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Theories of Solutions
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YALE UNIVERSITY
MRS. HEPSA ELY SILLIMAN MEMORIAL LECTURES
THEORIES OF SOLUTIONS
By Joseph John
Thomson, D.Sc, LL.D., Ph.D., F.R.S., Fellow of Trinity
S.
Hon. LL.D.
Profes-
THEORIES OF SOLUTIONS.
By Svante August
Arrhenius, Ph.D., Sc.D., M.D., Director of the Physico-Chemical Department of the Nobel Institute, Stockholm, Sweden.
THE PROBLEMS OF GENETICS. By William Bateson, M.A., F.R.S., Director of the John Innes Horticultural Institution, Merton Park, Surrey, England.
In preparation.
THEORIES OF SOLUTIONS
BY
SVANTE ARRHENIUS
DIRECTOB OF THE NOBEL INSTITUTE OF THE EOYAL SWEDISH ACADEMY
OF SOIENOEa, STOCKHOLM
WITH DIAGRAMS
Univebsity Press
Copyright, 1912
Bt Yale Universitt
Published
May, 1912
TO
JACQUES LOEB
IN ADMIRATION Or HIS APPLICATION OF
New
children, in
Haven, to be held in
memory
trust, as
of their beloved
On
this foundation
made
PREFACE.
The
lege for
me
how much
my
am
and the
a great privi-
University-town of
New
England.
colleagues, Professor B. B.
Gooch,
it is
President Hadley
during
New Haven
of 1911.
I shall
visit to
To my
the old
distinguished
tions during
my
stay in
where
New
I lived
Haven.
ser-
me
in correcting
proofs, I render
May my
ever keep
my
him
my
kindest thanks.
me
in friendly
New Haven
ix
Akehenius.
CONTENTS.
PAGE-
CONTENTS
INTRODUCTION
LECTURE I.
xi
xvii
philosophers.
"Osiris."
LECTURE
Goldschmidt's ex-
II.
17
XU
THEORIES OF SOLUTIONS.
N. Other physical methods of determining N.
Charge of single droplets. Planck's theory of
radiant energy. Movement of molecules or ions according to
Electric determinations of
Svedberg.
Avogadro.
LECTURE
III.
Suspensions
Methods
particles.
36
The
of preparing suspensions.
organic enzymes.
size of the
suspended
Color of suspensions.
Heat
of
suspension.
LECTURE
IV.
The
notes.
ence of temperature.
so-called
adsorption-formula.
55
Influ-
LECTURE
V.
Kirch-
on vapor pressure of solutions. Guldberg's fundamental applications of the thermodynamical laws of solutions.
The general laws of solutions deduced by Gibbs. Helmholtz's
hoff's studies
CONTENTS.
XUl
Le Chatelier's law.
pressure and the work of
Planck's theoretical deductions.
The osmotic
LECTURE
VI.
91
of electrolytic dissociation.
properties.
substances.
Valson's
investigations of
additive
LECTURE
VII.
Velocity of Reactions
Inversion of cane sugar studied
112
by WUhelmy
1850.
Law
of
Action of zjrmase
Action of chlorophyll.
Accelerating substances. Growth of bacteria. Retarding
processes. Schuetz's rule. Formation of ether according to Kremann. Radioactive processes. Dissolution in acids. Photochemical reactions. Decomposition of HI.
Spontaneous decomposition
of ferments.
Concomitant processes.
Influence of temperature.
Van't Hofif's rule.
LECTURE
VTII.
Kirchhoff's, Guldberg's
tions.
The work
of Berthelot
Strong electrolytes.
of Hittorf.
solutions.
Influence of temperature.
Godlewski's
determinations.
Noyes' work.
Peculiarity of
Alcoholic
H- and
THEOEIES OP SOLUTIONS.
XIV
Lorenz on fused
Carrara's opinion.
salts.
LECTURE
IX.
Equilibria in Solutions
153
Work
of Kahlenberg.
LECTURE
X.
ways
of
explaining
Jahn's
The hydration
opinion.
The
172
electro-
Hydration of ions.
Saturation. Specific weight of salt solutions. Expansion on
neutralization.
Electrostriction. Bousfield's and Riesenfeld's calWashburn's method. Correction of Hittorf's figures.
culations.
static
influence.
theory.
ity.
LECTURE XL
The Docteine of Eneegt
tions
in
Regard to Solu196
Discussion
phenomenon.
CONTENTS.
sociation.
tion.
XV
Noye's determinations.
BIBLIOGRAPHICAL REFERENCES..
INDEX OF AUTHORS
INDEX OF SUBJECTS
226
239
243
INTRODUCTION.
from this platform
where Willard Gibbs enunciated his standard work on "the theory of heterogeI also feel very much indebted for the
neous equiUbria.
invitation to give a series of Silliman lectures, which
have been delivered by the most prominent men of
the scientific world. I therefore extend to you my
warmest thanks for having conferred this rare distinction upon me.
The object of my lectures will be some chapters of
modern physical chemistry. This branch of science
has been treated in a rather great number of good or
even excellent text-books, here as well as in Europe.
It is therefore a difficult task to give something new
and something which has not already before been
worked out in a masterly manner. But it seems to
me as imprudent as to carry owls to Athens to give
you a course of physical chemistry as it is presented in
the text-books. Therefore I have confined myself to
some problems which are now under debate and which
are still not finished but which promise the greatest
It
is
an exquisite honor
to speak
'
'
Also
when
I refer
THEORIES OF SOLUTIONS.
XVIU
found
it
an idea
of the strict
is
generally represented as
like
fully
if it
had
developed from
Jupiter's head.
individual ideas.
On
it is
quite clear
that
physical chemistry.
an
But
of
branches of
modem
honor
and
important
to which I
such
have the
my exposition
will
be easily
filled
INTRODUCTION.
XIX
For
namely,
this chapter, a
number
their properties; it is
an extensive
science.
some few
of
Physics on
Physical chemistry
sciences;
it
is
it is
an intensive
Upon this depends its all-embracing feawhich has attracted so great admiration. But
on the other hand it has its profound quantitative character from the science of physics.
From this circumstance the great solidity and strength of our science
chemistry.
ture,
is
derived.
The
measm-e-
THEORIES OF SOLUTIONS.
XX
substances
is
very
difficult to
modem
the cause
development
German
Nemst.
The
and will
by this peculiarity that it has exerted such a great influence upon the
neighboring sciences, pure and apphed, and on this
theoretical side of physical chemistry is
may
it is
be regarded as an
natural sciences.
LECTURE
I.
we go very
far
but water
and Xenophanes
generally preferred. Empedocles
air,
is
Heraclitus
fire
foiu-
The
doctrine of Empedocles
THEOEIES OF SOLUTIONS.
and who
still
earth
air
by subdivision;
becomes
Under
fire,
all
their experi-
ence.
In antiquity the chief products of industrial chemwere the metals. Plato and especially Aristotle
istry
most valuable
as the
"mercmy
"ghost"
all
metals.
of the philosophers"
of the metals,
name
tians.
it acts as a
Olympiodoros says "Osiris is
principle of everything liquid, it is Osiris, which
name
Under
the
in contradistinction to the
common
to the seventeenth
we
direction given
by Nature and
everything to water"
used
it
(i.
e.,
at first transformed
it) "before they
According to van
dissolved
of his time,
sylvestre).
THEORIES OF SOLUTIONS.
4
"water
is
all
substances
modern
be reduced." Boyle, the father
chemistry (1626-1691) opposed the ideas of Aristotle
may
of
alchemical successors regarding the iowc elements; he expressed the opinion that only such sub-
and
his
undecom-
be transmuted into
The
all
other elements."
was summed up
circumstance
that
precipitations,
proceed
much more
regularly,
As the
solubility of a substance
its
problem
was
called "alcahest"
The
alcahest
when
the
was regarded
as
of chemistry
if
was
to find
This hypothetical
by Paracelsus (1493-
when he
using
it.
The most
interstices.
atoms
another substance.
of
Aristotle
opposed the
Democritus.
upon the
of
common
salt
As the
it
THEORIES OP SOLUTIONS.
The
off,
so that the
Reaumur
It
was necessary
Newton
of the phlogiston-theory,
scientific
world and
is
in
we do not suppose
solved
if
Very
of gravitation.
interesting
Newton namely that the dismolecules tend to get away from each other as
another statement by
other.
modern theory
now
So-called
found
and
of
difficult to
gravitation.
affi-
But even at an
is
early stage
soluble
it
was
is
independent
and
THEORIES OF SOLUTIONS.
O
It
was
salt or of
to simple solution.
Upon
On
He
by the use
of a solvent.
if
If I
heat a
salt
becomes liquefied,
seems obvious from
it
It
still
For
more evident as
perature.
Even
It
liquefaction
is
would mix
water, but
in
not so with
is
and water, a
fact
many
earhest times.
The
by the
Richter (1793)
Thus
for instance
tate salts
he says that
it is
possible to precipi-
salt has.
air
and
than the
air
has."
the latter one, indicate that his views do not stand very
severe criticism.
The same
is
He was
chemist BerthoUet.
them
of chemical
in constant proportions
typical
He
components
observed that
if
mercury-sulphate
is
dissolved in
THEORIES OF SOLUTIONS.
10
form
of crystallisation; other
Ta.Tnm a.nn
examples of similar
and by Loewenstein).
is
an absolutely untenable
From
this
idea.
still
actual discussion
its
solution diluted,
is
a certain indication
11
is a
BerthoUet seems also to have held
But the majority of scientists regard
chemical process.
this
opinion.
it
In reality
no sharp limit between physical and chemical
processes.
The best definition to decide between a
physical and a chemical process is the following: In a
there
is
With lowering
changed, some
formed into ice-molecules. Thereby the volume increases just as when water freezes to ice.
Of course the
ice-molecule has another structure (probably more
complex) from that of the water-molecule. It would
therefore be right to say that on coohng water below
4 C. a chemical process takes place.
chemical process.
The
ice-molecules as well as
by
far
THEORIES OF SOLUTIONS.
12
4 C.
and
0.
important and
is
But
if
we have
H.
If
CH3COOH
decomposed into
their ions
molecules are
CH3COO
and
water, the
sociated molecules.
The
being
split
up
most
is
on
dilution.
In this case
and
whole
acid
molecules
same degree
water-molecules to ice-molecules.
It
is
therefore
no
13
is
erly be regarded
Most
as in the
main a chemical
process.
Such
an assertion is connected with the ease with which it is
carried out in the direction from water to ice, as well as
in the opposite direction from ice to water.
If we do
say that
scientists
it
is
a physical one.
two modifications
consideration, the
fluid
of water,
namely
is
if
an
the presence
of
the
common and
rarely found.
Still
grey
tin.
more is this
The latter is
On common
tin
is
very
in-
it, it
14
THEOHIES OF SOLUTIONS.
difficulty,
processes.
who
conclusive,
The
and
do therefore not contain ions in appreciable degree.
Most reactions and especially the most important
ones ia inorganic chemistry are due to ions they are
water-free acids are non-conductors of electricity
characterized
This idea
is
by
carried out
by Ostwald
in his treatise
on
chemical analysis.
for
Baker.
formation of
small,
is
in
The
is
15
more
and
is
CeHe
+ HONO2 =
Probably benzene
is
K,0
- NO2
C6H5
NO2 and
positively charged.
OH
On
of
which
addition of
diminishes.
and NO3.
Of course
this
view
is
only a
may
modem
Similar
ical reaction
Sometimes
from the
it
electrolytic standpoint.
is
not
his
H ion
in the acid).
Similar circum-
16
THEORIES OF SOLUTIONS.
investigations
for
Here
the
is
number
of re-
a vast field of
extension
of
the
LECTURE
II.
At the end
ment
and from
this
time
we
we
are
of
quantitative methods in
science.
of
Certainly
there
neutralization of
certain quantity of
solutions
if
is
17
THEORIES OF SOLUTIONS.
18
compounds
It
is
N2O
Ammonia
NO
NH
Nitric acid
NOj
Water
Marsh gas
HO
CH2
Olefiant gas
Nitrous acid
.NjOs
CH.
and so
forth.
It is said that
it is
is
19
to a certain extent
if
thing
new
of great
The
THEORIES OF SOLUTIONS.
20
In
those
1,
The
discovered.
great progress
made
in
chemistry
tative measurements.
porportions
won an
When
it
all
times.
had begun
its
allied
it
theory of gases was born and developed by the foremost physicists, such as Clausius, Maxwell, and Boltz-
mann.
They
and magnitude
atoms and their compounds, the molecules, with
nearly the same certainty as an astromoner calculates
the magnitudes and the motions of the components of
calculated the motions
of the
double
stars.
as the
Then
came the
reac-
following manner.
It
is
true
that
21
in
chemical
the
com-
conversion into
the composition
product,
that
repeated
distillation,
is,
is
of
course dependent
words
And
To
is
equivalent to
it.
new law
this
law the
22
THEORIES OF SOLUTIONS.
configuration in space.
Nature
The opponents
to
23
fall
the
it
be observed with
He measured
their
whereas a formula of
v.
ment.
Perrin has worked out his experiments on a very
large
scale.
He
used
mastich in water.
He
suspensions
of
gamboge
or
d,
where
is
~^
3T.a.b'
the
and
N the num-
a was deter-
THEORIES OF SOLUTIONS.
24
and
T,
ir.
determined experimentally.
He
found
The
of
N=
were
of d
68.10^2.
in another way.
is
The
own
density.
number
65.1022.
known
lower ones.
wards
is
The
Now
Perrin inquired
in
and
From these
how many times one
instance, oxygen.
25
fluid.
Hence he
=
thrown out by a gram of radium per second, that
71. 10^^
Boltwood calculated the quantity of a-particles emitted by one gram of radium and the corresponding number of radium-atoms decomposed in a
certain time and compared this quantity with the
observed rate of decomposition of radium.
=
calculation the result is obtained that
From
71.10^^.
this
26
THEORIES OF SOLUTIONS.
Another method
of calculating
N = 71.10^^,
N=
Faraday,
= 62.W^
When we know
the
number
it is
easy to calculate
varies between
about 2.10^ and 6.10-8 ^m.
We see then that the molecular or atomic theory has
attained a very high degree of probability through these
recently made measurements. Ostwald has openly conceded that this theory does not seem open to question
but that one must admit a granular structure of matter.
It
is
27
structure.
In 1870 Helmholtz indicated that the most
simple way of interpreting the law of Faraday is to
which are
all of
is
what
is
now
called elec-
It has
but the negative electrons occur in the so-called cathoderays or (S-rays. It is therefore now generally admitted
that the charge of positive ions
negative electrons.
The
is
due to the
loss of
particles.
Science changes
When
trically
its
Ehrenhaft measured the movements of eleccharged particles under the influence of gravita-
Now
particles.
single particle.
THEORIES OF SOLUTIONS.
28
SO that the
observations
difiScult.
In moist
air or if
temperature-
was very
perceptible.
movement
yeUow phosphorus.
The charge of the metaUic
particles observed by
Ehrenhaft varied for platinum between 0.9 and 12.10-1''
units (instead of the constant charge 4.65. 10-" units),
similar results.
The observations
Przibram.
He
of Ehrenhaft
investigated
were continued by K.
the
charge of droplets
produced by
29
It
is
very
difficult to see
a simple
way
out of
n times
number
of molecules is
less.
The
general
mean was
still
4.6.10-' units.
is still
make thousands
The cause
In order
seems necessary to
undetected.
it
of single observations.
In some hundred cases Przibram succeeded in measuring the charge of the same droplet twice during its
fall,
taken place.
in
many
cases a discharge
had
THEORIES OF SOLUTIONS.
30
It should
summary
concise
is
R.
V.
Townsend
R. T. Lattey
J. J.
Quantity of
Helmholtz and
Richarz
H. A. Lorentz and
E. J. Stoney
T. S.
10"
Thomson
1890
1.29
1890
1.29-6.1
electricity
electrolysis.
Loschmidt's number
of atoms in a cubic
at
centimeter gas.
Falling nebula of drops.
1.2-1.5
1898
Stokes formula. De(1909)
5
termination of the
total charge.
Fallingnebula of drops.
Stokes formula. De1898-99 6.5-6.8(6.0-8.4)
termination of the
total charge.
f Constants of radiation
J
entering in the for1901
4.69
mulae of Stefan and
I
W. Wien (Planck).
M.Planck
I.
Nabl
1902
1903
Ionization
interruptor.
J. J.
Thomson
through
radium.
H. A. Wilson
1903
3.1 (2.0-4. 4)
H. PeUat
1907
2.4&-6.9
K. Przibram
1907
3.8 (1.7-6 2)
in electric fields.
trolytic solutions.
in electric fields.
R. H. Millikan and
L.
Begeman
1908
4.03 (3.66-4.37)
Method
of
H. A. Wil-
son.
E. Rutherford and
KGeiger
1908
4.65(4.15-5.5)
Counting of o-particles,
measuring of charge.
1908
R. Tabor and
E. T. Lattey
1909
A. Alexejew and
M. Malikow
F. Ehrenhaft
1909
1909
G. Moreau
1909
M. deBroglie
1909
J.
Perrin
1909
R. A. Millikan
1910
F. Ehrenhaft
1910
K Przibram
1910
4.79
31
THEORIES OF SOLUTIONS.
32
such an
expectation
the
all
Further, through
former measurements
come invaUdated.
many
It has
would be-
in
particles
Other deviations
law occur with very minute spheres. As
from
this
atomic distribution of matter rests chiefly on the observations of the movement of small suspended particles
in a surroimding Uquid.
its
energy con-
in
Stark
to
e.
Milli-
THE MODERN MOLECULAR THEORY.
discrete structure of energy
33
is
If
is
the
mean value
number is proportional
given by v. Schweidler.
llVn according
This theorem was
to
this
to a theory
verified
by
Regener.
If
we
circumstances
D=
4
Vd^
is
d,\
34
THEORIES OF SOLUTIONS.
d=42.3 per
nmnber
42.8
For the
solu-
35
Dalton says,
"At the time I formed the theory of mixed gases, I
had a confused idea, as many have, I suppose, at this
later.
same
size;
tains just as
hydrogenous
same
either in the
same volume or
umes
haps,
ago.
there
a nearer
LECTURE
III.
SUSPENSIONS.
Theough
work
of Perrin it has
manner.
Fluids containing suspended particles have attracted a very great interest in recent times; therefore a
short review of their properties wiU be very appropriate in this place.
There are
sions.
The
many methods
alcohol a substance,
in water,
e.
g.,
in
dissolving
mastich, which
water.
Then the
and the
particles of mastich
is
in
insoluble
is
37
SUSPENSIONS.
fluid by bubbling an
In a similar manner a suspension of sulphide of antimony (SbsSa) may be prepared.
In other cases sulphuretted hydrogen is
introduced into a dilute solution of a metallic salt
(for instance salts of iron, cobalt, nickel, palladium or
platinum), and a sulphide is formed, which remains
partially suspended in the liquid.
At the same time
is
it.
set free; to
remove
manner
all
it
the solution
it is
insoluble salts.
(Graham)
In an analogous
or
Some
salts,
e.
g.,
ferric
acetate
away.
may be
is
the reason
to them.
called
dialysis
(1862)
egg-albumen, gum-
arabic, etc., which do not pass through parchmentpaper colloids (from kolla, glue) in contradistinction to
crystalloids, which pass easily through the membrane.
But the suspensions have very Uttle similarity to glue
or albumen and therefore the name of colloid should
THEORIES OF SOLUTIONS.
38
when
The
It
gave a char-
brown
for silver,
dark brown for platinum and red or blue for gold (the
blue
corresponds
colour
coarse
to
for
But
This
particles).
common
metals as they
rents.
The
regarded as an arithmetic
mean between
may
is
be
those of the
As
As the
marked
the
Sved-
path
polarized.
It gives consequently
effected
by
if
was independby Siedentopf and Zsigmondy in Germany and by Cotton and Mouton in France. In this
ently invented
SUSPENSIONS.
beam
instrument a
They
39
by means
through
become illuminated.
its particles
of a microscope in a
beam
of light.
mm. may be
solar light.
is
detected,
If the total
known and
the
when they
are illuminated
by
number
mean
may
be determined. It is
usually assumed that the particles are of a spherical
form.
The
particles
0.000006
mm.
may
be of
They
still
are
then
invisible
with
the
by
If
was
of
mm.
40
THEORIES OF SOLUTIONS.
amount
But
these particles.
of the fluid
may remain
slowly and
unlimited time.
is
suspended in the
fluid for
an
particles of
the ultra-microscope,
for H2, O2, CI2, Br2 and I2 are according to the formula of
Emstein 0.06, 0.20, 0.20, 0.32 and 0.52 respectively in
the same units. Obviously the difference from a real
so ution
is
temperature
As
may
by the
It is evident
slightest inequality of
This indicates that they carry a cercharge. The surrounding fluid is charged
electric current.
tain electric
is
therefore carried in
SUSPENSIONS.
41
and aluminium,
hydroxides, etc.
we have water
in a
electrodes,
cells.
is.
movement
is
therefore
sponding velocity at 18 C.
is
for
K-ion 66.10-5).
The
same
It is of the
and proportional
to
it
and
now
must be doubled
is
If
same
difference of
THEORIES OF SOLUTIONS.
42
The
potential.
force
driving
is
the
(if
potential
hand according
(Stokes'
law
is
agrees
well
velocity
with experiment.
On
if
ground the
this
the dimensions of
This
suspended particles
may
particles.
As
electric
the
latter
are
generally
negatively
added, so that
it
is
base
Of other
ions,
much
the latter a
The suspended
SUSPENSIONS.
43
movement
of the particles
is
which
own.
Therefore the
generally
hampered by
its
Sometimes
it
may happen
is
AI2 (804)3
of
suspended
silver-particles,
was very
well
known
upon suspensions.
much more
Barus investigated
desirable).
44
THEORIES OF SOLUTIONS.
Similar experiments have been performed
by Bech-
KOH
oo
CaCIj
50
CdSOi
25
CuNjOe
45
SUSPENSIONS.
The
positive ions,
way
sol,
any influence at
The
all
by
Hardly
acid.
HCI
KI
>
NaCl
9.25
MgSOi
0.217
16.2
KCl
9.03
K2SO4
0.204
12.5
J^Ba(0H)2 0.42
H2SO4 aboutO.5
KaCrA
0.194
400
KBr
KNO3
11.9
J^BaCU
The
TI2SO4
9.64
bases (Ba02H2)
0.219
salts
of
much more
ion has
effective
and Picton.
Also
than inorganic
The hydrogen
suspensions.
The rule of
was
first
by the
following investigators.
46
THEORIES OF SOLUTIONS.
suspended particles of
noble metals was very thoroughly examined by Svedberg and his pupils. Just as spongy platinum destroys
of
natural,
since
velocity, as
was quite
The combined
figures
(vaUd at 25 C.)
TimeMinates.
Combined Gas
c.o.
Velocity
c.c.
per Min.
10
17.8
1.78
20
30
40
50
35.8
1.80
54.8
1.90
72.4
1.76
90.2
1.78
They then
was
to be
47
SUSPENSIONS.
sodium hydrate
of the
is
added.
With
maximum when
decreases again
if
if
first increases,
the solution
is
about
and afterwards
it
is
further increased.
obtained
increasing quantity
then reaches a
is
This
is
figures,
normal.
Cone, of
Time
in
NaOH.
minutes
255
34
28
24
25
22
of decomposition is for
34 34 70 162 520
low concentra-
i.
e.,
the
is
48
THEORIES OF SOLUTIONS.
49
SUSPENSIONS.
peculiar
action; at
paralyses the
sol,
by Jacobson.
In these changes, the reacting substances probably
we
and
many
condensed
This is prob-
in such
particles
and
able to
them
THEORIES OP SOLUTIONS.
50
caused
diffraction
of
the
light,
depend.
if
Thus
he prepared
He used,
gation.
method
of reducing
longer perceptible.
c
61
SUSPENSIONS.
The
the
same quantity
when the
The
is
Rappo by
according
this
emulsion
is
by
KNO3, KCl,
precipitated
THEOEIES OF SOLUTIONS.
52
Svedberg and his pupil Od^n investigated this phenomenon. They found that the solubility of this
sulphur
with
increased
temperature
approximately
From
temperature.
manner
grammolecule
Normal
in 0.2
in 0.3
in 0.4
in 0.5
Solubility at 20
Cal.
NaCl
NaCl
NaCl
NaCl
0.3
0.08
NaBr
The experimental
may be regarded
cal.,
that
on the
influence than
fluence
if
finds
if
in equimolecular,
in equivalent solution.
Oden has
He
NaCl
indicate
influence
that
different
preparations
of
more
fully.
suspended
is
represented
5 = 32,810
(100n)-2-8
54
THEORIES OF SOLUTIONS.
of action at
any concentration.
is
LECTURE
IV.
the
greatest
value
for
many
industrial
processes.
fibres,
such
powdered
glass-wool, powdered
kaoline, metastan-
nic acid,
silk
glass or
power as charcoal.
On
animal origin many dyeing and tanning processes depend; further the retention of carbonic acid, moisture
and
THEORIES OF SOLUTIONS.
56
Clearly they
many
investi-
gators.
The
chief problem,
Reymond
called
"adsorption,"
which
is
meant
to
is
only at-
solid
solution)
or
chemical
interaction.
These two latter processes sometimes accompany adsorption and so exert a disturbing influence.
It was found, as one would expect, that the adsorbed
quantity increases with the concentration of the surrounding gas or solution. In some cases there exists a
proportionality, reminding one of the law of Henry, for
instance, with gases in general at high temperatures
and with hydrogen and helium even at rather low temperatures ( 80 C). But in the majority of cases the
adsorbed quantity increases much more slowly than the
concentration considered, and this was expressed by
of a formula, which has often proved very useful
means
in interpolations, namely,
where a
is
kc",
g. of
adsorbent, k
57
than unity.
and plotting
controlled
log k
by giving
the form
it
+ n log c
The
points
0.333;
a (calculated).
a (observed),
0.41
1.94
2.21
2.51
3.94
3.99
13.74
7.65
41.64
10.49
10.1
12.97
12.9
85.86
Here, as
tion
0.
2.96 (Travers).
is
is
7.00
gas on one
i.
e.,
is
little
short
bent down
This phenomenon
0.25;
THEORIES OF SOLUTIONS.
58
is
Many
similar
With regard
1 to 2.
it
was
by the
measurements.
t
59
a maximal value of a.
would increase the value of the formula to a high
degree if A were zero or if it were a fimction of S, for
is
It
THEORIES OF SOLUTIONS.
60
8 gives 0.88
SA
0.55
0.484
System
Acetic
acid, charcoal
"
2.48
0.1670
0.414
"
10
"
1.36
0.3275
"
12
"
0.9052
0.4660
0.4218 Acetic
animal
origin.
charcoal
acid,
14
"
1.4570
0.245
"
16
"
1.7829
0.2276
0.4057 Acetic
animal
origin.
charcoal
acid,
0.00884
g.
As
is
61
c,
has reached a value higher than 0.9 (grams per 100 c.c).
The
mean
value of
constant, whereas
But
insignificant.
k infinite.
(in
lie
c)
k.
The
that
e.,
/c
mental
We
therefore conclude
errors.
As
will
be seen
later
on
it
is
very
The equation
of
Schmidt with
AS =
0.4343 corre-
da
dc
if
_1S
~
we have
a
a solution of the concentra-
THEORIES OF SOLtTTIONS.
62
by dc,
we then
if
to
it is sufficient
increase
add a quantity
i. e.,
0,
We
tion.
away
also see
all
and pure
charcoal,
from the
above how
figures
c in-
From this
by the
differential
equation.
on
is zero,
as
is
shown
dyes
The analogous
is
well
Dewar
known;
it is
all
of a
fact that at
smrounding
From
older investigations
how
it
gases would
was
perfectly
in ques-
63
results.
compared with a. For carbonic acid and ammonia at 76.5 and 23.5 he observed values of a
amounting to 114.1 and 154.4 c.c. perg. carbon, respec-
ity as
tively,
spectively.
Titoff
limit, especially in
As
of
is
is
seen from
had then
S =
114.6
and
158, re-
my
may
therefore
as
in
was used
cm. Hg.
Cabbonic Acid at
c is
same formula
expressed as pressure
64
THEORIES OF SOLUTIONS.
much
is
characteristic
and
Homfray
in
the same
Miss
65
i. e.,
at 0.
Qo
?o
is
qa
Nitrogen
Carbonic acid
0.330
Ammonia
0.502
number
the
0.347
quantity of carbon;
when
?i
0.210
0.293
0.384
of calories developed
7392
7772
11245
qi is
its
Q.
4700
6564
9408
by one cubic
adsorption in a large
Here p
is
_
~
Q
1.985 T^'
is
in equilibrium
as
is
THEORIES OP SOLUTIONS.
66
to
i. e.,
(or
c, cf.
too great.
as k
is
proportional
This
above.
ciirves
gent
towards the
0.5
and
for
them a
is
The
slope
on
67
and high
79)
THEORIES OF SOLUTIONS.
68
s
58
158
116
91
60
87
90
87
284
403
304
178
Ethylene
0.00883
41H.
Ammonia
Carbonic acid
0.00808
0.00701
Methane
0.00367
Carbonic oxide
Oxygen
0.00280
0.00269
Nitrogen
0.00268
71T.
30T. 28H.
9.4H.
3.2H.
2.5H.
2.35T. 2.0H.
Argon
Hydrogen
0.00259
1.67H.
127
154
0.00042
0.227T.
32
133
155
The exception
3.07.
is
there-
S>.
In the
one case through increased pressure new molecules are
carried into the sphere of the molecular attraction of
the carbon, in the same
molecules
are
forced
way
into
the sphere
of
new
molecular
69
wards, as
if
we may
if it
has
is
it
we have then
does not
make any
equal to the
sum
The
it is
propor-
acting pressure
and the
1J27
71
seems therefore as
if
It
phenomena.
culiarity
chemists,
was used.
is
critical points,
i.
e.,
o,
as
an inspec-
The
is
stant proportions
loose nature.
may
it
This instance
LECTURE
V.
DIS-
is
known
well
hydrates respectively)
As a
rule
it is
greatly increased.
The
ideas mentioned
upon
most convincing
they at
first
72
The new
had been
73
points of
and again
collected together a
demand
may
easily
progress in
it is
be traced
The
chief
of dissolved substances
most
r61e in chemistry.
far-
it its
phenomena
In
thermodynamics to the
peculiar to solutions
is
independent of the
first
instance,
we have
to treat the
to
regard
the
increasing
and
application
thereof
the
THEORIES OF SOLUTIONS.
74
the simultaneous
solutions.
It
is
Newton
phenomena
may
mutual repulsion
of those molecules.
"As
by a lowering
temperature
of
Dissolution is therefore in a
high degree connected with evaporation, namely in this
just as gaseous molecules are precipitated
75
with sulphate or selenate of sodium, the solubilitycurve shows a break and sometimes a fall with increas-
e. g.,
vapor-tension,
is
refuted
is
by means
of
the
assertion
is
subject to a transfor-
mation.
There
is,
dissolved substance.
criticises
the theory
of,
due to a force of
between the
calcium, which acts even
by the
is
insolubility)
Gay-Lussac expressed the opinion that when the solutions of two salts of different acids and bases were
mixed all the four possible salts were formed, e. g., in
the example above there existed in the mixed solution
not only K2SO4 and Ca(CH3C02)2 but also KCH3CO2
and CaS04. If then one of these four is very slightly
THEORIES OF SOLUTIONS.
76
soluble,
is
supersaturated with
precipitated,
regard to
it,
it
is
may
molecules of CaS04
acids
He came back
This
almost word for word the statement of Gay-Lussac.
The
different
colors
of
concentrated
and
diluted
by Bizio
molecules,
"The
77
phenomenon
but
which
this
view
is
expressed.
re-
markable conclusion that "the osmotic force is analogous to the elastic force of vapors. Between the fluid
column, which rises in an osmometer and the piston
Ufted by the elastic force of a vapor there is no other
difference than that of the medium in which the work
is
effected."
In 1869 and 1873 Horstmann deduced from thermodynamics the laws of chemical equiUbrium between
gaseous substances. As he had already tested his
theoretical results on known equilibria between gases,
he next subjected an equilibrium between dissolved
substances, namely the sulphates and carbonates of
potassium and of barium in the presence of precipitates
of the two barium salts, to the same formula as that
which had proved valid for gases.
This equihbrium had been studied by Guldberg and
Waage. In 1864 they had elaborated a theory of
chemical mass-action according to which the "chemical
force " with which two substances A and B in concentrations Ca, and Cb, act upon each other is proportional to
the product of these concentrations raised to certain
powers,
i.
e.,
E and F were
of
two
salts,
to
Ca C%.
If
then two
new substances
THEOBIES OP SOLUTIONS.
78
magnitude,
i. e.,
T7-
ria
fib
IT
O'
Cf
principal example.
was these experiments which Horstmann calculateH by means of the formula which had proved valid
for gases and he found them to be in good agreement
It
with
it.
He
(dissolved) salt
its
molecules, in the
property of
their
their
In this
way
79
was made
secondary actions
They say
perfect.
may be neglected
if
that
"these
manner, so that
permissible."
is
came a more
sceptical time,
when
may
it
Later on
was strongly main-
exist
and when
independently
it
was regarded
Nowadays we
it as
have come
proved that the molecules possess a motion, the energy
of which is proportional to the absolute temperature
(cf.
Lecture
II).
Regarded from
this point of
THEORIES OF SOLUTIONS.
80
upon the
some
fact that
and does
Walden
power
of a given Uquid."
substances.
e.
g.,
'
'
Therefore
we may
81
molecular weights."
On
closer
inspection
We
must therefore
reject
ment.
them and
this
In
was
thermodynamics to
it
To understand
we shall
He
its
He
82
THEORIES OF SOLtTTIONS.
retical deductions
water.
We now know
quite well
on
how important
the
hands of van't
were later
Hof. Raoult (1878 and 1882) deduced these laws
experimentally a little while afterwards and found the
true law of depression of the vapor-pressure:
similar deductions
log.
Pi
in the
N + n'
Another great advance was made in 1869 in Horstmann's application of Camot's theorem (or its special
form, the formula of Clapeyron) to the evaporation and
simidtaneous dissociation of sal-ammonia, and he calculated its heat of evaporation from the observed vaporpressure and found it to correspond very well with that
experimentally determined by Marignac. The calculation was exactly similar to that by which the heat of
evaporation of water is found from its vapor-pressure at
different temperatures.
by him
from
dlog p
is
ART^
dt
where p
2T^
temperature,
the absolute
heat of dissociation of
plified to
83
gram.
if
is
and q the
This formula
is
sim-
AR =
2 (better 1.985),
above.
THEOEIES OF SOLUTIONS.
84
But his important deductions were concealed in academwhich were only very httle known
and therefore did not exert any sensible influence on
In 1882 Helmholtz independscientific development.
ently wrote his well-known memoir on "free energy,"
ical transactions,
problem
failed, until
But the
last
if
year before
this,
p and
if
A similar expression
temperature as
is
formula.
85
directly
Pfeffer
De
is
same number
of
NaNOa
cells.
KNO3
But
and
same
same
cells.
Now
precipitated in the
86
THEORIES OF SOLUTIONS.
water and no water was pressed out from the solution of cane sugar through the cell walls. This pressure,
the so-called osmotic pressure of a solution of 1 per cent,
tilled
when
It is nearly-
the sugar-solu-
this is changed.
These results of Pfeffer's measurements were communicated to van't Hoff by his friend De Vries, who
asked for a theoretical explanation. Van't Hoff made
the following simple calculation.
gas containing
solution
(as
in
Gay-
As soon
same volume.
Hoff applied
all
same number
of molecules in the
87
was
stated, van't
from thermodynamics
for saturated vapors,
stances.
able to deduce
on
law of Raoult
little later
deduced
De
Vries)
THEORIES OF SOLUTIONS.
88
was found.
The
quantity of water.
To account
for
this
difference,
efficient)
its
form
first
(of 1864).
it
really spoilt
matter, but
it
of electrolytic dissociation.
of
introducing
the
coefficient i:
"Thus
it
and
theoretical deduction
of the
89
rii,
molecules of
is
valid
temperature):
U = nu+niUi+n2th+n-iU3+
where
is
same proportions.
The same
evolved.
of gases in the
expression
behavior of salts
is
The abnormal
due to a dissociation
of their
molecules.
The weakness
it
might
be that the expression quoted was true only for solutions so extremely dilute that they were not capable
of being
measured.
by means
of
thermodynamics
"nothing
could
be
and that
to this
significa-
tion."
90
THEORIES OP SOLUTIONS.
By
attacks
gave
a strong support to the new ideas in the eyes of chemists
and of scientists in general, and this was of a value
which should not be imderestimated, especially during
the first years of the growth and propagation of these
ideas, which otherwise seemed revolutionary and therefore evoked a rather determined resistance.
of physicists.
LECTURE
VI.
different roads,
modern theory
which have
of electrolytic
one,
first
entered upon
by Gay-Lussac,
through
salt solutions.
Under
rise in capillary
When
salts in
91
THEORIES OF SOLUTIONS.
92
which it is
most clearlyadditive scheme, which
bound
This
is
same number
we
The same
so forth.
is
and sulphates,
As an example
normal
solutions.
(The diameter
of the glass
15
C):
NH4CI
60.9,
KCl
56.9, Yi
CI -Br:
NH4 2.2,
CI-I: Li 3.8, K
CI-SO4/2: NH4
CI-NO3: NH4
The
K 2.2,
3.9,
J^
Y2
Cd
2.0,
Ba
3.8,
Yi
Mean
Zn
K 1.1, Na 1.2,
1.1, K 0.9, Yi Sr 1.1,
1.2,
2.1.
4.1,
Yl
Zn
1.1,
Yi.
Yi.
1.2.
may
be calculated.
The
third line
is
60.9-2.2
58.7, of
KBr
2.2
57.1
measurements.
93
Valson has drawn some conclusions from his measm-ements which I cite verbally because they have sometimes been misunderstood, which can well happen, as
many technical terms were used in a different sense
than now. He says: "Experience shows that the
effects
to the
but this
is
each other.
It therefore
seems that
may
it is
to
by Mr. Henri
of sufficient
be regarded as having
It is
something analogous
stated
necessary that
medium
phenomena
as
Sainte-Claire-Deville, according
different substances
do not
effects,
if
Here there
is
not observed.
more emphasized
is
THEOEIES OF SOLUTIONS.
94
this
This conclusion
ment
is
rather confusing,
really
with temperature.
and therefore we
shall
come back
to this special
The
capillary height
is
normal
solutions,
specific
is
subject
normal
solutions, or better,
when Valson a
It
which
is
generally
69 above)
whereas in reality
of a salt in water
it is
95
only 22.3
cal.
c.c. is
about 150,000
cal.,
this,
they stated
"which
it
would be
difficult
to define
original
e.
g.,
of
volume.
when we say
an
infinite
its
consequences
been
oo
above and
<
below
this
temperature.
that the
but that
is
NaCl
into Na
and CI.
We must therefore say that the ideas which have been
developed by Favre and Valson are rather far remote
from the theory of electrolytic dissociation.
pretended decomposition
On
of, e. g.,
was shown
in
many
THEORIES OF SOLUTIONS.
96
cases.
index of solutions,
of salts stated
by Hess
as
early as 1840.
properties of
salt
first
the
due to
For the relative compressibilities of 0.7 normal salt
= 1,000) they found the
solutions (that of water
following values
The
relative molecular
volumes
of 1.5
97
normal solu-
tions were:
NH4
I
Diff.
Diff.
Dlff.
Li
Diff.
THEORIES OP SOLUTIONS.
98
tially
property
is
which the
cals of
salt is
composed.
The molecular
smn
of the lowerings
20,
i. e.,
35, it
was observed
to be 35.8; for
be 8
aluminium
+ 6-20 = 128,
by De
99
on
them are
the
which act as
it is
if they
were simply
no necessary consequence
nevertheless confirms
it
It indicates
in its principle.
proper characters."
That there
tion
(it is
is
in reality
no question of a
particles,
real dissocia-
i. e.,
this
weak
were the
case,
acids (such as
HCN, CH3CO2H,
H2C2O4) always
of their molecules
Salt.
THEORIES OF SOLUTIONS.
100
Salt.
101
of
that the
same degree
weak
acids such as
acids
and
salts of
HCN) up
monovalent ions
exceptions,
in high dilution).
e. g.,
water, ammonia,
is
unity,
all
possess a
is
to unity.
As
displacement of chlorine by
NO3
or
OH
in dilute solu-
tion, in
formation
their
This is
easily done by aid of the tables given by thermochemists. The results of such calculations were given
following solution in a great quantity of water.
by myself
cal.)
THEORIES OF SOLUTIONS.
102
CI-NO3:
NOa-Br:
Br-OH:
OH-I:
The
Max.
%C&
Tl
Na
-19.9 -13.9 -13.7 - 9.6
+33.5 +24.4 +25.5 +16.9
(-49.6) - 8.1 - 6.1 -15.7
(+64.1) +23.1 +32.8 +26.8
aSi
14B
Dlff.
mann.
Compare
this table
KOH
HBr
or HI
HNO,
CI,
NaOH
LiOH
KOH
103
(nearly)
additive property.
is
the
first
one (1839)
C2H5OC2H6
latter is
therefore
is
proposed by BerzeUus.
first
stage
HOH
ether
is
the molecules.
that, in
all
in a
mixing two
Lussac maintained
(cf.
p. 75 above).
THEORIES OP SOLUTIONS.
104
Thus
H.Cl, an atom
same atom
H does not
of chlorine
another example:
if
we mix a
He
gives
still
again.
is
it.
For
in
changes of radicals
the
the
of his
solutions
these
electrolytic
we now say
ions
^go
on instan-
All attempts to
measure the velocity of reaction in cases, when electrolytes exchange their ions, have been in vain on
accoimt of their extreme rapidity. On the other hand
similar reactions, in which non-electrolytes (or perhaps
better stated extremely
weak
we shaU
such as CI,
CN, NO3,
105
CIO3,
tricity.
What
now happen
will
if
we
place a solution
The
left
as in the molecules in
a majority of the
HCl
2,
Une
2).
Or
at
their
left,
^o
^H
HCl
Ha
O*
COHH O*
CO
CI H
H
CI H
vo H CO H cr%o H cr^
90
CI
CI
0H
CI
0H
CI
CI
CI
CI
CI
o
Of,
CI H
H
CI H
90
^O
*0
CI
HCl ^ H CI
O* o
CI
Fig. 2.
Grotthuss' chain.
THEORIES OF SOLTJTIONS.
106
by Clausius
in a
memoir
of 1857 without a
Clausius tried
the law of Ohm may hold for electrowhich had been proved by experiment.
Ohm's law demands that even the least electric force
Hence if these were
causes a motion of the ions.
to explain
how
lytic solutions,
bound
was and
just this
is
minimum
would be necessary
this
is
an
electric current;
law.
Clausius drew
for establishing
in contradiction to
Ohm's
ions
supposed.
and secondly on the violency of the molecular movei. e., on the temperature."
ment,
then,
and perhaps
partial molecules
"The
relatively seldom,
(i. e.,
molecules
it
now and
an exchange
of the
explained in an unconstrained
way by
is
this theory,"
movement must
107
contribute to an increased
Of course
it
must be regarded
as very
much
strength-
their concentration,
whereas
it
i. e.,
number
of
to the square of
really increases
more
Also the
by
the
The renowned
Italian physicist
current.
THEORIES OF SOLUTIONS.
108
trolysis,
disappears slowly
by means
of diffusion of the
theory
is
The
is
first
and was
fur-
demands that the degree of dissociation is proportional to the third power of the acting electromotive
ther
force, that
is, if
no electromotive force
is
acts, it is zero
to a Hmit, which
inactive molecules
and tends
is
ones.
109
by Kohlrausch
is
not
An
position.
acid
At
all electrolytes of
is
whatsoever com-
its
con-
have the
same strength. These assertions were demonstrated
to be in accord with the thermochemical measurements
of Berthelot and Thomsen.
Similar rules are valid for
bases.
Chemical activity therefore coincides with electrical activity.
Water, alcohols, phenols, aldehydes,
exchange
etc., which
ions with electrolytes are also
ductivity
is.
The relative conductivity of water inmore rapidly with temperature than that of
electrolytes.
creases
The
results of
Thomsen's,
measurements
of chemical equilibria
their discrepancies
their salts
which
is
is
consumed
quantity of water.
in the activation of
The
an equivalent
value
is
THEORIES OP SOLUTIONS.
110
Therefore
by means
of ordinary reagents
on
iron,
which are
all electrolytes.
When this memoir was written (1883) the measurements of Raoult on the freezing point of salt solutions
had not appeared. Therefore it was regarded as too
bold to state verbally that the active molecules were
dissociated into their ions and it was only maintained
that they should be subject to the conditions demanded
by the hypothesis of equipollency. Soon afterwards
Raoult's aforementioned measurements were published
and their theory given by van't Hoff (1885). Immediately after that I calculated the coefficient of
of dissociation
tion.
with dilution.
is
proportional
Ill
Ostwald, Planck and van't Hoff and Reicher simultaneously and independently of each other appUed the
law of mass-action on the equilibrium between ions and
undissociated molecules of an electrolyte (1888). Ostwald found that this law really holds good for weak
Van't Hoff and Reicher were not content with
acids.
the figures already published regarding the conductivity
weak
called
acids
for
finally did
law to
this
special
Planck
not succeed
salts,
sociated electrolytes
still
Later on (1894)
persists.
is
weak
bases.
From
(cf. p.
83 and 84) I
ent
in perfect agreement
Kohlrausch
and Heydweiller did the same work for the most important and most difficultly determined of all examined
In two new memoirs I deelectrolytes, namely water.
termined the general laws of equihbrium between elecOstwald demonstrated the extreme usefultrolytes.
new theory for general and analytical
the
ness of
chemistry.
(1900 and 1904.)
The
LECTURE
VII.
VELOCITY OF REACTION.
The
first
was that on
cane-sugar investigated by WiUiebny,
the inversion of
in a solution
depends upon
it.
It
by
water, heated
by a
spirit
flame of constant
size,
or at
with water.
is
proportional to the
VELOCITY OP REACTION.
113
much
longer time).
As an example we
cite
nitric
acid at 15 C.
Time
of
ir
THEOBIES OP SOLUTIONS.
114
that the exceptional behavior, found by Henri, depends upon the abnormal rotatory power (the so-called
mutarotation) of the components of invert sugar, when
The
values of x,
sugar,
of
e.,
by great errors.
by adding a trace of
i.
the
were therefore, in
It is
alkali
disttu-bances.
The
light.
said hydrolysis
Most
sess the
same
is
(i. e.,
by
by
ultra-violet
enzymes.
also caused
High temperature or
VELOCITY OF KEACTION.
115
in the
Zymase transforms
it
is
of
(i. e.
hydroxyl ions)
that sunhght
is
KOH
They
boiled
of sunlight.
HjO = C6H12O6
water
2) CeHiaOa
-h C6H12O6 (catalyzer
glucose
H-ions or invertase or
laevulose
light).
= 2CH3CHOHCOOH
glucose
namely:
(catalyzer
OH-ions
lactic acid
or light or yeast).
3)
CaHeOs
lactic acid
= CaHeOH + CO2
alcohol
(catalyzer
OH-ions or
carbonic acid
Hght).
THEORIES OF SOLUTIONS.
116
when
H2O.
Thus
for instance
which accelerates
it.
copper in
Therefore
if
nitric
if
we
dissolve
formed, which
we put
pieces of
is
at
in,
first
weak
and
properties as
Madsen
found.
cane-sugar
by
degrees.
is left,
VELOCITT OP REACTION.
117
At first the hydroxyl ions of the water produce saponification just as bases. The product, acetic
of water.
more
slowly.
gen ions of the acetic also cause a saponification although they are not so active as the hydroxyl ions (they
act 140 times less), and when they have increased to a
sufficient
is
many
accelerated after
when
it
the hydrogen-
as the hydroxyl-ions.
This
g.,
bacteria,
e. g.,
coli bacilli,
number of
bacilli increases
according
THEORIES OF SOLUTIONS.
118
tity
may
reaction
The
present.
means
Now
formed.
the
number
is
followed
ammonium
by
acetate
ammonium
is
tity.
dx
dt~
where
is
K{A x) p
'
the quantity of
the
When
compared with
we
is
small
obtain:
xdx
= KAPdt
or integrated:
x^
This formula
tells
the quantity of
= 2KA .P.t.
ammonium
acetate
is
proportional to
The
figures,
t
is
n. ethyl
t
acetate at
z
obs.
calc.
14.8 C.
17.S
VT
VELOCITY OP BEACTION.
119
The time
50
p. c.
holds good.
The
is
time
is
and holds
for a great
digestion
by means
pro-
and
number
amongst others
lytic action of
Upases on
figures given
by
fats, etc.
Schiitz
may
As an instance some
THEORIES OF SOLUTIONS,
120
is
is
it is
have
we may
laid so
good
for
simple
this rule
it
The deduction
of
soon as one
is
nearly in-
also given
a formula which
formed again in a
Thus
for
instance, according to
1)
2)
CaHsOH
or taken together:
2C2H5OH = C2H6OC2H6
H2O.
VELOCITY OF EEACTION.
121
acid.
when a
is
very
much
retarded
He
The
an interval of 10 C.
to 3.63
is
CaHeHSOi) and
their increase
Hence we
hampered in a high degree
water and that in the higher degree
by the presence
of
is
is.
temperature
in
reactions.
In any case
that
greater
THEORIES OF SOLUTIONS.
122
ally
by Rutherford.
In some
cases, as
very beginning
Then the
is
may
esses
their
monomolecular, bimolecular,
to
the number
etc.,
reactions according
by the
VELOCITY OF BEACTION.
123
them a
istic.
In
many
cases, especially
is
is
character-
of
is
The
velocity k of reaction
is
then:
= B;K =
ko 10-'.
correct.
Temp.
8
85
100
170"
The
values given
if
his formula
by him are
k (obs.)
0.0004
0.074
0.17
8.50
0.0004
0.0456
0.115
(calo.)
8.50
B
0.0281
0.0307
0.0243
124
THEORIES OP SOLUTIONS.
The value
of
dlogk
~dT~ =
where
is
2^
log ^i=
a constant and
Ti-To
rpj,^
+ log
,
A;o
perature.
formulas above.
rilog k
dt
_A
T''^
^'
pirical
It
number
of empirical
VELOCITY OP KEACTION.
125
studied
2CO = C02+C,
which according to the chemical equation ought to be
bimolecular, as 2 molecules of
CO
The
1)
CO = C+0,
2)
C0+0 = C02.
is
Reduced
340.
300 abs.
to
found to increase
between 256 and
= 27
The extreme
values of the
to 1.77 at 27 C.
differs rather
by means
The temperature
of acids.
much
of esters
coefficient
of
was determined by Price. The proporreduced to 300 absolute and a 10 interval is about
2.35 for ethyl acetate and does not differ much for
these reactions
tion
1 to
The experiments
of
Kremann
namely
1 to 4.1 for
THEORIES OF SOLUTIONS.
126
solution the
first
error
is
all
(The experimental
C2H4
If
is
+ Br2 =
CzH^Brz.
it
gives
much
is
e. g.,
if
all
values are
to 300 absolute.
Hoff's rule.
that
A =
The second
0.
dilute acids.
is
when
chloric acid.
He
VELOCITY OP REACTION.
127
errors.
for 1.3re.
HCI
THEOEIES OF SOLUTIONS.
128
1 to 1.21
1 to 1.01
1 to 1.39
1 to 1.36
.
to 1.20
1 to 1.12
Reaction of oxalic acid and mercuric chloride.
The photographic process with silver bromide
.
1 to 1.00, to 1 to 1.03
gelatine
The
which
alters
very
little
with
2HI = H2
which reaction
is
I2
tion
by means
vaUd
on decomposi-
of
equation:
HI =
H+
I,
i. e.,
From
by the
and
I to
tively.
or I respec-
VELOCITY OF REACTION.
129
little less
vibriolysin,
The destruction
about 60.
On
the other
with other
hand the
approximately
by temperature.
It
is
10
THEORIES OP SOLUTIONS.
130
value of
an increase
of temperature of 10 C.
LECTURE
VIII.
As we have
gram
of
ammonia gas
at 20 214 cal.
These calcu-
considerations of
the
thermal
effect, leads to
no
and evaporation.
These deductions concern the heterogeneous equiUb-
of solution
131
THEOEIES OF SOLUTIONS.
132
its solution.
Much more important are the homoHorstmann had deduced the laws
and these are of coiKse
geneous equilibria.
The
ether.
reaction
cases
The
results of this
a homogeneous equihb-
(m
+ x)x =
4(1
x){n
x),
where x
and according to van't Hoff's law also for the disAnother example was the determination
the dissociation of nitrogen peroxide N2O4 into 2NO2.
state
solved state.
of
ments
of
CimdaU
In such experi-
determined colorimetrically.
The experiments
was
agree
133
success.
and
For all these so-called strong electrolytes van't Hoff gave an empirical formula, namely:
acids
bases.
much
greater
number
As
there
now
exists
really the
theory.
munber
we
are able
great degree of acciiracy. As these play a very important role in nature, as well in the waters of the
THEORIES OF SOLUTIONS.
134
and oceans, as
humors
in the
upon
The
of
little
this chapter.
is
performed
may be
written as the
by means
of the migration
They have
64.6,
67.5,
Cs
Kohh-ausch).
Ag
54.3,
MMg
Br
Rb
46.0,
yiZn
NH4
68,
46.7,
OH
174,
Tl 66.0,
YzPh
Na
61.3,
43.5,
315,
Li 33.4,
J^Ba
55.5,
46.6, CI 65.5,
67.0, 1 66.5,
33.7,
64.2,
45,
CH3CO2
i. e.,
the
creasing temperature as
figures calculated
pupils:
his
Temp.
18
100
64.6
206.5
Na
NH4
43.5
154.5
65.2
207.5
Ag
52.3
183.5
J^Ba
53.4
201.5
i^Mg
55.9
177.5
313.5
642.5
CI
65.5
207.5
H2PO4
24.5
87.5
NO,
63.5
183.5
J^SO,
58.2
248.5
CHsCOj
34.6
OH
173
130.5
339.5
156
312
242
315
295
325
287
772
313
158
275
403
208
593
135
306 C.
218
412
347
428
402
462
427
852
413
281
502
467
560
520
501
656
549
784
877
503
864
660
378
653
313
713
464
958
413
516
1165
474
weak
acids.
The
is
non-dissociated part (1
most
a) follows
i^it^u
of the valencies Vi
and
136
Vi
THEOKIES OF SOLUTIONS.
of the
two
tive table of
Type
ions.
Noyes gives the following
(1 a) expressed in per cent.:
Eq. per Lit.
instruc-
The conductivity
137
of the ions
conductivities at 18 in 0, 50, 80
of alcohol are the following:
Per Cent. Alcohol.
THEOEIES OF SOLUTIONS.
138
is
Per Cent
139
figures
added
There-
not
less
cent.).
The few
figiires
in the
red.
under
This observation may be explained in the following
manner.
The wandering
of the ions is
The
(of
hampered by
water or alcohol).
OH
and
may
set the
continue to carry
away
positive electricity.
it
It is
If another
water
molecule,
the effect
ion than
or
or OH in a water molecule
of an exchange with the
would be the same as a decomposition of the water into
H- and OH-ions, which would be accompanied by a rise
OH
hits the
which
is
impossible.
As the
alcohol
140
THEORIES OP SOLUTIONS.
but in
all
the
is
alcohol-molecules
so
to
insignificant
tivity
has long been maintained that the conducproportional to the fluidity. The change of
It
tions.
is
dilute salt-solutions.
two
the water.
and that
The main
this
difficulty
complex moved in
much
18
C. on, respectively.
tivity
is
is
The
of the conductivity
The same
is
taken as unity.
A
Fluidity
at 18"
180
100
156
1.000
5.894
2.863
HCl
379
1.000
3.717
2.243
NaOH
216.5
1.000
2.743
3.856
Ba(0H)2
222
1.000
2.905
3 815
(fl
141
A at IS"
18
100
156
KCl
NaCl
AgNOa
NaCHsCOa
130.1
1.000
3.183
4.805
109.0
1.000
3.322
5.092
115.8
1.000
3.168
4.921
78.1
1.000
3.648
5.761
BaNjOs
116.9
1.000
3.294
6.133
KzSOi
132.8
1.000
3.426
5.388
is
not too
much
changed.
The
trivalent La-ion
Na and
K.
water.
to
in
in
two monovalent
ions,
type KCl,
(3) salts of
monovalent
The experimental
BaCU.
THEOBIES OF SOLUTIONS.
142
Flaidlty.
Acetone
19
Methyl alcohol
21
26
26
30
Ethyl ether
lit Group.
2iid Group.
15.6
3rd Group.
4tli
Group
16.7
19.0
16.2
16.2
17.5
19.2
18.0
16.3
19.9
21.4
20.9
18.8
21.2
21.1
Ethyl alcohol
n-Butyl alcohol ... .30
Isoamyl alcohol
31
18.8
23.4
25.1
23.9
18.4
22.6
27.9
24.1
17.2
21.6
26.7
n-Propyl alcohol
.32
Isobutyl alcohol
33
Glycerol
33
Isopropyl alcohol. ..36
Dextrose
40
Galactose
40
19.5
27.3
27.8
27.0
19.5
24.4
28.0
26.5
20.5
22.7
26.0
25.0
20.3
25.6
27.7
26.9
25.0
24.4
29.9
33.4
30.9
Allyl alcohol
Mannite
Cane sugar
43
46
With weak
salts,
22.9
23.2
acids or bases
and
slightly dissociated
sociation
is
etc.,
the dis-
perceptibly diminished
ammonium
that
it
fluidity,
25 C).
225
200
172
165
138
124
120
96
Acetone
0.00316
Acetonitrile
0.00346
Acetylchloride
0.00387
Propionitrile
0.00413
Ethyl nitrate
0.00497
Methyl alcohol
Nitromethane
Methyl rhodanide
Ethyl rhodanide
0.00580
0.00775
84.5
0.655
Acetyl acetone
0.00780
82
0.640
0.00619
0.00719
0.711
0.692
0.666
0.682
0.686
0.719
0.743
0.690
0.00860
76
0.654
Epichlorhydrine
0.0103
66.8
Ethyl alcohol
0.0108
60
0.688
0.648
Benzonitrile
0.0125
66.5
0.706
Furfurol
0.0149
50
0.745
Diethyl sulphate
Dimethyl sulphate
0.0160
0.688
Nitrobenzol
0.0182
Benzyl cyanide
Asymmetric ethyl sulphite
Ethylcyanacetate
0.0193
43
43
40
36
0.0176
0.628
28.2
0.705
25
25
0.802
22.5
0.760
0.0422
16.5
0.696
0.0321
Anisaldehyde
ca.
(Glycol
0.1679
(Water
0.00891
and
1.32)
112.5
1.00)
is
K in ethyl
e.,
i.
0.703
ca.
0.695
0.0250
0.0281
Na
0.728
26.4
Formamide
This value
0.757
.0.0238
Salicylaldehyde
Anhydride
CI,
143
is
the vis-
Hence
ij
In the
table regarding the conductivities of ions the proportion between this magnitude in alcoholic
solution
tation 0.324,
CI
0.363,
OH
for
is:
Na
0.094,
0.324,
Salicylation
0.101,
in
aqueous
0.312, Ace-
(C2H6)2NH
0.352,
Cyanacetation
0.411,
0.329,
0.394,
and
NH4
eport.
the
The
difficulty
solutions.
tionally,
discrepancies
of
The
and
ions
OH
may
serve as a proof of
OH
and
144
THEORIES OP SOLUTIONS.
may
weak
and CaHsO.
Dutoit and Duperthuis investigated the relation
between
fluidity
and conductivity
of
Nal in different
They found the
27.95
11.85
Ethyl
/!
at
W
W
at
0.495
at 60
0.457
In
all
Ace-
Pyridine.
tone.
42.10
5.48
4.49
0.453
0.441
0.374
0.573
0.443
0.397
0.269
0.562
12.75
0.502
0.517 (at 40)
sinks
;/*
increasing
temperature,
water,
tj/z^
for
KI
to be
(,at
18)
which
is
the order of
tj
Con-
salt
of temperature.
solvents
He
found
The
is
done in most
cases.
asymptotically,
down towards
when
the
temperature
sinks
The same
true
is
The
145
(/)
if
being constant simultaneously decreases in the proportion 3.5:1 and 3.7:1 respectively.
to a value of
of
This corresponds
At 45 the value
lytes according to
nitrates
11
0.75.
of
lithium,
THEORIES OP SOLUTIONS.
146
at temperatures up to 500.
The conductivity is
not strictly proportional to the temperature, but
increases less and less rapidly as the temperature rises.
is
reciprocal
reproduced.
TempC
500
600
700
CaCIj
KCl
KBr
KI
800
900
1000
1100
1.90
2.32
2.66
(2.86)
2.19
2.40
2.61
1.75
1.95
1.39
1.64
(2.15)
2.56
2.70
2.83
(2.97)
4.48
4.76
4.98
5.14
3.18
3.34
3.50
3.68
2.52
2.64
0.30
0.55
2.72
0.80
1.30
1.54
Nal
AgCI
4.20
AgBr
Agl
NaPOj
3.02
(2.40)
(1.55)
7.10-'
B2O,
NaCl
1.05
21.10-'
3.34
SrClj
The
in
3.66
1.98
46.10-'
(3.98)
2.29
2.57
temperature.
The
conductivity of
KCl
or
NaCl
is
that of
still
and the
silver salts
more
slowly.
147
The conductivity
of CaCU and SrCl2
mean value
of the conduc-
tivities of
c concentration in
lent conductivity,
X
viscosity):
THEORIES OF SOLUTIONS.
148
this ir-
to
the presence
traces
of
explained as due
is
impurities,
of
especially
most
lytic
dissociation.
and Archibald,
who
by
Steele,
Mcintosh
and
acetone, in HCl,
that
dissociation of
compensated by
the conducting
may be more
than
The
KCN in acetamide.
They
fi
V Uters
at 282 C. for
of
HgCU
y=
149
THEORIES OF SOLUTIONS.
150
V=
0.999
151
is
cases,
one containing a
percentage of
less
ammonia
NH3
compared with that of the ions combined with smaller quantities of ammonia, just as the
4ons rich in
as
in aniUne,
some
tion.
to those observed
by Franklin.
Kahlenberg
the
abnormal
regarding
conductivity
Ruhoff
of
and
of Franklin similar older observations of
solutions of
silver
understood.
The
nitrate in
amylamine are
made by
assertion
easily
these authors,
molten mixtures of PbCU and KCl there exist compounds 2PbCl2 KCl, PbCU 2KC1 and PbCU 4KC1.
.
THEORIES OP SOLUTIONS.
152
One
of the
seeming discrepancies
Another of
in the one case as well as in the other.
the most experienced men in this field, Walden, has
expressed the same opinion in nearly identical words.
applicable
all
LECTURE
IX.
EQUILIBRIA IN SOLUTIONS.
The
is
that between a
gas and
NH3
or
CO2
the law
is
not
exact.
similar law
bisulphide of carbon
(at 18 C.)
Gram
Gram
I in 100 ex.
I in 100 CO.
0.032
12.9
1:403
0.016
0.010
0.009
6.6
4.1
1:412
1:410
0.76
1:400
of iodine in water
bisulphide of carbon.
and that
in
made by Ber-
thelot.
two
it
freezing point of
In such circum-
THEORIES OF SOLUTIONS.
154
not hold.
Nernst unproved
molecules.
is
If for instance
sists (chiefly) of
it
simple molecules
CeHsCOOH and
in
2C6H6COOH
and the law
(in
of
(concentration in water) ^
constant (concentration in
benzene).
(g.
in 100 c.c).
electrolytically
and
of
and vice
versa,
and
is
this quantity
centration.
The
which
itself
a dissolved substance in a
possesses
a perceptible vapor
and
NH4OH
in aqueous solution.
NH3
If
between NH3
namely this is
EQUILIBKIA IN SOLUTIONS.
155
THEORIES OF SOLUTIONS.
156
evidently (1
NH4
+ fe) ^
:
z"^,
if
ally done, is
NH4OH
5.10-* at 20 in the
equilibrium equation ky
NH4OH, as
\-
y oi
is
gener-
NH3 and
together.
The law
For
is
soluble in solid
and
in liquid
is
Other
in naphthalene
ammonia
in water
and
in red blood-
We
we know
as much
to
compound
just
some substance
it
is
in
157
EQUILIBEIA IN SOLUTIONS.
the liquid in which
it is
suspended.
which are sensitive to them and of so-called immune-bodies in red blood-corpuscles. In these two cases
a high degree of specificity prevails so that only a certain
teria
agglutinin
is
bacterimn,
e.
g.,
coli-agglutinin
by
by a given
by Bacterium
coli,
and a certain
kind of red blood-corpuscles takes up a given immunebody, namely corpuscles from that species of animals, by
the injection of whose corpuscles in the veins of another
animal the immune-body in question has been produced.
cholera-agglutinin
cholera-vibrions
the reagent.
tain only
cule of
two
it
thirds as
in the
much
smrounding
fluid.
It
was urged by
A=K.
where
its
is
C-",
that an adsorption
might be true
phenomenon
fluid, indicates
This
but in the
prevails here.
more of which
no example in the adsorption phenomena,
except perhaps at very small concentrations, where
proportionality rules between A and C.
The most important of all equihbria between dissolved substances is that proved for weak acids by
of
there
THEORIES OF SOLUTIONS.
158
of
from each
the molecules from which two
molecule, or at least
is
dissociated off
equilibrium
is
with dilution.
may
also act as
weak
bases,
so that a salt-like
The
dissociates into
simplest of
them
is
water, which
acids
Most
amido
EQUILIBRIA IN SOLUTIONS.
thereby giving
NH4OH.
The molecule
159
OH
NH3-
from
NH3
dis-
and H-ions
from its COO-side. It may even give off both and
then be regarded as an "inner salt." Bredig was the
first to study these interesting substances and he insociate off hydroxyl-ions
its
side
duced his pupil Winkelblech to continue this investigaThey used the conductivity and the hydrolysis
tion.
of the salts of these electrolytes to determine the dissociation constants of the
two
Finally
160
THEOEIES OF SOLUTIONS.
is
constant
K,
molecule
is
diluted,
and k
OH-
e. g.,
volume
is
in
The meta-acid was measured by Winkelblech and calculated by Walker, the ortho-acid was measured and
calculated by Lunden.
It is obvious
constant" k
is
from the
is
really
These
called k^ (the substance regarded as a base).
two constants were: for the meta-acid k = 1.63.10-^
and k, 1.23.10-", for the ortho-acid k, = 1.06.10-^,
k^
1.37.10-^^.
k^;
dissociation of H-ions
acid
is
The meta-
and as a base.
Rather remarkable
is
constant between t*
istic especially
when
64 and
k^
exceeds very
is
nearly
is
character-
much
the value
256, this
same temperature.
EQUILIBRIA IN SOLUTIONS.
there are just as
many H-
as
OH-ions in the
may
161
is
be rather high,
k^
solution.
independent of
is
is
e.
g.,
0.667, for
for
yet known).
40 and histidin k,
2.2.10-'
and
k^
5.7.10-' at 25.
as albumine
seem
The same
is
which
for
still
more
k^ is
from eggs
be more
more easily
also to
and
for tyrosin,
leucylglycin,
alanin,
and
alanylglycin and
k^,
mins, investigated
by
The chief
objection,
elec-
12
If
THEORIES OF SOLUTIONS.
162
salt is
marked
in
therefore
my
inaugural dissertation.
The two
ions
The
if
diffusion of salts
rate of diffusion
is
may
Nemst, proceeding further along the same lines calculated the electromotive forces, which arise through
the unequal diffusion of the ions in so-called concen-
EQUILIBRIA IN SOLtTTIONS.
163
which had been before treated thermodynamically by Helmholtz. In this case the powerful
charges of electricity, which in a free solution hinder the
unequal diffusion of the two ions, are carried away
tration
cells,
by means
of
The
and
results
mathematical
solution at
an
of
Pleijel,
who has
its
difficulties
earlier stage.
of diffusion
its diffusion
con-
is
THEORIES OF SOLUTIONS.
164
The
diffusionconstant
was now
2.50.
According to
The explanation
that
is
(i.
e.,
the
is
forces
dissociation constant
is
is
complete.
This phenomenon
is
EQUILIBRIA IN SOLUTIONS.
not be explained,
we suppose
if
165
salts
ions.
not to be
It is
in
supposed that
They found
experi-
(e.
g.,
others retard
it
NH4CI
(e.
ZnCU
g.,
in the
same
reaction).
proof.
Therefore at
many
terms and
a later stage
coefficients having reference to the foreign substances
result.
It
higher concentrations or
if
is,
the
carries their
name, was
for
But
nevertheless
it
THEORIES OF SOLTJTIONS.
166
we now know be
and it was
therefore quite natural that Guldberg and Waage
of rather different kinds
The
simplest case
complicated riddle.
this
is
Then a part
bound and the acid sulphate is formed.
is
On
Quite different
acids.
The
is
velocity of inversion
by means
of 0.25
c.)
and 15.48
This pe-
The
greatest action
by
acetic acid)
this case,
if
is
exerted on
is
/3
= K{1 -
is
of
V Uter
<x)V
is
in
equiUbrium holds:
a(a-f-n/3)
where
n gram-molecules
(e. g.,
(e. g.,
acetate).
In
gram-molecule of acetic acid with
NaCHsCOO
(p. 179).
acids
sodium
their salts
we have
weak
fi
1).
The
greater n
is
is,
is
very
1
the less
nearly pro-
EQUILIBRIA IN SOLUTIONS
portional to a.
velocity of reaction,
n=
167
when
F=
4:
THEORIES OF SOLUTIONS.
168
(NaOH,
Obaerred.
0.76
Nitric: dicMoracetic
HydrocMoric: dicMoracetic
.0.74
0.24
0.69
0.26
0.69
0.31
0.31
0.29
0.69
0.31
DicMoracetic: lactic
0.91
0.09
0.95
0.05
TricMoracetic: monocMora0.91
0.09
0.92
0.08
0.46
0.56
0.44
0.24
0.75
0.25
0.80
0.20
0.79
0.21
isobutyric
0.79
0.21
0.79
0.21
propionic
0.81
0.19
0.80
0.20
0.92
0.08
TricMoracetic: formic
0.97
0.03
Formic:
Formic:
Formic:
Formic:
Formic:
lactic
0.54
acetic
0.76
butyric
cetic
'
Formic glycoUc
0.44
0.56(?)
0.53
0.47
Acetic: butyric
0.53
0.47
0.54
0.46
Acetic: isobutyric
0.53
0.47
0.54
0.46
This
is
Water
is
fore it reacts
with
salts,
dissolved in
it,
There-
and hydrolyzes
theoretically that
the dilution.
when
was
dissolved, increased
Uter.
EQUILIBRIA IN SOLUTIONS.
Now
169
of his
of
nitro-compoimds.
from an investigation of
the conductivity of
weak acids
and water.
Wakeman
regarding
in mixtures of alcohol
c.)
from some grave systematic experimental error. Godlewski made very careful measurements on just the same
acids as Wakeman and found that these weak acids
follow the
demands
THEOEIES OF SOLtTTIONS.
170
He
found the
by
10^ for
10 20
95 83
370 360 210
138 131 85
Cyanacetic acid
Bromacetic acid
Wk
10fc
30
57
192
58
4050
3218
60
11
70
4.6
80
90
1.8
100
0.57 0.013
0.05
120 76.5 57.3 29.2 10.7 2.5
35 20.510.2 5.7 1.7 0.43 0.015
is
on further
addition of alcohol.
The
to their strength
is
EQUILIBRIA IN SOLUTIONS.
171
dissociation theory.
LECTURE
X.
The
A very
made
great
num-
1.
friction
with dilution.
action).
4.
ions.
to,
is, if
Now
for
172
we would,
most
way and
still
The
in the
173
this correction
(cf.
p. 133),
equihbrium
"constant" would increase still more rapidly with concentration for very dilute solutions, below 0.1 normal,
Yet
Jahn advocated a theory that the ionic friction increases
very markedly with dilution, e. g., by about 13, 10 and
8 per cent, for K, Na and H ions, when they are diluted
from 0.0334 normal solution to infinite dilution. Without further explanation, this hypothesis to which we
come back a little later, seems inadmissible.
the correction would be of very small importance.
The
move
solutions
equal to
and
this hypothesis
is
Now
monovalent
ions,
174
THEORIES OF SOLUTIONS.
constant of dissociation.
Now
by
the
is
supposed to be
proportional to the concentration Cj of the ions, but
according to the electrostatic attraction theory it ought
to increase more slowly.
If it were proportional to
Ci'^^, we would find again the rule found by van't Hoff.
In reahty it increases according to another law and
does not fit very well with the experimental determinations.
The greatest objection to this theory is, that
it would demand a decidedly smaller lowering of the
freezing point, especially in not too small concentrations, than that calculated from the determinations
of the conductivity.
o,
is
theoretical
is
experiment,
if
is
calculated as
The
by
some
cases,
e. g.,
for H2SO4,
K2CO3,
etc.,
But
he observed
more rapidly
Coppet
in
Where the
1871,
others.
175
remained unexplained.
Riidorff supposed that the said salts, which give a
in opposite direction
bound a
hydration,
e. g.,
number
if
we
This
in 100 molecules of
e. g.,
with about
many
molecules of
Of course the simplest case is that where no dissociai. e., with non-electrolytes.
These
were investigated by Abegg, who found that in many
cases these substances give an increasing molecular
tion takes place,
lowering of the freezing point with increasing concentration; in other cases the deviation
was
Some very
THEORIES OF SOLUTIONS.
176
directions,
i.
of water.
But
e.,
Sackiu*
showed that
at 0 C.
it
was
sugar
(as
is
of
-b) = RT
Noyes.
is
the
cal.)
0.
Mol.
Weight.
1,000!).
Weight
32
46
Methylalkohol
Ethylalkohol
Acetone
Acetamide
Ethylformate
Methylacetate.
58
59
74
..74
50
72
55
58
140
81
Glycerol
92
Chloral
147.5
Dextrose
180
180
Fructose
Saccharose
.342
1,000 6.
106
125
160
210
305
Difficulties arise
because
The
177
been treated in a masterly manner by Washburn in a monograph to which I refer for further intions has
formation.
Tammann
pressiure
of
cane
178
THEORIES OF SOLUTIONS.
to
alcohol
was
pressure of the
nomenon
The presence
of
the
^Evidently
this is the
same phe-
water.
He
is
influence
The
least
in 0.5
by only 4 per
cent.,
the greatest by
lithium chloride which in 0.5 equivalent normal solution gave an increase of 30.5 per cent.
Similar experiments were made with ethyl acetate with similar
results (changing between 10 per cent, for barium nitrate and 30 per cent, for sodium chloride in 0.5 equivalent normal solution).
on the velocity
This velocity
is
179
upon
increased
on adding a 0.5
by means
In saponification
and
The
different
action
is
salt.
The
by the presence
of the salt.
Ha, Oa,
an
may
be explained as due
stances
by the presence
of these salts.
Washburn has
phenomena
substance is in
All these
sure of a
THEORIES OF SOLUTIONS.
180
hand
who
by
the
formula:
A.
where
is
i is
the
A.i
number
+ B.a-
of ions (in
r),
(1
i)
A, is the
addition of the
crystallize
salt,
divided
181
true.
We may
as
same
degree as the salt in the soUd state at the same temperature (under normal conditions).
The constant A,
Of
them
Positive ion:
Density module
Positive ion:
Density module:
Negative ion:
Density module:
Negative ion:
Density module:
the
NH<
Na
Li
Rb
OH
sum
3.37
2.04
CNS
4.38
CjHaOj
2.88
NO,
ClOs
4.56
5.78
of the
4.67
4.06
3.08
3.14
IO3
5.48
CI
3.01
Ag
Cs
10.59 9.70
KBa
}^Pb
6.5310.37
Br
6.67
10.31
16.04
two modules
4.92
5.51
6.53
of a salt's ions, is
ionization
This
is
is
also well
THEORIES OP SOLUTIONS.
182
accompanying expansion Av
ture
by the
t
is
in a rather complicated
table
the base.
The
dependent on tempera-
maimer as
is
indicated
Now
183
may
therefrom
calculated
these acids,
Ostwald.
Subitance.
Formic acid
7.7 c.c.
Acetic acid
8.7
10.5
10.6
Propionic acid
12.2
12.4
Butyric acid
Isobutyric acid
Lactic acid
13.1
13.4
Succinic acid
11.8
11.2
Maleic acid
11.4
10.3
The agreement
is
13.8
13.3
11.8
12.1
contraction.
monia
of
at 15 C.
am-
two combined processes, the formation of NH4OH from the 59.4 per cent.
NH3 and a corresponding quantity of water and then
here be regarded as consisting of
THEORIES OP SOLUTIONS.
184
latter process
of
may
dielectricity
in
constant of water
compression.
mum,
in
its
is
Now
surroimdings.
The
dielectric
its
This contraction
is
ments.
and
electric
185
The
phere."
idea
appUed Stokes'
solutions.
surrounding
of that
Rb and Cs
might therefore suppose that Li should move more easily than Na
in a very dilute solution,
and that more easily than
the viscosity of which may be considered equal to
that of water. In reaUty this is the order of the rate
of diffusion of these metals (9.5 for Li, 7.3 for Na, 4.9
for K, 4.7 for Rb and 4.6 for Cs) in mercury, but the
increases
volume
from the
first
of Li,
Na, K,
to the last.
We
aqueous solutions
is
I give
below
18 and
38
C,
namely
2,
I,,
efficients
multiplied
Kohkausch
by
(Praktische
10^
at
Physik.,
18
11th
according
ed.,
to
1910).
THEORIES OF SOLUTIONS.
186
They
h
O4.10*
Tl
%Ci
3^Cd
34Ra
Br
68
212
66
215
51
46
245
58
239
67
215
Ion.
247
IO4
ClOi
48
64
os.104
Ion.
H
OH
at
31
+ 18.
at
+ 38.
318
174
154
179
203
206
207
215
217
220
223
226
231
231
232
233
236
0.801
1.000
1.196
1.541
1.828
2.078
239
240
244
245
255
256
261
269
61.8
66.4
ClOs
CI
57
Rb
67.9
74.6
65.4
NH4
%S0,
Ag
63.7
HSr
63
45.6
IO3
33.9
C2H3O2
34
57
49
69
54.7
J^Ba
J^Cu
J^ Pb
61.5
Na
J^Mg
43.5
}4Zn
46
Li
33.4
MCO3
70
46.0
The temperature
2.
46
KCs04
63
231
r
at
221
KCM)4
72
CnHeOi
BrOj
56.6
a.lO*.
NO3
is
CHOa
47
SON
ha.
at 18
are:
Cs
Ion.
jp
aj.lO<.
315
174
4.67
5.145
5.59
61.7
4.28
4.79
5.17
66.5
4.99
5.68
6.01
55
4.41
4.86
5.16
65.5
4.29
4.68
4.96
67.5
4.53
4.91
5.17
64.6
4.64
4.99
5.23
64
4.31
4.61
4.80
68.4
5.50
5.81
6.00
54.3
5.68
6.00
6.19
51.7
6.63
6.99
7.20
46.6
8.91
9.38
9.65
33.9
8.96
9.35
9.58
35
5.38
6.58
5.68
56.6
6.27
6.49
6.60
5.05
5.17
5.22
46
61
7.15
7.31
7.37
43.6
6.93
6.91
6.84
45
7.00
6.91
6.82
46
9.68
9.52
9.33
33.4
4.72
4.54
4.39
154
180
205
213
215
216
214
217
222
227
229
247
238
234
238
239
240
244
256
254
265
water
ions with
at
first arises
187
hypothe-
sis,
rises.
As an
at 40 25.7 molecules of
not at
all
H2O.
salts,
rising temperature,*
The
= 68)
great
it
number
Rb-
Na
com-
or Cs-ion.
solid state
Rb
56, and
Cs 71 cubic centimeters.) In the same manner
the F-ion has a greater volume than the Cl-ion and this
is
23.7, for
45.5, for
for
Ostwald at
first
showed
and
It
THEORIES OF SOLUTIONS.
188
The work
diluted
by addition
of water.
The main
parts of the
and determined
to be examined,
if
the concentration
current.
and
The
analytical
resorcine as indicators.
He
electrolyzed hydro-
the electrolysis.
Of course
is
it is
necessary to
know
189
manner as colloids. Indeed there are some experiments by Coehn which seem to indicate such a transport of cane sugar and probably raffinose behaves in
the same manner. In all cases Washburn stated that
with his experimental arrangements no such effect
could be observed.
The
ions,
latter
were chlorides
(of
H,
Li,
Na and
K).
The
The
a differential one.
effect is
If
same number
Therefore
we must
H+
0.28
HA K +
1.3
H2O,
Na
+ 2.0 H2O,
Li
+ 4.7
H2O.
If
we suppose
we must,
as
is-
add
THEORIES OP SOLUTIONS.
190
ity, i. e.,
in this case
65.5
315
0.2
(cfr. p.
134,
The corresponding
figures for K, Na and Li are according to Washburn
Thus for instance if we suppose
1.02, 1.61 and 2.29.
Washburn
+ 6,2.29
18.5.
Hittorf
ions.
Now
Steele
middle
portion
method
is
the
conducting
solution.
This
independent of the concomitant transporta-
of
tion of water.
the
it
191
compared
He
Corrected.
Denlson-Steele's
Method.
KCl
0.482
0.495
0.492
NaCl
0.366
0.383
0.386
The
figures of
for 1
significant.
wandered
salts
also, as
how
the
means
at his
is
at-
soUd
Na
and
is
The
water.
A new
THEOEIES OF SOLUTIONS.
192
96,560 coulombs
is
wji
From
as
is
(1
easily seen:
- wj K =
X.
mined by
determine
x, as
Washburn pointed
n^
if
w^
is
possible to
out, for
+ x/a,
water.
of n^
193
with concentration
(c
tions) is represented.
number
of water molecules
so great
that this
volume
is
accompanying water
propor-
is
accompanying
number of water molecides A and K. Hence as x is
known we have two equations for determining A and
K, and we may calculate both of them. Riesenfeld
and Reinhold now calculated the number of watervolumes,
i.
e.,
which x
figures
H2O
they
From
these
number
of
its
They
With the
numbers
of water molecules
Ion:
Ag
J^Cd
J^Cu
Na
Li
Number of HzO-molecules:
0.2
22
37
55
56
71
158
Ion:
OH
J^SOi Br
18
20
11
20
CI
21
NOa CIO3
25
35
a lithium-ion
14
THEORIES OF SOLUTIONS.
194
as
solid
salts
LiCl
Lil
molecule
H2O
Li
The motion
H2O may be
effort of
boimd
of a
to 1
complex
estimated to cause
dragging Li alone.
There-
ions.
water."
dif-
Noyes has
also
seems to conflict
with the assertion that on an average Li has only two
molecules of "ionic water." But as is well known from
first
The molecules
particle
of water, with
195
it.
the
number
of ionic
water molecules.
The nimiber
may
of course
be considerably greater.
number
of atoms,
The hydration
with dilution.
Therefore
we should
with dilution.
molecules.
LECTURE
XI.
The
free energy of
a dissolved substance
is
according
the
same quantity
molecule,
of matter in gaseous
i. e.,
A = RTlog,p-RTlog,p^
B is the gas constant 1.985 cal.,
temperature and p the osmotic pressure.
where
indicates the
work done
in compressing
(1)
T the
one gram-mole-
cide of a gas
Pa
is
absolute
This formula
A=RTlog,p
p.
If
(la)
where
v is
e,,
is
pv
by the
piston.
we
V is filled
tity is
lift
pv
= RT.
197
quan-
gas.
water, in which
a piston, loaded
liquid substance
in, e. g.,
case the
lifting
but not to the dissolved body, and separating a saturated solution over this body from a layer of pure solvent.
Of course
energy
all
are based
deal
The same
is
generally
expression should
be used for solutions if their condition was characterized by their osmotic pressure. But the osmotic pressure is very difficult to measure and instead of that
we
p = cRT.
We now
the for-
(2)
THEORIES OF SOLUTIONS.
198
tration
c,
which
is
tion:
Pa
c^RT.
(2a)
we
find:
A = Er(Iog.c-Iog.O.
(3)
we put c
one gram-molecule per
If
liter,
we
^usually-
get:
A = RT log, c.
(3a)
is
cilci.
We
dis-
centration into
For
its
two ions
this calculation
and that
other words no work
acid
is
Ci
we make
if
of each of its
is
done
two ions
when
Ci-
we transform a
if
Ci
In
certain
into its
Then
work to be calculated consists of three parts: (1)
The work done in the dilution of one gram-molecule of
the acid from the concentration 1 to the concentration C\
ions
their concentration is
c^
or vice versa.
the
A,
(2)
= RT
(log, 1
- log. cx).
Ci
mass
of
two ions, each of the concentration Ca at constant volume. This work is zero. (3) The work of condensing
199
A3
The
is
22er(log,C2-log,l).
work done
total
This work
is:
e.,
i.
we have an
If
solution.
lution
and
50 per cent.
it is
chloracetic acid at 25
then the
The
tion constant is 1.
expression above
is
due to
van't Hoff.
Evidently
K, and van't
it is
minations of Ostwald.
for
acetic acid
3,240,
acetic
The
A = +
free
of heat
A = 3,320,
C.
='
for trichlor-
60, etc.
energy or
affinity
developed in a reaction
equation, which
of
A =
is
easily
by the
following
thermodynamics:
t7
A-r^=
-RT^^^I^.
(5)
200
THEORIES OF SOLUTIONS.
we know A,
If
all
ot
a,t
temperatures, then
we may
calculate
U for
any
for
by
But we know
van't Hoff.
U=
A.
U we may determine A.
we develop A in a series in the neighborhood
absolute, we get
Then
knowing
If
= A,
A,
We
+ BT + CT^+
if
of 0
we do not
consider
= A,-
U,
CT'; U,
last
A,.
i. e.,
by the molec-
ular weight
is
a high degree
zero.
of
then
it
If
now
The determinations
of Schimpff
and
Pollitzer
The
were
said regu-
201
mation
for
has a
i. e.,
T
As we
because
and
opposite signs
B/2C.
temperature
have
(in
(cfr. fig. 5, p.
is
positive,
i. e.,
occurs,
212
).
is
put
A,
+ BT+
CT'
=U, = A- CT^
I find
BT = - 2CT\
At
this point
we
e.,
point
e.,T=-
B/2C.
also find:
dU/dt
i.
i.
= - 2CT =
B,
The A- and
point zero.
A-curve at the
points, at r =
and at r = - B/2C. In the
temperature interval between these two points they
two
A^
CT'
VAjC
THEORIES OF SOLUTIONS.
202
and
A
for A,
+ Br +
0,
we
CT^
The examples
find
.
= - B12C
of solutions given
A
it
J^l^^^.
are of the
same
sign.
two
solutions,
one prac-
tables
of
Landolt-Bomstein, third
is
upon the
low temperatures.
negative
The
solubility
we
sign of A, as
is
203
positive depends
always increases at
is,
shall
according to the
The
and U with temperature is given for
H3O3B, Ca(0H)2 and (C2H6)20 in the accompanying
vanishing in the neighborhood of absolute zero.
change of
diagram.
!*;oooo
[*S000
^TSOOO
Fig.
We now
U
is
is
Ca(0H)2.
Calcittm Htdbate
400
4.
positive at
heat
of
300
zoo
too
273
40 313
80 353
150 423
Ca (OH)2=74.
Diff.
dWIdt
V
F. 2.62
-1910 -1885 -25
+ 627 + 1643
0.01856 0.2688-2 -2331 -2332 + 1-9.6 +1799 + 4714
0.01196 0.0779-2 -2938 -2942 + 4 -14.3 +3130 + 8200
0.00446 0.6497-3 -4356 -4380 +24 -19.1 +5845 +15314
Br log, c = TF = -3100 + 18.12' - O.QZT^.
logc
0.0234
0.3691-2
jrob8.
Tfcalo.
THEOEIES OF SOLUTIONS.
204
A^
is
negative,
i. e.,
Just as
the substance
i.
e.,
for experiments.
B is
e.,
is
(if
(or increases
positive as
if
for
Ca(0H)2).
in saturated solution
is disso-
There-
is
if
i,
for gases
the
Berthelot found
U=
is
also in
good agreement
205
have found only a single class of dissolved subwhich the rule that A and C are negative
stances, for
increases steadily
it
and
for trimethylpyridine
The
first
at
it
solubility
c is
3.5
+20
40
60
80
Dlff.
0.857
260
- 90
0.597
0.7762-1
-15.0
-11.5
0.6810-1
0.368
0.5667-1
-321
-483
-587
0.48
-320
-485
-699
293
313
333
353
10,623
-112
602"
V
+4812
+3756
+2787
dW\dt
262
- 90
1.63
Br log. c^
2-4-6
W calc.
JToba.
lOgio C
0.2123
0.9329-1
269.5
+ 1753
+ 653
8.3
-10.7?
+ 0.0872.
121 (Rothmund).
Crit.
Point 5.7
*
10
20
40
80
120
160
180
logioC
283
293
0.6404
0.8065-1
0.2819
0.4500-1
313
353
393
433
453
0.1593
0.2021-1
0.1428
0.1547-1
0.1537
0.2417
0.1866-1
0.3832-1
0.3024
0.4806-1
W = BT
0.761
0.8816-1
20
40
50
60
273
293
313
323
333
338
0.898
1.044
0.9534-1
0.0188
1.296
0.1125
logioi:
0.2644
0.3805
W = RT
9,352
-1104
-1349
-1450
-1339
-1098
- 55T
-137
-48.6
-20.2
-148.3
+174
62.1
26.9
+171.2
+426.5
+622.4
log. c
calc.
16
25
11
U
+3746
+3342
+2495
dWldt
+357
W ob3. W
1.828
c=
Diff.
607
753
74 (Rothmund).
Phenol, CeHsOH
2.402
IT Oslo.
250
737
-1141
-1364
-1461
-1221
-1075
log.
65
PFobs.
+
+ 23 +
+ 0.077^.
+118
5.6
628
-1461
-3772
-5013
2.5
6.0
7.3
71
16
11.1
+190
+424
+584
18.8
10.9
2.5
48.4
= 35,328 -238r+0.4r2.
dWIdl
322.3
+
+
4.3
4.5
+14.4
+25.5
+39.2
+
+
-
5508
983
3859
6408
9022
-10572
THEORIES OF SOLUTIONS.
206
The
is
point,
three substances.
This point
is
For ether
at
by Le Chatelier.
is
satisfactory.
It is
lies in
value of
vations
fall in
These obser-
of these mixtures
and
it is
well
known
results.
We
exemplified.
207
to
draw conclusions
The
polation formulae.
great value of
inter-
causes an
But
still
experiments.
is
the following
{U expressed
o , ..-i-i ,in
Solubility
Substance.
Heatof Solution
/^
T.
i
Per
Cent.
4.22 at
(-U).
obserred. Calculated.
8.5
6.7
6.9
2.44 at 81
8.5
8.0
4.5,
2.19 at 75
6.5
6.8
0,
2.99 at 18
-2.8
-3.0
0.7
Succinic acid
2.88
at
Salicylic acid
0.16
at 12.6,
Benzoic acid
0.182 at
Amyl
4.23
at
Anilin
3.11
at 16,
Phenol
7.12
at
alcohol
in great calories)
0,
3.58 at 55
0.1
10.2
at 45
2.1
1.4
at 17.5,
18.5
at 23
4.6
4.9
at 10,
11.84 at 60
3.0
2.7
Boric acid
at
2.92 at 12
5.6
5.2
Mannite
16.8
1.95
1,
0,
(n
l)oi,
208
THEORIES OF SOLUTIONS.
where n
number of ions, into which the electroand a is the degree of dissociation, and
these cases is practically equal to zero, I have
is
the
lyte dissociates
a in
all
recalculated
must take
The
is
Ca(0H)2 above.
easily understood in
its
chemical formula*
is
RTc.
It is easy to see
from the
is
valid
to tabulate
A = iRT
(1
-|-
log, ic).
performed.
lated
how
I reproduce only
by Noyes, regarding
some few
silver
will
may
salts,
figures
figures calcu-
showing an
observed
by
209
210
THEORIES OP SOLUTIONS.
absolute temperature.
C.,
is
the
The temperature
interval
211
is
much
is
of
less
series.
may
perhaps be due
of these observations, perhaps also to
to the difficulty
members
in the inter-
positive values
and
T=
of
From
306,
DT^
is
negative,
i. e.,
of the
T=
156
of the
same
sign as
omitted term
C.
T=
given above
is
little
too high.
same
still less is
the variability of
(only as 1.9 to
1).
The
characteristic point,
temperature
for
for
for
for
i.
e.,
H2O;
T=17Q{t= -
T =
0)
97 C.)
154 C.)
81 C.)
139 C.)
of water.
THEORIES OF SOLUTIONS.
212
The
for
H2O
CH3CO2H
for
NH3
for
H3PO4
for
It
is
r
at r
at r
atT
at
is
=
=
=
=
at its
502
295
{t
318
209
(t
{t
(<
U=
0,
and
maximum,
lies:
= 229)
= 22)
= 45)
= - 64)
the variation of
with temperature.
In drawing a
U=
This point
0.
calculated above
the values r
and r
H3PO4
lies
scale
and
will
and
I actually find
The
U for
is
^40000
17
M l!
Tf
_o .riTTTT I
zoo
Fig.
The
that
4C0
rPT
600
5.
upon
The
213
about as great
It is therefore probable that the
f ormulse will give nearly right results also below 0 C. and
down to the neighborhood of absolute zero. I have
given a graphic representment of the formulae for water
in the accompanying curves and in these I have also
introduced the values of TJ calculated directly from
Noyes' figures. If the C/-curve had not a horizontal
tangent at T = 0, the value of dAldt would have an
In other
infinite value at the same temperature.
words, the A curve ought there to run vertically and
make an extremely sharp bend. This is not probable
although not quite impossible.
is
as that below 0 C.
if
moo
.9tOOVO
^sooo
t-
sooo
-10000
THEORIES OF SOLUTIONS.
214
mospheres.
If,
as generally done,
is
given in milli-
water in a reversible
way and
at constant temperature.
Fluid
W = ET log, p =
t
11394
+ 46.74r - 0.009273^.
215
of opposite sign
is
than in
Yet the
reality.
error in
i.
Ao
is
e.,
and that
little
greater
is probably not
without appreci-
tude
may
also
13.71
mm. Hg.
3.555,
i. e.,
Of course
this imit is of
no practical
may
remark
similar
K
A
decreases
by
13.717.,
is
much
by
the coefficient
13.71.
B decreases
The magnitude
of the
of water, therefore
units so
i. e.,
it is
BT.
of liter
As units
of
216
THEORIES OF SOLUTIONS.
for
ammonia
cubic millimeter.
we may
result.
formed.
It is only necessary to
T=
A =
Ao
Then the
CT'
formulae for
+ DT' + ET* +
U = Ao-CT' -
2DT'
A
.
and
.
are
.,
3ET^ ....
At low values of T we may omit the higher terms including T' and T* and then the condition, demanded by
Nernst for condensed systems, namely, that the Aand t7-curves shall be related to each other as object
and image in a mirror is true. But as soon as the
higher terms T^, etc., can no longer be neglected, which
happens in the cases investigated above, at temperatures above 150 to 250 degrees, then the similarity of
the two curves is spoiled.
There is no better proof of the small physical importance of the coefi&cient B than that it may be reduced to
zero or given any value by changing the units of measurement. Therefore it is clear that an assertion that B
is zero at the absolute zero would have very httle meaning in this case. The case is somewhat different if in the
homogeneous equiUbrium between gases or dissolved
number
change
through the transformation or if we work with pure
substances as in studying the dissociation of water or.
substances the
217
But even
we have
T =
0,
may
same concentration.
But
where
has
absolute,
have no
maximum
where of
real
vanishes
The
its
first
at 2,520
meaning.
is
value occurs at
very high,
Even
it is
calculated to 836 C.
much
sooner because of
U is zero
A goes
through
pressure
is 1
zero
is
just
at
the
point where
the vapor
if
we had chosen
atmosphere
THEORIES OF SOLTTTIONS.
218
By
differentiation
dA dU
dt
If
'dt
we
lie
find:
B
B + 2CT
/,
- 2CT = -(1+2^),
which
dissociation,
has
its
maximum
(or
With the
and dU/dt at 25 C.
we
298
temperature of A^^.
the absolute
the values of
see
how
A and U
some 30 C.
at 25;
it is
Lund^n
T^
are not
also gives
rather interesting to
far they
the point of
The
first
contains
which dissociate with absorption of heat, and the third those with production of heat
at 25 C.
ciation of
Through the subtraction of the heat of dissoa weak acid from that of water we obtain the
acid
is
change of free energy on neutrahzing the said subIn the neutrahzation of weak acids with weak
stances.
is
necessary to take the A and U values for both
it
bases
substances into consideration.
In Lund^n'swork these
: ::
219
do not find
it
nec-
in Ionization Processes at 25 C.
dAldt
dUldt
Water
-21,450
-13,450
-27
+50
Orthoaminobenzoic acid
-16,220
-11,840
-10,220
-21
+52
-7,780
-13.5
+35.5
-12
-17.5
+58
2,960
-32
4,840
-16.5
+
+
3,270
-12
-13
-19
+38
+55
+31
-18.5
+100
Pyridine
2, 4,
6 Trimethyl pyridine
5,510
-1,160
77
diss.
6,78Q 8,420
-6,070 - 5,690 - 5,600 - 5,560 - 4,720 - 4,470 -4,060 -12,570
Orthoaminobenzoic acid
Aminotetrazol
Cinnamicacid
Benzoic acid
Nitrourea (at 20)
m-oxybenzoic acid
m-nitrobenzoic acid
Nitro-urethane
Salicylic acid
9,110
-6,440
Ammonia
9,750
4,600
400
200
3,700
100
400
2,900
-18.5
-14.5
12
21
42
+ 26
+ 38
+65
+44
800
-11
110
1,310
-22
-22
2,240
-20.5
2,660
-22
3,180
-20.5
-19.5
+
+
+
+
+
diss.
-6,450
Acetic acid
+
+
+
+
+
+
+31.5
Water
0.46
137
-21,420
+29.9
-0.085
Orthoaminobenzoic acid
0.60
Pyridine
0.62
179
185
250
209
-17,770
-13,070
-11,980
+23.2
+31.2
+48.2
+32.6
-0.084
-0.087
-0.060
-0.085
4,750
-20.2
7,970
-0.02
-0.035
-0.064
2, 4,
Boric acid
p-Nitrophenol
3,920
3,900
3,000
2,510
0.84
6 Trimethyl pyridine
Ammonia
Acids with negative heat of
5,320
0.70
3,280
-8,625
30
35
23
29
28
"
diss.
-1.67 (-497)
0.21
0.68
63
203
-8,930
4.5
+26.2
220
THEORIES OP SOLUTIONS.
~C2rm
Aminotetrazol
0.76
Cmnamic
0.39
acid
Benzoic acid
Nitrourea (at 20)
m-oxybenzoic acid
m-nitrobenzoic acid
Nitro-urethane
SalicyUcacid
Acids with positive heat of
0.56
0.94
0.30
0.62
0.92
0.75
-18,350
+42.2
+12.0
+23.2
+93.5
-0.092
-0.052
-0.070
-0.167
-0.044
-0.064
-0.109
-0.074
r.
-1
226
116
167
277
89
185
274
223
-12,800
89
80
122
15
89
89
-5,020
6,460
3,980
7.7
-6,060 +23.4
1,258
+59.7
-7,360 +33.1
diss.
Acetic acid
0.30
Ortho
Ortho
Ortho
Ortho
Ortho
toluylic acid
0.27
chlorbenzoic acid
0.41
iodbenzoic acid
nitrobenzoic acid
0.05
bromcinnamio acid
0.30
0.30
770
340
890
1.0
+5.6
8.6
-0.039
-0.049
-0.047
-21,450
-10.925
-13,450
Water
Bases:
C/:.
t/:.
4
10
6
-6,112
-4,183
"20298
Water
0.46
Bases:
0.69
Acidswithneg. t/:.0.61
Acidswithpos. I/: .0.27
Tn
-6,168
-2,121
+2,130
A^
137
206
-21,420
-12,861
182.3
-7,819
-2,250
81
A-V
-8,000
-4,157
-3,991
-6,313
dAjdt
dVldt
-27
-16
-13.4
+50
+55
+46
-21
+29.4
B
+29.9
+33.8
+32.3
+8.7
C
-0.085
-0.080
-0.077
-0.051
differently
may
221
the value
A U is
going groups.
stances
that
is
consequence of these last two circumlies about 113 lower for the last
T^
and
first ones.
At this temperature
and diverge at higher temperatures,
coincide
it
two
positive sign of
come over
At
to the
values of Ao,
first
B and C
Ao
in the least.
regularity
is
that
dA
dt is
exam-
difficult to
THEORIES OF SOLUTIONS.
222
for all
examined
below 298 (the temperature of observation = 25 C.)The two highest values for nitro-virea and nitro-urethane
4 and
1 C, after these comes trimethylfall at
razol
and benzoic
acid.
ture, so that
dA
dt is negative,
Water has
groups.
its
dA
dU
dt positive
and
dt.
223
A=^RT
log.
and
U = - fir^^M^;
Uo
A,.
ones.
attached to the
do not
exist
groimds do not
exist in the
on
simi-
neighborhood of abso-
lute zero.
It is of
larities
a certain interest to remark that the regumuch more prominent with the process of
are
and
its
modification
as well
THEOEIES OF SOLUTIONS.
224
It
would be
Regarding
have fovmd that
the coefficient B is nearly a constant, about 44 for all
substances. The curves representing A therefore run
very nearly parallel to each other. As we have seen
above for the three groups of electrolytes there is a
certain parallelism between the magnitude of the
bility or
dissociation.
if
is
much more
obvious
al-
On
namely that regarding chemical equilibria. This problem is classical here in the world-renowned Yale
University, where one of the greatest thinkers in
natural philosophy, the immortal Willard Gibbs, has
of physical chemistry.
am
225
modem progress
16
skill
and
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f.
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d.
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W.
H. Freundlich:
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BIBLIOGRAPHICAL EBFERENCES.
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tiller von Berneck: Zeitschrift f. physikalische
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1909; 74, 513, 1910.
Od&:
Archiv.
f.
LECTURE
Cfr.
W. Ostwald: Lehrbuch
IV.
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d. allg.
ed., 7,
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78,
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129, 1910.
(6) 29,
68 and 505,
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40, 265,
1905-1906.
L. Michaelis
196, 1908.
LECTURE
V.
M. Gay-Lussac: Annales de
THEORIES OP SOLUTIONS.
230
W.
Tilden and
W. Shenstone:
by
Rep.
P.
Walden
in
Brit.
"Die Losungstheorien,"
p.
144, 1910.
Dmitri Mendelejeff: Joum. Russ. phys. chem. Soc, 16, 93, 184 and
643 (1884); cited by P. Walden
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und Chemie,
103, 177
(1858).
C.
M.
Guldberg:
H.
Ostwald's
50 and 441
(1885).
J.
20,
239 (1885).
(1884).
H.
J.
Dec.,
Zeitschrift
f.
26,
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Max
Zeitschrift
f.
LECTURE
VI.
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231
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M.
(3) 11,
2,
H.
V.
Annalen,
W.
Ostwald: Journal fur praktische Chemie, (2) SO, 93 (1884); (2) 31,
307 (1885).
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M. Planck: Wiedemann's Annalen, 3i, 147 (1888).
J. H. van't Hoff and Th. Reicher: Zeitschrift fur physikalische Chemie,
S, 7/7 (1888).
G. Bredig; Zeitschrift fur physikalische Chemie, 13, 191 (1894).
S. Arrhenius: Zeitschrift fur physikalische Chemie, 4, 96 (1889);
339 (1892).
F. Kohlrausch and Ad. Heydweiller:
Chemie, U, 317 (1894).
Zeitschrift fiir
Chemie,
2,
9,
physikalische
284 (1888);
5,
1 (1890).
W.
THEOKIES OF SOLXJTIONS.
232
LECTURE
VII.
Ostwald's
M. Nencki and N.
(1881).
A. A.
514 (1893).
No.
9,
1911.
S.
institut, 1,
E. Vetenskapsakademiens Nobel-
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376.
J.
1884.
M.
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Plotnikow: Zeitschrift
SS, Abt. II,
S7,
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Etudes BUT
W.
S.
K. Vetenskaps-Akademiens Handlingar,
Zeitschr. f. anorg. Chemie, 18, 83 (1898),
till
No. 4 (1897).
M. Guldberg and
C.
f.
T. Ericson-Aur^n: Bihang
Spring: Zeitschrift
Arrhenius:
P.
Waage: Ostwald's
les affinitfis
fiir
Le radium,
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fiir
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LECTURE
Knapp).
No.
30, pp.
7 and 14
(Mac-
VIII.
(1889).
G. Bredig: Zeitschrift
J.
F.
H. van't Hoff:
f.
Zeitschrift
Kohh-ausch: Zeitschrift
f.
f.
Elektrochemie,
U,
132
(1908).
Cf.
Technology quarterly,
17,
300 (1904).
Chemie,
S,
296 (1888).
234
THEORIES OF SOLUTIONS.
T. Godlewski: Bulletin
Zeitschr.
f.
of
the
Academy
Cracow,
of
6,
239, 1904.
E. Hagglund: Arkiv
f.
Kemi, Stockholm,
4,
No.
99, 229
11, 1911.
(1856).
Die Lehre
947 (1883).
C. Stephan: Wiedemann's Annalen, 17, 673 (1882).
E. Bouty: Journal de physique, (2) S, 351 (1884).
Fr. Kohlrausch: Proc. Roy. Soc, 71, 338 (1903).
Cf. Zeitschrift fur
Elektrochemie, U, 130 (1908).
S. Arrhenius: Zeitschrift f. physikalische Chemie, 9, 497 (1892).
P. Walden: Zeitschrift fur physikalische Chemie, 65, 207 (1906).
P. Dutoit and H. Rappeport: Journal de chimie physique, 6, 545 (1908).
P. Dutoit and H. Duperthuis: Journal de chimie physique, 6, 726 (1908).
M. R. Schmidt and Harry Jones: American chem. journal, 4S, 37 (1909).
P. Walden: Zeitschrift f. physikalische chemie, 7S, 257 (1910).
J. Kunz: Zeitschrift f. physikalische Chemie,^, 591 (1903), Inaugural
V. d. Elektricitat, Z,
(1908).
L. Pissarshewski
T.
H.
H.
K.
(1908).
B. D.
Steele,
A,
ms, 99
(1905).
J.
P.
(1907).
(1905).
Zeitschrift
f.
physikalische Chemie,
Edward C. Franklin:
W.
Zeitschrift
f.
A. Ssacharow: Joum. Russ. Phys. Chem. Soc, 4^, 683 (1910). Chemisches Zentralblatt, 81, 1523 (1910).
L. Kahlenberg and O. Ruhoff: Journal of Physical Chemistry, 7, 254
(1903).
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LECTURE
235
IX.
M.
M.
W.
S6,
396 (1872).
77,
1239
Arrhenius: Zeitschrift
Meddelanden
Cf. S.
f.
Vet.-Akad:s Nobelinstitut,
(1903),
No. 10 (1908).
Arrhenius Immunoohemistry, Chapter V, p. 144 and folfr.
1,
lowing.
W. Ostwald:
Chemie,
3, 186, 262,
280 and
386 (1889).
G. Bredig: Zeitschrift
f.
Elektrochemie,
6,
34 (1899).
385 (1910).
Nernst: Zeitschrift fiir physikalische Chemie, 4, 129 (1889)
H. V, Helmholtz: Sitzungsberichte d. Berliner Akademie d. Wias.,
W.
Juli,
1882,
5,
f.
236
S.
THEORIES OF SOLUTIONS.
J. Wallcer:
Chemie,
4,
319 (1889).
Cf.
d.
(1906).
J.
W. Commelin:
Joum.
of
Chemie,
64, 1 (1908).
LECTURE
J.
H. van't HofF:
H. Jahn:
Zeitschrift f
S. Arrhenius:
X.
Zeitschrift
f.
Zeitschrift
U, 1 (1901-1909).
Earl of Berkeley and E. G. J. Hartley: Proc. Roy. Soc, 73, 436 (1904).
Phil. Trans., A, B06, 481 (1906).
O. Sackur: Zeitschrift f. physikalische Chemie, 70, 477 (1909).
A. A. Noyes: Zeitschr. f. phys. Chemie,
ibidem, 4, 444 (1889).
E.
W. Washburn: Jahrbuch
(1909).
f.
B,
83 (1890).
Cfr. G. Bredig;
6,
69
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G.
Tammann:
237
Chemie, 9, 97 (1892).
Chemie, 73, 547 (19101.
R. Abegg: Zeitschrift fur physikalische Chemie, 11, 248 (1893).
A. C. D. Rivett: Meddelanden fr. K. Vetenskaps Akademiens Nobelinstitut, S, No. 11 (1911).
S. Arrhenius: Zeitschrift f. physikalische Chemie, 1, 110 (1887), and
4, 226 (1889).
S. Arrhenius: Zeitschrift f. physikalische Chemie, SI, 197 (1899).
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H. C. Jones: Zeitschrift fur physikalische Chemie, IS, 419 (1894).
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18, 328 (1878).
T. Fanjung: Zeitschrift fur physikalische Chemie, 14, 673 (1894)
P. Drude and W. Nemst: Zeitschrift fiir physikalische Chemie, 15,
The Svedberg:
79 (1894).
G. Carrara and M. G. Levi: Gazz. Chim. italiana, SO, II, 197 (1900),
Zeitschr. f. phys. Chemie, 36, 105 (1901).
P. Walden: Zeitschrift fur physikalische Chemie, 60, 87 (1907).
W. R. Bousfield: Zeitschrift f. physik. Chemie, 53, 257 (1905).
W. Ostwald: Zeitschrift f. physikalische Chemie, S, 840 (1888).
G. Bredig: Zeitschrift fiir physikalische Chemie, 13, 191 (1894).
W. Nemst, C. C. Garrard and E. Oppermann: Gottinger Nachrichten,
56, 86 (1900).
G. Buchbock: Zeitschrift f. physik. Chemie, 55, 563 (1906).
E. W. Washburn: Technology Quarterly, Bl, 168 and 290 (1908). Joum.
Amer. Chem. Soc, 31 (1909). Jahrbuch d. Radioaktivitat, 6,
94 (1909).
A. Coehn: Zeitschrift fur Elektrochemie, 15, 652 (1909).
R. B. Denison and B. D. Steele: Zeitschrift fiir physikalische Chemie,
57, 110 (1907).
E. H. Riesenfeld and B. Reinhold: Zeitschrift fiir physikalische Chemie,
66, 762 (1909).
G. Bredig: Zeitschrift fiir physikalische Chemie, 13, 228-238 (1894).
LECTURE
XI.
238
H. Schimpff-
THEORIES OF SOLUTIONS.
Zeitschrift
F. Pollitzer: Zeitschrift
f.
fiir
INDEX OF AUTHORS.
Abbgg, 175, 176, 178
240
INDEX OF AUTHORS.
Fanjung, 183
Faraday, 25, 27
Favre, 94, 95
Fink, 49
Fontana, 55
Foote, 148
Kahlbnbbhg,
174
Franklin, 150,151
Freundlich, 45, 48
Kjellin,
Garrard, 188
KoUrausch,
Gassendi,
5,
34
Haggltjnd, 137
Hannot, 115
Hantzsch, 169
Hartley, 176
Helmholtz, H. v., 27, 84, 87, 108,
163
Helmholtz, R. v., 30
Helmont, van, 3, 17
Henri, 113, 114
Henry, 56, 87, 153
Heraclitus, 1
Hess, 96
Heydweiller, 111, 180, 181
Hittorf, 14, 134, 150, 188-192
Homfray, Miss, 63, 64, 67, 68
Horstmann, 77, 78, 83
Hudson, 113
Isaac Hollandtjs, 3
Jacobson, 48, 49
Jahn, 96, 173, 195,
Jellet, 87
Johnson, 148
Johnston, 141
151, 170
Kalmua, 147
Klein, 10
Klobbie, 205
96, 109, 111, 134, 140,
145, 184-186
Kooy, 124
Koppel, 187
Kossel, 161
Kremann,
121, 125
Kunckel, 4
Kunz, 145
Ladenbtjrg, 32, 33
Landolt, 96
Landsteiner, 71
Latley, 30, 31
Lavoisier, 8, 9, 17
Le
L6mery, 5
Lenz, 162
Levi, 184
Lewis, 70
Ley, 169
Lincoln, 169
Linder, 45
Loewenstein, 10
Lorentz, 26, 30
Lorenz, 151
Loschroidt, 30
Lowitz, 55
Madsen,
116, 129
Mailey, 145
MaUkow, 31
Mallard, 10
Malmstrom, 174
Marignac, 82
Martin, 145, 148
Masson, 145
Maxwell, 20, 79
McCrae, 155
Mcintosh, 148, 149
Meisenheimer, 115
Mendelejew, 80, 81
Michaelis, 71
Millikan, 28, 30, 31
Moore, 155
INDEX OF AUTHOES.
Moreau, 31
Richarz, 30
Richter, 9, 17
Riesenfeld, 188, 191, 193
Rivett, 178
Robertson, 161
Morse, 175
Monton, 38
Bemeck, 46
Mtiller v.
Nabl, 30
Nencki, 115
Nemst,
XX,
188, 216
Newton,
Noyes,
162-164, 184,
154,
6, 7, 74,
112
Odn, 52
Oholm, 162
Olympiodoros, 3
Oppermann, 188
Ostwald, XX, 14, 21, 22, 26, 87,
132-135,
182, 183, 187, 199
Oudemans, 96
109-111,
158,
167,
Paracelstts, 4
Partington, 180
Payen, 55
St. Gilles,
132
Pebal, 161
Pellat,
30
Pissarshewski, 145
Planck, 26, 30, 32, 33, 89, 111, 133,
163
Plato, 2, 5
Pleijel, 163
Plotnikow, 126, 127
PoUitzer, 200
Price, 125
9, 18
Przibram, 28-32
Proust,
Ramsay,
63,
Rontgen, 96, 98
Rona, 71
Rosenstiehl, 77
Rothmund, 205
Roux, 31
Rudorff, 82, 174, 175
Ruhoff, 151
Rutherford, 25, 30, 122
Sacktje, 176
Ohm, 106
P6an de
241
223
Rappeport, 143
Rappo, 51
Rayleigh, 26
R6aumur, 6
Regener, 25, 31, 33
Regnauld, 22
Reicher, 111
Reinhold, 188, 191, 193
Reuss, 40
Sainte-Claire-Deville, 93
Sammet, xix
Saussure, de, 55
Schapowalenko, 145
Schfele, C, 18
Seh^ele, R., 55
SchimpfE, 200
Tabor, 31
Tammann,
10, 177,
178
242
INDEX OF AUTHORS.
Thomsen,
131,
Jul.,
79,
87,
102,
109,
204
Thomson,
J. J., 30,
33
TUden, 80
Titoff, 63-68
Townsend, 30
Traube, M., 85
Travers, 57, 58
Trouton, 224
Tyndall, 38
Wiedemann,
Wiedemann,
Wijs, 117
WUhehny,
Wien, W., 30
Valson,
Wurtz, 83
Waagb,
206-
Xenopanes,
YoTJNG, 223
Wakeman, 169
Wald, 21, 22
Zavbibfp, 14
Zsigmondy, 38, 40, 51
INDEX OF SUBJECTS.
Abnoemal
147-151
128
Acetic acid, 156, 210
Aceton, 169
Acids, 6, 17, 18, 42-44, 48, 53, 72,
109, 112, 113
weak, 157-158, 179, 182, 219222
Acid salts, 166
Active molecules, 108
Activity, 109
Additive properties, 91-103
scheme, 92, 97
Adsorption, 39, 43, 55-71, 122, 157
Affinity, 9, 74, 75, 196-225
tables of, 7
Aggregation, 70
state of, 2
Agglutinins, 157
Albuminous substances, 161
Alcahest, 4
Alcohol, 115, 169
Alcoholic solutions, 137
AUotropy, 11, 13, 21
Alpha-particles, 25, 33
Alums, decomposition in solution,
95
Amido-acids, 158-161
Amines, 150, 151
electrolytes,
Absorption of
Ammonia,
light,
210
Amphoteric electrolytes, 158-161
Analogy between gases and dissolved matter, 72-90, 110, 131,
132, 170, 171
Analysis, 110, 111
Anilin acetate, 168
Aqueous atmosphere
of ions, 185
Atoms, 5
Atomic volume, 185, 187
weight, 18, 54
Attraction, 1
molecular, 67, 68, 70
Autocatalysis, 116, 117
Brownian movement,
22, 34,
39
Caoutchouc, 170
Capillarity, see Surface tension
Capillary height, 91-93, 98
Carbonates, 19
Carbonic acid, 3, 115, 125, 148
Camot's theorem, 82
Casein, 161
Catalytic action, 48, 103, 110, 112
Cathode rays, 27
Cells, 85, 156,
157
Charcoal, 55-^8
Chemical force, 77
Chemical processes, 10-14
Chlorophyll, 116
Coagulation, 119
Coexistent phases, 13, 51
Cohesion, 75
Colloidal solutions, 32, 37, 71
Color, see Optical properties
Coloring matter, 55
Complexity, 76, 100, 148-151, 191
Compressibility, 68, 96
Concentration, 77, 78, 80
Concentration cells, 162, 163
Conductivity, electric, 14, 96, 106110, 195
Constant proportions, 9, 18, 71
Contraction, 6, 10, 95, 182-184
Corpuscular theory, 5, 6
Cosmogonical ideas on solutions, 1
Co-volume, 176
Critical temperature, 67, 70, 206,
Autoclaves, 113
Avidity, 87, 167, 168
207, 214
243
INDEX OF SUBJECTS.
244
Crystal fonn, 5
water, 6, 10, 181, 187, 191
CrystalloidB,
37
Decoloration,
55,
62
Dehydration, 120
Deliquescent salts, 9
Density, 80, 81, 91, 94, 98
modules, 181
Dibasic acids, 158
Dielectricity constant, 184, 187
Diffraction, 50
Diffusion, 39, 40, 74, 108, 161-164,
178, 185
Digestion, 116, 119
Disgregation, 78
Dispersing action, 53, 54
Dissociation constants, 169, 160,
169, 170, 192
Dissociation, degree of, 100, 101,
108, 134, 135, 142, 147, 159,
167, 179, 183
theory, 12, 14, 16, 82, 83, 95,
107, 147, 151, 152
Dissolution, 7
Droplets, 14, 23, 24, 26, 28
Dualistic electrochemical theory,
99
Dyeing
processes,
55
209-223
Electromotive force, 87, 107, 108,
162, 163
Electrons, 27
Equilibrium,
perature, 155
chemical, 11, 72, 77, 78, 84,
87, 109, 154, 166-170
heterogeneous, 131, 197
homogeneous, 132, 136, 148,
153-171, 198-200
Equipollency, 76, 103
Equivalents, 34
Esters, formation of, 15, 123
Ethylene, 126
Ethyl
ether,
156, 205
Evaporation, 196, 214, 215
Exchange of radicals, 75, 104
104, 162
Fats, 119
Ferments
120
(see also
Enzymes),
48,
Fever, 129
Fluidity (see also Viscosity), 2,
137-149, 194, 195
Foreign substances, 78, 165, 172,
179
Free energy, 84, 87, 196-224
Freezing points, 98-100, 110, 177,
178
Fulminating gas, 46
Fused electrolytes, 145-147, 151
Gamma-hats, 122
Gas-laws, 177, 196
Gas-reactions, 125, 132
Gastric juice, 119
Gay-Lussac's law, 20, 35, 197
Gelatine, 51
Gels, 119
Glucose, 115, 116
Gravitation, 6, 7
Growth, 117
Guldberg and Waage's law, 77-79,
83, 87, 109-111, 133, 167, 172,
195, 198
Elementary
Elements, chemical, 19
four, 1, 4, 19
Emulsions, 24, 122
Energy, 88, 196-225
radiant, 32
Enzymes (see also Ferments), 113,
114, 119, 129, 130
RaiMOLTSiNS, 129
Heat
of
of
of
of
of
of
199
activation, 109
adsorption, 65
combination, 94, 101
compression, 69
dilution, 79, 131
dissociation, 83, 84,
210-212. 218-228
111,
INDEX OF SUBJECTS.
Heat effect of evaporation, 214-21
of hydration, 155
of neutralization, 102-109
of solution, 131, 155, 202-209
of substitution, 101, 102
of suspension, 52
radiation of, 26
Helium, 25
Henry's law, 153
Hydrated
189-
195
Hydrates, 181, 187
Hydration, 12, 175, 179, 180
Hydriodio acid, 128
Hydrogen ions, 45, 53, 114-117,
125, 138-140, 181, 182
Hydroxyl ions, 44, 114-117, 125,
138-140, 181, 182
Hydrolysis, 37, 109, 112, 114, 168,
169
Hygroscopicity, 56
Ice, 12
molecules, 182
Iceland spar, 127
Immune-ljodies, 157
Inactive molecules, 108
Increase of boiling point, 81
Lead, 2, 5
Lecture experiments,
Life-elixiTj 4
xviii, xix
Magnetic
rotation, 96
Magnetism, molecular, 96
and
Waage's law
Maximum
effect,
54
Mercury, 2
Mercuric sulphate, 9
Metals, 2, 6
solution of, 126, 127
Migration of ions, 148, 190-193
Mixtures, osmotic pressure of, 177,
178
Moisture, 14
Molecular conductivity, 147-155
heat, 200
weight, 156
Molecules, 5, 11, 153
134
Inner salts, 159
Inorganic ferments, 48
Integral reactions, 21
Intermediary products, 120, 122
Inversion of cane-sugar, 112-116,
123, 125
Invertase, 113, 129
MonomolecuJar
Jelly, 51
Ohm's
Infinite dilution,
245^
Isotherm, 68
Isotonic
208
Kinetic theory
94, 106
Lactic
acid, 115
reactions, 46-48,
122, 125, 128
Monovalent, ions 42-45, 135, 141
Movement of ions, 95, 105, 185
Multiple proportions, 18, 19
Mutarotation, 114
Naphthalene, 156
law, 106
Optical properties, 38, 50, 51, 53
Organic chemistry, 16
Organic ions, 45
"Osiris," 3
Osmotic pressure,
INDEX OF SUBJECTS.
.246
Saccharose, 188
Salt action, 43-45, 51-54, 109, 110,
164-167, 179
Salts, 4, 5, 111
Palladium, 49
Saponine, 156
Saturation, 63, 68, 71
Sehutz's rule, 118-120
87,
153-157
between acids, 167
Pepsin, 116, 119, 129
Peptization, 119
Peptones, 161
Peroxide of hydrogen, 46
Scintillation,
Silver, 3
Soil,
Phlogiston theory, 6
Phosphorus, 28, 29, 40
Phosphoric acid, 210
Photochemical processes, 116, 127,
128
Physical processes, 10-14
Platinum, 46-49
sponge, 122
Poisons,
Polarization, electric, 108
Polonium, 34
Polybasic acids, 158
Polyvalent ions, 42-45, 141
Precipitate, 4, 9, 43-54, 76, 77,
104, 129
Precipitin, 129
Pressure, 49, 69
influence on dissociation, 183
Prime matter,
1,
Protamine, 161
Pseudoforms, 169
Pyridme, 170
Quantitative methods,
19,20
33
55
Sols 3955
SolubUity, 74r-76, 82, 84, 87, 131,
153, 179, 202-209
Solution, 5, 7, 56, 91-111, 197, 198,
202-207
sohd, 156
Solvent, 4, 75, 134, 137-151
Specific heat,
200
weight, 180
Specificity, 157
Sphere of action, 68,
69
Strength of acids and bases, 109,
110
Strong electrolytes, conductivity,
131-152, 172-195
Stokes's law, 23, 31, 195
Stone of the wise, 4
Subsidence, 43
Sulphur^ colloidal, 51-55
Sulphuric acid, 49, 166
vapor pressure, 81, 131, 149
Surface tension, 70, 91-94, 97
Suspensions, 22, 36-54, 157, 177
Tanning
processes, 55
Temperature, influence, 70, 74, 82,
xix,
17,
Quantity of matter, 17
Terpenes, 49
Tetanolysin 129
Tetraethyl ammonium iodide, 142
73, 79,
Tm, 3, 13
Tiophene, 156
Transition point, 13
Transmutabihty, 1, 2, 4
Trimethylpyridm, 205
Trypsin, 116, 119, 129
Tyndall s phenomenon, 38, 39
Ultramicboscope, 23, 38, 40
Ultraviolet Ught, 32, 114
247
INDEX OF SUBJECTS.
Water,
Vacta, 62
Valency, 135
Van't Hofi's rule, 124, 126, 129
82, 87, 131, 154
Velocity of reaction, 13, 46-49, 78,
104, 110, 112-130, 165
Vibriolysin, 129
Viscosity, 26, 107, 163, 185
Vital processes, 116, 117, 129, 130
Volume of dissociation, 182, 183
of neutralization, 182, 183
of reacting gases, 20
Vapor pressure,
specific,
94-97
214, 222
maximum
density
of,
11
of crystallization, 6
retarding processes, 121
Wehnelt, interrupter, 30
PRESS OF
pa.