[Comprehensive Analytical Chemistry 10] G. SVEHLA (Eds.) - Organic Spot Test Analysis the History of Analytical Chemistry (1980, Elsevier Science) - Libgen.lc

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Professor Emeritus: Honorary Senior Research Fellow, Faculty of Medicine,
University of Birmingham
G. den Boef, PH.D.

Professor of Analytical Chemistry, University of Amsterdam
A. Hulanicki, PH.D.
Professor of Chemistry, University of Warsaw
J. Inczedy, PH.D., D.SC.

Professor of Analytical Chemistry, University of Chemical Engineering,
Veszprem
H.M.N.H. Irving, M.A., D.PHIL., F.R.I.C.

Professor of Inorganic Chemistry, University of Cape Town
W.A.E. McBryde, PH.D

Professor of Chemistry, University of Waterloo, Ontario
G. Tolg, PH.D.
Professor of Analytical Chemistry, Max-Planck-Institute for Metal Research,
Stuttgart
D.W. Wilson, M.SC., F.R.I.C.

Head of the Department of Chemistry, City of London Polytechnic
Contributors to Volume X
L. Ben-Dor, Department of Inorganic and Analytical Chemistry, The Hebrew

U n i v e r s i t y o f J e r u s a l e m , J e r u s a l e m , Israel
E. Jungreis, Department of Inorganic and Analytical Chemistry, The Hebrew

U n i v e r s i t y o f J e r u s a l e m , J e r u s a l e m , Israel
A . R o b i n s o n , T h e Queen's University, Belfast, N . Ireland
F. Szabadvâry, Museum for Science and Technology, Budapest, Hungary

Wilson and Wilson's
COMPREHENSIVE
ANALYTICAL
CHEMISTRY
Edited by
G. SVEHLA, PH.D., D . S C , F.R.I.C.
Reader in Analytical Chemistry

The Queen's University of Belfast
VOLUME X
Organic Spot Test Analysis

The History of Analytical Chemistry
ELSEVIER SCIENTIFIC PUBLISHING COMPANY

AMSTERDAM OXFORD NEW YORK
1980
WILSON A N D WILSON'S
COMPREHENSIVE ANALYTICAL CHEMISTRY
V O L U M E S IN T H E SERIES
Vol. IA Analytical Processes

Gas Analysis
Inorganic Qualitative Analysis
Organic Qualitative Analysis
Inorganic Gravimetric Analysis
Vol. IB Inorganic Titrimetric Analysis

Organic Quantitative Analysis
Vol. IC Analytical Chemistry of the Elements
Vol. IIA Electrochemical Analysis

Electrodeposition
Potentiometric Titrations
Conductometric Titrations
High-frequency Titrations
Vol. IIB Liquid Chromatography in Columns

Gas Chromatography
Ion Exchangers
Distillation
Vol. IIC Paper and Thin-Layer Chromatography

Radiochemical Methods
Nuclear Magnetic Resonance and Electron Spin
Resonance Methods
X-Ray Spectrometry
Vol.IID Coulometric Analysis
Vol. Ill Elemental Analysis with Minute Samples

Standards and Standardization
Separations by Liquid Amalgams
Vacuum Fusion Analysis of Gases in Metals
Electro analysis in Molten Salts
Vol. IV Instrumentation for Spectroscopy
Atomic Absorption and Fluorescence Spectroscopy
Diffuse Reflectance Spectroscopy
Vol. V Emission Spectroscopy

Analytical Microwave Spectroscopy
Analytical Applications of Electron Microscopy
Vol. VI Analytical Infrared Spectroscopy
Vol. VII Thermal Methods in Analytical Chemistry

Substoichiometrie Analytical Methods
Vol. VIII Enzyme Electrodes in Analytical Chemistry

Molecular Fluorescence Spectroscopy
Photometric Titrations
Analytical Applications of Interferometry
Vol. IX Ultraviolet Photoelectron and Photoion Spectroscopy

Auger Electron Spectroscopy
Plasma Excitation in Spectrochemical Analysis
Vol. X Organic Spot Test Analysis

The History of Analytical Chemistry
Vol. XI The Application of Mathematical Statistics in

Analytical Chemistry
Mass Spectrometry
Ion Selective Electrodes
Preface
In Comprehensive Analytical Chemistry, the aim is to provide a

work which, in many instances, should be a self-sufficient reference
work; but where this is not possible, it should at least be a starting
point for any analytical investigation.
It is hoped to include the widest selection of analytical topics that

is possible within the compass of the work, and to give material in
sufficient detail to allow it to be used directly, not only by profes-
sional analytical chemists, but also by whose workers whose use of
analytical methods is incidental to their work rather than continual.
Where it is not possible to give details of methods, full reference to
the pertinent original literature is made.
Volume X contains two chapters. The first, on organic spot test

analysis, is complementary to P.W. West's shorter chapter on inor-
ganic spot test procedures, published in Volume IA more than 20
years ago. The fact that both authors were co-workers of Fritz Feigl,
the initiator of this simple but effective technique, is a recommenda-
tion in itself. They pay their homage to their late master at the begin-
ning of their text. It is perhaps fitting to remind our readers that
Fritz Feigl was, until his death, a member of the Advisory Board of
this Series, and provided valuable assistance to the Editors of the
day. The second chapter presents a brief history of analytical chem-
istry. Besides being a valuable source of references to early analytical
work, this chapter makes most amusing reading. Some years ago, I
translated an earlier book by Professor Szabadvâry into English and
enjoyed this work immensely. I hope that the present text, written
in association with a junior colleague of mine, will again be well
received by the public.
Dr. C.L. Graham of the University of Birmingham, England, assis-

ted in the production of the present volume; his contribution is
acknowledged with many thanks.
January, 1980 G. Svehla

Chapter 1
Organic spot test analysis

E. J U N G R E I S a n d L. B E N - D O R
Dedicated to the loving memory of our teacher, Fritz Feigl
1. Introduction
Spot tests are defined as an analytical technique which enables the

analyst to accomplish satisfactory semi-micro, micro and ultra-micro
tests with simple equipment and minimum consumption of sample
and time. These simple tests make use of the color and odor of the
organic compound in the preliminary stage of analysis and also the
identification of certain vapors and gases evolved during pyrolysis.
The observation of the organic sample on ignition (to give a smoky
or smokeless flame) can roughly differentiate between aromatic and
aliphatic as well as other classes of compounds. The test for acidic or
basic behavior can give a first indication of the presence of certain
functional groups, and the redox behavior of the organic compound
can give valuable information concerning the structure. The detec-
tion of metallic and non-metallic elements also belongs to this pre-
liminary stage of the analysis.
The main field of qualitative organic analysis is the detection of
certain groups of the compounds, the detection of characteristic
types of compounds and, whenever possible, the identification of
individual compounds. This goal is mainly attained through the
observation of the results of the chemical reactions into which the
functional groups enter. Such reactions include chelate formation,
catalysed and induced reactions, masking procedures, solid—solid
reactions at elevated temperatures, reactions in the gas phase through
contact with solid or dissolved reagents, reactions which yield
fluorescent or colored products or those which quench fluorescence.
References pp. 54—60 1

One should keep in mind that the enormous number of organic
compounds and the variety of their architecture pose an immense
challenge. It is well known that in qualitative inorganic analysis the
target is to detect the metallic and non-metallic elements and almost
always it is possible to do this by chemical means. Detection of
elements, however, in organic compounds has only an orienting
value, because the real aim of the analysis is the identification of
functional groups. The vast number of homologues would react
identically to a selective functional group reagent even if other
regions of the molecules differ greatly. Thus reliable tests of indivi-
dual compounds by purely chemical means are infrequent. The
revolutionary development in gas and liquid chromatography and the
coupling of chromatography with mass spectrometry are becoming
more and more important in solving these analytical problems. How-
ever, as was above defined, spot test analysis is considered simple,
time- and material-saving, and inexpensive. These qualitative tests
are instrumentally unsophisticated but their use has a considerable
practical importance. Analytical problems seldom involve totally
unknown materials. The information available concerning the origin,
method of preparation, color of the sample, etc. almost always gives
valuable clues as to the direction of the spot test examination. The
analytical problem is not always to detect a particular organic com-
pound but rather to find out whether members of a class of com-
pounds are present or absent and this goal is generally achieved by
spot test analysis.
The life-work of Fritz Feigl [1] has contributed overwhelmingly
to the field of spot test analysis. He not only adapted known reac-
tions (and syntheses) to analytical procedures but created a vast
variety of new ones thus enriching the chemistry of "specific, selec-
tive and sensitive reactions" [ 2 ] . Other significant contributors to this
field are Schenk [ 3 ] , Cheronis et al. [ 4 , 5 ] , Neunhoeffer [6] and
Duval [ 7 ] . During the last 15 years, a vast contribution to the field
was made by L. Légrâdi from Nitrokémia Co., Fûzfôgyârtelep, Hun-
gary.
Inorganic spot test analysis was critically and scholarly summarised
by West [211] in Vol. 1A of this series.
2
2. Preliminary tests
The preliminary test contributes to the identification of organic

compounds, but one has to be very careful not to exaggerate the
importance of this primary information. The color, the form and
behavior under heat can give an indication concerning the unknown,
but under no circumstances can the results serve as a definite proof.
One should use more trustworthy tests before drawing conclusions.
(A) SENSORY TESTS (COLOR A N D ODOR)
The most natural primary test makes use of the eye and the nose.
Although most pure organic compounds are colorless and odorless,
the appearance of color and odor has some diagnostic value. Yellow
material can indicate nitro, nitrozo and azo compounds, the shift to
longer wavelength might suggest the presence of conjugation, chela-
tion or dyestuffs. Fluorescence is sometimes helpful. Although the
appearance or quenching of fluorescence (under UV irradiation)
might be caused by impurities, the effect can be of significance when
it appears in carefully purified material (e.g. by sublimation or
recrystallization). Recently, this effect has been extensively used for
the detection and determination of carcinogenic materials [ 8 ] .
The detection of odoriferous materials can sometimes be extremely
sensitive. Materials like menthol, phenol, pyridine, butyric acid and
vanillin can be detected using this very subjective method in the
9 1 4
dilution range 1 : 10 —1 : 1 0 . Again, one should be very careful
not to be misled as slight contamination may cause the effect.
Good examples of very characteristic odors are the almond odor
of nitrobenzene and benzaldehyde, the garlic odor of ethyl sulfide,
the rancid odor of long-chained fatty acids and the familiar odors of
alcohols, ethers and thiocompounds.
(B) BEHAVIOR ON IGNITION
The burning test of organic compounds is based on the fact that

the various classes show different visual phenomena in spite of the
similar conditions. This can be attributed to the fact that different
chemical reactions occur during the combustion depending on struc-
ture, such as dehydration, thermal cleavage, pyrohydrolysis, redox
reaction, etc. Burning aromatic compounds and halogen compounds

gives a smoky flame whereas the lower aliphatic compounds burn
with a smokeless flame. Compounds containing a high percentage of
halogens do not ignite easily and oxygen-containing compounds
show a bluish flame. Carbohydrates and nitrogen-rich compounds
(proteins) burn with a characteristic odor resembling burnt hair.
(C) P Y R O L Y S I S
By pyrolysis is meant the rapid external heating of the substance

with a limited access of air. The decomposition resulting from the
heating leads to the formation of lower molecular weight compounds
which, due to their volatility, can be easily detected in the gas phase.
These pyrolytic cleavage products can be acidic or ammoniacal
vapors, hydrogen cyanide, dicyanogen, hydrogen halides, acetal-
dehyde, carbon monoxide, sulfur dioxide, hydrogen sulfide, nitrous
acid, phenols, etc. The release of hydrogen cyanide from nitrogeneous
organic material (tested with copper acetate and tetrabase acetate
reagent paper [9] ) is almost general. Thus, only a negative test might
be of diagnostic value. On the other hand, the detection of dicya-
nogen (by potassium cyanide *—oxine paper [10]) is almost specific
for uric acid and purine derivatives. Hydrogen halides are formed in
the gas phase by the pyrolysis of both aromatic and aliphatic halogen
compounds. The selective detection of these hydrogen halides is
achieved by demasking of silver ferrocyanide by the halide and the
formation of Prussian blue by the reaction of the liberated ferro-
cyanide with ferric iron [ 1 1 ] . A high analytical importance should be
attributed to the pyrolytical test of nitrogen—oxygen-containing
compounds which, without exception, split off nitrous acid (tested
with Griess reagent [12]). Aromatic compounds which have oxygen
atoms either in the nucleus or the side chain yield phenols on strong
pyrolysis. These are detected by 2,6-dichloroquinone-4-chloroimine
paper [13] which yields the blue indophenol dye.
(D) A C I D - B A S E A N D REDOX BEHAVIOR
The consumption and production of protons in an organic com-

pound are responsible for the basic or acidic behavior of the material.
* Instead of t h e e x t r e m e l y t o x i c p o t a s s i u m c y a n i d e , a n y strong base can be used

(E. Jungreis, unpublished results).
4
The derivatives of ammonia, hydroxylamine and hydrazine are the
stable bases. The detection of the basic character can afford a valu-
able clue for the detection of such functional groups. On the other
hand, functional groups which split hydrogen ions such as carboxy-
lic, sulfonic, sulfinic, arsonic nitroxylic, oximic, primary and second-
ary nitro enolic, thioenolic, phenolic, thiophenolic, acetylenic sulfon-
amidic and secondary acid amidic are detectable by acid character.
The acidity or basicity of compounds soluble in water can easily
be detected by conventional indicators; even a system of mixed indi-
cators has been described [ 1 4 ] for differentiating them according to
strength. An ingenious method has been described for the detection
of water-insoluble basic groups based on shifting of the reaction
equilibrium of either the formation of the red nickel dimethyl-
glyoxime chelate
2+ +
N i + 2 DMGH 2 -> Ni(DMGH) 2 + 2 H (1)
or the formation of the fluorescent zinc oxinate [ 1 5 ]
2+ +
Zn + 2 OxH -> Zn(Ox) 2 + 2 H (2)
After removal of the precipitates, the equilibrium solutions which
result may react with the basic unknown and the consumption of the
protons results in the appearance of either a red precipitate (1) or a
fluorescent material (2).
The familiar iodine formation from an iodate—iodide mixture in
the presence of protons is utilized for the very sensitive detection of
acidic organic compounds. If pre-fused potassium iodate (which con-
tains iodide) is heated even with insoluble, extremely weak organic
acid, iodine is liberated [ 1 6 ] .
Among organic materials, reducing behavior is much more pre-
dominant than oxidation. However, there are a few classes of com-
pounds such as polyhalides of organic bases, quinones and their tetra-
halogenide derivatives, peroxyacids, etc. which clearly are oxidizing
agents. Their identification is carried out by the oxidation of tetra-
base reagent paper to give the blue protonated derivative [ 1 7 ] .
C H N +
( 3 > 2 - ^ ( 0 ) - C H 2H ^ ) - - N ( C H 3 ) 2 + [Ο] m~ ( Ο Η 3) 2Ν ^ ( θ ^ - ^ Η = = < ^ ) = Ν ( Ο Η 3 ) 2 + OhT
There is a great variety of reducing organic compounds including

phenols, uric, ascorbic, rhodizonic, and rubeanic acids, benzidine,
tetrabase and other polyamines, benzaldehyde and its derivatives,
formaldehyde, sugars, etc. They are detected in the depression of a

TABLE 1
Detection of elements
Element Reagent Reaction mechanism Procedure and Refs. Ref. of Remarks

observation alternative
studies
c Solid molyb- t C ] + 4 M0O3 -> C 0 2 + 2 M o 2 0 Ashing with 25 26 Avoid presence of

5
denum reagent at ca. other reducing
trioxide 5 0 0 ° C . Blue agents
coloration
H Elemental 2 [ H ] + S - > H 2S Heating with 27
sulfur reagent to 250°C.
H 2S d e t e c t e d w i t h
lead acetate paper
in gas p h a s e . B l a c k -
brown coloration
0 Ethereal solu- Solvate formation of the dried The reagent, o n 28 29 Solid material
t i o n o f ferric reagent with o x y g e n - c o n t a i n i n g the tip o f a fine s h o u l d be dis-
thiocyanate sample glass r o d , is d i p p e d s o l v e d in o x y g e n -
into test solution. free organic sol-
Red coloration vent. A v o i d sulfur
and nitrogen donors
Ν Solid man- [N] + 2 M n 0 2 -> N 0 2 + 2 MnO Strong heating 30,31 47
ganese with the reagent
dioxide with a micro flame.
N 0 2 detected with
m o i s t Griess or
Saltzman reagent
filter paper o n t o p
of test tube. Pink
or red c o l o r a t i o n
MgCC>3
Halogens Magnesium RX 7—+ MgX2 Liberated halogen 32,33
carbonate fol- pyrolysis detected either
l o w e d b y sul- with thio Michler's
^ ' X 2 t
k e t o n e reagent
fochromic
acid p a p e r o r Ν,Ν-άϊ-
methyl p-phenyl-
e n e d i a m i n e paper,
Blue or reddish-
sdoudddjdtf
violet coloration,
respectively.
Halogens Succinic or R X + [ H 20 ] - > R O H + H X Pyrohydrolysis 34

(aliphatic) phthalic acid with reagent at
Og—frç dd
200-230°C.
Liberated H X
d e t e c t e d b y silver
ferrocyanide—ferric
sulfate paper.
Prussian blue p p t .
CaO
F Pyrolysis with 35 36
Calcium oxide —F — > C a F 2
or m a g n e s i u m reagent. Fluoride
oxide detected with
strongly acid red
z i r c o n i u m alizari-
nate solution.
Yellow coloration.
K M n 0 4+ H 2S 0 4
Cl P o t a s s i u m per- C h l o r i n e is s e l e c - 37 38,47 Although the
-x *x t2
manganate— ioo°C tively detected reagent liberates
sulfuric acid with diphenyl- all h a l o g e n s , t h e
amine trichloro- d e t e c t i o n is s e l e c -
acetic acid reagent tive for chlorine
paper. Greenish-
blue coloration
Br Sulfochromic — X — > X 2T B r o m i n e is s e l e c - 39 A v o i d large

acid tively detected amounts of
with p-aminophenol iodine
reagent paper.
TABLE 1 (continued)
Elements Reagent Reaction mechanism Procedure and Refs. Ref. of- Remarks
observation alternative
studies
MgC03
I Magnesium - X > MgX2 I o d i d e is o x i d i z e d 40 41,42,43,47
carbonate by chloramine Τ
solution to iodine
w h i c h in turn
o x i d i z e s tetra-
base t o the blue
dyestuff.
S Solid calcium C a C 20 4 + [ S ] -> C a O + C O S COS o n hydrolysis 44 45,46,49

oxalate + co 2 liberates H 2S
d e t e c t e d b y lead
acetate paper.
Brown-black stain.
HCIO4
Se Concentrated —Se ^ H 2S e 0 3 S e l e n i o u s a c i d is 47 Specific for
perchloric acid 250 c d e t e c t e d b y its selenium
reduction by
hydrazine to
the red elemental
selenium
CaO
Ρ Calcium oxide -P ^ C a 3( P 0 4) 2 P h o s p h a t e is 48
red heat detected with
molybdic a c i d -
nitric acid in t h e
presence of a
reducing agent to
give m o l y b d e n u m
blue.
spot plate by ammoniacal phosphomolybdic acid which is reduced to
molybdenum blue [ 1 8 ] .
Another procedure [19] uses ammonium molybdate and excess
perchloric acid in a differentiating detection test for certain classes of
organic reducing agents. This procedure distinguishes aliphatic from
aromatic aldehydes, alicyclic from acyclic and aromatic ketones,
phenols and saturated alicyclic alcohols from saturated acyclic alco-
hols.
(E) E L E M E N T A R Y A N A L Y S I S
The detection of the non-metallic and metallic elements in organic

compounds is generally preceded by the destruction of the material
and identification of the elements of the inorganic compound
formed. This destruction is carried out by pyrolysis with carbonates
[ 2 1 ] , strong oxidizing acids [ 2 2 ] , oxidants such as vanadium pen to x-
ide [ 2 3 ] , or heating the sample in aluminum foil under a stream of
oxygen [ 2 4 ] , Table 1 summarizes reactions for some of the impor-
tant non-metallic elements and gives references to alternative
methods. For the metallic elements, one should consult Feigl's Spot
Tests in Inorganic Analysis [ 2 0 ] .
3. Detection of functional groups
One of the most important targets of qualitative organic analysis

is the identification of functional groups. An organic molecule may
include several of such groups and their detection may largely
characterize its chemical and physical properties.
In this chapter, we intend to limit ourselves to the discussion of
the most common functional groups and to emphasize especially the
newer methods which have been published since the publication of
the 7th edition of Feigl's Spot Tests in Organic Analysis.
(A) AROMATIC COMPOUNDS
The classical method for the detection of aromatic compounds is

the Le Rosen test [50] which is based on the reaction of the aroma-
tic material with formaldehyde in concentrated sulfuric acid, ulti-

mately to give a semi-quinoidal color product, viz.
2 (O) + C H 20
( O ^ C H 2H Q > + 2 H 2S 0 4 - ( 0 ) - C H = < ^ ) = 0 + 3 H 20 + 2 S02
This test has several disadvantages, viz. a number of compounds are

colored by sulfuric acid alone and there is a lack of differentiation
for different classes of aromatic compounds, and finally the Le
Rosen test fails with aminobenzenes.
Pb(IV) and Tl(III) acetates in trifluoroacetic acid [51] serve as
spot test reagents for the detection of aromatic compounds avoiding
most of the above-mentioned shortcomings. This acid, as opposed to
sulfuric acid, is relatively inert and gives no coloration alone with the
aromatic material. By contrast to the Le Rosen test, para position
blocking does not seem to inhibit color production. The mechanism
of the reaction is probably as complex as that of the Le Rosen test,
involving oxidations and condensations. In the trifluoroacetic acid
test, the inertness of the supporting solvent is very important. The
function of the lead and thallium in their highest oxidation states
is doubtless an oxidizing action, although the mechanism of the
attack is not certain.
Within the framework of aromatic compounds, special spot tests
were elaborated for benzyl and benzal groups. Benzyl compounds,
when warmed with potassium cyanide, form benzyl cyanide which
can then be detected by the Zimmerman reaction [ 5 2 ] . The benzal
group can be detected by oxidative cleavage to give benzaldehyde
and its subsequent detection with thiobarbituric acid [ 5 3 ] ,
/θ)—CH = CHCOOH + 2 [θ] — < ^ 0 ) - C H O + CHOCOOH
OC—NH OC-NH
<^Ο^-0ΗΟ + H 2C C S ^Ô^-CH = C C S + H 20
OC — NH OC — NH
A newer test [52] for the benzal group has been suggested. The
test is based on the reaction with phenylhydrazine to give on further
oxidation with potassium bromate, a compound whose coloration is
due to nitrogen double bonds.
10
2<Ô>-NH-NH2 H ,
H H, ,
H
[O]
KBr03
ol
(B) U N S A T U R A T E D C O M P O U N D S
Double and triple bonds can be detected according to the familiar

reducing action on potassium permanganate or the addition of
bromine to such bonds [ 5 4 ] .
-HC=CH 2 + Br 2 > -HCBr—CH 2Br
The resulting primary bromide can be detected by heating with
sodium thiosulfate which ultimately gives off sulfur dioxide.
A more recent method is based on the epoxidation with peroxy-
benzoic acid and the subsequent color reaction with aromatic dini-
trosulfonic acids [ 5 5 ] . Instead of the unstable perbenzoic acid,
m-chlorobenzoic acid and its p-nitroderivatives can be used as rea-
gents [ 5 6 ] . These reagents exhibit a better stability pattern.
(C) H Y D R O X Y COMPOUNDS
There are no special difficulties in detecting hydroxyl groups but

the detection of the group itself does not elucidate the nature of the
compound. It is important to know whether the hydroxyl group is
aliphatic, aromatic or part of a heterocyclic compound. If the func-
tional group is alcoholic, one still needs to know whether it is
primary, secondary or tertiary.
The classical reaction such as that with metallic sodium is not only
characteristic for the hydroxyl group but indicates the presence of
any active hydrogen. On the other hand, an alkaline solution of diazo-
benzenesulfonic acid gives a red color product only with aliphatic
hydroxy compounds.
(1) Alcohols
Primary, secondary and tertiary alcohols react with the phenol

ester of 8-hydroxyquinoline with o-vanadic acid (see test procedure 1,
p. 43 ). Such compounds have the tendency to form stable red aleo-
holates [57] according to the formula
OH-(ROH)x
A variation of this test uses piperdine 8-hydroxyquinoline vandate

[58].
Another test is based on the reaction of all aliphatic alcohols with
1-chloromethylisatin to give alkoxymethylisatines [ 5 9 ] .
The reaction between diazotized sulfanilic acid and hydrazoben-
zene can be used for the selective detection of alcohols because the
intensity of the color formed depends on the alcohol chosen as
medium [60] ; e.g. methanol gives a violet red product, ethanol a red
product and propanol an orange product.
Primary and secondary alcohols can be detected [61] by their con-
version to xanthates followed by the violet product formation with
molybdate.
2
NaOH M0O4
ROH + C S 2 • CS(OR)(SNa) + H 2 0 ^ MoO a · 2 CS(OR)SH
Secondary alcohols [ 6 2 ] split off hydrogen sulfide, which can be
easily tested in the gas phase, when fused with elementary sulfur.
:CHOH + S -> CO + H 2 S t
Tertiary alcohols can be identified by the Lucas test [63] in which
a tertiary alkyl chloride is formed by the action of hydrochloric
acid—zinc chloride solution. This chloride forms immediately as a
separate phase and is thus identified.
ZnCl2
R3COH + HC1 • R3CCI + H 2 0
Though secondary alcohols react similarly, their reaction is rather

sluggish.
(2) Phenols
The familiar method for the detection of phenols is based on the
12
fact that all enolic hydroxides give colored complexes with ferric
chloride.
+
6 (θ^-ΟΗ + FeCI3 [ F e ( O - ^ Q ) ) 6] + 3 HCI + 3H
Based on the colored product, a rough differentiation among phenols

is possible; e.g. violet with phenol, resorcinol, salicylic acid, a-naph-
thol; blue with o , m-, p-cresol, hydroquinone, xylenol; green with
pyrocatechol, β-naphthol; red with nitrosalicyclic acid, oxyisoph-
thalic acid.
Another classical detection is the Liebermann test [ 6 4 ] for phenols
having a free para position. Such phenols form nitroso derivatives
with nitrous acid in concentrated sulfuric acid. These exist in tauto-
meric equilibria with quinone imines which give indophenol blue
with alkaline phenols (see test procedure 2, p. 43.)
-OH
Q=^ ^=N-OH + Η-^Ο^-ΟΗ ^ Q=<^ y=N-^Q^-Oh\ + H 20
A modification to this test [ 6 5 ] makes use of an appropriate

p-nitrosophenol directly; e.g. 5-nitroso-8-hydroxyquinoline in con-
centrated sulfuric acid in its oxime form acts directly with phenols to
form the analogous indophenol dye
Another test is based on phenols having a free ortho position [ 6 6 ]

by the Duff method. Hexamine, in its trialkylamine form, gives a
condensation product with such phenols which is easily saponified
with acids to give o-hydroxyaldehydes. The latter give fluorescent
aldazines with hydrazine. Recently, it was shown that the products
are, in fact, hydrazones [ 6 7 ] .
A test for selected phenols such as resorcinol, a- and /?-naphthol,
and others has been recently outlined [ 6 8 ] based on the Janowsky
reaction. An ethanolic solution of the phenol gives a characteristic
coloration with alkaline dinitrobenzene.
It is well known that Ce(IV) salts in nitric acid are selective oxir
dants and the resulting Ce(III) salts give colored molecular com-

pounds with phenolic and alcoholic oxidized products. This reaction
was recently modified by the introduction of soluble eerie salts in
the presence of hydroxylamine to form stable orange complexes with
phenols only [ 6 9 ] .
(3) Aliphatic poly hydroxides
Polyhydroxyalcohols with boric acid give stable complexes which,

in contrast to the weak boric acid, behave as strong electrolytes.
This behavior can be detected with acid—base indicators such as
methyl orange or phenolphthalein [ 7 0 ] . Polyhydroxyalcohols can
also be oxidatively decomposed to formaldehyde and formic acid
with an excess of periodic acid. Identification is made either by the
precipitation of the iodate formed with silver ions or by the fuchsin
aldehyde reaction [71] (see test procedure 3, p. 43.)
Pentoses, hexoses and their anhydrides hydrolyze with concen-
trated sulfuric acid to give furfural or its derivatives. These alde-
hydes form highly colored condensation products with a-naphthol,
violet Schiff bases with aniline [ 7 2 ] , a cationic type pentamethine
dye of the general formula
+
[ RS= CH-CH= C H - C = C H - S R ] X "
OH
with cystein [ 7 3 ] , or a sensitive color reaction with 2,2,5,5-tetra-
kis(carboxymethylthio)-!,4-dithian [ 7 4 ] .
HOOC-CHg-S'
(TCD)
A variety of reactions have been developed whereby the reducing

action of sugars is demonstrated. Two familiar examples are the
reduction of alkaline bismuth tartrate or ammoniacal silver nitrate
solution whereby blackening is observed due to the formation of
elementary bismuth or silver, respectively.
(D) CARBONYL COMPOUNDS
It is possible to divide the reactions for the identification of alde-

hydes and ketones roughly into two large groups: in the first, the car-
14
bonyl compounds from a precipitate or a weakly dissociated com-
pound with the reagents. In general these reactions are rather unspe-
cific; nearly all aldehydes and ketones give a similar positive test. In
the second are listed those reactions which are based on the reducing
action of aldehydes.
In recent years, reactions for carbonyls have been devised which
were based on the formation of free radicals or fluorescent products.
The latter is based on the fluorigenic reactions with o-aminodiphenyl
in dilute sulfuric acid; pyridoxal, higher fatty aldehydes, glycolalde-
hyde, glyoxylic acid and 2,3-pentanedione give brilliant fluorescent
spots in UV light when heated with the reagent spray [ 7 5 ] .
Phenylhydrazine and its 2,4-dinitro derivative are the most com-
mon reagents for detecting carbonyl compounds. The coloration of
the products is highly intensified when using azobenzene—phenyl-
hydrazine instead. These classical reactions are rather sensitive; for
example, it is possible to detect even small carbonyl impurities in
alcohols. The color of the phenylhydrazone precipitate is indicative
of the original aldehyde or ketone. Yellow coloration is character-
istic of a carbonyl group not in conjugation with any other func-
tional group. On the other hand, if a carbon double bond or benzene
ring is in conjugation with the oxo group, the color shifts to orange-
red.
Another differentiation among phenylhydrazones is based on their
relative stability towards oxidation with potassium bromate in
hydrochloric acid. On this basis, it is possible to detect mesityl oxide,
acetylacetone, acetone, m-nitrobenzaldehyde and salicylaldehyde in
the presence of other carbonyl compounds [ 7 7 ] .
An alternative general reaction for ketones and aldehydes is based
on the formation of the respective bisulfates which, unlike free bisul-
fate, do not discolor iodine [ 7 8 ] .
All aldehydes and ketones form a yellow coloration with ethano-
lamine and formic acid. The mechanism of the color reaction is not
yet fully understood. It does not involve quinone formation since ali-
phatic compounds also give a positive reaction. It is very likely that
the reaction proceeds via Schiff's base formation since no color reac-
tion is observed when the product obtained after addition of alde-
hyde to ethanolamine is reduced with LiAlH 4. Probably the Schiff s
base is rapidly converted into oxazolidine derivatives which react
with formic acid to give colored products [ 7 9 ] .

(1) Aldehydes
The reducing action of aldehydes can be demonstrated with the
Fehling and Benedict reagents. These react only with aliphatic alde-
hydes; on the other hand, the Tollens test is useful for aromatic alde-
hydes as well.
The fully aromatic p-fuchsin is decolorized by the action of sul-
furous acid. On the addition of aromatic or aliphatic aldehydes, a
partly quinoidal, violet to blue compound is obtained [ 8 0 ] .
The colored Schiff bases formed by the condensation of aromatic
and aliphatic aldehydes with o-dianisidine is a highly sensitive reac-
tion [ 8 1 ] . Another condensation reaction [ 8 2 ] makes use of indole
as a reagent (see test procedure 4, p. 44), viz.
H
pink-orange
R = alky I or a r y l
Detection of aliphatic aldehydes is based on their reaction with

propionaldehyde (3-phenyl-2-quinoxalinyl) hydrazone to give a red
dye. Ketones and aromatic aldehydes do not interfere [ 8 3 ] . Aliphatic
aldehydes and ketones react with 2,3-dimethyl-2,3-bis(hydroxy-
lamino)-butane to form a condensation product which can be con-
verted to intensely colored stable free radicals by the addition of
sodium periodate or lead dioxide [ 8 4 ] (see test procedure 5, p. 44).
red-blue
For the selective detection of aromatic aldehydes, use is made of

the Schiff base formation with iV,iV-dimethyl-p-phenylenediamine
and its subsequent protonation (intense red color) [85] (see test
procedure 6, p. 44).
The condensation [ 8 6 ] of aromatic aldehydes in concentrated
hydrochloric acid yields orange-pink monomethine chloride.
16
HO HO
H IC
ArCHO + <Λ5^-ΟΗ + [ A r - C H - ^ Q ) - O H ) ] CI + H 20
HO
Substituted aromatic aldehydes containing hydroxy or methoxy

groups form red compounds when heated with diphenylamine in the
presence of hydrochloric acid [ 8 7 ] . The mechanism of the reaction
is
H C
C 6H 5 6 5
"NH + HCI N H 2C I
Cf Hn
•6i 5
CI
+ C LN H
H 3C 0 ^ ( 0 ) - C C 2 ^ u • H 3C O - \ 0 > - C H = N ^ + H 20
H
\ / Ô C 6H 5 Ν / ^6 5
These aromatic aldehydes were also detected with 2,2,5,5-tetrakis-

(carboxymethylthio)-p-dithian [ 7 4 ] , a reagent already mentioned for
the detection of sugars.
Another color reaction for aromatic aldehydes (and their acetals)
is based on their reaction with o-phenylphenol [ 7 6 ] .
(2) Ketones
A well known test for ketones is based on their reaction with
sodium nitroprusside to give a yellow-red color which turns to pink-
violet on acidification (see test procedure 7, p. 44). Only ketones
which contain an enolizable CO group give this reaction [ 8 8 ] . A
recent test is a modification of this and uses aquopentacyanoferrate
as a reagent [ 8 9 ] .
The formation of indigo by the action of onitrobenzaldehyde on
ketones in alkaline solution is used for the detection of ketones and
also for the CH 3C = 0 group.
^ \ . C H O - ^ ^ . C H O HOC ^HC O C H a
+ CH3COCH3
[OT - [oT
\ ^ N 0 2 ^ ^ N 0 2
-CH3COOH ^CH=CH2 intramolecular
£Q£X condensation^ j-g^_Jj
N02
polymerization
Η Η
indigo
References pp. 54—60

17
Various α-substituted ketones are detected by chemiluminescence
following their oxidation with basic hydrogen peroxide. The a func-
tional groups, such as carbonyl oxygen or hydroxyl, increase the
fractional positive charge on the carbonyl group. The 1,2-diketones,
such as 2,3-butanedione, are known to react with the strongly
nucleophilic hydroperoxide anion to form unstable hydroperoxy
compounds of the type
o - o
I
R-C-CR
I
OOH
which decompose to give acids. These hydroperoxides are suffi-

ciently strong oxidants to produce chemiluminescence in luminol
[90].
(3) Acids and esters
Carboxylic acids and their derivatives are convertible to hydroxa-

mic acids which can be detected by the ferric hydroximate test. The
first step involves the formation of the acid chloride, by the action of
thionyl chloride, followed by reaction with alkaline hydroxylamine
[91] (see test procedure 8, p. 45).
SOCb N H 2O H
R C H
O O 1^. RCOCI ^ RCO(NHONa)
NaOH
Η
.NHOH 3+ +
,Ν-Ο
R_ C ^ + ^Fe • R-C I + H
2
•Ô Ô—Fe/3
red
Another test [ 9 2 ] proposed for carboxylic acids is based on their

transformation to the acid chloride which subsequently reacts with
o-nitrophenylhydrazine. The acid—base indicator formed is yellow
in acidic solution and violet or blue in alkaline media.
= =
RCOCI + Η2Ν-ΝΗΗ^Ο^> R-C = N - N = / )) ^==± R-C-NH-NH-Ô)
ι \ j O HH" - A
ο >r/
Ν Ο;
0 2N ο " Ν" ο 0 2N
Ο
violet yellow
Acid anhydrides react directly with o-nitrophenylhydrazine to give

the same indicator. The test does not respond to acid amides, imides,
18
esters, sulfamides and peroxides. By means of this reaction, it is pos-
sible to detect acid anhydrides in the presence of carboxylic acids by
spot test, e.g. 0.01% acetic anhydride in acetic acid [ 9 3 ] .
Chloromethylisatin was also used for identifying carboxylic acids.
Carboxylic acid salts with chloromethylisatin form isatinylmethyl
esters (monomers or dimers) which are well characterized [ 9 4 ] .
ο
[O
ΓδτΛ=ο
Ο \
C H 2- 0 - C O - R
OT /=° + RCOOH
Ν \ ^ Ο Q
or y °
C H 2C I
O< joj
Ν Ν
\ /
2 CH -0-CO-R-CO-0-CH
Alkyl esters, when heated with metallic sodium, form2 sodium salts
of enediols which react with 1,2-dinitrobenzene to give red nitroso-
nitrobenzene [ 9 5 ] (see test procedure 9, p. 45).
Na R-C-ONa ^ Ν 0 2 ^ ^ N O N a
RCOOR" II *~ L L
R-C-ONa ^ t ^ N 0 2N a
red
(E) E T H E R S
Ethers can be detected by their transformation to peroxides [ 9 6 ]

when heated to 230° C in a glycerol bath. The split-off oxygen, from
the perioxides, can be identified by numerous redox reactions such
as copper ethylacetoacetate—tetrabase (see test procedure 10, p. 45),
potassium iodide, thio-Michler's ketone, etc.
Ethoxy ethers, when treated with boiling alkali dichromate and
sulfuric acid, are hydrolyzed to ethanol and subsequently oxidized
to acetaldehyde. The latter is identified by the sodium nitroprus-
side—morpholine reagent [ 9 7 ] ,
Alkyl phenyl ethers heated with potassium iodide and oxalic acid
dihydrate are dialkylated and the phenols obtained are volatilized.
Gaseous hydrogen iodide, released by the action of the oxalic acid,
reacts according to
ArOR + HI -> RI + ArOH
The phenols are identified in the gas phase by the indophenol reac-
tion [ 9 8 ]

(F) AMINES
If nitrogen is detected in an organic sample during elementary

analysis and if this sample is insoluble in water but soluble in mineral
acid, it is highly probable that the unknown is an organic amine.
The detection of primary, secondary and tertiary amines, both ali-
phatic and aromatic, is possible via a reaction with 2,4-dinitrochloro-
benzene [99] which forms colored products due to the quinoidal
zwitterion structure formed.
Only free bases in the absence of acid or alkali condense in this

manner, e.g. aliphatic and aromatic amino acids do not give such a
reaction. Thus, amines can be detected in the presence of amino-
carboxylic or aminosulfonic acids (see test procedure 1 1 , p. 46).
Another general test is based on the reaction with a whole series of
nitro and dinitro compounds to give colored products with any
amine [ 1 0 0 ] . The test is used mainly for differentiation among
various amines in air pollution studies based on the different colora-
tion of the products.
Primary and secondary amines, both aliphatic and aromatic, are
detected through the familiar Schiff base formation either with
p-dimethylaminobenzaldehyde [ 1 0 1 ] or with p-dimethylaminocinna-
maldehyde [ 1 0 2 ] . The former gives yellow bases with monoamines
and orange products with polyamines. By the action of dilute acid,
the color is intensified due to protonation.
+
- N = C H - £ - NH = C H -
The use of p-dimethylcinnamaldehyde, on the other hand, allows a

differentiation between primary and secondary amines, the former
giving blue products and the latter purple products (see test proce-
dure 12, p. 46).
l-(Isothiocyanatomethyl)-isatin gives well-characterized products
with primary and secondary amines [ 1 0 3 ] ,
With carbon disulfide, even at room temperature, primary and
secondary aliphatic amines form dithiocarbamates [104] which can
subsequently be detected by the sodium azide—iodine catalysed test
20
(see test procedure 13, p. 46).
CS2+2NHRiR2 ^- sc
NRiR2
A selective test for primary aliphatic amines has been described
[ 1 0 5 ] , The test is based on the reaction of dibepin 2 in alkaline
medium with the amines, leading to the appearance of a blue-violet
coloration.
Ethyl- or isopropyl-2-oxo-but-3-ynoate condenses with primary
and secondary aliphatic amines and also with primary aromatic
amines to give a bright yellow product [ 1 0 6 ] .
The introduction of dimethylamino groups and their derivatives
into thiodiphenylamine and its subsequent oxidation by bromine
leads to the formation of methylene blue or to the respective thia-
zine dye. This reaction is the basis for a selective test for all secondary
amines [ 1 0 7 ] , viz.
(OT ΥΟΊ + 2 N H ( C H 3) 2 + 6 B r 2 • i j t | Π Br~ + 5HBr
With carbon disulfide and ammoniacal copper (II) salt, secondary

aliphatic amines form a brown chelate of the respective dithiocar-
bamic acid [ 1 0 8 ] (see test procedure 14, p. 46).
Glutaconic aldehyde formed by UV irradiation of pyridine con-
denses with primary aromatic amines to give polymethine dyes [ 1 0 9 ,
110].
H
c
S
^ UV HÇ^ CH Α Γ Ν Η 2· Η Χ H C ^ C H
H HO C
ÎST 2 ° HCONH4 ArN = C H CH-NHAr-HX
3-Bromo-2-nitroso-l-naphthol [ 1 1 1 ] was found to be a sensitive

reagent for the detection of aromatic amines.
Many aromatic amines and iV-heterocyclic compounds give inten-
sively and characteristically colored compounds with organic poly-
halogen compounds under UV irradiation or under sunlight [ 1 1 2 ] .
There are some preconditions for the reaction.
(1) There must be at least one direct N—aromatic bond in the
amine.
(2) At least one of the 2,4, and 6 positions in the ring must con-
tain a hydrogen atom.

(3) The reagent must contain a great number of loosely bound
halogen atoms, such as in CBr 4 or CHI 3.
No disturbance whatsoever was recorded by other compounds.
Aromatic amines, primary and secondary, give a color reaction
with potassium bromate. The reaction depends on the functional
group present, e.g. nucleophilic substituents accelerate the reaction
while electrophilic ones hinder it. It is possible, for example, to
detect p-anisidine in the presence of p-toluidine. The ortho isomers
of aromatic amines give the strongest color reaction; para isomers do
not react [ 1 1 3 ] .
A reaction having a very similar mechanism [114] was also used
for the detection of aromatic amines, but instead of potassium
bromate, AT-chlorophthalimide was used. The reagent contains a
labile chlorine atom which serves as oxidant to give a semiquinoidal
colored compound.
A sensitive reagent, derived from transaconitic acid and acetic

anhydride, was used as a color test for tertiary amines. The com-
pound formed, a - y anhydroaconitic acid, reacts with the amines to
yield a blue-red product [ 1 1 6 ] . This test is important for chromato-
graphic detection.
Tertiary amine functional groups present in anticholinergics, anti-
depressants, anticonvulsants, antischizophrenics, analgesics and hallu-
cinogens, can be detected by ethyl bis(2,4-dinitrophenyl)acetate
which acts as an acid—base indicator [ 1 1 5 ] .
(G) NITRO COMPOUNDS
Primary and secondary aliphatic nitro compounds are, in fact,

pseudo acids. The characteristic reaction of such compounds with
bases results in salts of the aci-form. While the ordinary nitro com-
pounds are colorless or faintly colored, the aci-form shows intensi-
fication of the color. Tertiary nitro compounds and all aromatic
nitro compounds cannot show this kind of tautomerism, nor do they
22
show this color variation. On the other hand, aromatic polynitro
compounds with strong bases are transformed to intensely colored
quinoidal compounds, viz.
-tor
N02
— XX
O-N-O"
Nitro compounds can be better detected using their oxidation

potential. When mixing nitro compounds with strong reducing agents,
it is possible either to detect the resulting amino compounds or
register the changes occurring in the reducing agent itself. The former
method is, of course, more specific.
Nitro compounds, when heated, form orange-red addition com-
pounds with molten tetrabase or diphenylamine.
C 6Hn
I6 5
NH*—0 = N— R
I I
C 6H 5 CT
In most cases, the color disappears once the melt cools [ 1 1 7 ] (see
test procedure 15, p. 47).
Primary aliphatic nitro compounds in their aci-form couple with
diazonium salts [ 1 1 8 ] to give colored condensation products, e.g.
tetrazotized di-o-anisidine (fast blue salt B) yields in alkaline solution
with primary nitroparaffins the following mono- or di-coupling pro-
ducts (see test procedure 16, p. 47).
+
cr H ; 2 M
~C> N=CR
OCH3 CH3O
Primary and secondary nitro compounds in alkaline solution are

oxidized to aldehyde and nitrite. The latter is detected by the Griess
reaction. Tertiary derivatives do not react because the nitronate
anion cannot be formed [119] (see test procedure 17, p. 47).
R - ^ C H 2 - N 0 2 + OH" -> R - C H = N O ^ + H 2 0
R - C H = N O ^ + H 2 0 2 -> RCHO + H 2 0 + NO^
Polynitro compounds containing an active methylene group or a
mobile hydrogen atom give a color reaction with alkali in alcohol
[ 1 2 0 ] . It is assumed that here there is an intermolecular reaction,

e.g.
A spot test is elaborated for mononitrobenzene derivatives with

phenylacetonitrile in an alkaline dimethylformamide medium. A blue
to yellow color indicates the presence of a nitro compound [ 1 2 1 ] .
About 60 nitro aromatic compounds of widely varying structure
were detected by this method. Compounds having electrophilic
groups such as —CHO, - C O C H 3 , —COOH, —CONH 2 gave positive
tests while compounds having nucleophilic substituents such as NH 2,
OH, CH 3 gave negative tests. The reaction mechanism for p-chloro-
nitrobenzene is
blue colorless
On a very similar basis [ 1 2 2 ] , it was possible to detect m-nitro-

toluene in the presence of the ο and ρ isomers.
Some aromatic nitro compounds form charge-transfer, via π—7Γ,
complexes with iV,AT-diethylaniline in chloroform [ 1 2 3 ] . A/îV-diethy-
laniline has the largest red shift in the C—Τ band maxima. The spot
test is applicable to all types of nitro compounds except for those
containing highly electron-donating groups such as CH 3, NH 2, etc.
Compounds containing both donor and acceptor groups cannot be
detected by the above method, e.g. nitrotoluene or nitroaniline.
(H) NITRILES
Aromatic and aliphatic nitriles (cyanides) react at 180° C with

hydrated oxalic acid through pyrohydrolysis to form amides, which
24
are subsequently transformed to oxamides by pyroacidolysis [ 1 2 4 ] .
The oxalic acid dihydrate serves here both as a hydrolytic and an
acidolytic reagent. The oxamides are identified by sintering with
thiobarbituric acid to give an orange product (see test procedure 18,
p. 48).
(R, Ar)CN + H 2 0 -> (R, Ar)CONH 2
2 (R, Ar)CONH 2 + (COOH) 2 -> 2 (R, Ar)COOH + (CONH 2) 2
It was shown also that aromatic and aliphatic nitriles as well as

compounds containing C=N groups, in open or closed chains, release
thiocyanic acid when melted with sulphur [ 1 2 5 ] . HSCN can be
detected through its familiar reaction with ferric ions. On the other
hand, pyrolitically, aliphatic nitriles only release hydrogen cyanide at
250°C.
A recent study describes the detection of both aliphatic and aroma-
tic nitriles using resin beads after hydrolysis with dilute sulfuric acid
to produce ammonium ions. These ions are retained by the ion
exchanger and thence detected by the blue indophenol dye resulting
from the sodium hypochloride—phenol reaction [ 1 2 6 ] .
(I) S U L F U R COMPOUNDS
If, sulfur is detected in a preliminary test, it is possible to differen-

tiate between the bonding types and oxidation states of the element.
Thioketones and thiols are detected by the catalytic reaction of the
iodine—azide reaction [127] (see test procedure 19, p. 48).
]
2 N a N 3 + I 2 ^ 2 Nal + 3 N 2 t
Other S-containing organic functional groups do not interfere. Thiols

can be further differentiated through their precipitation with
cuprous salts [ 1 2 8 ] . Primary and secondary thiols form H 2S when
boiled with concentrated ammonia; tertiary thiols and thioketones
do not react [ 1 2 9 ] .
Some reagents for the detection of thiols were developed: 2,2'-
dithiobis-(5-nitropyridine) and 2,3-dichloronaphthoquinone give
selectively characteristic colored products with thiols [ 1 3 0 , 1 3 1 ] .
Mercuric cyanide selectively reacts with acidic mercaptans and
their alkali salts to liberate cyanide which is subsequently detected

in the gas phase with tetrabase copper ethylacetoacetate reagent
[132].
2 RS~ + Mg(CN) 2 -> Mg(SR) 2 + 2 CNT
All sulfonic acids are pyrohydrolyzed with succinic acid at 200° C.
The superheated steam liberated reacts with the solid sulfonic acid
which is hydrolyzed to give sulfuric acid which is thence reduced to
sulfurous acid. The latter is detected with iron(III) hexacyano-
ferrate(III) indicator [133] (see test procedure 20, p. 48).
Sulfoxides are detected by the Dragendorff reagent, i.e. iodobis-
muthate solution. This reagent gives an orange to red colored pre-
cipitate with sulfoxides. The sensitivity of the test is dependent on
the total number of carbon atoms in n-C 4H 9SOR (R = alkyl) [ 1 3 4 ] .
4. Detection of technically important individual compounds

The exact identification of a pure organic compound is mainly
based on the measurement of its physical properties: melting and
boiling points, density, refractive index, optical activity, ultraviolet
and infrared absorption, Raman spectroscopy, NMR, etc.
The necessity of previous isolation of the material, however, and
the subsequent procedure to obtain it in a state of high purity makes
the physical laboratory methods rather lengthy and even cumber-
some. The development of modern chromatographic techniques,
mainly TLC, gas and HP liquid chromatography, greatly facilitates
the separation of the individual compounds, even close members of
a homologous series. Once the components of a mixture are sepa-
rated, one needs a good sensitive test but not necessarily a selective
one. Organic spot tests, based on chemical reactions, which are per-
formed rapidly rarely succeed in detecting specifically an individual
organic compound, although quite a number of specific tests for
important compounds do exist. On the other hand, this technique
has the advantage of not requiring sophisticated and expensive instru-
mentation. In the majority of cases, there is some previous know-
ledge about the origin of the sample, which supplements somewhat
the necessity of absolute specificity.
(I) A C E T O N E
It is possible to detect acetone [135] specifically through its con-

densation with salicylaldehyde to obtain a red conjugated compound
26
(see test procedure 2 1 , p. 49).
- 2 H 20
O ^ - C H O + CH3COCH3 + OHC-<^0
OH HO
Acetone can also be detected by means of a diazotized p-pheneti-

dine leading to a deep red coloration [ 1 3 6 ] .
(II) A C E T I C A C I D
A dark blue precipitate [ 1 3 7 ] results when lanthanum salts are

mixed with iodine and ammonia in the presence of acetic acid or
acetates. The color is due to an adsorption compound between
iodine and basic lanthanum acetate. A large number of anions do
interfere with this test, but the microdistillation [138] of the acetic
acid in the presence of concentrated phosphoric acid avoids most of
the disturbances. (See test procedure 2 2 , p. 49).
Capillary distillation in the presence of mercuric oxide and dihy-
drogen phosphate buffer also serves for the detection of acetic acid.
The distillate is tested with lead monoxide and sodium fluorescein.
The acid dissolves the oxide reacting with the fluorescein to give an
intense orange-red precipitate. In the absence of oxidizable organic
acids, the test for acetic acid proves to be highly selective [ 1 3 9 ] .
(1 ) Monochloroacetic acid
Monochloroacetic acid heated with ammonium thiocyanate forms

rhodanine which subsequently, due to its reactive ^ C H 2 group, forms
a p-quinoidal blue-violet condensation product with 1,2-naphtho-
quinone-4-sulfonate [ 1 4 0 ] .
H 20 HN CO
C H 2C I C O O H + N H 4S C N ( rhodanine )
SC,
(2) Dichloroacetic acid
Dichloroacetic acid mixed with Nessler's reagent immediately

deposits finely divided mercury [ 1 4 1 ] . Actually, alkali glyoxalate
is formed which, due to its aldehydic nature, reduces the iodo-mer-
curate.
OH~ [ H g l 4] 2—
CHCl2COOH OCH e o c r
ΟΗ

(3) Trichloroacetic acid
This strong acid splits off chloroform when treated with caustic
alkali. The chloroform liberated can be identified by the Reimer^-
Tiemann type formylation reaction leading to salicylaldehyde [ 1 4 2 ] .
The latter can be identified through the fluorescence of its aldazone
[67].
(III) A C E T Y L A C E T O N E
Acetylacetone, when warmed with formaldehyde in the presence

of ammonium salts, condenses to give a green fluorescent dihydro-
pyridine derivative [ 1 4 3 ] .
H 3C C O COCH3
2 C H 3C O C H 2C O C H 3 + C H 20 + NH; 3 H 20
H 3C .
(IV) ACETYLENE
An orange or yellow flocculent precipitate forms between acetyl-

ene and ammoniacal silver chromate and is used for the identification
of acetylene. An addition compound forms between silver acetylide
and silver chromate. It is insoluble in mineral acid and serves as a pro-
tective layer around silver chromate [144] (see test procedure 23,
p. 49).
(V)ANTHRACENE
Anthracene evaporated with concentrated nitric acid is oxidized to

anthraquinone. The latter can be identified by its reductive conver-
sion into red, water-soluble sodium salt of anthrahydroquinone
[145].
(VI) ASCORBIC ACID
For identification purposes, use is made of the reductive power of

ascorbic acid. Various reactions are possible, e.g. the reduction of
manganese dioxide, ammonium phosphomolybdate, chloranil-^di-
phenylmethane dyestuff mixture, iron(III) hexacyanoferrate(III), etc.
[146].
28
(VII) B A R B I T U R I C A C I D
Barbituric acid reacts almost instantaneously with nitrous acid to

give violuric acid. Its alkali salts are red-violet [147] (see test proce-
dure 24, p. 49).
O OH
Ο OH
Another study shows that the addition of various amines to anhy-

drous methanolic solutions of Co(II) thiocyanate produces a range of
reagents for the detection of barbiturates. Tertiary amines such as
trimethylamine and morpholine and its derivatives were found the
most satisfactory reagents. The use of 2,6-dimethylmorpholine,
resulting in violet-purple color, is recommended [ 1 4 8 ] .
(VIII) C A R B O N D I S U L F I D E
With secondary aliphatic amines, carbon disulfide forms dithio-

carbamates which are chelate-forming with transition metal ions. The
test solution containing carbon disulfide is added to an ammoniacal
copper solution containing dimethylamine resulting in the formation
of a yellow chelate precipitate [149] (see test procedure 25, p. 50).
(IX) C A R B O N MONOXIDE
Carbon monoxide can be detected through a heterogeneous cata-

lytic reaction with phosphomolybdic acid and palladium salts. Car-
bon monoxide alone does not reduce the reagent to give molyb-
denum blue. However, in the presence of palladium salts, the reac-
tion takes place [ 1 5 0 ] .
(X) CARBON TETRACHLORIDE
Carbon tetrachloride vapor releases chlorine when heated in the

presence of pulverized quartz sand; most likely a disproportiona-
tion occurs on the surface of the quartz.
CCl3 CCI2 -, Γ
2CCL - I - II + [CI]
4
CCI3 CCI2

The test is selective for carbon tetrachloride at 250° C; at higher tem-
peratures, other chlorine-containing organic material can also react,
e.g. chloroform [ 1 5 1 ] . (See test procedure 26, p. 50.)
(XI) C H L O R O F O R M A N D BROMOFORM
These two solvents are identified by their pyroammonolytic reac-

tion which splits off hydrogen cyanide
CH(Hal) 3 + N H 3 HCN + 3 HHal
The ammonia is produced in situ by the decomposition of guanidine
carbonate at 800° C [ 1 5 1 ] .
(XII) CINNAMIC ACID
This acid splits off benzaldehyde when heated with alkali per-
manganate solution. The vapors of the benzaldehyde are identified
through the Schiff s base formed with o-dianisidine [ 1 5 2 ] .
(XIII) CITRIC A C I D
Citric acid is converted by alkali permanganate into acetone dicar-

boxylic acid, which in the presence of bromine precipitates as penta-
bromo acetone [153] (see test procedure 27, p. 50).
C H 2C O O H n r C H 2C O O H _ _ CHBr2
HOOC-C-OH *~ 9 ° *~ V°
CιH 2C O O H CιH 2C O O H CI B r 3
(XIV) CYSTEINE
This compound may be detected on a spot plate by successive

treatment of the test solution with ammoniacal sodium nitroprusside
and sodium pyruvate. A red-violet color results [ 1 5 4 ] . (See test
procedure 28, p. 50.)
(XV) DIPHENYLAMINE
A sensitive and selective test for diphenylamine [155] is based on

the adsorption by resin beads of the colored Schiff s base formed
30
between diphenylamine and p-dimethylaminobenzaldehyde in acid
medium. The color is probably due t o a protonated structure. The
following mechanism was postulated.
N ( C) H
R ( C 6H 5) 2N H 2 + OHC-^0/- 3 2
ΔΤ
R ( C 6H 5) 2N - C H = ^ ^ ) = N ( C H 3 ) 2 ^ R ( C 6H 5) 2N - C H - ^ Q ^ - N ( C H 3 )
yellow bluish g r e e n
(XVI) ETHANOL
The selective detection of ethanol is based on its oxidation to ace-

taldehyde, which, in the vapor phase, can be detected with the nitro-
prusside—morpholine reaction [ 1 5 6 ] . (See test procedure 29, p. 51.)
(XVII) FORMALDEHYDE
Formaldehyde condenses with J-acid dissolved in concentrated

sulfuric acid which acts as an oxidant. A yellow xanthylium dyestuff
forms which fluoresces under UV radiation [ 1 5 7 ] . The yellow solu-
tion turns blue on dilution. (See test procedure 30, p. 51.)
Another test is based on the reaction of formaldehyde with
m-phenylenediamine hydrochloride where a water-soluble yellow
polymer is obtained [ 1 5 8 ] .
(XVIII) FORMIC ACID
A selective test for formic acid is based on its condensation with

p-alkylquinaldinium salts to form a blue-green cyanide dye-stuff
[159] (see test procedure 3 1 , p. 51).
Another color reaction which permits the identification of formic

acid (and formates) is based on the red color obtained from citric or
aconitic acid with formic acid in the presence of acetic anhydride
and isopropanol [ 1 6 0 ] .
(XIX) F U R F U R A L
Furfural, like other aromatic aldehydes, reacts with phloroglucinol

and hydrochloric acid to give an orange condensation product.
However, in contrast to other aldehydes, the product obtained from
furfural rapidly changes to green [ 1 6 1 ] .
CI" + H 20
(XX) GLYCEROL
The classical Skraub synthesis is used for the identification of

glycerol. 8-Hydroxyquinoline is obtained from the reaction between
o-aminophenol and acrolein. The latter is formed by the dehydra-
tion of glycerol with concentrated sulfuric acid. Although this micro
"synthesis" is of rather a low yield, the oxine obtained is detected
extremely sensitively through the fluorescence of its magnesium salt
[162].
t
OCH
<§U •
OH
(See test procedure 32, p. 52.)
(XXI) GLYOXAL
A specific test for the detection of glyoxal is based on its reaction

with 2-hydrazinobenzothiazole to form a product containing an
extended conjugated chain which is highly fluorescent [ 1 6 3 ] .
32
(XXII) LACTIC ACID
Lactic acid can be easily oxidized with lead dioxide to pyruvic

acid, which subsequently condenses with β-naphthylamine to give
a-methyl-j3-naphthocinchoninic acid. This acid is identified through
its reaction with citric acid in acetic anhydride leading to a red-violet
coloration [ 1 6 4 ] .
[o]
CH3CHOHCOOH — »» CH3COCOOH
0= C-CH3
' . COOH ^ (r^xÇ^T
C^
1 I
COOH COOH
(XXIII) MALONIC ACID
A specific test for malonic acid is based on its reaction with fused
urea whereby barbituric acid results. The latter is identified by its
reaction with pyridylpyridinium dichloride to give directly a red pen-
tamethine dye [ 1 6 5 ] . (See test procedure 33, p. 52.)
COOH NH2 CO-NH
I I I pyridy! p y r i d i n i u m d i c h l o r i d e
CO H ?C CO
CH2 I I I
NH2 CO-NH
COOH
OH
+
[ H O - ^ ^ C H - X H - C H - X H - H C - ^ ) - O H ] {
OH HO
(XXIV) METHANOL
Acidic permanganate oxidizes methanol to formaldehyde. The spe-

cific test for the latter with chromotropic acid to give, ultimately, a
bright violet p-quinoidal compound serves for the specific detection
of methanol [ 1 6 6 , 1 6 7 ] .
SO-,Η SO3H SO3H
[oj [o] HO- / / VcH=< > = 0

CH3OH
-HoO
SO-,Η

(XXV) NAPHTHALENE
Naphthalene vapor (50—70°C) reacts selectively with chloranil to

give a 1 : 1 brick-red molecular compound [ 1 6 8 ] . (See test proce-
dure 34, p. 52.)
(XXVI) OXAMIDE
Oxamide on heating with barbituric or thiobarbituric acid [169] or

phloroglucinol [170] condenses to form multi-conjugated colored
products. This deep black to brown coloration serves to detect
oxamide.
(XXVII) OXALIC ACID
Oxalic acid decomposes pyrolitically at 250° C to give formic

acid. The latter, with diphenylamine, forms leuco-aniline blue
which in contact with air transforms to aniline blue. This reaction
serves for the selective detection of oxalic acid [ 1 7 1 ] . (See test
procedure 35, p. 52.)
(XXVIII) PHOSGENE
Phosgene reacts rapidly with alkyl- and aryl-hydrazine to form

symmetric carbohydrazides owing to its two mobile chlorine atoms.
As diphenylcarbazide forms a deep violet chelate with cupric ions,
this could serve as a test for phosgene [ 1 7 2 ] .
C 6H 5- N H - N H 2 αχ C 6H 5- N H - N H
+ CO /C O + 2 HCI
C 6H 5— N H - N H 2 CI C 6H . 5- N H - N H
(XXIX) PIPERIDINE
Piperidine [ 1 7 3 ] , through its reactive N H 2 group, reacts with 1,2-

naphthoquinone-4-sulfonate to yield intensely colored brick-red
p-quinoidal condensation products. In the absence of ammonium
34
salts and amines, the test is selective provided the piperidine is carried
in the vapor phase with water vapor (90°C). (See test procedure 36,
p. 53.)
(XXX) PYRIDINE
The selective test for pyridine and its derivatives with a free para
position, is based on their action with bromocyanogen and o-toli-
dine. The resulting product is a red polymethine dye [ 1 7 4 ] .
^—»~ O C H - C H = C H - C H = CHOH
0 ) N = C H - C H = C H - C H = C H N H ( 0
Pyridine and its derivatives also react with cyanuric acid chloride
[175] to form a triazine compound, the alkali salt of which is
orange. A typical triazine is
OH
O.
(I)
In another test, trisodium pentacyanoammino ferrate forms a

colored compound with pyridine and its derivatives by replacement
of the ammonia with pyridine in the coordination sphere [ 1 7 6 ] , (See
test procedure 37, p. 53.)
(XXXI) QUINONES
Quinones give colored condensation products with rhodanine;

green or blue with p-quinones and violet-red with o-quinones [ 1 7 7 ] .
Another test [ 1 7 8 ] is based on the condensation with 4-nitrophenyl-
acetonitrile to give a blue or violet product. (See test procedure 38,
p. 53.)
CN _ CN
H 2 2
2 Q 2N ^ Q ^ ) - C H . 2C N + Q=<^ °»» 02N-(Oy-C=(^^C^(Q^-N02

(XXXII) SALICYLALDEHYDE
Salicylaldehyde and its easily oxidizable homologues (e.g. salicyl

alcohol) react with concentrated mineral acids to form a red color
due to the protonation of the carbonyl oxygen of the aldehyde. This
serves for the selective detection of salicylaldehyde [ 1 7 9 ] . Other
former studies were based on the fluorescence of either its phenolate
or its azine but these tests are not selective [ 1 8 0 ] . (See test procedure
39, p. 54.)
(XXXIII) TARTARIC ACID
Tartaric acid, when heated with concentrated sulfuric acid con-

taining some gallic acid, forms a blue-green colored product. Actu-
ally, the glycol aldehyde generated gives the colored condensate with
gallic acid [ 1 8 1 ] .
(XXXIV) THIOPHEN
Thiophen reacts with polyketones containing two adjacent CO

groups in open or closed chains to form quinoidal dyestuffs. Such a
poly ketone is the familiar ninhydrin which, in concentrated sulfuric
acid, immediately gives a red color on the addition of traces of
thiophen [ 1 8 2 ] .
(XXXV) TYROSINE
Tyrosine yields a deep purple color on the addition of a-nitroso-

/3-naphthol and nitric acid. The test is characteristic for tyrosine
among other α-amino carboxylic acids [ 1 8 3 ] .
(XXXVI) UREA
Urea is identified by the evolution of ammonia through the

enzymatic hydrolysis by urease [ 1 8 4 ] . (See test procedure 40,
p. 54.)
Urea also reacts with tetrachloro-p-benzoquinone (chloranil) to
give water-soluble violet-colored products, the structure of which is
dependent on the reaction medium. In general, these reactions
involve nucleophilic displacement of one of two of the chlorine
36
atoms by hydroxyl and/or amino groups. The detection of urea is
based on the reaction of chloranil with a neutral aqueous solution of
the sample which on heating gives 2,5-dichloro-3-amino-6-hydroxy-p-
benzoquinone.
The participation of urea in this reaction is probably based on its

decomposition to ammonia [ 1 8 5 ] .
5. Differentiation of isomers
In order to characterize organic isomers or homologues by their

physical parameters, one needs prior separation and isolation.
A variety of organic spot tests permits the differentiation of
isomers and homologues by chemical reactions without prior isola-
tion. In these cases, certain identification reactions occur only with
one of the isomers and fail with the others.
(A) AMINOBENZENESULFONIC ACIDS
The isomeric aminobenzenesulfonic acids, viz. orthanilic, metani-

lic, and sulfanilic acids, can be selectively detected in the presence
of each other. The ortho derivative forms a diazonium salt in acid
medium rapidly in contrast to the other isomers. By this reaction, it
is possible to detect orthanilic acid selectively. With diazotized ani-
line, the coupling is most rapid with the para derivative, thus the
detection of sulfanilic acid is facilitated in the presence of the other
isomers. The reaction rate of the meta derivative is highest for the
reaction with 2,4-dinitrofluorobenzene to give a red product. By this
method, it is possible to detect the meta and para isomers in presence
of the ortho. Differentiation between metanilic and sulfanilic acids is
based on the fact that KBr0 3/HCl in acetone preferentially oxidizes
the meta derivative. The bromination of all aminobenzenesulfonic
acids leads to the formation of tribromometanilic acid from the
meta derivative but to tribromoaniline from the two other isomeric
acids. This reaction also has an analytical application [ 1 8 6 ] .

(Β) AMINOBENZOIC ACIDS
These three isomeric acids are distinguishable in a mixture accord-

ing to the following. The alkali salts of o-aminobenzoic acid show a
blue fluorescence. Although the meta isomer shows the same phe-
nomenon, it is quenched by alkali addition in contrast to the
behavior of the ortho isomer. The third isomer, viz. p-aminobenzoic
acid displays no fluorescence [ 1 8 7 ] .
Aminobenzoic acids form anils with pyridine-2-aldehyde. These
anils produce violets chelates with ferric ions. However, only the
color reaction of m-aminobenzoic acid is unimpaired by alcohol
[188].
p-Amino benzoic acid is oxidized with potassium bromate solution
to give an intense violet-colored product which changes to yellow.
The ortho and meta isomers give a red and yellow color, respectively,
under the same conditions [ 1 8 7 ] .
(C) N I T R O A N I L I N E S
The detection of m-nitroaniline in the presence of the other

isomers is based on the fact that only this compound is decolorized
in dilute acid solution [ 1 8 9 ] . When nitroanilines are diazotized and
coupled with a -naph thy lamine or aniline, acid—base indicators are
formed, which are the basis for the identification of p-nitroaniline in
the presence of the other isomers and o-nitroaniline in the presence
of the meta isomer.
In another test [ 1 9 0 ] , m-nitroaniline can be selectively identified
by its nitration leading to 2,3- or 4,3-dinitroacetanilide. These com-
pounds behave similarly to o-dinitrobenzene with reducing agents
and yields intensely colored alkali salts of the tautomeric nitrohy-
droxyl aminobenzene derivatives of the type
The para isomer can be detected in the presence of the other

isomers by its diazotization. The resulting diazonium ion is a sensi-
tive spot test reagent for ammonia [ 1 9 1 ] .
HN02 NH3
0 2N - / 0 / - N H 2
0 2N - / 0 / - N = N
N-ONH4
red
38
(D) DINITROANILINES
For the detection of 2,4- and 3,5-dinitroanilines [ 1 9 2 ] , use is

made of their diazotization and coupling with l-naphthol-4-sulfonic
acid. The azo compounds obtained are acid—base indicators which
have different colors for the two isomers.
SO3H SO3H
yellow red
(E) N I T R O B E N Z A L D E H Y D E S
The ortho derivative is identified selectively in the presence of the

other isomers by the indigo synthesis [ 1 9 3 ] .
C H
O C H =2 C H
KOH ^ > y - Η,Ο condensation
f\ o^ "rΝ 0 TC ^H
( 3)2
R
CO CO
\ ^ N 0
2 2
indigo
In another test, the ortho derivative reacts with alkaline p-nitro-

phenylhydrazine to give a violet product. The meta compound under
similar conditions forms a red product [ 1 9 4 ] .
p-Nitrobenzaldehyde is identified by its condensation with benzyl-
amine to produce a colorless Schiff's base. In caustic alkali, the latter
turns into the intensively red nitronium salt [ 1 9 5 ] .
N
°2 ^(0^>-CH = N-CH 2--^0) - KOON=<^)=CH-N=CH-<^^>
colorless red

It is possible to identify the para derivative also by its blue p-nitro-
phenylhydrazine [ 1 9 4 ] .
(F) DIHYDROXYBENZENES
Pyrocatechol yields a blue color with phenyl methylpyrazolone

and ammonia. This reaction is selective for this isomer [ 1 9 6 ] .
Resorcinol treated with solid pyrocatechol and dilute sodium
hydroxide forms a blue-green color which turns gradually to intense
violet-red. The product is presumably a molecular compound [ 1 9 7 ] .
Hydroquinone is identified through its reaction with o-phthalalde-
hyde to form a blue-violet product [ 1 9 7 ] .
(G) T R I H Y D R O X Y B E N Z E N E S
Pyrogallol is identified by its reaction with a caustic alkaline solu-

tion of phloroglucinol to give a characteristic blue-green coloration
[ 1 9 8 ] . Hydroxyhydroquinone treated with p-phthalaldehyde in con-
centrated sulfuric acid forms a characteristic violet color which is
used for selective identification [ 1 9 8 ] .
Phloroglucinol in concentrated hydrochloric acid reacts with sali-
cylaldehyde to yield an orange-red condensation product [ 1 6 1 ] .
(H) NAPHTHOLS
α-Naphthol is detected by its reaction with potassium p-nitro-

phenylantidiazotate to give an azo blue dyestuff [ 1 9 9 ] .
j3-Naphthol condenses with j3-nitroso-a-naphthol (in its keto form)

and the product is oxidized by nitric acid to an intensely colored red-
violet compound [ 2 0 0 ] .
Another test to differentiate between the two naphthols is based
40
on their coupling with nitrophenylhydrazine to form acid indicators.
Although α-naphthol is a stronger acid than the β-isomer, it forms a
weaker acid indicator than the latter. The indicator obtained in
alkaline medium from the α -isomer is orange-red and that from the
]3-isomer is violet [ 2 0 1 ] .
(I) N A P H T H Y L A M I N E S
α-Naphthylamine, through its condensation reaction with nitro-

antipyrin, forms a violet azo dye. This reaction serves for the selec-
tive detection of α-naphthylamine [ 2 0 2 ] .
CH3
I
+ H 20
N=N-U 1=
The /^-isomer reacts with pyridine-2-aldehyde and ferrous sulfate

to give an intense violet chelate.
^CH
t II
F e - * N C 1 H0 7( / ? )
Although the α-isomer condenses to give the corresponding

Schiff's base, it does not form the iron chelate for steric reasons. This
reaction is thus selective for the detection of j3-naphthylamine [ 2 0 3 ] .
(J) A M I N O P H E N O L S
The ortho derivative is selectively detected [204] by the synthesis

of the specific reagent for calcium, namely glyoxalbishydroxy acid.
•d
m-Aminophenol when heated with glycerol and sulfuric acid forms

7-hydroxyquinoline. All the other aminophenols participate in the
Skraup synthesis but only the 7-hydroxyquinolate shows fluore-
scence [ 2 0 5 ] .

The para isomer is selectively detected by its oxidation to p-qui-
none-4-chloroimine which is a well known reagent for phenols with
which it forms a blue indophenol dye [ 2 0 6 ] .
[ox] / = \ phenol / = \ Ν /T^\
OH-/OVNH 2 — — O = / V=NCI • 0 = ^ / = " Λ Y-ONH4
blue
(K) NITROPHENOLS
The ortho and para derivatives are distinguished on the basis of

their difference in vapor pressure. The ortho isomer is detected by its
sublimation when heated to 120° C followed by identification in the
vapor phase of its yellow alkali salt [ 2 0 7 ] .
Due to its relatively strong acidity, only p-nitrophenol [207]
reacts instantaneously with fused hydrated sodium thiosulfate at
120° C. The unstable thiosulfuric acid formed decomposes to preci-
pitate yellow sulfur.
m-Nitrophenol [205] is detected by its reduction to m-aminophe-
nol which subsequently reacts with glycerol to produce the fluores-
cent 7-hydroxyquinoline.
(L) PHENYLENEDIAMINES
o-Phenylenediamine is detected by the brown-red inner complex

cobalt salt of the Schiff's base with salicylaldehyde. The reaction is
selective for the ortho derivative [ 2 0 8 ] .
HC = N N = CH
Co
y x
o o-<0)
The meta isomer is oxidized selectively with sodium nitrite (at pH

5) to give a red product [ 2 0 9 ] .
p-Phenylenediamine is detected selectively by its oxidation in the
presence of aniline to form phenylene blue [ 2 1 0 ] .
42
6. Selected test procedures
(1) Alcohols
In a micro test tube, mix

(a) 1 drop of test solution
(b) 4 drops of a benzene solution of vanadium oxinate (1 mg vana-
dium treated with 1 ml of a 2.5% solution of 8-hydroxyquinoline in
6% acetic acid, and shaken with 30 ml benzene). This reagent solu-
tion keeps for about one day. The mixture is heated in a water bath
at 60° C. A red color appearing after 6—8 min indicates the presence
of alcohols.
Identification limit range: 5—20 μg alcohol.
(2) Phenols
In a micro crucible
(a) 1 drop of test solution is evaporated and treated with
(b) 1 drop of a freshly prepared 1% solution of sodium nitrite in
concentrated sulfuric acid.
After a few minutes, the mixture is diluted with a drop of water and
made alkaline with 4 Ν sodium hydroxide.
The presence of phenols is indicated by the appearance of an
intense blue-red-green color (in accordance with the particular phenol).
Identification limit range: 1—10 μg phenol.
(3) Aliphatic poly hydroxides
In a micro crucible
(a) 1 drop of the test solution is mixed with
(b) 1 drop of 5% potassium periodate and
(c) 1 drop of 10% sulfuric acid and allowed to stand for five
minutes.
(d) Excess periodic acid is reduced with saturated sulfurous acid,
and treated with
(e) 1 drop of fuchsin—sulfurous acid ( S 0 2 is passed through 0.1%
solution of fuchsin until the color is discharged).
In the presence of polyhydroxides, a red to blue color appears.
Identification limit range: 2.5—100 μg polyhydroxide.
Citric acid, inositol, pentaerythritol, pentaacetylglucose, acetyl-
cellulose fail to give the reaction.

(4) Aldehydes
In a micro test tube

(a) 1 drop of test solution is treated with
(b) 5 drops of reagent solution (a few eg of purest indole dissolved
in pure concentrated hydrochloric acid. This reagent solution should
not be older than 15 min! !).
The appearance of a pink to orange color indicates the presence of
aldehydes.
Identification limit range: 0.0001—20 μg aldehyde.
(5) Aliphatic aldehydes and ketones
In the depression of a spot plate

(a) 1 drop of the solution is mixed with
(b) 2 drops of a 0.01 M aqueous solution of 2,3-bis(hydroxyl-
amino)-2,3 dimethylbutane sulfate.
After 5 min
(c) 2 drops of a 0.05 M aqueous solution of sodium periodate is
added. A pink color appears within 2 min in the presence of aliphatic
aldehyde or ketone.
Identification limit range: 0.2—250 μg aldehydes; 80—2000 μg
ketone.
(6) Aromatic aldehydes

(b) several mg of solid AT.iV-dimethyl-p-phenylenediamine and
warmed in a water bath.
The appearance of a red coloration indicates the presence of aroma-
tic aldehydes.
Identification limit range: 0.05—100 μg aromatic aldehyde.
(7) Ketones
In a micro crucible
(a) 1 drop of the aqueous or alcoholic test solution is mixed with
(b) 1 drop of 5% sodium nitroprusside solution and
(c) 1 drop of 30% sodium hydroxide solution.
44
Add, after a short time
(d) 1—2 drops glacial acetic acid.
A red or blue color indicates the presence of a ketone.
Identification limit range: 1—15 Mg ketone.
(8) Carboxylic acids
In a micro crucible
(a) 1 drop of the test solution is evaporated and treated with
(b) 2 drops of thionyl chloride evaporated almost to dryness.
(c) 2 Drops of saturated alcoholic solution of hydroxylamine
hydrochloride are added and
(d) a few drops of alkali until neutralization as indicated by litmus
paper.
(e) Heat the crucible and acidify with a few drops of 0.5 Ν hydro-
chloric acid and add
(f) 1 drop of 1% aqueous ferric chloride solution.
In the presence of carboxylic acid, a dark violet color appears.
Identification limit range: 11—33 μg acid (sodium acetate 100 μg).
(9) Alkyl esters of carboxylic acids
In a depression of a spot plate

(a) 1 small piece of metallic sodium is pressed.
(b) 1 drop of the benzene solution of the ester is added and
(c) 1 drop of a 2.5% benzene solution of dinitrobenzene. The mix-
ture is stirred and after 1—2 min
(d) 1 drop of water is introduced.
In the presence of esters, a violet color appears.
Identification limit range: 5—10 μ% ester.
(10) Ethers
In a test tube
(a) 1 drop of test solution plunged into glycerol bath heated to
230° C.
(b) The mouth of the test tube is covered with a disc of filter
paper moistened with a drop of 5% copper ethylacetoacetate and a
drop of a 5% chloroform solution of tetrabase.
A blue color appears in the presence of ether.
Limit of identification: 20 Mg diethyl ether.

(11) Amines (primary, secondary, tertiary; aliphatic and aromatic)

(a) 1 drop of ethereal test solution is treated with
(b) 1 drop of 1% ethereal solution of 2,4-dinitrochlorobenzene.
After the evaporation of the ether, a yellow color indicates the
presence of amines.
Limit of identification range: 0.2—5 μg amine.
( 12) Primary and secondary amines (aliphatic and aromatic)
On a piece of filter paper

(a) 1 drop of a methanol—trichloroacetic acid solution of p-dime-
thylaminocinnamaldehyde is spotted with
(b) 1 drop of the ethereal solution of the sample, or the aqueous
solution of its salt buffered with sodium acetate.
The filter paper is kept in an oven at 100° C for about 3 min. Primary
amines result in blue, secondary amines in purple coloration.
Limit of identification range: 0.02—2.2 μg amine.
(13) Primary and secondary aliphatic amines
In a micro crucible
(a) 1 drop of the alcoholic test solution is mixed with
(b) a few drops of a 1 : 1 alcohol: carbon disulfide mixture. After
about 5 min
(c) a few drops of an iodine—azide solution (3 g N a N 3 in 100 ml
0.1 Ν iodine) is added.
The evolution of nitrogen gas indicates the presence of aliphatic
primary and secondary amines.
Limit of identification range: 1—250 ^g amine.
(14) Aliphatic secondary amines

.(a) 1 drop of the acid test solution is added to
(b) 1 drop 5% copper sulphate.
The mixture is made basic with ammonia and
(c) is shaken with 2 drops of a mixture of 1 : 3 v/v carbon disul-
fide and benzene.
46
The presence of aliphatic secondary amines is indicated by the
appearance of a brown benzene layer.
Limit of identification range: 0.2 —10 μg amine.
(15) Nitro compounds
In a micro conical tube

(a) 1 drop of the ethereal or benzene test solution is mixed with
(b) 1 drop of a 5% tetrabase or diphenylamine benzene solution.
The tube is dipped into a boiling water bath.
The presence of nitro compound is indicated by the appearance of
an orange-red melt.
Identification limit range: 0.1—50 μg nitro compound.
(16) Primary aliphatic nitro compounds
On a filter paper, spot

(a) 1 drop of a freshly prepared, saturated alcoholic solution of
fast blue salt Β followed by
(b) 1 drop of the alcoholic test solution and
(c) 1 drop of 0.5 Ν sodium hydroxide.
The appearance of an orange-red spot which turns red after a few
minutes indicates the presence of aliphatic primary nitro compound.
Identification limit range: 0.5 μ% nitro compound.
(17) Primary and secondary aliphatic nitro compounds
In a micro test tube add

(a) 1—2 drops of the aqueous or alcoholic test solution united
with
(b) 2 drops of 12% sodium hydroxide solution and
(c) 1 drop of 30% hydrogen peroxide.
The mixture is carefully boiled over a micro burner for 5—6 min
and after that
(d) 1 drop of 0.1% nickel sulfate solution is added and boiled for
another 2 min.
After cooling
(e) 2 drops of 1% sulfanilic acid solution, acidified with 1 : 1
hydrochloric acid and
(f) some drops of 1% 2-hydroxy-3-naphthoic acid in 2 Ν sodium
hydroxide is added.

A red color indicates the presence of aliphatic nitro compounds.
Identification limit range: 0.02—0.5 μg nitro compound.
(18) Nitriles

(a) 1 drop of test solution is mixed with
(b) a few mg of hydrated oxalic acid.
The tube is immersed into a glycerol bath preheated to 200°C. After
5 min heating, the tube is cooled and
(c) a few mg of thiobarbituric acid are added.
The mixture is heated again to 140—160°C. The presence of nitriles
is indicated by the appearance of an orange color.
Identification limit range: 2—20 μg nitrile.
(19) Thioketones and thiols
On a watch glass
(b) 1 drop of iodine—azide solution (3 g sodium azide dissolved in
100 ml 0.1 Ν iodine solution).
Evolution of bubbles of nitrogen signals the presence of thioketones
and thiols.
Identification limit range: 0.0003—0.25 μg thioketone or thiol.
(20) Sulfonic acids

(a) 1 drop of test solution is evaporated and mixed with
(b) several eg succinic acid or phthalic acid.
The test tube is placed in a glycerol bath heated to 200°C.
(c) The mouth of the test tube is covered with a piece of filter
paper moistened with iron(III) hexacyanoferrate(III) solution [0.08
g of anhydrous FeCl 3 and 0.1 g of K 3 Fe(CN) 6 dissolved in 100 ml
water]. Subsequently, the temperature of the bath is raised to
250°C.
The presence of sulfonic acid is indicated by the appearance of a
blue spot on the filter paper.
Identification limit range: 1—20 μg sulfonic acid.
48
(21) Acetone
(a) 1 drop of a 10% alcoholic solution of salicylaldehyde is mixed
with
(b) 1 drop of 40% sodium hydroxide solution and
(c) 1 drop of the test solution.
The mixture is kept for 2—3 min in a water bath at 70—80° C. In
the presence of acetone, a deep red color appears.
Limit of identification: 0.2 acetone.
(22) Acetic acid
(b) 1 drop of a 5% solution of lanthanum nitrate and
(c) 1 drop of 1 Ν ammonia.
The development within a few minutes of a blue to blue-brown ring
indicates the presence of acetic acid.
Limit of identification: 50 μg acetic acid.
(23) Acetylene
In each of two small porcelain crucibles
(a) 1 drop of ammoniacal silver chromate (freshly precipitated
A g 2 C r 0 4 is dissolved in 1 : 5 ammonia solution, shaken and filtered.
The clear yellow solution is stored in a dark bottle) and
(b) 1 drop of 6 Ν acetic acid.
(c) Add 1 drop of the test solution to one crucible and 1 drop of
water to the other.
The mixtures are stirred for 1—10 min and treated with the same
number of drops of 1 : 10 H N 0 3 solution until the A g 2 C r 0 4 precipi-
tate in the blank disappears. In the presence of acetylene, a residue
of red-brown A g 2 C r 0 4 remains.
Limit of identification: 1 μξ acetylene.
(24) Barbituric acid

(b) 1 drop of 2 Ν acetic acid and
(c) 1 drop of saturated sodium nitrite solution.
A red-violet color appears in the presence of barbituric acid.
Limit of identification: 10 μ% barbituric acid.
(25) Carbon disulfide

(a) 1 drop of the test solution is treated with
(b) 1—2 drops of reagent solution (9 ml 0.2% copper sulfate solu-
tion treated with 1 ml cone, ammonia and 0.5 g piperidine or
dimethylamine chloride) and
(c) shaken with 2 drops of benzene.
A yellow-brown color in the benzene layer indicates the presence of
carbon disulfide.
Identification limit: 3 μg carbon disulfide.
(26) Carbon tetrachloride

(b) several eg quartz dust.
The tube is immersed in a glycerol bath preheated to 150° C. The
mouth of the tube is covered with a disc of Congo Red paper
moistened with 5% hydrogen peroxide. A blue stain indicates the
presence of carbon tetrachloride.
Identification limit: 5 mg carbon tetrachloride.
(27) Citric acid

(b) 1 drop of 0.01 Ν K M n 0 4 and
(c) 1 drop of saturated of bromine water.
The tube is warmed slightly and after cooling
(d) some solid sulfosalicylic acid is added.
In the presence of citric acid, a white precipitate forms.
Limit of identification: 6 μg citric acid.
(28) Cysteine

(a) 1 drop of test solution is treated with
(b) 1 drop ammonia (density 0.910) and
(c) 1 drop 0.2% sodium nitrosopentacyanoferrate(III) and
50
(d) 1 drop of 2% sodium pyruvate.
In the presence of cysteine, complete decolorization occurs within a
few minutes.
Identification limit: 0.5 cysteine.
(29) Ethanol

(b) 1 drop of 1 Ν potassium permanganate in 1 : 1 sulfuric acid.
The mixture is shaken, and the mouth of the tube is covered with
(c) a paper disc moistened with a freshly prepared mixture of
equal volumes of a 20% aqueous solution of morpholine and 5%
aqueous solution of sodium nitroprusside.
Identification limit: 3 μg ethanol.
(30) Formaldehyde
On a glass fiber filter paper

(a) to 1 drop of a 0.1% solution J-acid (6 amino-1-naphthoic-sul-
fonic acid in cone, sulfuric acid) add
(b) 1 drop of the aqueous test solution.
After 5—10 sec, a yellow fluorescence under UV indicates the pre-
sence of formaldehyde in contrast to the light blue fluorescence of
the blank.
(c) 1 Drop of water confirms the presence of formaldehyde by
forming a blue color.
Identification limit: 0.01 μg formaldehyde.
(31) Formic acid

(a) 1 drop of the aqueous test solution is treated with
(b) 10 drops of a 5% solution of iV-methylquinaldinium toluene-p-
sulfonate in dimethylsulfoxide, followed by
(c) 1 drop of pyridine and
(d) 1 drop of acetic anhydride.
The tube is warmed in boiling water for 1 min. In the presence of
formic acid, a blue to green color results.
Identification limit: 0.04 μg formic acid.

(32) Glycerol

(a) 2 drops of a 2% alcoholic solution of o-aminophenol are eva-
porated at 110°C.
(b) 1 Drop of the test solution is added followed by
(c) 4 drops of 1% arsenic acid in cone, sulfuric acid. The tube is
kept at 140°C for about 15 min, subsequently cooled, and
(d) 5 drops of cone, sodium hydroxide
(e) 1 drop of 2 Ν magnesium sulfate and
(f ) 3 drops of cone, ammonia are added.
The tube is agitated, and cooled with cold water. The presence of
glycerol is indicated by the appearance of a bluish-green fluorescence
in UV light.
Limit of identification: 0.5 μg glycerol.
(33) Malonic acid
(b) several drops of a saturated methanolic solution of urea. After
evaporation of the alcohol, the tube is heated for several minutes in a
glycerol bath at 120° C.
(c) 1 Drop of a 1% solution of pyridylpyridinium dichloride in
dimethylformamide is added.
The mixture is heated at 120°C for several minutes. In the presence
of malonic acid, a reddish-blue color develops on cooling, which
fluoresces red under UV light.
Identification limit: 50 μg malonic acid.
(34) Naphthalene
In gas absorption apparatus (see ref. 20, p. 53, Fig. 23)

(a) 1 drop of the ethereal test solution is placed in the bulb and
the solvent is evaporated.
(b) 1 Drop of a saturated solution of chloranil in benzene is placed
on the knob of the stopper and the solvent is evaporated.
The apparatus is closed, placed in water at around 40° C and the tem-
perature raised to 50—60° C. The knob turns brick-red in the pres-
ence of naphthalene.
Identification limit: 25 μg naphthalene.
52
(35) Oxalic acid

(a) 1 drop of the sample is evaporated to dryness and melted with
(b) a little diphenylamine over a free flame. After cooling add
(c) 1 drop of alcohol.
The appearance of a blue coloration indicates the presence of oxalic
acid.
Limit of identification: 5 μg oxalic acid.
(36) Piperidine

(a) 1 drop of acidic test solution is mixed with
(b) several eg of sodium carbonate.
The tube is immersed in a water bath heated to 90° C and the mouth
covered with a disc of filter paper moistened with
(c) a 2.5% aqueous solution of sodium l,2-naphthoquinone-4-
sulfonate. The presence of piperidine is indicated by the appearance
of a red spot on the yellow paper.
Limit of identification: 20 μg piperidine.
(37) Pyridine and derivatives
On Whatman filter paper No. 1

(a) 1 drop of test solution is sprayed with
(b) 1 drop of a 0.2% solution of trisodium pentacyanoaminofer
rate in pH 6.5 buffer solution (3 volumes of 0.1 M citric acid and
7 volumes of 0.2 M N a 2 H P 0 4 ) .
In the presence of pyridines, a yellow-orange coloration appears
within 5 min.
Identification limit range: 10—50 μg pyridine.
(38) Quinones

(a) 1 drop of the test solution is shaken with
(b) 1 drop of a saturated aqueous solution of rhodanine and
(c) 1 drop of ammonia.
In the presence of quinones, a green color appears gradually.

Limit of identification range: 0.5 μζ quinone.
(39) Salicylaldehyde
In a capillary tube
(a) 1 micro drop of the anhydrous test solution is introduced. The
tube is dipped into
(b) 1 drop 70% HC10 4.
In the presence of salicylaldehyde, a yellow coloration appears which
on standing for ca. 30 sec turns intensely red (in the meniscus).
Limit of identification: 2 μg salicylaldehyde.
(40) Urea

(a) 1 drop of the neutral or alkaline test solution is treated with
(b) several mg of urease and, after 2—5 min.
(c) 1 drop of Nessler solution.
The appearance of a brownish precipitate indicates the presence of
urea (in the absence of ammonium salts).
Limit of identification: 1 μg urea.
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9 1 G. A k s n e s , A c t a C h e m . S c a n d . , 1 1 ( 1 9 5 7 ) 7 1 0 .
9 2 L. L é g r â d i , M i c r o c h e m . J . , 1 6 ( 1 9 7 1 ) 1 .
9 3 L. L é g r â d i , M i k r o c h i m . A c t a , ( 1 9 7 0 ) 4 6 3 .
9 4 W. W e n d e l i n a n d F . K n o t z , M o n a t s h . C h e m . , 1 0 3 ( 1 9 7 2 ) 1 6 3 2 .
9 5 F . F e i g l a n d CI. C o s t a N e t o , s e e F . F e i g l a n d V . A n g e r , S p o t T e s t s i n
Organic Analysis, Elsevier, A m s t e r d a m , 7 t h edn., 1 9 6 6 , p. 2 1 4 .
9 6 F. Feigl, J.R. Amaral and D . Haguenauer-Castro, Mikrochim. A c t a , ( 1 9 6 0 )
821.
97 F. Feigl a n d E. Silva, A n a l y s t , 8 2 ( 1 9 5 7 ) 5 8 2 .
98 F. Feigl and E. Jungreis, Anal. C h e m . , 3 1 ( 1 9 5 9 ) 2 0 9 9 , 2 1 0 1 .
99 F. Feigl a n d J.R. Amaral, s e e F. Feigl and V. Anger, S p o t T e s t s in Organic
100 H.E. Malone, Talanta, 2 2 ( 1 9 7 5 ) 9 7 .
101 F . Feigl a n d J.R. A m a r a l , s e e F. Feigl a n d V. A n g e r , S p o t T e s t s in Organic
Analysis, Elsevier, A m s t e r d a m , 7th e d n . , 1 9 6 6 , p. 2 4 3 .
102 S. S a k a i K. S u z u k i , H . M o r i a n d M. F u j i n o , B u n s e k i K a g a k u , 9 ( 1 9 6 0 ) 8 6 2 .
103 F. K n o t z , Sci. Pharm., 3 8 ( 1 9 7 0 ) 2 6 .
104 F . F e i g l a n d G. F r a n k , s e e F . F e i g l a n d V . A n g e r , S p o t T e s t s i n O r g a n i c
Analysis, Elsevier, A m s t e r d a m , 7th edn., 1 9 6 6 , p. 2 4 4 .
105 G.Ya. Dubur and G.Ya. Vanag, Anal. Abstr. 17 ( 1 9 6 9 ) N o . 9 0 8 .
106 I.I. L a p k i n a n d Y u . S . A n d r e i c h i k o v , A n a l . A b s t r . ( 1 9 6 8 ) N o . 3 3 8 2 .
107 M. B r o i l a n d G. F i s c h e r , M i k r o c h i m . A c t a ( 1 9 6 2 ) 2 5 0 .
108 F. Feigl a n d L. Hainberger, see F. Feigl a n d V. A n g e r , S p o t T e s t s in Organic
Analysis, Elsevier, A m s t e r d a m , 7th e d n . , 1 9 6 6 , p. 2 5 0 .
109 F. Feigl, V. A n g e r a n d R. Zappert, see F. Feigl and V. Anger, S p o t Tests in
Organic Analysis, Elsevier, A m s t e r d a m , 7th edn., 1 9 6 6 , p. 2 4 5 .
110 S. O k h u m a a n d I. S a k a i , B u n s e k i K a g a k u , 2 4 ( 1 9 7 5 ) 3 8 5 .
111 I.M. K o r e n m a n , N . V . K u r i n a a n d T . Y a . P e s h c h e r k o v a , Tr. K h i m . K h i m .
Tekhnol., 2 (1969) 136.
112 K. W r a b e t z , Z. A n a l . C h e m . , 2 4 6 ( 1 9 6 9 ) 2 5 8 .
113 L. Légrâdi, M i k r o c h i m . A c t a , ( 1 9 6 9 ) 1 9 8 .
115 A . F i s c h e r , A . V i n c z e , S. F l a v i a n a n d C. L a c h m a n , P r o c e e d i n g s o f t h e 4 4 t h
A n n u a l M e e t i n g o f t h e Israel C h e m i c a l S o c i e t y , J u n e 1 9 7 7 , S e c t . M N , p a p e r
n o . 5.
116 A.B. Groth and M.E. Dahlen, Acta Chem. Scand., 21 ( 1 9 6 7 ) 2 9 1 .
117 F . F e i g l , CI. C o s t a N e t o a n d C. S t a r k - M a y e r , s e e F . F e i g l a n d V . A n g e r ,
Tests in Organic Analysis, Elsevier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p. 2 9 5 .
118 F . F e i g l a n d D . G o l d s t e i n , Z. A n a l . C h e m . , 1 5 8 ( 1 9 5 7 ) 4 2 7 .
119 T. Meisel and L. E r d e y , M i k r o c h i m . A c t a , ( 1 9 6 6 ) 1 1 4 8 .
57
1 2 0 L. Légrâdi, M i k r o c h i m . A c t a , ( 1 9 6 8 ) 7 3 9 .
1 2 1 A . Tsuji, A. N a k a m u r a a n d A . N a k a m u r a , M i k r o c h i m . A c t a , ( 1 9 6 8 ) 8 5 1 .
1 2 3 J.P. Sharma and R . D . Tewari, M i k r o c h i m . A c t a , ( 1 9 7 4 ) 3 2 3 .
1 2 4 F. Feigl and J.R. Amaral, see F. Feigl and V. Anger, S p o t Tests in Organic
1 2 5 F. Feigl, V. Gentil and E. Jungreis, M i k r o c h i m . A c t a , ( 1 9 5 9 ) 4 7 .
1 2 6 S.Z. Q u r e s h i a n d M . S . R a t h i , M i k r o c h i m . A c t a , ( 1 9 7 7 ) 1 1 .
1 2 7 F. Feigl, see F. Feigl and V. Anger, S p o t Tests in Organic Analysis, Elsevier,
A m s t e r d a m , 7th edn., 1 9 6 6 , p. 2 1 9 .
1 2 8 F. Feigl and D. Goldstein, see F. Feigl and V. Anger, S p o t Tests in Organic
Analysis, Elsevier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p . 2 2 2 .
1 2 9 F. Feigl a n d E. Jungreis, see F. Feigl a n d V. Anger, S p o t Tests in Organic
1 3 0 D . R . G r a s s e t t i a n d J . F . M u r r a y , Jr., J. C h r o m a t o g r . , 4 1 ( 1 9 6 9 ) 1 2 1 .
1 3 1 Κ. H o f f m a n , N a t u r w i s s e n s c h a f t e n , 5 2 ( 1 9 6 5 ) 4 2 8 .
1 3 2 F. Feigl, D. Goldstein and E.K. Liebergott, Anal. Chim. A c t a , 4 7 ( 1 9 6 9 )
553.
1 3 3 F. Feigl, D. Haguenauer-Castro and E. Jungreis, Talanta, 1 ( 1 9 5 8 ) 8 0 .
1 3 4 L. S u c h o m e l o v a , V . H o r a k a n d J. Z y k a , M i k r o c h e m . J., 9 ( 1 9 6 5 ) 1 9 6 .
1 3 5 V . A n g e r a n d S. Ofri, Z . A n a l . C h e m . , 2 0 6 ( 1 9 6 4 ) 1 8 6 .
1 3 7 D. Krueger and E. Tschich, Mikrochemie, 8 ( 1 9 3 0 ) 2 1 8 .
1 3 8 B.W. R o c k e t t a n d M. K i r b y , M i k r o c h i m . A c t a , ( 1 9 6 8 ) 1 2 7 7 .
1 3 9 P. L u i s , C . N . C a r d u c c i a n d A . S a , M i k r o c h i m . A c t a , ( 1 9 6 8 ) 5 6 .
1 4 0 F. Feigl and V. Gentil, see F. Feigl and V. Anger, S p o t Tests in Organic
1 4 1 F. Feigl a n d E. Jungreis, s e e F . Feigl a n d V. A n g e r , S p o t T e s t s in Organic
1 4 2 F. Feigl and V. Gentil, see F . Feigl and V. Anger, S p o t T e s t s in Organic
1 4 3 V . A n g e r a n d S. Ofri, Z. A n a l . C h e m . , 2 0 6 ( 1 9 6 4 ) 1 8 7 .
1 4 4 F. Feigl and D. G o l d s t e i n , see F. Feigl and V. Anger, S p o t Tests in Organic
1 4 5 F. Feigl a n d V. Gentil, see F. Feigl and V. Anger, S p o t Tests in Organic
146 F. Feigl H.T. C a r d o s o , M. Steinhauser, J.E.R. Marins, A . B o n d i and. D .
G o l d s t e i n , see F . Feigl a n d V . A n g e r , S p o t T e s t s in Organic A n a l y s i s ,
Elsevier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p. 4 7 3 .
147 F. Feigl a n d E. Jungreis, see F. Feigl and V. Anger, S p o t Tests in Organic
1 4 8 M.J. d e F a u b e r t M a u n d e r , A n a l y s t , 1 0 0 ( 1 9 7 5 ) 8 7 8 .
1 4 9 F . F e i g l a n d C. C o s t a N e t o , s e e F . F e i g l a n d V . A n g e r , S p o t T e s t s i n
Organic Analysis, Elsevier, A m s t e r d a m , 7 t h edn., 1 9 6 6 , p . 4 9 0 .
1 5 0 F. Feigl and D . G o l d s t e i n , see F. Feigl and V. Anger, S p o t Tests in Organic
1 5 1 F . Feigl, D . G o l d s t e i n and D . Haguenauer-Castro, R e c . Trav. C h i m . , 2 9
(1960) 531.
58
152 E. J u n g r e i s , s e e F . F e i g l a n d V . A n g e r , S p o t T e s t s i n O r g a n i c A n a l y s i s , E l s e -
vier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p . 4 5 6 .
153 V . Gentil, s e e F . Feigl a n d V. A n g e r , S p o t T e s t s in Organic A n a l y s i s , Else-
vier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p . 4 7 1 .
154 E. Konrad, Parfuem. K o s m e t . , 4 6 ( 1 9 6 5 ) 6 4 .
155 M. Q u r e s h i a n d S . Z . Q u r e s h i , A n a l . C h e m . , 3 8 ( 1 9 6 6 ) 1 9 5 6 .
156 F . F e i g l a n d C. S t a r k , C h e m i s t A n a l y s t , 4 5 ( 1 9 5 6 ) 3 9 .
157 E . S a w i c k i , T.W. S t a n l e y a n d J. Pfaff, C h e m i s t A n a l y s t , 5 1 ( 1 9 6 2 ) 9 .
158 L. L é g r â d i , Ε . P u n g o r a n d Ô. S z a b a d k a , A c t a C h i m . A c a d . S c i . H u n g . , 4 2
(1964) 89.
159 E . S a w i c k i , T . W . S t a n l e y , J. P f a f f a n d J. F e r g u s o n , A n a l . C h e m . , ( 1 9 6 2 ) 6 2 .
160 E . L a n g a n d H. L a n g , Z . A n a l . C h e m . , 2 6 0 ( 1 9 7 2 ) 8.
161 V . A n g e r a n d S. Ofri, Z . A n a l . C h e m . , 2 0 3 ( 1 9 6 4 ) 4 2 8 .
162 F. Feigl and W.E. Mannheimer, see F. Feigl and V . Anger, S p o t Tests in
163 E . S a w i c k i a n d W. E b e r t , T a l a n t a , 5 ( 1 9 6 0 ) 6 3 .
164 F . F e i g l a n d S. Y a r i v , T a l a n t a , 1 2 ( 1 9 6 5 ) 1 5 9 .
165 V . A n g e r a n d S. Ofri, T a l a n t a , 1 0 ( 1 9 6 3 ) 1 3 0 2 .
166 E. Eegriwe, Mikrochim. Acta, 2 ( 1 9 3 7 ) 3 2 9 .
167 E. E e g r i w e , Z. A n a l . C h e m . , 1 1 0 ( 1 9 3 7 ) 2 2 .
168 F . F e i g l , V . G e n t i l a n d C. S t a r k - M a y e r , M i k r o c h i m . A c t a , ( 1 9 5 7 ) 3 5 0 .
169 F. Feigl and D. Haguenauer-Castro, see F. Feigl and V. Anger, S p o t Tests
in Organic Analysis, Elsevier, A m s t e r d a m , 7 t h edn., 1 9 6 6 , p. 5 3 5 .
170 F. Feigl and E. Jungreis, see F . Feigl a n d V. A n g e r , S p o t T e s t s in Organic
171 F . F e i g l a n d O. F r e h d e n , M i k r o c h e m i e , 1 8 ( 1 9 3 5 ) 2 7 2 .
172 V . A n g e r a n d S. W a n g , M i k r o c h i m . A c t a , ( 1 9 3 8 ) 2 4 .
173 F. Feigl, Chemist Analyst, 5 0 ( 1 9 6 1 ) 1 5 .
174 F. Feigl and D. Goldstein, see F. Feigl and V. Anger, S p o t Tests in Organic
176 T.A. Larue, Anal. Chim. A c t a , 4 0 ( 1 9 6 8 ) 4 3 7 .
177 V . A n g e r a n d S. Ofri, M i k r o c h i m . A c t a , ( 1 9 6 3 ) 9 1 5 .
178 L. L é g r â d i , A n a l y s t ( L o n d o n ) , 9 5 ( 1 9 7 0 ) 5 9 0 .
179 J. P a u l , M i c r o c h e m . J., 1 3 ( 1 9 6 8 ) 5 9 2 .
180 F. Feigl and W.A. Mannheimer, see F. Feigl and V. Anger, S p o t Tests in
181 E. Eegriwe, Z. Anal. C h e m . , 8 9 ( 1 9 3 2 ) 1 2 1 .
182 F. Feigl and D. Goldstein, see F. Feigl and V. Anger, S p o t Tests in Organic
183 V. Anger, Oesterr. C h e m . Ztg., 6 2 ( 1 9 6 1 ) 3 5 4 .
184 G.B. G i b b s a n d P.L. Kirk, M i k r o c h e m i e , 1 6 ( 1 9 3 4 ) 2 5 .
185 S . S . M . H a s s a n , M i c r o c h e m . J., 1 8 ( 1 9 7 3 ) 2 9 4 .
187 F. Feigl a n d E. Jungreis, Z. A n a l . C h e m . , 1 9 8 ( 1 9 6 3 ) 4 1 9 .
188 F . F e i g l a n d L. B e n - D o r , T a l a n t a , 1 0 ( 1 9 6 3 ) 1 1 1 1 .
189 L. Légrâdi, Ζ. A n a l . C h e m . , 2 1 9 ( 1 9 6 6 ) 1 7 7 .
190 F . F e i g l a n d V . A n g e r , Z. A n a l . C h e m . , 1 8 3 ( 1 9 6 1 ) 1 3 .
59
191 Ε . J u n g r e i s , s e e F . F e i g l a n d V . A n g e r , S p o t T e s t s in O r g a n i c A n a l y s i s ,
Elsevier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p. 5 6 3 .
192 L. Légrâdi, Magy. Kern. F o l y . , 7 2 ( 1 9 6 6 ) 2 6 .
193 F. Feigl a n d V. A n g e r , Z. A n a l . C h e m . , 1 8 1 ( 1 9 6 1 ) 1 6 9 .
194 L. Légrâdi, Magy. Kern. F o l y . , 7 3 ( 1 9 6 7 ) 3 8 7 .
195 F. Feigl and V. Anger, Anal. Chim. Acta, 2 4 ( 1 9 6 1 ) 4 9 4 .
196 V. A n g e r a n d S. Ofri, M i k r o c h i m . A c t a , ( 1 9 6 3 ) 9 1 6 .
197 F . E e g r i w e , Z. A n a l . C h e m . , 1 2 5 ( 1 9 4 3 ) 2 4 1 .
198 E . E e g r i w e , Z. A n a l . C h e m . , 1 2 6 ( 1 9 4 3 ) 1 3 4 .
199 F . Feigl and V. A n g e r , Z. Anal. C h e m . , 1 9 1 ( 1 9 6 3 ) 2 7 4 .
200 V. Anger, see F. Feigl and V. Anger, S p o t Tests in Organic Analysis, Else-
vier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p. 4 2 1 .
201 L. L é g r â d i , M i k r o c h i m . A c t a , ( 1 9 6 7 ) 1 8 8 .
202 F . F e i g l , CI. C o s t a - N e t o a n d E. S i l v a , A n a l . C h e m . , 2 7 ( 1 9 5 5 ) 1 3 1 9 .
203 F . F e i g l , E . J u n g r e i s a n d S. Y a r i v , Z . A n a l . C h e m . , 2 0 0 ( 1 9 6 4 ) 3 8 .
204 F . F e i g l a n d D . G o l d s t e i n , Z. A n a l . C h e m . , 1 6 3 ( 1 9 5 8 ) 3 0 .
205 E. Jungreis and V. Lipetz, M i k r o c h i m . A c t a , ( 1 9 6 3 ) 8 8 6 .
206 E . J u n g r e i s , s e e F . F e i g l a n d V . A n g e r , S p o t T e s t s i n O r g a n i c A n a l y s i s , Else-
vier, A m s t e r d a m , 7 t h e d n . , 1 9 6 6 , p. 5 1 7 .
207 F. Feigl and D. Haguenauer-Castro, Chemist Analyst, 4 9 ( 1 9 6 0 ) 4 3 .
208 S. Y a r i v , Isr. J. C h e m . , 2 ( 1 9 6 4 ) 2 9 .
209 A . H i r s c h , S. F i s c h m a n , M. G o l d b e r g , M. O t t e n s o s e r a n d M. S c h a c h n o w ,
C h e m i s t A n a l y s t , 5 0 ( 1 9 6 1 ) 7.
210 O. H e i n , I n d . E n g . C h e m . A n a l . E d . , 7 ( 1 9 3 5 ) 1 4 6 .
211 P.W. W e s t , i n C . L . W i l s o n a n d D . W . W i l s o n ( E d s ) , C o m p r e h e n s i v e A n a l y t i c a l
Chemistry, Vol. IA, Elsevier, A m s t e r d a m , 1 9 5 9 , p. 3 8 2 .
60
Chapter 2
The history of analytical chemistry

F. S Z A B A D V Â R Y and A. R O B I N S O N
1. Analytical chemistry before 1700
(A) ANCIENT SCIENCE
Science can be said to have been forn 5000—6000 years ago. It

came about because of man's need to understand and classify natural
phenomena so that he might use this knowledge in agriculture, ship-
building, architecture, etc. This link between science and technology,
the one aiding the development of the other, has always been close,
although never so close as at present.
The Greeks, our best source of scientific knowledge in ancient
times, put their emphasis mainly on philosophical science and ob-
tained their views not by experiment, but by speculation. Rather
N
than analysing the natural sciences, they examined nature as a whole
and studied its pattern. In this respect, they were very advanced.
Before the advent of Greek civilisation, Sumerians, Egyptians,
Babylonians, Phoenicians, and Jews, living on the shores of the
Mediterranean had a considerable knowledge of mathematics and
physics as can be seen from their architectural achievements. Recent
studies have shown that numerous ideas, hitherto thought to be of
Greek origin, were known at a much earlier date. For example,
Aristotle's theory of the five elements, earth, water, fire, air, and
ether can be found in one of the earliest Hindu works. The historian
Diodorus of Sicily writes that
"Orpheus, Musaios, Homer, Lykurgos, Solon, Plato, Pythagorus,
Eudoxus and Democritus of Abdera travelled to Egypt, and surely it
was here that they learned much of that which was to make them
famous later" [ 1 ] .

In these oriental countries, however, scientific knowledge was in
the hands of powerful priests who kept their knowledge a closely
guarded secret. This contrasted with the democratic Greek states
where freedom of discussion allowed Greek philosophy to develop.
Its influence can be felt even to the present day.
The Macedonian Empire, under Philip II, on conquering the Greek
city-states, adopted their culture and subsequently assisted its spread
to Persia, Egypt, and part of India. This influence remained after the
disintegration of the Empire and resulted in the so-called Hellenistic
age, the cultural centre of which was Alexandria. This age saw the
origin and expansion of the natural sciences of today, possibly
because of Greek access to the knowledge of the Egyptian and
Babylonian priesthoods.
This period, which lasted until the 8th century, saw such great
masters as Archimedes (287—212 B.C.) and Heron (2nd century
B.C.) in mechanics, Euclid (3rd century B.C.) in geometry, and
Eratosthenes (276—195 B.C.) in astronomy.
Chemistry, stemming from the marriage of Greek philosophy and
the mystic, secret sciences of the East, first appeared towards the end
of this age.
(B) ORIGIN OF CHEMISTRY
Chemistry as a science did not exist in ancient times, but chemical

technology was used in many processes. Man could tan leather, dye
fabrics, make pottery, soap and cosmetics and, most important,
make metals and alloys from ores. The chemicals known at this time
included gold, silver, copper, tin, lead, iron, mercury and their oxides,
acetic acid and some acetates, lime and alkali-metal hydroxides,
copper and iron sulphates, potash from vegetable ashes and the
naturally occurring soda, saltpetre and rock salt. Operations such as
distillation, crystallisation, evaporation and filtration were also
known in pre-Hellenistic times.
Alchemy was born between the 2nd and 3rd century A.D. with
the intention of making gold and silver from base substances using
theory and experiment. The Roman Emperor Diocletian caused all
books in Egypt on alchemy to be burned lest the Egyptians became
rich enough to rebel against the Empire. This is the first recorded
event in the history of chemistry [ 2 ] . The first known use of the
word chemistry is in the book (336 A.D.) by the Sicilian astronomer
62
and mathematician Julius Maternus Firmicus on the influence of the
stars on the lives of men. Chemistry, he suggests, is recommended for
those born under Saturn [ 3 ] . The origin of the word is said to be
from the Egyptian for Egypt, Khemi, and so, literally, it means
Egyptian art. An alternate derivation could be from the Greek words
λνμσς meaning fluid and κβω meaning to pour.
The alchemists view that all substances are composed of four
primary elements, namely earth, water, fire, and air (a fifth one,
ether, having a spiritual character) can be traced to Aristotle. The
fact that chemical elements are dissimilar is due to them containing
different proportions of the primary components. In the light of
modern knowledge on the structure of matter, this assumption is
fundamentally correct. It was by changing the proportions of these
elements in a metal that they hoped to change one metal to another.
They inferred that new substances could be formed from existing
ones. For example, when iron was added to a solution of copper
sulphate, it disappeared and copper was formed. Also, when mercury
was melted with sulphur, a black substance was formed which on
heating changed its colour to red.
The age of alchemy lasted for more than a thousand years,
through the whole of the middle ages, and was even active until the
early 19th century.
Although it did not achieve its aim, a large amount of knowledge
and experience was gained on which the science of modern chemistry
was built.
(C) E A R L Y A N A L Y S I S
Analytical chemistry is the mother of modern chemistry. Sub-

stances must always first be examined to find their composition and
only then is it possible to use them for a definite purpose.
Analysis was first used extensively in quality control of goods and
merchandise, the most important of which were gold and silver. The
earliest known procedure for assay of gold and silver, which is still in
use today, is known as the fire assay or cupellation. This is a quanti-
tative procedure which depends on weighing the substance to be
tested before and after heating. In the Old Testament, there are
several references to its use. For example, "And I will bring the third
part through the fire, and will refine them as silver is refined, and will
try them as gold is tried" [4] and "Son of man, the house of Israel is

to me become dross: all they are brass, and tin, and iron, and lead, in
the midst of the furnace; they are even the dross of silver . . . . As
they gather silver, and brass, and iron, and tin, into the midst of the
furnace . . . so shall ye be melted in the midst thereof" [ 5 ] . Refer-
ences to the fire assay have also been found on the Tel al Amarna
tablets, cuneiform tablets in the Babylonian language found in the
the Nile Valley. The King of Babylon complains to Amenophis, the
IVth Egyptian pharaoh ( 1 3 7 5 - 1 3 5 0 B.C.), "Your Majesty did not
look at the gold which was sent to me last time, they were sealed
only by a clerk, therefore after putting them in the furnace, this gold
was less than its weight" [ 6 ] ,
The balance has been known since earliest times and is so old that
the peoples of the ancient civilisations attributed its origin to the
Gods. Babylonian stone weights still remain from 2600 B.C. These
were in the shape of geometric or animal figures and marked with
their weight and sacerdotal seals. The unit of weight was the "leight
mina" and equalled 491.29 g. This compares with the old French
pound (489.5 g), the Dutch pound (492.17 g) and that of Hannover
(489.6 g). From this and other information, Walden [7] infers that
old European measures were derived from Babylonian ones.
Cupellation was used in Rome to check for counterfeiting. Pliny
[8] describes how Marius Gratidianus introduced a bill ordering the
examination of coins to check for purity. The other method which
was in common usage for testing the purity of gold was by scraping it
on a touchstone and examining the colour and extent of the streak
produced. The earliest description of the touchstone occurs in
Theophratus' work On Stones (c. 380—287 B.C.) [ 6 9 0 , 6 9 1 ] . He tells
us that the best touchstones are to be found in the River Tmolus.
Pliny tells how the much more difficult separation of gold and
silver was undertaken.
"Into an earth vessel together with the gold must be placed two
parts of salt and three parts of misy, and covered with a mixture of
two parts of salt and one part schiste. The whole must then be placed
in the fire, when the mixture takes up everything that is not gold and
pure gold remains" [ 9 ] .
According to Strunz, "misy" is iron sulphate, salt, of course,
means sodium chloride, and schiste is brick powder. When the mix-
ture is heated, silver chloride is formed which then melts and is
adsorbed on the brick powder [ 1 0 ] . This procedure is called
"cementation" and was in use for hundreds of years.
64
Two ancient Egyptian manuscripts, known as the Stockholm and
Leyden papyri, tell of analytical methods. If gold undergoes no
change when it is heated, it is considered pure; if it becomes harder,
then it contains copper and if it becomes whiter, then it contains
silver. In examining tin, the metal is first melted and then poured
onto papyrus. If the papyrus burns to ashes, then the tin is pure, but
if the papyrus does not burn, it is an indication that lead is present
[ 1 1 ] . Evidently, the melting point of pure tin is higher than that of
tin alloys. Pliny records the use of extract of gall-nuts as a chemical
reagent when soaked on papyrus. Adulteration of copper sulphate
with iron sulphate could be detected by the papyrus becoming black
when dipped in the sulphate solution [ 1 2 ] .
The medical men of ancient times were concerned with the
examination of water. Pliny refers to sulphuric, acidic, saline and
iron-containing waters. Turbid waters were filtered and cleaned with
white of egg. Water was also distilled and it was noted that seawater
became drinkable after evaporating it and condensing the vapour
[ 1 3 ] . Vitruvius (1st century A.D.) determined the purity of water by
weighing the residue after distillation [ 1 4 ] .
These few examples show how limited is our knowledge of the
ancient methods for the examination of substances.
(D) ALCHEMY
With the collapse of the Western Roman Empire, political and

economic stability no longer existed in Western Europe and, under
these circumstances, science could not develop. However, in the east
under the Byzantine emperors, stable government ensured peace.
Industry and trade were carried on in the rich cities; libraries, scien-
tific research and classical literature all flourished.
This was interrupted by the Arab invasion which conquered
Mesopotamia, Syria, and Egypt. Once again, however, an uncultured
conquering nation adopted the culture of the vanquished. The Arabs
continued the study of the classics with great eagerness and trans-
lated many works from the original Greek. All branches of science
prospered under the Arabs and schools were formed around all the
large mosques. These temple schools, ancestors of our modern univer-
sities, were found in Damascus, Bagdad, Samarkand, Cairo, and
Cordova in Spain. The last exerted a great influence on Christian
Europe.

Meanwhile, Western Europe consolidated into small principalities
with the Church of Rome as the only co-ordinating factor. Contact
with the east came through the Crusades and proximity in Sicily and
Spain. At the beginning of the 12th century, Salerno opened a medi-
cal academy, followed by Montpellier in 1125, to teach the philoso-
phy of Aristotle as interpreted by Ibn Rusd (Averroes), the Arabian
philosopher.
This philosophy proclaimed the thesis of double truth, which is
that religious and scientific truths are quite separate. These views
were spread by St. Thomas of Aquinas in the 13th century and
accepted by the Church. To teach its own philosophical views, the
Church supported the founding of universities such as those at
Bologna, Paris, Coimbra, Salamanca, and Oxford. Theology was the
principal subject, but soon natural sciences were revived.
Before the end of the 19th century, when Berthelot and his
coworkers translated many Greek alchemical manuscripts [ 1 5 ] , little
or nothing was known of Greek alchemy; indeed, the origins of
alchemy had previously been thought to be Arabic. The Greeks
clearly had a great deal of alchemical knowledge and had developed
many chemical operations including distillation (Fig. 2). Most
notable of the Greek alchemists was Zosimos. His work is so mystical
and symbolic that its meaning is hard to decipher. An extract illus-
trates this.
"Prepare, my dear, a church of one lead white or alabaster stone,
in the building of which there is neither beginning nor end, but in the
inside there is a spring with clean water, and brightness which glows
like the sun. Watch where is the entrance of the church, take your
sword in your hands and look for the entrance. Because the place is
narrow, where the inside opening is and a dragon lies beside the door
guarding the church. Sacrifice this first".
The author of the book from which this extract is taken says that
it is not difficult to realise that the passage is a description of a
distillation apparatus [16] (Fig. 1). Chemistry requires a good
imagination at times.
The state of development of Arab alchemy is known mostly from
Latin translations. The Arab alchemists, although agreeing in principle
with Aristotle's theory, modified it slightly to include two further
primary elements, namely mercury and sulphur, which, of their
known elements, appeared to best represent the qualities of "moist"
and "dry" vapours.
66
F i g . 1. D i s t i l l a t i o n a p p a r a t u s f r o m t h e a l c h e m i s t i c m a n u s c r i p t o f Z o s i m o s . ( F r o m
Hoefer, Histoire d e la Chimie, 1 8 4 2 . )
Fig. 2. C h e m i c a l apparatus o f Greek a l c h e m i s t s . T a k e n f r o m a m a n u s c r i p t in

B i b l i o t h è q u e N a t i o n a l e . ( F r o m Bugge, D a s B u c h der grossen C h e m i k e r . )

Although Olympiodoros, an early Greek alchemist, refers to a
certain "nitronoil", which dissolves metals [ 1 7 ] , the identity of the
discoverer of nitric and sulphuric acids and of aqua regia hinges on
the identity of a man named Geber, which is a Latin corruption of
Jâbir Ibn Hayyân. He was an Arab physician and alchemist who lived
in the 8th or 9th century, about whom very little is known.
In a book attributed to Geber, Summa Perfectionis Magisterii, we
find the extract
"Let us distil a pound of cyprian vitriol (iron or copper sulphate),
one and a half pounds of saltpetre, a quarter of a pound of alum and
obtain the water (acid). This water dissolves metals very well. Its
effect will be even greater by adding a quarter of a pound of salmiac
to it (aqua regia)" [ 1 8 ] .
Ruska [19] claims that it is difficult to imagine that so much
knowledge was available in the 8th century, but he also says of some
authentic Arabic texts that he is amazed at the extent of Geber's
medical knowledge. Many authorities believe the book to be the
work of a Christian alchemist of the 13th century, the date the book
was first published in Europe. Such scepticism is quite understand-
able; ancient alchemists had the habit of ascribing their works to other
authors, partly to gain greater importance, and partly to remain
anonymous as the Church actively opposed alchemy. In spite of the
fact that many alchemists were priests, Pope John XXII, in 1317,
had forbidden the study of alchemy.
In the subsequent period of western alchemy, zinc, antimony, and
bismuth were all discovered and this initiated the use of salt solu-
tions and processes which occur in solutions. It was only later in the
16th century that alchemy adopted its dubious character, the form
of which it was to maintain until it finally collapsed.
(E) KNOWLEDGE O F A N A L Y S I S
The idea of specific gravity has been known since antiquity, or at

least since the time of Archimedes, the first known reference to the
use of a hydrometer being of Greek origin. Hippocrates had previ-
ously observed the variation in weight of the same volume of differ-
ent liquids and Galenus, the great Roman physician, checked the
density of salt waters recommended as a medicine with eggs [ 2 0 ] .
Synesios, a Greek alchemist of the 4th—5th century, had introduced
the use of a hydrometer for this purpose which he described as fol-
lows.
68
TABLE 1
Comparison of specific weights
Matter Density
According t o Albiruni Today

or Alchazini
Rainwater 1.000 1.000

Seawater 1.041 1.028-1.042
Wine 1.022 0.992-1.038
Honey 1.406 1.410-1.445
Olive oil 0.915 0.914
Milk 1.110 1.028-1.034
Vinegar 1.027 1.013-1.083
R o c k salt 2.19 2.161
Tin 7.32 7.28
Wrought iron 7.74 7.86 - 7 . 7 6
Copper 8.66 8.30 - 8 . 9 2
Lead 11.32 11.34
Mercury 13.560 13.546
Gold 19.05 19.21
"This is a cylinder-tube, on which horizontal lines are marked to

measure the depth it submerges into the liquid. In order to keep it in
a vertical position in the liquid, a small weight is attached to the
lower end" [ 2 1 ] .
This instrument he called a hydroscopium. The discovery of the
hydrometer was later forgotten and it was not until a thousand years
later that Boyle rediscovered it, although he gave full credit to
Archimedes for much of the original work [ 6 5 ] .
Albiruni, an Arab scientist (973—1048), determined the specific
weight of numerous substances and there also remain many data due
to Alchazini (12th century), author of the book About the Balance
and the Wiseness. Using a balance to determine specific weight, he
achieved results astonishingly accurate in comparison with present
day values [22] (see Table 1).
Geber also refers to specific weight as a characteristic criterion of
metals. These are similarly characterised by their melting point,
colour, lustre and ductility. To illustrate this, the descriptions of a
few metals taken from Geber's Summa Perfectionis Magisterii [23]
are given below.

"Gold. Metallic substance, its colour is lemon-yellow. It is very
heavy, lustrous, ductile on hammering, is resistant to the test (cine-
ritium), roasting and burning with coal. It is soluble, giving a red
solution and renovates the body, it can be alloyed easily with lead
and mercury. Only with the greatest effort can it be fixed with the
spirits (dissolved in acids?); this is the great secret of this art, which
slips out of the memory of those who have a hard head.
Lead. It is a dun-coloured or dull white, heavy, not clinging metal.
It is easily malleable, ductile with hammering and has a low melting
point. It forms cerussa (lead white) with acetic acid, and minium
when it is roasted. Though it is not at all like silver, with the help of
our art we can change it to silver! (The high silver content of lead
ores might have been the cause of this positive but erroneous declara-
tion.) Its weight does not remain constant during this change. (He
concludes by saying that lead is used for fire assays.)
Iron. It is a greyish-white, high melting metal, very clinging, not
very ductile and with difficulty malleable. It is very dense and is
difficult to work because of its high melting point. None of the
metals which are difficult to melt are suitable for "transmutatio"
(transformation of elements)."
These descriptions are extremely clear and completely different
from the language of the earlier Greek alchemists.
Fig. 3 . G o l d testing in the 1 5 t h century. ( F r o m Biringuccio, Pyrotechnia, 1 5 4 0 ) .
70
Both Geber and Albertus Magnus give clear descriptions of the
cupellation procedure for gold and silver [ 2 4 , 2 5 ] , This procedure
was in statutory use for the examination of gold by the 14th century.
A detailed account of the method is given in a statute of King Philip
of France in 1343. This can be regarded as the earliest example of a
standard method of analysis (Fig. 3).
The cupells are described as small, flat, recessed and well-washed
vessels made of vine-shoot ash and burnt leg bones of sheep. To free
it from any substances which may interfere with the test, it must be
well polished. Afterwards the cavity must be moistened with a liquid
which is a suspension of powdered deer antlers in water. This causes
a white glaze to be formed so that the examined substance can
occupy a better position and is easier to remove afterwards. The
decree also prescribes that the lead used for the tests should be of
good quality and must not contain either gold, silver, copper, or any
other impurity. It also mentions the precision required in weighing.
"The balance used for the test should be of good construction,
precise and should not pull to either side. The test should be carried
out in a place where there is neither wind nor cold and whoever
carries out the test must take care not to burden the balance by
breathing upon it" [ 2 6 ] .
The balances employed for these tests must have been quite sensi-
tive for breathing to have had any effect on them.
Antimony, which was discovered in the 15th century, was found
to remove copper and silver from gold leaving the gold as a regulus at
the bottom of the melting pot [ 2 7 ] .
The Middle Ages saw an improvement to the scratch or touchstone
test. By the early 16th century, a series of 23 needles of 1—23 carats,
plus one of pure gold, were employed, the scratch on a touchstone
from these needles being compared with the scratch of the examined
object [ 2 8 ] .
Metals were found to dissolve in mineral acids and it then became
possible to work with the solutions obtained. Most alchemists
believed the substance to have disappeared on going into solution.
Indeed, during the 17th century, only van Helmont stated definitely
that it had not done so. In spite of this, many procedures were
carried out using solutions and this point really marks the beginning
of analytical chemistry as we know it today.
Mineral acids were first used for the testing of gold and silver and
it was discovered that although "aqua regia" dissolves gold, silver

Fig. 4. A l b e r t u s M a g n u s ( 1 1 9 3 — 1 2 8 0 ) . Painting b y Fra Giovanni da Fiesola t o be
f o u n d in t h e D o m i n i c a n A b b e y in F l o r e n c e . ( F r o m Bugge, Das B u c h der grossen
Chemiker. )
is precipitated by it. It was also found that silver can be dissolved

with nitric acid, and this gave a simple method for the separation of
gold and silver. Albertus Magnus gives an account of the preparation
of nitric acid and describes some of its properties. He mentions that
it will dissolve silver, and that mercury and iron are converted by it
to the oxide [ 2 9 ] .
Albertus Magnus (1193—1280) (Fig. 4), a Dominican monk who
later became a bishop, was a professor at the Paris University and
also the teacher of Thomas Aquinas. He was one of the outstanding
scientists of the Middle Ages and a pioneer of the natural sciences.
At the beginning of the 15th century, nitric acid was adopted for
72
the industrial separation of gold and silver. At about this time, it was
also discovered that the separation is more effective if the ratio of
gold to silver is 1 : 3, and hence ores of a low silver content had silver
added to them before the separation. This resulted in the name
"inquartation" being given to the process. The earliest records of this
process are from Selmecbanya (Schemnitz) in the upper Hungarian
mining district (now in Czechoslovakia), which was one of the most
important noble metal producing areas in Europe in the Middle Ages.
The process was also used for the testing of gold and there are
numerous references to its use. In 1499, the citizens of Selmecbanya
complained of the unfairness of the test with nitric acid carried out
by an official tester [ 3 0 ] . By the 16th century, the separation of
gold and silver with nitric acid was widely used throughout Europe
[31].
Paracelsus tells us that after the separation of gold and silver with
nitric acid, the silver can be recovered from the solution by the addi-
tion of copper wire [ 3 2 ] ; addition of iron wire to the solution will
cause copper to be precipitated [ 3 3 ] . Raymond Lull, the Spanish
alchemist (1235—1315?) describes the preparation of nitric acid in
which he mentions that the water used must first be cleaned with
silver in order to remove the "pinguedo salis nitri". Probably by this
he meant chloride [ 3 4 ] , It is very probable that, apart from the few
chemical reactions described, the alchemists of the Middle Ages knew
of many similar to them and, although they had no idea of the
nature of the mechanism of these reactions, they still form the basis
of the knowledge on which modern chemistry and analytical chem-
istry has been built. The beginning of this development marks the
start of the period of medical chemistry, the next important era in
the history of chemistry.
(F) CLARIFICATION OF CHEMICAL CONCEPTS
The development of iatrochemistry commenced in that remark-

able period of European history known as the Renaissance. This was
a period of the rebirth of the natural sciences and marks the start of
their very rapid progress. The discovery of printing multiplied the
works of the ancient classics and these became far more widely read.
As the area of the known world expanded, due to geographical dis-
coveries, so the problem of safety in navigation turned attention
towards astronomy and then to mathematics and physics. Practice

and theory became closer as it was found that existing knowledge
was less useful in solving problems than a suitable examination of the
factors involved. The origin of this new method of research is gener-
ally attributed to Francis Bacon (1561—1626), the English philoso-
pher and statesman who pointed out the importance of the experi-
mental method.
"As in everyday life, natural endowments and the secret charact-
eristics and emotions of human soul manifest above all in trouble,
also the secret phenomena of nature manifest sooner by the effect of
mechanical interventions, than if it freely runs on its way" [ 3 5 ] .
Although Bacon clarified the scientific methods in use at that time
and stressed the importance of experiment, he was not the first to do
so. Leonardo da Vinci believed in the role of experience [36] as did
Bernard de Palissy (1499—1589). In one of the latter's works written
in the form of a dialogue between two people, the vain, empty
Théorique (theory) and the clever Practique (practice), the topic of
their conversation explains the inductive scientific method [ 3 7 ] , The
16th century was to see the clash between the new natural sciences
and scholastic ideology. The former had triumphed by the 17th cen-
tury and this was to result in the establishment of academies of
science [ 3 8 ] .
A new period of chemistry began when chemists turned their
attention from attempts to make gold to the making of medicines.
The first propagator of this new tendency was Aureolus Phillipus
Theophrastus Bombastus Paracelsus von Hohenheim (Paracelsus)
(1493—1541) (Fig. 5). He was a true Renaissance character, lawless,
passionate, unscrupulous and with something of a dual personality.
From a vagabond of the roads, he became a professor at the Univer-
sity of Basle, but was eventually compelled to leave because of his
extreme views, so he once again became a vagrant charlatan and
eventually died in a hospital for the poor in Salzburg. He fervently
attacked the ancient medical authorities, Hippocrates, Galenus, and
Avicenna, who he said were "unworthy to untie my sandal-straps".
He proclaimed
"And you, who have learned from these believe that you know
everything although you know nothing. You want to prescribe
medicines and yet cannot make them: chemistry solves for us the
secrets of therapy, physiology and pathology; without chemistry we
are trudging in darkness" [ 3 9 ] .
The study of chemistry was now largely undertaken by physicians,
74
F i g . 5. P a r a c e l s u s ( 1 4 9 3 — 1 5 4 1 ) . P a i n t i n g b y a n u n k n o w n m a s t e r . ( F r o m B u g g e ,
Das B u c h der grossen Chemiker. )
who helped to explain the processes going on in living organisms and,

because solutions played an important part in the mechanism of
these organisms, they turned their attention towards solution pro-
cesses. The discovery of the nature of these led to the development
of qualitative chemical analysis.
Paracelsus introduced a third element, "salt", to the alchemical
elements of sulphur and mercury. He claimed that all metals, organic
and inorganic substances were composed of these three elements.

Fig. 6. V a n H e l m o n t ( 1 5 7 7 — 1 6 4 4 ) . ( F r o m his A u f g a n g der A r t z n e i k u n s t , 1 6 8 3 . )
Jean Baptist van Helmont (Fig. 6) modified the alchemical view of

the elements; of the four elements of Aristotle, he considered only
water as a primary element. He proved this by a "quantitative analyt-
ical" experiment. Into a pot he weighed 200 lb. of dried soil and in
this he planted a willow branch which weighed 5 lb. A lid was used
to cover this and the branch was watered with rainwater daily for
5 years. After drying and reweighing the soil he found that the mass
was almost unchanged, a difference of 2 oz. less. However, the
willow branch by this time had become a tree and weighed 164 lb.
Van Helmont argued that as only rainwater had been added then the
76
tree had been formed from water. Then the tree was burnt, gases
were evolved and only soil (ash) remained; therefore both of these
had also been formed from water [ 4 0 ] . Despite a clear thinking
mind, van Helmont had alchemical ideas in that he believed in the
possibility of making gold and that mice were formed from a dirty
shirt dusted with wheaten meal.
Much later, Robert Boyle gave a definition of elements which is
extremely close to the modern one.
"I now mean by elements,. . . certain primitive and simple, or
perfectly unmingled bodies; which not being made of any other
bodies, or of one another, are the ingredients, of which all those
called perfectly mixed bodies are immediately compounded and into
which they are ultimately resolved." [ 4 1 ] .
In his works The Sceptical Chymist [ 4 1 ] and Origin of Forms and
Qualities [ 4 2 ] , Boyle distinguishes between primary elements, which
are intangible, and the actual elements. Although the relationship
between atoms and molecules is not very clear, he does make a clear
distinction between compounds and mixtures. He revived the con-
cept that elements consist of minute, indivisible particles which,
because of their affinity for one another, combine to form com-
pounds [ 4 2 ] . This was simply a restatement of the theory of
atomism originally proposed by Democritus in 400 B.C.
Even before Boyle, others attempted to revive the atomist theory.
One of these was Pierre Gassendi, the French mathematician and
astrologer (1592—1655) and many other philosophers and scientists
were to follow him [ 4 3 ] .
During the period of iatrochemistry, the first division of com-
pounds into acids, alkalis, and salts was made. Everything which was
soluble was salt; saltpetre, alum, borax, tartar, and even sugar being
included [ 4 4 ] . It was discovered that salts were formed with the
combination of acids and alkalis. Edward Jorden (1569—1632)
writes that the constituents of mineral waters or baths may be deter-
mined "by precipitation, whereby those minerall substances are
stricken down from their concrete juices which held them, by addi-
tion of some opposite substance. And this is of two sorts: either
Salts, as Tartar, Soape, Ashes, Kelps, Urine, etc. Or sour juices, as
Vinegar, Lemons, Oil of Vitriol, Sulphur, etc. In which I have ob-
served that the Salts are proper to blue colours, and the other to red:
for example, take a piece of Scarlet cloth, and wet it in Oil of Tartar
(the strongest of that kind) and it presently becomes blue: dip it

again in Oil of Vitriol, and it becomes red again." [ 6 9 2 ] . Boyle
defined acids as having the power to dissolve metals to varying
degrees, to precipitate sulphur and other substances dissolved in
alkalis, and also to change the colour of certain vegetable extracts to
red. The definition of alkalis was vague; they were known to give
blue or green colorations with certain vegetable extracts and to cause
effervescence with acids. This effervescence was later to become the
first indicator to be used in volumetric analysis.
Although the word affinity had been used by Albertus Magnus,
Glauber was the first to note that the tendency of a substance to
combine with other substances varies greatly and depends on the
nature of the second substance. He noted that sulphuric acid drives
out hydrochloric and nitric acids and that nitric acid dissolves metals
with increasing ease in the order gold, mercury, copper, tin, iron,
lead [ 4 5 ] . The first recorded observation of double decomposition
was also made by Glauber.
The discovery of gases also occurred during this period. Van
Helmont wrote
"In consequence of burning coal, spiritus sylvestris comes into
being. 62 lb. of oak-coal gives one lb. of ash, therefore it provides
61 lb. of spiritus sylvestris. This spiritus, which was formerly un-
known and cannot be kept in vessels and cannot be converted into a
visible form, I call by the new name "gas". (Hunc spiritum incognitum
hactenus, novo nomine gas voco) [ 4 6 ] .
The examination of gases led, in the next century, to the establish-
ment of modern chemistry. It can be seen that this period was
responsible for the clarification of many chemical concepts. This was
a direct result of the development of analytical chemistry.
(G) T H E B E G I N N I N G O F A N A L Y S I S IN A Q U E O U S S O L U T I O N S
Of all the processes occurring in solution, only the separation of

gold and silver with nitric acid was used for the purpose of analysis
during the Middle Ages. Georgius Agricola (1494—1555) says that
gold was hammered into a thin sheet and then rolled up and treated
with nitric acid [ 4 7 ] . Most of the chemical reactions on which the
classical system of qualitative analysis is based were only discovered
during the period of iatrochemistry. The most important of these dis-
coveries was that substances can be divided into groups on the basis
of these reactions and single substances can then be identified.
78
Basilus Valentinus was one of the first people to stress the impor-
tance of processes occurring in aqueous solution and used such words
as "precipitation" and "precipitate". He precipitated gold from aqua
regia with potassium carbonate and mentioned that the precipitate
must be air-dried because it explodes on direct heating [ 4 8 ] . He also
carried out experiments on the separation of metals with solutions of
different acids and alkalis.
In this era, a great deal of work was carried out on the examina-
tion of water, largely for its medicinal effects. One of the most
detailed books on this subject was Pison oder von Kaltem Warmer
Minerischen and Metallischen Wassern by Leonard Thurneysser
(1530—1596), published in 1572. He was a physician who led an
adventurous life, travelling about the world from England to Arabia.
In his method, a vessel is filled with rainwater, weighed, refilled with
the water under examination and weighed again. The amount of dis-
solved substance is deduced from the difference in weights. The
water is distilled off and the residue weighed; this is then redissolved
and allowed to crystallise. The crystals are separated and heated; if
they ignite, they are composed of nitrium (nitrate); if they are easily
soluble and on heating become red, they contain vitriol and if soluble
only with difficulty, they contain lead. The distillate is redistilled
and if the residue becomes blue on heating, then copper or gold is
present; if it evaporates, then it contains mercury. If it turns brown,
copper is present, whereas if it remains white, the water contains tin.
He also drew conclusions from the colour of a flame when a portion
of the residue was ignited in it [ 4 9 ] . The method of Thurneysser,
although containing several correct assumptions and observations, is
for the most part rather confusing.
Libavius' account of 1597 is more concise. He suggests the
presence of gaseous components and uses the extract of gall-nuts to
identify iron [ 5 0 ] . Gesner in 1576 also used "decoction of Gall
nuttes" to test for iron or aluminium [ 6 9 3 ] .
In Boyle's Memoirs of a Natural History of Mineral Waters [ 5 1 ] ,
he also uses the juice of gall-nuts to test for iron (black coloration)
and copper (red coloration or precipitate), but states that the
amount of gall-nut powder added must be carefully measured as the
strength of the colour then gives the amount of metal present.
Other reagents suggested are rose extract, juice of pomegranate,
brazil wood extract, etc., although these are not reliable. He made a
new reagent which he called "volatile sulphureous spirit" by melting

sulphur, adding gradually a similar quantity of potassium and distilling
the mixture with an aqueous solution of ammonium chloride [ 5 1 ] .
Only the last part of the distillate must be absorbed in water, because
this is the only part suitable for the purpose of the reagent. Gold and
mercury solutions gave a black precipitate with this reagent while tin
gave a yellowish-brown one [ 5 2 ] . Szabadvâry repeated this experi-
ment and found that hydrogen sulphide is formed [ 5 3 ] . Hydrogen
sulphide was not used in analytical practice after this until the end of
the following century.
Boyle found that if extract of violets became green in solution, the
water was alkaline. These waters also gave a precipitate with mercury
chloride and effervesced with acids [ 5 4 ] . He distilled the water and
did a fractional crystallisation on the residue, drawing conclusions
from the shape of the crystals.
In his Methodus Examinandi Aquas Salubres (1703), Friedrich
Hoffmann (1660—1743) describes the examination of numerous
mineral waters. Among many useful observations, he detects the
presence of magnesium salts and distinguishes them from calcium
salts.
Otto Tachenius carried out a systematic examination of the effect
of gall-nut extract by observing the colour formed with solutions of
many metals [ 5 5 ] . By treating urine with this extract, he established
that iron is not removed from the human body via the urine, as had
previously been supposed, because no colour was obtained [ 5 6 ] . This
is the first example of analysis being applied to biochemistry. He
determined that silicic marl ( S i 0 2 ) was an acid as it formed a salt
with potassium carbonate [ 5 7 ] . He also undertook applied analysis.
In Venice, where he lived, some solutions of rose-water, a scent taken
to prevent ascarides, caused the patient to vomit. Tachenius exam-
ined this problem and concluded that
"The cause of this is not the rose-water but copper particles which
have come from the copper flask used for the extraction. As proof of
this, if a few drops of alkali are added to the rose-water a green
precipitate immediately forms. After filtering, it is found that it will
not cause any further vomiting" [ 5 8 ] .
When discussing soaps, Tachenius noticed that fats contain a
"hidden acid" [ 5 9 ] . A somewhat neglected figure, a reappraisal of
his work would ensure him more recognition.
As it was still the practice to store wine in lead vessels, Eberhard
Gockel (1636—1703) discovered that when sulphuric acid is added to
80
the wine a white turbidity occurs if lead is present [ 6 0 ] .
Johann Rudolf Glauber (1604—1670), one of the great figures in
chemical technology, was also a skilled chemist and a successful busi-
ness man. His new method of making hydrochloric and nitric acids
from rock salt and saltpetre, respectively, he kept secret until near
the end of his life. He also found that silver chloride would dissolve
in ammonia solution and that silver gives a precipitate with alkali and
carbonates [ 6 1 ] . Lead chloride, he noted, was only slightly soluble in
water. Cochineal extract became scarlet when he added nitric acid to
it, but he did not pursue the possibility of using this as an acid—base
indicator, his only use for it being as a paint for hair and nails.
(H) ROBERT BOYLE
Many authorities consider that the work of Boyle marks the

beginning of chemistry as a science. Although reluctant to underesti-
mate the value of Boyle's discoveries, the authors consider this view
to be a slight exaggeration, though, without doubt, Boyle helped
chemistry to dissociate itself from the medical science to which it
had become bound and gave it new direction. "It is in my opinion,
one of the principal impediments to the advancement of natural
philosophy, that men have been so forward to write systems of it."
As these men, he observes, "had scarce any view but to the prepara-
tion of medicines or the improving of metals, I was tempted to con-
sider the art not as a physician or an alchemist but as a philosopher".
He continues "and truly, if men were willing to regard the
advancement of philosophy, more than their own reputations, it
were easy to make them sensible that one of the most considerable
services they could do the world is to set themselves diligently to
make experiments and collect observations without attempting to
establish theories upon them before they have taken notice of all the
phenomena that are to be solved" [ 6 2 ] .
From this we see that Boyle believed not in advancing theories,
but rather conducting experiments and from these drawing inferences.
He followed this principle, which was, in effect, the English empiricist
philosophy of the time, throughout the course of his work. Once
having chosen the pursuit of science, Boyle was fortunate enough to
have sufficient wealth to enable him to do so. His contributions to
the fields of mechanics, optics and chemistry are of equally great
importance.

F i g . 7. R o b e r t B o y l e ( 1 6 2 7 — 1 6 9 1 ) . ( F r o m h i s O p e r a V a r i a , 1 6 8 0 . )
Boyle contributed greatly to the development of analytical chem-

istry and indeed originated the word analysis in the sense that we
know it today. The first reference comes in a letter to Fredrick
Clodius [694,695] in April 1654 from his estate in Ireland.
"I live here in a barbarous country where chemical spirits are so
misunderstood and chemical instruments so unprocurable, that it is
hard to have any hermetic thoughts in it, and impossible to bring
them to experiment. . . For my part that I may not live wholly use-
less, or altogether a stranger in the study of nature, since I wont for
glasses and furnaces to make a chemical analysis of inanimate bodies,
I am exercising myself in making anatomical dissections of living
animals".
Robert Boyle (Fig. 7) was born in 1627, the 14th child of an
82
EXPERIMENTA
E T C O N S I D E R A T I O N E S
C O L O R I B U S ,
Primtm rx MffMt, rnltr élut quiflam Dutrikai^d Amicim
fcrift*, taux veri in litemprUirepfl*, ecu
1N1TIUM HISTORIEE EXPERIMENTALIS
D E C O L O R I B U S
ROBERTO BOYLE
N o l l L i Anglo, SociecatisRfçix Mcmbro.
Ktn fimfendmm, *wr excogitmdim, fid intHnitnimm, fid XM^M f*ciu ma first. Bacon.
G E N E y o£
Apud S A M U E U M DE TOURNES.
F i g . 8. T i t l e p a g e o f R o b e r t Boyle's book, Expérimenta et Considérationes de

Coloribus, 1680.
aristocratic family. The family estate was wealthy enough to provide

for all these children. He was given the best possible education and
afterwards made the "Grand Tour" of the continent. He returned to
England on hearing of the death of his father in the Civil War and
lived in Oxford from 1657 until 1668 and after this in London,
where he died in 1691. Boyle was in poor health throughout his life
and never married. He was a founder member of the Royal Society
and took an active part in its affairs and later became President. His
first book was published in 1659 and the rest followed almost un-
ceasingly, about forty in all. His works are concerned with many
problems in physics, chemistry, and the medical sciences and were
always based on his experiments. In a dry and non-committal way,
he describes more than a hundred experiments and discusses the con-
clusions that can be drawn from them (Fig. 8).

The most striking feature about Boyle's studies in chemistry lies in
his use of reactions to identify various substances. He introduced
many new reagents and initiated the use of certain vegetable and
animal extracts (the extracts of violets and cornflowers, cochineal,
and litmus solution) for testing for acidity and alkalinity and he used
these in a systematic manner.
When discussing precipitation, Boyle mentions Aristotle's view
which was that precipitation occurred when two substances had
"aversion" properties which were the arbitrary choice of the Creator.
Although the precipitation of acidic substances with alkalis could be
taken as confirmation of Aristotle's belief, Boyle showed that, for
example, silver nitrate precipitates hydrochloric acid from aqua regia
and sulphuric acid precipitates coral and pearl from an acetic acid
solution, all of these being acidic substances. There are examples of
precipitations where the weight of the precipitated substances is
equal to the weight of the dissolved substance (an example of this is
where metallic gold is separated by reduction), but it is more com-
mon as Boyle states
"That in many precipitations, a coalition is made betwixt the
small parts of the precipitant and those of the dissolved metal,
appears by the weight of the precipitate, which though carefully
washed and dried, often exceeds that of the dissolved metal; for if,
having dissolved silver in good aqua fortis ( H N 0 3 ) you precipitate it
with a solution of sea-salt (NaCl) in fair water and from the very
white precipitate was the salts; the remaining powder being dried and
slowly melted, will look much less like a metalline body, than a piece
of horn, whence it takes its name of Luna cornea (AgCl); so consider-
able is the addition of the saline to the metalline particles" [ 6 3 ] .
From this it is seen that the washing and drying of precipitates
before weighing them was customary at this time.
To illustrate the systematic nature of his methods, we shall look at
his examination of mineral waters for arsenic. Beginning with a dilute
solution of arsenic in mineral water, he first added ammonia which
gave a white precipitate; potassium carbonate gave a heavy white
cloudy precipitate and sulphuric acid gave no precipitate. From this
he concluded that arsenic was an acidic substance. He then added a
few drops of violet extract to another portion of the solution when
the colour changed to green instead of the expected red (probably
due to the alkalinity of the mineral water). A further portion was
tested with hydrogen sulphide (volatile sulphureous spirit), but no
84
precipitate was formed (too alkaline). He then found that "When a
portion of the arsenic solution was treated with a strong solution of
sublimate a thick white precipitate was formed, which is quite
natural in alkaline solution. However, the precipitate was white,
similar to that formed with ammonia and not brick-red, as is usually
formed with alkalis" [ 6 4 ] .
He concluded, therefore, that a solution of sublimate (HgCl 2) is a
good reagent for arsenic.
He also examined the sensitivity of the reaction between iron and
the extract of gall nuts and states that "one grain of vitriolate sub-
Fig. 9. H y d r o s t a t i c balance of R o b e r t Boyle. ( F r o m his Philosophical Works,

1725.)

stance would have been found capable of so impregnating six
thousand times its weight of common water, as to make it fit to pro-
duce, with galls, a purple tincture" [ 6 6 ] .
Boyle reconstructed the areometer and also designed a hydrostatic
balance for the determination of specific weights (a drawing of this is
shown in Fig. 9) [ 6 7 ] . It is probable that his ordinary weighing
balances were constructed in a similar manner.
2. The 18th century
(A) THE PHLOGISTON THEORY
The so-called phlogiston period of the history of chemistry started

at the end of the 17th century and lasted for about 100 years. At
this time, the feudalistic divided states of Europe governed by
despotic liege lords had given way to large areas under monarchies
which encouraged commerce. Industrialisation increased as raw
materials from the new-found colonies increased.
The rapid development of industry resulted in many problems
and, in many cases, analytical methods were required to deal with
them. This brought about great progress in analytical chemistry,
particularly in metallurgical analysis. In the 18th century, the need
for metals, especially iron, greatly increased with increased mecha-
nisation. As iron production still used wood as a source of charcoal,
the industry could not cope with demand as the wood supply
diminished. It was Abraham Darby in 1709 who succeeded in
replacing wood with coal. The iron, however, was more brittle. To
trace the causes of these faults it was necessary to develop accurate
methods of analysis. Although a great many chemists applied them-
selves to this problem, it was not until the second half of the century
that Bergman was able to establish the carbon content of various
irons with sufficient accuracy and to understand the role that this
plays. He also noted that phosphorus makes iron brittle.
With the aid of James Watt's much improved steam engine of
1769, flooding in mines could be largely avoided. This led to the
proliferation of mines and, consequently, new minerals. Analytical
chemistry, particularly analysis of minerals, enjoyed considerable
prosperity, especially in Sweden, as she possessed the richest ore
mines. That country was to remain the centre of metallurgical
86
analysis until the 3rd decade of the 19th century.
Research and technology were to be integrated more in the
phlogiston period, leading to the rapid improvement of industrial
methods. Scientific socieities and academies of science, some with
wealthy sponsors, allowed open discussion of the results of research.
The advent of periodicals meant that scientists had access to the
results of their contemporaries and could consider them in the light
of their own work. The Journal des Savants published by the
Academy of Paris and Philosophical Transactions published by the
Royal Society were among the first. With the foundation of the first
Institutes of Chemistry at the University of Marburg and the Jardin
des Plantes in Paris [ 6 8 ] , the universities became the main centres of
chemical research. However, practical instruction was not given at
the universities until the 19th century. The first institution to teach
practical chemistry was the Mining Academy at Selmecbanya.
Founded in 1735, it was both the cradle of chemical research in
Hungary and one of the main scientific centres of Europe [ 6 9 ] . Its
laboratory training attracted such famous students as Manuel del Rio
(1769—1841), discoverer of vanadium, the d'Elhuyar brothers, dis-
coverers of tungsten and Ferenc Miiller (1740—1825), discoverer of
tellurium. The method of teaching was later copied by the École
Polytechnique of Paris, founded in 1794.
We now come to a discussion of the phlogiston theory itself. This
stated that all substances are composed of a combustible and an
incombustible component. The combustible part of all substances is
identical and is known as phlogiston. When a substance is burnt,
phlogiston escapes. The greater the amount of phlogiston a substance
contains, the more readily does it burn. Phlogiston is also lost when
metals are combusted and a metal-lime oxide or calx remains. The
equation for this reaction is
Metal — Phlogiston = Metal-lime
The production of metals by reduction with coal is given by the
equation
Metal-lime + phlogiston = metal
The origins of the phlogiston theory can be traced to Joachim Becher
(1635—1682) in his work Physica Subterranea published in 1 6 8 1 .
According to Becher, the earth-like (inorganic) substances are com-
posed of three kinds of earth, namely the glass-like, the mercury-like,

and the combustible earths. When a substance is burnt, this com-
bustible or oily earth escapes. Georg Ernst Stahl (1659—1734)
elaborated this theory in many of his works [70] published at the
beginning of the 18th century.
The phlogiston theory was the first conscious attempt to explain
different chemical phenomena from a unified point of view, the
theoretical basis of alchemy having been rejected. The simplicity and
clarity of the theory made it immediately acceptable and by 1740 it
was the dominant theory in chemistry.
Many 19th century chemists were amazed at how the phlogiston
theory could have survived so long. One of its major faults was that
when/a metal was combusted it increased in weight, whereas the
theory suggested that its weight should have been less. Early historians,
such as the German Kopp, believed this to be due to qualitative not
quantitative work, i.e. not enough use of the balance. This, however,
was untrue. The balance was often used by chemists and as early as
the 15th century, Biringuccio, in his work Pirotechnia, refers to
metals increasing in weight when combusted.
However, it was easy for the phlogistonists to believe that some-
thing was lost on combustion; witness the burning of wood or coal.
Also, there already existed an explanation for the increase in weight
of metals on combustion. This explanation, by then a thousand years
old, was confirmed experimentally by Boyle. On combusting some
tin in a closed space, he found it to have increased in weight. He
attributed this to minute fire particles. Presumably he had opened
the flask before the second weighing and allowed air to rush in [ 7 1 ] .
Another point in favour of the theory was that redox phenomena
could be explained, i.e.
Reduction = taking up electrons = taking up phlogiston
Oxidation = giving off electrons = giving off phlogiston
However, the phlogiston theory hindered the development of chemis-
try, metals reverting to compounds and oxides becoming elements
again. But new discoveries and the complete failure to detect
phlogiston analytically began to make the theory untenable. As new
facts emerged, it was modified to fit these, eventually becoming
confused and complicated. Later, with the discovery of hydrogen,
this was thought to be phlogiston, especially as it is less dense than
air and can be seen to leave metals when they are dissolved in acids.
A process for the determination of phlogiston was devised in the
18th century by Jakob Winterl, Professor of Chemistry at the Univer-
88
sity of Buda, Hungary. Winterl was a chemist of great inventive
power who tended to draw conclusions from his experimental results
which were extravagant and often unwarranted. For instance, he
claimed to have found substances which were simpler than the
chemical elements. He called these andronia and thelyke [ 7 2 ] .
Andronia was later proved to be silicious marl. The basis of the deter-
mination of phlogiston is the supposition that it reacts with nitric
acid and in doing so evaporates. Apart from this erroneous assump-
tion, the method is extremely logical. Also, the stoichiometry of the
reaction is remarkable at a time when stoichiometry was absolutely
unknown. It also contains the earliest reference to the use of a blank
determination which the authors have found. He describes the meth-
od as follows.
"To 400 cubic inches of distilled water is added as much nitric
acid as is required to dissolve 1 oz. of fluorite. The mixture is then
evaporated to one third of its original volume. The nitric acid
remaining now dissolves 14 grains less of fluorite. This loss in weight
is proportional to the phlogiston content of the water. The next
stage in the procedure is the determination of equivalent weight of
phlogiston and fluorite. To do this, 4 gr. of soot, which is practically
pure phlogiston, is ignited in a closed crucible and mixed with
400 cubic inches of distilled water. As much nitric acid as is required
to dissolve 1 oz. of fluorite is added and again the mixture evapo-
rated to one third of its original volume. The soot is filtered, dried
and found to weigh only 3 gr. The nitric acid remaining only dis-
solves 2 drachms and 26 gr. of fluorite, consequently the decrease is
5 drachms and 34 gr. Subtract from this the 14 gr. "blank value",
then 320 gr. of fluorite remain. This corresponds to the missing nitric
acid which was oxidized by the 1 gr. of phlogiston, i.e. 320 gr. of
fluorite is equivalent to 1 gr. of phlogiston" [ 7 3 ] .
During this period, the phlogiston theory was universal and all the
great scientists explained their results on the basis of it. The whole
chemical literature of this time was written in "phlogiston language",
for example, the solution process and the formation of salts were
explained by the taking up or release of phlogiston. New substances
often referred to it in their names, i.e. oxygen was "dephlogisticated
air", nitrogen was "phlogisticated air", sulphurous acid was called
"phlogisticated sulphuric acid" and even hexacyanoferrate became
"phlogisticated alkali".

(Β) T H E BLOWPIPE
The chemist of today is often unaware of the importance of that

most simple instrument the blowpipe, which was so essential for
chemical analysis in earlier times. With the help of the blowpipe, the
qualitative composition of most minerals was ascertained and many
new elements were discovered in the 18th century.
The blowpipe, essentially a narrow tube with which air can be
blown into a flame, has been in use by goldsmiths since antiquity
and, by the 17th century, was widely used in the glass industry. The
journal of the Accademia del Cimento in Florence for the year 1660
describes a small pipe with the help of which glassblowers, using their
mouths as bellows, blow into the flame and achieve very fine glass-
work [ 7 4 ] . Kunckel describes this instrument in his book Ars
Vitraria Experimentalis oder Vollkommene Glasmacherkunst pub-
lished in 1679.
"The object of the blowpipe is to admit air into the flame and a
very fine and concentrated flame is blown on to the surface of the
glass which is being worked. The temperature of the flame is so high
that it melts the most resistant glass."
The lines with which Kunckel concludes his description of the
blowpipe are interesting.
"Also many possibilities are concealed in this art; in a chemist's
workshop, for example, it might prove to be very useful. For
example one use would be to melt a metal-lime in order to see what
metal it contains; there are many other possible uses. It is necessary
only to place the lime to be analysed into a hollow in a small piece of
charcoal and to blow the flame onto it for a very short time" [ 7 5 ] .
Stahl was the first to report the effect of a tubulo caementario
aurifabrorum on antimony and lead-lime (oxide) [ 7 6 ] . Johann Cramer
(1710—1777) in his work with the blowpipe used charcoal to ignite
on, but he also investigated borax smelt. His blowpipe was made of
copper and incorporated a small ball-like widening to collect the
condensation from the breath during blowing [ 7 7 ] . Marggraf makes
several references to it. On the addition of phosphoric acid to gold,
the precipitate formed easily became an opaque glass when heated
with a blowpipe. With reference to silver phosphate, "it yielded a
dark glass with the help of the blowpipe", and on adding soda to it,
"the crystallised salts with a blowpipe do not burst, but behave like
borax" [ 7 8 ] .
90
Johann Pott (1692—1777) was commissioned by the King of
Prussia to establish the composition of Meissen porcelain, which was
so profitable to his Saxon neighbour. Although he carried out more
than thirty thousand experiments, he never discovered the secret of
the porcelain, but his work was not in vain. An account of his investi-
gations published in 1746 [ 7 9 ] , together with two subsequent
accounts, contained much interesting information on the behaviour
of different minerals when heated and on the value of the blowpipe
to analysts. Oxygen was first used in blowpipe procedures by Achard
in 1779 (according to Lampadius) and Lavoisier and Meusnier [80]
also used an oxygen flame in 1782.
Bergman, who was the greatest analyst of the 18th century, pub-
lished, in 1779, a book entitled De tubo feruminatorio which con-
tained all the existing knowledge on the use of this instrument
(Fig. 10). He notes that the method is quick, requires little sample
and no furnace. He made the first reference to the difference
between quantitative and qualitative analysis in saying that quantita-
tive estimation is not possible with a blowpipe [ 8 1 ] . He used a
candle or vegetable oil burner for the flame and substances such as
sodium ammonium phosphate, sodium carbonate, and borax as
ταΊΓ
Fig. 1 0 . B l o w p i p e and its accessories in the s e c o n d half o f t h e 1 8 t h century.

(From Bergman, D e Tubo Feruminatorio, 1779.)

fusing agents. As well as charcoal, he used small silver or gold plates
on which to fuse his samples. Bergman's assistant, Gahn, refined the
technique, discovering the cobalt-pearl test [82] and introducing the
use of a platinum wire. Towards the end of his life, he worked with
Berzelius who records that Gahn was very skilful in the use of the
blowpipe [ 8 3 ] . When Ekeberg gave Gahn a sample of tantalum,
which he had just discovered, the latter detected the presence of tin,
although it did not exceed 1%. He also detected copper in a quarter
of a sheet of filter paper, although it had not previously been
thought that copper was a constituent of vegetable substances.
Berzelius did a great deal to popularise the blowpipe with his
book, published in 1820, Afhandeling om Blasrôrets Anwàndande i
Kemien och Mineralogien, although it contained little new informa-
tion.
Since the last half of the 19th century, the blowpipe has gradually
fallen into disuse, partly due to the improvement of wet methods of
analysis, but mainly due to the emergence of emission spectroscopy,
which is far more accurate and depends less on the skill of the
operator.
(C) F U R T H E R LIGHT O N R E A C T I O N S IN S O L U T I O N
Although the reactions of metal + acid had been used from a very
early period, those of metal + alkali were not properly investigated
until the beginning of the phlogiston period. The term alkali covered
a wide range of substances; in one text it referred to carbonate and in
another to hydroxide. Stahl had observed that iron hydroxide dis-
solved in a large excess of alkali [ 8 4 ] , but it was Sigismund Andreas
Marggraf (Fig. 11) who systematically examined the behaviour of
many different metals when treated with various alkalis [ 8 5 ] .
Born in 1704, the son of an apothecary, he studied and worked in
many parts of what is now Germany. In 1748, he went to the
laboratory of the mathematical physics department of the Berlin
Academy, becoming its director in 1767. He worked there until his
death in 1782. He was a solitary man who lived only for his work.
Distillation in a closed system, which is used for the extraction of
zinc, was the discovery of Marggraf, as was the process for extracting
sugar from sugar beet.
It was during his studies of metals in alkaline solution that he
examined the reactions of "alkali ignited with cattle blood", which
92
F i g . 1 1 . S i g i s m u n d A n d r e a s Marggraf ( 1 7 0 9 — 1 7 8 2 ) . ( F r o m B u g g e , D a s B u c h d e r
grossen Chemiker. )
is, in fact, potassium hexacyanoferrate(IV) [ 8 6 ] . This compound

first appeared in the form of Prussian blue around 1709. It is not
certain who discovered it, possibly a paint-maker named Diesbach,
who obtained from a merchant some potash, which gave a blue paint
instead of the expected red one. On investigation, it appeared that
the potash had been ignited with cattle blood [ 8 7 ] . It was not until
1728 that Woodward, in England, recorded the method of its
manufacture [ 8 8 ] . Marggrafs method of preparation was to heat to
incandesence a mixture of one part potassium carbonate and two
parts of dried blood. After cooling, the mixture was dissolved in a
little water, filtered and washed. He noted that gold and silver gave

precipitates with this reagent which then redissolved in the excess,
the precipitate of gold dissolving more rapidly than that of silver.
Mercury behaves similarly [ 8 9 ] .
Marggraf used Prussian blue to test for iron in lime salts, which he
separated by fractional crystallisation in his examination of water
[90].
"It is well known that Prussian blue owes its colour to iron. No
doubt it is possible to detect the presence of iron particles in lime
earths extracted from water by treating them with an alkaline solu-
tion of potash made incandescent with cattle blood" [ 9 1 ] .
He ignited potassium carbonate with lime salt, heated the precipi-
tate with sulphuric acid for one hour, by which time the acid had
extracted the iron and, after allowing the vessel to stand for another
hour, he filtered the solution. To this was added, drop by drop, a
large quantity of potassium hexacyanoferrate(IV) solution. This
separated the iron as a blue precipitate. He went on to detect iron in
limestone fluorite, human skull, coral, and the bile stone of an ox,
among other things. He failed to detect it in whale tooth, pearl, deer
antlers, egg shell, or the carapace of lobsters [ 9 2 ] .
Marggraf was the first person to produce phosphoric acid. He
found that 1 oz. of phosphorus increased its weight by 35 drachms
when burnt. The product easily absorbed moisture from the air and
with water formed a sulphuric acid-like oil [ 9 3 ] . He examined the
effect of phosphoric acid on different metals and its reactions with
various metal salt solutions.
Another important discovery made by Marggraf is that there is a
difference between vegetable and mineral alkalis. During his investi-
gation of rock salt to establish whether the alkali part is derived from
alkaline earths [ 9 4 ] , he made some interesting observations. First, he
removed the chloride with nitric acid and examined the resulting
sodium nitrate. He found that, although it was similar to saltpetre
( K N 0 3 ) in some respects, it was not the same. Firstly, the shape of
the crystals formed by evaporation was different and secondly, he
records that when placed on glowing coal "the flame of the former
( N a N 0 3 ) is yellow, while that of the latter (KNO3) is bluish" [ 9 5 ] .
This is the earliest reported application of a flame test to analysis. He
confirmed this experiment by converting the nitrates to sulphates,
chlorides, and carbonates and in each case a noticeable difference in
the two salts was observed.
Winterl first carried out the chemical separation of potassium and
94
sodium using tartaric acid, which forms the insoluble bitartrate with
potassium [ 9 6 ] . He also separated magnesium from iron by keeping
the iron in solution with Seignette salt and precipitating magnesium
as the hydroxide [ 9 7 ] . He was able to separate calcium from
magnesium using tartaric acid. That iron is not precipitated by alkalis
in the presence of many organic acids, including oxalic, tartaric, and
amber acid, was mentioned by Wenzel in 1777 before Winterl's meth-
od was published [ 9 8 ] . All these organic acids were first prepared by
Scheele who used oxalic acid for the separation of calcium.
Marggraf applied the microscope to analysis and used it to establish
that beet-sugar and cane sugar are the same [ 9 9 ] . He also used it to
examine the ores of the then little known metal, platinum [ 1 0 0 ] .
The work of Marggraf was invaluable to the progress of analytical
chemistry; it provided a wealth of new methods and experimental
facts and justified his reputation as one of the greatest analysts of all
time.
Numerous other discoveries were made which were later to be
applied to analytical chemistry. The most notable of these was due
to Black who observed the difference between strong and weak
alkalis, i.e. between the alkali carbonates and hydroxides.
Joseph Black (Fig. 12) was born in Bordeaux in 1728, the eighth
child of a rich Scottish wine merchant. At the age of 12, he went to
school in Belfast and afterwards studied medicine at the University
of Glasgow, continuing his studies at Edinburgh. A year after sub-
mitting his famous doctoral thesis, he was awarded the Professorship
of Chemistry at the University of Glasgow. After ten years, he took a
similar post at Edinburgh where he worked until two years before
his death in 1799.
Basing his examination of alkalis on the tests of Hoffmann, Black
showed that magnesium carbonate and limestone were two different
substances. Although both substances effervesce when treated with
acids, the shapes of their crystals are quite different. Magnesium car-
bonate does not form common lime when heated strongly. On
cooling, the residue (oxide) is insoluble in water but forms the same
salts as the original carbonate with acids, although without effer-
vescence. Observing that, during ignition, "air (carbon dioxide) is
lost, he supposed this to be responsible for the loss in weight and
effervescence with acids. To confirm this, he dissolved the magnesium
oxide in sulphuric acid and precipitated the magnesium with sodium
carbonate. The precipitate was found to be identical to the original

Fig. 1 2 . J o s e p h Black ( 1 7 2 8 — 1 7 9 9 ) . ( F r o m Bugge, D a s B u c h der grossen Chemi-
ker.)
magnesium carbonate and the change in weight very small. He con-

cluded that alkali carbonates were not elemental substances because
they give "air" to the magnesium oxide and this same "air" is
responsible for the effervescence with acids. Applying similar experi-
ments to lime and limestone, he established that the air which leaves
the carbonates is not identical to atmospheric air and is only a com-
ponent of it. Black called this "fixed air" and it is the part of air
which is absorbed by lime and the alkali hydroxides. Therefore, the
relationship between the alkalis and fixed air is similar to that
between alkalis and acids, in that the former are "in some measure
96
neutralised" by the fixed air. However, the relation between acids
and alkalis is stronger as the acid drives out the fixed air. Accordingly,
the weak alkalis (carbonates) contain strong alkalis (hydroxides) and
their corrosive properties result from their original form, which is
lost after taking up the fixed air. The affinity of lime for fixed air is
greater than its affinity for water, as limestone is precipitated by the
action of fixed air on an aqueous lime solution. He also observed that
the decrease in weight on heating limestone to drive out the fixed
air was equivalent to the weight of acid which was neutralised by the
corrosive alkali formed [ 1 0 1 ] .
Black was fiercely attacked, especially as his theory disproved the
existence of the so-called "fire-substance" in lime. He later expressed
appreciation for the work of Jacquin [ 1 0 2 ] , a teacher at the
Selmecbanya Academy who repeated Black's experiments and con-
firmed his findings.
These experiments introduced the art of gas analysis and, in this
field, some of the most important discoveries of the period were
made.
(D) GAS ANALYSIS
Many other gases apart from air are to be found in nature. Erup-
tions of natural gas were observed from very early times and the
dangers of fire-damp in mines was soon realised. Pliny refers to air
which cannot be breathed and which is inflammable [ 1 0 3 ] . Alchem-
ists often observed the evolution of gases during their experiments
and referred to them as spiritus, a term which also included acids.
They supposed these gases to be air and paid little attention to them.
Van Helmont, who first used the word gas, noted that carbon
dioxide, "gas sylvestre", is formed during the burning of oak coal,
given off when carbonate is treated with acid, and during fermenta-
tion [ 1 0 4 ] . However, the gas formed from the combustion of
sulphur and the nitrous fumes from the dissolution of silver in nitric
acid he also called "gas sylvestre" [ 1 0 5 ] .
Toricelli determined the weight of air in 1643. Boyle (and,
independently, Mariotte in France) examined the relation between
the volume of air and its pressure, also establishing that combustion
requires air. (This had already been noted by several earlier workers.)
Boyle studied the formation of hydrogen and devised a way of con-
taining it. He placed some iron nails in a narrow-necked flask of
sulphuric acid, covered the flask with a vessel filled with water and

Fig. 1 3 . Hales' gasometer. ( F r o m his b o o k , V e g e t a b l e Staticks, 1 7 2 7 . )
collected the bubbles which were evolved [ 1 0 6 ] . In spite of this he

did not believe that gases were essentially different from air.
Hales constructed the earliest form of the gas-collection apparatus
in use today (Fig. 13) [ 1 0 7 ] , The advantage of this apparatus was
that gas, evolved by the action of heat on a substance, could be
isolated. He measured the amount of gas obtained from a certain
weight of substance, although the quantitative aspect was rather
spoiled as he used water as the confining liquid. He succeeded in
isolating many gases but did not identify any of them, believing them
all to be air.
The greatest contributors in the field of gas analysis, Cavendish,
Priestley, and Scheele, all worked at about the same time, around
1770, and often discovered the same things independently of one
another. Their work formed the basis of the new chemical theory,
but they were so steeped in the traditions of the phlogiston theory
that they could not draw the necessary conclusions from their dis-
coveries and it was left to Lavoisier to incorporate them into his anti-
phlogiston theory. Indeed, all three opposed him and did not change
their views in their lifetimes.
98
These three great scientists resemble one another in that none of
them was engaged in chemistry as a profession, only as a pastime.
Scheele was a pharmacist, Priestley was a preacher, and Cavendish an
extremely rich member of the aristocracy. Instead of giving an
account of their discoveries, it is proposed to examine their experi-
mental methods, as these are their main contributions to the progress
of analytical chemistry.
Henry Cavendish (1731—1810) (Fig. 14) was born into one of the
most ancient aristocratic families and was even related to Royalty.
Fig. 1 4 . Henry Cavendish ( 1 7 3 1 — 1 8 1 0 ) . His o w n caricature drawing. (From

Bugge, Das B u c h der grossen Chemiker. )

He studied at Cambridge, though did not pass any examinations. He
dealt with problems in all branches of natural science, from
astronomy to chemistry. He lived in London, but was a lonely and
solitary man who seldom mixed in society. He opened his large
library to the public and then insisted on having a borrowing ticket,
as everyone else had. He was also very reluctant to publish his results.
As a result of parsimonious economy, he left one million pounds to
his delighted heirs. Cavendish was said to be the most scholarly of
the rich and the richest scholar.
Generally regarded as the discoverer of hydrogen, his most impor-
tant work was Experiments on Air published in 1784. He was also
the first to measure the densities of gases. This experiment was
carried out by filling bladders with the gas and weighing them.
Assuming the density of air to be unity, he found the density of car-
bon dioxide to be 1.57 and that of hydrogen to be 0.09 [ 1 0 8 ] .
Cavendish discovered that if air is passed several times over heated
charcoal and then through a solution of potassium hydroxide, an air-
like substance remains which is lighter than air and will not support
combustion. He called this "phlogisticated air". Cavendish only com-
municated his discovery in a letter to Priestley, so that Daniel
Rutherford [109] (who carried out the same experiment) was able to
announce the discovery of nitrogen first. He also discovered nitrous
oxide and its property of reacting with oxygen to form nitrogen
oxide which, when dissolved in water, gives nitric acid. This reaction
he used in establishing the composition of air and for this purpose he
constructed a eudiometer [ 1 1 0 ] . After carrying out four hundred
experiments at different localities and in varying weather conditions,
he concluded that the atmosphere contains 20.84% dephlogisticated
air (oxygen).
By passing an electric spark through a mixture of air and hydrogen
Cavendish was able to observe the formation of water, proving that it
was not a primary element. Later, he repeated the experiment using
pure oxygen and hydrogen in the correct proportions [111] (Fig. 15).
Cavendish devised an experiment to determine whether or not all
the nitrogen in the air could be converted into nitric air (nitric oxide).
He passed a spark discharge through a mixture of air and oxygen
until no further decrease in volume was apparent. The excess oxygen
was then removed with "hepar sulfuris". The residual volume of gas
occupied only about a one hundred and twentieth part of the original
volume of the nitrogen. He concluded that nitrogen was not an
100
Fig. 1 5 . Cavendish's gas e x p l o s i o n p i p e t t e . ( P h o t o g r a p h in t h e G e r m a n M u s e u m
in Munich. )
homogeneous substance. This fact was overlooked for a hundred

years until Rayleigh, in 1894, repeated Cavendish's experiment with
the same result [ 1 1 2 ] . This led to the discovery of the inert gases.
Joseph Priestley (1733—1804) (Fig. 16), the son of a poor weaver,
was orphaned at an early age. Largely self-taught, he became a
student at theological college where it became apparent that he had a
gift for languages, being able to speak nine. However, what should
have been a successful career became a succession of posts from
secretary to a rich aristocrat to pastor at a very poor village dissenter's
chapel. This was due to his passionate and outspoken manner which
led him to criticise the Church of England, the educational system,
the aristocracy and the English form of government.
In 1767, he was elected to membership of the Royal Society due
to the success of his book The History of Electricity. Later, while in
the service of Lord Shelburne, he visited France where he met
Lavoisier. He confided in him his discovery of "dephlogisticated air"

Fig. 1 6 . J o s e p h Priestley ( 1 7 3 3 — 1 8 0 4 ) . Painting b y Gilbert Stewart.
which Lavoisier later published as his own discovery. This brought a

violent protest from Priestley. It was at this time, from 1770 to 1780
that he did most of his work in chemistry. The results of his research
were published in six volumes entitled Experiments and Observations
on Different Kinds of Air.
In the course of this work, Priestley prepared oxygen by heating
mercury oxide or saltpetre using a lens to focus the sun's rays. By the
ingenious idea of using mercury instead of water as the confining
liquid in Hale's collection apparatus, he was able to discover hydro-
102
gen chloride, ammonia, nitric oxide, silicon tetrafluoride, sulphur
dioxide, and carbon monoxide. He also examined the properties of
these gases but, although he was a brilliant practical chemist, the
theoretical possibilities opened up by his discoveries often eluded
him. However, in his description of the preparation of oxygen, he
does weite, "This series of acts, relating to air extracted, seems very
extraordinary and important and, in able hands, may lead to con-
siderable discoveries" [ 1 1 3 ] .
When the French Revolution broke out, Priestley sympathised
with the Revolutionaries, had his house burnt by the Birmingham
mob, and subsequently emigrated to America at the age of sixty-one.
He lived out his life on a small farm beside the Susquehannah river,
writing essays on theological and social subjects.
F i g . 1 7 . Carl W i l h e l m S c h e e l e ( 1 7 4 2 - 1 7 8 6 ) .

Carl Wilhelm Scheele (1742—1786) (Fig. 17) became apprenticed
to an apothecary in Gothenburg at the age of 15. He avidly read
chemistry books and carried out experiments in his spare time,
keeping detailed records as he did so. After working as apothecary's
assistant in many parts of Sweden, it was in Uppsala that he met
Bergman. Scheele's employer noted the reddish-brown gas which was
evolved when saltpetre was treated with acetic acid. He inquired
from Gahn, then a young chemist under Bergman, who in turn asked
Bergman, but all were mystified. It was Scheele who suggested that it
was nitrous acid, a relative of nitric acid. Bergman was impressed and
the two worked together. Scheele began to publish his results and at
the age of 33, still an apothecary's assistant, he was elected a member
of the Swedish Academy of Sciences. In 1775, he became apothecary
in Kôping where he resisted offers of better posts saying, "I cannot
eat more than enough, and I earn enough for me to eat here in
Kôping". He died in 1786, only 43 years of age.
F i g . 1 8 . A s e t f o r gas a n a l y s i s a c c o r d i n g t o B e r g m a n . ( F r o m h i s b o o k , O p u s c u l a
Physica et Chimica, 1 7 7 9 . )
104
Amongst Scheele's great contributions were those in organic chem-
istry, which he originated. He prepared many organic acids, including
oxalic acid, which he employed as a reagent for calcium [ 1 1 4 ] , He
also discovered molybdenum [ 1 1 5 ] , tungsten [ 1 1 6 ] , manganese
[ 1 1 7 ] , and barium [ 1 1 8 ] . He discovered oxygen, hydrogen, and
nitrogen independently of his English colleagues and also analysed
air. He prepared chlorine from manganese dioxide and hydrochloric
acid and investigated its properties [ 1 1 9 ] . He isolated silicofluoric
acid from fluorospar and proved that it was composed of silica, the
acid of fluorospar, and alkali [ 1 2 0 ] .
Other workers in the field of gas analysis include Winterl and
Ôsterreicher. In their book Analyses Aquarum Budensium (1781),
they give methods for the determination of oxygen, hydrogen
sulphide, sulphur dioxide, carbon dioxide, and nitrogen dissolved in
water. All are chemical, not gasometric methods. For example, car-
bon dioxide is determined with lime water, hydrogen sulphide by
passing the gas through a solution of a silver salt, and oxygen by
treatment with ferrous sulphate solution.
Gas analysis methods did not improve very much until the time of
Bunsen (Fig. 18).
(E) T O R B E R N BERGMAN
Chemical analysis at this time was not a separate branch of chem-

istry. Processes such as filtration, washing, evaporation, etc. were
never described as a whole, only as they occurred in some specific
investigation. Only methods for the examination of noble metals and
water were described as a single subject. There was a great need for
all the existing methods to be classified so that some form of refer-
ence would be available. In the works of Torbern Bergman, we find
the earliest form of analytical textbook, in that they give a
methodical summary of the processes of analytical chemistry
grouped according to the nature of the substance analysed, although
they are primarily a record of his own research. Chemical analysis
had been practised for two thousand years before Bergman, but it
was he who gave it the status of a separate branch of science —
analytical chemistry.
Torbern Bergman (Fig. 19) was born in 1735 in the territory of
Westgotland in Sweden. He studied law, in accordance with his
father's wishes, at the University of Uppsala. Out of interest, how-

Fig. 1 9 . Torbern B e r g m a n ( 1 7 3 5 — 1 7 8 4 ) . A picture in t h e University Library o f
Uppsala.
ever, he also attended lectures in the faculty of medicine. As a result

of the extreme mental effort he became ill. When recovered he
studied medicine and mathematics and in 1761 became assistant
professor in mathematics. In 1767, the chair of chemistry became
vacant and such was his reputation that he was given it without pub-
lishing a single chemical paper. During the next sixteen years, his
research, mainly in analytical chemistry, filled five large volumes and
he soon became the leading authority on chemistry throughout
106
Europe. His students included Gahn, Gadolin, and the Spanish
d'Elhuyar brothers. His health, which had never been good, became
worse until in 1784 he died at Medev, the spa where he had gone for
convalescence.
In his first book, De Analyst Aquarum [ 1 2 1 ] , he deals comprehen-
sively with water analysis, suggesting two procedures. It can either be
tested in solution with a reagent or examined by fractional crystal-
lisation after evaporation. He goes on to define reagents as "sub-
stances which, when added to the solution, show the presence of
foreign substances by changing the colour or purity of it immediately,
or after a very short time" [ 1 2 2 ] . He lists the known reagents of that
time and some of these are given below.
Litmus. Sensitivity, 1 gr. concentrated sulphuric acid turns
172.300 gr. blue litmus solution red [ 1 2 3 ] .
Alkali phlogisticatum [potassium hexacyanoferrate(II)]. Dissolve
2 gr. iron sulphate in 1 cantharus of water; one drop of the reagent
should give the Prussian-blue colour. The reagent also gives a red
precipitate with copper and a white precipitate with manganese.
Oleum vitrioli (sulphuric acid). Diluted, with barium (terra
ponderosa) it gives a white precipitate. With waters containing car-
bonates it begins to effervesce.
Acidum sacchari (oxalic acid). The most sensitive reagent for the
detection of lime. 1 gr. lime in one cantharus of water gives a slightly
cloudy precipitate with one drop of the reagent.
Alkali volatile (ammonium hydroxide). Metals are precipitated
with this reagent. Of the earths, only magnesium, barium and
calcium do not precipitate (strontium was still unknown). Also
copper is not precipitated, but gives a blue colour.
Soap. If free acid is present, it combines with the alkali of the soap
and the fatty oil separates out. If either metal or earth bases are
present when soap is added, a precipitate separates [ 1 2 4 ] , Waters of
this type are called hard waters and are not good either for washing
or for cooking vegetables. Soap is better used as a solution in alcohol
than in water. One drop of a solution which contains 8 gr. alum,
magnesia, or lime salt per cantharus will give a turbidity with an
alcoholic soap solution.
Alcohol. Added in sufficient quantity, it will precipitate the salts
which are dissolved in the water, such as sulphates, nitrates, and
chlorides.
The first step in Bergman's water analysis is the isolation of the

volatile components [125]. The dissolved gases are boiled out into a
mercury-filled gas collecting apparatus. Shaking the gas with lime
water absorbs any carbon dioxide. Hydrogen sulphide is recognised
by its smell and its ability to colour litmus solution red.
To separate the heterogeneous components, some water must be
evaporated until its density has increased considerably [126]. Firstly,
carbonic acid lime separates out from its abundant carbonic acid
content. (Thus Bergman noted the difference between carbonates
and bicarbonates). Then silicic acid and calcium sulphate precipitate
out and, more slowly, the water-soluble salts in the reverse order of
their solubilities. The residue is then weighed and its components
separated with different solvents. Firstly, the salts should be digested
for a few hours in one finger's breadth of aléohol and then filtered.
The insoluble portion is treated with an eightfold volume of water
and again filtered. This residue is boiled with a fourfold volume of
water, filtered and the residue treated with cold acetic acid to dis-
solve the calcium and magnesium carbonates. The solid portion is
then extracted with hot acetic acid to dissolve lime and magnesium.
This hot solution is first treated with sulphuric acid to remove
calcium and then with alkali carbonate to separate magnesium. Any
insoluble portion remaining after these treatments is iron oxide, clay
earth, or siliceous earth. The first can be recognised by its colour, the
second can be dissolved in hydrochloric acid, while silicic acid can be
identified by a blowpipe examination.
The alcholic solution from above can contain calcium and
magnesium chlorides. This must be evaporated and the two salts
separated as described previously. Iron, if present, can be revealed
with the Prussian blue reaction.
After fractional crystallisation of the aqueous solutions, the frac-
tions are examined by their crystal shapes and their reaction with
certain reagents. The metallic salt and alkali content are easily identi-
fied but neutral salts are more difficult. Sulphuric acid removes the
salts of nitric acid, which can be identified by their smell, colour and
explosiveness when heated. Salts of hydrochloric acid can be identi-
fied by treating with silver nitrate solution, salts of sulphuric acid by
treating with lead or barium salts, but the salts of the two kinds of
alkali can only be distinguished by their crystal shapes.
Bergman concludes by recording the characteristic crystal shapes,
solubility, and the percentage composition of a great many crystal-
line compounds.
108
In the introduction to De Minerarum Docimasia Humida, pub-
lished in 1780, Bergman states "In the following I have tried to dis-
close methods which make the analysis of minerals possible by wet
methods alone, without having to resort to fusion", adding that
"generally wet methods, although they take longer to perform, give
more accurate and reliable results" [ 1 2 7 ] .
He goes on to give practical instructions for the analysis. The
mineral must be ground to a fine powder, the solvent must be puri-
fied as much as possible, dilute acids should be used and all precipita-
tions should be carried out in glass vessels. After precipitation, he
describes décantation, washing, filtration, drying, and finally
weighing the precipitate, not forgetting to subtract the weight of the
paper [ 1 2 8 ] .
In another section of this work, Bergman deals with specific ores,
describing the analysis of gold, silver, platinum, mercury, lead,
copper, iron, tin, bismuth, nickel, arsenic, cobalt, zinc, antimony,
and manganese ores. As an example, we shall look at the analysis of
lead in more detail [ 1 2 9 ] .
He states that lead occurs mainly in sulphuric ores which are
usually contaminated with silver, iron, or antimony. The ore can be
dissolved in nitric acid, when the sulphur separates out. This must be
filtered off, dried, and weighed. Its purity can be determined by dis-
solving it in a base. Lead is precipitated from the filtrate with soda. If
only lead is present and the weight of the precipitate is a, then the
quantity of metallic lead is (100/132)a. If silver is also present, it will
be precipitated with the lead and it must be extracted with ammonia.
If, after drying and reweighing the precipitate, the decrease in weight
equals 6, then the weight of silver present is (100/129)&. If the ore
also contains antimony, it is dissolved in concentrated sulphuric acid,
the acid taking up the phlogiston of the antimony and the antimony-
lime separating out. If, after filtration and drying, the weight of the
precipitate is c, then the amount of antimony present is (100/138)c.
If iron is present, the analysis is more difficult. After dissolution
in hydrochloric acid, most of the lead is precipitated. This precipi-
tate dissolves in a large volume of water, precipitating antimony.
After filtration, iron plates must be placed in the filtrate to displace
lead and silver. When this has also been filtered off, the iron is precip-
itated from the filtrate, either with soda or in the form of Prussian
blue. By reweighing the iron plates, the amount of iron dissolved
from them can be taken into account when calculating the result.

ιοο put. Plumbi alk. min aêrtro deder. 131
cauftico
vitriolaro 116
phlogiftic.
Cupri - - aërato *43
cauftico
phlogiftic. 194
Ferri - - aërtto 5
22
30
cauftico S
phlogiftic. 170
Stanni · - aërato 590
cauftico 131
phlogiftic. 130
Fifmuti - · aërato 250
cauftico 130
phlogiftic. 180
aqua pura 113
Niccoli · - aërato 135
cauftico 128
phlogiftic. 250
Arfemci- - aërato
cauftico
phlogiftic 180
Cobalti - · aërato 160
cauftico 140
phlogiftic. 142
Zinci - - aërato
cauftico 161
phlogiftic. 495
Antimonii - aërato 140
cauftico 138
phlogiftic. 138
Fig. 2 0 . Table o f equivalent weights. ( F r o m Bergman, D e Praecipitatis Metallicis,
1779.)
In his De praecipitatis Metallicis, Bergman discusses solvents for

metals, précipitants and their efficiencies and the properties of
precipitates [ 1 3 0 ] (Fig. 20). A few extracts from this work are given
below.
"Solvents. Nitric acid dissolves most metals with the exception of
gold and platinum. Sulphuric acid is not as effective as nitric acid,
silver and mercury for example only dissolve slowly. Hydrochloric
acid is a much less effective solvent than nitric and sulphuric acids,
but if it is dephlogisticated (chlorine removed), it attacks all metals
most vigorously. The other acids, hydrogen fluoride, arsenic acid and
110
the organic acids have much weaker dissolving powers.
The following are classed as alkalis: the caustic alkalis, namely
the hydroxides, the fixed alkalis, i.e. the alkali carbonates, the volatile
alkalis, i.e. ammonia, and the phlogisticated alkali, i.e. potassium
hexacyanoferrate(II).
Mercury, lead, and silver can be precipitated from nitric acid solu-
tion with hydrochloric acid. Tin and antimony are precipitated by
nitric acid because it takes away their phlogiston. Metals can displace
other metals from solutions of their salts and in this a certain
sequence is to be found. The order is zinc, iron, lead, tin, copper,
silver, and mercury; zinc will displace iron and so on." He remarks
that this sequence depends on the solvent [ 1 3 1 ] .
He also records in this book the colour of various metal precipi-
tates.
In another article, Bergman mentions that manganese can be
precipitated with oxalic acid in neutral solution [ 1 3 2 ] . He recognised
the different coloured manganese oxides and attributed this to the
varying phlogiston contents [ 1 3 3 ] . He also investigated the different
types of iron and concluded that their differing properties were
caused by differences in their composition, giving the following data.
Silicic acid Plumbago (graphite)

(%) (%)
Ferrum crudum (cast iron) 1.0 - 3 . 4 1.0 - 3 . 3

Ferrum cusum (wrought iron) 0.05-0.3 0.05-0.2
Chalybis (steel) 0.3 - 0 . 9 0.2 - 0 . 8
It is clear from these extracts from the work of Torbern Bergman

that he contributed as much as anyone to the development of analyt-
ical chemistry.
(F) QUANTITATIVE ANALYSIS BEFORE LAVOISIER
The time of Lavoisier has been called the age of quantitative chem-
istry. Although it is indisputable that the principle of conservation of
mass, the atomic theory of Dalton, and the new rules governing
stoichiometry heralded a new era in chemical history, these dis-
coveries did not arise out of nothing, but rather followed the work of
the preceding generation of scientists.

The French chemist Lémery (1645—1715) was the first to provide
quantitative results in his work. He found, for example, that when
1 oz. of silver was dissolved in nitric acid and then precipitated with
rock salt, the weight of filtered and dried precipitate was 1 oz. and
3 drachms (theoretical yield = 1 oz. and 2.6 drachms of silver chlo-
ride). He also established that 12.5 oz. of mercury can be obtained
from l i b . of cinnabar [ 1 3 4 ] . It should be noted that 1 oz. =
8 drachms = 480 gr. = 25—35 g (the weight of one gram varied in
different countries and often in different towns).
Kunckel, who lived at about the same time as Lémery, also carried
out many quantitative experiments. He found that 20 gr. of copper
would separate 60 gr. of silver from a silver solution (theoretical =
65 gr.). He precipitated silver in the form of silver chloride and ob-
tained 16 parts of white silver lime from 12 parts of silver treated
with rock salt (theoretical = 15.95 parts). It can be seen that
KunekePs work was remarkably accurate [ 1 3 5 ] .
Marggraf was the first to propose that the determination of silver
as silver chloride was more convenient than the very involved fire
test.
"Silver must be precipitated from nitric acid-^silver solution with
rock salt solution which is added until the solution is no longer
turbid. The solution should stand overnight and the clear liquid
removed next day. Next the precipitate must be washed and dried.
From 2 oz. of silver, 2 oz. 5 drachms and 4 gr. of precipitate are ob-
tained. The increase in weight originates from the acid of the rock
salt, consequently one oz. of this precipitate contains 6 drachms and
a few gr. of pure silver. If the silver is not quite pure, the precipitate
will have a smaller weight, because with this method only the silver
separates, so the copper remains in solution" [ 1 3 6 ] .
Bergman gives the quantitative composition of numerous crystal-
line salts obtained by aqueous procedures but gives no details of his
methods or record of his weighings; for example, his figures for alkali
vegetabile vitriolatum (potassium sulphate), with actual values in
parentheses [137] are 52 parts alkali (54.05 K 2 0 ) , 40 parts sulphuric
acid (45.95 S 0 3 ) , and 8 parts crystal water (0.0).
He remarks that "at a temperature of 15°, 1 part of salt dissolves
in 16 parts of water. Its taste is rather bitter. It melts with difficulty
and does not disintegrate on heating, but breaks up on vigorous
heating."
In his work De praecipitatis Metallicis, Bergman compiled a table
112
TABLE 2
A comparison of the analyses of Wenzel and Bergman
Compound Composition
Wenzel Bergman Theoretical
N a 2S 0 4 cryst. base 19.5 15 19.2

acid 24.3 27 25.0
water 55.2 58 55.8
M g S 0 4 cry st. base 16.9 19 16.3

acid 30.6 33 32.6
water 52.5 48 51.1
K 2S 0 4
base 54.8 52 54.05
acid 45.2 40 45.95
water 8
which gives the number of parts of dried precipitate that is equivalent

to 100 parts of pure metal for a variety of précipitants [ 1 3 8 ] . His
results were sometimes completely wrong, but such was his standing
in chemistry that these were accepted for quite a long time.
In 1777, Carl Friedrich Wenzel (1740—1793) published his book
Lehre von der Verwandschaft, which contained accurate research
work on the composition of about two hundred different kinds of
salt but, because he was quite unknown, where his results differed
from those of Bergman, they were simply ignored. It was not until
after his death that Berzelius examined his results and was amazed
at their accuracy (see Table 2). The following is an example of his
calculations.
To 240 gr. of sulphuric acid solution (which contained 75.75 gr.
"most acidic", namely concentrated), Wenzel added 120 gr. of mag-
nesium carbonate. 20 gr. of this were insoluble, therefore 100 gr.
must have reacted. He evaporated the solution in a vessel of known
weight and dried and weighed the residue, which weighed 247 gr.
Wenzel ignited 240 gr. of magnesium carbonate and found that
140 gr. of fixed air ( C 0 2 ) were given off. Therefore 100 gr. of mag-
nesium carbonate are equivalent to 43.67 gr. of earth. Consequently,
in the 247 gr. of salt there are 43.67 gr. of earth (base) and 75.75
of acid, the remainder being water [ 1 3 9 ] . It can be seen from
Table 2 that the result is very close to the exact composition of mag-
nesium sulphate.

Black, Cavendish, and others carried out some very accurate
quantitative work in the field of gas analysis. They established the
composition of air, the density of gases and the quantity of carbon
dioxide evolved from carbonates.
Although it can be seen that from about the middle of the 18th
century quantitative procedures were in widespread use, it was in the
time of Lavoisier that there was a great improvement in their scope
and nature.
(G) INDESTRUCTIBILITY OF M A T T E R
The principle of the indestructibility of matter was to become one

of the basic rules in chemistry after the work of Lavoisier. However,
as early as 500 B.C., Anaxagoras wrote "Nothing comes into being
and nothing disappears, everything is only the arrangement of such
things, which existed before". Democritus (ca. 420 B.C.) and
Aristotle (384—322 B.C.) also held this view. Lucianus of Samosta, a
Roman satirist (125—180 A.D.), tells how a sarcastic questioner
asked Demonax the philosopher "If I burn a hundred pounds of
wood, tell me please, how many pounds of smoke leaves?" To this
the philospher replied "Weigh the ash; what is missing, was the
smoke" [ 1 4 0 ] .
This idea was abandoned during the Middle Ages to be reborn in
the age of the Renaissance. Telesio (1508—1588), an Italian philoso-
pher, proclaimed that "The substance can neither be increased nor
decreased" [ 1 4 1 ] . Francis Bacon in 1620 wrote "Nothing is pro-
duced of nothing and nothing is reduced to nothing" [ 1 4 2 ] . Hooke
in 1765 [143] stated that matter and the kinetic quantum were con-
stant in their entirety and that their quantity may neither increase
nor decrease. Lomonosov wrote the following to Euler in 1748: "In
nature every change occurs so that if something is added to a system
then it must have been lost from another system in the same degree.
Consequently, a body must give up that substance by the same
amount" [ 1 4 4 ] .
Mihail Vasilievich Lomonosov (1711—1765) was born into a fairly
prosperous peasant family in Northern Russia near the shores of the
Arctic Ocean. After the considerable achievement of learning to read
and write, he studied in Moscow.
"All that I could afford to spend on food was half a kopek for
bread and half a kopek for kvas. I lived in this manner for five years,
114
while studying the sciences" [ 1 4 5 ] .
After studying in Europe, he became a lecturer and then Professor
of Chemistry in 1745 at the Academy in Moscow. He campaigned
for the founding of the first Russian University which is now named
after him. A poet, historian, sociologist, factory manager, and natural
scientist, his strenuous life led to his early death at the age of 54.
Besides the principle of the indestructibility of matter, he also
investigated the phenomenon of combustion, preceding the work of
Lavoisier. Repeating Boyle's experiment in which the weight of lead
increases if it is burnt in a closed vessel, Lomonosov comments
"From my experiments I have concluded that the view of the
famous Mr. Boyle is wrong, because if air from outside is not allowed
to enter then the weight of the substance after combustion remains
unchanged" [146] (1756).
In fairness to Boyle, he does state that the lead was heated for
two hours on coals in a "small retort with a long neck, wherein was
afterwards left but an orifice not much bigger than a pin's head"
[ 6 9 6 ] . The hole was then sealed and the vessel heated for a further
two hours. Boyle seems to have believed this to be sufficient to
exclude air. On weighing, 4 oz. of lead had increased in weight by
more than 13 gr.
When Lavoisier repeated this experiment twenty years later, a
radical change was brought about in chemical thought by the intro-
duction of the theory of combustion. Had he devoted his time
entirely to chemistry, Lomonosov might have seen the significance of
his work and provided a new chemical theory many years before its
actual formulation. This was left to Antoine Laurent Lavoisier
(1743—1794), one of the greatest scientists in history.
Lavoisier (Fig. 21) was a man of contrasts. His position in society
was as brilliant as the one he occupied in science. He was very rich,
his own inherited wealth being supplemented by the fortune of his
beautiful and intelligent wife. At the age of twenty-five, he was made
a member of the Academy. He was also a director of tobacco and
cordite manufacturing companies and the leader of the anti-phlogiston
school of chemical thought. However, he was very desirous of glory
and was not ashamed to appropriate the discoveries of others and
announce them as his own. His vanity often made him look ridicu-
lous. In 1789, he devised a mock trial of the phlogiston theory
before a large and distinguished audience, the outcome of which was
the ceremonial burning of Stahl's book. His brilliant career came to a

Fig. 2 1 . A n t o i n e Laurent Lavoisier ( 1 7 4 3 — 1 7 9 4 ) . Copper engraving, 1 7 9 0 .
sudden end with the French Revolution. He was called to account

for his position as chief tax-tenant and executed by guillotine in
1794 at the age of 51.
Lavoisier repeated many of the experiments of the earlier
phlogiston chemists. He decomposed water in a manner similar to
that of Cavendish, prepared oxygen after Priestley and Bayen [147]
and also carried out Boyle's experiment previously referred to on the
combustion of metal in a closed system. However, it is the conclu-
sion which he draws from these experiments not the experiments
themselves that make him famous. He first clarified the combustion
process. He established that oxygen is needed for burning and that,
when non-metallic elements are burnt, an acidic product is formed
and metallic elements give a basic product. He also made the first
116
clear distinction between elements and compounds and explained the
process of dissolving metals in acids. Other important aspects of
Lavoisier's work concern general chemistry and cannot be dealt with
here.
The principle of indestructibility of matter, which he first postu-
lated in 1789, is considered the greatest of his achievements. Lavoisier
himself did not think that this theory was revolutionary, but rather a
natural and well-known established fact. He writes about the fermen-
tation of must that
must = alcohol + carbon dioxide
"because nothing is created, neither in natural nor in artificial pro-
cesses and we can announce it as a principle that the quantity of the
substance is the same before and after all operations, only changes
and transformations are going on" [ 1 4 8 ] .
Lavoisier looked at the question of stoichiometry, the nature of
the numerical proportion which was apparent in chemical processes.
"The reacting and formed substances can be expressed in algebraic
equations, and if one member of these is missing it can be calculated"
[149].
However, he did not proceed any further with this problem and
much more work was necessary to establish the laws of stoichiome-
try.
Lavoisier is possibly best remembered for his banishment of
phlogiston. However, at the time, he was attacked by many people,
particularly outside France, and it was only with the passage of time
that they accepted the irrefutable logic and proofs which the new
theory supplied.
(H) STOICHIOMETRY
Stoichiometry, namely that part of chemistry dealing with the

quantitative relationship between the composition and formation of
compounds, could only develop when the concept of compounds
was made clear. During the period of iatrochemistry, salt formation
was discovered from the reaction of acid and alkali; neutralisation
being called "saturation". Helmont recorded that silicic acid when
dissolved in a base is precipitated by saturating the base with nitric
acid [ 1 5 0 ] . Boerhave had previously referred to the saturation point;
by adding acid to a base, a point is eventually reached where the
basic character just ceases.

Romberg, in 1699, added different acids to the same quantity of
potassium carbonate until effervescence ceased. He recorded the
amount of acid required and measured the increase in weight of the
crystallised salt [ 1 5 1 ] . His results, however, were incorrect, showing
almost the same weight in each case. He therefore concluded that the
acids differed only in their water content, being effectively the same
substance.
In 1767, Cavendish stated that a given quantity of alkali carbonate
was equivalent to a certain quantity of lime because both neutralise
the same quantity of acid [ 1 5 2 ] .
Wenzel, the most accurate analyst of this period, writes
"That all compounds must have definite and unchangeable compo-
sition which can neither be smaller nor larger, otherwise that nothing
certain could be established from their comparison is self-evident"
[153].
Consequently, Wenzel was postulating the law of constant propor-
tions but this was the limit of his speculation. Some historians attrib-
ute more to Wenzel than is his due. Walden [154] calculated the
values of equivalent weight and atomic weight for various metals
from WenzeFs results and concluded by suggesting that Wenzel was
the original discoverer of the significance of these weights. These
values can be calculated from his results only because we can calcu-
late stoichiometrically and because Wenzel's data are correct. Wenzel
himself did not draw any general conclusion from his analytical
results.
It was Jeremias Benjamin Richter (1762—1807) (Fig. 22) who
recognised the significance of the law of neutrality and established
the basic rules of stoichiometry.
Born in Silesia, he became an architect and served seven years in
the army in the corps of engineers. Objecting to the discipline, he
went to Kônigsberg to study mathematics and philosophy. Kant, one
of his lecturers, said of science "In the single branches of natural
science, real science is only as much as the amount of mathematics
that is in them". Richter went on to title his Ph.D. thesis, De Usu
Matheseos in Chemia (The Use of Mathematics in Chemistry). He
lived in poverty for much of his life, working in all his spare time
with that feverish activity peculiar to consumptives who feel that the
rhythm of life is quicker than themselves. Although his circumstances
improved, his health deteriorated and he died at the age of 45,
without the recognition which his work merited.
118
Fig. 2 2 . Jeremias B e n j a m i n R i c h t e r ( 1 7 6 2 — 1 8 0 7 ) . ( F r o m Bugge, Das B u c h der
grossen Chemiker. )
It was Richter who introduced the word "stoichiometry"

"Because the mathematical part of chemistry is constituted mainly
by such bodies, which are indivisible substances or elements, and,
because this science discusses the volume-proportions between them,
I could not find a shorter and more appropriate name for it than the
word "Stôchyometria", from the Greek oroLxetoy, which means
something like indivisible and μeτoeιy, which means the search for
volume proportions . . ." [ 1 5 5 ] ,
Anfangsgrunde der Stochyometrie (1793) is possibly Richter's
most important work. In the introduction he gives this mathematical
advice to chemists.
"If a number is added to another number then the mark + (which

is called plus) must be placed between them, whereas if we want to
subtract them, then we apply the mark — (which is called minus).
For example, 19 + 424 means that we add 19 to 424, that is 443;
and 424 — 1 9 means that we count back 19 from 424, that is 4 0 5 "
[156].
Either his opinion of their ability is very poor or they really were
in need of some mathematical instruction.
In the section on pure stoichiometry he postulates the idea of con-
stant proportions.
". . . if we form a compound from two elements then, because the
properties of the elements remain the same, one will always require
the same amount of the other, so for example if to dissolve 2 parts of
lime requires 5 parts of hydrochloric acid then 6 parts of lime will
require 15 parts of hydrochloric acid" [ 1 5 7 ] .
This is followed by his neutrality law.
"If two neutral solutions are mixed with one another, and double
decomposition occurs between them, then the products which are
formed will also be neutral, almost without exception . . . The basis
of this phenomenon is that the elements must have a definite volume-
relation between one another."
He goes on to say that if mass proportions of two compounds AB
and CD are known, then they will be known for their products on
double decomposition AC and BD [ 1 5 8 ] . He develops this in Vols. 2
and 3 of his work Applied Stoichiometry. Volume 1 of this work is*
best ignored as it contains artificial or supposed relations between
density, mass number and affinity, etc. It has contributed to Vols. 2
and 3 being seldom read. An example of his calculations is given
below.
"From 2400 gr. of C a C 0 3 , 1342 gr. of CaO are formed, conse-
quently C a C 0 3 : CaO = 1000 : 559; to saturate 5760 gr. of hydro-
chloric acid, 2393 gr. of C a C 0 3 were required, and after evaporation
and ignition of the salt formed it was weighed and found to be
2544 gr. Therefore HCI : C a C 0 3 = 5760 : 2393, and because CaO =
CaC0 3 X 559/1000, we can write that HCI : CaO = 5760 : 2392 X
559/1000 = 5760 : 1337. Consequently, this 1337 gr. is the earth in
the salt which was formed. Subtracting this from the salt obtained
(2544 gr.) then the acid part is 2544 —1337 = 1207 gr. Therefore
the proportion of the earth and acid in the salt is [159]
1207 : 1337 = 1000 : 1107
HCI CaO HCI CaO
120
59
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Stôchyometrie, 1792.)
Figure 23 shows the first entirely quantitative reaction equations

encountered in the history of chemistry. Taking as an example No. 2,
top left is barium, top right, HC1, bottom left, magnesium and
bottom right sulphate. Schwererden-Salz = barium chloride, Bitter-
Salz = magnesium sulphate, Magnesien-Salz = magnesium chloride,
and Schwer-Spath = barium sulphate.
TABLE 3
T h e first t a b l e o f e q u i v a l e n t w e i g h t s a c c o r d i n g t o F i s c h e r
Bases Acids
a
Magnesia 615 (411) Sulphuric acid 1000
a
Ammonia 672 (665) Hydrochloric acid 712 (714)
Lime 793 (572) Carbonic acid 577 (632)
Sodium hydroxide 853 (816) Phosphoric acid 979 (975)
Potassium hydroxide 1605 (1152) Nitric acid 1405 (1285)
Barite 2222 (2380) Oxalic acid 755 (897)
Citric acid 1683 (1303)
Present values calculated o n H 2S 0 4 = 1 0 0 are g i v e n i n p a r e n t h e s e s .

Most contemporary readers became lost in the mass of com-
plicated calculations and conflicting statements in Richter's works. It
was left to the keen brains of Dalton and Berzelius to realise their
true significance and develop his basic ideas further.
A chemist named Fischer drew up a table (Table 3) based on
Richter's data and included it in his translation of Berthollet's book
on affinity [ 1 6 0 ] , Berthollet included it in his work Essai de Statique
Chymique [ 1 6 1 ] . Although this book contradicted all the theories of
stoichiometry proposed by Richter, it assisted in spreading his views
and was read by Dalton.
Fig. 2 4 . Claude L o u i s B e r t h o l l e t ( 1 7 4 8 — 1 8 2 2 ) . D r a w i n g b y Wolf.
122
Claude Louis Berthollet ( 1 7 4 8 - 1 8 2 2 ) (Fig. 24), the famous
French chemist, unexpectedly entered the discussion with the
opposite theory that when two elements formed a compound, the
composition could vary between a maximum and minimum for all
proportions. Although this theory, if correct, would have destroyed
the whole theoretical basis of quantitative analysis, Berthollet's
eloquent and inspired reasoning caused many chemists to support
him. He was also aided by the unreliable analytical results of his day
and an ambiguous distinction between elements, compounds, and
alloys.
Joseph Louis Proust (1755—1826) disagreed with Berthollet on
the basis of his work with metal oxides and sulphides. Proust was
first to realise that if two elements form more than one compound
with one another then their proportions change in definite stages, so
that the compounds have a definite composition and no product of
intermediate composition can exist. He reported his results in terms
of per cent of element sought, e.g. with tin oxides
Tin (II) oxide Tin (IV) oxide
Tin (%) 88.1 78.4

Oxygen (%) 11.9 21.6
If he had calculated his results to show how much of one element

combined with the same amount of the other element in each case,
he would have obtained the values
Tin (II) oxide Tin (IV) oxide
Tin (%) 100 100

Oxygen (%) 13.5 27.5
This law of multiple proportions, which Proust had come very

near to establishing, was eventually discovered by Dalton from the
results of similar experiments with the oxides of carbon and nitrogen.
John Dalton (Fig. 25) was born in 1766 in Eaglesfield, Cumber-
land, the son of a poor handloom weaver. At the age of 12, he

Fig. 2 5 . J o h n D a l t o n ( 1 7 6 6 — 1 8 4 4 ) . Painting b y Lonsdale.
became a teacher at the village school and went to become a princi-

ple at a Quaker school in Kendal at about the age of 19. In 1793, he
moved to New College, Manchester, but left after 6 years to devote
more time to research. Remaining unmarried, he made daily observa-
tions of the temperature, pressure, and rainfall from the age of 15
until the day before his death. In physics, he discovered the law of
partial pressures of gases and, in medicine, studied the phenomenon
of colour blindness now named after him (daltonism). He reluctantly
became a Fellow of the Royal Society in 1822. He received many
distinctions including a pension of £ 300 per year from the Govern-
ment. He died in 1844.
124
The beginnings of his atomic theory came in a lecture given in
Manchester in 1803 when, on the subject of the absorption of gases
in water, he referred to the influence of atomic weights [ 1 6 2 ] . It was
not until 1808 with the publication of his book, A New System of
Chemical Philosophy, that he gave a detailed account. There was, at
the time, some controversy over the originator of the atomic theory.
Davy, while giving credit to Dalton, thought that William Higgins
(1762/3—1825), an Irish chemist, may have prior claim due to his
book A Comparative View of the Phlogistic and Antiphlogistic
Theories, published by J. Murray in London in 1789, in which he
deduced molecular formulae for water, the oxides of nitrogen and
sulphur and the composition of hydrogen sulphide, and he clearly
recognised the law of multiple proportions. His molecular diagrams
were probably superior to Dalton's, and seventy years before Kekulés.
However, "Higgins does not stand on the same level as Dalton"
[697].
The view that matter consists of minute indivisible particles did
not originate with Dalton. Many Greek philosophers, as well as
physicists and chemists from Democritus to Boyle, Descartes, and
Richter, held this view. Even Dalton's idea that the smallest parts of
the same element have the same weight and form was not original.
However, the essence of his theory was the idea that compounds are
formed from the uniting of whole atoms and that the weights of
different atoms can be expressed by numbers. On the basis of this,
the composition of chemical compounds can be expressed quanti-
TABLE 4
Dalton's table of atomic weights
Chemical element Atomic Chemical element Atomic

weight weight
Hydrogen 1 Stronician 46
Nitrogen 5 Barita 68
Carbon 5 Iron 38
Oxygen 7 Zinc 56
Sulphur 13 Copper 56
Magnesium 20 Lead 95
Lime 23 Silver 100
Soda 28 Platina 100
Potash 42 Mercury 167

tatively. He described his work as being to determine the relative
weights of the components of substances. He took hydrogen as 1 and
made all other atomic weights proportional to this (see Table 4). In
this table, the alkali and earth metals refer to the oxide. However,
the weakness of Dalton's atomic weights was their inaccuracy [ 1 6 3 ] .
This often happened in the progress of analytical chemistry and was
why the understanding of the basic rules of stoichiometry took so
long. The good analysts did not provide theories to explain their
work, while the good theoretical chemists did not assist the spread of
their views owing to their poor results. Eventually, one man appeared
who was outstanding in the fields of both theory and practice. This
man was Berzelius.
3. The period of Berzelius
(A) THE COMPOSITION OF MINERALS
A rapid development of mineralogy occurred between the years

1790 and 1810 which led to a large amount of analytical information
becoming available. During this time, the quantitative composition of
a large number of minerals and naturally occurring salts was estab-
lished with a fair degree of accuracy. Two chemists, Kirwan and
Klaproth, although only slightly more illustrious than most of their
contemporaries, give a good impression of the methods of analysis of
those days.
Richard Kirwan was born at Cloghballymore, Ireland, in 1733. As
a second son, he was destined for a profession, in his case that of a
priest. He studied at Poitiers, France, and developed an interest in
chemistry. In 1754, he went to Paris to enter the Jesuit noviciate and
a year later, he returned to Ireland to look after the estates on the
death of his brother in a duel. He then married Anne, daughter of the
Dowager Lady Blake and next day found himself in prison for her
debts. Richard lived happily with his wife, although the litigation to
recover his wife's fortune continued until after his death. He worked
at chemistry until Lady Blake persuaded him to take up law but
during his law studies, his wife died leaving a distressed Richard and
two daughters. He returned to science in 1769 spending that year
and the period 1777—1779 in London. The latter were fertile years
in his research. Although a supporter of the phlogiston theory for
most of his life, he was converted by William Higgins, a fellow
126
countryman. He was a member of the Royal Society, was awarded
the Copley Medal in 1782 and served as President of the Royal Irish
Academy. He died in 1812.
There was little in Kirwan's work which was new but the results of
his analyses were extremely accurate. His work An Essay on the
Analysis of Mineral Waters (D. Bremner, London, 1799) was out-
standing, mainly because of its comprehensive list of references.
Describing compounds found in water he remarks
"Aerated lime is itself soluble in an excess of fixed air ( C 0 2 ) , as
Mr. Cavendish first discovered, and here two questions arise impor-
tant to subsequent calculations, namely what quantity of aerated
lime can be held in solution by a given volume of water fully
aerated . . ." (p. 17).
The second part of his book is classified according to the different
compounds with a test for the identification of each one. For
example, he writes of carbon monoxide
"Heavy inflammable air or carbonated hydrogen. This air is
distinguished by the fact that it burns without explosion when mixed
with common air. It is not absorbed by lime-water, but water over
which it is burned precipitates lime-water, as fixed air is produced"
(p. 42).
Kirwan also carried out interference studies (p. 136) and gives
examples of salts which interfere with each other, e.g. alkali car-
bonates and metal salts, alkali sulphates and alkaline earth salts, and
magnesium sulphate and calcium nitrate or chloride. The reasons for
classifying some of these salt pairs as interfering are not very clear.
He suggests a simple procedure for the determination of the total
salt content of water by measuring specific gravity (p. 145). He also
mentions the need for a systematic approach to analysis.
"The usual method of applying tests is similar to that of sending
out adventurers to an unknown country to see what discoveries they
can make, hence that indications are vague and unconnected.
Whereas if t h e y were limited to some particular object, and so com-
bined and arranged to prove or disprove its existence, their indica-
tions might be rendered certain and precise and such information I
have already shown them capable of conveying, when employed with
single and definite views", (p. 162).
Kirwan's analytical work was famous in its time and his results
were cited all over Europe. However, at the turn of the 18th century,
another great chemist, Klaproth, played an even greater part than

Kirwan. There were few books of this period which did not refer to
some aspect of Klaproth's work.
Martin Heinrich Klaproth ( 1 7 4 3 - 1 8 1 7 ) (Fig. 26) was the son of a
provincial tailor. He became an apothecary's assistant at the age of
15 and after several changes of position, he went to work for
Valentin Rose in Berlin in 1771. Rose died only four weeks after
Klaproth joined him, entrusting to him the education of his children
and the direction of his pharmacy which was faithfully carried out.
In 1780, he married a niece of Marggraf and used her large dowry to
Fig. 2 6 . Martin Heinrich K l a p r o t h ( 1 7 4 3 — 1 8 1 7 ) . ( F r o m Bugge, D a s B u c h der

grossen Chemiker.)
128
purchase his own laboratory for mineral analysis. In 1809, he was
made first Professor of Chemistry at the new University of Berlin. In
his later years, he had many domestic troubles and was subject to
fits of apoplexy. He died on New Year's Day, 1817.
Although he lived in the same period as the great phlogiston
chemists, he repeated Lavoisier's experiments and became the first
important German chemist to openly accept his anti-phlogiston
theory. He had complete faith in his experiments and mere supposi-
tion did not interest him. He rarely took part in the heated debates
which were going on in chemical society at that time. When Antal
Ruprecht, Professor at the Selmecbanya Mining Academy, obtained
metals from alkaline earth oxides, hitherto considered to be ele-
mental substances, Klaproth decided to repeat his experiments. He
proved that the metals formed did not come from the earths but
from the contaminants in the chemicals. He concluded that the
simple earths did not contain metals. Consequently, when Davy
reduced the earths to metals using an electric current, Klaproth did
not believe him. It often happened that the older scientist, ingrained
in the old concepts, refused to accept new developments. It was said
of Klaproth that "He was an incorruptibly accurate researcher, but
was lacking only in ingenuity or intuitive thought" [ 1 6 4 ] .
His main discoveries were the three new elements, uranium,
zirconium, and cerium, although he also examined the previously
discovered titanium, strontium, and tellurium in more detail. He
published his collective results in a series of volumes entitled Beitràge
zur Chemischen Kenntniss der Mineralkorper (1795—1815). In these
books, he gave detailed experimental procedures to enable repetition
by other chemists. As an example, this is his analysis of zoisite.
"Chemical test. The specific weight of the ore is 3300. When
heated on a carbon block with a blowpipe it shows a foam-like
effervescence, the colour of the ignited part becomes reddish and it is
transformed into a fine powder. During the course of ignition the
loss is insignificant. It does not dissolve in acids.
(a) 100 gr. of finely powdered mineral I ignited moderately with
200 gr. of potassium hydroxide in a silver vessel for 2 hours: I
extracted the greenish white mass with water which was oversatu-
rated with hydrochloric acid and then evaporated it to dryness. After
extracting the residue with water I filtered thé precipitated silicious
acid which, after ignition, weighed 44 gr.
(b) I precipitated the filtrate with corrosive ammonia (NH 4OH). I

dissolved the precipitate, which had previously been washed by
décantation, in warm potassium hydroxide. The iron oxide remained,
contaminated with a little manganese oxide; after ignition the
weight of this precipitate was 2.5 gr.
(c) I precipitated again the aluminous earth with sal ammoniac
(ammonium chloride) from the solution made alkaline with potassium
hydroxide. I filtered, washed and ignited it. Its weight was 32 gr.
(d) I decomposed the former filtrate by boiling with soda when
36.5 gr. of carbonic acid lime separated, which is equal to 20 gr. of
lime-earth" [ 1 6 5 ] .
Accordingly, the composition of the zoisite is
Silicious earth (a) 44

Aluminous earth (c) 32
Lime-earth (d) 20
Iron oxide (b) 2.5
Manganese oxide trace
98.5
If his results differed much from 100%, Klaproth looked for the
cause of divergence and in this way discovered new elements or un-
suspected components. When examining the mineral elucite, he
found a 21% discrepancy after determination of aluminium oxide
and silicon dioxide. He tested for borax, phosphoric acid, and other
less frequent components but detected nothing. The residue remaining
after separation was evaporated and crystallised. The crystals were
quadratic, did not affect litmus, and were unaffected by ammonia or
soda solution. However, the taste was similar to that of potassium
chloride, so he evaporated with sulphuric acid obtaining crystals of
potassium sulphate and with nitric acid he found potassium nitrate.
By this method, he established the presence of potassium in this
mineral [ 1 6 6 ] . Hitherto, this had been thought to occur only in
vegetables, hence its name alkali vegetabile (Pflanzenalkali). Klaproth
suggested a change of name to kali and for alkali minérale (Mineral-
alkali) he preferred natron [ 1 6 7 ] . These were not accepted in either
the French or English languages.
He was first to use silver vessels in the technique of alkali fusion
and platinum vessels in the fusion of soda [ 1 6 8 ] . An indication of
Klaproth's exactness can be judged from the fact that he analysed
the mortar he used for grinding and found it to be almost pure silica.
130
TABLE 5
Klaproth's analytical data
Precipitate weighed Metal equivalent

(gr)
According to Klaproth Theoretical
4 6 AgCl 34.5 34.6 Ag

93 PbS04 66 63.6 Pb
56 S b 20 4 46 4 4 . 3 Sb
12 F e 20 3 9 8.39 Fe
1000 AgCl 428.5 4 0 7 . 7 NaCl
100 SrC03 114 125.2 S r S 0 4
1000 BaS04 592.5 6 0 8 . 4 N a 2S 0 4
When he ground a sample, he would reweigh it and if there was an

increase in weight, he subtracted this figure from the amount of
silicic acid. He was also first to note that precipitates must be dried
or ignited to constant weight. In order to obtain the high tempera-
tures sometimes required, he used the furnaces of the porcelain
factory in Berlin.
Klaproth developed his own ideas on stoichiometry. At first, on
obtaining compounds such as silver chloride or antimony oxide in an
analysis he would reduce them to the metal and weigh it [ 1 6 9 ] .
After a while he realised that the ratios were constant and omitted the
reduction step. He records later that a certain weight of precipitate
corresponds to a definite weight of metal or oxide (Table 5) [170]
and even used these conversion factors for identification purposes.
An example of this is his proof that the mineral strontianite contains
strontium and not barium. After dissolution in hydrochloric acid, a
sample of 100 gr. of the mineral weighed only 70 gr., therefore 30 gr.
of carbon dioxide were evolved. Had the substance been barium car-
bonate, then only 22 gr. would have evolved. Also, 100 gr. of the
sample, when treated with sulphuric acid, formed 114 gr. of strontium
sulphate of which 2.5 gr. were soluble in 8 oz. of warm water. Barium
sulphate was not soluble in hot water.
He also changed the established methods of water analysis,
wherever possible omitting the separations based on fractional crys-
tallisation ". . . because that does not give a sure result. So I have
devised a more reliable method which first of all involves the satura-
tion of free mineral alkalis with acid, and then I decompose the

neutral salts which are formed with a suitable reagent: at the same
time I carry out a trial experiment in order to make the relationship
clear and on the basis of this I calculate the result" [ 1 7 1 ] . On analysis
of 1 cubic inch (290 gr.) of Karlsbad water, he obtained 39 gr. of
mineral alkali ( N a 2 C 0 3 ) , 34.625 gr. of rocksalt, 70.5 gr. of Glauber's
salt, 2.5 gr. of silicic acid and 2.5 gr. of iron.
Klaproth was one of the most thorough investigators in analytical
chemistry and his work was used by many of his contemporaries.
(B) B E R Z E L I U S
Berzelius was born at the time when Lavoisier's book Traité Elé-
mentaire de Chimie was published. By the time he had grown up,
the storm over the phlogiston theory had abated. However, Lavoisier's
friends and the first followers of the new method, Fourcroy,
Berthollet, Guyton de Morveau, etc., were not able to develop the
new chemistry constructively, so that the turn of the 18th century
was a period of stagnation in chemistry. Shortly after this, new
inspiration was given by Davy's discovery of the phenomenon of
galvanism and Dalton's atomic theory.
The development of a branch of science often needs someone with
a systematic mind who is able to summarise and correlate the experi-
ments and discoveries of others, using these to construct a theory.
Lavoisier, as we have seen, was such a man; so, also, was Berzelius.
Jons Jakob Berzelius (Fig. 27) was born on the 20th August 1779
in Wâfversunda in Sweden [ 1 7 2 ] . His father, a teacher, died of tuber-
culosis in 1783 and two years later, his mother married a widowed
pastor named Ekmarck who already had five children, so the family
numbered ten. When his mother died in 1787, he continued to live
with his kind stepfather. However, Ekmarck remarried in 1790. His
new wife contrived to send the Berzelius children to their uncle,
Lieutenant Sjosteen. Although he made no distinction between
Berzelius and his own children, those children and their mother
always made him feel unwelcome.
In 1793 he went to secondary school in Linkôping. During vaca-
tion, he became a private tutor to a landowner's children, living in a
room where potatoes were stored. Although heated, it was just
enough to stop the potatoes from freezing. Returning to school, he
developed an interest in botany, became an enthusiastic plant and
bird collector and learned to hunt. He was almost expelled from
132
Fig. 2 7 . Berzelius in his laboratory. ( F r o m his S e l b s t b i o g r a p h i s c h e n Aufzeich-
nungen. )
school when he came close to shooting someone. He left school in

1796 with the hope of becoming a physician and a final report which
read " . . . he possesses excellent talents but his morals are not good,
so his future prospects are uncertain". He enrolled in the medical
faculty at the University of Uppsala, interrupted his studies to earn
some money, but continued them on obtaining a scholarship.
He first studied chemistry in 1798 when he attended lectures, sat
an oral examination, and only passed because of good results in other
subjects. Next term, he carried out practical exercises under Afzelius,

who was Professor of Chemistry at that time. His first experiment,
the ignition of iron sulphate, was due to last a week but Berzelius
finished it in a few hours. When he asked for another exercise he was
reprimanded for being too impatient. He mentions how Afzelius
rarely attended practical classes with the result that his assistant
Ekeberg knew more than he did. However, Ekeberg was almost deaf
and the students took advantage of him. It was he who later dis-
covered tantalum. Berzelius took to doing exercises for his own
curiosity or repeating experiments in the literature, even working
after hours, all without permission. Afzelius, after discovering these
intrigues, said that he did not approve of hidden paths but he would
be happier for him to use the normal entrance which would always
be open. Berzelius relates, "he treated me from that time with extra-
ordinary good will and confidence".
His first published paper, in 1800, was an analysis of mineral water
from a health resort [ 1 7 3 ] . Three earlier papers dealing with nitrogen
oxide and "nitric acid naphtha" were not published because they
used the nomenclature proposed by Lavoisier. Berzelius published
these in 1807 in the Journal which he established.
After receiving his diploma in 1802, he became an unpaid assistant
in the School of Surgery, Stockholm, and invested his small capital in
a scheme for producing artificial mineral water with a man called
Werner with whom he lived. He made friends with a factory owner
called Hisinger and together they examined the effect of the Volta
column on various salts. They established that the combustible sub-
stances, alkalis, and earths migrated to the negative pole while oxygen,
acids, and oxidised products went to the positive pole. They con-
cluded that salts decompose to metal oxide and acid anhydride. They
published this in 1803 [ 1 7 4 ] . Although it contained much that was
in Davy's famous article three years later, his was more important
because of his proof that the alkalis were compounds and his ability
to isolate metals from them. Berzelius's article shows the formation
of the ideas which later led to his dualistic electrochemical theory.
While investigating feldspar with Hisinger, he discovered the oxide
of cerium. Unfortunately, when he sent this to be published, he was
informed that Klaproth had just discovered it [ 1 7 5 ] . As a protest
against the official journal of the Academy, he started his own, again
with Hisinger [ 1 7 6 ] . Meanwhile, needing an income, he became
official physician to the poor for 66 thalers a year. He also estab-
lished a factory, with Werner, for making vinegar. It failed, Werner
134
absconded to Russia, and Berzelius took ten years to clear his debts.
In 1807, he became Professor at the School of Surgery. The next
year, the first part of his Ldrbok i Kemien (Schoolbook of Chemistry)
was published and he was elected a member of the Swedish Academy
of Science. He also became a partner in another factory, for making
sulphuric acid and vinegar, which was very profitable until it was
burnt down in 1826 with great financial loss. In 1812, he travelled
to England and met Davy, Watt, Wollaston, and others.
At this time, he published prolifically, mostly on atomic weights.
In 1818, he was raised to the nobility, had a nervous breakdown
through overwork, and decided to travel for his health's sake. Trav-
elling in Europe, he met Gay-Lussac, Berthollet, Dulong, Ampère,
Chevreul, and many others, learning a great deal from them. In 1820,
he became Secretary to the Swedish Academy of Science, a position
which he held until his death. From 1821 onwards, he published his
famous Jahresbericht annually. He was now financially secure with
a great reputation and his electrochemical dualism had woven the
fabric of chemistry into an attractive and unified whole. He began to
work less, travelled a good deal to Europe, and was subject to severe
migraine attacks. He retired in 1832 only to be recalled as President
of the Public Health Committee when cholera swept Sweden.
Berzelius had never married, preferring to devote himself to
science. However, at the age of 56, in 1835, he married the 25-year-
old daughter of his old friend Poppius. The king honoured him with
the title of Baron to mark the occasion. He wrote to Liebig just
previously
"The life of a bachelor especially in old age is a lonely and un-
happy one and this situation can only be avoided by getting married.
My fiancée is much younger than I; she is in fact nearly 25 years of
age, but she is considerably more intelligent than most older women,
so I hope that this will compensate for at least one decade in our age
difference" [ 1 7 7 ] .
However, his youth had gone. He wrote in 1837
"Sometimes stimulating ideas occur to me, but now instead of
being fearful lest someone solves the problem before me, I prefer to
allow someone else to carry out the experiments" [ 1 7 8 ] .
Meanwhile, some flaws had appeared in the theories of Berzelius
and his last years were spent in arguments in the chemical journals
defending them. However, Liebig wrote to Wôhler
"Berzelius has been asleep while we have been working and the

reins have now passed out of his hands. Now he is awake, but when
an old lion whose teeth are not sharp roars not even a mouse is
afraid" [ 1 7 9 ] .
His health declined rapidly; he suffered from gout and apoplexy
and finally his legs became paralysed. Berzelius died in a wheelchair,
while reading, on 7th August 1848.
Berzelius's qualities were his tremendous capacity for hard work,
always working to a plan, and his unbelievable energy. He produced
no shining discoveries like Priestley or Davy, nor did he enunciate
efficient hypotheses like Stahl or Dalton. His hypotheses were devel-
oped slowly as the result of much hard work. His most important
theory, that of electrochemical dualism, reigned, was discarded, only
to enjoy a second life in Arrhenius's hypothesis. He writes of it
"Atoms contain both types of electricity, these being placed at
different poles in them, but one type is dominant. Affinity is due to
the electrical polarities of the particles. Thus, all compounds are
composed of two parts, differing in the nature of their electricity and
bound together by attraction. All compounds can therefore be
divided into two oppositely charged parts irrespective of the actual
number of elements from which the compound is composed. For
example, sodium sulphate is composed of sulphuric acid and alkali,
both of which are capable of further subdivision into an electroposi-
tive and electronegative constituent" [ 1 8 0 ] .
Of even greater importance was his determination of the atomic
weights of the elements which, considering the conditions under
which he worked, was no mean achievement. The few chemicals
which were available commercially were sulphuric acid, a few metals
and metal oxides, soda, sulphur, phosphorus, borax, ammonium
chloride, rock salt, extracts of various plants, and a few others.
Everything else had to be prepared from these. Until late in his life,
he had to buy all his own chemicals and apparatus and he never had
more than one or two students with him at one time. Wôhler," a
student in the years 1823—1824 describes Berzelius's laboratory.
"The laboratory consisted of two ordinary rooms . . . . There was
neither furnace, hood, water, nor gas in it. In one of the rooms there
were two ordinary pinewood tables; at one of these Berzelius worked,
while I worked at the other. On the walls there were a few shelves
with reagents on them and in the middle of the room there was a
glass-blowing table and a mercury vessel. In one corner there was a
washing place, consisting of a stone vessel with a tap and a pot where
136
Anne, the housekeeper, washed the dishes every morning. In the
other room there was a balance and a large cupboard containing
instruments. In the kitchen where Anne did the cooking there was a
small furnace, seldom used, and a sand-bath which was kept con-
tinuously heated. There was also a small workshop with a lathe"
[181].
Mitscherlich, Mosander, Heinrich and Gustav Rose, Wôhler, and
Magnus were some of the most famous of his students. Although he
received most of the social awards of that time, being visited by
kings, he remained modest, disliking flattery intensely. When Rose
asked if he might name a selenium-containing mineral "berzelite", he
wrote
"I am an enemy of the bad fashion coming from England that
minerals are named after living persons. All mineralogists introduce
their friends into mineralogy and as a result the most complicated
and stupid names are formed" [ 1 8 2 ] .
Berzelius had many literary achievements. As well as his textbook,
he wrote books on electrochemistry [ 1 8 3 ] , mineralogical systems
[ 1 8 4 ] , and the blowpipe [ 1 8 5 ] , His Jahresbericht appeared regularly
for 27 years and continued in Germany after his death until 1912.
He exchanged letters, most of which have been published, with Davy,
Berthollet, Dalton, and many of his students. The Swedish Literary
Academy elected him a member for his contributions to the develop-
ment of Swedish technical language. He wrote letters with a sense of
humour. Wôhler sent a sample of a mineral to him saying
"This substance, I have called x, was obtained from pyrochlor, and
is either tantalic acid, in which case tantalic acid has some hitherto
unknown properties, or alternatively it is the oxide of a new metal."
To which Berzelius sent the reply
"Here I return your substance χ. I interrogated him to the best of
my ability, but he gave me inconclusive replies. I first asked him,
'Are you titanium?' and he replied 'Wôhler has already told you that
I am not titanium!' T h e n are you zirconium?' I asked him. 'No' he
replied, 'because with soda I form a white glass, whereas zirconium
does not.' 'Perhaps then you are tin?' I asked him. 'There is little of
the character of tin in me' he replied. 'Surely then you are tantalum?'
I asked him but your χ replied, Ί am related to tantalum, but potas-
sium bisulphide slowly dissolves me and I am precipitated from this
solution to give a brownish yellow coloured precipitate!' who are
you then you son of a devil?' I asked him finally. Ί am afraid that I

do not have a name yet' he replied. I am not quite certain about this,
however, because he said it from my right hand and as you know I am
rather deaf in my right ear. Therefore, I am sending you back this
fellow. Your ears are better than mine; try to examine him once
more" [ 1 8 6 ] .
This was unnecessary, however, as Rose had, in the meanwhile,
discovered this element and named it niobium [ 1 8 7 ] .
Berzelius describes a visit he made as a young man to Davy in
London.
"The French butler showed me into the dining room, where the
breakfast table was already prepared. There I was left alone for a
time, apparently in order for me to admire the luxury of my sur-
roundings. The first impression I gained was one of a man who has
acquired great wealth and who has not yet adjusted his style of living
to suit his circumstances. The butler then opened the door and Sir
Humphry entered. This impression did not last very long for very
soon Sir Humphry relaxed and became a very interesting chemist,
called Davy . . . " [ 1 8 8 ] .
We have gone into the personality of Berzelius in some detail
because of the extraordinary role which he played in the progress
of analytical chemistry. Let the young Bunsen, however, have the
last word.
"When one gets to know him well it is difficult to know what to
admire most about him, whether his ingenuity, or his shyness, or his
good heart!" [ 1 8 9 ] .
(C) A T O M I C W E I G H T S
In 1807, while Berzelius was writing a textbook for students of

medicine, he consulted, amongst others, the works of Richter.
"Of the several not very well known books that I consulted, the
work of Richter was remarkable for the light which it shed on the
subject of the composition of salts and the precipitation of metals
and yet nobody has taken any advantage of it! On the basis of the
analytical results of Richter, it is obvious that from the composition
of some salts the composition of other salts can also be established"
[190].
He resolved to continue the work of Richter.
When Dalton published his atomic theory and his law of multiple
proportions, Berzelius already had results which supported this.
138
However, realising that Dalton's atomic numbers were not accurate
enough, he decided to determine these himself more accurately.
To do this, two quantities were needed, the number of atoms in
the compound and relative weights of the single atoms. Berzelius
used oxygen as a standard because the determination of atomic
weights was based mainly on the analysis of oxides. To oxygen, he
gave an atomic weight of 100 [ 1 9 1 ] . Some of his figures he gives
based on hydrogen, as this was common in England and elsewhere,
but he uses 2H = 1, so his results are half today's value. Determina-
tions of numbers of atoms in a compound were often incorrect and
Berzelius would alter his atomic weights in the light of new evidence.
Two important discoveries made about this time greatly assisted
him in this task. Mitscherlich noted that compounds which contain
the same number of atoms and have similar structures, exhibit similar
crystal forms (isomorphism) and Dulong and Petit [192] stated that
the product of atomic weight and specific heat for a metal is con-
stant.
Meanwhile, an English physician named Prout proposed that
atoms of different elements were composed of hydrogen atoms and,
consequently, their atomic weights must be a multiple of that of
hydrogen [ 1 9 3 ] . Among many supporters for this was Thomson,
who published some results which he claimed confirmed this theory
[ 1 9 4 ] . However, it was not difficult for Berzelius to disprove
Thomson's results by his own careful work. How could the unfortu-
nate Thomson know that the natural elements are mainly mixtures
of isotopes!
An example of Berzelius's methods of determining atomic weights
will illustrate the problems involved.
"Chlorine. I established its atomic weight by the following experi-
ments: (1) From the dry distillation of 100 parts of anhydrous potas-
sium chlorate, 38.15 parts of oxygen are given off and 60.85 parts of
potassium chloride remain behind (good agreement between the
results of four measurements). (2) From 100 parts of potassium chlo-
ride 192.4 parts of silver chloride can be obtained, (3) From 100 parts
of silver, 132.75 parts of silver chloride can be obtained. If we assume
that chloric acid is composed of 2C1 + 5 0 , then according to these
data 1 atom of chlorine is 221.36. If we calculate from the density
of chlorine determined by Lussac (5.4252), the atomic weight is
220. If it is calculated on the basis of hydrogen then it is 17.735"
[195].

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Fig. 2 8 . Pages from Berzelius's table o f a t o m i c weights. ( F r o m his L e h r b u c h der

Chemie. )
The first atomic weight table of Berzelius was published in 1814

[ 1 9 6 ] . The table illustrated in Fig. 28 is taken from a later German
issue [ 1 9 7 ] . These values mostly agree with those of the 1818
Swedish version, but contain many changes from the original table.
Its significance is that the atomic weights are calculated on the basis
of the double hydrogen atom. Those data are correct therefore,
which show half the present day values of atomic weights. These
large numbers of atomic weights reflect great credit on Berzelius,
who in ten years carried out work which would have been a major
accomplishment to a modern, well-equipped research laboratory.
During the first half of the last century, there was great confusion
over the values of atomic weights, some chemists accepting Berzelius's
figures and some using other values. Gerhardt's introduction of the
concept of equivalent weights only made the situation more involved,
the formula of water being variously given as H 2 0 , HO, or H 2 0 2 . As
the development of atomic weights is strictly beyond the scope of
this work, it will be sufficient to note that Cannizzaro unified the
conflicting concepts and values at the international congress held at
140
TABLE 6
A t o m i c weights of Berzelius
Element Atomic Element Atomic Element Atomic

weight weight weight
0 8.013 Mo 47.96 Fe 27.181

Ρ 15.717 Ti 24.332 Zr 33.67
F 9.367 Pa 53.359 Mg 12.689
Se 39.631 Cu 31.767 Li 6.44
V 68.58 Pb 103.729 S 16.20
Ta 92.448 Co 29.568 I 126.567
Ir 98.841 Th 59.646 Si 22.221
Hg 101.431 Al 12.716 Sb 64.662
Sn 58.91 Ba 68.663 Ag 108.305
Ni 29.622 Ν 7.093 Zn 32.311
Ce 46.051 Br 78.392 Y 32.254
Be 26.544 Β 21.828 Na 23.31
Sr 43.854 As 37.665 Cr 28.191
Κ 39.257 W 94.795 Os 99.722
2 H 1 Au 99.604 Bi 71.07
Cl 17.735 Rh 52.196 Mn 27.716
C 6.12 U 217.26 Ca 20.515
Fe 64.25 Cd 55.83
Karlsruhe in 1860. His proposals were widely accepted, the only

exceptions being the French chemists and even they eventually came
to accept Cannizzaro's views. It can be concluded therefore, that the
basis of atomic weights, chemical formulae and the development of
analytical calculations based on stoichiometry, can today be attrib-
uted to Berzelius.
(D) A P P A R A T U S A N D M E T H O D S A T THE TIME OF BERZELIUS
Berzelius gives a comprehensive description of chemical apparatus,

operations, and methods in the last volume (Vol. 10) of his textbook
[198].
Vessels and apparatus were mainly made of glass. Berzelius, him-
self a good glassblower, invented apparatus such as the test tube and
separating funnel. He used sand and water baths for evaporation and
oil baths were in common use. Clay crucibles, widely used previ-
ously, were little used at this time. The porcelain crucible was still

a rarity so the platinum crucible was used for the ignition of precipi-
tates. The latter were expensive; for example, a platinum crucible
made in London in 1821 weighing 3 oz. and 5.5 quentchen (about
110 g) cost £ 3.18.0 (£ 3.90).
Ignition was carried out in various types of furnace, usually with
charcoal as fuel. Flames could also be used for ignition and vegetable
oil or spirit used as fuel. Drying was difficult, being either carried out
on a water bath or in a desiccator-like vessel over sulphuric acid or
calcium chloride.
Berzelius specially ordered unsized paper from the mills for use as
filter paper. He specified that it must have long fibres and be manu-
factured in the winter and allowed to freeze while wet. The freezing
expanded the pores so that it filtered efficiently. For quantitative
work, Lessebo paper contained only 1.962 parts of ash per
1000 parts of paper. Berzelius analysed the ash and found it to be
60.39% S i 0 2 , 12.55% CaO, 9.8% MgO, 2.39% A 1 2 0 3 and 16.08%
6
5
Fig. 2 9 . Berzelius's l a b o r a t o r y e q u i p m e n t . 1, Beaker; 2, device for a u t o m a t i c
w a s h i n g o f p r e c i p i t a t e s ; 3 , c a p i l l a r y r e g u l a t o r o f d e v i c e 2 ; 4 , filter h o l d e r w i t h
filter f u n n e l ; 5, i g n i t i o n o f p r e c i p i t a t e s ; 6 , a u t o m a t i c f i l t r a t i o n a p p a r a t u s ; 7, o i l
burner. ( F r o m his L e h r b u c h der C h e m i e . )
142
F e 2 0 3 . He subtracted this as pure silicic acid. Filtration has changed
little since his day. Round filter paper folded as we do today, placed
in a glass funnel with a conical axis of 60° and the paper dampened
first with solvent. Correct filtration is shown in Fig. 29(4).
He also used conical glass tubes filled with asbestos which had
previously been purified with concentrated hydrochloric acid.
Beakers were similar to those in use today, but had no pouring spout.
A small amount of fat was placed on the rim where the solution was
poured out so that it could not run down the side of the beaker.
During filtration, the solution had to be directed down a glass rod.
The nearer the angle between the rod and the beaker approached a
right angle, the more secure was the transfer. Nordenskjôld designed
a pouring device which Berzelius used but which later fell into disuse.
Figure 29 (2, 3) shows an automatic device for washing.
The book contains a large section on balances (Fig. 30). The
Fig. 3 0 . Analytical balance o f Berzelius.

smallest weight he used was 5 mg, although he mentions that Pfaff's
balance was sensitive to 1 mg if the loading was 10 g [ 1 9 9 ] , Berzelius
was the first chemist to systematically use French measures, i.e. the
weights of the metric system. However, he does give conversion
factors for older weight systems. Using the grain as a unit of weight
had the disadvantage that different countries, and, indeed, different
cities within a country, assigned a different weight to the grain. It
varied from 52.4 mg in Venice to 72.9 mg in Austria-Hungary. He
advocated the use of an international weight system and, in 1841,
criticised the English chemists for their use of out-of-date measures.
The first reference to rubber tubing dates from about 1840, as
does the grinding of glass and the construction of glass-stoppered
bottles.
Discussing the accuracy of analytical determinations, he thought
an error of 1—1.5% for a complete analysis to be good but, for only
two or three components, it should be no greater than about 0.5%.
He devised a method for the determination of platinum metals and
attempted to produce a scheme of qualitative analysis, at least for a
limited number of metals. Berzelius's description of quantitative
analysis is detailed and contains little fundamentally new but rather
gives small improvements, such as using 1 g samples instead of
Klaproth's 5—10 g, so for reasons of space it shall be omitted.
(E) E A R L Y A N A L Y T I C A L T E X T B O O K S
Early chemical books from the 15th and 16th centuries gave
practical instructions such as the recipe for gunpowder or medicines.
An analytical observation in a 15th century book describes a test for
the purity of sulphur used in gunpowder. A handful of sulphur was
made into a ball in the hand and squeezed. If it gave a creaking
sound, the sulphur was pure. Fortunately, gold analyses in these
books tended to be taken more seriously and serious analytical
prescriptions are to be found in them. The first examples of truly
scientific chemical textbooks were published in the 17th century.
According to Neville [ 6 9 8 ] , the earliest was Practique de Chymie by
Sébastien Matte La Faveur published at Montpellier in 1671 and only
sold at the author's house, hence its rarity. Next came Lemery's
Cours de Chymie (Paris, 1675) [English edition A Course of Chemis-
try (London, 1 6 7 7 ) ] , Boerhave's Elementa chimiae (1732), and
Jacquin's Lehrbuch der allgemeinen Chemie (Vienna, 1783). The
144
first book, to our knowledge, to be devoted entirely to analytical
chemistry is Gôttling's book, Vollstandiges chemisches Probekabinett
(Jena, 1790). It deals mainly with the analyses of minerals and
metals. Vauquelin's book Manuel de VEsseyeur (1799) deals mainly
with noble metal analysis.
Lampadius's Handbuch zur Chemischen Analyse der Mineralkor-
per (1801) deals primarily with the analysis of minerals. However,
the style is similar to later books in that he gives a detailed list of
apparatus, analytical methods, and reagents. He gives the earliest
record of standard methods used for testing the purity of analytical
grade reagents and in many cases these are similar to present day
methods.
"Hydrochloric acid. 1. Heavy earth solution (Ba) should not cause
turbidity, i.e. sulphuric acid earths should not be precipitated. 2.
From potassium cyanide turbidity should not be caused. 3. On
neutralisation with potassium hydroxide it should remain clear. 4.
After evaporation on a glass plate no residue should remain."
In describing tests for the more important salts, he attempts to
identify the salt itself, not the cation or anion. He did not realise that
it was sufficient to examine the reactions of the metals and acids;
this only became apparent after the introduction of Berzelius's
dualistic theory.
The first really general and comprehensive textbook was written
by Pfaff and entitled, Handbuch der Analytischen Chemie fiir Che-
miker, Staatsarzte, Apotheker, Oekenomen und Bergwerks Kundige
(J.J. Hammrich, Altona, 1821). He begins this book with a discussion
on the use of reagents, which is long since, in most cases, the prepara-
tion is described. In those days, few reagents could be obtained
commercially. Sometimes there are circulos vitiosos to be found in
Pfaff's book, for example in the preparation of acetic acid he recom-
mends lead acetate, while lead acetate is to be prepared from acetic
acid [ 2 0 0 ] . After the preparation, he gives the composition of the
reagent and its atomic weight according to Berzelius and finally, the
uses and, in some cases, the sensitivity, defined as the amount of a
test substance required to give a perceptible change with the reagent.
He records new reagents such as hydrogen sulphide, ammonium
sulphide, iodine, chlorine water, tin chloride as well as platinum
chloride for precipitation of potassium and mercury(I) nitrate to test
for ammonia [ 2 0 1 ] . He also uses the latter reagent for the determina-
tion of chromate which he precipitates in the form of mercury(I)

chromate; then, after evaporation and volatilisation of the mercury,
he weighs the residual chromium trioxide.
In his section dealing with water, he mentions that the evapora-
tion—extraction method is inferior to the new method recommended
by Murray [ 2 0 2 ] , which consists of determining the main con-
stituents by the addition of various reagents without previous evapo-
ration.
Pfaff's methods for the examination of metals would be valid
today. For each metal, he gives a description of its appearance, its
specific weight, melting point, oxide formation, and behaviour under
the blowpipe. He then lists reactions of the metal in solution and
finally gives details for its quantitative determination, methods of
separation, and analysis of its ores.
The book concludes with several chapters dealing with the analysis
of gases and organic substances.
After Pfaff's book had been published, it became customary from
time to time for textbooks to be written which collected, summarised,
and critically reviewed the existing methods of analytical chemistry.
Before the first World War, German scientists led this field. The
famous analytical textbooks of Rose, Fresenius, Treadwell, Mohr,
and Beckurts, which were published in many editions and in several
languages, were the working textbooks of all analytical chemists.
These books will be considered in more detail in later sections.
4. Qualitative and gravimetric analysis
(A) INTRODUCTION OF SYSTEMATIC TESTS FOR THE IONS
Most of the reactions of qualitative analysis, with the exception of

those involving synthetic reagents, were discovered before 1800,
often during water analyses. Analysis of minerals, the most important
field at that time, usually involved a preliminary test using the blow-
pipe followed by a quantitative analysis. Often, from an examina-
tion of the crystal form, it was possible to tell which elements were
present. In the case of silicates, it was usual to determine silicic acid,
iron, aluminium, calcium, and magnesium. Tests for other elements
were only made if the results of these analyses did not approximate
to 100%. Anomalous behaviour during such tests revealed new ele-
ments such as chromium, beryllium, and tantalum. Errors were some-
146
times made even by the most celebrated chemists. Klaproth did not
recognise the presence of phosphate in the mineral wavelite because
he incorrectly identified the precipitated aluminium phosphate as
aluminium hydroxide. This error was later corrected by Fuchs [ 2 0 3 ] .
Most of the fusion methods were also known. Marggraf carried out
fusions with alkali carbonate, while Klaproth used alkali hydroxide
and Berzelius used hydrogen fluoride. Fusion with potassium hydro-
gen sulphate was first carried out by Heinrich Rose.
However, one important reagent, hydrogen sulphide, was used
only to a very limited extent. Boyle had used it as a qualitative test
for tin and lead in water but it fell into disuse and had to be redis-
covered later. Hoffmann gives an account in 1722 of a gas with a bad
smell being evolved from alkaline sulphur solutions on treatment with
acids [ 2 0 4 ] . Bergman's observation that hydrogen sulphide gives
precipitates with many metals was, surprisingly, only used for the
detection of hydrogen sulphide. For the detection of lead in wines,
Fourcroy and Hahnemann, almost at the same time, recommended
the use of this gas [ 2 0 5 ] . The earliest form of generator was devised
by the English chemist Griffin. This was later modified by the Dutch-
man, P.J. Kipp (1808—1864), the owner of a firm producing scien-
tific apparatus. The first Kipp's apparatus appeared in 1864 [ 2 0 6 ] ,
Although Fourcroy was first to realise that the compound contained
hydrogen and sulphur, it was Gay-Lussac who gave hydrogen sulphide
its prominent place in analytical chemistry [ 2 0 7 ] .
Gay-Lussac first prepared iron sulphide by igniting a mixture of
iron filings and sulphur and by treating this with acid he produced
the gas. He noted that the effect of this reagent is dependent on the
acid strength of the medium, some metals being precipitated from
strongly acid solution, while others were only precipitated from
weakly acid solution. He also discovered that hydrogen sulphide can
reduce certain metals in their highest oxidation state, precipitating
sulphur in the process. He made another interesting point, namely
that metals which cannot be precipitated from strongly acid media
are precipitated if potassium acetate is added to the solution because
"by the effect of this the metal is transformed into an acetic acid
compound". This is the earliest application of the buffer principle.
When new elements were discovered, although their reactions were
examined, they were generally not used as reagents. Bromine and
iodine were exceptions to this rule and soon found important
applications mainly in volumetric analysis. Iodine was discovered by

Bernard Courtois (1777—1838) or, to be more accurate, by his cat. It
is said that his cat once pushed over a vessel containing seaweed. This
mixed with something that had been spilt on the floor and violet
vapours appeared. The characteristics, compounds, and reactions of
iodine were described by Gay-Lussac in a famous paper often cited as
an excellent example of chemical drafting [ 2 0 8 ] . The blue colour of
the iodine—starch reaction was discovered by Stromeyer in 1815
[ 2 0 9 ] . This was only used at first for the testing of iodine or starch
and did not acquire its important role as an indicator in iodometric
titrations until twenty-five years later.
Bromine was discovered by Balard in 1825. Testing for iodine in
the ashes of sea plants, he added chlorine water to it and observed
that, above the blue layer of iodine—starch, there was an intense
yellow layer. After distillation, he obtained the red liquid, bromine
[210].
Fig. 3 1 . Marsh's device for arsenic testing, 1 8 3 6 .
148
Marsh published his test for arsenic in 1836 (Fig. 31 shows his first
apparatus) [ 2 1 1 ] . In it, arsenic is reduced to hydrogen arsenide with
sulphuric acid and zinc. Thompson soon discovered that the test is
not specific and that antimony gives the same reaction [ 2 1 2 ] . Marsh
himself tried to distinguish between the two elements. He placed a
drop of water on the piece of porcelain on which the spot was devel-
oped and held it a short distance from a flame. Arsenic was then
oxidised to arsenious acid. On treating the water drop with silver
nitrate, it gave a yellow turbidity whereas antimony gave no reaction.
Of the classical inorganic reagents, ammonium molybdate was the
last to be discovered. It was recommended by Svanberg in 1848 as a
very sensitive test for phosphorus [ 2 1 3 ] .
The reagents for qualitative analysis were now available and all
that was required was to arrange the reactions in some systematic
order so that a scheme of analysis could be developed. It was impos-
sible for a practical analyst to sort out the large number of available
reactions as there were no guiding principles. His first real help came
from the next important textbook of analytical chemistry which was
Heinrich Rose's Handbuch der analytischen Chemie published in
Berlin in 1829.
Heinrich Rose (1795—1864) was born into chemistry. His grand-
father, Valentin Rose was assistant to Marggraf and later had Klaproth
as his apprentice. His father, bearing the same name, was a student of
Klaproth and published several chemical papers. Not surprisingly,
both sons, Heinrich and Gustav, also studied chemistry. After com-
pleting their studies in Danzig and Berlin, they worked for two years
in Stockholm under Berzelius. In 1823, Heinrich was appointed
Professor of Chemistry at the University of Berlin while Gustav
became Professor of Mineralogy there in 1826. They worked there
until their deaths. Heinrich discovered niobium and the crucible used
for ignition in a gas atmosphere was named in his honour.
Rose used a new concept in his book. Rather than treating the
different reagents separately and giving their reactions with the vari-
ous elements, he used the present system of presenting the different
elements in separate chapters and giving a summary of their reac-
tions.
Rose presents a general scheme of analysis which is similar to that
used today. Firstly, hydrochloric acid is added to the solution and
silver, mercury and most of the lead are precipitated. Hydrogen
sulphide is then bubbled into the slightly acid solution and the

precipitate extracted with ammoniacal ammonium sulphide to redis-
solve the gold, antimony, tin, and arsenic. Gold is detected with tin
by forming Purple of Cassius, while tin is similarly tested with gold.
If the solution becomes turbid on dilution, antimony is present. The
residue now contains cadmium, lead, bismuth, silver, and mercury.
Treating with nitric acid dissolves all these elements except mercury
sulphide. If a blue colour is formed on addition of ammonia, copper
is present. By testing with hydrochloric acid, silver, and with sulphuric
acid, lead can be detected. Turbidity on dilution indicates bismuth.
Cadmium can be detected with the blowpipe. To the filtrate from
the hydrogen sulphide precipitation, ammonium sulphide is added
and iron, nickel, cobalt, zinc, manganese, and aluminium are precipi-
tated. This precipitate is then dissolved in hydrochloric acid (in the
case of cobalt and nickel the solution is digested with nitric acid).
Iron and aluminium are precipitated from this solution with ammo-
nia, the precipitate redissolved and treated with alkali, precipitating
iron. If the filtrate from the precipitate with ammonia is blue, nickel
is indicated, while if it is pink, cobalt is present. These two are
precipitated with alkali and cobalt identified with the blowpipe by
the cobalt blue reaction. Zinc and manganese are precipitated from
the filtrate with ammonium sulphide. Barium, strontium, and
calcium are precipitated with ammonium carbonate from the first
main filtrate and, after filtration of this precipitate, magnesium is
precipitated with, sodium phosphate. Potassium is detected with
platinum chloride [ 2 1 4 ] .
Rose's book, therefore, was the first to describe the reactions of
the individual elements and present a systematic scheme of analysis.
This scheme was probably the work of Rose himself. However,
Fresenius remarks "I could perceive that in the great wealth of
material presented in the classical work of Rose, beginners are losing
their way, as this very fine book is not very clear to them" [ 2 1 5 ] .
Fresenius rectified this defect in his book Anleitung zur Qualita-
tiven Chemischen Analyse in which he proposed his scheme for
cation analysis. He chose the most important elements and separated
them into groups on the basis of their reactions. This book, pub-
lished in 1841, was one of the most successful ever written on
analytical chemistry. By 1897, at the time of the author's death, it
had reached 16 editions [ 2 1 6 ] . It started as notes which he wrote for
his own use, there being no practical laboratory instruction in those
days. His professor, Marguart found his notes interesting and
150
persuaded him to publish them, which he did.
Carl Remigius Fresenius (Fig. 32) was born in Frankfurt am Main
in 1818. He worked for several years as an apprentice pharmacist
before going to the University of Bonn. In 1841, he became a lecturer
at the University of Giessen and worked under Liebig. In 1845, he
became professor at the Agricultural College at Wiesbaden. As there
was no laboratory, he bought a house and built his own private one.
From five students in 1847, it expanded to sixty in 1855. The
F i g . 3 2 . Carl R e m i g i u s F r e s e n i u s ( 1 8 1 8 — 1 8 9 7 ) . ( F r o m Z e i t s c h r i f t fiir a n a l y t i s c h e
Chemie, 1897.)

reputation of this institute and that of its founder flourished and the
institute still exists today. Fresenius directed it and published his
journal up to his death in 1897.
In his book, Fresenius divides the metals, or rather the metal
oxides into six groups.
Group 1. Potassium, sodium and ammonium.
Group 2. Baryta, strontianite, lime and magnesia.
Group 3. Alumina and chromium oxide.
Group 4. Oxides of zinc, manganese, nickel, cobalt and iron, and
iron oxydule.
Group 5. Silver oxide, mercury oxide, mercury oxydule, lead
oxide, bismuth oxide, copper oxide, and cadmium oxide.
Group 6. Gold oxide, platinum oxide, antimony oxide, tin oxide,
tin oxydule, arsenious acid, and arsenic acid.
It can be seen that the grouping of the metals is similar to that of
today, although Fresenius's first group is now the last. He used fewer
reagents than his predecessors but he chose with care and most of
them we still use today.
For an example of his analysis, we can consider the fifth group,
second sub-group.
"The sulphide precipitate which consists of mercury, lead,
bismuth, cadmium, and copper must be dissolved in hot nitric acid.
If the dissolution is complete, apart from any sulphur, then generally
mercury is absent. The excess of nitric acid is removed from the
filtrate by boiling. To one portion of this solution sulphuric acid is
added and the solution heated. If no precipitate is formed then lead
is absent. To another portion an excess of ammonia is added and the
solution heated. If no precipitate is formed then bismuth is absent,
while if the solution becomes blue, copper is indicated. Small
amounts of copper, however, cannot be identified in this way, so
that the solution must be evaporated to dryness, acetic acid and
potassium hexacyanoferrate(II) must be added and if copper is
present a red precipitate is formed. The residual solution is tested for
cadmium with hydrogen sulphide. If copper is present then thé
copper sulphide obscures the cadmium sulphide. In this case the solu-
tion must be treated with potassium cyanide to dissolve the copper
sulphide while the cadmium sulphide remains".
In a pedagogical stance, Fresenius recommends that students
should be required to carry out 100 practical qualitative analyses to
obtain an adequate knowledge of the subject [ 2 1 7 ] .
152
In 1862, he founded the first journal devoted entirely to analytical
chemistry, entitled Zeitschrift fiir Analytische Chemie, which is still
published. This was the first journal to deal with only one branch of
chemistry. Fresenius thought it necessary because the explosion of
organic chemistry papers around the middle of the last century began
to squeeze out analytical papers in the established journals, such as
Liebig's Annalen. Other countries soon followed this example and
The Analyst, published in London in 1875, was next to appear.
The development of qualitative analysis was virtually complete.
The only further radical change was in the size of sample with the
introduction of microanalysis. Also, it is worth mentioning that the
Midlands Association for Qualitative Analysis has undertaken histori-
cal surveys of group separations, developed separations using new
reagents, and corrected many of the errors in existing textbooks
[699].
We now come to the introduction of the organic reagents. Although
the chemist thinks primarily of dimethylglyoxime, introduced by
Chugaev in 1905 [ 2 1 8 ] , the first analytical reagent of which there is
record, the gallnut liquid, recommended by Pliny for identification
of iron, is an organic reagent. The Griess—Ilosvay reagent, an admix-
ture of a-naphthylamine and sulphanilic acid, can be regarded as the
first specific organic reagent; with nitrite ions it gives a red colour.
The reaction was recommended by Griess for the identification of
nitrite in sulphuric acid medium in 1879 [ 2 1 9 ] . Griess, primarily an
organic chemist, mentioned its analytical applications only briefly
and, under the conditions given, the reaction is not sufficiently
sensitive. In 1889, Lajos Ilosvay made a study of the system and
recommended the use of an acetic acid medium. He also used the
reagent for the detection of nitrate after reduction with zinc [ 2 2 0 ] .
Peter Griess was born in Germany in 1829 and educated at the
technical school in Kassel and at the universities of Jena, Marburg,
and Munich. His studies were protracted as he was absorbing more
beer than knowledge. In 1856, he started work in an aniline dyestuff
factory and quickly became in industrious worker, mainly to clear
his considerable debts. In 1858, he discovered the basis of diazotisa-
tion and his friend W. Hoffmann invited him to London where he
continued his research. He was employed by a brewery in Burton-
on-Trent to disprove the accusation of a French professor that
English breweries added strychnine to their beer to increase the
bitter taste. He stayed there until his death in 1888.

Lajos Ilosvay was born in Dés, Hungary in 1851. He obtained
doctor's degrees in both pharmacy and philosophy at the University
of Budapest where he became a lecturer. In 1880, he was awarded a
two-year fellowship to work with Bunsen, Baeyer, and Berthelot
after which, in 1882, he became Professor of General Chemistry at
the Technical University of Budapest where he remained until 1934.
He died in 1936.
Diphenylamine was an organic reagent known before a-naphthyl-
amine and sulphanilic acid and was also used for the detection of
nitrite. The blue colour formed in sulphuric acid medium was first
discovered by Hoffmann [ 2 2 1 ] . The reaction, however, is not spe-
cific as a number of oxidising agents give the same colour.
Since then, the number of synthetic organic reagents which have
been recommended for qualitative tests has become enormous. The
main objective of specificity, however, has only been achieved by
very few. Two good examples of specific and selective organic
reagents, similar to the Griess—Ilosvay reagent, are dimethylglyoxime
and starch.
(B) GRAVIMETRIC A N A L Y S I S
Gravimetry is the oldest and most logical method of quantitative

analysis as the determinations are made by direct weighing. In
earliest times, metals were determined by converting them to the ele-
mentary state. A major advance came when metals were determined
in the form of easily precipitable compounds, the amount of metal
being found, at first, by experiment and, later, using stoichiometric
equations. In the earlier part of the last century, only gravimetric
methods of analysis were used. Both Klaproth and Berzelius used
only these methods and indeed it was not until the 1860's that vol-
umetric methods became accepted in analytical chemistry and
appeared in the standard textbooks. There has been no essential
change in the basic technique of gravimetric analysis since the middle
of the last century. An example of a method for the separation of
iron from manganese, given in the French edition of Rose's book
(Paris, 1832), is as follows.
"Separation of iron from manganese. This is a difficult problem
for an analyst. Ammonium chloride must be added to the solution
(this is not necessary if hydrochloric acid is present in any quantity)
and then ammonia added carefully until iron hydroxide just begins
to appear. This must be redissolved and then a neutralised solution of
154
succinic acid (sodium succinate) is added when iron succinate is
slowly precipitated. Care must be taken to prevent the succinic acid
reducing the iron during the ignition. This can be avoided by
moistening the precipitate with ammonia, when the hydroxide
(hydrous oxide) is formed, this being indicated by the colour change
and the decrease in volume" [ 2 2 2 ] .
Fresenius's quantitative analytical textbook was published soon
after his famous qualitative work in 1846. This book, in contrast to
Rose's textbook, gives very detailed experimental instructions. The
preface gives some useful advice to the beginner and, indeed, to the
trained analyst.
"Knowledge and ability must be combined with ambition as well
as a sense of honesty and a severe conscience. Every analyst occa-
sionally has doubts about the accuracy of his results and there are
times when he knows his results to be incorrect. Sometimes a few
drops of the solution were spilt or some other slight mistake made.
In these cases it requires a strong conscience to repeat the analysis
and not to make a rough estimate of the loss or apply a correction.
Anyone not having sufficient willpower to do this is unsuited to
analysis no matter how great his technical ability or knowledge. A
chemist who would not take an oath guaranteeing the authenticity,
as well as the accuracy of his work, should never publish his results,
for if he were to do so, then the result would be detrimental not only
to himself, but to the whole of science" [ 2 2 3 ] .
The book starts with a description of the weighing process and we
can see that the sensitivity of the balance was about the same as
today, i.e. 0.1 mg [ 2 2 4 ] . The first operation in an analysis consisted
of drying the sample, either using steam-jacketed metal containers or
a warm air current. The sample was dissolved and then precipitated.
The more insoluble the precipitate, the more accurate was the proce-
dure. Solubility could be decreased by evaporation of the solvent, or
in the case of, for example, lead chloride, calcium sulphate, and po-
tassium chloroplatinate, by the addition of alcohol. Filtration and
washing were carried out as nowadays, the final determination being
made by ignition or drying. On ignition, even the best filter paper
had an ash content of 0.3%.
Fresenius also deals with gravimetric methods for the determina-
tion of the individual elements. He records the percentage composi-
tion of the precipitates as well as their equivalent weights, i.e. their
molecular weights as we know them (based on a weight of 100 for

oxygen) [ 2 2 5 ] , For the determination of potassium, Fresenius
recommends sulphate, chloride, nitrate, and chloroplatinate [ 2 2 6 ] ,
for barium he recommends sulphate, carbonate and silicofluoride
[227] and for calcium, sulphate and carbonate. For aluminium,
chromium, nickel, and cobalt, only the oxides were known as
weighing forms while for zinc, manganese, copper, and bismuth, the
sulphides and carbonates are suggested. Silver can be determined as
TABLE 7
Compositions of analytical precipitates according t o Fresenius
Compound Composition
According to Fresenius Theoretical
Potassium sulphate KO 54.08 54.06

so3 45.92 45.94
S o d i u m chloride Na 39.32 39.33

CI 60.68 60.67
Sodium carbonate NaO 58.47 58.47

co 2 41.53 41.53
Barium sulphate BaO 65.64 65.70

so 3
34.36 34.30
Calcium oxalate CaO 38.36 38.37

C 20 3 49.32 49.31
1 aq 12.32 12.32
Aluminium oxide 2 Al 53.19 52.92

3 Ο 46.81 47.08
Zinc oxide Zn 80.26 80.33

0 19.74 19.67
Silver c h l o r i d e Ag 75.28 75.26

CI 24.72 24.74
Lead sulphate PbO 73.56 73.56

so 3 26.44 26.44
Arsenic sulphide As 60.95 60.89

3S 39.05 39.11
Lead chromate PbO 68.94 69.05

Cr03 31.06 30.95
Silicic acid Si 48.03 46.74

2 0 51.97 53.26
156
the chloride, sulphide, cyanide, or as metallic silver [ 2 2 8 ] .
Table 7 compares the results obtained by Fresenius for the compo-
sition of precipitates with present data. These formulae and symbols,
first used by Fresenius, agree fairly well with present ones.
Writing on separations, he recommends that, with calcium and
magnesium, the former must first be precipitated with ammonium
oxalate from ammoniacal medium. From the filtrate, magnesium is
precipitated with sodium phosphate in the presence of ammonium
chloride. If phosphate is also present in the solution, calcium can be
precipitated in acetic acid medium with oxalic acid, while magnesium
can be precipitated as magnesium ammonium phosphate [ 2 2 9 ] .
There was also a description of the simultaneous determination of
chloride, bromide, and iodide. Iodide was precipitated as palladium
iodide and from the filtrate the chloride and bromide were deter-
mined by an indirect method. First of all, the halides were precipi-
tated with silver nitrate. Let us assume that the weight of precipitate
was 20 g. The precipitate was then heated strongly in a stream of
chlorine gas for about 20 min transforming the silver bromide to
silver chloride. After cooling, the precipitate was again weighed. Let
us now assume that the decrease in weight of the precipitate was 1 g.
The "equivalent" weight of silver chloride is 1792.21, while that of
silver bromide is 2348.64, the difference being 556.43. This differ-
ence is proportional to the equivalent weight of silver bromide,
similarly the difference in weight of the precipitate is proportional to
the bromide content of the salt mixtures. Thus
556.43 : 2348.64 = 1 : χ
χ = 4.221
Thus the mixture contained 4.221 g of silver bromide and 20 —
4.221, i.e. 15.779 g of silver chloride.
Fresenius gives a similar example for the determination of potas-
sium and sodium in mixtures [ 2 3 0 ] .
He gives a method for the determination of the formula of a com-
pound from its composition. The results obtained in a determina-
tion of the composition of a salt were sodium oxide 17.93%, ammo-
nium oxide 15.23%, sulphuric acid ( S 0 3 ) 46.00%, and water 20.84%.
The "equivalent weight" of NaO is 391 and, as oxygen is 100,
then 17.93% contains 4.58% oxygen.
The "equivalent weight" of N H 4 0 is 325; oxygen is 100 so
15.23% contains 4.68% oxygen.

The "equivalent weight" of S 0 3 is 500, of which 300 is due to
oxygen, therefore 46.00% includes 27.60% oxygen.
The "equivalent weight" of HO is 112.5 of which 100 is due to
oxygen, thus from 20.84% there is 18.52% oxygen.
The results obtained for oxygen in the substance are, 4.58 : 4.68 :
27.60 : 18.52, which, ignoring any small variations due to experi-
mental error, are in the ratios 1 : 1 : 6 : 4 .
Therefore the formula of the salt is N a O S 0 3 · N H 4 O S 0 3 · 4 aq.
[231].
This type of problem was encountered much more frequently by
chemists in those days than it is today.
By 1847, the methods and techniques of gravimetric analysis were
almost the same as those of today. The technique of filtration, how-
ever, has been improved since then. In early gravimetric procedures,
the ash content of the filter paper had to be taken into account. In
1878, Austen, by using a hydrochloric and hydrofluoric acid treat-
ment, prepared a filter paper which gave practically no ash on igni-
tion [ 2 3 2 ] . In 1883, the firm of Schleicher and Schull (Duren)
produced ash-free filter paper for the first time. This greatly simpli-
fied the techniques of gravimetry and since 1898, filter papers have
been available which have an ash content of less than 0.1 mg [ 2 3 3 ] ,
which is negligible.
The earliest form of filter crucibles, devised by Ôsterreicher [ 2 3 4 ] ,
were glass tubes packed with broken glass. The first robust and
durable filter crucible was the Gooch crucible, recommended by
Gooch in 1878 [ 2 3 5 ] . Sintered glass crucibles were only introduced
in the 1920's by the glass firm of Schott in Jena.
The first synthetic organic reagent to be used in gravimetric
analysis was a-nitroso-j3-naphthol, recommended by Hinski and
Knorre in 1885 for the determination of cobalt in the presence of
nickel [ 2 3 6 ] . The precipitate obtained in acid medium was ignited in
a Rose crucible in a stream of hydrogen and the residue of cobalt
weighed. The organic metal complex itself was first used as a
weighing form by Brunck in 1907 [ 2 3 7 ] . Soon after this, Baudisch
introduced cupferron for the separation of iron and copper [ 2 3 8 ] .
After the first World War, the number of synthetic organic reagents
increased tremendously.
The accuracy of analytical methods increased during the last
century to such an extent that slight errors due to variation in the
factors which influenced precipitation had to be taken into account.
158
The development of crystal chemistry and the study of colloids gave
information on the conditions for precipitate formation and on the
phenomena of co-precipitation, occlusion, and inclusion, etc. and
this was used to optimise precipitate formation. A considerable
amount of research is still being carried out on the mechanism of
precipitation.
One of the most notable workers in this field was Lajos Winkler
(Fig. 33) who attempted to develop methods in gravimetric analysis
with the highest attainable accuracy. He critically examined the
Fig. 3 3 . Lajos Winkler ( 1 8 6 3 - 1 9 3 9 ) .

problems of precipitation, filtration, and effect of heating and tried
to select experimental conditions which would give the minimum
error.
Born in Arad, Hungary in 1863, he eventually became assitant to
Kâroly Than at Budapest university. On Than's death, his institute
was divided and Winkler put in charge of part of it. Despite a modest
array of instruments, he achieved many important results. The most
important of his 200 or so original papers deal with the determina-
tion of dissolved oxygen in water, iodine and bromine numbers,
absorption of ammonia in boric acid solution, and the determina-
tion of chlorine and iodine in water. He was probably the most
accomplished exponent of classical analysis of this century. He died
in 1939.
For the control of precipitation, many other methods were exam-
ined. One idea was to carry out the precipitation from an extremely
concentrated solution, which causes crystals of great internal tension
to be formed. These can easily be purified by recrystallisation after
dilution of the mother liquor. This technique was used by Kolthoff,
Njegovan, and Marjanovich [ 2 3 9 ] . The opposing idea is to carry out
the precipitation from an extremely dilute solution. In this method,
there is only relatively slight supersaturation, so that a crystalline,
easily filterable precipitate is formed (Hahn and Keim [240]). Precip-
itation from a homogeneous solution (PFHS) is another technique
and is based on the slow generation of the precipitating reagent in
the solution itself. The main advantage of this method is that a dense
crystalline precipitate of high purity is formed. This technique was
first described by Chancel who recommended sodium thiosulphate
for the precipitation of aluminium as the hydroxide [ 2 4 1 ] . A sys-
tematic study of PFHS has only been carried out more recently
pioneered by Moser [242] and, later, Willard.
Examination of the effect of heat on precipitates was initially
studied in order to improve the accuracy of gravimetric methods. It
was important, therefore, to establish the temperature over which a
precipitate was stable. To carry out these investigations, it was neces-
sary to construct a balance which could measure the weight of the
sample during ignition. The first experiment to construct a thermo-
balance was completed by Nernst and Riesenfeld in 19.04 [ 2 4 3 ] . The
earliest crude thermobalance for practice was designed by Honda
[244] and consisted simply of suspending a porcelain crucible from
one side of the balance beam into a furnace. From this early thermo-
160
balance, the study of thermogravimetry began and it is now a special-
ized branch of analytical chemistry. The fundamental principles of
thermogravimetry were established by Duval who, together with
coworkers, examined nearly a thousand analytical precipitates and
determined the temperature ranges over which they showed a con-
stant weight [ 2 4 5 ] . He used this technique not only to find the
optimum temperature for the drying or ignition of gravimetric
precipitates, but also to carry out differential analyses based on the
different decomposition temperatures of two precipitates. Duval calls
this "automatic gravimetric analysis".
Derivative thermogravimetry is a further development of thermo-
gravimetry. The derivative of the thermogravimetric curve is obtained
instrumentally by applying the principle of magnetic induction and
shows the rate of change of weight of the precipitate as a function of
temperature, giving a more precise indication of the starting and
finishing temperatures of the various transitions [ 2 4 6 ] .
(C) M I C R O A N A L Y S I S
Qualitative microanalysis is concerned with the identification of

very small amounts of substances and is quite different, both in
practice and in principle, from common wet qualitative analysis.
Identification of the compound is not based on the formation of a
characteristic precipitate but on the examination under the micro-
scope of the crystal form of the compounds produced with different
reagents. Therefore, reagents are chosen which give characteristic
crystal forms and a high molecular volume. In wet analysis, for
example, silver can be detected by the silver chloride reaction
because the latter is insoluble and therefore the reaction is sensitive
for silver. The microanalyst prefers to use silver chromate because,
although this is less sensitive, the volume is much larger and therefore
more suitable. Separation, evaporation, filtration, etc. on the micro
scale cannot be carried out by simply scaling down the techniques of
macroanalysis. An entirely different technique is needed.
Antoine van Leuwenhoek (1632—1723) was an accountant in a
draper's shop who studied optics as a hobby. He devised the micro-
scope and with it discovered bacteria, spermatozoa, and blood
corpuscles. Boyle mentions examining a drop of water under a micro-
scope and counting the particles moving in it but gives no opinion on
the nature of these particles. Marggraf established with a microscope

that beet and cane sugars are identical.
Tobias Lowitz (1757—1804), who was in charge of the apothecary
shop at the Court in Petersburg, examined various chlorides and
other salts under the microscope and recorded their crystal forms
and other characteristics as a basis for their identification [ 2 4 7 ] .
In his book Essai de Chimie Microscopique Appliquée à la Phy-
siologie, François Raspail (1794—1878) recommends the use of the
microscope for the identification of substances, particularly in
physiology, pointing out that "to work with small amounts of sub-
stances is not only economical but involves a new technique".
Physicians and biologists began to use the microscope more and, as
a result, the characteristics of a great many compounds were recorded,
but without any analytical application.
In chemistry, the microscope began a new life in the second half
of the last century, mainly in mineralogy. Sorby, 1869, used one for
the identification of the products formed with a blowpipe [ 2 4 8 ] .
The idea of a new method for the chemical identification of minerals
and ores using a microscope originates from Emanuel Boricky
(1840—1881). In 1871, he published a book, Elemente einer Neuen
Chemische-Mikroskopischen Mineral- und Gesteinanalyse, in Prague.
Samples of the mineral were treated with hydrogen silicofluoride on
a microscope slide and the slide covered with Canada balsam. He
examined the new crystals formed. The silicofluorides of the alkali
and alkaline earth metals form characteristic, easily distinguishable
crystals. However, this method was not too successful for other
metals. Although he died young, his imaginative work had created
interest.
Reinisch wrote in 1881
"The use of the microscope in analytical tests becomes more and
more important and approaches the spectroscope in the field of
analysis of small samples. It gives even more information about the
substance, because the approximate amount of the latter can also be
determined" [ 2 4 9 ] .
Rather over-optimistic, especially when one considers that very
little publication of microscopic examination was made in those
days, and no account of quantitative microscopic analysis could be
found. At the conclusion of his paper, Reinisch offered to analyse
12 samples for 10 marks, a high price for the job in those days.
Haushofer, in his book Mikroskopische Reaktionen (Braunschweig,
1885), describes characteristic microscopic reactions for almost all
162
the elements, with the shapes of the crystals illustrated. He devel-
oped some new microanalytical techniques. For instance, he used a
small test tube for the preparation of the crystal instead of a micro-
scope slide and obtained a better-shaped crystal [ 2 5 0 ] . If the amount
of sample available was very small, then he carried out the reaction
on a microscope slide, allowing the reagents to mix slowly through a
wool strip.
Theodor Behrens (1843—1905) developed a great many micro-
chemical techniques which he classified and published in his book
Anleitung zur Mikrochemischen Analyse (1894—1898) [English edi-
tion, A Manual of Microchemical Analysis (Macmillan, London,
1 8 9 4 ) ] . The crystal properties of 59 elements are described as well
as a number of new operations; thus the first reference to the use of
a centrifuge for the separation of precipitates is to be found there.
The development of quantitative microanalysis resulted in the
need for increased sensitivity of the chemical balance. Nernst
designed a microbalance based on the torsion in a quartz fibre. It had
a capacity of only a few centigrams but was extremely sensitive
[ 2 5 1 ] , Later, Kuhlmann's microbalance became very popular as it
was capable of weighing up to 20 g with an accuracy of ±0.001 mg
[252].
Two important subdivisions of microanalysis have no analogies on
the macro scale. The first of these is catalytic analysis. A very early
example of catalysis was the process of fermentation, known since
the beginning of recorded history. The true nature of catalysis was
only established at the beginning of the last century, when the role
of acids in the production of ether and in the conversion of starch
to sugar was studied. Both the name and concept of catalysis were
originated by Berzelius, who defined catalysts as those substances
which accelerate a chemical reaction without taking part in it (1836).
The analytical application of catalytic processes is based on the
fact that small amounts of substances can be detected or determined
by their catalytic effect on certain reactions. Guyard became the
first to use this principle when he identified vanadium by means of
its catalytic effect on the formation of aniline black. He recom-
mended aniline and potassium chlorate as reagents for vanadium
[ 2 5 3 ] . Witz and Osmond in 1885 attempted to quantify this reaction
by assuming that the aniline black colour formed over a given time is
proportional to the amount of vanadium [ 2 5 4 ] . Over 50 years were
to elapse before the next use of catalytic analysis by Sandell and

Kolthoff [ 2 5 5 ] . They found that iodide ions catalyse the reaction
between cerium(IV) ions and arsenite ions and that the elapsed time
from the mixing of solutions to the colour change of the redox
indicator was inversely proportional to the iodide concentration.
However, this method is suitable for few reactions.
The other specialised microchemical technique is the field of spot
analysis. Although it is essentially an old technique, the spot tests
of today are based on the fact that when a drop of solution is placed
on a filter paper, the dissolved substance will be concentrated in a
small area. Also, capillarity enables a separation to be made of very
small amounts of sample. The history of this method originates with
Runge who in 1834 detected free chlorine using potassium i o d i d e -
starch paper [ 7 0 0 ] . Schiff, in 1859, used a filter paper impregnated
with silver carbonate to identify uric acid in urine [256] and
Schônbein, in 1861, observed that, if a drop of an aqueous solution
is placed on a filter paper, the water spreads faster than the dissolved
substance and that the relative suction heights of the latter vary
according to its properties. He pointed to this as a possible method
for the separation of salts [ 2 5 7 ] . Trey, in 1898, gave a method for
the separation of copper and cadmium by spot analysis. He found
that by drawing the tube of a filter funnel into a capillary, bending it
to a shape, pouring the solution into the funnel and touching the end
of the capillary on the paper, a drop is formed which wets the paper
evenly [ 2 5 8 ] . These experiments are the basis of paper chromatog-
raphy. The classic studies of Goppelsroeder on the capillary rise of
solutions, the capillary spreading of drops of solutions in filter paper
and their analytical effects were collected in his book Kapillar-analyse
(Dresden, 1910).
In 1918, Fritz Feigl began a systematic study of spot tests. He
selected the best available reactions, discovered new ones and
recorded limits of sensitivity. His results were finally published in
book form [ 2 5 9 ] . A further development of spot colorimetry is the
ring-oven technique developed by Weisz in 1954 [ 2 6 0 ] . The ring-
oven evaporates the solvent in a ring around the spot so that the
dissolved substance is concentrated in a narrow band.
In recent years, ultramicroanalysis has developed a great deal. This
-3 -6
technique involves sample weights of 1 0 to 1 0 g, and volumes of
-3
less than 1 0 ml. To deal with these small samples, Benedetti-
Pichler, around 1930, developed many new methods and original
apparatus (micro-manipulators, etc.) [ 2 6 1 ] . Many of the more recent
164
improvements in methods and apparatus for ultramieroanalysis have
been described by Badry and Wilson [ 2 6 2 ] . ^Jimarin and Petrikova
combined this technique with chromatography and electrolysis and
8 10
were able to identify as little as 10~~ to 10"" g of certain com-
pounds.
5. Volumetric analysis
(A) EARLY HISTORY OF TITRIMETRY
Titrimetric analysis originated during the middle of the 18th cen-

tury, accompanying the rapid development of industry, where it was
used as a rapid and simple method of quality control. A glance at
industrial chemistry in the 18th century is advantageous at this point
to set the scene.
The first industrial chemical process was the lead-chamber process
for the manufacture of sulphuric acid of which the discoverer is un-
known. According to a German source [ 2 6 3 ] , John Roebuck first
used lead chambers in his sulphuric acid plant in Birmingham in the
year 1746. Potash was in great demand both for gunpowder manu-
facture, carried out in large plants in those days, and for the
bleaching of linen in the textile industry. It had to be imported and
so was expensive. Natural soda could be used for this purpose but
was available in insufficient quantities. Consequently, the French
Academy offered 12,000 francs for a method to produce soda artifi-
cially. (When payment fell due, the French revolution had broken
out, the Academy was dissolved, and the award never given.)
Malherbe transformed rock salt into Glauber's salt, heated this with
charcoal and iron, and obtained soda. De la Métherie converted
sodium sulphide, obtained from Glauber's salt, to the acetate and
ignited this to make soda. Finally, Leblanc discovered his famous
soda process. This became an important industry, particularly in
England with its textile industry and, indeed, the method was still in
use at the beginning of the present century. However, Nicolas
Leblanc (1742—1806) benefitted little by his discovery. His factory
was founded with the financial assistance of Philip, Duke of Orleans.
When the latter was executed in 1793, the factory was confiscated,
the patent published and Leblanc ruined. For the rest of his life,
misery remained his only friend. Finally, he shot himself in the aisle
of the Church of Saint Denis.

Scheele discovered chlorine and Berthollet and Tennant used chlo-
rine and hypochlorite for bleaching in the textile industry. For the
production of chlorine, hydrochloric acid had to be prepared, so that
process was also greatly improved.
Therefore, the main products of the chemical industry in the
18th century were sulphuric acid, hydrochloric acid, soda, and
chlorine water. These were mostly used by other factories so quality
became a matter of financial concern. Chemical methods had to be
developed to check purity and soon the laboratory became an impor-
tant part of the factory. However, Lampadius, in his analytical text-
book (1801) wrote that "those who cannot wait weeks and months
for the results should never begin analytical work" [ 2 6 4 ] . As one
may guess, industry could not wait weeks and months for the results.
Titrimetry developed from the need for rapid and simple methods of
determination of the most common chemicals. However, we should
begin the history of titrimetry at the beginning.
In one of Glauber's books of 1658, a method can be found which
contains some of the elements of titration. In the preparation of pure
saltpetre from nitric acid and potash, he states that the latter "must
be added dropwise to spritum nitri, until on further addition
bubbling ceases and both lose their inimical characteristics and kill
each other" [ 2 6 5 ] .
According to the excellent book by Rancke-Madsen [ 2 6 6 ] , the
year 1729 can be regarded as the birthdate of titrimetric analysis. In
that year, Claude Joseph Geoffroy presented a dissertation to the
French Academy on the concentration of vinegar. The text states
"Among the vinegars we must then choose by chemical operations
that which contains most acid. For this purpose several methods can
be used. For my investigations I take out from each type of vinegar
about 2 drachms, pour it into a glass and then weigh it accurately.
Then I add finely powdered, dry potash until the bubbling ceases.
The acids of the vinegar then disappear and the solution becomes
salty and if the bubbling has ceased I can determine the strength of
the vinegar from the amount of potash used for the absorption of the
acid. This is usually about four grains in the case of the weaker
Parisian vinegars, while it can be as much as eight grains in the case
of the stronger ones. The vinegar of Orleans may consume even
eleven grains, moreover, according to my experience, a vinegar from
Orleans may also reach twelve" [ 2 6 7 ] .
Thus, as far as we know, Geoffroy was the first to use neutralisa-
166
tion for analytical purposes. He also used a "standard solution", i.e.
solid potassium carbonate and an indicator (effervescence). The
strength of the acetic acid he characterised by the amount of con-
sumed "standard solution".
Although Monnier, in 1747, described a rather similar method for
determining the carbonate content of mineral waters [ 2 6 8 ] , the next
noticeable improvement came from Venel, in 1750, in his account of
the analysis of a mineral water from Seltz. He used a standard solu-
tion, together (for the first time) with an indicator, the extract of
violets.
"A volume of sulphuric acid, equal in volume to 1 oz. of water,
weighed 1 oz. and 6 gr. This I diluted with 6 parts of distilled water,
then I added this to half a libra of Seltz water, slowly, mixing the
solution and heating it constantly; the violet syrup turned to red
when 28 gr. of this dilute acid were used, which corresponds to 6 gr.
of concentrated acid" [ 2 6 9 ] .
He concluded that the water was not alkaline and that the stan-
dard solution was consumed by the indicator since repetition using
melted snow gave the same result.
In 1756, Francis Home (1720—1813), who was Professor of
Pharmacy at the University of Edinburgh, published a book entitled
Experiments of Bleaching. In it, he described the examination of
potash.
"In order to discover what effect acids would have on these ashes
and what quantity of the former the latter would destroy, from
which I might be able to form some judgment of the quantity and
strength of the salt they contained, I took a drachm of blue pearl ashes
and poured on it a mixture of one part spirit of nitre and six parts
water, which I shall always afterwards use and call the acid mixture.
An effervescence arose and, before it was finished, 12 teaspoonfuls
of the mixture were required. This effervescence with each spoonful
of the acid mixture was violent but did not last long" [ 2 7 0 ] .
The novelty of this method is that it is really a volumetric one,
because he measured the consumption of standard solution by
volume, even if it was only with a teaspoon. The earliest examples of
precipitation titrations also originate with Home. To determine the
hardness of water he added a solution of "alkaline salt" until precipi-
tation ceased [ 2 7 1 ] .
In 1767, William Lewis published a monograph in London entitled
Experiments and Observations on American Potashes. With an Easy

Method of Determining their Respective Qualities. In it, he prepared
an aqueous extract of the potash, separated from earthy impurities
by filtration and determined it by acidimétrie titration.
"The quantity of acid necessary for saturation of the lye should be
determined not by drops or teaspoonfuls, but by weight; and the
point of saturation, not by the ceasing of effervescence, which is
extremely difficult if not impracticable to hit with tolerable exact-
ness, but by some effect less ambiguous and more strongly marked
such as the change in colour produced in certain vegetable juices or
on paper stained with them. The finer sort of purplish-blue paper
used for wrapping sugar in, answers sufficiently well for this purpose."
Lewis' life and work was studied by Gibbs [701] and, more
recently, by Stephens [ 7 0 2 ] . Born the son of a Richmond brewer in
1708, he attended both Oxford and Cambridge Universities and
graduated from the latter with the MB degree in 1731. He set himself
up in London as a consulting chemist and applied himself to experi-
mental problems in the chemical arts. He was elected to the Fellow-
ship of the Royal Society in 1745. Shortly afterwards, he moved to
Kingston-upon-Thames, where he set up a laboratory especially
designed for work in the field of applied chemistry. He died in 1781.
By consulting the widely read chemical encyclopedia compiled by
Macquer (1766), we can conclude that the theory of neutralisation
titrations was well known at that time. He writes about water analysis
that "if the water contains free acid or alkali, this can be identified
by its taste or by its effect on the colour of litmus or violet liquor, as
well as by the addition of just as much acid or base to it as is needed
to reach the point of saturation" [ 2 7 2 ] .
Louis Bernard Guyton de Morveau (1737—1816), who had started
life as a lawyer and a poet, wished to make his saltpetre plant in
Dijon more efficient and so investigated the methods for obtaining
saltpetre from the mother liquor. During these investigations, he used
indicators for the first time in industrial technology for the neutrali-
sation of nitric acid. He eventually devised a method which, as he
says, "can be used in the hands of a less intelligent worker". His
procedure is as follows.
"1. First take out from the mother liquor two portions each of
three cubic inches.
2. Dissolve in a given amount of water a known amount of alkali
carbonate.
3. Dilute one of the samples of the mother liquor, place two paper
168
strips in it, the first having been treated with fernambuke and the
second with corcume extract. To this add the alkali solution, pre-
pared under 2, until the papers indicate that the point of saturation
is reached.
4. Now weigh the residual alkali. From the difference the amount
of acid present in the mother liquor can be calculated. This corre-
sponds to the total amount of the two acids, nitric and hydrochloric,
present in the mother liquor.
5. Dilute similarly the second mother liquor sample.
6. Prepare lead nitrate solution by dissolving a known amount of
lead in nitric acid and determine its weight.
7. Then add this lead nitrate solution in small portions to the
mother liquor until no further turbidity occurs. This can be observed
at the end by allowing the solution to clear before adding another
drop.
8. The lead nitrate solution must again be weighed and from the
difference the amount of hydrochloric acid can be calculated. From
the investigations of Wenzel we know that the amount of hydro-
chloric acid required to neutralise 11 parts of potassium carbonate
combines with 16 parts of lead; from this we can calculate the
amount of alkali consumed in section 4 and its proportion to the
amount of lead consumed in section 8, and hence to the amount of
hydrochloric acid. By subtracting this from the total amount of acid,
the amount of nitric acid can be calculated" [ 2 7 3 ] .
In another interesting method for the determination of dissolved
carbon dioxide in water, Guyton de Morveau describes a gas mea-
suring device, which he calls a "gasometre". As this was a cylindrical
glass tube with a paper scale glued to the outside, it can be regarded
as a forerunner of the modern burette [ 2 7 4 ] .
Kirwan, in 1784, first used potassium hexacyanoferrate(II) as a
standard solution for the determination of iron. He standardised it
against metallic iron dissolved in sulphuric acid and the strength he
noted on the hexacyanoferrate(II) solution label [ 2 7 5 ] .
(B) FROM DESCROIZILLES TO GAY-LUSSAC
It will be noticed that most of the contributors to the develop-

ment of titrimetry have been French. This was due to the close
connection between industry and science in that country after the
revolution. Many of the best chemists were employed by the govern-

ment to work on industrial problems. Berthollet was concerned with
textiles, Vauquelin with the production of chemicals and Guy ton de
Morveau with saltpetre plants. Likewise, Henry Descroizilles devel-
oped the first redox titration for use in the bleaching industry.
François Antoine Henry Descroizilles (1751—1825), of whom a
certain Madame Roland once wrote "I think that he makes court to
the world for financial purposes", had a liking for get-rich-quick
schemes. He was also something of an inventor designing light-
houses, a coffee-boiling machine similar to the expresso machines of
recent years, a portable alcohol distillation apparatus and a fire-
extinguisher. When a student of Berthollet demonstrated a new
bleaching technique to the town of Rouen, Descroizilles persuaded
the Lord Mayor of Fontenay to finance the construction of a pilot
plant. He noted the critical factor of the method to be the hypo-
chlorite concentration, so he devised his famous method for testing
this. Although this came to be quite widely known at the time,
Descroizilles did not publish his method until a few years later in
1795. The apparatus he used is shown in Fig. 34. The first piece,
which resembled a measuring cylinder, he called a berthollimeter,
whether through genuine regard or simple flattery. The second is a
pipette which he called a measure. This was immersed into the chlo-
rine water, a finger placed over the top, the level adjusted to mark A
and this volume run into the cylinder. The cylinder was graduated by
means of the measure, chlorine water reaching up to the zero mark.
Then by sucking the pipette-like device on the right the bulb D was
filled with a 1% solution of indigo in sulphuric acid. He advises one
to "cautiously let the blue solution pour into the berthollet-solution
(chlorine water), which destroys the colour immediately and the
solution turns reddish. Interrupt occasionally the pouring of the solu-
tion from the mouth-pump and shake the solution. Take care that no
foam or bubbles should be formed as this obscures the meniscus.
The reaching of the saturation point can be observed by the forma-
tion of a pale olive-green colour, which is the resultant of the red and
the small amount of blue. The latter disappears towards the end
more and more slowly. Water, saturated with chlorine at 10° above
freezing point shows 8 degrees in the berthollimeter if the indigo is
of a good sort and the test solution was prepared well" [ 2 7 6 ] .
This method was in use by the end of the century in almost all
bleaching plants in Western Europe. In this technique, the pipette
and burette appear in their earliest form, although Achard in 1785
170
F i g . 3 4 . T h e first t i t r a t i o n a s s e m b l y o f D e s c r o i z i l l e s , 1 7 9 5 . ( F r o m Rancke-
M a d s e n ' s b o o k , T h e D e v e l o p m e n t o f T i t r i m e t r i c A n a l y s i s till 1 8 0 6 . )
Fig. 3 5 . Descroizilles' burette for alkalimetry, 1 8 0 6 . ( F r o m his original paper.)
used a pipette for physical examinations [ 2 7 7 ] .

Returning to acid—base titrations, we find that, in 1792, Fordyce
described for the first time the use of alkali hydroxide for the deter-
mination of sulphuric acid, instead of alkali carbonate, using violet
liquor to detect the end-point [ 2 7 8 ] .
Black found and eliminated two small errors which were not really
considered by analytical chemists until a far later date. He boiled his
solution to eliminate "fixed air", i.e. carbon dioxide and made a

correction to allow for an alkaline impurity in his litmus indicator.
He was also the first to use a back-titration, adding excess acid and
then back-titrating with potassium carbonate solution to obtain a
sharper end-point [ 2 7 9 ] .
The principle of volumetric measurement in acid—base titrations
became well known after the publication of Descroizilles' paper in
1806 entitled Notices sur les Alcalis du Commerce [ 2 8 0 ] . The most
important contribution of this paper is the vessel called an alkali-
meter, which led directly to the development of the burette. This is
shown in Fig. 35 and was 20—22 cm long and 14—16 mm in diam-
eter. At the top, there was a lip for ease of pouring and a small hole
to allow the air to escape. The vessel held 38 g when filled to the
mark; the right-hand scale refers to half-gram quantities. The left-
hand scale allows it to be used as a berthollimeter, i.e. to determine
the strength of chlorine water. His method of determining potash
using the alkalimeter was simple. 10 g of potash were dissolved in
40 ml of water. The "burette" was filled to the zero mark with dilute
sulphuric acid and, with a finger over the hole at the top, the solu-
tion could be poured at the desired rate by movement of this finger.
When the solution reached the 40 mark, a drop was removed and
added to a little violet extract on a plate. This was repeated until the
indicator turned from green to red at the neutralisation point. The
average value was 55 and anything less was considered inferior
quality. He also determined sodium carbonate, sodium hydroxide,
tobacco ash, etc. by this method.
In 1809, Descroizilles mentions an important new piece of appara-
tus, the volumetric flask, which he describes as "a small jug, with a
volume slightly greater than 2 dl, on the neck of which a mark is
made with a diamond needle, indicating the place, up to which the
vessel contains just 2 dl".
After this, acid—base titrations only experienced small refinements
until the introduction of synthetic indicators towards the end of the
19th century.
In the field of precipitation titrations, Bartholdi in 1792 pub-
lished a method for the determination of sulphate in pigment
extracts. He precipitated the sulphate with lime water, which he had
previously standardised against pure magnesium sulphate [ 2 8 1 ] . In
the tenth volume of the Annales de Chimie (1802), a paper was pub-
lished by the Powder and Saltpetre Directory containing a method
for the examination of potash by an unnamed analyst [ 2 8 2 ] , Calci-
172
um nitrate was used as the titrant to precipitate both the carbonate
and the sulphate. It is mentioned that strontium or barium nitrate is
better for this purpose than calcium nitrate, strontium being first
choice "because its use is harmless". In this paper the word "titre" is
used, although, as in other early French papers on titrimetry, its
meaning is uncertain. The basic precipitation methods, therefore,
were worked out during the 18th century.
The only redox titration used for a long time was the determina-
tion of chlorine water and hypochlorite. Dalton, among many others,
tried to improve the method. He used standard ferrous sulphate solu-
tion. His method [283] is difficult to follow; Fe(II) ions are trans-
formed to "red iron oxide", Fe(III), when treated with the "oxidised
hydrochloric acid solution" (hypochlorite). This uncertain method
was used for a long time despite Otto's spot-test end-point detection
method using potassium ferricyanide [ 2 8 4 ] . Welter tried to improve
Descroizilles' method by standardising the indigo solution with chlo-
rine gas [ 2 8 5 ] . This was inaccurate because, as Gay-Lussac points
out, the amount of hypochlorite solution consumed depends on its
rate of addition to the indigo [ 2 8 6 ] . Welter tried adding all the
hypochlorite solution at once and got quite accurate results. Gay-
Lussac soon found a better method, titrating hypochlorite with
arsenious acid in the presence of indigo as a redox indicator. This
method started the development of redox indicators.
In all branches of titrimetry, we meet the same name, Joseph Gay-
Lussac. It was largely due to the widespread use of his methods that
this subject changed from an industrial technique to a distinct branch
of science.
Joseph Louis Gay-Lussac (Fig. 36) was born in 1778 in the small
town of Saint-Leonard of the ancient Limousin near the Auvergne.
He went to college in Paris joining the new École Polytechnique in
1796. When his exceptional ability was noticed he was offered the
post of laboratory assistant to Berthollet. He later became famous by
ascending to a height of 7000 m in a balloon to examine the com-
position of the air, its temperature and magnetic effects. In 1805—
1806, with his friend Humboldt, he observed a violent eruption of
Mount Vesuvius and carried out some geological investigations. In
1807, he was elected a member of the French Academy and, in the
same year, he married. The next year, he established the gas laws
which bear his name and became Professor of Physics at the Sorbonne
while retaining his chair of chemistry at the École Polytechnique. In

Fig. 3 6 . J o s e p h L o u i s Gay-Lussac ( 1 7 7 8 — 1 8 5 0 ) . ( F r o m Bugge, D a s B u c h der
grossen Chemiker. )
spite of numerous posts, he continued his research work including

the determination of vapour densities, the nature of solubility and
capillarity and investigation of the properties of iodine. He succeeded
Berthollet in the title Père de France. Although very ill towards the
end of his life, Gay-Lussac liked to keep up with developments in
science. His last words were reputed to be "It is a pity that I must
depart now, when it begins to become so interesting". He died in
1850.
174
Fig. 3 7 . Titrimetric device of Gay-Lussac, 1 8 2 4 . ( F r o m his original paper.)
The first titrimetric work of Gay-Lussac [286] was a critical

examination of the method of Welter, referred to earlier, recom-
mending certain modifications. The most interesting part of this
paper is a description of his titration apparatus (Fig. 37). F is a
3
"petite measure ou pipette" with a volume of 2.5 c m . It is immersed
in chlorinated lime solution which rises above the mark. It is adjusted
to the mark in the usual fashion as illustrated in G. The contents are
run into beaker H. A burette, I, is then used for the measurements of
the test pigment. The large marks correspond to the volume of the
small pipette F and these marks are further sub-divided into five
parts.
In 1828, Gay-Lussac wrote a paper on the examination of com-

mercial potashes [287] and in it he refers to Descroizilles who was
the first to examine alkalis in this way. In this method, Gay-Lussac
prepared a solution of 100 g of sulphuric acid (sp. gr. 1.84) and
diluted this to 11 (i.e. approx. 1 M). He found that 50 ml of this
solution are required to neutralise 4.807 g of potassium carbonate.
In his description of this titration, we find the first use of the verb
"to titrate". Below is part of this description.
"Take the beaker and pour into it the alkaline solution with one
pipette . . . pour into it so much litmus solution that should be defi-
nitely blue. Hold the beaker over a white paper to perceive better the
colour change of the litmus. Fill the burette to the mark 0 with the
normal acid. Hold the burette in one hand and the beaker in the
other; pour the acid into the alkaline solution and move the latter
constantly in small circles in alternative directions. At the beginning
the colour does not change, but if the potassium carbonate is exam-
ined after 11/20 parts of the saturation has taken place then the solu-
tion turns to wine red, owing to the liberated carbonic acid. Care
must be taken to avoid passing the saturation point. If the acid when
it is added to the solution only causes a slight bubbling, then con-
tinue the addition of the acid dropwise, testing after the addition of
each drop by placing a drop on litmus paper . . . As the saturation
point is passed, the wine colour of the solution turns to mushroom-
red and the colour of the paper turns to red and remains at this
colour. . ." [ 2 8 7 ] .
This method of titration was not easy to carry out, although with
practice it could be improved.
Gay-Lussac published his most famous method, the precipitation
titration of silver, in 1832. This method, named after him, is still
used today and its precision is not inferior to any of the indicator
methods [ 2 8 8 ] . He claimed that the old cupellation method gives a
low result, so that, in effect, the Government was losing money. To
test his assertion, the French Mint prepared accurately alloyed silver
samples and sent them to be examined at several places in Europe.
The deviations in the results completely proved Gay-Lussac's suppo-
sition [ 2 8 9 ] .
He used both a gravimetric and a titrimetric procedure. He
believed the method involving weighing the burette to be more
precise but the titrimetric method to be simpler. He prepared a stan-
dard sodium chloride solution of a concentration such that 100 ml
precipitated slightly less than 1 g of silver. Another sodium chloride
176
solution called tenth-solution, of which 11 would precipitate 1 g of
silver, was also prepared. 1 g of silver was accurately weighed. After
dissolution, 100 ml of the concentrated chloride solution were added
and the precipitate allowed to settle. Then the dilute chloride solu-
tion was added in 1 ml portions. After each addition, the sample was
shaken and then the precipitate allowed to settle. This was repeated
until a further addition did not cause precipitation, then this last
excess of chloride was back-titrated with a tenth silver nitrate solu-
tion.
Gay-Lussac realised that the volume of a standard solution
increases with temperature so he calculated temperature corrections.
He did not recommend filling pipettes by mouth suction but rather
by a device which he constructed. However, this was complicated
and inconvenient to use and fell into disuse [ 2 9 0 ] .
In 1835, he published a paper which, once again, dealt with the
determination of hypochlorite or chlorinated lime. Standard solu-
tions of arsenious acid, potassium hexacyanoferrate(II), and mercu-
ry (I) nitrate were used [291] and the apparatus was essentially the
same as that used in earlier methods. The experimental details were
only given for arsenious acid. He prepared a standard solution by
dissolving 4.439 g of arsenic trioxide in a little hot hydrochloric acid
and then diluting this to 11. 11 of chlorine gas dissolved in water
reacted exactly with this solution. The arsenious acid was then added
using a burette.
"If the arsenious acid solution is coloured slightly with a sulphuric
acid/indigo solution and the chlorine is added dropwise, the blue
colour remains until there is an excess of chlorine; this only occurs
when all the arsenious acid is transformed to arsenic acid."
This is the first recorded use of redox indicators in titrimetry. This
indicator, however, is irreversible and it is characteristic of the
accuracy with which Gay-Lussac worked that he subtracted a half
drop from the total titre to compensate for the excess of arsenious
acid at the end-point. He also determined the indicator blank and
allowed for this.
We have seen that Gay-Lussac developed accurate methods in all
the main branches of titrimetry but did not realise the possibility of
establishing a general system of titrimetric analysis. The concentra-
tions of his standard solutions had no chemical basis owing to differ-
ences in atomic weights and the undeveloped stoichiometry of those
days. His standard solutions could only be used for specific analyses

and for a given weight of sample and his burettes, although similar in
construction to each other, had to be calibrated separately for each
determination.
(C) F R O M G A Y - L U S S A C TO M O H R
As result of the work of Gay-Lussac, titrimetry became a rapid,

convenient, and reasonably accurate method, increasingly used in
practical analysis and in industry. However, the purely scientific
possibilities were investigated by the universities and, in the next few
decades, it is almost true to say that every known chemical was tried
as a standard solution for the determination of all other known
chemicals. Most of the methods published in this period did not
survive beyond their publication. Some, however, such as iodometry
and permanganatometry, are still used by analysts all over the world.
There is space here for a consideration of only a few of the more
important methods.
The discovery of the use of iodine and iodides in titrimetric
analysis was made by Houton de la Billardière in 1826, soon after
the discovery of the element. He boiled iodine with a solution of
sodium bicarbonate, potato starch and sodium chloride, diluted it to
11 and used this for the titration of chlorinated lime. Sodium iodide
is first formed, then oxidised by hypochlorous acid to iodate. At the
end-point, iodine is liberated and the solution becomes blue [ 2 9 2 ] .
This method was used repeatedly and often appeared as a new meth-
od. Several workers attempted to make the method more accurate by
altering the experimental conditions but were never completely
successful [ 2 9 3 ] .
Du Pasquier was the first to use iodine as a standard solution in
1840. He titrated the hydrogen sulphide content of water with a
solution of iodine in alcohol using starch as an indicator [ 2 9 4 ] .
Duflos determined iron iodometrically in 1845. He added potas-
sium iodide to the iron(III) solution and titrated the liberated iodine
with a standard solution of stannous chloride. 1 1 of a standard solu-
tion, containing one equivalent (atomic weight) of tin (5.90 g), con-
sumed 12.5 g of iodine [ 2 9 5 ] . This was therefore a normal solution
in the modern sense. An iodometric method for the determination of
tin was developed by Gaultier de Claubry in 1846, quite indepen-
dently of Duflos. In this method, the tin sample was dissolved in
hydrochloric acid, reduced with iron or zinc, and the Sn(II) titrated
178
with an alcoholic solution of iodine, using starch as indicator. During
the prior reduction, arsenic, antimony, lead, mercury, and copper
were precipitated in the form of the metal and therefore did not
interfere [ 2 9 6 ] .
The most important development in iodometry was made by
Bunsen, in 1853, when he utilised a general iodometric method for
the determination of oxidising substances. Hydrochloric acid was
added to the sample and the chlorine formed passed into a potassium
iodide solution. The liberated iodine was titrated with a standard
solution of sulphurous acid. It could not have occurred to him that it
was possible to treat the substance directly with potassium iodide or
possibly he did try this on one or two compounds but without
success. In a short paper of only twenty pages, he describes the deter-
mination of iodine, bromine, chlorine, hypochlorite, chlorate,
chromate, lead, manganese, nickel and cobalt oxides, cerium(IV)
salts, iodate, vanadate, ozone, selenic acid, permanganate, iron(III),
and arsenious acid and its salts [ 2 9 7 ] . A modern chemist would write
five or even ten papers to describe this amount of work.
In the same year, Schwarz recommended the use of thiosulphate
for the titration of iodine [ 2 9 8 ] . This method, undoubtedly the
most effective for this determination, has been in use for the past
hundred years without being superseded. In the words of Schwarz,
"It is difficult for me to say why I consider this method for the
determination of iodine to be the best; I think, however, that I can
recommend it with a good conscience because it is so simple and
accurate" [ 2 9 9 ] .
In 1846, Margueritte introduced another important oxidation
method, permanganatometry, which he used to determine iron. The
method is so simple that it could be carried out by the foreman in
charge of the casting and is based on the reaction between chamaeleon
( K M n 0 4 ) and the lower oxidation state of iron [Fe(II)].
"The reaction of iron protoxide and chamaeleon can be expressed
by the following equation.
2 7 2 2 5
M n 0 , KO = M n 0 + O + KO
2 2 5 2 2 2 2 2 3
M n 0 + O + KO + 5 F e 0 = M n 0 + 5 F e 0 + KO
The following steps must be made.
1. The ore must first be dissolved in some acid, for example hydro-
chloric acid.

2. The iron oxide formed must be converted to iron protoxide. To
accomplish this zinc, sulphurous acid or sodium sulphite can be used;
in the last case the solution must then be boiled to remove sulphurous
acid.
3. Then the normal chamaeleon solution must be added cautiously
until the solution becomes pink and the amount consumed noted
from the burette" [ 3 0 0 ] .
This was the first paper in which a redox process is expressed by a
chemical equation.
He recommended reduction with zinc as sulphurous acid also
reduced arsenic and copper and these then consumed the standard
solution. He also described the examination of ores and alloys,
pointing out that the method can be applied to the analysis of any
metal which forms a protoxide. Potassium permanganate solution
was called chamaeleon for a long time and, even today, very old
chemists sometimes use this name.
However, the usefulness of this method was not recognised by
contemporary chemists. In those days, the importance of the author,
not the content of the work, determined the importance of a meth-
od. In Berzelius's Jahresbericht, Margueritte got 12 lines, while on
the next page, a long-forgotten method by Pelouze, a well-known
university professor, which consisted of a titration of copper with
sodium sulphite in ammoniacal medium until the blue colour dis-
appeared, had a review of 92 lines [ 3 0 1 ] .
A year later, Bussy used permanganate for the determination of
arsenious acid, titrating with a very dilute (0.4 g/1) solution in hydro-
chloric acid medium [ 3 0 2 ] . Hempel [303] used a standard solution
of potassium permanganate for the determination of oxalic acid
[304] and pointed out that this method provided the basis for
several indirect procedures.
Clark, in 1841, devised a method for determining water hardness,
which is still used today. It involves titrating the water with a stan-
dard soap solution until a persistent foam remains after shaking the
solution for 5 mins. He gave his results in degrees of hardness, which
is the method used to this day, reminiscent of an age when all the
results of analysis were given in degrees of some kind. Clark's degree
is equivalent to 1 gr. of calcium carbonate per gallon of water (the
English hardness degree). He also managed to differentiate between
permanent and temporary hardness [ 3 0 5 ] . Bolley used a French
scale where 1° represented 0.01 g of calcium carbonate in 11 [ 3 0 6 ] .
180
Faisst expressed hardness as calcium oxide [307] and from this the
German hardness degree developed.
The determination of ammonia by a volumetric method, i.e.
distilling the ammonia into a known amount of hydrochloric acid
and back-titrating the excess, originates from Péligot, who collected
the ammonia in sulphuric acid. As an indicator, he used iron and
tannic acid which turned violet when the alkali was present in excess.
The standard solution he used was lime dissolved in a sugar solution
[308].
The first example of the titration of alkaloids was the determina-
tion of nicotine devised by Schloesing. He extracted the tobacco
with ammoniacal ether using a reflux condenser and, after boiling the
ammonia out of the solution, he titrated the base with standard acid
[309].
Potassium chromate solution for the determination of iron was
introduced simultaneously, though independently, by Schabus [310]
and Penny [ 3 1 1 ] . However, this involved a spot test with potassium
hexacyanoferrate(III) which Schwarz criticises because "Experience
shows that all such analyses where the end of the reaction must be
tested by taking out drops of the solution to test on a spot plate with
a reagent, tend to be inaccurate and should only be used if no alter-
natives are available" [ 3 1 2 ] .
Other oxidising and reducing standard solutions were examined
during this period but few were useful owing to the lack of a suitable
indicator. Later developments in indicators caused some of these to
become important.
Potassium iodate was first used by Berthet in 1846. He established
that, when potassium iodate is added to a soluble iodide in sulphuric
acid medium, iodine is liberated and that for every 5 atoms of iodide,
1 atom of iodate is consumed. Berzelius mentioned that "the method
seems to be better in writing than in practice" [ 3 1 3 ] .
A paper by Becquerel [314] describes the detection of sugar with
a solution of a copper salt (1831) and later Barreswill developed this
into a quantitative method for which he was awarded 1000 francs.
He dissolved 20 g of sodium carbonate in 200 ml of water followed
by 40 g of potassium hydrogen tartrate and 40 g of potassium
hydroxide. Another solution was prepared by dissolving 30 g of
copper sulphate in water and then the two solutions were mixed,
filtered, the filtrate diluted to 500 ml, placed in a porcelain dish, and
heated. 10 g of sugar were dissolved in 500 ml of water and placed in

a burette. When this was added to the copper solution, red copper
oxide was precipitated and the blue colour of the solution gradually
decreased, its disappearance denoting the end-point [ 3 1 5 ] .
The method was soon used by other workers and has since been
modified numerous times. Fehling, in 1849, established that 1 atom
of saccharum uvae reduces 10 atoms of copper oxide and recom-
mended different copper salt solutions [ 3 1 6 ] . However, his contribu-
tion was hardly sufficient to warrant naming the method after him,
as has been done.
In the field of precipitation titrations, the argentometric chloride
determination was adapted by Duflos [317] in 1837 for the deter-
mination of cyanide. Many now-forgotten precipitation titrations,
were suggested at this period. Among them were Pelouze's use of a
sodium sulphide standard solution for the determination of metal
ions and his use of uranium solution for determining phosphoric acid
[ 3 1 8 ] . Liebig recommended ferric chloride for this determination
[ 3 1 9 ] . This, too, was of little practical importance.
Around this time, the earliest methods based on complex forma-
tion appeared, the first being the cyanide determination of Liebig,
which is still in use today [ 3 2 0 ] . Liebig was also the first to use
mercury(II) nitrate solution, his original method being for the deter-
mination of chloride [ 3 2 1 ] .
During Gay-Lussac's time, and even for a considerable period after
him, the concentrations of solutions were chosen so that, for a given
weight of sample, the consumption of standard solution would give a
direct percentage of the component sought. From about 1840, the
practice of making up standard solutions based on atomic, molecular,
or equivalent weights gradually increased, despite disagreement over
the actual values. The use of normal standard solutions originated in
England where, due to a non-metric system of measures, it was com-
plicated to devise a method of analysis where the consumption of
reagent gave the percentage of component sought directly.
Andrew Ure was apparently the first to consider that the "atomic
weight" dissolved in the unit of volume would give a convenient stan-
dard solution. In his Dictionary of Arts, Manufactures and Mines he
describes the dilution of ammonium hydroxide so that it should
neutralise just one atomic weight of acids. Thus, as he wrote, "a
universal acidimeter is available" [ 3 2 2 ] . It is interesting that his stan-
dard solution of acid was not prepared on the same basis. In the fol-
lowing years, the number of papers describing the use of normal solu-
182
tions increased rapidly, but whether this was a result of Ure's work
or whether the advantages gained in using a solution of this type
were discovered separately is not known. It was not until the publica-
tion of Mohr's book, however, that the use of normal solutions
became really widespread.
Andrew Ure was born in Glasgow in 1778 and educated there. He
became Lecturer in Chemistry and Natural History at the Anderson
University, Glasgow, in 1801. He gave popular lectures for the
public, being of the opinion that if the workers had some slight
knowledge of science this would improve their production. In 1830,
he moved to London to work as an analyst. The Board of Customs
F i g . 3 8 . T h e first b u r e t t e w i t h t a p u s e d b y H e n r y i n 1 8 4 6 . ( F r o m Schwarz,
Praktische A n l e i t u n g zur Massanalysen, 1 8 5 3 . )

paid him 2 guineas for each analysis. He enjoyed a considerable
reputation and wrote several books about analytical and technologi-
cal questions. He died in 1857.
Henry describes the first burette with a tap in 1846 (Fig. 38). The
tube was made of glass, while the tap was copper [ 3 2 3 ] . It would
seem that the reason for the late development of the burette in its
modern form was the inability of the glass technologists to make a
tap out of glass. However, Henry's burette must not have been very
useful as the Gay-Lussac burette continued to be used until Mohr
appeared on the titrimetry stage.
(D) FRIEDRICH MOHR
Despite this successful period in its development, titrimetric

analysis was still only practised by a narrow circle of chemists. The
famous analytical chemists of this period were contemptuous of the
new methods. Berzelius said of Gay-Lussac's determination of borax
"I hope this method will never be introduced into science and that it
will never be used where a sufficiently accurate method is already
available" [ 3 2 4 ] .
These objections were probably due to unfamiliarity with the
technique as, before 1850, information on titrimetry was only to be
found in scientific journals. Books, on the other hand are very effec-
tive vehicles for disseminating new methods. The first textbook of
titrimetry, entitled Praktische Anleitung zur Massanalysen (Titrier-
Methode) was written by Karl Heinrich Schwarz (1824—1890) and
published in Braunschweig in 1850.
A slim volume, in its title we first find the word Massanalysen,
which apparently the author created from the French expression
dosage à liqueurs titrées. This word still exists in German and the
term "volumetric analysis" originates from it.
The many methods listed are presented in three sections, satufa-
tion analysis, oxidation and reduction analysis, and precipitation
analysis. Some are important, such as his own use of thiosulphate in
iodimetry, while some are so complicated that they are examples of
l'art pour l'art with no practical importance. His standard solutions
were selected so that for a 1 g sample, the consumption of solution
gave the percentage composition directly. He also mentions that it is
possible to use "aequivalent" amounts of substances which, when
dissolved in unit volume, yield "rational solutions". It is interesting
184
Fig. 3 9 . Friedrich M o h r ( 1 8 0 6 - 1 8 7 9 ) .
to note that Schwarz systematically uses reaction equations preceding

contemporary chemical books in which this treatment was lacking,
e.g. 10 FeO + M n 2 0 7 = 5 F e 2 0 3 + 2 MnO.
Only one edition of Schwarz's book appeared and, soon after-
wards, Mohr's famous Lehrbuch der Chemischen-Analytischen
Titriermethode was published in 1855.
Friedrich Mohr (Fig. 39) was born in Koblenz in 1806, the son of
a pharmacist. He also studied pharmacy. He went to university at
Bonn, Heidelberg and also Berlin, where he came under the influence
of Heinrich Rose. On graduation, he returned to run his father's
shop but, as this was not very profitable, he carried out experiments
in his spare time. He was something of a dilettante in his studies. He

would become immersed in a branch of science, publish a few papers,
possibly a book, and then move on to a new field. He also had an
irritable, critical, and rather disagreeable nature which caused Liebig
to write to him "you would find much less aversion if you tried to
avoid always offending others" [ 3 2 5 ] .
At one stage, his interest in chemical ferilizers became so great
that he sold his shop and bought a small estate where he became a
partner in a new chemical ferilizer plant. However, the plant failed
and at the age of 57, he had to search for a job. He became a Privât
Dozent at Bonn University and, in 1867, was made Deputy-Professor
of Pharmacy. However, he then turned to geology and later the con-
servation of heat. He died in 1879.
Mohr had the disadvantage of living in Germany at a time when
the only scientists were university professors and he therefore tended
to live beyond the fringe. Incidentally, the popular image of a
professor, bearded, bespectacled, aloof from every-day life, immersed
in books and absent-minded, was a reality in Germany at this period.
An example of this disability came when he wished to publish a
paper entitled Ansichten iiber die Natur der Wàrme in 1837. In it he
wrote [326]
"With force we can calculate just as any other measurable quantity.
It is divisible, part of it can be taken away or new amounts can be
added to it and the force is not lost nor will its amount change.
Apart from the 54 known chemical elements there exists one other
agent in the world and this is force; according to the circumstances
this can exist as movement, chemical affinity, cohesion, electricity,
light or heat and all these phenomena can be transformed into one
another. The same force which lifts up a hammer can cause all the
others."
We can see that Mohr discovered the law of conservation of energy
five years before Robert Mayer published his theory. However,
Liebig refused to publish it in Annalen der Pharmazie und Chemie
and Poggendorff, editor of Annalen fiir Physik, likewise rejected it.
Finally, he sent it to Zeitschrift fiir Physik in Vienna, but then lost
interest in it. It was thirty years later before he discovered by accident
that this last journal had actually printed it [ 3 2 7 ] .
He devised many methods and pieces of apparatus such as his
determination of iron and chloride, the Mohr pinch-cock, Mohr salt,
and the Mohr balance. He also invented the pinch-cock burette
[ 3 2 8 ] , the Liebig condenser [ 3 2 9 ] , the cork borer, and many other
186
Fig. 4 0 . C o c k burette in Mohr's t i m e . ( F r o m Mohr, L e h r b u c h der. c h e m i s e h -
analytischen Titriermethode, 1855.)
devices (Fig. 40). He would immediately communicate his inven-

tions to Liebig, who would test them. Liebig found the condenser
very useful and propagated its use. So it was that his name came to
be associated with it. Liebig greeted Mohr's invention of the cork
borer with the words
"Your cork borer is a very ingenious invention and this will soon
be used in all laboratories. You have made a great contribution to
organic chemistry which needs many fine stopper holes" [ 3 3 0 ] .
Of the more than one hundred publications which Mohr produced
on anything from geology to bee keeping, possibly his most successful
was his Lehrbuch der Chemisch-Analytischen Titriermethode, pub-
lished in two parts in 1855 and 1856 [ 3 3 1 ] .
He collected isolated papers on titrimetry, studied them and tested

them experimentally. Many methods he modified and some he
abandoned altogether, replacing them with better methods. His
chapters were named after the discoverers of the particular methods,
thus under "Gay-Lussac" he deals with acidimetry and alkalimetry
and under "Marguerite" (which he mis-spelt) we find permanganato-
metry. A chapter dealing with the arsenious acid—iodine system is
entitled "Mohr". Although he was first to use the system, it does
owe something to Bunsen with whom he deals only briefly. How-
ever, he did describe the titrimetric methods in great detail and gave
a list of results which he obtained under various conditions. At the
end of the book, he classifies the methods according to the elements
and evaluates each separately, as well as giving a recommendation on
the choice of method under various circumstances. There are few
references in the book and, in many cases, Mohr received the credit
for discoveries which was due to others. He claimed that the dis-
covery of back-titration, the use of sodium hydroxide standard solu-
tion, and the introduction of normal solutions were his, although
they were already known. It is true, however, that the use of normal
solutions became much more widespread after his book. He describes
them thus: "This system is based on one litre of solution containing
one tenth of one small atomic weight (i.e. equivalent weight),
expressed in grams of the dissolved substance" [ 3 3 1 ] .
With much difficulty, he obtained 1 kg of platinum which had
been standardised with the original 1 kg etalone in Paris. He cali-
brated his weights with this several times a year [ 3 3 2 ] .
He used oxalic acid for an acidimétrie standard as it, being a solid,
gave an easily prepared accurate standard solution. He prepared the
sodium hydroxide titrant from calcium oxide and sodium carbonate
and used a guard tube filled with calcium hydroxide and Glauber's
salt to prevent carbon dioxide being absorbed.
By modifying a method of Barreswill, he could determine
hydroxide and carbonate in the presence of one another. He first
determined the total alkali content by titration with oxalic acid and
then precipitated the carbonate with barium chloride. He filtered this
precipitate, dissolved it in a known quantity of nitric acid and deter-
mined the excess of acid alkalimetrically [ 3 3 3 ] .
He mentions that the colour change is not well-defined when
litmus is used in the titration of weak acids and that it is advisable to
titrate until the appearance of the final blue colour [ 3 3 4 ] .
For redox titrations, he recommends potassium chromate as a
188
standard oxidising agent and arsenious acid as a reducing agent on
the basis of ease of preparation, stability, and clarity of end-point
detection [ 3 3 5 ] . He also describes the preparation of potassium
permanganate, which would indicate that the salt was not commer-
cially available in those days. He standardised the solution using
either piano wire, oxalic acid, or ferrous ammonium sulphate, which
he prepared especially [ 3 3 6 ] .
The analysis of brown stone was very important in those days
because of the Weldon method of chlorine preparation. Mohr records
that, as today, every tenth shovelful must be placed on one side and
the large pieces broken with a hammer. This pile is divided in quarters
making a cross. Two opposite quarters are taken and the rest rejected.
This process is repeated until only 1 or 2 oz. remain, this being taken
to the laboratory. The manganese dioxide content was determined
with oxalic acid [ 3 3 7 ] .
Mohr developed the first method for the determination of dis-
solved oxygen in water. He added a known amount of ferrous salt to
the solution and made it alkaline. After allowing it to stand for a
time, he titrated the excess of ferrous ion with permanganate. His
results did not agree with the absorption coefficients established by
Bunsen. Mohr attributed the error in his own work to the presence of
carbon dioxide [ 3 3 8 ] . Thirty years later Lajos Winkler proved, with
his experiments, that the values given by Bunsen were inaccurate.
He also described the first permanganatometric titration of an
organic substance; this was the oxidation of uric acid to urea. He
devised it following the observations of a military physician by the
name of Scholz [ 3 3 9 ] .
Mohr described Dupré's method for the determination iodide and
amplified the sensitivity. In this method, the iodide is oxidised with
chlorine to iodate and the excess chlorine boiled off. Potassium
iodide is added and the liberated iodine titrated in the presence of
chloroform. The equations he gave as
IM + 6 CI + 5 HO = C1M + 5 C1H + I 0 5
I 0 5 + 5 IK = 5 KO + 6 I
The amplification factor is six and even a concentration of 1 mg
-1
m l of iodide could be determined [ 3 4 0 ] .
Mohr finally gave a price list for various calibrated flasks and
standard solutions, which he supplied. These were produced by a

factory in which he had an interest and which was later to ruin him.
For example, a burette with Mohr-clip and capacity 50 ml,
15 groschen; 10 ml, lOgroschen; volumetric flasks, 500 ml,
20 groschen; 100 ml, 10 groschen. 11 of standard Ν nitric acid cost
10 groschen, 11 of potassium permanganate solution unstandardised,
15 groschen; while various other 0.1 Ν solutions were 10—20 groschen
per litre except for silver nitrate which cost 1 thaler 15 groschen.
Chemicals were sold by the pound and varied in price from
10 groschen for sodium and barium chlorides to oxalic and nitric
acids at 1 thaler, potassium iodide at 4 thalers 14 groschen, iodine at
6 thalers, silver nitrate at 24 thalers and finally urea, most expensive
at 30 thalers [ 3 4 1 ] . This can be put in perspective when we realise
that Liebig's Institute at Giessen had an annual budget of 100 thalers
for apparatus and chemicals although Liebig considered this sum
ridiculously small.
(E) TITRIMETRY B E F O R E SYNTHETIC INDICATORS
By the 1850's, titrimetric apparatus and standard solutions were

similar to those of today. In the next few decades, few important
developments occurred. The existing standard solutions were applied
to a wider range of methods and the available methods improved and
refined. Of course, little was known of the theory of the processes
occurring.
Fresenius in 1862 proved that the hydrochloric acid medium of
Margueritte's permanganatometric iron determination should be
replaced by sulphuric acid [ 3 4 2 ] . Kessler reduced iron(III) with
tin(II) chloride and complexed the excess of this with mercury(II)
chloride [ 3 4 3 ] . He recommended this reduction for the chromato-
metric determination of iron as the hydrochloric acid liberated
would interfere in the permanganate method. Later, he found that,
in the presence of manganese(II) ions, hydrochloric acid did not
interfere in this method [ 3 4 4 ] . However, he failed to combine his
two observations; none of his suggestions was accepted and Kessler's
name was soon forgotten. In 1881, Zimmermann rediscovered the
effect of manganese(II) salts [345] and five years later Reinhardt
combined this with Kessler's reduction. This method is still in use
[ 3 4 6 ] . For the reduction of iron(III), Jones in 1889 recommended
a tube filled with finely divided zinc [347] and ten years later
Shimer found that amalgamation increased the reducing activity
[348].
190
In the last century, it was common to name a new method after
its discoverer. However, the honour did not always go to the correct
person. This is understandable when one considers that one person
may sketch the outline of a method while several others may con-
tribute to its development into something practicable. As most of the
writers of analytical textbooks at this time were German, they
tended to chose a German responsible for some modification and
name the method after him. An example is the Volhard—Wolff meth-
od for the determination of manganese. The principle of the method,
namely the oxidation of manganese(II) ions with hot potassium
permanganate solution, was originally used by a Frenchman, Guyard,
in 1863 [ 3 4 9 ] . In 1879, Volhard found that it was necessary to have
the salt of a bivalent metal in the solution for accurate results [ 3 5 0 ] .
Wolff's contribution was to eliminate the error in Volhard's method
caused by a slightly acidic medium by using an excess of zinc oxide
[ 3 5 1 ] . However, many others contributed to the development of this
method.
A few permanganate titrations are of note. In 1863, Czudnovicz
determined vanadium after reduction with zinc or hydrogen sulphide
[ 3 5 2 ] . Reduction with hydrochloric acid or hydrogen bromide was
introduced by Roscoe [ 3 5 3 ] . The arsenious acid—permanganate reac-
tion was used to determine manganese by Deshayes in 1878, using
lead peroxide for the oxidation of manganese [ 3 5 4 ] . In place
of lead peroxide, Smith used silver nitrate and persulphate [ 3 5 5 ] .
Titanium dioxide was determined for the first time in 1864, by
Pisani who also carried out the reduction with zinc in the absence
of air [ 3 5 6 ] . The oxygen consumption of water was determined by
Forchhammer as early as 1849; he titrated hot water with permanga-
nate to a permanent pink colour [ 3 5 7 ] . Schrôtter acidified the water
[3581 » while Schulze made it alkaline and then back-titrated the
excess of permanganate with oxalic acid [359] (1868). This method
is still used today.
In iodimetry, the standardisation of sodium thiosulphate was a
great problem. The purification of iodine was complicated and incon-
venient. Kâroly Than (1834—1908) (Fig. 41) suggested the use of
potassium bi-iodate [ 3 6 0 ] . Than, introduced potassium bicarbonate
as a standard for acidimetry and alkalimetry [ 3 6 1 ] . He also sug-
gested, in 1865, that the results of analyses should not be presented
in the form of salts but in the percentage of the equivalents of each
constituent. Ostwald, who later introduced this system, acknowl-
References pp. 261—282

191
Fig. 4 1 . Kâroly T h a n ( 1 8 3 4 - 1 9 0 8 ) .
edged the earlier suggestion of Than. Later, iodic acid [362] and
potassium iodate [363] were recommended for the standardisation
of thiosulphate. The discovery by Zulkovsky in 1868 that, under
certain conditions, dichromate reacts stoichiometrically with potas-
sium iodide was important for iodimetry [ 3 6 4 ] . By oxidising or
decomposing organic substances with dichromate, the amount of
organic substance present can be found from the amount of
dichromate consumed. Reischauer, in 1862, was the first to use this
method with methyl and ethyl alcohols, the excess of dichromate
being determined with iron(II) sulphate and permanganate [ 3 6 5 ] .
192
This method was used by Steinfels to determine glycerine [ 3 6 6 ] .
The scope of iodimetry was considerably increased when the
bromination of organic substances could be used for analytical
purposes. Landolt's bromination of aniline (1871) [367] was
adapted to a volumetric method by Waller by titrating the phenol in
sulphuric acid solution saturated with alum, directly with bromine
solution until the yellow colour persisted [ 3 6 8 ] . The first method
for the determination of the iodine number of unsaturated fatty acids
was devised by Hiibl in 1884. It consisted of treating the sample in
chloroform solution with iodine in the presence of a mercury chlo-
ride catalyst, the excess of iodine being titrated with sodium thio-
sulphate [ 3 6 9 ] . However, bromine is more widely used for this
purpose today.
In determining dissolved oxygen in water, Lajos Winkler used
manganese chloride in an alkaline medium instead of the iron(II)
sulphate recommended by Mohr. He eliminated air oxidation by
pouring the solutions under the water in a layer and carrying out the
the rest of the operation in a closed bottle (1888) [ 3 7 0 ] . Winkler's
results did not agree with those of Bunsen so he repeated the latter's
experiment and found them to be not sufficiently accurate.
Charpentier introduced alkali thiocyanate for use in precipitation
titrations in 1870. He determined silver and also chloride by an
indirect method using iron(III) ions as an indicator [ 3 7 1 , 3 7 2 ] . As he
published this in an obscure periodical, the method was named after
its second discoverer Volhard, who also used it to determine mercury
[ 3 7 3 , 3 7 4 ] . Jacob Volhard (1834—1910) wanted to be an historian
but, forced by his father and assisted by Hoffmann and Liebig, he
became a chemist. He was Professor at the University of Halle from
1882 and editor of Liebig's Annalen for 39 years [ 3 7 5 ] .
Lange, in 1861, used a standard cerium(IV) solution for the deter-
mination of iron and hexacyanoferrate(II), the end-point being indi-
cated by the yellow colour of eerie sulphate [ 3 7 6 ] . However,
because of the lack of a suitable indicator, eerie salts were little used.
Hexacyanoferrate(III) standard solution was used for the first time
by Gentele in 1859 for the determination of reducing sugars [377]
and for manganese, arsenic, antimony, and chromium in alkaline
medium by back titration with potassium permanganate. The search
for reducing agents to use for standard solutions was hampered by
their susceptibility to atmospheric oxidation. Dithionite [ 3 7 8 ] ,
mercury(I) nitrate [ 3 7 9 ] , and hydrogen peroxide [380] were tried

but none proved to be of any practical importance.
With complexometric titrations, mercury(II) nitrate only became
important when Votocek found a suitable indicator in the form of
sodium nitroprussiate [ 3 8 1 ] . Liebig used silver nitrate in alkaline
solution for the titration of cyanide [ 3 8 2 ] , the end-point being indi-
cated by the precipitation of silver cyanide. Drehschmidt used potas-
sium iodide as indicator which gave a better end-point [ 3 8 3 ] . The
complex-forming action of cyanides was also applied to mercury
[ 3 8 4 ] , copper [ 3 8 5 ] , and nickel [ 3 8 6 ] .
A great many useful methods never achieved any practical impor-
tance due to lack of a suitable indicator, this being most marked in
acid—base titrations. During the 1890*8, the synthetic indicators
appeared in considerable numbers, leading to a rapid development in
titrimetric analysis, but before describing this development a brief
account of the history of indicators should prove of value [ 3 8 7 ] .
(F) INDICATORS
It was no doubt known in very ancient times that the extracts of

some plants change colour when they are treated with certain sub-
stances, but it was not until the age of iatrochemistry that these
phenomena were examined. Jorden, as mentioned earlier, noticed
that scarlet cloth, when soaked in Oil of Tartar turned blue and if
then soaked in Oil of Vitriol it became red again [ 6 9 2 ] . Boyle used
plant extracts such as litmus, cornflower, and cochineal in systematic
qualitative tests in his work Experiments and Considerations Touching
Colours [ 3 8 8 ] . He even used indicator papers.
"Take a good syrup of violets, impregnated with the tincture of
the flowers, drop a little of it upon a white paper and on this liquor
let fall two or three drops of spirit, either salt or vinegar or almost
any other eminently acid liquor and upon the mixture of these you
shall find the syrup immediately turned red" [ 3 8 8 ] .
In the phlogiston period, F. Hoffmann stated that spiritum
minérale ( C 0 2 ) in mineral waters is an acid because it turns litmus
solution red [ 3 8 9 ] . It is possible that Neumann was first to consider
using indicators to observe neutralisation. He used extract of violets
to show the acid—alkali end-point in 1727 [ 3 9 0 ] . It was soon ob-
served that various plant indicators require different amounts of acid
to change their colour, in other words, they change colour in differ-
ent pH regions. Fontana, in 1775, noted that water containing
194
carbonic acid changes litmus to red but has no effect on the extract
of violets [ 3 9 1 ] . Bergman wrote
"Blue plant juices are sensitive to acids to varying degrees. Thus
nitric acid makes sugar paper (this is presumably the blue paper used
for wrapping sugar) turn red, whereas vinegar does not. Litmus, but
not syrup of violets, is made red by air-acid (carbonic acid). When in
this way all blue plant extracts are examined with regard to their
sensitivity, a suitable progression is obtained to measure the com-
parative strength of acids" [ 3 9 2 ] .
This is the method of pH determination using indicators, but it
was to be over one hundred years before this idea could be realised.
In the field of indicators, there was no change for some time and,
although a large number were tested, litmus remained the most
popular. Mohr, in his book, mentions the instability of litmus solu-
tions stored in stoppered bottles. In an unstoppered bottle, litmus
remains unchanged over a period of years.
However, none of the natural indicators was very satisfactory.
End-points were not sharp, especially with large salt concentrations
or the titration of weak acids or carbonates. The first synthetic com-
pound to be used was salicylic acid recommended by Weiske in
1875. This gives a violet colour with ferric chloride, which disappears
in the presence of acids but reappears at the neutralisation point.
However, it was inferior to available natural indicators [ 3 9 3 ] .
Kruger, in 1876, proposed fluorescein as a fluorescent indicator. Its
fluorescence in alkaline medium is destroyed by one drop of free
acid [ 3 9 4 ] . This did not achieve a great success for, in the following
year, the first synthetic colour change indicator appeared. This was
phenolphthalein introduced by Luck [ 3 9 5 ] . This was rapidly fol-
lowed by tropeolin [396] and by methyl orange introduced by
Lunge in 1878 [ 3 9 7 ] . This was Georg Lunge (1839—1923), Professor
of Chemical Technology at Zurich Technical High School, co-author
with Professor Berl of Darmstadt of the Lunge—Berl Industrial
Analytical Handbook, which is still used as a reference book in
industrial laboratories.
The first theoretical interpretation of acid—base indicators was
made, on the basis of the ionic theory, by Wilhelm Ostwald in his
book Die Wissenschaftlichen Grundlagen der Analytischen Chemie
(1894). According to Ostwald, if the indicator itself is a weak acid,
then other weak acids can give up their hydrogen ions so that the
indicator exhibits the colour of the non-dissociated form. These are

acid-sensitive indicators, e.g. phenolphthalein, where the undisso-
ciated indicator is colourless while its ions are coloured. Methyl
orange, on the other hand, is a moderately strong acid whose ions are
yellow, the undissociated indicator itself being red. In solution, it
dissociates considerably and therefore shows a mixed colour. When
hydrogen ions are added, the amount of dissociation decreases and the
solution becomes red. A weak acid, however, contains far fewer
hydrogen ions capable of changing the equilibrium when passing
through the neutralisation point. Methyl orange is therefore more
sensitive to bases [ 3 9 8 ] .
This ionic view of indicators was challenged by Hantzsch who
proposed his chromophoric theory of indicators which interprets the
colour change from the structural organic chemical aspect. The
colour change is caused by a structural change in which the ionogenic
form is formed from the pseudo one [ 3 9 9 ] . The two theories were
reconciled by Kolthoff. According to him the colour of the indicator
is determined by the equilibrium between the pseudo and ionogenic
forms as well as by the dissociation equilibrium of the latter [ 4 0 0 ] .
Recently, theoretical organic chemists have tried to interpret the
colour change of indicators as being due to mesomeric phenomena.
So, although our knowledge has grown since the end of the last
century, as with many branches of science, our uncertainties are
greater.
According to the Ostwald theory, the relation between hydrogen
ion concentration and colour change became clear. Friedenthal in
1904 [401] was the first to devise a colorimetric determination of
hydrogen ion concentration by means of indicators using solutions of
known hydrogen ion concentration. He makes the first reference to a
buffer solution which was recommended to him by his coworker Pal
Szily. The solution contained mono- and dihydrogen phosphates and
had a fairly well-defined hydrogen ion concentration, even near the
neutral point.
In 1907, Salm investigated the colour change of 55 synthetic
indicators [ 4 0 2 ] . S0rensen, who introduced the pH function, exam-
ined about 100 indicators but only found 22 completely satisfactory.
He experienced, for the first time, errors due to proteins and salts
and drew attention to these phenomena [ 4 0 3 ] . One of the most
common indicators, methyl red, was introduced in 1908 [ 4 0 4 ] . Lubs
and Clark, in 1915, prepared most of the sulphonphthalein group of
indicators with which they were able to develop a colorimetric meth-
196
od for pH determination, which is now widely used [ 4 0 5 ] , Proszt, in
1929, found that some indicators change their colour or exhibit a
second colour change at high acidities, in effect at negative pH values
[406].
Fluorescein, which fluoresces when irradiated with visible light,
has already been mentioned, but in 1910, Lehmann discovered a
wide range of subtances which emitted fluorescence when irradiated
with UV light [ 4 0 7 ] . There is now a large number of these indicators
known. More recently, Kenny [408] and Kurtz, as well as Erdey
[409] have recommended the use of chemiluminescent indicators.
They also detect the end-point by means of emission of light but the
energy required to produce the luminescence is obtained from a
chemical reaction and no external source is needed.
Redox indicators were developed later than those for acid—base
titrations, the majority after the first World War. Earlier isolated
examples occurred, however. Gay-Lussac determined hypochlorite
by titration with arsenious acid with a few drops of indigo as indi-
cator. The end-point was detected by decolorisation of the indigo
[ 4 1 0 ] . Spot test indicators were widespread in the middle of the
19th century. Potassium hexacyanoferrate(III) and potassium iodide
with starch were used as such. At the end of the last century, Linossier
determined dissolved oxygen in water by direct titration with
iron(II) solution using an alcoholic solution of phenosaphranine as
indicator [ 4 1 1 ] . Chromatometric methods, although they were
known from an early period, did not become widely used owing to a
lack of suitable indicators. Brandt, in 1906, suggested diphenyl-
carbazide as an indicator for the chromatometric determination of
iron(II). This indicator gives a violet colour with an excess of
chromate [ 4 1 2 ] .
The first definite redox indicator was diphenylamine introduced
by Knop in 1925. He recommended it for the chromatometric deter-
mination of iron(II) [413] and later for other redox titrations [ 4 1 4 ] .
Knop and his wife, Olga Kubelkova, discovered a large number of
triarylmethane-type redox indicators [ 4 1 5 ] . More recently, chemi-
luminescent redox indicators such as siloxene [ 4 1 6 ] , luminol, and
lucigenine [417] have been discovered.
Absorption indicators are a more recent innovation. The first was
fluorescein used by Fajans and Hassel in 1923 for the argentometric
determination of chloride [ 4 1 8 ] . Although they gave a theoretical
interpretation of the mechanism, a more recent one was developed

by Schulek and Pungor. According to this, the dyestuff anion is
adsorbed on the surface of the precipitate. A colour change occurs
because it removes silver ions from the excess of the titrant and the
colour of the slightly soluble product is different from that of the
indicator anion [ 4 1 9 ] .
During recent years, substances have been discovered which can
act as acid—base, redox, and absorption indicators at the same time.
The first of these so-called multiform indicators was p-ethoxychryso-
idine, recommended by Schulek and Rozsa [ 4 2 0 ] .
(G) M O R E R E C E N T TITRIMETRIC A N A L Y S I S
Titrimetric analysis is the largest branch of analytical chemistry.

Among the large number of methods and modifications of methods,
it is very difficult to select those which have made the most impor-
tant contribution to the progress of chemistry. What follows is only a
brief outline of the more recent developments.
In acid—base titrations, the first differential method was that of
Warder (1881) for the simultaneous determination of hydroxides and
carbonates, utilising methyl orange and phenolphthalein [ 4 2 1 ] . For
the titration of weak organic acids, the acid-sensitive indicators
permitted better and more accurate results. Degener studied phenol-
phthalein in this respect [ 4 2 2 ] .
An important method for water hardness determination was devel-
oped by Wartha and Pfeiffer using sodium hydroxide and sodium
carbonate standard solutions. Until the introduction of the EDTA
method, it was used all over the world [ 4 2 3 ] .
Kjeldahl applied the old method of displacing ammonia from its
salts to the determination of the nitrogen content of organic sub-
stances. The absorption of ammonia in boric acid and the direct titra-
tion with acids originates with Lajos Winkler (1913) [ 4 2 4 ] . The
reduction of nitrates to ammonia with metals was known for some
time before Devarda in 1892 recommended the use of the alloy now
named after him [ 4 2 5 ] .
In redox titrations, Gyôry introduced potassium bromate as an
oxidising standard solution for the determination of arsenic and
antimony [ 4 2 6 ] . For a long time, there was no suitable reversible
indicator for this procedure until Schulek introduced naphtho-
flavone or p-ethoxychrysoidine [ 4 2 7 ] .
In cerimetry, Willard and Young titrated iron(II) and oxalate using
198
diphenylamine as indicator in 1928 [ 4 2 8 ] , They subsequently deter-
mined several other substances using this standard solution.
Sirokomskii et al. used potassium periodate standard solution for the
determination of iron, antimony, arsenic, and tellurium, again using
diphenylamine in each case [ 4 2 9 ] . In fact, a whole series of methods
was made possible by the discovery of diphenylamine.
Chlorine water and hypochlorite were the first oxidising standard
solutions. As they were unstable, Noll recommended Chloramine Τ
(p-toluene sulphochloramide) as a standard solution; this can be
regarded as a stabilised chlorine solution [ 4 3 0 ] .
Ascorbic acid was used by Erdey [431] as a reducing solution. It
has a sufficiently low redox potential and yet is fairly inert to atmo-
spheric oxidation. It has been applied to the determination of
iron(III), silver, chlorate, bromate, iodate, and a number of other
ions [ 4 3 2 ] .
Mercury(I) nitrate and perchlorate standard solutions were
re-examined in this century and found to be of some use, particularly
for the determination of iron(III). They were suggested first by
Bradbury and Edwards [433] and later Belcher and West [ 4 3 4 ] .
The most negative redox potential is exhibited by the chromium-
(II) system, —0.41 V. First used by Dimroth and Fister, its use is
rather limited because of the difficulty of preparation and storage
[435].
The most notable method for the determination of moisture is the
iodimetric one of Karl Fischer devised in 1935 [ 4 3 6 ] . This method
can be used with iodimetric or electrometric end-point detection.
During the 1930's, it was found that certain amino-polycarboxylic
acids formed stable, soluble complexes with a large number of metals,
notably alkaline earths. Under the name "Trilon", I.G. Farbenindus-
trie marketed one of these compounds which became widely used in
industrial processes. A theoretical examination was begun in the
1940's and, as a result, Schwarzenbach developed methods for deter-
mining calcium and magnesium and also water hardness. Possibly the
best of the large number of complexones is ethylenediaminetetra-
acetic acid disodium salt. The introduction of metallochromic indi-
cators led to the development of a large number of methods involving
direct titration of the metal ion solution with a standard solution. In
these methods, the strength of the metal—EDTA complex is greater
than that of the metal indicator complex so that, at the end-point,
the colour of the free indicator appears. Schwarzenbach also intro-

duced the first of the metallochromic indicators, murexide (ammo-
nium purpurate) [ 4 3 7 ] . The growth in this area has been very great.
Even in 1958, a review could list one thousand original papers on the
analytical applications of EDTA alone [ 4 3 8 ] .
In the field of microanalysis, Mylius and Fôrster were the first to
carry out acid—base titrations with 0.001 Ν solution, using eosin as
indicator in 1891 [ 4 3 9 ] . The first microburette, which had a volume
of 3 ml, was constructed by Pilch [ 4 4 0 ] . One design for a micro-
burette using two parallel tubes was introduced by Bang in 1922
[441] and is still seen today.
Titrations in non-aqueous media were not investigated until this
century. Non-aqueous solutions had, however, been used from an
early period. Boyle recorded the insolubility of numerous water-
soluble salts in alcohol. Lowitz separated calcium chloride from
barium chloride using absolute alcohol (in which the latter com-
pound is insoluble) [ 4 4 2 ] . It was Lowitz who was the first to prepare
moisture-free solvents, namely absolute ether and glacial acetic acid
[ 4 4 3 ] . The first person to titrate in non-aqueous media was Vorlânder
in 1903; he titrated aniline with hydrochloric acid dissolved in
benzene [ 4 4 4 ] . The theoretical aspects of this subject were initially
considered more important until Foreman's method for the deter-
mination of amino acids showed the practical importance. This meth-
od involved the titration of amino acids in a mixed alcohol/acetone/
formaldehyde medium [ 4 4 5 ] . Other workers in this field were
Connant, Hall, Werner, Folin, Tomicek, Fritz, Kolthoff, Briickenstein,
Gautier, Pellerin, Chariot and coworkers. Acid—base titrations are
the most thoroughly studied. The first steps in the subject of redox
titrations in non-aqueous media were taken by Tomicek and
coworkers and by Erdey and Râdy.
6. Organic elemental analysis
(A) FROM LAVOISIER TO LIEBIG
Scheele was the first person to carry out a systematic examination

of the chemical constitution of plants and, as a result, he discovered
malic, citric, tartaric, oxalic, gallic, uric, and lactic acids as well as
glycerine. On the basis of this work, Scheele can be regarded as the
founder of scientific organic chemistry.
200
The early experiments of van Helmont showed that water was
formed when organic substances were burnt. Soon after the discov-
ery of carbon dioxide, this gas was found to evolve from the com-
bustion of coal and other organic substances. The theory of combus-
tion was thus disclosed, water is formed from the combustion of
hydrogen and carbon dioxide from carbon. The conclusion was ob-
vious: organic compounds are composed of carbon and hydrogen.
Lavoisier considered that organic compounds are composed of
carbon, hydrogen, and oxygen. Berthollet was first to discover
nitrogen in animal extracts at the end of the 18th century [ 4 4 6 ] .
The first experiment on the composition of organic substances was
carried out by Lavoisier. In it, he examined various oils using a rather
complicated apparatus [ 4 4 7 ] . He combusted the oil in a burner, led
the combustion products through a cooler and then through a
calcium chloride tube before absorbing in sodium hydroxide
(Fig. 42). The results, however, were not very reliable [ 4 4 8 ] . Using a
F i g . 4 2 . L a v o i s i e r ' s first a p p a r a t u s f o r c o m b u s t i o n a n a l y s i s o f o r g a n i c s u b s t a n c e s .
Drawing b y M m e . Lavoisier in t h e b o o k , Traité é l é m e n t a i r e de c h i m i e o f
Lavoisier ( 1 7 8 9 ) .

simpler apparatus, he found the ratio of hydrogen to carbon in
alcohol to be 3.6 : 1, while the correct value is 4 : 1. The accuracy
was very good when we consider that this was the first analysis of its
type. He tried an experiment using metal oxides, such as mercury
oxide and manganese dioxide, and potassium chlorate to provide the
oxygen for combustion. He tried to determine the composition of
sugar by this method but his attempts were unsuccessful [ 4 4 9 ] .
Despite inaccuracies, Lavoisier's main achievement was that he
showed the correct approach to organic elemental analysis. Subse-
quent methods were essentially improvements on his. experiments.
Contemporary analysts such as Klaproth were attempting to analyse
organic substances simply by dry distillation followed by determina-
tion of the amounts of gases, oils, and residue formed during the
process.
Gay-Lussac and Thénard, in 1810, devised a technically different
method, carrying out the combustion in tubes. The apparatus is
shown in Fig. 43 [ 4 5 0 ] . At the upper end of the combustion tube
was a tap with a hole in it rather than the usual channel. Into this
hole, the sample mixed with potassium chlorate was placed. Rota-
Fig. 4 3 . Apparatus for c o m b u s t i o n and analysis o f organic s u b s t a n c e s o f Gay-

Lussac and Thénard. ( F r o m their R e c h e r c h e s Physico-chimiques, 1 8 1 0 . )
202
tion of the tap caused the sample to fall into the heated part of the
tube. Air had been removed by a preliminary blank combustion. The
combustion products were led through mercury to a sealed vessel.
Carbon dioxide was absorbed by potassium hydroxide in the
mercury vessel and the amount determined from the volume decrease
of the gas. Next, the excess of oxygen was exploded with hydrogen
and the oxygen loss determined. The original amount of oxygen was
known since, in a previous experiment, the amount of oxygen
formed from potassium chlorate was determined. The decrease in
oxygen was considered to be due to the combustion of the hydrogen
content of the substance and thus the hydrogen content was found
in this indirect manner.
In principle, the method could only yield accurate results when
the substance itself did not contain oxygen. In practice, several other
errors existed. Also, the reaction was occasionally so violent that the
combustion tube shattered. In spite of all these difficulties, Gay-
F i g . 4 4 . C o m b u s t i o n a p p a r a t u s o f B e r z e l i u s . ( F r o m Pfaff, H a n d b u c h d e r a n a l y -
tischen Chemie, 1 8 2 1 . )

Lussac and Thénard examined about twenty organic substances and
obtained reasonably accurate results.
Berzelius used a horizontal tube heated uniformly over its length,
thereby combusting the whole sample (Fig. 44). To decrease the
vigour of the reaction, he mixed sodium chloride with the potas-
sium chlorate. An important improvement which he made was to
weigh the water directly. Most was condensed in the first receiver,
the rest being absorbed by a calcium chloride tube. The carbon
dioxide was measured in the bell volumetrically, although it was
possible to measure this gas from the increase in weight of a small
vessel of potassium hydroxide which had been allowed to stand
inside the bell for 24 h [ 4 5 1 ] . Berzelius's method was much more
accurate than those of his predecessors, although it still had a few
faults. To Liebig's criticism that it took Berzelius eight months to do
thirteen analyses, the latter replied that it was the purification of the
compounds which took so much time.
Gay-Lussac later discovered that copper oxide was far more
efficient than potassium chlorate [452] and, in an independent
investigation, Dôbereiner reached the same conclusion. A piece of
apparatus, which is in common use today, the U-tube, was designed
by Bussy who used it for the first time in 1822, filled with anhydrous
calcium chloride [ 4 5 3 ] .
(B) F R O M LIEBIG TO P R E G L
Born in 1803, Justus Liebig (Fig. 45) was one of eleven children
whose parents were not very rich. He failed examinations at school
consistently so his father took him away and apprenticed him to a
pharmacist. He eventually became interested in chemistry and read
avidly. On one occasion, an experiment of his exploded and almost
demolished the whole house. Finding himself unemployed as a result,
he eventually enrolled at the University of Bonn and later at
Erlangen. He got a fellowship in Paris and, working under Thénard
and later Gay-Lussac, obtained some interesting results. With some
help from Humboldt, the famous German explorer, he was given the
Chair of Chemistry at the small University of Giessen at the age of
24. Despite some resentment from the staff because of his age and
lack of money, he gained a great reputation for his teaching methods.
An extract from a letter illustrates the conditions under which he
worked.
204
Fig. 4 5 . Justus Liebig ( 1 8 0 3 — 1 8 7 3 ) . Trautschold's drawing from 1 8 4 5 . ( F r o m
K o p p , G e s c h i c h t e der C h e m i e , 1 8 4 7 . )
"I shall repeat the analysis more accurately as soon as the water in
my laboratory thaws."
Liebig published a great deal but was a sharp and objective critic
of other chemists.He also suffered from bouts of extreme depres-
sion, possibly aggravated by his poor financial position and large
family. He tried several business ventures to supplement his income
but none was successful until, in his old age, he became a partner in
an Argentinian meat extract firm. He had noticed that cattle there
were slaughtered for their hides, the meat being left to rot. The
Liebig meat cube resulted from this enterprise.
Meanwhile, his enthusiasm for teaching waned. When he accepted
a post at the University of Munich in 1852, it was with the stipula-

Fig. 4 6 . C o m b u s t i o n apparatus o f Liebig. ( F r o m his w o r k A n l e i t u n g zur A n a l y s e
organischer Kôrper, 1 8 3 7 . )
tion that he should not be required to teach. His interest in chemis-

try declined until his death in 1873.
Liebig was one of the most important figures in organic chemistry.
He analysed many organic substances never previously examined.
The theory of organic radicals and the explanation of the valency of
acids were due to him. He discovered that plants obtain the carbon
required for growth from the air and that fertile soil requires
nitrogen and phosphorus. He recognised the possibility and impor-
tance of the production of chemical fertilizers.
The determination of carbon and hydrogen in organic elemental
analysis is still carried out using Liebig's principles. His original
apparatus is shown in Fig. 46 [ 4 5 4 ] . Heating was carried out with
hot coal. With several sections in the combustion tube container,
the heating could be adjusted by varying the amount of coal. Carbon
dioxide could be measured by noting the increase in weight of the
potassium hydroxide in the small triangular glass apparatus. In the
horizontal tube before the C 0 2 absorber, anhydrous calcium chlo-
ride was packed to absorb the water.
The removal of combustion products was achieved by breaking off
the small end of the combustion tube and sweeping air through the
system. Liebig claimed that the error from C 0 2 in the air was offset
by the loss of water vapour from the potassium hydroxide. Berzelius
passed the air through potassium hydroxide before sweeping the
tube. The two men had bitter arguments over this question as they
had over how to connect the tubes. Liebig favoured cork stoppers
while Berzelius used rubber tubing. In practice, rubber was found
most suitable.
206
With the widespread use of gas lighting and the invention by
Bunsen of his gas burner [455] in 1857, coal as a source of heat was
abandoned.
Mulder recommended soda-lime to replace potassium hydroxide
solution. He filled seven-eighths of a U-tube with this absorbent and
the remaining one-eighth with calcium chloride to retain the water
liberated from the former [ 4 5 6 ] . For his analysis of starch, Brunner
took up Lavoisier's suggestion of combustion in an oxygen atmo-
sphere [ 4 5 7 ] . Hess was first to use a small vessel for the introduction
of the sample [458] and Kopfer discovered the benefits of using a
catalyst with oxygen combustion. He used platinum black and later
platinised asbestos. He also used silver fibres as catalyst for halogen-
containing samples [ 4 5 9 ] .
The accuracy of carbon determinations was limited by the accu-
racy with which the composition of carbon dioxide was known.
Lavoisier believed the ratio of carbon to oxygen to be 311 : 800.
Berzelius corrected this value to 306 : 800 while finally, in 1840,
Dumas found the ratio to be 300 : 800 which is correct [ 4 6 0 ] .
The nitrogen content of organic substances was first determined
by Gay-Lussac and Thénard using the method previously described
where the gas remaining after the explosion of the excess of oxygen
was considered to be nitrogen. After much work, Liebig determined
nitrogen, carbon, and hydrogen. The nitrogen and carbon dioxide
were collected in a eudiometer over mercury (water had previously
been absorbed), the carbon dioxide absorbed in potassium hydroxide,
and the nitrogen measured volumetrically. Difficulties arose in
removing air from the apparatus and finally removing the combus-
tion products. He heated a suspension of calcium hydroxide in a
vessel in the sealed end of the combustion tube to form water vapour
to flush out the tube.
In 1831, Dumas used a eudiometer tube filled with alkali hydroxide
thus eliminating the need for the separate absorption of carbon
dioxide. He also heated lead carbonate, generating carbon dioxide to
flush the system [ 4 6 1 ] . He reduced nitrogen oxides with copper
activated in a stream of hydrogen.
Jean Baptiste Dumas (Fig. 47) was born in Alais in 1800 and, like
many famous chemists before him, he became an apprentice
pharmacist. He moved to Geneva where he became quite famous.
Humboldt assisted his career as he had done earlier for Liebig and
persuaded him to go to Paris. He also became assistant to Thénard.

Fig. 4 7 . Jean B a p t i s t e D u m a s ( 1 8 0 0 — 1 8 8 4 ) . ( F r o m B u g g e , D a s B u c h der grossen
Chemiker.)
During this time, he developed his method for vapour density mea-
surement and discovered methyl alcohol in 1824. Dumas was asked to
investigate why the candles at a reception given by King Charles X
gave off clouds of soot and a gas which caused the guests to choke.
He discovered that the candle-maker had used chlorine to whiten the
wax and that hydrogen chloride gas was formed. As a result he exam-
ined the reactions of chlorine and bromine with organic compounds
and found that substitution of a halogen for hydrogen can take
place. This conflicted with Berzelius's dualistic theory and resulted in
a long and bitter argument between the two men.
Meanwhile, Dumas' reputation increased. He became Professor at
the College de France, a member of the Academy and, finally, Gay-
Lussac's successor at the Sorbonne. He dabbled in politics and
208
became Minister for Agriculture and Trade. When he died in 1884, he
was given a state funeral.
Since the work of Dumas, nitrogen determination has changed
little. In his method, however, it was difficult to fill the combustion
tube and then transfer the combusted gases over mercury into a
vessel to measure the volume. Dennstedt later wrote "The nitrogen
determination was a punishment for everybody, until azotometers
were introduced!" The first azotometer which proved to be of use
was introduced by Schiff [ 4 6 2 ] .
Because of the difficulties with nitrogen determination, interest
was turned to alternative methods. In 1831, in a letter to Gay-
Lussac, Dumas mentions that certain compounds, for example
oxamide and urea, give off ammonia when heated with alkali and he
suggests that this gas could be determined volumetrically. By the
time he had developed a method [ 4 6 3 ] , ten years later, two students
of Liebig, Varrentrapp and Will had introduced a much better meth-
od, now named after them [ 4 6 4 ] . On ignition of the compound with
barium hydroxide, the ammonia liberated was passed into hydro-
chloric acid and determined gravimetrically by precipitation as
ammonium hexachloroplatinate.
Péligot modified the method so that the ammonia was absorbed
in a known amount of hydrochloric acid and the excess back-titrated
using lime dissolved in water containing sugar [ 4 6 5 ] . This method
became widely used but was later found to be inaccurate.
In 1883, Kjeldahl tried using sulphuric acid to assist the decompo-
sition in the determination of the nitrogen content of proteins. This
proved successful and, after further studies, he published his method
[ 4 6 6 ] . To assist the digestion, he added phosphoric acid and potas-
sium permanganate to the sulphuric acid, collecting the ammonia in a
known amount of sulphuric acid and back-titrating. He did not
describe the apparatus in any detail; apparently he used ordinary
flasks. Later, specialised pieces of apparatus were designed as the
method became popular, Kjeldahl himself designing the distillation
assembly which is named after him [ 4 6 7 ] . Johan Gustaf Kjeldahl
(1849—1900) was in charge of the chemistry department at the
Carlsberg Institute which a man called Jacobsen, who was owner of
the Carlsberg beer factor, had founded for the purpose of research on
brewing and the beer industry. Later, Kjeldahl became its director.
Kjeldahl knew that the method had its limitations. In the case of
nitro and cyano compounds as well as alkaloids, the digestion was
not suitable. Asboth modified the method by omitting permanganate

and digesting nitro compounds by adding benzoic acid to the
sulphuric acid digestion mixture [ 4 6 8 ] . Jodlbauer reduced the diges-
tion time by using phenol instead of benzoic acid [ 4 6 9 ] . With nitro-
naphthalenes, Chenel effected digestion by adding iodine and phos-
phorus [ 4 7 0 ] .
As with nitrogen, attempts were made to replace combustion with
digestion for carbon determination. Rogers and Rogers determined
the carbon content of graphite in quartz by heating the sample in a
retort with sulphuric acid and potassium dichromate. The carbon
dioxide formed was passed into potassium hydroxide and back-
titrated [ 4 7 1 ] . Brunner, in 1855, used this method for organic sub-
stances, measuring the carbon dioxide volumetrically [ 4 7 2 ] . Legler
oxidised glycerine in this manner and measured the volume of C 0 2
formed [ 4 7 3 ] . However, wet procedures never achieved any real
importance because of the need to carry out a combustion to deter-
mine hydrogen.
The detection of sulphur in organic substances was first made by
Robiquet and Thibierge, who found it in mustard oil, while the first
method for the quantitative determination of sulphur in organic
compounds was devised by Henry and Plisson. They mixed the com-
pound with iron oxide and quartz sand and heated it in a stream of
oxygen, from heated potassium chlorate, in a combustion tube. The
carbon dioxide formed was absorbed in sodium tetraborate, while
the sulphur dioxide was measured volumetrically [ 4 7 4 ] .
Even Henry himself was not very satisfied with this method. In
1834, he digested the substance with fuming nitric acid and then,
after fusing with potassium hydroxide, determined the sulphate
formed gravimetrically [ 4 7 5 ] . In the same year, Zeise fused the sub-
stance with potassium nitrate in a crucible, following digestion with
aqua regia, finally determining it as sulphate [ 4 7 6 ] . The principle of
this method is still used today; only the order of the steps and the
purity of the oxidising agents have changed.
Naturally occurring organic halogen compounds were only dis-
covered in the middle of the 19th century; halogens had been deter-
mined only in synthetic products. Kekulé boiled the substitution
products of organic acids with sodium amalgam and water and split
off the bromine in this way [ 4 7 7 ] . Gustavson used sodium methylate
for this purpose, carrying out the reaction in a sealed vessel [ 4 7 8 ] .
Since then, other substances, especially alcohols, have been recom-
mended for this purpose. When this treatment is insufficient, a com-
210
bustion or digestion is used. Erdmann simply ignited the compound
with lime [ 4 7 9 ] . Piria, in 1857, used a mixture of lime with soda. He
placed the mixture in a platinum crucible and inverted this in a larger
crucible filled with soda—lime mixture, which he then heated [ 4 8 0 ] .
Kopfer's method, mentioned previously, using oxygen combustion
with a platinum catalyst, was applied by Zulkovsky and Lepez for
the determination of sulphur, halogens, carbon, hydrogen, and nitro-
gen [ 4 8 1 ] , but their method was improved by Dennstedt [ 4 8 2 ] .
Even this was not a great success and a convenient method for the
complete elemental analysis of organic compounds is still being
sought today.
The determination of other elements in organic compounds is
relatively simple because the element sought is finally converted to
an ionic form.
The most common constituent of organic compounds, apart from
carbon and hydrogen, is oxygen. Its determination is very difficult
and, even today, the oxygen content is usually found by difference.
It was only at the beginning of this century that any success was
achieved in direct oxygen determination.
Baumhauer was first to examine this in the 1850's [ 4 8 3 ] . The
combustion was carried out in a nitrogen atmosphere with a known
amount of oxygen. The'carbon dioxide, water, and unbound oxygen
were determined, thus giving the oxygen content of the sample.
Copper oxide was used as the source of oxygen. Later, Ladenburg
recommended silver iodate [ 4 8 4 ] . Unfortunately, it is impossible to
understand the latter's method and it is unlikely that anyone has
even tried to repeat it.
Hempel and Markert, in 1904, attempted to convert the oxygen to
carbon monoxide by passing the combustion products over incandes-
cent carbon. Although they were unsuccessful, Schutze in 1939 used
this principle with success. He mixed the substance with carbon,
heated it to a high temperature in a nitrogen atmosphere and then
led the gases through a further layer of carbon at 1000° C. The
oxygen was first converted to carbon monoxide and then, with
iodine pentoxide, to carbon dioxide, this being measured in the usual
way [ 4 8 5 ] .
Ter Meulen introduced catalytic hydrogénation using thorium and
nickel into elemental analysis. This method, when used for nitrogen,
sulphur, and the halogens, resulted in the formation of ammonia,
hydrogen sulphide, and hydrogen chloride, which can be easily esti-
mated [ 4 8 6 ] .

Macro methods of organic elemental analysis are seldom used
today, having been almost completely replaced by microanalysis.
This has the advantage of being quick, convenient, and accurate. It
plays an important role in physiology, biology, and biochemistry.
Microanalysis did not simply entail scaling down the apparatus and
procedures of macro methods. It required patience, skill, and original
thought, three qualities which abounded in the father of micro-
analysis, Fritz Pregl.
Fritz Pregl (Fig. 48) was born in Laibach, now Ljubljana, in 1869.
F i g . 4 8 . F r i t z Pregl ( 1 8 6 9 — 1 9 3 0 ) .
212
He studied at the University of Graz, becoming a lecturer in the
Institute of Physiology there. After a brief period with W. Ostwald
and later Emil Fischer, he returned to lecturing at Graz where, apart
from three years at the University of Innsbruck, he remained,
becoming a professor. He died there in 1930.
He became interested in organic analysis through his work in bio-
chemistry, and developed most of his methods between 1910 and
1917. At the end of this period, after few publications, he published
Die Quantitative Organische Mikroanalyse which opened up a whole
new field of chemistry. In 1923, he received the Nobel Prize for
chemistry, the first award for analytical chemistry.
Pregl first published his methods for the microdeterminations of
carbon, hydrogen, and nitrogen in 1912 [ 4 8 7 ] , He introduced a
universal tube filling, consisting of copper oxide, lead chromate, lead
peroxide, and silver metal, which can be used for all types of organic
compounds. Both the Dumas and Kjeldahl methods were adapted to
the micro scale but, as the latter is then less accurate, it is seldom
used. Pilch first employed it on the micro scale using sulphuric acid,
potassium sulphate, and mercury chloride for the digestion [ 4 8 8 ] .
The hydrogen iodide—phosphorus methods originate from Friedrich
[ 4 8 9 ] , while the micro apparatus was designed by Roth [ 4 9 0 ] .
The Zeise—Vohl method for the qualitative detection of sulphur
was adapted by Burger to a quantitative microdetermination [ 4 9 1 ] .
The compound is reacted with potassium in a sealed tube and the
sulphide formed titrated iodometrically. The first micro determina-
tion of halogens was devised by Emich and Donau early this century
by adapting the Carius method [ 4 9 2 ] . More recently, the flask meth-
od of Schôniger has been introduced where the compound is com-
busted in oxygen [ 4 9 3 ] .
Because of the large number of organic compounds, functional
groups, and possible reactions, a systematic scheme of qualitative
organic analysis is still being perfected today.
At the beginning of this century, Mulliken attempted to classify
compounds on the basis of the physical properties and chemical reac-
tions of their characteristic groups [ 4 9 4 ] . This has proved to be the
best basis for any scheme. The work of Staudinger on functional
group reactions in 1923 is noteworthy [ 4 9 5 ] . Stig Veibel and his
coworkers approached the problem from a different aspect. They
used quantitative methods for qualitative analysis by preparing the
derivatives of the original substance and then determining their

equivalent weights. From these, the original substance can be identi-
fied.
7. Instrumental methods
(A) ELECTROGRAVIMETRY
Although static electrical phenomena had been known since

ancient times, Luigi Galvani made an important advance in 1780. He
placed a frog's leg, which had a copper hook in it, on an iron plate.
The leg twitched. This started ten years of research for Galvani. His
experiments caused a great sensation in Europe and everywhere frogs
were caught. Adults and children repeated his miraculous experiment.
In 1800, Alessandro Volta (1745—1827) constructed the first
galvanic cell. This was known as the Volta pile and consisted of
thirty or forty (or often more) zinc and silver discs, placed alter-
nately on top of one another and separated by a small piece of cloth
impregnated with an acid or salt solution. This was the first durable
and convenient source of current. Very soon, enormous Volta piles
were constructed and used for experimentation; some of them con-
tained more than a thousand discs! Napoleon himself authorised the
construction of a large pile which he presented to Davy.
In the same year, two English chemists, Carlisle and Nicholson,
found that electricity decomposes water [ 4 9 6 ] , Another Englishman,
Cruickshanks, also in 1800, established that metals are deposited on
the negative pole, while acids (anions) are deposited on the positive
pole. He also recommended electrolytic deposition of a metal as a
qualitative test and described it as a test for copper [ 4 9 7 ] . This reac-
tion is also described in Pfaff's book, where copper is deposited on
zinc [ 4 9 8 ] .
In 1808, Davy made his famous discoveries of the electrolytic
decomposition of the alkalis and earths (which had previously been
considered elements) with the Volta pile and isolated the strange new
metals [ 4 9 9 ] .
Humphry Davy (1778—1829) (Fig. 49) was one of the greatest
chemists of all time. Early in his career, while working in a hospital,
he discovered nitrous oxide (laughing gas). Davy was invited to
become a lecturer at the recently founded Royal Institution and his
lectures were extremely popular. He made most of his great discov-
214
Fig. 4 9 . H u m p h r y D a v y ( 1 7 7 8 — 1 8 2 9 ) . Painting b y T h o m a s L a w r e n c e .
eries at this period but still had time for a hectic social life. Often in
a great hurry, he would put clean clothes on over old ones. It was
said that he once wore five pairs of stockings on top of one another.
He was knighted, married a rich and attractive widow, and
attempted to act the aristocrat but without much success.
He is famed for his discoveries of the arc light, the miner's safety
lamp, and of the fact that chlorine is an element. However, when
asked what he regarded as his most important discovery he replied
"Faraday". Michael Faraday had started his career as Davy's appren-
tice. Davy died at the early age of 50.

Regarding qualitative work, in 1812 Fischer detected arsenic by
electrolysis [ 5 0 0 ] . In 1830, Becquerel observed that, on electrolysis,
lead and manganese are deposited at the positive pole [ 5 0 1 ] . Cozzi
used it to identify metals in metallic salt solutions [502] and, in
1815, Gaultier de Claubry recommended the use of electric current
for the detection of toxic metals. He deposited the metals after diges-
tion with nitric acid on platinum. Despretz separated lead from
copper by electrolysis, the latter being deposited on the anode and
the former on the cathode [ 5 0 3 ] .
In 1864, Wolcott Gibbs (1822—1908) became the first to apply
the electrolytic reduction of metals to analysis by weighing the
amount of deposited metal. He determined copper by using a plati-
num crucible as the cathode attached to the negative pole of a
Bunsen cell. The positive pole was connected to a platinum wire
immersed in the solution in the middle of crucible. He passed the
current until a small sample of the solution gave no precipitate with
hydrogen sulphide. After the electrolysis, he rinsed the crucible with
distilled water, dried it in a vacuum over concentrated sulphuric acid,
and reweighed it. He carried out the determination of nickel in a
similar manner but from ammoniacal medium [ 5 0 4 ] .
Luckow, a chemist with a railway company, discovered electro-
gravimetry independently of Gibbs. At least he wrote, in 1865, that
since 1860 he had been determining copper and silver by electrolysis
from potassium cyanide solutions [ 5 0 5 ] .
As the electrolysis method for copper spread rapidly, it is under-
standable that other metals were soon determined in this way. Meth-
ods for zinc, lead [ 5 0 6 ] , mercury [ 5 0 7 ] , cadmium [ 5 0 8 ] , and
manganese [509] were developed in rapid succession. Yver also
carried out separations; he separated cadmium and zinc by electro-
lysing first from alkaline solution and then from acetic acid medium
[510].
Alexander Classen was the first to examine the influence of the
current and applied voltage and he also introduced the use of mea-
suring devices into the circuit [ 5 1 1 ] . He used accumulators instead
of galvanic cells and was the first to discover the advantages of using
warm solutions. This, combined with efficient mixing, enabled him
to develop rapid methods of electrolysis. Classen's first book on elec-
trogravimetry was entitled Quantitative Analysis auf Electrolytischen
Wege and ran to 52 pages. Twenty years later, the fifth edition had
336 pages, such was the growth in electrolytic methods.
216
The original crucible or pot-shaped platinum electrodes were used
for a long time without alteration. Paweck introduced the use of
metal-net electrodes for the electrolysis of mercury. They were disc-
shaped and made of brass [ 5 1 2 ] . C. Winkler developed the cylinder-
shaped net electrodes, which are still used today, as well as the spiral
platinum wire anode [ 5 1 3 ] . The use of a rotating anode to ensure
mixing of the electrolyte was introduced by Klobukhov [ 5 1 4 ] .
The development of theoretical electrochemistry clarified many
puzzling phenomena. Le Blanc determined the decomposition poten-
tial for many metal salt solutions [515] and as a result of this work,
Freudenberg, working in the Institute of Ostwald, attempted to
separate various metals by variation of deposition potential [ 5 1 6 ] .
Many other types of electrodes were tried but, in the end, it was
concluded that platinum was the best. Apart from this, only the
mercury cathode is of interest. Gibbs himself was the first to attempt
to deposit metals on a mercury cathode and to determine these as
amalgams [ 5 1 7 ] . Luckow separated zinc and silver with the aid of a
mercury cathode from iron, nickel, cobalt, and manganese as the
latter do not form amalgams [ 5 1 8 ] . Deposition at controlled poten-
tial was first suggested by Sand, who used an auxiliary electrode for
this purpose [519] and although he credits the first work on the
subject to C. Ullgren [ 7 0 3 ] , it is Sands' name which is associated
with the technique of internal electrolysis [ 7 0 4 ] .
The technique known as electrography is a branch of electrogravi-
metry. It is a qualitative method which has the advantage of sensitiv-
ity and of leaving the sample unaltered. The principle is that the sub-
stance under examination is made to function as the anode. It is
separated from the cathode by a strip of moistened filter paper
impregnated with a neutral salt to increase conductivity and a reagent
which will detect the required component. This method was dis-
covered independently, in 1929, by Glazunov and Fritz [ 5 2 0 ] .
Coulometry is a relative method and is a direct analytical applica-
tion of Faraday's Laws. It is based on the measurement of the
amount of current passed through the cell. Obviously, this can only
be applied where the electrode process is accurately known and when
no side reactions take place. The end-point is indicated by a suitable
chemical reaction, e.g. for an acid, a common acid—base indicator
can be used. Coulometry was introduced by Szebellédy and Somogyi
in 1938. They used a silver coulometer and determined the titre of
hydrochloric acid, sulphuric acid, thiocyanate, hydrazine, sodium
hydroxide, and hydroxylamine standard solutions [ 5 2 1 ] .

(Β) OPTICAL M E T H O D S
Optical methods of analytical chemistry are nowadays progressing

in two different directions. The first is in the application to specific
analytical procedures and the second is in the development of instru-
mental methods. The main optical methods are spectroscopy,
spectrography, flame photometry, spectrophotometry, and color-
imetry, although borderlines are rather diffuse and strict definitions
are difficult.
Spectroscopy is the oldest optical method whose foundations were
laid by Isaac Newton. In 1666, he observed that the image of a
narrow slit on the lattice of a window became wider and was
coloured if a prism was inserted between the light source and the
screen. He concluded from this experiment that the white light of
the sun is composed of light rays of differing refractive indexes and
that the colour of these rays is related to their indexes. He experi-
mented with different prisms, lenses, and slit widths finally ob-
taining a spectrum 25 cm long using a 1 mm slit width [ 5 2 2 ] .
The first chemist to contribute to spectroscopy was Marggraf who
noted the difference in the colour imparted to a flame by sodium
and potassium [ 5 2 3 ] . The flame emission of the alkaline earth metals
was first observed by Lowitz.
In 1800, Herschel, the famous astronomer, measured the tempera-
ture of the radiation in different parts of the spectrum of sunlight
and found that the temperature at the red end was highest. He also
found that, beyond the red end, some invisible radiation caused it to
be even higher [ 5 2 4 ] . A year later, Ritter discovered ultraviolet rays
by their effect on siver chloride. He established that their reducing
power, in effect their energy, was greater than that of the violet end
of the spectrum [ 5 2 5 ] .
In 1802, Wollaston noticed black lines in the sun's spectrum. How-
ever, he described this discovery inaccurately and did not pursue the
subject [ 5 2 6 ] . In the same year, Young calculated the wavelengths of
the different spectral lines using a diffraction grating [ 5 2 7 ] .
Following these investigations, Fraunhofer, in 1814, rediscovered
the black lines in the sun's spectrum. Josef Fraunhofer (1787—1826),
the tenth child of a poor family, could not read or write at the age
of 15 and was working in a glass factory when the building collapsed
and buried him. Just when it seemed that everything was against him,
his luck changed. He was found to be unhuçt and a generous mer-
218
chant, reading of the incident in the local press, took the boy into his
care and educated him. Although the merchant died soon after,
Fraunhofer got a job in an optical workshop. He studied hard,
became a partner in the firm and eventually a member of the Bavarian
Academy of Sciences. He died young, at the age of 39.
While studying the degree of dispersion of light by a prism,
Fraunhofer found that the limits of the spectrum were not suffi-
ciently sharp for this purpose. He repeated the experiment in dark-
ness using the light from a candle and noticed that there is a sharp
band between the red and yellow bands. He decided to use this line
to measure the refraction but, on repeating the experiment with sun-
light, he found the line absent and a dark line in its place. He
designed a special apparatus consisting of a slit, a prism and a
theodolite and used the telescope of the theodolite to examine the
spectrum. He found innumerable black lines and proved that these
were part of the solar spectrum and not errors in the apparatus. He
made a diagram of the lines and assigned capital letters to the most
prominent ones. He counted the smaller ones; for example, between
the Β and Η lines he recorded 754. However, as this work appeared
to have little practical importance, he stated that he would leave
further examination to the scientists [ 5 2 8 ] . Little did he realise what
technical importance his discovery would have one day.
In 1822, Herschel, son of the famous astronomer, said of his
investigations of the spectra of various flames
"It is very probable that these colours originate from the mole-
cules of the coloured substances which after being transformed to
the vapour state are in vigorous motion."
However, he must have been troubled by sodium as he concluded
that, at a certain temperature, all flames become yellow [ 5 2 9 ] .
In 1826, Talbot, whose name is well known in the history of
photography, constructed a device for the examination of flame
spectra. He dipped a wick into the substance to be examined, dried
it, lit it and, passing the light from the flame through a slit and a
prism, examined the emergent spectrum on a screen. This was a
primitive attempt at spectroscopy. He observed that potassium salts
emitted a characteristic red line, while sodium salts gave a yellow
line. Talbot was the first to connect the appearance of a given line
with the presence of a certain compound [ 5 3 0 ] .
Brewster, in 1832, suggested that the dark lines in the sun's spec-
trum are formed because of the absorption of some of the radiation

by the high temperature gaseous envelope surrounding the sun. He
proved this experimentally by passing light through nitric acid
vapour and showing the presence of dark lines [ 5 3 1 ] . Miller, even
earlier, had passed light through tubes containing bromine or iodine
vapour and showed the existence of dark lines in the emergent spec-
trum [ 5 3 2 , 5 3 3 ] .
The younger Herschel was the first person to photograph spectra,
in 1840. He passed sunlight through a narrow slit onto a brominated
light-sensitive paper. He found the UV region much larger than
expected and the extent of darkening greater than in the IR region
[ 5 3 4 ] . Although his photographs were not of such good quality as
those of Herschel, Draper incorporated a variable slit constructed
from two knife edges adjusted by a micrometer screw. He projected
the spectrum on to a white screen so that he could mark the lines. In
the visible violet region alone, he counted over 600 lines [ 5 3 5 ] . He
later used a diffraction grating [ 5 3 6 ] .
As a result of all this investigation, it gradually became clear that
the absorption lines in the sun's spectrum and the flame emission
lines are identical. We shall not, however, consider the further experi-
ments in this field but restrict our attention to those matters of most
concern to analytical chemistry.
Angstrom published a long and detailed paper describing the major
differences in the spectra of solid and gaseous substances in which he
records the fact that metals give the same spectrum as their com-
pounds. He came very near to the discovery of the reversal of spectral
lines. He made a diagram of the sun's spectrum alongside a spark
spectrum and commented, "When looking at this, one has the
impression that the first is the reverse of the second" [ 5 3 7 ] . This was
later to be elaborated by Kirchhoff.
In 1854, Alter, an American, stated that
"The spectrum emitted by an element differs from all others in its
number of bands, intensity and position so that the element can be
identified simply by observation . . . . The colours seen in the Polar
Light possibly indicate the elements being present. By the use of a
prism it is possible that the elements of the stars and the Earth can
also be identified."
He determined the spectral lines of the individual elements in the
visible region and published this in the form of tables [ 5 3 8 ] .
Swan, in 1856, discovered that the R line of the spectrum is due
to sodium and that this can be used to detect sodium even when it is
220
present in a concentration of only one part in two and a half million
[ 5 3 9 ] . Helmholst was the first to use a quartz prism to investigate
the UV region of the sun's spectrum [540] and Robiquet, similarly,
was the first to use an arc for producing spectra [ 5 4 1 ] .
1859 was the most important year for spectroscopy. Plucker
established that the spectrum of the discharge of a gas contained in a
sealed tube is characteristic for the gas. He also discovered the first
three lines of the hydrogen spectrum [ 5 4 2 ] . Van der Willigen investi-
gated the effect of different electrodes on gaseous spectra, as well as
the effect of metal salts evaporated on the electrodes and the separa-
tion of the electrodes [ 5 4 3 ] . Finally, it was also in 1859 that
Kirchhoff and Bunsen began to publish the first results of their
experiments with the first spectroscope, marking the start of a new
chapter in analytical chemistry [ 5 4 7 ] .
(C) K I R C H H O F F A N D B U N S E N
Although, as we have seen, Bunsen and Kirchhoff were not the

first workers in this field, nevertheless it was they who made spec-
trum analysis a practical method of analytical chemistry. They
Fig. 5 0 . First s p e c t r o s c o p e o f B u n s e n and Kirchhoff. ( F r o m their original paper,

1860.)

demonstrated it to be an extremely sensitive method and even their
first publication recorded the discovery of new elements in samples
previously examined by chemical methods [544] (Fig. 50).
At this time, Kirchhoff was Professor of Physics and Bunsen was
Professor of Chemistry at Heidelberg University. The former was
concerned with the optical side of the problem, while the latter dealt
with the chemical aspects. Bunsen described those days in a letter to
Roscoe.
"Now I am working with Kirchhoff which hardly gives us time for
sleep! Kirchhoff has made a miraculous discovery. He has discovered
the cause of the black lines in the sun's spectrum. What is more he
can magnify them and also produce lines in a colourless flame spec-
trum which correspond exactly to the Fraunhofer lines. You will
understand that this now makes it possible for us to determine the
composition of the sun and stars just as accurately as we can identify
chloride or sulphate in the laboratory. With the same degree of
accuracy we can identify the individual elements on earth also. For
example, we were able to detect lithium in 20 g of sea water! For the
identification of certain substances this method is far more sensitive
than any other. If you have a mixture consisting of lithium, sodium,
potassium, barium, strontium and calcium, you need only give me
one milligram for, with my apparatus, looking at it through a
telescope, without touching the substance at all, I can tell you which
elements are present" [ 5 4 5 ] .
They tried several different flames but found the characteristic
lines always remained constant. They discovered rubidium and
caesium in 1861 by examination of flame spectra [ 5 4 6 ] .
Kirchhoff was first to report the phenomena of reversed spectra
[ 5 4 7 ] , by which he meant that a coloured line disappears from the
spectrum to be replaced by a black line if a light source with a con-
tinuous spectrum is passed through a gas. He therefore explained the
dark lines in the sun's spectrum by suggesting that they were caused
by absorption of radiation by the gases which surround the sun's
glowing nucleus. This theory was proved experimentally several years
later when Janssen found some lines of unknown origin in the sun's
spectrum [ 5 4 8 ] . Lockyer repeated these experiments and explained
the results by postulating the existence of an unknown element,
which he called helium [ 5 4 9 ] .
By 1861, Bunsen and Kirchhoff were using an improved spectro-
scope where the spectra of two light sources could be examined
222
Fig. 5 1 . Kirchhoff's spectral device, 1 8 6 2 . ( F r o m his original paper.)
simultaneously and compared with a scale [ 5 4 6 ] . In the next year,

Kirchhoff replaced the single glass prism with four prisms in a semi-
circle and this gave a lengthening of the spectrum as well as an
improvement in the resolution (Fig. 51).
Also in 1861, Kirchhoff reported on his investigations of the sun's
spectrum and assigned lines to each element although, unfortunately,
he used an arbitrary scale. In his first paper, he records only those
lines between the D and F lines as his eyes became so tired that he
could not continue [ 5 5 0 ] . With the help of coworkers, he eventually
finished the work in 1863 [ 5 5 1 ] .
This work attracted great attention and some criticism, partic-
ularly from British scientists such as Kelvin, Brewster, and Crookes.
They maintained that Stokes, Talbot, or even Wheatstone [552]
were the discoverers of this phenomenon. Kirchhoff subsequently
published a paper in which he discussed the previous history of spec-
trum analysis, detailing the failures of his predecessors in contrast to
his own discoveries. If he had included this in his original paper, the
controversy may have avoided [ 5 5 3 ] . It is obvious that, as in other
branches of science, spectrum analysis did not originate from nothing.

Fig. 5 2 . Gustav Kirchhoff ( 1 8 2 4 — 1 8 8 7 ) . Engraving from the journal Berichte,
1887.)
There was a great deal of preliminary investigation upon which

Bunsen and Kirchhoff were dependent. However, it is indisputable
that only as a result of their work did spectrum analysis become a
usable method. Even in the 1860's, the method was named after
them. A catalogue of laboratory equipment published in 1866 by the
English firm Griffin advertised a Kirchhoff—Bunsen-type spectro-
scope for 5 guineas [ 5 5 4 ] .
Gustav Kirchhoff (Fig. 52) was born in 1824 in Kônigsberg and
subsequently studied natural science at the university there. After
224
graduation, he became a Privât Dozent in Berlin, until the University
of Breslau appointed him Professor of Physics. Bunsen became
Professor of Chemistry at Breslau shortly afterwards and a great
friendship developed. When Bunsen moved to the more illustrious
Heidelberg University, he contrived to have Kirchhoff appointed
there also. It was there that they collaborated in their research on
spectroscopy. After this work, Bunsen turned to the chemical
applications, whilst Kirchhoff examined the spectra of the stars. In
1879, he accepted the chair of physics at the University of Berlin.
Fig. 5 3 . R o b e r t Wilhelm B u n s e n ( 1 8 1 1 - 1 8 9 9 ) .

However, he suffered several illnesses and died in 1887.
Robert Wilhelm Bunsen (Fig. 53), one of the greatest personalities
in analytical chemistry, was born in 1811 in Gôttingen, a famous
University town. He studied physics, chemistry and geology at the
University. After graduating, he undertook a travelling fellowship,
later returning to Gôttingen as Privât Dozent. In 1834, he became a
teacher at the technical school in Kassel, in succession to Wôhler and
in 1839, he was offered a Professorship at the University of Marburg
from where, in 1851, he went to the University of Breslau. A year
later, he was given the chair of Chemistry at Heidelberg, which had
previously been occupied by Gmelin.
The first scientific works of the young Bunsen concerned organic
chemistry. He examined the cacodyl compounds and estabished that
the cacodyl component is a radical, providing invaluable proof of the
new organic theory of radicals. It is strange that he did not pursue a
career in organic chemistry, especially when one notes that chemistry
in Germany in that century meant organic chemistry. Indeed, it was
difficult to find anyone to fill the chairs of inorganic chemistry.
In 1838, Bunsen investigated the combustion processes occurring
in iron furnaces. Using gas analysis, he found that about 50% of the
fuel was lost. His results caused great interest and consequently he
was invited to England to examine the furnaces there which used
coal. Things were even worse there with 81% of fuel wasted. His
findings encouraged constructional changes in the furnaces to
improve economy. He published his methods in Gasometrische
Methoden (1857) which was the beginning of modern industrial gas
analysis.
In 1846—1847, he went to Iceland at the invitation of the Danish
government where he carried out geological observations and investi-
gated the geysers. He studied petrography but geology was only his
hobby until later life when he became fully occupied by it. He also
worked with Roscoe on photochemistry, examining the flame reac-
tions of individual elements for qualitative analytical purposes. In
1857, he constructed the famous Bunsen burner [ 4 5 5 ] . He also
designed the water pump in 1868 [ 5 5 5 ] . He introduced the labora-
tory stand and for many years the Bunsen battery was used in elec-
trochemistry. He can be regarded as the Edison of analytical chemis-
try, for in his long life he worked in many fields and made important
practical contributions to each of them.
Bunsen was essentially a practical chemist, remaining disinter-
226
estedly apart from the theoretical disputes which raged during this
period. His views are illustrated by two quotes "A hypothesis which
only leads to further possibilities has no value" and "A single deter-
mination of one fact is more valuable than the most beautifully con-
structed theory". He was a great teacher, his lectures being inter-
esting and well attended. These were never published and he made
no changes in them throughout a quarter of a century. Thus, they
became rather dated. He took charge of his laboratory classes
throughout his whole working life and his practical skill was a living
legend. His students stayed for one or two years before leaving for
other universities. The reason for this was that he never promoted
anyone, even objecting to students using books saying that they only
contained useless theories!
He was very modest, both in behaviour and requirements. He
never married saying that he never had time, although in later life he
complained of loneliness and isolation. He attributed little impor-
tance to the many honours he received. When someone congratulated
him on receiving a famous award he replied "Oh my God! The only
good thing about these honours was that they made my mother
happy but now she, poor soul, is dead". Many stories are told of his
absent mindedness. One of his colleagues visited him and after
talking for an hour and a half was about to depart when Bunsen said,
"you can imagine how poor my memory is, but when I first saw you
I thought that you were Kekulé". The visitor looked astonished and
said, "But I am Kekulé!"
Bunsen remained Professor at Heidelberg for thirty-seven years
until his retirement in 1889. Thereafter, he lived very quietly in a
street which had been named after him. He died in 1899.
(D) FURTHER DEVELOPMENT OF SPECTRUM ANALYSIS
The importance of spectroscopic analysis was proved in the next

few years by the discovery of several new elements. Shortly after
caesium and rubidium, thallium, indium, and gallium were discovered
by this method.
However, wavelengths of spectral lines were known only inaccu-
rately. Mascart recalculated these in 1863—1864 using a diffraction
grating with 400 lines per millimetre but his results were not accurate
[ 5 5 6 ] . Many other investigations were made [557] before Angstrom
finally made a thorough study [ 5 5 8 ] . He carried out his measure-

ments so carefully with instruments of such precision that the ques-
tion was considered solved. Ten years after his death, Thalén, one of
his coworkers, reported that an error in the measurement of the
grating width had made all the results inaccurate [ 5 5 9 ] . He gave a
correction according to which 13/100,000 of the value of each wave-
length must be added to it. Rowland constructed a grating marking
device which could inscribe 1720 lines per millimetre. He later con-
structed concave gratings which resulted in an increase in the disper-
sion and sharpness of the spectral lines. He measured about 1100 lines
of the sun's spectrum as well as arc spectra with an estimated error of
less than 0.01 Â over the range 2 1 5 2 . 9 1 - 7 7 1 4 . 6 8 Â [ 5 6 0 ] .
Langley introduced the bolometer at this period for measuring the
infrared part of the sun's spectrum [ 5 6 1 ] . Also, the development of
photography resulted in spectrographers using photographic plates to
record their spectra from 1880 onwards.
Quantitative spectrum analysis has only been developed in the
present century, although Lockyer earlier carried out a series of
experiments concluding that, while qualitative analysis is based on
the position of the lines, quantitative analysis could only be based on
the length, strength, and number of lines [ 5 6 2 ] . Pioneering work in
this field was carried out by Hartley and coworkers. They established
that, in the spectra of all the elements, there are lines which cannot
be detected under a given concentration limit [ 5 6 3 ] , Hartley, as well
as Leonard and Pollok and also de Gramont, attempted to develop a
system of quantitative analysis at the beginning of this century
[ 5 6 4 ] , Their methods were based on the fact that the amount of a
given element can be found from an examination of the number of
lines appearing in the spectrum. Unfortunately, inaccuracies occurred
due to disappearance of lines caused by the quality of the plate, the
amount of electrical excitement, and the time and method of
exposure of the plate.
Work on quantitative spectrum analysis lapsed for some time until
Gerlach solved the problem in 1924 [ 5 6 5 ] . His method, which
involves the use of homologous line-pairs, was later refined by
Schweitzer [ 5 6 6 ] . In this method, samples containing varying
amounts of the element to be determined also contain constant
amounts of a base element. Whereas the intensity of the lines of the
latter should remain constant, that of the former should vary with
concentration. It is then only necessary to find a pair of lines, one of
the base and one from the element being determined, which exhibit
228
similar intensity (blackness). When two lines of equal intensity have
been found, the concentration can be obtained from a calibration
curve or table.
Scheibe and Neuhàusser introduced the use of a rotating disc in
front of the slit, which is cut in the shape of a logarithmic curve. This
resulted in spectral lines of lower intensity being shorter than those
of greater intensity and hence from the relative length of two
homologous lines, their relative concentration could be estimated
[ 5 6 7 ] . The measurement of line intensities by photoelectric methods
was introduced by Lundegârdh in 1929 [ 5 6 8 ] . Quantometric
(spectrometric) methods based on the scanning of spectrum lines
with a photomultiplier unit originates with Dieke and Crosswhite
(1945).
X-Ray fluorescence analysis was first studied by Hadding (1923)
as well as Hevesy and Alexander (1932). However, it was in the
1950's that development began to gain impetus with the technical
improvement of radiochemical instruments.
The possibility of carrying out flame photometric measurements
(as we know them today) was first realised by Janssen in 1870. He
discovered that the amount of substance present was proportional to
the amount of illumination given out when the molecules were
excited in a flame [ 5 6 9 ] . This theory was proved experimentally
three years later by Champion et al. who determined sodium with
an apparatus which consisted of a spectroscope and an instrument in
which the extinction of light from a known amount of sodium, using
a blue glass, was compared with the required extinction for the sub-
stance to be determined [ 5 7 0 ] . De Gramont, in 1923, introduced the
oxygen—acetylene flame for use in spectrography [ 5 7 1 ] . Then, in
1928, Lundegârdh developed a flame photometer which consisted of
an atomiser, pressure control unit, and an acetylene—air flame [ 5 7 2 ] .
He first used a spectroscope but later employed a single mono-
chromator for the dispersion of the light and measured the light
intensity with a photocell. Schuhknecht, in 1937, replaced the
monochromator with simple coloured filters [573] and in this form
the flame photometer is still used today.
The use of atomic absorption spectroscopy as an analytical tech-
nique was suggested by Walsh in 1955 [ 7 0 5 ] . He proposed a hollow-
cathode lamp as source and a flame for the production of atoms of
analyte element from solution samples introduced as a fine mist in
air. Alkemade and Milatz [706] independently suggested using a

flame as radiation source and a second flame as sample cell. The first
monograph on the subject was written by Elwell and Gidley in 1966
[707].
(E) COLORIMETRY
Snelders [711] refers to what must be the earliest colorimetric

method. He notes that W.A. Lampadius, in 1838, estimated the iron
and nickel content of a cobalt ore by comparing the colour of the
corresponding filtrate with the colours of solutions of known metal
contents 5—50% Fe or Ni and 50—95% Co in cylindrical tubes.
Heine used a similar principle in 1845 when determining bromine
in mineral waters. He made a series of solutions with varying
amounts of potassium bromide dissolved in water. He then added an
equal amount of ether. On adding chlorine water, he achieved a
gradation in the reddish-brown colour of bromine in the ether layers.
He could then treat his sample in a similar manner and compare its
colour with that of the standards [ 5 7 4 ] .
The next year, Jacquelain devised a method for the determination
of copper, based on the comparison of the colours of copper—ammo-
nia complexes [ 5 7 5 ] .
Herapath determined iron in 1852 by a colorimetric procedure
using thiocyanate. He also used reference solutions which contained
iron in amounts from 1 to 250 mg. He compared the colours of the
solutions using a white paper screen [ 5 7 6 ] .
In 1853, Miiller constructed what he called "a complementary
colorimeter" (Fig. 54) and described its operation as follows.
"The coloured solution is placed in the vertical cylinder A. This is
made of glass and at the bottom (e) a colourless biplan glass plate is
used to seal it. On the side (dd) there is a scale graduated in milli-
metres. To the top of this cylinder a stopper (cc) is fitted and this
contains an adjustable glass tube through its centre, this tube also
being sealed by a colourless glass plate. This telescopic tube system
stands on the wooden box. The mirror (i) can be adjusted by the
knobs (kk) and allows sunlight to pass through the diaphragm and
through the glass disc (g) (made of the complementary colour to that
of the solution under investigation). Thus, the coloured light passes
through the solution placed in A and can be observed at a.
If the solution in A consists of diluted iron thiocyanate solution
then a kingfisher-blue plate (g) is used. The tube A is closed with an
230
Fig. 5 4 . Miiller's " C o m p l e m e n t e r c o l o r i m e t e r " , 1 8 5 3 . ( F r o m his original p a p e r . )
opaque shield. If the small tube is adjusted then, when it is in the

highest position, the bottom plate appears to be reddish-yellow, but
as the telescopic tube is gradually lowered the colour of this plate
gradually changes, passing through white until finally it appears to be
kingfisher-blue.
If one has some sense of colour, even in the case of slightly
coloured solutions, one can determine the position where the plate
appears to be white with an accuracy of some ten millimetres and I
base my colorimetric method on this fact.
We find the zero value of a dilute solution of known concentra-
tion and note the position on the scale. This could be, for example,

η. We mark this distance on the coloured glass plate used, i.e. the
height of the boundary liquid column. From the latter we can calcu-
late the amounts of coloured substances using this value and the
value obtained from the measurement; from the separation of the a
and e bottom plates the concentrations can be calculated by inverse
proportions" [ 5 7 7 ] .
He used this to investigate iron thiocyanate, chromate solutions,
and the copper—ammonia system. In the first, he found that he
could determine 0.75—3 mg/100 ml iron but the colour depends on
the free acid and thiocyanate concentrations. The weak point of the
procedure is the method of illumination which produces a com-
pletely uncontrollable light [ 5 7 8 ] .
Duboscq, in 1870, measured the colour density of the solution to
be determined directly with a comparison solution. He passed the
light through two glass prisms so that one half of a circular plate was
illuminated by the light passing through the sample solution while
the other half was illuminated by light passing through the com-
parison solution [ 5 7 9 ] .
With the introduction of this instrument, this field had reached its
peak, so we shall now consider another branch, photometry. These
two branches differ in the method of measurement. While in color-
imetry the optical part of the instrument is adjusted until equal
colour strengths are obtained, in photometry, monochromatic light is
used mainly and the intensity of this light is adjusted accordingly.
Absorption spectroscopy is based on the Beer—Lambert law.
These two workers did not collaborate, for a hundred years separated
them. It could equally well be called the Bougouer—Bernard law as
these two Frenchmen established it independently of their German
colleagues. Moreover, Bougouer long preceded Lambert while
Bernard was only a few months behind Beer.
Pierre Bougouer, in a work entitled Essai d'Optique sur la Gradua-
tion de la Lumière, (Claude Jombert, Paris, 1729) writes that a light
of 32 candle power gave an intensity of only 16 candle power when
viewed through a certain thickness of glass. Twice this thickness did
not completely obliterate the light but gave an intensity of 8 candle
power. Eventually, 5 thicknesses gave 1 candle power. He concluded
that this was a geometric progression.
Johann Heinrich Lambert used more mathematical exactness. In
his book Photometria [ 7 0 8 ] , published in 1760, he writes
"If a light beam with an intensity / passes through a layer of width
232
I (in this case through glass), its intensity will decrease to (l/n)Ith
of its original intensity, while if it passes through a further similar
layer its intensity will decrease to (l/n)I — (1/n) of its original value.
If the width of the layer is m fold of the first, the intensity of the
exit light will be
m
ΐ = I/n
In this work we can also find the following interesting sentence:
"The amount of captured light is the greater, the greater the number
of particles within a given volume and the larger the surface area of a
single particle." It is not certain whether by this he meant concentra-
tion, but it can be assumed to be so.
Lambert was born in 1728 in Muhlhausen into a poor family. He
was completely self-taught, became a teacher for various aristocratic
families, and studied hard in his spare time. He was very conceited
and while waiting for the king to appoint him to the Academy in
Berlin he is reputed to have said, "I am not impatient, but this is a
matter for his own glory. It would be a discredit to his reign in the
eyes of posterity if he did not appoint me". His appointment made,
King Frederick the Great, speaking to him at a reception, asked him
with which of the various branches of science he was most expert, to
which Lambert replied, "With all of them".
"Thus you are an eminent mathematician also?" asked the king.
"Yes, sir".
"Who was your master in this science?"
"I myself, Sir".
"That means that you are a second Pascal?"
"At least, Sir", replied Lambert.
After Lambert had left, the king commented that it seemed he had
appointed a great fool to the Academy. Lambert died in Berlin in
1777.
Later, in 1852, Beer pointed out that Lambert's law is also valid
for solutions and that, in certain cases, concentration plays a similar
role to the layer width [ 5 8 0 ] . Beer also defined the absorption
coefficient as did Bernard in the same year [ 5 8 1 ] .
The concept of the absorption coefficient was introduced into
analytical chemistry by Bunsen and Roscoe during their photo-
chemical investigations. Their definition of this function is the
reciprocal of the layer width at which the original light intensity is
decreased to l / 1 0 t h of its original value [ 5 8 2 ] . The absorption and

concentration are proportional to one another. This, however, was
only used for analysis by Vierordt.
Bahr and Bunsen were the first to use absorption spectroscopy for
quantitative analysis. They projected the spectra of a reference and a
sample solution, one above the other, and diluted the latter until it
gave lines of the same intensity as the reference. By this method,
they could calculate the concentration of the sample. However, the
method was rather difficult [ 5 8 3 ] , They did not realise the possibil-
ities of the absorption coefficient. The advisability of regulating the
light intensity rather than changing the concentration was first dis-
covered by Govi and Vierordt. Govi projected two light sources onto
a screen and varied their light intensities by adjusting their distance
from the spectroscope [ 5 8 4 ] .
The founder of photometry as we know it today was Vierordt. In
his apparatus, a glass cell was half-filled with the solution to be deter-
mined and placed in front of a slit. This slit had an upper and a lower
part, both of which could be adjusted with a micrometer screw. The
light from a petroleum lamp passed partly through the solution and
lower slit and partly above the solution and through the upper slit. It
then passed through a spectroscope. Naturally, the light travelling
through the solution was the weaker of the two, but by closing the
upper slit, the light intensities could be made similar. The micro-
meter screw was calibrated from 0 to 100 and gave a direct measure
of the transmission of the solution [ 5 8 5 ] . The main error occurred
because the monolateral alteration of the slit width affected the
quality of the light. Glan and Hiifner, independently, overcame this
problem by decreasing the light intensity using polarisation [ 5 8 6 ] .
However, these instruments were too complicated for routine
analysis. G. Kriiss emphasised the need for simplification in the first
comprehensive colorimetric monograph. He even attempted to design
some instruments, calling them spectrocolorimeters [ 5 8 7 ] .
As we have seen, the original spectrophotometers are older than
the slit-variation types, the latter being constructed for routine
laboratory work. Photometers incorporating photocells were only
developed this century. Berg produced one of this type using a
selenium element in 1911 [ 5 8 8 ] . This type of instrument only came
into general use after 1925.
234
(F) THE M E A S U R E M E N T OF pH
The earliest, and now most frequent, method for obtaining pH is

based on EMF measurement. In this system, two hydrogen elec-
trodes are used in a concentration cell where the concentration of
one compartment is known and the potential is measured by the
Poggendorf-type compensation. The hydrogen electrode was dis-
covered by Le Blanc in 1893 [589] but the form in which it is used
today was devised by Wilson and Kern [ 5 9 0 ] . Salessky and Salm also
measured pH with hydrogen electrodes and S0rensen combined a
hydrogen electrode with a calomel one. The calomel electrode had
been used by Kohlrausch even earlier.
S^rensen used a calomel electrode with 0.1 Ν potassium chloride
as the positive pole together with a hydrogen electrode. A pressure
of moist hydrogen gas of 1 atm and a temperature of 18°C was used
in all cases. S^rensen found that the voltage when 1 Ν acid was used
was 0.338 V.
pH measurement with a hydrogen electrode is not very convenient
so attempts were made to replace it with a more suitable one. This
brought about the introduction of the glass electrode. Cremer, who
was a biologist, was experimenting with the electrical properties of
tissues in 1906. He separated sodium chloride solutions with a glass
membrane 0.02 mm thick and added sulphuric acid to one of them.
He noted a potential difference of about 0.23 V between the two
solutions and considered that the membrane was responsible for this
[591].
In 1909, Haber and Klemensiewicz investigated this phenomenon
more extensively and found that the potential difference between
the solutions varied with the hydrogen ion concentration as the
hydrogen electrode potential changes in solutions of varying pH.
They used a calomel electrode as reference and noted the possibility
of replacing the hydrogen electrode with a glass one of Thuringen
glass [592] (Fig. 55). Their expectations were not realised for some
time. There were problems with the choice of the glass and the
sensitivity of the galvanometer. Thus, it was not until the 1920's that
interest revived. Mclnnes and Dole discovered a suitable type of glass
[593] and the introduction of vacuum tube voltmeters which made
accurate measurements possible.
Biilmann, in 1920, found that a shiny platinum electrode immersed
in a saturated solution of quinhydrone gave a potential proportional

Fig. 5 5 . Glass e l e c t r o d e of Haber and K l e m e n s i e w i c z , 1 9 0 9 . ( F r o m their orignal
paper. )
to the pH of the solution [ 5 9 4 ] . The antimony electrode was recom-

mended by Uhl and Kestranek in 1923, originally for the measure-
ment of the pH of soil. At first they added antimony oxide to the
solution, but later found that there was always enough oxide on the
electrode surface to enable it to function [ 5 9 5 ] .
A colorimetric method for pH determination was first devised by
Pal Szily for use with blood serum. He determined the hydrogen and
hydroxyl ion concentrations of the transition point of several indi-
cators (poirriers-blue, α-naphtholphthalein, phenolphthalein, litmus,
rosolic acid, and alizarin). He found the transition point to be depen-
dent only on the hydroxyl ion concentration and independent of the
nature of the residual solution [ 5 9 6 ] .
This method was improved by Friedenthal in 1904 [ 5 9 7 ] . He
prepared fifteen solutions with hydrogen ion concentrations ranging
- 14
from 1 to 1 0 in decreasing exponents and examined fourteen
236
indicators, tropaeoline, neutral red, methyl violet, methyl orange,
congo red, lacmoid, litmus, galleine, rosolic acid, p-nitrophenol,
sodium alizarin sulphonate, phenolphthalein, naphtholbenzoin, and
poirriers-blue. From these, he found an indicator which changed
colour in each of his standard solutions. His work was continued by
Salm, who examined the hydrogen ion concentration of the buffer
solutions with a hydrogen electrode and also investigated the colour
changes of several other indicators.
A more accurate colorimetric method was developed by S^rensen
in 1909. With this, the pH value could be determined to within one
tenth of a pH unit. The principle was identical to Friedenthal's meth-
od except that S^rensen used a larger number of indicators and
buffers [ 5 9 8 ] .
Several other workers devised series of buffer solutions, probably
the most important of which were those of Clark and Lubs. They
used potassium chloride, potassium hydrogen phthalate, boric acid,
sodium hydroxide, and hydrochloric acid as buffer solutions and
introduced the sulphonphthalein series of indicators. The sulphon-
phthaleins were very effective for this purpose because of their
regular gradation in colour [ 5 9 9 ] .
(G) POTENTIOMETRIC T I T R A T I O N
The first potentiometric titration was carried out by Behrend

(Fig. 56) in 1893 at Ostwald's Institute in Leipzig. In his paper
entitled Electrometrische Analyse [600] he writes
"In a cell, composed of mercury, N/10 mercurous nitrate —N/10
mercurous nitrate, mercury, the voltage is initially zero. If potassium
chloride is added to one of these solutions, mereury(I) chloride is
precipitated, thus the osmotic pressure of the mercury(I) ions
decreases on this side and a potential difference is set up, so that the
mercury will be more negative in the solution to which potassium
chloride is added relative to the unchanged mercury electrode. If
further equal amounts of potassium chloride are added the potential
difference increases slowly at first but later at an increasing rate. The
potential difference is measured by the correlation π = 0.058 l o g p 2 /
P i , provided that the small EMF at the junction of the solutions is
ignored. If p 2 is constant, the value of π will double if p x decreases to
3
one hundredth of its original concentration. To achieve this 990 c m
3
of N/10 KC1 must be added to 1000 c m of N/10 HgNQ 3, assuming

Fig. 5 6 . R o b e r t B e h r e n d ( 1 8 5 6 - 1 9 2 6 ) .
that both of these salts are completely dissociated. For a further one
3
hundred fold decrease only 9.9 c m of KC1 solution are required and
3
for the next decrease of this order only 0.099 c m are needed. The
addition of potassium chloride causes the most marked effect when
all the mercurous nitrate is precipitated, a sudden increase in the
potential difference then being observed. If additional increments of
potassium chloride are made there is only a very slight increase in the
potential difference, this of course being controlled by the law of
mass action. The product of chloride and mercurous ions is constant,
provided the mercury(I) chloride is present in excess and therefore
the osmotic pressure of mercury(I) ions decreases with the increasing
amount of chloride ions."
238
Thus, Behrend explained why the potential break occurred at the
equivalence point. He pointed out that this type of titration is also of
use for a number of redox and precipitation titrations. One of its
great advantages was "that its use is independent of the source of
light and can be used equally well in daylight or by lamp light".
Something of a modest appraisal of the advantages of potentiometric
titrations!
The next potentiometric method was described four years later. In
1897, Bôttger published a paper which dealt with the potentiometric
titration of acids and bases using a hydrogen electrode. This hydro-
gen electrode was made of gold plated with palladium and the
voltage was measured by a compensation method. The reference sys-
tem was another hydrogen electrode immersed into a solution of an
acid or a base. He titrated 14 different acids and bases by this meth-
od. He also added indicators and observed if the colour change corre-
sponded to the biggest potential change [ 6 0 1 ] ,
The third potentiometric method was recommended by Crotogino
[ 6 0 2 ] . He used the method previously used for precipitation and
acid—base titrations for redox titrations. He titrated halide ions with
potassium permanganate using a shiny platinum electrode and a
calomel electrode. However, he only obtained a satisfactory result
for iodide.
These first three potentiometric procedures were only considered
as curiosities in later years and were rarely used. It was not until
research was carried out in the 1920's that the method became more
widely known. However, several other potentiometric procedures
were devised. Dutoit and Weisse used polarised electrodes in 1911
[603].For some metal ions, there are no reversible electrodes avail-
able and so, to overcome this, a platinum electrode is used. If the
current is kept very low, a constantly renewed surface of the metal is
plated onto the electrode. Another modification was the titration to
zero potential, where the reference electrode system has a potential
equal to that of the indicator electrode at the end-point of the titra-
tion. Thus, it is not necessary to plot the EMF during the titration
but only to find the point where zero current is flowing with, for
example, a galvanometer. The method has the advantage of being
rapid, but the serious disadvantage that a different indicator system
must be chosen for each titration. It was recommended simulta-
neously by Pinkhof [604] and Treadwell and Weiss [ 6 0 5 ] in 1919.
In 1925, Cox showed the principle of differential titration [ 6 0 6 ] .

The solution is divided into two parts and connected by a salt bridge.
Both portions are titrated in the same manner except that one titra-
tion is kept 0.2 ml ahead of the other. The end-point is indicated by
the potential difference maximum.
The so-called "dead-stop" end-point detection is based on the
polarisation of the electrodes. In this method, a small voltage is
applied to the polarised platinum electrodes, so that the EMF of the
polarisation is just compensated. If the standard solution used for the
titration is able to depolarise the electrodes, then the first excess of
this will be indicated by the flow of current through the circuit,
which is detectable by a galvanometer. It can also be used in the
reverse manner with the cessation of current indicating the end-
point. The method was described by Foulk and Bawden in 1926
[ 6 0 7 ] . To be strictly accurate, it must be mentioned that Salomon
published a method based on a similar principle in 1897 [ 6 0 8 ] .
The first monograph on potentiometric titrations was written by
E. Millier in 1923 and entitled Die Elektrometrische Massanalyse.
Potentiometric titrations can also be carried out on the micro and
semimicro scales. There is now a wide range of miniature electrodes,
one of the first being constructed by Alimarin.
(H) CONDUCTOMETRIC TITRATIONS
Conductometric titrations are based on the change in conductivity

of a solution during a titration. For example, when an acid is titrated
with an alkali, hydrogen ions of high mobilities are removed to be
replaced by metal ions of low mobilities. The conductivity therefore
decreases steadily until the end-point where it begins to increase
slightly due to free hydroxyl ions. The conductivity is therefore a
minimum at the end-point.
The use of conductivity measurements for analytical purposes was
first suggested by Kuster and Griiters [ 6 0 9 ] . Their paper is short and
does not include a graphical representation of their results. There is
also no reference to their method of measurement; presumably they
used the bridge system recommended by Kohlrausch [ 6 1 0 ] , with a
set of head-phones to detect the null-point. This arrangement was
also suggested by Ostwald [ 6 1 1 ] . As there was no a.c. galvanometer
available to give visual indication of the conductivity, Jander et al.
developed a d.c. galvanometer used with a detector or thermocouple
[ 6 1 2 ] . Kolthoff published the first monograph on the subject in
1923 entitled Konduktometrische Analyse.
240
High frequency titrations are also based on the change of con-
ductivity of a solution during a titration. The main advantages are
that it can be used for very low concentrations and no internal elec-
trodes are needed. However, the apparatus is complicated and expen-
sive and the theory would be impossible to describe in a few lines. It
was introduced, in 1946, simultaneously by Foreman and Crisp, and
by Jensen and Parrack [ 6 1 3 ] . It should be noted that Blake had used
this principle for concentration measurement earlier.
(I) P O L A R O G R A P H Y
Polarography is simply electrolysis with a dropping mercury elec-

trode. Mercury is used because the overvoltage of hydrogen on this
metal is very high and, as a liquid, its surface is continually renewed.
Lippmann, in 1873, used mercury for the first time in his capillary
electrometer. When a current was passed through the cell, the mer-
cury electrode with the small surface area was immediately polarised,
while the anode, a large mercury pool, was practically unpolarised
because of the low current density. He used this devise for the deter-
mination of the surface tension of polarised mercury [ 6 1 4 ] . Kucera,
in 1903, modified this device by elevating the mercury reservoir until
the pressure caused the mercury to drop out of the capillary. He
determined the surface tension by weighing the mercury droplets
[ 6 1 5 ] . When he drew a graph of droplet weight versus polarising
voltage, Kucera obtained electro capillary curves and found some
secondary maxima, but did not suggest an explanation.
In 1918, Heyrovsky established that these are caused by the oxy-
gen in the air. He pointed out that the current on the surface is a
much more characteristic measure of the electrochemical reactions
taking place on the dropping surface than is the surface tension
[ 6 1 6 ] . These investigations led him to make a survey of the v o l t a g e -
current curves and thus to the development of polarography.
Heyrovsky, together with Shikata, invented the polarograph [617]
in 1925 (Fig. 57). Their paper records the polarograms of several sub-
stances including lead, zinc, cadmium, and nitrobenzene. Since then,
polarography has become much more sophisticated largely due to the
efforts of Heyrovsky and his coworkers.
Several methods for the production of derivative curves have been
developed during the last decade including a retarding electrode
[ 6 1 8 ] , a condenser [ 6 1 9 ] , and a transformer [ 6 2 0 ] .

F i g . 5 7 . T h e first p o l a r o g r a p h o f H e y r o v s k y a n d S h i k a t a i n 1 9 2 5 . ( H e y r o v s k y ' s
original p h o t o g r a p h . )
In oscillopolarography, the electrolytic processes occurring at the

surface of the polarised electrode are observed with a cathode ray
oscilloscope. In solutions without a depolarising agent, the dv/dt
curves are pure ellipses, the upper part showing the cathodic and the
lower part the anodic process. With a depolariser, breaks are observed
and the heights of these are dependent on the concentration. Now-
adays this method, originally devised by Heyrovsky [ 6 2 1 ] , is used
mainly for theoretical investigations.
For the determination of low concentrations, Kemula and Kublik
used a hanging mercury drop electrode. An electrolysis is carried out
prior to the polarographic analysis so that an amalgam is formed on
the drop. The oxidation current of this electrode is then recorded.
8 _1
The method has recorded concentrations as low as 1 0 ~ mole 1
[622].
Amperometry utilises changes in the polarographic diffusion
242
current to detect the end-point of a titration. It was first investigated
in detail by Majer [623] (who referred to it as polarometry) although
it was discovered by Heyrovsky in 1927 [ 6 2 4 ] .
8. Development of the theory of analytical chemistry
(A) DEVELOPMENT OF PHYSICAL CHEMISTRY
Immanuel Kant's statement that "In the various branches of the

natural sciences only that which can be expressed by mathematics is
true science" has tended to give chemists a feeling of inferiority. It
was in physical chemistry that any mathematics more complicated
than the calculation of direct ratios first appeared. Wilhelmy estab-
lished that, in the inversion of cane sugar, the rate of disappearance
of the sugar, dz/dt, is proportional to its concentration (1850).
Physical chemistry originated about the middle of the last century.
Lomonosov, a hundred years earlier, defined it as "that science
which, using the laws of physics, explains how compounds are
formed in chemical processes".
The concept of affinity had been studied by many great scientists
before Berthollet proposed a physical explanation for it. He con-
sidered that cohesion, elasticity, the mass of the substances in the
reaction, and even gravitational force should be taken into account.
Guldberg and Waage, building on Berthollet's speculations, replaced
the mass of the reactants with their concentrations and derived the
Law of Mass Action in 1867.
Much work had been done in establishing classical thermodynamics
by such scientists as Carnot, Mayer, Joule, and Thomson (Lord
Kelvin), but, as most chemists were concerned with organic chem-
istry, it appeared that the two sciences would never meet. However,
Horstmann, in 1870, applied thermodynamics to chemistry for the
first time to calculate the natural dissociation of gases. On the basis
of the entropy law, he was able to deduce the law of mass action.
Several important papers on thermodynamics were published by
Willard Gibbs from 1873 onwards in a little known journal, Transac-
tions of the Connecticut Academy (Vol. II, p. 309 and subsequent
papers). In these, he applied thermodynamics to chemical processes
and introduced the phase rule and the idea of chemical potential. His
work may also be found in The Collected Works of J. Willard Gibbs

(Yale University Press, New Haven, 1928, reprinted 1957).
In 1877, Pfeffer, a botanist, constructed a semipermeable mem-
brane. By immersing a membrane-vessel attached to a manometer
filled with sugar solution in water, he observed the height of the
liquid in the manometer rise proportionally to the concentration of
the sugar solution. In 1883, Raoult found that, for a given solvent,
equimolar amounts of different solutes depress the freezing point
and elevate the boiling point by equal amounts. The young van't
Hoff concluded from Pfeffer's results that the gas laws are also valid
for solutions. His theory, proposed in 1886, proved correct and
explained Raoult's observations, at least for organic substances. With
inorganic solutes, values two or three times the expected one were
obtained. This anomaly was solved by the electrolytic dissociation
theory of Arrhenius. At this point, the development of physical
chemistry originating from the idea of affinity crossed the other
approach from the phenomena of galvanism.
Grotthus, in 1819, suggested that with a Volta column, the nega-
tive side of molecules moves towards the positive electrode and the
positive side to the negative one, thereby cutting the molecule in
two. In 1833, Faraday discovered the laws of electrolysis. Daniell
found that salts are decomposed by electricity to give metals and
acid radicals, contrary to the metal oxides and anhydro acids of
dualistic theory. Hittorf determined ion mobilities in 1853 and intro-
duced the concept of transference numbers. Although it was ignored
for a time, Kohlrausch, in 1867, examined this work of Hittorf and
discovered that the velocity of a given ion is always constant and is
independent of the nature of other ions in solution or of the partner
with which it forms a molecule. There was considerable controversy
over this and other theories on the subject until Arrhenius's theory
of 1887 solved the problem. This theory also explained the phenom-
ena of galvanism as well as clarifying the anomalies observed in con-
nection with the van't Hoff theory.
(B) WILHELM OSTWALD
What was needed at this stage was someone to correlate these iso-
lated facts. Wilhelm Ostwald (Fig. 58) achieved this in his book
Lehrbuch der Allgemeinen Chemie. Born in Riga, Latvia, in 1853, he
studied there and at the University of Dorpat. After teaching at
Dorpat, he was offered the chair of chemistry at the Technical
244
Fig. 5 8 . Wilhelm Ostwald ( 1 8 5 3 — 1 9 3 2 ) . Drawing b y Klamrath.
University of Riga. Five years later, in 1887, he moved to the Univer-

sity of Leipzig where he did his most famous work. He retired in
1906 and died in 1932.
Arrhenius had just submitted a doctoral thesis at the University of
Uppsala, which expounded the ionic dissociation theory and was
accepted rather dubiously by the University. Ostwald, however,
realised the importance of this theory and travelled to Sweden to
meet Arrhenius. The latter was very encouraged by the interest
shown by the famous professor. Ostwald later told how Cleve,
Professor of Chemistry at Uppsala, showed him a flask containing
sodium chloride solution and asked, "Do you really think that the

sodium atoms are swimming in this glass by themselves?". When
Ostwald replied "Yes", Cleve was astonished.
In the decade after he accepted the chair of chemistry at Leipzig,
Ostwald virtually "organised" physical chemistry. He developed the
dilution law, introduced the concept of dissociation constants of
acids and bases, calculated the ionic product of water, investigated
the process of neutralisation, devised the theory of indicators, exam-
ined the heat of neutralisation, where he revived the long forgotten
law of Hess, and developed a theory of catalytic action. He wrote
many books on the subject, founded a journal and a society, pub-
licised physical chemistry all over the world, and still found time for
teaching. His students included Nernst, Beckmann, Bodenstein, and
many others.
Ostwald had many talents. He painted well, was an accomplished
musician and his total of 27 books would have done credit to a
novelist. He played the role of philosopher but, as he became older,
his views became more unusual. He rigorously opposed natural
philosophy, creating instead a new natural philsoophy, which he
called energetics. In 1908, he was awarded the Nobel Prize for Chem-
istry, in honour of his earlier achievements as, by this time, his work
had no bearing on chemistry at all. An example will illustrate his
work at this period. He considered that the human senses could be
explained in terms of thermodynamic equations, which led him to
propose a happiness equation, viz.
G = k{E + W)(E - W)
2 2
= k(E -W )
where G is the amount of happiness, Ε is the sum of energies directed
by the will, W is the energy used up for experiences opposing the
will, i.e. the sum of the energies used for overcoming obstacles, while
k is a factor for energetical-physical transitions which is dependent
on the individual [ 6 2 5 ] .
The theoretical explanation of analytical phenomena Ostwald
described in his book Die Wissenscha ft lichen Grundlagen der Ana-
lytischen Chemie (i.e. Theoretical Background to Analytical Chem-
istry). Published in 1894, it is a slim volume of 187 pages. In the
preface, he explains that his reason for writing the book was that,
while the techniques of analytical chemistry had been perfected to a
high level, theory had been largely neglected [ 6 2 6 ] .
246
His book begins with the identification and separation of differ-
ent substances. He deals with precipitation in great detail, with the
methods for increasing the crystal size of the precipitate, and with
filtration and washing. He deduces the relation between the decrease
in the concentration of any contaminants and the number of
washings of the precipitate [ 6 2 7 ] . However, he mentions that this
relationship is not valid in practice as the phenomenon of adsorption
is not taken into account.
The fourth chapter, entitled "Chemical Separation" is the most
important. After a presentation of the laws of solutions, in which
he discusses the theory of electrolytes, Ostwald considers the law of
mass action and applies this to the case of electrolytic dissociation.
He introduces the concept of dissociation constants and describes the
dissociation of multibasic acids.
"We can readily assume that in the case of an H 2 A type acid the
dissociation occurs according to the following scheme:
H 2 A ^ 2H- + A"
2
When the equilibrium would be as ab = fee. This, however, is not
so, as multibasic acids dissociate according to the scheme
H 2 A ^ H- + HA'
the univalent ion formed dissociates further according to the equilib-
rium
HA ^ H- + A"
The dissociation constant of the second process is always much
smaller than that of the first" [ 6 2 8 ] .
He then deals with the interactions of electrolytes, establishing
that, in a reaction, it is always the least dissociable substance which is
formed. He then explains displacement reactions.
"If we add a strong acid to the salt of a weak acid then, as we have
already mentioned, it does not matter whether the alkali or acid
corresponding to the salt is weak or strong, the salts are almost com-
pletely dissociated. The solution of a weak acid therefore contains
essentially only free ions. Now, if to this a strong acid is added, the
anions of the salt are united with the hydrogen ions and form the
undissociated weak acid. Thus, in the solution, apart from the cation
of the weak acid, the anion of the strong acid will be present, i.e. the
salt formed in the displacement is present" [ 6 2 9 ] .

He also explains the phenomenon, often used in analytical chem-
istry, of decreasing the acidity of a solution by adding the salt of a
weak acid. After a treatment of the roles of hydrolysis, heteroge-
neous equilibria, reaction velocity, and temperature, Ostwald turns
to precipitation processes, introducing the concept of solubility
product.
"In the saturated aqueous solution of an electrolyte, a com-
plicated equilibrium is set up. The solid substance is in equilibrium
with the undissociated substance in the solution and this in turn is in
equilibrium with the dissociated parts, i.e. the ions. The first equilib-
rium is governed by the relative concentrations and as the concentra-
tion of the solid substance is constant then the concentration of the
undissociated part in the solution must also be fairly constant. In the
second equilibrium for the most common case, i.e. dissociation to
give monovalent ions, if the concentration of the ions are a and 6,
while that of the undissociated part is c, then:
ab = kc"
The product of the two ions has a definite value and can be
referred to as the solubility product.
"If we consider the precipitation of SO4 ions, when an exactly
equivalent amount of barium salt is added, an amount of the SO4
ions remain in solution, this amount being equal to the Ba- · ions
formed from the solubility product equilibrium. If further amounts
of barium salt are added then one factor in the solubility product
equation will increase, resulting in a decrease in the SO4 concentra-
tion, so that more barium sulphate will be precipitated. A further
addition of barium salt will cause a similar effect; the concentration
of SO4 ions, however, will never decrease to zero as the concentra-
tion of Ba* · ions can never reach infinity" [ 6 3 0 ] .
Thus, Ostwald used the solubility product principle together with
the dissociation constant to explain phenomena which had been ob-
served for a very long time.
In the second part of his book, he describes the reaction of various
ions in detail. He begins by treating the hydrogen and hydroxyl ions
and in this section illustrates his theory of indicators. He also noted
the interference of carbon dioxide with acid—base titrations, as well
as phenomena occurring in the titration of polybasic acids. He
explains how to titrate phosphoric acid with various indicators. It
must be mentioned, however, that very few numerical values are
248
5
given for the deduced constants. One of these is a figure of 2.3 Χ 10"
for the dissociation constant of ammonia. He mentions that in 0.1 Ν
solution only 1.5% of the ammonia dissociates [ 6 3 1 ] . Here is an
extract from this part of the book.
"Among the salts of monovalent copper only the halogen com-
pounds are known . . . the iodide is sufficiently insoluble to be used
for the determination of copper. If to the copper(II) salt, potassium
iodide is added, then cuprous iodide and iodine are liberated:
Cu + 2 Γ ^ Cul + I
The reaction does not proceed to completion as the reverse reactions
may also take place. To shift the position of equilibrium to the right
it is necessary for one of the reaction products to be removed. There-
fore the addition of sulphurous acid to the solution removes the
iodine as it is liberated. This decrease in the concentration of the sub-
stances on the right hand side of the equation causes the reaction to
go to completion . . . " [ 6 3 2 ] .
These extracts from Ostwald's book illustrate very clearly the
importance of his ideas and no comment is needed to emphasise this.
(C) D E V E L O P M E N T O F T H E C O N C E P T OF p H
An important omission from Ostwald's book was any reference to

the Nernst equation, especially as Nernst developed it at Ostwald's
institute in 1889 [ 6 3 3 ] . The young Nernst based his arguments on
the thermodynamic aspects of the osmotic pressure of cells and from
this he was able to calculate the EMF of galvanic cells. This equation
can also be used for the calculation of the potential difference
between solutions of different concentrations.
The ionic theory provides a special relationship between the
hydrogen and hydroxyl ion concentrations and Nernst's formula
opened up the possibility for concentration determination. A dis-
covery of Le Blanc made possible the determination of concentra-
tions from EMF measurement of cells. He found that if a stream of
hydrogen is allowed to flow over the surface of a platinum elec-
trode coated with platinum (platinised platinum), then this behaves
as a hydrogen electrode [ 6 3 4 ] . Where two solutions interact, the
diffusion potential influences the results. Nernst tried to eliminate
this error by calculation but this was only possible in a few cases.
Tower discovered that if potassium chloride solution is used to effect

the electrical contact between the two solutions, then the diffusion
potential is decreased to such an extent that it becomes almost
negligible [ 6 3 5 ] . Bôttger, in 1897, was the first to use a hydrogen
electrode in the titration of an acid.
Several scientists about this time calculated the dissociation con-
stant of water. Arrhenius, in 1887, calculated it from the degree of
hydrolysis of sodium acetate [ 6 3 6 ] . In 1893, Ostwald used a con-
centration cell for this purpose [ 6 3 7 ] . In the same year, Wijs deter-
mined this constant from the saponification rate of methyl acetate
with water with hydroxyl ions as catalyst [ 6 3 8 ] . Finally, Kohlrausch
and Heydweiller calculated it from conductivity measurements
[ 6 3 9 ] . All these measurements were in close agreement and gave
14 - 1 4
values for the ion product between 1.1 X 1 0 ~ and 1.41 Χ 1 0 .
It was Pal Szily who discovered, while investigating blood serum,
that it was possible to prepare solutions of small but constant hydro-
gen ion concentrations. This was the first study and application of
buffer solutions [ 6 4 0 ] . Friedenthal recommended that the reac-
tion of a solution should be characterised by its hydrogen ion con-
centration as
+
H 2 0 ^ H + OH~
7
CH+ = C o h- = 1 0 -
- 14
so the hydroxyl ion concentration is found by dividing 1 0 by the
hydrogen ion concentration.
After Fels used ammonium hydroxide—ammonium chloride and
acetic acid—sodium acetate buffer systems [ 6 4 1 ] , Fernbach ob-
served that the enzyme action of a malt extract is only influenced
by acids or bases if a certain critical amount of the acid or base is
exceeded. The extract is therefore protected against acids and bases
to a certain degree. This was found to be due to the presence of
mono- and dihydrogen phosphates. Fernbach stated that "the mix-
ture behaves like the buffer disc of a waggon (tampon), it lessens the
effects of acids and bases" [ 6 4 2 ] . The English word buffer derived
from this.
The pH sign was introduced by S^rensen. He replaced the whole
number expression by the exponent (i.e. the negative logarithm)
which he termed the pH. S0rensen's original paper was entitled
Enzymstudien [ 6 4 3 ] . In it, he considered that the variation in
enzyme activity with acidity was not due to a particular acid but
250
rather to the hydrogen ion concentration. Therefore he needed a
simple method of expressing this. He needed a reliable method for
measuring it and also the ability to prepare solutions with accurately
known hydrogen ion concentrations. The S0rensen-type silico-phos-
phate buffer solutions resulted.
Although it has become very widely used, the concept of pH in
S^rensen's time was of interest to only a small group of scientists
with very few chemists among them. It was biochemists and enzy-
mologists who realised its practical importance. Much early work on
this subject was carried out at the Carlsberg Laboratory in Denmark.
The first monograph appeared in 1914 written by Michaelis entitled
Die Wasserstoffionkonzentration. He insisted that physiological
chemists needed a better understanding of pH. He cited the example
of an author who found that the efficiency of invertase is diminished
by the addition of blood serum and concluded that the blood serum
must contain some of the anti-substance of the invertase. However,
the decrease in activity is due simply to the pH of the blood serum
and any solution of this pH would have a similar effect.
In 1920, Clark, a physiologist, wrote a book entitled The Deter-
mination of Hydrogen Ions which renewed interest in the subject.
The first book devoted to the analytical aspects of this subject was
Kolthoff's Der Gebrauch von Farbindicatoren, published in 1921.
(D) THEORY OF TITRATION
The development of theories is far more difficult to trace than

practical achievements. Someone would pick up a certain idea,
develop it, and then pass it on to someone else. The theory of titra-
tion developed in this way.
It was well known that, for the titration of weak acids, different
indicators from those used in the titration of strong acids were
required. It had also been established that the titration of certain
polybasic acids gave entirely different results with different indi-
cators. In his indicator theory, Ostwald pointed out the cause of this
phenomenon but did not investigate it very deeply.
As the number of synthetic indicators available increased rapidly,
it became increasingly difficult for chemists to decide which indi-
cator was suitable for a given titration. In 1907, only the dissociation
constants of p-nitrophenol [644] and phenolphthalein [645] were
known.

Salm, in 1907, determined the dissociation constants of a number
of indicators by a colorimetric method. He made the important dis-
covery that the dissociation constant of an indicator corresponds to
the hydrogen ion concentration at which the indicator is 50% disso-
ciated. This is naturally the transition point of the indicator also.
From a knowledge of the dissociation constant, the indicator for a
given titration can be selected. He explained simply and clearly the
difference between equivalence and neutral points.
"The indicator must show that point where exactly equivalent
amounts of acid have been added to the base. This point we shall call
the equivalence point. This only becomes identical with the neutral
point in the case of strong electrolytes" [ 6 4 6 ] .
The principles of the theory of acid—base titrations are to be seen
in this publication for the first time. These later became the basis for
all other types of titration.
This subject was studied in greater detail by Noyes [647] and later
M •a
Q9
JO.•to
M JQ_
Q8
t JO
0,7 10
10Γ β
V-'MuttulRM'
10
r ft
JO
M
10
c.c.NaOH.
Fig. 5 9 . Theoretical titration curves o f Hildebrand ( 1 9 1 3 ) . ( F r o m t h e original

paper. )
252
Bjerrum who summarised it in his monograph Die Théorie der Alkali-
metrischen und Acidimetrischen Titrationen in 1915.
During this time, potentiometric titrations had been investigated
using a hydrogen electrode. Hildebrand was the first to carry out a
theoretical investigation of titration curves. He recorded the hydro-
gen ion concentration on the ordinate, corresponding to the poten-
tial. The inflexion point and potential break of the curves gave a
clear indication of the equivalence point and its correlation with pH
(Fig. 59). It was soon possible to select a suitable indicator for a
given titration by this method [ 6 4 8 ] .
Bjerrum, in 1915, proposed his theory regarding the titration error
[ 6 4 9 ] . He believed that three factors contributed to this error,
namely the hydrogen error, the hydroxyl error, and the acid or base
error. On this basis, he was able to calculate the pH at the equivalence
point. Moreover, he gave the values corresponding to the separate
steps in the dissociation of polybasic acids. He also calculated that
the limiting value for the titrability of acids is the dissociation con-
— 10 —4
stant of 1 0 and 1 0 for bases. Titrations could be calculated
theoretically, even for weak electrolytes. These curves and the meth-
od of calculation are today found in all analytical textbooks. The
first example is in Kolthoff's book [ 6 5 0 ] . The development of the
theory of acid—base titrimetry was essentially complete by the start
of the first World War.
Bjerrum attempted to compensate for deviations from the ionic
theory of Arrhenius exhibited by strong electrolytes by introducing
three coefficients. Of these the so-called activity coefficient was to
become the most important (1916) [651] and was first used by
Lewis [ 6 5 2 ] , As dilute solutions are generally used in analytical
chemistry, concentrations rather than activities tend to be used.
S^rensen determined the hydrogen ion concentrations of his solu-
tions from conductivity measurements. He established the potential
of the 0.1 Ν calomel electrode to be 0.338 V, referred to the poten-
tial of the normal hydrogen electrode. He recalculated this in 1924
and found it to be +0.3357 V [ 6 5 3 ] . This value has only been modi-
fied by a negligible amount since that time. As the electrode poten-
tial is defined not by the hydrogen ion concentration but by the
activity, then pH data, based on EMF measurements, cannot give an
accurate value for the concentration. In analytical practice, however,
the original definition of S0rensen can be used without involving any
significant error.

In 1923, Brônsted introduced a new theory of acids and bases
which could explain acid—base phenomena in non-aqueous media
[ 6 5 4 ] . Briefly, the theory states that acids are those substances
which are capable of donating a proton while bases are those sub-
stances which accept protons.
+
acid ^ base + H
The first analytical textbook to treat acid—base phenomena according
to the Brônsted theory was published by Chariot in 1942.
Turning to redox titrations, Ostwald pointed out that the elec-
trode potential of a system is a measure of its oxidising or reducing
power. The application of the Nernst equation in the case of redox
systems was examined by Peters, working in Ostwald's institute,
who made measurements of potential on the iron(III)—iron(II)
systems [ 6 5 5 ] . Peters' experiments led to the establishment of the
equation
π = A + (RT/F) l n ( C K e3 + / C F e2 +)
where the RT factor, which originates from the conversion of

osmotic to electrical energy, is constant. If the ratio of ferric to
ferrous ions is unity, then the expression becomes
π=A
The constant A is therefore the EMF obtained when the standard
electrode is combined with another electrode containing equimolar
amounts of ferric and ferrous ions [ 6 5 6 ] . This, therefore, is the
definition of the standard redox potential.
In 1900, Crotogino studied the reaction
Μηθ4 + 4 Η· = Μη· · + 4 OH' + 5 F-
where F- refers to the charge on the ions. He therefore deduced that
4 4
π = (RT/5F) ln(K [MnO'4] [Η·] /[Μη··][ΟΗ'] )
is obtained. He replaced the OH' ions with Η· ions using the ionic
product of water and thus obtained an equation which takes into
account the effect of hydrogen ions on the redox potential. This
enables calculation of the EMF of a system at any point during a
titration [ 6 5 7 ] . When redox indicators were introduced, the choice
of indicator with a transition point corresponding to the equivalence
point was now capable of being accurately made.
254
The theory of redox titrations was developed from an investiga-
tion of redox indicators, as the theory of acid—base titrimetry
derived from the study of acid—base indicators. These studies were
carried out by the same workers who made the pioneer investigations
into acid—base processes, viz. Clark and Michaelis. The theory of
redox titrations was developed by Kolthoff.He examined mathemat-
ically the variation in electrode potential as a function of the amount
of a standard solution added for various processes as well as calcu-
lating the equivalence-point potential in each case. This is also now a
major part of all analytical textbooks [ 6 5 8 ] .
9. Other methods of analysis
(A) RADIOCHEMICAL ANALYSIS
The investigation of the phenomena of radioactivity began in the

present century. An early problem was the production of measuring
devices. Nowadays, this is mainly carried out using counting or
scintillation methods. Geiger, together with Rutherford, prepared the
first counting tube in 1908. This consisted of a cylindrical metal tube
with an axial wire and an electric field between the cylinder wall and
the wire. The rays entering the tube ionise the gas, which is at low
pressure. The ions are attracted to the wire and register on an electro-
scope [ 6 5 9 ] , It was mainly due to Millier that it had evolved by 1928
to the form in which it is used today [ 6 6 0 ] .
The principle of the scintillation counter is the phenomenon
exhibited by zinc sulphide, which, when irradiated with a-rays,
re-emits part of the absorbed energy as visible light. Crookes and also
Elster and Geitel were the first to observe this in 1903. In 1908,
Crookes and Regener designed an instrument based on this called a
spinthariscope. However, the need for optical counting was a serious
disadvantage. Curran and Baker were the first to combine a scintilla-
tion counter with a photomultiplier [ 6 6 1 ] . Coltman and Marshall, as
well as Broser and Kallmann, were the first to use this device for
radioactive counting [ 6 6 2 ] . It is now possible to count j3- and
7-particles in this way.
Of the many radiochemical methods of analysis, one of the most
important is the use of isotopically labelled atoms. A radioactive
isotope is intimately mixed with the sample. After completion of any

subsequent operations, the radioactivity of a known amount of the
product may be measured. Hevesy and Paneth discovered the basic
principle in 1913 [ 6 6 3 ] . A related method is indicator analysis,
where the distribution of a substance, for example, in two or more
phases is measured by the distribution of the radiation. Erbacher and
Philipp were the first to apply this technique, in the examination of
1 9 8
the separation of gold and platinum using labelled A u as tracer
[664].
The pioneer of analyses using radioactive reagents was Ehrenberg
[ 6 6 5 ] . These methods only really became important since the 1940's
with the availability of artificial radioactive isotopes and most of the
classical analyses have now been attempted using them. Precipita-
tion titrations, where either the solution or titrant is radioactive were
introduced by Langer [ 6 6 6 ] . The end-point is indicated by a change
in activity of the solution.
Isotope dilution analysis is probably the most important radio-
chemical method. A radioactive isotope, whose specific activity is
known, is added to a sample. After a separation, which need not be
quantitative, a pure sample is taken and the activity measured. The
ratio of this activity to the initial activity (if necessary corrected for
decay), together with the weight of sample will give the amount of
inactive element present. This procedure, which is useful for deter-
mining one element in the presence of other similar elements, was
introduced by Hevesy and Hobbie in 1931 [ 6 6 7 ] . For the analysis
of trace elements, the radioactive precipitate-exchange method of
Bânyai et al. is of value [ 6 6 8 ] .
Hevesy also introduced neutron activation analysis where a sample
is irradiated by slow neutrons which react with the nuclei of the ele-
ment to be determined converting one of its isotopes into a radioac-
tive species. With certain precautions, the level of radioactivity corre-
sponds to the amount of the element present. Hevesy and Levi used
a radium—beryllium source coated with paraffin and succeeded in
determining the dysprosium concentrations in yttrium preparations
[669].
R.H. Miiller discovered that if j3-rays are allowed to impinge on a
sample, they are reflected, the angle of reflection being dependent on
the atomic number. The great advantage is that this method is non-
destructive [ 6 7 0 ] .
Certain substances were found to be very responsive γ-ray crystal
counters. Of these, the Nal crystal doped with thallium, first used by
256
Hofstadter, is the most important [ 6 7 1 ] . As a result, qualitative and
quantitative measurement of substances emitting 7-radiations with
varying energies became possible.
(B) CHROMATOGRAPHY
The history of chromatography begins with the work of Runge, a

physician, who observed that certain coloured substances, when
spotted onto a filter paper spread out into concentric rings. He
recorded these with the practised eye of a painter in his books Zur
Farbenchemie: Musterbilder fur Freunde des Schonen und zum Ge-
brauch von Maler (1850) and Der Bildungstrieb der Stoffe (1855).
The immediate predecessor to chromatography was capillary analysis.
Schônbein, in 1861, observed during the qualitative test for ozone
that, if an aqueous solution is spotted on a filter paper, the water
precedes the dissolved substances and that different substances are
drawn up the paper to varying degrees [ 6 7 2 ] , His work was carried
on by his student, Goppelsrôder, who published his first results in
1861 [ 6 7 3 ] . He continued the work in this field throughout his life
and finally published a monograph on the subject in 1901. Capillary
analysis shows many similarities to paper chromatography. While, in
the latter method, one drop of the solution is placed on the filter
paper, in capillary analysis, the edge of the filter paper is dipped in
the solution itself. In paper chromatography, the samples are moved
up the paper by the solvent flow, whereas in capillary analysis, con-
clusions are based on the height to which various components are
sucked up the filter paper. Thus the sensitivity of the latter could
never approach that of paper chromatography [ 6 7 4 ] .
In 1900, Day presented a paper to the 1st International Mineral
Oil Congress in Paris. He had filtered kerosene through a column of
fuller's earth and succeeded in separating single hydrocarbon fractions
[ 7 0 9 ] . Kvitka achieved the same result simultaneously and indepen-
dently. Albrecht and Engler also did useful work in petroleum
analysis [ 7 1 0 ] .
However, it was in 1903 that Mihail Tsvett (Fig. 60) wrote his
notable paper on adsorption phenomena [ 6 7 5 ] . Born in 1872 in
Russia, Tsvett moved with his family to Switzerland while still a
child. He studied there and received his doctorate in botany in 1894.
For the work which he did for this degree, he received the Davy
Award. In 1896, he went to lecture in Russia. In 1901, he moved to

Fig. 6 0 . Mihail Tsvett ( 1 8 7 2 - 1 9 2 0 ) .
Warsaw where, in 1908, he became Professor of Botany and Anato-

my at the Technical University. During the first World War, he was
forced to flee, first from Warsaw and later from Dorpat. He settled in
Voronyes where he died of tuberculosis in 1920.
His paper of 1903 was, in fact, the introduction to chromatog-
raphy. In one experiment, he passed a plant extract down a column
packed with inulin.
"It is very instructive to observe the adsorption phenomena during
filtration through a powder. First a colourless liquid flows out from
the bottom of the funnel, then a yellow one (carotene), while a
258
bright green ring forms at the top of the inulin column, below which
a well-defined yellow ring soon appears. On subsequent washing of
the inulin column with pure ligroin both rings, the green and the
yellow, are considerably widened and move down the column"
[675].
In the following years, he developed the method and published it
in 1906 [ 6 7 6 ] .
"If a chlorophyll solution dissolved in petroleum ether is filtered
through an adsorbent column (I use mainly calcium carbonate
suspension which I compact into a glass tube), the pigments are
separated from the top to the bottom of the column, according to
the order of their adsorption ability, and various coloured zones are
formed. The most strongly adsorbed substances force the less
strongly adsorbed ones further and further down the column. This
separation is made almost complete if, after the pigment solution is
passed down the column, a solvent is passed through the column
after it. Just as the light rays in the spectrum are separated, so the
various components of the pigment mixture are separated on the
calcium carbonate column and therefore they can be determined
qualitatively and quantitatively. This preparation is called a
Fig. 6 1 . Tsvett's c h r o m a t o g r a p h i c apparatus. ( F r o m t h e original paper.)

chromatogram and the method is called chromatography. It is un-
necessary to add that the method is not only suitable for pigment
mixtures for, as can be expected, all coloured and colourless chemi-
cal compounds are governed by this law."
Tsvett's apparatus is shown in Fig. 61. He named the method
chromatography because he wanted to indicate that it gives a picture
of the composition of coloured substances. The name persists
although the majority of samples today are colourless. His work
yielded some important results. For example, he found that a leaf
extract contained two chlorophylls, four xanthophylls, and carotene
[ 6 7 7 ] . Although he published the results of his work in a monograph
in 1910, it aroused little enthusiasm and his results were treated with
some scepticism by his contemporaries. It was over twenty years
later than Kuhn et al. [678] revived the method for the investigation
of carotenoids. This marked the beginning of the rapid development
of chromatography.
Partition chromatography, discovered by Martin and Synge in
1941 [ 6 7 9 ] , utilises the principle of counter current distribution, the
stationary phase being supported on a carrier. Martin and his
coworkers later used filter paper as a carrier and thus paper chroma-
tography originated [ 6 8 0 ] . The fact that the principle of partition
chromatography could be applied to gases led James and Martin to
develop gas chromatography [ 6 8 1 ] .
(C) ION E X C H A N G E
Apart from the miracle of Moses who made bitter salt water drink-
able by the addition of tree branches, which some people may con-
sider an application of ion exchangers, and from Aristotle's reference
to the use of clay filters for the same purpose, the introduction of
ion exchange methods took place about the middle of the last cen-
tury.
Thompson and Way, in 1850, observed that if an earth is treated
with ammonium sulphate or ammonium carbonate solution, it
adsorbs ammonia and calcium passes into the solution [ 6 8 2 ] .
Eichhorn, in 1858, established that the adsorption of elements from
earth waters to clay is a reversible process [ 6 8 3 ] .
The analytical use of ion exchangers only began in this century,
again introduced by biologists. At the end of the first World War, no
blood carbon was available to bind creatine in the determination of
260
ammonia in urine. Folin and Bell, in 1917, investigated the use of
the synthetic aluminium silicate of Gans to bind the ammonia while
the creatine remained in solution. Ammonia was subsequently
liberated by treatment with alkali and was determined with Nessler's
reagent [ 6 8 4 ] .
Natural zeolites were soluble in strong acids and peptised in alkaline
medium and so had limited uses. The introduction of synthetic ion
exchange resins made these methods much more widespread. The
first synthetic resin of any practical value was produced from phenol
and formaldehyde by Adams and Holmes in 1935 [ 6 8 5 ] . Samuelson
wrote the first monograph in this field [ 6 8 6 ] .
Ion exchange methods must be combined with some other com-
plementary measuring technique. One of the more important devel-
opments of this subject is ion exchange chromatography. Developed
during the second World War in the U.S.A. for the separation of
atomic fission products, it was perhaps first used by Russel and
coworkers in 1944 [ 6 8 7 ] .
Redox reactions can also be made to occur on ion exchange resins.
This type of method was recommended for the first time by Sansoni
[ 6 8 8 ] , while the first actual determinations were carried out by
Inczédy [ 6 8 9 ] .
(D) CONCLUSION
This history has covered about four thousand years from earliest
times until the middle of the present century. As events require the
benefit of the passage of time to be put into historical perspective,
this chapter will not attempt to collate more recent results.
The most obvious conclusion which can be drawn from a chapter
such as this is that almost nothing is completely new but is usually a
logical extension of what has gone before. However, it is the mark of
genius to have the foresight to see the next logical extension and the
practical skill to prove it.
We now leave it to the readers to write the next chapter in the
History of Analytical Chemistry.
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H e s s e a n d H. W e i l , M. W o e l m , E s c h w e g e , 1 9 5 4 .
676 M. T s v e t t , B e r . D t s c h . B o t . G e s . , 2 4 ( 1 9 0 6 ) 3 1 6 .
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679 A . J . M a r t i n a n d R . L . S y n g e , B i o c h e m . J., 3 5 ( 1 9 4 1 ) 9 1 , 1 3 5 8 .
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A . H . G o r d o n , A . J . P . M a r t i n a n d R . L . M . S y n g e , B i o c h e m . J., V o l . 3 7 ( 1 9 4 3 )
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681 A . T . J a m e s a n d A . J . P . M a r t i n , B i o c h e m . J., 5 0 ( 1 9 5 2 ) 6 7 9 .
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688 B. Sansoni, Naturwissenschaften, 3 9 ( 1 9 5 2 ) 2 8 1 .
689 J. I n c z é d y , M. K e r n . L a p j a , 1 4 ( 1 9 5 9 ) 4 0 9 .
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T h e a t r v m Orbis Terrarvm Ltd., A m s t e r d a m , N e w York, 1 9 7 1 .
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282
Index
A b s o r p t i o n c o e f f i c i e n t , first d e f i n i t i o n o f , —, G r e e k , 6 6
233 —, W e s t e r n , 6 8
A c e t a l d e h y d e d e t e c t i o n of, 3 1 , 4 4 A l c o h o l s , aliphatic, d e t e c t i o n of, w i t h
A c e t i c acid, capillary distillation of, 2 7 1-chloromethylisatin, 12
—, d e t e c t i o n o f , 2 7 , 4 9 —, u s i n g o - v a n a d i c a c i d , 1 2
—, e a r l y t i t r i m e t r i c a n a l y s i s of, 1 6 7 —, p r i m a r y a n d s e c o n d a r y , d e t e c t i o n of,
A c e t o n e , d e t e c t i o n of, 1 5 , 2 6 — 2 7 , 4 9 by conversion to xanthates, 12
A c e t y l a c e t o n e , d e t e c t i o n of, 1 5 , 2 8 —, s a t u r a t e d a c y c l i c , d i f f e r e n t i a t i o n f r o m
A c e t y l e n e , d e t e c t i o n of, 2 8 phenols, 9
A c i d , definition of, b y B o y l e , 7 8 —, t e r t i a r y , d e t e c t i o n o f , b y L u c a s t e s t ,
A c i d a n h y d r i d e s , d e t e c t i o n of, i n p r e s e n c e 12
of carboxylic acids, 18—19 —, t e s t p r o c e d u r e f o r d e t e c t i o n of, 4 3
A c i d — b a s e i n d i c a t o r s , first theoretical A l d e h y d e s , d e t e c t i o n of, 1 5 , 1 7 — 1 8 , 4 4
i n t e r p r e t a t i o n o f b e h a v i o u r of, 1 9 5 —, d i f f e r e n t i a t i o n b e t w e e n a l i p h a t i c a n d
A c i d — b a s e p r o c e s s e s , i n v e s t i g a t i o n s of, aromatic, 9
b y Clark a n d M i c h a e l i s , 2 5 1 , 2 5 5 —, s u b s t i t u t e d a r o m a t i c , d e t e c t i o n o f , 1 7 ,
A c i d — b a s e t i t r i m e t r y , first a p p l i c a t i o n o f 44
potentiometry to, 239 —, t e s t p r o c e d u r e f o r d e t e c t i o n of, 4 4
—, t h e o r y of, 2 5 2 Alicyclic ketones, differentiation from
Acidic organic c o m p o u n d s , test for, 5 acyclic and aromatic k e t o n e s , 9
A c i d i m é t r i e titrations, earliest applica- Aliphatic aldehydes, differentiation from
t i o n s of, 1 6 8 — 1 7 2 aromatic aldehydes, 9
A c o t i n i c a c i d , a p p l i c a t i o n of, t o d e t e c - A l i p h a t i c h a l o g e n s , d e t e c t i o n of, u s i n g
tion of formic acid, 3 2 succinic or phthalic acids, 7
A c t i v i t y c o e f f i c i e n t , first m e n t i o n of, 2 5 3 Aliphatic h y d r o x y c o m p o u n d s , detection
A d a m s , c o n t r i b u t i o n of, t o d e v e l o p m e n t of, using d i a z o b e n z e n e s u l p h o n i c
of ion exchangers, 2 6 1 acid, 1 1
A i r , d e t e r m i n a t i o n o f w e i g h t of, 97 Alkali, d e f i n i t i o n of, b y B o y l e , 7 8
—, e a r l y a n a l y s i s of, b y S c h e e l e , 1 0 5 Alkalis, early investigations o f solubilities
—, e x p e r i m e n t s o n , b y C a v e n d i s h , 1 0 0 of metals in, 9 2
Albiruni, determinations of specific —, s t u d i e s o f s t r o n g a n d w e a k , 9 5 — 9 7
weight by, 69 A l k a l i t h i o c y a n a t e s , a p p l i c a t i o n of, i n
Alchazini, determination of specific precipitation titrations, 1 9 3
weights by, 69 A l k a l o i d s , first t i t r i m e t r i c d e t e r m i n a t i o n
A l c h e m y , Arabic, 6 6 of, 1 8 1
—, b i r t h o f , 6 2 p - A l k y l q u i n a l d i n i u m salts, a p p l i c a t i o n of,
—, d e v e l o p m e n t of, 6 5 — 6 8 to detection of formic acid, 3 1
283
A l u m i n i u m g r a v i m e t r i c d e t e r m i n a t i o n of, of gold, 71
as d e s c r i b e d b y F r e s e n i u s , 1 5 6 —, d i s c o v e r y o f , 6 8
A m i n e s , d e t e c t i o n of, 2 0 — 2 2 , 4 6 —, titrimetric determination of, by
—, t e s t p r o c e d u r e f o r d e t e c t i o n of, Gentele, using hexacyanoferrate(III),
46-47 193
A m i n o acids, titration of, in n o n - a q u e o u s —, —, b y G y ô r y , 1 9 8
media, by Foreman, 2 0 0 A n t i m o n y e l e c t r o d e , first r e c o m m e n d a -
A m i n o b e n z e n e sulphonic acids, differen- t i o n of, for m e a s u r e m e n t o f p H , 2 3 6
tiation a m o n g isomers, 37 A q u a r e g i a , d i s c o v e r e r of, 6 8
A m i n o b e n z o i c acids, detection of isomers A r c h i m e d e s , early applications of the
of, 3 8 hydrometer by, 68
o-Aminodiphenyl, application of, to A r i s t o t l e , t h e o r y o f t h e five e l e m e n t s , 6 1
detection of carbonyl groups, 15 Aromatic aldehydes, differentiation from
o - A m i n o p h e n o l , a p p l i c a t i o n of, t o d e t e c - aliphatic aldehydes, 9
tion of glycerol, 3 2 A r o m a t i c c o m p o u n d s , d e t e c t i o n of, 9 — 1 1
A m i n o p h e n o l s , i d e n t i f i c a t i o n of, 4 1 — 4 2 A r s e n i c , d e t e r m i n a t i o n of, i n m i n e r a l
p - A m i n o p h e n o l r e a g e n t , a p p l i c a t i o n of, waters, by Boyle, 8 4
t o d e t e c t i o n of b r o m i n e in organic —, F i s c h e r ' s d e t e c t i o n of, b y e l e c t r o l y s i s ,
substances, 7 216
Amino-polycarboxylic acids, history of —, titrimetric determination of, by
t i t r i m e t r i c a p p l i c a t i o n of, 1 9 9 Gentele, using hexacyanoferrate(III),
Ammonia, discovery of, 103 193
—, e a r l y t e s t f o r , 1 4 5 - , - , by Gyôry, 198
—, titrimetric determination of, by Arsenic testing, Marsh's device for, 1 4 8 —
Peligot,181 149
A m m o n i u m m o l y b d a t e , d i s c o v e r y of, 1 4 9 A r s e n i o u s a c i d , h i s t o r i c a l a p p l i c a t i o n of,
A m m o n i u m p h o s p h o m o l y b d a t e , applica- in titrimetry, 1 7 7
t i o n of, t o d e t e c t i o n o f a s c o r b i c a c i d , —, h i s t o r i c a l d e t e r m i n a t i o n o f , b y p e r -
28 manganatometry, 180
Ammonium sulphide, early analytical A s c o r b i c a c i d , d e t e c t i o n of, 2 8
a p p l i c a t i o n s of, 1 4 5 —, i n v e s t i g a t i o n o f t i t r i m e t r i c a p p l i c a -
A m p e r o m e t r y , historical a s p e c t s of, 2 4 3 t i o n s of, 1 9 9
Analysis, early, 63—65 A t o m i c absorption s p e c t r o s c o p y , devel-
—, —, t e x t s o n , 1 4 4 — 1 4 6 o p m e n t of, 2 2 9
—, first s y s t e m a t i c s c h e m e f o r , 1 4 9 — 1 5 0 A t o m i c t h e o r y , e v o l u t i o n of, 1 2 5
Analytical chemistry, development of A t o m i c weights, according to Dalton, 125
t h e o r y of, 2 4 3 — 2 5 5 —, d e t e r m i n a t i o n of, b y B e r z e l i u s , 1 3 9 —
—, p r e - 1 7 0 0 h i s t o r y of, 6 1 — 8 6 140
A n g s t r o m , c o n t r i b u t i o n s of, t o early A t o m i s m , t h e o r y of, 7 7
spectroscopic research, 2 2 0 A z o t o m e t e r s , d e v e l o p m e n t of, 2 0 9
—, r e c a l c u l a t i o n o f w a v e l e n g t h s o f s p e c -
tral l i n e s b y , 2 2 7 — 2 2 8 B a c k s c a t t e r i n g , a n a l y t i c a l a p p l i c a t i o n s of,
A n i l i n e , titration of, in n o n - a q u e o u s 256
media, by Vorlânder, 2 0 0 B a c k - t i t r a t i o n , first a p p l i c a t i o n of, 1 7 2
A n i l s , a p p l i c a t i o n of, t o i d e n t i f i c a t i o n o f Balance, used by Berzelius, 1 4 3 — 1 4 4
a m i n o b e n z o i c acid isomers, 3 8 B a r b i t u r i c a c i d , a p p l i c a t i o n of, t o d e t e c -
A n t h r a c e n e , d e t e c t i o n of, 2 8 tion of oxamide, 34
A n t i m o n y , a p p l i c a t i o n of, t o purification —, d e t e c t i o n o f , 2 9 , 4 9
284
B a r i u m , d i s c o v e r y of, 1 0 5 —, h y d r o s t a t i c b a l a n c e of, 8 5
—, gravimetric determination of, as —, l i f e a n d w o r k of, 8 1 — 8 6
described b y Fresenius, 1 5 6 —, r e d i s c o v e r y o f t h e h y d r o m e t e r b y , 6 9
Beer, contribution of, to photometric B r o m i d e , g r a v i m e t r i c d e t e r m i n a t i o n of,
theory, 2 3 3 simultaneously with chloride and
B e h r e n d , R o b e r t , c o n t r i b u t i o n s of, t o iodide, 157
potentiometric titrimetry, 237 B r o m i n e , d e t e c t i o n of, in organic sub-
Belcher, R., r e c o m m e n d a t i o n o f mer- stances, 7
c u r y ( I ) n i t r a t e as t i t r a n t b y , 1 9 9 —, d i s c o v e r y a n d e a r l y a p p l i c a t i o n s o f ,
Benedict's reagent, 16 148
B e n z a l g r o u p , d e t e c t i o n of, i n o r g a n i c —, h i s t o r i c a l d e t e r m i n a t i o n of, i n m i n e r a l
compounds, 10 waters, 2 3 0
Benzyl groups, detection of using Zim- B r o m o c y a n o g e n , a p p l i c a t i o n of, t o d e t e c -
merman reaction, 10 tion of pyridine, 35
B e r g m a n , early gas analysis b y , 1 0 4 B r o m o f o r m , d e t e c t i o n of, 3 0
—, l i f e a n d c o n t r i b u t i o n s t o a n a l y s i s of, 3 -Bromo-2 -nitroso-1 -naphthol, applica-
1 0 5 - 1 1 1 , 112 t i o n of, in d e t e c t i o n o f aromatic
B e r n a r d , c o n t r i b u t i o n s of, t o p h o t o m e t r i c amines, 21
theory, 232 Brônsted, theory of acids and bases pro-
B e r t h o l l e t , t h e o r i e s of, 1 2 3 posed b y , 2 5 4
Berthollimeter, of Descroizilles, 1 7 0 B u f f e r s o l u t i o n s , e a r l y a p p l i c a t i o n s of,
Berzelius, determination of atomic weight 147,250
of chlorine by, 1 3 9 —, first r e f e r e n c e t o , 1 9 6
—, e a r l y a t t e m p t s t o a n a l y s e o r g a n i c c o m - —, i n t r o d u c t i o n o f , 2 3 7
pounds b y , 2 0 4 —, i n t r o d u c t i o n o f S ^ r e n s e n - t y p e , 2 5 1
—, l a b o r a t o r y e q u i p m e n t of, 1 4 1 — 1 4 4 Bunsen, Robert Wilhelm, contributions
—, l i f e a n d w o r k of, 1 3 2 — 1 4 1 to iodometry by, 179
—, s y s t e m o f i n t e r n a t i o n a l w e i g h t s p r o - —, i n t r o d u c t i o n o f c o n c e p t o f a b s o r p t i o n
posed b y , 1 4 4 coefficient by, 2 3 3
B i s m u t h , d i s c o v e r y of, 6 8 —, l i f e a n d a c h i e v e m e n t s of, 2 2 6 — 2 2 7
—, gravimetric determination of, as B u r e t t e s , d e v e l o p m e n t of, 1 8 4
described by Fresenius, 1 5 6 B u t y r i c a c i d , d e t e c t i o n of, 3
B i s u l p h a t e f o r m a t i o n , a p p l i c a t i o n of, t o
detection of ketones and aldehydes, C a d m i u m , early d e t e r m i n a t i o n of, b y
15 electrogravimetry, 2 1 6
B l a c k , J o s e p h , w o r k a n d findings of, 9 5 C a l c i u m , d e t e c t i o n of, b y o x a l i c a c i d , 1 0 5
B l o w p i p e , early d e v e l o p m e n t and applica- —, d e t e r m i n a t i o n o f , i n w a t e r , b y S c h w a r -
t i o n s of, 9 0 ^ 9 2 zenbach, 199
B o r i c a c i d , a p p l i c a t i o n of, t o d e t e c t i o n o f —, gravimetric determination of, in
poly hydroxy alcohols, 14 presence of magnesium, 157
B ô t t g e r , c o n t r i b u t i o n s of, t o p o t e n t i o - C a l c i u m o x i d e , a p p l i c a t i o n of, t o d e t e c -
metric titrimetry, 2 3 9 , 2 5 0 tion of phosphorus, 8
B o u g o u e r , P i e r r e , c o n t r i b u t i o n s of, to Calx, 87
development of photometry, 2 3 2 "Capillary analysis", development of
Boyle, Robert, definition of "element" chromatography from, 257
by, 77 C a r b o n , d e t e c t i o n of, u s i n g m o l y b d e n u m
—, e x p e r i m e n t s o f , c o n c e r n i n g i n d e s t r u c - trioxide, 6
tibility of matter, 1 1 5 —, d e t e r m i n a t i o n of, b y L i e b i g , 2 0 6
285
—, e a r l y d e t e r m i n a t i o n of, i n i r o n , 8 6 C h e m i l u m i n e s c e n c e , d e t e c t i o n of substi-
C a r b o n d i o x i d e , e a r l y d e t e r m i n a t i o n of, tuted ketones by, 18
in w a t e r , 1 6 9 Chemiluminescent indicators, introduc-
C a r b o n d i s u l p h i d e , a p p l i c a t i o n of, to t i o n of, 1 9 7
detection of amines, 20 Chemistry, origin of the w o r d , 6 3
—, d e t e c t i o n of, 2 9 , 5 0 C h l o r a m i n e T, a p p l i c a t i o n of, as titrimet-
C a r b o n m o n o x i d e , d e t e c t i o n of, 2 9 ric s t a n d a r d , 1 9 9
—, d i s c o v e r y o f , 1 0 3 —, —, t o d e t e c t i o n o f i o d i n e i n o r g a n i c
C a r b o n t e t r a c h l o r i d e , d e t e c t i o n of, 2 9 — substances, 8
30, 50 C h l o r i d e , g r a v i m e t r i c d e t e r m i n a t i o n of,
C a r b o n a t e , M o h r ' s d e t e r m i n a t i o n of, i n naphthalene, 34
presence of hydroxide, 1 8 8 —, —, t o d e t e c t i o n o f u r e a , 3 6 — 3 7
Carbonyl group, fluorimetric detection C h l o r a t e , i o d o m e t r i c d e t e r m i n a t i o n of,
of, 1 5 by Bunsen, 179
C a r b o x y l i c a c i d s , d e t e c t i o n o f , b y ferric C h l o r i d e , g r a v i m e t r i c d e t e r m i n a t i o n of,
hydroximate test, 1 8 , 4 5 in presence of b r o m i d e and iodide,
Carcinogenic substances, determination 157
of, b y f l u o r e s c e n c e q u e n c h i n g , 3 —, t i t r i m e t r i c d e t e r m i n a t i o n of, by
C a r o t e n o i d s , h i s t o r i c a l i n v e s t i g a t i o n of, Liebig, 1 8 2
by column chromatography, 260 C h l o r i n e , d e t e r m i n a t i o n of, in w a t e r , 1 6 0
C a s t i r o n , e a r l y a n a l y s i s of, 1 1 1 —, d e t e r m i n a t i o n o f a t o m i c w e i g h t of, b y
Catalytic processes, analytical application Berzelius, 1 3 9
of, 1 6 3 - 1 6 4 —, p r e p a r a t i o n of, b y S c h e e l e , 1 0 5
Cation analysis, Fresenius' s c h e m e for, Chlorine water, early analytical applica-
150 t i o n s of, 1 4 5
C a v e n d i s h , early w o r k of, 9 9 — 1 0 1 —, e a r l y d e t e r m i n a t i o n o f s t r e n g t h of,
" C e m e n t a t i o n " , early a p p l i c a t i o n of, t o 173
s e p a r a t i o n o f g o l d a n d silver, 6 4 C h l o r o f o r m , d e t e c t i o n of, 3 0
C e r i u m , d i s c o v e r y of, 1 2 9 —, —, d u r i n g t e s t f o r t r i c h l o r o a c e t i c a c i d ,
C e r i u m s a l t s , a p p l i c a t i o n of, t o d e t e c t i o n 28
of phenols, 1 3 1 - C h l o r o m e t h y l i s a t i n , a p p l i c a t i o n of, t o
C e r i u m ( I V ) salts, application t o titrimet- detection of alchols, 12
r y of, b y L a n g e , 1 9 3 —, —, t o i d e n t i f i c a t i o n o f c a r b o x y l i c
—, i o d o m e t r i c determination of, by acids, 1 9
Bunsen, 179 p - C h l o r o n i t r o b e n z e n e , d e t e c t i o n of, 2 4
" C h a l y b i s " , a n a l y s i s of, 1 1 1 Chlorophyll extract, Tsvett's separation
" C h a m a e l e o n " , e a r l i e s t a p p l i c a t i o n of, i n of, b y c o l u m n c h r o m a t o g r a p h y , 2 5 9
titrimetry, 1 7 9 — 1 8 0 C h r o m a t e , d e t e r m i n a t i o n of, b y Pfaff,
C h a n c e l , c o n t r i b u t i o n s of, t o p r e c i p i t a - 145
tion, 160 —, i o d o m e t r i c determination of, by.
Charpentier, contributions to titrimetry Bunsen, 179
by,193 Chromatogram, introduction of term,
Chemicals, mid-nineteenth century prices 260
of, 1 9 0 C h r o m a t o g r a p h y , d e v e l o p m e n t of, 2 5 7 —
C h e m i c a l literature, a d v e n t of, 8 7 260
C h e m i c a l t e a c h i n g , e a r l y d e v e l o p m e n t of, —, i n t r o d u c t i o n o f t e r m , 2 6 0
87 C h r o m i u m ( I I ) , a p p l i c a t i o n o f , t o titri-
286
metry, 199 —, —, b y t i t r i m e t r y w i t h s o d i u m s u l p h i t e ,
C h r o m i u m , g r a v i m e t r i c d e t e r m i n a t i o n of, 180
as described b y F r e s e n i u s , 1 5 6 C o p p e r a c e t a t e , a p p l i c a t i o n of, i n t e s t f o r
—, t i t r i m e t r i c d e t e r m i n a t i o n o f , u s i n g hydrogen cyanide, 4
hexacyanoferrate(III), by Gentele, 1 9 3 Copper ethylacetoacetate—tetrabase
C h r o m o t r o p i c a c i d , a p p l i c a t i o n of, to reagent, detection of ethers with, 19
detection of methanol, 33 Copper sulphate, historical assessment of
C i n n a m i c a c i d , d e t e c t i o n of, 3 0 purity of, 6 5
C i t r i c a c i d , a p p l i c a t i o n of, t o d e t e c t i o n C o p r e c i p i t a t i o n , e a r l y u n d e r s t a n d i n g of,
of formic acid, 3 2 159
—, d e t e c t i o n of, 3 0 , 5 0 C o u l o m e t r y , d e v e l o p m e n t of, for analyt-
Clark, d e t e r m i n a t i o n o f w a t e r hardness ical p u r p o s e s , 2 1 7
by,180 C o x , i n t r o d u c t i o n o f d i f f e r e n t i a l titri-
C l a s s e n , A l e x a n d e r , c o n t r i b u t i o n s of, t o metry b y , 2 3 9
electroanalysis, 2 1 6 C r o t o g i n o , c o n t r i b u t i o n s of, t o p o t e n -
C o b a l t , d e t e r m i n a t i o n of, i n p r e s e n c e o f tiometric titrimetry, 2 3 9
nickel, 1 5 8 Crucible, for i g n i t i o n in a gas a t m o s p h e r e ,
—, g r a v i m e t r i c d e t e r m i n a t i o n of, as d e s - 149
cribed b y Fresenius, 1 5 6 Crucibles, of Berzelius, 1 4 2
C o b a l t - p e a r l t e s t , d i s c o v e r y of, b y G a h n , —, s i n t e r e d g l a s s , 1 5 8
92 C r u i c k s h a n k s , c o n t r i b u t i o n of, t o e l e c t r o -
C o c h i n e a l , i n i t i a t i o n o f u s e of, b y B o y l e , gravimetry, 2 1 4
84 C u p e l l a t i o n , a p p l i c a t i o n of, t o d e t e c t i o n
—, s u i t a b i l i t y of, as t i t r i m e t r i c i n d i c a t o r , of counterfeiting, 6 4
194 —, B a b y l o n i a n r e f e r e n c e s t o , 6 4
Coins, assessment of purity, by cupella- —, e a r l y d e s c r i p t i o n s of, f o r g o l d a n d
tion, 64 silver, 7 1
C o l o r i m e t r y , a p p l i c a t i o n o f Miiller's c o m - —, o r i g i n s o f , 6 3
plementary colorimeter to, 230 C u p f e r r o n , i n t r o d u c t i o n of, for separa-
—, c o n t r i b u t i o n s o f D u b o s c q t o , 2 3 2 tion of iron and copper, 1 5 8
—, e a r l i e s t e x a m p l e s of, 2 3 0 C y a n i d e , t i t r i m e t r i c d e t e r m i n a t i o n of, b y
Column chromatography, development Duflos, 182
of, 2 5 7 - , - , by Liebig, 1 8 2 , 1 9 4
"Complementary c o l o r i m e t e r " as d e s - C y a n u r i c acid c h l o r i d e , a p p l i c a t i o n of, t o
cribed b y Mùller, 2 3 0 detection of pyridine, 35
C o m p l e x o m e t r i c titrimetry, historical C y s t e i n e , d e t e c t i o n of, 3 0 , 5 0
d e v e l o p m e n t of, 1 9 4 Czudnovicz, titrimetric determination of
Conductometric titrimetry, historical vanadium by, 191
a s p e c t s of, 2 4 0 — 2 4 1
Constant proportions, Richter's contribu- D a l t o n , life a n d w o r k of, 123—126
t i o n s t o s t u d i e s of, 1 2 0 D a v y , H u m p h r y , life of, 2 1 4 — 2 1 5
C o p p e r , d e t e c t i o n of, e x t r a c t o f g a l l - n u t s , De Gramont, application of oxy-acetyl-
79 ene flame to spectrography by, 2 2 9
—, —, i n r o s e w a t e r , 8 0 —, p i o n e e r i n g s t u d i e s o n s p e c t r u m anal-
—, g r a v i m e t r i c d e t e r m i n a t i o n of, as d e s - ysis b y , 2 2 8
cribed b y Fresenius, 1 5 6 Derivative thermogravimetry, develop-
—, h i s t o r i c a l d e t e r m i n a t i o n of, b y e l e c - m e n t of, 1 6 1
trolysis, 2 1 6 D e s c r o i z i l l e s , F r a n ç o i s , first a p p l i c a t i o n
287
of redox titrimetry by, 1 7 0 acid, 34
o - D i a n i s i d i n e , a p p l i c a t i o n of, t o d e t e c t i o n —, first a n a l y t i c a l a p p l i c a t i o n s of, 1 5 4
of cinnamic acid, 3 0 —, h i s t o r i c a l a p p l i c a t i o n s of, 1 9 9
Diazobenzene sulphonic acid, detection —, i n t r o d u c t i o n o f , a s r e d o x i n d i c a t o r ,
of aliphatic hydroxy compounds 197
using, 1 1 —, s e l e c t i v e d e t e c t i o n of, 3 0 — 3 1
D i c h l o r o a c e t i c acid, d e t e c t i o n of, 2 7 D i p h e n y l c a r b a z i d e , i n t r o d u c t i o n o f , as
2,3-Dichloronaphthoquinone, application titrimetric indicator, 1 9 7
of, t o d e t e c t i o n o f t h i o l s , 2 5 D i s s o c i a t i o n c o n s t a n t s , e v a l u a t i o n of, b y
2,6-Dichloroquinone-4-chloroimine Ostwald, 249
paper, a p p l i c a t i o n of, in test for p h e n - —, —, f o r i n d i c a t o r s , 2 5 2
ols, 4 Distillation, b y Greek alchemists, 6 6 , 67
D i c h r o m a t e , a p p l i c a t i o n of, t o d e t e r m i n a - —, c a p i l l a r y , s e p a r a t i o n o f a c e t i c a c i d b y ,
tion of organic substances, 1 9 2 27
D i c y a n o g e n , test for, 4 —, e a r l y a p p l i c a t i o n s of, t o w a t e r a n a l y s i s ,
Differential titrations, introduction of, 65
239 —, i n c l o s e d s y s t e m , d i s c o v e r y of, 9 2
D i h y d r o x y b e n z e n e s , i d e n t i f i c a t i o n of, 4 0 D i t h i o c a r b a m a t e s , f o r m a t i o n of, d u r i n g
p-Dimethylaminobenzaldehyde, applica- test for a m i n e s , 2 0 , 2 1
t i o n of, t o d e t e c t i o n o f a m i n e s , 2 0 —, —, d u r i n g t e s t f o r c a r b o n d i s u l p h i d e ,
—, —, t o d e t e c t i o n o f d i p h e n y l a m i n e , 3 1 29
p - D i m e t h y l a m i n o c i n n a m a l d e h y de, appli- 2,2'-Dithiobis-(5-nitropyridine), applica-
c a t i o n of, t o d e t e c t i o n o f a m i n e s , 2 0 t i o n of, t o d e t e c t i o n o f t h i o l s , 2 5
Dimethylglyoxime, 153 D o u b l e b o n d s , d e t e c t i o n of, in organic
2 , 6 - D i m e t h y l m o r p h o l i n e , a p p l i c a t i o n of, substances, 11
t o d e t e c t i o n o f barbituric acid, 2 9 D o u b l e d e c o m p o s i t i o n , o b s e r v a t i o n of,
D i n i t r o a c e t a n i l i d e s , a p p l i c a t i o n of, to by Glauber, 7 8
identification of nitroaniline isomers, D r a g e n d o r f f r e a g e n t , a p p l i c a t i o n of, t o
38 detection of sulphides, 26
Dinitroanilines, identification of isomers Duboscq, contributions of, to early
of, 3 9 colorimetry, 2 3 2
D i n i t r o b e n z e n e , a p p l i c a t i o n of, t o d e t e c - Duff m e t h o d , detection of phenols by, 13
tion of phenols, 13 Duflos, contributions to iodometry by,
2 , 4 - D i n i t r o c h l o r o b e n z e n e , a p p l i c a t i o n of, 178
to detection of amines, 20 Dulong and Petit's law, 1 3 9
2 , 4 - D i n i t r o f l u o r o b e n z e n e , a p p l i c a t i o n of, Dumas, Jean Baptiste, determination of
to detection of aminobenzenesulph- nitrogen b y , in organic substances, 2 0 9
onic acid isomers, 37 - , life of, 2 0 7 - 2 0 8
2,4-Dinitrophenylhydrazine, detection of D u Pasquier, contributions t o i o d o m e t r y
carbonyl c o m p o u n d s with, 15 by,178
D i n i t r o s u l p h o n i c a c i d s , a p p l i c a t i o n of, t o D u v a l , c o n t r i b u t i o n s of, t o t h e r m o g r a v i -
d e t e c t i o n o f d o u b l e and triple b o n d s , metry, 161
11 D y s p r o s i u m , d e t e r m i n a t i o n of, i n y t t r i u m ,
D i p h e n y l a m i n e , a p p l i c a t i o n of, t o d e t e c - by neutron activation, 2 5 6
tion of nitro c o m p o u n d s , 2 3
—, —, t o d e t e c t i o n o f s u b s t i t u t e d a r o - Electrochemical dualism, 1 3 5 , 1 3 6
matic aldehydes, 17 Electrode, d e v e l o p m e n t of hanging mer-
—, —, t o s e l e c t i v e d e t e c t i o n o f o x a l i c cury drop, 2 4 2
288
E l e c t r o d e s , d e v e l o p m e n t of, for e l e c t r o - Ferric h y d r o x i m a t e test, for carboxylic
analysis, 2 1 7 acids and esters, 1 8
Electrode potential, interpretation of, Ferric t h i o c y a n a t e a p p l i c a t i o n of, to
254 d e t e c t i o n o f o x y g e n in organic sub-
E l e c t r o g r a p h y , d e v e l o p m e n t of, 2 1 7 stances, 6
E l e c t r o g r a v i m e t r y , h i s t o r i c a l a s p e c t s of, Filter crucibles, 1 5 8
214-217 Filter paper, ash c o n t e n t o f 1 9 t h c e n t u r y ,
Electrolytes, Ostwald's contribution to 158
t h e o r y of, 2 4 7 —, u s e d b y B e r z e l i u s , 1 4 2
Elemental analysis, organic, 200—214 Filtration, d e v e l o p m e n t o f ash-free paper
E l e m e n t s , Aristotle's t h e o r y of t h e five, for, 1 5 8
61,63 Fire assay, B a b y l o n i a n references t o , 6 4
—, d i s c o v e r y o f , b y s p e c t r u m a n a l y s i s , —, o r i g i n s o f , 6 3
227 F i s c h e r , c o n t r i b u t i o n s of, t o u n d e r s t a n d -
E m i c h , c o n t r i b u t i o n of, t o o r g a n i c m i c r o - ing o f s t o i c h i o m e t r y , 1 2 2
analysis, 2 1 3 F i s c h e r , Karl, m o i s t u r e d e t e r m i n a t i o n b y
Equivalence-point potential, theory of m e t h o d of, 1 9 9
c a l c u l a t i o n of, 2 5 5 " F i x e d air", 9 5
"Equivalent weight", as used by Flame colorations, deductions from,
Fresenius, 1 5 8 during ignition of water residues, 7 9
Equivalent weights, according t o Berg- Flame p h o t o m e t r y , discovery of principle
man, 110 of, 2 2 9
—, a c c o r d i n g t o F i s c h e r , 1 2 1 F l a m e t e s t s , first a n a l y t i c a l a p p l i c a t i o n
E r d e y , c o n t r i b u t i o n s of, t o c h e m i l u m i n e s - of, 9 4
cent indicators, 197 Fluorescein, recommendation of, as
E s t e r s , a l k y l , d e t e c t i o n of, 1 9 titrimetric indicator, 1 9 5 , 1 9 7
—, d e t e c t i o n o f , 1 8 — 1 9 , 4 5 Fluorescence quenching, determination
E t h a n o l , d e t e c t i o n of, 3 1 , 5 1 of carcinogenic substances by, 3
—, h i s t o r i c a l d e t e r m i n a t i o n o f , b y titra- F l u o r i d e , d e t e c t i o n of, in organic c o m -
tion of dichromate, 192 pounds, 7
E t h e r s , d e t e c t i o n of, 1 9 , 4 5 Forchhammer, determination of oxygen
—, t e s t p r o c e d u r e f o r d e t e c t i o n of, 4 5 consumption of water by, 1 9 1
p - E t h o x y c h r y s o i d i n e , i n t r o d u c t i o n of, a s F o r m a l d e h y d e , d e t e c t i o n of, 3 1 , 5 1
"multiform" indicator, 1 9 8 F o r m i c a c i d , s e l e c t i v e d e t e c t i o n of, 3 1 ,
E t h o x y e t h e r s , d e t e c t i o n of, 1 9 51
Ethylbis(2,2-dinitrophenyl) acetate, F r a u n h o f e r , J o s e f , c o n s t r i b u t i o n s of, t o
a p p l i c a t i o n of, in d e t e c t i o n o f tertiary spectroscopy, 218—219
amines, 2 2 F r e s e n i u s , Carl R e m i g i u s , c o m p o s i t i o n
E t h y l s u l p h i d e , d e t e c t i o n of, 3 of analytical precipitates according t o ,
156
—, l i f e a n d w o r k of, 1 5 1 — 1 5 2
Fajans, introduction of fluorescein b y , t o —, s c h e m e o f , f o r c a t i o n a n a l y s i s , 1 5 0
argentometric titrations, 1 9 7 F r i e d e n t h a l , c o n t r i b u t i o n of, t o colori-
Fatty acids, determination of iodine num- metric measurement of pH, 237
bers o f unsaturated, 1 9 3 p - F u c h s i n , ' a p p l i c a t i o n of, t o d e t e c t i o n o f
F e h l i n g , titration o f sugar b y , 1 8 2 aldehydes, 16
Fehling's reagent, 1 6 Fuchsin—aldehyde reaction, application
Fehling's s o l u t i o n , earliest reference t o , of, t o d e t e c t i o n o f p o l y h y d r o x y a l c o -
182 hols, 14
289
Functional groups, detection of, in G l y c e r o l , d e t e c t i o n of, 3 2 , 5 2
organic substances, 9—26 —, h i s t o r i c a l t i t r i m e t r i c d e t e r m i n a t i o n of,
F u r f u r a l , d e t e c t i o n of, 3 2 193
F u s i o n m e t h o d s , review of early, 1 4 7 G l y c o a l d e h y d e , d e t e c t i o n of, 1 5
G l y o x a l , s p e c i f i c d e t e c t i o n of, 3 2
G a l l i c a c i d , a p p l i c a t i o n of, t o d e t e c t i o n G l y o x a l b i s h y d r o x y a c i d , a p p l i c a t i o n of,
o f tartaric acid, 3 6 to detection of o-aminophenol, 4 1
Gall-nuts, applications of extract f r o m , t o G l y o x y l i c a c i d , d e t e c t i o n of, 1 5
identification of iron, 7 9 , 1 5 3 G o c k e l , d e t e c t i o n o f lead in w i n e b y , 8 1
—, —, t o p u r i t y a s s e s s m e n t o f c o p p e r G o l d , earliest r e c o r d e d separation f r o m
sulphate, 65 silver, 6 4
G a l l - n u t e x t r a c t , e x a m i n a t i o n of, 8 0 —, e a r l y d e s c r i p t i o n o f p r o p e r t i e s of, 7 0
G a m m a rays, d e t e c t i o n of, b y scintillator —, e a r l y h i s t o r i c a l c h e c k s f o r p u r i t y of,
crystals, 2 5 7 65
G a s , e a r l y a p p a r a t u s f o r c o l l e c t i o n of, 9 8 —, fire a s s a y of, 6 3
—, o r i g i n o f w o r d , 9 7 —, p r e c i p i t a t i o n of, f r o m a q u a r e g i a , 7 9
G a s e s , d i s c o v e r y of, b y V a n H e l m o n t , 7 8 —, r e a c t i o n of, w i t h P r u s s i a n b l u e , 9 4
G a s a n a l y s i s , a s d e s c r i b e d b y Pfaff, 1 4 6 —, s e p a r a t i o n of, f r o m silver, u s i n g a c i d s ,
—, h i s t o r i c a l d e v e l o p m e n t of, 9 7 — 1 0 5 72, 73
—, i n d u s t r i a l , e a r l y d e v e l o p m e n t o f , 2 2 6 G o o c h crucible, 1 5 8
Gas chromatography, d e v e l o p m e n t of, Goppelsrôder, contributions of, to
260 chromatography, 257
Gas sylvestre, 9 7 G r a i n , v a r i a t i o n o f w e i g h t of, 1 4 4
Gay-Lussac, Joseph, applications of H2S Gravimetry, contributions o f Winkler t o ,
by,147 159—160
—, d e s c r i p t i o n s o f c o m p o u n d s a n d r e a c - G r i e s s , P e t e r , l i f e a n d w o r k of, 1 5 3
tions of iodine by, 1 4 8 G r i e s s — I l o s v a y r e a g e n t , first u s e of, 1 5 3
—, d e t e r m i n a t i o n o f n i t r o g e n b y , i n Griess reaction, 2 3
organic substances, 2 0 7 Griess reagent, 4
—, e a r l y a t t e m p t s t o a n a l y s e o r g a n i c Group separations, of Fresenius, 1 5 2
compounds by, 202 G u a n i d i n e c a r b o n a t e , a p p l i c a t i o n of, t o
—, l i f e a n d a c h i e v e m e n t s of, 1 7 3 — 1 7 8 detection of chloroform, 30
G e b e r , c o n t r i b u t i o n of, t o d i s c o v e r y o f G y ô r y , introduction o f potassium bro-
HNO3 a n d a q u a r e g i a , 6 8 m a t e as t i t r a n t , 1 9 8
—, d e s c r i p t i o n s o f m e t a l s b y , 6 9
Gentele, contributions to titrimetry by, H a b e r , c o n t r i b u t i o n s of, t o d e v e l o p m e n t
193 o f glass e l e c t r o d e , 2 3 5
G e r l a c h , c o n t r i b u t i o n s of, t o q u a n t i t a t i v e H a l i d e s , s i m u l t a n e o u s g r a v i m e t r y of, 1 5 7
spectrum analysis, 2 2 8 H a l o g e n s , a l i p h a t i c , d e t e c t i o n of, u s i n g
G i b b s , W o l c o t t , c o n t r i b u t i o n s of, to succinic or phthalic acid, 7
electrogravimetry, 2 1 6 , 2 1 7 —, d e t e c t i o n o f u s i n g s u l p h o c h r o m i c a c i d ,
G l a s s e l e c t r o d e , d e v e l o p m e n t of, 2 3 5 6
G l a u b e r , f i n d i n g s of, 8 1 —, h i s t o r i c a l m e t h o d s f o r d e t e r m i n a t i o n
—, o b s e r v a t i o n o f d o u b l e d e c o m p o s i t i o n of, i n o r g a n i c c o m p o u n d s , 2 1 0 — 2 1 1
by, 78 —, m i c r o d e t e r m i n a t i o n of, i n o r g a n i c
G l a z u n o v , c o n t r i b u t i o n of, t o e l e c t r o - compounds, 213
graphy, 2 1 7 H a n t z s c h , c o n t r i b u t i o n s of, t o t h e o r y o f
290
indicator behaviour, 1 9 6 of, t o p H m e a s u r e m e n t , 2 3 5
Hartley, pioneering studies o n spectrum Hydrogen halides, test for, 4
analysis b y , 2 2 8 Hydrogen ion concentrations, determina-
Hassel, introduction o f fluorescein b y , t o t i o n of, by conductivity measure-
argentometric titrations, 1 9 7 ments, 253
Herschel, contributions of, to early H y d r o g e n s u l p h i d e , e a r l y a p p l i c a t i o n s of,
spectroscopic research, 2 2 0 145,147
H e v e s y , c o n t r i b u t i o n of, t o r a d i o i s o t o p e —, e a r l y g e n e r a t o r s f o r , 1 4 7
dilution analysis, 2 5 6 —, e a r l y t i t r i m e t r i c d e t e r m i n a t i o n of, i n
Hexacyanoferrate(III), first titrimetric water, 1 7 8
a p p l i c a t i o n of, 1 9 3 , 1 9 7 H y d r o m e t e r , earliest k n o w n reference t o ,
Hexacyanoferrate(II), historical titrimet- 68
ric d e t e r m i n a t i o n of, b y c e r i u m ( I V ) , H y d r o q u i n o n e , d e t e c t i o n of, 4 0
193 H y d r o x i d e , M o h r ' s d e t e r m i n a t i o n of, in
H e x o s e s , d e t e c t i o n of, 1 4 presence of carbonate, 1 8 8
H e y r o v s k y , c o n t r i b u t i o n s of, t o d e v e l o p - Hydroxides, detection of enolic, with
ment of polarographic techniques, iron(III) chloride, 1 3
2 4 1 - 2 4 2 , 243 2-Hydroxy-3-naphthoic acid, application
Higgins, William, contributions to a t o m i c of, t o d e t e c t i o n o f n i t r o c o m p o u n d s ,
theory by, 125 47
High frequency titrations, introduction 7-Hydroxyquinoline, applications of
of, 2 4 1 f l u o r e s c e n c e of, 4 1 , 4 2
H i l d e b r a n d , c o n t r i b u t i o n of, t o t h e o r y o f 8 - H y d r o x y q u i n o l i n e , d e t e c t i o n of, 3 2
potentiometric titration curves, 2 5 3 —, p h e n o l e s t e r of, d e t e c t i o n o f a l c o h o l s
H o l l o w c a t h o d e l a m p , a p p l i c a t i o n of, t o with, 12
AAS, 229 H y p o c h l o r i t e , early d e t e r m i n a t i o n of,
H o l m e s , c o n t r i b u t i o n of, t o d e v e l o p m e n t 173
of ion exchangers, 2 6 1
H o m o l o g o u s l i n e - p a i r s , first i n t r o d u c t i o n
of, t o s p e c t r u m a n a l y s i s , 2 2 8 I a t r o c h e m i s t r y , d e v e l o p m e n t of, 7 3 , 7 7
Hiibl, determination o f iodine n u m b e r s Ilosvay, Lajos, life of, 1 5 4
by,193 Indestructibility of matter, studies con-
H y d r a z i n e , a p p l i c a t i o n of, t o d e t e c t i o n cerning, 1 1 4 — 1 1 7
of selenious acid, 8 Indicators, development of metallo-
2-Hydrazinobenzothiazole, application chromic, 200
of, t o d e t e c t i o n o f g l y o x a l , 3 2 —, d e v e l o p m e n t o f t i t r i m e t r i c , 1 9 4 — 1 9 8
H y d r o c h l o r i c a c i d , as p r e c i p i t a n t , 1 1 1 —, e v a l u a t i o n o f d i s s o c i a t i o n c o n s t a n t s o f ,
—, e a r l y p u r i t y t e s t i n g o f , 1 4 5 252
—, p r e p a r a t i o n o f , b y G l a u b e r , 8 1 —, t h e o r y of, as p r o p o s e d b y O s t w a l d ,
H y d r o g e n , d e t e c t i o n of, using e l e m e n t a l 248
sulphur, 6 I n d i c a t o r b l a n k , first a p p l i c a t i o n o f , 1 7 7
—, d e t e r m i n a t i o n o f , i n o r g a n i c s u b s t a n - I n d i g o , a p p l i c a t i o n of, a s r e d o x i n d i c a t o r ,
ces, b y Liebig, 2 0 6 197
—, d i s c o v e r y o f , 1 0 0 , 1 0 5 —, e a r l y a p p l i c a t i o n as r e d o x i n d i c a t o r ,
H y d r o g e n chloride, discovery of, 1 0 3 173,177
Hydrogen cyanide, test for, with copper Indigo synthesis, application of, to
acetate,4 identification of nitrobenzaldehydes,
H y d r o g e n e l e c t r o d e , earliest a p p l i c a t i o n s 39
291
I n d o l e , a p p l i c a t i o n of, i n d e t e c t i o n o f —, s e p a r a t i o n of, f r o m m a g n e s i u m , 9 5
aldehydes, 16, 44 —, —, f r o m m a n g a n e s e , 1 5 4
I n d o p h e n o l d y e , f o r m a t i o n of, in test —, t i t r i m e t r i c d e t e r m i n a t i o n of, with
for phenols, 4 potassium chromate, 181
Indophenol reaction, detection of phenols Iron(III) chloride, detection of enolic
by 19 hydroxides with, 13
I n q u a r t a t i o n , origin of, 7 3 —, t i t r i m e t r i c a p p l i c a t i o n of, i n L i e b i g ' s
Interference studies, by Kirwan, 1 2 7 determination of phosphoric acid, 1 8 2
Iodide, gravimetric determination of, I r o n ( I I I ) t h i o c y a n a t e , a p p l i c a t i o n of, t o
simultaneously with bromide and d e t e c t i o n o f o x y g e n in organic sub-
chloride, 157 stances, 6
—, i m p r o v e d d e t e r m i n a t i o n o f , b y M o h r , I s a t i n y l m e t h y l e s t e r s , a p p l i c a t i o n of, t o
189 characterization of carboxylic acids,
Iodimetry, historical efforts t o standard- 19
ise t h i o s u l p h a t e f o r , 1 9 1 Isomers, differentiation of, by spot
I o d i n e , d e t e c t i o n of, i n o r g a n i c c o m - tests, 37—42
pounds, 8 I s o m o r p h i s m , o b s e r v a t i o n of, b y M i t s c h e r -
—, d e t e r m i n a t i o n of, i n w a t e r , 1 6 0 lich, 1 3 9
—, d i s c o v e r y a n d e a r l y a p p l i c a t i o n o f , l-(Isothiocyanatomethyl)-isatin, applica-
145, 1 4 7 - 1 4 8 t i o n of, t o d e t e c t i o n o f a m i n e s , 2 0
—, e a r l i e s t a p p l i c a t i o n s of, i n t i t r i m e t r y , I s o t o p e d i l u t i o n a n a l y s i s , d e v e l o p m e n t of,
178 256
—, first t i t r i m e t r i c d e t e r m i n a t i o n of, b y
thiosulphate, 179 J - a c i d , a p p l i c a t i o n of, to detection of
—, i n v e s t i g a t i o n o f p r o p e r t i e s o f , b y G a y - formaldehyde, 31
Lussac, 1 7 4 J a m e s , c o n t r i b u t i o n of, t o g a s c h r o m a t o g -
I o d i n e n u m b e r , first d e t e r m i n a t i o n o f , f o r raphy, 2 6 0
unsaturated fatty acids, 1 9 3 Janowsky reaction, detection of phenols
I o d i n e — s t a r c h r e a c t i o n , d i s c o v e r y of, 1 4 8 by, 13
Iodometric titrations, application of J a n s s e n , c o n t r i b u t i o n of, t o d e v e l o p m e n t
iodine—starch reaction in, 1 4 8 of flame photometry, 2 2 9
I o d o m e t r y , e a r l y a p p l i c a t i o n s of, 1 7 8 — J o n e s r e d u c t o r , first a p p l i c a t i o n of, 1 9 0
179 K e k u l é , d e t e r m i n a t i o n o f h a l o g e n s b y , in
I o n s , early tests for, 1 4 6 — 1 4 7 organic substances, 2 1 0
I o n e x c h a n g e , d e v e l o p m e n t of, 2 6 0 K e m u l a , c o n t r i b u t i o n s of, t o e l e c t r o -
Ion exchange chromatography, develop- analysis, 2 4 2
m e n t of, 2 6 1 K e n n y , c o n t r i b u t i o n s of, t o c h e m i l u m i n e s -
I r o n , d e t e c t i o n of, u s i n g P r u s s i a n b l u e , 9 4 cent indicators, 197
—, e a r l y d e s c r i p t i o n o f p r o p e r t i e s o f , 7 0 K e t o n e s , d e t e c t i o n of, 1 5 , 1 6 — 1 7 , 4 4
—, e a r l y d e t e c t i o n o f , u s i n g g a l l - n u t s , 7 9 —, d e t e c t i o n o f α - s u b s t i t u t e d , 1 8
—, h i s t o r i c a l d e t e r m i n a t i o n o f , u s i n g t h i o - —, differentiation between alicyclic,
cyanate, 2 3 0 , 2 3 2 acyclic and aromatic, 9
—, h i s t o r i c a l i o d o m e t r i c d e t e r m i n a t i o n of, —, t e s t p r o c e d u r e f o r d e t e c t i o n o f , 4 4
178 K i p p , H 2S g e n e r a t o r d e s c r i b e d b y , 1 4 7
—, h i s t o r i c a l t i t r i m e t r i c d e t e r m i n a t i o n of, Kirchhoff, G u s t a v , life a n d a c h i e v e m e n t s
by cerium(IV), 1 9 3 of, 2 2 2 - 2 2 5
—, s e n s i t i v i t y o f r e a c t i o n w i t h g a l l - n u t K i r w a n , Richard, early analyses b y , 1 2 6 —
e x t r a c t , as d e t e r m i n e d b y B o y l e , 8 5 127
292
Kjeldahl, Johan Gustaf, determination of L i e b i g , J u s t u s , c o m b u s t i o n a p p a r a t u s of,
n i t r o g e n in organic s u s b t a n c e s b y , 1 9 8 206
—, d e t e r m i n a t i o n o f n i t r o g e n i n p r o t e i n s - , life of, 2 0 4 - 2 0 5
by,209 - , t i t r i m e t r y o f P O | " , CI" a n d C N " b y ,
K l a p r o t h , life and findings of, 1 2 8 — 1 3 2 182,194
Klemensiewicz, contributions of, to L i t m u s , i n i t i a t i o n o f u s e of, b y B o y l e , 8 4
d e v e l o p m e n t o f glass e l e c t r o d e , 2 3 5 —, s u i t a b i l i t y as t i t r i m e t r i c i n d i c a t o r , 1 9 5
K n o p , introduction of diphenylamine b y , L o m o n o s o v , w o r k a n d f i n d i n g s of, 1 1 4 —
197 115
K o l t h o f f , c o n t r i b u t i o n s of, t o t h e o r y o f Lucas test, 12
indicator behaviour, 1 9 6 L u c i g e n i n e , i n t r o d u c t i o n of, as c h e m i l u -
—, t h e o r y o f r e d o x t i t r a t i o n s b y , 2 5 5 minescent redox indicator, 1 9 7
Kuhlmann, microbalance proposed by, L u c k , p r o p o s a l o f p h e n o l p h t h a l e i n as
163 titrimetric indicator, 1 9 5
K u h n , c o n t r i b u t i o n s of, t o c o l u m n c h r o - Luckow, contribution of, t o e l e c t r o -
matography, 260 gravimetry, 2 1 6 , 2 1 7
L u m i n o l , a p p l i c a t i o n of, t o d e t e c t i o n o f
ketones, 18
L a c t i c a c i d , d e t e c t i o n of, 3 3 —, i n t r o d u c t i o n of, as c h e m i l u m i n e s c e n t
Lambert, Johann Heinrich, contributions redox indicator, 1 9 7
of, t o p h o t o m e t r i c t h e o r y , 2 3 2 — 2 3 3 L u n d e g â r d h , c o n t r i b u t i o n s of, t o f l a m e
Lambert's law, author's description o f photometry, 229
d e r i v a t i o n of, 2 3 3 Lunge, Georg, introduction of methyl
Lampadius, assessment of purity by, 1 4 5 orange by, 1 9 5
Lange, application of cerium(IV) to
titrimetry by, 1 9 3 M a g n e s i u m , d e t e r m i n a t i o n of, i n w a t e r ,
L a n t h a n u m salts, a p p l i c a t i o n of, t o d e t e c - by Schwarzenbach, 199
tion of acetic acid, 2 7 , 4 9 —, g r a v i m e t r i c d e t e r m i n a t i o n o f , i n p r e s -
Lavoisier, a n t i - p h l o g i s t o n t h e o r y of, 9 8 ence of calcium, 157
—, c o m b u s t i o n a n a l y s i s o f o r g a n i c s u b - —, s e p a r a t i o n o f , f r o m i r o n , 9 5
stances b y , 2 0 1 M a g n e s i u m c a r b o n a t e , early s t u d i e s of, b y
—, l i f e a n d w o r k o f , 1 1 5 — 1 1 7 Black, 9 5
L e a d , d e t e c t i o n of, in w i n e , 8 1 M a g n e s i u m s u l p h a t e , e a r l y a n a l y s e s of,
—, e a r l y d e s c r i p t i o n o f p r o p e r t i e s o f , 7 0 113
—, h i s t o r i c a l d e t e r m i n a t i o n o f , b y e l e c t r o - Majer, c o n t r i b u t i o n s of, t o d e v e l o p m e n t
gravimetry, 2 1 6 of amperometry, 2 4 3
—, —, i n m i n e r a l s , 1 0 9 M a l o n i c a c i d , s p e c i f i c d e t e c t i o n of, 3 3 ,
Lead(IV) acetate, a p p l i c a t i o n of, to 52
detection of organic substances, 1 0 M a n g a n e s e , d e t e r m i n a t i o n of, b y a r s e n i -
L e a d o x i d e , i o d o m e t r i c d e t e r m i n a t i o n of, ous acid—permanganate reaction, 1 9 1
by Bunsen, 179 —, d i s c o v e r y of, 1 0 5
"Leight mina", 64 —, gravimetric determination of, as
L é m e r y , c o n t r i b u t i o n s of, t o a n a l y t i c a l described b y Fresenius, 1 5 6
chemistry, 112 —, h i s t o r i c a l d e t e r m i n a t i o n o f , b y e l e c t r o -
L e o n a r d , c o n t r i b u t i o n s of, t o s p e c t r u m gravimetry, 2 1 6
analysis, 2 2 8 —, titrimetric determination of, by
Le Rosen test, 9—10 Gentele using hexacyanoferrate(III),
Liebermann test, for p h e n o l s , 1 3 193
293
- , - , by Volhard-Wolff method, 199 Metals, action of phosphoric acid o n , 9 4
M a n g a n e s e ( I V ) o x i d e , a p p l i c a t i o n of, t o —, h i s t o r i c a l m e t h o d s f o r d e t e c t i o n of, b y
d e t e c t i o n o f n i t r o g e n in o r g a n i c s u b - electrolysis, 2 1 6
stances, 6 —, h i s t o r i c a l s t u d y o f d i s s o l u t i o n of, 1 1 0
Manganese oxide, iodometric determina- M e t a n i l i c a c i d , s e l e c t i v e d e t e c t i o n of, 3 7
t i o n of, b y B u n s e n , 1 7 9 M e t h a n o l , d e t e c t i o n of, 3 3
M a n g a n e s e o x i d e s , e a r l y s t u d y of, 1 1 1 M e t h y l o r a n g e , i n t r o d u c t i o n of, as titri-
Marggraf, c o n t r i b u t i o n s of, t o d e v e l o p - metric indicator, 1 9 5
ment of spectroscopy, 218 M e t h y l red, i n t r o d u c t i o n of, 1 9 6
—, p r o p o s a l s of, c o n c e r n i n g d e t e r m i n a - Michaelis, investigation o f acid—base pro-
t i o n o f silver, 1 1 2 cesses b y , 2 5 1 , 2 5 5
—, r e s e a r c h w o r k o f , 9 2 M i c r o a n a l y s i s , d e v e l o p m e n t of, 1 6 1 — 1 6 5
Margueritte, r e c o m m e n d a t i o n of perman- —, o r g a n i c , d e v e l o p m e n t of, 2 1 3
ganate for titrimetry b y , 1 7 9 M i c r o b a l a n c e , d e v e l o p m e n t of, 1 6 3
Marius Gratidianus, c o i n examination M i c r o b u r e t t e s , d e v e l o p m e n t of, 2 0 0
ordered by, 6 4 Microchemical techniques, development
Marsh's device, for arsenic testing, 1 4 8 — of, 1 6 3
149 M i c r o s c o p e , e a r l y a p p l i c a t i o n s of, t o anal-
M a r t i n , c o n t r i b u t i o n s of, t o p a r t i t i o n ysis, 9 5
chromatography, 260 M i c r o s c o p y , a p p l i c a t i o n of, t o e a r l y anal-
Mascart, recalculation of wavelengths o f yses, 161—162
spectral lines b y , 2 2 7 Midlands Association for Qualitative
M e n t h o l , d e t e c t i o n of, 3 Analysis, survey of group separations
M e r c a p t a n s , d e t e c t i o n of, w i t h m e r c u r y - by,153
(II) c y a n i d e , 2 5 M i n e r a l s , b e h a v i o u r of, w h e n h e a t e d w i t h
M e r c u r y , early tests for d e t e c t i o n of, 8 0 blowpipe, 91
—, h i s t o r i c a l d e t e r m i n a t i o n o f , b y e l e c t r o - M i n e r a l a c i d s , e a r l y a p p l i c a t i o n s of, t o
gravimetry, 2 1 6 gold testing, 7 1
M e r c u r y c a t h o d e , first d e p o s i t i o n of Mineral analysis, Bergman's c o n t r i b u t i o n s
metals on, 217 to, 109—110
Mercury(II) cyanide, detection of mer- —, e a r l y d e v e l o p m e n t of, 8 6
captans with, 25 M i n e r a l w a t e r s , a n a l y s i s of, b y B e r z e l i u s ,
M e r c u r y d r o p e l e c t r o d e , i n t r o d u c t i o n of, 134
242 —, e a r l i e s t t i t r i m e t r i c a n a l y s i s of, 1 6 7
M e r c u r y i o n s , b e h a v i o u r of, w i t h P r u s s i a n —, h i s t o r i c a l d e t e r m i n a t i o n o f b r o m i n e i n ,
blue, 9 4 230
M e r c u r y ( I ) n i t r a t e , a p p l i c a t i o n of, to " M i s y " , a p p l i c a t i o n of, t o s e p a r a t i o n o f
redox titrimetry, 1 9 9 gold f r o m silver, 6 4
—, e a r l y a n a l y t i c a l a p p l i c a t i o n s of, 1 4 5 Mitscherlich, observation of isomorphism
Mercury(II) nitrate, titrimetric determina- by,139
t i o n of, i n L i e b i g ' s d e t e r m i n a t i o n o f Mohr, Friedrich, cost of equipment sold
chloride, 1 8 2 by,190
Mesityl o x i d e , d e t e c t i o n of, 1 5 —, d e t e r m i n a t i o n o f d i s s o l v e d o x y g e n b y ,
Metal i o n s , P e l o u z e ' s d e t e r m i n a t i o n of, 189
by titration with s o d i u m sulphide, —, l i f e a n d a c h i e v e m e n t s of, 1 8 4 — 1 9 0
182 Moisture, iodimetric determination of,
Metallochromic indicators, development 199
of, 2 0 0 M o l y b d e n u m , d i s c o v e r y of, 1 0 5
294
Molybdenum blue, 9 Nitric acid, discoverer of, 6 8
M o l y b d e n u m t r i o x i d e , a p p l i c a t i o n of, t o —, e a r l y p r e p a r a t i o n a n d d e s c r i p t i o n o f
d e t e c t i o n o f c a r b o n in o r g a n i c s u b - properties of, 7 2 , 7 3
stances, 6 —, e a r l y s t u d y o f s o l v e n t p o w e r o f , 1 1 0
M o n o c h l o r o a c e t i c a c i d , d e t e c t i o n of, 2 7 —, e a r l y t i t r i m e t r i c d e t e r m i n a t i o n of, 1 6 8
M o r p h o l i n e , a p p l i c a t i o n of, t o d e t e c t i o n —, p r e p a r a t i o n of, b y G l a u b e r , 8 1
of ethanol, 5 1 N i t r i c o x i d e , d i s c o v e r y of, 1 0 3
Muller, complementary colorimeter N i t r i l e s , d e t e c t i o n of, 2 4 — 2 5 , 4 8
devised b y , 2 3 0 — 2 3 1 N i t r i t e , first s p e c i f i c t e s t f o r , 1 5 3
Mulliken, classification o f c o m p o u n d s by, Nitroanilines, identification of isomers,
213 38
M u l t i p l e p r o p o r t i o n s , d i s c o v e r y o f l a w of, N i t r o a n t i p y r i n , a p p l i c a t i o n of, t o d e t e c -
123 tion of a-naphthylamine, 4 1
m - N i t r o b e n z a l d e h y d e , d e t e c t i o n of, 1 5
N a p h t h a l e n e , s e l e c t i v e d e t e c t i o n of, 3 4 , Nitrobenzaldehydes, identification of iso-
52 m e r s of, 3 9
a- a n d j3-Naphthols, d e t e c t i o n of, b y N i t r o b e n z e n e , d e t e c t i o n of, 3
Janowsky reaction, 13 N i t r o b e n z e n e d e r i v a t i v e s , d e t e c t i o n of, 2 4
N a p h t h o l s , i d e n t i f i c a t i o n of, 4 0 — 4 1 Nitrocompounds, test procedure for
1 , 2 - N a p h t h o q u i n o n e - 4 - s u l p h o n a t e , appli- d e t e c t i o n of, 2 2 — 2 4 , 4 7
c a t i o n of, t o d e t e c t i o n o f m o n o c h l o r o - N i t r o g e n , d e t e c t i o n of, u s i n g m a n g a n e s e -
acetic acid, 27 (IV) oxide, 6
—, —, t o d e t e c t i o n o f p i p e r i d i n e , 3 4 —, d e t e r m i n a t i o n of, in o r g a n i c s u b -
α - N a p h t h y l a m i n e , a p p l i c a t i o n of, t o iden- s t a n c e s , as r e c o m m e n d e d b y K j e l d a h l ,
tification of nitroaniline isomers, 3 8 198
|3-Naphthylamine, application of, to —, —, —, b y D u m a s , 2 0 9
detection of lactic acid, 3 3 —, —, —, b y G a y - L u s s a c a n d T h é n a r d , 2 0 7
N a p h t h y l a m i n e s , d e t e c t i o n of, 4 1 —, —, i n p r o t e i n s , b y K j e l d a h l , 2 0 9
Nernst e q u a t i o n , i n t r o d u c t i o n of, 2 4 9 —, d i s c o v e r y of, 1 0 0 , 1 0 5
Nessler's reagent, a p p l i c a t i o n of, t o d e t e c - " N i t r o n o i l " , d e s c r i p t i o n of, b y O l y m p i o -
tion of dichloroacetic acid, 27 doros, 66
—, —, t o d e t e c t i o n o f u r e a , 5 4 N i t r o p h e n o l s , i d e n t i f i c a t i o n of, 4 2
N e u t r o n activation analysis, d e v e l o p m e n t 4 - N i t r o p h e n y l a c e t o n i t r i l e , a p p l i c a t i o n of,
of, 2 5 6 to detection of quinones, 35
N e u t r o n s o u r c e s , d e v e l o p m e n t of, 2 5 6 o - N i t r o p h e n y l h y d r a z i n e , a p p l i c a t i o n of,
N i c k e l , g r a v i m e t r i c d e t e r m i n a t i o n of, as to detection of carboxylic acids, 18
described b y Fresenius, 1 5 6 —, —, t o d i f f e r e n t i a t i o n b e t w e e n n a p h -
N i c k e l d i m e t h y l g l y o x i m e , a p p l i c a t i o n of, thols, 4 1
in d e t e r m i n a t i o n o f acid or basic char- Nitroprusside—morpholine reaction,
acter, 5 a p p l i c a t i o n of, t o d e t e c t i o n o f e t h a n o l ,
Nickel oxide, iodometric determination 31
of, b y B u n s e n , 1 7 9 5-Nitroso-8-hydroxyquinoline, detection
N i c o t i n e , first t i t r i m e t r i c d e t e r m i n a t i o n of phenols with, 13
of, 1 8 1 a - N i t r o s o - | 3 - n a p h t h o l , a p p l i c a t i o n of, t o
N i n h y d r i n , a p p l i c a t i o n of, t o d e t e c t i o n o f detection of tyrosine, 36
thiophen, 36 —, r e c o m m e n d a t i o n of, f o r d e t e r m i n a t i o n
N i o b i u m , discovery of, 1 3 8 , 1 4 9 of cobalt, 1 5 8
N i t r a t e , d e t e c t i o n of, b y I l o s v a y , 1 5 3 β - N i t r o s o - a - n a p h t h o l , a p p l i c a t i o n of, t o
295
detection of β-naphthol, 4 0 —, first c o m b u s t i o n a n a l y s i s o f , 2 0 1
m - N i t r o t o l u e n e , d e t e c t i o n of, i n p r e s e n c e —, h i s t o r i c a l a s p e c t s o f d e t e r m i n a t i o n o f
of isomers, 24 o x y g e n in, 2 1 1
N i t r o u s o x i d e , d i s c o v e r y of, 1 0 0 —, m i c r o a n a l y s i s of, 2 1 3
N o b l e m e t a l s , early t e x t s c o n c e r n i n g anal- O r t h a n i l i c a c i d , s e l e c t i v e d e t e c t i o n of, 3 7
y s i s of, 1 4 5 Oscillopolarography, development of,
242
Optical m e t h o d s of analysis, early devel- O s t e r r e i c h e r , filter c r u c i b l e s p r o p o s e d b y ,
o p m e n t of, 2 1 8 — 2 3 0 158
O r e s , a n a l y s i s of, b y B e r g m a n , 1 0 9 O s t w a l d , W i l h e l m , c o n t r i b u t i o n s of, t o
Organic elemental analysis, 2 0 0 — 2 1 4 precipitation theory, 2 4 7 — 2 4 8
Organic oxidizing substances, identifica- —, —, t o t h e o r y o f i n d i c a t o r b e h a v i o u r ,
t i o n of, 5 195-196
O r g a n i c r e a g e n t s , d e v e l o p m e n t of, f o r —, i n t e r p r e t a t i o n o f e l e c t r o d e p o t e n t i a l
analysis, 1 5 8 by,254
—, i n t r o d u c t i o n o f , t o a n a l y s i s , 1 5 3 — 1 5 4 - , l i f e of, 2 4 4 - 2 4 6
Organic reducing substances, identifica- —, t h e o r e t i c a l e x p l a n a t i o n s o f a n a l y t i c a l
t i o n of, 5 phenomena by, 246
Organic substances, d e t e c t i o n of a l c o h o l O x a l i c a c i d , a p p l i c a t i o n of, as a c i d i m é t r i e
groups in, 1 2 standard by Mohr, 1 8 8
—, d e t e c t i o n o f a l i p h a t i c h a l o g e n g r o u p s —, —, t o s e p a r a t i o n o f c a l c i u m , 9 5
in, 7 —, d e t e c t i o n of, 3 4 , 5 3
detection of benzyl and benzal groups —, h i s t o r i c a l a p p l i c a t i o n of, t o d e t e c t i o n
in, 1 0 , 1 1 of calcium, 105
detection of bromine in, using sulpho- —, h i s t o r i c a l d e t e r m i n a t i o n of, b y per-
chromic acid, 7 manganatometry, 180
, detection of carbon in, 6 O x a m i d e , d e t e c t i o n of, 3 4
detection of fluoride in, using calcium O x a m i d e s , i d e n t i f i c a t i o n of, 2 5
oxide, 7 O x a m i d e f o r m a t i o n , a p p l i c a t i o n of, to
d e t e c t i o n o f f u n c t i o n a l g r o u p s in, 9— d e t e c t i o n o f nitriles, 2 5
26 O x y g e n , d e t e c t i o n of, u s i n g i r o n ( I I I )
, detection of halogens in, 6 thiocyanate, 6
detection of iodine in, using magne- —, d e t e r m i n a t i o n o f d i s s o l v e d , i n w a t e r ,
sium carbonate, 8 160
, detection of nitrogen in, 6 —, —, —, b y M o h r , 1 8 9
, detection of o x y g e n in, 6 —, d i s c o v e r y of, 1 0 5
d e t e c t i o n o f p h o s p h o r u s i n , u s i n g cal- —, h i s t o r i c a l a s p e c t s o f d e t e r m i n a t i o n of,
cium oxide, 8 in organic s u b s t a n c e s , 2 1 1
d e t e c t i o n o f s e l e n i u m i n , using per- —, p r e p a r a t i o n of, 1 0 2 , 1 0 3
chloric acid and hydrazine, 8 O x y g e n c o n s u m p t i o n , of water, historical
, detection of sulphur in, 6, 8 methods of determining, 1 9 1
determination of carbon and hydrogen O z o n e , i o d o m e t r i c d e t e r m i n a t i o n of, b y
in, by Liebig, 2 0 6 Bunsen, 179
determination of nitrogen in, b y
Dumas, 209 Pal S z i l y , c o n t r o b u t i o n of, t o a p p l i c a t i o n
t —, b y G a y - L u s s a c a n d T h é n a r d , 2 0 7
of buffer solutions, 2 5 0
determination of sulphur in, by Henry Paper chromatography, 2 5 7
and Plisson, 2 1 0 P a p y r u s , a p p l i c a t i o n of, t o a s s e s s m e n t o f
296
purity of tin, 65 P h e n y l e n e d i a m i n e s , i d e n t i f i c a t i o n of, 4 2
Paracelsus, p h i l o s o p h i e s of, 7 4 — 7 5 P h e n y l h y d r a z i n e , a p p l i c a t i o n of, t o d e t e c -
Partial p r e s s u r e s , l a w of, 1 2 4 tion of benzal groups, 1 0 , 11
Partition chromatography, introduction —, d e t e c t i o n o f c a r b o n y l compounds
of, 2 6 0 with, 15
Péligot, d e t e r m i n a t i o n o f n i t r o g e n in Phenylhydrazones, differentiation among,
organic c o m p o u n d s b y , 2 0 9 15
Pelouze, titrimetry of metal ions and P h e n y l m e t h y l p y r a z o l o n e , a p p l i c a t i o n of,
phosphoric acid b y , 1 8 2 to detection of pyrocatechol, 4 0
P e n t a b r o m o a c e t o n e , f o r m a t i o n of, during P h l o g i s t o n , p r o c e s s f o r d e t e r m i n a t i o n of,
test for citric acid, 3 0 89
2 , 3 - P e n t a n e d i o n e , d e t e c t i o n of, 1 5 Phlogiston theory, 87—89
P e n t o s e s , d e t e c t i o n of, 1 4 P h l o r o g l u c i n o l , a p p l i c a t i o n of, t o d e t e c -
P e r m a n g a n a t e , i n t r o d u c t i o n of, t o t i t r i m - t i o n o f furfural, 3 2
etry, 1 7 9 —, —, t o d e t e c t i o n o f p y r o g a l l o l , 4 0
—, i o d o m e t r i c determination of, by —, r e a c t i o n of, w i t h s a l i c y l a l d e h y d e , 4 0
Bunsen, 179 P h o s g e n e , d e t e c t i o n of, 3 4
P e r o x y b e n z o i c a c i d , a p p l i c a t i o n of, t o P h o s p h a t e , d e t e c t i o n of, 8
d e t e c t i o n o f u n s a t u r a t i o n in o r g a n i c P h o s p h o m o l y b d i c a c i d , a p p l i c a t i o n of, t o
substances, 11 detection of carbon monoxide, 29
Pfaff, g e n e r a l a n a l y t i c a l t e x t b y , 1 4 5 P h o s p h o r i c a c i d , first p r o d u c t i o n of, 9 4
Pfeffer, construction of semi-permeable —, L i e b i g ' s t i t r i m e t r i c d e t e r m i n a t i o n of,
membrane by, 244 using iron(III) chloride solution, 1 8 2
p H , d e v e l o p m e n t o f c o n c e p t of, 2 4 9 —, P e l o u z e ' s d e t e r m i n a t i o n of, b y titra-
—, h i s t o r i c a l d e v e l o p m e n t o f m e t h o d s f o r tion with uranium solution, 1 8 2
m e a s u r e m e n t of, 2 3 5 — 2 3 7 P h o s p h o r u s , d e t e c t i o n of, i n o r g a n i c s u b -
—, i n t r o d u c t i o n o f c o l o r i m e t r i c m e t h o d s stances, 8
for m e a s u r e m e n t of, 2 3 6 —, e f f e c t o f , i n i r o n , 8 6
pH determination, d e v e l o p m e n t of colori- P h o t o g r a p h i c p l a t e , a p p l i c a t i o n of, t o
metric m e t h o d s for, 1 9 6 spectrum analysis, 2 2 8
pH function, introduction of, by Photometry, contributions of Bougouer
S^rensen, 1 9 6 to, 232
p - P h e n e t i d i n e , a p p l i c a t i o n of, t o d e t e c - —, c o n t r i b u t i o n o f L a m b e r t t o , 2 3 3
tion of acetone, 27 —, c o n t r i b u t i o n o f V i e r o r d t t o , 2 3 4
P h e n o l , d e t e c t i o n of, 3 —, h i s t o r i c a l d e v e l o p m e n t o f i n s t r u m e n t a -
Phenols, detection of, by various tion for, 2 3 4
methods, 13 o-Phthalaldehyde, application of, to
—, d i f f e r e n t i a t i o n f r o m s a t u r a t e d a c y c l i c detection of hydroquinone, 4 0
alcohols, 9 p-Phthalaldehyde, application of, to
—, L i e b e r m a n n t e s t f o r , 1 3 detection of hydroxyhydroquinone,
—, r e a c t i o n of, w i t h h e x a m i n e , 1 3 40
—, t e s t p r o c e d u r e s f o r d e t e c t i o n of, 4 3 Phthalic a c i d , a p p l i c a t i o n of, in d e t e c t i o n
P h e n o l p h t h a l e i n , r e c o m m e n d a t i o n of, a s of halogens, 7
titrimetric indicator, 1 9 5 P i n k h o f , c o n t r i b u t i o n of, t o p o t e n t i o -
P h e n o s a p h r a n i n e , a p p l i c a t i o n of, as r e d o x metric titrimetry, 2 3 9
indicator, 1 9 7 Piperidine, d e t e c t i o n of, 3 4 , 5 3
m - P h e n y l e n e d i a m i n e , a p p l i c a t i o n of, t o Piperidine 8-hydroxyquinoline vanadate,
detection of formaldehyde, 31 a p p l i c a t i o n of, t o d e t e c t i o n o f a l c o -
hols, 12
297
Pisani, d e t e r m i n a t i o n o f t i t a n i u m d i o x i d e Précipitants, historical s t u d y of, 1 1 0
by,191 Precipitates, c o m p o s i t i o n o f analytical,
Platinum chloride, early analytical appli- according t o Fresenius, 1 5 6
cation of, 1 4 5 —, e f f e c t o f h e a t o n , 1 6 0
P l a t i n u m e l e c t r o d e , first r e c o m m e n d a t i o n Precipitation, early studies of, b y B o y l e ,
of, f o r m e a s u r e m e n t o f p H , 2 3 6 84
Platinum ores, early m i c r o s c o p i c e x a m i - —, O s t w a l d ' s c o n t r i b u t i o n t o t h e o r y o f ,
n a t i o n of, 9 5 247-248
Platinum wire, use of, during o p e r a t i o n o f —, t e c h n i q u e s o f c o n t r o l l i n g , i n g r a v i m -
blowpipe, 9 2 etry, 1 6 0
Polarised e l e c t r o d e s , i n t r o d u c t i o n of, 2 3 9 Precipitation from h o m o g e n e o u s solu-
Polarography, historical aspects of, 2 4 1 — tion, 1 6 0
242 Precipitation titrations, application o f
P o l l o k , c o n t r i b u t i o n s of, t o s p e c t r u m alkali t h i o c y a n a t e s i n , 1 9 3
analysis, 2 2 8 —, e a r l i e s t a p p l i c a t i o n s o f , 1 6 7 , 1 7 2
P o l y h y d r o x y a l c o h o l s , d e t e c t i o n of, using Pregl, Fritz, life of, 2 1 2 - 2 1 3
boric acid, 1 4 —, m i c r o d e t e r m i n a t i o n s o f C , H a n d N ,
Porcelain, early a t t e m p t s t o analyse, 9 1 213
Potash, analysis of, b y Gay-Lussac, 1 7 6 Priestley, w o r k a n d findings of, 1 0 1 — 1 0 3
Potassium, first separation of, from Proteins, determination o f nitrogen in, b y
sodium, 9 4 Kjeldahl, 2 0 9
—, gravimetric determination of, as Proust, analysis o f tin o x i d e s b y , 1 2 3
described b y Fresenius, 1 5 6 Prussian b l u e , early i n v e s t i g a t i o n s of, 9 3
Potassium b r o m a t e , i n t r o d u c t i o n of, as Purine derivatives, test for, 4
titrant, 1 9 8 Purple o f Cassius, d e t e c t i o n o f gold b y
Potassium cyanide—oxine paper, 4 f o r m a t i o n of, 1 5 0
Potassium hexacyanoferrate(II) applica- Pyridine, d e t e c t i o n of, 3 , 3 5 , 5 3
t i o n of, in titrimetric d e t e r m i n a t i o n o f P y r i d i n e - 2 - a l d e h y d e , a p p l i c a t i o n of, t o
iron, 1 6 9 d e t e c t i o n o f 0-naphthylamine, 4 1
Potassium hexacyanoferrate(IV), early —, —, t o i d e n t i f i c a t i o n o f a m i n o b e n z o i c
investigations of, 9 3 acid isomers, 3 8
Potassium hydrogen sulphate, applica- Pyridoxal, d e t e c t i o n of, 1 5
tion in fusions, b y Rose, 1 4 7 Pyridylpyridinium dichloride, application
P o t a s s i u m i o d a t e , first t i t r i m e t r i c a p p l i - of, t o d e t e c t i o n o f m a l o n i c a c i d , 3 3
cation of, 1 8 1 P y r o c a t e c h o l , identification of, 4 0
—, r e c o m m e n d a t i o n o f , f o r s t a n d a r d i z a - Pyrogallol, d e t e c t i o n of, 4 0
tion of thiosulphate, 1 9 2 P y r o l y s i s , a p p l i c a t i o n s of, in teats f o r
P o t a s s i u m i o d i d e , a p p l i c a t i o n o f , a s titri- organic c o m p o u n d s , 4
metric indicator, 1 9 4 —, o f o r g a n i c c o m p o u n d s , w i t h v a n a d i u m
P o t a s s i u m p e r m a n g a n a t e , see also: "Per- pentoxide, 9
manganate" —, —, w i t h c a r b o n a t e s , 9
—, M o h r ' s p r e p a r a t i o n o f , 1 8 9 Pyrolytic cleavage products, 4
Potassium sulphate, early analysis of, 1 1 2
Potential, deposition at controlled, devel- Qualitative analysis, Fresenius' s c h e m e of,
o p m e n t of, 2 1 7 152
Potentiometric titrimetry, introduction Quantitative analysis, contribution o f
of, 2 3 7 Fresenius t o , 1 5 5
—, h i s t o r i c a l a s p e c t s o f , 2 3 7 — 2 4 0 Q u a r t z fibre, a p p l i c a t i o n o f , t o m i c r o -
298
balance technology, 1 6 3 ration o f gold f r o m silver, 6 4
Q u i n o n e s , d e t e c t i o n of, 3 5 , 5 3 Schloesing, determination of alkaloids by,
181
R a d i o c h e m i c a l anlaysis, d e v e l o p m e n t of, S c h ô n b e i n , c o n t r i b u t i o n of, t o paper
255-256 chromatography, 257
R a d i o m e t r i c t i t r a t i o n s , d e v e l o p m e n t of, S c h ô n i g e r , flask m e t h o d o f a n a l y s i s p r o -
256 posed b y , 2 1 3
Radium—beryllium neutron source, 2 5 6 Schulek, introduction of p-ethoxychryso-
R e a c t i o n s , s t u d y of, in s o l u t i o n , 9 2 — 9 7 idine b y , 1 9 8
R e d o x i n d i c a t o r s , d e v e l o p m e n t of, 1 9 7 Schulze, determination of oxygen con-
R e d o x reactions, o n ion e x c h a n g e resins, sumption of water by, 1 9 1
261 S c h u t z e , d e t e r m i n a t i o n o f o x y g e n b y , in
R e d o x t i t r a t i o n s , e a r l i e s t e x a m p l e s of, organic c o m p o u n d s , 2 1 1
170,173 S c h w a r z , Karl, d e s c r i p t i o n s o f titrimetry
—, t h e o r y o f , 2 5 5 by,184
R e s o r c i n o l , d e t e c t i o n of, 1 3 , 4 0 —, r e c o m m e n d a t i o n o f t h i o s u l p h a t e f o r
R h o d a n i n e , a p p l i c a t i o n of, t o d e t e c t i o n titrimetry by, 1 7 9
of quinones, 53 S c h w a r z e n b a c h , c o n t r i b u t i o n s of, t o c o m -
R i c h t e r , i n t e r p r e t a t i o n o f f i n d i n g s of, b y plexometric titrimetry, 1 9 9 — 2 0 0
Berzelius, 1 3 8 S c i n t i l l a t i o n c o u n t e r s , d e v e l o p m e n t of,
- , l i f e a n d w o r k of, 1 1 8 - 1 2 1 255
Ring oven technique, 1 6 4 Selenic acid, iodometric determination
Roscoe, introduction of concept of of, b y B u n s e n , 1 7 9
absorption coefficient by, 2 3 3 S e l e n i o u s a c i d , d e t e c t i o n of, u s i n g h y d r a -
R o s e , H e i n r i c h , l i f e a n d w o r k of, 1 4 9 — zine, 8
150 S e l e n i u m , d e t e c t i o n of, i n o r g a n i c s u b -
Rose water, detection of copper in, 8 0 stances, 8
Rozsa, introduction of p-ethoxychrysoi- Semi-permeable membrane, first con-
dine by, 198 s t r u c t i o n of, 2 4 4
R u b b e r t u b i n g , i n t r o d u c t i o n of, into Separations, early electroanalytical, 2 1 6
laboratory practice, 1 4 4 —, F r e s e n i u s ' d e s c r i p t i o n of, as a p p l i e d t o
R u n g e , c o n t r i b u t i o n of, t o c h r o m a t o g - gravimetry, 157
raphy, 257 S h i k a t a , c o n t r i b u t i o n s of, t o d e v e l o p m e n t
Rutherford, Daniel, discovery of nitrogen of polarography, 2 4 1
by,100 Silicofluoric acid, isolation of, by
Scheele, 105
S a l i c y l a l c o h o l , d e t e c t i o n of, 3 6 S i l i c o n t e t r a f l u o r i d e , d i s c o v e r y of, 1 0 3
S a l i c y l a l d e h y d e , d e t e c t i o n of, 1 5 , 2 8 , 5 4 S i l o x e n e , i n t r o d u c t i o n of, as c h e m i l u m i -
—, s e l e c t i v e d e t e c t i o n o f , 3 6 nescent redox indicator, 197
Sampling practice, of Mohr, 1 8 9 Silver, earliest r e c o r d e d separation f r o m
S a n d , c o n t r i b u t i o n s of, t o e l e c t r o a n a l y s i s , gold, 64
217 —, fire a s s a y of, 6 3
S c h e e l e , w o r k a n d findings of, 1 0 4 — 1 0 5 —, gravimetric determination of, as
Schiff bases, a p p l i c a t i o n of, in test for described by Fresenius, 1 5 7
aldehydes, 16 —, h i s t o r i c a l d e t e r m i n a t i o n of, b y e l e c -
S c h i s t e , a p p l i c a t i o n of, t o h i s t o r i c a l s e p a - trolysis, 2 1 6
299
—, p r e c i p i t a t i o n of, b y c h l o r i d e , 1 1 2 Specific gravity, analytical e x p l o i t a t i o n
—, r e a c t i o n o f , w i t h P r u s s i a n b l u e , 9 4 of, 6 8
—, r e c o v e r y f r o m s o l u t i o n s , b y a d d i t i o n S p e c i f i c w e i g h t s , d e t e r m i n a t i o n of, 6 9
of copper wire, 7 3 Spectra, reversed, discovery of p h e n o m e -
—, s e p a r a t i o n of, f r o m g o l d , u s i n g a c i d s , n o n of, 2 2 2
72, 73 Spectral lines, recalculation of wave-
—, t i t r i m e t r i c d e t e r m i n a t i o n of, b y G a y - l e n g t h s of, b y M a s c a r t a n d A n g s t r o m ,
Lussac, 176—177 227-228
S i l v e r c h r o m a t e , a p p l i c a t i o n of, t o d e t e c - Spectral line intensity, photoelectric
tion of acetylene, 28 m e a s u r e m e n t of, 2 2 9
S i l v e r c o u l o m e t e r , e a r l y a p p l i c a t i o n of, Spectroscope, of Bunsen and Kirchhoff,
217 221
S i l v e r f e r r o c y a n i d e , a p p l i c a t i o n of, i n t e s t S p e c t r o s c o p i c m e t h o d s o f analysis, devel-
for h y d r o g e n halides, 4 o p m e n t of, 2 1 8 — 2 2 9
S k r a u b s y n t h e s i s , a p p l i c a t i o n of, t o d e t e c - Spectrum analysis, application of p h o t o -
tion of glycerol, 3 2 graphic plate t o , 2 2 8
S o a p s , e a r l y s t u d i e s of, 8 0 —, d i s c o v e r y o f n e w e l e m e n t s b y , 2 2 7
S o a p s o l u t i o n , h i s t o r i c a l a p p l i c a t i o n of, —, e a r l y , 2 2 3 — 2 2 4
to determination of water hardness, —, q u a n t i t a t i v e , 2 2 8
180 S p o t t e s t s , s y s t e m a t i c s t u d i e s of, 1 6 4 —
S o d i u m h y d r o x i d e , historical determina- 165
t i o n of, 1 7 2 Standard m e t h o d o f analysis, earliest
S o d i u m i o n s , first s e p a r a t i o n of, f r o m e x a m p l e of, 7 1
potassium ions, 9 4 S t a n d a r d s o l u t i o n s , first r e p o r t e d titri-
Sodium metal, detection of aliphatic m e t r i c u s e of, 1 8 2
hydroxy compounds with, 11 Staudinger, study of functional group
S o d i u m nitrate, s t u d y of characteristics reactions by, 2 1 3
of, 9 4 S t e e l , e a r l y a n a l y s i s of, 1 1 1
S o d i u m n i t r o p r u s s i a t e , a p p l i c a t i o n of, as Steinfels, titrimetric determination of
titrimetric indicator, 1 9 4 glycerine b y , 1 9 3
S o d i u m n i t r o p r u s s i d e , a p p l i c a t i o n of, t o S t o i c h i o m e t r y , e a r l y s t u d i e s of, 1 1 7 — 1 2 6
detection of cysteine, 30 Stromeyer, discovery of iodine—starch
—, —, t o d e t e c t i o n o f k e t o n e s , 1 7 reaction by, 1 4 8
S o d i u m s u c c i n a t e , a p p l i c a t i o n of, t o s e p a - S u c c i n i c a c i d , a p p l i c a t i o n of, in d e t e c t i o n
ration of iron from manganese, 1 5 4 of halogens, 7
S o d i u m s u l p h a t e , e a r l y a n a l y s e s of, 1 1 3 —, —, i n d e t e c t i o n o f s u l p h o n i c a c i d s , 2 6
S o d i u m sulphide, titrimetric determina- S u g a r , e x t r a c t i o n of, f r o m s u g a r b e e t , 9 2
tion of metal ions with, 1 8 2 —, h i s t o r i c m e t h o d f o r d e t e c t i o n of, w i t h
S o d i u m thiosulphate, historical a t t e m p t s c o p p e r salt, 1 8 1
to standardize, 1 9 1 —, m i c r o s c o p i c e x a m i n a t i o n of, 9 5
Solubility product, introduction of con- S u g a r s , d e t e c t i o n of, 1 4
c e p t of, b y O s t w a l d , 2 4 8 —, r e d u c i n g , first t i t r i m e t r i c d e t e r m i n a -
Solutions, analysis of a q u e o u s , 7 8 — 8 1 t i o n of, b y h e x a c y a n o f e r r a t e ( I I I ) , 1 9 3
S o m o g y i , c o n t r i b u t i o n of, t o c o u l o m e t r i c S u l p h a n i l i c a c i d , s e l e c t i v e d e t e c t i o n of,
anlaysis, 2 1 7 37
S^rensen, c o n t r i b u t i o n s of, t o a p p l i c a t i o n S u l p h a t e , h i s t o r i c a l d e t e r m i n a t i o n of, 1 7 2
of pH theory, 2 5 0 S u l p h o c h r o m i c a c i d , a p p l i c a t i o n of, i n
—, i n t r o d u c t i o n o f p H f u n c t i o n b y , 1 9 6 test for halogens, 6, 7
300
S u l p h o n i c a c i d s , d e t e c t i o n of, 2 6 , 4 8 T h a l l i u m ( I I I ) a c e t a t e , a p p l i c a t i o n of, to
S u l p h o x i d e s , d e t e c t i o n of, 2 6 detection of organic substances, 1 0
S u l p h u r , a p p l i c a t i o n of, t o d e t e c t i o n o f " T h e A n a l y s t " , f o u n d i n g of, 1 5 3
h y d r o g e n in organic s u b s t a n c e s , 6 Thénard, determination of nitrogen by,
—, d e t e c t i o n of, i n o r g a n i c s u b s t a n c e s , 8 in organic s u b s t a n c e s , 2 0 7
—, —, —, b y Z e i s e — V o h l m e t h o d , 2 1 3 —, e a r l y a t t e m p t s t o a n a l y s e o r g a n i c c o m -
—, e a r l y p u r i t y t e s t i n g o f , 1 4 4 pounds b y , 2 0 2
—, h i s t o r i c a l m e t h o d s f o r d e t e r m i n a t i o n T h e r m a l a n a l y s i s , d e v e l o p m e n t of, 1 6 0
of, i n o r g a n i c s u b s t a n c e s , 2 1 0 T h e r m o b a l a n c e , c o n s t r u c t i o n o f first, 1 6 0
—, m i c r o d e t e r m i n a t i o n o f , i n o r g a n i c s u b - T h e r m o g r a v i m e t r y , d e v e l o p m e n t o f prin-
stances, 2 1 3 c i p l e s of, 1 6 1
S u l p h u r c o m p o u n d s , d e t e c t i o n of, 2 5 — 2 6 T h i o b a r b i t u r i c a c i d , a p p l i c a t i o n of, t o
S u l p h u r d i o x i d e , d i s c o v e r y of, 1 0 3 d e t e c t i o n o f nitriles, 4 8
S u l p h u r i c a c i d , d i s c o v e r e r of, 6 8 —, —, t o d e t e c t i o n o f o x a m i d e , 3 4
S u n , e a r l y r e s e a r c h i n s p e c t r u m of, 2 2 3 T h i o c y a n a t e s , alkali, a p p l i c a t i o n t o precip-
Svanberg, application of ammonium itation titrations, 1 9 3
molybdate by, 149 —, a p p l i c a t i o n of, t o h i s t o r i c a l d e t e r m i n a -
Synesios, description of the hydrometer tion of iron, 2 3 0
by , 6 8 - 6 9 T h i o k e t o n e s , d e t e c t i o n of, 2 5 , 4 8
S y n g e , c o n t r i b u t i o n s of, t o partition T h i o l s , d e t e c t i o n of, 2 5 , 4 8
chromatography, 260 T h i o Michler's k e t o n e , a p p l i c a t i o n of, t o
S z e b e l l é d y , c o n t r i b u t i o n s of, t o c o u l o m - detection of ethers, 19
etry, 2 1 7 —, —, t o d e t e c t i o n o f h a l o g e n s , 6
T h i o p h e n , d e t e c t i o n of, 3 6
Tachenius, examination of soaps by, 8 0 T h i o s u l p h a t e , first r e c o m m e n d a t i o n f o r
Tantalum, d e t e c t i o n of traces of tin in, titrimetric use, 1 7 9
using b l o w p i p e , 9 2 T h o m p s o n , H . S . J . , c o n t r i b u t i o n of, t o i o n
—, d i s c o v e r y of, 1 3 4 exchange, 260
T a r t a r i c a c i d , a p p l i c a t i o n of, t o e a r l y T i n , d e t e c t i o n o f t r a c e s of, in t a n t a l u m ,
separations of potassium and sodium, using the b l o w p i p e , 9 2
95 —, e a r l y h i s t o r i c a l t e s t s f o r p u r i t y of, 6 5
—, d e t e c t i o n of, 3 6 —, e a r l y i o d o m e t r i c d e t e r m i n a t i o n of,
T e m p e r a t u r e c o r r e c t i o n s , first a p p l i c a t i o n 178
of, in t i t r i m e t r y , 1 7 7 T i n o x i d e s , e a r l y a n a l y s i s of, 1 2 3
T e r M e u l e n , c o n t r i b u t i o n s of, t o o r g a n i c T i t a n i u m d i o x i d e , first d e t e r m i n a t i o n o f ,
elemental analysis, 2 1 1 b y Pisani, 1 9 1
T e t r a b a s e , a p p l i c a t i o n of, t o d e t e c t i o n o f T i t r a t i o n , d e v e l o p m e n t o f t h e o r y of, 2 5 1
nitro c o m p o u n d s , 2 3 Titration curves, theory of p o t e n t i o -
T e t r a b a s e p a p e r , a p p l i c a t i o n of, i n d e t e c - metric, 2 5 3
tion of oxidizing substances, 5 T i t r a t i o n e r r o r , B j e r r u m ' s t h e o r y of, 2 5 3
T e t r a b a s e r e a g e n t , a p p l i c a t i o n of, to T i t r i m e t r y , a p p l i c a t i o n of, t o d e t e r m i n a -
d e t e c t i o n o f i o d i n e in organic s u b - tion of water hardness, 1 8 0
stances, 8 —, c o n t r i b u t i o n o f C h a r p e n t i e r t o , 1 9 3
Tetrachloro-p-benzoquinone, application —, c o n t r i b u t i o n s o f D e s c r o i z i l l e s t o , 1 7 1 —
of, t o d e t e c t i o n o f n a p h t h a l e n e , 3 4 172
—, —, t o d e t e c t i o n o f u r e a , 3 6 — 3 7 —, c o n t r i b u t i o n s o f G e n t e l e t o , 1 9 3
T e x t b o o k s , early analytical, 1 4 4 — 1 4 6 —, c o n t r i b u t i o n s o f K n o p t o , 1 9 7
301
—, contributions of Liebig t o , 1 8 2 , 1 9 4 p - T o l u e n e s u l p h o c h l o r a m i d e , see: " C h l o r -
—, contributions of Mohr to, 184—190 amine T"
—, contributions of Pelouze to, 182 T o u c h s t o n e t e s t , a p p l i c a t i o n of, t o d e t e c -
—, contributions of Schwarz to, 184 tion of counterfeit coins, 64
—, contributions of Schwarzenbach to, —, i m p r o v e m e n t i n , f o r t e s t i n g g o l d , 7 1
199-200 Tracer m e t h o d s o f analysis, 2 5 6
—, c o n t r i b u t i o n s o f U r e t o , 1 8 2 — 1 8 3 T r e a d w e l l , c o n t r i b u t i o n of, t o p o t e n t i o -
—, d e t e r m i n a t i o n o f i o d i n e n u m b e r s b y , metric titrimetry, 2 3 9
193 T r i c h l o r o a c e t i c a c i d , d e t e c t i o n of, 2 8
—, d e t e r m i n a t i o n o f o x y g e n c o n s u m p t i o n T r i h y d r o x y b e n z e n e s , i d e n t i f i c a t i o n of, 4 0
of water by, 191 T r i p l e b o n d s , d e t e c t i o n of, i n o r g a n i c s u b -
—, d e v e l o p m e n t o f b u r e t t e s , 1 8 4 stances, 11
—, d e v e l o p m e n t o f c o m p l e x o m e t r i c , 1 9 4 T r o p e o l i n , r e c o m m e n d a t i o n of, as titri-
—, d e v e l o p m e n t o f i n d i c a t o r s f o r , 1 9 4 — metric indicator, 1 9 5
198 T s v e t t , M i h a i l , c o n t r i b u t i o n s of, t o c h r o -
—, e a r l i e s t a p p l i c a t i o n s of, 1 6 5 — 1 6 8 matography, 257—258
—, e a r l y u s e o f r e a c t i o n e q u a t i o n s i n , b y T u n g s t e n , d i s c o v e r y of, 1 0 5
Mohr, 185 Tyrosine, characteristic test for, 3 6
—, first a p p l i c a t i o n o f b a c k - t i t r a t i o n i n ,
172 Ultramicroanalysis, 164—165
—, first a p p l i c a t i o n o f i o d i n e i n , 1 7 8 U r a n i u m , d i s c o v e r y of, 1 2 9
—, first a p p l i c a t i o n o f p o t a s s i u m i o d a t e Uranium solution, application by Pelouze
in, 1 8 1 of, i n t i t r i m e t r y o f p h o s p h o r i c a c i d ,
—, first a p p l i c a t i o n o f r e d o x i n d i c a t o r s 182
in, 177 U r e , A n d r e w , c o n t r i b u t i o n s of, t o t i t r i m -
—, first a p p l i c a t i o n o f s t a n d a r d s o l u t i o n s etry, 1 8 2 — 1 8 3
in, 1 8 2 U r e a , a p p l i c a t i o n of, t o d e t e c t i o n o f
—, first a p p l i c a t i o n o f t e m p e r a t u r e c o r r e c - malonic acid, 3 3
tions in, 1 7 7 —, d e t e c t i o n of, 3 6 — 3 7 , 5 4
—, first d e t e r m i n a t i o n o f a l k a l o i d s b y , U r e a s e , a p p l i c a t i o n of, t o d e t e c t i o n o f
181 urea, 3 6
—, first d e t e r m i n a t i o n o f a m m o n i a b y , Uric acid, Mohr's permanganatometric
181 t i t r a t i o n of, 1 8 9
—, i n n o n - a q u e o u s m e d i a , 2 0 0 —, t e s t f o r , 4
—, i n t r o d u c t i o n o f p e r m a n g a n a t e t o , 1 7 9
—, i n t r o d u c t i o n o f p o t a s s i u m b r o m a t e t o , V a n a d a t e , i o d o m e t r i c d e t e r m i n a t i o n of,
198 by Bunsen, 179
—, i n t r o d u c t i o n o f t h i o s u l p h a t e t o , 1 7 9 o - V a n a d i c a c i d , a p p l i c a t i o n of, t o d e t e c -
—, m i c r o b u r e t t e s f o r , 2 0 0 tion of alcohols, 12
—, M o h r ' s p r e p a r a t i o n o f p e r m a n g a n a t e Vanadium, catalytic determination of,
for, 1 8 9 163
—, " m u l t i f o r m " i n d c a t o r s i n , 1 9 8 —, titrimetric determination of, by
—, u s e o f n o r m a l s o l u t i o n s i n , 1 8 8 Czudnovicz, 191
T o b a c c o a s h , h i s t o r i c a l d e t e r m i n a t i o n of, V a n a d i u m o x i n a t e , a p p l i c a t i o n of, t o
172 detection of alcohols, 4 3
o - T o l i d i n e , a p p l i c a t i o n of, t o d e t e c t i o n o f V a n a d i u m p e n t o x i d e , a p p l i c a t i o n of, i n
pyridine, 35 elemental anlaysis, 9
Tollens test, 16 V a n H e l m o n t , discovery o f gases b y , 7 8
302
Varrentrapp, d e t e r m i n a t i o n o f nitrogen in Wenzel, account of analyses by, 1 1 3
organic c o m p o u n d s b y , 2 0 9 Wines, determination of lead in, b y hy-
V i e r o r d t , c o n t r i b u t i o n s of, t o p h o t o m - drogen sulphide, 147
etry, 2 3 4 Winkler, Lajos, c o n t r i b u t i o n s t o gravim-
V i o l e t e x t r a c t , as t i t r i m e t r i c i n d i c a t o r , etry b y , 1 5 9 — 1 6 0
167,194 —, d e t e r m i n a t i o n o f d i s s o l v e d o x y g e n i n
V i o l u r i c a c i d , f o r m a t i o n of, d u r i n g t e s t water by, 1 9 3
for barbituric acid, 2 9 W i n t e r l , c o n t r i b u t i o n s of, t o gas a n a l y s i s ,
Vitruvius, determination of purity of 105
water by, 65 —, m e t h o d p r o p o s e d b y , f o r d e t e r m i n a -
V o l h a r d , J a c o b , l i f e of, 1 9 3 tion of phlogiston, 8 9
Volhard—Wolff m e t h o d , for permangana- W r o u g h t i r o n , e a r l y a n a l y s i s of, 1 1 1
t o m e t r y determination of manganese,
199 Xanthates, detection of alchols by con-
Volumetric equipment, mid-nineteenth version t o , 12
century prices for, 1 9 0 X-Ray fluorescence analysis, development
V o l u m e t r i c f l a s k , first d e s c r i p t i o n of, of, 2 2 9
172
Vorlànder, contributions to non-aqueous Zeise, c o n t r i b u t i o n s of, t o d e t e r m i n a t i o n
titrimetry of, 2 0 0 o f sulphur in organic c o m p o u n d s , 2 1 0
Votocek, recommendation of sodium "Zeitschrift fur A n a l y t i s c h e Chemie",
n i t r o p r u s s i a t e as t i t r i m e t r i c i n d i c a t o r f o u n d i n g of, 1 5 3
by,194 Zeolites, recognition of ion exchange
p r o p e r t i e s of, 2 6 1
Walsh, c o n t r i b u t i o n s of, t o A A S , 2 2 9 Zero potential, introduction of titration
Water, d e t e r m i n a t i o n of arsenic in, b y to, 239
Boyle, 84 Z i m m e r m a n n , c o n t r i b u t i o n s of, t o p e r -
—, d e t e r m i n a t i o n o f d i s s o l v e d o x y g e n i n , manganatometry, 190
b y Winkler, 1 9 3 Z i m m e r m a n r e a c t i o n , a p p l i c a t i o n of, t o
—, d e t e r m i n a t i o n o f h a r d n e s s of, b y detection of benzyl groups, 10
Wartha and Pfeiffer, 1 9 8 Z i n c , d i s c o v e r y of, 6 8
—, —, e a r l i e s t m e t h o d s of, 1 6 7 —, gravimetric determination of, as
—, d e t e r m i n a t i o n o f o x y g e n c o n s u m p t i o n described by Fresenius, 1 5 6
of, b y F o r c h h a m m e r , S c h r ô t t e r a n d —, h i s t o r i c a l d e t e r m i n a t i o n of, b y e l e c t r o -
Schulze, 191 gravimetry, 2 1 6
—, e a r l y a n a l y s i s o f , 7 9 — 8 0 Z i n c o x i n a t e , a p p l i c a t i o n of, i n d e t e r m i -
—, e a r l y h i s t o r i c a l t e s t s o f p u r i t y of, 6 5 nation o f acid or basic character, 5
—, f o r m a t i o n of, b y C a v e n d i s h , 1 0 0 Z i r c o n i u m , d i s c o v e r y of, 1 2 9
Water analysis, Bergman's c o n t r i b u t i o n s Z i r c o n i u m a l i z a r i n a t e , a p p l i c a t i o n of, t o
to, 1 0 7 - 1 0 8 d e t e c t i o n o f fluoride in organic sub-
—, K l a p r o t h ' s c o n t r i b u t i o n s t o , 1 3 2 stances, 7
Water hardness, d e t e r m i n a t i o n of, b y Z o i s i t e , e a r l y a n a l y s i s of, 1 3 0
Clark, 1 8 0 Z o s i m o s , a l c h e m i c a l d o c u m e n t s of, 6 6
—, d e t e r m i n a t i o n of, b y S c h w a r z e n b a c h ,
199
303

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ELSEVIER SCIENTIFIC PUBLISHING COMPANY

335 JAN VAN GALENSTRAAT

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D.W. Wilson, M.SC., F.R.I.C.

L. Ben-Dor, Department of Inorganic and Analytical Chemistry, The Hebrew

E. Jungreis, Department of Inorganic and Analytical Chemistry, The Hebrew

A . R o b i n s o n , T h e Queen's University, Belfast, N . Ireland

F. Szabadvâry, Museum for Science and Technology, Budapest, Hungary

G. SVEHLA, PH.D., D . S C , F.R.I.C.

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Organic Spot Test Analysis

ELSEVIER SCIENTIFIC PUBLISHING COMPANY

COMPREHENSIVE ANALYTICAL CHEMISTRY

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Vol. IIC Paper and Thin-Layer Chromatography

Vol.IID Coulometric Analysis

Vol. Ill Elemental Analysis with Minute Samples

Vol. V Emission Spectroscopy

Vol. VI Analytical Infrared Spectroscopy

Vol. VII Thermal Methods in Analytical Chemistry

Vol. VIII Enzyme Electrodes in Analytical Chemistry

Vol. IX Ultraviolet Photoelectron and Photoion Spectroscopy

Vol. X Organic Spot Test Analysis

Vol. XI The Application of Mathematical Statistics in

In Comprehensive Analytical Chemistry, the aim is to provide a

It is hoped to include the widest selection of analytical topics that

Volume X contains two chapters. The first, on organic spot test

Dr. C.L. Graham of the University of Birmingham, England, assis-

January, 1980 G. Svehla

Organic spot test analysis

Dedicated to the loving memory of our teacher, Fritz Feigl

Spot tests are defined as an analytical technique which enables the

References pp. 54—60 1

The preliminary test contributes to the identification of organic

(A) SENSORY TESTS (COLOR A N D ODOR)

(B) BEHAVIOR ON IGNITION

The burning test of organic compounds is based on the fact that

References pp. 54—60 3

By pyrolysis is meant the rapid external heating of the substance

The consumption and production of protons in an organic com-

* Instead of t h e e x t r e m e l y t o x i c p o t a s s i u m c y a n i d e , a n y strong base can be used

There is a great variety of reducing organic compounds including

References pp. 54—60 5

Element Reagent Reaction mechanism Procedure and Refs. Ref. of Remarks

c Solid molyb- t C ] + 4 M0O3 -> C 0 2 + 2 M o 2 0 Ashing with 25 26 Avoid presence of

Halogens Succinic or R X + [ H 20 ] - > R O H + H X Pyrohydrolysis 34

Br Sulfochromic — X — > X 2T B r o m i n e is s e l e c - 39 A v o i d large

S Solid calcium C a C 20 4 + [ S ] -> C a O + C O S COS o n hydrolysis 44 45,46,49

The detection of the non-metallic and metallic elements in organic

3. Detection of functional groups

One of the most important targets of qualitative organic analysis

(A) AROMATIC COMPOUNDS