Electro Chemistry For Organic Compounds - 1906 (From Scanned PDF

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ELECTROCHEMISTRY
OF
ORGANIC COMPOTJNT
RD
BY
DR. WALTIIER LOB

Privatdocent in the University of Bonn
AUTHORIZED TRANSLATION FROM THE AUTHOR'S ENLARGED AND

REVISED THIRD EDITION
ELECTROLYSIS AND ELEOTROSYNTHESIS

OF
ORGANIC COMPOUNDS
II. W. F. LOJiENZ, A.M., Pii.I).
{
Graduate of the University of Berlin I
Formerly Instructor of Organic Glwmtetrii in the University of J^nnttylvania (
Z^ramlalor of Lawar-Cohriti "Urinary Analysis^ etc, (
WITH TEN ILLUSTRATIONS
FIRST EDITION
FIKST THOUSAND
NEW YORK
JOHNXWILEY <fe SONS
LONDON : CHAPMAN'& HALL, LIMITED

1906
fe
£19
AUTHOR'S PREFACE TO TIIK THM.'h
GEliMAN EDITION'.
THE great progress which the elerfwIi'-TW *>

compounds has made in the past, f< w \iniv ?*'»$* J- *»•
to rearrange the whole* nut ferial, un«l I** r\pt»
title the extension of the ta.^k whieh the hunK * * J
The theoretical disruîons vvbieh I'urw an n^
the experimental part of eltrtr**Iy-i' ;iie * i f n ii
' tially hypothetical charuetiT, thai the jtn * i**
knowledge of the mechanism of the e|»«r!n«' 4 <* • <
prevent from btdng olheruine. But the ni> * «t $> !• *
trustworthy as aidn in direct ing :tn«i jinnnj'ii?v iu
work; perhaps tliey will fr i»i|iialiy -/ii'u**t • ii!«- * > .
withstanding - the possibilit y ami ju^tihh}<t!it \
views.
The object of the; work IIIH remain''*! flit* » * t r
as in the old form: In giv** a, ronitf He»| , m -,« •
s
been done, and to incite to furl}n r i'(ln|t iit k^« t
I desire here to expre^ in\ thanl*-. tr Hi |,
helped me in looking over the lihruhuv «»n f Jj ,i,l
The second Eiiglinli edit Inn, 4'ofrf*'>j»*ririim* »- i
German edition, will ap|xuir htiortly.
II ii i
BONN, April, 1905.
ii.
3
v
' ' *
TRANSLATORS PRKFA<'K TO SE
AME.RKJAN EDITION.
A NEW edition of Port or f/»!»V Imok nn thin infi»ri

and important subject h:is bwiffit* n*rr»?try, hfcvwM' of flu*
great increase in the past ff»w yivu'.* in t i n * t j t t m i i i f y of nr*vv
experimental niatiina,L Tin* jiufhor IIHN I m i l !iii*f HUM
requirement in his prrwnt work on tin* ''Ml
chemistry of Organic {1<»ni ortnr f,ol> !i?w ^
no -pains to bring the* HihjfH-maft Irifflv up fn *l afr
has ent irely rewritten and rârni tlif* n«if«*riii{ H » to
present it in the host poHîbir form
Two spociul diuptors have* h«-*« ff>
more thorough dlseuHHion of flic t 1111* ,
organic electrochemistry, and nlw* n t*Itapif«r on «'|r<*fri«
«»n-
dosmose. The whole* of ]*nrt I f , nu i*iiMipiltif*riiii*' pronv..:f»ji
and the silent electric (liwlwrg*4, & m»\v.
Complying with fl i p wiVfi of flu* iiiiffmr in t i t I'M n# ; r ) jj|ft
first tr«analation, t l m ori/>;ih;il fi*xf. h:w Mtiinviî I»y tin*
translator an c»lowly ?IH [mîlilr*,
It is hope* I that this inn? relit ion will IJn* wi
cordial reception acconlcwl flir* i*arlii»r «!n*
SPRINGFIELD, OHIO,
CONTENTS.
INTRODUCTION
PART I.
ELECTROLYTIC PROCESSES.
CHAPTER I.
THE OR ETICS .......................................
1. F o r m s o f R e a c t i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Properties of Electrolyt ic Processes ..... ..... .... .
£. Significance of the Velocity of Reaction .............
4. Reaction Velocity and Specific Effect of Reducers and Oxidizers 13
5. Electrode Potential and Reaction Mechanism .......... " 14
6. Electrode Processes . .... ... . ..... ... . , ....... ft
A. C a t h od ic Pr o c e ss e s . . . . . . . . . . . . . . . . . . . . . . ...... 1 R
a. Unattackable and Attackable Cathodes. . ." .' " " " " ' ." .' . . " 18
6. Excess Potential and the Reduction Action. . . " . * ' * * " * 2Q
c. Concerning Substances Reducible with Difficulty. . . . 23
B. Anod ic P r oc e s se s . . . . . . . . . . . . . . . . . . . . . . . . . .
7. Theory of the Reaction Velocity in Electrolytic Processes. " . .* .* " 30
o . D i f f us i o n Th e o r y . . . . . . . . . . . . . . . . . . . . . . . .
6. Osmotic Theory of Electrical Reduction. ..."." . ." . ] . ." " " 34
c. Summary of the Theories. ... ........ .......... 0-
..... * • • • • • • • .
CHAPTER II.
.................... . .........
M B T H OD I C S
•
1. The Cells. . . . . . ........ *
» « . . .. .. .. . .. .. .
. . . . . . . . . . . . .
2. Arrangement of Experiments and Measurements of Potential' " "AA

3. The E l ect r ode s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . **
* *"""** ** ** ** ....... • ol
vii
viii CONTENTS.
CHAPTER III.
PAGE
ELECTBOLYSIS OF ALIPHATIC COMPOUNDS............................................. 54
1. Carbon and Hydrocarbons ..................................................... 54
2. Nitro-derivatives of Hydrocarbons............................................ 56
3. Hydroxyl Compounds............................................................. 57
4. Derivatives of the Alcohols ..................................................... 05
5. Aldehydes, Ketoncs, and their Derivatives............................. 66
a. Aldehydes ............................................................... 66
b, Ketoncs __ ..........................................................,. 00
6. Acids.................................................................................... 75
I. Monobasic Acids, OnH2nO3............................................................. , ............. 77
II. Monobasic Alcohol- and Ketonic Acids............ ,............... 05
a. Alcohol-acids ........................................................... 05
b. Ketonic Acids........................................................... 99
III. Dibasic Acids............................................................... 102
IV. tlnsaturated Dibasic Acids ........................................... 115
V. Folybasic Acids............................................................. 116
7. Ami nee, Acid Arnides, ImidcK and Nitrites ............................. 118
8. Carbonic-acid Derivatives....................................................... 121
9. Sulphur Derivatives of Carbonic Acid....................................... 130
CHAPTER IV.
ELBCTEOLTSIS OF AROMATIC COMPOUNDS .............................................. . . . . 132
1. Hydrocarbons. ....................................................................... 133
2, Nitro- and Nitroflo-compounds. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
a. General Observations on the Reduction of Nitre-Com-
pounds. .................................................................... 180
fe. Reduction of Nitrobenzene.............................................. 145
I. Chemical Relations .............................................. 145
II. Significance of the Electrical Relation*.. . . . . . . . . . . . 149
III. Presentation of the Reduction of Nitrotanzene 154
c. Substitution Products of Nitrobenzene.. . . . . . . . . , , . , . , . , iflS
I. General Laws Governing Substitution.. . . . . . . . . . . ..ififj
II. Homologuea of Nitrobenzene. . , . . . . . . . . . . . / , , . . . . „ liig
III. Halogen Derivatives of Monoaitro-bodies,. . . . . . . . . . 174
IV. Nitrophenols,, ...................................................... 175
V. Nitranilines. . . . . . . . . . . . * . . . . . . . . . . . . . . . . . . . . . . . , 177
VI. Nitre-derivatives of Diphenyfamine of Amidotri-
ph©nyim.etha.ns.. . . . . . . . . _ . . . . . . . . . . . . . . . . . . 180
VII. Nitroaldehydes and .». . . . . . . . . , . , . , , 181
VIII. Nitrobenzene»carl>oxyHe Acids . . . . . * , , . . ». . , , . . , . , l§$
IX. Nitrobenzene-Rulphonic Aeidi, . . . . . . , , . . . . . . . , . ». , igo
X. Further Reduction of Nitro-bodien* . . . . * . , . . . . . . . . ]g$
I
CONTENTS.
XI. Nitre-derivatives of the Naphthalene-, Anthracene-,

and Phenanthrene Series..................................... «. 190
XII. Nitroso- and Nitro-derivatives of the Pyridine and
Quinoline Series....................................................... 192
3. Amido-derivatives.......................................................................... 193
4. Phenols .......................................................................................... 199
5. Alcohols, Aldehydes, Ketones, Quinones........................................ 202
6. Acids ............................................................................................. 211
7. Acid Amides and Nitriles ............................................................... 215
8. The Reduction of Indigo................................................................. 210
9. Pyridine Derivatives and Alkaloids.............................................. 217
10. The Camphor Group ...................................................................... 225
11. Electrolysis of Blood and Albumen................................................. 229
CHAPTER V.
ELECTROLYSIS WITH ALTERNATING CURRENTS . 230
CHAPTER VI.
ELECTRIC ENDOSMOSE ................................................................................ 233
PART II.
ELECTROTHERMIC PROCESSES AND THE SILENT ELECTRIC
DISCHARGE.
CHAFFER I.
THEORETICS AND METKODICS ...................................................................... 235
1. Theoretics...................................................................................... 235 „
2. The Reaction Temperatures ................................................* . . . . 238
3. Arrangements ...................................................... ' ........................ 241
CHAPTER II.
TBCE SPAEK DISCHAEGK ANB THE VOLTAIC ABC. .....*.. ...................... , 244
1. The Spark Discharge...................................................................... 244
2. The Voltaic Arc .............................. ---- ....................................... 240
CHAPTER ILL
THE UTILISATION" OF CTOBENT HBAT IN SOLID COOTWCTOBS.
rr-------------
X CONTENTS.
CHAPTER IV.
PAGE
THE SILENT ELECTRIC DISCHAEGE AND THE EFFECT OF TESLA-CTJRRENTS . 261

1. The Silent Electric Discharge .................................................... 261
a. Arrangements .................................................................. 26&
6. Chemical Results............................................................ 265
I. Carbonic Acid and Carbon Monoxide ...................... 266
II. Hydrocarbons .......................................................... 270
IH. Alcohols.................................................................. 273
IV. Aldehydes and Ketones ........................................... 276
V. Acids and Esters ..................................................... 277
VI. 1. Concerning the Binding of Nitrogen to Organic Sub-
stances.............'............................................... 279
2. Behavior of Vapors towards Tesla-currents ............................... 288
LIST OF AUTHORS .................................................................................. 293
INDEX ................................................................................................... 297
ELEOTKOCHEMISTHY
OF
ORGANIC OOMPOUNDH.
CHAKACTKKJSTirH AX1» C'LAHKIFH'ATION OK TIIK
TICK application of electrical <*ner/fy for rf

reactions wag tried long ago and in Ihr rno;;| various way*.
Tho ofjHorvations, hou'i^T, u*<Tr*iil fir^f IVw in ?iiinilwi% kviflin;:
points of vic»w wen* lacking and HH* n^tilf^ wi*n* iii*'«i|n*ri'iil
and often contradictory. A (Hiniff Hl»rt in /itt;iclJniu; Hit*
many problems which are presented l*y orpnnli' ehi*nii.'fry iva;i
not made* until larger f*!ec(rieal i*r{tnpriirrtt>i in»n* introdticrd
into Hci(»nfific and technical ent^^firin1^. For itbciiil ,*i dee/ide
organic electrochemistry hw< b*en nitdf*rgolti|f m quiVf (nil
steady dcvelopriif^nt.
Klc^tricaJ energy can tic* employed ditwfly or hidir**f*fly
for accomplishing rhemiVal nwt'unw ftiri'dty^ if flu* fit*ltj
triiverHc*d by Ifn* c«m»rit i^ of mi Htf'twlytir m»ttm»; imiimi !yl
If a tnuisforiiiiilion of i»fi*rfririi! bio o(hr-r ioriii/4
place, wliidi— for itiHtnncrs luiit or ean
chemical phenornriiii outMide of tin* eurmit Helil, Hotii
form« of electrieity itre of tftiwHjfiil |>riu*lif*nf ii
the former in <*lwtwly*i«f fiiirlirtifurly in fi*iiiii«f}i«tf
2 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
and substitution reactions, the latter in pyrogenic and photo-

chemical processes. Another kind of electrochemical action,,
and one in which the connection between electrical.work and
chemical effect is still hidden in obscurity, is the glow, or silent
discharge. In spite of the few facts known about this form
of electrical energy, it can be claimed positively that it is of
fundamental importance in the synthesis of simple organic
bodies and is, perhaps, a means for explaining the methods
which living nature employs in building up substances.
A survey of the great number of organic electrochemical
investigations shows a very unequal distribution of scientific
labor among the separate parts of the extensive domain. The
electrolytic reactions have been by far most thoroughly investi-
gated, particularly the reduction processes. Oxidation and
substitution reactions have more rarely been the subject of
successful researches.
Pyrogenic decompositions and syntheses of organic substances
produced by the induction spark, the electric arc, or highly
heated conductors of the first class have been numerously
mentioned. However, we are just beginning to obtain scientific
results in this line of work. It has already been mentioned
that our knowledge of the action of the glow and convective.
discharge on carbon compounds is extremely insignificant.
The varied properties of organic bodies explain this unequal
treatment and the result. The reduction of carbon compounds
occurs usually at certain reducible groups in the molecule with-
out destroying this latter. The whole molecule is usually exposed
to the action of the electrolytic oxygen. The final product of
a reduction is closely related chemically to the material started
out with; the end result of an oxidation is often the complete
combustion of the molecule. Quite a number of possibilities
exist between a slight attack by oxygen upon and the complete
destruction of a compound by oxidation. A realization of
these, if at all possible, depends upon most painstaking observa-
tions of fixed experimental conditions, which are often difficult
to determine. Hence oxidation processes are much more com-
INTRODUCTION. 3
plicated than reduction processes, and usually less profitable.

These same points of view also apply to electrolytic substitu-
tion, which, being an anodic process, is often only with difficulty
protected from the oxidizing action of the current.
The relatively great sensitiveness of most carbon, compounds
to high temperatures confined electrothermic decompositions and
syntheses of organic bodies to a small area, so long as the heat
was derived from the induction spark, or the electric arc.
Electrical energy has, however, proved itself a convenient
medium for investigating the behavior of sensitive substances
at relatively high temperatures, ever since metallic wires, or
carbon filaments, have been used as sources of heat which
can be easily regulated by increasing or decreasing the current
pressure.
The properties of electric energy as well as those of the
carbon compounds require special forms of experiment for
organic electrochemistry. These differ entirely from the purely
chemical art of experimentation, i.e., partially new experi-
mental methodics are necessary. The more it was possible to
recognize the important points in the course of an electro-
chemical process the clearer the viewpoints became regarding
the choice of the most suitable conditions for experiment.
The endeavor theoretically to represent and unite the numerous
observations went hand in hand with the experimental develop-
ment. Theoretical considerations led to new experimental
conditions and new problems. The theory becomes closely
associated, by certain requirements, not only with the subject «
of the experiment but also with its arrangement. A descrip-
tion of organic electrochemistry must fully recognize theory
and methodics as well as the chemical results.
Depending upon the forms in which electrical energy is
employed in organic chemistry, we can distinguish three
processes, electrolytic, electrothermic, and electric-discharge
reactions. A threefold division into theory, methodics and
experimental results, hence, naturally follows for the disposi-
tion of each of the three resulting chapters.
It may be remarked, particularly in regard to the description

of the methods, that only the necessary and important data
are mentioned here. The author does not intend to give a
practical guide for making experiments. Only original investi-
gations or special text-books 1 can serve such a purpose. It is
the object of the respective descriptions in this book to dis-
cuss the general. principles and to lead the reader to a clear
understanding and a correct interpretation of the various
methods.
1
See, for instance, Oettel, Electrochemical Experiments, 1897 (trans-
lated by E. F. Smith); also Oettel, Practical Exercises in Electrochemistry,
1897 (translated by E. F. Smith, Phila.); Elbs, Experiments for the Electro-
lytical Preparation of Chemical Preparations, Halle, 1902.
1 '
PART I.
ELECTROLYTIC PROCESSES.
CHAPTER I.
THEORETICS.
1. FORMS OF REACTION .
Two possibilities must be distinguished in the electrolysis

of organic bodies. The carbon compound is either an electro-
lyte, i.e., a salt, base, or acid, or it is a non-electrolyte.
In the first case the compound itself furnishes the ions
which condition the conductivity. The work of electrolysis
than consists in the transportation of these ions to the anode
and cathode, and it is a secondary question whether these
ions are liberated molecularly or atornically, or whether they
react with one another, or with the substance still present in
the solution, or with the solvent.
Of the organic ions the anions are almost exclusively taken
into consideration, since organic cations, like the organic
ammonium ions, have been little investigated as to their
behavior in electrolysis. The actual liberation of the ions can-
not'be observed, because when deprived of their electrical
state they cannot exist. On the contrary, the anions oftea
react with one another after their discharge. Thus eithey a
union of several anions occurs or, far oftener, more complicated
transpositions and decompositions accompany these reactions.
5
An example of the first kind of decomposition is furnished
,
by the electrolysis of potassiumr xanthate1:
f
2 C2H5OCSSK =2 C2H5OCSS' +2 K\
2 C2H5OCSS=C2H5OCSS-SSCOC2H5.
In this case two anions unite to form xanthic disulphide. On
the other hand, in the electrolysis of sodium acetate, .the
anions are united, but carbonic acid is simultaneously split off:
2 CH3COO=C2H6+2C02.
The anions of the fatty acids show this behavior to a greater
or less degree under certain current conditions.
But if the organic compound does not conduct the current,
other ions must be present for accomplishing the electrolysis.
For this purpose usually an inorganic acid, base, or salt—
corresponding organic compounds can of course also be used—
is dissolved in the solution. Then, primarily, the passage .of
the current does not at all affect the organic non-electrolyte.
Only the ions are driven to the electrodes where they can dis-
charge themselves. At the instant, however, when the dis-
charge occurs, the r&le of the organic body begins. If it can-
not react with the discharged ions it remains unchanged,
and is not affected by the action of the electrolysis. This
possibility will naturally not be considered in the present
discussion. The fact to be observed is, that the carbon com-
"
pound reacts with the discharged ions—it then becomes a
depolarizer.
Many organic acids, bases, and salts can act as depolarizers
when ions are discharged which react easily with them. For
example, p-nitrobenzoic acid in alkaline solution is reduced
l;
smoothly to p-azobenzoic acid. The sodium ions which are
discharged react so rapidly with the nitro-group that the
f
nitrobenzoic acid does not behave as an electrolyte but essen- f
tially as a depolarizer, particularly since the ions of the sodium
1
Schall, Ztschr. f. Elektrochemie 3, 83 (1896).
'
THEORETICS. /
lution take care of the conductivity. Organic elec-

also furnish the ions which act upon an organic
Thus, if an acid is electrolysed in absolute alcohol
cnetiincs formed:
RCOO +C2H/)H - IICOOC2H5 + OH.
the alcohol is at the same time a solvent and a
"ore divide the phenomena of electrolysis of carbon,

rito two classes: Either the organic bodies thern-
• electrolytes—the; effect of the electrolysis is the
£.1 the eventual additional reaction of their ions at
;•*» (primary reactions)—or they are depolarizers
'actions).
r class in by far the larger. It can again be sub-
two group**, the cuithcxlic and the anodic dope-
is very wit loin that a body acts simultaneously
3 and anodic dfipolarizer. Moro often, a cathodic
ripolarizer, bj reacting with the cations (or atiions),
•faculty of now depolarizing ano-clieally (or cathtxl-
s, for 'example, an easily r&ducibb body may bo
eathodic reduction into cine easily oxidizcxl, i.e.
the action of tlie unions. However, it is more*
clearness to adhere to the division into cathodic
iopolorizers and to determine the nature of the
• ions.
3>epolari2ers.—Hydrogen and metal ions pass to .
4f \votakortoaccountof t lie small and unimpor-
of organic cations. Hydroijcn and me tab can
ygcii, I.e. dooxulize; and the hydrogen can also
rectly to the compound Such bodies that can
or up hydrogen, or do both simultaneously,
compounds. They llieitiselveg arc;; hence
fie property it Is to destroy positive
The at the cathode is called reduction. '
tie depolarizer is reduced by the electrolysis.
THEORETICS. 7
hydroxide solution take care of the conductivity. Organic elec-

trolytes can also furnish the ions which act upon an organic
depolarizer. Thus, if an acid is electrolyzed in absolute alcohol
an ester is some times formed:
RCGO -fC2H5OH =RCOOC2H54~ OH.

In this case the alcohol is at the same time a solvent and a
depolarizer.
We therefore divide the phenomena of electrolysis of carbon
compounds into two classes: Either the organic bodies them-
selves act as electrolytes—the effect of the electrolysis is the
discharge and the eventual additional reaction of their ions at
the electrodes (primary reactions)—or they are depolarizers
(secondary reactions).
The latter class is by far the larger. It can agaia be sub-
divided into two groups, the cathodic and the anodic depo-
larizers. It is very seldom that a body acts simultaneously
as a cathodic arid anodic depolarizer. More often a cathodic
(or anodic) depolarizer, by reacting with the cations (or anions),
acquires the faculty of now depolarizing anodically (or cathod-
ically). Thus, for example, an easily reducible body may be
changed by cathodic reduction into one easily oxidized, i.e.
accessible to the action of the anions. However, it is more
conducive to clearness to adhere to the division into cathodic
and anodic depolarizers and to determine the nature of the
possible reactions.
Cathodic Depolarizers.—Hydrogen and metal ions pass to
the cathode-—if we take no account of the small and unimpor-
tant number of organic cations. Hydrogen and metals can
withdraw oxygen, i.e. deoxidize; and the hydrogen can also
be added directly to the compound. Such bodies that can
yield oxygen or take up hydrogen, or do both simultaneously,
are called reducible compounds. They themselves are hence
oxidizers whose characteristic property it is to destroy positive
discharges. The reaction at the cathode is called reduction.
Every cathodic depolarizer is reduced by the electrolysis.
The reduction of nitrobenzene to nitrosobenzene furnishes

an example of deoxidation:,
C6H5N02 + 2H = C6H5NO + H20.
In the conversion of azobenzene to hydrozobenzene an addition

of hydrogen takes place:
C6H5N » NC6H5 H~ 2H = C6H5NH - NHC6H5.
A withdrawal of oxygen and addition of hydrogen occurs simul-

taneously in the reduction of nitrobenzene to phenylhydroxyl-
amine:
Anodic Depolarizers. — The conditions are somewhat more

complicated at the anode. All the anodic depolarizers are
oxidizable; it is true, even reducing substances which destroy the
negative charges-. But the reaction-picture is more varied at
the anode than at the cathode — due to the individual variety
of the anions. If the action consists merely in a withdrawal of
hydrogen and an addition of oxygen, or both, it is called oxi-
dation.
Examples of such oxidations are the conversion of hydrazo-
benzene into azobenzene :
C6H5NH - NH - C6H5 + 0 = C6H5N - NC6H5 + H20;
the conversion of benzene into hydroqumone by a direct addi-

tion of oxygen :
the production of nitrobenzoic acid from nitrotoluene by the

addition of oxygen and withdrawal of hydrogen:
N02C6H4CH3 4-3 0 = N02C6H4COOH + H20.

THEORETICS. ' [... I r 1 /' *' 9
V
Discharged ions, like the halogens, are also often added directly'',
to an organic, unsaturated body. An additfon ••<}
parable with the addition of hydrogen at the cathode,
CH CHBr2
+4Er = 3fi
CHBr2
or , a substitution takes place, i.e. an anion — simple or compound
— replaces ari element or group of elements of the depolarizer ; —
e.g. in the electrolysis of acetone in hydrochloric acid:
CH3COCH3+2 C1=CH2C1COCH3 + HC1.
Possibly the anion itself undergoes changes before it acts
upon the depolarizer, so that the organic compound can no-
longer be spoken of as a true depolarizer for the anion but
only for its decomposition products. Thus, in the presence
of a base, the anion CH3COO would behave in such a manner
that, after it was split up into ethane and carbonic acid, only
the latter would react with the base. However, such a reaction
can no longer be regarded as an electrochemical one.
It seems particularly difficult to determine in a simple
way the nature of an electrolytic reaction where there are
so many possible ways for a reaction to take place. We shall
see later on, however, that, by a proper consideration of the sub-
ject, a definition is obtained.
Another form of reaction occurs in the electrolysis of organic-
compounds.. While it cannot be regarded as purely electrical,,
no more so than the preceding one, it appears only in a utDizable-
way among the peculiarities of the electrical method. The-
product resulting primarily, or secondarily, can. occur first int
an unstable modification, and can then rapidly undergo further-
changes. I shall here only refer to the intermediate formation
of phenylhydroxylamine in the reduction of nitrobenzene in
concentrated sulphuric acid, which, as is well known, im-
mediately rearranges itself into amidophenol: •
10 KLECTIKXJHKMISTKY OK ORGANIC COMPOUNDS.
Gattenmum l has shown that the unstable modification can be

isolated by adding benzuldehyde to the original electrolytic
fluid. The aldehyde reads more rapidly with the intermediate
product phenylhydroxylumine than the sulphuric acid can act
to effect a molecular rearrangement.
Intermediate phases of elee.trioul oxidation and reduction
can similarly be isolated by adding to the electrolytes various
substances which react more rapidly with the phase than the
oxidation or reduction (regulable by the current conditions)
can take place. This artifice, utilized by Lob2 and Ilaber.,3
makes it possible to obtain theoretically important insights into
the successive and often very transitory conditions of compli-
cated processes.
2. PHOPKRTIKB OF Ku'XrmoLVTio PitoeKbSKs.
The electrolytic method .possesses a number of proper-
ties which markedly distinguish it from all other chemical
methods. In the first place* the current produces the effect
which the chemical method can accomplish only through the
agency of certain materials, such an load peroxide, chromic
acid, etc., in the case of oxidations, and xinc, stannous chloride,
iron, etc., in the presence of acids or alkalies in reductions.
This effect is solely produced by ion-discharges, forces which are
ultimately derived from a source of electrical energy, i.e. water
power or coal.
A consumption of energy replaces a consumption of material.
The economic ratio of thctno, which is of great practical impor-
tance, depends upon the factors controlling the prices of , material
and energy.
In such proeeHHOB which require, even in electrolysis, the
prenonco of certain subst uncos endowed with characteristic*
oxidizing and reducing proportion as a necessary component in
the react ion, the actual material consumption is nevertheless
very incousidombh1. Tho. mibstancoH hi question, for instance
___._„,_'^-' " "
f,
fi, mt\
THEORETICS. 11
the metallic salts, need only be present in the electrolyte in

very trifling quantity, since, after accomplishing their purpose
they are regeneratedv by the, current and can be reused for
accomplishing innumerable reactions. In this case, also, only
the question of energy need be considered.
Moreover, the electrochemical method allows the confining
of the reaction to a certain space within the chemical system.
The reaction occurs only in the immediate neighborhood of
the electrode,—thus the reactions of the ions themselves take
place on the electrode surface at the instant of their discharge,,
those of the depolarizers in proportion to the quantity coming
in contact with the electrode surface, either by diffusion or
stirring. The extent of the space in which the reaction occurs
therefore depends upon the extent of the electrode surface;
it can be considered as an extremely thin layer which is in
intimate contact with the electrode. In this layer the reaction
processes occur in accordance with .the known laws of reaction
kinetics, i.e. their velocity depends upon the concentration of
the active molecules. These are, however, the ions just dis-
charged, either alone, when they react with one another, or
simultaneously with the molecules of the depolarizer. The
concentration of the latter is independent of the electrical
conditions, but the concentration of the ions IKS determined by
the intensity of the current, according to Faraday's law.
3. SIGNIFICANCE OF THE VELOCITY OF REACTION.

The electrically feasible reaction conditions are (1) the
extent of the reaction space and (2) the quantity of reactive
ions in the latter, i.e. the concentration of the ions can be
regulated in a purely electrical way and within the broadest
limits. The highest dilutions can be realized just as well with
weak currents and large electrode surfaces as the highest con-
centrations with strong currents and small surfaces. That
most important factor of reaction kinetics, the reaction velocity,
is thus determinatively influenced by these concentrations.
The importance of the reaction velocity is especially f undamen-
! tal for the course of the reaction; for in the majority of cases
•j it is a case of processes vying with one another, the reaction
1[ velocities of which determine the preponderance, and hence
i
i the result, of the one or the other process.
•i The last remark, that competitive reactions occur almost
1
always, needs a brief explanation. One reaction possibility
,• is electrolytically always present—the liberation of the ions
in a molecular state on the electrode. This liberation is a
! reaction which must not be confounded with the discharge
j which precedes it. The discharge takes place in accordance
I with Faraday's law, and since the discharged ions—they are
! ' either atoms orci unsaturated " groups formed by dissociation—
| cannot exist, they react with a certain but unknown velocity.
' They thus combine to form molecules or complexes, and the
j stable end-products are liberated in conformity with Faraday's
j law, the quantity separated being proportional to the discharge.
1 But if a depolarizer is present, the discharged ions have the
i opportunity to react- with it instead of being set free. The
1 . depolarization reaction also takes place with a certain velocity.
I The two velocities, however, are decisive for the partitive
»! ratio between an ionic liberation and a reaction with the depo-
\ larizer. Herein lies the importance of reaction velocities in
j electrolytic processes.
j The question follows: How can we regulate ad libitum these
j velocities, i.e. usually make the reaction with the depolarizer
t the most predominating one? Apparently this is only possible
\ within the bounds set by the chemical nature of the active
•t molecules—by a shifting of concentrations in the reaction
\ space, which can be regulated on the one hand by the variation
| in the quantity of the depolarizer, and on the other hand by
I the concentration of the discharged ions and the size of the
; - reaction space, i.e. the electrode surface. The velocity of
I
*»/ I liberation is also increased by increasing the current
strength,
upon which the prevailing concentration of the discharged
ions in the unit of time depends, likewise by decreasing the
electrode surface, which has the same effect as the increase
in concentration. It will therefore be the experimental problem
THEORETICS. 13
to choose the current strength, electrode dimension, and depo-

larizer quantity in such a manner as to produce the desired
effect.
* The ratio of the current strength to the electrode surface is
called current density. This latter and the quantity of the
depolarizer therefore are decisive factors in electrolysis.
4. REACTION VELOCITY AND SPECIFIC EFFECT OF
REDUCING AND OXIDIZING AGENTS.
These conditions can only give an insight into the quanti-
tative course of an electrolysis. The qualitative course of the
reaction is conditioned by the chemical forces of affinity specific
of the single elements or compounds and characteristic of the
reacting masses.
In the majority of the electrolyses of organic bodies the
circumstances are very much simplified by the fact that it
is only a question of two different forms of reaction, viz. reduc-
tion and oxidation. The limits within which a reduction can
take place at all are already given in the case of a cathodic
depolarizer by its nature, no matter which reducing agent
is employed. For instance, only nitrosobenzene, phenylhy-
droxylamine and aniline need be considered in the reduction
of nitrobenzene, and the chemical nature of the reducing ions
cannot enlarge these boundaries. Since the single reduction
phases are quantitatively related to one another, the one follow-
ing being always the direct reduction product of the preceding
one, arid since the obtainable phase depends solely upon the
more or less strong reduction, the special efficacy of the various
reducing agents presents itself as a quantitative order which
can be repeated at will. The individual properties of the
reducing agencies become mutually comparable in a quantitative
way. For instance, if nitrobenzene is reduced to aniline with
copper and sodium hydrate, but, using zinc and sodium hydrate
solution, only to azobenzene, the specific action of the copper
and zinc is shown qualitatively, but the quantitative connection
exists also at the same time that copper is a stronger reducing
agent than zinc, i.e. a qualitatively equal agent.
The effects producible by choosing a suitable reducing

agent can also be obtained electrically. The important prob-
lem arising in electrolysis is to convert the qualitative phenom-
ena into quantitative ones, and to find a uniform measure for
the changing effects. Naturally, the above applies in like
manner to an oxidizing agent.
As we have already seen, the current density is the regu-
lator of the electrically obtainable concentration conditions
for the discharged ions, and thereby becomes codeterminative
of the velocity of reaction. The obtainable phase of an oxi-
dation or reduction is intimately related to the velocity of
reaction, for as soon as the reaction velocity of the liberation
of reducing or oxidizing ions greatly exceeds the reduction
or oxidation velocity with the depolarizer, the reduction or
oxidation stops. Thus the obtainable phase, i.e. the quality
of the reaction, occurs also as a function of the reaction
velocity.
5. ELECTRODE POTENTIAL AND REACTION MECHANISM.

The question touched upon above can be more fully defined
as follows: Do we know of a factor which includes both the
concentration conditions at the electrodes—the functions of the
current density and depolarizer concentration—and also takes
into consideration the individual character of the active masses,1
i.e. the ions of the depolarizer? The answer is affirmative.
All these influences are contained in the electrode potential.
This claim becomes intelligible if we consider more care-
fully the nature of the electrode material. It is necessary to
choose a certain theory among the various ones which have
been proposed—with more or less justification—on the electrical
mechanism of reaction. I select that one which seems to me
to have the best foundation. The fundamental idea of this
theory has been derived from Tafel.2 Its general usefulness
1
The nature and the efficacy of the electrode metal are included in the
term of "active masses", the ions. This will be shown below.
2
Ztschr. f. phys. Chemie 34, 199 (1900).
THEORETICS. 15
I * have explained in conjunction with R. W. Moore. The

whole idea will bo hero predicated and developed.
Without laying too much stress upon the most modern
view, that of regarding electricity atomieally by means of the
idea, of electrons, all known phenomena justify us in dealing
with positive and negative electrical quantities as with chemic-
ally active masses, and applying to them the principles of reac-
tion kinetics.
The ions are accordingly chemical compounds, so to speak,
of atoms and electrons.
The process in an electrolysis is the following: The ions
migrate to the electrodes, the cations to the cathode and the
unions to the anode*. This takes place as soon an they come
within such proximity of the electrodes that a neutralisation
of the electricity can occur. Wo, are justified in assuming that
this phenomenon takes place on the border line between, the
metal and the* solution in such a manner that the ions touch the
electrode, strike* against it, but without being on the, electrode;
the discharge of the* ions will occur in an extremely thin layer
immediately above the surface of the electrode. In the case
of elementary ions, this discharging process yields free ele-
mentary atoms of great affinity; complex ions give very react-
ive* groupH which are unnaturated and possess "free" val-
encen, mid hence are very prone to react further.
The .supposition of such a discharge which, precedes, the
deposition is not arbitrary, but necessary. The supposition
that the discharge does not take place on the electrodes but at
the latter, Heornn at firot Home what arbitrary. However, the
behavior of attackable cathodes proves conclusively that
the discharge cannot occur on the electrode. We also arrive
at formulas which conform to the observations, if we suppose
that the discharged but not yet liberated ions obey the laws
of osmotic pressure, i.e. the laws governing gases. Thin fact
clear, and agrees with our knowledge of the matter,
if the discharged ions are in a liquid layer, no matter how thin
. L phyH. Chomio 47, 418 (1004).
this may be. It is very difficult to understand, if the ions

discharge themselves upon the metal surface. We would
then be compelled to assume that the solution of any atoms
in solid metals obeyed the laws of gases, an assumption which
is very improbable and leads, especially in anodic phenomena,
to impossible consequences.
The gist of this view is the strict division of the electrode
process into the ionic discharge, by which the ions are trans-
ferred into the atomistic or unsaturated (very reactable) state,
and into the molecular separation of the discharged ions. This
second process takes place with a certain velocity the true
value of which is unknown to us. It is in general so rapid that
discharge and separation appear to us to occur simultaneously.
The discharge takes place according to Faraday's law; likewise
the separation, after a stationary equilibrium prevails between
the discharged ions, the atoms or unsaturated groups, and
the separation products.
We can write the first process as a cathodic reaction:
the second as
2K=K2,
whereby the second equation may be perhaps reversible, as

above mentioned. Accordingly, apparent divergences from
Faraday's laws may occur at the beginning of the electrolysis.
If we also assume the first equation as reversible, the partici-
pation of the electrolytic osmotic pressure would follow from
simple reaction-kinetic considerations.
The second equation is of more interest here. It takes
place evidently with a finite velocity so that other velocities
can compete with it. This last is afforded by the reaction of
the discharged ions with the depolarizer. When this velocity
is far the most important one a separation of ions cannot be
observed; as is the case with many oxidations and reductions.
Chemical work, with which a certain amount of heat and
external work (increase in volume, overcoming pressure) is
H
often associated, is done at tli « 1 r
in electrolysis is supplied from tr<
the product of potential :IL»! t*^
The quantity of electricity i^m-^ry f : . ,^< t
gram-equivalent of ion? I< ctlway- :L ! -,.:..
drawn from Faraday's hnvs. Th»T< ft ns C % I / -\
plished by a gram-equivuleu < » f \n\ - n i.» , t. - ^
work, external work and |XK<il»ly Li}* rat. ! ^ J ;
portional to the elect rot le poifiituil. If iL* , \
consists only of a chemical reaction, h :i « l.-i:.^ :
energy of the reacting system, the { « u-i/Li : ^-<
be determinative for the value if the T.\ '1 . ! *
It is, of course, an entirely ilifltTs'iif « f * » - * i :.
chemical products are formed. Tlie cL k i . . n . i 'i
character of the reacting bodie< rcir.i^ :ir ? 5 ._'
known fact that the end- product uf a n..i ::.»:, -j.
of the value of the energy change t:t kii/z ph. - - >
1
always more or less related to the r.iar.rLil- <:,.**
The sequence of these considerations i< tli.*t t',j; ,'
can produce only like dynamic etfeets.
If the potential is expressed by the Xernst for
f (
in which f i is the concentration of the dischar^N : " \ •* A' L
obeying the laws of gases, seek to re~entfT tin1 « > j . 't r >.*• '•"*"•
a certain pressure—the electrolytic iviiit^tk* [,r*^>;j»'" ..', : .
is the concentration of the ions? in the eltH*tro!y*t , : t - • :y
evident that the potential must contain, apart fr»'Li Mr 'i:**
f
concentration of the electrolyte, all infliieiict s »vlii^L ai ir:i :!"
1
the concentration of the discharged ion? , r j \ T!ie>i* i/! ; :*•• ^
are, primarily, the current density whoso «izt rr«:u^;^ fin*
number of the ions discharged in a unit of tpiit* at a uv^.1
electrode surface, hence regulating its coneentniti M: ^ <»o:* !-
arity, the reactions of the IOBS Tvith one another and \v.th tin
depolarizer. For variations in the concc ntration of tii** \idue
d occur through both processes and, since the velocity of the

reaction of the discharged ions with the depolarizer also de-
pends upon its chemical nature and concentration, these two
last-mentioned factors are also embraced by the potential.
A more thorough knowledge of these relations is gained by a
consideration of the typical electrode processes. ,
6. ELECTRODE PROCESSES!
A. Cathodic Processes.
a. Unattackable and Attackable Cathodes.
In organic chemistry only those cathode processes are of
importance which occur with the reduction of an organic
depolarizer. This reduction is done by the ions discharged at
the cathode. The chemical nature of these -ions can be very
variable and, conjointly therewith, the reduction can occur in
a variable manner.
In acid solution—assuming the depolarizer to be a non-
electrolyte—hydrogen ions will occur, and in alkaline solutions
alkali ions, and by making suitable additions any desired kind
of ions can be brought into action at the cathode; thus any
metal ions may be set free. The metal ions are either added
directly to the electrolyte in the form of a metallic salt or
hydroxide, or they are derived from the cathode metal itself,
in case the cathode is " attackable", and pass from this into
the electrolyte.
The various reduction processes can be brought about simply
if the cathode metal is primarily considered and a distinc-
tion is made between attackable and uriattackable cathodes.
The former are such as give no active ions in the presence of
the respective electrolyte and depolarizer, so that only the
cations of the electrolyte can be shown to be discharged by the
current. Attackable cathodes are those which send traceable
irl quantities of ions into the electrolyte during the passage of the
current, or in its absence. Naturally, only those attackable
cathodes which can yield reducing ions are of interest here.
Since some investigators seer^ to believe that every redtie-
THEORETICS. 19
tion must be referred to the action of hydrogen, let it be emphat-

ically pointed out here that, besides many chemical phenomena,
the fact that it is immaterial whether the reduction is made
at an attackable cathode or by the addition of the ions of this
cathode metal to the electrolyte at an unattackable electrode
proves the reducing capacity of the metal. In both cases
similar results are obtained. But if ions of attackable metals
tiro added, this metal is not deposited on an unattackable
electrode so long as sufficient quantities of the depolarizer are
present and the velocity of depolarization sufficiently outweighs
the velocity of discharge. Although the cathode metal, say
platinum, always remains the same, an effect occurs neverthe-
less, similar to that which would be obtained at a cathode
composed of the attackable metal in the electrolyte. The
conclusion follows necessarily that these metal ions in the
electrolyte, and not the hydrogen atoms, determine the reducing
action by their separation on or in the electrode.
Wo can hence consider conjointly the case of attackable
electrodes with that of the presence of metal ions in the
electrolyte at unattackable electrodes, and contrast this with the
reduction by hydrogen at unattackable electrodes.
For the latter we will suppose that the hydrogen atoms
discharge themselves in the cathode boundary surface, and
that these discharged ions' have two reaction possibilities at their
disposal. They are either separated molecularly on the cathode,
or they reduce the depolarizer. The reduction, velocities of both
processes are determinative for the ratio of division. If the
reduction takes place far more quickly than the formation
of hydrogen molecules, practically no hydrogen will be evolved.
The velocity of hydrogen formation is hence of importance in
the utilization of the current action for reduction. It depends
to a great degree upon the chemical nature and surface condi-
tion of the cathode, arid is very likely related to the catalytic
nature of the metal These phenomena will be considered
conjointly under the discussion on " excess potential/'
Ions are sent off from attackable cathodes immediately into
the electrolyte, so that the relations in the latter are qualita-
lively the same && when metal ions are aclciecl directly to the
electrolyte. The metal employed as cathode is hence immaterial
for trie effect so far as it has not actually reacted with the elec-
trolyte, and can often be replaced by an unattackable cathode.
Under these conditions the metal ions play the role of
hydrogen atoms, as above explained. They discharge them-
selves in the cathode boundary surface and, depending upon
their reaction velocities, affect the reduction of the depolarizer
and the metallic deposition. With a great reduction velocity,
therefore, no metal whatever is deposited on the cathode so long
as sufficient quantities of the depolarizer are present. 1
An important result of these considerations, and one which
confirms the observations, is the knowledge obtained that dlions,
which reduce when, discharged, are again converted by this reduction
•performance info the ionic state and are -not at all separated.
b. Excess Potential and the Reduction Action.
Although the evolution of hydrogen by galvanic action at
platinized platinum, electrodes is a well-nigh reversible phenom-
enon, it proves irreversible at all other cathodes.
To convert, in a given electrolyte, a gram-equivalent of
hydrogen from the ionic into the molecular state at atmospheric
pressure, the same amount of work, which is, of course, depen-
dent upon the beginning and end condition, is always required.
But the electrical work is different at different electrodes and,
since the same quantity of electricity is combined with a gram-
equivalent of hydrogen, the potential of hydrogen evolution is
different with the individual metals. Naturally, with the
equality of the initial and final state the surplus of the electrical
work performed must be compensated by an equivalent gain
in work. Calorific phenomena probably accompany the in-
crease in required work necessary for the hydrogen evolution;
the results of experimental work on this subject, however, are
not yet at our disposal. Excess potential is the excess of the
discharge potential of hydrogen over the potential value of a
1
D. R. P. I17GO7 (1900) of C. F. Boehringer u. Sohne; Lob and Moore,
Ztschr. f. phys. Chemle 47, 418 (1904).
THEORETICS 21
ydrogen electrode in the corresponding electrolyte. The

uantity of heat produced by the excess potential can be very
Dnsiderable. If we designate the absolute potential of the
^versible hydrogen evolution by a, and the value of the excess
otentia! by e, then the electrical work in the separation of a
ram-equivalent of gaseous hydrogen in the first case is
nd in the second
Ai=96540(a+e).
ince the total work in both cases must be equal, there results.,
, as assumed, a production of a quantity of heat q occurs, the
guation
96540a=96540(a-fe)-g,
r
g=96540s.
or mercury e is=0.78 volt, from which q= 18026 cal. results.
[96540 coul. X1 volt = 23110 cal.]
According to Caspar!,1 these excess potentials have the
)Uowing values with individual metals:
At platinized platinum ...................... 0.005 volt,
"' bright platinum ........................... 0.09 ''
u
nickel ........................................... 0.21 "
" copper ......................................... 0.23 "
".tin ............................................... 0.53 "
" lead ............................................. 0.64 "
CI
" zinc ............................................. 0.70
t'C
" mercury ....................................... 0.78
ernst, who introduced the conception of excess potential into
ie science of electrochemistry, accepts as the cause of these
lenomena the varying solubility of hydrogen in the metals.
. f. phys. Chem. 30, 89 (1899V

22 ELECTKOCMlKMIHTliV OF nitClAXIC COMPOUNDS.
Since the energy erf rcHlurlmn djl-nds HtlHly u,Hm th« hdght
of the cathode potential, f h.> hip «T f I,.* i-xn-ss potential is the
stronger the former must I M *. so IOIIR ah hydrogen is the reduc-
ing agent. , .t t,
A great nurrilx'r of lads af,w « with thin rune-option. The
assumptions repcnnling t l w fWtriral miudion inodianism,
according to wlii<''» f lic* ilfcrhnrp- of hydro^n ions rniwt be
distinctly (listing ^MI<|C| frnlfl lhl/Ir li;nl«'|i||l!ir w*iKinilion, loud
to the same coiu'Iusiotts. Tin* rfwttofi velocity c»f molecular
formation from th«' iliM-iiarpMl hy«ln.jrMi icms Is lc»wm>d at
metals with exc»cw [Hifpniial, H» thai the fiivimon ImUveen
molecular formation and rnhirtin^ «> f f l «* poiariwT turns in
favor of the ln/M<*r. Thin retanlali^n i»f liyclnipen evolution
is shown in the hitfh'T f»i»teiitiaL in the excenn vulla^c. With
a high excess voltage in the «ii*ehanrinE ^pac-e H«rcing(»r con-
centrations of c Uncharged reactive hy«lrdgen \nm ran accu-
mulate, so that the reiltirtiiw f«f Inwlie^ rechu-ibli* with difii-
culty, which doc*s no! f»rwr it! phit iiit»"ii platinum electrodes,
succeeds at zinc or rnerrury i'«tln«les.
Since in the fuiuhiiiM'tital views n »*pumtion <>f hydrogen
in or upon the c*ath<Mle «!i«^ not enter into Hit* rjtiestionf the
close connection of thin wpurution with tin- Hoittbility of Itydro-
ogen in the mot.nlH cannot In* eiineetveil. In thin eitse it is
more plausible to think of f l w rrarfioit luring mtuiytically
influenced by tlic.* rnetnl. ArroniiiiKly, tin* pktlnizcd platinum
would be the naotal which accelerate the
reaction
2/7 •-'//..-.»
The higher the c*xceHH jwttfiiflal the ^nmller the* catalytic accel-
eration of the rxMtcfion, :iit«l henre the htniiifer tht* concurrent
reduction.
1
S. Tafel, Ztscltr. f. phy»» Hutu III, »*» flfWtj; Lnii, 7.1-dir f, Kkkir«-
chemie 7, 320, 3S:i (HlCMI'l^lIi; f r«'1ift( fj«i'iir I Kl**k!rf**h«mi»» t, 042
(1903).
2
E. Miiller giv<%« n htifiitar «^p!mmti«4t, l*nf fUff"* t«*t ion tlie catalytic
action, which is Herf* parfiritliiilv rfn|il*nH/wI ^fwltr f, aiw>rg, (1n*m r 20,
1 (1901).
THEORETICS 23
The Idea of excess potential is useful in applying the process

of separating a certain kind of ions at unattackable cathodes.
For reduction it has up to the present only been proved for
hydrogen; it is nevertheless possible that the separation poten-
tial of every ion changes with the nature of the electrode,
.since the opportunity for the reaction of discharged ions being
catalytically influenced to form stable molecules is always
present. E. Miiller 1 and Coehn 2 have shown that the excess
potential phenomenon also occurs in anodic processes.
The generally disseminated idea, however, that the excess
potential of hydrogen also plays a part in the case of attackable
•cathodes is untenable. With metals which furnish reducing
ions—and each cation is capable of reducing—hydrogen does
not take part, or at least plays only a secondary role. The
specific reducing actions of copper, zinc, tin, and lead cathodes
.are not to be explained by the excess potential of hydrogen,
Since attackability is also a function of the electrolyte, the
rule of excess voltage may be applicable in one case and not
in another. For example, Tafel3 could explain the strong
reducing action of a lead cathode in sulphuric-acid solution
by the high excess potential of the lead, while the same metal
is attackable in alkaline electrolytes and yields reducing ions,
whereby the hydrogen action seems excluded.4
c. Concerning Substances Reducible with Difficulty.
Besides the discussion on the strong depolarizers thus far
•considered, it will be well to make a few special remarks on
substances reducible with difficulty. The insight into the theo-
retical relations here existing has not yet been cleared up, and
is much more difficult than in the ease of the substances which
consume practically all the cations which are discharged.
However, it is not at all necessary to add special views to
those already generally developed. They suffice for the present
1
Jahrb. f. Elektrpchemie VIII, 292; Ztschr. f. anorg. Chem.'26,1 (1901)
2
Ztschr. f. Elektrochemie 9, 642 (1903).
8
Ztschr. f, phys. Chemie 34,199 (1900).
4
C1 Ldb and Moore, Ztschr. f. phys. Chem. 46, 427 (1904).
FMlST!!Y UF OW.ANN1
24 "
in explaining tli<- 1 !u»n«)ii»'na urrtirrhig ISITP , and we may

infrpn'talinn. The
sibly get along ^v | h a iu i if l f n ii
lC ,.,,,, iriti(.s I ( I I t l l l . nilllw l l f ,,vc,ry
importance of r<** ^ ^ ^
< i x l l l : n i : i t i l l l l of U|C .
cal action req*^*rr
of the influences < in ^t |« . rf.ii«>.. .,f tin- n-acticm to
that fundament al
therefore, be we'll In em.n.ler the*, ml!
ticular side and to a-k what relaticw < i < » the electrical factors
bear to the rotation velnrity, nntl in what niainuT do they
act on the lattc*r. It aj*pai>' tliut the rHtirii^ , u.t; lon ()f
difficultly redvKTil»l<* sul*1awt* :it uimtlarkable c-uthodc-K takoft
place different! \% <lc|H-iiiliiiK îjHin tin- mati'rial of iho latter.
This diversity cran 1«* rxplaini'd l»y utift|ujil nuluftion veloci-
ties. The lêr clc»|i^MtI UJMIM tin* <Htnn*ntration of tin* react-
ing substances which H« far »*< the ion:-' al«mi' to lx» taken
into consideration an* ri»fici*rn«Ml b? regulated liy tlie current
strength, the c*l«'iuicat rr>-i*ifance it f tin* hyutcin, I.e. the
nature of the fneiHuni, sun I l*y catalytic*. iuiiucnm< which,
with the choice* cil* snitahli* ct»utiitiMrtH. are to lie iwerilml to the
.electrode metitl. The ineaMirnhle cli*ctrical factor, the poten-
tial, comprises si part nf llii^nr am! it ist of conse-
quence to thxiH know !h«* itetcnnining the
potential in s\ic*li u ttmnner fl»* rtniiiirliciii with the reac-
mm tion velocity rc^fnainH clear.
Substances .reiiurllilf* ililliniliv an* tnrli
trifling polarising value, - In H I P oW
unessentially lowers 1 the cu ' jmft*iitLiI whii-h warn
mined for the i>nn* rlrHrnlyli*
been fully invc;*Mtignti*fl tiy 1
In the COBO <if of rriiucgd In aeid
solution at priM^ticmlly the consump^
tion of hydrojaccm by llti* m
quantity of hyclrr>gi*ti liy iin* m that
1
With caffeine? ntu! in an in
1? potential occurs «utt CMV
m' the Influence of ttit? fiitlimli* «»tlin erf Sub-
stances Reducible
THKOKKTH'H.
always takes place into hydrogen consumed !•> <* * < '•• * ;
T lr
and hydrogen evolved molmilarly a* a «r:» - ^ •
preceding explanations, it is dourly evidri.t th i t *
potential must play a decisive* part in all tb »• r . . >
forms an expression for the above- mention* ^ f n i t " "' »
in proportion to the reaction velocities H v» »• • < > , •
velocity of formation of molecular h\dnw» •' ^ " » '
influenced catalytically by the- electrode materi.d, ^ • '
the excess potential of the eledrode in J*UP> :»»*id *u'i," *
depolarizer will be decisive* for the reduction «•»<»•!"*, j *
that the catalytic property is not ini»li!i«"l by H" * ' » :
The latter, under similar expenm«9iital 1'itiifSiUNii , j*,-i i i 8
no catalytic acceleration of the mlitHtoit if * h *«MV "
1
always with a similar velocity with tb I i \ * l i * » f * ^ I
change in the division ratio between hydmfHi <-v«*hiM"?. *
duction is only determined l>y a chnitp* in %vk«*tH nj f t , - *
' Naumann's l experiments aKn»cv with t hi ;, II*' !«« *u * • I f * 1,1*
f
velocity with which catTeinc* in reduce* I at l *»itl r»tiiM»li 4* i
f
upon the cathode potential in pure arid, Th«* i* *i'i« ^j* J* •
the more energetically the higher Ilie e\ci«» . |»nf*'i<fi !t n
acid. This rule does, not apply when tin* e,ttli«i<S»4 in* i -J ti
ally iniluences the actual velocity of i* '«liu MMH i > t - v ,
between hydrogen and tho depolarizer Thn%* ? ilf* lu* i M ',
more quickly at mercury than at lead rlt-Hfi, it i( ^?j..
both metals possess the name1 cathode p*»teiifi-d *î th
excess potential in pure acid. The* v««!oe$ty *if * M I ,^*M-
evolution of hydrogen can al«o b* n taid^d l*y tl-« } «>* ** LI
the caffeine molecules, as t!ie caffeine* moifrtilt • t«* u » n « -
illustration, increase the chemical re.^taric** in «Jai ! » • ! » » $ '
the electrode surface. In this ease Uw i XI*Â ptif ^t<t ul n^ ? »
and with it the cathode potential, At flu* w*> t$n;i
depolarizing action of the caffeine* HH «|U lu Itrni-r t{,« * , * »r
potential. If the first action— with fjiitiniiin/ *,j i a?*
—is the stronger, an increase in pnteiitint h at lit f r,K;,.f » , ,
spite of the addition of caffeine. By fu w
1
Sen note on. 21.,
26 ELKC T1U X'UKMISTRY OF OUCiANK' COMPOUNDS.
of caffeine, the potrntial is finally <.;m**d to drop % stronger

depolarizing eflVc-tSK This phriif>mi»m>H nfrurs ; t t lead but not
at mercury cttUic»l''s ^N««W«"»^- I» the I; UHT rase* only the
depolarizing action nf raiiVtiir i sdimvn; this is pfrhap* dopon-
ent upon t he diO'i'ivnf surfan* rnnditinns nf tanl and mercury.
The cathode* | t < » t i * n t i a l i» dHi*nimn*d nn th*» nm* hand by
the electrolytic' <înntii- prr.-. un nf ihi <.;<ihnd<'f i . (» , ? by the
quantity of hy< Ir«*kr|'» \U»ifh i »'vu|\xl i *Ii 'c !n »l yi i rj i l l y at uimt-
' tackable catho«!*v in ih*- unit nf <iiu... With thb Isyftn^n, the
ions discharsc*cl in thr hnun*i;iry lavt-r, uhii-h unii»» to form
molecular hy<In*tr**n, ; MV in i'»|.'iilil*rwui. Thi «*lertn*lyti«
.osmotic prossun* i - , th<-n«jnri', iu<it«p* u<t*'Ht » *f ib i[Uantity of
hydrogen ust»<l l » y t!i»' «l*«| »i*l iri/iT, Mun-nMT, fin* poii'iitial is
determined by thi' «'«»nrfnii,Mti»tn »1 fin* iiyilmui'ii i*»ns in the
.electrolyte, \vhir-h I'^nr^nir i t i » t 'i i-u/ hi* lalj'ii a- «*onsJant
when strong :i<-M * i t i * ? i . t "j .
The coiiclu^l«Hi 'i i !» »'A i » }n«n»*i I*v XjiiUiiatin» It * In* drawn
"from theses coir i » l «'!at i * m- ! ;irr* U«M Jnlln\\inj5- \t ifii*rc»ury
cathodes, \v-ho.-f «*\rf - ptf^fjlh! i !>f* t i i i l l i p i i r i 'f i hy the*
caffeine, the* c*;it<^»»J»» pittMnhal in»i f •** «*i*ijti jl it-i-If nf c*vc»ry
.moment during f i ^ f t H"lM'ti'»n » * * IJ »»nlv ihr f'h**'frnlyfii' i*\alu-
tion of hydrof5**ii firriiH*"} an»l tin* rnrniit rfiii4iiiii*d in [\w
reduction of t l i « * i ali-Mm* «lrl imt inihimi'M if hfijjhf At lead
•electrodes, H</\\v*\«t, ?l^** tîf{i»îi» |iMfrntij»)-» ar? alttjiy** MI»II»-
what higher fliifinji th«* initiction thun in tin* âiiu* i*I«*Hro«
lytic hydrog^ti ^v?4iili*>n in th«* jaw* arid, jinn* (!»*« in«*r«»a<t* in
•excess potentiul rati^*«l IA ih«* rn*-!^*iit»* i* add«*d to i t ,
It is cvi<h*iif 'from ji t fi i t 'i »l i i ; i i i *i i i nf flii">* variously pw
••sible influeiK*i*Hf ^fn-ii ?* • lh»* rh;uiv«* in *)<" «*tf<*^ jtnffntin
'Caused by tin* >l**jrt4ni»*r» tin* rnf i l i t r artiun nf ib* iiii4it
upon the vc*l€ic*if v l«itli nf lip* itiiiifinibr tfttftiiifpitt nf liydrngH
.•and the reaction l#'tiv****i j l iydr^'H tin* d» f jft4iiirf*r -ll ni'
t he val u e of t i n * i / i fl i i ul i * P riiiif|ltiriiii*i! hy a MWH o
1
Naumannf in lii^ tiiu*«*rf4tf<*ft» fit*^ «i**tl'*r «)i^hiittît v brti,
contains the hyf »«»f }<*'•»., tiifit tip* ti,i|f«i«< f<*im»ti<'f* ?tti4 fir ntl*Mii«m «»ae
•tions are of the HHIn*< t
THEORETICS.
moments which can be independent of one another. Hence

the reduction effect can vary even with equal potentials at
different electrodes, which is true, for example, with caffeine
at lead and mercury cathodes. 1
B. Anodic Processes.
A theoretical insight into this part of the electrolysis of
organic compounds is much less clear than in the ease of ciitho< lie-
processes.
The pure action of oxygen is in every way comparable with
that of hydrogen. Only a greater variety is hens possibly
because ozone as well as oxygen can be formed. At platinum
electrodes, for instance, the formation of oxygen occurs at 1 .OS
volts as measured with a hydrogen electrode at zero value,
and that of ozone at 1.67 volts. Moreover, the great suscepti-
bility of the carbon compounds towards oxygen, as already
alluded to, which may easily lead to their complete destruction,,
and the great number of oxidation phases to which each molecule
may in a greater or less degree be subject, render difficult an
insight into the electrical oxygen actions.
It has already been mentioned that the excess potential
phenomenon occurs also with the oxidation phenomena. Thus
it is possible to conyert p-nitrotoluene into p-nitroboriHoic acid
at' lead-peroxide anodes, while at platinum anodes only the
alcohol is formed. It still seems inexplicable how thin peculiar
action of the anode material takes place. The simplest yet
sufficient .explanation is to assume that the anode in capable of
influencing catalytically the oxidation process an well as the*
formation of molecular oxygen. If the first process is acceler-
ated and the second retarded, we obtain the excess potential
by which the evolution of oxygen occurs only at a higher
potential. Inversely, the oxygen and ozone formation can be
made reversible, and the oxidizing action decreased.
A further complicating moment in electrolytic oxidations,
as opposed to reductions, is the variety of possible ionic
l
Tafel and Schmitz, Ztschr. 1 Elektrochemie 8r 281 (1002),
THEORETICS. 27
moments which can be independent of one another. Hence

the reduction effect can vary even with equal potentials at
different oloetnxles, which is true, for example, with caffeine
at loud and mercury cathodes.1
B. Anodic Processes.
A theoretical insight into this part of the electrolysis of
organic compounds is much loss clear than in the case of cathodic
processes.
The pun* action of oxygen is in every way comparable with
that of hydrogen. Only a greater variety is here possible,
because ozone us well as oxygon can be formed. At platinum
electrodes, for instance, the formation of oxygon occurs at 1.08
volts as measured with a hydrogen electrode* at zero value,
and that of ozone at 1.07 volts. Moreover, the great suscepti-
bility of the carbon compounds towards oxygen, as already
alluded to, which may easily lead to their complete destruction,
and the grout number of oxidation phases to which each molecule
may in a greater or less degree be subject, render difficult an
insight into the electrical oxygen, actions.
It has already been mentioned that the excess potential
phenomenon occurs also with the oxidation phenomena. Thus
it is possible to conyert p-nitrotolueno into p-nitrobenzoic acid
at loud-peroxide anodes, while at platinum anodes only the
alcohol is formed. It still seems inexplicable how this peculiar
adion of the anode material takos place. The simplest yet
sufficient, explanation is to jissumo that the anode, is capable of
influencing eafalytieally the oxidation process an well as the
formation of molecular oxygon. If the first process Ls acceler-
ated and the second retarded, we obtain the excess potential
by which tho evolution of oxygon occurs only at a higher
potential. InvcTHfly, the oxygen and ozone formation can be
nmdo rovorsible, and the* oxidizing action decreased.
A further complicating moment in electrolytic oxidations,
HHoppoMni to rodwtionH, ia the* variety of possible ionic actions,
'TaM ami S , Xtsebr, f. Eloktrochomio H, 281 (1002).
While the process at the cathode always ends finally in with-

drawal of oxygen or in taking up of hydrogen, the number of
possible reactions at the anode—aside from solution-phenomena,
which are without interest here—is a much greater one. For,
each ion which is capable of substituting can pass into the
reactive state at the anode and produce reactions which
^cannot be numbered with the real oxidations. In the first
place numerous substitutions can occur in difficultly oxidizable
bodies, especially aromatic compounds, for instance the chlori-
nation of phenols and phthalei'ns, nitration of acids, diazotizing
of amines, etc. Substitution and oxidation processes often
occur simultaneously, as in the electrolytic formation of iodo-
form from alcohol.
A great many more individual varieties of reactions must
be taken into consideration in anodic processes. However,
the same fundamental law holds good for each of the separate
possible processes as with the reductions, in that the energy
of the action of the anion is determined by the anode potential.
Thus 0. Dony Renault,1 carefully observing limited anode
potentials in the electrical oxidation of the alcohol, could
.obtain acetaldehyde or acetic acid at will.
The reason for the prominence of reduction processes as
apposed to the less prominent electrical oxidations has already
been given. Besides the complexity of the phenomena, it
•must be taken into consideration that the oxygen evolved at
platinum anodes has a low potential. The action of an oxi-
dizer depends upon the oxidation potential with which the
oxygen attacks the depolarizer. Even though the oxidation
potential can, within certain limits, be varied by the anode
potential, for instance by the material of the anode, it never-
theless does not attain the value of the strong chemical oxi-
dizers, as for example chromic acid or permanganic acid.
This follows from the small activity of electrolytic oxygen in
regard to separate bodies.
Since it is not possible always to obtain the entirely iiidi-
1
\v
HY
THEORETICS. 20
vielual action of these two bodies on organic -ccîpqUTiels with

the aid of eled.rolytically evolved oxygen,, it Beemed advisable,
to use the chemical oxidizers, which have already been men-
tioned, in the electrolytic cell. This was done by employing
the electrical process only for the regeneration of the chromic or
permanganic acids which, an such, oxidize organic bodies in
a purely chemical way, being themselves converted thereby
into lower stages of oxidation. The advantage of such a method
lies in a saving of both the oxidising acids, because; on account
of the regeneration to their highest state of oxidation, very
small quantities suffice* to oxidize unlimited quantities of organic
bodies. This oxidation process is hence* both a secondary and
a chemical one*. Nevertheless, it possesses the essential feat-
ures of an electrochemical process, the substance being replaced
l>y the energy.
Attackable anodes, which are brought into solution by
the unions of the electrolyte1, are1, of ne> value1, or only of a wholly
secondary one, in the elect rolysls of organic compounds. But
in Hid* eases where, by reason of the attackubility, oxidizing
nubBtancoH arc formed on the; anode, the latter can assume the
function** of an oxygen carrier. Thus, if a lead anodo is super-
ficially coated with load peroxide, thin latter offoota the oxida-
tion, being in turn reduced but always regenerated by the
current. But if a lead-peroxide anode, prepared in this man-
ner, aetB merely by means of its excess potential for the clis-
rliarged oxygen, without reacting directly with the elepohtrmvr,
if naturally exercises only the functions of an unattackablc
a node*.
Finally may be mentioned the purely catalytic action of
the electrodes upon the reaction products produced by the
eled.rolynis, a sphere of phenomena which lies outside* the
purely" electrical relation**. This is the ease, for instaneie,
in the decomposition of hydrogen peroxide* by electrical
oxidation at platinum anodes into water artel oxygon. But
even the electrical conditions can te modified by such reac-
tion^ if change** in the concentration relations of the pre-
dominating ions are combined with them.
r
4
r.walWfe,*
<o!3
7. THEORY OF THE REACTION VELOCITY IN ELECTROLYTIC

PROCESSES.
The ease with which the reaction conditions can be con-
! trolled makes electrolytic processes especially adapted for
•| studying the laws of reaction, particularly those of
reaction
,| velocities. The dependence of the reacting agents upon the
I current strength, according to Faraday's laws, makes* it pos-
| sible to vary ad libitum the temporal total course of a reaction
! within wide limits—a possibility which in purely chemical
} operations, by changing the conditions of pressure and tempera-
I ' ture, exists to a far less extent.
* Attempts have not been lacking to regard electrical proc-
I esses from a reaction-kinetic point of view, and to use them
| , directly for determining reaction velocities. Even though
these experiments are based naturally upon single simple
examples—mostly reduction experiments — their theoretical
results have, especially for physicochemical speculations of
organic reactions, such general importance that the reasoning:
involved in the most important theories will briefly be out-
lined here.
a. The Diffusion Theory.
Since, according to the preceding descriptions, the reac-
tion space of electrolytic processes consists of an extremely
thin layer in contact with the electrode—the contact surface
of electrolyte and electrode—these processes can generally be
regarded as reactions in heterogeneous systems. Nernst 1
lias proposed a theory for such systems, which has been
tested experimentally by Brunner.2 The principle of this
theory consists in basing the reaction velocities on th& dif-
| / ; fusion velocity.
The equilibrium between two phases at their boundary
surface must be produced with extremely great rapidity,,
1
Ztschr. f. phys. Cheinie 47, 52 (1904). See also the earlier investigation:
Noyes and Whitney, ibid. 23, 689 (1897)
2
Ztschr. f. phys. Chem. 47, 58 (1904)
THEORETICS. 31
otherwise infinitely great, or at least very great, forces would

develop between the extremely close points between which
the reaction occurs. Those would, however, bring about
the equilibrium practically instantly. In such a case the
reaction velocity is conditioned by the velocity with which
the mobile components reach the border-line of the phases,
i.e. by the diffusion velocity.
The contact surface1, of both phases will now actually pos-
sess a thin but measurable layer of the thickness 8, within which
the whole diffusion process occurs.
If we designate the concentration of the diffusing sub-
stance at the surface of the fixed phase by (7, its concentra-
tion in the solution by c, its diffusion constant by D, and the
surface* of the solid body by F, then in the period dt the quan-
tity of substance
will diffuse to the contact surface and immediately react.

The speed of reaction becomes
( hx n J ^ Z£
dt d '
If wo consider that 0 possesses an extremely small and
negligible value, on account of the csquilibirum which occurs,
instantly, the following equation results:
dx DF
dt** . F' C "
The speed of reaction is proportional to the concentration
of the* diffusing mibstanee.
In applying these results to electrochemical reactions there
is to be added, only the condition that the concentration of
the reacting substance in the immediate vicinity of the elec-
trode munt always possess a very small- value, which can
easily be attained by choosing a suitable current tension. Then
the reaction velocity will depend only upon the quantity of
I the substance reaching the electrode. Electrolytic transfer-

| ence must be considered as well as the diffusion, if ions are
| involved.
\ Since the quantity of the discharged ions depends upon
I the current strength, it represents a measure of the reaction
I velocity, if (1) side reactions are excluded — for instance, if no
$ ions are discharged without reacting — and (2) the current
I strength chosen is not so small that the reaction velocity
I possesses a higher value than the discharging velocity of the ions
I regulated by the intensity.
; In other words: The current strength is then only a direct
I measure of the reaction velocity, if the maximum current
I strength at which all the liberated ions are just able to react
I is employed. The production of this condition can be easily
I recognized experimentally by the fact that the least increase
I of this maximum intensity leads to side reactions, most fre-
I quently to a molecular separation of the discharged ions.
I Before the Nernst theory was proposed, H. Goldschmidt l
I had already employed this idea for studying the relation between
reaction velocity and concentration of aromatic nitro-bodies.
If the maximum current strength at which 110 hydrogen
is yet evolved, is designated by Jmj the concentration of the
body to be reduced by C, the experimental equation resulted
C* is the concentration of a cross-section, i.e. the reaction

takes place directly at the electrode surface. If we suppose
that the adjustment of the equilibrium takes place there with
•extreme rapidity, according to Nernst, then the reaction velocity
will have to be based solely on the diffusion velocity, and will,
therefore, be directly proportional to the concentration of the
depolarizer in the electrolyte. The theory hence demands the
formula
T ' __ T T m rt
Jm — J\. -0.
1
Ztschr. f. Elektrochemie, 7, 263 (1900).
THEORETICS. 33
The lack of conformity has not yet been explained. Perhaps

the supposition of a very rapid attainment of the equilibrium
at the electrode does not apply to the reduction of nitrobenzene;
which abounds in phases,
The results of Akerbergl concerning the velocity of the
•electrolytic decomposition of oxalic acid in the presence of
sulphuric acid agree better with the theoretic requirements.
So long as the proportion of oxalic acid is considerable, the
decomposition takes place according to Faraday's laws/ i.e.
without evolution of oxygen. But if the solution has reached
a certain dilution, the electrolysis occurs—independently of
the* current density—accompanied by an evolution of oxygen
proportional to the concentration of the oxalic acid in the
solution. The decomposition of the oxalic acid then takes
place in the; same proportion as new oxalic acid diffuses from
the* okictrolyto to the electrode* boundary surface. Conse-
quently, according t;o Nernst's theory, the electrolytic oxida-
tion velocity henceforth becomes a diffusion velocity.
The hypothesis of the latter Is always the instantaneous
equilibrium at the contact surface of heterogeneous phases;
hut. the fulfillment of this condition is not to be accepted forth-
with, particularly in the case of many organic processes which
—for instance, the reduction of nitre-bodies—are able to give
a whole series of intermediate phases up to the final equilibrium.
The influence of the electrode material upon the velocity
of reaction decides particularly against its significance in all
cases as a diffusion velocity.
Finally, to view electrolytic processes as heterogeneous sys-
tetriH does not seem at all sound, according to the description
of the electrochemical reaction mechanism given in our intro-
duction. If the first proceas, in accordance with the given
^position, is the diacharge in the electrode boundary surface,
and if the second is the separation on the electrode or the
f. anorg. Ohemic $!, 161 (1002). Bee also Brurmer, Reaction

'V«tk>citl« in Heterogeneous Systems, p. 52, Thesis, Gflttingen, 1003. Of.
fito Luther arid Brittle^ 2tnchr. f. phy». Ohemie 45, 216 (1903),
reaction of the ions present in the boundary surface with the-

depolarizer, hence in the fluid system, then the actual reaction
takes place in a homogeneous system. The typical influence of
the reacting ions will then show itself in the velocity constant
of this reaction; likewise, if the ions are derived from the lat-
ter, the typical effect of the electrode metal will be seen.
A sharp distinction will then exist between the discharge, which
can occur with an extremely great velocity, and the actual chem-
ical reaction with the depolarizer, the velocity of which will be
measurable and distinctly individualistic. In this case the
velocity of diffusion alone cannot represent the velocity of
reaction.
With the aid of other ideas concerning the electrical
reaction mechanism, particularly the reduction mechanism,
Haber and Russ1 arrive at the same interpretation . They
advance the proposition: " The . reducing phase Is formed
at the cathode with an immeasurably great velocity constant,
but the velocity with which it acts chemically on the depolarizer
depends upon the latter's peculiarities and is often measur-
ably small/ ;
By a " reducing phase" is meant hydrogen or any metal
phase which is supposed to stand in a dynamic equilibrium
with it, so that the action of the different cathode materials
can be taken as equal, a condition which can be experimentally
obtained by the choice of a cathode potential which remains
always the same.
H 2
6. Osmotic Theory of Electrical Reduction.
Haber . was the first to publish a theory of electrical reduc-
tion which is in many points free from the limiting conditions
of the diffusion theory. Later, conjointly with Russ,3 he
brought it to the form given below.
'i, 1
i\ \ 2
I' Ibid. 32, 193 (1900).
8
Ibid. 47, 263 (1904).
THEORETICS. 35
The sphere of validity of this theory, in conformity with

the experimental material, extends to the use of unattackable
cathodes at current strengths which, in contradistinction to
those chosen by Goldschmidt, lie considerably below those
necessary for developing hydrogen. The conditions are hereby
simplified, because, on the one hand, the reduction must pro-
ceed exactly according to Faraday's laws, and, on the other
hand, it can be regarded as being always accomplished by
the same agent, hydrogen. This latter hypothesis, since it per-
mits the assumption that the reducing agent obeys the laws
of gases, is extremely weighty for the theory. Herewith is
assumed that the hydrogen is present in the electrode surface
with the concentration CH- If we want to assume the re-
placement of the hydrogen by a metal, the latter must also be
regarded as obeying the laws of gases. It hence suffices to
deduce the theory only for hydrogen as a reducing agent. If
CH be the concentration of the hydrogen atoms at the cathode,
then the potential E, according to Nernst's osmotic formula, is
Off
in which R is the gas constant, and T the absolute temperature.

If the hydrogen in the cathode now reacts with the depolar-
izer M, for instance according to the equation
the speed of reduction is
or, neglecting the subtractive member,
dt
According to the above-mentioned hypotheses, we can
^directly substitute the current strength / for the speed, which
36 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS,
is proportional to it,
~~dt ==klJf
1
= C2 H or, more simply, 77777- = @2 H>
/V wJW"
'M
If this value is introduced into the potential equation,
there results
RT. J
6r if CH- is considered as constant, and the constant kf is placed

in the formula as subtractive member,
•prn r
E =-7r-ln79—const.
^ ^M
The relations were now tested for the constant / in an

alcoholic nitrobenzene solution; as a result the formula can also
be written in the following manner:
const. ;
furthermore, lor constant nitrobenzene concentration,

KT
V , T
E «-rt-lnj — const.,
and finally for constant cathode potential, the relation
r*-------= const.
So far as a logarithmic connection between E on the one

hand, and / and CM on the other resulted, the theory is veri-
\ THEORETICS. 37
I fled by the observation. However, the constant factor before

\ . RT
I the logarithm was not found at •—. It always possessed a
tf larger and somewhat variable value.
| Haber and Russ l therefore changed the original formula to
iH [ rym T
I r, / /V/ , J
E = x ( -T;— In -77-" — const.).
This expression was substantiated by experience when the

influences of diffusion were avoided as much as possible. The
factor x appears as a function of the electrode condition
It would lead too far to enlarge upon the meanings of the
factor x which were discussed by Haber arid Russ.2
c. Nummary of the Theories.

Tho two theories of Nernst and Haber above mentioned seem
to contradict one another in important points. The electrical
speed of reaction in the diffusion theory (Nernst) is directly a
speed of diffusion; Haber's formula holds good only in case the
diffusion is excluded as much as possible.
The contradiction is only an apparent one, and the difference
between the theories lies in the hypotheses. The measurement
of the speeds of reaction depends upon the conditions of the
experiment. If the reaction between two components of re-
action actually takes place instantaneously, we can vary the
time of reaction entirely at will by the period of time during
which we add one of the components. If the latter is used up
with immeasurable rapidity, the measured velocity of reaction
muflt naturally always remain proportional to the added quan-
tity of the reaction components. The Nernst theory is based on
relations in which this subsequent delivery "m effected only by the
diffusion, the reacting agent furnished by the current being
1
ZtMhr. f phy*. Chamie 47, 204 (1004).
2
Cf, atari; Hum, Concerning Reaction Accelerations and Reaction Retar-
dations in Electric Reductions and Oxidations. Ztschr. f. phys. Chemie 44,
641 (1003) Hoe also the chapter on electrode material
r
kept at the electrode by the potential relations in an infinitesi-

mal concentration as opposed to the external concentration.
Since the reaction can only proceed further if new quantities
of the agent reach the electrode, and this subsequent delivery
can be brought about only by transference and diffusion, the
first conclusion drawn is that these two factors determine
the current strength. The current can reach the electrode
only by means of ions. Since, moreover, the measurable
velocity of reaction is regulated by the current strength, it
follows further that this velocity of reaction is also regulated
by the effects of diffusion and transference. It is mentioned
in Ackerberg's experiments what'the ratios are in the presence
of a depolarizer. The theory holds good if the measurable speed
of reaction, which need not be identical with the actual velocity,
is artificially made a diffusion velocity. The considerations of
Haber suppose that the ions and depolarizer are in such great
concentrations at the electrode that the ions derived from the
great surplus bring about the reaction in accordance with the
current strength—independently of that which is subsequently
delivered by diffusion. The relations of Haber are therefore
valid only in such cases where impoverished phenomena are
excluded at the cathode. Those of Nernst are true only in
such where complete impoverishment exists, i.e., where almost
t zero concentration of the depolarizer is created at the direct

border line of reaction. For the reaction can progress only
in this case in the same proportion as the depolarizer enters
by diffusion into the reaction layer.
f;
We easily obtain results having the advantage of better
proof, if we base the reaction-kinetic speculations upon the
views developed on the reaction mechanism, according to
which the discharge of the ions at the electrode is strictly to
be distinguished from the separation on the electrode or the
reaction with the depolarizer. This kind of proof is naturally
of greater significance for the Haber than for the Nernst deduc-
tions. For even if the whole reaction, according to our sup-
position, takes place in the fluid phase, i.e. in a homogeneous
system, the principles of the reaction can practically be appli-
THEORETICS. 39,
cable in heterogeneous systems. In the localization of the dis-

charging space in the immediate vicinity of the electrode,
the layer in which the discharged ions are present may be
considered as an extremely thin film which behaves as a
heterogeneous formation towards the electrolyte. The con-
centration of the discharged ions in this film is undoubtedly
extremely small at the great velocity of reaction with which
they separate or react. Thus the progress of the reaction
depends upon the velocity with which diffusion and transference
conduct new ions to this film. If the concentration of the de-
polarizer is strong, only the last-mentioned factors will influence
the reaction velocity; if it w weak, the quantity of the depolar-
izer, which is supplied by diffusion, plays an important part.
Our views, that the laws of gases can actually be applied
to the concentration of the discharged ions, form a desirable
confirmation of Haber's relations. For the discharged ions,
which are not in or upon the electrode but in the solution,
must haw an osmotic; pressure proportional to the concentra-
tion in the discharging space, i.e. the current strength, accord-
ing to Habor'8 conditions. The validity of the laws of gases,
if we suppose a solid solution of the ions in the electrode, is
difficult to explain, particularly if the case is one of metal ions
whicli reach the cathode and there produce reduction effects.
The deductions of Haber remain unchanged formally, but their
sphere of validity appears enlarged, however, since under the
necessarily limited conditions the behavior of attackable
cathodes becomes also theoretically representable. A repe-
tition of thoso (Inductions, however,will not be given here.
The theoretical treatment of the physicochemical material,
which organic, chemistry places HO abundantly at our command,
is yet in its initial state. Not only do the many obscure points
incite to a continuation of the work, but the few results and
the numerous problems rather justify the opinion that the
phenomena of organic electrolysis are especially adapted to
carry the teachings of physical chemistry into the domain
of organic chemistry.
C HAPTER II.
METHODICS.
d
IT is assumed that the reader is familiar with the general
o
arrangements of electrochemical experiments. In the follow-
a
ing pages only those particulars will receive attention which
t;
are of special importance in the electrolysis of organic com-
pounds. The arrangement which permits the observation of
a
the decisive potentials, and their control and maintenance at I
a' constant, is particularly important. Of importance are
Cl
certain electrolyzing apparatus suitable for particular pur-
0;
poses, and also arrangements for stirring, which often de-
t]
cisively influence the course of an experiment.
n
1. THE CELLS. ct
Cells of the most varied constructions, depending upon
E
the problem in hand, are required. The conductivity of the
oi
electrolyte, the necessity of collecting gases, the separation
of the cathode and anode chambers, regulation of the tem-
p|
d
perature, the variation of the size of the electrode, all demand
certain requirements and arrangements.
Of course, the comprehensiveness of the experiment is also
of great importance. However, only the conditions which enter
into the question of scientific investigations are of interest a
rij
here. We shall, therefore, waive the repetition of the technical
arrangements for organic electrochemical processes. *JJ
In the simplest case it suffices to immerse the two electrodes J
ofi
always in a certain position in a glass vessel, and usually
parallel to one another. The vessel is closed with a hermetic-
ally fitting stopper when gases are to be collected. Three
40
be -obtained by putting in glass or porcelain worms through, the shape fir

which a continuous current of water is conducted. Metallic figs. 1-4 rep
worms must only be used if they are to serve at the same time It is evic
as electrodes. Otherwise they act in an undesirable manner as
diaphragms.
intermediate conductors in the electrolysis. Often it is impor-
In using
or cathodie-
especially if
. 2, -ft
Ga» or «
FIG, 1.—Arrangement for Cooling the Electrodes. electrolyte
the
tant to keep the electrodes cool, since their surfaces limit the for the utiif
.actual reaction space.
mt
Cooling of the electrodes is done either by using worm
electrodes, as above mentioned, or, if this is made impossible by
into
the-nature and form of the electrodes, by choosing hollow, cy- •fa ft
lindrical electrodes,—through which water is passed,—and of
647 (1 800).
METHODICS. 41
perforations are required in the stopper, one for a glass tube,,

urul the other two for the electrodes, the latter being sealed in.
A little mercury closes the circuit. Changes in temperature
are obtained by outwardly heating or cooling the vessel.
Stirring is caused by the eleetrolytically evolvod gases.
The current conditions can be varied in the most different
ways. By a choice* of concentrations, or by additions, the con-
ductivity can bo increased or diminished; also by raising or
lowering the voltage. The height of the electromotive force
developed in the coll determines the current strength; the ratio
of the hitter to the electrode surfaces gives the current density,
and to the volume of the electrolytes, the current concentra-
tions.1
This simplest form of arrangement seldom suffices; usually
a separation of the cathode and anode spaces is required.
This is oftonest obtained by the use of a diaphragm, or by
connecting, with a siphon arrangement, two separate vessels,—
one containing then anode and the other the cathode fluid;
this latter method is more rarely used, however, because the
resistance is liable to become too great. Porous earthenware
cylinders or plates arc* usually employed as diaphragms.
Diaphragms, which often answer well, are sometimes made
of gypsum, pressed asbestus (only utiliâble in alkalies 2 )r
porous cement, and parchment paper. So-called " acid-proof5>
diaphragms are also used. Cylindrical vessels arc1, simply placed •
in the \viderj|uier vessel, and plates arc* fitted in tightly, or
cemented simpler method is to make the cell of two sep-
arate part if fit ting upon ono another. Between these the di-
aphragm platn is tightly wedged with screws by means of a
ruMxT ring or a caoutchouc frame. The Wehrlin 3 cell is made in
thin fashion. Cooling and Btirring in eleetrolytical experiments-
are of Bpi*c*5i.il Importance, Aside from the external cooling
of the ('Uwtrolyfe, u constant temperature of the latter can
•Tufal, XtHchr. f. phyi*. <!hom. 34, 201 (1900).

1
Ix'Sibinc, KtHchr. f. Kl«kfcrf»ch«mi« 7, 290 (1901).
* Ibid, 3, 4aiCIH07),
be -obtained by putting in glass or porcelain worms through

which a continuous current of water is conducted. Metallic
worms must only be used if they are to serve at the same time
as electrodes. Otherwise they act in an undesirable manner as
intermediate conductors in the electrolysis. Often it is impor-
FIG. 1.—Arrangement for Cooling the Electrodes.
tant to keep the electrodes cool, since their surfaces limit the
.actual reaction space.
Cooling of the electrodes is done either by using worm
electrodes, as above mentioned, or, if this is made impossible by
the-nature and form of the electrodes, by choosing hollow, cy-
lindrical electrodes,—-through which water is passed,—and of
METHOD ICS. 43
the shapes first proposed }>y Lob l and later modified by Tui'el.2
Figs. 1-4 represent types of electrolytic cells variously employed.
It is evident from the drawings that, by choosing suitable
diaphragms, the reaction chambers can be closed from without.
In using earthenware cylinders, the reaction fluid—anodic
or cathoclic—is most suitably placed in the earthenware cylinder,
especially if the gases arc* to be determined.
^x j
..
11.
Jn
1. 1
u
.
j 1
:" " "
\
(h U 't
22ffi2ilffiia^^
FIG. 2. Tafel'n Electrolytic Cell. Fio. 3,—Wcjhrlin'B (toll.
Gas or mechanical stirrera are made UHC», of for ntirring the*

electrolytes Mechanical stirrem, however, are ernpbyed only if
the e»le»ctre)lytiei ganc*H arc* to be investigated, unless the.wi suffice
for the stirring, as Is the case in experiments with high cur-
rent strengths. By permitting the base of the stirresr to dip
into mercury,3 the? mechanical stirring can easily be arranged
in a manner so as to obtain a herrnetieul se»uL
1
Ztschr. f. Kicktrr>chernie 2, «(W5 (1890). -------------.
3
Her. cl deutffch. chcin. Clwwlliich. $&> 222,1 (HKK».
'Ldb^tschr, f, Elektrochcmic 7, 11 7 (HKK)); KtMchr. f, phya Chf*rnii* S4,
647 (1900).
The gas-tight electrode stirrers are based on the same

principle. They have the advantage of using the electrodes
themselves,—which may have any shape,—for stirring. A
troae sun&ue mo ^^«^— -r—/. -™- ™^^ A0 ^ great; im-

portance in a series of reactions, for instance in the simultane-
fine division of the components is thus assured on the elec-
trode surface the (reaction space). This matter is of great im-
•__ - ,-^wrt« r\-f vckor»'firinQ "f
FIG. 4.—Electrolytic Cell (Hofer's) FIG. 5.—Gas-tight Electrode

Stirrer.
ous reduction of two nitro-bodjies to a mixed azo-body, or
in the electrolytic preparation of azo-dyes, etc. (See Fig. 5.)
The current is conducted through mercury, which is poured
into the glass tube in which the electrode is sealed.
2. ARRANGEMENT OF EXPERIMENTS AND MEASUREMENTS OF
POTENTIAL.
The typical arrangement for an electrical decomposition is
that in which the main current flows through an ammeter and the
METHODICS. 45
cell, and the* terminals of a voltmeter, in branch circuit, are

connected directly to two points at the electrodes.
The potential of the electrode at which the respective
reaction takes place is of decisive importance on the course of
the electrolysis; it may be the cathode or anode potential or
sometimes both. The potential difference between the elec-
trodes, which is influenced by many contingencies, such as
the resistance of the diaphragm, etc., is, on the contrary,
generally without importance for the reaction. The volt-
meter shows the consumption of electrical energy only in com-
bination with the ammeter.
The potential of an electrode is determined in combination
with a second constant electrode which does not belong to
the actual electrolytic system. This subsidiary or standard
electrode, whose* potential is either arbitrarily taken as zero
or has a certain absolute value, is connected by a siphon with
the liquid surrounding the experimental electrode. The electro-
motive force of this galvanic combination is then measured
by one of the well-known methods, with a galvanometer
or capillary electrometer. If the potential difference of the
standard electrode is correctly subtracted from the obtained
value, the difference in potential of the reaction electrode,
based on the agreed-upon zeroi value of the potential, is
obtained.
Two subsidiary or standard electrodes are in use, the calo-
mel electrode of Oswald l and the hydrogen electrode of
Nernst.2 The former, consisting of a combination of mercury
covered with rnorcurous chloride* an depolarizer and immersed
in a solution of Vio a-potassium-chloride solution, has, accord-
ing to the best rneasuromeritH, an absolute potential of
0.013 volt-4-0.0008 (t°~18), in the nonse that mercury is posi-
tive, tin* solution negative*. The standard hydrogen electrode
r, FJiyMicoch^micfti McuimiromentH, p. 383, Leipzig, 1902.

*Ztnehr. f. KtoktrochVmie 4, 377 (1898); 7, 253 (1900); see also Wils-
fc, JStMchr, f, |>hy«. (*h«*m, #5, 291 (1000); (Mwald-Wilwnore, Ztachr. f.
phy*. Ch«n. 30, 91 (1901).
consists of a platinum sheet charged with hydrogen in a normal

electrolyte, i.e. normal as to the hydrogen ions. In preparing
the hydrogen electrode, the sheet platinum (or palladium)
is arranged so as to lie half in the electrolyte and half in
hydrogen gas, and the saturated state is maintained by
having a constant current of hydrogen pass through the
electrolyte. The half of the electrode not in the electrolyte
must thus be surrounded during the entire time of the ex-
periment by an atmosphere of hydrogen. Nernst gives the
hydrogen electrode the arbitrary value 0.
Depending upon the form of the cell, the connection with
the standard cell can be made by means of a siphon or other
method. Of • course the electrolyte of the normal electrode
must not react appreciably with that of the experimental
cell, and in most cases it will be of value to separate both, by
a suitably adjusted diaphragm.
The problems to which the measurement of the electrode
potential gives rise are manifold.
The task is often to determine at what potential a reaction
begins; in other words, what discharge potential the separated
or reacting ion possesses in the presence of the depolarizer.
The determination of this value is most simply made by measur-
ing the decomposition potential.1 This method is based upon
the fact that a permanent decomposition of an electrolyte can
only take place by using a certain electromotive force which
is just able to overcome that of the polarization. If we begin
to polarize with a small electromotive force, the current cannot
at first permanently pass the cell. Only when the electro-
motive force exceeds the value of the polarization does the
sudden deflection—the "'rebound'7 of a galvanometer enclosed
in the circuit for observation—phow the passage of the current,
revealing the decomposition value of the electrolyte. If in a
coordinate system the electromotive forces are considered as
abscissas, the current strengths or deflection factors of the gal-
vanometer as ordinates, then curves are obtained which show
JLe Blanc, Ztschr. f. phys. Chem. 8, 299 (1891); 12, 333 (1893).
MBTHODICS.
characteristic breaks at the decomposition
values. If the elec-
trode at which the reaction is expected to
occur is combined
with a normal electrode, and the difference in
potential at the
work-electrode is observed for increasing current strengths, it
will be found that at a certain value of the latter, a sudden
passage of the current, which appears as a break in the curve,
occurs. This break i's characteristic for the beginning of any
kind of reaction, whether it be that of the separation of ions
or their reaction with the depolarizer. When several kinds of
ions are separated or react at different electromotive forces,1
these* breaks can repeat themselves in the curve.
The simplest method of determining the beginning or non-
occurrence of a reaction consists in measuring the discharge
potential of the cations or aruons before and after the addition
of the depolarizer which is to be acted upon. A change in
potential at the addition shows the beginning of the reaction.
It is of especial importance to know the potential interval
within which one or several distinct reactions take place. The
determination of this depends upon the change in potential
which the presence of a depolarizer produces as opposed to
an electrolyte containing no depolarizer. For example, if it is
desired to learn if chlorine derivatives of phenol can be pre-
pared at the anode by electrolysis of a hydrochloric-acid solu-
tion of phenol, then the point of decomposition of the chlo-
rine ion, in combination with the hydrogen electrode, is found
at Uil volts in a l /i n-hydrochloric-acid solution. If phenol
is uddfid to this solution, the break in the curve occurs
already at 0.9 volt.2 Therefore the span in potential, within
which the reaction for the formation of chlorine derivatives
of phenol rriunt take place, lies between 0.9 arid 1.8 volts. In
thin manner l)ony~H£nault, among others, determined the
dtwompoHition potential of the OH ions, in combination with
the* hydrogen electrode, in. dilute sulphuric-acid solution both
without and with the addition of ethyl alcohol. He found
/ ... » H . d h ^ BweTibid
6 ,1 K J 08 9 8 ).'
"i *Cf. Dony-H^nnult, Ztsehr, f. Klektrochemie 6, 533 (1900).
1 48 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
I
1
1
in the first case that the discharge potential was at 1.66
volts, in the second case at about 1.2-1.3 volts. Either
acetaldehyde or acetic acid can be formed by the action of
hydroxyl ions upon alcohol. A measurement of the decom-
position potential of the hydroxyl ions in dilute sulphuric acid
I'I and in the presence of acetaldehyde did not perceptibly lower
the potential. The acetaldehyde, under the existing circum-
stances, does not act as a depolarizer, so that, if the potential
during electrolysis is kept between 1.3-1.6 volts, an almost
FIG. 6.—Arrangement of Experiment (Ilaber).
quantitative yield of acetaldehyde must be obtained. The

: •;• experiments completely verified this theoretical deduction.
The second problem, which often occurs, is to keep this
potential at a certain value, or within certain limits. This
METHODICS. 49
is accomplished by setting the cell, which consists of the

work-electrode and the normal electrode, at the desired ten-
sion by choosing the suitable polarizing current strength—
according to the compensation method,—and by taking care
that the tension existing between the work electrode and
the standard electrode retains the value of the compensating
potential by varying the current strength, as may become
necessary during the course of the. experiment. Haberl has I
used this method of procedure for limited potentials, and Lob
and Moore2 employed it for an entirely distinct constant'
potential during prolonged electrolyses, Figs. 6 and 7 are '
sketches of the arrangements of their experiments. The
requirements for the reduction of nitrobenzene, as expressed
in the theoretical part of this book, were proved by these
experiments,—namely, that, by reason of the necessary limi-
tations, only the cathode potential is decisive for the obtainable
reduction phase.
If in simpler cases, which are naturally rarer in organic
electrolysis, the only point is to keep the total decomposition
tension between the electrodes below a certain value, then
it will suffice to employ suitably small electromotive forces,
or such limited by branching.
Finally, the measurement of single electrode potentials is
of importance m itself for obtaining the depolarizing values,
i.e., the potential differences of an. electrolyte in connection with
a certain electrode with or without a depolarizer. It is evident
that these depolarizer values are characteristic quantities for
the chemical nature of the depolarizer, and are very closely
related to the constitution and configuration of the molecule.
Introductory experiments on this question for nitro- and nitroso-
bodies have been made by Panchaud de Bottens.8 Lob and 11
Moore 4 have also measured the depolarizing values for nitro-
benzene at different electrodes and current strengths. It was
, i Ztschr. f. Elektrochemie 4, 507 (1898).
* Ztschr. f. physik. Chena. 47, 432 (1904).
Ztschr. f. Elektrochemie 8, 305, 332 (1902).
* Ber. d 5. Internat. Kongr. f. angew. Chemie, Berlin, 1903, 4, 656.
50 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS^
found that they- generally became smaller with increasing

current strengths. Single electrode metals, however, show
peculiarities which suggest the occurrence of variable reactions.
Besides the usual method of arrangement mentioned at the
beginning of this chapter, in which the current derived from
any suitable source of electricity passes through the cell,
the apparatus can often be suitably simplified—especially
for electrical reductions—by employing Lob reaction cells1
Main Current: ----- —— A, Current Source, £ Rheostat, C Ammeter, D Anode, E Cathode,

F Plate Kettintance, % Experimental (Jell.
Measuring Current: ...........A'Compensation Accumulators, ft 1 JProciHion Voltmeter, C'Plate
Resistance, I)' Ballast IlemAtance, JKf Galvanometer, f" Instan-
taneous Cutout, O Standard Electrode.
FIG. 7.—Ldb's Experimental Arrangement
or short-circuiting cells. Cells can be constructed, which do

away with the primary-current production in laboratory
work, based upon the fact, already used by Iloyer2 in the
reduction of oxalic acid, that a reaction producible by the
current can inversely serve as a part of a suitably constructed
electric cell. If, for instance, nitrobenzene is dissolved in con-
centrated sulphuric acid, the solution poured into an earthen
ware cylinder, a piece of platinum dipped in the latter and the
1
Ber. d. deutsch. chem. Geseilsch. 29, 1390 (1806).
2
Compt. rend. 69, 1374 (1869); see also Lapeyri&re, Tommasi, Trait6
d'Elecbcochimie 724,720 (1899).
METHODICiS. 51
cylinder with its contents placed in another vessel containing di-

lute sulphuric acid in which is immersed a piece of amalgamated
zinc, we have nn electric cell or battery. On making a metallic
contact between the zinc and platinum with a binding-screw,
quite a considerable; current circulates even at a low tension
since the resistance is small. After a few hours the contents
of the earthenware cylinder solidifies, forming a pasty mass of
amidophonol sulphate*. Such systems can be prepared in very
many suitable forms, particularly in such a manner that heat,
or pressure, etc., can be applied during the operation.
3. THE ELECTRODES.
The nature of the electrodes is of great importance for the
course of electrolytic processes. The material is not only
decisive for the effect, as already fully discussed, but the nature
of the surface and the.*, previous treatment of the electrodes
can decidedly influence the; course of the electrolysis. In the
first place it is obvious that the size of the surface wetted by
the electrolyte is codeterminative for the potential and current
density, and even on this account its smoothness or roughness
form decisive factors; but its form, and the mutual position of
both, electrodes, must also be taken into consideration, for on
these; depend the distribution of the lines of force on the surface.
In general, the data em the current densities and of the potentials
refer to mean values; actually both are usually unlike at different
points of the surface, since the number of the discharging
current lines is an uneven one.
If IH, the»re*fore, often to be recommended, especially in
aeerurate potential measurements, to "'touch over " the surface.
Ilalxr l d<x»ft this by shaping the siphon end of the standard'| •
electrode into a capillary tube, which he conducts along the \
electrode surface. If the object is to obtain tolerably equal
current doriBiticB without this accurate checking of the re-
suits, the relative! size arid position of both electrodes must r|
y
;
Ztechr. f. phya. Chemto 8£, 209 (1900).
I ,' be taken into consideration. They may be chosen of similar

, ! ,i dimensions and like form, and hung parallel in the bath.
1
j ' A better way is to choose concentric arrangements such as
! (i mentioned by Lobl and Tafel.2 These electrodes consist of
I concentric cylinders between which the electrolysis takes place.
I It has already been mentioned, in the discussion on the excess
f , •( potential phenomenon, in what manner the nature of the- elec-
v (
! trode potential is of importance for the potential, leaving out
of the question the changed dimensions. The evolution of
hydrogen is well-nigh reversible at platinized platinum (0.005
volt excess potential); at bright.(polished) platinum it is already
•? 0.09 volt. This influence possibly occurs in a similar manner
with,all electrode materials. Tafel,3 by reducing difficultly re-
I( ducible substances in sulphuric-acid solution, was able to obtain
if] good results only at a lead cathode, the surface* of which was
coated with a layer of spongy lead. Such a surface can easily
be prepared by first coating the electrode anodically with a thin
film of lead peroxide and then reducing this cathodically. Sim-
ultaneously a solution of the foreign metals in the surface coat is
brought about by the anodic process and a pure lead sur face
', obtained by reduction. Tafel, by a great number of exam ples,
has likewise demonstrated how important it is to have a pure
cathode. Even traces of impurities can decisively modify the
effect. The simplest supposition is that the velocity of separa-
tion of the discharged ions is catalytically influenced by the traces
of impurities. This assumption agrees best with the experimen-
tal results. Indeed, if the reduction energy is lowered by the
impurities, we must conclude that an accelerated catalytical
action of the hydrogen formati on occurs; this agrees with the
.,;' observation of Tafel. that , wit h a constant-current source and
i"» outer resi stance, a disturbance of the reduction goes hand in
', 'I h an d w i t h a n i n cr e a s e ot t he c u r r e nt , or , w h at i s t he s a m e
IS thing, a lowering of the potential difference at the cathode.
1
2
Ber. d. deutsch. chem. Gesellsch. 33, 2223 (1900).
a
Ztschr. f. phys. Chem. 34, 187 (1900).
METHODICS. 53
Lob and Moore'1 have obtained the suitable surface con-

stitution and purity of the cathode in a different manner from
"Tafel. They start with a carefully platinized platinum gauze
electrode? and coat this electrolytically with the desired metal
by electrolysing a pure salt solution under suitable conditions.
They thus succeeded, even with attackable cathodes, in ob-
taining quite constant cathode potentials for a long period.
Russ2 has observed a peculiar influence of the pretrcatment '
of the electrodes. If strong currents are sent through the cell
for a longer period, so that an energetic evolution of hydrogen
occurs in the presence of a depolarizer, the cathode potential
soon drops, even if the current remains constant, and the evolu-
tion of hydrogen ceases. The original potential and renewed
hydrogen evolution, after a short interruption of the current,
reoccurs when the current is again turned on. Hence,, the elec-
trodes depolarize butter after being charged with hydrogen
than without the latter. The extent of this influence varies
with different metals.
1
i. c.
2
ZtHchr. f. phy» Chem. 44, 041 (1903).
CHAPTER III.
ELECTROLYSIS OF ALIPHATIC COMPOUNDS.
ORGANIC compounds which are decomposed in solution by

a direct current can be divided into those that behave as elec-
trolytes and those that act merely as depolarizers. This
division is not, however, altogether appropriate, because both
effects often occur simultaneously, so that a strict carrying out
of this disposition is not possible without arbitrariness and
numerous repetitions. The classification into oxidation and
reduction processes, which proved practical in the theoretical
part, would also be serviceable in the presentation of the ex-
perimental data, even though anodic and cathodic effects are
sometimes observed side by side, or successively, in an elec-
trolysis. However, the advantages of the latter division
are combined with the greatest possible survey of the material
r if this is arranged only in accordance with the chemical, character
of the substances which serve as the starting-point. The
Li sequence of the latter is prescribed by the familiar arrange-
ment employed in text-books on organic chemistry. Moreover,
the property of depolarizing, anodically or cathodipally, depends
upon the nature of the materials which serve as the starting-
point, each group of bodies exhibiting a fixity in its electro-
chemical behavior, whereby an almost separate grouping of
the oxidation and reduction processes naturally follows.
1. CAEBON AND HYDROCARBONS.

'$;< Carbon.
Carbon, the characteristic element of all organic com
pounds, is, as such, also the primal product in the eleetro-
54
ELECTROLYSIS OF ALIPHATIC COMPOUNDS, 55
synthesis of organic substances. The well-investigated electro-

thermie processes of carbide formation on the one hand, and,
on the other, the little explained phenomena of the electrolytic
solution of carbon by the action of the anode current, form
the introduction to these syntheses. That this solution occurs
when carbon is used as the anode in an acid electrolyte, has
been repeatedly observed; likewise the frequently occurring
presence1 of carbon in the cathode precipitate in galvanic metal-
deposition luts also been rioted. In the electrolysis of dilute
sulphuric aeid, using carbon electrodes, Bartoli and Papasogli1
had found that the anode carbon is attacked, which was shown
by the appearance of carbon mon- and dioxide. Coehn2
then demonstrated that carbon goes into solution under suit-
able conditions, coloring the sulphuric acid; as a constituent
part of the cation it wanders to the cathode arid deposits itself,
like a metal, as a conductive1, coating upon the platinum cathode.
The nature* of the solution (carbon hydroxide?) and of the pre-
cipitate has not yet been explained. Coehn3 was able, how-
ever, to prove that the solution of the carbon conforms to
Faraday's law arid leads to the expected electrochemical equiv-
12
alerit -j- « 3.
Hydrocarbons.
The great chemical resistibility of aliphatic hydrocarbons
and the aggregate state of their members poor in carbon make
thorn appear as unsuitable material for electrolytical experi-
ments. Only the addition-reactions of unsaturated hydro-
carbons offer an experimental field. Thin has riot yet been
developed. These reactions are cathodic in the addition of
hydrogen, and anodic in the addition of halogens, etc. The
fact that such hydrocarbons occur in the decomposition of
aliphatic acids gives us an indication as to their behavior, which
will be mentioned at the proper place.
. chtm. 14, 90; IB, 401 (1885); Comp. rend. 102. 303 (1886).
s
ZtHchr. f, Klektrochemfo 2, 640, 010 (1896).
•Ibid Sr 424 (1807),
Acetylene is the only hydrocarbon which has been used as a

primal material.
Acetylene. — Coehn and Billitzcr1 have subjected acetylene
to the action of the oxidizing current in alkaline and acicl
solution with limited anode potential The discharging poten-
tial of oxygen, which is in the neighborhood of 1.7 volts in a
pure potassium-hydroxide solution, is lowered by acetylene to
1.22 volts. At this potential a reaction begins. It is possible
in the same experiment to convert the process into a quantita-
tive one, if the tension is kept between 1.22 and 1.6 volts, a
potential at which a second reaction begins, as shown by the
sudden jump in the current strength. At 1.35 volts formic
acid is produced exclusively, according to the following equa-
tion:
C2H2 + 6 OH - 2 H20 + 2 HCOOIL
In sulphuric-acid solution the process proceeds differently.
By conducting acetylene into sulphuric acid, aldehyde is first
produced. This causes a depolarization of about 0.19 volt.
A quantitative oxidation of the aldehyde to acetic add occurs
if the tension remains below the discharging tension of oxygen:
, CH3CHO + 2 OH - CHaCOOH + H2O.
Nothing is as yet known regarding the reduction of acetylene

and the addition of halogens.
2. NlTRO-DERTVATIVES OP HYDROCARBONS.
The reduction of aliphatic nitro-hycirocarbons in dilute

alcoholic sulphuric-acid solution has been accomplished by
Pierron.2 The /J-alkyl-hydroxylamines are obtained at plati-
num anodes and at a'temperature of 15°-20P:
RNO S +4H- RNHOH+HaO,
1
2
Bull, soc, chim. [3] 21, 780 (1809).
i ELECTROLYSIS OF ALIPHATIC COMPOUNDS. 57
and at 70°-75° the amines:

RNOo+611 - RNH2 + 2H20.
Nitromethane thus yields either methylhydroxylamine or
methylamine. When concentrated hydrochloric or sulphuric
acid in used, hydroxylarninc and formaldehyde are formed, i,e.
the decomposition products of an oxime which was probably
li
formed first:
CII3N02+2H«CH2 : NOH + II2O = NH2OH + CH30.

Under similar conditions nitroethane is converted into /?-
ethylhydroxylarnine or othylamine; and 7^-nitropropane int<&
/?-n-propylhydroxy lamina or n-propylamine.
3. HYDROXYL COMPOUNDS.
Oxidation products are principally to be expected with the
aliphatic hydroxyl compounds as the lowest stage of oxidation.
In fact, hydrogen is evolved unused, even if the cathode and
anode are not separated by diaphragms, while the oxygen is-
absorbed.
Methyl Alcohol.—We are indebted to Renard,1 Almeida
and Dehc'rain,2 Jaillard,3 Habermann 4 and Cdnnell & for numer-
ous experiments on the electrolysis of methyl alcohol.
The results obtained with methyl alcohol can be summed
up MS follows: Hydrogen being evolved, the oxidation products-
formed arc*:
1. In aqueous sulphuric-acid solution: Methyl formate,
methylal, methyl acetate, acetic acid, and methyl-sulphuric
add, a little carbon dioxide and monoxide, but no formic
aldehyde*.
* Compt. rend, 80, 105, 230 (1875).

2
Ibid. 51, 214 (1865).
s
Ibid. 68, 203 (1863).
*Monatnch. 7,2590886).
•Pogg. Ann, n, 487 (1835).
Renard considers the formation of acetic acid as ;due to

reciprocal action between the alcohol and carbon monoxide:
CHsOH + CO = CH3 - COOH.
Jahn 1 thinks the formation must be traceable to the presence

of ethyl alcohol.
2. In aqueous solution, on addition of potassium acetate
(Habermann): Besides carbon dioxide and carbon monoxide,
methane and potassium methyl-carbonate.
3. Without a solvent, by itself or with the addition of a little
alkali: Chiefly potassium carbonate; also hydrogen, oxygen,
carbon monoxide, and carbon dioxide.
While these experiments, which were carried out without
giving a theoretical insight into the nature of the electro-
chemical reaction, yielded almost all the possible oxidation
products in the oxidation of methyl alcohol, Klbs arid Brunner 2
have discovered a method which gives 80% of the current
yield in formaldehyde. This is exactly the substance which
could not be proven present up to that time among the electro-
lytic oxidation products of methyl alcohol. Elbs and Brunner
electrolysed an aqueous solution of 160 g. methyl alcohol
and 49 to 98 g. sulphuric acid in a litre. They employed a
bright platinum anode in an earthenware cylinder, using a
current density of 3.75 amp.'and a temperature of 30°. Only
traces of formic acid and carbonic acid and a little carbon
monoxide, aside from the 80 per cent, of formaldehyde, were
formed. Plating the platinum anode with platinum decreased
the yield of formaldehyde at the expense of the carbon dioxide.
With an anode of lead peroxide the carbon dioxide exceeded
the aldehyde.
Dony-H6nault,3 by measuring the depolarizing action of
the alcohol in 3 n-sulphuric acid, found no indications of the
1
Jahn, Grandriss d. Elektrochemie 201 (1894).
2
Ztschr, 1 Elektrochemie 0, 604 (1900).
8
Ibid.,533 (1900).
ELECTROLYSIS OF ALIPHATIC COMPOUNDS. 59
production of formaldehyde, and also obtained a negative

result in an (.experiment.
The significance of all the conditions, for instance the acid
concentration, plainly follows from the different results of the
liist-namod investigators.
Ethyl Alcohol.—In the case of this alcohol the more impor-
tant results have been obtained by the investigators above
mentioned. Schonbein l and Becquerel,2 and Bartoli and Papa-
sogli3 also later 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. In sulphuric acid solution: Aldehyde, acetic ester,
formic ester, ethylidene oxyethyl ether [ CHs—CH< Xn TJ 1
\ \UU2-tl ,5/
(Renartl), and ethyl-sulphuric acid.
2. Almeida and DelwSrain state that in the electrolysis of
a nitric-acid solution they observed, in addition to these oxida-
tion products, carbonaceous derivatives of ammonia at the
negative pole.
3. In hydrochloric-acid solution4 chlor-acetic acids occur,
in addition to the corresponding oxidation products (Riche 5).
Habermann, on electrolysing the alcohol in alkaline solution,
obtained, besides carbon dioxide, an aldehyde resin (Liidersdorf
and Connel 6) from which he isolated a body closely related
to cinnarnic aldehyde. In aqueous solution, on the addition
of potassium acetate, the alcohol was split up into ethane,
potassium ethyl-carbonate, carbon dioxide, and acetic ester.
Jaillard7 and Riche8 proved the formation of aldehyde in
sulphuric- and acetic-acid solution. In hydrochloric-acid solu-
1
ToinmaHi, Truit.6 d'Klcetrochirme 726 (1889).
3
Compt. r«nd. 81, 1002 (1875) et al. places of Compt rend.; Tommasi,
d'KIectrochimie 726 (1889).
'Wiedcm. Beibliiiter 7, 121 (1882).
4
Fogg. Ann. 19,77 (1830).
•TornmaKi, Trait/* d'Eleetroehimie 728 (1889),
9
Pogg. Ann. 30, 487; Phil Mag 18, 47.
Utampt. rend. 58, 203 (1804).
8
Tommasi, Trait^ d'Kloctrochimie 728 (1889).
, ',8,
tion Liidersdorf1 obtained ester like compounds containing

chlorine. Dony-Henault2 and Elbs and Brunner3 have shown
how to obtain certain products, depending upon definite con-
ditions. While the former directed his aim to the anode
potential; the latter sought to determine precisely the chemical
factors which influence the reaction.
Dony-Henault observed that alcohol is oxidized in sulphuric-
acid solution already at an anode potential of 1.3 volts, .as
measured in connection with the hydrogen electrode- The
oxidation of acetaldehyde, on the contrary, requires a potential
of 1.66 volts to convert the aldehyde into acetic acid. Hence,
the alcohol can be oxidized only to aldehyde between 1.3 and
1.66 volts. The experiment proved that, when a platinized
platinum electrode is employed, only acetaldehyde is formed,
and this quantitatively. The aldehyde yield decreases at
a higher potential, the acid content of the electrolytes in-
creases, and, at the same time, ethyl-sulphuric acid can be
detected, as already shown by Ilenarcl. Dony-Henault ascribes
the formation of this acid to the discharge of the SCVions.
According to Elbs, a purely chemical action of the sulphuric
acid (which becomes concentrated at the anode) on the alcohol
is the more probable.
Elbs and Brunner electrolysed an aqueous solution con-
taining 5 g.-molecule equivalents of alcohol and 0.5-1 g.-mole-
¥,n
cule equivalent of sulphuric acid. They obtained acetalde-
hyde, acetic acid, and carbon dioxide, but no carbon monoxide.
Acetic acid is the principal product at a bright (polished) plati-
num electrode. It is formed with a current yield of over 80%,
the yield of aldehyde amounting to about only one twentieth
of the weight of the acetic acid,
lodoform from Ethyl Alcohol—Chloroform and bromoform
cannot be prepared eieetrolytically from alcohol (Elbs and
Herz 4 ). This is contrary to the claims of the I). II. P. No.
l
Pogg. Ann. 19,77 (1830).
2
Ztsehr. f. Elektrochomie 0, 533 (1900).
s
Ibid 6, 604 (1900)
4
Ibid. 4, 118 (1807),
ELECTROLYSIS OF ALIPHATIC COMPOUNDS, 61
29771 (1884). Coughlin 1 has .substantially verified the results

of Elbs in the case of bromoforrn. He obtained only small
quantities of this body which can be easily prepared electro-
lytically from acotone. The* formation of iodoform, on the
contrary, takes place smoothly. It is obtained technically
according to the above-mentioned patent. Elbs and Herz
have established the following conditions for this reaction.
The course of the reaction is illustrated by the equation:
10 I + H20 = CHI3+C02+ 7 HI.
The electrolysis is best performed as follows: A solution of
13-15 g. calcined soda and 10 g. potassium iodide in 100 cc.
water and 20 cc. alcohol is placed in a porous earthenware
cylinder with platinum anode. The cathode, of nickel, is
surrounded by a strong solution of sodium hydroxide. The elec-
trolysis is carried out at a temperature of 70° C., with a current
density at the anode of 1 amp. per 100 sq. cm., arid is continued
for 2-3 hours. After several hours the iodoform crystallizes
out, the current yield being from 60-70 per cent. The chief
by-product remaining in the mother liquor is sodium iodate.
The reduction of the iodoform by the electrolytically gener-
ated hydrogen is insignificant, according to the observations
of Forster and Mewes.2
This behavior permits the discarding of the earthenware
cylinder. It suffices to envelop the cathodes with parchment
paper, whereby the resistance and the consumption of electrical
energy is considerably diminished. The diffusion of the free
alkali hydroxide away fromtho cathode necessitates the continu-
ous introduction of carbonic-acid gas, because caustic alkali pre-
vents the formation of iodoform, while carbonate promotes it.
When using the covered cathodes, 20 g. calcined soda, 20 g.
potassium iodide, and 50 cc. alcohol in 200 cc. water are
electrolysed at a temperature of 50°-70°, a current of carbonic-
acid gas .being conducted into the solution between anode and
1
Am. Ctosm. Journ. 27, 63 (1901).
2
»tochr. f. Klektwxshflmie 4, 268 (1897),
cathode. The current density at the platinum anode can be

from 1 to 3 amp., at the platinum cathode 4 to 8 amp., for
100 sq. cm.1 The current yield is about 80%. A series of
; secondary reactions, which are not mentioned in the above

equation, occur in this process. The hydriodic acid reacts with
the soda, liberating carbonic acid and forming sodium iodide,
which in turn is subject to decomposition. The iodine is con-
verted at the anode into hypoiodite which converts the alcohol
by oxidation and substitution into iodoform. Alkali-iodate is
also formed by oxidation of the hypoiodite.
The reaction is the same as that involved in the usual
chemical preparation of iodoform, whereby a colorless solution
of hypoiodite (obtained by dissolving iodine in a sufficient
quantity of potassium-hydroxide solution) is made to react with
alcohol. The^ decomposition potential of potassium iodide,
investigated by Dony-Henault,2 shows that the iodine as such
does not act on the alcohol, but only after its conversion
into hypoiodite. The iodine ions are set free at the same
anode potential no matter if alcohol is added or not. The
alcohol does not act as a depolarizer towards the iodine ion;
the electrical iodoform synthesis is a typical secondary
process.
Preparation of Chloral.—Chloral is obtained according to a
process3 devised by the Chemische Fabrik auf Aktien (vorrn. E.
Schering), if alcohol is permitted to flow into the anode chamber
'f ' I of the cell during the electrolysis of a potassium-chloride solu-
tion. Glucose, starch, and sugar thus also yield chloral
Incidentally it may also be mentioned that Sand and
Singer 4 have prepared alcohols electrolytically by reducing the
mercuric-iodide compounds of alcohols. The cathode is a
large sheet of platinum which is immersed in the solution of
1
Elba, tFbungsbeispiele fur die elektrolytische Darstellung chemischer
Praparate (Halle, 1902), 95.
2
8
Elektrochem. Ztschr. 1, 70 (1894).
4
the iodide in a 10% potassium-hydroxide solution:

IHgCH2 • CHaOH + 2 H = Hg + HI + C2H5OH.
of
Propyl Alcohol. — n-Propyl alcohol offers a considerably
greater resistance to electrical oxidation than methyl or ethyl
alcohol, according to experiments made by Elbs and Brunner.1
1- Propionic acid is formed as the principal product, with a cur-
Dl rent- yield of over 90%, at bright (polished) and platinized
is platinum anodes, as well as at lead peroxide anodes when the
alcohol is electrolysed in sulphuric-acid solution. A little pro-
il pionic aldehyde also occurs at lower current densities. The
n formation of carbon mon- and dioxides is likewise very insig-
it nificant.
h Isopropyl Alcohol, under conditions similar to the above
ji electrolysis of n-propyl alcohol, decomposes in accordance with
i
h the equations:
Q
I. CHaCHCOHJCHa+O-CHaCOCHs+HaO;
e
e II. CH3COCH3+30=CH3COOH+HCOOH;
III. HCOOH + 0-C0 3 +H2 0.
Acetone, acetic acid, formic acid, and carbonic acid are formed.
The oxidation takes place more easily than in the case of the
primary alcohols, and yields up to 70% acetone, which, however,
is readily oxidized further. In alkaline electrolytes the alcohols
are converted at the anode into complicated condensation
products of the aldehydes.
Isoamyl Alcohol. — The amyl alcohol produced during
fermentation was likewise exposed by Elbs and Brunner to
the anodic current action in sulphuric-acid solution. It is
converted into isovaleric acid with a current yield of about
80%. Some carbonic acid also formed, but isovaleric aldehyde
was not present under the chosen conditions.
GlycoL — Of diatomic alcohols only glycol seems to have
been the subject of investigation. Renard 2 observed in the
1
2
Aim. chim. phys. [5] 17, 303, 313 (1879); Compt. rend. 81, 188 (1875),
82, 562 (1870} .
electrolysis of a sulphuric-acid solution of glycol, besides the

formation of hydrogen, carbon mon- and dioxide, arid oxygen,
that trioxymethylene, glycolic acid, formic acid, arid a sub-
stance isomeric with-glucose were present in the solution.
In phosphoric-acid solution the results arc* similar.
Glycerin.—Ilenardl also investigated the behavior of glycerin.
In the electrolysis of a dilute sulphuric-acid solution he obtained
besides the gases, hydrogen, oxygen, carbon monoxide and
dioxide,—trioxymcthyleno, formic acid, acetic acid, glyceric
aldehyde, arid a body to whose barium compound he gave the
formula (CsHaO^Ba (glyceric acid?). Further electrolysis of
glyc&ric aldehyde gave the ordinary oxidation products, and,
as in the case of glycol, a substance closely related to ordinary
glucose. Stone and McCoy2 found similar results in acid
solution.
Bartoli and Papasogli3 repeated these experiments, varying
the material of the electrodes, and obtained the following
results:
Carbon anode and platinum cathode gave trioxymethylene,
formic acid, glyceric acid, a substance similar to glucose, and a
resin.
Graphite and platinum electrodes yielded the same products,
but a larger per cent of formic acid was formed on using the
latter. Mellogen was formed at the positive electrode.
Experiments on the electrolysis of glycerin in alkaline solu-
tion were made by Werther,4 Itcnard,5 Voigt,6 and Stone and
McCoy.7 As principal products there* resulted acrolem and
acrylic acid, besides glyceric aldehyde or its condensation
products, and glyceric acid, graphitic acid, formic acid and,
according to Voigt, also propionic acid.
1
Compt. rend, 81, 188 (1«75), 82, 562 (1876).
2
Amer. Chem. Journ. 15, 666 (1803),
8
Gam chim. 18, 287 (1883).
4
Journ, prakt, Chem, 88, 161 (1868).
6
Compt. rend. 82, 562 (1876).
8
Ztschr. f. angew. Chcmie 107 (1894).
7
Amer. Chem.* Journ. 15, 656 (1893).
;•*§
ELECTEOLYSIS OF ALIPHATIC COMPOUNDS. 65
Mannite.—This hexatornic alcohol has been investigated

by Renard.1 Bizzarini and Campani2 have published the re-
sults of an investigation on erythrite.
In the elcctrolyzed. fluid from mannite Renard obtained
formic acid, trioxymethylene, oxalic acid, a sugar isomeric with
glucose, and an acid, C6H8O8, which he regarded as the aldehyde
of saccharic acid. He could not detect mannonic acid.
Erythrite is oxidized to a great extent.
4. DERIVATIVES OF THE ALCOHOLS.
Mercaptans. — Bunge3 electrolysed the alkali salts of

ethyl and methyl rnercaptans and observed the formation
of disulphides at the positive pole. In the case of the sulpho-
compounds, however, the free acids were generated.
Methyl-Sulphuric Acid.—This acid, investigated by Renard,4
yielded hydrogen at the negative pole, while formic acid, carbon
dioxide, carbon monoxide, and trioxymethylene, besides free
sulphuric acid, were found at the positive pole.
Potassium Trichlonnethyl-Sulphate.—This compound, elec-
trolyzed by Bunge/ gave hydrogen and alkali at the negative
pole; and at the positive pole oxygen, carbonic-acid gas,
chlorine, sulphuric acid, and perchloric acid.
Potassium Trichlonnethylsulphonate.—This salt was elec-
trolyzed by Kolbe 6 in neutral concentrated aqueous solution
and gave the following results:
The solution became strongly acid and contained free hydro-
chloric and sulphuric acids. Hydrogen was gradually evolved
at the negative pole, After the decomposition was complete
the solution contained potassium perchlorate, which was also
observed in the case of potassium trichlormethyl-sulphate.
1
Ann. chim. phys. [5] 17, 289, 316 (1879).
2
Gaza, chim. 13, 490 (1883).
8
Her. d. deutsch. chenx. Gesellseh. B, 295, 911 (1870).
4
Ann, chim. phys. [5] 17, 289 (1879).
6
Ber. d, deutsch. chenx Geseilsch. 3, 911 (1870).
1
Joum. prakt. Chan. 62, 311 (18,54).
Ethyl-Sulphuric Acid.—Ethyl-sulphuric acid, on being sub-

jected to electrolysis gave, according to Renard,1 at the negative
pole hydrogen, and at the positive pole acetic acid, some formic
acid, aldehyde, and sulphuric acid. In concentrated solution a
great er proportion of acetic acid was formed. The potassium
salt on electrolysis breaks up, according to Hittorf, 2 into the
i ons K- and -OS0 2 -OC 2 H 5 .
By using a diaphragm, Guthrie 3 obtained aldehyde and
carbonic acid at the anode.
Ethyl-Phosphoric Aci d yielded Renard l carbonic acid,
aldehyde, and free phosphoric acid.
Potassium Isoamyl-Sulphate, according to Guthrie,3 is de-
composed into oxygen, valeric acid, and sulphuric acid, while
Potassium Isoamyl-Phosphat e is split up into val eric acid
and phosphoric acid.
I ijjj Potassium Isethi onat e breaks up (Bunge 4 ) i nto hydrogen
and free acid.
5. ALDEHYDES , KETONES , AND THEIR DERIVATIVES .
(a) Aldehydes.
Aldehydes occur as oxidation products of primary alcohols.
They are readily converted into acids and give, when reduced,
primary alcohols. The ketones, the oxidation products of
secondary alcohols, are oxidized with difficulty. They can
only be converted into acids by simultaneously splitting up
the carbon chain. On being reduced they are again converted
into secondary alcohols. This behavior is also apparent upon
electrolysis; however, the reaction becomes more complicated
as the molecule becomes more complex by an enlargement of
the carbon chain and the entrance of substituents. Extensive
decompositions then occur readily and the decomposition prod-
1
Ann. chim. phys. [5] 17, 289 (1879).
2
Pogg. Ann. 106, 530 (1859).
8
Lieb. Ann. 99, 64 (1856).
4
Ber. d. deutsch chern. Gesellsch. 3, 911 (1870).
. ucts, which are, naturally, often neither aldehydes or ketones; are

[ - changed further in accordance with their individual nature.
Aldehydes and ketones (like the alcohols) are non-electrolytes,
and act merely as depolarizers. The acids, however, which
; are formed by the reaction, often play a decisive part in the
current conductivity, so that more thorough experiments are
required in many cases to fully learn the conditions electrically
dominating.
The fact that aldehydes occur among the reaction products
of the alcohol electrolyses is perhaps the reason why they have
rarely been chosen as the starting-point in special experiments.
|, Considering the important role the aldehydes play as intermedi-
? ate members of syntheses, the treatment of this subject would
be highly remunerative, particularly 'with the aid of potential
adjustments at certain values. More attention has recently
been given to work on the ketones.
Derivatives of Formaldehyde and Acetaldehyde.—According
to Tafel and Pfeffermann,1 the phenylhydrazones of aldehydes
are readily converted into amines by reduction in sulphuric-
acid solution at a lead cathode. Thus ethylidene phenyl-
t, hydrazine yields about 60% of the theoretical percentage of
|; pure ethylamine salt. The decomposition of glyoxime is more
complicated. Besides ammonia and glyoxal and a small
quantity of an acid (glyoxylic acid ?) there is formed as the
, principal product the crystalline sulphate of a base, C2H8 02N2,
^ the nature of which could not be determined with certainty.
/ Ethylenediamine is not formed. Nor was a diamine obtained
| from methylglyoxime.
(; The condensation products of aldehydes with ammonia or
I amido-eompounds are easily reduced to amines in sulphuric-acid
f solution at lead cathodes. Thus hexamethylenetetramine yields
I methylamine (Knudson 2); ethylideneimine, ethylamine; the base
from acetaldehyde and ethylamine, diethylamine. Aromatic
aldehydes behave similarly. The Farbwerke vorm. Meister,
1
Her. d. deutsch. Gesellsch. 35,1510 (1902).
2
D. R. P. No, 143197(1902).
,68 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
Lucius and Br lining 1 obtain the same effect in neutral or am-

moniacal solution of the condensation products of fatty alde-
hydes with ammonia.
Chloral Hydrate. — Tommasi 2 electrolysed a sulphuric-acid
solution of chloral hydrate and was able to detect the presence
of hydrochloric acid. On using diaphragms an abundance of
chlorine was evolved at the anode, and acetalhedyde collected
at the cathode.
Grape Sugar. — This sugar (investigated by Renard 3) on
,
being subjected to the action of the current broke up into
V carbon mon- and dioxide, formic acid, trioxymethylene, and
saccharic acid. O'Brien Gunn4 mentions that the aqueous
glucose solution is converted by cathode reduction into mannite:
Cane Sugar. — On electrolyzing a concentrated solution of

cane sugar, Brester 5 found that the solution turns strongly
I acid and acquires reducing properties, very little carbon di-

oxide being evolved. He was unable to determine the nature
of the substance which he isolated by distillation, and which
was free from formic and acetic acids. Continued electrolysis
produced further oxidation.
The same author made some experiments on the electrolysis
of dextrine, gum arabic, and collodion, but obtained no note-
worthy results.
The general impression gained from these investigations is
one of successive oxidation. The electrolytic oxygen gradually
oxidizes the substances, the final product being carbon dioxide.
Intermediate products are formed during the electrolysis, their
quantity varying with the duration of the electrolysis. In fol-
lowing out these processes it. is of especial importance imme-
diately to withdraw the electrolyzed liquid from the action
1
D. R. P. No. 148054 (1903).
2
Tommasi, Trait6 (TEIectrochimie 741 (1889).
3
Ann. chim. phya [5] 17, 289 (1879).
4
D. R. P. No. 140318(1900).
5
Bull. soc. chim. 8, 23 (1866).
m
of the current, in the manner practiced by Miller and Hofer,1

by allowing the solution to flow slowly over the electrodes.
Experiments of this nature haê not yet been made here.
Ulsch2 has made some observations on the complete elec-
trochemical oxidation of cane sugar to carbonic acid and water.
In a sulphuric acid of 1.15 sp. gr.; with the addition of manganese
sulphate as an oxygen-carrier, about 98% of the theoretically
calculated amount of carbonic acid is obtained. The oxidation
at 40°-SO° in barium-hydrate solution is also fairly complete,
but not directly to carbonic acid; oxalate appears also to be
formed.
The apparently successful attempts at electrical purification
of sugar juice, for which a large number of patents3 have been
taken out, may be briefly mentioned here. The gist of the
various methods lies, on the one hand, in the destruction of
the impurities by oxidation at the anode, and, on the other
hand, in the production of precipitates which carry down
colored organic substances and facilitate crystallization of the
sugar'by eliminating these impurities.
I. Ketones.
Acetone.—Friedel,4 by electrolyzing a sulphuric-acid solu-

tion of acetone, obtained carbonic acid, acetic acid, and formic
acid. Mulder 5 and Riche 6 were able to isolate mono- and
dichloracetone from the hydrochloric-acid electrolyte, and
monobromacetone from a hydrobromic-acid solution.
These older investigations are supplemented by more recent
researches with more exact results.
According to a process patented by E. Merck,7 acetone is
1
3
3
Ibid. 1, 251 (1894), 3, 16 (1896); Jahrb. d Elektrochemie 8, 322
(1896), 8, 628 (1901).
«Lieb. Ann. 112, &76 (1859).
5
Jahresb. f. Chernie 339 (1859).
• Compt. rend. 49, 176 (1859).
7
D. R P. No. 113719 (1899).
reduced in acid and alkaline solution at a lead cathode to

isopropyl alcohol and pinacone. The yields of the latter,
however, are better in acid solution. About 40 parts of
isopropyl alcohol and 20 parts of pinacone are obtained from
100 parts of acetone, if a sulphuric-acid electrolyte is employed.
The reactions take place according to the equations:
1. CH3COCH3 +2H =OH3CH(()H)CH3,
2. 2CH3COCH3 +2H -CH
The claims of the patent were verified by Klbs.1 Elbs and

Brand2 publish the following details: In a 10% sodium-hydrox-
ide solution the reduction of acetone at a loud cathode proceeds
even with a low current density, hydrogen being continually
liberated. The yield of isopropyl alcohol and pinacone is
9-m'
im- small; and the by-products are mosityloxide, phorone, and
other condensation products. About 120 g. pure isopropyl
alcohol arid GO g. pinacone hydrate worfc obtained in dilute
sulphuric-acid solution from 300 g. acetone, load cathodes
being; also used in this ease. At mercury cathodes the reduc-
tion of acetone leads to a smooth conversion into isopropyl
alcohol (Tafel3 ), without appreciable quantities of pinacone
being formed. The cathode electrolyte was 40% sulphuric
acid. The experiments were made by keeping the solution
cool with ice.
Richard 4 reverts to the attempts of Mulder arid Riche to
prepare halogen compounds of acetone. These substitution
processes occur, of course, at the anode. With a low anode
current density and in concentrated hydrochloric-acid solution
(3 vol. acetone to 2 vol. hydrochloric acid) rnonoehloraeetone
is produced, the fluid being ice-cooled, and unattackable elec-
1
Ztschr. f. Blektrochemie 7, 644 (1901). Bee also Bibs and Schmitz,
Journ. f. prakt. Chem. 51, 891 (1895).
3
Ztschr. f. Elektrochemie 8, 78$ (1902).
8
Ibid, 288 (1902).
4
Compt. rend, 133, 878 (1901).
li
,J
I
trades without diaphragms employed. Monobromacetone is

obtained in a similar manner, but a diaphragm and a some-
what higher temperature (35°-40°) are advantageous in its
preparation.
Chloroform.—Tceple * has verified the claims of Schering's2
patent as to the preparation of chloroform from acetone. The
solution of the problem consisted simply in electrolyzing a
solution of a chloride in the presence of acetone under condi-
tions that would continuously give the greatest possible yield
of hypochlorite. The most important conditions for this
purpose are a temperature below 25°, a solution containing
no alkali; or as little as possible; a high current density at the
cathode, and a comparatively low one at the anode (Oettel,
Forstcr, etc). Teeple gives the following details: In an
ordinary cylinder of 150-200 cc. capacity place 100 cc. water,
20 g. sodium chloride, and 4 cc. acetone; a platinum cylinder
serves as anode, and a platinum wire as cathode; close the
vessel with a cork connected with a reflux condenser; cool the
apparatus with running water and electrolyze, passing in a slow
stream of chlorine as needed to neutralize the alkali; anode
current density about 6 amp. per sq. dm. or less. After 8
to 10 frours a layer of chloroform may be removed from the
bottom of the electrolyte.
The electrolysis of a calcium-chloride solution in the presence
of acetone would be the best method of forming chloroform
if the high resistance due to the deposits forming on the cathode
could be overcome in some way.
Bromoform.—As already mentioned, bromoform is not formed
from alcohol under the conditions which are suitable for the
preparation of iodoform. It is possible, however, to convert
acetone quantitatively into bromoform (Coughlin3), if acetone
arid potassium bromide are subjected in aqueous solution at
25° to the anodic current action and soda is gradually added.
A diaphragm is used. More thorough experiments on this
1
Journ. Amer. Cliena. Soc. 2C, 536 (1904).
2
D. R. P. 29771 (1884).
2
Am. Chem. Joum. 27, 63 (1902).
method were carried out by Miiller and Loebe.1 They showed

that the diaphragm becomes unnecessary if a strong current
of carbonic-acid gas is passed through the electrolytes kept at
15°-17°. They thus obtained a current yield of 90.2% bromo-
form. With a lower yield, oxidation and further bromination
occurs besides the formation of bromoform. This latter takes
place in stoichiometrical proportions according to the equation
CH3COCH3 -J-6Br + H20 -CHBr8 + CH3COOH + 3EBr,
or in the form of an ionic equation,

3Br'+6@ + H20 +CH3COCH3 -CHBr8+CH8COOH+3H'.
I' This formula is not intended to show that the acetone acts
;
| I directly as a depolarizer of the bromine ion. The reaction
| mechanism has not yet been completely elucidated.
Ii lodoform* from Acetone.—Teeple3 mentions a method by
$' which almost the theoretical yield of iodoform can be obtained
I] by the electrolysis of a potassium-iodide solution in the presence
of acetone. No diaphragm is required, the essential feature
being the gradual addition of a substance like hydrochloric
acid, hydriodic acid, or, better, iodine, to neutralize the excess
of potassium hydroxide as fast as it is formed. The tempera-,
ture is kept below 25°, and the electrolyte thoroughly stirred;
in fact the same current conditions should be observed as in
the case of chloroform above mentioned, the aim in this case
also being to maintain the conditions always favorable for the
production of a maximum amount of hypoiodite.
Oxidation of Ketoximes.—According to an investigation
made by J. Schmidt,4 ketoximes, on electrolysis in dilute sul-
phuric-acid solution, are decomposed in such a way that pseudo-
nitroles are formed besides other nitroso-compounds. If
acetoxime is oxidized at a temperature not over 10° in a 2%
1
2
See also p. 60.
3
Journ. Amer. diem. Soc. 26, 170 (1904).
4
sulphuric-acid solution, using a platinum anode, and an earthen-

ware cell as diaphragm, the anode fluid is soon colored blue;
at the same time a white crystalline substance is precipitated
upon the anode. This substance is propylpseudonitrole,,
2
This was formed perhaps in the following;
manner :
4(CH3)2C :NOH + 3N204 = 4(OH3)2C<;Q2 +2H20 +2NO.
A part of the aeetoxime will split up upon electrolysis, oxides1
of nitrogen being given off, and these latter in the nascent
state will convert any unchanged aeetoxime into propylpseu-
donitrole. A blue nitroso-compouncl can be isolated from the
anode solution. A diaphragm is unnecessary in these experi-
ments. Diethylketoxime and methylethylketoxime behave just
like aeetoxime.
Isopropylamine is formed in the reduction of aeetoxime in
sulphuric-acid solution at a lead cathode (Tafel and Pfeffer-
mann 1 ). This process is a general one. The electrolytic
reduction of ketoximes leads, like that of the aldoximes and
phenylhydrazones, to the final formation of amines. About
66% of the theoretically possible quantity of isopropylamine
is formed from aeetoxime; acetonphenylhydrazone gives about
the same yield.
Glyoxime, OHN = CH:CH:NOH, under similar conditions,
yields, as the chief product (about 60% yield) a substance
whose reactions probably characterize it as /?-ethyleriedihy-
droxylamine :
CH:NOH CH2NHOH
| Hh 2H 3 - |
CH-.NOH CHaNHOH.
The electrolyte also contains ammonia, glyoxal, and small

quantities of acid (glyoxalic acid).
J
Ber. d. deutsch, chem. Gesellsch. 35, 1510 (1902); see also D. R. R.
No. 141346 (1902).
ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
Isonitrosoacetone. — Ahrens and Meissner l electrolyzed

isonitrosoacetone, CH3COCHNOH, in sulphuric-acid solution
to obtain amidoacetone. However, a poor yield of dimethylpy-
razine, CeHgMg (ketine) was obtained.
Methylethylketone. — This substance, reduced at a lead
cathode in the same manner as acetone by Elbs and Brand, 2
gives very unfavorable results in alkaline solution. In sul-
phuric-acid solution, although the yield is insufficient, there
were obtained the modification of methylethylpinacone melting
at 50°,
r<TT nw
OH3v /Utl 3
>C(OH)-C(OH)<
X
C2H/ C2H5,
and secondary butyl alcohol, CH3CH(OH)-CH2-CH3.
Acetylacetone.— This is said to pass, in alcoholic solution,
into tetracetylethane (Mulliken 3):
CH3 - CO, CH8C(X /CO - CH8
2 >CH2= >CH~CH< +H2.
C H s-C O / CH3CCK XIO-CHs
The substance therefore breaks up into H" and (CHaCO^CH';
the anions unite at the anode to the resulting compound.
Acetylacetondioxime, in a 30% sulphuric acid at a lead
cathode, is converted into dimethylpyrazolidine and 2.4-dia-
minopentane (Tafel and Pfeffermann 4).
CH3
C:N-OH CH-NH CH-NHa
CH2 H2
C:N-OH CH-NH CH-NHa
CHs CH.3
Acetylacetonedioxime. Dimethylpyrazolidine. Diaminoptotane.
Pyrazolidine is the chief product.

1
Ber. d. deutsch. chem. Gescllsch. 30, 532 (1897).
2
3
Amer. Chem. Journ. 15, 323 (1893).
4
Ber. d. deutsch. chem. GesellscL 30, 219 (1903).
lution 6. ACIDS.
xylpy- While the substances thus far discussed are active only as
louci depolarizers, but not as electrolytes, the conditions are different
in the case of acids and their salts. These are primarily elec-
trolytes ; their ions take care of the current conductivity and
are first separated or brought into reaction at the electrodes.
In general, hydrogen ions are discharged at the cathode when
.elting
acids form the electrolyte, and metal ions in the case of salts;
acid-radical ions are discharged at the anode. The latter have
the form RCOO and are subject to a series of reaction possi-
bilities. By reacting with water the acid is again regenerated,
oxygen being evolved*
u.tlon, RCOO + H20 = RCOOH + OH.
Often, however, two anions unite, carbon dioxide being split off:
2RCOO==R2+2C02,
wherein, if R is a hydrocarbon radical, like methyl, ethyl, etc.,
1. hydrocarbons are formed having double the number of carbon
i, loud atoms contained in the radicals united with the carboxyl
. 4 -dia- group. Thus ethane is synthecized from acetic acid. This
simple form of reaction is often not the predominating one,
which will be explained more fully under the separate sub-
stances.
An acid can often develop acid properties at other than the
carboxyl groups, e.g. hydroxyl and methylene groups. In
that case there must occur the corresponding ions which are
able to direct the reaction in entirely different channels from
those mentioned. Thus, as is well known, the methylene group
placed between two carboxyl or ester groups is capable of
forming salts. Such salts as, for instance, sodium cliethyl-
malonic ester, behave, on electrolysis, in a manner analo-
gous to that of the salts of carboxylic acids. By determining
their conductivities, Ehrenfeld l has recently proved that the
1
IT
methylene groups of succinic acid, malonic acid, and glutaric

acid are capable of forming hydrogen ions. .
The first successful experiments in the electrolysis of ali-
phatic carboxylic acids were made by Kolbe.1 These experi-
ments are supplemented by the researches of Kekule,2 Brown
and Walker,3 Mulliken,4 and Weems,5 who amplified our knowl-
edge regarding this subject which, still further investigated
11 In the most varied directions by a number of investigators,
tl i! , has yielded valuable results.
/ ' ' Carbonic Acid. — Carbonic acid deserves mention here be-
>f cause it can be converted electrolytically into formic acid.
I Royer 6 observed its formation at zinc and zinc-amalgam elec-
*> \ trodes in the electrical reduction of carbonic acid dissolved
| in water, a current of the gas being conducted through the latter
during electrolysis. Klobukow 7 was likewise able to prove
the presence of formic acid in water which was electrolysed
and through which a current of carbonic-acid gas was passed.
Lieben 8 has made extensive experiments on the reductivity
of carbonic acid. He obtained formic acid as the sole reduction
product of carbonic acid. The supposition of Bach 9 that
formaldehyde must also be formed is false. The formation
of formaldehyde was never proved. Quite recently Coehn
,and Jahn 10 have shown that formic acid is the only
tangible reduction product. They succeeded in obtaining
quantitative current yields, using carefully prepared amal-
gated zinc electrodes, as already previously employed by
Royer, and using a cold saturated potassium-sulphate solution
i
as electrolyte. According to Constam and Hansen,11 potassium
1
Lieb. Ann. 69, 257 (1849), 113/244 (1860)7"
2
Ibid. 131, 79 (1864).
a
lbid. 261, 107 (1891), 274, 41 (1893).
4
Amer. Chem. Journ. 15, 523 (1893).
5
Ibid. 16,569 (1894).
6
Compt. rend. 70, 731 (1870).
7
Joum. 1 prakt. Chem. [2] 34, 126 (1887).
8
Monatshefte f. Chem. 16, 211 (1895), 18, 582 (1897).
9
Compt. rend. 126, 479 (1898).
l0
Ber. d. deutsch. chem. Gesellsch. S7, 2836 (1904).
11
Ztschr. f. Elektrochem. 3, 137 (1896), 3, 445 (1897).
percarbonate is formed when a saturated solution, of potassium

carbonate is electrolysed at -10° to -15°, particularly at a
high current density, the anions KC03 uniting -when set free:
KOX
0>
K2C2 06= |
°\
The potassium salt is precipitated )CO
as a blue powder. It has ~KO/
not been possible to isolate other
salts and free percarbonic
acid. The experiments of Salzer,1 however, indicate that the
free acid may' occur perhaps intermediately. He proved the
presence of active oxygen in a solution of potassium bicarbonate
through which was passed a continuous current of carbonic-
acid gas.
1. MOWOBA.SIC ACIDS, CnH2?i02.
Formic Acid. — This acid and its salts have "been the sub-
jects of thorough electrolytic investigations. These were
carried out chiefly by Brester,2 Renard 3 and Bourgoin;4 Bar-
toli and Papasogli,5 Jahn,6 etc.
The progress of the decomposition is accompanied by the
evolution of carbon dioxide and oxygen at the positive pole
and hydrogen at the negative pole. The quantitative relations
of the decomposition products vary with the concentration of
the solution and the density of the current. The reactions
occur according to the following equations -
HCOOH=HCOO-fH,
2HCOO -hH20=2HCOOHH-0,
+ OH=H2 0+C02 .
1
Ztschr. f. Elektrocten. 8, 902 (1902).
2
Ztsclir. f. Chem. 60 (1866).
8
Ann. chirn. phys. [5] 17, 289 (1878)
* Ibid. [4] M, 157 (1868).
6
Gazz. chim. lfc, 22, 28 (1883).
9
Wied. Ann. (N, 3?.) 37,408 (1889).
It is therefore theoretically impossible to effect the com-

plete decomposition of the formic acid present. In the elec-
trolysis of sodium formate, carbon dioxide and formic acid
are in fact always formed at the positive pole and hydrogen
and sodium hydroxide at the negative pole.
A splitting up of the anions HCOO into H and 002 at the
anode does not occur, since the oxidizing hydroxyl ions split
off the hydrogen as water (Hofer and Moest x). The discussion
.7 of the other salts is unnecessary since their behavior is quite
i analogous.
^ The dependence of the decomposition of formic acid upon
the conditions of the experiment has been investigated by
Petersen 2 and Salzer. 3
Petersen found that, if the solution was concentrated, the
'I , current strength exercised only a trifling influence on the
I decomposition phenomena in the electrolysis of sodium formate.
•{' According to Salzer's researches, formic acid in sulphuric-acid
solution cannot completely suppress the evolution of oxygen
*f • at a platinized anode. Sodium formate is for the most part
converted into carbonate; in neutral solution small quantities
>!, of percarbonate are also formed.
'4 I Formic ester in sulphuric-acid solution is attacked only
,{1 with difficulty in the cathode chamber (Tafel and Friedrichs 4 );
f acetic ester, cyanacetic ester, and phenylacetic ester, it may
/;j, , be remarked here, are not attacked at $11.
/.' Acetic Acids.

Ui < , Acetic Acid.—Glacial acetic acid is a poor conductor of elec-
an | / *
5
111 tricity. According to Lapschin and Tichanowitsch, its de-
f 11« ' composition when effected by 900 Bunsen elements yields at
||| , the anode carbon mon- and dioxide, and at the cathode carbon
l
, Lieb. Ann. 323, 284 (1902).
2
3
|, Ztschr. f. Elektrochemie 8, 893 (1902).
' * Ber. d. deutsch. chem. Gesellsch. 37, 3187 (1904).
5
Neue Peters. Acad. Bull. 4, 81 (1861).
and a small quantity of a gas the nature of which was not

established.
Bourgoin,1 on electrolysing the dilute acid, observed hydro-
gen. 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;2 on decomposing a concen-
trated solution of potassium acetate, obtained a hydrocarbon
in addition to other decomposition products. According to
the idea then prevailing, acetic acid underwent oxidation in
the sense that it was thereby changed into carbon dioxide
and 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 oxide. The hydro-
carbon evolved was in fact ethane, 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
the solution, while Bourgoin observed no decomposition products
other than carbon monoxide and dioxide. Jahn, 3 who em-
ployed currents of very low electrode density, obtained by the
electrolysis of an almost saturated solution of sodium acetate
only carbon dioxide, ethane, and hydrogen. The formation
of ethane can be explained by assuming either the direct oxida-
tion of the acetic acid.,
or the decomposition of the anion,
1 Ann. chirn. phys. [4] 14, 157 (1868).

2
Lieb. Ann. 69. 279 (1849).
Crundriss d. Eleteochemie (1895), 292.
Kekul6 1 advanced a theory based upon the phenomena of

decomposition, 'and from this deduced certain formulae which
make it possible to predict the nature of the products resulting
from the electrolysis of monobasic and dibasic acids of the
fatty-acid series. Since, however, the reaction is influenced
by the slightest variation of conditions, his formula hold good
only in the case of the decomposition of perfectly pure sub-
stances, a condition seldom met with in practice.
Lob2 is in favor of accepting in certain cases the theory
advanced by Kekul<§, who sought by experiments to prove the
intermediate formation of the anhydride, while Schall3 assumes
the formation of an acid superoxide:
R-COO
2RCOO -
R-COO
i R-COO
f =R.R+2C02.
"I R-COO
11>f
I This conclusion is drawn from the observed fact that the
]l, dithionic acids, on the electrolysis of their alkali salts, actually
<V give acid supersulphides which correspond with the superoxides:
):" • - R-CSS—+R-CSS— -R-cm.
'$'' R-CSS/ '
v| j In contrast to the acid superoxides, the acid supersulphides
V> are stable compounds.
;;l ' Bourgoin draws the following conclusions from his experi-
j| ments : He considers the intermediate anhydride formation
iîi as the most important process in the electrolysis of organic
1^1 ' acids; this brings about the secondary oxidation processes,
$j| I:! oxygen being given off. He also considers as secondary reac-
|ll • tions. the transition from the acid anhydride to the hydrate
" ' • with the taking up of water, and the oxidation, of acids by the
I oxygen clerived from the acid itself. This explanation agrees
•1 __,_ , ,..........._r,
|......... . .,______________________________________________________________________________________________ _____^ _ _ ^_ q ^- _ ^_ ^_ _ , „ ...........', „, ,„ „ ..„ ..„
| îeb. Ann. 131,70 (1864).

1 * Ztschr. f. Electrochemie 3, 43 (1896).
1 8
Ibid. 3, 83 (1896).
with the fact that water is a weak electrolyte and serves prin-
cipally as a dissociating medium. The typical processes in
the electrolysis of acetic acid are hence the following:
Electrolytic decomposition:
2CH3COOK = >0 + 0 + 2K.

3 \CH3C(X
Characteristic oxidation:
CH3-C
Kolbe and Kampf,1 on electrolyzing a concentrated potassium- p

acetate solution, obtained at the anode acetic methyl ester, ^'
formic methyl ester, ethane, ethylene, and carbon dioxide; W
and at the cathode hydrogen and potassium hydroxide. In 4
an alkaline solution of the salt Bourgoiri2 obtained, amongst )
other products, sodium formate (by reduction of the carbonic •*!
i,
acid); but so far as hydrocarbons were -concerned he could
only prove the presence of ethane and ethylene.
^
Besides the alkali salts, the copper, lead, manganese, and
uranium saUs were subjected to electrolysis by Dupre,3 Wiecle-
mann,4 Despretz,5 and Smith.6 The metals were precipitated
on the cathode, a portion of the manganese and lead in the form
of superoxides.
Elbs,7 by the electrolysis of lead diacetate in glacial-acetic-
acid solution, obtained at the anode crystallized lead tetracetate:
2 (CH3COO) 2Pb - Pb + (CH3COO) 4Pb.
Fused potassium acetate, according to the experiments of
Lassar-Cohn, 8 yields at the cathode methane, hydrogen, and
1
Journ. prakt. Chcm. [2] 4, 46 (1871).
2
Ann. cliim. phys. [4] 14, 157 (1808).
3
Arch. d. scienc. phys. et. nat (Geneva) 85, 998 (1871).
4
Poggend. Ann. 104, 162 (1858).
5
Compt. rend. 45, 449 (1857).
8
Amer. Chem. Journ. 7, 329 (1885). Electrochemical Analysis (Smith),
p. 94.
1
Ztschr. f. ELefctrochemie 3, 70 (1896).
8
Lieb. Ann. 251, 358 (1889).
carbon; at the anode carbon dioxide. This result has recently

been substantiated by Berl,1 who also proved by special experi-
ments that this decomposition is the result of the action of
the potassium; set free cathodically, on the fused potassium
acetate.
Very careful and comprehensive experiments on the elec-^
trolysis of the alkali salts of organic acids have very recently
been made by Petersen.2 The latter made exact analyses of
the gases occurring at the electrodes and thereby obtained an
insight into the quantitative course of the reactions, and deter-
mined their nature.
Petersen3 was enabled to wholly confirm the earlier state-
ments regarding the electrolysis of acetic acid by Murray,4
who investigated the influence of the concentration, current
strength, and temperature upon the course of the electrolysis
and found, like earlier investigators, carbonic acid, oxygen,
hydrogen, ethane, and methyl acetate. Murray disputes only
the occurrence of ethylene which Kolbe and Kampf declare
they found.
Petersen, however, clearly proved the presence of the
latter in small quantities, and expressed the decomposition of
acetic acid by the following equations:
I. 2CH3COOH - 2CH8COO -f- H2.
II. 2CH3COO+H20-2CH3COOH+0.
III. 2CH3COO-C2H6+2C02.
IV. 2CH3COO -CH3COOCH3+C02.
i' I ! V.
In general, equations I and III predominate; V is always
only traceable.
Hofer and Moest 6 report upon the formation of alcohols in
the electrolysis of salts of fatty acids.
êr.-d. deutsch. chem. Geaellsch. 37, 325 (1904).
2
Ztschr. f. phys. Chem. 33, 90, 295, 698 (1900).
» Ibid. 108 (1900).
IP • * Journ. of the Chen. Soc. 61, 10 (1892).

6
Lieb. Ann. 323, 284 (1902). D. R. P. No. 138442 (1901).
.11
I
They found that copious quantities of methyl alcohol, but

no perchloric acid esters, were produced by the electrolysis of
a mixture of sodium, acetate and sodium perchlorate. The
reaction takes place in the same manner as in the case of some
homologues of acetic acid, and it was found that aa addition
of alkali sulphate or carbonate acts like the perchlorate.
The general nature of the reaction is that the carboxyl
group is replaced by hydroxyl, so that an alcohol is formed
having one carbon atom less than the acid ; thus methyl alcohol
is obtained from acetic acid :
CH3COO+OH=CH3OH+C02.
The hydroxyl ion can be derived from the water, or be formed
in. the regeneration of the inorganic acid acting as electrolyte:
C1044-HOH=HC104-f-OH.
The formation of methyl alcohol can hence be formulated as
follows:
If the electrolysis is carried out between platinum electrodes

without diaphragms but with continual stirring, up to 90%
of the theoretical. yield of methyl alcohol can be obtained from
acetic a,cid and the above-mentioned inorganic salts.
The method can -also be employed in the preparation of
formaldehyde, since the methyl alcohol on further oxidation
is converted into formaldehyde (see p. 58).
Quite recently FSrster and Piguet 1 have investigated the
electrolysis of potassium acetate, using various anodes. In
the earlier experiments polished platinum had served as the
anode. Indium, gives the same results as platinum; with iron
and palladium anodes, however, not a trace of ethane is formed,
but essentially aa evolution of oxygen occurs besides the
oxidation of the acetic acid to carbon dioxide. At platinized
platinum electrodes there occurs, depending upon the current
tension, either an evolution of oxygen and oxidation to carbonic
acid (no ethane being formed), or ethane is produced, with
1
Ztschr. f. Elektrocheniie 10, 729 (1904).
84 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS. *
I very little evolution of oxygen and a very considerable oxida-

tion of the acetic acid to carbon mon- and dioxide,
i Forster and Piguet recognize three processes:
1. Evolution of oxygen.
2. Oxidation of the acetic ester formed to carbon dioxide
or carbon monoxide.
l 3. Formation of ethane.
1
They find that the anode potential determines the effect.
, • The first reaction, which occurs predominatingly at iron and
<;, ' palladium electrodes, requires the lowest potential. With
;." • platinized platinum electrodes the potential lies higher; the
I oxidation action can exceed the evolution of oxygen; and with
I a particularly high potential, which is obtained by prepolarizing
f1 the platinized anode,1 ethane is produced. With polished plati-
1 num and iriclium anodes the potential is still higher than with
I!" prepolarized platinized platinum anodes. Thus the production
I - o f ethane predominates over the oxidation of acetic ester.
»", ' Regular fluctuations of the anode potential, which often occur
)•', in electrolysis, seem to point to the formation of transition
'}?,« , resistances by intermediately occurring phases of poor conduc-
£ tivity (acetic acid, acetic anhydride).
1] ; ' The presence of free alkali is always injurious to the pro-
';j"' duction of ethane. The evolution of oxygen at platinized plati-
>f num increases with increasing alkalinity and decreases at
'' ( ' polished anodes, while the oxidation of acetic ester increases.
['? .' Hofer and Moest2 call attention to the great part which
\* the production of the methyl alcohol demands in the oxida-
,'i ' tion effects, and which Forster and Piguet have neglected to
/SV ! , point out. They formulate the principal
processes in the
following manner:
II I. CH3 'COO ©2 = C2H6+2C02;
CH3 ' +
o CH3 COO'
£J*
OH' Q2 = CH3OH+C02,
3. CH3 COO' +
CH3COO' ©2 = OH3COOCH3 + C02.
1 + Friessner, Zeitschr. f. Elektrochem. 10, 270 (1904).
S.
2
Ztschr. f. Elektrochem, 10, 833 (1904).
An impartial decision has not yet been given as to whether

the ethane production depends upon a direct union of the
anions or upon the oxidation of an intermediate product, ft
like acetic acid, acetic anhydride, or acetyl superoxide. f\
Monochloracetic Acid } according to Kolbe,1 is reduced to V
acetic acid, hydrochloric acid being split off; at the same time
free chlorine is evolved (Bunge 2). /''
Sodium Dichloracetate yields, besides carbon mon~ and dioxide J'1
and oxygen, a very easily decomposable oil containing chlorine, »h
whose natur& has not yet been made clear. (Troeger and ,^s
Ewers.3)
|
4
Trichlor acetic Acid was electrolysed by Elbs and Kratz 4
as sodium or zinc trichloracetate. Trichlor acetic trichlor-
methyl ester was formed:
2CC13COO = CC13COOCC13 + 2C02.
Potassium Cyanacetate.—With this Moore 5 obtained at the

positive pole carbon dioxide, besides traces of nitrogen and
ethylene cyanide; at the negative pole hydrogen and potassium
hydroxide, bodies analogous to those obtained in the decom-
position of sodium acetate.
Thioacetic Acid.—On electrolysis this gives acetyl disul-
phide at the anode (Bunge 6 ):
2CH3COSH = CH3COS
I +H2 .
CH3COS
1
Lieb. Ann. 69, 279 (1849).
2
Jorn. russ. chem. Gesellsch. 1, 690 (1892); see also Troeger and Ewers,
3
4
Ibid. [2] 55, 502 (1897).
5
8
Ibid. 3, 297 (1870).
w 86 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
Propionic Acids.
Propionic Acid. — The electrolysis of a concentrated solution
of sodium propionate was carried out by Jahn l and, when
density of the currents employed was not too great, yielded
hydrogen, ethylene, and carbon dioxide, but little butane,
the quantity of which further decreased when the electrolyte
was diluted. This result Petersen 2 confirmed. The evolution
of oxygen increases as the butane yield decreases. The amount
of ethylene increases with increased dilution up to a maximum,
which is reached at a concentration of the electrolyte corre-
spending to about 14% potassium propionate. On further
dilution it again decreases. Petersen 2 also found that ethyl
propionate is always produced, corresponding to the analogous
process in the case of acetic acid. He expresses the course of
the electrolysis by the following equations:
I T 9P
r ( 1. ^/\J2
' TT or* XT rv~\r\ i XT r\ or* TT rv~^r\TT i r\
i, 11. ^L^lisvAJU + liovJ = JU 2 ri5L'UL)JLl -f U.
IV 9P
4» JL V . -i j v y o
II V 2C
t^ ]
'!< , Miller and Hofer' 3 have been successful in introducing
;/ - iodine into propionic acid by electrolysing an aqueous solution
11' ' of sodium propionate and potassium iodide.
if ', Ethyl alcohol can be obtained in small quantity from
f
*l >frf, ' sodium propionate and sodium perchlorate in concentrated
* s" j £ solution (Hofer a nd Moes t 4 ) in the sa me manner a s me thyl
|J ;;;4i ', , alcohol and formaldehyde are formed from acetic acid and
I > Sf perchlorate:
1
Wied. Ann. (N. F.) 37, 430 (1889); see also Bunge: Chezn. Centralblatt 1,
382 (1890).
2
8
Her. d. deutsch. chem. Gesellsch. 28, 2436 (1895).
. 4 Lieb. Ann. 323, 284 (1902).
'ELECTROLYSIS OF ALIPHATIC COMPOUNDS. 87
Acetaldehyde is formed as the oxidation product of the latter.

Sodium a-Dichlorpropionate behaves analogously to sodium
a trichloracetate (Troeger and Ewers*). There is formed,
a besides carbonic acid and oxygen, the crystalline a-dichlor-
1 propionic a-dichlorethyl ester:
2CH3CCI2 COO = CH3 CC12COOCC12CH3 +C02.
Sodium fl-iodopropionate, according to the last-named
investigators, yields a little iodoform besides iodine; the gases
formed are principally carbonic acid. Carbon monoxide and
oxygen occur only in small quantity. >f
Butyric Acids.
Butyric Acids.—The two butyric acids -were eiectrolyzed
by Bunge.2 With isobutyrie acid it was not possible to obtain
hexane, but the normal acid yielded some butane besides larger
quantities of propylene.
Careful and reliable investigations on the electrolysis of
the potassium salts of butyric and isobutyric acids have been
published by M. P. Hamonet.3 His apparatus consisted of a
copper beaker 23 cm. high and 8 cm. in diameter, which served
as the cathode. A porous earthenware cell, which contained
the anode and was closed with a three-hole stopper, stood in the
beaker. The perforations in the stopper held a thermometer,
a gas-delivery tube, and the electric conductor leading to the
anode. The anode used in some experiments ivas a platinum
wire 1 mm. in diameter and 2 m. in length; in others a platinum
cylinder 14 cm. high and 2.5 cm. in diameter. This variation
of current density was, however, of second&ry importance.
Solutions of the potassium salts having a specific gravity of
1.08-1.19 were used as the electrolyte. Current strengths of
4-5 amp. were reached with a difference of potential at the
poles of 6-9 volts. The electrolysis was continued 2-3 hours,
1
Journ. f. prakt. Chem. 58,121 (1893).
2
Journ. f. russ. pliys. Gesellsch. 21, 525 (1889).
3
Coinp. rend. 125,252 (1895).
the solution being kept cool. The following results were ob-
tained :
Potassium Butyrate,
CH3-CH2.CH2.COOK,
yielded 225 g. propylene bromide (CH3-CHBr-CH2Br), corre-
sponding to 47 g. propylene (CH2~CH==CH2); 18 gr. isopropyl
alcohol (CHa-CHOH-CHs); 4.5 g. butyric isopropyl ester
(CH,vCH2-CIl2-COOCH(CH3)2); and 4.5 g. complicated prod-
ucts, which became resinous when the ester was saponified by
1, boiling with alkali hydroxide. Hexane (CH3-CH2-CH2-CH2
•CH2-CH3), and propyl alcohol (CH8-CH2-CH2OH) could not
•1; be detected. They could, therefore, have been formed only
in trifling quantity.
The very remarkable formation of isopropyl alcohol can
only be explained by assuming the hydration of propylene
or the molecular rearrangement of the group CHsCH^CHs -.
Potassium Isobutyrate,
(CH8)2 :CH.COOK
This salt gave 300 g. propylene bromide (CH3 • CHBr - CH2Br)
equivalent to 62. g propylene (CH3 -CH:CH2); 26 g. isopropyl
alcohol, (CH3)2:CH-OH; over 12 g. isobutyric isopropyl ester,
(CH3 )2 :CH.COO-CH:(CH3 )2 ; and 6 g. of an oil having a
pepper-like odor and boiling at 130°~150°.
In this case also the paraffin isohexane (CHa) 2: CH - CH: (CH3) 2
was not formed.
Hamonet draws the following conclusions from these results:
1. The equation
2CnH2n+l • COO - C2nH4n+2 +2C02,
representing the reaction in the electrolysis of the alkali salts

of the fatty acids, which since the experiments of Kolbe has
been almost universally accepted, can no longer claim to repre-
sent the truth in the case, since no or almost no paraffins result
from this operation.
2. The olefine CnH2?t sometimes predominates among the

products formed by the electrolysis of the alkali salts of the
fatty acids;
CnHsn+lCOOK
The general nature of the reactions is represented by the

following equation:
3. An alcohol with n carbon atoms is always formed if

the acid contains (n-f-1) carbon atoms. The structure of the
alcohol is not always that which is expected. Frequently
more than a third of the energy of the current is expended in
the formation of the alcohol. Whether the alcohol is generated
by the saponification of the ester present, according to the
equation
2CnH2n+i - COO =CnH2n+1 - COOCnIWi +C0
or whether it is formed by the hydration of the defines,,
CnH2u+H2O = CwH2w+iOH, is still uncertain. (Compare the
explanation of Hofer and Moest, p. 84.)
A more thorough investigation of the substances resulting
from the electrolysis of compounds possessing higher molecular
weights is yet wanting.
Petersen l was able to obtain n-hexane and propyl butyrate
in small quantity from butyric acid; from isobutyric acid he
got diisopropyl (isohexane) in addition to the products observed
by Hamonet.
If butyric acid is electrolysed with perchlorate, according
to the procedure of Hofer and Moest72 hexane is the prepon-
derating product; there are also obtained propyl alcohol and
its oxidation product, propionic aldehyde:
CHaCHflCHaCOO + OH - CH3CH2CH2OH + C02.
i Bull. d. 1'Acad. roy. deDanemark (1897) 397; Ztschr/f phys. Chem. 3&
115 (1900).
:'90 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
Isobutyric acid yields, accordingly, isopropyl alcohol and

:acetone.
Trichlorbutyric Acid.—According to Troeger and Ewers,1
a tetrachlorhexyleneglycol is formed at the anode from sodium
#a/?-trichlorbutyrate. The authors assume the following equa-
tions from this process:
i. 2CH3 • CHOI-ca2 coo =
CH3 • CHC1 • CC12 ™ CC12 - CHOI - CH8 + 2CO,;
II. CH.3 • CHOI - CC12 ™ CC1* • OHC1 • CH»+2H,0
. = CHsCHOH - CC12 - CC12 • CHOI! - CH*+2HCI.
i Accordingly, a hexachlorhcxane would be first formed in
•a normal manner, C02 being split off; secondarily, the two very
mobile /^-chlorine atoms would be torn away by water, hydro-
chloric acid and tetrachlorhexyleneglycol resulting.
f Valeric Acids.
Valeric Acids.—Kolbe2 electrolyzed the potassium salt of
isovaleric add in concentrated aqueous solution and obtained
&8 chief product octane (dissobutane):
$
C
Besides thisH there appeared as decomposition products
hydrogen, carbonic acid, butylene, and the butyl ester of valeric
acid.
Brester,3 who performed his experiments under different
conditions, obtained at the anode a gaseous mixture of carbon
dioxide, butylene, and oxygen.
Petersen 4 subjected the behavior of both acids to a thorough
investigation. He established the formation of normal octane
I .and butyl valerate in the decomposition of n-valeric acid; among
1
2
Lieb. Ann. 69, 257 (1849).
8
Jahresb. f. Chern. 86 (1859), 757 (1866),
4
Ztsehr. f. phys. Chem. 33V 295' (1900).
the evolved gases butylene and also hydrogen and oxygen

were found. A small quantity of butyl alcohol, which was fur-
ther oxidized to butyric aldehyde, was also formed by the
saponification of butyl valerate.
The oil which is formed in the electrolysis of potassium
isovalerate is composed of diisobutyl and triniethylniethyl
isovalerate, besides a small quantity of isobutyl isovalerate
and isobutyrie aldehyde. By saponification of the ester, tri-
methylcarbinol accompanied by a trifling quantity of isobutyl
alcohol is found in the solution.
/5-butylene and isobutylene could be detected in the evolved
gases.
Petersen adduces the following equations of reactions as
the predominating ones:
I. 2(CH3)2:CH.CH2-OOOH-2(CH3)2:CB:.CH3.COO+H2;.
II. 2(CH3)2:CH.CH2 .COO-+H20
=2(CH3)2:CH.CE2-COOH+O;
III. 2(CH3)2:CH'CH2-COO
IV. 2(CH3)2:CH-CH2-COO
V. 2(CH3 )2 :CH.CH2 -C0040
To the above may be added the following equations of minor

importance:
VI. (CH3)2:CH.CH2-COO-C:.(CH3)34-H20 -
VII.
= (CH8) 2 :CH-CH2COOH + (CH3)2 :CH «CH2OH;
VIII. (CH3 )2:CH.CH2OH-hO=(CH3)2 :CH.COH-fH20.
Even this complicated scheme cannot claim to be complete.
Probably some entirely different reactions which have thus
far not been elucidated, occur also. Considerable differences
between the yields theoretically expected aad those actually
obtained point to such, a supposition.
•92 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
Trimethylacetic Acid (Pivalic acid) — the third of the valeric

acids — has also been investigated by Petersen. It yields
trimethylcarbinol and probably hexamethylethane, besides an
isomeric body, and also two isomeric butylenes, isobutylene
predominating with perhaps also /3-butylene. Aldehyde is not
formed ; neither is an ester formed.
The principal processes taking place are the following:
I. 2C(CH3)3COOH =2C(CH3)3COO+H2;
II. 2C(CH3)3COO + H20 -2C(CH3)3COOH + 0;
III. 2C(CH3)3COO-C(CH3)3-C(CH3)3-l-2C02;
IV.
The trimethylcarbinol, a secondary product, is probably

formed l by the addition of water to the isobutylene.
•i The electrolysis of these three isomeric acids affords thus
a; •considerable qualitative differences in the results. Summing
;
: up the whole matter, it can be said that the electrolysis of a
l
fir
valeric acid gives octane, butyl valerate, butylene, butyl alco-
hol, and butyric aldehyde.
1. The normal valeric acid yields normal compounds exclu-
sively.
2. Isovaleric acid gives diisobutane, triniothylmothyl iso-
valerate, and trimethylcarbinol, also a little isobutyl isoval-
erate, isobutyl alcohol, and isobutyric aldehyde, and, finally,
two isomeric butylenes, isobutylene and /9-butylenc.
The products resulting from the electrolysis of trimethyl-
acetic acid have been summarised above.
The fourth isomeric valeric acid (active), ethylmethylacetia
acid, has not yet been investigated.
n-Caproic Acid. — A concentrated solution of the potassium
salt gave decane, and traces of the amyl ester of caproic acid,
both of which are normal ' decomposition products. The
electrolyses were made by Brazier and Gossleth,2 and by Wurtz.3
1
Ztschr. f. phys. Chemie 33, 710 (1900),
2
Licb. Ann. 75, 265 (1850).
s
Ann. chim. phys. [3] 44, 291 (1855).
il
en
The electrolytic relations in the decomposition of caproic

acid were investigated by Rohland,1 who electrolyzed the alkali
.salt. He obtained normal decane, CioH2 2.
Petersen 2 investigated the electrolysis of potassium capro-
ate on a larger scale. The oil which separated during the
passage of the current consisted of normal decane, a little
amyl caproate and arnyl alcohol, a trifling quantity of amylene^
and an aldehyde, probably CH3 (CH2 )3 COH. The greater
quantity of the amylenes formed during the electrolysis
was found in the gaseous mixture; isopropylethylene,
(CEsJsCHCHrCH^ was probably present with the normal
.amylene, CH3CH2CH2CH:CH2.
n-Heptylic Acid, Oenanthylic Acid.—The normal acid was
electrolyzed by Erazier and Gossleth,3 under conditions similar
to those for caproic acid, and gave two hydrocarbons^
Ci2H2 6 and Ci2H24, in addition to hydrogen, potassium car-
bonate, and acid potassium carbonate.
On electrolysing a concentrated solution of potassium
n-heptylate, Eohland4 obtained, besides dodecane, C^Bê, a
small quantity of a mixture of unsaturated hydrocarbons of the
series CJtisn boiling at 145°.
n-Caprylic Acid.—Rohland5 electrolyzed a concentrated
potassium-salt solution of this acid and obtained the hydro-
carbon tetradecane, CuHso-
Pelargonic Acid, under similar conditions, gives the hydro-
carhcn dioctyl.
The formation of defines, in the electrolysis of aliphatic
monocarboxylic aeids, depends, perhaps, not apon an oxidation
process,
1
2feselir. f. Elektrochemie 4, 120 (1S&7).
2
2fcschr. f. ph^s. Ch&n. 53, 317 (1900).
3
lieb. Ana. 75, 265 (1850).
4
Ztschr. f. Elektrochemie 4,120 (18^7).
•1, c.
but upon a mutual reaction of the anions, analogously to that

which causes the formation of saturated hydrocarbons:
II. 2CJWlCOO -CnH2n
The occurrence of secondary or tertiary alcohols depends

presumably upon the addition of water to the olefines :
According to Petersen,1 the equations expressing the general

decomposition of aliphatic acids are the following:
I. 2C3nH 2n+ iCOOH-20^^+1000+H2 ;

IL 2CnH2n+iCOO+H20=2CnH2n+1COOH-hO;
III. 2CnH2n+1COO-C2nH4n+2+2C02;
IV. 2C»H2n+iCOO -CnH2»+iCOOCnH2n+i +C02;
V. 2CnH2n+iCOO-CnH2n+iCOOH+CnH2n+C02;
VI. CnH2n + H20 -CnH2n + iOH; ) Secondary
VII. CnH2n+CnH2n+iCOOH=CnH2n^lCOOCnH2n + 1 . f tertiary.
Of the unsaturated monocarboxylic acids, undecylenic acid

and olelc acid have been investigated by Rohland.2 Both
yielded, on electrolyzing their potassium salts in aqueous solu-
tion, a mixture of unsaturated hydrocarbons, the nature of
which was not determined.
Electrolysis of Mixtures.—Wurtz 3 was the first to conceive
the extremely fruitful idea in electrosynthesis of making syn-
theses of substances with mixed radicals by electrolyzing two
components. After discovering Ms hydrocarbon synthesis,
which depends upon the action of sodium upon alkyl iodides,
and the use of the method in the preparation of "mixed radi-
cals " from two different alkyl iodides, he also tried to obtain
1
Ztschr. f. phys. Chem. SS, 720 (1900).
2
l.c.
8
Arm. chim. phys. [3] 44, 275 (1855); Jahresb. f. Chem. 1855, 575.
ELECTROLYSIS OF ALIPHATIC COMPOUNDS.
9
5
mixed hydrocarbons by electrolyzing the salts of fatty acids,

using Kolbe's hydrocarbon synthesis:
RiCOO+R2 COO = RiR2 +2C0 2 .
The successful results of these experiments prompted various
investigators to select, as the materials for the starting-point
of their electrolysis, mixtures of substances whose electrolytic
intermediate products could mutually react, v. Miller and Hofer
made use of these forms of reactions in the fatty-acid series
for accomplishing the syntheses of acids. Lob in a similar
manner prepared mixed azo-compouncls in the aromatic series.
The following are the experiments made by Wurtz:
Potassium acetate and potassium cenanihylate yield trifling
quantities of heptane (methylcaproyl, Wurtz):
CH3COO 4- COO - (CH2) 5 • CH3 = CH3 - (CH2) 5 - CH3 4-2C02.
Potassium valerate and potassium cenanthylate give the ex-
pected mixed hydrocarbon, a decane, as chief product (butyl-
caproyl, Wurtz):
(GH8) 2: CH • CH2 • COO + COO - (CHa) 5 • CH3
There are formed also a little octane, dodecane, and un-

saturated hydrocarbons.
In the following discussion the description of the electrolysis
of mixtures is given under the heading of the highest hydro-
carbon component, since the reaction in electrolysis depends
upon the nature of the components of the mixtures; thus
the behavior of each separate component will then have been
previously described.
II. Monobasic Alcohol- and Ketonic Acids.

a. Alcohol- (Hydroxy-) Acids.
While the acid anions of the unsubstituted aliphatic mono-
carboxylic acids react preponderatingly by splitting off carbonic
acid, without further oxidation of the radical united to the

carboxyl group, the anion of the hydroxy-acids is regularly
oxidized further. The extent of the oxidizing action depends,
among other circumstances, to a great extent upon the con-
centration. For example, glycollic acid in concentrated solu-
tions is oxidized almost completely to formaldehyde, and to a
less extent to formic acid and carbonic acid. By increasing
the dilution carbon monoxide occurs in place of formaldehyde.1
', TT ^ T T r\tJfr^/~\r~\ i O /™\ TT r*r\ \ r^r\ i OTT f~\

11. UH2OHUUU + oOli =LU + oU2"roll2U.
The subst i t ut i on of met hyl for hydroxyl d oes not affect

the easy oxidability. It is evident from the theoretical explana-
tions given in the first chapter that the changes in concentration
are of importance for the course of the reaction only in so far
I I
keeping
as they influence the anode potential. By artificially
the latter constant , the products must remain the same, being
independent of the conditions of concentration. In general,
4 't the following rules can be adduced for t he electrolysis of
4; oxy-acids (chiefly worked out by Miller and Hofer, 2 and
^f . Hamonet 3 ):
f
j' a-Oxy-acids are converted by electrolysis in concentrated
^ • solution int o aldehydes or ketones. If the solution is more
<£ ,, i highly diluted, the compound is oxidized to carbon monoxide.
iftj /9-Oxy-acids behave more like acetic acid; they are, at
p'i least partially, converted into glycols, or t heir others:
y;| I. 20H.CnH m COO-OH.C w H«.C n H w .OH+2C0 2 ;

1 jj ,, II. 2RO - CJU300 - RO - CWHW • GnBU - OR+2C02.
|| In the case of dioxy-acids the oxidation affects both hydroxyl

•groups, the intermediate CHOH-groups being oxidized to
carbon mon- or dioxide.
1
Ber. d. deutsch. chern. Gesellsch. 27, 461 (1894).
2
Ibid.
8
Compt. rend. 132, 259 (1901).
ELECTROLYSIS OP ALIPHATIC COMPOUNDS. 97
The experiments of Miller and Hofer were made by passing

wl \
the electrolyte in a slow stream through the cell (Apparatus,
Fig. 4, p. 44) . This made it possible to find decomposition prod-
ucts which would otherwise have been changed by further
111
electrolysis; a more complete expression of the course of the
decomposition was thus obtained. It is to be regretted that
the researches do not mention the necessary data regarding
the electrical conditions.
Gly collie Acid. — If a solution of 30 ,g. sodium glycollate in
38 cc. water is electrolysed with a current strength of 1 amp.,
there are formed chiefly carbonic acid and formaldehyde,
.besides a little carbon monoxide, formic acid, and oxygen
(Miller and Hofer1). Walker2 obtained aldehyde in the
electrolysis of the sodium salt of ethyl glycollic ether.
Methoxylglycollic Acid. — The electrolysis of its sodium salt tiff*
was made by the same authors 3 and yielded formaldehyde,
methylal, formic acid, and carbonic acid; in dilute solution also
carbon monoxide and a little methyl alcohol.
A mixture of potassium glycollate and potassium acetate
unites at the positive pole to form ethyl alcohol (Miller and
Hofer 4) ; some acetaldehyde is also formed by further oxida-
tion:
CH2(OH)COO + CH3COO =CH3CH2(OH) +2C02.
Oxypropionic Acids.
Ordinary Lactic Acid. — As Kolbe 5 had already discovered,

the concentrated solution of the potassium salt gave carbon
dioxide and acetic aldehyde. The investigators above men-
tioned also observed the presence of some formic acid. When
the solution surrounding the positive pole was kept slightly
1
* Journ. Chem. Soc. 65, 1278 (1896).
a
4
Ibid. 28, 2437 (1895).
5
Lieb. Ann. 113, 214 (1860).
,1;
!' alkaline, aldol and crotonic aldehyde were formed instead of
i acetic aldehyde.
Sarcolactic Acid.— When the solution surrounding the posi-
tive pole was kept neutral, a concentrated solution of the sodium
salt yielded acetic aldehyde and carbon dioxide.
Hydracrylic Acid (Ethylenelactic Acid = /?-oxypropionic Acid) .
[ — Resin and a little formic acid were found present in the
electrolyte surrounding the positive pole.
;| | ,- •] The potassium salt of the alcoholic amyl ether of this acid,
;1 >t ,', , the /?~amyloxypropionic acid, was electrolysed by Hamonet.1
I It gave about 50 per cent of the theoretical yield of 1.4-butan-
(
f dioldiamyl ether (diamyl ether of butylene glycol) .
2C5HnO-CH2-CH2COO
Glyceric Acid (Dioxypropionic Acid). — This acid decom-

poses into carbon mon- and dioxide, formaldehyde, and formic
acid (Miller and Hofer).
Oxy butyric Acids.
a-Oxybutyric Acid (CH8-C3H2-CHOH-COOH).— This sub-

stance was converted into carbon dioxide, propionic aldehyde,
and some formic acid (Miller and Hofer) .
a-Oxyisobutyric Acid ((CH3)2:CHOH-COOH).— This com-
pound, investigated in the same manner, was found to be par-
tially oxidized at the anode to acetone. Much carbonic acid
and a little carbon monoxide is also evolved.
. ^-Oxybutyric Acid (CH3 -CH(OH)-CH2 .COOH).— From this
acid were obtained in the positive electrolyte crotonic aldehyde
• and a little formic acid, also resinous substances. Considerable
quantities of carbonic acid, also a little carbon monoxide and
unsaturatecl hydrocarbons, are formed. The small quantities
[ELECTROLYSIS OF ALIPHATIC CGMPOI(Nl?Sp ^
of saturated hydrocarbons are derived probably from impurities

in the acid (presence of acetic acid) . " ^ t~ "^ t " ,p> *>
r-0xybtityric Acid (CH2OH - CH2 • CH2 • COOH) .— I&monet *
electrolyzed the alkali salt of ^-isoamyloxybutyric acid in
order to obtain symmetrical hexylene glycol, or its diamyl
ether. The desired reaction did not take place :
2C5Ci iOCH2 - CH2 - CH2 • COO

=C5Hn - OCE2 -
/9-Methylglyceric Acid (a-/?-Dioxybutyric Acid (M. Pt. 74-

75°)=CH3 -CHOH.CHOH.COOH).—When the potassium salt
of this acid is electrolyzed (Pissarshewski 2 ) it breaks up
into carbon mon- and dioxide, formaldehyde, formic acid,
acetaldehyde, acetic acid, and another substance having the
property of reducing Fehling's 'solution. This latter compound
was not isolated.
/CH-COOH
/?-Methylglycidic Acid, 0<; | behaves similarly.
XJH-CHs
6. Ketonic Acids.
Pyroracemic and Isevulinic acid, i.e., an a- and a f-ketonic
acid are the only monobasic ketonic acids which have been
electrolyzed. The electrolysis of a representative of a /?-ketonic
acid, acetoacetic acid, could not be carried out, on account of
the instability of the free acid and its salts. The reactions
take place partly in a manner similar to those occurring in the
decomposition of acetic acid; the anions unite to form a dike-
tone, carbonic acid being split off; and partly in a further
oxidation to acetic acid, with the occurrence of carbon mon-
and dioxides.
1
Compt. rend. 136, 96 (1903).
2
Ztschr. d. russ. chem. phys. Gesellsch. 29, 289, 338 (1897).
Pyroracemic Acid. — Potassium pyroracemate gives (Hofer)-*

chiefly acetic acid and also a little diacetyl:
=CH3COOH+C02;
II. 2CH3 -CO - COO = CH3 • CO • CO - CH3 + 2C02,
Rockwell 2 found at %he anode some acetaldehyde, and
at the cathode the normal reduction product of pyroracemie
acid, i.e. a-lactic acid:
CH 8-CO.COOH+H2-CH3 -CHOH-COOH;
also some propionic acid, probably formed by further reduction.
Lsevulinic Acid. — This acid is much better adapted for the
synthesis of the corresponding diketone -than, is pyroracemie
acid. Hofer,3 on electrolyzing the potassium salt of the acid*
obtained about 50% of the theoretically expected quantity of
2.7-octandion:
2CH3-CO-CH2-OH2-COO
Considerable quantities of acetic acid are also formed, and some

• carbon monoxide is produced by the oxidation of the methylene
, groups.
Acetoacetic Acid. — If the sodium compound of acetoacetie
• ester (Weems 4 ) in alcoholic solution is electrolyzed, there is
' formed diacetylsuccinic ester:
" COCH8 COCH3
' I I
2CHNa =2CH +2 Na
, | )
' COOC2H6 COOC2H6
.' COCH3
'• 'I
! 2CH =C2H 5 OOC-CH.CH.COOC 2 H5
;
( COOC2H5 H 3 CCO COCH 8 .
f
j- • -
| HI » Ber. d. deutsch. chem. Gesellsch. 33, 650 (1900).
I !i * Journ. Amer. Chem. Soc, 24, 719 (1902).
s
J «, l. c.
;4s;f Amer. Chem. Journ. 16, 569 (1894).
m
Pyroracemic Acid. — Potassium pyroracemate gives (Hofer) -

chiefly acetic acid and also a little diacetyl:
II. 2CH3 - CO - COO = CH3 • CO * CO • CH3 + 2C02,

Rockwell 2 found at %he anode some acetaldehyde, and
at the cathode the normal reduction product of pyroraceirie
acid, i.e. a-lactic acid:
CH3.CO-COOH4-H2=CH3-CHOH.COOH;
also some propionic acid, probably formed by further reduction.
Laevulinic Acid. — This acicl is much better adapted for the
synthesis of the corresponding diketone -than is pyroracemic
acid. Hofer,3 on electrolyzing the potassium salt of the acid*
obtained about 50% of the theoretically expected quantity of
2,7-octandion:
2CH8-CO-CH2-CH2-COO
Considerable quantities of acetic acid are also formed, and some

carbon monoxide is produced by the oxidation of the rnethylene
groups.
1i
Acetoacetic Acid.—If the sodium compound of acetoacetic
ester (Weems4 ) in alcoholic solution is electrolyzed, there is
formed diacetylsuccinic ester:
" COCH3 COCH3
, 2/~1TT"\T-. <T) /""1TJ" I O "\Tr»
OJuLisa ~ £ UJti ~r^ IN a

C
COOC2H5 COOC2H5
COCH3
2CH =C2 H5OOC-CH-CH-COOC2H 5
COOC2HS H3CCO COCH3 .
!J 1
2
Joura. Amer. Chem. Soc. 24, 719 (1902).
»1. c.
Amer. Chem. Joum. 16, 569 (1894).
U
According to Tafel and Friedrichs,1 acetoacetic ester can

be easily reduced in sulphuric-acid solution. This reduction
evidently extends to the carbox-ethyl group because a molecule
of the ester requires almost six atoms of hydrogen.
Acetylmalonic Add, CH3-00-CH:(OOOH)2, and Acetone-
dicarboxylic Acid, CO: (CH2 COOH) 2 , do not permit their
anions to unite (Weems2 ).
In connection with his investigation of ketonic acids, Hofer 3
has used the electrosynthetic reaction, previously discovered
with Miller/ which consists in electrolyzing potassium salts of
organic acids in mixture with potassium acetate and other
lower fatty acids. The general nature of the reaction is that
the two anions unite, as in Kolbe? s synthesis, carbonic acid
being split off, e.g.,
R-CO-COO + Ri-COO-R-CO-Ri+2C02.
Potassium Pyroracemate and Potassium Acetate thus yield
acetone as the chief product:
CH3OOCOO+CH3COO -CH8COCH3+2C02.
Some acetic methyl ester and traces of diacetyl are also
( formed.
Potassium Pyroracemate and Potassium Butyrate unite to
1
• form methylpropylketorxe:
I CH3-CO-COO+CH3-CH2.CH2-COO
= CH3-CO-CH2.CH2.CH3+2C02.
Some diacetyl is also formed in this case, with trifling
quantities of esters of butyric acid, and larger quantities of
hydrocarbons, chiefly hexane and decane. The hexane was
formed from the butyric acid, the decane from caproic acid,
an impurity in the butyric acid.
1
Ber. d deutsch. chem. Gesellsch, 37, 3188 (1904).
»1. c.
3
Her. d. deutsch. chem. Gesellsch. S3, 650 (1900).
4
Ibid. 28, 2427 (1895).
5?
X
^f
•£« O
i
o Ol fe ^ fi
-f
?r M
**** t «• x ft
Ct
— J: *H r$ ac-
£c j: "§
X
*C3
£ c i
as
^ *r - _ > ^
i5-1i
5-« t, sT *««****
" I
^" i,<^^!J~-ft:3=?:-'^^% 1
ELECTROLYSIS OF ALIPHATIC COMPOUNDS. 103 «'
K'
e st er g r ou p s, a cc o r d i ng t o a n ex p eri m en t of G ut hri e, 1 ar e 'k
ele ct rol yti call y ina ctiv e ; the m on o-est ers of dib asic a cid s be h a ve |;
l i k e m o n o b a s i c a c i d s, i . e . c a r b o n d i o x i d e i s s p l i t o f f a n d d i - '/,
e st er s o f h i g h e r d i b a s i c a c i ds a r e f o r m e d , s a p o n i f i c a t i o n c o n- \*
vert i ng t h e esters i nt o t h e fre e di basi c a ci ds: .']
2R O O C( C H 2 ) , CO O =E O O C( CH 2 ) X - ( CH ^ CO O R + 2C 0 2 .
Thus the diethyl ester of succi nic acid i s form ed fr om et hyl \>
potassium malonate:
V
2C2H5OOCCH2COO - C2H5OOCCH2CH2COOC2H5 + 2C02.
Von Miller and Hofer2 broadened the possibility of the electro- •*:
syntheses of dibasic acids by borrowing an idea of Wurtz and J
using the results of Brown and Walker. Wurtz,3 as already \•
mentioned, had electrolysed mixtures of two fatty-acid salts* i
and accomplished the union of the different radicals to form
the corresponding hydrocarbons. In the same manner, von
Miller and Hofer electrolyzecl mixtures of fatty-acid salts and
mono-esters of dicarboxylic acids. Hereby the esters of mono-
carboxylic acids containing a higher number of carbon atoms
are formed. If, for instance, a mixture of potassium acetate
and potassium ethyl succinate is subjected to electrolysis,
butyric ethyl ester is formed, according to the following equa-
tion:
CHaCOO+COOCH2CH2COOC2H •
-CH3CH2CH2COOC2H5+2C02.
If the two carboxyl groups of dibasic acids are esterifiecl,

such a di ester can behave as an acid only when methylene
groups possessing a decidedly acid character are present. Mulli-
ken4 and Weems 5 investigated such compounds. The sodium
1
Lieb. Ann. 99, 65, 1856.
* Ber. d. deutsch. chem. Gesellsch.' 28, 2427 (1895).
3
Jaheresber. d. Chem, 575 (1855).
4
Amer. Chem. Joum. 15, 323 (1893).
5
Ibid 16/569 (1894).
compounds of diethyl esters of dibasic acids in particular fre-

quently behave in a manner analogous to that of the carboxylic
acids, the anions uniting. The same compounds are thus ob-
tained as are formed by the elimination of sodium by iodine.
Thus sodium diethylmalonic ester gives ethanetetracarboxylie
ester;
COOC2H5 COOC2H5
6J W
2CHNa =2CH~ +2Na

it
3002H5 COOC2H5
COOC2H5 COOC3H5 COOC2H5S
•J \~ 2 CH» = CH ----------------------------CH
A I5 COOC2H5 COOCaHs.
If the methylene groups of dicarboxylic
acids contain
electrolytically sensitive radicals, the reaction picture is shifted,
as will be touched upon in the special cases.
Oxalic Acid.—The deportment of the saturated solution
of the free acid on electrolysis was determined by Brester,1
Bourgoin,2 Balbiano and Alessi,3 Bunge,4 and Renarcl.5 The
general result was that oxygen and carbon dioxide were obtained
at the anode and hydrogen at the cathode. It is possible to
completely oxidize oxalic acid to carbon dioxide. On this
property depends the great importance of oxalic acid in quanti-
tative electrolytic analysis, into which it has been introduced
by Classen.6
The ability of ammonium oxalate to form soluble double
salts with many difficultly soluble or insoluble metallic salts
is in accord with the favorable conduct of the acid on eleetroly-
1
Jahresb. f. Chem. 87 (1866).
2
Compt. rend. 67, 97 (1868).
8
Gazz. chim. 12, 190 (1882); Ber. d. deutsch. chem. Gesellsch. 15, 2236
(1882).
4
Ber. d. deutsch. chem. Gesellsch. 9, 78 (1876),
5
Ann. chim. phys. [5] 17, 289 (1878).
8
Classen, Quan. Analysis by Electrolysis (Wiley & Sons, N. Y.).
KLEf.mtOLYSTS OP ALIPHATIC COMPOUNDS. 105
pis, by whk'b operation it may bo entirely removed from the

solution in the form of gas.
The redwing effects off the current on oxalie acid were also
observed. Tims on electrolysing both the free acid and its
sodium salt Balbluno arid Alessi were able to prove the presence
of Klyrollir acid. Tafel and Friedrichs l obtained a good yield
of giyo.xylir arid hy reducing oxalic acid in sulphuric-acid
solution at lead or mercury cathodes. Oxalic ester and oxal-
acetic ester are easily reduced also.
The oxidation is not complete if the electrolysis is conducted
in th*' cold solution, carbon monoxide as well as carbon dioxide
being then formed at l i t e positive polo.
The decomposition reactions of oxalates are entirely analo-
gous to those of I he free arid. In alkaline solution the oxidation
proceeds more rapidly than in neutral solution because of the
letter {•oMilwtivity of the alkalies.
Xatiintlk* ethyl potassium oxalate cannot react in accord-
ance with the scheme of the Brown and Walker's synthe-
2
KI*H . When it was electrolysed both investigators observed
t i n * pre.sewe of ethytene. This unsaturated hydrocarbon was
very likely derived from the. enter group.
h'tenson3 iuu* fonimlated the following equations of decom-
position:
L
!L
I I I. f(!C)0)2-2C()2;
IV.
tbfii on the* c»loctroly«is of oxalic acid must be sup-

t by tlio«» regarding itB rtuluction to glycollic acid,
«c*ici, and th« reduction to formic acid (Royer 4 ),
f
l.lrtr, d. dmiUeh. chcm. Ckswollacli. 37, 3180 (1004).
»Lwh. Aim . 274, 70 (1893).
.»Zuwhr. f. ptiys. Chem. S^l, 098 (1000).
<Compt. rentl §9,1374 (1869), 70,731 (1870).
106 ELECTROCHEMISTRY OK ORGANIC COMPOUNDS.
which is brought about when using oxalic acid in place of nitric

acid in a Grove coll.
A scries of n%seur<:hus. concerning the relation between the oxi-
dation of oxalic acid and the electrical conditions have been
made. Oettel l discovered that the current consumption
required for an oxidation proems is greater when a smaller
current density is used than when a higher density is employed.
Ackerberg2 determined that the* oxidation, which is trifling at
a polished platinum anode, is quantitative under the same con-
ditions at a platinized anode. Salzer3 investigated the elec-
trolysis of oxalic, acid, as to the tension conditions and oxida-
tion action, in sulphuric-acid and in aqueous solutions at polished
(bright) and platinized anodes.
Malonic Acid, -Thin acid waft investigated by Bourgoin.4
In a concentrated solution of slrupy consistency it, like oxalic
acid, is only slowly oxidized to carbon dioxide, with evolution
of oxygon. A strongly concentrated solution of the unaltered
acid is found surrounding the positive electrode, even after an
electrolysis of long duration. On electrolysis of the sodium
salt carbon monoxide1 is also present in the gaseous mixture
evolved. The proportions of the various gases, carbon rnon-
and dioxide, and oxygen, remain fairly constant during the
period of electrolysis (85.8%, 9.7%, 4.5%).
In alkaline solution the decomposition products are the
same as in neutral solution, only the proportions of the individual
gases being different, and varying according to the duration of
the electrolysis.
Miller,6 on electrolyzing znalonates, was able to detect a
trifling quantity of ethylene.
Petersen 6 verified this fact- He formulated the following
reactions:
1
Ztqchr. f. Elektrochemie 1, 90 (IHOI),
2
Ztachr. 1 anorg. Chen, SI, Id! (1002).
8
* Ann. ohim. phys. [1] 14,157 (1857); Bull d. i. soc. cMm. S3, 417 (1889).
5
Joum. 1 prakt. Chemie 127, 328 (1870).
« Ztschr. f. phys, Cheraio 33, 7CM) (1000).
,
*
- ELECTROLYSIS OF ALIPHATIC COMPOUNDS. 107
II. CI Ia
III. 2(JII
IV. CIl2
in which, hovrovor, III is inconsiderable.
The Brown- Walkor l method has been found to be of ex-
<-«-»llont scrvico in the electrolysis of the potassium salts of the
mono-esters of makmie acid. The formation of the cliethyl
cst.or of sweinic acid from ethyl potassium malonate has already
IK »OII mentioned (p. 103).
If the* othyl potassium salts of substituted acids are chosen
as the starting-point ., it is possible to obtain (lisubstituted acids,
according to the above reactions.
^
1. Ethyl potassium methylmalonate yields the two sym-
metrical (limethylsuccinic acids having the melting-points 193°
and 121°. , '|
2. Ethyl potmwium ethylmalonate yields the corresponding
symmetrical didkylxumnic ocwis, with the melting-points 192°
and 130°.
3. Ethyl pota«wium dimethylmalonate affords tetramethyl-
tsuecinic acid.
4. From ethyl potassium (Hethylmalonate a substance having
the conipoKitioti Ci-iHgeO^ and which differs from the expected
tetniothyl-HUCciaic acid by (^H^ was obtained. The nature
of this body has not yet teen determined.
Hyclrobromic acid splits off alcohol, the com
which has perhaps the furfurarie formula
0:0 0:0
being formed.
All thofics reactions do not take place smoothly, but are
accompanied by secondary reactions; principally oxidations,
n. c.
nr,
which are limited as much as possible by working with strong

concentrated solutions and low temperatures. Moreover, the
formation of esters also is always possible according to the
equation
2 CH3.C( )() - cn»c( )( )CH3 + cc >2 ;
and, finally, the formation of imsut united esters may take
place analogously to the formation of othylcne from propionie
acid :
2 C2HfiCOO <= C2I U + C02 + C2H5COOH.
Thus it was possible to isolate methylacrylic acid by the

electrolysis of ethyl potassium diiudhylm (donate:
: 2 C2 -1 C21 Ifi
Amer. Ohem. Joum. IS, 323 (1803).
2
Ibid. IS, 569 (1804).
8
Ber. d. deutsch. ehana. Gosellsch. 28, S438 (1895).
In the same way ethylcrotome arid is formed from the ethyl
potassium salt of diethylmalonic acid.
Mulliken,1 on electrolysing sodium malonic diethyl ester in
alcoholic solution, obtained ethanetelrdcarboxylic ester, as already
2
mentioned. Weems, on elcctrolyzing the corresponding com-
pound of methylmalonie. acid, obtained dimetliylethanetetracar-
boxylic ester, whereas ethylmalonic ester gave diethylethanetetror
carboxylic ester.
The method of von Miller/1 electrolysing potassium ethyl-
malonate with potassium salts of aliphaiic carboxylic acids, also
.gives satisfactory results. If potassium acetate is chosen as
the second component of the electrolytic mixture, propionie
•ethyl ester is formed; and likewise by using potassium pro
pionate or potassium butyrate we obtain butyric ethyl ester or
valeric ethyl ester respectively.
Nitromalonic Acid.—According to Ulpiani and Gasparini,1

a hydro-alcoholic solution of nitromalonic ethyl ester does not
conduct the current, but an aqueous solution of the ammonium
salt does. According to this the ester appears as a true nitro-
compound:
COOC2H5
CHN02 ,
COOC2H5
but its ammonium salt, on the contrary, as an isnitro-salt:
COOC2H5
C = NOONH4.
COOC2H5
The electrolysis of this latter does not give the free isonitro
acid at the anode, but the dinitroethanetetracarboxylic ester:
2 CNOO = (COOC2H5)2C(N02)C(N02)(COOC2H5)2.
(X)OC2H5
The ammonium salt of nitromalonamide yields at the anode,
only free nitromalonamide, whereas julminuric acid (nitrocyan-
acetaniick'),CN-CH(N02)-0^jjjj, on electrolysis of its am-
monium salt, gives a new reaction product which has not yet
been investigated,
Succinic Acid.—Bourgoin 2 and KekuM 3 found that the free
acid underwent oxidation with difficulty, only a small quantity
of carbon monoxide in addition to some oxygen and carbon
dioxide being formed.
The neutral sodium salt gave the same products, as did also
the alkaline solution of this salt, except that in the latter ex-
periment the formation of carbon monoxide predominated. If,
however, four molecular equivalents of sodium succinate were
* Gazg. chim, $2, II, 235 (1902); Ztschr. f. Elektrochemie 9, 477 (1903).
9
Ann, de chim. et phys. (4) 14, 157 (1866).
»Lieb. Ann. 1*1,84(1864).
treated with one equivalent of sodium hydroxide, ethylene and

a little acetylene could also be detected. Kolbe l states that
methyl oxide is also formed; Bourgoin, however, was unable
to confirm this statement.
Clarke and Smith, 2 on oxidizing succinic acid in alkaline
solution, obtained, besides oxygen, carbon mon- and dioxide,
ethylene, methane, tartar ic acid, and oxalic acid.
Petersen3 was unable to detect either carbon monoxide or
acetylene in a slightly acid electrolytic solution of potassium
succinate. The following equations essentially express the
course of the electrolysis:
I. C2H4(COOH)2 = C2H4(COO)2 + H2;

II. C2H4(COO)2 + H20 - C2H4(COOH)2 + 0 ;
III. (C2H4)(COO)2-02H4 + 2
Small variations in the conditions of the experiment, as well

as in the degree of acidity, the temperature, arid the kind and
size of the electrodes, exert a great influence on the course of the
electrolysis.
According to the method of Brown and Walker,4 adipic
diethyl ester is formed from ethyl potassium succinate :
COOC2H5
2(CH2)2 •(CH2)4
300 COOC2H5
fl
?*?.<4
Fairly large quantities of propionic and acrylic esters are
also formed, probably by the reaction
2COOCH2CH2COOC2H5
. - CH3 2 : CHCOOC2H5 + 2C02.
1
Lieb. Ann. 113, 244 (1800).
3
Joura. Amer. Ghem. 8oc. 21, 907 (1899).
8
Ztschr. f. physik. Chem. Si, 701 (1900).
*l.c.
ELECTROLYSIS OF ALIPHATIC COMPOUNDS. Ill
Bouveaultl claims that the yield of adipic acid is better on

electrolysing the methyl ester-salt in methyl-alcoholic solution.
He obtained a yield of 80% by using a mercury cathode and
a hollow platinum spiral anode, through which a current of cold
water was passed. The acid succinic methyl ester occurs as the
principal by-product, also a neutral methyl ester of a tribasic
acid which was not investigated.
Sodium succinate and sodium* perchlorate, electrolyzed by
Hofer and Moest,2 gave hydracrylic acid as the chief prod-
uct, besides acetaldehyde, acetic acid; methyl alcohol, and
formic acid. The splitting off of carbonic acid and the intro-
duction of the hydroxyl group occurs only at one carboxyl
group:
CH2-COO CH2-OH
CH2 -COOH +OH= I +C02.
CH2-COOH
Von Miller and Hofer 3 have also carried out the principle
of the electrolysis of mixtures, discussed under malonic acid,
using potassium ethyl succinate, and submitting the latter to
electrolysis at the anode with potassium salts of monocarboxylic
acids. They thus obtained on the addition of potassium acetate
about 69% of the theoretical quantity of butyric ethyl ester:
CH3 • COO+COO • CH2 - CH2 • COOC2H5

= CH3 • CH2 - CH2 - COOC2H5+2C02.
- Incidentally a yield of about 22% of adipic ester was ob-

tained.
The synthesis of valeric ethyl ester from potassium ethyl
succinate and sodium propionate was accomplished in the same
way:
CH3 • CH2 • COO + COO(CH2) 2COOC2H5
-CH3(CH2)3COOC2H54-2C02.
1
Bull. soc. chim. 29, 1038, 1043 (1903).
»Lieb. Ann. S23, 284 (1902).
3
Ber. d. deutsch. chem. Gesellsch. 28,2431 (1895).
112 ELECTROCHEMISTRY OF ORGANIC' C'OMI'ot'NDS.
Furthermore, by using a mixture of potassium ethyl sumn

and potassium isobutyrale, isobutylucHir rstcr was obtained:
(CH3)2 :CHCOO + COO(CI W '*< H K'
Vanzetti and Coppacloro 1 have oxtpndi'd tl»» von Mil

Hofer method to the olro.trolysis of a mix! wo of /•//*/// /uttu
r
mdonate and e%/ jmtamtnn snccinntr. riv*y ohtaincMt a p«w»r
yield of the desired glut uric diefhvl ester:
COOC2H5 • CHo • COO -f (^00 . ( 'II, . ( '! f , - ( '( H H y I,

I.vt'Ha-CIL.-CHyCOCHyf;, i 2('0a.
Moreover, suecinic diethyl f*st(»r \va.s formal from thi* iti

acid, and adipic diethyl entcT from the* sttmttif acid.
Pyrotartttric J( n'tl^
Glutaric Acid (Normal ryrntartnri*' And).- ......... Thc» n'suIlM ob-
tained by Rehoul and Bourgoiit2 an* thr followium: A
part of the acid remains unrhangfil, while n small part IB
decomposed according to the* following equal ion:
C'll^,
A hydrocarbon of the* compos! t ion | /Mlz not ol>-
C f ff/
tained; nor was an olefme formed.
Similar observations were* ramie in the* !*foetroly#i& of

sium glutarate, also in alkaline flotation. *
Petersen3 expresses the of tho by the
following equations:
1
Atti R. Accad. del Ltneei 12, If, 2«!l f HICI3),
3
Bull. soc. chim. 27, 545 (1877) ; CmnpL wnd. HI, 12*11, mm
3
Ztschr. f. phys. ehem. IS, 703
I
'I
•
X
x rr
114 ELECTROCHEMISTRY OF OIKUNIC1 CoMPOl'MXS.
The strong aldehyde reaction of flic* olfofrolytp, uffpr the

experiment was finished, indicates that the* primary alcohol
is partially oxidized further to propionir altli'liyrlf. or that
the propylene can yield propylew* ox do through (hi* influence
of the anodic oxygen, and, by molecular w*arranj?einent, the
a dehyde :
Oils Cir« OH.1
CH + 0 = 011 \ - ( ' I I 2
CH2 CI12/
Ethylmalonic Acid.— The Ix'havior of ethyl potassium
ethylmalonate has already been im»nfione<l in flu* di^cuHsion
r
of malonic acid. The potassium «alt, in it 20 ,' slightly acid
l
solution, yields propyleno (Peterwri )j «nil probably, like* pyro-
i
tartaric acid, primary and sc eonclary propyl alrohol.
Adipic Acid.— The ethyl potiiHBitiin will- tfonvcrfwl into
1
the sebacic diethyl ester by Brown and Wnlkor :
C000 2 Hs
2(CH2 )4 «
coo
Pimelic Acid. — In the flame? rnunncTy th<» iiii*f]iyl of
n-decanedicarboxylic acid is formed from tiif*
2 3
salt of pimelic acid (Komppa, aho Walker ami Liiffim!f*n ).
n-Pentenecarboxylic ethyl ester occurs us a by-prodtjct at tlia
anode:
I. COOC2H5 COOCaH*
2(CH2)5 -(CH2)iD +2f!C)2;
CO COOC2H5
II COOC2H5 OOOCalU
. 2(CH2 )5 «(CH,)3
COO CH
CHa
"1. c.
2
Ber. d. deutsch. chem. 14, 9W
8
Journ, Chem. Soc. 70,1197 (IJ0I)
JL -r
f .5 I ill I I1f^ J "g I
"IK £» "*'* *&. *•»
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H^ *2 H * ^ S »i * f «£ i * *f i j 5 ® 1
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ELECTEOCHKMISTMY OF OHUAX1C
along with tliis compound, sonic

propylcne was forme
a portion of the acid was always regenerated.
Citraconic Acid.- . 'flu*- concentrated solution of t i n
salt likewise* elect rolywd by Aarland,1 yielded, Inîdes
carbon, C3ILi, small traces of acrylic and inesaconie aei
Mesaconic Acid, under similar conditions, IIP .stiir
îves 1
hydrocarbon and traces of acrylic and itnconic arids.
The unsutumtcd acids, on electrolysis,
consequentl; s. lik«
to give no synthetic products at all. The aromatic
;n
phthalic and Ixjiizyhnalonir acid. Mum- similarly.
V. Polybasic Acids.
Malic Acid.—The electrolysis of malic acid was effected l»y
Bourgoin2 and Bresteiv1 Bnlli list* frei- acid, which is hut sli»\vly
decomposed, and the neutnil alkali salt, p:w* the same prinluct.s
carbon dioxide and it little carlnm nif»hf»xio!n and oxypeii.
After the completion of the p\|»rrimcnt I lie solut"u»n contained
some aldehyde and acetic acid. Von Miller and Ilofei"1 alô
found crotonaldc»hydc».
Tartaric Acid (I)extr<H-c»t:iry).--The free ucid is partially
oxidized (Bourgoin5 and Ki*kuli: fl i to carb(»n flioxiflc and
carbon monoxide, while the solution contains awt'ic itri«l
Neutral pottisaium turtntte principally car I ion dioxidt*
besides a little carl>on monoxiile an«l oxygen, ncid p«ifiiK4itiii
tartrate being at the wmw* tiitit* depciHifed. In alkaline sc»hitionrt
the same gases carry with tlicin truces of ethane, the formation
of which is due to potasHiuniiU"i»tnli*f wliicli is foutul pres«*nt in
the solution at the end of the openifion; alno some ethylene.
Von Miller and Ilofcr7 ohtiiinrul from a coitccntrated Rtlutiou
of potassium tartrate* eiirtion moil- and dioxitleH mid
1
Journ. prakt. (1u«n, (2] 7, 112 MH7»>,
2
Bull. see. chim. [2] 0, 427 (IHtiH).
3
Ibid. 8, 23 (1867),
4
Ber. d. doutach. chem, «7f 470
8
Compt. rend. 05, 11.44 uoc. chim. (2] II, 4CIS
e
'Lieb. Ann. 131, 88 (ISIM),
7
Ber. d. deutseh. chem. «7, 470
ELECTROLYSIS OF ALIPHATIC COMPOUNDS. 117 /"
with a little formaldehyde and formic acid, but no acetic acid

!
and ethylene as affirmed by Bourgoin. The ethyl ester behaves
in a like manner.
]
Racemic Acid. — The same investigators found that racemic
acid, on electrolysis of the sodium salt in aqueous solution, \
gives carbon mon- and dioxides and an aldehyde which was
not further investigated.
Ethyltartaric Acid. — This gave the same gases, but any
other substances which may have been formed were not identi-
fied.
Methanetricarboxylic Acid. — Mulliken1 employed the method,
which has already been discussed (p. 104), in the electrolysis
|
of the sodium salt of the triethyl ester of this acid and ob-
tained othanchoxacarboxylic ester, besides some malonic ester.
Further oxidation caused the formation of sodium bicarbonate:
2(COOC2H6)3C = (COOC2H5)3C-C(COOC2H5)3.
Tricarballylic Acid. — The potassium salt of the diester of
this acid wus subjected by von. Miller 2 to the Brown-Walker
reaction, but without success. The ester-acid was in part
regenerated. When potassium acetate, however, was added to
the anode solution the expected reaction occurred; ethylsue-
cinic ester was produced:
CH2 COOC2H5
I COOC2H5
CH2-COO
The peculiar fact that the di-esters of tricarballylic acid, when
electrolysed by themselves, do not afford the expected synthet-
ical reaction, while the electrolysis of a mixture of the acid
with potassium acetate gives these synthetic products, was
made use of by von Miller with several aromatic acids which
had previously proven unsuitable for synthesis when used alone
(see these).
1
Am. Chem. Journ. 15, 323 (1893)
2
Ztsch. f. Elektrochemie 4, 55 (1897).
•''•
Aconitic Acid. — On electrolyzing a concentrated; strongly

alkaline solution of the potassium salt, Berthelot l observed
oxygen, carbon monoxide, and a little acetylene at the anode.
Marie2 was able to convert aconitic acid into tricar ballylic
acid at a mercury cathode surrounded with a solution of the acid
half neutralized with sodium hydrate. Sixty per cent of the
theoretical yield was obtained :
CH-COOH CH2-COOH
C-COOH +2H-CH-COOH
CH2-COOH CH2-COOH.
7. AMINES, ACID AMIDES , IMIDES, AND NITRILES .

The literature on these subjects is very scarce. Little is
known regarding the electrolysis of amines, whose anodic
behavior would probably be very interesting. They are stable
at the cathode, and can be obtained electrolytically by reduction
I of the nitriles. Weems 3 has electrolysed acid amides in the form
of their sodium or mercury compounds. He obtained only the
1; ,
unchanged material used as the starting-point.
Tetrajnethylammonitim Hydrate. — Palmaer 4 electrolyzed a
solution of the hydrate in liquid ammonia in a Dewar vessel
at about — 41°. Deep-blue rings having the color of a solution
of sodium in liquid ammonia appeared at the cathode when the
circuit was closed. A solution of free tetramethylammoniurn
is probably formed, which could not be isolated. The chloride
behaves like tetramethylammonium hydrate.
Tetraethylammonium Chloride. — Goecke 5 has investigated
the behavior of the iodide of this compound in aqueous solution.
He found at the anode tetraethylammonium triiodide :
1
Compare Bourgoin, Bull. soc. chim. [2] 9, 103 (1868).
2
Compt. rend. 136, 1331 (1903).
3
Am. Chem. Journ. 16, 569 (1894).
* Ztschr. f . Elektrochenu 8, 729 (1902).
5
Ibid. 10,250 (1904).
o
M. x
iC 'x
X ~
^ •£ m
•ft
4I
<S
3
—••-•= n j| ~ £ ~ ^S^
if?;; ••
120 EI.Ecnv!iCHl!KMl>Titt «Ml*«r\hs.
A motlrrati* yirltl i f f jH I- niiUnr

p-tolylsuccinimide in U*V ,' M
CH.»-(U
\\MYJ l-Hlli i
Acelylpyrroliclone ran In* i*

50',' <' HSilplsurir a«'i<i flafrl an-1
/N'riMlI;! + 21!;* V* 11-, II. M.
Hydrocyanic Acid. In uljVyn
of Hiilpliiirir -ifiti J
I l l J ? * » i^
y *? f i f ^ * / i «
OWU
l to
mid nw'tlitif :«i id ;*

Fu
fill *'l«'HM,
l)lur* fi nl ihf *iii«wi»\ l«4ti|f lii^ Ii

product of jwilitÎiiiii f<*rrfM),*»m<!<,
Sodium On **I*'r?i^
this salt for n |>n»|ittifnî j««n«»»l 1'Mtli" MI '«*} •!*»' f^n>ri!i
»i
1
!. c.
3
Aw rlilm |»hv«« 7H, IMS rl>tJl <
1
JahntMb. f. CliHrt IHu'i, Ii«fi
* Tnw HI ui*i, Tr «il/ rf I'll <*t r**I«iitii«' 7y>
§
Jtrtin», f }trnUt. rliniiP* Si, 1 1 » flHj'ts
•Fjlff l*,t l Xo 7126 aHHUj ; |>ft
i f. riiifii, ihm, mi
i2 ^tU ««•£» « *•* SB -
7, 4r ^ ^ ^ H E *>•» ^ ~
••"* M 5*"*°* zr "^ ** "**• "~"*<«!* "**• *******%^' *p

S — «^"w ^- »* _^ i
^, j" r* *•• « ^ »«• C» i* sr *«** ***
I f f* *! T *H -I 11 i ^ ^ X s
,
- «t
I
I
X X
u
< "
iff,
tit-' 122 ELECTROCHEMISTRY OP ORGANIC COMPOUNDS
E. Fischer claims that the members of the uric-acid group

can be considered as derived from purin, a parent substance:
(6)
(1) N = CH;
I (7)
(2) CH(5)C-NH\
>CH.
(3) N - C-N
(4) (9)
Accordingly, uric acid appears as 2, 6, 8-trioxypurin, arid

caffeine as 1, 3, 7-trimethyl-2, 6-dioxypurin:
HN-CO CH3N-CO
NH- \
>
U- ^
HN-C-NH- I | CH3
Uric acid CO C-
Caffeine
H.
In the electrolytical reduction of the investigated purin
derivatives, it appeared that the oxygen in position (6) of the
purin nucleus is the only one that can be eliminated for
hydrogen. But an addition of hydrogen occurs also without ii
loss of oxygen; this happens in the conversion of uric acid into
tetrahydrouric acid. Further particulars will be mentioned
under the individual substances.
Parabanic Acid, the urei'de of oxalic acid and oxidation
product of uric acid obtained by the action of nitric acid, is
converted into hydantoi'n and ethyl urea (Tafel and Reindll).
Methyluracyl, the reaction product of acetoacetic ester and
urea (water and alcohol being eliminated)^ can be easily reduced
in sulphuric-acid solution (Tafel and Weinschenk2). Methyl-
trimethylene urea is formed, also a considerable quantity of 1.3-
diaminobutane:
1
Ber. d. deutsch. chem. GeseDseh. 34, 3286 (1901).
2
Ibid. 33, 3378 (1900).
KI.W'lIinLV.SIS iF ALIPHATIC CoMI'or.NDH.
•>'» <--fH:, NU -CJH-CH;,

I. n» <'H ll, ( ! ( ) ( 'H2 .f.n8 0
<>(f
Ml Nil (HI;,
N'H HI-CH,
. <*'» HI. i H,0 _,,Co2.
NfH3--(!IIs
Barbituric AcW, ,\fnlnn;/l I'm/. W.MS invest igut.o<! by the
Hani" an! IIMI- {* iik«-wi?a- jrivc-s two products, syl
hydroiinwsl
gi ami triHii'thyli'in' urea:
MI CO XII -(JHa
j ! i
J i. CO Cfi^L'ili
» co (';n a+n ao;
MI Co 1
XH co
!
XII CO XH-.C!Ia
1 '•
1 !
II, CO l'H ri4H 3 CO CH-I-2H-/]
•
I
XII CO
• i i
Nfl-CIIu
'J1i<- JMtfivcilihility «»f uuiiutty) iircu inio friwictftrlcwe urea
>
t:*k«'jj itM-niiUt'Ctioit m-itfifhw ti''* r>inj»o-';(l»ilitv <»fUi«' rvHiruI tireuH
lain 'iiir iiiin , rujii rvirltoiitc aHil uffonU ft Kitiiftlc method of
Mltt.iihiiip J,.'J 'IJ,iJi»iiiftj<r<>j«trtt' from ntiil'nijf iichl in the name,
ucmit'-r u • Mi i)i.'iruir«thutniie is proiittrci! frotn methyl uracyl:
xn nij Nrt z off,
CO riljiHaf) - <IH»KJOa.
!
i i
MI nia N!r a -oir2
IMnltirfc AcW, Tfrrlrttnjfi £/rm.— Tufel and Jleiiull ' rr<ciu<w<!
iiJtt) Stic*' ntiii oht;»ined M <-hii*f redact bn product Iiydro-
umryl, sSî «»«(»« JrimethyleiH' urea nrtd oxytrimethylenn ?iro«,:
1
Ifcr «J «
11:

NH-CO N H - C H 2
i
,I. CO CHOH+3H2=CO CH2+2H20;
NH-CO NH-CO
NH-CO NH-CH2
II. CO CHOH + 5H2 = CO CH2+3H20;
II II
NH-CO NH-CH2
NH-CO NH-CH2
III. CO CHOH+4H2 = CO CHOH+2H20. t
ftp NH-CO NH-CH2

i Uramil is the reduction product of violuric acid, which is
the isonitroso-compound of barbituric acid:
NH-CO
CO CH-NH2.
NH-CO
It is easily reducible, ammonia being split off, and forms hydro-
uracyll as the solely erystallizable body. The same product is de-
rived in considerable quantity in the electrolytic reduction of
Alloxan, Mesoxalyl Urea. There are also produced in this
reduction alloxantin, which is difficulty soluble and can only
slowly be reduced further, and large quantities of non-crystal-
lizable gummy substances:
NH-CO NH-CH 2
I. CO CO+4H2=CO CH2+2H20;
II II
NH-CO NH-CO
if NH-CO
II. 2CO
NH-CO
CO-NH
CO+H2=CO 0 / CO + HsO.
I? NH-CO
CO-NH
NH-CO Alloxantin
1
Ber. d. deutsch. chem. Gesellsck. S4, 3290 (1901).
!CLKCTItnf,VSIH OF ALIPHATIC COMPOUNDS. 125
Uric Acid. The reduction of uric mid can IK * conducted in

HitHi a way l l i ; i t if taken place principally according to the fol-
lowing t ' f jtiatif m (TafeP;:
<V,iM>:i\4 Hill -CWiAjXi l-H/i
Tafel ealln thf resulting product puron, and given it tli(»
follmvint!; ffiriiiiilji;
XII I ' l l ,
n> ru \it
! n).
MI ni NII-
It i ? fWiuni nliiiu i »*\r!»jîv«*Iy in the reduction of uric acid
in j* T.V ' ulphuiir Ht'l I ;it * I M V 1 and uith lil^h cuirrent con-
ei'iiffifiHii, A j f t r t t i f flu* punm i/i inolc^nilnrly rc*n,rntngc*d
;j|?«*:i'i^ at J'J ! V» !»tr!iiifi|4 mi i^ciiitf*rk* suhstunnc*, isopuron*
l i » fn;*'tiir*' *»1 fh*' l i t l i T IIIIH not yrt b'eii i»xpluin<*d, Tetra-
h* IiMnri«' af)*t aiid i^npurnrt iin» formed in KC)% nulphuricj acid
at 'in at,'i with ;i l«ito**r rtim*nt wneerifritfiorL
1'ir i^rKfti****^ *%'iii b* rxpn.'HHc»il iiy
MS o» t!ie following equations:
Nil-(U1 2
I, « ' « * r \||
MI « MI
i • , i ,t
X1I--(;II-N»-
MJ < ' » l*iif«t*
I I . r«» r Ml X
>C;CM-I[20;
.\H r Mr VH/
XII CIIj
!
XII CO
- v
or j >00.
00 -NIK
CH-NH
Si, JWH (mil).

The structure of the last-mentioned acid has not yet been

determined with certainty. 1
Strange to state, the methylated uric acids, when reduced,
do yield purons which (excepting tetramethylpuron) can be
molecularly rearranged into isomeric isopurons, but the corre-
sponding hydrated uric acids are not produced (Tafel2).
3-Methyluric Acids.—The two isomeric and structurally
identical 3-methyluric acids, the 5- and £-acids, give 3-methyl-
purons. These latter are extremely similar, but show differ-
ences in solubility which point to the possibility of an isomerisrn.
A certain quantity of isopurons was already formed during
electrolysis by the rearranging action of the 60-70% sulphuric
acid used as electrolyte:
N H -C O NH~CH 2
CO C-NHV CO CH-NHV
| || >CO+3H2 = | | >CO+H2Q.
CH 3 N - C-NH/ CH 3 N - CH-NH/
i.3-Dimethyluric Acid. — The reduction to 1.3-dimethyl-
puron takes place very slowly in a 75% sulphuric acid solution.
The molecular rearrangement to isopuron is also very slow.
3.9-Dimethyluric Acid gives similarly a 3.9-dimethylpuron
which, if heated in a 10% sodium-hydrate solution, smoothly
rearranges itself to form the iso-compound. The electrolytical
effect is hence a normal one:
NH-CO NH-CH2
CO C -NHX CO CH~NHX
| || >CO+3H 2 - | | >CO+H20.
CH 3 N -C -N / N -CH-N /
!
CH3 CH3 CH3
7.9-Dimethyluric Acid gives correspondingly a 7.9-dimethyl- l|fl
purcm- ___________ .__________________________ ^ V
1
Ber. d. deutsch. chem. GeseUsch. 34, 1181 (1901). if
2
Ibid., 279 (1901). |
•** it 2?* *s»- ** sr tr si* £• «2
^ m 3& *•* £ *•*
1E
n sr •* ~ ~
* •£ *' C 5 ~ •*« S
X X *
-' » a r. | S. s 1 t x— -,-=:
S. ~- * .5 » ~ £• ~| a" 2
i . g J T ' f S Z . a - S j i p. rr
s' 1 I*» * i Z I. i
ija*.* ? 3 5 -4 5-5 *< :
IT S£ §" " * 1 .?
rf "^§ U«<:B -* n^ 5 9r: H, '<* 3

2. 5 5 ^ ^ nr, .x
i
»^ * O C- *» »S- -^'
I.,5 2.^ * i" ~ zr. *' x
"» a g ^ s. g - * , . H 5- S
S» 3 ? S P SS
sa x t« — -
3" ° ~ ~"
s:. ? s s * n --.,
,1
3
rl
r 3
i
?s * £-
ill
fc'rt- ''<
quantity. The reaction takes place in accordance with the fol-

lowing equation:
NH-CH2
NH-CO
CO C-NHX CO C-
1 || >CH+2H2 CH+HaO.
N H- C - W NH-C-
Xanthine Desoxyxanthine
The latter compound is therefore to be regarded as 2-oxy-

1.6-dihydropurin. These experiments were made by Tafel
and Ach.1
3-Metliylxantliine gives analogously 3-methyldesoxyxan-
4
thine or 3-methyl-2-oxy-1.6-dihydropurin (Tafel and Wein-
schenk2), and
Heteroxanthine, 7-Methylxanthine, yields desoxyhetero-
xanthine, or 7-methyl-2-oxy-1.6-
dihydropurin:
NH-CO
NH-CH 2
I CO C-NH-
! II CO C-NHx
CH3N -C- N- >.4-2Ha- I i|
>CH+H20
NH-CO .
I I CH 3 N -C-N '
II.
NH-CH2
| | CH3 || CH
CO C-NX CO ~C-
| || >CH+2H2= | || „
NH-C-N^ NH-C-N^
EF desoxy-compounds are suitably oxidized, they lose two
atoms of hydrogen and pass into oxypurins. 3-Methyldes-
oxyxanthine is thus converted into 3-methyl-2-oxypurin:
N = CH
CO C-NH\
I II >H,
C H 3 N- C - W
1
Ber. d. deutsoh. chem. GeseUsch. 34,1165 (1901).
3
Ibid. 33, 3369 (1900).
and desoxyheteroxanthine gives the corresponding 7-methyl-
2-oxypurin. These • oxidation products furnish the proof of
the constitution of desoxy-compounds. The constitution for
some of the members had been determined by E. Fischer through
synthesis.
Theobromine, or 3.7-Dimethylxanthine, was reduced by
Tafel 1 in 50% sulphuric acid. He obtained desoxytheobro-
mine, or 3.7-dimethyl-2-oxy-1.6-dihydropurin:
NH-CH 2
| | CH3
CO C-Nv
H.
I II
CH 3 N - C-
3.7-Dimethyl-2~oxypurin is formed on oxidation with an excess
of silver acetate.
Caffeine, or 1.3.7-Trimethylxanthine; was reduced in 50%
sulphuric acid to desoxy caff erne by Tafel and Baillie,2 while
they were investigating the reduction of acylamines to
alkylamines. In a later investigation3 they showed that
desoxycaffe'ine is to be designated as 1.3.7-trimethyl-2-oxy-
1.6-dihydropurin:
CH3N-CH2
| | CH3
CO C-Nv
CH.
By oxidising it with lead peroxide, 3.7-dimethyl-2-oxy-

purin-1-rnethylhydroxide is obtained:
OH
CEkN-CH
| | CH3
CO C-
1
Ber. d, deutsch. chem. Gesellsck. 32, 3194 (1899).
2
Ibid, 686(1899).
* Ibid., 3206 (1899).
130 ELECTEOCHEMISTRY OF ORGANIC COMPOUNDS.
This is a compound which corresponds to the 3-methyl-2-

oxypurin obtained from 3-methyldesoxyxanthine. Its strongly
basic properties are conditioned by the methyl group in posi-
tion (1). It may be here mentioned that Tafel has worked
out his valuable method chiefly by the use of caffeine. The
corresponding investigation has already been considered (p. 24
and p. 52).
Guanine, 2-amino-6~oxypurin, when electrolytically reduced
in a 60% sulphuric acicl, is converted into desoxyguanine,
a base containing no oxygen (Tafel and Ach l):
NH-CO NH-CH2
NH2C C-NH- NH2C
\CH+2H2 = CH+H20.
V
Desoxyguanine, 2-amino-1.6-dihydropurin, is easily oxi-

dized to 2-aminopurin : .;
Pi.
NH2C C-NH-
[U VV — IN JO.N.
,1
II II > H.
N-C - W
This substance is isomeric with adenine and is vef/ sta% i
lar to it. Nitrous acid converts it into 2-oxypurin, an
isomer of hypoxanthine.
The firm of C. F. Boehringer & Sohne (Waldhof-Mannheim)
has patented 2 TafePs process for reducing xanthine bases.
9. DERIVATIVES OF CARBONIC ACID CONTAINING SULPHUR.

/0
Potassium Xanthate.—C. Schall3 ^ obtained; by the elec-
iff
lit f trolysis of potassium xanthate in aqueous solution and with
1
Ber. d. deutsch. chem. Gesellsch. S4; 1170 (1901). '
2
See especially D. R. P. No. 108577 (1808): Process for the preparation
of xanthines containing less oxygen by means of the electrolytic reduc-
tion in .acid solution of alkylated xanthines.
8
Zeitschr. f. Elektrochemie 2, 475 (1896); 8, 83 (1897).
' J > Is t 'I
%1 fiiiM
O'J pIllH HI f4J
i PUB * -i^n qo si îîp^
S S- MS
>\> '
l; ;
•<) ir".y 11^)0- ' ''iiîu-
1C I ») ;)UVH«friV .-In K!.<A'tn,JL r | | J

CHAPTER IV.
THE ELECTROLYSIS OF AROMATIC COMPOUNDS.
IN the aliphatic series the carboxylic acids furnish the

principal material of electrolysis. This is due to the reactive-
ness of their anions, which readily split off carbonic acid, thus
affording manifold syntheses. In the aromatic series, however,
the nitro-compounds are the more interesting, on account of
their easy reducibility and the importance of their reduction
products. The facts which give to electrochemical reduction
pre-eminence over oxidation have already been explained in
the introduction (p. 2).
Single oxidation processes have, however, also become
important. Besides the oxidability of easily oxidizable sub-
stances, for instance aniline, or easily oxidizable groups like
methyl, the peculiar reaction which seems to occur very
frequently in the electrical oxidation in sulphuric acid, and
which consists of the entrance of oxygen into the benzene
nucleus, must be emphasized. Hydrocarbons, phenols, quin-
ones, and azo-compounds seem to behave alike in this respect.
Electrolytic substitutions furnish a further general point of
view.
Although the substitution processes afforded by the action
of the primarily discharged anion of an inorganic salt upon an
organic body are to be included among the simpler reactions,
the results obtained so far in this domain have been very scanty,
especially in regard to aromatic substances. The above-
mentioned investigations of Elbs and Hertz, as well as those of
Forster and Mewes on the electrolytic preparation of iodofonn,
132
THE ELECTROLYSIS OF AROMATIC 133
can serve as an indication that many interesting and reitu.ment~

tive problems yet await solution in this field.
1. HYDROCARBONS.
Benzene.—Renard, 1 by the anodical action of the current
in.an alcohol-sulphuric-acid solution of benzene with plntinum
anodes, obtained a body melting at 171° which Gattowmtm and
Friedrichs 2 recognized later as hydroquinone. The la/tter is
also formed (Kernpf3) if a mixture of benzene and n 1 ()',,'•
sulphuric acid is eloctrolyzod at lead-peroxide anodes rind lend
or zinc cathodes. Quinone is first produced at the anode with
the aid of the lead peroxide. It is then reduced at the enthodo
to hydroquinone.
The process very likely occurs in the same way at a plntinum
anode. Hydroquinone itself, when oxidized electrolyticully,
yields only traces of quinone (Liebermann 4 ), quinhydronc*
being the chief product.
However, it is not impossible that at platinum miod<»s
a direct introduction of hydroxyl groups into the l:>c»nssonn
nucleus, i.e. a primary formation of hydroquinone*? taken
place, especially if concentrated sulphuric acid is clioson J I B
the electrolyte. Chemical as well as -electrochemical *vxjK»ri-
ences indicate this. Thus, by means of persulphuric iteid or
its salts, obtained by the electrolysis of sulphuric acid or its
salts, nitrophenol can be directly converted into nitrohydro-
quirione, salicylic acid into hydroquinonecarboxylie acid,
anthraquinone into alizarin, and this latter into alissuriii-bcir-
deaux and alizarin-cyanine.
It may be here mentioned that oxygen can thus "bo c*ledro-
lytical'ly introduced into azobenzene. Heilpern,6 by eleciroiyr/lng
azobenzene in concentrated sulphuric acid, obtained totruoxy-
1
Compt. rend. 91, 175 (1880).
2
3
D. R. P. No. 117251 (1899).
*Ztschr. f. Eiektrochemie 2, 497 (1896).
5
Ibid. 4, 89 (1879).
.v,
fev *
azobenzene, a fast dye, soluble in concentrated sulphuric acid

with a cherry-red color and resistant to the action of light and
acicls.
Toluene.—According to Renard,1 this compound, by elec-
trolytic oxidation in alcoholic-sulphuric acid, forms benzaldehyde
and phenose, C6H6(OH)6(?). According to Puls,2 there are pro-
duced in the same electrolyte, using a diaphragm and a platinum
anode, benzaldehyde, benzoic acid, benzoic ethyl ester, and, as
chief product, p-sulphobenzoic acid. Under the same con-
ditions, Merzbacher and Smith3 had obtained a poor yield of
benzoic ethyl ester.
Law and Mollwo Perkin 4 report on the electrolytic oxidation
of toluene, the three xylenes, mesitylene, and pseudocumene.
In a sulphuric-acid-acetqne solution of toluene they obtained
a little benzaldehyde and perhaps benzyl alcohol. The elec-
trolysis of an emulsion of toluene and dilute sulphuric acid
leads to a complete combustion of the toluene to carbonic acid
and water.
The three xylenes, electrolyzecl in acetone and dilute sul-
4 phuric acid, yield principally the three toluic aldehydes, rn-
Xylene, even when sodium acetate and acetic acid are employed
as electrolyte, gives the m-toluic aldehyde.
Pseudocumene, in the presence of acetone and sulphuric acid,
gives apparently a mixture of the three isorneric dimethyl-
benzaldehy'des. Analogously, mesitylene is oxidized to mesity-
lenic aldehyde.
Naphthalene.—This substance, electrolysed by Panchaud
de Bottens 5 in a sulphuric-acid-acetane solution at platinum
and lead anodes, gives, besides a brown by-product, principally
a little a-naphthoquinone. In glacial-acetic-sulphuric acid
traces of phthalic acid are formed at platinum electrodes.
' * Compt. rend. 91, 175 (18SO).

2
Chem. Ztg. 25, 263 (1901).
8
Journ. Am. Chem. Soc. 22, 723 (1900).
4
Trans, of the Faraday Soc. I (25/10, 1904).
6
THE ELECTROLYSIS OF AROMATIC COMPOUNDS. 135
2. NlTRO- AND NlTROSO-COMPOUNDS.
Of all organic substances which have been tested as to

their behavior towards the action of the electric current,
aromatic nitro-compounds have received the most accurate
treatment and attained the greatest importance. The reason
for this lies, on the one hand, in the fact that the nitro-group,
being extremely reducible, reacts only at the cathode, whereby
the end-products are closely and simply related to the product
started with; and, on the other hand, in the variety of the
reduction phases which the nitro-group can develop, depending
upon the conditions of the experiment.
It thus happens that the class of nitro-bodies not only affords
the greatest number of important results and smooth reactions,
and thereby is of great importance technically and for the
manufacturing side of organic chemistry, but it also offers the
suitable starting-point for the treatment of general and special
theoretical questions. So far as these are of a general nature,
treating of the relation of the reaction velocity to the reduction
velocity and referring to the importance of the cathode material,
they have already been discussed in the first chapter. The
theoretical relations, which are of importance only for the
reduction of nitro-bodies, will be briefly considered here. They
can be divided into purely chemical and electrochemical ones.
The former, which obtain in every method for the reduction of
nitro-bodies, deserve mention because they were first understood
in closest connection with the electrical reduction; they refer to
chemically possible reduction phases and their gradation. The
latter encompass the dependence of the chemical results upon
the electrical conditions of experiment and the special r61es of
the separate decisive factors.
The importance, thus shown, of our knowledge of the
electrical reduction of nitrobenzene in regard to the practical
and theoretical exploitation of the electrolysis of organic sub-
stances makes it desirable to first give a short historical survey
of the development of the views and the importance of the

separate observations.1
a. General Observations on the Reduction of Nitro-compounds.

Hiiussermann 2 reduced nitrobenzene and nitrotoluenes both
in alkaline and acid solution, the former with iron, the latter
with platinum, electrodes. By reduction in alkaline solution,
he obtained as principal product hydrazobenzene and hydrazo-
|- toluene respectively; in sulphuric-acid solution he got from
nitrobenzene, as chief products, benzidine sulphate and azoxy-
benzene, besides an easily changeable body which was not further
determined. o-Nitrotoluene 3 under like conditions gave o~tolui-
dine sulphate, besides small quantities of o-toluidine; p-nitro-
toluene yielded principally p-toluidirie.
Elbs, on the contrary, obtained entirely different results
II I'l, i,
I I I .!
when he electrolytically reduced p-nitrotoluene and nitrobenzene
in acid and in alkaline solution with other cathode metals.
There were formed in the reduction of nitrobenzene in alkaline
I solution at a lead or mercury cathode varying quantities of
azoxy- arid azobenzene} the former mostly preponderating.
p-Nitrotoluene behaves similarly if reduced in the same manner,
—-p-azoxy- and p-azotoluene being produced. The reduction
takes place much more slowly and less completely in this case
than when nitrobenzene is used. Hausserrnann observed the
same with o-nitrotoluene. o-Nitrophenol behaves quite differ-
ently; the chief product is o-amidophenol, besides red and
brown substances which could not be obtained pure. In the
reduction of nitrobenzene in sulphuric-acid solution Elbs
employed a zinc cathode and obtained chiefly aniline.
Elbs4 draws the following conclusion: " Without consider-
ing the other conditions of experiment, the kind of metal
1
This classification (a) has been partially taken from the dissertation
of my pupil Jos. Schmitt: '' Concerning the Importance of the Cathode
Material in the Electrolytic Reduction of m~ and ]>-Nitrotoluene/; Bonn, 1904.
2
I 3
Chem. Ztg. 17, 129, 206 (1893).
Ibid, 209 (1893).
III
employed as electrode seems to exert an important influence,

since Haussermann obtained benzidine and azoxybenzene
from nitrobenzene at a platinum electrode/' Gattermann
and Koppert,1 by electrolytically reducing nitrobenzene in con-
centrated sulphuric acid with the addition of a few drops
of water, obtained other results. After several hours' electrol-
ysis the contents of the earthenware cell, which contained
the reduction fluid together with a platinum cathode, solidi-
fies, forming a colorless mass of crystals of p-amidophenol
sulphate, which was permeated by a blue-green liquid.
After these observations, Gattermann and his pupils 2
continued their investigation on the reduction of aromatic
nitro-bodies to amiclophenol derivatives. They thus examined
mono- and dinitrohydrocarbons, nitroamines, nitrocarboxylic
and nitrosulphonic acids, also the esters of the acids. After
the reaction had been successfully tested in over 40 cases it
was adjudged to be of general applicability.
The important result of these experiments is that nearly
all nitro-bodies with an unoccupied para-position are con-
verted by electrolytic reduction in concentrated sulphuric
acid into p-amidophenol derivatives, i.e. not only is the nitro-
group reduced completely to the amido-group, but in most
cases the hydrogen atom in p-position to the amido-group is
simultaneously substituted by the hydroxyl group.
A short time after the publication of the interesting experi-
ments of Gattermann, A. A. Noyes and A. A. Clement3 made
known their studies on the electrolytic reduction of nitro-
benzene in sulphuric-acid solution.
Noyes and Clement used concentrated sulphuric acid of
L84 to 1.94 sp. gr. as a solvent for nitrobenzene. Gatter-
mann and Koppert had treated the sulphuric-acid solution
before the reduction with a few drops of water. Noyes and
Clement obtained from 50 g. nitrobenzene at platinum elec-
trodes 30 g. anhydrous p-amidophenol-o-sulphonic acid, cor-
1
Chem, Ztg. 17, 210 (1893).
* Ber. d. deutseh. chem. Gesellsck 26,1844,2810 (1893); 27,1927 (1894).
8
Ibid. 20, 990 (1893).
responding to a yield of 40 per cent, of the theoretically pos-

sible quantity.
Three years later Elbs l reverted to the experiments of
Gattermann. On repeating the. same he obtained, indeed,
the same results, but simultaneously observed that consider-
able quantities of aniline are always formed besides the p-ami-
dophenol. When Elbs used glacial acetic acid as a diluent of
the sulphuric acid he found a considerable increase in the
yield of p-amidophenol, but the yield of aniline kept apace
of that of the latter. If he used a lead in place of a platinum
cathode, the reduction was accelerated, being favorable to
the aniline formation at the expense of the p-amidophenol.
Lob2 found a reaction analogous to that of Gattermann
when he reduced nitrobenzene in hydrochloric-acid solution
or suspension, using platinum electrodes.
In this process there is formed as chief product a mixture
of o- and p-chlor aniline. The formation of this can be explained
thus : The primarily formed phenylhydroxylamine reacts with
the hydrochloric acid, simultaneously rearranging itself:
= C6H5NHC1 -I- H20.
The same mechanism of molecular rearrangement must

be assumed in Gatterrnann's reaction:
Direct proof of the correctness of this view was produced

by Gattermann3 on adding benzaldehyde to the solution of
nitrobenzene in sulphuric acid. Benzylidenephenylhydroxyl-
amine is formed:
/0\
CeH5NHOH+OHOC6H5-C6H5-N— HC-C6H5;
1
* Ber. d, deutsch. chem. Gesellsch. 29, 1804 (1896).
8
Ibid,, 3034, 3037, 3040 (1896).
i.e. the condensation product of phenylhydroxylamine with

benzaldehyde.
A similar influence of the cathode material, as observed
by Elbs in replacing the platinum electrode by a lead cathode
in sulphuric-acid solution, was found by Lob l when he used
a lead cathode in hydrochloric-acid solution. No chloraniline
was formed, aniline being produced almost exclusively.
Further observations concerning the influence of the cathode
material in reductions were made by Lob 2 in his studies on
the electrolytic preparation of benzidine. His results are
briefly the following:
1. Platinum and nickel electrodes behave alike in the
experiments to reduce nitrobenzene in acid solution to ben-
zidine. Carbon cathodes, ons the contrary, give only little
benzidine; zinc and amalgamated zinc electrodes yield no,
or extremely little, benzidine, while aniline, as already pre-
viously observed by Elbs, results as the principal product.
2. Mercury, nickel, copper, zinc, lead, iron, brass, and zinc
amalgam were tried as electrode material in respect to their
reduction behavior in the reduction of azobenzene to benzi-
dine in alcohol-sulphuric—acid solution. It was shown that
the furthest utilizable reduction was obtained with mercury;
the usefulness of the other metals was determined to be in
the following order: Lead, sheet nickel, nickel-wire gauze,
copper, zinc, iron, and brass.
3. In the reduction experiments of nitrobenzene to azo-
benzene in alkaline-alcoholic solution mercury electrodes prove
good; however, nickel-wire—gauze electrodes give excellent
results. This had been already shown by Elbs.3
4. The same is true in the reduction of nitrobenzene to
azoxybenzene igt an alkaline aqueous suspension.
Finally, the employment of a strong hydrochloric acid and
a tin cathode, or an unattackable cathode with addition of
1
2
Ibid 7, 337, 597 (1900-1901).
8
Ibid. 5, 108 (1898).
stannous chloride, was ascertained to constitute a

condition for the reduction of azoxybenzene and azoben0< *
to benzidine.
The practical results of all these investigations for t
reduction of nitrobenzene ancl its reduction phases are
the following:
At attackable electrodes, like zinc, lead, and tin, the
tion generally proceeds further than at unattackable electro <1<
such as platinum, nickel, and mercury. The attempts
utilize technically these properties of the cathode metals $
a series of nitro-bodies led to important patents.
Thus Boehringer & Sohne l (Mannheim) patented a proc*<
by which, when employing tin-cathodes (or cathodes of otlh
indifferent metals with an addition of a small quantity of
tin salt), fatty or aromatic mtro-compouncis, dissolved
suspended in aqueous or hydro-alcoholic hydrochloric ac*3
can be reduced' in almost theoretical yields to the correspori
ing amines.
In hydrochloric-acid solution, as already mentioned, chic
anilines are produced q,t platinum electrodes.
According to another patent 2 of the same firm, cop fH
lead, iron, chromium, and mercury can be used instead of I i
if these metals are added in the form of their salts or as a fine:?
divided powder to the cathode electrolyte.
After the publication of these patents Elbs and Silbermaii I
reported that if a lead cathode in sulphuric acid is employ*
the same results are attained. It proved to be true that
order to obtain the best yields of aniline diluted alcohol serv
as a better diluent for the sulphuric acid than the glacial aec*i
acid formerly employed. Zinc behaves in sulphuric-acid
tions like lead; however, the precipitation of difficultly
ble zinc double salts is a hindrance. Elbs likewise obtain
90 per cent of the theoretical yield of toluidines from o- ;uu
1
D. R. P. No. 116942 (1899).
2
D. R. P. No. 117007 (1900).
3
Ztschr. 1 Elektrochemie 7, 589 (1901).
m-nitrotoluene; the yield from p-nitrotoluene was a few per

cent. less.
A supplementary patent of Boehringer & Sohne l extends
the process of the D. R. P. No. 116942 to the reduction of
azo-bodies to amines.
The patent claim is as follows: "Process for the reduction
of azo-bodies to the corresponding amines; consisting in
reducing azo-bodies in acid solution by simultaneously con-
ducting a constant electric current either with a tin cathode,
or with an indifferent cathode and the addition of a tin salt
or pulverized metallic tin.7;
In a later patent2 C. F. Boehringer & Sohne point out that
the nitre-compounds in acid solution can not only be reduced to
amines with such metals as easily evolve hydrogen with dilute
acids, but also with copper. This fact offers particular technical
advantages, because copper can be most easily and completely
regenerated electrolytica ly from the liquors. While in the
above-mentioned methods the reduction to the amines is made
in acid solution, C. F. Boehringer & Sohne have obtained a
patent3 according to which it is also possible to reduce nitro-
bodies to the corresponding amines in alkaline and alkali-salt
suspension, if a copper cathode with or without the addition
of copper powder is employed.
According to an investigation by Elbs and Brand,4 the
addition of copper powder is absolutely necessary for obtaining
the desired effect.
In 1899 the Farbenfabriken vorm. Friedr Bayer & Co.5
(Elberfeld) patented a process for electrolytically preparing azo-
and hydrazo-eompounds. The method is characterized by the
fact that the nitro-body to be reduced is held suspended in the
alkaline cathode liquid, and is reduced during continuous vigor-
*D. R. P. No. 121835 (1900). See also the English Pat: No. 19879
(1901).
2
D. B. P. No. 127815 (1901),
3
D. R. R No. 130742 (1901)..
* Xtschr. f. Elektrochemie 8, 789 (1902).
*D. R. P. No. 121899(1899).
ous stirring and the addition of a metallic oxide solution of zinc,

tin, or lead.
This method was then extended by a supplementary patent,1
according to which the reduction of aromatic nitro-bodies is
carried out in aqueous alkaline suspension instead of in the
presence of alkali-soluble oxides of the heavy metals and the
use of such metal cathodes the oxides of which are soluble in
alkalies.
It is very evident, from all these observations, what influence
the cathode material exercises on the obtainable reduction
phase of nitrobenzene and its derivatives. There is no lack of
attempts to explain this influence. The expressed opinions can
be grouped under three points of view:
1. The specific action of the cathode metal is a purely
chemical function.
2. It is a purely electric function, and depends upon the
potential values obtainable on the various metals.
3. A summation of electrical and chemical influences occurs.
Elbs 2 defends the first view. He explains the aniline forrna-
fp tion at lead and zinc cathodes in sulphuric-acid solution in the
11
|l following manner:
'' We will have to suppose that the lead sponge occurring at
the lead cathode reduces the nitrobenzene to aniline. Men-
tioriable quantities of lead sulphate cannot be found, since this
is continually reconverted to lead sponge by the freed hydrogen
ions. This process is analogous to the one previously published
"by me3 in which a hydro-alcoholic solution of nitrobenzene
acidified with sulphuric acid gives aniline when a zinc cathode
is used. Considerable quantities of zinc sulphate do not occur.
At a platinum cathode, under the same conditions, no aniline is
formed, but azoxybenzene and hyclrazobenzene or benzidine
form. This has been confirmed by Haussermann." 4
The explanation attempted by Elbs agrees in general with
1
D. R. P. No. 121900 (1899).
2
8
Chem. Ztg. 17, 209 (1893).
4
Ibid., 129 (1893).
i
Ilifttll I I
4T I
f/JtlJUJ^ pill! f; ff)iOi"tii|Ilf;) A*q p*lJff«Up!:? f«(Jt

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p jo 8u!pU!:j
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li'I
lead cathode is primarily reduced almost exclusively to hy-

clroxylamine, which can only with great difficulty be changed
elcctrolytically into ammonia. At copper electrodes ammonia
exclusively is formed. Since nitric acid cannot be reduced to
hydroxylamine to any appreciable extent chemically by copper,
nor electrically at copper electrodes, Tafel supposes that an
intermediate product is formed in the electrolysis of nitric acid;
possibly dihydroxylamine Nil (OH) 2 possesses the property of
being chemically reduced by copper to ammonia. Thus the
reduction to hydroxylamine would be a purely electrical process,
while the formation of ammonia at copper electrodes depends
on a combination of electrical and chemical reductions.
Two important results can be derived from all these investi-
gations: The certain insight into the course of the reduction of
the single phases and the clear knowledge of the importance of
the cathode potential.
Since the decisive relations have been worked "out with
the simplest representative of a nitro-body, nitrobenzene, the
necessary data on this substance will be discussed first, arid
these data will be supplemented so far as necessary under the
derivatives of nitrobenzene.
b. The Reduction of Nitrobenzene.

I. Chemical Relations.
The course of electrical reduction, like that of purely chem-
ical reduction, depends decisively upon whether the reduction is
carried out in an alkaline or acid solution. But these relations
are of a positive nature in electrolysis only so long as they are
not compensated by the electrical factors, such as cathode
material and potential. To avoid a complication, it is necessary
to limit the considerations primarily to unattackable cathodes
and to take no account of an adjustment to certain and constant
cathode potentials, and to exclude a secondary interference of
the solvent, for instance by molecular rearrangements. In..
this general comprehension of the problem it can be said
that the weU-knawn chemical rule reoccurs in electrolytical
reduction; viz., in acid solution the f«»nnati'»n of aniline ^
favored, in alkaline solution thai « < f axi»xy=- and ;*/."hfn/,»'n",
Lob l has. tried to explain these farts nn th«* ba.*-i- »* f the
electrolytic dissoriat»on theory. He enij»ha.,-i/r-- f ! t « - faet that
in alkaline solution sodium inn-, in arid vuiuH'in hvdr«c r »-n
ions, lend chiefly t c i efferf. reduction. In th«' biUrr »'a>»- ?hi»
tion of hydra xo~ and nmido-cnjupout

i[
scale. Kven if these* considerations
sit ion thai in alkaline elect rt»lyfe>. i;
marily the reducing agent, are Hm;
Bci^rii unsuitable as a ba-sis of a jr«*i because I hiber
has proved by thî p!, in\ the typically
alkaline reduc-fioii product,*, ;*/osy- nnd a/ f o-
!>en%ene, possess a sec'ondary chanicter, -do not l*«lM.nj*; lo
tlie normal coursr* of n*ac!ion. but are first fWiwd by the mn-
d(»ns:iti(»ns of iifinjiul r**dnction phu-Ne^. Siiif* l!al*«»r lin^
also shown that, the primary reduction jirf«iiipf^ i t s alKalinr*
and aci«l electn»lyfes art* flu* .suiiits the ilivergf^M*!*^ in tin*
resul ts ran be expl ained only by the rewtion veloci-
ties with \vlilfli the iii!*!itiii!if*d f«iiiiif*ii«itiniiH ficrur, HI iliiit
in this the i nfluence of lli e ion*
shown itself.
2
We are iii«lf»bt«l to the lal»»rMof hi#
;i
artel t-o Iial«T*H ^xfiîHvi* for tin*
of the* reduction mcHuuifciri.
The typical order In in b:
iT, fiiifher ti»tltirti"fi^ uhich ofi**i« ii4t«*rnipf ill**

of flie process from iiifroiîixi'nr t<* iwrtir If**
tweeti the«e wtmpli* rr*»lucfion proiluct^ A nf fiw-i-
MlitieH hinder the* iipjii»aniiiri» of flu* ttlm*<Mni*!ft}r»w«f(
reaction Mcheine urilfss e>pi»ili! rnffiiif 11111*1 mt* rrnifwl;
* ZtHrhr, fur EIi4i n»c*ti#tii$i* i, Ilfl f i viii,
*Ik»r (i. clriilicli riirni, CliwIbrJ* 31, (Wfr)t
f ail HHWH;; f
in the first instance the condensation of nitrosobenzene with

phenylhydroxylamine to azoxybenzene, which is further re-
ducible to hydrazobenzene; also the reaction of the hydrazo-
benzene thus produced with unchanged nitro- or nitrosobenzene
to azobenzene, which is likewise a primary source of hydrazo-
benzene; then the rearrangement of the latter to benzidine,
that of phenylhydroxylamine to amidophenol or its derivatives,
and finally the .capability of phenylhydroxylamine to yield
azobenzene in alcoholic-alkaline solution with the splitting off
of water
The different processes occur in varying proportions quan-
titatively or qualitatively, depending upon the nature of the
electrolyte and of the cathode material, and upon the current
conditions.
The following reduction and reaction scheme can be given
in support of Haber's descriptions for the electrolytic processes:
I
C6H5NCK
NC6H5
• V
HNC6H5
G6H6NH2
Azoxybenzene is therefore formed by condensation of nitro-

sobenzene and phenylhydroxylamine. This reaction, like the
production of azobenzene, takes place very rapidly under
the influence of sodium ions; the ready occurrence of both of
these substances ia alkaline solution is thus easily explained.
Azobenzene is mostly produced by a condensation of nitro-
- H — X
* _-
C *""* *—I
oe s G
S J5
- -r u-=^--
II. Significance of the Electrical Relations.

It is evident that the whole connection between experi-
mental conditions and the obtainable reduction phase is regu-
lated by the reaction velocities of the competing processes.
The possibility of the formation of each reduction product
is always present in the reduction of nitrobenzene; only
those products, however, can become the principal products
which are so rapidly produced that the other possible processes
cannot find time to take place to any appreciable extent.
Thus only aniline will be principally produced if the inter-
mediately occurring phenylhydroxylamine is not rearranged
more quickly than the reduction takes place. Inversely,
to obtain arnidophenol; the rearrangement velocity must be
so increased that the reduction velocity of phenylhydroxyl-
amine will be trifling.
The point is to determine the factors upon which the
velocity of reaction leading to the separate phases depends.
This question can be divided and simplified'. It is, therefore,
apparent that a whole series of circumstances must be decisive.
The nature of the cathode will regulate the actual reduction
speed (p. 11 et seq.), either by furnishing the reducing ions, or by
influencing catalytically the reaction between the discharged
ions and the depolarizer; or by both injfluences making them-
selves felt simultaneously. The concentration of the acid
influences the velocity of rearrangement, either of that of
the phenylhydroxylamine or of the hydrazobenzene. The
nature and concentration of the alkali, arid the presence or
absence of alcohol, determines the velocity of the condensa-
tions or of the splitting off of water from phenylhydroxyl-
amine, and these relations mutually permeate one another. If
the problem can thus be subdivided into individual problems,
it can also be considerably simplified by the form of the
interrogation: Is there one factor in which all these relations
are decisively expressed; is there one quantity which determines
clearly the velocities of the possible reactions ?
The answer, under certain limitations, is an affirmative
150 KLK<!TMi)C!HKMISTH.Y OF Ul(t;\Nfr c '< »MI'«
one. The value of the* cathode potential wholly includes all

single4 factors- - a certain value of the cathode potential corre-
sponds to a wholly certain reduction product, IP * matter if it
occurs primarily or secondarily. To emphasize only th»' /////•
important point - s o long as a hotly acts as a depolarizer it
ar ts codefenninnfivcly on the value of the potential. If
its depolarizing propeily is destroyed hy rearrangements,
or hv condensations which hart* iif^tliiiig to ilu ilin*<»ily with
the clcc'lnra.! process, t j j i s reaction must express itself in tin*
vahi(» of tin* potential. Of < f *»urse a rertitin phasr rannof
l>c» protluctMl tuiiier .ill rotiilitif»ns, for instaun*, nf optional
concent rat ions of the electrolyte; tliis ^Jiown itsi-lf in tin*
fact, that it in not then possible to ohfuin tin* jwttential con-
ditioning this phas**- the potential always remain.** the fuea.^
lire for lite* possihle efffcf. However, these considerations
an* only true provisionally in the C»M * \vhere the reialirm in
which the potential stand* to the current strength « t i i f l to
the concentration of flu* depolarizer is a |'*'riwiti**nt one, which
can c\'isilv IK* fulfilled by a nuitahle clioicn* i»f f*ondif ions. Kxcej>-
tioim to the rule* and the of the excrptioiiH will I*c ex|«lns!ii*(l
preni'fitly,
in iictf always uuule of I hi1- iifj{0*fUnit fuct in prai'fice;
I* HC *
the existing chemical i*\piit'iief*;% th** îrnpticttv <*f Ili»* e\j*»»ri-
inents often render if le;»/i}»Jf to produce fi t * - »l*'*tr»'d »1Ji*ct
with certainty hy ohs«»rvinK a s<'rt«*< uf «^r4ly con>rnH«'«{ run*
ditioni4 such as ciiiireiifrafitiii, teiuj»»Tatur**. *»!«»«*!r«^l>* ttmte-
rial, and current di'tiHity hut Hiwe rfinfliiloii'/ the-n hav*»
only the effect of liuiiting the {ififniliiil f t * tip* valuer wre^-siry
for ohtitiniiig the n*Hu!f. lf k* flrfi*ritiifii*tsrtfi of this ri4ufi*iii
required some tinii% and i*vf*u to-day flp* i*iiiiiti*rli««i lrfw»*fn
potential and midioit vc»IcM?ity in mil rct'ogmmi liy ali iiivr*«"
tigators*1
i unrl
1
Tlitw Klbs linn rwwttly r**fi*rn*il lii«* «l$ffi*ri*tif
fHifKlK f in flu* p'lltirt if »n «f ||ii» fttfr#»
*tr «rf fl*»* ft-, m«f
IiirirlraniM*/* laying i*w ilir i lu*t

I ' 01 th« wiltiirlifiu i!i*p'ficl« tin*
!.
Haber 1 deserves the credit of having determined the

importance of the potential at unattackable cathodes in the
reduction of nitrobenzene. Later Lob and Moore2 experi-
mentally proved for a whole series of cathode metals and
additions that with equal cathode potentials the results are
always qualitatively and quantitatively the same; but if
the potential is neglected the most varied products result.
But the potential is only a measure for the reduction energy
if the total current work is essentially employed for the reduc-
tion process, and if greater quantities of it are not used up for
accomplishing certain other work at the electrodes. Cases
in which this occurs have been observed by Russ/ 3 and by
Haber and Iluss. 4 They tried to explain these, as touched
upon in the first chapter. It appears, namely, that the elec-
tric energy necessary for a certain fixation of the potential
of the cathode often depends not only upon the chemical
material of the cathode, but also upon its surface and its pre-
vious treatment. Retarding or accelerating influences can occur
at the electrode; a pre-polarization especially can convert it into
an active labile condition, whose cause—perhaps the formation
of a gas film absorbed by the electrode—has not yet been
explained. If the renewal of such a gas film, or more gen-
erally speaking, the restoration of the changeable electrode
conditions, demands appreciable quantities of the total work,
the potential^ can no longer serve solely as an expression for
the chemical changes at the cathode.
Lob arid Moore have experimentally proven the decisive
importance of the potential in the reduction of nitrobenzene;
the electrodes investigated by them were riot seriously affected
Elektrochcmie 10, 579 (1904). In reality it is a question of competi-

tive reaction velocities which must find their expression in the potential.
1
Ztschr. f. Elektrochemie 4, 511 (1898); Ztschr. f. phys. Chemie 32, 193
(1900).
3
3
Ibid. 44, 041 (1903).
* Ibid. 47, 257 (1904).
. . 152 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
by the last-mentioned influences. The results of their investi-

gation are the following:
In the reduction of nitrobenzene in a 2% aqueous sodium.-
hydroxide solution, according to previous publications, azoxy—
benzene is formed at platinum and nickel electrodes, azobenzeno
at lead, tin, and zinc cathodes, and aniline at copper cathodes,
especially in the presence of copper powder. It was found
that, in an unchangeable experimental arrangement, a cathoclo
potential of 1.8 volts, as measured in connection with the deed-
normal electrode, could be carried out with all the chosen
cathodes and additions. At this constant potential, by using
different metals and adding various metallic hydroxides, the
whole reduction was carried out and the nature and quantity
of the reduction products determined in each case. It turned
out that the emphasized differences in the results disappeared
arid that, with an equal potential of all cathodes, similar yields
of azoxybenzene and aniline and traces of azobenzene resulted.
The cathodes were of platinum, copper, copper and • copper*
powder, tin, platinum with addition of stannous hydroxide^
zinc, platinum with addition of zinc hydroxide, lead, platinum
with addition of lead hydroxide, and nickel. The yields of
azoxybenzene varied from 41-65%; of aniline 23-53%.
Considering the trifling quantity of the product started
with which had to be chosen in order to at all carry out the
experiments, and considering the difficulty with which a,n
accurate quantitative separation and determination of tlxe
\
reduction products could be carried out, the proposition thett
can be laid down as a sure result of the above is that the cathode
potential -is the measure for the reduction energy for nitrobenzerz^
when a 2% sodium-hydroxide solution is employed as electrolyte.
Another investigation may here be mentioned which™—
chiefly carried out with nitro-bodies—contains ideas which
become of general importance and can perhaps furnish a new*
physicochemical method for determining constitutions.
Panchaud de Bottens l has determined the drop in potential
1
Ztschr. f. Elektrochemie 8, 305, S32 (1902).
to which a hydrogen electrode is subject on the addition of bodies

of the aromatic series. Tnese"" depolarizing values/' when,
measured under exactly similar circumstances, are a function
of the chemical nature of the depolarizer and are closely related
to their composition and constitution. It might be of particular
interest to choose an oxygen electrode in place of a hydrogen
electrode, since perhaps all organic substances .show a depolariz-
ing value when measured by the former. The results are tile-
following:
The depolarization of a hydrogen electrode in the presence of
a reducible body was investigated, fifty-three aromatic bodies
being thus examined: Nitroso-, nitro- and nitrosamine-,
isodiazo- and diazonium-bodies. The investigation of the depo-
larization was made by taking into consideration its course in
time and in connection with the concentration.
1. The reduction energy of hydrogen at platinized platinum
electrodes can be given in comparison with reducible bodies as
" depolarization value " in volts.
2. Analogously constituted bodies have analogous depolar-
ization values.
3. Different groups of depolarization values correspond to
differently constituted groups of bodies.
4. The absolute valued of the classes of bodies investi-
gated in acid solution (n/i H2S04 or n/i CH3COOH) are the fol-
lowing :
a. Nitroso-eompounds = 0.64 —0.5 volt,
b. Mononitro-compounds = 0.33 —0.23 volt,
c. Nitrosamines and isodiazohydrates = 0.16 -0.09 volt^
d. Diazoriium compounds = 0.47-0.37 volt,
e. Isodiazotates, normal diazo-compounds, do not de-
polarize.
5. Regular laws have not resulted in the case of isomera
within a group.
6. In acid solution, in the case of isomers of nitro-disubsti-
tution products, the ortho-position proved to be the one which
depolarized the hydrogen electrode the most.
7. The method for the determination of the depolarization

value shows in the case of the two investigated isodiazohydrates
(isodiazobenzenehydrate and p-nitroisodiazobenzenehydrate)
that they belong to the nitrosamines.
III. Presentation of the Reduction Phases of Nitrobenzene.
An idea of the electrolytic behavior of nitrobenzene is best

obtained by the use of the reduction scheme, by carrying out
the experiments according to the chief products occurring in
the reductions. For after the first observations of Kendall,1
Elbs,2 Hiiussermann,3 and Lob,4—who all taught and showed
the variety of obtainable products that it is possible to bring
about electrolytically at almost every reduction stage—a desire
predominated to find out the conditions which make possible
and favor the preponderating formation of a certain substance.
The primary reduction products are nitrosobenzene, phenylhy-
droxylamine and aniline. Secondary substances, i.e. those
produced by chemical action, are azoxybenzene and azobenzene,
which in turn can give hydrazobenzene or benzidine and aniline.
Phenylhydroxylamine can pass into amidophenol and also
undergo other rearrangements and condensations. The pos-
sibility of causing at will certain phases to yield the chief prod-
ucts of reduction is of great importance for the manufacturing
and technical side of the electrolysis of nitrobenzene. The
following is known concerning the formation of the separate
reduction stages:
Nitrosobenzene.—It is natural that so good a depolarizer as
nitrosobenzene is at the cathode cannot be separated as such
under the conditions of a continuous reduction. Haber,5 ,by
adding a-naphthol and hydroxylamine to the electrolyte in
alkaline solution, could, however, prove the presence of nitro-
sobenzene in the form of its characteristic condensation product,
1
B. R. P No. 21131 (1883).
2
Chem. Ztg. 17, 209 (1893).
8
Ibid., 129, 209 (1893).
4
5
Ibid. 4, 511 (1898).
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the great reactivity of the body, which reactivity exposes it,

•even during the electrolysis, to further reactions. In alkaline
•solution it is chiefly the condensation of phenylhyclroxylamine
with its predecessor in the reduction, nitrosobenzene, to azoxy-
benzene; or in alcoholic-alkaline solution the condensation of two
molecules to azobenzene. In acid solution the rearrangement
phenomena caused by the acids are chiefly important. Owing to
the dependence of the rearrangement velocity upon the acid
concentration, concentrated acids are best suited for the pur-
pose. The nature of the acid is often decisive for the
rearrangement products.
Amidophenol.—On reducing nitrobenzene in concentrated
sulphuric acid, Noyes and Clement1 obtained p-amido-
phenolsulphonic acid. Gattermann and Koppert,2 by using
nitrobenzenesulphonic acid in tolerably concentrated sul-
phuric acid, got p-amidophenol sulphate. Gattermann,3 on
varying the experimental conditions, also employing con-
centrated sulphuric acid, obtained para-amidophenol directly
from nitrobenzene. He explains the latter's formation by
assuming the intermediate production of phenylhyclroxyl-
amine, which in further reduction rearranges itself into the
end-product.
C6H5N02 4- 2H2 = C6H6NHOH -1- H20,
C6H6NH(OH) =NH2C6H4OH.
Some o-amidophenol is formed besides the p-compound.
Chloraniline.—Lob 4 has found that p- arid o-chloraniline
•are obtained by the electrolytic reduction of nitrobenzene
suspended in fuming hydrochloric acid, nitrobenzene dissolved
in alcoholic hydrochloric acid, and nitrobenzene dissolved in
mixtures of hydrochloric and acetic acids. With hydrobromic
acid the corresponding bromanilines are formed.
1
*Chem. Ztg. 17, 210 (1893).
8
Ber. d. d&itsch. chem. Gesellsch. 26, 1844 (1893).
4
Ztschr. f. Elektrochemie 8, 46 (1896); Ber. d. deutsch. chem. Gesellsch.
29, 1894 (1896).
The reaction takes place as shown in the following equations:
2. CeHsNHOH + HCl-CeHsNHCl + HaO.

3. C6H5NHC1=03C1C6H4NH2.
The phenylchloramine formed by the action of hydro-

chloric acid on phenylhydroxylamine changes by molecular
rearrangement into o- and p-chloraniline.
Condensation Products with Aldehydes. — Gattermann1 has
obtained direct proof of the intermediate formation of phenyl-
hydroxylamine in the preparation of amidophenol by adding
benzaldehyde to the solution at the beginning of the elec-
trolysis. He was thus able to isolate a condensation product
of phenylhydroxylamine with benzaldehyde. In this way he
obtained from nitrobenzene benzyUdene-phenylhydroxylamine,
The presence of formaldehyde in the eleptrolytic reduction

of nitre-compounds produces an effect entirely different
from that caused by the addition of benzaldehyde. The
phenomena occurring in this case have been thoroughly
investigated by Lob.2
The fundamental object of his researches differs from
that of Gattermann, in that 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 moment of their formation, com-
bine with formaldehyde, producing condensation compounds
which do not undergo further decomposition. By regulat-
ing the potential or density of the current the reaction can at
1
Ber. d. deutsch. chem. Gesellsch. 29,. 3040 (1896).
2
158 ELECTROCHEMISTRY OF ORGANIC COMPOt*
will be checked at a perfectly definite phase ol

tion.
In the electrolysis of nitrobenzene by this in
were formed:
1. p-Anhydrohydroxylaminebenzyl alcohol,
CH3OH
which may also be directly prepared by the ac*

maldehyde on phenylhydroxylamine.
2. Methylenedi-p-anhydroamidobenzyl alcohol,
a reaction product of formaldehyde and aniline.

3. Anhydro-p-amidobenzyl alcohol,1
r /CH2-,
C6H4< | JL
L \NH
which can be likewise obtained by the action of fn

upon aniline.
Azoxybenzene.—This substance was recognized
ago in the investigations of Elbs;2 Haussermann,3 IS
as one of the reduction products occurring both
and alkaline electrolytic reduction of nltrohc*rix
berger and Haber then explained its format ion I
densation of phenylhydroxylamine and nitroHobmz
by electrolyzing nitrobenzene suspended in clilii
alkaline or alkaline-salt solutions at unattaekabl
1
Ber. d. deutsch chem. Gesellsch. 81, 2037 (1898).
2
Chem. Ztg. 17,209 (1893).
3
Ibid., 129 (1893).
*D. R. P; No. 79731 (1894).
8
Ztschr. f. Elektrochemie 7, 335 (1900); Ztschr. f. phy»v C
(1900).
(platinum, nickel, mercury), succeeded in finding a method

which gives a good material- and current-yield of azoxyben-
zene almost free from other reduction products. In this
case the unattackable cathode plays a leading part, aside
from the use of aqueous electrolytes. The choice of attack-
able cathodes modifies the process very considerably, the
nature of the metal producing individual effects.
Azobenzene. — Alcoholic-alkaline solutions act differently
from aqueous-alkaline electrolytes. Even if unattackable
electrodes are employed with the former, the process can be
regulated so as to give very good yields of azobenzene. This
was demonstrated by Elbs and Kopp.1 Two concurrent
processes determine presumably the azobenzene formation,
firstly, the splitting off of water from two molecules of phenyl-
hydroxylamine produced by the influence of the alcoholic-
alkaline solution; secondly, the reaction of hydrazobenzene
(resulting from the azoxyberizene formed secondarily) with
unchanged nitrobenzene or nitrosobenzene. That the latter
reaction occurs is shown by the fact that, if the electrolysis
is prematurely interrupted, azoxyberizene and azobenzene and
hydrazobenzene are always present. When alcoholic electrolytes
were employed It proved advantageous to substitute for the
free alkali sodium acetate which, on account of its easy solubility
in alcohol, its good conductivity and trifling action on the
diaphragm, possesses considerable advantages over sodium
hydroxide. These processes are not technically valuable on
account of the employment of alcohol.
Bayer & Co.2 seek to avoid this latter inconvenience by
reducing nitrobenzene, suspended in aqueous alkaline or alkali-
salt solutions, in the presence of such metallic cathodes, or the
addition of such metallic salts, whose oxides are soluble in
caustic alkali,—for instance lead, zinc, tin, or their salts. The
yields of azobenzene obtained by this method are said to be
1
Ztschr. f. Elektrochemie 5, 108 (1898); D. R. P. No. 100233, 100234
(1898).
2
D. R. P. No. 121899 and 121900 (1899).
I
«\ 'if II '
; i t l f»N «I *H '
»«fl
Ct}
JUJ
ffJf
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'• f il
JJut
•"iwi ill
fii *n|| tii »iii*i j /fM«j««if jit nni|iui

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III Hi41,
,c i 4
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theory azobenzene is a condensation product of hydrazobenzene

and nitre- or nitrosobenzene.
Benzidine.—That nitrobenzene; by electrolytical reduction
in acid solution, can directly yield benzidine, was first proved by
Hiiussermann,1 who used sulphuric acid. Lob 2 later proved the
same to be true for hydrochloric-, acetic-, and formic-acid
electrolytes. However, several reactions predominate in this
direct acid reduction, which prevent the carrying out of the
reaction up to hydrazobenzene, or the formation of benzidine.
Phcnylhydroxylamine may particularly be mentioned in this
connection. In alcoholic-acid solution it is partly rearranged
to amidophenol or its ethers, and partly reduced to aniline.
Azoxybenzene, in acid solution, is the starting-point in the
benzidine formation; however, in this case, the combining
velocity of nitrosobenzene and phenylhydroxylamine is not very
great, so that the latter is to a very considerable extent subject
to the more rapidly acting influence of the acid.
Besides azoxybenzene, azobenzene also gives hydrazo-
benzene, as already mentioned, e.g. in acid solution benzidine
results. Azobenzene, however, is formed only in very small
quantity.
Lob, 3 convinced of the futility of thus being able to obtain
a good yield of benzidine by a direct reduction of nitrobenzene
in acid solution, sought to carry out the benzidine process
by a careful realization of the conditions theoretically required—
primary preparation of azoxy- or azobenzene in the best quan-
titative yields, i.e. in electrolytes, containing alkali or alkali-
salt, then reducing thfese products in acid solution. Two
processes / thus resulted. In the first one the electrolytic
reduction was carried out to azobenzene in alcoholic-alkaline
solution, then the cathode solution was acidified with sulphuric
acid, and the further reduction and molecular rearrangement
combined in one operation. The second process, which was
* Chem. 2Jtg. 77, 108 (1893).
2
Ztschr. f. Elektrochemie S, 471 (1897); Ber. d. deutsch. chem. Gesellsch.
29, 1894 (1896).
8
£tschr. 1 Elektrochemie 7, 320, 333, 597 (1900-1901).
i
I
162 KLK(THorrU.MIS*Il;\ * * l « » i i ( i \ M « M
workcnl out aft<T t i n - di-fowTy of t j , r i'«tM ; ^ p , ^ , ! - r tl

of H7,oxyb<*nwn«*, a\oi»l. ill'* ui»j*'r'»*>i i nj ,o * •' i/ !. , » » . i
takes phirT priiaaril\ in ; n | - i ' « m ; liini *i tt/jîti
at.- unatlafkabli* ralliuil'' vail ;i/*- t/ i^ i, « o« • »• .!• If
apiw*ar.s tliat u/«o\\lrt'ii/« !*»% in ( i , j h in»f , , ; • * '? i
an <*xfn'i!ic*h' poor <i«'p«»l'inx» r, l*ui f ! i " f ' ! »
fakes pla<*<* v»*ry nvulil;- i f i a l i S ' U " » 5 i '
with flu* addition of a t i i l i i n i r *j!?"»''. »' ?!
of hyilraxolrf'iww U-ti»if it i« • n. </" v » t/

Aniline* HP * nartinn vJ i*'h f » J « ! K
I.M»n7/n.iin<( pr«*paralion " i « - * < l H nl : - ! • ^n
preparation of anilitM* I * * r< ^r'iui i 1 ;.r
eliilly fli<* ns'tt'tiu'ij** * of f l i i ph< i i! 1. In
fuitliH' r*iiij *'tinv fo ^ " 1^ 1

of iirlt * m;i l»!NUir iii ;,hn ,t
i r< *'^ *•!
r
i alilc* ctiif!if«|c' iu«i;il'., Uli fii f « » < ^ r j «, M^f « ,
flu* c'atlii«!«* tii*l;il in th«* *l<'Mni*;»u* J*' / - A
I , s,?
Lcib lut<»r um*!»- fli^ MU »* 4* # i • » i j -
tll<» ri*plMff*!!I«1it of f l i « p', "I ''il/, ^ i l j
i««^ *» .1
«icli*rably favi»n«l t l i » IOHU Mo;* »f ' il n '!,« •
III tt(*i<l HotuHon* I ' l l * ! * !i« nMUL1'! *
Hiiini* mifTi^Hliii IT* ill tii«ii ,11 i S i r t » » 4
with the* iiiiflitioii of ;» /in»* f*lf |{,« , i
{ircivi*«l in jipninii n * u«li< 4 t l *
iiiil in ûllrtii*' ;** i *l j »!**u
plaiinuni c§athcwli»,
Loh,1 inti<k|M»f>fi(*ntiy nf fh*-^* fflrii\;jif
an iiliiic^f qiiniifitiitivi* yi«'l«I «4' !*;«i
in h«lr<rlil«*t5«
f W»
8, 172 ^M«,
4
HIM!, 4»4S»
THE ELECTROLYSIS OF AROMATIC-COMPOUNDS. 163
later Elbs and Silberjnann l also obtained 90 per cent of the

theoretical yield of aniline with the aid of a lead cathode.
We are indebted to C. F. Boehringer & Sohne2 for the
comprehensive exploitation of the influence of cathode material
in the preparation of aniline. They have patented the results
of their experiments. The importance of the decisive condi-
tions of the experiments, as in those of Elbs and Silbermann
and of Lob, lies in the increase of the reduction velocity of
phcnylhydroxylaminc to aniline, so that competing rearrange-
ment and condensation reactions are given no time to occur.
Almost quantitative yields of aniline are obtained. The nature
of the process consists in reducing the nitrobenzene in acid
solution, or suspension, by means of indifferent electrodes and
with the addition of a tin, copper, iron, chromium, lead, or
mercury salt, or the corresponding metal in a finely divided state.
The metal employed, or the corresponding degree of quanti-
valence of the metal ion, is regenerated by the current, depend-
ing upon the greater or less electrolytic ismotic pressure of the
metal. Cathodes of tin can also be employed instead of the tin salt.
It may be mentioned incidentally, that according to in-
vestigations by Holier3 a strong odor of phenylisocyanide,
CeHsN —C, occurs in the electrolysis of nitrobenzene in alco-
holic-alkaline solution and without a diaphragm. But a sepa-
ration of the carbylairiine could not be made. Homologues
of nitrobenzene, when electrolyzed under analogous condi-
tions, also yield isonitrile.
c. Substitution Products of Nitrobenzene.
I. General Laws governing Substitution.
The reduction scheme sketched by Haber for the reduction
of nitrobenzene also holds true for the substitution products of
nitrobenzene in so far as the formation of their reduction
phases can be coordinated to the same reduction, condensation,
or molecular rearrangement processes. But the decisive influ-
1
* D. R. P. No. 116942 (1899); 117007 (1900).
* Ztschr. f. Elektrochemie 5, 463 (1898).
11)4 KLWTHOCHKMISTHV < » F uK<;.\Nir f 'iiMH HAJ i-
once of (he subsf itucnts manifests it-elf in varioir. H ; I V I % f f }

the first place, the experimental condition.- deirnuined f<*r t i n *
preparation of certain reduction stag's of ni!ro|n-n/»'ij»- t i n nut
obtain for It s derivatives, at fi*ast nnly in a l i i i i i f ^ - u imnn'-r.
The position and nature of the HtlHif tsnif "-• a l - » < > n » M i hindir
the preparation of single phases, In nihi-r \\nriix; ib* r»'ar-
ranêiitenl take plan* is fundanientallv inJlnen<'''d.

v
Nevertheless . t»ine reacti<ije- are known which pn*"=**«>.M ;i
v 1
certitiii general applicability. *I*hi * i' " tru«* »*s îiiff^rujiiiiir;-
reduction in concentrated sulphuric acid, whii'li iiivr"- ino>-!ly
nniidoj)h(*nols, if the ortho- or para-pt>siti«iu i-, unnci*upiiM|,
4
Only [i-nilrotoliieiif* and the nitroaldehydeH form «*\rt jf!i«.ii$'%
whicli will lie dixMjsse*!.
Tlie redticlion in alkaline olution liUny » J. • d . ^ ? j » < * i
alwayn to n7*o« and axoxs-lwitlie1 . i » i hydi i/« ho-li* Tl«* L i n -
here prcdrjiai natinjir have fii ifflv bo-n iir*^ ti^d* ! h\ | |h l
mid his pupil^. The exception 1 ' f f » tit 1 * fu!«, tb*» **i*pan« j>r«* of
expliiiited b\ Klb-'. P-,\itn»i*ilini4 . «I»riroh7»>(r! MI* 1» > t j > » * UIIP*

conditions which i r iv#* in iliaii idnhMi/w ir*«?y iii ntH-iM^jj**,
yieldn only p-'pliiiiUiiiediufiiiiif*, Thi - pltMM/»4**'t*oii i ba »«|
on tlic* fact thiit p-iiilniiiiliii*1 !t;i*Iiiy yi»*M 'jtii^Mi e * l i * t n ttn«^t
but in-riitniiiiiiiii* dw»H nut, rh*j fK<»
-*
which on further n»dii*'tii«i niti yifM r»nlv ,i *li:inmi>*'
,.xi!<m ' XH
i. < VHI ' »ivi» - IM ».
\H/ XII
,
1L (%ff^" U!j t(VH
Ml
Or this ri»«rriiiigf*riii*iit omirMAlrfwl} isi tin- tiifn^f»»|»h;^t%
to the :
NO
I , f,
XII
7, 13.4, t II
Since the tendency to form quinone derivatives is lacking

in m-nitraniline, the nitroso- and hydroxylamine phase can
unite normally to the. azo-body.
For the same reason perhaps the exclusive formation of
o- arid p-amidophenol occurs:
/NO JSTOE
CTgJuL4<
T / v r* TT &
—> V^gllÂ
/NHOH .NOH
or C6H4<; ^C 6 H 4 ^ +H 2 0.
\OH %Q
These quinone derivatives, by further reduction, can pro-
duce only amidophenols. If the quinone formation is prevented
from taking place, for instance by esterifying the hydroxyl-
group, the normal reaction to azoxy-bodies occurs, o- and p-
Nitroanisol pass smoothly into azoxy- or azo-derivatives. The
acylizing of the arnido-group in the case of o- and p-nitroamines
hinders likewise the quinone, and, therewith the arnine, forma-
tion. The azoxy-body is smoothly formed, thus:
'NO H O HN \ r
XÔCeHs '
CoHs
C6H5CCK
But the alkylization does not prevent the formation of
quinone and therefore the reduction to the amido-phase:
/NO
C6H4<
\NHC6H5
/NHOH
or C 8 H< -^C6H4C +H2O.
X
\NHC6 H5 NC6H5
Elbs sums up in the following manner the rules which apply
to the electrochemical reduction of aromatic mononitro-bodies
in alkaline solution. Hereby it must be taken into considera-
tion that the primarily formed azoxy-body, under the condi-
tions chosen by Elbs, leads to the azo-body.
166 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS. '
1. Nitrobenzene and its homologues give azo-bodies; amines

do not occur, or only in traces.
2. Halogenized nitrobenzenes and their homologues yield
azo-compounds; difficulties occasionally occurring are caused
by the alkaline cathode fluid attacking the halogen made mobile
by the nitro-group, or inversely the nitro-group made mobile by
several halogen atoms.
3. Mtrobenzene-m-sulphonic acid and its homologues give
azo-bodies.
4. Mtrobenzenecarboxylic acids yield azo-compounds, but
only the o-acids behave differently.1
5. m- and p-Nitroacid-nitriles yield azo-bodies, with or with-
out a partial saponification, depending upon the conditions of
the experiment.
6. m-Nitraniline and its homologues give azo-bodies, but
o-and p-nitraniline and its homologues, on the contrary, give
diamines.
The same rule obtains for the secondary and tertiary amines
derived from the three nitranilines.
7. Acylized nitranilines (acidnitroamides) and their homo-
logues give azo-bodies, no matter which position the nitro-
group occupies in regard to the acylized amido-group. The
cathode fluid must be kept approximately neutral during
reduction, otherwise the acid amides are saponified if the
solution becomes considerably alkaline.
8. o- and p-Nitrophenols give amidophenols.
9. Nitrophenol ethers give azo-bodies, no matter what
position the nitro-group occupies.
These rules do not hold true for dinitro-bodies.
The experiences gained in the electrolysis of nitrobenzene
concerning the influences of the cathode material have also
obtained in great measure, with the substituted nitrohydro-
carbons. The general result can be summed up in the state-
ment that at unattackable cathodes, such as platinum, nickel,
1
Lob, Ztschr. f. Elektrochemie 2, 532 (1896).
T
and mercury, in aqueous-alkaline solution azoxy-bodies1 are

produced, and at attackable cathodes, such as lead or copper,
azo-, hydrazo-,2 and even amido-compounds are formed. The
latter are obtained by the method of C. F. Bohringer & Sohne,3
using a copper cathode, or an unattackable cathode with
addition of copper powder. o-Toluidine, m-phenylenediamine
from m-nitraniline, and a-naphthylamine, in addition to ani-
line, were prepared in good yields by this method.
In alcoholic solution this difference does not occur so dis-
tinctly; it is also easy to reduce to the hydrazo-phase at
unattackable electrodes.
The influence of the cathode' metal is much more mani-
fest when acid electrolytes are employed than in alkaline
reduction. In alkaline solution at copper electrodes, if we
except the last-mentioned process, the rapidly occurring con-
densation of the first reduction phases—of the nitroso- and
hydroxylamine body—always leads immediately to the azoxy-
body and makes this appear to be the typical product of the
alkaline reduction, which can in turn be further reduced. In
acid solution this condensation takes place so slowly that
the molecular rearrangement of the hydroxylamine and its
further reduction to amine has time to take place alongside
the formation of the azoxy-bocly and the reduction of the
latter to the hydrozo-compound or benzidine.4
The increased reactivity of the whole molecule or single
groups, which is often associated with the entrance of nitro-
groups, is also apparent in the capability of some nitro-bodies to
be relatively easily oxidized. The little that is known is ap-
pended to the description of the behavior of the individual
members. The characteristic features of the oxidation processes
in question have been explained in the first chapter (p. 27
et seq.)-
1
2
D. R. P. No. 121899 and 121900 (1899).
8
D. R. P. No. 130742 (1901).
4
Cf. Haussermann, Chem. Ztg. 17, 209 (1893).
ftiffHlt
*X
K:r '? Wi
IMMI
f fl f t tf
''fi ' l '
•'j:r»Hi; i-îr, *
.) ni i^r/AjojiJ^p jt ^
|t: |V7M*K{(M)!U'0 jo (*|ii»t.i J'»
f lf * fllfHH Jl!|fl f 1I«* ji,f'/I|i|\0 |f
t? til f?Mi|fi}tjJp?
40 S'«»j«tf||»U fill '*J'V|"4J<><*1«» |»I«l!»'^l!,Iti|l[.}i)J|l,\ij 1! Ill .

|f
«PS1 |i.»|4ÂftO.) *M{ U1M tj.>lt{.tt * / * | ^ > * j JO hS.MO,l«lj iMMU
l
*AJt Ji!i*».l ,ilj| fill ji,j!!!.Jil| Î .M.tlj | f tlOlXllpHlsilS h'IlO«mI)1
ni |MXA|o4),i.^> j{ '.>iM*/u.x|!!'/fU[»A't{ jiuir -o'/u jo ttoi}iuut

40J :<|tMI!!ti p.ittf)!|fMtri-»».\OI{t! 4it|t jo KhMJUJli «H( I Ml U
.U J.i!||jf!| till 'jllIU Mftif JtlJliS .)![o!{O.I|IN<MI![!?>{p»' fU |I.MM|KU<I

x»J«,*<jn'j puv </d(Io\j
%ip,\ij»ip|tr/si.H| j
OJ
it}
ns t
THI*; KLKCTUULYSIS oF AKoMATK' COMPOUNDS. 10!)
FJectrolyxed in alcoholic-alkaline solution, according to

thi* directions of Klbs, in-ascot oluenc is almost quantitatively
produced; the further current' action gives ni-hydniHololuene
(Holtde1).
hub and Schwitt- electrolysed jn-nitro(oluene in alkaline-
aqueous susjrt'iision. employing various cathode* metals in
order to determine their influence. The other conditions of
the experiments were the* same. w-Axoxytoluene, which is to*
a small extent converted info hydrascofoluene, and m-toluidine
an* produced. The yields vary, depending upon the nat.ure of
the eathod**: the reduction was weakest at nickel cathodes, i.e.,
il hardly passed beyond flu* axoxy-pha.se; aJ. xinc, cop|»crt aiul
cop)XT in the presence « if <-(»p|HT powder, I lie yield of nmlne
incn*ases in the given series of the metals, while that of
ascoxytoiuene decreases. The following table shows these rela-
tions. Five grams m-nitrotoiucne gave:
Nirki-i.
Kiitr, . 2. V2
I .lf i
I . 3H II 1 I. f»K
Pif*rrc»ii»:i by oxi<ii?Jtig electrolytU'ully m-nitrotoliu*ne under

the* ronditioriH 4*lvmm for flu* o-iitlrotci!«i»nef obtained about
20 JKT conf. ni-nitrolx*fixal(lf*hyfl(*.
p-NItrot01tt«Be-•••—• In «lilutf» milpliurlcHicid Holutiou, HUUHHIT-
nutnn 4 cilitniiied {>tninifliiii* IIH th« chief product; Ciutfer-
iiiitiiti Kop{nTt,* by refi iici ng in concentrated Huijihuri c
p. f, K!f*ltr*r!ti'r«iÎ f 322
§
Ili*f» 4 flout !i4 20, 2S1CI CmilS); I). It 1», No.
fcf tf *| ** J
f.iiififl S **X *«! 'If '<Ie
'fJSfj 'fl|S *|^|p«*»f) im»jj tf«jte|ts4ft p M;*tf |
r
1Lf
no ^
^fJÎ {11.111
jMlli *ttl|iff!jfi| <| Jil faUjWlJll li«l||t:HU.t|MtCM If JHW OHIp

?
1II|H|JA1| I tfltlfMf jififflJlif ,UU U»I{| \i|iil|«.|jiJt:iII4Uj JO «Mlt*JH*Xld
PtJ|«\ff -iK
MtJ II! %
ll f t l t
If 111 OJ
jo
JO *llfll|lfli'lj!j«l *UtUI *p1Mj M»xMoi> 'ill)
•f, innnu
of p,)p[H! SI
|.U1J
*|iniLioj .if|| ShiiAi'n pin?
SI
OZl
T1IK KLKCTHOLYSIS OF AIJOMATK? C M'NUS. 171
The excess of formaldehyde present in the Iiqui<l aâin

acts on the tnluidine, so that ;i mixture of dimet hylioluidine
and trintej hylehetritoluidine results.
1 2
In alcoholic-alkaline Dilution Klbs, Klbs and Knpp, a.nd
:|
Lob obtained p-azof oluenc. If the elect rolvsis is prema-
turely interrupted, the electrolyte contains large quantities
of p-a/o\ytolu«'jjc; on prolonged electrolysis p-hydra/*(»t<)Itu»n<*
is quantitatively prod wed, areording to the prongs of Mlhs.
Ldli and Srhinitf J invest iâ.fed f!ie, behavior of p-nitro-
foliii'ne in alkaline-aqitfotis suspen.sior» at di(Ter<»nt. <'a.thodes.
The result is similar to that obtained in (lie ra.se of m»ni(n>
toluene, hut f! i « ' azoxy-body was always coiitaiiiinated with
,«onie a/*(M'ciiiipf*und. Five grains p-nif.rofoluenc*
following:
Vi»*M in
Tnlui/liw,
2, IIIl o,c»7
Zinc*, ,, C). HH
< V f|»f !!T, 3UO
nfi*I !, 70
If the I'jirreiit yieidn ribfriiiied under Miiiiilitr (jonditioiiH from

in- and p»iiifrot«iliiei«f» lire fompiired with one* another, it is
found thai i l r fêoinpoiiiid H iiion* ca.siiy reduetble than the
m-liod, Tin* ifiiitrnee nf the po/itioii of lite methyl group
thus in
mui both in the flieiniral teHitlt and tho reHiHtanai!
f
ri*fliii ing ag^fifa
/ by eli HI ruly tlrully imldhm^ f)-nitrotoltic*rM» in it
of rciin»nfr:«feii iiN*fr and «i!phutic iwuln at a large*
platinum HIKII!I % rditnintnl {îiilroliitii^yl alcohol,— ûrnait
yield
Md 41) |ii*r cc*nt,
/,!«. 17, am MH»3); /44rbr f, F4

f Kl<4frirlii*iiii«4 I If)
4
ItrnL 10, 7M flfK
1
liiwi g» r*^2
ri
ii:.
If the electrolysis is carried out in 80% sulphuric acid,
"both p-nitrobenzaldehycle and the alcohol are obtained (Lab-
hardt and Zschoche x).
C. F. Boehringer &*S6hne 2 add 0.1 part by weight per litre
of manganese sulphate to the anode electrolyte,—a mixture of
sulphuric and acetic acids; —and obtain smoothly p-nitrobenzoic
acid at a lead-peroxide anode.
NlTROXYLENES.
Nitro-p-xylene, reduced in concentrated sulphuric acid,

gives the corresponding amidoxylenol (Gattermann and Heider3 ):
CH8 (1)
C6H2; 'NH2 (2)
CHa (4)
OH (5)
Gattermann, 4 by adding benzaldehyde during the reduction,
obtained the benzylidene-derivative
(CH3)2C6H3N -CECeEg.
B \0/
p-Nitro-o-xylene was reduced by Elbs and Kopp6 in alco-
holic alkaline solution with addition of sodium acetate. They
obtained good yields of azoxy-, azo- and hydrazoxylene.
p-Mtro-m-xylene, when treated similarly gives analogous
products.6
Elbs and his pupils6 obtained in the same manner the
corresponding azoxy-, azo- and hydrazo-bodies from o-nitro-
benzylqniUne, p-nitrobenzylaniline, nitrotolylaminophenylmeth-
ane, NH2CeH4CH2 • C6H3CHsN02, and m-nitroleucomala-
chite green [(CEaJaNCGE^CE-06^^62; but the last-men-
tioned substance was not reduced to the azo-phase.
1
2
D. R. P. No. 117129 (1900).
8
Ber. d. deutsch. chem. Gesellsch. 27,1930 (1894).
4
Ibid. 29, 3040 (1896).
5
8
Ibid. 7, 136 (1900).
m-Dinitrobenzene, on reduction in concentrated sulphuric

acid, is converted into o-p-diamidophenol (Gattermann and
Abresch 1).
o-p-Dinitrotoluene (2.4) is analogously reduced to 2.4.5-
diamidocresoL Sachs and Kempf2 oxidized this substance
electrolytically in sulphuric acid solution at a lead anode and
obtained a medium yield dinitrobenzoic acid.
2 - 4- 6-Trinitrotoluene gives analogously trinitrobenzoic acid.
p-Dinitrostilbene. While carrying out some experiments on
the dye "'sun yellow/7 which is obtained by warming p-nitro-
toluenesulphonic acid with sodium hydroxide, Elbs and Kre-
mann3 worked on the etectrochemical reduction of several
stilbene derivatives.
They obtained the following results: p-Dinitrostilbene, re-
duced in alkaline solution, gives p-azoxystilbene; in hydro-
chloric-acid solution with addition of stannous chloride (method
of C. F. Boehringer & Sohne), p-diaminostilbene.
o-Mtrodiphenyl and p-nitrodiphenyl in alkaline electrolytes
give the azoxy-derivativos (Elbs); p-nitrodiphenyl also gives
inconsiderable quantities of p-amidodiphenyl, while in alcoholic-
sulphuric acid at platinum and lead cathodes it is easily reduced
to p-amidodiphenyl (Fichtc and Sulzberger 4).
2.2-Dinitrodiphenyl was reduced by Wohlfahrt;5 in accord-
ance with Elb's process, and gave a very good yield of phen-
azone, while in hydrochloric-acid electrolyte with the addi-
tion of stannous chloride hydrophenazone hydrochloride was
formed.
/N«N-
The method of Wohlfahrt has been extended by Ullniann

and Dieterle 6 to several o-dinitrodiphenyl derivatives. The
1
2
Ibid. 35, 2712 (1902).
8
4
6
Journ. f. prakt. Chem. [2] 65, 295 (1902).
8
K! *>
S lisi 2 £r*
f?
g a1« ?g.l
^ §! -
r s. *
i1
*
bit & *"•?"* £T* C*r *T*
C^ o s s» — os i* 3 s-3
C 35
§5tr tr*>
S
V
3
3 •< ^, f*"* JL «"*** S* »•»•* r §. g
. S s: 5 s - • 2 3*§ 4
x S 2 S H" 4
is ». c 2.
1
•* -^. Q
~ —^4-
~ ^*3cr
Q*
N «
t~r:r x 55 B' S S
c ^
i
g|§l
O «- »5
X 5 i
& x x 5r- T. •?».
'V V
? s ?r •* a 9 ~* M,
I Ili-frl S
n. »o
2 * ~
8 2 T ^ * ^* ^. ^^ "
it
I ! -!:! «M *" t
Iff Ni
® *^ ** •» SJ CT.
va
a 55 ifLHa <"
J* 2 ^ g ^* ^*
X
£f x £. a
ST 1*
I :: I I 5 S 3 % £ I- I s I |
«• f ^ **5
....
1s 2- « ^ r
| g """ ' ""
ill"! ^'l-s-lI- f I
H* ^ r SL
__,. *^ ^_ ***
^* s SS. ***
« a
Us-
! II
r
(2,5)nitrobenzene (by-products: p-dichloraniline and chlor-

aminophenol (ClOHCeHsNBW, o-bromnitrobenzene, m-brom-
5 2 1
nitrobenzene, p-bromnitrobenzene, m-iodonitrobenzene, p-iodoni-
trobenzene, o-chlor-m-nitrotoluene (by-products: o-chlor-m-to-
luidine), o-chlor-p-nitrotoluene, p-chlor-o-nitrotoluene, p-chlor-
m-nitrotoluene (by-products: o-chlor-m-toluidine and o-amino-
m-cresol).
Gattermann's reaction also proceeds smoothly with the
halogen derivatives, if the para-position to the nitro-group
is not occupied.
p-Chlornitrobenzene, on account of the mobility of its chlo-
rine atom, is converted in concentrated sulphuric acid into
p-amidopheriol (Noyes and Dorrance 1).
m-Bromnitrobenzene gave a good yield of brornamidophenol
(Gattermann and Heider2).
p-Brom-o-nitrotoIuene gives the bromamidocresol.
CD
NH2
(2)
(4)'
^Br (5)
p-Brom-m-nitrotoluene \OH yields analogously the
bromamidocresol.
/CHa (1)
r H/ > N H2 (3)
Ce H
<Br (4)'
X
OH (6)
IV. Nitrophenols.
o-NItrophenol, reduced electrolytically, gives a good yield
of o-ainidophenol both in alkaline-aqueous solution at plati-
num cathodes (Lob3) and in alcoholic potassium-hydroxide
solution at lead or mercury cathodes (Elbs 4).
o~Nitroanisol, electrolyzed under the same conditions as
1
2
Ibid. 27,1931 (1894).
8
* Jouna. f. prakt. Chemie. 43, 39 (1891).
*"*•* t~*" f^
I 1 I ^ 5. S I- ** 5
; ^ o a ^ g^ := 9 :
*- ts ^ ^ ^ ^ H. O^C r&*^^"
S E 5! r. ^ ^ -"*-*4*~*f?^^
r a, a. s. ^ 5 O *4
* -*
§, J
Till'; KLWTKOLY.SIS OF AROMATIC COMPOUNDS. 177
Nrriioi'itKNYi, KTHKHH,
Heveral representatives of this class of compounds wore

investigated as to their behavior in alkaline reduction (llaus-
sermarm and Schmidt l ) . These* Investigators confirmed the
rules which Klb established for nitrophenyl ethers.
o-Nitrophenyl ether, p-Nitrophenyl ether are smoothly
converted intu axoxyphenyl ethers.
p-Nitrophenyl-p-tolyl ether gives similarly the p-uHoxy-
j»hi*nyl"p-t ol\ 1 ft her.
Hydroxyquinone-p-nitrodiphenyl ether yields p~a,%oxydiphenyl
filler,
p-An»iriophenyl p-tolyl eiher is smoothly formed from p-
nitrophenyl-p-tolyl ether in hydnrhloric-acid susp(»nsiou with a
till cutlioiir,
V. Nitraniiines.
o-NitraniIinef when electrolysed in alkaline solution (Klhs
and Holide 2i yieldn sniootlily o-phenyl<iiH*diamin<^ wltilc4 the
iiiti'nn«*<liat«*ly refiirriug nitroso- or hydroxyl'imine-phasc*^
similar to tlm^* in the jKsrries, readily rearrange* th(»jtus(;lvc»H
into ijiiiiioin* *ii*rivativeH,
m-Kilraniilne lK*lmvi*H dtflwfttly, Tliis Hiibstttriw, by c»l<»c-
trol\>i>* in mi alkaline elertrolytr, given a good yield of m-ciiam-
inoii/tiib'iixeiif* i'KlbM ami Kopp,:i and Lclh "J)f also u little uôxy-
eompfiiitpl rind true* M of in-plienvlenedhmine. TIu* rc*dtjciion
can al.-o Hi* <*;»rriet| of it to the hvinixo-IiaHi*, jrn-Nitranilinc?
Koh<le n Jri^ tnvesfigatnl the inlhienn* of methyl groupn in

flu* :tini«i^-|(roiip> in alkit lini* redt
7
or the }iviln»7,o»body. reduced it in
1
fii r ft ih'titwh. rlwtti. Omillsc'Ii, 91, 87<W (IfKli),
?
7fîir f, Mi*ktroc*lt«tmi«f 7t H-l, 3-111 (HKK)).
1
ibiii, r». mi
* lliiil -!S
» |«JT «l d«'Ul'<rh rliHti, (^^*H»u*h S!B, IH-IO
f, EIi4f twfififilf* 7t 32Kf :i;iK (1IMKI)
f, iiiiic«iwt rinitii* 107 CtHltf).
ITS
iKMiSTUY nF oK'UAXjr i f 4! h if "\1»,
mitrafnl xulpliurir nn*l ami thus r-Miiv»T!i'.| if into i.^.j.

dhiiHliyl tlininiiinplirnol.
///-A itrtMHlitttt'tlif/ltrnlttiir ran ! » • ronvrrtrpl l , v f ; ;,j fsT.
murm's prnn-ss into iu-|»-.|ini'*Hjyl.|i:ijni.!..|.i»,-j,Ml • Ahiv-.-,.^ r
ut-Xilfuwvtltttliinrlinr MKIY»'S l i k » - fa- i t i f rîm^li* !;, M ]i n »..
If is convert p« I in alk;tliii(M-Jir!rolyti<y i n ? o« l i H i . - f ! , >] jn-Ii.-unH^
axolK'iixrni*, nr -Iiyilra/olM-n/i'iji*.
p-Nitranilinc, l»y rpiliiriiiijj i n r n i i r i . i , f r ; i f . - i l MjlphuH,. ;,ri,|.
yii'lii an ajiiiilfijilniin! |*.r;iiisr t i n - ji- j , . , î j i,,u J, i^rujli.-il'
yc's ami Domtiic'i^ mint,,! it ,„ j^Jirtiiiiilnl-M,/.-,^ 1 ,^
JH roil
Th<* Irliaviiir of fi-AHnHwnlww riunv inrMmtally Ir

?/
/ "'t IIW^ltiiilifMi hiTf. Tills *ui*taiin. |,y fli-rtriJv^H ill ari«| s-ululjr,,,
with a i i n mtlioii, % or mlttitifj!, of âiiiiMiiMri,l,,rii|i.. J, . , , f ,
of
in alkaliii- «*liitif * luili i f , fa.
foriiiaiinn fr«m, j j i . , . , . . Mf p
Nj |C(M,
I of ^
i, b uif |
|. t n
if
ordinnr
up uito (Imu'f hvlatfiififf* ;jml frrl|f ,,
nil
I!*ld fHt
£ '
^
THK ELECTROLYSIS OF AROMATIC COMPOUNDS. 179
Hinc, by elect rolytical reduction in concen-

trated sulphuric and, is converted into the important inter-
inedint f product of dycst tiff manufacture, p-aniido-ni-oxy-
diethylaaiiinc.
Col I/ -OH
1
gives the name compound.
lln* nitrotolwdinrs \vh«»n rc'du<$(»d (»l(»ctrolytically in acid

and alkaline solution lH»hav<i like* th<* nitranilincs. The position.
of th«( in*'thyl gr«mp inuHt, of rour.so, bc» bonu* in inind.
p~Nitro-o-toluidine is ônvortcul by Gutt(*nimnirs proccBS2
into <iiaiuid(»W'i-'ol:
r / Nil- (2)
NH a (2) i U 2 - * * ' H t a : - . N H s (4)
N
OH (f,).
lii this r:i*' tin* hyclroxyl group occupioH the o-position

in n*HjH'H. to i t i * 4 tirlginal nltro-grcntp,
hi ulkalitH* rffinrtloit {»4oliiyk*iic»cliniiilnf! is produced (Klbn).3
o-Nitro-p-toiuidina in Hiilpliuric*. acid solution givtw tlic
«ikfiiif!«>pri'*Hol IIH f.>-nitr<H)-toh.ad5m>, tho liydroxyl group
I IP * pnni-pfwition to tin* original nitro-group,
lip* I'lfftrical mlfidiwi in an alkaline* clootrolyto leads
to !i yii*!«l of o-toIuyh»nf*(Jiamino. If tho n*<luction is
carru**! out in nolutiort, m-nitro~p~toluidine arid rn*witro-
iiili>M% «j* |K « Hup|xifl(!(i, are eonvc»rted into assoxy-,
hyilra2ltH*oni|'HMHl«lH.
m-NItrodto«t%I-p-t01iiidift0 dimcithylbenzimidazolo
(Pinnow 4)
1
I), 1C F S%>, HHI2JJ
* Il*«r 4 dtfiitxrti cl»r»iiif CJiw*IlÎi» ill, IH/K) (IK03).
1
f, ElAtrfii*liiwili^ 7, 14JJ (HKKI).
* Jwurn. f, «, S« (WIl); Oftf 570 (1902).
CH3
N
N- C H
CH3
and dimethyltoluylenediamine. The reaction is carried out
in Lob's short-circuit cell (p. 50). An addition of graphite
powder accelerates the reaction, which probably is mainly
caused by the intermediately occurring nitroso-compound split-
ting off water, and thus yielding the diinethylbenzimidazole,
- -N
\N(CH3 )
N-CH
CH3
m-Nitrodimethyl-o-toluidine. — This substance, reduced in
alkaline electrolytes, gives tetramethyl-m-dituaido-p-azotoluene.
andtetramethyl-m-diarnido-p-hydrazotoluene.
VI. Nitro-derivatives of Biphenylamine and Amidotripheny 1m ethane.
p-Nitrodiphenylamine, by reduction in alcoholic-alkaline solu-
tion according to Elbs7 method, gives a good yidd of p-aniido-
diphenylamine (Rohde1); the primary production of quirione
probably prevents the formation of the azoxy-compound :
/N0 2 NHOH .NH
NH— C6H6 — C6H4
NH2
NHC6H5
Benzoyl-p-nitrodiphenylamine cannot yield a qiuaonedi-
1
Ztschr, f. Elektroehemie 7, 320 (1900).
THE KLKCrrUOLYHIS OF AROMATIC COMPOUNDS. LSI
imido-derivat ive. Benzoyl-p-axoxydiphonyliimino as well as

the azo-com pound an* hence produced if u saponification of
tin* beuxoyl group by the free alkali is prevented by neutralis-
ing with acetic acid, or if ammonium acetute is employed in
plan* of tin* sodium acetate in the cathode fluid.
p-Nitrodiamidotriphenylmethane, on electrolytic reduction
in concentrated sulphuric acid by a method of the (Josollsc.haft.
fin* ('hem. Industrie in Basel l can be. converted into p-rosan-
iliue. The method Is of geiu-ral applic-ubility : earbinoles
XIl-^j C f < J!,| - ( V M I i H - j result in the reduction of nilro-louc.o-
bodii's of the type N<)a - ClsILr- •CMIIlo. ( I n these • formula! it
<-it (i)
df*notes ar«»inulic^ nuliciils with primary, secondary, or tcrtia.i\y
amid<^r<>up.s ^r with hyilroxyl-groups.)
Thus is formed p-nitrc»-bitter-alm()n<l-oil-gr(utn from j)-nitro-
tHrttwrt It i/ltl i<itn!thttriitltt'tH/tttirih-(irw.
Besiiles f i n * mentioned products nerving an klw .starting-point,
I here w« »rr* also use* 1 it-tnlroilinundu-u-ditolyl-niclhunv, p-nitrotctra,-
ifu'tii/l-nH'tfiant') and other analogous compounds,
VIL Nitroaldehydes and Nitroketones.
Kaufnuutri and Hof2 nubjc'cttul m-
to reduction in alkaline-alcoholic solution and
thus ohtainiui nwMti\wiM<Av acid HH the principal product and
iiKixobenxyi alcohol an u secondary product. Hince the* yiehl
cif lilt* latter in extremely small when compared with that of the
Conner, the autliors USHUHWM! that there occurred a, further do-
Hfrurtive action of thi* alkali on the* prirruirtly form<*<! nitrobenssyl
tilriilio! in Hiicli a way that 8 moli»culeH of the alcohol give* 1
molepule jixoxyf^'fiicyl alcoiiol and »J molcrtileH a.S5oxyfx'nBoie
acliL Th**M* rfiibhtaiiceH are then convert c^cl l>y the* further
action of flu* rum*nt into the* eon*eHponding u'/o-compountl,
thiiH liiwtMnK fctii«deffilily the quantity ratio of the* primarily
formed aci<l in cumpiirwon with the* alcohol (nc*e p. 1X8). By
Ihw n*ncfion further Lob3 wan li'<l to a ByntheBtH of
!«fK*uitipmi!id«; tlic*w» will be mentioned later. If
1
1), l i , N«*. M«07 MHttt). C Vtn. XtK. 20, 242
r, f,
nitroaldehydes are reduced in sulphuric-acid solution, either

the free aldehydephenylhydroxylamines, or their condensation
products with unchanged nitroaldehycle, i.e., nitrobenzylidene-
aldehyde-phenylhydroxylamines, are formed, m- and p-Nitro-
benzaldehyde were investigated. The formation of these bodies
is expressed by the following equations:
XCHO XCHO
I. C6H4< + 2H2 = C6H4<
X
NHOH
II. C6H4< +OHCC6H4N02===H20

\ N H OH
/CHO
+C 6 H 4 < /0\
\N -- CHC 6 H 4 N0 2 .
On further reduction the process can again repeat itself, so
that similar higher molecular compounds are formed. The nitro-
benzylidenealdehydophenylhydroxylamines are produced from
the two mentioned aldehydes. If the p-nitrobenzaldehyde
is reduced beyond the compound mentioned in the equation,
the n-p-formylphenyl ether of p-azoxybenzaldoxirne is formed
(Always 1), as shown in the following equations:
•N02 /N0 2
on YJ / i /i"pr _ P TJ /
_ ZL/6-o-4sv ~r TtJci —• veJnL-iN.
X
\CHO CH - NC6H4CBIO,
\0/
/N0 2
II. 2C6H4<
X!H—NC6H4CHO+6H
\0/
/.
Ill
NC6H4CHO
C6H4
0 +3H20.
sl.\
NC6H4CHO
[/ /U^
X3H—:
1
Ber. d. deutsch. chern. GcseEsch. 29, 3037 (1896); 3ft, 23 (1903); Ztsehr
f. Elekfcrochemie 3, 373 (1897).
In the reduction of aromatic nitroketones in concentrated

sulphuric acid the normal reaction, i.e.7 the formation of p-
amidophenol derivatives, occurs (Gattermann *).
m-Mtroacetophenone gives amidooxyacetophenone.
m-Mtrobenzophenone and m-nitropheayl-p-tolylketone give
analogous bodies.
In alkaline-alcoholic solution Elbs and Wogrinz 2 obtained
m-azoxy- and m-azoacetophenone from m-nitroacetophenone.
The reduction to the hydrazophase was only partially successful.
By using a copper cathode with addition of copper sulphate,
in place of the previously employed nickel gauze cathode, a
good yield of m-aminoacetophenone is obtained in sulphuric-
acid solution; in alkaline solution a poor yield results.
m-Nitrobenzophenone, on electrolysis in alkaline solution at
ordinary temperature, gives an almost quantitative yield of
iH-azoxybenzophenone; when reduced at the boiling tempera-
ture, a good yield of m-azobcnzophenone is obtained, while
in sulphuric-acid solution m-aminobenzophenone readily results.
In the above processes the carbonyl group apparently does not
participate in the reduction of the nitroketones.
VIII. Nitrobenzenecarboxylic Acids.

Nitrobenzoic Acids.—The m~ and p-acids, by reduction in
alkaline solution, are smoothly and almost quantitatively
converted into the corresponding azo-acids, while the o-acid,
according to Lob's 3 researches, under similar conditions yields
o-azoxy- and o-hydrazobenzoic acid and complex blue decom-
position products. This deportment is of particular interest
because the o-acid also occupies an exclusive position in the
chemical reduction, and similar experiences seem to repeat
themselves with the nitrobenzenesulphonic acids (Gattermann 4).
In dilute sulphuric acid Hostmaim6 converted o-nitro-
1
2
8
Ibid. 2, 532 (1896).
* Ibid. 10,581 (1904).
5
Chem. Ztg. 17, 1099 (1893).
184 ELECTKOCIIKMISTHY OF ORGANIC 1 COMPOUNDS.
benzoic acid into o-azo-, hydraxoberixoic acid and untlirani

acid.
In concentrated sulphuric; acid oyxanthranilir arid,
/(.'<)( )H ( l j
Colls--. N!I2 (2),
\OH (5)
is produced by (he* method oif (latte'rrnann,1 from flu* * » r f i

acid; l-3-(kimidosalieylie acid Ls formed from the* metu-aei*
p-Nitrobenxoic acid, according to Clement and N<*y*'
gives the p-urnidophenolsulphonie acid when electndywl
very concentrated sulphuric acid.
The (h and m-nilrobMizoir, es-ter.v, on electrolysis, dep*
themselves like the free acids (('Jattcrnmrm). Tiie latter iiiv^
tigutor,8 by pn^puring the l)enzylicleni* fom|K»ijud hy the ii^t
method, proved the* intermediate formation of the Jiy
ainint* phane in the* reduction of the nt-ncid,
The experiments ofHcliall and Klein 4 concerning the
tion of riitrolx*nxene from o-nitrofK*nxoir* acM arc cjuife
ing. If a solution of soda in molten o-nitrol>cnzoi<*aci<i (ntrl«-*i
acid escapes during the* solution process, so (hat a snluti
of the sodium salt in the acid itself is obtained) is electrolys*
at 200° and at platinum electrodes, rc'lutively large* i}iiiinfi!
of nitrobenizc^ne are prexluceti; at the* name time* a gun in rvolv
at the* anode (OOja?). During an electre^lysis last>ing etnr*
two hours, with 0,8 to 1 amp., about 1 <*c, was obtained. T
experiments were .made with the expectation erf
reaction, among the aromatic acids similar to Koll»f»X Alt In »ti
in the case of the aliphatic adds a limit hydrex?arlK>n is
by the union of two unions with splitting off of
acid, for instance,
1
Ber. d, deutuch. chem. Oamjikch, '26, tit,
2
Am. Chem. Journ. 16, 511 (1894).
1
Her. d. dcutaeh. ehem. Ge«fll«Ii. 2t»
* Ztschr. f. Elektrocheraii! I, 266 (1898),
ihonitrocinnami
» *w ?s •^ £ J^% X 1C
5" 1-3 •< i •^3 •-
s:
-Nitrocinnamic
% ,
*w* X
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3* £i?i X 5
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1 86 ELKCT ROCIIEMIST ItY OF O KUAXir rn.MPc >rM> S.
The ethyl, ester leads to the same cuimutrin-.....either by

saponifioation of the nitro-esl^r befon* tin* r<Mlurtinn. '»r by
the splitting off of alcohol from the intermediately
aiiiiclooxyciiiiuauie ester.
a-Nitrophthalic Acid \vns ronverted by KIbs' l method into

azo- and and hydrafcophthalie a.eid; traei%s of a-aminoj»hlliaiir
acid were also produced.
/J-Nitrophthalic Acid behaves similarly.
Mtroisophthalic Acid.^ This substance, hy eleelrcilylii8 r«*-
(luctiou in concent nitcM,! sulphuric arid, according t « » f t a i t »*r-
maim,2 is converted into the* sulphate of oxyainidoL-ojilif lialir
acid. Nitroterephthatw acid gives an ainiilooxy I fTeplit halir aciil.
m-Nitrobenzonitrile can be1 converted hy Klhs* ;< rm*f ii'«!»

depcaiding upon tin* conditions of the exjtf'riwi'nt, cif hrr \viflinut
saponification into ni-a!5olx»n/.onitril«(t or with Haponificatinn into
in-a55oxyb(?nxaniid<* and in-a/*olH*nx:uni<lt(,
p-Nitrobenzonitrile gives juuilogously axo- and a/.oxyuiiriU*
or azo- and azoxybenza,mide.
IX. Nit robenzt'nesul phonic
Those1 sulphonic aeicis which huvc the* S(');iII.groiip In th«*
m-position to the* nitrogroup, havi* hr*rn p'trtictiiarh for. » • -
tigated. Under tli<k conditions choM*n In Iilh^« \\n*\ \ i « ' J < i
universally azo- aiul Iiydni7,o-hndif^t llin^ nitruli* n,'t H* m-
sulphonic acid, o-witmtoluene-iwulithtiftlc ncttl, p-nitntttiiw /^ **-
sulphonic add arc convcrtc<l into the rcirr«*Hjicindiitg axcr- «»i
hydrazo-compounclH.
p-Nitrobenzenesulphonic Acid nlj*o in*havf*H nornmllv nn
electrolytic reduction in slightly nlkiiliiii* solution at
cathodes (Elba and Wohlfahrt 5 j; it yields HZCH , or hv*l
1
Ztsehr. f. Ei«ktroch(*mic 7, 113 (HlfMl)
3
Bcr. d. dcmtflch, chf»m. C*i*«41irli, 0lt lK
•Ztachr. f. ElektrDcheraic 7, 143 OtiOO).
4
Ibid. 7, 142 (ICMKI).
s
Ibid. 8, 780 (1002)
THE KLKCTKOLYSIS OF AROMATIC' COMPOUNDS. 1S7
acid. In t i n 4 case of the o-nitro-acid, on the contrary, the,

reduction is far from normal; complicated products and o-
aminosulphonic acid are chiefly produced.
p-Nitrotoluenesulphonic Acid. 'The (lescllschaft f. diem.
Industrie of Basel ! prepares orange <lyes by using as cathode*
fl i i i i l nn alkaline solution of the yellow condensation products
of t~nit.rtrfttltti'twxiiljiht>nir und. "' «t
tik
f(*,g. a mixture of axoxystilbenedisulphonic acid, aôstilbencv

disulphonic arid, and dinitrcistilbenc*disul phonic, acidj. The
reduction, however, must not be continued until amido-eorn-
potmds result.
Klbs and Kremann" have likewise inveHtigatcMl th(» el(*ctr<v
chemical behavior of the dye **sun yellow*' fonnec] in alkaline
solution of the p-fiitrotctltif*ncHulphomc aeid, and found the
following:
1. "Sun yellow" consists chiefly of jMi^>xyHtilbcnodiHul~
phonic aciil.
2. Ifediiffd in alkiiliui* solution it yield; as end product,
I>-axot«*lu(*ni**lij4ulphonic acid,
.'{. Iii nci«l Mil sit kin with addition of ntannoUH chlorido there
lire* ffiniied |Mliainino.stiIliene(li.sulphoni« acid and p-lolui-
Hit* lollnu'ing may be remarked concerning the reduction in-

ncii! /oiutioti; Aironling ti» HiiiiHwrmann/1 rnet-anilic acid IK
^bfjiiiieii from m*iutnthvnzenehul[thmie acid in dilute
ri^ a**id; in concent rated acid JM-
iven mrnilarly 2 -4-5-ttnano-

a< id,
1
fug. Frit . No. (IKttty.
Zfwbr, I, Eli!ktrwlw*»iie % 410 (1 003).
1
!k?r. *I (IctitJtch. d«tm. (k» . S7, HWH (1804).
p-Dinitrostilbenedisulplionic Acid (according to Elb^

Kremann1 ), like p-azostilbenesulphonic acid, yields in ii^*
solution p-azotoluenedisulphonic acid, while in acid so' !
with the addition of stannous chloride the end-product
diaminodibenzyldisulphonic acid.
p-Binitrodibenzyldisulphonic Acid yields in-alkaline s< ^ 1
p-azodibenzyldisulphonic acid; in acid solution, in the pr* '•'
of-stannous chloride, p-diaminodibenzyldisulphonic acid-
X. Other Reductions of Nitro-compounds.
Lob has utilized the possibility of conducting the red*J
2
in alkaline solution up to the azo-phase for accompli^! * i

direct electrosynthesis of mixed azo-bodies and azo-dyes.
The components of the desired compounds are redu*"*
equimolecular proportions under conditions which make p««
the union of the two radicals during the azo-phase. By 11
of this method azo-compourids in which the • substitute o*
in any desirable position to the azo-bond; and which i*r<
obtainable by the Griess method, can be prepared.
Thus m-nitrobenzaldehyde, which in alkaline sc.*i
gives equal molecules, of m-nitrobenzoic acid and m-nitrol *
alcohol, yields as chief product m-m-azobenzoic-acid-t M *
alcohol,
m-COOHC6H4N=NC6H4CH2OH,
i
and as secondary products m-azobenzoic acid and m-azof *
alcohol.
Kaufmann and Hof3 (p. 181) had subjected m-nitrrj
aldehyde to reduction in alkaline solution, but they <li«
observe the occurrence of the mixed azo-compound; thcj* i
only the azo-alcahol and the azo-acid7 and explained tit**
yield of the former by the behavior of the m-nitrobenzyl n 1
towards alkalies, as shown in the equation:
2
Ber. d. deutsch. chem Gesellsch. 31,2201 (1898); Ztschr. f. Elektr**
15, 456 (1899).
8
Chem. Ztg. 20, 242 (1896).
II -,
5^
-1
»-*• 1.1 3- O
:
S i^'
n.
c ^— §2 ' ?^*
B o 5 '- ~) 00
^r s V* P 53
OMr* f*; "5 ?£ »~* !-i ^ 1
^ g
: V-C § l * s
If t
5<
*
*£
NS
*-« *F* 5 *<
"*"*
fS
X J~** J£
^ ^ 3- f ^ * j; »•* ^
1
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Is! f 5 'i & ? •<

.-, gt - « i —- ^
*-» * *. ^5
-^ tC -*
45 ** 3 H* X O c
0
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iE ^ E- £- 5
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3 I
1 1. 3
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2
5 !5
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^ 5. c"
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1 o o
1- 1
•f'SSjJs***^-* •sm^s^'vesis;-
There result from

o-Mtrobenzeneazophenol, phenolphentriazole; from
o-Mtrobenzeneazosalicylic acid, salicylic-acid-phentriazole,
/
X
/\N=NC 6 H3 < f ] 3
COOH;
\/N0 2 N/NN/
and from
o-Nitrobenzeneazo-a-naphthol, a-naphtholphentriazole :
XI. Nitro-Derivatives of the Naphthalene, Anthracene, and

Phenanthrene Series.
Since only the nitro-group is subject to reduction by the
cathodic action of the current on nitro-compounds, nothing
new can here be added regarding the possible reduction phases.
The conditions which with the benzene derivatives lead to
certain stages, cannot always be directly applied to these sub-
stances; this is due to the influence which the whole molecule
possesses over the reaction velocity of the separate processes.
This deportment is especially shown by the nitro-derivatives of
the anthracene series. Nevertheless, some of the more general
conditions also obtain here; for instance, nitronaphthalene
derivatives in acid electrolytes at attackable cathodes, accord-
ing to the process of Boehringer & Sohne,1 are also easily
reduced to amines. Gattermann's method has also been ser-
viceable in the preparation of amidonaphthols.
a-Mtronaphthalene,2 in aqueous acetone solution was re-
duced by Voigt to nitrosostyrol besides a little naphthylamine.
The latter is quantitatively obtained if #-nitronaphthalene is
*D. R. P. No. 116942 (1899); 117007 (1900)
2
Ztschr. f. angew. Chemie (1894) 108.
reduced in a hydrochloric-acid electrolyte with an attackable

cathode, or with addition of salts of the latter.1
aî-Mtronaphthalene-as-sulphonic acid was converted by
Voigt 2 into hydrazonaphthidenesulphonic acid and some
naphthylaniine. Gattermanri 3 obtained by Ms method the
aminonaphtholsulphonic acid in a normal manner. Analogously
behave
#i-Mtronaph.thalene-/?3- and /34-stilplionic acids and the di-
sulphonic acids (/?2, fa, and p<$£ of a-Nitronaphthalenc.4
(aia4 )Dinitronaphthalene (according to a patent of the
Badisclie Anilin- u. Sodafabrik) alone, or mixed with (a 1.0:2)
dinitronaphthalene j gives in concentrated sulphuric-acid solu-
tion a product which, by heating with dilute acids, can- readily
be converted into naphthazarin.6
aia%- and aia^- Dinitronaphthalene, if reduced according
to Tafel; in a mixture of acetic and sulphuric acid with prepared
lead cathodes, gives the 1-6- and 1 • 8-naphthylenediamincs
(Holler 6).
a-Mtro-/9-naphthyl ethyl ether, . — This naph-
thol ether, unlike the nitrophenol ethers, gives a-amido-/9-naph-

thyl ethyl ether as end-product of the alkaline reduction
(Rhode7).
o-Nitroanthraquiaone has been reduced by Moller 8 in
alcoholic-sulphuric acid arid in slightly alkaline solution to o-
amidoanthraquinonc. By electrical oxidation in concentrated
sulphuric acid there is formed, according to Weizrnarm,9 nitro-
oxyanthraquinonc; with alternating currents alizarinamide was
produced; and in the presence of glycerin, mannit, etc., blue arid
1
D. R. P. No. 116942 (1899); 117007 (1900)
2
Ztschr. f. angew. Chemie. 1894, 108.
* Her. d. deutsch. chem. Gesellsch. 26, 1852 (1893).
*I>. II. P. No. 81621 (1893).
8
D, R. P. No. 79400 (1894).
6
Elektrochem. Ztschr. 10, 199, 222 (1903-1904).
7
Ztschr. f. Blektrochemie 7, 340 (1900).
8
Ibid., 741, 797 (1901).
9
Fr. P. No. 265292 (1897).
green reduction products resulted. The action of the cathodic

IT current on
11:1 i • 2-Dinitroantnraquinone and i • 5-Dinitroanthraquinone in
a solution of glacial acetic acid with addition of sulphuric acid
produces diamidoanthraquinones;1 the yield, however, is poor.
The employment of lead cathodes, as shown by Tafel, may
perhaps increase the latter.
According to experiments of the Badische Anilin- u. Soda-
fabrik,2 a dinitroanthraquinone dissolved in fuming sulphuric
acid is changed by electrolytic reduction to blue mordant dyes.
Dinitroantlirarufindisulplionic Acid and Dinitrochrysazindi-
sulphonic Acid.—These substances are easily reduced electrolyti-
cally in sulphuric-acid solution to diamidoanthrarufmdisul-
phonic acid and diamidochrysazindisulphonic acid.3
p-Nitrophenanthrene has been converted by Schmidt and
Strobel4 into 9-azoxyphenanthrene by Elbs' process.
2-Nitrophenanthrenequinone in acid solution at lead cathodes
gives 2-aminophenanthrenequinone (Holier).
2 -y-Dinitrophenanthrenequinone is converted in acid solution
into 2 • 7-diamidophenanthrenequinone (Holier).
XII. Nitroso- and Nitro-Derivatives of the Pyridine and QuinoHne

Ser es.
Nitrosopiperidine, on electrolytic reduction in sulphuric-
acid solution (Ahrens 5); gives piperylhydrazine, piperidine, and
ammonia; at the anode there are formed at the same time a
diamine, CioHis^; of the fatty acid series, and two isomeric
amidovaleric acids, besides hydrochloric acid and piperidine.
Under similar conditions
Nitroso-a-pipecoline gives a-methylpiperylhydrazine, a-
pipecoline and ammonia at the cathode, and at the anode a
1
Elektrochem. Ztschr. 10, 199, 222 (1903-1904).
2
D. R. P. No. 92800, 92998 (1896).
8
D. R. P. No. 105501 (1898).
4
6
Ztschr. f. Elektrochemie 2, 578 (1896); Ber. d. deutsch. Gesellsch
30, £33 (1897); 31, 2272 (1898).
diamine and an amidocaproic acid. In the same manner the

other nitroso-derivatives of homologous piparidines on elec-
trical reduction give corresponding piperylhydrazines.
Ahrens and Sollmannl similarly prepared from
Mtroso-/?-pipecoline the /?-pipecolylhydrazinc; from
Nitroso-^-pipecoline the f-pipecolylhydrazine; from
Nitroso-a-a-lupetidine the a-a-dirnethylpiperylhydrazine;
from
Nitrosoaldehydecopellidine the aldehydecopcllidinehydra-
zine; and from
Nitroso-s-trimethylpiperidine the s-trimethylpiperylhydra-
zine.
Nitrosotetrahydroquinoline. —- Concerning the experiments
of Ahrens and Widera 2 on the oxidation of nitroso-derivatives
of pyridine and quinoline there is yet to be mentioned the
smooth conversion of nitrosotetrahydroquinoline into tetrahy-
droquinoline. The nitroso-group is found as nitric acid in
the anode fluid.
4-NitroquinoUne and i-o-Nitroquinoline, reduced in con-
centrated sulphuric acid, give 1.4-oxyamidoquinoline and
1.4-amidooxy quinoline (Gattermann 3),
4-Nitro-3-toluquinoline gives likewise a 4-amido-l-oxy-
3-toluquinoline •
N02r NH;
H3Cp
N
OH N
u
3. AMINO-DERIVATIVES,
Aniline.—Rotondi 4 electrolysed aniline in an ammoniaeal
solution. After a period of three days, during which hydrogen
was continually evolved at the negative pole and a tarry sub-
1
Chem. Ztschr. 2, 414 (1003).
2
Her. d. deutsch. chem/Geeellsch. 81, 2276 (1898).
3
Ibid. 27,1939(1804).
4
JTahresh. f. Chemie, 1884, 270.
Ill
stance was deposited at the positive pole, Rotondi interrupted
the electrolysis and was able, with more or less certainty, to
establish the following processes :
1. The formation of diazo-compounds :
C6H5NH2(HN03) -hHN02=C6H5N2N03 +2H20.
2. The formation of diazoamido-compounds :
2C6H5NH2 + HN02 = CeHsNzNHOeHs + 2H20.
C6H5N2N03 + C6H5NH2 = CeBU^NE - C6H5 + HN03.
3. The formation of azo-compounds by direct oxidation of

aniline :
2C6H6NH2 -{-20 = 2H2
4. The formation of amidoazo-compounds by molecular
rearrangement of diazoamido-compounds. The nitrous acid
and nitric acid were oxidation products of the ammonia which
was added.
C. F. Boehringer & Sohne add a manganese salt to the
electrolyte l in the presence of a strongly dissociating acid and
thus smoothly oxidize aniline to quinone.
The fact that aromatic amines are often directly convertible
by oxidation into dyes, early directed attention to the elec-
trolytic oxidation of amines for the direct preparation of dyes.
The investigations of Goppelsroder,2 which were carried out
some time ago, have primarily this end in view.
GoppelsroderTias compiled the technical results in a small
pamphlet: lt Farbelektrochemische Mitteilungen " (Mulilhausen,
1889). They may be briefly mentioned here.
If a galvanic current is conducted through acid or neutral
aqueous solutions of aniline, there is formed at the positive
1
D. R. P. No. 117129 (1900).
2
Dringler, Polytechn. Journ. 221, 75; 223, 317, 634; 234, 92, 209 (1876)-
1877). Cf. also: Concerning the Preparation of Dyes, and their Simul-
taneous Formation and Fixation in the Fibers with the Aid of Electrolysis,
Goppelsroder, Reichenberg, 1885.
pole, besides other coloring matters, aniline black, C24H2iN4Cl.

Under similar conditions dyes are obtained at the positive pole
from the salts of toluidine, me«hylaniline, diphenylamme f di-
tolylamine, and phenyltolylamine.
On electrolysis of a mixture of anthraquinone and caustic
potash Goppelsrocler obtained alizarine.
The numerous experiments which led to the formation of
dyes at the anode, when aniline, toluidine, mothylaniline,
diphenylandne, methyldiphenylamine and naphlhylamine or their
salts were electrolyzecl, have, however, not been scientifically
investigated and, hence, still remain unsolved. The same
holds true of Goppelsroder's investigations concerning the oxi-
dation of phenol and anthraquinone. The most important dis-
covery is the fact that aniline salts smoothly yield aniline black
at the anode; the naphthylamine salts give naphthylamine-
violet.1
Voigt,2 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 Goppelsrocler; namely, the preparation directly in the
bath of the important dyes of the aniline scries.
1
The following literary data will serve as a guide:
Research 1.* Preparation of aniline black.
Research 2.f Electrolysis of aniline with excess of aniline.
Electrolysis of toluidine.
Electrolysis of mixtures of aniline with toluidine igomcrs.
Research 3.J Electrolysis of aniline and toluidine salts in the presence
of potassium nitrate, nitrite, or chlorate in aqueous solution.
Research 4.§ Electrolysis of the salts of methylaniline.
Electrolysis of the salts of diphenylamme.
Electrolysis of the salts of methyldiphenylamine.
Electrolysis of phenol.
Electrolysis of the salts of naphthylamine.
Research 5- |[ Conversion of anthraquinone into alizarine by th© elec-
trolysis of a mixture of anthraquinone and potassium hydroxide.
2
Ztsch. f. angew. Chemie, 1894, p. 107.
* Dingier, Polytechm. Jotirn. 221, 75 (1670).
Ubid. 233,317 (1877).
I Ibid. 223, 634(1877).
§ Ibid. 224, 92 (1877).
U Ibid. 224, 209 (1877). .*-
•mi
If electrolytic oxygen is permitted to act upon aniline in

concentrated acetic-acid solution, acetanilide is formed (Voigt);
by using a dilute solution, however, amidohydroquinone is
obtained.
These investigations have not been satisfactorily concluded,
1
which is also the case with those of Foelsing, who, by the
oxidation of p-phenylenediamine and benzene-p-phenylene-
diamine, obtained indigo-blue dyes.
According to Lob's2 experiments (see p. 176) by electro-
lytic reduction of nitro-compounds in a solution of fuming
hydrochloric acid in an excess of an aromatic amine, incluline-like
dyes—not identical with the known induline dyes—are obtained.
Szarvasy,3 however, by anodic electrolysis of molten aniline'
hydrochloride, obtained electrolytically the indulines themselves.
If a mixture of aniline and aniline hydrochloride is electrolyzed
at 70°~90°, there is obtained a rich yield of azophenine, the
known intermediate product of the indulines. By electrolysis
of the pure molten salt at about 150°-300°, induline, anilidoindu-
line, and induline 6 B, besides the intermediate products of the
induline formation, could be detected as products of the anodic
oxidation. The oxidizing agent in these processes, which were
carried out without an oxygen-containing electrolyte, was
chlorine, which probably first produces azo-compounds that
react further in the molten mass with aniline hydrochloride.
4 5
The interesting research of Votocek, Zenisek and Sebor
may also be referred to in this connection. This permits the
Sandmeyer-Gattermann reaction (substitution of the diazo-group
by chlorine and bromine) to be carried out electrolytically. For
this purpose the diazotized "solution of the amine is electrolyzed
—for instance 50 g. aniline, 120 g. HC1, 38.5 g. NaN02—between
copper electrodes with addition of cuprous chloride or copper
sulphate. At the end of the experiment (ceasing of the nitrogen
1
2
Ibid. 6, 441 (1900).
3
Ibid. 6,403 (1900).
4
Ibid. 5, 485 (1899).
6
Ibid. 7, 877 (1901).
evolution) 64% chlorbenzene and 10% azobenzene could be

isolated. This process could be used successfully for obtaining
brombenzene by addition of copper sulphate and potassium
bromide, also for p-chlortoluene and 0-chlornaphthalene. The
method is not applicable for preparing fluorbenzene and
a-chlornaphthalene.
The direct diazotization and preparation of azo-dyes in one
electrochemical process was discovered by Lob.1 His method—
an anodic process—is based on the following principle:
As is well known, azo-dyes are generally prepared by cliazo-
tizing the amine in acid solution or suspension at a low tempera-
ture and then bringing together the diazotizecl solution with the
usually alkaline solution of the components to be joined.
The same 'effect can be reached electrochemically, if amine,
nitrite; and the coupling components of the compound desired are
simultaneously exposed in a neutral or sometimes alkaline
electrolyte to the anodic action of the current at an unattackable
electrode.
The first stage of the process consists undoubtedly in the
action of the discharged N02 ions on the amine, as-shown in the
equation
RNH2 + N02 -»RN - NOH 4- OH.
However, if an amine alone is subjected to the anodic current

action in the presence of the nitrite, complicated products
result; besides the action of the N02 ions upon the amido-group
and the typical decomposition of the diazo-body by the electro-
lyte, substitution and oxidation processes seem to occur.
It is therefore necessary to add components to the electrolyte
already before the electrolysis, which react so rapidly with the
intermediately occurring cliazo-bodies that the latter is with-
drawn from the other disturbing influences.
Phenols are particularly suited as addition substances for
fixing the diazo-bodies. Experiments have shown that the
coupling of the diazo-compound with the acid component takes
1
Ztschr. f. Elektrociiemie 1ft, 237 (1904).
place much more rapidly than its decomposition by the men-

tioned influences. In the presence of phenols the formation, of
the azo-dyes can therefore be made the predominating one. It
is very evident that in this process amines are not applicable as
components for coupling purposes, because they are themselves
subject to the action of the nitrite ions; and other complicated
reactions.
The experiments are generally conducted by putting the
aqueous solution, or suspension, of amine, coupling component—
preferably in the form of a soluble salt—and nitrite, in equi-
molecular proportions, in the anode chamber, which is suitably
separated from the cathode chamber by a diaphragm. Platinum
is the best anode material; any suitable metal can serve as
cathode. The current conditions chosen may vary greatly—from
50-600 amp. per square meter of anode surface. It is very
important that the anode fluid be stirred during the whole
experiment.
An increase in temperature is sometimes beneficial, but is
generally unfavorable for the yield and purity of the dyes.
An artificial lowering of the temperature, which is necessary
for the chemical diazotizing process, is never required. Several
examples are classified in the following table:
Benzidine Sodium.
Sodium Benzidine 1.4-
Sulphanilat Naphthion- Dianisidine NaphthyI-
e ate /?-Naphthol Sodium aminesul-
Anode 0-Naphthol Sodium Sodium Salicylate phonate.
solutions : Nitrite XflJ.y.Ij. n
Sodium /9-Naphthol
Sodium
Nitrite "WTo f n-f Nitrite Sodium
Water Sodium Water Water Nitrite
s
Hydroxide Water
Results : Orange II Congo Dianisidine- Chrvsamine Rocceline
blue "G
Dimethylaniline, electrolyzed in sulphuric-acid solution at

platinum electrodes in the presence of some chromic acid, gives
tetramethylbenzidine. In this case the oxidizer is chromic
RY
THE ELECTROLYSIS OF AROMATIC COMPONDS.
acid; the current action consists only in the

generation of the latter (Lob *).
Triamidotriplienylmethane. — The Farbwerken vorm. Meister,
Lucius, & Briining,2 by electrolytically oxidizing those sub-
stances which are formed in the treatment of the hydro-
chloric-acid salts of homologues of triamidotriphenylmethane
with fuming sulphuric acid in the presence or absence of sul-
phur, succeeded in preparing blue, basic triphenylmethane
dyes.
4. PHENOLS .
Phenol. — Bunge, Bartoli and Papasoli 4 submitted phenol

3
to the action of the electric current. Bunge observed that the

decomposition of potassium phenolate was analogous to that
of an acid or a salt ; the potassium phenolate was split up into
K (cation) and CeHsO (anion), the latter combining with
water to form phenol, with the liberation of oxygen. Bartoli
and Papasogli, on electrolyzing solutions of phenol in potas-
sium and sodium hydroxide, and using electrodes of coke,
graphite, and platinum, obtained an acid having the com-
position CrHeO^t, which melted at 93°, reduced ammoniacal
silver solution and Fehling's solution on being heated, and
when in aqueous solution was not precipitated by acids. When,
however, retort 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 solution to the
action of the electric current they were able to isolate a com-
pound, Ce5H48022, soluble in alkali and precipitated from such
solutions by mineral acids. This latter compound on being
oxidized with nitric acid formed picric acid. When allowed
to remain in solution in the presence of dilute acids for a pro-
1
2
D. R. P. No. 100556 (1897).
8
Ber. d. deutsch. chem. GeseUsch. S, 296 (1870).
z. chim. 14, 103 (1884).
longed period, it underwent decomposition according to the

following equation:
The electrolysis of neutral sodium-phenolate solution gave

an acid having the formula C29H2o08, which likewise is decom-
posed on boiling with dilute acids:
=
C iy
The compound C^HioOs is soluble in alcohol, melts at 75°,

and is isomeric with the hydroquinone ether obtained by
Etard from chlorchromic acid and phenol. It has tne com-
position
The relations which exist between the potential and the

pressure with which a discharged ion, like chlorine, bromine,
or iodine reacts with phenol nave been determined by Zehr-
lant1 with the following results:
The substitution of chlorine in phenol in dilute acid solution
does not take place, nor does that of bromine, since the oxida-
tion begins earlier, at a lower potential, than the halogen
discharge. Iodine also does not act on phenol in acid solution.
A bromination can, however, be obtained if, on the one hand,
the potential for the beginning of the oxidation is raised by
decreasing the oxygen- or hydroxyl-ionic concentration; on
tlie other hand, the discharge potential of bromine is lowered
by increasing the bromine concentration i.e., if concentrated
hydrobromic acid (multiple normal) is employed, bromination
occurs.
Thymol.—In alkaline solution halogen substitution takes
place very rapidly with phenols. This fact has led to the
. f. Elektrochemie 7, 501 (1901).

electrolytic preparation of dithymoldiiodidc, the antiseptic

aristol, as made by Messinger and Vortmannl by the electrolysis
of an alkaline solution of thymol with the addition of potassium
iodide.
Directions for the preparation of a whole series of iodides of
phenols are mentioned in the same patent papers; e.g., from
fi-naphthol, phenol, resorcin, salicylic acid, crexolinic acid, carva-
crol, p-isobutylphenol, o-m-p-isobutylcre$ol, etc.
Nosophen, a tetraiodophenolphthalcin, from phenolphtha-
lei'n (Classen arid Lob 2), is obtained in like mariner.
With these methods of preparation there corresponds a simi-
lar process, which the Societe chimique cles usines clu llhonc anc.
Gilliard, Monnet et Cartier patented in Germany,3 for the clec-
trolytic preparation of cosine arid other halogen derivatives of the
fluorescein group. The solutions of the fluorescei'ns in alkali-
hydroxide or in alkali-carbonate solution serve as anode fluids.
The halogens, such as chlorine or bromine, are introduced into
the anode compartment, whereby salts of the halogen acids
form and simultaneous halogermtion of the fluorescent occurs.
Since the salts are again decomposed by the current, with
splitting off of the halogen, which in turn reacts on tho fluores-
cei'ns, the quantitative—very important for bromine and iodine
—utilization of the halogen can take place. The well-known
eosins are said to be obtained in excellent yields and in a high
state of purity.
Phenylmercaptan. —Bunge,4 who had obtained othyldi-
sulphide from ethyl meraiptan (see p. (55), also investigated
phenylmercaptan. Phenyldisulphido, (GoH$) 282, was formed
from phenylmercaptan at the positive pole.
Hydroquinone.—If an acid hydroquinone solution with
addition of a manganese salt, according to the process of 0. P.
Boehringer & Sohne,6 is electrolysed, quinone is smoothly pro-
J
D. R, P. No. 64405 (1891).
2
Ber. d. deutsch. chern. Gcscllsch. 28, 1603 (1895).
3
D. It P. No. 108838 (1899).
4
Ber d. deutsch. chem. Gesellsch. S, 911 (1870).
5
D. R. P. No. 117129 (1000).
duced. But if a weak sulphuric-acid solution without addition

is electrolyzed, quinonehydrone is precipitated at the anode
(Liebmann x) .
Resorcin. — Alefeld and Vaubel,2 by electrolytic oxidation,
have obtained dyes of different shades from resorcin and other
Lydroxyl derivatives of the aromatic series, such, as gallic acid,
tarinic acid; fhiorescems and eosins. An investigation of the
dyes was not made.
Pyrogallol (pyrogallic acid).— According to A. G. Perkin
3
and F. M. Perkin, purpurogallin CnEgOs, can readily be ob-
tained by electrochemical oxidation of pyrogallol in dilute
sulphuric acid with addition of sodium sulphate at a platinum-
iridhini anode.
Gallic Acid behaves likewise. Purpurogallincarboxylic
acid, CnHrOsCOOH, is probably obtained.
4
Eugenol. — The firm v. Heyden Nchfg. obtains vanillin elec-
trolytically from eugenol. The latter is rearranged by alkalies
into isoeugenol and then oxidized electrolytically in alkaline
solution:
/OH /OH
C6H3f-OCH3 - aeOCEs
\CH 2 CH=CH 2 \CH«CHCH3
Eugenol Isaeugenol
OH
+30 +CH3C300H.
- \ C HO
\CH=CHCH3
Isoeugenol
5. ALCOHOLS, ALDEHYDES, EEJTONES, ANI> QUINONBS.
These classes of bodies, owing to their peculiarity in being

both reducible and oxidizable, present many interesting phe-
nomena respecting their electrolytic behavior. Since every
1
Ztschr. f. Elektroehemie 2, 497 (1896).
2
Chemu Ztg. 22, 297 (1898).
* Proceed. Chem. Soc. 19, 58 (1903).
4
D. R.P. KTo. 92007 (1895).
electrolytic cell performs both functions at both electrodes, the

problem presents itself to apply both of these effects of the
current to one and the same substance. We shall see that this
possibility has actually been realized in individual cases.
Salicin, saligenin-glucose, by the action of the enzymes
ptyalin and emulsion, is known to split up into glucose and
saligenin (i.e. o-oxybenzyl, e.g. salicyl alcohol) . On boiling with
dilute acids the same decomposition occurs, but saligenin is res-
inified to saliretin. Tichanowitz l and Hostmann 2 found that
salicin on electrolysis splits up into glucose and salicyl alcohol,
the latter being partially oxidized to salicylic aldehyde and
salicylic acid.
Benzaldehyde. — Kauffmann,3 by electrolyzing benzaldehyde
in a 12-15% solution of potassium bisulphite, obtained at
the cathode a mixture of hydrobenzom and isohyclrobenzi'on.
4
According to his statements, an alcoholic solution of sodium
hydroxide is more suitable for the reaction than the aqueous
solution of bisulphite. Other aldehydes and ketones show &
behavior similar to that of benzaldehyde, as will be explained
under the individual substances.
5
Tafel and Pfeffermann have discovered a useful method
for preparing amines. They electrolytically "reduce oximes
and phenylhydrazones in sulphuric-acid solution. Thus
BenzyKdenephenylhydrazone, the condensation product of
benzaldehyde and phenylhydrazine, gives 43 per cent, of the
theoretical yield of benzyl amine, besides some aniline:
C6H5CH =NNHC6H5 -f 4H -> C6H5CH2NH2 +C6H5NH2.
Bendaldoxime, by reduction, is split up, yielding 69 per cent.

of the theoretically possible quantity of benzylamine:
C6H5CH = NOH+4H -> C6H5CH2NH2 + H20.

1
Chem. Centralb. 613 (1861).
2
Chem. Ztg. 17,1099 (1893).
3
Ztschr. f. Elektrochemie 2, 365 (1893)
* Ibid. 4, 461 (1898).
5
Ber. d. deutsch. chem. GesellscK 35,1510 (1902).
Salicylaldehydephenylhydrazone, by electrolytical oxidation

in alkaline solution at a platinum anode can be converted into
salicyl-a-osazone (Biltz1).
20EC6H4CH = NNHC6H5 4- 0
OHCeH^CCeBUOH
II || +H 2 0.
C5H5HNN NNHCeHs
Acetophenone, Cells • CO -CH3. — Acetophenone yields aceto-
phenonepinacone,
CeHsv /CeHs
>C(OH)-C(OH)<
X
CR/ CH3
if reduced in alcoholic sodium hydroxide (Kauffmann 2) . Elbs
and Brand3 employed an alcoholic-alkaline solution and lead
cathodes; electrolyzing at the boiling temperature, they also
obtained acetophenonepinacone and a moderate yield of methyl-
phenyl carbinol:
C6H5CH(OH)CH3.
In sulphuric-acid solution and at lead cathodes the same sub-
stances are produced in almost equal yields.
Acetophenoneoxime, investigated by Tafel and Pfeffer-
mann4 in the same way as benzaldoxime, gives phenylethyl-
amine sulphate :
v
>C =NOH 4-4H -+ >CHNH2 4-H20.
/
Benzophenone, on being reduced in alkaline solution at lead
cathodes (Elbs and Brand5), gives benzhydrol almost quanti-
tatively,
1
Lieb. Am. 305, 167 (1899).
2
3
Ibid. 8, 784 (1902).
4
Lc.
f1 TT
5
\CHOH,
while in sulphuric-acid solution the reduction becomes more

complicated. If the warm solution is electrolyzed with a mod-
erate current density, there occurs as chief product /?-benz-
pinacoline, which is to be regarded as a molecular rearrange-
ment product of the primarily formed benzophenonepinacone
with splitting off of water:
C5
\C(OH)—C(OH)/ 6
S \f^T
C656H
With a very small current density and at a low
temperature
(0°-2°) the yield of /9-benzpinacoline is trifling, benzhydrol and
diphenyl me thane being chiefly produced.
If the alcohol and sulphuric acid are replaced by acetone
and phosphoric acid respectively, and the electrolysis is carried
out with a high current density and with a warm solution,
there will be formed, by the action of phosphoric acid with
simultaneous splitting off of water, a-benzpinacoline, the re-
arrangement product of benzophenonepinacone:
/ CeH,
6ll5\
C(OH)— C(OH)< \p Csf
X
C6H5 ,/C~
C6H5 X
C6H5.
Benzophenoneoxime. —This substance, on
electrolysis in a
60% sulphuric acid at lead and mercury electrodes — the latter be-
ing preferred on account of the difficultly soluble sulphate which
i$ formed — is reduced to benzhydrylamine (Tafel and Pfeffer-
mann -
NOH +4H CHNH2 +H20.
Elbs and Brand2 also investigated the following ketones:
L c. n.c.
Phenyl-p-tolylketone, by alkaline reduction, gives almost

quantitatively phenyl-p-tolylcarbinol :
The same product, together with phenyl-p-tolylpinacone,

is produced in sulphuric-acid solution at a low current density
and temperature. With a higher current density and tempera-
ture the formation of carbinol is trifling, and a good yield of
phenyltolylpinacone is obtained :
C6H5-C(OH)C6H4CH3
C6HB-C(OH)C6H4CH3.
Phenyl-m-xylylketone. — The reaction product of the alka-

line reduction is a liquid modification of phenyl-rn-xylylcarbinol;
but in sulphuric-acid-acetone solution at the boiling temperature
phenyl-m-xylylpinacone is- obtained. The yield of the latter is
40-50 per cent, of that theoretically possible.
Phenyl-a-naphthylketone. — A satisfactory yield of phenyl-
a-naphthylcarbinol is obtained in alkaline electrolytes; in acid
solution only phenyl-a-naphthyl-/?-pinacoline,
results. This is due to the fact that phenylnaphthylpinacone is

very sensitive towards acids; thus only its conversion product is
obtained above,
The same is true in acid solution of
p-Ethoxybenzophenone, which yields p-ethoxybenz-/?-pina-
coline :
C2H5OC6H4
THE 'ELECTROLYSIS OF AROMATIC COMPOUNDS. 207
p-Oxybenzophenone.—While this ketone is not reducible in

alkaline electrolytes, the normal reduction product, p-oxybenz-
pinacone, is produced in alcoholic-sulphuric acid:
C6H5C(OH)C6H4OH
C6H5C(OH)C6H4OH.
p-Oxybenzophenonebenzoate.—This substance is reduced to
the carbinol in sodium-acetate solution. To prevent saponifica-
tion during reduction, the free alkali must be continually neu-
tralized with acetic acid.
Phthalyl-p-aminobenzophenone.—This compound, by reduc-
tion in sulphuric-acid solution, gives a poor yield of pinacone.
Elbs and Brand sum up the results of their investigation as
follows:
1. The electrochemical reduction of ketones in alkaline
solution at lead cathodes gives the same products as the chemical
reduction with sodium amalgafn or with zinc dust and alkali;
the process is in many cases suitable for the preparation of
benzhydrols.
2. The electrochemical reduction of ketones in acid solution
(dilute sulphuric or phosphoric acid) at lead cathodes leads to
pinacones; if these are sensitive towards acids, the corresponding
a or /? pinacolines are obtained in their stead. For this reason
the electrochemical process is not so generally applicable for the
preparation of aromatic pinacones as the method employing
glacial acetic acid and zinc dust, which has been worked out by
Elbs and Schmidt;1 but the electrochemical reduction is more
energetic than that with zinc dust and glacial acetic acid.
, Fatty ketones are reduced like the aromatic ketones, with the
difference that fatty and fatty-aromatic ketones give simul-
t, taneously alcohols and pinacones, whereas pure aromatic ketones
I yield chiefly only pinacones.
Tetramethyldiamidobenzophenone, Michler's ketone, accord-
ing to Kauffmann,2 when electrolytically reduced in alcoholic
1
2
sodium-hydroxide solution, gives the corresponding benzhydrol:
/C6H4N(CH3)2 /C6H4N(CH3)2
C0< 4-2H=CHOH
\C6H4N(CH3)2 \C6H4N(CH3)2
Elbs and Brand 1 obtained the same result.
Êscherich and Moest 2 made an extensive investigation with
the object of preparing electrolytically tetra-alkylated diamido-
benzhydrols. They discovered that, by observing certain
experimental conditions, the reduction can at will be directed to
the hydrol or the pinacone. This is particularly true with
Michler's ketone. We can thus obtain chiefly pinacone, for
instance, by employing copper cathodes in a dilute sulphuric-
acid solution; nickel cathodes, under the same conditions, yield
about equal quantities of pinacone and hydrol, wnile by using
lead cathodes and mercury cathodes, hydrol is chiefly produced.
Moreover, the pinacone reaction occurs the more easily the more
concentrated the solution is of the acid. Because of the resisti-
bility of the resulting reduction products towards anodic oxygen,
separate electrode chambers are not required.
Since
Tetramethyldiamidodiphenylmethane,
(CH3)2NC6 H4v
(CH3)2NC6H
on electrolytic oxidation in dilute sulphuric acid at a lead
anode also readily yields the hydrol, the oxidizing action of the
current can also be employed, besides the reducing action,
in the preparation of the hydrol, if a mixture of tetra-
methyldianiidodiphenylmethane and .tetramethyldiainidobenzQ-
phenone in molecular proportion is electrolyzed. Escherich
and Moest actually obtained a very good yield of the hydrol,
— without an evolution of gas, — at the cathode and anode.
Dibenzylketone. — Elbs and Brand3 have published a short
1
2
Ibid. 8, 849 (1902); D. R. P. No. 133896 (1901).
note on this substance. The reduction seems to take place

like that of other ketones; but the nature of the oily reaction-
product was not determined.
Benzile.— The aromatic diketone benzile, CeHsCO • CO • CeH5,
gives peculiar results (Kauffmann 1). By reduction in an alka-
line alcoholic solution a whole series of bodies is formedyi.e.,
benzoic acid, benzilic acid, tetraphenylerythrite:
C6H5-CHOH
C6H5-COH
C6H5-COH
C6H5-CHOH,
and a substance, C28H260a, containing one less atom of oxygen,
which has probably the constitution
C6H5-CHOH
C6H5-COH
CeHs-CHOE.
Tetraphenylerythrite is also formed by the direct reduction of

benzoin.
Benzoin. — Benzile, by reduction in dilute alcoholic sodium
hydroxide and in alcoholic sulphuric acid, according to James,2
can inversely be converted into benzoin. Oxidation of benzoin
in alkaline and sulphuric-acid solution gives a poor yield of ben-
zoic acid. In alcoholic hydrochloric acid, especially at a high
current density, benzile is formed.
Anthraquinone. — The first researches concerning the elec-
trolysis of this substance were made by Goppelsroder (see p.
194), who, by suspending anthraquinine in potassium hydroxide,
1
2
Journ. Am. Chem. Soc. 21, 889 (1899).
suspected reduction products, such as oxyanthranol or hydro-

anthroquinone, among the substances deposited on the cathode
electrode. If the current is sent through a mixture of anthra-
quinone and molten alkali, oxyanthraquinone first, then alizarate,
and then purpurate, is supposed to be formed. These experiments,
however, require to be repeated with greater exactitude.
According to Weizmann,1 anthraquinone, dissolved in concen-
trated sulphuric acid, is converted by electrolytic oxidation
into monoxy-, dioxy-, and trioxyanthraquinone. An addition
of oxalic acid to the sulphuric acid is suitable for obtaining
dioxyanthraquinone. A nitrooxyanthraquinone, which is con-
vertible by electrical reduction into amidoalizarin, is similarly
obtained from mononitroanthraquinone.2 The amidoalizarin can
be directly obtained from nitroanthraquinone if its solution is
electrolysed with an alternating current. The sulphonic-acid
derivatives of anthraquinone behave like anthraquinone.
The phenomena occurring with these oxidations were later
more accurately investigated by Perlin.3 From anthraquinone
in 92% sulphuric acid 90 to 96% dioxyanthraquinones and a
small quantity of monoanthraquinones were obtained. Besides
a- and /9-monooxyanthraquinone, quinizarin, alizarin, and pur-
purin could be isolated. If the anthraquinone-sulphuric acid
solution is employed as cathode fluid, anthranols, anthrones,
and hydroanthranols are formed. If the sulphuric-acid con-
centration of the anode solution is increased, there are formed
sulphurated oxyanthraquinones.
a-Mononitroanthraquinonej under like conditions, gives a
nitrooxyanthraquinone besides a mixture of di- and trioxyan-
thraquinone.
Dibromanthraquinone gives violet crystals, perhaps a tetriir-
oxydibromanthraquinone.
Phenanthrenequinone, according to Perlin, is electrolytically
oxidized in concentrated sulphuric-acid solution to a mixture
of mono- and trioxyphenanthrenequinone.
1
F. P. No. 265291 (1897).
2
F. P. No. 265292 (1897).
*Diss. Berlin, March, 1899.
All these oxidation processes illustrate the possibility already

mentioned (p. 132) of introducing oxygen electrolytically into
the benzene nucleus.
6. ACIDS.
ti
The electrolysis of aromatic acids by no means offers results
which are comparable to those obtained by the electrolysis
e
of aliphatic acids. In so far as the aromatic acids ; or their
ft
salts, act as electrolytes, a regeneration of the acid from the
anion RCOO and water, with evolution of oxygen, occurs
almost exclusively. A splitting off of carbonic acid, which
p
makes possible the manifold reactions of aliphatic acids, almost
never occurs here. The results obtained with aromatic acids
are, therefore, only of a more general interest so far as the
acids, by substitutions in the benzene nucleus, can act as
'I'l
M (o
cathodic or anodic depolarizers, and can in this way exert rA^'t
reduction and oxidation effects.
Benzole Acid.—Benzole acid and its salts were examined M
by several investigators, first by Matteuci,1 then by Brester7 2
but most thoroughly by Bourgoin.3
The result of all these? investigations is to show that here $
•1 no secondary reactions take place, as was observed in the case
litR
of the fatty acids, but that the only effect of the current is to
produce a separation into hydrogen (or metal) and the acid
radical, the latter regenerating the acid at the positive pole.
In an alkaline solution it is possible to so increase the oxida-
a tion that the benzole acid is destroyed. The decomposition prod-
1 1*" • ucts which thefi appear at the anode are carbon dioxide, carbon
monoxide, and sometimes acetylene. The odor of bitter
almonds is also frequently observed.
A thorough investigation was made by L6b; 4 who employed
Sy a current having a potential of 6-7 volts and a current density
re* of 15-20 amp. per sq. cm. and obtained a small quantity of
1
Bull. soc. chim. 10, 209 (1868).
2
Jahresb. f. Chem. (1866), 87.
3
* BuU. soc. chim. 9, 431 (1867).
4
Ztschr. f. Elektrochemie, 2, 663; 3, 3 (1896).
I ' 212 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
1
' . a substance containing sodium, but the chemical nature of
: ' •' which has not yet been determined. There is formed besides
this compound a small quantity of benzaldehyde, as well as
J acetylene and carbon monoxide. Under no circumstances do
• , diphenyl or other hydrocarbons occur; nor do fatty acids
'! appear, which is otherwise generally the case in an extensive
! oxidation of this character.
l According to the investigations of Schall,1 diphenyl does,
$ however, occur if a solution of sodium benzoate in molten
j benzoic acid is electrolyzed at 100 volts between silver elec-
trodes.
Benzoic Esters.—Tafel and Friedrichs,2 by conducting the
electrolysis in alcoholic-aqueous sulpnuric acid at lead or mer-
cury cathodes, obtained methyl benzyl ether and the ethyl benzyl
* * ether from benzoic methyl and benzoic ethyl esters respectively.
/ * , Mettler,3 by a similar arrangement, obtained chiefly benzyl alco-
* hoi and some benzyl methyl ether from benzoic methyl ester.
[ ,f The esters of monochlor- and brombenzow acids also yield the
I • corresponding ethers and alcohols.
TMobenzoic Acid.—On electrolyzing this acid Bunge4 ob~
\ tained the bisulphide of benzoyl.
I Sulphobenzoic Acid.—This acid, according to the
statements
« ' of the same investigator, is not changed by the current.
Phthalic Acid.—Bourgoin 5 states that the electrolysis of
this acid and of its neutral or alkaline salts resulted in the
- formation of the unchanged acid at the positive pole. The
appearance of small quantities of carbon dioxide and carbon
monoxide, however, was an evidence that a small portion of the
acid had undergone oxidation.
;! The potassium salt of the mono-ethyl ester of phthalic acid,
K when electrolyzed by Brown and Walker,6 became dark-colored,
I . and a resinous substance was .formed, but the isolation of any
1
Ztschr. f. Elektrochemie 6, 102 (1899),
2
3
Ibid. £7, 3692 (1904).
4
Ibid. 3, 296 (1870).
6
Jahresb. 1 Chem. 631 (1871).
6
Lieb. Ann. 274, 67 (1893).
new electrolytic product was not possible. Phthalic esters,

according to Tafel and Friedrichs, 1 can be readily reduced in
the presence of sulphuric acid at lead or mercury cathodes.
Phenylacetic Acid. — This acid, electrolyzed in the form of
its potassium salt by Slawik,2 yielded free phenylacetic acid. *%!*S
w*
p-Toluic Acid. — According to an incomplete research by «;u>»
Labhardt and Zschoche,3 p-toluic acid in alkaline solution -at $>v v
polished platinum anodes is oxidized to terephthalic acid :
§^
COOH
COOH JOOH.
p-Toluenesulphonic Acid. — This acid gives at platinum and
lead electrodes a poor yield of p-sulphobenzoic acid (Sebor4 ).
Cinnamic Acid. — Cinnamic acid; investigated by Brester,5
showed a similar behavior in the electrolysis of both the free acid
and the neutral solutions of its salts. Lob 6 has reported an
accidental observation on the formation of bromstyrene by
electrolysis of cinnamic acid in the presence of potassium bromide.
In acid solution Marie7 converted cinnamic acid almost
quantitatively into hydrocinnamic acid.
Benzylmalonic Acid. — When this acid in the form of its
ethyl-potassium salt was submitted to electrolysis by Brown and
Walker 8 it exhibited a bejiavior materially different from that of
malonic acid. The solution became dark-colored, but contained
no new compound. If oxidation occurred; it was a complete B,
oxidation into carbon dioxide and carbon monoxide; such as has
been observed in the case of unsaturated acids.
However, when v. Miller 9 electrolyzed the ethyl-potassium
l
l. c.
2
8
4
Ibid. 9,370 (1903).
5
Jahresb. 1 Chem. 87 (1866).
9
7
Compt. rend. 136, 1331 (1903).
8
Lieb. Ann. 274,67(1893).
8
salt of this acid in the presence of potassium acetate, not only

a'-methylhydrociimamie ester,
XCOOC2H5
C6H5CH2CH<
^CH 3
but also dibenzylsuccinic ester,
C6H5 - CH2 - CH - COOC2H5
C6H5 - CH2 - CH - COOC2HS,

was produced, as was to be expected according to the Brown-
Walker reaction. There are also present the normal by-
products of the electrolysis of such kind of acids, in this case
hydrocinnamic acid and cinnamic acid. On repeating these
l
experiments, Hauser was also able to isolate propylbenzene, the
formation of which was brought about by the electrolysis of
hydrocinnamic ester—readily formed from the material started
with—and potassium acetate.
The electrolysis of the ester-salt of benzylmalonic acid
with potassium butyrate and caproate takes place just as with
potassium acetate. Good yields of propylhydrocinnamic ester
and amylhydrocinnamic ester, besides dibenzylsuccinic ester
and cinnamic and hydrocinnamic esters, are obtained.
Dibenzylacetic Acid. — This substance, on electrolysis of
its potassium salt, and a mixture of this salt with fatty acid salts,
gives no tangible products.
Salicylic Acid.—The formation of yellow mordant dyes,
which are obtained by the electrolytic oxidation of aromatic
oxycarboxylic acids in sulphuric-acid solution (Badische Anilin-
u. Sodafabrik2 ), seems to be based on the frequently mentioned
introduction of oxygen into the benzene nucleus. The materials
serving as starting-point, aside from salicylic acid, were sym-
metrical m-dioxybenzoic acidf gallic add, tannin, gallaminic acid,
esters of the adds, m- and p-oxybenzoic acid, and other oxy-acids.
1
Dissertation Munich (1901).
3
D. R. P. No. 85390 (1895).
The electrolytic introduction of halogens into salicylic acid

has been mentioned under phenols (p. 201).
Von Miller and Hofer 1 have applied their method for the
electrolysis of organic oxy-acids to several aromatic acids con-
taining substituents; these experiments may briefly be men-
tioned here.
Plienyl-/?-lactic Acid. — This acid gives at the anode
benzaldehyde, besides resinous bodies.
Mandelic Acid. — This substance yielded at the anode chiefly
carbonic acid, a little carbon monoxide, and also benzaldehyde.
The same body was formed in the electrolysis of phenyl-
glyceric acid.
Suip&oanthranilic Acid. — This substance, according to a
patent 2 of Kalle & Co., can be converted into anthranilic acid
if electrolyzed in neutral or slightly acid solution at a mercury
cathode.
7. ACID AMIDES AND NITRILES.
According to the investigations of Baillie and Tafel,3 the
reduction of acid amides in sulphuric-acid solution at lead
cathodes leads to amines, as shown in the equation:
RCONH2 + 4H = ECH2 - NH2 + H20.
Benzamide yields only a little benzylamine; benzaldhyde,
which probably contained benzyl alcohol, was also formed.
In a similar manner
Bimethylbenzamide gives dimethylbenzylamine;
Acetanilide gives ethylaniline ;
Acetyl-o-toluidine gives ethyl-o-toluidine; and
Succinanil gives phenylpyrrolidone:
CH2—OCX CH2— OC
I >NC 6H5+4H = | ;,
CH2— OCX CH 2 ~CH
1
Ber. d. deutsch. chera. Gesellsch. 27, 461 (1894).
2
D. K. P. No. 146716 (1902).
8
(The same reaction in the aliphatic series, p. 119, in the

pyridine and quinoline series, p. 218.)
o-ToIuenesulphonamide (o-Toluenesulphamide).—According
to a patent of F. v. Heyden Naehfolger, 1 benzoylsulphon-
imides can be prepared by the electrolytic oxidation of toluene-
sulphonamides in alkaline, or earthy-alkaline solution; for
example* o-benzoylsulphonimide (benzoic sulphimide), or sac-
harin, from o-toluenesulphonamide:
/ SOs- NHs /S02V
C6H4< + 30 = CoH/ >NH + 2H2 0.
X
XHs CO /
The p-nitro-substitution products of o-toluenesulphcnamide-
are said to behave similarly.
Just as amines are easily obtained by reduction of nitriles-
with sodium amalgam or sodium and alcohol, so this reaction
can be carried out electrolytically (p. 121).
Benzonitrile.—Ahrens,2 by electrolytic reduction of this
substance in dilute 'sulphuric acid at a platinum cathode^
obtained benzylamine; in like manner,
Benzylcyanide gave the corresponding phenylethylamine.
8. THE INDIGO REDUCTION.
The reduction of indigo by electrolytic hydrogen in alkaline
suspension, the fluid being warmed, has already been carried.
out by Fr. Goppelsroder3 and v. "Wartha.4 Mullerus 5 easily
reduced indigosulphonic acid.
Thorough studies regarding the process of the reduction of
indigo by the electric current have recently been made by
A. Binz,6 and Binz and Hagenbach7; these show that most
probably zinc and not hydrogen plays the chief part in the
reduction. Thus when indigo is electrolytically reduced in
1
D. R. P. No. .85491 (1895). " ~~"
2
Ztsdhr. 1 Elektrochemie 3, 100 (1896).
3
Preparation and Fixation of Dyes with the Aid of Electrolysis, Reichen-
berg, 1885.
* Chan. Ztg. 8, No. 25 (1884).
5
Ibid. 17,1454 (1893).
«Ztschr. 1 Elektrochemie 5, 5, 103 (1898); 9, 599 (1903).
f
Ibid. $, 261 (1899).
alkaline solution, almost no formation of indigo-white occurs,,

but if alkaline-zinc solutions and zinc cathodes are employed
a smooth reduction (formation of the vat) takes place.
Binz concludes further that the conversion of indigo into
indigo-white depends upon a withdrawal of oxygen and not
upon the taking up of hydrogen, as hitherto supposed. The
phenomena observed in the reduction of indigo agree with the
views regarding the behavior of attackable cathodes, as men-
tioned in the introduction (p. 18). The reducing agent is the
discharged zinc-ions, whose separation on the cathode and whose
reaction with the depolarizer indigo occurs in a proportion
which depends upon the velocities of the two processes. The
cathode potential appears as a measure for the reduction energy,,
whose value is naturally determined by the chemical nature
of the zinc, and cannot forthwith be attainable by any other
reducing agent such as hydrogen. In this respect we can say
with Binz that the indigo reduction is based upon the direct
action of the metal.
Without entering upon the subject of the electrolytic prepa-
ration of reducing substances which are useful for vat forma-
tion, such as hydrosulphites, a processl of the Farbwerke-
Meister, Lucius and Briining in Hochst may here be mentioned
by which sulphite solutions are electrolyzed at higher tempera-
tures in the presence of indigo. Hereby the sulphites are con-
verted into hydrosulphites, which accomplish the reduction of
indigo, the sulphites being regenerated. The latter are again
continually reduced. In alkaline electrolytes a vat is imme-
diately formed and in acid solutions solid indigo-white is pre-
cipitated. The current density and cathode material can at
wil] be chosen within wider limits.
9. PYEIDINE DERIVATIVES AND ALKALOIDS .
The pyridine ring is easily reducible. Hydropyridines are
formed from pyridine and its derivatives, and piperidines by
complete hydration. Quinoline and acridine are also easily
converted into hydro-compounds.
1
D. H. P. No. 139567 (1902).
2 IS ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
These reductions can easily be obtained with the electric

current under suitable conditions; the alkaloids, which have a
pyridine nucleus, also behave analogously.
Pyridine. — Ahrens l accomplished the electrolytic reduction
of pyridine and the derivatives of pyridine, and obtained piperi-
dine from pyridine, and a-pipecoline from a-picoline. In these
electrolyses lead cathodes and 10% solutions of sulphuric acid
were employed.
If strong sulphuric acid and a platinum cathode are used
there is formed a substance containing nitrogen and sulphur,
the chemical nature of which has not yet been determined.
Benzoylpiperidine. — On the occasion of their experiments re-
garding the reduction of acicl amides, Baillie and Tafel,2 by
electrolytical reduction in sulphuric acid at a lead cathode,
converted benzoylpipericline into benzylpiperidine and obtained
a yield of 77 per cent, of the latter compound.
Quinoline was electrolyzed by Ahrens 3 in a 10% sulphuric
acid. The cathode was of lead, and the anode of platinum.
An apparent!}7 tri-molecular hydroquinone (CgH9N)3 was chiefly
formed at the cathode, besides small quantities of hydroquinoline
(C9H9N)2 and tetraliydroqumoline, C9HiiN2.
According to a later patent of E. Merck, 4 if quinoline
is electrolyzed in dilute sulphuric acid containing for 1 equiv-
alent of the base at least 4 equivalents of the acid, and free from
metallic salts, a good yield of dihydroquinoline is obtained.
Acetyltetrahydroqttinoline. — As in the case of benzoyipiperi-

dine, Baillie and Tafel 5 were able to reduce this compound, and
obtained a good yield of ethyl tetrahydroquinoline.
1
Ztschr. 1 Elektrochemie 2, 577, 580 (1898) ; also D. R P. No. 90308 (1896).
2
Rer. d. deutsch. chem. Gesellsch. 32, 74 (1899).
5
4
D. R. P. No. 104664 (1898).
6
Berd. deutsch chem. Gesellsch. 32, 74 (1899).
Quinaldine (a-methylquinoline), according to the process of

Ahrens,1 can be converted into dihydroquinaldine, CioHioNH,
and tetrahydroquinaldine, Ci0 Hi 3 N.
The nitroso- and nitro-derivatives of the pyridine and quin-
oline series have already been discussed (see p. 192).
The coca-alkaloids, like cocaine, atropine, etc., contain per-
haps a combination of a piperidine ring with a pyrrolidine ring.
This combination is also expressed in their behavior in electroly-
sis. At present the following is known.
Atropine, CirHtaNOs.—From the neutral sulphate of atro-
pine crystallized atropine is gradually precipitated at the
cathode, 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 wras not ob-
served (Bourgoin2 ).
Atropine is decomposed by baryta water into tropic acid and
Tropine.
— CH—CH-2
CH3N CHOH=C8HiS NO.
CH2 — CH—CH2
This substance? on electrolysis in alkaline and acid solution at

lead electrodes, and at a low temperature, is converted into tro-
pin one.3
CH.2—CH—CH2
CH3N CO
CH2 — CH—CH2.
A good yield of this substance is obtained. Pseudotropine

behaves in the same manner.
1
2
Bull. soc. chim. 12, 400 (1869).
8
D. R. D. No. 118607 (1900).
?'
220 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS,
Tropinone.—This compound can inversely be easily reduced

t-0 o pure tropine. The chem. Fabrik vorm. E. Sobering 1
e employs as electrolyte an aqueous ammoniacal ammonium
sul-
phate solution.
E. Merck,2 by electrolysis of a slightly alkaline solution, ob-
tains, besides tropine, pseudotropine. The yield is 50 per cent.
of the tropinone employed.
Opium Bases.
Opium. — If opium is subjected to the action of the electric
current, morphine (Ci7Hi9NO(OH)2) goes to the cathode and
ineconic acid (oxypyronediearboxylie acid) to the anode
(Lassaigne).3
Morphine, CiyH^NOs -fH20. — Pommerehne,4 by the elec-
trolysis of a solution of morphine acidified with sulphuric acid,
obtained after a few days crystals of oxydimorphine sulphate at
the anode. The solution became dark-colored.
Codeine (methylmorphine) Ci7H17NO(OH)0 • CH3. — On
electrolysis of the neutral sulphate hydrogen is evolved, codeine
is precipitated, and the solution turns brown (Bourgoin 5).
The acid sulphate undergoes more complete decomposition,
and carbon dioxide, carbon monoxide, oxygen, and nitrogen are
split off.
Cotarnine, C^HisNC^ — This compound is converted quanti-
t tatively by the electrolytic hydrogen into pure hydrocotarnine
- (Brandon and Wolffenstein 6) :
Hydrastimne, CuHisNOs, which does not, indeed, belong to-

the opium bases, may nevertheless be mentioned here. This sub-
stance is similarly converted into hydrohydrastinine, Cn
1
D. R. D. No. 96362 (1898).
2
D. R. D. No. 115517 (1900).
3
Tommasi, Trait4 d'Electrochimie 788 (1889).
4
Arch. Pharm. 2S5, 364 (1897).
* Bull. soc. chim. 12, 400 (1869).
€
Ber. d. deutsch. chem. GeselLsch. 81, 1577 (1898); D. R, P. No. 94949
THE ELECTROLYSIS OF AROMATIC COMPOUNDS 221
Quina- and Strychnos Bases.

Quinine, C2oH24N202-—Although the neutral sulphate is a
Tery poor conductor, the acid sulphate is readily decomposed
into carbon dioxide, carbon monoxide, and nitrogen. The
color of the solution changes to a dark brown.
Besides the last-named gases, the above-mentioned alkaloids
split off various other products, principally complicated nitro-
gen-containing compounds (Bourgoin1 ).
Pommerehne,2 by electrolysis of a sulphuric-acid quinine
solution, obtained a green resinous mass; which is perhaps
identical with thalleioquin (?).
Quinine, cinclwnine (CigB^Ô), and cinchonidine
(Ci9H22N"20), on electrolysis at lead cathodes in a 50% sul-
phuric-acid solution, are converted into non-crystallizable
tetrahydro-bodies (Tafel and Naumann3 ).
Strychnine, C2iH22N202.—The neutral sulphate suffers but
little change. The solution becomes slightly colored, hydrogen
•and oxygen are given off, and crystals of strychnine collect at
the cathode.
The acid sulphate behaves in a like manner, except that in
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 splitting off of nitrogen does not occur (Bourgoin 4).
Tafel and Naumann 5 have made more thorough investiga-
tions regarding the electrolytic reduction of strychnine in strong
sulphuric acid solution at lead cathodes. According to Tafel's
researches, strychnine is to be regarded as a cyclical acid anilide
of the formula:
yCO
(C20H22ON)<J .
_______________________________ ^ N
1
Bull. soc. chim. 12, 400 (1869).
*1. c.
3
4
Bull. soc. chim. 12,400 (1869).
5
Lieb. Ann. 301, 291 (1898); Ber. d. deutsch. chem. Gesellsch. 34
3291 (1901).
i • 222 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
The water-soluble tetrahydrostryelinine is first formed:

3H2OH
(C2oH22ON) '
which by further reduction is converted ink) strychnidine:
(C20H22ON)
.
N
The quantity of the former preponderates at a low temperature.

On the other hand, the higher the temperature the greater the
quantity of strychnidine formed.
Brucine, C2sH26N204. — A solution of the neutral sulphate
turns red and the sulphate is decomposed. Hydrogen is evolved .
at the negative pole, but the brucine completely absorbs the
oxygen at the positive pole (Bourgoin).
The acid salt is very energetically decomposed, becoming
first red and then brown. At the anode carbonic-acid gas,
carbon monoxide, oxygen, and nitrogen escape (Bourgoin1).
Besides the gases mentioned, the above alkaloids break up
into other products, principally complex compounds containing
nitrogen.
According to Tafel's and NaumannV investigations,
brucine behaves like strychnine in so far as that by reduction
under similar conditions tetrahydrobrucine is produced; how-
ever, to obtain the crystalline product the temperature must
not exceed 15°. But a body corresponding to strychnidine
was not found among the products of the electrolytic reduction
of brucine.
If we give brucine the following formula (Moufang and
Tafel*):
CO
1
1. c.
M. c.
3
Lieb. Am. 804*24 (1898).
then tetrahydrobrucine has most probably the formula :

CH2OH
Brucidine, corresponding to strychnidine, is formed from

tetrahydrobrucine if this is heated to 200°, water being split
off:
/CH2
Sv
[C2oH2o(OCH3)aONK X •
N
Morpholone. — Lees and Shedden l have investigated the

electrolytic reduction of pheno- and naphthomorpholones in
sulphuric-acid solution. Morpholines are produced only as
by-products, the morpholone ring being for the most part
broken up.
Phenomorpholone, CH
O2'
•NH-
gives as end-products of the reduction acetyl-o-aminophenol,
/OH
C6H4<
X
NHCOCH3,
also ethyl-o-aminophenol,
/OH
C
X
6H4<
N
and also isoacetyl-o-aminophenol,
/OH
C 6 H<
^
1
Proceed. Chem. Soc. 19,132 (1903); Journ. Chem. Soc. 83, 750 (1903)
n-Methylphenomorpholone,
C6H4<
CH3
gives, besides n-acetylmethyl-o-aminophenol,
OH
/COCH3>
<
X
CH3
and n-methylethyl-o-aminophenol,
/OH
C6H4< /CHaCH3,
\
also n-methylpiienomorpholine,
C6H.
C
H
n-Methyl-/?-naphthomorpholone gives n-methylethyl-a-
amino-/?-naphthol:
and n-methyl-/?-naphthomorpholine:
°\
I
'< «» C CH2
H
/
frj
10. THE CAMPHOR GROUP.
Camphor.—This substance, as shown by the synthesis car-
Tied out by Romppa, 1 has certainly the formula proposed by
Bredt:
CH3
CH2----- CH----- CH2

Being a ketohe it can be reduced to the secondary alcohol
>borneol:
CH3
CH2 ---------C------- CH(OH)
CH2-
This reduction has been carried out electrolytically by Tafel
Schmitz 2 in sulphuric-acid solution at mercury catnodes.
They obtain thus about 45 per cent, of the theoretically possible W'.
yield, with a maximum current consumption of 38 per cent.
.At lead cathodes no satisfactory reduction can be effected.
Camphoric Acid,
CH3
m
CHo-- C --- COOH *
CH2---- CH -- COOH
is the oxidation product of camphor with nitric acid.
Brown and Walker3 also electroylzed (see p. 102) the
.sodium-ethyl salt of camphoric acid and obtained two esters
"-which they were able to separate by means of fractional dis-
1
Ber. d. deutsch. chem. Oesellsch. 86, 4332 (1903).
2
*Lieb. Ann. 274, 71(1893).
tillation. One of these (boiling-point 212°-213°) on being;

saponified yielded an unsaturated monobasic acid, CoHÔ^
cwnpMytic add; the other having a higher boiling-point
(240°-242°), was the neutral ester of a diabasic acid, CisHscAi,
to which Walker gave the name of camphothetic acid. These
experiments are of great importance, because they prove t he-
dibasic nature of camphoric acid, a fact which was doubted
by Friedel.
1
Walker and Henderson found, moreover, that upon
electrolysis of concentrated aqueous solutions of the ethyl-
potassium salt of allocamphoric acid there are formed as chief
products the ethyl esters of a dibasic acid, CieE
and of a monobasic acid, CgHisCOOH:
xCOOCsHs /COOCaHs
1. 2C8H14< -2C02 + C16H28<
X X
COO COOC2H5
xCOOC2H5
2. 2CgHi4<' = CsHi4<T
X
N COO COOH
It has been found on further investigation 2 that

besides the
strongly dextrorotary unsaturated acid designated as allocam-
pholytic acid, CgH^COOH, an isomeric acid is formed which,
although slightly dextrorotary as obtained, is perhaps even
laevorotary in an entirely pure condition. The latter on being"
heated to 200° splits off carbon dioxide and yields a hydrocarbon,
CsHi4, which boils at 120-122° and appears to be identical with
laurolene,
CH2 -CR
1 ,
:
y CH2—
made from camphoric acid.
A ketonic acid, C8 Hi 3 O-COOH, melting-point 228°, is also-
found as an additional product of the electrolysis of potassium
1
Journ. Chem. Soc. 67, 337 (1895).
2
Ibid. 69, 748(1897).
alloeamphoric ethyl ester. The authors concluded from their

observations that camphoric acid contains the group
H
H-O * •i
-0 / H
V\COOH
-C-COOH,
a deduction which had, of course, to be later modified.

According to later experiments of Walker and Cormack, 1 it-
is possible to obtain isolauronolic acid by eleetrolyzing the
methyl-ester-potassium salt of camphoric acid:
/COOCH3 ,COOCH3
2CSH14< - CSH14< +C0 2
X X
COO - COOH
+CSH13COOCH3.
The free optically inactive isolauronolic acid,
CH2—CCOOH
II
CH3C
CH2—i
°
The electrolytic reaction
\
CH3
was obtained from the latter ester.
occurs hence in a normal direction.
Camphoric-acid imide,
>NH
mi
CH3
CH2—C ------ COs
CH2—CH—CO/
was reduced in sulphuric-acid solution at a prepared lead
cathode. The experiment was made by Tafel and Eckstein,2
in connection with their investigations concerning the electro-
^Proceed. Chem. Soc. 16, 58 (1900).
2
Ber. d. deutsch. chem. GeseUsch. M, 3274 (1901); see also D. R. P
No. 126196 (1900).
Ivtic reduction of succinimide (p. 119). Just as succinirnide, by

replacement of one of the two oxygen atoms by two hydrogen
atoms, is converted into pyrrolidone and, by complete elimina-
tion of the oxygen, into pyrrolidine—although only to a very
slight extent—so camphoric-acid imide gives two perfectly-
analogous products, camphidone and camphidine.
Camphidone occurs in two isorneric modifications, separable
in the form of the picrates, a-camphidone and /3-camphidone:
CH3 CH3
CH2 ~C CH2 —C-CH2
NH and >NH.
CH3CCH3 CH 2 —CH-CO'
CE 2 -CE-CH 2 '
Which one of these is the a- and which the /3-camphidone

remains undecided.
Camphidine,
CH3
CH2— C — CH2*
is always produced besides
CH 2 -
camphidones, and can be readily
separated from these, since it possesses a decidedly basic char-
acter.
As the camphidones are extremely resistant towards further
reduction, they form no intermediate phase in the camphidine
formation. We must suppose that only those acid-imide
molecules, both of whose carboxylic groups are by accident
simultaneously attacked by the reducing agent, are changed into
camphidine. Or, a carbinol-like intermediate product, in
which the second carboxylic group—in contradistinction to
that of camphidone—is electrolytically attackable, is already
formed during the transition from camphoric-acid imide to the
camphidone.
11. ELECTROLYSIS OF BLOOD AND ALBUMEN .

Blood.1—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 Daniell cells. At
the negative pole he observed the following phenomena:
The blood became brown and alkaline, and contained
neither white nor red corpuscles; it possessed the property of
gradually dissolving blood-corpuscles and had the odor of putrid
meat.
At the positive pole uridecomposeci and partially decomposed
blood-corpuscles were present in large quantities. The fluid
gave a precipitate of albumen with nitric acid, mercuric chlo-
ride and lead acetate.
Albumen.2—When an albumen solution was electrolysed by
Dumas and Prevost7 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 at the negative pole (by the alkali present), while at
the positive pole the solution remains clear.
As Lassaigne has shown, pure albumen in aqueous solution
is a non-conductor of electricity; the addition of salts or acids
is therefore necessary in its electrolysis.
m
The Pharmaceutical Institute of L. W. Gans of Frankfurt3 t:Pi
has made known a process for electrochemically preparing
fluorine-substitution products of albumens. The latter are
suspended, or dissolved in a dilute aqueous solution of hydro-
fluoric acid or salts of this acicl, and subjected at a platinum
electrode to the anode current action. The discharged fluorine
reacts with the albumen, forming substitution products.
1
Tommasi, Trait6 d'Electrochimie 800 (1889),
2
I.e.
S
D. R. P. No. 116881 (1898).
CHAPTER V.
~ ELECTROLYSIS WITH ALTERNATING CURRENTS.
IF the polarity of the current is not allowed to change too

rapidly, it is possible, since oxidation and reduction occur suc-
cessively at each pole, to accomplish electrolyses with alternat-
ing currents. Experiments with this end in view have been
made by Drechsel.1 Dehydration is a case of simultaneous
reduction and oxidation. The supposition that in living organ-
isms carbamide is produced from ammonium carbamate by the
splitting off of water prompted Drechsel to make experiments in
this direction. When an aqueous solution of ammonium car-
bamate is electrolysed with a current from a battery of 4-6
Grove cells, and platinum electrodes used, carbamide is obtained
independently of the electrode material when alternating currents
are employed. The reactions are supposed to be either
I. NH2COONH4-f 0 =NH2COONH2 4-H20;
II. NH2COONH2 +2H=NH2CONH2+H20,
or
II.
The observation that the platinum electrodes were strongly
attacked, with the formation of platinum salts, caused Gerdes 2
to investigate the platinum bases. As the principal product he
found a compound to which he gave the following formula :
/3,
C0< Pt
X}NH3 J
* Journ. prakt. Chem. 22, 476 (1880); Ber. d. deutsch. chem. Gesellsch.
18,2436 (1880).
2
Journ. prakt. Chem. 26, 257 (1882); see also Inaug-Dissert., Leipzig
1882.
230
ELECTROLYSIS WITH ALTERNATING CURRENTS. 231
and the chloride of which is said to have the composition

C1NE3N / s a
>Pt< Ptam-2E 2 0.
C1NH/ XNH3NH3CF "
Gercles also examined the nitrate and sulphate of this base.
In the course of further researches l Drechsel found that
when alkaline solutions were used platinum "was present in the
electrolysed fluid. Copper when used as electrode showed a
similar behavior; lead was less attacked, gold but very slightly,
and palladium not at all.
The formation of phenylsulphuric acid in living organ-
isms is supposed, like carbamide, to be the result of dehydra-
tion. Taking this into consideration, Drechsel carried out the
following experiment:
A saturated solution of aeicl magnesium carbonate was mixed
with an equal volume of a solution of magnesium sulphate and
the mixture was saturated with commercial carbolic acid.
When this solution was electrolyzed for thirty hours with
alternating currents, using platinum electrodes, then the follow-
ing products were obtained :
1. /--Diphenol. 7. Succinic acid.
2. Pyroeateclin. 8. Malonic acid (?).
3. Hydroquinone. 9. n- Valeric acid (?).
4. Phenylsulphuric acid. 10. n-Butyric acid (?).
5. Oxalic acid. 11. Some cyclohexanone,2
6. Formic acid. CsHioO.
According to Drechsel the formation of the phenol ester of
sulphuric acid is probably represented by the following equa-
tions:
I. C6H5OHH- KOS03H +0 - C6H6OOS03H+H20;
Later Drechsel 2 electrolyzed normal caproic add with alter-

nating currents. The electrolytic solution contained, in a vol-
1
Joum, prakt. Chera. 29, 229 (1884).
2
Ibid. M, 135 (1886).
ume of 3 liters, 200 g. of caproic acid as magnesium salt and

was nearly saturated with acid magnesium carbonate. Plati-
num electrodes were used. At the end of the experiment the
following compounds could be identified in the solution:
1. Valeric acid. 5. Adipic acid.
2. Butyric acid. 6. Oxycaproic acid.
3. Oxalic acid. 7. Glutaric acid.
4. Succinic acid.
In a still later research on the electrolysis of phenol with
alternating currents Drechsell detected phenylsulphuric acid,
dioxybenzenes, a number of acids of the fatty acid series, and
in addition to these an oil which he identified as hydropheno-
ketone,
CH2*
H2C C:0
If . II'
< H-2C CH.2
; \y
CH2
and whose phenylhydrazine compound he was able to isolate.
Drechsel regards hydrophenoketone as the origin of the
i fatty compounds formed. By the direct addition of water to
this compound caproic acid results, and this then breaks up
into the acids and other decomposition products mentioned
above.
;j Some of the above acids have been mentioned as decompo-
1
sition products of phenol in the investigation cited on the elec-
| ; trolysis of phenol.
1
' * ,, • Journ. pract. Chem. 38, 65 (1888).
*, ,
$ !'
CHAPTER VI.
ELECTRIC ENDOSMOSE.
BY electric endosmose or cataphoresis is meant the often

observed phenomenon of the migration or flow of a fluid, under
the influence of potential differences, through the diaphragm
separating the cathode and anode chambers. This flow or trans-
portation of fluid always occurs in a certain direction, either
to the anode or to the cathode, depending upon the nature
of the substances and the diaphragm; it has no connection
with the electrical phenomena following Faraday's laws. If
the rigid d'aphragm is replaced by fine suspensions which act
like a movable diaphragm, the fluid remains at rest, but the
suspended particles migrate, i.e., are urged in the fluid towards1
the electrode. This directed movement depends undoubtedly
upon a polar charge of the suspended particles contrary to that
of the water. Since the organic colloids, like the colloid solutions
of albumen, carbohydrates, haemoglobin, indigo, and of natural
dyes, act as an extremely fine suspension, cataphoresis also
possesses great importance for organic substances, as to their
suspension, coagulation and sedimentation phenomena. The
scientific treatment of this field has begun. Bredigl mentions'
that the direction of albumen depends upon the chemical com-
position of the fluid; for instance, whether the aqueous medium
is alkaline or acid.
Electric endosmose is of technical importance for the4
dehydration of organic, finely suspended substances containing1
very much water, for example, the drying of peat, according,
1
to the experiments of Schwerin. 1 The peat, at a tension of

4 to 5 volts per centimeter peat layer, migrates to the anode
and is deposited on the latter in a firm coat, while at the cathode
the water becomes clear. Aqueous dye-pastes behave simi-
larly. The technical purification of albumens by cataphoresis
is also said to be feasible.
Another field in which cataphoresis, or the convective con-
duction as the process is also called, has apparently already
become of great importance, is the tanning industry.
If the skin to be tanned is brought between the cathode
and anode in a dilute tannic-acid solution, a migration of the
colloidally dissolved tannic acid takes place through the skin
from the positive to the negative electrode. By a regular
slow change of the "current direction the tannic-acid solution
can be pressed into the pores of the skin and thus a considerable
saving in time is accomplished.2
Note.—It has been known for a long time that many finely
divided bodies suspended in water, as gold, copper, graphite,
silica, feldspar, sulphur, lycopodium, etc., as well as minute drops
of liquids, such as 682 and oil of turpentine, and bubbles of
oxygen, marsh-gas, etc., show cataphoresis phenomena. All
these are urged in water towards the positive electrode, but in
oil of turpentine the direction is reversed except in the case of
particles of sulphur; the direction is also reversed for silica in
carbon disulphide. The earlier experiments along these lines on
solid particles contained in fluids of high resistance were made
by Faraday, Jiirgensen, Quincke, etc.—Translator.
1
Ztschr. f. Elektrochemie 9, 739 (1903); D. R. P. No. 131932 (1901).
2
S. Foelsing, Jahrb. d. Elektrochemie 2, 269 (1895).
PART II.
.4
,'!'
ELECTROTHERMIC PROCESSES AND THE SILENT
ELECTRIC DISCHARGE.
yj'VV
* >
CHAPTER I.
THEORETICS AND METHODICS.
1. THEOBETICS.
ACCORDING to Ohm's law the strength or intensity of the
electric current, i.e. the quantity of electricity which is con-
ducted by an electric conductor or a system of conductors
in a given time, is directly proportional to the effective electro-
motive force, and inversely proportional to the resistance
of the current field:
li-
w
where i is the current strength, e the electromotive force or
the tension, and w the resistance. The work which elec- fe;
trical energy can perform in a current field is expressed by
the product of the electromotive force existing in this field
and the current strength
where A denotes the work to be done.

Substances are known which interpose a more or less strong
resistance to the passage of the current, and such whose resist-
235
ance is so great that practically no passage of the current

takes place. The former are called, conductors of electricity;
the latter non-conductors or insulators. The conductors
themselves are in turn again subdivided into two sharply
defined classes; those which conduct the current without
being materially changed, i.e. the passage of electricity pro-
duces no change in the chemical composition of the substance,
and those—presenting a remarkable contrast to the former—
in which the passage of electricity results in the chemical
decomposition of the substance of the conductor at points
where the electric current enters and leaves the body, i.e.
Ranges of the substance occur. To the former class of con-
ductors belong all metals and carbon, the conductors of the
first class; to the latter the bases, acids, and salts in solution,
particularly aqueous solution, or in a molten, and also, under
certain conditions, in a solid, 1 state. They form conductors
of the second class, or electrolytes.
Ohm's law is equally applicable to both classes. The
work which the current can do, however, depends upon the
nature of the conductor. If the circuit is completely metallic
and closed, the total electric energy can be converted into
heat; but if the circuit contains an electrolyte, a large part
of the electric energy is used up in the production of chemical
,and physical effects which occur wrhen the circuit is closed.
To determine in a simple way the connection of the electric
•energy with the calorific energy caused by it, an electric cir-
cuit can be closed by a metallic wire placed in a calorimeter,
.and the current measured calorifically by the heat effects
produced by the different electromotive forces and intensi-
ties. The result of such measurements is the equivalence of
the heat occurring in the conductor with the electric energy,
hence with the product of electromotive force into the electric
quantity
Q = kei,
where Q denotes the heat generated in the wire. The factor k
is the electrical equivalent of heat, which permits a numerical
, - __ , —.. - . -,--...- - ______ u
-1 See Nemst, on "solid electrolytes/' Zeit. f. Elektrocheinie 6, 41-43 (1899).
fJ
THEORETICS AND METHODICS. 237
comparison of the two forms of energy. It follows, that

0.239 cal = l voltxl coulomb.
If we introduce from Ohm's law tJtie factor iw for the elec-
tromotive force e, then
The amount of heat generated in a given time varies directly

as the product of the resistance of the conductor into the
square of the current strength. This relation is called Joule's l
law, named after its discoverer. The heat which is thus derived
only from the current quantities, but not from chemical changes,
is also called Joule's heat.
If, besides the metallic connections, an electrolyte is included
in the closed circuit, a part of the electric energy is used up
in chemical work. The electrical energy is then transformed
in various ways,—in all parts of the current 'field heat is j|| | f
developed proportional to the resistance of each separate
part and the square of the current strength, but chemical
work and material changes and disarrangements in the elec-
trolyte are also accomplished.
In utilizing the heat produced by the current for reactions of H fy
organic bodies, only those systems are taken into, account in
which the current, by forming a spark discharge or luminous *'$;\
arc, is forced either to pass through gases or vapors with high I |f I
resistance, or to heat wires or filaments to high temperatures.
While the extremely high temperatures, which can be attained
by means of the voltaic arc in the electric furnace, have through ^vr-ui
Moissan's investigations become of great importance for mineral
chemistry, it is a peculiarity of organic substances, whose con-
ditions of existence, with few exceptions, are connected with
relatively low temperatures, and are mostly quite sensitive,
that the methods applicable here must allow a fuller scope in
temperature than is accorded by the spark discharge or luminous
arc. RuhmkorfPs coils, and less often frictional electric machines,
1
Phil. May 19, 260 (1841).
are usually employed for giving sparks. The resistance fur-

naces, in which a tube of carbon is heated by the current, seem
more suited for carrying out pyrogenic reactions of carbon com-
pounds. Both heating methods have already been used. Lep-
sius 1 has employed the luminous arc for decomposing gases and
demonstrating volumetric proportions, also for preparing water
gas. Bredig2 made some qualitative tests on the behavior of
separate organic fluids towards the luminous arc, while Hofmann
and Buff3 have also investigated the effect of electrically incan-
descent platinum and iron wires on some gases and vapors.
Legler,4 in his experiments on the incomplete combustion of
ether, also employed electrically heated platinum. Moreover,
Haber,5 by making the heated conductor (of platinum, plati-
num-iridium, or carbon) tube-shaped and conducting the cur-
rent of gas through the hollow centre in which was placed a
glass or porcelain tube, perfected the principle of resistance
ovens for the chemical investigations of gases. But these in-
vestigations did not lead to an extensive use of these- electrical
methods for obtaining pyrogenic reactions with organic bodies.
Most of the material of such reactions has so far been collected
with the spark discharge between metallic electrodes; of late
years numerous experiments on the pyrogenic reactions of or-
ganic bodies have been undertaken with electrically incandes-
cent wires or filaments.
2. THE REACTION TEMPERATURES .
Before taking up the subject of the individual results, some
remarks on the attainable temperatures, the possibility of their
variation, their measurement and calculation will be made.
No very accurate measurements of the temperatures occur-
ring in the spark discharged are available, great difficulties
1
Ber. d. deutsch. chem. Gesellsch. 23, 1418, 1637, 1642 (1890).
2
3
Lieb. Ann. 113, 129 (1860).
4
Ibid. 217, 381 (1883); Ber d. deutsch. chem. Gesellsch. 18, 3350 (1885).
5
Experimental Investigations on the Decomposition and Combustion
of Hydrocarbons (Munich, 1896) 43.
being encountered in their determination. Calorific methods

are best suited for investigating the temperature of the lumi-
nous arc, or the radiant energy is employed for learning the
temperature. In the latter case a bolometer or photometer
is used.
According to Violle,1 the temperature of the positive car-
bon point and of the carbon particles in the voltaic arc equals
the evaporation temperature of carbon. This was determined by
breaking off the incandescent tip of the carbon and dropping it
into a calorimeter. One gram carbon requires 1600 cal. to heat
it from 0° up to its evaporation temperature. As 300 cal. are
necessary to heat it from 0° to 1000°, 1300 cal. remain for raising
the temperature from 1000° to 3°, if x is the evaporation tem-
perature of carbon. If we take the specific heat of carbon
at 0.52, then 1300 cal. represent 2500° more, so tliat the evapo-
ration temperature of carbon, x} and the hottest parts of the
luminous arc, equal 35000.2
Langley, Paschen, Violle, and Le Chatelier2 sought to
determine the temperature of the heated body by means of
the radiant intensity.
The use of the thermopile in the form of Le Chatelier 7s3
platinum, platinum-rhodium thermocouple, a so-called pyrom-
eter, has obtained especial importance. This can be used to
measure temperatures up to 17000.4 The electromotive force is
measured either by one of the well-known methods, or else direct
reading precision-voltmeters (or galvanometers), whose scales are
divided both into millivolts and into the corresponding degrees
Celsius or Fahrenheit, are employed. The determination of the
1
Cpmpt. rend. 115, 1273 (1892); 119, 949 (1894).
2
Bams, Die physik. Behandlung und die Messung hoher Temperaturen,
Leipzig, 1892; also Bredig, Uber die Ghemie der extremen Temperaturen,
Leipzig, 1901.
3
Le Chatelier et Boudouard, Mesure des temperatures elevens, Paris,
1900. Le Chatelier, Compt. rend. 114, 470 (1892) etc. Holborn u. Wien.
Ann. 56, 360 (1895); 59, 213 (1896); Holborn u. Day, Wied. Ann. C8, 820
"(1899), etc.
4
Wanner's Optical Pyrometer indicates up to 4000° C. See Journ. Am.
Chem. Soc., 1904.
temperature from the electromotive force is based upon the

fact that on heating the joint where the platinum wire is fused
to the platinum-rhodium wire, an electromotive force of about
one millivolt for every 100° C. is produced. The ratio of the
electromotive force to the temperature of the fused joint
is accurately determined by the Physik-tech. Reichsanstalt,
and the result accompanies the calibrated pyrometer. The
data always refer to an arrangement whereby the connections
between the thermocouple and the conducting wires are at 0°,
while the fused joint of the couple is placed in the space
whose temperature is to be measured.
The resistance thermometer l is extremely convenient for
measuring wide ranges of temperature. The electric resistance
of pure metals increases with the temperature about 0.4%
per degree (C.); but the temperature coefficient for different
metals and also for different temperature intervals is by no
means constant. 2 If the temperature coefficient is known,
for accurate purposes the resistance during the experiment
can be measured with a "Wheatstone bridge; for less accurate
measurements it will often be sufficient to determine the ten-
sion of the incandescent wire and the intensity in the current
circuit, and to calculate the resistance according to Ohm's
law. Care must, however, be taken that the conducting wires
connected with the wire whose temperature is being inves-
tigated are practically without resistance. For showing the
dependence of the resistance upon the temperature an equa-
tion of the following form usually suffices:
or
The values a, 6, and c, or a, /?, and f are given in the tables.

Pyrogenic reactions, whose course remains the same within
* Holborn and Wien, Wied. Ann. 56, 383 (1895); 59, 213 (1896). Cal- *
lendar, Phil. Mag. 32, 104 (1891).
2
Landolt-Bornstein, Physik.-Chemische Tabellen.
larger temperature intervals, permit of a further simplification,

naturally at the cost of accuracy. If we make
in which the range of the respective temperature must be con-

sidered in the choice of a, then
QL'W0
a is for iron about 0.0045, for nickel 0.0036; for platinum

0.0033, and for platinum-indium (20% iriduini) 0.00105, all
metals in wire shape. Tliis approximate determination is
convenient, even if pyrogenic reactions are brought about by
the wire itself, whereby an accurate determination of reaction
temperature often becomes illusory for the most .various reasons.1
3. ARRANGEMENTS.
Little can be said about the arrangements to be chosen for
the pyrogenic reactions of organic bodies. Both the spark
discharge and the luminous arc can be produced in fluids or
molten substances. Lob,2 in decompositions with, the luminous
arc, employed a small flask with three tubulures, about the
shape aad size of the boiling-vessel employed in Beckmann/s
method for determining molecular weights. Each of the two
side tubes of equal dimensions supports a thin carbon rod
passed through the perforation of a tightly fitting stopper,
so that the electrodes in the inside of the vessel are at an angle
to one another. The centre tubulure supports a return con-
denser to which is attached an arrangement for collecting the
generated gases. By regulating the "volume of the liquid in
the decomposition flask the luminous arc can at will be pro-
duced in the liquid or its vapor. In the latter case the sub-
stance is heated to boiling and the circuit closed as soon as the
air in the apparatus is displaced by the vapor.
1
LOb, Ztschr. f. Elektrochemde 7, 903 (1901).
2
Ber, d. deutsch. chern. Gesellsch. 34, 915 (1901).
The degree of decomposition by the voltaic arc depends

of course, to a great extent upon the chemical nature of the
liquids and vapors in which the luminous arc is produced-
While ether, methyl alcohol, ethyl alcohol, glacial acetic acid,
and other aliphatic fluids and their vapors are subject to decom-
positions with very trifling charring, and give products which are
chemically closely related to the products started with, benzene,
toluene, nitrobenzene, aniline, naphthalene, phenol, and other
members of the aromatic series are destroyed, and considerable
charring results.
For this reason the method worked out and employed by
Lob,1 replacing the luminous arc by metallic and carbon re-
sistances, proves in general to
be more suitable for the pur-
| pose of obtaining pyrogenic re-
actions of organic substances.
A round flask with a long
neck is closed with a thrice-
perforated stopper. Two small
glass tubes with strong platinum
hooks sealed in the lower ends
are passed through the two side
perforations; a little mercury
forms the connection between
the hooks and the conducting
wires leading in. Or, strong
wires bent into hooks at one end
FIG. 8.—Eleetropyrogenizer. are directly stuck through the
stopper, which can be done with-
out injuring the tight fit. The incandescent wire, a metallic wire
of about 0.2 mm. diameter, is fastened to the hooks by wrapping
it around or hooking it on. A return condenser is placed in
the centre perforation. Lob, when making decompositions in a
perfectly air-tight apparatus and under diminished pressure,
replaces the stopper by a ground-glass stopper in which the
1
L6b, Ztschr. 1 Elektrochemie 7, 904 (1901); 10, 505 (1904).
small tubes with platinum hooks are sealed in. The return
condenser, which serves as an internal cooling apparatus,
is attached to the side; another glass tube sealed in the wall
of the flask (not shown in the figure) serves for admitting air,
or for the passage of other gases for special purposes (see
Fig. 8). This apparatus is particularly adapted for pyrogenic
reactions of high-boiling substances in a partial vacuum. The
substance is placed in the round bulb. Direct heating converts
it into vapor, which, after the air has been removed, is per-
manently in contact with the incandescent wire.
CHAPTER II.
THE SPARK DISCHARGE AND THE VOLTAIC ARC.
1. THE SPARK DISCHARGE.

It is well known that most of the gaseous hydrocarbons of
the aliphatic series when exploded with an excess of oxygen are
converted into the end-products of combustion, carbonic acid
and water. This fact is made use of in quantitative gas analysis.
The combustion is often not complete; intermediate products
can be obtained if we start with hydrocarbon derivatives instead
of the hydrocarbons themselves.
Berthelot gave a comprehensive exposition of the results
known at that time on the effect of the spark discharge upon
the formation and decomposition of carbonic acid and hydro-
carbons and the herewith occurring equilibrium phenomena
(Berthelot, Essai de M<§canique Chimique II, 336-362, Paris,
1879).
Methane.—The induction sparks decompose this substance
into carbon and hydrogen (Hofmann 1 and Buff), which fact
Dalton had already observed.
Berthelot 2 obtained hydrogen, carbon and acetylene. If
the latter is continually gotten rid of, the greater part of methane
can be converted into acetylene,'otherwise the latter is decom-
posed and changed in a complex manner.
Methane is also produced by the reaction of carbon monoxide
with hydrogen under the influence of the induction spark
1
Lieb. Ann. 113,129 (1860).
2
Ibid. 123,211 (1862).
244
THE SPABK DISCHARGE AND THE VOLTAIC ARC. 245
(Brodie a), a fact which, explains the formation of hydrocyanic

aeid from carbon monoxide, hydrogen, and nitrogen, as will
be mentioned further on.
Ethylene is decomposed "by the spark discharge into its
elements (Dalton, Hofmann, and Buff2). According to Wilde,3
acetylene is first formed, and is then decomposed into its
elements. Besides, according to Thenard and Berthelot,4 a
fluid and solid product are produced.
W. G. Mixter 5 has. recently investigated the combustion
phenomena of several hydrocarbons by means of a weak electric
spark discharge, and has proven among other things that
ethylene can also yield acetic acid besides carbonic acid. The
pressure under -which the gases react is important for the course
of the experiment. Mixter sought to determine the relative
reaction -velocities as compared with, that of an oxyhydrogen
mixture, under equal conditions.
Acrolem, CH2:CH-CHOJ according to E. von Meyer,6 is
formed when ethylene with an excess of oxygen is exploded in
a eudiometer.
Formic Acid.—Wilde 7 found that the action of the electric
spark on gaseous mixtures of oxygen and alcohol, hydrogen and
carbon dioxide, and methane and carbon dioxide, produced
formic acid. In the first and last mentioned of these mixtures
acetic add is also formed.
Acetylene.—The spark acts, as already mentioned, by
reason of its high temperature which, according to Berthelot,8 is
sufficient to produce acetylene from a mixture of carbon disul-
phide and hydrogen, sulphur being precipitated.
1
Lieb. Ann. 1G9, 270 (1873).
2
Ibid. 113,129(1860).
3
Ztschr. f. Cheniie 2, 735 (1866).
4
Tralt<§ de M<§caiiique chirnique II, 350 (1879).
8
Ann. Joum. of Sc. [4] 4, 51 (1897); Jotirn. Chem. Soc. 73, 246 (1898);
Proceed. Chem. Soc. 39 (1898).
• JOUTH. f. prakt. Cheniie [2] 10, 113 (1874).
7
Bull. soc. cliixn. [2] 5,267 (1866).
• 8 Tommasi Trait 6* d'Eleetrochimie 715 (1879).
Hydrocyanic Acid. — Berthelot1 obtained this substance

by passing the electric spark through a mixture of acetylene and
nitrogen. The acid is in fact frequently produced in far-
reaching decompositions by the electric spark; thus from a
mixture of ethylene or aniline vapor with nitrogen (Berthelotx),
from a mixture of acetylene with nitric oxide (Huntington2),
•ammonia with benzene, or ether and nitrogen (Perkin3), etc.
The reactions are also in a certain sense reversible. Hydrocyanic
acid is readily split up by the current (Gay-Lussac 4), and in the
presence of hydrogen (Berthelot 5), into acetylene and nitrogen.
The union of acetylene and nitrogen to hydrocyanic acid
takes place rather smoothly if the easy decomposability of
acetylene is lessened by dilution with hydrogen, as was already
done by Berthelot. 6 His experiments were recently again
taken up by Gruszkiewicz.7 The electrodes were blackened by
a deposition of carbon except with a maximum content of
acetylene of 5 per cent, by volume (composition of tne gas
mixture-: 5 per cent, acetylene, 5 per cent, nitrogen and 90 per
cent, hydrogen).
Gruszkiewicz obtained better results by using a mixture of
carbon monoxide, hydrogen, and nitrogen. He found that the
proportion of the components was essentially decisive for the
yield and the reaction velocity. A mixture approximately cor-
responding in composition to that of water gas, Dowson gas,
generator gas, etc., gave encouraging results. Thus, if 3 liters
of a gas mixture of 54.62 per cent. CO, 24.88 per cent. N£, and
20.50 per cent. H2 were permitted to flow for an hour through
the space through which the sparks were discharged, then about
12 cc. hydrocyanic acid were obtained. Carbon dioxide, like
carbon monoxide, is reduced by hydrogen in the spark dis-
1
Bull. soc. chim. [2] 13, 107 (1869).
2
D. R. P. No. 93852 (1895).
8
Jahresb. f. Chemie. 399 (1870).
* Ann. chim. phys. 78, 245 (1811); Gilberts Ann. 1811.
8
Bull. soc. chim. [2] 13, 107 (1869).
6
Trait£ de MScanique chimique II, 355 (1879).
7
THE SPARK DISCHARGE
AND THE VOLTAIC ARC.
247
charge, and changed, by uniting

with nitrogen, into hydrocyanic
acid. The reaction can be shown in the equation,
2CO+3H2 4- N2 = 2HCN + 2H20;
or, 2CO+6H2=2CH4+2H20
2CEU+N2«2HCN+3H2.
Cyanogen shows the same easy decomposability as hydro-
cyanic acid. Both Berthelot l and Hofmann and Buff2 ob-
served that cyanogen, was decomposed into its elements by the
action of the electric spark. The least trace of water in the
gas caused the formation of hydrocyanic acid and acetylene.
The observation of Morrens,3 who claimed to have obtained
cyanogen in an atmosphere of nitrogen by passing the induction
spark between two carbon electrodes, is therefore incorrect.
The decomposition of cyanogen by the action of the electric
spark has, moreover, been noted by Davy, and by Andrews
andTait.4
Ethyl Alcohol.—In an atmosphere of ethyl-alcohol vapors,
M. Quet5 and Perrot 6 obtained, besides some carbon, a sub-
stance which exploded on being heated, the chemical nature of *\
which they were unable to determine. The liquid became acid
but Perrot found that no water was formed in the decomposi-
tion of the alcohol; he was also unable to prove the presence
of carbonic acid gas. Melly 7 and Lommel8 made similar ex-
periments, the latter employed a Holtz machine. The gas
escaping in the decomposition of the alcohol probably contains
acetylene and ethylene.
Ethyl Ether.—According to Wilde's9 experiments, ethyl
ether, under reduced pressure, also yields ethylene besides other
1
Compt. rend. 82, 1360 (1876).
m
2
Lieb. Ann. IIS, 129 (1860).
3
Compt. rend. 48, 342 (1859).
4
Journ. Chom. Soc. 13, 344 (1861).
1
Compt. rend. 46, 903 (1858).
8
Ibid 46, 180 (1858); 47, 351 (1859).
7
Tommasi, Trait6 d'Electrochimie, 724 (1879).
8
Ibid, 725 (1879).
8
Ztschr. f. Chemie 2, 735 (1866).
gases, and a deposition of carbon. Truchotl observed methane

:
and hydrogen besides the ethylene. Perrot,2 by the action of
bromine upon the gases obtained by the action of the electric
* spark, was able to isolate a liquid, C3 H5Br3; boiling at 135°-
140°, and isomeric with tribrornhydrin. Klobukow, 3 by heat-
ing ether vapor to 250°-300° and passing the spark through
the-latter, obtained carbon monoxide, hydrogen, methane, ethyl-
ene, and acetylene.
Acetone.—Wilde4 investigated the action of the electric
spark on acetone vapor in a Torricelli vacuum. Acetylene was
1
formed in the gas mixture and carbon was deposited on the
sides of the vessel.
Formic Acid, on the contrary, does not yield acetylene
^. (Wilde). Nor could he prove the presence of this gas in the
%t
f , decomposition of acetic acid.
Metlaylamine.—-The electric spark, when passed through
|> methylamine vapor by Hof mann and Buff,5 gave primarily hydro-
; ^ gen and methylamine hydrocyanide; further action brought about
4' complete decomposition, tarry substances being deposited.
Trimethylamine was investigated by the same authors. It
also is completely broken up, tarry products being formed.
Ethylamine.—Hof mann and Buff obtained tar-like products
and a non-alkaline gas having an odor like that of ethyl cyanide.
' The experiments carried out on the behavior of compounds
of the aromatic series when subjected to the electric spark have
so far given very few results.
; ^Benzene.—Destrem6 investigated the action of the indue-
/ tion spark between two platinum points on benzene, and ob-
\ tained a gas mixture of acetylene and hydrogen, while the liquid
\ contained diphenyl and a crystalline substance which was not
:j closely investigated Benzene vapor, under reduced pressure,
^,^ . -------------------------------------------------- ...........—.
'4 i Compt. rend. 84, 714 (1877).
,f * Ibid. 46, 180 (1858).
8
|| Journ. f. prakt. chemie [2] 34, 126 (1886).
',{ * Bull. soc. chim. [2] 5, 267 (1866).
j| * Lieb. Ann. 113, 129 (I860).
6
"' Bull. soc. chim. 42, 267 (1884).
m
i :
THE SPARK DISCHARGE AND THE VOLTAIC ARC. 249
is decomposed by the electric spark, likewise producing acetyl-

ene (Wilde2).
Toluene. — Destrem1 obtained from toluene, as from ben-
zene, acetylene, and hydrogen. The liquid contained, besides.
diphenyl, a solid substance which was not further investi-
gated.
Naphthalene. — Wilde2 also investigated the behavior of
naphthalene vapor under reduced pressure when subjected to-
the action of the induction spark. He obtained a gas mixture,
containing acetylene.
Aniline. — Destrem3 investigated the action of the electric-
spark from an induction apparatus on aniline vapor, and
observed a decomposition into acetylene, hydrogen, hydro-
cyanic acid, and nitrogen.
Pyrogenic reactions of organic compounds with the "'electric:
flame/' (flaming discharge) as produced at a lower tension and
higher intensity than required for the production of the spark
(at about 2000-4000 volts and 0.05-0.15 amp.) have not yet
been carried out.
According to the investigations of W. Muthmann and EL I
Hofer,4 interesting results are also to be expected in its appli-
cation to organic compounds. I
2. THE VOLTAIC ARC .
As already mentioned in the introduction, the enormously
high temperature of the luminous arc is only applicable in
certain cases to organic compounds.
Several reactions have, however, become of fundamental,
theoretical and practical importance; for instance, Berthelot's
acetylene synthesis, the preparation of carbides, and some
other processes.
1
Bull. soc. chim. 42, 267 (1884).
2
Ibid. 5, 267 (1866). '
•1. c., see also Jahresb. f. Chem. 272 (1884).
4
Ber. d. deutsch. chem.Gesellsch. 36, 438 (1903).
Acetylene.—Berthelot1 showed that carbon and hydrogen

combined to acetylene on passing the voltaic arc over carbon
points in an atmosphere of hydrogen. The synthesis of acety-
lene from its elements first made possible the complete syn-
thesis of a whole series of organic compounds. Acetylene, as
is well known, is produced by the decomposition of many
organic compounds at high temperatures. Bredig 2 thus
obtained acetylene, besides other hydrocarbons, when he pro-
duced the luminous arc in liquid petroleum.
The Metal Carbides.—These are of great technical and scien-
tific importance. They have been repeatedly and thoroughly
described, hence a reference to various works upon this subject
will suffice here.3
Bolton4 succeeded in combining chlorine and carbon. He
employed the voltaic arc between carbon electrodes in an at-
mosphere of chlorine. Perchlorethane is principally produced;
hexachlorbenzene is formed in lesser quantity. As both of these
chlor-hydrocarbons are produced by the complete chlorinatlon
of carbon tetrachloride, Bolton assumes their intermediate
existence; the intermediate occurrence of gaseous or fluid
compounds like perchlorethylene does not seem improbable.
Bromine and iodine appear to react analogously (Bolton4 );
experiments with the latter halogens yet await a scientific
treatment. They would undoubtedly prove remunerative.
Lob 5 has made several other decompositions by means of
the voltaic arc between carbon points. These were carried out
with the following vapors and liquids:
Methyl Alcohol yields formic acid, and also about 39 per cent,
methane, 45 per cent, hydrogen, small quantities of carbonic
1
Ann. chim. phys. [4] 13, 143 (1868); see also Berthelot: EssaideMe-
canique CMmique II, 332-336 (1879).
2
Ztschr. f. Elektrochemie 4, 514 (1898). '
3
Moissan, The Electric Furnace, Ahrens: Die Metallkarbide (Sammlung
m chemisch-technischer Vortrage), Stuttgart, 1896, Haber: Grundriss der tech-
nlscher Elektrochemie, Miinchen und Leipzig, 1898. See also," Recent liter-
ature on carbides," Journ. Am. Chem. Sac. 1904, p. 200.—Trans.
4
Ztschr. f. Elektrochemie 8, 165 (1902); 9, 209 (1903).
5
Ber. d. deutsch. chem. Gesellsch. 34, 9l5 (1901).
THE SPARK DISCHARGE AND THE VOLTAIC ARC. 251
acid carbon monoxide, and acetylene. Formaldehyde is not

formed.
Glacial Acetic Acid yields about 35 per cent, carbon monoxide,
26 per cent, hydrogen, 15.5 per cent, carbonic acid, and 12 per
cent, saturated and 7 per cent, unsaturated hydrocarbons.
Benzene.—The benzene is colored brown and is considerably
charred; no substance could be isolated from the liquid. The
escaping gas consists of 86-90 per cent, hydrogen as well as
small quantities of saturated and unsaturated hydrocarbons.
Fapfrthalene likewise yields chiefly hydrogen, the residue
being greatly charred.
Cyanogen is completely decomposed by the voltaic arc, as
shown by Hofmann and Buff.1
Cyanides.—The attempts to prepare cyanides by the direct
or indirect" union of nitrogen and carbon must be mentioned
here; they are of importance particularly for the problem of
utilizing atmospheric nitrogen. Since the reactions take place
at a high temperature, we can also make use of electrically pro-
duced heat, as suggested by Readmann; 2 but in his process—
a mixture of oxides or carbonates of alkalies, or earthy alkalies,
with carbon is heated in the voltaic arc between two carbon
points in the presence of nitrogen—electrolysis occurs as'an
important factor. The conditions are similar in his attempts,
undertaken with Gilmour,3 to prepare potassium ferrocyanide.
1
Lieb. Ann. 113, 129 (1860).
2
Eng. Pat. No. 6621 (1894).
3
Eng. Pat. No. 24116 (1892).
CHAPTER III.
THE UTILIZATION OF CURRENT HEAT IN SOLID
CONDUCTORS.
Methane. — Davy decomposed methane with an electrically

incandescent platinum wire into carbon and hydrogen, an
effect which was also later obtained by Hofmann and Buff1
with an electrically incandescent iron spiral.
Ethylene, according to the last named investigators, i like-
wise breaks down, under similar conditions, into its elements.
Cyanogen. — Cyanogen also is completely split up by an
incandescent iron wire into carbon and nitrogen.
Haber 2 has made some experiments regarding the decompo-
sition of several hydrocarbons in the electric furnace. The gas
current was conducted through a glass or porcelain tube which
was placed in an electrically heated tube of platinum; platinum-
iridium, or carbon.
Hexane. — No considerable decomposition of hexane vapor
occurs at about 600°; at 800°-940°, however, there were pro-
duced the following percentages of gases, based on 100 per cent.
of the vaporized 'hydrocarbon :
Methane . ............ 27 .77 %
Olefines (ethylene). ... 22. 14%
Acetylene ............ 1. 00%
Hydrogen ..... ...... 2.44%
Benzene ............. 6. 76-10%
Carbon .............. 3.27 %
Tar ............... . . 29.2 2%
1
Lieb. Ann. 113, 129 (1860).
2
Experimental-Untersuchungen iiber Zersetzung und Verbrennung von
.Kohlenwasserstoffen, 43-77 Munich (1896).
252
CURRENT HEAT IN SOLID CONDUCTORS. 253
At a still higher temperature hexane is for the greater part

converted into its elements.
Trimethylethylene is split up at 930°-940° in the following
manner. From 100 per cent, of material started with there
were obtained.
Methane.......................... 27.72% .
Ethylene ........................ 8.10%
Hydrogen ....................... 1.76%
Gaseous by-products. .. . 4.46%
Acetylene........................ 0.30%
Carbon........................... 5.09%
Benzene.......................... 8.00-13.41%
Tar ................................. 33.71-39.12%
The above figures represent percentages by weight. At
1000° trimethylethylene is also extensively decomposed.
Ethyl Ether.—For obtaining a slow combustion of the ether,
Legler1 passed a mixture of ether vapor and air over an elec-
trically incandescent platinum wire and obtained a mixture
of formic acid, acetic acid, formaldehyde, acetaldehyde, and
hexaoxymethylene peroxide (CHÔÔa+SEÔ.
Lob has recently carried out a great number of pyrogenic
reactions and syntheses, employing the already • described
arrangement (p. 242) with electrically incandescent metallic
wires and carbon filaments.
Methyl Alcohol.2—On employing a cherry-red incandescent
iron wire, this substance yielded, besides formic acid and a
little trioxymethylene, a gas mixture containing about 72
per cent, hydrogen, 20 per cent, carbon monoxide, 6.5 per cent,
methane, and traces of carbon dioxide. The figures represent
percentages by volume, the same as below.
Chloroform.3 —This compound, when brought into contact
with an incandescent wire of iron, nickel, platinum,, or platinum-
iridium heated to 850°-950°, is decomposed, there being formed
perchlorbenzene (10%), perchlorethane (12%), and perchlor-
1
2
Ibid. 34, 917 (1901).
3
ethylene (30%). The figures refer to percentages by volume

based on the original material. Much hydrochloric acid is
also produced, and, after the passage of the gases through
water, a small quantity of carbon monoxide. If a mixture of
chloroform with water is subjected to a similar pyrogenic decom-
position, a good deal of carbon monoxide is evolved. Its
formation is to be explained by the intermediate presence of
dichlormethylene.
Ctiloroform and Aniline.1 — The vapors of these two sub-
stances, blown with steam against the incandescent metallic
wire, unite chiefly to triphenylguanidine, while decomposition
products of chloroform alone, perchlorbenzene, perchlorethane
and perchlorethylene, are present in considerably smaller quan-
tities. The formation of triphenylguanidine is easily under-
• \| stood by supposing that dichlormethylene is intermediately
- '' produced. Phenylisocyanide is primarily formed from this
substance and aniline; the isocyanide- immediately takes up
v chlorine, which is derived from the accompanying process,
'* 3C2CU = Cede + SCk, and unites further with the excess of aniline
' to triphenylguanidine :
II.
III. C6H6NCCl2+2CiHaNH2«C6H5NC(HNC6H5)2+2Ha.
On the basis of these experiments Lob arranges the follow-
ing scheme for the pyrogenic chloroform decomposition, which
affords a complete expression of all the observed phenomena :
CC1 3 H -- >CC12 +HC1
1
The arrows show the direction and the possible reversibility

of the reactions; stable end-products are printed in heavy type.
Carbon Tetrachloride.1 —This compound, when decomposed'
alone by an arrangement similar to that used for chloroform,
gives off great quantities of chlorine; perchlorbenzene, perchlor-
ethane (in very trifling quantity), and perchlorethylene are
also produced. The presence of water in this case also increases
the yield of carbon monoxide. Aniline leads to triphenyl-
guanidine, some resin being also formed.
The scheme of decomposition for tetrachlormethane is the
following:
CC14
C2C16
If air is blown simultaneously

with the
tetrachlormethane vapors against
the incandescent wire, there is produced
phos-
gene, which is probably formed by direct oxidation of dichlpr-
methylene :
Perchlorethylene2 yields a gas mixture of chlorine and a

little carbon monoxide, and also phosgene in the presence of air.
The residue in the flask consists principally of perchlorbenzene
besides traces of perchlorethane. Addition of water consider-
1
ably increases the quantity of carbon monoxide. II
3
Chloral Hydrate, when subjected to pyrogenic decomposi-
te.
2
l. c.
8
Ztschr. f. Elektroehemie 10, 504 (1904).
1!
tion alone or mixed with water vapors, breaks up in the same

manner. The reactions are expressed in the following scheme:
C C13CHO------ »CC12+C1HCO
1 C2C14
C2C16 HC1 + CO
I
CC1 /
III +C ^
CC1 .
I
C6C16.
Besides the products observed in the decomposition of

chloroform, carbon monoxide also occurs as a direct decomposi-
f tion product of the unstable formylchloride.
I
Trichloracetic Acid is completely decomposed at higher
temperatures into gases; Joist1 could detect hydrochloric acid,
chlorine, carbon monoxide, and carbon dioxide, besides traces
of phosgene. The decomposition takes place, perhaps with the
aid of moisture, as shown in the equation:
2CC13COOH -f H20 = C12 + 4HC1+SCO + C02.
Phosgene is formed secondarily from chlorine and carbon
monoxide.
Acetyl Chloride breaks up (Joistl ) completely into approx-
imately equal volumes hydrochloric acid, carbon monoxide, and
unsaturated hydrocarbons (mostly ethylene). The reaction
is expressed in the equation:
2CH3COC1 = 2HC1 + 2CO + C2H4.
Bromoform splits off hydrobromic acid and some free bro-
mine, and yields as chief product perbromethylene, also per-
brom benzene (Joist*). Hexabromethane occurs only in traces;
this was to be expected on account of its easy decomposability
into bromine and perbromethylene. Some carbon monoxide
1
The experiments have not yet been published. Bonn (1904).
escapes. If the brornoform vapors are mixed with aqueous

vapors the products remain the same; but no gas is evolved,
and the water contains, besides hydrobromic acid, small quan-
tities of formic acid. The following expresses the decomposition: '
CBr 3H > CBr 2 + HBr
Presence of water determines the reaction:
CBr 2+2H20 = HCOOH+2HBr,
while with chloroform the reaction is
CC12 + H20==CO+2HC1,
carbon monoxide being produced.

Benzene, as is well known, is easily converted at high
temperatures into diphenyl and complex hydrocarbons. Lob'sl
method is very well suited for preparing diphenyl on a small
scale. Metallic wires serve the same purpose as carbon filaments.
Diphenylbenzene occurs as a by-product in small quantity.
Nitrobenzene, blown in vapor form against the incandescent
wire, decomposes violently, sometimes explosively, producing
a charred mass and large quantities of nitric oxide. The reaction
is moderated by diluting the vapors with aqueous vapor, but
the obtainable products are so complex that their determination
has not yet been accomplished (Lob 2 ).
m
1
Ztschr. f. Elektrochemie 8, 777 (1902)'.
2
Ber. d, deutsch. chem. Gesellsch. 34, 918 (1901); Ztschr. f. Elektro-
chemie 8, 775 (1902). 11
iti
o-Nitrotoluene. — Although the pure vapors of o-nitrotolu-

ene behave like those of nitrobenzene, o-nitrotoluene diluted
with aqueous vapors yields anthranilic acid, in addition to a
little o-cresol and salicylic acid and considerable resinous sub-
stances (Lob x). It is possible that anthranil is primarily formed
from o-nitrotoluene, water being split off; the anthranil is then
converted into anthranilic acid by the highly heated steam,
just as by boiling with alkalies:
/N0 2
C6H4< -C6
X
CH3
The presence of salicylic acid must evidently be referred
to the action of the hot aqueous vapors upon anthranilic acid:
/NH2 OH
C6H4< H20 + NH3.
X
COOH OOH
Slight traces of ammonia could be detected. The o-cresol

was evidently formed from o-nitrotoluene and aqueous vapor,
with splitting off of nitrous acid.
The material of the glower is mostly without any influence
on the reaction. Platinum, platinum-indium, nickel, iron
and carbon gave qualitatively equal results; only copper
wires are not applicable for the preparation of anthranilic
acid. They primarily cause a reduction to o-toluidine and
then complete combustion is brought about by the copper
oxide which is formed.
Aniline.2— This compound is colored brown, ammonia is
split off and some gas evolved. Diphenylamine and car-
bazole could be isolated.
Diphenylamine.2 — On conducting the. vapors of this sub-.
stance mixed with those of chloroform over metallic glowers,
1
2
Ber. d. deutsch. chem. Gesellsch. 34, 918 (1901); Ztschr. f. Elektro-
efcemie 7, 913 (1901).
diphenylamine combines with chloroform and gives a small

yield of acridine.
Benzyl Chloride, benzol chloride and benzotrichloride, when
subjected like chloroform to pyrogenic decomposition, behave
quite like the latter compound; a dissociation into hydro-
chloric acid, or chlorine and phenylmethylene, or chlorphenyl-
1
methylene, seems to occur first (Lob ).
Benzal Chloride gives smoothly stilbene, with splitting off
of hydrochloric acid:
2C6H5CH2C1 -» 2C6H5 - CH+2HC1

f
CgHs • CH: CH • CgHg.
Benzal chloride also splits off hydrochloric acid, but no

chlorine; a mixture of a- and /3-tolane dichlorides results:
2C6HS • CHC12---------- > 2C6H5 • CC1 + 2HC1
I I
C6H5-CC1 C6H5-CC1
C1C-C6H5
Benzotrichloride at first gives off chlorine, which does not,

however, escape, but is absorbed by a part of the primarily
formed tolane-dichlorides; these are thereby converted into
tolanetrichloride and tetrachloride.
2C6H5 • CC13---------- > 2C6HS • CC1+2C12
C6HS-CC1
/"* TT /"^^l
C6 H5 -CC1 C 6 H5 -CC1 -> ~^~ -->>^^ V/AJC15 • V> v/J.2
P aTTr- - PPI , PIP PnTTVt ____________________ ^
"f\^ TTT
— > _ _f\fV\
_ - „
V/gJDL5 • L»v/l2
x
Ber. d. deutsch. chem. Gesellsch. 36, 3059 (1903); Ztschr. f. Elektro-
chemie9, 903 (1903).
If a mixture of benzotrichloride and water is subjected

to pyrogenic decomposition, the yield of tolane dichlorides,
tri- and tetrachlorides is very small, although these substances
do not entirely disappear. Benzaldehyde and benzoic acid
become the chief products. The benzaldehyde is apparently
the reaction product of chlorphenylmethylene with water, and
the benzoic acid the oxidation product of the benzaldehyde by
the intermediately occurring chlorine. Benzalchloride, in the
presence of water, gives benzaldehyde; no benzoic acid is
formed.
'4
CHAPTER IV.
THE SILENT ELECTRIC DISCHARGE AND THE ACTION OF

TESLA-CTJRRENTS.
I. THE SILENT ELECTRIC DISCHARGE .

WHILE the action of the induction spark upon organic
bodies, gases and vapors is undoubtedly a thermic process., in
the silent electric discharge the electric energy plays a more
important part, either as such or in the form of radiant energy.
In this case we are dealing with a constant passage of an electric
current through gases. Even if the theory of the conduction
in gases is still in its primitive stages; many phenomena already
point to ionic formations or electron effects. The silent electric
discharge takes place continuously between two conductors
separated by a dielectric such as glass, or gases, if the poten-
tial difference of the two conductors exceeds a certain value.
In rarefied gases the discharge is accompanied by luminous
appearances (glow discharges), which are often suited for in-
vestigations in spectrum analysis; under ordinary pressure
and in daylight the gases do not glow; but in the dark and with
a sufficiently high tension, even without rarefaction, the glow
occurs.
The rise in temperature during the discharge is trifling; there-
fore reactions which are brought about by the latter's influence
often assume a different role than those produced by the in-
duction spark. In the latter case stable compounds are pro-
duced, which is very natural, considering the high temperature.
The formation of labile, often endothermic substances, is incited
by the silent electric discharge. These substances are easily
decomposed by stronger calefaction. The great value of these
reactions for simple syntheses—as employed by nature in plants
262 ' ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
for producing the labile compounds, which serve as plant nourish-

ment, from the most stable products started with—lies in this
property. This problem is extremely important. The syn-
thesis of substances important for nature—the carbohydrates,
albumens—in the laboratory with our usual chemical resources
is only a first step in the realm of actual synthesis. This will
only be found when we can follow the paths which nature
herself chooses in preparing her products. Her methods are
undoubtedly much simpler than the artificial, chemical proc-
esses that we must make use of in reaching the same goal.
The whole primary material upon which we can base the
formation of the most various substances of organic nature is
the atmosphere—are carbonic acid, oxygen, nitrogen, and water.
The synthesis of complex substances from these materials
is known to take place under the influence of light rays and the
absorption of energy. Such a transformation of a system of
lower energy into one of higher energy usually occurs only at
high temperatures. The silent electric discharge occupies a
prominent place among the forms of energy which, like light,
favor endothermic reactions at ordinary temperatures.
Berthelot,1 in pointing to the nature of the reactions occur-
ring under its influence, which are particularly similar to those
of plants, advanced the following views: In clear weather there
exists between two strata of air only one metre apart a potential
difference of 20-30 volts which, in rainy weather, can increase
to about 500 volts. Reactions can already take place under
the influence of such tensions; thus at 7 volts a fixation of nitro-
gen by carbohydrates can already occur; the decomposition
of carbonic acid requires higher tensions.
Opportunities for reactions on the surfaces of plants, by
the formation of potential differences, are likewise continually
present. In other words, Berthelot ascribes a leading part in
natural syntheses to atmospheric tensions, which can neutralize
one another in the form of invisible discharges (convective dis-
charges) through thin strata of air acting like dielectrics.
1
Compt. rend. 131, 772 (1900).
THE SILENT ELECTRIC DISCHARGE. 263
Even if this hypothesis does not seem to be scientifically

well founded, it is nevertheless suitable for showing the im-
portance of this but little investigated domain.
We still know nothing of the consumption of energy in the
reactions produced by the silent electric discharge. The spent
energy can be easily determined by employing certain current
conditions; it is difficult to calculate experimentally the utilized
energy; this is due to the insignificance of the obtained reac-
tions and the simultaneously occurring heat quantities.
The fact that Faraday's law is not applicable shows that
the reactions which are. caused by the discharge are not of a
purely electrochemical nature. The chemical effect is usually
larger than can be accounted for by the minimum quantities
of electricity. As shown by the kind of reactions, thermic
effects are also unlikely, although an influence of the tempera-
ture produced by the discharge is always manifest. The suppo-
sition is more probable that the invisible electric discharge, in
which cathode and ultra-violet rays are present, introduces into
the system great quantities of kinetic energy by the movement
of electrons; this energy is then transformed into chemical
energy. This kinetic energy would then have to be equivalent
to the heat of formation of the occurring substances, taking into
account the part directly converted into heat. Bichat and
Guntz1 have shown by a simple example, that of ozone, that
the heat developed in the induction tube and calorimetrically
measured, plus the heat of formation of the produced ozone,
is equal to the calorific equivalent of the spent electrical energy.
The actual efficiency of ozonizers is extremely small. With
the best ozone apparatus and under the most favorable circum-
stances only about 15 per cent, of the total energy can be
utilized for the chemical reaction.
a. Arrangements.
The well known and variously shaped small ozonizers of
Berthelot and Siemens are generally satisfactory for scientific
1
Aim. chim. phys. [6] 19, 131 (1890).
experiments. According to a recommendation of Losanitsch

and Jovitschitsch the apparatus are suitably called " electrizers."
The principle employed in their construction is always the
same. An air space or chamber, chosen as narrow as possible,
exists between two conductors, either metals or electrolytes,
which axe connected with the terminals of an induction coiL
Vacuum Pump
FIG. 9. FIG. 10.

The metals serving as electrodes are in most cases separated —
electrolytes of course always — from the discharging chamber by
thin glass walls. Suitable small tubes attached to the appara-
tus afford means of ingress and egress for the gases or vapors
to be acted upon. The space between the walls in the dis-
charging chamber is of great influence (A. de Hemptinne *).
Some apparatus used by myself in experiments as yet un-
finished may be mentioned here. The difference from
former 269
r A cad r o y d e
constructions exists (in Fig. 9) in the constant production of

the vapors in a flask with a ground-glass neck made to fit one
end of the induction tube; the flask contains the reaction fluid.
This apparatus has an arrangement for cooling the vapors and
one for working under diminished pressure. In Fig. 10 the
apparatus can be taken apart at the ground-glass connection &•
in such a way that liquids, solids, and electrodes of various*
materials, especially for investigating catalytic effects, can-
be brought into it. The current connections with the outer-
coat is made in Fig. 10 by means of a* platinum loop a, fused
into the side of the tube, in which is hooked the spiral electrode,
of any kind of metal wire.
Special attention in these experiments must be paid to the-
interrupter (rheotome*); platinum, and mercury circuit-break-
ers and electrolytic ones are applicable. The former pos-
sesses the disadvantage of great wear and tear, and in prolonged
experiments requires frequent regulation. If kept clean, the-
mercury circuit-breaker is very convenient. The Wehnelt
circuit-breaker interrupts high current strengths very exactly,
and, when suitably made, can be used both with alternating j^ ,-„,
and direct currents. To save the consumption of platinum I «r' '<f
construct the electrolytic interrupters by placing in front of a
large carbon plate the point of a nickel wire 2 mm. thick as
active electrode in a 2-3% sodium-hydroxide solution. Glass
worms regulate the temperature with high current strengths.
This simple and cheap arrangement has proven serviceable.
b. Chemical Results.
The action of the silent electric discharge upon organic fs,,|j
compounds takes its starting point in the observation that
oxygen under its influence is polymerized to ozone. Although
the work done in this field, which until recently was chiefly
carried on by the French school, has not yet shown great prac-
tical results, we need not doubt that these phenomena deserve
1
See also Leitfaden des Rontgenverfahrens, published by Dessauer and
Wiesner, Berlin, 1903.
the greatest interest and are closely related^ as already em-

phasized, to the fundamental questions of synthesis in general.
Besides the experiments on the behavior of organic vapors,
the observations which have been made on the synthesis of
simple organic compounds from carbonic acid and carbon
monoxide—substances which we are not accustomed to regard
as organic—are of particular interest. The results so far obtained
are mentioned below. We are mostly indebted to Berthelot's
investigations along this line of work.
I. Carbonic . Acid and Carbon Monoxide.
Carbonic Acid. — Berthelot l observed the decomposition into

carbon monoxide and oxygen. The reaction is reversible, an
equilibrium occurs, in which, however, the partially ozonized
oxygen converts carbon monoxide into carbonic acid and a
solid carbon suboxide, CUOs, which Brodie 2 had already formerly
observed. Carbon dioxide, under a pressure of 3-10 mm.
mercury, splits up very rapidly and up to 70 per cent, into
carbon monoxide and oxygen (Norman Collie 3).
Carbonic acid, in the presence of., water, is converted into
formic acid and oxygen (Losaftitsch and Jovitschitsch 4) ; the
latter, partially ozonized, produces hydrogen peroxide.
Lob 5 showed that moist carbon dioxide also always yields
carbon monoxide and only the latter forms the starting point
for formic acid. The following reactions occur:
2. CO + H20-HCOOH,
3. 3 02 = 2 03,
4.
1
Essai de Me*canique chimique II, 377 (1879).
2
London R. Soc. Proceed. 21, 245 (1873); Lieb. Ann. 169, 270 (1873).
Uoum. of the Chem. Soc. 465, 1063 (1901).
* Ber. d. deutsch. chem. GeseUsch. 30,135 (1879).
5
Sitzungsberichte d. niederrheinischen Gesellschaft fur Natur- u. Heil-
kunde (1903).
Carbonic acid and hydrogen, according to the experiments

of Losanitsch and Jovitschitsch, 1 also unite to form formic
acid.
Carbon Monoxide. — Considering the easy decomposability of
carbonic acid with splitting off of carbon monoxide, the latter 's
behavior is particularly interesting. According to Berthelot2
it breaks up into carbonic acid and the above-mentioned sub-
oxide :
Moist carbon monoxide, according to the concordant results

of Losanitsch 1 and Jovitschitsch, of Lob 3, and of Hemptinne,4
yields formic acid. There are also always formed some car-
bonic acid (Maquenne; 5 and Hemptinne) and hydrogen (Ma-
quenne). The dimensions of the "'electrizer," particularly
the distance of the walls between which the discharge occurs,
are of special influence on the result (Hemptinne) .
The influence of the experimental conditions is shown in
the action of the silent discharge upon a mixture of carbon
monoxide and hydrogen. Thenard, Brodie, and Berthelot &
found a solid body (X^HsOs)™; Berthelot also observed a little
carbon dioxide, acetylene, and an olefine-like hydrocarbon.
Losa.nitsch and Jovitschitsch 7 obtained formaldehyde and
its polymers; Hemptinne observed an oily liquid, without
being able to say anything definite regarding the formation
of formaldehyde.
At any rate all these experiments are worthy of the most
thorough study. If the assertion of Phipson 8 is correct, that
in plants hydrogen peroxide first produces formaldehyde from.
the carbonic acid (C0 2 -f ^C^CTÔ + Os), the possibility of
1
J. c.
2
Essai de M£canique chimique II, 379 (1879).
3
See note 5 on page 266.
4
Bull, de 1'Acad. roy. de Belg [3] 34, 269 (1897).
5
Bull. soc. ohixn. [2] 89, 308 (1883).
8
Essai de M6canique chimique II, 382 (1879).
7
l.c.
8
Chem. News, 50, 37, 288 (1884).
the formation of sugar by polymerization is at once given. The

well-known Bayer theory, of the formation of sugar in plants;
in connection with the above-mentioned view of Berthelot on
the importance of atmospheric tensions for the chemical re-
actions of plants thus obtains new essential, and experimentally
accessible, facts.
Recent investigations of Berthelot l deserve the greatest-
attention exactly in this connection. He found:
1. Carbon monoxide and carbon dioxide condense with an
excess of hydrogen to carbohydrates ;
n(C02 + 2H2) = »-h nH20.

» 2. If only a little hydrogen is
present, complicated com-
pounds rich in oxygen result.
3. In a mixture of carbon monoxide, carbon dioxide, hydro-
gen, and nitrogen, the discharge produces nitrogen containing
compounds having the formula :
(COH3N;W, or (COH3N)n+nH20,
which are comparable with hydrocyanic acid, and the com-
pounds of the carbamide and xanthine groups.
With an excess of carbon monoxide Berthelot finds sub-
stances which seem related to parabanic acid. If water occurs
II; in the reactions, ammonium nitrite is present.
Berthelot's observations are confirmed by the experiments of
A. Slosse,2 who, by subjecting a mixture of 1 volume carbon
monoxide and 2 volumes hydrogen to the induction action in an
ozonizer, obtained a crystalline, fermentable sugar which could
have been formed from formaldehyde and methyl alcohol —
;,s both of which can be shown to be present — by the further
\f action of the discharge :
;t
2 -CH 2 0;
2 = CH3OH.
'Compt. rend. 126, 609 (1898).

2
Bull, de PAcad. roy. de Belg. 35, 547 (1898).
i *4
''•A
Berthelot has published a paper1 on the apparatus em-

ployed in his experiments, the methods of the quantitative
determinations, the influence of the conditions on the reaction
velocity, and the dependence of the results upon the duration
of the experiment. The latter is particularly important for
the theoretical interpretation of the results. Simple, binary
compounds are primarily formed which are secondarily poly-
merized to complex compounds — similarly as in physiological
processes, in which the assimilated substances, after being
split up into simpler substances for the purpose of nutrition,
are again united to complicated compounds.2
Losanitsch and Jovitschitsch, 3 by the action of the silent
electric discharge upon a mixture of carbon monoxide with
other gases, have also accomplished the following syntheses.
They obtained:
1. From carbon monoxide and hydrogen sulphide : Formalde-
hyde and sulphur, and thioformaldehyde and its polymers
respectively, besides water,
HCOH + H2S - HOSH + H20.
2. From carbon monoxide and hydrochloric acid: The un-

stable f ormylchloride :
CO+HC1-HCOC1.
3. From carbon disulphide and hydrogen : Hydrogen sulphide
and carbon monosulphide :
4. From hydrogen sulphide and carbon monoxide: Carbon

oxysulphide and carbon monosulphide:
CS2+CO-COS+CS. *
— - — — - - - • - _ _ _ _ _ _ _ — , - . — . . . . . . . . . . . . _ _ _ _ _ ,
1
Compt. rend. 126, 561 (1898); 131, 772 (1900).
2
1. c.
8
Ber. d. deutsch. .cliem. Gesellsch. 30, 135 (1897).
In the further description
of the results obtained in the
5. From carbon monoxide and ammonia: Formamide:

realm of silent discharges we will first consider the behavior of
According to Slosse,1 1 vol. CO and 2 vols. NH3 give a

crystalline substance resembling urea.
6. From nitrogen and water: Ammonium nitrite:
single organic substances, then that of mixtures.
//. Hydrocarbons.
Methane. — Aliphatic hydrocarbons, exposed to the action
of a high-tension discharge, yield hydrogen, a little acetylene,
which in the course of the experiment can again disappear by
polymerization, and polymerized hydrocarbons. From methane
Berthelot 2 obtained the last-mentioned gases, a resinous hydro-
carbon, and traces of a fluid possessing a turpentine odor. He
found — in percentages by volume — from 100 CH4: 105.2 H2>
4.4 CBU, a solid hydrocarbon of the empirical formula CioHig.
Methane and oxygen, according to Maquenne,3 yield formal-
dehyde besides considerable formic acid.
Methane and carbon monoxide, according to Losanitsch and
Jovitschitsch/ unite to acetaldehyde and its condensation and
polymerization products; according to Hemptinne,5 aldehydic
substances.
Methane and carbonic acid condense (Thenard and Berthe-
lot2 ) to an insoluble carbohydrate; Berthelot observed the
presence of a trace of butyric acid. The residual ga'ses con-
tained a little acetylene and considerable carbon monoxide.
1
Bull, de 1'Acad. roy. de Belg. 35, 547 (1898).
2
Compt. read. 82, 1360 (1876); TraitS de Mecanique Chimique II,
379 (1879). See also Compt. rend. 126, 561 (1898).
8
Bull. soc. chim. 37, 298 J1882).
4
5
Bull, de TAcad. roy. de Belg. [3] 34, 275 (1897).
Methane and nitrogen in the mixture 100 CH4-f 100 N2 give

117.7 H2, 3.4 CH4, 74 N2, and a solid body having approxi-
mately the composition, C8Hi2 N"4 (Berthelot !).
Ethane. — From pure ethane Berthelot, at the beginning
of the experiment, obtained (1. c.) a little acetylene and ethylene
besides a resinous hydrocarbon. He found at the end of the
experiment, from 100 C2H4 i 107.8 H2; 0.7 CH4, Ci0Hi8. The
unsaturated hydrocarbons had become polymerized.
Ethane and carbon monoxide yielded Hemptinne (1. c.) chiefly
acetaldehyde, also some acetone:
Ethane and nitrogen. — There were obtained from 100 C2H6 +

100 N2 (Berthelot) : 98.2 H2 , 3.0 CH4, 73.5 N2, Ci6H32N4 .
Ethylene.— 100 C2H4 gave 25.15 H2, 4.35 C2H6 (C8Hi4)ra
(Berthelot). In former experiments Berthelot had obtained a
fluid (C2oHi6.e) already observed by Th^nard.
Ethylene and nitrogen. — 100 C2H4 + 100 N2 gave 28.6 H2,
0.4 C2H6; 62.2 N2, Ci6H32N4.
Propylene.— 100 parts yielded: 34.2 H2, 0.7 CH4, Ci6H26.
Propylene and nitrogen. — 100 CaHe + lOO N2 gave 17.8 H2;
60.5 N2j Ci5 H28 N4 . '
Trimethylene.— 100 C3H6 -» 37.3 He, 1.4 CH4, Ci5H26.
Trimethylene and nitrogen. — 100 C3 H6 + 100 N2~»41.4H2,
1.6 CH4, 61.4 N2, Oi5H26N4.
Acetylene.— 100 C2H2 -> 1.8 H2, 0.8 C2 H4, 0.08 C2H6; and an
explosive substance. In the presence of hydrogen this sub-
stance is partially absorbed by the acetylene.
Acetylene and nitrogen. — 100 C2H24-100N2 gave no hydro-
gen and no hydrocarbon, but 88.6 N2 and a solid substance,
Ci6Hi6N2.
AUylene.— 100 C3H4-»3 H2, (C16Hi9)2.
Allylene and nitrogen. — 100 C3H4 + 100 H2 -> 82.2 N2,
Ci5H20N2.
In the experiments of Berthelot the gas analyses refer to
the residual gas volume after the discharge has acted on the
•
I'-
gaseou formed as polymerization products.
s 2. The olefines CnEfen also polymerize with loss of hydrogen.
mixtur The solid products hereby formed, (CJ32Jm — H2, in which
e for m equals 4 or 5, or a multiple of these values, remind one of
24 the camphenes, so far as their composition is concerned.
hours. They certainly belong to the cyclical hydrocarbons.
The 3. The acetylene hydrocarbons, Cn3.2n-2, polymerize without
high loss of hydrogen.
molecu 4. All hydrocarbons take up nitrogen, forming probably
lar cyclical polyamines; methane and ethylene hydrocarbons seem
formul to give tetramines; and acetylene hydrocarbons, diamines.
ae Benzene gave Hemptinne2 resinous substances, several
give hydrocarbons, a little acetylene, and hydrogen.
approxi Benzene and hydrogen easily unite under the influence of
mately the discharge. Berthelot 3 found that 1 cc. benzene takes
the up 250 cc. hydrogen, i.e., about 2 equivalents, forming a
compos solid polymeric hydrocarbon (CeH^n.
ition of Benzene and nitrogen, according to Jterthelot,4 form a
the polymeric condensation product, one part by weight of ben-
solid zene taking up about 0.12 part by weight of nitrogen. The
conden substance, on being heated, splits off ammonia and seems to
sation be a diphenylenediamine. Recently Berthelot 5 has found that
product argon is also absorbed by aromatic compounds, especially by
s. mercury phenide, forming a mercurargon phenide. Mercury
Ber metMde, on the contrary, does not absorb argon, but if nitrogen
thelot1 1
See also Jahrb. d. Elektrochemie of Nernst and Borchers, V, 202 et seq,
thus (1899).
2
summa Ztschr. f. phys. Chemie 25, 298 (1898)
3
Compt. rend. 82, 1360 (1876).,
rizes ' 4 Ann. chim. phys. 1J, 35 (1897).
his 5
Compt. rend. 129, 71, 378 (1899).
experie
nces as
to these
reactio
ns:
1. T
he limit
hydroca
rbons
Gn~H.2
n+2 lose
2 atoms
of
hydroge
n
per
molecul
e.
Solid
hydroca
rbons,
most
probabl
y of a
cyclical
nature;
are
THE SILENT ELECTRIC DISCHARGE.
273
is simultaneously present, it condenses with this to a con-
densation product of approximately the formula C2oH34N5.
Turpentine (C2oH16) unites with about 2.5 equivalents of
hydrogen to a solid polymeric body.1
///. Alcohols.
Methyl Alcohol.—According to Maquenne,2 the vapor of
methyl alcohol is decomposed by the silent discharge chiefly
into methane and carbon monoxide; some hydrogen, ethylene,
and acetylene and very little carbonic acid; are also produced.
The quantity of hydrogen increases with increasing pressure
(from 3-100 mm. mercury pressure), that of the other products
decreases:
Pressure. - 3 mm. 100 mm.
CO ..................... 24 3 19 6
CO 2 00 0 0
CVEl + OJL .......... 43 09
51.0 30 7
20 4 42 8
H. '"'.'.'.'. ....
A decomposition is caused by a high temperature similar to
that produced by the discharge.
A.'Hemptinne subjected a large number of substances to
rapid electric oscillations in an arrangement which, according
to the method of Lecher,3 permitted an investigation of the
influence of various wave lengths.4 He found that methyl
alcohol 5 at 15 mm. pressure and with weak oscillations gave:
Undecomposed alcohol......................... 2.0%
Carbonic acid...................................... 4.2%
Carbon monoxide .......... ..................... 30.4%
Hydrogen ........................................... 30.5%
Methane (and other hydrocarbons). .. 32.9%
1
Trait^ de M6canique chimique II, 382 (1879).
2
Bull. soc. chim. [2]37,298 (1882); 40,60 (1883).
8
Wied. Ann. 41, 850 (1890).
4
Ztschr. f. phys. Chem, 22, 358 (1897).
5
Ibid. 25, 284 (1898).
I
Stronger oscillations produced about the same effects.

Hemptinne suggests the following three problematical equa-
tions for explaining the reaction:
the oxygen acts in turn upon the methane and forms C02 , CO,
and H20, while methane itself simultaneously breaks up into
hydrogen and other hydrocarbons. /
The following processes seem to him less likely:
II. CH3OH = CO+2H2,
because the solid reaction product of hydrogen and carbon

monoxide, which Berthelot found, is not present, and:
IIL
with subsequent polymerization, since here the formation of

large quantities of methane is difficult to explain.
Owing to the present existing difficulty of explaining the
complex action of electric oscillations, I should like to here
refer, but only by way of suggestion, to a further possibility
which takes account of the polymerizing influence of the oscil-
lations. It is imaginable that primarily two or several mole-
cules of methyl alcohol become associated and yield a product
which is broken up during the progress of the experiment.
The decomposition products thus formed are then further
effected by the influence of the oscillations. The total equation
would then be the following:
m As some carbon dioxide is always formed from carbon

monoxide and water, such a breaking up of the molecules would
agree with the analytical results of Hemptinne.
Ethyl Alcohol. — Maquenne 1 obtained a gas which possessed
soc. chim, [2] 37, 298 (1882); 40, 61 (1883).

a strong aldehydic odor, and contained hydrogen, ethane,
ethy-
lene, acetylene, carbon monoxide, and carbon dioxide. He
determined the following results for various pressures:
Pressure. 2 mm. 110 mm.
CO2 2 2 0 0
CO
CnH«~f
.................
OnH/1 ..............................................
11 0 ) „, 0
14 0 > 14.8
cX .. ... ...... 30 1 • 19 8
£..*....................... 42 6 65 4.
Hemptinne l found:
Undecomposed alcohol ..........................". 3%
Carbon dioxide....................................... 2%
" monoxide .........................,____ 22%
Hydrogen.............................................. 25%
Ethane and methane ............................ ,
To prove the supposition of a decomposition:
= C2He + 0, Hemptinne added some phosphorus to the vapors,
for immediately binding the oxygen occurring intermediately ^
He actually found a decrease in carbon monoxide and the
hydrocarbons and a considerable increase in the quantity of
hydrogen. Carbon dioxide was not present. On the con-
trary, if oxygon is added directly to the alcohol vapor, the
quantities of carbon mon- and dioxide and of the hydrocarbons
increase considerably, while the quantity of hydrogen decreases.
These phenomena, of course, do not prove the primary process,
C2H50H = C2He+0, which is altogether unlikely. For the chief
change occurs in the proportion of hydrogen to hydrocarbon
(without P: 20% H2 , 62.5% C 2 H6 + CH4 ; with P: 65% H2 ,'
27% C2H0 + CH4); it points to the influence of the medium
upon the reaction velocity and the equilibrium, but does not
permit a decision as to the course of the reaction. The explana-
tion of these processes occurring with simple substances still
requires a great deal of experimental work.
Absolute, fluid alcohol, according to Berthelot,1 breaks up

slowly with evolution of hydrogen and ethane. Aldehyde is
simultaneously produced and a complex hydrocarbon having
perhaps the composition CJEan-
Hemptinne2 also investigated the following alcohols:
Propyl Alcohol.—Result:
Undecomposed alcohol .......................... 2%

Carbon monoxide.................................. 16%
Hydrogen.............................................. 37%
Propane, ethane, and methane ............... 45%
Isopropyl Alcohol breaks up, under similar conditions, in

almost exactly the same way as the normal alcohol.
Allyl Alcohol was .exposed for only a minute to electric oscil-
lations; it yielded:
Undecomposed alcohol.......................... 35%

Hydrocarbons, CnBfen ............................ 35%
Carbon monoxide................................. 10%
Hydrogen, and other hydrocarbons. .. . 20%
Glycerin.—The gaseous products formed are carbon dioxide,

carbon monoxide, and hydrogen.
Glycol gives carbon dioxide, carbon monoxide, hydrogen,
and methane.
Phenol is decomposed, splitting off a gasc omposed of car-
bon mon- and dioxide and hydrogen.
IV. Aldehydes and Ketones.

Aldehydes and ketones were also investigated by Hemp-
tinne.2
Acetaldehyde gives carbon monoxide, hydrogen, and methane.
Paraldehyde.—The gaseous products formed are carbonic acid,
1
Compt. rend. 126, 693 (1898). »l. c .
THE SILENT ELECTRIC D ISCHARGE. 277
hydrocarbons (CnH2n), carbon monoxide, hydrogen, and meth-

ane.
Propylaldehyde breaks up in a different manner than the
isomeric allyl alcohol. The gas, separated from the aldehyde,
contained carbonic acid, methane, and ethane, hydrocarbons,
CnH27i, carbon monoxide, and hydrogen.
Acetone, likewise isomeric with allyl alcohol, gives the same
products as propyl aldehyde. As the quantity of carbon mon-
oxide does not decrease in the presence of phosphorus, Hemp-
tinne concludes that the following decomposition process occurs :
According to Maquenne l acetone vapor is decomposed by

the electric discharge into hydrogen, ethane, and carbon mon-
oxide, a small quantity of acetylene and carbon dioxide being
also formed. The quantity ratios are less dependent upon the
pressure than in the case of methyl and ethyl alcohol :
Pressure. Trifling. 100 mm.
(XL 11 06
CO ............................. 37.5 42.1
O JL 43 29
C2H0 ............................ 32 4 30 0
24.7 24 4
rf,.;:. .:..::::: :
Glyoxal breaks up into carbonic acid, hydrocarbons (CnH2J,
and hydrogen.
V. Acids and Esters.

Formic Acid.—Maquenne2 has investigated the action of
the discharge upon formic-acid vapor under various pressures.
He found carbon monoxide, carbonic acid, and hydrogen. With 'f S r
increasing pressure (2-100 mrn. mercury) the quantity of da I!
carbon monoxide decreases, while the quantities of carbonic
1
BuU. soc. chim. [2] 40, 63 (1883).
2
Ibid. 39, 306 (1883).
acid and hydrogen increase correspondingly. Hemptmne l ob-

tained similar results.
Formic Methyl Ester yielded the following gases (Maquenne 2) :
C ar bon dioxide . . . . .. . . . . . . . . . . . . . . 8. 1 %
" monoxide . . . . . . . . . . . . . .. . . . 4 6. 8%
Et hylonc . . . . . . . . . . . . . . . . . . . . . . . . . . 0. 5%
M et hane . . . .. . . . . . .. . . . . . .. . . . . . .. 20. 6%
H ydr oge n . . . . . . . . . . . . . . . . . . . . . . . . . 2 4 . 0 %
Formic Ethyl Ester gives (Hemptinne) :
Carbon dioxide ..... ..... . ......... 13%
"' monoxide . . . . . . . . . . . . . . . . . . 42%
Hydr oge n. . , . . . . . . . . . . . . . . . . . . . . . . 25%
Ethane and methane ................ 20%
Acetic Acid.— Besides hydrogen, carbon mon- and dioxides,
.{ Maquenne 3 also obtained methane; ethylene, and acetylene,
With increasing pressure he found an increase in hydrogen and
'i carbon monoxide, a decrease in-carbonic acid and hydrocarbons.
Hemptinne observed similar results with his experimental
arrangement. He accepts the following as the primary decom-
position process, corresponding to that of the alcohols :
Hemptinne does this to explain the presence of large quantities

of ethylene.
Acetic Methyl Ester, according to Hemptinne, breaks up
quantitatively almost in the same manner as the isomeric formic
ethyl ester:
Ca r bon dioxide . . . . . . . . . . . . . . . . . . . . . . 11%
" monox ide. . . . . . . . . . . . . . . . . . . . 47%
?;<; >j H yd r o g e n . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 0 %
'* ,»'
J •/':;; Et hane and met ha ne . . . . . . . . . . . . . . . . . 22%
I ' ;^ 1
1. c.
il i,| * Bull. soc. chim. [2] 40, 64 (1883).
»' Ibid. 39, 306 (1883).
279
Propionic Acid gives carbonic acid, hydrocarbons (C»H2tt),

carbon monoxide, hydrogen, and saturated hydrocarbons.
Glyceric Acid.—Although glycerin did not yield any hydro-
carbons, there were obtained, on using glyceric acid, besides
carbon mon- and dioxides and hydrogen, about 20% methane.
Glycoffic Add.—This acid, CH2OHCOOH, breaks up smoothly
into hydrogen (70%) and carbonic acid (30%).
Oxalic Acid splits off carbonic acid, carbon monoxide, and
hydrogen.
Benzoic Acid gives the same products. Hemptinne, who
has investigated the last-mentioned acids, draws the conclusion
from his observations that the molecule is burst by the influence
of the electric vibrations, whereby isomeric substances often
give the same bodies, and sometimes various decomposition
products.
VI. Concerning the Binding of Nitrogen to Organic Substances.

(Berthelot;s Investigations.)
Alcohols and Nitrogen. 1
Berthelot subjected weighed quantities of the alcohols and
certain volumes of nitrogen to the action of the silent electric
discharge. In most cases the action was limited to 24 hours
(when it was continued for a longer period, an absorption
of nitrogen no longer occurred). He obtained the following
results
Methyl Alcohol. — 0.0515 g. and 11.5 cc. N2 were used.
Composition of the resulting gas: H2—18.5 cc., COÔ.9 cc.,
absorbed nitrogen: 9.4 cc. ' '
These values correspond to the process:
a body of the composition C4Hi2N204 or [C2H(OH)NH2 + H20]2 " >f fff

must therefore have been formed. This formula points to the
formation of an amidine or its hydrate.
1
Compt. rend. 126, 616 (1898).
The alcohol is also decomposed by itself, which could be

proved by experiments of short duration in which no notable
absorption of nitrogen had taken place. According to the gas
analyses, the decomposition of the alcohol occurs as shown
in the equations:
2CH3OH = CH4+C02 + 2H2,
CH3OH=CO+2H2.
(Cf. the experiments of Hemptinne, p. 274.)

The other alcohols behave analogously.
Ethyl Alcohol. — There were employed 0.056 g. and 19.1 cc.
N2. Gas obtained: H2 = 26.8 cc., C02 = 0.2 cc., N2 = 8.2 cc.;
absorbed nitrogen, 10.9 cc.
These values represent the reaction
from which (taking into consideration the alcohol decomposed

without absorption of nitrogen) the formation of an amidine
of the formula
C4H8N202 = [C2H(OH) NH2]2
results.
Normal Propyl Alcohol. — Employed 0.082 g. and 19.6 cc.
nitrogen. Gas ob tained: H 2 =23 .4 cc., C0 2 = 2.0 cc. ;
00 = 0.2 cc., N2=7.4 cc.; absorbed nitrogen, 12.2 cc.
Process: C3H7OH-H2-f K,
from which the formation of the amidine,
[C3H2(NH2)H20]2 or [C3H3(OH)NH2]2,
is inferred.
Isopropyl Alcohol shows the same ratios as the normal
alcohol.
•
AHyl Alcohol.— Employed: 0.150 ^g. and 23.5 cc. N2 ~ l|

Residual gas: H2 = 6.8 cc., N2 = 4.3 cc. Absorbed nitrogen^ 'Jii
19.2 cc.
Process: 3C3 H5OH4-N2 --fH,
"
from which is inferred the formation of the amidine, £
Phenol and pyrocatecMn readily absorb nitrogen; pyrogallol^

hydroquinone, and resorcin absorb the gas quite slowly.
Ethers and Nitrogen. 1
Ethylene Oxide. — 100 cc. C2H40 and 115.5 cc. N2 giver

H2 =5.5 cc., C2H6 = 0.4cc., N2=10.1 cc. Absorbed nitrogen
105.9 c.c. The formation of a body,
is inferred; It could be considered as an isomer of a hydrate

of cyanamide. 1',!^
Methyl Ether.—100 cc. (CH3 )2 0 and 127.9 cc. lsT2 give-
H2 = S6 cc., N2 = 65.6 cc. Absorbed nitrogen: 62.3 cc.
The ratio of the elements which react is the following:
(CH3 ) 2 0-1.72H-fl.25N.
The proportions are similar to those of the isomeric ethyl alco-
hol, but in the case of methyl ether they indicate a mixture.
Ethyl Ether.—100 cc. (C 2 H 5 )0 and 141 cc. N 2 give::
H2 = 174.2 cc.; N2 =44.6 cc. Absorbed nitrogen: 96.4 cc.
Ratio of the reacting elements:
(C2H5)0-~3.58H+N2.
Ethyl ether therefore gives off twice as much hydrogen and
absorbs twice as much nitrogen as methyl ether; which seems
to point to a fixed ratio between the nitrogen compounds farmed
and the molecular weight of the compounds started with.
Aldehydes, Ketoaes, and Nitrogen.1

Acetaldehyde.—Employed: 24 cc. CH3CHO and 22.8 cc. N2.
Based on 100 cc. aldehyde, there were obtained at the end
of the reaction: H2 = 25.8 cc.; H2 = 59.6 cc. Absorbed nitro-
.gen: 35.4 cc.
The ratio of the reacting elements is expressed by the
formula
C2H3.5ON0.35.
The ratio also remains constant with an excess of nitrogen,
.and leads to the reaction product
which, judging from its marked basic character, seems to con-

tain amido-groups.
Ethylene oxide, isomeric with this aldehyde, combines with
iive times as much nitrogen.
Propyl Aldehyde.—A large excess of nitrogen being present,
there were formed, based on 100 cc. C2H5CHO vapor: 112s
43.6 cc., C0 2 +C0 = 4 cc. Absorbed nitrogen: 66.7 cc.
These quantities correspond to a product CgHieNâ, in
which there are likewise supposed to be several amido-groups.
Acetone.—By employing an excess of nitrogen, there were
formed, based upon 100 cc. CH3COCH3 vapor: H2 = 33.3 cc,
Absorbed nitrogen: 89 cc.
These relations are expressed by the formula
[C3H(OH)(NH2)2]n.
Allyl alcohol, which is isomeric with acetone, absorbs only

one third as much nitrogen as acetone takes up and only half
that taken up by propyl aldehyde.
Methylal.—With an excess of nitrogen there are formed
from 100 cc, CH2 (OCH 3 ) 2 : H 2 =71.1 cc., C0 2 = 4.4 cc.,
CO=2.2 cc. Absorbed nitrogen: 128.9 cc.
1
Compt. rend. 12G> 671 (1898).
Berthelot seems to refer the calculated composition of the

reduction product
6H20
to polyamines having many hydroxyl groups and derived from.

the type (CHN)n; i-e., bodies which were obtained by him from
carbon monoxide, hydrogen, and nitrogen by means of the
silent electric discharge.
The following experiments could not be carried out to the-
end of the reaction on account of the trifling vapor tension of
the materials started with.
Aldol takes up large quantities of nitrogen, giving off trifling;
amounts of hydrogen; paraldehyde behaves similarly. Trioxy-
methijlene, on the contrary, and formaldehyde solution absorb
nitrogen only very slowly.
Camphor takes up nitrogen, forming a basic body.
Benzaldehyde, benzoin, cinnamic aldehyde, salicylic aldehyde^
furfurol, and quinone, under the influence of the discharge,
absorb nitrogen more or less rapidly.
Glucose, cellulose (paper), and dextrine1 can slowly take up
nitrogen; likewise the humus substances obtained by the action.
of concentrated hydrochloric acid upon sugar.
Acids and Nitrogen.2

Formic Acid. — Since formic acid is easily split up by the silent
electric discharge into carbon mon- and dioxides and hydrogen^
a noticeable absorption of nitrogen does not occur, but formic
methyl ester, although being likewise fundamentally broken.
up, takes up larger quantities of nitrogen.
Acetic Acid. — This acid absorbs nitrogen, forming trifling;
quantities of ammonia and a product which, according to the
analyses of the gases obtained by the discharge, is said to have
the composition of an amine or amide (Berthelot). The be-
havior of acetic methyl ester gives results which call to mind.
1
Essai de Mfemique chimique II, 388 (1879).
2
Compt. rend. 126, 681 (1898).
ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
those of acetic acid and methyl alcohol when each substance

is subjected by itself to reaction with nitrogen.
Other acids investigated were:
Propionic acid, crotonic acid, benzole acid, succinic acid,
malei'c and fumaric acid, phthalic acid, camphoric acid, glycollic
acid, lactic acid, malic acid, tartaric acid, the oxybenzoic acids,
pyroracemic acid, laevulinic acid, dehydracetic acid, and aceto-
acetic acid (or its esters).
All these substances (with the exception of fumaric and
phthalic acid, which, under the experimental conditions, do
not absorb nitrogen) take up more or less readily varying
quantities of nitrogen. The m-oxybenzoic acid absorbs con-
siderably less easily than its isomers.
Nitrogen Compounds and Mtrogen.1
Methylamine. — Hydrogen and nitrogen are split off, a

4 - solid product with alkaline reaction, and probably possessing
/' \ the composition of hexamethylenetetramine, being formed.
4 f Bimethylamine absorbs nitrogen, splitting off water in ratios
that likewise indicate the formation of hexamethylenetetramine.
Trimethylamine. — This substance, by absorbing a corre-
spondingly greater quantity of nitrogen, also seems to lead
to the same compound.
Ethylamine does not react with nitrogen, but it gives -off
,a quantity of hydrogen which indicates the formation of a
body homologous to hexamethylenetetramine.
Normal Propylamine absorbs nitrogen and gives off hydro-
:gen. The course of the reaction indicates the formation of
tetramines, which are derived from methyl- and ethylamine.
Iso-Propylamine shows the same behavior as the normal
compound.
Allylamine develops hydrogen, but neither absorbs nor splits
off nitrogen. The reaction product has a strong odor of piperi-
dine and perhaps the composition CgHigNs or C^HsoISU.
Compt. rend. 126, 775 (1898).
Aniline, Methylaniline, Benzylamine, the Toluidines, Pyridine,

and Piperidine take up nitrogen. Experimental, essential facts
for determining the nature of the resulting products are
lacking.
Ethylenediamine.—The volume of this compound is rapidly
increased by the action of the silent electric discharge. Hydro-
gen is primarily developed, with some ammonia, nitrogen, and
methane or ethane. Absorption of nitrogen and ammonia soon
occurs, and hydrogen is split off. In the second stage the
formation of condensation products (polyamines) presumably
predominates, while in the first period the decomposition of
the material started with prevails.
Propylenediamine behaves precisely like ethylenediamine,
Phenylenediamine (m- and p-), Benzidine and Nicotine absorb
very little nitrogen.
Acetamide and Glycocoll absorb little nitrogen, and the
quantity of the latter seems to depend upon the nitrogen ab-
sorption capacity of the respective acids.
Sulphocarbamide remains unchanged.
Nitriles (acetonitrile, benzonitrile, tolunitrile, benzyl cya-
nide) absorb nitrogen, the last three by direct addition without
giving off another element, while acetonitrile gives hydrogen
and some methane.
Aldoxkne (CHs-CHrN-OH) combines with nitrogen and
splits off water.
Phenylhydrazine is slightly decomposed, splitting off hydro-
gen and nitrogen.
Mtrometliane is fundamentally broken up, presumably by
internal oxidation, and with formation of condensed products;
hydrogen, oxygen, carbonic acid, and nitrogen are developed.
Nitroethane, unlike the last-mentioned compound, absorbs
nitrogen. The behavior of nitromethane corresponds to that
of formic acid, and that of nitroethane to that of acetic acid.
Nitrobenzene takes up little nitrogen.
« The following substances were also investigated:
Pyrrol, Indol, Indigotin, Azobenzene, and Albumens, all ab-
sorbing nitrogen.
t "
Ttdophene. — This compound under the influence of the
electric discharge absorbs as much as 8.6 per cent of its own
weight of nitrogen, (C4H4S)2N being formed (Berthelot).1
The following conclusions can be drawn from Berthelot 's
observations :
1. All the investigated alcohols fix nitrogen, forming amido-
like substances.
2. The aliphatic alcohols thereby lose hydrogen (excepting
allyl alcohol), an atom of nitrogen replacing a molecule of
hydrogen.
3. The loss of hydrogen is related to the behavior of the
hydrocarbons, which form the basis of the alcohols, when the
former are subjected to the same conditions.
4. Phenols bind nitrogen in varying proportions, but without
giving off hydrogen.
5. The isomeric aliphatic alcohols behave alike. They
thus differ from the three dihydroxybenzenes.
6. All aldehydes bind nitrogen by forming condensation
products. Amines or amides are produced. These are closely
related to the ammonia derivatives of the aldehydes, particularly
the glycosins, glyoxalines, and polyamines containing little
hydrogen.
7. Organic acids, just like the alcohols, aldehydes, and
hydrocarbons, generally combine with nitrogen, but no hydro-
gen, or but very little, is split off. Only phthalic acid and
fumaric (contrary to maleic) acid do not absorb nitrogen.
8. Most of the investigated nitrogenous compounds absorb
an additional quantity of nitrogen, and polyamines, polyamides,
and condensation products seem to be produced. Exceptions,
which do not show this behavior of absorbing nitrogen, are:
ethylamine, allylamine, phenylhydrazine, sulphocarbamide,
ethylenediamine, and propylenediamine. Methylamine and
nitromethane even give off nitrogen; this is probably due to
the low percentage of carbon.
9. Aliphatic nitrogen-containing compounds in taking up
1
Ann. chim. phys. 11, 35 (1897).
nitrogen lose about as much hydrogen as their corresponding

hydrocarbons and alcohols. Compounds are produced whose
cyclic character becomes more pronounced with an increasing
number of carbon atoms in the original molecules. Exceptions
to this rule are compounds rich in oxygen, like nitroethane and
glycocoll.
10. Cyclical compounds in absorbing nitrogen do not give
off hydrogen any more than cyclical hydrocarbons and
phenols. Piperidine, on the contrary, being a hydrated com-
pound, loses hydrogen in absorbing nitrogen, just like aliphatic
substances.
11. All compounds taking up nitrogen by simple addition—
without giving off hydrogen—i.e., hydrocarbons, alcohols, alde-
hydes, acids, and bases, when subjected to the influence of the
silent discharge, yield substances which behave like amides or
amines. Since the formation of these substances cannot, of
course, be based upon a substitution of NH2; NH, or N in place of
hydrogen, we must ascribe cyclic constitutions to the products
obtained.
12. The following table shows a comparison of polyamines
formed from hydrocarbons, alcohols, and bases by reaction
with nitrogen through the influence of the discharge. The
formulae of the reaction products are not rational ones, but
merely arranged in such a way that the quantities of the separate
elements in the molecule always refer to four nitrogen atoms.
This is done to express, in a comparable manner, the atomic
relations between the elements in the polyamines.
Composition of Polyamines formed from
Bases.
Hydro- Alcohols.
carbons.
Primary. Secondary. Tertiary.
Methane Series CaH18H4

Ethane Series
Propane Series
Allyl Series
•288 ELECTROCHEMISTRY OF ORGANIC COMPOUNDS.
'' The followi ng relations result from t he t ables:

For an equal weight of nitrogen the condensation of the
hydrocarbon residue combined w ith the nitrogen incr eases in
the t ransit ion from derivatives of hydr ocarbons to those of t he
.alcohols, except ing the polyamines resulting from the methane
series. This is very evident if t he composition of the m en-
tioned hydrocarbon residues is referred to an equal number of
c a r bo n a t o m s . T h e s a m e i n c r ea s e i s f o un d i f w e pa s s fr o m
the derivatives of the alcohols to those of the primary bases;
excepting t he compounds of the ethane series. This condensa-
tion is tw ice as large with the products from diamines as wi th
:
those from m onamines.
'; NL 2. B E HAVIOR OF VAPORS T OW ARDS T E SL A CURR ENTS .

4 A few remarks may be made here concerni ng obser vations
^ \ in a realm w hich promises to become especially important for
^ t h e or e t i c a l o r ga n i c c he m i s t r y . I t h as b e e n kn o w n f or s o m e
tli * time that highly rarefied gases or vapors, when subjected to
',! ,' the action of highly tensioned electric vibrations, become
, " luminous. Eemptinne, 1 by using Tesla currents and organic
,* s u b st an c e s, ha s r e c e nt l y t a k e n up t h e s ub j e c t o f t h e r el a t i o n
'£ b e t w e en l u m i n o si t y a n d c he m i c a l a c t i o n a n d t he d e p en d e nc e
\, ,; o f t h e ph e no m e n a up o n t he p r e ss u r e . H e f ou n d t ha t t h e
/ luminosity of the various substances in the arrangement of Tesla
|, is dependent upon the pressure. A perceptible decom position
4
I occurs from the beginning of the luminosity.
| i' A connection exists between the pressure at which the
I *' light effects of organic subst ances begi n and their molecular
I fy w e i g h t s ; b ut t he s e r e l a t i o ns h a v e no t y e t b ee n s u f f i ci en t l y
I, ;|i f explained.
2
I .?!?) H. Kaufmann has made extensive investigations concern-
l
I fill ^tschr. f. phys. Chemie 22, 358; 23, 483 (1897); Bull, de 1'Acad roy de
Betg. 11, 775 (1902).
2
' '' p Ztschr. f. physik. Chem. 2^, 719 (1898); 27, 519 (1898); 28, 673 (1899);
Ber. d. deutsch. chem. Gesellsch. 33, 1725 (1900); 34, 682 (1901); 35, 473,
.3668 (1902); 36, 561 (1903).
ing the luminosity of organic vapors under the influence of Tesla

currents at atmospheric pressure. He was thus enabled to for-
mulate a series of remarkable laws.
His experiments were arranged in the following manner:
The electric field in which the vapors are excited to lumi-
nosity is produced by a Tesla transformer, on the inside of a some-
what wide test-tube which has been converted into an ozonizer.
The outer layer, 5 cm. high and consisting of thin sheet copper,
is wrapped half way up around the test-tube; the outer layer
has a narrow vertical slit for conveniently observing the inside
of the tube. The inner coat, of mercury or tin, is placed in a
small, narrow glass tube, which is kept rigid and exactly in the
axis of the test-tube by a stopper closing the latter. The
stopper also supports a return-condenser arrangement, usually
a rising tube. The substances to be investigated are placed
in a solid or liquid state in the test-tube, and the whole tube
is then filled with vapor by vigorous boiling.
Some unimportant changes in the arrangement, such as
lowering the layers, etc., are made with very difficultly volatile
substances and such that readily char.
The luminous phenomena in these ozonizers occur in the
shape of more or less wide, colored bands of light, mostly in a
horizontal and radial direction. Non-luminous vapors either
remain wholly dark or become,—this is oftener the case,—
interspersed with green-colored sparks. The sparks very
rapidly decompose the vapors, precipitating carbonaceous
substances; the luminosity itself, on the contrary, produces
only extremely trifling changes in the substances.
The color of the luminous effects, in the majority of cases,
is violet, with numerous gradations between blue and red,
rarely yellow and green.
The hitherto observed regularities refer to the vapors
emitting the first-mentioned colors. We shall emphasize only
a few points among the great number of observations:
1. Aromatic substances usually possess an extraordinarily
higher luminosity than aliphatic compounds. However, simple
.aromatic hydrocarbons like benzene, its homologues and benzene
derivatives, possessing two or more nuclei linked by aliphatic?

residues, are either non-luminous or only slightly so. But
hydrocarbons containing two or more directly linked benzene
nuclei like diphenyl, carbazol, and condensed nuclei like naph-
thalene, anthracene, and phenanthrene show a brilliant violet
luminosity.
2. Substituents exert a powerful influence upon the light
effects. The introduction of several hydroxyl groups into
aromatic hydrocarbons of one nucleus produces luminous
effects which do not occur with only one hydroxyl group in the
molecule. The ammo-group always excites luminosity even
in mono-nuclear hydrocarbons. The effect of the amino-group
often enforces that of the hydroxyl group, thus aminophenols
produce luminous effects which are often very intense.
3. Acetyl, benzylidene, nitro-groups, the halogens, chlorine,
and bromine, and the carboxyl group, on the contrary, con-
siderably decrease the luminosity, sometimes completely.
Kaufmann seeks to employ these facts for obtaining an
i * insight into the ring system of benzene. Instead of using the
term "constitution/' he uses that of "condition," and shows
that in the luminous compounds the benzene nucleus is in an
unstable condition, one in, which it is disposed to change into
a quinone-like structure. The condition of the benzene nucleus,
determined by the chemical behavior of the ring, changes from
substance to substance in the greatest variety. These condi-
tions have possibilities which are represented by the Kekule,
the diagonal (Glaus and Korner), and the Dewar formula with
only one para-bond. The condition characterized in the first
formula, according to Baeyer's investigations, is found in
phloroglucin; the diagonal formula agrees excellently for phthalie
acid; and the Dewar formula, for instance, for dimethyl-p-
phenylenediamine.
The conditions for most of the benzene derivatives differ
from these three limiting conditions and assume1 mostly an
intermediate position which approximates more or less that of
the one or other limiting condition,
The luminosity caused by the action of Tesla currents indi-

cates that the ring of the respective substance exists in Dewar's
condition; the stronger the luminosity the more pronounced the
latter must be.
The one para-bond in Dewar's ring is unstable, and is char-
acterized by the fact that it can easily be broken down, by | jj
oxidizers; it thus differs from the three para-bonds of the two ;yj
other f ormute. I1.*
4. In the aliphatic series Tesla currents are absorbed and Kj
•converted into light by the vapors of aldehydes and ketones; |.|j
the carbonyl group is the sole carrier of the luminosity. The \ l\
latter disappears with derivatives of aldehydes and ketones Jî,
which do not have the carbonyl group. The luminosity de- i;<i
creases: Firstly, with increasing number of carbon atoms (intro- f-'1
cluction of methyl groups); secondly, with the entrance of a jj ij
•earboxethyl group; and thirdly, especially in the presence of f;||
a phenyl residue (benzaldehyde, acetophenone, etc., show no ^!!!
luminous effects). Ring ketones without a double bond be- If;,
tween carbon atoms can be luminous; such with double bonds
cannot.
Kaufmann explains the luminosity of aldehydes and ketones
by the supposition that the carbonyl group, the carrier of the
luminous effects in those substances" can occur in various states
•or conditions, like the benzene nucleus. Only such bodies
which have the atoms of the carbonyl group loosely bound
&nd in a reactive state can show luminosity. Reactability
and luminosity run parallel. The latter is, hence, present in
.aldehydes and ketones, but not in acids, acid anhydrides, esters,
and amides, all of which contain the same group but in a con-
dition of extremely trifling reactability; or, we can say, the
.atoms of this group are firmly bound.
I
The luminosity of vapors under the influence of Tesla oscilla- |J
tions is undoubtedly closely related to the constitution of the
substances. It also seems true that a continuous transition
from the non-luminous to the luminous vapors takes place, so that
only quantitative, but no substantial, differences exist between
the conditions characterized by the luminosity. In order to-

obtain a better understanding of the relations, it is necessary
to measure these phenomena and, on the basis of quantitative
determinations, to seek determinative connections, just as,
for instance, has been done in the case of the conductivity of
'electrolytes. , . ,
613 - ' >•'•• •
vv^ or
>r
LIST OF AUTHOK . SM
Aatfand, 115, 116 • , Buff, 238, 244, 245, 247, 248, 251
Abrefcch, 168, 173, ITS-. > Bunge; 65, 85, 87, 104, 199, 201, 212-
Ach, 129,-ISO '
Ahrens, '74, 121, 192, 193/216, 21$, Cainpani,"65r
Campari, 21
219 ' '. le Chatelier, 239
Akerberg, 33, 38, 106 Chflesetti, 143,144
"Alefeld, 202 Clark, 110
Alessi, 104, 105 Classen, 104, 201
Almeida, 57, 59 Clement, 137, 156, 184
Always, 182 Coehn, 22, 23, 55, 56, 76
Andrews, 247 Collie, 266
Connel, 57, 59
Bach, 76 Constan, 76
Baillie, 119, 129, 215,218 Coppadoro, 112
Balbiano, 104, 105 Cormack, 227
Bamberger, 146, 158 Coughlin, 61, 71
Bartoli, 55, 59, 64, 77, 119, 199
Becquerel, 59, 229 Dalton, 244, 245
Berl, 82 Davy, 247, 252
Berthelot, 118, 244, 245, 246,247, Deh&ran, 57, 59
250, 266-279 Despretz, 81
Bichat, 263 Destrem, 248
Billitzer, 56 Dieterle, 173
Biltz, 204 Dorrance, 178
Binz, A., 216 Drechsel, 230, 231
Bizzarini, 65 Dumas, 229
le Blanc, 46 Dupre*, 81
Bolton, 250
Bourgoin, 77, 79, 81, 104, 106, 109- Ehrenfeld, 75
112, 113-116, 117, 211, 212, 219- Eckstein, 227
221 Elbs, 4, 58, 60, 63, 70, 74, 81, 85,
Bouveault, 111 136, 138-142, 150, 154, 158-175-
Bottens, Pauchand de, 49, 134, 152 179, 183, 186-189, 204 205, 207,
Brand, 70, 74, 141, 204, 205, 207- 208 208
Brandon, 220 Escherich, 208
Brazier, 92, 93 Etard, 200
Bredig, 233, 238, 250
Bredt 225 Ewers, 85, 87, 90
Brester, 68, 77, 90, 116, 211, 213
Brislee, 33 Faraday, 30, 234
Brodie, 245, 266, 267 Fichte, 173
Brown, 76, 102, 103, 105, 107, 110, Fdlsing, 196
113, 114, 212, 213, 225 Forster, 61,83
Bruimer, 30, 33, 58, 60, 63 Friedel, 69, 226
293
:294 LIST OF AUTHORS.
Friedrichs, 78,101,105, 133, 211, 213 Klobukow, 76, 248

Knudson, 67
Gans, 229 Kolbe, 65, 76, 79, 81, 85, 88, 90, 97
Gasparini, 109 Komppa, 114
•Gattermann, 10, 133, 136, 137, 138, Kopp, 159, 160, 168, 171, 172, 177
156, 157, 164, 168-175, 177, 183, Koppert, 137, 156, 169
184, 186, 187, 191 Kraszler, 131
Gay-Lussac, 119, 246 Kratz, 85
Gerdes, 230, 231 Kremann, 173, 187
Gilmour, 251
Glaser, 47 Lebhardt, 172, 213
Goecke, 118, 170 Langley, 239
Goldschmidt, H., 32, 35 Lapsehin, 78
Goppelsroder, 194, 195, 209, 216 Lassaigne, 220, 229
•Gossleth, 92, 93 Lassar-Coehn, 81
•Gruszkiewicz, 246 Law, 134
Gunn, O'Brien, 68 Lecher, 273
Guntz, 263 Lees, 223
•Guthrie, 65, 103 Legler, 238, 253
Lepsius, 238
Haber, 10, 34, 37, 48, 51, 143, 146, Lieben, 76
147, 151, 154, 155, 158, 163, 238, Liebermann, 133
252 Liebmann, 202
Habermann. 57, 58, 59 Lob, 10-20-22, 23, 43, 49, 52, 80, 95,
.Hagenbach, 216 138, 139, 143, 146, 151, 154, 156,
Hamonet, 87, 89, 96, 98, 99 157, 158, 160, 161, 162, 163, 164-
Hansen, 76 173, 175, 177, 181, 183, 188, 196,
Hauser, 214 197, 199, 201, 211, 213, 241, 250,
Haussermann, 136,142,154,158,161, 253, 254, 257, 258, 259, 266, 267
168, 169, 176, 177, 187 Lobe, 72
Heider, 168, 172, 175 Lommel, 247
Heilpern, 133 Losanitsch, 264, 266, 269, 270
Hemptinne, 264, 267, 270-279 Liidersdorf, 59
Renault, 0. Dony-, 28, 47, 58, 60, 62 Lumsden, 114
Henderson, 226 Luther, 33
Herz, 60
Hittorf, 65 Maquenne, 270, 273, 274, 277
Hof, 181, 188 Mane, 118, 213
Hofer, 69, 78, 82, 84, 86, 89, 96, 97, Matteuci, 211
100, 101, 108, 111, 116, 215, 249 McCoy, 64
Hofmann, 238, 244, 245, 247, 248, 251 Meissner, 74
Hostmann, 183, 203 Melly, 247
Htmtington, 246 Merzbacher, 134
Messinger, 201
Jahn, 58, 76, 77, 79, 86 Mettler, 212
Jaillard, 57, 59 Mewes, 61
James, 209 Meyer, E. v., 245
Joist, 256 v. Miller, 68, 86, 95, 96, 97,101,103,
Jovitschitsch, 264, 266, 269, 270 106, 108, 111, 116, 117, 213, 215
Jurgenseu, 234 Mixter, 245
Moest, 78, 82, 84, 86, 89, 111, 208
Kampf, 81 Moissan, 237, 250
Kaufmann, 181, 203, 204, 207, 209, Moller, 191, 192
288 Moore, 15, 20, 49, 53, 85, 143, 151
Keiper, 189 Monfang, 222
K<§kul<§, 76, 80, 109,115,116 Miiller, 22, 23, 72, 163
Kempf, 133, 173 Mulder, 69
Kendall, 154 Mullerus, 216
Klappert, 176 Mulliken, 74, 76,103,108, 117
Klein, 184 Murray, 82
LIST OF AUTHORS: 295
Muthmann, 249 Singer, 62 •

Slawik, 213
Naumann, 24, 25, 221, 222 Slosse, 268, 270
Nernst, 17, 21,30,33,35,37,45 . Smith, E. R, 4, 81, 110, 134
Noyes, 30, 137, 156, 178, 184 Sollmann, 193
Sonneborn, 178
Oettel, 4, 106 Stern, 119, 120
Stone, 64
Oswald, 45 Straub, 158, 160
Strobel, 192
Palmaer, 118 Sulzberger, 173
Papasogli, 55, 59, 64, 77, 119, 199 Szarvasy, 196
Paschen, 239
Perkin, 134, 202, 246 Tafel, 14, 22, 23, 27, 43, 52, 67, 70,
Perlin, 210 73, 78, 101, 105, 119, 122, 123,
125, 126, 128, 129, 143, 144, 145,
Petersen, 78, 82, 89, 90, 93, 10G, 110, 191, 192, 203-205, 212, 213, 215,
113,114 218, 221, 222, 225, 227
Perrot, 119, 247, 248 Tait, 247
Pfeffermann, 67, 73, 203-205 Teeple, 71, 72
Phipson, 267 Thenard, 245, 270
Pierron, 169 Thomas, 119
Piguet, S3 Tichanowitsch, 78, 203
Pinnow, 179 Tornmasi, 68
Pissarshewski, 99 Troeger, 85, 87, 90
Pommerehne, 220, 221 Truchot, 248
Prevost, 229
Puls, 134 Ullmann, 173
Ulpiani, 109
Quet, M., 247 Ulsch, 69
Quincke, 234
Vanzetti, 112
Readmann, 251 Vaubel, 202
Reboul, 112, 113 Violle, 239
Reindl, 122, 123 Voigt, 64, 177, 190, 191, 195
Renard, 57, 58, (i3, 64, 65, 66,68, Vortmann, 201
77, 104, 133, 134 Votocek, 196
Richard, 70
Riche, 59, 60 Walker, 76, 97, 102, 103, 105, 107,
Rockwell, 100 108, 110, 113, 114, 212, 213, 225-
Rohde, 169, 176, 177, 178, 180, 191 227
Rohland, 93, 94 v. Wartha, 216
Romppa, 225 Weems, 76, 100, 101, 103, 108, 118
Russ, 34, 37, 53, 151 Weinschenk, 122, 128
Rotundi, 193
Royer, 50, 76, 105 Weith, 119
Weizmann, 191, 210
Sachs, 173 Werther, 64
Salzer, 77, 106 Whitney, 30
Sand, 62 Widera, 193
Schall, 6, 80, 130, 131, 184, 211 Wiedemann, 81
Schlagdenhauffen, 119 Wilde, 245, 247, 249
Schmidt, 72, 177, 192, 207 Wogrinz, 183
Schmitt, 135, 169, 171 Wohlfahrt, 173, 186
Schmitz, 27, 225 Wolffenstein, 220
Schonbein, 59, 119 Wurtz, 92, 94, 95, 103
Schwerin, 234
Sebor, 196, 213 Zehrlant, 200
Shedden, 223 Zenisek, 196
Shields, 115 Zschocke, 172, 213
Silbermann, 140, 162, 163
LIBRARY
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X f i S ^G A LS ^
INDEX.
Acetaldeyhde, 50, 59, GO, 07, 87, 97, Aconitic acid, 118
98, 99, 100, 111, 11(5, 253, 270, 27(> Acridine, 259
Acetaldehyde and nitrogen, 282 Aerolem, 64, 245
Acetamide and nitrogen, 285 Acrylic acid, 64, 116
Acetanilide, 190, 215 Acrylic ester, 110
Acetates, 79, 81, 82 Adenine, 127
Acetic acid, 57, GO, 63, 64, 69, 78, 99, Adipic acid, 111, 114, 232
100, 111, 245, 248, 251, 253, 278 Adipic diethyl ester, 112
Acetic acid and nitrogen, 283 Adipic ethyl ester, 110
Acetic aldehyde, see Acetaldehyde Albumen, 229, 233
Acetic anhydride, 80 Albumen and nitrogen, 285
Acetic esters, 59, 78, 84,101, 278,283 Alcohols, 62, 202, 211, 273
Acetoacetic acid, 100 Alcohols and nitrogen, 279
Acetoacetic acid and nitrogen, 284 Aldehydecopellidinehydrazine, 193
Acetoacetic ester, 100 Aldehydephenylhydroxylamine, 182
Acetone, 63, 69, 98, 248, 277 Aldehyde resin, 59
Acetonedicarboxylic acid, 101 Aldehydes-, 66, 157, 202, 276
Acetonephenylhydrazone, 73 Aldol, 98
Acetonitrile, 121 Aldol and nitrogen, 283
Acetonitrile and nitrogen, 285 Aldoxime and nitrogen, 285
Aoetonylacetone, 102 Aliphatic corripounds, 54
Acetopnenone, 204 Alizarin, 133, 195, 210
Acetophenone-oxime, 204 Alizarinamide, 191
Aeetophenonepinaeone, 204 Alizarin-bordeaux, 133
Acetoxime, 72 Alizarin-cyanine, 133
Aeetylacetone, 74 Alkaloids, 217
Aeetylacetonedioxime, 74 Alkyl-disulphides, 65
Acetylaminophenol, 223 Alkyl-hydroxylamines, 56
Acetyl chloride, 256 ALlocampholytic acid, 226
Acetyl disulphide, 85 Allocamphoric acid, 226
Acetylene, 56, 110,115,118,211, 244, Aliocamphoric ester, 227
245-250-271, 278 Alloxan, 124
Acetylene and nitrogen, 271 Alloxantin, 124
Acetylmalonic acid, 101 Ally! alcohol, 276
Acetylmethylaminophenol, 224 Allyl alcohol and nitrogen, 281, 282
Acetylpyrrolidone, 121 Allylamine and nitrogen, 284
Aeetyltetrahjdroqmnoline, 218 Allylene, 271
Acetyltoluidme, 215 Allylene and nitrogen, 271
Acid amides, 118, 215 Alternating currents, 230
Acidnitroamides, 166 Amidoacetone, 74 .
Acids, 75, 277 Amidoacetophenone, 183
Acids and nitrogen, 283 Amidoalizarin, 210
Acid superoxides, 80 Amidoanthraquinone, 191
Acid supersulphides, 80 Amidoazobenzene, 178
298 INDEX.
Amidoazo-compounds, 194 Anthranilic acid, 184, 258

Amidobenzophenone, 183 Anthranols, 210
Amidobenzyi alcohol, 170 Anthraquinone, 133, 195, 209
Amidocaproic âcid, 193 Anthrones, 210
Amidocoumarin, 185 Argon, 272
Amidocresol, 168, 175 Aristol, 201
Amidoeresolsulphonic acid, 187 Aromatic compounds, 132
Amidocresotinic acid, 185 Atropine, 219
Amidodihydropurm, 130^ Attackable electrodes, 18
Amidodimethylaniline, 178 Azoacetophenone, 183
Amidodiphenyl, 173 Azoanisol, 176
Amidodiphenylamine, 180 Azobenzamide, 186
Amidohydroquinone, 196 Azobenzene, 133, 136-159-163
Amidonaphtholsulphonic acids, 191 Azobenzene and nitrogen, 285
Amidonaphthyl ethyl ether, 191 Azobenzoic acid, 181, 183, 188
Amidonitrophenol, 176 Azobenzoic-acid-benzyl alcohol, 188
Amidooxyacetophenone, 183 Azobenzonitrile, 186
Amidooxycinnamic acids, 185 Azobenzophenone, 183
Amidooxydiethylaniline, 179 Azobenzyl alcohol, 181, 188
Amidooxypunn, 130 Azo-compounds, 194
Amidooxyquinoline, 193 Azo-dyes, 197
Amidooxyterephthalic acid, 186 Azophenine, 196
Amidooxytoluquinoline, 193 Azophenol, 176
Amidophenantnrenequinone, 192 Azophthalic acid, 186
Amidophenols, 136, 137, 138, 149, Azostilbenedisulphonic acid, 187, 18S
154,156-176 Azotoluene, 136, 168, 171
Amidophenol sulphate, 137 Azotoluenebenzoic acid, 189
Amidophenolsulphonic acids, 137, Azoxyacetophenone, 183
156, 176, 184, 187 Azoxyanisol, 176
Amidophenylhydroxylamine, 164 Azoxybenzaldpxime, 182
Amidophenyltolyl ether, 177 Azoxybenzamide, 186
Amidophthalic acid, 186 Azoxybenzene, 136-143-147-158-163
Amidopurin, 130 Azoxybenzoic acid, 181, 183, 184
Amidosalicylic acid, 184 Azoxybenzonitrile, 186
Amidosulphonic acids, 187 Azoxybenzophenone, 183
Amido valeric acids, 192 Azoxybenzyl alcohol, 181
Amidoxylenol, 172 Azoxydiphenyl ether, 177
Amines, 57, 67, 73, 118, 121, 203, Azoxylene, 172
215, 216, etc. Azoxyphenanthrene, 192
Amino, see Amido Azoxyphenyl ethers, 177
Ammonia, 246 Azoxyphenyltolyl ether, 177
Ammonium carbamate, 230 Azoxystilbene, 173
Ammonium dithiocarbamate, 131 Azoxystilbenedisulphonic acid, 187
Amyl alcohols, 63, 93 Azoxytoluenes, 136, 168, 169, 171
Amyl caproate, 92, 93 Azoxyxylenes, 172
Arnylenes, 93
Amylhydrocinnamic ester, 214 Barbituric acid, 123, 124
, '<$ Amyloxypropionic acid, 98 Benzal chloride, 159
?;W Benzaldehyde, 134,138,157,168,170,
Anhydroamidobenzyl alcohol, 158
Anhydrohydroxylaminebenzyl alco- 203, 212, 215, 260
hol, 158 Benzaldehyde and nitrogen, 283
Anilidoinduline, 196 Benzaldpxime, 203
Aniline, 136-162-163, 176, 193-198, Benzamide, 215
203-246, 249, 254, 258 Benzene, 133, 246, 248, 251, 253,
Aniline and nitrogen, 285 Jo 7
Aniline black, 195 Benzene and hydrogen, 272
Anisidine, 176 Benzene and nitrogen, 272
Anodic depolarizers, 8 Benzeneazonaphthol, 155
Anodic processes, 27 Benzeneazonaphthylamine, 155
Anthraiiil, 258 Benzenephenylenediamine, 196
INDEX. 299
Benzhydrol, 204, 205 Butyl caproyl, 95

Benzhydrylamine, 205 Butylenes, 90, 91, 92
Benzidine, 136, 139, 140, 142, 160, Butyl valerate, 90, 91
161, 167 Butyrates, 88, 101
Benzidine and nitrogen, 285 Butyric acids, 87, 89, 231, 232, 270
Benzile, 209 Butyric aldehyde, 91
Benzilic acid, 209 Butyric ethyl ester, 108, 111
Benzoic acid, 134, 209, 211, 200, Butyric isopropyl ester, 88
279 Caffeme>a127, 120
Benzoic acid and nitrogen, 284 Camphidine, 228
Benzoic esters, 212 Camphidone, 2^8
Benzoic ethyl ester, 134 Campholytic acid, 226
Benzoin, 209, 283 Camphor, 225
Benzoin and nitrogen, 283 Camphor and nitrogen, 283
Benzonitrile, 121, 21(5 Camphoric acid, 225, 227
Benzonitrile, and nitrogen, 285 Camphoric-a-cid-imide, 227
Benzophenone, 204 Camphoric acid and nitrogen, 284
Benzophenone-oxime, 205 Camphoric esters, 225
Benzophenonepinacone, 205 Camphothetic acid, 226
Benzotrichloride, 259 Cane-sugar, 68
Benzoylazoxydiphenylamine, 181 Caproic acid, 92, 101, 231, 232
Benzoylbisulphide, 212 Caproic amyl ester, 92, 93
Benzoylnitrodiphenylamine, 180 Caprylic acid, 93
Benzoylpiperidine^ 218 Carbamic acid, 230
Benzoylsulphonimides, 216 Carbamide, 230
Benzpinacoline, 205 Carbazole, 258
Benzyl alcohol, 134, 212, 215 Carbides, metal, 250
Benzylamine, 121, 203, 215, 216 Carbohydrates, 268
Benzylamine and nitrogen, 285 Carbolic acid, see Phenol.
Benzyl chloride, 259 Carbon, 54, 250
Benzyl cyanide, 121, 216 Carbon disulphide, 245
Benzyl cyanide and nitrogen, 285
Benzyl ethers, 212 Carbon disulpnide and hydrogen, 269
Benzylidenephenylhydrazone, 203 Carbon hydroxide, 55
Benzylidenephenylhydroxylamine, Carbonic acid, 76, 266
138, 157 Carbonic-acid derivatives, 121
Benzylidenetolylhydroxylamine, 168, Carbon monosulphide, 269
169 Carbon monoxide, 267
Benzylmalonic acid, 116, 213 Carbon monoxide and ammonia, 270
Benzylpiperidine, 218 Carbon monoxide and dioxide, 268
Blood, 229 Carbon monoxide and hydrochloric
Borneol, 225 acid, 269
Bromacetone, 71 Carbon monoxide and hydrogen sul-
Bromamidocresol, 175 phide, 269
Bromamidophenol, 175 Carbon oxysulphide, 269
Bromanilines, 156 Carbon suboxide, 266
Brombenzene, 197 Carbon tetrachloride, 250, 255
Brombenzoic acid, 212 Carvacrol, 201
Brombenzoic esters, 212 Catalytic influences, 24
Bromine, 250 Cataphoresis, 233
Brommaleie acid, 115 Cathode material, 152, 167, 169, 171
Bromnitrobenzene, 175 Cathodic depolarizers, 7
Bromnitrotoluene, 175 Cathodic processes, 18
Bromoform, 60, 71, 256 Cells, 40
Bromstyrene, 213 Cellulose and nitrogen, 283
Brucidine, 223 Chloracetic acids, 59, 85
Brucine, 222 Chloracetone, 69, 70
Butane, 86, 87 Chloral, d62
Butandiol diamyl ether, 98 Chloral hydrate, 68, 255
Butyl alcohol, 74, 91 CUoraminophenol, 175
300 INDEX.
Chloranillne, 138, 139, 140, 156, 174 Diamidobenzene, 164, 178

Chlor benzene, 197 Diamidobenzhydrols, 208
Chiorbenzoic esters, 212 Diamidobutane, 123
Chlor-hydrocarbons, 250 Diamidochrysazindisulphonic acid,
Chlorine, 250 192
Chlornaphthalene, 197 Diamidocresol, 173
Chlornitrobenzene, 174 Diamidodibenzyldisulphonlc .acid, 188
Chlornitrotoluenes, 175 Diamidodimethyloxyphenazone, 174,
Cliloroform, 60, 70, 253 179
Chloroform and aniline, 254 Diamidonitrophenol, 176
Clilorphenylmethylene, 259 Diamidopentane, 74
Chlorpropionic acid, 87 Diamidophenanthrenequinone, 192
Chlortoluene, 197 Diamidophenazone, 174
Chlortoluidine, 175 Diamidophenol, 173, 176, 177
Chrysamine G, 198 Diamidophenyltolylmethane, 170
Chrysaniline, 195 Diamidopropane, 123
Cinchonidine, 221 Diamjdostilbene, 173
Cinchonine, 221 Diamidostilbenedisulphonic acid, 187,
Cinnamie acid, 213 188
Cinnamic aldehyde and nitrogen, 283 Dianilidoquinoneanil, 176
Cinnamic ester, 214 Dianisidine-blue, 198
Citraconic acid, 116 Diatomic alcohols, 63.
Coca-alkaloids, 219 Diazoamido-eompoimds, 194
Cocaine, 219 Diazo-compounds, 194
Codeine, 220 Dibasic acids, 102
Collodion, 68 Dibenzylacetic acid, 214
Colloids, 233 Dibenzylketone, 208
Congo, 198 Dibenzylsuccinic acid, 214
Cotarnine, 220 Dibromanthraquinone, 210
Cresol, 258 Dichloracetic acid, 85
Cresotinic acidr 201 Dichloracetone, 69
Crotonic acid and nitrogen, 284 Dichloraniline, 175
Crotonic aldehyde, 98, 116 Dichlonnetjiylene, 254
Cyanacetates, 85 Dichlornitrobenzene, 175 ,
Cyanacetic ester, 98 Dichlorpropionic acid, 87
Cyanides, 251 Dichlorpropionic dichlorethyl ester,
Cyanogen, 121, 247, 251, 252 87
Cyclohexanone, 231 Diethylamine, 67
Diethylamrnonium diethyldithiocar-
Hecahexanedicarboxylic acid, 115 bamate, 131
Decane, 92, 93, 95, 107 Diffusion theory, 30
Deeanedicarboxylic acid, 114 Dihydroquinoline, 218
Dehydracetic acid, 284 Dihydroxylamine, 145
Depolarizers, 6, 7, 8 Diisobutane, 90
Desoxy-bodies, 127, 128 Diisobutyl, 91
Desoxycaffeme, 129 Diisopropyl, 89
Desoxyguanine, 130 Dimethylamine, 284
Desoxyheteroxanthine, 128, 129 Dimethylaniline, 198
Desoxytheobromine, 129 Dimethylbenzaldehydes, 134
Desoxyxanthine, 127 Dimethylbenzamide, 215
Dextrine, 68 Dimethylbenzimidazole, 179
Dextrine and nitrogen, 283 Dimethyl benzylamine, 215
Diacetyi, 100, 101 Dimethyldiamidoazobenzene, 178
Diacetyldiaraidoazoxybenzene, 178 Dimethyldiamido phenol, 178
Diacetylsuecinic ester, 100 Dimethylethanetetracarboxylic acid,
Dlalurie acid, 123 108
Diamldoanthraquinones, 192 Diraethyloxydihydropurin, 129
Diamidoanthrarufindisulphonic acid, Dimethyloxypurpn, 129
192 Dimethyloxypurinmethylhydroxide,
Diamidoazobenzene, 164, 177 129
INDEX. 301
Dimethylphenazone, 174 Electrodes, 18, 51

Dimethyipiperylhydrazine, 193 Electrolysis of mixtures, 94
Dimethylpurons, 126 Electrolytic processes, 10
Dimethyipyrazine, 74 Electropyrogenizer, 242
Dimethylpyrazolidme, 74 Endosmose, electric, 233
Dimethylsuccinic acid, 107 Eosin, 201, 202
Dimethyltoluidine, 170, 171 Erythrite, 65
Bimethyltoluylenediamine, 180 Ethane, 59, 79,81,116, 271, 275, 276,
Dimethyl uric acids, 126 278
Dimethylxanthine, 129 Ethane and carbon monoxide, 271
Dmitroanisidine, 174 Ethane and nitrogen, 271
Dinitroanthrarunndisulphonic acid, Ethanehexacarboxylic ester, 117
192 Ethanetetracarboxylic ester, 108
Dinitroanthraquinone, 192 Ether, ethyl, 246, 247, 253
Dinitrobenzene, 173 Ethers and nitrogen, 281
Dinitrobenzidine, 174 Ethoxybenzophenone, 206
Dinitrobenzoic acid, 173 Ethoxybenzpinacoline, 206
Dinitrochrysazindisulphonic acid, 192 Ethyl alcohol, 59, 97, 247, 274
Dinitrodibenzyldisul phonic acid, 188 Ethyl alcohol and nitrogen, 280
Dinitrodiphenyl, 185 Ethylamine, 57, 67, 121, 248
Dinitroditolyl, 174 Ethylamine and nitrogen, 284
Dinitroethanetetracarboxylic acid, Ethylaminophenol, 223
109 Ethylaniline, 215
Dinitronaphthalene, 191 Ethylcrotonic acid, 108
Dinitrophenanthrenequinone, 192 Ethyl cyanide, 248
Dinitrophenol, 176 Ethyldioxysulphocarbonate, 131
Dinitrostilbene, 173 Ethylene, 81, 86, 106, 110, 116, 245,
Dinitrostilbenedisulphonic acid, 187, 246, 247, 248, 252, 253, 256, 273,
275
188 Ethylene and nitrogen, 271, 278
Dinitrotetraethyldiamidodiphenyl,
174 Ethylene cyanide, 82
Dinitrotetramethyldiamidodiphenyl, Ethylenediamine and nitrogen, 285
174 Ethylenedihydroxyiamine, 73
Dinitrotoluene, 173 Ethylenelactie acid, 98
Dioctyl, 93 Ethylene oxide and nitrogen, 281,
Dioxy-acids, 98, 98 282
Dioxyanthraquinone, 210 Ethyl ether, 246, 247, 253
Dioxybenzene, 232 Ethyl ether and nitrogen, 281
Dioxybenzoic acid, 214 Ethyl glycollic ether, 97
Dioxybutyrie acid, 99 Ethylhydroxylamine, 57
Diphenol, 231 Ethylideneimine, 67
Diphenyl, 212, 248, 249, 257 Ethylidene oxyethyl ether, 59
Diphenylamine, 195, 258 Ethylidene phenylhydrazone, 67
Diphenylamine and chloroform, 258 Ethylmalomc acid, 108, 114
Diphenylbenzene, 257 Ethylrnethylacetic acid, 92
Diphenylenediamine, 272 Ethylphosphorie acid, 66
Diphenylmethane, 205 Ethyl potassium diethylmalonate,
Diphenylthiocarbazide, 131 107, 108
Bisulphide, acetyl, 85 Ethyl potassium dimethylmalonate,
Dithiocarbamic acid, 131 107, 108
Dithiondisulphides ,131 Ethyl potassium, ethylmalonate, 107
Dithymoldiiodide, 201 Ethyl potassium fumarate, 115
Ditolylamine, 195 Ethyl potassium glutarate, 113
Dodecane, 93, 95 Ethyl potassium maleate, 115
Dodecanedicarboxylic acid, 115 Ethyl potassium malonate, 103, 104
Dowson gas, 246 Ethyl potassium methybnalonate,
107, 112
Electric flame, 249 Ethyl potassium oxalate, 105
Electrode potential, 14 Ethyl potassium succinate, 112
Electrode processes, 18 Ethyl propionate, 86
302 INDEX
Ethyl pyrrolidone, 120 Heptane, 95

Ethylsuccinic acid, 117 Heptylic acid, 93
Ethyl-sulphuric acid, 59, 60, 66 Heteroxanthine, 128
Ethyltartaric acid, 117 Hexachlorbenzene, 250
Ethyltetrahydroquinoline, 218 Hexachlorhexane, 90
Ethyltoluidine, 215 Hexamethylenetetramine, 67, 284
Ethyltrithiocarbonic acid, 131 Hexane, 88, 89, 101, 252
Ethyl urea, 122 Hexamethylethane, 92
Eugenol, 202 Hexaoxymethylene peroxide, 253
Excess potential, 20, 27 Hexyleneglycol, 99
Experimental arrangements, 44 Hydantoin, 122
Hydracrylic acid, 99, 111
Hydrastinine, 220
Flaming discharge, 249 Hydrazoanisol, 176
Fluor-albumens, 229 Hydrazobenzene, 136-160-168
Muoreseei'n, 201, 202 Hydrazobenzoic acids, 183, 184
Formaldehyde, 57, 58, 66, 67, 76, Hydrazobenzoi'n, 203
93, 97, 98, 99, 117, 157, 171, 251, Hydrazo-compounds, 141
253, 267, 268, 269, 270 Hydrazonaphthalenesulphonic acid,
Formaldehyde and nitrogen, 283 191
Formamide, 270 Hydrazophthalic acid, 186
Formic acid, 56, 63, 64, 65, 66, 68, Hydrazotoluene, 136, 168, 169, 171
69, 76, 77, 96, 97, 98, 99, 105-111- Hydrazoxylene, 171
"117, 231, 245, 248, 250, 253, 257, Hydroanthranols, 210
266, 267, 270, 277 Hydroanthraquinone, 210
Formic acid and nitrogen, 283 Hydrobenzoi'n, 203
Formic ester, 59, 78 Hydrocarbons, 54, 133, 244, 270
Formic ethyl ester, 278 Hydrocinnamic acid, 213, 214
Formic methyl ester, 278 Hydrocyanic acid, 121, 245, 246, 247,
Formic methyl ester and nitrogen, 249
283 Hydrocotarnine, 220
Fonnyl chloride, 256, 269 Hydrohydrastinine, 220
Formylphenyl ether, 182 Hydrophenoketone, 232
Fulmmuric acid, 109 Hydrophenazone, 173
Fumaric acid, 115, 284 Hydroquinaldine, 219
Furfurol and nitrogen, 283 Hydroquinoline, 218
Hydroquinone 133, 201, 218, 231
Gallaminic acid, 214 Hydroquinone and nitrogen, 281
Gallic acid, 202, 214 Hydroquinonecarboxylic acid, 133
Generator gas, 246 Hydroquinone ether, 200
Glucose, 62, 68, 203 Hydroquinone-p-nitrodiphenyl ether,
Glucose and nitrogen, 285 177
Glutaric acid, 112, 232 Hydrouracyl, 123, 124
Glutaric diethyl ester, 112 Hydroxycaffeme, 127
Glyceric acid, 64, 98, 279 Hydroxylamine, 57, 145
Glyceric aldehyde, 64, 279 Hydroxyl-cpmpounds, 57
Glycerine, 64, 276 Hypoxanthine 127
Giycocoll and nitrogen, 285 Humus substances and nitrogen, 283
Glycol, 6S, 276
^Glycollic acid, 64, 96, 97, 105, 279 Imides, 118
dycollic acid and nitrogen, 284 Indigo reduction, 216, 217
c ethyl ether, 97 Indigotin and nitrogen, 285
67, 73, 277 Indol and nitrogen, 285
Glyomlic acid, 73 Induline dyes, 196
Glyox%e, 67, 73 Iodine, 250
Glyoxylil^cid, 67, 105 lodonitrobenzene, 175
Grape-sugilk 68 lodoform, 60, 72, 87, 119
Graphitic acM^CS, 64 lodopropionic acid, 87
Guanine, 127,'. Isethionic acid, 66
Gum arable, 68 Isoacetyl-o-aminophenol, 223
i
INDEX. 303-
Isoamyl alcohol, 63 Mercuric-iodide compounds of alco-

Isoamylphosphoric acid, 66 hols, 62
Isoamylsulphuric acid, 66 Mercury methide, 272
Isoamylxanthate, 131 Mercury phenide, 272
Isobutylacetic ester, 112 Mesaconic acid, 116
Isobutyl alcohol, 91 Mesitylene, 134
Isobutylcresol, 201 , Mesitylenic aldehyde, 134
Isobutylene, 92 Mesityloxide, 70
Isobutyl isovalerate, 91 Mesoxalyl urea, 124
Isobutylphenol, 201 Metanilic acid, 187
Isobutyl valerate, 91 Methane, 58, 81, 110, 244, 245,
Isobutyl xanthate, 131 250, 252, 253, 270, 273, 276, 277f
Isobutyric acid, 87, 89 278
Isobutyric aldehyde, 91 Methane and carbon dioxide, 270
Isobutyric isopropyl ester, 88 Methane and carbon monoxide, 270
Isoeugenol, 202 Methane and nitrogen, 271
Isohydrobenzoi'n, 203 Methane and oxygen, 270
Isohexane, 89 Methanetricarboxylie acid, 117
Isolauronic acid, 227 Methodics, 40, 235
Isordtroacetone, 74 Methoxylglycollic acid, 97
Isopropyl alcohol, (>S 70, 88, 89, 276 Methylacetate, 57, 79, 81
Isopropyl alcohol and nitrogen, 280 Methylacrylic acid, 108
Isopropylamine, 73 Methylal, 57, 97, 282
Isopropylamine and nitrogen, 284 Methyl alcohol, 57, 83, 97, 111, 2SHr
Isopropylpyrrplidone, 119 258, 268, 273
Isopropylsuccinimide, 119 Methyl alcohol and nitrogen, 279
Isopurons, 125, 126 Methylamine, 57, 67, 195, 248
Isovaleric acid, 63, 90 Methylamine and nitrogen., 284
Itaconic acid, 115, 116 Methylaniline, 194, 285
Methylazobenzene, 189
Ketones, 66, 69, 270 Methyl benzyl ether, 212
Ketones and nitrogen, 282 Methylcaproyl, 95
Ketones, aromatic, 202 Methylcarbonic acid, 58
Ketonic acids, 99 Methyldesoxyxanthine, 128,130
Ketoximes, 72 Methyl diphenylaniine, 195
Methylene di-p-anhydroamidobemsyi
Lactic acids, 97,100 alcohol, 158
Lactic acid and nitrogen, 284 Methyl ether, 79
Licvulinic acid, 100, 102 Methyl ether and nitrogen, 281
Lsevulinie acid and nitrogen, 284 Methylethyl-a-amino-/9~naphthol, 22$
Laurolene, 226 Methylethylaminophenol, 224
Lead diacetate, 81 Methyiethylketone, 74
Lead tetracetate, 81 Methylethylketoxime, 73
Leucaniline, 195 Methylethyl-^-naphthomorpholone^
224
Methylethylpinacone, 74
Maleic acid, 115, 284 Methyl formate, 57, 81
Malei'c acid and nitrogen, 284 Methylglyceiic acid, 99
Malic acid, 116 Methylglycidic acid, 99
Malic acid and nitrogen, 284 Methylpyoxime, 67
Malonic acid, 106, 112, 231
Malonic ester, 117
Malonyl urea 123
Mandelie acid, 215
Mannite, 65, 68
Meconic acid, 220
MeUogen, 64,121 Methylhydrox "
Mellitic acid, 120 M.ethylhydr
Mercaptans, 65 Methylisopu
Mercurargon phenide, 272 Methylmalo
Methylmorr ,
Methylnapnthomorpholine^*224
Methylnaphthomorpholojife, 224
Methyl oxide, 110
Methyloxydih^dropurins, 128
Methyloxypurin, 128
304: INDEX.
Methylphenomorpholine, 224 Nitrobenzonitriles, 186

Methylphenomorpholone, 224 Nitrobenzophenone, 183
Methylphenyl carbinol, 204 Nitrobenzyl alcohol, 168, 171
Methylpiperylhydrazine, 192 Nitrobenzylaniline, 172
Methylpropylketone, 102 Nitrobenzylidenealdehydophenylhy-
Methylpurons, 126 droxylamines, 182
Methyl quinoline, 219 Nitro-bitter-almond-oil-green, 181
Methylsuccinic acid, 113 Nitroearboxylic acids, 137
Methyl-sulphuric acid, 57, 65 Nitrocinnamic acids, 185
Methyltrimethylene urea, 122 Nitro-compounds, aromatic, 135-193
Methyluracyl, 122 Nitrocumic esters, 185
Methyluric acids, 126 Nitrocyanacetamide, 109
Methylxanthine, 128 Nitro-derivatives, 56
Methylxanthate, 131 Nitrodiamidotolylmethane, 181
Michler's ketqne, 207 Nitrodiamidotriphenylmethane, 181
Monobasic acids, 77 Nitrodiethylaniline, 179
Monobasic alcohol-acids, 95 Nitrodimethylaniline, 177, 178
Monobasic ketonic acids, 95, Nitrodimethyltoluidine, 179
Monobromacetone, 69, 71 Nitrodiphenyl, 173
Monochloracetic acid, 85 Nitrodiphenylamine, 180
Monochloracetone, 69 Nitroethane, 57
Morphine, 220 Nitroethane and nitrogen, 285
Morpholines, 223 Nitrogen, 246, 251
Morpholones, 223 Nitrogen and water, 270
Naphthalene, 134, 249, 251 Nitrogen and carbon monoxide, 268,
Naphthazarine, 191 270
Naphthol, 154, 201 Nitrogen and hydrocarbons, 271-273
Naphtholphentriazole, 190 Nitrogen, binding of, to organic sub-
Naphthomorpholones, 223 stances, 279
Naphthoquinone, 134 Nitrogen compounds and nitrogen,
Naphthylamine, 155, 167, 191, 195 . 284
Naphthylenediamine, 191 Nitrohydroquinone, 133
Nicotine, 285 Nitroketones, 181
Nitranilines, 164, 166, 167, 177 Nitroleuco-bodies, 181
Nitrites, 118, 121, 215 Nitroleucomalachite green, 172
Nitriles and nitrogen, 285 Nitromalonamide, 109
Nitroamines, 137, 165 Ntromalonic acid, 109
Nitroamido-o-benzyl alcohol, 170 Nitromethane, 56
Nitroacetanilide, 178 Nitromethane and nitrogen, 285
Nitroacetophenone, 183 Nitromethylaniline, 178
Nitroacid-nitriles, 166 Nitronaphthalene, 190
Nitroanisol, 165,175, 176 Nitronaphthalenesulphonic acid, 191
Nitroanthraquinone, 191, 210 Nitronaphthylamine, 190
Nitrobenzaldehyde, 169, 172, 181, Nitronaphthyl ethyl ether, 191
188 Nitrooxyanthraquinone, 191, 210
Nitrobenzene: Nitrophenanthrene, 192
(1) General observations, 135-145 Nitrophenanthrenequinone, 192
(2) Reduction of, 145-163 Nitrophenetol, 176
(3) Substitution products, 163-167, Nitrophenols, 133, 136, 166, 175, 176
184,189,257 Nitrophenyl ethers, 177
(4) —and nitrogen, 285 Nitrotolyl ether, 177
Nitrobenzeneazonaphthol, 190 Nitrophenyltolylketone, 183
Nitrobenzeneazophenol, 190 Nitrophthalic acids, 186
Nitrobenzeneazosalicylic acid, 190 Nitropropane, 57
Nitrobenzenecarboxylie acid, 166 Nitroprusside, sodium, 127
Nitrobenzenesulphonic acids, 156, Nitroquinoline, 193
183,186,189 Nitrosoaldehydecopellidine, 193
Nitrobenzoie acids, 172,183,188,189 Nitrosobenzene, 135-163
Nitrobenzoic esters, 184 Nitroso-compounds, 134-163
Nitrosodiethylaniline, 179
INDEX. 305
JSfitrosodimethylaniline, 178 Farabanic acid, 122, 168

Nitrosolupetidine, 193 Paraldehyde, 276
Nitrosopipecplines, 192, 193 Paraldehyde and nitrogen, 283
Nitrosopiperidine, 192 Peat, 233
Nitrosostyrol, 190 Pelargonic acid, 93
Nitrosotetrahydroquinolme, 1 93 Pentenecarboxylic ethyl ester, 114
Nitrosotrimethylpiperidine, 193 Perbrornbenzene, 256
Nitrotetraethyldiamidotriphenylme- Perbrommethylene, 253
thane, 181 Percarbonic acid, 77
Nitrotetramethyldiamidotriphenyl- Perchlorbenzene, 253, 254, 255
methane, 181 Perchlorethane, 253, 254, 255
Nitrotoluenes, 136,141,164,168-172, Perchlorethylene, 250, 253, 254, 255
189, 258 Persulphide, acetyl, 85
Nitrotoluenesulphonic acids, 173,186, Petroleum, 250
187 Phenanthrenequinone, 210
Nitrotoluic acid, 185 Phenazone, 173
Nitrotoluidines, 179 Phenetidine, 176
Nitrotoluquinolines, 150, 193 Phenol, 199, 20?., 231, 232, 27G
Nitrotolylamidophenylmethane, 172 Phenol and nitrogen, 281
Nitroxylenes, 172 Phenolphthalein, 201
Nosophen, 201 Phenols, 199
Phenomorpholone, 223
Octane, 90, 95 Phenose, 134
Octandion, 100, 102 Phentriazole, 189, 190
Octodecandi-acid, 115 Phenylacetic acid, 213, 215
CEnanthylic acid, 93 Phenylacetic ester, 78
defines, 93 Phenylchloramine, 157
Oleic acid, 94 Phenyldisulphide, 201
Opium, 220 Phenylenediamine, 164,167,177,178,
Orange II, 198 193, 285
Osmotic pressure, electrolytic, 26 Phenylethylamine, 204, 216
Osmotic theory, 26 Phenylglyceric acid, 215
Oxalic acid, 65, 104, 110, 231, 232, Phenylhydrazine and nitrogen, 285
279 Phenylhydrazones, 67, 203
Oxalic esters, 105 Phenylhydroxylamine, 138-146-155-
Oximes, 203 163
Oxy-acids, 96 Phenylisocyanide, 163, 254
Oxyamidoisophthalie acid, 186 Phenyllactic acid, 215
Oxyamidoqumoline, 193 Phenylmercaptan, 201
Oxyanthranol, 210 Phenylmethylene, 259
Oxyanthraquinones, 210 Phenylnaphthylcarbinol, 206
Oxyanthranilic acid, 184 Phenylnaphthylketone, 206
Oxybenzoic acids, 214 Phenylnaphthylpinacone, 206
Oxybenzoic acids and nitrogen, 284 Phenylpyrrolidone, 119, 215
Oxybenzophenone, 207 Phenylsulphocarbazinic acid, 131
Oxybenzophenone-benzoate, 207 Phenylsulphuric acid, 230
Oxybenzpinaeone, 207 Phenyltolylamine, 195
Oxybenzyl alcohol, 203 Phenyltolylcarbinol, 206
Oxybutyric acids, 98, 99 Phenyltolylketone, 206
Oxycarbostyril, 185 Phenyltolylpinacone, 206
Oxycarboxylic acids, 214 Phenylxylylcarbinol, 206
Oxycaproic acid, 232 Phenylxylylketone, 206
Oxydihydropurin, 128 Phenylxylylpinacone, 206
Oxydimorphine sulphate, 220 Phorone, 70
Oxyphenanthrenequinones, 210 Phosgene, 255, 256
Oxypropionic acids, 97 Phthalic acid, 116, 134, 212
Oxypunns, 128, 130 Phthalic ester, 212, 213
Oxytrimethylene urea, 123 Phthalylaminobenzophenone, 207
Oxypyronedicarboxylic acid, 220 Picoline, 218
Ozonizers, 263 Picramic acid, 176
306 INDEX.
i , Picric acid, 176, 199

Pimelie acid, 11-i
Propylbenzene, 214
Propyl butyrate, 89
Pinacolines, 207 Propylene, 88, 113, 114, 271
Pinacones, 70, 207 Propylene and nitrogen, 271
Pipecoline, 192, 218 Propylene bromide, 88
Pipecolyihydrazine, 193 Propylenediamine and nitrogen, 285
Piperidlne, 192, 218 Propylene oxide, 114
Piperidine and nitrogen, 285 Propylhydrocinnamic ester, 244
Piperylhydrazine, 192 Propylhydroxylamine, 57
Pivalic acid, 92 Propylnitrile, 121
Poly amines, 283 Propylpseudonitrole, 73
Polybasic acids, 116 Prussian blue, 120
Potassium acetate, 95, 97, 101, Pseudocumene, 134
111, 214 108, Pseudonitroles, 72
Potassium butyrates, Pseudotropine, 219, 220
88,101,108,214 Purins, 122
Potassium caprcate, 93, 214 Purons, 125, 126
Potassium cyanacetate, 85 Purpurin, 210
Potassium cyanate, 120 Purpurogallin, 202
Potassium cyanide, 120 Purpurogallincarboxylic acid, 202
Potassium ethyl-carbonate, 59 Pyrazolidine, 74
Potassium ethyl malonate, 108 Pyridine, 218, 285
Potassium ethyl succinate, 111 Pyridine derivatives, 217
Pyrocatechin, 231
Potassium ethylthiocarbonate, 131 Pyrogallol, 202
Potassium ferricyanide, 120 Pyrogallol and nitrogen, 282
Potassium ferrocyanide, 120 Pyrometers, 239
Potassium glycollate, 97 Pyroracemic acid, 100, 101, 102
Potassium heptylate, 93 Pyroracemic acid and nitrogen, 284
Potassium isethionate, 66 Pyrotartaric acid, 113
Potassium isoamyl-phosphate, 66 Pyrrol and nitrogen, 285
Potassium isoamyl-sulpnate, 66 Pyrrolidone, 119
Potassium isoamylxanthate, 131
Potassium isobutylxanthate, 131 Quinaldine, 219
Potassium isobutyrate, 112 Quinhydrone, 133
Potassium Isevulinate 100, 102 Quinia bases, 221
Potassium methyl-carbonate, 58 Quinine, 221
Potassium methylxanthate, 131 Quinizarin, 210
Potassium cenanthylate, 95 Quinone, 133,164, 165,177, 180,194,
Potassium percarbonate, 77 201
Potassium phenylsulphocarbazinate, Quinone and nitrogen, 283
131 Quinonediimide, 164
Potassium propionate, 86, 108 Quinonehydrone, 202
Potassium pyroracemate, 100, 101
Potassium succinate, 110 Racemic acid, 117
Potassium trichlormethylsulphonate, Reaction temperatures, 238
65 Reaction velocity, 11, 30
Potassium valerate, 95 Resorcin, 201,202
Potassium xanthate, 6, 131 Resorcin and nitrogen, 281
Potential difference, 44 Rocceline, 198
Potential, electrode, 14 Rosaniline, 181, 195
Potential, excess, 20
Propionic acid, 63, 64, 86, 100, 279 Saccharic acid, 68
Propionic acid and nitrogen, 284 Saccharic aldehyde, 65, 203
Propionic aldehyde, 63, 89, 98, 114, Saccharin, 216
279 Safranine, 195
Propionic aldehyde and nitrogen, 282 Salicin, 203
Propionie esters, 108 Salicyl alcohol, 203
Propyl alcohols, 63, 88, 89, 113,114, Salicylaldehydephenylhydrazone,204
276 Salicyl-a-osazone, 204
Propyl alcohols and nitrogen, 280
Propylamine, 57, 121, 284
INDEX. 307
Salicylic acid, 133, 201, 214, 258 Tetraethylammpnium triiodide, 118

Salicylic-acid-phentriazole, 110 Tetraethyldiaminophenazone, 174
Salicylic aldehyde, 283 Tetraethylthiuramdisulphide, 131
Salicylosazone, 204 Tetrahydrobrucine, 222
Saligenin, 203 Tetrahydroquinaldine, 219
Saligenin-glucose, see Salicin Tetrahydroqumoline, 193
Saliretin, 203 Tetrahydrostrychnine, 222
Sandmeyer-Gattermann reaction, Tetrahydrouric acid, 125
electrolytic, 196 Tetraiodophenolphthalein, 201
Sarcine, 127 Tetramethylammonium hydrate, 118
Sarcolaetic acid, 98 Tetramethylbenzidine, 198
Sebasic acid, 115 Tetramethyldiamidoazobenzene, 177
Sebasic diethyl ester, 114, 115 Tetramethyldiamidoazotoluene, 180
Short-circuiting cells, 50, 180 Tetramethyldiamidobenzophenone,
Silent electric discharge, 235, 261 207
Sodium acetoacetic ester, 100 Tetramethyldiamidodiphenyimeth-
Sodium dichloracetate, 85 ane, 208
Sodium dichlorpropionate, 87 Tetramethyldiamidohydrazotoluene,
Sodium formate, 81 180
Sodium glycollate, 97 Tetrarnethyldiamidophenazone, 174
Sodium iodopropionate, 87 Tetramethyldiamidophenazone ox-
Sodium malonic diethyl ester, 108 ide, 174
Sodium nitroprusside, 120 Tetramethylpuron, 127
Sodium propionate, 86, 111 Tetramethylsuccinic acid, 107
Sodium succinate, 111 Tetramethyluric acid, 127
Spark discharge, 244 Tetraphenylerythrite, 209
Standard electrodes, 45 Tetraoxyazobenzene, 133
Stilbene, 259 Tetraoxydibromanthraquinone, 210
Strychnidine, 222 Thalleioquin, 221
Strychnine, 221 Theobromine, 127, 129
Strychnos bases, 221 Theoretics, 6, 235
Suberic acid, 113, 115
Substances reducible with difficulty, Thioacetic acid, 85
23 Thiobenzoic acid, 212
Succinanil, 119, 215 Thiocarbonic acid derivatives, 130
Succinic acid, 109, 115, 231, 232 Thioformaldehyde, 269
Suceinic diethyl ester, 103, 112 Thiophene, 286
Succinimide, 119 Thiuramdisulphide, 131
Sugar, 268 Thymol, 200
Sugar-juice purification, electrolytic, Tolane chlorides, 259
69 Tolidine, 168
Sulphoanthranilic acid, 214 Toluene, 134, 249
Sulphoazobenzoic acid, 189 Toluenesulphamide, 216
Sulphobenzoic acid, 134, 212, 213, Toluenesulphonamide, 216
Sulphocarbamide, 285 Toluenesulphonic acid, 213
" Sun yellow," 173,187 Toluic acid, 213
Toluic aldehydes, 134
Tannic acid, 202 Toluidine, 136, 140, 167, 169, 170,
Tannic, 214 195
Tanning, electric, 234 Toluidines and nitrogen, 285
Tartaric acid, 110, 116 Tolunitrile and nitrogen, 285
Tartaric acid and nitrogen, 284 Toluylenediamine, 179
Tartronyl urea, 123 Tolylpyrrolidqne, 120
Terephthalic acid, 213 Tolylsuccinimide, 120
Tesla currents, 261, 288 Triamidotriphenylrnethane, 199
Tetracetylethane, 74 Tribromhydrin, 248
Tetrachlorhexyleneglycol, 90 Tricarballylic acid, 117, 118
Tetrachlormethane, 255 Trichloracetic acid, 85, 256
Tetradecane, 93 Trichloracetic trichlormethyl ester,
Tetraethylammonium chloride, 118 85
Trichlorbutyrate, 90
SOS INDEX.
Trichlorbutyric acid, 90 Tropinone, 219, 220

Trimethylacetic acid, 92 Turpentine, 273
Trimethylamine, 248
Trimethylamine and nitrogen, 284
Trimethylcarbinol, 91, 92 Unattackable electrodes, 18
Trimethylene, 271 Undecylenic acid, 94
Trimethylenetritoluidine, 170, 171 Unsaturated acids, 115
Trimethylene urea, 123 Unsaturated esters, 108
Trimethylethylene, 253 Uramil, 124
Trimethylisopuron; 127 Urea, 270
Trimethylmethyl isovalerate, 91 Uric acid, 122,125
Trimethyloxydihydropuron, 129
Trimethylpiperylhydrazine, 193 Valeric acids, 90, 92, 231, 232
Trimethylpuron, 127 Valeric ethyl ester, 108, 111
Trimethyluric acid, 127 Vanillin, 202
Trimethylxanthine, 129 Vapors and Tesla currents, 288
Trinitrobenzoic acid, 173 Velocity of reaction, 11, 13
Trinitrophenol, 176 Violuric acid, 124
Trinitrotoluene, 173 Voltaic arc, 244, 249
Trioxyanthraquinone, 210
Triphenylguanidine, 254 Xanthates, see Potassium xanthate
Triphenylmethane dyes, 199 Xanthate, potassium, 131
Trioxymethylene, 64, 65, 68, 253 Xanthic disulphide, 6
Trioxymethylene and nitrogen, 283 Xanthic supersulphide, 131
Tropic acid, 219 Xanthine, 127
Tropine, 219, 220 Xylenes, 134
"N. I.'

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ff

DR. WALTIIER LOB

AUTHORIZED TRANSLATION FROM THE AUTHOR'S ENLARGED AND

ELECTROLYSIS AND ELEOTROSYNTHESIS

II. W. F. LOJiENZ, A.M., Pii.I).

WITH TEN ILLUSTRATIONS

LONDON : CHAPMAN'& HALL, LIMITED

THE great progress which the elerfwIi'-TW *>

A NEW edition of Port or f/»!»V Imok nn thin infi»ri

2. Arrangement of Experiments and Measurements of Potential' " "AA

XI. Nitre-derivatives of the Naphthalene-, Anthracene-,

THE SILENT ELECTRIC DISCHAEGE AND THE EFFECT OF TESLA-CTJRRENTS . 261

CHAKACTKKJSTirH AX1» C'LAHKIFH'ATION OK TIIK

TICK application of electrical <*ner/fy for rf

and substitution reactions, the latter in pyrogenic and photo-

plicated than reduction processes, and usually less profitable.

It may be remarked, particularly in regard to the description

Two possibilities must be distinguished in the electrolysis

An example of the first kind of decomposition is furnished

lution take care of the conductivity. Organic elec-

RCOO +C2H/)H - IICOOC2H5 + OH.

the alcohol is at the same time a solvent and a

"ore divide the phenomena of electrolysis of carbon,

hydroxide solution take care of the conductivity. Organic elec-

RCGO -fC2H5OH =RCOOC2H54~ OH.

The reduction of nitrobenzene to nitrosobenzene furnishes

C6H5N02 + 2H = C6H5NO + H20.

In the conversion of azobenzene to hydrozobenzene an addition

C6H5N » NC6H5 H~ 2H = C6H5NH - NHC6H5.

A withdrawal of oxygen and addition of hydrogen occurs simul-

Anodic Depolarizers. — The conditions are somewhat more

C6H5NH - NH - C6H5 + 0 = C6H5N - NC6H5 + H20;

the conversion of benzene into hydroqumone by a direct addi-

the production of nitrobenzoic acid from nitrotoluene by the

N02C6H4CH3 4-3 0 = N02C6H4COOH + H20.

Gattenmum l has shown that the unstable modification can be

the metallic salts, need only be present in the electrolyte in

3. SIGNIFICANCE OF THE VELOCITY OF REACTION.

to choose the current strength, electrode dimension, and depo-

The effects producible by choosing a suitable reducing

5. ELECTRODE POTENTIAL AND REACTION MECHANISM.

I * have explained in conjunction with R. W. Moore. The

this may be. It is very difficult to understand, if the ions

whereby the second equation may be perhaps reversible, as

d occur through both processes and, since the velocity of the

tion must be referred to the action of hydrogen, let it be emphat-

ydrogen electrode in the corresponding electrolyte. The

. f. phys. Chem. 30, 89 (1899V

The Idea of excess potential is useful in applying the process

in explaining tli<- 1 !u»n«)ii»'na urrtirrhig ISITP , and we may

of caffeine, the potrntial is finally <.;m**d to drop % stronger

moments which can be independent of one another. Hence

moments which can be independent of one another. Hence

While the process at the cathode always ends finally in with-

vielual action of these two bodies on organic -cc^ipqUTiels with

7. THEORY OF THE REACTION VELOCITY IN ELECTROLYTIC

otherwise infinitely great, or at least very great, forces would

will diffuse to the contact surface and immediately react.

I the substance reaching the electrode. Electrolytic transfer-