Beruflich Dokumente
Kultur Dokumente
ELECTRO-CHEMISTRY
TRANSLATED FROM THE
GERMAN
EDITION
JOHN McCRAE,
With 58
Illustrations.
BY
PH.D.
8vo,
9-r.
6d. net.
NEW
CO.
THEORIES OF
CHEMISTRY
BEING
RHENIUS
DIRECTOR OF THE NOBEL INSTITUTE, STOCKHOLM
EDITED BY
T.
SLATER
PRICE,
1907
A II
rights reserved
PREFAC E
THE
fornia, in Berkeley,
to
me
more
the
by
followers
its
and by
its
opponents,
quite independent of the
new and
Many seem
are the
more
In
be less correct.
It
is
just
my
new developments
the circumstance
that
the
new
I hope to
make
is
to
me
their
most promising
new
knowledge in the
that
it is
last century.
possible to
If the scientists,
who
believe
of this
scientific edifice,
would
find
These opponents
would, therefore, be better advised to confine themselves to the
attacks.
PREFACE
vi
the elaboration of
some
and Dalton
If
we
scientific
as the materials,
as
when
is,
on the whole,
modern chemistry.
when they
we
new
builders,
know, or
at least
the
did not take into consideration, the plans of the older parts.
Nevertheless, we observe that similar styles have been used
both
that
now and
we have
in the past.
This fact
work by the
learnt to
is
It is scarcely of use to
examine
opinion,
which
is,
mode
of
my
personal
is
the most
working
In
reality, the
ones,
them
by many
which
who
To the
am
indebted to
my
friends Prof.
some remarks
on theoretical ques-
W.
PREFACE
and Dr.
many
vii
and
for
the publication of
By
many pleasant memories to
and colleagues, who gave me such a
criticisms.
my
Californian
cordial
friends
THE AUTHOK.
STOCKHOLM,
February, 1907.
CONTENTS
FAGB
PREFACE
CHAPTER
on one another
CHAPTER
II
Lockyer's hypothesis
Sir
CHAPTER
Wm. Eamsay's
hypothesis
12
III
acetic acid
21
CHAPTER IV
DISCUSSION OF THE VALIDITY OF DALTONS LA
The three
Hylotropic mixtures Wald's opinion
Influence of capillary forces Influence of
temperature A force, acting according to the laws of gravitation,
oannot operate between the atoms in a molecule Ostwald's views
Ethereal vortices
states of aggregation
39
CONTENTS
CHAPTER V
ELECTRICAL FORCES BETWEEN THE ATOMS THE
LA W OF FARADA Y
PAGE
...
CHAPTER
47
VI
CHAPTER
58
VII
CHAPTER
72
VIII
Kathode rays
distances
Kaufmann
Rutherford's views
CHAPTER IX
THEORY OF GASES
Gay-Lussac's discoveries The law of combining volumes
Avogadro's hypothesis Abnormal gas densities Partial dissociation The kinetic theory of gases Energy of gases Maxwell's law
Boyle's law
89
CONTENTS
xi
PAGE
of the distribution of velocities
and
conduction of heat
Dimensions of the molecules
Number of
molecules in 1 c.c. of gas Stoney's theory of the atmospheres of
109
planets
CHAPTER X
CHEMICAL KINETICS AND STATICS
Strength of acids Theory of Bergman Berthollet's and Gay-Lussac's
opinions Rose's work Study of chemical equilibria from Marggraf
to Malaguti Velocities of reaction.
Wenzel, Malaguti, Wilhelmy
The formation of esters. Berthelot and Pean de St. Gilles Saponification.
Warder
Salt-action
Formation
of ethers.
Williamson
Ostwald
The equilibrium
calculation
Horstmann's
theoretical
investigations
Van't Hoff's
Ostwald's
work
132
CHAPTER XI
THE INFLUENCE OF TEMPERATURE AND PRESSURE
DISSOCIA TION
St. Claire Deville's investigations
tions of Planck and van't Hoff
Dissociation of iodine
The equa-
NO
2
HeteCon-
CHAPTER
OSMOTIC PRESSURE GENERAL
146
XII
SUBSTANCES
Active and inactive molecules
Experimental data
Solid solutions
CHAPTER
157
XIII
ELECTROLYTIC DISSOCIATION
Calculation of the degree of dissociation from electrical and cryoscopic
measurements Separation of ions by diffusion Consequences of the
CONTENTS
xii
Electromotive forces
169
CHAPTER XIV
PROBLEMS TO BE SOLVED OBJECTIONS
The
INDEX
-Isohydric
194
,
205
THEORIES OF CHEMISTRY
CHAPTEE
before
chemistry.
To commence,
ourselves
"
:
then,
What
is
strength of a current (estimated either according to the brightness of the sparks produced on breaking the circuit, or from the
its
the time,
so
that
it
was very
difficult
for,
to
data.
Ohm, 1 however,
Cf.
Ohm, Die
and Peuticke,
Wien
Toeplitz
THEORIES OF CHEMISTRY
a parallelepiped, the ends of which are maintained at the constant temperatures ti and t respectively, is proportional to the
cross-section
is
(i.e.
was not that used in the calculation, or that a wrong value had
been assumed for the constant representing the electrical conWe should then have made a new
ductivity of the wire.
the electromotive force and the
care
that
experiment, taking
of
the
were
conductivity
supposed values, and then observed
the value of the current agreed with that of the previous
observation or with the calculated value, within the limits of
if
INTRODUCTION
and
the
it
Before a theory
which
is
established,
on
we
later
may develop
may
be regarded as the
The work
of
Ohm
last
of our statement.
The introduction
of statistical
THEORIES OF CHEMISTRY
"
the word " theory is often used in the same sense as hypothesis ;
still, this has no influence upon our study of theories in exact
sciences.
The main
bearing upon
ments must
constructed by Schweigger.
According to the definition
measured phlogiston,
nature.
after
He
known
to science for
INTRODUCTION
As we have
made
hypothesis.
said,
of
But
lost its
THEORIES OF CHEMISTRY
to
to
Such persons
made
these
men
is
workman who
rejects
to
We
"
is
We
Kelvin
may
INTRODUCTION
may
new
of
of
any kind."
first
wonderful development of
No
modern
other
THEORIES OF CHEMISTRY
development begins.
is
to
combine the
common
and general features, but leaving out those occasional peculiarities occurring in every experiment owing to unavoidable
errors.
wholly conceal the law that we seek. We may then use two
methods of procedure. The more rational one is to
different
to construct
We
number
the
mean
of ten observations,
tions
only the tenth part of that of ten. The experimental
error of the mean is in general inversely proportional to the
square root of the number of observations. As is evident, it is
is
by
its help, so
mean
Some laws
of Nature
seem
to be exactly true.
made
Thus, for
highest that
we can
INTRODUCTION
material bodies
quantities
laws of thermodynamics.
But there is another class of laws, and these seem to be the
more common they are only valid within certain limits. As
;
was
exact.
exactness of Boyle's law, that they overlooked the rather inAs we now
significant deviations which they had observed.
namely, that
they
fall as
much
Errors
that fall in one direction only, are called systematic errors, and
they are due to a definite cause, working always in the same
direction.
As now no
Eayleigh, Trans. Boy. Soc., 1901, 196, 205; Proc. Roy. Soc., 1905, 74,
A., 1905, 204, 351.
THEORIES OF CHEMISTRY
io
Waals, and
it
of the gases.
But
still
further research
made
of the wonderful
upon
We
effect.
work
is
is
of theoretical
that
is,
water.
Here the
dissolved
e.g.
salts in a
substance flows
from
that of Fourier or of
Ohm.
is
not confined
out.
Mathematics was
and
11
way
extensive
science
than physics;
it
thermodynamics
to explain
last quarter of a
phenomena
won
theoretical
as in the
domain of
science
is
theoretical research.
for
CHAPTER
II
little
This feature
is
in
the
work
of
As
far
B.C.,
we except
"
believe from observation that water
passage in Timaios
becomes stone and earth by condensation, and wind and air by
subdivision ignited air becomes fire, but this, when condensed
:
We
and extinguished, again takes the form of air, and the latter is
then transformed to mist, which resolves into water. Lastly,
To put it more
rocks and earth are produced from water."
hot
it
had
been
observed
that
by cooling
gases (" fire "),
simply,
cool gases (" air ") were obtained, and that by condensation of
12
13
in the water.
"
We
we
for
making
Mayow
Probably
was the reason he did not obtain wider recognition for his ideas, which
were soon forgotten. A century later, however, Lavoisier rediscovered and
established the same principles, and caused the abandonment of the phlogistic
this
hypothesis.
2
As we have seen
already, Archimedes
THEORIES OF CHEMISTRY
by
"
theory,
chemical science.
physical
and
new demonstration
cesses,
observed.
not yet been settled what may be the cause of these small
deviations. It is possible that the vessels used, and which were
of glass or quartz, were not absolutely impervious to the
But there is
substances formed during the chemical reactions.
to
a
that
after
still no sufficient ground
suppose
thorough and
made
so
3
Heydweiller, Physikal. Zeit., 1900, 1, 527
1901, 5, 394.
1902, 3, 425
Ann. Physik.,
15
products
when
remained
no quantitative conclusions were drawn from it till the time
It seems as if the idea of Democritus prevailed
of Dalton.
over the seemingly more simple idea that everything may be
divided indefinitely, and which was preferred by most of the
"
the notion
element
and showed that only the undecomposable constimatter (and not, for instance, the changeable qualities
of matter) should be called elements.
According to Boyle's
alchemists,
tuents of
chemical compounds.
acids, bases,
call
role.
amounts
of
equivalent
to
latter are
find,
ac-
THEORIES OF CHEMISTRY
bases,
whether we use
nitric, hydrochloric,
sulphuric, or
any
other acid.
tained in them.
oxygen con-
in
is
characteristic of
may
be varied continuously.
little
known
at that time.)
A fellow-countryman of Berthollet,
pounds which
tin forms
17
1
by consideration of the behaviour of the gases of the atmosphere,
to investigate the relative weights in which -these gases and
other elements combine with each other in their compounds.
His experimental work was not very accurate, as we may see
from his
figures,
if we let
represent 4 unit- weights of nitrogen,
1 of hydrogen, C 4*5' of carbon, and S 17
5 '6 6 of oxygen,
unit-weights of sulphur, Dalton showed, as a result of his
symbols, and
Nitrous oxide,
Nitrous gas,
Nitrous acid,
Nitric acid,
Water,
Marsh
gas,
NO
N0
HO
CH
Ammonia,
NH
Oxide of carbon,
Carbonic acid,
CO
C0 2
Sulphurous
Sulphuric acid,
SO
S0 2
Olefiant gas,
CH
now
acid,
experimental
Later on
Dalton improved his figures (1808), and put the combining
weight of oxygen as 7 instead of 5'66, and that of carbon as
"
5 instead of 4*5, but they still were far from exact.
Neverto be the real compositions of these substances.
and
diffuse hypothesis of
Cf.
"
New View
of Dalton's
Macmillan: 1896.
C'
THEORIES OF CHEMISTRY
whole number
Since the
of another kind,
number
and
of a third kind,
and so
forth.
compounds only
elements.
The quantities
of one element
The theory
value to
of
that
till
He
now.
we put
work
of
Berzelius
many
scientists
have
unity.
of
of Stas,
others, proves
lines of
many
other elements.
Now,
it
is
Hence
Sir
19
led to enunciate
the idea that at very high temperatures all elements are decomposed into hydrogen atoms. But the most recent researches seem
to indicate that stars
which are
also oxygen).
still
through
we abandon
if
speed that the half of it remains after 800 years, as the measurements of the helium quantity evolved indicate, then, if the
earth had originally consisted of pure radium, after 16,000 years
only the millionth part of it would be so constituted, and it would
not be richer in radium than a good specimen of pitch-blende.
After a further 16,000 years
its radio-activity
would scarcely be
perceptible.
be found in the
minerals
different
Mme.
different
and
was just the reason for searching for a new element (latery
called radium) in the most radio-active one of them, namely
quantities
as the investigations of
Curie indicate
this
Lockyer,
THEORIES OF CHEMISTRY
20
r
If all minerals containing uranium were decompitch-blende.
radium
into
at the same rate (and all specimens of
posed
ratio
each other.
exist
can be
to
be
1*35
X 10 6 molecules
of
uranium
to
every
molecule of radium.
1*6
vision will
.Strutt, Proc.
2
Bpltwood,
Sill.
Phil.
Mag.
(6),
1905, 9, 599.
4
G. von dem
(4), 1905, 20, 55.
Borne (1906) comes to the conclusion that in the rocks investigated by him,
"
there is no sign of proportionality between uranium content and radio-
activity."
5
(4),
CHAPTER
III
These mixtures
and as
it
examine
it
As
is
well known,
This per-
THEORIES OF CHEMISTRY
22
chemical compounds
H S0 + 6H 0,
2
and
of
with
acid
sulphuric
water,
H S0 H S0 + H 0, H S0 + 2H 0,
H S0 + 150H 0. If p
the con-
4,
i.e.
tion of the
curve
(corresponding to
20C
100^
FIG.
it
its
1.
H S0
2
exist to
some extent
in solution.
23
For
we must examine
other properties of
for instance, their conductivities
l
property F. Kohlrausch has made very accurate
determinations at 18 C., the results of which are given below
Of the
first
SO,
THEORIES OF CHEMISTRY
24
to
H S0
2
and
H S04 -f H
2
Pickering
dp
but only abrupt changes of direction.
The least ambiguous evidence on this question was given by
Jones 2 in his research on the freezing-points of mixtures of
sulphuric acid and water in acetic acid as solvent.
researches of Eaoult and others, we know, that if
From the
we dissolve
much
in all cases,
Two gram-
We might,
add A parts of
another
solution of
grams of acetic acid and 0'753 gram (A) of water. The water
alone would give a depression (a) of 4-69 C. 3 By special excaused by the sulphuric acid alone
(fc)
was found, and likewise the lowering (c) by A -f- B was
c = d.
experimentally determined. The difference (a + I)
B.
6.
c.
a.
+ 6.
25
d.
2-349
2-020
2-607
4*475
6-495
3119
2-600
2-752
4*410
7'010
4-258
3-829
3-185
3-037
4*345
7*530
4-493
4-520
3*888
THEORIES OF CHEMISTRY
26
to give molecules
H S0
2
+ 2H
H S0
2
-f
2H 2
as
number
the
of the
4
2
number
of water-molecules
to be twice as great as
number
&,
This is approximately
present.
d is not only twice as great as &, but a little greater
;
but always less than three times I (about 2'256).
learn
from this that with excess of water there may probably exist
of
S04 molecules
the case
We
H S04 + 2H
H
2
2 S0 4 -f 3H 2 0.
present) a higher degree of hydration, such as
In these researches the presence of the acetic acid interfered
somewhat, and we might therefore expect that in mixtures of
is
the case.
we summarize
If
we
find
If
more water
is
added, molecules
new
the composition
2 S0 4 +
2 0, and a correspondingly smaller
proportion (15 %) of the water-molecules are free. At higher
dilutions it seems as if nearly all the sulphuric acid were con-
The higher
hydrates
H S0 + 6H 0, H S0 +
2
different
seem
150H 2 0,
to exist.
same method
for indicating
them
27
as in
These hydrates
as for
acid,
existence.
sulphuric
Con-
worthiness.
From
to lack trust-
is possible to deduce
physical properties of
also see that many of the discontinuities
the existence
it
But we
which Mendeleeff thought he had found, and which he used
solutions.
for
critical
The same
examination.
is
most of the
2C 2 H 5 OH
+ 9H 0.
2
From
this fact it
this
But a
to
corresponding
that
it
is
2C 2 H 5 OH
2C 2 H
(5
+ 5H
2 0.
It
is
therefore
evident
at other temperatures
hydrates such as 2C 2
H OH -f 5H
5
at
55, and
to
assume
at intermediate
temperatures
tion
analogous case occurs with acetic acid, but there the change
rather small ; from 79 % at
to about 77 % at 60.
The
is
composition 77
1
% corresponds
to the formula
CH3 COOH + H2 0.
THEORIES OF CHEMISTRY
28
Now, it
a general rule, as I
is
latter.
viscosity of
which
is
maximum.
The same
is also
valid if the
the
From
soluble in water.
this
circumstance alone,
it is
evident
The same
holds
for
the
conductivities
of
electrolytes.
acetic acid
contains
16*6
tion
CH 3 COOH + 17H2 0.
maximum
In the study
of
i.e.
zero.
C.
of the vapour pressure of water below
vapour pressure of ice is proportional to the
fusion of ice (per gram-molecule).
29
the curve
heat of
of a substance
the
case.
sulphate,
is
classical
the
stable
example
is
crystallizes
Na2 S0 4
temperature
t.
C.)
m is
THEORIES OF CHEMISTRY
30
on
we
freeze a solution of
maximum.
if
sodium
H S0 + 4H 0.
2
to the composi-
- 25
C.
Solutions
all
homogeneous substance, from which the same substance cryBut in reality it only proves
stallizes out in the solid form.
freezes out from solutions of
that the hydrate H 2 S0 4 + 4H 2
The curve shows similar maxima for
the said composition.
H 2 S0 4 + 2H2 0, H 2 S0 4 + H 2 0, H 2 S0 4 and
water,
pure
H 2 S0 4 4- S0 3 in regions where these compounds separate out
,
mum,
viz. for
S0 3
The minima
from which
so-called
and a
2
ing to a solution of 31 grams S0 3 in 100 grams
out of
the
is
characterized
of
75
C.,
freezing
by
temperature
pure ice and
S0 4
+ 4H 2
remains unchanged.
There
is
com-
evidently
tell
interest
which do not
alter
mixtures
40rC
so
20
10
-10
-zo
-JO
40
-50
-60
-70
-80
1
00% HO
2
FIG.
3.
10
JO
20
40
50
60
70
80
90
JOO
To
is
increased,
and therefore
its
freezing-point
THEORIES OF CHEMISTRY
32
sodium
chloride.
its
tion,
If,
then,
saturation-point
more
is
salt to
the formula
+ 9H
NaCl
we had had
very nearly.
On
if
On
about 70.
Then the
the temperature became
21*3 C.
would contain 35'5 parts of salt to 100
of water, just as in the preceding case, and conse-
would go on
saturated
parts
till
solution
we
find that
ice or salt
commences
without changing
its
composition.
NaCl
+ 9H
We
on freezing a
solution there must finally separate a mixture of ice and
in constant proportions, but we are not entitled a priori to
salt
phenomenon very
like
that just
described
occurs on
Pure water
Guthrie, Phil. Mac/. (4), 1875, 49, 1; (5), 1876, 1, 49; 2, 211; (5),
1884, 17, 482.
33
we always
mixture,
If
we
distil
such a
it
On
solutions,
is
of the
and of purifying
it
distillation.
If
we
conditions
4) reaches a
maximum
at
110
20*24% (point
Therefore,
if
c)
we
C.,
when
the
of hydrochloric
distil a solution
we have reached
till
after
at
which
it
Cf.
3,
1876-1878.
34 and 219.
THEORIES OF CHEMISTRY
34
We
therefore
This time
acid.
to the point
we
If
c.
we
distil
+120
+100
+
80
+ 60
+ 40
-40
-80
10
FIG.
4.
BO
30
40
50
60
70
80
90
and hydrochloric
100%
acid.
their
succeeds
in.
most
cases,
maximum boiling-point
of the solution.
no
They
view
is
HC1
+ 8H
70, 80,
maximum
The composition
That
exist.
35
who
this
distilled
pressures, namely,
of the solutions of
to be different
We
There
is
The
we
latter
freeze a
solution
HC1
SH^O.
If
composition would remain constant, just as in the distillaThis is not the case, however ; water freezes out, and the
its
tion.
freezes out,
solid,
22, in
is
a real
state).
1
Soc.,
THEORIES OF CHEMISTRY
36
This
boiling-point for a certain composition of the mixture.
occurs for solutions of propyl alcohol in water, the boilingpoints of which are represented by the diagram (Fig. 5).
If
we examine
we
find that pure water boils at 100 C., and pure propyl alcohol
at 98 C.
admixture of the one of these substances with
An
the other lowers the boiling-point, so that for a certain composi% of alcohol), there occurs a minimum boiling-point
tion (about 70
20
FIG.
40
60
80
100
5.
we now take
(87
If
C.).
point
alcohol,
37
we may approximate
to a distillate of the
The
As
exercise
of Jones,
who
The most
dissolved
certain
method
methods of Eaoult.
by
compounds which
THEORIES OF CHEMISTRY
38
150H 2 0,
2 S0 4
the
existence
of which had, from
2
different physical properties, been inferred, seem not to exist in
solution, at all events to any extent. It seems that in inorganic
molecular weights
25H2 0,
or even
HC1
+ 8H
number
of atoms are
CHAPTER IV
DISCUSSION OF THE VALIDITY OF DALTON'S
LAW
As we have
molecules.
space.
motion
is
different in
also
it is
to
the simplicity of
the
so
far as I
know,
new
THEORIES OF CHEMISTRY
40
phenomena
or
new
On
laws.
it is
very difficult
have
existed
from
the
it
the
called
hylotropic.
itself.
we imagine
If
Such mixtures
a hylotropic mixture
which
a chemical individual.
dividual, because
retains the
we may
is
distil it or freeze
same properties
it,
a chemical in-
and
it
always
we
(as
Deville
proved).
The same
compound.
composition
elements.
under
all
have a constant
would be called
as
external conditions
Wald,
Zeit.
41
among
their readers
meets the objection that Nature also produces chemical individuals by stating that chemically pure substances are very
rare in Nature, and, further, that the processes by which Nature
produces chemical individuals show an evident similarity to
laboratory work.
In order to understand this statement better,
we
will briefly
The philosophers
If
we have two
The same
is
valid for
fore suppose
Here, however,
it
We
1
here neglect the extremely small influence of gravitation (or other
external forces) upon these equilibria.
THEORIES OF CHEMISTRY
42
When we come
we
only fluid, i.e. liquid and gaseous, but not solid bodies, react
The molecules of solid substances differ from those
chemically.
of liquids by the peculiarity that they are fixed in a given
position relatively to each other.
They may possibly possess
motion, but it consists only of oscillation about a mean position.
There are some very remarkable exceptions to this rule. Some
"
solid substances mix with each other, forming so-called
solid
solutions," first characterized
by van't
Hoff.
"
the cases of
solid solution
capillary forces.
us suppose that
To
we have
eight drops of water, each O'Ol millione drop of double the diameter; the
first
cases,
The
for solid
e.g.
had time
On
to
grow
43
to sizes
substances.
Now, most
work
therefore Dalton's laws hold good for them also; and indeed
we saw that Dalton deduced his law mainly from observations
on
gases.
no substances existed
it
is
We may
says that
1
good example
He
as a proof of chemical
air.
THEORIES OF CHEMISTRY
44
purity,
This
Indeed,
if
compounds
to
different quantities of
a quantity
of
evidence,
experimental
accumulated
it
during
the
seemed
could be used in the examination of
this law, it
as
consistently
45
chemistry."
Attention has recently heen called to the views of Wald,
because Ostwald, in his Faraday Lecture, has supported them
law of multiple
from the law of
and
law
of
the
combining
weights
proportions
If three elements, A, B, and C, form the
constant proportions.
compounds AB, AC, BC, and ABC, we first think of the com-
pound
AB
being formed by
definite proportions.
In
ABC.
if
AB
The quantity
of
is
The law
similar way, and the same objections may be made.
of multiple proportions may be illustrated graphically as
follows
which combines with different
The quantity of
quantities of
B and C
points
quantities of
is
AB AB3
(distance
2,
apart
etc.,
6)
is
The composition of
represented by equi-
on the
axis,
i.e.
of
the
in
proportions.
THEORIES OF CHEMISTRY
46
the constant
multiples of I and c respectively. Now, the law of
that the
demands
ABC
the
only
compound
composition of
ratio of the quantities of B and
shall be independent of the
C which
method
which represents this comcompound.
pound graphically may have any position in the co-ordinate
to
system BC, and no a priori conception can, in contradiction
The
AC
AC
point, however,
of preparation of this
CHAPTER V
ELECTRICAL FORCES
FARADATS LAW
As we have
second kind.
close
proximity
attraction
charge a
"b.
bodies, B, until
a compound,
A+
wB,
is
formed which
is
is equal to but
electrically neutral, so that the charge a of
of opposite sign from that rib of the %B bodies.
As we know
bound
THEORIES OF CHEMISTRY
48
We
1
must, with Helmholtz and J. J. Thomson, suppose
an atomic constitution of electricity as well as of matter. But in
unit.
We
research.
He subjected
physics and chemistry of gases.
influence of electric sparks, and found that an acid
He
mistook
it
air
to
the
was formed.
oil and
was evolved. Van Marum repeated the researches of Beccaria
and Priestley on a larger scale. He found that the electric
through
spark not only reduces metallic oxides, but that it also sometimes causes the oxidation of certain metals, e.g. lead, with the
aid of the oxygen of the air.
He also found that many liquids
and solids, as, for instance, alcohol and camphor, give hydrogen
under the influence of electric sparks. In his experiments,
"
Thomson, Electricity aiid Matter."
This history is given in detail in Ostwald's " Elektrochemie, ihre
"
Geschichte und Lehre (Leipzig, 1896).
1
Cf. J. J.
ELECTRICAL FORCES
49
Ammonia
little
They employed a
in.
frictional
was
filled
The
Probably the greater part of the gas evolved was due, as later
1
experiments of Perrot seem to show, to the thermal effect of
the spark, and not to its electrolytic action.
Eitter repeated this experiment, using electrodes of silver
wire and a solution of a silver salt instead of water. He found
that a thin deposit of silver was deposited on the negative
On reversing the current this silver deposit was dissolved
pole.
again.
is
obtained
if
the metals
are
ranged
The construction
a
new
character
to
effects
THEORIES OF CHEMISTRY
50
and then they found that the oxygen formed at the positive pole
was given off as a gas, although its quantity was not so great as
that of the hydrogen evolved from the negative pole.
They
were very astonished at this result, as they had expected to find
both oxygen and hydrogen liberated at each pole. They also
observed that litmus turned red at the positive pole, and that
chemical processes were going on in the pile itself while it was
producing
Davy
electricity.
also
the voltaic
pile,
and was
and in
this
way proved
At
that
it
partially dissolved
by the water.
few years
later
Davy
pre-
ELECTRICAL FORCES
The
51
brilliant
Davy supposed
About
the
same time
Berzelius
published the
himself
and Baron
by
drew
the
conclusions
from their
They
following
(1807)
Hisinger.
experiments
Neutral salts are decomposed by the electric current. In
general chemical compounds are decomposed by the current,
:
point
was
of importance
for
the
electro-chemical
views of
it
Since
it
was
all
liberated
5-
end of his
series, and the stronger the acid was the nearer the
substance in question was placed to oxygen.
In the same manner Berzelius showed potassium to be the
Oxygen
ELECTRICAL FORCES
electricity.
to
53
be concentrated
around two
this
manner
came
more
electricity
FIG. 7.
chemical compounds equivalent quantities of the different products appearing at the electrodes these products were called
were set free by the same quantity of electricity. To
his
law, he passed the same quantity of electricity through
prove
ions
When
two vessels arranged in series, as shown in Fig. 7.
the current had been passing for a certain time, the quantities of
For instance,
ionic products in both the vessels were measured.
the one vessel contained stannous chloride, kept molten by
means of a spirit-lamp, and the other was a voltameter containHe found that 3*2 grains of tin were
ing acidulated water.
3
'8
inches of oxy hydrogen gas were
and
5
cubic
deposited,
evolved in the voltameter, corresponding to 0*497 grain.
the equivalent weight of water (or oxyhydrogen gas)
Since
is
9 (9
THEORIES OF CHEMISTRY
54
weight
32
u
as 58
Sn
tin,
calculated
= 57*9.
according
to
Faraday's
law,
is
of
= 118-8).
In the same way Faraday determined the so-called
chemical equivalents of
different
substances
(that
electrois,
the
quantities which are liberated by the same amount of electricity as that required to liberate the unit weight of hydrogen),
and he found that the electro- chemical equivalents correspond
completely with the chemical equivalents.
It is very astonishing to find that Faraday, as can be seen
from
e.g.
surrounding liquid.
By
this
may
fore,
be placed at any desired distance apart. We must, therenot be surprised that Eitter put forward the idea that
hydrogen
is a compound of hydrogen and oxygen only, and therefore Grotthuss formulated the following hypothesis, which was
generally accepted to explain the conduction of electricity
water
8).
The molecules
ELECTRICAL FORCES
55
are arranged in a manner analogous to the supposed arrangement of the small molecular magnets in a magnet. Electrolysis
"
by Faraday from a Greek word signifying path of electricity ")
by which the positive and negative electricities entered the
and positive ions.
electrolyte to combine with the negative
After the first ions are deposited, the chlorine atom of the
8, b).
01
01
o
o
FIG.
8.
Under the
move about
If
we now
dip
THEORIES OF CHEMISTRY
56
positive electrode
positively
same
velocities
for all
under
are
(practically)
completely dissociated
the
is
they
escape
the neutral state, they must have
given up their whole charge
to the liquid.
This charge must have
gone to the dissolved
for
the
other parts of the liquid are
sodium,
unchanged. Therefore the sodium ions in the new solution
carry just as much
positive electricity as the chemically equivalent quantity of
hydrogen ions did before. This is one way of expressing FaraIn exactly the same way as above, we can
day's law.
prove
that if a positive ion is replaced
by another whereby
necessarily
ELECTRICAL FORCES
57
other so-
called
The
tively.
K FeC N"
6
charges, because
carries
it is
one atomic
chloride,
are
C6H 5 NH3
(because
it
may
be regarded
as replacing
in KC1) and 01, each carrying one atomic charge.
If zinc is substituted for hydrogen in hydrochloric acid, every
of zinc replaces two atoms of hydrogen ; therefore we say
that the zinc ion carries two atomic charges of electricity.
This
evidently corresponds to the chemical expression that zinc
atom
is
a divalent
body.
aluminium ion
which
signifies that
mercurous, and
Hg
in mercuric compounds.
CHAPTER VI
ELECTRICAL FORCES BETWEEN THE ATOMS (CONTINUED): CHEMICAL VALENCY AND AFFINITY
EVIDENTLY we here come into
the difficult
rules of valency.
As long as we consider ordinary electrolytes
the case is extremely simple.
But if we draw the obvious
ELECTRICAL FORCES
59
"
acid.
may
we know
"
electrolytes
electrolyte
pupil of Helmholtz,
He
the electrometer,
corresponding
and
oil of
to
observed deflections of
the
the
0'9 volt
different metal
them
for a potential
difference.
"
If the connection
electrolytes."
"
is
not at
THEORIES OF CHEMISTRY
60
the facts that every unit of affinity is charged with one equivalent either of positive or of negative electricity, they can
form compounds, being electrically neutral, only if every unit
charged positively unites under the influence of a mighty elecwith another unit charged negatively. You see
tric attraction
atoms, makes
tralization is
by neutralization
Unsatuj-ated compounds
nected units of affinity, offer no objection to such an hypothesis
they may be charged with equal equivalents of opposite elec;
tricity.
existing only at high temperatures, may be explained as dissociated by intense molecular motion of heat in spite of their
liarities,
future researches."
ELECTRICAL FORCES
61
NO
Chemists, therefore, have given up the old idea that unsaturated compounds always show an "even number of unconnected
units of affinity."
At the present time most of them seem to
incline to the opinion that nitrogen may be 1-, 2-, 3-, 4-, or
its
motive
force.
Now, according
0'24 calorie).
one
work done
'
in electrolysing a gram-equivalent
A=
96,500^ joules
is
23,070e calories
and therefore
this
is
proportional
magnitude may be
to
is
affinities.
The
forces
holding
together
the
molecules
may
be
of
THEORIES OF CHEMISTRY
62
different
kinds.
Berzelius,
of hydrogen
is
96,500 coulombs
28,950
X 10 l
electrostatic
units.
The
two
they would
attraction
10" 10 dynes, or, since a dyne is equal to T02 x 10" 6 kgm., with
a force of 1*02 x 10~ 16 kgm. weight.
Further, the attraction is
proportional to the charges on both the particles, so that if
these were charged with the quantity of electricity carried by one
gram of hydrogen, their attraction at a kilometer distance would
be 28,950
= 8'54 x
10 12
kgm.
We may
radii
3'65
would be 1750 times less than that of the earth, that is,
km. From this it is apparent how much greater are the
electrical attractions
forces.
ELECTRICAL FORCES
tear asunder the
atoms of a molecule,
One gram
of water.
of
hydrogen at
for instance, a
C.
63
molecule
occupies 11,200
at
to
C.
erg
41 Q
x iQ5~^
calories.
Hence,
if
jj^Qg cal.
= 0-27xlO- 17 cal.
The
term
is
of
of
electrical
work is
therefore
2356 X 10 20 x 0'27 X 10
17
636120
calories.
there
THEORIES OF CHEMISTRY
64
We
magnitude that we need not look for other forces for this
purpose, and it is also probable that these electrical forces are
the only, or at least the chief, forces which- bind the atoms
together.
and Ebert, 2 which are based on the heats of dissociation of nitrogen peroxide (l^O*), iodine, and hydrogen. The
l
Kicharz
may
be
i.e.
amount
of
Ebert,
Of. also
3
Richarz, Sitzungsber. d.
ELECTRICAL FORCES
65
is
to
By
measure the
PdH
OHK N0 K N0 H
3
HPd.
solutions of caustic
by the arrow,
foil
potash, saltpetre,
and
foil
Pd
|
HOH KN0
|
KN0
HHPd.
|
KOH
somewhat
0'675
this
= 15,570
process
is
mixing the solutions of two easily soluble salts, e.g. AgCl from
AgN0 3 and NaCl. A galvanic cell of the following
a mixture of
composition
is
made up
AgAg
When
ClKa
NONa N0
|
Ag
Ag
combination becomes
Ag
AgCl
THEORIES OF CHEMISTRY
66
i.e.
a change from
into
AgCl and
ZnZn
S0 4 Zn
The electromotive
S0 4 Cu
Cu = Zn
|
ZnS0 4
ZnS0 4
CuCu.
|
corresponding
to
earlier
thermodynamics
23,0706^
dT
where
23,070e
i.e.
-^p,
Jul.
ELECTRICAL FORCES
matter of
and in
67
An
1
investigation by Helmholtz on the electromotive force
of the so-called concentration cells has played a very important
In these
part.
cells
two solutions
of the
same
salt,
but of
salt.
Such a
cell
is,
and
for
Cu
cone.
|
When
CuS0 4
dil.
|
is
CuS0 4
Cu.
|
is
A=
1-99T log,
*P
firstly,
cell
particular subject.
There are a large
in
added on,
e.g.
water, alcohol,
pound by evaporation.
1
2
etc.,
(p)
during this
Planck.,
Ann. Physik.
u.
Chem.
(3), 1890,
40, 561.
THEORIES OF CHEMISTRY
68
the affinity
is often
compound.
term due to Helmholtz.
Considering further the question of water of crystallization,
is well known that many substances can add on different
"
called the
it
i.e.
This work
1
containing water of crystallization have, according to Pareau,
the following pressures of aqueous vapour at 50 C.
:
CuS0 4
4*4
+ 1H 2 Q CuS0 + 3H
4
mm.
30
CuSQ 4 + 5H 2 O
47 mm.
mm.
(pure water)
91 mm.
is
at
the free energy of the water and that of the water of crystallization, is much less than the heat evolved (W) at the same time,
as the figures given below (Thomsen 2 ) show.
As can readily be
seen, this heat is equal to the difference between the heats of
solution of CuS0 4
rcH 2 and CuS0 4
1)H 2 0.
(n
Pareau,
Ann. Physik.
Thomsen,
J. pr.
Chem.
1878, 18,
1.
ELECTRICAL FORCES
Salt.
69
THEORIES OF CHEMISTRY
70
the
first
NH
three molecules of
three last.
above.
creasing temperature.
At
a high
i.e.
the
to exist
the
unstable, and
As we
shall
pressure in
of affinity. 3
see
later,
it is
characteristic of chemical
compounds that
the properties of the components have almost completely disappeared. One, therefore, readily assumes that in salts containing
water of crystallization the components of the water-molecules
salt.
Horstmann,
1, 5.
ELECTRICAL FORCES
71
valencies.
with
monovalent
negative ions,
as
chlorides, etc.
The
theless
investigations of Hittorf on the migration of ions nevershowed that in many cases the so-called molecular
K and AuC]
4.
6,
compound
that this
to the ideas
which prevailed
It
at that
CHAPTER VII
THE DEVELOPMENT OF THE DOCTRINE OF
VALENCY
As
old as
is
bine with each other, i.e. become a new and definite substance,
losing at the same time their most striking physical properties,
just so old is the symbolic representation of the union by joining
together two
was gradually recognized that not only one, but often two or
more new compounds could result from the union of two subIn some such cases Proust proved that the different
stances.
products of combination differed from each other in the relative
quantities of their components, and that each one was characdefinite ratio of the weights of the components.
recognized such an invariable composition as the sign of a
terized
He
by a
definite chemical
compound
(Proust's
day
his
we
of the alphabet.
In
Gay
to
the old
make
of
we can say
method
of repre-
73
Instead of the
neglect of theoretical methods of consideration.
atomic weights, the so-called equivalent weights were used, and
method
With
it
soon
many
organic
compounds; many
of
them
are
volatile,
and
in representing the
organic chemistry,
applied
to
inorganic
THEORIES OF CHEMISTRY
74
We
fit
One
of the
first
difficulties
of
carbon
just as
many
1
Van't Hoff, "Voorstel tot uitbreiding der structuur-formules
"
Ruimte," Sept., 1874. Cf. Van't Hoff, Chemistry in Space."
2
Le Bel, Bull. Soc. Chim. Paris, Nov., 1874.
in
de
75
have the same composition and are alike in every other property,
with the exception of the effect they have on the rotation of the
1
plane of polarization of light.
They possess numerically equal
rotations, but of opposite sign. It is assumed that the two bodies
can only differ from each other in the sense that the molecule
of the one is so built up that it forms the mirror image of the
other the two molecules stand in the same relation to each
other as do the right and left hands.
In explanation of this, it
;
as
shown
9).
dotted lines are supposed to lie towards the back.) The order of B, C,
and D, as seen from A, is left to
FIG.
9.
gruent
figure
top.
when
A and B
are the
same
the four valencies of the carbon atom are joined to four different
atoms or atomic complexes. Van't Hoff has
tested this conclusion in a large
number
of
carbon atom, as
is
The
(7),
may
also
1896, 8, 373).
be different
for the
THEORIES OF CHEMISTRY
76
and
(COOH).
and hence
it is
they
lie as far
clusion had
J.
grounds.
it
An atom
is
its
place
now a molecule in
C and D, are bound to one
and B, which may possess equal
Consider
different atoms, A, B,
carbon atom.
The atoms
electric charges,
e.g.
from the molecule, and it may happen that they are both
It is therefore possible for
separated at one and the same time.
them
to
again.
equal
known depends
solely
on the
77
small to be noticeable.
the
reaction
The matter
is
altogether different in the cis- and transor atomic complexes, occupy different
The atoms,
modifications.
positions with respect to each other, and not the same, as is the
The two isomeric bodies have,
case with the optical isomers.
different
therefore, essentially
physical and chemical properties,
it is
anhydride by
to split off water at higher temperatures becomes active. Maleic
acid can again be obtained from the anhydride.
I cannot agree that these transformations in any way contradict the idea of localized valencies in the atom, as Werner
maintains.
In
later times
otherwise
if
Wedekind,
etc.).
THEORIES OF CHEMISTRY
78
The formation
by the
upon
of an inactive mixture
We
compounds,
S0 2 and S0 3
Kelations similar
pairs.
inorganic chemistry.
Kekule's doctrine of the constant valency of the elementary
atoms was therefore given up, and it was assumed that the
etc.
In order
to
Cl 3Fe
it,
Fe01 3
ferric chloride
was written
made up
1
Fischer, Ber., 1894, 27, 3189.
1904, 86, 1249.
Cf. also
Soc.,
79
form of vapour, consist of monatomic molecules. This was considered to be just as it should be, since it was assumed that
the two valencies of these divalent atoms neutralized each
This explanation was no longer valid, however, when
Victor Meyer 1 showed that iodine and bromine consist of
The same is true for the
single atoms at high temperatures.
other.
vapour of the monovalent alkali metals. Later on measurements of the freezing-points of mercury solutions 2 led to the
40 C., i.e. at very low temperatures,
results that even below
V.
nearly all the metals consisted of monatomic molecules.
3
sufficient
assumption.
It would probably be still more difficult to bring into line
the compounds with so-called water of crystallization, alcohol
of crystallization, ammonia, etc.
these difficulties
Tammann,
Abegg.,
Zeit. physikal.
Zeit. anorg.
side,
of
Braunschweig, 1905.
THEORIES OF CHEMISTRY
8o
1
All return to an idea of Berzelius, which in a certain
Abegg.
sense formed the basis of his dualistic system.
Berzelius'
is
as follows:
Under
Two
to
ternary,
e.g.
to
salts
possessed.
present time, to
a conception which
is
in the
The conceptions
main points
of Berzelius
1
Abegg, Christania Vidensk. Selsk. Skrifter math.-naturv. XL, No. 12,
1902; Abegg and Bodlander, Zeit. anorg. Chem., 1899, 20, 496.
81
electric
Other valencies
In order,
we
if
possible, to find a
to electrical ones.
way
out of these
difficulties,
NH
condition, and
NH C1
4
On
compound.
lytically into
tive charge.
being vaporized,
two components,
it
is
a molecular
NH C1
In aqueous
dissociates electro4
4 with a positive charge, and Cl with a negaTwo views have been put forward with respect to
solution
NH
THEORIES OF CHEMISTRY
82
NH
ion;
firstly,
posi-
H-atoms by means
NH
4 C1
strongly dissociated, H
are
when ammonia
retained
is
all,
added,
HC1
ammonium
chloride,
tively.
hardly at
respec-
fact that
NH
tion with
3.
which
may
(HOH2 N)
dissociated,
much
is
less so
other
is strongly
analogous manner that every weak acid,
an essentially
83
different constitution
from
e.g.
that the
atoms is different.)
cannot, therefore, assume otherwise than that in the
We
ammonium
ion, as it exists in
electrically charged.
The
linking may be of the same
negative.
order as that between a positive and a negative valency, corre"
sponding to the principal valency "-linking. "We will assume
that the two charges in the ]STH 3 and HOI are at an equal
strength of this
distance from each other, and that the molecules approach each
other so that the median plane c between the two charges on
H and 01, and the plane of symmetry E', which lies between the
two charges on the NH 3 coincide with each other. We then
,
THEORIES OF CHEMISTRY
84
We
same distance
apart.
NH
-j.
01
H+
->
<e
10-0
5'0
3-0
2-0
I'O
0-5
0-3
0-2
0-1
0-05
o-oio
0-038
0-103
0-211
0-586
1-106
1-425
1-612
1-801
1-900
FIG. 11.
it
When
-3
become equal.
Now, it
is
One can
therefore
It is
linking is generally much weaker than the single one.
obvious that the double linking cannot be broken by means of
same
time.
The
fall
force is zero.
It is a peculiarity of electrical double linkings that the
linkings within the individual molecules remain completely
undisturbed when the one molecule, e.g. HOI, links itself to the
NH
other,
e.g.
3.
85
in
NH
NH
single, e.g.
There
the
negative valencies.
Kecently
themselves compelled
to
1
Baeyer and Villiger.
behave similarly to water itself; the alcohols, ethers, esters,
oxygen acids and their salts, sugars, etc., can be considered as
e.g.
The addition
of a large
when
or
dissolved in
molecules or
that in
still
solvents
higher complexes.
It
must
also be
double
assumed
Baeyer and
Iii
THEORIES OF CHEMISTRY
86
in
Similarly,
ammonia and
all its
substitution
products,
"
ing ammonia of crystallization split off ammonia as vapour
almost according to the same rules that regulate the giving off
In
of water from salts containing water of crystallization.
it is
well
known
of
valencies of the
when
place.
As
regards
the
molecules
H N
2,
2,
and
0%,
for
example, one can scarcely make any other assumption than that
the one atom is positively and the other negatively charged.
complex
by the
splitting
off
electrons
87
may
electrolytic
test,
that
it
valency,
ammonium
ion a
NH
3 by means of a subsidiary
hydrogen atom is linked to
valency, and at the same time possesses a free principal
the
(NH 3)6PtCl 4
salts
KNHaClfiPt
in the ions
3 TSTCl 5 Pt,
(NH3)5 ClPtC] 3
and
K PtCl
2
(H3
6.
to
)6 Pt,
and Cl 6 Pt
,
six
in the ions.
of this
He
points out that very many salts possess six molecules of water of crystallization, and expresses the opinion
bodies.
His attempts
lization,
analogous
salts,
satisfactory.
At
88
fact that the
THEORIES OF CHEMISTRY
number
The different
groupings occurring in inorganic chemistry.
dissociation tensions of the different
molecules
in salts
2
containing water,
e.g.
by Werner's theory.
CuS0 4
-f-
5H 2 0,
cannot be understood
CHAPTER
VIII
sign.
AB
B
FIG. 12.
the
The cathode
the plane end of K, and
Cf. also
between
(4), 1903,
12, 714.
THEORIES OF CHEMISTRY
90
"
passed through a small
window
"
of thin
aluminium
plate, /,
so that they proceeded along the axis of the tube AB. This tube
could be filled through the side tube r with gases at different
The strength
pressures.
taking advantage
whether
electrons,
consists of the
ways in the
different materials.
becomes
different.
This depends probably on the position of
the electric charges on the atoms, which are able to cause a
sensible deviation of the electrically charged cathode rays, if
if I
and
are measured,
is
found
to be
Using this formula, Lenard calculated the folio wing absorptiona for cathode rays possessing a velocity of 10 cm.
1
coefficients
per second
J-
velocity of light), in a
medium
of density S
ELECTRONS
91
THEORIES OF CHEMISTRY
92
shows the
velocities,
least absorp-
leaves
of metal
up
in
mm.
to 0*03
There
travel through thousands of molecules.
must, therefore, exist very great interstices between the electrons
electrons
of
may
is built up.
definition the absorption- coefficient is a measure of
of the cross -sections of all the obstructing particles in
Now, by
the
sum
Ice.
increases
rays
approaches
mm.
sum
pressure, the
where
is
13
sq.
N hydrogen molecules
cm.
in 1
If
c.c.
Q =
we now
gas at 1
N?rR 2
is
of gases,
R is
about 0'2
2000r2
(0-2
about 0*0000006
R2
13,
and
is
also
X 10~7)2
=6
x 10~ 7
13
2000
x no~ 13> 3
"
>
(0-2
X 1Q- 7 )3
'
~
X 10 13
'
*'* leSS
than the
is
namely
billionfch
P art
'
Hydrogen gas
if it
=2
itself,
13
ELECTRONS
93
fill
We
Now
its
In
plates.
and found
assumed
J. J.
to agree
We
have
cally neutral
the
atom
to be
number being
(3),
1879, 7, 337
"
;
Wiss. Abhand-
THEORIES OF CHEMISTRY
94
move
and
charges
to the
attraction of
the
total
positive charge.
special case in which the
electrons are arranged in circles around the centre of the atom.
He calculates that the highest number of electrons which can
move
common
centre
is five.
If there
circle, their
motion
unstable, whatever
a great
number
may
placed on several
number
is
move round
The
number
third, 8
on
the
not
it
may
figure
In
this
way we
of
ion.
According
to the
number of negative
95
hydrogen.
NH C1,
4
is
many
of
(Prometheus,
1903)
15,
97-102,
121-125,
129-134,
145-151
THEORIES OF CHEMISTRY
00
2|
ll
es
CO
PH
51
<S
bfc
HH
HH
!
O
iH
its
97
by the addition
1
special group 0, containing the elements without valency.
(The
group 1 is composed of the elements with the valency 1, and so
and
Both
on.)
of these
Now,
before helium
was known
known
in
the protuberances, and above the sunspots), which was not found in the
spectrum of any substance of terrestrial origin. The physicists,
therefore,
an
unknown elementary
we may
know
search for
the element
it
in the
on the
earth.
and
it
might, therefore, be
1
There are a number
ment of the elements, as,
to
Abegg, Kamsay,
etc.
is
They
no special
THEORIES OF CHEMISTRY
98
From
what
As
less.
it
0, it will,
its relative
only
0'2, or
belong to the
group
0,
and
The element
element Y.
the immortal
to
X is
be a gas
called
1) is therefore
ought also to
lighter than the
Newtonium,
From very
physicist.
still
bold
honour of
in
theoretical
con-
O'OOOOOl.
Its
to
we
to
built up.
This
is
many great
difficulties
A
which
aid of the
We may,
series,
Ne
Na
19-9
23'05
Elements
At
wt.
Diff.
3-15
and compare
Mg
24
1-05
2-9
Al
Si
Cl
27'0
28'4
31-0
32'06
35'45
1-4
2'6
1-06
3'39
this series
19
ELECTRONS
99
THEORIES OF CHEMISTRY
ioo
forth.
compounds with
positive
hydrogen and
its
substituents.
meet the
it
has
efforts to
now
to contend.
One
difficulties
of these difficulties
is
with which
inherent to
The one is argon, which has a higher atomic weight than potassium (39'8 against 39*1). The figure 38 for argon given by
Mendeleeff
is
"
"
only a theoretical value, computed in order to
l
retain the simplicity of his scheme ; the experiments of Eamsay
give 39*8 for argon, and potassium has been very accurately
with the
between 1-05
in
a
somewhat
and 3'39, i.e. in the proportion 1
3*2,
irregular
manner. In other series this variation is of the same order.
But there are other difficulties not specially characteristic of
Mendeleeff s scheme itself, but only of its representation by
Thomson. After the second series with 20 electrons in the outer
elements.
In the
Kamsay and
come a
series
101
element;
the
therefore
number
if it
were worked
out, differ
appear
lying parallel to one another, but by some other arrangement of
the electrons, which would correspond better with the threedimensional configuration of the atoms.
But,
as
Thomson
makes the
difference
as the differences
be necessary to assume
THEORIES OF CHEMISTRY
IQ2
The
latest calculations of J. J.
new
out a
perspective.
of measurements,
and
Thomson
may
perhaps open
They
result
number
that the
Bontgen rays by
air
gave the
is
much
it
to
Thomson's scheme,
of the
in every series.
Thus, in series 3, neon should corregroup
both
to
the
58-atom
and to that composed of 59 electrons.
spond
We
know nothing
0.
group
loses one of
its
electrons,
why
should
it
regain
its stability
by
simply adding on the lost electron to its outside, and not just as
well by attracting a negative monovalent atom, e.g. a chlorine
in other words,
why
phenomena
of matter.
He
supposes electrons to
move
J. J.
(6),
ELECTRONS
103
Lenard has shown that in the arc light the principal series
and Na) is developed in the outermost edge of the arc,
the first subsidiary series in a zone which lies within this edge,
the second subsidiary series in a zone which lies still more
towards the centre, and so on. Since there is no doubt that the
temperature increases towards the centre, this would indicate,
according to the second law of thermodynamics, that the splitting
(of Li
accompanied by
loss of heat,
which
is
Na
ion,
and
so on.
In any
case, Lenard' s
series
and the
first
subsidiary series
on
by
THEORIES OF CHEMISTRY
104
spond
radium
in 28 minutes (all the times corre50 %). These substances are all
to a decomposition of
to
Ra. D,
Ra. F,
Ra. G, inactive
143 days,
end product ?
(Polonium.)
Ra. E,
6 days.
40 years.
(Radio lead.)
Active deposit.
FIG. 13.
Slow change.
Now, we imagine
ex-
pulsion
ford assumes
them
to be
helium atoms
10
possessing, according
'
sec.
Rutherford holds the opinion that every change accompanied by a-rays is characterized by the loss of one atom of
helium, so that finally the radium atom would lose five helium
light.
Rutherford,
"
Cambridge
would have an
:
1905, p. 450.
4=
ELECTRONS
105
205 (He
about
From
at
out 4
X 10~ 4
time
is
number
of emitted a-rays.
From
X 10 8 and
x 10 6 x 1250 = 25 X 10 8
years respectively.
THEORIES OF CHEMISTRY
io6
radium
If
is
is
easy to calculate
Soddy
year.
NH
4
composite metal, something analogous to ammonium,
Metallic
4
alloyed with mercury, was prepared by Berzelius.
it gives ammonia gas, correBy the loss of one
NH
2
sponding to the emanation of radium, and by the further loss
of an atom of H, diamide (NH 2) 2 the mother substance of the
,
hydrazines, discovered by
Emil
NH
would give
2
4
hydrogen
known except in the form of
Fischer.
NH
2
its
By
further
loss of
By
hyponitrous acid.
still
under
loss of helium.
motion
is
of the surrounding
velocity of
this
light.
rapidly than the kinetic, and would, if this speed were attained,
therefore the electron can never have the
become infinite
;
velocity of
light.
Soddy, Phil. Mag., 1905, 9, 768. Cf. also pp. 19, 20.
Concerning the electrochemical affinity of ammonium,
Zeit.
cf.
Coehn,
609.
Zeit.
If
any mass,
107
necessary to
of the supplied
it is
not only for the kinetic energy of the mass in motion, but also
for the magnetic energy.
As both these at the commencement
are proportional to one another, we may substitute for the
were
we might
true,
its
apparent mass
some very
interest-
1
ing experiments of Kaufmann seem to indicate such an increase
in the apparent mass of the electrons.
His figures on the mass
of the electrons of /3-rays obtained from radium preparations,
Mass
2'36
2'48
2*59
272
2'83
1-5
1-68
2-01
2-55
3-12
1'83
2'04
2'43
3'09
is
x 10 10
of electrons
(observed by Kaufmann)
Mass
of electrons
(calculated
son)
1'65
by J.J. Thorn)
of the electron at
Abraham's 2 and
J. J.
low speed
Kaufmann show an
to 1.
is
put equal
increase, as
velocity approaches to 3
X 10 10
on
ed.),
skilful
1906, 653.
in
his
remarkable
io8
THEORIES OF CHEMISTRY
"
"
The eruptions on
matter endowed with such high velocities.
the new star in Perseus (February, 1901) did not attain a
7
velocity greater than 7'5 X 10 cm. per second, and the greatest
observed velocity of the protuberances on the sun is 8*5 X 10 7
cm. per second, exceeding that of our most rapid projectiles by
CHAPTEK IX
THEORY OF GASES
HITHERTO we have
of
atoms
now we
molecules.
very dissimilar
properties.
In the seventeenth century, Boyle carried out his fundamental work on gases, and discovered the law that bears his
name. He enclosed a quantity of gas in a U-tube, of which
law
is
therefore
where
K-, or pv
K, or p
= KG,
enclosed gas,
is
the pressure, v
At
is
may
C =
-,
the
the beginning of the last century, Gay-Lussac, in determining the dilatation of gases by heat, made a new discovery.
He found that all gases have very nearly the same coefficient
THEORIES OF CHEMISTRY
io
where VQ
sure,
is
Boyle, and on
Lussac.
making p constant we
get
The law
Boyle.
Mariotte tested
it
it
for higher
pressure.
below 760
About
mm.
forty years
enclosed
air,
this
disappearance of the oxygen and an equivalent quantity of hydrogen from the gas-mixture. In order to ascertain the quantity
of oxygen, it was evidently necessary to know what fraction of
the diminution of volume was due to the disappearance of the
This
fact, in
THEORY OF GASES
in
to the circumstances
2:1. In the last case the carbon dioxide formed occupies the
same volume as the carbon monoxide. In the decomposition of
ammonia gas, the volume of the compound is found to be
double the volume of the combined nitrogen, and two-thirds
that of the combined hydrogen. Water in the gaseous state
occupies the same volume as the component hydrogen, and
double the volume of the component oxygen.
Gay-Lussac showed how it was possible, by means of his
law and the known densities of the elementary gases, to calculate
the densities of their compounds.
Berzelius understood perfectly the importance of the connection between Gay-Lussac's discovery and Dalton's law, and
wrote the following remarkable words to Dalton (1812) " You
:
are quite right that without the atomic hypothesis the theory of
multiple proportions is a mystery, and, as far as I know, all
results hitherto obtained contribute to the verification of this
hypothesis.
But
this
theory, as
Gay-
Lussac's measurements; Berzelius used them for the determination of atomic weights. For instance, Dalton supposed an
"
"
THEORIES OF CHEMISTRY
ii2
H 0, just
as
Berzelius
we do now.
asserted
that
is
equal volumes of
He
(under the
same conditions of temperature and pressure) contain the
same number of molecules. One molecule, i.e. two atoms, of
hydrogen and one molecule, i.e. two atoms, of chlorine give
different
gases
THEORY OF GASES
found that the vapour density of sal-ammoniac (which is a compound of hydrochloric acid and ammonia in equal volumes, and
therefore must have the composition
4 C1 or a multiple of it)
NH
only 1*01, only a little more than half that calculated accordSuch " abnor4 C1, viz. 1'84.
ing to the molecular formula
mally" low vapour densities were also found for the comis
NH
NH CN, PH
pounds
NH OCONH
PH
4 Br,
4 C1,
(NH 4)2 S,
NH SH,
PC1 5 and
As
of different
2.
compounds
temperatures.
fore, natural
at
high
It seemed, thereto
suppose that
NH
4 C1
decomposed for instance,
3 and HC1.
This was shown to be true
;
into
NH
tube,
r,
in
the
axis
of
In
A narrow glass
tube,
t,
Blue
led to the
top of
just above the opening
of the tube r, and another narrow
FIG. 14.
Dissociation of sal-
ammoniac
(v.
Pebal).
NH
diffuses
v. Pebal,
acid,
HC1.
If,
therefore,
Ann. Chem.
u.
THEORIES OF CHEMISTRY
ii4
NH
decomposed into
NH
above
whom we
find curiously
of this
explanation,
among
new
ideas.
They
come
this objection, v.
asbestos diaphragm
subject were carried out, and they all supported the idea of
dissociation.
Especially interesting were the determinations
of vapour densities over considerable intervals of temperature,
by which the increase of the dissociation with temperature was
air
temp.
1.)
155 163 172 185 210 225 237 248 268 295 310 319 360 C.
density 5'27 5-23 5-17 5-13 4-26 4-19 3-83 3-30 3-10 3-09 3-08 2-88 2-61
till it is
C.
densities.
v.
Analogous
recent
THEORY OF GASES
We
115
led to
correct deductions.
It
of all laws.
pv
ET.
is now a
p, v, and T have here the same meaning as before, but
natural constant, the same for all gases, provided that we work
HN
we may
pv
one erg
are
is
now dyne X
^-5
T7)5
cm.,
i.e.
the
calories, therefore
pv
= 8316 X
10 6 T ergs
may
= T99T
calories.
easily be deduced
from a simple
velocities.
The consequences
of this
view
"
kinetic
are developed in an admirable way in the so-called
This theory was founded by Daniel Bernoulli
theory of gases."
in 1738
it
perfectly elastic
sphere, such
as
a molecule
is
imagined to
THEORIES OF CHEMISTRY
ii6
be, travelling
2 mu,
u, is
if
the mass of
is
If
mole, that
is,
the breadth
I,
b,
]~
Kb
till
^n A
NJ
move
we may
parallel to
i.e.
h,
to
again, and
If every molecule moves
so
xl
FlG 15
u,
A will
21
be
it
2mu
exert a pressure K
,,
~i
will
The pressure
gives -^ impacts to A.
is
exerts a pressure
we
parallel to
I,
Hence K molecules
A is n^ 2mu
.
o/-
TT
=$
-LI-L
Now Uh
is
p,
we have
the formula
pv
= JMw
law, that
pv
ET,
Consequently we
have
JMu" =
or
10 6 T ergs
x 10 6 T\/249-5
cm. per second.
83-16
\/M
From
this
formula we
molecules of a gas.
At
may
C.,
i.e.
THEORY OF GASES
Hydrogen, u
Atm.
=
=
=
=
air,
Oxygen,
Nitrogen,
Argon,
u
u
u
u
1837
m.
117
Carbon dioxide, u
394
=
=
=
u =
u
u
Ethylene,
Water- vapour, u
Marsh
485
461
492
424
gas,
Ethyl ether,
m.
sec.
sec.
651
493
615
304
o.
The
is
|~
number
FIG. 16.
same pressure
in V, inversely proportional to the square root of the molecular
This was, indeed, found to
weight, or of the density of the gas.
be true by
Graham
in 1846,
who gave
CH
Time
*/(T
Gas.
C2H4
Air
....
....
C0 2
....
0-263
0-745
of efflux.
0-276
0-753
0-985
0-987
0-986
0-986
1-0
1-0
1-051
1-053
1-237
1-203
The same law also holds good for the velocity of efflux of a
gas into a gas-filled space, as has been verified by Bunsen.
As we see from the expression for u, the molecules have
greater velocities at higher temperatures.
Suppose that we
have one mole of a monatomic gas (that is, a gas the molecules
of which consist of single atoms, e.g. mercury) enclosed in a
gas-molecules.
more atoms, a part of the energy supplied may be used up in
increasing the distance apart of the atoms against the force of
their attraction for each other, or in augmenting their speed of
THEORIES OF CHEMISTRY
ii8
We
gram
of a substance at constant
its specific
we have
Therefore
from v to v
VQ
5^5).
vt
#0^770
Z (o
The
therefore
= Mcv + f Mcv =
= 1-67 cv
t
This relation
as
it
is
we have
is
Mcp
and cp
mole,
equal
volume
is
the increase of
denoted by cp and
This is also equal
,
t.
1-67
Mcv
VQ).
t,
THEORY OF GASES
119
in Mendeleeff s
scheme
group
gases were determined from their densities according to Avogadro's law, but since they do not form any compounds there
of determining
atomic weights
their
unity, the
pressure
is
heated through
p(v t
If,
Rt
= T99
(cp
cv )
cv
at constant
is
cv is
1,
cal.
= Mfe -
put equal to
and Mcp
k,
cv )t.
we have
Jc
1/99
A/
~~
T
JL
to a gas on heating it 1
C.
two parts the increase in the kinetic energy of the
rectilinear motion of the molecules, and the increase in the
so-called internal energy of the molecule.
The -latter consists
of the increased speed of rotation of the atoms raund their molecular centre, and of the work done in separating the atoms from
each other. This internal energy may be called U. Its
U
increase between the temperatures t and t is U
We have seen that according to Avogadro's law
consists of
|M^=|x
for all
gases.
Avogadro's law
l'99Tcal.
may
also be
law says, according to the last formula, that the kinetic energy
of the rectilinear motion of the molecules contained in one mole
THEORIES OF CHEMISTRY
120
T99
to
heating
cal.
at constant pressure
it
given by the
is
through
formula
(1-99*
2-9850
2'5
1-99* cal.
Mcp*
or 1-99^-^-s-f
1
K
if
1*4
HI
04 =
2-5
is
+U -U
X 1-99* + U - U
1-99*
2-5
approximately
1'4,
and consequently
3'5.
U -
TJ
1-99* cal.
consequently K
j-^r1
4-23.
In this case U t
is
U =
173 x
1'99*.
k
= 4'33, U - U
For ammonia and marsh-gas k = 1-30 and
K
= 1-83 X 1-99*. For ethyl ether k is only T03, and we find
U, - U = 32 x 1-99*.
t
JL
from
work
is
for the
monatomic gases
THEORY OF GASES
121
mean
This
number
is
is
proportional to
0,8
0,6
0,4
0,2
FIG. 17.
We
learn from
it,
mean
rare.
Now,
gases.
THEORIES OF CHEMISTRY
122
If the
when
Thus, for
the one
were
at
if
instance,
sulphuretted hydrogen
prepared
end of a tube 400 metres long, the smell of it would be observed
diffuse
other by
means
of gas-currents,
it
will take
many
years before
can be smelt at 400 metres' distance from the point of proThis depends on the collisions of the molecules of
duction.
it
2 S with the molecules of the air, and the time for reaching
the point 400 metres distant will be the greater, the greater
the number of colliding air molecules.
This phenomenon
By measuring
it,
we
is
called internal
The
third
The molecules
at the
is
by
We may
its
upper
upper end will then possess a
mean
Evidently this
path of the
possible, by experiments on the
conduction of heat, as well as by determinations of the rate of
diffusion or of the viscosity, to determine the cross-section of
free
it is
the molecules.
The method that has been used is to determine the crossby measurements of the viscosity, and
THEORY OF GASES
thereafter to calculate the coefficients of diffusion
123
and
of con-
This matter
discussed in a very
0. E. Meyer (second
is
of gases, to
and also
density,
to the
mean
free
is
arrived at by Maxwell, has also been verified by experimental researches carried out by himself, 0. E. Meyer, and
other scientists. At very low pressures the law of Maxwell
first
ture,
conclusion,
way
may
which
infers
to liquids, is also
that
found
This
behave in an opposite
be in good agreement with
gases
to
experience.
The
of
gas under a
by blowing a current
through a narrow tube.
definite
pressure
the viscosity the molecular free path and the total crosssection of the molecules in a given quantity of gas may be
determined.
From
The following
viscosity,
path,
I,
and the
r\ y
Q, in sq. cm.,
of
the
molecules
contained in
V,
total cross-section,
The experiments
1 c.c. gas at
C. and 76 cm. pressure.
were carried out by Graham the table is from 0. E. Meyer's
book
;
124
THEORIES OF CHEMISTRY
THEORY OF GASES
If
we
125
mean
we
x 10 9
for
oxygen
to
9'5
free path,
This quantity
X 10 9
for hydrogen,
c.c.
C.
1 sq.
Up
if
it is
we wish
we must
introduce some
new
This hypo-
thesis evidently gives too high a value for the real volume of
the molecules, for there must also be some interstices between
Not only do
also for
of the deviations
Van
(p
Here
the determination of
pressure of a gas I
molecular volume.
dielectric constant
K-l
THEORIES OF CHEMISTRY
126
K=
n*, where n is
According to a law deduced by Maxwell,
the refractive index of the gas in question hence, it is not
in cases where this law holds good, if n is
necessary to know
;
determined.
We
THEORY OF GASES
N =
X 10 20
127
from b,
and from v, 1'5 X 10 18
Now, according to van der
Waals, the real volume is about a fourth of the volume, v, of the
The last figures are thus about 16 times too small, and
liquid.
on correction would give a value for N of about 27 X 10 18
On the other hand, the relation between the dielectric constant (K) and the volume of the molecules was developed by
Mossotti on the assumption that the molecules are perfect
conductors throughout. Now this may be true for the atoms in
the molecule, but not for the molecule itself, for because of
their rapid rotation around their gravitational centre the atoms
collide with foreign molecules which enter within a surface
much greater than the cross-section of the atoms, and this
8'5
0-98
X 10
or
in
18
surface
value of about 20
X 10 18
is
c.c.
different investigators.
The
last
or 28,950
x 10 10
is
electrostatic units.
Since 1
gram
of
hydrogen
and 76 cm. pressure occupies 11,200 c.c., the total charge
on the atoms in 1 c.c. hydrogen is 2'59 x 10 10 electrostatic
If we divide this value by the value of one atomic
units.
10
we obtain 55 X 10 18 as the number of
charge, 4' 69 X 10~
atoms in 1 c.c. hydrogen. This value is double the number of
molecules, because one molecule of hydrogen contains two atoms.
at
C.
We
N=
27*5
X 10 18 which
,
calculated above.
calculated on similar
gives the cross-section
1
Planck,
J. J.
(J. J.
528.
THEORIES OF CHEMISTRY
128
C.
is
it is
-=
xXI
X 10- 6 cm.
There are
and as a
We have
better agreement must not be expected.
supposed that the space surrounding a molecule, and into
which no foreign matter can penetrate, is spherical in shape.
0. E. Meyer
This is probably only a rough approximation.
has endeavoured to show that the molecules have a flat shape,
strict, as
pointed out by
The kinetic theory of gases was for a long time held in the
Boyle's law may be derived from it very
highest estimation.
simply, and
and
also, recently,
laws
2
regarding the breadth of the lines of the spectrum (Michelson),
were discovered with the help of this theory. But, on the other
many
difficult to
is
d.
allg.
Chemie,"
2nd
edit.,
vol.
i.
p.
215.
THEORY OF GASES
129
which are of great interest, respecting the atmoJohnstone Stoney called attention
of
bodies.
celestial
spheres
to the fact that a body moving upwards with the velocity of
certain facts,
H'2 km.
For the moon and the sun the corre2 km. and 613 km. per second
we
have
seen
Now,
previously that hydrogen
sun's attraction).
by the
sponding
respectively.
molecules at
second.
new hydrogen
the hydrogen,
if it
any remaining,
once existed on the moon, would have very
it.
its
molecules
is
The velocity
for oxygen.
molecules, i.e. about 0*58 km. per second at 150 C. This is only
But according to Maxwell's law of
0'29 of the critical speed.
distribution, about 0*03 % of all the oxygen molecules have
and therefore it is no
no trace of an atmosphere on the moon.
which may originally have existed on the
course of time have been absorbed through
find
wonder that we
Carbon dioxide,
moon, will in
the process
of
weathering.
atmo-
much
and 357.
25
if it
1899, 9,
were absorbed
1
THEORIES OF CHEMISTRY
i3o
air.
Therefore, if the helium did not flow away from
the atmosphere as rapidly as it is produced, we might expect a
much higher quantity of this gas in the air than that now
from the
if
of
helium at
it
does.
C. is 1'12
km. per
second, about the tenth part of the critical speed for the earth's
atmosphere. Observations of the temperature of the upper
and, in
it
helium
(at
Therefore
Cook 1
by
much
less density
when
(as,
springs during the period which has since elapsed has not been
greater than the present quantity of helium in the air.
Stoney's hypothesis must, as will be seen from these considerations, be worked out much more fully than it is at
2
But
it
resemble the
Of. v.
Eogovsky, Astrophys.
THEORY OF GASES
131
In the
a most important
role.
During
this
process
the so-called
why
already come
to
CHAPTEK X
CHEMICAL KINETICS AND STATICS
EARLY in the history of science it had been found that different
acids have a very different affinity for the same base, and in
this sense it was said that sulphuric acid is the strongest of all
acids, for
by means
tables
of affinity," in
(e.g.
different
The
compounds.
Generally speaking,
of
Bergman's system
never limited.
it
may
Bergman prevailed
till
lately.
is
133
inverse
value of the
affinities,
them experimentally.
In
reality,
false hypothesis that all acids are of the same strength, if they
Berthollet regarded all
are present in equivalent proportions.
"
chemical
reactions as incomplete, and introduced the idea of
equilibrium."
solid form.
Berthollet,
"
action
Untersuchungen
e.g.
tiber die
felspar
Gesetze
cler
is
decomposed
Verwandschaft
"
;
THEORIES OF CHEMISTRY
134
acids as carbonic
is
ful,
weak
relative masses.
It
"
it.
He
K C0 BaC0 3
and
BaHPO*
2
3
was
show
that
the
NaaCrO*.
equilibrium
independent of the way in which the salts were mixed; for instance,
the end result was the same, if he started with BaC0 3 and
K 2 SC>4 (and a given quantity of water), or with BaSO* and
similar cases,
He
for instance,
and
tried to
He found
nitrate, and precipitated them by adding alcohol.
that the precipitate showed the conversion of this system into
that of potassium nitrate and lead acetate to the extent of 92 %.
On dissolving the two latter salts and precipitating, he found
that 9 % had been converted.
Evidently he should have found
8 %, and then the final result would have been independent of
the starting-point.
BaC0 3
135
the
the original
K S0
2
so
is
that
mobile."
salts.
to
To represent
it
K C0 3 + BaS0
2
$K S0
2
+ BaC0
e.g.
3.
i.e.
He
an
acid.
according to him, a reaction would proceed with a velocity proportional to the quantity of reacting substances which
remained to be transformed in order to attain equilibrium.
views
had
CiaHaaOn
+H
= 2C Hi
6
6.
Cane-sugar is dextrorotatory towards polarized light, wherethe mixture of dextrose and laevulose is laevorotatory.
This change of the angle of rotation had been long used for
determining, by means of instruments called saccharimeters,
as
instrument (1850).
1
etc.
carried
on
at high
THEORIES OF CHEMISTRY
36
if
by (A
#),
This gives
the equation
A
log
where KI
A-
log
(A -
x)
reaction.
This,
Kit
Wilhelmy
(in minutes).
137
HN0
number
of reactions,
and, inversely,
if
equivalent quantities
C 2 H 5 OH
equation
2 0.
it
is
pro-
Benzene
The
to
Of.
little
influence
on reactions
THEORIES OF CHEMISTRY
138
in liquids.
completely transformed
Another
reaction, in
when equilibrium
is
reached.
so that
action
to the equation
by Warder,
Weak
in 1881.
solutions (0'05
normal or
less)
had
measurements
to
be made.
dx
The
velocity of reaction,
-=7,
is
x), and of
proportional to the concentration of the base, (A
if
the
are
used in
the ester, also (A
x),
reacting substances
equivalent quantities).
The
reaction-velocity is therefore
fif
l/fccl/
where
K is
the velocity-constant
A
Warder found
this
on integration gives
A(A
x)
A being
= KA-
Knain.)
16
A^aT)
5-76
(A la?)
0-563
15
9-87
1-601
0-107
25
11-68
2-705
0-108
35
12-59
3-69
0106
55
13-69
5-94
0-108
120
14-90
13-55
0-113
Warder,
0113
139
by Spohr,
myself,
and
others.
all
They
confirm
This reaction
reactions,
present in such great excess that its quantity does not sensibly
alter during the process.
Therefore it may be put as a constant
in the equation, which in this way becomes similar to that for
so-called monomolecular reactions.
An
explanation of this
wanting.
C 2 H 5 OH + H 2 S0 4 = C 2 H5 OS0 2 OH + H 2 0,
+ 2C2 H 5 OS0 2 OH = C2 H 5 OC2H5 + 2H2 S0 4
by a continual change
In the same manner
takes place.
1
3
4
5
Cohen,"
THEORIES OF CHEMISTRY
HO
which
of intermediate products
He
pointed out that at one and the same time probably only very few molecules exchange their ions for the ions
of other molecules.
current.
Theoretical
work
was carried
1
and
Guldberg
Waage, who
reaction
two substances,
and B,
at constant temperature is
where C A and C B represent the concentrations of the two substances, and k is a constant which increases with the temperaIf by the interaction of A and B the substances E and F
ture.
are formed according to the chemical equation
an equilibrium
racterized
is
by the opposite
This
is
cha-
that
This
is
valid
for
homogeneous
If a
equilibria.
if,
solid
for instance,
"
subis
Guldberg
iiber
d.
cbem.
Affinitat,"
(constant) solubility.
141
If
solid
K C0 + BaS0
2
^K S0
+ BaC0
3,
if
the
&C B
= hCJF
or
-p
OE
const.
"active mass"
its
that
pax
+x
200
39*5
4-06
250
50-0
4'00
350
250
300
200
71-9
3-87
25
30-0
4-00
25
40-8
3-94
50
0-5
3-95
Mean
3'97
THEORIES OF CHEMISTRY
142
experiment.
ments. 1
be
should
15,700
find
(= 0-845 x 1400). This indicates that the sulis neutralized to the extent of 84*5 %, and that 15*5 %
acid
phuric
of the sodium monochloracetate remains intact.
There exists,
1183
cal.
the
that
7
T
lo'o
strength
or
"avidity" of
the
sulphuric acid
is
acid.
and
and 2
litres of
Ostwald
65.
of these different
143
The discussion of these data will find its proper place later
on in the consideration of the theory of electrolytic dissociation.
suffice now to state that, according to these determinathe
chemical equilibria which exist in these cases are in
tions,
accordance with the theory of Guldberg and Waage.
It
may
The
classical
is
that studied
ethyl alcohol, equilibrium is reached as soon as these are transformed to the extent of two-thirds into ester and water. This
where p
is
the
number
of
x)
x\
is reached when x
x = 1
x = J, by
f and p
which value the equation evidently is satisfied.
In 1877, using this equation, van't Hoff 1 calculated x for
different values of p, and compared his results with the results
of the measurements made by Berthelot and Pean de St. Gilles.
He thus found the following calculated values, tabulated at
librium
0-05
corresponding to different
THEORIES OF CHEMISTRY
144
may
"
determined the avidities
"
of the acids in
He
number
is
we
measurements on the
catalysis
means
1
4,
635;
Ann.
d.
Chem.
342
145
This
is
due
to the
simple as in
formation of neutral salts
we
CHAPTEE XI
THE INFLUENCE OF TEMPERATURE AND PRESSURE.
DISSOCIATION
"
ammonium
Dissociation
is
on lowering the temperature the products of dissociaA chemical equilibrium exists between the
tion re-combine.
original molecules and the products of their decomposition, and
i.e.
and we
of dissociation a little
phenomenon
The simplest
the
detail.
case of dissociation
more in
is
split
up
the following vapour densities at the pressures 0*1, 0'2, 0*3, and
0'4 atmospheres and at the given temperatures, referred to air at
the same pressure and temperature
:
Temp.
p=
0-1
0-2
p =
0'3
p =
0'4
650
800
8-8
8-8
8-8
8'8
7'42
7'88
8-21
8-52
900
6-58
7-22
7*45
7'78
1000
5-95
6-72
6-83
7*15
Crafts,
Temp.
1100
1200
1300
1400
1500
p=
O'l
5-40
p=
0'2
6-00
6'24
p = 0-4
6'44
0-3
4-92
5-36
5'62
5'82
4-6
4-82
5'02
5'25
4-5
4-54
473
5'0
4-48
4-52
4'61
147
At higher temperatures
very rapidly; up to about 1200 the
the dissociation
increases
"
increase in the
degree of dissociation," i.e. in the fraction of dissociated molecules, is about 15 % for an increase in temperature of 100.
dissociation
may
Already in
thermodynamics that
for
the equilibrium
expressed by the
equation
I2
21,
const
2
(cone, of I-molecules)
When
number
I 2 -molecules
decomposed in unit
i
of
THEORIES OF CHEMISTRY
148
number
is
sinks to half its former value, the concentration of the I 2 -molecules must simultaneously decrease to the fourth of the original
value.
We
table that the lower the pressure the less is the vapour density.
This is a special case of a general law. If there is equilibrium
of this
RT
loge const.
_ A
dp
the absolute temperature, E is 82 '9 atmospheres
p the pressure in atmospheres, A the
alteration in volume (in cubic centimetres) at constant pressure,
where T
is
with temperature
where
loge const. _
"
represents the so-called heat of dissociation (at constant pressure), that is, in the present case, the heat absorbed
during the transformation of 1 gram-molecule (= 254 grams)
149
into 2 gram-molecules I
T is the absolute temperature, and
const.
,
,,
.,,
T T
f ,1
is the increase in the natural logarithm of she con^-j7
;
d loge
28,500
cal.
pressure).
Another example is the dissociation with increasing temIt has been studied by many
perature of N2 04 into 2N0 2
3
others
physicists, among
by St. Claire-Deville and Troost,
.
A. Naumann, 4
W.
5
Gibbs, Horstrnann, E. and L. Natauson. The
given by
Temp.
26-7 39-8 49'6 60-2 70-0 80-6 90-0 lOO'l 111-3 121'5 135-0
Density
29 2 4
The density
the
of N"2
dissociation
is
'
is
1-68
52 8 65 6 76 6 84 8
'
'
'
3-18, that of
'
'
89 2
N0 = 1'59.
2
1'65
^' l
1-62
'
96 2
1-60
'
98 7
In this case
temperatures.
proved.
1
(3),
27, 606.
6
1888,
THEORIES OF CHEMISTRY
i5o
further example of dissociation increasing with the tem(p. 114), namely, the decom-
shown by the
two components,
its
as
investigations of Wiirtz.
A dissociation
process,
we have
phases
2
(CaC0 3 and CaO) and one gaseous phase (C0 2 ).
The
C0 2 )
is
shall
inappreciable, at
at
calculation of
and 865
W = 29,300
is
C.,
(according to
perature.
C.
at 745
At
4*6 cm.,
1-99T 2
dt
is
Hg
it is
d log
definite value.
610 C.
Thermodynamics requires
where
have a
using
30,800
am-
"
"
called the homogeneous parts of a heterogeneous system the
of
phases
In the equilibrium between ice, water, and water-vapour at
that system.
one solid (ice), one liquid (water), and one
C., there are three phases
gaseous (water-vapour).
*
151
12-3
16-3
20'7
24-9
31-5
Na 2 HP0 4 + 7-12H 2 0; a=
Na 2 HP0 4 + 0-7H 2 0; b=
Water
c =
7-4
9-9
14-1
18-2
30'2
4-8
6'9
9-4
12-9
21-3
Temp.
-=
36-4
4<K>
30-5
41-2
0-72
0-78
0-78
0-88
0-46
0-50
0-52
0'55
0-62
0-68
0-75
atmosphere,
is
called
solves in
As
it loses its
efflorescence.
it
will be seen
value
1,
and
temperatures
than
1, i.e.
water.
at about 65
-
(above
two
salts
and
At about 52
C.
52) and
(above
At higher
65) would be
greater
HP0
At temperatures above 52
12H 2
HP0
52
C.,
(In
is
Na2 HP0 4
THEORIES OF CHEMISTRY
152
This
is
of crystallization.
moisture and form combinations with less water of crystallizaThis simple protion, until finally the anhydrous salt is left.
(Na 2 S0 4 .10H 2 0)
Cryst..
Epsom
+ 13H
Water.
Cryst. astrakanite.
salts.
ice.
stable below
is
the equilibrium
pressures the latter
At
is
ordinary
and the former above this
C.,
of ice
The following
and Eegnault's
measurements
ICE.
Temp.
Vapour-pressure
18
Wi
-30
-20
-10
0*292
0787
1-974
.-
672
673
.0
C.
4'579
666
mm.
cal.
WATER.
Temp.
-20 -10
Wi
Systems
582
580
C.
mm.
cal.
in
Cf. Scheel,
1-99T 8
dt
and
WL
loge PI _
~
~~
d logg p
pi)
153
we have
'
water (p)
__
where Wi and
are the latent heats of evaporation of 1 grammolecule (18 grams) of ice and of water respectively. From this
it
follows that
pi
&
-p
where
Q = Wi
W- W
is
"
'
1-99T2
1-99T 2
dt
theory.
of
10
values
way
that
we
melt
first
it
The
the water.
797
cal. at
0, and 75
cal. at
10
C.
by
direct calori-
metric measurements.
is
Q
1-99T 2
dt
THEORIES OF CHEMISTRY
154
The heat
is
given by
T99T2
We
thus find
Q=
1575
cal.
dT
and Qi
3105
The
cal.
later
As an example
of
researches of Isambert
may
be cited.
0-3
Temp.
30
on the vapour-pressure
of
AgC1.3NH 3
They gave
12'9
18'8
50
70
22'6
90
25'3
110
27-9
130
31-0
150
34'2
1713
57-0
48'5
24U
488
C.
mm
of
for
t
-16
AgCl
for
2AgCL3NH 3
155
mm.
one solid
known
we may
definite values.
of
the
THEORIES OF CHEMISTRY
156
the other.
equilibrium point
is zero.
temperature, pressure, and the concentration of each of the substances in one of the phases.
The same condition holds, namely,
that if the concentration of one substance in one of the phases,
of the salt in the liquid phase, is known, its concentration in
e.g.
Four ( = n + 2) phases
definite
but
at
one
may coexist,
only
temperature, namely,
21*3 C.
These four phases are water-vapour at O73 mm.
pressure liquid, containing 36 grams of salt to 100 grams of
all
water
ice
and
NaC1.2H 2 0.
number
and
21*3 C.), but
trarily, e.g. the temperature (between
then the other variables become fixed, so that the composition
and the pressure of the saturated vapour can only
have a certain definite value.
of the solution
we may
and
its
concentration,
number
of
become
Gibbs
fixed.
is
of possible combinations of
any number
of substances
CHAPTEE
OSMOTIC PRESSURE.
XII
into
an
acid)
Now,
was measured by
its conductivity.
the order of different acids, as regards their power
thermochemical measurements.
same
as that of their
me
molecules are identical with electrically active ones, and therefore the conductivity of an acid was regarded as a measure of
its
few
the law.
Arrhenius, Bihang
Nos. 13 and 14 (1884).
till
Kongl.
Svenska
Vet.
Akad. Handlingar,
8,
THEORIES OF CHEMISTRY
158
electricity.
why
The
this
show
it
regularities
of the solvent.
He
where
0-63w
Later
solvent were not in good agreement with this equation.
on van't Hoff showed that Eaoult's equation was not correct.
On
p
1
it
159
was because
it on
Guldberg had already, in 1870, from thermodynamical considerations, deduced the connection between the lowerings of the
If Raoult had been
vapour- tension and of the freezing-point.
cognizant of Guldberg's work he would have been able to deduce
the correct law for the freezing-point. However, being unaware
of the previous theoretical work, he only established the fact
that there was proportionality between the two lowerings (1878).
Later on he also found proportionality between these lowerings
and the
power possessed by
n a solution of less
osmotic pressure.
Fm.
rounding weak
18.
salt
cells of
In a solution of equal
osmotic pressure.
Plant
cells,
solution.
according to
When
was
De
Vries.
established,
and no water
the
protoplasm contracted and did not fill out the surrounding cellwall (see Fig. 18, A, B, C.). This could be observed under the
1
THEORIES OF CHEMISTRY
i6o
microscope, especially
colouring matter
De
Vries,
if
monovalent
ions, e.g.
litre,
of cane-sugar or of glycerine
molecules as the corresponding
solutions of the binary salts which were isotonic with the same
On the other hand, such salts as CaCl 2 MgCl 2
cells.
2 S0 4
many
When
this is
too
which corresponded to
and found results wholly in accordance with those
De
solutions
Vries.
3
had
Already in 1867 the German physiologist Traube
succeeded in -producing
many
as,
for
instance,
porous pot in the following manner He took a porous earthenware pot and sucked water through it till the pores were
:
2
3
4
9, 26.
was then
It
air.
with a solution of
filled
bath
in
placed
161
of
copper
one another.
cells.
freely,
It
of cane-sugar
slowly.
Pfeffer filled the cell
A (see
latter
was sucked in
Fig. 19)
fitted
it
in
water-bath
tem-
constant
at
perature.
cell
contained
in
inanometric
the
tube.
this in order
was reached
at
which no
When
Pfeffer
cane-sugar,
cell.
cell.
filled
the
cell
osmotic
pressures at
14 C. :Percentage of sugar,
Osmotic pressure, p.
Katio,j?:c.
The numbers
pressure
solution
He
is
;
c.
2 '74
535
1016
508
1513
4
2082
554
521
535
nearly proportional
to
indicate
the
3075
513
that
mm. Hg.
the osmotic
concentration of the
this conclusion
also
as
gum
THEORIES OF CHEMISTRY
62
arable,
For
Percentage of
KN0
c.
3l
Osmotic pressure,^.
Ratio,
In
pic
the ratio
case
this
0'80
143
1304
1630
2185
is
3'33
1530
due to the
perfectly semi-
especially
high pressures. The salt slowly
passed through the membrane, although with a much less
speed than the water. This is generally the case with such
membranes the copper ferrocyanide membrane is the best
at
permeable,
of
all
those
gelatine, etc.
hitherto
prepared
tannate of
(prussian blue,
1
).
Temperature
Osmotic pressure
.
(observed)
(calculated)
The
5Q5
.
Osmotic pressure
.
6*8
JJ
5Q5
13-5
32
22'0
14-2
^ ^ ^ ^
^
36 C.
567
mm. Hg.
51g
are calculated
figures in the last line
on the assumption
increase between 6 8
calculated.
to this point when De Vries
his
Hoff
van't
asked
opinion concerning the nature of osmotic
Hoff
Van't
perceived the similarity of the laws for
pressure.
Cf.
Berkeley and
163
proportionately to
able to osmotic
phenomena was
still
wanting.
cane-sugar
Hg =
61'5
61'5,
279-8.
The two
values are so very close that after this calculation van't Hoff
did not hesitate to enunciate his important law, which is
the
:
at
the same
temperature.
how
correct expression
where dT
T*
1-99
>
100
'
n
in
Eykman,
Zeit.
Eykman
showed by direct
THEORIES OF CHEMISTRY
i6 4
experiments that the equation of van't Hoff agrees with experiment, whereas that of Eaoult often gives very incorrect
results
(cf. p.
For the
but then
158).
solvent.
By the help of these equations we may determine the molecular weights of all substances which can be dissolved in a
solvent whose freezing-point or boiling-point is at an accessible
temperature.
As examples of
may be cited. The
(I)
I.
0-0102
0-0108
0-0105
0-0105
THEORIES OF CHEMISTRY
66
as giving
state.
An
molecular lowering
Some
figures of
Eykman's
are given
The values
superiority of van't Hoff s law over Raoult's rule.
calculated according to the two methods are indicated with an
Solvent.
167
may
is
nitrate
of
Eaoult and
by a wall
of ice.
We may
now keep
this
which melts on the other side, so that water diffuses into the
solution.
By choosing an appropriate temperature we may
regulate this process so that just as much ice is melted on
the one side as freezes out from the water on the other.
We
also,
frozen solvent
some
is
cases occur in
which the
This
The
solid solvent
then contains a
may
be
vapour-pressure is greater than it would be if the vapourThe total vapourpressure of the solute were inappreciable.
and
is
therefore
the
observed
measured,
pressure
lowering of
168
THEORIES OF CHEMISTRY
the vapour-pressure
is
less
If the dissolved substance has a high vapour-pressure compared with that of the solvent, e.g. if alcohol is dissolved in
it
These
all
an explanation by
of
the
existence
solid
solutions,
assuming
any more than by
that
are
in
formed
the
solution by the
assuming
complexes
molecules aggregating together, for in both these cases the
observed lowering of the freezing-point should then be less than
the calculated one.
CHAPTEE
XIII
ELECTROLYTIC DISSOCIATION
ELECTROLYTES in solution behave similarly
to substances
with
NH
van't
to
of
a partial
We
recalls the
the
solution of
sodium
NaCl
gram
of
chloride,
in
it
Hoff s equation,
1'85 C.
is,
according to van't
We
a matter of
normal solution
1
of
fact, is
NaCl.
(3),
1879, 6,
1.
THEORIES OF CHEMISTRY
In the same way I l examined (1887) solutions of all the
substances for which Eaoult had determined the freezing-point,
and
for
ninety in number.
more
closely,
with the
newly
(The same
other solutions.
is
and giving
electrically con-
shows
freezing-point, and
that at the concentration
0-4
FIG. 20.
0-5 Cone
is at-
tained.
the
Why
same
result
We may
little
more in
detail.
If a
1, 631.
ELECTROLYTIC DISSOCIATION
171
sodium ions in the solution below. Now, the ions carry their
electrical charges with them, so that the water above should
become charged negatively, and the solution below it positively.
Because of this electric charge, the negative chlorine ions are
held back, and the positive sodium ions attracted upwards
from the
is
by F
many sodium
as
ions as
is
and of chlorine
this effect.
We
By chemical
analysis
it
can be easily recognized by electrical means. It was exactly in this way that Nernst l calculated
the electromotive force of concentration elements consisting of
this quantity, which, however,
of
it is
Helmholtz, Sitzungsber.
AM.,
II.,
979.
GesammeUe
THEORIES OF CHEMISTRY
1/2
acceptance of the
The combined
and of
electro-
we take
consideration
into
that
by means
of the laws
of
only gases (which play a far less important role than solutions)
could be subjected to theoretical treatment by means of their
equations of condition.
By
numerous
electrical
phenomena were
covered so wide a
On
new
ceptions.
Here
I can
known
Now,
it is
well
the
etc., in
ELECTROLYTIC DISSOCIATION
the only absolutely additive property of matter.)
accurate examination of this law by Landolt,
173
The extremely
years ago believed that he had found some very small, but,
nevertheless, not unimportant exceptions to it, have finally
resulted in a perfect proof of the accuracy of Lavoisier's conceptions (see p. 14).
There are other such properties, which are only approximately additive for instance, the molecular volume of a com;
To
molecular volumes
for
20 C.
may
KC1,
37-4
NaCl,
27-1
Diff.
In
10-3
be used
KBr, 44-3
NaBr, 33'8
Diff.
(i.e.
volumes of a gram-molecule) at
10-5
Br
Br
KI, 54-0
Nal, 43-5
Diff.
01
01
=
=
6-9
6-7
- Br =
- Br =
9-7
9-5
10-5
volumes of
K and Na may
by 10*4 units.
The specific gravities of aqueous solutions are closely connected with the molecular volumes of the substances in solu-
As long ago
tion.
as 1870,
Valson
differ
same
which
more thoroughly investigated
2
by Eontgen and Schneider, who verified the results of Valson.
The latter was so strongly impressed by these regularities, that
1
Valson,
20, 361.
2
u.
(3),
(4),
1870,
THEORIES OF CHEMISTRY
174
behaved as
As an
C. are
ELECTROLYTIC DISSOCIATION
175
H S0
2
4,
we make use
in chemical analysis.
give the characteristic reactions of the ferrous ion, e.g. they are
precipitated by alkali carbonates or hydrates, they give with
as a ferrous salt.
This
is
due
to the
my
structive
silver
say
formulation
is
ions
are
reagents
for
Now we
chlorine ions.
This
reaction.
3
4
(3),
Chem.
u.
1865, 127,
THEORIES OF CHEMISTRY
176
chloride
formed
them
from
according
to
the equation
of
equilibrium
Ag+Cl^AgCl
shall exceed the soluble quantity of this salt.
To
such an
effect
may
be considered as a
is
regarded
These
great dilution in which they are present in the body.
cases have been treated with great success from the point of
view of the electrolytic dissociation theory by Kronig and
4
5
3
2
Paul, Kahlenberg, Loeb, Clark, and others.
property which is of physical character, but
much
is
It
To
The curves in
"
Cf. Ostwald's
Scientific
Zeit.
Zeit.
177
in
fluorescein
itself
(that is, the formation of a potassium salt from the acid) comInstead of a single
pletely alters the absorption spectrum.
absorption band in the blue for the acid, we find two absorption
bands in the blue and the blue-green part of the spectrum for
the salt.
similar observation may be made for tetraiodofluo-
BCdD
mm
Fluorescein,
Potassium
salt,
12
KH
2
Tetrabromfluor.,
10
NaCl 2 H 9
Dichlor fluoresc.,
Tetraiodofluor., I 4
Br4 H 6
K I Ha
Diethyltetraiodofluor., (C H ) I H
Tetrabrom-dichlorfluor., K Br Cl H
Tetraiodo-dichlorfluor., K I C1 H
Tetrabrom-dinitrofluor., K (NO ) Br H
Tetraiodofluor salt,
S 2
FIG. 21.
of pararosaniline,
their
THEORIES OF CHEMISTRY
178
absorption spectra.
FIG. 22.
is
sensibly weaker in
some
permanganates (Ostwald).
1.
2.
3.
4.
5.
Laevulinic acid.
Acetic acid.
Chloric acid.
Benzole acid.
Hydrochloric acid.
6.
7.
8.
9.
10.
Sulphanilic acid.
Nitric acid.
Phtbalimidoaceticacid.
Butyric acid.
Phenyl propiolic
acid.
is
ELECTROLYTIC DISSOCIATION
the pararosaniline
salts), so
179
Since the
electrolytes examined may be regarded as complete.
other ions present show no absorption, that which is observed in
the solutions of all permanganates is the absorption due to the
same quantities of the permanganate ion, and in the solutions of
pararosaniline salts (in the cases where there is no appreciable
hydrolysis) that due to the same quantities of the positive pararosThe spectra belonging to each of these two groups
aniline ion.
must therefore be identical with each other. Observation has
verified this, and the complete resemblance in every part of
the spectrum
may
dissociation theory.
views used in
The
and its ions. Ostwald 1 found that weak acids conform very closely
+
to the
ions of an acid
HA,
Cone, of
To
illustrate this,
if
HA =
some
const, (cone, of
figures of van't
Hoff
cone, of A).
may be
cited,
which
is
dissolved.
a obs
is
ions
and
CH C0
3
2 is
THEORIES OF CHEMISTR
i8o
V
0-994
0-402
0-42
2-02
0-614
0-60
1-66
1'67
15-9
178
178
18-9
1500
3010
14-7
15-0
20-5
20-2
7480
15000
30-1
30-5
40-8
401
oo
100-0
100-0
centrations.
instance,
by adding an
acetate
to
acetic
acid.
As
for
follows
HA
By
results of observations
calculation.
Chem,, 1890, 5,
1.
ELECTROLYTIC DISSOCIATION
181
salts.
Their relative
p. 142.
Obs.
Nitric acid
acid
dichloracetic
Hydrochloric acid
Trichloracetic
076
074
071
Calc.
0*24
0'69
0*31
0'26
0'69
0'31
0*29
0'69
0'31
0'09
0'95
0'05
Dichloracetic
lactic
0'91
Trichloracetic
monochloracetic
0'92
0'08
0'91
0'09
formic
0'97
0'03
0'92
0'08
lactic
0'54
0'46
0'56
0'44
acetic
076
0'24
075
0'25
butyric
0'80
isobutyric
079
propionic
0-81
glycollic
0-44:0-56
0-53:0-47
butyric
0'53
0'47
0'54
0'46
isobutyric
0'53
0'47
0'54
0'46
Formic
Acetic
to the result
0'20
079:0-21
0'21
079
019
0'80
0'21
0'20
two acids
At
out
THEORIES OF CHEMISTRY
82
(cf.
p.
176).
In
agree.
two
+
contains H-ions, or as a very
acid, for it
contains
H-ions.
is
may
Therefore
it
weak
base, since it
partially displaces
phenomenon which
is
weak
acids
known
as
magma
of the
HA
H and
XOH
quantities of a
X and
OH.
are completely
On mixing equivalent
and a very dilute strong
:
and
together represent the salt, which is
at
dissociated
high dilutions. The neutralization of
completely
a strong acid by a strong base corresponds to the formation of
water from
1
3
4
5
6
its
component
ions,
and OH.
The process
Noyes,
is
ELECTROLYTIC DISSOCIATION
183
independent of the nature of the acid and base used, and therefore the same quantity of heat (13,500 cal. at 18 C.) is always
evolved on the neutralization of strong acids by strong bases, as
1
The theory of electrolytic dissociation
found.
Jul. Thomsen
has thus furnished an explanation of this important law of
thermochemistry.
If the acid
formula given on
comparison gives
Heat
....
....
Hydrobromic
....
Nitric
Acetic
....
....
Propionic
....
Butyric
Succinic
....
Dichloracetic
....
....
Phosphoric
Hypophosphorous acid
....
Hydrofluoric acid
Hydrochloric acid
On
of neutralization.
Calculated.
Observed.
13,447
13,740
13,525
13,550
13,680
13,263
13,400
13,598
13,480
13,957
13,800
12,430
12,400
14,930
14,830
14,959
14,830
15,409
15,160
16,320
16,270
13,750
volume.
the
1
"
neutralization volume."
Thomsen,
cf.
Untersuchungen,"
2
As
241
"
;
Thermochemische
THEORIES OF CHEMISTRY
84
volume
is
were
Neutralization by
KOH
Nitric acid,
HN0 3
20'0
Hydrochloric acid,
HC1
Hydrobromic
HBr
Hydriodic
The small
acid,
acid,
....
....
HI
NaOH
.
19'8
19'5
19'2
19'6
19'3
19'8
19*5
differences
This
KOH
Volume
Formic
acid
Acetic
Propionic
Butyric
Isobutyric
Lactic
12*2
The agreement
2
...
Maleic
10-5
Succinic
...
of neutralization.
Observed (Ostwald).
7*7 c.c.
Calculated (Fanjung).
.
8'7
10'6
124
131
13'4
13'8
13'3
121
11-8
11*8
11/2
11'4
10'3
is satisfactory.
Planck,
Ann.
Fanjung,
Zeit. pliysikal.
c.c.
ELECTROLYTIC DISSOCIATION
185
heat of neutralization.
10 s
Temp.
2 C.
...
...
...
...
...
...
...
...
10
18
26
34
42
50
The agreement
is
6
by 10
106 fc
fc obs .
0-0107
caic
0-0103
0-0158
0-0238
0-0236
0-0386
0-0386
0-0606
0-0601
0-0890
0-0901
0-1294
0-1305
0-1839
0-0162
01807
and Heyd-
of
C. only 0-35
2 -48
litre of
water into
X 10' 7
its ions is so
at 25
C.
T04 X
in calcu-
THEORIES OF CHEMISTRY
86
force
of different galvanic
(Ostwald *), and from its catalytic action in decomposing methylacetate (Wys 2).
These different methods give results which
agree well with the measurements of Kohlrausch and Heyd-
weiller.
is
confirmed by
all
these different
measurements.
3
Already at an early stage (1883), 1 showed by theoretical considerations that the catalytic actions of different acids depended on
"
"
their strength.
The strength of an acid is only another ex-
+
pression for the H-ions contained in a given volume.
Therefore,
we should expect
indicate
Acid.
ELECTROLYTIC DISSOCIATION
Acid.
187
THEORIES OF CHEMISTRY
88
ammonia
is
of the presence of
(cf. p.
180), as I
electrolytic dissociation
the velocity of
diffusion is produced by difference in the osmotic pressure
of the ions in solutions of different concentration.
There-
we know
coefficient of diffusion at
difference
KOH, T85
and 2'07
The agreement
phenomenon
1
of diffusion.
ELECTROLYTIC DISSOCIATION
189
There
which
is
acid
is
Now,
is
for
a substance such as
if
is
617
movement
of the diffusing
always hindered, so long as they consist of nonwhen the diffusing molecules are not electrically
i.e.
electrolytes,
Therefore, if the molecules of HC1 were not dissociated
charged.
molecules
is
is
the case.
The
only draws back the H-ions, but also the Na-ions. The force
acting is, so to say, divided between a greater number of molecules,
HC1
and
it is
there are
+
n molecules
the H-ions (we say of the acid) will have the following values
(at 12 C.):
n
k
=
=
01
2-20
2-09
If the
number
0-2
2-30
of
0-51
2'58
2'96
NaCl molecules
3'52
444
is
10
5'07
oo
617
ment
THEORIES OF CHEMISTRY
190
filled
HC1
the diffusion-constants
was
filled
with
54w.
NaOH, and
solvents being pure water, 0*067^ NaCl, and 0'25w NaCl solutions
The following diffusion-constants of the base (really
at 12 C.
of the
1*15, 1*51,
and
1*90,
whereas the
result,
way
representation of the
mode
produced.
is
"
tendency of a substance to go into solution, just as the vapourpressure of a liquid denotes the tendency of the liquid to assume
the gaseous state.
doing work
is
greater tendency
In the Daniell cell,
when
side,
and
order
that
much
has.
is
in
has of
cell
Zinc has a
flow
copper
no
opposing
must simultaneously
side
to
the
electrostatic
copper
charges
it
ELECTROLYTIC DISSOCIATION
mechanical analogy
is
as follows
Two
vessels, the
191
one contain-
ing ethyl ether and the other water, are connected by means of a
Air and other gases are
cylinder in which is a movable piston.
combination
the
Cu
dilute
|
CuS0 4
X 10~4
1-99T
cone.
|
_________
CuS0 4
2v
.
'
f\(f
Cu
pi
*
p%
where pi and p.2 are the concentrations of the dilute and concentrated solutions respectively ; u is the migration velocity
of the anion (see p. 55), and v that of the cathion; n is the
valency of the ion which is deposited, and in this case is 2.
For a concentration cell of the second order and with unpolarizable electrodes,
Hg Hg2 012
e.g.
HC1
dilute
|
1-99T
cone.
X 10n
HC1 Hg2 01 2 Hg
1
2u
-f
log
b
pi
-*.
pz
and KAg(CN) 2
An
is
based on such
THEORIES OF CHEMISTRY
192
by the equation
$ 3I
+ 6H + 51 $ 3I
HI0 3 + 5 HI
I0 3
or
and
+ 3H
+ 3H
2 0,
also the corresponding equilibrium for bromic and hydroIf only a very small quantity of HI is present,
acids.
bromic
the reaction
is
left to right.
In
solid
AgI0 3
in the presence of
by
titration.
It
by measurements of electromotive
force,
and found
to be in
method
nature.
+
reaction
1
which
Sammet,
is
Zeit. physical.
viz.
the
ELECTROLYTIC DISSOCIATION
193
CHAPTER XIV
PROBLEMS TO BE SOLVED.
OBJECTIONS
ALKEADY
much more
truly to-day,
now
that
it,
its
nearly
all
electrolytes
more
increases
where n
1
673.
is
following table,
Jahn,
Zeit.
physikal Chem., 1900, 33, 545, 35, 1; 1901, 37, 490 and
PROBLEMS TO BE SOLVED.
n
OBJECTIONS
195
THEORIES OF CHEMISTRY
196
last
The velocity
reaction
of
enters
the equation of
it would be more exact
equilibrium (cf. p.
to write the two factors of this equation, not as the product of
the concentrations of the reacting molecules (or ions), but as the
into
Now,
as
electrolytes
said
do
the
above,
not
follow
the
concentration.
water
concentrations deviations occur, just as in the case of canesugar, and in most cases the observed freezing-point is lower
than the calculated one. As Noyes l has recently shown, the
difference between
the calculated (from the electrical conductivity) and observed values of the lowering of the freezing-point does not exceed more than 2 or 3 %, as long as the
concentration of the salts examined (of the type KC1 and
The heat of solution
K^SO*) is not greater than O 25 normal.
f
same degree
This seems to
me
of
therefore,
minimum
value
At medium
of
the
con-
molecular
Noyes, Zeit. physikal Chem., 1898, 26, 699; Science, 1904, 20, 599.
PROBLEMS TO BE SOLVED.
lowering
is
OBJECTIONS
197
concentration.
1888
for solutions of
An
and CdI 2
acid,
The most
irregular manner.
5
4
of
some
results
Kablukoff, Euler,
explain
6
8
7
Godlewski, Kahlenberg and Buhoff, Plotnikoff and especially
9
Lincoln, who have found solutions, in which the molecular
water behave
difficult
electrolytic
rather
are
to
conductivity,
Steele,
in
i.e.
dissociation,
10
Mclntosh, and Archibald have obtained similar
results.
J.
49, 82
4
5
6
7
7, 254.
10
THEORIES OF CHEMISTRY
198
(=2
electro-
The law of
which may
to other similar
and of
investigations
nevertheless
cannot,
as
show that
yet, be
the
considered
apparent
final,
but they
is not
contradiction
altogether inexplicable.
The researches of other investigators have led to similar
An investigation by J. Wallace Walker and F.
results.
1
of the conductivities of
in acetamide
Godschall Johnson
KCN
have no
sufficient foundation.
weak
his
Wakeman 2
difficulties will
be disposed of
Wakeman,
Zeit. pliysikal.
PROBLEMS TO BE SOLVED.
some empirical
rules,
OBJECTIONS
199
till
their
(Cone.
XA) =
Van't
electrolytes.
--
Hoff
in the equation
const, (cone.
X)
2
,
XA
AgN0 3
is
=
v
j,and
K^-~-V
v
\
K is the
THEORIES OF CHEMISTRY
200
1
to Noyes, the power in different cases varies between the
In this manner it is possible to represent
values 1'43 and 1/56.
power
On
also for salts composed of a greater number of ions.
theoretical grounds it seems necessary to assume that it cannot
be applicable to extremely dilute solutions, for in this case the
law of mass-action must be fulfilled.
Another rule, which has been found to be approximately
true, says that salts of the same type are dissociated to nearly
the same extent at the same molecular concentration, and that
the undissociated fraction remaining at this concentration is
proportional to the product of the valencies of the two ions.
-
KC1
(valencies 1
reaches a
and
mean value
05 normal solutions of
1),
salts of the
type
of 13*5
C.
CaCl 2 or
3
2
Noyes, of a statement by Ostwald.
of
The general laws
equilibrium indicate that
solutions of two
weak
acids,
HA
if
we mix
HA) =
HA)
is
+
const, (cone, of
H) X
(cone, of A).
1 to n, the
term
1),
the
-
4*
-i
3
Of. Walden,
Ostwald, Zeit. physikal. Chem., 1887, 1, 74, 97.
physikal Chem., 1887, 1, 529; 1888, 2, 79; 1891, 8, 775.
Zeit.
PROBLEMS TO BE SOLVED.
OBJECTIONS
201
if equilibrium originally existed between the concentrations in the solution of the acid HA, it will also exist after
follows that
The same
solutions.
If
HAi.
we
+ vi) =
av
KN0
NaN0 3
or
which are
equinormal solutions,
dissociated
that
the
to
the
difference
same degree in
A between the
18-5 C.)
(at
c.c
0-5 normal
KNO.,
8
4
2
0-9
8
8
4
2
The
differences,
do not very
is
0'9
+
+
+
+
+
+
+
+
+
+
c.c.
'5
normal
KC10B A = -0'03%
-0-22%
-0-26%
- 0-00 %
8
8
-0-06%
-0-10%
NaNO,
0-01
-0-00%
-0'05%
- 0-05 %
-0-30%
-0'33%
8
8
8
much
(3),
1887, 30, 51
Zeit.
physikal
o 2
THEORIES OF CHEMISTRY
202
e.g.
living body.
In the
calculation
of
the
degree of dissociation of an
that the friction of the
electrolyte
moving ions against the surrounding fluid may be regarded as
independent of the concentration of the salt. This is doubtless
true for dilute solutions, but even in 0*1 normal solutions the
correction for the alteration in this friction probably reaches
2 to 3
friction,
by putting
it
is
friction of the solution over that of pure water ; or, still better,
equal to the corresponding percentage decrease of the diffusion
lent
now
PROBLEMS TO BE SOLVED.
OBJECTIONS
203
form in
its
place
(Conc.ofundiss.XA)
_ const
( conc - of iops
X)(conc. ofjons A)
+
(total conc.
As
large
oftheionsX+X
We
are
com-
not entitled to
P.
Walden,
Zeit. physical.
INDEX
views developed by Rutherford, Soddy
Abegg,
Ramsay, 103-106
conception
Abraham, 107
186
Acetamide, 124
Aggregation, state
of,
B
Baeyer, 85
Barkla, 102
Bartoli, 7, 172
41
of.
50
Amylene hydrobromide,
144, 181,
as solvent, 198
Actinium, 20
Additive properties, 172-177
Affinity, tables of, 132
Ampere, 53
Amphoteric
127
of valencies, 80-82
Beccaria, 48
Becker, 89
Beckmann, 166
Bergman, 132
Berkeley, 162
197
114, 150
Archibald, 197
Archimedes, 12, 13
Argon, 100
Aristotle, 12, 15
143
Berthollet, 16, 44 chemical equilibrium,
133, 135, 140
188,
Astrakanite, 152
well as of matter, 48
of
Dalton, 4,
15
14
of
4, 14,
Atomic weight,
chemistry, 58, 80
17, 18
metallic
ammo-
Boltwood, 20
Boltzmann, 1, 7, 115, 119; heat of
dissociation, 149
Boyle, 9, 10, 15, 115, 125, 128 B. and
;
157-159
Democritus,
189,
investigations on con185, 186,
ductivities of electrolytes,
Atomic theory
formation
of esters, 137,
205
INDEX
206
Dalton,
critus, 14,
of,
17
validity of his
150
Lussac, 111
atomic theory
C
Cane-sugar,
4,
186
Daniell, 80
and the
80
dualistic theory,
Cannizzaro, 113
42
Carbon atom, asymmetric, 74-78
Capillarity,
Carlisle, 50, 5
Carnelley, 152
Carnot, 7
Catalytic processes, 135-137, 18G, 192;
Williamson's explanation, 139, 140
149
dissociation, 146,
system,
134, 140
reactions, 135-145
Chemical reactivity and electrical con;
Clark, 176
Clausius, 7, 115, 140; hypothesis of, 158
Coehn, 106
.
Colding, 7
Colour of solutions, 176-179
Combination, heat
of,
of,
146-155, 169
trolytic,
heat
phenomena
of,
149
elec-
g[.v.
for,
Dittmar, 35
153
Compressibility, 174
Concentration
Ebert, 64
elements, electromotive
n.
tures,
Electrical conductivity
of, 68, 69,
88
Coronium, 97
Cotton, 75
Coulomb's law for electrical quantities, 9
Crafts on vapour-densities, 146
Cryohydrates, 31, 32
Curie, Mme., 19 ; radium, 19
of electro-
Co-ordination number, 87
sulphuric
and chemical
re-
between, 157
between the atoms
activity, parallelism
Electrical
forces
48
of,
55
INDEX
58-67; Faraday's
Leblanc's experiment, 64, 65
Electrolysis, 49-56,
law, 61
chemical
Arrhenius'
electrically
compounds
169;
157,
lecules,
60
are,
157-159
investigation,
active and inactive mo-
properties
of
velocity
aqueous solutions
of,
172-179
Electrolytic dissociation, 165, 169-193
207
Ether
vortices,
Ethyl
solvent,
27;
34
39
alcohol,
of solutions,
boiling-points
139;
of,
33,
as
Exner, 6
Experiment, error of, 8
Eykman, 163, 166
Arrhenius)
wide-reaching ap-
172-175;
properties
and
poisonous
of
salts,
curative
Ostwald's
176;
176,
194-
solved,
89-108
atoms,
hypothesis,
J.
93-102;
composition of
Thomson's
J.
Nagaoka's
as-
system
12;
of, 86,
tions of,
97
Mendele'eff's
87,
95-98
periodic
modifica-
n.
Ernpedocles, 12, 13
his standpoint, 13
Epsom
Lecture,
electrical forces
Fraenkel, 193
tions,
194-197
Frowein, 70, 154
and Lavoisier, 14
Energy,
of, 7
sumptions, 102
Elements,
Fumaric
77
acid, 76,
salts,
152
saponifica-
Galileo, 10
116-118
(see Molecule);
atmosphere
137
147, 179;
125, 126
for, 144,
of,
law of equilibrium
refractive index
Gassendi, 15
INDEX
208
phase
155
rule, 150,
Hydrolysis, 182
Hylotropic mixtures, 40
Gladstone, 175
Glauber's salt, 152
critus', 4,
14
Lockyer's, 18
Indium
7
of neutrali-
118-120; con122
74, 93;
atomic
Johnson, 198
Jones, 24, 172 n.
researches on hydrates,
37
Juhlin, 152
24, 26,
cells,
K
Kablukoff, 197
Kekule,
73, 74,
valency, 73, 78
Hisinger, 51
;
Kelvin, Lord,
meter, 6
Hood, 139
Horn, 162
Horstmann,
79
of dissociation,
68, 69
of combination, 153
Hittorf, 55
of,
Heat of solution,
Helmholtz,
of,
Helium,
duction
Ions,
203
Hautefeuille, 149
Heat,
186, 187
Iodine, 79, 100, 149
Harden, 17 n.
Hartley, 162
79
passim
Hamburger, 160
Hankel, 6
149
laws of equi1 47
studies
in dissociation, 149, 154
Hydrate theory of solutions, 21-38 re70,
158;
77,
6, 7, 42,
78;
66
constant,
his electro-
Kohlrausch, W., 23
Kolbe, 74
Kaoult,
sions
Jones, 21-37
and
vapour-ten-
discontinuities,
cryohydrates, 31
28-31
doubtful value of
Konowalow,
Kopp, 173
33,
36
Kronig, 176
Kundt, 118
conclusions obtained, 37
Hydrates, 68, 69, 85-88, 150-152
of,
149
distilling
Langer, 149
Latent heat of evaporation, 153
INDEX
Lavoisier, 4, 54
Law, Ohm's,
10
1, 8,
72;
Newton's, 9; Coulomb's, 9;
Snell's 9
Boyle's (Mariotte's), 9, 10,
;
Van
110, 115;
72
Kaoult's, 24
thermodynamics,
Gibbs', 33
9, 33,
66
Fara-
Charles', 110;
Le
Bel, 74
209
of,
86
Metals, vapour-densities
Methyl
acetate,
186
electrolytic
experiment,
Lemoine, 149
Lenard, 89; modification of Prout's
hypothesis, 89, 95; experiments on
the absorption of cathode rays, 89-92
hypothesis of the spectra, 103
Lescoeur, 154
;
of,
compounds,
table of vis-
on vapour-den-
liquids, 41
67-71, 86-88,
150-155
64,65
Le Chatelier, 150
Light, theories
Lincoln, 197
Molecular
and
Miscibility of gases
Leblanc, 64;
78, 79
of,
Molecule, properties
82,
velocity
and
of,
109-131;
of,
116-120 diffusion,
and conduction, 121-124
specific heat,
viscosity,
Muller-Erzbach, 154
M
N
Marggraf, 134
See Boyle
Marvin, 152
Mariotte.
Mass-action, law
'
119,121,123,126
Mayer, 7
Mayow, 13
Mclntosh, 197
McKenzie, 78
n.
Newton, 6, 9, 15
Newtonium, 98
Nicholson, 50, 54
law of
attraction, 9
INDEX
210
Nilson, 79
Planck,
Nitrogen, stereochemistry
of, 60,
of.
77
oxides
149
7, 67,
184
; electric charge on an
equation of equilibrium,
atom, 127;
148
Plato, 12
Plotnikoff,
197
Poisons, 176
Polarization capacity, 93
Ohm,
1,
Ohm's law,
1, 2, 8,
Polonium, 104
10
of
plant-cells,
isotonic
159;
cells,
166;
w.,
45
144, 181,186;
phenomena
of
of,
100
146-156
Priestley, 44, 48
dissociation,
Proportions, stoichiometric, 15
(Proust), 16, 44, 72;
constant
multiple (Dai-
Lenard, 89, 95
on conductivities of
157
electrolytes,
Pope, 77 n.
Potassium, atomic weight
Potential series, 51, 52
exposition
analytical
of
chemistry,
Oudemans, 175
104
Oxidation, 4, 13, 14
Oxygen, tetravalency
Radium: Mme.
176
of,
85
giving
and y-
rays,
104
159
Rayleigh, 9, 18, 195
Reactions,
Paul, 176
Pebal, 113
Perkin, 175
P<&n de
143; formation
of esters, 137
Permanganates, 177-179
Perrot, 49
Pettersson, 79
on osmotic pressure, 160Pfeffer, 160
162, 167
Phase rule, Gibbs', 150, 155, 156
Phlogiston hypothesis, 4, 13
Picker, 59
Pickering, 24
;
Reversibility,
64
Richarz, 64
Richter, 15, 16,
73
54
Roberts- Austen, 42
Ritter, 49, 52,
Rocks, weathering
Rogowsky, 130
of,
133, 134
Rontgen
INDEX
Roscoe, 17 w., 35
Rose, 133, 134 mass-action, 133
Rousseau's maxim, 8
211
Strutt, 20, 91
Rudolphi, 199
Ruhoff, 197
of,
21-26, 30,
on decompo-
Tammann, 79
S
Scheele, 16
3, 6, 14; its
176
32
of, 68,
solubility
and hydrates
70
Solution-pressure, 190
Solvents,
non-aqueous, 164,
165, 197,
198
Spectra, Lenard's hypothesis
absorption, 176-178
103;
19
of,
of stars,
and composition
atomic
Timaios, 12
Transition point, 29, 152
Traube, on osmotic pressure, 160
Travers, 100
Troost, 149
True, 176
Stark, 103
atmosphere
investigations on
constitution of electricity, 48 ;
hypothesis of the constitution of the atoms,
93-102 representation of Mendeleeff 's
Spohr, 139
Stars,
146, 150,
70,
150-154
Sodium sulphate,
of, 29, 30
to,
Smoluchowski, 130
Snell's law of refraction of
light, 9
Soddy, 19, 20, 103, 106
of, 31,
of chemical equilibrium
Thomsen,
Sjoqvist, 182
Sodium
179
how
regarded, 5 of equivalence of
different kinds of energy, 7
Thermodynamics, two laws of, 9; relation
;
of,
of,
129-131
19
spectra
Stas, 18
Statical methods, 8
Steele,
197
Stereochemistry, 74-77
Stoichiometric proportions, 15
130
Storch, 199, 203
on helium, 129,
Valency, 57, 58
development of doctrine
of,
72-80;
tions,
73, 78
stereochemistry, 74-77
and
INDEX
212
Berzelius'
Werner's,
dualistic
Abegg's,
80-82;
conception,
verified
by system
80;
system,
Darnell's
and
doctrine
of Mendeleeff ,
of,
86
W
Waage,
16,
Guldberg, law
Wakeman, 198
of,
Wald, Franz,
45
Walden, 200 ., 203
Walker, James, 197
Walker, J. W., 198
Warder, researches on
138. 139
position
researches on reactions,
equilibrium mobile,
139, 143;
ammonia compounds,
28
discontinuities,
28-31
Velocity of efflux of gases, 117
Villiger,
chemical products,
saponification,
Water
abnormal, 113,
146-149
Vapour-tensions,
85
solu-
150-152
Waterston, 115
Wedekind, 77 n.
Wenzel, 15, 135
conception
Wien, 7
Wilhelmy, 135, 136; catalytic effects,
135-137
Williamson, 76; studies on reactions,
139. 140
Winkelmann, 153
Wislicenus, J., 76
Vogel, 177
Volta, 49, 50, 52
and
79;
Vapour-pressure,
40,
of
eudiometer, 110
Wys, 186
THE END
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