Electrolysis and Electrosynthesis of Organic Compounds

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U U
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ELECTROLYSIS
AND
ELECTROSYNTHESIS
OF
ORGANIC COMPOUNDS.
BY
DR.
WALTHER
LOB,
Privatdocent in the University of Bonn.
AUTHORIZED TRANSLATION FROM THE AUTHOR'S ENLARGED AND REVISED EDITION

BY
H. W.
F.
LORENZ,
A.M., Ph.D.,
Graduate of the University of Berlin.
FIRST EDITION.
NEW YORK JOHN WILEY & SONS. LONDON CHAPMAN & HALL, LIMITED.
: :
1898.
Copyright,
1898,
BY
H.
W.
F.
LORENZ.
ROBERT DRUMMOND, rRINTER. NEW YORK.
AUTHOR'S PREFACE TO THE AMERICAN

EDITION.
IN the two and a half years that have passed since

the
appearance of the
first
edition
of the
present
work, the application of the electric current in organic
chemistry has undergone such a marked development

that the
book
in
its
original
form could no longer
claim to give an adequate idea of our present knowl-
edge of
organic
electrolysis
and
electrosynthesis.
During these last two years in particular a series of

important researches which systematically invade this
new
field of
chemistry have been brought out in rapid
succession.
Since
am now engaged
edition, the
in
the preparation of a
new German
desire of Dr.
H. W. F.
Lorenz to translate the book affords an excellent

opportunity for presenting the revised and completed
edition directly to his fellow countrymen.
I
that his excellent translation
may
also tend to
hope draw
the attention of his American colleagues to this broad
IV
AUTHOR'S PREFACE TO AMERICAN EDITION.

field,
and interesting
and that
electricity, possessing
such a diversity of applications,

recognized
position
in
may soon
chemistry.
obtain a
organic
In
the
realization of this
hope the author and

Dr.
translator see
a rich reward for their efforts.
WALTHER
LOB.
BONN, June,
1898.
TRANSLATOR'S PREFACE.
IN presenting
permission
of
this excellent
little
work, with the

English-reading
the author,
to
the
public, scarcely anything remains to
be added to what
Dr. Lob has
already said in his prefaces to the
German
and American editions.

script
He
has read
the manu-
and made the necessary changes and additions so as to have it correspond to the second German
edition which
is
about to appear. The translator has adhered as closely as possible to He has made some additions and the original text.
added
a table of contents
will
he thinks
and a complete index, which enhance the value of the book.
To
Dr. B. B. Boltwood of the Sheffield Scientific

University,
School of Yale
who has had

and
the kind-
ness to revise the manuscript, grateful acknowledg-
ments
are
due
for
his
painstaking
valuable
services.
SPRINGFIELD, OHIO,
November,
1898.
AUTHOR'S
PREFACE TO
THE FIRST
GERMAN
EDITION.
THE
object of electrochemistry
is,
among
others,
that of performing, with the aid of the electric current, reactions which have
up
to the present been carried

of energy.
out by the employment of other forms

Its
very nature suggests the possibility of solving
synthetical and analytical problems which have as yet
remained unanswered.
In this respect
its
province
is
both that of inorganic and organic chemistry. Experiments have recently been made for utilizing electricity
in
the latter.
Few
only of the
many
tasks presenting
themselves have been undertaken.
This book aims
to give, as briefly as possible, a review of
what has
already been accomplished, and at the same time to

create an interest in the performance of experiments
on the electrolysis and electrosynthesis of organic
compounds.
AACHEN,
Electrotechnical Laboratory of the Polytechnic Institute.
November.
1895.
vi
CONTENTS.
INTRODUCTION
I.
xi
ELECTROLYSIS AND ELECTROSYNTHESIS OF ALIPHATIC COMPOUNDS.

i.
(a)
Hydroxyl Compounds.
Propyl alcohol Ethyl alcohol Butyl Methyl alcohol alcohol (lodoform, Chloroform, Brornoform). [Aristol,
Nosophene.]
Glycol
Glyceric aldehyde Chloral hydrate Mannite Cane Hexatomic alcohols Grape sugar
1-6
Glycerine
sugar
Dextrine
Gum
(b)
arable
Collodion
Starch
6-10
Ketones.
Acetone
tone
Chlor-acetones
Acetyl-acetone
Brom-acetones
Isonitroso-ace10-1 1
(c}
Acids.
Formic
acid
Formyl chloride
Formamide
Acetic
etc.
acid
Rohland's experiments: capronic, caprylic and heptylk acids, undeChlorcylenic and oleic acids Acetic acid, continued
Kolbe's experiments, Kekule's theory,
acetic acids
Propionic acid conclusions

acid
1 1-20 Cyan-acetic acid Thio-acetic acid Butyric acid; isobutyric acid, Hamonet's
Valeric
acid
Capronic
acid
acid
Oxalic acid
Malonic acid
Succinic
CEnanthylic 20-24 Glutaric acid
Pyrotartaric acid Itaconic acid Citraconic acid Mesaconic acid Malic acid Tartaric acid Bourgoin's deductions
KSkule; maleic, brom-malelc and fumaric acids.. 25-31
VUl
CONTENTS.
EXPERIMENTS OF MILLER AND HOFER.
(1)
Glycolic acid
Ordinary lactic acid Sarco-lactic acid a-Oxy-butyric acid a-Oxy-isobutyric acid Tartaric acid Hydracrylic acid /S-Oxy-butyric acid PhenyU/3-lactic acid Methyl-glycolic acid Mandelic acid Glyceric acid Malic acid Racemic acid Phenyl-glyceric acid
Ethyl-tartaric acid
:
(2)
Electrosy ntheses
Butyric ethyl ester
31-33 Succinic ethyl ester
Capronic and isobutyl-acetic ethyl esters Ethyl alcohol Ethyl esters of propionic, butyric, and valeric acids
Ethyl-succinic ester.
[<r-Methyl-hydrocinnamic ester,
34~35
Iso-
Dibenzyl-succinic ester.]
Monobasic oxy-acids. [Mandelic acid Hydrobenzoin, hydrobenzoin.] Formation of aldehydes

Oxy-acids
/7-Iodo-propionic acid
35~36
37
Nitro-ethane
ELECTROSYNTHESES OF BROWN AND WALKER.

Formation of di-esters of dibasic acids.
Adipic
acid
Succinic acid
acid
Suberic acid
Sebasic
n-Dodecane-
n-Decahexane-dicarboxylic acid 37-38 Dimethyl-succinic acids Diethyl-succinic acids Tetramethyl-succinic acid Methyl-acrylic acid Ethyl-crotonic acid. [Campholytic acid Camphothetic acid Allocampholytic acid Laurolene.] 38-42 Electrolysis of ethyl-potassium malonate and fumarate 42
:
dicarboxylic acid Disubstituted acids
ELECTROSYNTHESES OF MULLIKEN AND WEEMS.

Ethane-tetracarboxylic ester
Ethane-hexacarboxylic ester
Diacetyl-succinic ester Dimethylester ethane-tetracarboxylic Diethyl-ethane-tetracar-
Tetracetyl-ethane
boxylic ester
Electrolysis of
Diacetyl-succinic ester
42-43
Acid amides
2.
43~44
Cyanogen Compounds.
Cyanogen
Hydrocyanic acid, electrolysis and electrosynthesis of Potassium cyanide Potassium ferrocyanide Potassium ferricyanide- Sodio-nitro-prusside Prussian
,
blue
44-46 [Aro46-47
Reduction of nitriles Aceto-nitrile n-Propio-nitrile. matic nitriles Benzo-nitrile Benzyl-cyanide.]
OF THK
UNIVERSITY
x
3.
Compounds Containing
acid
Sulphur.
-
Mercaptans
Sulpho-compounds
Sodium isethionate
Potassium-trichlorrmethyl Methyl-sulphuric Potassium-trichlor-methyl sulphonate phate Ethylsulphuric acid Potassium-isoamyl sulphate Potassium xanthate Dimethyl-dithiocarbamic acid 47~49 49 Thiophene
II.
sul-
ELECTROLYSIS AND ELECTROSYNTHESIS OF
AROMATIC COMPOUNDS.
i.
Phenols.
-51-53
Phenol
Phenyl-mercaptan
2. Aldehydes and Ketones. Benzaldehyde Michler's ketone Aceto-phenone Benzile 54~56 Anthraquinone (Nitro-aldehydes and ketones, see Nitro-Compounds.)
.
3.
Acids.
Thio-benzoic acid Benzoic acid Sulpho-benzoic acid Phthalic acid Ethyl-potassium phthalate Phenyl-acetic acid Cinnamic acid 56-58 Benzyl-malonic acid
4.
Amido-Compounds.
59-60
Aniline, electrolytic products of
INVESTIGATIONS OF GOPPELSROEDER.
Preparation of aniline black from aniline; naphthylamine violet from naphthylamine salts; alizarine from anthraquinone Toluidene Methyl-aniline Diphenylamine
60-62 Methyl-diphenylamine Naphthylamine Preparation of rosaniline, crysaniline, safranine, and p-lenkAcetanilide aniline PreparaAmido-hydroquinone tion of p-phenylene-diamine Electrolysis of benzene p-phenylene-diamine 62-63
5.
Electrolytic Reduction of Nitro-Compounds.
Nitro-benzene
o-Nitro-toluidene
uene
Nitro-phenol N it ro-benzene-sul phonic acid Dinitro-benzene o-p-Dinitro-tolm Nitro- ben zoic acid Nitro-o- toluidene
-
CONTENTS.
.
PAGE
Nitro-toluic
acid
Nitro-terephthalic
acid
Nitro-iso-
phthalic acid a,<2 3 -Nitro-naphthalene-sulphonic acid... 63-65 Reaction of Gattermann Nitro-toluenes Nitro-r-xylene Lob's experiments Aromatic nitramines Nitro-car-
boxylic
acids
Nitro-sulphonic acids
Nitro-derivatives
of the quinoline series
66-70
Nitro-
Nitro-acetophenone benzophenone m-Nitro-phenyl-p-tolylketone p-Nitraniline p-Nitro-phenol Chlor-nitro-benzene

toluene-sulphonic acid
Nitro-aldehydes
Nitro-ketones
70-72 Nitro-
Dinitro-stilbene-disulphonic acid
Dinitro-naphthalenes Nitro-leuco-bodies 72-75 Picoline Nitro-piperidines Nitroso-a-pipecoline Pyridine Nitroso-aldehyde-capellidine Quinoline Quinaldine 75~76
6.
Electrolytic Oxidation of Nitro-Compounds.
Nitroso-piperidine
tion
of
Nitro-toluene Azo-benzene, introduchydroxyl groups Toluene-sulphone-amides Saccharine p-Nitro-o-toluene-sulphone - amide Oxida tion of aromatic oxy-carboxylic acids 76-78
7.
Electrolysis of Alkaloids.
(Caffeine,
Theme)
Cotarnine
cine
Atropine Opium Morphine Codeine Cinchonine BruQuinine Strychnine

78-80
8.
Camphor and Glucosides.

80
81
Terpentine hydrochloride
Salicine
9.
Electrolysis of Blood Electrolysis of
81
10.
Albumen
81-82
II.
Electrolysis and Electrosynthesis with Alternating Currents.
Ammonium carbamate Dehydration. acid Phenol Capronic acid

LIST OF
Phenol-sulphuric 82-86
87
91
AUTHORS
INDEX
INTRODUCTION.
WHILE
the electrolysis of inorganic compounds has
already obtained a recognized position in pure and
applied science, the action of the electric current, as

a productive
means
for carrying out the synthesis or
decomposition of organic substances,

results
has not given
which are entirely
satisfactory.
is
The
reason
for this lies in the great difficulty that

in investigations
encountered
aimed
in
this direction
by the ap-
pearance of secondary, complicated processes in the

cell,
in contrast to
the gen- rally simple decomposielectric current.
tions of inorganic
compounds by the
The very
different conditions required for inorganic
and organic electrolysis give a distinctive character to In inorganic the history of these two branches.
electrolysis
one investigation follows as a continuation

it.
of those preceding
The
later investigators stand
upon
case
the shoulders of their predecessors.

is
sys-
tematic and regular development

is
the result.
The
in-
different in organic electrolysis,
Difficulties
which were seldom surmounted have caused each

xi
Xll
1NTROD UCTION.
vestigator wishing to arrive at profitable results to
attack the problem from a

tory, therefore,
is
new
standpoint.
Its his-
not that of a gradual development,

in great part incoherent, facts.
is
but consists of many,
This characteristic
ture.
plainly reflected in the litera-
Scattered in
all
possible periodicals are found
researches which, although having the
same end
in
view, frequently diverge considerably in their results.
sis
While engaged in investigations on organic electrolyand electrosynthesis, I undertook to compile the

on the subject as completely as
possible, at
literature
first
only for
it
my own
guidance.
On
the supposition
that
I
may be
of service to
some
fellow investigator
publish this
resumed
Considering the difficulty of

entire literature of this
becoming acquainted with the

field,
this publication
does not claim to possess an

I
exhaustive
completeness.
hope,
however,
that
nothing of importance has been overlooked.
While
in inorganic electrolysis chief attention is given to the
primary processes in the cell, in organic electrolysis the secondary actions claim our special interest, since the factors which are chiefly active in effecting the
synthesis or decomposition of
i.e.,
organic
are
compounds,
result
hydrogen,
oxygen,
etc.,
the
of
a In
it
primary decomposition of the organic electrolyte.

a systematic description
of
the results obtained
would therefore be better
for the
sake of clearness
not to consider the actual electrolytic processes, but
INTRODUCTION.
to
Xill
make
a division, according to the final chemical

substitution or
products, into oxidation, reduction,

addition, and condensation reactions. are confronted
eral
But here we
by the
difficulty that frequently sev-
different
processes
occur
at
the same time,
making the indicated classification difficult to accomplish.

I
regard
it
as the simplest
method
to treat
the subject in accordance with the chemical character

of the electrolytes.
ELECTROLYSIS AND ELECTROSYNTHESIS OF ALIPHATIC COMPOUNDS.
I.
(a)
Hydroxyl Compounds.
The
investigations on the behavior of the
mon-
atomic alcohols have been confined almost entirely to methyl and ethyl alcohol, both of which show complete analogy in their reactions.
In those cases where
platinum electrodes were used and similar results were

obtained both with and without porous separating
cells,
the decompositions are almost without excepprocesses.
tion oxidation
Being
in
the pure state
poor conductors, the alcohols require strong currents

for their electrolysis.
The
addition of potassium car-
bonate or dilute acid increases the conductivity of the solution, but of course influences the results.
which the primarily formed decomposition products, oxygen and hydrogen, act in the
in
The manner
simplest case,
i.e., in
aqueous solution, depends solely

of the electrolytes.
ali-
upon the chemical constitution

It is evident, therefore, that in
the electrolysis of
ELECTROLYSIS AND ELECTROS YNTffESIS
phatic hydroxyl compounds, only oxidation products

will
appear.
In
fact
hydrogen
is
evolved at the
is
negative pole, while the greater part of the oxygen
absorbed.
attempts to electrolyze alcohols were confined to the action of the electric spark from an induction apparatus on the vapor of an alcohol. By
first
The
thus treating ethyl alcohol M.

obtained, besides
Quet
and Perrot
some carbon,
a substance which ex-
ploded on being heated, the chemical nature of which Perrot found that they were unable to determine.
no water was formed

alcohol; he
in
the decomposition of the

3
was
also unable to
carbonic acid gas.
Maquenne
prove the presence of obtained a gas which

odor, and
possessed
a strong aldehydic
contained
hydrogen, ethane, ethylene, acetylene, carbon monoxide, and carbon dioxide.
The results obtained by the use of direct currents were much more satisfactory than the above. We
are
indebted to
Renard,
7
Jaillard,'
and Habermann
Almeida and Dehrain, for the most thorough ex-
periments on this subject.
alcohol
Methyl Alcohol. The results obtained with methyl can be summed up as follows: Hydrogen
being evolved, the oxidation products formed are:

1
Comp.
8
5
rend., 46, 903. Bull. soc. chim., 37, 298.
4
'
Comp.
rend., 51, 214.

7, 259.
Comp. Comp. Comp.
rend., 46, 180.

rend., 80, 105, 236. rend., 58, 203.
Monatsch. Wien,
OF A LIPHA 7^1C COMPOUNDS.

1.
In
aqueous sulphuric
acid
solution:
methyl
formate, methylal, methyl acetate, acetic acid, and
methyl-sulphuric acid, a
little
carbon dioxide and
monoxide, but no formic aldehyde. Renard considers the formation of acetic acid as
due to reciprocal action between the alcohol bon monoxide,
CH OH
3
'
+ CO = CH .COOH.
3
Jahn
thinks the formation must be traceable to the
presence of ethyl alcohol.

2.
In aqueous solution, on the addition of potas-
sium acetate (Habermann): besides carbon dioxide and carbon monoxide, methane and potassium methylcarbonate.
3.
Without a solvent, by
chiefly
itself
or with the addition
of a little alkali:
potassium carbonate; also
hydrogen,
dioxide.
oxygen,
carbon
monoxide,
and
carbon
Ethyl Alcohol.
important results
In the case of this alcohol the more
have been obtained by the investiSchonbein a and Becquerel gators above mentioned. later also carried out some investigations on the same
subject.
The
results of the researches are, in general,
that the final products formed are the following:

1
Jahn, Grundriss
d.
Elektrochemie, 1894,
p. 291.
Tommasi, Traite d'Electrochimie, 1889, p. 726. 8 Comp. rend., 81, 1002, and various other places journal Tommasi, Traite d'Electroch., 1889, p. 726.
;
in the
same
4
1.
ELECTROLYSIS AND EL EC TROS YN THESIS

In
sulphuric
acid
solution:
aldehyde,
acetic
ester,
formic
ester,
ethylidene
oxy-ethyl
ether
CH^
acid.
2.
H)
(Renard) and
ethyl-sulphuric
Almeida and Deherain
state that
in
the elecin
trolysis
of a nitric acid solution they observed,
addition to these oxidation products, carbonaceous

derivatives of
3.
ammonia
at the negative pole.

1
In hydrochloric acid solution,

8
chlor-acetic acids
occur in addition to the corresponding oxidation products (Riche

).
Habermann, on electrolyzing the

3
alcohol in alkaline solution, obtained, besides carbon

dioxide,
nel
4
an aldehyde resin (Ludersdorf and Confrom which he isolated a body closely related
In aqueous solution, on the
to cinnamic aldehyde.
addition of potassium acetate, the alcohol was split
up into ethane, potassium ethyl-carbonate, carbon Also with propyl and dioxide, and acetic ester.
butyl alcohols, to which potassium acetate had been
added, analogous results were obtained by Haber-
mann.
Exact statements regarding the strength of the In consideration of the current are in no case given.
1
Pogg. Ann.,
19, 77.
Tommasi, Trait6 d'Electrochimie,
1889, 728.
Pogg. Ann., 19, 77. Pogg. Ann., 36, 487; Phil. Mag., 18,
47.
OF ALIPHATIC COMPOUNDS.
importance of these data and the
of the electrolysis
is
fact that the result
dependent upon the density and potential of the electric current and the influence of
the dissociative power of solutions, a strong incentive
for
repeating
the
experiments,
with
the
help of
is
modern
scientific
and
technical
advancement,
offered to the investigator.
lodoform* The complete conversion of ethyl alcohol into iodoform by electrolysis in alkaline iodide
solution
is
a process
now made
2
use of in industrial
is
chemistry.
The
course of the reaction
illustrated
by the equation (K. Elbs
and Herz
CH CH OH
S 2
10!
+ H = Ci}- CO, + ;HI.

2
The
electrolysis
is
solution of 10-15 g-
performed as follows: calcined soda and 10 g. potaswater and 20

cc.
best
A
is
sium iodide
placed
in
in
100
cc.
alcohol
a porous earthenware cylinder with platinum
anode.
The
cathode, of nickel,
is
surrounded by a
strong solution of sodium hydroxide.

sis is
The
electroly-
carried out at a temperature of

I
current density at the anode of
70 C., with a amp. per 100 sq.
cm., and
is
continued for 2-4 hours.
After standing for several hours iodoform crystallizes from the solution, the current yield being 601
German
Ztschr.
Patent, 29,771.
f.
Elektroch., 4, 113.
Oettel, Elektroch. Uebungsaufg., 1897, p. 53.
O
70$.
ELECTROLYSIS AND ELECTROS YNTHESIS

Sodium
iodide remains in the mother-liquor as
the principal secondary product.
Chloroform and Bromoform are formed if the chloride or bromide of the alkalies is used (comp. Elbs
and Herz, who deny

stitution reactions
is
this*).
Analogous to these sub9
the formation of aristol? a di-thy-
mol-di-iodide, as
made by Messinger and Vortmann,

Similar to
this also
is
by the
electrolysis of
thymol with the addition of

the prea tetra-iodo-phenol-phthalein
potassium
iodide.
paration of nosophene,
(Classen and
Glycol.
Lob
).
Of diatomic alcohols only glycol seems to have been the subject of investigation. Renard
6
observed
in
the electrolysis of a sulphuric acid solu-
tion of glycol, besides the formation of hydrogen,
carbon monoxide, carbon dioxide, and oxygen, that

trioxy-methylene, glycolic acid, formic acid, and a
substance isomeric with glucose were present in the

solution.
Ethylene Glycol under similar conditions gives the
same products (Renard ). Renard "also investigated the behavior Glycerine.

Zeitschr. Elektroch., 4, 118.
German patent, 64405. German patent, 64405; Lum. Chem. Ber., 28, 1603.
Traite d'Electrochimie
p.
61.,
52, 226.
Ann. chim. phys.,

82, 562.
[5] 17, 303, 313;
Tommasi, 1889, Comp.
p. 730.
rend., 8l, 188; ibid.,
* Translator.
of glycerine.
In the electrolysis of a dilute sulphuric
acid solution he obtained besides the gases, hydrogen, oxygen, carbon monoxide and dioxide, trioxy-
methylene, formic acid, acetic acid, glyceric aldehyde,
and a body to whose barium compound he gave the

formula (C 3 H 3 O 4 ) 2 Ba (glyceric acid?).
Further electrolysis of glyceric aldehyde gave the

ordinary oxidation products, and, as in the case of
glycol, a substance closely related to ordinary glucose.
Bartoli
and Papasogli
repeated these experiments,
varying the material of the electrodes, and obtained

the following results:
Carbon anode and platinum cathode gave trioxymethylene, formic acid,

similar to glucose,
glyceric acid,
resin.
a substance
and a
Graphite and platinum electrodes yielded the same

products, but a larger per cent of formic acid was
formed on using the

of
latter.
The
alkaline solution
glycerine,
electrolyzed
3 by Stone and McCoy,
gave condensation products of glyceric aldehyde similar to those which have been obtained in the
synthesis of glucose.
present.
Glyceric acid also was found
Tommasi
electrolyzed a sulphuric acid solution of
chloral hydrate and
was able to prove the presence
of
hydrochloric acid.
1
On working
with isolated elec-
a Gazz. chim., 13, 287. Amer. Chem. Journ., 15, 656. Tommasi, TraitS d'Electrochimie, 1889, p. 741.
ELECTROLYSIS AND ELECTROS'YN THESIS

abundance
of chlorine
trodes, an
was given
off at the
cathode and acetic aldehyde collected at the anode.
Hexatomic Alcohols.
The decomposition phenom-
ena of hexatomic alcohols and sugars are similar to

those of glycerine.
either to carbon
part
is
completely oxidized
to
monoxide and carbon dioxide or
formic acid, while the remainder, on timely interruption of the experiment, gives lower oxidation products
which vary with the configuration of the alcohols and

sugars.
Mannite.
In the electrolyzed fluid from mannite

acid,
Renard obtained formic

alic acid,
trioxy-methylene, ox-
a sugar isomeric with glucose, and an acid,
C,H O
8
which he regarded as the aldehyde of sacHe could detect no mannonic acid. charic acid.
8
,
This sugar, investigated by Renard, on being subjected to the action of the current broke up into carbon monoxide, carbon dioxide, formic
Grape Sugar.
acid, trioxymethylene,
and saccharic
a
acid.
Cane Sugar.
Brester
found on electrolyzing cane
sugar that the solution turns strongly acid and possesses reducing properties, very little carbon dioxide
being given
off.
He was
free
not able to determine the

distilla-
nature of the substance which he isolated by

tion and which was
from formic and acetic acid.

it
On
further electrolysis
1
gave the usual

[5] 17, 289.
final
oxida-
Ann. chim. phys.,
Bull. soc. chim., 8, 23.
tion products.
9
the same
arable,
The experiments made by
author on the electrolysis of dextrine,

collodion,
gum
The
and starch gave no noteworthy general impression gained from the investigaresults.
tions of the alcohols, aldehydes,
mentioned,
is
and alcohol-aldehydes that the general reaction is one of suc-
cessive oxidation.
The
electrolytic
final
oxygen gradually
are
oxidizes the substances, the
product being carformed,
bon dioxide.
their quantity
electrolysis.
Intermediate products
depending upon the duration of the

following these
In
processes
it
is
of
especial importance whether the oxidation products
are soluble or insoluble and whether they are electrolytes or not.
The
possibility of isolating the products
which are formed depends on these properties. If the product of oxidation first formed is a good conductor of the electric current
further oxidation;
if
it
will, of course,
it
undergo
it
is
insoluble
escapes the
further action of the current.
In order, therefore, to
obtain a comprehensive idea of the decomposition of

organic
substances
it
is
necessary
immediately to
withdraw the electrolyzed fluid from the action of the Miller and Hofer current. accomplished this by
1
allowing the solution to flow slowly over the electrodes. But very few experiments of this nature have
been made.
Mannite serves as an
illustration of
such
it
an oxidation process.
1
As
already
mentioned,
Chem.
Ber., 27, 461.
10
ELECTROLYSIS AND ELECTROS YN THESIS
breaks up into formic acid, oxalic acid, a sugar, and
an acid,
lowing:
HO
8
The
reactions are probably the fol-
C.H.A - C H - C H -> CH O - C H O -> CO - CO
HM
-4
a
Whether any intermediate products have escaped

observation, and the nature of these, can naturally be
determined only by new and careful experiments. Since organic substances, apart from acids, bases,
poor conductors of electricity, the addition of a mineral acid to an organic electrolyte prosalts, are
and
duces a complication of conditions, since oxidation reactions occur in combination with substitutions.
After
it is
once made possible to establish and regu-
late the oxidizing
and reducing
effects of the current,

is
the field of substitution reactions

offers the
the one which
most promising
(b)
results.
Ketones.
electro lyzed
Acetone.
1
Acetone has been

Friedel.
1
by Mulan
der,
Riche,* and
The
electrolysis of
acetone solution acidified with sulphuric acid
gave
In
di-
carbon dioxide, acetic acid, and formic acid.

hydrocloric acid solution mono-chlor-acetone
chlor-acetone could be isolated; in
1
and
hydrobromic acid
Jahresber.
f.
Chemie,
1859, p. 339.
1 *
Comp. rend., 49, 176. Ann. Chem. Phar., 112,
376.
solution mono-brom-acetone.
action
of
II
Wilde
'
investigated the
the
electric
spark on
acetone vapor in
Acetylene was formed in the gas mixture and carbon was deposited on the sides of * the vessel. According to Maquenne acetone vapor
Torricelli's
vacuum.
decomposed by the electric discharge into hydrogen, ethane, and carbon monoxide, a small quantity
is
and carbon dioxide being formed. On the other hand, Hemptinne* syntheticized both aceof acetylene
tone and aldehyde by passing a silent electric dis-
charge through a mixture of carbon monoxide and

ethane, the gases being kept cool by the use of a
freezing mixture.
Isonitroso-acetone.
Ahrens and Meissner

electrolytically
tried to
reduce
acetone.
this
compound
to
amido-
They, however,
obtained
dimethyl-pyra-
zine, ketine,
C,H
N,, in small quantity.

alcoholic
Acetyl-acetone in an on solution electrolysis gave tetracetyl-^.

Acetyl-acetone.
THH
Acids.
UNIVERSITY
The
investigation of acids has beefr^much-^nlore
extensive than that of those classes of bodies which
have been thus

1
far discussed.
The
conditions here
Bull. soc. chim., [2] 5, 267. Bull. soc. chim., 39, 306; ibid. 40, 60. Bull. Acad. roy. Beige, [3] 34, 269.
t
4
6
Chem.
Ber., 30, 532.

d. Cheoiie, p.
Ahrens, Handb.
482 (1896).
12
ELECTROLYSIS AND ELE CTROS YN THESIS
are
much
simpler,
since the acids are mostly
conductors of electricity,
both
in
solution
good and in
salts.
the free condition, as well as in the form of
Kolbe's
'
classical investigations
on the electrolysis of
organic compounds,
in
which he demonstrated the
formation of the hydrocarbons from the acids, are the
foundation of later investigations.

3
4
continuation
a along the same line are the researches of Kekule,
Brown and Walker, Mulliken, and Weems. They the electric as a current valuable means for employed
effecting the synthesis of a complete series of
com-
pounds.
For the sake of clearness the researches here given will be arranged chiefly in accordance with their
chemical characteristics.
Although up to this point, in the investigations mentioned, it has been necessary to consider chiefly oxidizing reactions,
field
Formic Acid.
we now
enter
upon a
of a
comprising those reactions which
involve the
process of reduction, and in which

relatively high
compounds
of formic
6
stage of oxidation are
the startingacid
points.
The
electrolytic
formation
from oxalic acid, as observed by Royer,

tion reaction of this nature.
1
is
a reduc-
8 4
6
Lieb. Ann., 69, 257. Lieb. Ann., 131, 79. Lieb. Ann., 261, 107.
Amer. Chem. Journ., Amer. Chem. Journ., Comp. rend., 70, 731;
15, 523.
16, 569.
Bull. soc. chim., [2] 14, 226.
OF A L IPHA TIC COMPO UND S.

Wilde
1
found that the action of the
electric spark
on gaseous mixtures of oxygen and alcohol, hydrogen and carbon dioxide, methane and carbon dioxide pro-
duced formic
acid.
Losanitsch and Jovitschitsch
obtained formic acid by treating carbon monoxide or

dioxide and water in Berthelot's ozone apparatus.
The behavior of the acid itself as well as its salts has been made the subject of thorough investigation carried out chiefly
3
by
Brester,
8
Renard* and Bourgoin,
Bartoli
and Papasogli.
The
by
progress of the decomposition
is
accompanied
the evolution of carbon dioxide and oxygen at the
positive pole
and hydrogen
The
quantitative relations of the decomposition products
vary with the concentration of the solution and the

density of the current.
The
reactions occur accord-
ing to the following equations:
HCOOH = HCOO + H, HCOO + HCOO = H + 2CO 2HCOO + H O = 2HCOOH + O.

a
a,
It is therefore theoretically
impossible to effect the
complete decomposition of the formic acid present. In the electrolysis of sodium formate, carbon dioxide
Bull. soc. chim., [2] 5, 267.
Ber., 30, 135. Zeitsohr. f. Chemie, 1866, p. 60.
Chem.
Ann. chim. phys., Ann. chim. phys.,
[5] 17, 289.
[4] 14, 157. 88.
Gazz. chim., 13, 22 and
14

in fact
and formic acid are

tive pole
always formed at the posiat the

is
and hydrogen and sodium hydroxide
negative pole.
The
discussion of the other salts

is
unnecessary since their behavior
quite analogous.
(?) has been obtained by Losanitsch and Jovitschitsch from a mixture of carbon monoxide and hydrochloric acid by the action of the electric discharge, and by a like method formamide has been
For my I Chloride
prepared from carbon monoxide and ammonia.

Acetic Acid.
sis
Acetic acid
is
formed
in the electroly-
of methyl
is
spark
and ethyl alcohol when the electric passed through a mixture of alcohol vapor
and oxygen, or methane and carbon dioxide. On the other hand acetic acid can be converted into alcohol
by
electrolytic reduction,
if
the acid
is
substituted in
place of nitric acid in the porous cup of a Bunsen
element.
Glacial acetic acid
is
a poor conductor of electricity.

a
According to Lapschin and Tichanowitsch

position
its
decom-
when
effected with the use of
elements yields at the anode, carbon
900 Bunsen monoxide and
carbon dioxide; at the cathode, carbon and a small

quantity of a gas the nature of which could not be
established.
3
Bourgoin,
on electrolyzing the dilute
ibid., 70, 731;

*
Tommasi, TraitS d'Electrochimie, Chem. Ber., 29, 1390. Neue Peters. Acad. Bull., 4, 81. Ann. chim. phys., [4], 14, 157.
724;
Comp.
rend., 69, 1374;
acid,
15
observed hydrogen at the negative pole and oxygen, carbon dioxide, and traces of carbon monoxide at the positive pole.
The
reactions involved in the decomposition of the
alkali salts are
more
interesting.
Kolbe, on decom-
posing a concentrated solution of potassium acetate, obtained a hydrocarbon in addition to other decom-
According to the idea then prevailing acetic acid underwent oxidation in the sense that it was thereby changed into carbon dioxide and
position products.
methyl, both of which appeared at the positive pole,

while at the negative pole only hydrogen was evolved,
and a part of the methyl was oxidized to methyl The hydrocarbon evolved was in fact ethane, oxide.
which always accompanies the decomposition of potassium acetate solutions, while the other decomposition products formed vary with the density of the electric
current and the temperature of the solutions.
Thus
Kolbe
identified
methyl ether and methyl acetate in

than carbon
the solution, while Bourgoin observed no decomposition
products
Jahn,
other
a
monoxide
and
dioxide.
who employed
currents of very low
electrode density, obtained
by the electrolysis of an
almost saturated solution of sodium acetate only car-
bon dioxide, ethane, and hydrogen.
The formation
Lieb. Ann., 69, 279. Grundriss d. Elektrochemie, 1895,
p. 292.
ELECTROLYSIS AND ELECTROSYNTHESIS

be explained by assuming either the
of ethane can
direct oxidation of the acetic acid,
or the decomposition of the anion,
CH COO\ _ c H 4- 2 CO U CH COO/- ^""t

3
''
Kkule advanced
l
a theory based on the phenom-
ena of decomposition, and from this deduced certain

formulae which
of
make
i*
possible to predict the nature
products resulting from the electrolysis of monobasic and dibasic acids of the fatty acid series.
the
Since, however, the reaction
is
influenced
by the
hold
slightest
variation of
in
conditions, his
formulae
good only
fectly
the case of the decomposition of perin
pure substances, a condition seldom met

a
practice.
Lob
is
in favor of
in
accepting the theory advanced
by Kekule, who
acids sought
the case of phthalic and acetic

to prove the intermediate
8
by experiment
formation of the anhydride, while Schall

formation of an acid superoxide:
assumes the
R.COO --h R.COO
= R.COO\
R.COO/
a
'
R.COO\ R.COO/
1
TJ
-m
8 3
Lieb. Ann., 131, 79. Ztschr. f. Elektrochemie, 3, 42. Ztschr. f. Elektrochemie, 3, 83.
OF A LIPHA TIC COMPO UNDS.

This conclusion
is
drawn from the observed
fact
that the dithionic acids

alkali salts give acid
upon the
electrolysis of their
supersulphides which correspond
with the superoxides:
R.CSS
-L-
R.CSS
= R.CSS\ ( UNIVERSIT
R CSS/
'
'Vû
In contrast to the acid superoxides, the acid supersulphides are stable compounds.
The
salts of
reactions and the
corresponding electrolytic
products which occur

1
in the electrolysis of the alkali
the fatty acids were thoroughly investigated
by Rohland,
who
electrolyzed
the
alkali
salts
of
capronic, caprylic, and heptylic acids.
Potassium Capronate gave normal decane, C, H M Potassium Caprylate analogously gave normal tetra;
decane,
J4
30
while
,
a small
Potassium Heptylate gave besides dodecane, C 12 H 26 quantity of an unsaturated hydrocarbon,
probably octylene,
18
The
ently.
fatty acids with ethylene
bond behave
differ-
In their case no smooth reaction occurs.
The
electrolysis of undecylenic acid, for example, yielded a
mixture of several unsaturated hydrocarbons, a result similar to that obtained in the investigation of potas-
sium
oleate,
the only outcome of which was a mixture
of various
compounds which could not be separated.

1
Ztschr.
f.
Elektrochemie,
4, 120.

Kolbe and
Kemp
obtained by the electrolysis of a
concentrated potassium acetate solution, at the anode,
hydrogen, methyl-acetic ester, methyl-formic ester, ethane, ethylene, and carbon dioxide; at the cathode,
hydrogen and potassium hydroxide. In an alkaline solution of the same salt Bourgoin' obtained a mixture of sodium formate, but so far as hydrocarbons
were concerned could only prove the presence of ethane and ethylene.
Besides the
alkali
salts,
the
copper,
lead,
man6
ganese, and uranium salts were subjected to electroly6 by Dupre, Wiedemann, Despretz, and Smith. The metals were precipitated at the anode, a portion
sis
of the
manganese and lead

7
in in
the form of superoxides.

the electrolysis
of
According to Bauer,
acetic
the
acid
salts
of
metals possessing
4
,
constant
Al),
valence (K, Na,
NH
Mg, Ca, Zn, and

and
when
cold, moderately dilute solutions
relatively high
current densities are employed, gases consisting chiefly

of ethane
and carbon dioxide are given
off
at
the
anode.
No
in
inconsiderable quantities of ethylene are
formed
the case of calcium, magnesium, and potas-
Journ. prakt. Chemie, [2] 4, 46. Ann. chim. phys., [4] 14, 157. Archiv. ph. nat., 35, 998.
4
5
Pogg. Ann., 104,
162.
6
1
Comp. Chem.
rend., 45, 449.
Ber., 13, 151. Dissert. Giessen, 1897; Wied. Beibl., 21, 601.
sium acetate solutions.
contrary result
Very small amounts on the
from the electrolysis of the sodium,

zinc salts.
ammonium, and
At the
boiling tempera-
ture the gases consist mostly of

in addition a little
oxygen and contain carbon dioxide and a very small

Metals with several valences
quantity of ethane.
change to the higher valence.

Monochlor-acetic Acid, according to Kolbe,
1
breaks
acids,
:
up on
electrolysis into hydrochloric
and acetic
as a result of the action of the electrolytic
hydrogen
CH C1.COOH
S
+ 2H = CH COOH + HC1.
8
Trichlor-acetic
in addition also,
Acid gives the same products and

according to Elbs, tri-chlor-methyl
3
.
ester,
CC1,.CO 3 .CC1
Cyan-acetic Acid.
Moore
obtained at the positive
pole carbon dioxide besides traces of nitrogen, and
hydrogen and potassium hydroxide, bodies analogous to the decomposition products of sodium acetate.
ethylene cyanide
;
at the negative pole
Thio-acetic
5
Acid."
This compound
is
gives
acetyl
formed at the positive pole disulphide. if a solution of pure acetic acid which has been satacid
The
urated with hydrogen sulphide

1
is
subjected to elec1889, p. 750.
Tommasi, Trait6 d'Electrochimie,

Journ. prakt. Chemie,
[2]
47, 1104; ibid., [2] 55, 502.
Chem.
Ber., 4, 519.
f.
4
6
Zeitschr.
Elektroch.,
3, 42.
Chem,
Ber., 3, 297.
2O
ELECTROLYSIS AND ELECTROS YNTKESIS

and a slow current of the gas
is
trolysis
conducted
through the solution during the operation.

Propionic Acid.
The
electrolysis of a concentrated
solution
1
of
sodium propionate was carried out by
Jahn
and yielded, when the density of the currents employed was not too great, hydrogen, ethylene, and
Butyric Acid.
carbon dioxide, but no butane.
The two
2
butyric
acids were
acid
it
elec-
trolyzed
by Bunge.
With
isobutyric
was
not possible to obtain hexane, but the normal acid yielded some butane besides larger quantities of
propylene.
The
sity,
great influence of concentration, current denis
and especially of temperature

in
again empha-
sized
The various of Bunge. inindividual the followed were conditions which by

the
researches
vestigators explain sufficiently the frequent differences
occurring in the results.

trolytic
The
repetition of an elec-
experiment
all
is
only possible
is
when an exact
This requirethe published
in
statement of
the factors
given.
ment
however, entirely omitted experiments above mentioned.

is,
Careful and reliable investigations on the electrolysis
of the potassium salts of butyric
and
isobutyric
3
acids have been published
by M. F. Hamonet.
His
Grund. d. Elektroch., 1895, 293. Journ. d. russ. phys. Gesellsch.,
I, 525.
Comp.
rend., 123, 252.
21
apparatus consisted of a copper beaker 23 cm. high
and
cm.
in
diameter, which served as the cathode.
A porous earthenware cell,

beaker.
which contained the anode

in the
and was closed with a three-hole stopper, stood
Through the perforations
of
the
stopper
passed a thermometer, a gas-conducting tube, and the

electric
used in
in
conductor leading to the anode. The anode some experiments was a platinum wire i mm.
in length, in others
diameter and 2 m.
a platinum
cylinder 14 cm. high and 2.5 cm. in diameter.
This
variation of current density was, however, of second-
ary importance.
Solutions of the
potassium
salts
having a specific gravity of 1.08-1.12 were used as

the electrolyte.
Current strengths of 4-5 amperes
were reached with a difference of potential at the poles of 6-8 volts. The electrolysis was continued 2-3
hours, the solution being kept cool.
results
The
following
were obtained
Potassium Butyrate,
CH
225
g.
.CH,.CH .COOK.
2
3
sponding to
1
(CH .CHBr.CH Br), correCH = CH ); 47 g. propylene (CH 8 g. isopropyl alcohol (CH,.CHOH.CH ); 4.5 g. butyric isopropyl ester (CH .CH .CH .COOCH(CH ) );
propylene bromide
2
4.5 g. complicated products, which
became resinous
alkali
when the
hydroxide.
ester
was saponified by boiling with
22

3 2 2
Hexane (CH .CH .CH .CH .CH .CH ) and propyl alcohol (CH .CH .CH OH) could not be detected.
a
2
3
They
could,
therefore,
only have been
formed
in
extremely small quantities. The very remarkable formation of isopropyl alcohol can only be explained
by assuming the hydration

ular rearrangement of the
of propylene or the molec-
group
CH
.CH,.CH
Potassium Isobutyrate,
(CH
This
salt
9) a
:CH.COOK.
propylene bromide (CH,. CHBr.CH a Br), equivalent to 62 g. propylene (CH
gave
300
g.
CH:CH );20
a
g. isopropyl alcohol ((CH 3 ) a :CHOH);
over 12
g. isobutyric isopropyl ester,
((CH,),:
CH.COOCH(CH
8) a
);
g. of
an
oil
having a pepper-like odor and boiling at
130-160.
In this case also the paraffine isohexane
(CH
),:CH.
CH :(CH
8) a
was not formed.

the
following
Hamonet draws
these results:
I.
conclusions
from
The equation
2C.H M+l .COO-= C.H 4K+2 + 2CO.,

representing the reaction in the electrolysis of the
alkali salts of the fatty acids,
which since the experi-
ments
of
2$
Kolbe has been almost universally accepted,

in
can no longer claim to represent the true fact

case, since
the
this
no or almost no paraffines
result
from
operation.
2.
The
olefine
C M H 2W sometimes predominates
among
the products formed by the electrolysis of the
alkali salts of the fatty acids,
The
general nature of the reactions

:
is
represented
by the following equation
2C,H , + .COO
1 I
C.H - + .COOH
1
+ C.H M + CO..
is
3.
if
An
of
alcohol with n carbon atoms
always formed
the acid contains (n

the
alcohol
+
is
i)
carbon atoms. always

that
The
strucis
ture
not
which
Frequently more than a third of the energy of the current is expended in the formation of
expected.
the alcohol.
Whether the
alcohol
is
generated by
the saponification of the ester present, according to

the equation
2CH
or
2B
,COO- =
it
C.H M + .COOC.H,. +1
I
+ CO,,
uncer-
whether
is
formed by the hydration of the

2
defines,
tain.
C,H
1(I
+HO=
C w H aM+1 OH,
is
still
To
decide this question a more thorough investiga-
tion of the substances resulting from the electrolysis
24
of

compounds possessing higher molecular weights
Valeric Acid.
is
required.
Kolbe
electrolyzed
the potassium
(di-
salt
and obtained as the chief product octane
isobutane),
[J'\CH.CH,.CH..CH/[:{*.
Besides this there appeared as decomposition products
water,
carbonic acid gas,
butylene,
and
the
butyl ester of valeric acid.

Brester,"
who performed
his
experiments under
different conditions, obtained at the
anode a gaseous mixture of carbon dioxide, butylene, and oxygen.

Capronic Acid.
concentrated
solution
of
the
potassium
ester
of
gave decane and traces of the amyl capronic acid, both of which are normal
salt
3
decomposition products. The electrolyses were made 4 by Brazier and Gossleth, by Wurz, and by Rohland. The normal acid was electro(Enanthylic Acid.
lyzed
similar
by Brazier and
to
Gossleth
capronic
and*
6
,
under conditions
those
for
ia
acid,
24
,
and gave two

addition
to
hydrocarbons,
26
Cn H
in
hydrogen, potassium
carbonate.
1
carbonate and acid potassium
Lieb. Ann., 69, 257.
Jahresber.
f.
Chem.,
1859, P- 86; ibid., 1866, p. 87.

6
Tommasi, Traite
4
d'Electroch., 1889, p. 757.

Ibid.
Ibid.
Oxalic Acid.
2$
The deportment
2
of the saturated solu-
tion of the free acid on electrolysis

1
was determined
3
4 by Brester, Bourgoin, Balbiano and Alessi, Bunge, The general result was that oxygen and Renard.
6
and carbon dioxide were obtained
at the
anode and
completely
this prop-
hydrogen
at the cathode.
It is possible to
oxidize oxalic acid to carbon dioxide.
On
erty depends the great importance of oxalic acid in
quantitative electrolytic analysis, into which
it
has
been introduced by Classen.
The
double
ability of
salts
ammonium
many
oxalate to form soluble
with
is
difficultly soluble or insoluble
metallic salts
of the acid
in
accord with the favorable conduct
on
electrolysis,
by which operation
in the
it
may
be entirely removed from the solution

gas.
form of
The reducing
its
effects of the current
on oxalic
acid were also observed.
Thus on
salt
electrolyzing both
the free acid and
sodium
Balbiano and Alessi

acid.
is
were able to prove the presence of glycolic
The
oxidation
in
is
not complete
cold
solution,
if
the electrolysis
conducted
the
carbon monoxide
as well as carbon dioxide being then
formed at the
positive pole.
1
Jahresber.
f.
Chemie,
1866, p. 87.
8
3
Comp.
Chem.
rend., 67, 97.

p. 190;
Gazz. chim., 1882,

Ber., 9, 78.
Chem.
Ber., 15, 2236.
4
5 8
Ann. chim. phys., [5] 17, 289. Classen, Quan. Analysis by Electrolysis (Wiley
& Sons,
N.
Y.).
26
The decomposition
reactions of oxalic acid salts are
entirely analogous to those of the free acid.

line solution the oxidation
in neutral solution
In alka-
proceeds more
rapidly than
because of the better conductivity
of the alkalies.
Malonic Acid.
1
This acid was investigated by Bour-
goin.
In a concentrated solution of sirupy consisit,
tency
like oxalic acid, is only slowly oxidized
to
carbon dioxide, with the evolution of hydrogen.

strongly concentrated solution of the unaltered acid
A
is
found surrounding the positive electrode, even after an electrolysis of long duration. On the electrolysis of the sodium salt carbon monoxide is also present in
the escaping gas mixture.
The
ratio of the different
gases, carbon dioxide, carbon
monoxide, and oxygen,
remains
sis
fairly
constant during the period of electroly-
(85.8$, 9.7*, 4.5*).
In alkaline solution the decomposition products are

the same as in neutral solution, the ratio only of the
separate gases being different, and varying with the
duration of the electrolysis.

2 Bourgoin and Kekule found that the free acid underwent oxidation with difficulty, only
Succinic Acid.
a small quantity of carbon
monoxide
in addition to
some oxygen and carbon dioxide being formed.

1
[i] 14, 157; Comp. rend., 90, 608. Bull. soc. chim., [2] 9, 301; ibid., 21, 1695. Lieb. Ann., 131, 84.
Ann. chim. phys.,
2J
as
The
in
neutral sodium salt gave the
same products,
did also the alkaline solution of this salt, except that
the latter experiment
the
formation of carbon
monoxide predominated. If, however, four molecular equivalents of sodium succinate were treated with one
equivalent of sodium hydroxide, ethylene and a
little
acetylene could also be detected.
Kolbe
states that
methyl oxide
is
also
formed
Bourgoin, however, was
unable to confirm this statement.

Glutaric Acid.
2
The
results
which
Reboul
and
Bourgoin
obtained with this acid are the following:
The
greater part of the acid remains unchanged,

is
while a small part only
decomposed according
to
the equation
C.H.O.
+ 70 = 2CO, + 3 CO + 4 H.O.
of the composition
A hydrocarbon
was not formed.

Similar observations were
made
in the electrolysis
of potassium glutarate, likewise in alkaline solution.
Pyrotartaric Acid.
The
investigators
just
men-
tioned, on electrolyzing a solution of the neutral potassium salt, observed the immediate precipitation
1
Lieb. Ann., 113, 244.
Comp.
rend., 84, 1231.
28

(Different behavior from glutaric
of the acid salt.

acid, in the case of
salt
which the formation of the acid

After a time the crystals
does not take place.)

the
free
disapppear,
acid
being regenerated.
In
alkaline solution also, the formation of the acid salt
occurs, after a longer period of electrolysis.

theless the continuous,
Never-
though limited, evolution of

is
carbon dioxide and carbon monoxide

partial oxidation.
a proof of
Itaconic Acid.
The concentrated
by Aarland
3 4
,
solution of
the
alkali salt electrolyzed
bon isomeric with

have the formula
allylene, C H CH = C = CH
2
gave a hydrocarwhich is said to
2.
Along with
this
compound, some propylene was formed, while a portion of the acid was always regenerated.
Citraconic Acid.
3
The concentrated
solution of the
sodium
salt, likewise electrolyzed
by Aarland, yielded,
besides a hydrocarbon,
small traces of acrylic
and mesaconic acid.

Mesaconic Acid, under the same
the same hydrocarbon and
itaconic acid.
conditions, gives
of
acrylic
traces
and
Malic Acid.
The
electrolysis of malic acid

4
was per-
formed by Bourgoin* and Brester.
The
free acid,
Journ. prakt. Chem., [2] 6, 256. Journ. prakt. Chem., J, 142. Bull. soc. chim., [2] 9, 427.
Jahresb.
f.
Chem.,
1866, p. 87.
which
alkali
is
2$
neutral
only slowly decomposed, and the
salt
both gave the

little
dioxide and a
same products, carbon carbon monoxide and oxygen.
After the completion of the experiment the solution

contained some aldehyde and acetic acid.
Tartaric Acid (Dextrorotary).
of the
deportment of
this
1
For our knowledge acid on electrolysis we are
also indebted to Bourgoin.
The
free acid
is
partially
oxidized to carbon dioxide and carbon

while
the
solution
monoxide,
Neutral
contains
acetic
acid.
potassium tartrate gives principally carbon dioxide besides a little carbon monoxide and oxygen, acid potassium tartrate being at the same time deposited.
In alkaline solutions the gases carry with them traces
of ethane, the formation of
which
is
due to potassium
acetate which
is
found present in the solution at the
end of the operation.

Before proceeding to a discussion of the acids
still
3
to be considered, the deductions which Bourgoin
draws from his numerous experiments

tioned briefly.
will
be men-
He
regards the intermediate formation
of the anhydride as the
most important process
in
the
electrolysis of organic acids, since
by the splitting off
of
oxygen
this
produces secondary oxidation products.

the transformation of the
He
considers, moreover,
acid anhydride into the hydrate,

1
by the addition
of
Comp.
rend., 65, 1144.

[4], 14, 157.
Annal. chim. phys.,
3O
and the oxidation of the acids by oxygen formed from the acid itself as belonging to the
water,
secondary processes. This explanation coincides with the fact that water is not an electrolyte, or at least
only a poor one, and acts chiefly as a dissociation
medium.
The
typical reactions in the electrolysis of
acetic acid are, for instance, the following:
Electrolytic decomposition,
2CH .COOK =
S
>
+ Q + K,.
Characteristic oxidation,
A too strict adherence

is
to the chemical arrangement
not conducive to clearness.

1
After mentioning the
investigations of Kekule,
the later experiments of

etc., will
Miller and Hofer,
Brown and Walker,
be
discussed in this connection.
Kekul
'
investigated the electrolysis of maleic acid

acid.
and brom-maleic
The former gave
acetylene,
besides a small quantity of succinic and fumaric acid;
the
latter,
acid and carbon monoxide.
on the contrary, gave only hydrobromic Like malic acid, fumaric
acidj at the beginning of the experiment,
gave only pure acetylene, but after the operation had continued
1
Lieb. Ann., 131, 79.
for
31
some time the acetylene was found
to be
mixed
with oxygen.
EXPERIMENTS OF MILLER AND HoFER.

I.
The
investigations carried out
by Miller and
Hofer are improvements over those previously made,

since they give a
much
clearer insight into the process
of the decomposition.
In the
method which was
employed, namely, that of allowing the solutions to

slowly flow over the electrodes, the
compounds
first
formed were removed from the region of electrolytic

action.
In this
stances
way
it
which
was possible to isolate certain subwould otherwise have undergone

In
secondary decomposition.
below,
the
researches
cited
however,
accurate
data concerning current

3
relations
are lacking.
Classen
has accurately ex-
plained what data are necessary for repeating an electrolytic
experiment.
Glycolic Acid.
The concentrated
and some formic
solution of
the
sodium
salt
yielded at the positive pole
formaldehyde
in large quantities
acid, the latter
breaking up from the action of the current into carbon
monoxide and dioxide.

1
Chem.
Ber., 27, 461.
Classen,
"
Quan. Analysis by Electrolysis," page
23.
32

Ordinary Lactic Acid.
As Kolbe
'
had already
dis-
covered, the concentrated solution of the potassium

salt
gave carbon dioxide and acetic aldehyde. The investigators above mentioned also remarked the
presence of some formic acid.
When
the solution
about the positive pole was kept slightly alkaline, aldol and crotonic aldehyde were formed instead of
acetic aldehyde.
Sarco-lactic Acid.
When
the solution surrounding
positive pole was kept neutral a concentrated solution of the sodium salt yielded acetic aldehyde
the
and carbon dioxide.

^-Oxy-butyric Acid.
This substance was converted
into carbon dioxide, propionic aldehyde,

acid.
and formic
<*-Oxy-isobutyric Acid.
This compound gave carthe electrolysis of a concen-
bon dioxide, carbon monoxide, and acetone.

Tartaric Acid.
From
trated solution of potassium tartrate, carbon dioxide,
carbon monoxide, oxygen, a
little
formic aldehyde,
and some formic acid were obtained, but no acetic

acid and ethylene, as stated
by Bourgoin.
little
Hydracrylic Acid.
Resin and a
in
formic acid
were found present

tive pole.
the electrolyte about the posi-
/?-Oxy-butyric Acid.
From
this acid
were obtained
carbon monoxide, carbon dioxide, crotonic aldehyde,

1
Lieb. Ann., 113, 214.
a
little
33
of unsatuinvesti-
formic acid, a resin, and a
number
rated hydrocarbons which were not further
gated.
Phenyl-/?-lactic Acid.
sis
The
solution after electroly-
contained benzaldehyde, besides resinous bodies.

Methyl-glycolic Acid.
The
solution
of
this
acid
after electrolysis contained formic

acid,
aldehyde, formic
and possibly methyl alcohol. Oxygen, carbon monoxide, and carbon dioxide were evolved.
Mandelic Acid.
The
electrolysis of
this acid
re-
sulted
in
the
formation
of
benzaldehyde and the
gases mentioned above.
Like mandelic acid, glyceric acid was decomposed into carbon monoxide, carbon dioxide, and oxygen, formic aldehyde and formic acid
Glyceric Acid.
being found in the solution.

Phenyl-glyceric Acid.
The products
resulting from
the electrolysis of this acid were the same as those
obtained from mandelic acid.

Malic Acid.
ide,
This compound yielded carbon diox-
oxygen, carbon monoxide, acetic aldehyde, and
crotonic aldehyde.
Racemic Acid.
On
the electrolysis of this acid the
gases given above were obtained and also an aldehyde
which was not further investigated. This gave the same gases, but Ethyl-tartaric Acid. which other may have been formed were gases any
not identified.
34
2.

Electrosyntheses.
1
The same
investigators
this subject
re-
cently
added
to our
knowledge on
solutions
by
submitting to electrolysis
containing the
potassium
salts
of
mono-basic acids and the ethyl

salts of dibasic acids dis-
esters of the
mono-potassium
solved
in
equi-molecular proportion.
This was
in
accordance with the experiments made by Brown and
Walker.
In this
way they prepared
butyric ethyl ester from
potassium acetate and potassium- ethyl succinate.

synthesis of the ethyl ester
of
valeric,
capronic,
The and
isobutyl-acetic acid was also effected.
The
reactions
all
take place according to the follow-
ing equation:
XCOOK + COOKY.COOC H = K + 2CO, + XY.COOC H

2 5
In accordance with a similar principle they obtained

ethyl alcohol from potassium acetate and potassium
glycolate.
If
potassium-ethyl malonate was taken as
one of the
salts
and a solution of
this
with potassium
acetate, propionate, or butyrate
was electrolyzed there
was formed
the ethyl ester
of propionic, butyric, or
valeric acid, respectively.

v.
Miller" applied
this
method
to a
number
of
other mixtures.
Thus
upon the electrolysis of a mix-
ture of acetic ester with tricar bally lie ester, one third
1
Chem.
Ztschr.
Ber., 28, 2427; Zeitschr.

f.
f.
Elektroch., 4, 55.
Elektroch., 4, 55.
of
35
which was saponified, there was formed principally If aromatic ester acids were ethyl-succinic ester.
electrolyzed with potassium acetate a similar synthesis
occurred.
By
this
method a-niethyl-hydrocinnamic
ester,
6
,
H - CH - CH - COOC H CH
6
was prepared from potassium-ethyl benzyl-malonate and potassium acetate. Dibenzyl-succinic ester is formed
at
same time, according C. Brown

the
:
to
the
reaction
of
C C
H - CH - CH - COOC H H - CH, - CH - COOC H

B
This reaction does not take place

acetate
If
is
if
potassium
not present.
the deportment of the alkali salts of the mono-
analogous to that of sodium acetate the chief products to be expected are

basic oxyacids
upon
electrolysis
is
symmetrical glycols:
2C n H ro (OH)COO
the
case.
- = C M H W (OH), + 2CO,.
1
According to Walker's
generally
experiments
the
this
is
not
of
From
potassium
i.e.,
salt
mandelic acid the expected product,

of hydrobenzoin
a mixture
formed only in small quantities; benzaldehyde, however, is formed

isohydrobenzo'in,
is
and
in larger quantities.
1
Journ. Chem. Soc., 45, 1278,
36

The
alkali salts of
oxyacids give,
in addition to the
above,
many
other substances, principally aldehydes,

if
and the results are the same even
the attempt
is
made
to
weaken the action
of the electrolytic
oxygen
by converting the alcohols into esters.
Thus from the sodium
salt of glycolic
acid
(CH,OH.
COOH), ethyl-glycolic acid (CH.OC.H..COOH), and a-lacttc acM (CH 9 .CH(OH)COOH) the chief product
obtained
is
acetic aldehyde,
and
it is
quite possible that
the production of hydrobenzom and isohydrobenzom
from mandelic acid
is
due to the
electrolytic reduction
of the benzaldehyde originally formed.
This view
1
is
supported by the investigations of

actually obtained
Kauffmann, who
hydrobenzom and
isohydrobenzoin by the direct electrolytic reduction

of benzaldehyde.
3
Elbs
emphasizes the
fact that
it
is
not necessary
to suppose that aldehydes are a result of secondary
oxidation produced by the
oxygen available
in the
region of the anode, but that their formation can also
be regarded as analogous to that of ethylene from

propionic acid:
2CH .CH .COO - = CH .CH .COOH

3
2CH .CH(OH)COO - = CH .CH(OH).COOH

3 3
CH
1
.CHO.
Ztschr.
f.
Elektroch.,
2, 367.
Jahrbuch.
d. Elektroch., 3, 295.
37
still
further advance in this field
is
the successful
substitution of iodine
trolysis.
and
of
nitro-groups by elec-
On
in
electrolyzing propionic acid and potas-
aqueous solution fi-iodo-propionic acid was formed, due to the int rim ill ill fgPjmtliii of
i
ium iodide
succmic acid
OF THE
UNIVERSITY
COOH.CH .CH .COOK + KI

3 a
= ICH
.CH .COOH
2
+ 2K + C0
nitrite.
Nitro-ethane was probably obtained in small quantities
from sodium propionate and sodium
ELECTROSYNTHESES OF BROWN AND WALKER.'
A systematic
current was
first
synthesis with the aid of the electric
attained in the researches of
Brown
and Walker.
on the
fact
Their investigations are based partly observed by Kolbe that monobasic fatty
acids yield hydrocarbons,
the experiments of Guthries,

ester
and partly on the results of 2 who found that the
group
the
is
electrolytically inactive.
These
facts
justified
hypothesis
that
the
mono-esters of
dibasic acids
current,
like
would behave, under the action of the

monobasic
acids,
i.e.,
carbon dioxide
Lieb. Ann., 261, 107; ibid., 274, 41. Lieb. Ann., 99, 65.
38

split off
would be
and esters
of higher dibasic acids
would be formed according to the equations
- CH - COOK =C H .OOC-CH -CH -COOC H +2K +C0 2C H - OOC.CH .CH .COOK

2C,H .OOC
6 2 6
=C H .OOC.CH
a 6
.CH .CH .CH .COOC

a 2 a
Their experiments, conducted
in fairly
concentrated
solutions with currents of high density, completely
confirmed this supposition.

the following syntheses were
I
.
Under
made:
these conditions
Succinic acid from ethyl-potassium malonate.
2.
3.
Adipic acid from ethyl-potassium succinate.

Suberic acid from ethyl-potassium glutarate.
Sebacic
4.
acid from the ethyl-potassium salt of
adipic acid.
5.
n-Dodecane-dicarboxylic acid
salt of suberic acid.
from
the
ethyl-
potassium
6.
n-Deca-hexane-dicarboxylic acid from the ethylsalt of sebacic acid.
potassium
If
the ethyl-potassium salts of substituted acids are

it
taken as a starting-point
is
possible
to
obtain
disubstituted acids according to the above reaction.

1.
Ethyl-potassium methyl-malonate gave the two
symmetrical dimethyl-succinic acids, having the melting-points 193

2.
and 121.
Ethyl-pctassium ethyl-malonate gave the corre-
spending symmetrical diethyl-succinic melting-points 192 and 130.
3.
39
acids,
with the
Ethyl-potassium dimethyl-malonate gave tetra-
methyl-succinic acid.
4.
From
ethyl-potassium
diethyl-malonate a sub4
,
stance of the composition
C 14 H 2e O
which
differs
from
the expected tetraethyl-succinic acid by C 2 4 was The nature of this body has not yet been obtained.
,
determined.
Hydrobromic acid
splits off alcohol
the
compound
ia
ao
O,,
which has perhaps the furfurane formula

(C 2 H & ),:C-C:(C a
i
),,
O C
:
C O
:
being formed.
All these reactions did not take place smoothly, but
were accompanied by secondary reactions, principally oxidations, which were limited as much as possible by working with strong concentrated solutions and
low temperatures.
also
is
Moreover, the formation of esters
always possible according to the equation
2CH..COO
- = CH,COOCH, + CO
and, finally, the formation of unsaturated esters
may
take place as illustrated in the simplest case:
40

6 a 4 2 B
2C,H 2C H
2
COO - = C H + CO, + C H COOH, OOC.CH CH,.COO - = 2C H OOC.CH -CH .CH CH +C H OOC.CH .CH .COOH+CO
6 2
2 5 2
a.
In this
way
it
was possible to
isolate methyl-acrylic
acid by the electrolysis of ethyl-potassium dimethylmalonate, and ethyl-crotonic acid by electrolyzing a

solution of the ethyl-potassium salt of diethyl-malonic
acid.
On
the electrolysis of sebacic acid the

9
:
ethyl
ester of an unsaturated acid,
CH CH(CH .COOH,
2) 6
was formed.
Brown and Walker

ethyl salt of
also electrolyzed the
sodium-
camphoric acid and obtained two esters

frac-
which they were able to separate by means of

tional distillation.
One
of these (boiling-point
212-
213) on being
monobasic
having
acid,
saponified
yielded
an
unsaturated
H O
14
2,
campholytic acid ; the other,
(240-242), was the to which neutral ester of a dibasic acid, C 18 H 30 O

a higher boiling-point
4
,
Walker gave the name
of camphothetic acid.
The
experiments are of great importance, because they

prove the dibasic nature of camphoric acid, a fact
which
doubted by Friedel. 5 Walker and Henderson found,

is
moreover,
that
upon the electrolysis of concentrated aqueous solutions of the potassium salt of allocamphoric ester there
1
Lieb. Ann., 274, 71.
Journ. Chem. Soc., 67, 337.
are
4!
formed as chief products the ethyl esters of a dibasic acid, C 18 H a8 (COOH) a and of a monobasic acid,
,
H COOH: /COOC H
13
__
/COOC H
a a
6
2.
2U
/COOC H
a
/COOC H
C
8
H COOC H
13
a
l
It has
been found on further investigation

the
that
acid
besides
strongly dextrorotary unsaturated

as allocampholytic acid,
is
designated
isomeric
H COOH,
13
an
acid
formed which,
is
although
slightly
dextrorotary as obtained,
in
perhaps even laevorotary
heated to 200
an entirely pure condition. The latter on being splits off carbon dioxide and yields a
,
and hydrocarbon, C 8 H 14 which boils at 120-122 appears to be identical with laurolene, made from
camphoric acid.
A ketonic acid,
is
also
3 melting-point 228, found as an additional product of the electroly-
H O.COOH,
The potassium allocamphoric ethyl ester. authors conclude from their observations that camsis
of
phoric acid contains the group
H-C1
42

It is
expected that these results tural formula for camphoric acid.

'
will give
the struc-
Following the experiments of Brown and Walker,

Schields
investigated the deportment of ethyl-potas-
sium maleate
and fumarate on
electrolysis.
His
results confirm the experiments of Kekule.
During
the electrolysis carbon dioxide, oxygen, and unsat-
urated hydrocarbons were evolved, and the unchanged maleic or fumaric acid and the corresponding ethyl
esters, respectively,
remained
it
in the solution.
would appear that unsaturated acids form no synthetic products on electhese experiments
trolysis,
From
and the aromatic acids
phthalic acid and

in
benzyl-malonic acid
conduct themselves
a similar
manner.
Finally
may be mentioned
the electrolysis
of ethyl-potassium oxalate, which yielded ethylene in
addition to carbon dioxide.
ELECTROSYNTHESES OF MULLIKEN' AND WEEMS.
Mulliken electrolyzed the sodium compounds of the

diethyl esters of dibasic acids in alcoholic solution and
obtained
compounds which were formed when sodium was removed by iodine. He thus
made:
1
the same
Lieb. Ann., 274, 64; Journ.
Chem.
Soc., 69, 737.
Amer. Chem. Journ.,

Ibid., 1 6, 569.
15, 323.
1
.
43
Ethane-tetracarboxylic ester from sodium-diethylester.
ma Ionic
2.
Ethane-hexacarboxylic ester from sodium-methane-
tricarboxylic ester.
3.
Tetracetyl-ethane from acetyl-acetone.
4.
thick
oil
which contained a small quantity of
diacetyl-succinic ester
from aceto-acetic
ester.
The
conclusion reached by Mulliken, that in the
electrolysis of certain
weak organic
acids a portion of
the anions unite in pairs without undergoing decom-
was closely examined by Weems as to its general applicability and as to the exact nature of the All direct chemical changes which take place.
position,
attempts to oxidize malonic ester with hydrogen peroxide, potassium permanganate, and chromic acid, and
to produce an effect similar to that caused
current,
by the
were without success.

electrolyzing the sodium salt of methyl-
Weems, on
malonic ester in alcoholic solution, obtained dimethylethane-tetracarboxylic ester; ethyl-malonic ester yielded
diethyl-ethane-tetracarboxylic
ester
ester;
and
aceto-acetic
was changed
to diacetyl-succinic ester.
In the electrolysis of cyan-acetic ester the formation

of dicyan-succinic ester could not be observed; like-
wise a union of the anions of benzyl-malonic ester,

acetyl-malonic ester, and acetyl-dicarboxylic ester did
not take place.
Electrolysis of acid amides in the
44
form of their sodium or mercury compounds yielded
unchanged amides. The review which has been given of the investigations on the electrolysis of the aliphatic carboxylic
acids
this
is
believed to include
all
present information on
subject.
is
Of the
investigations
mentioned, an
advance
shown only in those of Kolbe-Bourgoin, Brown-Walker, and Mulliken-Weems. The action of

effecting a limited
the electric current has been used, in these cases at

least, for
number
of organic synof the
theses.
number
of papers
on the action
electric current
and sulphur
will
on compounds containing cyanogen next be mentioned.
2.
Cyanogen Compounds.
J
Cyanogen.
Berthelot
into
its
observed that cyanogen was
decomposed
elements by the action of the

slightest trace of water in the gas
electric spark.
The
caused the formation of hydrocyanic acid and acetylene.
action
By submitting moist cyanogen gas of the voltaic arc Buff and Hofmann
to
8
the
noted
the formation of carbon dioxide, carbon monoxide,
and ammonia.
Cyanogen can be obtained by the

solution of potassium ferrocyanide.
1
electrolysis of a
Comp.
* 8
rend., 82, 1360. Lieb. Ann., 113, 135.

p. 45.
See potassium ferrocyanide.
Hydrocyanic
Acid.
45
Berthelot
l
Electrosynthesis
acid
obtained hydrocyanic
by passing the
electric
spark through a mixture of acetylene
and nitrogen.
The
reaction
is,
however, reversible.
On
allowing
it
the electric spark to act on hydrocyanic-acid gas
was decomposed into acetylene and nitrogen.

cyanic acid
is
Hydroelectric
also obtained
by passing the
spark through mixtures of ethylene or aniline vapor with nitrogen, acetylene with nitric oxide (Huntington
a
),
nitrogen with benzol (Perkin
),
etc.
Electrolysis:
In
sulphuric-acid
solution
hydro-
Gayand Concentrated Lussac, cyanogen. hydrogen a drop of sulphuric acid to which acid hydrocyanic has been added gives carbon monoxide and ammonia
4
cyanic acid breaks

into
up
smoothly, according to
(SchlagdenhaufTen
).
Potassium Cyanide.
salt,
In the investigation
of
this
conducted by the author last mentioned, it was found that no oxygen escaped at the anode, but the potassium cyanide was oxidized to potassium
cyanate.
Potassium Ferrocyanide.
This compound gives at
the anode hydrocyanic acid and Prussian blue and at

the
cathode
hydrogen
and
potassium hydroxide
English patent, 14855;

Jahresb.
f.
German
patent, 93852.
Chem., 1870, p. 399. Gilbert's Ann., 1811-1815; Ann. chim. phys., 78, Jahresb. f. Chem., 1863, p. 305.
245.
46

1
(Perrot
hauffen.
);
8
also
cyanogen,
according to
Schlagden-
Potassium Ferricyanide likewise gives on electrolysis Prussian
blue at the anode.
Sodio-nitro-prusside.
On
electrolyzing a dilute solu-
tion of this salt for a prolonged period
Weith
noted
the formation of
ammonia and the
precipitation of
metallic iron; at the positive electrode Prussian blue
appeared, and nitrogen, oxygen, and,
if
the operation
off.
was long continued,

at the cathode
nitric
oxide also were given
In a concentrated solution
much ammonia was formed

according to
and
nitric
oxide appeared at the anode.
Prussian blue can
also be obtained
Luckow's method
for the general preparation of in-
soluble compounds.
Nitriles.
Ahrens,
by means
of
the
electrolytic
addition of hydrogen, succeeded in converting nitriles

into primary amines, while simultaneously with the
reduction
partial
saponification
of
the
nitriles
occurred, as represented
by the following equation:
R.CN
Aceto-nitrile.
+ 2H O =
2
R.COOH
although
+ NH,.
a
This substance yields only a small

considerable
quantity
1
of
ethylamine,
* 1
Tommasi, Traite d'Electrochimie, 720. f. Chem., 1863, p. 305; J. prakt. Chem., 30, 145. Jahresb. f. Chem., 1863, p. 306; ibid., 1868, p. 311; Bull.
Jahresb.
soc.
chim., [2] 10, I2i.

4
6
German
Ztschr.
patent, 91707.
f.
Elektroch., 3, 99.
Of ALIPHATIC COMPOUNDS.
quantity of /z-propylamine
nitrite.
is
47
formed from n-propio-
The
reduction of aromatic nitrites takes place with-
out the occurrence of secondary reactions.

illustrated
in
This
is
benzo-nitrile
benzylamine from and of phenyl-ethylamine from benzylof
the
formation
cyanide.
3.
Compounds Containing Sulphur.

'
Mercaptans.
Bunge
electrolyzed the alkali salts of
mercaptans and observed the formation of disulphides

at the positive pole.
In the case of the sulpho-com-
pounds, however, the free acids were regenerated.

Sodium-isethionate.
The same author
also investi-
gated sodium isethionate, but could note the formation

of only the free acid at the positive pole.
This acid, investigated by Renard, yielded hydrogen at the negative pole, while
Methyl-sulphuric Acid.
3
formic acid, carbon dioxide, carbon monoxide, and
trioxy-methylene, besides free sulphuric
acid,
were
found present at the positive pole. Potassium - trichlor - methyl Sulphate.

8
This
com-
pound, electrolyzed by Bunge, gave hydrogen and

alkali
at
the
negative
pole,
at
the
positive
pole
Chem.
Ber., 3, 911.
[5] 17, 289;
Ann. chim. phys.,
Comp.
rend., 90, 175, 531; ibid.,
92, 965.
*
Chem.
Ber., 3, 911.
48
oxygen, carbonic-acid gas, chlorine, sulphuric acid, and perchloric acid.

Potassium-trichlor-methyl Sulphonate
l
This
salt
was
electrolyzed by Kolbe in neutral concentrated aqueous solution and gave the following results:
The
free
became strongly acid and contained hydrochloric and sulphuric acid. Hydrogen was
solution
gradually evolved at the negative pole.
After the
decomposition was complete the solution contained

potassium perchlorate, which was also observed
case of potassium-trichlor-methyl sulphate.
in the
Ethyl-sulphuric Acid.
2
Ethyl-sulphuric
acid
gave,
according to Renard, on being subjected to electrolysis,
at the negative pole hydrogen,
and
at the positive
pole acetic acid, some formic acid, aldehyde, and sul-
phuric acid.
In concentrated solution a greater pro-
portion of acetic acid was formed.

salt
The potassium
3
on electrolysis breaks up, according to Hittorf, and OSO .OC H into K

2 a
.
Potassium-isoamyl Sulphate, according to Guthries,

is
decomposed
into
oxygen, valeric acid, and

4
sul-
phuric acid.
Potassium Xanthate.
electrolysis of
C. Schall
obtained, by the
potassium xanthate
in
aqueous solution,
xanthogen
supersulphide, as
1
might be expected:
Journ. prakt. Chem., 62, 311. Ann. chim. phys., [5] 17, 289.
Pogg. Ann., 106,

Ztschr.
f.
530.
Elektroch., 2, 475.
49
ft
O.C
/O.C.H. 2CS
/O.C,H CS
\
CS
\S-
\S
S/
According to Schall
'
Dimethyl-dithiocarbamic Acid.
the electrolysis of the potassium salt of dimethyl-
dithiocarbamic acid resulted in the formation of tetra-
ethyl-thiuram disulphide,
[CS.N(C,H.),],S,.
This compound under the influence of the electric discharge absorbs as much as 8.6$ of its
Thiophene.
own weight
3
of
nitrogen,
(C 4
S) 2
being formed
(Berthelot
).
Ztschr.
f.
Elektroch., 3, 83.
35.
Ann. chim. phys., n,
OF AROMATIC COMPOUNDS.
THE
data on the results of investigation in this
branch of the subject are considerably more limited

than in the case of the aliphatic
reasons for this
is
series.
One
of the
the difficulty with which the ben-
zene nucleus undergoes oxidation, a condition which permits of comparatively few reactions.
the
reactions
all
Nearly
all
involve substituted groups only.
In
almost
altered.
cases the benzene nucleus remains un-
In accordance with the
method
of presentation pre-
viously adopted, the investigations on the electrolysis

of the
hydroxyl compounds
will
be
first
discussed in
the following synopsis.

i.
Phenols.
9
Phenol.
Bunge, Bartoli and Papasogli
submitted
phenol to the action of the electric current,

I
Bunge
Chem.
Ber., 3, 296.
19.
II
Gazz. Chim., 14,
51
52
observed that the decomposition of potassium phenolate was analogous to that of an acid or a salt;
the
potassium
phenolate was
6
split
up
into
(cathion) and C
HO
5
(anion), the latter combining
with water to
oxygen.
form phenol, with the liberation of Bartoli and Papasogli, on electrolyzing solu-
tions of phenol in potassium and sodium hydroxide, and using electrodes of coke, graphite, and platinum,
obtained an acid having the composition
HO
6
which melted
tion
in
at
93, reduced ammoniacal
silver solu-
and Fehling's solution on being heated, and when aqueous solution was not precipitated by acids. When, however, coke was used as the positive electrode,
an
extensive
decomposition of
the
phenol
occurred and a resin was formed.
On
subjecting a neutral potassium phenolate solu-
tion to the action of the electric current they were
able to isolate a
compound, C 66 H 48 O a2 soluble
,
in alkali
and precipitated from such solutions by mineral This latter compound on being oxidized with
acid formed picric acid.
acids.
nitric
When
allowed to remain in
solution in the presence of dilute acids for a prolonged

period,
it
underwent decomposition according to the
following equation:
C, t
<8
0,,
+ H.O = C ,H0 + C..H..O..

4
lt
The
electrolysis of neutral
sodium phenolate
solu-
tion
53
gave an acid with the formula C M H,

is
which
likewise
decomposed on boiling with dilute acids:
29
30
=
1Q
C
10
17
H
8
10
+C H
la
10
0,.
at
The compound C H O is soluble in alcohol, melts 75, and is isomeric with the hydroquinone ether,
obtained by Etard from chlorchromic acid and phenol. It has the composition
Christomanos
only
observed that while

dissolved
sodium
acts
monobrom-benzene, diphenyl can speedily be obtained by placing sodium in the solution and connecting this metal with the
positive pole of a battery of
very slowly on
two Bunsen elements, whose electrodes are immersed in the solution; diis
phenyl
sodium.
likewise obtained
by using zinc instead of

a
Phenyl-mercaptan.
mercaptan
alkyl
in
Bunge investigated phenylthe same manner as the corresponding

Phenyl-disulphide, (C.H B ) a S a
,
compound.
was
formed at the positive pole.

1
Gazz. Chim., 1875,
p. 402.
Chem.
Ber., 3, 911.
54
2.
Aldehydes and Ketones.

Kauffmann,
1
Benzaldehyde.
by the
electrolysis of
in a 12-15$ solution of potassium biobtained at the cathode a mixture of hysulphide, dro-benzoin and iso-hydrobenzoin. According to his
benzaldehyde
statements, an alcoholic solution of sodium hydroxide

is
more
suitable for the reaction than the aqueous
solution of bisulphide.
Other aldehydes and ketones

Michler's
ke-
show a behavior
similar to benzaldehyde.
Tetramethyl-diamido-benzophenone.
tone,
J /C
HN \C H N
6 6
4
(CH ) (CH,y
3
gives the corresponding benzhydrol,
/C H
6
.N
(CH.).
(HO)CH
\C.H .N
4
:(CH,) a
.
Aceto
phenone,
H .CO.CH
6
Aceto
phenone
yields aceto-phenone pinacone,
C.H
^-C
\C(OH).C(OH).
Ztschr.
f.
Elektroch., 2, 365.
4, 461.
Benzile.
55
The aromatic
di-ketone benzile,
C,H CO.
6
CO.C
5,
gives peculiar results.
On
reduction in an
alkaline alcoholic solution a
whole
series of bodies is
formed,
i.e.,
benzoic acid, benzilic acid, tetraphenyl6 4
erythrite,
C a8 H, O
C.H^HOH
H .COH C H,COH
C
e
5
6
C.H..CHOH,
and a substance, C, 8 H a6 O s containing one less atom of oxygen, which has probably the constitution
,
C.H
6
.(j;OH
C,H .CH C H .CHOH.

8 5
Tetraphenyl-erythrite
reduction of benzoin.
is
also
formed by the direct
Anthraquinone,
H //CO \C ^ H
4
6
*'
According to Weizmann,
sulphuric
acid solution
is
this
compound when
in
converted by electrolytic
oxidation into monoxy-, dioxy-, and trioxy-anthra1
French Pat. 265292.
56
ELECTROLYSIS AND ELECTROS YN THE SIS
quinone.
of
The cathode
fluids
employed were solutions

chromates, permangaacids.
alkalies,
alkali carbonates,
nates, acidulated water,
and dilute
Both
direct
and alternating currents were used. On the electrolysis of anthraquinone and potassium hydroxide
alizarine
is
formed.
Nitro-aldehydes and nitro-ketones will be discussed

in the chapter
on nitro-compounds.
Acids.
its salts
3.
Benzoic Acid.
Benzoic acid and
were ex1
amined by several investigators, first by Matteuci, 8 then by Brester, and most thoroughly by Bourgoin. The result of all these investigations is to show
8
that here
no secondary reactions take
place, as
was
observed in the case of the fatty acids, but that the

only effect of the current
into
hydrogen
(or
to produce a separation and the acid radical, the metal)

is
latter regenerating the acid at the positive pole.
In
an alkaline solution
it
is
possible to so increase the

is
oxidation that the benzoic acid
destroyed.
The
decomposition products which then appear at the anode are carbon dioxide, carbon monoxide, and
sometimes acetylene.
The odor
of bitter
almonds
is
also frequently observed.

1
thorough investigation
Jahresb.
8
f.
Chem.,
1866, p. 87.
57
on the electrolytic decomposition of sodium benzoate He employed a current having a was made by Lob.
1
potential of 6-7 volts and a current density of 15-20
amp., and obtained a small quantity of a substance containing sodium, the empirical formula for which
was
C,H.O.Na,
but the chemical nature of which has not yet been
determined.
a small
There
is
formed besides
this
compound
amount
of benzaldehyde, as well as acetylene
and carbon monoxide.
Under no circumstances do
otherwise generally the case in
diphenyl or other hydrocarbons occur, nor do fatty

acids appear,
which
is
an oxidation of
this character.
Thio-benzoic Acid.
On
electrolyzing this acid Bunge'
obtained the bisulphide of benzoyl.

Sulpho-benzoic Acid.
This acid
is
not changed by
the current according to the statements of the same

investigator.
*
Phthalic Acid.
of this acid
in
Bourgoin states that the electrolysis

its
and of
neutral or alkaline salts resulted
the formation of the unchanged acid at the positive
pole.
The appearance
of small quantities of carbon
dioxide and carbon monoxide, however, was an evi-
Zeitschr.
f.
Elektroch., 2, 663,
ibid., 3, 3.
Chem.
Ber., 3, 296.
f.
Jahresb.
Chem,,
1871, p. 631.
58
dence that a small portion of the acid had undergone

oxidation.
The potassium
phthalic
1
salt
acid,
when
mono-ethyl ester of electrolyzed by Brown and

of
the
Walker,
became dark-colored and a resinous subof
stance was formed, but the isolation electrolytic product was not possible.
Phenyl-acetic Acid.
8
any new
in the
This acid electrolyzed

salt
form of
its
potassium
by Slawik
acid,
yielded free
phenyl-acetic acid.
Cinnamic Acid.
8
Cinnamic
investigated
by
Brester,
showed a
similar behavior in the electrolysis
of both the free acid

salts.
and the neutral solutions
of its
Benzyl-malonic Acid.
of
its
When
4
this acid in
the form
elec-
ethyl-potassium salt was submitted to
trolysis
by Brown and Walker
it
showed a behavior
acid.
materially different
solution
from that of malonic
The
became dark-colored and contained no new

If
compound.
oxidation occurred
it
was a complete
oxidation into carbon dioxide and carbon monoxide,
such as has been observed

rated acids.
in
the case of the unsatu-
Chem.
Lieb. Ann., 274, 67. Ber., 7, 1051.

p. 87.
Jahresb. f. Chem., 1866, Lieb. Ann., 274, 67.
OF AHOMAT1C COMPOUNDS.
4.
Amido-Compounds.
*
Aniline.
Destrem
investigated the action of the
electric spark
from an induction apparatus on aniline
vapor and observed a decomposition into acetylene, E. Rohydrogen, hydrocyanic acid, and nitrogen.
tundi
a
electrolyzed aniline.
Since pure aniline
is
an
extremely poor conductor he made the solution

able
for electrolysis
suit-
by the addition of ammonia. After a period of three days, during which hydrogen was continually evolved at the negative pole and a
tarry substance
was deposited
at the positive pole,
Rotundi interrupted the electrolysis and was able, with more or less certainty, to establish the following
processes
1.
:
The formation
6
of
diazo-compounds:
a
H NH (HNO.) + HNO = C H N NO, + 2H

a 6 6 3
O.
2.
The formation
fl
of diazo-amido-compounds:
6 6
H NH + HNO, = C H N NHC H + 2H O. H N NO + C H NH = C H N NH.C H + HNO,.

2C
5 B
3.
The formation
of
azo-compounds by
direct oxi-
dation of aniline:
2C
1
H NH, + 2O = 2H O + C H N C H
6 3 6
6
Jahresb.
Atti.
d.
f.
Chem.,
1884, p. 272.
R. Acad. d. Scienze d.
Torino, 39, 4
Jahresb.
f.
Chem.,
1884, p. 270.
6O
4.
The formation
of
amido-azo-compounds
by
molecular rearrangement of diazo-amido-compounds.
The
nitrous and nitric acids were oxidation products
of the
ammonia which was added.
INVESTIGATIONS OF GOPPELSROEDER.'
These
relate to aniline
and
its
derivatives,
and aim
at preparing the
series.
the
cell
most important dyes of the aniline Although the reactions which take place in have not as yet been explained, the researches
Goppels-
form valuable material for consideration.
roeder has gathered the technical results in a small " " Farbelektrochemische Mitteilungen pamphlet:
(Muhlhausen, 1889).
If
a galvanic current
is
conducted through acid or

is
neutral aqueous
solutions of aniline there
formed
at
the positive pole, besides other coloring matters, aniline black,
24
H N Cl.
ai
4
Under
similar conditions dyes
are obtained at the positive pole from the salts of

toluidene,
methyl- aniline,
diphenylamine, ditolylamine
and phenyl-tolylamine.
naphthylamine violet. On electrolysis of anthraquinone and potassium hydroxide, 8 Goppelsroeder succeeded in obtaining alizarine.
Naphthylamine
salts give
ibid.)
*
Dingier, Polytech. Journal, 221, 75; 224, 92 and 209. See also p. 56.
ibid.,
223, 317 and 634;
61
All these reactions are to be attributed to the action

of electrolytic
will
oxygen.
it
In the brief survey which
here be given
is
not possible to go into the
details of the researches.

will serve as a
The
following literary data
guide:
1
Research
Research
aniline.
I.
2
Preparation of aniline black.

Electrolysis of aniline with excess of of
2.
Electrolysis
toluidene.
Electrolysis
of
mixtures of aniline with toluic acids.
Research
salts in the
3.'
Electrolysis of aniline
and toluidene
presence of nitrate,
nitrite, or chlorate of
potassium
in
aqueous solution.
4."
Research
aniline.
Electrolysis of the salts of methyl-
Electrolysis of the salts of diphenylamine.

of
Electrolysis
the
salts
of
methyl-diphenylamine.
Electrolysis of phenol.
Electrolysis of the salts of
naphthylamine.
Research
zarine
5.
Conversion of anthraquinone into
ali-
by the electrolysis of a mixture of anthraquinone and potassium hydroxide.

Liebmann's
electrolytic
fl
attempts to make
of
aniline
quinone by the
oxidation
or electrolytically
prepared aniline black were unsuccessful.

1
Dingier, Polytechn. Journ., 221, 75.

Ibid., 223, 317.
Ibid., 223, 634. Ibid., 224, 92.
Ibid., 224, 209.
* 3
4
6
'
Ztschr.
f.
Elektroch.,
2,
497.
62

Hydroquinone
in
an aqueous solution acidified with sulphuric acid could be quantitatively converted into quinone at the anode:
2C.H (OH)
4
+ O = H,0 + C H (OH) .C,H 0,

6
4
The same compound was

nating currents were used.
1
also
formed when
alter-
Voigt,
by the
electrolytic
oxidation of suitable
mixtures of bases, prepared rosaniline, chrysaniline,

safranine,
and p-leucaniline. His object in these researches was the same as that of Goppelsroeder;
namely, the preparation of the important dyes of the
aniline series.
If
electrolytic
oxygen
is
permitted to act upon
aniline, dissolved in concentrated acetic acid solution,
acetanilide
is
formed;
by using a
is
dilute
solution,
however, amido-hydroquinone So far as can be learned from the literature these

investigations have not been concluded, which
is
obtained.
also
the case with those of Poising,
who by
the oxidation
of p-phenylene-diamine obtained a beautiful blue
dye
similar to indigo.
Poising obtained p-phenylene-diamine by the electrolytic reduction of amido-azo-benzene.
From
the electrolysis of benzene -p-phenylene-diamine

1
Ztschr. Ztschr.
f. f.
angew. Chem.,
Elektrochemie,
1894, p. 107.
2, 30.
63
there likewise resulted at the anode a blue dye, which
showed a behavior analogous to that

obtained from p-phenylene-diamine.
of
the dye
5.
Electrolytic Reduction of Nitro-Compounds.
In general, azo-, hydrazo-, and amido-compounds
from the electrolytic reduction of nitro-comIn this way Kendall obtained aniline from pounds.
result
1
nitre-benzene,
and Elbs a and Haussermann
prepared
the normal reduction products of nitfo-phenol.
The
formation of azoxy-, azo-, amido-, or hydrazo-com-
solutions were employed.
pounds was dependent upon whether acid or alkaline If nitro-benzene is reduced

to
in a concentrated acetic or formic acid solution,
which a few drops of concentrated sulphuric acid (to increase the conductivity) have been added, the
corresponding
salts of
4
benzidene result; a fact further
confirmed by Lob.
in
According to the investigations of the same author, the electrolysis of an ammoniacal solution azois
benzene
formed as the chief product and hydrazo-
benzene as a secondary product. Gattermann and Koppert * obtained p-amido-phenol1
German
Pat., 21131.
4
5
Journ. prakt. Chem., 49, 39. Chem. Zeitung, 17, 129, 209. Ztschr. f. Elektrochem., 3, 471.
Chem. Zeitung,
17, 210.
64

reduction of nitro-benzene-sulphonic
sulphate by the
acid.
Noyes and Clement, on the reduction

1
of
nitro-
benzene
obtained
a
in
a concentrated sulphuric acid solution,

acid.
p-amido-phenol-sulphonic
Gatter-
mann,
starting with a similar solution, by varying
the conditions of the
He p-amido-phenol. ing the intermediate formation of phenyl-hydroxylamine, which on further reduction changes by molecular rearrangement into the final product.
experiment obtained directly explains the reaction by assum-
By
similar
treatment were formed:
an
amido-cresol-monosulphonic
toluene;
acid 3 from
o-nitro-
the o-p-diamido-phenol from m-dinitro-benzene;

diamido-cresol from o-p-dinitro-toluene;
o-p-diamido-phenol from m-nitr aniline; a diamido-cresol from o-nitro-p-toluidene;

the same diamido-cresol from p-nitro-o-toluidene;
an amido-salicylic acid from m-nitro-benzoic acid; an amido-cresotinic acid from m-nitr o-p-toluic acid;
a corresponding amido-oxy acid from nitro-terephthalic
acid;
a corresponding amido-oxy-acid from nitro-isophthalic

acid;
1
Chem.
Ber., 26, 990.
8 8
Ibid., 26, 1840.
Ibid., 27, 1929.
an amido-naphthalene-sulphonic acid from
naphthalene-sulphonic acid.
65
aôe^-nitro-
The
following
is
is
true in
all
these cases where the
reduction
carried out in a concentrated sulphuric
acid solution:
The
nitro-groups are completely reduced to amido-
groups and a hydroxyl-group is taken up, always in a As in the para-position to one of the amido-groups.
case of o-nitro-toluene sometimes also a sulpho-group
is
taken up.
p-nitro- toluene
on
electrolysis
behaves
differently.
Here the
a
,
final
product has the composiis
tion
14
H u N,O
and
its
formation
is
as follows:
p-tolyl-
p-Amido-benzyl alcohol
tion of p-nitro-toluene)
formed from
hydroxylamine (an intermediate product in the reduc-
by molecular rearrangement,
_
/CH OH
3
The amido-benzyl
alcohol thus formed condenses

influ'
with one molecule of nitro-toluene (under the ence of the sulphuric acid), water being
split off
'
u H /CH,OH
TT /CH, r Cehl
*\N0
nitro-amino-o-benzyl-toluene,
C.H
- -CH -C H
6
/3 + Ha0
Chem.
Ber., 26, 2810,
66
ELECTROLYSIS AND ELECTROS YN THE SIS

In a third paper
1
to a large
number
Gattermann applies this reduction of compounds which for lack of
space cannot here be enumerated.

reaction
is
The nature
The
of the
the same in
all
cases.
esters of the
carboxylic acids
show the same behavior
as the acids
themselves.
These reduction products have

jects of patents.
2
all
become the suband
Lob and Gattermann have produced

direct evidence that the
direct
in-
amido-phenols are actually formed by the molecular rearrangement of phenylhydroxylamine, which occurs as an intermediate
product.
Lob
has found that p- and o-chlor-aniline are ob-
tained by the electrolytic reduction of nitro-benzene
suspended
dissolved
in
in
fuming hydrochloric
in
acid, nitro-benzene
nitro-
alcoholic hydrochloric acid, and
benzene dissolved
acetic acid.
mixtures of hydrochloric and

acid the correspond-
With hydrobromic
ing brom-anilines are formed.
The
reaction takes place as
shown
in the following
equations:
2.
C
1
NHOH+
HCl
H NHCl+H O
6 a
Chem. Ber., 2J, German Patent,

Ztschr.
f.
1927.
75260 and additions to the same,

3, 46.
Elektrochem.,
3.
67
C,H NHC1
6
=
NH,
NH.
and
^CC1
I
HC
II
I
UNIVERSIT
Cl
The phenyl-chloramine formed by the

by molecular rearrangement,
aniline.
action of
hydrochloric acid on phenyl-hydroxylamine changes,

into
o-
and p-chlor-
Gattermann has obtained
direct proof of the inter-
mediate formation of phenyl-hydroxylamine by adding benzaldehyde to the solution at the beginning of the
electrolysis.
He was
thus able to isolate a condensa-
tion product of
hyde.
In this
phenyl-hydroxylamine with benzaldeway he obtained benzylidene-phenyl-
hydroxylamine,
O C.H N- -CH,C H
6
6
',
from nitre-benzene benzy lidene-o-tolyl-hydroxylamine,
.CH
N.C
.CH
from o-nitro-toluene, and the corresponding benzylidene compounds from m-nitro-toluene, p-nitro-toluene,
nitro-p-xylene,
and m-nitro-benzoic
of
1
acid.
in
The presence
formaldehyde
the electrolytic
Chem.
Ber., 29, 3040.
68

of
reduction
nitro-compounds produces an effect entirely different from that caused by the addition of
benzaldehyde.
The phenomena
occurring in this case

1
have been thoroughly investigated by Lob. The fundamental object of his researches from that of Gattermann,
in that
differs
Lob undertakes
to
establish the separate phases of the reduction of the
nitro-group.
This he accomplishes by the addition of formaldehyde to the electrolyte under varying conditions,
and as a
result
the
intermediate products, at the

formal-
moment
of
their
formation, combine with
dehyde, producing condensation compounds which do not undergo further decomposition. By regulating
the potential and density of the current the reaction
can at will be checked at a perfectly definite phase of

the reduction.
In the electrolysis of nitro-benzene by this
there were formed
1.
:
method
p-Anhydro-hydroxylamine-benzyl alcohol,
,
'
H n /NH.OH *\CH OH
3
'
which may also be directly prepared by the action of formaldehyde on phenyl-hydroxylamine.

2.
Methylene-di-p-anhydro-amido-benzyl alcohol,
F /NH.C.H.CH^ CH '\NH.C H CH L
6 4
Ztschr.
f.
Elektroch.,
4, 428.
a condensation
69
product of formaldehyde and aniline.

of p-nitro-toluene
is
The behavior
different, since in
this case, the p-position
being occupied by the nitrois
group, an analogous reaction with formaldehyde

impossible.
While p-nitro-toluene
solution smoothly into
is
converted
in
an alkaline
azo-toluene and in an acid
solution into p-toluidene, nearly equal quantities of
two
different products are obtained in the presence of

viz.
:
formaldehyde,
1.
p-Dimethyl-toluidene.
2.
Dimethylene-ditoluidene.
nature of the reaction
is is
The
such that the reduc-
tion proceeds until p-toluidene
formed, and not
till
then does a condensation with formaldehyde occur:
2C
H .CH .NH
4
8
+ 2CH =
2
2H,O.
The dimethylene-ditoluidene thus formed on

reduction
further
breaks
up
into
dimethyl-toluidene
and
toluidene, the latter becoming again subject to the
action of the formaldehyde
CH
,C 6
.N(CH
8) a
f 4H=* + H N.C.H CH
s
i
state of equilibrium exists
between the dimethyl-
7O
ELECTROLYSIS AND ELECTROSYNTHESlS
toluidene and the dimethylene-ditoluidene at the end

of the operation.
further application
of
Gattermann's reaction
has been found in the case of aromatic nitramines*
which
phuric
if
reduced
give
in a
concentrated solution of sul-
The amido-phenol derivatives. process can also be applied to the esters of nitroand results in the formation of carboxylic acids
acid
8
amido-phenol-carboxylic esters.
Nitro-sulphonic
acids
*
show a
similar
behavior,
while the
toluidenes,
p-nitro-
or p-nitroso-alkyl-anilines*
case
of
and
to
as
the
may
be,
are
reduced
p-amido-derivatives
their
alkylated
m-oxy-anilines or
homologues.
nitro-derivatives of the quinoline* series
similar
The
show a
of
deportment
benzene.
to
that
of
the
derivatives
Nitre-aldehydes which Gattermann

^
has also chosen
thorough investigation, conduct themselves differently from the nitro-compounds thus

for
the subject
of
far described.
If
the nitro-aldehydes are reduced there are formed the free aldehyde-phenyl-hydroxylamines, or
either
German
Pat., 77806.
Ibid.. 78829.
Ibid.. 79865.
Ibid., 81621.
Ibid...
81625.
Ibid., 80978.
Chem.
Ber., 29, 3037;
German
Pat. 85198.
condensation products of the same with
71
the nitro-
aldehyde present.
The nitro-benzylidene-aldehydo:
phenyl-hydroxylamines are thus formed
+ 4H = H + C H '\NHOH.
'
2.
H /CHO
/O\ \N CH.C H .NO

6
4
II
p-Nitro-benzylidene-p-aldehydo-phenyl-hydroxylamine y
HC
I
# \
C.CHO
CH
II
HC
/ ^
I
C.NO,
CH
'
HC
V/
CH
HC
_N
/o\ --
CH-
\ c //
CH
may thus be prepared from p-nitro-benzaldehyde. From m-nitro-benzaldehyde an analogous compound

is
formed.
1
Gattermann,
ketones,
on reducing several aromatic
nitro-
obtained the
corresponding derivatives of
amido-phenols.
By
a similar treatment amido-oxy-acetophenone,
Chem.
Ber.
29, 3034.
72
is

formed from m-nitro-acetophenone ; amido-oxy-ben
zophenone,
from m-nitro-benzophenone ; and amido-oxy-phenyl-ptolylketone,
from m-nitro-phenyl-p-tolylketone. The process which Straub employs to prepare hydrazo-compounds from nitro-hydrocarbons is yet to
'
be mentioned.
is
The
chief feature of his experiments
that
the
original
material
and
all
intermediate
products are retained in solution during the electrolysis by the selection of a suitable solvent, and the
hydrazo-compounds are withdrawn from the action

the current by precipitation.
of
Straub attains this end by subjecting the nitro-
hydrocarbons to electrolytic reduction in a solvent made a conductor by the addition of potassium hydroxide.
The quantity
keep
of the liquid used
must be
sufficient to
in solution the azo-
and azoxy-com-
pounds corresponding to the nitro-hydrocarbon. 3 Noyes and Dorrance have applied Gattermann's
reaction to p-nitraniline and
some other substances.

sulphate
In this
way they obtained p-diamido-benzene

1
German Patent, Chem. Ber., 28,
79731.
2349.
from
p-nitr aniline,
73
acid
p-amiô-phenol-sulphonic
from p-nitro-phenol, and p-amido-phenol-sulphonic acid from p-chlor-nitro-benzene.
They
explain the reactions in the following manner:
C -' H
(
'
"
'CH,
S
C H
'
'\CH,OH,
/NO, CH
3
\NH
/NO,
The phenomena
1
of
the
reduction
of
nitro-com-
pounds in alkaline solution have been investigated by In his first experiments he used nitro-benzoic Lob. It was found that m-nitroacids and nitro-phenols.
and p-nitro-benzoic acid were smoothly reduced to the corresponding azo-acids, while the o-acid under similar
conditions yielded o-azoxy-benzoic acid and o-hy-
drazo-benzoic acid.
The
nitro-phenols
in
alkaline
solutions gave amido-phenols.
The
fact that the reduction in
an alkaline solution
may be
carried as far as the azo-phase has been

1
made
Zeitschr.
f.
Elektroch., 2, 529: ibid.,
3, 45.
74
use of by
of the
Lob
in
performing a direct electrosynthesis
mixed azo-bodies and azo-dyes.
The com-
ponents of the compounds desired,
in exactly equi-
molecular proportions, are reduced under conditions
which render the union of the two residues possible. In this way azo-compounds are obtained in which the
substituents
are
in
the
meta-position
compounds
which could not be prepared by the Griess method. Kaufmann and Hof a subjected m-nitro-benzaldehyde to
reduction in alkaline solution and
thus
obtained m-azo-benzoic acid as the principal product
and m-azo-benzyl alcohol as a secondary product.

the
electrolysis
By
ob-
of
m-nitro-benzaldehyde
Lob
tained m-azo-benzoic acid and m-azo-benzyl alcohol

as secondary products. of a
acid,
The
chief product consisted
mixed azo-body, azo-m-benzyl-alcohol-m-benzoic
m - CH OH.C H
3 6
.N
N.C,H .COOH
4
- m.
of
The
Gesellschaft
f.
Chem.
Industrie
Basel*
prepare orange dyes by using as cathode fluid an alkaline solution of the yellow condensation products
of p-nitro-toluene-sulphonic acid,
CH
1
'-
H '\S0 H
3
Ztschr.
f.
Elektroch., 4, 530.
1896.
Chemiker Zeitung,
Ztschr.
f.
Elektroch., 4.
English Pat., 22482.
?5
(namely, a mixture of azoxy-stilbene-disulphonic acid,

azo-stilbene-disulphonic
acid,
and
dinitro-stilbene-
disulphonic acid).
The
until
reduction,
however, must not be continued

result.
amido-compounds
are
'
Other
reduction
u.
processes
used
by the
or
Badische
Aniline
Sodafabrik
for
making
naphthazarine
from
aâIn
in
dinitro-naphthalene
aâ^-dinitro-naphthalene.
first
these cases intermediate products are
formed
the electrolytic reduction, and these are transformed

into naphthazarine
by heating.
2
The
of
Basel
company
of
mentioned
above
obtains
triphenyl-methane dyes by the electrolytic reduction

nitro-leuco-bodies result
4
the type
NO
(4)
H .CHR
4
a,
(i)
which
(4)
in
the
formation
ofthecarbinoles
NH-C,H
Ahrens
py.ridine
4
.COH.R,
accomplished the electrolyut reduction of
and the derivatives of pyridine, and obtained piperidine from pyridine, and pipecoline from picoline.
In
these
electrolyses lead cathodes and
10$
solutions of sulphuric acid were employed.

If
strong sulphuric acid and a platinum cathode

Pat., 79406.
Pat., 84607. In these formulae A" denotes aromatic radicals with primary, secondary, or tertiary amido-groups, or with hydroxyl-groups.
3
German German
Ztschr.
f.
Elektroch., 2, 577, 580.
were used there was formed a substance containing nitrogen and sulphur, the chemical nature of which
has not yet been determined.
on electrolytical reduction give piperylhydrazines, ammonia is split off, and piperNitro-piperidines

idine
is
in part
regenerated.
ammonia, and <*-pipecoline a-methyl-piperylhydrazine. In a like manner from nitroso-aldehyde-copellidine
Nitroso-a-pipecoline gives, in addition to
(CH
.C 2
.C 6
H N.NO)
8
:
there
is
formed ammonia, a
3
large proportion of copellidine
(CH
.C a
.C 5
NH),
and also the corresponding methyl-ethyl-piperylhydrazine:
CH
Quinoline
in
.C a
.C 6 H 8
:N.NH
a.
10$ sulphuric-acid solution gave a polymeric dihydro-quinoline and tetrahydro-quinoline

(Ahrens
').
Quinaldine, likewise in sulphuric-acid solution, gave
dihydroquinaldine and tetrahydro-quinaldine.

Electrolytic Oxidation of Nitro-compounds.
influence which the nitrosois
6.
The
exert on the other substituents
and nitro-groups especially shown in
oxidation
reactions,
which here occur much more
readily than in the case of
compounds which have not
Chem.
Ber., 29, 1123.
been nitrated.
piperidine
3
TJ
By the
'
electrolytic oxidation of nitroso-
Ahrens
obtained
dipiperidyl
(C 10 H ao N Q ).
Elbs
secured a satisfactory yield of p-nitro-benzyl
alcohol from p-nitro -toluene.
The
introduction of hydroxyl-groups into azo-ben3
zene, which
accomplishing, If azocan also be regarded as an oxidation process.
Heilpern
succeeded
in
benzene be dissolved
in as small a
quantity of cone,
sulphuric acid as possible and this solution be subjected to electrolytic action at the anode, chiefly tetra-
oxy-azo-benzene
is
formed
2
13
H ON =
10 4 a
(OH) C H,N
6 4
NC H (OH)
6
8
According to a patent benzoyl-sulphone-imides can be prepared by the electrolytic oxidation of toluenesulphone -amides ;
for
example,
o-benzoyl-sulphone:
imide, or saccharine, from o-toluene-sulphone-amide
"""XCH,
'+
C61
p-nitro-o-
The corresponding p-compound, and

toluene-sulphone-amide,
.
NO
show a
.CH
.C 9 H,.SO,NH,
similar behavior.
Yellow mordant dyes are obtained by the Badische

Aniline u. Sodafabrik
1
by the oxidation
of aromatic
Ztschr.
Ibid.
t
f.
Elektroch., 2, 579.
522.
2,
Ibid., 4, 89.
4
6
F. v.
Heyden's Nachfolger, German

Pat., 85390.
Pat.. 85491.
German
78
oxycarboxylic acids in sulphuric acid solution, by the
use of
ammonium
persulphate or by electrolysis.
whole
series of acids
have been investigated: m-dioxy-
benzoic acid, gallic acid, tannin, the ethyl ester of gallic

acid,
gallamide
((OH) C
s
H CO.NH
a
2 ),
o-,
m-,
and
p-oxy-benzoic acids, cresotinic acid, etc.
7.
Electrolysis of Alkaloids.
Caffeine,
Theine,
H NO
]0
4
On
permitting the
electric current to act for several
days on a solution
of caffeine acidified with sulphuric acid
Pommerehne
obtained amalic
acid,
formic
acid,
ammonia, and
methylamine.
Atropine,
1T
H NO
23
From
the neutral sulphate of
atropine crystallized atropine

at the cathode,
is
gradually precipitated
while at the anode carbon dioxide,
carbon monoxide, oxygen, and nitrogen are evolved.
The
acid sulphate behaves in a similar manner, but
the evolution of nitrogen was not observed.
Opium.
If
opium
is
subjected to the action of the
electric current the acid goes to the
cathode and the
base to the anode.

dicarboxylic acid)
Thus meconic
was found
2
acid (oxy-pyrone-
at the positive pole
and
morphine (C 17 H
1
17
NO(OH) )
Donate Tommasi: Trait6 d'Electrochimie, Th6orique

Arch.
f.
et Prac-
tique, Part 4, 788.

2
Pharm., 235,
364.
79
Bourgoin, however, showed that the reaction does not take place smoothly, but is always accompanied
by secondary
Morphine.
solution of
reactions.
Pommerehne,
by the
electrolysis of a
morphine acidified with sulphuric acid, obtained, after a few days, crystals of oxy-dimorphine
sulphate.
The
solution
became dark-colored.
Codeine (methyl-morphine), C 17
H NO(OH)O.CH,.
17
On
is
the electrolysis of the neutral sulphate hydrogen

is
evolved, codeine
precipitated,
and the solution
sulphate undergoes more and carbon dioxide, carbon complete decomposition, monoxide, oxygen, and nitrogen are split off.
turns
brown.
The
acid
Cotarnine,
ia
H NO
1B
4.
This compound
is
converted
by the
electrolytic
hydrogen quantitatively into pure
hydro-cotarnine,
(C,,H, t NO,),.H,0.
Quinine,
ao
H NO
a4
a
Although the
neutral
sulis
phate
is
a very poor conductor, the acid sulphate
decomposed into carbon dioxide, carbon monThe color of the solution oxide, and nitrogen.
readily
changes to a dark brown.

3
Cinchonine,
nitrate of this
19
H N
2Q
O.
On
the electrolysis of the
compound an
oil-like
body appears
at
the anode.
1
Arch.
f.
Pharm., 235,
Pat., 94949.
3*4.
*
3
German
Journ. prakt. Chem., 72,
73.
80

1
Strychnine,
suffers
31
H NO
aa
a
a.
but
little
change.
The The
neutral
solution
sulphate
becomes
off,
slightly colored,
hydrogen and oxygen are given
and
crystals of strychnine collect on the cathode.
The
that in
acid sulphate behaves in a like manner, except

its
case the formation of carbon dioxide and
carbon monoxide as well as oxygen and nitrogen shows that a part of the substance undergoes complete
decomposition.
In strongly acid solutions the split-
ting off of nitrogen does not occur.

1
Brucine,
C
is
83
H NO
26
a
solution
of
is
the
neutral
sulphate turns red and the sulphate
decomposed.
Hydrogen
pole.
evolved at the negative pole, but the
brucine completely absorbs the oxygen at the positive
The
acid salt
is
very energetically decomposed,
becoming
first
red and then brown.
At the anode
carbonic-acid gas, carbon monoxide, oxygen, and ni-
trogen escape.
Besides the gases mentioned, the above alkaloids
break up into other products, principally complicated
compounds containing
8.
nitrogen.
Camphor and
Glucosides.
Terpentine hydrochloride.
trolysis in
This compound on elecin

10
the melted condition or
an alcoholic
16
acetic-acid solution gave camphor,
H O
(Richard-
son
).
1
English patent, 3555.
Salicine,
salicylic
81
1S
H OV
18
Salicine
on electrolysis yielded
1
aldehyde and
salicylic acid
(Tichanowitsch
).
9.
Electrolysis of Blood.
The
defibrinated blood of a
dog was submitted
to
electrolysis
by Becquerel.
He made
use of platinum
electrodes and a current furnished
by a battery
of
three Daniel
cells.
At the
negative pole he observed
the following phenomena:
The blood became brown and
alkaline,
it
and conpossessed
tained neither white nor red corpuscles;
the property of gradually dissolving blood-corpuscles
and had the odor of putrid meat.
At
the positive pole undecomposed and partially

in
decomposed blood-corpuscles were present

quantities.
large
The
fluid
gave a precipitate of albumen
with
nitric acid,
mercuric chloride, and lead acetate.
10.
Electrolysis of Albumen.
When
Dumas
an albumen solution was electrolyzed by and Prevost, under conditions similar to those
used by Becquerel for blood, the alkali metal went to

the negative pole, hydrogen was evolved, and acetic
and phosphoric acids appeared at the positive pole. The result of this is that the albumen is coagulated
1
Chem.
Centralblatt, 1861, p. 613.
82
ELECTROLYSIS AND ELECTROS YNTHES1S
at the negative pole (by the alkali present), while at
the positive pole the solution remains clear.
As Lassaigne
solution
of
salts
is
has shown, pure albumen in aqueous
a non-conductor of electricity; the addition

is
or acids
therefore necessary in
its
elec-
trolysis.
ii.
Electrolysis and Electrosynthesis with Alternating Currents.

the current
If
the polarity of
does not change
altogether too rapidly, since oxidation and reduction
occur successively at
each pole,
it
is
possible
to
accomplish
electrolyses
and
electrosyntheses
with
alternating currents.
Experiments with this end in

1
view have been made by Drechsel. Dehydration is The a case of simultaneous reduction and oxidation.
supposition that in living organisms carbamide
is
prooff
duced from ammonium carbamate by the splitting

of water
prompted Drechsel
3
to
make experiments
in
this direction.
If
an aqueous solution of ammonium carbamate was electrolyzed with a current from a battery of 4-6
Grove elements and platinum electrodes were used, carbamide was obtained independently of the elec-
Journ. prakt. Chem., 22, 476.

Ibid.
trode
material
83
when
alternating currents were
em-
ployed.
The
reactions are supposed to be either
H
II.
O,
NH .CO.ONH,+ 2H
2
=r
NH
.CO.NH,
+ H O,
a 2
or
I.
II.
NH .COONH + 2H = NH .CONH + H O, NH .CO.NH + O = NH .CO.NH + H.O.

2 4
The
Gerdes
fact that the
attacked, with the formation of platinum

'
platinum electrodes were strongly salts, caused
to investigate the platinum bases.
As
the
principal product he found a
compound
to
which he
gave the following formula:

J
/ONHJ \ONH
3
1 t
/NH
XNH
is
NH,0\ L
NH 0/
3
and the chloride of which

tion
said to
have the composi-
CINHXp/NH, NH C1 >J: Q L1*^

3
NH,CI
Ha
Gerdes also examined the nitrate and sulphate of

this base.
In the course of further researches

that
Drechsel found
were used platinum was present in the electrolyzed fluid. Copper when used as electrode showed a similar behavior; lead was less
alkaline solutions
1
when

Ibid., 29, 229.
84
ELECTROLYSIS AND ELECTRO SYNTHESIS
attacked, gold but very slightly, and palladium not

at all.
The formation
in living
of the phenol ester of sulphuric acid

is
organisms
supposed,
like
carbamide, to be
this into consid-
the result of dehydration.
Taking
eration, Drechsel carried out the following experiment:
magnesium carbonate was mixed with an equal volume of a solution of

solution of acid
A saturated
magnesium "sulphate and the mixture was saturated

with commercial carbolic acid.
1
was electrolyzed for thirty hours with alternating currents and platinum electrodes were used, the following products were obthis
When
solution
tained:
1.
^-Diphenol.
Pyrocatechin.
7. 8.
Succinic acid.
2.
3.
Malonic acid
(?).
(?).
4.
Hydroquinone. Phenol ester of

phuric acid.
9. n-Valeric acid
sul-
10.
n-Butyric acid
(?).
5.
Oxalic acid.
n. Some cyclohexanone," C H O.
6
10
6.
Formic
acid.
According to Drechsel the formation of the phenol

ester of sulphuric acid
is
probably represented by the
following equations:
I.
II.
C C
H OH+HO.SO H+O=C H .OOSO H+H,O, H .OOSO H + 2H = C H .SO H + H O.

6
8 6
Journ. prakt. Chem.,

Jbib.
t
[2] 29, 229.
[2] 38, 67.
Later Drechsel
'
8$
electrolyzed normal capronic acid
with alternating currents.

contained, in a volume of 3
acid as
The
electrolytic solution
liters,
200
g. of
capronic
magnesium
salt
acid
magnesium
carbonate.
and was nearly saturated with Platinum electrodes were
used.
At
the end of the experiment the following

identified in the solution:
compounds could be
1.
Valeric acid.
5.
Adipic acid.
2.
3.
Butyric acid.
6.
7.
Oxy-capronic acid.
Glutaric acid.
Oxalic acid.
Succinic acid.
4.
In a
still
later research
on the electrolysis of pheno

2
with alternating currents Drechsel

sulphuric acid, dioxy-benzenes, a
detected phenylof acids of

oil
number
the fatty acid series, arid in addition to these an
which he
identified as hydro-pheno-ketone,
/\
H,C
CH,
C
I
O
,
H,C
\/
CH,
CH,
and whose phenylhydrazine compound he was able to
isolate.
Drechsel regards the hydro-pheno-ketone as
the origin of the fatty compounds formed.

1
By
the

..
3$, 6$.
86
ELECTROLYSIS
AND ELECTROSYNTHESIS.
compound
up
capronic
into the acids and
direct addition of water to this
acid results, and this then breaks
other decomposition products mentioned above.
critical
review of the subject-matter which has
here been presented will bring out, concerning the

electrolysis
and
electrosynthesis
of
organic
com-
pounds, several important points which promise to be of great assistance, at no very distant date, in connection with future research in the field of organic
These points may be summarized as follows: the oxidation reactions which occur in the
chemistry.
electrolysis of acids of the aliphatic series, the reduc-
tion reactions in the case of the aromatic series, and,

lastly,
the reactions involving substitutions, concern-
ing which but few researches have been published.
Of these the
Since
first is
in all
apparently the most promising. the experiments which have thus far
been made the dependence of all reactions upon current density, temperature, and concentration is
clearly
evident,
the
attention
of
experimenters
is
again called to the importance of exact data con-
cerning the conditions of experiment.
AUTHORS.
PAGE
Aarland
28
Ahrens
Alessi.
n,
46, 75, 76, 77
25
2,
*
Almeida
Balbiano
Bartoli
7,
4
25
13, 51, 52
Bauer
Becquerel
Berthelot
3,
18
81
44, 45,
13, 14, 18, 25, 26, 27, 28, 29, 32, 44, 56, 57,
49
79
Bourgoin
Brazier
24
8, 13,
Brester
24, 25, 28, 56, 58
Brown
Buff
12, 30, 34, 35, 37, 40, 42, 44, 58
44
20, 25, 47, 51, 52, 53, 57
53
6,
Bunge
Christomanos
Classen
25, 31
Clement Connel
64
4
2,
Deheran
Despretz
18
Destrem Dorrance
Drechsel
59
72
82, 83, 84, 85

81
18
Dumas
Dupre
87
88
A UTHORS.
PAGE
Elbs
tard
5,6, 19, 36, 63, 77

53
Pulsing Friedel
62
10,
40
Gattermann
Gay-Lussac Gerdes
Goppelsroeder Gossleth
Guthries
63, 64, 66, 67, 68, 70, 71, 72
45
83
60, 62
24
37,48
2, 3,
Habermann Hamonet Haussermann

Heilpern
20 63
77
Hemptinne Henderson Herz

Hittorf
u
40
5,
48 74
9, 30,
Hof
Hofer
31
44
45
Hof man n
Huntington
Jahn
Jaillard
3,
15,
20
2
Jovitschitsch
13,
14
Kauffmann Kekule
36, 54, 74
12, 16, 26, 30,
:
42
18
Kemp
Kendall
.'
63 48
63
14
82
61
Kolbe
12, 15, 18, 19, 23, 24, 27, 32, 37, 44,
Koppert
Lapschin
Lassaigne
Liebmann Lob
Losanitsch
6, 16, 57, 63, 66,
68, 73, 74
13,
14
Luckow
46
A UTHORS.
Ludersdorf
89
4
2,
Maquenne
Mattenci
n
56
McCoy
Meissner
n
6
9,
Messinger
Miller
3.
3*. 34
Moore Mulder
Mulliken
12, 42, 43,
19
10
44
Noyes
Papasogli Perkin ,
.
.'
64, 72
7. 13, 5i,
52 45
Perrot
'
2,
46
Pommerehne
Pre vost
Quet,
78, 79
81 2
M
2, 4, 6, 8, 13, 25, 47,
Reboul
27
Renard Richardson
Riche
48 80
4,
10
17
Rohland
Rotundi,
59
12
Royer
Schall,
16, 48, 49
Schields
42
45, 46
Schlagdenhauffen Schonbein
3 58
1
Slawik
Smith
Stone
Straub
8 7
72
14, 81
Tichanowitsch
Tommasi
Voigt
62
Vostmann
Walker
12, 30, 34, 35, 37. 4O, 42, 44, 58
QO
A UTHORS.
PAGE
12, 42, 43,
Weems
Weith
44
4;
55
18
Weizmann Wiedemann
Wilde
Wttrz
11,13
24
INDEX.
PAGB
Acetanilide
Acetic acid...
62
3, 4, 7, 10, 14, 18, 19, 29, 32, 34, 35, 48, 62, 81
Acetic aldehyde Acetic ester Aceto-acetic ester
4, 8,
n,
29, 32, 33, 36,

3, 4, 15,
48
34
43
t
Acetone
Aceto-nitrile
10, 32
46
54
Aceto-phenone
Aceto-phenone pinacone
Acetyl-acetone
1 1,
54
43
43
19
Acety 1-dicarboxylic ester

Acetyl disulphide
Acetylene
Acetyl-malonic ester Acids, aromatic
Acids, fatty
2,
n,
27, 30, 45, 56, 57, 59
43
56
n,
85
Acid superoxides Acid supersulphides

Acrylic acid
16, 1 7
17
28
38, 85
Adipic acid
Albumen
Alcohol aldehydes Alcohols.
. .
bi
g
I, 23,
75
Aldehyde,
see acetic
aldehyde.
/I
Aldehyde-phenyl-hydroxylamines
Aldehyde resin Aldeh\dcs
4
9, 36,
54
Q2
INDEX.
PAGE
Aldol
Alizarine
32
61 78
Alkaloids
Alkyl-oxy-anilines Allocamphoric acid
70
40, 41
Allylene
28
78
Amalic acid
Amides
Amido-acetone
Amido-azo-benzene
43
n
62
Amido-azo-compounds Amido-benzyl alcohol
60
65
59, 63, 75
Amido-compounds
Amido-cresol-monosulphuric acid Amido-cresotinic acid
64
64
Amido-hydroquinone
Amido-naphthalene-sulphonic acid
62
65
71
Amido-oxy-acetophenone
Amido-oxy-benzophenone
Amido-oxy-phenyl-p-tolylketone
72
72
Amido-phenol-carboxylic esters
70
6^, 66, 70, 71, 73
Amido-phenols
Amido-phenol sulphate
Amido-phenol-sulphonic acid
Amido-salicylic acid
,
63
64, 73
64
Amines
46
Ammonium
carbamate
16,
82
Anhydride, formation of
Anhydro-hydroxylamine-benzyl alcohol
Aniline
Aniline black
45, 59, 60, 61, 62, 63,
29 68
69
60, 61
Aniline dyes
60, 62
Anthraquinone
Aristol
55, 60, 61
6
78
73
63, 77
Atropine
Azo-acids
Azo-benzene
INDEX.
93
PAGE
Azo-benzoic acid
74
74
Azo-benzyl alcohol Azo- m-benzyl-alcohol-m-benzoic acid
74
59, 63, 72, 74
Azo-compounds
Azo-dyes
Azo-stilbene-disulphonic acid
74
75
Azo-toluene
69
73
63, 72
Azoxy-benzoic acid
Azoxy-com pounds
Azoxy-stilbene-disulphonic acid
75
33, 35, 36, 54, 57, 67,
Benzaldehyde Benzene
Benzene-phenylene-diamine
68 45
62
54
Benzhydrol Benzidene
Benzile
Benzilic acid
63
55
55
55, 56
Benzoic acid
Benzo-nitrile
47
77
Benzoyl-sulphone-imides
Benzylamine
Benzyl-cyanide
Benzylidene compounds
47
47
67
,
Benzylidene-phenyl-hydroxylamine
Benzylidene-tolyl-hydroxylamine
67
67
35, 42, 43,
Benzyl-malonic acid
58
81
Blood
Brom-anilines
66
Brom-maleic
acid.
30
6
...
Bromoform
Brucine ....
80
20
Butane
Butyl alcohol
4
24
20, 34, 84, 85
Butylene
Butyric acid
Butyric ethyl ester

Butyric isopropyl ester... ,,,,
,
34
21
94
INDEX.
PAGE
Caffeine
78
Campholytic acid
Camphor
Camphoric acid Camphothetic acid Cane sugar
Capronic acid.
40 80
40, 42
40
8
17, 24, 85, 86
Capronic amyl ester

Capronic ethyl ester
Caprylic acid
24
34
17
Carbamide
Carbinoles
Chlor-acetic acids
84
75
4
7
,
Chloral hydrate
Chlor-anilines
66, 67
.>
Chlor-nitro-benzene..
73
6
Chloroform
Chrysaniline
62
79
58
Cinchonine
Cinnamic acid
Cinnamic aldehyde
Citraconic acid
4
28
Codeine
Collodion
Copellidine Cotarnine
Cresotinic acid
79 9
76
79
78
Crotonic acid
40
32, 33
Crotonic aldehyde
Cyan-acetic acid
19
Cyan-acetic ester
43
44, 46
Cyanogen Cyanogen compounds
44
84
Cy clohexanone
Decahexane-dicarboxylic acid
38
17, 24
Decane
Dehydration
82
INDEX.
Dextrine
Diacetyl-succinic ester
95
9 43
72
Diamido-benzene sulphate
Diamido-cresol.
64
64
59
Diamido-phenol
Diazo-amido-compounds
Diazo-compounds
Dibenzyl-succinic ester
59 35
Dichlor-acetone
10 43
Dicyan-succinic ester
Diethyl- ethane-tetracarboxylic ester
43
39,
Diethyl-malonic acid
Diethyl-succinic acids
40
39
76
76
Dihydro-quinaldine
Dihydro-quinoline Di-isobutane
24
Dimethyl-dithiocarbamic acid
Dimethylene-ditolidene
Dimethyl-ethane-tetracarboxylic ester Dime thy 1-malonic acid
Difnethyl-pyrazine, ketine
49 69
43
39,
40
n
38
Dimethyl-succinic acids
Dimethyl-toluidenes Dinitro-benzene
Dinitro-naphthalenes
Dinitro-stilbene-disulphonic acid
69 64
75
75
D in itro- toluene
Dioxy-anthraquinone
Dioxy-benzenes
Dioxy-benzoic acid
64
55
85 78
Diphenol
84
53
60, 61
Diphenyl
Diphenylamine
Dipiperidyl
77
Disulphides Dithionic acids

Di-thymol-di-iodide
,
47
17
,
, .
96
INDEX.
PAGE
Ditolylamine
60
17
Dodecane
Dodecane-dicarboxylic acid
38
60, 62
Dyes, aniline
Dyes, orange
Dyes, triphenyl-methane Dyes, yellow mordant
Esters
74
75
77
36, 38, 39
*
Ethane
Ethane-hexacarboxylic ester
Ethane-tetracarboxylic ester Ethyl alcohol
2, 4,
u,
15, 16, 18, 19, 29
43 43
i, 2, 3, 5, 13, 14, 34,
39 46
Ethylamine
Ethyl-crotonic acid
40
2, 1 8, 20, 27, 32, 36, 42,
Ethylene..
45
19
Ethylene cyanide
Ethylene glycol
Ethyl-glycolic acid
36
4 38
...
Ethylidene oxy-ethyl ester
Ethyl-malonic acid
Ethyl-malonic ester
Ethyl-succinic ester
43
35
4,
Ethyl-sulphuric acid
Ethyl-tartaric acid
48
33
Formaldehyde
3, 31, 32, 33, 67, 68,
69
14
Formamide
Formic acid
6, 7, 8, 10, 12, 14, 18, 31, 32, 33, 47, 48, 78,
84
4
14
Formic
ester
Formyl chloride
Fumaric acid
Furfurane
30, 42
39
78 78 78
6, 7, 8
Gallamide
Gallicacid
Gallic ethyl ester
Glucose
Glucosides
Glutaric acid
, . ,
80
27, 28, 38, 85
INDEX.
Glyceric acid
Glyceric-aldehyde
Vp
^FNIVCTKWV
7>
* * *
33
7
Glycerine
Glycolic acid
^ÂUKO^^:,
7
6, 7, 25,
6, 7,
31, 34, 36
6, 7,
Glycols
35
8
Grape sugar
Gum arabic
Heptylic acid
9
17
20, 22
Hexane
Hydracrylic acid Hydrazo benzene
32 63
73
63, 72
Hydrazo-benzoic acid
Hydrazo-compounds
Hydrobenzoln
Hydrocarbons
Hydro-cotarnine
35, 36, 54
12, 37, etc.
79
44, 45, 59
Hydrocyanic
acid
Hydro-phenoketone
85
62, 84
,
Hydroquinone
Hydroquinone ether Hydroxylamine derivatives

lodoform
lodo-propionic acid
53
64-68, 71
......
37 34
Isobuty 1-acetic acid

Isobutyl-acetic ethyl ester
34
20,
Isobutyric acid
22
22 22
Isobutyric-isopropyl ester
Isohexane
Isohydrobenzoin
Isonitroso-acetone
35, 36, 54
1 1
Isopropyl alcohol
Itaconic acid
21,
22
28
Ketones
Lactic acids
10,
54
32, 36
Laurolene
Leukaniline
41
62
,
Maleic acid
.30,
42
98
INDEX,
PACK
Malic acid
28, 33
Malonic acid
26, 34, 38, 42, 58, 84
Malonic ester Mandelic acid

33, 35
1
43
36
g
8
Mannite
8,
Mannonic
acid
,
Meconic acid
Mercaptans Mesaconic acid
c
78
.47, 53
28
3,
Methane
Methyl-acetic ester
Methyl-acrylic acid
13 f 14
18
40
3
i,
, ,
Methylal
Methyl alcohol
2, 14, 33
Methylamine
Methyl-aniline
78
60, 61
Methyl-diphenylainine
61
Methylene-di-p-anhydro-benzyl alcohol
68
15
Methyl ether
Methyl-ethyl-piperyl-hydrazine
76
18
Methyl-formic ester
Methyl-glycolic acid.
33
,
Methyl-hydrocinnamic ester Methyl-malonic acid
35
38,
43
7g
76
Methyl morphine
Methyl-piperyl-hydrazine
Methyl-sulphuric acid Michler's ketone
-3,
47
54
Monobrom-acetone
n
53 19
Monobrom-benzene
Monochlor-acetic acid
Monochlor-acetone
10
55
78, 79
Monoxy-anthraquinone
Morphine
Naphthazarine
75
60, 61
Naphthylamine.
Naphthylamine
violet
,..,,.,,,
60
INDEX.
Nitramines
Nitraniline
Nitriles
99
70, 72
64, 73
46
72
56, 70, 71
Nitro-acetophenone
Nitro -aldehydes
Nitro-alkyl-anilines
Nitro- alkyl-toluidenes
..
,
70 70
65
71,
Nitro-arni no-benzyl -toluene.
Nitro -benzaldehydes Nitro-benzene
74
63, 64, 66, 67, 68
Nitro-benzene-sulphonic acid
Nitro- benzoic acids
64
64, 67, 73
Nitro-benzophenone
Nitro-benzyl alcohol
72 77
71
7
Nitro-benzylidene-aldehydo-phenyl-hydroxylamine
Nitro-carboxylic acids, esters of Nitro compounds, oxidation of
Nit ro-compounds, reduction of
76
63
, . *
Nitro-ethane
37
37, 65, 76
Nitro-groups
Nitro-hydrocarbons
Nitro-isophthalic acid
72
64
,
Nitro-ketones
Nitro-leuco-bodies
56, 71
75
Nitro-naphthaiene-sulphonic acid
Nitro-phenol.
65
63, 73
Nitro-phenyl-tolylketone
Nitro-piperidines
72
76
".
Nitroso-aldehyde-copellidine
Nitroso-alkyl-anilines
Nitroso-alkyl-toluidenes,
76
70
70
76
76
Nitroso-groups
Nitroso-pipecoline Nitroso-piperidine
76
Nitro-sulphon ic acids
Nitro-terephthalic acid
70 64
64, 65, 67, 69, 70, 77
Nitro-toluenes
1OO
INDEX.
PAGE
Nitro-toluene-sulphone-amide
Nitro-toluene-sulphonic acid
Nitro-toluic acid
77
74
64
67
6
Nitroxylene
Nosophene
Octane
Octylene
CEnanthylic acid
Olefines
24
17
24
23
Oleic acid
17
78
8,
Opium
Oxalic acid
10, 12,
25, 42, 84, 85

35, 36
Oxy-acids
Oxy-anilines
70
78
Oxy-benzoic acids.
Oxy-butyric acids
32
85 78
Oxy-capronic acid
Oxy-carboxylic acids
Oxy-dimorphine sulphate
Oxy-isobuty ric acids
.
79
,
. .
32
78
Oxy-pyrone-dicarboxylic acid Phenol

Phenol-sulphuric acid
Phenyl-acetic acid
51, 61, 84, 85
84
58
,
Phenyl-chloramine
Phenyl-disulphide
67
53
62, 63
Phenylene-diamine
Phenyl-ethylamine
Phenyl-glyceric acid
47
33
64, 66, 67, 68
Phenyl-hydroxylamine
Phenyl-lactic acid
33
53
Phenyl-mercaptan
Phenyl-sulphuric acid
85
,
Phenyltolylamine
Phthalic acid
Picoline
Picric acid
60
16, 42,
57
75
52
INDEX.
10 1
PAGE
Pipecoline
Piperidine
75. ?6
75, 76
Piperylhydrazines
76 45
Potassium cyanate Potassium cyanide

Potassium ferricyanide Potassium ferrocyanide
Potassium-isoamyl sulphate.
Potassium-trichlor-methyl sulphate
Potassium-trichlor- methyl sulphonate
45
46
44 45
>
48
47
48 48
20, 34, 36, 37
Potassium xanthate
Propionic acid
Propionic aldehyde
Propionic ethyl ester
Propio- nitrile
32
34 47
4, 22
Propyl alcohol
Propylamine
Propylene
Propylene bromide
Prussian blue
20, 21, 22,
47
28
21, 22
45,
46
II
Pyrazine
Pyridine
75
Pyrocatechin
Pyrotartaric acid.
84 27 76 79
...70, 76
61, 62
Quinaldine
Quinine
Quinoline
Quinone Racemic acid

Resinous bodies
Rosaniline
Saccharic acid
Saccharic aldehyde
,
33
7, 21, 32, 33, 52,
58 62
8 8
Saccharine
Safranine
Salicine
Salicvlic acid
77
62
81
81
102
INDEX.
fAGR
Salicylic
aldehyde
7, 38,
81
Sebacfc acid
40
43 47 43
Sodium-diethyl-malonic ester Sodium-isethionate

Sodium-methane-tricarboxylic ester
Sodium-nitro-prusside Starch
46
9
Strychnine Suberic acid

Succinic acid
80
38
26, 30, 34, 37, 38, 84, 85
8
Sugars
Sulpho-benzoic acid
57
Sulpho-compounds Tannin
Tartaric acid
....
11
,
47
78
29, 32
Terpentine hydrochloride
Tetracetyl-ethane
80
,
43
17
Tetradecane
Tetraethyl-succinic acid
39
Tetraethyl-thiuramdisulphide
49
76
Tetrahydro-quinaldine
Tetrahydro-quinoline
Tetra-iodo-phenol-phthalein
76
6
54
38, 39
Tetramethyl-di-amido-benzophenone
Tetramethyl-succinic acid
Tetraoxy-azo-benzene.
Tetraphenyl-erythrite
77
55
Theine
Thio-acetic acid
78
19 57
Thio-benzoic acid
Thiophene
49
,
Thymol
Toluic acids
6
77
Toluene-sulphone-amides
,
61
60, 61,
=
Toluidenes
69
65
Tolyl-hydroxylamines
Tricarballylic ester.
34
INDEX.
103
PAGE
Trichlor-acetic acid
19 19
55
6, 7, 8,
Trichlor-methyl ester
Trioxy-anthraquinone
Trioxy-methy lene
Triphenyl-methane dyes
Undecylenic acid Unsaturated acids
47
75
17
17,
42
39
Unsaturated esters
Unsaturated hydrocarbons
Valeric acids
17, 33,
42
24, 48, 84, 85

,
Valeric butyl ester. ...;
24
34,
Valeric ethyl ester
Xanthogen supersulphide
48
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"
"
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125
STEAM AND ELECTRICAL ENGINES,

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p. 6.)
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Electrolysis and Electrosynthesis of Organic Compounds

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Electrolysis and Electrosynthesis of Organic Compounds

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REESE LIBRARY

Privatdocent in the University of Bonn.

AUTHORIZED TRANSLATION FROM THE AUTHOR'S ENLARGED AND REVISED EDITION

Graduate of the University of Berlin.

ROBERT DRUMMOND, rRINTER. NEW YORK.

AUTHOR'S PREFACE TO THE AMERICAN

IN the two and a half years that have passed since

work, the application of the electric current in organic

chemistry has undergone such a marked development

form could no longer

claim to give an adequate idea of our present knowl-

During these last two years in particular a series of

chemistry have been brought out in rapid

Lorenz to translate the book affords an excellent

that his excellent translation

the attention of his American colleagues to this broad

AUTHOR'S PREFACE TO AMERICAN EDITION.

such a diversity of applications,

hope the author and

a rich reward for their efforts.

work, with the

public, scarcely anything remains to

Dr. Lob has

already said in his prefaces to the

and American editions.

and a complete index, which enhance the value of the book.

Dr. B. B. Boltwood of the Sheffield Scientific

who has had

ness to revise the manuscript, grateful acknowledg-

to the present been carried

out by the employment of other forms

very nature suggests the possibility of solving

synthetical and analytical problems which have as yet

themselves have been undertaken.

This book aims

to give, as briefly as possible, a review of

already been accomplished, and at the same time to

on the electrolysis and electrosynthesis of organic

ELECTROLYSIS AND ELECTROSYNTHESIS OF ALIPHATIC COMPOUNDS.

Propionic acid conclusions

CEnanthylic 20-24 Glutaric acid

KSkule; maleic, brom-malelc and fumaric acids.. 25-31

Butyric ethyl ester

31-33 Succinic ethyl ester

Monobasic oxy-acids. [Mandelic acid Hydrobenzoin, hydrobenzoin.] Formation of aldehydes

ELECTROSYNTHESES OF BROWN AND WALKER.

dicarboxylic acid Disubstituted acids

ELECTROSYNTHESES OF MULLIKEN AND WEEMS.

Diacetyl-succinic ester Dimethylester ethane-tetracarboxylic Diethyl-ethane-tetracar-

Reduction of nitriles Aceto-nitrile n-Propio-nitrile. matic nitriles Benzo-nitrile Benzyl-cyanide.]

ELECTROLYSIS AND ELECTROSYNTHESIS OF

Aniline, electrolytic products of

Electrolytic Reduction of Nitro-Compounds.

of the quinoline series

Nitro-acetophenone benzophenone m-Nitro-phenyl-p-tolylketone p-Nitraniline p-Nitro-phenol Chlor-nitro-benzene

Electrolytic Oxidation of Nitro-Compounds.

Atropine Opium Morphine Codeine Cinchonine BruQuinine Strychnine

Camphor and Glucosides.

Electrolysis of Blood Electrolysis of

Electrolysis and Electrosynthesis with Alternating Currents.

Ammonium carbamate Dehydration. acid Phenol Capronic acid

the electrolysis of inorganic compounds has

already obtained a recognized position in pure and

applied science, the action of the electric current, as