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CHEMICAL KEACTIONS
I
THETR THEORY AND MECHANISM

^ BY

K. GEORGE FALK, Ph.D.

HARRIMAN RESEARCH LABORATORY,
THE ROOSEVELT HOSPITAL, NEW YORK

NEW YORK
D. VAN NOSTRAND COMPANY
EIGHT WARREN STREET
1920
 Copyright, 1920

D. VAN NOSTRAND COMPANY

Printed in the U. S. A.
 TO

D. L. F,
 PEEFACE

The central idea of this book is the development of a

general theory of reactions which will include both in-
organic and organic reactions. The fundamental view upon
which this theory is based is the "addition" theory accord-
ing to which when two or more substances react a primary
addition is the first step. This theory is not new. It has
been used in more or less isolated cases for a number of
reactions and may have been suggested as of general appli-
cability. As far as the writer is aware, however, this is the
first time that it is published in an extended form with

modern conceptions of chemical structures, which them-

selves rest upon the development of valence views.
The modern interest in valence appears to have started
in 1899 when Thiele published his paper on partial valence.
Some years later, 1904, J. J. Thomson suggested the basic
ideas of the electron conception of valence, but applied
these to very few cases. From that time on, the electron
conception of valence occupied the minds of a number of
chemists who attempted its application as shown in sporadic
publications. Professor Nelson and the writer believe that
they were the first, dating from 1909 on, to publish extended
applications of the electron conception of valence to organic
as well as to inorganic compounds and reactions, and to
develop certain lines of chemical theory from this point of
view. In the development of these views, they travelled
over a certain course of chemical thinking. Unquestion-
ably, others have followed the same or similar lines of
thought and reached similar conclusions. Among those
who have pul)lishcd along these lines may be mentioned
II. S. Fry, W. A. Noyes, J. Stieglitz, L. Jones, G. N. Lewis,
VI

R. F. Brunei,
J.
W.
Stark, H. KaufFmann,
attempt will be
CHEMICAL REACTIONS.

C. Bray and G. E. Branch, S.

made
and a number of others.
to give a historical review of the
1
Dushmanj
No

problem or to determine who is responsible for any par-

ticular part of the theory. That it was possible for certain
workers to publish before others does not negative the
fact that such theoretical views may have been taught and
used in planning experimental work by either group long^
before their publication.
For practical reasons, it was not possible for Professor
Nelson and the writer to add to the experimental data from
the newer point of view, but it seemed at the time as if

sufficient facts were recorded in the literature to permit

of a conclusive test of the theory.
The electron conception of valence has now apparently
been widely accepted. At the same time, a number of
chemists still speak of polar and non-polar valences. To
the writer, no useful purpose is served by such a distinction.
As stated, chemical reactions form the keynote of this
book. The first three chapters are preliminary in the
sense that they treat of the underlying theoretical concep-
tions used in the later chapters. Certain parts of Werner's
theoretical views are used. At present, these appear to offer
the only explanation which is at all satisfactory for what
have been termed at various times '^molecular" compounds.
In recent years, G. N. Lewis and I. Langmuir have developed
certain conceptions of molecular structures from the point
of view of electron distribution. These conceptions are
of the utmost importance and indicate new methods of
formulation. To apply them chem-
to the consideration of
ical reactions At least,
appears to be somewhat premature.
it appears to the writer that for him to attempt it would

be so. Since their views are not used here and since this
is in no way a historical treatise, they have not been given
in detail. On the other hand, it is believed that enough of
 PREFACE. . vii

the general theoretical side has been given to permit any

one interested to follow intelligently any further develop-
ments of structural chemical theory.
Questions of stereochemistry have not been included.
It would appear that spatial chemistry is enteringupon a
new phase. The experimental and theoretical work on the
arrangements of atoms in crystals as exemplified in the
publications of the Braggs and of others, points to an entirely
new conception of stereochemistry, while at the same time
stereochemical explanations, such as steric hindrance, which
have been accepted heretofore, are being superseded by
explanations based upon different relationships.
A number of new points of view and explanations are
advanced here. Many of these have been presented by
Professor Nelson to his students at Columbia University
during the past years. Whatever value this book may
possess is due in a large measure to him, both in the develop"

ment of the views and in the collection of material. Among

others who have aided in various ways in the development
of the views leading up to the preparation of this book and
towhom thanks are due are Professors G. B. Pegram and
H. T. Beans, of Columbia University, and Dr. Marston
L. Hamlin.
New York, N. Y.,
June 15, 1920.
 CONTENTS

CHAPTER I.
PAGE
Introduction; Valence 1

CHAPTER II.

Valence (continued); Co-ordination Number 21

CHAPTER III.

Acids and Bases 41

CHAPTER IV.
Catalysis -.
60

CHAPTER V.
Chemical Reactions; General Considerations. . . 76

CHAPTER VI.
Some Chemical Reactions 94

CHAPTER VII.

Some Chemical Reactions (continued) 120

CHAPTER VIII.
Olefins and their Reaction Products 135

CHAPTER IX.
Oxidation-Reduction 166

CHAPTER X.
Some Oxidation-Reduction Reactions 190

IX
 CHEMICAL EEACTIONS
CHAPTER I.

INTRODUCTION; VALENCE.
In order to classify chemical reactions so that it will
be
possible to obtain aknowledge of the relations involved
when chemical changes take place without considering each
chemical reaction as an individual unrelated to any other,
must be established. These theories
certain general theories
have been developed gradually as the number and kinds
of chemical reactions increased. They are not complete
enough yet to account for all possible changes but they
serve a useful purpose and make possible the study of
relationships which would be obscure without them. The
general principles upon which the theories of the mechanism
of chemical reactions depend and which will be used here
include I. The atomic and molecular theories; II. Valence,
including atomic valence and the electron conception of
valence, and co-ordination number; III. Reaction velocity,
especially as controlled by the physical conditions and by
the law of mass action.
These principles indicate the lines which will be followed
in the correlation of chemical reactions. Thermodynamic
relations will be considered only secondarily. Molecular
and atomic chemistry, and in general, kinetic relationships
will be the keynote of the explanations advanced. The
atomic and molecular theories together with valence con-
ceptions form the foundations. Reaction velocities are the
important features in considering chemical reactions and
the course these may take under given conditions. It is
impossible to treat of a reaction velocity without treating
1
2 CHEMICAL REACTIONS.

at the same time the velocity of the reaction in the opposit

direction, or in other words, the equilibrium of the reactioi
Equilibria are therefore arrived at from the kinetic an
molecular standpoints. This is as far as the theoretics
side of the treatment in this book will go. It may b
pointed out that the thermodynamic treatment reaches th
same point from the opposite direction. From the energ;
relationships, deduced from the laws of thermodynamics,
the equilibria relationships of chemical reactions are arrivec
at. One of the future problems of thermodynamic chem
istry is the development of reaction velocity relationship.'
from the equilibria concepts.
The reader of this book is supposed to have completed a

course in general inorganic and organic chemistry from th(

modern point of view. The relations of chemistry are
supposed to have been studied in such a way that the
elementary facts and phenomena are accurately described,
and the theories which develop from these facts and phe-
nomena applied and used in a rational manner. Such a
study would include a portion of the subject matter of
what is very often taken up at present under "physical
chemistry."
The atomic theory is based upon the laws of definite and
multiple proportions. Exact analyses of many substances
have shown that the constituent elements of these sub-
stances are combined in such quantities that definite
amounts or their multiples are always combined with each
other. The atomic theory gives a definite and simple
theory to account for this. The molecular theory is based
upon the existence of certain quantitative relationships
between the chemical compositions of substances and their
relative volumes in gas form or osmotic pressures in dilute
solutions. These theories were based upon quantitative
experimental data and accounted for them satisfactorily.
In recent years the existence of atoms and molecules has
 INTRODUCTION: VALENCE. 3

)een demonstrated experimentally so that no question

emains as to their existance. The reader is referred to the
)ook entitled ''
The Atom " by J. Perrin for an account of
his work.
The terms equivalent or combining weight and formula
veight have been used in place ofatoms and molecules as
lot involving the theories of atoms and molecules. While
hese terms may have been useful at a time when the exis-
ence of atoms and molecules were to some extent hypo-
hetical, the proof of their existence in recent years has
aade the use of such terms unnecessary.
Following the atomic and molecular theories, the study
»f the chemical compositions of substances led to the
loctrine of valence or saturation capacity. Each atom is

;onsidered to be capable of combining with a definite

lumber of atoms of its own kind or a different kind. The
Trangement of the elements in the Periodic System of
viendeleeff brings out clearly these valence numbers. The
ntroduction of dots and dashes in chemical formulas to
epresent valence linkings forms a convenient method of
epresentation.
Sometimes confusion has been caused by taking valence
inkings to represent some form of combining power or
tability. This question must be made clear and the mean-
ng of valence defined carefully for a proper understanding
»f the questions to be taken up. In order to do this,
•hemical energy will be taken up for a moment and the
elation betweenit and valence described.

For some purposes, it has been considered that energy

night be assumed to be the product of two factors, an
'intensity" factor and a "capacity" factor. For example,
n mechanical work or energy, in which the work is taken
o be equal to the product of force into distance, the force
v^ould be the intensity factor and the distance the capacity
actor. This division of energy into factors is entirely
4 CHEMICAL REACTIONS.

arbitrary. It serves a useful purpose in certain cases, hw

its limitations must be remembered. The intensity am
capacity factors of mechanical energy need bear no relatioi
except in name, to the intensity and capacity factors o
electrical energy or of chemical energy or of any other fom
of energy. For each form of energy a different divisior
may be made. This can be shown most directly by express-
ing the two factors of some of the different forms of energy
in terms of the C.G.S. system of length (L), mass (M), and
time (T) units. The dimensions of energy are always given
by the expression MUT~^. In energy considered as me-
chanical work, force may be called the intensity factor and
is given by the product of mass times acceleration or ML T~^,
and the displacement the capacity factor equal to L. In
electrical energy, for an electrostatic current, the electro-

motive force may be called the intensity factor and is given

by the expression M'^'^D'^T~^, and the electricity or charge
or coulombs the capacity factor and given by the expression
jj^i/22^1 1/2 2^-1 'pjjggg i^Q gg^g Qf factors show the usual

way of viewing the intensity and capacity factors of these

two forms of energy. For chemical energy, still another
way of viewing the possible energy relations is customary.
Here, the intensity factor may be considered to be given
by the change of free energy of the reaction under certain
definite conditions to be formulated presently. This is the
chemical affinity, and the units in which it is expressed
given by MUT~^. Obviously then, the capacity factor of
chemical energy would be a number. This numerical
capacity corresponds to what is known as valence.
This brief statement required further explanation, how-
ever. If the change in free energy is referred to the com-
bination taking place between equivalent weights of chem-
ical substances, that is to say, between the unit weights of
chemical combination, then, when considering molecules
or formula weights, the numbers of equivalents taking
 INTRODUCTION: VALENCE. 5

part would indicate the capacity factor or valence. Valence

is therefore represented as a number and the product of
change in free energy per equivalent and valence represents
the change in free energy in the formation of the substance
in the molecular state. In ferrous chloride, for example,
the free energy or chemical affinity of the two chlorine
atoms in combination with the iron may be assumed to be
the same; in ferric chloride, similarly, that of each of the
three chlorine atoms may be assumed to be equal, but not
necessarily the same as for the chlorine atoms in ferrous
chloride. The difficulty, if not impossibility of determining
when two atoms of a more complex
the free energy change
molecule combine, makes it necessary in practice to speak
only of the change in free energy in the formation of a
compound and not of the separate combinations between
atoms in the compound.
pairs of
Keeping in mind the significance of the terms intensity
and capacity factors, they will now be used in discussing
chemical energy as they form a convenient method for
presenting certain definite relationships. The chemical
energy contained in a given compound having a definite
molecular formula involves the number of atoms in the
molecule and the affinity with which these atoms are com-
bined with each other. The chemical affinity involved in
a compound is a definite quantity. It is given numerically
as the value of the affinity of that compound compared to
the value of the affinity of the substances from which it

is formed. That is to say, the chemical affinity of a com-

pound is given as a difference, not as an absolute value.
It may be measured in any of the ordinary units of energy,
and represents the external work which may be obtained
when the substance is formed from its component parts by
a reversible isothermal reaction. This external work is

generally known as the change in free energy in the forma-

tion of the compound and is the true measure of the change
6 CHEMICAL REACTIONS.

in the chemical affinity. The actual measurements

these values may be carried out in several ways. A direct
method involves the electromotive force measurements of
a reversible cell under definite conditions. A more general
method is the determination of the equilibrium constants
of definite reactions. At the present time very few organic
reactions are available for the former method, while for™
the latter, the accurate determinations of a large number of
equilibria in organic reactions have not been carried out.
There are, consequently, comparatively few data at hand
to enable the exact relative thermodynamic stabilities of

organic compounds to be calculated. It is very desirable

that such determinations be made, as they represent one
of themost important problems in chemistry at the presents
time. Such values would give a true measure of the rela- '

tiye stabilities of compounds, or the magnitude of the__.

chemical affinities. Many organic chemists have been in^j
the habit of speaking of the stability of a compound when
the rate at which the compound reacted was meant. Re-
action velocities bear no simple relation to the stability or
affinity, and deductions with regard to the affinity with
which two atoms are combined, simply on the basis of the
rate with which they react with other substances, are wrong
in principle and fact.

The terms upon which the intensity factor of chemical

energy or the chemical affinity depend may be indicated
as follows : Every reaction is (thermodynamically) rever-
sible. The greater the affinity which causes two substances^B
to combine or react, the greater will be the proportion or
amounts of the products formed, and the more difficult

will it be to decompose the products. The chemical affinity

will consequently be greater, the more the equilibrium lies

in the direction of the formation of the products; or, in

other words, the value of the chemical affinity is connected

with, or may be calculated from some function of the
 INTRODUCTION: VALENCE. 7

equilibrium constant. Van't Hoff, in 1883, showed this

function to be given by the equation

(1) A = RT log. K-RTlog.^^^^^.

for a chemical reaction represented by the equation

(2) UaM + 7i,iV + . . . = n'a'M' + n\'N'+ . .

.,

in which A represents the change in free energy or the

chemical affinity of the reaction (2); R, the gas constant;
Tj the absolute temperature at which the reaction takes
place; K^ the equilibrium constant of the reaction repre-
sented by equation (2) and the different values of C in
;

the second term of the right-hand side of equation (1)

the concentrations of the reacting substances of equation
(2). If these concentrations are chosen as equal to unity,
the chemical affinity is found to be

(3) A = RT loge K.
The between the equilibrium constant, K, of a
relation
reaction,and the heat, of the reaction at constant volume Q,
both at the absolute temperature T, was shown by Van't
Hoff to be

The following equation, (5), is known as the Gibbs-Helm-

holtz equation.

(5) A = Q+T^.
This shows the relation between the change in free energy,
or the chemical affinity of a reaction, the heat of reaction
at constant volume, the absolute temperature at which
the reaction proceeds, and the temperature coefficient of
the chemical affinity, dAjdT, of the reaction. These three
8 CHEMICAL REACTIONS.

equations are fundamental for the relations between

chemical affinity of a reaction and other physical and
chemical quantities.
The last equation shows that only if T = or if

dA/dT = is the heat of reaction equal to the chemical

affinity. The
equality of these two is therefore only a
special case, and as T increases, they are likely to diverge
more and more. Whether the heat of reaction is greater
or less than the chemical affinity will depend upon whether
the change in the chemical affinity with the temperature is

negative or positive. In equation (5) the electromotive

force of a reversible cell per gram-equivalent of substance
transformed (since one faraday of electricity is associated
with one gram equivalent of substance) may be substituted
for A, since it is a measure of the change of free energy of
the chemical reaction taking place in such a cell.

The capacity factor of chemical energy may be considered

to be valence. Valence is a number, and is a distinct factor
not involving chemical For reasons which have
affinity.

already been given, the chemical affinities of organic com-

pounds have been determined only in isolated cases. On
the other hand, valence has been a valuable aid in classifying
the compounds of organic chemistry, so that it is the latter
which has been used to the greater extent in that field.
At the same time another reason for this may be given. 1

The change in free energy, or the thermodynamic stability,

while of the greatest importance, has nothing to do with
That is to say, it gives the stability of a
the time factor.
compound when equilibrium has been reached. Now the
element carbon often shows great inertia or chemical re-
sistance in many of its compounds and reactions. The
velocity with which it enters into reactions is often very
small even though the free energy involved in the chemical
change is very great. As a result, compounds of carbon
are known which have no thermodynamic right to exist,
 INTRODUCTION: VALENCE. 9

that is to say, if equilibrium were attained, none or only

infinitesimal amounts of the substances would be present.
The rate of reaction is so small, however, that equilibrium
ordinarily is not attained, and therefore organic chemistry
has very often to deal with these (thermodynamically)
unstable substances. While, therefore, undoubtedly, the
affinity relationships of organic compounds will ultimately
be of predominant importance, until more is known of
these, valence, which is not affected by the time factor in
this way, has had to serve as the classifying principle.
But in using valence in this way it is not permissible to
introduce exact measures of the comparative stabilities as
has been attempted so often, as already pointed out. All
that can be done as a result of the comparative study of
large numbers of compounds is to say which would probably
exist under ordinary conditions and whether some would
react more rapidly than others. These qualitative factors
do not give any information concerning the real quantitative
measures of relative stability.
A single linking between two atoms gives no information
as to the stability of the union between these atoms. A
double linking between two atoms cannot give any more
information with regard to the stability of the union.
Qualitatively, it has been found that the rate of reaction
for compounds containing double linkings is greater in some
ways than the rate for compounds containing single linkings,
and that with certain reagents, decomposition at the double
linking occurs more rapidly than at other parts of the
molecule, but this is manifestly different from a discussion
of true stabilities of compounds. The double linking in
the ordinary language signifies two units of valence just
as the single linking denotes one unit of valence, and in this
sense, the only permissible one, the representation of a
double linking by two lines or dashes is a correct picture
of the union when one line is used for the single linking.
10 CHEMICAL REACTIONS.

These valence views may now be carried further and the

later conceptions involving the electrons and the electron
conception of valence described. These developments did
not take place suddenly but occurred gradually as new
experimental work showed that the older views were not
sufficient to include all the facts known. For instance,
oxides are at times spoken of as acid oxides and basic oxides.
Electrolytic studies on the decomposition of salts and other
substances in solution indicate a real difference between
the two parts of the molecules. The distinction may be
and acid-forming elements and base-forming
carried further
elements designated, as brought out, for instance, by the
oxides of the elements of the different groups in the Periodic
System. The names non-metals and metals may be taken
to be practically synonymous with acid-forming and base-
forming elements, and finally these may be used inter-
changeably with electronegative and electropositive ele-

ments. This development of terminology leads to the

following definition or description of valence: The valence
of an element is equal to the number of equivalents of the
acidic or of the basic constituents combined with or
associated with one formula weight of that element.
Arrhenius's theory of ionization has shown that certain
of the atoms or groups actually do carry electric charges,
and has fixed the terms electropositive and electronegative
as having a readily demonstrable existence with these
substances.
J. J. Thomson, in 1904, put forward as a possible develop-

ment a new view of valence. Instead of quoting the brief

presentation given by him, an attempt will be made to
develop the subject more completely. If a solution of
ferrous chloride is placed in beaker A, and a solution of
potassium permanganate in beaker B, the two solutions
connected by a salt bridge C containing a solution of some
neutral salt dipping into both solutions, and by a wire with
 INTRODUCTION: VALENCE. 11

, galvanometer in circuit connecting the two electrodes D

nd D' which dip into the solutions, it will be noticed that
, positive current will flow in the direction 5 to ^ in the
ire. If the contents of beaker A be examined now, it

dll be seen that the iron has been oxidized to the ferric
rm. If the amount of positive electricity flowing through
he circuit from B to A were measured and the amount of
rrous iron changed into ferric iron were also measured,
would be found that for every formula weight, or mol, of
errous iron changed into ferric iron, 96,500 coulombs of
ilectricity had passed through the circuit. Therefore it
ay be said that one mol of ferrous iron differs from one
npl of ferric iron by 96,500 coulombs. In this way it may
)e brought out that

One mol of iron = 56 grams of iron.

" " " ferrous iron = 56 grams of iron— 2 X 96,500
coulombs negative electricity.
'' " " ferric iron = 56 grams of iron— 3 X 96,500
coulombs negative electricity.

rom these values it is evident that the amount of positive

electricity' associated with the mol of iron corresponds to
the number of mols of atomic chlorine that the mol of iron
can hold in chemical union, or, in other words, there is a
definite relation between the amount of electricity and the
valence of the iron.
If, instead of a solution of ferrous chloride, an alkaline
solution of formaldehyde is placed
in beaker A, it will be found that
^y^^^^Mj/
again a positive current will flow
Tom B to A, in the wire, and if

the constants of beaker A are ex-

._J
amined, it will be noticed that the
ormaldehyde has been changed
into formic acid, or oxidation has taken place. The amount
12 CHEMICAL REACTIONS.

of current passed through the circuit when compared to the

number of mols oxidized is not as readily measured as with
the former experiment, but this experiment shows that
oxidation, and therefore reduction, with organic compounds
as with inorganic compounds is accompanied by electrical
changes.
If the amount of electricity in any oxidation-reductio I
it will be found
reaction involving electrolytes be measured,
that, for everymol of an element undergoing oxidation or
reduction, 96,500 coulombs or a simple multiple of this
quantity, are always involved. Similarly, if the charge,
either positive or negative, carried by one mol of any ion in
a solution be measured, it will also be found to be 96,500
coulombs or a simple multiple of this quantity. The quan-
tity of electricity in all of these reactions appears to obey
a law of definite and multiple proportions. Just as the
atomic theory of matter is based upon these laws, so
electricity may be regarded as atomic in character, and
96,500 coulombs represents one combining unit, or if the
expression may be used, one combining weight of elec-
tricity. The smallest quantity of electricity associated with
one atom of matter is generally known as an electron.
The existence of the electron has been proven by the w^ork
of a number of physicists, especially by J. J. Thomson and
R. A. Millikan.
Taking into consideration the definition of valence given
before and the experiments and conclusions therefrom just
described, it is now possible to give a general definition of
valence which may be applied readily and used as simply
as the older definition of valence. The valence of an element
may he defined as the number of negative electrons an atom of
that element loses or gains to form chemical Unkings. In
accordance with the modern developments of physics, the
negative electron (or corpuscle) is accepted as a unit (or
atom) of electricity. This view of valence states that
 INTRODUCTION: VALENCE. 13

every chemical linking between two atoms involves the

transfer of a negative electron from one atom to the other.
This transfer of a negative electron requires, assuming the
atom itself to be electrically neutral, that the atom which
loses the electron acquires a unit positive charge, the atom
which gains the electron, a unit negative charge.
The question now naturally arises: How is it possible to
ascertain which atom is positive and which is negative in a
compound? For substances which conduct the current in
solution, the charges manifested by some of the atoms or
groups of atoms will show directly the distribution of some
of these electric charges. In general, the relative positions
of the elements in the Periodic System, which is itself an
expression of the chemical properties of the elements, serves
as a guide in determining this point. In the horizontal
rows, the elements of larger atomic weights are usually

negative to those of smaller atomic weights; thus, NaCl;

NH3; CH4; CCI4; etc. In the vertical series the main

and subgroups must be considered separately.
The older terms, positive and negative elements, now
acquire a more precise meaning. A positive element is
one, whose atom, in chemical combination, has lost one or
more negative electrons; a negative element, one whose
atom in chemical combination has gained one or more
electrons. When an atom is reduced, it gains negative or
loses positive charges. any given compound, the
Since, in
atom which acquires the electron is the one which has the
greater attraction for it under the given conditions, and
since the loss or gain of an electron signifies that the element
is either oxidized or reduced, the following generalization
may be stated : That element in a compound is the positive
element, which shows the smaller oxidizing or greater reduc-
ing potential (or has the smaller attraction or affinity for
the negative electron) ; and conversely, that element which
14 CHEMICAL REACTIONS.

eanit^
has the greater oxidizing potential (or the greater affinitj
for the negative electron) is the negative element. This
generalization substitutes the affinity of the elements for
the electrons for the affinity of the elements toward each
other as was done formerly. The relative oxidizing poten«
tials signify the same relations as the chemical affinity of
different atoms for each other. Just as with the other,
measures of the intensity factor of chemical energy, th^
use of the oxidizing potential must for the present be limite<
to qualitative relations with most organic substances.
It is possible to conceive of compounds in which the tw<
elements which enter into chemical combination have oxi-j

dizing potentials so close to each other in value that two'

combinations are possible in which the positive and negative^
elements are interchknged in the two compounds. As aiSI
example of this type of isomerism, the two isomeric iodine
chlorides may be mentioned. Since chlorine has the higher
oxidizing potential, it is highly probable that in the more
stable of the two isomers the iodine atom is positive, while
in the less stable, the chlorine is positive. The formulas
+ -
for the two compounds may be written ICl for the stable

form, and CI I for the unstable form. When the oxidizing

potentials of the elements differ very much in value, iso-
merism of this form would not be so likely. Thus with
hydrogen chloride, the form HCl would very likely be so
unstable that it would be impossible for it to exist under
ordinary conditions, and it would therefore be unknown.
It has often been observed that the conditions, such as the
presence of other substances, influence the oxidizing poten-
tials of the elements or, as formerly expressed, the affinity
of the elements for each other. Likewise, the pressure and
temperature of a mixture of methane and water may be
such that the negative carbon of the methane is oxidized
to the positive carbon of carbon monoxide or dioxide. It,

therefore, seems possible that differences in conditions may

 INTRODUCTION: VALENCE. 15

also give rise to electroisomers. Moreover, for many com-

pounds of carbon in which several atoms of carbon are
joined with each other, it is often very difficult to know
which of the carbon atoms is positive.
It may also be repeated that the chemical resistance or
the inertia of carbon compounds may also give rise to
electroisomers, since one of the isomers while very unstable
may still exist due to its extremely slow rate of decomposi-
tion.
The theory of electric dissociation of Arrhenius showed
that the ions in solution carried definite charges. The
number of these charges, taken in connection with the
general views of positive and negative elements, and acidic
and basic constituents compounds, were found to be
of
identical with the valence numbers of these atoms and
groups. In this way arose the one direct experimental
method of determining valence; the measurement of the
electric charges on the ions. This method is of limited
application, however, since many substances are not ionized
in solution, and this gave rise to the view that if a substance
did not ionize, its atoms were not united in the same way
as the atoms of a substance which did ionize. The possible
action of the solvent was not considered in this connection.
Two kinds of valence were, therefore, adopted by a number
of chemists, polar valence and non-polar valence. Since
inorganic compounds, mainly, are ionized in solution, and
organic compounds not ionized, this division was roughly
applied in such a way that inorganic compounds were
assumed to contain polar valences, and organic compounds,
non-polar valences.
There are a number of arguments against the assumption
of two kinds of combining forces in place of one kind (])olar).
The untenabiHty of the dual view may be seen most readily
with some of the phenomena of oxidation and reduction.
As already stated, the correct definition for oxidation and
16 CHEMICAL REACTIONS.

reduction with inorganic compounds, as generally accepted,

is unquestionably that involving a change in the electrical
charges of the atoms; for oxidation, gain of positive charges,
or loss of negative charges, for reduction, the reverse
In the explanation of oxidation-reduction involving th
transfer of electrons, it becomes evident that in speakin
of oxidation-reduction it would be more correct to say tha
a particular element in a compound is oxidized or reduced
Thus in the case of the oxidation^ involved in changin
ferrous chloride into ferric chloride, it is the iron which is

oxidized, the chlorine is neither oxidized nor reduced

Because of the incorrent way of saying that a compoun
has been oxidized or reduced, the meaning of the termi
oxidation and reduction has in many become
instances i
vague. If electrons are not responsible for the union be
tween atoms in molecules which are not electrolytes, th
electrical definition of oxidation and reduction becomes^
inapplicable and it is necessary either to fall back upon som
of the older definitions or to use an entirely new one fo
these cases. So far no new definition has been proposed
and the older definitions are still used in organic chemistry
Thus the addition of oxygen, or the removal of hydrogen,
is taken to be the common characteristic for an oxidation.

To illustrate this point: The conversion of methane into

carbon dioxide and water by means of oxygen, would be
considered oxidation, according to the older definitions.
Methane can also be converted into carbon dioxide by
treatment with chlorine, that is substitution, and sub-
sequent hydrolysis, neither action being oxidation according
to the older definition. Many other examples might be
mentioned, and the general conclusion is arrived at, that
it would be impossible to give any satisfactory definition of
oxidation applicable to all cases. Furthermore, the oxida-
tion of formaldehyde by permanganate as described before
showed that the oxygen from the permanganate did not
 INTRODUCTION: VALENCE. 17

add to the formaldehyde since the permanganate was not

in the same beaker. There was a current of negative elec-
tricity flowing from the formaldehyde solution to the
permanganate solution. A similar experiment may be
carried out with ethyl alcohol in place of the formaldehyde.
The formaldehyde and ethyl alcohol belong to the class of
non-electrolytes, and unless the union between the atoms
is considered polar in character, it would be very difficult

to find a suitable definition or description for this form of

oxidation.
Since the experimental evidence at hand is no more
against than in favor of the view that electrons are respon-
sible for valence in the case of non-electrolytes than in the
case of electrolytes, while indirect evidence is in favor of
this view, it is much simpler to adopt the view of one kind
of force acting between atoms in all compounds, that is,
that due to the electron associated with the atom. This
at once furnishes one definition for all oxidation-reduction
reactions applicable to all cases and easily understood.
A few words regarding the application of valence may
be of value here. Valence is a number. Experimental
facts have made the negative electron (the atom of elec-
tricity) the basis on which to build. From the chemical
side, the valence of an atom shows the number of. atoms (or
groups of atoms) held in combination by that atom when
the hydrogen atom as it exists in most of its compounds is

taken as the positive unit (loss of one negative electron).

These relations of positive and negative make it clear
that in speaking of valence, it is not sufficient to give a
number for its value, but that at the same time it must be
stated whether the number is positive or negative, that is

to say, whether negative electrons have been lost or gained

in the combination of the atom in question. This has
evidently developed as a matter of practical expediency
from the experimental evidence upon which the theory of
18 CHEMICAL REACTIONS.

valence is would be possible to construct a

based. It
theory of valence using as the basis the atoms of the
elements which have gained the greatest number of negative
electrons among all the elements in the formation of chem-
ical linkings, and to consider all other combinations as
positive valences. This treatment would simply amount to
a shift of the standard of reference from what is now con-
sidered to be an electrically neutral atom, to an atom
carrying the maximum number of negative charges (which
is eight), and to consider the valence as positive when
compared with this new zero standard. This method of
treatment would obscure somewhat the relative positive
and negative relations of the elements, which have been
developed as the result of experience. At any rate, while
it is important to point out that the standard or basis in
use is arbitrary in the sense that it is based upon experi-
mental facts which were obtained without reference to
any theory of valence, in order to retain the connection
between the theory of valence and other fields of science,
the standard evolved will be adhered to strictly in the
further developments.
Earlier in this chapter it was pointed out that change in
free energy per unit (equivalent) weight multiplied by
valence would give the change in free energy per molecule
in the formation of the substance in question. In using
valence in this way, the electropositive or electronegative
character of the atom would not be included in determining
the change in free energy of the molecule, since the positive
or negative sign of this free energy change depends upon
other factors and comparative units used and the method
of calculating these values as developed historically. This
statement is made to avoid confusion in the use of valence
as a number (not positive or negative) in free energy calcula-
tions, and valence (relative positive and negative states of
the atoms) in connection with the electron conception of
valence.
 INTRODUCTION: VALENCE. 19

Nitrogen in ammonia has a valence of — 3, (NH3).

Nitrogen in nitrous acid has a valence of + 3, (HO N O).

Nitrogen in ammonia therefore differs from nitrogen in
nitrous acid by six units of valence. The great difference
in the properties of the nitrogen in the two compounds is an
expression of the difference in valence. (On the former
non-polar view of valence, nitrogen was considered to have
a valence of 3 in both compounds.) Nitrogen in nitric
acid has a valence of + 5. The difference between the
nitrogen in the extreme states is eight units of valence.
Oxidation of an atom consists in the loss of negative charges
or the gain of positive charges, and therefore the change of
nitrogen in ammonia to the nitrogen in nitric acid consists
of an oxidation of eight units. The other atoms combined
with the nitrogen in these compounds do not change their
charges, or are neither oxidized nor reduced, oxygen having
a valence of — 2 and hydrogen a valence of + 1 in all three.

The compounds of carbon show similar relationships.

—— +
Carbon in methane has a valence of — 4 (C H4)
++
. Carbon
++ -

in carbon tetrachloride has a valence of 4 (C CI4) The + .

difference in the valence of the carbon in the two com-

pounds is eight units, or the carbon in carbon tetrachloride
is in a state of oxidation eight units greater than that of

the carbon in methane. In methyl chloride (CH3CI), the

carbon atom has lost one negative electron and gained
three, or its valence is — 3 + 1, and its state of oxidation
— 2; in dichlormethane, the valence of the carbon is

— 2+2 and its state of oxidation 0; in chloroform, the

valence of the carbon is — 1 + 3 and its state of oxidation

+ 2. This compounds shows the importance of

series of

stating in full the charges of theatoms which go to make

up the valence, and it also illustrates the meaning of the
term oxidation of an atom. The state of oxidation of an
20 CHEMICAL REACTIONS.

atom conveys a definite meaning chemically only in com-

parison with the atom in the other states of oxidation.
The change atom is the significant
in the valence of the
fact in speaking of oxidation, and while the state of oxida-
tion may be shown by the number and sign of its valence,
its importance is only clear and definite in comparison with

other states of oxidation of the same atom.

In general terms, the extreme difference which an atom
shows in its valence is eight units; for example, chlorine in
hydrogen chloride (—1) and chlorine in perchloric acid
(+ 7); sulfur in hydrogen sulfide (—2) and sulfur in
sulfuric acid (+ 6); nitrogen in ammonia (—3) and nitro-
gen in nitric acid (+ 5); carbon in methane (—4) and
carbon in carbon tetrachloride (+ 4). This difference
same relation to which MendeleefF referred in
refers to the
his PeriodicSystem when he stated that the sum of the
valences toward oxygen and toward hydrogen of the ele-
ments of the V, VI, and VII Groups was equal to eight.
The compounds of the elements of the I, II, and III Groups
in which they gain negative electrons are at present not
sufficiently well defined and extensively studied to indicate
the general relations existing there.
As a matter of convenience, the direction in which the
negative electron is transferred in the formation of a chem-
ical linking may be indicated by an arrow, as suggested
by J. J. Thomson, the head of the arrow giving the direction
of the transfer of the electron. The lines representing
linkings as written heretofore in structural formulas will
therefore be replaced by arrows; H ~> CI in place of H — CI,
etc. This saves the cumbersome use of plus and minus
signs, but in case of doubt or for the sake of clearness, it is

also advisable to use these signs in connection with the

formulas.
 CHAPTER II.

VALENCE (CONTINUED); CO-ORDINATION NUMBER.

It has been emphasized that in simple compounds the
valence is the capacity of an atom of one element to hold
in chemical combination a certain number of atoms of
some other element. It will now be necessary to consider
another form of combining capacity which appears to mani-
fest itself in the case of molecules of compounds combining
with definite numbers of molecules of some other com-
pound. As examples may be mentioned hydrates such as
CaCl2.6H20, CrCl3.6H20, CUSO4.5H2O; ammoniates such
as AgC1.2NH3, CuSO4.4NH3.H2O; and double salts such
as 4KCN.Fe(CN)2, 2KCl.PtCl4. These compounds have
as components simpler compounds which are combined in
definite proportions just as the elements in the simpler
compounds are combined in definite proportions. It be-
comes evident, therefore, that apparently combining capaci-
ties of molecules for other molecules exist here in much the
same way as in the case of the combining capacity of atoms
for other atoms.
A. Werner, in the last twenty years, has systematized
compounds of varying degrees of complexity. In order to
explain the formation of addition compounds, as for ex-
ample, sulfur trioxide with water, ammonia, hydrogen
chloride, etc., platinic ammonia, water,
chloride with
hydrogen chloride, etc., ammonia with
water, hydrogen
chloride, etc., he makes the assumption that various atoms
such as the sulfur in the sulfur trioxide, the platinum in
the platinic chloride, and the nitrogen in the ammonia, etc.,
possess a residue of unsaturated affinity, which permits
such groups to mutually satisfy each other. When the
amount of this affinity is sufficient to bring about a stable
21
22 CHEMICAL REACTIONS.

combination between the single molecules,

tically the same role as the ordinary valence, viz; it effects
it
i
assumes prac-

an interdependence between two elementary atoms, and in

this way unites two radicals to a molecular complex. These
new valences differ, however, from ordinary valences, in

that they are not able to unite univalent radicals and in

order to distinguish them from the latter he calls them
"auxiliary valences."
In the case of ammonium chloride, the unsaturated
auxiliary valence of the nitrogen atom in the ammonia
would be saturated by the auxiliary valence of the hydrogen
atom of the hydrogen chloride. The formation of the
ammonium chloride would be formulated therefore as
Hv Hv
H-9N + HCl = H-^N • • • HCl.

" Since according to this formula, four hydrogen atoms are

bound to nitrogen, it is hardly to be supposed that one

hydrogen atom is up by a greater amount of affinity
linked
than any of the remaining three; it is far more probable
that a state of equilibrium is reached in which all the
hydrogen atoms are linked by the same ampunt of affinity.
Ammonium is therefore a complex radical, NH4, in which
the nitrogen is the central atom having the four hydrogen
atoms linked to itself with the same amount of affinity in
each case. On each hydrogen atom of the complex NH4,
there is still a certain amount of unsaturated affinity, which
the radical is able to utilize externally to itself and becomes
in this way monovalent. Ammonium salts have, therefore,

the following structure:

E. C. C. Baly approached this general question in a

different way. His views may be stated briefly as follows
 VALENCE; CO-ORDINATION NUMBER. 23

(Jour. Amer. Chem. Soc. 37, 979 (1915)): From the study
of the absorption in the ultraviolet region of the spectrum
of reacting substances before, during, and after the reaction,
he concluded that every chemical molecule is surrounded
by a condensed force field of electromagnetic type. If
molecules of different substances are brought close together,
they tend to form an associated system, or addition com-
pound, with a loss of energy, and establishment of potential
gradient. If this potential gradient is steep enough, a
transfer of electrons will occur with the formation of a
true chemical compound. Thus the compounds HX and
YOH may unite to form HX.YOH, and then rearrange to
XY.H2O, a system containing less energy than HX.YOH.
If the force lines of the two molecules form completely
closed systems, no reaction will occur between them until
their force fields are opened up, perhaps by molecules of
some other substance as the solvent or a catalyst.
It is apparent that a similarity exists between the views
of Werner and of Baly concerning the mechanism involved
in the formation of these addition compounds. Both con-
sider that simple compounds such as ammonia and hydrogen
chloride possess unsaturated properties, Werner, auxiliary
valence, and Baly, open force fields, which enable these
compounds to combine to form addition compounds.
According to Werner, after the two simple compounds
come together, there is a readjustment of this affinity, or
auxiliary valence, between the nitrogen atom of the am-
monia and the hydrogen atom of the hydrogen chloride in
such a way that all the hydrogen atoms in the ammonium
chloride are united to the central nitrogen atom in the
same way, while the chlorine atom is held finally by the
new res'dual affinities of the four hydrogen atoms in the
NH4 radical. Baly considers that after the force fields
have brought the two simpk; compounds together in the
case of a compound like ammonium chloride, there is a
 N

24 CHEMICAL REACTIONS.

readjustment of these forces, causing a formation of tl

stable compound.
If the valences in the ammonium chloride are assumed to
be due to electrons as described in the first chapter, then the

structure of the compound would be h — ^^» ^^^i"

eating the direction of transfer of the negative electrons

H-^ >^H
by means of arrows H—^N *
This formula for the
R^ "^Cl
structure of ammonium chloride has all the advantages of
the Werner formula, viz; it agrees with the results of V.
Meyer and M. Lecco's Ann. 180, 173 (1876)) experi-
(Lieb.
ments that the four hydrogens bear the same relation to
the molecule, and it shows that the chlorine bears a different
relation to the nitrogen than the hydrogen. Furthermore,
it has the advantage over Werner's formula in that only

one kind of valence is necessary. Also, it is readily seen

that neither oxidation nor reduction is involved in the
formation of an addition compound of this type. If only
the auxiliary valence idea of Werner is used in this connec-
tion, the positions of the electrons are not definite, so that
itwould be difficult to state by means of the structures
whether any oxidation or reduction had occurred.
Many compounds similar to ammonium chloride, such
as derivatives of the amines, have been prepared and
studied. These compounds were for some time thought
to follow the law of definite proportions. For example,
an equal number of molecules of amine and acid combined
to form the definite substituted ammonium salts. Although
this generalizationappeared to hold for a number of such
compounds, other substances were prepared after a time
in which these simple relations were not observed. Thus,
the^^compound (NH3)4HC1 (cf . Werner, Neuere Anschauun-
 VALENCE; CO-ORDINATION NUMBER. 25

gen) was prepared, then compounds such as AgCl(NH3)2,

PtCl4(NH3)2, PtCl4(NH3)6, CUSO44NH3H2O, etc., which did
not follow such simple laws, and for which the ordinary
ideas of valence did not suffice. Some of these compounds
were in fact termed "anomalous," because they did not fall
into a scheme of simple formulas as it was expected they
should. It was thought that the reaction between am-
monia or an amine, and hydrochloric acid, was similar to
the reaction between a base and an acid to form a salt,
but the combinations between ammonia and salts to form
the compounds just indicated showed that this was not
the case and that ammoniates, as these compounds are
called, did not require the participation of an acid.

C. Friedel, in 1875 (Bull. Soc. Chim. [2] 24, 160, 241),

showed that in cooling a solution of hydrogen chloride in
ether, a crystalline compound was formed containing an
equal number of molecules of ether and of hydrogen
chloride. This observation was an isolated one for some
years. J. N. Collie and T. Tickle (Trans. Chem. Soc. 75,

710 (1899)) found that dimethyl pyrone formed compounds

with the halogen hydrides which showed
the properties characteristic of ammo- HgC C . C CHg
.

nium halides, and later were found to ^q gjj

ionize in solution in a manner similar ^^
to ammonium salts, and were therefore ^
comparable to them. A. Baeyer and
V. Villiger (Ber. 34, 2679 (1901)) then made an extended
study of the salts formed with a number of acids by different
groups of oxygen compounds including ethers, ketones,
esters, etc. These salts or oxygen compounds are analogous
to the nitrogen (ammonium) compounds. They are not
as stable under ordinary conditions, and their isolation and

preparation in quantity for study is difficult for most of

them. Certain acids have been found to be especially
suitable for the preparation of these stable oxonium salts,
 .

26 CHEMICAL REACTIONS.

hydroferrocyanic acid (by Baeyer and Villiger) and per-

chloric acid (by K. A. Hofmann, Ber.
I
43, 1080 (1910)).
In order to determine whether definite compounds are
formed, it is necessary to study the " Property-Composition
Curves" of mixtures of their components, such as, for
example, the freezing-point curves.
The application of the principles of the Phase Rule (cf
A. Findlay's "Phase Rule," or any of the larger modern
text-books of general chemistry) shows the existence of
such oxonium salts and their composition, since it may be
stated in general terms, that each maximum point of such
a freezing point curve plotted with abscissas as relative
content of the two components in the mixture and ordinates
as the freezing points, shows such a compound of the com-
position given by the point on the abscissa axis. The
application of such studies (and of analogous studies on the
properties depending upon thermodynamic relations such
as vapor pressure, etc.) to aqueous solutions indicated that
compounds of water and salts exist similar to the ammoni-
ates. It is readily conceivable that the hydrate of hydrogen
chloride may be compared with ammonium chloride, some
of the chemical properties differing because of the difference
between nitrogen and oxygen. This question will be taken
up again later. For the present, reference to a number of
papers describing such compounds may be given.
Among those who have worked in this field may be
mentioned J. N. Collie and T. Tickle, Trans. Chem. Soc.
75, 710 (1899); J. N. 971 (1904); A. Baeyer
Collie, Ibid. 85,
and V. Villiger, Ber. 34, 2679, 3612 (1901); 35, 1201 (1902);
S. Hoogewerff and W. A. van Dorp, Rec. trav. chim. 21,
349 (1902); J. Thiele and F. Strauss, Ber. 36, 2375 (1903);
D. Vorlander, Lieb. Ann. 3^1, 1 (1905); V. A. Plotnikoff,
J. Russ. phys. chem. Ges. 36, 1088 (1904); 40, 64 (1908);

H. Stobbe, Lieb. Ann. 370, 93 (1909); K. A. Hofmann and

co-workers, Ber. 43, 178, 183, 2624 (1910); D. Mcintosh,
 VALENCE; CO-ORDINATION NUMBER. 27

Jour. Amer. Chem. Soc. 32, 542 (1910); O. Maass and D.

Mcintosh, Ibid. 34, 1273 (1912); 35, 535 (1913); M.
Gomberg and L. H. Cone, Lieb. Ann. 376, 183 (1910); J.
Kendal, Jour. Amer. Chem. Soc. 36, 1222, 1722 (1914);
J. Kendall and C. D. Carpenter, Ibid. 36, 2498 (1914);
J. Kendall andW. A. Gibbons, Ibid. 37, 149 (1915); as well
as a number of others.
Water, then, may add to salts to form the so-called
"water of crystallization" or hydrates in a way similar to
the action of ammonia.
The structures of some of the simpler molecular com-
pounds will now be developed before going on to the more
complex ones and the double salts. Ammonia is formulated
NH3, hydrogen chloride, HCl, and ammonium chloride,

NH4CI. The state of oxidation of nitrogen in ammonia

and in ammonium chloride is the same, — 3 and — 4+1
= — 3. The difference in the nitrogens consists in the
fact that one negative electron was taken up and one given
off in the formation of the ammonium salt. A comparison
of the similar simple molecular compounds of other elements
brings to light the same fact, that in each the "central"
element takes up and gives off a negative electron in forming
the molecular compound but does not change its state of
oxidation. Thus, there may be mentioned phosphonium
phosphorus — 4 + 1 = — 3), sul-
(state of oxidation of
fonium (- 3 + 1 = - 2), oxonium (- 3 + 1 = - 2),
iodonium (— 2 + 1 = — 1), selenonium (— 3 + 1 = — 2),
arsonium (— 5 + 1 = — 4), stannonium (— 3 + 1 = — 2),
and stibonium (— 5 + 1 = — 4) compounds.
The characteristic property of these simple molecular
compounds, which may be grouped under the name of
"onium compounds," is the fact that the atoms or groups
combined directly with the "onium" forming or central
element, act as a unit with the centralatom in many phys-
ical and chemical transformations and are often termed
28 CHEMICAL REACTIONS.

radicals. This is shown for physical phenomena in the con

duction of the electric current where these groups act very
often as ions, and in chemical reactions in metatheses where
the groups are capable of replacing other atoms or groups.
When ammonia is added to platinic chloride, it appears
that two methods of combination exist. The first two mole-
cules of ammonia add to form the compound PtCl4.2NH3,
which is not ionized in solution, and does not yield a precipi-
tate of silver chloride when treated with silver nitrate. If

a compound containing a third molecule of ammonia is

prepared, PtCU.SNHs, this substance ionizes and one of

the four chlorine atoms may be precipitated by silver
nitrate. The third ammonia molecule evidently exerts a
different influence in the molecule than the other two. In
the substance PtCl4.4NH3, two chlorine atoms are ionized,
while in PtCl4.6NH3, four chlorines are ionized. The last
four ammonia molecules play a different part from the
first two in causing the chlorine to assume new properties.
The hydrates of chromic chloride show similar phenomena.
The electrical conductivity of the greyish blue hydrate,
CrCl3.6Il20, is practically constant, four ions are present,
and all the chlorine may be precipitated with silver nitrate.
In a freshly prepared solution of the isomeric green com-
pound at 0°, only one third of the chlorine is precipitated
by silver nitrate, and the conductivity at first is much less
than that of the former, but increases gradually, until it

finally reaches the same value as that of the other isomer.

The chlorine in these two compounds is evidently combined
differently. Three hydrates of chromic chloride, having
the composition CrCl3.6H20, are known. In one, one
chlorine may ionize, in another two chlorines ionize, and in
the third all the chlorines are ionic in solution (cf. Werner,

Neuere Anschauungen, III Edition, (1913) p. 333).

It has been stated that platinic chloride will add ammonia
just as hydrogen chloride does. The only difference at the
 N

VALENCE; CO-ORDINATION NUMBER. 29

present time is that the ammonia can exert two distinct

influences or can add in two ways in connection with
platinum chloride, while it is probable that it can add in
one way only to hydrogen chloride, although an allotropic
modification of ammonium chloride was described recently
(F. E. C. Scheffer, Chemical Abstracts 10, 411 (1916)).
Ammonium chloride in aqueous solution yields chlorine
ions just as the platinum chloride-ammonia compound,
2NH3.PtCl4 with 1, 2, 3, or 4 additional molecules of
ammonia does. Since ionization was pointed out as a
characteristic property determining in which way the am-
monia had added to the platinic chloride or the influence
it exerted in the compound, it is likely that the ammonia

in the ammonium chloride is combined with the hydrogen

chloride in the same way that the ammonia is combined
with the platinic chloride when the chlorines of the latter
become ionic. If, therefore, the structure of ammonium
chloride known, it
is is possible to assign a structure to the
addition compounds of platinic chloride and ammonia as
far as the ammonia molecules which cause the chlorine
atoms to become ionic are concerned.

Sincediammono platinic chloride, (NH3)2PtCl4, combines

with ammonia in a similar way to that of hydrogen chloride,
the structure of the addition product may be written in a
(NHs)^ Pt CI3
H \
^ N—
similar way,

sive molecules of
namely

V ^Cl Introducing succes-

ammonia, analogous structures follow,

until when all four chlorines are ionizable, the structure

HHH HHH
Cl^N N-*C1
Pt (NH8)9
CI— N-Cl
/t\ /W
HHH HHH
30 CHEMICAL REACTIONS.

or (NH3)2Pt(->NH3 -^Cl)4 is obtained. The questioi

lestioiT
which now presents itself is the way in which the other two
molecules of ammonia are combined in the last compound
and also in (NH3)2PtCl4. The only evidence which is

available is that starting with platinic chloride, in which

the valence of the platinum is + 4, no oxidation or reduction
of any of the atoms is observable when the successive
molecules of ammonia are added. Platinic chloride is also
capable of adding two molecules of hydrogen chloride,
forming H2PtCl6, in which two hydrogen atoms are ioniz-
able. This last reaction indicates that platinum, like
nitrogen, is capable of acting as an onium element, forming
molecular compounds. If this assumption is made, then
the structures of the combinations can be expressed as

H^ Cl^ CI ^H
H"^ Cf" "^Cl ^^H
etc. In this way, only one kind of valence is present, and,
so long as no evidence exists against these structures, and
evidence (partly indirect, it is true) in favor of them, they
will be adopted.
In writing the structures of addition compounds, Werner
indicates auxiliary valence by dotted lines and ordinary
valence by full lines. This is illustrated by his structure
HsN:^ CI

for the di-ammoniate of platinic chloride, H3N- — — Pt CI

CI CI
When ammonia combine with the
additional molecules of
di-ammoniate, Werner considers these ammonia molecules
to be held by auxiliary valences in the same way as the
first two ammonia molecules, or in other words, that

ammonia adds to the platinum in one way only. This is

different from the idea developed here. Since the addition
 VALENCE; CO-ORDINATION NUMBER. 31

of the third, etc., molecules of ammonia give rise to ionic

chlorine, Werner considers that the entering ammonia
takes a between the platinum atom and the
position
chlorine atom, crowding the latter away from the central
platinum atom into a separate zone. Since the distance of
the chlorine atom from the central platinum is greater than
when it is bound directly, the latter acquires different
chemical properties, which manifest themselves in the ionic
character of the chlorine, etc. (Werner). Thus, the indirect
union is characterized by Atoms which
ionic properties.
are directly attached to another atom either by principal or
auxiliary valence are in the first zone. The number of
atoms or of molecules in the first or inner zone determines
the "Co-ordination Number." Atoms which are indirectly
joined to the central atom are in the second or outer zone.
Werner writes the structures for the ammoniates of
platinic chloride containing more ammonia than di-am-
moniate, as follows:

HsN.^ CI H3N, NH3

H3N--->t— CI CI; H3N- Pt CI Ck)
HsN' ~Cl H3N CI

HsN.^ ..NH3
H3N -;Pt---NH3 Cl3,etc.
HaN^ ^^Cl

The question of nomenclature is an important one and

must be considered in this connection. Werner introduced
certain terms in the development of his theory involving
main and auxiliary (or secondary) valences, and these
terms are useful. The consideration of a group in a mole-
cule in which the atoms react as a unit, as the inner zone
or sphere, and another group as the outer zone is used by
Werner, the former to denote the group consisting of the
central atom combined with other atoms or groups by
32 CHEMICAL REACTIONS.

and ionizing in solution.

auxiliary or principal valences
J
The method introduced by Werner of writing these groups
is extremely convenient, the inner zone being enclosed
in brackets. The expressions inner zone and outer zone
and the use of brackets will be followed in this book, but
the significance of the combinations between the atoms
from the point of view of the electron conception of valence
must be kept strictly in mind. In using the terms intro-
duced by Werner, it is not intended to endow the groups
with the physical significance which the meanings of the
words might imply. The expressions inner zone and outer
zone simply mean different groups which have a partially
independent existence under special conditions (the most
common one being in solution), and the atoms comprising
such a group act as a unit very often. The terms inner and
outer mean nothing more and must be looked upon as a
convenient phraseology.
The force field theory of Baly assumes the primary forma-
tion of an addition product, which, under certain conditions
can become a definite compound in which the atoms are
combined by ordinary valences. The views outlined here
may be used similarly. The first addition of ammonia and
hydrogen chloride may produce a compound H3N Z^ HCl,
or H3N CIH, presumably the former by analogy as will
;;:!:

be pointed out later, and this then rearranges or tauto-

merizes to the more usual form H4NCI. These two steps
correspond to the steps of Baly. The onium valence corre-
sponds in a number of compounds to the auxiliary valence
of Werner, and the reaction just given may be stated in
Werner's terms as due to a compound being formed of
molecules combined by an auxiliary valence, which under
certain conditions may become principal valences. The
views given here have an advantage over other views in
postulating only one kind of valence, and in keeping the
difference between valence and chemical affinity strictly

in mind.
 VALENCE; CO-ORDINATION NUMBER. 33

The structures developed with platinic chloride can

evidently be applied to a great number of compounds, such
as hydrates, other ammoniates, and molecular compounds
in general. A comparison of the structures of hexammono-
platinic chloride and the hexahydrate of calcium chloride
will show this:

-4 -4 -8 -3
.+ +1 +1 +
Cl^ HgN NHg CI HpQ .OHi -CI

, ;t\^i/;U f +1 . - +1 +
ff3N^Pt^NH3 CI HgO^^Ca
. '=^.Ca __
OHt CI
+ A/^ X+1 +
HgN^ NH3- CI >.0^ ^OH
From the foregoing it is evident that the co-ordination
number of the platinum in platinic chloride di-ammoniate,
(NH3)2PtCl4, or in platinic chloride hexa-ammoniate,
(NH3)2PtCl44NH3, is six, while the co-ordination number
of nitrogen in ammonium chloride is four, etc.
Calcium chloride may combine with six, four, or two,
molecules of water of hydration or exist in the anhydrous
state. The co-ordination number of the calcium in the
hexahydrate is six, but what it is in the tetrahydrate is

difficult to say, since it is not known whether the chlorine

is in the inner or outer zone. In the di-hydrate it may
be four, and in the zero hydrate it can only be two.
The external physical conditions such as concentration,
vapor pressure, and temperature, determine the number of
molecules of water of hydration of the calcium chloride.
This shows that the co-ordination number of the calcium
is dependent upon external conditions just as the ordinary
valence is.

Calcium chloride combines with eight molecules of am-

monia, or the calcium has the co-ordination number eight
in this compound. A large number of salts have been
found to crystallize with six molecules of water. With
regard to ammonia, copper sulfate can combine with four
 :

34 CHEMICAL REACTIONS.

molecules, silver chloride with two, etc. Werner showed

J
that the co-ordination number of an element is, in general,
four, six, or eight.
These definite numbers show a capacity for combination
and are therefore of the nature of valence numbers. They
are not identical with the atomic valence as already defined,
which is due to the transfer of a negative electron, but
indicate a different kind of capacity factor of chemical
energy. The manner
which this is to be interpreted, and
in
the underlying properties upon which it depends, cannot
be settled at present. A possible suggestion that it depends
upon spacial configuration and arrangement of the atoms
around a central atom may be put forward. The stereo-
chemistry of the compounds, as shown by A. Werner, the
deductions of T. V. Barker, and the theoretical and experi-
mental researches of W. H. and W. L. Bragg and of A.C.
Crehore, point in this direction. Whatever the cause may
be, this capacity factor exists, and as shown, may be inter-
preted by means of the general valence linkings of the
electron conception. In the later chapters, the significance
of co-ordination number in this sense is used where reference
is made to a definite combining capacity of this nature.
Although the platinum atom in the ammoniates of
platinic chloride has been considered as the central atom,
the nitrogen of the ammonia (except with the first two
molecules of ammonia) also may be taken to be the central
atom. Thus, when the di-ammoniate, (NH3)2PtCl4, com-
bines with ammonia, it really plays the same part as the

hydrogen chloride in the formation of ammonium chloride.

In both cases, the chlorine of the hydrogen chloride and
of the di-ammoniate, (NH3)2PtC]4, becomes ionic. The
structures for the tri-ammoniate, (NH3)2PtCl4NH3, and
ammonium chloride are analogous

Tl^H (NH3)2 Pt Cl3;| H

N: Cl
CI
H H
 VALENCE; CO-ORDINATION NUMBER. 35

When hydrogen chloride and platinic chloride combine

to form the addition compound, chlorplatinic acid, H2PtCl6,
the platinic chloride plays a role somewhat similar to that
of ammonia in the formation of ammonium chloride, that
is, both are added to hydrogen chloride. There is a differ-
ence, however, in that the addition of platinic chloride to
hydrogen chloride causes the hydrogen of the hydrogen
chloride to become ionic, while the addition of ammonia to
hydrogen chloride causes the chlorine of the hydrogen
chloride to become ionic. In other words, in the first case,

the hydrogen is in the outer zone; in the second, the

chlorine is in the outer zone. Since ionogens are produced
in both cases, both the ammonia and the platinic chloride,
according to Werner, enter between the hydrogen and the
chlorine atoms in the hydrogen chloride. In one case, the
hydrogen is crowded out into the outer zone, while in the
other, it is the chlorine of the hydrogen chloride. Accord-
ingly, the structures of the two compounds may be written

-4
"h. -H
+ CI and CI— Pt^cl +
H H H
The two complexes, (PtCU) and (NH4), bear the same
relation in the addition compounds, the only difference
being that the charges have different signs, the former
being negative and the latter positive. The reason for this
lies in the electrical nature of the two central atoms.
Platinum an electro-positive element, and nitrogen in
is

ammonia is It becomes evi-

an electro-negative element.
dent in looking over a large number of complex salts, that
they ionize in such a way that the element in the outer
zone has an electric charge of the same sign as that of the
central atom to which it is attached. Thus, in addition,
of those with positive central atoms, potassium ferro- and
ferri-cyanides, where the positive iron atom serves as the
 :

36 CHEMICAL REACTIONS.

central atom, potassium chromium oxalate, KaCr (€204)3,

may be quoted out of the great number with which the
reader, no doubt, is familiar. As compounds of the type
in which the central atom is negative, may be mentioned
besides ammonium chloride, and the tri-ammoniate, tetra-
ammoniate, etc., of platinic chloride, the hydrates of calcium
chloride, aluminium chloride, chromium chloride, etc., since
in these hydrates just as in the ammoniates, the oxygen
the water may serve as the central atom.
It has been stated that water like ammonia can be adde I
in two ways in the formation of addition compounds such
as the hydrates, calcium chloride hexahydrate, etc., similar
ammonia in the hexa-ammoniate
to the of platinic chloride,
PtCUGNHs. When platinic chloride is dissolved in water,
the aqueous solution does not contain chloride ion as would
be expected if the water combined with the chloride as the
ammonia does. The platinic chloride combines with the
water, however, to form the di-hydrate, PtCl42H20, which
+
is an acid and yields the ions 2H and PtCl4(OH)2, and should
therefore be formulated H2PtCl4(OH)2. The water behaves
towards the platinic chloride just as the hydrogen chloride
does in the formation of the chlorplatinic acid, H2PtCl6.
The platinic chloride enters between the hydrogen and the
hydroxyl of the water molecule, analogous to the way it

does in the case of hydrogen chloride, and in each case

forces or transfers the hydrogen into the outer zone. The
structures of the two complexes, PtCl4(OH)2 and PtCle,
ought therefore to be alike. They may be written as
follows

and

I II

The water molecule here has added as H and OH. In order

 VALENCE; CO-ORDINATION NUMBER. 37

to get a definite picture of the differences between the three

ways in which water can function in these addition com-
pounds, the reader may compare structure I with the struc-
ture of the hexa-hydrate of calcium chloride. With the
latter, part of the water enters between the calcium and
chlorine atoms, producing chloride ions, and part of the
water is simply added to the calcium atom by onium valence
or "auxiliary" valence or "force field," symbolized by
the two arrows in opposite directions. It was stated
previously that the first ammonium
stage in the formation of
chloride from ammonia and hydrogen chloride may be the
formation of a primary addition compound, H3N ^ HCl,
due simply to the onium valence, or the auxiliary valence
or the force field between the nitrogenand the hydrogen
atoms, and that this preliminary compound then tauto-
merizes into (NH4)C1 with the chlorine in the outer zone.
Now this preliminary stage possibly may occur in the for-
mation of all these addition compounds, no matter what the
subsequent rearrangement happens to be. Thus, in the for-
mation of the hexa-hydrate of calcium chloride, all the mole-
cules of water first may add to the calcium atom through the
force field, and then tautomerism may set in, the chlorine
leaving the calcium to combine with the oxygen of the water.

HgO^ H2
HgO;^ -^0112 H,0:^ 0- -^Cl
HaO^^^x-Cl H^O-^Ca 0- -^Cl
YLo.0^^ ^Cl HaO^^ H2

Similarly with the di-hydrate of platinic chloride,

H2PtCl4(OH)2, all the water molecules may add to the
platinum atom through the force and then
field first rear-
rangement set in and the hydrogens become ionic.
Ci OH.

CI ^OUy
 :

38 CHEMICAL REACTIONS.
1
In the case of the hexa-ammoniate of platinic chloride,
the ammonia may behave in a way analogous to that of
the water in the hexahydrate of calcium chloride. Whether
or not all the water molecules or ammonia molecules must
first be combined with the platinum or calcium atoms in
this way before any tautomerism can take place, it is im-
possible to say.
Potassium chloride adds to platinic chloride, in the same
way that hydrogen chloride does, forming potassium chlor-
platinate. The latter would therefore have a structure

similar to that of the acid, or

_C1^ "Cl_
the case of the formation of the other addition compounds,
here, too, probably, the intermediate stage may occur
where the potassium chloride is added to the platinum
atom in the onium way and then rearranges, the potassium
going into the outer zone.
It is well known that ammonium chloride can add to
platinic chloride just as potassium chloride does, forming
the ammonium chlorplatinate. Chlorplatinic acid, H2PtCl6,
adds to ammonia just as hydrogen chloride does, forming
the ammonium chlorplatinate ; the di-ammoniate of platinic
chloride adds to hydrogen chloride, forming ammonium
chlorplatinate. In each of the above cases an addition
compound plays the same role as a simple compound,
forming addition compounds with other molecules.
From what has been said in regard to the probable
structures of the hexachlorplatinic acid, H2PtCl6, and the
tetrachlorplatinic acid, H2PtCl4(OH)2, it is possible to assign
structures to the whole series of platinic acids, as Werner
has done (Neuere Anschauungen auf dem Gebeite der
anorganischen Chemie, 3d ed. (1913), pp. 40-1).
 H H O HH
VALENCE: CO-ORDINATION NUMBER. 39

CI- qi\^«,^ci 1 + Cl^ll^Cl ^

Cl- -Pt— CI H, Cl— Pt^Cl ^ Ha CI—Pt-O-H
Cl^
"^ ^Cl C\^ ^0-H_ Cl^ ^0-H '

Chlorplatinic Pentachlorplatinic Tetrachlorplatinic

acid acid acid

CK^i/O-H +
CK ±1 /O—
CI— Pt— O— Hg CI—Pt— O— Hs
c\^ \o— fi fi— ^ "^O —
Trichlorplatinic acid Dichlorplatinic
(not known) acid

Cl^ +
-2
6 O— H — 0\ +6 /O —
-0 ^Pt- 0— Ho H— 0—Pt— O—
H— Q/^ ^O— H— 0^ \o—
Monochlorplatinic Platinic
acid acid

The fact that these acids are all dibasic proves that the
acidity is not connected with the hydrogen of the hydroxyl
groups, and by comparing the whole series from chlor-
platinic acid to platinic acid, it is evident that the ionizable
hydrogens are those combined directly with the positive
central atom, platinum in this case. The salts of these

acids have similar structures.

It will have been observed that tautomerism has been
spoken of a number of times as occurring with different
compounds. The idea of tautomerism is familiar from
organic chemistry, but it appears to be of much wider
applicabilitythan has been heretofore assumed (cf. also
W. C. Bray and G. E. K. Branch as well as G. N. Lewis,
Jour. Amer. Chem. Soc. 1440-1455 (1914)). In tautomeric
rearrangements, none of the atoms in the molecules is

reduced or oxidized; each remains in the same state of

oxidation as before. This is brought out by the following
formulas which represent the tautomeric forms of a number
of substances:

h->c5n and ii-^n:ic

ii3Nr:n->ci and Il4N->Cl

40 CHEMICAL REACTIONS.

H3N::!:S63 and H2N<-Sd2~>6H

-4 +7 -4 +8 -4

(H3N)3::lPtCl4 and (H3N)2::lPt(Cl3) -^NHs ->C1

-3 +6 '^ J.

(H20)2;lPtCl4 and H2PtCl4(SH)2,

and so on.
These examples show the possibilities of tautomeric

inorganic compounds. The valence or state of oxidation

of none of the atoms has changed. Although tautomeric
changes in molecules will be used in the later chapters,
will not be referred to explicitly or in detail.
 CHAPTER III.

ACIDS AND BASES.

The valence views upon which the structures and classi-

fication of substances depend have been given in some
detail in the preceding chapters. Before proceeding to
consider the theory of chemical reactions which it is desired
to emphasize here, some further applications of the valence
views may be of interest. Acids and bases form two of the
most interesting and widely studied groups of substances
in chemistry, and the bearing of the theoretical relations
described upon their reactions and formulations will be
given. The considerations bear also upon the state of
substances in solution.
The theoretical view of the chemical nature of acids was
put upon a very much more satisfactory scientific basis by
Arrhenius in 1887. He showed that the acid properties of
substances in solution depended upon the presence of hydro-
gen ion,and that the concentration of this hydrogen ion
could be measured in a number of different ways. In the
electrolytic dissociation in solution in which the positive

hydrogen ion is produced, the rest of the molecule forms

the negative ion, but for the characteristic properties of
the acid only the hydrogen is of importance.
The theory of ionization in solution showed that hydrogen
ions are the essential constituents of acids. However, the
part played by the solvent in the ionization, or in other
words, the probable mechanism of reaction according to
which the ions are i)r()(luced, is not shown in the theory of
Arrhenius. It is true that the relative degrees of ionization
of substances in different solvents were shown to be paral-
leled by certain other properties of the solvent, such as the
dielectric constant, and that combination of the solvent
41
42 CHEMICAL REACTIONS.

with the ion has been proven to exist in a number of casesjll

but these facts are far from a satisfactory theory of the
reactions taking place when a substance is considered to
undergo ionization.
The views of Werner with regard to acids may be stated
in the form in which he summarized them (Neuere An-
schauungen, pp. 273-275), There are anhydro acids
(1)
and aquo (2) Every compound which can form a
acids.
hydrate with water, and which then yields hydrogen ions
in is an anhydro
aqueous solution as a product of ionization,
acid. Every hydrate which ionizes in aqueous solution
(3)
yielding hydrogen ions, is an aquo acid, or in short, an acid-
In terms of the ionic electrochemical viewpoint, the follow-
ing definition is given by Werner for an anhydro acid:
A compound which, in aqueous solution, combines with the
hydroxyl ions of the water, and in this way shifts the
equilibrium for the electrolytic dissociation of water to a
limiting value for the hydrogen ion concentration character-
istic for the compound, is an anhydro acid.
These views of Werner, involve a theory of the mechanism
of acid production in solution, and are of general interest.
The structures which he gives are of the same nature as
those he gives for salts, etc., as will be seen presently when
comparing them with the structures developed in connection
with the electron conception of valence.
The views with regard to acids which follow from the
electron conception of valence and from the principles
outlined in the earlier chapters will now be given.
It will be of interest to take up a number of acids contain-
ing oxygen. Sulfuric acid may serve as a typical example.
Its structure is formulated ordinarily as:

o/ ^OH
This structure is based upon a number of experimental
 ACIDS AND BASES. 43

facts, such as the reactions of organic derivatives of the

acid and related compounds, the successive replacement of
the hydroxyl groups, etc. From the discussion of the
platinum acids in the preceding chapter, it appears to be
highly improbable or a substance possessing this structure
to ionize as an acid. If, however, the structure is written
in the tautomeric form, this difficulty disappears and sul-
furic acid falls in line with the platinum acids. The tauto-
meric forms of sulfuric acid are:

^S^crS ^S^H
O^ ^O ^
and
O^ %
The formation of dibasic acids through the addition of water
to both sulfur trioxide and platinic chloride becomes, from
the above considerations, a similar phenomenon. Accord-
ing to the older view, the formation of sulfuric acid from
and water is due to the opening up of one
sulfur trioxide
of the double bonds between the sulfur and one of the
oxygen atoms, and the addition of the water as hydrogen
and hydroxyl to this opened up group.

028=0 -> O2S-O+H-OH -^

^Kou
This explanation cannot be applied to the mechanism in-
volved in the formation of the tetrachlorplatinic acid,
H2PtCl4(OII)2.
The addition of hydrogen chloride to sulfur trioxide,
becomes analogous to the addition of hydrogen chloride to
platinic chloride, yielding in the first case, chlorsulfonic
acid, IISO3CI, and in the second case, chlorplatinic acid,
ir2PtCl6.
The addition of potassium chloride to platinic chloride
toform potassium chlorplatinate, K2PtCl6, is similar to the
formation of potassium sulfate from potassium oxide and
sulfur trioxide.
 : ,,,

44 CHEMICAL REACTIONS.

The addition of ammonium chloride to platinic chlorr

to form ammonium chlorplatinate, (NH4)2PtCl6, is similar
to the reaction between chromium trioxide and ammonium
chloride to form Cr03ClNH4 (Werner). (It is impossible
to go into all the examples which may be given along these
lines, and the reader is referred to Werner's book for more
complete information.)
theM
It is possible to formulate the reaction involved in
formation of the first stage addition compound, in the case
™
of many of these substances as follows

SO3 + H20^^S03:!:H20, SO3 + hcis-^S03:;!:hci,

SO3 + NH3^-^S03:rNH3,

PtCU + 2H20^^PtCl4H|j['Q

PtCl4 + 2HCls-^PtCl4H^ci >

PtCl4 + 2NH3^- Pt Cl4H^|[{^

PtCU + 2KCls^PtCl4H|Q

AUCI3 + KCis-^AuCi3::!:KCi,

AUCI3 + NH4Cle^AuCl3:;!:NH4Cl,
etc.

These primary addition products may then rearrange or

tautomerize into the structures for the acids or salts which
have already been given and which represent the customary
formulations.
It has been mentioned that addition compounds which
more than one zone are ionogens by definition or
consist of
description,and that if the components in one zone are
hydrogen or hydrated hydrogen, the compound is an acid.
The hydrogen bearing this relation to the addition com-
 ACIDS AND BASES. 45

^ound corresponds to the hydrogen ion of Arrhenius. A

substance dissolved in water will be an acid (that is, it will

furnish hydrogen ionH+) if it forms hydrates containing

hydrogen or hydrated hydrogen in one of the zones. For
example, hydrogen chloride forms hydrates when dissolved
in water and is an acid, but when dissolved in some solvent
with which it does not form an addition compound, a
hydrocarbon for example, then it does not have the proper-
ties of an acid. The hydrate of hydrogen chloride in dilute

aqueous solution will undoubtedly have a great number

of water molecules attached to it, and its probable structure

may be expressed as CI The part within

the brackets is, therefore, an example of hydrated hydro-

gen.
Hydrogen chloride may also form an acid by combining
with other compounds than water. Thus it may do so by
reacting with either platinic chloride to form chlorplatinic
acid by displacing water in
or tetrachlorplatinic acid,

H2PtCl4(OH)2, and thus forming chlorplatinic acid. In

chlorplatinic acid, the platinic chloride may be said to serve
the same purpose as the water does in the hydrate of hydro-
gen chloride, that is, it separates the hydrogen and the
chlorine of the hydrogen chloride into the two zones. It

might be said, therefore, that since water is often spoken of

as an ionizing medium for electrolytes, that the platinic

chloride is also in the same sense an ionizing medium for

certain electrolytes such as hydrogen chloride, potassium

chloride, etc.
Since the behavior of ammonia toward hydrogen chloride
is similar to that of water and of platinic chloride, it also

should yield an acid in forming an ammoniate with hydrogen

( liloride. This is in fact the case, for when ammonium
 :

46 CHEMICAL REACTIONS.

chloride or hydrogen chloride is dissolved in liquid imom^

ammonif
and this solution treated with magnesium or a similar
metal, hydrogen is evolved, and the metal is dissolved. At
the present time, however, it is not customary to consider
such an ammoniate as an acid.
Hydrogen chloride by itself is not an acid, but becomes
one when dissolved in water by virtue of the formation of
hydrates. In the same way, sulfur trioxide is not an acid
and only becomes one when combined with some compound
containing hydrogen, such as water. However, sulfuric
acid is more closely related in the formulations to the tetra-
chlorplatinic acid, H2PtCl4(OH)2, than to the hydrate of
hydrogen chloride. The sulfur trioxide and the platinic
chloride first add to the water and then tautomerism and
shifting of the hydrogen to the outer zone takes place.
On the other hand, with the hydrate of hydrogen chloride,
the water first adds and then the chlorine enters the outer
zone. Sulfuric acid, H2SO4, which is itself an addition
compound, may add to water to form compounds of the
H2SO4H2O; H2SO4.2H2O. The con-
third order such as
stitution of such higher hydrates may be indicated as follows

[(IS)J[H.=(H.O).],

It therefore becomes evident that the mono-hydrate,

SO3.H2O, will have the constitutional formula H2(S04) and
be similar to tetrachlorplatinic acid H2(PtCl4(OH)2), while
the hydrates of the higher orders will have hydrogen in the
hydrated form, and correspond to the hydrates of hydrogen
chloride.
The structures of acids as outlined are not complete for
the co-ordination number of the hydrogen has not been
taken into account in their development. Unfortunately,
the co-ordination number of hydrogen is not known. At
the same time, it has not been established experimentally
 ACIDS AND BASES. 47

whether it is necessary for the co-ordination value of a

central atom to be satisfied before ionization will take place,
or in other words, in order that the compound shall exist
in what has been termed inner and outer zones. As far
as this point has been investigated, as for platinum, cobalt,
and chromium compounds, it seems as if the co-ordination
number (maximum) must be satisfied before ionization
takes place. With hydrogen chloride and ammonia, for
example, ammonium chloride, NH4CI, would not be an
ionogen, but only becomes one when more molecules of
ammonia in liquid ammonia solution, or water molecules
in an aqueous solution collect about the hydrogen atom
until the co-ordination value is reached. If the co-ordina-
tion number of assumed to be
hydrogen is four, then the
formulas for ammonium chloride would be

Hp:^^ ^H^O
H and H or H
H, .0^ ^O-- CI H.O^ CI

non-ionogen

These formulas involve the view that when ammonium

chloride is dissolved in water it undergoes hydration.
The mechanism of the ionization of hydrogen chloride
in water may be expressed similarly. The water molecules
play the same part as the ammonia forming the hydrate
H,0;^ :H,0
::h:
which may be represented as follows: H,0 CI

That part of the compound within the brackets or inner

zone is the hydrated hydrogen ion. Since water is the
common solvent for most electrolytes, it is customary when
speaking of hydrated ions to refer to the central atom or
group acting as ion, or in this particular case, the hydrated
hydrogen ion. When however part of the water molecules
48 CHEMICAL REACTIONS.

are displaced by ammonia, then they are spoken of ai

ammonium and not hydrogen (or hydrated hydrogen)
ion
ion. The similarity is further emphasized by reactions
such as the solution of zinc in a water solution of ammonium
chloride or the solution of magnesium in a liquid ammonia
solution of hydrogen chloride with evolution of hydrogen
similar to the solution of a metal in an aqueous solution o:

an acid.
It further emphasizes the point that ammonium
are only hydrogen compounds where the hydrogen atom
salt
I
has associated with one ammonia, while if it has associated
with itmore ammonia molecules it is generally considere
as an abnormal addition compound. Ammonium salts ar<
only one particular case of ammoniated hydrogen com
pounds. Similarly, oxonium salts are only a particula:
case of the series of hydrates of hydrogen and similar
i
compounds.
It is also possible by this theory to correlate the fact that
platinic chloride dissolved in aqueous hydrochloric acid
forms chlorplatinic acid with the formation of addition
compounds similar to ammoniates. Since the co-ordination
number of the platinum atom is six, the platinic chloride
can combine with two molecules of hydrogen chloride to
form a compound similar to the diammoniate. Since,
however, the addition compound exists in a water solution,
the hydrogen chloride can also form the hydrate and equal
the co-ordination number of hydrogen. In this case the
hydrogen chloride will become ionized just as with the
ammonium chloride in the water solution. In other words,
which make up the co-
either the water or platinic chloride
ordination value of the hydrogen of the hydrogen chloride
will enter between the hydrogen and the chlorine and

separate or ionize them. It is probable that in this case

the platinic chloride enters between the hydrogen and the
chlorine and hence the structural formula for chlorplatinic
 :

ACIDS AND BASES. 49

acid may be written as follows —assuming the co-ordination

number of hydrogen to be four

It is to be noted that in the case of chlorplatinic acid the

platinic chloride is really considered to be the ionizing
agent of the hydrogen chloride, while in the case of the
hydrate of hydrogen chloride, water is considered to be the
ionizing agent. Furthermore, when platinic chloride acts
as the ionizing agent then the hydrogen or hydrated
hydrogen occurs in the outer zone or in other words the
separate ion, and the chlorine in the inner zone or the
complex ion containing the platinum atom. When am-
monia or water acts as the ionizing agent in the case of
ammonium chloride in a water solution, then the chlorine
occurs in the outer zone or in the part which does not remain
in the complex ion. If upon the various
the valence charges
atoms compounds are taken into account,
in these addition

it also becomes evident that the atom with the same charge

as that of the atom which enters in between the two atoms

is the one which appears in the outer zone. Thus when the
ammonia ionizes the hydrogen chloride the nitrogen is the
entering atom and is predominatingly negative and there-
fore the chlorine would be in the other zone, while when
platinum which is predominatingly positive is the entering
atom, then the hydrogen which is positive occurs in the
other zone from the platinum atom.
It has already been pointed out that hydrogen chloride
when dissolved in water acquires the properties of an acid.
In the form of its hydrates the maximum co-ordination
number of the hydrogcMi is probably equalled and the water
entering between the hydrogen jind i\w clilorine of the
 J

50 CHEMICAL REACTIONS.

hydrogen chloride causes ionization, which is indicated in

H
4
the formula by two zones When pla-
H
—h-^ui -^Cl

tinic chloride is added to an aqueous solution of hydro-

I
chloric acid, or hydrate of hydrogen chloride, the di-
basic acid chlorplatinic acid is formed, generally given the
formula H2(PtCl6) and assigned by Werner the structure

01 "1
[01
OlPtOl .

Ol 01

Here again the co-ordination number

considered as well as that of platinum.
of hydrogen
In other words,
will I
just as in the case of hydrogen chloride in water, the sub-
stance does not ionize until the co-ordination value of the
hydrogen is reached, and consequently the more correct
formulation would be (H20::l)a:H2[PtCl6]. The part
actually played by the platinic chloride in forming the
chlorplatinic acid in a water solution of hydrogen chloride,
is that platinic chloride replaces the ionizing molecule of
water in the hydrate of hydrochloric acid.

H2
(H20:^L H-0- Cl + Pt Cl4>^ —^ (H20:i^)xH2=^Pt = Cl2

It is interesting to note the frequency of the occurrence

of complexes in the inner zone in which the co-ordination
number of the central atom is eight. H2(S04), H(Mn04),
H(C104), H3(As04), (RUO4), (OSO4), etc., all conform to
the general type (AO4) for the inner zone, water of hydra-
tion being omitted in these formulas. In determining the
co-ordinationnumber of an atom, the rule is followed here
that a univalent atom such as chlorine and a compound
such as hydrogen chloride counts as one, while a bivalent
atom such as oxygen counts as two. This rule is arbitrary.
 ACIDS AND BASES. 51

For the present it is necessary to have some such rule and

collect data. It will undoubtedly be possible in the future
to find a more general rule and method of determining these
capacity numbers.
It was stated before that it has been customary to assign
the hydroxyl structure to sulfuric acid and its hydrates.

HO. ^O H .OH HO^ ^OH

SC^ S-OH HO S^— OH
HO^ ^O H 0^ ^0 HO^^ ^OH
SO3.H3O SO3.2H2O SO3.3H2O

According to these structures the double linking between

the oxygen and the sulfur opened up and added the hydro-
gen and hydroxyl of the water, forming in this way two
hydroxyl groups combined with the sulfur in place of one
oxygen

H-OH +
^O
-0-s::;;'
^0
= HO^ ^O
^O
HO-^
sc"

Accordingly, the dihydrate should be a tetrabasic acid if

the acidity were due to the hydrogen of the hydroxyl, but

this is contrary to experimental facts. Similarly, osmium
and ruthenium oxides might be expected to show a greater
tendency to form acids than sulfur trioxide since they con-
tain more oxygen atoms with double linking to combine
with the water. It is evident, therefore, that a knowledge
of the co-ordination number as well as of the atomic valence
is necessary in order to determine the basicity of an acid.
Just as there is a series of acids in which the co-ordination
number of the central atom is eight, a series of acids exists
in which the co-ordination number is six. An example of

this series is nitric acid II(N03). The atomic valence of

the nitrogen is plus five, the co-ordination number six,
and the basicity one. The same is true of chloric acid
1I(C1()3), iodic acid 11(103), etc. Meta-phosphoric acid>
IlCPOs), belongs to this group, although ortho-phosphoric
 '

52 CHEMICAL REACTIONS.

acid, H3PO4, belongs to the group in which the co-ordinatioi

number is eight. This brings up the question of whethei
an acid, the co-ordination number of whose central atony ,

six, can be converted into one whose central atom hal| |

co-ordination number of eight by means of hydration

This appears to be possible, for example, in passing from
metaphosphoric acid to the ortho acid. On the other hand
nitric acid, and the nitrates of the alkali metals, form hy-
drates, but only mono-basic nitric acid has been observed
experimentally. The additional molecules of water in the
hydrates of nitric acid may, therefore, be combined with
the hydrogen atom which would act as a second central
atom, or be combined with the nitrogen in such a way as
not to tautomerize the hydrogen of these water molecules
into the outer zone, or they may be added to the double
linking between the oxygen and nitrogen and be present
as hydroxyl groups.

0^/OH
[(H20)n^=^H] [NO3] or h[N03^=^(H20)] or H N
>^^
The co-ordination number is a function of external
physical conditions. Its value in the case of the nitrogen
in nitric acid is six in all the conditions under which nitrates
have been studied. With the acids of phosphorus, however,
the co-ordination number may change from six to eight.
This change is similar to the changes which occur with
atomic valence. Some elements can show several different
show only one.
states of valence, while others
The showed that bases yield hydroxyl ions
ionic theory
in aqueous solution, and that a base might be defined as a
substance which in solution forms hydroxyl ions.
Since ammonium salts can be formed directly by the
addition of ammonia and acid to each other, ammonia
itself has sometimes been spoken of as a base. Similarly,
since amines are like ammonia in this respect, they also
 ACIDS AND BASES. 53

have been considered to be bases. At first, in order to

distinguish them from the true metallic alkalies, they were
sometimes called alkaloids (A. W. Hofmann, Lieb. Ann.
73, 91 (1850)). This term, however, is now reserved for
the more complicated amines which occur in nature, which
show marked physiological properties. Two different defi-
nitions for the term base have been current with the amines.

(1) They furnish hydroxide ion in aqueous solution. (2)

They combine with acids to form substituted ammonium
salts. This, naturally, has led to some confusion, since
amines have frequently been called strong bases or weak
bases, depending upon the amount to which ammonium
salts were formed when they were added to an acid.
According to the ionic theory, the relative strengths of
different bases are given by the ionization constants as
calculated from the Ostwald dilution law, these depending
upon the concentrations of ionized and un-ionized sub-
stances present in solution. The equation for calculating
the ionization constant (which naturally should hold for
all substances in solution, not merely bases) is as follows
for a substance BA, ionizing into B"*" and A~:

[B+][A-]
^'
[BA]

in which the terms in brackets denote the concentrations.

Highly ionized substances, including the bases sodium
and potassium hydroxides, etc., give values for the ioniza-
tion constants which vary with the concentration. On the
other hand, slightly ionized bases, among which may be
included some of the substituted ammonium hydroxides,
give constant values, and it appears as if the strengths of
these bases might be compared in this way. A difficulty
arises, however, which prevents a direct comparison. Dis-
tribution experiments with organic solvents and an a(|ueous
solution of ammonia, showed that in the water only a part
 CHEMICAL REACTIONS.
54
I
of the latter was present as ammonium hydroxide, the rest
being dissolved as such (ammonia) or more probably as a
hydrate. The ionization constant, to show the strength
of the base should be calculated from the concentration of
the ammonium hydroxide from the equation
[NH4+][0H-]
[NH4OH] ^'*

At the same time, the equilibrium

[NH3][H20] _
[NH4OH] ^''

orsome similar equilibrium, must be taken into account.

The same is true for the substituted ammonium hydroxides.
The values of the ionization constants for these bases, as
determined ordinarily, are apt to be misleading for this
reason. A few of the values hdve been determined cor-
rectly. The influence of the solvent is shown here, but a
satisfactory interpretation of. its action in the ionization of
these bases and of other bases is not given in the ionic
theory. The further developments, just as with the acids,
follow the lines indicated by Werner and the conceptions
developed here.
According to Werner (Neuere Anschauungen, pp. 268-
270), an anhydro base is a substance which forms a hydrate
with water and then yields hydroxide ion and a complex
positive ion in aqueous solution. The anhydro base
ionizes in this way by combining with the hydrogen ion of
the water, and producing hydroxide ions (from the water)
in a concentration characteristic for the substance. Aquo
bases, or bases, are addition compounds of substances with
water which yield hydroxide ions in aqueous solution.
The method of indicating these relations with hydroxy 1
in the outer zone, etc., follows from what has been said
before. The introduction of the electron conception of
valence shows the distribution of the charges, etc. It will
not be necessary to develop these relations further here.
 ACIDS AND BASES. 55

The statement is sometimes made that tetramethyl

ammonium hydroxide is so strong a base that neither
sodium nor potassium hydroxide can separate it from its

salts, but that silver hydroxide must be used for this

purpose. It is much more probable that the reason for
the silver hydroxide being much more efficient than the
alkali hydroxide is the low solubility of the silver halide
usually formed as one of the dissociation products of the
intermediate addition compound. In place of using silver
hydroxide, the same reaction may be brought about by
allowing the reaction to take place in some other solvent
such as alcohol. This is a way of changing the external
physical conditions so as to favor the dissociation of the
intermediate addition compound in the desired direction

as will be explained in later chapters, because of the smaller

solubility of the sodium or potassium chloride in alcohol.

The state of substances in solution will now be taken up

briefly. The electrolytic dissociation of a large number of
substances is dependent evidently upon the properties of
the solvent as well as upon the character of the dissolved
substance (solute), because on the one hand all substances
do not ionize in a solvent such as water, and on the other
hand, a substance may ionize in one solvent, hydrogen
chloride in water, and not in a different solvent, hydrogen
chloride in benzene. The solvent must, therefore, also

be considered in the ionization relationships and the manner

in which it may be done follows directly from what has

been said.

As pointed out, hydrogen chloride in itself is not an acid,

but only becomes one when it forms a compound of a
higher order, or in other words, an addition compound.
Hydrogen chloride is al)le to form compounds of higher
orders with the compounds of the first order, ammonia,
platinic chloride, sulfur trioxide, auric chloride, water, etc.,
the compounds of the second order which are formed being
 66 CHEMICAL REACTIONS.

formulated as follows: [HNHalCl, H2[PtCl6], mSOaCl],

H[AuCl4], [HzOHlCl, etc. The linkings between the indi-
vidual atoms, however, follow the principles outlined in the
first chapter, the division of the compounds into zones as a
rule not influencing the distribution of the electric charges
due to the combinations between the atoms, except for
some cases of intramolecular oxidation and reduction.
The last of the compounds given in the preceding para-

graph was [H20H]C1. This compound with water would

evidently be an example of the compounds formed when
hydrogen chloride is dissolved in water. Many substances
combine with water to form compounds containing water
of crystallization. In the last fifteen years much evidence
has been accumulated which shows that hydrates exist in
solution as well, and also that ions are hydrated. The
most careful work in this field was done by E. W. Washburn
and by G. Buchbock, the former studying the relative
hydration of the positive and negative ions of the chlorides
of lithium, sodium, potassium, and caesium, and the latter
of hydrochloric acid. That is to say, they determined the
ratio between the number of water molecules combined
with the lithium, sodium, potassium, csesium, or hj^drogen
ion, and the number of water molecules combined with the
negative chlorine ion for certain definite concentrations of
aqueous solutions of these salts. Different amounts of water
were found to be combined with the positive ions, but in every
case, more water was combined with or associated with,
the positive ion than with the negative ion. It was im-
possible to determine directly whether any water was asso-
ciated with the negative ion, since the method permitted
only of the determination of the relative extents of hydra-
tion.

The existence of hydrated ions rests therefore upon a firm

experimental basis. The formula for the compound hydro-
gen chloride with water was given as [H20H]C1. In detailt
 :

ACIDS AND BASES. 57

k
this would be in which the oxygen is in the

onium state with a valence of — 3 + = —

1 2. The pre-
dominatingly negative oxygen holds the positive hydrogen
in the inner zone and the negative chlorine in the outer
zone, and the ions are [H30]+ and CI", omitting the addi-
tional water molecules which may be combined with the
hydrogen and the chlorine.
It is necessary to mention here the fact that water may
also be in combination with, or associated with the negative
ion, as well as with the positive ion. A salt such as hydrated
magnesium The composition of
sulfate will illustrate this.
this substance MgS04.7H20. It has been shown by vapor
is

tension measurements that six of the water molecules bear

the same relation to the molecule as a whole, but different
from the seventh molecule. Furthermore, the study of the
optical activity (rotation of the plane of polarized light) of
the substance, indicates that one molecule of water is

associated with the SO4 group. This indicates that the

water may be present in combination with either of the
two parts of the molecule which form the ions, or that both
positive and negative ions may be hydrated.
It was shown previously that hydrates and ammoniates
belong to the class of addition compounds. The substance
CrCl3.6H20, for example, is similar in structure to the
substance PtCU-GNHs, etc. The water in these compounds
is in combination with the metallic atom in the inner zone

or sphere, where the latter functions as the central atom.

The structures of some of these compounds may therefore
be given as follows

CI
11,0^ Cr: ili^O^Al
o-fci IIjjO^ II '^
k.H2 \ll2
'O- CI 0-Cl
Cr Cla.GIIgO Al Clo.GlUO Ca Clg.OHaO
 :

58 CHEMICAL REACTIONS.

was pointed out that the co-ordination number of

It
the central atom varied, depending upon certaiji physical
conditions such as temperature, etc. This means that the
number of molecules of water in the hydrated salts varies
with the conditions, but there are certain limits within
which a hydrated salt having a perfectly definite composi-
tion is stable. A study of these substances from the point
of view of the phase rule shows the compositions and ranges
of stability of the various hydrates and other compounds.
For calcium chloride, the forms which are known include
CaCl2, CaCl2.2H20, CaCl2.4H20, and CaCl2.6H20. The
graphic formulas for these substances might be written
as follows

+ 2 Cl
Ca^_ H.O^Ca'^Cl H^O^Ca-^O-
^Cl HoO-

Ca CI2 Ca CI2.2H2O
'CI
H^O^
Ca Clo.4HpO
^Cl H,0 ^ o-
CI

CI
Ca CL.GH9O

Several relations are brought out by these formulas

In the first place, the calcium is taken to be in the same
state of oxidation (+ 2) in all the compounds. In the
second place, according to these formulas, the only sub-
stance which would ionize in solution is the last which
would form the ions [Ca.6H20]++ and 2C1. At present
there is no experimental evidence available to test this
question, and the reason for writing the formulas in this
way and indicating this fact is that with similar compounds,
such as the hydrates of chromic chloride and the am-
moniates of platinic chloride, the chlorine only appears in
the outer zone and forms ions when the final hexahydrate
or hexammine stage is reached. For this reason the di-
and tetrahydrates are formulated as non-ionogens.
It has been possible so far to assign definite structural
formulas tomany of the compounds which are made up of
two or more simpler molecules (compounds of the second
 ACIDS AND BASES. 59

and higher orders). The formulas assigned have been

based upon certain definite chemical and physical reactions
or relations. The compounds have a fairly considerable
range of stability so that the study of their reactions makes
it possible to treat of a portion of the molecule at a time,
leaving the remainder constant or unchanged. In develop-
ing the subject, it is now necessary to take up more complex
substances; that is to say, the compounds of the second,
third, etc., order, or the binary, ternary, etc., compounds.
These compounds of higher orders are made up of com-
pounds of the first order, and must be considered in the
same way as far as possible. A difficulty is encountered
in the practical treatment. That definite compounds are
formed may be proved conclusively in many of these
binary or ternary mixtures, but the linkings between the
atoms cannot be determined as definitely. The methods in

use for determining the graphic formulas cannot be applied

to these more complex substances, partly because of their
ready dissociation into their constituent molecules, partly
because of the internal rearrangements which take place
readily, and perhaps for other reasons. The difficulty of
assigning definite structural formulas to a number of these
substances must be faced squarely. An attempt to write
the formulas with insufficient evidence is of no value, but
on the other hand it is possible to use the classifications
involving these compounds of higher orders without assign-
ing graphic formulas to them. In a way this appears to

go no further than to designate these compounds as molecu-

lar compounds, but it will be shown in succeeding chapters
how different classes of reactions may be grouped together
so that even without the use of all the linkings between the
atoms, light will be thrown upon the mechanism of a
number of reactions. This is true especially when the
distribution of the charges on the atoms constituting the
molecules is taken into account.
 CHAPTER IV.

CATALYSIS.

The conceptions upon which the structures of molecules

are based have been elaborated in the preceding chapters.
The next step to be taken involves the changes which may
take place when twomore molecules interact. This
or
would include changes which take place in chemical re-
actions and an attempt will be made to outline a general
theory of chemical reactions from the standpoint of struc-
tural chemistry in this and the following chapters.
In considering such a general theory of chemical reactions,
it is desirable to proceed from simple to more complex
phenomena. In order to lead up to chemical reactions in
general, catalytic reactions will first be taken up as simple
examples. This apparently reverses the customary order
of treatment, but a short discussion of catalysis as it is

ordinarily presented and as it will be presented here will

serve to show the relations.

A catalytic action is generally defined as one in which the
is modified by the presence of a sub-
velocity of a reaction
stance which unchanged at the end of the reaction.
is itself

The substance which causes such an action is called the

catalytic agent or catalyst. The following general relations
have heretofore been assumed to apply to catalytic actions.
In the first place, the catalyst has the same chemical
composition at the beginning and at the end of the re-
action. A small amount of the catalyst is able to effect
the transformation of a large amount of the reacting sub-
stance. A catalyst can only modify the velocity of a
reaction, it is incapable of starting a reaction. A catalytic
agent does not affect the final state of equilibrium of a
reaction, or, in other words, the velocities of two opposing
60
 CATALYSTS'. ^1

Reactions are affected to the same extent hy ifie catalyst.

The state of equilibrium is independent of the nature and

quantity of the catalytic agent.
These general relations have been taken to hold for
I
catalytic actions as a result of the description of various
reactions. They are therefore, used as definitions of cata-
lytic reactions. If, by definition, a reaction follows these
laws, it is catalytic, otherwise it is not. While it is neces-
sary for purposes of classification, to have some definitions
of this kind, the way in which the classification of catalytic

reactions developed, that is, very often by the introduction

of the term catalyst when unknown factors were involved,
has confused the relation of these reactions to chemical
reactions in general.
In place of the relations pointed out, a catalytic action
will be taken to be based upon the definition of a catalyst
as a substance which may modify the velocity of a reaction
without itself undergoing a change in chemical composition.
No further limitations will be introduced, and it will be
shown how the conclusions from this point of view compare
with the conclusions derived from or based upon the descrip-
tion of catalytic reactions. used heretofore. The definition
given when used with the general equation of a chemical
reaction evidently simplifies it from the structural or com-
,
positional point of view, because the chemical composition
of one of the initialand final products of the reaction is the
same. The way which such a substance may modify
in
the velocity of a reaction must next be considered, and it is
this point which forms the crux of the general theory to be
used. The general theory consists of what has been called
the "addition theory" of chemical reactions.
In considering the mechanism of chemical reactions, this
theory states that primary addition is involved in chemical
reactions between molecules even when the final products
obtained indicate substitution or other change. It repre-
6^ 6HEMICAL HEACTIONS.

sents the most general case of chemical reactions. Evidence

for an explanation for a number of reactions on this basid
and the view that it was of general application was pre-
sented some years ago in a short paper (K. G. Falk and
J. M. Nelson, Jour. Amer. Chem. Soc. 37, 1732 (1915)).

Catalytic reactions will be taken up as a group of addition

reactions following the same laws as other chemical re-
actions, with one condition fixed, namely, that one of the
original substances which takes part in the reaction also
appears as one of the products of the reaction. The com-
plete change may be represented by an equation of the form,
A+ B+ '•'+D = E + F+ "•+D, ^
in which the substance typified by D acts as the catalyst.
A reaction such as this may be considered to proceed by an
addition compound being formed by the reacting com-
ponents with the catalyst, and this complex compo>und then
reacts further to reform the catalyst and one or more new
molecules. The proviso for a reaction to be considered
catalytic is that one of the substances going to make up the
addition product is formed again when the addition product
breaks down or reacts further. .This substance, the cata-
lyst, which has gone through a cycle of changes and has
returned to its original condition, is evidently able to go
through the cycle of changes again with fresh material.
The action of the catalytic substance, as outlined, may
result in an acceleration of the changes taking place in the
other substances present, a retardation, or finally show no
effect on the velocity of the reaction. If a retardation
would result when the catalyst takes part in the reaction,
then, since reactions would be taking place simultaneously
without and with the catalytic substance as part of the
intermediate addition compound, the net result observed
with regard to the velocity would be that in which the
catalytic substance was not involved unless the latter
 tJATALYSI^. 63

were present in more than a very small quantity. The

experimental evidence directly in favor of the view of the
production of addition compounds in a number of catalytic
reactions will be considered next and then some theoretical
developments will be given.
In the lead chamber process for the manufacture of
sulfuric acid, nitric oxide, oxygen (from the air), sulfur
dioxide, and water (steam), interact. The nitric oxide
acts as the catalyst, and is present at the end of the action,
with the sulfuric acid. It acts as "oxygen carrier." One
of the intermediate compounds which is formed contains
nitrogen peroxide (NO2), sulfur dioxide, and water. It
may be obtained in crystalline form, known as "chamber
crystals" which have the composition HSO3NO2, nitro-
sulfonic acid, under certain conditions. This substance is

decomposed in the presence of an excess of steam or water

vapor into sulfuric acid and nitric oxide, or better, nitrogen
trioxide, N2O3. While the exact formulation of the inter-
mediate compounds is not simple under the various condi-
tions, the evidence at hand is sufficient to make the' existence
of at least one intermediate compound certain.
The reaction between an alcohol and an acid to form an
ester, catalyzed by the addition of acid, takes place with
the formation of a complex intermediate compound con-
taining the catalyst as a constituent. The evidence for this
and a more complete discussion of this reaction will be
presented in Chapter 6. The existence of such intermediate
compounds is only referred to here, because they have been
shown definitely to exist in a number of cases.
In the formation of ether and water, or of ethylene and
water from alcohol and sulfuric acid, or the reverse reactions,
sulfuric acid plays the part of the catalyst, and the inter-
mediate addition compound may be represented by alky!
sulfuric acid, RSOJI, or a hydrate of it.

Similarly in the formation of ethylene and water from

64 CHEMICAL REACTIONS.

ethyl alcohol, zinc chloride acts as catalyst, and the inteiV

mediate compound is represented by the formula ZnC^.-
C2H5OH.
Condensation reactions with aluminium chloride as
catalyst also involve the formation of intermediate complex
compounds which have been isolated in some cases. These
will be taken up in detail in Chapter VII.

The catalytic reactions which have been quoted give

direct experimental evidence of the existence of intermediate
compounds of the reacting substances with the catalyst.
The list as given is not complete by any means, and a
study of the scientific and patent literature of the past few
years will show many more reactions of this kind. P.
Sabatier, in his book "La Catalyse en Chimie Organi-
que,'' 1913, assumed the formation of an intermediate
compound of catalyst with reacting substances in all

catalytic reactions. The fact that intermediate compounds

have been isolated shows that a capacity for combination,
or, in other words, an unsaturation, is present in the reacting

substances. may depend upon a Tiefinite

This unsaturation
atom upon a group of atoms combined
of each molecule, or
in such a way as to show unsaturation of two or more atoms
(as, for example, with two carbon atoms united by a double

linking or two units of valence), but in all cases, the impor-

tant feature at present is the property of unsaturation in
connection with the formation of the intermediate com-
pound.
The fact that intermediate complex compounds have
been isolated in a number of catalytic reactions, naturally
does not prove that they are formed (with the catalyst)
in all such cases. Some evidence will now be presented to
indicate that unsaturation of certain molecules plays an
important part in catalytic reactions which apparently do
not, at first sight, fall into the classification.
It has been known for some time that a given reaction
 CATALYSIS. 65

may proceed faster in one solvent than in another. As an

example, the reaction between triethylamine and ethyl
iodide in which tetraethylammonium iodide is formed, and
for which the ratein different solvents was studied by N.
Menschutkin, may be quoted. Menschutkin mixed one
volume of equimolecular amounts of the reacting substances
with fifteen volumes of the solvent, and heated the mixtures
in sealed glass tubes at 100° for definite periods of time.

Velocity of Combination of Triethylamine with Ethyl Iodide in Various

Solvents.

Velocity
Constants. Ratios.

Hydrocarbons.
Hexane CeHu 0.000180 1 0.13
Heptane C7H16 0.000235 1.3 0.17
Xylene C6H4(CH3)2 0.00287 15.9 2.2
Benzene CeHe 0.00584 38.2 4.4

Halogen compounds.
Propylchloride C3H7CI 0.00540 30 4.0
Phenylchloride CeHsCl 0.0231 128 17.4
Phenyl bromide CeHeBr 0.0270 150 20.3
a Bromnaphthalene CioHyBr 0.1129 627 84.9

Simple Ethers.
Ethyl isoamyl ether CaHsOCsHn 0.000630 3.5 0.47
Ethyl ether CaHsOCzHs 0.000757 4.2 0.57
Phenetol CzHsOCeHe 0.0212 117.7 16.0
Anisol CHsOCeHs 0.0403 223.9 30.3

Esters.
Isobutyl acetate C4H9.O.CO.CH3 0.00577 32.1 4.3
Ethyl acetate C2H5O.CO.CH3 0.0223 123.9 16.7
Ethyl benzoate CzHsO.CO.CeHs 0.0259 143.9 19.4

Alcohols.
Isobutyl alcohol C4H9.OH 0.0258 143.3 19.4
Ethyl alcohol C2H5.OH 0.0366 203.3 27.5
Allyl alcohol C3H5.OH 0.0433 240.5 32.5
Methyl alcohol CH3.OH 0.0516 286.6 38.0
Benzyl alcohol CeHs.CHa.OH 0.133 742.2 100.0

Ketones.
Acetone CH3.CO.CH3 0.0608 337.7 45.7
Acetone (14.5 vol.) + Water (0.5 vol.) 0.0889 493.9 66.9
Acetophenone CHj.CO.CbHs 0.1294 718.7 97.3
66

The determination
CHEMICAL REACTIONS.

amounts of tetraethylammonium'
of the
iodide formed, enabled him to calculate the velocity con-
1
stants for the reaction using the equation for a bimolecular
reaction. Some of these values (k) for the reaction in differ-
ent solvents are given in the accompanying table [Z. physik.
Chem. 6, 43 (1890)]. The ratios given in the last two
columns show the relative rates of reaction, first when coiis|
pared to the slowest reaction, whose velocity is placed equar^
to one, and second, on the basis of the most rapid reaction
which is placed equal to 100.
The results given in this table do not indicate clearly
that the velocity is directly connected with the unsaturation
as ordinarily considered. Roughly it is so, and if certain
solvents are omitted, this relation is very nearly true. For
the present, it may be stated that the unsaturation is

important in that it shows the capacity to form addition

products, but that in some of the solvents, polymerization
of the solvent molecules themselves occurs. The un-
saturation shows itself in two ways, as polymerization and
as formation of complex molecules with other substances,
and the action of the solvent is determined by these two
factors and their relative predominance.
It may be said for the present, therefore, that a rough
parallelism between the unsaturation of the solvent and
the magnitude of the velocity constants for this reaction
exists.

Unsaturation may therefore be used as the property

upon which the catalysis of these reactions depend. With-
out entering into the structural formulas of the addition
products at present, this property means that addition
compound formation of one or all of the reacting substances
with the catalyst precedes or accompanies the reactions.
D. Klein [Jour. Phys. Chem. 15, 1 (1911)] in studying the
relative rates of the reaction between hydrogen sulfide

and sulfur dioxide in a number of organic substances,

 CATALYSIS. 67

accounted for the results obtained by the assumption of

intermediate compounds involving the reacting compounds
and the solvents as catalysts. The evidence in other re-
actions is also strong enough to have caused a number of
workers to assume the existence of such intermediate
products, without actually having isolated them. Some of
these reactions are given by J. W. Mellor in his " Chemical
Statics and Dynamics."
The theoretical views of E. C. C. Baly, based upon the
absorption in the ultraviolet region of the spectrum of the
reacting substances, before, during, and after the reaction,
and outlined in Chapter II may be referred to in this
•connection.
A group of catalytic agents which is continually increasing
In importance is included under the general term of enzymes,
the catalysts produced by living organisms and which are
of the greatest significance in all life processes. Within
recent years there have been distinct advances made in the
elucidation of the chemical nature of some of the enzymes,
but there is no definite evidence at the present time that
any has been obtained in a pure state, that is, as a definite
chemical compound. Notwithstanding this lack of knowl-
edge, a study of the kinetics of a number of enzyme reactions
has led to the view that primary addition products are
formed between the enzyme molecule and the substrate
(substance acted upon) and that the addition products
then react further to reform the enzymes and the other
products of the reactions. One of the lines of evidence for

this view may be With a small amount

indicated briefly.
of enzyme material, increasing the amount of substrate will
at first, with small quantities of the latter, show a larger
amount of decomposition in a given time interval, up to a
certain amount of substrate. Increasing the concentra-
tion of substrate beyond this will result in the same amount
of action as with the smaller amounts, evidence that the
 .

68 CHEMICAL REACTIONS.

given quantity of enzyme can take care of only a certai

quantity of substrate, or that a compound of the two
formed. The possible question of adsorption will be take
up presently. Another way of stating the same observi
tion is that with small amounts of enzyme, the amount
substrate transformed in a given time interval is propo
tional to the length of the time interval. Among otherS;

this was found to be true for the action of invertase on can<

sugar by J. M. Nelson and W. C. Vosburgh (Jour. A:
Chem. Soc. 39, 790 (1917)), by J. Duclaux [Chemie Biolog-
ique, Paris, 1883; and Traite de Microbiologic, Tome II
Diastases, Toxines, et Venims, Paris, 1899], by A. Brow
(Trans. London Chem. Soc. 81, 373 (1902)] and by
Michaelis and M. L. Menten (Biochem.>Z. 49, 333 (1913));'
of amylase on starch by H. T. Brown and T. A. Glendinning
[Trans. London Chem. Soc, 81, 388 (1902)]; of the action
of lactase, maltase, and emulsin by E. F. Armstrong
[Proc. Roy. Soc. 73, 500 (1904)]; of lipase on glyceryl tri-
acetate by K. G. Falk and K. Sugiura [Jour. Amer. Chem.
Soc. 37, 227 (1915)] and of urease on urea by D. D. van
Slyke and G. E. Cullen [Jour. Biol. Chem. 19, 141 (1914)].
The well-known lock and key simile of Emil Fischer for
such reactions indicates also a belief in a chemical combina-
tion as the first step. H. D. Dakin [Jour, of Physiol. 30,
253 (1904) found evidence for the existence of intermediate
]

compounds in the action of optically active liver lipase

material on a racemic mixture of esters of mandelic acid,
the dextro-component reacting more rapidly than the laevo.
"The dextro- and Isevo-components of the inactive ester
first combine with the enzyme, but the latter is assumed
to be an optically active asymmetric substance, so that the
rates of combination of the enzyme with the d- and 1-esters

are different. The second stage in the reaction consists

complex molecule (enzyme
in the hydrolysis of the ester) +
Since the complex molecule (enzyme +
d-ester) would not
 CATALYSIS. 69

i
be the optical opposite of (enzyme + 1-ester), the rate of
change two cases would again be different. Judging
in the
by analogy with other reactions one might anticipate that
the complex molecule which is formed with the greater
velocity would be more rapidly decomposed. In the present
case, it would appear that the dextro-component of the
inactive mandelic ester combines more readily with the
enzyme than the Isevo-component does, and that the com,-
pjex molecules (d-ester + enzyme) are hydrolyzed more^
rapidly than the (1-ester + enzyme), so that if hydrolysis be
incomplete dextro-acid is found in solution and the residual
ester is Isevo-rotatory."
The views so far presented in this chapter may be sum-
marized as being based upon the primary formation of
addition compounds when two or more molecules react, these
addition compounds then breaking down to form new mole-
cules. In catalytic reactions, the first stage of the reaction
is the same, but in the second stage, one of the substances
formed in the breaking down of the intermediate compound
is identical in composition with one of the substances which
took part initially in the reaction in the formation of the
addition compound. While the experimental evidence is

favorable to this view of catalytic reactions in many cases,

it may be objected that physical influences may often
modify the velocity of the reaction between gases. At
present there is no experimental evidence of any kind
available to prove or disprove the formation of definite
chemical compounds in such cases, but on the other hand,
evidence is accumulating that adsorption (or perhaps the
solution of a gas or a liquid in a solid) is the important
factor here. Just how far phenomena of this nature may
be identical with the formation of definite chemical com-
pounds (possibly so-called "loose" combinations) on a
is not at present certain, but until direct evidence
surface
is obtained that such reactions must be included in a
70 CHEMICAL REACTIONS.

ScKfeme different from the one outlined hefe, the pi'esenf

i'esentl

classification may be used to include all these reactions,

although the composition, and even in many cases the
nature, of the intermediate compounds, is not known.
The reactions between two or more molecules take place
with the formation of intermediate compounds. For thH
sake of completeness, it will be necessary to refer to the
l^eactions in which one substance only is changing or re*
acting. This substance may be a simple molecule reacting,
or may be a molecule of a complex intermediate addition
compound, made up two or more simpler molecules.
of
The rate of such reactions appears to depend entirely upon
the nature of the substance, and while it is influenced by
the temperature, a certain fraction of the amount present
is transformed in each unit of time, the monomolecular

reaction velocity rate, or the logarithmic law, being fol-

lowed. A number of theories have been suggested to
account for the fact that only such a part reacts, and not
the whole amount, such as an attempt to distinguish be-
tween active and inactive molecules of a substance, of which
only the former react, while a constant ratio exists between
the concentrations of the two kinds. None of these theories
has been satisfactory, and for the present at least it is

advisable simply to state the fact without attempting to

explain it. «

Some theoretical relations with regard to catalytic re-

actions will now be taken up. A simple mechanical analogy
developed by Professor J. M. Nelson and Dr. J. H. North-

rop, may be of interest here in considering the energy or

affinity relationships, although it does not include the
view of addition compound formation.
•
A vessel of water. A, is filled to the level C. A syphon, D,
filled with water dips into this water, while its other,
lower, end reaches to the vessel B placed lower than A, so
that the level of the water in B (E) at the beginning is
 CATALYSIS. 71

higher than the bottom of vessel A. The water will flow

from vessel A into vessel B until the levels in the two are
the same. In this analogy, the substances initially are
represented by the water in A, p
the substances after the reac-
tion by the water in B, the
difference in the content of
free energy is shown by the dif-
ference in level in the two ves-
sels. The change of the substances from vessel or state
A to vessel or state B of lower free energy content takes
place through the syphon, and may occur in a number of
ways, depending upon the syphon. Change takes place
until equilibrium is reached, and the rate of change depends
upon the bore, etc., of the syphon, which includes therefore
the catalytic influences. The raising of the water in the
left arm of the syphon may work necessary
represent the
to overcome the chemical work being re-
resistance, this
gained in the other arm of the syphon. The catalytic
properties of the syphon remain, after the reaction, the
same as before, and the reaction would proceed, even if
the bore of the tube were infinitesimal, but at an infinitesi-
mal rate.
The general conditions which had been assumed to hold
for -catalytic reactions and which were used to determine
whether a substance acted as catalyst, were given earlier in

this chapter. They were evolved gradually as more and

more reactions of this nature were studied, and it is not
surprising therefore that this superstructure of conditions
became top-heavy and that some of the conditions assumed
to be essential in a catalytic reaction, at times were found
not to hold. The question whether the equilibrium point
of a reaction is changed by a catalyst is a case in point.

If a catalyst only changes the vel()(!ity of a reaction, and

exerts no other influence whatsoever, as assumed in the
72 CHEMICAL REACTIONS.

customary statement of catalytic changes, then the catal^l

cannot change the equiHbrium of the reaction; otherwise
perpetual motion would be possible.
From time to time statements have appeared in the
literature taking exception to the view that a catalyst does
not change the equilibrium, without, however, going to the
root of the question and attempting a classification and
description of catalytic actions which would eliminate such
contradictions. Thus, G. Bredig (Ergebnisse der Physio-
logic I, 139 (1902)) showed that a change in the vapor
pressure of a catalyst necessitates a difference in the work
required to remove the catalyst from the reaction mixture.
Only as long as this work is the same under the same condi-
tions before and after the reaction, does the equilibrium
remain unchanged. If the catalyst is present in large
excess it acts as solvent. A change in the nature of the
solvent changes the equilibrium, and only in dilute solution
will the equilibrium remain the same. E. Abel [Z. Elektro-
chem. 13, 555 (1907)] stated, assuming the formation of
intermediate products with the catalyst, that if the catalyst
is end of the
in a different chemical or physical state at the
reaction from what
was at the beginning, that it has
it

given up or received energy, and that a change in the

equilibrium was quite conceivable. W. J. Jones and A.
Lapworth [Trans. London Chem. Soc. 99, 917 (1911) found
experimental evidence for the change in the equilibrium
between ethyl alcohol, acetic acid, ethyl acetate,and water,
by the addition of the catalyst hydrogen chloride. M. A.
Rosanoff (Jour. Amer. Chem. Soc. 35, 173 (1913)) also
speaks of the possibility of a catalyst influencing the equi-
librium, and that it does not do so only when the molecular
state of the reagents is not affected by the catalyst. A
number of other chemists may be quoted in the same sense.
Recently, W. D. Bancroft (Jour. Physical Chemistry 21,
573 (1917)) reviewed certain phases of catalytic reactions
 :

CATALYSIS. 73

If a catalytic reaction is defined as a reaction in which

one of the products is identic^ in chemical composition
with one of the original substances involved in the reaction,
the view which is used here, then it may be possible to
arrive at definite general conclusions. No further limita-
tions are introduced in the definition. In the general
formulation of a chemical reaction

Viai + F2«2 + • • •
niAi + n2A2 + • •
•

= F/a/ + V2'a2' + • • •
nMi' + Th'A^' + • • •

in which aia2, • • •
aiS a2^, represent the molecular species
• • •

in the solid state taking part in the reaction, Ai, A2, A^', • • •

A2, '
' •
the molecular species either as gas or in solution,
and Vi, V2, Vi, V2,
• • •
ni, n^, • • • • • •
Ui, rh',-" the corre-
sponding molecular species formed in the reaction, then the
definition of catalytic action advanced requires only that
one of the molecular species a\, a^y ^1', A2 is • • •
j
• • •

identical in composition with ai, ce2, • • •

^1, A2, • • •. The
definition does not, a priori, state anything concerning the
velocity of the reaction. Since one of the substances ap-
pears as a product of the reaction, obviously it may go
through the cycle of the reaction again with fresh initial
material. This substance is the catalyst, and therefore
a small amount of this substance may react with a large
amount of the other substances. This phenomenon has
always been taken to be one of the most characteristic
properties of a catalyst. With regard to the possibility of
the reaction taking place in the absence of the catalytic
substance, everyone of the substances at the beginning
if

and at the end of the reaction is present in the pure state,

then the equilibrium constant derived from the hiw of mass
action would be independent of the catalytic substances, the
equilibrium would be the same whether the catalyst were
present or not, and reaction would proceed in the presence
74 CHEMICAL REACTIONS.

or absence of catalyst, although the rates in the different

4
cases may well be different. Furthermore, it is impossible
to state the effect of the catalyst; it might increase the rate
of the reaction, it might decrease it, or it is possible that
no effect at all would be noticeable upon the rate of the
reaction. The so-called "negative catalysis" (cf. Mellor.
I.e.) is then simply a special case of catalysis in general, the
catalyst here retarding the reaction instead of accelerating
it.

In practical work, the substances taking part in a reaction

are hardly ever isolated in a pure state, so that a develop-
ment of the ideal case just presented will be necessary.
If, in the general formulation of a chemical reaction given
above, the concentrations of the substances Ai, A2, Ai, • • •

A2 , • • • in the free state before and after the reaction are

denoted by (7i, C2, • • •
(7/, C2 ,
•and their concentrations
• •

at equilibrium by c/, c^' , • • • , then it may readily be shown

that the change in the free energy {A) of the reaction is

given by the equation.

A = RT log. ^k^, RT log. ^,^

f
(This equation is developed with the aid of the conception
of the equilibrium box (van't Hoff) into which the reacting
substances in dilute solution or the gaseous state are intro-
duced through suitable semi-permeable membranes, in

which the reaction proceeds, and from which the products

are removed through suitable semi-permeable membranes,
all isothermally and reversibly, the work done in the
different steps being calculated by the aid of the gas laws.)
The fraction of the second term of the right side of the
equation is the equilibrium constant K. If the states of
the substances are such that each exists independently
before and after the reaction, then, even if Ci"^ = Ci"^^

as necessary for a catalytic change, the work done will be

 CATALYSIS. 75

the same whether the catalyst is present or absent, and the

equiHbrium will be unchanged. If, however, work is done

in introducing or removing the catalyst, some sort of chem-

ical compound is formed between two or more of the molecu-
lar species, whether this be termed chemical combination,
solution, adsorption, physical change, etc., and then the
terms involving the concentrations will not be the same as
before. Thus the concentration term Ci"^ may denote a
complex containing the catalyst, while in the denominator
the catalyst may be represented in a different complex.
It may be said, therefore, that in the chemical changes as
ordinarily observed, if a catalyst is involved in the reac-
tion, that, as long as the substances are not present in the
pure state or possessing the same properties before and
after the reaction, there may well be a difference in the
change in free energy of the reaction in the absence and
presence of the catalyst and that the equilibrium will be
changed correspondingly. That such changes have not
been observed more frequently than has actually been the
case is doubtless due to the small changes in the equilibria
which have resulted by the addition of the catalyst. It
must remembered that the law of mass action as de-
also be
veloped in the thermodynamic treatment as indicated,
holds only for dilute solutions and for gases at compara-
tively low pressures. For concentrated solutions and gases
at high pressures, the theoretical considerations cannot as
yet be applied satisfactorily.
 CHAPTER V.

CHEMICAL REACTIONS; GENERAL CONSIDERATIONS.

In the preceding chapter chemical reactions were dis-

cussed with one condition fixed, namely, one substance

involved in the reaction having the same chemical composi-
tion in the beginningand at the conclusion of the reaction.
Such a reaction was treated as a catalytic reaction in which
the substance unchanged in composition as a result of the
reaction acts as the catalyst and causes a change in the
velocity of the reaction. The explanation of such a change
in velocity is to be found in the addition theory of chemical
reactions according to which a reaction between two or
more molecules takes place by the formation of a more
complex intermediate compound which then breaks down
again to form different molecules. The presence of the
catalytic substance may accelerate the formation (or the
decomposition) of the complex intermediate compound and
in this way increase the velocity of the reaction, being
itself reformed as one of the products of the decomposition
of the intermediate compound. This theory of addition
compound formation will now be applied to chemical reac-
tions in general.
The formation of ammonium chloride was discussed to
some extent in the preceding pages. The reaction is a
common one, relatively simple, and as will be seen, repre-
sentative of a large group of chemical transformations.
Omitting the influence of catalytic agents, this reaction
may be considered to consist in the formation of the addition
compound ammonium chloride from ammonia and hydrogen
chloride. The simplest and most common way of express-
76
 :

GENERAL CONSIDERATIONS. 77

ing this reaction in the form of a chemical equation is the

following
NH3 + HCl = NH4CI (1)

The reaction indicated by this equation does not take

place under ordinary conditions with appreciable velocity.
When ammonium chloride is obtained from ammonia and
hydrogen chloride, water or moisture is present as a rule,
and under these conditions, the reaction takes place rapidly.
The equation as written does not, therefore, represent the
reaction which is ordinarily observed. It is incomplete
in that the possible action of the catalyst, water, is omitted.
The action of the catalyst is of the highest importance here
and any complete explanation of the reaction must neces-
sarily include it.

it was pointed out that the action

In the last chapter,
of the catalyst due to the formation of addition com-
is

pounds between the catalyst and the reacting components

and that these addition compounds may then dissociate
or undergo rearrangement, yielding the final reaction
product and the catalyst.
In the particular reaction under discussion, the formation
of ammonium chloride, water is known to form addition
compounds with both the reacting components and with
the final products. Before going into the details of this
reaction, the reaction between ammonia, hydrogen chloride,
and platinic chloride will be taken up, as it is analogous in
certain respects, and will throw some light on the nature
of the intermediate products or addition compounds.
The behavior of ammonia and hydrogen chloride toward
platinic chloride is similar to their behavior toward water;
that is, addition compounds are formed in both groups.
Because of the different characters of the water and the
platinic chloride, it is to be expected that the dissociation
or decomposition of these addition compounds (in other
 :

78

words, their
CHEMICAL REACTIONS.

measured by certain equilibrium

stabilities, as

constants) would not take place to the same extent. Bear-

d
ing this difference in mind, the formulations may now bea
indicated.
The definite compound ammonium chlor-platinate
(NH4)2PtCl6, is made up of, and may be prepared from, i
ammonia, hydrogen chloride, and platinic chloride. It may
dissociate in a number of different ways, the most importan
of which are indicated by the following equilibria

NH4 Zci
= 2NH4CI + PtCU (a)

>Pt^Cl = 2NH3 + HaPtCle (6)

NH4 \\C1 = 2HC1 + (NH3)2PtCl4 (c)
\ci
CI
= 2NH3 + 2HC1 + PtCl4 (d)

The possible intermediary compounds such as (NH4)PtCl6

in equilibrium (a), (NH3)2HPtCl5 in equilibrium (c), etc.,

are not given, as they add nothing to the principles which

these equilibria are intended to illustrate. Equilibrium (d)

represents the reaction between the three components and

the "ternary" intermediate addition compound. The
products formed according to the equilibria represented by
equations (a), (6), and (c), may all be present, or only

some of them may be formed. The extent to which the

different products are found depends upon the equilibria
of the various reactions under the conditions of temperature
and pressure (or concentration) under which the reaction is
being studied. The equilibria may, of course, be deter-
mined experimentally, and the values of the equilibrium
constants give a measure of the relative chemical affinities
of the reactions. If the conditions are such that, besides
equilibrium (d), only or predominatingly the products
shown by equilibrium (a) are present, then the platinic
chloride plays the part of a catalyst in the formation of
ammonium chloride from ammonia and hydrogen chloride.
Again, if, besides equilibrium (d), mainly the products
 GENERAL CONSIDERATIONS. 79

given by equilibrium (b) are formed, then the platinic

chloride is not the catalyst, but on the other hand, ammonia
would be acting as the catalyst in the formation of hydrogen
chlorplatinate from platinic chloride and hydrogen chloride.
Similarly, if equilibrium (c) were the predominating re-

action,hydrogen chloride would act as the catalyst in the

formation of diammono platinic chloride from ammonia
and platinic chloride. The concentrations of the reacting
substances, according to the law of mass action, would
control to a great extent in any given case, the nature of
the products obtained. If the reaction is not allowed to
go to completion, then the relative reaction velocities of
the various reactions would determine the composition of
the mixture at any instant.
This reaction is particularly instructive, since the com-
position of the intermediate addition compound is perfectly
definite. With equilibria (a) and (d) it is seen that the
platinic chloride acts as the catalyst for the reaction (either
formation or decomposition, depending upon the concentra-
tions of the reacting substances) between ammonia, hydro-
gen chloride, and ammonium chloride.
The influence of water on the reaction between ammonia
and hydrogen chloride to form ammonium chloride may
be taken up in the same way. Although very little is
known of the way the water actually catalyzes the formation
of ammonium chloride, the reaction considered in Chapter
IV in the formation of tetraethylammonium iodide from
triethyl amine and ethyl iodide in the presence of different
solvents indicated the method of action of the catalyst.
It was found that unsaturation of the solvent paralleled
to a certain extent the increase in the velocity of the
reaction. Ability to form addition compounds, inter-
mediate or otherwise, seemed to be the controlling factor.
Unfortunately, the composition of the intermediate addition
compound is not so definite in the present case. In order
80 CHEMICAL REACTIONS.
I
to show the reaction in as simple a form as possible, at the
same time coinciding with the facts as far as known, it will
be assumed that the "ternary" addition compound contains
one molecule of hydrogen chloride, one molecule of am-
monia, and one molecule of water. The formulation of the
different equilibria, similar to equations (2), will then be
as follows:
= (H2O.HCI) + NH3 (a)
HCl
= (H2O.NH3) + HCl (b) (3)
H2O = H2O + (NH3.HCI) (c)
NH3
= H2O + NHa + HCl (d)

Starting with water, ammonia, and hydrogen chloride,

[equilibrium (d)], it is found experimentally that ordinarily
the products indicated by equilibrium (c) are obtained, or
vice versa. Water acts as a catalyst for the reaction between
ammonia, hydrogen chloride, and ammonium chloride, just
as platinic chloride did in the preceding reactions. A
difference between the two sets of reactions, (2) and (3),

may lie in the fact that in the former, (2), the value of
the equilibrium constants may be such as to show the
intermediate "ternary" compound, ammonium chlor-
platinate, to be more stable than the intermediate "ternary"
compound in the latter, (3). Under different physical
conditions, such as increase in temperature, etc., it is

possible that the reaction in equations (3) would proceed

in such a way as to favor the formation of the products of
The changing of the values of the equilibrium
(a) or of (b).

constants when the conditions are varied may well cause

the reaction to assume a different course. All the possi-
bilities, with one molecule of each reactant, are given in the
equations, however, and the deductions are similar to those
from equations (2). The concentrations of the reacting
substances here also play a predominating role in deter-
mining which products will be found in a reaction mixture.
 GENERAL CONSIDERATIONS. 81

The actual composition of the ternary compound is not

known definitely, and has, therefore, been given in the
simplest form, but even if different numbers of the reacting
molecules were contained in it, the same principles and
relations may be applied although the equations would be
much more complicated. The relative velocities of the
compound would determine
dissociation of the intermediate
which products are observed at any time, if the complete
reaction has not been allowed to come to equilibrium.
It is perhaps more usual to speak of the velocities of the
various reactions than of the values of their equilibrium
constants.
To return to the formation of ammonium chloride in the
neutralization of ammonium hydroxide by hydrochloric
acid, the equation for the change may be written as follows
in which the presence of the solvent, water, is indicated:

HCI.H2O + NH3.H2O = NH3.HCI + 2H2O.

It is evident that this reaction would amount to a change

consisting in the replacement of water in the hydrate of
hydrogen chloride by ammonia, or a replacement of water in
ammonium hydroxide by hydrogen chloride. This reaction
may be elaborated further. When an amine, such as
ammonia, is dissolved in water, it combines, in part at any
rate, with the water to form the addition compound written

in its simplest form as H3N.OIT2 (or graphically H3NXOH2

an onium addition compound) . This compound may tauto-
merize to ammonium hydroxide, NH4OH, the base from
the ionic point of view, which may be written
+
-4 H
-[0^5]
H H
in two zones to indicate the ionization, and wliich sIkiws all
 :

82 CHEMICAL REACTIONS.

that is known structurally of the compound, except the^

formation of hydrates (which were indicated in a preceding
chapter). When an acid, such as hydrochloric acid in

water, reacts with this compound, in place of assuming a

direct combination between hydrogen and hydroxyl ions
as in the ionic theory, following the general schemes out-
an addition compound is considered to be formed first.
lined,
The complete reactions may be indicated in the most general
way as follows:

(1)
NH3+H.0=[NH^]. (2) Ha+H.O = [HC;],
NH3
(3)
[S]+[SS]=[f«J=[S§]+-.o- »|
In equations (1) and (2) one molecule of water is assumed
to take part. The exact number is unknown and is im-
material for the principle. The "binary" compounds are
written as double molecules. Tautomerism of these into
the ionizable forms may take place and probably does
so and reaction (3) to form the "ternary" compound follows
the combination of the two "binary" compounds. This,
then,may dissociate according to equation (4) to form
ammonium chloride (or more probably a hydrate) and
water. It must be recalled that these equations are all
in fact really equilibria, and that the reverse reactions may
also take place. Thus, if carbon dioxide, CO2, were used in

place of hydrogen chloride, very little of the products

indicated in the equation corresponding to (4) would be
present. This method of treating the subject includes also
the generalizations derived from the ionic theory, such as,
for example, the heats of neutralization of highly ionized
acids and bases, which are practically identical in dilute
solution. This is brought out by the following set of
equations
 GENERAL CONSIDERATIONS. 83

(1) K0H + H20 = S"]^[g.or+ioHr,

HCl
(2) HC1 + H20 =
H2O
KOH
[KOH] rHCll
(3)
,

HCl +^^
LH2O J"^LH20j "[3H20j"L3H20j
2H2O
In dilute aqueous solution, in reactions (1) and (2) a greater
number of molecules of water undoubtedly is involved
than is indicated. The "ternary" addition compound of
equation (3) is made up as indicated but may rearrange and
then ionize. Comparing the final product of (3) with the
substances present in great excess in (1) and (2), as shown
by the determinations of the degrees of ionization, it is

evident that the net change, since excess of water is present*

is the combination of hydrated H"^ ion and OH ion, as

postulated by the ionic theory. The mechanism of the

change shows the part played by the solvent and brings
the reaction into line with the general addition reactions of
chemical changes.
To come back to the main subject, it becomes evident
that many of the neutralizing, hydrolyzing, and double
decomposition reactions are in fact nothing more than
replacement reactions whose course is governed by the

factors indicated, as well as by the atomic valences and co-

ordination numbers of the constituents with respect to the
particular substances which make up the intermediate ad-
ditioncompound.
Werner (I.e. pp. 232-7) has combined all these reactions
into a general one, which may perhaps be indicated as
follows:

XJA5MX] + H2O = Xn[AMlW]X = Xn[A6M0II] + HX.

(1) (2) (3) (4) (5)

One molecule of water may react with compound (1) to

84 CHEMICAL REACTIONS.

form compound (3). This primary compound may thenfl

dissociate to yield compounds (4) and (5). As a concrete
example chromium chloride may be taken as the primary
compound. Here M
is Cr, X is CI, and n is 2. The
equation becomes:

Cl2[(H20)5CrCl] + H2O = Cl2[(H20)5Cr(H20)]Cl

(1) (2) (3)

= Cl2[(H20)5CrOH] + HCl.
(4) (5)

Compounds (1) and (2) combine to form (3); this is hydra-

tion. Compounds (1) and (2) undergoing double decom-
position form (4) and (5); this is hydrolysis. The forma-
tion of (1) and (2) from (4) and (5) is neutralization. The
formation of (1) and (2) or of (4) and (5) from (3) is dissocia-
tion.
In the same way that the formation of ammonium
chloride from ammonium hydroxide and hydrochloric acid
could be considered to be a displacement of water by
hydrogen chloride, so it is possible to consider the above
set of reactions in the case of the chromium chloride to be
a set of displacement reactions. Compound (3) may be
regarded as an addition compound containing both hydro-

gen chloride and water, since the part p pi is equivalent

[TTci n
r OH * Compound (3) therefore can dissociate in

either direction, giving as one of the products hydrogen

chloride or water. The reaction in which compounds (1)
and (2) form (4) and (5) (hydrolysis), is therefore a dis-
placement of hydrogen chloride by water. Likewise, the
reaction in which compounds (4) and (5) form (1) and (2)
(neutralization), is a displacement of water by hydrogen
chloride.
The reactions considered so far belong to the general
 GENERAL CONSIDERATIONS. 85

group which may be classed together and explained most

satisfactorily as addition reactions, in which intermediate
addition compounds are formed which are in equilibrium
with various sets of products. If the initial and final

products only are considered, then the reactions very often

appear to be simple replacement reactions. In none of
these reactions has the charge or state of oxidation of any
of the atoms changed; that is to say, no oxidation or reduc-
tion has taken place. The treatment of the large and im-
portant group of reactions involving oxidation and reduc-
tion of different atoms in the molecules which take part in
chemical reactions will be taken up in the chapters following
these on addition and replacement reactions.
The dissociation of an intermediate addition compound
into several sets of products may appear at times to be a
simple reaction which leads to a few products. To indicate
the manifold possibilities and complexities which might
arise from the dissociation of a ternary compound, the
following scheme may be given:

(Am'Bn')b-{-\ {Am' Bn')u-b j<\

FiAt, Bn).-al^ III

^ 4" pJ'A^-

-1
-{At. B-.).
{A'„:'B',?)y
_{A'n»B'^'')z\ ^ {A'r:,B'n>\ +
{A'.i.> B'n>)y^\ etc.

% VI
[{A'm Bn), n
{A'^i>B',:r,), + \{A':.,B'n')y
{A',:.,B'n')y etc.
-hB7>
{A'^i'B\[r,),^A
VII

111 scheme, starting with x molecules of A^Ji~, y

this
molecules A[^>B'jy and z molecules A['/>B'^>T, the ternary
iddition compound I is formed. The molecules A^B~
86 CHEMICAL REACTIONS.

are assumed not to exchange positive or negative con-

1
stituents, but to dissociate as the integral molecules which
make up the ternary compound. Under these simplified
conditions, it is seen how the dissociation may take place,
and the number of possible equilibria involved in a reaction
of this type. If the various positive or negative constitu-
ents may in addition replace or displace each other, the
number of equilibria is correspondingly increased. This
scheme shows why the number of products in many organic
reactions is so large. In inorganic reactions, in which the
number of reacting components is smaller as a rule, the
possibilities as to the number of products formed are smaller,
but itmust be emphasized again that the general principles
of the mechanism of chemical reactions apply throughout,
whether these be grouped for convenience of treatment or
for any other reason as inorganic and organic reactions.
Since the ionic theory has been so successful in correlating
a number of previously separated phenomena, including
the possible explanation of certain chemical reactions,
especially those taking place in aqueous solution, it is of
importance to try to find to what degree the explanations
based upon it are accepted at present, and how the objec-
tions may be met most satisfactorily by the newer develop-
ments. In this book the facts of the ionic theory are
accepted, but some of the shortcomings of the theory, such
as the part played by the solvent, have already been
pointed out. It was shown how the mechanism of a
number of chemical reactions might well be explained more
satisfactorily on the basis of the addition theory. The
statement made by a few zealous supporters of the ionic
theory that only ions take part in chemical reactions may
be dismissed without much consideration. This has never
been the view of the greater number of workers who have
always recognized the occurrence of reactions especially
with organic compounds in which no ionization (as the
 X
GENERAL CONSIDERATIONS. 87

ionic theory understands ionization) was present. This

fact, however, at once separates reactions into two groups,
ionic and non-ionic. Just as with the suggestion of two
kinds of valence, polar and non-polar, as shown in an earlier
chapter, this divides chemistry into two branches, with
separate sets of explanations for each. The addition theory
includes all and formulations, and offers one set
reactions
of explanations for the two sets, at the same time including
the relations developed by the ionic theory as part of the
general development. Reference may be made to a paper
by J. W. Walker (Trans. Chem. Soc. 85, 1082 (1904)) in
this connection. To indicate the application of the addi-
tion theory to inorganic reactions, a typical example of a
reaction, explained heretofore on the basis of the ionic
theory, will be described.
The reactions between some metallic salts, ammonium
salts,and ammonia will be taken up briefly. Many of the
bivalent metals such as nickel, magnesium, etc., form
hydroxides insoluble in water but soluble in solutions of
ammonium salts. The generally accepted explanation for
the solubility in solutions of ammonium salts or for the
non-precipitation by ammonia, if ammonium salts are
present, is that the ammonium ion of the ammonium salts
drives back or represses the electrolytic dissociation of the
ammonium hydroxide so that the hydroxide ion is not
present in sufficient concentration to exceed with the metal
ion the solubility product of the metal hydroxide. The
new explanation depends upon hydrolytic reactions and
equilibria as outlined.
A bivalent metal halide, MX2, will be chosen as
H,
^^O X
In water the compound M\^ be
^O —
an example. will

Ha
present and negative X combined with O carrying a pre-
7
88 CHEMICAL REACTIONS.

domin'atingly negative charge will ionize into [M(OH2)2^

and 2X. It is probable that a substance of this sortj
will take up more (generally four) molecules of water
in onium combination with the metal element. These
additional molecules of water are not directly involvec
in the theoretical views to be developed and will therefore^

be omitted. The substance M (0112)2X2 may undergo]

hydrolytic dissociation as shown in equilibrium (6) of thej
reaction.

^^O—X = [mCOH^),]" + 2X (a)

"^O— X = M(0H}2 + 2HX (b)

The reaction which will be observed depends upon th(

equilibria (affinity relationships) of (a) and (b) in the given

equations, and upon the addition or removal of any of the
products. For instance, equilibrium (6) will proceed to
the right if a base is added. The addition of the base
removes HX and causes more M
(0112)2X2 to undergo
hydrolysis until ultimately only M(0H)2 will be present.
This reaction will take place especially if M(0H)2 is in-
soluble, but it is important to note from these equations
that it is due to the removal of HX by the base rather than
direct metathesis. The simplest way of looking at the
change, if only the initial and final substances and their
formulas are used, is MX2 + 2M'0H = M(0H)2 + 2M'X;
but this, for one thing, leaves out of account the action of the
solvent. Written in the ionic form M + 26R = M(0H)2,
while apparently going back to more fundamental relation-
ships, does not show what direct part, if any, the solvent
plays. By means of the equilibrium reactions as formu-
lated, the part the solvent plays is made evident. Further-
more, the reaction is brought into line with a great number
of others included among hydrolytic reactions.
 :

GENERAL CONSIDERATIONS. 89

Ammonia is analogous to water in its reactions. As

stated before, onium compounds are formed to a greater or
more readily observable extent with it than with water. If
ammonia is added to a solution of MX2, it is evident that
a compound (H3N:;!:)4M(->NH3->)2X2, or (omitting the
four ammonias in onium combination with M), M(NH3)2X2,
may be formed. The relative amounts of (0112)2X2 and M
of M(NH3)2X2 which will be formed, or the distribution of
MX2 between water and ammonia, depend upon the
will
relative stabilities of these compounds under the given
conditions. The substance M(NH3)2X2 undergoes electro-
lytic dissociation as follows (omitting possible intermediate
ions)
H3
M<^ I X = [M(NH3)J+++2X.
H3

Ammonolytic dissociation to form M(NH2)2 and HX,

analogous to the hydrolysis of the hydrated salt, does not
seem to occur with these compounds under these condi-
tions. (Possibly the mercury ammonia compounds dis-
sociate in this way ui;der suitable conditions.) The addi-
tion of a base has, therefore, no direct action on a substance
of this formula in the way of influencing the equilibrium.
Beyond the possibility of a direct metathetical reaction, the
base plays no part, as it does in the hydrated salt, even if

the hydroxide is not soluble. To sum up, the possible

reaction between a base and a substance MX2 in water in
the presence of ammonium salts or ammonia, will depend

upon the relative amounts of hydrated and ammoniated salt

present; if an appreciable amount of the former is present,
M(0II)2 may be precipitated; if the salt is entirely present
as the latter, no M (011)2 will be precipitated.
In the past years, F. Ephraim published some very
careful studies on the stability of the metal ammoniates.
lie determined the temperatures at which the hexa-
90 CHEMICAL REACTIONS.

ammonia (and substituted ammonia) derivatives of a

number of salts of the bivalent metals (including Be, Ni, Co,
Fe, Cu, Mn, Zn, Cd, Mg) showed definite vapor pressures.
The resuHs give a measure of the relative stabilities of
these compounds, and consequently also for solutions of
them. This gives no direct evidence as to the distribution
of any given salt between water and ammonia with both
present in solution, but does give a relative measure of the
amounts of the ammoniates formed by a number of different
salts. For instance, the salt NiCl2.6NH3 shows a vapor
pressure of 500 mm. at 130°, while the salt MgCls-GNHs
shows the same vapor pressure at 24.5°. This means that
a very much smaller concentration of ammonia would be
needed in solution to form the hexa-ammoniate with a
nickel salt than would be necessary for a magnesium salt.
Consequently, as a result of the distribution of the salt
between the ammonia and the water, the concentration of
ammonium salt needed to prevent the precipitation of the
metal hydroxide if a base is added would be much less for

the nickel salt than for the magnesium. The salts studied
by Ephraim may be arranged in a series showing the relative
amounts of ammonium salts needed to prevent precipitation
if a base is added.
The views Werner that compounds of the first order
of
are not electrolytes butmust go over into compounds of
higher orders before becoming electrolytes bear upon this
question. They have already been given and need only
be mentioned here.
Reference may also be made
two experimental investi-
to
gations bearing on this Isbekow [Z. anorg.
question:
Chem. 84, 24 (1914)] found that by dissolving the sub-
stances mercuric bromide, antimony bromide, bismuth
bromide, carbon tetrabromide, etc., in molten aluminium
bromide as solvent, solutions were obtained which gave
abnormally high molecular weights for the solute and which
 :

GENERAL CONSIDERATIONS. 91

conducted the Isbekow attributed this

electric current.
high molecular weight to association of the solute or to a
combination of the solute with solvent, and thought that
these complex substances were responsible for the ioniza-
tion and conduction of the current. Isbekow's discussion
of his results is of interest and may be given
as follows
" The associated condition of the electrolytes dissolved in

AlBrs is not a general characteristic of molten salts and their

mixtures. Although Lorenz [Z. phys. Chem. 70, 230
(1910)] has shown that a marked association occurs in the
case of molten salts, still as has been pointed out by the
investigations of Sackur [Z. phys. Chem. 78, 550 (1912)],
the substances dissolved in molten salts, in many cases,
break down into simple ions, and in dilute solutions of
salts of the type MX2 as solvent, the dissociation com- is

plete. A relationship of this kind was by

also observed
Tolloczko [Z. phys. Chem. 30, 705 (1899)] and by Klemen-
siewicz [Bull, de I'academie des Sc. de Cracowie (1908) p.
485)], in solutions of the alkali salts in SbCls. On the
other hand, electrolytes dissolved in molten HgCl2 show
association as in AlBra. The individual influence of each
solvent is also evident in the case of molten salts, one
solvent possessing the ability to ionize principally simple
molecules another principally complex molecules. There-
fore, each electrolyte solution is undoubtedly the result
of a particular interaction between the two components,
since the same substance, in one solvent conducts and in the
other does not. This interaction manifests itself in many
cases in the participation of the solvent in the formation of
the complex molecule or complex ion. It is not improbable,
that in the above thermal experiments, such a participation
of the solvent occurs." If Isbekow's interpretation is

correct; the solvent and solute interact to form the electro-

lyte, similar to the formation of the ionogen ammonium
chlorplatinate, (NIl4)2rtCl6, from platinic chloride and
92 CHEMICAL REACTIONS.

ammonium chloride. The constitution of these ionogens

would be of the form (AlBr3)n(MX)^.
It was shown by Plotnikoff (J. Russ. Phys. Chem. Soc.

(3) 466 (1902)) and later confirmed and studied more

thoroughly by H. E. Patten (J. Physical Chem. 8, 564
(1904)), that aluminium bromide dissolved in ethyl bromide
gives a solution which has a relatively low electrical re-
sistance, and from which aluminium may be deposited
electrolytically just as in the case of a solution of an
aluminium salt m water. Another interesting fact about
I
these results is that ethyl bromide has a very low dielectric
constant (8.9) and still serves as an ionizing medium for
the aluminium bromide. This solution is analogous to the
solutions described by Isbekow.
It must be borne in mind, however, in interpreting these
last results, that the separation of a metal or other sub-
stance at an electrode bears no relation necessarily to the
nature of the ions which may be present in solution. For
example, copper may be deposited on the cathode from a
solution of potassium copper cyanide, in which all except
perhaps a minute part of the copper is contained in the
anion.
Other evidence with regard to the combination of solvent
and solute might be quoted, but the general trend of the
views is apparent. As for the reasons for a substance
being able to dissolve another substance and of inducing
ionization, a number of suggestions have been put forward,
especially for the latter phenomenon. Thus, W. Nernst
and J. J. Thomson have considered it to be due to the
dielectric constant of the solvent, J. Briihl to the (chem-
ically) unsaturated nature of the solvent, etc. While all

of these views possess a certain amount of truth for various

solvents, there is at present no general explanation which
covers all the facts. Possibly the development of the views
put forward here involving addition compounds, tautomeric
 GENERAL CONSIDERATIONS. 93

rearrangements, and equilibria with different sets of

products may permit of a more general theory, but at
present, the quantitative data with regard to these addition
products are too meagre to permit of more than a suggestion
of this as a general explanation.
 CHAPTER VI.

SOME CHEMICAL REACTIONS.

The principles developed in the preceding chapters will
now be applied to chemical reactions, the substances re-
acting, and the probable mechanism or course of the
reactions, involving at the same time a classification of these
changes. The difficulty which arises in these applications
is 4ue to the wealth of material available, especially in the

changes included in organic chemistry. There is a strong

temptation to include all reactions which have been de-
scribed and if this were done this book would resolve itself

into a compendium of reactions, interesting perhaps in

itself, but lacking a point of view by which it was intended
to systematize such reactions as far as possible. The
applications in this and the following chapter in the first
place will include only reactions in which none of the atoms
in any of the reacting molecules shall have changed its
valence or become oxidized or reduced. Reactions in-
volving such changes will be taken up in later chapters.
In this and the following chapter a number of reactions
will be discussed from the point of view of the mechanism
or course of the reactions. Since so much material is

available in the field of organic chemistry, practically all

these reactions involve changes in organic compounds, and

be shown how a number of reactions which heretofore
it will

have been considered to be different may be included in

one general point of view. In the succeeding chapter, the
changes which one group of substances, the olefins, undergo
will be discussed and compared with the changes taking
place in various organic and inorganic reactions. In this
way, by considering first the changes involved in a series
 SOME CHEMICAL REACTIONS. 95

of reactions,and then the changes undergone by a group

of substances it is hoped to bring out the general principles
involved in the mechanism of chemical reactions, without
unduly elaborating the details of innumerable reactions.
The Friedel-Crafts reaction is one of the most useful
reactions in preparative organic chemistry. In most text
books, the reaction is discussed in connection with the
synthesis of alkyl and acyl derivatives of the aromatic
hydrocarbons. It will be seen in the following pages how-
ever that this is a somewhat misleading and incomplete
view, since there are a great number of reactions involving
the use of aluminium chloride which are not included in the
above classification. With regard to the changes occurring
in the Friedel-Crafts reaction, the aluminium chloride does
not appear in the final product. The reaction as carried
out in the laboratory is very often done in steps, first

bringing together the components, perhaps in the presence

of a diluent such as carbon disulfide; and second, decom-
posing the reaction mixture with water with the formation
of the desired substance or substances and removal of the
aluminium as chloride or hydroxide, etc. Since aluminium
chloride may be present after the reaction has proceeded
to a certain point, it may be assumed as a first consideration
to play the part of a catalyst. A brief review of the
theoretical explanations proposed at different times to
account for the mechanism of the reaction will first be given.
C. Friedel and J. M. Crafts described the reaction in
1877 [J. pr. Chem. 16, 233.] Two typical reactions given
by them were (1) the formation of amylbenzene from amyl
chloride and benzene and (2) the formation of benz()i)hen()ne
from benzoyl chloride and benzene, both in the j)resence of
aluminium chloride and giving hydrogen chloride as by-
product. They suggested the following equations as an
explanation of the first i;eaction:
 :

96 CHEMICAL REACTIONS.

CeHe + AI2CI6 = HCl + AI2CI5C6H5,

(hypothetical compound)
AI2CI5C6H5 + CsHnCl = AI2CI6 + CeHsCCoHn).

They assumed the formation of the hypothetical intei

mediate compound AI2CI5C6H5 in this reaction and of simih
compounds in other reactions. This theory has nev(
been demonstrated experimentally to be true and has
therefore, been superseded by other theories.
The dominating idea in Friedel and Crafts' original theoi
and in most of the theories attempting to explain the re-
action is the formation of more complex compounds first,

followed by their decomposition or further reaction. jfl|

G. Perrier [C.r. 116, 1300 (1893); Ber. 33, 815 (1900)]
found that in the Friedel-Crafts reaction for the formation
of ketones from hydrocarbons and acyl halides, the acyl
halides and also the ketones formed in the reaction formed
addition compounds with the aluminium halides which he
was able to isolate ^

2RC0C1 + AI2CI6 = (RCOCl)2Al2Cl6,

(RCOCl)2Al2Cl6 + C^Hn = 2HC1 + (RCOC^H„_i)2Al2Cl6.

The decomposition of the addition compound (which formed

a crystalline compound) with cold water yielded the ketone.
The formation of these compounds has since been confirmed
by several other investigators and has enabled them to study
the kinetics of this reaction in the case of acyl halides.
G. Gustavson proposed the theory that the aluminium
chloride formed intermediate addition compounds of the
type AlXsCeHe and AIX3.3C6H6 [J. pr. Chem. 68, 209

(1903)1,and that in the course of the reaction these addi-

tion compounds reacted with the alkyl halides to form the
reaction products. For the preparation of these addition
compounds, he passed dry hydrogen chloride into a mixture
of aluminium chloride and the hydrocarbon [Ber. 11, 2151
 SOME CHEMICAL REACTIONS. 97

(1878)]. They could not be obtained in crystalline form

however and recently some doubt has been cast on their
existence. Gustavson finally succeeded in obtaining a
crystalline compound which had the composition 2 AICI3.-
2 C6H3[CH(CH3)2]3.HC1 [C.r. UO, 940 (1905); J. pr. Chem.
72, 57 (1905)], but this does not conform to the above type
and is really a ternary compound.
B. N. Menschutkin [J. Russ. Phys. Chem. Soc. U, 1089
(1909); Chem. Zentralb. 1910, 1, 167] showed that the
freezing point curves of mixtures of aluminium halides and
benzene or toluene gave no indication of the formation of
any such addition compounds as claimed by Gustavson.
Many chemists are inclined to accept the results of Men-
schutkin as conclusive evidence that aluminium halides and
benzene or toluene do not form any addition compounds.
On the other hand, all that the freezing point curve shows
under these conditions is that, even if formed, not enough
of the addition compound was present to saturate the
solution. Furthermore, Menschutkin found that in the
case of other metal halides such as antimony chloride,
addition compounds such as SbCls.CeHe can be obtained
[C. A. (1911) 1434)]. It must also be borne in mind in

comparing these results with the results of Gustavson, that

the latter in his experiments had hydrogen chloride present
as well.
J. Boeseken and co-workers [Rec. trav. chim. 32, 184
(1913); 3S,?>\1', 34, 7S; 35,109; Verslag Akad. Wenschap-
pen 21, 979] studied the Friedel-Crafts reaction in connec-
tion with sulfonyl chlorides such as p-brombenzene-
sulphonechloride, etc. These combined with the aluminium
chloride. The resulting compounds then reacted with the
aromatic hydrocarbon. The sulfone formed in the reaction
'ombined with the aluminium chloride, and if formed in
considerable amount decreased the velocity of the reaction
by decreasing the concentration of the double salt of the

sulfone chloride and aluminium chloride.

 :

There is
CHEMICAL REACTIONS.

considerable experimental evidence at hand,

J
therefore, for the formation of double salts or binary com-
pounds from acid chlorides and aluminium halides. In
addition to the examples given, E. P. Kohler [Am. Chem. J.
24, 390 (1900)] iso^ated the compounds A^Brs CeHsSOgCl,
AlBra.CeHsCOCl, AlBrs-POCla, AlBra.CeHsCOCHa, and
AlBr3.C6H5N02, and Abegg [Handbuch der anorganischen
Chemie, vol. 3, part 1, p. 74 (1906)] mentions the com-
pounds AICI3.SCI4; AICI3.2PCI3; AICI3.2KCI; AICI3.4KCI;
AICI3.4NH4CI; etc. The ability of aluminium halides to
combine to form complex compounds is also shown in the
following substances which have been described
AlCl3.HgCl.C6H6 W. Gulewitsch [Ber. 37, 1560 (1904)];
AlCl3.(C2H5)20; AICI3.C6H5OCH3; AICI3.C6H5CO2C2H5;
C2H5Br.H2S.AlBr3 [V. A. Plotnikoff, J. Chem. Soc. Abstr.
(1913), 1, 1295], etc.
The evidence for the formation of binary compounds with
aluminium halides and acyl halides, inorganic halides and
a number of organic substances containing oxygen but no
halogen is satisfactory. On the other hand, the evidence
at hand concerning addition compounds from aromatic
hydrocarbons and alkyl halides has failed to show their
presence. For example, A. Wroczynski and P. A. Guye
[J. chim. Phys. 8, 189 (1910)] found that the freezing point
curve of a mixture of benzene a^nd chloroform gave only one
eutectic, and Schmidlin and Lang observed the same with
the benzene-bromoform system.
B. N. Menschutkin [Chem. Zentralbl. (1910), I, 167] and
also J. Boeseken [Chem. Zentralbl. (1911), I, 466] suggested
that in the Friedel-Crafts reaction the three reacting com-
ponents combined to form a ternary compound which then
reacted further. This view was adopted and elaborated by
J. SchmidHn and R. Lang [Ber. 45, 899 (1912)]. They
considered the evidence for the existence of binary com-
pounds described above, and concluded that the only satis-
 SOME CHEMICAL REACTIONS. 99

factory explanation lay in the formation of ternary com-

pounds. As positive evidence they cited the solubility of
aluminium chloride in cold mixtures of benzene or toluene
and alkyl halides forming filterable solutions which evolve
hydrogen chloride upon being warmed, and also the increase
in conductivity observed when benzene or toluene was
added to a solution of aluminium chloride in ethyl bromide
[J. W. Walker, Trans. Chem. Soc. 8J^, 1082 (1904)].
There have been several other theories proposed for the
mechanism of this reaction where no consideration was
given to the existence of addition compounds. Among
these may be mentioned the theory of J. U. Nef [Lieb. Ann.
298, 253 (1897) ]. He considers that the aluminium chloride
splits out the hydrogen halide from the alkyl halide forming
in this way an olefin which is added to the aromatic hydro-
carbon. This is in line with his views concerning reactions
of carbon compounds in general.
In conformity with the general principles outlined in
previous chapters the view of the mechanism of the Friedel-
Crafts reaction which will be adopted here will be that of
Menschutkin, Boeseken, and Schmidlin and Lang, based
upon the formation of a ternary compound. This view
brings the Friedel-Crafts reaction in line with many other
organic reactions, and permits of a more systematic classi-
fication of the various types.
In the Friedel-Crafts reaction then itmay be assumed
that a ternary compound consisting of aluminium chloride
and the two reacting components is formed which is in
equilibrium with various sets of substances. The following
example will illustrate the formulations:

/c.HJl\ rcji.HCn
)-Laici, («
liici J+<^'""
100 CHEMICAL REACTIONS.

In this reaction, as generally viewed, ethyl benzene is

formed from ethyl chloride, benzene and aluminium chlor-

ide. Some of the equilibria in this reaction with the ternary
(or considering ethyl chloride to be made up of ethylene
and hydrogen chloride, quarternary) intermediate com-
pound are indicated. Only a few of the possible reactions
are shown. Taking equilibria (a) and (c), it is evident
that this represents the reaction as ordinarily viewed. In
[HCl 1
A ip, may also be in equiHb-

rium with its components. If acetyl chloride is used in

place of ethyl chloride, a binary compound of acetophenone
and aluminium chloride is formed which may be decomposed
by water. The presence of aluminium chloride in the
reaction mixture appears to favor the formation of con-
densation products, that is, more complex bodies from the
simple substances. In the presence of aluminium chloride
the products of certain definite equilibria are obtained.
With other so-called "condensing agents" or catalysts, such
as sulfuric acid or sodium hydroxide in place of aluminium
chloride, other products may be formed due to other of the
possible equilibria being favored. As indicated in Chapter
V, a large number of equilibria and products are possible
with a ternary compound. The part that a substance such
as aluminium chloride plays in such reactions, is to cause
certain definite equilibria to dominate over others as already
indicated. Other added substances would cause other
equilibria to dominate. For instance, if alkali were added
to a mixture such as the above, the reaction by which
ethylene and hydrogen chloride is formed from ethyl
chloride might predominate. While there are definite
differences in these changes, the principle which is brought
out is that with a certain number of reacting substances
which go to make up a ternary or even more complex
compound, and which is in equilibrium with a large number
 SOME CHEMICAL REACTIONS. 101

of different sets of products, the addition of a new substance

to the reacting mixture will cause certain of the reactions or
equilibria to predominate over others, and each different
added substance may result in a different equilibrium being
observed experimentally. There is nothing said as to
whether the added substance acts as a catalyst or not.
This question is evidently a secondary one. From the
theory of catalytic actions developed in Chapter IV, a
reaction is catalytic if one of the reacting substances appears
as an initial substance and
final product. With acetyl
chloride, benzene,and aluminium chloride, a compound of
acetophenone and aluminium chloride is obtained. If the
reaction is considered to be at an end here, aluminium
chloride may be considered to act as a catalyst since its

composition is unchanged. If, however, water is added to

the reaction mixture, as is generally done experimentally,
then the aluminium chloride is decomposed and would not
be called a catalyst in the reaction. This view of the
function of the action of aluminium chloride as a possible
catalyst in the Friedel-Crafts reaction holds throughout.
Whether assumed to act as a catalyst depends upon
it is

where the reaction is assumed to stop. In this connection

it may be pointed out that the action of aluminium chloride

has been considered by some from two points of view.

Either it has been considered to act catalytically or as in
an ordinary chemical action taking part in a definite
stoichiometrical ratio; but it is seen that this difference is

more one of definition and classification than a real difference

in the mechanism of the reaction.
Since there is number of the re-
definite evidence in a
more complex intermediate com-
actions' that ternary or
pounds are formed, and there is evidence of comi)lex
compound formation with a numl)er of other compounds of
aluminium and similar metal halides, the general exj)lana-
tion of the Friedel-Crafts reaction may be taken to be that
102 CHEMICAL REACTIONS.

indicated with a complex compound of the third or higher

order as intermediate compound. The readiness with which
such complex compounds are formed and their stabilities

will depend evidently upon the nature of the reacting sub-

stances, and it should be possible to find regularities in the
compositions of these reacting hubstances, upon which the
ready formation of the condensation products in this re-
action depends. A comparison of such groupings which
facilitate this reaction (either by more rapid formation of
intermediate products and their decomposition in certain
directions, or in shifting the equilibria, or in some other
way), with the groupings which facilitate the same or
other condensation reactions in the presence of other
catalytic or condensing agents, should be of value in develop-
ing the general theory of the mechanism of such reactions,
of which the Friedel-Crafts reaction has been chosen as a
well-known example.
A number of reactions which are aided or accelerated by
aluminium chloride will now be given. Only the initial
and the final products which are of immediate interest will
be outlined. The probable complex intermediate compound
will not be formulated although it will be understood to be
present and involved in the different equilibria in every
case. The reactions only in exceptional cases proceed
quantitatively as indicated, and there are as a rule a
number of other products formed in the reactions. These
will not be indicated here. It is evident that a careful
quantitative study of these reactions would be of great
value.
1. C2H5CI +
CeHe = C6H5C2H5 + HCl. '

2. CH3COCI +
CeHe = CH3COC6H5 + HCl.
3. CHCI3 + SCeHe = CH(C6H5)3 + 3HC1.
4. O2NCCI3 + SCeHe = 02NC(C6H5)3 + 3HC1.
5. C6H5CH2CH2COCI
= C6H4 - CH2 - CH2 - CO + HCl.i
IF. S. Kipping, Trans. Chem. Soc. 65, 480 (1894).
 .

SOME CHEMICAL REACTIONS. 103

6. CH3COCI + CH3COCI + CH3COCI

= CH3COCH2COCH2COCI + 2HC1.2
7. 3C3H7COCI
= C2H5.CH.CO.CH (C2H5) .CO.CH (C2H5) .CO^
+ 3HC1.
8. (C6H5)3CC1 + HOCH3
= (C6H5)3COCH3 + HCl^ (Etherification).
9. CH3CI + C6H5NH2.HCI
= C6H4(CH3)N(CH3)2 + 3HC1^ (Alkylation of
amines)
10. C2H5Br + H2S = C2H5SH + HBr.5
11. 2C6H5CH2CI = (C6H5)2C C(C6H5)2 + 2HC1.« :

12. CH2 CH2 + CeHe

: = C6H5CH2.CH3.^
13. CH CH + CeHe
: = CeHsCH CH2.« :

14. CN.CN + CeHe = CN.CfCeHs) NH.« :

15. CH2.CH2.CH2 + CeHe = C6H5.CH2.CH2.CH3.«

16. C6H5.N C O + CeHe = CeHs.NH.CO.CeHs.^
:
•

17. CO2 + CeHe = CeHsCOOH.^

18. SO2 + CeHe = C6H5SO2H.7
19. CO + CeHe = CeHsCHO.io
20. O2 + 2C6H6 = 2C6H5OH.7
21. S + CeHe = C6H5SH.7
22. R.CH(CH2)2.C0.6 + CeHe
= R.CH(OH)CH2.CH2.CO.C6H5.«
23. CHCl : CCI2 + CCI4 = CCl3.CHCl.CCl3.«
24. CHCl : CCI2 + CHCI3 = CHCl2.CHCl.CCl3.«
2 A. Combes, C. r. 103, 814 (1886); Ann. chim. phys. [6] 12, 199
(1887); F. S. Kipping, Proc. Chem. Soc. 9, 208 (1893).
3 A. Combes, C. r. 103, 814 (1886).
4 C. Fricdel and J. M. Crafts, Ann. chim. [6] I, 503 (1884).
^ V. A. PlotnikofT, Chem. Soc. Abstr. (1913) I, 1295.
J.
« H. J. Prins, J. pr. Chem. 89, 14, 432 (for further references) (1914).
>
C. Friedel and J. M. Crafts, Ann. chim. [6] H, 433 (1888).
8 II. Varet and G. Vienne, Bull. Soc. chim. 47, 918 (1887).
» S. Krapivin, Chem. Zentralb. (1910) I, 1335.
">L. Gatterman and J. A. Koch, Ber. 30, 1622 (1897); Lieb. Ann.
547, 347 (1900).
8
104 CHEMICAL REACTIONS.

25. C2H4+ HX = C2H5X.

26. C2H5ONO2+ CeHfi = C6H5NO2 + C2H5OH.11
27. CsHnONO + CeHe = CeHsNO + C5H11OH.11
28. CICH2CO2C2H5 4- CeHe
C6H5C2H5 + CICH2COOH.4
=
29. CICO2C2H5 + CeHe C6H5C2H5 + HCl + C02.^
=
30. C6H5CH3 + PCI3 C6H4(CH3)PCl2 + HCI.12
=
31. 3CH3I + CHCI3 = CHI3 + 3CH3CP3 (CH3CI volatile).
32. 2C6H6 = CeHs.CeHs + H2.

"-
34. CeHo
CO =
=aTTX)-
^ ^
+ Brg CeH^Br +
'2
(4) (7)

HBr
The first striking fact in these reactions is the large
number compounds whose reactions are ac-
of different
celerated by aluminium halides. Not all reactions which
have been studied are included in this list, but the variety
is sufficiently great to show the general applicability of the
reaction. Those given may be divided into groups: Re-
actions 1 to 11 include the elimination of hydrogen halide
in the formation of the condensation product; reactions 12
to 25 include direct addition of the components, accelerated
by the presence of aluminium halide; reactions 26 and 27
show that nitrogen compounds may be included; reactions
28 and 29 that with certain groupings, in place of the
elimination of hydrogen halide as the dominant reaction,
different groups may be eliminated; reaction 30 shows a
further possibility; while reactions 31 to 33 are in reality
oxidation-reduction reactions and should be treated in a
later chapter but are included here for the sake of complete-
ness; and reaction 34, really an oxidation-reduction reaction
also, is included to show the action of halogenation. A
number of other reactions which are catalyzed by aluminium
11
E. Boedtker, Bull. Soc. chim. IV (3) 726 (1908).
12
A. Michaelis and C. Panek, Ber. 13, 653 (1880).
13
J. W. Walker, J. Chem. Soc. 85, 1089 (1904).
 SOME CHEMICAL REACTIONS. 105

chloride but which are in reality oxidation-reduction re-

actions in the sense that certain atoms in the molecules
change their valence or state of oxidation, may be men-
tioned. For example, xylene at its boiling temperature
with the addition of 2 to 4 per cent, aluminium chloride
yields 12 per cent, toluene and also benzene and poly-
methylated benzene (F. Fischer and H. Niggeman, Ber. Jf9,

1475 (1916). The action of aluminium chloride on petrol-

eum was studied by A. Pictet and I. Lercynska (Bull. soc.
chim. IV, 19, 326 (1916)). Cyclohexane was found to
rearrange in part to methylpentamethylene on heating to
boiling for 48 hours in the presence of aluminium chloride
(I.Aschan, Lieb. Ann. 32^, 1 (1902)).
In addition to the evidence regarding complex addition
compounds already given, another line of proof may be
mentioned. The reacting mixtures in the Frie^el-Crafts
reaction as a rule develop more or less color, starting with
colorless compounds. The formation of colored Compounds
in the case of somewhat diflferent reactions has been taken
to show addition compounds [J. Kendall, Jour. Amer.
Chem. Soc. 37, 149 (1915) for aldehyde and ketone addition
compounds with acids, and H. Wieland and E. Wecker, Ber.
4.3, 699 (1910) as forerunners of a number of substitution

reactions.]
With regard to the chemical constitutions or structures
of the intermediate addition compounds, not much can
be said. The element which appears to be specifically
responsible for the formation of these compounds is alumi-
nium. Aluminium salts readily form " onium " or molecular
compounds or compounds of the second and higher orders.
The occurrence of complex aluminium salts in nature, such
as the aluminium silicates, bauxite, etc., shows that complex
inorganic aluminium compounds are capable of existing
and are apparently extremely stable. The complex organic
compounds of aluminium, some of which have been proven
106 CHEMICAL REACTIONS.

to exist and others which are assumed to be formed in the

Friedel-Crafts reaction, parallel these inorganic compounds.

The difference between the two sets lies in the tendency
of the organic part of the compounds to reach a more
stable condition and the velocity with which this condition
is attained. Otherwise the two sets of compounds are
similar. Besides the fact that chemical combination is

probably due primarily to the ability of the aluminium to

form.onium compounds under the given conditions, it is
difficult to say more at present with regard to the chemical

structures of these complex intermediate compounds.

In place of the aluminium chloride used in the Friedel-
Crafts reaction, it has been found that some of the chemical
changes may be accelerated by the addition of other
catalysts to the reaction mixtures. Anhydrous zinc chloride
has been used to some extent in this way. The following
reactions are a partial list of such changes. The part
played by the zinc chloride, in the formation of the probable
complex intermediate compounds and the equilibria of the
latterwith various sets of products, is omitted and only
the main reactions or changes are shown just as in the
Friedel-Crafts reaction.

35. 2CH30QHn+CH3COCI^^^j|^^^+_^^^^^Q^^J^^.

r>OH
CO '^=j^

-CX>-0°=CC '/"-«."
CO \oV^N(CH3)2
37. C6H5CCI3+2 CoH5N(CH3)2= C^HsCClCX^
kJx(CH3)2+2HCl
38. CI3CHO + SCeH N(C2H5)2
= [(C2H5)2NC6H4]3C.CH[C6H4N(C2H5)2]2
+ H2O + 3HC1.
39. CeHsCHO + CH3NO2 = CeHsCH CHNO2 + H2O.
:
 :

SOME CHEMICAL REACTIONS. 107

40. (CH3)2(C2H5)C(OH) + CeHaOH

= C4H9<^-OH+H20.
OH OH
41. CH3COOH + (^__y OH = CH3CO <3)-OH+H20.
X^y-OH
42. HCOOH + 3C6H5OH = ^\ + 2H2O.

OH
It is evident that zinc chloride is almost as universal a
catalyst for such reactions as aluminium chloride, and
undoubtedly it would be found experimentally that in
many of the Friedel-Crafts reactions zinc chloride
would
answer as well as aluminium chloride.
Concentrated sulfuric acid is also employed very often
in such condensation reactions. It can be used in reaction
36 as well as zinc chloride. Other reactions in which it
has been used as catalyst are as follows (formulated in the
same way as the preceding reactions)

43. 2C6H6 + (CH30)2CH2 = (C6H5)2CH2+ 2CH3OH.

44. 2C10H8 + CH2O = H2C(CioH7)2 + H2O.

45. 2C6H5NO2 + CH2O = h^cOp; ^^% H,0

\_}-N02
46. CeHsCHO + 2C6H6 = CHCCel^a + H2O.
47. /OH
C6H4^CHO + CH3COCH2CI
/OH
= C6H4-CH :CH.C0CH2C1+ H2O.

Other catalysts or so-called condensation agents may be

considered in the same way. Without elaborating further,
it may be said that the same principles apply to all these
reactions; the formation of a complex intermediate addition
108 CHEMICAL REACTIONS.

product which may be in equilibrium with various sets of

products, and the course of the reaction in the presence of a
definite catalyst being dependent upon the concentrations
of the various reacting substances according to the principle
of mass action and the relative velocities of the reactions
if equilibrium has not been attained. In a number of cases
the intermediate compound has been isolated. The reac-
tions are quantitative only in exceptional cases. As a rule
a number of products are obtained,
above equations represent the products which were of
but those given in the
in-
I
terest at the time the reaction was studied.
It will have been observed that a certain awkwardness in
nomenclature has occurred in the discussion of the reac-
tions. In the formulations of the different reactions, equi-
have been spoken of at times without the intention of
libria

conveying the meaning that the various substances taking

part existed at definite equilibrium concentrations. The
term equilibrium was used in these cases in place of the
more usual "chemical equation" to emphasize the signifi-
cance of reversibility and mass action effect.
A definite group of reactions which has been studied
extensively is that in which a nitro-group is introduced
into an organic compound, combined with carbon and in
place of a hydrogen atom. This reaction is commonly
known as nitration, but in conformity with the general
chemical nomenclature it should be called nitronation.
However, for the present in this book, the older term
nitration will be used. Before taking up nitration reactions
in detail, some general relations developed in the reactions
already considered and some additional ones will be dis-
cussed briefly.
It is well known that the presence of certain side chains
on the benzene nucleus facilitates the introduction of
various substituent groups in place of the hydrogen of the
benzene nucleus. This is true for the Friedel-Crafts re-
 SOME CHEMICAL REACTIONS. 109

action, halogenation, sulfonation, nitration, etc. The ques-

tion of the possible relation of this phenomenon to the
mechanism of the reactions has been studied more carefully
in nitration than in other reactions.
It has been found that aniline, phenol, and similar com-
pounds of this type are nitrated to a greater extent by a
given strength of nitric acid than is benzene itself. It has
been observed quite frequently that an intermediate com-
pound is formed in which a hydrogen of the amino or
hydroxyl group on the benzene ring has been replaced by
the nitro or other entering group. This compound then
rearranges under certain conditions so that the entering
group substitutes in the ortho or para position. Such
rearrangements are very general and were first studied
systematically for the rearrangement of hydrazobenzene
to benzidine. This type is therefore commonly known as
the benzidine rearrangement. The question has been con-
sidered whether such intermediate compounds always occur
in the nitration, etc., of derivatives of benzene when ortho
and para derivatives are obtained, or whether substitution
in the ortho and para positions can take place directly.
This led to the development of two theories of substitution:
(1) Direct substitution, which takes place with benzene

compounds having an amino or hydroxyl group already

present; (2) Indirect substitution, which always occurs
when ortho and para compounds are formed. Holleman
carried out a serie of experiments to test these views, and
came to the conclusion that it is not essential for an inter-
mediate compound such as is assumed in indirect substitu-
tion to be formed, and that indirect and direct substitution
are essentially the same.
In discussing this question, it seems simplest to look
upon it as analogous to the etherification of alcohol with
sulfuric acid as catalyst. In this reaction, it has been
suggested that the etherification takes place in several
no CHEMICAL REACTIONS.

steps; first the formation of ethyl hydrogen sulfate, and

then the action of more alcohol with the latter to form
ether. The evidence adduced by those holding this view
is that ether can be formed by starting with ethyl hydrogen
sulfate and that ethyl hydrogen sulfate can be formed from
ethyl alcohol and sulfuric acid, and therefore that the ethyl
hydrogen sulfate is an intermediate product which is always
formed. It has been pointed out in a previous chapter
however that a more correct view of this reaction is that
the ethyl alcohol and sulfuric acid form an addition com-
pound which can dissociate in different ways and is there-
fore in equilibrium with various sets of products; for
example, to form ethyl hydrogen sulfate in one reaction;
ether in another, olefin in another, and so on. The product
actually obtained depends upon the conditions (chemical
and physical) as already pointed out.
It seems that the question of indirect substitution is a
similar one and that here also an intermediate addition
compound is formed which may dissociate on the one hand
to form a compound with the substituent in the side chain,
and on the other hand with the substituent in the benzene
nucleus.
In taking up a more detailed study of nitration, the
general methods of preparing nitro compounds may first
be mentioned. The usual methods involve the action of
nitric acid alone, or in the presence of sulfuric acid, or of
water, or of a non-ionizing medium such as ether. Other
methods involve the use of ethyl nitrate or of nitrosulfates
(NO2.OSO2.OH), nitroacetates (or acetyl nitrate), etc. For
methods used in isolated cases reference must be made to
the books of Weyl, Lassar-Cohn, and others.
J. U. Nef's view of nitration is of interest. He considers
the reaction to be analogous to an aldol condensation and
formulates it as follows (Jour. Amer. Chem. Soc. 26, 1566
(1904)):
 SOME CHEMICAL REACTIONS. Ill

r^H +0=N-OH»-^Q-N
r^?-^^ >^Q ,x-^N02
U O
+ H,0

His general theory for this and similar reactions may

be given in his own words: "Excluding reactions called
ionic, a chemical reaction between two substances always
first takes place by their union to form an addition product.
The one molecule being unsaturated and in a partially active
condition absorbs the second molecule because it partially
splits or dissociates it into active portions. The resulting
addition product then often dissociates spontaneously,
giving two new molecules. The similarity of such reactions

to those called ionic is at once apparent, but their relation-

ship cannot, in the present state of our knowledge, be
clearly understood." Nef's view of this reaction is similar

to the one developed here and differs mainly in that he

formulates the manner in which the hydrogen atom of the
benzene acts specifically.

Nitro compounds may be obtained by the action of ethyl

nitrate and aluminium chloride. Since many of the Friedel-
Crafts reactions may be carried out with sulfuric acid in
place of aluminium chloride, and since in nitration with
nitric acid, sulfuric acid is very often used, the fact is

brought out again that nitration belongs to the same

general type of reaction as the Friedel-Crafts reaction.
This similarity may be brought out in the following manner.
The reaction
/R_^C6H5\ /R
2C6II5 + O = C-R ^ C6H5-C-R + PT2O
(A) (B)

is accelerated either by sulfuric acid or aluminium chloride

In the compound (B) the oxygen atom plays the part of the

clilorine in the usual Friedel-Crafts reaction. If in place

of the oxygen compound, the ketone, B, the oxygen com-
])ound nitric acid be substituted, the reaction would be
similar. The same is true if (B) represented an aldehyde.
112 CHEMICAL REACTIONS.

Such reactions with aldehydes were illustrated in reactions

44 to 47 above where sulfuric acid was the special catalyst.
Reaction 26 illustrated nitration with ethyl nitrate and
aluminium chloride. Remembering the fact that in the
final product condensation has taken place with the elimina-
tion of the oxygen of the ketone, aldehyde, or nitric acid,
whether the catalyst was sulfuric acid or aluminium
chloride, and comparing the initial and final products
obtained with the initial and final product of the reaction
when a base is neutralized by an acid;

HX + BOH = BX + H2O

it is evident that the benzene plays the part of the acid,

and the ketone, aldehyde, or nitric acid that of the base.

In discussing the entrance of a new substituent in a ben-

zene derivative, it will be found that a number of reactions
can be very much simplified if it is considered that the para
(or ortho) hydrogen atom to the group present takes part
in the reaction. To explain by means
of an example In :

aniline it may be assumed that an equilibrium exists be-

-3
-4
+1
tween the two tautomeric forms T ^^g ^zz^ jT NH,
j J^
(A) (B)

In (B) the nitrogen is in the onium form, and the benzene

nucleus (or more strictly, the para carbon atom) plays the
part of the acid. This equilibrium is similar to the one pres-

;!
ent in glycine; namely, H02C.CH2.NH2::;=^ O.QC.CH2.N H3
There is evidence to show that the equilibrium exists in the
latter case. In the former, the assumption of such a
similar equilibrium helps to explain a number of reactions,

in fact, it may be taken to be the fundamental phenomenon

in all "benzidine rearrangements."
 SOME CHEMICAL REACTIONS. 113

Taking the simplest case, the nitration of benzene, the

reaction may be formulated as follows:
OH
HO.NO,

+ H20

NH-NOc
+ H2O
These equilibria represent a more or less ideal case, since
as a rule other substances are present, and also the nitro-
amine which may be formed reacts farther. If sulfuric

acid is present, a ternary intermediate compound would

be formed. If acetanilide were used instead of aniline,
the general reaction would be similar. If, however, a
large excess of sulfuric acid were used in the reaction, then
the aniline would be present practically entirely as aniline
sulfateand there would not be the tautomeric form present.
Under these circumstances, the intermediate compound
would not be the same as before, and the nitration would
proceed as if benzene itself were being nitrated. Mainly
meta compound would be obtained under these conditions.
The velocity of nitration of benzene derivatives containing
different substituents was studied by H. Martinsen [Z.

physik. Chem. 60, 385 (1905); 69, 605 (1907)]. He found

the velocities to be dependent upon the substituents in the
following way:

N02<S03lI<C02lI<Cl<CH8<OCH3<OC2ll6<OII.
< ¥
Smaller velocity greater velocity
114 CHEMICAL REACTIONS.

Those groups which when present diminish the velocity

orient the nitro group into the meta position, those which
increase the velocity orient the nitro group into the para
and ortho positions. A reason for the increase in the
velocity of substitution by amino and hydroxyl groups
may well be due to the unsaturation of these groups and
their ability to form addition compounds. The nitro,
sulfonic acid, etc., groups being more saturated, have the
opposite effect.
In the nitration in the presence of sulfuric acid, W.
Markownikoff [Ber. 32, 144 (1899)] and others consider
the nitrating agent to be nitrosulfuric acid,

SO2

In the presence of acetic anhydride or acetic acid, a similar

compound of nitric and acetic acids, acetyl nitrate, is
assumed [A. Pictet and P. Genequand, Ber. 35, 2526 (1902)],
and with benzoic acid, benzoyl nitrate [R. Willstatter,
Ber. 42, 4152 (1909)]. Whether these compounds play
the part assigned is similar to the question of whether ethyl
sulfuric acid is always formed in the preparation of ether,
and may be handled similarly. If it is formed at some
stage of the reaction, it will probably be more able to form
an addition compound, since it is obtained by loss of the
elements of water from two other molecules and is probably
more unsaturated. In this way, the velocity of the reaction
might be accelerated, but an intermediate addition com-
pound would still be formed.
Nitration in solvents other than water is to be preferred
at times. In acetic acid for example, besides the advantages
just spoken of, the solvent effect of the acetic acid may be
of aid in increasing the concentration of the hydrocarbon.
Such conditions as the hydrogen ion concentration of the
mixture may also play a part and may be influenced favor-
 SOME CHEMICAL REACTIONS. 115

ably by changing the solvent. Another factor to be con-

sidered is that in some reactions nitric acid will cause oxida-
tion, and the choice of the solvent will sometimes obviate
this. These special cases have not as yet been investigated
quantitatively with sufficient care to enable general con-
clusions to be drawn as to the reasons for these conditions.
compounds cannot as a rule be prepared
Aliphatic nitro
in the same way as the aromatic nitro compounds. The
more rapid oxidation of aliphatic hydrocarbons by nitric
acid is the main interfering factor, so that conditions must
be chosen which minimize oxidation and promote nitration.
The oxidation reactions are of such complexity in these
cases that no attempt will be made to formulate them.
Only a summary of the conditions favoring nitration will
be given. The use of a solvent such as ether for carrying
out the reaction is often successful. Also dilute nitric acid
has been used, and alkyl (generally ethyl) nitrate. In the
Friedel-Crafts reaction with ethyl nitrate, aluminium chlor-
ide is used as catalyst. In aliphatic nitrations with ethyl
nitrate, alkalis such as metal alkoxides (NaOC2H5) are
found to be best. The use of alkalis brings out the simi-
larity of this reaction to aldol condensations which are
also favored by alkalis. An example of aliphatic nitration,
in comparison with an aromatic one may be given:
/COCH3 . ^COCHa
C2H5ONO2+H2C/ MoOPW
^aOCjHfi
NO2CH +C2H6OH,
^COiCHfi -^COaCaHfi
CjHfiONOz+H.CeHs
j^^^ NOzCeHo+CaHsOH.

The presence of unsaturated or so-called ''negative" groups

on the carbon atom being nitrated appears to be necessary
for a satisfactory carrying out of the reaction.
Another method for the aliphatic nitration is the reaction
of alkyl halide with silver nitrite, in which considerable
nitro compound is formed. With alkali nitrite on the other
hand, very little nitro compound is formed. This diflVrence
 :

116 CHEMICAL REACTIONS.

is evidently due to the different oxidizing potentials of the

silver and the and the equilibria between various
alkali,

sets of products and the intermediate addition compound.

Similar questions come up with other sets of isomeric com-
pounds, cyanides and isocyanides; oxygen and nitrogen
ethers of cyanic acid, etc. This question will be taken up
again in a later chapter.
While the explanation of the benzidine rearrangement
has been applied specifically to nitration only, it evidently
holds for all similar reactions. With benzidine, the formula-
tion may be given as follows

NH — NH ( >^K >-NH[^nhV~\
(A)
'

^ (B)

-NH^—NH^

(C)

Equilibrium may exist between the three compounds (A),

(B), and (C). In the presence of strong acid or other
suitable catalytic agent, complex additions of (A), (B),
and (C) with the former may take place, and these may
then decompose in different directions, giving in addition
to (A), (B), and (C), compounds such as

H.N-^NH^ , H,N-O^NH.,
(D) (E)

etc. The conditions of the reaction, such as the formation

of more stable salts from the sulfuric acid and (D) or (E)
may control the yield of the different products obtained,
and in this way, (E) would be obtained from (A).
The formation of diazo compounds may be taken up
briefly. First the reactions in which no hydrocarbon
 SOME CHEMICAL REACTIONS. 117

radicals are present will be described. It will be recalled

that in the formation of amides the reaction was treated
in the same way as the formation of esters from acids and
alcohols;
AOH + HNH2 = ANH2 + H2O,
or
AH AH
+ NH3 = H2O = rAH] + H2O.
HoO NH3
I
The same principle can be used to explain the formation of
amides of nitric and nitrous acids (or the formation of
nitroamines and diazotization). If A= NO2, then
O2NOH + NH3 = O2NONH4 O2NNH2 + H2O,
or or
r02N0H] [N2O + H2O]
L NH3 J
and if A = NO
ONOH + NH3 = ONONH4 ONNH2 + H2O.
[N2 + H2O]
The nitroamine and nitrosoamine are unstable under ordi-
nary conditions (since nitrogen apparently does not possess
the inertia of carbon), differing in this way from the nitro-
derivatives of the hydrocarbons. Nitroamine, known often
as nitramide, or its tautomer, hyponitrous acid, decomposes
readily into nitrous oxide and water, while nitrosoamine
forms nitrogen and water (analogous to diazo compounds).
It was pointed out in the Friedel-Crafts reaction that
the hydroxyl group or a chlorine atom might be eliminated
in the condensations; for example,

ROH + IIC6ll5»-^RC6ll5 + H2O,

or
RCl + HCeHsa^RCeHe + HCl.

Similarly with the reactions with ammonia,

AOII + IINIIi-^ANHi + H2O,

 :

118 CHEMICAL REACTIONS.

or
ACl + HNH2J«^ANH2 + HCl.
The action of nitrosyl chloride on ammonia is similar;
namely,
ONOH + HNH2^-^ONNH2 + H2O,
and
ONCl + HNH2s-^ONNH2 + HCl.

The action of nitrous acid on amines is indicated very

often as follows:

RNH2 + 0N0Hs^RN20H + H2O.

In looking at this reaction from the point of view of inter-

mediate addition compound formation, it is evident that
it belongs to the same group of reactions. The intermediate
addition compound might be formulated omoh
and the following components can be recognized and woulc
be present in the various equilibria,

H2O, olef.HOH, RNH2, HNO2, NH3, etc.

The diazotization reaction may also be formulated simi

larly to the action of a base on an acid

BOH + HA = BA + H2O,

With
ONOH + HNHR = ONNHR +
nitrosyl chloride or ethyl nitrite in place of nitrous
H2O.
I
acid, the same holds except for CI or OC2H5 instead of OH.
The nitrous acid in this reaction corresponds to the base,
and the amine to the acid. This formulation also shows
how general a classification may be developed from a
simple scheme and that although the reactions of organic
chemistry appear to be most complex and different, in
reality a great many conform to simple fundamental prin-
ciples and changes. If A= CeHs, then the reaction corre-
sponds to the formation of nitrosobenzene, etc.
 SOME CHEMICAL REACTIONS. 119

It has been noticed that in some reactions the part played

by alcohols corresponds to the part played by the acid, HA;
for instance, in the formation of esters from acid chlorides
and alcohols, in the type reaction

BX + HA = BA + HX.
This corresponds to the neutralization reaction just given
except that X is used in place of theOH. The general
principle of intermediate compound formation, though not
mentioned every time, must be understood to apply to all
these reactions. If nitrous acid plays the part of BX
and an alcohol that ofHA, then the ready formation of
nitrite esters is not surprising when the two interact. From
this point of view the nitrite esters are the aquo-esters of

nitrous acid, and diazo compounds are the ammono-esters

of nitrous acid, ON.OR and ON.NHR (not considering
tautomeric rearrangements within the molecule).
 CHAPTER VII.

SOME CHEMICAL REACTIONS (CONTINUED).

The discussion of the mechanism of the reactions con-
sidered so far may be summarized as follows:
(1) Reactions occurring in organic chemistry are similar
to those in inorganic chemistry.
(2) The theory of reactions in aqueous solutions, hereto-
fore based upon ionization relationships, can be accounted
for by addition compound formation involving the solvent.
(3) All reactions appear to take place through the inter-
mediate formation of an addition compound. If the re-
action is catalytic, the catalyst is one of the components of
the addition compound.
(4) When water is considered as the catalyst for reactions
taking place in aqueous solutions, the hydrates formed may
give rise to ionization.
The reactions may be based upon the general equation:

BX + HA = BA + HX.
They may be grouped in outline as follows:

I. Neutralization of an acid by a base; B = metal,

X= OH, A = acid group.
NH4OH + HCl = NH4CI + H2O,
NaOH + HCl = NaCl + H2O.
Water may act as the catalyst in these reactions.

II. Friedel-Crafts reaction; B = R, X= CI or OH,

A= CeHs, etc.

RCl -I- HPh = RPh + HCl,

ROH + HPh = RPh + H2O.
120
 SOME CHEMICAL REACTIONS. 121

Aluminium chloride, zinc chloride, sulfuric acid, hydrogen

chloride, etc., may act as the catalyst.

III. Aldol condensation; BX = aldehyde or ketone, A= so-

called "negative" group combined with a-carbon
atom.

RC = + H2CA2 = RCH : CA2 + H2O.

H
Various catalysts; zinc chloride, hydrogen chloride,
alkalies, etc.

IV. Esterification; B = alkyl, A= acid group, X= CI

or OH.
ROH + HA = RA + H2O,
RCl + HA = RA + HCl.

Catalysts; zinc chloride, sulfuric acid, hydrogen chloride,

etc.

V. Etherification; B = alkyl, A= alkoxyl group, X= CI

or OH.
ROH + HOR' = ROR' + H2O,
RCl + HOR' = ROR' + HCl.
Catalysts as in reactions IV.

VI. Amide formation; B = acyl group, X = OH or CI,

A= amino group.
AcOH + HNH2 = AcNHz + H2O,
AcCl + HNH2 = AcNHa + HCl,
AcOH + HNRj = AcNR^ + H2O.
VII. Amine formation; B = alkyl or aryl group, X= CI
or OH, A = amino group.

ROH + HNH2 = RNH2 + II2O,

RCl + HNH2 = RNII2 + HCl,

ROH + HNR^' = RNR2' + H2O.
I
 122 CHEMICAL REACTIONS.

VIII. Formation of nitro compounds; B = NO2,

^
X = OH
or substituted OH group, A = alkyl or aryl group.

O2NOH + HC6H5 = O2NC6H5 + H2O,

O2NOC2H6 + HC6H5 = O2NC6H5 + C2H5OH,
O2NOSO2OH + HC6H5 = O2NC6H6 + H2SO4,
O2NO2CCH3 + HC6H5 = O2NC6H5 + HO2CCH3.

IX. Formation of nitroso compounds; B = NO, X = OH,

CI, or substituted OH group, X = alkyl or aryl group.

ONOH +
HCeHs = ONC6H5 + H2O,
ONCl + HCeHg = ONCeHg + HCl,
ONOC2H5 + HC6H5 = ONCeHg + C2H5OH.
X. Diazotization; B = NO, X = OH or CI, A= amino
or alkylated or arylated group.

ONOH + HNHR = ON2HR + H2O,

ONCl + HNHR = ON2RH + HCl.
XI. Benzidine rearrangement; B = NO2, X and A=
NHC6H4.
H
I

O2N - NH - C6H4H = NH - C6H4 - NO2.

Catalysts: sulfuric acid, phosphorus pentachloride,

I
etc.

These examples, while by no means complete, show how

general the given type of reaction is, and that many of the
apparently different groups of reactions of organic chem-
istry may be classed together and treated from one general
point of view. Some general relations may be developed
from these equations. The formation of certain products
in any given case depends as stated repeatedly upon equi-
librium relationships, velocities of the different reactions,
and concentrations of the various substances involved.
Taking any one set of reactions, it would be possible to
develop regularities with regard to various groups present
 SOME CHEMICAL REACTIONS. 123

in the reacting molecules and the products obtained. To

attempt to do this here would lead too far from the main
questions which it is desired to present. At the present
time, comparable quantitative data with regard to the
relative velocities of various reactions are not at hand.
In fact, quantitative measurements of very few organic
reactions are available, so that it is evident that such a
comparison of the constitutional factors upon which the
formation of certain sets of products in reactions apparently
dissimilar but fundamentally belonging to the same type,
is not possible at present. This however does not apply
to the possibility of such studies in isolated groups of com-
pounds. For one thing, it is only necessary to refer to
Holleman's work on the substitution derivatives of benzene
and benzene derivatives, to indicate the nature of the work
which may be done in systematizing such reactions. The
velocities of esterification of substituted acids and alcohols
also offer a large field where much systematic work has
already been done and many new and interesting relations
have been developed.
There is, however, one set of relations which appears of
interest in comparison with reactions of inorganic chemistry.
It will have been noticed that in the general reaction

BX + HA = BA + HX,
the velocities of the reactions of the hydrogen compounds,
HA, vary with the character of A just as do the strengths or
ionization constants of organic and inorganic acids. It has
been customary for some years now to attribute the re-
actions of many inorganic substances in solutions to the
presence of ions, and the primary reason for the reactions
and their great velocities to certain properties of the ions.
In Chapter III it was shown in the development of the
theories of the structures of acids, how the ionic theory
played an important part in the evolution of the subject,
124 CHEMICAL REACTIONS.

and that at present, the view of acids is based upon an

outgrowth of the ionic theory and included in the modern
views of Werner. Similar relations may be shown to hold
for organic reactions where there has been no evidence of
ionization as the term is accepted in the theory of electro-
lytic dissociation.
If, in the above general reaction, A of HA represents an
alkyl group, the activity of the compound HA is very small
ordinarily. By activity in this connection is meant the
amount of reaction in a definite time. very It is used in a
rough qualitative sense here, as general quantitative com-
parisons are not possible at present. If, into the alkyl
group are introduced in place of the hydrogen atoms acid
groups, so-called negative groups, then the activity of the
compound increases in the same way that the ionization 1

constant or strength of an acid in aqueous solution is

increased when similar groups are substituted for the

hydrogen atoms of the a-carbon atom of the acid. In the
former case however, ionization according to its present
definition need not be apparent. If HA represents an

aromatic hydrocarbon, the introduction of these negative

groups exerts an opposite effect to that which is noted if

they are introduced into an aliphatic hydrocarbon, the

former being especially marked when the negative group is
in the ortho or para position to the H of HA. On the other
hand, with the so-called positive groups OH, NH2, OR, etc.,

in the ortho or para position to the H of an aromatic HA,

the HA corresponds in reaction velocity, etc., to a stronger
or more highly ionized acid, while HA is an aliphatic
if

hydrocarbon the groups have the opposite effect. If B

in BX represents an aromatic group such as (CeHsCH) = 0,
(B)
then the NO2 group for example will make the base (as BX
may be considered) more active, corresponding to the
greater ionization constants of bases. It has been observed,
 SOME CHEMICAL REACTIONS. 125

with reference to the explanation of the mechanism of the

reactions, that the readiness of formation of addition com-
pounds in general increases with the strength of the acid
(cf. J. Kendall and others).
The advantage of classifying reactions of organic chem-
istry in the given manner also becomes apparent in connec-
tion with such reactions as the decomposition of ketones by
alkalies, the "acid" decomposition of acetoacetic ester, the
decomposition of acids into hydrocarbons and carbon
dioxide, the hydrolysis of tetranitromethane to form trini-

tromethane, etc. They may also be classed together as the

same type "double decomposition" reaction.
of so-called
It is from this point of view that esters may be
also evident
decomposed with benzene in an analogous manner to their
hydrolysis by water. The relation between aldol condensa-
tion, ester ification, etherification, etc., is brought out.
Again, a point of similarity to inorganic reactions is the
effect of the catalyst. It is well known that different sol-
vents influence the electrolytic dissociation of inorganic
acids, for example, to different extents. A similar phe-
nomenon is observable in these double decomposition
reactions. It is found, in the type equation, that when A
is and B is alkyl, that aluminium chloride, sulfuric
aryl
acid, and zinc chloride act as good catalysts, or in other
words, that HA and BX are highly active, corresponding
to large ionization in inorganic reactions. On the other
hand, if A is aliphatic in nature, it appears that very often
alkalies are superior to acids as catalysts, alkalies, amines,
and alcoholates being used, as for example, in the aldol

condensation. This corresponds to a change in the solvent

with different substances in order to obtain a greater
degree of activity of the reacting substances.
The statement has already been made in the preceding

pages that the present definition for ionization is inadequate.

At present a compound in solution is considered to be in
126 CHEMICAL REACTIONS.

the ionic condition when it conducts the electric current

1
if placed between two electrodes of different potentials.
To emphasize more fully the probability that the concep-
tion of ionization is not altogether satisfactory, a few re-
actions may be considered in more detail. The hydrolysis
of an inorganic salt is explained by the ionic theory as^

follows: I^ H^ ^s ^ weak acid (slightly

hoht-^OH'i H^
4t
MeOH HX
It M
^
ionized) then the H+ from the H2O will remove the X~ as
HX in solution, increasing the concentration of the Me"^
and 0H~, and resulting in the hydrolysis of the salt. If

the MeOH is a weak base then the 0H~ from the H2O
willremove Me+ from solution and cause hydrolysis. It is
assumed in each case that the salt MeX is highly ionized.
If in the first case, HX is insoluble and in the second

MeOH is insoluble, hydrolysis of the salt will take place

as well. The 0H~ or H+ concentrations may be increased
by the addition of alkali or acid to the solution of the salt.
A specific example may be taken, namely:

MgCla + 2H0H = Mg(0H)2 + 2HC1.

This reaction takes place especially if KOH is used instead

of HOH, since the concentrations of the various ions at the
equilibrium condition of the system are such that the
solubility product of the Mg(0H)2 is exceeded. If, how-
ever, in place of MgCk, MgRCl is used, that is to say the
Grignard reagent, it will be observed that this compound
is decomposed more rapidly by the HOH than is the MgC^.
This reaction is generally considered only from the double
decomposition standpoint, the resultants and reactants, in
organic chemistry, and is not considered from the ionic
standpoint. It is impossible to state whether this sub-
stance is ionized in a water solution since it is immediately
 SOME CHEMICAL REACTIONS. 127

decomposed. But in ether it does conduct the electric

current (J. M. Nelson and W. V. Evans, Jour. Amer. Chem.
Soc. 39y 82 (1917)), but up to date the nature of the ions is
uncertain. The reaction with water is hydrolysis and very
likely of similar character to the decomposition of the
MgCk. MgRX + 2H0H = Mg(0H)2 + RH + HX or
MgRX + HOH = MgOHX + RH. With these equations
it is still possible to consider the same explanation, namely
ionic, for the decomposition of the Grignard reagent and
of the magnesium chloride. It is well known, however,
that the Grignard reagent is used to a great extent in
organic syntheses in which it is decomposed by oxygen com-
pounds other than water. Thus, aldehydes, ketones, carbon
dioxide, cyanides, etc., stated in organic chemistry to con-
tain unsaturated groups, react with the MgRX. The
simplest way to account for the reactions is to compare
them with the hydrolysis of the RMgX by water.
= Mg(f +HII Mg^$gVc(^=Mg<J-gS
^0-C=0
MgCx\;j-0 = C = = Mg<.x Ri

This way of indicating the changes makes it evident that

the aldehyde and the carbon dioxide act in the same way
as the water, but the aldehyde and the carbon dioxide
are not considered as electrolytes and hence the ionic
explanation seems to be inadequate.
The classifications and general relations developed here
together with evidence presented in a paper published some
years ago (K. G. Falk and J. M. Nelson, Jour. Amer. Chem.
Soc. 37, 1732 (1915)) apparently justify the conclusion
that the changes occurring in chemical reactions do not
depend upon the electrolytic dissociations of the reacting
substances. The chemical changes are accompanied very
often by electrolytic dissociation phenomena, but the latter
128 CHEMICAL REACTIONS.

parallel the former (or vice versa) and do not necessarily

sanlv
precede or cause them. For organic reactions it need not
be necessary to present further evidence in this connection.
With inorganic reactions, however, the question appears nolH
to be so simple. The theory of electrolytic dissociation does
not necessarily postulate that only ions react. For some time
after the theory of electrolytic dissociation was proposed, itS
was attempted to apply the theory to every possible case
where there was the slightest possibility of an explanation
based upon it. In recent years the trend of thought has taken
a different turn, and the explanations of certain reactions,
which at one time had been assumed to be purely ionic in
character, considered the un-ionized molecules as also taking
part in the reactions. The first steps in this development
were taken by G. Senter (J. Chem. Soc. 91, 467 (1907))

and by S. F. Acree (Am. Chem. J. 37, 410; 38, 258 (1907)),

and these have since been followed by S. Arrhenius, G.
Bredig, H. C. S. Snethlage, H. Goldschmidt, H. M. Dawson,
A. Lapworth, H. S. Taylor, J. Stieglitz, and others, who
favor the view that both ionized and un-ionized molecules
are active in chemical changes even in aqueous solution
and present evidence bearing on the question.
According to the views presented here, electrolytic dis-

sociation is not the forerunner of chemical reactions and in

fact chemical reactions do not depend upon the presence
of ions as postulated in that theory. Certain physical
properties of substances, which, early in the history of
the electrolytic dissociation theory, were considered to be
dependent upon ionization, have since been shown to be
independent of it. Thus, the color of a salt in solution

was assumed to be made up of the different colors of the

ions and the un-ionized molecule. Later work showed that
ionization changes do not affect the color of the substance.
Reference maybe made here to a detailed review of these
relations published by J. Lifschitz (Sammlung chemischer
 SOME CHEMICAL REACTIONS. 129

und chemisch-technischer Vortrage, Vol. 21, Nos. 5-7,

p. 175 (1914)). The explanations advanced at different
times with regard to the color changes of indicators illus-

trate these views very well. Ostwald in 1894 (" Die wissen-
schaftlichen Grundlagen der analytischen Chemie," p. 104)
attributed the different color of an indicator in acid or
alkaline solution to the different colors of the ions and un-
ionized molecules. If the indicator substance itselfwas
an acid, the color in acid solution would be that of the
un-ionized molecule, while in alkaline solution the color
would be that of the negative ion. If the indicator sub-
stance was a base, the color in alkaline solution would be
that of the un-ionized molecule, in acid solution that of the
positive ion.This theory was shown not to be general
enough to include the observed phenomena, and was re-
placed by the " chemical' theory
' first suggested (for phenol-
phthalein) by Bernthsen and developed by J. Stieglitz
(Jour. Am. Chem. Soc. 25, 1112 (1903)) and especially by
A. Hantzsch Ber. 39, 1090 (1906) and numerous articles
since) who showed the ionic theory of indicators to be
highly improbable. The view considers every
present
change in color of an organic substance to be due to an
intramolecular rearrangement. Indicators form a special
group in so far as the intramolecular rearrangements in
their case are tautomeric in character and include, therefore,
in most cases the shifting of a hydrogen atom in passing
from one form to the other. The production of ions is

secondary in the tautomeric changes, and if the ions are

colored, it is because the un-ionized molecules from which
they are derived are colored. The equilibrium between the
tautomeric forms of a substance depends upon a variety
amounts of
of factors, such as solvent, temperature, small
certainadded substances such as acids or bases, etc.
Hantzsch has shown the important part played by solvents
in affecting the equilibrium (and therefore the color change)
 y

130 CHEMICAL REACTIONS.

between the tautomeric forms of some indicators (Ber. 48

158 (1915)). Such actions take place with indicators in
solution in practical titrations where the indicator substance
is present in such small concentration that the color change

which accompanies the transformation of one tautomer into

the other is very marked with the relatively small amount
of added substance necessary to produce it (cf A. A. Noyes,
.

Jour. Amer. Chem. Soc. 32, 815 (1910)). Other changes of

conditions may be considered similarly for the indicators as
a special class of tautomeric substances. In general, it

may be stated that the various factors which influence the

equilibrium between tautomers also influence the equi-
librium between the different tautomeric forms of indicators,
and that the question of the electrolytic dissociation of the
indicator substances does not enter into the theory of their
color changes as assumed in the earlier theory, although it

appears to be connected with one of the factors involving

the sensitiveness.
It is evidently possible to extend this method of treatment
to other reactions. No more will be taken up at present,
but the view will be emphasized that chemical reactions
need not be considered to depend upon electrolytic dissocia-
tion. With the atoms in a molecule all carrying electric
charges, certain properties of a solvent make some of these
charges evident to experimental methods, while certain,
perhaps very often the same, properties of the solvent
increase the extent or rate of a reaction. These phenomena
are independent of each other but both dependent upon the
solvent, or possibly some other underlying cause. Many, if
not all, of the changes which have been considered hereto-
fore as metatheses, involve, without doubt, primary addition
and subsequent decomposition or splitting off in various
ways of the reacting molecules.
The question of tautomerism and the factors influencing
it may be considered further in the same way as organic
 SOME CHEMICAL REACTIONS. 131

reactions in general. To illustrate: In the general type

reaction BX + HA = HX + BA, if instead of considering
both molecules to be separate entities, they are considered
to be components of a single more complex molecule, then
the change would be a case of tautomerism. The following
examples will show this:

X A H
B
= N-N-"^
4-

OH
= HOHX+BN = N A
OH"

vCH3C,- CHC0,C,H,^ = ^CHeC^ CHCO^C^

|o^ H p (o-H^ r
B X 4-H A B X H A

Since A an aliphatic "negative" group in the second

is

example, the compound is more "active" and shows tauto-

merism more readily. The factors which influence the

activity of organic compounds as pointed out before in-
fluence the activity of these compounds enabling them to
show the tautomerism or to exist more readily in mutually
convertible forms. Tautomeric changes may therefore be
included in this group of organic reactions and the same
laws and relations apply to all.

The and explanations of the mechanisms

classifications
of reactions which have been developed have been illus-
trated by means of qualitative examples. Innumerable
examples of the reactions might be cited but unfortunately
the quantitative data at hand are too few to permit of
general conclusions. The possibilities in the way of dif-

ferent products being formed also complicate the quantita-

tive study with many organic reactions.
A beginning has been made in the problem of obtaining
quantitative measures of relative stability for a number of

organic compounds. Reference may be made to several

papers by C. G. Derick bearing on this question (Jour.
Amer. Chem. Soc. 32, 1333 (1910); 33, 1152 (1911)).
132 CHEMICAL REACTIONS.

Some of his conclusions from his experimental work may be

given:
In his first paper he takes up the question of stability of
isomeric compounds which rearrange to form more stable
substances to a practically irreversible extent under the
given conditions. Quantitative data are supplied for afl
series of such changes. The rearrangement of a number
of acidsand bases to more stable configurations was given.
The stability of these compounds toward ionization was
used as a measure. The equation A = RT loge K was
made use of, A representing the free energy of ionization;
R, the gas constant; T, the absolute temperature; and K,
the ionization constant. The free energy of ionization of
acids and of bases is shown as the change in free energy of the
reactions ^ +
H A H+ A" for acids and ROH R+ OH" ^ +
for bases (omitting the part played by the solvent), when
the initial and final substances are at unit concentration. It
is evident, therefore, that the free energy of ionization is

directly proportional to the natural logarithm of the ioniza-

tion constant, and that to determine the relative stabilities
of two acids (or bases) in terms of the free energy of ioniza-
tion, it is only necessary to compare the logarithms of their
ionization constants. Since an acid is more stable toward
ionization when it possesses a smaller ionization constant
or smaller free energy of ionization, the stability toward
ionization of an acid is greater the smaller its ionization
constant. The exact measures of stability are given by the
logarithms of these ionization constants. Derick gives the
results of a number and draws
of isomeric organic acids,
some general conclusions with regard to their structures
and relative stabilities toward ionization. For example, for
tetrahydrobenzenecarboxylic acids, he finds that "whenever
the unsaturation is A^ with respect to a given carboxyl

group true rearrangements of the non-reversible type are

possible" and alsor "the compounds from which Thiele
 SOME CHEMICAL REACTIONS. 133

deduced his theory of partial valence, as well as other acids

which obey the same rule, must be compounds which are
formed with weak reducing agents involving small energy
changes and where the speed of reaction is small so that
compounds result which are very unstable toward ioniza-
tion, and therefore toward rearrangement." In addition to
these quantitative results, a number of rearrangements are
grouped in Derick's first paper under various headings.
These relations are, however, only qualitative in character.
In a second series of papers, Derick goes farther and
studies the "polarity of elements and radicals measured in
terms of a logarithmic function of the ionization constant."
This is evidently the direction in which advance is to be
expected, a study of the action of various groups on the
equilibria of certain reactions in terms of affinity changes.
The following definitions are given by Derick:
1. An element or radical possesses positivity if, when it is

substituted for a hydrogen of water, it increases the hy-

droxyl ionization. It is therefore said to be positive.
2. An element or radical possesses negativity if, when it

is substituted for a hydrogen of water, it increases the

hydrogen ionization. It is therefore said to be negative.
Water is used as the standard for determining the polarity
of various groups. The relative free energies toward
ionization of the various substances are used to determine
the relative stabilities, and in this sense the classification is

limited. however useful and important as a com-

It is
parison of the stabilities toward a certain transformation
and giving a measure of the effect on a definite reaction of
different groups. A table is given of a number of these
ionization constants (Ka and K^ for acidic and basic ioniza-

tion) and the free energy values (RTlogoK). In the

succeeding papers (and also later (with O. Kamra) in the
Jour.Amer. Chem. Soc. 39, 388 (1917)) Derick takes up a
number of reactions and discusses the effects of various
134 CHEMICAL REACTIONS. I
groups upon the stabilities of the reactions. No attempt
will be made to discuss in detail the applications and con-
clusions of Derick here, but the reader is referred to his
papers for a careful study of the work. This is perhaps the
first systematic attempt to study in a quantitative way
the affinity relationships of a large number of organic com-
pounds, and to obtain exact data with regard to the effects
of different groups on the equilibrium constants and there-
fore the stabilities in certain reactions in various molecules.
The importance of this work must therefore be emphasized
as marking a beginning of the systematic quantitative study
of reactions such as have been given in these chapters,
where for lack of sufficient data, only the qualitative aspects
could be presented.
 CHAPTER VIII.

OLEFINS AND THEIR REACTION PRODUCTS.

It was stated in the preceding chapters that the reactions
of organic chemistry may be treated from the same point
of view as the reactions which have been classed under
inorganic chemistry. The same general relations apply
to all reactions in chemistry, even if, because of convenience
in grouping or presentation, they have been classed sepa-
rately. A certain justification for the separate treatments
is found in the fact that characteristic phenomena are pre-
dominant in some reactions which are more in the back-
ground in other reactions. Even if this is true, it must
be remembered that the same underlying principles apply
to all and that the laws or generalizations of
reactions
all chemical phenomena,
chemistry must necessarily hold for
and not one set of laws for some compounds and another
set for other compounds. At most, no sharp dividing line
is ever supposed to exist between the two, but only a

gradual transition set of compounds or reactions, which

may belong to one group or to the other. The point of

view to be emphasized is again similar to the point of view

presented in Chapter I, in which it was shown that two
kinds of valence, polar and non-polar, were unnecessary in
the development of atomic valence structures.
In taking up some of the reactions of organic chemistry,
the group of compounds which come to mind as being very
reactive, reactive in the sense of reacting rapidly with a
large number of different reagents, is the olefins. This
property of reacting with many compounds is well brought

out for these compounds in the term "unsaturated hydro-

carbons." The use of the term " unsaturated " was applied
in Chapter V to other compounds which formed addition
10 135
136 CHEMICAL REACTIONS.
I
compounds also. Ammonia was used there as a typical
example. Because of the general point of view which is
emphasized here, the comparative study of the unsaturated
properties of the olefins and of ammonia will be of value.
The combination of olefins with acids to form esters, etc.,

is strikingly similar to the combination of ammonia and

acids to form salts. In the great majority of these com-
pounds one molecule of the olefin or ammonia combines
with one equivalent of the acid. The reaction is also
reversible in both series. Designating the olefin by the
symbol En, (ethylene as example), the following reactions
may be given.
En + HCl = EtCl (Et denoting Ethyl),
En + H2O = EtOH (Water taking the part of
the acid),
C5H10 + HO2C.CCI3 = C5H11O2CCCI3,
En + H2SO4 = EtHS04,
CH3C02Et = En + CH3CO2H
(A. Oppenheim and H. Precht, Ber. 9, 325, (1876).

Esters may be regarded as the olefinates of acids, just as

ammonium salts can be looked upon as the ammoniates of
acids. Just as ammonia combines with salts such as PtCU,
CaCl2, etc., to form ammoniates, so may olefins combine
with salts to form olefinates. Compounds of this last
type have not been studied extensively, but the following
may be mentioned: (CH3)2C CHCH3.2ZnCl2 (from iso-
:

butylene and zinc chloride) [J. Kondakow, J. pr. Chem.

(2) 48, 474 (1893)]; C2H4.PtCl4 [V. Meyer and P. Jacobson,

Lehrbuch der organischen Chemie, Vol. 1, p. 832 (1907)];
etc.

So-called "anomalous" olefinates, which contain a dif-

ferent proportion of acid or salt than the 1 : 1 ratio are also

known. The zinc chloride compound just given is an

example; partially saturated poly olefins, such as the mono-
 c
OLEFINS AND THEIR REACTION PRODUCTS. 137

halogen addition products of terpenes as menthadienes,

belong to this group; ethyl ether may be looked upon as a
diolefinate of water; the compound (CH3)20.dH4 [G.
Baume and A. F. O. Germann, C.r. 153, 569 (1911)] may
be written (CH2)4.H20; C2H4.7H2O [R. de Forcrand, C.r.
135, 959 (1902)] is an example; a complex alkyl halide

>c —
CH3 /H
"^
CHo CI CH3
such as may be formed by the combin-
/CH3

C2H5 ^CHg
and one mole-
ation of several molecules of simpler olefins
cule of hydrogen chloride (Meyer and Jacobson, pp. 833,
836); etc.
Mixed addition compounds containing olefins have also
been described; for example, FeCl2.C2H4.H2O [J. Kachler,
Ber. 2, 510 (1869)]; FeBr2.C2H4.H2O [C. Chojnacki, Z.f.
Chem. 1870 p. 419)]; (CH3)20.NH3, an olefinate and am-
moniate of water, etc.
These reactions show the similarity between the olefins
and ammonia, and that the common property of unsatura-
tion in both leads to the formation of analogous products.
The simplest compounds which are formed from the
olefins are the alkyl halides, which correspond to the
ammonium halides. There is at present no direct experi-
mental evidence of the action of catalysts in their formation,
but in their dissociation into olefin and hydrogen halide,
aluminium chloride, zinc chloride, etc., affect the rate of
reaction greatly [P. Sabatier and A. Maihle, C.r. 138y 407
(1904); HU 238 (1905)]. This shows itself more particu-
larly in the lower temperature necessary for their rapid
dissociation. The alkyl chlorides dissociate more readily
than do the bromides, and these more readily than do the
iodides. Although no exact quantitative data regarding the
138 CHEMICAL REACTIONS.

velocities
may be considered
and equilibria of these reactions are at hand, they
to be analogous to the relative degrees of
{
dissociation of the ammonium halides studied by A. Smith
and co-workers [Jour. Amer. Chem. Soc. 87, 38 (1915)].
The action of certain substances such as alkalis in these
reactions will be taken up later in this chapter.
A further relation of the alkyl halides may be mentioned.
Under the same conditions, the primary halides dissociate
more readily than the secondary, and the secondary more
readily than the tertiary (Sabatier and Maihle, I.e.). In
the study of this reaction, no statement was made as to the
probable equilibria. [It will have been noticed that in the
discussion of organic reactions, the experiments often are
not definite or quantitative. This leads to uncertainty in
the theoretical treatment, as to whether a ready formation
of a compound refers to the velocity under certain conditions
or to the amount present under equilibrium conditions.
Careful regulation of conditions and quantitative working
are essential for the further development of the science of
reactions included in organic chemistry.] It is possible to
conceive of the tendency of the n-alkyl halides going over
into the iso on boiling, or of the formation of isopropyl
benzene from 7i-propyl chloride and benzene by the Friedel-
Crafts reaction, as due to the different equilibria of the
olefinand hydrogen halide with different sets of products
(normal, iso,and tertiary halides); the one which is found
experimentally depending upon the conditions of the various
equilibria, or the relative velocities of the reactions.
Connected with this is the reaction in which hydrogen
halide is added to an olefin, the halogen being finally com-
bined mainly with the carbon with least hydrogen; that is to
say, toform the tertiary compound preferably, secondarily
the iso-compound [A. Michael Ber. 39, 2138 (1906)]. An-
other example of the same kind is the formation of 2-brom-,
2, 2, 1, trimethyl ethane by heating 1-brom-, 2, 2, 2-
trimethylethane
 OLEFINS AND THEIR REACTION PRODUCTS. 139

CH3 CH3 CH3 CHg ^^Hg ^CHg

I^CH
^^3 = r
C +CHoBr
3 = I

C-CH3
H— C — Br y \H
I

H ^H
H
H
[L. Tissier, Ann. de chim. et de phys. (6) 29, 359, 361, 364
(1893)].
A general method, used very often practically, for the
preparation of olefins consists in the action of an alcoholic
solution of potassium hydroxide on an alkyl halide. This
reaction is analogous to the production of ammonia from
ammonium chloride and an aqueous solution of an alkali.
The equations for the latter are generally given as the
following:

NH4CI = NH4+ + CI, (1)

KOH = K+ + OH, (2)

NH4+ + OH = NH4OH, (3)

NH4OH = NH3 + H2O. (4)

Omitting the action of water in these equations, (1) and

(2) represent the ionization in solution. Equation (3)

shows the equilibrium between NH4 and OH ions and

un-ionized NH4OH. Equation (4) shows the equilibrium
between the last named substance and its dissociation

products, ammonia and water. Since the last reaction

takes place to a great extent to form the products of dis-
sociation, there will be a progressive action to form am-
monia, especially if it is removed from the sphere of action
by heat or in some other way, or if the concentration of OH
is very large, until, finally, all the ammonium chloride has
reacted to form ammonia. If the same explanation were
applicable to the alkyl halide, the following equations
would hold:
140 CHEMICAL REACTIONS.

C2H5CI = C2H5+ + CI,

KOH = K + OH,
C2H5+ + OH = C2H5OH,
C2H5OH = C2H4 + H2O.
This explanation is not satisfactory for olefins. In the
first place, no evidence is at hand indicating that the alkyl
halides ionize. One of the arguments advanced to meet
this criticism is that the solvent in the case of the formation
of the olefin not water and therefore the two cases are
is

not comparable. If water were used as the solvent, the

solubility of the alkyl halide would be so small that ioniza-
tion in solution could not be detected by any of the present
methods. On the other hand, very small concentrations of
ions can be detected experimentally. Most chemists, there-
fore,do not attempt to explain the reactions of alkyl halides
on the ionization basis. The two reactions, the formation
of ammonia and the formation of olefins, consequently are
considered to be quite different.
If the formation of ammonia from ammonium salts is
considered from the addition-dissociation and displacement
point of view, the two reactions become analogous. Upon
this basis the formation of ammonia may be indicated as
follows:

HCl Solution of the ammonium

NH4CI + nHaO = NH3 chloride. (NH4CI might be
(H20)„ written for NH3, HCl.)

HCl
HCl
[KOH NH3
NH3 + LH20)„ ]= (H20)n+m
(H20)„
KOH
[NHs
~ L(H20)p. ^ L(H20) n-\-m-
 :

OLEFINS AND THEIR REACTION PRODUCTS. 141

Or it may be represented according to the general type

reaction (chapter 5) as follows:

[(H20)^NH4C1] + KOH = [(H20):.NH4K0H]C1

= NH3+(H20).+i+KCl.
Similarly for the alkyl halides; in aqueous solution the
equations would be

[(H20)yC2H5Cl] + KOH = [(H20)^C2H5K0H]C1

= C2H4+(H20Ui+KCI
and in alcoholic solution:

[(C2H50H),C2H5C1] + KOH = [(C2H50H),C2H5K0H]C1

= C2H4 + (C2H5OH). + H2O + KCl.
It is true that this explanation appears to be more com-
plicated than the ionic explanation, but it has in its favor
the fact that more general, and unquestionably repre-
it is

sents more nearly the mechanism involved.

For most purposes it is not necessary to write the reactions
in such a complicated way, the following being sufficient:

KOH
KOH + C2H5CI = HCl = KCl + C2H4 + H2O,
C2H4
KOH
KOH + NH4CI = HCl = KCl + NH3 + H2O.
NH3
When potassium hydroxide is dissolved in alcohol, there
is likely to be some potassium ethoxide, KOC2H6, formed.

(It is incorrect to name compounds of this type alcoholates,

since alcoholates correspond to hydrates, while these com-

pounds correspond to hydroxides.) There is, therefore, a
possibility of the formation of ethers when alkyl halides

are treated with an alcoholic solution of potassium hydrox-

ide.
142 CHEMICAL REACTIONS.

C2H5CI + KOC2H5
C2H4
HCl
=
[h^5']
(or C2H5OH) + KCl + C2H4

KOH =
C2H4 [hS^'1
(«^ (C2H5)20) + KCl, etc
Another very interesting point in connection with the
reactions of the alkyl chlorides, bromides and iodides, is the
fact that the iodides show a tendency to give a larger yield
of olefin than do the chlorides in the presence of alkali
[A. Lieben and A. Rossi, Lieb. Ann. 158, 164 (1871)].
This is the opposite to what would have been supposed
from the behavior of the halides in the presence of catalysts
such as aluminium chloride. Furthermore, the chlorides
yield ether more readily than do the corresponding bromides
or iodides [M. Wildermann, Z. phys. Chem. 8, 661 (1891);
and S. Brussow, Ibid. 34, 129 (1900)].
All of these reactions depend very likely upon the relative
velocities of the various possible dissociations of the inter-
mediate addition compounds under the given conditions.
The reason why ordinarily mixed ethers of the type
C2H5ONH4 are not obtained is that they undergo dissocia-
tion at such low temperatures. If the alcohol-ammonia
mixtureis cooled sufficiently, these compounds are formed,

and may be isolated. For example, CH3OII.NH3 and

(CH3)20.NH3 (G. Baume and co-workers, J. de Chim.
Phys. 12, 216, 225 (1914)) belong to this type.
A reaction similar to that of ammonia and of the amines
is that by which olefins may be alkylated to form olefins
containing a greater number of carbon atoms. Thus,
amylene treated with methyl iodide yields hexylene and
heptylene [(M. Eltekoff, Ber. 11, 412 (1878); J. Lermontoff,
Lieb. Ann. 196, 116 (1879)].

C5H10 + CH3I = C6H12 + HI,

C5H10 + 2CH3I = C7H14 + 2HI.
 OLEFINS AND THEIR REACTION PRODUCTS. 143

The alcohols may be regarded as a group of compounds

similar to the alkyl halides in being olefinates of water in
place of acid, just as ammonium hydroxide is an ammoniate
of water. The formation of an alkyl halide from an alcohol
may therefore be looked upon as the displacement of water
by hydrogen halide.

[C2H4.H2O] + HCl = [C2H4.HCI] + H2O,

[NH3.H2O] + HCl = [NH3.HCI] + H2O.
The from those of the hydrogen
olefinates of water differ
halides in that the tertiary alcohols appear to lose water to
form the olefins more readily than do the secondary, and
the secondary more readily than do the primary. This is

the opposite to the order observed with the halides, but

whether this difference refers to the actual thermodynamic
stability or to the relative velocities under certain conditions
is not definite.
The formation of olefins from alcohols is similar to the
formation of ammonia from ammonium hydroxide:

[C2H4.H2O] = C2H4 + H2O,

[NH3.H2O] = NH3 + H2O.
The olefin formation is influenced very much by the
presence of other substances which act as catalysts. Sul-
furic acid is one of those most commonly used in this
reaction. The efficiency of the sulfuric acid in this reaction
is often connected with its tendency to combine with water,
or its dehydrating property. In the final products, it is

true that the elements of water have been removed from

the alcohol, but the mechanism of the reaction is un-
questionably not so simple. The continuous formation
of ethylene by running ethyl alcohol into warm sulfuric
acid; the formation of alcohol from an olefin and dilute
sulfuric acid [A. Butleroff, Lieb. Ann. 180, 245 (1876)];
the formation of alcohol from olefin and concentrated sulfuric
 CHEMICAL REACTIONS.

i
144

acid as well as the saponification of the ester formed

all speak against such a simple interpretation. Since ethyl
alcohol and and sulfuric acid, form
sulfuric acid, or olefin
ethyl sulfuric acid, Et HSO4, which breaks down, on heating,
into olefin and the acid, most textbooks state that the first
step in this reaction is the formation of this ester. Accord-
ing to the general theory of addition reactions advanced in
this book, the intermediate compound would be more com-
plex, and the ethyl sulfuric acid itself would be one of the
products of the dissociation. A number of equilibria may
be given to represent the possible dissociation products.
This list is not complete but will indicate the possibilities
of the reaction.

a EtOH + H2SO4 + (b-a)H20 (1)

(En)a ^^En H2SO4 + b HgO + (a-l)En (2)
=a.En + H8SO4 (HgOb (3)
(H20)b =a En + bHgO + H2SO4 (4)

H,SO, ^.aEna H^O + H2SO4 + H^O

(b^f) (5)

^^Eng. + (a-2) En + H2SO4 + bHgO (6)

Equilibrium (1) represents the reaction between ethyl

alcohol, sulfuric acid and water to form the intermediate
product; (2) the formation of the ethyl sulfuric acid; (3)
the formation of ethylene; (4) the formation of ethylene
and the simultaneous giving off of water; (5) the formation
of ethyl ether; (6) the formation of a polymer of ethylene.
All of these reactionshave been observed experimentally,
and the products actually obtained under given conditions,
depend upon these conditions and the principles of the
law of mass action. This list served to indicate the possi-
bilities for the quantitative study of a common reaction
presumably well-known.
If a different catalyst were used in the above reaction,
while the various equilibria would be identical in principle,
the products actually obtained under any set of definite
I OLEFINS AND THEIR REACTION PRODUCTS. 145

conditions might be different due to the specific action of

the catalyst on the different equilibria.. The action of zinc
chloride may be cited. With trimethyl ethylene, the com-
l)ound (CH3)2C : CH CH3.2ZnCl2 has been isolated. With
water it gives dimethylethyl carbinol, (CH3)2.C.CH2.CH3;
I

OH
with hydrogen chloride, tertiary amyl chloride; if heated
alone, diisoamylene [J. Kondakow, J. pr. Chem. (2) 4^,
475 (1893)]. Sulfuric acid and isoamylene under suitable
conditions yield diisoamylene also. This polymerization
reaction is used commercially in the formation of synthetic
rubber from the octadiens. The specific action of the
particular catalyst employed is shown also by the fact that
iso-propyl bromide dissociated at the temperature of boiling
amylene in the presence of asbestos, while the n-bromide
did not. [D. Konowalow, Ber. 18, 2808 (1885).]
Although liquid ammonia is an associated liquid [E^ C.
Franklin and C. A. Kraus, Amer. Chem. J. 21, 14 (1899)]
similar polymerization reactions have not been observed
with ammonia or amines.
The acetylene hydrocarbons may be studied from the
same point of view as the olefin hydrocarbon. They only
differ in the degree and amount of unsaturation.
It was shown that alkyl halides may be formed from
olefins and acids and may be looked upon as salts of the
hydrogen halides, or, as organic chemists have been in
the habit of calling such salts, as esters of the halogen acids.
In speaking of the alkylation of olefins, it was pointed out
that alkyl halides add to olefins, the alkyl radical playing
the same part as the hydrogen of the hydrogen halide in
such reactions. Zinc chloride facilitated the addition of
the alkyl halide to the olefin as J. Kondakow [J. pr. Chem.
S4, 452 (1896)] showed. He described the reaction as
follows:
146 CHEMICAL REACTIONS.
(CH»)2C : CH CH8+ Cl.C(CH3)2(C2Hj) + ZnCh
= (CH,)2C-CHCH«
01 0(OH8)202H,
+ ZnOlj.
As he did not examine the intermediate addition com-
pound of the three reacting components, but treated the
mixture directly with water, removing the zinc chloride,
he could not determine the action of the latter. He did
notice, however, that when the olefin-zinc chloride addition
compound was treated with hydrogen halide, the latter
replaced the zinc chloride and formed the corresponding
alkyl halide [J. pr. Chem. 48, 475 (1893)]. At higher tem-
peratures, large amounts of the polymerized olefin were
formed. These various reactions can be accounted for
on the basis of various equilibrium equations.
Many other salts have properties similar to those of zinc
chloride. Thus, G. Gustavson [J. pr. Chem. (2) 34, 161
(1886)] found that aluminium bromide formed a compound
with butylene, and the use of mercury salts for the hydra-
tion of olefins and acetylenes, etc., may be quoted. For the
further discussion of the addition of alkyl halides to olefins,
the reader is referred to the chapter on the Friedel-Crafts
reaction. Just as amines and ammonia react with acid
anhydrides and acid chlorides, so do the olefins. J. Konda-

kow [Ber. 27, Ref. 309, 941 (1894)] was able to bring about
the addition of these substances to olefins in the presence
of zinc chloride, etc. The external conditions must, how-
ever, be regulated carefully in order to obtain the desired
products; that is to say, to have the intermediate addition
compound dissociate along the lines of the necessary
equilibrium.
Since some of the oxides of nitrogen may be looked upon
as similar in constitution to anhydrides of oxygen acids, it is

readily understood why addition products can be obtained

from these oxides and the olefins. When nitrogen trioxide
 OLEFINS AND THEIR REACTION PRODUCTS. 147

is passed into a cooled ethereal solution of trimethylethylene,

amylene nitrosonitrite, (CH3)2 C — CHCH3, is formed.
I I

ON - O NO
A compound such as this is subject to tautomeric change
and polymerization. For further details concerning these
reactions, the reader is referred to books on the chemistry
of the terpenes.
When acids add to olefins, the olefinates formed may be
termed salts or esters. The formation of olefinates is

therefore one form of esterification similar in principle to

the formation of ammonium salts and of hydrates of acids
or oxonium salts. Similarly, the hydration of olefins to
form alcohols and ethers really belongs to the same class
of reactions, alcohols and ethers from this point of view
being esters of the acid water. So far the olefinates, the
alkyl halides, have been considered in some detail. Accord-
ing to the terminology in general use, these are esters formed
from organic alcohols and inorganic acids, the hydrogen
halides. The esters formed with organic acids will now be
taken up in the same way first, and then the general
question of esterification will be considered.
The formation of esters with organic acids has been
studied in detail with the olefin, amylene. This is doubtless
due to ease of manipulation and experimental technic in
general. The results with this olefin may be carried over
to other olefins, and the general principles will hold for all.
D. Konowalow [Ber. 18, 2808 (1885)] showed that gaseous
amyl acetate dissociated at 180° with appreciable velocity
when substances like asbestos, barium sulfate, glass wool,
etc., were present. N. Menschutkin [Ber. 15, 2512 (1882)]
had observed that this ester dissociated into amylene and
acetic acid, even in the liquid state at a comparatively low
temperature, and that the velocity of this dissociation
increased as the reaction proceeded. D. Konowalow [Z.
148 CHEMICAL REACTIONS.

physik. Chem. 1, 63 (1887)] showed this auto-catalytic

action to be due to the increasing concentration of acid
which was formed in the reaction, and that the stronger the
acid (the more highly ionized in aqueous solution) so formed,
the greater its action [Z. physik. Chem. ^, 6 (1888)]. Thus,
the amyl ester of trichloracetic acid dissociated more
rapidly than the amyl ester of acetic acid. The addition of
hydrogen halide also caused the dissociation of amyl
acetate, with the subsequent formation of amyl halide.
The equations showing these changes are as follows:

Am hI]+hx
HAc
HX
= Am + HAc+HX

W. Nernst and C. Hohmann [(Z. physik. Chem. 11, 352

(1893)] showed that in the reaction between olefin and acid
to form ester, the stability of the ester, as measured by the
equilibrium constant

^acid ^olefin -rr-

increased, and the value of the constant K decreased, with

the strength of the acid. Similar conclusions were reached
by J. Kendall Am. Chem. Soc. 36, 1722 (1914)] and
[J.

others. Nernst and Hohmann also showed that the velocity

of formation of amyl trichloracetate from amylene and the
acid was proportional to the square of the concentration of
the acid. In benzene as solvent, the velocity was greatly
increased, because of the association of the acid; in ether,
on the other hand, the velocity was less, the acid not being
associated in it. At the same time it is probable that the
ether and the trichloracetic acid form a complex, indicated
perhaps by the following equilibria:
 OLEFINS AND THEIR REACTION PRODUCTS. 149

AcOH"
rAcOH"! ^ ^ TAcOH] TAcOH
AcOH ^
,
"I

nEtaO
The influence of benzene and ether as solvents on the
velocity of the ester formation is similar to their influence
on the reaction between triethylamine and ethyl iodide
described in Chapter V.
Just as zinc chloride accelerates the reaction between an
olefin and water to form the alcohol and the reverse re-
action, so also does it accelerate similar reactions in which

an acid or an alkyl halide takes the place of the water.

J. Kondakow [J. pr. Chem. 48, 479 (1893)] found that when

zinc chloride was added to a solution of trimethylethylene

and acetic acid, an addition compound, CsHio-ZnC^.-
(H0Ac)3 crystallized out. Treated with water, this addi-
tion compound yielded amyl acetate. By altering the con-
ditions so as to obtain the maximum yield, that is, by
isolating this intermediate addition compound, and treating
it with water, Kondakow was able to obtain a 20 per cent,

yield of ester, although, ordinarily, in the equilibrium mix-

ture containing amylene, acetic acid, and amyl acetate,
only 2 per cent, of ester was present (Nernst and Hohmann).
If the reaction mixture was allowed to stand for some time
before water was added, a considerable amount of diamylene
was formed. The reaction may be formulated as follows:
XC5H10 + yHOAc + zZnCk
C5H10
(CsHio)^ = a + zZnCk
HOAc
(HOAc),
C5H10
(ZnCW. h
CfilTio
+ yHOAc + zZnCl2
(CsHio)*
(C6Hio)x
(HOAc)„ + nllaO = (noAc)v
(ZnCk).
KZnCk)..
(Il20)n
rzncin
"^
LlIOAcJ bw J
 :

150 CHEMICAL REACTIONS.

The other equilibria which are possible with these substances

are not given. They would be similar to the equilibria in
which sulfuric acid is present in place of zinc chloride, which
were given on a preceding page. In this reaction, the zinc
chloride plays the same part as the extra molecule of acetic
acid in the associated acetic acid in the formation of amyl
acetate, the only difference being that the zinc chloride
addition compound under the conditions of its formation,
does not form appreciable amounts of ester, but only when
treated with water. A. Behal and A. Desgrez [C. r. 114,
676 (1892)] have used this method for the formation of
esters of higher olefins.
Since the esters of organic acids are olefinates, it is clear
why, in the distillation of esters like the waxes, etc., where
a high temperature is necessary, olefins are often formed

C15H31CO2C18H37 = C15H31CO2H 4" CigHae.

So far esters have been considered only in relation to their

formation from olefins and acids. The usual method for
preparing esters consists in the action of an alcohol on an
acid in the presence of a catalyst. The mechanism of this
reaction has been studied extensively in recent years, and
all the evidence indicates the formation of intermediate
addition compounds in the reaction. The most direct
evidence of the existence of such intermediate compounds
composed of alcohol, acid, and catalyzing inorganic acid
was given by G. Baume and G. P. Pamfil [J. Chim. Phys.
12, 260 (1914)] and by J. Kendall and J. E. Booge [J. Am.
Chem. Soc. 38, 1712 (1916)]. Kinetic studies by J. Stieglitz
and by H. Goldschmidt showed that addition products
must be assumed to be present in the reaction mixtures,
but the exact nature of these products could not be deter-
mined.
From what has been said of the mechanism of reactions
so far, it may be stated that esterification from the point
 :

OLEFINS AND THEIR REACTION PRODUCTS. 151

of view of the addition theory may be placed in parallel

with the neutralization of an acid by a base. Both reactions
belong to the general type of reaction given earlier:

AnMX + H2O = AnMHaOX = A„MOH + HX

<r- I
> II
^III
< IV
< V
I. Neutralization; II. Hydration; III. Hydrolysis or dis-
sociation; IV. Dehydration or dissociation; V. Addition.
In the formation of a salt from an acid and a base accord-
ing to I, the reaction would be:

HA + MOH = r^A^l = MA + H2O; (a)

and in the formation of an ester from an acid and an

alcohol, the reaction would be

HA + ROH = [Ia^I = RA + H2O. (6)

The presence of a third substance which is capable of

forming addition compounds with the reacting components
may accelerate greatly both sets of reactions. In (a),
water serves the purpose, and acts therefore as the catalyst
for this reaction; in (6) some other substance such as
sulfuric acid or hydrogen chloride may produce a similar
effect. The formulations, including the catalysts may be
given as follows:

nA + c...-[^*], R0H + C...-[5^],

IIA+Cat. HiO+Cat,
11
152 CHEMICAL REACTIONS.

For the particular reactions in question, these would

come: For (a)

HA + H.0 =
[2oh] ^ MOH + H.O = LHOH
[^J|] ,

rHA [MOHI -1
HA rH20
"^ MOH Lma I+2H2O
LhohJ LhohJ 2H0H --MA+HzO
(dehydration, if MA is insoluble, etc.).
For (6)

HA+HCl=[S^j], R0H + HC1=[™],

HA
ROH fRA
1 +
J~ 2HC
LHCiJ"^ Lhci LhciJJ Lhci J'
HOH
[|^J=RA+HC1, [HCl + ROH PJ+H.O.
Since the neutralization of an acid by a base takes place
practically instantaneously, and since this reaction has
been explained in past years as due to ions, rapid reaction
has been taken to be a characteristic property of ionic
reactions. Other reactions in aqueous solution have also
been taken to bear out this view. It was shown previously
how the addition theory explains the neutralization reac-
tion; the same explanation applied to esterification shows
the advantage of a common viewpoint for the two sets of
reactions. The differences in velocities of the two may be
explained as due to the difference in efficiency of the two
catalysts, water and acid, which is in turn related to the
formation of the intermediate addition compounds and
their properties.
In the formation of esters in absolute alcohol, it has been
found that salts such as zinc chloride increase the formation
of esters especially when hydrogen chloride is also present.
This is one of the common methods used in esterification.
R. Engel (cf. Werner, p. 113) pointed out that the addition
 :

OLEFINS AND THEIR REACTION PRODUCTS. 153

of one molecule of hydrogen chloride to a molecule of zinc

chloride caused at the same time the addition of at least
two molecules of water to form the compound ZnCkHCL-
2H2O. Just as with the platinic chloride compounds with
hydrogen chloride or water or both, hydrogen is found in the
outer zone. Since water and alcohol are very much alike
in many respects, it is possible that where absolute alcohol
serves as the solvent, the salt effect of the zinc chloride is

similar to the salt effect in aqueous solutions.

For the further discussion of similar reactions, the reader
is referred to Chapter VI. In general, the term hydrolysis
is taken to mean the decomposition of a substance by
water. Since water is one of the products in the formation
of esters from alcohols and acids, hydrolysis becomes the
reverse reaction of esterification in this case. Therefore
what has already been stated concerning esterification
applies also to hydrolysis.
Since water is closely related to the alcohols, it is not
surprising that in certain reactions alcohols play a part
similar to that of water in hydrolysis. Thus, instead of:

En
^TEn 1
HOH + En.HA = HA
LhohJ +
HA,
HOH
the following may be written:
En
En
EnHOH + EnHA = HA
HOH -[Soh]+ha
and, as examples of such reactions may be cited

EtOH + EtI = EtOEt + HI,

CHs.COOCbHii + CH3OH = CH3COOCH3 + CgIThOH.

Among other methods used in the formation of esters may

be mentioned the acylation of alcohols by means of acid
 154 CHEMICAL REACTIONS.

chlorides and acid anhydrides. These reactions really be-

long to the same type as the others, as can be seen from the
following equations: (Cf. D. Konowalow, Z. physik. Chem.
U 67 (1887))
ACl = AOH.En + HCl
ACl + EnHOH = En
HOH = EnHCl + AOH
It is is only an alcoholysis of the acid
evident that this
chloride,and corresponds to reaction III above. In a
great many cases alkali aids in the formation of esters by
this method. This corresponds to the addition of alkali
to an aqueous solution of a salt to aid its hydrolysis. The
latter is generally explained on the ionic basis as due to
increasing the concentration of 0H~. It might, however,
be explained equally well by the formation of the inter-
mediate addition compound, which then dissociates into
water, and the salt of the acid and alkali used. In other
words, it favors the equilibrium for hydrolysis, by removing
the acid as fast as it is liberated.
When acid anhydrides are used instead of acid chlorides,
the acid group, OOCR, plays the same part as the halide in
the acid halide. What has been said with regard to acid
halides and their alcoholysis, applies also to the anhydrides
and their alcoholysis. m
Instead of alkali, other substances such as pyridine,
quinoline, aniline, etc., may be used. In the case of these
substances, experimental evidence shows that the pyridine,
for example, combines with the acid halide. The simplest
way of writing the reaction taking place would be:

En
rEn -1 HOH ^TEn rPy I -I
ACl + Py =
LhohJ + ACl LhoaJ^ Lhcij
LPy
Acid chlorides, etc., of inorganic acids also react with

Jl
 OLEFINS AND THEIR REACTION PRODUCTS. 155

alcohols to form esters of the acid or of the hydrogen halide.

The reaction between alcohols and phosphorus halides are
examples of this kind.

En = rHOPCl.-|^jjCj
[HOHI -l

LEn J
HOPCI2 + HCl, HOH
PCl7J = H0PCl.+[S"J'
PCI5 + PhOH = Cl2P(OPh)3

(W. Autenrieth and A. Geyer, Ber. 41, 146 (1908)),

ROH + PCI5 ~> ROPCI4 + HCl

ROPCI4 -> RCl + POCI3
(W. Anschutz and W. 0. Emory, Lieb. Ann. 253 120). y

The reaction between aluminium chloride and alcohols is

similar in character, as follows:

AICI3
rAl(0H)3l
AICI3 + SEn.HOH 3En
LEn3
+ 3HC1;
3H0H J
etc.
The formation of ethers may be considered from the
same point of view as the formation of esters. This was
indicated in connection with the reaction between ethylene
and water, with sulfuric acid as catalyst, where the produc-
tion of ether was shown in one of the equilibria. The
reaction between alcohol and sulfuric acid to form ethyl
sulfuric acid, and then, with more alcohol, ether, is also of
historical interest.
Thcreactions between ethylene, water, and sulfuric acid,
in which it was shown the products which may be formed,
were given on a previous page and need not be repeated
here. Ether is formed according to equilibrium (5), if

the external conditions are suitable, and the substances

present in suitable concentrations.
The graphic formula for ether is based mainly upon the
156 CHEMICAL REACTIONS. I
proof of the structure for alcohol as ROH. The latter
rests upon the proof that one atom hydrogen acts of
differently from the rest when treated with a metal like
sodium, and that a hydroxyl is present, as shown by treat-
ment with phosphorus halide. As shown in a former chap-
ter with acids, tautomerism is possible and the alcohol

may react in the form ^C=*^0 just as acids do.

Ionization is not probable for this compound, since posi-

tive hydrogen is combined with carbon predominatingly
negative.
This brings up the question of the structures of organic
acids, which, while not pertinent to the subject under dis-
cussion, still may be interpolated in this place. Up to this
point, the acyl group in organic acids has been treated as
a unit and generally indicated by the letter A. The re-
semblance of acyl halides to alkyl halides in their reactions
with amines and alcohols, etc., the similarity between
ethers and esters, and between amines and amides, points
strongly to a similarity in chemical makeup or constitution.
This relationship can be most simply expressed or accounted
for by considering the organic acids as water which is not
only olefinated, as in the case of alcohols, but as also having
carbon monoxide combined with it, and thus giving them
"CO '

the structure HOH , the carbon monoxide being an un-

_En
saturated compound like water, olefin, ammonia, etc. Be-
cause of tautomeric changes within these addition com-
pounds, just as in the hydrates and ammoniates of platinic
chloride and the oxygen acids, sulfuric and nitric acids, the
atoms may occupy different positions in the molecule.

CO O O
HOH .En^-^ = ^H^
0= C^H
II II

En , C^OH ^En
(i)^ (2) (3)
 OLEFINS AND THEIR REACTION PRODUCTS. 157

Formula (2) corresponds to the structure which is used in

organic chemistry at present, the proof for which is out-
Meyer and Jacobson's Lehrbuch der organischen
lined in
Chemie ((1907) Vol. 1, p. 76) and other textbooks. The
reactions cited in this proof of structure may in general
be applied equally well to all three structures. The con-
sideration of the three structures shows a closer relationship
between organic acids and inorganic acids than does struc-
ture (2) alone.
Carbon monoxide bears the same relation to formic acid
that sulfur trioxide bears to sulfuric acid, or that platinic
chloride bears to chlorplatinic acid, etc. Carbon monoxide
also bears the same relation to the higher organic acids
such as acetic, propionic, etc., acids that sulfur dioxide
bears to the sulfonic acids, or that the anhydride of nitrous
acid bears to the nitro compounds, etc.

V
.

Hy\ OH
V
O. O

tl
En En En
Organic acid Sulfonic acid Nitro compound.

Furthermore, by the aid of these structures, it is possible

to recognize the relationship between acid halides, esters,
amides, and the acids themselves, more readily:

HOHi rncn rnoHEni rNHa

CO CO CO CO
En En En En
or
CO CO CO CO
/\ /\ /\ /\
Enll OH Enll CI EnH OR Enll NII2
acid chloride cater aniido

Formic acid from the other acids of the organic

differs

series in being simply hydratcd carbon monoxide. This

158 CHEMICAL REACTIONS.

structure for formic acid agrees with all the properties of

the acid. It is not at all surprising that its dissociation into
carbon monoxide and water is effected by catalysts such as
hydrochloric acid, etc. (G. E. Branch, Jour. Amer. Chem.
Soc. 57, 2316 (1915)), since an addition reaction, similar
it is

to the formation of ammonium chloride from ammonia and

hydrogen chloride. The explanation for the decomposition
of formic acid into carbon dioxide and hydrogen is evident
from formula (3) for acids given above.
H
V O
= Ho + COc

This reaction involves oxidation-reduction and will there-

fore be discussed more fully in a later chapter. The other
organic acids, such as acetic acid, etc., behave in the same
way when heated with concentrated sulfuric acid, or in
some cases when heated alone [W. Oechsner de Coninck,
C. r. 136, 1069 (1903)].

CH3COOH = CH4 + CO2

EnH O
C^ == EiiHg + CO3

Aromatic acids can also be included under the structures

given. With them, the phenylene group plays the same
part as the olefin with the aliphatic acids.
Oxalic acid would have the following structure; that of
a mixed acid similar to dithionic acid.

CO "SO2 1

HOH oxalic acid. HOH dithionic acid

CO2 SO3
This indicates the dissociation of oxalic acid into carbon
monoxide and carbon dioxide, and of dithionic acid into
sulfur dioxide and sulfuric acid.
 OLEFINS AND THEIR REACTION PRODUCTS. 159

If the explanation of the relation between alcohols and

ethers is accepted, it becomes easier to understand alkyl
compounds and their reactions in general. They fall into
the same class as the ammoniates and the hydrates, and
may be called olefinates. Alcohol and ether are water
olefinated to different degrees. Their constitutions may
be expressed as follows (01 : olefin) : Alcohol, Ol.HOH;
ether, OI2.HOH; alkyl iodide, Ol.HI; ethyl sulfuric acid,
En.H2S04; etc. The reaction for the formation of ethyl
ether may be expressed as follows:

En
^TEn 1
En.HOH + Na = HOH + H,
Na L HONa J

En2
En.HONa + En.HI = HONa = [SSH]+Nal.
HI

This explanation indicates that the action of sodium

upon alcohol is sodium upon water,
really the action of
partially olefinated. The ethyl iodide upon
action of
sodium ethoxide is not the replacement of the sodium by
ethyl so much as the action of olefinated hydrogen iodide
upon olefinated sodium hydroxide. It is the same type of
reaction as the neutralization of sodium hydroxide by
hydriodic acid in aqueous The hydrated
solution. hydro-
gen iodide reacts with hydrated sodium hydroxide. The
water bears the same relation to the latter reaction that
the olefin does to the former.
The difference in properties of the various compoundated
hydrogens can be shown by a comparison of the following
compounds: ethyl iodide, ammonium iodide, and oxonium
iodide. Ethyl iodide requires the highest temperature for
its dissociation and the hydrate of hydrogen iodide the

lowest. This shows why hydrogen is evolved if a metal is

dissolved in an aqueous solution of an acid, or if a metal such
160 CHEMICAL REACTIONS.

as magnesium is dissolved in a solution of an acid such as

hydrogen chloride in liquid ammonia, while, if a metal
like sodium or magnesium is dissolved in an ethereal solu-
tion of an alkyl halide, the olefinated hydrogen is evolved.
(The ether in the Grignard reaction plays the same part as
the water in an aqueous solution of the hydrated hydrogen
iodide, the excess of liquid ammonia in theammoniacal
solution of theammoniated hydrogen iodide, and if it were
possible to have a solution of hydrogen iodide in liquid
ethylene, containing an excess of ethylene, this ethylene
would very likely act just as the solvent ether does.)
Ethers are generally spoken of as inert compounds.
What is meant is that they do not react with metals,
really
alkalies, and most acids at ordinary temperatures with
appreciable velocity. As pointed out, the properties of
the olefinated hydrogen afford an explanation. The same
holds true for tertiary amines. It has already been pointed
out that a difference is shown in the stability, or better,
the reactions of the olefinated hydrogen depending upon
the other substances present. Thus, in the presence of
chlorides, such as zinc chloride, etc., ethyl iodide reacts
less rapidly than the chloride. The same relative order was
observed with ammonium chloride, bromide, iodide, and
hydroxide. The decomposition of ethers by heating with
hydrogen iodide, a method used for the determination of
the amount of ether groups present in compounds, may be
explained on the same basis. They are simple displacement
reactions. The existence of the intermediate addition com-
pounds (oxonium salts) has been proven:

En2.H0H+HI= HOH LhOhJ LhiJ

.HI J = 2 ^jJ+HOH.
Other acids are capable of decomposing ethers. Concen-
 OLEFINS AND THEIR REACTION PRODUCTS. 161

trated sulfuric acid dissolves ether with the evolution of

considerable heat, and the mixture is heated for some
if

time at 100 degrees, ethyl sulfuric acid and ethyl sul-

fate are formed. Also acid chlorides react similarly with
ethers.

[nro]— flJ=[r]+[r]-
HOH
The reaction
/CH3CI + CH3COOC5H11
2CH3OC5H11 + 2CH3C0C1^
CfiHnCl + CH3COOCH3

may be quoted as example (F. Wedekind and J. Hausser-

mann, Ber. 34, 2081 (1901)).
The amines differ from the ethers and alcohols in that
they are olefinated ammonia or ammoniated olefins. What
has been said with regard to ethers and alcohols applies
also in a general way to the amines. Primary and secondary
amines correspond to the alcohols while the tertiary amines
correspond to the ethers. Because of properties of the
aminated compounds or ammonium salts as compared with
the oxonium salts or etherates these two series of com-
pounds as a rule are looked upon from entirely different
standpoints. With the nitrogen series, the properties of
the central nitrogen atom of the aminates and ammoniates
predominate, while in the oxygen series the properties of
the olefinated hydrogen and also of the hydrogen with the
alcohols are more prominent than those of the central oxygen
atom. It is only in recent years that much attention has
been paid to the etherates and in general to the oxonium
salts.

Because of the properties of the ammonium salts and

aminates which permit of their existence under ordinary
conditions, it is much easier to show the mechanism involved
in the formation of amines, than in the corresponding
162 CHEMICAL REACTIONS.

cases of the alcohols and the ethers. It has been possible

to show the occurrence of the intermediate addition com-
pound at ordinary temperatures with the nitrogen com-
pounds, while with the oxygen compounds lower tempera-
tures, and the application of the principles of the Phase
Rule were necessary to prove the existence of such com-
pounds. The formation of amines from ammonia and
alkyl halides may be represented by the following equations,
which differ only slightly from the way A. W. Hofmann
originally expressed the reactions:

En 1 r-^ -,

En.HX + NH3 = NH3 =

[n"h.]
+ hx 1° amine.
HX
En2 "1
rEn2
En.HX + En.NHs NH3
LNH3J
+ HX 2° amine.
HX
Ens
En.HX + EnaNHa = NH3 -[nS.]+hx 3° amine.
HX
The acid of the alkyl halide plays the same part in the
formation of amines as it does in the formation of ethers.
This is emphasized in the formation of diphenylamine from
aniline hydrochloride and aniline

Ph2NH
or rNH3-|
+ NHaPh =
,

PhNHa.HCl
Pen2-|+[HClJ-
NH3J (Pen= Phenylene)
The reason for not considering the acid of the alkyl halide
to play this part in the formation of ethers, is to be found
in the intermediate addition compound, the alkyl am-
monium which combines with the acid so that under
salt,

ordinary conditions the latter is not liberated and allowed

to go through the cycle again. Even in the formation of
the diphenyl amine where the intermediate compound dis-
 OLEFINS AND THEIR REACTION PRODUCTS. 163

sociates, the acid is taken up by the ammonia, and thus

prevented from acting as the catalyst. It will be recalled
that in the chapter on catalysis it was pointed out that
platinic chloride might act as the catalyst in the formation
of ammonium ammonia and hydrogen chlor-
chloride from
ide, if the conditions were such that the intermediate com-

pound dissociated and liberated the platinic chloride.

Since ethers may be formed from two molecules of alcohol,
and secondary and tertiary amines from two molecules of
amines of lower order it should be possible to combine
alcohols and amines. Such compounds have been formed
by treating alcohols with ammoniated zinc chloride (V.
Merz and K. Gasiorowski, Ber. 17, 623 (1884)).
ROH RNH2
or [NHs or ^TH^O 1
pn
En 1 + LZnCl2 [En + LznCkJ
"l
HOH
LHOHJ LnHsJ
H. Goldschmidt and C. Wachs (Z. physik. Chem. 24,
353 (1897)) showed that the formation of amides (anilides)
followed the same laws as the formation of esters. With
both, the reaction is bimolecular in the absence of a strong
acid, being autocatalyzed by the organic acid itself. The
amine plays the same part in the formation of an amide
as the alcohol in the formation of an ester. Instead of an
oxygen ester, a nitrogen ester is formed. The same relations
apply to both, and they may be formulated similarly.

En '

HOH
HOA_
En
HNH2
AOH
If the catalyst is taken into account, the following equations
may be given: If no strong acid is present:
 :

164 CHEMICAL REACTIONS.

I
En
[En l.fHOH 1
= HOH
[Soh] +
(hoa)„
.(HOA)n
-LHOAj + L(HOA)n-iJ'
En
= NH3 [En "1 [HOH 1

[nh3] +
(hoa)„ =
LH2NAj'*"L(H0A)n-iJ*
L(HOA)„J
With an acid HX present:
En
En
HOA
[En [HOAl
"1 HOH En
LhohJ "^ LHX J HOA HOA ^
moH-i
HX HX LhoaJ

[£]"-'-
En
[En [HOA] "] HNH2 En
Lhnh2J"^Lhx J HOA [ H2NA ]+[r]-
HX
Amides may also be formed by other methods similar to
the methods used for the acylation of alcohols, that is, with

acyl halides and acid anhydrides

En
En
HNH2
ACl
ANH ] + HCl,
~En
En
+ A(OA) - A(OA) 1 + HOA.
U"J NH3
ANH2

The formation of amides from ammonium salts of oxygen

acids is in fact only a part of the dissociation of the inter-
mediate addition compound in amide formation from an
amine and an acid. The formation of amide from ester
and ammonia is similar to the formation of amide from
 :

OLEFINS AND THEIR REACTION PRODUCTS. 165

amine and acid except for the olefinated acid in place

+ ANHo
En

of the acid
AOH = HOH + n
I^hJ
[En

HNHg
+ AOH
Amides may be hydrolyzed and saponified just as esters.
This is only the reverse reaction to their formation. Just
as with the esters, amides may also undergo alcoholysis.
The reactions are as follows:

En
l-En 1
ANH2 + ANH2
LHOHj HOH
(Meyer and Jacobson, p. 609),

En
[En rEn' 1 En'
+
LhoaJ LhohJ
"^ HOA LhoaJ + lhohJ*
HOH
etc.
 CHAPTER IX.

OXIDATION-REDUCTION.

In the last four chapters a number of chemical reactions

were taken up and classified according to certain principles
laid down in the earlier chapters. In Chapter V, the
general consideration of reactions was outlined and some
of the principles elaborated. Chapters VI and VII con-
tained a classification of reactions based upon certain
general types of chemical change, the actual substances
taking part being subordinated to the general scheme.
In
Chapter VIII the point of view was shifted in that the
change in composition of the substances reacting was
emphasized. The various reactions, considered before from
the standpoint of type of reaction were here developed from
the position of the reacting substances, and as the special
group of substances chosen, the chemical changes undergone
by the olefins were outlined. In these four chapters, how-
ever, one important limitation was introduced. In the
reactions and compounds which were taken up, none of the
atoms in any of the molecules changed its state of oxidation.
This limitation excluded all oxidation-reduction reactions
which will be taken up in this and the following chapters.
It seems advisable first to define and describe the phe-

nomena and reduction from the newer chemical

of oxidation
viewpoints, and then to apply these definitions and descrip-
tions to a number of reactions.
The valence of an element is defined as the number of
negative electrons an atom of that element loses or gains
to form chemical linkings. Stated in somewhat different
terms, the valence of an element may also be defined as the
number of equivalents of the acidic or of the basic con-
stituents combined with, or associated with, one formula
166
 OXIDATION-REDUCTION. 1 67

weight of that element. The symbolism used heretofore

in this book and which applies with the first definition will
be used here as well. The production of every chemical
linking involves the loss of (at least) one electron by one
atom and the gain of (at least) one electron by another
atom. The formation of this linking will therefore involve

a simultaneous oxidation of one atom and reduction of the

other. Thus, starting with a neutral hydrogen atom and a
neutral chlorine atom, in order to form a molecule of
hydrogen chloride, the hydrogen atom loses a negative
electronand acquires a positive charge, and the chlorine
atom gains a negative electron and acquires a negative
charge.
Some of the arguments in favor of such a polar view of
valence have been given in the first chapter. The conclu-
sions with regard to such charged atoms were not specially
emphasized in the reactions described in previous chapters,
but it is evident from what has been said already, that the
valence of an atom or the nature of its electric charge is of
paramount importance and significance in oxidation-reduc-
tion reactions. Change of valence is the significant feature
of oxidation and reduction; the participation of oxygen or
hydrogen as such has nothing necessarily to do with the
reaction.
The actual charge or valence of an atom in combination
is of importance in the reactions to be considered, and
when, under certain conditions or by various treatments,
the valence is changed, the mechanism of the reaction
involving such a change is of interest. These questions are
fundamental and will be considered in detail as occasion
arises.

The experiments described in Chapter I showed that in

any oxidation-reduction reaction involving electrolytes,
that for every mol of an element undergoing oxidation or
reduction, 90,500 coulombs of electricity or a simple

12
168 CHEMICAL REACTIONS.

multiple of this quantity are involved. This holds true

for organic substances undergoing oxidation or reduction
as well as for inorganic substances, as long as the substance
can be brought into solution and satisfactory electrical
measurements made. (A practical method of illustrating
such changes is by means of the "Chemometer" described

first by W. Ostwald, Z. physik. Chem. 15, 399 (1894).)

In the equation for the change in free energy or the
chemical affinity of a reaction as stated in Chapter I,

A^RT log. '',:/' - RT log. K,

O2
Li • • •

if the electromotive force of a galvanic cell in which the

current is produced by the chemical reaction isdenoted
by E, and one gram equivalent of the substance in question
is transformed, then
E= A,

under similar conditions of reversibility, etc., under which

A may be measured, using suitable units. W. Nernst de-
veloped the osmotic theory of current production, showing
the mechanism by which the chemical reactions produced
the electric current. Thus, the difference in potential of
two solutions containing univalent ions of a completely
ionized electrolyte of concentration rii and n^ with mobilities

of cation and anion equal to u and v (motion under a

definite potential gradient) is given by the equation

£ = ^^J^7•log.^.
Vu-f- rii

In an analogous manner, for the solution of a metal in a

solution of its salt, E = RT loge Pip when one gram
equivalent of the metal acting as electrode is dissolved,
in which P represents the electrolytic solution tension of
the metal, and p the osmotic pressure of the univalent ion
 OXIDATION-REDUCTION. 169

of the metal in the solution. In place of the pressures,

P and p, the corresponding concentrations, C and c, may
be used. Similar relations may be developed for negative
ions and elements. A comparison of the electromotive
forces developed, for example, with metals and solutions of
their ions will show the relative oxidizing or reducing
potentials of these elements; that is, the chemical aflfinities
with which these elements enter into chemical combination.
As pointed out before, an element entering into chemical
combination forms definite chemical linkings, that is to say,
gains or loses electrons. These electromotive force values
are fundamental therefore for studying the chemical affini-
ties of the simplest reactions. The theoretical and experi-
mental developments of W. Nernst have made possible
the quantitative study of the phenomena postulated by J.
Berzelius more or less definitely in his electrochemical
theory. N. T. M. Wilsmore (Z. physik. Chem. 35, 291
(1900)) calculated from the best data available the relative
electromotive forces shown by a number of elements as
electrodes against solutions containing normal concentra-
tions of their ions. These are known as the decomposition
potentials and are based upon the value of hydrogen as
zero. These values can be used to determine the replace-
ment of metals, etc., by each other, the electromotive forces
of galvanic combinations, etc. They apply directly to the
concentrations indicated. For other concentrations some-
what different values must be used.
The quantitative theory of electromotive force produc-
tionand its relation to chemical combination outlined very
brieflyand superficially (for more exhaustive treatments
the reader is referred to suitable text books on physical
chemistry) may
be extended to chemical phenomena in
general, in the same way that the experimental measure-
ments of valence on the basis of the ionic theory of solutions
were extended and elaborated in the electron conception of
170 CHEMICAL REACTIONS.

valence to include all chemical compounds. Evidently

this comparison is deep-seated. Since all chemical com-
pounds are formed by the transfer of electrons producing
the linkings, the atoms are all charged electrically in these
compounds. The chemical affinity may then be con-
sidered to be given by the aiBfinity of the given atom for an
electron under the conditions pertaining to that compound,
or in other words by a value which might be said to corre-
spond to electric potential in electromotive force measure-
ments. These electric potentials are not as yet susceptible
to quantitative measurement in the same way as the electro-
motive forces in galvanic cells, but the principle is similar
and the chemical affinity of a given combination may be
expressed as electromotive force or electric potential, or
more in conformity with the valence views used, an electron
potential. This electron potential of an atom in combina-
tion will manifestly be different in different compounds,
just as the electromotive force of an element is different in
different combinations of solvent, etc. The electron poten-
tial cannot be measured quantitatively at present as already
stated except in isolated cases, but it can be used in a
qualitative sense in a classification of reactions. Recalling
the definition of oxidation and reduction, it is plain that
for electron potential when used to compare different sub-
stances, may be substituted relative oxidizing and reducing
potentials, or what amounts to the same thing, the affinity
of the element for the electron under the given conditions.
The theoretical developments outlined apply to all chem-
ical compounds and reactions. The next step will be to
study the distribution of the valence electrons in a molecule,
or the valences of the different atoms in a molecule. A
clear understanding of these valences (positive or negative)
is necessary for the formulation of compounds on the basis
of the electron conception of valence, just as fifty years
ago the arrangement of atoms in a molecule and their
 OXIDATION-REDUCTION. 171

linkings formed one of the outstanding problems in chem-

istry. The reactions of the various substances preferably
with simple reagents at that time formed the basis for the
elucidation of the structures, the valences of the atoms
then forming the general underlying groundwork for further
developments. The combined study of the valences and
the reactions together with the underlying principles re-
sulted in the great growth of structural chemistry.
The same general method must now be used newer in the
developments of chemical structures involving the electron
conception of valence. On the basis of previous knowledge
and some fundamental assumptions (as few as possible)
definite rules of electron linkings may be These
developed.
will then be used in connection with certain simple chemical
reactions, and the structures modified when necessary.
In this way by correlating the relations found by these
methods, certain rules for indicating structures will be
developed and then applied to classifying reactions. The
knowledge of the exact distribution of the valence electrons
was not absolutely essential to the reactions discussed in
the preceding chapters as long as there was no change in
this distribution involving oxidation and reduction. Since
oxidation and reduction reactions involve the change in
electric charge of certain atoms, a knowledge, as complete
as possible under the conditions, of the initial states of
oxidation of the atoms reacting, is essential. The remainder
of this chapter will be devoted to a review of some of the

principles of use in the determination of the electron struc-

tures, and in the following chapter will be presented a
number of oxidation-reduction reactions using the structures
developed.
In the first chapter, some of the fundamental principles

upon which the electronic structures of compounds may be

based were outlined. Thus, the older ideas of positive
and negative atoms and groups were shown to have attained
172 CHEMICAL REACTIONS.

a definite and precise meaning with the electron conception

of valence. The experimental determinations of trans-
ference numbers and conductances of ionized substances
were shown to be a direct method for finding some of the
charges on some of the atoms or groups. The arrangement
of the elements in the Periodic System of Mendeleeff is, in
part, an expression of the differences in the properties under
discussion, and probably serves as the most general method
for indicating the relative oxidation potentials of the differ-
ent elements under ordinary conditions. The atom of an
element of high oxidizing potential would, in forming a
chemical linking, receive a negative electron from an atom
of an element of low oxidizing potential, or, in other words,
elements of high oxidizing potentials are ordinarily negative
toward elements of low oxidizing potentials. The arrange-
ment of the elements in the Periodic System brings out
regularities such as the relative positive and negative
properties of the elements. In the horizontal rows, the
elements of larger atomic weights are negative toward
those of smaller, receive electrons to form chemical linkings,
possess higher oxidation potentials; in the vertical rows,
the elements of smaller atomic weights receive negative
electrons from those of larger atomic weights in forming
chemical linkings.
These regularities apply however only to the stable forms
of chemical linkings. It is readily conceivable that under
special conditions compounds will be formed in which the
linking is less stable and in which the negative electron is
transferred in the direction opposite to that of the stable
linking. This would be the case with elements whose
oxidation potentials, or aflBnity for negative electrons, do
not differ widely, or with elements with great inertia whose
velocity of reaction is slow so that they would exist for a
measurable time in unstable forms of combination. These
questions will be taken up again.
 OXIDATION-REDUCTION. 173

In order to determine the structural formulas of sub-

stances, physical or chemical
methods or both simultane-
ously may be used. The use of a physical method will
now be given in some detail. The linking of carbon with
carbon, in which partly owing to inertia to reaction, the
states of oxidation of the carbon atoms cannot be deter-
mined readily, is involved in these structures (cf. K. G.
Falk, Jour. Amer. Chem. Soc. 33, 1140 (1911)).
The structures of organic acids as deduced from their
ionization constants in aqueous solutions will be developed.
The ionization constants (K X 10^) of the acids as calcu-
lated from the Ostwald dilution law.

Kl-7)'
in which v = the volume in cubic centimeters containing
one mol of the acid, and y = the degree of ionization found
from the conductance ratio, will be used. Only those acids
will be considered for which a fairly reliable value of K has
been obtained. This eliminates the highly ionized acids
for which K
varies with change in concentration. The
data refer to 25°.
In considering the structures of the organic acids, it is

evident that the a-carbon atom (the one combined directly

with the carboxyl group) influences the ionization constant
of the acid to the greatest extent. A classification of the
acids will be given which depends upon the direction of the
valences by which this a-carbon atom is combined with the
other atoms in the molecule, or its valence, or its oxidation
potential. This divides the acids into four general classes
which may be formulated as follows:

I ^€.€0211; II ^C.COzH; III ^C.COzH; IV ^C.COill.

The carboxyl group is assumed to be negative to the a-

carbon atom and to exert practically the same effect on the
174 CHEMICAL REACTIONS.

valence throughout. The acids belonging to class I are

those in which three electropositive groups are combined
with the oj-carbon atom; those belonging to class II, two

electropositive and one electronegative; to class III, one

electropositive and two electronegative. The ionization
constants are found to increase in the order of the classes
I, II, III, IV. The acids represented by formula IV, such
as trichloracetic acid, are too highly ionized to give satis-
factory dissociation constants, and will not be considered
here.
This method of consideration differs from the ordinary
one, which attributes the variation of the ionization con-
stant directly to the nature of the neighboring atoms or
groups, in assuming that the influences determining the
magnitude of the ionization constant are the positions of
the electric charges on the atoms. These positions indeed
are determined by the nature of the adjacent atoms or
groups, so that the new view is to be regarded as a develop-
ment of the older idea, which serves to give it greater
definiteness. The influences exerted by the double or
triple bond, according to the newer point of view, are
made up additively of the influences exerted by the two or
three single bonds or valences. The groups combined with
the j8-carbon atom, or the directions of the valences of this
atom, doubtless influence the ionization constant; but as
will be seen, this influence is in most cases of small im-
portance when compared with the influence exerted by the
bonds of the a-carbon atom. The groups combined in the

7, d, etc., positions doubtless exert an influence on the

constants also, but this influence is negligible in the con-
sideration of this classification.
Although the classification depends primarily upon the
directions of the valences, the specific effect of certain
groupings may be great enough at times to exert a pre-
dominating influence and obscure the relations mentioned.
 OXIDATION-REDUCTION. 175

These which are unquestionably present with every

effects,

atom or group in an acid, are too small to be perceived with

the present methods of experiment and calculation and
therefore do not interfere when the acids are divided into
the general classes depending upon the directions of the
valences of the a-carbonatom except, possibly, in individual
cases. Acids which contain an amino group will not be
included in the discussion, and all acids containing sulfur
will be omitted as well.
Saturated Monobasic Acids. —In the aliphatic acids con-
taining only carbon and hydrogen in combination with the
carboxyl group, the arrangement of the bonds of the a-
carbon atom may as stated be represented by the formula
^C.C02H. The values of the ionization constant for these
acids vary between 0.0011 and 0.0020 and include the follow-
ing, arranged in the order of increasing values for the
constant : pelargonic, caprylic, caproic, isobutyric, heptylic,
isocaproic, butyric, valeric, ethylmethylacetic, isovaleric,
acetic, tetramethylenecarboxylic, and diethylacetic. The
following acids and their dissociation constants contain the
same bonds for the a-carbon atom as the acids just con-
sidered, but are substituted by halogens, hydroxyl groups,
phenyl groups, etc., in the jS-, y-, or d-positions: 5-chlor-

valeric, 0.0020; benzoylpropionic, 0.0022; hydrocinnaraic,

0.0023; levulinic, 0.0026; ^-hydroxy propionic, 0.0031; jS-

chlorpropionic, 0.008G; i3-chlorbutyric, 0.0089; jS-iodbuty-

ric, 0.0090; jS-brompropionic, 0.0098; and eleven substi-

tuted /3-hydroxypropionic acids, 0.0015 to 0.0045. To

these may be added phenylacetic, 0.0056, and hydroatropic,
0.0043, indicating that the phenyl group as a substituent
exerts an influence on the ionization constants of acids
similar to that exerted by the methyl, etc., groups. The
ionization constants for these acids arc less than 0.005
except for the three i3-halogen propionic and i)hcnylacctic
acids, and for these they are less than 0.01. The constitu-
176 CHEMICAL REACTIONS.

live effect is evident here, but is it not great enough to

mask the additive influence of the bonds (as will be seen
presently with the a-halogen substituted acids). For the
acids containing the grouping i:^C —
CO2H, the constant
may be taken in general to lie between 0.001 and 0.005 with
variations due to the constitutive effect of the substituting
groups up to 0.01 and possibly higher.
(The data for the acids refer to 25 degrees and were
taken from the results of the following observers: W. Ost-
wald, Z. physik. Chem. 8, 170, 241, 369 (1889); H. G.
Bethmann, Ibid., 5, 385 (1890); M. Berthelot, Ann. chim.
phys., (6), 23, 43 (1891); A. Crum Brown and J. Walker,
Lieb. Ann., 261, 116 (1891); J. Walker, Trans. Chem. Soc,
61, 696 (1892); P. Walden, Z. physik. Chem., 8, 433 (1891);
10, 646 (1892); F. Stohmann and C. Kleber, J. prakt.
Chem., 45, 475 (1892); A. Hantzsch and A. Miolati, Z.
physik. Chem., 10, 23 (1892); E. Franke, Ibid., 16, 482
(1895); H. Euler, Ibid., 21, 264 (1896); B. Szyszkowski,
Ibid., 22, 173 (1897); W. A. Smith, Ibid., 25, 194 (1898);
W. A. Bone and C. H. G. Sprankling, Trans. Chem. Soc,
77, 654 (1900); D. M. Lichty, Lieb. Ann., 319, 369 (1901);
W. A. Bone, J. J. Sudborough and C. H. G. Sprankling,
Trans. Chem. Soc, 85, 534 (1904); K. Drucker, Z. Physik.
Chem., 52, 642 (1905).)
The formula for the aliphatic acids containing a halogen
or similar (negative) substituent in the a-position may be
represented by ^C — CO2H. The acids belonging to this
class which have been studied are iodacetic, 0.075; a-
brombutyric, 0.106; ce-brompropionic, 0.108; bromacetic,
0.138; «-chlorbutyric, 0.139; a-chlorpropionic, 0.147;
chloracetic, 0.155; sulfocyanacetic, 0.265; cyanacetic,
0.370; and For acids of this
a, jS-dibrompropionic, 0.67.
class, the constant may be taken as lying between 0.1 and

0.4 unless modified very markedly by some constitutive

influence.
 OXIDATION-REDUCTION. 177

Few acids containing two negative substituents in the

a-position of the formula ^C — CO2H have been studied,
a, a-Dibrompropionic, 3.3, and dichloracetic, 5.2, are the
only ones for which data were found. Acids containing
three negative substituents in the a-position are too highly
ionized for the purpose in view and do not give a satisfactory
constant.
The constants for the acids so far considered may be
summarized as follows: For the grouping ^C — CO2H, less
than 0.01; for ^C - CO2H, 0.1 to 0.4; for ^C - CO2H,
greater than 2. Individual substituents modify these
values to a greater or less extent, but the differences be-
tween the three classes appear to be great enough to
enable a decision to be reached as to the structure of a
given acid in most cases.
A group of acids for which the constants lie between
those for the acids containing the groupings i^C — CO2H
and i^C — CO2H is known. This group comprises the
acids diisopropylglycollic, 0.013; lactic, 0.014; glycollic,

0.015; glyceric, 0.023; ethoxyacetic, 0.023; methoxyacetic,

0.034; mandelic, 0.042; phenoxyacetic, 0.076; andbenzilic,
0.092. The OR {R = H or hydrocarbon radical) is evi-
dently the reason why these acids occupy an intermediate
position between the acids containing no negative a-group
and those containing one. This OR group is generally
taken to have an effect similar to a negative group, and
would therefore be formulated ~^0R in the acids. Some
of the acids approach the values for acids of the class

^C — CO2IT, but for most of them the difference is so

large that it must be assumed that either the OR group

exerts a constitutive influence masking to a great extent
the effect of the bonds or that there is some action (such as

inneroxonium salt formation, similar to that taking place

with amino acids) between the ether or hydroxyl oxygen
178 CHEMICAL REACTIONS.

and the hydrogen or other part of the earboxyl group which

decreases the values of K for this group of acids as com-
pared with the acids containing a different negative substi-
tuent in the a-position, resulting in a constant of from 0.01
to 0.1. It may be pointed out, however, that the class to
which any given acid belongs may readily be ascertained
as the composition taken in connection with the dissociation
constant shows the structure of the a-carbon atom. An
acid such as trichlorlactic, 0.465, must be formulated
somewhat differently and probably is best represented by
CClg,^
the structure HO ^— C — CO^H , or intermediate JDctween the

;^C — CO2H and l^C — CO2H classes, just as lactic acid

is intermediate between the ;^C — CO2H and ^i^C — CO2H

classes.
Saturated Dibasic Acids. —W. Ostwald was the first to
point out that the constants obtained by his dilution law
for the organic dibasic acids referred to the first hydrogen
ion which was formed from the acid and that the second
hydrogen ionizes only in very dilute solutions, so that it

does not enter into the constant as ordinarily determined.

For some acids the second hydrogen begins to ionize appre-
ciably at a dilution of about 500 liters, but the constant as
determined experimentally in the usual way is found to
increase rapidly with the dilution when this occurs. A
study of the constants for the dibasic acids may therefore
follow the lines laid down for the monobasic acids by con-
sidering the earboxyl group containing the un-ionized
hydrogen as a negative substituent.
Malonic acid, from this point of view, is earboxyl acetic
acid, and should belong to the i^C — CO2H class. Its

constant is found to be 0.164. The following substituted

malonic acids, with their ionization constants, have been
measured: dimethylmalonic, 0.076; a, a-tetramethylenedi-
 OXIDATION-REDUCTION. 179

carboxylic, 0.080; isobutylmalonic, 0.090; octylmalonic,

0.095; heptylmalonic, 0.102; butylmalonic, 0.103; propyl-
malonic, 0.112; hexamethylenetetracarboxylic (1, 1, 3, 3),

0.12; isopropylmalonic, 0.127; ethylmalonic, 0.127; benzyl-

malonic, 0.151; allylmalonic, 0.154; ethylmethylmalonic,
0.164; j8-benzoylisosuccinic, 0.250; methylbenzylmalonic,
0.266. These acids evidently all belong to the class

^C - CO2H.
Two substituted malonic acids have been measured
which doubtless belong to the ^C — CO2H class; chlor-

malonic, 4, and a, a-trimethylenedicarboxylic, 2.1.

Succinic acid may be represented by the formula

(a)H02C - CH2 -> CH2 - C02H(iS).

If the a-hydrogen is ionized more easily than the /3, succinic

acid should belong to the ^C — CO2H class; if the /3

more easily than the a, to the i^C — CO2H class. A

study of the constants for succinic acid and the acids
derived from it, in which a hydrogen atom of one of the
methylene groups is replaced by hydrocarbon radicals
shows that the acids belong to the i^C — CO2H class

(analogous to acetic acid), the negative carboxyl substituent

in the jS-position exerting a constitutive effect similar to
that exerted by the halogens in the /3-substituted propionic
acids. The results for these acids are as follows: Succinic,
0.0068; isopropylsuccinic, 0.0075; asym. dimethylsuccinic,
0.0081; methylsuccinic, 0.0085; ethylsuccinic, 0.0080;

isobutylsuccinic, 0.0088; propylsuccinic, 0.0089; benzyl-

succinic, 0.0091 ; and allylsuccinic, 0.0109. The three acids,

bromsuccinic 0.278, chlorsuccinic 0.284, and sym. brom-
methylsuccinic 0.478, evidently belong to the ;;:^C — CO2H
class analogous to chloracetic acid and must be formulated
na=^C-COj,U
(for the first named as example) CU [
,
"» ^^'^»*'^'^^

n—^c-ccu
180 CHEMICAL REACTIONS.

each of the carbon atoms combined with a carboxyl has

gained two and lost one negative electron.
The higher homologs of the saturated dibasic acids may
be considered as derived from the higher fatty acids con-
taining a negative substituent which exerts only a minor
influence upon the ionization constants as compared with
the effect of the bonds. They should therefore belong to
the -*-C — CO2H class, and, in fact, the constants for those
measured are found to between 0.0022 and 0.0059. The
lie

following acids are included and are arranged in the order

of increasing values for K: Camphoric, sebasic, azelaic,
suberic, co, co'-dipropylpimelic, co, co'-diisopropylpimelic, n-
pimelic, w, co'-dimethylpimelic, oj, w'-diethylpimelic, adipic,
glutaric, w, oj'-dibenzylpimelic, a-methylglutaric, a, a!-
diethylglutaric, jS, /3'-dimethylglutaric, a, a'-dimethylglu-
taric, and jS-methylglutaric.
Unsaturated Acids. —The unsaturated acids will be taken
up same way as the saturated, and the double bond
in the
will be assumed to have the same effect upon the dissocia-
tion constant as if it were made up of two single bonds.
It will be seen that a perfectly rational classification follows
from this method of treatment and that the acids containing
a double bond between two carbon atoms fall into the same
groups depending upon the directions of the valences and
considering their influence as purely additive, as the
saturated acids. Caution must be used however with
regard to the data for some of the isomeric acids, as the
methods of isolating the pure substances had not been
worked out very satisfactorily when some of the measure-
ments were made. The following monobasic acids contain-
ing a double bond between the a- and i3-carbon atoms in
four cases and between the /3- and 7- in one case may first
be quoted: Methylethylacrylic, 0.0011; sorbic, 0.0017;
hydrosorbic, 0.0024; trimethylacrylic, 0.0039; and acrylic,
0.0056. These acids evidently belong to the -^C — CO2H
 OXIDATION-REDUCTION. 181

class, whether the a-carbon atom is combined with the

other atoms in the molecule by means bonds
of three single
or one double bond and one single bond.
In the case of the isomeric unsaturated acids, maleic and
f umaric acids may be considered in some detail, since these

substances were isolated in a state of purity early and

the measurements for finding the values of K may be con-
sidered to be accurate. Furthermore, the composition of
the two acids is simple and it should be possible to draw
perfectly definite conclusions. The ionization constant of
fumaric acid was found to be 0.093, and that of maleic
acid 1.17. The possible structures for these acids are
(a) CO2H.CH Zl CH.CO2H and (6) CO2H.CH i: CH.CO2H.
Since the ionization constants refer to one hydrogen ion
and the carboxyl group may be considered as a negative
substituent, fumaric acid from the value of its constant
should belong to the i^C — CO2H class and must be as-
signed formula (a). Maleic acid should then be repres-
ented by formula (6) . An acid of this formula can ionize
in one of two ways, either from the l;C — CO2H group or
from the i^C — CO2H group. The ionization constants
for the acids belonging to these classes differ widely, and
the value found for maleic acid, 1.17, shows that the ioniza-
by the first of the methods indicated. Maleic
tion takes place
acid may then be classed with dichloracetic acid, and fumaric
acid with monochloracetic acid in considering the ionization
of the first hydrogen.
The acids containing a triple bond can be disposed
of briefly, as few have been measured. Tetrolic acid,

0.246, is to be represented by the formula CIl3::;^C.C02lT,

and phenylpropiolic acid, 0.59, by the similar formula

C6H6C^C.C02lI.
Aromatic Acids. —The aromatic acids are taken to include
those in which a carboxyl group from which the hydrogen
 H

182 CHEMICAL REACTIONS.

is ionized is in direct combination with a carbom atom of the

benzene nucleus. This carbon atom corresponds to the
atom in the saturated acids, and the bonds of this
o:-carbon
carbon atom are the ones which determine the ionization
constant of the acid in question. It may be expected that a
greater constitutive effect is exerted by the benzene ring
on the constants. This is true to a certain extent as the
general arrangement (or directions) of the valences and
their influence upon each other between the carbon atoms
in the ring are not known, but the aromatic acids may be
grouped in the same way as the aliphatic acids and the
probable reciprocal influences of the bonds discussed with-
out specifying the particular directions of all the valences.
In general terms, the benzene ring is assumed to contain
alternate single and double bonds.
The ionization constant for benzoic acid was found to
be 0.0067. This indicates that benzoic acid belongs to the
3^C — CO2H class, and that its graphic formula is

COoH

H— C — C=^=C-^— !

H— C — C = C<—
, II I

t
H
the direction of the bonds indicated by dashes being un-
known. Other aromatic acids in which the directions of the
valences for carbon (1) are the same as for benzoic acid, but
for which the arrangement of the other bonds is unknown
except that no strong constitutive effect is manifested by
the two carbon atoms in position (2) and that therefore the
directions of the bonds in these are not such as would be
expected if only negative groups were combined with them,
are the following: p-Hydroxybenzoic, 0.0029; vanillic,

0.0030; isovanillic, 0.0032; anisic, 0.0032; veratric, 0.0036;

mesitylenic, 0.0048; m-toluic, 0.0051; p-toluic, 0.0052;
 OXIDATION-REDUCTION. 183

methylsalicylic, 0.0082; m-hydroxybenzoic, 0.0083; 1, 3,

5-dihydroxybenzoic, and p-chlorbenzoic, 0.0093.
0.0091;
The following acids may be assigned to the same class
as benzoic acid; m-fluorbenzoic, 0.0136; m-brombenzoic,
0.0137; m-chlorbenzoic, 0.0155; m-iodbenzoic, 0.0163; m-
cyanbenzoic, 0.0199; isophthalic, 0.0287; m-nitrobenzoic,
0.0345; o-toluic, 0.0120; p-nitrobenzoic, 0.0396; and 1, 2,
4-resorcylic, 0.0515. In the first seven of these acids, the
negative substituent in position (3) (or corresponding to
the 7-position in the aliphatic acids) apparently exerts a
constitutive effect on the constant comparable with some
of the effects exerted by negative constituents in the /3-

position of the aliphatic acids. This effect may be due

to the influence of the negative constituents on the direction
of the valences between the carbon atoms (2) and (3),
causing the valences for (2) to assume directions, which, if

present in aliphatic acids, would cause similar changes in

the constants. Similar reasoning may be applied to the
last three acids.

The following acids must be assigned to the ^C.C02H

class, and the probable structure of part of the molecule
CO^H
may be formulated as ^ j, ^^ : salicylic, 0.102; 1,2,
• • ••
5-hydroxysalicylic, 0.108; 1, 2, 3-hydroxy salicylic, 0.114;
o-phthalic, 0.121 ; o-chlorbenzoic, 0.132 ; o-brombenzoic,
0.145; m, m-dinitrobenzoic, 0.162; and o-nitrobenzoic, 0.616.
The only acid which appears to belong to the ^C.C02H
class is 1, 2, 6-resorcylic, 5.0.
These results show a method for finding the directions

of the valences or the distribution of some of the valence

electrons on the carbon atoms of the benzene ring, and the

possibilities of rearrangement of these electrons when
different groups are substituted for the hydrogens of the
benzene,
13
184 CHEMICAL REACTIONS.

Chemical methods can also be used to determine the dis-

tribution of the charges in a molecule, or the valence of the

atoms and should prove of more general applicability.
Although no one reaction can be chosen as an infallible
guide, the reaction which can be relied upon most frequently
is that involving hydrolysis (cf. T. Selivanow, Ber. 25, 3617

(1892); W. A. Noyes, Jour. Chem. Amer. Soc. 86, 769

(1913); etc.). In this reaction, when an atom or group is
replaced by a hydrogen atom or hydroxyl group derived
from water, unless there is very distinct evidence to the
contrary, it may be assumed that no change in the electrical
states of the atoms taking part in the reaction occurs. If

acid or base is present and accelerates the hydrolysis,

there may be a greater possibility of electrical change, but
still unless there is evidence to the contrary, no change may

also be assumed here. With substances containing single

bonds only, the oxidation potentials of the atoms should as
a rule be so different that only one form of the substance
is stable.
With compounds containing a double bond, the conditions
are not so simple, however. It is necessary to consider all
the possible cases and from a study of the reactions decide
which formula may be assigned to a given compound.
Taking up substances which contain a double bond between
two carbon atoms first, it is evident that these compounds
may in general be divided into classes: (1) compounds in
which the two halves of the molecule are similar; and (2)
compounds in which the two halves of the molecule are
dissimilar. To the first class belong substances of the types

CR, :::: CR^; CR2 1: CR2; crr' ::: crr'; crr' :: crr^
If two isomers any case, because of the difference
exist in
in valence of the carbon
atoms or their oxidation potentials,
one would be expected to be more stable than the other; if
only one substance of the general type exists, then it may
 OXIDATION-REDUCTION. 185

be that the other is too unstable to be formed permanently,

going over into the stable form, and
it would be a question

then to determine by means of the chemical reactions, to

which of the two types its reactions show it to conform
best.
Of substances derived from the formula CR2 CR2, none :

is known to exist in two forms. The directions of the

valences, or the charges of the atoms in the compounds of
this group might be determined by following some of the
addition reactions of closely related compounds. Since
the molecule is symmetrical, it makes no difference in the
resulting compound, in which way another substance, HI
for instance, is added. If however, as a typical example,
propylene CH3.CH CH2, is taken, there would be three
:

possibilities; MeCH CH2 and MeCH i: CH2 or MeCH

:;!:

tl CH2. On treatment with HI, if either of the last two

represents the structural formula, the I would all go to one
carbon atom, and the H to the other, only one substance
being formed; while if the first represents the structure,
a mixture of two substances should be formed, the H and I

being divided between the two carbon atoms. The reac-

tions in this case might be represented as follows:

MeCH :;:: CH2 = MeCHg -> CH2I and

H ->I
I <-H
MeCH ::: CH2 = MeCHI <- CH3.

The extent to which each of the products would be formed

would depend upon the influence of the methyl group as
compared with the hydrogen or the double bond, and upon
the difference in polarity between the hydrogen and iodine;
the smaller the difference the more nearly equal would be
the amounts of the two products formed. The following
results were obtained by A. Michael (J. pr. Chem. 60, 286,
409 (1899)):
186 CHEMICAL REACTIONS.

Propylene + HI formed principally (CH3)2CHI together

with a little C2H5CH2I.

Propylene + ClBr yielded 5 parts CHg.CHBr.CHaCl to 7

parts CHs.CHCl.CHaBr.
Propylene + ClI yielded 1 part CH3.CHLCH2CI to 4 parts
CH3.CHCI.CH2I.

Propylene + HOCl formed principally CH3.CHOH.CH2CI

and perhaps a little CH3.CHCI.CH2OH.

These examples indicate that the compounds belong to the

CR27^CR2 type, although propylene does not belong to
this symmetrical type. In general, therefore, if one form
exists, this formula is assigned to it, if two forms, the more
stable possesses this formula.
Of substances derived from the structure CRR' CRR' :

a large number of isomers are known, of which maleic and

fumaric acids may serve as examples. From what has
been said, the more stable, fumaric acid, may be assigned
the formula CRR':;1CRR', the less stable, maleic acid,
the formula CRR'ltCRR'. These structures agree with
the structures developed from the ionization constants of
acids.
With substances containing a double bond in which the
two halves of the molecule are dissimilar, there are a greater
number of possibilities with three possible isomers in each
case. The three isomers are not known for any one sub-
stance with certainty. The reason for this may be found
in the fact that if the two halves of the molecule are made
up of groups differing very much in properties, of the two
isomers in which the two valences act in the same direction,
one will exhibit very much greater stability than the other,
making it extremely difficult, if not impossible, to isolate
With compounds containing a double
the less stable form.
bond between two unlike atoms, the carbonyl group CO, :
 OXIDATION-REDUCTION. 187

for example, the valences assigned may be indicated as

: Cl^O, since the properties of the two atoms differ so
widely.
It must be pointed out that, although very good reasons
exist for assigning the structures indicated to the various
compounds on the basis of chemical reactions, the possi-
bility remains that the reagent added may itself cause or
influence the oxidation potentials of the reacting atoms, so
that the structures assigned may be due primarily to the
reagent used, and secondarily to the structure actually
present initially. Although this possibility does not appear
to apply in the great majority of cases, it must be pointed
out here, as unquestionably it does occur at times.
H. S. Fry, some years ago (Z. physik. Chem. 76, 387
(1911); cf. also L. W. Jones, Jour. Amer. Chem. Soc. 36y
1268 (1914); K. G. Falk and J. M. Nelson, Science, 46, 551
(1917)), denoted by the term electromerism the phenomenon
of electronic tautomerism, including substances structurally
identical, but mutually transformable by an exchange of
negative electrons between the atoms composing the mole-
cules. Thus, ammonium nitrate, NH4NO3, and hydroxyl-
amine nitrite NH3OHNO2, while mutually transformable
by a suitable exchange of negative electrons, since as far
as the charges on the atoms are concerned they differ only
in the valence or state of oxidation of the nitrate and
nitrite nitrogen atoms, are not structurally identical and
would not, therefore, be classed as electromers. L. W.
Jones applied the electromerism view to a number of com-
pounds of nitrogen in several papers published recently.
The conception of electromerism involves the isomerism
of maleic and fumaric acids, and in fact all isomerism
heretofore classed under cis-trans or geometrical isomerism,
without considering spatial relationships at all. Another
group of substances may also be included under elec-
tromerism. Werner has placed in parallel the so-called
188 CHEMICAL REACTIONS. I
geometrical isomerism of double bonded carbon atoms and
the isomerism due to plane configuration of certain cobalt,
chromium, and platinum compounds:

W ^X X/ ^R R/ ^X X/ \r

Whatever explanation is accepted for the double bond

isomerism, the same explanation will apply to the isomerism
of the platinum compounds. Werner considers that the
explanation of the spatial configuration applies to both.
On the other hand, if the double bond isomerism is due
to the directions of the valences, or the states of oxidation
of the atoms, or the distribution of the negative electrons,
then the explanation of the isomerism of the platinum
compounds should be based upon the distribution of the
electrons in the platinum atom. There is, however, only
one atom involved here, so that it appears as if this isomer-
ism would furnish a method for showing the distribution or
arrangement of some of the electrons in an atom. These
platinum and similar compounds would then belong to the
class of electromeric substances. Since this explanation
means that the spatial arrangements of atoms or groups
around a central atom depend primarily upon the spatial
arrangement of the valence and also other electrons of that
central atom, a further logical deduction would include all

optically active isomers in organic and inorganic chemistry

in the The spatial arrangements of
group of electromers.
of the atoms or groups here would also be governed or
controlled primarily by the arrangement of the electrons
of the atom showing the optical activity.
In developing the structures of the acids, it was shown
that the arrangements of the valence directions in the
benzene nucleus were different in different acids, or, in
other words, that the substituting group influenced the
 OXIDATION-REDUCTION. 189

valence electrons of the carbon atoms of the benzene

nucleus. The states of oxidation of these atoms were
different depending upon the substituting group. The
benzene nucleus, therefore, in different compounds contain-
ing various substituents acts as an electromeric substance,
and a number of reactions of benzene derivatives will un-
doubtedly be explained upon some such basis.
Considering the states of oxidation of the carbon atoms
of the benzene ring as changed and basing explanations
of reactions upon them seems more logical than the pro-
cedure of H. S. Fry, who more or less arbitrarily considers
hydrogen and chlorine to be either positive or negative
when combined with the benzene nucleus, and then bases
explanations of substituting and other reactions upon these.
While the explanations of Fry and of those using the different
charges on the hydrogen atoms may for the case of benzene
amount to the same thing and one view be no more advanta-
geous than the other, in studying chemical reactions in gen-
eral and building up a logical consistentsystem of chemical
theory, it seems better to treat of the hydrogen combined
with carbon as positive until direct evidence to the con-
trary is at hand, and to assign the changes in charges in

benzene derivatives to the carbon atoms.

 CHAPTER X.

SOME OXIDATION-REDUCTION REACTIONS.

The structures which have been developed in the last

chapter with special reference to the states of oxidation of
various atoms in molecules will now be applied to a number
of reactions. As in the other classifications given in this
book, emphasis is placed on the fact that the same principles
apply to both organic and inorganic reactions and that any
reaction in one branch of chemistry can be paralleled by a
reaction in the other branch. In oxidation-reduction re-
actions, certain simple principles may first be poitted out.
In these reactions, when an oxidation takes place, it is

always a particular atom which is oxidized. It is incorrect

to speak of a group or a molecule being oxidized, the change
actually taking place with one atom in the group or mole-
cule whose reactions are being followed and perhaps for this
reason giving the impression that the group of which it
forms a part is being oxidized. The same is, of course, true
for reduction. It is permissible to speak of a group as pre-
dominatingly positive or negative, but if the predominating
charge changes, it is because of the changes in the charges
of one or more of the atoms making up the group. If oxida-

tion takes place in a reaction in the sense that a given

atom loses one or more negative electrons, then it is neces-
sary that some other atom in one of the molecules taking
part in the reaction must be reduced (gain one or more
negative electrons) to a corresponding extent.
A simple reaction which may be mentioned first is that in
which a metal replaces another one combined as a salt.
For example, if metallic sodium is fused with magnesium
chloride, metallic magnesium and sodium chloride are

190
 :

SOME OXIDATION-REDUCTION REACTIONS. 191

formed according to the equation

2Na + MgCk = Mg + 2NaCl.

Such reactions are common in inorganic chemistry and
serve for the preparation both on a laboratory and on an
industrial scale of a number of metals. If this reaction

takes place in solution, as for example when zinc is immersed

in a solution of copper sulfate, forming zinc sulfate and
copper, while the formulation of the mechanism of the
reaction is not quite as simple as in the first case, the oxida-
tion-reduction changes are the same. Such reactions also
are very common, and are the source of electric currents
in galvanic cells using various combinations of metals and
solutions, the electromotive forces under certain conditions
being a measure of the affinity of the chemical reaction
taking place.
These simple and well-known reactions of inorganic
chemistry are paralleled in organic chemistry by the Wiirtz
and Fittig syntheses and the Barbier-Grignard reaction.

The Wiirtz and Fittig syntheses may be formulated in most

general terms as follows:

RX + R'Y+ 2Me = RR' + MeX + MeY, (1)

in which R and R^ represent hydrocarbon radicals (aliphatic

or aromatic) X andY halogen atoms, and Me a metal such

as sodium. The symbol Me signifies an uncharged or un-
combined atom of the metal. In the Wiirtz synthesis,
aliphatic hydrocarbon halide and sodium are used, as for
example
2CH3i + 2Na = IhCClh
(ox^)
+ 2Nai. (2)

In this reaction the neutral sodium atoms arc oxidized,

at the same time that a carbon atom of one of the methyl
iodide molecules is reduced two units of valence from
 192 CHEMICAL REACTIONS. I
— 3+1= — 2 to — 4. The analogy to the inorganic
reactions outlined is evident. In the same way, the Fittig
synthesis deals with an aromatic halide and an aliphatic
halide, as for example:

CeHfiBr + CgHsBr + 2Na = C6H5C2H5 + 2NaBr. (3)

The reaction is similar to the Wiirtz reaction, but the

distribution of the valence electrons or the charges on
the separate atoms are not known with the same certainty.
In these reactions, only the initial and final substances
have been indicated. It is possible that the actual mechan-
ism of the reaction is not so simple and that it takes place
in several stages. Evidence for this view is to be found
in an analogous reaction, in which magnesium is used in
place of sodium. This reaction can be used in a great
number of syntheses and is generally known as the Barbier-
Grignard reaction. The ordinary formulation is as follows:

RH-Mg=Mg<J^; Mg<J^+R'I=Mgl2+RR'. (4)

The presence of some solvent such as ether, dimethyl-

aniline, etc., is necessary for the reaction to proceed with
measurable speed or at all. Instead of a molecule R'l
taking part in the second step of the reaction, a great
variety of other substances may be used and various com-
pounds synthesized. The reader is referred to appropriate
text- and laboratory books of organic chemistry for these.
The formulation of equation (4) using the electron concep-
tion of valence would be as follows:

R—H-Mg=Mg(^ =Mg( Mg;_+R-I=Mg( +R R (5)

^R ^R \ V
(a)

The first action consists of the combination R+I~ and

atomic uncharged magnesium. The possible intermediate
 SOME OXIDATION-REDUCTION REACTIONS. 193

product (a) is given and may represent the first stage of

combination and perhaps be equivalent to a combination
such as would be produced by the force fields of Baly or
some similar view as discussed in some detail in an earlier
chapter. In the formation of the definite compound
++ ^I~
Mg\T»-> the magnesium has been oxidized two units of

valence and one of the carbon atoms of the group R reduced

two units of valence. The second step of the reaction
consists of a simple reaction involving ultimately an ex-
change without oxidation or reduction. As stated before,
a number of substances may take part here. The net
result is a reaction analogous to the reactions just described
with the added interest that intermediate products have
been isolated here which were not possible in other cases.
Because of these intermediate products, it has also been
possible to develop themechanism of such reactions some-
what and to bring out further analogies between
farther
inorganic and organic reactions (cf. in this connection
J. M. Nelson and W. V. Evans, Jour. Amer. Chem. Soc.

55, 82 (1917)). It was stated that ether or some similar

solvent was necessary for the Barbier-Grignard reaction
to take place. The ether takes part in the reaction and
undoubtedly forms onium (molecular) compounds with the
reacting molecules. It plays the same part in these re-

actions that water plays in the reactions involved in galvanic

cells. This is shown by the following measurements
clearly
of the resistances of a number of solutions:

Resistance in Ohms (Ordinary Conductivity Apparatus).

Ether above 1 X KF
Ether containing ethyl bromide above 1 X 10'
Ether containing 1.2 gmH. Mg as Grignard reagent
(MgCjHtBr) per 10() CO 7.1 X 10»

Same with 0.3 mg. Mg . . 1.0 X 10»

0.02 M KCi aqueous solution . 1 .20 X 10«

194 CHEMICAL REACTIONS.

A cell constructed with magnesium and platinum as elec-

trodes, and a dry ethereal solution of ethyl bromide contain-
ing a small amount of previously prepared Grignard reagent
as solution, gave electromotive forces of from 0.5 to 1.5
volts.
These and similar results show that the reactions in
aqueous and ethereal solutions are strictly analogous and
that similar chemical forces govern all chemical reactions,
organic as well as inorganic.
The reaction involving addition to a double bond between
two carbon atoms was discussed very briefly in the pre-
ceding chapter. From the evidence at present available,
it may be said that if the two halves of the molecule do not
differ too greatly in such compounds, the linking may be
db St

represented as : C^C : the charges indicated being only

those due to the double linking. If a halogen hydride is

added to such a linking, it is not necessary to assume any

oxidation or reduction reaction taking place. If, however,
an element added which in the stable form is negative to
is

carbon, as for example chlorine, then, if the chlorine is

considered to be in the state of neutral atoms, after the
addition each atom will have been reduced one unit of
+ -
valence, or if a chlorine molecule Cl-^Cl is considered to
have reacted, one of the chlorine have been
atoms will
reduced two units of valence, while at the same time, one
of the carbon atoms will have been oxidized two units of
cl ci
valence to give the group tt t=t . This would be a true

oxidation-reduction reaction. Similarly, if hydrogen were

added to a double carbon linking, since hydrogen is normally
positive toward carbon, the hydrogen would be oxidized
and one of the carbon atoms reduced. These considerations
refer only to the initial and final compounds of the reactions.
Probably, as in the Barbier-Grignard reaction, intermediate
 SOME OXIDATION-REDUCTION REACTIONS. 195

compounds are formed. These reactions may be illustrated

by the following examples:
CeHs - CH = CH - CeHs + 2Na
= CeHs -
CHNa - CHNa - CeHg, (6)
CeHs - CHNa - -
CHNa CeHs + 2H2O
= C6H5 - CH2 - CH2 - CeHs + 2NaOH,
(W. Schlenk, J. Appenrodt, A. Michael, and A. Thai, Ber.
47, 473 (1914)),

CeHs - CH = CH - CeHs + 2Br

CeHs - CHBr - CHBr - CeHs,
= (7)

CeHs - CHBr - CHBr - CeHs + 2H2O

= CeHs - CH(OH) - CH(OH) - CeHs + 2HBr.
The action of water here involves neither oxidation nor
reduction as far as can be told and is a simple hydrolysis.
On the basis of the theoretical developments, the simplest
view to take is that equation (6) part 1 involves a reduction
of one carbon atom two units, and equation (7) part 1 an
oxidation of one carbon atom two units. The hydrolysis
reactions indicate this difference also. As pointed out
at the end of Chapter IX, these explanations represent the
facts most nearly at the present time, but the possibility
exists that the oxidation-reduction changes are actually
brought about by the reagents added in the attempt to
determine the structures, water in the present instance.
The possibility exists and must be borne in mind even
though the evidence at present available is against this
explanation and in favor of the one given in greater detail.
The number of these reactions can be increased in-
definitely.The addition and substitution of halogen are
among the most common of the reactions in organic chem-
istry. As shown here and also in Chapter I in discussing
polar and non-polar valence, they are actually oxidation
reactions, carbon being oxidized. The rraction may be
 :

196 CHEMICAL REACTIONS.

considered to be analogous on the one hand to the trans-

formation of ferrous chloride to ferric chloride for example,
in which ferrous iron is oxidized to ferric iron and chlorine
added, and on the other hand to the transformation of a
compound such as phosphine to phosphorus trichloride (if

this direct transformation could be carried out experi-

mentally) in which the phosphorus is oxidized from — 3
to + 3. Reduction reactions may be treated similarly and
need not be taken up in further detail here.
These reactions take place as a rule between two or more
reacting molecules in which in the ultimate products two
or more atoms have changed their valence. In a number
of decomposition reactions of more or less complex sub-
stances, an intramolecular oxidation and reduction may
take place, in such a manner that one atom is oxidized and
another reduced at the same time that simpler molecules
are formed. A simple reaction of this type is given by the
decomposition of formic acid as follows

H2O + CO (a),

I
0-
(8)
+4 o
H2+CO2 (6).

In formic acid and its decomposition products, the direc-

tions of the valences or the charges on the atoms are fairly
definitely known; as definitely perhaps as in any compound.
The formula for formic acid is given in the brackets as an
equilibrium between the two tautomeric forms as discussed
in some detail in Chapter II. It will be noticed that in
both formulas, the state of oxidation of the carbon atom is
the same, 2.+ Formic acid is known to decompose in
two ways; (a) carbon monoxide and water are formed and
 :

SOME OXIDATION-REDUCTION REACTIONS. 197

(b) carbon dioxide and hydrogen are formed. Reaction

(a) takes place by warming with sulfuric acid; reaction (6)
by heating, or in the presence of finely divided rhodium,
ruthenium, or iridium. It is probable that both sets of
products are present to a slight extent ordinarily, but that
on suitable treatment one set predominates. The products
of the reaction are simple so that the states of oxidation of
the various atoms in the molecules are known. It is

evident therefore, that reaction (a) involves no oxidation or

reduction of any of the atoms in the molecule, and that in
reaction (6) the carbon atom of the formic acid is oxidized
two units of valence to form carbon dioxide, and one of the
hydrogen atoms reduced two units of valence to form the
neutral hydrogen molecule. As stated in previous chapters,
such reactions represent in reality equilibria and it may
therefore be noted that the reverse of reaction (a) to form
formic acid can be brought about with carbon monoxide
and sodium hydroxide, and the reverse of reaction (6) with
potassium or sodium amalgam, carbon dioxide, and mois-
ture.
The decomposition of oxalic acid by sulfuric acid or heat

is analogous to reaction (a) with formic acid

OH f2 44
CO + CO2 + HgO (9)
O
*c'^
OH

No oxidation or reduction of any of the atoms is involved

in this reaction. That such reactions are not peculiar to
carbon compounds is shown by the fact that the analogous

sulfur compound, dithionic acid, undergoes a similar de-

composition, as follows:

[H2S2O6I = SO2 + SO3 4- IT2O. (10)

198 CHEMICAL REACTIONS.

The structural formula of dithionic acid with the charges

on the atoms can be developed in the same way as with
oxalic acid.
Some more complex reactions, involving hydrocarbon
groups will be taken up next, but the development will

follow the same lines as in the reactions just outlined to-

gether with the general principles developed. While un-
questionably the reagents added influence the course a
reaction takes under given conditions, these reagents are
not included in the present formulations. It is intended
to bring out here the possible changes in valence of certain
atoms (oxidation or reduction) in fairly simple reactions,
so as to lay a possible foundation for a future general
classification of such oxidation-reduction reactions when a
knowledge of the valence of the atoms, their charges under
given conditions, and their oxidizing potentials or affinity
for the negative electrons shall have been determined more
precisely, especially for organic compounds, than is the
case at present.
The decomposition of acetic acid may be formulated in a
way similar to that of formic acid; namely as follows:

ll +2
HXOH + CO (a),

;! I (11)
-* +* rh\
=CU^ + CO2 w-
H O

The formula for acetic acid is represented as an equilibrium

between the two tautomeric structures as explained in
Chapter II. In both the carbon atom of the carboxyl
group is in a state of oxidation of + 2. The direction of

the valence between the carbon atom of the methyl group

and that of the carboxyl group is given by the consid-
 SOME OXIDATION-REDUCTION REACTIONS. 199

eration of the structures of the organic acids and their ioniza-

tion constants in Chapter IX. It was shown there that
malonic acid belonged to the same group of acids as chlor-
acetic acid, only one of the carboxyl group hydrogen atoms
being ionized and the other carboxyl group acting as a nega-
tive substituent. The valence of carboxyl and chlorine
toward the carbon atom of the organic acid is the same, and
therefore, until definite evidence to the contrary is found, in
the linking between the carbon atom of the carboxyl group
and that of the methyl in acetic acid, the latter is taken to
give up one valence electron to the former as represented in
the formula. Reaction (a) takes place without any of the
atoms in the molecules changing valence, but in reaction (b)

the carbon atom of the carboxyl group is oxidized two units

forming carbon dioxide, and the carbon atom of the methyl
group is reduced two units forming methane. As in the
VI and VII, the principle of
reactions described in Chapters
mass action governs to a great extent the nature of the
products obtained under certain given conditions. The
reverse of these reactions, to form acetic acid, can be carried
out; for example in reaction (a) with carbon monoxide and
sodium methylate, in reaction (6), with the Barbier-Grignard
reaction using carbon dioxide.
A number of reactions involving simple derivatives of
acetic acid may be formulated similarly. For example, with
propionyl chloride (propionyl is used instead of acetyl to
illustrate the simple formation of an olefin) the reaction is

formulated as follows:

QHb - C^^, = C2H4 + IICl + CO. (12)

In this reaction no oxidation or reduction has taken place.

There does not appear to be the same possibility of oxida-
tion-reduction as with acetic acid.
The reactions of an ester are as follows:
14
200 CHEMICAL REACTIONS.

= '^'cOg + CgHe 4- C2H4 (a),

CgHg J^^"" (13)
oe^H^ = CO + H2O+2C2H4 (5).

In reaction (a) oxidation of the carbon of the carboxyl

group has taken place, and reduction of a carbon atom of
one of the hydrocarbon groups. In reaction (6) no oxida-
tion or reduction of any of the atoms in the reacting mole-
cules has taken place.
The reactions of acetoacetic ester represent a somewhat
more complex case, but can be treated in the same way.
Acetoacetic ester may decompose in two ways; on treat-

ment with dilute alkali (boiling) or with dilute sulfuric

acid, it undergoes the "ketonic decomposition" with the
formation of a ketone, an alcohol, and carbon dioxide;
treatment with concentrated alcoholic alkali results in the
"acid decomposition" and formation of acid and alcohol.
These transformationsmay be formulated as follows:
-3 -1 _3 _i -3 -2 -3
4 1+3 +1 +3^0
HgC-^CO-CHg-C^ - CHs-^CO-CHs+COg+CgHsOH (a),

(R) ^OC^Hs CR) (Ri) /14

-3 -1 -3 -1 ^^^
(Ri) +1 +3 -+-1 +3
nHpO = CH3C02H+CH3C02H+C2H50H(6).
(R) (Ri)

Reaction {a) represents the ketone decomposition, reaction

(6) the acid decomposition. R and Ri can be used to
represent a variety of different groups. The exact relation
of R to the carboxyl group with which it iscombined is of
secondary importance, as long as it does not change in
the course of the reaction. The distribution of the charges,
or the valence of the atoms follows from the principles
already given. In reaction (6), the acid decomposition,
there is apparently no oxidation or reduction involved.
This reaction involves the use of concentrated alcoholic
alkali, a reagent which is supposed to cause or assist oxida-
 SOME OXIDATION-REDUCTION REACTIONS. 201

tions in organic reactions. Whether it does or not, in this

reaction at any no oxidation appears to occur. Pos-
rate,
sibly it influences the changes occurring by removing the
acetic acid as soon as formed and causing the reaction to
take the indicated course (6) according to the principle of
mass action. In reaction (a) on the other hand, an oxida-
tion-reduction has occurred, analogous in every respect to
the oxidation-reduction with acetic acid. The group
CH3COCH2 in the former corresponds to the group CH3 in
the latter; in the former the product acetone corresponds
to the product methane in the latter. The possibilities of
tautomeric forms and intermediate products are much
greater with acetoacetic ester than with the simple acids,
and no attempt will be made here to formulate them.
The reaction between chloroform and alkali in which
the former is hydrolyzed may be represented as follows:

fHCClal
L2H2O J
HCO2H + 3HC1. (15)

No oxidation or reduction is involved here. In order to

show the uncertainties with regard to some apparently
simple reactions, the decomposition of trichloracetic acid
(which may take place on heating an aqueous solution)
may be shown:

CLC- -'c^ (a)

^on +8

or IlCClg + ^COa (10)

CI3C (b)

on

The question which arises is as to the structure of trichlor-

acetic acid; whether it is to be represented by formula (a)
202 CHEMICAL REACTIONS.

or (6). The ionization constant does not give any clue,

since it varies too greatly with the dilution to permit of
classification. The small difference in potential between
the two carbon atoms of trichloracetic acid also adds to the
uncertainty as there is nothing to indicate whether one is

positive or negative to the other. If formula (a) is correct,

no oxidation or reduction is involved; if formula (6) is

correct then the carbon atom of the carboxyl group is
oxidized two units of valence and the other carbon atom
reduced two units of valence in the reaction. As stated,
there is no definite evidence to indicate the true nature of
the reaction.
The reactions of benzenesulfonic acid have been of
interest in connection with questions of valence for some
time. On hydrolysis with acid, benzene and sulfuric acid
are formed, with alkali, phenoland sulfite. The question
of oxidation and reduction in these reactions can be ap-
proached best by considering first the structure of the
benzene sulfonic acid as developed from simple principles
and analogies.
In the first place, in general when carbon combines with
sulfur, the carbon atom loses a negative electron to the
sulfur atom. This is evident from the relative positions of
these elements in the Periodic System. In the second
place, in thedevelopment of the structures of the acids in
Chapter IX, it was found that benzoic acid belongs to the
same class as acetic acid. There is every reason to believe
that in these acids, the carboxyl group as a whole is negative
to the hydrocarbon group as a whole, whatever their internal
structures may be, although of course the various charges
are present on the individual atoms. The formation of
benzoic acid from benzene and carbon dioxide might then
be formulated as follows:

[CeHs]- <- H+ + CO2 = [CeHsf -^ CO2H. (17)

 :

SOME OXIDATION-REDUCTION REACTIONS. 203

A reaction of this kind might be involved in the Barbier-

Grignard reaction with the formation of salicylic acid from
phenol, etc., without considering the intermediate products,
but only the compositions and structures of the initial and
final substances. The change involves the reduction of
the carbon of the carbon dioxide and the oxidation of one
of the carbon atoms of the benzene. It is exactly the
same change as was shown in reaction (116) in the for-
mation of methane and carbon dioxide from acetic acid
which was shown to be an oxidation-reduction reaction.
The sulfonation of benzene, in which SO3 plays a similar
part to that of the CO2 should then follow the same rules.

The formulation may be indicated as follows:

[CeHs]- <- H+ + SO3 = [C6H61+ -> SO2 -> OH. (18)

Here, also, the reaction may be considered to be oxidation-

reduction; the sulfur being reduced from +6 to +4
(+ 5 —
1), and onecarbon atoms of the benzene
of the
ring oxidized correspondingly. This agrees, also, with the
directions of the valences as deduced from the Periodic
System, although too much stress must not be laid upon
this point.
The hydrolysis reactions of benzene sulfonic acid may
now be indicated, as follows

(ACID) CfiHs^-H + Sa (6),

OH
(10)
CeHe +6
.SO3 (ALKALI) C6H6->OH + S02 (a).

_ H
These decomposition reactions (the formation of sulfuric
acid and of sulfite is not given in the equations but
must
be understood to occur) are analogous to the drcomposition
reactions of acetic acid, equations (11).
Reactions (a)
204 CHEMICAL REACTIONS.

in both cases involve no oxidation or reduction, reactions

(b) are oxidation-reduction reactions. The detailed exposi-
tion with benzene sulfonic acid need not be gone into, since
it follows the corresponding changes with acetic acid.
Another type of reaction may be mentioned here, which,
while not oxidation-reduction, shows some of the possibili-
ties in the way of relative oxidizing potentials of different
atoms, or the relative affinities of the atoms for valence
electrons. Silver nitrite and sodium nitrite when treated
with an alkyl halide give different products. With the
former, a nitro compound obtained mainly; with the
is

latter a nitrite predominates. While according to the older

views, this would point to different structures for the two
nitrites, according to the principles developed in this book,
the explanation of these differences involves tautomerism
and several chemical equilibria. The reaction may be
given in general terms as follows:

1^0 MeX + R-^NC

^ (^)'

+RX (20)
o
N^
< ^0-^Me
MeX +
O^R
(5).

The silver and sodium nitrites may exist in tautomeric

forms as shown in the formula and outlined in Chapter II.

There is no evidence at hand at present to show which form
predominates under any given conditions. When the
nitrite is treated with the alkyl halide RX, in all probability
an addition compound is formed which is not given in the
equations, and this addition compound is in equilibrium
with the two sets of products represented by equations (o)
and (6). There is no oxidation or reduction involved in
either of these equations. Unquestionably both sets of
products are obtained with any metallic nitrite. Which
 SOME OXIDATION-REDUCTION REACTIONS. 205

product is obtained in greater amount with a given nitrite

will depend upon the relative oxidizing potentials of the
various atoms in the molecule. This is, in reality, only a
different way of stating that the relative amounts of the two
sets of products depend upon the chemical affinity or the
states of the equilibria. Because of the similarity of the reac-
tions, it would not be expected that the velocities would differ
greatly, but this possibility must also be kept in mind as pos-
sibly the dominating factor in controlling the course of the re-
action observed. To speak of the relative oxidizing poten-
tials toward oxygen and nitrogen of the metal instead of
the chemical affinities does not add directly to the knowledge
of the reaction but brings it into line with the newer point
of view developed in this book, and may aid in developing
a future classification of such reactions. If the metal is

sodium in reaction (20), the reaction follows course (6)

mainly, if silver, course (a). It may be possible to deter-

mine the relative oxidizing potentials of sodium and silver
toward oxygen and nitrogen in these reactions by suitable
measurements of the equilibria under comparable condi-
tions. This point of view may evidently be extended to a
number of other reactions which show similar changes.
Finally, a classification of chemical reactions which in-
cludes all reactions in a general scheme based upon the
valences and changes in the valences of the atoms in the
reacting molecules may be given. In every reaction, either
I. The algebraic sum of the positive and negative charges
on a definite atom of the molecules involved changes; or
II. The algebraic sum of the positive and negative charges
on a atom of the molecules involved remains con-
definite
stant.
If I, the algebraic sum changes; either, i4, the number
of negative electrons on the atom in question is increased,

or the number of positive charges on the atom is decreased

(or reduction) ; or, 2?, the number of negative electrons on
 —

206 ^
CHEMICAL REACTIONS.

the atom is decreased, or the number of positive charges on

the atom is increased (oxidation).
If II, the algebraic sum remains constant; either. A, the
arithmetical sum and negative charges on
of the positive
the atom the atom in question
in question changes; i.e.,

gains or loses the same number of positive and negative

charges simultaneously (molecular or onium compound
formation); or, B, the arithmetical sum of the positive
and negative charges on the atom in question remains
constant; i.e., the electric charge on the atom in question
remains unchanged.
To sum up: In every reaction
I. If the algebraic sum of the positive and negative
charges on a definite atom of the molecules changes; either,
A, the number of negative electrons on the atoms increases;
or, B, the number of negative electrons on the atom
decreases;
II. If the algebraic sum of the positive and negative
charges on the atom remains constant; either, A, the
arithmetical sum changes; or, B, the arithmetical sum
remains constant.
Applied to chemical reactions, lA includes reduction
IB oxidation reactions, 11^ molecular or onium
reactions,
compound formation and decomposition, IIB metatheses
in which none of the changes lA, IB, or 11^ takes place.
Stated slightly differently, the classification includes re-
actions involving reduction, oxidation, molecular or onium
compound formation and decomposition, and simple re-
placement or rearrangement.
 INDEX
Authors' Names in roman, Subjects in italics

Abel, E., 72 Baly, E. C. C, 22, 23, 32, 67,

Abegg, E., 9'8 193
Acetic acid decomposition, 15&, Bancroft, W. D., 72

198, 199, 201 Barbier, P., 191, 192, 193, 194,

Acetoacetic ester decomposition, 199, 203

200, 201 Barhier-Grignard reaction, 191,

192-194, 199, 203
Acetylenes, 145, 181
Barker, T. V., 34
Acree, S. F., 128
Baume, G., 137, 142, 150
Adsorption, 69
Behal, A., 150
Aldol condensation, 111, 115, 120,
Benzene nucleus, 182, 183, 188,
125
189, 203
AlJcyl halides, 136-143, 145-147,
Benzenesulfonic acid decomposi-
156, 160, 162, 204
tion, 202-204
Aluminium compounds (com-
Benzidine rearrangement, 109,
plex), 105, 106
112, 116, 122
Amides, 121, 156, 157, 163-165
Benzoic acid decomposition, 202,
Amines, 53, 65, 121, 142, 146, 203
156, 160, 161-163 Bernthsen, A,, 129
Ammoniates, 21, 25, 26, 28, 29, Berthelot, M., 176
30, 31, 33, 34, 36, 38, 45, 46, Berzelius, J., 169
48, 57, 58, 89, 90, 136, 137, Bethmann, H. G., 176
143, 150, 159, 160, 161, 163 Boedtker, E., 104
'
' Anomalous '
' compounds, 24, Booseken, J., 97, 98, 99
25, 48, 136 Bone, W. A., 176

Anechiitz, W., 155 Booge, J. E., 150

Appenrodt, J., 195 Bragg, W. H., vii, 34
Armetrong, E. F., 68 Bragg, W. L., vii, 34
Arrhenius, S., 10, 15, 41, 45, 128 Branch, G. E. K., vi, 39, 158

Aschan, Biay, W. C, vi, 39

I., 105
Bredig, G., 72, 128
Atomic theory, 1, 2, 3
Brown, A., 68
Autenreith, W., 155
Brown, II. T., 68
*' Auxiliary {secondary) val-
Bruhl, J., 92
ence," 22, 23, 24, 30, 31, 32,
Brunei, R. F., vl
»7
BrusHow, S., 142
Biiclibock, G., 66
Bacyor, A., 25, 26 Butlcroff, A., 143

207
208 INDEX.

Carpenter, C. D., 27 Electromerism, 187, 188, 189

Chemical affinity, 4, 5, 6, 7, 8, 14, Electromotive force, 168, 169,
32., 78, 1321-134, 168', 169, 170, 170, 191, 194
191, 205 Electron, 12, 17, 167, 169, 170,
Chemical energy, 3, 4, 5, 14 172, 183, 187, 188, 189, 190,
Chemometer, 168 192, 198, 205, 206
Chojnacki, C, 137 Electronic valence, v, vi, 10, 11,
Classification of reactions, 205, 12, 13, 18, 24, 32, 42, 49, 54,
206 56, 169, 170, 171, 172, 173,
Collie, J. N., 25, 26 188, 192, 199, 204
Color, 105, 128 Eltekoff, M., 142
Combes, A., 103 Emory, W. O., 155
Cone, L. H., 27 Energy, capacity and intensity
Co-ordination number, 31, 33, 34, factors, 3-^5
46, 47, 48, 49', 50, 51, 52, 58, Engel, E., 152
83 Enzymes, 67, 68, 69
Crafts, J. M., 95, 103 Epliraim, F., 80, 90
Crehore, A. C, 34 Equilibria, chemical, 2, 6, 7, 9,
Crum Brown, A., 176 53, 54, 60, 71-75, 78, 82, 86,
Cullen, G. E., 68 88, 93, 101, 102, 108, 112, 113,
122, 129, 130, 138, 140, 144,
Dakin, H. D., 68
146, 149, 150, 197, 204, 205
Dawson H. M., 128 Esterification, 63, 119, 121, 123,
de Coninck, W. O., 158
125, 147, 150^154
de Forcrand, E., 137
Etherification, 63, 109, 110, 121,
Derick, C. G., 131, 132, 133, 134
125, 147, 155
Desgrez, A., 150
Euler, H., 176
Diazo reaction, 116-119, 122
Evams, W. V., 127, 193
Dilution law, 53, 173, 178
Dithionio acid decomposition, Falk, K. G., 62, 68, 127, 173,
158, 197 187
Double bond isomerism, 180, 181, Findlaj, A., 26
184r-18i6, 187, 188, 194
Fischer, E., 6S
Drucker, K., 176 Fischer, F., 105
Duclaux, J., 68 Fittig, E., 191, 19'2
Dushman, S., vi Fittig synthesis, 191, 192
"Force fields," 23, 32, 37, 193
JElectroisomers, 15 '

Formic acid decomposition, 196,

Electrolytic dissociation, 10, 15, 197
28, 29, 35, 36, 41, 42, 45, 47, 48, Franke, E., 176
49, 52, 53, 54, 55-57, 82, 83, Franklin, E. C, 145
86-88, 90-92, 123, 124, 125, Free energy, 4, 5, 6, 7, 8, 18, 75,
126, 127-130, 139, 140, 148, 132-134, 168
152, 156, 169, 172, 173 Friedel, €., 25, 95, 103
 INDEX. 209

Friedel-Craft s reaction, 64, 95- Kacliler, J., 137

106, 108, 111, 115, 117, 120, Kamm, O., 133
125, 138, 146 Kauffmann, H., vi

Fry, H. S., v, 187, 189 Kendall, J., 27, 105, 125, 148,
150
G-asiorowski, K., 163 Kipping, F. S., 102, 103
Gatterman, L., 103 Kleber, C, 176
Genequand, P., 114 Klein, D., 66
Germann, A. F. O., 137 Klemensiewicz, Z., 91
Geyer, A., 155 Koeh, J. A., 103
Gibbons, W. A., 27 Kohler, E. P., 98
Gibbs, W., 7 Kondakow, J., 136, 145, 146,
Glendenning, T. A., 68 149
Goldschmidt, H., 128, 150, 163 Konowalow, D., 145, 147, 154
Gomberg, M., 27 Krapivin, S., 103
Grigmard, V., 126, 127, 160, 191, Kraus, C. A., 145
192, 193, 194, 199, 203
Grignard reagent, 126, 127, 160, Lang, R., 98, 99
193, 194 Langmuir, I., vi
Gulewitsch, W., 98 Lapwortb, A., 72, 128
Gustavson, G., 96, 97, 146 Lecco, M., 24
Guye, P. A., 98 Lercynska, I., 105
Lermontoff, J., 142
Hantzsch, A., 120, 176 Lewis, G. N., v, vi, 39
Haussermann, J., 161 Lichty, D. M., 176
Helmholtz, H., 7 Li-ben, A., 142
Hofmaiin, A. W., 53, 162 Lifsehitz, J., 128

Hofmann, K. A., 26 Lorenz, K.> 91

Hohmann, C, 148, 149
Maass, O., 27
Holleman, A. F., 109, 123
Hoogewerff, S., 26 Mcintosh, D., 26, 27
Maihle, A., 137, 138
Hydrates, 21, 26, 27, 28, 33, 36, *
'
' Main {principal ) valence, *
37 38, 45, 46, 47, 48, 49, 51,
31, 32
52, 56, 57, 58, 81, 82, 83, 89,
Markownikoflf, W., 114
120, 141, 147, 151, 156, 157,
Martinsen, H., 113
159, 160
Mellor, J. W., 67, 74
Mendel6eff, D., 3, 20, 172
Indicators, 129, 130
Menschutkin, B. N., 65, 97, 98,
Ionization constant, 53, 54, 147,
99 147
148, 173-182, 202
W. A., 90, 91, 92 Menten, M. L., 68
Isbekow,
Merz, v., 163
M6y«r, v., 24, 136, 187, 157,
Jacobean, P., 136, 137, 157, 165
Jones L. W., v, 187
Jones, W. J., 72 Michael, A., 195
 210 INDEX.
Michael, Arthur, 138, 185 Platinum-ammonia compounds,
Michaelis, A., 104 28-31, 33, 34, 36, 38, 39, 44,
Miehaelis, L., 68 188
58,
MiUikan, R. A., 12 Plotnikoff, V. A., 26, 92, 98, 103
Miolati, A., 176 Polar and non-polar valence, vi,
Molecular theory, 1, 2, 3 15, 16, 17, 19, 87, 135, 167,
195
Nef, J. U., 99, 110, 111 Potentials, oxidizing and re-
Nelson, J. M., v, vi, 62, 68, 70, ducing, 13, 14, 116, 169, 170,
127, 187, 193 172, 173, 184, 187, 198, a02,
Nernst W., 92, 148, 149, 168, 169 204, 205
Niggeman, H., 105 Precht, H., 136
Nitration, 108, 109, 110-115, 122 Prins, H. J., 103
Nitrite reactions, 204, 205
Northrop, J. H., 70 Beaction velocity, 1, 6, 9, 60, 61,
Noy^s, A. A., 130 62, 65, m, 69, 70, 71, 73, 76,
Noyes, W. A., v, 184 79, 81, 97, 106, 108, 113, 114,
122, 123, 124, 137, 138, 142,
Olefinates, 136, 137, 143, 147, 147, 148, 149, 152, 160, 172,
150, 156, 159, 160, 161, 165 205
Onium compounds, 27, 28, 30, 32, Rosanoff, M. A., 7^
38, 57, 81, 88, 89, 105, 106, Rossi, A., 142
112, 193, 206
OnAum valence, 30, 32, 37, 38, 57 Sabatier, P., 64, 137, 138
Oppenheim, A., 136 Sackur, O., 91
Organic acids {structures), 156- Salt hydrolysis, 126
158, 173-184 Scheffer, F. E. C, 29
Ostwald, W., 53, 129, 168, 173, Schlenk, W., 195
176, 178 Schmidlin, J., 98, 99
Oxalic acid decomposition, 158, SeUvanow, T., 184
197 Senter, G., 128
Oxonium salts, 25, 26, 48, 147, Smith, A., 138
159, 160, 161, 177 Smith, W. A., 176
Snethlage, H. €. S., 128
Bamfil, G. P., 150 SpraDkling, C. H. G., 176
Panek, C, 104 Stark, J., vi
Partial valence, v, 133 Stereochemical capacity, vii, 34
PatteB, H. E., 92 Stieglitz, J., V, 128> 129, 150
Periodic system, 3, 10, 13, 20, Siobbe, H., 26
172, 202, 203 Stohmann F., 176
Perrier, G., 96 Strauss, F., 26
Perrin, J., 3 Sudborough, J. J., 176
Phase rule diagrams, 26, 58, 97, Sugiura, K., 68
98, 162 Sulfuric add condensations, 107,
Pictet, A., 105, 114 111, 125, 143, 144, 145
 INDEX. 211

Szyszkowski, B., 176 van't Hoff, J. H., 7, 74

Varet, R, 103
Tmitomerism, 32, 38, 39, 40, 43, Vienne, G., 103
M, 46, 52, 81, 88, 92, 112, 113, Villiger, v., 25, 26
117, 129, 130, 131, 147, 156, Vorlander, D., 26
187, 196, 198, 201, 204 Vosburgh, W. C, 68
Taylor, H. S., 128
Thai, A., 195 Waclis, C, 163
Thiele, J., v, 26, 132 Walden, 176
P.,
Thomson, J J., v, 10, 12, 20, 92 Walker, 176
J.,
Tickle T., 26, 26 Walker, J. W., 87, 99, 104
Tissier, L., 139 Washburn E. W., 56
Tolloczko, S., 91 Wecker, E., 106
Trichloracetic acid decomposi- Wedekind, F., 161
tion, 201, 202 Werner, A., vi, 21, 23, 24, 28, 30,
31, 32, 34, 35, 38, 42, 44, 50,
Unsaturation, 23, 64, 66, 79, 92,
54, 83, 90, 124, 152, 187, 188
115, 127, 132, 135, 136, 137,
Wieland, H., 105
145, 180, 181
Wildermiann, M., 142
Valence, v, 1, 3, 4, 5, 8, 9, 10, Willstatter, E., 114
11, 12, 15, 17, 18, 19, 20, 21, Wilsmore, N. T. M., 169
22, 24, 30, 32, 34, 51, 52, 57, Wroczynski, A., 98
83, 105, 135, 166, 167, 169, Wiirtz, A., 191, 192
170, 171, 173, 174, 183, 184, Wiirtz synthesis, 191, 192
185, 187, 188, 191, 193, 194,
196, 197, 198, 199, 200, 202, Zinc chloride condensations, 106,
203, 204, 205 107, 125, 145, 146, 149, 150,
Valence Unkings, 3, 9, 20, 34, 64, 163
167, 170, 171, 172 Zones, inner and outer, 31, 32,
van Dorp, W. A., 26 35, 37, 38, 44, 45, 46, 47, 49,
van Slyke, D. D., 68 50, 52, 54, 56, 57, 58, 81
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