
FIG. 3.
box, the spaces between being tightly filled with
bromoform and carbon tetrabromide, lead kieselguhr or brown-coal ashes, depending upon
bromide, and as principal impurity from 1 to whether the bromine is exported or sold for
4 as chloride of bromine. The
p.c. of chlorine inland consumption.
oldest method
of purification consisted in agitat- The principal applications of bromine,
ing the crude bromine with a solution of potas- whether in the free state or in the shape of
sium or ferrous bromide. On account of the bromides, are in photography, in medicine, in
frequent breakages of the glass vessels employed, the manufacture of coal-tar dyes (especially
this method was replaced
by that of redis- eosine), and in scientific and analytical chemistry;
tillation. In some places glass retorts were in the latter it has to a great extent taken the
used for this purpose, place of chlorine, owing to the greater con-
containing about 15 kgs. venience of its manipulation. A
similar substi-
and heated in sand-baths. tution has been proposed for many technical
Only 3 or 4 charges could purposes. It is used in the extraction of gold
be worked in one vessel, and the refining of platinum, and in connection
and fracture of the retorts with the manufacture of Prussian blue and
was a not unfrequent oc- potassium permanganate. It is also a disin-
currence. In Stassfurt fectant, and has found some application for
sandstone stillswere and this purpose, especially in the shape of bromum
are still employed. These solidificatum patented by Frank (Ger. Pat. 21644).
were square troughs with This is kieselguhr made plastic by means of
a stone cover, holding molasses, &c., pressed into sticks of J- and J-inch
about 1 cubic metre. The diameter, dried, burned to the extent that the
distillation is carried out sticks acquire a sufficient degree of hardness
in the presence of ferrous without losing their porosity, and saturated
or calcium bromide, these with liquid bromine in wide-mouthed stoppered
liquors being, when used glass bottles. After the excess of bromine has
up, added to the original been poured off, the sticks remain behind, con-
mother liquors. Of late taining about 75 p.c. of the weight of bromine,
years advantage has been and are sold in the same bottles. This is a very
taken of the improved convenient form of applying it, as a certain
products of the stoneware industry, and stills of number of sticks represent a given weight, and
this material are
largely used. To avoid the no weighing out of liquid bromine is required.
occasional cracking of these stills, Mitreiter Bromide of iron is made at Stassfurt, and
employs vessels of boiler plate lined with a serves principally as raw material for the
bromine resisting material. manufacture of potassium and sodium bromide.
The still is charged with 200 litres ferrous It is a compound of the formula Fe 8 Br s , con-
bromide solution of 13 to 18Be, and about taining 56-70 p.c. bromine, up to 0-6 chlorine,
600 litres crude bromine. The temperature is 18-19 p.c. iron, and 10-15 p.c. water and in-
gently raised by direct steam up to the boiling- soluble matter. The older method for its manu-
point. Double decomposition ensues between facture consists in passing bromine vapours free
chlorine and ferrous bromide, and bromine from chlorine over iron borings or turnings
570 BROMINE.
contained in a cast-iron or stoneware vessel, and For pharmaceutical purposes a dilute solu-
kept moist by a stream of water. The solution tion of hydrobromic acid may be prepared by
obtained is passed through a filter cloth or dissolving 84J grains of potassium bromide in a
sand filter to remove impurities, notably carbon, fluid ounce of water and adding 9 grains of
and evaporated in cast-iron pans, whereby enough tartaric acid to the solution. After standing, acid
bromine is added to obtain the compound potassium tartrate crystallises out and the
Fe 3 Br,. The brown-red solution is concen- solution contains about 10 p.c. of hydrobromic
trated to a pasty consistency and allowed to acid. Hydrobromic acid has been used in the
cool to a black crystalline mass. treatment of ear complaints. R. L.
The Associated Chemical Works of Leopolds- BROMIPIN. A combination of bromine with
hall have introduced a method whereby a sesame oil employed in medicine (v. SYNTHETIC
charge of 1 ton of steel wire and turnings is DRUGS).
treated in a closed stone trough with a mixture BROMITE or BRpMYRITE. Native silver
of bromine vapour and steam in the right bromide, found in Mexico and in Chili (v. SILVER).
proportion. The admission of bromine is so BROMOCOLL v. SYNTHETIC DRUGS.
regulated that no bromine vapours are visible BROMOFORM. TribrommethaneCHBT 3 . This
through a sight-glass provided on the outlet pipe substance is occasionally met with
in the liquid
which is connected to a little scrubber acting as a left after the rectification of bromine, in which it
catch-box. As soon as brown vapours and the occurs associated with chlorobromoform CHBr 2 Cl
falling of the temperature from 170 to 100 indi- (Dyson, Chem. Soc. Trans. 43, 46) and carbon
cate a lessening of the activity of the iron, the tetrabromide CBr 4 (Hamilton, ibid. 39, 48).
operation is terminated and the solution run off. Preparation. It may be obtained by mixing
Being sufficiently concentrated, the solution 100 c.c. soda lye, 200 c.c. acetone, and 20 c.c.
obtained in the process may be run direct into bromine. When the reaction has ceased, 10 c.c.
the transport barrels, where it is allowed to acetone are added to remove the yellow colour
crystallise. of the hypobromite, the layer of bromoform
Bromine salt. In connection with the which separates being tapped off and rectified.
manufacture of bromine a substance commonly Yield 75 p.c. (Deniges, J. Pharm. Chim. 24, 243).
'
called ' bromine salt is produced which finds
)
It may also be prepared by the simultaneous
application in the extraction of gold ores. It is action of bromine and caustic potash on alcohol,
practically the mixture NaBr0 3 +2NaBr, and of bromine and lime on acetone (Beniger,
is made by saturating concentrated caustic soda Amer. Pharm. 63, 80) ; of calcium hypo-
J.
solution with bromine. The solid salt obtained chlorite and potassium bromide on acetone
after draining off the mother liquor which is (Fromm, Pharm. Zeit. 39, 164), and by the
evaporated has the approximate composition action of alkalis on bromal. It has been made
!NaBr0 3 +5NaBr. To this sodium bromate, electrolytically from potassium bromide
and
electrolytically prepared from bromide, is added, alcohol (Fabrik vom Schering, D. R. P. 29771);
and the mixture finely ground and packed in from potassium bromide and acetone (Coughlin,
Amer. Chem. J. 27, 63 and Miiller and Loebe,
;
Hydrobromie acid. HBr. Bromhydric acid ; Zeit. Elektrochem. 10, 409), and from calcium
Hydrogen bromide. A colourless pungent gas bromide, alcohol, and water (Trechcinoki, Chem.
of irritating smell fumes strongly in the air.
; Zentr. 1907, i. 13).
Condenses to a liquid at 73. May be ob- Properties. It is, when
pure, a colourless
tained synthetically by passing bromine and liquid, solidifying at 9 and
boiling with slight
hydrogen through a hot tube or over heated decomposition at 146 under 751 mm. (Wolff
platinum. Best prepared by action of phos- and Schwabe, Annalen, 291,241), at 151 under
phorus and bromine on water, 5Br+P+4H 2 0= ordinary pressure. Sp.gr. 2-902, 15/15 (Perkin,
H s P.O 4 +5HBr; or by the action of a concen- Chem. Soc. Trans. 45, 533). It is decomposed
trated solution of 3 P0 4
Hon KBr ; or by drop- by potash into potassium bromide, hydrogen
ping Br upon melted paraffin heated to 185. bromide, and carbon monoxide, and may be
Gas very soluble in water ; solution when estimated by means of this decomposition
saturated forms a colourless, strongly acid liquid (Desgrez, Compt. rend. 125, 780, and Annalen
of sp.gr. 1-78, and contains 82 p.c. HBr by 23, 76; andRichaud, Pharm. Chim. 1899, 232).
J.
weight, corresponding to the formula HBr,H 2 0. Under the influence of light and air it decomposes,
If the concentrated acid be heated at ordinary the decomposition products depending on the
pressures, the gas is evolved until the amount time of exposure and the amount of available,
of HBr in the solution sinks to 47-48 p.c., when oxygen (Schoorl and Van den Berg, Chem. Zentr.
the Liquid boils constantly at 126 under a 1906, i. 441). It has been used to a slight
pressure of 760 mm. This proportion of HBr extent as an anaesthetic, and in the treatment of
corresponds to HBr+5H 2 0, but the liquid is diphtheria. Bromoform in water to
which a
not a true hydrate, since the composition is littlealcohol has been added, has been success-
altered by varying the pressure ; thus if the fully used in cases of whooping-cough compli-
pressure be raised to 1-95 mm., the solution boils cated with pneumonia (Stepp and Goldschmidt,
at 153 and contains 46-3 p.c. HBr. J. Soc. Chem. Ind. 1890, 213).
The sp.gr. at 15 and p.c. composition of BROMOL, BROMOLEIN, BROMOTAN v.
aqueous solutions of
hydrobromic acid, is given SYNTHETIC DRUGS.
in the following table (Wright, Chem. News, 23, BROMURAL. Trade name for a-monobrom-
242) :
isovalerianylurea. Employed as a hypnotic.
Sp.gr. HBr p.c. Sp.gr. HBr p.c. Forms white needles, slightly bitter in taste;
1-080 10-4 1-385 40-8 readily soluble in hot water, alcohol,
and ether,
1-190 23-5 1-475 48-5 sparingly soluble in cold water; m.p. 147.
1-248 30-0 1-515 49-8 BRONZE v. Tor.
BROOM TOPS. 571
BRONZE POWDERS. The manufacture of

these powders is and
carried on largely at Fiirth
Nuremberg in Bavaria. Bronze powders are
composed of copper, zinc, tin, and antimony,
melted together in the requisite proportions.
In the process of manufacture, the alloy is cast
into rods \ inch in diameter and 3 feet long.
These are rolled until about 2 inches wide, and
then cut into lengths suitable for handling. The
pieces are hammered out thin, and cleansed by Colour of
immersion in dilute sulphuric acid. The dried powder
material is then beaten out by steam-hammers
until the limit of thickness is reached, when it is
cut up by shears into small particles or ' clip
pings.' These are then pulverised in stamp mills,
and the powder sifted, to separate the heavier
and better quality powder from inferior material.
The latter is mixed with quartz powder and
sold very cheaply (J. Soc. Chem. Ind. 1893, 12,
475).
The expense of the above process lies mainly
'
in the production of clippings,' which necessi-
tates a great deal of handwork, and a number of
methods have been patented for reducing the
alloy to a finely divided state by mechanical
means. According to one method, the molten
alloy rained into a sheet-iron chamber, in
is
which a shaft carrying blades is rapidly rotated,
so as to greatly agitate the air and thereby
minutely subdivide the metal at the moment of
solidification (Fr. Pat. 331371, 1903). In
another, the molten metal flows in a thin film
into a receptacle, where it meets a current of
compressed air or else a jet of water, the object
being to produce bronze foil or leaves (Eng.
Pat. 9064, 1903). Methods have also been
patented for casting the metal in thin films on
the inner surface of a rotating hollow cylinder
or in the annular space between two rotating
cylinders (J. Soc. Chem. Ind. 1903, 22, 150 ; Fr.
Pat. 335112, 1903).
After the powdered metal has been sifted,
the coarser grades are polished in a closed steel
cylinder, in which steel wire brushes rub against
the walls. When it is necessary to reduce the
powder to a finer state of division, it is rubbed
with gum-arabic solution, washed and dried at
the lowest possible temperature.
Zinc-dust is frequently coated with brass by
simple immersion in a copper and zinc cyanide
solution, the powder being kept agitated by
means of brushes (J. Soc. Chem. Ind. 1894, 13,
893, 958) ; the product is treated finally in a
polishing mill, and used as a bronze powder.
Bronze powders have also been described
containing 5-10 p.c. of aluminium, and 0-05-
0-1 p.c. of bismuth. The shade of colour is
altered by varying the percentage of aluminium,
and by heating in air (D. R. P. 44242, 1887).
Few analyses of bronze powders have been
published
'
(J. Soc. Chem. Ind. 1910, 29, 1062).
' '
Gold' and bronze powders were found to
contain 70-85 p.c. of copper, and 30-15 p.c. of
zinc, together with small amounts of lead, tin,
'
arsenic, iron, and aluminium ; aluminium '
powders consist of nearly pure aluminium ; and
' '
silver powders contain 77 p.c. of zinc and
21 -5 p.c. of aluminium.
Bronze powders are coloured in various ways.
One method consists in heating the powder in
an open vessel with oil and vinegar, or with
wax, paraffin, or oils containing sulphur.
572 BROOM TOPS.
dry hydrogen, 754 mm. (Moureu and Valeur, The latex of this urticaceous tree (cow-tree, milk-
Compt. rend. 137, 194). With acids spar- tree), growing in Venezuela, approximates to
teine combines, forming crystallisablo salts : :ow's milk in composition. It contains 35-2 ]>.<.
B"(HCl) 2 PtCl 4 2Aq., yellow crystalline powder of wax and saponifiable matters, which are used
(Mills); B"(HCl) 2 AuCl 3 (Mills); B"H 2 S0 4 , large in the manufacture of candles (Boussingault,
prisms, v. sol. water (Bamberger) ; B'HI, Pharm. J. [3] 9, 679).

four-sided plates, sol. hot water (Bamberger) ; BROUSSONETIA PAPYRIFERA (Vent.).
B"(HI).,, silky needles (Bamberger). Spartei'ne The Paper mulberry. The fibrous bark is used
is a narcotic poison resembling nicotine, but in China and Japan for the manufacture of a
less active (Stenhouse; cf. See, Compt. rend. 101, kind of paper, and in Polynesia in the manu-
1046). A
characteristic orange-colour reaction facture of Tapa cloth.
is said to be produced when spartei'ne or its BROWN, ACID, v. Azo- COLOURING MATTERS.
salts are added to sulphydrate of ammonium BROWN, ANILINE BISMARCK BROWN, ;
(Grandval a. Valser, J. Pharm. Chim. [5] 14, 65). MANCHESTER BROWN, PHENYLENE
The more important reactions of sparteine BROWN, VESUVINE, LEATHER BROWN.
are 1. Nitric acid converts it into a compound CINNAMON BROWN, ENGLISH BROWN, or
:
which yields chloropicrin when treated with GOLD BROWN v. Azo- COLOURING MATTERS. ;
chloride of lime (Stenhouse). 2. Oxidised with BROWN, ANTWERP, v. PIGMENTS.

potassium permanganate, it yields formic and BROWN, ARCHIL, v. Azo- COLOURING MAT-
oxalic acids (Bamberger ; Ahrens). 3. Oxidised TERS.
by peroxide of hydrogen, a new base, dihydroxy- BROWN, BONE, v. PIGMENTS.
sparteine C 16 H 26 N 2 O 2> is
syrupy, formed. It is BROWN, CALEDONIAN, v. PIGMENTS.
colourless, not crystallisable, and distils with BROWN, CAPHEK, v. PIGMENTS.
difficulty with steam. Platinum salt BROWN, FAST, v. Azo- COLOURING MATTERS.
B"(HCl) 2 PtCl 4 blackens at 235
, and gold salt ; BROWN, FUSCANINE, v. AMINOPHENOL.
B'(HCl)AuCl 3 melts at 143-146 (Ahrens). BROWN, GARNET. The potassium or am-
4. Reduced by nascent hydrogen, a colour- monium salt of isopurpuric acid (C 8 HN 4 6 S K or
less oil, dihydrosparteVne C 1B H 28N 2 results. C 8H 8N8 8Obtained by Hlasiwetz in 1859 by
).
It boils at 281-284, and forms a crystalline the action of potassium cyanide on picric acid
platinum salt B"(HCl) 2 PtCl 4 , which blackens at (Annalen, 110, 289). Forms a dark-brown
239 (Ahrens). 5. With alkyl iodides and alcohol powder, readily soluble in hot water with red-
sparteine reacts, forming (C 15 2; EtN 2 )I 2 (Mills) H dish-brown colour. Dyes wool and silk brown
H
and (C 15 27 MeN 2 )I 2 (Coninck), which compounds in an acid-bath. No longer is use (v. also
by the action of oxide of silver yield the hy- ISOPURPURIC ACID).
H
droxide (C 15 27 EtN 2 )(OH) 2 (Mills), and by the BROWN, MADDER, v. PIGMENTS.
N
action of soda (C 1 5H 26 2 )EtIand(C 15 2tt 2 )MeI H N BROWN, NAPHTHYLAMINE, v. Azo.
(Bamberger). MUls also obtained a diethyl COLOURING MATTERS.
H
di-iodide (C 15 26 Et 2 2 )I 2 . N
6. Heated with con- BROWN, PHENYL, v. PHENYL BROWN.
centrated hydriodic acid at 200, methyl in the BROWN, PICRYL, v. PICRYL BROWN.
form of methyl iodide is removed, and there BROWN, PIGMENT, v. Azo- COLOURING
H
remains a newbase C 14 24 N 2 , b.p. 276 (Ahrens). MATTERS.
This, however, according to Herzig and Meyer BROWN, PRUSSIAN, v. PIGMENTS.
(Monatsh. 16, 605), is only impure sparteine. BROWN, RESORCIN, v. Azo- COLOURING
7. When sparteine is distilled with lime the MATTERS.
distillate contains ethylene, propylene, (7)-pico- BROWN, SOUDAN, v. Azo- COLOURING
line, and a new tertiary base (Ahrens). MATTERS.
Scoparin was obtained by Stenhouse from BROWN, VANDYKE, v. PIGMENTS.
broom tops, after a series of processes to free it BROWN, VERONA, v. PIGMENTS.
from the chlorophyll with which it is associated, BROWN BERRIES. The fruit of Rubus
as a pale-yellow powder which crystallises with fruticosus.
difficulty. It is
sparingly soluble in water, but BROWN COAL v. FUEL.
is soluble in alcohol and alkalis. Its solution in BROWN HAEMATITE v. IRON, ORES OF.
ammonia is deep yellow-green. With chloride BROWN IRON ORE (Limonite) v. IRON,
of lime a green colour is produced. Nitric acid ORES OF.
converts it into picric acid. Melted with potash BROWN OCHRE. A soft variety of brown
it gives phloroglucinol and protocatechuic acid iron ore occasionally used as a pigment.
(Hlasiwetz, Annalen, 138, 190). Recent investi- BRUCINE v. VEGETO- ALKALOIDS.
gations show that scoparin, which melts at BRUCITE. Native magnesium hydroxide
202-219, according as it is slowly or quickly Mg(OH) 2 found as platy crystals with perfect
,
heated, has the constitution OH-C 19 16 8 H micaceous cleavage, or as lamellar masses, in

OMe+5H 2 0. It gives a violet-blue colour serpentine rocks, at Unst, one of the Shetland
with ferric chloride, quickly becoming dark- Isles, at Texas in Pennsylvania, &c. It some-
brown, and reduces Fehling's solution (Gold- times contains a small amount of iron (ferro-
schmidt and v. Hemmelmayr, Monatsh. 14, brucite) or manganese (manganbrucite). A
202 15, 316
; A. G. Perkin, Chem. Soc. Proc.
; fibrous variety is called nemalite. L. J. S.
1899, 123). Heated with alcohol a less soluble BRUNSWICK BLACK is prepared by fusing
modification, isoscoparin, is formed, which is 2 Ibs. of asphalt, and mixing thoroughly with
readily reconverted into scoparin by solution in 1 pint of hot boiled oil. When cool, 2 pints
alkali and precipitation by an acid (Stenhouse). of turpentine are added to the mixture. An
/soscoparin melts at 235 (Goldschmidt and v. inferior but cheaper black may be made by
Hemmelmayr). A. S. boiling gently together for five hours
25 Ibs.
BROSIMUM GALACTODENDRON (Don.). each of black pitch and gas tar asphaltum ;
BUCKTHORN. 573
8 gallons of linseed oil, and 10 Ibs. each of litharge leaves of Barosma
serratifolia yield 1 p.c. of an
and red lead are then mixed in, and the whole oil which remains liquid under similar conditions.
boiled. After cooling, the mixture is thinned by to Kondakoff and Bochtschiew
According
the addition of 20 gallons of turpentine (v. also (J. pr. Chem. 1901, 63, 49), the best oil of
BONE OIL). bucco or buchu leaves contains 10
p.c. of
BRUNSWICK GREEN. An oxychloride of hydrocarbons, consisting of a variety of d-
copper, used as a pigment. Copper filings or limonene and dipentene 60 p.c. of a ketone
;
turnings are moistened with a solution of sal- Ci H 18 0, [o] D -166', b.p. 208-5 - 209-5,
,
ammoniac, and left in contact with the air ; the which, on reduction, yields a menthol not identi
oxychloride so formed is washed off with water, cal with the natural product 20 p.c. of dios ;
and dried at a gentle heat. The term is also ap- 5 p.c. of resin and 5 p.c. of other
phenol ; ;
plied to chrome green and to emerald green constituents (Kondakoff, J. pr. Chem. 1896,
(v. COPPER and PIGMENTS). 54, 433). After removing diosphenol from the
BRUSHITE. A
hydrated phosphate of lime oil of buchu leaves,
HCaP0 4 ,2H 2 O Tschugaeff succeeded in
occurring in the guano of Aves obtaining xanthogenide derivatives of d-menthol
Island and Sombrero in the Caribbean Sea. from a traction of the residue J. Russ. Phys.
BRUSSELS SPROUTS. A
variety of the Chem. Soc. 1910, 42, 714; Skovortsoff, ibid.
(
cabbage (Brassica oleracea), in which numerous ii.

55). Diosphenol or buchu camphor (Bialo-
small heads are developed along the stalk from
the axils of the leaves, instead of one terminal
brzeski, I.e. ; Kondakoff, I.e. Semmler and ;
McKenzie, I.e. ; Semmler, Chem. Zeit. 1906,

head.
30, 1208; Kondakoff, Chem. Zentr. 1905, ii.
The edible portion contains, according to 1252 ; Chem. Zeit. 1906, 1090, 1100) is optically
American analyses :
inactive, has m.p. 82, b.p. 109-110/10 mm.,
Water Protein Fat Carbohydrates Ash
88-2 4-7 1-1
232/755 mm. Its composition is probably
4-3 1-7
C ]0 H 1?
2 It is a phenolic aldehyde, yielding
.
(see CABBAGE). H. I. an oxime, m.p. 156 (Semmler and McKenzie

BRYOIDIN OLEO-RESINS.
v.
125). With hydrochloric acid it yields thymol
BRYONY ROOT. Contains a white, very and a little carvacrol. With hydriodic acid it
bitter dextrorotary glucoside, bryonin, of the yields a hydrocarbon C 10 H 20 b.p. 165-168/762 ,
formula C 34 4g 9 H yielding, by hydrolysis mm. whilst with sodium in alcoholic solution

;
H
bryogenin C 14 19 0,,; m.p. 210, dextrorotary it forms (1) a menthol
(2) a crystalline glycol
;
]D
=: + 105 , soluble in cone, sulphuric acid, C 10 H 18 (OR) 2 m.p., 92; and (3) an isomeric
forming a red solution changing to purple on glycol, b.p. 141-5-145/13 mm. With alco-
heating, and giving a purple precipitate on the holic potash, a hydroxy acid of the terpene
addition of water (Masson, J. Pharm. Chim. [5] series, m.p. 94", is obtained. This acid has been
27, 300). synthesised, and is identical with the natural
BUBULIN (from &ovs, ox). The name of a product. The dibromide C 10 H 14 2 Br 2 and
peculiar substance, said by Morin to exist in cow- other derivatives of diosphenol have also been
dung, and -to be precipitated by metallic salts, obtained.
tincture of galls, and alum, and therefore to be BUCKTHORN (Rhamnus cathartica [Linn.]).
active in the application of cow-dung to calico- This plant is a native of England ; it
grows
to a height of from 15 to 20 feet ; its flowers
printing.
BUCHU v. OILS, ESSENTIAL. are greenish-coloured, and its berries four-
BUCHU or BUCCO. The leaves of three seeded. The juice of these when in an unripe
varieties of Barosma (ord. Rutaceae), viz. B. state has the colour of saffron ; when ripe
betvlina (Bartl et Wendl. f.), B. crenidata (Hook.), and mixed with alum, it forms the sap or
and B, serratifolia (Willd.), are known under this bladder-green of the painters (v. PIGMENTS) j and
name. The leaves are used medicinally by the in a very ripe state the berries afford a purple
South African natives. colour. The bark also yields a fine yellow
Their composition has been studied by dye.
Brandes (Arch. d. N. Apoth. Ver. 22, 229), The berries of the Rhamnus carthartica (also
Landerer (Buchner's Re'pert. 84, 63), Fliickiger known as Hungarian berries) have been examined
(Pharm. J. 3, 4, 689 ; [3] 11, 219), Wayne (ibid. by Tschirch and Polacco (Arch. Pharm. 1900,
3, 6, 723). By extracting the leaves with light 2o8, 409), and evidently contain substances
petroleum, Bialobrzeski (Chem. Zentr. 1896, ii. chemically distinct from those which are present
551) obtained chlorophyll, a resin, and an in Persian berries.
ethereal oil
containing chiefly diosphenol, Ether extracts from an aqueous extract of
H
together with a terpene C 10 18 b.p. 174-176, ,
the berries rhamnocitrin, rhamnolutin, rhamno-
and a ketone isomeric with menthone, and chrysin, and the residual watery liquid on boiling
having the constitution C 10 18 O, b.p. 206- H with dilute sulphuric acid gives, in addition to
209 ; it yields an oxime and a tribrom deriva- rhamnocitrin, ^-rhamnocitrin. The berries al-
tive. After extraction with light petroleum, ready extracted with water contain rhamno-
the leaves, on treatment with cold alcohol, emodin and rhamnonigrin.
yield 3 p.c. of a brownish-green bitter resin Rhamnocitrin C 18 H 10 3 yellow needles, melts
,
insoluble in benzene, and when the alcoholic at 221-222, and soluble in alkaline solutions,
is
extract is treated with sodium carbonate or with a yellow colour. Alcoholic lead acetate
by other methods diosmin is deposited, forming gives an organic coloured precipitate, and ferric
tasteless, odourless crystals, m.p. 244. chloride a green colouration. The solution in
Semmler and McKenzie (Ber. 1906, 1158) sulphuric acid possesses an intense green
found that the round leaves of Barosma betulina fluorescence.
yield about 2 p.o. of an oil which crystallises on Triacetylrhamnocitrin C 13 H 7 5 (C 2 H 3 0) 3 forms
standing at ordinary temperature ; but the long colourless needles, melting at 199-200.
574 BUCKTHORN.
Rhamnocitrin appears to be a dihydrotrihy- /8-rhamnetrin of Schutzenberger (see PERSIAN
droxyxanthone, and probably possesses the follow- BERRIES).
ing constitution : Rhamnoemodin C]5 H 1(j0 5 m.p. 254-255,
,
OH OH is similar to frangula emodin (R.

frangula) which,
according to Oesterle, melts at 250.
HC Rhamnonigrin is converted by boiling with
nitric acid into chrysamminic acid, and
by
HCxx
Y /C\
xo/ VCH ' digestion with boiling alcoholic potash into
emodin.
OH H The alder buckthorn (Rhamnus frangula)

grows naturally, and is very abundant in woods
It dyes with iron mordant a green-brown, and and thickets, in some parts of Britain. The
with aluminium mordant a bright-yellow colour. berries of this species are often substituted for
H
Rhamnolutin C 15 10 6 small canary-yellow those of the above but they are easily detected,
, ;
needles, melts above 260, and gives with lead since they contain only two seeds. In a green
acetate an orange-red precipitate, with ferric state they dye wool green and yellow ; when
chloride a green-black colouration. Its sulphuric ripe, bluish-grey, blue, and green. The bark also
acid solution posseses a strong green fluorescence. dyes yellow, and, with preparation of iron, black
H
Tetraacetylrhamnolutin C 1 5H 6 O (C 2 3 0) 4 , colour- (Lawson)
fi
less needles, melts at 182-183. Rock buckthorn (Rhamnus saxalilis), yields

Rhamnolutin dyes aluminium- and iron- berries which are used to dye morocco leather
mordanted fabrics respectively canary-yellow yellow. These, in common with the narrow-
and green-brown shades. It appears to be a leaved buckthorn berries (R. alaternus [Linn.])
tetrahydroxyflavone, isomeric with luteolin and and those of the yellow-berried buckthorn (R.
fisetin. infectorius [Linn.]), are sold as Avignon berries.
&- Rhamnocitrin C 13 10 H 5
is sparingly soluble The wood of the Rhamnus erythroxylon (which
in alcohol and acetic acid, but is distinct from is a native of Siberia, but grows freely in this
rhamnetin (C 12 H 10 and does not contain
5 ?), climate), in a ground state yields the bright-red
methoxy- groups. above 260, and,
It melts colour known to dyers under the name of
generally speaking, its reactions are the same as redwood. A. G. P.
those of rhamnocitrin itself, but, on the other BUCK WHEAT (Fagopyrum esculentum
hand, it
possesses stronger dyeing property. [Moench.]) isgrown mainly for poultry and also
H
Diacetyl-p-rhamnocitrin C 13 8 5 (C 2 3 0) 2 forms H for pig- and cow-f ceding in Europe. Its flowers
colourless needles melting at 190-191. furnish excellent pasturage for bees. Kellner
^-Rhamnocitrin, according to Tschirch and gives the following analyses :
Polacco, appears to resemble very closely the
BUTEA FRONDOSA. 575
Fr.) The
resin of Picea excdsa (Link.) purified Butin crystallises from alcohol in colourless
by melting in hot water and straining. It is an needles with |H 2 0, m.p. 224-226, and from
opaque, yellowish-brown, hard, brittle resin ; its water in pale-yellow needles with 2H a O ; dissolves
taste is sweet and aromatic. It is very soluble in alkaline solutions with a pale
orange-red tint,
in glacial acetic acid, acetone, and alcohol. and gives with alcoholic acetate of lead a faintly
Used in making plasters. It is much adulterated. yellow almost colourless precipitate. It forms
The substance usually sold by this name in a triacetyl derivative C 15 H 9 O 5 (C 2 H S 0) 3 colour-
England is made by melting colophony with less leaflets, m.p. 123-125, and a
tribenzoyl com-
palm-oil or some other fat, and stirring in water pound Ci 5 H 9 5 (C,H 5 0) 3 colourless needles, m.p.
,
to make the mixture opaque (Morel, Pharm. J. 155-157. On fusion with alkali at 200-220
[3] 8, 342) (v. RESINS).
butin gives protocatechuic acid and resorcinol.
BURNETT'S FLUID. A solution of zinc When butin is boiled with dilute potassium hy-
chloride is commonly known as Sir William droxide solution, the pale-coloured liquid becomes
Burnett's disinfecting fluid. It is used as a much darker, and on acidifying an orange
disinfectant and as a preservative of construc- crystalline precipitate separates which consists
tional timber. of butein.
BURTON WATERCRYSTALS contain, ac- Butein H
C 1S 12 5 ,H 2 0, needles, melts at
cording to Moritz and Hartley, 31-8 CaO, 40-4 213-215 dissolves in alkaline solutions with a
;
S0 3 , 1-04 Cl, 5-46 MgO, and 21-19 OH

2 (J. Soc. deep orange-red colour, and with alcoholic lead
Chem. Ind. 2, 82). acetate gives a deep -red precipitate. Acetyl
BUSSORAH GUM v. GUMS. H H
butein C 15 8 B (C 2 3 0) 4 pale-yellow needles,
,
BUTALANINE v. VALINE. melts at 129-131.

BUTANE v. BUTYL- COMPOUNDS. When fused with alkalis butein gives resor-
BUTANONE (Methylethylketone) v. KETONES. cinol and protocatechuic acid, whereas by the
BUTEA FRONDOSA. The Butea frondosa, action of boiling 50 p.c. potassium hydroxide
also called Dhak or Pulas, is a fine tree, 30-40 solution, protocatechuic acid and resacetophenone
feet high, belonging to the order Leguminosce. are produced.
It is common throughout India and Burma, and By methylation with methyl iodide butin
is found in the North- West Himalaya, as far as gives butintrimethylether C 15 9 2 (OCH 3 ) 3 , H
the Jhelum River. The flowers, which in the colourless plates, m.p. 119-121, and also butein-
dried condition, are known as tisu, ke'su, kesuda trimethylether C, 59
H
2 (OCH 3 ) 3 yellow leaflets, ,
or palas-keppiil, have a bright orange colour, m.p. 156- 158. In a similar manner, butein
and, although they are much larger, closely re- yields not only buteintrimethylether, but also
semble in appearance the common gorse-flower butintrimethylether.
(Ulex europceus), with which, indeed, they are The constitution assigned to butein is that
botanically allied. Large quantities of the of a tetrahydroxybenzylidene aceiophenone (tetra-
March and April, and
flowers are collected in hydroxychalkone) (1), and to butin that of the
employed by the natives to produce a yellow corresponding flavanone (2) :
dye, much used during the Holi festival. The OH

dyeing operation, which consists in steeping the / \OH
material in a hot or cold decoction of the flowers, (1) OHf \OH
is virtually a process of staining, because the
J CO CH=CH-
colour can be readily washed out. On the other
hand, a more permanent result is sometimes
produced either by first preparing the cloth with (2) OH \_0-CH OH
alum and wood ash or by adding these substances
to the dye- bath. -CO CH,
From the Butea frondosa is also obtained and that these formulae are correct has been
' ' '
the so-called Butea gum or Bengal kino,' established by the synthesis of butein and butin -
employed by the natives for tanning leather, trimethylethers. Thus by the condensation of
and the tree is of additional interest because in
resacetophenonemonomethylether with vera-
many parts of India the lac insect (Coccus lacca) tricaldehyde, buteintrimethylether (1) is
is reared upon it. This, as is well known, causes
the formation of stick lac, from which shellac
produced :
OCH 3
and lac dye are prepared.
Butin C t 5 H
2 5 . The flowers are extracted
j
with I.
OCHg/V-OH \)CH S
water, and the extract digested at the boil with ^ J CO CH==CH I
;
a little sulphuric acid. A light viscous precipi-
tate devoid of dyeing property separates, and this ..pCH,
is removed while hot and the filtrate left over-
The clear liquid is now decanted from
OCH o CH / V)CH S
night. II.
a small quantity of tarry substance, and -CO CH,
partially evaporated on the water-bath. A
further quantity of a black viscous precipitate and this, when
digested with boiling dilute
thus separates, and when this has been removed alcoholic sulphuric acid, a method devised by
the nitrate, after some days, deposits crystals of Kostanecki and his colleagues (Ber. 1904, 37,
the colouring principle. For purification the 784, 773, 779), gives butintrimethylether (II).
product is dissolved in a little alcohol, the Butein itself is also cqnverted into butin by
mixture poured into ether, and the solution well means of dilute alcoholic sulphuric acid, and the
washed with water. The liquid is evaporated, butin can again be transformed into butein by
and the residue repeatedly crystallised from the action of potassium hydroxide solution.
dilute alcohol. With alcoholic potash butintrimethylether also
576 BUTEA FRONDOSA.
gives buteintrimethylether, and these changes chromium, deep terracotta ; with aluminium, a
are readily explained if it is assumed that the bright orange ; with tin, bright yellow ; and
intermediate compound or its trimethyl ether with iron, a brownish-olive. The chromium
OH colour is characteristic, and is much redder in
tint than that yielded by any known natural
OHf OH CH(OH) < )OH yellow dye. A. G. P.
BUTEA GUM. The juice of Butea frondosa
CO CH. (Roxb.), often sent into the market instead of
isthe first product of the reaction in each case, genuine kino. It forms black-brown, slightly
and that this subsequently, by loss of water, lustrous, brittle lumps, has an astringent taste,
and yields pyrocatechin by dry distillation.
passes into either chalkone or flavanone, or both.
When butein dissolved in acetic acid is BUTTER. Butter is the fatty product pre-
treated with a few drops of sulphuric acid, and pared from the milk of the cow. When similar
substances are obtained from the milk of other
the solution is boiled, a new substance gradually
separates in the form of crystals, which possess
mammals, their origin is indicated in the descrip-
tion, e.g. goats' butter, buffalo butter. Fatty
a beetle-green iridescence, and dissolves in
food substances of vegetable origin and similar
alkaline solutions with a deep-blue colour. The
to butter in consistency are also sometimes
acid liquid decanted from the crystals, on dilu-
described as butter, but with a prefix, as vege-
tion with water, gives a brown precipitate
table butter, cocoa-nut butter.
soluble in alkalis with a bluish- violet colouration,
which dyes mordanted calico shades of a similar Butter consists of milk- or butter-fat, with
character to those yielded by anthragallol. It water, and small quantities of milk proteins,
lactose, mineral salts, and natural colouring
appears likely that this more soluble substance matter. The proteins and lactose, together
represents the product of the reaction, and
first
is converted into the green with the mineral matter associated therewith,
subsequently are spoken of collectively as curd. Commercial
iridescent compound. A consideration of the
butter may also contain common salt, preserva-
formula of butein renders it unlikely that these
new substances are anthraquinone derivatives tives, and colouring matter, added during
;
on the other hand, it is suspected that the manufacture. The added salt and preservatives
formation of a ring takes place, and that an are not included with the curd in giving the
indone derivative of the following type is first composition of butter, but are separately esti-
mated.
produced :
Fat exists in milk in the form of minute

OH
globules in a state of suspension in the milk
serum. In the process of churning, the fat
globules coalesce, producing irregularly-shaped
granules of butter. These are strained from the
Butin and butein dye mordanted woollen serum, or buttermilk, washed with water, and
worked into a mass on a table by means of
cloth identical shades, though as butin gives
mechanical rollers, or, as in older processes, by
with an alcoholic lead acetate a practically
hand. Salt, preservatives, colouring matter,
colourless precipitate, it is not to be regarded as
are added, if desired, after washing the butter
a colouring matter. In other words, butin is
granules with water.
merely a colouring principle, and is converted Milk may be directly churned for the purpose
during the dyeing operation by the action of of obtaining butter, and,'in some remote districts,
the mordant into the colouring matter butein.
this process is still followed. It is, however,
The following shades are obtained :
usual to churn cream, that is, the fatty layer
Chromium, Aluminium Tin Iron which rises to the surface on allowing milk to
lleddish-brown Brick red Full yellow Brownish black
stand or on subjecting it to centrifugal action.
and these are strikingly similar to those yielded Cream may be churned in a fresh condition
by some of the phenylketocumaran colouring before souring has taken place. In such a case,
matters artificially prepared by Friedlandec and the period of churning is longer, and the opera-
Rudt (Ber. 1896, 29, 879). tion must be carried out at a lower temperature
than when ripened cream or milk is employed.
(Y >
\/\co/
CH
-O It is therefore usual to churn ripened cream.
The ripening may be effected by standing the
cream, and is accelerated by the addition of a
The Butea flowers contain but a trace of little buttermilk or pure culture starters con-
free butin or butein, and the glucoside present,
taining suitable bacteria.
and which has not yet been isolated, is probably Various views are held as to what takes
that of butin. This glucoside does not decom-
place during the operation of churning. Fleisch-
pose readily during the dyeing process, hence the mann (Book of the Diary, 159) states that ' the
flowers do not dye mordanted cotton. In wool- milk-fat is converted from fluid to solid condi-
dyeing, where acid- baths are employed, a better tion by the shaking which it undergoes,' that is,
result is obtained, although in this case the that churning results in the solidification of fat
shades possess but little strength. If the which in milk is in a superfused condition. On
glucoside is first hydrolysed by boiling the flowers the other hand, Richmond's results (Dairy
with dilute hydrochloric acid, or 5 sulphuric
Chemistry, Ap. 339) would indicate that the
acid is employed, and the acid then neutralised fat before churning may be in a solid condition.
with sodium carbonate, a material is obtained Whether fat as present in milk is surrounded
which readily dyes by the usual methods. Such with some form of membrane (Bechamp, Storch)
products give the following shades with
: or with a thin watery covering (Fleischmaun),
BUTTER. 577
the mechanical operation of churning appears (J. Amer. Chem. Soc. 1899, 613) finds 1-0 p.c.
to rub away or remove the protective coating, of dihydroxystearic acid ; but Lewkowitsch
and thus enable the milk globules to coalesce, throws doubt upon the presence of any hydroxy
forming butter. As to the theories regarding acids (Oils and Fats, 4th ed. ii. 667). The
the structure of the fat globules in milk, see composition, as given by Bell (Chem. of Foods,
papers by Storch (Analyst, 1897, 22, 197), Beau 48), is compared with that given by Browne (J.
(Revue Generate du Lait, 2, 15, 1903), and Amer. Chem. Soc. 1899, 21, 807).
Richmond (Analyst, 1904, 29, 185). 100 parts of fat on saponification yield :
The quantity of water remaining in finished Bell Browne

butter is governed by the conditions of manu- Butyric acid . . 6-13 5-45
facture. Churning at too high a temperature Caproic . .1 2-09
renders the removal of excess water during Caprylic . .
|
2-09 0-49 2-90
working difficult. It results in over-worked or Capric . .
)
0-32
' '
butter or butter with an excessive Lauric . . 2-57
greasy ;
quantity of water. The maximum limit per- Myristic . . 1 9-89

missible in England for water in butter is 16 p.c. Palmitic . . 38-61 50-33
[49-46
Canada, Queensland, Holland, have the same Stearic . .
)
1-83
limit. Victoria has 15 p.c. Germany, 16 p.c.
;
Oleic . . 36-10 32-50
for salted, and 18 p.c. forunsalted; and Belgium, Dihydroxystearic acid 1-00
16 p.c. Caldwell and Hurtley (Chem. Soc. Trans.
The proportion of curd may vary from 0-2 1909, 95, 853) have fractionally distilled samples
to 2-0 p.c. according to method of manufacture, of butter fat in the vacuum of the cathode
lower quantities being present where freshly light, and determined certain values of the
separated cream is churned than in the case of distillates. They conclude that there is no
ripened cream. Well-made butter rarely con- tributyrin in butter-fat, and probably no tri-
tains so high a quantity as 2 p.c., and where this olein, the oleic acid being distributed among the
quantity is found, examination should be made glycerides present, most of it as oleostearo-
for the presence of added non -fatty milk solids. palmitin. Caldwell and Hurtley (I.e.) have also
No limits have been fixed as to the non-fatty similarly distilled the fatty acids.
milk solids permissible in butter, but the Butter The most characteristic feature of butter-fat
and Margarine Act, 1907, gives power to the is the presence of fatty acids soluble in water
Board of Agriculture and Fisheries to make and volatile in steam ; and the earliest work on
regulations on the point. butter was directed to the estimation, directty
Van Slyke and Hart (J. Amer. Chem. Soc. or indirectly, of butyric acid, the largest con-
1905, 27) state that when 0-5 p.c. or over of stituent of the soluble or volatile portion.
lactic acid is in the cream, the casein is present Hehner and Angell (Butter its Analysis and
:
in the butter as casein lactate, but in butter Adulterations, Churchill, 2nd ed. 1877), following
made from sweet cream as calcium casein. They the suggestion of Chevreul, proposed in 1874 to
also make suggestions with regard to the obtain the butyric acid by distillation of the
relation between casein compounds and mottled acids liberated by dilute sulphuric acid after
butter. Richmond (Analyst, 1906, 31, 178) has saponification of the fat with alkali. In con-
found the average amount of casein to be sequence of the variation in the results, they
0-38 p.c., and not to exceed 0-5 p.c. proposed the determination of the acids insoluble
The mineral matter in butter (to which no in water, Dupre subsequently adding in the
foreign substance has been added during manufac- same process the titration of the water-soluble
ture) consists of the inorganic substances derived acids (Analyst, 1876). The quantity of insoluble
from the buttermilk enclosed within the butter fatty acids is frequently spoken of as the
granules, and from the caseous matter adhering
'
Hehner value.' The process consists in saponi-
to the fat. It is really the ash of the curd, or fying a weighed quantity of the fat with alcoholic
the non-fatty milk solids of the butter. potash, liberating the fatty acids from the
When butter is heated, the fat melts and aqueous, alcohol-free, soap solution with excess
separates from the aqueous, curdy portion. of dilute sulphuric acid, filtering and washing
After allowing this to settle, the fatty layer is with hot water the insoluble acids, finally weigh-
filtered through a warm funnel, and the fat ing these, and titrating the dissolved acids. The
obtained as a clear oil, usually of a yellow colour, quantity of soluble acids usually falls between
but under certain conditions almost colourless, 4-2 and
6-0 p.c. (calculated as butyric acid), and
setting to a granular crystalline mass. The fat the weight of the insoluble acids between 90 and
so obtained consists of glycerides of fatty acids 87-5 p.c.
together with the natural or added colouring Reichert adopted a modification of Chevreul
matter, if any, of the butter, and some unsaponi- and Hehner 's distillation of the butyric acid,
fiable substances, e.g. cholesterol, associated with operating with a definite quantity of fat under
the natural fat. The total quantity of the prescribed conditions, and thus avoiding the
unsaponifiable matter does not exceed 0-4 p.c. necessity of the distillation of the whole of
(Bomer, Zeitsch. Nahr. Genussm. 1901, 4, the volatile acids. Reichert took 2-5 grams of
1070). fat ; and the number of cubic centimetres of deci-
The
glycerides of butter-fat contain butyric, normal alkali required to neutralise the distillate
caproic, caprylic, capric, lauric, myristic, from this quantity, operating as described, was
palmitic, stearic, and oleic acids, as triglycerides, the original Reichert number (Chem. Soc. Trans.
with a possibly small quantity of mono- and di- 1879, A, 406 ; Zeitsch. anal. Chem. 1879, 18, 68).
glycerides. Bell has shown the presence of Meissl suggested the use of 5 grams of fat
' '
mixed glycerides, and describes (Chemistry of (Chem. Soc. 1880, A, 828), and Wollny added
Foods, 45) an oleopalmitobutyrate. Browne a number of modifications (Chem. Soc. 1888,
VOL. I.T.
578 BUTTER.
A, 200). This process was adopted by a com- of 24 ; Germany, of 25 ; Sweden, of 23 the;
mittee consisting of the Principal of the Govern- United States, of 24 ; Italy declares butter with
ment Laboratory and the members of the a Reichert-Wollny number below 20 adulterated,
Society of Public Analysts, as the method to be between 20 and 26 suspicious, above 26 pure ;
used in the estimation of butter-fat in margarine Belgium declares butter to be abnormal, and its
(Analyst, 1900, 25, 309). The conditions of sale is prohibited, if the Reichert-Wollny number
distillation must be strictly observed, as the falls below 28, and if in addition the fat has a
whole of the volatile acid is not distilled during Zeiss number above 44 at 40, a sp.gr. below
the experiment. Richmond (ibid. 1895, 20, 0-865 at 100, a saponification value below 222,
218) found only 87 p.c. of the total volatile acids and a Hehner number above 88-5.
in the distillate.Jensen's results confirm this Handby Ball (Analyst, 1907, 32, 202) gives
(Zeitsch. Nahr. Genussm. 1905, 272). Leffmann results of butters produced in Ireland, and shows
and Beam used soda dissolved in glycerol for that during the months of December and January,
the saponification (Analyst, 1891, 16, 153). The when the output of milk is lowest, the Reichert-
details of the process, as adopted by the com- Wollny number frequently falls below 24. The
mittee, are :5 grams of clear, melted fat are lowest numbers occur when the milk is derived
weighed into a flask of a capacity of 300 c.c., from cows at the end of the lactation period.
and saponified with 2 c.c. of soda (prepared by Brownlee (Jour. Dept. Agric. for Ireland,
dissolving sodium hydroxide in equal weight of 1910, 10, 438) has published results of analyses
water), and 10 c.c. of alcohol, by heating on a of Irish butter produced in 1908-9. He found
hot water-bath under reflux condenser for 15 16-2 p.c. of samples below 24, 11-4 p.c. below 23,
minutes. After evaporation of the alcohol, 5-5 p.c. below 22, and 1-4 p.c. below 21. The tables
the dry soap is dissolved in 100 c.c. of hot given by Brownlee show that throughout the
water, 40 c.c. of normal sulphuric acid and a year the Reichert-Wollny number varies in each
few fragments of pumice are added, and the case with the percentage output of butter from
flask connected with a condenser. It is then the particular dairy, and the results confirm the
heated so that 110 c.c. of distillate are collected opinion that the chief factor influencing the
in about 30 minutes. The distillate is shaken, Reichort-Wollny number is the lactation period
100 c.c. filtered off, and titrated with deci- of the cows supplying the milk.
normal alkali, using phenolphthalein as indi- The conclusion that butter is genuine because
cator. (Further details as to size of flask, tubes, the Reichert-Wollny exceeds 24, may be erro-
still-head, condenser, will be found in the Analyst, neous, as this number may have been the result
1900, 25, 309. ) The number of cubic centimetres of mixing genuine butter having a high Reichert-
of decinormal alkali required for neutralisation, Wollny number with some other fat. On the
when multiplied by 1-1 and corrected to 5 grams, other hand, butter falling below 24 may be
'
is the Reichert-Wollny number.' genuine but abnormal. In order to be in a
The proportion of volatile acids in butter- position to establish the genuineness of butter,
fat varies. In the late autumn season, in the the Netherlands Government has organised a
case of cows fed in the open, the butter-fat system of butter control, by means of which the
contains less butyric acid than it does during associated creameries are frequently inspected
the spring and summer. Towards the close of and the butter produced regularly analysed.
the lactation period, butter fat also shows a Consignments from the factories bear a govern-
depreciation in the amount of volatile acids. ment label, giving particulars of origin, so that
Among other factors affecting the character of the officials can trace the butter and ascertain the
the fat are the nature of the food, and the Reichert-Wollny number of the butter produced
sensitiveness of the cows to varying climatic at the creamery.
conditions and their surroundings. Hence the Higher homologues of butyric acid volatilised
uncertainty as regards the limits that should be in the steam during the Reichert process do not
adopted. In the case of butter made from the wholly dissolve in the distillate, and the deter-
milk of mixed herds, when the influence of mination of the insoluble portion affords another
individual cases does not seriously depreciate index to the character of the fat, as will be seen
the butter from the whole herd, the proportion later.
of volatile acids under ordinary conditions of Butter-fat has a sp.gr. at 37-8/37-8 of
feeding and housing reaches a maximum in 0-910-0-913 (Thorpe, Chem. Soc. Trans. 1904,
April-May-June, and is at a minimum in 249). The individual data in Bell's results
October-November. Lewkowitsch has collected range from 0-9094 to 0-9139, but he states the
a number of results representing the produce of ordinary range is 0-911 to 0-913. The sp.gr. i
different countries (Oils and Eats, 4th ed. ii. 686). affected by prolonged heating of the fat and also
Although the milk from individual cows or small by the storage of the fat for a lengthened period.
herds may, in consequence of special circum- The reading with the Zeiss butyro-refracto-
stances, occasionally yield butter-fat giving a meter at 45 falls usually between 38 and 42.
the
Reichert-Wollny number below 24, the butter In 371 samples of genuine butter examined,
from the mixed milk of herds under normal range was 37 to 45 (Com. on Butter Regns.,
conditions usually has a Reichert-Wollny number Ap. 685). Excluding 14 exceptional butters,
falling between 24 and 32. The Committee on the average range was 39-4 to 42-0 (Chem. Soc.
Butter Regulations appointed by the Board of Trans. 1904, 249). (Zeiss readings are taken at
Agriculture in this country recommended that various temperatures by different observers.
the figure 24, arrived at by the Reichert-Wollny To convert the scale divisions observed at i
method, should be the limit below which a pre- lower temperature into the scale divisions at
s
sumption should be raised that butter is not higher temperature, deduct 0-55 of a divisio
genuine (Com. on Butter Regns. Report, Cd. for each degree of temperature that the reading
1749, 18). France has fixed a minimum limit has been taken below the required temperature ;
BUTTER. 579
conversely, add 0-55 a division for each

of
degree of temperature that the reading has been
taken above the required temperature).
The saponification value of the fat was
suggested by Koetstorffer (Frdl. 1879, 199), and
is frequently known as the Koetstorffer number.
It is the quantity of potash expressed in milli-
grams required to saponify 1 gram of fat. The
glycerides in butter-fat contain acids of com-
paratively low molecular weights; inconsequence,
the quantity of potash for saponification will be
relatively high when compared with fats in
which the glycerides contain only acids of high
molecular weight, as in animal fats in general.
Butter-fat gives figures on the average between
219-9 and 232-5 (Thorpe). Koetstorffer gave
227 as a mean figure. This value bears a close
relationship to the Rejchert number.
The iodine value varies considerably, falling
between 26-0 and 35-0 (Hiibl), 29-0 and 43-0
(Jensen), and 26-0 and 38-0 (Wollny).
The various data show their dependence
upon one another, within certain limits, when a
comparison is made. This parallelism is shown
in the following table (Thorpe, Chem. Soc.
Trans. 1904, 254) :
580 BUTTER.
Vegetable fats, unless specially prepared, 353) shows the variation in insoluble acids
contain phytosterol, and the detection of this number for the same soluble acids number.
substance establishes the presence of foreign Hesse (Chem. Zentr. 1905, 1, 566) says the limits
fat. Other fats, as cotton seed and sesame, give given by Polenske should be higher. Hesse and
specific reactions, and may therefore be directly Harris (I.e.) point out the importance of follow ing
tested for. It has, however, been established exact details of process, particularly in regard
that the constituent giving the reaction may be to size of pumice. Harris gives varying results
communicated to a slight extent to milk and obtained by operating with pumice of different
thence to butter through feeding the animals sizes.
with oil-cakes made from these seeds. Positive Cocoa-nut fat gives a soluble acids number
reactions in these cases must therefore be by this process of 7-9 and an insoluble acids
supported by other evidence. With the object number of 15-18. Hence the addition of this
of detecting the addition of foreign fat, it is fat to butter depresses the Reichert-Wollny
enacted in some countries that margarine and number, and increases the insoluble volatile
margarine fats must contain, when prepared for acids number. At the same time, the Zeiss and
sale, a small quantity of sesame oil, as a tell- iodine numbers would be lowered, and the
tale substance when butter with which such fat saponification value would be increased. Thus,
has been mixed is examined. while the Polenske value alone might not itself
(a) The soluble volatile acids
are estimated be sufficient evidence of adulteration in cases of
by the Reichert-Wollny process described above. small quantities of admixed cocoa-nut fat, the
Reychler (Bull. Soc. chim. 1901, 25, 142) disturbance of the co-relation between the other
proposed the extension of the Reichert-Wollny numbers would establish the presence of the
process to include the estimation of the volatile adulterant. Palm-kernel fat has a Reichert-
insoluble acids. Wauters (Analyst, 1901, 26, Wollny number of 5, and insoluble volatile acid
128) modified the Reichert process and made two number of 10-12 ; other vegetable and animal
distillations,determining the values for both fats have a total volatile acids number less than
soluble and insoluble volatile acids. 1. The addition of palm-kernel oil would
Polenske (Zeitsch. Nahr. Genussm. 1904, operate in a similar manner to that of cocoa-nut
273) adopts the Reichert-Wollny process and fat ; animal fat would depress both the soluble
estimates in the same operation the soluble and and insoluble volatile acids, but the former to
insoluble volatile acids. 5 grams of the fat are a greater extent than the latter. Thorp
weighed into a 300 c.c. flask and saponified with (Analyst, 1906, 31, 173) makes a second distilla-
2 c.c. of soda solution and 20 grams of glycerol tion in the ordinary Reichert process, after
by heating the flask over the free flame. The addition of more water, and obtains an increased
flask is cooled below 100, and 90 c.c. of hot value for the total insoluble volatile acids. He
water and a little powdered pumice are added. gives results of examination of butters and
When the soap is in solution the fatty acids are mixtures.
liberated with 50 c.c. of sulphuric acid (25 c.c. Muntz and Coudon (Mon. Sci. 1904, 18;
pure H 2 SO 4 in one litre), the flask attached at Analyst, 1905, 30, 155) have devised a similar
once to a condenser arranged vertical^, and method for determining the ratio between the
heated so that 110 c.c. of distillate are collected soluble and insoluble volatile acids. They
in about 20 minutes. The heating is then saponify 10 grams of fat with hot strong aqueous
stopped, and the receiving flask replaced by
a potash, dissolve the soap in water, add phosphoric
measuring jar to catch the drainings of the con- acid solution, and distil 200 c.c., using a spiral
denser. The distillate is cooled to 15, gently dephlegmator of considerable length. The dis-
shaken, and 100 c.c. filtered off and titrated tillate is filtered, and the soluble acids titrated.
with decinormal soda. The number of cubic The insoluble acids in the condenser tube and
centimetres (multiplied by 1-1 and corrected flask, and on the paper are also dissolved in
to 5 grams) is the Reichert-Wollny number. alcohol and titrated. They found that pure
The remainder of the distillate is poured on butters yielded from 4-79 to 6-01 p.c. of soluble
the filter paper, and then washed with three volatile acids (as butyric acid) and 0-5 to 0-87
quantities, of 15 c.c. each, of water,
each of p.c. of insoluble ; while cocoa.-nut fat gave
which has been passed in succession through 1-15 to 1-27 p.c. soluble, and 3-01 to 3-63 p.c.
the condenser tube, the measuring jar, and the insoluble. They determine the following ratios :
110 c.c. flask. These washings are rejected.

The 110 c.c. flask is then placed under the
filter funnel, and the water-insoluble acids dis-
solved in alcohol by passing three quantities, for genuine butter, and 250-3 to 282-3 for cocoa-
of 15 c.c. each, of neutral alcohol, successively nut fat.
through the condenser tube, measuring jar, and Vandam (Analyst, 1901, 26, 320) determined
filter paper. The
alcoholic filtrates are titrated the ratio between the total fatty acids soluble
with 1/10 normal soda, using phenolphthalein as in 60 p.c. alcohol, and those soluble in the alcohol
indicator. The number of cubic centimetres but insoluble in water. Robin (Compt. rend.
acids number.
required is the insoluble volatile 1906, 143) practically applies the same principle
In butter-fat this number varies with the
in his method. He found that the ratio -
soluble acids number. Polenske (I.e.) gave a
range of 1-35 insoluble for 20-0 of soluble, to X 10 was 8-3 to 12-7 butter, 232 for margarine,
3-0 insoluble for 30 of soluble. Individual and 226 for cocoa-nut fat. Shrewsbury and
butters may, however, give numbers outside Knapp (Analyst, 1910, 35, 385) remove the acids
this range. Rideal and Harrison (Analyst, 1906, soluble in water, and then determine the
31, 254) give results of examination of a number
dilute
solubility of the remaining fatty acids in
of English butters. Harris (ibid. 1906, 31, alcohol. They find a solubility figure of 28 for
BUTTER. 581
butter and 163 for cocoa-nut fat. It has been quantities of cocoa-nut fat can be detected by
shown (Caldwell and Hurtley, Analyst, 1909, the fractional distillation in a high vacuum of
34, 274) that lauric and myristic acids are the the fatty acids.
chief constituents of cocoa-nut fatty acids, but (b) The foregoing tests for the detection of
that these acids are only present to a slight the adulteration of butter-fat are based upon the
extent in butter ; and these processes are disturbance of the ratio existing in normal or
therefore based upon the solubility in 60 p.c. average butter-fat between the proportions of
alcohol and insolubility in water of these acids. soluble and insoluble acids. It has, however,
Fendler (Zeitsch. Nahr. Genussm. 1910, 19, 544 ; been shown that special feeding may affect this
Analyst, 1910, 35, 355) has a similar process. relationship and produce butter giving abnormal
Ave'-Lallemant (Zeitsch. Nahr. Genussm. results. Uncertainty as to the conclusions to
1907, 14, 317) precipitates the neutralised, be drawn may be removed if direct evidence is
alcohol-free soap solution with barium chloride, obtained from the application of specific tests.
and determines the baryta values for the soluble The following qualitative tests may be applied :
barium salts, and for the insoluble barium salts. Phytosterol test for detection of vegetable fats
He finds that normal butter has insoluble baryta (Bomer, Zeitsch. Nahr. Genussm. 1901, 4, 1070,
value of 247 to 251, and soluble baryta value of and 1902, 5, 1018). The absolute alcohol
50 to 65. The value [insol. (200+soluble)] is extract of the unsaponifiable matter from 100
negative for butter, whereas other fats have a grams of fat is treated with acetic anhydride,
positive value not less than 39. (See also the excess of which is removed, and the acetates
Fritzsche, Zeitsch. Nahr. Genussm. 1907, 14, 329.) dissolved in alcohol, crystallised, and recrystal-
Ewers (ibid. 1910, 19, 529) proposes a method lised several times. Cholesteryl acetate melts at
depending upon the different solubility of the 113-5 to 114-5, while the melting-point of
magnesium salts of the fatty acids, and on the Phytosteryl acetate is about 129. If the melt-
varying solubility in petroleum spirit of the ing-point of the mixed acetates from the sample
fatty acids from the soluble magnesium salts. under examination is between 116 and 117, it
Various methods have been proposed to is probably adulterated with vegetable fat ; if
distinguish between cocoa-nut fat and butter above 117, vegetable fat is certainly present.
fat by means of the solubilities of the silver The test is not of value if paraffin wax is also
salts of the distilled acids in the Reichert-Wollny present.
process (K. Jenson, Analyst, 1905, 30, 396 ; Rinks' test for cocoa-nut fat (Analyst, 1907,
0. Jenson, Zeitsch. Nahr. Genussm. 1905, 10, 32, 160). 5 c.c. of the fat are dissolved in
265 ; Kirschner, ibid. 1905, 9, 65 ; Wijsman and 10 c.c. of ether, and the solution cooled in ice.
'
Reijst, ibid. 1906. 11, 267 ; Dean, Ann. Chim. After half an hour, it is rapidly filtered, the
anal. 1906, 11, 121). ether evaporated from the filtrate, and the fatty
Dons
(Zeitsch. Nahr. Genussm. 1908, 15, 75) residue dissolved in 96 p.c. (vol.) alcohol. The
has modified the process. The mixed fatty solution is cooled to 5 for 15 minutes, filtered
acids are treated with water to remove the rapidly, and the filtrate cooled to 0. The
soluble portion. Caprylic acid, which remains deposit which separates at this temperature is
behind with the insoluble acids, is removed by then examined on a cold slide under a power
distillation, and estimated in the distillate by of about 250. Butter fat yields a deposit
precipitation with silver nitrate solution. Pure of round granular masses ;cocoa-nut fat, fine
butter-fat gives a value 1-6 to 2-0 and cocoa-nut needle-shaped crystals and mixtures of butter
;
fat 5-3. and cocoa-nut fat, fine feathery crystals attached

Juckenack and Pasternack (Zeitsch. Nahr. to the granular butter masses. The test is
Genussm. 1904, 7, 193) proposed to determine capable of detecting 5 p.c. of cocoa-nut fat in
the presence of cocoa-nut oil in butter from the butter fat.
relationship between the Reichert - Wollny Badouin test for sesame oil. 5 c.c. of the fat
number and the saponification value. They are mixed in a tube with 5 c.c. of HC1 (sp.gr.
point out that according to the formula [R.W. 1-19) and 0-1 c.c. of a 2 p.c. furfural solution.
(sapon. value 200)J butter fluctuates between The mixture is well shaken and allowed to stand.
3 5 and -(-4-25.
-
j?or cocoa-nut oil its value is The aqueous layer which separates assumes a
47. Harris (Analyst, 1906, 31, 355) has shown reddish colour in presence of sesame' oil. Butters
that the method of reasoning suggested is of coloured with some aniline dyes give with hydro-
no value for small admixtures of cocoa-nut fat chloric acid a pink-to-violet colouration, and in
with butter. such a case the acid and fat mixture must be
Paal and Amberger (Zeitsch. Nahr. Genussm. heated until colourless before the addition of
1909, 17, 23) distil separated solid fatty acids in the furfural solution.
a current of steam in special flask, and precipi- Halphen test for cotton seed oil. 5 c.c. of the
tate the cadmium salts in distillate. fat are dissolved in 5 c.c. of amyl alcohol, 1 c.c.
Hanug (ibid. 1907, 13, 18) and Hanus and of a solution of sulphur in carbon disulphide is
Stekl (ibid. 1908, 15, 577) and Fendler (ibid. added, and the mixture heated for 20 minutes
1910, 19, 544) propose methods based upon the at 105 in a brine-bath. A red colouration is
distillation of the ethyl esters of the fatty acids. produced in presence of cotton-seed oil. The
1'Vudler prepares the esters after the manner of chromogenetic substance may, however, in
Henriques (Analyst, 1898, 23, 181) and collects exceptional cases, be communicated to butter by
the esters boiling below 300. This fraction feeding cows with cotton cake ;
and a positive
j
would include the ethyl esters of the acids up to reaction must be confirmed by other data of
and including myristic acid. The volume in the examination.
the case of butter ranges from 2-5 to 6-1 ; cocoa- (c) The specific gravity
and the Zeiss reading
nut fat, 40 to 42 and lard, 0-5 to 1-1 c.c.
;
should be taken and considered in conjunction
Caldwell and Hurtley (I.e.) state that small with and relation to the data for the Reichert-
582 BUTTER.
Wollny number, saponification and iodine through which a mark or design has been scratched
values. with a fine instrument. In presence of fluoride
Of other physical methods there may be the glass will be etched.
mentioned : O. and C. W. Hehner (Analyst, 1902, 27,
Valenta 3
of fat are dissolved in
test. c.c. 173) indicate how to remove the boric acid if
an equal volume of glacial acetic acid, and then present before testing for fluoride.
allowed to cool while being stirred with a ther- (d) Benzoic acid and benzoates. 10 grams of
mometer. Immediately a turbidity is noted, the butter are heated for some time with alcohol
temperature is read. A modification introduced acidified with dilute sulphuric acid. The
by Jean is to measure the volume of acid dissolved alcoholic extract, after dilution with water, is
in the fat at 50. extracted with ether in a separator. The ether
Crismer test. This method is an official solution is then shaken with dilute ammonia,
one in Belgium. 0-5 c.c. of melted fat and 1 c.c. and the ammoniacal extract evaporated to
of absolute alcohol are placed in a tube fitted dryness in a porcelain dish. The residue is
with cork and thermometer, the bulb of which dissolved in water, just acidified with acetic
dips into the liquid. The tube is gently heated acid to ensure that no free ammonia remains,
inside a larger tube until the liquid becomes and a drop of ferric chloride solution added.
homogeneous. It is then allowed to cool, and Benzoic acid gives a buff-coloured precipitate.
the temperature noted when turbidity appears. (e) Salicylic acid. A
portion of the alcoholic
This point is the critical temperature of disso- solution prepared for benzoic acid is tested
lution (Crismer, Analyst, 1897, 22, 71). directly with a drop of ferric chloride solution.
3. Examination for preservatives. (a) Boron Salicylic acid gives a violet colour.
compounds. Boric acid or borax is detected (/) Richmond (Analyst, 1908, 33, 116)
by moistening a strip of turmeric paper (filter points out that formic acid and glucose are also
paper soaked in an alcoholic solution of curcuma used as preservative agents.
and dried) with a drop of water squeezed from Colouring matters. The colour of butter
the butter, or with the aqueous layer obtained prepared without addition of artificial colouring
on melting the butter. The paper is then dried. matter, varies according to the food of the cows.
Free boric acid gives a pink colour changed to Winter butter from stall-fed cows is nearly
green with alkali. For borax a drop of dilute colourless. Colouring matter is frequently
hydrochloric acid must be added to the paper added to butter during manufacture. Annatto,
before drying. turmeric, carrot juice, saffron, marigold, safflower
The boric acid is estimated by Richmond and and aniline dyes are among the artificial colours
Harrison's method (Analyst, 1902, 27, 179) or by employed. Agitation of the butter fat with hot
washing the butter in a separator with hot alcohol will give an indication whether colour
water, evaporating the aqueous portion after has been added. Cornelison (J. Amer. Chem.
addition of soda, incinerating, and proceeding as Soc. 1908, 30, 1478) shakes thoroughly 10 grams
in Thomson's process. of melted fat with 10 to 20 grams of glacial
Amethod suitable for rapid determinations acetic acid at about 35. The acid layer is
is as follows : 10 grams of butter are shaken in a drawn off and tested with various reagents for
separator with 20 c.c. of hot water and 10 c.c. of the detection of aniline and vegetable dyes.
decinormal sulphuric acid. The aqueous layer is Leeds (Analyst, 1887, 150) has also proposed a
run off after a few minutes, and the fat washed scheme for identification of dye.
twice more with small quantities of hot water. Annatto and azo- dyes may be rapidly
The mineral acid in the combined water extracts tested for as follows 5 c.c. of melted fat are
:
is then neutralised, with lacmoid as indicator.

placed in each of two test-tubes. To one 5 c.c.
2 grams of mannite are now added, and phenol- of hydrochloric acid are added, and the mixture
phthalei'n. Decinormal soda is then added until shaken. Azo- dyes will impart a reddish colour
pink colour is permanent. The quantity of to the acid layer. To the second tube add 5 c.c.
soda used after the solution was neutral to of ether, and shake, and then 5 c.c. of 10 p.c.
lacmoid indicates the proportion of boric acid potash solution. Shake and allow to separate.
present. A control experiment should be If annatto is present, the alkaline layer will be
carried out with pure butter and indicators. coloured yellow. To confirm the annatto, the
The Committee on Preservatives in Food alkaline liquid is evaporated to
Avithdrawn,
recommended that borax or boric acid should j dryness, and touched with a drop of sulphuric
be the only preservative allowed in butter, and acid. Annatto gives an indigo-blue to violet
that the quantity should not exceed 0-5 p.c. colouration.
calculated as boric acid. Crampton and Simons (J. Amer. Chem. Soc.
(b) Formalin is detected by the
application 1905, 27, 270) point out the use of palm oil as
|
of Hehner's test (Richmond, Analyst, 1896, 21, \

a colouring substance, and its detection by the
92). A
little milk is added to the aqueous
layer Halphen and Liebermann-Storch methods for
from melted butter, and the mixture poured on rosin oil.
to the surface of sulphuric acid containing a The further examination of the butter
1
i.
trace of ferric chloride. In presence of formal- concerned with appearance, rancidity.

its flavour,
dehyde a blue ring appears at the juncture of As regards rancidity, the quantity of free aci<
the aqueous and acid layers. dissolved in alcohol may be ascertained, but tl
(c) Fluorides. Fluorine is detected by eva- is frequently no guide to or measure of the
porating the aqueous portion rendered alkaline rancidity, which is best judged by smell
and taste.
from about 30 grams of butter, The definition of 'butter 'in the Margarine Act,
incinerating, '
and heating the ash in a platinum crucible !
1887 (50 & 51 Viet. c. 29) is as follows The :
with strong sulphuric acid. The crucible is word " butter " shall mean the substance
covered with a watch-glass coated with wax usually known as butter, made exclusively from
BUTYL OR TETRYL. 583
milk or cream, or both, with or without salt or (2) CH 3 -CH 2 -CHX-CH 3 (secondary) ;
other preservative, and with or without the (CH 3 2 CH-CH 2 X

(3) ) ;
addition of colouring matter.' (4) (CH 3 3 CX (tertiary).

)
The Butter and Margarine Act, 1907 (7 Edw.

' BUTYL COMPOUNDS.
7, c.21) describes milk- blended butter as any
mixture produced by mixing or blending butter Butyl alcohol. Tetryl alcohol C 4 H 9 OH. All
the four possible bodies corresponding to this
with milk or cream (other than condensed milk
formula are known.
or cream).' By the provisions of this Act
1. Normal butyl alcohol: butanol ;
milk-blended butter may contain a maximum propyl
of 24 p.c. of water.
carbinol CH 3 -CH 2 -CH 2 -CH 2 ; b.p. OH
115,
' ' ' Lieben and Rossi (Compt. rend. 68, 1562)
'
Renovated or process butter is a pro-
117-2 (Bruhl, Annalen, 203, 16); sp.gr.
duct mainly of the United States. It is defined
'
by Act of Congress as butter which has been

0=
0-8233, 20 0-8109, 40 = 0-7994, 98-7 = =
subjected to any process by which it is melted, 0-7738, 20/4
=
0-8099 (B.) ; ^ 1-39909, mol. =
clarified, or refined and made to resemble refraction =35-45 (B.). Occurs in the heavy
genuine butter.' Butter which is unsaleable oil of Cognac brandy to the extent of 49 p.c.
through rancidity, mould growths, or other Is not formed in the fermentation of sugar
causes, is melted, and the oil separated from the produced
by elliptical yeast (Claudon and Morin,
curd and water. The oil is then aerated by Chem. Soc. Trans.
' ' 1887, ii. 714). Is produced
blowing with air, and afterwards emulsified
by the action of sodium amalgam upon butyryl
with fresh milk inoculated with a bacterial chloride and
butyric acid (Saytzeff, Zeitsch.
culture. It is then churned and worked as for
Chem. 1870, 108; Linnemann, Annalen, 161, 178).
ordinary butter. Also by the fermentation of glycerol by Bacillus
Crampton (J. Amer. Chem. Soc. 1903, 25, butylicus and certain other bacteria in presence
358) gives details of analyses and tests. Several of calcium carbonate and various foodstuffs,
similar processes have been patented here, and
e.g. ammonium tartrate ; the yield amounts to
in some factories the melting and purification 9 p.c. of the glycerol used. Butyric acid and a
of inferior butter is now carried on. Hence little
ethyl alcohol are also formed (Fitz, Ber. 9,
such products might contain crystalline fat, 1348
; Vigna, Ber. 16, 1348). Is also produced
and the microscopical examination is now of no
by the action of nascent hydrogen (iron and
value as a test for foreign fat.
' '
acetic acid) upon crotonaldehyde and trichloro-
Factory butter is butter which has been butyraldehyde (Lieben and Zeisel, Monatsh. 1,
reworked or blended with other butter; by
825, 842).
butter is understood butter made at
' '
dairy Beyerinck has shown that the Bacillus
the farmer's homestead, whether from whole milk
' ' butylicus of Fitz (Ber. 1882, 867) is in reality
or cream and the term creamery
;
butter is
the butyric ferment. The true butylic ferment,
generally applied to butter made from cream Granulobacter butylicum, has been isolated in a
separated by centrifugal force from the mixed
pure condition, and an account of the whole
milk of a number of herds in premises specially fermentation
process is given ( J. Soc. Chem. Ind.
utilised for the purpose (see the Report of the
1894, 167 ; ibid. 969). (See also Emmerling,
Committee of the Department of Agriculture for Ber. Buchner and
1896, 2726 ; 1897, 451 ;
Ireland, on the Irish Butter Industry, Cd. 5092,
Meisenheimer, Ber. 1908, 1410.)
1910). Colourless liquid, soluble in 12
Properties.
In hot countries, owing to the rapid decompo-
parts of water, from which solution it can be
sition ofordinary butter, the clarified fat, free separated by means of calcium chloride. Soluble
from water and curd, is prepared for sale, as in concentrated hydrochloric acid ; is readily
schmelzbutter, ghee. G. S.
oxidised to butyric acid. Fused zinc chloride
BUTTERINE v. MARGARINE. abstracts water, and yields /3-butylene and
BUTTER SUBSTITUTES v. MARGARINE. smaller amounts of normal butylene (Le Bel
BUTTER SURROGATE v. MARGARINE. and Greene, Amer. Chem. J. 2, 24).
BUTTER, VEGETABLE. A greasy substance Bromine on acting -butyl alcohol yields,
expressed from the kernel of the Bassia butyracea with some difficulty, mono-brombutaldehyde,
(Roxb.), a native of North India. This grease 235 The
is said to make excellent soap. Shea butter is b.p. (Etard, Compt. rend. 114, 753).
obtained from the Butyrospermum Parkii, of
action aluminium amalgam on the butyl
of
West and has been used in making alcohols, producing liquid aluminium alkoxides,
Africa,
has been studied by Tistshenko (Chem. Soc.
candles and soap. The butter-tree of Sierra
Abstr. 1899, i 408).
Leone is the Pentadesma butyracea (Subine), the
2. Iso-butyl alcohol, isopropyl carbinol-
fruit of which yields much grease, and is eaten
OILS and FATS). a-hydroxy 0- methylpropane ( CH 3 ) 2 CH-CH 2 OH,b.p.
by the negroes (v.
108-4 (Linnemann, Annalen, 160, 238) ; sp.gr.
BUTTER YELLOW. Benzeneazodimethyl 0-7265 at 106-6/4 (Schiff, Annalen, 220, 102),
aniline C 6 H,-N : N-C 6 H 4 -N(CH 3 ) 2 . A yellow 0-8168 at (L.), 0-8069 at 15/15, 0-8008 at
colouring matter (m.p. 115) ; insoluble in water,
soluble in dilute HC1, with red colour soluble ;
25/25 Perkin (Chem. Soc. Trans. 1884, 468) ; sp.
in fats. Used for colouring butter (Witt. Griess. heat=0-686 molecular rotation=4-936 at 17-7
;
Ber. 1877, 10,528) (v. Azo- COLOURING MATTERS). (P.) ; molecular refraction
=
35-41 ; ,u 1-4007. =
P
BUTTERS, MINERAL. A term formerly ap- Sp.gr. aqueous solutions (Duclaux,
of Ann.
plied to several of the metallic chlorides, e.g. Chim. Phys. [5] 13, 91) :
chlorides of antimony, tin, bismuth, zinc, &c.

BUTYL or TETRYL. A
univalent radical
yielding four isomeric mono- derivatives :
'
9915 '
9875
(1) CH S -CH 2 -CH 2 -CH 2 X (normal) ;
584 BUTYL OR TETRYL.
Occurs in fusel oil from potatoes and beet (For combinations and derivatives of isobutyl
(Wurtz, Ann. Chim. Phys. [3] 42, 129), and alcohol, v. Gladstone and Tribe, Chem. Soc.
combined with angelic and isoltmtyric acids in Trans. 1881, 6; Pierre and Puchot, Annalen,
Roman oil of chamomile (Kobig, Annalen, 163, 274; and Heindl, Monatsh. 2, 208.)
195, 96). ^.Secondary butyl alcohol, 2-hydroxybu-
Preparation. By the action of sodium tane, methyl ethyl carbinol, biitylene hydrate.
amalgam and water upon 0-chlonsobutyl alcohol, S
which results from the actionof hypochlorous j
njj ^>CHOH; b.p. 99 at 738-8 mm. (Lieben,
acid upon isobutylene (Butlerow, Annalen, 144, ! Annalen, 150, 114) ; sp.gr. 0-827 at 0, 0-810
24). Is formed in small quantity by the action at 22 (L.).
Formed by the action of water upon the
j
of elliptical yeast upon sugar or glycerol

(Claudon and Morin, Chem. Soc. Trans. 1887, compound of zinc-ethyl and aldehyde :
ii. 714). By the reduction of isobutyric aldehyde CH,CH(C,H 5 )0-Zn(C 1 H 5)

with sodium amalgam (Linnemann and Zotta,
thus:
Annalen, 162, 11). |
'
Properties. Colourless liquid, soluble in CH 3 CH(C 2 H 5 )0-ZnC 2 H 5 +H 2

10-5 parts of water, from which calcium chloride =C 4 H OH+ZnO+C H
9 2 6
causes it to separate. Smells like fusel oil.
(Wagner, Annalen, 181, 261). Also by acting
Is oxidised by chromic acid into isobutyric acid, i
upon secondary butyl iodide with silver acetate
acetic acid, carbon dioxide, acetone, and other and saponifying the resulting acetate by means
products (Kramer, Ber. 7, 252 ; Schmitt, ibid. of potash. Normal butyl alcohol may be
8, 1361). Zinc-dust yields water and iso- !
changed into the secondary alcohol the normal ;
butylene (Jahn, ibid. 13, 989). iodide is heated with potash, and the normal
Treated with iodine and aluminium, alumi-
butylene so obtained on treatment with hydri-
H
nium trusobutoxide A1(C 4 9 0) 3 is formed. It is
I
odic acid yields secondary butyl iodide (Saytzeff,

a liquid which may be distilled in vacuo (Glad- Zeitsch. anal. Chem. 1870, 327). It may also be
stone and Tribe, Chem. Soc. Trans. 1881, 6).
[
prepared from the normal isomeride by treating

/sobutyl alcohol may be catalytically '
n-butylamine with nitrous acid (Meyer, Ber. 10,

oxidised to isobutyl aldehyde. The vapour of ;
130 ; Kanonnikoff and Saytzeff, Chem. Soc.
the alcohol mixed with air, is passed over warm Trans. 1875, 626).
freshly reduced copper spirals and the products Properties. Liquid, with strong odour ; upon
collected. A yield of 50 p.c. is obtainable (E. oxidation yields a ketone C 2 5 -CO-CH 3 (b.p.H
Orlow, J. Soc. Chem. Ind. 1908, 957). 80), and acetic acid (Kanonnikoff and Saytzeff,
When chlorine is passed into dry isobutyl Chem. Soc. Trans. 1875, 626). Heated with
alcohol, and the solution subsequently heated a trace of hydrochloric, hydrobromic, or hydri-
gently, the product can be separated into two odic acid, in a sealed tube, to 240, yields C 4 8 H
fractions, boiling at 80-100 and 170-250. (pseudo-butylene). It has been separated into
The lower fraction consists of cMorisobutalde- its optical antipodes by R. Meth (Ber. 1907, 695) ;
hyde, boiling at 90-91; sp.gr. 1-186, 15/4. It the alcohol has [a] 0-32.,
combines with sodium hydrogen sulphite, and

when oxidised with alkaline permanganate yields 4. Tertiary fyutyl alcohol, trimethyl
acetone and hydroxyzsobutyric acid C(CH 8 ) a OH- carbinol (CH 3 ) 3 C-OH. A solid; in.p. 25-45
CO OH, melting at 78. A termolecular polyme- (De Forcrand, Compt. rend. 136, 1034) ; b.p.
82-94
H
ride C, 2 21 C1 3 3 which melts at 107, is
,
(corr.) (Linnemann, Annalen, 162, 26);
81-5-82 (Perkin, Chem. Soc. Trans. 1884, 468).
obtained by shaking with strong sulphuric acid
If the Sp.gr. 0-7792 at 37 (L.) ; 0-7788 at 30 (Butlerow,
(A. Brochet, Compt. rend. 114, 1538).
alcohol is kept cold, the chief product is dichlor- Annalen, 162, 229) ; 0-7864 at 20/4, 0-7802 at
isobutyl oxide C(CH 3 ) 2 C1-CHC1-0-CH 2 CH(CH 3 ) 2
26/4 (Briihl, Annalen, 203, 17); 0-7836 at
boiling at 192-5/760, and of sp.gr. 1-031, 15/4.
25/25, 0-7761 at 35/35 ; molecular rota-
Water is without action on this product at low
,
|
tion at 24-3 =5-122 (P.); M =1-3924; mole-
temperatures, but at 100 produces hydrogen j

cular refraction =
35-53 ; crit. temp. 234-9 =
chloride and a-chlon'sobutaldehyde and diiso- ;
(Pawlewski, Ber. 16, 2634).
butylmonochlomobutyralC(CH 3 ) 2Cl-CH(OC 4 H 9 ) Formed from asobutyl iodide by treatment
boiling at 218, and of sp.gr. 0-9355, 15/4 |
with acetic acid and silver oxide (Linnemann ;
(A. Brochet, Compt. rend. 118, 1280 v. also ; Butlerow, Annalen, 168, 143) ; also from iso-
Brochet, Bull. Soc. chim. 1896, 16 ; ibid. 20). butylamine by treatment with nitrous acid, and
When chlorine is led into hot zsobutyl alco- from tsobutyl carbimide CO-N-C 4 H 4 by action ,
hol, chlomobutyricisobutyl ester, aj3-dichlor?so- of potash (Linnemann, Annalen, 162, 12). Can
butyric acid, tsobutyl ester, mono- and dichlor- ;
be prepared by allowing 20 grams of tertiary
i'sobutyric aldehyde, iso butyric acid, oxyiso- butyl iodide and 50 grams of water to stand in
butyric acid, crotonic acid CO,C0 2 , and methyl contact for two or three days (Dobbin, Chem.
chloride are produced. Treating aqueous iso- Soc. Trans. 1880, 238).
butyl alcohol with chlorine water produces /aobutyl alcohol heated with excess of hydro-
isobutyric acid, and a-chlomobutyric acid chloric acid yields a mixture of secondary and
isobutyl ester. Chlorine acting on cold dry tertiary butyl chlorides, and when heated with
isobutyl alcohol in the light produces 1 : 2- six volumes of water only the latter is decom-
dichlomobutyl ester (Brochet, Ann. Chim. posed, yielding the alcohol and hydrochloric
Phys. [7] 10, 363). acid (Freund, J. Pharm. Chim. [2] 12, 25).
/sobutyl alcohol, when acted on by bromine, Properties. Forms rhombic plates or prisms.
readily yields zsobutyl bromide, mixed with ; Unites with water to form a liquid hydrate
wobutyl isobutyrate, and bronu'sobutaldehyde H
2C 4 10 0,H 2 O (b.p. 80; sp.gr. 0-8276 at
(Etard, Compt. rend. 114, 753). (Butlerow, Annalen, 162, 229). On oxidation
BUTYL OR TETRYL. 585
yields acetone, carbon dioxide, acetic acid, and

1. Normal butyl chloride, a-chlorbutane
a small quantity of isobutyric acid (Butlerow, CH 3 CH 2 -CH 2 -CH 2 C1 ;
Zeitsch. Chem. 1871, 485).

b.p. 77-96 (Linnemann, Annalen, 61, 197):
(corr.)
The existence of the hydrate C 4 Hi O,2H 2 O, sp.gr. 0-9074 at 0, 0-8874 at 20 (Lieben and
m.p. 0,confirmed by cryoscopic, density
is 0-9074 at
Rossi, ibid. 158, 161) (L.), 0-8972;
and determinations (Paterno and

viscosity at 14. Formed by the
action of chlorine upon
Mieli, Atti. R. Accad. Lincei. 1907 (v.), 16, ii. w-butane (Pelouze and Cahours, J. 1863, 524).
153). More easily by the action of hydrochloric acid
In sunlight it combines with chlorine, form-
upon n-butyl alcohol (Lieben and Rossi).
ing tertiary butyl chloride and other substances 2. Isobutyl chloride, fi-methyl- a-chlorpro-
(D'Otreppe, J. 1881, 512). pane (CH 3 ) 2 CH-CH 2 C1 b.p. 68-5 (Linne- ;
Trimethyl carbinol explodes feebly when mann, Annalen, 162, 17) 68-5-69 (Perkin, ;
treated with bromine, yielding isobutylene Chem. Soc. Trans. 1884, 451); sp.gr. 0-8798 at
bromide C(CH 3 ) 2 Br-CH 2 Br boiling at 148 15 (L.), 0-8953 at 0, 0-8651 at 27-8, 0-8281
(Etard, Compt. rend. 114, 753). at 59 (Pierre, Puchot, Annalen, 163, 276),
Tertiary butyl alcohol has a slightly narcotie 0-8835 at 15/15, 0-8739 at25/25 (P.). Mole-
action when taken internally, and is found in cular rotation at 21-3=6-144 (Perkin). Formed
the urine in combination with glycuronic acid by the action of hydrochloric acid or PC1 5 upon
(Thierfelder and v. Mering, Chem. Soc. Abstr. the alcohol (Wurtz, ibid. 93, 113). By the
1885, i. 1002). action of chlorine, hexachlorbutane is produced.
Nitrohydroxybutanes may be obtained quanti- Isobutyl chloride is also produced by the
tatively as follows: By the action of nitromethane interaction of chlorine and isobutane in diffused
on formaldehyde, in presence of a little potassium sunlight (Mabery and Hudson, Amer. Chem. J.
carbonate, nitrotrihydroxybutane
tertiary 19, 245) ; and also by treating jisobutylamine
N0 2 -(CH 2 OH) S a white crystalline solid, melting
, cooled to 15 with nitrosyl chloride (Solonina,
at 158-159, is produced. Nitroethane pro- Chem. Zentr. 1898, ii. 887).
duces tertiary nitrodihydroxybutaneN0 2 -C(CH 3 ) 3. Tertiary butyl chloride, fi-methyl-f)-
(CH 2 OH) 2 melting at 139-140. Secondary
, chlorpropane (CH 3 3 CC1 b.p. 51-52 (Perkin,
) ;
nitropropane yields nitroisobutyl alcohol Chem. Soc. Trans. 1884, 451); sp.gr. 0-8658
N0 2 -C(Me) 2 -CH 2 OH, melting at 82 (L. Henry, at (Puchot), 0-8471 at 15/15, 0-8368 at
Compt. rend. 1895, 121, 210). 25/25 ;
molecular rotation at 15 6-257 =
Butyl bromides. Tetryl bromides C 4 H 9 Br. (Perkin).
1. Normal butyl bromide, a-bromobutane Formed (1) by the chlorination of tertiary
CH 3 -CH 2 -CH 2 -CH,Br ;
butane (Butlerow) (2) by the action of iodine
;
monochloride upon isobutyl iodide (Linnemann,

b.p. 99-9 (corr.) (Linnemann, Annalen, 161,
Annalen, 162, 18) (3) by the action of hydro-
sp.gr. 1-3050 at 0, 1-2792 at 20, 1-2571
;
193) ;
at 40 (Lieben and Rossi, ibid. 158, 161).

chloric acid upon isobutylene at 100 (Zalessky,
Formed from normal butyl alcohol and Ber. 5, 480 ;
Le Bel, Bull. Soc. chim. 28, 462) ;
by saturating trimethyl carbinol at with

hydrobromic acid (L. and R.). (4)
HC1 gas (Schramm, Monatsh. 9, 619).
By the action of bromine, o/3-dibrombutane Heated with five or six vols. of water to 100,
C 4 H 8 Br 2 (b.p. 166) is formed (L.).
the alcohol is produced (Butlerow, Annalen,
2. Isobutyl bromide, a-bromo--methyl
144, 33). Chlorine in diffused daylight, in the
propane (CH 3 ).,CH-CH 2 Br b.p. 92-3
106-107), C 4 H 7 C1 3
(corr.)
;
91-3 cold, forms C 4 H,CL (b.p.

(Linnemann, Annalen, 162, 34) (Perkin,
and C 4 H 5 C1 5 whilst C 4 H 4 C1 6
;
in direct sunlight
Chem. Soc. Trans. 1884, 459); sp.gr. 1-2038 at
,
16 (L.), 1-2722 at 15/15, 1-2598 at 25/25 (P.). (b.p. in partial vacuum about 115), and other
Molecular rotation =8 -003 at 16-2 (P.). From products are formed (D'Ottreppe, J. 1882, 441).
tsobutyl alcohol, bromine, and phosphorus Tertiary butyl chloride is also formed by the
action of PC1 5 on trimethyl carbinol ( Janschenko,
(Wurtz, Annalen, 93, 114). Unites with bromine
at 150 to form C 4 7 Br 3 (L.).H Chem. Zentr. 1897, ii. 334). It also results,
3. Tertiary butyl bromide, fr-bromo-$-methyl together with isobutyl chloride from the action
of nitrosyl chloride on tertiary butylamine in
propane (CH 3 ),CBr ; b.p. 72 at 761-5 mm.;
20 (Salonina,
xylene solution at 15 to
sp.gr. 1-215 at20, 1-2020 at 15/15 , 1-1892 at ibid.
25/25; molecular rotation =8 -238 at 17-8 (P.). 1898, ii. 888).
Formed when tsobutyl bromide is heated to 240 4. Secondary butyl chloride, fi-chlorobu-
(Eltekow, Ber. 8, 1244). Also from trimethyl

tane CH
3 -CH,-CHC1-CH 3 ,
is produced by the
action of nitrosyl chloride on secondary butyl-

carbinol and phosphorus pentabromide(Reboul,
amine in xylene solution at 20 (Solonina,
J. 1881, 409). May also be prepared by leading Chem. Zentr. 1898, ii. 888).
tsobutylene into a solution of hydrobromic acid
of sp.gr. 1-7 (Roozeboom, Ber. 14, 2396). Is Butyl cyanates. Only the iso-cyanates have
been described.
readily decomposed at 300 into isobutylene
and hydrobromic acid. Water, in the cold, forms 1. Isobutyl isocyanate. Isobutyl carbi-
the alcohol. mide (CH 3 2 CH-CH 2 -NCO
) b.p. 110 obtained ;
4. Secondary butyl bromide, /3-brom- by the distillation of isobutyl iodide with silver
butane CH 3 -CH 2 -CHBr-CH 3 b.p. 90-93 (V. ;
cyanate and sand (Brauner, Ber. 12, 1877).
2. Tertiary butyl isocyanate
Meyer and Miiller, J. pr. Chem. [2] 46, 183) ;
obtained from secondary butyl alcohol by the (CH 3 ) 3 C-NCO ;
action of hydrobromic acid, and yields (y)- b.p. 85-5 (corr.); sp.gr. 0-8676 at ; remains
dibrombutane by warming with iron and liquid at 25. Is formed, together with other
bromine. substances, when silver cyanate acts upon isobutyl
Butyl chlorides. Tetryl chlorides C 4 H 9 C1. iodide (Brauner, Ber. 12, 1874). By the action
586 BUTYL OR TETRYL.
of hydrochloric acid, forms tertiary butylamine 203, 21) ; sp.gr. 1-643 at 0, 1-6136 at 20 (Lieben
ONH
;
((JH 3 ) 3 2 Potash produces symmetrical

.
j
and Rossi, ibid. 158, 163), 1 -6166 at 20/4 (Bruhl).
ditsobutyl urea, melting at 242. From w-butyl alcohol and hydriodic acid (Linne-
Butyl cyanides. C 4 9 CN. H mann, ibid. 161, 196). By the action of iodine
1. Normal butyl cyanide, valeronitrile
'
trichloride at 250 it yields hexachlorethane ,( 'I .
CH 3 -CH 2 -CH 2 -CH 2 CN ; (Krafft, Ber. 10, 805).

2.
Isobutyl iodide,
b.p. 1404 at 739-3 mm. ; sp.gr. 0-8164 at
a-iodo-&-methylpro-
(Lieben and Rossi, Annalen, 158, 171).
pane (CH 3 } 2 -CH-CH 2 I b.p. 120-0 (corr.);
2. Isobutyl cyanide (CH 3 2 -CH-CH,-CN ) ;

(Linnemann, Annalen, 160, 240 192, 69) ; ;
126-128 at 714 mm. (Erlenmeyer and 83-83-25 at 250 mm. (Perkin, Chem. Soc.
b.p.
Trans. 1884, 451); sp.gr. 1-6401 at (L.),
Hell, Annalen, 160, 266); 129-3-129-5 at
1-6056 at 20/4 (Bruhl, Annalen, 203, 21), 1-6138
764-3 mm. (R.Schiff, Ber. 19,567); sp.gr. 0-8227
at 15/15, 1-6007 at 25/25 (P.). Molecular
at 0, 0-8069 at 20 (Erlenmeyer and Hell) 0-6921
rotation at 19-4= 12-199 (P.).
;
at 129/4 (S.). Formed by the oxidation of

From wobutyl
alcohol, phosphorus, and iodine (Wurtz, Annalen,
gelatin (Schlieper, Annalen, 59, 15) or casein
93, 116).
(Gunckelberger, ibid. 64, 76) with chromic acid ;
also by the action of P 2 5 upon ammonium
3. Secondary butyl iodide, fi-iodobutane
isovalerate (Dumas, Malaguti, and Leblanc, C 2 H 5 -CHI-CH 3 ;
ibid. 64, 334). May be prepared by heating 300 b.p.117-118 (Luynes, Bull. Soc. chim. 2, 3);
grams isobutyl iodide, 98 grams of potassium 119-120 (Lieben, Annalen, 150, 96); sp.gr.
cyanide, 98 grams of alcohol, and 25 grams of 1-6263 atO/0, 1-5952 at 20/0 , 1-5787
at 30/0
water for three days on the water-bath (Erlen- (Lieben). Formed by distilling erythritol with
meyer and Hell). hydriodic acid (Luynes) or from w-butylene and
3. Tertiary butyl cyanide (CH 3 ) 3 OCN; hydriodic acid (Wurtz, Annalen, 152, 23). (See
m.p. 15-16; b.p. 105-106. Formed by also Clarke, Chem. Zentr. 1908, ii. 1015.)
mixing 100 parts of tertiary butyl iodide, 110 4. Tertiary butyliodide, &-methyl- ft-iodo-
propane (CH 3 ) 3 CI ; b.p. 98-99 (with decom.)

'
parts of mercury potassium cyanide Hg(CN) 2
2KCN with 75 parts of dry magnesia, and allow- (Butlerow) 100-3 (Puchot, Ann. Chim. Phys. ;
ing the mixture to remain for two or three days [5] 28, 546) sp.gr. 1-571 at 0, 1-479 at 53 (P.). ;
at a temperature not exceeding 5. The mass is From tertiary butyl alcohol and hydriodic acid
then treated with water, and distilled on the or tsobutylene and hydriodic acid (Butlerow,
paraffin-bath (Butlerow, Annalen, 170, 154). Annalen, 144, 5, 22) ; is easily decomposed (by
4. Secondary butyl cyanide, methylethyl silver oxide, potash, or by heating with zinc i
acetonitrile C 2 H 6 -CH 3 -CH-CN ; b.p. 125; sp.gr. I

and water), into hydriodic acid and isobutylene
0-8061 at 0. Sodium
eqv.) (
is dissolved in (Butlerow, Zeitsch. Chem. 1867, 362). Is also
acetonitrile in benzene, and ethyl iodide (1 eqv.) j decomposed by water in the cold, yielding
added (Hanriot and Bouveault, Bull. Soc. chim. hydriodic acid and tertiary butyl alcohol. On
(3), 1, 172). heating with sodium, yields a mixture of hydro-
Butyl hydrides. Butanes, tetranes. gen, tsobutylene, and triisobutylene (C 1 ,H., 4 )
1. Normal butane, diethyl, methylpro- (Dobbin, Chem. Soc. Trans. 1880, 236).
pane CH 3 -CH 2 -CH 2 -CH 3 ; b.p. 1 (Butlerow, Butyl mercaptans C 4 9 -SH. H
Zeitsch. Chem. 1867, 363); sp.gr. 0-60 at 1. Normal butyl mercaptan
(Ronalds, Chem. Soc. Trans. 1865, 54). CH 3 -CH 2 -CH 2 -CH 2 -SH;
Occurs in crude petroleum (Ronalds, Lefebvre, 97-98 0-858 at and
b.p. ; sp.gr. (Saytzeff
Zeitsch. Chem. 1869, 18

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lMiV.

SIR EDWARD THORPE, C.B., LL.D., F.R.S.

Assisted by Eminent Contributors

REVISED AND ENLARGED EDITION

5 Vols. Medium 8vo, 2 $s. net per volume.

LONGMANS, GREEN, AND CO

SIR EDWARD THORPE, C.B., LL.D., F.R.S.

PROFESSOR OP GENERAL CHKMISTRT AND DIRECTOR OP THE CHEMICAL LABORATORIES OP THK

LATE PRINCIPAL OF THE GOVERNMENT LABORATORY, AND A PAST PUK8IDKNT OF THE

ASSISTED BY EMINENT CONTRIBUTORS

REVISED AND ENLARGED EDITION

LONGMANS, GREEN, AND CO

All rights reserved

Chemistry is practically a new work.

tions, is prefixed to the several volumes in which these contributions appear.

strators, Assistant-Demonstrators, and Assistants in the Chemical Department

Dr. Arthur Clayton Mr. A. T. King, B.Sc.

Mr. E. G. Couzens, B.Sc. Mr. F. P. Dunn, B.Sc.

Amer. Chem. J. American Chemical Journal.

ASPARAGUS AVOCADO PEAR ; BANANA BARLEY BATATAS BEAN BEET-ROOT

BETAINE BLACKBERRIES BRAN BREAD FRUIT BUCK WHEAT CABBAGE CARROT

CASSAVA CASTOR OIL SEEDS

Dr. RUDOLF LESSING, Consulting Chemist, London. [BROMINE.]

NUT OIL CASTOR OIL ;CHAULMOOGRA OIL GROUP.] ;

CESIUM ; CERIUM METALS AND EARTHS.]

B. E. R. NEWLANDS, Esq., F.I.C. (Messrs. Newlands Brothers, Analytical Chemists, London).

BUCKTHORN BUTEA FRONDOSA CATECHU CATELLAGIC ACID CHAY ROOT CHESTNUT

Dr. HENRY ROBINSON, M.A. [ANESTHETICS.]

ABABOBA POWDER BALSAMS ; ; BLACK HELLEBORE ROOT ; BROOM TOPS ; CALUMBA ;

CAMPHOBS CASCABA SAGBADA; ; CASCAEILLA BARK.]

ABGENTITE ABGYRODITE ASBESTOS

BORONATROCALCITE BOSTONITE BOURNONITE BRAUNITE BROCHANTITE BBOGGEBITE

BRUCITE BUHBSTONE CALCITE

CERARGYRITE CERUSSITE CHALCANTHITE CHALK CHALYBITE.]

GEORGE STUBBS, The Government Laboratory, London. [BUTTER.]

EDWARD R. TAYLOR, Penn Tan, N.Y., America.

in the quantity and suppresses the

bitter principle extracted from the dried leaves

absinthium Composites), a plant

constituent, boiling at 203, has the formula Trans. 69, 1196).

to tetrahydroacenaphthene (Sabatier and Sen-

derens, Compt. rend. 132, 210, and 566) ; with

(Graebe and Gfeller, Ber. 25, 652 Jaubert, ;

Semmler, Ber. 25, 3343 and 27, 895). J. C. 1

14, 156 ; Stas, Ann. Chim. Phys. [3] 19, 146 ;

the distillate again rectified the fraction 100-

acetal. sp.gr. 1-0418 at 0, 1-026 at 15 (Klien) 156- :

mixture, passing dry hydrogen chloride to satu- 34 Krey, I.e.

acid (Fischer and Giebe, Ber. 30, 3053 31, 545).

and Fuchs, Ber. a green mass, changing to blood red on addition

Annalen 229, 165; ferric chloride gives no blood-red colouration

Ber. Acidum Aceticum. C 2H 4 2

37 1775 Steinkopf, Ber. 41, 3571 Swartz,

Monatsh. of organic matter.

as Antifebrin, is prepared by heating

1888 1111), at 305 (corr.) (Perkin, Chem. Soc.

Alcohol. Acetic acid.

sulphuric acid (Hantzsch

and producing acid. It is formed by the

Thorpe's Dictionary of Applied Chemistry Vol.1

Thorpe's Dictionary of Applied Chemistry Vol.1

Thorpe's Dictionary of Applied Chemistry Vol.1