Chemical Reactions Their Theory and Mechanism

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T HE I R T HE ORY A ND ME CHA N I SM
BY
K . G E OR G E EA LK , P H D . .
H A RR I M A N R E SE A R OH L A B OR A T OR Y ,
T HE R OOS E V E L T H OS P I T A L , N E W Y OR K
N E W Y O RK
’
D , V A N N OS T R A N D C O M P A N Y
E I G HT W A RR E N S T R E E T
1 9 20
www.EngineeringBooksPdf.com
P RE F A C E
T HE central idea of this book is the development of a

general theory of reactions wh i ch will include both i n
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 a ppli
cab il
it y . As far as the writer is aware however this i s 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 h is paper on partial valence .
S ome years later 19 04 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 it s application as shown in sporadic
publications Professor Nelson and the writer believe that
.
they were the first dating from 19 09 on to publish extended

, ,
applications of the electron conception of valence to organi c

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 U nquestion .
ably others have followed the same or similar lines of

,
th ought and reached similar c o nclusions Among those .
who have published along these lines may be mentioned

H S Fry W A Noyes J S tieglitz L Jones G N Lewis
. .
, . .
,
.
,
.
,
. .
,
Vi C HEM I CA L REACTI O N S .
R F B runel , W C B ray and G E B ranch ,

. . . . . . S . D ushman ,
J S tark H Kau ffmann and a number of others No
.
, .
, .
attempt will be made t o g i ve a historical review of the

problem or to determine who is responsible for any par
t i c ul
ar part of the theory That it was possible for c ertain .
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 pub lication .
For practical reasons it was not possible f or Professor ,
Nelson and the writer to add to the experimental data from

the newer point of view but it seemed at the time a s if ,
sufficient facts were recorded in the literature t o 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 T o -

.
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 conce p

’
tions used in the lat er chapters C ertain parts of Werner s .
theoretical views are used At present these appear t oo ff er .

,
the only explanation which is at all satisfactory for what

“ ”
have been termed at various times molecular compounds .
I n recent years G N L ewis and I L angmuir have developed

(
, . . .
certain conceptions of molecular structures from the point

of view of electron distribution These conceptions are .
of the utmost importance and indicate n ew methods of

formulation To apply them to the consideration of chem
.
ical reactions appears to be somewhat premature At least .

,
it appears to the writer that for him to attempt it would

be so S ince 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 b elieved that enough o f

.
,
P RE FA C E . Vi i
the general theoretical s ide has been given to permit any

one interested t o follow intelligently any further develop
ments of structural chemical theory .
Q uestions of stereochemistry have n ot been included .
It would appear that S patial chemistry is entering upon a

new phase The expe rimental and theoretical work on the
.
arrangements of atoms in crystals as exemplified in the

publications of the B raggs and of others points t oan 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 M any of these have been presented by
.
Professor Nelson to his students at C olumbia U niversity

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 A mong .
others who have aided in various ways in the development

of the views leading up to the preparation of this book and
to whom thanks are due are Professors G B Pegram and . .
H T B eans of C olumbia University and D r M arston

. .
, , .
L Hamlin
. .
N E w YORK N Y , . .
,
Ju n e 15, 19 2 0 .
C ON T E N T S
CH APTE R 1 .
PA G E
I N T ROD U C T I ON ; VA L E N C E . 1
C H APTE R I I .
VA L E N C E ( C ON T I N U E D ) ; C o O RD INATI O N N U M B E R
-
. 21
C H APTE R I II .
AC I D S A ND B A SES 41
C H APTE R IV .
C A T A L YS I S 60
C H APTE R V .
C HE M I CA L R E A C T I ON S ; G E N E RA L 76
C H APTE R VI .
SO M E C HE MI C A L R E A C TI O N S 94
C H APTE R VI I .
SOM E C HE M I CA L RE A C TI O N S ( C ONTIN U E D )
~
120
C H APTE R VIII .
O L E FI N S A ND T HE I R RE A C TI O N P R O D U C T S 1 35
C H APTE R I X .
OX I D ATI O N RE D U C TI ON
-
1 66
C H APTE R X .
SO M E OX I D ATI O N-R E D U C TI O N RE A C TI ON S 19 0
ix
C H E M I C A L R E A C T I ON S
C H APTE R I .
I N TRO D UC TI O N ; VAL E NC E .
IN order to classify chemical reactions so that it will be

possible t o obtain a knowled g e of the relations involved
when chemical changes take place without considering each
chemical reaction a s an individua l u nrelated t o any other ,
certain general theories must be established These 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 M ol e cular .
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

c e p t i on s form the foundations. Reaction velocities are the
important features in considering chemical reactions and
the course these may take under given conditions It i s .
impossible to treat of a reaction velocity without treating
’“
9 1
CHEM I CA L RE AC TI O N S .
‘ 3 velocity of the reaction in the opposite

direction or in other words the equilibrium of the reaction
, , .
E quilibria are therefore arrived at from the kinetic and

m ol ecular standpoints This is as far as the theoretical
.
S ide of the treatment in this book will go It may be .
pointed o ut that the thermodynamic treatme nt reaches the

same point from the opposite direction From the energy .
relationships deduced from the laws of thermodynamics

, ,
th e equilibria relationships of chemical reactions are arrived

at One of the future problems of thermodynamic chem
.
i st ry i s the development of reaction velocity relationships

from the equilibria concepts .
The reader of this book is supposed to have completed a

course in general inorganic and organic chemistry from the
modern point of view The relations of chemistr y 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
n om e n a applied and used in a rational manner S uch a .
study would include a portion of the subj ect matter of

“
what is very often taken up at present under p h y slcal
”
chemistry .
The atomic theory i s based upon the laws of definite and

multiple proportions E xact analyses of many substances
.
have shown that the constituent elements of these su b

stances are combined in such quantities that definite
amounts or their multiples are always combined with each
other The atomic theory gi v es a definite and simp le
.
theory to account for this The molecular theory i s 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 rec en t years the existence of atoms and molecules has
INTRO DUC TION VA L E N C E . 3
been demonstrated experimentally so that no question

remains as to their existance The reader is referred to the
.
“ ”
book entitled The A tom by J Perrin for an account of
.
this work .
The terms equivalent or combining weight and formula

weight have been used in place of atoms and molecules as
no t involving the theories of atoms and molecules While .
these terms may have been useful at a time when the e x i s

tence of atoms and molecules were to some extent hypo
thetical the proof of their existence in recent years has
,
m ade the u se of such terms u rine ce ssa ry .
Fo llowing the atomic and molecular theories the study ,
of the chemical compositions of substances led to the

doctrine of va lence or saturation capacity E ach atom is .
considered to be capable of combining with a definite

number of atoms of i t s own kind or a different kind The .
a rrangement of the elements in the Periodic S ystem of
M e n d elée ff brings out clearly these valence numbers The

‘
.
introduction of dots and dashes in chemical formulas to

represent valence lin ki n g s forms a convenient m ethod of
representation .
S ometimes confusion has been caused by taking valence

li n ki n g s to represent some form of combining power or
stability This question must be made C lear and the mean
.
ing of valence defined carefully for a proper understanding

of the questions to be taken up In order to do this
.
,
chemical energy will be taken up for a moment and the

relation between it and valence described .
For some purposes it has been considered that energy

,
might be assumed to be the product of two factors an ,
“ ” “ ”
intensity factor and a capacity factor For example .
,
in mechanical work or energy in which the work is taken

,
to be equal to the product of force into distance the force ,
would be the intensity factor and the distance the capacity

factor This division of energy into factors i s entirely
.
4 C HEM ICAL RE A CTION S .
arbitrary It serves a useful purpose in certain cases but

.
,
its limitations must be remembered The intensity and .
capacity factors of mechanical energy need bear no relation

except in name to the intensity and capacity factors of
,
electrical energy or of chemical energy or of any other form “
of energy For each form of energy a different division

.
may be made This can be S hown 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 M L T Z 2
In energy considered as me
‘
c h a n i ca lwork force may be called the intensity factor and

,
is given by the product of mass times acceleration or M L

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 express i on M L T and the electricity or charge
1’
2 1 /2 l ‘
or coulombs the capacity factor and given by the expression

These two sets of factors S how 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 g i v e n

,
»
by the change of free energy of the reaction under certain

definite conditions to be formulated presently This is the .
chemical a ffinity and the units in which it is expressed

,
given by M L T 2 2
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 h ow ,
ever If the change in free energy is referred to the c om

.
bination taking place between equivalent weights of chem

ical substances that is to sa y between the unit weights of
, ,
'
chemical combination then when considering molecules , ,
or formula weights the numbers of equiva l , ents taking
INTRO DUCTION VAL E NC E . 5
part would indicate the capacity factor or valence Valence .
i s therefore represented as a number and the product of

change in free energy per equ i valent and valence represents
the change in free energy in the f orm a t lon of the substance
in the molecular state In ferrous chloride f or example
.
, ,
the free energy or chemical a ffinity 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 n ot impossibility of determining

.
,
the free energy change when two atoms of a more complex

molecule combine makes it necessary in practice t o speak
,
only of the C hange in free energy in the formation of a

compound and not of the separate combinations between
pairs of atoms in the compound .
Keeping in mind the significance of the terms intensity

and capacity factors they will n ow 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
bi n e d with each other .The chemical affinity in volved in
a compound is a defini t e quantity It is given numerically .
as the value of the a ffinity of that compound compared to

the value of the a ffi nity of the substances from which it
is formed That is to say the chemical affinity of a com
.
,
pound is given as a di ff erence 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 i s.
generally k nown as the change in free energy in the forma

tion of the compound and is the true measure of t h e chan g e
6 C HEM ICA L REACTION S .
in the chemical a ff inity The actual measurements of

.
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 A t the present time very few organic
“
reactions are available for the former method while for ,
the latter the accurate determination s of a large n umber of

,
equilibria in organic reactions have not been carried ou t .
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 the most important problems in chemistry at the present

time S uch val u es would give a true measure of the rela
.
tive stabilities of compounds or the magnitude of the

,
chemical affinities M any organic chemists have been in

.
the habit of S peaking of the stability of a compound when

the rate at which the compound reacted wa s meant Re .
a ctio n velocities bear no S imple relation to the stability or
a ffinity,
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 .
T h e terms upon which the intensity factor of chemical

e nergy or the chemica l a ffinity depend may be indicated
as follows : E ve ry reaction is ( thermodynamically ) rever

sible The greater the affinity which causes two substances
.
t o combine or react the greater will be the proportion or

,
amounts of the products formed and the more difficult ,
w ill it be to decompose the products The chemical a ffinity

.
will consequently be greater the more the equilibrium lies

,
i n the direction of the formation of the products ; or in ,
other words the value of the chemical a ffinity is connected

,
with or may be ca lculated from some function of the

,
8 CHEM I CA L RE ACTION S .
equations are fundamental for the relations between the

chemical affinity of a reaction and other physical and
chemical quantities .
The last equation shows that only if T 0 or if

dA/d T 0 is the heat of reaction equal to the chemical
affinity The equality of these t wo is therefore only a
.
specia lcase and as T increases they are likely to diverge

, ,
more and more Whether the heat of rea ction is greater

.
or less than the chemica la fii n it y will depend upon whether

the change in the chemical a fii n it y 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
f or 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 ene rgy may be considered

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

.
already been given the chemical a ffi nities of organic c om

,
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 .
A t the same time another reason for this may be given .
The change in free energy or the thermodynamic stability

, ,
while of the greatest importance has nothing to do with

,
the time factor That is to sa y i t g i v e s the stability of a

.
,
compound when equilibrium has been reached Now the .
element carbon often shows great inertia or chemical r e

s i s t a n ce in many of its compounds and reactions The .
velocity with which it enters into reactions is often very

sm a ll even though the free energy involved in the chemical
change is very great A s a result compounds of carbon
.
,
are known which have no thermodynamic right to exist ,
INTRO DUC TION : VA LE N C E . 9
that is to s a y 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 s ubstances While therefore undoubtedly the
.
, , ,
affinity relationships of organic compounds will ultimately

be of predominant importance until m ore is known of
,
these valence which is not affected by the time factor in

, ,
this way has had t o serve as the classifying principle

, .
B ut in using valence in this way it is not permissible t o

introduce exact measures of the comparative stabilities as
has been attempted so often as already pointed ou t A ll
,
.
that can be done as a result of the comparative study of

large numbers of compounds i s 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 q a nt it at i v e

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 .
Q ualitatively it has been found that the rate of rea ct i on

,
for compounds containing double lin ki n g s is greater in some

ways than the rate for compounds containing single lin ki n gs ,
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 T h e double linking in

.
the ordinary language signifies t wo units of valence j ust

as the single linking denotes one unit of valence and in this ,
sense th e only permissible one the representation of a

, ,
double linking by two lines or dashes is a correct pictur e

of the union when on e line i s used for the single linking .
10 C HEM ICA L RE ACTION S .
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
suffi cient to include all the facts known For instance .
,
oxides are at times spoken of a s acid oxides and basic oxides .
E lectrolytic studies on the decomposition of salts and other

substances in solution indicate a real di fference between
the two parts of the molecules The distinction may be
.
carried further and acid forming elements and base forming

- -
elements designated as brought out for instance by the

, , ,
oxides of the elements of the different groups in the Periodic

S ystem 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 term inology 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 form ula weight of that element .
’
Arr h e n i u s s theory of ionization has shown that certain
of the a tom s or g roups 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 19 04 p ut 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 p laced in beaker A and a solution of ,
potassium permanganate in beaker B the two solutions ,
connected by a salt bridge 0 containing a solution of some

’
neutral salt dipping into both solutions and by a wire with,
INTRO DUC TION VAL E NC E . 11
a galvanometer in circuit connecting the two electrodes D

’
and D which dip into the solutions it will be noticed that
,
a positive current will flow in the direction B to A in the

‘
wire If the contents of beaker A be examined now it

.
,
will be seen that the iron has been oxidized to the ferric
form If the amount of positive electricity flowing through
.
the circuit from B to A w ere measured and t he amount of

ferrous iron changed into ferric iron were also measured ,
it would be found that for every formula weight or mol of , ,
ferrous iron changed into ferr ic iron coulombs of

,
electricity had passed through the circuit Therefore it .
may be said that one m ol of ferrous iron differs from one

mol of ferric iron by coulombs In this way it may
.
be brought out that

One mol of iron 5 6gram s of iron .
ferrous iron 5 6 grams of iron X

coulombs negative electricity .
( C “
ferric iron —
5 6 grams of iron 3 X
coulombs negative electricity .
From 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
ca n hold in chemical union or in other words there i s a
, , ,
/
definite relation between the amount of electricity and the

valence of the iron .
If instead of a solution of ferrous chl oride a n alkaline

, ,
sol ution of formaldehyde is placed

in beaker A it will be found that
,
again a positive current will flow

from B to A in the wire and if
, ,
the constants of beaker A are ex

a m i n e d it will be noticed that the
,
f orm al d efiyd e has been changed

into formic acid or oxidation has taken place The amount
,
.
l2 C HEM ICA L REACTION S .
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 compound s

, ,
as with inorganic compounds is accompanied by electrical

changes .
If the amount of electricity in any oxidation reduction -
reaction involving electrolytes be measured it will be found ,
that for every mol of an element undergoing oxidation or

,
reduction , coulombs or a simple multiple of this

'
quantity are always involved S imilarly 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

,
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 s o ,
electricity may be regarded as atomic in character and ,
coulombs represents on e combin ing unit or if the ,
expression may be used on e combining weight of elec

,
t ri c i t y
. 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 wor k

of a number of physicists especially by J J Thomson and
, . .
R A M illikan
. . .
Taking into consideration the definition of valence given

before and the experiments and conclusions therefrom j ust
described it is now possible to give a general definition of
,
valence which may be applied readily and used as S imply

a s the older definition of valence The va l
. ence o f a n e lem en t
ma y b e defi n ed a s the n u mb f g
er o n e a ti ve e l
ectr ons a n a to m f
o
tha t el ement l os es or ga i ns to f or m chemi ca l l i n ki ngs 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
.
INTRO DUC TION VA LE NC E . 13
every chemical linking betw een 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 C harge, .
The question now naturally arises : How is it possible t o

ascertain which atom is positive and which is negative in a
compound ? For substances which conduct the current in
solution the charges manifested by s ome of the atoms or
,
groups of atoms will S how d ireCtly the distribution of some

of these electric charges In general the relative positions
.
,
of the elements in the Periodic S ystem 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 , Na Cl;

2 + ii
N H3; C H4; CC 14; etc
In the vertical series the main
.
and subgroups must be considered separately .
The older terms positive and negative elements now

, ,
acqu ire a more precise meaning A positive element i s .
on e whose atom in chemical combination has lost on e or

, , ,
more negative electrons ; a negative element one whose ,
atom in chemical combination h a s gained one or more

electrons W hen an atom is reduced it gains negative or
.
,
loses positive charges S ince in any given compound the

.
, ,
atom which acquires the electron is the one which has the
greater attrac tion for it under the given conditions and ,
S ince 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 re d u c
,
ing potential ( or has the smaller attraction or a ffinity for

t h e negative electron ) ; and conversely that element which ,
l4 C HEM ICA L RE ACTION S .
h as the greater oxidizing potential ( or the greater affinity

f or 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
.
t ial s signify the same relations a s the chemical affinity of
different atoms for each other Just as with the other .
measures of the intensity factor of chemical energy the ,
use of the oxidizing potential must for the present be limited

to qualitative rela tions with most organic substances .
It is possible to conceive of compounds in which the two

elements which enter into chemical combination have oxi
d i z i n g potentials so clo se to each other in value that two
combinations are possible in which the positive and negative
elements are interch anged in the two compounds A s an .
example of this type of isomerism the two isomeric iodine ,
chl orides may be mentioned S ince 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 IClfor the stable

form and ClI 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 HCI 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 ,
p resence o f other substances influence the

, oxidizing poten
t i al s o f th e elements or as formerly expressed the a ffinity
, ,
of the ele me nts for each other L ikewise the pressure and
.
m
.
,
t emperature of a ixture of methane and water may be

s u ch that the neg ative c arb o n of the methane is oxidized
t o the p ositive carb on o f c arb on monoxide or dioxide It .
,
t h e r ef ore seems ossi ble that di ff ere nces i n c onditions may

’
,
p
reduction with inorganic compounds as generally accepted , ,
is unquestionably that involving a C hange 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 r e d u ct lon I nvolving the

-
transfer of electrons it becomes evident that in speaking

,
of oxidation reduction it would be more correct to sa y that

-
a particular element in a compound is oxidized or reduced .
Thus in th e case of the oxidation involved in changing

ferrous chloride into ferric chloride it i s the iron which is,
oxidized the chlorine is neither oxidized nor reduced

,
.
B ecause of the i n c orr e n t way of say i ng that a compound

has been oxidized or reduc ed the meaning of the terms
,
oxidation and reduction has in many instances become

vague If electrons are not responsible for the union be
.
tween atoms i n molecules which are not electrolytes the ,
electrical definition of oxidation and reduction becomes

inapplicable and it is necessary either to fall back upon som e
of the older definitions or to use an en tirely n e w one for
these cases S o 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 t o 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 t o the older definitions .
M ethane can also be converted into carbon dioxide by

treatment with chlorine that is substit ution and s u b
, ,
sequent hydrolysis neither action being oxidation according

,
to the older definition M any other examples might b e

.
mentioned and the general conclusion is arrived at that

, ,
it wo uld be impossible t o give any satis factory definition of

oxidation applicable to all cases Furthermore the oxida
.
,
tion of formaldehyde by permanganate as describe d befor e

showed that the oxygen from the permangana t e did not
INTRO DUC TION VA LE N CE . I7
add t o the formaldehyde since the permanganate was not

in the same beaker There was a current of negative elec
.
t ri ci t y 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 C haracter it would be very difficult

,
to find a suitable definition or description for this form of

oxidation .
S ince the experimenta l evi d ence at hand is n o more

against than in favor of the view that electrons are r esp on
sible for valence in the case of non electrolytes than in the
-
case of electrolytes while indirect evidence 18 l n favor of

,
this view it is much simpler to adopt the view of one kind

,
of force acting between atoms in all compo unds 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 E xperimental
. .
facts have made the negative electron ( the atom of elec

t ri c i t y) 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 speaki ng of valence it is not su fficient to give a
,
\
number for i t s value but that at the same time i t 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
valence is based It would be possible to construct a

.
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 lin k i n gs and to consider all other combinations as
,
positive valences This treatment would simply amount t o

.
a shift of the standard of reference from what is now con

s i d e re d t o be an electrically neutral atom to an atom
,
carrying the maximum number of negative charges (which

is eight ) and to consider the valence a s 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 a s the result of experience A t any rate while

.
,
it is important to point out that the standard or basis in

use is arbitr ary in the sense that it is based upon exp eri
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 .
E arl ier i n 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 S ign of this free energy change depends upo n

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 .
INTRO DUC TION VAL E NC E . 19
Nitrogen in ammonia has a valence of 3,
Nitrogen in nitrous acid has a valence of 3 ( HO N O ) , .
Nitrogen in ammonia therefore di ff ers 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 h a s a valence of 5 The difference between the

.
nitrogen in the extreme states i s 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 a m monia to the nitrogen l n n i tric 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 S how similar relationships .
C arbon in methane has a valence of 4( C H4) . C arbon

it
'
in carbon tetrachloride has a valence of 4( C C 14) The .
di ff erence 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

:1 4 .
the carbon in methane In methyl chloride ( C H3C l) the

.
,
carbon atom has lost one negative electron and gained

three or its valence is
, 3 1 and its state of oxidation
,
orm e t h a n e the valence of the carbon is

2 ; in d i chl ,
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 series of compounds shows the importance of
.
stating in full the charges of the atom s which go to make

up the valence and it also i llustrates the meaning of the
,
term oxidation of an atom The state of oxidation of an

.
atom conveys a definite meaning chemically only in com

parison with the atom in the other states of oxidation .
The change in the valence of the atom is the significant

fact in speaking of oxidation and while the state of oxida
,
tion may be S hown by the number and S ign of its valence ,
i t s importance i s 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 i t s valence is eight units ; for example chlorine in ,
hydrogen C hloride 1 ) and chlorine in perchloric acid

sulfur in hydrogen sulfide 2 ) and sulfur in
sulfuric acid nitrogen in ammonia 3) and nitro
gen i n nitric acid carbon in methane 4) and
carbon in carbon tetrachloride This difference
refers to the same relation to which M en d elé e ff referred in
h i s Periodic S ystem when he stated that the su m 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 .
A s 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

.
l i n k i n gs as written heretofore in structural formulas will

therefore be replaced by arrows ; H C1 in place of H Cl ,
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 u se these signs in connection with the

formulas .
C H A PTER II .
VA LE N C E ( C ONTIN UED ) ; —
C C O RD IN A TION N UM B ER .
IT has been emphasized that in simple compounds the

valence is the capacity of an atom of on e 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
.
C 3C 12 0H2 0 C I C 13 OH2 O C u SO4 5 HzO; ammoniates such

.
,
‘
.
,
.
as Ag C l2 N H3 C U SO4 4NH3 H2 0; and double salts such

.
,
. .
as 2 KC 1 P t Cl
4 These compounds have . .
as components S impler compounds which are combined in

definite proportions j ust 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 f or ex ,
ample sulfur trioxide with water ammonia hydrogen

, , ,
chloride etc platinic C hloride with ammonia water

, .
, , ,
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 C hloride and the nitrogen in the ammonia etc

, ,
.
,
possess a residue of unsaturated a ffinity which permits ,
such groups to m utually satisfy each other When the .
amount of this a ffi nity i s sufficient t o bring about a stable

21
22 C H EM I CA L RE ACTION S .
combination between the single molecules it assumes prae ,
tically the same r é le a s the ordinary valence viz ; it effects ,
an interdependence between two elementary atoms and in ,
this way unites two radicals to a molecular complex These .
new valences diff er however from ordinary valences in

, , ,
that they are not able to unite univa l ent 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

H H
o o o
1 .
“
S ince according to this formula four hydrogen atoms are ,
bound to nitrogen it is hardly to be supposed that one

,
hydrogen atom is linked up by a greater amount of affinity

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 amount of a ffinity .
A mmonium is therefore a c omplex radical N H4 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 N H4
.
,
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 A mmonium salts have therefore
.
, ,
the following structure :

H
N / X
/ \ H
.
E . C . C . B aly approached this general question in a

different way . His views may be stated briefly as follow s
24 C HEM IC A L RE ACTION S .
readjustment of these forces causing a formation of the

,
stable compound .
If the valenc es in the ammonium chloride are assumed to

be due to electrons a s described in the first chapter then the ,
A —
4 fi '
structure of the compound would be or , indi
fi / \ Ci
cating the direction of transfer of the negative electrons
H\ / H
by means of arrows This formula for the
/ \
Cl 11
structure of ammonium C hloride has all the advantages of

the Werner formula viz ; it agrees with th e results of V
,
.
’
Meyer and M L eeco s ( L ieb A nn 1 8 0 1 7 3
. . e xpe ri
.
,
ments that the four hydrogens bear the same relation to

the molecule and it S hows 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 A lso 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
, ,
it would be difficult to state by means of the struc t ures

whether any oxidation or reduction had occurred .
M any compounds S imilar to amm o nium 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 ammoni um salts Although .
this generalization appeared to hold for a number of such

compounds other substances were prepared after a time
,
in which these simple relations were n ot observed Thus .

,
th e compound ( N H3) 4HC1 ( cf Werner N e ue re Ans ch a uu n

.
,
VA LE NC E ; C O O R D I N ATI O N
-
N U M B ER . 25
gen ) was prepared then compounds such as Ag Cl( N H3) 2

, ,
Pt Cl 4( N H3) 6 C U SO44
4( N H3) 2 P t C l ,
N H3H2 0 etc which did
, , .
,
not follow such simple laws and for w hich the ordinary ,
ideas of valence did not suffi ce S ome of these compounds .
“ ”
were in fact termed anomalous because the y did not fall ,
into a scheme of simple formulas a s it was expected they

should It was thought that the reaction between a m
.
monia or an a mine and hydrochlor i c 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 j ust indicated S howed 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 18 7 5 ( B ull S oc C him [ 2 ] 2 4 1 60

.
,
. . .
, ,
showed that in cooling a solu tion of hydrogen chloride in

ether a crystalline compound was formed containing a n
,
equal number of molecules of ether and of hydroge n

chloride This observ a tion wa s an isolated one for som e
.
years J N C ollie an d T Tickle ( Trans C hem S oc 7 5

. . . . . . .
,
7 10 found that dimethylpyrone formed compounds

with the halogen hydrides which showed
the properties C haracteristic of ammo
nium halides and later were found to
, H0 CH
ionize in solution in a manner S imilar
to ammoni um salts and were therefore ,
0
D i m e th y lp yron e
comparable to them A B aeyer and . .
V Vil
. i ger ( B e r 34 2 67 9
l . 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 analo gous

, .
to the nitrogen ( ammonium ) compounds They are n ot .
as stable under ordinary conditions and their isolation and ,
preparation in quantity for study is difficul t for most of

them C ertain acids have been found to be e spe ci a lly
.
.
s u itable for the preparation of these stable oxonium salts ,
hydroferrocyanic acid ( by B aeyer and Villige r) and per

chloric acid ( by K A Hofmann B e r 4 3 108 0 . .
, .
,
In order to determine whether definite compounds are

“
formed it is necessary to study the Property C omposition
,
-
”
C urves 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 Ru le or any of the larger modern ,
text books of general chemistry ) shows the existence of

-
such oxonium salts a nd their composition since it may be ,
stated in general terms that each maximum point of such ,
a freezing point curve plotted with abscissa s as relative

content of the two components in the mixture and ordinates
a s the freezing points shows such a compound of the c om ,
position given by the point on the abscissa axis The .
application of s uch 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 S imilar 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 .
A mong those wh o have worked in this field may be

mentioned J N C ollie a nd T Tickle Trans C hem S oc
. . .
, . . .
7 5 7 10 , J N C ollieTIbi d 8 5 9 7 1 . A B aeyer
. .
, .
and V Vi lliger B er 342 67 9 3612

.
, 35 12 01.
, , ,
S Hoogewerff and W A v a n D orp Re c trav chim 2 1

. . .
, . . .
,
34 9 J Thiele and F S trauss B e r 36 2 37 5

. .
, .
,
D Vorl .an d e r L ieb A nn 34 1 1 , V A Pl ot n i koff

. .
, . .
,
J Russ phys chem G es

. . 1088 .
4
0 64 . .
,
H S tobbe L ieb A nn 37 0 9 3
.
,
K A Hofmann and
. .
, . .
c o workers B e r 4
- 3 17 8 18 3 2 62 4
,
. D M c I nt osh
, , , .
,
—
VA LE NC E C C O RD INATION N UM B ER . 27
Jour Amer C hem S oc

. . O M aass and D
. . . .
M cIn t osh Ibid 34 12 7 3

,
35 5 35
.
,M , .
Gomberg and L H C one L ieb A nn 37 6 18 3

. . J , . .
, .
Kenda l Jour A mer C hem Soc 36 1 2 2 2 1 7 22

‘
.
, . . .
, ,
J Kendall and C D C arpenter Ibid 36 2 49 8

. . .
,
.
,
J Kendall and W A Gibbons Ibid 37 149 ( 19 15 ) 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 .
NH g, hydrogen chloride , HCl , and ammonium chloride ,
N H4C l .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 on e g i ven

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
.
,
( state of oxidation of phosphorus 4 1 s ul
f oni u m 3 1 oxonium ( : 3 1 d
iodonium 2 1 selenonium 3 1
arsonium 5 1 s t a nn on i u m 3 1
and stibonium 5 1 4) compounds .
The characteristic property of these S imple molecular

compounds which may be grouped under the name of
,
“ ”
onium compounds is the fact that the atoms or groups
,
“ ”
combined directly with the o n ium forming or central
element act as a unit with the central atom in many phys
,
ical and chemical transformations and are often termed

radicals This is shown for physical phenomena in the c on

.
duction of the electric current where these groups act very

o ften as ions and in chemical reactions in metatheses where
,
the groups are capable of replacing other atoms or groups .
When ammonia is added to plat i nic chloride it appears ,
that two methods of combi nation exist The first two mole .
cules of ammonia add to form the compound Pt C l 4 2 N H3 .

,
which is not ionized in sol ution and does not yield a preci p i
,
tate of silver chloride when treated with S ilver nitrate If .
a compound containing a third molecule of a mm on la 1 s

4 3N H3 this substance ionizes and one of
'
prepared P t C l
, .
,
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 t wo In .
the substance P t C l44N H3 two chlorine atoms are ionized

.
, ,
while in P t Cl4 6NH3 four chlorines are ionized The last

.
, .
four ammonia molecules play a di fferent 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 ,
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 c om

pound a t only one third of the C hl orine 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 CI C l3 OH2 0 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 A nschauungen III E dition ( 19 1 3) p , ,

.
It has been stated that platinic chloride wil ladd ammonia

j ust as hydrogen chloride does The only difference at the .
VALE N CE ; —
C O O R D IN AT ION N UM B ER . 29
present time is that the ammonia can exert two distinct

influences or c a n add in two ways in connection with
'
platinum chloride while it is probable that it ca n add in

,
on e way only to hydrogen chloride although an allotropic

,
modification of ammonium chloride was described recently

( F
. E. C. S cheffer C hemical
, A bstracts 1 0 411 ,
A mmonium chloride in aqueous solution yields C hlorine

—
ions j ust as the platinum chloride ammonia compound ,
2 N H3 P t C l
.
4 with 1 2 3 or 4 additional molecules of
, , ,
ammonia does S ince ionization was pointed out as a

.
characteristic property determ i ning in which way the a m

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 i s combined with the hydrogen

chloride in the same way that the ammonia is combined
with the p latinic chloride when the chlorines of the latter
become ionic If therefore the structure of ammoni u m
.
, ,
chloride i s known it 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 .
S ince d ia mm on o p latinic chloride ( N H3) 2 Pt C l4 combines

, ,
with ammonia in a simi lar way to that of hydrogen chloride ,
the st ructure of the a d dition product may be written in a

( NB 3)2 P t 013
H \
S imilar way namely — Introducing succes
E
, NA
C1
H
H
S l ve molecules of ammonia analogous structures follow
, ,
until when all four chlorines are ionizable the structure

’
30 C HEM ICA L R E ACTION S .
2 3+
or ( N H3) 2 Pt ( N H3 C1) ; is obtained The question .
which now presents itself i s the way in which the other two
molecules of ammonia are combined in the last compound
and also in ( NH3) 2 Pt Cl4 The only evidence which is .
available i s that starting with platinic chloride ,in which

the valence of the platinum i s 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 t wo molecules of hydrogen C hloride ,
forming H2 P t C 16 in which two hydrogen atoms are i on i z

,
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 Cl H
\ \
H Cl Cl H
etc In this way only one kind of valence is present and

.
, , ,
s o long as no evidence exists against these structures and ,
evide nce ( 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
.
H 3N Cl ‘
for the d
O
l- a
O
a t 1n 1c c h l
mm on la t e of pl
0
orld e , H3N
O O
Pt —C l
Cl Cl
When additional molecules of ammonia combine with the
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 i s .
different from the idea developed here S ince the addition .
auxiliary or principal valences and ionizing in solution .
The method introduced by Werner of writing these groups

is extremely convenient the inner zone being enclosed
,
in brackets The exp re ssmn s I nner zone and outer zone

.
and the u s e of brackets will be followed in this book but ,
the significance of the combinations bet ween the atoms

from the point of view of the electron conception of valence
must be kept strictly in mind In using the terms intro
.
d u ced by Werner it is not intended to endow the groups

,
with the physical S ignificance which the meanings of the

words m ight imply The expressions inner zone and outer
.
zone simply mean di ff erent groups which have a partially

independent existence under special conditions ( the most
common one being in solution ) and the atoms comprising ,
'
such a grou p a ct as a unit very often The terms inner and .
outer mean nothing more and must be looked upon as a

convenient phraseo l ogy .
The force field theory of B a ly assumes the primary forma

tion of an addition product which under certain conditions
, ,
c a n become a definite compound in which the atoms are
combined by ordinary valences The vie ws outlined here .
may be used similarly The first addition of ammonia and

.
hydrogen chloride may produce a compound H3N Z HC l ,
or H3N Z C l H presumably the former by analogy as will

,
be pointed out later and this then rearranges or tauto

,
m eri z e s to the more usual form H4N C l These two steps .
correspond to the steps of B aly The onium valence corre.
i
Sp on d s n a number of compounds to the auxiliary valence
of Werner and the reaction j ust given may be stated in

,
’
Werner s terms as due to a compound being formed of
molecules combined by an auxiliary valence which under ,
ce rtain 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 ,
di ff erence between valence and chemical a ffinity strictly

i n mind
.
VA L E NC E ; —
C O O R DI N A TI O N N U M B ER . 33
The structures developed with platinic chloride c a n :
evidently be applied to a great number of compounds such ,
as hydrates other ammoniates and molecular compounds

, ,
in general A compari son of the structures of h exa m m on o

.
platinic chloride and the hexahydrate of calcium chloride

will S ho w this :
4 -
3 “
3
if N 6
+
ii
’
CI Cl
ns
3 2
:i / ri
‘
:g l
—P t — 1I
.
Cl
: 3
+
2
2
R
.
/ E. or BB/ \ 25
From the foregoing it is evident that the co ordination -
number of the platinum in platinic chloride di ammoniate -

,
( N H3) 2 Pt Cl4 or in platinic chloride hex aammoniate

,
-
,
( N H3) 2 P t C l44N H3 is s i x while the c o ordination number

, ,
-
of nitrogen in ammonium chloride is four etc ,

.
C alcium 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 s ix b ut what it is in the tetrahydrate is

,
difficult to say S ince 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 S hows th at the co ordination number of the calcium

-
is dependent upon external conditions j ust as the ordinary

valence is .
C alcium chloride combines with eight molecules of a m

monia or the calcium has the c o ordination number eight
,
-
in this compound A large number of salts have been

.
found to crystallize with s ix molecules of water With .
regard to ammonia copper sulfate ca n combine with four

,
34 C H E M IC A L RE ACTION S .
molec ul es S ilver chloride with two etc Werner showed

, , .
that the Co ordination number of an element is in general

-
, ,
four six or eight

, , .
These definite numbers S how 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 t o the transfer of a negative electron but ,
indicate a different kind of capacity factor of chemical

energy The manner in which this is to be interpreted and
.
,
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 B arker and the theoretical and e xper i

. .
,
mental researches of W H and W L B ragg and of A C . . . . . .
C re h ore point in this direction

, Whatever the cause may .
be this capacity factor exists and as shown may be inter

, , ,
p r e t e d by means of the general valence i

l n k i n g s of the
electron conception In the later chapters the significance
.
,
of c o 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 ( N H3) 2 P t C l4 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 ( N H3) 2 Pt Cl

-
4 becomes ionic The
structures for the tri —
.
, ,
ammoniate ( N H3) 2 Pt C l4N H3 and , ,
ammonium chloride are analogous :

NH3) 2 P t 013
C] c1
H
VA L E NC E ; —
C o O RD I N A TI O N N UM B ER . 35
When hydrogen Chloride and platinic chl oride combine

to form the addition compound ch lorpla t i n i c acid H2 P t C16
, , ,
the platinic chloride plays a r é le somewhat similar t o that

of ammonia in the formation of ammonium chloride th at ,
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 t o
,
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 z one ; in the second the ,
chlorine is in the outer zone S ince 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 i s crowded out into the outer zone while i n the ,
other it is the chlorine of the hydrogen chloride A ccord

,
.
i n gly the
, structures of the two compounds may b e writte n
Cl and
The two complexes ( Pt ClG ) and ( NH4) bear the same

, ,
relation l n 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 i s an electro positive element and nitrogen in

-
,
a m m on la 18 an electro negative element

-
It becomes evi .
dent i n 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

-
,
central atom potassium chromium oxalate

, ,
may be quoted out of the great number with which the

reader no doubt is familiar A s 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 j ust as in the ammoniates the oxygen of ,
the water m ay serve as the central atom .
It has been stated that water like ammonia c a n be added

in two ways in the formation of addition compounds such
as the hydrates calcium chloride hexahydrate etc similar
, , .
,
to the ammonia in the hexa ammoniate of p latinic chloride

-
,
P t Cl46N H3 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 Pt Cl42 H2 0 which

, ,
-
, ,
is an acid and yields the ions 2 B and and should

therefore be formulated H2 P t Cl4( OH ) 2 The water behaves .
towards the platinic chloride j ust as the hydrogen chloride

does in the formation of the c hlorpla t i n i c acid Ht C le , .
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 ch loride and in each case ,
forces or transfers the hydrogen into the outer zone The .
structures of the two complexes P t C l4( OH) 2 and Pt C ls ,

,
ought therefore to be alike They may be written a s .
follows :
and
I II
The water molecule here has added as H and OH . In order
VA LE N CE ; —
C C ORD IN ATION N UM B ER . 37
to get a definite picture of the diff erences between the three

-
ways in which water ca n function in these addition com

pounds the reader may compare structure I with the strue
,
ture of the hexa hydrate of calcium chloride With the

- .
latter part of the water enters between the ca lcium and

,
chlorine atoms producing chloride ions and part of the

, ,
water is S imply added to the calcium atom by onium valence

“ ” “ ”
or auxiliary valence or force fiel d symbolized by
,
the two arrows in opposite directions It was stated .
p re v rou sly that the first stage in the formation of ammonium

chloride from ammonia and hydrogen chloride may be the
formation of a primary addition compound H3N < HCl )
,
2
,
due S imply to the onium valence or the auxiliary valence

,
or the force field between the nitro g en and the hydrogen

atoms and that this preliminary compound then tauto
,
m eri z e s into ( N H4) C lwith the chl orine in th e outer zone .
N ow this preliminary stage possibly may occur in the for

mation of a llthese 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 se t in the chlorine
, ,
leaving t he calcium to combine with the oxygen of the water .
/
, o Cl
C1
aN
o C1
C1
S imilarly with the di hydrate of platinic chloride

-
,
H2 Pt Cl
4( 0H) 2all the water molecules ma y add to the
,
platinum atom through the force field first and then rear
rangement set in and the hydrogens become ionic .
H2
0H2
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 c a n take place it is im ,
possible to sa y .
Potassium chloride adds to platinic C hloride in the sam e ,
way that hydrogen chloride does forming potassium chlor

,
platinate The latter would therefore have a structure

.
sim i lar to that of the a c1 d , or : Just a s In
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 j ust as potassium chloride does forming ,
the ammonium ch lor pla ti n a t e C h lorpla t i n ic acid Ht C le

.
, ,
adds to ammonia j ust as hydrogen chloride does forming ,
the ammonium chlorpla t i n a t e the di ammoniate of platinic

-
chloride adds to hydrogen chloride forming ammonium ,
c hl orpl a t i n a te
. In each of the above cases an addition
compound plays the same r 61e as a simple compound ,
forming addition compounds with other molecules .
From what has been said in regard to the probable

structures of the h e xa chlorpla t i n i c acid Hg Pt Clfi and the
, ,
orp l
t e t ra ch l a t i n i c acid H2 P t C l
, 4( OH) 2 it is possible to assign
,
structures to the whole series of platinic acids as Werner ,
has done ( Neuere A nschauungen auf dem G ebe i t e der

anorganischen C hemie 3d ed , . pp 40 .
40
.
C HEM IC A L RE A C TION S .
—— —
HN so—
-4 +7
+6 —
E3s o
1 2 2 2
s and g > OHe 2
(HgN) 3Z PfCl
4 and 9 3
1133 6
3 1
— —
Ht
2 2 +
and C h ( OH) 2 ,
and so on .
These examples S how the possibilities of tautomerism in

inorganic compounds The valence or state of oxidation
.
of none of the atoms h a s changed A lthough tautomeric.
changes in molecules will be used in the later chapters it ,
will not be referred to explicitly or in detail .
C H A PTE R I II .
A CI D S A N D B ASE S .
T HE valence views upon which the structures and classi

fi ca t ion of substances depend have been given in some
detail in the preceding chapters B efore proceeding to .
consider the theory of chemical reactions which it is desire d

to emphasize here some furthe r applications of the valence
,
views may be of interest A cids 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 upo n 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 188 7 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 di ff erent ways In the .
electrolytic dissociation in solution in which the positive

hy d rogen ion is produce d the rest of the molecule form s
,
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 produced i s not shown in the theory of

,
Arrhenius It i s true that the relative degrees of ionization

.
of substances in different solvents were S hown to be paral

leled by certain other properties of the solvent such as the ,
dielectric constant and that combination of the solvent

,
41
with the ion has been proven to exist in a number of cases ,
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 th em ( Neuere An
s ch a u u n g e n
, pp 2 7 3
.
( 1 ) There are anhydro acids
an d aquo acids ( 2 ) E very compound which can form a
.
hydrate with water and which then yields hydrogen ions

,
in aqueous sol ution as a product of ionization is an anhydro ,
acid ( 3) E very hydrate which ionizes in aqueous solution

.
yielding hydrogen ions is an aquo acid or in short an acid

, , ,
In terms of the ionic electrochemical viewpoint the fo l low ,
ing definition is given by Werner for an anhydro acid :

A compound which in aqueo u s 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 va lue for the hydrogen ion concentration character
i st i c 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 th e principles
outlined in the earlie r chapters will now be given .
It will be of interest to take up a number of acids contain

ing oxygen S ulfuric acid may serve as a typical example
. .
Its structure is formulated ordinarily as :

on
S
/
\ OH
This structure is based upon a number of experimental
ACI D S A N D B A S E S . 43
facts such as the reactions of organic derivatives of the

,
acid and relate d c ompounds 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 Tor a substance possessing this structure

to ioni z e as an acid If however the structure is written
.
, ,
in the tautomeric form , this diffi culty disappears and sul

furie acid falls in line with the platinum acids The tauto .
meric forms of sulfuric acid are :

0“ O H
B H and
S
1/
0 H
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 A ccord

, .
ing t o the older view the formation of sulfuric acid from

,
sulfur trioxide and water is due to the opening up of one

of the double bonds between the sulfur and one of the
oxygen atoms and the addition of the water as hydrogen
,
and hydroxyl t o this opened up group .
— —
0 8 O + H OH
2 02 s <OH
OH
This explanation cannot be applied t o the mechanism i n

volved in the formation of the t e tra ch lorp la t i n i c acid ,
H2 Pt C l4( OH) 2 .
The addition of hydrogen chloride to sulfur trioxide ,
becomes analogous to the addition of hydrogen chloride t o

platinic chloride yielding in the first case ch lors u lfon i c
, ,
acid HSOgCl and in th e second case chlorpla ti n i c acid

, , , ,
HgPt C le.
The addition of potassium chloride to platinic chloride

to form potassium ch lorpla t i n a t e K2 Pt C 16 is similar to the
, ,
formation of potassium sulfate from potassium oxide and

sulfur trioxide .
The addition of ammonium chloride to platinic chloride

to form ammonium chlorpla t i n a t e ( N H4) 2 P t C 16 is similar
, ,
to the reaction between chromium trioxide and ammonium

chloride to form C I Og C lN H4 ( 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 ) .
It is possible to formul ate the reaction involved in the

formation of the first stage addition compound in the case ,
of many of these substances as follows :
8 03 H2 09 8 03Z H2 0, 8 03
8 03 N H3 5 ‘
9 S03Z N H3,
H2 0
H2 0 2
_ HCl
Pt Cl 2 HC 1S
<
4
P t Cl
4
KC l
Pt C l
4 2 K Cl
fi + Pt Cl
4I
KC P
Au C 13 KC l
%
Au C 13 N H4C lE
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

consist of more than one zone are ionogens by definition or
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 c om
ACI D S AN D B AS E S . 45
pound corresponds to the hydrogen ion of A rrhenius A .
substance dissolved in water will be an acid ( that is it will ,
furnish hydrogen ion H ) if it forms hydrates containing

+
hydrogen or hydrated hydrogen in one of the zones F0? .
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 01 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 C hloride to form c h lorpla t i n i c

acid or by displacing water in t e t r a chlorpla t i n i c acid ,
and thus forming ch lorpla t i n i c acid In .
ch l a t i n i c acid the platinic chloride may be said to serve

orp l ,
the same purpose as the water does in the hydrate of hydro

gen chloride that is it separates the hydrogen a n d the
, ,
C hlorine of the hydrogen chloride into the two zo nes It: .
might be said therefore that since water is ofte n sp ok e n of

, ,
‘
as an ionizing medium for electrolytes tha t the platinic , ,
chloride is also in the same sense an ionizi ng; me diu m for

certain electrolytes such as hydroge n ch lori de pota s siu m ,
chloride etc
,
.
S ince the behavior of ammoni a toward hydrog en chl or i d e

,
is similar to that of water a nd off pla ti ni c; chloride i t also ,
should yield an acid in f orm ln g amammoni a te w i th h y d r ogen

chloride T his is in fa ct the ease, fior w hen ammoniu m
‘
46 CHE MI CA L REA CT ION S .
chloride or hydr ogen chloride is dissolved in liquid a m monia

and this solution treated with magnesium or a similar
metal hydrogen is evolved and the metal i s dissolved A t
, , .
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 ,
on e 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

ch l or p l a t i n i c acid H2 P t C l4( 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 S ulfuric acid H2 S O4 which is itself an addition
.
, ,
compound may add to water to form compounds of the

,
third order such as H2 SO4H2 O H2 8 042 H2 0 The c on . .
s t i t u t i on o f such higher hydrates may be indicated as follows :
H2 0) Z l
b
a
It therefore becomes evident that the mono hydrate -

,
SOg H2 0 will have the constitutional formula H2 ( S O4) and

.
,
be s imilar to t e tra ch lorplat ini c acid while

t h e hydrates of the higher orders will have hydrogen in the
h y dra ted form and correspond to the hy d rates of hy drogen
,
The structures of acids a s outlined are not co m pl et e for

the co ordination number of the hydrogen h as not b een
-
taken into account in their development Unfortunate ly .

,
the co ordination number of hydrogen i s not known A t

- .
t h e same time it h as not been esta b lishe d experimentally

,
are displaced by ammonia then they are spoken of as

,
ammonium ion and not hydrogen ( or hydrated hydrogen )

ion The S imilarity is further emphasized by reactions
.
such as the solution of zinc in a water solution of ammonium

chloride or the so lution of magnesium in a liquid ammonia
solution of hydrogen c hloride with evolution of hydrogen ,
similar to the solution of a metal in an aqueous solution of

an acid .
It further emphasizes the point that ammonium salts

are only hydrogen compounds where the hydrogen atom
h a s associated with on e ammonia while if it has associated
,
with it more ammonia molecules it is generally considered

as an abnormal addition compound Ammonium salts are
.
only one particular case of ammoniated hydrogen com

.
pounds S imilarly oxonium salts are only a particular

.
,
case of the ser i es of hydrates of hydrogen and S imilar

compounds .
It is also possible by this theory to correlate the fact that

platinic ch loride dissolved in aqueous hydrochloric acid
forms chlorpla t i n i c acid with the formation of addition
compounds similar to ammoniates S ince the c o ordination
.
-
number of the platinum atom is six the platinic chloride

,
c a n combine with two molecules of hydrogen chloride to
form a compound similar to the d ia mm on i a t e S ince .

,
however the addition compound exists in a water solution

, ,
the hydrogen chloride ca n also form the hydrate and equal

the c o ordination number of hydrogen In this case the
-
.
hydrogen chloride will become ionized j ust a s with the

ammonium chloride in the water solution In oth e r words
.
,
either the water or platinic chloride which m ake up the c o

ordination value of the hydroge n of the hydrogen chloride
will enter be twee n the hydrogen and the chlorine and
sep ara te o r ioni ze them It is probable that in this case
.
th e platinic chloride enters between the hydrogen and the

chlorine and hence the structural formula for chlorpla t i n ic
—
acid may be written as follows assuming the co ordination
number of hydrogen to be four : t C16]
It is to be noted that in the case of ch lorpla t i n i c acid the

plati nic chloride is really considered to be the ionizing
agent of the hydrogen chloride while in the case of the
,
hydrate of hydrogen chloride water i s 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 i on containing the platinum atom When a m .
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 i on If the valence charges upon the various
.
atoms in these addition compounds are taken into account ,
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 on e 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 hydrogen is probably equalled and the water

entering between the hydrogen and the chlorine of the
50 CHE M I C AL RE A C TI ON S .
hydrogen chloride causes ionization which is indicated in

,
the formula by two zones When pla
tini o chloride is added to an aqueous solution of hydro

chloric acid or hydrate of hydrogen chloride the di
, ,
basic acid chlorpla t i nic acid is formed generally given the ,
formula H2 ( Pt C16) and assigned by Werner the structure

Cl Cl
H2 C lP t C l
01 Cl
Here again the co ordination number of hydrogen will be

-
considered as well as that of platinum In other words .

,
j ust as in the case of hydrogen chloride in water the sub ,
stance does not ionize until the co ordination value of the

-
hydrogen i s rea ch e d and consequently the more correct

.
,
formulation would be The part

actually played by the platinic chloride in forming the
ch lorpla t i n i c acid in a water solution of hydrogen chloride ,
18 that platinic chloride replaces the ionizing m olecule of
water in the hydrate of hydrochloric acid .
H2 0: )x ( H2 02 ) X H2
It is interesting to note the frequenc y of the occurrence

of complexes in the inner zone in which the co ordination -
number of the central atom is eight H2 ( S O4) , .
H( C lO4) H3(AS O4) (Ru O4) ( Os O4) etc all conform t o

, , , ,
.
,
the general type ( A O4) for the inner zone water of hydra ,
tion being omitted in these formulas In determining the .
c o ordination number 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 t wo This rule is arbitrary

.
,
A CI D S AN D B A SE S . 51
For the present it is necessary t o 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 t o assign

the hydroxyl structure to sulfuric acid and its hydrates
“
H o\ II HO OH
S
/
*
8 II
H o
/
0 HO OH
8 03 H2 0
. $03 2 H2 0
.
A ccording to these structures t hB double linking between

the oxygen and the sulfur opened up and a dd e d t h e hydro
gen and hydroxyl of the water forming in this way t wo ,
hydro xyl groups combined with the sulfur in place of on e

oxygen
o
—
H OH —
o
HO\
/
¢
s
HO
A ccordingly , the dihydrate should be a tetrabasic acid if

the acidity were due to the hydrogen of the hydroxyl but ,
this i s contrary to experimental facts S imilarly osmium .

,
a n d ruthenium oxides might be expected t o S how a greater
tendency to form acids than sul fur trioxide S ince they con
tain more oxygen atoms with double linking t o combine
with the water It is evident therefore that a knowledge
.
, ,
of the c o ordination number as well as of the atomic valence

-
is necessary in order t o determine the basicity of an acid .
Just as there i s a series of acids in which the co or d ination -
number of the central atom is eight a series of acids exists ,
in which the co ordination number is s i x A n example of

-
.
this series is nitric acid The atomic valence of

the nitrogen is plus five the c o ordination number six
,
-
,
and the basicity one The same is true of chloric acid

.
H( C 103) iodic acid H( IO3) etc M eta phosphoric acid

, , .
- ,
H( P 03) belon g s to th i s g r ou p although Or th ophosphoric

, ,
-
acid H 3PO4 belongs to the group in which the c o ordination

, ,
-
number is eight This brings up the question of whether

.
an acid the c o ordination number of whose central atom is

,
-
si x can be converted into one whose central atom h a s a

,
c o ordination number of eight by means of hydration

-
.
T h i s a pp e a r s 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 h y

, ,
d ra t es 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 combin ed 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 .
[ NO3 or
[
H NO3 or H
The c o ordination number is a function of externa l

-
physical conditions Its val ue 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 c o ordination number may change from s ix t o eight

- .
This change is similar to the changes which occur with

atomic valence S ome elements can S how several di ff erent
.
states of valence while others S how only one,

.
The ionic theory showed that bases yield hydroxyl ions

'
in aqueous solu ti on a n d that a base might be defined as a

,
substance which in solution form s hydroxyl ions .
S ince ammonium salts c a n be formed directly by the

addition of ammonia and acid to each other ammonia ,
itself has sometimes been S poken of a s a base S imilarly .

,
since amines are like ammonia in this respect they also ,
ACI D S AND B ASE S . 53
have been considered to be bases A t first in order to .

,
distinguish them from the true metallic alkalies they were ,
sometimes called alkaloids ( A W Hofmann L ieb A nn. .

, . .
73 9 1
,
This term however i s now reserved for
, ,
the more complicated amines which occur in nature which ,
show marked physiological properties Two different d e fi .
n it ion s for the term base have been current with the amines .
( )
1 They furnish hydroxide ion in aqueous solution ( 2 ) .
They combine with acids to f orm substituted ammonium

salts This naturally h as led to some confusion since
.
, , ,
amines have frequently been cal l ed strong bases or weak

bases depending upon the amount to which ammonium
,
salts were formed when they were added to an acid .
A ccording 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 u n ionized s u b -
stances present in solution The equation for calculating

.
the ionization constant (which naturally S hould hold for

all substances l n solution not merely bases ) is as follows
,
+
for a substance B A ionizing into B and A
,
“
K’
[ B A]
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 S lightly 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 d i fli c u lty .
arises however which prevents a direct comparison D i s

, ,
.
t ri bu t i on experiments with organic solvents and an aqueous

solution of ammonia showed that in the water only a part
,
of the latter was present as ammonium hydroxide the rest ,
being dissolved as such ( ammonia ) or more probably as a

hydrate The ionization constant t o S how the strength
.
,
of the base should be calculated from the concentration of

the ammonium hydroxide from the equation
OH
—
[ N H4 l[ l+
Kl'
[ N H4OH]
At the same time the equilibrium
,
[ N Hall ol
K2 ’
[ N H4OH ]
or some similar equi librium must be taken into account
, .
The same i s true for the substituted ammo nium hydroxides .
The values of the ionization constants for these bases a s ,
determined ordinarily are apt to be misleading for this

,
reason A few of the values h ave been determined cor

.
rect l
y . The influence of the solvent is shown here b i t 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 j ust as with the acids
.
, ,
follow the lines indicated by Werner and the conceptions

developed here .
A ccording to Werner ( Neuere A nschauungen pp 2 68 ,

.
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 combi ning with the hydrogen ion of

the water and producing hydroxide ions ( from the water )
,
in a concentration characteristic for the substance A quo .
bases or bases are addition compounds of substances with

, ,
water which yield hydroxide i ons in aqueous solution .
The method of indicating these relations with hydroxyl

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 the s e relations furth er here ”
formulated as follows : [ HNH3] CI H2 [ P t C16] H[ SO3C1] , , ,
H[ Au C l ,4] [ H2 0H] C l etc The lin kin gs 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 intra m olecular oxidation a n d reduction .
The last of the compounds given in the preceding para

graph wa s [ H2 OH] C 1 This compound with water would
.
evidently be an example of the compounds formed when

hydrogen chloride i s dissolved in water M any substances .
combine with water to form compounds containing water

of crystallization In the last fifteen years much evidence
.
has been accumulated which S hows that hydrates exist in

solution as well and also that ions are hydrated The
,
.
most careful work in this field was do n e by E W Washburn . .
and by G B u ct ck 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 s a y they determined the

.
,
ratio between the number of water molecules combined

with the lithium sodium potassium c aesium or hydrogen
, , , ,
ion and the number of water molecules combined with the

,
negative chlorine ion for certain definite concentrations of

aqueous solutions of these salts D ifferent amounts of water .
were found to be combined with the positive I ons but in every ,
case m ore water was combined with or associated with

, ,
the positive ion than with the negative ion It was i m .
possible to determine directly whether any water was asso

c i a t e d 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
.
g e n c hloride with w a ter was given as [ H2 OH] C 1 In detail .
ACI D S A N D B A SE S . 57
4
.
H
this would be in which the oxygen is in the
Cl
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 chlor i ne l n the outer
‘
zone and the ions are [ H30] and C l omitting the addi
,
+ ‘
t i on a l water molecules which may be combined with the

hydrogen and the chlorine .
It is necessary to mention here the fact that water m ay

also be in combination with or associated with the negative,
ion as well a s with the positive ion A salt such as hydrated

,
.
magnesium sulfate will illustrate this The composition of .
this substance is M g SO47 Hg O It h a s been shown by vapor

. .
tension measurements that s ix 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 molec ule of water is
,
associated with the S04 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 S hown previously that hydrates and ammoniates

belong to the class of addition compounds The substance .
CI Cl
‘
3O H2 0 for example is similar in structure to the

.
, ,
substance Pt Cl46N H3 etc The water in these compounds

.
, .
is in combination with the metallic atom in the inner zone

or S phere where the latter functions as the central atom
,
.
The structures of some of these compounds may therefore

be given as follows :
6 H
Cl
91
Cl 0 Cl
It was pointed out that the co ordination number of -
the central atom varied depending upon certain physical

,
conditions s uch as temperature etc This means that the , .
number of molecules of w ater in the hydrated salts varies

with the conditions but there are certain limit s wi t hi n
,
.
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

,
Ca C lg
, .
z 4
C 3C 12 2 H2 0 C a C l H2 0 and C 3 C 12 0H2 0 The
,
.
, . .
graphic formulas for these substances might be written

as follows :
é/ C
a Cl
a
.
Cl Cl
C 3 012 C a C 3 012
; . 4H2 0 C3 ;
Several relati ons are br ought ou t by these formulas

I n the first place the calcium is taken to be in the same
,
state of oxidation 2 ) in all the compounds In th e .
second place accord ing to these formulas the only s u b

, ,
stance which would ionize in solution is the last which
would form the ions and 2 C1 A t present .
there is no e X p erIm e n t a l 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 ,
s uch as the hydrates of chromic chloride and the a m

m on i a t e s of platinic chl oride the chlorine only appears in
,
the outer zone and forms ions when the final hexahydrate
or hexammine stage i s reached For this reason the di .
and t e tra h yd r a te s are formulated as non ionogens - .
It has been possibl e so far to assign definite structural

formulas to many of the compounds which are made up of
t wo or more simpler molec ules ( compounds of the second
and higher orders ) The fo rmulas assigned have been

.
based upon certain definite chemica land physical reactions

or relations The compounds have a fairly considerable
.
range of stability so that the study of their reactio n s makes

it possible to treat of a portion of the molecule at a time ,
leaving the remainder constant or unchanged In develop .
i n g the subject it is now necessary t otake up more complex

,
substances ; that is to s a y 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 a s far as possible A d i ffi cult v is encountered

.
i n the practical treatment That definite compounds are

.
formed may be proved conclusively in many of these

binary or ternary mixtures but the link i n g s between the
,
atoms cannot be determined as definitely The methods in .
u s e 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 di ff iculty of
, .
assigning definite structural formulas to a number of these

substances must be faced squarely A n attempt to write .
the formulas with insufficient evidence is of no value but ,
on the other hand it is possible to u se the classificatio n s

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 thes e compounds as m ole c u

lar compounds but it will be shown in succeeding chapters
,
how di fferent classes of reactions may be grouped together

i n ki ngs between the
s o that even witho u t the u se of all the l
atoms light will be thrown upon the mechanism of a

,
number of reactions This is true especially when the

.
d i st ri bu t lon of the charges on the atoms constituting the

molecules is taken into account .
C H APTE R IV .
CA TA LYSI S .
T HE 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 two or more molecules interact This .
would include changes which take place in chemical r e

actions and an attempt will be made to outline a general
theory of chemical reactions from the standpoint of str u c
tural chemistry in this and the foll owing chapters .
In considering such a general theory of chemicalreactions ,
it i s 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 S hort discussion of catalysis as it is

,
ordinarily presented and as it will be presented here wil l

serve to S how the relations .
A catalytic action i s generally defined as one in which the

velocity of a reaction i s modified by the presence of a s u b
stance which i s itself unchanged a t the end of the reaction .
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 h as 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 s ub

stance A catalyst can o nly 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
CATA LYS I S . 61
reactions are affected to the same extent by the 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

catalytic actions a s 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 n e ce s

, , .
sary for purpose s of classifica tion to have some de fi nitions

,
of this kind the way in which the classification of c a talytic

,
reactions developed that is v eIy often by the introduction

, ,
'
of the term catalyst when unknown factors were invo l ved ,
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 mo d ify the velocity of a reaction
without itself undergoing a change in chemical composition .
No further limitations will be introduced and it will be ,
shown h ow the concl usions from this point of view compare

with the concl usions derived from or based upon the d es cri p
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 initial and final products of the reaction is the

same The way in which such a substance may modify
.
the velocity of a reaction m ust next be considered and it is ,
this point which forms the crux of t h e general theory to be

used The genera l theory consists of what has been called
.
“ ”
the addition theory of chemical reactions .
In considering the mech a nism of chemical reactions this ,
theory states that primary addition i s involved in chemical

reactions between molec ules even when the final products
obtained indicate substitution or other change It re pre .
62 C HEM I C AL REACTIO NS .
sents the most general case of chemical reactions E vi d e nce .
for an explanation for a number of reactions on this b asis

and the view that it was of general application w a s pre
sented some years ago in a S hort paper ( K G Falk and . .
J M Nelson Jour A mer C hem S oc 37 1 7 32

. .
, . . . .
,
C atalytic reactions will be taken up as a group of addition

reactions following the same laws as other chemical re
actions with on e condition fixed namely that one of the
, , ,
original substances which takes part in the reaction also

appears as on e of the products of the reaction The com .
ple t e change may be represented by an equation of the form ,
A + B +
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
p o n e n t s with the catalyst and,this complex compound then
reacts further to reform the catalyst and one or more new
molecules The proviso for a reaction to be considered
.
catalytic is that on e 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
.
,
ly st 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
, ,
e ff ect 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
64 C HEM I CA L R E ACTION S .
ethyl alcohol zinc chloride acts as catalyst and the inter

, ,
mediate compound is represented by the formula Z n C 12 .
C2 H5 OH .
C ondensation reactions with aluminium chloride as

catalyst also involve the formation of intermediate complex
compounds which have been isolated in s ome cases These .
will be taken up in detail in C hapter 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 S how many more reactions of this kind P . .
“
S abatier in his book L a C atalyse en C himie Organi
,
”
que , 19 1 3 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 This unsaturation may depend upon a definite

.
atom of each molecule or upon a group of atoms combined

.
,
in such a way as to S how unsaturation of two or more atoms

( a s 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 i n

connection with the formation of the intermediate c om
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 S ome evidence will now be presented to
.
indicate that unsaturation of cert ain 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 reactio n
CATA LYS I S . 65
may proceed faster in one solvent than in another A s an .
example the reaction between triethylamine and ethyl

,
iodide in which tetraethylammonium iodide is formed and ,
for which the rate in di ff erent solvents was studied by N .
M e n sch u t k i n m ay be quoted M e n sch u t k i n mixed on e

, .
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 °

.
Vel f
oci ty o C ombi n a ti on f
o T ri eth yla m i n e wi th E th ylI odi d e i n Va ri ou s
S olven ts .
V e loc i t y
C ons t a n ts .
R at i os .
H yd roca rb on s .
H exa n e C 6H14 1
H e p ta n e C 7 H16
Xy le n e C 6H4( C H3) 2
B e n z en e C sHe
Ha l og e n m p ou n d s co .
P rop ylchl ori d e C 3H7 C l .

30
P h e n ylchl ori d e C 6H5C l .
12 8
P h eny l b r om i d e C eH5B r 15 0
a B ro mn a ph t h a le n e C 1 0H7B r 62 7
S i m p l e E t h e rs .
E t hyl i s oa my l e th er C s OC a
E t h y l et her C H 0C H 2 5 2 5
Phe n et ol C H OC 6H z 5 5
C H3006H5
li s t ers .
Is ob u t y l a cet a t e
E t hy l a cet at e C H 0 C O C H 2 5 . .
3
Eth yl b en z oat e C H 0 C O C 6H 2 5 . . 5 .
Alcoh ols .
Isob utyl al ohol C 4H O H

c 9 .
a l coh ol
A lly l a l oh ol C H O H
c 3 5 .
M th y l l coh ol C H O H
e a 3 .
B n y l a l cohol C 6H C H OH
e z 5 .
2 .
Ke t on es .
A ceton e C H3 C O C H3
. . .
A cet on e vo l) . W a ter
Acetop he n on e C H 3 C O C 6H5
. . 29 4
66 C HEM ICAL RE AC TI O N S .
The determination of the amounts of tetraethylammonium

iodide formed enabled him to calculate the velocity con
,
St a nt s for the reaction using the equation for a bimolecular

reaction S ome of these values ( k) for the reaction in differ
.
ent solvents are given in the accompanying table [ Z physik . .
C hem 6 43
.
, The ratios give n in the last t wo
columns S how the relative rates of reaction first when com ,
pared to the slowest reaction whose ve locity is placed equal

,
to on e and second on the basis of the most rapid reaction

, ,
which is placed equal to 1 00 .
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 t o form addition

products but that in some of the solvents polymerization
, ,
of the solvent molecules themselves occurs The u n .
saturation S hows 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.
U nsaturation may therefore be used as the property

upon which the catalysis of these reactions depend With .
out entering into the s tructural 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 C hem 1 5 1

. . . in studying th e
.
,
relative rates of the reaction between hydrogen sulfide

and sulfur dioxide in a number of organic substances ,
CA TA LYS I S . 67
accounted for the results obtained by the assumption of

intermediate compounds involving the reacting com pounds
and the solvents a s catalysts The evidence in other r e
.
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 S ome of
, .
these reactions are given by J W M ellor in his C hemical

. .
”
S tatics and D ynamics .
The theoretical views of E C C B aly based upon the

. . .
,
absorption in the ultraviolet region of the spectrum of the

reacting substances before during and after the reaction
, , , ,
and outlined in C hapter II may be referred to in this

connection .
A group of catalytic agents which is continually increasing

in importance i s included under the general term of enzymes ,
the catalysts produced by living organisms and which are

of the greatest signifi cance 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 18 no definite evidence at the present time that

any has be e n obtained in a pure state that i s 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
p roducts of the reactions One of the
. lines of evidence for
this view may be indicated br i efly With a small amount .
of enzyme material increasing the amount of substrate will

,
at first with small quantities of the latter S how a larger

, ,
amount of decomposition in a given time interval up t o a ,
certain amount of substrate Increasing the con centra

.
tion of substrate beyond this will result in the same amount

of action as with the smaller amounts evidence that the ,
68 CHEM I CA L RE ACTION S .
given quantity of enzym e can take care of only a certain

quantity of su bstra t e h or that a compound of the t wo is
formed The possible question of adsorption will be taken
.
up presently A nother way of stating the same observa

.
tion is that with small amounts of enzyme the amount of ,
substrate transformed in a given time interval is propor

t i on a lto the length of the time interval A mong others .
,
this was found t o be true for the action of invertase on cane

sugar by J M Nelson and W C Vosburgh ( Jour A m
. . . . . .
C hem S oc 39 7 9 0
. by J D u cla u x [ C hemie B i olog
.
, .
ique Paris 188 3; and Trait é de M icrobiologie Tome II

, , , ,
D iastases T oxines e t Ve n i m s Paris

, by A B r o wn , , , .
( Trans L ondon C
. hem S oc 8 1 37 3 and by L . .
, .
M ichaelis and M L M enten ( B iochem Z 4 9 333 . . . .

,
of amylase on starch by H T B rown and T A Glendinning . . . .
[ Trans L ondon C hem S oc 8 1 38 8

. of the action . .
, ,
of lactase malta se and emulsin by E F A rmstrong

, , . .
[ Proc Roy S oc 7 3 5 00
. . of lipase on glyceryl tri
.
,
acetate by K G Falk and K S ugiura [ Jour A mer C hem

. . . . . .
S oc 37 2 2 7
. and of urease on urea by D D van
, . .
S lyke and G E C ullen [ Jour B iol C hem 1 9 141

. . . . .
,
The well known lock and key simile of E mil Fischer for
-
such reactions indicates also a belief in a chemical combina

tion a s the first step H D D akin [ Jour of Physiol 30 . . . . .
,
253 found evidence for the existence of intermediate

compounds in the action of optically active liver lipas e
material on a racemic mixture of esters of mandelic acid ,
the dextro component reacting more rapidly than the l aevo

-
.
“
The dextro and l aevo components of the inactive ester -
first combine with the enzyme but the latter i s assumed ,
to be an optically active asymmetric s ubstance so that the ,
rates of combination of the enzyme with the d and lesters -
are different The second stage in the reaction consists

.
in the hydrolysis of the complex molecule ( enzy me ester ) .
S ince the complex molecule ( enzyme d ester ) would not -
C ATA LYS I S . 69
be the O ptical opposite of ( enzyme lester ) the rate of -

,
change in the two cases would again be different Judging .
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 compone nt of the

,
-
inactive mandelic ester combines more readily with the

enzyme than the l aevo component does and that the com
-
,
plex molecules ( d ester -

enzyme ) are hydrolyzed more
rapidly than the ( lester -
enzyme ) so that if hydrolysis be
,
incomplete dextro acid i s found i n solution and the residual

-
”
ester is l aevo rotatory
-
.
The views s o far presented in this chapter may be su m

m a r i z e d as being based upon the primary formation Of .
addition compo unds when two or more molecules react these ,
addition compounds then br ea l d n g 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 O ften

modify the velocity of the reaction between gases A t .
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 importan t
factor here Just how far phenomena of this nature may
.
be identical with the formation of definite chemical c om

“ ”
p ounds ( possibly s o called-
loose combinations ) on a
surface is not at present certain but until direct evidence
,
is obtained that such reactions must be included in a
70 CHEM I CAL RE AC TI O N S .
Sc he m e different from the one outlined here the present

.
c l a ss ification may be used to include all these reactio ns ,
al thoug h the composition and even in m any ca se s the

,
n ature of the intermediate compounds is not known

, , .
T h e reactions between two or m ore m olecules take place

w ith the formation of interm ediate co pounds For the m .
sake of completeness it will be necessary to refer to the

,
reactions in which on e substance only is changing or re

acting This substance may be a simple molecu l e reacting
.
,
or may b e a molecule of a complex intermediate addition

c o mpound made up of two or more simpler molecules
, .
T h e rate of such reactions appear s to depend entirely upon

the nature of the substance and while it is influenced by
,
the temperature a certain fraction of the amount present

,
i s 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 t o

a ccount for the fact that only such a part reacts and not ,
t h e whole amount such as an attempt to distinguish be

,
t ween 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

,
advisa ble simply to state the fact without attempting to

exp lain it .
S ome theoretical relations with regard to catalytic re

a ctions will now be taken up A S imple mechanical analogy
.
d eveloped by Professor J M Nelson and D r J H North

. . . . .
r op may be of interest here in considering the energy or

,
a ffinity re lationships although it does not include the

,
view of addition compound formation

A vessel of water A is filled to the level 0 A syphon D
, , .
, ,
filled with water dips into this water while its other , ,
lower end reaches to the vessel B placed lower than A s o

, ,
that the leve l of the w a ter in B ( E ) at the beginning i s

72 C HEM ICA L RE A CTION S .
customary statement of catalytic changes then the catalyst ,
cannot change the equilibrium 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 B r e d i g ( E rgebnisse der Physio
.
, .
logie I 1 39
, showed that a change in the vapor
pressure of a catalyst necessitates a difference in the work
req u ired to remove the catalyst from the reaction mixture .
Only as long as this work i s the same under the same condi
tions before and after the reaction does t h e equilibrium ,
remain unchanged If the catalyst i s present in large

.
excess it acts as solvent A change in the n ature of the

.
solvent changes the equilibrium and only in dilute solution ,
will the equilibrium remain the same E A bel [ Z E lektro . . .
chem 1 3 5 55
.
, stated assuming the formation of ,
intermediate products with the catalyst that if the catalyst ,
is in a different chemical or physical state at the en d of the

reaction from what it wa s at the beginning that it has ,
given up or received energy and that a change in the ,
equilibrium was quite conceivable W J Jones and A . . . .
L apworth [ Tran s L ondon C hem S oc 9 9 9 1 7 ( 1 9 1 1) 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 . . .
Rosa n off ( Jour A mer C hem S oc 35 17 3

. . 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 B ancroft ( Jour Physical C hemistry 2 1

,
. . .
,
573 reviewed certain phases of catalytic reactions

and took up some of the questions discussed here .
CATA LYS I S . 73
If a catalytic reaction is d efined as a reaction in which

on e of the products is identic al in chemical composition
with one of the originalsubstances involved in the reaction ‘
the view which is used here then it may be possibl e to ,
arrive at definite general conclusions No further limita .
tions are introduced in the definition In the general .
formulation of a chemical reaction :
V1 a 1 + -o
A2 +
I
nl A 1
r r _ I
Vl a l + V2 +
/ I l I
a2
j n2
in which ma g ,
l l
represent the molecular species
a l , ag ,
in the solid state taking part in the reaction AI A2 A1 , , ,

,
,
’
Ag ,
o
the molec ula r species either as gas or in solution ,
’ ’ ’ ’
and VI V2
, , n 1 n2 , Vl Vg , n l nz
o
the corre
, , , ,
o
sp on d i n g m olecular species formed in the reaction then the ,

f
definition of catal ytic action ad vanced requires only that

’ ’ ’ ’
one of the molecular species a l a z A 1 A2 is , , , ,
identical in composition with a l a 2 A1 A2 The , ,

o
, ,
definition does n ot a p ri ori state anything concerning the

, ,
velocity of the reaction S ince on e of th e substances a p

.
pears as a product of the reaction obviously it may g o ,
through the cycle of the reaction again wi th 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 s ubsta nces This phenomenon has .
always been taken t o be on e 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 if everyone of the substances at the beginning
,
and at the end of the reaction is present in t h e pure state ,
then the equilibrium constant derived from the law of m a ss

action would be independent of the catalytic substances the ,
equilibrium wou ld be the same whether the catalyst were

present or not and reaction would proceed in the presence
,
74 CH EM I CA L RE ACTION S .
or absence of catalyst although the rates in the di ff erent

,
cases may well be di fferent 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 e ff ect at all would be noticeable upon the rate of the

“ ”
reaction The s o called negative cataly sis ( cf M ellor
.
-
.
,
LC ) i s 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 s o that a develop ,
ment of the ideal case j ust presented will be necessary .
If in the general formulation of a chemical reaction given

,
’
above the concentrations of the substances AI A2
, Al , , ,
’
Az , in the free state before and after the reaction are
denoted by 01 02 ,Cl
’
,
o
and their concentrations
,
at equilibrium by then it may readily be S hown

that the change in the free energy ( A ) of the reaction is
given by the equation ,
o o o o o c
A R T log , ' ,n 1
/
I n2
" g a 1
n1 / ,2
.
C 02
[
1 01 02
( Th is equation developed w ith the aid of the conception

of the equilibrium box ( van t Hofl ) into which the reacting
’ ’
substances in dilute solution or the gaseous state are intro

d u ce d 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 fractio n 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 , ,
as necessary for a catalytic change the work done will be ,
CATA LYS I S . 75
the same whether the catalyst is present or absent and the ,
equilibrium will be unchanged If however work is done .

, ,
in introducing or removing the catalyst some sort of che m ,
ical compound is formed between t w oor more of the m ole c u

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
. may denote a
complex containing the catalyst while in the denominator ,
the catalyst m ay be represented in a di ff erent complex .
It may be said therefore th a

, t in the chemical changes as
,
ordinarily observed if a catalyst i s involved in the re a c

,
tion that a s long as the substances are not present in the

, ,
pure state or possessing the same properties before and

after the reaction there may wel l 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 also be remembered that the law of mass action as de

v el op e d in the thermodynamic treatment as indicated ,
holds only for dilute solutions and for gases at compara

t ivel
y low pressures For concentrated solutions and gases
.
at high pressures the theoretical considerations cannot as

,
yet be applied satisfactorily .
C H A PT ER V .
C HEMI CA L RE AC TI O N S; G E N ERA L CO NSI D E RA TI O N S .
IN the preceding chapter chemical reactions were d i s

'
cussed with one condition fixed namely one substance

, ,
involved in the reaction having the same chemical composi

tion in the beginning and at the conclusion Of the reaction .
S uch a reaction was treate d 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 suc h a change
.
in velocity is to be found in the addition theory of chem ical

reactions according to which a reactio n between two or
more molecules takes place by the formation of a more
complex I ntermediate 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 w ay increase the velocity of the reaction being ,
itself reformed a s one of the products of the decomposition

of the intermediate compound . This theory of addition
compound f or m a t lon W lll now be applied to chemical r e a c
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 r e pr e

, , ,
se n t a t i v e 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
G E NERA L CON S I D E RATION S . 77
ing this react i on In the form of a chemical equation is the

following :
N H3 HC l N H4C l
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 meces
s a r il
y include it .
In the last chapter it was pointed out that the action

,
of the catalyst is due to the formation of addition com

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 B efore going into the details of this
.
reaction the reaction between ammonia hydrogen chloride

, , ,
and platinic chloride will be taken up a s 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 chlor ide toward

platinic chloride is similar to their behavior toward water ;
that is addition compounds are formed in both groups
,
.
B ecause 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 othe r
words their stabilities as measured by certain equilibrium

, ,
constants ) would not take place to the same extent B ear .
ing this difference in mind the formulations may now be

,
indicated .
The definite compound ammonium chlor platin ate -

,
( NH4) 2 Pt C 16 is made up of and may be prepared from

, , ,
ammonia hydrogen chloride and platinic chloride It may

, , .
dissociate in a number of different ways, the most important

of which are indicated by the following equilibria :
2 N H4Cl Pt C l
4 (a)
2 NH3 H21 t C le
)
( b)
NH , 2 HC 1 + ( NH3) 2 P t C 14
(2)
( c)
2a 2 HC 1 + P t C l 4 ( d)
The possible intermed i ary compounds such as ( N H4) P t C l5
in equilibrium ( a ) ( NH3) 2 HPt Cl5 in equ ilibrlu m (c) etc
, ,
. ,
are not given as they add nothing to the principles which

,
these equilibria are intended to illustrate E quilibrium (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 ) ( b) 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
b eing studied The equilibria may of course be deter
.
, ,
mined experimentally and the values of the equilibrium

,
c onstants give a measure of the relative chemical affinities
of the reactions If the conditions are such that besides

.
,
e quilibrium ( d ) only
, or predominatingly the pro d ucts
S hown 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 .
A gain if besides equilibrium ( d) mainly the products

, , ,
80 C HE M ICA L R E ACTION S .
to S how the reaction in as S imple a form as possible at the ,
same time coinciding with the facts as far a s known it will ,

“ ”
be assumed that the ternary addition compound contains
one molecule of hydrogen chloride one molecule of a m , ,
monia and one molecule of water The formulation of the

,
.
different equilibria similar to equations

, will then be
as follows :
( H2 0 HC 1) NH, ( a )
.
( H2 0 N H3) HC l ( 5)
.
( 3)
H2 0 ( N H3 HC 1) ( )
0 .
H2 0 N H3 HC l (d)
S tarting with water ammonia and hydrogen chloride

, , ,
[ equilibrium it is found experimentally that ordinarily

the products indicated by equilibrium (0) are obtained or ,
vi ce vers a
. Water acts as a catalyst for the reaction between
ammonia hydrogen chloride and ammonium chloride j ust
, , ,
as platinic chloride did in the preceding reactions A .
difference between the two sets of reactions ( 2 ) and ,
may lie in the fact that in the former the value of

,
the equilibrium constants may be such as to S how the ‘
“ ”
intermediate ternary compound ammonium chlor ,
”
platinate to be more stable than the intermediate ternary
,
compound in the latter ,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
( a ) or of ( b) The. changing of the values of the equilibrium
constants when the conditions are varied may well cause
th e reaction to assume a different course A ll the possi .
bilit ie s with one molecule of each reactant are given in the

, ,
equations however and the deductions are similar to those

, ,
from equations The concentrations of the reacting

substances here also play a predominating r 61e in deter
mining which products will be found in a reaction mixture .
G E N ERA L CON S I DERATION S . 81
The actual composition of the ternary compound is not

known definitely and has therefore been given in the
, , ,
S implest form but even if different numbers of the reacting

,
molecules were contained in it the s a me principles and

,
relations may be applied although the equatio ns woul d be

much more complicated The relative velocities of the
.
dissociation of the intermediate compound would determine

which products are observed at any time if the complete
.
,
reaction has not been allowed to come to equilibrium .
It is perhaps m ore usual to S peak 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 : , ,
It is evident that this reaction wou ld 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 chl oride 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
4 -3
in its s1m ple st form as H3N OH2 ( or graphically H

+ 1 +1
.
3N Z OH2
an onium addition compound ) This compound may tauto

.
merize to ammon ium hydroxide NH4OH the base from , ,
the ionic point of view which may be written

,
in two zones to indicate the ionization and which shows all,
that is known structurall y 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 g eneral schemes ou t
,
l ined an addition compound is considered to be formed first

, .
The complete reactions may be indicated in the most general

way as follows :
( 1) NH , H2 0 ( )
2 HC 1 + H2 0
H2 0
N H3
N H3 HC 1
( 3) 2 H2 0 .
( 4)
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

“ ”
s o 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 equatio n s are all
.
in fact really equilibria and that the reverse reactions may

,
also take place Thus if carbon dioxide C 02 were used in

.
, , ,
place of hydrogen chloride very littl e 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 examp le t h e heats of neutralization of highly ionized

,
a cids and bases which are practically identical in dilute

,
solution This is brought out by the following s e t of

.
equations :
G E NERA L CON S I DER ATION S . 83
( 1) KOH + H2 0 =
H2 0 H2 0
(a Ha + HD = + cn
KOH HC 1 KC 1 K
( 3) 3H2 0 3H2 0
+ 01
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 indica ted but may rearrange and

then ionize C omparing the final product of ( 3) with the
.
substances present in great excess in ( 1 ) and as S hown

by the d e t e rm in a t ion s of the degrees of ionization it is
.
,
evident that the net change S ince excess of water is present

, ,
is the combination of hydrated H i on 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 doub l e , ,
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 c o
,
ordination numbers of the constituents with respect t o the

particular substances which make up the intermediate a d
dition compound .
. .
—
Werner ( lc pp 2 32 7 ) has combined all these reactions
.
into a general one which may perhaps be indicated as

,
follows :
H2 0 X, [ A5M H2 0] X x [ A5M OH]
. RX .
( 1) (2 ) ( 3) ( 4) (5)
One molecule of water may react with compound ( 1) to
form compound This primary compound may the n

dissociate to yield compounds (4) and AS a concrete
example chromium chloride may be taken a s the primary
compound Here M i s C r X is C l and n is 2 The
.
, , .
equation becomes :
H2 0
( 1) (2) ( 3)
HC 1 .
(4) (5)
C ompounds ( 1) and ( 2 ) combine to form ( 3) this i s hydra

tion C ompounds ( 1 ) and ( 2 ) undergoing double d ec om
.
position form (4) and 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
,
s e t of reactions in the case of the ch rom lu m chloride t o be
a se t of displacement reactions C ompound ( 3) may be

.
regarded as an addition compound containing both hydro

gen chloride and water S ince the part
, is equivalent
to C ompound ( 3) therefore can dissociate in

either direction giving as one of the products hydrogen
,
chloride or water The reaction I n which compounds ( 1)

.
and ( 2 ) form (4) and ( 5 ) ( hydrolysis ) is therefore a dis

,
placement of hydrogen chloride by water L ikewise 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
G E NERA L C ON S I DERATION S . 85
group which may be classed together and explained m ost

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 S imple replacement reactions In none of .
these reactions has the charge or state of oxi d a t lon of any

of the atoms changed ; that i s to sa y no oxidation or re d u c ,
tion has taken place The treatment of the la rge and i m

.
portant group of reactions involving oxidation and redue

tion of di ff erent atoms in the mblec u le s which take part in
chemical reactions will be taken up l n 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 :

—— ( A3 B ; ) : x — a
(A xB h h l (A 3
r 2 v 5
+
(A B
(A s B 6
“
1 11
( 1 4 3 51
(A mB )
n a
a m s) .
m “ H
(A t,
II H ( A m"B ’) y y V
(A gZ B
-
n
6+
if m y
"
) . ( A ne w.
I etc .
( A 25 8 5 ) .
,
VI
:7 1,
4
57' 513
7 etc .
227 B x
; /
2
VII
In this scheme starting with :1: molecules of A a

, y
‘
,
' ' '
molecules A mf B T and :3 molecules A mTCB X the ternary
n
H
’
+
addition compound I is formed The molecules A B
“
are assumed not to exchange positive or negative con

s t i t u e n t s but to dissociate as the integral molecules which
,
make up the ternary compound U nder these simplified

.
conditions it is seen how the dissociation may take place

, ,
and the number of possible equilibria involved in a reactio n

of this type If the various positive or negative con st it u
.
ents may in addition replace or displace e ach other the ,
number of equilibria is correspondingly increased This .
scheme shows why the number of products in many organic

reactions is s o 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 it must be emphasized again that the general principles‘
of the mechanism of chemical reactions apply throughout ,
whether thes e be grouped for convenience of treatment or

for any other reason as inorganic and organic reactions .
S ince the ionic theory has been s osuccessful in correlating

a number of previously separated phenomena including ,
the possible explanation of certain chemical reactions ,
especially those taking place in aqueous solution it 1S 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 ou t It was S hown 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
88 CH EM I C A L REACTION S .
dominatingly negative charge will ionize into

and 2 X It i s probable that a substance of this sort
.
will take up more (generally four ) molecules of water

in onium combination with the metal element These .
additional molecules of water are not directly involved

in the theoretical views to be develope d and will therefore
be omitted The substance M ( OH2 ) 2 X2 may undergo
.
hydrolytic dissociation as S hown in equilibrium of the

reaction .
H2
/
—X 2X ( ) a
M\ O
—X M (OH )2 ( b)
g 2
2E X
The reaction which will be observed depends upon the

equilibria ( a ffinity relationships ) of ( a ) and ( b) in the given
equati ons 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 ( OH2 ) 2 X2 to undergo

hydrolysis until ultimately only M ( OH ) 2 will be present .
This reaction will take place especially if M ( OH ) 2 is i n

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

,
2 M OH 2M X
’
formulas are used i s M X2 , M ( OH ) 2 ’
but this for one thing leaves out of account the action of the
, ,
solvent Written in the ionic form M 2 0H M ( OH ) 2

.
,
while apparently going back to more fundamental relation

ships does not show what direct part if any the solvent
, , ,
plays B y means of the equilibrium reactions as f orm u

.
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 .
G E NERA L CON S I DER ATION S . 89
Am m on la 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 M X2 it is evident that

a compound ( H3N 2 ) 4M ( —
,
> N H3 or ( omitting the

four ammonias in onium combination with M ) M ( N H3) 2 X2 , ,
may be formed The relative amounts of M ( OH2 ) 2 X2 and

.
of M ( N H3) 2 X2 which will be formed or the distribution of

,
M X2 between water and ammonia will depend upon the ,
relative stabilities of these c m p ou n d s under the g i ven

q
conditions The substance M ( N H3) 2 X2 undergoes electro
.
lytic dissociation as follows ( omitting possible intermediate

ions ) :
H3
M<
§
H3
%
3
3
Ammonolytic dissociation to form M ( N H2 ) 2 and H X ,
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 under 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 .
B eyond 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 s u m up the possible

.
,
reaction between a base and a substance M X2 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 ( OH ) 2 may be precipitated ; if the salt is entirely present

a s the latter no M ( OH ) 2 will be precipitated
, .
In the past years F E phraim published som e very

, .
careful studies on the stability of the metal ammoniates .
He determined the temperatures at which the hexa
90 C HEM ICA L RE ACTION S
'
.
ammonia ( and substituted ammonia ) derivatives of a

number of salts Of the bivalent metals ( including B e Ni C o , , ,
Fe C u M n Zn C d M g ) S howed definite vapor pressures

, , , , , .
The resu ts give a mea sure of the relative stabilities of

l
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 N i C 12 6N H3 shows a vapor
.
,
.
pressure of 5 00 mm at while the salt M g C l2 6N H3

. .
S hows the same vapor pressure at 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 .
C onsequently 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 E phraim may be arranged in a series showing the relative

amounts of ammonium salts needed to prevent precipitation
if a base is added .
The views of Werner that compounds of the first order

are not electrolytes but must 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 al so be made t o two experimental investi

g a t i on s bearing on this question : I s be k ow [ Z a n or g . .
C hem 8 4 2 4 . found that by dissolving the s u b

,
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
92 C HEM I CAL R E A CTION S .
ammonium chloride The constituti on of these ionogens

.
would be of the form

It wa s shown by P lot n i koff ( J Russ Phys C hem S oc . . . . .
( 3) 466 and later confirmed and studied more

thoroughly by H E Patten ( J Physical C hem 8 5 64
. . . .
,
that aluminium bromide dissolved in ethyl bromide

gives a solution which has a relatively low electrical re
s i st a n ce ,and from which aluminium may be deposited
electrolytically j ust as in the case of a solution of an
aluminium salt in water A nother interesting fact about
.
these results is that ethyl bromide has a very low dielectric

constant and still serves a s an ionizing medium for
the aluminium bromide This solution is analogous to the
.
solutions described by Isbe k ow .
It must be borne in mind h owever in i nterpreting these

, ,
l ast re s ults that the separation of a metal or other s u b

,
stance a t 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 ,

i
perhaps a m i n u t e part of the copper is contained in the

anion .
Other evidence with regard to the combination of solvent

and solute m ight be quoted but the general trend of the ,
views is apparent A s 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 l atter phenomenon Thus W Nernst .

, .
and J J Thomson have considered it to be due to the

. .
dielectric constant of the solvent J B r ii hl to the ( chem , .
i ca l ly ) 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 gener al explanation which
,
covers all the facts Possibly the d evelopment of the views

.
put forward here involving addition compounds tautomeric ,
G E NERA L CON S I DERATION S . 93
rearrangements and equilibria with di fferent sets of

,
products may permit of a more general theory but at ,
present the quantitative data with regard to these additio n

,
products are too meagre to permit of more than a suggestion

of this as a general explanation .
C H A PT ER VI .
S O ME C HEM ICA L RE ACTION S .
T HE principles developed in the preceding chapters will

now be applied to chemical reactions the substances r e
,
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 due 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 S hall have changed its
valence or become oxidized or reduced Reactions i n .
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 S ince SO much material is
.
avail able in the field of organic chemistry practically all ,
these reactions involve changes in organic compound s a n d ,
it will be shown how a number of r eactions which heretofore

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 ole fi n s undergo

, ,
will be discussed and compared with the changes taking

'
place i n various organic and inorganic reactions In this .
way by considering first the changes involved in a series

,
94
C 6H6 A12 C 16 Al 5 C 6H5 ,

gCl
( hypothetical compound )
A12 C 15 C 6H 5 C 5H11 C l gCl
Al s C 6H 5 ( C 5H 11) .
They assumed the formation of the hypothetical inter

mediate compound A 12 C 15 C 6H 5 in this rea ction and of S imilar
compounds in other reactions This theory has never
.
been demonstrated experimentally to be true and h as ,
therefore been superseded by other theories

, .
’
The dominating idea in Friedel and C raft s original theory
and in m ost of the t heories attempting to explain the r e
action is the formation of more complex compounds first ,
followed by their decomposition or further reaction .
G Perrier [ C r 1 1 6 1 300
. . .
,
B e r 33 8 15 .
,
found that in the Friedel C rafts 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
w a s able to isolate :
Cm Hn
The decomposition of the addition compound (which formed

a crystalline compound ) with cold water yielded the ketone .
The formation of these compounds h a s since been confi rmed

by several other investigators and h a s 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 A1X3C6H6 and A1X3 3C 6H6 [ J pr C hem 68 2 09
. . . .
,
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 [ B e r 1 1 2 15 1 .

,
S O ME C HEM ICA L R EACTION S . 97
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 A1C 13 .
2 [ C r 1 4
0 9 40 ( 1 9 05 ) J pr C.hem .
, . . .
72 57
, but this does not conform to the above type
and is really a ternary compound .
B N M e n sc h u t k i n [ J Russ Phys C hem S oc 4

. . 1 1089 . . . .
,
( 19 09 ) C hem Z e n t ra lb 19 1 0 1 1 67 ] 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 .
M any chemists are inclined to accept the results of M en

s c h u t ki n 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 en o ugh , ,
of the addition compound wa s present to saturate the

solution Furthermore M e n sc h u t k i n found that in the
.
,
case of other metal halides such as antimony chloride ,
addition compounds such as SbC 13 C 6H6 ca n be obtained .
[ C A ( 19 1 1 )
. . It must also be borne in mind i n
comparing these results with the results of Gustavson that ,
the la tter in his experiments had hydrogen chloride present

as well
J B Oe se ke n and c o—
.
. workers [ Re c trav chim 32 18 4 . . .

,
33 31 7 ; 347 8 ; 35 109 ; Ve rsl

, a g A kad W e n sc h a p
, , .
pen 2 1 9 79 ] studied the Friedel C rafts reaction in connec

,
-
tion with sulfonyl chlorides such as p brombenzene -
s ul p h on e c h l
o r i d e etc These combined
, with
. the aluminium
chloride The resulting compounds then reacted with the
.
aromatic hydrocarbon The su lfone formed in the reaction .
combined 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 .
98 C H EM I CA L RE ACTION S .
There is considerable experimental evidence a t hand ,
therefore for the formation of double salts or binary c om

,
pounds from acid chlorides and alumin ium halides In .
addition to the examples given E P Kohler [ Am C hem J , . . . . .
'
2 4 39 0
, i soa t e d the compounds AlB r3 C 5 H5SO2 C 1 ,
Al B r3 C 6H5 C OC l Al
. B r3 P OC l 3 Al B r3 C 6H5 C OC H3 and
, .
, .
,
Al B I 3 C 6H5N 02 and A begg [ Handbuch der anorganischen

'
.
,
C hemie vol 3 part 1 p 74

, . mentions the com
, , .
pounds A1C 13 SC I4; A1C 13 2 P C 13; A1C 13 2 KC 1; A1C 13 4KC 1;

. . . .
A1C 13 4 N H4C 1 etc

. The ability of aluminium halides to .
co mbine to form complex compounds is also shown in the

following substances which have been described :
A1C 13 Hg C lC 6H6 W G ul
. e w i t s c h [ B e r 37
. 1 5 60 . .
,
A1C 13 C 6H5 OC H3; . A1C 13 C 6H5 C 02 C2 H5 ;

.
C2 H5B r H2 S A1B r3 [ V A Pl
. ot n i k off ,
. . . J C hem S oc A bstr
. . . .
etc1, .
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 f r om a rom a t ic .
hydrocarbons and alkyl halides has failed to S how their

presence For example A W r oc z y n ski and P A Guye
.
, . . .
[ J chim Phys 8 18 9 . found that the freezing point

.
,
curve of a mixture of benzene a nd chloroform gave only one

eutectic and S chmidlin and L ang observed the same with
,
the benzene brom oform system -

.
B N M e n sc h u t ki n [ C hem Z e n tra l
. . bl I 1 67 ] and . .
,
also J B Oe s e ke n [ C hem Z e nt ra lbl

. I 466] suggested . .
,
that in the Friedel C rafts reaction the three reacting c om -
p on e n t s combined to form a ternary compound which then

reacted further This view was adopted and elaborated by .
J S chmidlin and R L ang [ B er 4

. 5 899 They . .
,
considered the evidence for the existence of binary c om

pounds described above and concluded that the only sati s ,
1 00 C HEM ICA L RE ACTION S .
In this reaction as generally viewed ethyl benzene is

, ,
formed from ethyl chloride benzene and aluminium chlor,
ide S ome of the equilibria in this reaction with the ternary

.
( or considering ethyl chloride to be made up of ethylene

and hydrogen chloride quarternary) intermediate c om
,
pound are indicated Only a few of the possible reactions

.
are S hown Taking equilibria ( a ) and (c) it is evident

.
,
that this represents the reaction as ordinari l y viewed In .
( )
0 of course the compound may also be in e qu i i
l b
Al
ri u m 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 c on

densation products that i s 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 i n d i cat e d in C hapter . t
V a large number of equilibria and products are possible

,
with a ternary compound The part that a substance such

.
a s aluminium chloride plays in such reactions i s 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
com pou nd and which i s in equilibrium with a large number
,
S O ME C HEM ICA L REACTI ONS .
of different sets of products t h e addition of a new substance

,
to the reacting mixture will cause certain of the reactions or

equilibria to predominate over others a n d e a ch different , .
added substance may result in a diffe rent 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 sec ondary one From the .
theory of catalytic actions developed in C hapter IV a ,
reaction i s 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 i s considered to be at an end here aluminium ,
chloride may be considered to a ct as a catalyst since its

composition is unchanged If however water is added to
.
, ,
the r eaction mixture as i s 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 C rafts reaction holds throughout
-
.
Whether it is assumed to act a s a catalyst depends upon

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 .
E ither it has been considered to act catalytically or as in

an ordinary chemical actio n taking part in a definite
stoichiometrical ratio ; but it i s seen that this difference is
more one of definition and classification than a real difference
in the mechanism of the reaction .
S ince there is definite evidence in a number of the r e

actions that ternary or more complex intermediate c om
pounds are formed and there is evidence of complex
,
compound formation with a number of other compounds of

aluminium and similar metal halides the general e X p la n a
,
t ion of the Friedel C rafts reaction may be taken to be that

-
C HEM ICA L RE ACTION S .
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 su b
stances and it S hould be possible to find regularities in the
,
compositions of these reacting s ubstances upon which the ,
ready formation of the condensation products in this r e

action depends A comparison of such groupings which
.
facilitate this reaction ( either by more rapid formation of

intermediate products and their d e com p ositi n in certain -
directions or in S hifting 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 C rafts 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 a s indicated and there are as a rule a ,
number of other products formed in the reactions These .
will not be indicated here It i s e v i d e nt that a careful .

o
quantitative study of these reactions would be of great

value .
1 C2 H5 C l
. C 6H6 C 6H 5 C2 H 5 HC 1 .
2 . C H3C OC 1 + C 6H5 C H3C OC6H5 HC 1 .
3 C HC 13
. 3C 6H6 C H ( C 6H 5) 3 SHC l .
4 Og N C C l3
. 3C 6H6 O2 N C ( C 6H5) 3 3HC 1 .
5 C 6H5 C H2 C H2 C OC 1
.
C 6H4 C H2 C H2 CO HC 1
.
1
1
F . S . Ki pp i ng , Trans . C he m Soc 65 480
. .
,
104 C H EM I CA L REAC TION S .
C2 H4 C2 H5 X .
26 . C2 H 50N 02 C sHfi C 6H 5N 02 C2 H 5OH .

11
C 5 Hn ON O C 6H6 C 6H5N O C 5H11 0H .

11
28 . C lC H2 C 02 C2 H5 C 6H6
4
C 6H 5 C2 H 5 C IC H2 C OOH .
4
29 . C O2 C2 H5
Cl C 6H6 HC 1 + CC2
C 6H 5 C2 H 5 .
30 . C 6H5 C H3 P C 13 C 6H4( C H3) P C12 HC 1 12

.
OHL, 3C H3C 1 ( C H3C 1 volatile )

l3
.
2 C 5H5 C 6H 5 C 6H 5 H2 . .
33 .
2 ( 4) ( 7)
H I2
34 0 H E rz C B Hs B r
°
6 6 HB r
The first striking fact in these reactions is the large
number of different compounds whose reactions are a c
ce le ra te d by a lu m i n i u m halides Not all reactions which .
have been s tudied 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 1 1 include the elimination of hydrogen halide

in the formation of the condensation product ; reactions 12
t o 2 5 include direct addition of the components accelerated ,
by the presence of aluminium halide ; reactions 2 6 and 2 7

show that nitrogen compounds may be included ; reactions
2 8 and 2 9 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 act i on of halogenation A

, .
number of other reactions which are catalyzed by aluminium

E B oed tk e r B u ll Soc chi m I V ( 3) 7 2 6
11
.
, . . .
A M i ch aelis a nd C P a n ek B er 1 3 65 3
12
. .
, .
,
13
J . W W a lk er , J C h e m Soc
. . . . 8 5 , 1 089
S O ME C HEM I CA L REAC TION S . 1 05
chloride but which are in reality oxidation reduction re -
actions in the sense that certain atoms in the mo l ecules

change their valence or state of oxidation may be men ,
- x
t i on e d For example xylene at its boiling temperature

.
,
with the addition of 2 to 4 per cent aluminium chloride .
yields 1 2 per cent toluene and also benzene and poly

.
methylated benzene ( F Fischer and H Ni gge m a n B e r 4

. 9 .
, .
,
14 75 The action of aluminium chloride on petrol

e u m was studied by A Pictet and I Le r c y n s k a ( B ull s oc
. . . .
chim IV 1 9 32 6
.
, ,
C yclohexane was found to
rearrange in part to m et h ylpe nt a m e t h yle n e on heating to
boiling for 48 hours in the presence of aluminium chloride
( I
. A schan L ieb A nn 3
,2 4 1 . .
,
In addition t o the evidence regarding complex addition

compounds already given another line of proof may be ,
mentioned The reacting mixtures in the Frie del C rafts

.
-
reaction a s a rule develop more or less color starting with ,
colorless compounds The formation of colored compounds

.
in the case of somewhat different reactions has been taken

to show addition compounds [ J Kendall Jour A mer ,
. .
C hem S oc 8 7 149 ( 19 15 ) for aldehyde and ketone addition

. .
,
compounds with acids and H Wieland and E Wecker B e r

,
. .
, .
4 3 699 ( 19 10) as forerunners of a number of substitution

,
reaction s ]
With regard to the chemical constitutions or structures
of the intermediate addition compounds not much c a n ,
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 hi g her 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 o rganic .
compoun d s of aluminium some of which have bee n proven ,
1 06 C HE M I CA L REAC TION S .
to exist and others which are ass umed to be formed in the

Friedel C rafts 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 B esides the fact that chemical combination is

.
probably due primarily to the ability of the aluminium to

form on 1um compounds under the given conditions it is ,
difficult to sa y more at present with regard to the chemical

structures of these complex intermediate compounds .
In place of the aluminium chloride used in the Friedel

C rafts reaction it has been found that some of the chemical
,
changes may be accelerated by the addition of other

catalysts to the reaction mixtures A nhydrous zi nc chloride
.
has been used to som e 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

latter with various sets of products is omitted and only ,
the main reactions or changes are shown j ust as in the

Friedel C rafts reaction
-
.
/ C H3C I C H3C 02 C 5HH

35 2 C H30C 5H 1 1 C H3C OC 1 '
\\ C 5H11 C l C Hg C OOC Hg
.
36 0 + 2
.
H2 0
/
N(C H3) 2
37 C 6H5 C 013+ 2 C 0H N ( C H3) 2 = C H C C 1
U
.
5 6 5
NfC H3l
z + 2 HC 1
38 .
gC HO
Cl 5 O6H N ( C2 H5) 2
H2 0 3HC l .
C 6H 5 C H I H2 0 .
1 08 C H EM I CA L REA C TION S .
product which may be in equilibrium with various sets of

products and the course of the re a ct i on i n the presence of a
,
o
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 h a s not been attained In a number of cases
.
the intermediate compound has been isolated The rea c .
tions are quantitative oply in exceptional cases A s a rule .
a number of products are obtained but those given in the

,
above equations represent the products which were of i n

t e re st at the time the reaction was studied .
It will have been observed that a certain awkwardness in

nome n clature h a s occurred in the discussion of the r e a c
tions In the formulations of the different reactions equi
.
,
libria have been spoken of at times without the intention of

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 sign ifi
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 n itron at i on .
However for the present in this book the older term

, ,
nitration will be used B efore 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 C rafts re
.
-
S O ME C H EM I CA L REAC TION S . 1 09
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 si m
.
, ilar 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 s o that the entering

group substitutes in the ortho or para position S uch .
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

.
s i d e re d 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 ca n take place directly .
This led to the development of two theories of substitution :

( )
1 D irect 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 form ed Holleman .
carried out a serie of experiments to test these vi ews and ,
came to the conclusion that it i s not essential for an inter

mediate compound such as is assumed i n indirec t s u bst it u
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 e th e ri fi ca t i on of alcohol with

sulfuric acid as catalyst In this reaction it has been
.
,
suggested that the e t h e r ifi ca t i on takes place in several
1 10 C H EM I CA L REACTION S .
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 c a n be formed by starting with ethyl hydrogen

sulfate and that ethyl hydrogen sulfate ca n 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 su lfuric acid form an addition c om
pound which can dissociate in different ways and i s there
fore in equilibrium with various sets of products ; for
ex a mple 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 ou t .
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 on e 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 ma y 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

,
-
.
m ethods i nvolve the u se of ethyl nitrate or of n i t ros ul fates

(N n it roa ce t a t es ( or acetyl nitrate ) etc For , .
methods used in isolated cases reference m ust be made to

the books of Weyl L assar C ohn and others
,
-
, .
’
J U Nef s view of nitration is of interest He considers
. . .
the reaction to be analog ous to an aldol condensation a n d

formulates it as follows ( Jour A mer C hem S oc 2 6 1 5 66
. . . .
,
1 C H EM I CA L REAC TION S .
S uch reactions with aldehydes were illustrated in reactions

44to 47 above where sulfuric acid was the special catalyst .
Reaction 2 6 illustrated nitration with ethyl nitrate and

al uminium 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 + B OH E X + H2 0
it is evident that the benzene plays the part of the acid ,
and the ketone aldehyde or nitric ac i d 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
,
c a n 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 ass umed that an equilibrium exists be

-
3
O N H2 H3
H
tween the two tautomeric forms
( A)
In ( B ) the nitrogen is in the onium form and the benzene ,
nucleus ( or m ore strictly the para carbon atom ) plays the

,
part of the acid This equilibrium is similar to the one pres

.
‘
3 +1
ent in glycine ; namely ,

HOzC C H2 NH2 2
. . O OC C H2 N H3
. . .
There is evidence to show that the equil ibrium exists in the

latter case In the former the assumption of such a
.
,
similar e q uilibrium helps to explain a number of reactions ,
in fact it may be taken to be the fundamental phenomenon

,
“ ”
in all benzidine rearrangements .
S O ME C H EM I CA L REAC TION S . 1 13
Taking the simplest case the nitra tion

, of benzene the,
reaction m a y be formulated as follows :

OH
HO N02
.
02 N
N 02
NH 2
H2 0
—
H N0 2
H2 0
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

sulfate and there would not be the tautomeric form present .
U nder the se circumstances the intermediate compound

,
would n ot be the same as before and the nitration woul d

,
proceed as if benzene itself were being nitrated M ainly .
meta compound would be obtained under these conditions .
The velocity of nitration of benzene derivatives containing

different substituents was studied by H M artinsen [ Z . .
'
physik C hem 5 0 385
. .
, 5 9 605 ,
He f ou n d
the velocities to be dependent upon the substituents in the
following way :
N O2 < SO3H < C O2 H < C l < C H3< O C H3< 0C2 H5 < OH .
S maller velocity greater velocity

I 14 C H EM I CA L REAC TION S .
Those groups which when present diminish the velocity

orle n t 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 n itro .
,
sulfonic acid etc groups being more saturated have the

, .
, ,
opposite effect .
In the nitration in the presence of sulfuric acid W , .
M ar kown ik off [ B er 32 144 . and others consider

,
the nitrating agent to be n itrosulfuri c acid ,
/ OH
8 02
\
ON O2 .
In the presence of acetic anhydride or acetic acid a similar

compound o
,
f nitric and acetic acids acetyl nitrate is , ,
assumed [ A Pictet and P G e n e qu a n d B e r 35 2 5 2 6

. .
, .
,
a rid with benzoic acid benzoyl nitrate [ R W illst éi tter

, .
,
B er 4
. 2 4
, 15 2 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 w a t er f rom two other molecules and is probably
more unsaturated In this way the velocity of the reaction
.
,
might be accelerated but an intermediate addition c om

,
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
.
,
j ust spo k en of the solvent effect of the acetic acid may be

,
of aid in increasing the concentration of the hydrocarbon .
S uch conditions as the hydrogen ion concentration of the

m ixture may also play a part and may be influenced favor
1 16 C H EM I CA L REAC TION S .
is evidently due to the different oxidizing potentials of the

silver and the alkali and the equilibria between various
,
sets of products and the intermediate addition compound .
S imilar questions come up with other sets of isomeric c om

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 S pecifically to nitration only it evidently ,
holds for all similar reactions With benzidine the formula

.
,
tion may be given as follows :
NH — NH Nfl g
—
NH
(A )
—NH2 —
N H2
E quilibrium 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
, , compounds such as
Hz N
O NH -
O H2 N N H2 ,
(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
.
S O ME CH EM I CA L REAC TION S . 1 17
radicals are present will be described It will be recalled .
that in the formation of amides the reaction wa s treated

in the same way as the formation of esters from acids and
alcohols ;
H2 0 ,
01
‘
H2 0
N H3
.
N H3
The same principle can be used to explain the formation of

amides of nitric and nitrous acids ( or the formation of
.
n i t r oa m i n e s and diazotization ) If A
. N02 then ,
OzN OH N H3 O2 NONI I4 ’
O2 NNH2 H2 0 ,
or or
O2 N OH [ N2 0 H2 0]
N H3
and if A N0
ONOH NH, ONON H4 ONN H2 H2 0 .
[ N2 H2 0]
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 N it roa mi n e known often

.
,
as n itra m i d e 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 C rafts reaction that

-
the hydroxyl group or a chlorine atom might be eliminated

l n the condensations ; for example ,
HC6H59 R06H5 H2 0 ,
'
01
S imilarly with the reactions with ammonia ,
E 2 0,
I 18 C H EM I CA L REAC TION S .
01
‘
AC 1 HN H2 E -
> A NH2 HC 1 .
The action of nitrosyl chloride on ammonia is similar ;

namely ,
and
ON C 1 + HN H2
=
4+ 0NN H2 HC 1 .
The action of nitrous acid on am i nes 1s I ndic a te d very

often as follows :
RN H2 ONOH re -’ -
u > RN2 0H H2 0 .
In looking at this reaction from the point of V iew of inter

mediate addition compound forma tion it is evident that ,
it belongs to the same group of reactions The intermediate .
0 ef HN H2
a d d lt lon compound m i ght be formulated
.
ON OH
and the following components c a n be recognized and would
be present in the various equilibria ,
e f HOH, RN H2 , HN O2 ,
E 2 0, ol . N H3 etc , .
The diazotization reaction may also be formulated simi

a rl
l y to the action of a base on an acid :
B OH HA BA H2 0 ,
ON OH HN HR ONN HR H2 0 .
With nitrosyl chloride or ethyl nitrite in place of nitrous

a 01d the same holds except for C 1 or O C2 H 5 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

c iple s and changes If A . C 6H5 then the reaction corre
,
s p on d s to the formation of n it ros obe n z e n e etc , .
C H A PT ER VI I .
SOM E CHEM I CAL RE AC T I ONS ( C O NTINUED ) .
discussion of the m echanism of the reactions con

T HE
si d ere d s o far m ay be summarized a s follows :
( 1) Reactions occurring in organic chemistry are sim ilar

t o those in inorganic chemistry .
( 2 ) The theory of reactions in aqueous solutions hereto ,
fore based upon ionization relationships can be accounted ,
f or by addition compound formation involving the solvent .
( 3) All reactions appear to take place through the inter

m ediate formation of an addition compound If the re .
action is catalytic the catalyst i s one of the components of

,
the addition compound .
( 4) When water is considered as the catalyst f or reactions

ta ki ng place in aqueous solutions the hydrates formed may ,
give rise t o i on i zation .
T h e reactions may be based upon the genera l e q uation :
EX + HA B A + HX .
They may b e grouped in outline as follows :

I . Neutralization of an acid by a b ase ; B m etal ,
X OH A , a cid group .
N H40H HC1 N ILC1 + E 2 0,

Na oH HC1 N a Cl H2 0 .
Water m ay act as the cata l yst in these r eact ions o
II Friedel C rafts reaction ;

.
-
B R, X C1 01
‘
OH ,
A CeHs etc , .
RCl HPh RPh Ho i ,
BOH HPh RPh H2 0 .
120
S O M E CHEM I CAL REA C TION S . 12 1
I
Al u m inium c hlori d e ,
zinc chl oride s ulf uric a ci d hydrogen , ,
chloride etc m ay act a s the catalyst

, .
,
.
III Al dol condensation ; B X aldeh y

. d e or ketone A s o ,
“ ”
called negative group co m bined with oz carbon -
ato m .
RC o HzCAz RC H C AZ H2 0 .
H
Various catalysts ; zinc chloride , hydrogen c hloride ,
al kalies etc , .
IV . E st eri fi cati on ; B al kyl , A acid group , X C1

or OH .
ROH HA RA H2 0 ,
RC1 + H A RA HC 1 .
C atalysts ; zinc chl oride sulfuric acid hydrogen ch l oride

, , ,
etc .
V Eth eri fi cation ; B

. a lkyl A al k oxyl group X , , C1
or OH .
ROH HOR ’
ROR ’
H2 0 ,
RC 1 + HOR ROR ’
HC1
’
.
C atalysts as in re actions IV
VI A mide f or m ation ; B
. acyl group X , OH or Cl ,
A amino group .
Ac OH HN H2 AC NH2 H2 0 ,
Ac Cl HN HZ AcNH2 HC1 ,
Ac OH HN Rz AcNRz H2 0 .
VII A mine formation ; B

. al kyl or aryl gr oup X , C1
or OH A amino group , .
ROH HNH2 B NE 2 H2 0 ,
RCl HNH2 RNH2 HC l ,
ROH HNRQ ’
B NR z
’
H2 0 .
122 C HEM I CA L RE ACTIONS .
VIII For m ation of nitro co m pounds ; B

. N02 X OH ,
or substituted OH group A alkyl or aryl group , .
H C 6H 5 O2 N ceH5 H2 O ,
O2 N OC2 H5 H C5H 5 O2 N 06H5 C2 H 5OH ,
H C 6H 5 O2 N C 6H5 H2 8 04 ,
OzNO2 CC H3 H C 6H 5 O2 N C 6H 5 H02 C C H3 .
I X For m ation of nitroso compounds ; B

. NO X OH , ,
C1 or substituted OH group X
, alkyl or aryl group , .
ONO E H C 6H 5 ON 0611 5 H2 0 ,
HC6H5 ON C 6H 5
ONOC2 H5 HCsH5 C5H5 C2 H 5 OH .
X . D iazotization ; B NO X , OH or Cl , A amino
or alkylated or arylated group .
ONOE HNHR ON2 HR H2 0 ,
ON Cl HN HR ON2RH HC 1 .
XI . B enzidine rearrangement ; B N 02 , X and A

N E C 6H4 .
H
O2 N NH OsHi H NH C6H4 N O2 .
C atalysts : sulfuric acid phosphorus pentachloride etc

, , .
These examples while by n o means complete S how h ow

, ,
general the given type of reaction is and that many of the ,
apparently different groups of reactions of organic che m

i str y may be classed together and treated fro m one general
point of view S ome general relations may be developed
.
from these equations The formation of certain products

.
in any given case depends as stated repeatedly upon equi

libriu m relationships velocities of the different reactions
, ,
and concentrations of the various substances involved .
Ta k ing any on e set of reactions it would be possible t o ,
develo p regul arities with regard t o various groups present
124 C HE M I CA L REA C TI O N S
. .
and that at present the view of acids i s based upo n an

,
outgrowt h of the ionic theory and incl uded in the m odern

views of Werner S imilar relations may be shown t o hol d
.
f or organic reactions where there has been n o evidence of

ionization as the ter m is accepted i n the theory of electro
lytic dissociation .
If in the abo ve general reaction A of H A represents an

, ,
alkyl group the activity of the compound H A is very small

,
ordinarily B y activity in this connection i s meant the

.
amount of reaction in a definite time It is used in a very .
rough qualitative sense here as genera l quantitative com

,
parisons are not possible at present If into the alkyl .

,
group are introduced in place of the hydrogen ato m s acid

groups so called negative groups then the activity of the
,
-
,
compound increases in the same way that the ionization

constant or strength of an acid in aqueous sol ution is
increased when similar groups are substituted for the
hydrogen atoms of the oz carbon atom of the acid In the
- .
former case however ionization according to its present

,
definition need n ot be apparent If H A represents an .
aromatic hydrocarbon the introduction of these negative

,
groups exerts an O pposite effect t o 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 tothe H of H A On the other .
hand with the so called positive groups OH NH2 OR etc

,
-
, , , .
,
in the ortho or para position t o the H of an aromatic H A ,
the H A corresponds in reaction velocity etc t o a stronger , .

,
or more highly ionized acid while if H A is an aliphatic ,
hydrocarbon the gr oups have the opposite e ffect If B .
in B X represents an aromatic group such as ( C 6H5 C H ) O ,
(B)
then the NO2 group f or example will make the base ( as B X
may be considered ) more active corresponding t o the ,
greater ioniz ation constants of b ases I t h as b een obser ved .

,
S O M E C HEM I CAL REAC T IO NS . 12 5
with reference t o the explanation of the mechanism of the

reactions that the readiness of formation of addition com
,
pounds i n general increases with the strength of the aci d

( cf
. J K endall and others )
. .
The advantage of classifying reactions of organic chem

i stry in the given manner also becomes apparent in connec
tion with such reactions as the deco m position of k etones by
“ ”
alkalies the acid decomposition of acetoacetic ester the
, ,
decomposition of acids into hydrocarbons and carbon

dioxide the hydrolysis of tetranitromethane t o form trini
,
t r ometh a ne etc They may al so be classed together as the

, .
“ ”
same type of so called double decomposition reaction
-
.
It is also evident from this point of view that esters may be

decomposed with ben zene in an analogous manner to their
hydrolysis by water The relation between aldol condensa
.
tion e st erifi cati on eth erifi ca ti on etc is brought out

, , , .
, .
A gain a point of similarity to inorganic reactions is the

,
effect of the catalyst It is well known that di ff erent sol

.
vents influence the electrolytic dissociation of inorganic

acids f or example t o different extents A similar phe
, ,
.
no me n on is observable in these double decomposition

reactions It i s found in the type equation that when A
.
, ,
is aryl and B is alkyl that aluminium chloride sulfuric

.
, ,
acid and zinc chloride act as good catalysts or in other

, ,
words that H A and B X are highly active corresponding

, ,
t o large ionization in inorganic reactions On the other .
hand if A is aliphatic in nat ure it appears that very often

, ,
alkalies are superior t o acids as catalysts alkalies amines , , ,
and alcoh olate s being used a s f or example in the aldol, ,
condensation This corresponds t o a change in the solvent

.
with different substances in order t o obtain a greater

degree of activity of the reacting substances .
The statement has already been made in the preceding

pages that the present definition f or ionization is inadequate .
A t present a co m pound in solution i s considered t o be in
12 6 C HE M I CAL REAC TIO N S .
the ionic condition when it conducts the electric c ur rent

if placed between t wo el e ctrodes of di ff erent potentials .
T o emphasize more f ully the probability that the con cep

tion of ionization i s n ot altogether satisfactory a few r e ,
actions may be considered in more detail The hydrolysis .
of a n inorganic salt is explained by the ionic theory a s

M eX Ma
i lX -
fol l ows : HOH =OE+ E + If HX is a wea k a cid ( slightly

ll ll
M eOH E X
ionized ) then the H fro m the H2 0 wil l remove the X as
+ "
HX in solution increasing the concentration of the M e

,
+
and OH and resulting in the hydrolysis of the salt If

“
.
,
the M e OH is a weak base then the OH from the H2 0

“
will remove M e from sol ution and cause hydrolysis It is

+
.
assumed in each case that the salt M e X is highly ionized .
If in the first case HX is insoluble and in the second

,
M e OH i s insoluble hydrolysis of the salt will take place

,
as well The OH or H concentrations may be increased

+ ‘
by the addition of alkal i or acid t o the sol ution of the s alt .
A specific exa m p l e m ay be ta k en na m e l y : ,
M gC12 2 HOH M g ( OH) 2 Z HO1 .
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 M g ( OH) 2 is exceeded If h ow .
,
ever in place of M g Clg M gRClis used that i s t o say the

, , ,
Grignard reagent it will be observed that this compound

,
i s decomposed more rapidly by the HOH than is the M g C l g .
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 i s ionized i n a water solution since it i s immediately
12 8 C HE M I CAL RE AC TI O N S .
paral l el the former ( or vice versa ) and do n ot necessarily

precede or cause them For organic reactions it need n ot .
be necessary to present further evidence in this connection .
With inorganic reactions however the question appears not , ,
t obe s osimple The theory of electrolytic dissociation does

.
n ot necessarily postulate that only ions react For some time .
after the theory of electrolytic dissociation was proposed it ,
was attempted to apply the theory to every possible case

where there was the slightest possibility of an exp lanation
based upon it In recent years the trend of thought has taken
.
a di ff erent tur n and the explanations of certain reactions

, ,
which at one time had been assumed to be purely ionic in

character considered the u n ionized molecules as also taking
,
-
part in the reactions The first steps in this development .
were taken by G S enter ( J C hem S oc 9 1 467 . . . .

,
and by S F A cree ( Am C hem J

. . 410; 38 2 58 . . .
,
and these have since been followed by S Arrhenius G .

, .
B re d ig H C S Snethl
, . . a g e H Goldschmidt H M D awson
.
, .
, . .
,
A L apworth H S Taylor J S tieglitz and others who

.
, . .
, .
, ,
favor the V iew that both ionized and u n ionized molecules -
are active in chemical changes even in aqueous solution

and present evidence bearing on the question .
A ccording 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 C ertain physical .
properties of substances which early in the history of , ,
the electrolytic dissociation theory were consi dered to be ,
dependent upo n ionization have since been shown t o 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 u n ionized molecule L ater work showed that
-
.
ionization changes do not affect the color of the substance .
Reference m ay be made here to a detailed review of these

relations published by J L ifschitz ( S ammlung chemischer .
SO M E CHE M I CAL REAC TIONS . 12 9
und chemisch technischer Vortr age Vol 2 1 Nos

-
, .
, .
—
5 7 ,
p 17 5
. The explanations advanced at different
times with regard to the color changes of indicators illus
trate these views very well Ostwald in 189 4 D i e wissen
i ch en Grundlagen der analytischen C he m
.
s ch a f tl ie p 1 04)
”
, .
attributed the d i fl ere nt color of an indicator in acid or

al k aline solution t o the different colors of the ions and u n
ionized molec ules If the indicator substance itself wa s
an acid the color in acid soluti o
.
, n wo uld b e that of the

u n ionized molecule
-
while in alkaline solution the color
,
would be that of the negative i on If the indicator su b .
stance was a base the color in alkaline solution would be

,
that of the un ionized molecu l e in acid sol ution that of the

-
,
positive i on This theory was shown n ot t o be genera l

.
enough t o inc l ude the observed phenomena and was re ,

“ ”
placed by the chemical theory first suggested ( for phenol
phthalein ) by B ern th sen and developed by J S tieglitz .
( Jour A m C hem Soc 25 1 112

. . . and especially by
.
,
A Ha nt z sch B er 39 109 0 ( 19 06) and numerous articles

. .
,
since ) wh o showed the ionic theory of indicators t o be

highly improbable The present view considers every
.
change in color of an organic substance to be due t o an

intramolecular rearrange m ent 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 t o the other The productio n of ions is .
secondary in the tautomeric changes and if the ions are ,
colored it is because the u n ionized m olecules from which

,
-
they are derived are colored The equilibrium between the .
tautomeric forms of a substance depends upon a variety

of factors such as solvent temperature small amounts of
, , ,
certain added substances such as acids or bases etc ,

.
Ha nt z sch has shown the important part played by solvents

'
in affectin g the e quili b rium ( and therefore the color change )
1 30 CHE M I CAL REAC TI O N S .
between the tautomeric for m s of some indicators ( B er 4 8 .

,
1 58 S uch actions take place with indicator s 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 m arked with the relatively small amount
of added substance necessary t oproduce it ( cf A A Noyes . . .
,
J our Amer C hem Soc 32 8 1 5

. . . .
,
Other changes of
conditions may be considered similarly f or the indicators as
a specia l 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 n ot enter into the theory of their
color changes as assumed in the earlier theory although it ,
appears t o be connected with one of the factors involving

the sensitiveness .
It is evidently possib l e t oextend this method of treatm ent

t o other reactions N o more will be taken up at present
.
,
but the V iew will be emphasized that chemical reactions

need n ot 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 M any i f
,
.
,
no t all of the changes which have been considered hereto

,
fore as metatheses invo l ve without doubt primary addition

, , ,
and subsequent decomposition or splitting off in various

ways of the reacting molecules .
The question of tautomerism and the factors influe ncing

it m ay be considered further in the same way as organi c
1 32 CHE M I CAL RE ACTION S .
S om e of h is concl usions fro m his experi m e nta l wor k m ay be

given :
In his first paper he ta k es up the q uestion of stability of
isomeric compounds which rearrange to form more stabl e
substances to a practically irreversible extent under th e
given conditions Q uantitative data are supplied f or a
.
series of such changes The rearrangement of a number

.
of acids and bases t o m ore stable configurations was given .
The stability of these compounds toward ionization was

used as a measure The equation A . RT log K was ,
m ade 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
“
f or bases ( omitting the part played by the solvent ) when ,
the initial and fina l substances are at unit concentration It .
is evident therefore that the free energy of ionization i s

, ,
directly proportional t o the natural logarithm of the ioniza

tion constant and that to determine the relative stabilitie s
,
of t wo acids ( or bases ) in terms of the free energy of ioniza

tion it is only necessary t o compare the logarithms of their
,
:
ionization constants S ince an acid is m ore 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 th e
.
logarithms of these ionization constants D eric k gives the

.
results of a number of isomeric organic acids and draws ,
some general concl usions with regard t o their struct ur es

and relative stabilities toward ionization For example f or
.
,
“
t etrah ydroben z en ecar boxyl i c acids he finds that whenever
,
2
the unsaturation is A with respect t o a given carboxy l
group true rearrangements of the n on reversible type are
-
” “
possible and a l so the compounds from which Thiele
S O ME C HEM I C AL REAC TION S . 1 33
deduced his theory of partial va l ence as well as other acids ,
which obey the same r ule must be compounds which are ,
formed with weak reducing agents involving small energy

changes and where the speed of reaction is smal l s o that
co m pounds res ult which are very unstable toward ioniza
”
tion and therefore toward rearrangement
, In addition t o .
these quantitative results a nu m ber of rearrang ements are

,
’
grouped in D erick s fir st paper under various headings .
These relations are however only qualitative in character

, ,
.
In a S econd series of papers D erick goes farther and ,

“
studies the polarity of element s and radicals measured in
”
terms of a logarithmic function of the ionization constant .
This is evidently the direction in which advance is t o be

e xpected a study of the action of various groups on the
,
equilibria of certain reactions in terms of a ffinity changes .
The following definitions are given by D erick :

.1 A n element or radical possesses positivity if when it is ,
substituted f or a hydrogen of water it increases the h y ,
d roxyl ionization It is therefore said t o be positive

. .
.2 A n element or radical possesses negativity if when it ,
is substituted f or a hydrogen of water it increases the ,
hydrogen ionization It is therefore said to be negative

. .
Water is used as the standard f or determining the polarity

of various groups The relative free energies toward
.
ionization of the various substances are used t o deter m ine

the relative stabilities and in this sense the classification is
,
limited It i s however usef ul and important a s a com

.
parison of the stabilities toward a certain transformation

and giving a measure of the effect on a definite reaction of
di fferent groups A table is given of a number of these
.
ionization constants ( K and Kb f or acidic and basic ioniza

a
tion ) and the free energy values ( RT log K) In the . .
succeeding papers ( and also later ( with O Kamm ) in the .
J ou r Amer C hem Soc 39 388

. . . D erick takes up a
.
,
n um ber of reactions and discusses the effects of various
1 34 C HEM I CA L REAC TI O N S .
groups upon the stabilities of the reactions N o attempt

.
will be made t o discuss in detail the applications and cO n
clu si on s of D erick here

, but the reader is referred t o his
papers f or a careful study of the work This is perhaps the
.
first systematic attempt t o study in a quantitative way

the a ffinity relationships of a large num ber of organic com
pounds and to obtain exact data with regard t o the effects
,
of different groups on the equilibrium constants and there

fore the stabilities in certain reactions in various molecules .
The importance of this wor k must therefore be emphasized

as mar k ing a beginning of the systematic q uantitative study
of reactions such as have been given in these chapters ,
where f or lack of su ffi cient data only the qualitative aspects

,
co uld be presented .
1 36 C HE M I CAL REAC TION S .
compounds also Am monia was used there as a typical

.
example B ecause of the general point of view which is

.
emphasized here the comparative study of the unsaturated

,
properties of the olefi n s and of ammonia will be of value .
The combination of olefi n s with acids t o form esters etc , .

,
is strikingly similar t o the combination of ammonia and

acids t o form salts In the great majority of these com
.
pounds one molecul e of the olefin or ammonia combines

with on e equivalent of the acid The reaction i s also .
reversible in both series D esignating the olefin by the

.
symbol E n ( ethylene as example ) the following reactions

, ,
may be given .
En HC1 Et Cl( E t denoting E thyl ) ,
En H2 0 E t OH ( Water ta king the part of

the acid ) ,
C 5H1 () C 5H11 02 C C C 13 ,
En H2 SO4 E tHSO4 ,
( A Oppenheim and H Precht B er

. .
, . 9 , 32 5,
E sters m ay be regarded as the ol

e fi n at e s o
acids j ust as f ,
ammonium salts can be looked upon as the ammoniates of

acids Just as ammonia combines with salts such as Pt Cl4
.
,
C 3C l 2 etc to form ammoniates s o may olefi n s combine

, .
, ,
with salts t o form olefi n ate s C ompounds of this last

.
type have not been studied extensively but the following ,
may b e mentioned : ( C H3) 2 C C HC H3 2 Z n C12 ( from iso .
butylene and zinc chloride ) [ J Kon d akow J pr C hem , . . .
(2) 4 8 4 74
, C2 H4 P t Cl
4 [ V M eyer and P Jacobson
. . .
,
Le hr buch der organischen C hemie Vol 1 p 8 32 , .

, .
etc.
“ ”
So called
-
anomalous olefi nat es which contain a dif ,
f ere nt proportion of acid or salt than the 1 1 ratio are also

k nown The zinc chloride compound j ust given is an
.
example ; partially saturated p olyolefi ns s uch a s the m ono ,
O LE FIN S AN D TH E I R REAC TION PRO D U C TS . 1 37
halogen addition products of terpenes as me nth a d ie ne s ,
belong t o this group ; ethyl ether may be looked upon a s a

d i ol
efi n a t e of water ; the compound ( C H3) 2 O C2 H4 [ G r .
B aum e and A F O Germann C r 1 5 3 5 69

. . . m ay ,
. .
,
be written C2 114 7 H2 0 [ R de Forcra n d C r . .

, . .
1 35 9 5 9
, is an example ; a complex alkyl halide
01
% / H
9
“
C H3 Cl OH3
such as may b e formed by the co mbi n
C H3
/
/ C O
\
02 11 5 C H3
ation of several molecules of simp l er olefi n s and one m ole

cule of hydrogen chloride ( M eyer and Jacobson pp 8 33 , .
,
etc .
M ixed addition compounds containing olefi n s have also

been described ; for example FC C12 C2 H4 H2 O [ J Kach ler , . . .
,
B er 3 5 1 0
.
,
Fe B r2 C2 H4H2 0 [ C C hoj nacki Z f
. . .
, . .
C hem 18 7 0p
. . an olefi na t e and am
m oni a t e of water etc , .
These reactio ns show the similarity between the olefi ns

and ammonia and that the common property of u nsat ura
,
tion in both leads t o the formation of analogous products .
The simplest compounds which are formed from the

ol e fi n s are the alkyl halides which correspond t o the ,
ammonium halides There is at present n o direct exp eri

.
mental evidence of the action of catalysts in their formation ,
b ut in their dissociation into olefin and hydrogen halide ,
aluminium chloride zinc chloride etc affect the rate of

, , .
,
reaction greatly [ P S abatier and A M ai ble C r 1 38 407

. .
,
. .
,
141 2 38 , This shows itself more p arti cu

l arly in the lower temperature necessary for their rapid
dissociation The alkyl chlorides dissociate more readily
.
than d o the bromides and these more readily than d o the

,
i odi des Althou gh n oexact quanti tative data re gardin g the

.
1 38 C HE M I CAL REAC TION S .
velocities and e q uilibria of these reactions are at hand they ,
may be considered to be analogous t othe relative degrees of

dissociation of the ammonium halides studied by A S mith .
and co workers [ Jour Amer C hem Soc 37 38

- . . . .
,
The action of certain substances such as al k alis in these

reactions will be taken up later in this chapter .
A further relation of the alkyl halides m ay be mentioned .
U nder the same conditions the primary halides dissociate

,
more readily than the secondary and the secondary more ,
readily than the tertiary ( S abatier and M aible In ,
the study of this reaction no statement was made as t o the

,
probable equilibria [ It will have been noti ced that in the

.
discussion of organic reactions the experiments often are ,
not definite or quantitative This leads t o uncertainty in

.
the theoretical treatment a s t o whether a ready formation

,
of a compound refers to the velocity under certain conditions

or t o the amount present under equilibrium conditions .
C areful regulation of conditions and quantitative working

are essential for the further develop m ent of the science of
reactions included in organic chemistry ] It is possible t o
—
.
conceive of the tendency of the n alkyl halides going over

into the £30 on boiling or of the formation of isopropyl
,
benzene from n propyl chloride and benzene by the Friedel

-
C raft s reaction as due to the different equilibria of the

,
olefin and hydrogen halide with different sets of products

( n orma l 73
8 0 and terti a ry halides ) ; the on e which is found
, ,
experimentally depending upon the conditions of the various

equilibria or the relative velocities of the reactions
,
.
C onnected with this is the reaction in which hydrogen

halide is added to an olefin the halogen being finally com
,
bi n ed mainly with the carbon with l east hydrogen ; that is t o

s a y to form the tertiary compound preferably secondarily
, ,
the i so compound [ A M ichael B er 39 2 138

-
. 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 -
, ,
t r i meth yl
eth ane
140 C HE M I CAL REACTION S .
C2 H5C l C2 H5 +
Cl ,
KOH K OH ,
O,H. +
OH €2 H50H,
€2 H50H O2 H4 H2 0 .
This explanation is n ot satisfactory f or olefi n s In the .
first place no evidence i s at hand indicating that the alkyl

,
halides ionize One of the arguments advanced t o meet

.
this criticism is that the solvent in the case of the formation

of the olefin is n ot water and therefore the t wo cases are
no t comparable If water were used as the solv en t the
.
,
solubility of the alkyl halide wo uld be so small that ioniza

tion in solution could n ot be detected by any of the present
m ethods On the other hand very small concentrations of
.
,
ions can b e detected experi m entally M ost chemists there

.
,
fore d on ot attempt t oexplain the reactions of alkyl halides

,
on the ionization b asis T h e t wo reactions the for m ation

.
,
of am m onia and the formation of ol e fi n s consequently are ,
considered t o be quite different .
If the formation of ammonia from ammonium salts i s

considered from the addition dissociation and displacement
-
point of V iew the t wo reactions become analogous U pon

, .
this basis the for m ation of ammonia m ay be indicated a s

follows :
HC1 S olution the ammoniu m
of
NH4Cl a O NH, chloride ( NH4C 1 might be
.
( H2 0) written f or NH3 HC1 ) ,

.
HCl
KOH N H3
H2 om Ho
3
( 2 0)
H
NH;
( H2 034 .
O LE FIN S AN D T HE IR REAC TION PR O D UC TS . 1 41
Or it m ay be represented according to the general type

reaction ( chapter 5) as follows :
KOH
NH, KC1 .
S imilarly the alkyl halides ; in a q ueous so l ution the

f or
equations wo uld be :
[ ( H2 O) y C2 Hbcll KOH [ ( H2 O) y C2 H5K0Hl C1

C2 114 ( H2 O) y +1
and in alcoholic so l uti on : 0
[ (C s ol Q s Cll KOH [ ( C2 H50H) C2 H5KOHl

2 Cl
C2 H4 ( C 2 H5 0H) H 2z0 1 K 01 ‘ ‘
It is true that this explanation appears t o b e more com

plicated than the ionic explanation but it h as in its favor
,
the fact that it is more general and unquestionably repre

,
sents more nearly the mechanism involved .
For most purposes it is n ot necessary t owrite the reactions

in such a complicated way the following b eing sufficient :
,
KOH C2 H5Cl HC 1 KC 1 + C2 H4 H2 0 ,
KOH NILCI HC1 KC 1 + NH3 H2 0 .
When potassium hydroxide is dissolved in alcohol there ,
is likely t o b e some potassium ethoxide KO C2 H5 formed

, , .
It i incorrect o name compounds of this type al

coh olat e s
( s t ,
since alcoh olate s correspond t o hydrates while these com

,
pounds correspond t o hydroxides ) There is therefore a

.
, ,
possib ility of the formation of ethers when alkyl h alides

are treated with an al coholic solution of potassium h ydrox
id e.
CzH5Cl KO C2 H 5
C2 II4 Cm“ ( or C H 0H) KC l C2 114
H01 H2 0 2 5
KOH
H2 0
( or ( 02 11 32 0) KC 1, etc .
C2 114
A nother very interesting point in connection with the

reactions of the alkyl chlorides bromides and iodides is the , ,
fact that the iodides show a tendency t o give a larger yield

of olefin than d o the chlorides in the presence of alkali
[ A L ieben and A Rossi L ieb A nn 1 58 1 64
. .
, . .
,
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 Fur thermore the chlorides .
,
yield ether more readily than d othe corresponding bromides

or iodides [ M W i l d erm an n Z phys C hem 8 661
.
, . . .
,
and S B russow Ibid 34 12 9

.
, .
,
Al l of these reactions depend very likely upon the relative

velocities of the various possible dissociations of the inter
m ediate addition compounds under the given conditions .
The reason why ordinarily mixed ethers of the type

C2 H5ONH4 are n ot obtained is that they undergo dissocia
tion at such low te m peratures If the alcohol ammonia .
-
mixtur e is cooled su fli cie ntly these compounds are formed , ,
and may be isolated For example C H30H NH3 and .

, .
( C H3) 2 O NH3 ( G B aume and co workers J de C him

. .
-
, . .
Phys 12 2 16 2 2 5
.
, , belong t o this type .
A reaction si m ilar t o that of ammonia and of the a m ines

is that by which olefi ns may be alkylated t o form olefi n s
containing a greater number of carbon atoms Thus .
,
amylene treated with methyl iodide yields hexylene and

heptylene [ ( M Eltek off B er 1 1 412
. J Lermontoff
, .
, .
,
L i eb A nn 1 9 6 116
. .
,
C 5H1() C eH12 1 ‘ ‘
HI ,
C aHlo 071114
144 CHEM I CAL RE A C TION S .
acid as well a s the s ap onifi ca ti on of the ester formed ;

all speak against such a simple interpretation S ince ethyl .
alcohol and s ulfuric acid or olefin and sulfuric acid for m

, ,
ethyl sulfuric acid Et H S O4 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 A ccord .
ing to the general theory of addition reactions advanced in

this book the intermediate compound would be more com
,
plex and the ethyl s ulfuric acid itself would be one of the
,
products of the dissociation A number of equilibria may .
be given t o represent the possible dissociation products .
This list is n ot complete b ut will indicate the possibilities

of the reaction .
Et OH H2 8 04 ( ba ) II 2 0 ( 1)
-
-
a
( E nla
é EA b H2 0
H2 8 04 ( Hzol
( a n -
E n (2 )
( H2 0) b — a
a
, En
En bH2 0
b
H2 8 04
( 3)
4
( )
2
E 20 (5 )
En bH,O ( 6)
E quilibrium ( 1) represents the reaction between ethyl

alcohol sulfuric acid and water t o 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 .
A ll of these reactions have 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 t o indicate the possi
.
bilit i es for the quantitative study of a common reaction

presumably well known - .
If a different catalyst were used in the above reactio n ,
whil e the various equilibria would be identical in principle ,
the prod ucts a ct ually obtained under any set of definite
OLE FIN S AN D THE IR RE AC TION PRO DU CTS . 145
conditions m ight be different due t o the specific action of

the catalyst on the different equilibria The action of zinc .
c hloride may be cited With trimethyl ethylene the com

.
,
pound ( C H3) 2 C C H C H3 2 Z n C 12 has been isolated With

. .
water it gives d imeth yleth yl carbinol ,
OH
with hydrogen chloride tertiary amyl chloride ; if heated
,
alone d ii soamyle ne [ J Kond ak ow J pr C hem ( 2 ) 4

, 8 , . . .
,
47 5 S ulfur ic acid and isoamylene under suitable

conditions yield d ii soa myle ne also This polymerization .
reaction is used commercially in the formation of synthetic

rubber from the octa d ien s The specific action of the .
partic ular catalyst employed is shown also by the fact that

i s o propyl bromide dissociated at the temperature of bo i ling
—
-
amylene in the presence of asbestos while the n bromide ,
did n ot [ D Konowalow B er 1 8 2 8 08
. .
,
.
,
Although liquid ammonia is an associated liquid [ E C . .
Fran klin and C A Kraus Amer C hem J 2 1 14

. .
, . . .
similar polymerization reactions have n ot been observed

with a m monia or amines .
The acetylene hydrocarbons may be studied from the

same point of V iew as the olefin hydrocarbon They only .
differ in the degree and amount of unsatur ation .
It was shown that alkyl halides may be formed from

Ol e fi n s and acids and may be looked upon as salts o f the
hydrogen halides or as organic chemists have been in
, , .
the habit of c alling such salts as esters of the halogen acids

,
.
In speaking of the alkylation of olefi n s it was pointed ou t ,
that alkyl halides add t o olefi n s 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 t o the olefin as J Kon d ak ow [ J pr C hem . . .
54 4
, 52 showed He described the reaction as
.
follows
I46 CHEM I CA L REAC TI O NS .
( C H3) 2C C H C H3 Z n C lz
( C H3) 2 C C H C H:
Cl C ( C H3) zc s
Z n C lz .
As he did not examine the intermediate addition com

pound of the three reacting components but treated the ,
mixt ure directly with water removing the zinc chloride , ,
he could n ot determine the action of the latter He did .
notice however that when the olefi n zinc chloride addition

, ,
-
compound was treated with hydrogen halide the latter ,
replaced the zinc chloride and formed the corresponding

alkyl halide [ J pr C hem 4 8 475 . A t higher tem .
,
p er a t ur e s large amounts of the polymerized olefin were

,
formed These various reactions can be accounted f or

.
on the basis of various equilibrium equations .
M any other salts have properties similar t o those of zinc

chloride Thus G Gustavson [ J pr C hem ( 2 ) 34 1 61
.
, . . .
,
found that al uminium bromide formed a compound

with butylene and the use of m ercury salts f or the hydra
,
tion of olefi n s and acetylenes etc may be quoted For the ,

.
, .
further discussion of the addition of alkyl halides to olefi n s ,
the reader is referred t o the chapter on the Friedel C rafts -
reaction Just as amines and ammonia react with acid

.
anhydrides and acid chlorides so do the ole fi n s J Konda ,

. .
kow [ B er 2 7 Re f 309 9 41
.
, was able to bring about
.
,
the addition of these substances to olefi n s in the presence

of zinc chloride etc The external conditions must how
, .
,
ever be regulated caref ully i n order to obtain the desired

,
products ; that is t o s ay t o have the intermediate addition

,
compound dissociate along the lines of the necessary

eq uilibrium .
S ince some of the oxides of nitrogen m ay be looked upon

a s similar in constitution t o anhydrides of oxygen acids it is ,
readily understood why addition products can be obtained

fro m thes e oxides and the olefi n s When nitrogen trioxide .
148 CHEM I CA L R EA CTI O N S .
physi k C he m 1 63
. showed this auto catalytic
.
,
-
action t o 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 sol ution ) soformed ,
the greater its action [ Z physik C hem 2 6 . 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 amy l halide
,
.
The equations showing these changes are as follows :
[ fitd w x
HA c .
Am + HA c + HX
W Nernst and C Hohmann [ ( Z physik C he m 11 352

. . . . .
,
showed that in the reaction between olefin and acid

t o form ester the stability of the ester as measured by the
, ,
equilibriu m constant
C a ci d C olefi n
K
G es ter
increased and the value of the constant K decreased with

, ,
the strength of the acid S imilar conclusions were reached

.
by J Kendall [ J Am C hem Soc 36 17 2 2

. . and . .
,
others Nernst and Hohmann also showed that the velocity

.
of formation of amyl t ri ch l
oracet a t e from amylene and the
acid was proportional t o 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 n ot being
, ,
associated in it A t the same time it is probable that the

.
ether and the trichloracetic acid form a complex indicated ,
perhaps by th e following e q uilibri a :
OLE FIN S AN D THE I R REA CTION PRO D U CT S . 149
AcOH
nE tz O AcOH
a E
) ta
n EQ O
The influence of benzene and ether as solvents on the
velocity of the ester formation is similar t o their influence
on the reaction between triethylamine and ethyl iodide
described in C hapter V .
Just as zinc chloride accelerates the reaction between an

olefin and water t o form the alcohol and the reverse r e
action so also does it accelerate similar reactions in which
,
an acid or an alkyl halide ta k es the place of the water .
J Kond ak ow [ J pr C hem 4
. . 8 4 79
. found that when
.
,
zinc chloride was added to a solution of trimethylethylene

and acetic acid an addition compound C5H10 Z n C 12
, ,
. .
H
( OAc) 3 crystallized ou t Treated with water this addi
.
,
tion compound yielded amyl acetate B y altering the con .
d i t ion s s o as to obtain the maximum yield that is by , ,
isolating this intermediate addition compound and treating ,
it with water Kon d ak ow was able to obtain a 2 0per 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 mixt ure was allowed to stand f or some time

before water was added a considerable amount of diamylene
,
was formed The reaction may be formulated as follows :

.
X C5 H10 Z Z II C l
2
( C5H1o) x a Z Z II C 12
C 5H1 0
( Z HG I2 ) y HOAC Z Z n Cl
C 5H10
Z z
€ H ( C 5H10) x
( 5 10)x H
( OAc) ,
( HOAc) , a O
( Z II C I2 ) 3
( Z n C 12 )z
C5H1 0
0
l
l
1 50 CHEM I CAL REAC TION S .
The other equi l i b ria which are possible with these substances
are n ot given They wo uld be similar t o 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 f ormation of amyl
acetate the only di fference being that the zinc chloride
,
addition compound under the conditions of its formation ,
does not form appreciable amounts of ester b ut only when ,
treated with water A B é h aland A D e sgre z [ C r 11 4

. . . . .
,
67 6 have used this m ethod f or the for m ation of

esters of higher olefi n s .
S ince the esters of organic acids are olefi n at es it is clear ,
why in the distillation of esters like the waxes etc where

, ,
.
,
a high temperature is necessary olefi n s are often for m ed : ,
CI 5H31 C O2 C18H37 C 15H31 C 02 H C1 8H36
Sofar esters have been considered only in relation t otheir

formation from olefi n s and acids The usual method f or .
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 B aume and G P Pa mfi l[ J C him Phys

. . . . .
12 2 6
, 0 and by J Kendall and J E B ooge [ J A m . . . .
C hem Soc 38 1 7 12
. . Kinetic studies by J S tieglitz
,
.
and by H Goldschmidt showed that addition products

.
m ust be assumed t o be present in the reaction mixtures ,
b ut the exact nature of these products could n ot be deter

mined .
From what has been said of the mechanism of reactions

so far it may be stated that e st eri fi c at i o
,
n fro m the point
15 2 CHEM I CAL REA C TION S .
For the particular reactions in question these would be ,
come : For ( a )
HOH HOH
HA
+ 2 HZ O
2 HOH M A + H2 0
( dehydration if M A is inso l uble
, ,
For
HA HC1 ROH HC 1
2 HC 1
RA HC1, ROH H2 0.
S ince the neutralization of

an acid by a base takes place
practically instantaneously and since this reaction has
,
been explained in past years as due t o ions rapid reaction ,
has been ta ken t o be a characteristic property of ionic

reactions Other reactions in aqueous solution have also
.
been taken t o bear out this V iew It was shown previously

.
h ow the addition theory explains the neutralization rea o

tion ; the same explanation applied t o esterifi ca t ion shows
the advantage of a common viewpoint for the t wo sets of
reactions The differences in velocities of the t wo m ay be
.
explained as due t o the difference in e ffi ciency of the t wo

catalysts water and acid which is in turn related to the
, ,
formation of the intermediate addition co m pounds a nd

their properties .
In the formation of esters in ab solute a l coho l it has b een ,
found that salts such as zinc chloride increase the for m ation
of esters especially when hydrogen chloride is also present .
This is one of the common methods used in e sterifi cat i on .
R E nge l (cf Werner p 1 1 3) pointed ou t that the a ddition

. .
,
.
OLE FIN S AN D T HE I R REACTION PR O DUC TS . 153
of one m olecule
hydrogen c hloride t o a molec ule of zinc
of
chloride caused at the same time the addition of at least
t wo molecules of water t o for m the compound Z n C l gHCL
2 H2 0 Just as with the platinic chloride compounds with

.
hydrogen chloride or water or both hydrogen is found in the

,
outer zone S ince water and alcohol are very much ali k e
.
in many respects it is possible that where absolute alcohol

,
serves a s the solvent the salt e ffect of the zinc chloride is

,
similar t o the salt effect in aqueous solutions .
For the fur ther discussion of similar reactions the reader ,
is referred t o C hapter VI In general the term hydrolysis

.
,
is taken t o m ean the decomposition of a substance by

water S ince water is one of the products in the for m ation
.
of esters fro m alcohols and acids hydrolysis becomes the

,
reverse reaction of e st erifi ca ti on in this case Therefore .
what has already been stated concerning e sterifi cat ion

applies also t o hydrolysis .
S ince water is closely related t o the a l cohols it is n ot ,
surpr i s i ng that in certain reactions alcohols play a part

sim ilar t o that of water in hydrolysis Thus instead of :
.
,
HOH B u HA
. HA HA ,
the following m ay be written :

HOH HA
En En
E uHOH E nHA
HOH HA
and as examp l es of such reactions m ay be cited :

,
E t OH EtI E t OEt HI ,
C H3 C OOC5H11
. C5H11 0H .
A mong other methods used in the formation of esters m ay

be m entioned the acylation of alcohols by m eans of acid
1 54 C HEM I CAL RE A CTI O N S .
chlorides and acid anhydrides These reactions really be .
long t othe same type as the others as can be seen from the ,
following equations : ( C f D Kon owalow Z physik C he m . .

, . . .
1, 67
AC1 AOH En . HC1
AC1 E nHOH En
HOH E nHCl A OH
It is evident that this is only an alcoholysis of the acid

chloride and corresponds t o reaction III above In a
, .
great many cases alkali aids in the formation of esters by

this method This corresponds t o the addition of alkali
.
t o an aqueous solution of a salt t o aid its hydrolysis The .
latter is generally explained on the ionic basis as due t o

increasing the concentration of OH It migh t 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 f or 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 .
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

, ,
f or example combines with the acid halide

,
The simplest .
way of writing the reaction taking place woul d be :
En Py
AC 1 Py
AC1 HOA HC 1
A ci d chlorides etc ,
.
, of inorganic acids also react with
156 C HEM I CAL REACTIONS .
proof of the struct u re for alcohol as ROH The latter .
rests upon the proof that on e atom of hydrogen acts

differently from the rest when treated with a metal like
sodium and that a hydroxy l is present as shown by treat
, ,
ment with phosphorus halide A s shown in a former chap

.
ter with acids tautomerism i s possible and the alcohol

,
H H
\ /
may react in the for m C 2 0 j ust as acids d o .
H H
Io nization is not probable f or this compound since posi ,
tive hydrogen i s combined with carbon predominatingly

nega tive .
This brings up the q uestion of the structures of organic

acids which while n ot pertinent t o the subj ect under dis
, ,
c u ssi on still may be interpolated in this place

, U p t o 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 t o alkyl halides in their reactions

with amines and alcohols etc the similarity between
, .
,
ethers and esters and between amines and amides points

, ,
strongly t o a similarity in chemical m akeup or constitution .
This relationship can be most simply expressed or accounted

f or by considering the organic acids as water which is not
only ole fi n a t e d as in the case of alcohols but as also having
, ,
carbon monoxide combined with it and thus giving them ,
the structure the car b on m onoxide being an un
saturated compound like w ater olefin ammonia etc B e

, , , .
cause of tautomeric changes within these addition com

pounds j ust as i n the hy d rates and ammoniates of platinic
,
chloride and the oxygen acids sulfuric and nitric acids the
, ,
atoms m ay occupy different positions in the m olecule .
0 o
II Eu * - *
H H
é
H
\\
C é
ofl C H En
(2) ( 3)
O LE FI NS AN D THE I R REAC TION PRO DUC TS . 15 7
Formula ( 2 ) corresponds to the structure which is used in

organic chemistry at present the proof for which is out
,
’
lined i n M eyer and Jacobson s L ehrbuch der organisch e n
C hemie Vol 1 p 7 6) and other textboo k s The
.
, . .
reactions cited in this proof of structure may in general

be applied equally well t o all three structures The c on .
sideration of the three structures shows a closer relationship

between organic acids and inorganic acids than does strue
ture ( 2 ) alone .
C arbon monoxide bears the same relation to formic acid

that sulfur trioxide bears t o sulfuric acid or that platinic ,
chloride bears to ch lorp la ti n i c acid etc C arbon monoxide , .
also bears the same relation to the higher organic acids

such as acetic propionic etc acids that sulfur dioxide
, , .
,
bears t o the sulfonic acids or that the anhydride of nitrous

,
acid bears to the nitro compounds etc , .
0
l
l
i
En En Bn
Organic acid S ulfonic 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 themse l ves more readily :

, ,
HOH HC 1 HOH En N H3
CO CO
En En
01
‘
CO CO CO CO
E nH OH En H C l En H OR En H NH2
a ci d ch l ori d e e s t er a mi d e
Formic acid differs from the other acids of the organic

series in bein g simply hydrated carbon monoxide This .
1 58 C HEM I CAL REAC TION S .
structure f or formic acid agrees with al l the properties of

the acid It is n ot at all surprising that its dissociation into
.
carbon monoxide and water is effected by catalysts such as

hydrochloric acid etc ( G E B ranch Jo ur Amer C hem
, . . .
, . . .
S oc 37 2 316
.
, since it is an addition reaction similar ,
t o the for m ation of ammonium chl oride from ammonia and

hydrogen chloride The explanation f or the decomposition
.
of formic acid into carbon dioxide and hydrogen is evident

from formula ( 3) f or acids given above .
H
= H2 002
H O
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 Oech sner de C oni nck .

,
C r 1 36 1069
. .
,
C H3C OOH C H4 C 02
= E D H2 003
H
/
Aromatic ac i ds can also be included under the structures

given With them the phenylene group plays the sam e
.
,
part as the olefin with the aliphatic acids .
Oxalic acid would have the following structure ; that of

a m ixed acid si m ilar t o dithionic acid .
HOH oxalic acid , HOH dithionic acid .
This indicates the dissociation of oxalic acid into carbon

m onoxid e and carbon dioxide and of dithionic acid into ,
sulfur dioxide and sulfuric acid .
160 CHEM I CA L REAC TIO NS .
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 olefi n at e d 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 the ammoniacal
,
sol ution of the ammoniated 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 li kely act j ust as the solvent ether does ) .
E thers are generally spoken of as inert compounds .
What is really meant is that they do not react with metal s ,
alkalies and most acids at ordinary temperatures with

,
appreciable velocity A s pointed out the properties of

.
,
the olefi n ate d hydrogen a ff ord an explanation The same .
holds true f or tertiary amines It has already been pointed

.
ou t that a di fference i s shown in the stability or better , ,
the reactions of the Olefi n at e d 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 m ethod used f or the determination of

,
the amount of ether groups present in compounds may be ,
explained on the same basis They are simple displace m ent

.
reactions The existence of the intermediate addition com

.
pounds ( O xonium salts ) has been proven :
E n2 HOH
. HI HOH
HI 2 HOH .
Other acids are capa bl e of decomposin g ethers . C oneen
O LE FIN S AN D THE I R RE AC TION PRO DUC T S . 1 61
t rate d
sulfuric acid dissolves ether with the evol ution of
considerable heat and if the mixture i s heated f or some
,
time at 1 00 degrees ethyl s ulfuric acid and ethyl su l

,
fate are formed Also acid chlorides react similarly with

.
ethers .
AC 1 AC 1
The reaction
/ COH3C 1 + C H3C OOC5H11
2 C H,OC .H11 2 C H3C OC1
\ C5H11 Cl C H3C OOC H3
m ay be quoted as example ( F Wedekind and J H ausser . .
mann B er 342 08 1
, .
,
The amines differ from the ethers and alcohol s in that

they are ole fi n a te d ammonia or ammoniated Olefi n s What .
has been said with regard to ethers and alcohols applies

also in a general way t othe amines Primary and secondary .
amines correspond t o the alcohols while the tertiary amines

correspond t o the ethers B ecause of properties of the
.
aminated compounds or ammonium salts as compared with

the oxonium salts or e th erate s 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 wh ile in the oxygen series the properties of
,
the olefi n ate d hydrogen and also of the hydrogen with the
alcohols are more prominent than those of the central oxygen
ato m It is only in recent years that much attention has
.
been paid t o the et h era t e s and in general t o the oxonium

salts .
B ecause of the properties of the ammonium salts and

aminates which permit of their existence under ordinary
conditions it i s much easier toS how the mechanism involved
,
in the formation of amines than in the correspondin g ,
1 62 C HEM I CAL REACTIONS .
cases of the alcohol s and the ethers It has been possible .
t o S how the occurrence of the intermediate addition com

pound a t 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 t o prove the existence of such com

pounds The for m ation 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 :
E n HX
. NH; N H, HX 1
°
amine ,
E n HX
. E n NH3 . N H3 HX 2
°
amine ,
E n HX
. E D2 NH3 N H, HX 3
°
a m ine .
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
Ft H
Ph NH2 HC 1 NH2 P11
HC I
.
NHs ( Pen Phenylene )

The reason f or n ot considering the acid of the al kyl halide
to play this part in the formation of ethers is t o be found ,
in the intermediate addition compound the alkyl am ,
moni um salt which combines with the acid so that under

,
ordinary conditions the latter is not liberated and allowed

t o go through the cycle again E ven in the formation of
.
the dipheny l amine where the intermediate compound dis
1 64 CHEM I CA L REACTION S .
En
( HO A )” HOH
( HO A)
En
( HO A ) NH3
,
11, — 1
With an acid HX present :
HOH HOA ,
HX
En
En En
HO A E zNA
HX
A mides m ay also be for m ed by other m ethods si m i l ar t o

the methods used f or the acylation of a l cohol s that is with
, ,
acy l halides and acid anhydrides :

En
AC1 HNH2 HC1
,
A ( O A) A ( O A) HO A .
NH;
The for m ation of amides from a mm oniu m salts of oxygen

acids is in fact only a part of the dissociation of the inter
m ediate addition compound i n amide formation from an
amine and an acid The formation of a m ide from ester
.
and ammoni a i s S i m ilar t o the formation of amide from
OLE FINS AN D T HE I R REA CTION PRO DUCT S . 165
amine and acid except for the efi n a t e d

ol acid in place
E
En
AN H ,
OE
of the acid : H OH
AO H
A mides may be hydrolyzed and sap oni fi e d j ust as esters .
This is only the reverse reaction t o their formation Just .
as with the esters amides m ay also undergo alcoholysis

,
.
The reactions are as follows :
En A OH
ANHz AN Hz
En
HOH NHs
AO
( M eyer and Jacobson p , .
En
’
En
' En
HOH
etc .
C H A PT ER IX .
O XI D ATION RE D UC TION
-
.
I N the last fo ur chapters a number o

f che m ical reactions
were taken up and classified according to certain principles
laid down in the earlier chapters In C hapter V the .
,
general consideration of reactions wa s Outlined and some

of the principles elaborated C hapters VI and VII con
.
t a i n e d a classification of reactions based upon certain
g eneral types o f chemical change the actual substances

,
taking part being subordinated to the general scheme In .
C hapter VIII the point O f view was shifted in that the

change in composition of the substances reacting wa s
e mphasized . The various reactions considered before from
,
t h e standpoint of type of reaction were here developed from

the position of the reacting substances and as the specia l ,
group of substances chosen the che m ical changes undergone

,
by the Olefi n s were outlined In these four chapters h ow

.
,
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 .
Th is limitation excluded all oxidation reduction reactions -
which will be taken up in this and the following chapters .
It seem s advisable first to define and describe the phe

no me n a of oxidation and reduction from the newer chemical
viewpoints and then to apply these definitions and d e scrip
,
tions t o a number of reactions .
The valence of an element is defined as the number of

n egative electrons an atom of that element loses or gains
to form chemical link i n g s S tated in so m ewhat different

.
terms the valence of an element may also be defined as the

,
number O f equivalents of the acidic or of the basic con

st it u e nt s co mb ined with, or associated with one for m ul a ,
1 66
1 68 C HEM I CA L REACTION S .
m ultiple of this quantity are involved This holds true .
for organic substances undergoing oxidation or reduction

a s well as f or inorganic substances as long as the substance ,
c a n be brought into solution and satisfactory electrical
m easurements made ( A practical method of illustrating

.
“ ”
such changes is by means of the Ch em ometer described
first by W Ostwald Z physik C hem 1 5 39 9
.
, . . .
,
In the equation for the change in free energy or the

chemical affinity of a reaction as stated in C hapter I ,
A RT log e l K,
02
nz
,
1
if the electromotive force of a galvanic cell in which the

current is produced by the chemical reaction is denoted
by E and one gram equivalent of the substance in question
,
is transformed then ,
E = A,
under S imilar conditions of reversibility etc under which , .

,
A may be measur ed using suitable units

, W Nernst de . .
op e d the osmotic theory of current production S howing

v el ,
the mechanism by which the chemical reactions produc ed

the electric current Thus the difference in potential of
.
,
t wo sol utions containing univalent ions of a completely

ionized electrolyte of concentration m and nz with mobilities
of cation and anion equal t o u and a ( motion under a
definite potentia l gradient) is given by the equation
u 1) m
E = ~
R T log
E
e
u + v
In an analogous manner f or the solution of a metal in a

,
solution of its salt E RT log P /p when on e gram

, e
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 univa l ent i on
,
O XI D ATIO N—
RE D UC TION 1 69
of the metal in the solution In place of the pressures .

,
P and p the corresponding concentrations 0 and 0 may

, , ,
be used S imilar relations may be developed f or negativ a

.
ions and elements A comparison of the electromotive

.
forces developed f or example with m etals and solutions of

, ,
their ions will S how the relative oxidizing or reducing

potentials of these elements ; that is the che m ical a ffinities ,
with which these elements enter into chemical combination .
AS pointed ou t before an element entering into chemical

,
combination forms definite chemical lin ki n g s that is to say , ,
gains or loses electrons These electromotive force values

.
are fundamental therefore for studying the chemical a ffi n i

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 .
B erzelius more or less definitely in his electrochemical

theory N T M W ilsmore ( Z physik C hem 35 2 9 1
. . . . . . .
,
calculated from the best data available the relative

electromotive forces S hown by a number of e l ements 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 a s

zero These values c an be used to determine the replace
ment of metals etc by each other the electromotive forces
.
, .
, ,
of galvanic combinations etc They apply directly t o the

, .
concentrations indicated For other concentrations some

.
what different values must be used .
The quantitative theory of electromotive force produc

tion and its relation to chemical combination outlined very
briefly and superficially ( for more exhaustive treatments
the reader is referred t o suitable text books on physical
chemistry ) may be extended t o 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 CHE M I CA L RE ACTION S .
val ence to include all chemical co m pounds E vidently .
this co m parison is deep seated S ince all chemical com

-
.
pounds are formed by the tr ansfer of electrons producing

the link i n gs the atoms are all charged electrically in these
,
compounds The che m ical affinity m ay then be con

.
si d er e d t o be given by the affinity o f the given atom f or an

electron under the conditions pertaining t o that compound ,
or in other words by a value which might be said t o corre

sp o n d t o electric potential in electromotive force meas u re
ments These electric potentials are n ot a s yet susceptible

.
t oquantitative m easurement in the same way as the electro

motive forces i n galvanic cells b ut the principle is similar
,
and the che m ical a ffinity of a given combination m ay be

expressed as electromotive force or electric potential or ,
m ore in conformity with the valence views used an electron ,
potential This electron potential of an atom in combina

.
tion will m anifestly be d ifl erent in different compounds ,
j ust a s the electromotive force of an element is different in

different combinations of solvent etc The electron poten
, .
tial cannot be m easured quantitatively at present a s already

stated except in isolated cases b ut it can be used in a
,
qualitative sense in a classification of reactions Recalling .
the definition of oxidation and reduction it is plain that ,
f or electron potential when used t o compare di fferent su b

stances m ay be substituted relative oxidizing and reducin g
,
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 che m

ical compounds and reactions The next step will be t o
.
study the distribution of the valence electrons in a molecule ,
or the valences of the different atom s in a m olecule A .
clear understanding of these valences ( positive or negative )

i s necessary for the formulation of compounds on the basis
of the electron conception O f valence j ust as fifty years ,
a g o t h e arrange m ent o f atoms in a m olec ule an d their
172 CHE M I CAL RE A C TIONS .
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 t o be a direct method f or finding some of the
charges on some of the atoms or groups The arrangement.
of the elements in the Periodic S ystem of M e nd el ée ff is in ,
part an expression of the di fferences in the properties under

,
discussion and probably serves as the most genera l method

,
f or 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 l ow oxidizing potential or in other words

, , ,
elements of high oxidizing potentials are ordinarily negative

toward elements of low oxi d i z m g potentials The arrange .
m ent of the elements in the Periodic S ystem brings out

regularities such as the relative positive and negative
p roperties of the elements In the
. horizonta l rows the ,
elements of larger atomic weights are negative toward

those of smaller receive electrons t oform chemical linki ngs
, ,
possess higher oxidation potentials ; in the vertical rows ,
the elements of smaller atomic weights receive negative

electrons from those of larger atomic weights in for m ing
chemical linki ngs .
These regularities apply however only to the stable form s

of chemical l i nk i n gs It is readily conceivable that under
.
S pecial conditions compounds will be formed in which the

linking is less stable and in which the negative electron is
transferred in the direction O pposite t o that of the stable
linking This would be the case with elements whose
.
oxidation potentials or affinity f or negative electrons do

, ,
n ot differ widely or with elements with great inertia whose

,
velocity of reaction is S low so that they would exist f or a

measur able time in unstable forms of co m bination These .
questions will be ta k en up again .
—
O X I D ATI O N REDUC TI O N 17 3
In order t o determine the structura l formulas of s ub

stances physical or chemical m ethods or both S imultane
,
y m ay be used
ou sl The use of a physical m ethod will ‘
n ow be given in some detail The linking of carbon with

.
carbon in which partly owing to inertia t o reaction the

, ,
states of oxidation of the carbon atoms cannot b e deter

m ined readily i s invo l ved in these structures ( cf K G
, . . .
Falk Jo u r Amer C hem Soc 33 1 140

, . . . .
,
The structures of organic acids a s deduced from their

ionization constants in aqueous Sol utions w i ll be developed .
The ionization constants ( K X 10) of the acids as caleu

5
lated from the Ostw ald dilution law ,
2
7
K
7 )
in which the volume in cubic centimeters containin g
0
one molof the acid and y ' the degree of ionization found
,
from the conductance ratio will be used Only those acids

, .
will be considered f or which a fairly reliable value of K has

been obtained This eliminates the highly ionized acids
.
f or which K varies with change in concentration The .
data refer t o
In considering the structures of the organic aci d s it is ,
evident that the oz carbon atom ( the one combined directly

-
with the carboxyl group ) influences the ionization constant

of the acid t o 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 genera l classes

.
which may be formulated as follows :
I : . H
C C 02 ; I I : C C 02 H ; I I I : . H
C C 02 ; v
I : C C 02 H . . .
The car b oxyl group is assumed t o be negative t o the oz

carbon atom and t o exert practically the same effect on the
1 74 C H EM I CAL RE AC TION S .
valence thr oughout The acids belonging t o class I ar e

.
those in which three electropositive groups are combined

with the a carbon atom ; those belonging to class II two
-
,
electropositive and on e electronegative ; t o class III one ,
electropositive and t wo electronegative The ionization .
constants are found t o increase in the order of the classes

I II III IV
, , ,The acids represented by formula IV such
.
,
as trichloracetic acid are t oo highly ionized to give satis

,
factory dissociation constants and will n ot b e considered ,
here .
This method of consideration di ff ers from the ordinary

on e which attributes the variation of the ionization con
,
stant directly t o the natur e of the neighboring atoms or

groups in assu m ing that the influences determining the
,
m agnitude of the ionization constant are the positions of

the electric charges on the atoms These positions indeed .
are determined by the nature of the adj acent atoms or

groups SO that the new V iew is t obe regarded as a develop
,
m ent of the older idea which serves t o give it greater ,
d efi n i t e n e s s The influences exerted by the double or

.
triple bond accordin g t o 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 B carbon atom or the directions of the valences of this

-
,
ato m doubtless influence the ionization constant ; but as

,
will be seen this infl uence is in most cases of small i m

,
portance when compared with the influence exerted by the

bonds of the oi carbon atom The groups combined in the
- .
7, 6 etc positions doubtless exert an influence on the

,
.
,
constants also but this influence is negligible in the con

,
sider ation of this classification .
Al though the classification depends pri m arily upon the

directions of the valences the specific effect of certain ,
groupings m ay be great enough at times t o exert a pre

dominatin g infl uence and obscure the relations mentioned .
176 CHEM I CAL REA C TION S .
tive e ffect is evident h ere b ut is it n ot great enough t o ,
mask the additive influence of the bonds ( as will be seen

presently with the a halogen substituted acids) For the -
.
acids containing the grouping : C C O2 H the constant ,
may be taken in general t olie between and with

variations due t o the constitutive effect of the substituting
groups up to and possibly higher .
( The data f or the acids refer t o 2 5 degrees and were

taken from the results of the following observers : W Ost .
wald Z physik C hem 3 1 7 0 2 41 369

, . . H G .
, , ,
. .
B ethmann Ibid 5 385 , M B erthelot A nn chim

.
, , .
,
. .
phys .
, 23 4 3 A C rum B rown and J Wal k er
, . .
,
L ieb A nn 2 61 1 1 6( 18 9 1) J Walker Trans C he m Soc

. .
, , .
, . . .
,
61 69 6( 18 9 2 ) P Walden Z physik C hem 8 4

, 33 .
, . . .
, ,
10 6
, 46 F St oh m a nn and C Kleber J p rakt . .
,
. .
C hem 4 5 4 . 75, A Han t z sch and A M i ol

, at i Z . .
,
.
physik C hem 1 0 2 3
. E Franke Ibid
.
,
48 2, .
~
,
.
,
H E uler Ibid 2 1 2 64 . B Sz ysz k owsk i

, .
, , .
,
Ibid 22 1 7 3
.
, W A S mith Ibid 2 5 1 9 4
, . .
, .
, ,
W A B one and C H G Spr a n klin g Trans C hem Soc

. . . . .
,
. . .
,
7 7 654
, D M L ichty L ieb A nn 31 9 369 . .
, . .
, ,
W A B one J J S udborough and C H G Spranklin g

. .
, . . . . .
,
Trans C hem S oc 85 5 34( 19 04) K D rucker Z Physik

. . .
, , .
,
. .
C hem 5 2 642 .
, ,
The formula for the aliphatic acids containing a halogen

or similar ( negative ) substituent in the oz position m ay be -
represented by : C 002 11 The acids belonging t o this .
class which have been studied are i od acet ic oz ,
brombu t yri c oz br ompr op i oni c

, bromacetic -
, ,
o orbu t yr i c ,
z chl -
orprop i on i c ,
z-ch l
o
chloracetic f ocya n a cet i c
s ul , cyanacetic , ,
and oz B d ibrompropi oni c For acids of this

,
-
,
class the constant may be taken as lying between

,
and
unless m odified very m arkedly by so m e constitutive
influence .
O XI D ATIO N REDUCTION
-
. 177
Few acids containing t wo negative substituents in the

a position o
- f the formula : C G O2 H have been studied .
a, a D ib
-
rompr op i oni c ,
and dichloracetic are the ,
only ones f or which data were found A cids containing .
three negative substituents in the oz position are t oo highly-
ionized f or the purpose in view and d on ot give a satisfactory

constant .
The constants for the acids so far considered m ay be

summarized as fol l ows : For the grouping C — C OzH less >
—
,
than f or C -
C OzH
>
to f or, C Og H C ,
greater than 2 Individua l substituents modify these

.
values t o a greater or less extent but the di fferences be

,
tween the three classes appear t o be great enough t o

enable a decision t o be reached a s t o the structure of a
given acid in most cases .
A group of acids for which the constants lie between

those f or the acids containing the groupings C-
C 02 H >
and : C G OgH is known This group comprises the

.
acids d ii sopropylglycollic , lactic glycollic , ,
glyceric , eth oxya ce t i c met h oxya cet i c

, ,
mandelic , phenoxyacetic and benzilic , ,
T h e 0B (R H or hydrocarbon radical ) is evi

d e n tl
y the reason why these acids occupy an intermediate
position between the acids containing n o negative oz group -
and those containing on e This OR group is generally

.
taken to have an e ffect similar t o a negative group and

—
,
would therefore be formulated ) OR in the acids S ome .
of the acids approach the values f or acids of the class

:C C O2 H but f or most of them the difference is so
,
large that it must be assumed that either the OR group

exerts a constitutive influence m asking to a great extent
the effect of the bonds or that there i s some action ( such a s
inner oxonium salt formation similar t o that taking place
,
with amino acids) b etween the ether or hydroxyl oxygen
1 78 C HE M I CA L REAC TION S .
and the hydrogen or other part O f the carboxyl group which

decreases the values of K f or this group of acids as com
pared with the acids containing a different negative su bst i
tuent in the oz position resulting in a constant of from
-
,
to It may be pointed out however that the class t o

, ,
which any given acid belongs may readily be ascertained

as the composition taken in connection with the dissociation
constant S hows the structure of the oz carbon atom A n -
.
acid such as t ri ch lorla ct i c must be formulated

,
somewhat di fferently and prob ably i s best represented by

C C lg
\
the structure H O C C 02 H ,or intermediate between the
/
H
-+
C C O,H and : O C 02 H classes , j ust as lactic acid
:
is inter m ediate between the C C OM and : C C 02 11
classes
—
.
Sa tu ra ted Di b
asi c Aci ds W Ostwa l d
. the first t owa s
point ou t that the constants o b tained by his dilution law
f or the or g anic dibasic acids referred t o the first hydrogen
i on which was formed from the acid and that the second
hydrogen ionizes only in very dilute solutions SO that it ,
does n ot enter into the constant a s ordinarily determined .
For some acids the second hydrogen begins to ionize a ppre

c i ab ly at a di l ution of about 5 00liters but the
, constant as
determined experimental l y in the usual way is found t o
increase rapidly with the dilution when this occurs A .
study of the constants f or the d ibasic acids m ay therefore

follow the lines laid down for the monobasic acids by con
s id e ri ng the carboxyl gr oup containing the u n ionized -
hydrogen as a negative substituent .
M alonic a cid from this point of view is carboxyl acetic

, ,
acid and should bel ong t o the 1:C C 02 H class Its .

,
constant is found t o be The following substituted

m alonic acids with the ir ionization constants have been
, ,
m easured : d imeth ylmalonic o z t e tra met h l

z o -
n d i
, , y e e
180 CHEM I CA L REACTION S .
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 m ay

be considered as derived from the higher fatty acids c on
taining a negative substituent which exerts only a minor
influence upon the ionization con st a nt s a s compared with
the effect of the bonds They should therefore belong t o
.
the C: C 02 H class and in fact the constants for those

, , ,
measured are found to lie between and The

following acids are included and are arranged in the order
of increasing val ues for K : C amphoric sebasic azelaic , , ,
’ ’
suberic w w d iprop y1p imelic w w d ii sopr op ylp imelic n
, ,
-
, ,
-
,
’ ’
pimelic w w d im e th ylp i melic w w d ie th ylp imelic adipic
, ,
-
, ,
-
, ,
glutaric w w d iben z ylp i m elic a meth ylglu t ari c oz oz

,
’
,
-
,
’
-
, ,
’ ’
d i et h yl l i -d i m e t h ut ar i c , o d im e th yl
t , B, B yl
gl gl
u -
g a r c z, a u
taric , and fi-m e t h ylglut ari c .
Uns a tu ra ted A midst —The unsaturated acids will be ta k en

up in the same way as the saturated and the double bond ,
will be assumed to have the same e ff ect upon the dissocia

tion constant as if it were made up of two S ingle 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 C aution must be used however with

.
regard to the data for some of the isomeric acids as the ,
methods of isolating the pure substances had n ot been

worked out very satisfactorily when some of the measure
ments were made The following monobasic acids contain
.
ing a double bond between the oz and B carbon atoms in -
four cases and between the B and 7 in on e case may first

be quoted : M e t h yleth yla crylic sorbic , ,
hydrosorbic , t r i m e t h yl ic
acryl and acrylic , ,
These acids evidently belong t o the C : G O2 H
O XI DATION—
RE D UCTION . 18 1
class whether the oz carbon atom is com b ined with the

,
-
other atoms in the molecule by means of three single bonds

or on e double bond and on e single bond .
In the case of the isomeric unsaturated acids maleic and ,
fumaric acids may be considered in some detail S ince these ,
substances were isolated in a state of purity early and

the measurements f or finding the values of K may be con
s i d ere d t o be accurate Furthermore the composition of
.
,
the t wo acids is simple and it S hould be possible t o draw

perfectly definite conclusions The ionization constant of
.
fumaric acid was found to be and that of maleic

acid The possible structures f or these acids are
( a ) C OaH C H Z C H C 02 H and ( b) C OaH C H I :C H C 02 H
. . . . .
S ince the ionization constants refer t o one hydrogen ion

and the carboxyl group may be considered as a negative
substituent fumaric acid from the value of its constant
,
should belong t o the : C C OaH class and must b e as

signed formula ( a ) M aleic acid should then be re pre s
.
e n t e d by formula A n acid of this formula can ionize

in one of two ways either from the : C
, C 02 H group or
from the : C C 02 11
group The ionization constants
.
for the acids belonging to these classes differ widely and ,
the value found for maleic acid S hows that the ioniza
,
tion takes place by the first of the methods indicated M aleic .
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 .
,
is t o be represented by the formula C H3EC C 02 H .

,
and ph e nylprop i olic acid by the similar formula

,
H :
C 5 5C C C 02 H
. .
A roma ti c A d da —The aromatic acids are ta ken t oinclude

those in which a carboxyl group from which the hydrogen
182 C HEM I CAL RE ACTI O N S .
is ionized is in direct combination with a carbom atom of the

benzene nucleus This carbon atom corresponds t o the
.
a carbon atom in the satur ated acids and the bonds o

-
, f this
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 t o 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 n ot 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
ou t S pecifying the particular directions of al l the valences .
In general terms the benzene ring is assu m ed t o contain

,
alternate single and double bonds .
The ionization constant for benzoic aci d was found t o

be This indicates that benzoic acid belongs t o the
-
C>
C O2 H class and that its graphic for m ul a i s
,
002 H
H —H
l
H
the direction of the bonds indicated by dashes being u n
k nown Other aromatic acids i n which the directions of the
.
valences for carbon ( 1) are the same as f or benzoic acid but ,
for which the arrangement of the other bonds i s unknown

except that n o strong constitutive effect is manifested by
the two carbon atoms in position ( 2 ) and that therefore the
directions of the bonds in these are n ot such as would be
expected if only negative groups were co m bined with them ,
are the following : p Hydroxyben z oic

-
, vanillic ,
isovanillic , anisic , veratric ,
mesitylenic , m toluic
-
, p toluic
-
,
1 84 C HEM I CAL REAC TION S .
C hemical methods can also be used t o deter m ine

the dis
t ri bu t i on of the charges in a molecule or the valence of the
,
atoms and should prove of more general applicability .
Although no on e reaction c an be chosen a s an infallible

guide the reaction which can be relied upon most frequently
,
is that involving hydrolysis ( cf T Seliv a now B er 2 5 3617

. .
, .
,
W A Noyes J our C hem Amer S oc 35 7 69

. .
,
. . . .
,
( 1 9 1 3) In this reaction when an atom, or group i s
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 n o 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 t othe contrary no change may ,
also be assumed here With substances containing S ingl e

.
bonds only the oxidation potentials of the atoms should a s

,
a rule be so different that only on e form of the substance

is stable .
With compounds containing a double bond the condition s ,
are not so simple however It is necessary to consider all

, .
the possible cases and from a study of the reactions decide

which form ula may be assigned to a given compound .
Taking up substances which contain a double bond betwee n

two carbon atoms first it is evident that these compound s
,
may in general be divided into classes : ( 1) compounds i n

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
.
’ ’ ’ ’
C R2 2 C R2 ; G E 2 2:C R; ; C RR Z C RR ; C RR Z C RR .
If two isomers exist in any case because of the difference

,
in valence of the carbon atoms or their oxidation potentials ,
one would be expected to be more stable than the other ; if

o nl y one substance of the gener al type exists then it may ,
O XI DATION REDUC TION
-
18 5
be that the other is t oo unstable t o be formed permanently ,
going over into the stable form and it would be a question

,
then to determine by means of the chemical reactions , t o

which of the two types its reactions S how it to conform
best.
Of substances derived from the formula C R; C R4 none » ,
is known t o 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 S ince .
the molecule is symmetrical it l n a k es n o difference in the

,
resulting compound in which way another substance HI

, ,
for instance is added If however as a typical example

, .
, ,
propylene C H3 C H C H2 is taken there would be three

.
, ,
possibilities ; M e C H 2 C H2 and M e C H 2: C H2 or M e C H
2 C H2 . On treatment with HI if either of the last t wo
,
represents the structural formula the I would all go t o one

,
carbon atom and the H to the other only one substance

, ,
b eing formed ; while if the first represents the structure ,
a mixture O f t wo substances should be formed the H and I ,
being divided between the two carbon atoms The rea c .
tions in this case might be represented as follows :
M e C H 2 C H2 M e C Hz C HzI and
H I
I H
M e C H I: C H2 M e C HI C H3 .
The extent t o 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 t wo products formed The following .
results were obtained by A M ichael ( J pr C hem 60 2 8 6

. . . .
, ,
409
18 6 CH EM I CAL RE A C TION S .
Propylene H1 for m ed pr i nc i pally ( C H3) 2 C HI together

with a little C2 H5 C H2 1 .
Propylene Cl
Br yielded 5 parts C H3 C HB r C H2 C lto 7 . .
parts C H3 C HC1 C H2 B r
. . .
Propylene CH yielded 1 part C Ha C HI C H2 Clt o 4parts . .
C H3 C HC 1 C H2 1
. . .
Propylene HOC lfor med principally C H3 C HOH C H2 C 1 . .
and perhaps a little C H3 C HC1 C HzOH . . .
These examples indicate that the compounds belong t othe

C Ra Z C Ra type although propylene does n ot belong t o
,
this symmetrical type In general therefore if one form

.
, ,
exists this formula is assigned t o it if t wo forms the more

, , ,
s table possesses this formula .
’ ’
Of substances derived from the structure C B R G RR
a large number of isomers are known of which maleic and ,
f u maric acids may serve as examples From what h a s .
been said the more stable fumaric acid may be assigned

, , ,
’ ’
the form ula C RR Z C RR the less stable maleic acid
, , ,
’ ’
the form ula C RR Z C RR These structur es agree with
.
the structures developed from the ionization constants of

acids .
With substances containing a double bond in which the

two ha l ves of the molecule are dissimilar there are a greater ,
nu m ber of possibilities with three possible isomers in each

case The three isomers are not known f or any one s ub
.
stance with certainty The reason f or this may be found

.
in the fact that if the two halves of the molecule are made
up of groups differ ing very much in properties of the t wo ,
iso m ers in which the t wovalences act in the same direction ,
on e will exhibit very m uch greater stability than the other ,
m aking it extremely difficult if not impossible to isolate , ,
the less stable form With compounds containing a double

.
bond between t wo un l i k e ato m s the car b onyl group C O , ,
188 CHEM I CA L REA C TIONS .
geometrica l isomerism of double bonded carbon atoms and

the isomerism due t o plane configuration of certain cobalt ,
chromium and platinum compounds :

,
R X R R
:
X X X
\ O2 / \ O/ \ / /
Pt
> Ff
.
R/ \ X K/ N R R / \ X \ R
( P t ( N Hs) 2012 , et c .
)
Whatever explanation is accepted for the double bond

isomerism the same explanation wil l apply t othe isomerism
,
of the platinum compounds Werner considers that the

.
explanation of the spatial configuration applies t o 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
.
, ,
on e 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 t o the

class of electromeric substances S ince 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 group of electromers The spatial arrangements of
.
of the atoms or groups here would also be governed or

,
controlled primarily by the arrangement of the electrons

of the atom showing the O ptical 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 di ff erent acids or in , ,
other words that the substituting group influenced the

,
O XI DA TION—
REDUCTION 18 9
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 u m

doubtedly be explained upon some such basis .
C onsidering the states of oxidation of the carbon atom s

of the benzene ring as changed and basing explanations
of reactions upon them seems more logical than the pro
c e d ur e of H S Fry who more O
. .
, r 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 a d v a n t a
g ou s than the other in studying chemical reactions in gen
e ,
eral and building up a logical consistent system of chemical

theory it seems better to treat of the hydrogen combined
,
with carbon as positive until direct evidence to the con

t r ar y is at hand and to assign the changes in charges in
,
benzene derivatives to the carbon atoms .
C H A PT ER X .
SOME —
O XI D ATI O N RE D U C TION REAC TION S .
The structures which have been developed in the last

chapter with special reference t o the states of oxidation of
various atoms in molecules will n ow be applied t o a number
of reactions A s in the other classifications given in this
.
book emphasis is placed on the fact that the same principles

,
apply t o both organic and inorganic reactions and that any

reaction in one branch of chemistry ca n be paral l eled by a
reaction in the other branch In oxidation reduction r e
.
-
actions certain simple principles may fir st be poi nted out

, .
In thes e reactions when an oxidation takes place it is

, ,
always a particular atom which is oxidized It is incorrect .
t o speak of a group or a molecule being oxidized the change ,
actually taking place with on e atom in the group or mole

cule whose reactions are being followed and perhaps f or this
reason giving the impression that the group of which it
forms a part is being oxidized The same is of cour se true
.
, ,
f or reduction It is permissible t o S peak 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 on e 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 on e or more negative electrons then it is n e ce s
,
sary that some other atom in one of the molecules ta king

part in the reaction must be reduced ( gain on e 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 m agnesium an d sodium chloride are

,
1 90
I92 CHEM I CA L RE AC TION S .
3 1 4 The analogy to the inorganic

2 to .
reactions outlined is evident In the same way the Fit t i g

.
,
synthesis deals with an aromatic halide and an aliphatic

halide as f or example :
,
C 6H5B I ‘
C2 H5B I ‘
2 Na C 5H 5 C2 H 5 Z N RB I ‘
.
The reaction is similar t o the W ii rt z reaction but the ,
distribution of the valence electrons or the charges on

the separate ato m s 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

.
i sm Of the reaction is not so simple and that it takes place

in several stages E vidence for this V iew is to be found
.
in an analogous reaction in which magnesium is used in

,
place of sodium This reaction c a n be used in a great

.
number of syntheses and is generally known as the B arbier

Grignard reaction The ordinary formulation is as follows :
.
lRR
- -
’
. 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 I .
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 con cep

tion of valence would be as follows :
o f 1 I
Mg / Mg +R +R R
R ( 5)
a \
R
'
\f
(a )
The first action consists of the combination R I and + "
atomic uncharged m agnesium The possible intermediate .
SO M E O X I DA TIO N—
RE D U C TION REAC TION S . 19 3
product ( oz) i s given a n d may represent the first stage of

_
combination and perhaps be equivalent to a combination

such as would be produced by the force fields of B aly or
some similar view as discussed in some detail in an earlier
chapter In the formation of the definite compound
.
M g\ _ the m agnesium has been oxidized two units of

R
,
valence and on e of the carbon atoms of the group R reduced

t wo units of valence The second step of the reaction
.
consists of a Si mple reaction i n yolv i n g ultimately an ex

change without oxidation or reduction A s stated before .
,
a number of substances may take part here The net .
result is a reaction analogous to the reactions j ust described

with the added interest that intermediate products have
been isolated here which were not possible in other cases .
B ecause of these intermediate products it has al so been ,
possible to develop the mechanism of such reactions some

what farther and to bring out further analogies between
inorganic and organic reactions ( cf in this connection .
J M Nelson and W V E vans Jour A mer C hem S oc

. . . .
, . . . .
39 8 2
, It was stated that ether or some simil ar
solvent was necessary for the B arbier Grignard reaction -
t o take plac e The ether takes part in the reaction and

.
undoubtedly forms onium ( molecular ) compounds with the

reacting molecules It plays the same part in these r e
.
actions that water plays in the reactions involved in galvanic

cells This is shown clearly by the following measurements
.
of the resistances of a number of solutions :
R E S I ST AN C E IN O HM S (O RD I N ARY C OND U C T IV I T Y AP P A RA T U S ) .
Ether . . ab ov e 1 X 10 7
E t her cont ai ni n g et hy l b romi d e a b ov e 1 X 10 7
E t her conta i ni ng g ms M g as . G ri g n ard reag e n t
( M gOzHaB r ) p er X 10 3
S a me wi t h mg M g . X 105
M KC 1 a que ou s s oluti on X 10 2
1 94 C HEM I CA L RE A CTION S .
A cel l constructed with m agnesium and platinum a s elec

trodes and a dry etherea l solution of ethyl bromide contain
,
ing a small amount of previously prepared Grignard reagent

a s solution gave electromotive forces of from
, to
volts .
These and similar resul ts S how that the reactions in

aqueous and ethereal solutions are strictly analogous and
that similar chemical forces govern al l chemica l reactions ,
organic as well as inorganic .
The reaction involving addition toa double bond between

t wo carbon atoms was discussed v ery briefly in the pre
ceding chapter From the evidence a t present available
.
,
it may be said that if the two halves of the molecule d o n ot

di ff er t oo greatly in such compounds the linking may be ,
represented as : C Z C the charges indicated being only

those due t o the double linking If a halogen hydride is .
added to such a linking it is n ot necessary t o assume any

,
oxidation or reduction reaction taking place If however .

, ,
an element is added which in the stable form is negative t o

carbon as f or 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 on e unit of

valence or if a chlorine molecule Cl ) Cl is considered t o
,
—
have reacted one of the chlorine atoms will have been
,
reduced two units of valence while at the same time one , ,
of the carbon atoms will have been oxidized t wo units of

C 1 C1
valence t o give the group T
— T his would be a true
a:
:C ) C:
oxidation reduction reaction S imilarly if hydrogen were

-
.
,
added to a double carbon linking since hydrogen is normally ,
positive toward carbon the hydrogen wo uld be oxidized

,
and one of the carbon atom s reduced These considerations .
refer only t othe initial and final compounds of the reactions .
Probably as in the B arbier Grignard reaction intermediate

,
-
,
19 6 C H EM I CAL REAC TION S .
considered to be analogous on the one hand t o the trans

formation of ferrous chloride to ferric chloride for example ,
in which ferrous iron is oxidized t o ferric iron and chlorine

added and on the other hand to the transformation of a
,
compound such as phosphine t o phosphorus trichloride ( if

this direct transformation could be carried ou t exp eri
mentally ) i n which the phosphorus is oxidized from 3
to 3 Reduction reactions may be treated similarly and
.
need n ot be taken up in further detail here .
These reactions take place as a rule between t woor 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 on e atom i s oxidized and

,
another reduced at the same time that simpler molecules

are formed A S imple reaction of this type is given by the
.
decomposition of formic acid as follows :
= Hfl + CO
(8)
H
\ 3 t
—m+ +4
(w
H
3 . cd
In formic acid and its decomposition products the dirc o ,
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 C hapter 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 m onoxide and water are formed and
—
S O ME OXI DA TION REDUC TI O N RE AC TION S . 19 7
carbon dioxide and hydrogen are for m ed Reaction .
( )
a takes place by warming with sulf u ric acid ; reaction 1
( )
7
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 ordinaril y b ut that ,
on suitable treatment one se t predominates The product s

.
of the reaction are simple so that the states of oxidation of

the various atoms in the molecules are known It i s .
evident therefore that reaction ( a ) involves no oxidation or

,
reduction of any of the atoms in the molecule and that in ,
reaction the carbon atom of t h e formic acid is oxidized

t wo units of valence to form carbon dioxide and on e of the,
hydrogen atoms reduced t wo units of valence to form the

neutral hydrogen molecule A s 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 c a n be brought about with carbon monoxide
and sodium hydroxide and the reverse of reaction
, with
potassium or sodium amalgam carbon dioxide and mois
, ,
ture.
The decomposition of oxalic acid by sulfuric acid or heat

is analogous t o reaction ( a ) with formic acid :
0H +2 +4
CO 002 E 20
(9 )
N o oxidation orreduction of any of the atoms is involved

in this reaction That such reactions are not peculiar t o
.
carbon compounds is S hown by the fact that the analogous

sulfur compound dithionic acid undergoes a similar de
, ,
composition as follows :
,
[ H2 82 06l Se a So . H2 0 .
( 0)
1
198 C HEM I CA L RE A CTION S .
The structural formula of dithionic acid with the charges

on the atoms can be developed in the same way as with
oxalic acid .
S ome more complex reactions involving hydrocarbon ,
groups wil l be ta ke n up next but the development will

,
follow the sa m e lines as i n the reactions j ust outlined t o

gether with the general principles developed While u n .
que st i onably the reagents added influence the course a

re action takes under given conditions these reagents are ,
n ot incl uded in the present form ul ations It is intended .
t o bring ou t here the possible changes in valence of certain

atoms ( oxidation or reduction ) in fair ly simple reactions ,
s o as t o l a y 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 ,
g iven conditions and their oxidizing

, potentials or affinity
f or the negative electrons shall have been determined more
precisely especially f or organic compounds than is the
, ,
case at present .
The decomposition of acetic acid may be form ulated in a

way S imilar to that of formic acid ; namely a s follows :
H3C i
s O :
3
+2
i
l
\ = H c OH 00 ( a)
C 3 ,
H3
1 l
l
6 O +4
( 1 1)
6
+
\ / b
8 = CH +
4 0 2
( )
\
O
The formula f or acetic a cid is represented as an e q u il ibrium

between the two tautomeric structures as explained in
C hapter II In both the carbon atom of the carboxy l
.
g roup 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 car b oxyl group is given by the consi d
2 00 C HEM I CA L REACTION S .
1
_
02 H5 + C
\ 2
062 11 5 CO H2 0 2 02 11 ,
( b),
In reaction ( a ) oxidation of the carbon of the carboxyl

group h a s taken place and reduction of a carbon atom of
,
on e of the hydrocarbon groups In reaction ( b) no oxida .
tion or reduction O f any of the atoms in the reacting mole

cules has taken place .
The reactions of acetoacetic ester represent a somewhat

more complex case but c a n be treated in the same way
, .
A cetoacetic ester may decompose in t wo 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 transformations may be formulated a s follows :
:1 : 40 a? :
2
:3
3
+ 4
C H3 C O C H3+ C Oa+ C a H5 0H
» «-
(a) ,
\
(R ) oc a n g ( R) (R 1 )
( R1 )
( 14)
I f :3
1 + f :3
1111 2 0 C H3C 02 H+ C H3002 H+ 02 H5 0H ( b
) .
(R) ( R1)
Reaction ( a ) represents the ketone decomposition , reaction

the acid decomposition R and R1 can be used t o .
represent a variety of different groups The exact relation .
of R to the carboxyl group with which it is combined i s of

secondary importance a s 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 ( b) the acid decomposition
.
, ,
there is apparently n o oxidation or reduction involved .
This reaction involves the use of concentrated alcoholic

al k ali a reagent which is supposed t o cause or assist oxida
,
—
S O M E O XI DATIO N RED UC TIO N RE A C TI O N S . 2 01
tions in organic reactions W hether it does or not in this

.
,
reaction at an y rate no oxidation appears t o occur Pos

, .
s ibl it influences the changes occ rr i n g by re m oving the

‘
y u
acetic acid as soon as formed and causing t h e reaction t o

take the indicated course ( b) according t o the principle of
mass action In reaction ( a ) on the other hand an oxida
.
,
tion reduction has occ urred analogous in every respect t o

-
,
the oxidation reduction with acetic acid T h e group

- .
C H3C OC H2 in the former corresponds t o the group C H3 in

the latter ; in the former the product acetone corresponds
t o the product m ethane in the latter The possibilities of
.
tautomeric forms and inter mediate products are m uch

greater with acetoacetic ester than with the S imple acids ,
and n o attempt wil l b e made here t o formulate them .
The react i on between chloroform and alkali in which

the former i s hydrolyzed m ay be represented as follows :
HCOaH 3HC l.
( 15 )
No oxidation or re d uction i s i nvolve d hereIn order t o .
S how the unce rtainties W i th regard t o some apparently

simple re actions the decomposition of trichloracetic acid
,
( which may ta k e place on heating an aqueous s olution )

m ay be shown :
i f +4
0
0130
+3
1 + 4
'
01 H0013 + C O, ( )
1 6
+ 3 0
.4
G I3G
A
2
OH
The question which arises is as t o the struct ure of trich lor

acetic acid ; whether it is t o be represente d by fo rm ula (a )
202 C HEM I CA L RE A CTI ON S .
or b
( ) .The ionization constant does not give any c l ue ,
since it varies t oo greatly with the dilution t o per m it of

classific ation The small difference in potential between
.
the t wo carbon atoms of trichloracetic acid also adds t o the

uncertainty as there is nothing t o indicate whether one is
positive or negative to the other If for mula ( a ) i s correct .
,
no oxidation or reduction i s involved ; if form ula ( b) i s

correct then the carbon atom of the carboxyl group i s
oxidized t wo units of valence and the other carbon atom
reduced t wo units of valence in the reaction As stated .
,
there i s n o definite evidence t o indicate the true nature of

the reaction .
The reactions of be n z e ne sulfon i c acid have been of

interest in connection with questions of v ale nce f or some _
time On hydrolysis with acid benzene and sulfuric acid

.
,
are formed with alkali pheno l and s ulfi te The question

, ,
.
of oxidation and reduction in these reactions can be a p

p r o a c h e d best by considering first the structure of the
benzene sulfonic acid as developed from simple principles
and analogies .
In the first place in genera l when carbon combines with

,
sulfur the carbon atom loses a negative electron t o the

,
s u lfur atom This is evident from the relative positions of

.
these elements in the Periodic S ystem In the second .
place in the development of the structures of the acids in

,
C hapter I X it was found that benzoic acid belongs t o the

,
same class as acetic acid There i s every reason t o believe

.
that in these acids the carboxyl group as a whole is negative

,
t othe hydrocarbon group a s a whole whatever their internal ,
structur es may be although of course the various charges

,
are present on the individual atoms The formation of .
benzoic acid from benzene and carbon dioxi d e m ight then

be for m ulated a s follows :
f oH
i
[ CeHsf
'
H +
60
2 [ CsHsl +
a .
( 17 )
2 04 C HEM I CA L REAC TION S .
in b oth c ases involve no oxidation or reduction reactions ,
( b) are oxidation r eduction reactions The detailed e xp osi

-
.
tion with benzene sulfonic acid need not be gone into since ,
it follows the corresp onding changes with acetic acid .
A nother type of reaction m ay be mentioned here which , ,
whil e not oxidation reduction shows so me of the possibili

-
,
ties i n the way of relative oxidizing potentials of di fferent

atoms or the relative a fli nit ies of the atoms f or valence
,
e l ectrons S ilver nitrite and sodium nitrite when treated

.
with an alkyl h alide gi ve di fferent products With the .
for m er a nitro compo un d is obtained mainly ; with the

,
latter a nitrite predo m inates While according t othe older

.
views this wo uld point t o di fferent structures f or the two

,
nitrites according t o the principles developed in this book

, ,
the explanation of these di ff erences involves tautomeris m

a n d severa l chemica l equilibria The reaction m ay be
.
g i ven in genera l ter m s as follows :

+4 0
MeX l R‘ "
( )
a :
o
+ EX
M eX N b
\ ( ) .
O<- Me Oé - R
The silver and sodi um nitrites may exist i n tautomeric

forms as shown in the formula and outlined in C hapter II .
There i s noevidence at hand at present t o S how which form

predo m inates under any given conditions When the .
nitrite i s treated with the alkyl halide RX in all probabilit y ,
an addition compound is formed which is n ot given in the

equations and this addition compound is in equilibri um
,
with the two sets of products represented by equations ( a )

and ( b) There is no oxidation or reduction involved in
.
either of these equations U nquestionably both sets of

.
products are obtained with any m etallic nitrite Which .
S O M E O X I D A TION RE D UC TION REAC TION S
-
. 2 05
product i s obtained in greater a m ount 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 a ffinity or the
states of the equilibria B ecause of the similarity of the re ac
.
tions it would n ot be expected that the velocities would differ

,
greatly b ut this possibility must also be k ept in mind as p os

,
sib l y the dominating factor in controlling the course of the r e
action o b served T o spea k of the relative oxidizing poten

.
t i als toward oxygen and nitrogen of the metal instead of
the chemical affinities does not add directly t othe knowledge

of the reaction but brings it into line with the newer point
of V iew developed in this book and may aid in developing
,
a fut ure classification of such reactions If the metal i s

.
sodium in reaction the reaction follows cour se ( b)

mainly if silver course ( a ) It may be possible to deter
, , .
mine the relative oxidizing potentials of sodium and si l ver

toward oxygen and nitrogen in these reactions by suitable
measur ements of the equilibria under comparable condi
tions This point of view may evidently be extended t o a
.
number of other reactions which S how similar changes .
Finally a classification of chemical reactions which i n

,
e l udes all reactions in a general sche m e based upon the
valences and changes in the valences of the ato m s 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 definite atom of the molec ules involved remains con

stant .
If I the algebraic sum changes ; either A the number

, , ,
of n eg ative electrons on the atom in question is increased ,
or the number of positive charges on the atom is decreased

( o r reduction ) ; or B the
, number
, o f negative electrons o n
2 06 C HEM I CA L RE ACTIONS .
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 su m of the positive and negative charges on

the atom in question changes ; t e the atom in question . .
,
gains or loses the same number of positive and negative

charges simultaneously ( molecular or onium compound
formation ) ; or B the arithmetical su m of the positive
, ,
and negative charges on the atom in question remains

constant ; t e the electric charge on the atom in question
. .
,
remains unchanged .
T o su m 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 .
A pplied t o chemical reactions IA includes reduction ,
reactions IB oxidation reactions IIA molecular or onium

, ,
compound formation and decomposition I IB metatheses ,
in which none of the changes IA IB or IIA ta k es place , , .
S tated slightly differently the classification includes re

,
actions involving reduction oxidation molecular or onium

, ,
compound formation and decomposition and S imple r e ,
p lacement or rearrangement .
2 08 IN DEX .
Carpent er , C . D .
,
27 E l ectromeri s m, 1 8 7 , 1 8 8 , 1 89
C h emi cal a fii ni ty, 4, 5 , 6, 7 , 8 , 1 4, ec tr o
El moti c e f orce, 1 68 , 1 69 ,
32 , 7 8 , 1 68 , 1 69 , 1 7 0, 17 0,
1 9 1 ,
1 94
1 9 1, 2 05 E l ectron, 12 , 1 7 , 1 67 , 1 69 , 1 7 0,
Ch emi ca l energ y, 3, 4,
5 ,
14 1 7 2 , 1 8 3, 1 8 7 , 1 8 8 , 1 8 9 , 19 0, 1
Ch emome t er, 1 68 1 9 2 , 1 9 8 , 2 05 , 206

Ch ojnacki , 1 37 ectr o
El ni c y al
enc e, v, vi , 1 1,
C las s i fica ti on r eacti o 2 05 , 12 , 1 3, 1 8 , 2 4 42 , 49 , 54,
'
of ns,
,
32 ,
5 6, 1 70, 1 7 1 , 1 7 2 , 1 7 3,
C oll i e , J . N .
,
2 5 , 216 1 88 , 1 92 , 1 99 , 2 04
Col or, 1 05 , 1 2 8 ,
M
E lt ek ofi .
, 142
C omlbes, A .
,
1 03 E mory, W . 115 5
G one , L H , 27 E nerg y, p ac i ty a nd i nt ensi ty
—
. . ca
Coord i nat i on
- nu mber, 31 , 33, 34, f ac tors, 3 5
46, 47 , 48 , 49 , 5 1, 5 8, E ng el , R , 1 5 2
.
83 E nz ymes, 67 , 68 , 69
Craf ts , J . M .
,
95 , 1 03 E ph ra i m, E .
,
89 , 90
Creh or e , A C 34 E qui l i bria , ch e mi ca l, 2 , 6, 7 , 9 ,
—
. .
,
Cru m B rown , A .
,
1 76 54,
60, 7 1 75 ,
7 8 , 8 2 , 86,
Cull en , ’
G E . .
,
68 8 8 , 93, 1 01 , 1 02 , 1 08 , 1 12 , 1 1 3,
1 2 2 , 1 2 9 , 1 30, 1 38 , 1 40, 1 4
4,1
Da ki n,H D , 68 . .
146, 149 , 1 5 0, 19 7 , 204, 2 05
D aws on H M , 12 8 .
E s t er i fi ca ti on, 63, 1 1 9 , 12 1 , 1 23,
—
.
de C oni nck , W . 1 58
1 2 5, 1 47 , 1 5 0 1 54 1
d e F or cr an d , R , 1 8 7
E th er i fica ti on, 63, 1 09 , 1 1 0, 1 2 1 ,
.
D eri ck , C G 1 31 , 1 32 , 1 33, 1 34
. .
, 1 25 , 1 47 , 1 5 5
—
De sgr ez , A .
,
115 0 E uler, H . 17 6
,
D i ae o r eact i on, 1 1 6 1 1 9 , 1 2 2 E vams , W V 1 2 7, 1 9 3
,
. .
D i lu ti on la w, 5 3, 1 7 3, 1 7 8
D i th i oni c aci d p
d ecom osi ti on, Fa l k , K . G .
,
62 , 68 , 1 2 7 , 1 7 3,
115 8 , 1 97 1 87
D ou bl e bond i s omeri s m, 1 8 0, 1 8 ] Fi n dlay, A 26
,
.
1 84- 1 8 6,
1 8 7 ,
1 8 8 ,
19 4 F i sch er , E .
, 68
Dr u ck e r , K .
,
17 6 Fi s ch er , F . 105
D u claux, J 68 Fi tti g , R , 1 9 1 , 1 92
.
D u sm an,
,
vi F i t ti g s ynt h es i s , 19 1, 1 9 2
fiel d s
”
ll
F or c e , 2 3, 32 , 37 , 1 9 3
ectr o
El i s omers, 1 5 F or mi c aci d p
de com os i ti on, 1 9 6,
E l ectrolyti c d i s s oci a ti on, 1 0, 1 5 , 19 7
2 8 , 2 9 , 35 , 36, 41 , 42,45,47,48, F ra nk e , E 17 6
—
.
,
49 , 52 , 5 3, 5 4, 5 5 5 7 , 8 2 , 8 3, F r a nk l in , E 145
— —
.
8 6 88 9 0 9 2 , 1 2 3, 1 2 4 1 2 5 F r ee 4, 5 , 6, 7 , 8, 1 8 , 75,
—
en erg y,
—
, , ,
1 2 6, 1 2 7 1 30 ,
1 39 , 1 40, 1 48 , 1 32 1 34,
1 68
1 5 2 , 1 5 6, 1 69 , 1 7 2 , 17 3 F ri ed el , C .
, 25 , 9 5 , 1 03
I ND E X . 2 09
F r i ed e l -Craf t s r eacti on, 64, 9 5 Kaeh le r ,

J 1 37
1 06, 1 08 , 1 1 1, 1 1 5, 1 1 7 , 1 2 0, Km ,
1 33
12 5 , 1 38 , 1 46 K a u fi ma n n , vi
F ry, H . v ,
1 8 7 , 1 89 K e nd all , J , 2 7 , 1 05 , 1 25 , 1 48 ,
.
1 50
G a si orowski ,
K .
,
163 K i p pi ng ,
F . 1 02 , 1 03 «
G att er ma n
,
L .
, 1 03 Kleber , 176
G ene qu an d , P .
, 1 14 Kl ei n , D , 66 .
G er mann ,
A . F . 1 37 :
Kleme ns i e wi cz , Z .
,
91
G eyer, A .
,
1 55 K och J A
, . .
,
1 03
G i bb o ns ,
W . A .
,
27 Ko hle r E P
,
. .
,
98
K on d ak ow, J 1 36, 1 4
45, 1 46,
G le nde nn i n g , T A 68 4
. .
,
1 9
G o ld sch mi dt ,
E .
,
1 2 8, 1 5 0, 1 63 K on owa low, D 145 , 1 47 , 1 54
.
,
o er
G mb g , M , 217 .
Kr api vi n ,
S .
,
10
3
G r i gn a r d , V , 1 2 6, 1 2 7 , 1 60
.
,
1 9 1 , Kr a u s C A 145
, . .
,
1 9 2 , 1 9 3, 19 4,
1 99 ,
2 0
3
G ri g na rd r eag en t, 1 2 6, 12 7 , 1 60, L an g , R , .
1 9 3, 1 94
:
G ewi ts ch
ul
,
W .
,
98 L apwort h , A , 7 2 , 1 28 .
G u st avs o n G ]
,
.
, 9 6, 9 7 , 1 46 L ecco, M , 2 4 .
G uye P A , . .
,
98 L e r cyns k a , I .
, 1 05
L er m on toff , J 142
Hant zsch , A , 1 29 , 1 7 6 . L e wi s, G N . v ,
v i ,
Hfi u sse rm ann , J 1 61 i Li c h ty, D M . .

, 1 76
H elmh olt z , E , Z . L i e ben , A .
,
142
Hof ma n n, A W , 1 62 . . L i f s chi tz , J
Hof m ann , K A , 2 6 . . L ore nz , R , 9 1 .
H oh man n, 14 8 , 149
Hol le ma n, A F , 1 0 9 , 123 . .
Ma a ss , 27
Hoogewerfi , 26 M cI n t osh , D , 2 6, 2 7 .
Hyd r a tes, 2 1 , 26, 2 7 , 2 8 , 33, 36, Mai ble , A , 1 37 , 1 38 .
37 38 , 46, 47 , 48 , 5 1, 1
“
M ai n ( p ri nci p a l) va l ence,
’9
5 2 , 5 6, 5 8 , 8 1, 83, 89 , 31 , 32
M a rk owni k ofi , W , 1 1 4
‘
1 20, 1 41, 14
57 , 1 5 1 , 1 5 6 1 57, .
Ma r t i n s e n , E , 1 1 3
,
15 9, 16
1
0 .
Mel lor, J W , 67 , 7 4. .
I nd i c a tors , 1 29 , 1 30 M en d elé e if , D , 3, 2 0, 1 7 2 .
cons t a/nt, 5 3, 5 4 4 Me ns ch utki n, B N , 65, 9 7 , 9 8 ,

—
I oni z a ti on ,
1 7 ,
. .
148 , 1 7 3 1 82 , 262 9 9 14
47
I sbek w, W o . A .
,
9 0, 9 1 , 9 2 M enten , M L . .
,
68
Mer z , V , 1 63
.
Ja c obson , P .
,
1 36, 1 37 , 1 5 7 , 1 65 Me yer, V , 2 4, . 1 36, 1 37 , 15 7 ,
Jone s L W . .
, v ,
1 87 :
Jon es , W . J , 72 . Mi cha e l, A .
, 1 95
2 10 I N D EX .
Mi ch ael, A rt h ur, 1 38 , 1 85
Mi cha e li s, A , 1 04 . 2 8 - 31 , 33, 34,
36,
38 ,
39 ,
44,
Mi ch ae l i s, L , 68 . as, 1 9 9
Mi llik a n , R A , 1 2 . . P lotni k ofi ,
v . A .
,
26, 9 2 , 9 8 , 1 03
Mi ola ti , A , 1 7 6 . Pol ar a nd non- p ol a r va l ence, vi ,
M ol ecu l ar th eory, 1 , 2, 3 15 , 1 6, 1 7 , 1 9 , 9 7 , 1 35 , 1 67 ,
1 95
N ef , J . U .
,
99 , 1 1 0, 111 Pot enti a ls ,
oxi d iz i ng and re
N el s on, J M . .
,
v , vi
,
62 , 68 , 7 0, d uci ng , 1 3, 1 4 ,
1 1 6 ,
1 69 ,
1 7 0 ,
1 8 7, 1 9 3 1 7 2 , 1 7 3, 1 9 4,
1 8 7 ,
2 9 2 ,
N e r ns t W .
,
9 2, 148 , 149 , 1 68 , 1 69 29 4,
2 05
N i g g em an , E 10
5 Pr ech t E 1 36
—
.
, , .
,
N i t ra ti on, 1 08 , 1 09 , 1 1 0 1 15 , 1 2 2 P ri n s H ,
. J
N i t ri t e r eacti ons , 2 04,
2 05
N orthr op , J H , 70 . .
Reac ti on vel oci ty, 1 , 6, 9 , 60, 61 ,
N oye s, A A . .
,
1 30 62 , 65 , 66, 69 , 7 0, 7 1 , 73, 7 6,
N oye s, W A . v 1 84 79 , 8 1 , 9 7 , 1 06, 1 08 , 1 1 3, 1 1 4,
,
.
,
1 22, 124,
1 37 ,
1 38 ,
1 42 ,
Olefina tes, 1 36, 143, 1 47 , 1 47 , 1 48, 1 49 , 1 5 2 , 1 60,

1 7 2 ,
1 5 0, 1 5 6, 1 5 9 , 1 60, 1 61 , 1 65 205
Oni u m comp oun d s, 2 7 2 8 , 30, 32 , Rosan off , M A . .
,
72
38 , 5 7 , 8 1 , 8 8 , 8 9 , 1 0 5 , 10 6, Rossi , A .
, 142
1 1 2 , 1 9 3, 2 06
Oni u m va l ence, 30, 32 , 37 , 38 , 5 7 t
Sa ba i e r, P .
,
64, 1 37 , 1 38
Oppe nh e i m, A , 1 36 Sa ck u r, 91
—
.
Org a ni c aci d s ( s truc tu r es ) , 1 5 6 S a l t h yd rol ysi s, 1 26

'
1 5 8, 1 7 3 1 84 Sch e fl er , E 29 .
Os twa l d , W . 5 3, 1 29 , 1 68 , 1 7 3, Schlenk , W .
,
1 95
,
1 7 6, 1 7 8 c
S hmidli n , J 98 ,
Oxa li c ac id d ecom osi ti on, 15 8 ,p i van ow, T

Sel .
,
1 84
197 Se nte r, G .
, 1 28
Ur ani um s a l ts , 25 , 2 6, 48 , 147, S mi th ,
A .
,
1 38 *
1 59 , 1 60, 1 61 , 1 7 7 S mi t h ,
W A . .
,
1 76
S n ethla ge , H C' . . 1 28
P a mfi l, G P 1 50 i ng , C H G
Sp r an k l . . .
, 176
,
. .
Pa ne k ,
104 t
S a rk , vi J
P a rt i a l val en ce v 1 33 , ,
St er eoch emi c a l ca p a ci ty , v11 , 34
Pa tten H E 9 2
, . .
,
t t
S i e gli z , J , , 12 8, 1 2 9 , 1 50 . v
P eri odi c s yst em 3 1 0 , , ,
1 3, 2 0, t
S obbe, E , 2 6 .
1 72, 202 , 203 St oh ma nn F .

,
1 76
Pe rri er 96 St ra u ss , F .
,
26
,
Pe rri n J ,
3 S u dborou gh J , . 176
P h as e ru l e d i ag r a ms , 2 6, 5 8 , 9 7 , S u gi ura K 68 ,
.
,
9 8 , 1 62 Sul f ur i c aci d cond en s a ti ons , 1 07 ,

Pi ct et A .
,
105 , 1 1 4 1 1 1 , 1 26, 1 4 4, 1 45
3, 1 4
,
L I T E RA T U R E OF T H E
CH E MI CA L I ND U ST RIE S
On ou r s he lv e s i s the mo s t co mplete s toc k of

technical in dus trial, engineering an d s cienti fi c
,
b oo k s in the Unite d State s T h e technicalliter

.
'
atu re of e v ery t ra d e i s W ellr ep re sente d , a s i s also
the literatu r e relating to the v ariou s s ciences ,
b oth the b ook s u s efulfor reference a s wella s

’
tho s e fi tte d f or s tu d ent s u se a s text b ook s .
Al arg e nu mb er of thes e W e p u bli sh an d for an

e v er inc reasing nu mb er we are the s o le agent s .
ALL I N Q UI RI ES M A D E OF US A RE C H EE R
F ULL Y AN D C A R EF ULLY A N SW E R E D
AN D C OM P LE T E C A T A L OG S A S W E LL AS
SP E C IA L LI ST S SE N T F REE ON RE Q UEST
D . VAN N OST RAN D C OM P ANY

P ubi shers
l a nd l
B ookselers
s W A RRE N ST REE T N E W Y ORK

Chemical Reactions Their Theory and Mechanism

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Chemical Reactions Their Theory and Mechanism

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J O 4 a d )

T HE central idea of this book is the development of a

been used in more or less isolated cases for a number of

ﬁrst time that it is published in an extended form with

selves rest upon the development of valence views .

The modern interest in valence appears to have started

S ome years later 19 04 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

they were the ﬁrst dating from 19 09 on to publish extended

applications of the electron conception of valence to organi c

develop certain lines of chemical theory from this point of

over a certain course of chemical thinking U nquestion .

ably others have followed the same or similar lines of

th ought and reached similar c o nclusions Among those .

who have published along these lines may be mentioned

R F B runel , W C B ray and G E B ranch ,

attempt will be made t o g i ve a historical review of the

workers to publish before others does not negative the

For practical reasons it was not possible f or Professor ,

Nelson and the writer to add to the experimental data from

sufficient facts were recorded in the literature t o permit

The electron conception of valence has now apparently

chemists still speak of polar and non polar valences T o -

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 conce p

theoretical views are used At present these appear t oo ff er .

the only explanation which is at all satisfactory for what

I n recent years G N L ewis and I L angmuir have developed

certain conceptions of molecular structures from the point

of the utmost importance and indicate n ew methods of

ical reactions appears to be somewhat premature At least .

it appears to the writer that for him to attempt it would

is in no way a historical treatise they have not been given ,

in detail On the other hand it is b elieved that enough o f

the general theoretical s ide has been given to permit any

Q uestions of stereochemistry have n ot been included .

It would appear that S patial chemistry is entering upon a

arrangements of atoms in crystals as exempliﬁed in the

new conception of stereochemistry while at the same time ,

stereochemical explanations such as steric hindrance which

have been accepted heretofore:are being superseded by

A number of new points of view and explanations are

Professor Nelson to his students at C olumbia U niversity

possess is due in a large measure to him both in the develop ,

ment of the views and in the collection of material A mong .

others who have aided in various ways in the development

H T B eans of C olumbia University and D r M arston

IN order to classify chemical reactions so that it will be

certain general theories must be established These theories

have been developed gradually as the number and kinds

general principles upon which the theories of the mechanism

including atomic valence and the electron conception of

especially as controlled by the physical conditions and by

These principles indicate the lines which will be followed

relations will be considered only secondarily M ol e cular .

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

impossible to treat of a reaction velocity without treating

‘ 3 velocity of the reaction in the opposite