Professional Documents
Culture Documents
IN
CHEMICAL DYNAMICS.
-STUDIES
CHEMICAL DYNAMICS
BY
J.
H.
v A N
H O F F
'T
ERNST COHEN
DR.
Amsterdam
TRANSLATED BY
THOMAS EWAN
M.
Sc.,
J.
H.
Ph. D.
College,
Leeds
VAN
'T
HOFF
AND
AMSTERDAM
FREDERIK MULLER
LONDON
WILLIAMS & NORGATE
& Co
I
896
Harms &
Co.
PREFACE
The
,,
I.
new
desirability of a
however,
This,
at
represented,
edition
gave
rise to a difficult
publisher.
the 'Etudes'
'
problem
my
advanced.
To
to
introduce
original
change
E. COHEN'S
now
nothing
would
is
proposal
to
be
to
contribute
nothing to
to the public.
revise
the
'
very
so,
successfully
may
this
assisted,
work serve
came
moment, and
tory history.
H. VAN
'T
HOFF.
PREFACE
The
first
edition
then
Since
to
be
known
many
uncommonly
facts,
of
this
title
II.
'Etudes de
Dynamique ChimiqueS
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
German
been
memoir
homogeneous whole
as a
is
not merely to
which have
engendered
edition
by
;
it
together
in doing this,
ERNST COHEN.
The appearance of a
'Etudes
classical
wished-for
de
opportunity
of introducing
to
it
'T
HOFF'S
to provide a
a wider
circle of
in
language
dealing
desirable.
The
simplicity
change and
and
affinity
originality
makes
it
uncommonly suggestive
sense
of
the
original,
is
The
sufficiently
indicated in the
am
greatly indebted to
my
friend A. C.
WEIGHT M.
A., B. Sc.
May
1896.
THOS. EWAN.
UNIVERSITY"
C*7
CONTENTS,
THE COURSE OF CHEMICAL CHANGE.
First Part.
REACTION.
Page.
I.
The monomolecular
reaction.
Decomposition of arsenic
1
hydride
II.
III.
IV.
The bimolecular
,,
reaction.
Hydrolysis
,,
The polymolecular
Simplicity of
reactions.
many
I.
Chapter
Effect of the
.........
I.
medium on
26
II.
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.
II.
25
Chapter
15
DISTURBING ACTIONS.
of contact
II.
Second Part.
I.
...
of esters
31
43
50
of oxidation
and aldehyde
of phosphorus,
sulphur,
61
CONTENTS.
II
Page.
Chapter
I.
II.
Methods
and
III.
of
Third Part.
I.
APPLICATIONS.
A.
Method
in
which the
99
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
1.
III.
91
II.
86
of
.107
.
110
dibrom-
113
b.
esters by acids
Hydrolysis of
115
....
.116
VELOCITY CONSTANT K
a.
Application of thermodynamics
b.
122
.
...
.127
CONTENTS.
Ill
Page.
-.
.129
:l.
4.
5.
Influence
130
reaction
130
of
the
132
7.
8.
Influence
9.
133
133
sugar
of the temperature on the action of sodium
133
from syn-aldoxime
acetates
133
Second Part.
THE TEMPERATURE
OF IGNITION
134
.136
CHEMICAL EQUILIBRIUM.
First Part. THE
I.
Homogeneous systems.
a.
b.
II.
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
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
Relation
4.
salt
and of solutions of
179
it
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
188
1.
Solutions
2.
.192
Electrical methods.
2.
1.
Electrical
2.
Further methods
....
stable
and
198
203
CONTENTS.
Page.
Second
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
The
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
b.
In-
219
compatible systems
III.
The
homo222
geneous systems
AFFINITY.
I.
II.
III.
229
affinity
salts.
....
230
235
CONTENTS.
VI
Page.
IV.
Applications.
Work
1.
done by
241
Influence
3.
b.
The
The
pressure
of
ammonium
laevo-
into sodium
and
248
sodium
dextro-tartrates
1.
2.
3.
250
electrical
Appendix ...
Name
of
Diagram
2.
a.
V.
work done
of the
index
Subject index
cell.
251
.
254
267
274
276
279
I.
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
the process
ition,
On
these
is
subject to the
grounds we
same law.
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
where C
t,
constant.
1
ture,
It
is
of course assumed
here that
is
we assume
with
in
the following;
As
If
studied
H =
3
As
3 H.
ance
Let
the
and
be
the
and
Then
P
*t
p +
n
-t
"
t).
or
Ct
The apparatus
for
(3
(1)
The
Time
in hours
t
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
k have been
column
log*
J
G;
down
From
clusion,
the preceding
which
we may draw
in the
case
of a monomolecular reaction.
and
2,
which remain
we
log
obtain
__
kt
log
-^
AI
__
- ^g
from which
-=r-
AI
-=-,
log
2-
-J
A2
or Xi
= X
lo S
2.
IA
t,
will
II.
Hydrolysis of Esters.
We
will
molecules
call
in
change
is
is
we
If
G!
call
C2
and
the
=
at
where
kj
CJL
^=
C 2 and
at
k2
C2
is
As the
unit
are considering,
of a body
of concentration
molecular weight of
it,
we
If
we
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
at the ordinary
in
takes place
,
-
dt
LIES. Ann. 228, 257, 1885.
Berichte. 14, 1361, 1881.
its
this
d Ci
reaction
this
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
solution
moment during
can
be
C% that of
Consider
concentration of the
:>
the
the reaction
is
its
We
the base be
if
after
have then,
k Ci
-~
d_Ci
this the
from
C w be determined
concentratration,
complete.
be calculated
may
2,
an acid
with
titration
by
reaction
determined
then at any
(Ci
we
obtain
_ CA
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
-
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).
of the apparatus, A,
G;
p-7p
bi (U
logarithms
log
first
is
is
of these
conducted
F and
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
way
by means of a thermometer
temperature
To prevent evaporation
liquid
this
of a degree to be read.
Fig.
according as
or too low.
in
produced
and which
it
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
of
of
filling,
mixing,
off samples.
is first
placed in
filled
alkali
be
shall
It
present.
therefore necessary to
is
know
to
shown
placed
base,,
ally
alkali
is
the
the
way
described,
temperature
of
when
so that
the
the temperature in
filling,
liquid
In
air),
which
in
ester,
in the figure,
in
F is regulated
the apparatus
it
is
about
is
quite full
0.4 below
that
by the thermometer D.
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
is
now
placed in
its
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
displaces
the
liquid
and 100
cc.
mark E,
the tap
is
When
closed again,
measured
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
the tap is
each time
a sample
and
amply
is
drawn
off,
and since
is
is
the
cc.
of the liquid
is
for
be
the
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
Time
in minutes.
l
:
CALCULATION OF RESULTS.
T! (T t
cubic metre,
of
- Tw
)'
values
the
since
be written thus
rp
/rp
may
(the
of the
caustic
soda in
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)'
of the
The equation
leads
us
TH.
k Cl C,
in the reaction
L.
f=
REICHER
is obtained, whether
excess of caustic soda, or of the ester, be employed.
In this case also, the hydrolysis of ethyl acetate
caustic
by
10
is
2.
be exposed to the
or
duction,
itself.
The apparatus
X)-
consists of
two
fairly strong
mark U
the
100.2
was
125.7 cc v
from
to
cc.
being
exactly
carefully
filled
from
titre,
cleaned
to
the apparatus,
and
dried,
the piece of
is
V;
2.
of
of the
is
now
it
apparatus A (fig.
united to V by a
it
this
can
two layers.
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
for at least
This
is
attaching
connected
out to the
to
mark
11
mixture
allowed
are
100.2
second
ratus
The
flow
cc.
way
into a
This
in excess.
of liquid
is
after
T, in the
to
which must be
phuric acid
now
is
just described.
contained in the
following table:
Time
in minutes,
t
of caustic soda.
12
T w must
k (page
for
9) so that in table b
2.
3025X100
TCO
TX (T t
og
Nt
(T x
a considerable
TM)
Tcy
number of researches on
changes
+
+
examples of bimolecular
and that
2
are to be mentioned.
of bases on lactones studied by P. HENEY
A simplification which may be introduced by using the react,
in
not
does
we may
^=
k, Cx
C 2 and
~=
k, C,
C2
d C
k C2
dt
we
obtain
p\j
kt
constant
(1)
n
C
t
.
-
Cx
therefore
|-
Zeit. phys.
Chem.
(2),
27, 1, 1883.
13
INFLUENCE OF VOLUME.
we
in equation (1),
On comparing
for the
get
(L
\C t
this
IV
'
d/
JL
"id
Tt
3),
3T.-2TY
l
a great difference
While
in
the
is
apparent.
its
value
is
(t),
in
also a function
of the
in the courses
In a bimolecular reaction
the
cular
reaction
differs
is
reaction,
C2
its
not
in the equation
d C,
IT
kl Cl
is
that
is
the
process
takes
in
place
molecular reaction.
Processes of this kind have been examined in great number.
1
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
BUCHANAN
C2
Cl
As may be
as
if
In
of
+ H
C 2 H,
acid
litre
per
was heated
ing
water.
and
the
The
titre
Cl.
chloracetic
+H
foreseen,
were monomolecular,
it
water
reaction
containing
grams
in boil-
cooling,
of N/io ammonia.
Ci
the
and
TI
decomposition,
we have
ct
the relationship
2 Tx
c,
Tl
The following
Time
in hours,
t
60
15
III.
In
order to determine
process which
C2
is
Cl
this,
analogous to a
Na
NaOH
hydrolysis,
C2
Na
-f-
NaCl.
'^^^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-
tioned
We
men-
may be employed.
have then only to take into
3.
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
at
given
moment.
Since
of sodium
chloracetate
and
See also
1.3879
for saturation,
BUCHANAN,
caustic
2,
a mixture
soda in the
grams
F)'s- 4
16
desired
proportions
is
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
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).
It is
is
17
not normal.
the reaction,
refer
to
fact
in
Chloracetic acid
C2
in the ratio
Na OH;
formation of sodium
the
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
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
decreasing
irhich
We
it
concentration
to
see
and which
"is
certain
limit
(0.13),
after
accordingly,
kt
const,
was
remains constant.
cular reaction,
is
numbers which
18
is
sufficiently
This
may be
concentration
called
the gaseous
concentration,
- 0.023.
viz
temperature and pressure in the gaseous condition
of
a
series
of
This experimental result was the origin
experi:
concentration
0.04984);
Time
in minutes,
t
they
in a very
were
weak
carried
solution
out with
19
in the
centration.
IV.
We may
tial
now go
more
for
equations
complicated cases.
to the mutual action of n mole-
reaction
we have
cules,
^=
where
k,
C 1? C 2
d
.
(V
Cn
.C n
When
the
which they
the
are
^=
kn
concentrations
.
C,
the
C2
.C n
of the substances
bodies are
reacting
take part in
etc.;
t is
the time.
reaction,
the
equations
may
be
had
in
dC
where C
is
Integrating this,
we
find
C
in
which
the
value
of
is
(n
+
1)
constant,
it
would be interesting if it were possible to realise the different cases which follow from this equation, that is if it were
It
3),
or quadri- (n
= 4),
molecular reaction.
It
1
is
is
not
difficult
supposed to be constant.
which represent
20
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
Researches
H =
as
that the
This
mechanism
is
mono-
is
or
all
cases
bi molecular,
rarely trimolecular.
position
phosphorus
(or
takes place
arsenic)
hydride
as if
were monomolecular,
it
PH = P
Ha
4-
be bimolecular.
to
be
will
slow
oxidation
under
may,
stances,
course,
Fig.
described below,
of
phosphine
circum-
certain
6.
molecular reaction.
He
may
the
Phil.
Zeit. phys.
Mag,
(1)
(2)
P
P
(3)
(5).
H +
H +
3
4-
= H
=
=
P
P2
2
H P
+ H
3
2
21
OXIDATION OF PHOSPHINE.
in the ordinary
By means
(3) could
studied;
Oxidation
The
is
to
principal condition
be excluded;
to
phosphorous acid.
which must be
is
oxidation
can
only in this
The
flask
c closed;
instantaneous
be
way
e is
with
or
the
p;
pipette
the tap b
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
mm.
The
39
stationary during these 65 admissions
of gas,
0.7
full
in the flask.
flask
solid
and
22
crystalline
the
gave
of
reactions
phosphorous
acid,
to the change
points therefore
Everything
and
63
at
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
is
explosion.
The
one;
reaction accompanying
(fig.
PH
+
+
+
1
1
1
1
1
is
experiment
quantitative
already described
it
6)
quite different
carried
in
the
apparatus
+ 1+ 1+ 1-
1
1
1
indicates
an
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
entering
the
at 281/4
mm.
left
flask,
manometer unchanged
Formation of metaphosphorous
acid.
PH 3 +
= H
+ HP0 2
the
compound
HP0
2,
the
23
OXIDATION OF PHOSPHINE.
formation
which
of
is
of
place
brown
a yellow or
it
in
when
25
action
is
mm.
/2
are suitable.
with
the
25i-'2
mm.;
pump, and
air
too violent,
the air
filled
pump
The manometer
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
air
in
anticipated.
The
flask
feathery
had
crystals
phosphorous
70,
In
H P0
3
in the
acid;
at
which
were
at
once
seen
to
glittering,
differ
80. (H 3 P0 3
from
melts at
17).
addition,
characteristic
coating
solidified entirely,
of phosphorous acid,
HP0 + H
2
- H P0
3
24
The change
The question
ivhich occurs
as to
still
11.89
remained to be answered.
6.69 cc. of oxygen were mixed
phosphine and
eudiometer and
of
cc.
6.2
cc.
5.69
6.69
2.59
4.1
cc.
2:3.
we
processes
= JB P0 ....
PH + 3
PH f O = HP0 + H
2
and
That the
latter
(a)
(ft)
is
part
left
at
50.
residue of 196
unchanged, 70
mm,
mm.
Therefore,
177
42
135
PH
3,
and 361
196
165
The volume
is
25
mm.
PH
mm.
65
the ratio
This
and
quantities
2,
obtain
in
2:3.
result
oxidation
mm.
95
we
of hydrogen,
with
well
very
agrees
takes
the
that the
hypothesis
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.
;
therefore
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
many
are interesting
C 2N 2
whilst
in
the
CO +
2,
second
is
oxidised to
carbon dioxide.
We
reaction represented
by the equation
C 2N 2
= N +
2
C0 2
The
trimolecular
acquainted will be
reactions
more
with
which
small.
we
are
at
At present
present
it
may
SECOND PART.
DISTURBING ACTIONS.
Chapter
I.
I.
It
is
in
place
is
subject
are
so
resolves
reaction
disturbing
effects.
manifold,
itself
For
to
that
a
great
extent
into
that
of
the
lack
are
phenomena, because in
the influences under consideration are very little felt and
easily
much
up
in
place
eliminated,
greater
whilst
difficulties
the
study
in this respect
of the
gases presents
later.
If
reaction
is
27
of irregularity
influence of the
It
that
evident
is
this
if
influence
exist,
really
data
the
of the reaction.
which
that
cluded;
is
therefore, really
exists.
medium on
the
of
influence
nature
the
af
medium
they
were
not
in a
in
homogeneous condition
to
medium
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
reaction in a
way
The following
differing entirely
from a contact
observations, against
Berichte
9,
action.
512
et seq.
1,
209, 1887.
28
be
cannot
tioned
medium
to
action of the
the
establish
alone:
BERTHELOT
(1)
seem
raised,
gram molecule
of
was transformed
it
JO
(2)
of experiments,
solvents
molecules of alcohol.
made by MENSCHUTKIN
series
way
100
in 4 hours at
that
the
influence
the
of
velocity
chemical
reactions
in
very
different degrees.
iodide
in hexane, the
for
may
which
is
therefore
taking
also
in
part
is
itself
liquid bodies
an unfavourable
medium.
An
excess
of
for
aniline
way
example retards
35 percent!
Ms changed by
9Q
^y
.
,,
L.
MEYER
<
>
1^1
own
action on
molecules of aniline
155.
drawn attention
has
its
to
the
fact
that
the
by excess of benzene.
Along
researches
1
2
3
4
5
with
these
of LANDOLT
the
CONTACT ACTION.
it
there
of
is
little
probability
29
is
which
To
stitution
an
who
those
alteration
in
will
it
The
of a
velocity
small
reaction
the
displacements;
is
slow
very
much
course
of
affected
by such
monomolecular
the
other in
such a
way
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
arrangement
in space,
connexion
In
(turpentine)
of the
that
them
with
the
experiments
which
he
has recently
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
the
On
exists,
that
is,
that the
Zeit. phys.
Chem.
I,
627
et seq.
1887;
fi.
41
et seq.
1890.
30
II.
many
is
influenced by pressure
made on
is
proved by
the subject.
REISER
atmospheres,
whilst
at
'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
The
it
is
in liquid
VAN
'T
cinic acid,
HOFF
also
when
found that
in the
dissolved in water,
is
transformed at
100,
is
in-
in
some recent experiments by RONTGEN 5 may be menwhich the influence of pressure on the rate at which
RONTGEN concludes
by pressure.
He
is,
that
the
rate
of inversion
is
diminished
GROTH'S
Amsterdam, 1883.
2
Bulletins de 1'Academie royal de Belgique, [2] vols. 45 and 49. Berichte 15. 595, 1882.
98, 1892.
1862.
For
from
the
if
his
in
be calculated
it
different
is
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
at
The
the
by RONTGEN
differences observed
under
version
errors
the
in
different
are
pressures
magnitude,
measurable
with
occur
of
acceleration
weak
the
*.
reaction
should
however
2
,
as in
the external
pressure
exerts
very
Chapter
II.
I.
bare
in
it
is
fairly
the
simplicity,
material
studies
in
it
is
When
this
number of
its
the
and to lay
See
See
TAMMANN,
TAMMANN,
work
originally
researches,
Zeit.
pliys.
Zeit. phys.
by
other
32
with
less
the
of the
requirements
deduced above.
This
on the
ation of milk
sugar
become innumerable.
The
position
however,
is,
different
quite
when we
turn to
arsine
(BODENSTEIN).
the
On
HOFF,
which
disturbances
greatly
'T
affect
of the medium,
The
of
oxidation
of
rate
phosphorus
is
affected
in a
PH 3
of
Viooo
1
,
in air is prevented
2 S,
/ 50
by mixing the
x
of ether vapour,
or
/45o
1
/uu
of
of
turpentine vapour
According
to
3,
GRAHAM,
188182;
Phil.
Mag.
5,
The
literature
1894. (Trans.)
p.
of
623.
this
subject
is
given
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
,
It is in place,
the
of
presence
aqueous
rate of decomposition of
THAN
to
'
aqueous
may
vapour
ammonia
at
the
also diminished
is
by
it.
may be
Similar results
was diminished
to the extent of
3
)
PRINGSHEIM
Zeit. phys.
BAKER
Cbem.
12, 329,
unfortunately
EWAN'S experiments on
p.
does
/iooo
10
'/iooo
7
,
of hydrogen,
Viooo of oxygen,
60.2
of chlorine.
have further
1893.
not
mention
the
pressure
POGG. Ann. 100, 499, 501, 502, 1857. Also OSTWALD'S Klassiker der
schaften,
No. 34.
See
68.
exact.
Wissen-
p. 81.
WIED. Ann.
Manchester
OWENS
College Researches, 1.
623.
34
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
.
reaction
HOFF
no
has
case
is
ammonium
simultaneous
though
formation
ammonium
of
carbonate
on
experiments
Special
this point
have shown
equation
NH
by
.HC0 3
C0 2
NH + H
-f
0,
volatilising
first
place
velocity,
C0 2 +
NH = NH
3
.COOHN,,
NH .COONH + H
4
Fig.
7.
The
servations
and the
figure
on
the
retarding
apparatus
acceleration
effect
7.
Ibid.
1894, 617.
of
= NH
which
was
produced
alcohol
.HC0 3
used
by
vapour
+ NH3
in
aqueous
is
the
ob-
vapour
represented in
The
35
side tube
blowpipe.
carbamate
the
with which
it
allowed to begin,
may be
maintained constant.
This
into
is
whenever
it
is
or B.
reaction
in
been properly
filled,
Both
warmed
in an air
bath so as to decompose
When
them
The
rate
in
is
is
evident.
The retarding
a
similar
way,
influence
while
air
was established
of alcohol vapour
had no
effect
even
when
in
present in
Since
reaction
the
is
existence
proved experimentally
in
of a
it
is
we have
deduced.
This
is
the case
36
also,
'T
1.
2.
3.
into water.
4.
water.
1.
Polymerisation of formaldehyde.
we know
that
is
gaseous
very probably C 3 H 6 3
This reaction was investigated as
.
interest,
it is
of special
(fig.
8) consists of a
large
Fig. 8.
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
it
is
placed in position in
is maintained con-
the volume
3
.
Time.
37
38
vessel
(fig.
to
of a cylin-
B was
attached.
it
the
cooled
The
liquid acid
receiver J,
is
(fig.
which
by means of which
may
Fig. 10.
10).
be
with the
its
contents
communication
put
in
air
pump.
The
air still
filling,
blowpipe and
The following
Time.
the
is
39
FOKMATION OF WATER.
electrolytic
The transformation
its
of electrolytic
was therefore
simplicity,
carefully studied.
resembled
large thermometer
it
was
filled
electrolytic
by means of
Fig. 11.
the
gas
burette
gas.
By means
this
way
(fig.
11)
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
of
C being
left
is
filled
closed,
now
it
is
the
of
part
tween C and B.
the
is
then opened so as
\
Fig. 12.
of
suitable
fig.
12).
mercury shutting
off a
column of
air
The tube
The bath
in
(fig.
is
visible at C,
13) consists
Two windows
1877, p. 76.
40
The quantity
in a PERROT'S gas
l
.
known
interval of time,
was
deter-
Fig. 13.
The length
parts.
of the column of
on the
scale
versely
proportional
which
The
Time
shown
air,
all its
measured
in the figure.
2
.
in hours.
L, was then
in the
41
FORMATION OF WATER.
The
4.
of
results
this
electrolytic
A\
the same
filled in
were made
in
in figure 14,
is
alterations
the reservoir
way
as formerly
of a
mer-
cury.
This
tion
from
transferred
lowering F),
tained in
While
to
C,
dry
sulphuric
acid
with
contact
in order to
(by
it
by
con-
Fig.
which
will be
whole
of the
later) the
gaseous mixture
contained in A, and the tap D
is
is
closed.
When
The quantity
mined by means of
volume
The
1
its
pressure
at
is
then deter-
2
.
from coining in
when the
means of
the cathetometer.
42
Time
in hours.
43
II.
Formation
of cyamelide
of phosphine.
the
Since
deviations
from
the
normal
course
of change in
It
to prove
this
the
when we
is
satisfied
are
dealing
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
addition
to the
more
1.
2.
1.
of
cyamelide
l
On
this
the
walls
*.
ac-tio.i,
see
NAUMANN,
44
The
divisions
and
6:1.
By
heating
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.
the
takes
reaction
place
two
at
entirely
divisions.
188.4 mm.
146. 8
in A.
"157
B.
Fig. 15.
1.33
The
fore
2.
and B,
:
1.
much
is
there-
the greater.
This
is
some
a matter which
is
action.
worthy
example when a
on
them.
deposited
Although observations of
NAUMANN,
this kind
was
it
still
be
thought to
45
order
in
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.
a.
The
influence
which
of cyamelide,
is
was
stu-
died
in the
and
vessels
The following
results
were obtained
49.5 mm.
Initial pressure
(44.5 mm.
.
A
1
The
b.
is
in
32.4
A.
B.
and B,
3.42.
therefore rather
The
Older experiments.
it
as
it
proceeded.
The
Initial pressure
when
.........
997.7 mm.
for
...........
when
having
been
filled afresh,
used for
with electro-
filled
980
3.5
,,
gave:
Initial pressure
mm.
801.1
448
Decrease
for
per hour
The
the
20 hours 788.8
of pressure
....
0.6
.,
walls,
The
vessel A,
used
along
with
second,
new
vessel
of
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
pressure in
them-;
was
vessels,
and
the blowpipe.
The two
vessels
were heated
in the
same way,
in
two PERROT'S
They
47
were
immersed
in
the
vapour
to cool,
and immersed
in
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
of the
course
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
The
final
experiments
were
was found that the normal course of the reaction could not be
realised.
The
Number
of the experiment
Bulb
of the electro-
II
27.83
III
IV
28.2 53.71
63.29
1.
26.41
2.
ly tic gas
From
the
combined \
these results,
most
carefully
cleaned glass
surfaces
is,
that even
possess irregularities
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
49
numbers show:
as the following
Etched bulbs
l
]
The exclusion
of
glass surfaces
was
33.8
2.
51.1
Glass
also unsuccessful.
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
the
of
action
heated
but that the results are completely irregular in this respect also.
Bulb previously heated
for
to 518
New
bulb
24 81
22
24
26
28 hours,
c.
the
course
of
gaseous phosphine at
1
from
Totally
light.
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
to 82.3.
50
recently
the
observed
velocity
the
effects
of the reaction.
of the
surface
of the vessels on
New
Time
in hours.
vessel
1
.
results.
(Tem-
the
the
reaction,
There
number of
however,
are,
increases
latter
is
51
facts
increases.
true.
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
In
cotton wool.
an
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
forte
et
en
le
rarefiant.
1'air
ou de 1'oxigene
1'eprouvette
opere
20
il
se produit tout-a-coup
1'eprouvette."
DUMAS
phosphine
PH
to 1
similar.
He
1
says:
127. 1832.
1
Phil. Trans.
1817, 49.
See also
52
a flash of light
when admitted
be made by an excellent
To
of Nairn's construction."
pump
Arsenic,
similar
be added.
may
oxidise, according to
JOUBERT \
sufficiently dilute.
is
and
way,
to BERTHELOT, nickel
according
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.
and the
tap,
C,
opened.
The volume
of the mixture
The observation
firmed in
this
way,
phenomenon
The investigation could not however be begun,
Fig. 17.
of
ments
of
the
mercury which
is
in
contact
mixture.
These sur
la
1.
is
so sensitive
53
such
to
great
movements,
that
attended with
is
difficulties.
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
is
until they
fill
the whole
are
now
closed,
The
containing the globule of mercury.
reason of this may possibly be found in
local
dilutions
by
given below.)
In order to avoid this cause of combustion,
viscid
solution
of
calcium
chloride
in
Fig. 18.
is
it
expansion
than
that
which gave
rise
ijr
to the ex-
ture
may
is
produced,
in the
J.
D. VAN DE STADT
made
a careful
pressure
and
the gas
was
in
After
filling
the apparatus,
it
was
heated to 50
in a
Initial pressure.
1.
2.64
cc.
h.
9.
55
That the
2.
is
explosion
viz.
3),
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
com-
50,
so
Some calcium
first
series.
50,
at
All
left to
chloride
the
solution
pressures
itself at
in hours.
4.
1.99 cc.
as in the
Time
PH
3,
and 1.03
cc.
2.
56
No.
Time
in hours.
6.
1.44
cc.
2.
The determination of
extremely
difficult,
this
limit
as
is,
57
if
it
both
which
the
gases
were
introduced
through
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
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)
0.54
over
drying
cc.
0.95
soda-lime
cc.
PH
The upper
Volume
the
limit of pressure
was
0.11 atmosphere.
also found to be
0.1 atmo.
lower
gases.
limit
of
VAN
cc.
'T
The explosive
of phosphine,
and 0.5
cc.
at
which a mixture of
58
The
explosion
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
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
The
that
fact
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.
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
'T
days.
VAN
as
the
as
had elapsed.
substances H P0 2 and
As soon
as
the
hygroscopic
at first
H P0
3
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.
50.
VAN
'T
1
-'
See
p.
to
the
33.
p.
20.
Fig. 20.
60
to
not
fill
shown
The
taps
F and
The
the figure.
and
mark near
F was
then
filled
Gr,
disconnected.
brought into
which had previously been
filled
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.
is
at this
ceases to be luminous in
oxygen gas,
rises
62
cool
by
water bath in
water
of
current
The
of the
made
water,
meter,
follows:
as
bottle,
then
phosphorus
area of
its
at
repeated
is
very
surface
may
acted
of time.
Since
the
on during an experiment,
the
intervals
suitable
little
table.
it,
kx
is
where p
is
Pt
and
is
the time.
The values of
the
that
kj
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
........ =
air.
,,
phosphorus
(cf.
p.
52).
,,
=
=
20. 2
--
20. 4
17.8 mm.
0.113
mm
1
.
Time
in
minutes
t.
63
dp
lo
(2)
-Pi
order to
calculate
the
values
of k,
integrated.
we have p
quantity,
a.
""
P-a
12
Pl
we
series,
24
(2),
obtain
t,
The
Pi
values
means of
of
in the table on
values of ki
we may
there-
of oxidation of phosphorus
in moist air is really
portional
to
pro-
the pressure of
the oxygen.
for
it is
oxidation
does
Fig. 21.
b.
By means
1
not
oxygen
well
known that
of
phosphorus
take
place
in
at higher pressures.
of the apparatus
With phosphorus p x
is
shown
in the
accompanying drawing,
now made
were
measurements
at
all
pressures
65
at
which the
oxidation occurs.
The
glass vessel
EPA,
70
cc.,
C was made,
at
junction
with mercury,
or
tubing.
the
at
same height
so
that
the tube
in
the
mercury always
D;
apparatus
be
could
read
naphthalene
and the vapour of the bromon the course of the reaction. The
more accurately,
had no
efiect
acid,
and washing
it.
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
five times.
it
is
apparatus.
'the pressure
had
0,
been
is
when
it
occurred even at
mm.
Phil.
See
the
Mag.
(5),
complete
tables
given
in
the
Zeit. pliys.
Chcm. 16
p.
321, 1895, or
66
of the oxygen
but
not
723 mm.
at
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.,
that JOUBERT,
21,
under pres-
who has
published
5/0
(375
two
series of
luminosity
is first
visible.
The
curve,
(fig.
22),
illustrates
the
connexion
between the
the
as
of the
those
ordinates,
I,
mean
20), and
dt
as abscissae.
oxygen
Curve
shows that
with the
the
In curve
the oxygen.
of
pressure
taken
oxidation
of
rate
67
value
pressure
falls,
considerable
range
the
velocity
at
then
of pressure
(viz.,
first
very rapidly as
limits over a
narrow
between
varies
500100
from
mm.), and
Curve
II
represents
pressure
of
the
of
volatilisation
the
phosphorus
dp
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
This
at
is
higher
value
520 mm.;
700 mm.
at
exists
to a pressure of about
of
rate
of phosphorus
oxidation
in moist
dp
-IT
tp log
dt
Above
with
the
certain
2.
much more
Phosphorus
data
Phil.
from
in the
wLich
the
p.
is
'
Pl
ceases to be true,
this
temperature
pressure
limiting
the reaction
slowly.
in
dried oxygen.
The
experi-
is
drawn
68
except
in
21).
(fig.
Two
was
in contact
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
of oxidation
is
(fig.
23),
Setting out from the pressure of 200 mm., the velocity of the
reaction
without
appears
to increase
reaching
continuously
maximum
value
as
the
case
when
the
Fig. 23.
is
constant.
It is
ob-
tained
the
values
however,
that
the
rate
of
oxidation between
and 70
We
may
therefore write:
(3)
mm.
is
oxygen.
OXIDATION OF SULPHUR.
After
we
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
rate
it
is
oxidised by dry
This
mm., above
It is
70
the deposition of a
latter.
from
they decrease.
on the
that,
say,
this equation
irregularity
probably
by means of
calculated
experiments,
mm.,
is
of Iq
is
only
true
(at
20) up
to a pressure of
6070
maximum
velocity of oxidation
at
SULPHUR.
II.
As we have
the
surface
of
study
of
the
takes place
the
rate
phosphorus
phosphorus pentoxide on
introduces
is
The
process
is
volatile.
The apparatus shown in figure 24 was used in these experiments by means of it the pressure may be kept constant during
;
the
other
about
160
6 grams of soda-lime.
is
maintained
constant temperature of
by
is
graduated in Vm
cc.,
and contains
70
mercury the
reservoir
ing
B.
level
of which
a three
is
bromnaphthalene
may
way
tap,
a small
to be
made equal
bottle F.
may
Fig. 24.
The
is in
of
The diminution
standard
pressure,
then
proportional
when reduced
to
to
some
reaction.
When
is
reduced,
further readings
The following
In
Av
it
At
tap
is
71
made
new
at the
pressure.
diminution
the
of the
the
rate
of
dt
pressure
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
while k
by the formula
calculated
is
As the
table
shows,
the
experimental
results
are in
much
than
pressure,
is
put
with
10
WO
200
C)OO
8OO
Pressure.
Fig. 25.
The curves
in
rate of oxidation
Curve
fig.
25
I is
dt
of the
as
pressure
blance
to
oxygen,
that
It
and those
23);
(fig.
abscissae
as ordinates,
in
both
cases,
Curve II
roots
of
is
the
73
OXIDATION OF ALDEHYDE.
by
figure
The
dv-
at
log
Jr
pi
circles.
mation.
It
of interest
is
corresponds
the
to
oxygen between
part
and 70 mm.
Whether
maximum
velocity
as
further experiments.
ALDEHYDE.
III.
or
to
It
appears,
however,
from
the
of
this
result,
experiments
aldehyde-vapour.
The
at
reaction
20.
It
was found
to
at
the
acetic
acid
of
Compare
fig.
23 on page 68.
14, p. 41.
74
The
kept
60
takes
oxidation
at
70
place
in
bulb
the
The
cc.
is
its
volume
is
determined by means of
or
lowering the tube C, the
raising
BCD. By
the manometer
which
26),
(fig.
is
the
of
level
always brought
before a reading
The
mark
is
made.
pressure,
measured
be
is
mercury
to the
on
vertical
CD
of a cathetometer.
is
mercury
serves
the air-trap
retain
to
which
bubbles
any
air
may
leak
glass
By means
of the three-way
tap
pump through
Fig. 26.
F,
or with a
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
by
G
and
is
then removed,
current
through
F H.
reaction
is
of oxygen,
The tap
is
ended.
the
is
fre-
The
OXIDATION OF ALDEHYDE.
requires
in
75
As soon
as
therefore,
very
dilute
solution
of caustic potash
used in
was allowed
to flow into
volume
water
into
of
- -
it,
the
apparatus
The
difference
between the
determined by weighing
it
full
of
drawn
in the residue.
The following
Time
in
Time
in
OXIDATION OF ALDEHYDE.
order
In
of
quantities
is
it
change,
to
from
calculate,
the
decrease
of
the
pressure,
and
Let
the
77
initial
is
of
pressure
that of
elapsed,
mm.
mm.
2x
with
of
At
aldehyde.
first
the
acetic
formed
acid
vapour and
form
to
volume of
PO
The pressure
t
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
+ N,
so that
2 x
After
its
If
acetic
t.
its
maximum
pressure,
and
time
P,
we assume
acid
pressure
that
follows
of the aldehyde, p 2
acetic acid.
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
which
is
acid,
acid
the
assumption
the
Putting
total
equal
pressure
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
the
equation x
may be obtained
this
we
to
small.
is
the
in
known.
is
the
oxygen
The
analysis
of the
by
and the
oxygen,
partial
trations
of
oxidation
-j
P!
which
pressures,
is
of aldehyde
concentrations of the gases - - or
rate
p2
kpi
(A)
a
P2
dpi
'-
kl (x
-r^)
Pl
dT
This gives
dx
V,
IT
from which we obtain,
x)
after
2 x
kl
(x
nffl
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
is
0.
when
(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
" X) +
1
t"
(b
C nSt
6 are calculated
that,
in
up
to an
by
oxygen
results.
much
As
may
be seen from
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
As we have already
molecular reaction
about 450
of mercury at
20.
may be
_^l
mm.
expressed as follows,
k Cl
(D)
(C)
80
where
and
numbers
the
are
the
of
molecules
99,
p.
we have
-r
later,
be calculated from
may
-~
proportional to
(page 78). GI
dt
(it
C2
It
Comparing
with equation
this
m =
1,
is
propor-
we
dpi
obtain
kp2 Pl
we
and n
'
find
1/2,
is
is,
C 2 EU
The
of
to the reaction
this
Applying
exists
kinds
shown
unknown.
they are
that
be
measurements
Making
different
It will
C2
normally
in
knowledge of the
oxygen
gas,
in
is
H4
way
2.
subject.
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
at a sufficiently
would,
atoms.
Equilibrium
molecules will be established
when
where
C( 02
is
)
the
Phil.
This
Mag.
is
(5),
C<o),
concentration
on the temperature
2
.
Since
atoms
such a
way
atoms
oxygen
its
is
will be smaller
however,
will,
81
probably
C (02
We
take
may
the
concentration
).
is
of the pressure.
we assume
If
of
oxidation
the
the
aldehyde,
rate of oxidation
must also be
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
= P
P4 +
The
'.
proportional
the
concentration
of the
would then be
This
oxygen atoms.
view
is
also in
is
such as
The
PA,
are formed.
the
that
J.
J.
oxidation
THOMSON
electrodes)
is
has
passes
is
found
that
much more
the
easily
through
the
2
3
for
the
The
work
existence
of
82
of
oxidation
phosphorus,
not
only
oxygen but
moist
in
also,
We
part
far,
is
here
question, however,
with atoms,
view
received
or with ions,
VAN
on
'T
HOFF
the subject,
one
slow
the
in
The
arises
that
so
have,
in
oxidation,
while
formation of ozone.
E WAN'S
From
oxidation
is
proportional
the oxygen,
molecule
is
previous to
If
we
experiments,
it
if
that
kind
rate
of
oxygen
it
exists
it.
of
2 0,
the
the
the oxidisable
one
show
and
which
it
is
conceivable that
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
may
the
potassium iodide.
They therefore, resemble the cloudiness which
was observed by R. v. HELMHOLTZ in electrified steam. 4
Chem.
Zeit. phys.
The meaning
way
is
explained later.
83
We
not ozone,
is
because
it
stops
it;
it
might
in
to
was
first
determined,
it
compare
2
,
and LEEDS
results.
SCHONBEIN'S
in
determinations,
in
of indigo,
dilute solution
way:
following
so as to allow of quantitative
large
either
small
flask together
stick
of
with a very
as indigo sulphate, or as
com-
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
diameter
by
drawing
it
up while melted
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,
4,
247.
until
the
84
was brought
solution
indigo
acquired in the
to the
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
mgrs.
1-H =6.66
unchanged.
dark so as
final series of
avoid
to
the
experiments was
possible
oxidation
now made
of indigo
by the
and the
of the light.
action
in the
slow combustion
way, because
different
took place
escence
is
in
two
first
it
was seen
different stages.
seen;
product formed in
phosphoric
this
stage
in the
is
when such
practically
small
the only
of
quantities
water,
after
this
50,
the
On
repeating
10
0;009S7
cc.
of this
1.11
indigo
solution
mgrs. oxygen.
required
14.1
cc.
permanganate, or 14.1
85
on
decolourised;
were
indigo
the
in
standing
cold
an
additional
cc.
of
gradually decolourised,
disappeared.
50
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
it
condition,
phosphoric acid
and
thus
is
of indigo
cc.
The
2.83 mgrs.
is
oxidised,
the
0.00987
It
decolourising 44
in
that
so
solution,
is
difference
0.5
acid;
it
is
first
perhaps
amount of
larger
It
of
oxidation
directions,
also
may
possible
active oxygen.
be
phosphorus, ozone
luminous phenomena just
present
the
in
oxidation
of
atmosphere
the
sufficient quantity,
since
described
of
the
on opening the
with the
air.
may
be
due
to
the electric
is
account of
That the
its
conductivity.
effect of
the shaking,
viz.,
8b
by
proved
not
the
fact
that
when phosphorus,
seen
and water
air,
alone
are
is
used,
without indigo.
It
also
is
to
be
noticed
the
that
inhibitory
JOUBERT
may be
disappears
very
explained.
Chapter
III.
METHODS
FORM AND
USE
OF A SOLVENT.
The
Disturbing actions.
The
The
1.
2.
influence of the
effect of a
the reaction.
The
The
3.
of changes in
occurring during the reaction.
4.
influence
See note
p.
the
walls
of
the
apparatus
52.
Soc. Journ.
THEIR ELIMINATION.
Methods of eliminating
1.
Form and
2.
Use of a
3.
will
Form and
which
action
Any
87
evidently
be
is
diminished
in
intensity
by diminishing the
by increasing
volume.
By
using
flasks
spherical
and the
effect
which the
Use of a solvent.
2.
is
gaseous system
of change,
course
We
may
be a gas
when
a reaction in a
under consideration.
is
First,
its
by
we
use
obtain
the
dilution
which
is
often
of the
reaction
is
of the solvent.
Further,
special
experiments
although
Since
the
disturbing
systems,
the
effect
actions
are
systems.
In
order
to
prove
88
is
and
can be determined
when
when
1,
2,
1
the acid
it
alone present,
is
is
air.
....
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.
.
From
numbers
these
it
which the
difference
the addition of
In order to
the
in
1.1
1.
will
that
and B:
is,
velocities is due,
diminished by
is
air.
show that
which the
ivalls
of the
shown
in fig. 7,
page 34.
After
was determined,
1,
2,
1.
when
when
air.
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.
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
3.
77.4 in A, 79.4 in B.
Initial pressure
Here,
the
also,
velocities
the
is,
influence
is
layer of
of a protecting
it
influence
the
walls
the
by
with them.
Moistening the walls.
3.
This
the
diminishes
artifice
influence
formed
are
it
we
certain
in
shall
The walls
case.
of
one
for example,
The
of
manipulation
the
an enormous difference
the two
The
owing
divisions,
velocity in B,
greater
than
that
it
experiment
is
is
the
same
as
that
in
A,
both
with
the
walls
diminishes
the
accelerative
the pores
liquid.
influence
of the
The reason
of this
deposits of
is
probably
by the
90
must
It
the
must be
also
of
choice
viscid,
the
whether
arises,
it
is
which have
it
is
necessary to differentiate
and those taking place
in liquids,
in gaseous systems.
In
liquid
certainly
But
the
in
the
systems,
to
suffice
practically
As we
The
is
it
in several cases.
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
rable
in
conditions
the
than
with
be
avoided
will
be
we may remark
that
it is
to
shown
in
very conside-
liquid
are
gases.
URECH
while
*,
invert sugar,
a curious
he
used,
the
first
observed,
larities
way when
in
were
which have
cyanic acid,
1
91
oxide.
This
who
experiment
should
serve
a warning to investigators
as
whenever a deposit of a
solid
is formed,
the difficulties to be expected are such that
even under the favourable conditions existing in liquids, considerable irregularities may be found.
reaction
II.
Chemical induction.
The
first
chemical
An
dynamics.
frequently
encountered
in
exceedingly
viz. the
it,
is
of special interest in
curious
phenomenon
velocity
of the reaction
and
',
is
maximum
is
value.
"initial acceleration"
views which have been put forward in this book, it was submitted
to experimental examination. This showed that the cause of the
phenomenon
is
to be
of this kind.
The
existence
of an
by the
following observations.
1.
is
due,
mixture
observed
of
the
chlorine
acceleration
and
hydrogen
in
to
"
chemical induction"
question
light.
on
In
exposing a
one of their
92
experiments
was
They observed
on tartaric
with
being excluded,
the
to
regard
in
phenomenon
the
in
general
follow-
ing way:
"The
acid, light
occurrence of such
depend, not
some
on
maximum
appears, therefore, to
BAEYEE
affinity itself."
in
working
3.
of certain
same pheno-
metallic oxides
"In
all
be
to
almost
is
an accelerating
rate
maximum
until
rate
is
it
so slight
as
goes on
at
attained,
when
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
dans
les
POGG.
premiers instants."
Ann.
100,
488, 1857.
OSTW AID'S
34, p. 93.
2
(3) 66,
26, 1862.
p.
93.
93
INITIAL ACCELERATION.
More
recently
made
MENSCHUTKIN
We
PEAN
and
which BERTHELOT
etherification
observed."
the
phenomenon of
initial
change.
given
consequence,
it
having
an
initial acceleration
action,
and
Mn0
the
acceleration
which
enters
into
the
is
2,
first.
Berichte,
two stages
2
It is
also
exhibits
the
was
this
SPRING on
15,
2512,
1882.
KONOWALOW,
Phil. Trans.
1866, 201.
Chem.
1,
Zeit.
phys.
217, 1887;
Chem.
1,
1,
63, 1887.
468, 1887.
See
94
NAUMANN
secondary
a mixture of ammonia and carbon dioxide into
;
mate he
ammonium carbamate
of the solid
URECH
formed.
"These
point of view,
if
then
for
AUBEL
maximum
the
results
substitution,
carba-
it
finally,
ammonium
must occur
velocity
at the
1 '
of
the
in
another,
upon
zinc (con-
initial
to a chemical change, or
acceleration
whether
it
is
in order to dis-
something essential
merely a result of
is
secondary actions.
1.
initial acceleration
sulphur.
T. L. REICHER
5
,
the
large
quantity
thermometer
(fig.
27)
the
bulb
contains a
of rhombic sulphur together with sufficient sulfill the bulb and part of the
capillary
tube,
the
Berichte,
Zeit. phys.
8,
4
5
QUOTE'S
was
539, 1875.
Chem.
1,
217, 1887.
1,
465, 1887.
Zeitschrift
Amsterdam 1883,
whole
45.
fur Krystallographie,
8,
593, 1884.
Inaugural Dissertation,
95
INITIAL ACCELERATION.
temperature being at an
rise of
The expansions,
as follows
1, 2, 4, 5,
The
8,
maximum
its
which were
value
first,
reaching
known
well
which
influence
the
of
presence
monosymmetric
formation of water.
2.
into
figure
index
and
hydrogen,
electrolytic
duced
the
apparatus
represented
in
12,
mixture
of
being examined.
and
oxygen
at the time
undergone change
46.5 (L t
and
is
the
beginning
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
air,
L, at the
t.
Therefore
1
2.28
1.28.
-Lit
There
is
acetate studied
2
remarkable
similarity
by MENSCIIUTKIN.
Berichte,
96
The
Time
in hours.
INITIAL ACCELERATION.
The cause
97
which
was found
in the
is
since
it
conditioned
may
be
by
the
produced
is
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
to time.
Time
in hours.
acid
(at
98
DISTURBING ACTIONS IN
GASEOUS SYSTEMS.
actions,
ary
and therefore
the
described
may
be referred to second-
phenomenon may be
of service
way which
is
APPLICATIONS.
DETERMINATION OF THE NUMBER OF MOLECULES
WHICH TAKE PART IN A CHEMICAL REACTION.
I.
METHOD
A.
IN
The
in
which
in
the
this
which
difference
different
is
In
the
first
part of
The
principle on
for the
course
of
reaction
is
very simple,
is
represented by
in the reaction,
polymolecular
the equation
^
dt
where n
the
is
-kC
The
given will
be used,
lg
1
The value
Cf. p. 19.
of k
viz
~7T
is
(n
or
1)
rt a
times
-i
kt
that which
it
constant,
100
and we
shall
IN A
REACTION.
The decomposition
We
this
of phosphine
have
has
to
PH =
t GH
P*
2,
that
is
their
of hydrogen.
pressure, at con-
volume,
decomposition.
We
have then
where
and
and
the
=
P
same
are
Co (3
pressure
and concentration
initially,
Ct
The
the
on
p.
2,
The following
Time
in
hours.
The steady
increase of the
numbers given
101
in the last
column
to the
quadri-molecular equation
^rJ
kfc
const.
-f-
is
equation
On
H = P +
po
log
3~p^~-
t"
pT
From
is
this result
we
monomolecular, that
is,
PH = P +
3
3H,
and
II.
METHOD
of
on
the
volume,
investigation
that
which
IN
which has
of the
is
about
influence of a change of
102
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
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
initial
changes of concentration
disturbances
to
which the
again,
result is
of
the
still
we
substitute
inaccurate, since
reaction,
-Y-,
we assume
at
undergoes a considerable diminution. This error is partially eliminated owing to the fact that the same assumption is made
with
respect
ever, difficult to
say to
what extent
and dC 2
this occurs.
It is
it
is,
how-
much better
According to
what
is
it
said
possible to
is
from which,
calculate n exactly.
l
molecular reaction,
d C
am
indebted to Mr. A. A.
different form.
[E. COHEN].
No YES
/>,
somewhat
103
after integration,
or,
kt
....
'
H- const.
(1)
By making two
iCa and iC e
it a
and
it e ,
values
into
equation
and
2ta
2 te ,
we
obtain, introducing
(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
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/
(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
k in this equation
is
(n
1)
it
is
104
We
IN
A REACTION.
greater certainty.
The method described in the preceding section becomes valueless
for example, in those
in cases in which disturbing actions occur
;
which
cases,
observed,
frequently
in
be too small.
These
may be
influences
is
variable.
is
them
mono-molecular reaction
is
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
is
the
reaction
appears to be
method, a more careful investigation by means of
shows it to be bimolecular. A similar result was
peroxide
first
that
example,
is
less noticeable.
obtained
Zeit.
phys.
Chem.
18,
118, 1895.
means of the
105
l
by
The
first
method
with
was
volume
variable
used
also
in
the
investigation of:
1.
2.
3.
chloride. (NOYES.)
1.
The formation
which make
the
it
These
volume.
constant
partial
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
cannot
A,
bromine by
lose
evaporation.
solu-
acid,
of the small
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
106
quantity
ments
is
Time
The
of thiosulphate employed.
contained in the following table.
in minutes,
t.
IN A REACTION.
result
of the experi-
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
it
as bimolecular.
2.
We
are
thus
are
met with
be
to
formed.
is
difficulties
which
in liquid systems;
deal
the
in
much more
It
is
for
acid,
this
difficulty
becomes very
this
of
cyamelide
formed
extending,
with
with
acid
cyanic
the
five
variable
in the
formation of
subject
intervals,
method
cyanic
serious.
molecules
of
of
case
may
volume,
been pointed out, has to be improved, in this case, by the realisation of a special condition.
This
consists
in
comparing
the
velocities
of
the
reaction,
The
initial velocities
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.
The
velocities
ratus used
No.
is
A REACTION.
IN
described.
is
same
first
as in
b.
Comparison of
The
the
109
in perfectly
clean vessels.
initial velocities
the
way
When
(Experiment
1,
I.
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
by a
layer of cyamelide.
ment
2,
I.)
Fig. 29.
entered
it
acid, after
In
another
of this
experiment
29
through
equally
restored.
The
and
finally
mean
2.9.
the
original condition
was
values of the
first
110
c.
Comparison of
in
fig.
A REACTION.
IN
same apparatus,
same as in b.
was used
the
Both
in this case.
half
of
velocity in
again measured.
n obtained was
in
4,
II.)
The value of
2.8.
(Experiment
air
dry
repeated,
one case,
added to the
being
cyanic
the walls of the vessel (Experiment 5), in another the further
precaution was taken of keeping the temperature constant by
2.9 and n
This apparatus
ties in clean
then
vessels,
in
From
3
it
is
this
in
way
The
initial velo-
A, (Experiment
7,
(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
the equation
3CNOH =
All
doubt
would be removed,
on the subject
CsNaOgHg.
effect of
if it
3.
The
ferric
which
chloride
has
were not
occurs
been
between
carefully
action
may
be.
ferric chloride.
stannous
investigated
chloride
recently
and
by
A.
NOTES \
A.
taking part in
Ill
number of molecules
in
it.
According
should be trimolecular.
+ SnCl 2
2 FeCl 3
it
to the equation
2 FeCl 2
SnCl 4
memoir
referred to will
on
103
p.
may
considering.
500
800
was placed
stannous
of
solution
cc.
chloride
From
shaken.
thorougly
time
to
time
portions
of the liquid
were
at
stopped;
the time
at
was noted.
The
ferrous
salt
solution
the
t.
Zeit phys.
Chem.
16,
546, 1895.
is
memoir.
The concentration of
this solution
and
112
I.
Ca
0.1
IN
A REACTION.
113
RECOGNITION OF MIXTURES.
III.
A
is
by
it
whether a
substance
in a mixture of
is
---kC
dt
changes
take
a mixture,
is
two
equations
and
_ L?
mixture,
that
it
dc --kc
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
IN
A REACTION.
was
easily
The following
where
to increase
titre
had
reaction
was
titre
the
is
115
from
to T! and
reckoned
proceeded,
for the
Tj.
we
After eliminating x
find,
2 T!
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
k may be obtained.
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
fully described
6.
It will,
therefore,
to
sufficient
9. 4.
k
Sodium hydroxide
2.370
Potassium
2.298
Calcium
2.285
Strontium
2.204
Barium
2.144
(2),
116
The
influence
The
Temp.
k.
Ester.
3.493
Methyl acetate
Ethyl
2.307
........
Propyl
1.920
1.618
Isobutyl
Isoamyl
1.645
,,
Temp.
3.204
Ethyl acetate
propionate
2.816
butyrate
1.702
,,
isobutyrate
,,
isovalerate
it
is
0.614
0.830
therefore,
appears,
in the molecule of
is
1.731
.......
benzoate
It
14. 4.
k
Ester.
,,
9. 4.
number
of atoms
hydrolysed.
b.
The
lished
methyl
catalytic action of
OSTWALD'S
by
it
acetate,
classical
appeared
researches
on
the
hydrolysis of
in the
1/2
litre,
were
filled
with
N/io hydrochloric
ature of which was
maintained
constant
at
WARDER
Zeit. phys.
found 3.240.
Chem.
13,
561, 1894.
25.
In order to
117
of the glass, the flasks were previously filled with strong* hydrochloric acid and allowed to stand for several days. That the
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,
N/ 10 baryta
in
solution;
this
way
50
Since
cc.
way.
At
suitable
this
in order to avoid
among
number
capacity,
50
intervals
were
removed and
purpose;
from the
flasks
cc.
of
cc.
titrated.
the
Two
first
of acid
excess
is
titrated with
by
N/ 20
baryta solution.
The
velocity constant
is
After
we
integration
obtain
k
where C
is
log
The degree
its
Compare
pp. 2
of
and
purity
3.
of
the
ester
118
concentration
the
culated
from
the
known,
and,
therefore,
k can be
cal-
hydrolysis which
the
is
in
this
case requires
a rather prolonged
time.
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
when 60
The following
Time.
may be
small
119
obtained
of hydrolysis
by
DE
HEMPTINNE
as the
by
Table
Ester.
A.
25.
120
Table
Ester.
B.
acid.
25.
121
Ester.
when
any other
acid
We
employ here
shall
be
will
Application of thermodynamics.
later
given
formula the
the
in
chapter
strict
dealing
proof of which
with
chemical
equilibrium.
as
concrete
we may
example,
it
represent
in the
following way,
N
We
directions,
^=
N0
2.
namely
N0
2,
and 2
N0 = N
2
It
be
which we
will call
proved,
values of kx and k 2
4.
first,
may
in opposite
d log k i
d log k 2
dT
dT
"
q
'
2T 2
is
The proof
of this equation
f
is
123
APPLICATION OF THERMODYNAMICS.
kgrms.) of the
first
it
seeking,
this relationship
=
A
where
we put
If
and
A =
we
0,
(2)(VAN'THOFF)
obtain
B ......
(3) (BEETHELOT).
equation
was proposed
on
are constants.
-jjTjT^
This
B.
etherification.
As
be
will
shown
later,
in
0,
and
consequently
d log k
By
integration of (4)
we
log k =:
So
This
~f~
that q
constant.
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
quantity
is
however,
is,
^
-
is
erature to
we have assumed
far,
erature.
equation
obtain
d log k
Chem.
+ BT
--
Zeit.
Appendix, note
Inaugural Dissertation, Amsterdam 1893. Zeit. phys. Chem. 12, 155, 1893.
phys.
4,
226, 1889.
3.
124
From
log k
If
we
this equation,
=
in
log
equation
(5),
we
....
^-,
-|-
we put
obtain by integration,
constant.
obtain
(6)
or after integration
log k
Equation (4),
ment with the
p.
= B
log
which
123,
T +
in
constant.
cases
many
is
in
observations
on the velocity of a
reaction.
that if
change
equation
(4)
k!
log K
2
= AA
T!
T2
,
J-l
-^2
ki
log
We
see
from
this,
k7
and on
10
TTT;
which
increase
in
Proc.
Roy.
Soc.
58,
112,
1895.
D. M. KOOY,
loc. cit.
and
a..
at the temperatures
Tj and
T.2 ,
12S
APPLICATION OF THERMODYNAMICS.
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
Reaction.
126
*,
of plants. The quantities of carbon dioxide expired in equal intervals of time increase rapidly when the temperature rises between
and
25. A
Above 25
is
rise of
and
smaller,
50
above
it
to
approximates
that which
is
With regard
the
to
temperatures, KooyV
between 310
at temperatures
and 512
The following
= A
10
=-=-.
J-l
i2
for
differences
310_367,
367
of
temperature
446, 446
512,
of
of
magnitude
as
10,
in
the intervals
10
it
the
is
is 1.2,
number 2.92
Decomposition of phosphine.
Temperatures.
127
Experimental treatment of
b.
The
what
1.
been
has
the subject.
studied
number of
in
Influence
cases
follows.
in
>
dibromsuccinic acid.
Since
acid
it
decomposes
100
at
in
aqueous
C,
Br 2
C4
Br
+ H
Br,
it
reactions
the
dioxide,
formed
by the secondary
removed before making
the
(fig.
30)
The tubes
titre.
brought,
kind of exsiccator containing a pice of caustic
being
vacuum
for
24 hours.
The following
allowed
to
remain
in
the
partial
table
contains
and at
different
temperatures.
Special
way without
experiments
loss of
had
shown
hvdrobromic
acid.
that
may
be removed in this
128
75
EXPERIMENTAL TREATMENT.
129
Puttmj
A =
we
0,
0.0412, and
273,
obtain
log k
2.
= 0.0412
6.02219.
and
caustic soda.
Temperature.
130
solution.
EXPERIMENTAL TREATMENT.
The
results obtained
were as follows.
131
132
5.
between potassium
chlorate
in presence of
sulphuric acid.
This
0.5637
reaction
grams
chlorate,
The progress
of the oxidation
was followed by
titrating 10 cc.
Temperature.
The
results
EXPERIMENTAL TREATMENT.
6.
133
We
shall
reference
has already
Temper-
been made.
The
WARDER
to
which
134
10.
of
and phosphorus.
so far considered
have
fairly
of arsenic
much
200
as
velocity
at temperatures as
apart.
Arsenic hydride.
The apparatus
used,
are
made,
wide range.
a.
were
the
were determined
the
walls
of the
the velocity
vessel
may have
a considerable influence on
heating.
By
changed very
taking
little,
The following
these
all
it
was
and
by avoiding prolonged
Temperature.
135
EXPERIMENTAL TREATMENT.
b.
Phosphine.
310
(anthraquinone), 446
(diphenylamine), 367
(sulphide of phosphorus).
512
The
as those with
the
hydride,
same way
in the
(sulphur) ; and
calculated
d log
"
T2
dT
not satisfactory.
this case the
is
'
In
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
ESSON
gives
fairly
page 124.)
The formula
correct
results,
as
of HARCOURT and
the
following
SECOND PART.
One
THE TEMPERATURE OF
IGNITION.
of
the
conclusions
arrived
at
in
further
requires
The
to
which
considerations
are
directed,
of
been
ignition
sudden occurrence at a
exceptions
to
this
led
to
influence
phenomenon
its
this
which have
experiments
by
attention
that
conclusion
The
out of
change,
the
be
to
appears
to
this respect.
indicate,
however,
continuity.
L.
MEYER
expresses himself
as
temperature
of ignition,
"
might be
called,
in
general,
There
have
is
here
distinct
contradiction
of
the
views which
been
velocity
of
sudden
any
suppose
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 proof
three
we
inflammation
By
phenomenon.
shall
:-
The
The
2.
more or
reaction occurs
less rapidly
erature of ignition.
The
3.
The
reaction
is
of
necessity
the
first
facts
by
rather
of the
truth
by
equally
it
considering
The
following,
The
detail.
the
are
then,
observations
which appear
to
drogen
and
more
in
*,
RAUM
\V.
formation
of
water
is
so
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
On
heating
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
following
percentages
of the electrolytic
at
100,
0.4,
1.3.
138
been observed
The same
the
temperature of ignition.
is
place more or
at temperatures
less slowly
determine ignition or explosion.
The
phenomenon
To prove
this,
of
susceptible
and suppose
(fig.
may occur.
suppose we have
substance which
is
not
chemical
its
On removing
31).
rig. 31.
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
ance to a combustion.
by a phosphorescence which
is
139
OT and the
is
distances along
it
will call /\
during the
first
moments
of
its
progress.
air.
of
kind
the
described,
but
wave
especially
at
will
Fig. 32.
We
of
the
far
as
will
now
substance which
The matter
is
simple, so
140
is
concerned;
than
rapidly
ated; this
it
is
chemical
change
have in addition to
which diminishes
the
tends
to
increase
now produce
another
by the
A T w^
is
it
it,
we
the case,
being
A T,
we
to diminish /\
This
propag-
When
it ;
which tends
action
is
31.
in fig.
which increases
this influence,
T2A2
it
however,
occurs,
more
will fall
to
owing
before,
erature between
wave
of the hot
temperature
rises.
initial
its
T2A2
line
at
temperature
(fig.
still
is
by the
represented
32).
initial
higher
temperature,
T 3 would
.
rise to
give
hot
rise
can
is
only
those
the whole
of
this
unchanged;
which gives
The temperature T 2
of the substance.
rise to a
therefore,
would
It
be
not
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.,
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
words there
is
is
definite
pressure
at
which
141
different
pressure
of
the
velocity
JOUBERT
value which
Temp.
the
is
oxygen
given.
was diminished
to
the
corresponding
142
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
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.
yields results
which form
Since,
mics
experimental
frequently
the
difficulties
much
smaller than
in
is
the
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
An
1
,,
HOMOGENEOUS SYSTEMS.
a.
In
,,
may
example of the
in
be gaseous,
first
of these
liquid,
is
or solid.
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
homogeneous
solid system.
144
has
CHEMICAL EQUILIBRIUM.
been
already
of
mentioned,
the
of
dissociation
peroxide
nitrogen
NA
The following
^=
N0
2.
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
to be regarded
is
velocity
in
directions,
opposite
permits
us
to
so
that,
in
when
attained.
is
N,0,
NO,,
at
GI and
C2
kjCj,
and
respectively,
in
the
units
-~
k2C 2
at
of the systems
and
N0
been employed
rip
and
at
<
at
d =
k2C 2
or in general,
~>
"
Page
4.
is
the same.
145
where
r\i
in
each of the
be noticed,
to
is
from
it
the equation
dC
dt
which
also
is
same
is
The
restriction,
derived equation
and where
this
restriction
is
in
used
in
The
investigation
concentrations
of
the
of
the
equili-
brium constant.
We
If,
have thus,
for example,
velocity
of one
Iq
BERTHELOT
and
an
acid
is
convertible
much
ester
into
as possible,
what part of
it
with a given
by treating
quantity of an alcohol.
1
-'
Also
(2),
Ann.
(3),
VAN
Chim.
'T
Phys.
19,
05,
69
et seq.
3S5,
1879.
1*02;
(3),
146
CHEMICAL EQUILIBRIUM.
The
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)
l&i
'
constants.
Or,
kl (1
When
of
the
ki
e ) (a
e)
k2e
(e
w)
(I)
different
equilibrium
"limiting
(their
may
equation
of the mixture
/3
experiment gives
/3 ,
is
for a
and
w =
(l-
k,
2
/ 3)
(!-'/)
k2
That
is,
0.
we
get,
V/8,
or
it
g-
[4 (a
Since
+ 1) +
V 16 (a
a 4- 1)
+ 8 w (a +
1)
+w
were made with mixtures of acid and alcohol without the addition
of water,
we must put w
e
a/3
(a
- V
a*
a -f~T)
and find
ISOTHERMAL EQUILIBRIUM
The following
of alcohol used
HOMOGENEOUS SYSTEMS.
one molecule of
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,
is
is
pre-
true for
b.
Application of Thermodynamics.
The
is
d log
q
ITr*
dT
where
system
This
the
is
when
evolved
is
*,
absolute temperature,
equation,
which
at constant volume.
first
homogeneous and
is
in gases
heterogeneous equilibrium
be obtained in the following
way
for
may
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
H. VAN
239, 1885.
operations
volume of an
by unity
is
where P
whole
'T
HOFF,
S VCD ska
Lois
Vet.
de
Akad.
i'equilibre
Handlingar,
21,
dans
1885;
1'etat
gazeus on
Xecrland. 20,
dilue,
Archiv.
149
INFLUENCE OF TEMPERATURE.
absorbed when
Is
the
into
When
second
obtained
the
external
so that
from the
cals,
we
n!
is
formed
(viz.
(viz.
-^==
\dV/ T
mav
also
total
\dv/ T
obtain
dv/ T -\dv/ T
If
converted
viz.
is
system
be
first
molecules
of the
"
VdiVv
dr
....(1)
first
PV
[>!
x)
m +
(n 2
(1
n2
x] RT.
(2)
Therefore
P
_
-; [
- -
nO
R
]
and
f**\
/dx\
(1),
we obtain
/dx\
T-'R
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
n2
nj
we
d log
/dx\
VdT/v
dT
"
d log
Jq
This
equation
likewise
applies
(3),
it
_q_i
"
RT 2
dT
obtain
becomes
T2
to
equilibrium, for equations (2) and (4) apply equally well in this
case
when
ules
the
the
equation
of
ation
the
"
~Vrp
makes no
~o~rm"
in.
in.
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.
This
entropy by
formula
has
also
VAN DEVENTER,
Zeit.
Phys. Chem.
2,
1888.
of the
INFLUENCE OF TEMPERATURE.
d log
151
dT
An
equilibrium
or
elevation
We
of
depression
therefore
ibrium
is
this
obtain
has no
effect
by
rule:
trill
As examples
may be mentioned
The equilibrium of
1.
CH 3 COOH
C 2 H 5 OH
C2 H3
:j=
C2 H 5
0.
220
reached
is
the limit
2.
is
no heat,
when
is
it
the
by
At 10
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
evolution
two
systems;
its
value
should be zero at
1700.
:!
4
r>
isc,heu
bei
Gasen. II.
p.
HORSTMANN
33.
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
The value of
b.
In this case
is
zero.
and by means
of the equation
d log
K
"
ciT
it
2T 2
the equilibrium,
of
from observations
As an example
of this
we
NA
The
quantities
which occur
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
to calculate q.
peroxide,
1
2
7,
at
pressure,
at
density of nitrogen
different temperatures.
120, 1891.
Zeit. phys.
3
.
Chcm.
INFLUENCE OF TEMPERATURE.
The
fraction
which
of the peroxide
153
exists as
2N0
is
ob-
compared with
air,
~~
3.179
where 3.179
and
is
is
d log
"
~~df~
2T-
KI and
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?)
the
temperatures
obtain
xl
and
T2
in equation (1),
154
CHEMICAL EQUILIBRIUM.
The following
table
T.
155
156
CHEMICAL EQUILIBRIUM.
one
with
hand,
exist
its
products
in
the
solid
gas
or
substances,
that
so
NH
the
S or CaC 2
existing as
in
ated vapour,
and the
exists here
or
gaseous,
is
governed
--
cllogK
hold
in
good
referring,
however,
We
in
not
that
must, therefore,
displaced
the
value
by a
of
and
way
as
Cases investigated.
As an example of a calculation of
dissociation of ammonium sulphide,
NH S
5
NH
^=
The value
this kind,
4-
2
:
K7
q
2
2 S,
log
we
/I
IT,
1\
a >'
157
For
this purpose,
we put
rij
\\ e
have,
C2
2,
the
further,
maximum vapour
and n 2
K =
and, therefore,
0,
pressure
concentration C 2
its
^
where
(C 2 )
and
temperatures
(C 2 ) 2
are
T2
and
T!
(C 2 ),
the
experimentally by
&
concentrations at
pressures.
log
-^
log
~, we
obtain
Pi-
/ 1
T (^
1
.
the absolute
"\
TJ-),
158
CHEMICAL EQUILIBRIUM.
by FROWEIN
studied
ered here.
we may apply
to
this
case,
n 2 =.
1, and, therefore,
That
which
the
aqueous vapour,
C2
so
that ni
in
0,
is,
is
is
therefore,
and
md
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
expression
is.
~.
dT
1
Zeit. phys.
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
the
is
which
heat
is
159
HETEROGENEOUS SYSTEMS.
IN
EQUILIBRIUM
evolved
The quantity
qK
is
By
which
of heat
7^
^w
qs
dT
is
the
and the
we
from
log
~-
determined calorimetrically,
is
ratio
(1),
we
obtain
qw
2T 2
vapour pressure
both at T.
salt
Calling this F,
obtain
d log
qK
"
2T*
~~dT~
where q K
is
<
Assuming that
vals
of
is
qK
we
temperature,
obtain by integration
F2
The apparatus,
a terisimeter,
the
pressures
loyed in determining
salts
vapour
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.
B.
been
closed
before
the
121, 1887.
160
CHEMICAL EQUILIBRIUM.
the
finally sealed at
24
hours
in
crystallisation
the
c.
vertical
may
measurements
be
of
position,
equally
pressure
left
to itself for
in
water of
distributed
are
Two
The following
table
Temperature.
contains the
results of the
experiments
161
THOMSEN'S
direct
determination gives
qK
3410
cals.
from which
it
may
Salt examined.
The
162
CHEMICAL EQUILIBRIUM.
heats
of
solution
of CuCl 2
KC1
calories.
pressures
in detail.
CuCl 2 2KC1.
Temperature.
a mixture of
163
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
from
its
Here,
is
reformed
components.
again,
qK
may
be
calculated
from
the
dissociation
of a tensimeter
(fig.
36)
Temperature.
H 0,
2
164
CHEMICAL EQUILIBRIUM.
The behaviour
iso tropic.
127,
the
crystals
becoming doubly-refractive. On
still
further
be
obtained
in
good
fairly
crystals
On
ordinary
temperature.
formed, at about 87
We
is
latter
may be
represented thus,
NH N0
4
The
rhombohedric
^=
the
below 120
temperature
possessing
NH N0
4
phenomenon
the equilibrium
regular.
is
that,
on cooling
transition point,
The kind
l
GROTH'S
When
of
properties
equilibrium
expression
just
"transition
is
the
is
described
1,
point",
may be
106, 1877.
or
"transition temperature"
considered later.
expected to
is
is
always meant.
used,
The
The
cases
be proved,
may
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
separate
out
The laws of
ibrium.
out
separates
shall
which
in the solution
corresponding to saturation,
the concentrations of
to
Owing
substance
is,
definitely
fixed
all
after
last
the
all
further
these
cannot increase
evaporation
it,
and
it
to
solid state.
From
in
this
equivalent
it
quantities,
whole
the
to
system
which the
last
not
equivalent
quantities
substances
to
The coexistence
is,
used,
this
of both
are
VAN
'T
again
HOFI- and
the
condition
VAN DEVENTER,
Zeit.
of
affairs
phys.
Chem.
described above; by
I
164, 1887.
166
CHEMICAL EQUILIBRIUM.
and
remains constant,
less
with
of
condition
by
possible,
that
this
in
solution,
be
will
it
substance
of the
the
there
substances
or
raising
concentration
approach
of
equilibrium
saturation
point,
and
it
is,
therefore, conceivable
At
is
and
temperature,
at
it
only,
is
the separation of
the
all
where
(C 2
(C,
is
(Ci.
.)
first
Calling c 2 and
Cx
system.
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
The temperature T
is
it
167
is
at this
temperature
When we
out
K < M,
for
substances
c-2
and
the
CJL
for
only
we may
in equation (1),
.,
occurred,
having
and C L
.,
.
first
one
except
C2
values of
K > M,
have
^> M
replace
the
all
except one, by
this unreplaced
concentration,
cannot
separate
out
for
<M
the
through
this point.
Cases investigated.
The examples
of the
may
The
The
a.
b.
transition temperature of
transition
temperature
bodies.
polymorphous
of
salts
water of
containing
crystallisation.
d.
decomp-
osition.
e.
omena
and
that
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
bodies.
been investig-
detail later
the subject
case
simple
polymorphous
is
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
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
and
equilibrium,
below
it
LEHMANN'S observations on the changes of the different crystalmodifications of ammonium nitrate into each other have
line
b.
salts containing
water
of crystallisation.
salts containing
Phenomena
out
salts
hydride
chloroform
acid
5
,
4
,
6
.
It is well
erature
in
is
transition
GROTH'S
Zeitschrift
fiir
Krystallographie
8,
593. 1884.
Inaugural Dissertation,
Amsterdam, 1883.
2
3
4
5
6
7
Na 2 S0 4 IGHoO
which
and
HOFF
Na 2 S0 4
;*-
169
DOIT.LE SALTS.
10H 2 0,
-f-
DE VENTER,
'T
VAN
where
34, of ZnS0 4 .7H 2
Na
and
of
2 HP04.12H 2 0,
40,
about
the
salt
in the formation
of double
which
at
converted into
is
37.
at about
c.
of water of crystallisation
molecules
seven
containing
the
about
and decomposition
salts.
The formation
1.
The equilibrium
Na a S0 4 10H
.
and
the
salt
is
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.
finely
after
time
short
temperatures below
in
order
E.
E.
E.
to
prevent
COHEN and
21. 5,
of
loss
D. M. Kooi.i,
Zeit.
COHEN
loc.
:!
A. E.
VAN
phys.
561,
Chem.
1882,
14,
71, 1894.
cit.
BATH,
'T
17.
if it
Xcit. phys.
Cliem.
18,
180, 1895.
Zeit.
See
phys. Clunu.
p.
1,
203.
170, 1887.
Cf.
170
CHEMICAL EQUILIBRIUM.
21. 5
above
however,
astrakanite
formed
is
is
more
time.
of two
do
sulphates to
with
the
NH
C4H4
NaNH
transition
HOFF
and VAN
.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,
to VAN
powdered
in the proportion
is
6H 2 0.
according
which
and
prepared by SCACCHI.
dextro-
to
(NaNHAH
temperature
"
to
we have
while here
ammonium
sodium
of
C 4 H40 G .4H 2 0,
2(NaNH 4 C
The
we were
form a double
combination
laevo-tartrates,
to
later.
2.
'T
or
if
readily,
sooner
27,
the
some time
and
The formation
that
to
of
potassium
of the sodium
ammonium
salt.
The
transition tempera-
Rendi
conti di
Napoli,
3
4
Aufl.
1865,
1894,
p.
p.
Zeit.
VAN
'T
34.
also Zeit. pliys.
Chem.
17, 47,
1895.
4EJ 2 0)
^L (C H
4
K Na. 3H
0,
at
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
'T
(Na
0) 2
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-
ammonium racemates
30, and
at
also in
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.
similar
ammonium
4) 2
'T
+ [(NH
6) 2
6 )] 2
6) 2
+ 16H
2 0.
+ 12H 0.
2
the
sometimes
salts
he thought
it
sometimes in the
REICHER
showed that
this is the
case,
Zeit. phys.
Zeit. phys.
'
MI._,0
Zeit. phys.
Chem.
Chem.
Chem.
The composition
221, 1887.
is
investigated
by RUDOUFF
(,11,0.,) ,.011,0.
an equilibrium ocurring
CuCa(C 2 H jO.>)j.
:
172
CHEMICAL EQUILIBRIUM.
Cu Ca (C 2 H 3
2) 4
^= Cu (C 2 H 3
2) 2 .
of
and
astrakanite
2) 2 .
-f-
The formation
Ca (C 2 H 3
-f-
of
which we have already considered, occurs on raising the tempwhile in this case the double salt
erature,
than about
temperatures lower
at
77,
erature
into
change
its
decomposition
transition from one system
that
the
double
tetragonal
takes
components
the other
to
salt
is
is
is
accompanied by a
due to the facts
is
while the
blue,
The
place.
metric
monosym-
needle-shaped
5.
J.
CuCl 2
by
salt
different
2H 2 0, which
2KC1.
crystallises
in
formed from
is
it
its
2H 2
CuCl 2 2KC1.
.
This case
is
constituents.
CuCl 2 KC1
^=
-f-
KC1 -h 2H 2 0.
CuCl 2
The
salts
1
2 KC1. 2
researches
-+-
of
CuCl 2 2
.
J.
^=
2 CuCl 2
4
Chem.
3,
336, 1889;
5,
-f-
4 H,0.
KC1
MgS0 4
i.
e.
schoenite,
97, 1890.
Zeit. phys.
Inaugural Dissertation, Amsterdam, 1893. Zeit. phys. Chem. 12, 416, 1893.
Chem.
7,
173
DOUBLE DECOMPOSITION.
K Mg(S0
2
4) 2 .
6H 2 0,
d.
in
cases of double
decomposition.
*
SCHIFF
and
of
this
supposition
which occurs
is
is
correct,
+ 2KC1
Na 2 S0 4 10H 2
.
^=
the
0,
3. 7.
ammonium
chloride
an
erature of which
The
e.
is
10. 8.
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
succeeded
after
'
:>
:>
who
at a
at
my
disposal
174
CHEMICAL EQUILIBRIUM.
temperature
125
of
for
six
hours,
under
pressure of two
was
place
the
175,
product
is
consists of well
ure
produced.
baryta solution,
reddened when
it
titration
with
sufficient
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.
could
not
3.
The
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
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
UNIVE1
175
may fail
to take
stable system.
It is,
especially
place,
in
the
absence
of
the
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
saturated
The
solution,
when placed
in contact
of sodium sulphate
may
Glaubers
with
Na 2 S0 4
salt,
or
contained
in
pure anhydride.
these solutions
is
Temp.
The
quantities of
176
are also
CHEMICAL EQUILIBRIUM.
two
above
32. 65,
at
32. 65,
the solution
Temp.
the
the
concentrations
of the
product
a salt and
between
equilibrium
Again,
which
is
ously C cl C Br
,
etc.,
a constant
is
obtain,
etc.
the
calling
k2
saturated solution
ions
we
CMBI-
its
the
of
177
we
all
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
to
is
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
number
each con-
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
existence,
and
approximate
Na 2 S0 4 10H 2
.
4- 2
KC1
^^
results.
12
178
Temp.
CHEMICAL EQUILIBRIUM.
A.
Temperature.
With
falling temperature.
179
180
Temperature.
CHEMICAL EQUILIBRIUM.
181
Electrical methods.
S.
Electrical
2.
Electrical
phases.
method with
stable phases.
Each of
its
these
application
and examples of
general methods
which
after
given,
some
less
a.
majority
of
cases,
the
that,
in
substances present
by
accomp-
is
constant, a
of
The
for
specific
example
is
volume
1/2.07,
of
rhombic sulphur
2
,
that of monosymmetric
monosymmetric sulphur
is
accompanied by
an expansion.
The dilatometer
(fig.
27,
p.
94),
which
is
the
thermometer.
The bulb
which
is
to be examined,
W. SCHWAKZ,
is
See also
CHEMICAL EQUILIBRIUM.
182
and
pump,
such as
then
or mercury,
petroleum,
be observed on a paper scale which
oil,
can
latter
filled
is
glued to the
capillary tube.
35 may be used in
fig.
in
cases
The
in
reservoir
diameter,
is
diameter,
70
In
to
order
is
sealed
is
then introduced at
the
excess
of
it
convenient
to
oil
remaining
at
is
/',
The
escapes
through the
in the apparatus,
In order to
air
poured out,
which
is
The height of
easily regulated.
the
oil is
read on a
The
observations
are
in a
thermostat
successive
alteration
in
oil in
may
is
be
temperature
been found advisable in
of the
system which
is
all
has therefore
commencement of the
reaction
is
in this
avoided.
little
way
183
By
much more
rapidly,
it
below the
is
is
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
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
this
tube
is
that
constant,
practically
is,
the
The
dilatometric
chemical
the
is
reaction
95
6.
in
in all cases in
which
is
is
it
For example,
mixture
stances
with
(Na S0 4
2
10
are
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
.
4H
0)
all
heat,
is
The occurrence
time.
the
maximum
the
of
4 atmos.
often reversed.
95. 6. T. E.
WIEDEMANN, WiED. Ann.
it
was
at
E.
BAKHUJS ROOZEBOOM.
sign 100
is
H 2O
are dissolved in
'
100 mols.
Zeit.
4
phys.
chem.
2,
515, 1888.
of water.
ROOZEBOOM
MgS0 4 and
uses the
2.9 mols. Na 2 S0 4
185
THERMOMETRIC METHOD.
wide
in a
thermometer, and
The following
K Mg(S0
2
4) 2 .
+ H
:^
K S0 4 +
2
Falling temperature.
Time
t.
MgSO,.
0.
186
CHEMICAL EQUILIBRIUM.
which we
conclude
may
this temperature.
c.
^~ (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,
it
d.
W.
MEYERHOFFER
temperature
become
the
the
identical
of
pointed
of
that
at
the
transition
the
solutions
in
out
We
also the
two
the
temperature.
if all
has
and
solubilities,
solutions
were to be represented
of the temperature, the curves would
graphically
as
functions
proof
will
now be
We
solubility.
already
convertible
have
mutually
Determination of
Bull. Soc.
Zeit. phys.
ature,
the
VAPOUR PRESSURE.
187
(p.
175).
The numbers
results of
are molecules
Temperature.
188
CHEMICAL EQUILIBRIUM.
millimetre
scale
read without
saturated
sulphate
allows
solutions
have
the
been
of
Glauber's
Temperature.
salt
determined
The vapour
by E. COHEN,
2
pressures of
the results
are
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
its
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
ot 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
be
it,
as
way
amount
dissolved
pressure
it
would
the
in
effloresce
air;
maximum
if
a sufficiently large
water
will
mined the
water
In
latter
only,
amyl alcohol
using
order
to
concentration
cooling
it
until
concentration
of
it
corresponding
to
the
temperature
at
which the
turbidity appeared.
flask
"
2
;!
also
way:
Losungateusion"
preferable
in the following
to the
more
is
generally
" solution
pressure",
translated
strictly equivalent
term
''
which
is
perhaps
T. E.
solution tension".
2,
190
CHEMICAL EQUILIBRIUM.
warmed
was
number
0.5,
that
so
degree
they
may
be affected by a
accuracy which
of
maximum
error of
is
purpose.
The following
Amyl
is
alcohol
Water
0.769
^
(j w
amyl alcohol
Concentration.
8.72
15
9.14
25
9.67
32
10.00
36
10.20
t,
0.05 (168
between
If the temperature at
and calculate
and
40.
t).
6.
at different temperatures.
Temperature.
in
cent.
solutions of water in
To
Ga
Gw
8-72 per
^~rT
(j
-f-
The following
=
=
it is
only necessary
c.
is
inconveniently
From
40).
now appears
the
initial
191
SOLUTION PRESSURE.
concentration
of the solution
is
easily
8.591
30,
= 0.05
Cl
+ 30) =
(168
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
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
The
is
way
anhydrous
flask
with
its
viously
the
of the
concentration
in the
1
for
way
described.
become
identical
at
the
water
contained in
dissolves
transition
is
was determined
little
temperature,
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
192
The following
CHEMICAL EQUILIBRIUM.
table contains the results of the experiments.
TJNI
Temperature.
ELECTRICAL METHODS.
193
194
CHEMICAL EQUILIBRIUM.
combination
the
following
described,
direction
of the current
is
the
ZnS0 4 -solution,
Zn.
>
concentrated
Concentration
differ
for
the
cells
S0 4
example,
electrodes are
with this
more
dilute solution.
We
know
then,
first,
temperatures
at
equal
current
above
or
below
the
transition
point,
become
that
From
these
facts
it
is
concentration
77iermomcfer
Zn
Sealing
.S"
Glass tube
current
As an example, the
ZnS0 4
H2
195
ELECTRICAL METHODS.
ZnS0 4
+ H
will be taken.
made may be
are
which
sulphate,
few
'
finely
is
water,
in this
been
has
of
drops
the vessels
cell
placed
in
the
narrower
parts
of
way
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,
i/g
covered
are
cm. of
their,
A small thermometer,
shown
are filled
in order
is
with some
indifferent
to
When
in
such as
salt,
graduated
is
with
lower
which
is
of
is
the
mercury,
sulphate,
with
unpolarisable
must be employed
used.
respect
to
is
made by means
Only
a few
grams of the
salt
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
The form
of
these experiments.
transition
cell
which
may
also be used in
196
The
CHEMICAL EQUILIBRIUM.
transition cell
Unpolar-
is
now
of
ZnSO
0, which
very
slowly
minutes
five
Every
is
now allowed
is
ZnS0
to rise
that
so
this,
of the
occurrence
the
197
ELECTRICAL METHODS.
the
circuit is closed,
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.
is
40j
4l.g
4Zg
US
454
4W
is
47.S
at
then
6M
Fig. 39.
concentrations
temperature;
of
the
at
the
solutions
transition
the
current
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
the
198
CHEMICAL EQUILIBRIUM.
The following
with Glauber's
salt;
the temperature
is
given under
t,
the deflection
means
of
ELECTRICAL METHODS.
199
system.
is
The
cell is
Unpolarisable
electrode.
200
CHEMICAL EQUILIBRIUM.
contains a paste of finely ground Glauber's salt and the same solution.
Conducting
is
provided
Fig. 40.
by
about
Oj-tube
in the
cm.
wide
fille
d with cotton
wood soaked
resistance,
which
is
method.
b,
two J_-shaped
by means of
a small water-
motor,
the
b
so
electrodes
remains
gether
by
r,
that
saturated.
The
wooden frame
at
in
to pieces,
which
also
201
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
'
volt
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.
solution.
202
CHEMICAL EQU1LIBBIUM.
E!
= 16.63
E2
The
10.12
-!-
0.548
0.297
0.00622
h 0.0253
t
t
2
.
2
.
is
33
30Cell
20
JO
20 c
Temperature
Fig. 41.
fl '/>
ru)rm,aL
.0.
203
EQUILIBRIUM.
SECOND PART.
of equilibrium between
two
different systems,
in
matter,
maximum
in the evaporation of
may be
There
may
is,
as
we
water
shall
^n:
see,
water vapour.
classes,
which
are
quite
similar
to
may
be divided into
those
in
2.
3.
in the case
which the
205
HOMOGENEOUS SYSTEMS.
I.
The
such as
N0
2,
the
cause
deviations
from
the
GAY
HETEROGENEOUS SYSTEMS.
NH HS ^=+ NH + H
4
is
2 S,
to be regarded as completely
^zr
Liquid water
Steam.
d
,
from which
where
2T
d log
~r^
^~,
the
From
is
Ca
we
q
obtain,
by
/J_
integration,
l_\
206
EQUILIBRIUM.
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
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
sufficiently well
The
equilibrium, and
may
be represented as follows
Undissolved substance
the solubility
it
is
^z:
dissolved substance.
is,
As
is
well known,
the
may
be
are
the
numbers
of
each
of
the
in the reaction,
different
and
where a x and a 2
kinds of molecules
J.
dissous.
H.
VAN
Also,
'T
HOFF.
Lois
1'etat dilue,
gazeui ou
207
SOLUBILITY.
C2
is
its
^a^ =
saturated solution,
0,
and therefore
is
temperature
1
C
that
at
is,
K,
the
temperature
given
substance has a
soluble
definite solubility.
which represents
we
obtain
cUogC
.
"
dT
_q_
dlogG
"
dT
2T2'
_q "
2iT 2
from
by the separation
the
saturated
of
solution,
solution
is
saturated solution.
This
theoretical
large
quantity
water
(integral
heat
of
solution)
may
differ
copper
chloride
dissolves
it
in
large
quantity
dissolves in its
own
of water
with
saturated solution
between
is
negligible,
for
since
there
is
very
little
difference
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,
1).
of binary
solutions
when
noticed that
e.,
with
become
(2)
identical.
When
change
LE
heat
the
HOFF.
'T
with
CHATELIER
the
of
(ALEXEJEFF
sodium
chloride
calcium
),
The
and
solubilities
sulphate
DEVENTER
(VAN
the
zero
is
temperature.
3
alcohol
solution
(LE
VAN
DE
of
isobutyl-
and of
CHATELIER),
STADT
in
water
when
temperature
Finally
evolved
with
q be
positive,
that
heat
is,
is
absorbed
which
the
if
when
the substance
rising temperature.
is
According
to VAN
maximum
'T
solubility at about
d log C
"
The deduction
of
this
(MARIGNAC).*
relatiouship
2lT 2
dT
1
38
is
to be
'
found in the
Zeit. phys.
Chem.
17,
546, 1895.
2
Compt. rend. 85, 440, 1877, Compt. rend. 100, 50, 1885.
5
Ann. Chim. Phys. (5), 1, 274, 1874.
Chem. Tahellen, 2te Aufl. 238.
6
Loc.
cit.
p.
206.
See also
209
SOLUBILITY.
may
q,
when
the solubilities
By
integration we obtain
and therefore,
log
log
JL
(^
:=
are known.
const.,
2i^- -^
r-
logg
-|-),
...... (3)
temperatures
The following
Substance.
is
calculated
210
EQUILIBRIUM.
It
is
noteworthy
that
gives
binary electrolytes,
LAAR'S
VAN
KC10 3
for
III.
The
CONDENSED SYSTEMS.
which
characterised by the
is
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,
The
which
In the change
one system,
precisely the same thing is found in
temperature
is
solidification.
of the
consider
the
ice.
influence
on the
So
far,
however,
namely
respect,
tered
considerable
obviously
different
between them
There
in
one
among chemical
to
difference
be
equilibria.
found
conditions
of
physical equilibrium
is
in
in a
take part.
Again,
it
is
system
is
found in
its
211
to fusion.
is
reached.
While
perchlor-ethane,
rapidly attained
the
this
is
of hydrated salts
salts
dissociation
may
The same
difference
is
is
also noticeable
change
indeed.
It
is
therefore
necessary,
in
the
experimental
study of the
to take cases of
chemical
change,
for
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
application
facilitated
by
the
diagram
and has
made
it
which
will
now be
is
greatly
described;
this
temperature
of sulphur.
d log
~~dT~~
we
will
take
the
values
of
q
2T2'
as
abscissae.
The
of sulphur
may
Representing
solid
R! R
2,
two
crystalline modifications
equation
d log C r
qr
dT
2T 2
'
213
where q r
vapour
is
in
the
rhombic
without
form,
the
performance
of
external work.
also
Monosymmetric sulphur
reached a certain
maximum
evaporates until
pressure
way
its
the equilibrium
by the curve
vapour has
may
MiM
2,
there
corres
Cm
"
dT
qm
2T
2'
Cm
modifications
pressure
metric
of
of
the
sulphur
rhombic
modification,
are
is
identical
from which
it
214
EQUILIBRIUM.
T rm rhombic
higher than
sulphur in
emits vapour
at
than
pressure
greater
the
monosymmetric
sulphur.
T rm
third
curve
have
been
described
which
is
may now
FiFo
this
be
the
represents
physical equilibrium
exists
it
corres-
qf
"
2T
dT
where Cf
and
sulphur
so
T rf
that
two
transition
temp-
is
scale.
We
to
in the points
point of
no external work
occurs,
opposite
condition,
liquid
C,
eratures.
F XF 2
is
the
to
vapour
sulphur
being done.
The curve
'
is
C corresponds
are
now
in a position to obtain,
to the melting
scale.
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
relation
is
it
possible
to
From
at these temperatures.
T rm
i.
e.,
The
lines,
ABC
triangle
since
follows
the
may
angles
BAG
215
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
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
Tmf
and
T rf
T rm
the different
Tmf
qm
qf
=
is
273
T rf
120,
273
qr
qf
is
According to BERTHELOT,
qm
1
114.5.
qf
qr
1,
qm
0.15
0.04
216
EQUILIBRIUM.
So that we obtain
387.5
5.5
393 2
or
T rm
The
of sulphur
by
273
is
therefore 96
direct experiment as
Experiment and
agreement.
.3.
96.3.
two
crystalline modifications
95. 4.
calculation
EQUILIBRIUM.
FOURTH PART.
equilibrium lead to
Every
equilibrium
different
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)
well
as
the
finally,
of
fact
It
depression
that
if
of the
no system
temperature;
is
ciple
cases
equilibrium"
of equilibrium.
will
now
expresses,
it
equilibrium,
I.
The two
in
this
equilibrium,
are,
on the
solid,
218
EQUILIBRIUM.
on
hand the
other
the
that
which
one,
the
is
the
when
increase
at
lowered
that
that
requires
principle
is
the temperature
is
to say,
b.
As we have already
Cf
an
IK?
hold
good here,
whose
is
is
GI
dlogK
_q_
"2 T
dT
2'
the
being
concentration
in heterogeneous systems.
heat
those
the
it
is
demon-
in
metallic iron,
H +
where
ii!
FeO ^=
Fe,
is
We
will
and n 2
1.
be
which
later
explained
equilibrium.
in
0,
together
with
homogeneous
former
chemical
only
one
of
the
systems
ii 2
n
L
2
Iv
and1
dlogK
r~
and therefore
2
d log C 2
dT
2 T*
219
From
is
C2
this
it
is
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
NH HS
4
is
^=
+ NH
3,
NH HS,
4
is
II.
a.
Fusion and
The
falls.
solid
here.
The
solid,
the
solidification.
quantity
when
of the liquid
evolution of heat
is,
at the expense
fusion absorbs
solidification evolves,
heat.
b.
Incompatible systems.
In
the
principle
physical
is
obvious,
of chemical
equilibria
it
is
the
just
considered the
phenomena
also in complete
of the
known
we
truth
being so well
definite
These equilibria
220
EQUILIBRIUM.
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
fig.
2
it
concentrations
pressure,
abscissae,
subsist
vapour which
by taking the
and
which
43.
modifications of sulphur.
modification
to
which the
It
MI
below
it
that referred to by KI
refer
line
to the
2.
221
that which
is
The
is
MI M 2 and K! K 2
equations,
ations, are
d log C r
dlogC m
q r_
"
dT
T2
'
qm
"
dT
T2
'
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
The
this
results
of
qm
the evolution of
positive, as is required
by the
conclusion.
is
monosymmetric sulphur
ation.
is
is
LEHMANN
nitrate
depressed,
found
undergoes
The researches
likewise
formed
of
is
the
while
different
changes
at
which
ammonium
lend
produced when
1
that
the temperature
falls.
GROTH'S
is
is-
222
EQUILIBRIUM.
III.
two
of
existence
substances
different
is
in cases where,
for
any
In
of
case
CD)
where q
is,
system of concentration
We
may
Cj.
at constant volume.
which q
those in which
it is
When it is positive,
negative.
positive and
is
that
is,
when heat
is
constant of equilibrium
the
erature,
and
therefore
because Ci
invariable.
When
will
GI
C 2 remains
increase
GI,
temp-
the expense of
at
C2
is
constant, the
at
the
expense
depression
of
the
first
of temperature
when
the
temperature
falls.
The equilibrium
N
may
^i
N0
According
known
The
to the principle of
will be
formed at lower
N0
2,
which
is
well
to be the case.
makes
223
possible
is
NH
2N0
^-*r
NH + H S
.HS ^z
more
increase
will
more
and
on the
left
hand
side
at
the
majority
above
observations
absolute
it
zero,
is
about 273
is
made,
is
relatively low,
This
of heat.
view
is
however,
it
of chemistry;
is
is
which as
is
^i
H +
2
2,
shown by DEVILLE
system
when
which
temperature,
oxygen
This
is
allowed to
displacement
owing
the temperature
experiment.
of
is
to occur,
1000. According
is
fall
such
is
the
water,
this is corroborated
that,
at
the
by
ordinary
224
EQUILIBRIUM.
most diverse
chemical
now,
If,
equilibria
temperature, displaced
with evolution of heat,
occur
ichich
towards
it
is
in
actions.
the
systems
must
in the majority of
take
show that
place,
at very
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
calculations,
the
shown
by numerous applications.
is
also
this subject,
in
more
place
here
to
"
is
BERTHELOT
principle of
in
maximum
tends
There
is
both of them
1
261,
1853;
91,
83,
1854;
92,
34, 1854;
(4),
18, 103,
225
heat
While THOMSEN,
recognises
fully
"
Thermochemische Untersuchungen",
the exceptions to his earlier statement which
in his
Mecanique
The
that
it
is
to
exist,
predict
free
the
a great
in
entirely
from
mobile
of
principle
deduction
us
Chimique",
many
cases,
when
that
at
the
The
application
will be
accompanied by
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.
equilibria,
whether physical or
it
By means
is
of
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
we
In a case of homogeneous equilibrium the quantitative expresof the principle of mobile equilibrium is contained in the
sion
equations
C?
....... (I)and!
dlogK
-
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.
Since q
is
becomes
we
log
it
is
problem
result
is
may
when T
==
(II)
which gives
== 0,
S
only
the
system
heat,
will
zero,
in
be
other
NH
present
words
4.
^=
NH
HS, which
is
H-
2 S,
have disap-
peared.
The
brium,
application
viz.
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
evolution
of heat
given
alone
is
is
in
present
with
case
at a
the
Suppose that
monosymmetric
is
C. in
the equilibrium
rhombic sulphur
We
have
then to
^n
monosymmetric sulphur.
that on cooling the system
prove
will
it
pressure,
the
of
centration
the
qr
log Cr
'
dT
Jlr_
2T 2
d log C m
qm
2T 2
'
'
dT
'
and therefore,
__
qr
dT
where q mr
is
--
qm
2T
2'
rhombic sulphur.
symmetric
The conditions which must be
into
system which
is
fulfilled
in
order
that
the
Cr
According
T =
0,
to
the
>
C m and q mr
above
>
differential
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
temperature
to be proved.
From
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
it
which may
a conception
at
is
For example,
point.
systems,
the
such systems
in
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
affinity,
the
or
that
See
p.
172.
is
Nal,
between the
difference
is
zero
at
affinities
which are
at
work
in
230
CHEMICAL AFFINITY.
on passing
changes sign.
affinities,
is,
92. 4,
at
MEASUREMENT OF AFFINITY.
II.
The magnitude of
crystallisation in salts.
We
now
will
MITSCHERLICH
in
taken
1844,
up
What
namely:
is
the magnitude of
the affinity which binds the water of crystallisation in decahydrated sodium sulphate
u If a
crystal of hydrated sodium sulphate be introduced into
the Torricellian
vacuum
at
9,
of
8.72
crystallisation
mm. and
for the
Although the
therefore
the
sodium sulphate
affinity
is
of the water of
equal to a pressure of
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
or,
as
it
might be
between a solution
and water.
This
attraction
cell,
by means of
in the walls
of
Aufl.
565.
p.
4.
231
salt.
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
is
of the experiment,
is
Temperature.
with a
232
CHEMICAL AFFINITY.
taining
is
water,
by a semi-permeable
divided
sure
the
at
prevailing
therefore
being
its
in
two compartments
and
The aqueous
partition.
into
maximum
pres-
temperature,
and
with
the
equilibrium
brium, which
is
Fig 44
re-established
into
semipermeable membrane,
through the
directly
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
to
A may
vapour
in
be
The pressure
is
atmospheres.
The
of the
attraction
rise
D and
two
tities
of
The weight
1 litre of
may be
taken as
kgrm., and
233
We
0.000806
- log S
Sw
::
Sw
be
,
the
we
find,
^ft +
const.
of water at T,
vapour pressure
we have
for
:= 0.
D
common
or. introducing
4.55
|s
0s
log
logarithms,
D =
where S s
kgrms.
j-j~
therefore write,
may
If
y2
10.5
T Log |S
os
is
The value
of
~- may
o
solution from
GULDBERG
solution
its
means of thermodynamics.
freezing point by
has
shown
t,
being
that,
the
following
exists
between
it
and -^-:
bs
hL-
Ss
0.00954
D
1
I,
10.5
757.
Log
(1
we
0.00954
obtain
t)
2te Auti.
234
CHEMICAL AFFINITY.
RAOULT
has
solution of sugar
The following
found
is
that
the
value
of
O.054.
Temperature.
by PFEFFER,
(2) calculated
by means
235
The values
of
if
is
its
CuS0 4 5H 2
.
39
at
.7
we
III.
The quantity
magnitude will
affinity of
known
If a
of
PAREAU
the
remains,
crystals
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
owing
A=
to the affinity
1300
X 10333 X
18
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
236
CHEMICAL AFFINITY.
this
18 kgrms. of water,
will
_ 2T log
1 ft
10333
-,
is
j|L
^
calories.
|=
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
is
the
MgS0 4 7H
.
water of crystallisation;
its
D =
iS s
4.55
and
SS
it
(log lO s
therefore,
is,
log
=
%)
Q
2
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
being
A ~
4.55
S /
s
^~
metres
calories.
The following
table contains
Gr.
'
WIEDEMANN
of
some of
magnesium
at different
temp-
eratures.
Journ.
in the table
prakt.
are,
Chem.
(2)
9,
338, 1874.
MgS0 4 7H 2 0,
is
decidedly
not affected.
Temperature.
238
The
CHEMICAL AFFINITY.
Temperature.
dlogC m
239
qm
'
2T
dT
'
q m being
MgS0 4
+ H
= MgS0
4.
0.
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
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
2T
concentrations
we may
are
by
the affinity,
in
the
same
ratio as
write
240
CHEMICAL AFFINITY.
A =
we
2T
log
obtain
A =
or. in
the work,
words;
expressed in calories,
at
place
given
is
temperature,
equal
to the
ivliich
the affinity
quantity of heat
transition point,
and
erature
transition point
of
the
and
reaction occurs.
when
takes
it
place
in
reversible
way,
it
will evidently
be
by means of thermodynamics.
which one condensed system is trans-
let
first
of the
two systems
replaced
the
Suppose
formed: The
is
calories.
converted
is
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
place in a reversible
calories.
The temperature
is finally
~~
in this cycle
being
all
rever-
of thermodynamics)
P
T
and therefore,
A _
1
The
practical
means
by
which
P
q
this
T
p
may
be approximately realised,
depend on
the
work done by
case
special
A =
0,
that
is,
the
zero.
is
APPLICATIONS.
IV.
Work done by
241
BY AFFINITY.
we have
T,
1.
1)0\E
Diagram of
work done.
the
The equation
A
shows
that
absolute
at
:= q
zero
-^p
q,
that
is,
the
work which
may be
the
This
on
is
in
where
228,
page
maximum work"
is
it
is
pointed
out
of
evolved
of
affinity
heat evolved,
the
temperature
this
can
zero
reached,
at
and
at
higher temp-
eratures
its
sign
that
to
is
be performed
is
reversed,
in order to
Fio
45
The change
which occurs
Employing
242
CHEMICAL AFFINITY.
we
BERTHELOT,
therefore
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.
line q
temperature we
may
represent
it
2.
It
is
latter
is
expressed
dp
where
425.7
dT
-r
is
unit
the
volume
of
the
in
and
the
rig 46
same
I,
425.7 kgrm.metres].
10333
243
of pressure
-case
the
on
the
transition
work done by
quantities of
affinity as ordinates.
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
_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,
point, and
at
10333
AC)r
4^o
dp
T)
(7
calories,
{7
T)
the change of
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.
this equation in
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
'
REICHER'S
refer
experiments
that
about
the
to
found,
transition
95. 4,
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.
temperature.
O erves
o
to
collect
millimetre scale
wool
introduced
is
water
Fig. 47.
of
small
the
filled
is
the
into
is
is
bisulphide
in
183),
p.
salt.
with mercury.
At C
a thread
precaution
the
evolved
order to take up
filling
bulb
the
mixture
of carbon
and
ments impossible.
Zeit. phys.
der umkehrbaren
2
See
p.
184.
95. 6 and
Chem.
1,
is
heated to a constant
227, 1887.
See also
W. SCHWARZ,
rise.
Gottingen 1892.
The
Time.
245
246
CHEMICAL AFFINITY.
Under a pressure
of
is
calculated by
103 33
425.7 r'
dp
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
experiment.
The experiments
modifications
of
of S.
ammonium
nitrate
2
.
He
ition
rising
3
.
however,
some
degrees,
the
of
influence
the
to be the
on the transition
pressure
same
in
both cases.
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
(<r
r).
On
Transition temperature at
250
A
See also BELLATI and
ROMANESE,
On
heating.
35.45
1 atmosphere
42 .76
7.31
cooling.
30.55
37 .95
(6),
=
4,
7.40
1395,
18856.
247
248
CHEMICAL AFFINITY.
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
3.
The
a.
The diagram
qP
represents the
on the
however, that
qP
point
difference
P,
because
between the
is
out,
work
By means of
must be pointed
It
this
diagram
it
is
2
.
temperature of
the allotropic modifications of sulphur. To
ition
do
so,
we
represent
will
the
first
work
solidification
or
fusion of the
two mod-
ifications of
sulphur in
a
diagram, fig. 48.
Let the quantities of
rig. 48.
heat
q rf
(on the
absolute
scale)
be
measured along
Appendix, note
3.
T.
The
straight
249
T rf and
q rf
q mf
T mf
in
OT
work in question.
At any point P
PR
the
are
quantities
and
work
of
will
a point of intersection at B,
T rm
corresponding temperature
work
zero
is
its
it
is
evident that at
these
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
q mf
i[5
o
T rf
273
114.5, and
T mf
273
120
we obtain
T rm
273
95.2.
at
atmospheres
246
the change for 1
p.
under the pressure of sulphur
pressure,
temperature
250
CHEMICAL AFFINITY.
The transformation
b.
of a mixture of sodium
'T
is
VAN
HOFF,
DEVENTER,
and
GoLDSCHMIDT,
JoRISSEN
llUVC
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)
is
At 34.5,
2
(NaNH 4 C JI 4
The
35
6.
0) 2
= (Na
6) 2
+ [(NH4 )
C 4 H4
t 4
H0
of SCACCHI
salt
C4H 4
The temperature
and
at
into
dextro-tartrates
the
racemates
individual
laevo-
ac-
occurs,
(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
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
and
P C
34.5)
by the change.
Fig. 49.
Similarly
which
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
intersection
Chem.
1,
P 1?
173, 1887;
see also p.
170.
OF
THJ--
UNIVER;
251
at
SCACCHI, that
is,
(1),
(273
26.6).
The
as
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.
and
Since
5660
differs
P!
P
P
very
AO
AO = PB
DO - PC
little
OB
OC.
DO = PC
PB.
PB
The
34.5
7.9,
f 2.9
= 29.5;
29.
V.
26.6
It
has been proved above that the work which can be done
by the force of
may
General considerations.
affinity
A =
T
5
CHEMICAL AFFINITY.
"252
The magnitude
way
it
which
in
of this quantity of
the
reversible.
is
HELMHOLTZ
in such a
producing
of
current
or
electricity,
is
in
reversible.
one direction
the
made
be
may
it
to
is
evident,
At
undergo
erature
change absorbing q
be then depressed from P to T.
allowed
is
current
to
of
take
produce
electrical
work equivalent
is
then
being
calories,
brought back
At the
now
latter
temper-
calories,
initial
its
do
will
it
simultaneously
to
calories.
electricity;
to
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
of electricity.
calories
This
raised
from
to
P and
the
thermodynamics to
it,
and obtain
:P
A
1
II,
~~~~
T'
III,
92.
p.
or
This
result
of
the
then
is
system
produced
heat evolved
words as follows
is
the
by
is
proportional
l
.
reaction
therefore
may
be
by
and the
expressed in
to
which
and
electromotive
proportional
~p*
its
work, A, which
by the reaction
The
:=
may
253
difference
between
it
and
the temperature
multiplied
at ivhich the
reaction occurs.
work done by
is
the latter
By
dA
dT
Eliminating
P'
P by means of
dA
or
== q
'
dA
+ m
T
^.
dA
is
obtain
dT
we
work done by
the change.
HELMHOLTZ
in his
1
of
memoir
equivalent.
quantity of electrical
work
This
is also
23116
kgrm. degree
calories.
T. E.]
254
and
CHEMICAL AFFINITY.
it
by CZAPSKI
As
is
GOCKEL
',
well
and JAHN
3
.
known,
is
GIBBS,
Thermodynamics of
The equation
A-q
shows that
if
by
the
into
work
the electrical
the change
other,
of
one
it
being
of
of
two
be furnished
convertible
mutually
assumed that
course
systems
the change
takes
electrical
we may
A =
and see to what results
It
is
q
it
T,
dA
...... (1)
leads.
Since
it
vanishes
at the transition
temperature
without reference
2
3
below
it
obvious
is
to
the
its
sign)
transition
2,
23, 1888.
255
temperature, and increase above it. The values of the electroshow similar behaviour,
motive force which are proportional to
as
shown by the
is
sign
below
A =
0,
the
consideration
little
dA
will
-r^-
transition
temperature;
at
this
temperature
and therefore
^-
TT
meta- stable
W.
show
phases
i.
e.
that
A =
q,
is
The value of
dA
the
at
-r^-
by
erroneous, for at
transition temperature
may
is
zero.
be cal-
will
be
the
quantity of
from the change
when
set in motion.
salt,
transition
cell (fig.
were connected
up against a Daniell
solution
in
cell
kgrm. equivalent of
zinc
had passed
and
an
equivalent
quantity
have
S0 4
ions
would
transference
of
also
the
S0 4
the
to
256
CHEMICAL AFFINITY.
were allowed
sulphate.
to furnish the
same
would
Everything
point.
the
Suppose
be
to
cell
working
in
its
Na 2 S0 4
for
Na
in
SO
^ ions
n)
(1
The n sodium
combine
ions
the
of
precipitation
S0
with
molecules
Glauber's
of
from
salt
the
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
.
We
zn
The migration
b
^-- -16-
molecules of sodium
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,
the
anhydride
and
of
^-7-
-.
molecules of the
The
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
molecule,
calorimeter as
where b
10)
by LOEWEL
Equation
=^r-
....
'
2 (b
the
(3)
10)
to each molecule
The numerical
16509
calories,
_T
=
=
15.6
,,
,,
we
obtain
LOEWEL.
305.6.
(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
-^
obtain
dE
1.2 millivolts,
dl
1
2
3
temperature
Chem.
of
Glauber's salt
it
at
9. At
the transition
17
258
CHEMICAL AFFINITY.
The electromotive
both
with
and
determined by
means
of
the
by
apparatus represented
on page 196; the following numbers were obtained.
stable
Electromotive force
in millivolts. E.
Temperature.
28 .2
30
5.2
2.9
.2
32
.7
0.5
= --2.05+1.57t--0. 0466
dE
point,
t2,
32.6,
1.5 millivolts.
-TT=
may be
This
consideration.
If
we
temperature
at
q,
evolved
by the
temperatures
Zeit. phys.
^,
Chem.
(4)
energy of the
solution
above
is
we have
q! is the chemical
heat
stable
of
T
A,
of
(fig.
in a condition of saturation
modification
where
is
no meta-stable phase
maintained
at
cell,
that
is,
the quantity
during
for
the
the passage
is
quantity
of unit
According
to
the
259
quantity of electricity
through the cell, and A!
obtainable
the same circumstances.
under
energy
a
for
Similarly,
is
we have
the electrical
cell
A,
is
+ T
q2
......
^|-
(5)
at the transition point the two cells have the same electromotive
force at that temperature, and therefore at T o;
A2
-r^r
dl
branches
electromotive
presents
qi
q2
T
of
the
the curve
of
measure
affords
dl
(at
the
of
heat which
is
q 2 re-
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
electromotive
force
and
Ei
=Q +Bt+
where
is
(7)
(8),
By
and
+ R^ + S^ for
QJL
subtracting,
we
obtain the
t,
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)
....
.
1.6 millivolts.
-h
+
+
1.2
1.1
on the
absolute
scale,
transition temperature
2 (b
and
si
il ar
^2
ly
at
at temperatures
Na 2 S0 4 10H 2
salt
anc^
salt at its
is
Glauber's
Na 2 S0 4
^'
~~ur\
10)
L (b
for
q,
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)
10504
dA,
dT"
~dT~
or,
dT
dT
From
Wj
dAa
is
16509
below
0.36
15.6 ..
:
805.6X2(15.6-10)
23116 E,
where
is
1.2 millivolts.
number
experimentally,
is
i.
e.
in
satisfactory
1.3 millivolts.
261
VAN
'T
dA
dT
be
may
used
calculate
to
cells of the
set
may
increments
the
crements
of
of
and
to
make
finite in-
it
normal solution
A =
since
1/4
1/4
normal
this temperature,
below
lies
it
immersed
of
that
is
salt is
is
a saturated solution
in
in
cell III,
first
Taking
the
cryohydratic
temperature.
It
may
be
dlogC
Q
T2
_
"
dT
which
the
is
true for
strictly
concentration and
'
dilute
solutions,
and in which C
is
little
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),
_9_
and replacing
we
the
Naperian
obtain
10
"
2.3026
5.02
V273X283/'
/4o
grams
5.02
g 1.775
1
Zeit.
phys.
Chem.
""
x_
_\
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,
= 16. 2
in
obtain x
make
sufficient to
we
calculate
to
is
it
Q from
eliminating
and 20.
which
of heat
quantity
This-
sented by l/2(Na 2
S0 4) bH 2 0,
to the
1/4
this process
may
be considered
by the removal of
A! evolved
1.
1/2
(Na 2 S0 4) b
from an
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
last
of
is
200
400
9430 -- 9380
Heat evolved
first five
50
9255
9021
(Na 2 S0 4 ).
25
-
7.8
- 8689 -- 7495
1/2
100
i/ 2
fusion
2.
when
A2
is
(Na 2 S0 4 )
Na 2 S0 4
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
sulphate.
A!
9430-9380
and
its
We
value
is
approximately
-r
Temperature.
oo
is
positive
calories.
CHEMICAL AFFINITY.
use
of
the
mean
values
Temperature.
Temperature.
A.
CHEMICAL CHANGE.
266
CHEMICAL AFFINITY.
The agreement
if
is
satisfactory
the fact be taken into account that the difference between the
electromotive
forces
of the
cells
containing
is
normal
and
1/4
The
solution
cells
may
in this
1/4
normal
way.
mean
solutions.
1/2
normal
of those of the
The following
stable phases
we
find,
is
--1.5
cell
millivolts (p.
258).
3.
From
of the
coefficient
temperature
267
the equations
by solving
q and
for
(2)
tained in (1),
AA
T
__dT
"
2T
and therefore,
by
integration,
equal to zero,
log
Since
by
is
a reaction,
equilibrium
The
A
2T*
proportional
at the
is
motive force
K=
this electro-
!
.
case of
ammonium
NH
sulphide
^ NH
be taken as an example,
may
3
+ H
2 S.
of
at the temperature
log
where ni
0,
VAN
HOFF, Lois de
'T
and n 2
is
2,
and
157.
The
K=
T may
K=
under consideration
and therefore
268
CHEMICAL EQUILIBEIUM,
A
C2
z=
log C 2
The
of
metre.
the
If
0.761 grams,
mixture of gases
the
ammonia
is
of
pressure
17 kgrms.
is
be
will
of
litre
be
mm.
ammonia gas
0.761XPX273 "
_
"
mm.
and 760
at
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
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
electromotive
calories.
5132
.1
4T
log
force
A
==
&
that,
X OQol lo
of
the
= 0.129 volt.
a determination of an
conditions,
must lead
to a
change tends.
For example, suppose that a DANIELL
cell at
can furnish a
kgrms.
solution
of
CuS0 4
is,
containing 159
269
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
ratio
is
a certain definite
The
salts.
zinc sulphate
calculation
would be 10 40
is
exists
further
to
possible
together
studied
(C),
investigated
1.
and
The
Brucine
used
alkaloids
(B),
the
is
brought
of
were
following
Quinine
equilibria
(Q),
being
Equilibrium
between
Quinine,
Codeine
chlorides.
Q +
1
relationship
hydrochloride
JELLETT.
by
Codeine
the
is
C.
HC1. ^=
Q. HC1.
270
CHEMICAL AFFINITY.
2.
Equilibrium between
Codeine,
chlorides,
B +
HC1 ^=
B.
3.
C.
HC1.
chlorides,
B +
Q.
C.
B.
observed
is
the
of
ratios
OHOl
JELLETT
B. HC1.
quantities
of the
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
Let
the
of
values
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
Since
the
initial
condition
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
independent
may
same
the
Since
of
The
of
any similar
series
of equilibria,
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
differ
little,
the
K K
2
we
== 1,
obtain
><
(I:),
We
,*,='
have also
Q0.
From
the
C.HC1
B.HC1
HCl
HCl
result obtained
electromotive
Taking
example
Q.
by JELLETT
force
B.
_
which
by
it
'
found.
is
produced
HCl
HCl
change
it
is
will proceed.
systems such as
2
Ag
Cu 2 C1 2 ^z
AgCl
-f-
2 Cu,
which
is
F. BRAUN.
in
272
CHEMICAL AFFINITY.
From
these
the second
is
117500= 14100
calories;
sarily
is,
case
will
it
be
direction
of the reaction.
reaction can do
2200
The
when
still
is,
calories.
first
it
97000
is
occurring
same direction as
the
in
change
at absolute zero.
The
will
first
systems
may
to
together, above
exist
the
it
first
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
At T
the exception of P.
is
2200
calories, that of
numbers we
lies
at 51
C.
be
find
It is
324
to
As
a further example
we may
however
equilibrium such as
2
According
to
the
Ag Br
;^z: 2
Ag + Br2
when placed
bromide,
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
maximum
vacuum
in
lose
maximum
273
of
may
A =
also be calculated
2T
log fsi.,
^AgBr
where S Br
of the
= 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.
bromide
until the
2.9X10" 53 mm.
5.4
10- 75 mm.
THE END.
APPENDIX
Note
(page
1,
There
2).
to
are,
a cubic metre.
in
Co
x)
(1
of the gas
-y
~
T _(l-x)C
~c
Pt
+ f xC
-.
Ct
a,
Note
2,
32.7
cc.
(1
^-to- +
2)
then Ct
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
^5 o
or,
since
-t
the lengths
We
46 5
.
By
at this
"P
the translator.
20 34
.
276
APPENDIX.
Note
quantities of heat evolved by the conversion of a material system, A, into another, B, at different temperatures
may be obtained as follows:
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
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
Na
we
call the
i.
e. 11
=2
Note
is
the quantity of
ions
(1
11)
5,
the
p. 89.
Valvolin
is
a trade
solution
NAME
Alexejeft*.
Arrhenius
208
....
INDEX.
Duclaux
Dumas
94
Engelraann
Esson
.
....
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
.
93,
(du)
196
135
171
125
33, 56, 61, 82
189
52,
Ettling
92
246, 247
52,
36,
86
169, 203
Boguski
Bois-lleymond
168
51
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
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
12
Hittorf
Davy
81
32, 33, 59
163
.
211,
205
254
254
81, 170, 171, 250
32
145, 206, 233
178,
....
Chancel
162,
257
Hoff (van
't)
151,
206,
208,
Hofmann
Hood
........
36
132
Horstmann
143, 145, 151
Houton de Labillardiere
51, 52
20, 125,
278
INDEX.
56, 61
156, 157
Ikeda
Isambert
Ostwald
254
Jahn
Jellett
Jorissen
52, 171,
Joubert 52,
Joule
Kahlbaum
Konowalow
Kooy 32, 49,
93,
125,
123,
250
254
254
75
125
125, 126,
12,
13,
27,
Pareau
Parmentier
Pe"an de Saint Gilles
235
168
28,
30 36, 92,
....
Pfaundler
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.
Reinizer
83, 96
Rennie
Rodwell
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,
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,
Roscoe
Rose
51
Riidorff
171
'
Sabatier
Salzer
170, 186,
Schiff
173,
Schonbein
Schwab
...
Schwarz
Schwicker
.
Scott
Shenstone
Skalweit
Smithells
Spohr
125,
125
85
250
178
83
130
244
105
104
34
83
25
133
248
Xaumann
...
43,
Nernst
Noyes.
Ogier
44,
93,
188, 194,
......
63
152
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
Waage
145, 206
225, 262,
94,
107,
133
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,
Arsenic oxidation
Astrakanite,
of,
transition
.52
of
point
gas.
8286
80,
116, 120
8286
Active oxygen,
Activity
Affinity
....
coefficient.
.........
at absolute zero,
measurement
of,
208
229
241
230235
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,
Cadmium
...
racemate,
sulphide, dissociation
of, 155, 156, 157, 205
219, 223, 267
of, in wa-
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,
Cane
sugar,
inversion
30,
of,
....
hydroxyl ions,
Chemical induction
116, 121
9198
....
INDEX.
282
Chlorine,
action
of,
on hydrogen,
93
8691
83, 91,
.18
gaseous,
of a system,.
unit of,
.
4
163
....
incompatibility
165
of
temperature in cases
169, 173,
of,
229
12
...
Condensed systems,
203
Electrical conductivity,
methods of determining
.
.2629,3134
Contact action,
calcium acetate,
30, 171,
172, 247
affinity of for
sulphate,
hydrated, 158,160
heat of formation
160, 161
method of deter-
of hydrated,
Crystallisation
mining the transition temperature,
186
3638, 4345,
107110,
173,
of,
174,220223
25
Cyanogen,
acid
Cyaiiuric acid, see cyanic
Cycle of chemical equilibria, 271
233
47
199
Electrolytic gas, transformation into
water.
36,
3942, 4549,
Electromotive force,
.,
#-Dichlorhydrine, decomposition of
125
178
Differential tensimeter,
94, 181
Dilatometer,
.
....
Dissociation,
144, 152,
salts,
155157
of hydrated
158161, 188
pressure
by means
of direction of change
272
Electromotive force, measurement
196
of
of,
Equilibrium, constant.
223-228
.
145
connexion of
Dibromsuccinic acid,
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,
30
on,
Ethyl acetate,
125,
130, 131, 133, 147
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,
115121,
28
Hydrated
salts,
of,
168
on
bro-
mic
of,
104
acid,
116121
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,
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,
on chemical change,
192, 193,
198203,
230,
255257
....
93
146
heat of
for-
Limiting
equation,
Magnesium
sulphate,
mation of hydrated,
of,
148150
stant,
Heat evolved by
nexion
of,
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.
125
of,
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,
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,
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.
...
dation of phosphorus,
66, 69
Pressure, influence
sition temperature,
Pressure, influence of,
sition
phosphorus,
5],
of,
.
25,33,
50-61
32,
33,
6169, 8186
73
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,
of molecules participating
in a change,
99 112
29
equilibrium be151
of active
83
oxygen by oxidation
Number
Optical activity,
isomers,
tween,
25.
5061
...
Normal
of,
....
135
20
33,
Polymorphous
Nickel carbonyl, oxidation
134,
of,
temperature
on the
of sulphur,
244246
Principle
of mobile equilibrium,
217228
Racemates,
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,
Sodium ammonium
Sodium
tartrate, 170,
171, 186,
250
action
of
129
chloracetate,
on,
on
of,
133
Sodium hydrogen phosphate, hydrated, heat of formation of, 161
drated,
temperature,
169, 203
170,
171
Sodium
Sodium
product
Solubilities,
of,
177
206209
Solubility
Solubility of water in
189, 190
Solution heat
231, 234
of,
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
181183,
168,
221,
..43
133
acetates,
System, unit of concentration of a, 12
253
quantity of a,
Synaldoxime
92
Tartrates, transition temperature of,
Temperature
sition
cell,
257259, 266
199,
Temperature, influence
librium,
....
of,
on equi-
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,
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,
Velocity constant,
....
chemical
affinity,
241
absolute zero,
Work,
electrical,
change,
done by chemical
251, 252
Work,
Work,
226, 242
242
......
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,
STAMPED BELOW
AN INITIAL FINE OF
25
CENTS
>94