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STUDIES

IN

CHEMICAL DYNAMICS.

-STUDIES

CHEMICAL DYNAMICS
BY

J.

H.

v A N

H O F F

'T

REVISED AND ENLARGED BY

ERNST COHEN

DR.

Assistant in the Chemical Laboratory of the University of

Amsterdam

TRANSLATED BY

THOMAS EWAN

M.

Sc.,

Demonstrator of Chemistry in the Yorkshire

WITH A PREFACE BY PROFESSOR

J.

H.

Ph. D.
College,

Leeds

VAN

'T

HOFF

AND

49 FIGURES IN THE TEXT

AMSTERDAM
FREDERIK MULLER

LONDON
WILLIAMS & NORGATE

& Co
I

896

Printed by the Amst. Boek- en Steendrukkerij v/h. Ellerman,

Harms &

Co.

PREFACE

The

,,

I.

Etudes de Dynamique Chimique" being out of print, the

new

desirability of a

however,

This,

at

represented,

was suggested by the

edition

gave

rise to a difficult

publisher.

the 'Etudes'
'

problem

the time of their publication, a certain stage in

chemical thinking, beyond which, doubtless, everyone

my

advanced.

To

away from the


while

to

introduce
original

change

E. COHEN'S

now

many changes would, however, take


work its desired documentary character,

nothing

would

making the contents acceptable


Dr.

is

proposal

to

be

to

contribute

nothing to

to the public.
revise

the

'Etudes' in the form

'

of the old laboratory programme, in carrying out which he has

very
so,

successfully

may

this

assisted,

work serve

came

just at the right

moment, and

as a suitable record of our little labora-

tory history.

Stuhlingen, October 1895.


J.

H. VAN

'T

HOFF.

PREFACE

The

first

edition

years ago under the

then

Since
to

be

known

many

uncommonly
facts,

of

this

title

II.

work was published about twelve

'Etudes de

Dynamique ChimiqueS

of the views put forward in

on

fruitful,

the

one hand

in

by suggesting new

on

the

other,

of

the

present

have proved

it

explaining

directions for

investigation.

The

object

reproduce

the original book,

German

been

memoir

homogeneous whole

as a

is

not merely to

but also to present the researches

which have

engendered

edition

by
;

it

together

in doing this,

with the parent

much which has

not hitherto been published has been included.

Amsterdam, October 1895.

ERNST COHEN.

NOTE BY THE TRANSLATOR.

The appearance of a
'Etudes

classical

wished-for

de

revised edition of Professor VAN

Dynamique Chimique' seemed


1

opportunity

of introducing

to

it

'T

HOFF'S

to provide a

a wider

circle of

English readers by means of a translation; the paucity of works


our

in

language

dealing

with the subject made this the more

desirable.

The

simplicity

change and

and

affinity

of the treatment of chemical

originality

make the book

of the greatest value to the

student seeking clear views on the fundamental problems of our

makes

science, whilst the fertility in ideas

it

uncommonly suggestive

to the chemist already familiar with the outlines of the subject.

The nature of the contents


preceding prefaratory notes.
the

sense

of

the

original,

is

The

sufficiently

indicated in the

translation adheres closely to

occasional notes having been added

for the sake of greater clearness.


I

am

greatly indebted to

my

friend A. C.

WEIGHT M.

A., B. Sc.

for his kindness in reading the revised proofs.

May

1896.

THOS. EWAN.

UNIVERSITY"
C*7

CONTENTS,
THE COURSE OF CHEMICAL CHANGE.
First Part.

THE FORMAL CHEMICAL

REACTION.
Page.

I.

The monomolecular

reaction.

Decomposition of arsenic
1

hydride
II.

III.

IV.

The bimolecular
,,

reaction.

Hydrolysis

Effect of molecular volume

,,

The polymolecular
Simplicity of

reactions.

many

I.

Chapter
Effect of the

.........

I.

medium on

the velocity of reaction. Action

26

II.

The order of magnitude of the disturbing

The nature
a.

The

b.

The

30

actions in

gaseous systems
The nature of the disturbing actions in gaseous systems.
Action of the walls of the vessel. Formation of cyamelide and of water; decomposition of phosphine
.,

III.

Disturbing actions in gaseous systems.

II.

25

Disturbing actions in liquids.

Influence of pressure on the velocity of reaction

Chapter

15

DISTURBING ACTIONS.

of contact
II.

reaction. Slow oxidation of phosphine,

Second Part.

I.

...

of esters

31

43

of the disturbing actions in gaseous systems.

50

rate of oxidation of phosphine


rate

of oxidation

and aldehyde

of phosphorus,

sulphur,

61

CONTENTS.

II

Page.

Chapter
I.

II.

eliminating the disturbing actions. Form


dimensions of the apparatus. Use of a solvent.

Methods
and

Elimination of the disturbing actions

III.

of

Third Part.
I.

APPLICATIONS.

A.

Method

in

which the
99

Determination of the number of molecules which take


part in a chemical reaction.

B.

Method

in

which the

volume varies

-.
Polymerisation of cyanic acid.
The action of stannous chloride mi ferric chloride

.2.

3.

of

mixtures.

Decomposition
and iso-dibromsuccinic acids

Recognition
succinic,

IV.

101

105

Action of bromine on fumaric acid

1.

III.

91

Determination of the number of molecules which take


part in a chemical reaction.
volume remains constant

II.

86

Moistening the walls of the vessel


The first period of chemical change. Chemical induction

of

.107
.

110

dibrom-

113

Comparison of the velocities of different reactions.


a.

Hydrolysis of esters by bases

b.

esters by acids

Hydrolysis of

115

....

.116

THE INFLUENCE OF TEMPERATURE ON


CHEMICAL CHANGE.
First Part.

THE RELATION BETWEEN THE

VELOCITY CONSTANT K

AND THE TEMPERATURE.

a.

Application of thermodynamics

b.

Experimental treatment of the subject


1.

122
.

...

.127

Influence of the temperature on the rate of decomposition of dibromsuccinic acid.


127
.

CONTENTS.

Ill

Page.
-.

Influence of the temperature on the rate of the reaction

between sodiumchloracetate and caustic soda

.129

:l.

Influence of the temperature on the rate of change of

4.

Influence of the temperature on the rate of hydrolysis

5.

Influence

130

chloracetic acid in aqueous solution

of ethyl acetate by caustic soda

reaction

130

temperature on the velocity of the


between potassium chlorate and ferrous

of

the

132

sulphate in presence of sulphuric acid


<).

Influence of the temperature on the rate of hydrolysis

7.

Influence of the temperature on the inversion of cane

8.

Influence

9.

Influence of the temperature on the formation of nitriles

of ethyl acetate by caustic soda

133

133

sugar
of the temperature on the action of sodium

133

ethylate on methyl iodide

from syn-aldoxime

acetates

and on the change of

133

the latter into the anti-modifications


10.

Influence of the temperature on the rate of decomposition

of the hydrides of arsenic and phosphorus.

Second Part.

THE TEMPERATURE

OF IGNITION

134

.136

CHEMICAL EQUILIBRIUM.
First Part. THE
I.

Homogeneous systems.
a.

b.

II.

THREE FORMS OF EQUILIBRIUM.

At constant temperature
The temperature is variable
Application of thermodynamics

148

Applications

150

Heterogeneous systems
Cases

143
148

i/tcextif/ated

155

....156

UN

CONTENTS.

IV

Page.
III.

1.

Condensed systems

163

2.

Cases investigated

167

The

a.

transition

of polymorphous

temperature

bodies
b.

The

c.

The

transition temperature
water of crystallisation

transition

temperature

168
the

in

.and decomposition of double salts

The

d.

transition

temperature

formation
.

.169

cases of double

in

173

decomposition

The

e.

transition

pounds
Solubility and

3.

67

of salts containing

temperature

of

com-

isomeric

173
vapour

pressure

at

the transition

174

temperature

between the transition temperature of a


hydrated salt and the vapour pressures of the

Relation

4.

salt

and of solutions of

179

it

Methods of determining the transition temperature 180

5.

The

dilatometric method
The thermometric method
The crystallisation method
The identity methods

a.
b.
c.

d.

181
]

186
.

Determination of solubility
Determination of vapour pressure.

os,.

(B.

1.

Vapour pressures of

2.

Pressure of dissociation

The

7.

84

186

186

187

solutions

188

solution pressure methods.

188

1.

Solutions

2.

Solution pressure of dissociation

.192

Electrical methods.

2.

method with both

1.

Electrical

2.

meta- stable phases


193
Electrical method with stable and without
meta-stable phases

Further methods

....

stable

and

198

203

CONTENTS.

Page.

Second

THE THREE FORMS

part.

OF PHYSICAL EQUILIBRIUM.

I.

Homogeneous systems

205

II.

Heterogeneous systems
Condensed systems

205

III.

Third par

t.

DIAGRAM

ON EQUILIBRIUM.

210

OF THE

DETERMINATION

INFLUENCE
OF

THE

OF

TEMPERATURE

TRANSITION POINT OF

212

SULPHUR

Fourth

DISPLACEMENT

part.

OF

EQUILIBRIUM

WITH THE

217

TEMPERATURE. PRINCIPLE OF MOBILE EQUILIBRIUM


I.

The

principle of mobile equilibrium applied to hetero-

geneous systems.
a.

Physical

The

systems.

217
Evaporation and condensation
Chemical equilibrium in heterogeneous systems. 218

b.

II.

equilibrium in heterogeneous

principle

of mobile

equilibrium

applied to con-

densed systems.
Physical equilibrium in condensed systems. Fusion

a.

and

219

solidification

Chemical equilibrium in condensed systems.

b.

In-

219

compatible systems
III.

The

principle of mobile equilibrium applied to

homo222

geneous systems

AFFINITY.

I.

II.

The comparison of chemical affinities


Measurement of affinity. The magnitude of the
which

III.

the water of crystallisation in


Determination of the work done by affinity
retains

229
affinity

salts.

....

230

235

CONTENTS.

VI

Page.

IV.

Applications.

Work

1.

done by

241

on the transition point. 242

Influence

3.

Calculation of the transition point.

b.

The

The

pressure

allotropic modifications of sulphur

The transformation of a mixture

of

ammonium

laevo-

into sodium

and ammonium racemates

and

248

sodium

dextro-tartrates

1.

work performed by a chemical change.


General considerations

2.

Thermodynamics of the transition

3.

Equilibrium- constant and electromotive force

250

electrical

Appendix ...

Name

of

Diagram

2.

a.

V.

affinity at absolute zero.

work done

of the

index

Subject index

cell.

251
.

254
267

274
276
279

THE COURSE OF CHEMICAL CHANGE.


FIRST PART.

THE NORMAL CHEMICAL REACTION.


THE MONOMOLECULAR REACTION.

I.

Decomposition of Arsenic Hydride.

The

most

chemical

simple

change

is

that

which

can

be

accomplished within a single molecule, a change for the accomplishment of which the mutual action of several molecules is not
requisite.

Whether

it^be a question of isomeric change, or of decompos-

the process

ition,

On

these

is

subject to the

grounds we

same law.

will call the chemical reaction of this

kind the monomolecular reaction.

Experiment will show us that in this case there is proportionality between the quantity of substance still decomposable, and
the quantity which undergoes decomposition in each instant,
which

may

be represented by the following equation,

where C
t,

is the concentration, (quantity in unit volume),


the time, and k a constant \ which we will call the velocity

constant.
1

ture,

It

is

of course assumed

here that

the reaction takes place at constant temperait may be neglected.

and consequently the heat evolved or absorbed by

THE MONOMOLECULAR REACTION.

The decomposition which was


equation

is

we assume
with

in

order to test this

the following;

As
If

studied

H =
3

As

3 H.

that the arsenic hydride decomposes in accord-

simple equation just given \ it will be easy,


by determining the pressure of the decomposing gas (at constant
volume), to calculate the undecomposed part of it in unit volume.

ance

Let

the

and

be

the

concentration of the arsenic hydride,

and the total pressure at the beginning,

C t and P t the values

and

after a partial decomposition.

Then

P
*t

p +
n

-t

"

t).

or

Ct

The apparatus

for

(3

(1)

making the determinations of the pressure

will be fully described later,


(p. 41).

The

results obtained are given in the


following table.

Time

in hours
t

THE MONOMOLECULAH REACTION.

We

find

log
the

Eliminating
(1),

we

get:

the

values
third

constant.

constant

integration

C
-

--

log>

in

kt

by means of equation

These

of

1
--

=
-

-2P

3P

calculated, and are set

k have been

column

log*
J

G;

down

of the table; [their constancy shows that

the requirements of the differential equation are satisfied.


A further example of a monomolecular reaction is the decomposition of phosphine,

From
clusion,

the preceding

which

will be considered later.

we may draw

the following general con-

which however contains nothing unexpected

in the

case

of a monomolecular reaction.

The quantity decomposed in unit time is independent of the


volume of the decomposing substance.
This proposition may also be proved in the following way:
Suppose that two equal quantities Q occupy at the beginning
of two experiments two different volumes Vi and V 2 it is easy
,

to see that the corresponding quantities

and

2,

which remain

undecomposed at the end of the same interval of time


be the same in both cases.
Applying the equation
kt

we

log

obtain

__
kt

log

-^
AI

__

- ^g

from which

-=r-

AI

-=-,

log

2-

-J
A2

or Xi

= X

lo S

2.

IA

t,

will

THE BIMOLECULAR REACTION.

II.

Hydrolysis of Esters.

We

will

molecules

call

in

change

which the interaction of several

required, poly molecular.

is

The most simple

case of this sort

the reaction between two

is

molecules, or the bimolecular reaction.

we

If

G!

call

C2

and

the concentrations of the two reacting substances


decrease of concentration which the substances

the

undergo in each instant, will be proportional to the concentrations


of both of them, that is

=
at

where

kj

CJL

^=

C 2 and

at

k2

C2

the time, and ki and k 2 are constants.

is

As the

unit

are considering,

of a body

of concentration

molecular weight of

it,

we

will choose the

in kilograms in a cubic metre.

If

we

for example, the hydrolysis of ethyl acetate by

the concentration is unity when 40 kgrms of caustic


jaaustic soda,
soda and 88 kgrms of the ester are present in a cubic metre.

As will be seen in what follows, the accuracy of the equations


has been confirmed by experiment the experiments on this point
l
were carried ont by L. T. REICHER.
;

The

hydrolysis

acetate

of ethyl

by

caustic soda,

represented

by the equation

NaOH
was

H-

C aH B OOCH 8

= CH COONa +
3

studied.

WARDER

had already found that

at the ordinary

in

takes place

,
-

dt
LIES. Ann. 228, 257, 1885.
Berichte. 14, 1361, 1881.

its

case of verifying the equation

this

d Ci

reaction

this

temperature with a velocity which allows of

course being followed.


It is thus a question

C 2 H 5 OH,

p
K p
\Ji L 2
i

HYDROLYSIS OF ESTEES.

where Ci

the

is

the ester,

caustic

soda,

now an aqueous

of base and ester, which

solution

are acting on each other at a given temperature;

moment during
can

be

C% that of

the time, and k some constant.

Consider

concentration of the

:>

the

concentration of the ester,

the reaction

is

its

We

the base be

if

after

have then,

k Ci

-~

d_Ci

this the

Substituting this value in the original equation,

from

C w be determined

concentratration,

complete.

be calculated

may

2,

an acid

with

titration

by

used in excess and

the concentration of the base, C 1?

reaction

determined

then at any

(Ci

we

obtain

_ CA

from which by integration

log
^
^w

we make two

If

time

~
VI

determinations,

them

between

intervening

kt

constant.

v^a>

is

t,

and C t

Ci

say

we

find,

and

if

the

eliminating the

constant of integration;

or

introducing

common
k

C t (d

1
7
t

p
Ow

2.3025
-

As the apparatus used


In

order

to

into

water

the

supply

Log

will

CCQ)
-

in

^
d

(Ci

(C t

p-ri
^v>)
place

of the Naperian,

Ceo)

Co)'

be referred to again,

it

is

fully

1).

obtain a constant temperature the essential part

of the apparatus, A,

G;

p-7p
bi (U

logarithms

described here. (Fig.

log

first
is

is

placed within two glass cylinders

of these

conducted

F and

water at a high pressure from the


by two fine jets from the tubes L

THE BIMOLECULAR REACTION.

und Ly

by means of the

uniform temperature
This temperature

which allows

The second

currents

is

maintained.

is

determined

/io

vessel

the

G,

contains

the

is

glass

ice

water,

or

warm

water,

1.

is

too high

of the ester during the reaction the

placed in the glass vessel A,


tap C,

way

by means of a thermometer

of the water supply

temperature

To prevent evaporation
liquid

this

of a degree to be read.

Fig.

according as
or too low.

in

produced

and which

it

which may be closed by

completely

fills;

liquid

may

be

APPARATUS.

removed from

the titrations,

for

by means of mercury,

which

by displacing

allowed

is

it

run

to

through C
from the

in

funnel B.

The manipulation
and drawing

A
the

the experiments~requires the cooperation

of

two observers, and

of

consists of three operations

filling,

mixing,

off samples.

quantity of the aqueous solution of the ester

is first

placed in

when the latter is subsequently wholly


addition
of
the
alkaline solution, a small excess of
the
by

apparatus, such that

filled

alkali

be

shall

It

present.

therefore necessary to

is

know

to

begin with, the concentrations of the solutions of ester and soda,

and also the capacity of A.


The apparatus is then filled with the solution of
in position as

shown

(protected from the carbon dioxide of the

placed
base,,

introduced graduthat the solutions of ester and

ally

alkali

is

the

the

needed for the

way

described,

temperature

of

when

so that

the

During the time

the temperature in

filling,

liquid

desired; this will be indicated

In

air),

through H in such a way


form separate layers over each other.

which
in

ester,

and the solution of the

in the figure,

in

F is regulated

the apparatus

it

is

about

is

quite full

0.4 below

that

by the thermometer D.

order to mix the liquids thus introduced, some mercury

is

allowed to flow through B into A, the tap C closed, the apparatus removed from the cylinder, and shaken uniformly several
times so that the mercury effects the mixture of the liquids; if
necessary the temperature is then raised to the desired point by

warming with the hand. The apparatus

is

now

placed in

its

original position and the real experiment may be begun as soon as


the temperature of the water in the cylinder F has reached the

desired point.

Before
ding

to

drawing of a sample, a volume of mercury corresponthe part of the apparatus which projects above the

water in F,
tap

this

is

poured in through the funnel B, on opening the

displaces

the

liquid

in that part of the apparatus

which possibly does not possess the correct temperature.


the mercury has fallen to the

and 100

cc.

mark E,

of mercury poured into B.

the tap

is

When

closed again,

The one observer then

THE BIMOLECULAR REACTION.

measured

of sulphuric acid of known


quantity, R,
strength under the opening K, and quickly opens the tap C completely; the time is noted by the second observer on a chrono-

brings

meter

indicating

has

mercury

C the

closing

reached,

seconds,

fallen
last

very
small

when

also

nearly

repeated

the

hydrolysis

is

the

to the

moment
mark E.

at

which the

By

partially

quantity flows out slowly until E


closed completely. This manipulation

the tap is
each time
a sample

sulphuric acid employed


present,

and

amply

is

drawn

off,

and since

is

is

the

sufficient to neutralise the alkali

taking place in 100

cc.

of the liquid

is

few seconds (about 9).


time allows, the excess of sulphuric acid is at once titrated
with baryta water of known strength using phenol-phthalem
as indicator (or rosolic acid in experiments with ammonia).
stopped at a given time, in the space of a
If

Samples are drawn off at intervals of some minutes until only


about 100 cc. of the mixture are left in the apparatus, which
serve

for

be

the

determination of the final

titre after

the reaction

24 hours).
regarded
complete (viz.
obvious that after the last sample has been taken the temperature need no longer be regulated.

may

as

after

at

least

It is

The

results obtained are contained in the


following table

Time

in minutes.

l
:

CALCULATION OF RESULTS.

the quotient, the logarithm of which occurs,

T! (T t

cubic metre,

of

- Tw

)'

of C (the concentrations, in kgrm. mols. per


of the free caustic soda) are proportional to those
quantities of free caustic soda expressed in cc. of

values

the

since

be written thus

rp

/rp

may

(the

the baryta solution employed).


Co, is the final concentration (in

of the

caustic

kgrm. mols. per cubic metre)


the mixture in which the reaction has

soda in

taken place, the concentration being unity


are present in each cubic metre.
If the baryta solution is

times normal

100

These

values
their

of

practical

are

100

T w Nt

table \

we have

therefore

2.3025

NaOH

C--T,
The value of k becomes

when 40 kgrms

entered

identity

(T!

T! (T t

in

TM)
T)'

the third column

of the

shows that the requirements of

the original differential equation are satisfied.

The equation

leads

us

TH.

k Cl C,

to the conclusion, that each of the bodies


taking part

in the reaction

L.

f=

has an equal influence on its velocity.


2
has confirmed this experimentally, and has

REICHER

shown that the same value of the constant k

is obtained, whether
excess of caustic soda, or of the ester, be employed.
In this case also, the hydrolysis of ethyl acetate
caustic

by

soda was studied.

LIEB. Ann. 238, 276, 1887.

THE BIMOLECULAR REACTION.

10

The apparatus used is shown in fig.


The most important condition to be
ments,

is

2.

fulfilled in these experi-

that the free soda contained in the mixture, must not

be exposed to the

air either during its introafterwards within the apparatus

or

duction,
itself.

The apparatus

X)-

consists of

two

fairly strong

and Q, which communicate by a


thick-walled tube, and which may be closed
vessels,

above by taps R and S. At U and T there


The volume from R to
are two marks.

mark U

the

100.2

was

125.7 cc v

from

to

cc.

In order to find the final


after

being

exactly

carefully

filled

from

titre,

cleaned
to

the apparatus,

and

dried,

with the alkaline

solution of known strength through the tube

the piece of

is

V;

tube V R is then cleaned and filled

with mercury, and finally, through S, so much


more of this metal introduced that in all 10 cc.
rig,

2.

of
of the
is

now

it

have been employed. The exit tube K


1) which has already been described,

apparatus A (fig.
united to V by a

short india rubber tube, and with the

help of mercury which is poured into the funnel B, the mixture


of caustic soda and ester is allowed to flow into P so slowly
that

it

this

can

remains as a separate layer over the solution of soda ;


be plainly seen by the sharp boundary between the

two layers.

The apparatus being

filled

in

this

way

to the

mark

T, the

taps are closed, and the liquids mixed by transferring the mercury
alternately from one vessel to the other 100 times, shaking

vigorously meanwhile.

The

contents are then allowed to stand

24 hours, after which the titration is proceeded with.


done by first pouring in some mercury above S, and
a tube for drawing off the liquid at V;
is then

for at least

This

is

attaching
connected
out to the

to

mark

gas holder containing air and the liquid driven


T, after which (from T to U) 100.2 cc. of the

11

EXCESS OF BASE OR ESTER.

mixture

allowed

are

100.2

second

ratus

The

flow

cc.

way

measured quantity of sul-

into a

This

in excess.

of liquid

is

running mercury into

after

T, in the

to

which must be

phuric acid

now

is

then titrated back.

driven out of the appa-

through S up to the mark

just described.

results obtained with this apparatus are

contained in the

following table:

(Temperature 15. 8).


a.

Experiments with excess

Time

in minutes,
t

of caustic soda.

12

THE BIMOLECULAK KEACTION.

T w must

of ester was used, the sign of

k (page

for

be changed in the formula

9) so that in table b

2.

3025X100
TCO

At the present time

TX (T t

og

Nt

(T x

a considerable

TM)
Tcy

number of researches on

this subject are in existence; as further

changes

+
+

examples of bimolecular
and that

the action of acids on acetamide (OSTWALD) \

2
are to be mentioned.
of bases on lactones studied by P. HENEY
A simplification which may be introduced by using the react,

ing substances in equivalent quantities will now be pointed out.


In this special case, the ratio of the concentrations of the substances
units

in

not

change during the reaction; by choosing the


a suitable way, only one single concentration need be

does

taken into account.


This concentration, which refers to both bodies, will be called
the concentration of the system.
In place of the equations

we may

^=

k, Cx

C 2 and

~=

k, C,

C2

write the following,

d C

k C2

dt

being the concentration of the system.


Integrating

we

obtain

p\j

kt

constant

(1)

Considering for example the hydrolysis of an ester by caustic


soda, (in equivalent quantities), the concentration of the system is
proportional to the titre of the alkali in the solution,

n
C
t

.
-

Cx

therefore

|-

where GX and T! are the original values of the concentration and


titre, Ct and T t their values after a partial decomposition.
1

Journ. prakt. Chem.

Zeit. phys.

Chem.

(2),

27, 1, 1883.

10, 96, 1892.

13

INFLUENCE OF VOLUME.

Eliminating by means of this equation the constant of integration

we

in equation (1),

On comparing
for the

get

(L

\C t

this

IV

'

d/

JL

"id

Tt

expression with that which was obtained

monomolecular reaction, (page

3),

3T.-2TY
l

a great difference

While

in

the

is

apparent.

case of a monomolecular reaction the value of

k depends exclusively on the choice of the unit of time


the case of the bimolecular reaction

its

value

is

(t),

in

also a function

of the unit of concentration (C).

The following statement indicates the difference


mono- and bi-molecular reactions -

of the

in the courses

In a bimolecular reaction

the quantity decomposed depends on


volume of the decomposing system.
This proposition is obvious, when one remembers that the bimole-

the

cular

reaction

differs

from the monomolecular,

in the fact that

in the former, the encounter of the reacting molecules must occur.


further simplification takes place if in a bimolecular reaction

one of the reacting bodies


is
then
concentration, C 2

is

reaction,

C2

present in great excess. For since

its

perceptibly changed during the

not

in the equation

d C,

IT

kl Cl

to be considered as a constant, so that

is

that

is

the

process

takes

in

place

the^same way as a mono-

molecular reaction.
Processes of this kind have been examined in great number.
1

This expression corresponds in every way to that obtained on page


3

3,

2 Ft

WITTWKR,
WILHELMI, Ostwald's Klassiker der exacten Wissenschaften, No. 29.
HARCOURT and ESSON, Phil. Trans. (1866) 193; (1867)
Pogg. Ann. 94, 593 (1855).
117. __ OSTWALD, Journ. prakt. Chem. 28, 449 (1883); 29. 385; 31.307.

14

THE BIMOLECULAR REACTION.

has studied the action of a large excess of water on


monochloracetic acid at 100, and found that it takes place

BUCHANAN

according to the following equation:

C2

Cl

As may be
as

if

In
of

+ H

C 2 H,

acid

litre

per

was heated

sealed tubes, (of 15 cc. capacity),

ing

water.

and

the

The

titre

Cl.

because the concentration of the

may be regarded as constant.


order to confirm this, a solution

chloracetic

+H

the reaction in this case goes forward

foreseen,

were monomolecular,

it

water

reaction

containing

grams

for a definite time in

which were suspended

was then stopped by sudden

in boil-

cooling,

of the acid in the solution determined by means

of N/io ammonia.

Ci
the

being the concentration and titre respectively at


after partial
beginning, and C t and T t the same quantities

and

TI

decomposition,

we have
ct

the relationship

2 Tx

c,

Tl

The following
Time

in hours,
t

60

table contains the experimental results.

15

THE BIMOLECULAR REACTION.

III.

Effect of molecular volume.

In

order to determine

process which

C2

is

Cl

SCHWAB investigated the following

this,

analogous to a

Na

NaOH

hydrolysis,

C2

Na

Assuming that the change takes place

-f-

NaCl.

in accordance with the

above chemical equation, the quantity


of the undecomposed compound in unit

'^^^s^

volume,
of

may

the

be determined by means
of

titre

which

solution

the
is

alkali

the

in

the

undergoing

change.
If the sodium chloracetate and the
caustic soda be used in molecular
pro-

portions, the simplification before

tioned

We

men-

may be employed.
have then only to take into

consideration the concentration of the

system, which refers both to the sodium


F ig.

chloracetate, and to the caustic soda.

3.

The experiments were


apparatus shown in fig. 3.

made with the


The large flask contained
soda

caustic
2

solution

at a

NaOH)
B in which
racetic

acid

(containing

temperature of
there
3

were

could

be

553 9
.

initially

100;

1.9935

cc.

of a

grams

the small flask

2.3542 grams of chloshattered

at

given

moment.
Since

the molecular ratio between the


quantity

of the acid and of the soda was

of sodium

chloracetate

and

See also

Prepared from sodium amalgam.

1.3879

for saturation,

BUCHANAN,

caustic

2,

a mixture

soda in the

Berichte. 4. 863, 1871.

of this acid required 18.18 cc. of 0.8077


the calculated quantity being 18.2 cc.

grams

F)'s- 4

caustic soda solution

THE BIMOLECULAR REACTION.

16
desired

proportions

is

produced by bringing the two liquids to-

gether.
After a suitable interval the titre of 17.75
cc.

of the liquid

ing

way

was determined

The

liquid

in the follow-

was expelled

at

C by

blowing, and poured through a funnel into


the tube D, which was surrounded by ice in
order to stop the reaction.

The funnel was then removed and


quid

transferred to the

titration

was

pipette E.

The
lowing

Time in minutes,
t

vessel

to take place

(fig.

in

the

li-

which the

by means of the

5).

results obtained are given in the foltable.

ACTION OF SODA ON CHLORACETIC ACID.

It is
is

17

obvious that the course of the reaction here investigated


The values of k obtained at the beginning of

not normal.

the reaction,

refer

an aqueous solution, whilst those

to

fact

in

which were obtained

by the action of the sodium chloride formed during the reaction.


SCHWAB has avoided this difficulty by studying the decomposition in very dilute aqueous solution; with this object he used
later are affected

solutions of different initial concentrations.

Chloracetic acid

C2

in the ratio

was mixed with


Cl

caustic soda in dilute solution

Na OH;

formation of sodium

the

glycolate being prevented by cooling.


From this solution five others were prepared which contained
16, 8, 4, and 2 grams of chloracetic acid per
These solutions were brought into glass tubes which were
then sealed. Six tubes of each series were kept for a certain

respectively 32,
litre.

time in boiling water, after which the titre of their contents was
by means of N/ 2 o sulphuric acid. From this the

determined

quantity undecomposed was calculated.

The following mean values of k


Value of

were, found in this way.

Concentration.

k.

0.2

0.18

deviation

concealed

in

0.163

0.099

0.14

0.059

0.128

0.038

0.131

0.015

comes

to

these

in

light

the experiments described on p. 16,

nevertheless of a fundamental character.


icith

decreasing

irhich

We

it

concentration

to

see

and which

"is

The value of k decreases

certain

limit

(0.13),

after

that here the equation for the bimole-

accordingly,

kt

const,

only true for small concentrations.


1

was

remains constant.

cular reaction,

is

numbers which

Inaugural Dissertation, Amsterdam 18S8.

THE BIMOLECULAR REACTION,

18

The agreement between the requirements


the numbers found experimentally

is

of the formula and

sufficiently

good for concen-

trations smaller than 0.038.

This

may be

concentration

called

the gaseous

concentration,

removed from that which the mixture


because it
of sodium chloracetate and caustic soda would have at normal
is not very far

- 0.023.
viz
temperature and pressure in the gaseous condition
of
a
series
of
This experimental result was the origin
experi:

ments on the course of the decomposition


(initial

concentration

0.04984);

great care in sealed tubes.


The following are the results.

Time

in minutes,
t

they

in a very

were

weak

carried

solution

out with

THE POLYMOLECULAR EEACTION.

19

space occupied by the reacting bodies vanishes in comparison


with the whole volume, on the other hand the deviation changes

way which might

in the

be expected, k increasing with the con-

centration.

THE POLYMOLECULAR REACTION.

IV.

We may
tial

now go

more

for

equations

a step further and write

down the differenIf we consider a

complicated cases.
to the mutual action of n mole-

which may be ascribed

reaction

we have

cules,

^=
where

k,

C 1? C 2

d
.

(V
Cn

.C n

reacting on each other, k x

When

the

which they

the

are

^=

kn

concentrations
.

C,

the

C2

.C n

of the substances

k n are constants, and

bodies are

reacting
take part in

etc.;

t is

the time.

present in the proportions in

reaction,

the

equations

may

be

had

in

simplified to one single expression,

dC

where C

the concentration of the system.

is

Integrating this,

we

find

C
in

which

the

value

of

is

(n

+
1)

constant,

times that which

it

the differential equation.

would be interesting if it were possible to realise the different cases which follow from this equation, that is if it were
It

possible to study the course of a tri- (n

3),

or quadri- (n

= 4),

molecular reaction.
It
1

is

is

not

difficult

to find chemical equations

supposed to be constant.

which represent

20

THE POLYMOLECULAR EEACTION.

three,

four,

more molecules

or

+ 6FeO

KC10,
on

this

=:

example

*,

KC1

3 Fe 2 0,.

however, shown

have,

subject

as for

interacting;

Pi

by HOOD

or the case investigated

Researches

H =

as

that the

greater number of such equations give an entirely false idea of


the mechanism of the reactions, only expressing the quantitative
aspect of them.

This

mechanism

is

generally very simple, in almost


it

mono-

is

or

all

cases

bi molecular,

rarely trimolecular.

So for example the decomof

position

phosphorus

(or

takes place

arsenic)

hydride

as if

were monomolecular,

it

that is according to the equation,

PH = P

Ha

4-

whilst Hood's reaction appears

be bimolecular.

to

According to the researches


2
of J. VAN DE STADT
which
,

be

will

slow

oxidation

under

may,

stances,

course,
Fig.

described below,
of

phosphine
circum-

certain

follow a very simple


namely that of a bi-

6.

molecular reaction.

He
may

the

found that the following are the principal changes which


occur during this slow oxidation:

Phil.

Zeit. phys.

Mag,

(1)

(2)

P
P

(3)

(5).

H +
H +
3

4-

= H

=
=
P

P2
2

H P
+ H

3
2

20, 323, 1885.

Chem. 12, 322. 1893. Inaugural Dissertation. Amsterdam, 1893.

21

OXIDATION OF PHOSPHINE.

Equation (1) represents the change which occurs


combustion of phosphine.

in the ordinary

of the apparatus shown in figure 6, changes (2) or


be brought about at will, and so could be separately

By means
(3) could

metaphosphorous acid which was previously unknown


was prepared in the course of this investigation.

studied;

Oxidation

The
is

to

principal condition

be excluded;

to

phosphorous acid.

which must be

fulfilled if reaction (1)

that the gases must be brought together in

is

a suitably dilute condition and as dry as possible

oxidation

can

only in this

The

flask

c closed;

instantaneous

insured, and excess of one or other avoided,

be

way

e is

evacuated at d by means of the air pump, and


connected to the phosphine, f to the oxygen gasis

holder, while p acts as a gas pipette the contents of which may


be transferred to
by turning a. The tap a is so arranged
that V may be placed in communication with the manometer

with

or

the

p;

pipette

the tap b

allows the apparatus to be

placed in communication with e or with f, or to be closed entirely.


In the dark room the gas required is admitted, one pipette full
at a time, into the flask until its admission fails to produce

further

it

to

be

in excess.

any

The

present
luminosity, showing
following results were obtained, the + sign indicates that luminosity was observed after admission of the gas;

P
1

+
+

+
+

1+1

13 X-

26

The manometer remained

mm.

The

39
stationary during these 65 admissions

although one pipette

of gas,
0.7

full

alone produced a pressure of

in the flask.

flask

was covered with a coating which became

solid

and

THE POLYMOLECULAR REACTION.

22

on standing over night, and then melted

crystalline

the

gave

of

reactions

phosphorous

(melting point 70).

acid,

having taken place

to the change

points therefore

Everything

and

63

at

entirely according to equation (2).

Oxidation accompanied by liberation of hydrogen.


the experiment just described the admission of the gas
be brought about slowly by opening the tap a gradually,
a greenish blue flame, which is frequently intermittent and which
in

If

to

a
daylight only betrays its existence by the formation of
in
which
flame
acid
the
of
cloud, is seen instead
phosphorous

in

the

dark

almost blinding and often accompanied by a slight

is

explosion.

The
one;

reaction accompanying

(fig.

PH
+
+
+

1
1

1
1
1

is

experiment

quantitative

already described

it

6)

quite different

carried

from the former

in

the

apparatus

gave the following result;


2

+ 1+ 1+ 1-

The manometer now

1
1
1

indicates

an

ponding to an increase of pressure of


pipette full

out

gave 0.7

+
+
+

+
+
+

1
1
1

evolution of gas,

53/4

mm., that

nearly 9 pipettes

mm.,

full.

is,

corres-

since one

Therefore the

a third
gases react together in equal volumes, and leave behind
them.
A
to
either
of
volume
in
substance
very
equal
gaseous

may be

obtained by adding oxygen


carefully to phosphine in excess; the addition of 17 consecutive
pipettes full of oxygen, each of which produced a blue flame on
accurate confirmation of this

entering

the

at 281/4

mm.

left

flask,

the level of the

manometer unchanged

Formation of metaphosphorous

acid.

Although the gas produced in the last experiments was found


to be hydrogen, and the equation for the change was therefore
probably

PH 3 +

= H

+ HP0 2

the

compound

HP0

2,

the

23

OXIDATION OF PHOSPHINE.

formation

which

of

assumed, could not be isolated with the

is

experimental arrangements described.


In

of

place

brown

a yellow or

it

was partly moist and soluble

in

was formed, which


water, and in short was evidently
deposit

non-homogeneous product of secondary reactions.

good result was however at once obtained when the two


gases were mixed by diffusion instead of by allowing them to
flow into each other.
They must also be very dilute; at a

when

pressure of 50 mm., even


the

25

action

is

mm.

/2

are suitable.

these circumstances, the flask

with

the

25i-'2

mm.;

pump, and

air

the gases diffuse into each other

and no pressures greater than about


To obtain the necessary quantity under

too violent,

the air

V was allowed to remain in connexion

with phosphine at a pressure of


was filled with oxygen at 251/2 mm.,

filled

pump

and the tap a opened.

The manometer

indicated the gradual combination

by a decrease

of pressure.

This was

after 2 hours 3

21

This

decrease

volumes
0.69

1,

the

of

91/2

the

corresponds to

and

flask

decrease

mm.

11

24

,,

1/3

of

the

desired change, for as the

pump were in the ratio


mm. would be

air

pressure of about 101/2

in

anticipated.

The

flask

feathery

had

crystals

phosphorous

70,
In

H P0
3

in the

acid;
at

meantime become covered with

which

were

at

once

they did not melt at

seen

to

glittering,

differ

80. (H 3 P0 3

from

melts at

17).

their behaviour with aqueous vapour was very


on admitting a very little water through a, the
of crystals first liquefied, and then after a few minutes

addition,

characteristic

coating

solidified entirely,

forming long needles, which plainly consisted

of phosphorous acid,

HP0 + H
2

- H P0
3

24

THE POLYMOLECULAE KEACTION.

subsequently these again liquefied, and the aqueous solution now


formed showed the well known reaction of phosphorous acid

with silver nitrate.

The change

The question

ivhich occurs

as to

during slow oxidation.

which of the above changes occurs during


what extent it

the slow oxidation of phosphorus hydride, and to


occurs,

still

11.89

remained to be answered.
6.69 cc. of oxygen were mixed

phosphine and
eudiometer and

of

cc.

heated in a water bath to 50


together in a
until the pressure no longer decreased.
The volume of gas remaining, 10.3 cc., was free from oxygen,

and contained 6.2


11.89

6.2

cc.

phosphine and 4.1 cc. hydrogen.


P 3 and 6.69 cc. 2 had thus
cc.

5.69

disappeared forming 4.1 cc. H 2


Assuming that the latter had
been formed in the same way as before, that is from 4.1 cc. P 3
we have 5.69
and 4.1 cc.
4.1
and
1.59 cc. P
2
3
.

6.69

2.59

4.1

cc.

which have reacted together in some


form phosphorous acid as their volumes
2

other way, probably to


are approximately in the ratio

2:3.

In the slow oxidation, therefore,

we

are dealing with the two

processes

= JB P0 ....
PH + 3
PH f O = HP0 + H
2

and

That the

does not occur alone

latter

(a)
(ft)

doubtless due to the

is

very considerable concentration (the pressure was approximately


one atmosphere) at which this slow oxidation took place.

The following observations, made by VAN 'T HOFF, confirm this


result. Oxygen and phosphine in the ratio of 361
177 were allowed
:

to react partly at the ordinary temperature,

part
left

at

50.

residue of 196

unchanged, 70

mm,

mm.

but for the greater


and 42 mm. PH 3 was

being produced at the same time.

Therefore,

177

42

135

PH

3,

and 361

196

165

had undergone change.


1

The volume

of the gases being constant, the


quantity

is

measured by the pressure.

SIMPLICITY OF MANY REACTIONS.

25

According to equation (&), 70 mm. of hydrogen are formed


from equal amounts of phosphine and oxygen, so that after
subtracting 70 from each of the above quantities in order to

mm.

allow for the formation of the 70

PH

mm.

65

the ratio

This

and

which are nearly

quantities

2,

obtain
in

2:3.

result

oxidation

mm.

95

we

of hydrogen,

with

well

very

agrees

takes

the

that the

hypothesis

according to equation (a),

place partly
partly
according to (b) only in this case, owing to the greater quantity
of oxygen, rather more of the phosphine (just half of it) is
changed into phosphorous acid than in the first experiment.
;

The slow oxidation

takes place approximately ac-

therefore

cording to the equation

which

in

HP
4

PH

the

4-

HP0 +

H P0 +

occur

acid might

phosphorous

2,

as the pyro-acid

As bearing on
SMITHELLS

the simplicity of

and DENT

reactions the results of

many

are interesting

they found that the com-

bustion of cyanogen takes place in two phases, viz

C 2N 2
whilst

in

the

CO +

2,

phase the carbon monoxide

second

is

oxidised to

carbon dioxide.

We

this case, not with a trimolecular

are dealing therefore, in

reaction represented

by the equation

C 2N 2

= N +
2

C0 2

but with a bimolecular reaction.

The

trimolecular

acquainted will be

reactions

more

with

be mentioned that their number


1

Jonrn. Chem. Soc. 1894. 603.

which

fully treated later.


is

small.

we

are

at

At present

present
it

may

THE COURSE OF CHEMICAL CHANGE.

SECOND PART.

DISTURBING ACTIONS.
Chapter

I.

Disturbing actions in liquids.

EFFECT OF THE MEDIUM ON THE VELOCITY OF


REACTION. ACTION OF CONTACT.

I.

It

is

in

place
is

only in rather rare cases that a chemical change takes


the simple way indicated.
The influences to which it

subject

are

so

resolves

reaction

disturbing

effects.

manifold,
itself

For

to

that
a

the study of the course of a

great

extent

into

that

of

the

this reason these secondary actions will

be separately considered here.


In this special chapter such obvious causes of irregularity as
of homogeneity of the reacting substances, evolution of
heat by the reaction, occurrence of secondary transformations and
so on, will not be considered.

lack

Attention will rather be directed to less evident disturbances.

As we have chosen the normal course of change for our point


of departure, we shall first turn to the reactions which take
liquids

are

phenomena, because in
the influences under consideration are very little felt and

easily

much
up

liquids in order to study these

in

place

eliminated,

greater

whilst

difficulties

the

study

in this respect

of the

gases presents

and can only be taken

later.

If

reaction

take place in a liquid there

is

only one cause

27

INFLUENCE OF THE MEDIUM.

which merits special attention here, namely the


medium on the velocity of the reaction.

of irregularity
influence of the
It

that

evident

is

this

if

influence

exist,

really

data

the

comparable with each other in


the different periods of its course, because the medium is gradof the products
ually modified in consequence of the accumulation
relating to the reaction will not be

of the reaction.

Such an influence of the medium on the velocity of the reaction


quite certainly exists, and is of considerable magnitude even in
those cases in which a chemical, or any analogous process which
might be supposed to produce such effects, appears to be ex-

which

that

cluded;

called action of contact,

is

therefore, really

exists.

The numerous observations which have been made on the

medium on

the

of

influence

the velocity of a reaction can be

referred in the majority of cases to actions which are due to the

nature

the

af

medium

they

do not in the least compel us to

admit the reality of the mysterious action of contact.

Thus the following two categories of observations appear


be wholly unsuited to solve the question.
There are in the first place those actions of the
(1)

which are evidently of a chemical nature.


We have secondly those observations
(2)
bodies

were

not

in a

in

homogeneous condition

to

medium

which the reacting


these cannot be

regarded as decisive.

The
classed

effects

with

these,

acids),

certain

an

(and

this

remark

rate

at

alteration

salts

to

it)

perhaps be
which is not yet

may

platinum
a

is

point

on the

Further,
2

this

though

completely elucidated.
BOGUSKI

by spongy

produced

of

may

the

marble

medium

the

to

applies

which

experiments

dissolved

is

(such

by

of

dilute

as the addition of

favour the renewal of the decomposed


may influence the velocity of the

acid near the marble and thus

reaction in a

way

The following

differing entirely

from a contact

observations, against

See also OSTWALD, Lehrbuch der Allgem. Chemie,

Berichte

9,

action.

which the objections menII.

512

et seq.

1646, 1876; see also SPRING, Zeit. phys. Chem.

1,

209, 1887.

28

DISTURBING ACTIONS IN LIQUIDS.

be

cannot

tioned

medium

to

action of the

the

establish

alone:

and PEAN DE ST. GILLES

BERTHELOT

(1)

seem

raised,

in virtue of its presence

found that an excess

of alcohol retards the etherification of acetic acid in such a


that a

gram molecule

of

was transformed

it

to the extent of 118

JO

(2)

of experiments,

solvents

molecules of alcohol.

thorough investigation of the subject has recently been


3
who has shown by means of an extended

made by MENSCHUTKIN
series

way

100

[28 per cent

in 4 hours at

that

the

influence

the

so called chemically indifferent

of

velocity

chemical

reactions

in

very

different degrees.

Whilst for example the combination of triethylamine and ethyl


takes place with a velocity
1 when they are dissolved

iodide

same combination occurs with benzyl alcohol


which is 742.2 times greater.

in hexane, the

for

solvent with a velocity


It

may

which

is

therefore

taking

also
in

part

happen that one of the


the reaction

is

itself

liquid bodies

an unfavourable

medium.

An

excess

of

for

aniline

acetic acid in such a

way

example retards

35 percent!
Ms changed by
9Q
^y
.

,,

into acetanilide in 15 minutes at


(3)

L.

MEYER

<

>

1^1

own

action on

molecules of aniline

155.

drawn attention

has

its

that, of a gram, molecule of acetic acid

to

the

fact

that

the

velocity of nitration of benzene increases proportionately to the


square of the quantity of nitric acid used, whereas it is diminished

by excess of benzene.

Along
researches
1

2
3

4
5

with

phenomena we may here mention

these

of LANDOLT

the

on the change in the optical rotatory

Ann. Chim. Phys. (3), 66, 90, 1862.


SCHWAB, Inaugural Dissertation p. 37; cf. p. 17.
Zeit. phys. Chem. 1. 627, 1887; 6, 41, 1890; Berichte, 15, 1618, 1882.
Zeit. phys. Chem. 2. 713, 1888; Berichte, 22, 18, 1889.
Das optische Drehungsvermogen.

CONTACT ACTION.

power of a substance when

it

there

of

is

little

probability

29

dissolved in liquids with

is

which

a chemical reaction, for example

turpentine dissolved in alcohol, benzene, or acetic acid.

To

regard the rotativity as a function of the con-

of the molecule, (without regard to any special hypothesis),

stitution

an

who

those

alteration

in

be an indication of some displacement

will

it

of the molecular equilibrium.

The

of a

velocity

small

reaction
the

displacements;

is

slow

very

much

course

of

affected

by such

monomolecular

the

reactions proves, for example, that the different molecules, although


apparently placed in identical conditions, still differ from each

other in

such a

way

that in a given time only a part of

undergoes change.
LANDOLT expresses himself as follows:
"It

conceivable

is

(alcohol)

the

latter,

when molecules

the atomic

of

foreign

active

body

substance

modification

certain

that

so

their

atoms,

in

is produced in the structure


each molecule the distances between

arrangement

in space,

and also the nature of

movements are changed."

connexion

In

come between the molecules of an

(turpentine)

of the

that

them

with

the

experiments

which

he

has recently

made MENSCHUTKIN says


"This behaviour shows that
:

certain contact action occurs

between the so called indifferent solvent and the dissolved

body,
consequence of which solutions of a body exhibit different
chemical behaviour with regard to the changes in the velocity
of chemical reactions taking place in such solutions, according*

in

to

11

composition and structure of the indifferent solvent.


the whole, experience forces us to admit that contact action

the

On
exists,

that

is,

that the

medium may by its mere presence influence


The greatest attention must therefore

the velocity of a reaction.

be paid to this influence in studying the course of a reaction.

Zeit. phys.

Chem.

I,

627

et seq.

1887;

fi.

41

et seq.

1890.

30

INFLUENCE OF PRESSURE ON THE VELOCITY


OF REACTION.

II.

That the rate of reaction

many

is

influenced by pressure

of the researches which have been

made on

is

proved by

the subject.

has shown that the transformation of moriosymmetric


into rhombic sulphur takes place at 96. 2 under a pressure of 16

REISER

atmospheres,

whilst

at

atmospheric pressure the change in the

opposite direction occurs at this temperature. Later, SPRING and VAX


acetate, which decomposes into
under atmospheric pressure, undergoes this
same decomposition at 40 when the pressure is 6000 atmospheres.
2
SPRING
has prepared compounds of sulphur and arsenic with

HOFF found that copper calcium

'T

constituents at 77

its

A great number
metals by using very high pressures.
3
of reactions may be brought about by sudden pressure
These effects of pressure will, however, be considered below,
various

for the present

The

it

is

sufficient to point out their existence.

influence of pressure on the rate of reactions taking place

media has only been examined in a few cases.


4
BERTHELOT and PEAN DE ST. GILLES could find no difference

in liquid

rate of etherification of an alcohol

VAN

'T

cinic acid,

HOFF

also

when

found that

in the

by an acid at different pressures.


the rate at which dibromsuc-

dissolved in water,

is

transformed at

100,

is

in-

dependent of the pressure.


Finally
tioned,

in

some recent experiments by RONTGEN 5 may be menwhich the influence of pressure on the rate at which

sugar is inverted by hydrochloric acid was studied. The


pressure used was 500 atmospheres, whilst BERTHELOT and PEAN
DE ST. GILLES worked at 50, and VAN 'T HOFF at 6 atmospheres.
cane

RONTGEN concludes

by pressure.

He

is,

that

the

rate

of inversion

is

diminished

however, not justified in drawing this con-

clusion from his experiments.


l

GROTH'S

Zeitschrift fur Krystallographie, Vol. 8. p. 593, 1884. Inaugural Dissertation,

Amsterdam, 1883.
2

Bulletins de 1'Academie royal de Belgique, [2] vols. 45 and 49. Berichte 15. 595, 1882.

MEYER. Dynamik der Atome. 1883, 393.

Ann. Chim. Phys.

WIED. Ann. 45,

(3) 66. 45,

98, 1892.

1862.

For
from

the

if

his

in

velocity constants for the inversion

be calculated

it

different

found that the values of the constants

is

with the same solution

experiments

differ

more considerably, than do the constants obsolutions which have undergone inversion on the

from each

other

with

tained

31

numbers,

obtained

hand

one

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

the ordinary pressure, on the other under a pres-

at

sure of 500 atmospheres.

The
the

by RONTGEN

differences observed

under

version

errors

the

in

in the course of the in-

accordingly smaller than


experiments, which are of not inconsiderable

different

are

pressures

and which can be completely accounted for by the

magnitude,

variations of the temperature of the solutions

measurable
with

occur

of

acceleration

weak

the

*.

reaction

should

however

acids or acids of intermediate strength,

such cases, according to the calculations of TAMMANN

2
,

as in

the external

considerable influence on the degree of


electrolytic dissociation of the acid.

pressure

exerts

very

Chapter

II.

Disturbing actions in gaseous systems.

THE ORDER OF MAGNITUDE OF THE DISTURBING

I.

ACTIONS IN GASEOUS SYSTEMS.


While
occur

bare

in

it

is

easy to eliminate the disturbances which

fairly

course of reactions in liquid systems,

the

the true character of the course

simplicity,

material

so that reactions of this kind


for

studies

in

with gaseous systems.

form the most convenient

it

is

frequently difficult to realise

normal course of the reaction.

When

this

number of

its

chemical dynamics, it is quite different


There the irregularities of the reactions

are of such importance that

the

and to lay

of the reaction in all

See

See

TAMMANN,
TAMMANN,

work

originally

researches,

Zeit.

pliys.

Zeit. phys.

by

appeared there was in existence


chemists, on the course of

other

Chem., 14, 444, 1894.


Chem., 17, 725, 1895.

32

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

which agreed more or


equations which have been

reactions in liquid systems, the results of

with

less

the

of the

requirements

deduced above.

was the case with the researches of BUCHANAN

This

on the

decomposition of chloracetic acid by caustic soda, and of aqueous


solutions of chloracetic acid; with those of URECH on the birot3
and
and on the inversion of cane sugar
4
on hydrolysis; since then they have
also with those of WARDER
2

ation of milk

sugar

become innumerable.

The

position

however,

is,

different

quite

when we

turn to

chemical reactions in gaseous systems the only researches in this


department, which up to the present time have been brought to
a satisfactory conclusion are those on the rate of change of
;

arsine

and phosphine (VAN

(BODENSTEIN).

the

On

Koou), and of hydriodic acid

HOFF,

the other hand our experimental knowledge of

which

disturbances

greatly

'T

reactions in gaseous systems has

affect

increased without any comprehensive explanation of the

phenomena having, so far, been given.


The following observations appear to point to a contact action

greater part of the

though other hypotheses have been proposed to

of the medium,

account for them.


(1)

The

of

oxidation

of

rate

phosphorus

is

affected

in a

remarkable way by various gases.

For example the oxidation


air with 1 / 3 of its volume of
ethyl ene,

PH 3

of

Viooo

1
,

in air is prevented

2 S,

/ 50

by mixing the
x

of ether vapour,

/ 18W of petroleum vapour,

or

/45o
1

/uu

of
of

turpentine vapour

In recent years a great number of cases have been investi(2)


more
especially by DIXON and BAKER, in which the influence of
gated,
G
minute traces of aqueous vapour on chemical changes is apparent
.

Berichte 4, 863, 1871.

15, 2457, 1882.

16, 2270, 1883.

Amer. chem. Journ.

According

to

3,

GRAHAM,

188182;
Phil.

Berichte 14, 1361, 1881.

Mag.

5,

408, 1834, liquid hydride of phosphorus

shows a similar behaviour.


6

The

literature

1894. (Trans.)

p.

of

623.

this

subject

is

given

in the Journal of the Chemical Society

33

INFLUENCE OF MOISTURE.
l

According to DIXON a perfectly dry mixture of carbon monoxide and oxygen cannot be exploded at all, or only with great
If a minute trace of moisture
difficulty, by the electric spark.
be brought into the mixture, the explosion occurs at once without
The explosion may also be induced by other gases
difficulty.
such as H 2 S,
3
HC1, C 2 H 4 i.e., such as contain hydrogen,

NH

while

S0 2 CS 2 C0 2 C 2 N 2
,

are without action.

Furthermore the quantity of the aqueous vapour present has a very


great effect on the velocity with which the explosion is propagated.
however, to point out here that in other reactions

It is in place,

the

of

presence

aqueous

rate of decomposition of

THAN

to

'

aqueous

retard the change;

may

vapour

ammonia

at

the

high temperatures according

diminished by about 98 per cent by the presence of


and according to VAN DE STADT 3 the rate of
vapour
is

oxidation of gaseous phosphine

also diminished

is

by

it.

Among BAKER'S numerous observations, the experiment in which


phosphorus was found not to burn in very carefully dried
oxygen even when heated to 150
it was only
ticularly interesting

may be

pointed out as parafter the admission of a small


,

quantity of moist air that inflammation occurred.

Similar results

were obtained with sulphur, carbon, etc.


(3.) Whilst studying the action of hydrogen on chlorine under
BUNSEN and ROSCOE

the influence of light,


of change

found that the rate

was diminished

to the extent of

37.8 per cent


9.7

3
)

PRINGSHEIM

Phil. Trans. 1884, 618.

LIEB. Ann. 131, 121, 1864.

Zeit. phys.

BAKER

Cbem.

12, 329,

unfortunately

EWAN'S experiments on

p.

does

/iooo

10
'/iooo

DIXON and HARKER

7
,

of hydrogen,

Viooo of oxygen,

60.2

of chlorine.

and also BAKER

have further

1893.
not

mention

the

pressure

of the oxygen used.

POGG. Ann. 100, 499, 501, 502, 1857. Also OSTWALD'S Klassiker der

schaften,

No. 34.

See

68.
exact.

Wissen-

p. 81.

WIED. Ann.

Manchester

Journ. Chem. Soc. 1894,

32, 384, 1887.


Lit.

ami Phil. Soc. 1890.


p.

OWENS

College Researches, 1.

623.

34

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

much more

slowly when
aqueous vapour is excluded than when it is present.
(4.) The formation of ozone by the electric discharge is completely stopped by the addition of traces of chlorine, while nitrogen,

shown that

hydrogen,

this

takes

change

and fluoride of

place

aqueous vapour
2
and BAKER
SHENSTONE

'T

effect

In this

according to

3
.

which was carefully studied by VAN

reaction

HOFF

no

has

case

silicon are favourable to it

closely allied to these so called catalytic

is

actions; he found that the formation of

ammonium

carbamate was accelerated by the presence of aqueous

vapour whilst alcohol vapour retards it.


It is to be noticed that the acceleration produced
by the aqueous vapour is not be ascribed to the

simultaneous

though

formation

ammonium

of

carbonate

this certainly occurs.

on

experiments

Special

this point

have shown

that the mixture of steam,


dioxide

ammonia, and carbon


which may be obtained according to the

equation

NH
by

.HC0 3

C0 2

NH + H

-f

0,

ammonium carbonate, forms in the


ammonium carbamate with very great

volatilising

first

place

velocity,

C0 2 +

NH = NH
3

.COOHN,,

and then, very slowly, ammonium carbonate,

NH .COONH + H
4

Fig.

7.

The

servations

and the
figure

on

the

retarding

apparatus

acceleration
effect

7.

Compt. Rend. 91, 762, 1880.

Journ. Chem. Soc. 1888, 53.

Ibid.

1894, 617.

of

= NH

which

was

produced

alcohol

.HC0 3
used

by

vapour

+ NH3
in

aqueous
is

the

ob-

vapour

represented in

FORMATION OF AMMONIUM CAKBAMATE.

The

35

C was filled with carbamate und closed before the


The whole apparatus was then filled with mercury and

side tube

blowpipe.

placed in position in the burette D which also contained mercury.


On heating the salt, the mixture of carbon dioxide and ammonia

produced displaces the mercury from the vessels A and B. When


a sufficient quantity of the mixture is obtained the formation
of

carbamate

the

with which

it

allowed to begin,

may be

and the velocity

takes place in the two vessels compared.

This is done by determining the pressures of the gaseous


mixture in the two vessels from time to time, the volume being

maintained constant.

This

to flow out of the burette

into

is

accomplished by allowing mercury

whenever

it

is

on the point of rising

or B.

If the apparatus has

reaction

in

been properly

the two divisions of

filled,

the velocities of the

are found to be exactly equal.


then introduced in a little glass
it

A small quantity of water is


bulb into A. The quantity used is that which can evaporate at
the ordinary temperature into the space available (0.0004 gram,
or 4 per cent, of the carbamate employed).

Both

warmed

vessels are then

in an air

bath so as to decompose

the carbamate which has deposited on their walls.


In this way
the mixture of carbon dioxide and ammonia is regenerated in
and
B, but with the difference that water vapour is now present in A.

When

the two divisions of the apparatus are brought back to


the initial temperature a decided difference in the rates at which

them

the reaction occurs in

The

rate

in

is

is

evident.

approximately doubled by the introduction

of the aqueous vapour.

The retarding
a

similar

way,

influence

while

air

was established

of alcohol vapour

had no

effect

even

when

in

present in

fairly large quantities.

Since
reaction

the
is

existence

of these disturbances in the course

proved experimentally

in

of a

such a variety of cases,

it

not surprising that the greater part of the reactions occurring


in gaseous systems which have been studied
up to now do not

is

follow the equations which


1

Sec the exceptions on p. 32.

we have

deduced.

This

is

the case

36

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

with the experiments of BERTHELOT and PEAN DE SAINT GILLES on


etherification, and with those of LEMOINE on the formation and
decomposition of hydriodic acid.

The following changes

which were investigated by VAN

also,

HOFF, lead to similar results

'T

1.

2.

3.

The polymerisation of formaldehyde.


The polymerisation of cyanic acid.
The transformation of moist electrolytic gas

into water.
4.

The transformation of dry

electrolytic gas into

water.

1.

Polymerisation of formaldehyde.

Through the researches of HOFMANN

we know

formaldehyde possesses the formula


that
this body gradually changes into
and
CH^O,
a solid polymeric substance, the formula of which

that

is

gaseous

very probably C 3 H 6 3
This reaction was investigated as
.

interest,

it is

of special

being probably trimolecular.

The apparatus used

(fig.

8) consists of a

large

Fig. 8.

A, attached to a barometer tube B.


far as possible with the air pump, (to

round

flask

After

evacuating it as
about 2.01 mm.), the gaseous formaldehyde, evolved by heating
the compound C 3 H 6 3 in a small retort, was admitted over

mercury.

Having thus

filled

the

apparatus

of the burette

the mercury

stant and the pressure of the

from time to time.


lowing table

it

is

placed in position in
is maintained con-

the volume

unchanged formaldehyde measured

The numbers obtained

are given in the fol-

3
.

Berichte, 2, 156, 1869.

Compare with D in fig. 7, page 34.


The total pressure, reduced to 0, is

in the apparatus (2.01 mm.).

corrected for the initial pressure of the air

POLYMERISATION OF CYANIC ACID.

Time.

37

38

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

The apparatus used


drical

vessel

(fig.

in this investigation consisted


9)

to

of a cylin-

B was

which a small manometer

The liquid cyanic acid which was employed in filling


was prepared by heating anhydrous cyanuric acid in the
retort H, and condensing it in

attached.
it

the

cooled

The

liquid acid

receiver J,
is

(fig.

small, well cooled bottle C,


is

which

then connected with the tap F,

by means of which

may
Fig. 10.

10).

poured into the

be

with the

its

contents

communication

put

in

air

pump.

The

air still

remaining in the bottle having been pumped out, it is put in


communication with the apparatus A B which has previously
been fused to E by means of the side tube D, and is vacuous.
After

filling,

blowpipe and

The following

Time.

apparatus is disconnected by means of the


then ready for the measurements of pressure.

the
is

table contains the results

which were obtained.

39

FOKMATION OF WATER.

the equations proposed. The experiment,


always yielded the same result.
3.

The transformation of moist

repeated several times,

electrolytic

gas into water.

gas into water was found


to take place at 440 sufficiently slowly to admit of its course
being followed; this change, especially attractive on account of

The transformation

its

of electrolytic

was therefore

simplicity,

carefully studied.

The apparatus which was employed with moist


gas

resembled

large thermometer

it

was

filled

electrolytic

by means of

Fig. 11.

the

gas

burette

gas.

By means

this

way

(fig.

11)

which contained the electrolytic

apparatus to
be filled (shown in the figure in a horizontal position; may be
connected either with the air pump through D, or with A; in
it

is

of the

first

tap

Some mercury

the tube to the

of

C being

left

is

filled

closed,

now

with the gaseous

it

is

sealed off be-

introduced into the part

of the tap, which

the

of

part

evacuated and then

mixture, after which, the tap

tween C and B.

the

is

then opened so as

\
Fig. 12.

to obtain a short index of

of

suitable

fig.

12).

mercury shutting

off a

column of

air

length in the capillary tube of the apparatus (L in


is finally sealed up before the blowpipe.

The tube

The bath

in

which the apparatus was heated

(fig.

of an iron cylinder A, containing boiling sulphur.


of mica, one of which

is

visible at C,

13) consists

Two windows

permit the height of the

sulphur vapour to be observed.


1

This was constructed in the way described by BUNSEN, Gasometrische Methoden,

1877, p. 76.

40

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

The bath was heated


a gas regulator

The quantity

in a PERROT'S gas

furnace provided with

l
.

of the gaseous mixture remaining after the heat-

ing had been continued for a

known

interval of time,

was

deter-

Fig. 13.

mined by placing the apparatus in a horizontal position


water M, (fig. 12), so as to equalise the temperature in

The length

parts.

of the column of

on the

scale

versely

proportional

which

of the residual gas

The
Time

shown

air,

all its

measured

This length is into the pressure, and thus to the quantity


is

in the figure.

2
.

results obtained are as follows:

in hours.

L, was then

in the

41

FORMATION OF WATER.

The

experiment, which was repeated several


times, also do not agree with our equations.

4.

of

results

this

The transformation of dry

electrolytic

For these experiments the following


the apparatus just described

gas into water.

A\

the same

filled in

were made

in

in figure 14,

is

alterations

the reservoir

way

as formerly

through E, but it is now made to


communicate with the parts C, D
and F, which are united by means
flexible tube containing

of a

mer-

cury.

This

arrangement allows a por-

of the gaseous mixture to be

tion

from

transferred

lowering F),
tained in

While

to

C,

dry

sulphuric

acid

with

contact

in order to

(by
it

by

con-

C over the mercury.


the

apparatus is beingheated in the sulphur bath (not in


the apparatus

Fig.

which

will be

whole

of the

B shown in the figure,


mentioned

later) the

gaseous mixture
contained in A, and the tap D

is

is

closed.

When

mixture has been heated for the time desired, the


tap is opened and the tube F raised and lowered about a hundred
times so that the gas is dried while it is cooling.
the

The quantity

of the gaseous mixture remaining

mined by means of
volume

The
1

its

pressure

at

is

then deter-

constant temperature and

2
.

results are the following:

The lower part

with the three side pieces serves to prevent

from coining in

contact with the iron cylinder in which the sulplur in boiled.


2
The reservoir
is
placed in water from the water supply, and the temperature, the
height of the barometer, and the difference in level between the mercury in C aud F

when the

gas occupies a given volume, read off by

means of

the cathetometer.

42

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

Time

in hours.

43

THE NATURE OF THE DISTURBING ACTIONS IN


GASEOUS SYSTEMS. ACTION OF THE WALLS
OF THE VESSEL.

II.

Formation

of cyamelide

and of water ; decomposition

of phosphine.
the

Since

deviations

from

the

normal

course

of change in

gaseous systems appeared be of a secondary nature, the question


as to their cause presented itself.

was found possible

It

to prove

by experiment the existence

of disturbing actions in the cases which have been described.

Turning in the first place to the disturbing actions in liquid


systems, the volume occupied by the reacting substances must
be taken into account

this

when compared with

the

volume must be a vanishing quantity


whole volume of the system. This

when we

with gases under


atmospheric pressure; the other condition, that the nature of the
medium shall remain unchanged during the reaction is, however,
condition

is

satisfied

are

dealing

not satisfied in gaseous systems.


It is clear that in a reaction taking place between
gaseous
substances, as for example the formation of water from electro-

medium undergoes
example mentioned, the medium at

is

the

gas,

lytic

electrolytic

at the end,

gas,

it

a profound change.
In the
the beginning of the process
is the aqueous
vapour which

has been formed.

two disturbing actions which are found in


liquid systems, there are two other causes of irregularity which
In

addition

to the

exert their influence

more

especially in gaseous systems, viz

The area of the surface of the walls of the vessel.


The nature of the surface of the walls of the vessel.

1.

2.

Influence of the area of the surface of the walls of the vessel.

1.

Polymerisation of cyanic acid.

The apparatus shown


effects

of

cyamelide
l

On

this

the

walls

15 was used to investigate the


of the vessel on the rate of formation of
in figure

*.

ac-tio.i,

see

NAUMANN,

LIEB. Ann. 160, 16, 1871.

44

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

The

divisions

and

have the same volume, but the areas

of their walls are in the ratio

6:1.

A little anhydrous cyanuric acid having been


brought into D the apparatus is placed in
a burette containing mercury and evacuated

by means of the air pump which is attached


The tube D is then closed
to it at D.
before the blowpipe.

By

heating

both compartments are

filled

On lowering the
with gaseous cyanic acid.
A and B
between
communication
apparatus
which the pressure of the
unaltered cyanic acid is measured from time

is

cut off,

after

to time.

These measurements of the pressure show


that

the

takes

reaction

different rates in the


Initial pressure

After one day

place

two

at

entirely

divisions.

188.4 mm.

146. 8

in A.

"157

B.

Fig. 15.

Ratio of the velocities in

1.33

The
fore

2.

and B,
:

1.

velocity in the division with the greater surface

much

is

there-

the greater.

Influence of the nature of the surface of the ivalls of the vessel.

Since the superficial area of the walls of the vessel influences


the rate of the reaction, it may be surmised that the nature of
these walls will also have

This

is

some

a matter which

is

action.

worthy

namical studies in which the reaction

example when a
on
them.
deposited

in the walls, as for


is

Although observations of
NAUMANN,

this kind

LIEU. Ann. 160, 16, 1871.

of special attention in dyitself

produces some change

solid product of the reaction

had previously been made \

NATURE OF THE WALLS OF THE VESSEL.

was

it

still

be

thought to

45

of special importance to study the

phenomena more completely,

order

in

that their effects might

be eliminated.

made on,
The polymerisation of cyanic acid.
The transformation of electrolytic gas

Investigations were
a-.

b.

The decomposition

6'.

into water.

of phosphine.

Influence of the nature of the ivalls of the vessel on the

a.

polymerisation of cyanic acid.

The

influence

which

of cyamelide,

is

deposited on the walls

of the vessel during the polymerisation of cyanic acid,

was

by means of the apparatus represented in figure 7.


The division B was filled with gaseous cyanic acid,

stu-

died

in the

(p. 35). As soon as the


walls had, in consequence of the polymerisation, become coated
with cyamelide, the unaltered cyanic acid was divided between A

way which has already been described

and

by raising the apparatus; the communication between the


was then interrupted by lowering it again, and the
measurements of the pressure proceeded with.
two

vessels

The following

results

were obtained

49.5 mm.

Initial pressure

Pressure alter one day

(44.5 mm.
.

Ratio of the velocities in

A
1

The

rate of the reaction

in the division the walls of

b.

is

in

32.4

A.
B.

and B,
3.42.
therefore rather

more than trebled

which are coated with cyamelide.

Influence of the nature of the surface of the ivalls on the

transformation of electrolytic gas into water.


1.

The

Older experiments.

results obtained in the study of this reaction (p. 40) ap-

peared to point to a disturbance, arising during the progress of


the reaction, and retarding

it

more and more

as

it

proceeded.

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

apparatus shown in figure 14,


lytic gas, gave the following results,

The

Initial pressure

when

.........

Pressure after heating to 448


5 hours

997.7 mm.

for

...........

Diminution of pressure per hour


After

when

having

been

filled afresh,

used for

with electro-

filled

980
3.5

,,

130 hours, the same apparatus,

gave:
Initial pressure

mm.

801.1

Pressure after heating


to

448

Decrease

for

per hour

The
the

20 hours 788.8

of pressure

....

0.6

.,

change in the nature of


produced by heating

walls,

the vessel for 130 hours, has thus

reduced the velocity of the reaction to one sixth of its original


value.

This result was confirmed by

means of the apparatus represented in figure 16.

The

vessel A,

which had been

used in the experiments just mentioned,


Fig. 16.

used

along

and which had therefore

been heated for 150 hours, was

with

second,

new

vessel

The two were connected by means

of

of the same shape.

capillary tube

C D.

After evacuation, through E, both vessels were filled with electrolytic gas, and a column of mercury was introduced into C D
in order to interrupt the

to

measure

the

communication between the

pressure in

them-;

was

vessels,

and

finally closed before

the blowpipe.

The two

vessels

were heated

in the

same way,

in

two PERROT'S

gas furnaces provided with therm o-regulators (see p. 40).

They

47

NATURE OF THE WALLS OF THE VESSEL.

were

immersed

in

the

vapour

of boiling sulphur contained in

cylinders of the form described on page 39.

The heating was


allowed

to cool,

discontinued from time to time, the vessels

and immersed

in

water from the water supply

same temperature.
The height of the mercury column was then read

to bring

them

to the

millimetre scale.

Time

in

hours.

off

on the

48

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

BUNSEN and ROSCOE had observed that exceedingly small


quantities of impurity, have a very great influence on the normal
Since

of the

course

reaction between chlorine and hydrogen

KRAUSE, and ASKENASY

took

MEYER,

to

pains
prepare absolutely pure
With electrolytic
gas for use in their experiments.
of
traces
other
had
containing
gases, they
previously ob-

electrolytic

gas

tained entirely irregular results.

Their experiments were performed as follows - - Small glass


bulbs,
containing about 20 cc., after being filled with the
explosive gas, were heated for a certain time, either in a liquid
:

bath, or in the vapour of a boiling liquid.

The

final

experiments

made with an extremely pure

were

mixture of oxygen and hydrogen prepared by electrolysis, which,


14 days
in order to avoid impurity, had been passed for 10

through the bulbs which were to be filled, (the bulbs being


It
united with each other by means of glass capillary tubes).

was found that the normal course of the reaction could not be
realised.

For example, two very carefully cleaned glass bulbs were


heated simultaneously, for exactly two hours, in the same bath,
(phosphorus sulphide, boiling at 518), after which the quantity
of electrolytic gas remaining was determined.

The

results are as follows:

Number

of the experiment

Bulb

of the electro-

II

27.83

III

IV

28.2 53.71

63.29

1.

26.41

2.

19.34 100.00 100.0 57.29 100.00

ly tic gas

From
the

combined \
these results,

most

carefully

the only conclusion possible

cleaned glass

surfaces

is,

that even

possess irregularities

which exert a variable influence on the transformation of

elec-

trolytic gas, and that the surfaces of two glass bulbs which have
been prepared with the greatest care in the same way, may be
different, or may become so during the reaction, to
account for the entire irregularity in the results of the experiments.
The attempt to prepare identical smooth bulbs was abandon-

sufficiently

See page 33.

NATURE OF THE WALLS OF THE VESSEL.

49

and the internal surfaces made completely rough, as it was


thought possible that in this way they might be more easily
ed,

This remedy was however a complete failure,

obtained the same.

numbers show:

as the following

Etched bulbs

l
]

Percentage of electrolytic gas transformed


into water.

The exclusion

of

glass surfaces

was

33.8

2.

51.1
Glass

also unsuccessful.

bulbs coated internally with silver yielded results similar to those


obtained with the etched ones.
Silvered bulbs.

L
Percentage of electrolytic gas
transformed into water

Vessel

II.

III.

1.

19.8

7.5

15.6

2.

97.7

92.9

35.2

These bulbs were heated in aniline vapour, at 183, for two


hours, it having been found that the change takes place at a
considerably lower temperature in contact with a surface of silver,
than in glass vessels.
It has already been noticed, that MEYER and ASKENASY found
that the devitrification, which probably occurs in consequence of

aqueous vapour on the walls of the


glass vessels, does not always retard the formation of water, as
the older experiments of VAN 'T HOFF (p. 47) appear to show,
the

the

of

action

heated

but that the results are completely irregular in this respect also.
Bulb previously heated
for
to 518

Percentage of electrolytic gas


transformed into water at 518

New

bulb

24 81

22

24

26

28 hours,

21.8 29.3 78.7 37.4

Effect of the nature of the ivalls of the vessel on the

c.

decomposition of gaseous phosphine.


In

the

course

of

gaseous phosphine at
1

from

Totally
light.

into water varied


!

results

irregular

In

Zeit. phys.

one

on the decomposition of
"
higher temperatures, D. M. KOOY has also
an

series

from 11.3

Chem.

of

investigation

were

also

obtained

in

bulbs which had been protected

experiments the percentage of gas which was changed

to 82.3.

12, 155, 1893.

Inaugural Dissertation, Amsterdam, 1892.

50

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

recently

the

observed

velocity

the

effects

of the reaction.

of the

surface

of the vessels on

The experiments were made with

the apparatus represented in figure 14.

The following table contains the experimental


perature = 446).

New
Time

in hours.

vessel

1
.

results.

(Tem-

INFLUENCE OF PRESSURE ON OXIDATION.

the

the

reaction,

There

that the opposite to this

when the former

number of

however,

are,

increases

latter

is

51

facts

increases.

which seem to show

true.

found that at the ordinary temperature and normal


pressure, pure oxygen does not act upon phosphorus, whilst air
FOURCROY

oxidises

In

it

vigorously.

MARUM

VAN

1798,

observed that a

piece of phosphorus

glows much more brightly in diluted air than in air under the
normal pressure, and that the phosphorus even takes fire at low
be wrapped in a

if it

pressures

little

1817, HOUTON DE LABILLARDIERE

In

cotton wool.

observed, in the course of

investigation on phosphine, a very remarkable phenomenon,


which be described in the following words:

an

"Le gaz hydrogene protophosphore

du perphosphore en ce qu'il n'a pas la propriete de s'enflammer par le contact de Pair. II est cependant a remarquer qu'on peut enflammer
ce

dans

gaz

On

Fair,

la

temperature

se distingue

ordinaire

s'assure de ce fait en introduisant dans

longue, entouree d'un grillage de


les morceaux si le vase venait a casser, de

forte

et

en

le

rarefiant.

une eprouvette tresfil

de fer pour eviter

1'air

ou de 1'oxigene

Fhydrogene protophosphore, en maintenant le mercure dans


1'eprouvette au niveau du mercure exterieur; alors, en elevant
et de

de maniere que le mercure de 1'eprouvette soit a


deux decimetres environ au-dessus du mercure du bain lorsqu'on

1'eprouvette

opere

20

il

se produit tout-a-coup

une detonnation dans

1'eprouvette."

This experiment appears to have received no special attention.


4
repeated it and showed that the presence of an excess of

DUMAS

phosphine

PH

to 1

necessary for the success of the experiment. (2 vols.


vol.
DAVY 5 appears also to have noticed something
2 .)
is

similar.

He
1

says:

"I found that phosphuretted hydrogen produced

Meaioires de 1'acad. des Sciences, 1788.

Verhandelingen uitgegeven door Teylers Gcnootschap. 10, 1798.


"

Ann. Chim. Phys. (2) 6, 304, 1817.


Ann. Chini. Phys. (2), 31, 119, 124, 1829.

127. 1832.
1

Phil. Trans.

1817, 49.

See also

ROSE, POGG. Ann. 24,

52

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

a flash of light

when admitted

be made by an excellent

To

into the best

of Nairn's construction."

pump

these facts the following similar ones

Arsenic,

and sulphur begin to

only when the oxygen


a

similar

be added.

may

oxidise, according to

JOUBERT \

sufficiently dilute.

is

FRIEDEL and LADENBURG

vacuum, that could

found that silicon hydride behaves in

and

way,

to BERTHELOT, nickel

according

carbonyl does so also.

and

REICHER

JORISSEN

named substance

found

however,

that

the

spontaneously inflammunder
a
able in oxygen
pressure of 13 atmospheres.
4
Further, according to ENGELMANN
oxygen appears

last

is

still

have

to

more

organisms when

stimulating

its

LABILLARDIERE'S

action

pressure

is

on certain low

decreased.

experiment was repeated with the

apparatus shown in the accompanying diagram (fig. 17).


The tap C being closed, the tube is filled with

mercury, the mixture of phosphine and oxygen introD


duced, and the opening, F, closed with a cork.
is
then put in communication with the air pump,

and the

tap,

C,

opened.

The volume

of the mixture

of gases increases, and an explosion takes place.

The observation
firmed in

this

of LABILLARDIERE having been con-

way,

the conditions under which the

occurs were more carefully investigated.

phenomenon
The investigation could not however be begun,

Fig. 17.

until a special cause of the inflammation of the mixture

of

phosphine and oxygen, had been discovered and eliminated.


It was found that this inflammation may be caused by move-

ments

of

the

mercury which

is

in

contact

with the gaseous

mixture.

The following experiment shows that the mixture


Phosphorescence du Phosphore, 1874, Paris.

These sur

Ann. Chim. Phys. (4), 23, 430, 1871.


Maandblad voor Natuurwetenschappen, 1894, No.

la

Botanische Zeitung, 1882, p. 320.

1.

is

so sensitive

53

KATE OF OXIDATION OF PHOSPHINE.

such

to

great

movements,

the use of mercury

that

attended with

is

difficulties.

The apparatus shown

in

a mixture

mercury,
vols.

of air

then

closed;

C and E,

is

18

figure

of

mercury

vols.

into

brought

being

it

initially

full

of

of phosphine and 5

through A, which

is

then pumped out through

is

as in the previous experiment, so that the

mixed gases are expanded

until they

fill

the whole

apparatus. (75 vols.)

The taps C and B

are

now

the dilute gas

closed,

the two separate divisions B and D, in one of


which a globule of mercury has been left
Combustion
in
is now produced by the slightest shock
the division
filling

The
containing the globule of mercury.
reason of this may possibly be found in
local

dilutions

of the gas, produced

by

the mobile mercury. (See the explanation

given below.)
In order to avoid this cause of combustion,
viscid

the mercury was replaced by a

solution

of

calcium

chloride

in

most of the experiments which follow.

Fig. 18.

is

it

Using the apparatus in figure 17,


was proved that the explosion is not

produced by expansion alone. No change


produced by a sudden, and much more considerable

expansion

than

that

which gave

rise

ijr

to the ex-

plosion in the former experiments; the gaseous mix-

be preserved in this dilute condition without


the explosion
undergoing any change whatever

ture

may

is

produced,

however, by the diminution of volume

which takes place when the tap is opened, after D


Fig. 19.
has been brought below the surface of the calcium chloride solution.
Investigation of the rate of oxidation of phosphine near the
explosive limit.

Having cleared up the nature of the reactions which occur

in the

DISTURBING ACTIONS- IN GASEOUS SYSTEMS.

slow oxidation of phosphine,

J.

D. VAN DE STADT

made

a careful

study of the rate of oxidation.


For this purpose he used the apparatus represented in figure 19.
serves as a manometer the apparatus having been completely

with mercury, with the help of an air pump, the gases


are admitted through g, mercury flowing out through h; the
volume of the gas is obtained by weighing the latter. The
filled

pressure

was read with a cathetometer,

and

the gas

was

in

contact with calcium chloride solution.

First series of experiments.

After

filling

the apparatus,

it

was

water bath, for periods of one hour; at the


the
end of each period
pressure was diminished by about 100 mm.

heated to 50

in a

by running mercury out through


No.

Initial pressure.

1.

2.64

cc.

h.

PH., and 1.55 cc.

9.

RATE OF OXIDATION OF PHOSPH1NE.


It follows
1

55

from these data,

That temperature, pressure, and quantity remaining approxi-

mately the same, the velocity of change varies considerably


from 0.2 in No. 2 to 2.0 in No. 3.

That the

2.

is

explosion

acceleration of the reaction,

without any explosion (No.


by an explosion. (No. 1).

viz.

not preceded by any well marked


but that large velocities may occur

3),

while small ones

may

be followed

Second

series of experiments.
In the experiments No. 1 and
- the
took
in No.
3,
explosion
place during an operation,
on diluting, and in No. 3 while bringing the apparatus into

No.
1

the water bath

in order to avoid these external influences

com-

pletely, the artificial decrease of the pressure at the end of each

hour was abandoned,

50,

so

Some calcium
first

series.

50,

at

All

left to

chloride

the

solution

pressures

was again added,

itself at

in hours.

4.

1.99 cc.

as in the

given relate to the temperature

which they were measured.


No.

Time

and the apparatus simply

as to bring about spontaneous inflammation if possible.

PH

3,

and 1.03

cc.

2.

56

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

No.

Time

in hours.

6.

1.44

cc.

PH., and 1.48 cc.

2.

EATE OF OXIDATION OF PHOSPHINE.

The determination of
extremely

difficult,

this

limit

as

is,

57

VAN DE STADT found,

the gases be completely dried.

if

The phosphine usually burns when

it

conies in contact with

the oxygen, with a visible flame, or formation of a dense cloud,

complete combustion taking place.

At the ordinary temperature, a definite result could only be


obtained in a few experiments.

The observations were made in a thick walled tube closed at


ends by taps.
This was first filled with mercury, after

both

which

the

gases

were

introduced

through

the upper tap, the

mercury displaced through the lower one being weighed in order


to measure the volume of the gases. After
closing the upper*
tap and mixing the gases, they were caused to expand by allowing mercury to flow from the lower tap into a vacuous space;

was done very slowly and without shaking, (compare page 53),
which purpose the lower tube was drawn out to a capillary.
Only one of the many experiments in which the gases were

this

for

was

dried over phosphorus pentoxide

2.09

cc.

0.51

cc.

PH

Volume

2 09

Pressure of oxygen
9^ Q

After

successful.
at the explosion

=0.1

21.9

cc.

atmosphere. (10)

following experiment was


successfully carried out without any cloud being formed.

0.54

over

drying

cc.

0.95

soda-lime

cc.

PH

The upper

Volume

Pressure of the oxygen

the

limit of pressure

was

at the explosion 5 cc.

0.11 atmosphere.

also found to be

0.1 atmo.

after drying over crystallised glycerine.

lower

gases.

limit

of

pressure does not exist in the case of dry

The explosion always occurs when working with dry

gases, even at the greatest dilution.


2.

VAN
cc.

'T

The explosive

limit with moist gases.

HOFF determined the volume

of phosphine,

and 0.5

cc.

at

which a mixture of

of oxygen explodes, by means of

58

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

the apparatus shown in figure 18. The mercury was covered by


a layer of calcium chloride solution.

The

explosion

was produced sometimes by expansion, some-

by compression following on a sudden expansion, (compare p 53.) The volume of the gas at the moment at which the
explosion took place, was measured on the scale on the tube A;

times

the

reddish-brown

deposit

which

covers the walls of the tube

after the explosion, facilitates the reading considerably.

The following table contains the values of the volumes, (in cc.)
5 cc. of the mixture at the time of the explosion;
occupied by 1
the corresponding pressures of the oxygen are also given.

Expansion.

59

RATE OF OXIDATION OF PHOSPHINE.

The

that

fact

of aqueous vapour completely stop the

traces

change at great dilutions, is of some interest, since the experiments of DIXON, BAKER, and others have shown that the presence
of water

absolutely necessary in

is

PH

If the

many

reactions.

had been dried over phosphorus pentoxide, soda-

lime, or crystallised glycerine,

frequently took

it

fire

spontaneously
This fact explains the curious
2
behaviour of mixtures of phosphine and oxygen, which, as ROSE
the

in

and VAN

some

as

air,

if

it

were P 2 H 4

HOFF observed, often explode only

'T

after standing for

days.

VAN

HOFF brought together 130 cc. of phosphine and 8 cc.


of oxygen and noticed, that as the diffusion progressed, a cloud
'T

was formed, this being followed, on one occasion after two


hours, on another after 20 hours, by an explosion.
If the oxygen be replaced by air the same phenomenon occurs
soon

as

oxygen has reached the necessary pressure.


and 49 cc. of phosphine being mixed, for example,

the

as

15.5 cc. of air

had elapsed.
substances H P0 2 and

the explosion did not occur until 30 hours

As soon

as

the

which are formed

hygroscopic

at first

H P0
3

by the slow oxidation, have taken up the

moisture present, and thus dried the gases, the explosion takes place.
The table on the preceding page shows that when two limits
of pressure exist,

The upper
VAN

'T

HOFF

they

lie

close together.

limit of pressure has

been accurately determined by

at the ordinary temperature,

and by VAN DE STADT at

50.

HOFF used the apparatus shown


in figure 17.
By means of the pipette,
into the
(fig. 20), the gases were brought

VAN

'T

apparatus in measured quantities.


The pipette was filled with mercury and

oxygen gasholder, the


tubes by which the connection was made
having first been freed from air by filling
connected

1
-'

See

p.

to

the

33.

POGG. Ann. 24, 158, 1832.


See

p.

20.

Fig. 20.

60

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

them with mercury.


as

to

not

fill

shown

The

taps

F and

the pipette with gas up to a


in

The

the figure.

and

were then opened so


which is
Gr,

taps were then closed, and the

oxygen between F and

pipette, containing 0.5 cc.

The tube between

mark near

F was

then

filled

Gr,

disconnected.

with mercury, and

the lateral opening of the explosion apparatus A,

brought into
which had previously been

filled

with a viscid solution of calcium

chloride.

The phosphine was introduced in the same way, after which the
expansion was brought about in the manner described previously,
(page 52).
In this way, mixtures containing 0.5 cc. oxygen and varying
The following table
quantities of phosphine were examined.
contains the results obtained.

PH 3
CC.

RATE OF OXIDATION OF PHOSPHINE.

temperature considerably higher, viz. 180 mm.


This
result is analogous to that obtained by
approximately.
JOUBERT, who found that the pressure above which phosphorus
however,

is

at this

ceases to be luminous in

oxygen gas,

rises

with rising temperature.

If the gases are saturated with moisture, and at the ordinary

temperature, the limiting pressure is depressed somewhat, owing


to the presence of the water vapour, (as it is also by increasing
the Quantity of the phosphine, see the foregoing table). The
following table shows the effect of moisture.

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

62
cool

by

same temperature as the


which the apparatus stood. The experiments were

water bath in

water

of

current

The

of the

containing air, and a little


was placed in the thermostat, connected with the manoand allowed to stand until it had assumed the tempera-

made
water,
meter,

follows:

as

bottle,

ture of the bath.

The phosphorus was then quickly placed in position in the


apparatus, and the pressure noted. The readings of the pressure
were

then

phosphorus
area of

its

at

repeated
is

very

surface

may

acted

of time.

Since

the

on during an experiment,

the

intervals

suitable

little

be regarded as remaining unchanged.

The numbers which were obtained


In

table.

it,

kx

are given in the following


the velocity constant of the oxidation, cal-

is

culated from the expression

which on integration becomes,

where p

is

the partial pressure of the oxygen initially,


after partial oxi-

Pt

dation of the phosphorus,

and

is

the time.

The values of
the

that

kj

which were obtained increase


of

oxidation

slightly,

of

show-

moist

in

air
phosphorus
ing
of
the
decreases somewhat more slowly than the partial pressure
oxygen. IKEDA had also drawn this conclusion from his experi-

rate

ments.

Phosphorus in moist

Temperature

........ =

Pressure of the aqueous vapour


.,

air.

,,

JOUBERT, These, 1874.

phosphorus
(cf.

p.

52).

,,

=
=

20. 2

--

20. 4

17.8 mm.

0.113

mm

1
.

OXIDATION OF PHOSPHORUS IN AIR.

Time

in

minutes

t.

63

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

dp

lo

(2)

-Pi

This equation states, that the rate of oxidation of phosphorus


is not only proportional to the pressure of the oxygen, but also
to the rate of evaporation of the phosphorus.
In

order to

calculate

the

values

equation (2) must be

of k,

integrated.

a be the sum of the partial pressures of the nitrogen and


aqueous vapour in the mixture of gases, and therefore a constant
If

we have p

quantity,

Substituting this value in

a.

and developing the logarithm in a

""

P-a

12

Pl

we

series,

24

Integrating between the limits P! and

(2),

obtain

t,

and neglecting small

terms \ this gives,

The

Pi

values

means of

of

page 63 are calculated by


more nearly constant than the

in the table on

this equation; they are

values of ki

we may

there-

fore conclude, that the rate

of oxidation of phosphorus
in moist air is really

portional

to

pro-

the pressure of

the oxygen.

This, however, can only


be true within certain limits,

for

it is

oxidation

does
Fig. 21.

b.

By means
1

not

oxygen

well

known that

of

phosphorus

take

place

in

at higher pressures.

Rate of oxidation at higher pressures.

of the apparatus

With phosphorus p x

is

shown

in the

accompanying drawing,

small compared to a at the ordinary temperature.

OXIDATION OF PHOSPHORUS IN MOIST OXYZEN.

now made

were

measurements

at

all

pressures

65
at

which the

oxidation occurs.

The

glass vessel

EPA,

the volume of which was 50-

70

cc.,

communicates, by means of capillary tubes of 0.5 mm. internal


The
diameter, with the tap B and with a manometer at D.

C was made,

at

junction

with mercury,

or

either by a ground glass joint luted


a
short
by
length of thick-walled indiarubber

tubing.

The manometer was arranged


stood

the

at

same height

so

that

the tube

in

the

mercury always

the volume of the

D;

therefore remained constant.


A mercury manometer
was usually employed, though in a number of experiments a
brom-naphthalene manometer was substituted for it; the latter

apparatus

be

could

read

naphthalene

and the vapour of the bromon the course of the reaction. The

more accurately,

had no

efiect

phosphorus was purified by melting


potassium bichromate and sulphuric

under a weak solution of

acid,

and washing

it.

this phosphorus was brought into the apparatus


melted at P, (in an atmosphere of carbon dioxide,

of

piece

E,

through

it

or in vacuo,) and spread out over the upper surface of the bulb
as

in

thin

solidify.

layer

little

A, the opening

at

as possible,

after

which

it

was allowed

to

water having been brought into the apparatus

was sealed up before the blowpipe.


in this way, was placed in a constant

The apparatus, prepared

temperature water bath, after which it was evacuated and oxygen


allowed to enter. The latter operations were repeated four or
In doing this

five times.

it

is

of importance to keep the phos-

phorus at a sufficiently low temperature, as otherwise it is very


apt to take fire when the oxygen is admitted to the vacuous

The inflammation takes

apparatus.
'the pressure

had

0,

been

is

place particularly easily

when

low and the phosphorus dry. With oxygen which

dried over phosphorus pentoxide,

under a pressure of about

it

occurred even at

mm.

The greater part of the experiments were made at 20 *.


Two experiments, which were made at 20, on the limiting
1

Phil.

See

the

Mag.

(5),

complete

tables

given

in

the

Zeit. pliys.

Chcm. 16

p.

321, 1895, or

38, 512, 1894.


5

66

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

pressure above which no oxidation takes place, gave the following


results; the reaction just began in one case when the pressure

of the oxygen

but

not

was 696 mm.,

723 mm.

at

phorus only oxidises

which are

sures
It

is

of

less

interest

We

in another case

may

oxygen, at 20
than about 700 mm.
in moist

to notice,

it

began

at

671 mm.,

therefore conclude that phos-

that JOUBERT,

21,

under pres-

who has

published

5/0

(375

experiments on the pressures at which phosphorus


luminous in oxygen, finds, at 20. 2, in the first
becomes
just
series 787 mm., in the second 666 mm., as the pressure at which

two

series of

luminosity

is first

visible.

The pressure found here seems,

therefore, to agree with those

obtained by JOUBERT, from which it follows that the pressure at


which the oxidation begins is the same as that at which the

phosphorus becomes luminous.

The

curve,

(fig.

22),

illustrates

the

connexion

between the

OXIDATION OF PHOSPHORUS IN DRIED OXYGEN

the

as

of the

those

ordinates,

the values of -[- are

I,

mean

20), and
dt

partial pressures of the

as abscissae.

oxygen
Curve

shows that

with the
the

In curve

the oxygen.

of

pressure

taken

of phosphorus in moist oxygen (at

oxidation

of

rate

67

value

pressure

falls,

considerable

range

the

of the reaction beginning

velocity

700 mm. increases at

at

then

of pressure

(viz.,

first

very rapidly as
limits over a

narrow

between

varies

500100

from

mm.), and

finally decreases again rapidly.

Curve

II

represents

pressure

of

the

graphically the connexion between the


oxygen and the rate of oxidation, the rate of

of

volatilisation

the

phosphorus

being supposed constant,

dp

The experimental numbers


circles

the

is,

represented

on a straight

lie

evidently

That

origin.

viz.,

corrected

in

the figure by

through the

line passing
is

velocity

proportional to the

pressure of the oxygen.

This
at

however only true up

is

higher

value

520 mm.;

700 mm.

at

At the ordinary temperature,


between the

exists

to a pressure of about

pressures the velocity rapidly decreases, reaching the

of

rate

therefore, the following connexion

of phosphorus

oxidation

in moist

oxygen and the pressure:

dp

-IT

tp log

dt

Above
with

the

certain

2.

much more

Phosphorus

Quite a different result

ments were made


The
cited.

data

Phil.

from

in the
wLich

Mag. Dec. 1894.

the
p.

is

'

Pl

which probably varies

ceases to be true,

this

temperature

taking place very

pressure

limiting

the reaction

slowly.

in

dried oxygen.

obtained in this case.

The

experi-

same way as those with moist oxygen,


curve
505.

is

drawn

are contained in the paper


already

68

DISTUKBING ACTIONS IN GASEOUS SYSTEMS.

that phosphorus pentoxide

except
in

substituted for the water

21).

(fig.

Two

was

experiments were made; in the first the oxygen was left


with the phosphorus pentoxide for a week, in the se-

in contact

cond for two days.

The

now

reaction

first

began

at a

much lower

pressure than

moist oxygen.
Under a pressure of oxygen of 377 mm.
no reaction occurred, at 202 mm. it went forward very slowly.

with

The connexion between the pressure


rate

of oxidation

is

of the oxygen, and the

represented graphically in curve I

(fig.

23),

Setting out from the pressure of 200 mm., the velocity of the
reaction

without

appears

to increase

reaching

continuously

maximum

value

as

as the pressure falls,


is

the

case

when

the

gas is moist. (Compare the curve in fig. 22).


Curve II represents the rate of oxidation in dry oxygen when

Fig. 23.

the rate of evaporation of the phosphorus

is

constant.

It is

ob-

used in drawing curve I by the


by dividing
corresponding values of the rates of evaporation of the phosphorus.
The numbers obtained in this way are very irregular it appears

tained

the

values

however,

that

the

rate

of

oxidation between

and 70

proportional to the square root of the pressure of the

We

may

therefore write:

(3)

mm.

is

oxygen.

OXIDATION OF SULPHUR.

After

we

a series, and integrating,

the

logarithm in
small
terms
neglecting

expanding

obtain

69

The
the

values

at higher pressures

The

of

coating
therefore

due,

oxide

in

at

part

any

to

rate,

oxygen

is

the

We may

of evaporation of the phosphorus

rate

it

is

oxidised by dry

proportional to the square root of the pressure of the

This

mm., above
It is

70

the deposition of a

surface of the phosphorus.

being supposed constant, the rate at which

latter.

from

they decrease.

on the

that,

say,

this equation

of the results obtained in these experiments

irregularity

probably

by means of

calculated

remain approximately constant below 60

experiments,

mm.,
is

of Iq

is

only

true

(at

20) up

to a pressure of

6070

this pressure the velocity is smaller.

of interest that the

maximum

velocity of oxidation

at

constant rate of evaporation of the phosphorus


occurs at a pressure of y io atmosphere; this pressure is also the most favourable
to the reaction between phosphine and oxygen (p. 60).

SULPHUR.

II.

As we have
the

surface

of

study

of

the

takes place

seen, the deposition of

the
rate

phosphorus

phosphorus pentoxide on

introduces

a difficulty into the

of oxidation of this substance.

more regularly when sulphur

is

The

process

used as the oxidis-

able substance, because the product of the reaction

is

volatile.

The apparatus shown in figure 24 was used in these experiments by means of it the pressure may be kept constant during
;

measurements, the volume being variable. It consists of a


glass tube S, on which two bulbs are blown, and having a capacity
of 60
70 cc. One bulb, S, contains 1 2 grams of sulphur,
the

the

other

about

160

6 grams of soda-lime.
is

maintained

constant temperature of

immersing the apparatus in the


which is contained in the flask.

by

vapour of boiling turpentine,

The measuring tube

is

graduated in Vm

cc.,

and contains

70

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

mercury the
reservoir

ing

B.

level

of which

a three

is

bromnaphthalene

may

way

be adjusted by means of the

tap,

a small

which allows the pressure

the apparatus to the left of

to be

made equal

gauge containin the part of


to that in the

bottle F.

By means of the tap E, these two parts of the apparatus


be put in communication with each other.

may

Fig. 24.

The

which serves to keep the pressure constant,


communication with the manometer Gr and with an air pump.
The part of the apparatus which is seen in the figure to the
reservoir F,

is in

D, was first filled with oxygen at a somewhat greater


pressure than that existing in F, the tap E opened for a moment
to equalise the pressure on both sides of D, and the position of
the mercury in A read off. By raising B it is easy to maintain
left

of

the pressure constant, and equal to that in F.

The diminution
standard

pressure,

of volume per minute,


is

then

proportional

when reduced
to

to

some

the velocity of the

reaction.

When

the velocity has become constant, the pressure in

is

RATE OF OXIDATION OF SULPHUR


the

reduced,

further readings

The following
In

Av
it

At

tap

is

71

opened to equalise the pressure again, and

made

new

at the

pressure.

table contains the results.

diminution

the

of the

volume per minute, the

volume being measured at pressure P.


is

the

rate

of

dt

pressure

819.7 mm. ; and

is

Pressure
P.

of

the

volume,

calculated for a

is
proportional to the quantity
converted into sulphur dioxide per minute,
to the rate of the reaction.

of

of oxygen which

that

change

is

72

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

while k

by the formula

calculated

is

As the

table

shows,

the

experimental

results

are in

much

better agreement with the first of these equations, in which the


rate of oxidation

than

pressure,

is

proportional to the square root of the


the second, in which it is supposed to be

put

with

proportional to the pressure itself.

10

WO

200

C)OO

8OO

Pressure.
Fig. 25.

The curves

in

rate of oxidation

Curve

fig.

25

represent the connexion between the

and the pressure.

drawn with the values of -=~

I is

dt

of the

as

pressure

blance

to

oxygen,

that

It

and those

has a strong general resem-

which was obtained with phosphorus and dried

23);

(fig.

abscissae

as ordinates,

in

both

cases,

the velocity increases contin-

uously as the pressure falls.

Curve II
roots

of

is

the

drawn with ordinates proportional to the square


The experimental values
corresponding pressures.

of the velocity of oxidation corrected for the rate of evaporation

73

OXIDATION OF ALDEHYDE.

by

figure

The

dv-

of the sulphur, viz.

at

log

Jr

are represented in the

pi

circles.

theoretical curve represents these points with fair approxi-

mation.
It

that the whole curve here, up to 800 mm.,

of interest

is

corresponds

the

to

oxygen between

of the curve for phosphorus and dried

part

and 70 mm.

Whether

maximum

velocity

was observed with phosphorus and oxygen, occurs also


with sulphur and oxygen at higher pressures, must be decided by
such

as

further experiments.

ALDEHYDE.

III.

or

In experiments with solid or liquid bodies, such as phosphorus


melted sulphur, the rate of evaporation has such a great

on the velocity of the oxidation, that it is not easy


determine with perfect certainty what influence the concentration of the oxygen has upon it.
influence

to

It

appears,

however,

from

the

foregoing experiments, very


probable that the rate of oxidation in dried oxygen is proportional
to the square root of its pressure.
In order to further test the
truth

of

this

result,

experiments

were made with oxygen and

aldehyde-vapour.

The
at

reaction

20.

It

was found

take place with convenient speed

to

was assumed that aldehyde-vapour

at

20, and under

pressures which do not exceed about 550 mm., may be considered,

with sufficient approximation, as a perfect gas.


Numerous attempts were made to absorb

the

acetic

acid

formed, by means of some solid substance without action on


aldehyde; Pb 0, ZnO, BaC0 3 anhydrous KC 2 H 3 2 were tried,
but all produced a more or less rapid diminution in the quantity
,

The experiments were therefore made


aldehyde-vapour.
without any such absorbent, and by means of apparatus similar

of

to that represented in fig.


1

Compare

fig.

23 on page 68.

14, p. 41.

74

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

The
kept

60

takes

oxidation
at

70

place

in

bulb

the

constant temperature in a thermostat;

The

cc.

is

its

volume

is

determined by means of
or
lowering the tube C, the
raising

pressure of the gas

BCD. By

the manometer

which

26),

(fig.

is

the

of

level

always brought

before a reading

The

mark

is

made.

BD, may then

pressure,

measured

be

is

mercury
to the

on

vertical

millimeter scale or by means

CD

of a cathetometer.

is

barometer dipping below the


at

mercury

serves

the air-trap

retain

to

which

bubbles

any

air

may

leak

through between the


and rubber tubes.

glass

By means

of the three-way

the apparatus may be


connected either with an air-

tap

pump through

Fig. 26.

F,

or with a

vessel containing liquid


the lower limb of the tap.

little

aldehyde, G, which

is

ground

to

fit

admitted by putting the apparatus evacuated as far as possible - - in communication with the liquid

The aldehyde-vapour

G by

aldehyde in
replaced

is

repeating these operations the air is completely


is then closed, the
The tap
aldehyde-vapour.
;

by

apparatus placed in the thermostat,

G
and

is

then removed,

current

through

F H.

reaction

is

connected up to the oxygen gas holder,


dried over CaCl 2 led for some time

of oxygen,

The tap

and the pressure observed.

then quickly opened to admit the


oxygen to the apparatus, closed again, and the pressure observed.
Further readings are then made from time to time until the
Since

is

ended.

the

gases do not mix immediately, the velocity

is

fre-

quently rather small at the beginning of the reaction.

The

calculation of the rate of oxidation from the experiments,

OXIDATION OF ALDEHYDE.

knowledge of the composition of the gas remaining


the apparatus at the end of an experiment.

requires
in

75

As soon

as

therefore,

the last reading of the pressure had been made,

very

dilute

solution

of caustic potash

used in

was allowed

to flow into

order to be polymerise the aldehyde


the apparatus from a weighed flask.

volume
water
into

of

- -

it,

the

apparatus

and the volume

The

difference

between the

determined by weighing

it

of the caustic potash solution

full

of

drawn

gave the volume of the oxygen and nitrogen contained


The oxygen was absorbed by alkaline pyrogallol *.

in the residue.

The experiments were made in the dark, special experiments


having shown that light has some influence on the velocity of
the reaction.

The following
Time

in

table contains the results,

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

Time

in

OXIDATION OF ALDEHYDE.

order

In

of

quantities

is

it

change,

to

from

calculate,

the

decrease

of

the

pressure,

aldehyde which have undergone the


oxygen
to
take
account of the solvent action of
necessary

and

the liquid acetic acid which

Let

the

77

initial

formed on the aldehyde.


the aldehyde be a mm.,

is

of

pressure

that of

oxygen b mm., and of the nitrogen N mm. Further, call


the total pressure of the gaseous mixture after t minutes have
the

elapsed,

mm.

and suppose that x

mm.

2x

with

of

At

aldehyde.

of oxygen have combined

first

the

acetic

formed

acid

remains in the condition of vapour, and since its density at 20


is double the normal value, we shall have 2 volumes of
aldehyde-

vapour and

volume of oxygen combining

form

to

volume of

acetic acid vapour.

The pressure and volume


same

PO

The pressure
t

of the acetic acid are, therefore, the

oxygen from which

as those of the

of the mixture

\cL

V \_|_/"U
\\j
JL)

therefore

is

v\

v
X

4-

XJ

formed.

is

it

O
v
^i X

o-^-K
a
D

4r XT
IN

_L
i

XT
iM

The pressure at the beginning of the experiment was PI = a + b

+ N,

so that

2 x

After

its

If

acetic

t.

the acetic-acid vapour will attain

its

maximum

mms., after which liquid acetic acid will be deposited,


m.
quantity will be proportional to x

pressure,

and

time

P,

we assume
acid

pressure

the quantity of aldehyde dissolved in the

that

follows

Henry's law, it will be proportional to the


and also to the quantity of liquid

of the aldehyde, p 2

acetic acid.

The pressure of the aldehyde


p 2 -- a

2x

therefore

is

k t (x

m) p 2

or
"

Here,

formation

2 x

of

is

the

2 x
a_j
+ kj (x - - m)'

diminution

of pressure

into

acid,

aldehyde

acetic

kx

due to
(x

the

m) p

trans2,

that

78

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

which

produced by the solution of aldehyde in the liquid

is

acid,

and ki some constant.


If

acid

the

aldehyde-vapour dissolves in acetic


according to Henry's law is not strictly accurate, no great
that

assumption

error will arise, since the quantity dissolved

the

Putting

total

equal

pressure

pressures of the different gases,

Substituting in this

p
From

(b

- -

(b

- x)

x)

pressure

a
-h

obtain,

p2

sum of the

-f

+ N.

2X
r

kx (x

the

when

-'

it

+ m +

becomes

N.

m)

diminution
ki

partial

value of p 2 found above,

the

equation x
may be obtained

this

we

to

small.

is

the

in

known.

is

the

oxygen

The

analysis

gas at the end of an experiment gives an independent


determination of x, from which k : may be found.

of the

The connexion between the


vapour
their

by

and the

oxygen,

partial

trations

of

oxidation

are proportional to the concen-

expressed by the equation

-j

P!

which

pressures,

is

of aldehyde
concentrations of the gases - - or
rate

p2

kpi

(A)

is the partial pressure of the oxygen, p 2 that of the aldehyde.


In order to integrate this equation, substitute (see p. 77)

a
P2

dpi

'-

kl (x

-r^)

Pl

dT

This gives

dx

V,

IT
from which we obtain,

x)

after

2 x

kl

(x

nffl

performing the integration,

dx

IT

UNT
OXIDATION OF ALDEHYDE.

79
'/ 2

2 kj

ki a

-TT-

Vs

1
-

-4-

_/2b-

x) 4- const.

kj (b

(B)

The value of
= 0, when t

the constant

obtained from the condition that

is

0.

when

This form of the equation can only be used


is

(2

a)

positive.

When

and (2 b - - a) is therefore
negative, the integrated equation may be transformed into
k

excess of aldehyde

k ia

1 2 kirn
'

'

/o_9K\V,

The values of k

is

used,

(b

xY/2

/o

9MV.

tan

in the tables

on

pp..

75

means of equations B and C. They show


pressure of 450 mm., these equations are
experimental

" X) +

1
t"

(b

C nSt

6 are calculated
that,

in

up

to an

by

oxygen

harmony with the

results.

When the partial pressure of the oxygen is higher than about


450 mm., however, the values of k decrease. This appears to point
to the existence of an upper limit of pressure, above which the reacforward with a velocity very
smaller than that which would be deduced from equation A.
a matter of fact, no oxidation took place when the

tion either stops altogether, or goes

much
As

pressure of the oxygen exceeded 530 mm., as

may

be seen from

the numbers tabulated.

The experiments show,


vapour by

therefore, that the oxidation of aldehyde

oxygen takes place with a velocity which

is
proportional
of the aldehyde-vapour and to the square root
of the pressure of the oxygen, and further that there is
probably

to

the

pressure

a certain pressure of the

place more slowly,

As we have already
molecular reaction

oxygen above which the reaction takes

about 450

of mercury at

20.

seen on page 19, the velocity of a poly-

may be

_^l

mm.

expressed as follows,

k Cl

(D)

(C)

80

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

where

and

numbers

the

are

the

of

molecules

taking part in the reaction.


that the values of
and n

99,

p.

we have

-r

later,

be calculated from

may

-~

proportional to

(page 78). GI

dt

(it

tional to the pressure of the aldehyde,

C2

It
Comparing

with equation

this

m =

1,

is

propor-

to that of the oxygen.

we

these substitutions in equation D,

dpi

obtain

kp2 Pl

we

and n

'

find
1/2,

the reaction takes place between aldehyde molecules and

is

oxygen atoms, and

is,

to be written in the following

C 2 EU

The

of

between aldehyde and oxygen,

to the reaction

this

Applying

exists

kinds

shown

unknown.

they are

that

be

of the velocity of the reaction in cases in which

measurements

Making

different

It will

C2

supposition that a certain small

normally

in

knowledge of the

oxygen

gas,

in

is

H4

way

2.

number of oxygen atoms

accordance with our present

subject.

The mathematical theory of reactions between


is also
was published in 1884 by J. J. THOMSON

gases,

which

in agreement
with the results obtained with aldehyde and oxygen.
It is probable,
on other grounds, that oxygen gas contains
,

free

atoms;

there can be

little

doubt that the oxygen molecule

high temperature, be dissociated into its


between the dissociated and undissociated

at a sufficiently

would,

atoms.
Equilibrium
molecules will be established

when

the concentration of the atoms

has reached a value determined by the equation


C( 02

where

C( 02

is
)

the

Phil.

This

Mag.
is

(5),

C<o),

of the oxygen molecules, C(


k a constant the value of which depends

concentration

that of the atoms, and

on the temperature

2
.

18, 233, 1884.

treated fully further on.

EXISTENCE OF FREE ATOMS IN OXYGEN GAS.

the heat of formation of the oxygen molecule from

Since

atoms
such a

that at lower temperatures the concentration of the

way

atoms

oxygen

its

probably positive, the equilibrium well be displaced, in

is

than at higher temperatures. It


never become zero, and we shall have

will be smaller

however,

will,

81

probably

therefore at the ordinary temperature

C (02

We

take

may

the

concentration

).

of the oxygen molecules as

being proportional to the pressure of the gas; the concentration


of the oxygen atoms

is

therefore proportional to the square root

of the pressure.

we assume

If

of

oxidation

that the oxygen atoms alone take part in the

the

the

aldehyde,

rate of oxidation

must also be

proportional to the square root of the

Although the

oxygen pressure.
with aldehyde may be explained
whether this is also the case with

results obtained

way, it is doubtful
phosphorus and sulphur.
in

this

It is possible that

the reaction between oxygen and phosphorus

or sulphur takes place in different stages, for example,

= P

P4 +
The

'.

velocity of each of these partial processes


to

proportional

the

concentration

of the

would then be
This

oxygen atoms.

agreement with the fact that when phosphorus


burnt with a limited supply of oxygen, the lower oxides,

view
is

also in

is

such as

The

PA,

are formed.

fact that the presence of moisture accelerates the oxidation

of phosphorus and sulphur

the

that
J.

J.

oxidation

THOMSON

electrodes)

is

has

passes

is

also in accordance with the view

due to the action of oxygen atoms,

found

that

much more

the
easily

through

the moist, than

through the dry gas; the moisture apparently favours


formation of the atoms which carry the electricity.
1

the
2
3

for

electric discharge (without

the

of this oxide, discovered by LE VERRIER, is rendered probable by


REINIZER and GOLDSCHMIDT (Berichte 13. p. 845. 1880).
Compare the experiments of BAKER and of DEWAR. See also page 33.

The
work

existence

of

British Association, Oxford, 1894.


6

82

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

It must, however, be pointed out that the above hypothesis


does not explain the formation of ozone which accompanies the

of

oxidation

phosphorus,

not

only

oxygen but

moist

in

also,

according to MARCHAND, in the dry gas.

We
part

far,

always spoken of oxygen atoms as taking

is

here

question, however,

with atoms,

with positively or negatively charged atoms.

has investigated this question.


According to the commonly

view

received

or with ions,

VAN

on

'T

HOFF

the subject,

half of the oxygen molecule

one

slow

the

in

The

the oxidation of aldehyde, etc.

whether we are dealing

arises

that

so

have,

in

oxidation,

while

may be regarded as employed


the other half brings about the

formation of ozone.

E WAN'S

From
oxidation

is

proportional

the oxygen,

molecule

is

previous to
If

we

experiments,

it

if

that

dissociation -of the

kind

rate

of

oxygen
it

exists

it.

are really dealing with the equilibrium

of

2 0,

atoms are oppositely charged,

the

the

not a consequence of the oxidation, but that

the oxidisable

one

show

to the square root of the pressure of

would follow that the

and

which

it

is

conceivable that

should show preference for those with


the remainder giving an electrical charge

substance
charge,

oxygen which

is
finally removed by some secondary
such
as
the
formation
of ozone, or the decolonisation
reaction

the

to

of indigo.

Some

indications that this

may

be the case are to be found in

literature of the subject.


The white fumes formed during
the oxidation of phosphorus, for example, are due chiefly to the
condensation of steam, and persist in air which, after being in

the

contact with phosphorus, has been freed from ozone by means of


3

potassium iodide.
They therefore, resemble the cloudiness which
was observed by R. v. HELMHOLTZ in electrified steam. 4
Chem.

Zeit. phys.

The meaning

MEISSNER, Untevsuchungen iiber den Sauerstoff. 1863, 20, 218.


Wied Ann. 32, 1, 1887; also MEISSNER, loc. cit.

16, 411. 1895.

of equations written in this

way

is

explained later.

83

We

oxygen made active by contact with

shall also see that in

phosphorus the primary product

not ozone,

is

because

the luminosity of phosphorus, while ozone favours

it

stops

it;

it

might

be electrically charged oxygen.

The maximum quantity


actions which accompany
order

in

to

was

first

determined,

with the quantity of oxygen employed

it

compare

of oxygen taking part in the secondary


a slow oxidation

in the oxidation itself.

The determinations of SCHONBEIN

2
,

and LEEDS

give very different

results.

SCHONBEIN'S

method was modified,


the

in

determinations,

in

of indigo,

dilute solution

way:

following

phosphorus was placed

so as to allow of quantitative

large

either

small

flask together

stick

of

with a very

as indigo sulphate, or as

com-

sodium sulphindigotate, the oxidation value of which


been determined by means of a standard permanganate

mercial

had

solution by SKALWEIT'S
It

was found

in

essential

absolutely

method.

some preliminary

experiments that
use small quantities of phosphorus, and that

to

necessary

to

the

keep

temperature

it

it

is

is

low during the

oxidation (40), and to shake the flask vigorously.


21.3 mgrs. of phosphorus were used; to obtain such quantities
easily, the phosphorus was cast in thin sticks about 1 mm. in

diameter

by

drawing

it

up while melted

into a thick walled

glass tube.

These sticks were easily removed from the tube, after which
they were cut into pieces of known length by bringing them into
a short piece of the same tube, which had been ground flat at
both ends, and cutting off the projecting parts with a knife.
First experiment.
60 cc. of indigo solution, to which 10

cc.

of sulphuric acid had been added, were shaken with 21.3 mgrs.
of

phosphorus

disappeared.

3
4

It

phosphorus had
was then found that an equal volume of the

and

excess

of

air,

Chim. 35, 419, 1881.


Journ. prakt. Chem. 53, 501, 1851.
LIEB., Ann. 200, 295, 1880.
CHAPPUIS, Bull. Soc

Eepertorium der analyt. Chemie.

4,

247.

until

the

84

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

was brought

same greenish tint as that


with 79.5 cc. permantreatment
experiment by

solution

indigo

acquired in the

to the

ganate solution, (0.00987 N).


During the oxidation of 21.3 mgrs. of phosphorus, therefore,
79.5
6.28 mgrs. of oxygen had taken part
0.00987
8

in

00. 57
secondary reaction. The atomic ratio is thus P
Second experiment. This was carried out in a similar way,

the

phosphorus was

the

except

that

parts.

The 60

cc.

introduced

solution

of indigo

of oxygen

or

Oo. 6

gradually in four

were now almost com-

pletely decolourised, loosing the green tinge.

mgrs.

1-H =6.66

were therefore used in the secondary reaction,

In some further experiments without sulphuric acid it was


noticed that the acid accelerates the reaction considerably, the
ratio

between the phosphorus and the oxygen, however, remained

unchanged.
dark so as

final series of

avoid

to

the

experiments was

possible

oxidation

now made
of indigo

by the
and the

Sodium sulphindigotate was used,


of the phosphorus conducted in a special way.

of the light.

action

in the

slow combustion

The phosphorus was brought into a condition of fine division


in the same way as in the earlier experiments, by warming the
phosphorus melted, and then shaking it thoroughly.
From this point the experiment was conducted in a somewhat

flask until the

way, because

different

took place
escence

is

in

two

first

it

was seen

different stages.

seen;

product formed in

phosphoric

this

stage

in the

dark that the oxidation

The well known phosphoracid

is

when such

practically

small

the only
of

quantities

phosphorus are employed. Secondly, if the particles of phosphorus


are completely covered by the liquid, luminosity is seen throughout the whole flask, and phosphorous acid is also formed.
To give an example, the flask was placed in water at

taken out and shaken


the

water,

after

this

50,

well about thirty times, and replaced in

the

luminosity was seen.

On

repeating

these operations the same results were obtained.

9.18 mgrs. of phosphorus were used, and after 277 repetitions


1

10

0;009S7

cc.

of this
1.11

indigo

solution

mgrs. oxygen.

required

14.1

cc.

permanganate, or 14.1

FORMATION OF OZONE BY SLOW OXIDATION.

85

of the shaking and luminosity, 40 cc. of indigo solution had been

on

decolourised;

were

indigo

the

in

standing

cold

an

additional

cc.

of

and the phosphorus totally

gradually decolourised,

disappeared.

50

of the indigo solution were equivalent to 40.73 cc. of

cc.

0.00987

oxygen

used

permanganate

and oxygen

active

The

ratio

the
is

of

quantity

44

^7

between phosphorus

.e-

when an atom

of phosphorus

is

converts approximately half an atom of oxygen into

it

independently of whether phosphorous or


formed.

condition,

phosphoric acid

and

thus

is

of indigo

cc.

The

2.83 mgrs.

therefore probable that

is

oxidised,

the

0.00987

It

decolourising 44

in

that

so

solution,

is

between the quantity of oxygen actually found


appears to be real, and may be due to the fact that

difference

0.5

phosphorus appears to take place in two


and chiefly, with formation of phosphorous
and phosphoric acids, and secondly, to the extent of about 15
per cent according to SALZER, with formation of hypophosphoric
the

acid;

it

is

first

perhaps

amount of

larger
It

of

oxidation

directions,

also

may

possible

active oxygen.

be

pointed out here that in the oxidation of


The
does not appear to be formed at first.

phosphorus, ozone
luminous phenomena just
present

the

in

oxidation

of

atmosphere

the

sufficient quantity,

since

that the latter process produces a

described
of

the

show that something was


flask

which prevented the

phosphorus; oxygen was obviously present in


and there was no lack of phosphorus vapour

flask phosphorescence was seen in contact


The experiments of CHAPPUIS show that ozone

on opening the

with the

air.

promotes the phosphorescence.


This inhibitory action, which

may

be

due

to

the electric

charge, or to the excess of positive or of negative oxygen ions,

removed by shaking with indigo solution, in which process


sulphuric acid has a marked accelerative effect, possibly on

is

account of

That the

its

conductivity.

effect of

the shaking,

viz.,

rendering possible a renewed

8b

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

appearance of the phosphorescence, is not due merely to a


is
renewed saturation of the air with phosphorus vapour
,

by

proved
not

the

fact

that

the characteristic phosphorescence

when phosphorus,

seen

and water

air,

alone

are

is

used,

without indigo.
It

also

is

to

be

noticed

the

that

substance exercising the

gradually when the flask


is
not shaken, so that a spontaneous outburst of luminosity
In this
appears, which is repeated at intervals of a few hours.
which
intermittent
was
noticed
the
by
phosphorescence
way
action

inhibitory

JOUBERT

may be

disappears

very

explained.

Chapter

III.

Elimination of the disturbing actions.


I.

METHODS

FORM AND

OF ELIMINATING THE DISTURBING ACTIONS.

DIMENSIONS OF THE APPARATUS.

USE

OF A SOLVENT.

MOISTENING THE WALLS OF THE VESSEL.

The

object of the preceding studies

was not only the discovery

of the disturbing actions but also their elimination.

The secondary actions which have been examined may now


be enumerated together with the methods which may be adopted
in order to avoid them.
These methods will then be more
fully explained.

Disturbing actions.

The
The

1.

2.

influence of the
effect of a

volume of the bodies undergoing change.

change in the nature of the medium during

the reaction.

The
The

3.

influence of the walls of the apparatus.

of changes in
occurring during the reaction.

4.

influence

See note

p.

the

walls

of

the

apparatus

52.

[Also BAKER, Phil. Trans. 1888, p. 583;


p. 569, 1890. T. E.]

THORPE and TUTTON, Chem.

Soc. Journ.

THEIR ELIMINATION.

Methods of eliminating

the disturbing actions.

1.

Form and

2.

Use of a

3.

Moistening the walls of the vessel.


1.

will

dimensions of the apparatus.


solvent.

Form and

dimensions of the apparatus.

which

connected with the walls of the vessel

action

Any

87

evidently

be

is

diminished

in

intensity

by diminishing the

internal surface of the apparatus, and therefore, also


its

by increasing

volume.

By

using

of considerable diameter, both the

flasks

spherical

influence of the walls on the reaction,

and the

effect

which the

reaction frequently exerts on the walls, will be diminished.

Use of a solvent.

2.

One of the most important


through a

is

take part in the change.


a "solvent", although it

gaseous system

conditions for obtaining the normal

that the reacting substances be distributed


large excess of some substance which does not itself

of change,

course

We

will call a substance of this kind

may

be a gas

when

a reaction in a

under consideration.

is

solvent of this kind serves several different ends.

First,

its

by

we

use

obtain

necessary in order to reduce

the

dilution

which

is

often

the influence of the volume of the

reacting substances to a negligible quantity, secondly, the change


in the nature of the medium which is caused by the accumulation
of the products

of the

reaction

is

diminished by the presence

of the solvent.

Further,

special

experiments

have shown that the influence

of the three other disturbing actions which have been mentioned


is
it

reduced to a great extent by the use of a solvent,


is not totally eliminated.

although

most prominent in gaseous


of a solvent on them was studied in such

Since

the

disturbing

systems,

the

effect

actions

are

systems.
In

order

to

prove

that the effect of the walls of the vessel

88

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

by the addition of a solvent gas, the apparatus


represented on p. 44 was used by means of it the ratio between
the rates of polymerisation of cyanic acid in the two divisions
diminished

is

and

can be determined

when
when

1,

2,
1

the acid
it

alone present,

is

mixed with excess of dry

is

air.

Cyanic acid alone.

....

209.9 in A, 210.3 in B.
Initial pressure
Pressure after 19 hours 190.0 in A, 198.0 in B.
Ratio between the velocities in A and B: -- 1.6
:

2.

Cyanic acid

ivitli

an

excess of

dry

1.

air.

677.2 in A and B.
Initial pressure
Pressure after 41 hours 661.5 in A, 662.9 in B.
.

Ratio of the velocities in

From

numbers

these

it

towards the same value;

which the

difference

the addition of
In order to

the

in

1.1

1.

be seen that the velocities tend

will

that

and B:

is,

the influence of the walls, to

velocities is due,

diminished by

is

air.

show that

which the

the effect of the changes

ivalls

vessel undergo is diminished by the presence of a solvent


a
similar
series of experiments was made with the apparatus
gas,

of the

shown

in fig. 7,

page 34.

depositing a coating of cyamelide on the wall of B,


the ratio of the rates of polymerisation of cyanic acid in A and B,

After

was determined,
1,

2,
1.

when
when

the acid alone was present,


it

was mixed with an excess of dry

air.

Cyanic acid alone.

89.8 in

Initial pressure

and B.

88
in A, 85.3 in B.
Pressure after 3 days
1
Ratio between the velocities in A and in B 2.5.
.

2.

Cyanic acid after addition of dry air.


Initial pressure
542.3 in

and B.

532.4 in A, 529.3 in B.
Pressure after 15 days.
1
Ratio of the velocities in A and in B
1.3.
.

89

MOISTENING THE WALLS.

Cyanic acid alone.

3.

77.4 in A, 79.4 in B.

Initial pressure

Pressure after three days 74.5 in A, 71.6 in B.


2.7.
Ratio of the velocities in A and in B - - 1
:

Here,

the

also,

velocities

tend towards the same value; that

of the deposit of cyamelide, which accelerates


diminished
the change,
by the addition of air. The explanation
of the action of the solvent gas is to be found in the formation

the

is,

influence
is

layer of

of a protecting

The change, which

near the walls.

it

occurs most rapidly in the neighbourhood of the walls, removes


the cyanic acid from the gaseous mixture existing there, so that
of

influence

the

cannot be exerted until the cyanic

walls

the

acid has been replaced

by

diffusion in the layer of gas in contact

with them.
Moistening the walls.

3.

This

the

diminishes

artifice

influence

of the deposits which

changes in a very remarkable way; by


become
acquainted with the surprising magnitude
using
of the disturbing actions which come into play in these reactions.
The apparatus shown in fig. 7, p. 34, was also used in this

formed

are

it

we

certain

in

shall

The walls

case.

of

of the two divisions,

one

for example,

were covered internally with a coating of valvolin. The effect


of this coating on the rate of formation of ammonium carbamate
and of trioxymethylene was then investigated.

The

of

manipulation

the

already described, so that


is

an enormous difference

the two

The

owing

divisions,

velocity in B,

greater

than

that

it

experiment
is

is

the

same

as

that

only necessary to say that there

between the rates of the reaction


to

in

the influence of the liquid coating.

the walls of which were not moistened, was


in

A,

both

with

the

carbamate and with

trioxymethylene, the ratios of the velocities being 6:1, and


16
1.
This difference shows, therefore, that moistening the
:

walls

diminishes

the

accelerative

carbamate and of trioxymethylene.


that

the pores

liquid.

influence

of the

The reason

of this

deposits of
is

probably

of the substances deposited are filled up

by the

90

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

must

It

the

must be

be pointed out that special care is required in


it
liquid with which the walls are covered

also

of

choice

viscid,

the

have a very small vapour pressure, and dissolve

the reacting gases as sparingly as possible.

The question now

whether

arises,

normal course of the reaction

it

is

possible to realise the

in the different cases

which have

been considered, by making use of the methods which have been


described for eliminating the disturbing actions.

In answering this question,


between reactions taking place

it

is

necessary to differentiate
and those taking place

in liquids,

in gaseous systems.

In

liquid

certainly

But

the

in

the

systems,
to

suffice

use of a solvent in large excess does


eliminate the disturbing actions.

practically

case of gases, a gaseous solvent cannot be used to

the same extent, because great difficulties are introduced by the


large volume needed.

As we

shall see, however,

normal course of the reaction

The

is

it

has proved possible to realise the

in several cases.

found in those cases in which the

greatest difficulty
gases undergo a change which produces a deposit on the walls
of the vessel which increases in quantity as the reaction progresses.

How

this

difficulty

is

subsequent chapter; here,


even

rable

in

conditions

the

than

with

be

avoided

will

be

we may remark

that

it is

to

shown

in

very conside-

systems where, as we have already seen,


much more favourable to a normal course

liquid

are

gases.

The following experiments may be mentioned

as yielding additional evidence in support of this.

URECH

while

*,

studying the action of FEHLING'S solution on


found that the velocity of the change increased in

invert sugar,

a curious

he

used,

the

first

observed,
larities

way when

in

were

although in a lesser degree, all the irregubeen described in the polymerisation of


and which are due to the accelerative action of the
short,

which have

cyanic acid,
1

vessels with a larger internal surface

noticed that the rate of change increased during


period of the reaction reaching a maximum value, he
also

Berichte, 15, 2687, 1882.

CHEMICAL INDUCTION OR INITIAL ACCELERATION.

91

This indicates that the phenomena observed


by URECH had a similar cause, namely, the formation of cuprous
deposit of cyamelide.

oxide.

This

who

experiment

should

serve

a warning to investigators

as

are engaged with the study of reactions in gaseous systems

whenever a deposit of a

solid

substance which accelerates the

is formed,
the difficulties to be expected are such that
even under the favourable conditions existing in liquids, considerable irregularities may be found.

reaction

THE FIRST PERIOD OF CHEMICAL CHANGE.

II.

Chemical induction.

The

period of a chemical change

first

chemical

An

dynamics.

frequently

encountered

in

exceedingly
viz. the
it,

is

of special interest in

curious

phenomenon

velocity

of the reaction

increases during this period, finally attaining a

The names "chemical induction

and

',

have been given to this phenomenon.


Since an acceleration of this kind

is

maximum

is

value.

"initial acceleration"

incompatible with the

views which have been put forward in this book, it was submitted
to experimental examination. This showed that the cause of the

found in the disturbing actions which have


It showed also what importance must
already been mentioned.
be attached to the occurrence of an initial acceleration in studies

phenomenon

is

to be

of this kind.

The

existence

of an

initial acceleration is established

by the

following observations.
1.
is

BUNSEN and ROSCOE, to

due,

mixture

observed
of

the

chlorine

whom the term

acceleration

and

hydrogen

in

to

"

chemical induction"

question
light.

on
In

exposing a
one of their

92

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

the quantity of change in the eighth minute


ten times that which occurred in the first.

experiments

was

They observed
on tartaric
with

and expressed themselves

being excluded,

the

to

regard

in

phenomenon

the

in

general

follow-

ing way:

"The

a similar acceleration of the action of bromine

acid, light

occurrence of such

depend, not

some

on

maximum

appears, therefore, to

special peculiarity in the action of light,

but on the mode of action of the force of

BAEYEE

affinity itself."

BUNSEN'S laboratory, found another


instance of chemical induction in the action of bromine on lactic
2.

in

working

acid in presence of hydrobromic acid.

WEIGHT, LUFF, and RENNIE

3.

again, found the

menon while studying the reduction

of certain

same pheno-

metallic oxides

by hydrogen and carbon monoxide; they say:

"In

all

be

to

cases for a length of time the action

almost

is

or quite imperceptible; after which

an accelerating

rate

maximum

until

rate

is

it

so slight

as

goes on

at

attained,

when

again diminishes .... it is evidently a case of the chemical


induction studied by BUNSEN and ROSCOE."
it

4.

and

The expression
PEAN

DE

etherification

SAINT

and

"initial acceleration

GILLES

they

considered

it

to

1 '

noticed

be

is

due to BEETHELOT

it

in the process of

of a specific character.

They say:
"Pour concevoir

1'acceleration

initiale

il

faut

admettre une

sorte d'inertie, de resistance a vaincre qui retard la combinaison

dans

les

POGG.

premiers instants."

Ann.

100,

488, 1857.

OSTW AID'S

Klassiker der exacten Wissenschaften,

34, p. 93.
2

POGG. Ann. 100, 513, 1855.

LIEB. Ann. 103, 178, 1857.

Journ. Chem. Soc. 1879, 495.

Ann. Chim. Phys.

(3) 66,

OSTWALD'S Klassiker. 34,

26, 1862.

p.

93.

93

INITIAL ACCELERATION.

More

recently

made

MENSCHUTKIN

similar observations on the

formation of acetanilide, and says: "


find here a phenomenon similar to the acceleration of the

We

PEAN

and

which BERTHELOT

etherification

DE SAINT GILLES have

observed."

In the course of his researches on tertiary amylacetate he met


"

with the same phenomenon again.


The examples cited have caused

the

phenomenon of

initial

acceleration to be regarded as a characteristic feature of chemical

change.

Another interpretation of these phenomena may however, be


;

they may be regarded as due to secondary actions.


BUNSEN and ROSCOE found a sufficient explanation of the acceler-

given

ation observed in the action of light on mixtures of chlorine and

hydrogen, in the fact that the light, when it is absorbed by the


mixture of chlorine and hydrogen, brings about what might be

which does not produce


has reached a certain magnitude.
however, of their observation that a similar

called a "dislocation" of the molecules,

chemical change until


In

consequence,

it

phenomenon occurs with tartaric acid when light is excluded,


they expressed the view which has already been quoted.
3

HARCOURT and ESSON


observed

having

an

appear to incline to the opposite opinion


of the reaction between
;

initial acceleration

potassium permanganate and oxalic acid in the presence of sulphuric


acid and manganese sulphate, they considered it to be due to a
secondary

action,

and found that

reaction taking place in the

and

Mn0

the

acceleration

which

enters

into

the second reaction which


this

the

is

2,

actually observed and which

hardly surprising, since the


second reaction is a product of
is

first.

Berichte, 15, 1616, 1882.

Berichte,

two stages
2

It is

also

really the case, the

KMn0 4 + 3 MnS0 4 + 2 H = K S0 4 + 2 H S0 4 + 5 Mn0


Mn0 + H S0 4 + H C 4 = MnS0 + 2 H
+ 2 C0

exhibits

the

was

this

SPRING on

15,

2512,

1882.

KONOWALOW,

this subject. Zeit. phys.

Phil. Trans.

1866, 201.

Chem.

1,

Zeit.

phys.

217, 1887;

Chem.
1,

1,

63, 1887.

468, 1887.

See

94

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

NAUMANN

appears to regard the initial acceleration as


having observed an acceleration in the conversion of
also

secondary
a mixture of ammonia and carbon dioxide into
;

mate he

did not hesitate to ascribe

ammonium carbamate

of the solid

URECH

formed.

of the action of bromine on fatty acids, says

"These

point of view,

if

then

for

AUBEL

maximum

the

beginning of the reaction.


3
SPRING
also found an
solution

would be incomprehensible from a theoretical


the action of the bromine consisted of a simple

results

substitution,

carba-

to the accelerative action

it

having observed the phenomenon in the case

finally,

ammonium

must occur

velocity

at the

1 '

example of chemical induction in the


marble in dilute mineral acids, and SPRING and VAN

of

the

in

another,

action of dilute acids

upon

zinc (con-

taining 0.6 per cent, of lead).

The following experiments were made


cover whether the

initial

to a chemical change, or

acceleration

whether

it

is

in order to dis-

something essential

merely a result of

is

secondary actions.

The experiments were made on


1.
The change of rhombic, into monosymmetric
2.
The formation of water.
3.
The polymerisation of cyanic acid.
The

1.

initial acceleration

sulphur.

of the change of rhombic

sulphur into monosymmetric sulphur.

The experiments were made by

T. L. REICHER

5
,

the

expansion which occurs during the change being measured.


- has
The apparatus used - - a dilatometer
the form of
-

large

quantity

thermometer

(fig.

27)

the

bulb

contains a

of rhombic sulphur together with sufficient sulfill the bulb and part of the

phuric acid (sp. gr. 1.77) to


rig. 27.

capillary

tube,

the

LIBB. Ann. 160, 21. 1876.

Berichte,

Zeit. phys.

8,

4
5

QUOTE'S

was

heated in boiling water.

539, 1875.

Chem.

1,

217, 1887.

1,

465, 1887.

Zeitschrift

Amsterdam 1883,

whole

45.

fur Krystallographie,

8,

593, 1884.

Inaugural Dissertation,

95

INITIAL ACCELERATION.

The expansion produced by the

temperature being at an

rise of

end, a further slow expansion indicates the progress of the change.

The expansions,
as follows

1, 2, 4, 5,

The

11, 13, 15, 18, 17, 17, 16, 14, 12, 9, 7, 5, 4, 3, 2, 1.

8,

velocity of the change therefore increases at

maximum

its

read off every five minutes, were

which were

when approximately one

value

first,

reaching

half of the rhombic


l

sulphur has been converted into the monosymmetric modification.


It has been found that this acceleration is simply due to the

known

well

which

influence

the

of

presence

monosymmetric

sulphur exerts on the change.

formation of water.

Initial acceleration in the

2.

While studying the course of the transformation of electrolytic


in presence of nitrogen, 13.8 cc. of
gas into water at 440
the

into

figure

index

and

hydrogen,

electrolytic

duced

the

apparatus

represented

in

page 39; the mixture of gases was separated by an


from the column of air L, the length of
I,
measured in the way already described, gives the

12,

pressure of the gas which


of

mixture

of

being examined.

Calling the quan-

and

oxygen

at the time

undergone change

46.5 (L t

and

is

hydrogen present at the


of the experiment unity, and the quantity which has

the

beginning

of purified air were intro-

cc.

of

of mercury

which,

tity

32.7

reservoir

being

the

n,

t,

-L =
)

we

"

obtain

20.34 n

t,

of the column of

lengths

beginning of the experiment, and at the time

air,

L, at the

t.

Therefore
1

2.28

1.28.

-Lit

There

is

acetate studied
2

remarkable

similarity

by MENSCIIUTKIN.

See appendix, note 2.

in this respect to the

Berichte,

15, 2512, 1882.

change of tertiary amyl

96

DISTURBING ACTIONS IN GASEOUS SYSTEMS.

The

results are given in the following table.

Time

in hours.

INITIAL ACCELERATION.

The cause

97

of the acceleration in this case

which

was found

in the

formed promotes the change of


the cyanic acid in a very marked way, as we have already seen.
fact that the cyamelide

The following experiment


ation

is

since

it

conditioned

may

be

by

the

produced

is

gives a further proof that the acceler-

change in the walls of the


at

any

period

vessel,

of the change,

and

by any means confined to the initial period. The apparatus shown in fig. 7 was used in the experiment, the reservoir
is

not

B was

filled

pressure

of

with cyanic acid vapour,


the

to time.

Time

in hours.

acid

(at

with mercury, and the

constant volume) measured from time

98

DISTURBING ACTIONS IN

GASEOUS SYSTEMS.

The experiments which have been


ical induction, or initial acceleration,

actions,

ary

and therefore

the

described

may

show that chem-

be referred to second-

phenomenon may be

of service

in investigations relating to chemical dynamics, since it indicates,


in

way which

is

not to be undervalued, that some necessary

precaution has been omitted.

THE COURSE OF CHEMICAL CHANGE.


THIRD PART.

APPLICATIONS.
DETERMINATION OF THE NUMBER OF MOLECULES
WHICH TAKE PART IN A CHEMICAL REACTION.

I.

METHOD

A.

WHICH THE VOLUME KEMAINS CONSTANT.

IN

Decomposition of arsine and phosphine.

The
in

which

in

the

this

which

difference
different

is

found in the course of chemical reactions

numbers of molecules take part may be employed

solution of an interesting problem.

In

the

first

part of

book the course of a reaction was deduced from the number

of molecules taking part in it in this part, inversely, the number


will be determined from the observed course of the reaction.
;

The

principle on

for the

course

of

which the determination depends


a

reaction

is

very simple,

is

represented by

number of molecules taking part

in the reaction,

polymolecular

the equation

^
dt

where n

the

is

and we have to determine

-kC

this quantity experimentally.

Since this can be done in different ways, we shall first develop


those methods which depend on the investigation of the course

of the reaction at constant volume.

The

integrals of the differential equation

given will

be used,

lg
1

The value

Cf. p. 19.

of k

viz

~7T
is

(n

which has just been

or
1)

rt a

times

-i

kt

that which

it

constant,

has in the differential equation.

100

NUMBEK OF MOLECULES TAKING PART

and we

shall

IN A

REACTION.

have to find which of these equations represents

the experimental results.

The decomposition

been investigated with


decide, by experiment, whether this
object.
decomposition really takes place in accordance with the equation
which is usually assumed to represent it, viz. -

We

this

of phosphine

have

has

to

PH =

t GH

P*

2,

whether four molecules of phosphine really produce, by


mutual action, one molecule of phosphorus and six molecules

that

is

their

of hydrogen.

The experiment was made by measuring the


stant
its

pressure, at con-

of a quantity of phosphine at different stages of

volume,

decomposition.

We

have then

where

and

and
the

=
P

same

are

Co (3

pressure

and concentration

initially,

quantities after partial decomposition.

Ct

The

apparatus used was that which is described on page 41, only


in place of the boiling diphenylamine which was used in a
copper bath for maintaining a constant temperature of 310
in

the

on

p.

very similar experiments with arsenic hydride described

2,

sulphur boiling at 440

The following

Time

in

hours.

was employed here.

table contains the results of the experiment.

METHOD AT CONSTANT VOLUME.

The steady

increase of the

numbers given

101
in the last

column

shows that the course of the reaction does not correspond

to the

quadri-molecular equation

^rJ

kfc

const.

-f-

and that the decomposition, therefore,

not represented by the

is

equation

On

H = P +

the other hand the values of

po

log

3~p^~-

t"

pT

are strikingly constant.

From
is

this result

we

are justified in concluding that the change

monomolecular, that

is,

that each molecule of phosphine decom-

poses independently of the others, according to the equation

PH = P +
3

3H,

that the molecules P 4 and


2 are formed subsequently by
the combination of the atoms of phosphorus and hydrogen.

and

II.

DETERMINATION OF THE NUMBER OF MOLECULES


WHICH TAKE PART IN A CHEMICAL REACTION.
B.

METHOD

While the method

of

taking part in a reaction

on

the

volume,

investigation

that

which

IN

WHICH THE VOLUME VARIES.

determining the number of molecules


just been described depends

which has

of the
is

about

course of the reaction at constant


to

be considered depends on the

volume on the velocity of a reaction.


This influence depends on the number of molecules taking part

influence of a change of

102

NUMBER OF MOLECULES TAKING PART

the

in

This

reaction.

a c

is

shown by the
*

IT

k Cl

'

and

equations,

d
'

A REACTION.

IN

IT

therefore,

d C2

dt

dt

or

^1r_^f

log

The

of n from this differential equation cannot,


claim
to
however, lay
any great degree of accuracy.
For if we substitute for the differentials dCi anddC 2 the very
small changes of concentration which take place at the very
calculation

beginning
accurate
due,

of the reactions, for example, the result will be inon account of the magnitude of the experimental error

partly,

measured,

to

the

smallness of the

and partly, to the

initial

changes of concentration

disturbances

to

which the

reactions are subject.


If,

again,

result is
of

the

still

we

substitute

a large change of concentration the

inaccurate, since

reaction,

-Y-,

we assume

implicitly that the rate

remains constant while the concentration

at

undergoes a considerable diminution. This error is partially eliminated owing to the fact that the same assumption is made

with

respect

to both the differentials dC^

ever, difficult to

say to

what extent

and dC 2

this occurs.

It is

it

is,

how-

much better

to deduce the strictly accurate integrated equation,

under certain circumstances,

According to

what

is

it

said

possible to

is

from which,
calculate n exactly.
l

on page 19 we have for an n-

molecular reaction,
d C

am

indebted to Mr. A. A.

different form.

[E. COHEN].

No YES

/>,

of Boston for this calculation in a

somewhat

METHOD AT VARIABLE VOLUME.

103

after integration,

or,

kt

....

'

H- const.

(1)

independent experiments, in which we will call


the concentrations in the first experiment at the times
and similarly, 2 C a and 2 C e the concentrations in the

By making two
iCa and iC e
it a

and

it e ,

second experiment at the times


these

values

into

equation

and

2ta

2 te ,

we

obtain, introducing

and eliminating the integration

(1),

constant,

n-l\

1 \

2^ a

If

now

the

]t a

ti

ti

where

Ce

jt^

and

t2

2ta

change of concentration

is,

2 t e<

both experiments,

in

the same fraction of the initial concentration, that

p
2^a

l^a

is

and therefore,
n

l^e

2^6
,
and
-^-,
2^a

l^a

/ 2

C e\

-^\lW

/2^a\

-^-

\l^a/

equation (2) assumes the following simple form

(n

1) log

&. =
l^a

og

*!.,

*2

and therefore
log

Under

the

this equation
1

conditions

(t t

specified,

t,)

n may

be

calculated

from

with complete accuracy.

k in this equation

is

(n

1)

times greater than

it

is

in the differential equation.

104

NUMBER OF MOLECULES TAKING PART

We

have here a method which

IN

A REACTION.

not merely similar to that


described in the preceding section, but one which is considerably
more simple, and in which the measurements can be made with
is

greater certainty.
The method described in the preceding section becomes valueless
for example, in those
in cases in which disturbing actions occur
;

which

the products of the


the change. If the change be retarded by the products of the reaction, the value obtained for
n will be too great, if it be accelerated, the value found will
so

cases,

observed,

frequently

in

reaction accelerate or retard

be too small.

These

avoided by means of the method in

may be

influences

which the volume

is

variable.

This advantage of the method

is

due to the fact that the same

change of volume produces very different changes in the velocities


of different reactions, according to the number of molecules taking
part in
of

them

volume be doubled, the velocity

for example, if the

mono-molecular reaction

is

reduced to one half, that of a

bimolecular reaction to one fourth that of a trimolecular reaction


to one eighth.

actions

become

The value

No YES and
volume

of this

SCOTT

leads

l
.

to

the

to

owing

Where such
method

method

hydrogen
the

completely

occurrence

by
the

second

inaccurate results,

of disturbing actions,

in

at constant

many

cases,

while the true

while

is

the

reaction

between hydriodic acid and


trimolecular when examined

appears to be
method, a more careful investigation by means of
shows it to be bimolecular. A similar result was

peroxide
first

clearly seen in the researches of

brought to light by the application of


with variable volume. No YES and SCOTT found, for

that

example,

is

They show that the method

nature of the reactions


the

great differences exist the disturbing

less noticeable.

with the action of bromic acid on hydriodic acid


the reaction, which according to the results of the first method
is to be regarded as trimolecular, is really bimolecular.

obtained

Finally, the decomposition of potassium hypoiodite in presence of


/
1

Zeit.

phys.

Chem.

18,

118, 1895.

METHOD AT VARIABLE VOLUME.


a small quantity of iodine, which

means of the

105
l

was studied by SCHWICKER

by

method, and which he considered to be triturns


on examination by the second method to be
out
molecular,
really monomolecular under certain conditions.

The

first

method

with

was

volume

variable

used

also

in

the

investigation of:
1.

2.

3.

The action of bromine on fumaric acid.


The polymerisation of cyanic acid.
The action of stannous chloride on ferric

chloride. (NOYES.)

Action of bromine on fumaric acid.

1.

The formation

of dibromsuccinic acid by the addition of bromine

to fumaric acid in aqueous solution exhibits certain irregularities

which make
the

it

impossible to apply the method at

These

volume.

constant

partial

irregularities are due to

conversion of the dibromsuccinic acid

formed into brommaleic and tartaric

The method

at

acids.

variable

volume, however, at
once yields satisfactory results.
The experiments were made by REICHER by means
of the apparatus
of which

is

contained

acid,

shown

in fig. 28,

the advantage

that the solution of bromine and fumaric


in

cannot

A,

bromine by

lose

evaporation.

The apparatus is completely filled with the


tion, which contains 2 3 grains of fumaric

solu-

acid,

and an equivalent quantity of bromine, per litre


this can be caused to flow out through the tap by
depressing the cylinder B into A, after which a
;

known volume, measured by means

of the small

burette E, can be brought into a solution of pot-

assium

rig. 28.

by

means

system,
1

Zeit.

of

which
phys.

iodide.

The

iodine

sodium thiosulphate,
is

Chem.

to

16,

be

determined,

303, 1895.

the

liberated

is

concentration

titrated

of

the

being proportional to the

106

NUMBER OF MOLECULES TAKING PART

quantity

ments

is

Time

The
of thiosulphate employed.
contained in the following table.

in minutes,
t.

IN A REACTION.

result

of the experi-

METHOD AT VARIABLE VOLUME.

we must expect
from an integer. The
case

this
less

makes

to

find a

result

107

number

obtained,

differing
1

87,

more or

therefore r

permissible to regard the reaction under consideration

it

as bimolecular.

2.

Polymerisation of cyanic acid.

The course of this change, also, exhibits irregularities which


make it impossible to employ the method at constant volume.
The irregularities in this case originate in the accelerative action
of the cyamelide which

We
are

thus

are

opposed here by the greatest

met with

be

to

formed.

is

difficulties

which

in the study of the course of a reaction;

experiments of UKECH, to which reference has already been


made, have shown that the formation of a deposit having an
the

accelerative action on the change


in a

in liquid systems;

deal

the

in

much more
It

is

for

acid,

this

difficulty

becomes very

reason that the question as to the number of

this

of

cyamelide

formed

extending,

with

with

which take part

acid

cyanic

the

five

variable

in the

formation of

of a very protracted research,


over several years and in the course

subject

intervals,

which more than

method

cyanic

serious.

molecules

of

of

case

be very troublesome even


gaseous system, with which we have to

may

hundred experiments were made. The


the advantages of which have

volume,

been pointed out, has to be improved, in this case, by the realisation of a special condition.

This

consists

in

comparing

at very different concentrations,

the

velocities

of

the

reaction,

and in vessels the walls of which

are as far as possible identical.

The experiments may be arranged


a.

The

initial velocities

in three groups, according as r

were compared

in clean vessels.

b.
The velocities were compared in different parts of the
same apparatus, the walls of which were covered by a layer of

cyamelide.

108
c.

NUMBER OF MOLECULES TAKING PART

The

velocities

synopsis of the results

ratus used

No.

is

A REACTION.

were compared in the same

dition of the walls being the

IN

described.

is

same
first

as in

vessel, the con-

b.

given, after which the appa-

METHOD AT VARIABLE VOLUME.


a.

Comparison of

The
the

the initial velocities

109

in perfectly

clean vessels.

object of this part of the investigation being to compare

initial velocities

at different concentrations in vessels of the

same form, the apparatus represented

in fig. 29 was employed.


The lower extremity of the apparatus having been

under mercury, the compartments A and B


were evacuated, and the tap separating them closed.
The division B was then filled with cyanic acid in
placed

the

described on page 38, and the initial velo-

way

city of polymerisation determined.


in the table.)

When

(Experiment

1,

I.

at least half of the cyanic acid

the tap was opened, the apparatus


depressed in the burette so as to transfer the cyanic

had disappeared,
acid
at

and the

to A,

smaller

the

(Experiment,

apparatus.
b.

again determined
concentration which obtained in the
initial velocity

Comparison of the
same apparatus,

of the

1,

II).

Result, n

= 2.9.

velocities in different

parts

the walls being covered

by a

layer of cyamelide.

For this purpose a globe (fig. 8) was used which


was evacuated, and filled with cyanic acid. (Experi-

ment

2,

I.)

The globe was then depressed

Fig. 29.

entered

it

so that the mercury


and doubled the concentration of the cyanic

which the rate of polymerisation was again determined


(Experiment 2, II.) This experiment gave n = 3.3.

acid, after

In

another

kind the apparatus shown in


(with omission of the tap) was used. The cyanic acid
was first contained entirely in the compartment A, the mercury
filling B; then by raising the apparatus the acid was distributed
fig.

of this

experiment

29

through

equally
restored.

The

and

and lead to the value n :=


and

finally

results are given

-r-i are the

mean

2.9.

the

original condition

was

under experiment 3 in the table,


1

values of the

first

and third observations.

110

NUMBER OF MOLECULES TAKING PART

c.

the velocities in the

Comparison of

condition of the walls being the

The apparatus shown

in

fig.

A REACTION.

IN

same apparatus,
same as in b.

was used

the

Both

in this case.

compartments were completely evacuated, and one of them, A,


filled with cyanic acid, the rate of polymerisation of which was
then

determined. (Experiment 4, I.) By raising the apparatus


the cyanic acid was transferred from A to B, and the

half

of

velocity in

again measured.

n obtained was
in

4,

II.)

The value of

2.8.

The experiment was


acid

(Experiment
air

dry

repeated,

one case,

added to the

being

in order to diminish the influence of

cyanic
the walls of the vessel (Experiment 5), in another the further
precaution was taken of keeping the temperature constant by

means of a current of cold water from the water supply which


(Experiment 6.) The results are,

circulated round the vessel A.

2.9 and n

This apparatus
ties in clean

then

vessels,

in

From
3

it
is

also suitable for comparisons of the velociat different concentrations.


in

this

in

way

The

initial velo-

A, (Experiment

7,

after transferring the half of the residual

(Experiment

acid

is

was measured

city

it.

3.

the

7,

Result,

II.)

results

and
into

3.2.

the

obtained,

I.)

acid

mean

value of n found

is

appears very probable that the polymerisation of cyanic


a tri-molecular reaction which takes place according to

the equation

3CNOH =
All

doubt

would be removed,

on the subject

that the experiments on the


cribed on page 89 have

CsNaOgHg.

effect of

if it

shown how very large the disturbing

of the deposit of cyamelide formed during the reaction

3.

The
ferric

The action of stannous chloride on


reaction

which

chloride

has

were not

moistening the walls des-

occurs

been

between

carefully

action

may

be.

ferric chloride.

stannous

investigated

chloride

recently

and

by

A.

NOTES \

A.

taking part in

METHOD AT VARIABLE VOLUME.

Ill

order to determine the

number of molecules

in
it.

According

should be trimolecular.

The data which

+ SnCl 2

2 FeCl 3
it

to the equation

2 FeCl 2

SnCl 4

are contained in the

memoir

referred to will

how the method which was explained


be applied in solving the problem which we are

be used in order to show

on

103

p.

may

considering.

solution of ferric chloride, as neutral as possible,

500

800

was placed

capacity, which stood in a water bath


the temperature of which was maintained constant at 25. The
air in the flasks was first expelled by carbon dioxide. The neutral
in flasks of

stannous

of

solution

cc.

chloride

was then quickly added from a


was noted, and the flasks

pipette with a wide opening, the time

From

shaken.

thorougly

time

to

time

portions

of the liquid

were

removed by means of a pipette and mixed with excess of


mercuric chloride solution, by which means the reaction was
once

at

stopped;

the time

at

which the mixture took place

was noted.

The

ferrous

salt

formed was then titrated by means of N/ 10

potassium bichromate solution, potassium ferricyanide serving as


indicator.

The initial volume of the liquid in which the reaction occurred


was usually 300, sometimes 600 cc., the portion titrated varied,
according to the concentration, from 25 to 100 cc.

The following table


by XOYES. C a is the

contains the experimental results obtained


initial

concentration of the ferric chloride

employed, hi gram equivalents per litre, C a C e gives


number of equivalents of ferric chloride reduced at the time
The times are given in minutes.

solution

the
t.

Zeit phys.

Chem.

16,

546, 1895.

Further proofs that this


original

is

really a trimolecular reaction are to be found in the

memoir.

The concentration of

this solution

and

also that of the solution of ferric chloride

were determined with N/ 10 potassium bichromate solution.


4
The mercuric chloride oxidises the remaining stannous chloride.

112

I.

NUMBER OF MOLECULES TAKING PART

Ca

0.1

IN

A REACTION.

113

RECOGNITION OF MIXTURES.

III.

Decomposition of dibromsuccinic and isodibromsuccinic acids.

A
is

further application of the study of the course of a reaction

to be found in the possibility of determining

by

it

whether a

a single compound or a mixture of isomers.


given
Suppose, for example, that a -monomolecular reaction takes place

substance

in a mixture of

is

two isomeric substances, the course of the reac-

tion will not correspond to the equation

---kC
dt

because, owing to the fact that the substance


will

changes

take

a mixture,

is

two

place simultaneously, in accordance with the

equations

and

_ L?

Supposing we were unaware that we were dealing with a


it would only be possible to take account of the variation
of the total concentration C
C^ + C 2 and it would be found

mixture,

that

did not follow the equation

it

dc --kc

but rather an equation of the form

In order to test this experimentally the course of the change

was investigated in the following three cases


The decomposition of dibromsuccinic acid.
1.
:

The decomposition of isodibromsuccinic acid.


The decomposition of a mixture of the two.

2.

3.

Since
1

both

the

iso-acid

and

its

isomer

split off a

molecule

The two equations give the same result only when k 1 rrk 2 that is when both
decompose at the same rate. No account is taken, in these considerations, of
,

isomers

any catalytic action of the one isomer on the rate of change of the other.
8

114

NUMBER OF MOLECULES TAKING PART

IN

A REACTION.

of hydrobromic acid, the course of the decomposition

was

easily

followed by titrating the aqueous solution of the acid after heating


it in sealed tubes at 50.

The following

table contains the results.

COMPARISON OF THE VELOCITIES OF REACTIONS.

where

to increase

titre

had

reaction

was

titre

unknown time which would be needed

the

is

115

from

to T! and

reckoned

proceeded,

for the

the time during which the


from the time at which the
t

Tj.

we

After eliminating x

find,

2 T!

COMPARISON OF THE VELOCITIES OF DIFFERENT

IV.

REACTIONS.
Hydrolysis of esters by bases.

a.

the

If

it

together

any

the

other

that

should

when

velocity constant

it

is

reactions

will

fulfilled,

are

to

be compared

normal courses,

their

be realised.

obtained

results

hand,

different

essential

is

disturbances,

fulfilled

of

velocities

not

free

If this condition

be

comparable,

from

be not

on the

perfectly definite values of the

k may be obtained.

In order to determine the hydrolysing power of different bases


the

rate

which they bring about hydrolysis has been deterand more recently, and very comprehensively,

at

mined by REICHER,

by OSTWALD.
REICHER'S

apparatus

work was

carried out by the

which have been


be

fully described

method and with the


on page

6.

It will,

give here the rates of hydrolysis of


ethyl acetate which were found when different bases were used.

therefore,

to

sufficient

Hydrolysis of ethyl acetate at


Base.

9. 4.
k

Sodium hydroxide

2.370

Potassium

2.298

Calcium

2.285

Strontium

2.204

Barium

2.144

LIEB. Ann. 228, 275, 1885.

Journ. prakt. Chem.

(2),

35, 112, 1887.

COMPARISON OF THE VELOCITIES OF REACTIONS.

116

The

of the nature of the alcohol and acid forming

influence

The

the ester was also investigated by REICHER in a similar way.

base used was sodium hydroxide.


Influence of the nature of the alcohol.

Temp.

k.

Ester.

3.493

Methyl acetate
Ethyl

2.307

........

Propyl

1.920
1.618

Isobutyl

Isoamyl

1.645

,,

Influence of the nature of the acid.

Temp.

3.204

Ethyl acetate
propionate

2.816

butyrate

1.702

,,

isobutyrate

,,

isovalerate

it

is

0.614
0.830

therefore,

appears,

that the greater the

an ester the smaller

in the molecule of

is

1.731

.......

benzoate
It

14. 4.
k

Ester.

,,

9. 4.

number

of atoms

the velocity with which

hydrolysed.

Hydrolysis of esters by acids.

b.

The
lished

methyl

catalytic action of

OSTWALD'S

by

it

acetate,

the hydrogen ion having been estab-

classical

appeared

researches

on

the

hydrolysis of

to be of interest to investigate the

action of acids on the esters mentioned in the preceding section.

This investigation was carried out by A. DE HEMPTINNE


following way:
Flasks,

in the

capable of containing about

1/2

litre,

were

filled

with

acid and placed in a water bath the temper-

N/io hydrochloric
ature of which was

maintained

constant

at

diminish, as far as possible, the error arising


1

WARDER

Zeit. phys.

found 3.240.

Chem.

13,

561, 1894.

25.

In order to

from the solubility

117

HYDROLYSIS OF ESTERS BY ACIDS.

of the glass, the flasks were previously filled with strong* hydrochloric acid and allowed to stand for several days. That the

was thus reduced

error

to negligible dimensions

was proved by

titrations.

of

quantity
1

such that

ester,
1

or

when

it

was dissolved

in the

more

dilute
necessary
solution would result, was then weighed out in a small tube.

acid,

This

to

/ 20

with

tube,

normal,

the

if

still

was placed

ester,

in

one of the

flasks,

which was then corked up and well shaken, whereupon 50 cc.


of the contents were at once titrated with an approximately

N/ 10 baryta

in

solution;

this

way

the exact quantity of base

required to neutralise the hydrochloric acid was obtained.

50

Since

of the solution were removed for each titration,

cc.

the empty space in the flask increased rapidly


this the contents of the flask were distributed

of smaller flasks of about 60


curely corked up.
in this

way.

At

suitable

this

in order to avoid

among

number

which were then se-

capacity,

Errors arising from evaporation were avoided

50

intervals

were

removed and

purpose;

from the

flasks

cc.

of

cc.

titrated.

the

liquid contained in the

Two

burettes were used for

a quantity of N/io baryta solution,

first

exactly equivalent to the hydrochloric acid present, is run in,

means of the second the

of acid

excess

is

titrated with

by

N/ 20

baryta solution.

The

velocity constant

calculated from the equation

is

After

we

and elimination of the integration constant

integration

obtain

k
where C

is

log

the concentration of the ester at the beginning of

the experiment, and C t

The degree

its

concentration after partial decomposition.

having been determined


beforehand by decomposing a weighed quantity of it with baryta,
1

Compare

pp. 2

of

and

purity

3.

of

the

ester

COMPARISON OF THE VELOCITIES OF EEACTIONS.

118

concentration

the

culated

from

the

known,

and,

therefore,

k can be

cal-

titrations without awaiting the completion of

hydrolysis which

the

is

in

this

case requires

a rather prolonged

time.

Some preliminary experiments with

acetic

acid

showed that

does not possess a catalysing power which is at all comparable with that of hydrochloric acid.
Using a N/ 20 solution
of ester, the acceleration produced by the acetic acid set free
it

during the hydrolysis


part of the change.
only

when 60

The following

Time.

may be

small

neglected during a considerable


acceleration becomes perceptible

to 70 per cent of the ester has been decomposed.


results

were obtained with methyl acetate.

119

HYDROLYSIS OF ESTERS BY ACIDS.


results

obtained

the same units

of hydrolysis

by

DE

HEMPTINNE

and LOWENHERZ expressed in

numbers obtained by REICHER for the rate


caustic soda, which are also included in the

as the

by

table to facilitate comparison.


1.

Influence of the nature of the alcohol.

Hydrolysis of different esters of the same acid at

Table

Ester.

A.

25.

120

COMPARISON OF THE VELOCITIES OF REACTIONS.


2.

The influence of the nature of the

Hydrolysis of different esters of the same alcohol at

Table

Ester.

B.

acid.

25.

121

HYDROLYSIS OF ESTERS BY ACIDS.

known, the corresponding values

for the esters of

may be approximately calculated from them,


one of the series has been determined.
l

Ester.

when

any other

acid

the value for

THE INFLUENCE OF TEMPERATURE ON


CHEMICAL CHANGE.
FIRST PART.

THE RELATION BETWEEN THE VELOCITYCONSTANT K AND THE TEMPERATURE.


a.

We

employ here

shall

be

will

Application of thermodynamics.

later

given

formula the

the

in

chapter

strict

dealing

proof of which

with

chemical

equilibrium.

Taking the chemical equilibrium which occurs with nitrogen


peroxide

as

concrete

we may

example,

it

represent

in the

following way,

N
We

are dealing here with

directions,

^=

N0

2.

two changes taking place

namely

N0

2,

and 2

At any given temperature the

N0 = N
2

It

be

which we

will call

by means of thermodynamics, that the


must satisfy the following equation: -

proved,

values of kx and k 2

4.

and k 2 for the second change.

first,

may

velocity constant of each of

these changes has a perfectly definite value,


ki for the

in opposite

d log k i

d log k 2

dT

dT

"

q
'

2T 2

the absolute temperature, and q the quantity of heat, in


calories, which would be evolved by the transformation of unit
1

is

The proof

of this equation
f

is

given on p. 148 et seq.

123

APPLICATION OF THERMODYNAMICS.

quantity (in this case 92


second at constant volume.

kgrms.) of the

first

system into the

Although this equation does not directly give the relationship


between the constants k and the temperature, which we are
shows that

it

seeking,

this relationship

=
A

where

we put

If

and

A =

we

0,

(2)(VAN'THOFF)

obtain

B ......

(3) (BEETHELOT).

corresponds to the expression k =: ab*, which


by BERTHELOT in connexion with his experiments

equation

was proposed
on

are constants.

-jjTjT^

This

B.

must be of the form

etherification.

As

be

will

shown

the results of experiment are often

later,

good agreement with the formula when we put

in

0,

and

consequently

d log k

By

integration of (4)

we

log k =:

So

This

~f~

that q

constant.

independent of the tempcertainly not allowable when the


is

The

some

extent.

and writing q T
bT, where
q
the difference between the specific heats of the two systems, 2
obtain, in place of equation (4),

Taking

we

FfT

of heat evolved by a reaction changes with the temp-

quantity

is

however,

is,

^
-

applied to considerable intervals of temperature.

is

erature to

we have assumed

far,

erature.

equation

obtain

this into account,

d log k

Chem.

+ BT
--

Zeit.

Appendix, note

Inaugural Dissertation, Amsterdam 1893. Zeit. phys. Chem. 12, 155, 1893.

phys.

4,

226, 1889.

3.

124

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.

From

log k
If

we

this equation,

=
in

log

equation

(5),

we

....

^-,

-|-

we put

obtain by integration,
constant.

obtain

(HARCOURT and ESSON)

(6)

or after integration
log k

Equation (4),
ment with the

p.

= B

log

which

123,

T +

in

constant.
cases

many

is

in

good agreewhich have been made, makes it

observations

possible to calculate the effect of a given change of temperature

on the velocity of a

reaction.

BERTHELOT'S equation reproduces the chief characteristic of the


relation

that if

between velocity of reaction and temperature, which is


the temperatures form an arithmetical series the rates of

form a geometrical series.


By integration between the limits T! and T 2 we obtain from
at these temperatures will

change

equation

(4)

k!

log K
2

= AA

T!

T2
,

J-l

-^2

k 2 being here the velocity constants at the temperatures


and
T 2 respectively.
T!
For a rise of temperature of 10 degrees, therefore,
ki and

ki

log

We

see

from

this,

k7

and on

10

TTT;

this point all the functions

which

have been proposed are in agreement, that at higher temperatures


the

increase

in

the ratio of the velocity constants produced by

a rise of temperature of 10 degrees will be smaller than at lower


temperatures.
1

Proc.

Roy.

Soc.

58,

112,

1895.

HARCOURT and ESSON

the connexion between the rates of reaction


as follows

D. M. KOOY,

loc. cit.

and

a..

express, in this paper,

at the temperatures

Tj and

T.2 ,

12S

APPLICATION OF THERMODYNAMICS.

The great majority of

cases

which have

been investi-

as yet

gated in this direction have been studied in the interval of tempand 184, and it is very striking that
erature lying between
the ratio of the velocity constants for two temperatures differing
by 10 degrees has a value between 2 and 3 approximately. In
other words, a rise of temperature of 10
doubles or trebles the
velocity of a reaction.

The following

table will serve to illustrate this.

Reaction.

126

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.

to the researches of CLAUSEN

to be observed in the respiration

*,

of plants. The quantities of carbon dioxide expired in equal intervals of time increase rapidly when the temperature rises between

and

25. A

temperature of 10 increases the quantity


2.46 times (on the average) with wheat, 2.45 times with lupins,
and 2.47 times with syringa (lilac).

Above 25
is

rise of

the increase in the rate of the metabolic changes

and

smaller,

50

above

it

to

approximates

that which

is

found at lower temperatures.

With regard

the

to

temperatures, KooyV

of the velocity constants at high


experiments on the decomposition of phosphine
ratio

between 310

at temperatures

and 512

confirm the result which

was obtained from the equation


kt
log rK2

The following

= A

10

=-=-.
J-l

i2

table contains the velocity constants determined

experimentally at different temperatures.


If the ratio
ately,

for

of the velocity constants be calculated approxim-

differences

310_367,

367

of

temperature

446, 446

512,

of

while for the interval of temperature


is

of

obtained, so that at lower temperatures

magnitude

as

10,

in

the intervals

the value obtained

10
it

the
is

is 1.2,

number 2.92

of the same order

the ratio found already for other reactions at

the ordinary temperature.

Decomposition of phosphine.
Temperatures.

127

DECOMPOSITION OF DIBROMSOCCINIC ACID.

Experimental treatment of

b.

The
what

1.

influence of the temperature on the velocity of a reaction

been

has

the subject.

studied

number of

in

Influence

which are described

cases

follows.

in

>

of the temperature on the rate of decomposition of

dibromsuccinic acid.

Since
acid

it

was found that dibromsuccinic

decomposes

100

at

in

aqueous

solution in only approximate accordance

with the equation

C,

Br 2

C4

Br

+ H

Br,

became necessary to investigate the secondary


which occur at different temperatures.

it

reactions

With this object the increase which the titre


of a solution of the acid undergoes on heating
to

75, 100, 125, and 150 was determined.


The solution was heated in sealed tubes and
carbon

the

dioxide,

formed

by the secondary
removed before making

decomposition of the acid,


determinations of the

the

(fig.

30)

The tubes

titre.

were opened after being heated, and


by means of the hook E, into a

brought,
kind of exsiccator containing a pice of caustic

This was connected, at D, to the


potash at B.
air pump and partially evacuated, the tubes
then

being

vacuum

for

24 hours.

The following

allowed

to

remain

in

the

partial

table

contains

the augmentations of the titre

produced by heating for different periods of time

and at

different

temperatures.

Special

way without

experiments
loss of

had

shown

hvdrobromic

acid.

that

the carbonic acid

may

be removed in this

128

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.

75

EXPERIMENTAL TREATMENT.

129

Puttmj

A =
we

0,

0.0412, and

273,

obtain

log k

2.

= 0.0412

6.02219.

Influence of the temperature on the rate of the reaction

between sodium chloracetate

and

caustic soda.

The experiments on this point were made by SCHWAB in the


way which has already been described on page 17.
The following table contains the experimental results, together
with those calculated.

Temperature.

130

THE INFLUENCE OF TEMPERATUEE ON CHEMICAL CHANGE.


3.

Influence of the temperature on the rate of change of


chloracetic acid in aqueous

solution.

This series of experiments also was carried out by SCHWAB.

EXPERIMENTAL TREATMENT.

The

results obtained

were as follows.

131

132
5.

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.


Influence of the temperature on the velocity of the reaction

between potassium

chlorate

and ferrous sulphate

in presence of

sulphuric acid.

This

0.5637

has been very carefully investigated by HOOD;


of ferrous sulphate, 0.2057 grams of potassium

reaction

grams

and 3.099 grams of sulphuric acid were brought into


was kept at the desired temperature by means
which
flask,
of a thermostat, and diluted to 260 cc.

chlorate,

The progress

of the oxidation

was followed by

titrating 10 cc.

of the liquid with permanganate from time to time.


are contained in the following table.

Temperature.

The

results

EXPERIMENTAL TREATMENT.
6.

133

Influence of the temperature on the rate of hydrolysis of


ethyl acetate by caustic soda.

We

shall

reference

consider here the experiments of

has already

the following table.

Temper-

been made.

The

WARDER

to

which

results are contained in

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.

134

Influence of the temperature on

10.

the hydrides of arsenic

the rate of decomposition

of

and phosphorus.

While the reactions which we have

so far considered

have

been investigated only within rather narrow limits of temperature,


we have here a case in which determinations of the velocity

have been made over a

fairly

KOOY has determined


position

of arsenic

much

200

as

constants for the decom-

velocity

at temperatures as

apart.

Arsenic hydride.

and the way in which the experiments


described on page 41. The velocity constants

The apparatus

used,

are

made,

wide range.

and phosphorus hydrides

a.

were

the

at the boiling points of

amyl benzoate (256 ) r


and
anthraquinone (373).
diphenylamine (310),
We have already seen (p. 43) that changes in the nature of

were determined

the

walls

of the

the velocity

vessel

may have

a considerable influence on

of a reaction, so that to obtain results at different

temperatures which would be comparable with each other


necessary to avoid disturbances arising from this cause.

was achieved by making


velocity in the same new vessel
This

heating.

By

changed very

taking
little,

The following

these

all

it

was

the determinations of the

and

by avoiding prolonged

precautions the nature of the walls

and the values of k obtained are comparable.

table contains the results.

Temperature.

135

EXPERIMENTAL TREATMENT.
b.

Phosphine.

The experiments were made


arsenic

310

(anthraquinone), 446
(diphenylamine), 367
(sulphide of phosphorus).

512

The

as those with

rate of decomposition being determined at

the

hydride,

same way

in the

(sulphur) ; and

have already been given in the table on page 126,


moisture had no influence on the value of k.
results

The agreement between the observed values of k and those


by means of the formula of ARRHENIUS,

calculated

d log

"

T2

dT
not satisfactory.
this case the

is

'

intervals of temperature are large, and the

In

variation of q with the temperature cannot therefore be neglected,


so that it is better to employ the formula

d log k

or,

BT

T2

dT

'

after integration,

log k

The values

~ +

of

log

likewise

table shows.

Temper-

const. (See

k calculated by means of

better with the observed numbers.

ESSON

gives

fairly

page 124.)

this equation agree

The formula

correct

results,

as

of HARCOURT and

the

following

THE INFLUENCE OF TEMPERATURE ON


CHEMICAL CHANGE.

SECOND PART.

One

THE TEMPERATURE OF

IGNITION.

of

the preceding section

the

conclusions

arrived

at

in

further

consideration, since it appears


with
the
harmony
phenomena of inflammation.

requires

The

to

which

considerations

are

has so far been

directed,

of

been

ignition

sudden occurrence at a

exceptions

to

this

led

to

was a continuous one; the


and the theoretical
described,

influence

which have been advanced agree in

phenomenon
its

this

which have

experiments

by

attention

that

conclusion

The

out of

investigations on the influence of temperature on chemical

change,
the

be

to

appears

to

this respect.

indicate,

however,

definite temperature, that there

continuity.

L.

MEYER

expresses himself

on the subject in the following way:


" The lowest
temperature at which a given chemical reaction
occurs, which in the case of combustible substances is known
the

as

temperature

of ignition,
"

might be

called,

in

general,

the temperature of reaction.

There
have

is

here

distinct

contradiction

of

the

views which

been

velocity

advanced as to the influence of temperature on the


of reactions. These views do not admit the possibility

of

sudden

any

suppose

of the reaction, and require us to

that

will also

it

acceleration

if a reaction
occur at any given temperature
forward
at
go
any other temperature, although with

a different velocity.
1

Dynamik

der Atome, 1883, p. 417. Also BUNSEN, Gasom. Methode, 1877, p. 336.

137

THE TEMPERATURE OF IGNITION.

study of the subject will, however, show that


the phenomena of ignition do not in the least oblige us to
admit the existence of a temperature at which the reaction
begins the occurrence of inflammation then falls into line with
closer

the ideas which have so far been acquired.

The proof

of this statement depends on the fact that there are


conditions fulfilled by every reaction which exibits the

three

we

inflammation

By

phenomenon.

shall

understand here not

of combustion, but also any complete chemical

only the phenomena


transformation which occurs in consequence of a local elevation
of the temperature to the so-called temperature of ignition.
In every change of this kind the following conditions are
fulfilled
1

:-

The
The

2.

reaction which produces the inflammation evolves heat.

more or

reaction occurs

less rapidly

below the temp-

erature of ignition.

The

3.

The

reaction

is

of

necessity

accelerated by an elevation of temperature.

the

condition being sufficiently proved

first

which are generally known, it will suffice to cite the


sparse observations which lead to the admission of the

facts

by

rather

second; the third condition appears to be fulfilled


all chemical changes so that there is no reason for

of the

truth

by

equally

it

considering

The

following,

show that the

The

detail.

the

are

then,

observations

which appear

to

reactions occur below the temperature of ignition

oxidation of phosphorus, phosphine, arsenic, sulphur, hy-

drogen

and

more

in

hydriodic acid, carbon monoxide, ether, and paraffin, has

*,

striking example of this

RAUM

\V.

formation

of

water

is

so

given in the most recent experiments of V.

is

2804,

28,

moderate

to

gas

electrolytic

(Bcrichte,

on

1895)

At

temperature.

small

that

it

MEYER

of prolonged exposure of
the ordinary temperature the rate of
the

effects

practically cannot be observed.

On

heating

10 days to 300, the formation of water could not be


and night for 65 days, to this temperature, a distinct

electrolytic gas continuously for

proved,

but

formation

of

temperatures
for

heating day
water occurred.

it

(see

p.

It

is,

would be possible

sufficiently

been referred
bulbs

on

to,

to

therefore, natural to suppose that even at lower

demonstrate the formation of water, by healing


In the experiments at 300, which have

prolonged period of time.


the

following

percentages

of the electrolytic

gas contained in three

4S) were transformed into water;


9.5,

No change could be detected

at

100,

0.4,

1.3.

after heating for

218 days and nights.

138

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.


considerably below

been observed

The same

the

temperature of ignition.

true of the chemical transformations undergone

is

by ozone, chloride of nitrogen, cyanic acid, mixtures of chlorine


and hydrogen, and of chlorine and hydrocarbons, etc.
they take
l

place more or

at temperatures

less slowly
determine ignition or explosion.

The

below those which

three conditions mentioned being fulfilled, a

phenomenon

of the nature of ignition

To prove

this,

of

susceptible

and suppose
(fig.

may occur.
suppose we have

substance which

is

not

chemical

its

change, for example, atmospheric air,


to TI
temperature to be raised locally from

On removing

31).

the source of heat, the increased temp-

rig. 31.

be communicated to the surrounding gas, and will,


therefore, give rise to a kind of hot wave which will be propagated
with a certain velocity, its temperature sinking continually
erature

will

towards
l

2155,

Bull.

Soc.

1832;

16,

Chim. 13, 1, 1370. Compt. Rend. 78, p. 1853, 1874. Berichte, 15,
139 and 478, 1883. VAN 'T HOFF observed that the slow oxidation

of heated paraffin is accompanied

ance to a combustion.

by a phosphorescence which

is

very similar in appear-

139

THE TEMPERATURE OF IGNITION.

The curve T^Ai, which


atures along

OT and the

is

obtained by measuring the temper-

distances along

OD, represents graphically


the relation between the temperature of the wave and the distance
which

it

has travelled from the starting point. For brevity we


T the diminution in the temperature of the hot wave

will call /\

during the

first

moments

of

its

progress.

Suppose, now, that a chemical reaction which satisfies the


three above-mentioned conditions may occur in the gas suppose
for example, that we have electrolytic gas in place of atmospheric
;

air.

of

local elevation of temperature will then produce a

kind

the

described,

but

wave

with the difference that the temp-

sink less rapidly during its


first,
because
the
chemical
propagation,
change produced by the elevation of temperature evolves heat. The value of /\ T will thus
erature,

especially

at

will

be diminished, and the graphical representation of the temperature


of the hot wave will be given by the curve TjAx (fig. 32).

Fig. 32.

We
of

the

far

as

will

now

consider the effect of a greater initial elevation

temperature in the two cases.


the

substance which

The matter

is

simple, so

does not undergo chemical change

140
is

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.


the

concerned;

than

rapidly

ated; this

and the medium through which

it

represented by the curve

is

chemical

change
have in addition to

which diminishes

the

tends

to

increase

now produce

another

by the

exceed that which

A T w^

evident that the value of

is

it

it,

we

the case,

being

A T,

we

a greater quantity of heat.

to diminish /\

diminish as the initial temperature

This

propag-

When

for the chemical change, accelerated

it ;

which tends

action

is

31.

in fig.

which increases

this influence,

higher temperature, will


If

T2A2

it

as with electrolytic gas,

however,

occurs,

more

will fall

the greater difference of temp-

to

owing

before,

erature between

wave

of the hot

temperature

rises.

perceive the possible existence of a

which the value of /\ T will be zero, in


2
temperature,
other words, of a temperature at which the wave will preserve

initial

its

T2A2

line

at

temperature
(fig.

still

is

by the

represented

32).
initial

higher

temperature,

T 3 would
.

rise to

give

wave the temperature of which, instead of falling, would


until it reached the temperature which the total transform-

hot
rise

capable of producing. (T 3 A 3 fig. 32.)


obvious that those waves the temperature of which falls

ation of the substance


It is

can

is

give rise to a very minute quantity of change, while


of which the temperature rises lead to the transformation

only

those

the whole

of

this

unchanged;

which gives

The temperature T 2

of the substance.

rise to a

therefore,

wave of constant temperature, corresponds

in every particular to the ignition temperature.

would

It

be

not

mathematical symbols, but


as follows:

The
loss

It

ignition temperature

due

accounted

for

by the

that,

inous

in

oxygen

in

the

preceding

into

in

words

which the

initial

preferable to express

it

given

other

is

the temperature at

conduction

etc.,

is equal to the heat evolved

the chemical reaction.

however,

at

limit;

to

same time by
must,

is

of heat,

in the

it

translate

to

difficult

be

remarked that

facts

are not

It is

known

certain

foregoing considerations.

no

longer lumtemperature, phosphorus


a certain
exceeds
gas the pressure of which

words there

is

is

definite

pressure

at

which

141

THE TEMPERATURE OF IGNITION.

different

of the reaction suddenly assumes a finite value.


found that the luminosity first became visible at the
temperatures given in the following table, when the

pressure

of

the

velocity

JOUBERT

value which

Temp.

the
is

oxygen

given.

was diminished

to

the

corresponding

142

THE INFLUENCE OF TEMPERATURE ON CHEMICAL CHANGE.

suddenly begins, in other words, we find, on raising the temperature, a per saltum transition from conditions under which no
oxidation occurs to conditions under which

Mathematically

considered the

it

does occur.

phenomenon perhaps

indicates

that the equation


%

d log k

j\._

~~dT~

!?'

where t would
t),
containing (T
the
which
discontinuity occurs.
represent the temperature at

should have

another

term

CHEMICAL EQUILIBRIUM.
FIRST PART.

THE THREE FORMS OF CHEMICAL


EQUILIBRIUM.
The study of chemical equilibrium

yields results

which form

a very important addition to our knowledge of chemical change.


This will be obvious if, with PFAUNDLER, we regard equilibrium
as the result of two changes

taking place in opposite directions

with equal velocity.


according to HORSTMANN, the principles of thermodynamay be applied to chemical equilibrium, and since the

Since,

mics

experimental
frequently

the

which are encountered

difficulties

much

smaller than
in

is

the

in its study are

the case in dynamical researches,

domain of chemical equilibrium

gained
advantageously be applied in the study of chemical change.
Three kinds of equilibrium may be distinguished experience

may

Equilibrium in

1.

2.

,,

3.

I.

homogeneous systems.
heterogeneous
condensed

cases

At constant temperature.

of equilibrium

forming the system

An
1

,,

HOMOGENEOUS SYSTEMS.
a.

In

,,

may

example of the

in

homogeneous systems the bodies

be gaseous,

first

of these

liquid,
is

or solid.

found in the case, which

This latter form of equilibrium will not occupy us further; the so called "solid
and also many diffusion phenomena in solid bodies show, however, that it

solutions",
is

probably justifiable to speak of equilibrium in

homogeneous

solid system.

144
has

CHEMICAL EQUILIBRIUM.

been

already

of

mentioned,

the

of

dissociation

peroxide

nitrogen

NA
The following

^=

N0

2.

an example of a homogeneous equilibrium

is

in a liquid system,

C 2 H 5 OH

CH COOH
3

As we have already
as the result of

+ H 0.

CH3 COOC 2 H 5

observed, the equilibrium

to be regarded

is

two changes taking place with the same

velocity

the case of a homogeneous


the
of
the
velocities
of the opposing reactions
equilibrium,
study

in

directions,

opposite

permits

us

to

so

that,

in

between the concentrations of

calculate the ratio

the two systems

when

the state of equilibrium

attained.

is

In the example chosen \

N,0,

NO,,

the velocities of the two reactions are given by the equations,


-

at

GI and

C2

kjCj,

and

are the concentrations

respectively,

in

the

units

-~

k2C 2

at

of the systems

which have already

and

N0

been employed

(92 kgrms, per cubic metre).

Equilibrium having been attained, the velocities of the reactions

rip

and
at

<

at

are equal, and therefore

d =

k2C 2

or in general,

Henceforward the system written

to the left of the

~>

"

sign will be called the "first

and Iq will be used with


system", that to the right the "second system", the letters Cj
reference to the first, C 2 and k 2 to the second. This choice is of course purely arbitrary,
since the part taken by the two systems in producing equilibrium
2

Page

4.

is

the same.

145

ISOTHERMAL EQUILIBRIUM IN HOMOGENEOUS SYSTEMS.

where

and n 2 are the numbers of molecules

r\i

in

each of the

systems which take part in the reaction.


An equation of this form has already been given by GULDBERG
and WAAGE, by PFAUNDLER, and also by HORSTMANN.
It

however, that we have deduced

be noticed,

to

is

from

it

the equation

dC

dt

which
also

exactly true only for great dilution.

is

same

therefore subject to the

is

The

restriction,

derived equation

and where

this

observed the experimental results are found to be


with
those obtained from the equation.
agreement
Just as the determination of the velocity constants may be

restriction

is

in

used

order to calculate the ratio between the concentrations

in

of the opposing systems in the state of equilibrium, so this ratio


may be employed to obtain a knowledge of the velocity constants.

The

investigation

concentrations

of

the

of

equilibrium gives the values of the

the

systems taking part in it, and, therefore,


that of the ratio between the velocity constants Iq and k 2 which
henceforth will be denoted by the letter

and called the

equili-

brium constant.

We

If,

have thus,

had been determined by the study of the


of the two opposing changes, the value of the

for example,

velocity

of one

Iq

velocity constant of the other change

would be obtained from a

study of the equilibrium.

BERTHELOT

and

PEAN DE SAINT GILLES

conditions which were varied as

an

acid

is

convertible

much

ester

into

have determined, under

as possible,

what part of

it

with a given

by treating

quantity of an alcohol.
1
-'

Also

Juurn. prakt. Chetn.

(2),

Ann.

(3),

VAN

Chim.
'T

Phys.

19,
05,

69

et seq.

3S5,

1879.

1*02;

(3),

60, 5, 1862; (3), 68, 225, 1863

MOIT, Bcrichte, 10, 069, |s?7.


10

146

CHEMICAL EQUILIBRIUM.

The

reaction takes place as follows,

Acid

we bring

If

^z

alcohol

water.

-f

gram-molecule of acid,

together

Ester

w gram-molecules

of water, and a gram-molecules of alcohol, we have in the condition of equilibrium when e gram-molecules of ester have been

formed,
-

(1

where

is

(a

e)

e)

(w

e)

the volume of the mixture, and

l&i

'

and k 2 are the velocity

constants.

Or,
kl (1

When
of

the

ki

e ) (a

e)

k2e

(e

w)

(I)

and k 2 are known, this equation allows the quantities


substances which will exist side by side in

different

equilibrium

values") to be calculated, and the

"limiting

(their

therefore be called the limiting equation.

may

equation

The experiments of BERTHELOT and PEAN DE SAINT GILLES show


that when acid and alcohol are mixed together in molecular
proportions,

of the mixture

/3

experiment gives

/3 ,

is

for a

converted into ester.


1,

and

w =

Putting these values into the limiting equation

(l-

k,

2
/ 3)

(!-'/)

k2

That

is,

0.

we

get,

V/8,

or

it

Introducing this value into the limiting equation, and solving


for e, we obtain

g-

[4 (a

Since

+ 1) +

V 16 (a

a 4- 1)

+ 8 w (a +

1)

+w

the experiments of BERTHELOT and PEAN DE SAINT GILLES

were made with mixtures of acid and alcohol without the addition
of water,

we must put w
e

a/3

(a

in the last equation,


1

- V

a*

a -f~T)

and find

ISOTHERMAL EQUILIBRIUM

The following
of alcohol used

HOMOGENEOUS SYSTEMS.

table contains, under a the


to

one molecule of

molecules of ester formed.

IX

acid,

number

under

147

of molecules

e the

number of

148

CHEMICAL EQUILIBRIUM.

be written

If the equation

3.

-e

(1

we

w =

find for

cx5

that

o,

(a

e)

formation of ester

is,

vented by a very large addition of water. The same


addition of a very large quantity of ester.

is

is

pre-

true for

Tlie temperature is variable.

b.

Application of Thermodynamics.
The
is

influence of the temperature on the equilibrium constant

expressed by the following equation

d log

q
ITr*

dT

where

system
This

the

is

when

evolved

is

*,

absolute temperature,

q the quantity of heat

unit quantity (in kgrm. molecules) of the second

transformed into the

equation,

which

at constant volume.

first

homogeneous and

true both for

is

and in dilute solutions,

in gases

heterogeneous equilibrium
be obtained in the following

way

for

may

Let us suppose that equilibrium exists between (1


x) kgrm
molecules of the first and x kgrm. -molecules of the second system,

volume

the

that

reversible

of

the
of

cycle

which we

system for

l_

is

J.

dissous.

the

is

/dPv
""

IdT/v

/dQ\

VdVV

quantity

of heat

Koflgl

which

is

absorbed when the

indefinitely large quantity of the system is increased

at the temperature T. Call

H. VAN

239, 1885.

operations

the pressure acting on the system.

volume of an

by unity

V, and the temperature T.


may be carried out with the

is

shall have, (from thermodynamics),

where P

whole

'T

HOFF,

S VCD ska

Lois
Vet.

de

Akad.

i'equilibre

q the quantity of heat which


chimique

Handlingar,

21,

dans

1885;

1'etat

gazeus on
Xecrland. 20,

dilue,

Archiv.

149

INFLUENCE OF TEMPERATURE.

absorbed when

Is

the

into

When

second

unit quantity of the


without any external

the quantity of heat absorbed by this,

obtained

the

external

so that

from the

cals,

we

work being performed.

n!

is

formed

(viz.

(viz.

-^==

\dV/ T

mav

also

total

amount of heat absorbed,

\dv/ T

obtain

dv/ T -\dv/ T
If

converted

by subtracting the quantity of heat equivalent to


work done by the system during the expansion,

viz.

is

system

the volume of the system changes at constant temperature

a certain quantity of the second system

be

first

molecules

of the

"

VdiVv

dr

....(1)

and n 2 molecules of the second

first

system take part in the reaction, we have

PV

[>!

x)

m +

(n 2

(1

n2

x] RT.

(2)

Therefore

P
_

-; [

- -

nO

R
]

and

f**\

Substituting this in equation

/dx\

(1),

we obtain
/dx\

T-'R

At constant temperature, we have the

relationship

r"

f^)"
K,

or

....

K,

(4)

and therefore,
log

(n 2

- -

ni) log

V =

n 2 log x

nj log (1

x).

150

CHEMICAL EQUILIBRIUM.

By

partial differentiation with respect to V, this yields

n2

nj

we

Similarly differentiating with respect to T,

d log

/dx\
VdT/v

dT

"

Introducing these values into equation

d log

Jq

This

equation

likewise

applies

(3),

it

_q_i

"

RT 2

dT

obtain

becomes

T2

the case of heterogeneous

to

equilibrium, for equations (2) and (4) apply equally well in this

case

when

ules

the

gaseous or dissolved substances which take part


reaction. Since the values of i\i and n 2 do not appear

the

equation

of

ation

and n 2 are taken to mean the numbers of molec-

the

"

~Vrp

makes no

~o~rm"

in.

in.

alteration in their signific-

t^is

difference.

Applications.
In applying the equation to homogeneous chemical equilibrium

we have

to distinguish

b.

The value
The value

a.

The value of q

a.

In

this case

may change

two cases:

we have

of q

is

zero.

of q

is

5 zero.

is

zero.

equilibrium between two systems which

into each other, at constant volume, without evolution

or absorption of heat, consequently


1

This

entropy by

formula

has

also

VAN DEVENTER,

been deduced from

Zeit.

Phys. Chem.

2,

the principle of the increase


92,

1888.

of the

INFLUENCE OF TEMPERATURE.

d log

151

dT

which indicates that

An

equilibrium
or

elevation

We

of

depression

therefore

ibrium

is

this

obtain

has no

effect

independent of the temperature.


kind is therefore not displaced

by

of the temperature at constant volume.

If a displacement of the equilon the temperature, a change of temperature


the

rule:

not displace the equilibrium.

trill

As examples

of equilibria which are unaffected by changes of

temperature the following

may be mentioned

The equilibrium of

1.

CH 3 COOH

C 2 H 5 OH

ether ifi cat ion.

C2 H3

:j=

C2 H 5

0.

The opposing changes


evolution of heat,

are here accompanied by an insignificant


and the equilibrium is found to be practically

unaffected by a change of temperature.


ation

220

reached

is

the limit
2.

is

when 65.2 per

of optical isomers developes

no heat,

found that the equilibrium between them is unaffected


a mixture of them which is inactive at
temperature
;

when

the ordinary temperature remains inactive


3.

Equilibrium between optical isomers.

is

it

the

by

the limit of etherific-

found at 66.5 per cent.

The mutual transformation


and

At 10

cent has undergone change, at

The following

case

is

CO ^=L

-f-

is

it

heated.

also of interest,

At moderate temperatures

this

C0 2

-f-

change

is

accompanied by an

of heat, which diminishes as the temperature rises in


consequence of the difference between the specific heats of the

evolution

two

systems;

its

value

should be zero at

1700.

Bull. Soc. Chiro. 31, 352, 1879.

BERTHELOT, Essai de Mecanique Chimique, II, 73.


VAN 'T HOFF, Die Lagerung der Atome im Raume, 1894,

:!

4
r>

isc,heu

Compt. Rend. 93, 10*, 1881.


Ucber Verbvennnngsem-heinungeu
med. Vereins zu Heidelberg.

bei

Gasen. II.

p.

HORSTMANN

33.

Vcrhandlungen des natiu-histor-

152

CHEMICAL EQUILIBRIUM.

has found that the equilibrium ceases to be displaced at a temperature which he estimates to be 2250. The difference between

and 2250

1700

may

well be due to the difficulty of determin-

ing such high temperatures.

The value of

b.

In this case

is

zero.

will vary with the temperature,

and by means

of the equation

d log

K
"

ciT
it

2T 2

will be possible to calculate the value of q

the equilibrium,

of

from observations

and to compare the value so obtained with

that directly determined by experiment.

As an example

of this

we

NA
The

quantities

which occur

shall consider the equilibrium

2.

in the equations

K_ q
~TT~ ~2T 2al

d log

2N0

C2

^T'

have the following signification in this special case: G! and C 2 are the concentrations of the first and second
systems

that

respectively,

is

the

quantities of N.2

and

2N0

both cases, 92 kgrms;


per cubic metre,
ni and n 2 are the numbers of molecules forming the first and
unit quantity being, in

second systems, in this case, their respective values are 1 and 2;


q is the heat, in calories, which is evolved when 92 kgrms. of
the second system are converted into the first at constant volume.
The dissociation of nitrogen peroxide has been studied by
whose observations will be used in order
DEVILLE and TROOST,
l

to calculate q.

peroxide,
1

2
7,

at

They determined the vapour


atmospheric

pressure,

at

density of nitrogen

different temperatures.

Compt. Rend. 64, 237, 1867.


See also A. J. SWART, Inaugural Dissertation, Amsterdam, 1890.

120, 1891.

Zeit. phys.

3
.

Chcm.

INFLUENCE OF TEMPERATURE.

The

fraction

which

of the peroxide

153

exists as

2N0

is

ob-

compared with

air,

tained from the expression

~~

3.179

where 3.179
and

the vapour density of

is

that of the dissociated mixture.

is

In order to calculate q, the equation

d log

"

~~df~

2T-

must be integrated, whence we obtain

KI and

are here the equilibrium constants at the absolute

temperatures TI and
Further since

we

T2

obtain

T,

where
existing

Xi

and

Substituting

we

x2

are

form

the

in

(1

the
2

value

this

x*)

fractions

N0

at

(1

(1

of the ratio

T,

(1

x?)

of the dissociated mixture

the

temperatures

obtain

xl

and

T2

in equation (1),

154

CHEMICAL EQUILIBRIUM.

The following

table

contains the experimental data, and the

results of the calculation.

T.

EQUILIBRIUM IN HETEROGENEOUS SYSTEMS.

155

156

CHEMICAL EQUILIBRIUM.

one

with

hand,

exist

its

of decomposition, which likewise

products

the gaseous or dissolved state, on the other hand with

in

the

solid

gas

or

substances,

that

so

NH

the

S or CaC 2

existing as

solution remain constantly in the condition of satur-

in

ated vapour,

or of saturated solution, at the given temperature.

The equilibrium which


precipitated

and the

between the condensed, or


dissolved parts of the same

exists here

or

gaseous,

substance belongs to the class of physical equilibria.


The law by which this latter class of equilibria

is

governed

requires that the concentration of the gaseous or dissolved part,


which is proportional to the vapour pressure or solubility of the

substance, shall depend only on the temperature and not on the

volume of the system.


It has already been pointed out on page 150 that the formulae

--

cllogK

hold

in

good

referring,

the case of heterogeneous equilibrium, n x and n 2

however,

only to those substances which exist in the

gaseous or dissolved condition.

We
in

not

that

must, therefore,
displaced

the

value

by a
of

conclude that a heterogenous equilibrium

change of temperature ivhen g


may be calculated, in the same

and

way

as

formerly, from determinations of the equilibrium, and compared


with the value obtained from calorimetric determinations.

Cases investigated.
As an example of a calculation of
dissociation of ammonium sulphide,

NH S
5

NH

^=

which was investigated by ISAMBERT.

The value

this kind,

4-

2
:

K7

Compt. Rend. 92, 919, 1881.

q
2

will take the

2 S,

of q will first be calculated

log

we

/I
IT,

by means of the equation

1\

a >'

157

EQUILIBRIUM IN HETEROGENEOUS SYSTEMS.

For

this purpose,

we put

rij

\\ e

have,

C2

2,

the

further,

maximum vapour

and n 2

K =

and, therefore,

0,

pressure

following connexion between the


p of the mixture of ammonia and

sulphuretted hydrogen, which was determined


LSAMBERT, and

concentration C 2

its

^
where

(C 2 )

and

temperatures

(C 2 ) 2

are

T2

and

T!

(C 2 ),

the

experimentally by

&

concentrations at

pressures.

Substituting this for log


P2

log

-^

log

~, we

obtain

Pi-

/ 1

T (^

1
.

from which q may be calculated.

The experimental data

the absolute

and p x and p 2 are the corresponding

are the following:

"\

TJ-),

158

CHEMICAL EQUILIBRIUM.

The value calculated (21550) is, therefore, in good agreement


with that found by direct experiment (2146021830).
The dissociation of salts containing water of crystallisation,
b.
which has been

by FROWEIN

studied

and others with special


may suitably be consid-

reference to the thermodynamical equation,

ered here.

Taking, for example, the equilibrium


.

we may apply

to

this

case,

n 2 =.

1, and, therefore,

That
which

the

aqueous vapour,

C2

so

that ni

in
0,

equal to the concentration of the aqueous vapour


in equilibrium with the salt. Call this concentration C s

is,

is

is

therefore,

and
md

n 2 refer only to the uncondensed substances,

and

nx

the equations

K
when

+ H 0,

^=: CuS0 4 4H 2

CuS0 4 5H 2

is

here

which

heat

of

the

is

when 18
CuS0 4 .4H 2

evolved

q
quantity
kgrms. of aqueous vapour combine with the salt
to form CuS0 4 .5H 2 0; calling this q s our equation becomes
,

"

dT
This

'

2T

may, however, be transformed so that q s

expression

is.

replaced by the quantity of heat determined calorimetrically,


that is, the quantity of heat which is evolved by the combination of 18 kgrms. of liquid water with the dehydrated
salt.

~.

bince the general equation,


ical as well as to

dT
1

Zeit. phys.

See page 205.

Chem.

1,

1,

1837.

'

=.

Cll

chemical equilibrium

dlog_Cw

~K

d log

qw

2T

'

2
>

7^7,
u1

applies to phys-

we may

write

where C w

concentration of saturated steam, and q w the


by the condensation of 18 kgrms. of

the

is

which

heat

is

159

HETEROGENEOUS SYSTEMS.

IN

EQUILIBRIUM

evolved

saturated steam at the temperature T.

The quantity
qK

is

By

which

of heat

the difference between q s and q w

7^
^w

qs

dT
is

the

and the

we

from

subtracting equation (2)

log

~-

determined calorimetrically,

is

ratio

(1),

we

obtain

qw
2T 2

between the dissociation pressure of the


of water,

vapour pressure

both at T.

salt

Calling this F,

obtain

d log

qK

"

2T*

~~dT~
where q K

is
<

the heat evolved by the combination of 18 kgrms.


of liquid water with the partially dehydrated salt.

Assuming that
vals

of

is

qK

constant for small inter-

we

temperature,

obtain by integration

of the above equation

from which q K may be calculated when F x and


are known at the temperatures Tj. and T 2

F2

The apparatus,

a terisimeter,

which was emp-

the

pressures

loyed in determining
salts

vapour

containing water of crystallisation

is

of

shown

in fig. 34.

Two

bulbs,

powdered
rig.

u.

acid

similar

tensimeter

and

and

dry

respectively

by means of a U-tube
The openings at a
of pressure.

A
;

half filled

was

and
used

salt,

having

by

BREMER
6,

contain

the

finely

and

strong sulphuric
they are connected together
with olive oil.

Rec. trav. ohim. des Pays-Bas,

B.

been

closed

before

the

for the determination of differenced

121, 1887.

160

CHEMICAL EQUILIBRIUM.

blowpipe, the apparatus is placed in a horizontal position, the oil


collecting in the bulbs C and D, connected to the air-pump at c,

and evacuated, the last trace of air being removed by warming


whole apparatus with the flame of a spirit-lamp
it is

the

finally sealed at

24

hours

in

crystallisation

the

The apparatus having been

c.

vertical

may

measurements

be
of

position,

equally
pressure

left

to itself for

order that the

in

water of

distributed

throughout the salt,


begun. These are made by

are

means of a cathetometer, the tensimeter being immersed in a


HERWIG'S water bath the temperature of which is maintained
constant by continual stirring.

Two

separate tensimeters were used

each experiment. After the completion of the


simultaneously
observations, the bulbs containing the salt were detached and
in

the water of crystallisation determined.

The following

table

with copper sulphate.

Temperature.

contains the

results of the

experiments

161

EQUILIBRIUM IN HETEROGENEOUS SYSTEMS.

THOMSEN'S

direct

determination gives

qK

3410

cals.

agreement is thus satisfactory.


The whole of FROWEIN'S results
table,

from which

it

may

are given in the following


be seen that there is a good agreement

between the values of q K obtained directly and indirectly.

Salt examined.

The

162

CHEMICAL EQUILIBRIUM.

heats

of

solution

of CuCl 2

KC1

KC1 and CuCl 2 2KC1 2H 2

the mean of two experiments gave 3063


The apparatus used in measuring the
in principle as that

calories.

pressures

was the same

employed by FROWEIN but somewhat different

in detail.

The pressure of the aqueous vapour evolved by


2H 2 0, CuCl 2 KC1, and KC1 was:

CuCl 2 2KC1.

Temperature.

a mixture of

163

EQUILIBRIUM IN CONDENSED SYSTEMS.

which occurs

at temperatures

equation

2(C 4 H 4

NaK. 4H 2 0)

C4 H4

K2

higher than 55

according to the

+ C H,0 Na
6

2.

2H 2

-4- 5i/ 2

has been studied by J. DOCTERS VAN LEEUWEN.


At temperatures lower than 55 the double salt

from

its

Here,

is

reformed

components.
again,

qK

may

be

calculated

from

the

dissociation

pressure of the crystals.

The pressures were determined by means

of a tensimeter

(fig.

36)

containing finely powdered and partially dehydrated Rochelle salt


in the bulb d, and concentrated sulphuric acid in the bulb e.

Temperature.

H 0,
2

164

CHEMICAL EQUILIBRIUM.

In the course of an investigation on ammonium nitrate LEHMANN*


made the following observations
"
When fused ammonium nitrate is allowed to solidify, skeleton
:

crystals belonging to the regular system are formed.

The behaviour

of these crystals in polarised light shows them to be completely


On further cooling a sudden change occurs at about

iso tropic.

127,

the

crystals

becoming doubly-refractive. On

still

further

cooling needle shaped rhombic crystals are formed at about 87,


these can also be obtained from a hot alcoholic solution. These
crystals generally change while still in contact with the solution,
and invariably on removing them from it, into a fourth modification which also belongs to the rhombic system and which may

be

obtained

in

good

fairly

from aqueous solutions at

crystals

On

heating this fourth modification


gradually, it passes through all the changes described, but in
the other rhombic modification is
inverse order, at about 36
the

ordinary

temperature.

formed, at about 87

We

the rhombohedric, and at 120 the regular".

are therefore dealing here, not with an equilibrium such

found in homogeneous and in heterogeneous systems which


is continuously displaced by a continuous change of temperature r
but rather with per mltum displacements of the equilibrium at
as

is

36, 87, and 120.


At the

temperature an equilibrium exists which

latter

may be

represented thus,

NH N0
4

The

rhombohedric

^=

characteristic part of the

the

below 120

temperature

possessing

NH N0
4

phenomenon

the equilibrium

regular.

is

that,

on cooling

displaced totally tosystem


wards the left-hand side of the equation, on raising the temperature
above 120 it is displaced completely towards the right. A

transition point,

The kind
l

GROTH'S

When

of

properties

equilibrium

expression

just

"transition

the transition temperature under the


influence of pressure

is

of this kind will be called a

for the system concerned.

Zeitschrift fur Krystallographie,

the

is

described
1,

point",

may be

106, 1877.
or

"transition temperature"

pressure of one atmosphere

considered later.

expected to

is

is

always meant.

used,

The

INCOMPATIBILITY OF CONDENSED SYSTEMS.

occur when none of the substances are in the gaseous or liquid


condition; viz. in so called condensed systems.

The
cases

necessity of the existence of a point of transition in such

be proved,

may

from the known laws of

quite generally,

equilibrium.

an

Consider

example two
then

osition,

between

equilibrium

dissolved

for

substances,

which have undergone a partial double decomporder to find what the condition of equilibrium

salts

in

will be in the absence of the solvent we may remove it


gradually,
at constant temperature, by evaporation.
During the evaporation all the dissolved substances will separate
out except one, in the special case considered three of the salts

the remaining substance (the fourth salt) cannot separate


owing to the laws governing solubility and chemical equil-

separate

out

The laws of

ibrium.

out

separates

shall

solubility require that each substance

have a certain concentration

which

in the solution

while those of chemical equilibrium

corresponding to saturation,

require that these shall be a certain definite relationship between

the concentrations of
to

Owing
substance

is,

definitely

fixed

all

after

last

others have partially separated out,

the

all

further

the dissolved bodies.

two conditions the concentration of the

these

cannot increase

evaporation

it,

and

it

must, therefore, remain equally far removed from the concentration

corresponding to saturation even when the solution is evaporated


dryness. This last substance can thus never separate in the

to

solid state.

From
in

this

equivalent

it

follows, that in case the substances are present

quantities,

whole

the

body belongs must be absent

to

system

which the

last

in the condensed condition, while

not

only the excess of the


can
Both
belonging
system
separate out.
systems, therefore, cannot exist together in the solid condition. This
may be called the law of the incompatibility of condensed systems.
if

equivalent

quantities

substances

to

The coexistence
is,

used,

this

of both

systems in the condensed condition

however, possible under certain exceptional circumstances.


Consider

are

VAN

'T

again

HOFI- and

the

condition

VAN DEVENTER,

Zeit.

of

affairs

phys.

Chem.

described above; by
I

164, 1887.

166

CHEMICAL EQUILIBRIUM.

evaporating a solution containing a number of substances in


chemical equilibrium with each other all of them had been caused
to separate out partially, except one, the concentration of which

and

remains constant,

less

than the concentration corresponding

to saturation, so long as the temperature does not change.

Since the concentration of a saturated solution generally changes


the temperature, and since this is also the case with the

with

of

condition

by

possible,

that
this

in

solution,

be

will

it

substance

of the

the

there

substances

lowering the temperature, to cause the


which has not separated out to

or

raising

concentration

approach

of

equilibrium

saturation

point,

and

it

is,

therefore, conceivable

At

a temperature at which this will be reached.

is

and

temperature,

at

it

only,

is

the separation of

the

all

substances, and, therefore, the coexistence of both systems in the

condensed condition, possible. It must now be shown that above


and below the temperature at which the two systems can coexist
either the one or the other of them is in stable equilibrium,

and that the name "transition temperature" is therefore justified.


In order to do this we may write the equation for a chemical
equilibrium in the form

where

(C 2

(C,

is

the product of certain powers of the con-

centrations of the constituents of the second system, and


is

(Ci.

.)

the same for the

first

Calling c 2 and

the concentrations corresponding to saturation,

Cx

system.

and substituting them in the above equation, we obtain a value


of K which we may call M.

K and
will vary in different ways with the
and
be represented by curves which
therefore
temperature,
may
at this point K and
will cut each other at some temperature T
In

general

are

they

equal

differ.

to

each other, at temperature above or below

The temperature T

is

it

thus the temperature at which

THE TKANSITION TEMPERATURE.

167

equation (1) is satisfied when the solution


all the substances which are in equilibrium,

just saturated for

is

at this

temperature

the substances will separate out of the solution on evaporation,


and consequently the two systems can coexist.
all

When we
out

K < M,

for

substances

c-2

and

the

CJL

for

the second system only can separate

only

we may

in equation (1),

.,

partial separation of all the

occurred,

having

and C L

.,
.

first

one

except

C2

values of

K > M,

have

^> M

replace

the

all

except one, by

this unreplaced

concentration,

must be smaller than the concentration corresponding to


saturation, must occur in the denominator, that is the first system
which

cannot

separate

out

for

<M

second system must be

the

absent in the solid condition for similar reasons. There is thus,


"
as the name
transition temperature'' clearly indicates, a complete transformation of the one system into the other on passing

through

this point.

Cases investigated.
The examples

of the

phenomenon which have been investigated

be grouped under the following headings

may

The
The

a.
b.

transition temperature of

transition

temperature

bodies.

polymorphous

of

salts

water of

containing

crystallisation.

The transition temperature in the case of the formation


c.
and decomposition of double salts.
The

d.

transition temperature in the case of double

decomp-

osition.

The transition temperature of isomeric bodies.


The very close relationship which exists between

e.

omena

and

that

pointed out here.


a.

An
1

The

of ordinary

transition temperature of

exceedingly

Kenntniss

literature of

der

or

solidification,

may

be

It is considered in

The

fusion,

these phen-

more

umkehrbaren

of this kind has

bodies.

been investig-

detail later

the subject

See also SILVIO LUSSANA,

case

simple

polymorphous

is

given pretty fully by

Umwandlungen polymorpher

Nuovo Cimento,

(4),

vol

1,

W. SCHWARZ,

Korper,
97, 1895.

Eeitrage zur
1892.

Gottingen

168

CHEMICAL

ated

REICHER

by

The equilibrium

referred to

symmetric sulphur.

95. 4,

method which

by

The

EQUILIBRIUM.

is

will

be described

that between rhombic and

transition temperature

was found

later.

monoto be

is,
atmospheric pressure rhombic and monosymmetric sulphur can exist side by side at 95 .4, while above

under

that

this temperature only the

and

equilibrium,

below

monosymmetric modification is in stable


on
only the rhombic modification

it

passing through the point of transition a complete transformation


of the one into the other occurs.

LEHMANN'S observations on the changes of the different crystalmodifications of ammonium nitrate into each other have

line

already been mentioned.

The transition temperature of

b.

salts containing

water

of crystallisation.

The apparent melting of

water of crystallisation is often due to a chemical change which occurs above a


certain temperature and which is reversed at lower temperatures,
as is shown by the fact that a salt containing less water than
the

salts containing

original substance oftenseparates

Phenomena

out

during the fusion.

of this kind are observed not only in the case of

containing water of crystallisation, but also with many


3
other hydrates, such as those of carbon bisulphide
phosphorus

salts

hydride

sulphuretted and seleniuretted hydrogen, methyl chloride

chloroform
acid

5
,

4
,

sulphur dioxide, bromine, chlorine, and hydrobromic

6
.

It is well

erature

in

known that Glauber's salt " melts" at a definite temp7


MULDER 8 );
its own water of crystallisation (LOEWEL
,

the apparent melting-point

is

however nothing but the

transition

point in the equilibrium


1

GROTH'S

Zeitschrift

fiir

Krystallographie

8,

593. 1884.

Inaugural Dissertation,

Amsterdam, 1883.
2
3

4
5
6
7

DUCLAUX, Compt. Rend. 64, 1099, 1867.


CAILLETET and BORDET, Compt. Rend. 95, 58, 1882.
DE FORCRAND, Compt. Rend. 94, 967, 1882.
CHANCEL and PARMENTIER, Compt. Rend. 100, 27, 1885.
BAKHUIS ROOZEBOOM, Sec. des Trav. Chim. des Pays-Bas, 3 and 4, 1885-86.
Ann. Chim. Phys. (3), 29, 62, 1850; (3), 37, 157/1853; (3), 49, 32, 1857.
Geschiedenis van het scheikundig gebonden water, Rotterdam, 1864.

THE TRANSITION TEMPERATURE.

Na 2 S0 4 IGHoO
which

and

HOFF

Na 2 S0 4

;*-

169

DOIT.LE SALTS.

10H 2 0,

-f-

DE VENTER,

COHEN and BREDIG, and


VEKSCHAFFELT have found, by different methods, to be about 33
Similar changes have been investigated in the cases of CdClo.
2H 2
which loses a molecule of water of crystallisation at
VAN

'T

VAN

where
34, of ZnS0 4 .7H 2
Na
and
of
2 HP04.12H 2 0,
40,

about

the

salt

The transition temperature

in the formation

of double

which

at

converted into

is

37.

at about

c.

of water of crystallisation

molecules

seven

containing

same thing occurs

the

about

and decomposition

salts.

few characteristic cases will be fully described.

The formation

1.

The equilibrium

Na a S0 4 10H
.

and

the

salt

is

represented by the following equation.

is

+ MgSO,. 7H

transition

known

of astrakanite.

temperature

+ 13H 0,

Na 2 Mg(SO,) 2 4H 2

^i

about

is

as

mineralogically

21. 5.

astrakanite,

The double
simonyite,

or

bloedite.

powdered astrakanite be mixed with water in the


proportion represented by the above equation, at temperatures
below 21. 5, the thin paste which is at first formed solidifies
If

finely

after

time

short

to a dry, solid mixture of the sulphates of

sodium and magnesium; at temperatures higher than 21. 5 this


does not take place. A finely powdered mixture of the hydrated
sulphates of sodium and magnesium remains completely unchanged
at

temperatures below

in

order

E.

E.

E.

to

prevent

COHEN and

21. 5,
of

loss

D. M. Kooi.i,

Zeit.

WIEDEMANN, WIED. Aun.

COHEN

loc.

:!

A. E.

VAN

phys.

561,

Chem.
1882,

14,

71, 1894.

investigated several sulphates.

cit.

BATH,
'T

17.

be preserved in closed flasks


water; on warming the mixture,

if it

Xcit. phys.

Cliem.

18,

HOFF and VAN DEVKNTER,

180, 1895.
Zeit.

See

phys. Clunu.

p.
1,

203.
170, 1887.

Cf.

170

CHEMICAL EQUILIBRIUM.

21. 5

above

however,

astrakanite

formed

is

The last-mentioned change


some

this it occurs after

accelerated, and takes place

is

more

time.

In the case of astrakanite

of two

do

sulphates to

with

the

NH

C4H4

NaNH

transition

HOFF

and VAN

dealing with the combination


salt,

.4H 2 0)

first

^=

is

DEVENTER,

about

who found

thin

the

in

paste

6.

27,
that

O) 2

-f-

if finely

completely

mixture

solid

dry,

that at temperatures above 27

to VAN

powdered

in the proportion

at first obtained solidifies after

is

6H 2 0.

according

above equation, at temperatures below

which

and

prepared by SCACCHI.

sodium ammonium racemate be mixed with water


given

dextro-

to

form the racemate (Na

(NaNHAH

temperature
"

to

we have

while here

ammonium

sodium

of

C 4 H40 G .4H 2 0,

.H 2 0)2, which was

2(NaNH 4 C
The

we were

form a double

combination

laevo-tartrates,

to

later.

The formation of sodium ammonium, and of


sodium potassium racemate.

2.

'T

or

astrakanite be added to begin with, but even without

if

readily,

sooner

by the water liberated.

partial fusion being apparently produced

27,

the

some time

of the two tartrates,

and

this does not occur.

Further, the finely powdered mixture of equal quantities of the

two tartrates may be preserved without change in closed vessels


at temperatures below 27, whereas on warming it above 27
the formation of racemate occurs after a more or less prolonged
period, the water set free giving rise to partial liquefaction.

sodium racemate, a salt which


was first prepared by WYROUBOFF, 3 has been investigated by VAN
4
who found it to be completely analogous
'T HOFF and (JOLDSCHMIDT,

The formation

that

to

of

potassium

of the sodium

ammonium

salt.

The

transition tempera-

ture in the equilibrium


1

Rendi

conti di

Napoli,

atome im Raume, zweite


2

3
4

Aufl.

1865,
1894,

p.
p.

250. See also

phys Chem. 1, 170, 1887. See


Ann. Chim. Phys. (6) 9, 224, 1886.
Zeit. phys. Chem. 17, 505, 1895.

Zeit.

VAN

'T

HOFF, Die Lagerung der

34.
also Zeit. pliys.

Chem.

17, 47,

1895.

THE TRANSITION TEMPEBATURE.


2 (C 4

4EJ 2 0)

^L (C H
4

K Na. 3H

Sodium ammonium racemate, which


and laevo-tartrates

0,

at

formed from the dextro-

is

27,

monium

NH

racemates.

C 4 H4

6.

The change
(K Na C 4 H 4

The

6.

0) 2

^= (Na 2 C 4 H 4

in the case of

cording to VAN
2

decomposes again according to VAN


into sodium and amat 35
HOFF, GOLDSCHMIDT, and JORISSEN

'T

(Na

0) 2

The decomposition of sodium ammonium, and


of sodium potassium racemate.

3.

6.

about

is

K Na.

171

DOUBLE SALTS.

0) 2

^= (Na 2 C 4 H 4

transition temperature

C4H4

6] 2

is

6) 2

2
,

ac-

is,

quite similar.

+ (K

C 4H4

0) a

+ 8 H 0.
2

41.

about

laevo-

mixture of sodium and

ammonium racemates

30, and

at

also in

the case of the analogous mixture of the potassium sodium

with which the change occurs at

The decomposition

of

salts,

33.

(Na 2 C 4 H 4 6 ) + [(NH 4 ) C 4 H 4
4(NaNH 4 C 4 H 4 6 4H 2 0)
4(K Na C 4 H 4 6 4H 2 0) ^= (K 2 C 4 H 4 6 2H 2 0) + (Na 2 C 4 H 4
4.

+ 4H 0.

change occurs in the case of a mixture of sodium


and dextro-tartrates which changes into a

similar

ammonium

4) 2

potassium sodium racemate

HOFF and GOLDSCHMIDT

'T

+ [(NH

6) 2

6 )] 2
6) 2

+ 16H

2 0.

+ 12H 0.
2

copper calcium acetate.

It has been observed by H. KOPP that from solutions containing


the acetates of copper and calcium in equal molecular quantities

the

sometimes

salts

form of the double

crystallise out separately,


salt

he thought

it

sometimes in the

probable that the temper-

ature might be the determining factor.

REICHER

showed that

this is the

case,

which may be represented as follows,


1

Zeit. phys.

Zeit. phys.

'

MI._,0

Zeit. phys.

Chem.
Chem.
Chem.

The composition

17, 47, 1895.


17, 505, 1895.
1,

221, 1887.

of copper calcium acefate

is

often erroneously given as

on the authority of ETTLING (LIEU. Ann.

investigated

by RUDOUFF

(,11,0.,) ,.011,0.

an equilibrium ocurring

CuCa(C 2 H jO.>)j.
:

286. 1832). It has heen more fully


(Berichte, 21, 279, 1888) who found that the formula is CuCa
1,

172

CHEMICAL EQUILIBRIUM.

Cu Ca (C 2 H 3

2) 4

^= Cu (C 2 H 3

2) 2 .

of

and

astrakanite

2) 2 .

-f-

76. 2 and 78.

the transition point lying between

The formation

Ca (C 2 H 3

-f-

the double racemates,

of

which we have already considered, occurs on raising the tempwhile in this case the double salt

erature,

than about

temperatures lower

at

while above this temp-

77,

erature

into

change

of colour from blue to green which

its

decomposition
transition from one system
that

the

double

tetragonal

takes

components
the other

to

salt

is

the stable system

is

is

accompanied by a
due to the facts

is

while the

blue,

The

place.

copper acetate is green, and the small


crystals of calcium acetate are colourless.

metric

monosym-

needle-shaped

The decomposition of copper bi-potassium

5.

choride and of schonite.


The first-named
VRIENS

J.

CuCl 2

by

salt

different

was studied by W. MEYERHOFFER and


methods. It was found that the salt,
l

2H 2 0, which

2KC1.

crystallises

blue tabular crystals,

in

decomposes into copper potassium chloride, CuCl 2 KC1, potassium


chloride, and water at about 92, while below that temperature
.

formed from

is

it

its

2H 2

CuCl 2 2KC1.
.

This case

is

constituents.

CuCl 2 KC1

^=

-f-

KC1 -h 2H 2 0.

quite analogous to that of copper calcium acetate.

a molecule of copper chloride, CuCl 2 2H 2 0, be added to the


3
double salt to begin with, the transition temperature is depressed
to about 56, which is to be regarded as the transition tempIf

erature in the equilibrium

CuCl 2

The
salts
1

2 KC1. 2

researches

-+-

of

CuCl 2 2
.

J.

^=

VAN DER HEIDE

2 CuCl 2
4

Chem.

3,

336, 1889;

5,

-f-

4 H,0.

show that the double

which may be formed from K^SO^ and


Zeit. phys.

KC1

MgS0 4

i.

e.

schoenite,

97, 1890.

194, 1891; Inaugural Dissertation, Amsterdam, 1890.


3
This depression of the transition temperature is quite analogous to the depression
of the freezing-point of a solvent by the addition of a foreign substance.
2

Zeit. phys.

Inaugural Dissertation, Amsterdam, 1893. Zeit. phys. Chem. 12, 416, 1893.

Chem.

7,

THE TRANSITION TEMPERATURE.

173

DOUBLE DECOMPOSITION.

and potassium asfcrakanite, K 2Mg(S0 4) 3 4H 2 0,


undergo decompositions which are quite analogous to that which
has just been considered.

K Mg(S0
2

4) 2 .

6H 2 0,

The transition temperature

d.

in

cases of double

decomposition.
*

observed that on grinding together potassium chloride


Glauber's salt, the mixture liquefied, which he supposed to

SCHIFF

and

be due to a double decomposition accompanied by the formation


2
water. VAN 'T HOFF and REICHER
subsequently showed that

of

this

supposition

which occurs

is

is

correct,

and that the double decomposition

represented by the equation

+ 2KC1

Na 2 S0 4 10H 2
.

^=

the transition temperature being


If

the

K S0 4 + 2NaCl -f- 10H


2

0,

3. 7.

potassium chloride be replaced by

ammonium

chloride

analogous double decomposition occurs, the transition temp-

an

erature of which

The

e.

is

10. 8.

transition temperature of isomeric compounds.

3
According to TROOST and HAUTEFEUILLE the vapour of cyanic
acid condenses in the form of cyanuric acid or of cyamelide
according as the temperature at which the condensation occurs

above

is

cyamelide

or

below

into

150.

cyanuric

WELTZIEN

acid

by heating

it

in converting

with concentrated

some days crystals


From these facts it would appear

sulphuric acid until decomposition began


of cyanuric acid separated out.

succeeded

after

that a point of transition exists for the change

cyamelide ^rz: cyanuric acid.

These observations have been confirmed by VAN DEVENTER


found that the vapour of cyanic acid when maintained
l
'-'

'

:>

:>

who
at a

LIEB. Ami. 114, 68, 1860.


Xt-it.

phye. Chern. 3, 482, 1889.

Compt. Rend. 67, 1345, 1868.


LIEB. Ann. 132, 222, 1864.

By experiments \vhich have not yet been published, kindly placed


by the author. (E. COIIKX.)

at

my

disposal

174

CHEMICAL EQUILIBRIUM.

temperature

125

of

for

six

hours,

under

pressure of two

atmospheres, condensed in the form of a finely divided film, which


insoluble in water and under the microscope appeared to

was

be mainly amorphous, isolated crystalline fragments being visible


in several places.
When the condensation is allowed to take
at

place

the

175,

product

is

completely soluble in water and

formed doubly-refracting crystals.


In order to convert cyamelide into cyanuric acid directly, VAN
DEVENTER heated small tubes containing cyamelide, subsequently
determining the quantity of cyanuric acid contained in the mixt-

consists of well

ure

The determinations were made by

produced.

baryta solution,
reddened when

it

titration

with

having been found that phenol phthalei'n is


baryta has been added to convert the

sufficient

It was found in this


cyanuric acid into the di-hydrogen salt.
that
the
of
into
way
cyamelide
cyanuric, acid occurs at
change

temperatures higher than 135 (uncorr.), and that it is considerably facilitated by the addition of ready formed cyanuric
No increase in the quantity of cyanuric acid could be
acid.
detected after heating to 135

The

for

40 hours.

reversal of the change at temperatures below 135

could

be produced; perhaps a better result might be obtained by

not

the use of a solvent.

3.

The

Solubility and vapour pressure ab the


transition temperature.

transition temperature has been defined as the temperature

two systems in equilibrium can separate out of a solution containing them when it is
evaporated, so that at this temperature a solution may exist which

at which all the substances belonging to

saturated for

is

two

systems

both

therefore

above

or

systems.
intersect

below

The curves
at

the

of solubility of the

transition

only the

first

point;

at

or the second

it,
temperatures
system can separate out in the solid state, because, as has already
been proved, a solution which is saturated for one system is

unsaturated for the constituents of the other.


1

Compare page 87.

UNIVE1
175

THE TRANSITION TEMPERATURE.

Although, at any given temperature, only one of the systems


is

in a condition of stable equilibrium, the

change of the unstable

may fail

to take

stable system.

It is,

(or meta-stable) system into the stable condition

especially

place,

in

the

absence

of

the

generally possible to prepare two different solutions


saturated at the same temperature, by bringing together one or
therefore,

other system with the same solvent. These solutions will possess
different concentrations, the solution of the system which is stable
at the temperature in question being the

more

dilute,

while that

of the meta-stable system possesses the characteristics of a super-

allowing salt to crystallise out when placed


in contact with the constituents of the stable system.

saturated

The

solution,

existence of these supersaturated solutions, which do not

deposit the dissolved material spontaneously but only

when placed

with the substances for which they are supersaturated,


is very intimately connected with the existence of a transition
the two phenomena constantly accompany each other,
point

in contact

every transition temperature giving rise to two series of solutions


supersaturated with respect to the one system, or the other,
according to whether the temperature is above or below the
transition point.
It

was observed by LOEWEL

of sodium sulphate

may

Glaubers

with

Na 2 S0 4

salt,

or

contained

in

that two distinct saturated solutions

be obtained by mixing water with pure


the

pure anhydride.

these solutions

is

table together with the temperatures at

Temp.

The

quantities of

given in the following

which they are saturated.

176
are also

CHEMICAL EQUILIBRIUM.

two

different supersaturated solutions, viz.,

above

32. 65,

the saturated solution of Glauber's salt supersaturated with respect


to the anhydride, below 32. 65, the saturated solution of the

anhydride supersaturated with respect to Glauber's salt


is saturated for both salts.

at

32. 65,

the solution

Similarly, the following numbers were obtained with astrakanite \


the numbers giving the percentages of salt in the solution.

Temp.

THE TRANSITION TEMPERATURE.


In

the

the

concentrations

of the

product

a salt and

between

equilibrium

Again,

which

is

saturated with respect to

ously C cl C Br
,

etc.,

a constant

is

obtain,

etc.

concentrations of the ions in the solution

the

calling

k2

saturated solution

ions

we

quantity, at constant temperature, so that

CMBI-

its

the

of

177

we

all

the four salts simultane-

obtain

CM- C C

KI,

C M C Br
.

ka

etc.

and therefore,
2

Cm- C Br

MBI

C mBr

From which

that

is,

the

products of the solubilities of the bodies belonging

to

the opposing systems are equal at the transition point.


It

is

above and below

also easy to see that

of

the

the

of

the

this

temperature

product
pair of salts is
smaller than that of the ineta-stable pair.
When the salts dissociate into more than two ions, the above
concentrations
of ions;

if

solubilities

must be raised

the

dissociation

to a

stable

power equal

to the

into ions be incomplete,

number

each con-

centration must further be multiplied

by the activity coefficient.


At greater concentrations deviations from the rule which has

just been established will occur; this detracts, however, but little

from

its

practical utility,

information
position
its

of

as

to

the

transition

since

it

probable
point,

is

still

able to give valuable

existence,

and

approximate

which may then be sought and

position accurately determined by experiment.

For example, the equilibrium

Na 2 S0 4 10H 2
.

4- 2

KC1

^^

was examined with the following

SO, -h 2 NaCl 4- 10H 2

results.
12

178

Temp.

CHEMICAL EQUILIBRIUM.

THE TRANSITION TEMPERATURE.

A.

Temperature.

With

falling temperature.

179

180

Temperature.

CHEMICAL EQUILIBRIUM.

DETERMINATION OF THE TRANSITION TEMPERATURE.

181

Electrical methods.

S.

Electrical

2.

Electrical

method with both

stable and meta-stable

phases.

method with

stable and without meta-

stable phases.

Each of
its

these

application

and examples of
general methods

will be considered separately

which

after

given,

some

less

will be briefly noticed.

a.

THE DILATOMETRIC METHOD.


This
REICHER

has been most extensively employed by


in his researches on the conversion of

rhombic into monosymmetric sulphur.


The method depends on the fact
the

majority

of

cases,

the

that,

in

substances present

before and after the change have different specific

volumes, so that the transformation


anied

by

accomp-

an increase or diminution of volume.

The temperature being maintained


change

is

constant, a

volume therefore indicates that the

of

reaction has taken place

The
for

specific

example

is

volume
1/2.07,

of

rhombic sulphur

2
,

that of monosymmetric

sulphur 1/1.96, so that the conversion of rhombic


into

monosymmetric sulphur

is

accompanied by

an expansion.

The dilatometer

(fig.

27,

p.

94),

which

is

used in determining the transition temperature by


this method, consists of a cylindrical glass bulb
to

which a thick-walled capillary tube is fused,


whole having the appearance of a large

the

thermometer.

The bulb
which

is

to be examined,

W. SCHWAKZ,

is

partly filled with the substance

evacuated by means of a water air-

Beitrage zur Kenntniss der umkehrbaven Umwandlungen


pohmorpher Korper, Preisschrift, Gottingen, 1892; also KOPP, FOGG. Ann. 80, 175, 1850.
2
LANDOLT und BORNSTEIN, Physikalisck-Chemiscue Tabcllen, 2te Aufl. p. 119.
1

See also

CHEMICAL EQUILIBRIUM.

182
and

pump,
such as

then

or mercury,

petroleum,
be observed on a paper scale which

oil,

can

latter

completely with some indifferent liquid,


so that the position of the

filled

is

glued to the

capillary tube.

The form of dilatometer shown

35 may be used in

fig.

which only a small quantity of substance is available.


which is 12 cm. long and 1 cm. in internal
b'c,

in

cases

The

in

reservoir

diameter,

prolonged into a narrower tube ab, of about 4 mm.


which serves for filling it. The capillary cd is about

is

diameter,

cm. long and 1 mm. wide at c there is a small glass bulb


with a narrow stem which fits loosely into the capillary and prevents
its stoppage by particles of the substance contained in the bulb.

70

In

to

order

introduce the petroleum, the apparatus

is

sealed

up before the blowpipe at a, inverted, and the end of the capillary


d connected with the tube f by means of a caoutchouc stopper;
petroleum

is

then introduced at

means of the water air-pump.


petroleum, which takes its place
bring

the

excess

of

it

convenient

to

oil

remaining

at

is

/',

and the whole evacuated by

The

escapes

through the

in the apparatus,

In order to

air

level in the capillary tube the

poured out,

and the apparatus

again evacuated, the small quantity of air remaining in the bulb


expands and forces a quantity of petroleum out of the capillary

which

is

The height of

easily regulated.

the

oil is

read on a

paper scale glued to the capillary tube.

The

observations

are

made by heating the dilatometer

in a

for a considerable time at temperatures rising by


increments of a degree. The change in the mixture,
which gives rise to the change of volume, is indicated by a slow

thermostat
successive

alteration

in

the height of the

oil in

the capillary, which goes

on for several hours.

Taking sulphur for example, if the bulb be filled with the


rhombic modification alone, the change into the monosymmetric
modification

may
is

be

delayed very considerably


higher than the transition point.

temperature
been found advisable in
of the

system which

the delay in the

is

all

even when the


It

has therefore

cases to add, to begin with, a

formed by the change, as

commencement of the

reaction

is

in this

avoided.

little

way

183

THE TRANSITION TEMPERATURE. DILATOMETER.

By

alternately heating the bulb above, and cooling

much more

rapidly,

it

below the

caused to take place


change
so that dilatometers which have been used

transition point several times, the

several times (with the

is

same contents) allow of much more rapid

measurements. The addition of a solvent

is

also often favourable

to the change. REICHER, for example, filled the bulb of a dilatometer with rhombic sulphur and a mixture of 1 volume of carbon
bisulphide to 5 volumes of turpentine. About half of the sulphur

was converted

into the

monosym metric

modification by he at, after


s

which the position of the liquid in the capillary was read off at
the following temperatures

Temperature 95

Time

in minutes.

184

CHEMICAL EQUILIBRIUM.

At

temperature the height of the liquid in the capillary

this

tube

is

that

constant,

practically

is,

two systems are

the

equilibrium, and the transition temperature

The

dilatometric

chemical

the

is

method may be applied

reaction

95

6.

in

in all cases in

which

accompanied by a change of volume


no change of volume

is

this is not invariably the case, for example,

occurs in the conversion of Glauber's salt into anhydrous sodium


2

sulphate and water.


In order to calculate the amount of expansion or contraction

which accompanies a change

is

it

necessary to take into account

the composition of the systems in the immediate vicinity of the


transition point.
in the formation of astrakanite from a dry
of hydrated sodium and magnesium sulphates, the sub-

For example,
mixture
stances

with

(Na S0 4
2

10

are

and a solution saturated

astrakanite

the

that

so

astrakanite,

equation

which

the

represents

actual change
5.9

formed

really

is

b.

This method

0) -h 7.6(MgS0 4 7
.

0) -*=* 3 (Na 2 Mg(S0 4 ) 2

4H

0)

THE THERMOMETRIC METHOD.


is

based on the fact that

all

changes of the kind

under consideration are accompanied by an evolution or absorption


of

heat,

that system which

is

stable at the higher temperature

being formed with absorption of heat.


The transition point may be determined by this method by
observing the times which are required in order to heat or cool
the system through equal intervals of temperature, or by observing
the changes of temperature which occur in equal intervals of

The occurrence

time.

the

maximum

the

of

chemical reaction coincides with

retardation of the change of temperature, in fact

the sign of the change of temperature


1

To prevent evaporation the

4 atmos.

often reversed.

95. 6. T. E.
WIEDEMANN, WiED. Ann.

the pressure within

it

was

at

E.

BAKHUJS ROOZEBOOM.

sign 100

is

dilatometer was sealed up

H 2O

are dissolved in

'

100 mols.

Zeit.
4

17, 575, 1882.

phys.

chem.

2,

515, 1888.

to indicate that 4.6 mols.

of water.

ROOZEBOOM

MgS0 4 and

uses the

2.9 mols. Na 2 S0 4

THE TRANSITION TEMPERATURE.

185

THERMOMETRIC METHOD.

The method is practically carried out as follows


The substance which is to be investigated is placed
:

wide

in a

test-tube surrounded by cotton wool, in which a thermometer is


placed, it is then heated or cooled and well stirred with the

thermometer, and

The following

temperature read from time to time.


results were obtained in the decomposition of
its

schoenite represented by the equation

K Mg(S0
2

4) 2 .

+ H

:^

K S0 4 +
2

Falling temperature.

Time

t.

MgSO,.

0.

186

CHEMICAL EQUILIBRIUM.

which we

conclude

may

that the decomposition takes place at

this temperature.

THE CRYSTALLISATION METHOD.

c.

This method was employed in the investigation of the equilibrium


2

^~ (Na NH 4 CJ3A)

Na NH 4 CJIA- 4H 2

0.

allowing the salts to crystallise out from solution, WYand SCACCHI have shown that above 27 sodium ammonium
KOUBOFF

By

racemate

and

is

while below

deposited,

a mixture of the dextro-

it

Isevo-tartrates crystallises out.

THE IDENTITY METHODS.

d.

W.

MEYERHOFFER

temperature

become
the

the

identical

of

pointed
of

that

at

the

transition

the

mutually convertible systems


have already seen that
every respect.

solutions
in

out

We

also the

vapour pressures of the saturated

two

systems are identical at the transition


MEYERHOFFER says further, " There is no doubt that

the

temperature.
if all

has

and

solubilities,

solutions

the other properties of the solutions such as specific volume,

were to be represented
of the temperature, the curves would

refractive power, viscosity, conductivity, etc.

graphically

as

functions

intersect at the transition temperature."

The methods which


experimental

proof

will

now be

described all depend on the

of the identity of the saturated solutions of

the mutually convertible systems. According as solubility, vapour


pressure, or some other property of the solution be used as the
criterion,

the methods of determining the transition temperature

vary in experimental detail, so that we obtain the different methods


mentioned on p. 180, which will now be explained fully.
a.

We

solubility.

already

seen that the solubility curves of the two

convertible

systems intersect at the transition temper-

have

mutually

Determination of

Bull. Soc.

Zeit. phys.

Chim. 41, 210, 1884; 45, 53, 18S6.


Chem. 5, 105, 1890.

THE TRANSITION TEMPERATURE.

ature,

the

VAPOUR PRESSURE.

187

and have found by interpolation the temperature at which


and anhydrous sodium sulphate

solubilities of Glauber's salt

become equal from the observations of LOEWEL


BAKHUIS ROOZEBOOM
astrakanite by

(p.

175).

has determined the transition temperature of

means of determinations of solubility, the

which are given

in the following table.

The numbers

results of

are molecules

of the salts to 100 molecules of water in the saturated solutions.

Temperature.

188

CHEMICAL EQUILIBRIUM.

millimetre

scale

read without
saturated

sulphate

allows

solutions

have

the

difference of level of the oil to be

using the cathetometer.

been

of

Glauber's

contained in the following table.

Temperature.

salt

determined

The vapour

and of anhydrous sodium

by E. COHEN,
2

pressures of

the results

are

THE TRANSITION TEMPERATURE.

189

SOLUTION PRESSURE.

Just as a liquid possesses a certain power of expanding, in consequence of which it evaporates into any vacant space until the
of

pressure

maximum

vapour reaches a certain

its

as the vapour pressure of the liquid, so a liquid,

another liquid, in which

with

contact

is

it

known

value

brought into

if

soluble to a limited

extent, will dissolve until the dissolved part has reached a certain

maximum

osmotic pressure which, on account of the complete


the processes of evaporation and solution, NERNST
between
analogy
l

has called the solution tension


If a foreign
is

ot the liquid.

body be dissolved in the liquid

same way as
in which water

diminished in the

some

If

liquid

its
is

its

solution pressure

vapour pressure.
soluble to a limited extent

placed in contact with a hydrated salt which is insoluble in


the hydrate will give up water to the liquid in the same

be
it,

as

way

amount
dissolved

pressure

it

would

the

in

effloresce

of the salt be used a

air;

maximum

if

a sufficiently large

osmotic pressure of the

be attained, corresponding to the vapour


of dissociation of the salt in vacua, and which may

water

will

therefore be called the solution pressure of dissociation.

Since at a given temperature the solution pressure only depends

on the concentration of the dissolved water, VERSCHAFFELT deter-

mined the
water
In

latter

only,

amyl alcohol

using

as the solvent and

as the soluble liquid.

order

determine the concentration of the water in the

to

amyl alcohol solutions, a series of measurements of the solubility


of water in amyl alcohol at different temperatures was made;
the

concentration

cooling

it

until

concentration

any solution could then be obtained by


just became turbid, and interpolating the

of
it

corresponding

to

the

temperature

at

which the

turbidity appeared.

The determinations were made


Exactly
the
1

flask

"

2
;!

also

way:

weighed quantities of the liquids were brought into


of an EYKMAN'S freezing point apparatus 3 and the

Losungateusion"

preferable

in the following

to the

more

is

generally

" solution
pressure",

translated

strictly equivalent

term

''

LINKBARGKR, Zeit. phys. Chem. 13, 500, 1894.


The apparatus is described in the Zeitschrift fur phys. Chem.
in OSTWALD'S Lehrbuch der allgem. Chem. 1, 766.

which

is

perhaps

T. E.

solution tension".

2,

964, 1888, and

190

CHEMICAL EQUILIBRIUM.

thermometer placed in position, after bringing the mercury to


a suitable position on the scale, and comparing its readings with
those of a standard thermometer.

warmed
was

The apparatus was then slowly

water bath, and vigorously shaken until the mixture


homogeneous, after which it was placed in a beaker of
in a

water which was allowed to cool by radiation.

The temperature at which the turbidity appeared could be


observed with an error of a few tenths of a degree in the table
which follows, the temperatures are given to the nearest whole
;

number
0.5,

that

so

degree

they

may

be affected by a

accuracy which

of

maximum

error of

sufficient for the present

is

purpose.

The following

Amyl

is

an example of the numbers obtained.


8 046 grams

alcohol

Water

0.769

Concentration of the water =. 100

^
(j w

amyl alcohol

Concentration.

8.72

15

9.14

25

9.67

32

10.00

36

10.20

The following equation

represents the connexion between the

concentration c and the temperature


c

t,

0.05 (168

between

into this equation,

If the temperature at

and calculate

and

40.

t).

obtain the concentration of any solution,

to introduce the observed temperature at


it

6.

at different temperatures.

Temperature.

in

cent.

are the percentage concentrations of the saturated

solutions of water in

To

Ga
Gw

8-72 per

^~rT
(j

-f-

Temperature at which saturation took place

The following

=
=

it is

only necessary

which turbidity appears

c.

which turbidity appears

is

inconveniently

high or low, a known quantity of amyl alcohol, or water, may


be added in order to bring the temperature between suitable

THE TRANSITION TEMPERATURE.


limits (20

From

40).

now appears

the

initial

191

SOLUTION PRESSURE.

the temperature at which the turbidity

concentration

of the solution

is

easily

calculated; for example,


grams of a solution were taken
and 0.207 grams of water added to it, the turbidity appeared at

8.591

30,

so that the concentration of the

= 0.05

Cl

+ 30) =

(168

The whole amount of the water

Wl

and the

o on

initial

(8.591

is

solution

9.90 per

was

cent.

therefore,

+ 0.207) =

0.871 grams,

quantity,

0.8710.207

=i

from which the concentration, which

66.4
c

After

new

these

KOI
Q
0.591

=7.72
it

preliminaries,

0.664 grams.
is

to be determined,

per cent.

was possible

to determine the

transition temperature of Glauber's salt in the following

The

is

way

powdered salt was placed in a flask of about 100 cc.


and
treated with amyl alcohol which had been saturated
capacity,
the
salt takes up water from this forming a saturated
with water
finely

The flask was well closed and maintained at


aqueous
a constant temperature in a thermostat, being well shaken from
time to time. In order to obtain a supercooled solution of
solution.

sodium sulphate the

anhydrous

flask

with

its

contents was pre-

some time to a temperature above 33.


been
attained, after about an hour, the salt
Equilibrium having
settle
to
and
the amyl alcohol filtered, after which
was allowed
heated

viously

the

of the

concentration

in the
1

for

way

described.

This aqueous solution

become

identical

at

the

water

contained in

dissolves

transition

is

was determined

little

amyl alcohol, but sinco the two systems


they both dissolve the same quantity

temperature,

of amyl alcohol and though the solubility of the salt

temperature

it

is

changed a

little

the transition

unaffected.

2
PFEIFFEK, Zeit phys. Chem. 9, 445, 1892, has shown that the addition of foreign
bodies to a mixture of two liquids may displace the temperature at which the turbidity appears to a considerable extent. Special experiments on this point showed, however,

that

sodium

appreciable

sulphate

effect.

is

not

sufficiently

soluble

in

moist amyl alcohol to have any

192

The following

CHEMICAL EQUILIBRIUM.
table contains the results of the experiments.

TJNI

THE TRANSITION TEMPERATURE.

Temperature.

ELECTRICAL METHODS.

193

194

CHEMICAL EQUILIBRIUM.

combination

the

following

described,

direction

of the current

is

the

ZnS0 4 -solution,

Zn.

>

Zn, dilute ZnSO-solution

concentrated

have been constructed by NERNST 2 which


from those of MOSER'S type in the fact that, with ZnS0 4

Concentration
differ

for

the

cells

S0 4

example,

electrodes are

used instead of zinc

with this

arrangement the current flows from the more concentrated to the

more

dilute solution.

We

know

then,

first,

that in an equilibrium between condensed

substances the solubilities of the two systems, which are different


at

temperatures
at

equal
current

above

or

below

the

transition

point,

become

point, and secondly, that when a concentration


flows between two solutions it will disappear when the

that

concentrations of the solutions become indentical.

From

these

facts

it

is

evident that the disappearance of the

concentration
77iermomcfer

Zn

Sealing

.S"

Glass tube

current

As an example, the

ZnS0 4

transition temperature in the reaction

H2

195

ELECTRICAL METHODS.

THE TRANSITION TEMPERATURE.

ZnS0 4

+ H

will be taken.

The apparatus with which the determinations

made may be

are

with meta-stable phase it is represented


in fig. 37, and consists of two \essels, A and B, which are
connected by a syphon with limbs of equal length. Zinc

called the transition

which

sulphate,

few

'

finely

is

water,

in this

been

has

of

drops

the vessels

cell

powdered and moistened with

placed

in

the

narrower

parts

of

the solutions, being in contact with a

way

great excess of the solid salt, are maintained in a saturated


condition when the apparatus is warmed.
The syphon is filled with cotton wool saturated with a solution

of zinc sulphate, and the projecting ends of the wool are pressed
into the moist salt in A and B.

Two amalgamated
with

sealing-wax

rods

of

which

zinc,

the exception of about

i/g

covered

are

cm. of

their,

A small thermometer,

extremities, serve as electrodes.


?

shown

are filled

substance, such as sealing-wax,

in order

is

with some

indifferent

prevent any movement

to

When

in

of the electrodes during the experiment.

such as

salt,

graduated

is

introduced through the glass tube which


The wider parts of the vessels A and
the figure.
in Yio

with

lower

sodium sulphate, the metal of which


is under examination an electrode

cannot be used as an electrode,

which

is

of

is

the

mercury,

sulphate,

with

unpolarisable

must be employed
used.

respect

to

the anion of the salt

with sodium sulphate, for example, an electrode


surface of which is covered with mercurous

Connexion with the mercury

is

made by means

of a platinum wire fused through a glass capillary tube.


1

Only

a few

grams of the

salt

are needed, so that, on warming, the solution very

quickly becomes saturated.


2

Any

dissimilarity

of

the

electrodes,

which

would give

rise

to

a current,

is

avoided by short-circuiting the cell and allowing it to stand in that condition for some
If after a
time; the cells when not in use should always be kept in this way.
considerable

time some

inequality

still

remains,

it

may be allowed

for

by applying a

correction to the experiments.


3

The form

of

these experiments.

transition

cell

which

will be described later

may

also be used in

196

The

CHEMICAL EQUILIBRIUM.
transition cell

Unpolar-

is

now

to be arranged in the following order

THE TRANSITION TEMPERATURE.


to depress the temperature
ability

of

ZnSO

into the system

much more than


6

0, which

temperature, then becomes too great,


The temperature of the thermostat

very

slowly

minutes

five

Every

since the prob-

is

stable at the lower

now allowed

is

ZnS0

to rise

the solutions remain constantly saturated.

that

so

this,

change of the system

of the

occurrence

the

197

ELECTRICAL METHODS.

the

circuit is closed,

and the deflection of

the galvanometer needle noted this becomes smaller and smaller


as the temperature rises, a point being finally reached where the
;

deflection

30.8 3iS

the

in

is

which the

opposite

deflection

3M 3M JW 3&S 362

37-f

3&g

JM

The temperature

direction.

zero (the transition temperature)

is

40j

4l.g

4Zg

US

454

4W

is

SIS 5SJI 53S

47.S

at

then

6M

Fig. 39.

obtained by interpolation. The explanation of the diminution of the


current is to be found in the diminution of the difference between
the

concentrations

temperature;

of

the

at

the

solutions

transition

the

current

raising the temperature

the

current

from

what

solubility.

transition

become

the

is

said

When
point

identical,

on

p.

temperature,

same,

are

trations

in

is
is

and

with rising
where the concen-

zero,

and

reversed,

as

on

further

is

obvious

174 on the course of the curves of

the

temperature is maintained above the


for some time the solutions in A and B again

and the current disappears.

198

CHEMICAL EQUILIBRIUM.

The following
with Glauber's

table contains the results

salt;

the temperature

of the galvanometer under &.

is

which were obtained

given under

t,

the deflection

THE TRANSITION TEMPERATURE.

means

of

ELECTRICAL METHODS.

199

the transition cell without the presence of the meta-

The saturated solution of the meta-stable phase


an
unsaturated solution of known concentration,
replaced by
which remains unchanged (neglecting the small thermal expansstable

system.

is

ion) at all temperatures.

The

cell is

Unpolarisable

electrode.

put together as follows:

200

CHEMICAL EQUILIBRIUM.

a solution of sodium sulphate of known


the mercury in the tube
strength is poured to a depth of 4 or 5 cm., while the tube b
,

contains a paste of finely ground Glauber's salt and the same solution.

communication between the two liquids

Conducting

is

provided

Fig. 40.

by

about

Oj-tube

in the

cm.

wide

fille

d with cotton

wood soaked

This tube has a relatively small


of importance for the sensitiveness of the

sodium sulphate solution.

resistance,

which

is

method.
b,

two J_-shaped

by means of

a small water-

Just above the surface of the mercury in a and


glass stirrers,

motor,
the
b

so

electrodes

remains

gether

by

r,

that

are caused to rotate

pasty mass of crystals and the solution


are kept in constant motion, and the solution
the

saturated.

The

wooden frame

at
in

parts of the apparatus are held toeasily taken

to pieces,

serves to support the apparatus in the thermostat.

which

also

THE TRANSITION CELL.

201

\Vith Glauber's salt, the solution becomes saturated in about two


hours, after which the electromotive force remains constant.

The

measurements of potential were made by means of the compensation method of POGGENDORFF and Du Bois REYMOND with the
;

galvanometer

used

difference

was appreciable.
Three different cells were

of potential

of less than Vsoooo

'

volt

investigated, the solutions of constant

N/ 2 and N/ 4 respectively.
The other solution being a solution of sodium sulphate saturated with respect to the modification which is stable at the

concentration being N,

temperature
force

given,

the

(in millivolts)

Cell

I.

following

values

of

the

electromotive

were obtained.

Normal sodium sulphate

solution.

202

CHEMICAL EQU1LIBBIUM.

E!

= 16.63

E2
The

10.12

-!-

0.548
0.297

transition temperature obtained

0.00622

h 0.0253

t
t

2
.

2
.

from these numbers

is

33

30Cell

20

JO

20 c

Temperature
Fig. 41.

fl '/>

ru)rm,aL

.0.

THE TRANSITION CELL.


Cell III.

N/4 sodium sulphate solution.

203

EQUILIBRIUM.
SECOND PART.

THE THREE FORMS OF PHYSICAL EQUILIBRIUM.


The occurrence

of equilibrium between

two

different systems,

general between two different forms of the same kind of


is not confined to the domain of chemistry. An
analogous
physical phenomenon, evaporation, was known long before anything
or

in

matter,

of the kind had been discovered in chemistry.

The equilibrium which,

water for example,


exists between water and steam, when the latter has reached its

maximum

in the evaporation of

may be

explained by the simultaneous occurrence


of two changes in opposite directions, the one being the conversion of water into steam, the other the conversion of steam into
pressure,

water with equal speed.

The symbolic representation which has been used


of chemical equilibrium
special case

which we have taken being represented by the symbol:


liquid

There

may

is,

as

we

water

shall

^n:

see,

water vapour.

a far reaching analogy between

chemical and physical equilibria. The latter


three

classes,

which

are

quite

similar

to

may

be divided into

those

in

chemical equilibria were arranged, namely


1.

Physical equilibrium in homogeneous systems.

2.

Physical equilibrium in heterogeneous systems.


Physical equilibrium in condensed systems.

3.

in the case

therefore be employed here also, the

which the

205

HOMOGENEOUS SYSTEMS.

I.

The

physical analogue of a homogeneous chemical equilibrium

such as

N0

2,

phenomenon which, though not well marked, is of very


general occurrence, namely those molecular attractions which
is

the

cause

deviations

from

laws of BOYLE and CHABLES (or

the

GAY

LUSSAC); these attractions do not tend to the formation of any


sharply defined product were there any such tendency we should
;

have a case of chemical equilibrium.


II.

HETEROGENEOUS SYSTEMS.

heterogeneous chemical equilibrium, such as

NH HS ^=+ NH + H
4

which has already been described,

is

2 S,

to be regarded as completely

analogous to a physical evaporation, such as

^zr

Liquid water

The equations which were used


we have
the second

Steam.

in the first case apply also to

d
,

from which

where

2T

d log

~r^

^~,

the

concentration of the vapour, q the quantity of


heat which is evolved by the condensation of 18 kgrms. of water
vapour, without external work being performed.

From

is

the above equation

Ca

we
q

obtain,

by

/J_

integration,

l_\

where GI and C 2 are the concentrations of the saturated steam


at the absolute temperatures T! and T 2
.

206

EQUILIBRIUM.

equation we can calculate the value of q by


introducing the vapour pressures p t and p 2 at the temperatures

From

this

T 2 we have

T! and

^2

r
^1

P2

^T
J-2

Pi

A!

and therefore,
p2

log

--

Pi

log

q
:

T7

Introducing the following numerical values,

273

T!

T2

273

+ 11.54

Pl

p2

=10.02

4.54

we find q = 10100.
The heat of evaporation of a kgrm. mol.
is 10854 cals. To obtain q from this number,

of water at

the external

5. 7 7
work

which accompanies the condensation must be subtracted this is


2T = 558 cals., and therefore q = 10296 cals., -which agrees
;

sufficiently well

The

with the number calculated.

solution of solid bodies

equilibrium, and

may

be represented as follows

Undissolved substance

The equations which apply


applicable to this case.

the solubility

it

another example of this kind of

is

^z:

dissolved substance.

to chemical equilibrium are also

In employing them to calculate q from

however, necessary to remember that they are

is,

only strictly true for very dilute solutions.

As

is

well known,

law of GULDBERG and WAAGE

the

may

be

written in the form

for very dilute solutions at constant temperature,

are

the

numbers

which take part

of

each

of

the

in the reaction,

different

and

where a x and a 2

kinds of molecules

depend on the nature

of the solvent and of the dissolved substance, and the summations


extend to all the bodies belonging to each system.
L

J.

dissous.

H.

VAN

Also,

'T

HOFF.

Lois

de 1'equilibre chimique dans

Archives Neerlandaises 20, 291, 1885.

1'etat dilue,

gazeui ou

207

SOLUBILITY.

Since Saiii relates to the dissolved bodies forming part of the


first system, we have, in the special case of equilibrium between

a solid body and

C2
is

its

^a^ =

saturated solution,

0,

and therefore

the concentration of the dissolved substance, and

is

equal to the value of

for this substance, so that at constant

temperature
1

C
that

at

is,

K,
the

temperature

given

substance has a

soluble

definite solubility.

Introducing this value of

into the equation

the influence of temperature on the equilibrium,

which represents

we

obtain

cUogC

.
"

dT

_q_

dlogG

"

dT

2T2'

_q "

2iT 2

This equation represents the relation which exists between the


change of the solubility C with the temperature T and the heat
evolved

from

by the separation

the

saturated

of

solution,

kgrm. mol. of the substance


which is its molecular heat of

with reversed sign. By the molecular heat of solution


meant here the heat of solution of the substance in its own

solution
is

saturated solution.

This

theoretical

large

quantity

(Final, fictitious or theoretical heat of solution).

heat of solution and the heat of solution in a


of

water

(integral

heat

of

solution)

may

differ

very considerably from each other, and even be of opposite sign.


REICHER and VAN DEVENTEE, 2 for example, have shown that

copper

chloride

dissolves

evolution of heat, while

it

in

large

quantity

dissolves in its

own

of water

with

saturated solution

with absorption of heat.


It is to be noticed however that with sparingly soluble bodies
the difference between the integral and the theoretical heats of
solution

between

is

negligible,

for

since

there

is

very

little

difference

saturated solution and pure water, they have very


nearly the same action on the salt.

the

1
C. M. VAN DEVENTEU and J. VAN DE STADT, Zeit. phys. Cliem.
BAKHUIS ROOZEBOOM, Rec. des Trav. Chim. des Pays-Bas, 8, 96, 1888.
2
Zeit. phys. Chem. 5, 559, 1890.

9,

43, 1892.

208

EQUILIBRIUM.

J.

LAAR

VAN

J.

dlogC

has

obtained

the

for

expression

following

"

dT

dlogC
dT
where

the

is

T2

called

so

The formula

is

only

electrolytes.

It

is

_q^

be

dilute

to

applicable

to

coefficient

activity

(z

=.

i.

1,

= 2, equations (1) and

1).

of binary

solutions

when

noticed that

non-electrolytes, and also when

e.,

with

become

(2)

identical.

Equation (1), p. 207, shows that the sign of the change of


solubility with rise of temperature is determined by that of the
heat of solution
ously with VAN

When
change

LE

heat

the

obtained this result simultane-

HOFF.

'T

with

CHATELIER

the

of

(ALEXEJEFF

sodium

chloride

calcium

),

The
and

solubility will not

solubilities

sulphate

DEVENTER

(VAN

the

zero

is

temperature.
3

alcohol

solution

(LE

VAN

DE

of

isobutyl-

and of

CHATELIER),

STADT

in

water

illustrate the correctness of this result.

If the heat of solution

when

temperature
Finally

evolved

with

q be

positive,

that

heat

is,

is

absorbed

the substance dissolves, the solubility increases with rising

which

the

if

when

the case with the majority of substances.


heat of solution be negative, that is, heat is
is

the substance

rising temperature.

is

dissolved, the solubility decreases

All the gases, and also ether, carbon

bisulphide, bromine, and nicotine (LE CHATELIER) belong to this


Lime and calcium sulphate may likewise be added to the
class.
list,

the latter having a

According

to VAN

maximum

'T

solubility at about

d log C

"

The deduction

of

this

(MARIGNAC).*

relatiouship

2lT 2

dT
1

38

HOFF G the equation

is

to be

'

found in the

Zeit. phys.

Chem.

17,

546, 1895.
2

Compt. rend. 85, 440, 1877, Compt. rend. 100, 50, 1885.

Compt. rend. 100, 442, 1885.


Zeit. phys. Chem. 9, 43, 1892.

5
Ann. Chim. Phys. (5), 1, 274, 1874.
Chem. Tahellen, 2te Aufl. 238.
6

Loc.

cit.

p.

206.

See also

LANOOLT and BORXSTEIN, Phys

209

SOLUBILITY.

may

be employed to calculate the value of

q,

when

the solubilities

of a substance at two temperatures, and the value of

By

integration we obtain

and therefore,

log

log

JL

(^

:=

where (^ and C 2 are the


Tj and T 2

are known.

const.,

2i^- -^

r-

logg

-|-),

...... (3)

solubilities at the absolute

temperatures

The following

shows that the values of q calculated in this


way agree satisfactorily with those which are determined directly.
The substances examined are all rather sparingly soluble these
table

bodies were chosen because the equation by which q

only applies to dilute solutions.

Substance.

is

calculated

210

EQUILIBRIUM.

It

is

noteworthy

that

gives

binary electrolytes,

LAAR'S

VAN

formula, which applies to

KC10 3

for

10.1, the observed

value being 10.0.

III.

The

CONDENSED SYSTEMS.

class of chemical equilibria

which

characterised by the

is

existence of a transition temperature possesses a complete analogue

changes of fusion and

in the physical

~^^ monosymmetric

rhombic sulphur
there

is

below

it

certain

the other

physics in the

stable

above

phenomena

may

nature

reaching

apparent when we

the

be written,

water ^~*~
far

sulphur,

of fusion and solidification, the change,

taking water for example,

The

which

In the change

one system,
precisely the same thing is found in

temperature
is

solidification.

of the

consider

the

ice.

analogy will become more


of pressure

influence

on the

transition temperature of condensed systems.

So

far,

only the fundamental resemblance which exists between

chemical and physical phenomena has been pointed out.


is,

however,

namely

respect,

tered

considerable

obviously
different

between them

There
in

one

phenomena encounThe reason of this variety is

in the surprising variety of the

among chemical
to

difference

be

equilibria.

found

conditions

of

physical equilibrium

is

in

while the number of

the fact that,


substance

which can take part

in a

limited to three (solid, liquid and gas) no

such limitation exists in the case of chemical equilibrium. The


parallelism of the two classes will therefore be most evident
in those cases of chemical equilibrium in

which only two bodies

take part.

Again,

from what has been said

it

is

evident that physical

equilibrium may be regarded as merely the most simple form of


chemical equilibrium.
Chemical equilibrium in a homogeneous

system

is

found in

its

most simple form in the physical deviations


Chemical equilibrium in a

from the laws of BOYLE and CHARLES.

FUSION AND SOLIDIFICATION.

211

heterogeneous system becomes, in its simplest form, evaporation


or condensation equilibrium of incompatible systems corresponds
;

to fusion.

further difference between physical and chemical equilibrium

found in the velocity with which the condition of equilibrium

is

reached.

While

very great in physical changes, a


certain shuggishness is observed in similar chemical changes.
KAUMANN *, for example, found that in evaporating naphthalene, or
is

perchlor-ethane,
rapidly attained

the

this

is

maximum vapour pressure is much more


than with ammonium carbamate. The equilibrium
the

of hydrated salts

generally attained only


after the lapse of a considerable time, and' the inaccurate results
of many measurements of the pressures of dissociation of such
in

salts

dissociation

may

be due to this circumstance.

The same

difference

is

is

also noticeable

between the phenomena

of fusion and the similar chemical changes in condensed systems;


while the former change is complete almost immediately after
the

change

of temperature, the latter

takes place very slowly

indeed.
It

is

therefore

necessary,

in

the

experimental

changes which tend to bring about equilibrium,

study of the

to take cases of

only in such cases is the course of the


to be susceptible of measurement.
slow
change sufficiently

chemical

change,

for

Berichte, 4, 646 and 780,

FROWEIN,

Zeit.

pliys.

1871.

Chem.

1,

1,

1887.

EQUILIBRIUM.
THIRD PART.
DIAGRAM OF THE INFLUENCE OF TEMPERATURE
ON EQUILIBRIUM. DETERMINATION OF THE
TRANSITION POINT OF SULPHUR.
The

of the laws governing equilibrium

application

facilitated

by

the

diagram

simplifies the expression of the

and has

made

it

which

will

now be

is

greatly

described;

this

complex phenomena very considerably,

-possible to predict the transition

temperature

of sulphur.

In order to obtain a graphical representation of the equation

d log

~~dT~~

we

will

take

the

values

of

q
2T2'

as ordinates and those of

as

abscissae.

The

transition temperature of the

of sulphur

may

Representing
solid

R! R

2,

two

crystalline modifications

then be calculated in the following way.


first

the physical equilibrium which occurs between

rhombic sulphur and sulphur vapour, we obtain the curve


the ordinates of which are the concentrations of the sulphur

vapour, the abscissae the corresponding absolute temperatures.


Since the concentration C r of the sulphur vapour in equilibrium
with rhombic sulphur is equal to K, this curve represents the

equation
d log C r

qr

dT

2T 2

'

213

CALCULATION OF THE TRANSITION POINT OF SULPHUR.

where q r
vapour

is

in

the heat evolved by the condensation of the sulphur

the

rhombic

without

form,

the

performance

of

external work.
also

Monosymmetric sulphur

reached a certain

maximum

evaporates until

pressure

fore be represented in a similar

way

its

the equilibrium

by the curve

vapour has

may

MiM

2,

there

corres

ponding to the equation


d log

Cm

"

dT

qm

2T

2'

Cm

being the concentration of the vapour of monosymmetric sulphur


at its maximum pressure, and q m the heat evolved by the condens-

ation of sulphur vapour in the form of monosymmetric sulphur,


without the performance of external work.
The two curves RiR 2 and MiM 2 intersect at A, corres-

ponding to the temperature T rm At this point the concentrations,


and therefore the pressures of the vapour given off by the two
.

modifications

pressure

metric

of

of

the

sulphur

rhombic

modification,

above it the vapour


than
that
of the monosymgreater

are
is

identical

from which

it

follows that at temperatures

214

EQUILIBRIUM.

T rm rhombic

higher than

sulphur will change into monosymmetric

consequence of a kind of distillation, since the rhombic

sulphur in

emits vapour

at

than

pressure

greater

the

monosymmetric

sulphur.

At temperatures lower than T rm


forward, so that

T rm

third

curve

have

been

described

which

the opposite process will go

the transition temperature.

is

may now

FiFo

this

added to the two which

be

the

represents

physical equilibrium

between fused sulphur and sulphur vapour,

exists

it

corres-

ponds therefore to the equation


d log C f

qf

"

2T

dT
where Cf

and

sulphur

M^M^ and RiR 2

cuts the curves

so

T rf

that

two

transition

temp-

the melting point of rhombic

is

scale.

Similarly the point of intersection

We

to

in the points

represents the temperature T rf above which rhombic


passes into the liquid condition and below which the

sulphur on the absolute

point of

no external work

occurs,

opposite

condition,

liquid

which therefore correspond

C,

eratures.

F XF 2

the heat evolved by the condensation

is

the

to

vapour

sulphur

being done.
The curve

'

the concentration of the saturated vapour in contact

is

with liquid sulphur, and q f


of

C corresponds

monosymmetric sulphur on the absolute

are

now

in a position to obtain,

to the melting

scale.

by means of the diagram r

the relationship which exists between the three transition temperatures T rm T rf and T mf and the quantities of heat which are
,

evolved
this

by the changes occurring

relation

is

it

possible

to

From

at these temperatures.

calculate the value of

T rm

i.

e.,

the transition temperature of the two crystalline modifications of


sulphur.

The
lines,

ABC

triangle
since

follows

the

be regarded as bounded by straight


C A, and
are very small.
This

may

angles

BAG

from the fact that the concentrations of the sulphur

vapour in the neigbourhood of the transition temperatures (about


100) viz. AT rm BT rf and CT mf are very small.
,

215

CALCULATION OF THE TRANSITION POINT OF SULPHUR.

We

have therefore,

AB

AB

which

in

BC

BC

BCA

sin

T rm

T rf

T rf

T mf

BAG

sin

approximately.

T rm B
Again, owing to the small values of
the following relation holds good approximately
,

T rf

and C

T mf

QRPA
om
JtJbA

RAP

oJbJAO
sin

_dlogC m

d Cf

d
Cm -

dlogCf

d Cr

dlogC

dlogC r
dT

dT

From

our previous equations

dlogC m
dlogCf
dT

d Cm

__ q m

we

have,

dlogC m

dlogC r

qf

qr

dT

9T
^Imf

2T
^-l-m

therefore,

BCA

Sin

BAC = **

sin

2Tmf

2T mr

or

T rf

-T

rm

:T mf -Trf =

-f

2T mt

:-=^
2T
mr

In order to calculate the transition temperature


numerical values must now be introduced.

Tmf

and

T rf

T rm

the different

the melting points of monosymmetric and rhombic


sulphur respectively, have been determined by BRODIE who found
,

Tmf
qm

qf

=
is

273

T rf

120,

273

the heat evolved by the conversion of fused sulphur

monosymmetric modification, that is its heat of fusion,


similarly the heat of fusion of the rhombic modification.

into the solid


-

qr

qf

is

According to BERTHELOT,

qm
1

114.5.

qf

qr

Proc. Roy. Soc. 7, 24, 1856.


Essai de Mecanique Chimique

1,

qm

0.15

413 aud 553.

0.04

216

EQUILIBRIUM.

So that we obtain
387.5

5.5

393 2

or

T rm
The

transition temperature of the

of sulphur

by

273

is

therefore 96

direct experiment as

Experiment and
agreement.

.3.

96.3.

two

crystalline modifications

REICHER determined this temperature

95. 4.

calculation

are therefore in very satisfactory

EQUILIBRIUM.
FOURTH PART.

DISPLACEMENT OF EQUILIBRIUM WITH


THE TEMPERATURE. PRINCIPLE OF MOBILE
EQUILIBRIUM.
The observations which have been made on the
of

equilibrium lead to

be expressed in the following

Every

equilibrium

different

a simple general conclusion,

between

way
two

forms

which may

different

conditions

of matter

is
displaced by lowering the temperature, at constant
towards
that system the formation of which evolves heat.
volume,
This principle applies to every possible case, both of chemical

(systems)

and physical equilibrium.


as

well

as

the

finally,

of
fact

It

depression
that

if

indicates the effect of an elevation,

of the

no system

temperature;
is

ciple

cases

equilibrium"

of equilibrium.

will

now

expresses,

present the formation of

which evolves heat, a change of temperature


the equilibrium. This principle, which will be
of mobile

it

will not displace

called the "prinbe demonstrated for all

The three forms of chemical

equilibrium,

and the three forms of physical equilibrium will accordingly be


considered.

I.

THE PRINCIPLE OF MOBILE EQUILIBRIUM APPLIED


TO HETEROGENEOUS SYSTEMS.
a.

The two
in

this

Physical equilibrium in heterogeneous systems.


Evaporation and condensation.
different states of

equilibrium,

are,

matter with which we have to do

on the

one hand, the liquid or

solid,

218

EQUILIBRIUM.

on

hand the

gaseous state; the liquid state being


formed with evolution of heat from the gaseous

other

the

that

which

one,

the

is

quantity of liquid should

the

when

the expense of the vapour

increase

at

lowered

that

that

requires

principle

is

the temperature

is

that cooling must favour condensation

to say,

nothing further need therefore be said on this point.


Chemical equilibrium

b.

As we have already

seen, the equations


2

Cf
an
IK?

hold

good here,

whose

is

is

GI

dlogK

_q_

"2 T

dT

2'

evolved when the system


and
formed,
ni and n 2 relating to

the

being

concentration

in heterogeneous systems.

heat

those bodies which are not in the condensed condition. In


strating the principle here,

those
the

it

is

demon-

convenient to distinguish between

which n! and n 2 both differ from zero, as in


equilibrium between hydrogen, ferrous oxide, steam and
cases

in

metallic iron,

H +
where

ii!

FeO ^=

Fe,

and n 2 are both unity, and those in which n t or n 2

is

equal to zero, as in the classical equilibrium

CaC0 3 ^n^ CaO + C0 2


where ni

We
will

and n 2

1.

shall only consider the latter case here, since the

be

which

later

explained

equilibrium.
in

0,

together

with

homogeneous

former

chemical

Confining ourselves then to heterogeneous equilibria

only

one

of

the

systems

contains substances in the

uncondensed condition, and calling the concentration of this system


C 2 the equations, after putting i^
0, take the following form
:

ii 2

n
L
2

Iv

and1

dlogK
r~

and therefore
2

d log C 2

dT

2 T*

219

THE PRINCIPLE OF MOBILE EQUILIBRIUM.

From
is

C2

this

it

evident that the system whose concentration

is

will increase or diminish in quantity, at the expense of the

other system, when the temperature rises, according as q is positive or negative, while a fall of temperature will produce the
opposite result.

The equilibrium

therefore

is

always

displaced

by a

fall

of

temperature towards the system which is formed with evolution


of heat, as the principle enunciated above requires.

The equilibrium above mentioned,

NH HS
4

is

^=

+ NH

3,

good example of the application of the principle the system


the formation of which from H 2 S + NH 3 evolves heat,
;

NH HS,
4

is

produced at the expense of the latter when the temperature

II.

THE PRINCIPLE OF MOBILE EQUILIBRIUM


APPLIED TO CONDENSED SYSTEMS.
Physical equilibrium in condensed systems.

a.

Fusion and

The

falls.

solid

here.

The

solid,

the

solidification.

and liquid states of matter are to be considered


principle of mobile equilibrium requires that the
of

quantity

when

of the liquid

evolution of heat

which suddenly increases

the temperature sinks,


that

is,

at the expense

shall be formed with

fusion absorbs

solidification evolves,

heat.

Chemical equilibrium in condensed systems.

b.

Incompatible systems.

In

the

principle

physical
is

obvious,

shall see that

of chemical

equilibria

it

is

the

just

considered the

phenomena

also in complete

of the

known

we

harmony with the phenomena

equilibrium in condensed systems.

undergo sudden displacement at a

truth

being so well

definite

These equilibria

temperature the demon;

stration of the truth of the principle in this case, depends therefore

on showing that the change, which, at the transition point, is


brought about by lowering the temperature, will always lead to

220

EQUILIBRIUM.

the production of the system which is formed with evolution of heat.


Taking for example the change of rhombic into monosymmetric
sulphur, or that of cyanuric acid into cyamelide, cases in which

each system contains only one substance and in which the vapour
evolved by both systems is the same, the truth of the principle

may

be shown as follows.

Fig. 43.

The

equilibria

and the

maximum
K! K

as

of

the

vapour, measured at
the temperatures

and

ordinates,

its

as

Suppose that in the figure the lines MI M 2


represent these quantities for the two allotropic

fig.
2

it

concentrations

pressure,

abscissae,

between each of the two systems


emits may be represented graphically

subsist

vapour which

by taking the

and

which

43.

modifications of sulphur.

According to what is said on p. 213 the point of intersection,


A, which represents the temperature at which the vapour pressures
B the
are equal, is the transition point above the temperature
;

modification

to

which the

It

MI

refers will exist,

below

it

For sulphur, therefore, MI M 2 would


monosymmetric, K! K 2 to the rhombic modification.
must now be shown that the modification which is stable

that referred to by KI
refer

line

to the

2.

221

THE PRINCIPLE OF MOBILE EQUILIBRIUM.


at the lower temperature

that which

formed with evolution of heat from

is

The

stable at the higher temperature.

is

MI M 2 and K! K 2

of which the curves

equations,

are the graphical represent-

ations, are

d log C r

dlogC m

q r_

"

dT

T2

'

qm

"

dT

T2

'

C r and C m being the

concentrations of the saturated vapour


rhombic
and
by
monosymmetric sulphur respectively,
and q m being the quantities of heat evolved by the

off

given

and q r
formation of rhombic and monosymmetric sulphur from sulphur
vapour, no external work being performed.
The heat evolved by the conversion of monosymmetric into
rhombic sulphur is q r q m and from the figure it is evident that
-

dlogC m

dT
from which q r

>

qm

and therefore q r

heat accompanying the change,


principle of mobile equilibrium.

The
this

results

of

qm

the evolution of

positive, as is required

by the

experiment are also in agreement with


MITSCHERLICH found that heat is evolved when
direct

conclusion.

transformed into the rhombic modific-

is

monosymmetric sulphur
ation.

is

TROOST and HAUTEFEUILLE

observed that the conversion of

which takes place when the tempaccompanied by an evolution of heat-

cyanuric acid into cyamelide,


erature

is

LEHMANN

nitrate

depressed,

found

undergoes

The researches
likewise

formed

of

is

the

while

different

changes

at

which

ammonium

cooling give rise to liberation of heat.

FROWEIN and of VRIENS (pages 158 and 161)

support to the principle that the system which


the expense of the other with evolution of heat

lend

produced when
1

that

the temperature

falls.

POGG. Ann. 88, 328, 1853.

Compt. rend. 67, 1345, 1868.

GROTH'S

Zeitschrift fur Krystallographie, 1, 106, 1877.

is
is-

222

EQUILIBRIUM.

THE PRINCIPLE OP MOBILE EQUILIBRIUM


APPLIED TO HOMOGENEOUS SYSTEMS.

III.

The physical equilibria which come under this heading may


be neglected, since the principle relates to equilibria between two
different states of matter, and there is no reason for assuming
the

two

of

existence

substances

different

action occurs which, however,

is

in cases where,

for

show that some molecular

example, deviations from BOYLE'S law

insufficient to give rise to

any

sharply defined product.


the

In

of

case

homogeneous chemical equilibrium, the proof

of the truth of the principle depends on the equations

CD)

where q

as before, the heat evolved

is,

system of concentration

We

may

Cj.

by the formation of the

at constant volume.

which q

distinguish between cases in

those in which

it is

When it is positive,

negative.

positive and

is

that

is,

when heat

evolved by the formation of the system of concentration

is

constant of equilibrium

the

erature,

and

therefore

because Ci

invariable.

When

will decrease with falling

will

GI

C 2 remains

increase

GI,

temp-

the expense of

at

C2

volume being maintained


the
first
system is formed with
negative

is

constant, the

absorption of heat, and the second, therefore, with evolution of


heat the second system, of concentration C 2 will then be formed
,

at

the

expense

depression

of

the

first

of temperature

when

the

temperature

falls.

thus always increases the quantity of

the system the formation of which evolves heat.

The equilibrium

N
may

^i

serve as an example of this.

of mobile equilibrium the system

N0

According

temperatures at the expense of the system 2

known
The

to the principle of

will be

formed at lower

N0

2,

which

is

well

to be the case.

application of the principle of mobile equilibrium

makes

223

THE PRINCIPLE OF MOBILE EQUILIBRIUM.


it

which any given chemical

to predict the direction in

possible

equilibrium will be displaced at higher or at lower temperatures.

Since the equilibrium

displaced, on depressing the temperature,

is

towards those systems which are formed with evolution of heat,


these will predominate at lower temperatures, while at higher
temperatures they will disappear more and more, giving place to
those which are formed with absorption of heat.
In the equilibria
.N 2

NH

2N0

^-*r

NH + H S

.HS ^z

Cyamelide y~*~ Cyanuric acid


for example, the quantities of the systems

more

increase

will

more

and

on the

left

hand

side

the expense of those on the

at

temperature falls, so that at lower temperatures


right
the fraction of the substance which exists in equilibrium in the
as

the

form of the system to the left will be very considerable. Since


the temperature on the surface of the earth, at which the
of

majority

above

observations

absolute

it

zero,

is

about 273

is

made,

is

a priori to be expected that under

relatively low,

ordinary conditions the majority of chemical equilibria have been


displaced towards those systems which are formed with evolution

This

of heat.

view

to see this clearly,


detail

is

fully verified in all parts

however,

it

of chemistry;

necessary to consider more in

is

those equilibria which are so completely displaced in one

direction that their true character

is

not at once obvious. Consider

for example, the equilibrium

which as

is

^i

well known, was

H +
2

2,

shown by DEVILLE

to the partial decomposition of steam, at about


to our principle, the equilibrium

system

when

which

temperature,

oxygen

This

is

allowed to

displacement

owing

must be displaced towards

formed with evolution of heat, that

the temperature

experiment.

of

is

to occur,

1000. According

is

fall

such

is

the

water,

this is corroborated

that,

at

the

by

ordinary

water represents the stable condition of a mixture


and hydrogen, the latter being converted practically

224

EQUILIBRIUM.

most diverse

entirely into water under the influence of the

chemical

now,

If,

equilibria

temperature, displaced
with evolution of heat,
occur

ichich

towards
it

is

in

actions.

general are, at the ordinary

the

which are formed

systems

evident that those chemical changes

must

at the ordinary temperature

in the majority of

cases be accompanied by evolution of heat.

Similar considerations, based on the principle of mobile equilibrium,

take

high temperatures the opposite must


and that the changes which occur under these con-

show that

place,

at very

ditions will in general absorb heat. This conclusion also

is

fully

corroborated by experience.
It is perhaps not superfluous to point out that these conclusions are based on the exact laws of thermodynamics, since the
principle of mobile equilibrium itself

may,

principle

numerical

is

deduced from them. The

further, be brought into a

calculations,

the

form which allows of

accuracy of which has been

shown

by numerous applications.

compare these results with the


views which have been expressed by THOMSEN and BERTHELOT on
It

is

also

this subject,

in

more

place

here

to

especially because the ideas of BERTHELOT, although


'

contradicted by the facts and recently abandoned


by the author
himself, are still represented in many text books as being in

accordance with experience.


2
In 1853 THOMSEN
expressed himself thus

"

Every simple or complex change of a purely chemical nature


accompanied by an evolution of heat."

is

BERTHELOT
principle of

in

1867 put forward his views in the form of the


"
ivork, which states that:
Every chemical

maximum

change, accomplished without the intervention of external energy


towards the production of the bodies or of the system
which evolves the greatest quantity of heat."

tends

There

is

both of them
1

great similarity between these two statements; in


the principal idea is that chemical change evolves

Compt. rend. 118, 1378, 1894.


POGG. Ann. 88, 349, 1853; 90,

261,

1853;

91,

83,

1854;

92,

34, 1854;

Berichte, 6, 423, 1873.


3
Compt. rend. 71, 303, 1870. Ann. Chim. Phvs.
Chim. 19, 485, 1873.

(4),

18, 103,

1869. Bull. Soc.

225

THE PRINCIPLE OF MOBILE EQUILIBRIUM.

THOMSEN confines the application of the statement to purely


chemical changes, while BERTHELOT confines it to those which

heat

occur u without the intervention of external energy" (une energie


et range re).

While THOMSEN,
recognises

fully

"

Thermochemische Untersuchungen",
the exceptions to his earlier statement which
in his

have been discovered, and seeks for a hypothesis which shall be


in better accordance with the facts, BERTHELOT, in his "Essai de
3

upholds his view, attempting to bring


the facts into harmony with it, and it is only recently that he
has abandoned it.

Mecanique

The
that

it

is

to

exist,

predict

free

the

a great

in

equilibrium possesses the advantage

from any hypothesis, being a rigorouslaws of thermodynamics. It further allows


that under ordinary conditions equilibrium will

entirely

from

mobile

of

principle

deduction
us

Chimique",

many

cases,

when

the substances are present

almost entirely in the form of the system which is formed with


evolution of heat, and therefore that the majority of changes

which occur under ordinary conditions


an evolution of heat.
also,

that

at

the

The

application

will be

accompanied by

of the principle shows,

very high temperatures, equilibrium will exist in


of cases when the system which is produced with

majority
absorption of heat predominates, and therefore that most changes
which occur at high temperatures will absorb heat we might
;

this

in

case,

principle of

following the

minimum

work.

of mobile equilibrium places

example of BERTHELOT, speak of a


It is also to
all

be noted that the principle

equilibria,

whether physical or

chemical, on the same footing, emphasising the great similarity


of the two classes of phenomena, and embracing all equilibria

between material systems.


importance that the principle is capable of
quantitative expression, and may therefore be applied to numerical
calculations, as has been shown in the examples already considered.
Lastly,

it

By means

is

of

of this quantitative expression of the principle

possible to determine the conditions


1

1883, vol. Ill, 523.

Vol.

I,

under

ivhich

it is

the principle of

421.

15

226

EQUILIBRIUM.

maximum work

rigorously true.

is

To do

this

we have

to find the

under which

conditions

any given equilibrium will be displaced


in
the
direction
of the system which is formed with
completely
evolution of heat

we

shall see that this only occurs at absolute zero.

In a case of homogeneous equilibrium the quantitative expresof the principle of mobile equilibrium is contained in the

sion

equations

C?

....... (I)and!

dlogK
-

Suppose that the system whose concentration is C, is formed


with evolution of heat, and that q is therefore positive. The
of

second system C 2

the

case

K =

when

that q

is

0.

constant,

K =

This gives

This

zero.

Integrating equation
obtain

(II),

is

evidently the

on the assumption

K=

when T

JL_

Const.

0.

not quite independent of the temperature (see p. 123)


better not to employ the integrated equation, since the same

Since q
is

becomes

we

log

it

which the concentration

to find the conditions under

is

problem

result

is

may

when T

==

be obtained from equation


and q is positive.

(II)

which gives

== 0,

Quite similar considerations apply to heterogeneous equilibria;

taking for an example the equilibrium

S
only

the

system

heat,

will

zero,

in

be

other

NH

present

words

4.

^=

NH

HS, which

is

H-

2 S,

formed with evolution of

in a condition of equilibrium at absolute


its

dissociation pressure will

have disap-

peared.

The
brium,

application
viz.

of the principle to the third form of equili-

that in condensed systems,

is

of considerable interest,

condensation will
for, at absolute zero physical

have reached

its

limit, and therefore we might have dispensed with the consideration of homogeneous and heterogeneous equilibria, in which

<

UNIVEI
5

227

THE PRINCIPLE OF MOBILE EQUILIBRIUM.

condensed condition either do not participate or do


It is possible to show that in an equilibrium
so only partially.
between condensed systems, only that one which is formed with
bodies in

evolution

of heat

given
alone
is

stable at absolute zero.

is

the condition of equilibrium,

in

present

with

case

at a

whose formation absorbs heat

temperature the system

the

Suppose that

sulphur at about 100

monosymmetric

is

as, for example,

C. in

the equilibrium

rhombic sulphur

We

have

then to

^n

monosymmetric sulphur.
that on cooling the system

prove

will

it

pass through a transition point, so that before reaching absolute


zero the system which is formed with evolution of heat will
have taken the place of the other. As before call C r the con-

pressure,

the

of

centration

the

qr

vapour of rhombic sulphur at its maximum


heat evolved by its condensation to rhombic

and C m and q m the corresponding quantities for monosymmetric sulphur, then


sulphur,

log Cr

'

dT

Jlr_

2T 2

d log C m

qm
2T 2

'

'

dT

'

and therefore,

__

qr

dT
where q mr

the heat evolved

is

--

qm

2T

2'

by the transformation of mono-

rhombic sulphur.
symmetric
The conditions which must be
into

system which

is

fulfilled

in

order

that

the

formed with absorption of heat (monosymmetric

sulphur) shall exist alone in stable equilibrium are,

Cr
According

T =

0,

to

the

>

C m and q mr

above

>

differential

and therefore the value of

C
.

0.

equation
-

C
^Om

must be equal

when
to unity

228

EQUILIBRIUM.

some

at

temperature

the

temperature

C
~-

1=

is

Om
was

the

at

intermediate

which

transition

^^m

>

between
1

absolute

zero

and

the temperature at which

temperature

the existence of which

to be proved.

From

the preceding, therefore, all chemical equilibria without


exception are displaced completely at absolute zero towards those

systems which are formed -with evolution of heat, and only under
these circumstances is the principle of maximum work rigorously true.

AFFINITY.
THE COMPARISON OF CHEMICAL

I.

AFFINITIES.

This section will be devoted to the determination of the magof chemical affinity in different cases by means of the

nitude

conceptions

and

obtained,

already

without

any

using

special

hypotheses.
If

be

affinity

considered

be expressed in
and the work which it can effect

as

or in atmospheres,

kilograms

a force,

it

may

kilogram-metres or in calories.

in

serve

as

condensed

of

CuCl 2
it

on

in the equilibrium

2H 2

2KC1.

reverse

by the fact
equilibrium,

takes

that
is

Equilibrium

CuCL.KCl

^z

4-

KC1

has been proved experimentally that above


the right completely replaces that on the
the

it

which may

a conception

at

characterised by the existence of a transition

is

For example,

point.

systems,

detailed consideration of the

starting point of our further studies.

the

such systems

in

which produces chemical change

force

by means of a more

shall arrive,

equilibrium

the

as

it

Regarding

we

at

the

This

place.
it

both

transition

2H 2 0,

4-

92. 4

the system
while below

left,

temperature,

characterised

simultaneously exist in
The law of the
temperature.

systems

incompatibility of condensed systems makes it possible to predict


the existence of a transition temperature in every such equilibrium, for example in the reaction

KI + NaCl ^7^ KC1


the

affinity,

the

or

that

See

p.

172.

is

Nal,

the force which brings

between the

difference

the two systems,


1

is

zero

at

affinities

about the change,

which are

at

work

in

the transition temperature; further

230

CHEMICAL AFFINITY.

through the transition temperature the value of the

on passing

affinity, or of the difference of

changes sign.

affinities,

In the case of copper bi-potassium chloride, for example, the


affinity which brings about the formation of the system to the
equal to that bringing about the formation
of the system on the left, or, what is the same thing, the difference between the two affinities is zero at this temperature.
right

is,

92. 4,

at

MEASUREMENT OF AFFINITY.

II.

The magnitude of

retains the water of

the affinity ivhich

crystallisation in salts.

We

now

will

MITSCHERLICH

in

taken
1844,

up

question which was attacked by

What

namely:

is

the magnitude of

the affinity which binds the water of crystallisation in decahydrated sodium sulphate

MITSCHERLICH expresses himself as follows

u If a
crystal of hydrated sodium sulphate be introduced into

the Torricellian

vacuum

at

9,

the mercury falls 5.45 mm., owing

to the water evaporating after having escaped from combination.

Under the same circumstances water alone produces a depression

of

8.72

crystallisation

mm. and
for the

3.27 mm., or about

Although the

therefore

the

sodium sulphate

affinity
is

of the water of

equal to a pressure of

kgrm. per sq. cm/'


attraction which sodium sulphate exerts on
/ 84

its-

water of crystallisation is, as will be shown later, many thousand times greater than MITSCHERLICH supposed, yet a connexion
be shown to exist between the magnitude of this attraction
and the diminution of the vapour pressure.

may

Consider the attraction which a solution of a salt exerts on pure


water,

or,

as

it

might be

called, the affinity

between a solution

and water.
This

attraction

has been measured by PFEFFER

a piece of apparatus consisting of a porous

cell,

by means of

in the walls

of

which a membrane of copper ferrocyanide has been precipitated.


1

Lehrbuch der Chemie, 4te

Osmotische Untersuchungen, Leipzig, 1877,

Aufl.

565.
p.

4.

231

OSMOTIC PRESSURE A MEASURE OF AFFINITY.

which contains the solution of the

salt.

The copper ferrocyanide

membrane

is semi-permeable, that is, it possesses the property of


water
to pass through it, while the salt is unable to do so.
allowing
If now the cell, filled with the solution of the salt, be immersed

pure water, after closing its open end and connecting it to a


manometer, the pressure within it will be seen to increase, the
in

through the membrane

water passing in
attraction

of

equilibrium

cell
it

of

the
is

increasingly

entirely.

meter,

i.

e.

salt

attained,
resists

After

solution.

the

in

consequence of the

some time

a condition

because the pressure in the porous


inflow

The pressure which

is

of water, finally stopping


then indicated by the mano-

the osmotic pressure of the solution at the temperature

of the experiment,

is

evidently a measure of the affinity between

the solution of the salt and pure water.

The following numbers were obtained by PFEFFER'


solution containing one per cent, of sugar.

Temperature.

with a

232

CHEMICAL AFFINITY.

Suppose we have a closed vessel, fig. 44, filled partly with


steam E, partly with water. The lower part of the vessel, conthe

taining

is

water,

by a semi-permeable

divided

sure

the

at

prevailing

therefore

being

its

in

two compartments

and

The aqueous

partition.

vapour having attained

into

maximum

pres-

temperature,

and

with

the

equilibrium

water, an infinitesimal quantity of some salt


is dissolved in the water in A. The equili-

brium, which

is

disturbed by the attraction

of the salt for the water, will tend to be

by the passage of water from


by two different paths, first,

Fig 44

re-established

into

semipermeable membrane,

through the

directly

secondly, indirectly in the condition of

vapour through E.

The

direct

osmotic

passage

which

pressure

manometer

in

as

of

the

water

into

will

means

might be measured by

PFEFFER'S

experiments

let

its

produce an

value

of

be d

atmospheres.
of vapour from E
measured by determining the diminution in the
pressure of the vapour at E which would just suffice to prevent
condensation in A. This will be the case when the pressure of the

The pressure which brings about the flow

to

A may

vapour

in

be

The pressure

equal to the vapour pressure of the solution A.


which causes the flow of vapour from E to A is

is

therefore equal to the diminution in the vapour pressure of water


d S
which is produced by dissolving the salt in it let this be
;

atmospheres.

The

of the

attraction

salt solution for

water thus gives

rise

D and

d S, according as it acts on liquid


forces,
water or on aqueous vapour. Assuming that the attraction of
the solution in A for a molecule of water is independent of the
to

two

aggregation of the water, the ratio between the two


forces of attraction will be the same as that between the quanstate

tities

of

of water contained in equal volumes of liquid and vapour.

The weight
1 litre of

of 1 litre of liquid water

may be

taken as

kgrm., and

aqueous vapour under the pressure of S atmospheres weighs

233

CALCULATION OF ITS VALUE FROM OSMOTIC PRESSURE.

We

0.000806

Integrating this expression

- log S

Sw

::

Sw

be
,

the

we

find,

^ft +

const.

of water at T,

vapour pressure

we have

for

:= 0.

The integration constant may be


and we obtain

D
common

or. introducing

4.55

eliminated by means of this,

|s
0s

log

logarithms,

D =
where S s

kgrms.

j-j~

therefore write,

may

If

y2

10.5

T Log |S
os

the vapour pressure of the solution of the salt.

is

As an example of the application of this equation, the values


of D may be calculated for the solutions of sugar the osmotic
pressures of which were determined by PFEFFER.

The value

of

~- may
o

be calculated approximately for a given

solution from

GULDBERG
solution

its

means of thermodynamics.

freezing point by

has

shown

t,

being

that,

the

the freezing point of an aqueous


relation

following

exists

between

it

and -^-:
bs
hL-

Ss

0.00954

Introducing this into the equation for D,

D
1

I,

10.5

Compt. veud. 70, 1349, 1870.

757.

Log

(1

we

0.00954

obtain
t)

OSTWALD, Lehrbuch der Allgem. Chem.

2te Auti.

234

CHEMICAL AFFINITY.

RAOULT

has

solution of sugar

The following

found
is

that

the

value

of

for a one per cent,

O.054.

table contains the values of the osmotic pressure

of a one per cent, solution of sugar, at the different temperatures


given, (1) observed directly
of the above equation.

Temperature.

by PFEFFER,

(2) calculated

by means

235

CALCULATION OF ITS VALUE FROM OSMOTIC PRESSURE.

The values

of

-^ have been calculated from the numbers


^s

obtained by FROWEIN (pp. 160 and 161).


The statement that the value of D for

1300 atmospheres, means that


two molecules, for example, of

if

is

its

CuS0 4 5H 2
.

39

at

.7

copper sulphate, from which


water of crystallisation had

been removed, were brought, at the temperature mentioned, into


PFEFFER'S osmometer, a pressure of 1300 atmospheres would be
required in order to prevent the water from penetrating the semipermeable membrane and combining with the copper sulphate.
The experiment could not of course be actually carried out in

we

the usual way, since

are here dealing with a solid substance.

DETERMINATION OF THE WORK WHICH


CAN BE DONE BY AFFINITY.

III.

The quantity
magnitude will

of work which can be done by


now be calculated.

affinity of

known

If a

kilogram-molecule of hydrated copper sulphate (249 kgrms.


of CuS04- 5H 2 0) be taken, and a molecule of water (18 kgrms.)
be removed from it by means of the air pump, the vapour pressure

of

PAREAU

the

remains,

crystals

according to the experiments of


is, the salt tends to retain

that

completely constant,
water which is being removed from it, from beginning to
If the salt
end, with a force of 1300 atmospheres (at 39. 7).
*,

the

CuS0 4 4H 2
.

pressure)

the

were

brought into a PFEFFER'S cell (under this


work which would be done by the 18 kgrms, of

water on passing into

owing

A=

to the affinity

1300

X 10333 X

through the semipermeable membrane,


of the salt for it, would be
it

18

Generally, the problem

nitude of the affinity

is,

= 241792 kgrai.metres,
may be

De Pompbarometer.

treated as follows:

according to

D =

4.55

or 568 calories.

what

is

the

mag-

said on p. 233,

log f^.

bs

Inaugural Dissertation. Utrecht, 1875.

236

CHEMICAL AFFINITY.

The work which

force can do,

this

18 kgrms. of water,

will

_ 2T log

1 ft

10333
-,

during the transport of

is

j|L

^
calories.

|=

more complicated case will now be considered.


be calculated which comes into play when

force

a salt, say
another hydrated salt, say
instead of combining with water in the free state.
say a priori that this can only take place when the

FeSO^. 6H 2 0,
MgS0 4 7H 2 0,
.

We

The

may

water from

takes up

of the

dissociation pressure

FeSO^.TH^O

smaller than that of

is

at the given temperature. The force D which


2
the
about
transference
of the water is equal to the differbrings
ence between the forces with which each of the sulphates retains

the

MgS0 4 7H
.

water of crystallisation;

its

D =
iS s

4.55

and

SS

it

(log lO s

therefore,

is,

log

=
%)
Q
2

magnesium sulphates respectively.


The work which can be done by
T)

may now
transition

the

10833

or,

This

4*
i&s

be

of

TooeT kgrm
log

extended by

point.

measurements

this affinity

therefore

is

1 ft

4257?

of the

log

the dissociation pressures of the ferrous and

being

A ~

4.55

S /

s
^~

metres

calories.

the introduction of the idea

The following

table contains

the dissociation pressures

and ferrous sulphates made by

Gr.

'

WIEDEMANN

of

some of

magnesium

at different

temp-

eratures.

Journ.

in the table

prakt.
are,

Chem.

(2)

9,

338, 1874.

Although the numerical data contained

according to FROWEIN'S determinations on

MgS0 4 7H 2 0,

inaccurate, the truth of the principle which they serve to illustrate

is

decidedly
not affected.

MEASUREMENT OF THE WORK DONE BY AFFINITY.

Temperature.

238

The

CHEMICAL AFFINITY.

following table contains the results of the calculation.

Temperature.

MEASUREMENT OF THE WORK DONE BY AFFINITY.

dlogC m

239

qm

'

2T

dT

'

the heat evolved by the reaction

q m being

MgS0 4

+ H

= MgS0

4.

0.

The heat evolved by the conversion of the second system


the

first

FeS0 4

being

q,

+ MgS0 4

z^r FeSO,.

+ MgS0 4

we have
q

and

into

in the equilibrium

qf

- -

qm

therefore,

q
'

dT

T2

This

with

equation is easily integrated since q changes but little


the temperature and may be regarded as
independent of

we

it;

obtain,

log

Since

we

at

the

=
c7

~2T

const>

transition temperature P,

C f and C m

are equal,

obtain

and therefore,
-

Cf
Since,

further,

the

the vapour pressures,

2T

concentrations

we may

are

Finally, introducing the value of the

by

the affinity,

in

the

same

ratio as

write

work which can be done

240

CHEMICAL AFFINITY.

A =
we

2T

log

obtain

A =
or. in

the work,

words;

expressed in calories,

can perform, when

in a given chemical reaction

at

place

given

is

temperature,

equal

to the

ivliich

the affinity

the reaction takes

quantity of heat

evolved by the reaction, divided by the absolute temperature of the

transition point,

and

erature

transition point

of

the

multiplied by the difference between the temp-

and

the temperature at which the

reaction occurs.

Considering that the maximum quantity of work which affinity


can perform is equal to the quantity of work done by the change

when

takes

it

place

in

reversible

way,

it

will evidently

be

by means of thermodynamics.
which one condensed system is trans-

possible to obtain equation (1)

Let us take any case in


formed into another, and

let

be the absolute temperature of

the transition point, below which the

first

of the

two systems

by the second completely with evolution of q

replaced

the

Suppose
formed: The

is

calories.

following cycle of reversible operations to be perfirst

converted

is

system

into the second at the

calories; the second system,,

transition

temperature absorbing q
formed in this way, is cooled to the temperature T, at which
it is allowed to
change into the first. In doing so the work done

by

affinity will

be equivalent to A calories, if the process take


way and the heat evolved will therefore be
!

place in a reversible

calories.

The temperature

point in order to bring the

is finally

raised to the transition

system into its initial condition.

The changes which have occurred


sible, we have, (from the second law
q

~~

in this cycle

being

all

rever-

of thermodynamics)

P
T

and therefore,

A _
1

The

practical

means

by

which

the nature of the case considered.

P
q

this

T
p

may

be approximately realised,

depend on

MEASUREMENT OF THE WORK


In

the

work done by

case

special

affinity at the transition

A =

0,

that

is,

the

temperature, (and there-

zero.

is

APPLICATIONS.

IV.

Work done by

241

BY AFFINITY.

we have

T,

fore the force of affinity itself)

1.

1)0\E

affinity at absolute zero.

Diagram of

work done.

the

The equation

A
shows

that

absolute

at

:= q

zero

-^p

q,

that

is,

the

work which

may be

obtained from the change is equivalent to the whole of


heat which it evolves. At absolute zero the change could

the

thus occur either with evolution of q calories and without doing


any work, or evolving no heat and doing a quantity of work
equivalent to q calories.

This

on

is

complete agreement with the conclusion arrived at

in

where

228,

page

maximum work"

is

it

is

pointed

out

that the "principle of

rigorously true at absolute zero, the quantity

being then a measure of the work which can


be done by affinity, and its sign therefore indicating the direction
in which the change will occur. This is no longer the case at
heat

of

evolved

higher temperatures. The work which can be done by


is then equivalent to a part
only

of

affinity

heat evolved,

the

the two have the same sign,

however, until the transition


is

temperature
this

can
zero

reached,

at

point the work which


be done by affinity is

and

at

higher temp-

eratures

its

sign

that

to

say work must

is

be performed

is

reversed,

in order to

Fio

45

bring about the reaction.

The change

of sign accompanies the change in the direction of the reaction

which occurs

Employing

at the transition point.

the language of the views formerly entertained by


16

242

CHEMICAL AFFINITY.

we

BERTHELOT,

therefore

the transition point from a


work" to one of " minimum work". This

pass

at

"principle of maximum
may be represented diagrarnmatically by taking the quantities of
work which can be done by affinity at different temperatures as

the

OA

ordinates

and

the

corresponding

temperatures as the

abscissae of a curve.

For T

A -

0,

q,

and for

P,

A =

0.

P passing through these points represents the work


be
done by affinity at different temperatures.
can
which
Since the heat evolved by the change varies but little with the
The

line q

temperature we

by the straight line qq parallel


to OT. It is evident that A and q have the same sign up to the
point P, while beyond it they have different signs.

may

represent

it

Influence of pressure on the transition point.

2.

has already been pointed out on page 210 that there

It

is

analogy between the transition temperature of condensed


systems and the melting point of solid bodies.
close

The connexion between the


by the well known equation

and the pressure

latter

is

expressed

dp

where

425.7

dT
-r

is

the elevation of melting point produced by an increase


of one atmosphere in the pressure, T is the absolute temperature,

unit

the

volume

of

weight of the substance


liquid, and T that in

the

in

the solid condition,

and

the

latent heat of fusion.


It is

natural to inquire whe-

ther, mutatis mutandis, the

rig 46

same

equation represents the influence


1

See R. CLAUSIUS, Die mech. Warmetheorie,

kgvms. per square metre,

I,

kgrm. degree calorie

172, (1887). [1 atmosphere

425.7 kgrm.metres].

10333

243

INFLUENCE OF PRESSURE ON THE TRANSITION POINT.

That this is the


temperature.
is easily shown by means of the diagram (fig. 46), in which
temperatures are taken as abscissae, and the corresponding

of pressure
-case

the

on

the

transition

work done by

quantities of

affinity as ordinates.

At temperatures higher than

the

transition point the

work

The
represented by
work which can be done by affinity at a temperature Pi degrees
above
is represented by at. From the diagram we then obtain
done

continuation

the

is

of the line qP.

_Pt ==

OP

at

Oq'

Now Pt is equal to

dT, the difference between the transition temperature at atmospheric pressure and that at a pressure d p atmos-

= T,

OP

pheres greater,

the absolute temperature of the transition

point, and

at

10333
AC)r
4^o

dp

T)

(7

calories,

being the increase of volume, in cubic metres, which


accopamnies the change of 1 kgrm. of the substance (for example,

{7

T)

the change of

kgrm. of rhombic into monosymmetric sulphur);

quantity of heat absorbed by the change


takes place without doing external work.
Making these substitutions we obtain the equation

Oq

r,

the

dT

(r

when

it

-T

425.7 r'
which

is

point

when

thus true for a transition point as well as for a meltingthe quantities occurring in it have the meanings

given above.

The propriety of applying

this equation in

such cases has been


!

MALLARD and
shown, by quantitative experiments, by REICHER
2
3
LE CnATELiER
and quite recently by SILVIO LussANA while SPRING
,

REICHEII,

Inaugural

Krystallographie, 8, 593,
2

Bull. Soc.

Nuovo Cimento,

Dissertation,

1884; see

Min. de France.
(4),

1,

7,

Amsterdam,

also p.

185 ante.

478, 1884.

97, 1895.

1883

GROTH'S

Zeitschrift

fur

244

CHEMICAL AFFINITY.

and VAN

HOFF

'T

and LUSSANA have tested the accuracy of an


may be made from it.

'

interesting deduction which

REICHER'S

refer

experiments

monosymmetric sulphur. Having


the

that

about

change of rhombic into

the

to

by means of the dilatometer,

found,

temperature under atmospheric pressure is


he went on to investigate the influence of an increased

transition

95. 4,

means of the apparatus

by

pressure

in

represented

which
the

is

This consists

47.

fig.

of a dilatometer

the

apparatus

AB

with

left,

serving

the

of

for

the

on

the

pressure,
production
right, with the closed manometer

by means of which

of

capillary

connected, on the

the

E F,

pressure

is

measured.

The pressure is developed by heating


sodium bicarbonate, contained in the
bulb A, in an oil bath at constant
The

temperature.
O erves
o

to

collect

millimetre scale

of the manometer, which

wool

introduced

is

water

by the decomposition of the

Fig. 47.

of

small

the

filled

is

the

into

is

is

bisulphide

in

183),

p.

salt.

with mercury.

At C

a thread

capillary of the dilatometer in

any water which may pass over from B this


necessary since at 95 water decomposes the carbon

precaution

the

evolved

attached to the tube

order to take up

filling

bulb

the

mixture

of carbon

bisulphide and turpentine

part of the dilatometer not occupied by sulphur (see


by evolving carbon dioxide renders the measure-

and

ments impossible.

The apparatus being thus arranged


temperature of

Zeit. phys.
der umkehrbaren
2

See

p.

184.

95. 6 and

Chem.

1,

is

heated to a constant

the pressure allowed to

227, 1887.

See also

W. SCHWARZ,

Umwandlungen polymorpher Korper.

rise.

Beitrage zur Kenntniss-

Gottingen 1892.

INFLUENCE OF PRESSURE ON THE TRANSITION POINT.

The

following table contains the results obtained.

Time.

245

246

CHEMICAL AFFINITY.

4 atmospheres the transition point was


11.8
found to be 95. 6 \ an increase of pressure of 15.8 -- 4

Under a pressure

of

atmospheres has therefore raised it from 95. 6 to 96. 2, orO.6;


the elevation of the transition temperature by an increase of pressure
of one atmosphere

is

therefore given by experiment as 0.05.

The same quantity may be

means of the formula

calculated by

103 33

425.7 r'

dp

by introducing the following numerical values;

c-

95.6 = 368.6
r
0.00001252
r = 2.52.

273
-

This gives

dT

10333

dp
value

which agrees

X 0.00001252
X 2.52

368.6

425.7

well

sufficiently

with that obtained by

experiment.

The experiments
modifications

of

LUSSANA were made with the various

of S.

ammonium

nitrate

2
.

He

determined the trans-

temperatures at different pressures, the determinations being

ition

made both with


The

rising

and falling temperature

3
.

results are given in the following tables in which,

however,

only those results which were obtained with rising temperature


The results obtained with rising temperature
are
included.
differ
from
those obtained with falling temperature by
always

some

degrees,

the

of

influence

point was however found

the

to be the

on the transition

pressure

same

in

both cases.

See page 184.


See page 164

No

agreement was found between the experiments and the values obtained from
im
he ascribes this to the inaccuracy of RODthe equation for -- in the case of HgI2
3

WELL'S determinations of the value of


4

For example, with ammonium

(<r

r).

nitrate (first modification).

On

Transition temperature at

250

A
See also BELLATI and

ROMANESE,

On

heating.

35.45

1 atmosphere

42 .76

7.31

Atti dell' Institute Veneto,

cooling.

30.55
37 .95

(6),

=
4,

7.40
1395,

18856.

INFLUENCE OF PRESSURE ON THE TRANSITION POINT.

247

248

CHEMICAL AFFINITY.

SPRING'S compression apparatus,

occurred

The change
under a pressure of about

to a great pressure.

40

at

quite unmistakably
atmospheres, that is, the transition temperature w;is
depressed by the application of this pressure by about 40.

6000

Calculation of the transition point,

3.

The

a.

allotropic modifications of sulphur.

The diagram

on page 242, being quite generally applicable


to equilibrium in condensed systems, applies also to the simple
cases of fusion and solidification.
In these cases the line

qP

represents the

work which can be

done by the forces producing solidification or fusion when Oq


represents the latent heat of fusion q, and OP the melting point

on the

absolute scale of temperature.

however, that

qP

equilibrium, only represents the


ition

point

difference

P,

because

between the

is

out,

work

in question near the trans-

function of the temperature, the

specific heats of a substance in the solid

and liquid states being not inconsiderable

By means of

must be pointed

It

here, in contradistinction to the case of chemical

this

diagram

it

is

2
.

possible to calculate the trans-

temperature of
the allotropic modifications of sulphur. To

ition

do

so,

we

represent

will

the

first

work

which may be done by


the

solidification

or

fusion of the

two mod-

ifications of

sulphur in

a
diagram, fig. 48.
Let the quantities of

rig. 48.

and q mf which are evolved during the solidification of


liquid sulphur to rhombic or monosymmetric sulphur respectively
be measured along
A, and let the melting points T r and T mf

heat

q rf

(on the

absolute

scale)

be

measured along

Bull, de 1'Acad. Roy. de Belgique, 49, 344.

Appendix, note

3.

T.

The

straight

249

CALCULATION OF THE TRANSITION TEMPERATURE.


lines

T rf and

q rf

q mf

T mf

will then represent the quantities of

in

OT

erect a perpendicular, then

work in question.
At any point P

PR

the

are

quantities

and

which can be obtained when

work

of

form of monosymmetric or rhombic


and
their difference R
therefore
represents
sulphur respectively,
the quantity of work which can be obtained from the change
liquid sulphur solidifies in the

of monosymmetric into rhombic sulphur


Since there
the

will

at the temperature given.

a point of intersection at B,

T rm

corresponding temperature

work
zero

is

change and that

its

it

is

evident that at

the sign of this quantity of

value at this temperature will be

are the characteristics of the transition temperature

these

of the two modifications.

From

we

the figure

see that,

l rf
Qlir
ciHU.j

T1
-i-

mf

l rm

T rm

l rf

-*-

l rm

Jj

T'-mf

q r f,

R T"rm

*-*

*-Jmf'

Therefore

Tr

T rm

A mf

*-

T rf
T mf

rm

:HL
-

'

1-

or
I

T^rm
3*

(JL

T mf /

qnf ^T rf

Introducing the numerical values (page 215)


*&-

q mf

i[5
o

T rf

273

114.5, and

T mf

273

120

we obtain

T rm

273

95.2.

The transition temperature calculated is therefore 95. 2, that


found experimentally being 95 .4.
Another (approximate) calculation on page 216 gave 96 .3.
l

REICHER found 95. 6

at

atmospheres

atmosphere being 0.05, the transition


6
will be 95. 4.
vapour at 95

246
the change for 1
p.
under the pressure of sulphur

pressure,

temperature

250

CHEMICAL AFFINITY.

The transformation

b.

ammonium laevosodium and ammonium racemates.

of a mixture of sodium

and dextro-tartrates into


This case
VAN

'T

analogous to that which we have just considered.

is

VAN

HOFF,

DEVENTER,

and

GoLDSCHMIDT,

JoRISSEN

llUVC

described the following changes:

At 26.6,
2

(NaNH4 C 4 H 4
The

6.

0)

(NaNH, C 4 H 4

racemate

so-called

of SCACCHI

6.

0) 2

(1)

here formed from the

is

mixture of Isevo- and dextro-tartrates.

At 34.5,
2

(NaNH 4 C JI 4
The
35

6.

0) 2

= (Na

6) 2

+ [(NH4 )

C 4 H4

t 4

H0

decomposes at temperatures higher than

of SCACCHI

salt

C4H 4

into the individual racemates.

The temperature
and

which the change of the mixture of

at

into

dextro-tartrates

the

racemates

individual

laevo-

ac-

occurs,

cording to the equation

(NaNH 4 C 4 H 4

6.

be

may

H 0) - (Na
2

calculated

in

C4H4

6) 2

+ [(NH

4) 2

C4 H 4

6] 2

same way as before

the

16

0.

in the case of

sulphur.

The

work

which

can

done

be

by reaction

(2)

of

the

the line

may be
a function

represented as

temperature

A B,

fig.

49,

by

OB

representing the transition


temperature on the absolute scale (273

and
P C

34.5)

by the change.

Fig. 49.

Similarly

which

A the heat absorbed


the

work

may be represented by
by
a line DC, C being the transition temperature to be calculated,
and
D the quantity of heat absorbed by the change.
can

be

The point of
1

Zeit. phys.

done

the change (3)

intersection

Chem.

1,

P 1?

173, 1887;

corresponds therefore to the temp-

17, 49, 1895;

see also p.

170.

OF

THJ--

UNIVER;
251

CALCULATION OF THE TRANSITION TEMPERATURE.

which no work can be obtained from the change of


the mixture of Isevo- and dextro-tartrates into the racemate of
erature

at

SCACCHI, that

is,

the transition point of change

(1),

(273

26.6).

The

quantities of heat evolved by the changes may be taken


approximately equal to the differences between the heats of

as

solution of the different systems concerned. These are as follows

NaNH 4 C H
NaNH 4 C H
1/2 (Na C 4 H
4
4

6.

11726

H
+ (NH 4

cals.

7922

)2

C 4 H4

6)

5660

therefore

OD
The

OA -

figure

11726

P!

OC

7922

5660

= 6066

2262.

shows further that

and
Since

5660

differs

P!

P
P

very

AO

AO = PB
DO - PC

little

OB

OC.

from OB, we may write

DO = PC

PB.

Introducing numerical values we obtain, since

PB

The

34.5

7.9,

transition temperature required is therefore 26.6

f 2.9

= 29.5;

29.

dilatometric experiments gave

V.

26.6

THE ELECTRICAL WORK PERFORMED BY A


CHEMICAL CHANGE.
1.

It

has been proved above that the work which can be done

by the force of

may

General considerations.

affinity

which brings about a chemical reaction

be represented by the equation

A =

T
5

CHEMICAL AFFINITY.

"252

The magnitude

way
it

which

in

work is independent of the


chemical reaction takes place, provided that

of this quantity of

the

reversible.

is

HELMHOLTZ

has shown that a chemical reaction which occurs

way that it does electrical work


The chemical change may take place

in such a

producing

of

current

or

electricity,

is

in

reversible.

one direction

the

made

be

may

it

to

proceed in the opposite direction by passing a current from


an external source. In such cases the electromotive force prouced by the reaction is the same as that required to reverse it.

from these considerations, that the expression for


A represents the electrical work which the chemical change is
capable of producing. This may also be proved by means of the
It

is

evident,

following cycle of reversible operations:

At

the transition temperature

undergo
erature

change absorbing q
be then depressed from P to T.

ature the chemical change, which will

allowed

is

current

to

of

take

produce

electrical

work equivalent

is

then

being

calories,

brought back

At the

now

latter

temper-

occur in the opposite

calories,

initial

its

do

will

it

simultaneously
to

Let the temp-

calories.

place in a galvanic cell so as to

electricity;

to

quantity of the system

let unit

chemical

direction,

quantity

quantity

The system

evolved.

condition

of

of heat,

by raising the

temperature to P.
This cycle of changes

is reversible; we
might begin by cooling
from
P to T, at which temperature it might
the original system
be caused to undergo the chemical change by passing a current

would do a quantity of work equivalent to


A calories would be absorbed.
on the system, and q

of electricity.

calories

This

The temperature might then be

raised

from

to

P and

the

chemical change allowed to take place, evolving q calories.


The cycle being reversible, we may apply the second law of

thermodynamics to

it,

and obtain
:P

A
1

II,

~~~~

T'

Sitzungsberichte der Kon. Preuss. Akad. 1882,

958 aud 979;

III,

92.

p.

823. Gesammelte Abhandlungen,

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

or

This

result

of

the

then

is

system

produced
heat evolved

words as follows

is

the

by

is

proportional

to the electromotive force

The connexion between

l
.

reaction

therefore

may

be

by

and the

expressed in

to

which

a chemical change can produce


the heat evolved by the reaction, q, divided by
force

and

the absolute temperature of the transition point, P,


the

electromotive

proportional

~p*

equivalent weight in kilograms. The


done by the change of unit quantity

its

work, A, which

by the reaction

The

:=

be further simplified by considering as unit

may

quantity of the system,


electrical

253

difference

between

it

and

the temperature

multiplied

at ivhich the

reaction occurs.

Since the electromotive force


to the

work done by

is

thus shown to be proportional

the diagram (p. 241) representing


be
applied to the former also.
may evidently
2
the
equation for A with respect to T we obtain
differentiating
affinity,

the latter

By

dA
dT
Eliminating

P'

P by means of
dA

the original equation

or

== q

'

dA
+ m
T

^.

dA
is

obtain

dT

we

the temperature coefficient of the electrical

work done by

the change.

HELMHOLTZ
in his
1

of

memoir

has already obtained this equation in another way


"
On the thermodynamics of chemical processes,"
:

[According to FARADAY'S law the quantity of electricity carried by an equivalent


3
any substance is constant, it is found to be 96587 X 10 coulombs per kgrm.

If E be tbe electromotive force produced by a reaction, the electrical work


done by a kgrm. equivalent of change will be A
E X 96587 X 103 volt-coloumbs.
1 volt-coulomb
107 ergs
0.0002395 kgrm. degree calorie, so that the above

equivalent.

quantity of electrical

work

This

See the note on page 252.

is also

23116

evident from figure 45.

kgrm. degree

calories.

T. E.]

254
and

CHEMICAL AFFINITY.

has been confirmed experimentally in a number of cases

it

by CZAPSKI

As

is

GOCKEL

',

well

and JAHN

3
.

the view that in reversible processes the

known,

chemical energy is completely converted into electrical has been


advanced by JOULE, WILLIAM THOMSON (Lord KELVIN), and also by
That this view
HELMHOLTZ accordingly we should have A
q.

is

incorrect has been proved by BKAUN

latter giving the


2.

GIBBS,

and HELMHOLTZ, the

above-mentioned equation for the electrical work.

Thermodynamics of

the transition cell.

The equation

A-q
shows that

if

by

the

into

work

the electrical

the change
other,

of

one

it

being

of

of

-pin a galvanic cell

two

be furnished

convertible

mutually
assumed that

course

systems

the change

place in a reversible way, then at the transition point,


where P =. T, this work will have the value zero.

takes

method of determining the transition tempboth


stable
and meta-stable phases, (page 193) is
erature, using
implicitly based on this deduction from the above equation.
COHEN'S

electrical

Since the change in the transition cell used in this method


reversible

we may

at once apply to it the equation

A =
and see to what results
It

is

q
it

T,
dA

...... (1)

leads.

has already been proved that

and q have the same sign

at temperatures below the transition temperature, while at temperatures above

Since

it

they have opposite signs.

vanishes

at the transition

temperature
without reference

that its magnitude (considered


must decrease, with rising temperature
1

2
3

below

it

obvious

is

to

the

WIED. Ann. 21, 209, 1884.


WIED. Ann. 24, 618, 1885. See also W. NERNST, Zeit. phys. Chein.
WIED. Ann. 29, 21, 1886.
WIED. Ann. 5, 182, 1878; 16, 561, 1882; 17, 593, 1882.

its

sign)

transition

2,

23, 1888.

255

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

temperature, and increase above it. The values of the electroshow similar behaviour,
motive force which are proportional to

as

shown by the

is

table on page 198.

sign

below

A =

0,

the

consideration

little

dA

show that q and T

will

-r^-

transition

are always quantities of opposite

temperature;

at

this

temperature

and therefore

^-

TT

This equation may be called the equation of the transition cell.


The results obtained with the transition cell with stable and

meta- stable

W.

show

phases

clearly that the view put forward

THOMSON (Lord KELVIN),

i.

e.

that

A =

q,

is

the transition temperature where q has a large value

The value of

dA
the

at

-r^-

by

erroneous, for at

transition temperature

may

is

zero.

be cal-

by means of equation (2); it may also be determined by


experiment and the two values so obtained compared. Taking the
case of Glauber's salt, which has been investigated experimentally,
culated

will

be

heat evolved by the change which produces the


work A, A being the electrical work obtainabel

the

quantity of
from the change

when

equivalent of the salt

the quantity of electricity carried by one


is

set in motion.

37), in which the change occurring


below the transition point is the conversion of anhydrous sodium
sulphate and saturated solution of Glauber's salt into solid Glauber's
If

salt,

transition

cell (fig.

were connected

up against a Daniell

allowed to flow, then after


into

solution

in

cell

and the current

kgrm. equivalent of

zinc

had passed

the latter an equivalent quantity (200 kgrms.)

of mercury would have separated in the metallic state at the


electrode contained in the saturated solution of the anhydride,

and

an

equivalent

quantity

been formed at the electrode


salt.

have

of mercurous sulphate would have


in the saturated solution of Glauber's

corresponding quantity of Na and


The
passed through the solutions.

S0 4

ions

would

transference

of

also

the

S0 4

ions does not affect the concentrations of the solutions since

the

S0 4 combines with mercury

to

form insoluble mercurous

256

CHEMICAL AFFINITY.

were allowed

If the transition cell

sulphate.

to furnish the

same

quantity of electricity everything would take place in the reverseorder.

would

Everything

also be reversed above the transition

point.

the

Suppose

be

to

cell

working

in

its

normal way below

the transition point, let n be the migration constant

Na 2 S0 4

for

Na

in

then n sodium ions migrate from the more concentrated


(anhydride) solution to the weaker (Glauber's salt) solution, while
,

SO

^ ions

n)

(1

migrate in the opposite direction.

The n sodium

combine

ions

sulphate and so form

the

from the mercurous

molecules of sodium sulphate, this causes

of

precipitation

S0

with

molecules

Glauber's

of

from

salt

the

saturated solution according to the equation

Na 2 S0 4

2-

&

where b

(x

4-

Na 2 SO,. bH 2

number of molecules

the

is

7a n)

~ Na 2 S0 4 10H 2
.

of water to each molecule

of sodium sulphate in the saturated solution of Glauber's salt.

We

obtain from the above equation

zn
The migration

b
^-- -16-

of the sodium ions towards the Glauber's salt

molecules of sodium

solution has, further, the effect of removing

sulphate

causing
result

I Na

is

from

the

saturated

molecules

of

the

solution

to

anhydride

the

anhydride,

thus

The

final

dissolve.

therefore

S0 4 +

| (^5) Na S0
2

or in words, J(b

molecules

of

4.

bH2 =

Appendix, note

4.

j g-^ Na S0
2

4.

2 0,

molecules of Glauber's salt are formed from


lUj

the

anhydride

and

saturated solution of Glauber's salt.


1

of

^-7-

-.

molecules of the

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

The

quantity of heat to be taken into account in equation (2)


the quantity evolved by the formation of

therefore

is

257

2(b
molecules

of

temperature
given
a

for

kgrm.

The

'.

(2) (p.

calories.

may now be

255)

written

n b

Q
T

by means of the

been determined

has

16509

dA
dT
is

latent heat of fusion of Glauber's salt,

molecule,

calorimeter as

where b

10)

Na 2 S0 4 10H 2 0; the value of b depends on the


and may be obtained from the tables of solubility

by LOEWEL

Equation

=^r-

....

'

2 (b

number of molecules of water

the

(3)

10)
to each molecule

of sodium sulphate in the saturated solution of Glauber's salt at

the transition temperature

The numerical

values of the quantities occurring in equation (3)

are the following:

16509

calories,

n =: 0.36 according to HITTORF.


b

_T

=
=

15.6

,,

,,

we

obtain

LOEWEL.

305.6.

Introducing these into

(3)

dA
dT

16509

0.36X15.6

305.6

2(15.6

10)

or
rlA

di
and since (note
force in volts,

p.

we

253)

27.09 calories

ppr;;,
ol
Ib

-^

being the electromotive

obtain

dE
1.2 millivolts,

dl
1

2
3

Ann. Chim. Phys. (3), 49, 1857.


E. COHEN, Zeit. phys. Chem. 14, 85, 1894.
POQG. Ann. 100, 377, 1859. This value was obtained

temperature

Chem.

of

Glauber's salt

13, 191, 1894, found n

it

at

9. At

the transition

should be somewhat higher, since BREDIG, Zeit. phys.


0.4 at 25.

17

258

CHEMICAL AFFINITY.

The electromotive
both

with

force of this sodium sulphate transition cell

and

meta-stable phases was

determined by
means
of
the
by
apparatus represented
on page 196; the following numbers were obtained.
stable

E. COHEN and G. BEEDIG

Electromotive force
in millivolts. E.

Temperature.
28 .2

30

5.2

2.9

.2

32

.7

0.5

These data may be represented by the formula

= --2.05+1.57t--0. 0466

from which we obtain, at the transition

dE

point,

t2,

32.6,

1.5 millivolts.

-TT=

may be

This

regarded as being in sufficiently good agreement


with the number obtained by calculation (
1.2 millivolts), the
smallness

of the electromotive forces

consideration.

The equation obtained above


ition cell containing

If

we

temperature

at

q,

evolved

by the

temperatures

Zeit. phys.

described on page 198.

40) containing a solution


by the presence of the

stable above the transition

^,

Chem.

(4)

energy of the
solution

above

which passes into solution


1

is

we have

q! is the chemical

heat

stable

the system which

of

T
A,

of

(fig.

in a condition of saturation

modification

where

also applicable to the trans-

is

no meta-stable phase

consider a cell of this kind

maintained

measured being taken into

at

cell,

that

is,

the quantity

of the modification which


calculated

during

for

the

the passage

is

quantity
of unit

14, 540, 1894.

note on page 257 the result given by the calculation should


probably be higher.
3
E. COHEN and G. BKEDIG, Zeit. phys. Cheni. 14, 535, 1894.

According

to

the

259

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.


I

quantity of electricity
through the cell, and A!
obtainable
the same circumstances.
under
energy
a

for

Similarly,

is

stable at temperatures below

we have

the transition point,

the electrical

containing the saturated solution of the

cell

modification of the system which

A,

is

+ T

q2

......

^|-

(5)

Since the two saturated solutions have the same concentration

at the transition point the two cells have the same electromotive
force at that temperature, and therefore at T o;

from which we obtain


d.

A2

-r^r

dl

branches

electromotive
presents

qi

q2

T
of

the

angle between the two

representing the connexion between the

the curve

of

measure

affords

dl

(at

force of the cell and the temperature, qi

the

of

heat which

is

q 2 re-

evolved by the trans-

quantity
formation of that modification of the system stable at tempera-

below

tures

the

temperatures,

transition

calculated

point

for

into

that

stable

at

higher

the quantity which dissolves at

when unit quantity of electricity passes through the cell.


The graphical representation, on page 202, of the connexion
between

the

electromotive

force

of a cell of this type and the

temperature shows that the curve consists of two parts meeting


at an angle. Each of these parts may be represented by an
empirical equation of the form,

and

Ei

=Q +Bt+

where

is

temperatures between 35 and 45


2
S 2 t' for temperatures between 20 and 30

(7)
(8),

the temperature centigrade.

differentiating these empirical equations with respect to

By
and

+ R^ + S^ for

QJL

subtracting,

we

obtain the

t,

value of the sudden change in

Unit quantity of electricity is taken to mean that quantity which migrates with
1000 coulombs).
equivalent of an ion (96587

A kgrm.

260

CHEMICAL AFFINITY.

the

transition temperature

The

values of -j~

For

cell

of

coefficient

temperature

(32. 6):

- RO

(R 2

-~

(p.

201)

II (p.

202)

III (p.

203)

the

which

cell

occurs

at

the

(S 2

- SO-

.(9)

found experimentally were:

....
.

1.6 millivolts.

-h

+
+

1.2
1.1

The mean value being 1.3 millivolts.


The same "quantity may be calculated from other data by
means of equation (6), in which T the transition temperature
,

on the

absolute

scale,

transition temperature

2 (b

and

si

il ar

^2

ly

them (page 257), and


kgrm. molecule of
and
temperatures above T

at

at temperatures

Na 2 S0 4 10H 2
salt

anc^

salt at its

the heat evolved by the solution of 1 kgrm. molecule of

is

Glauber's

have the meanings already

Na 2 S0 4

^'

~~ur\
10)

L (b

for

q,

the heat evolved by the solution of

is

is

where n

2,

.6

10)

ascribed to

305

is

Wi

Equation

cals.).

'

this,

dA 2

since

the

cell,

A =
dE

This

^TT,

dl

(G)

may

thus be written

nb

'

2 (b

'

10)

introducing numerical values,

10504

dA,
dT"

~dT~
or,

dT

dT

From

Wj

dAa

therefore the heat evolved by the fusion of Glauber's-

is

16509

below

0.36

15.6 ..
:

805.6X2(15.6-10)

23116 E,

where

is

the electromotive force of

1.2 millivolts.

number

experimentally,

is
i.

e.

in

satisfactory

1.3 millivolts.

agreement with that found

261

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

VAN

HOFF, COHEN and BREDIG

'T

dA

dT
be

may

used

the electromotive force of transition

calculate

to

have shown that the equation

type which we have just considered. To do this we


out from the temperature at which A = 0, and sum

cells of the

set

may

increments

the

crements

of

of

with T, taking sufficiently small

and

to

make

finite in-

permissible to regard their

it

ratio as constant during the increment.

normal solution

A =
since

1/4

1/4

sodium sulphate, the temperature at which


at which the saturated solution of Glauber's

normal

however, cannot be observed

this temperature,

below

lies

it

immersed

of

that

is

salt is

is

of Glauber's salt and the other in a

a saturated solution

in

which the one electrode

in

cell III,

first

Taking

the

cryohydratic

temperature.

It

may

be

calculated with considerable accuracy from the formula

dlogC

Q
T2

_
"

dT
which
the

is

true for

strictly

concentration and

'

dilute

solutions,

and in which C

is

a quantity connected with the heat of

solution and varying but

little

with the temperature.

dissolve 5.02
LOEWEL 100 parts of water at
According
9
at
and
10. Substituting these
parts
parts of sodium sulphate
to

values

in

(2)

(after

integration),

logarithm by that to the base 10,


J

_9_

and replacing

we

the

Naperian

obtain

10

"

2.3026

5.02

V273X283/'

At a temperature x degrees below zero the saturated solution


of Glauber's salt will be 1/4 normal, and will therefore contain
71

/4o

grams

1.775 grams (approximately) of sodium sulphate to 100

of water, whence as before

5.02

g 1.775
1

Zeit.

phys.

Chem.

""

x_

2.3026 V273 (273

16, 453, 1895.

_\
x)/'

262

CHEMICAL AFFINITY.

By
that

A =

is,

In

20

order

16

at

equation

by the

evolved

is

(1)

the

represents

which

process

0, 10,

16.2,

The most important quantity entering


it

= 16. 2

use of the values of -7= at fairly

large intervals of temperature, say at

in

obtain x

the electromotive force of the cell at

make

sufficient to

we

these two equations


.2.

calculate

to

is

it

Q from

eliminating

and 20.

into the calculation is

which

of heat

quantity

produces the current.

This-

the transference of 0.36 molecule of i/s(Na 2 S0 4 ) from


process
the saturated solution, the composition of which may be repreis

sented by l/2(Na 2

S0 4) bH 2 0,

to the

222.4H 2 0. The heat evolved by

1/4

normal solution !/2(Na 2 S0 4 )

this process

may

be considered

to consist of three parts:

by the removal of

A! evolved

1.

1/2

(Na 2 S0 4) b

from an

indefinitely large quantity of the saturated solution, and by the


which would then become saturated in
return to it of b H 2

accordance with the equation

i/ 2

The

(Na 2 S0 4)

is

the

are

following

1/2 (Na 2 S0 4 )

5H

quantities

r-^-p
of

i/ 2

heat

(Na 2 S0 4 )bH 2 (X
evolved

the solution formed contains n molecules of water to

The
last

of

is

200

400

9430 -- 9380

Heat evolved

first five

50

9255

9021

(Na 2 S0 4 ).

25
-

7.8

- 8689 -- 7495

numbers have been determined by THOMSEN, the

of Glauber's salt and from THOMSEN'S determination of

the heat of hydration of

1/2

100

i/ 2

calculated from COHEN'S determination of the latent heat

fusion

2.

when

dissolved in a quantity of water such that

A2

is

(Na 2 S0 4 )

Na 2 S0 4

evolved by diluting V 2 (Na 2 S0 4 ) b 2


222.4H 2 0; it also ma^ be calculated from

the heat

to

the

above numbers.
3.

A3

is

indefinitely

the
large

from an
evolved by removing 222.4
2
quantity of a 1/4 normal solution of sodium

heat

263

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

sulphate.

A!

and A 2 are negative quantities, while A 3

9430-9380
and

its

We

value

is

approximately

-r

thus obtain the following numbers.

Temperature.

oo

is

positive

calories.

CHEMICAL AFFINITY.

use

of

the

mean

values

of the temperature coefficients in the

different intervals of temperature;


been calculated in this way.

Temperature.

the following numbers have

ELECTRICAL ENERGY OBTAINABLE FROM

Temperature.

A.

CHEMICAL CHANGE.

266

CHEMICAL AFFINITY.

The agreement
if

is

satisfactory

and becomes somewhat better

the fact be taken into account that the difference between the

electromotive

forces

of the

cells

normal solutions of sodium sulphate,

containing
is

normal

and

1/4

proportional to the absolute


l

temperature just as in the case of a concentration cell containing


dilute solutions; allowance has been made for this in calculating
the numbers in the fourth column.

The

solutions of sodium sulphate contained in these cells being

dilute the electromotive force of cell II containing a

solution
cells

may

be calculated by taking the

containing normal and

numbers are obtained


Temperature.

in this

1/4

normal

way.

mean

solutions.

1/2

normal

of those of the

The following

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

stable phases

we

find,

is

--1.5

with both stable and meta-

cell

millivolts (p.

258).

Equilibrium constant and electromotive force.

3.

From

of the

coefficient

temperature

267

the equations

by solving

q and

for

(2)

substituting the value ob-

tained in (1),

AA

T
__dT

"

2T
and therefore,

by

integration,

putting the integration constant

equal to zero,
log
Since

by

is

a reaction,

equilibrium

The

A
2T*

to the electromotive force produced


each determination of the value of a constant 'of

proportional

at the

is

motive force

K=

same time a determination of

this electro-

!
.

case of

ammonium

NH

sulphide

^ NH

be taken as an example,

may
3

+ H

2 S.

The experimental data have been given on page


value

of

at the temperature

by means of the equations

log

Since a gaseous system

where ni

0,

VAN

HOFF, Lois de

See page 206.

'T

and n 2

is

2,

and

157.

The

be calculated from them

K=

T may

K=

under consideration

and therefore

1'equilibrc cliiinique, p. 54.

268

CHEMICAL EQUILIBEIUM,

A
C2

z=

log C 2

being the concentration of the second system.


unit of concentration of the second system

The
of

ammonia and 34 kgrms.

metre.

the

If

Since the weight of a

0.761 grams,

mixture of gases

the

ammonia

the pressure of the

is

of sulphuretted hydrogen per cubic

of

pressure

17 kgrms.

is

be

will

of

litre

be

mm.

ammonia gas

0.761XPX273 "

_
"

mm.

and 760

at

concentration under a pressure of

its

mm.,

mm.

is

17X2X760XT

124. 4T'

and therefore

A =

We

124.

thus obtain

A.

Temperature.

9.5
25

The number
that

dicates

5992

6000

found,
if

calories

formation

the

34 kgrms. per cubic metre, were


10

producing

of

current,

On

the

other

knowledge

of

hand

it

is

force,

under

the

condition

ammonium

10,

sulphide

in-

from

at concentrations of 17

electromotive

the

clear

definite

of

approximately at

and

to take place in a galvanic cell

combination would be approximately

electromotive

calories.

5132

.1

ammonia and sulphuretted hydrogen


at

4T

log

force

A
==

&
that,

X OQol lo

of

the

= 0.129 volt.

a determination of an

conditions,

must lead

to a

equilibrium towards which the

change tends.
For example, suppose that a DANIELL

cell at

can furnish a

quantity of electrical energy equivalent to 50300 calories, during


the separation of a kgrm. atom of copper from the copper
sulphate

kgrms.

solution

of

CuS0 4

of unit concentration, that

is,

containing 159

per cubic metre, and the solution of the zinc

269

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

already containing 161 kgrms. of zinc sulphate per


cubic metre, then the final condition of the equilibrium
a

in

liquid

ZnS0 4 + Cu
at

0,

We

CuS0 4

Zn,

known.

is

have, namely,

C
-

and

^
I

K,

therefore

A
'

log

50300
'

2T

TYaTI

2-

In this expression

therefore

from which

p
log

At
the

will

^^2

^2

therefore, equilibrium

sulphates

pl

92.1 or

40

10

between the copper and zinc and

be reached when there

between the concentrations of the two

ratio

shows that the concentration of the

is

a certain definite

The

salts.

zinc sulphate

calculation

would be 10 40

times that of the copper sulphate.


It

is

exists

further

to

possible

between the values of

The equilibrium which


with

together
studied

(C),

investigated
1.

and

The

Brucine

reached when an alkaloid

used

alkaloids
(B),

the

is

brought

another alkaloid has been

of

were

following

Quinine

equilibria

(Q),

being

Equilibrium

between

Quinine,

Codeine

and their hydro-

chlorides.

Q +
1

relationship

in a cycle of chemical equilibria.

hydrochloride

JELLETT.

by

Codeine

the

is

show that a general

C.

HC1. ^=

Q. HC1.

Transactions of the Royal Irish Academy, 25, 371, 1875.

270

CHEMICAL AFFINITY.

2.

Equilibrium between

Brucine, and their hydro-

Codeine,

chlorides,

B +

HC1 ^=

B.

Equilibrium between Brucine,

3.

C.

HC1.

Quinine, and their hydro-

chlorides,

B +

The determinations of the


different salts in these

Q.
C.

B.

observed

is

the

of

ratios

OHOl

JELLETT

B. HC1.
quantities

of the

three cases gave the following results

HC1
HC1

obtained

Q +

HC1 ^z

Q.

Q.

that

RHC1

HC1

further

the

HC1
of the

product

numbers

approximately unity.

2.03

1-58

show that

It is possible to

0.32

1.026.

this relationship,

found in a special

case by JELLETT, holds good quite generally.

Let

the

of

values

in the three equilibria be

K K
1?

and

3
any given temperature; the changes which lead to these
equilibria will be able to do quantities of electrical work A 1?

at

and

trations

for

the

of

gram

equivalent of change

mutually

convertible

systems

when
are

the concenunity.

We

have then,
log K!

-giji,

logK 2

~,

andlogK8 =

2T

and therefore,
Ai

4-

AQ

+ A3

log

of the system remains unaltered


taken place, the sum of the
have
changes
quantities of electrical work done by them must be zero, that is,

Since

the

initial

condition

after these isothermal

A!

+ A 2 + A3 =

0,

and therefore,

K!
that

is,

to unity.

the

product

of

K K
2

the

1,

constants

of equilibrium

is

equal

271

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

independent

may

same

the

Since

of

The

of

any similar

series

of equilibria,

number, the following general proposition


The product of the values of
in a cycle of

be enunciated.

chemical equilibria

true

is

their

is

case studied

equal

to

unity.

by JELLETT

an example of

is

this,

for since

K =
and the

values

of

Zai

from each other very

differ

little,

the

equilibria studied being similar, and further

K K
2

we

== 1,

obtain
><

(I:),

We

,*,='

have also
Q0.

from which the

From

the

C.HC1
B.HC1

HCl
HCl

result obtained

electromotive

Taking

example

Q.

by JELLETT

force

possible to predict the direction in


for

B.
_

which

by

it

'

found.

is

produced

HCl
HCl

change

it

is

will proceed.

a case of equilibrium between condensed

systems such as
2

Ag

Cu 2 C1 2 ^z

AgCl

-f-

2 Cu,

the sign of the quantity of heat evolved determines the direction


in which the reaction will proceed at absolute zero
that system
;

which

is

formed with evolution of heat will alone be present

a condition of equilibrium at this temperature.

The following data have been obtained by


Reaction.

F. BRAUN.

in

272

CHEMICAL AFFINITY.

From

these

the second

is

numbers the formation of the

first system from


an
of
evolution
heat
of 131600
accompanied by

117500= 14100

at absolute zero, therefore,

calories;

formed at the expense of the second. This


the

sarily

is,

at the ordinary temperature;

case

will

it

be

however, not necesthe heat evolved

no longer equivalent to the work which the change is capable


of producing, and it cannot therefore be used to predict the
is

direction

The work which the

of the reaction.

reaction can do

may be measured by means of the electromotive force produced


by it. When the first system is formed from the second this
work

2200

The

when
still

according to the numbers given above, 99200

is,

calories.
first

it

97000

is

system thus represents the condition of the system

in equilibrium at the ordinary temperature, the

occurring

same direction as

the

in

change

at absolute zero.

The

be present alone, in equilibrium,


system
until the transition temperature is reached; at which point both
continue

will

first

systems

may

to

together, above

exist

the

it

system will give

first

place to the second.

We must now calculate the transition temperature having


done so the condition of the system in a state of equilibrium is;

known

at all temperatures.

In the equation

A _
the

all

(273

is,

calories.

known with

the

approximately)

14100

is

that

are

quantities,

P
q

value

From

of

these

the transition temperature

At T

the exception of P.

is

2200

calories, that of

numbers we
lies

at 51

C.

be

find

It is

324

noted that small changes in the values of A, q, and


have a considerable influence on the value of P obtained.

to

As

a further example

we may

however

consider a case of heterogeneous

equilibrium such as
2

According

to

the

Ag Br

;^z: 2

Ag + Br2

laws governing equilibria of this kind the

ELECTRICAL ENERGY OBTAINABLE FROM A CHEMICAL CHANGE.

bromine must, at each temperature, attain a


which vanishes only at absolute zero.
Silver

when placed

bromide,

temperature, must therefore


attained the extremely small

bination

this

latter

has

pressure corresponding

This pressure

may be

calculated

way.

work which may be obtained from the comof metallic silver and liquid bromine is known it has

The quantity
been

pressure,

at the ordinary

bromine until the

maximum

to the prevailing temperature.


in the following

vacuum

in

lose

maximum

273

of

determined by measuring the electromotive force to which


reaction gives rise.
From the table on page 271 it is

equivalent to 85000 calories.

This quantity of work

may

A =

also be calculated

2T

from the equation

log fsi.,
^AgBr

where S Br
of the

the vapour pressure of liquid bromine, S AgBr that


bromine from silver bromide at the temperature T. At
is

the boiling point of bromine (about

= 273 +

60, S Br

60) we

have

760 mm.,

and therefore

S AgBr

That

vacuum

is,

silver

at 60

pressure of

2.9

10

53

mm.

will decompose when exposed to a


bromine vapour evolved has reached a

bromide

until the

2.9X10" 53 mm.

A similar calculation shows that the pressure of chlorine


evolved from silver chloride at the ordinary temperature is
S AgC1

5.4

10- 75 mm.

THE END.

APPENDIX
Note

(page

1,

There

2).

begin with, Co kilogram molecules of arsenic hydride


At the time t a fraction x of them has undergone

to

are,

a cubic metre.

in

decomposition; the concentration of the arsenic hydride


Q

Co

x)

(1

of the gas

-y

and that of the hydrogen molecules


is

proportional to the concentration

~
T _(l-x)C
~c
Pt

+ f xC

-.

Ct

a,

Note

2,

32.7

cc.

(1

^-to- +

2)

then Ct

Since the pressure

we have

Therefore

is

2'

Co

(page 95).
of pure air (saturated with aqueous vapour at 0, and under
pressure of 760 mm.) would occupy 32.45 cc. when dry, and would
cc. of oxygen. The hydrogen added (13.8 cc.) is in excess;
quantity of electrolytic gas is thus 3 X 6.78 =z 20.34 cc. initially.
the time t a fraction 11 has undergone change, that is 20.34 11 cc.

contain 6.78
the

At
The

fraction of the

~P

time

is

whole quantity of gas which has disappeared

^5 o

or,

since

-t

the lengths

of the column of air are in-

versely proportional to the pressures,


L<t

We

thus obtain the expression

46 5
.

By

at this

"P

the translator.

20 34
.

276

APPENDIX.

3, (pp. 123 and 248).


The connexion between the

Note

quantities of heat evolved by the conversion of a material system, A, into another, B, at different temperatures
may be obtained as follows:

At the temperature T, let one gram of A be converted into B, q T calories


being evolved. Now let the temperature of B change to To, C B (T T )
calories being evolved, where C B is the specific heat of B. At T let
the substance be reconverted into A, with evolution of
q calories,
and finally let the system be brought back to the temperature T, the

quantity of heat evolved being CA (T


T) calories, where C A is the
If
of
A.
the
heat
external
work
done
specific
during these changes be
zero or negligible

qT

Note
If

4,

we

we may

write

C B (T
qo
or q T =:qo

To) -f CA (T

+(CA

(page 256).
u the velocity with which

call

T)

C B )(T-T

Na

0,

).

move through

ions

a solution

of NaoS04 under the influence of a given E. M. F., and v the velocity


of the SO4 ions under the same circumstances, the quantity of Na ions

which move out of the solution surrounding the anode, i. e. the loss
of NaaSCh there, will be proportional to u, and similarly the loss of
Na2S04 from the solution round the kathode will be proportional to v
the whole quantity of NasSCU decomposed being proportional to (u -j- v).
The migration constant for the Na ion is the ratio between the diminution in the quantity of Naa S04 in the solution round the anode, and
r

the whole quantity decomposed,


If

Na

we

call the

i.

e. 11

=2

whole quantity decomposed unity, n

quantity of SCh ions which


kathode.
the
surrounding

Note

is

the quantity of

which moves out of the solution round the anode, and

ions
(1

11)

5,

the

p. 89.

Valvolin

is

a trade

moves out of the

solution

name for vaseline, used in Hamburg.

NAME
Alexejeft*.

Arrhenius

208

....

123, 131, 133

INDEX.
Duclaux

Dumas

94

Engelraann
Esson
.

....

32, 33, 59, 81,

Baeyer
Bellati

Berthelot
123,

28,

30,

Evans

Ewan
Eykman

92,

253
168
51
52

Faraday
Forcraiid (de)

Bodenstein

32
27
.

.201

Bordet

168
205, 210, 222
Boyle
Braun
254, 271
Bredig 169, 198, 257, 258, 261, 263
Bremer
159, 178
Brodie
215
Buchanan
14, 32
Bunsen
33, 39, 48, 91, 93, 136
.

13, 93, 124,

93,

215, 224, 225, 242

(du)

196
135
171
125
33, 56, 61, 82
189
52,

Ettling

92
246, 247
52,

36,

86

169, 203

124, 145, 146, 151, 154, 163,

Boguski
Bois-lleymond

168
51

42, 47, 48, 49

Askenasy
Anbel (van)
Baker
Baur

Fourcroy
"
Friedel

Frowein

158, 161,
221, 235, 236.

Gay-Lussac
Gibbs
Gockel
Goldschmidt

Graham

Cailletet

168
168
83, 85
205, 210
126
242

Chappuis
Charles

Clausen
Clausius

Cohen

Conrad

125, 133

254

Czapski

51
25

Dent

Deveuter (van) 150, 165, 169, 170,


173, 187, 207, 208, 250.
152, 223

Deville

Dewar
Dixon
Docters van Leeuwen.

Guldberg

...

Harcourt
Harker

Hautefeuille

Hecht
Heide (van der)
Helmholtz H
Helmholtz E

Hemptinne
Henry

135
33
173, 221
125, 133
172
252, 253, 254
82

13, 93, 124,

(de) 116, 118, 119, li>l

12

Hittorf

Davy

81
32, 33, 59
163
.

211,

205
254
254
81, 170, 171, 250
32
145, 206, 233

169, 188, 193, 198, 254, 257,


258, 261, 262, 263.

178,

....

Chancel

162,

257

Hoff (van

't)

24, 30, 32, 34, 36, 49,

57, 59, 82, 123, 138, 145, 147, 148,

151,

165, 169, 170, 171, 173, 187,

206,

208,

Hofmann
Hood

243, 247, 250, 261, 267

........

36
132
Horstmann
143, 145, 151
Houton de Labillardiere
51, 52
20, 125,

278

INDEX.
56, 61
156, 157

Ikeda
Isambert

Ostwald

254

Jahn

269, 270, 271

Jellett

Jorissen

52, 171,

Joubert 52,
Joule

61, 62, 66, 86, 141,

Kahlbaum
Konowalow
Kooy 32, 49,

93,

125,

123,

250
254
254
75
125

125, 126,

12,

13,

27,

115, 116, 119

125, 193, 199, 233.

Pareau
Parmentier
Pe"an de Saint Gilles

235
168
28,

30 36, 92,

93, 145, 146.

....

Pfaundler

143, 145, 161


Pfeffer 230, 231, 232, 233, 234, 235
Pfeiffer
191

201
33

Poggendorff
Pringsheim

134, 169.

171, 181

Kopp
Krauel

42,

47,

48

Raoult
Reicher

Laar (van)

208, 210

52

Ladenburg
Landolt

28, 29

Le Chatelier

Lehmann

....

181,
249.

183, 207, 216, 243, 244, 247,

Reinizer

83, 96

Rennie
Rodwell

164, 168, 221

4, 9, 30, 52, 94, 105, 115,

116, 119, 125, 130, 168, 171, 173,

208, 243

Leeds

Lemoine

36
193
81
Leverrier
133
Ley
189
Linebarger
Loewel 168, 175, 187, 257, 261, 263
Lowenherz
118, 119, 180
92
Luff
Lussana
167, 243, 244, 246

Romanese

Lescoeur

Rontgen

Mallard

243
82
208
51
82
95
136
137
186
199
234
194
168

Scacchi

211

Stefan

254

Swart

....

Marchand
Marignac

Marum

(van)

Meissner

Menschutkin
Meyer L
Meyer V
.

28,

29,

42, 47, 48, 49,

Meyerhoffer
Miller (Lash)
Mitscherlich

93,

28, 30,

172,

221, 230,

Moser
Mulder

193,

234
137

...

Raum

81
92
246

246, 247
30, 31

Roozeboom

(Bakhuis)

176,

168,

184, 187, 207.

Roscoe
Rose

33, 48, 91, 93

51

Riidorff

171
'

Sabatier
Salzer

170, 186,

Schiff

173,

Schonbein

Schwab

...

Schwarz
Schwicker
.

15, 17, 28, 129,

167, 181, 185, 203,

Scott

Shenstone
Skalweit
Smithells

Spohr

125,

125
85
250
178
83
130
244
105
104
34
83
25
133
248

Spring 27, 30, 93, 94, 243, 247,


Stadt (van de) 20, 33, 54, 57, 58,
59, 60, 207, 208.

Xaumann

...

43,

Nernst

Noyes.
Ogier

44,

93,

188, 194,

......

63
152

102, 104, 111

154

Tammann

.31

279

INDEX.

Than
Thomseii

Thomson
Thomson

161,
J.

224,

Thorpe
Tollens
Troost

Tutton

Urech

32,

Verschaffelt

90,

91,

33
264
80, 81
254, 255
86
37
152, 173, 221
86

Vriens

161, 172, 221

Waage

145, 206

225, 262,

94,

107,

133

169, 188, 199

Walker
Warder

199
4,

33,

Weltzien

Wiedemann E
Wiedemann G
Wilhelmi
Wittwer
Wright
Wyrouboff

116,

125,

130, 133

173
169, 184

236
13
13
92
170, 186

SUBJECT INDEX.
Acetamide, decomposition
acids,

of,

by
125
28

12,

Acetic acid, etherification of,


Acids, influence of the nature of,
on the hydrolysis of their esters

Arsenic oxidation
Astrakanite,

of,

transition

.52

of

point

169, 176, 178, 179, 184, 187

Atomic condition of oxygen

gas.

8286

80,

116, 120

8286

Active oxygen,
Activity
Affinity

....

coefficient.

.........
at absolute zero,

measurement

of,

208
229
241

230235

of salts for water of crystallisation,

230, 234

by, 235240
Alcohol, influence of the nature of,
on the hydrolysis of its

work done

esters,

....

retarding

116, 119

action

of,

Barium

chloride,

affinity

234
hydrated, heat
of formation of,
161
28
Benzene, nitration of,.
Bimolecular reaction
4, 9, 15
Birotation of milk sugar,
32
Bloedite (astrakanite) 169, 176, 178
179, 184, 187
Bromic acid, action of hydriodic
acid on.
140
.

28,

35
80
Alkaloids,
269, 271
33
Ammonia, decomposition of
Ammonium carbamate, 34, 89, 94
34
carbonate,
nitrate, 164, 168, 221
246, 247
34,

Aldehyde, rate of oxidation of,73

Cadmium

choride (hydrated), tran169

sition point of,

Calcium carbonate, dissociation

...

racemate,

transition point of, 170,


171, 250

sulphide, dissociation
of, 155, 156, 157, 205
219, 223, 267
of, in wa-

Arayl alcohol, solubility


ter

Aniline, action

of,

on

189, 190
acetic acid,

28, 93
Anti-benzaldoxirne acetate
133
Arsenic compounds, preparation of
30
by pressure,
hydride, decomposition of
1, 2, 20, 32, 99, 134
.

....

of,

218

sodium

for

of,

water,

Calcium oxalate, action of acids


155
32
125, 133
33
Carbon, oxidation of
monoxide, explosion of
with oxygen, 33
action of, on metallic oxides, 92
action of,
on
151
water,
31 34
Catalytic action,
of hydrogen and
on,

Cane

sugar,

inversion

30,

of,

....

hydroxyl ions,
Chemical induction

116, 121

9198

Chloracetic acid, action of water on,


14, 32, 125, 130
Chloracetate of sodium, action of
NaOH on,
15, 125, 129

....

INDEX.

282
Chlorine,

action

of,

on hydrogen,

Disturbing actions, elimination of

93

8691

tranColour, determination of the


203
sition point by,
193, 194
Concentration currents,

in gases, 31, 43, 50


26
in liquids,

83, 91,

.18

gaseous,
of a system,.
unit of,
.

4
163

....

incompatibility
165

of

temperature in cases

169, 173,

of,

229

12

...

Condensed systems,

Double decomposition, transition

203
Electrical conductivity,
methods of determining
.

the transition point, 193-203

.2629,3134

work done by chemical

Copper, action of on ZnSO-i, 269


bipotassium chloride, decomposition of, 161, 162,
172, 229

Electrodes, unpolarisable, 195, 196,

Contact action,

calcium acetate,

30, 171,
172, 247
affinity of for

sulphate,

water, 234, 235


dissociation of

hydrated, 158,160
heat of formation
160, 161
method of deter-

of hydrated,

Crystallisation
mining the transition temperature,

186

Cuprous chloride,action of, on silver,


271

Cyamelide, see cyanic acid.


Cyanic acid, polymerisation

3638, 4345,
107110,

173,

of,

88, 96, 97,

174,220223
25

Cyanogen,

acid
Cyaiiuric acid, see cyanic
Cycle of chemical equilibria, 271

233
47

Depression of freezing point,


Devitrification,

change, 251, 252, 254, 255

199
Electrolytic gas, transformation into

water.

36,

3942, 4549,

Electromotive force,
.,

with equilibrium constant 267


Electromotive force, determination

#-Dichlorhydrine, decomposition of
125
178
Differential tensimeter,
94, 181
Dilatometer,
.

Dimethyl ethylene hydrochloride,


125
decomposition of,

....

Dissociation,

144, 152,

salts,

155157

of hydrated
158161, 188

pressure

by means

of direction of change

272
Electromotive force, measurement
196
of
of,

Electromotive force, produced by


253
chemical change
143
Equilibrium, chemical,
analogy with
211
physical,
in
condenchemical,
Equilibrium,
sed systems,
163180, 219
.

Equilibrium, chemical, in heteroge155 168, 218


neous systems,
.

Equilibrium, chemical, in homogeneous systems,


143155, 222
Equilibrium, influence of tempe.

rature on, 148, 212, 217,

Equilibrium, constant.

223-228
.

145

connexion of

Dibromsuccinic acid,

30, 113, 114,


115, 125, 127, 128

95

.253, 264
connexion of
.

of with E.

M. F

Equilibrium, physical,

267
204

in condensed
210, 219
systems,
Equilibrium, physical, in heterogeneous systems,
205, 217
Equilibrium, physical, in homo205, 222
geneous systems,
Equilibrium, principle of mobile,
217, 228
.

TJNIVERJ
283

INDEX.

Esters,

formation

36,

28,

of,

92,

146, 151

Esters,

hydrolysis

of,

Etherincation,

11,

4,

28, 36, 92, 146, 151


influence of pressure

30

on,

Ethyl acetate,

125,
130, 131, 133, 147

4, 8, 11, 28, 115,

Ethylene hydrochloride, decomposition of

Evaporation, equilibrium

of,

125
204

206, 217
63, 64
Evaporation, rate of,
Explosive limit for dry phosphine
56
and oxygen,
Explosive limit for moist phosphine
and oxygen,
57 61

...

of,

158161, 188

32,

130, 131, 133

115121,

28

Hexane, rate of reactions in,


Hydrated salts, dissociation

Hydrated

salts,

transition point of,


168, 179, 180

Hydrates, transition point

of,

168

Hydriodic acid, action

on

bro-

mic

of,

104

acid,

Hydriodic acid, action of, on hy104


drogen peroxide,
Hydriodic acid, decomposition of,
32, 36
Hydrolysis of esters, apparatus and
methods,
6, 10
Hydrolysis of esters by acids,

116121

Explosion, velocity of, in dry gases,33

Hydrolysis of esters by bases, 4,


11, 32, 115, 116, 130, 131, 133
85
Hypophosphoric acid,

Fatty acids, action of bromine on, 94


Ferric chloride, action of, on SnCls,

Identity methods of determining


the transition point,
186

110112
Ferrous

action

sulphate,

of,

on

KClOs, 132
Formaldehyde, polymerisation of,
36, 89
Freezing point, depression of, 233
Fumaric acid, action of bromine on,
105, 106
Fusion,
210, 219, 243

...

Gaseous concentration
Glauber's

nium

salt,

action of on

18

ammo173

chloride,

action of on potassium chloride.


173, 177, 178
Glauber's salt, transition point of,

Glauber's

salt,

...

136 142
Ignition temperature,
165, 219
Incompatible systems.
.91 98
Induction, chemical,
Initial acceleration,
91 98
Inversion of cane sugar, 30, 32, 133
Invert sugar, action of, on Fehling's
.

90

solution,

lonisation, effect of pressure on, 31


Isodibrom succinic acid, 1 13, 114, 115

Isomers, equilibrium of optical, 151


transition point of,
173
.

Lactic acid, action of bromine on, 92


12
Lactones, action of bases on,
.

Light, effect of,

on chemical change,

168, 169, 175, 179, 180, 184, 188, 191,

192, 193,

198203,

230,

255257

....

93
146

heat of

for-

33, 91, 92,

Limiting

equation,

Magnesium

sulphate,

mation of hydrated,

Heat evolved by reactions at high


or low temperatures, 224 228
Heat evolved by reactions, connexion

of,

with equilibrium con-

148150

stant,

Heat evolved by
nexion

of,

conwith velocity constant,


reactions,

122126
Heat

of solution,

207, 208

161
Marble, rate of solution of, 27, 94
Maximum work, principle of,
224, 242
Medium, action of the, 26, 27, 43
Mercuric iodide, transition temperature of,
203
Metaphosphoric acid, action of
water on,
125
Metaphosphorous acid, 21, 22, 23
.

.......

284

INDEX.

Methyl ethylene hydrochloride, decomposition

125

of,

M ethyl iodide, action of, on sodium


125, 133
behaviour of, to

ethylate,

Micro-organisms,
oxygen,
Milk-sugar, birotation of,
Minimum work, principle

52
32

of, 225,

242
Mixtures, recognition of, 113 115
Moisture, influence of, on chemical
3235, 58, 59, 81
change,
Moistening the walls of the vessel,
.

8991
Molecular volume, influence ofoii
the rate of reaction,

Monomolecular

reaction,

.15
1,

13

Phosphine, decomposition of, influence of temperature on, 126,


oxidation

Phosphine,

52
28
133
Nitriles, formation of,
Nitrogen peroxide, 122, 144, 205, 222
Nitrogen peroxide, heat evolved by
the dissociation of,
152 155

Nitration of benzene,

reactions,

perature and pressure on, 61, 66, 141


86
21
Phosphorous acid,

Phosphorescence, intermittent,
formation

Phosphorus,

32, 33.

8186

27
Polymerisation, see cyanic acid and

formaldehyde.
Poly molecular reaction,
formation

4,

....

of,

Potassium astrakaiiite

167, 203

of,

7380

magnesium

sulphates.

172, 173, 185

Potassium sodium racemate, 170,171


Pressure, influence of, on the luminosity of phosphorus, 61, 66, 141
Pressure, influence of, on the oxi79
dation of aldehyde,.
Pressure, influence of, on the oxi-

...

dation of phosphorus,

66, 69

Pressure, influence of, on the rate


30
of reactions in liquids,

Pressure, influence

sition temperature,
Pressure, influence of,
sition

phosphorus,
5],

of,
.

25,33,

50-61
32,

33,

6169, 8186

sulphur, 33, 52, 69

73

Oxygen, atomic condition of, 80, 82


Ozone, formation by the silent dis34
charge
Ozone, formation during the oxidation of phosphorus, 82 86

Phosphine, decomposition of, 3, 20,


32, 43, 45, 49, 50, 99-101, 139

on

20
FeO,
Potassium chlorate, action of, on
125, 132
FeS04,
Potassium hypoiodite,
104

93

ganate,

Oxidation of aldehyde,
phosphine. 20

173

action

chlorate,

19

trans-

substances,

....

Osmotic pressure,
189, 230235
connexion of with
n
n
vapour pressure
232, 233
Oxalic acid, action of, on perman-

of,

Phosphorus, oxidation of,


51, 61-69,
Platinum sponge,

of molecules participating
in a change,
99 112

29
equilibrium be151

of active
83

oxygen by oxidation

Number

Optical activity,
isomers,
tween,

25.

5061

Phosphorescence, influence of tem-

...

Normal

of,

....

135

20

33,

Polymorphous
Nickel carbonyl, oxidation

134,
of,

temperature

on the tran242, 243


tran-

on the

of sulphur,

244246
Principle

of mobile equilibrium,

217228
Racemates,

170, 171, 186, 250

Respiration of plants,.
Rochelle salt, decomposition
.

of,

Rotativity
Salts,

hydrated,

dissociation

126
162
29
of,

158161, 188

285

INDEX.

172, 185

Schonite,

Semipermeable membrane,.

231

52
Silicon hydride, oxidation of,
Silver bromide, vapour pressure of,
273

vapour pressure of

Silver chloride,

273
Silver iodide, transition temperature

.247

of,

Simonyite, see astrakanite.


Sodium ammonium racemate, 170,
171, 186, 250

Sodium ammonium
Sodium

tartrate, 170,

171, 186,

250

action

of
129

chloracetate,

.... 15, 125,


Sodium ethylate, action
methyl iodide, .... 125,
NaOH

on,

on

of,

133
Sodium hydrogen phosphate, hydrated, heat of formation of, 161

Sodium hydrogen phosphate, hytransition

drated,

temperature,
169, 203

Sodium potassium racemate,

170,

171

Sodium

sulphate, anhydrous, 168,

177180, 184, 188,


191, 192, 193, 198-203, 230, 255-257

169, 173, 175,

Sodium

sulphate, decahydrated, 168

169, 173, 175, 177180, 184, 188,


191, 192, 193, 198-203, 230, 255-257

product

Solubilities,

of,

177

206209

Solubility

Solubility at the transition temperature,

174178, 186, 187


amyl alcohol,

Solubility of water in

189, 190

Solution heat

231, 234

of,

Sulphur compounds, preparation of


30
by pressure,
Sulphur, oxidation

of, 33, 52,

pressure,

188192

of dissociation,
189, 192

143
supersaturated, at the
transition point,
175
.27 29
Solvents, indifferent
use of, in eliminating dis-

turbing actions,

Stannous chloride,
FeCls,
Steam, dissociation

.8789

action

of,

on

110112
of,

...

2r2o

Sulphur, transition point,

181183,

168,

30, 94, 95,

210, 212216, 220,


244246, 248, 249

221,

Surface of the walls of the vessel,


area of,
Surface of the walls of the vessel,
nature of,
4350

..43

133
acetates,
System, unit of concentration of a, 12
253
quantity of a,

Synaldoxime

Tartaric acid, action of bromine on,

92
Tartrates, transition temperature of,

Temperature
sition

163, 170, 171, 186, 250


coefficient of the tran-

cell,

257259, 266

199,

Temperature, influence
librium,

....

of,

on equi-

148, 212, 217

Temperature, influence

on the

of,

of reactions, 122
Temperature of ignition, 136

135
142
Tensimeter,
158, 187
Thermometric method of determining the transition point, 184, 185
Transition cell with stable and
metastable
194, 195,
phases,
velocity

254259
with stable and
without metastable phases, 198

Transition

cell

Transition

point

(temperature),

point,

calculation

203,

258266
164, 165

.,

of,

212216, 248251

6973

change of rhombic
into monosymmetric,
94, 95
rate of

207

of,

Solutions, solid,

Sugar, osmotic pressure of solutions

determination of by
the dilatometer,
181183
Transition point, determination of
.,

197
by electrical methods
Transition point, influence of pressure on
242, 243
Transition point, methods of deter180, 181, 203
mining the..
.

286

INDEX.

Triethylarnine, action

of,

on ethyl
28

iodide,

Trimethylethylene

hydrochloride,
125
Trimolecular reaction, 25, 110, 113
29
Turpentine,

...:...

Units of concentration,
Unit quantity of a system,
.

electricity

,.

4,

12
253
259

Walls of vessel,

effect of

moistening,
86, 89, 90
Walls of vessel, influence of area of,
43
Walls of vessel, influence of nature
of,
43, 50
Water, influence of, on chemical
change, 32, 33, 34, 37, 58, 59, 81

Work done by
Work done by

89, 275

Valvolin,

Vapour
point,

pressure at the transition


.

178, 179, 180, 187, 188


1

Velocity constant,

influence of tem122 135


perature on,
Velocity of explosion, effect of
33
moisture on,

....

chemical

affinity,

235, 236, 238, 240


chemical affinity at

241

absolute zero,

Work,

electrical,

change,

done by chemical
251, 252

Work,

principle of maximum, 224,

Work,

principle of minimum, 225,

226, 242

242

......

Velocity of reaction in mixtures, 113


Volume, change of, at the transition
184
temperature,
Volume, influence of, on the rate
13
of bimolecular reactions,
Volume, influence of, on the rate
3
of monomolecular reactions,
Volume, molecular, influence of, on
the rate of reactions, 13, 15, 18
.

94
Zinc, action of acids on,
Zinc sulphate, action of coppei on.
.

269

Zinc

hydrated, affinity
234
Zinc sulphate, hydrated, heat of
161
formation of,
sulphate,
of for water,

Zinc sulphate, hydrated, transition


169
temperature of,
Zinc sulphate transition cell, 194, 195

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