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THE ELEMENTS
OF
PHYSICAL CHEMISTRY
BOSTON
CHICAGO
SAN FRANCISCO
MACMILLAN &
LONDON
CO., LIMITED
BOMBAY CALCUTTA
MELBOURNE
THE MACMILLAN
CO. OF
TORONTO
CANADA,
LTD.
^n
T
:
THE ELEMENTS OF
PHYSICAL CHEMISTRY
BY
\jfN
HARRY Of JONES
PBOI-ESSOR OF PHYSICAL CHEMISTRY IN THB
FOURTH
EDITION, REVISED
Nein
AND ENLARGED
fforfe
BY
Reprinted
August, 1903.
New edition,
New edition,
New
J. 8.
Norbootj
Berwick & Smith Co.
Gushing Co.
Norwood, Mass., U.S.A.
October,
PREFACE
IT is now generally known that within the
new branch of science* has come into existence.
is
known
as physi-
We
chemistry.
last
work
older work.
It, however, appears to the writer that in order to appreciate the
gigantic strides made by the new physical chemistry, it is not necessary to reject, or even ignore the work of such men as Kopp, Bun-
this
PREFACE
vi
organic
istry
plex that
it is difficult
we
statics
find experimental
much
law
and
The phase
lems.
and applied,
it- is
rule,
wherever
was
possible.
cially
Chemie,
wald's great Lehrbuch der allgemeinen
Chemie, to Nernst's Theoretische
Chemie, and to Van't Hoff's Vorlesungen iiber theoretische und physikalische CJiemie for references to the literature.
These have made
PREFACE
it
much
Vll
moment.
need be said at this date in reference to the importance of
It has already extended
into nearly every field of chemical science, contributing largely to
the interpretation of phenomena hitherto not understood. It has
thrown light on so many problems in chemistry that it has now
become an integral part of that science. And it is recognized that
no chemist to-day, scientific or technical, can omit physical chemistry without losing an essential part of his training.
Physical chemistry has also thrown light on a number of physical
problems, especially in connection with the study of primary cells,
Little
as
we
shall see
when we study
electrochemistry.
work
to find its
last
The wide-
almost
decade and a half of the nine-
HARRY
C.
its
JONES.
it
up
few years has been unusually rapid, and an enormous amount of new
and important material has been published since the first edition of
The more important developments have
this book appeared in 1902.
been discussed, as far as possible, without unduly enlarging the book.
Since, however, much that is both new and valuable could not be
brought directly within the scope of the text, it has been decided
to give a fairly large number of references at the bottom of the
pages, to the more important investigations bearing on the subject
under discussion. In this connection practically all of the original
papers in the Zeitschrift fur physikalische Chemie have been examined, and, further, the "Referate" in this same journal have been
carefully consulted up to the appearance of the Physikalisch-cheAll of the volumes of the latter have
misches Centralblatt in 1904.
made more
least
from
its
the
H. C.
J.
The
this work,
science.
H.
C. J.
CONTENTS
CHAPTER
....
...
CHAPTER
4
18
37
II
GASES
Laws of Gas-pressure
The Kinetic Theory of Gases
46
54
Heat
The Spectra
of Gases
of Gases
....
57
.;.',.
.68
...
.
79
CHAPTER HI
LIQUIDS
Relations between Liquids and Gases
*
.
Boiling-point of Liquids
.84
99
Heat of Vaporization
Specific Heat of Liquids
The Refractive Power of Liquids
109
Ill
115
Magnetic Property
Specific Gravity and Volume Relations of Liquids
Viscosity of Liquids
Surface-tension of Liquids
125
135
138
.
.139
141
143
154
xi
CONTENTS
xii
CHAPTER IV
SOLIDS
PAOB
'
Crystals
J2
Ibl
Relations between
Properties of Crystals
Crystallographic
Form and
Properties
.165
Melting-points of Solids
Latent Heat of Fusion
Specific
171
Heat of Solids
CHAPTER V
SOLUTIONS
176
Solutions in Gases
Solutions in Liquids
Osmotic Pressure
**
202
208
214
222
256
(Rise in Boiling-point)
Diffusion
273
287
298
Color of Solutions
Pressure of Solutions
Recent
Work on
Wolfgang Ostwald's
Perrin's Study of the
319
320
324
325
....
....
305
317
318
.326
Brownian Movement
327
The Ultramicroscope
327
328
Indicators
CHAPTER VI
THERMOCHEMISTRY
Development of Thermochemistry
Conservation of Energy applied to Thermochemistry
Thermochemical Methods
.
....
,
330
334
337
CONTENTS
xiii
PAGE
341
343
345
Some
351
........
........
Compounds
CHAPTER
VII
ELECTROCHEMISTRY
of Electrochemistry
Development
Electrical Energy Units
The Law of Faraday
;
Nomenclature
359
370
378
374
389
Electrolytes
454
Measurement
of Differences of Potential
Work
Mixed Solvents
in
503
.....
504
.514
.,
-.
,
CHAPTER
.
..-
.506
510
VIII
PHOTOCHEMISTRY
Actinometry
Results of Photochemical Measurements
.
Photochemical Action of Newly Discovered Forms of Radiation
.
Production of
483
494
...
Recent
405
431
511
Radium
517
531
.532
CHAPTER IX
CHEMICAL DYNAMICS AND EQUILIBRIUM
Historical Sketch
The Law
of
534
Mass Action
546
Chemical Dynamics
.
Chemical Equilibrium
The Phase Rule and its Application to Chemical Equilibrium
Equilibrium in Solutions of Electrolytes
.
550
585
594
613
Catalysis
Effect of Pressure on Chemical Reactions
621
Allotropy
623
623
liv
CONTENTS
CHAPTER X
MEASUREMENTS OF CHEMICAL ACTIVITY
....
PACK
625
635
THE ELEMENTS
OF
PHYSICAL CHEMISTRY
Law
The study
of chemical
phenomena,
stances, and it was also noted that the substances formed as the
result of the reaction have many properties which are very different
These
mere fact that from certain things other things are formed
is
not
phenomenon of chemical activity, and entirely lacks any quantitaThe qualitative stage is followed, wherever it is possithe
Known
ble,
quantitative; and so it has been in chemistry.
y
of
were
substances
and
the
of
amounts
the
subquantities
used,
stances formed determined.
Almost as soon as chemists began to
work ,ith known masses of substances, the remarkable fact was
>.d that in chemical transformations mass remains unaltered,
remarkable because it is the only property which remains
"ged in chemical reaction. When two or more substances
tive basis.
,.
nearly
all of
Indeed,
lost
We
fix
our attention.
is
sometimes referred to as
is
we
greatly to be preferred to the latter, since it states just what
have established by experiment. The latter goes far beyond the
Ostwald has pointed out, is pure theory.
question as to whether there is any change in weight in
chemical reaction has recently been thoroughly investigated by
Landolt. 1 In his work the most refined balances that have ever been
facts and, as
The
work
is
a classic for
present.
The law
of constant proportions
was
Ztschr. phys.
Chem.
12, 1 (1893)
55,
2
by Berthollet.
stances used, but also the composition of the products formed. Two
substances could unite in a great many proportions, and the composition of the product depended chiefly on the relation between the
6 to
1.
The
latter
as
much
examined, in which simple ratios between the masses of the conwere discovered.
From these and similar facts Dalton
arrived at the law of multiple proportions, which may be stated
thus:
*
stituents
shown
New
The discovery
tions,
is
Why
come^to
atomic theory, in contradistinction to the older imaginative
molecules. The view that matter is
speculations about atoms and
scientific
definite
composed of indivisible particles or atoms, which have
these
between
takes
action
chemical
partiplace
weights, and that
of the laws of mulcles, was to Dalton the only rational explanation
If matter is composed of
tiple proportion and combining weights.
such ultimate parts or atoms, then a constant number of atoms of
one substance combine with one atom of another substance to form
a definite compound, and we have the law of constant proportions.
One atom of one substance may combine with one atom of another
substance, or a number of atoms of one substance may combine with
one of another; but the number must be a simple rational whole
number; whence the law .of multiple proportions.
Since the atoms have definite weights, and the laws of constant
and multiple proportions are true, the law of combining numbers
with,
one another.
We
will take
up
5
first
the method of
to
made
in
many
cases.
ratio
bining number
the
hydrogen.
We
selected.
It is perfectly clear that neither the
compound, nor
of the
its
methods
Molecular Weights
of gases are proportional
Lussac 1 showed in 1808 that the densities
rational
to
or
multiples of them.
simple
to their combining weights,
react are either
which
volumes
the
If two gases react chemically,
another.
one
to
And,
relation
rational
a
bear
simple
equal, or
is a gas, its volume bears a simple
formed
if
the
product
further,
which it was
rational relation to the volumes of the gases from
one volume
with
combines
formed. Thus, one volume of hydrogen
One
acid
of
gas.
hydrochloric
of chlorine, and forms two volumes
formof
volumes
two
with
combines
hydrogen,
volume of
oxygen
From
account for these, we see that every chemical reaction takes place
between a definite number of atoms, and the number is usually
small.
Therefore, the discovery of Gay Lussac leads to the conclusion that
We
have thus
far,
cal value of this relation, and, therefore, cannot use the discovery
of Gay Lussac alone to determine relative atomic weights.
2
Mem
d.
Arcueil, T.,
II.
(1808).
made up
another.
many
directions, that it is
the well-established
difference between
atoms and molecules, and rationally explains why different gases
should obey the same law of volume and of pressure, and have the
same temperature coefficient of expansion. It has been tested from
both the physical and mathematical standpoints, and now lies at
laws of nature.
the basis of
much
of our
knowledge of
gases.
Given the
Hypothesis and Molecular Weights.
hypothesis of Avogadro, the determination of the relative molecular
weights of gases is very simple. If there is an equal number of
molecules contained in equal volumes of the different gases, the
Avogadro's
We
the smallest density, and this is hydrogen. From what has been
said, however, in reference to the union of hydrogen and chlorine,
forming hydrochloric acid, it is certain that the molecule of hydro-
gen contains at least two atoms. We will, therefore, call the molecular weight of hydrogen two, and calculate the molecular weights
of other elements in terms of this standard.
The densities of substances are usually determined in terms of air as the unit.
It is a
matter
to
in
two.
recalculate
of
as
these
terms
simple
hydrogen
The density of hydrogen in terms of air as the unit is 0.06926. 2
We
must multiply
1
2
Lettre de M.
this
by 28.88
to
obtain
our
new
unit two
CHEMISTRY
THE ELEMENTS OF PHYSICAL
- 28 88).
kno^ with
006926
are
term
of "hydrogen
= 2.
These
in the
llecuTr weights of the substances
as two.
The Totula/weight of hydrogen
in
than one, but it cannot be less. This is the key to the problem.
Suppose we wish to determine the number of hydrogen atoms in a
molecule of hydrogen. We must examine compounds into which
it
may
be more, but
it
cannot be
less.
By examining
it
may
in reality be
composed of a
The molecule
the weight of
ing table
10
11
12
The law
The
makes
it
is
the
possible to greatly
is
would be very
an element whose
difficult to
determine.
compound with the element lead. The specific heat of lead chloride
has been found by Eegnault to be 0.0664; 206.4 parts of lead
yield
277.1 parts of lead chloride. Multiplying this number
by the specific heat of lead chloride, we obtain the molecular heat.
277.1 x
0.0664
18.4.
Subtracting the atomic heat of lead, 6.5, we have 11.9
as the atomic heat, corresponding to 70.7
Since
parts of chlorine.
the atomic heat of the elements is about
6, we have in 70.7 twice
the atomic weight of chlorine, or the atomic
weight of chlorine
way
spe-
discrepancies exist.
Lieb.
(1831).
p. 100.
It
was
13
the power of forcing other substances to take their own crystal form.
Mitscherlich l interpreted this fact quite differently. He studied
the salts of arsenic and phosphoric acids, and found that those which
determining
its crystal
" An
position."
If this relation
was
true, it
light
on the num-
ber of atoms in a compound, and therefore be of service in determining atomic weights. Given two isomorphous substances such*as
BaCl 2 2
and BaBr2 2
H 0,
2
If
we know
showed
thai/ the
compounds
BaMn
8,
Na S0
2
4,
and Na^SeC^
NaS
14
and
dealing
with one or more atoms.
In determining atomic weights we must choose some
element as
our standard. We would
naturally take the lightest element, hydroThis has been done, and all atomic
gen, and call it unity.
weights
referred to this unit.
But it is
unfortunately true, as has been
stated, that hydrogen does not combine
directly with many of the
elements and form stable
compounds which can be analyzed.
Oxygen, on the other hand, does combine with a
large number of
the elements, forming some of the most
stable compounds with which
are acquainted.
It therefore
by no means
Lieb.
Ser.
free
from
objections,
Ann.
d.
132, 29 (1864).
chem. Gesell.
12, 909
(1879).
15
basis.
wt. element
= at. wt.
oxygen
We
referred to,
may
arise,
oxygen.
It is evident that the more direct the comparison of the atomic
weight of the element with that of oxygen, the better; since the
accumulation of experimental errors, resulting from indirect com-
parisons, is avoided.
Some of the most refined experimental work which has ever been
done has had to do with the problem of relative atomic weights.
It is obviously necessary that these constants should be determined
with the very greatest degree of accuracy, since all chemical analysis
16
and Marignac,2
3
recent investigations those of Morley and
among the
and among the more
especially
Richards.
The work
between
of Stas
silver
had
to
is
simply wonderful
we
which
when
it
was
by
different methods,
sults, to be 1
re-
15.879.
is
oxygen
*
= 16.
Untermch.
'
and
the *""'<"
their
*""<
Chem. (1894-1901).
ELEMENT
17
18
of
Front
It
if
we chose
of a large
the atomic weight of hydrogen as one, the atomic weights
or
numbers
whole
either
very nearly whole
number of elements were
numbers.
The
error.
and suggested
might be found in the assumption that all the elements are simply condensations of hydrogen. The atoms of the
different elements are composed of hydrogen atoms, the number
by the atomic weight of the element. This asbeing
weights,
cal regularity
expressed
of Prout,
sumption, which has come to be known as the hypothesis
1
was also made some three years later by Meinecke.
Dumas
in
1859,
when he suggested
step
by
that one-fourth the atomic
Handbuch
19
Mallet. 1
That
it is
an
such elements was almost exactly the mean between the atomic
This will be seen from the
first and last members.
weights of the
following examples
20
mean
of chlorine
and iodine
triads.
and from their discoverer as Dobereiner
Chancourtois.
De
The Work of Cannizzaro and of
triads,
was
It
should be reached
impossible that any comprehensive generalization
until some uniform
with
any property,
connecting atomic weights
had been adopted. Confusion was reduced
system of atomic weights
He considered Avogadro's law
to order in this line by Cannizzaro.
and gave us the conas the basis of atomic weight determinations,
which still prevails. With these comparable atomic
ception of atom
and relations between those weights
weights chemists could now deal,
which have proved to be of the
of the
and properties
elements,
of inorganic chemistry,
greatest service in the development
were
was
soon pointed out. It is thought by some that De Chancourtois
be
can
which
relations
to
regarded
attention
call
fairly
to
the first
as the logical precursors of the periodic law.
the atomic weights be arranged in a particular
He
way
suggested that
in the form of a
the positions of
screw, and showed that relations existed between
obscure
In
an
the elements and their properties.
way he seems to
later discovery,
the
idea
fundamental
the
have hinted at
underlying
that the properties depend* upon the atomic weights, but certainly
this was neither clearly conceived nor tersely expressed.
The question of relations between
The Octaves of Newlands.
News,
Equivaamong
he arranged the elements in the order of their equivalents,
and stated that " it will be observed that elements having consecutive numbers frequently either belong to the same group or occupy
similar positions in different groups.
The difference between
the number of the lowest member of a group and that immediately
above it is 7; in other worcls, the eighth element starting from a
given one is a kind of repetition of the first, like the eighth note of
an octave in music." In the following year Newlands announced
lents,"
his
"
Law
4
:
Chem. Neics,
etc.
(1864).
4
JMdg
12> gg (1866)>
Paris, 1863.
21
arranged in the order of their equivalents with a few slight transpositions, it will be observed that elements belonging to the same
group usually appear on the same horizontal line. It will be seen
that the
7,
or
NEWLANDS' TABLE
22
23
They must therefore be set aside and left out of the system.
Then we come to copper, which is very questionably placed with the
members of group I. Then irregularities appear again. At the end
of the sixth series we find three or four more elements which do not
metals.
fit
into the scheme, but after leaving these, regularities again begin
to manifest themselves.
relation,
and
little later.
cylinder so that the right and left sides touch; therefore, nickel next
which, in this arrangement, fall into the same vertical column, form
a natural family, the members of which, however, bear a very unequal
ments
1
is
shown
Lieb.
Ann. Suppl.
7,
354 (1870).
Ibid., p. 368.
ele-
24
25
and
regularities,
Os0 4
series.
We would express the combining power of the elements
toward chlorine as follows
:
Nad, MgCl 2
A1C1 3
SiCl4,
PC15
S02C12
(WC1 6 )
oxygen exists here. The elements in group I have the smallest power
of combining with chlorine, and this increases by unity from group
to group as we pass from left to right reaching a maximum of six
in the sixth group. We know of no element which has the power
of combining directly with more than six atoms of chlorine.
When we examine the power of the elements to combine with
hydrogen, a regularity is observed, but of a different kind from those
The elements in groups I, II, and III in general
already considered.
also combine directly with hydrogen to form fairly stable compounds hydrides of most of these elements being known. When we
come to group IV, we find in carbon a remarkable power to combine
with hydrogen. The highest valence of the elements towards hydrogen is manifested in this group, where one atom of the element com;
26
As we pass to the
bines directly with four atoms of hydrogen.
with
combine
to
hydrogen decreases,
the elements
right the power of
three atoms of
with
combines
and decreases regularly. Nitrogen
with
with two, and fluorine with one. Starting
hydrogen, oxygen
group IV, we have
LiH,
CaH
2,
BH CH NH OH
3,
4,
3,
2,
FH.
itself to
from
group IV. and diminishes regularly
degree in
both directions.
maximum
this point in
The
elements.
many
Some
umns
which
in
fall in
very
sight
very
while purely empirical, are of
profound interest, and
give to the Periodic Law a deep significance. It is
certainly true
that the members of even series are more
closely related to one
These
facts,
27
another than they are to members of odd series, and the same
obtains for the relations between the odd series. We seem to have
here not only a Periodic System of the elements, but one such system
within another.
than
The
difference
now
more, now less basic or acid properties, depending upon condibut in the last column of the last well-defined group we have
tions
elements which manifest only acid-forming properties. The hydrogen and hydroxyl compounds of the halogens are always acids, and
As we
all
other substances.
pass upward
Many
istry,
Lieb.
IL
Ann. Suppl.
8,
133-229 (1872).
Mendeteeff, Principles of
Chew
28
Meyer
plotted
volume with increase in atomic weight, and found that it had remarkable properties. The curve is shown in Fig. 1. The abscissas
are atomic weights, and the ordinates atomic volumes.
In some cases the specific gravity of the element in the solid form
could not be determined as with hydrogen, oxygen, nitrogen, fluoIn the places corresponding to these elements the curve
rine, etc.
is a dotted line.
see at once from the curve that the atomic volume is a peri;
We
Mendele'efFs table.
OllflOlV
29
30
own
e.g.
arms of the curve. Kelations between a number of physical properThese include reand atomic volumes have been pointed out.
fraction of light, specific heat, power to conduct heat and electricity,
magnetic properties, etc. But the most interesting and closest rela1
tions have been discovered between fusibility and atomic volumes.
between
connections
Some striking
Fusibility and Volatility.
the melting-points of elements and their atomic volumes have been
ties
brought to
light.
The
There
is
of atomic volumes.
The maxima and minima of the two curves, howdo not coincide i.e. the elements with the largest and smallest
atomic volumes do not melt, respectively, at the highest and lowest
atomic volumes.
ever,
points.
The following
relations
fusi-
weight
mercury by
Richards
Ztschr. phys.
Chem.
40,
169, 597
(1902)
41,
129 (1902)
49, 15 (1904).
2
31
most
tion
dissolves
The order
Copper
than
less
In, Tl
most rapidly.
The metals of the mercury group, in genThe farther the element is removed from
mercury, the less the solution and diffusion. These relations are
clearly shown in the following table. The arrows point in the direction of increase in solubility
SERIES
and
diffusion.
32
and physical nature of the element showed that it must come between lithium and boron, and, indeed, be the head of the magnesiumcalcium group. The true atomic weight was subsequently shown to
be 9.08. Similarly, uranium was supposed to have the atomic weight
60, 120, or 180, and it was difficult to decide between these values.
But it was more probably 240 in terms of the Periodic System and
this conjecture has' also been verified. It should be observed that in
these cases the vapor-density method of determining the number of
atoms in the molecule could not be employed.
The Periodic System has been used not simply to decide between
an atomic weight and a multiple of this quantity, but to actually
correct atomic weights imperfectly determined.
Bunsen found the
atomic weight of csesium to be 123.4. This value was smaller than
would be expected from the Periodic System. The correct atomic
l
weight of caesium was found later to be 132.9, which is in perfect
accord with the system. More recent work in connection with
osmium, iridiurn, platinum, and gold make it very probable that
;
is
the
weight
and other properties of an element can be determined from the
properties of the two neighboring elements in the same series and
the two neighboring elements in the same half of the same
group.
The properties are as a rule the mean of those of the four elements.
These four elements were termed
by Mendeleeff the Atomic
of the element in question.
example
Analogues
This will be clear from the following
of strontium is the
mean
33
properties.
On
when the Periodic Law was announced. The element predicted was
named from the element in the same group which immediately pre"
adding the prefix eka." In the third group the element
immediately following boron was unknown, and was termed ekaSince it followed calcium with an atomic weight of 40, and
boron.
preceded titanium whose atomic weight is 48, its atomic weight
must be 44. The oxide must have the composition Eb2 3 and have
cedes
it,
magnesium oxide. The sulphate must be less soluble than aluminium sulphate, just as calcium sulphate is less soluble than magnesium
The carbonate would be insoluble in water. The salts
sulphate.
would be colorless and form gelatinous precipitates with potassium
hydroxide and carbonate, and disodiurn phosphate. The sulphate
would yield a double salt with potassium sulphate. Few of the salts
would be well crystallized. The chloride would probably be less
volatile than aluminium chloride, since titanium chloride boils higher
than silicon chloride, and calcium chloride is less volatile than
magnesium chloride. The chloride would be a solid, and its density
about 2. The specific gravity of the oxide Eb 2 3 would be about
3.5.
Ekaboron would be a light, non-volatile, difficultly fusible
metal, which would decompose water only\on warming. It would
dissolve in acids with evolution of hydrogen, and would have a
specific gravity of
about
3.
In a similar manner Mendeleeff predicted the existence and properties of an element between aluminium and indium, terming it
ekaaluminium. The atomic weight would be approximately 68.
Again, an element should exist between silicon and tin, and this
was termed ekasilitium, with an atomic weight of 72.
The properties of the last two elements and their compounds are
described in considerable detail from the properties of their atomic
2
analogues, but for these the original paper must be consulted.
These elements have now all been discovered. The element
described by Nilson
an atomic weight of
1
Lieb.
44.
Ann, Suppl.
8
Ber.
d.
8,
196 (1872).
Loc.
cit.
34
dran,
And germanium,
hydrogen
very outset there is evidence of this incompleteness
does not fit at all into the scheme, and yet it is one of the most important elements. In the very first group of the elements, again,
there is apparent inconsistency. Along with lithium, potassium,
which con-
find
manganese
find the
at all
Compt. rend. 81, 493, 1100 82, 168, 1036, 1098 83, 611, 636, 663, 824,
86, 941, 1240 (1875-1878).
Ser. d. chem. OeselL 19, 210 (1886) Journ. prakt. Chem.
[2], 34, 177
;
1044
(1886)
towards oxygen.
all
35
this element.
It seems better to recognize these elements as distinct exceptions,
which do not fit into the Periodic System at all satisfactorily yet
even here we must recognize a certain periodicity in the recurrence
of these exceptions, and that they occur in every case in groups of
three.
The Periodic System seemed to be hard pressed for a time to
find a place for some of the elements described by Ramsay as occur;
we can
It also contains
by Ramsey
in the atmosphere.
is
that a
number
of
Mendeleeff table are made the ninth and tenth series in the new table.
This system has marked advantages over the earlier forms. It
real existence
since not a
member
covered.
known
elements.
Staigmtiller
36
37
ELEMENTS
The Ratio
J. J.
for the
The
Cathode Particle.
entirely
new
light
This result
recent
work
of
is
Thomson's
of these particles.
He
was
constant,
was
passed.
He then tested whether the nature of the cathode had any effect
on the value of this ratio. He made his cathode of widely different
metals such as platinum, silver, aluminium, zinc, iron, copper,
etc.,
The value
x 10 7
in
This
for the
of
tin,
is
X 10 4
Thus,
the value of this ratio for the cathode particle is one thousand times
its value for the hydrogen ion of acids.
In order to determine the
Native masses of the ion in the gas, and the ion in solution
we must know the relative values of e in the two cases.
of acids,
it is
necessary to
know
e,
by the
ion.
38
nuclei around
When
a gas in which
the
number
9 u
the velocity with which the particles fall, or the cloud
or mist settles, g the gravitational constant, r the radius of the drop,
and u the coefficient of viscosity of the gas. By measuring v, the
in
which v
is
velocity with
of the drop.
radius.
that
by measuring the current that passes through the gas under a given
electrical force.
It was found in this way that the value of e, or the charge carried
by the gaseous ion, is the same as that carried by a univalent ion, such
as the hydrogen ion in the solution of acids.
The Mass
Since
for the
is
10 4,
and since
of the
Phil Mag.
is
39
all gases,
no matter how produced, and since e is also the same for all negative
gaseous ions, it follows that the mass of the negative ion that is split
off from all gases is the same, and is about one one-thousandth that of
the hydrogen ion.
which can be
1
.
17 65
gases regardless of their
constituent of the atoms of all matter.
from
This ion,
chemical nature, is a common
This ultimate unit of matter of which all the atoms are composed,
having a mass about -^-^ of that of the hydrogen atom, and carrying
split off
all
par-
ticle of
ion,
We shall
now
of the
Thomson pointed
itself
be of electrical origin.
ing sphere,
uncharged.
to determine
whether there
is
The
Kaufmann determined
cles.
The following
results
were obtained
L
m
2.36
1.31
2.48
1.17
2.59
0.975
2.72
0.77
2.83
0.63
Phys. Zeit.
4,
54 (1902).
velocities.
m by
107 :
40
It is obvious
from these
results that, as v
becomes greater,
be-
comes
Since
less.
e,
of electrical origin.
This raises the further question, is all the mass electrical ? If
mass is of electrical origin ? Thomson has
not, what part of the
on this
Assuming that the whole mass is
thrown
is
question.
calculated the ratios of the masses of the particles moving with different velocities, to the mass of a slowly moving
which is constant. He compared his calculated values with
light
electrical,
Thomson
particle
the corpuscle
highly probable that the whole of the mass of
is
of
elec-
trical origin.
The Electron.
Thomson
The electron is a unit charge of negative electricity, entirely disembodied from what we have hitherto regarded as matter. It is the
It is the fundamental
ultimate unit of which all matter is composed.
unit of all the chemical atoms the atom of one substance differing
;
it.
of as attached.
We
We
are inclined to
usually take just the opposite view.
regard matter as the reality, and energy as hypothetical. It is interesti
J.
41
it.
atoms.
from
arranged within
the atom.
An atom, in
terms of the electron theory, is made up of a large number of electrons, the number being expressed by the atomic weight of the
element multiplied by 1765. The electrons are moving with high
1 For a fuller discussion of these matters see the
following work by the
author of this volume, from which a part of the above sketch was taken: The
Electrical Nature of Matter and Radioactivity.
New York, 1906, D. Van
Nostrand Company.
2
Phil Mag. 7, 237 (19Q4).
42
space occupied by
say that the spaces taken by the electrons are incomparably small,
The atom can be
as compared with the distances between them.
electrons
are playthe
in
which
solar
a
small
as
looked upon
system
ing just about the same role as the planets.
These electrons, 1 or negative charges, are
moving in a sphere of
uniform positive electrification. Thomson has not yet been able to
solve the problem as to the arrangement of the electrons within the
entire sphere, but has solved it for a plane through the sphere.
In order that we may have equilibrium, the electrons must ar-
The
twenty
total
is
number
59
an outer ring of
given by Thomson.
62
61
NUMBER
63
IN SUCCESSIVE
IN
THE PLANE
64
65
66
67
RINGS
20
20
20
20
20
20
20
20
20
16
16
16
17
17
17
17
17
17
13
13
13
13
13
13
14
14
15
10
10
10
10
10
233334455
we should
1906, D.
New
York,
43
Let
striking, especially in connection with the Periodic System.
first the system with a total of 59 electrons in the plane.
This is the smallest total number of electrons that can have 20 in
us take
and would
it
a rearrangement.
positive element.
It
to a bivalent electro-
with
its
electrons less
readily than the system with 60, and would, therefore, be less
strongly electropositive than the system with 60.
Similarly, the system with 62 electrons could lose three, and thus
become a trivalent electropositive element.
Turning now to the other end of the series, we have the system
with 67 electrons. We cannot add even one electron to this system
without making it unstable and necessitating a rearrangement, since
the system with 68 electrons would have 21 in the outer ring.
The system with 67 .electrons, like the system with 59, would
then correspond to an atom with no valence.
The group with 66 electrons could add one, and only one electron,
without passing beyond the number 67, which is the limit of stability
with 20 in the outer ring. It would correspond to a univalent electronegative element.
become a
add three
electrons,
and thus
44
electronegative element,
ists.
sources,
(1900).
8
Nature, March 31st, 1870. Reprinted in Amer. Journ. Science [2], 50, 38
Also Lieb. Ann. 157, 54 (1871).
(1871).
45
five
hundred
number
of
Numbers
terms with which the mind can deal. This has already been done
l
by Lord Kelvin in the last paragraph of his paper
for us
Perhaps the best demonstration of the/ almost unlimited divisibility of matter is furnished by some of the aniline dyes or by fluorescein, where one part is capable of coloring or rendering fluorescent
at least one hundred million parts of water.
The absolute size of the molecules has been calculated on entirely
different grounds by Nernst, J. J. Thomson, and others. The results
obtained are, in general, of the same order of magnitude, and in many
mous
1
difficulties
LOG.
(1902).
cit.
"Weight
of
Atoms."
See Kelvin
we
Phil.
Mag.
CHAPTER
II
GASES
LAWS OF GAS-PRESSURE
Properties of Gases.
tion gas, liquid, and solid.
states of aggrega-
These
differ
movement of the parts, the inner friction being many times greater
than in a gas; while in a solid the parts are relatively fixed, and
movement is accomplished only by subjecting the solid to very great
pressures.
solids,
changes in pressure. A solid has its own definite shape and volume,
independent of the shape and size of the containing vessel. This
volume varies with the temperature according to definite laws, and
only slightly changed by change in pressure. Gases differ from
and solids also in that they represent matter in a very dilute
form. A little matter is distributed through a large space, or as it
is
liquids
is
Some
at
of these
first
sight
appear, since a gas can be compressed to a liquid, and a liquid converted into a solid. And, similarly, a solid can be liquefied, and a
liquid converted into a gas.
Indeed, most of the forms of matter
with which we are acquainted are known in all three states of
aggregation.
46
GASES
47
Of the three
since
it
Law
at its
placed
of Boyle.
pressure to
p=
If v
is
expressed thus
may
be
pv
c is
cd.
= cm.
If p is the pressure
and v the volume of a given mass of gas, and p l and v 1 the pressure
and volume of the same mass of gas under other conditions, Boyle's
law may be expressed thus
:
The product
number
shown.
The
best,
2
investigation of Amagat on this problem is probably the
is certainly the most fundamental which has ever been
and
carried out.
He
Ann. Chim.
48
increases
Natterer, that the product of pressure and volume, pv,
for
in
with increase
very high pressures. Amagat plotted
pressure
the results obtained for hydrogen, nitrogen, carbon dioxide, oxygen,
etc.,
20
in curves. 1
40
60
80
100
120 140
160 180
Pressures in metres of
mercury.
Fia. 3. ETHYLENK.
19, p.
379 (1880).
49
GASES
small pressures, so that the curve for hydrogen does not show any
minimum, but is very nearly a straight line. This will be seen from
Fig. 4.
Amagat
from the law of Boyle. Some of his earlier work l indicated that the
values of pv, with increase in pressure, remained more nearly constant
at higher temperatures.
This led him to carry out an elaborate in-
vestigation,
42
40
KM
,36
J34
32
26
20.
40
60
80
100 120
260.
4.
HYDROGEN.
and
4.
cury.
in metres of mer-
The values of pv for ethylene and all the other gases studied, with
the exception of hydrogen, at first decreased, then reached a minimum, and finally increased as the pressure increased. It will, however, be seen
1
50
If the law of
less as the temperature increases.
be a straight line parallel to the
would
curve
the
Boyle applied,
This condition is more and more nearly realized as the
abscissa.
and for ethylene at 100 the minimum is far less
rises
becomes
less
and
temperature
16.3. The deviation from Boyle's law
sharp or pronounced than at
in temperature also in the case of
rise
with
becomes less and less
be seen by consulting the curves
will
as
and
carbon dioxide
methane,
;
marked exception.
The value
of
very
in this case
between
no
that
there
is
deviaseems
large
quite probable
It, however,
tion from Boyle's law shown by very dilute gases; i.e. where the
pressure is small and there are relatively few gas particles in a
sults obtained are so conflicting that it is impossible to decide
them.
given space.
If a gas is kept under constant pressure
The Law of G-ay-Lussac.
and its temperature raised, the volume will increase. If the volume
The remarkable
-^
B,
If
is
constant for
we keep
Its
all gases.
approximate value
is
is
0.003665.
warm
P=p
+ 0.003665
(1
t).
If, on the other hand, the pressure is kept constant and the volume allowed to increase with rise in temperature, the volume at t, V,
is
volume
V= v
at
(1
0,
% thus
+ 0.003665
t).
If both pressure
Loc.
cit.
GASES
=pv
pv
*=
from which,
ft
51
(1+0.003665
t)
(1+00036660-
This
what
760
C.
is
taken as
mm.
The
of mercury.
value of the constant 0.003665 is determined either
by keeping
the pressure constant and measuring the increase in volume with rise
in temperature, or by keeping the volume constant and measuring the
increase in pressure as the temperature rises.
The values found by
the two methods differ only slightly, and we take 0.003665 as very
nearly the true value of the temperature coefficient of a gas.
is very nearly
which means that if a gas is cooled down
^7-3-,
273 C. its volume would become zero if the law of Gay-Lussac
held down to the limit. This temperature, termed the absolute zero,
has now been nearly realized experimentally. It is quite certain that
temperatures have been produced which are within twenty degrees of
this point. It is, however, very probable that the laws of gas-pressure
would not hold at these extreme limits.
If we represent temperature as measured from the absolute zero
by T, the combined expression of the laws of Boyle and Gay-Lussac
This
to
We usually
represent *3LJ by R,
273
Law
of Gay-Lussac.
ex-
expansion of ethylene
of results taken
1
is
[5], 22,
353 (1881).
75^.,
p. 383.
52
PRESSURE IN
METRES OF Ho.
GASES
notice.
53
metre's pressure
milli-
The
pressure used with hydrogen varied from 4.7 mm. to 0.077 mm.
The coefficient of expansion at the higher pressure was 27 *8 5
This
remained practically constant until the pressure was diminished to
.
-^
Q 8
The
Law
of Avogadro.
The law
of
thus:
assumption
of course,
is,
is
therefore
Horstmann Ber. d. chem. Gesell. 14, 1242 (1881). Van't Hoff: Ztschr.
Chem. 1, 491 (1887), Scientific Memoir Series, IV, p. 24.
:
phys.
54
just as
we combined
in the equation
PV= RT.
litre, is
If
we use
the equation
1,
we
273
= 0.082
This
is
T.
and Avogadro.
Apparent Exceptions
ber of substances
tions to the
to the
Law
known which,
law of Avogadro.
of Avogadro.
nium
our subject.
comparatively simple, and the nature of gas-pressure, mechanically considered, not very complex.
gases
is
GASES
is
55
cles or molecules of
in straight lines
We
theory and
take into account the space occupied by the gas molecules themselves.
We must introduce into the equation which expresses both the laws
b,
There
is
is still
The assumption is made that the particles of gas do not exert any
attraction upon one another, and it is quite certain that such an
attraction exists.
Van der Waals 1 has taken this into account, and
1
56
v.
This term
must be added
pressure.
Van
is
4\(v-V)
then
= RT.
v,
and
b the space
IT
occupied by the molecules is also small. The gas under these conditions would be more likely to accord with the simpler expressions,
and such is in general the fact, with perhaps a few exceptions at
very small pressures, and here experimental errors are large. As the
pressure increases the two correction terms acquire finite values, but
If a has a large value, the volume is appreact in opposite senses.
ciably diminished,
and pv decreases, as
is
for
b at all
by
theory of gases.
1
Ostwald
Lehrb.
d.
Allg.
Chem.
I, p.
226.
GASES
DENSITIES
Densities
57
The determination
of the
is to
be preferred to
air,
of the latter varies slightly from time to time and from place to place.
The density of air is 14.37 times the density of hydrogen, and since
by
d,
m = dx 28.74.
In this way the molecular weights of gases can be calculated from
their densities.
we know
it
therefore
we
the weight of the empty flask. The weight of the flask being
known, and the weight of the flask plus the substance which just
filled it with vapor, we know the weight of the substance.
By deter-
know
58
The
flask of
mined are introduced into the flask, the neck drawn out to a capillary,
and the flask placed in a bath which is at least ten or fifteen de-
The substance
grees above the boiling-point of the substance.
vaporizes, drives out the air, and when the vapor of the substance
ceases to escape, the capillary is fused shut. The flask after cooling is weighed. The fine point is then cut off under mercury and
the flask filled with mercury. The flask may then be weighed
again, or the mercury poured out and measured, giving the volume
of the flask. 1
The method
of
Dumas
is
In the
sidered later.
is
difficult to
first place, it
so small
errors
result
that
relatively large
this
source.
from
method
tures,
at
The method
rate.
of
Dumas
can-
FIG. 5.
to
For
rausch
ir
(1860).
Lieb.
Ann.
Also
GASES
59
the vapor, by
2 the weight of the vessel filled with air, and by
3
the weight of the vessel in which there is a vacuum, the relative
density of the vapor and air is expressed thus
:
Wj-TT,
W- W
2
'
After vessels of the same volume and weight have once been
prepared, this method of procedure is more convenient and far
more rapid than that originally described by Dumas.
The method
of
Dumas
is
used
less to-day
than
it
was formerly,
The method as originally proposed by Gay-Lussac conplacing a known weight of liquid in a calibrated vessel over
mercury. The whole is then warmed until the liquid is converted
into vapor.
The temperature is noted, also the volume of the vapor.
The latter is reduced to standard conditions, a correction being introduced for the tension of the mercury vapor. This method has
measured.
sists in
4
by Hof mann
Buff: Pogg. Ann. 22, 242 (1831). Marchand: Journ. prakt. Chem. 44, 38
Victor Meyer: Ber. d. chem. Gesell. 13, 399, 2019 (1880).
(1848).
2
Biot:
consists
Ber.
Traite,
d.
I,
p. 154.
p. 291.
chem. Gesell.
1,
198 (1868)
9,
1304 (1876).
60
The apparatus
pressure.
The calibrated tube
is
shown
rests in a
is
brought
of the
The advantage
of the modi-
FIG.
6.
Ber.
d.
The tube
is
GASES
stopper,
61
to,
and
under, a Calibrated tube filled with water and dipping into a water
The substance to be used is weighed in a weighing tube
reservoir.
When
r.
The
air
displaced air
tube
t,
weight
of
the
substance
introduced.
We
know
by this method,
and the method can be used at very high
7.
temperatures.
At higher temperatures
vessels
is
The
Biltz
62
amount of substance required, is that the temperature of the experiment does not need to be known. It is only necessary te keep the
temperature constant before and after the introduction of the substance.
at
is
it
replaced by an indifferent
Ber.
Ber.
*Ibid.
d.
Monatsh.
20, 505,
909 (1899)
d.
p. 34.
Bleier
Physikalisch-chemische Methoden,
Monatsh. 20, 909 (1900).
Gasomet. Method., p. 160.
Physikalisch-chemische Methoden,
p. 34.
GASES
Of the methods considered
for
63
determining the densities of
The
vapors, that of Meyer is by far the most generally applicable.
method of G-ay-Lussac and the modification proposed by Hofmann
The method
of
Dumas
is
elementary gases have shown many interesting and surprising relabetween the number of atoms contained in the molecules of
these substances. The molecular weights of a number of elementary
tions
gases, calculated from their densities, show that the molecule is made
up of two atoms. This applies to hydrogen, oxygen, nitrogen, chlo-
bromine, and a number of others. The vapor-densities of mercury, cadmium, and glucinum show that the molecule is monatomic,
or that the molecule and atom are identical.
On the other hand, the
rine,
At temperatures
is especially interesting.
600 the molecule of iodine consists of two atoms. As
the temperature rises, V. Meyer 2 on the one hand, and Crafts and F.
Meier 3 on the other, found that the vapor-density decreases, and
that above 1400 the density is only about one-half the value at the
lower temperature. Above 1600 it is quite certain that the vapordensity of iodine would remain constant, since at this temperature
the atom and molecule would be identical, and no further dissoci-
The
case of iodine
from 200
to
2
8
d.
64
'
was nothing
broken
class of
We
phenomena.
ammonium
like
chloride,
NH
vapor-density
[2], 68,
440 (1838).
GASES
65
mann l found by
NeuThis
decreased with rise in temperature up to 290, where it became conSimilar results were found by Cahours. 2
number of
stant at 3.7.
other examples similar to the above were known, but these suffice to
The explanation of these abnormal results was
illustrate the point.
not furnished at once, and for a time the hypothesis of Avogadro was
rather at a discount because of their existence.
we
shall
now
The
see,
explanation,
chloride
How
could this
it
ties.
to detect either
Pebal. 6
He made
vapor of
near the top of the inner tube, which is open above. A stream of
hydrogen is passed through a into the outer part of the apparatus,
1
Lieb. Ann. Suppl.
*Ann. Chim. Phys.
Compt.
5,
341 (1867).
[3], 20,
rend. 45, 857.
Lieb.
373 (1847).
66
and another stream through b into the inner part of the apparatus.
The whole is heated above the boiling-point of ammonium chloride.
If the salt is
the
decomposed when
ammonia being
chloric
acid would
it volatilizes,
above the
wad
excess
of
ammonia
of asbestos
must contain an
FIG.
8.
The
raised
by
heat.
facilitated
the breaking
down
ignored.
To
is
little
This objeccould
not be
foundation,
Lieb.
Ann.
is
made out
is
of
GASES
67
ammonium
ammonium
two
chloride.
Nitrogen is passed through the tube, the
chloride d heated with a lamp, and the vapors in the
sides passed over colored litmus, as in the experiment of Pebal.
The vapor
ammonium
chloride
was found
to
monium
chloride.
It is thus
chloride
acid,
is
by heat
The work
alone.
l
of
is
pentachloride
it
through the space between the two glass tubes. If the vapor of the
pentachloride was dissociated by heat into the trichloride and chlorine, these would diffuse with different velocities into the upper
portion of the vessel, since they have different vapor-densities.
They would then be swept out by the current of air in different
quantities, the chlorine being in excess since it is the lighter, and
would, therefore, diffuse more rapidly into the upper portion of the
vessel.
itself.
The vapor
of chloral hydrate
CC1 3
COH H
.
was shown by
its
Compt. rend.
Compt. rend.
52, 549
68
counted
for,
real ex-
ceptions to the law of Avogadro, they furnish a beautiful confirmation of the law.
Products of Dissociation.
posed
is
lessened.
Thus,
ammonium
chloride
is less
dissociated
if
is
The vapor-density
This
is
the
importance
SPECIFIC
HEAT OF GASES
The amount
amount
of heat
heat capacity
capacity
represent
and the rise in temperature by dt, the
expressed thus
added by
c is
d$,
,.&
dt
1
GASES
The heat
69
specific heats.
is
expressed thus
<7
= l^.
m dt
The specific heat of a gas has been found to vary greatly with
If the gas is allowed to expand as it is heated, so
the pressure.
that the pressure remains constant, it has a definite specific heat,
which is termed its specific heat at constant pressure. This is usuIf, on the contrary, the volume of the gas
by Cp
the
constant
as
the pressure increasing,
kept
temperature rises,
the gas has a different specific heat.
This is termed its -specific
heat at constant volume, and is usually written Cv
ally represented
is
These two
we
shall see,
different, as
them.
Constant Volume.
The gas
is
work
of E.
Wiedemann. 2
specific heat of
was a
Paris, 1862.
Ztschr.
70
GASES
71
we should
volume,
difference
why
And
since,
perature,
we
could see
why
and made
amount of
merely qualitative stage,
heat consumed in compressing a gas was exactly equivalent to the
amount of work done. He thus showed that heat and work are of
similar nature, and that force, or
indestructible as matter.
what we now
call energy, is as
If heat
definite
it
72
work,
it still
the amount of heat required to raise one gram of water from zero
to one degree is equivalent to about 42,550 gram-centimetres of work.
have now expressed, in the mechanical equivalent of heat, the
We
Law of
energy,
is
impossible.
relation between the specific heat of a gas at constant
pressure and the specific heat at constant volume, can be calculated
The
at once
from the
first
law of thermodynamics.
relation
dO
==
dE +
dW.
(1)
But the external work, dW, is equal to the pressure, p, times the
change in volume dv, supposing the pressure to remain constant
:
d9
The
= dE+pdv.
(2)
and volume
The
change
last
member
in volume,
when no
ex-
(2)
(3)
GASES
If the
volume
is
73
= 0. v J|=ff
djj.cu.
constant, dv
= C + p ^.
d^
Cp
which we
But
cL J.
The term
will
||
cH
now
the specific
is
u/J.
J.
Therefore,
C,= C,-hpf,
(4)
= RT,
we
see
RdT.
constant, pdv
p
Substituting this value of pdv in equation (4),
that
is
we
obtain
Cp = C + R.
(5)
constant for
all gases.
R very
simply, since
R = ^^,
Z( o
as
we have
1033.2
<
273
We
calorie.
or
Therefore,
R = 2 calories,
to recent determinations of the mechani-
For a
Ostwald
Lehrb.
d.
Allg.
Chem.
I,
234.
74
volume by
becomes then
at constant
where
(7,.
stant volume.
The following
In the
last
GASES
75
by experiment.
successfully accomplished.
Determination of the Relation between the Specific Heats of a Gas.
number of methods have been suggested and used to determine
the ratio of the two specific heats of a gas, but of these only one
will be considered.
the best and most convenient of them all
Reference 1
The gas
the gas
is
obtained thus
Ml?
Z^U 28.88
Z2
The
ratio
between the
determined by the
Miiller:
2
8
from the
By exam-
76
culated
The
specific
1
heats in the case of mercury gives a considerably higher value.
And the same applies to argon and helium, as will be seen below
:
GASES
The
77
warm
=
"cv
3^'
2(
is
K= E
)'
o.
=
|=1.666.
less in
to
Therefore
?~
quently
< 1.666.
^
G,
would
Conse-
78
is
exactly
ratio of the
gases, as
two
what we
find in
The conclusion
atom
in the molecule.
many
wave-lengths of light.
or subdivide.
Indeed,
doubt in the case of mercury, and it is almost certain that the same
would be obtained with argon and helium.
The Second Law of Thermodynamics.
The calculation of the
result
modynamics.
GASES
79
motion
but since
fpdv.
Since pv
= RT,
is
expressed thus:
vi
W=Cpdv
= ETln^l.
v
80
very high temperatures are converted into vapor between the carbon
poles of an electric arc, and then their spectra examined.
By means of spectrum analysis, then, the lines which are characteristic of the elements can be studied, and their wave-lengths
determined.
of
all
the
unknown
material
is
suspected, resort
is
some foreign
spectroscope.
If white
Absorption Spectra of Gases; Law of Kirchhoff
light is passed through a gas and then through a prism or thrown
in the
upon,a grating, it is seen to contain dark lines
.
exactly
places
Phil.
Mag.
GASES
phenomena up
81
discovered that
when
is
is
we have a means
exist in the sun.
dark lines in
which of our
elements are present in the sun. In this way a large number of the
dark lines in the solar spectrum have been " identified," as it is stated
;
shown
to
the remaining terrestrial elements may occur in the sun. Among the
we find most of the metals which occur on the earth.
solar elements
also been applied to the stars, planets, commoon, nebulae, etc. but for the results obtained reference only
can be made to the excellent little book of Landauer, Die Spectralets,
analyse.
An
ele-
Some
(1868).
93.
is
regarded as a
(1868).
82
iifferent wave-lengths.
between the wave-lengths of the vibrations sent out by the same element was made lay Lecoq de Boisbaudran, 1 but the first successful
2
He showed that the wave-lengths of
attempt was made by Balmer.
the first spectrum of hydrogen can be accurately calculated from the
equation
*
n
\-A tf~^l'
n having the values 3 to
15,
and
A the
value 3647.20.
3
however, Kayser and Eunge, who first deduced any general relation which obtained for a number of the elements.
Their
It was,
equation
is
taking instead of the wave-length X, its reciprocal. To test their formula they redetermined more accurately the wave-lengths of the lines
of
many
of the elements,
series of lines.
The
first series,
known
as the
Primary Se-
very bright
lines,
equal.
The relations between the lines of other elements were not as well
defined as with the alkalies. Certain elements showed the
existence
of secondary series,
but, in general, as
in the Periodic
om rend 69 6 94.
2
med Ann 25 80 (1885)
*Abhandl. Berlin. Akad. 1888,
1889, 1890, 1891, 1892, 1893. Wied.Ann.52,
British Ass. Report, 1888,
(1894).
Chem. Zeitg. 16, 633.
p. 576.
-
>
14
GASES
lines of
less distinct.
83
For further
details in this
more and more toward the red. This has since been
shown by Ames 3 not to be strictly true in the case of magnesium,
zinc, and cadmium.
The work of Kayser and Runge, and of Rydberg, 4 are again of
of different elements.
(2) Cu,
(3)
Mg,
Ca, Sr.
Cd, Hg.
(5) Al, In, Th.
(4) Zn,
Within these groups the spectrum tends more and more toward
This is what we might exthe red, with increasing atomic weight.
pect, the heavier atom vibrating more slowly and sending out fewer
As we
pass, however,
these elements to another, the spectrum tends toward the violet, with
increase in atomic weight.
These relations must, of course, be refirst approximations to any general truth, and when
consider that some elements vibrate in thousands of periods, or at
garded as only
we
ent elements.
Loc.
Landauer
cit.
:
Die Spectralanalyse, p.
Phil.
be-
69.
CHAPTER
III
LIQUIDS
gation.
The
increase in the
is
EXPANSION OF WATER
TEMPERATURE
is
taken
85
LIQUIDS
If
we
form than
gases.
many
gas occupies
must be taken
the liquefaction of a
3
Bussy worked
at
He
liquefied sulphurous acid, and made the important discovery that when this liquid was allowed to evaporate in the air, a
ures.
Kopp
[2], 26,
I,
p. 121.
63 (1824).
Pogg. Ann.
1,
237 (1824).
86
faction of the
resistant gases.
Utilizing this
^fact,
Bussy was
He
purpose.
studied a
carbon dioxide,
its
number
etc.,
and liquid
to
come
Faraday published
in 1845. 3
The
the results
incentive,
number
rier's
mixture.
[2], 60,
427 (1835).
87
LIQUIDS
"
permanent gases had baffled all attempts to liquefy them, and
But during this period the nature of gases
still continued to do so.
was studied more closely, and knowledge acquired which made
"
more
This
is
it
was shown
it
cannot be
it is
subjected.
is
It soon
down
in the tube containing the hydrogen, when the pressure was reThe experiments of Pictet 4 cannot be described in detail.
moved.
He
succeeded in liquefying oxygen, as has been stated, and possibly hydrogen also, and, indeed, may have obtained a little solid
hydrogen.
We now come
Poles,
to
the very
WroUewski and
Olszewski.
2 Ibid.
Compt. rend. 85, 1217 (1877).
85, 1214, 1220 (1877).
9 Ann.
Chim. Phys. [5], 15, 132 (1878).
4
88
89
LIQUIDS
on a commercial
air
scale.
liquid form.
was
liquefied
re-
is,
187, and at
this
Phil.
4 Proc.
Proc. Soy. Inst. 1886, 550.
Boy. Inst. 14, 1 (1896).
Trans. Roy. Soc. 186, 253 (1895). Communicated by Ramsay.
Compt. rend. 124, 1202 (1897); 125, 505 (1897).
6
6
7
8
Mag.
18,
210 (1884).
Chem. News,
90
experimentally
made by working
now that we have
That many
We
are
slightly
important discoveries will be
quantity at hand.
In tracing the development of the
principles and methods involved in liquefying gases, it was
pointed out that there is a temperi
little
4
Chem News
.
91
LIQUIDS
Tour observed
it
was
cannot be liquefied.
by Andrews the
called
Critical
This temperature
The
Temperature of the gas.
work
of
Andrews was
When the
dioxide.
105
tube
100-
of
13.l,
and the
gas
subjected to a pressure
of 48.9 atmospheres, a
90
85
without
ish
con-
any
75
siderable
70-
in
65-
what
60
tures,
higher
13
50
Although
VOLUMES
ume
pressure, yet no liquid separated.
there was
marked decrease
FIG. 10.
(31.l
results of a
tempera-
however
and 32.5),
55-
liquid
increase
At
still
in vol-
at a certain definite
92
pressures.
The curve
is
mospheres
any marked
for 13.l shows that when a pressure of nearly 50 atreached, the volume diminishes very greatly without
This means that the gas has
increase in pressure.
passed over into liquid at this pressure. The curve for 21. 1 is
An abrupt transition from gas to liquid
similar to the lower curve.
The curves for 31.l, 32.5,
takes place, but at a higher pressure.
less
and
less abruptness,
peratures
any liquid produced. The curve at 48. 1 shows no break,
being perfectly smooth throughout. The temperature above which
carbon dioxide cannot be liquefied was found by Andrews to be
is
is,
Many
The
2
by Heilborn, but since some of these have been quite recently determined with greater, accuracy, the original papers bearing upon the
liquefaction of gases and the properties of the liquids formed must
be consulted. The critical temperatures and pressures of some well-
known
93
LIQUIDS
is
but did not cool the gases down to the critical temperatures. After
these gases were sufficiently cooled they were liquefied at moderate
pressures.
It
Continuity of Passage from the Liquid to the Gaseous State.
from what has been said in reference to critical tempera-
will be seen
ture and pressure, that a liquid can be transformed into vapor without becoming heterogeneous at any time. If the liquid is warmed
any extent, yet the substance which was originally liquid remains
homogeneous. The passage from the liquid to the gas is thus
perfectly continuous, and it is impossible to say where the liquid
state ends and the gaseous begins.
The condition of matter at
and near the critical point has always perplexed men of science,
and many opinions have been expressed concerning it. Andrews
discussed this condition in connection with carbonic acid.
He
pointed out that if this gas above the critical temperature is subjected to a pressure considerably above the critical pressure, there
is
condition
is
this
the two.
point
equal.
critical density.
The
critical
then, that at
Ramsay
state
may
persist
beyond the
critical
94
and
the term "vapor" for matter just above the critical point. It,
however, seems best to still limit the states of matter to three,
gas, liquid,
do,
and
solid,
as
volume, but capable of nearly indefinite expansion, it is obvious that a substance above the critical point is in the gaseous
condition.
have just seen to exist between liquids and gases has led to the
Since the
application of the kinetic theory of gases also to liquids.
passage from a liquid to a gas, and vice versa, under certain conditions is so gradual that
tion ends
it is
to the other.
We
Ann. Chim.
95
LIQUIDS
We
tiire.
can clearly see the reason for this in terms of our theory.
The molecules of the vapor, in their movements through the confining space, come in contact with the surface of the liquid. Some of
these are continually coining within the range of the attractive forces
of the liquid molecules, and are drawn down, as it were, into the
equilibrium is reached. Equilibrium is established when the vaporpressure has reached such a point that the same number of gaseous
molecules are condensed in any unit of time as there are liquid molehave seen that it is only the molecules converted into vapor.
kinetic
the
with
cules
greatest
energy which can so far overcome the
molecular attractions as to escape from the liquid as vapor, and this
We
We
that
when
mean
off as
vapor in a
condition.
When
this is arranged
v,
we have
96
hut of the
the one that of the liquid, the other that of the vapor
we know nothing. If we construct the curve corresponding to
;
third
the above equation, we will have the following figure (Fig. 11).
The abscissas represent volumes, and the ordinates pressures. Each
to curve 6.
increases from
pressure decreases from C to E, the volume still continues to deAs the pressure increases again from E, the volume contincrease.
ues to decrease.
If we compare this curve
with the results of experiment,
say Andrews' work
with carbon dioxide,
we
find that the first part of
curve 1 corresponds to the
results
obtained.
When
subjected
increasing
volume depressure,
creased as represented by
the
the curve
AB.
Since the
is
below the
temperature
critical,
when
certain
the
gas
liquefied.
The
VOLUMES
corresponding to that of
the liquid was reached.
This is represented by the
FIG. 11.
97
LIQUIDS
is
critical,
is
liquid.
i.e.
other,
it is
obvious that
it
impossible to proceed
of the instability of these
it
is
states.
we have the
equal to that of the liquid, or where there is no discontinuity between the two states. It is only at this point that gas and liquid
can be transformed .into one another isothermally and without loss
in continuity.
The temperature,
respectively, the
are,
critical
volume.
critical
stance.
The method
of obtaining this
point
is
It is only necessary to draw a number of isothermal curves for constant values of a and b in the Van der Waals equation, starting at a
say that
and
we can
critical
volume of a substance.
98
many
We
many
substances
in the liquid state are complex, while in the gaseous state the molecule is generally the simplest conceivable.
On account of the very
account for
Van
all
der Waals.
In this section the attempt has been made to point out the most
striking relations between liquids and gases, and in doing this some
must now
general properties of liquids have been considered.
We
any relations which may exist between properties and chemical composition on the one hand, and properties and constitution on the
other.
Indeed, it was right in this field that much of the earlier
The question was raised, and
physical chemical work was done.
answered as far as possible, how does the introduction of a CH 2 group,
or of an oxygen or chlorine atom, affect the physical properties of
the compound into which it enters ?
Or what is the difference
between the effect on one compound produced by a given atom or
group, and the effect on other compounds? Then the question of
the effect on physical properties of an atom or group in one state of
combination, as compared with the effect produced by the same atom
or group in a different state of
combination, arose.
What,
for ex-
99
LIQUIDS
of Liquids.
When
a liquid
is
in contact
with free space, it continually sends off particles into this space, as
we have seen. Given a liquid in contact with an inclosed space
particles are constantly escaping from the surface of the liquid, but
at the same time vapor-particles are condensing.
Finally, an
;
its
In speaking of the vaporpressure of liquids we must, then, always state the temperature to
which the vapor-pressure refers. In comparing the vapor-pressures
of liquids we could select some temperature and measure the pressures
of their vapors at this temperature
this method has been extensively
perature the greater the vapor-pressure.
used.
The
method,
is
100
different liquids
measured
at this
mometers.
In the
in the dynamical
stances agree very closely, showing that there is for any liquid a
The apparent
definite vapor-pressure for any given temperature.
differences between the results of the two methods have been shown
to be due to the large error produced by traces of volatile impurities,
when the statical method is used. 2
many
cases.
d.
101
LIQUIDS
t'
+f(t
- 100).
the
the boiling-point of
is
stant factor.
cases;
to
it.
The
3
by Ramsay and Young should, however,
relation discovered
If
which again
is
R=R+
When
= 0,
R'
= J2,
c (t'
equal zero
may
then
t).
ratio
between the
or fifteen sub-
stances with one another, that their formula agrees with the facts to
within a comparatively small limit. They 4 tested still further the
relation
a constant at
tljat
all pressures.
Wied Ann
.
12,
40 (1881).
102
103
LIQUIDS
1
Kopp pointed out in 1844 that this is not the case.
perature.
Ethyl acetate and butyric acid are isomeric, yet the former boils 82
latter.
He
Methyl acetate,
Ethyl formate,
Methyl valerate,
Amyl
formate,
Ethyl butyrate,
CH3 COOCH8
HCOOC 2 H 5
CH3 CH2 CH 2 CH 2 COOCH 3
HCOOC 6 H U
CH 3 CH 2 CH 2 COOC 2 H 6
56
55
115
116
115
work a number
his results will
few of
show that
by the
facts.
Methyl alcohol,
CH4O
Ethyl alcohol,
C2H6
Propyl alcohol,
C 3 H8O
Butyl alcohol,
C 4 H 10O
Formic
HCOOH
acid,
......
......
......
......
.....
.....
.....
.....
.....
BOILING-POINT
65
78
96
109
105
Acetic acid,
CH3 COOH
117 C
Propionic acid,
C 2 H 6 COOH
142
Butyric acid,
C 3 H 7 COOH
156 C
Ethyl formate,
HCOOC 2 H5
Ethyl acetate,
CH3 COOC 2 H6
74
Ethyl propionate,
C 2 H 5 COOC 2 H 6
96
55<
22
composition.
i
Lieb.
Ann.
The
50, 71 (1844).
8
104
CH
difference in composition of
compounds, and is equal to 19."
2,
is
the same in
many
series ol
He
perature, that of ethyl formate being the greater throughout.
the
of
and
are
as
gives
equal vapor-pressures,
temperatures
they
follows
'
Ethyl formate
Methyl acetate
...
.
20
26
33
43
53
21. 7
27. 8
34. 7
44. 5
54. 4
perature,
is
BOILING-POINT
Octyl formate,
Heptyl acetate,
Amyl
butyrate,
Butyl valerate,
C 9 Hi 8 O 2
C 9 H 18 O 2
C 9 Hi 8 O 2
C 9 Hi 8 2
......
198. 1
191. 3
184. 8
185.8
Kopp
of
by
lemmer 2 not
some of their
derivatives, as the following results will show. b.-p. represents the boiling-point, and d. the difference between the
boilingpoints of two successive members of a homologous series.
L
Lieb.
Lieb.
LIQUIDS
105
106
The
effect of constitution
b.-p.
CeH6 .C 2 H 6
133-135
b.-p.
b.-p.
107
LIQUIDS
Normal butyl
alcohol,
Isobutyl alcohol,
CH 3 CH2 CH 2 CH2 OH
^>CH.CH S OH
CH 8 CH2 CHOH CH3
CH3
.
H8 C
OH
116
109
99
.....
82. 5
CH3
The normal compounds, or those with a chainlike structure,
have the highest boiling-points. The larger the number of side
This is somechains, the lower the boiling-point of the compound.
times expressed by saying, the more symmetrical the compound the
lower its boiling-point. Naumann l attempts to explain the higher
boiling-point of the normal compounds as due to their chainlike
The molecules constructed in this way make better constructure.
than when there are side chains to the molecules, and the
larger the number of side chains the poorer the contact between
tact
The
the molecules.
pound conforms
point.
We
two
compounds.
Of the isomeric substitution products of benzene the ortho compounds in general boil higher than the meta, and these, in turn, a
little higher than the para compounds.
This again is only an approximate relation, to which many exceptions are known.
Effect of Certain Atoms or Groups on the Boiling-point of Liquids.
- The
boiling-points of compounds are affected with some regularity
the
introduction of certain atoms or groups. Thus, the introducby
tion of a chlorine atom into a methyl group raises the boiling-point
of the compound about 60 to 65.
The introduction of a second or
1
7,
173 (1874),
108
third chlorine
point.
This
products.
is
LIQUIDS
109
HEAT OF VAPORIZATION
Heat
of Vaporization.
Methods
of Determining.
We
have seen
We
Whenever a
sumed in vaporization. It is far simpler to measure the heat liberated during condensation, and this has been done. The apparatus
devised by Schiff l has some advantages over that constructed'several
2
years earlier by Berthelot.
To
Lieb.
Ann.
110
stances
zation
liquids boil.
That this relation is very nearly true is seen
vaporization,
and
Schiff.
Mh
is
the substance.
111
LIQUIDS
classes of substances.
ing the energy relations of the liquid and gaseous states of aggregation.
Heat
the critical point is that at which all differences between the liquid
and its saturated vapor disappear. It is, therefore, necessary that
at the critical point the heat of vaporization should become zero.
known
SPECIFIC
HEAT OF LIQUIDS
Heat
Methods of Determining.
Just as the
of Liquids.
Specific
amount of heat required to convert comparable quantities of different
liquids into vapor varies for every liquid, so, also, the amount of
heat consumed in raising a liquid through any given range of
The relative
temperature varies from one liquid to another.
amounts of heat required to raise unit quantities of different substances through the same range of temperature are known as the
Water is taken as the
specific heats of the substances in question.
and
the
of
other
heats
substances
unit,
specific
compared with
the specific heat of water. The amount of heat required to raise
the temperature of one gram of water from
to 1 C. is termed a
2
The
earlier
methods of determining
[6], 21,
69 (1890).
These
will
be considered under
112
The
Since water
is
It is
has been termed the "method of mixtures.'
obvious that a number of corrections must be introduced, as in all
calorimetric measurements, for the specific heat of the vessel, etc.
of this
method
Bunsen
measuring
it
specific heats.
From
ice,
but this
is
In connection with his determination of the mechanihe reinvestigated the problem and found that
heat of water decreases from 5 C. up to about 30 C., and
the specific
ROWLAND'S RESULTS
LUDIN'S RESULTS
113
LIQUIDS
Kowland 1 says
in connection with
Ms
"However remarkable
this fact
results,
first
may
be,
being the
first
Relations between
Heats.
Composition
relations exist
Specific
between
heats,
We
MOLEC. HEAT
Methyl alcohol,
Ethyl alcohol,
MOLEC. HEAT
114
The
on molecular heats
effect of constitution
shown by
is
the
MOLEC. HEAT
C4 H8 2
I Isobutyric acid, C 4 H 8
f Allyl alcohol, C 3 H 6
t Propyl aldelyde, C 3 H 6
f
Butyric acid,
.
.
47.4
47.6
38.1
32.6
the molecular heats are not very different. If, however, the isomeres
have constitutions which are very different, the molecular heats may
The
specific
He
heats."
arid also a
number
investigated
of other classes
As
and a
what he termed a
the esters having the formula CoH 2n 2
"
Equal weights at equal absolute temperatures have equal heat
law 2 for
all
capacities."
"
Equal volumes at equal fractions of the absolute critical temperature have equal heat capacity."
The relations between specific heats and composition and constitution, like the relations between boiling-points and composition and
constitution,
must be regarded
as only approximations.
When these
Lieb.
Lieb.
Ann.
Ann.
Ztschr. phys.
Chem.
1,
376 (1887).
115
LIQUIDS
by
r,
expressed thus
is
sm
tive
liquid,
is
spectrometer.
Beyond
at
294 (1895).
is
8,
47
15, 389.
Ztschr. phys.
Chem.
18,
116
V-ZV
sin
e.
This apparatus has a number of advantages over all other forms for
determining indices of refraction. It is very simple to use, and gives
accurate results it requires but little time to measure the refractive
;
it is
power of liquids
is
'
results.
= const.,
light.
The
number
of cases.
= const.
d
Landolt 8 tested this formula at different temperatures and found
that it held very closely for many substances. He also
applied this
1
2
8
117
LIQUIDS
equation to mixtures, and found that
it
light,
On the whole the latter expresthe facts quite as well as the more complex formula.
3
Dufet, in 1885, and Sutherland, in 1889, furnished a theoretical
of
law.
demonstration
Gladstone's
fit
nd
and showed that
it
= const.,
not at
the facts.
it is
Indeed,
Landolt,
^d
This expression
this is multiplied
have the
~
is
termed the
2
8
specific
refractivity.
molecular refractivity =
1
= const.
M we
9
When
Phil.
17,
473 (1895).
118
of substances we must
covering relations between the refractivities
refractivities.
molecular
compare their
Relations between the Molecular Refractivities of Substances.
The
relation
M(n - 1)
H2O
Water,
Methyl alcohol,
CH4
Ethyl alcohol,
C 2 H 6O
Formic acid,
CH 2 O 2
Acetic acid,
C2 H4
Propyl alcohol,
C 8H8
Propionic acid,
C8 H6
Butyric acid,
C4 H 8
Butyl alcohol,
C 4 H 10
Amyl
C 6 Hi 2
13.17
20.70
28.30
36.11
43.89
>7.60
7.20|
I
7.46
7.53
7.95
7.81
i
!
7.78
7.65
2
alcohol,
M(n-\)
d
Ethyl formate,
C 3 H6
29.80\
Ethyl acetate,
C4H8
36.16<
Ethyl butyrate,
C 6 Hi 2
Ethyl valerate,
C 7 Hi 4
;>6.36
y 2 x 7.58
M.88
59.20 /
51.32 <^
are given.
119
LIQUIDS
2x5 + 6
1.3
+ 1x3 = 20.8.
refrac-
120
The molecular
very considerably from one another. There are appreciable differences in some cases, but even these are not very great.
The effect of constitution on molecular refraction, while recognized by Landolt, was not carefully investigated by him.
considerable
from
number
He
LIQUIDS
121
122
about four units higher than that calculated, then there are two
double unions in the molecule and so on.
This method was applied by Brtihl to
Constitution of Benzene.
We have seen from results already given that the molecubenzene.
is
JCH
HClL
and three doubly united carbon atoms, and on the whole is probably
the most generally accepted formula for benzene which we have
to the present.
It should, however, be stated here that another
physical chemical method has led to exactly the opposite conclusion
viz. that in benzene we have all the carbon atoms united
by single
up
bonds.
clusions, but the fact that such different results are obtained
make us
by
dif-
results obtained
of a
number
of the
CH
hydrogen
of carbon
is
very close to
1.3.
*
8
Gladstone also
still
larger value
Mem. Akad.
123
LIQUIDS
determined by
its refractive
power.
This
mula
of Kekule.
He
fractivity,
union
III
on
re-
and found that it corresponded to 2.02. If in the formafrom three molecules of acetylene, the three triple
tion of benzene
unions were transformed into nine single unions, then the molecular
refraction of liquid benzene should be about 6.06 smaller than that
of three molecules of acetylene gas.
The difference as found was
only 1.19. Therefore, when acetylene passes into benzene the triple
unions are not converted into single unions.
1
Lieb.
(1887).
Ann.
Ztschr. phys.
Chem.
1,
307
124
and
which
is
HC=CH = 3 - HC = CH -
The above
line of reasoning is so clear and so satisfactorily confirmed by experimental evidence at every point, that there would
seem to be no escape from the conclusion were it not for the conflicting result, which, as we shall see, is furnished by another physical
chemical method.
final result,
of Gladstone and especially of Brtihl, it can be stated that the molecular refraction of a compound is, in general, the sum of the atomic
refractions of the atoms which enter into the molecule.
This is
we have
marked
refractivity.
The atomic refracapproximately constant under all conditions only for the
univalent elements. Oxygen in the carbonyl condition has a greater
refractive power than in the hydroxyl condition.
The presence of
tion
influence in
some cases on
is
its refractivity,
we have
as
That constitution
The
and
is
line.
Column
II
LIQUIDS
125
126
decimetre
in length, or if a solution
of the active substance in the volume
it
of one cubic
centimetre.
is
in question.
127
LIQUIDS
Since the
it
is
=
100
Id
A
the molecular rotation thus
is
expressed thus
av
mL
M= 100
av_
Ip
tivity
cations, the one turning the plane of polarization to the right, the
other to the left.
If a solution of sodium ammonium racemate is
evaporated at low femperatures, rhombic, hemihedral crystals sepahaving the composition Na.NH 4 .C 4 4 6 + 4 2 0. The crys-
rate,
however, not
The
some
from those on other crystals. Indeed,
the crystals divided themselves sharply into two classes, the one
tals are,
all identical.
tetrahedral faces on
We
[3], 24,
442 (1848)
28, 56 (1850)
31, 67 (1851).
128
the
left.
"
When
this
is
The
polarization to the right.
laevo-racemic acid rotated the plane of polarization just as much to
From racemic acid Pasteur was
the left, as the dextro to the right.
thus able to obtain two acids, the one rotating the plane of polarization to the right, the other to the left
the racemic acid itself being
He was, however, not content to stop here. If
optically neutral.
;
down
into
constit-
when
uents, then,
crystals of racemic acid separated in abundInstead of dextro-racemic, ordinary dextro-tartaric, acid could
be used, since the two are identical.
ance.
/^.
(-3^ 2 8, 56 (1850)
129
LIQUIDS
known
in which the
work
Hoff and Le
Bel.
any wide-reaching
of Pasteur
the constitution of
exists only in the crystalline molecule, only the crystal will be active ;
on the contrary, it belongs to the chemical molecule, the solution
if,
we must regard
is
the
This
130
illustrates
known
this
substances
principle
at that time,
opti-
cally active
H
I
CH
COOH
OH
Le Bel pointed out at the very close of his important paper, that we
never obtain by direct synthesis the dextro or the laevo acid, but
always the inactive or racemic modification, which is a combination
of equal parts of the two active forms.
Van't Hoff l also pointed out that in every optically active substance there is at least one carbon atom in combination with four
asymmetry
CH
La Chimie dans
VEspace.
Rotterdam, 1875.
131
LIQUIDS
metric,
carbon
theory
asymmetric
atom"
These simple suggestions lie at the foundation of all stereochemistry, which is one of the most interesting and important phases of
We can see
organic chemistry during the last quarter of a century.
impossible to construct two tetrahedra which cannot be superimposed. This can readily be seen by means of models. If, on the
other hand, all four atoms or groups are different, then two tetrahedra
it is
activity.
Le
The theory also explains the very important fact pointed out by
Bel, that by synthesis we never obtain the dextro or the Isevo
form alone, but always a mixture of both forms. Since optical activity depends only on the arrangement of the constituents in the molecule, from the law of probability we would have just as many
molecules formed having the one configuration as the other. For
every dextro-rotatory substance there would thus be an equal quantity of the corresponding laevo compound formed.
Here, again, the
theory furnishes a satisfactory explanation of facts which, without
its aid,
The presence
atom
is
necessary, as
we
is
and from
to be
on the
is
laevo
132
COOH H OH
.
OH H COOH.
.
and of
we never obtain one active subThe two optically opposite varieties are
Indeed,
always formed together, and the mixture of these two, or the racemic
modification, is the result. We have already seen in one ease how it
is possible to obtain optically active varieties from a racemic mixture
;
we
tions.
mixture.
from
this
isomeric components an optically active substance which will combine with them. The two compounds formed may differ sufficiently
in properties to enable
solubility, crystal form,
them
to be separated.
They may
etc.
differ in
By utiliz-
alkaloids.
III.
third method of separating the constituents from a racemic
modification consists in treating the mixture with certain microorganic forms. These will often destroy one of the active modifica-
133
LIQUIDS
Schtitzenberger, he says
another inactive substance
"
The theory
in
many new
lines
3
He attempted to discover relations between the nature
by Guye.
and magnitude of the rotation, and the nature of the atoms or groups
which are combined with the carbon atom and occupy the corners
of the tetrahedron.
If
we assume
the four solid angles of a regular tetrahedron, the six planes of symmetry of the compound CR 4 represent what Guye termed the planes
of symmetry of carbon.
When
the carbon
is
2
8
134
symmetry.
When
the carbon
lie
is
symmetry by d d d3 d4 ds d 6)
,
,
respectively, the product of these
This product is
as the product of asymmetry.
the carbon is symmetrical, but has different values as the
l}
six values is
zero
when
known
by Guye is,
hypothesis
product of asymmetry can then serve as a measure of the asymmetry
of the carbon, and it is but natural to suppose that the rotatory
:
as this product."
of this
hypothesis
should be increased. If, on the contrary, the centre of gravity approaches more nearly the planes of symmetry, the rotatory power
should decrease.
III.
If
is
replaced from
moved
EOTATION
Methyl tartrate
Ethyl tartrate
-f 2.
14
+7.66
Propyl tartrate
-f
12.44
Isobutyl tartrate
19.87
135
LIQUIDS
atoms
by a group of mass
The
121.
- 88.78
- 60.02
Methyldibenzoyl tartrate
Ethyldibenzoyl tartrate
Isobutyldibenzoyl tartrate
41.95
Since this hypothesis was proposed, Guye has carried out many
and elaborate investigations l to test its validity. The result of all
this work is to show that the hypothesis accords with the facts in
many directions. But it is only a partial expression of the truth.
It alone is not sufficient to account for optical activity.
In addition
we must take
into account
to the effect of
mass on
optical activity,
the relative position of the four groups, their mutual action on one
another, their configuration, and the chemical nature of the atoms
The phe-
nomenon of
optical activity
is,
114, 473
Phil Trans.
136, 1 (1846).
119, 906
136
pendent influence.
800
63, 67
67,
255
69,
M&
/
[5], 12, 5 (1877).
[2], 32, 523 (1885).
137
LIQUIDS
it.
Similarly,
conditions.
few of the
by Perkin
Take first the
results obtained
by him.
will
show what
influence of the
rela-
CH
138
MAGNETIC PROPERTY
2
Faraday found that
Paramagnetic and Diamagnetic Bodies.
divide
themselves
into
two
classes with resubstances in general
spect to their behavior toward a magnet. Those which were attracted
by the magnet, such as iron, cobalt, nickel, manganese, chromium,
Those which were
platinum, etc., were termed paramagnetic.
such
as
the
tin,
magnet,
bismuth,
repelled by
"mercury, copper,
arsenic, iridium, uranium, tungsten, etc., were called diamagnetic.
The magnitude of the attractive and repellent forces was measured by Plticker. 3 He found that the magnitude of the attractive
force was proportional to the number of magnetic molecules present.
Work of Wiedemann. The most accurate work which has been
done on the magnetic properties of substances is that of G-. Wiedemann. 4 He measured the force by means of the torsion of a German
silver wire.
The
specific
magnetic attraction,
/*,
is
expressed thus
A
BC*
where
A is the
C, the
Jf, is
of the substance,
mi
/n,
Wiedemann confirmed the conclusion of Plticker, that the magnetic attraction is proportional to the number of molecules of dissolved salt. He also used different salts of the same metal, and
found that the molecular magnetic attraction was the same for the
different salts, if the magnetic metal was in the same state of oxidation in all of the salts.
1
Ztschr. phys.
Chem.
19,
1.
323 (1896).
139
LIQUIDS
More Recent Work.
1
Henrichsen, working in part with "Wletigel,
number of measurements on the
magnetic property of substances. He has somewhat modified the
torsion method of Wiedemann, and has used a number of diamag-
and
netic substances.
According to him, molecular magnetic repulsion,
at least, is an additive property being approximately the sum of the
atomic repulsions. Certain constitutive influences manifest them;
concludes that
when
when
dilation occurs,
diamagnetism
increases.
SPECIFIC
We
is
of the substance
Methods
method
Mohr
This
is
ing the volume of the solid immersed in the liquid, we know the
volume of the liquid displaced by the solid. A more convenient
1
140
method
in
pycnometer.
mark
to the
at ra
c.
liquid
by
S
.
Work
of Kopp.
W2
w +A
t
1
He found that
certain liquids were early pointed out by Kopp.
constant differences in composition corresponded to constant differ-
compound
is
Kopp's
LIQUIDS
141
The
effect of constitution
1
studying isomeric substances.
C2 H4 2
\ Methyl formate, C 2 H 4 O 2
f Ethyl valerate, C 7 Hi 4 O2
I Ainyl acetate, C 7 H 14 O 2
/-Propionicacid, C 3 H 6 2
J Ethyl formate, C 3 H 6 2
( Methyl acetate, C 3 H 6 2
f
Acetic acid,
MOLECULAR VOLUME.
63.6
...
....
63.4
173.6
......
173.4
85.4
85.3
84.8
Kopp
also
5.5, of
hydroxyl oxygen 7.8. From these values Kopp calculated the molecular volumes of a large number of liquids, and showed that they
agree very closely with the values found experimentally at the
boiling-points of the substances.
than in the saturated condition. Thorpe found that isomeric substances have approximately, but not exactly, the same molecular
is
VISCOSITY OF LIQUIDS
Methods of determining Viscosity.
The methods
of determin-
ing the inner friction of a liquid, or its viscosity, are based upon two
Either a solid body is moved in the liquid and the
principles.
i
Lieb.
Ann.
LoCt c ^; 172.
Lieb.
Ann. Suppl.
4,
129 (1865).
142
resistance
1
apparatus consists of a bulb attached to a
of vessel at the other
capillary tube, arid a bulb or some other form
end of the capillary to receive the liquid. The volume of the first
noted.
bulb
is
The form
of
this
and probably
the most accurate work which has ever been done on the viscosity of
2
These authors review the
liquids, is that of Thorpe and Rodger.
work which had already been done on viscosity, and then discuss
The aim of their investigation was to throw light on the
relation between the viscosity of homogeneous liquids and their
chemical nature. The method was to measure the time required by
a liquid to flow through a capillary tube. The viscosity could be
measured from zero up to the boiling-point of the liquid.
The
formula of Slotte was used for calculating viscosity
their own.
rj
rj
= c (1
-+-
bt) U.
is
c, 6,
and u are constants, varying with the nature of the liquid. The
viscosities of some seventy liquids were measured at different temTo discover quantitative relations between viscosity and
peratures.
chemical nature, some temperatures must be chosen at which the
liquids are in comparable condition with respect to their viscosities.
Comparisons were made at the boiling-points of the liquids, but it
rate of change of
temperatures of
equal slope.
CH
143
LIQUIDS
Alcohols and acids give exceptional results.
influence on the viscosity coefficient, as
marked
Constitution has a
shown by compar-
is
for
VISCOSITY CONSTANTS
Hydrogen.
Carbon
.
...
.V
...
44.5
166.0
......
......
256.0
.
-
Hydroxyl oxygen
Carbonyl oxygen
Chlorine in monochlorides
Bromine
in
monobromides
Iodine in monoiodides
Double linkage
Ring grouping
.'
31.0
.
198.0
374.0
499.0
244.0
48.0
r ,
SURFACE-TENSION OF LIQUIDS
Method of Measuring.
While gases tend to
their
and
increase
the
surface
of a liquid tends to
volume,
expand
contract and occupy a smaller volume.
This potential energy,
present at the surface of liquids, produces a tension which is known
"as surface-tension.
Any force which tends to increase the size of
Surface-tension.
lows
tube of radius
the gas in which the experiment is carried out, and g the acceleration
of gravity the surface-tension y is obtained from these values
:
i-
ghr
(D
Eelations
Relations between Surface-tension and Composition.
between surface-tension and composition were pointed out in 1860
144
were published in
by Mendeleeff, but more extended investigations
2
He compared the capillarity coefficients of
1864 by Wilhelmy.
the consubstances, which he termed a. This was obtained from
1
by multiplying by S, the
and dividing by 2
stant
specific
alcohol
\ Amyl formate,
2.43
a
2.36
2.45
1.75
2.75
a
2.45
2.63
3.94
/ Ethyl formate, C 3 H 6 O 2
\ Methyl acetate, C 3 H 6 2
/ Ethyl butyrate,
2.32
C 3 H6O 2
CsH 6 O8
similar constitution
does not
Acetone, C 3 H 6
Ethyl formate,
a
.2.42
...
......
.........
.........
.......
.......
........
........
C 2 H6
Acetone, C 3 H 6 O
Amylene, C 6 H 10
Xylene, C 8 Hi
Alcohol,
Lactic acid,
CH
......
....
....
......
Methyl alcohol
Ethyl alcohol
Amyl
in composition of
C 6 H 12 2
C 6 H 12 O 2
........
........
......
.....
.
a
2.63
2.58
2.55
2.61
points has
shown that
this temperature
Compt. rend.
Lieb.
50, 52
51, 97.
An
represents
an analogous
composition corresponds
extensive bibliography
145
LIQUIDS
CAPILLARITY
CONSTANT
Allyl alcohol,
Acetone,
C 3 H6 O
C 8 H6
57.87
6.006
57.87
5.189
Among
C = 2H;
= 3H;
C1
= 7H.
later
investigations, but
in
atom
fatty acids,
is
may
cases
so on.
From
the above
affected
by
is
Lieb.
to be sharply distinguished
Ann.
223, 53 (1884).
from the
146
dt
we
Mv,
If
Mv =
where
critical
is
temperature downward.
Ramsay and
Shields
They must
y=
A
B and
and the
investigated are introduced through (7, and this is then drawn out as
shown in the figure. The tube is then connected with a pump, and
the liquid boiled until all the air has been removed. When the tube
contains only the vapor of the substance, it is closed by fusion.
The
1
2
Phil. Trans.
A. 662 (1893).
147
LIQUIDS
raise or lower the capillary so that the surface of the liquid inside
the tube shall be only a few millimetres below the
1
\
nite temperature
methyl
for-
is
The
few
Methyl
alcohol, ethyl alcohol, and acetic acid preThe value of c is not a constant,
sent exceptions.
]~H
[-H~]
this
may
be true,
M must vary
or, in a word, the molecules of these substances are more complex at low temperatures than
ture
FIG. 13.
in temperature are
known
as "associated."
with change
The degree
of associa-
148
first
a non-associated liquid
y at 19.4
y at
46.l
= 33.58
= 29.41
carbon bisulphide
y(Mv)* at 19.4
.
differential
dCyCafi;)*]
dt
46.l
y(Jfv)* at
= 515.4
= 461.4
is
46.1-19.4
Since this value differs so slightly from the 'mean value 2.121 for
we conclude that carbon bisulphide belongs to
non-associated liquids,
this class.
= 37.47
at 46.4 = 34.42
at 79.8 = 30.80
= 424.4
y(Mv)$ at 46.4 = 397.7
y(3fv)* at 79.8 = 364.6
y at 16.8
y
y
Between the
first
y(Mv)* at 16.8
*-\
- 397.7
'
'
46.4-16.8
= 397.7 - 364.6
'
79.8-46.4
dt
The value of c differs greatly from the normal value 2.12 for non
associated substances, and, therefore, the molecules of formic acid
are associated into complexes.
l
Ztschr. phys.
(1909).
Chem.
12,
462 (1893).
See Walden
149
LIQUIDS
x.
is
obtained by multiplying the association factor by the simplest molecThe molecular weight of formic acid
ular weight of the substance.
and the
like.
The
results of
We
They
it
can be compared.
As
150
normal
liquids, the
asso-
further very
much
rises
ture.
reached.
is,
however,
still
open to some
doubt.
to
but even this does not seem to be entirely free from objection.
The surface-tension method enables us, then, to distinguish be-
tween liquids which are not associated and those which are; it
probably makes it possible to determine very roughly the degree
of association, or the number of the simplest molecules combined
to form the liquid molecule.
The Method of Longinescu for determining the Molecular
3
Weights of Pure Homogeneous Liquids.
Longinescu found that
l
Ztschr.
Chem.
phys.
15,
98
Proc.
(1894).
Roy.
Soc.
56,
162
(1894).
2 Ibid.
See D. Berthelot: Compt. rend. 126, 954 (1898).
15, 111 (1894).
See D. Berthelot: Journ. de Phys. (3) 8, 263 (1899). See D. Berthelot:
Compt. rend. 128, 553, 606 (1899). Forch: Wied. Ann., 68, 801 (1899).
Dutoit and Friedrich Ibid. 130, 327 (1900). Dutoit and Friedrich: Arch. Sc.
phys. Nat. 11, 105 (1900). Guye
Compt. rend. 132, 1043 (1901). Whatmough
:
Ztschr. phys.
Chem.
1,
Bogdan
289 (1903).
(1906).
Pann:
151
LIQUIDS
the
following
liquids
empirical
relation
holds
for
a good number of
which
Longinescu found that those liquids for which the above relation
did not hold, were the very ones that had been shown by the surface-tension method to be polymerized.
He, therefore, used the
above relation to determine the amount of the polymerization of such
liquids.
T =
The numerical value
in the form:
= constant.
many
liquids
maximum
and since
To
n,
we have
calculate the
number
liquid,
only necessary to determine experimentally the absolute
at which the liquid boils, and its density
at zero
temperature
it is
degrees.
The method
laboratory.
is
152
few
ciated liquids
COMPOUND
153
LIQUIDS
method
tion.
In this case
D is its
is
density.
Taking
its
the absolute
The
values
value as 70,
we
have
1,
154
and by
its
molecular weight,
In the above equation the first term is equal to 37 and the second
For a large number of liquids the first term is less than 37
and the second greater than 27, showing that the two values of
obtained from the above equation of the second degree find their
counterpart in the liquid. That is to say, in a liquid we may have
the molecules that
both polymerized and dissociated molecules
are dissociated being broken down into their constituent- atoms or
to 27.
Dielectric Constants of
Some
of the
More Common
Solvents.
The
is
property and the power of liquids to break down molecules into ions.
This relation will be taken up later, when the dissociating power of
different liquids is under consideration.
The meaning of the term " dielectric constant of a
medium "
is
155
LIQUIDS
capacity of the medium, and has since
dielectric constant of the medium.
A number
come
to be
known
as the
methods have been devised for determining dielecshould mention especially those of Thwing, 1
2
3
The method of Drude is, on the whole, the
Nernst, and Drude.
It consists in measuring the length of stationary electrical
best.
waves in the medium in question. These are a function of the
The
dielectric constant of the medium, and a very simple function.
the
root
of
wave
to
the
of
is
length
square
inversely proportional
the dielectric constant of the medium.
of
We
tric constants.
The
dielectric constants of
some
of the
at
DIELECTRIC CONSTANT
Hydrogen dioxide
Water
Formic acid
92.8 ?
Nitrobenzene
36.0
Methyl alcohol
33.7
Ethyl alcohol
Propyl alcohol
Ammonia,
Amyl
liquid
alcohol
77.0
63.0
26.9
......
11.0
Aniline
7.3
Chloroform
Ether
Carbon disulphide
5.0
......
Benzene
It
was thought
constant of any
22.0
16.0
Ethylene chloride
tric
22.0
4.4
2.6
2.3
for a long time that water has the highest dielecknown solvent.
solutions of salts in liquid
When
of
*
Phys. Rev. 8, 38 (1899). Turner: Ztschr. phys. Chem. 35, 385 (1900).
" Dielectric Constants of Gases and
Vapors." See Badeker Ibid. 36, 305
See Palmer: Phys. Rev. 14, 38 (1902).
Schlundt
Journ. Phys.
(1901).
Chem. 8, 122 (1904). Von Wilier: Phil. Mag. (6) 7, 665 (1904). Walden:
Ztschr. phys. Chem. 70, 569 (1910).
:
156
Calvert
to this property.
intensified.
is
a close relation
between many of the physical properties of liquids and their composition and constitution.
Many of these relations are thus far
their
meaning and significance being entirely unpurely empirical,
known. Yet, in most cases, such relations have been clearly established beyond question, by very elaborate and careful investigations.
While at present we fail to see the real significance of most of these
lie
ulti-
it
chapter; and instead of these empirical generalizations being neglected, they should stimulate to renewed effort to discover what they
really mean.
1
Ann. der Phys. 1, 473 (1900). "Dielectric Constants." See Nernst:
Wied. Ann. 57, 209 (1896). Abegg Ibid. 60, 54 (1897). Pewar and FlemWied. Ann. 60, 527
ing: Proc. Soy. Soc. 61, 1, 299, 316 (1897). Drude
(1897). Stark: Ibid. 60, 629 (1897). Dewar and Fleming: Proc. Hoy. Soc.
:
CHAPTER IV
SOLIDS
General Properties of Solids.
The third state of aggregation of
is known as the solid state.
We have seen that when any
matter
is
gas
state.
solid.
it is subjected.
these sufficiently and in the right direction, it can be
either of the other forms.
By
made
varying
to take
and liquid
solids.
states
shall
The most
states.
Another striking difference which really lies
at the foundation of those just referred to, is the relative rigidity of
the parts in a solid. The particles are firmly fixed, and move over
one another only with the greatest difficulty, enormous pressures being
required to change the form of solids. As it is said, the resistance to
movement or the inner friction of solids is very great. With liquids
there/ is
some inner
friction,
movement
inversely as pressure.
even when the pressure
The volume
is
very great.
is
much less
157
volume varies
of solids
is
158
Liquids are compressed but little by great pressure, but the change
in volume is greater than with solids.
The density of solids is much greater than that of gases, and, in
This is just what we would
general, greater than that of liquids.
expect, since the solid state represents matter in the most condensed
form. It is true that some liquids are heavier than some solids, but
is
generally true.
The change
in the
volume of
In
in either of the other states of aggregation.
will not react at all with another substance, but
much
many
when
cases a solid
it
less of the
is
melted
chemistry
true with
is
quite short.
CRYSTALS
Most of the solid substances with which we
Crystal Systems.
are familiar tend to take certain definite geometrical forms, which
more or less characteristic of the substance. This is true
whether the solid is formed from a homogeneous liquid or from
In the latter case, however, there is generally better
solution.
opportunity for the particles to arrange themselves according to
are
SOLIDS
159
of the
Some
known
system,
all at right
all
This
from the remaining systems in that all the properties of the crystals
This system includes such wellare the same in every direction.
The
as the octohedron, cube, dodecahedron, etc.
regular system is distinguished from all the other crystallographic
systems, in that it has the largest number of planes of symmetry.
known forms
II.
are built
from the other two all the angles between the axes
In such crystals the axis which is longer or
being right angles.
shorter than the other two is placed vertically, and the two axes of
different length
equal length are placed, therefore, in the horizontal plane. The symmetry here is evidently of a lower order than in the regular system.
is
that the
lateral axes,
system.
160
VI. In the triclinie or asymmetric system the three axes are all
and are all inclined to one another. There is no
of unequal lengths,
lost,
A given crystal
Tetartohedrism.
the planes present as an octahedron, a
When all the planes belonging to a given
prism, a pyramid, etc.
form occur, we have a complete or holohedral crystal.
form may occur with
It frequently
all
octahedron
is
the tetrahedron
of the hexagonal
bohedron, etc.
In a similar manner only one-fourth of the planes of the holohedral form may occur. In this way tetartohedral forms are produced, and examples of tetartohedrism are not wanting.
Importance of Crystallography for Chemistry and Physical ChemThe subject of crystallography has an important chemical
istry.
and physical chemical bearing. A given substance not only crystalin certain characteristic forms, but the angles between the
planes are constant for the same substance. This fundamental law
The crystal form
of crystallography is known as the law of Steno.
lizes
and
same form, we
SOLIDS
161
We
thus see from the above that while crystal form alone is not
an
absolute guarantee of the purity of a substance, it is of
always
very great aid to the chemist in determining whether he is working
with a chemical individual or with a mixture. All that has been
said above in reference
to the application of
crystallography to
form
by means of
certain hemihe-
form on other crystals. And this was the beginning of what has
been developed into an entirely new branch of science viz. stereo;
chemistry.
However, in addition to
all this,
162
They have no isothrough such crystals in which the two rays into which light is broken travel with the
same velocity. These are known as the optical axes, and hence such
crystals are termed biaxial.
The relations between crystallographic form and optical properties become perfectly clear when we regard light as a vibratory
motion of the ether. We must regard the crystallographic axes as
light passes as through an isotropic substance.
There are, however, two directions
tropic axis.
expressing the relative densities of the ether in the different directions through the crystal.
Thus, when all the axes are of the same
length, the density of the ether is the same in all directions through
then move in
When we come
complicated.
The
it
moves in
we
fore, the densities of the ether are different in the directions of the
three axes.
SOLIDS
163
There
crystallographic axis will necessarily be broken up into two.
in
such
the
directions
two
through
crystals,
plane of
are, however,
greatest and least density, along which the two beams of light move
with equal velocity. These two optic axes are placed symmetrically
with respect to the directions of least and greatest density. These
directions may, or may not, coincide with the crystallographic axes,
by
crystals
is
is
a neces-
what cases
we
by passing
it
crystal.
close relationship
A
between the geometrical forms of crystals
and their optical properties is thus evident. Indeed, the form is
an index to the condition of the ether in the crystal
a geometrical
expression of the relative densities of the ether in different directions
all directions
with
rise
in temperature.
Crystals in all of the other systems expand differ1
ently in different directions. Fizeau has shown that crystals in the
tetragonal
Compt. rend.
164
soid of revolution.
triclinic,
it
will
the melted
ellipse.
Electrical Conductivity.
Our knowledge of the electrical con2
Plates of
ductivity of crystals we owe chiefly to G-. Wiedemann.
were
covered
with
some
non-conducting powder, such as
crystals
Ann.
Pogg.
[3], 21, 457 (1847); 22, 179 (1848).
73, 191 (1848); 74, 190 (1849); 75, 50 (1849).
Lang Pogg. Ann. 135, 29
:
(1868).
2
SOLIDS
if
up
165
the ether
is
generally true,
it is
lizes in
this temperature it passes over slowly into a gray crystalline modification, which has very different properties from the ordinary white
tin.
Ztschr. phys.
Chem.
33, 57 (1900)
passes rapidly
166
back into the white again. While the exact crystallographic change
which takes place has not yet been worked out, it is quite certain
that the transformations in the case of tin are strictly analogous to
those which take place with sulphur.
The presence
of calcium carbonate,
which can
crystallize in either
have on the form which another will take, may even be so great as
to force it to take a form in which it would never crystallize if left
own forces.
The examples
to its
where a substance crystallizes in two forms, which have thus far not
been transformed into one another. Thus, diamond and graphite
have not been mutually transformed into one another, although the
latter has been obtained from the former.
That there is really any
inherent difference between this case and those above considered,
where such reciprocal transformations have been effected, no one can
believe.
The two or more forms in which the same kind of matter
more
clearer
when we come
same substance may crystallize in more than one form. This raises
the question as to whether different substances ever crystallize in the
same form. This question was answered once for all by Mitscherlich.
In an investigation l carried on in part in the laboratory of Berzelius,
he showed that a number of different substances may crystallize in
1
SOLIDS
167
which are
same
crystalline
form ; and
number and
relative position
This conclusion, as
is
manner produce
same crystalline form is independent
atoms, and is determined only by the
the
of the atoms."
number
of alums.
In the light of polymorphism and isomorphism, one would naturally ask, can crystal form be used at all as a characteristic of chemical composition ? The answer is, it can. Most substances crystallize
under ordinary conditions in characteristic forms, and crystal form
has been of the very greatest service in identifying and testing the
purity of chemical substances.
MELTING-POINTS OF SOLIDS
The method of deterMethod of Determining the Melting-point.
mining the melting-point of a solid, which is generally employed, is
very rough. The solid is placed in a fine glass tube closed at the bottom, and attached to a thermometer. The whole is then immersed in
sulphuric acid in a small glass bulb, and the acid warmed to the meltIt is evident that such a method can give only
approximate results, however slowly the sulphuric acid is heated.
There is nothing to protect the thermometer from the effect of radiation, and the warm bulb is constantly radiating heat outward on to
the colder objects around it. In order that any measurement of tem-
it is
screen, as nearly as
168
own temperature. In making an accurate meltingpoint determination, the bulb of the thermometer should be surrounded by a screen of platinum foil, which is also immersed in the
possible at its
same liquid
as the
it
may
be heated to
the same temperature. Since this precaution has been for the most
part disregarded, the melting-point determinations, especially of organic compounds, may contain some considerable error.
employed when only a small amount of subamount is available, the whole mass
may be heated above its melting-point and converted into liquid.
stance
is
is
at disposal.
If a larger
The
which
substance.
When
trifle
below
its
freezing-
point, it
its
is
true freezing-point.
An
to cause
made
ing chlorine compounds, and the nitro compounds higher than the
bromine compounds. Of the disubstitution products of benzene the
Ztschr. phys.
Peterson, Ber.
Chem.
d.
chem. GeselL
7,
68 (1874).
169
SOLIDS
C 4 H6 4
acid, CsH 8 O 4
Succinic acid,
Pyrotartaric
180
97
148
Suberic acid, C 8 Hi 4 4
Azelaic acid, CgHjgO*
Sebasic acid, Ci
18 4
140
Brassylic acid,
H
CnH20
103'
106
127
4
108
members
MELTING-POINT
C 2 H 4O2
Propionic acid, C 3 H 6 2
Butyric acid, C 4 H 8 O 2
Valeric acid, C 5 H 10 O 2
Caproic acid, C 6 Hi 2 O 2
(Enanthylic acid, C 7 Hi 4
Acetic acid,
MELTING-POINT
]
-f
16
+
+
+
30
-f
59.9
12
62
J
of
170
not pure, and that we are dealing with a mixture. The presence
of a very small amount of a foreign substance affects the meltingpoint quite considerably, usually producing a lowering of this point,
is
purity.
but the temperature does not rise until all of the solid has passed
over into the liquid condition.
During the process of melting, a
This
large amount of heat is consumed and disappears as such.
was early termed " latent heat," and the name still persists. The
amount of heat required to melt one gram of a substance at a fixed
is termed the latent heat of fusion of the substance at
the temperature in question. This quantity multiplied by the molecular weight of the substance gives the molecular heat of fusion.
When the melted substance solidifies, exactly the same amount of
temperature
is
The
the temperature does not rise, but the liquid passes over into vapor.
The heat required to convert a liquid into vapor is usually very
large indeed, the latent heat of vaporization is much greater than
the latent heat of fusion.
The large amount of heat consumed in
;
passing from the solid to the liquid state, and from the liquid to the
gaseous condition, does internal work driving the molecules farther
of heat
any substance, but in measuring the heat liberated by a given quantity of a molten substance at its melting-point when it solidifies.
This heat of solidification
is
fusion.
The
SOLIDS
a few of the more
table
common
solvents
171
is
79.7 cal.
Benzene
29.1 cal.
'
Nitrobenzene
Formic acid
.....
.
22.3
58.4 cal.
Acetic acid
43.7 cal.
SPECIFIC
Law
Dulong and
cal.
HEAT OF SOLIDS
Petit.
to this section
172
The sub
elements
that the
l
half
the
tain elements to
The
all.
The
to vary greatly with the nature of the material.
lowest value, 0.146, was found with the diamond, and the highest,
Values ranging all the way between
0.260, with animal charcoal.
and found
these two extremes were found with graphite, anthracite, coke, and
wood charcoal. This was evidently at variance with the law under
consideration, and especially so since the highest value found
far too low to accord with the law.
Regnault
was
discovered the same discrepancy in the cases of siliTheir specific heats were far too low to give the
when
it
was multiplied by
Work
five
tremendous piece of
sions reached can be pointed out.
was found to hold approximately
details of this
ele-
The elements
carbon, boron, and silicon present exceptions to this law, as Regnault had found. If the
molecular heat of many compounds is divided by the number of
Kopp
First,
may
1
vary somewhat with the temperature and density of the subAnn. Chim. Phys.
Dumas and
* Ibid.
3,
289 (1864-1865).
1,
202 (1840).
Compt.
SOLIDS
173
Work
of
sented, as
of others, that the higher the temperature the greater the specific
heat found. He determined to work at higher temperatures, and
which both were heated. The specific heat of carbon between 600
and 1000, multiplied by the atomic weight of carbon (12), gave 5.4
Dulong and
Petit.
the specific
and Petit holds also for these elements at more elevated temperatures.
most of the work thus far considered belongs to the period previous
and also true that a very large proportion of what follows
was done subsequent to that date.
But the distinction which we wish to draw is far more fundamental than that of years. The physical chemistry of to-day differs
not only in degree from that of twenty-five years ago, but in kind.
What was studied and taught at that time under this head bears no
close relation whatsoever to the work which is being done at present
by the modern physical chemist. We have already seen what are
to 1885,
174
who
is
familiar with
obscured by the brilliancy of the newer results, but the work of men
Guy Lussac, Avogadro, Bunsen, Kegnault, Stas, Helmholtz, and Landolt will ever lie at the foundation of modern chemical
like Dalton,
science.
obtained.
Modern physical chemistry has revolutionized
chemical thought in many directions, it has thrown light on a number of important physical problems, and has already made its way
into physiology and other branches of biology, and is now finding
results
its
way
We shall
science.
CHAPTER V
SOLUTIONS
pure condition.
We
form.
are,
One element
and
of- solutions.
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
These are
may
solid.
Our study
all of
of solutions con-
175
176
SOLUTIONS IN GASES
When
where no
chemical action takes place, that the term " solution of one gas in
another " is applied. When one gas dissolves in another, the condition is always fulfilled that any quantity of the one can dissolve in
other.
When any gas dissolves in another without acting chemically upon it, it is always soluble to an unlimited
extent, and this is a characteristic of the kind of solutions with
dealing.
PV=
V(Pl
+ P +-)
i
Indeed, this would be expected, since, when the gasnumerous in a given space, their effect
play.
sum
It
may, how-
mixtures of dilute
con-
stituents.
power
same as in a vacuum.
A number of
vacuum
is
Gilb.
Ann.
12,
;
385 (1802).
15, 21 (1802-1803).
*
*
air.
Some
Mem. Ac.
of the apparent
SOLUTIONS
177
SOLUTIONS IN LIQUIDS
In dealing with solutions in
of Gases in Liquids.
as
must
between the cases where
we
solvent,
distinguish
liquids
chemical action takes place between the dissolved substance and the
Solutions
known
ure,
of a gas dissolved
the gas
to be
by a liquid
known
is
as Henry's law.
The amount
is
subjected.
tested his law for several gases at pressures ranging from
one to three atmospheres, and found that it held quite closely. It
Henry
has since been subjected to more careful test by Bunsen and others, 2
with the result that the law has been shown to agree very closely
2
8
Pi
il.
Trans. (1803).
Gilb. Ann. 20, 147 (1805).
Khanikof and Louguinine: Ann. Chim. Phys. [4],
Li b. Ann. 112, 349 (1859).
N
11,
412 (1867).
178
water
is
and similar
results
When
the gas
We
solutions.
We shall see that practically all of the relations which
have been found to hold for dilute solutions fail to hold in concentrated solutions. That Henry's law should not apply to concentrated
solutions should, therefore, not be a matter of any surprise.
In dealing with solutions of
Solutions of Liquids in Liquids.
liquids in liquids we must distinguish sharply between two cases.
First, where the liquids are infinitely soluble in each other, or, as
we say, where they are miscible in all proportions, as alcohol and
water. This case suggests the solution of one gas in another. Here,
as we have seen, we always have infinite solubility,
gases mixing
with one another in all proportions. Second, where the liquids are
miscible to only a limited extent, as water and ether.
Here we
encounter a new condition, which we shall frequently meet with
hereafter in dealing with solutions, i.e. limited solubility. The properties of these two classes of liquid solutions, as we shall see, are
In addition to the above cases, there are liquids
quite different.
which are practically insoluble in one another hence, mixtures of
such liquids cannot be regarded in any true sense as solutions, since
the constituents can be readily separated mechanically. There is,
however, no liquid which^is absolutely insoluble in any other liquid,
;
is
The
is
evolved
in others
of such mixtures.
it is
Sometimes heat
when
absorbed.
No relation
has thus
evolved
when
there
is
con-
expansion in volume.
The properties of liquid mixtures, however, are often not widely
different from the sum of the properties of the constituents.
In
such cases, where the properties of the mixture are nearly " additive," they can be approximately calculated from those of the conthere
is
stituents.
If the volumes of the two liquids before they are
are VA and v2y the volume of the mixture v is approximately
Lieb.
Ann. Suppl.
5,
227 (1865).
mixed
SOLUTIONS
179
Take the
will suffice to illustrate this point.
of the
the
we
If
refract
to
of
weight
represent
light.
liquids
power
mixture by W, the index of refraction by N, and the density by
One other example
Landolt
w zL=l
D =Wl
^ ^ ^
d
+w
d2
+w
d3
..,
ture
is
d,
is p,
The percentage by
p:
spectrum, and found that the difference between the value calculated
for the mixture and that found experimentally was about one per
now
are
They
are, at best,
i.e.
The work
156, becomes liquid under boiling water, and when heated with
water in a closed tube a little above 100, this liquid mixes with
1
3
2 Ztschr.
Lieb. Ann. Suppl. 4, 1 (1865).
phys. Chem. 9, 349 (1892).
Journ. prakt. Chem. 133, 518 (1882); Bull Soc. Chim. 38, 145 (1882).
180
solutions
all
formed
that of
in B,
and that of
in
if
there
is
In
of the one constituent present than will' saturate the other.
the above case we have a solution of salicylic acid in water, and a
more
mix
20
10
30
10
60
70
80
90
100
110
120 130
140
TEMEERATUBE8
FIG. 14.
benzoic acid
(3),
temperatures
At the lower
aniline phenolate (4), and aniline (5).
in each case two distinct solutions represented
we have
of each curve.
The lower arm represents the solution
of the substance in water, there being relatively little substance and
much water present in this solution, as is shown by the small value
The upper arm represents the solution of water in the substance in question, the latter
being present in very large per cent, as shown by the large value of
of the ordinate of this branch of the curve.
the ordinate.
SOLUTIONS
181
become
identical,
proportions.
would mix
Vapor-pressure, Boiling-point, and Distillation of Liquid MixI. If the liquids do not mix to any appreciable extent, each
exerts its own vapor-pressure independent of the other liquids which
tures.
be present. The vapor-pressure is, then, the sum of the vaporpressures of the liquids which are brought in contact with one
This has been verified experimentally by Kegnault. 1
another.
few of his results are given in the following table
may
TEMPERATURE
182
relative vapor-pressures at the temperature of disto this simple rule have been discovered.
Some exceptions
tillation.
In these cases
boiling-point
would
it is
be.
boiling constituent.
When
distilled,
all
of the
The composition
lation
than
would be
the
higher
boiling.
solu-
more rapidly
T=8875
|
|3
results
in
curves.
The
T~8io
['
s
|>
f
'
T60?o
/
T^4io
dif-
SOLUTIONS
ferent temperatures.
The
183
of alcohol present.
a constant composition. When the excess of alcohol present becomes so large that all the remaining water present
can dissolve in it, the vapor-pressure again changes with the compoThe vapor-pressure
sition, as is shown by the fall in the curve.
and the
distillate
pure alcohol.
given
off
of the
most
The vapor
volatile constituent.
compo-
We
When
pure con-
184
Konowalow l
mix
The
in all proportions.
from his
results
The curves
for
methyl
the
amounts
of
alcohol
the
increase,
increases.
vapor-pressure
The curves show
no sign of any
minimum
maximum
or
of
vapor-pressure,
and since the tendency is for
the
lowest
Mixtures such as
greater.
methyl alcohol and water, and
ethyl alcohol and water, can
then be separated by fractional
All
distillation.
mixtures
less
completely by fractional
distillation.
Konowalow 2
ing-point.
also
propyl alcohol, and water and formic acid. His results are plotted
in the following curves
The curves for mixtures of water and propyl alcohol at different
:
Loc.
cit.
SOLUTIONS
185
If
we
several times,
finally,
T=55,0
not
FIG. 18.
water
or
having the
T=350
shall obtain
pure
maximum
vapor-
and, consequently,
the lowest boiling-point.
tension,
The curves
and by
tillation
we can
by
fractional dis-
Instead of obtain-
ing
186
taining 68 per cent of nitric acid in water has a constant boilingand many others are known.
point,
Eoscoe l has proved that these mixtures are not definite chemical compounds, by showing that the composition of the distillate
changed when the distillation was effected under different pressures.
Thus, when a mixture of hydrochloric acid and water was distilled
under a pressure of two atmospheres, the mixture which had a constant boiling-point contained 19 per cent of the acid, instead of 20.2
per cent as when the distillation was carried on under a pressure of
one atmosphere.
There is, then, not the slightest reason for regarding these mixtures with constant boiling-points as chemical compounds.
Solutions of Solids in Liquids.
Whenever a
This is perfectly general for, as we shall see, even metallic platinum dissolves
to a slight extent in water.
When we consider the number of solids
;
it is
number
of such solutions is
we have become
so accustomed to solutions
Indeed,
of this class, that when the term " solution " is used, we think first of
the solution of a solid in a liquid solvent. The most striking char-
almost
infinite.
weight of water at 18
dissolves
2.9
parts
of
strontium
per-
Lieb.
Ann.
Dissertation, Johns
SOLUTIONS
187
of the solid at a given temperature is known as the point of saturation, and such a solution is known as a saturated solution.
The
If it is desired to saturate a* solvent at a given temheated to a somewhat higher temperature and shaken
with the substance to be dissolved. The amount which is readily
dissolved at the higher temperature is more than sufficient to satuWhen the solution is
rate the solution at the lower temperature.
temperature.
it is
perature,
cooled
solution
some
tions
is
Just as we
may have
solutions
We
and the
have a
already in solution,
it is
a supersaturated solution.
Supersaturated
188
most readily by
water of crystallization.
form supersaturated
number
solutions.
When a saturated
should mention especially the calcium salts.
solution of a calcium salt, say of citric acid, is heated to a higher
temperature than that at which it was saturated, some of the salt in
solution is deposited as a precipitate. When the solution cools again
the precipitate redissolves. Similar results are obtained with salts
of other metals and other acids. The decrease in solubility with
rise in
Much work
as solvents,
OSMOTIC PRESSURE
Osmotic Pressure.
placed in a vessel, and over this solution the pure solvent is poured,
we shall find after a time that the substance is not all contained in
that part of the solvent in which it was originally present, but a
part of it has passed into the layer of the pure solvent which was
filled
SOLUTIONS
The water passed
bladder in water.
189
and the
alco-
the property of allowing the solvent to pass through them, but hold
These precipitates include copper
back the dissolved substance.
of
and
a
number
similar gelatinous substances.
ferrocyanide,
good method
now
that
we can
This
is
The top
its
lower sur-
The
tube
beneath the cork. The apparatus is then set in a quiet place for
some days. After a day or two, if the experiment is successful, the
liquid will begin to rise in the capillary, and may reach a height of
from 40 to 50 cm.
The experience
ments succeed.
Indeed, the number which give a good demonstrais only about one-third of the total attempts
The frequent
failure is doubtless
due in part
parchment used.
The method by which the semi-permeable membrane
1
p. 87 (1867).
is
formed
in
190
on either side by the material of the wall. The results of our experiments in this direction appear to have justified the expectation."
In order to remove the air contained in the walls of the cup they
made use " of the strong endosmose which appears when a current is
passed through a porous wall separating two portions of a dilute solution in which the two electrodes are immersed."
A dilute boiled
solution of potassium sulphate was used for this purpose. " On passing the current between the electrodes in the direction of the one
within the cup, the liquid in the cup rises with a rapidity which
increases with the dilution of the solution, and with the intensity of
the current.
formed by
filling the
26, 80 (1901).
SOLUTIONS
191
The current
means of the
membrane can be formed much more compactly
than by simply allowing them to pass into the wall by diffusion.
With such a cell it is possible to demonstrate osmotic pressure in a
current
that the
is
When
the cell
is
filled
with a normal
the capillary at the rate of more than a foot an hour, and in one day
a pressure of thirty feet of the sugar solution is easily secured. This
so far surpasses all other demonstrations of osmotic pressure thus
The
far devised, that they become insignificant by comparison.
demonstration of osmotic pressure on the lecture table by means
method has become as simple a matter as many of the daily
experiments in inorganic and organic chemistry.
This method promises much for the quantitative study of osmotic
The ease with which the cells can be prepared, arid the
pressure.
great resistance offered by the membranes formed by the electrical
of this
section.
tive
his
own words
1
4
:
first
the cup.
* Ibid.
J. S.
Ames.
Scientific
4-6.
Edited by Pro!
192
ing as follows
The
pears,
less at
all
other
places,
since the
"The
glass pieces v and t, inserted in position, are shown in median longitudinal section.
The porcelain cells
which
tube
FIG. 20.
same manner.
of this are
shown
in the
figure."
graph
SOLUTIONS
193
formed either in the wall or upon the surface, according to the prinIn order that this should be done successciple already indicated.
a
of
number
fully,
precautionary measures are necessary, and these
will now be discussed.
Since I experimented chiefly with membranes of copper ferrocyanide, which were deposited upon the inner
surface of porcelain cells, I will fix attention especially
"The
upon
this case.
first
was also filled with this solution. The interior of the porcelain cell
was then rinsed out once quickly with water, well dried as quickly
as possible by introducing strips of filter paper, and after the outside
had dried off somewhat, it was allowed to stand some time in the air
until
it
and
solution of potassium
had a
After
and
suitable fine-
grained porcelain cells are chosen, the preparation of good semi-permeable membranes offers no serious difficulty. Pfeffer states that he
Scientific
Memoirs
Edited by
Co.).
194
the
cell,
The whole
cell,
including
the
temperature coefficient of
osmotic pressure. The temperature of the experiment
was accurately determined
by means
of carefully stand-
ardized thermometers.
Some
of Pfeffer's Results.
different
FIG. 21.
concentrations.
13.5 to 14.7.
C = CONCENTRATION
IN
PER
SOLUTIONS
From
these results
it
195
p= a
G
is
propor.
constant, or
that
C=
CONCENTRATION IN PER
196
would seem
it
at first
would leak, and the true value of the maximum pressure was never
shown by the manometer. This conclusion was made very probable
by the behavior of these membranes during the experiments. Of
all the membranes tried by Pfeffer, only copper ferrocyanide was
capable of withstanding the pressure, and only those results which
were obtained with this membrane can be regarded as the true
expressions of the osmotic pressures of the solutions employed.
l
Further, Ostwald has devised an ingenious method for proving
theoretically that the osmotic pressure of a solution
of the nature of the membrane used in measuring
cylinder, Fig. 22.
is
independent
Given the
it.
first
in
pressure
until
the
reached.
l}
2,
pressure p2 is
Then the solvent
The
through
As soon
through MI.
.,
,.
as the
'
FIG. 22.
z,
Since
will continue to flow in through
v
the pressure could, then, never rise to p l} the solvent will continue to
would
flow in through
and to flow out through 2
1 forever,
the
We
Lehrb.
d.
Allg.
Chem.
I,
left.
p. 662.
the reverse of
SOLUTIONS
the
is
it
is
first direction.
impossible.
at
is,
substance
If
197
of course,
is such as
of Adie. 1
The
whom
to determine just
we
shall
now
deal
is
due.
He
found
and do not change their size or shape when the cell is immersed in solutions of other substances.
These walls are easily
permeable to water and aqueous solutions. The cell- walls are lined
on the inside with a very thin, colorless membrane, which is filled
with the colored contents of the cell. This membrane is
semi-permeresistant,
able, allowing water to pass, but holding back the dissolved substance.
The contents of the cell is an aqueous solution of glucose,
Chem. News,
Ztschr. phys.
Chem.
2,
198
able membrane lining the cell- wall distends when the contents of
the cell increases in volume, and contracts when the volume of the
contents diminishes.
The method
it is
placed will be
FIG. 23.
When
the cell
is
pressure as the contents of the cell, the cell has the normal appearance as shown in
When the cell is immersed
in the figure.
in a solution having a smaller osmotic pressure than its own con-
figure.
Water
The
cell contents,
having
in different plants.
SOLUTIONS
as
shown
in
also contract
199
cell contents,
By
starting with
rounded by the solution, and continually diluting it, noting its action
on the cell at every stage of dilution, a solution is finally reached in
which the cell will just preserve its normal form. The solution then
has the same osmotic pressure as the contents of the
cell.
The
solu-
Since each
these solutions analyzed and their strengths determined.
of these solutions has the same osmotic pressure as the contents of
This method has been called by De Vries the plasmolytic. He 1 determined the concentrations of quite a large number of substances
which were isosmotic with the cell contents. These isosmotic or
isotonic concentrations
The
of
De
SUBSTANCE
few
200
An
The salts
stant, and which have the value of approximately 2.
from
to
3
5.
have much higher coefficients
The
ranging
meaning
of these facts will appear in due time.
We have seen above how vegeMethod employing Animal Cells.
table cells can be used to measure relative osmotic pressures.
We
can use certain cells of animals for the same purpose. Hamburger *
has used the red blood corpuscles of the deer and frog. If to defibrinated deer's blood a solution of potassium nitrate, 1.04 per cent, is
added, the red blood corpuscles will settle completely to the bottom
and will be covered by a clear, almost colorless liquid. If the solution of potassium nitrate has a concentration of 0.96 per cent, or less,
the separation into the two layers is not complete. The corpuscles
do not settle to the bottom completely, and, consequently, the supernatant liquid is somewhat colored
the more deeply colored the
more dilute the solution of potassium nitrate added. By proceeding
carefully, a solution of potassium nitrate can be
red blood corpuscles will just settle and leave a clear liquid above
them. Such solutions have the same osmotic pressure; and from
these data
may
Bacillus
Zopfii,
rubrum,
subtilis,
Bacillus
Ztschr. phys.
W. Loeb
Hedin:
8
The movements
etc.
Chem.
6,
same substance of
319 (1890).
different concentra-
H. Koppe
and 1896).
S. G.
SOLUTIONS
201
strengths that they had the same influence on a given kind of bacand then their relative concentrations determined. The con-
teria,
We
more
the
the current rises or falls from the drop, to determine the relative
concentrations of the two solutions. In these observations a refrac-
tometer
used, slight currents being detected by the different ref racis, of course, possible to prepare the two solutions of such
concentrations that water will pass neither the one way nor the
tivities.
is
It
The two
other.
solutions
202
who
It
This method
is
obviously sub-
tions
doubtless
to,
and
saw
Ztschr.phys. Chem.
1,
481 (1887).
Scientific
Memoirs
SOLUTIONS
203
some of these
'
is
shown by the
fact that
experimental error.
p
C
is
Van't Hoff also points out that the work of De Yries leads to the
De Yries took solutions of potassium nitrate,
potassium sulphate, and cane sugar, and determined the concentra-
same conclusion.
tions
cell.
He
then used
sium
nitrate.
SERIES
204
the warmer portion of the tube to exert the same pressure as exists
In a word, the gas would tend to become
in the colder portion.
more concentrated in the colder portion, and more dilute in the
warmer portion
of the tube. 1
If the osmotic pressure of solutions obeys the laws of gas-pressphenomenon similar to the above should be observed with
ure, a
is
It should, of course,
somewhat
ideal.
The gas
it is
[5], 22,
293 (1881).
SOLUTIONS
205
must stand
for
months
Avogadro's
Law
The
0.08995 grams
weighs per
litre
206
TEMPERATURE
SOLUTIONS
207
tension,
and
We
have just seen that the three best known laws of gaspressure apply to the osmotic pressure of solutions of substances
We might conclude from this that the laws of gaslike cane sugar.
ure.
The osmotic
quite as numerous as those which conform to the rule.
pressure of most salts, of all the strong acids, and all the strong
bases, is much greater for all concentrations than would be expected
from the osmotic pressure of solutions of substances like cane sugar
same concentrations. The osmotic pressures of these three
classes of substances are always greater than would be expected from
for the
we have
This applies directly to the osmotic pressure of solutions of substances like cane sugar.
But in order that it may apply to solutions
of salts, acids, and bases, a coefficient must be introduced, which,
for these substances, is always greater than unity.
This coefficient
was called by Van't Hoff i, and it has come to be known as the Van't
Hoff
i.
to acids, bases,
and
salts
See Lovelace
208
nineteenth century.
It is always of interest to follow the line of thought which leads
any great discovery. The steps by which Van't Hoff was brought
in contact with the work of Pfeffer on osmotic pressure, and was led
to the study of dilute solutions from this standpoint, were developed
in full by Van't Hoff in a lecture before the German Chemical
Society in 1894, and which appeared in the Berichte, Vol. 27, 6. A
brief account of this lecture was given by the present writer in his
to
'
p. 77.
'
so, also, in a large number of cases, the osmotic pressure is abnormally large, and in the first case, as was afterwards shown, there is a
breaking down into hydrochloric acid and ammonia, so also with
solutions we would naturally conjecture that in such cases a similar
Yet it must be conceded that
decomposition had taken place.
anomalies of this kind existing in solutions are much more numer-
It may then
salts, the strong acids, and the strong bases. ...
have appeared daring to give Avogadro's law for solutions such a
prominent place, and I should not have done so had not Arrhenius
pointed out to me, by letter, the probability that salts and analogous
substances when in solution break down into ions."
the
Ztschr. phys.
Edited by
Chem.
1,
500 (1887).
Co.).
Scientific
Memoirs
SOLUTIONS
The
209
physicist Arrhenius, to
Work of Arrhenius.
shall
now
turn.
title
On
whose work we
the Dissocia-
'
We
will
now
it
is
well-known example. We regard these substances under such conditions as broken down into simple atoms..
" The same
expedient may, of course, be made use of to explain
the exceptions to Van't Hoff's law; but it has not been put forward
up to the present, probably on account of the newness of the subject
and the many exceptions known, and the vigorous objections which
would be raised from the chemical side to such an explanation."
Arrhenius then puts forward the assumption of the dissociation
of certain substances dissolved in water to explain the exceptions
number
of dissolved particles.
Ztschr. phys.
Scientific
210
and salts, represented by hydrochloric acid, potassium hydroxand potassium chloride, are the substances which show the ab-
bases,
ide,
it,
as
we
here that
The
water will
effect electrolysis.
weak
decompose a molecule of
Therefore, some of the molecules
to
SOLUTIONS
21V
experimentally.
them
cuss
The methods
chapters.
ions.
= H + Cl,
KOH = K + OH,
HC1
KC1
= K + CL
The
is
hydrogen
N0
It
the nature of
may
etc.
The
anioiis
be chlorine,
the group
is
It
may
and cations of
be
salts
salt.
They depend upon the nature
and the base which have combined to form the salt.
It was stated that hydrogen is the cation into which all acids
dissociate.
It may be added that this is the characteristic ion of all
acids, and whenever it is present we have acid properties.
Further,
we never have acid properties unless there are hydrogen ions present.
The same may be said of the hydroxyl ions into which bases dis-
of the acid
sociate.
This
is
of electrolytic dissociation,
and the objections which have been urged to it, will be presented as
the subject develops.
One misconception which has arisen so often
must, however, be anticipated in advance.
It has been repeatedly urged that the theory claims that a compound like potassium chloride dissociates into potassium and chlorine, and since neither potassium nor chlorine can remain in the
"Osmotic Pressure
of Concentrated Solutions,"
1 '
tion,
Ewan
31, 22 (1899).
Ztschr. phys.
Chem.
of Electrolytic Dissocia-
212
tube.
The
On
done
Tolman
to be
The
effect
increases
in the
Ann.
SOLUTIONS
213
rapidly with the length of the tube and the rate of rotation; and a
very powerful centrifugal machine is now being constructed for the
and also the undissociated molecules are probably denser than the
aqueous medium, all of these are thrown outwards by the centrifugal
force, so that the solution will increase in concentration at the outer
interior.
periphery.
much more
214
made
to separate in
See Bredig
Ztschr. phys.
Chem.
17,
459 (1895).
in length.
2
3
26,
80 (1901).
SOLUTIONS
215
first trial
may have
been, the cell is taken down, washed, and soaked for several hours in
It is then resubjected to the membrane-forming
distilled water.
process, again washed, and immediately thereafter it is filled and set
up with a view
However
membrane a number
It
of times."
details in connection
The measurements
cells,
with
the ther-
Column
is
II
full,
216
SOLUTIONS
OSMOTIC PRESSURE OF GLUCOSE
217
218
is to
which
on the
to bear
the solution.
apparatus
is
given.
FIG. 24.
24.
AB is
DD
matine rings
are compressed, when the two parts
and
of the outer gun-metal vessel are screwed together.
The ends of this
cage have shallow radial grooves cut out of them, so as to prevent
the dermatine rings from rotating and rubbing the membrane during
1 The
porcelain tubes are similar in
preliminary communication.
all
SOLUTIONS
219
"
The
The
joint between
good by another dermatine ring X, which is com
pressed between the metal ring / and the nuts JJ.
"The ends of AB are closed by pieces of thick- walled rubber
tubing KKj through which the brass tubes LL are passed a watertight joint between LL and the inside of the porcelain tube is
obtained by compressing the rubber between the metal washers
and the nuts NN. 1 The brass tubes are joined by rubber tubing, one
to a glass tap and the other to an open glass capillary
the latter,
which we shall call the water gauge, was graduated in millimeters
and calibrated; one centimeter of the bore contains 0.00312 cu.
and
have threads cut on them to
cm. The outer ends of
receive the brass rings 00, which in their turn are perforated by
E and F is made
MM
solution,
"The Semi-permeable Membranes. The membranes were deposon the surface of the porcelain tubes by the following means.
The porcelain tube is placed in a copper sulphate solution (50
grams in a litre) in a desiccator and the air exhausted, until no more
bubbles come off from ^he tube
this takes place only after several
the tube is withdrawn, wiped inside and outside with a clean
days
linen duster, and allowed to dry for J hour.
The ends are then
ited
It
seems advisable to point out that the rubber tubing JOTis unaffected by
upon the
solution.
220
it is set
up
for electrolysis.
The same
solutions
strength are used the tube is plugged at one end, and at the other
is fitted with a perforated plug and thistle funnel, through which a
;
down
CANE SUGAR
CONCENTRATION GRAMS IN A LlTBB
180.1
13.95
300.2
26.77
420.3
43.97
540.4
67.61
660.5
100.78
133.74
750.6
DEXTROSE
99.8
13.21
199.5
29.17
53.19
319.2
448.6
87.87
121.18
648.6
GALACTOSE
260
380
500
35.5
62.8
05.8
SOLUTIONS
100
110
125
Galactose.
150
120
75
125
250
Concentrations
in
500
Grams per
Litre of Solution.
150
30
221
222
279 (1894).
(1896)
(1902).
5,
141 (1897)
(1901).
Cohen
Vegard
Riidorff
Coppet.
It
nature
water.
is
The
best illustration
the sea.
which we have of
this
it
is
fact in
Here, as in so
many
is
proportional to the
come
to be
known
amount of
as the
Law
of
As a
is
first
attempt at a generali-
important.
116, 55 (1862).
who
SOLUTIONS
223
An
He
used molec-
number
not only acids, bases, and salts, but also a large number of organic
compounds.
By thus widely extending the field of cryoscopic
measurements he was able to point out a number of relations which
given,
and
ing, T,
= MA.
of this fact for determining the molecular weights of organic compounds soluble in water. I will now show that analogous results
is
solidified,
and
IV, 71.
8
Scientific Memoirs Series, IV, 71.
Ann. Chim. Phys. [5], 28, 137 (1883).
Edited by
Co.).
224
SUBSTANCE
SOLUTIONS
SOLUTIONS IN
SUBSTANCE
WATER
225
226
We
the coefficient
A gives 37.
we must adopt
gives 18.5.
weights of the dissolved substances determined in a number of solThe importance of the freezing-point method in determining
molecular weights will be taken up a little later reference is made
vents.
to
it
Raoult's
Law
it is
solvents, the
1
vents, taken from the paper by Raoult,
is
The
given below
SOLUTIONS
point of this liquid
is
227
'
If the
compound was
two
ions, the
barium chloride, the molecular lowering was nearly three times the
if the solutions were dilute.
These facts accord perfectly with the results of the measurements of osmotic pressure, and furnish strong evidence in favor of
the theory of electrolytic dissociation
an ion lowering the freezingpoint to the same extent as a molecule.
Arrhenius 2 saw the significance of these facts in connection with
his theory, and pointed out that we have here a method of testing
the theory. He used the freezing-point method to determine the
values of the coefficient i, which had been introduced by Van't Hoff
normal,
If a gram-molecular weight of a non-dissociated compound is dissolved in a litre of water, the lowering of the freezing-point of the
water
number
dissociation at once
came
Scientific
Memoirs
into prominence.
633 (1887).
Edited by
Co.).
228
and
of solutions,
Neither the
to this time, were necessarily not very refined.
apparatus employed nor the method used admitted of any very high
degree of accuracy. An important step
toward the improvement of both method
up
after a
is
to receive the
tube
by means of a
The
cork.
The
is stirred by
liquid in
means of a glass rod bent in a
circle of sufficient diameter to
to
pass
through.
The
FIG. 26.
JT IG<
27.
If the solvent freezes appreciably above the freezing-point of water, it is only necessary to
use water and ice. If we are working with water as the solvent, the
ing.
freezing-mixture more
be taken that not too
commonly used
m uch
is ice
and
salt.
Care must
SOLUTIONS
229
means
it is
By
of a degree.
The unique
feature of the
Beckmann thermometer
is
however
amount
of
the thermometer, and to so adjust the amount that the top of the column will come to rest at any desired point on the scale, when the
instrument
is
The
freezing-point of
any solvent or solution can, then, be adjusted at any desired position on the scale, and the difference between the freezing-points of
This differential thermometer
the solvent and solution determined.
of
try, and has contributed more to our knowledge, in the field which
we are now studying, than any other invention or device which has
ever been proposed. The Beckmann thermometer plays a role in
physical chemistry which may be compared with that of the potash
The method
of
working with
Beckmann apparatus
is
The two readings should not differ more than a very few
thousandths of a degree. When the water is being cooled down in
the vessel, it does not freeze as soon as it reaches the zero point,
but undercools, sometimes as much as two or three degrees, before
the ice begins to separate. Ice will then separate until heat enough
mined.
warm the remaining water up to the freezing temperaAfter the freezing-point of the water has been accurately determined on the thermometer,
and this must always be done just
is
liberated to
ture.
230
we then
The
prosolution
can be prepared in either of two ways. The water in the freezingvessel can be weighed and then a weighed amount of the substance
introduced or the solution can be prepared in a measuring flask,
;
using some of the same water whose freezing-point has just been determined. The method chosen for preparing the solution depends
upon the amount of substance available, the solubility of the substance, concentration of solution desired, etc.
must now be
de-
We
The
difference
is
up
warm
to its freezing-point.
evidently,
which
is
obviously equal to
its
heat of
no correction to be
introduced for the separation of the solid phase, since the remainder
of the liquid is unchanged.
In the case of a pure solvent there
fusion.
When
is
is
quite different.
The pure
Since
solid separates from a solution as from the solvent alone.
none of the dissolved substance separates, the solution becomes more
Since
concentrated, due to the freezing out of some of the solvent.
the solution whose freezing-point is determined is more concentrated
= /,
trated,
where / is the amount by which the solution will be concendue to the separation of
Determination
of
ice.
Molecular
Weights by
the
Freezing-point
Ztschr. phys.
Chem.
12,
624 (1893).
SOLUTIONS
231
unknown molecular
weight,
W the weight of
the solvent,
that of
M_
100
ATF
A word in reference to
When
a gram-molecular weight of a completely undissociated substance is dissolved in 1000 grams of water, the freezing-point of the
This value
is
known
232
Other common solvents which do not favor the formation of molecular complexes are formic and acetic acids, phenol, aniline, etc. ;
while, association frequently takes place in benzene, nitrobenzene,
ethylene bromide, and the like.
One
it
in
us, as we believe,
the molecular weight of the substance in solution, and in solution in
From such results conclusions
the particular solvent in question.
are often drawn as to the molecular weight of the pure, homogeneous
this connection.
The
substance.
Indeed, attempts have been made to show that certain
isomeric and polymeric substances have the same molecular weights,
because, when dissolved in some solvent, they show the same molecular weight.
do not know the
This is, of course, all entirely unjustified.
connection between the molecular weight of a substance in solution
We
and its molecular weight in the pure state, and until such a relation
has been discovered, we must always bear in mind that the freezingpoint method gives us only the molecular weight of the substance in
the presence of the solvent with which we are working.
Dissociation as measured by the Freezing-point Method.
The
second important application of the freezing-point method to physical chemical problems will now be taken up.
The lowering of the
freezing-point of water produced by electrolytes is always greater
than that produced by non-electrolytes of the same gram-molecular
concentration.
This is explained, as we have seen, by assuming
that a larger or smaller part of the molecules are dissociated into
ions, the number depending upon the concentration of the solution
To compounds which
point method is applied
are dissociated
SOLUTIONS
233
than two), the freezing-point lowering will be double that produced by an undissociated substance if into three ions, the lowering
will be three times as great; and so on.
The method of calculating
dissociation is obvious from the above statements.
If the molecular
less
lowering
is
cofficient
i.
The
dissociation
we
obtain the
is
obtained
-!.
down
into
f-1
*=^->
and the same principle holds for electrolytes which yield a larger
of ions.
It is thus possible to determine the amount of the
number
dissociation of
normal.
The method devised by Beckmann for molecular weight determinawork of this kind. We shall examine some
of the more refined methods for determining freezing-points.
A method
More Accurate Methods of measuring Freezing-points.
which was apparently an improvement on that of Beckmann was
devised in 1892 by Jones. 1 This work was undertaken at the sugAt this
gestion of Ostwald, in whose laboratory it was carried out.
time there were two general methods of measuring dissociation,
tions is far too crude for
which
was
iZtschr. phys. Chem. 11, 110, 529 (1893); 12, 639 (1893).
234
and
from
when
0.1 to 0.001
this
salts, in
normal
factorily.
little
below that
work was done. His last work was thus a beautiful investigation
along the same lines which brought him into prominence many years
This investigation will stand as a crowning glory to a
devoted with unusual zeal to the cause of pure science.
ago.
life
SOLUTIONS
235
by the
freezing-point method.
Jones and Knight, 2 in their work on double chlorides and bromides, found that the molecular lowering increased with the concentration from a certain point, and then increased again from this
point with the dilution, as would be expected. The increase in the
molecular lowering became very marked at great concentrations;
indeed, so pronounced that the molecular lowering of a normal solution
was
ing
when
as great as, or greater than, the theoretical molecular lowerall the salt was completely dissociated.
careful study.
time systematically, and determined the freezing-point lowerings produced by a number of chlorides and bromides.
They found
that the phenomena described above were probably general, holding
for nearly all of the salts with which they worked.
first
The
investigation
2 Ibid.
Amer. Chem. Journ. 22, 5 (1899).
22, 110 (1899).
See Abegg: Ztschr. phys. Chem. 15, 209 (1894).
Ponsot Compt. rend. 118, 977 (1894).
i
Ponsot
13, 67 (1894).
(1894).
Abegg
Loomis:
Kaoult
Abegg
Loomis
Whetham:
Loomis
Osaka
Walker and Robertson Proc. Eoy'. Soc. Edinb. 24, 363 (1903).
Jahn Ztschr. phys. Chem. 50, 129 (1905).
8 Amer.
Chem. Journ. 23, 89 (1900).
* Ztschr.
phys. Chem. 46, 244 (1903).
Phys. Bev. 18, 146 (1904).
:
236
is
the concentration,
the molecu-
lar lowering.
CALCIUM CHLORIDE
FREEZING-POINT MEASUREMENTS
MAGNESIUM BROMIDE
FREEZING-POINT MEASUREMENTS
SOLUTIONS
CHROMIUM NITRATE
FREEZING-POINT MEASUREMENTS
237
238
Concentration.
FIG. 28.
removing
is
it
from the
molecule of
lowering
of one
concerned.
water,
SOLUTIONS
239
is
cr N0 3 )
Fe(N(
13
*
N03)3 8H E
Mg(N
3)2-6
^/
HZ
C,a(NO
CO(N
**
4
KK0
NH4 N
3' |
NOa
Z
Concentration
FIG. 29.
Ten
240
six, eight,
by those
and nine molecules of
water of crystallization.
Similar relations manifest themselves
The
water can
literature contains
fact.
Another
146 (1904).
SOLUTIONS
241
the hydrates are less stable in solution, and are still less stable when
know of a large number
out of the presence of an excess of water.
We
amount
of water at
and
Spectroscopic Evidence.
FIG. 30.
The evidence in question is based upon the view that the phenomenon of absorption as presented by solutions is one of resonance.
The energy
greatest extent
its
own.
The period
of vibration of a dissolved
it
of
water molecules
The
particle, the
37,
000 (1907)
Monograph No.
60.
37,
242
solutions in which the hydrates were the most complex would have the
narrowest absorption bands.
This conclusion can be very easily tested experimentally. The
work of Jones and his assistants has shown that the more dilute the
The more
that this
is true.
FIG. 31.
is
the scale.
SOLUTIONS
243
The absorption
FIG.
32.
244
FIG. 34.
The
amount
of water is ad-
FIG. 35.
is
SOLUTIONS
245
chloride in ethyl alcohol (Fig. 36). The strip next to the numbered
scale represents the solution with the
largest amount of water, while
FIG. 36.
is
corresponds to
neodymium
FIG. 37.
1
The
chloride in methyl
246
The evidence for the existence of hydrates, from the study of the
absorption spectra, is thus entirely satisfactory. Another line of
evidence bearing upon the present hydrate conception will be considered when we come to study the temperature coefficients of conductivity.
Approximate Composition
stances.
The evidence
of the
The conductivity
its
dissociation.
The symbols
m is
lar
33,
27, 433 (1902)
31, 303 (1904)
82, 308 (1904)
(1905); 34, 291 (1905); Ztschr. phys. Chem. 46, 244 (1903); 49, 385
(1904) ; 52, 231 (1905) Carnegie Institution of Washington Monograph No. 60.
;
684
SOLUTIONS
solvent
wi
247
the
CaCl 2 HYDRATES
248
AlCLj
in
HYDRATES
SOLUTIONS
How
249
Mendele'eff
is
not in itself a
new
acid of
H S0
2
H S0
-H 2 0;
-2H 20;
H S0
2
-25H2 0, and
H S0
2
H 0.
100
Mendele'eff's conclusion
acid
by sulphuric
acetic acid.
Ber.
d.
2 Ztschr.
See Badenrecht
8
Ztschr. phys.
Chem.
16, 1
(1894).
250
There is combination
freezing-point lowerings were explained.
between the dissolved substance and a part of the solvent, removing
this part of the solvent from the field of action as far as rise in
boiling-point is concerned.
It thus seems that the power of dissolved substances to combine with
more or less of the solvent is general. The amount of the solvent held
in combination depends upon the nature of the substance
the
larger the amount of the solvent combined as solvent of crystallization, the larger in general is the
the substance
when
The amount
amount held
in combination
by
in solution.
solution the
which, as
we
shall learn, is
in keeping with the law of mass action which controls this phenomenon. The law of mass action has been applied to the problem of
1
hydration by Jones and Stine, and in the following manner. The
effect of one salt on the hydration of another salt was studied pretty
thoroughly. The salts were chosen to fulfil the following con-
through
SOLUTIONS
251
1
by Tammann. The value of the constant for mercury, as calculated
which will soon be discussed, was found to be 425.
method
a
by
Tammann worked with solutions of potassium, sodium, thallium,
zinc, and bismuth, in mercury, and determined the molecular weights
of the dissolved metals. The molecular weights calculated from
252
If
we
perature will remain unchanged until the whole has solidified. The
temperature will also remain unchanged until the whole is melted
again.
*
Guthrie
He
there
is
stances.
A very
theoretically.
Vries, as we have seen, measured the relative osmotic pressures of solutions of different substances, and determined the concen-
De
trations
Mag.
1,
49,
and
Bruni
I,
637 (1897).
2,
211 (1876).
SOLUTIONS
number
253
SUBSTANCE
254
to
make
little
clearer.
The
solution with
which we
of substances dissolved in
n gram-molecules
The
specific lowering,
however,
is
= A-
M =^'
Therefore,
But n =
JL
and substituting p = n
in the
last equation, it
= CMn,
A = Cn.
J^A
becomes
or,
The
/$
(1)
i.e.
we allow
as
as
much
would contain
N molecules.
n
ent
is X,
X.
which has separated is fused by warming to the temperature T, and the liquid allowed to mix with the solution by
passing through a semi-permeable membrane. An osmotic pressure
If the volume of the solution
will be exerted, which we will call p.
is v, the work done is pv.
The
ice
is
X,
we have
pv:\=&:
Tz,
n
the
This
is
amount
T the
added
initial
*Q' = ^
amount
of heat lost
where
is
by the body,
SOLUTIONS
255
pvn __ A
~N\~~~T
or,
Since
pv
JRT,
Substituting JT
and
R=
100
=
2 calories,
where
is
we have
solvent,
nM'
A=
From
(2)
100
(2),
O=
j^f
2T2
100
A.
we
we
have
c=~ 2T
100Z,'
The
From
this
the
compared the
256
A normal
by multiplying by
is
22
4-
r^~
=Ax
*)*)
^
A.
.
1 .86
The freezing-point method has, indeed, three distinct applicaThe determination of the molecular weights of non-electro-
tions
we now
pass to another
property of solutions.
DIS-
Work.
definite temperature at
We
freezing-point.
vapor-tension.
SOLUTIONS
this field
was Wiillner. 1
He
257
evidently analogous to the law of Blagden for freezing-point lowering, and, as we shall see, like the latter is only an approximation
which holds
in certain cases.
About a quarter
He also pointed
had been early pointed out by Von Babo, that the relation between
the vapor-pressure of the solution and the solvent is independent of
the temperature, at least from 20 to 95.
passing through the solution, took up an amount of water corresponding to the vapor-pressure of the solution. The second tube
containing the solution lost but little water, and, therefore, this
solution underwent no appreciable change in concentration.
The
from the solution into the pure water, and here took up
more water, since the vapor-tension of the solvent was greater than
air passed
The
air,
now
the experiment, was then passed over the sulphuric acid, to which it
gave up practically all the water which it had taken both from the
solution and the solvent.
Walker
states
258
Em den.
by
ether.
He
the
effect
Ann. Chim. Phys. [6], 15, 375 (1888). Ztschr. phys. Chem.
Memoirs Series, IV English by H. C. Jones.
Scientific
2,
353 (1888).
SOLUTIONS
259
IN 100
GRAMS OF ETHER
260
and
number
of molecules
f
,
where
N represents
solution.
ETHER
the
of the
SOLUTIONS
SOLVENT
261
262
constant.
Since
/-/_ n
/ ~N+n
If
we
= -^
Making
M, and
we have
M+w
M=
wf
7f-
measurement
SOLUTIONS
263
as
carried out
by Beckmann consists
in
determin-
shown
tube
The
in Fig. 38.
is
glass
boiling-point is to be determined.
Into this liquid the thermometer
dips, as
shown
In
in the figure.
denser
as
is
shown
tube
is
the figure.
This
surrounded by a doublein
whose boiling-point
be determined in A.
is
to
This
is
FIG. 38.
The
liquid in
is
boiled
609 (1897). Meyerhoffer Ibid. 22, 619 (1897). Bigelow Amer. Chem. Journ.
22, 280 (1899).
McCoy: Ibid. 23, 355 (1900). Batteli and Stefanini: Ann.
Chim. Phys. (7) 20, 64 (1900). Riiber: Ber. d. chem. Gesell. 34, 1060 (1901).
Beckmann: Ztschr. phys. Chem. 39, 129,385 (1902); 40, 129 (1902). Beck:
mann:
Leipzig (1906).
264
modifications
Carrying out a Molecular Weight Determination with the BeckThe pure solvent is poured into the tube A, the
Apparatus.
filling-material (beads or garnets) introduced, and the thermometer
inserted so that when the cork is forced into the top of tube
the
bulb of the thermometer is entirely covered by the liquid, but does
not touch the glass beads.
The mercury in the Beckmann ther-
mann
filling-material a
thermometer
is
is
poured
The
in.
Some
of the
pure solvent is poured into the vapor-jacket, and boiled simultaneously with that in the tube A. The position of the mercury is
carefully noted on the thermometer, after the solvent has boiled
about twenty minutes, and the barometer
is
is
is
Ztschr. phys.
661 (1895)
21,
Chem.
15,
656 (1894)
18,
492 (1895)
18,
245 (1896).
Determining
Molecular
Freezing-point, Boiling-
SOLUTIONS
265
If we represent
the weight of the substance
used by w, the weight of the solvent by TF, and the rise in the
boiling-point of the solvent by R, we have
cules of the solvent
the
CWQw
RW
The value
is
Molecular weights, as determined by the boiling-point method, usually are the simplest possible, though there are many exceptions to
this generalization.
number
of
Beckmann.
of modifications of the
might not come in contact with the thermometer before it had been
He also, by means of a glass cap into which notches had
reheated.
been filed, caused the steam to rise in very fine bubbles through the
He thought that
liquid just around the bulb of the thermometer.
in this way he could secure a better stirring of the liquid just around
the thermometer. The apparatus of Hite is undoubtedly an improvement on any which had been proposed up to that time. In. an
2
attempt to improve the Hite apparatus, Jones devised and used
form
the following
Into the glass tube A, some glass
(Fig. 39).
beads or garnets are introduced. To the side tube A, the condenser
Into the beads a cylinder of platinum
is attached.
is inserted by
placing the finger upon the top of the cylinder and gently shaking
the whole apparatus. The liquid whose boiling-point is to be deteruntil the bulb of the thermometer, placed
mined is introduced into
shown in the
as
figure, is
covered.
The
l
essential difference
266
is
is
der
is
to the boiling-point.
mum.
mometer
is surrounded only by
the boiling liquid, or even if a
layer of asbestos is wrapped
boiling
liquid
in
which
it
is
is
reduced
minimum.
The apparatus is exceedingly
simple, and when applied to
to a
was found
considered a
FIG. 39.
little later.
is
based upon a
See Johnston
SOLUTIONS
somewhat
267
of heating the
liquid.
The
solvent or solution
boiling-point
is
method
heated to the
solvent.
The apshown in Fig. 40.
The vapor is led
solution.
surrounded
is
by a larger tube E,
which is connected
with a condenser C.
from
the
through
hole
there
JET,
and
conse-
is
quently a layer of
vapor between
and E. The lower
end of
contains
a number of perforations
which
escapes.
through
vapor
The bulb
the
prevents
the
The pure
vent
sol-
poured into
until the bulb
of the thermometer
is
N
is
just
The
in
covered.
pure solvent
FIG. 40.
F is boiled after
known amount
of dissolved substance in a
given volume is added. The boiling-point of the solution is determined in the same manner as that of the solvent. The solution is
continually changing concentration due to the condensation of vapor
1
268
is deter-
mined, the inner tube, with thermometer and delivery tube, are
weighed. Knowing the weight of this part of the apparatus empty,
and the weight of the substance, we know the weight of the solvent.
If a number of Determinations are desired, using the same quantity
of substance, the passage of the vapor is interrupted from time to
time, the boiling temperature read, and the amount of solvent present
determined. In such cases the volume of the solvent is read off, the
tube
being graduated for this purpose. In reading the volume
the thermometer and delivery tube are removed in each case- from
the solution. The object of heating the solution by means of its own
nitrate.
The
one another to within a per cent or two, and made it very probable
that electrolytic dissociation could be measured by this boiling-point
method to within a very few per cent.
Hoff).
SOLUTIONS
of the
269
is
given in the following table. The results with the alcohols are taken
from the measurements of Jones, using the boiling-point method.
SUBSTANCE
270
tainly suggestive.
Relation between Lowering of Vapor-tension and Osmotic PresDe Vries 2 has shown experimentally that a proportionality
sure.
exists
SUBSTANOB
SOLUTIONS
271
The
when
of the
f'=f-hd.
The Value of d.
Let v be the volume of a gram-molecule of the
vapor of the solvent D, and / the pressure of this vapor
:
=
f'
If
is
v'
M
~d~'
RT
Mf
f'
in
which
PV=BTxn,
P is the osmotic pressure of the solution, and V its volume.
1
Ztschr.phys. Chem.
3,
115 (1889).
272
Let
practically the
dilute solutions)
Substituting,
h- nRT
9
Substituting the values h
and d
= -^=,
f'=fhd, we
iJ-
have
Mf
nMf
f-f' = nM
T
which
is
verified
amply
/-/ =
where
dent that
is
the
number
by experiment,
is
^=^:when the
usually
It is evi-
identical.
Relation between Rise in Boiling-point and Lowering of FreezingEaoult has shown experimentally that the lowerings of
point.
the freezing-point produced by some eighteen salts stand in the same
relation to one another as the rise in boiling-point produced by these
The same relation has been repeatedly estabsame substances.
by the fact
two
that the formula which
is
is
freezing-point constant of a solvent can also be employed to calcuThe formula deduced (p. 255) for the
late the boiling-point constant.
2 T
C= 100
Lt
2
freezing-point constant,
SOLUTIONS
if
we represent by
T the
273
L the
and by
given below
Acetone
Ether
.17.1
....
Ethyl alcohol
21.6
11.7
Aniline
Benzene
Chloroform
32.0
26.1
Methyl alcohol
Carbon bisulphide
35.9
Water
25.3
Acetic acid
The
8.4
.23.5
5.1
and
relations
rise in boiling-point
these properties.
These three properties of solutions are
DIFFUSION
What
is
Diffusion?
When
become homogeneous.
two solutions are of the same substance, the dissolved submore concentrated to the more
If the two soludilute solution, until homogeneity is established.
If the
homogeneous.
This phenomenon
is
known
as diffusion.
importance of this property cf
274
ard solutions could not be preserved for any appreciable time. Since
diffusion exists we can preserve a homogeneous solution for any
length of time, provided only that we keep all parts at the same temThe importance of this property is at once evident; we
perature.
shall now study it quantitatively.
The first experiments of any considerExperiments of Graham.
able importance on diffusion were those of Graham. 1 He did away
with the use of any separating membrane, and used simply widemouthed vessels into which the solution was introduced. The vessel
was then completely covered with water, allowed to stand, and the
amount of substance which passed out by diffusion determined after
a time. He found that the rates at which different substances diffuse varied greatly with the nature of the substance. Acids in general diffused more rapidly than salts, and the different salts varied
his law is probably the most important which has ever been discovered in connection with this phenomenon. Tick stated his law
thus 2 " The amount of salt which diffuses through a given cross-section
is proportional to the difference in concentration of two cross-sections
and
Lie*.
1851, 483.
Ann.
77, 56,
Wied. Ann.
7,
469,
SOLUTIONS
275
viously used. This method was based upon a principle which will
brief description
be considered in detail under electrochemistry.
If two plates of the same
of the principle must suffice in this place.
dif-
A cylindrical
plate of zinc.
zinc salt.
this
E = Ae
is
is
long
is
the time
_El kt
H2
of the experiment,
7T*
If the
law of Pick
is
Jc is
a constant,
n3
DATS
^2*
4- 6
6- 6
6- 7
0.2032
0.2066
0.2046
7- 8
8- 9
9-10
0.2027
10-11
0.2049
0.2027
0.2049
276
tested
by a number of
Scheffer
different experi-
SOLUTIONS
277
Tnra
278
We
by keeping the
different parts
-^
diffusion.
osmotic pressure
conditions.
there
move
is
is
Equilibrium
comparatively
freely.
The
little
friction in solutions is
through space. Inner friction is, then, the chief cause for the long
time required for diffusion to establish equilibrium.
much
SOLUTIONS
279
"
Given, for the sake of simplicity, a diffusion cylinder of constant cross-section, and let us assume that the concentration in every
If there is an osmotic pressure p at the
cross-section is the same.
place #, in the layer qdx there exists a pressure on the substance in
If c is the concentration, i.e. the number of
solution of
qdp.
gram-molecules of the substance in question contained in a cubic
centimetre, the force which at the place
molecule
is
--rqdxc
= ---f-c
If
dx
we
designate by
must
move
it
with
~ qzdp
the amount of substance in gram-molecules which wanders through
the cross-section q in time z, if two layers about one centimetre apart
show a
dissolved substance does not polymerize with increasing concentration, the osmotic pressure is proportional to the concentration, i.e.
p =jp c,
where pQ
is
we
obtain
Since, however, in such great dilutions that the friction of the molecules of the dissolved substance against the molecules of the solvent
is
at once derivable
from the
a concentration
c (at
*!
where
k' is
solvent.
-f-
dx this
is c
+ dc) is,
<2>
280
Prom
(1)
and
we have
(2)
X 10 4 seconds
in a day).
obtained from the volume occupied by a grammolecular weight of a gas at 0, and one atmosphere of pressure, i.e.
the volume occupied by 2 grams of hydrogen or 32 grams of oxygen
The pressure pQ
is
22,350 (l
Since an atmosphere
is
1.033 (1
23,080 (1
Substituting this value of
+ 0.0367 t)
+ 0.0367
pQ
kgt)
cnv
and solving
K, we have
7T=-i 1.99 x 10 9
To
is
Po = 22,350
for
+ at)=p
(1
+ 0.0367
necessary to
know
kg.
ing substances
SOLUTIONS
From
the calculations of k
number
of substances.
281
basis of
K for a
282
1.
The
latter
colloids.
These two classes of substances can, in general, be easily separated from one another.
and
ham
dialysis,
effecting
such separations a
dialyzer.
Colloidal Solutions.
etc.
show osmotic
Colloidal Suspensions.
A large number of apparent solutions that
resemble true solutions even less closely than colloidal solutions do,
are
known
as colloidal suspensions.
SOLUTIONS
these
283
suspensions
Colloidal suspensions of a
sus-
suspensions
not only of the neutral, amorphous, organic
substances, but of the
metals themselves.
number of years ago Carey Lea 1 showed how
method
The
will be described
Fig.
.,,.
_.
FIG. 42.
it is filtered
In-
light.
Bredig and Von Berneck found that this liquid has quite remarkIt decomposes hydrogen dioxide lik
organic ferments, and resembles the latter in many other particulars. A gram
atomic weight of platinum in 70,000,0000 1. of water decomposes
hydrogen dioxide appreciably, thus resembling organic ferments
able properties.
Amer. Journ. Science, 37, 476 (1889) 38, 47, 129, 237 (1889).
Ztschr. phys. Chem. 31, 258 (1899).
8
Ztschr. f. angew. Chem. 1898, 951.
Ztschr. Elektrochem. 4, 514 (1897).
Zsigmondy: Ztschr. phys. Chem. 33, 63 (1900).
;
284
where a very small quantity can effect a large amount of decomAn even more striking analogy between the action of
position.
the colloidal platinum and organic ferments is to be found in the
A very small amount
effect of certain poisons upon both of them.
of certain substances will entirely destroy the activity of organic
ferments. Exactly the same was found to be the case with the col-
which
it
yields
and
its theoretical
significance, is
the following:
Two
chemical compounds which react in the presence of an electrolyte and give a- precipitate, will nearly always give a colloidal suspension if no electrolyte is present. Thus, hydrogen sulphide reacts
with arsenious chloride and forms a precipitate of arsenious sul-
When
hydrochloric acid being formed in the reaction.
of
arsenic
into
a
solution
is
trioxide,
passed
hydrogen sulphide
arsenious sulphide is formed, but is not precipitated. It remains
phide,
It should be
in the water in the form of a colloidal suspension.
noted that in this reaction no strongly dissociated electrolyte is
Water is formed as one of the products of the reaction,
present.
Such
particles can be
removed by
11,
145 (1907).
filtration
SOLUTIONS
285
and of metallic
gold.
has not yet been definitely settled whether these colloidal suspensions manifest any of the properties of true solutions, even to a
It is somewhat doubtful whether they even show
slight degree.
It
moves with the current towards the cathode, while colloidal arsenious
sulphide moves against the current towards the anode. The ferric
hydroxide is, therefore, charged positively, and the arsenious sulphide negatively. The above property seems to be a general one for
colloidal suspensions; the hydroxides of the metals moving towards
the cathode, while other colloidal suspensions, including the metal
l
Further, it has been shown by Hardy that egg-albumen migrates
towards the anode in an alkaline solution, but towards the cathode
in an acid solution.
Two
silicic
Egg-albumen can combine with both acids and bases, and form
In the presence of an acid it would yield the anion of the
In the
acid, and the colloidal residue would be charged positively.
presence of a base it would yield the cation of the base, and the
salts.
Ztschr. phys.
Chem.
Beckhold: Ibid.
286
This
theory
seems
to
account
fairly
satisfactorily
for
the
facts.
It is highly probable
the ion or charged
that all precipitation takes place around ions
particle serving as the nucleus around which the coagulation takes
place.
precipitated,
we have ions present. It is obvious that this is a fact of the profoundboth for qualitative and quantitative analysis.
The suspension of the colloidal particles is probably closely
associated with the electrical charges which they carry. When two
colloidal suspensions having the same kind of charge are mixed, no
However, when two such suspensions having
precipitation results.
opposite electrical charges are mixed, there is a coagulation of both
colloids and by using suitable quantities, both colloids can be comThus, when arsenious sulphide and ferric
pletely coagulated.
hydroxide, both in the state of colloidal suspension, are mixed,
coagulation results and both are precipitated.
est significance
When
more than
The
action
This diminis
nothing to
SOLUTIONS
draw the
287
and produce a
precipitation.
When
less
and
less.
As
this difference
becomes
less,
Experimental work, carried out in the laboratory of J. J. Thomson, and which it would lead us too far to discuss in detail, confirms
the above explanation.
COLOR OF SOLUTIONS
If we are dealing with
Color of Solutions of Non-electrolytes.
i.e. substances which exist in solution entirely as
non-electrolytes,
The
Our knowledge
Properties
Zacharias: Ztschr. phys. Chem. 39, 468 (1902).
Winssinger: Bull. Acad. Belg. (3) 15, Nr. 2 (1888).
Van Bemmelen
Krafft
Barus
Krafft
d.
(1901).
Miiller
Duclaux
288
in this field is not yet sufficient to enable us to deal with this problem satisfactorily yet it is quite certain that the color of molecules
is due primarily to the nature of the chemical atoms which enter
That constitution also has an influence is made
into the molecules.
clear by many facts which are known.
The problem, however, which is of special interest here, deals
not with the color of molecules but with the color of ions i.e. with
;
the electrolyte
and
to
these
Some
the cobalt ion, since such solutions are completely dissociated and
Here the facts confirm the
the anion in each case is colorless.
have
All
such
salts
exactly the same color in dilute
theory.
solutions.
Ostwald. 1
to say that they should all have the same absorption bands.
These bands were both carefully measured and photographed by
Ostwald. These salts show five absorption bands in the yellow and
green, and four of these were measured for thirteen salts of permanthe
ganic acid. The results of Ostwald's measurements are given in
is
following table
Ztschr. phys.
Chem.
9,
579 (1892).
SOLUTIONS
PERMANGANATES.
ABSORPTION BANDS
289
290
p-rosaniline
and aniline
given below.
yellow-green.
Levulinic acid
L.
SOLUTIONS
291
carry,
FIG. 44.
a complex ion, the color of the complex may have no simple relation
The cobalt ion
to that of the element when present alone as an ion.
is red.
When
is colorless.
K Co(CN)
3
dissociates into
Fox
Dissertation,
Jena (1906).
it
292
of this
is colorless.
compound
We have just
may be
color.
which
it
molecule
dissociates, or it
colorless molecule
colored
is
which
less ions.
Upon
these facts
An
is
indicator is a
analysis.
color when the solution passes from the acid to the basic condition,
and vice versa.
indicator is always either a weak acid or a weak
An
all.
anion
and
it is
this latter
this indicator.
In using this indicator, a small quantity is brought into the presence of the acid, which is to be titrated against a strong base. The
indicator, in the presence of pure water, is almost completely undisIn the presence of the strong acid which contains many
sociated.
free
hydrogen
ions, it
less
than in pure
the acid
yzed,
i.e.
is
SOLUTIONS
293
before enough base had been added to completely neutralize the acid.
The result would be the appearance of a faint color on the addition
of a little alkali, and this color would increase in intensity as more
alkali was added.
There would, then, be no sharp change
in color when all the acid had been neutralized, and the indicator
and more
known
It is well
theory.
weak acids or
weak
bases.
an indicator
is
phenolphthalem as such, or to a transformation product of this substance, is interesting and important, but is subordinate to the fundamental question as to the general principle involved in the action of
indicators.
294
If an alkali is added,
colored.
formed, and this dissociates into
the metallic cation and into the anion C 6 4 (N0 2)0, which is deep
yellow in color. The action of this substance as an indicator will
weak
is
slightly
acid
is
It
is,
however, sufficiently
dis-
the solution.
If a strong acid is added to an aqueous solution of para-nitrophenol, the dissociation of the latter is driven back, due to the addi-
tion of the
common hydrogen
ion,
colorless.
is
colored, but
deep blue. Litmus, like phenolphthale'in, cannot be used satisfacwith weak bases. These would form salts with the litmus,
which would be hydrolyzed and prevent a sharp color reaction or
their salts, with any but the strongest acids, would undergo some
hydrolysis and prevent a sharp appearance of color. In order that
torily
of a base the
anion.
salfc is
are titrated with strong acids. In these cases there is but slight
hydrolysis of the salts formed, and also but slight hydrolysis of the
salt
formed by the methyl orange and the weak base, since the
cator
indi-
is
it
SOLUTIONS
weak
must always be
acids
titrated
295
be employed.
Weak bases, on the other hand, must be titrated with strong
acids, and a strongly acid indicator must be employed.
As an example of
Basic indicators are but little used in practice.
acid indicator
this class
may
we may take
This
cyanine.
is
The molecules
but
little dissociated.
base,
suffice to illustrate
the different
is
There is thus a
between potassium or sodium hydroxide, and
marked
difference
ammonium
It
hydroxide.
would be
difficult to interpret
little
several cubic
or no dissociation of the
ammonium
The addition
hydroxide
is effected.
64v
<
The complex anion
1
Bottger
NH
and
OH
/C 6H 4
/>C<>C, H OH
}6
Ztschr. phys.
Chem.
18,
377 (1896).
Salm
296
different
first
The addition
The
It remains
corresponding solutions of
ammonium
hydroxide.
Indeed, a solution
with phenolphthalein.
All of these points were tested experimentally by the conductivity method, with the result that the theory of electrolytic disso-
solution of
the aqueous
appear where
then gradually added to the cylinder, when the red color will appear,
at first faint, then stronger, as the amount of water increases. When
the red color has become intense, add a considerable volume of
alcohol, and the entire color will 'disappear, leaving the solution
slightly yellow again.
Fluorescence and Dissociation.
of water,
is
only
water a
once.
shown by
little
This
is
alkali is added,
SOLUTIONS
theory.
Fluoresce'in is a
weak
297
and very slightly dissociated by it. Being an acid, it would dissociate into a hydrogen cation and a complex organic anion.
The hydrogen cation is evidently not fluorescent, since all acids
yield hydrogen cations as one of the products of dissociation, and
solutions of acids in general are not fluorescent.
The fluorescence of
be
due
to
the
must, then,
complex organic anion formed
fluoresce'in
It is
conditions there
is
The
it is
phenomenon observed
here,
and
phenomena observed with indicators, were due to the formation of alkali salts, and that these persisted as such in the solutions,
also the
we
way
in the light of
We
now know
that
termed amphoteric
electrolytes.
following schemes
1
Bredig
298
E0 + H;
EOH = E, +
OH.
We have here,
electrolyte.
we
exist only in the molecular condition, and it is obvious that all of the
properties are the properties of the dissolved molecules plus those of
the solvent.
See R. Meyer Ztschr. phys. Chem. 24, 468 (1897). Bredig and Winkelblech :
Ztschr. Electrochem. 6, 33 (1899).
Hantzsch Ber. d. chem. Gesell. 37, 1076
Hantzsch: Ibid. 56,
(1904). Luiide'n: Ztschr. phys. Chem., 54,532 (1906).
67 (1906).
Walker Ibid. 56, 575 (1906). Johnston Ibid. 57, 557 (1907).
:
Camming
Walker
Ber.
Ibid. p. 409.
4 Zeit.
6
d.
chem Gesell
p. 389.
SOLUTIONS
299
The
sum
the
We
are additive.
we
shall see in a
moment how it
Meanwhile, a word
The
Chemical Properties of Completely Dissociated Solutions.
chemical properties of solutions which contain only ions must be
Some surprising facts,
the chemical properties of the ions present.
the
when
we
chemical
come
out
however,
properties of ions.
study
An
properties.
Chlorine
silver.
CH
C 2 5 C1, etc.,
3 C1,
Further, chlorine in compounds like
not precipitated by silver nitrate, because these compounds are
not dissociated by water, and the chlorine is, therefore, not in the
nitrate.
is
ionic condition.
Again, chlorine
precipitated
by
may
silver nitrate, if it is in
forms part of an
The
chlorine
is
ion.
illustrate the
S0 4
same
is its
point.
The most
char-
300
++
S0 4
is in combination
with a complex group, it may not precipitate barium sulphate at all.
Thus, if sulphuric acid and alcohol are warmed together there is
ion
If the ion
sulphate.
TT \.
VT
^>
S04
This, like
ethyl-sulphuric acid.
in this case C 2 5 S0 4
the compound forms the anion
When a
solution of ethyl-sulphuric acid is treated with barium chloride, no
.
precipitate is formed.
These examples
suffice to
of substances under
different
of
conditions,
knowing
eral, additive, will be seen from a brief account of some of the work
which has been done on solutions of salts. Only a few physical
we have an
increase in
in volume will
DlFF.
KC1
26.7
9.0
NaCl
17.7
KBr
(8.4)
35.1
8.4
NaBr
(9.0)
26.7
(10.3)
45.4
9.3
Nal
(9.4)
36.1
KI
SOLUTIONS
results in the
hands of Ostwald. 1
He
301
produced by neutralizing potassium, sodium, and ammonium hydroxThe solutions contained a gramides with a large number of acids.
equivalent of the substance in a kilogram.
are expressed in cubic centimetres.
The changes
in
volume
302
tive ion
the same.
also
A number
upon the
cation.
some length by Arrhenius 5 when he proposed the theory of elecHe then took up a number of the properties
trolytic dissociation.
in this section, and, in addition, other
have
considered
we
which
which it would be premature to conof
solutions
physical properties
at
The
Ber.
635 (1885).
Jour. Chem. Soc. 55, 680 (1889).
d.
chem. GeselL
Beibl. Wied.
Ann.
6,
1073 (1873).
4
9,
Ztschr. phys.
SOLUTIONS
303
constants,
We
Hydrolytic Dissociation.
what
It
is
meant by
now remains
the molecule
is
not broken
weak
acid,
K C0 + 2 H = 2 KOH + H C0
2
etc.,
number
of salts of strong
304
bases with
weak
acids,
acetate,
much
solution
is
concentration.
The
investigations
of
Noyes and his coworkers, Kato, Sosman, and Kanolt, have led to
very interesting results. They have studied especially ammonium
acetate and sodium acetate, using the change in conductivity to
calculate the amount of the hydrolysis.
They have also calculated
the dissociation of pure water over a wide range in temperature.
Their results for ammonium acetate in one-hundredth normal
.
per
litre.
and
TEMPERATURE
the lonization
of Water
Ammonium
Acetate
SOLUTIONS
305
is
that water at
H 0,
2
most of the
molecules being polymerised; with rising temperatures these molecular complexes break down into the simple molecules
The
2 0.
number of 2 molecules in water is thus rapidly increasing with
rise in temperature.
molecules
SOLUTIONS IN SOLIDS
Solutions of Gases in Solids.
Many
solids
Our knowledge
we mean,
which there
See Rose Pogg. Ann. 83, 132, 417 (1851). Foussereau: Ann. Chim. Phys.
Arrhenius: Ztschr. phys. Chem. 5, 1
(6) 11, 383 (1887); 12, 553 (1887).
(1890); 13, 407 (1894).
Bredig Ztschr. phys. Chem. 13, 214 (1894). Noyes
:
18,
240 (1895).
(1894); Ibid. 77,5 (1900); Ztschr. phys. Chem. 4, 319 (1889); 32, 137 (1900).
Spring: Bee. Pays Sas, 16, 237 (1897). Walker and Appleyard: Journ.
Chem. Sac.
d.
and Derby
1 The above
account of the work on hydrolysis at elevated temperatures has
been communicated privately by Noyes to the author.
306
no chemical action between the gas and the solvent. The fact
that gases can form solutions in solids is often utilized to remove
the gas from regions where it is not desired.
The solubility of a gas
is
in a solid
the fact that such solutions have been very little studied, owing in
In solutions
part to the difficulties involved in dealing with them.
of liquids in solids it is difficult to say just when chemical action
between the two ceases, and true solution begins. Our lack of
due to the fact that the concepare so new that sufficient time
has not yet elapsed to push the studies, in terms of these concepThat there is much which can be learned
tions, into remote fields.
in reference to solutions of liquids in solids, will probably be shown
knowledge in
tions of
how interesting
facts
become when some one has pointed out their meaning and importance.
Little or nothing was heard of solid solutions until Van't
Hoff 1 published his now well-known paper about eleven years ago.
When
was proposed.
other than water, they give abnormally small depressions of the freezThis could be explained by assuming the presence of
ing-point.
complex molecules of the substance dissolved. If this assumption
true, then, as the dilution is increased, the complex molecules
should gradually break down into single molecules, and for very
dilute solutions the molecular lowering found, for such substances
should agree with the theoretical value.
But the largest value
is
" Ueber
feste
Eykman
322 (1890).
Ztschr. phys. Chem. 4, 497 (1889).
5,
festen Kor-
SOLUTIONS
that
when
807
which separates
is
not the pure solvent, but a mixture of the solvent and the dissolved
The facts known at that time
substance forming a solid solution.
this point were then considered by Van't Hoff in the
paper above cited.
If a solid solution is a solid, homogeneous complex of several
substances, in which the properties can change without destroying
which bore on
In isomorphous mixall
proportions, corre-
and by
show no isomorphism.
forms such crystals with the " ous " chlorides of
manganese, nickel, etc. Ferric chloride is taken up by am-
double
salts,
Ammonium chloride
iron,
chlorides.
When enough ferric
two form also a double salt, which can
be distinguished from the mixed crystal. Further, there are many
colored minerals known in which the ground mass is colorless.
Yet,
optical investigations have shown them to be completely homogeneous.
There are many amorphous, solid solutions, as the glasses and
is
etc.,
hyaline minerals.
l
Spring has furnished the following interesting example, showing
the mutual solubility of solids. When an equimolecular mixture of
When
action
308
Austen. 2
gaseous pressure.
4
When
I,
SOLUTIONS
309
310
tension of the dissolved body the other with that of the solvent.
If we are dealing with the tension of the dissolved body, the
;
problem reduces itself to determining whether there is proportionbetween the gas-pressure and the concentration of the solid
solution formed
whether in any given case Henry's law holds. If
it does, the dissolved gas has the same molecular weight as the free
ality
gas.
or
H, the values
of
p
6QQ
2.
Were
When
THIOPHENE IN BENZENE
PER CENT
SOLUTIONS
ever, that
is
a constant, makes
it
311
solids in solid
solutions.
Most
we owe
to
ing-point.
be abnormally small.
form
solid
italics
solutions
It
with
the solvent
indicated
just above
in
Benzene.
and tetrahydroquinoline.
Phenanthrene.
Carbazol, anthracene, acridine,
and hydrocarbazol.
Diphenyl.
312
same order;
have
little to
shown by the
do with
fact that
Work
of
Kiister
2
8
SOLUTIONS
313
quantity taken up by the same volume of the other, would be a conThat this is true has been shown experimentally l by quanstant.
titative determinations of the division of a substance between two
solvents,
and
is
of course be reached
used in any experiment was known. The amount which was taken
by the water was determined by the lowering of the freezing-point
of the water produced by the ether.
The difference between these
two quantities was the ether which had been taken up by the caoutchouc.
Care was taken to construct a freezing-point apparatus
which would prevent loss of ether by evaporation. The time required for equilibrium to be established between the ether and the
two solvents was duly regarded, and was shown not to exceed three
hours.
314
Ck
is
ether
= 100
The value
t-
Ck
of -77
is
is
increases as the
~\/
CTf
Cw
The value
of
Ck
Cw
Ztschr. phys.
Chem.
8,
112 (1891).
SOLUTIONS
315
The
The Molecular Weight of a Pure Homogeneous Solid.
work described up to this point has shown, according to Kuster,
that ether dissolved in caoutchouc consists partly of single and partly
of double molecules the number of double molecules increasing as
the concentration of the ether increases, and as the temperature is
;
lowered. This tells us, however, absolutely nothing as to the molecular weight of pure ether in the solid condition.
The second investigation 1 of Kuster aims at a solution of the
know
If
we could
we
we
would, therefore,
can regard as the solvent.
The division of one constituent of the isomorphous mixture
between the other (which we will regard as a solid solvent) and a
liquid solvent, would, as seen above, throw light on the molecular
weight of the constituent of the mixture first mentioned. It was
difficult to find
fulfil
the con-
dition that only one constituent should be soluble in the liquid solvent.
Kuster, however, secured such in a mixture of naphthalene
and
naphthalene was practically insoluble. The experimental work consisted, then, in determining the division of the /?-naphthol between
the water and the naphthalene. Isomorphous mixtures of /2-naphthol
and naphthalene of known composition were added in turn to measured volumes of water, and shaken with it until the water became
saturated with the /8-naphthol.
The amount of /?-naphthol present
in the water by
mixture by
and
the
in
the
concentration
of
that
which
remains
Kw,
Km, we have
If
Kw
The values found experimentally vary from
1
11.8 to 20.8.
316
(C 10
8) 2
and (C 10 H 80) 2
There are certain assumptions involved in this process of reasoning, so that the conclusion
final.
We
We
other changes which always take place to some extent when substances react chemically. Thus, thermal changes always accompany
chemical reaction. Again, if the reaction takes place under certain
problems for the chemist in the first half of the nineteenth century.
During the latter half of the century, however, more and more atten-
tion
until the
new
trans-
almost impossible to
overestimate their importance, since they are probably the cause of
all chemical activity.
Substances react chemically because of differ-
formations.
that
it
is
See Vaubel
SOLUTIONS
317
ergy into
The
electrical,
relations
material of Photochemistry*
can also study the velocities with which chemical reactions
We
We may
also
substances.
We
shall take
up
first
which seems
to be both rapid
1 These
subjects are taken up in the above order, since in terms of our prevailing theories we deal first with heat, then with electricity, and finally with
light.
2
(1914).
318
The form
in
= constant X
W.
This constant once known for benzene, we can calculate directly the
surface-tension of any other liquid when the drop-weight of the
liquid in question from the standardized tip at the given temperature
is
known.
excellent agreement.
GUYE'S
'
= 2,
We
have x=vmr.
From
this
we
From
a large
the above
number
of examples
X
becomes Jf=1.8
Guye shows
that
V=
when
Thus we
is
6,
211 (1890).
SOLUTIONS
319
WEIGHT-NORMAL CONCENTRATION
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
IN ATMOSPHERES
0.9
1.0
320
It will be
dilution
the ratio
to leak.
0.1
The much
4.317
0.2
8.976
0.3
13.768
0.4
18.772
0.5
24.162
0.6
29.635
is
obvious from
It
SOLUTIONS
same
321
salt in water.
the hydrates.
vent affecting the absorbing power of the dissolved substance. An
examination of Fig. 37 will show that neodymium chloride has a very
different absorption spectrum in water from what it has in methyl alcohol.
The uppermost
strip of
is
Figure
spectogram
solution.
We
large
of bands
one corre-
their investigation to a
much
larger
number
dymium
salts
a
IN
WATEB
GROUP
322
Jones and
Guy
The
and not simply their positions. The photographic method of determining the intensities of the various bands, gave hardly more than
and the whole system turns about a vertical axis. A mirror attached
shows the amount of turning when
The amount
fall on the junction.
radiation
to
is
allowed
any given
to the quartz fibre suspension
See Phil. Mag., May, 1912 Journ. Franklin Inst., December, 1913.
Amer. Chem. Journ. 47, 30 (1912); 49, 1, 265 (1913); 50, 257 (1913);
Phys. Zeit. 13, 649 (1912); Carnegie Institution of Washington, Publication
;
No. 190.
SOLUTIONS
323
the junction.
1
Jones, Guy, and Shaeffer studied the effects on the absorption
of light by water, both of salts that do not hydrate appreciably, and
those that have the power of combining with a large amount of
we
Very
At
when magnesium
practically all
chloride
of the concen-
The question
Phys. Zeit. 14, 278 (1913); Amer. Chem. Journ. 49, 265 (1913).
Phys. Zeit. 15, 447 (1914); Carnegie Institution of Washington, Publication No. 210.
2
324
still
more
little
ordinary temperatures is small, and the depression of their vaportension by dissolved substances is a small part of a small quantity,
difficult to
measure.
The
the two
is
The
degree of accuracy.
The problem
are equal, these two points just touch the two mercury surfaces in
the two limbs. This is taken as the zero of the instrument.
When
SOLUTIONS
325
The tilting is
points should just touch, the two mercury surfaces.
effected by means of a long lever with nut and screw at the end,
and
means of a microscope.
The limit of accuracy
difference in level of the
This
determined by
is
the one mercury surface being subjected to the pressure of the vapor
of the solvent, and the other to the pressure of the vapor of the
NORMAL
CONCENTRATION
DEPRESSION
os-
VAPOR-TENSION
mm.
mm.
0.0915 mm.
0.057 mm.
0.6
0.156
0.122
0.4
0.3
0.2
They
diffuse,
i.e.
molecules as they
Pfeffer
of
gum
7.2 cm.
26.3 cm.
18
120.0 cm.
sugar.
Colloids were found to lower the vapor-tension and also the freezFrom
ing-points of solvents, very much less than true solutions.
326
if true,
are
aggregation
of true solution.
ical suspension.
means
of finding out.
Phil.
Mag.
28,
38(1889).
Chem. Centralb.
1,
10 (1891).
Chem. News,
59,
296 (1889).
SOLUTIONS
PERRIN'S STUDY OF
327
Brown 1 found
movement was
The
first
to
Einstein. 2
The relation between the viscosity of the solvent and the amplitude of the vibrations was studied by Svedberg 3 while Seddig 4
studied the effect of temperature on the amplitude of the vibrations.
The result was to show that the Brownian movement is due to the
;
The suspended
on
particle is
bombarded
is
movement
of
THE ULTRAMICROSCOPE
beam of light is allowed to enter an air-chamber which conno suspended particles, or is passed through water which is
carefully freed from suspended matter, the path of the light neither
through the air nor through the water will be visible to the eye.
If, on the contrary, the air contains dust in suspension, and if a
If a
tains
colloidal solution
is
Phil.
*
6
Mag.
8, 18, 1 (1909).
328
in the air scatter the light in all directions and these become individWhen such a beam of light is focussed in a colloidal
ually visible.
two cases
is
We
limits of microscopic perception are far beyond the limits of microThe particles as seen in the ultramicroscope appear
scopic visibility.
amount
surrounding
INDICATORS
The Ostwald theory
of indicators simply
acid or base used as the indicator had a different color from its
ionized
salt.
The weak
slightly dissociated.
we
was only
added to the indicator
When
an acid or base
is
formed.
is
it
dicator.
Stieglitz
makes
it
indicator,
is
4, 10, 1
8
(1903).
Ibid. p. 1118.
SOLUTIONS
329
new
CHAPTER VI
THERMOCHEMISTRY
DEVELOPMENT OF THERMOCHEMISTRY
Earlier Observations;
Law
of Lavoisier
and Laplace.
It
was
chemistry.
is
and it was often difficult, not to say impossible, to deal with such
from the thermochemical standpoint. Hess showed that the heat
evolved in a chemical process is the same whether it takes place in one
or in several stages.
made
which otherwise would lie entirely out of the scope of thermochemical measurements.
Take, for example, the burning of
reactions
sulphur in oxygen.
If
we know
when sulphur
is
(Euvres de Lavoisier,
8
Pogy. Ann.
II, 283.
Klassik.
d.
exakt. Wissen. 9.
THERMOCHEMISTRY
at once the
was burned
331
is
it
dioxide,
would be the
two quan-
tities.
Hess made a second very important contribution to thermoWhen solutions of neutral salts are mixed there is no
thermal change, and Hess expressed this fact in his Law of the ThermoWe shall see that this law is extremely
neutrality of Salt Solutions.
chemistry.
we
Indeed,
shall learn
how
the law
is
a necessary consequence of
this theory.
to explain the law of the thermo-neutrality of
on the assumption that the heat evolved in salt
formation depends only on the nature of the acid and not at all on
the nature of the base. This assumption was erroneous and, therefore, the explanation based upon it.
So important is the work of Hess that he is regarded as the
Hess attempted
salt solutions,
father of all
Work
modern thermochemistry.
The determination
of temperature alone is
matter, but this is but the first stage in determining the quantity
of heat.
To determine the amount of heat, we must allow this to
warm some substance like water, and must know the rise in temperaThe experimental
ture produced and the amount of water used.
solution to a thermochemical problem, therefore, involves several
steps.
When
the heat
is liberated in
36, 1
332
in
some form of
vessel,
and
this vessel
Further, the
vessel and water, as quickly as they become warmed above the
temperature of surrounding objects, begin to radiate heat outward
water
itself
thermochemical measurements.
The work
of Favre
Thermochemistry in recent
66, 31 (1841-1845).
Thermochemische Untersuchungen.
4 volumes (1882).
THERMOCHEMISTRY
333
number
not have been dealt with under ordinary conditions. The work of
Berthelot, like that of Thomsen, will constantly appear throughout
this chapter.
The three fundamental principles or generalizations
at which he arrived should, however, be mentioned in this place.
I. The thermal change in a chemical reaction, if no external
work
conditions.
II. The heat evolved in a chemical process is a measure of the
corresponding chemical and physical work.
III. " Every chemical transformation which takes place without
maximum amount
of heat."
if it is
The
known
is
as the
We
[4], 6,
290 (1866).
we
shall turn to
Mec. Chim.
*
Loc.
oit.
I,
29.
334
may
is
final
upon
quali-
The
portance
we
shall
now
consider.
Ztschr. phys.
Chem.
In chemical reactions
12, 1 (1893).
THERMOCHEMISTRY
1.
A change
335
which
react,
except mass.
is
susceptible."
then, the same after the reaction as before.
Before the reaction the total energy was in the form of chemical or in-
The
total
energy
is,
trinsic energy.
After the reaction a part still remains in the form
of intrinsic energy, a part is transformed into heat, and if there is a
is
spent in doing
have
The law
is
fundamental to the
as
tion of energy,
which
is
the
little
first
value
principle of thermodynamics,
is,
The
definite temperature, and the solution of the acid must have a certain definite concentration.
If the acid varies in concentration, the
1
art. 74.
336
products formed
amount
may
of intrinsic energy
The
very different amount of heat will be liberated.
change in intrinsic energy, dE, is the same, but in the second case a
part has been converted into electrical energy, and, therefore, the
amount which remains to be converted into heat is less.
If we represent the second condition in terms of the general energy equation, we must introduce another term for the electrical
energy into which a part of the intrinsic energy has been transformed.
Let us call this dEe
We should then have
tration, a
dE =
dO
+ dE +dW.
e
The importance
Importance of Thermochemical Measurements.
measurements will appear at once from what has
preceded. We have no means of measuring directly the intrinsic energy contained in a substance. The best we can do is to measure the
difference in intrinsic energy between a system and another system into
of thermochemical
which
The
best
method
of measuring this
react,
and the
THERMOCHEMISTRY
337
such work.
of a
reaction
is
and the other negative. Since the heat evolved is so large with
respect to the work done, the sign of this factor essentially conditions the sign of the heat tone.
THERMOCHEMICAL METHODS
The problem
in thermochemical
is
known quantity
measurements
is
to determine
allowed to
In
warm
A platinum
calorimeter.
from
one-half
to
one
litre.
This
usually employed, holding
is surrounded by a known quantity of water, which is placed in an
outer vessel of silver or some other metal. This outer vessel is then
surrounded by poorly conducting material so as to diminish the loss
of heat by radiation.
The substances which are to react either in
vessel surrounded
vessel
is
the water
is
338
has already been stated, was that devised by Favre and Silbermann. 1
For a number of modifications consult the works of Berthelot 2 and
Thomsen. 3
One form
will be described in
some
is
thelot
c.c., is
surrounded by a vessel
FIG. 45.
a silver
pf thin copper, which, in turn, is closely surrounded by
The whole is introduced into a double-walled vessel of
vessel B.
sheet iron
agitated by means
1
2
8
I, p.
140.
THERMOCHEMISTRY
339
glass.
The
calibrated
the end in a very brief period of time, if they take place in the
presence of oxygen under increased pressure. For this purpose, an
The form
of
bomb which
is
used at present
is
by Andrews,
is
to be determined.
1
2
8
An
known
iron wire of
[6], 10,
433 (1887).
340
The bomb
filled
is
cylinder
by
tightly
down
screwing
the
arranged calorimeter.
The
current is passed
the
wire,
through
which burns in the
oxygen and ignites
and
the substance
the combustion of the
;
quickly completed.
The heat
liberated is
in
calorimeter
usual manner.
large
corrections
number
have
be introduced into
of
to
all
such measurements.
Thus, the heat which
is liberated when the
iron wire burns, must
be taken into account.
Further, the
filled
with
outset,
and the
gen of this
heat,
bomb
is
air at the
FlG 46
-
nitro-
THERMOCHEMISTRY
In addition, there are
all
details
341
the apparatus.
not been shown that the specific heat of water varies with the temThe work of Kowland and others has made it certain
perature.
that the
of water
K = 100 cals.
= 10 K = 1000 cals.
;
Cal
Thermochemical Symbols.
The methods of expressing the rethermochemical measurements are simple. The symbols of
the substances which react mean gram-atomic weights of the sub
sults of
stances.
Thus
H + O = H + 68,360 cals.
2
342
g.
g.
of oxygen, form-
ing 18
g. of water at ordinary temperatures, there are 68,360 calThese same facts are sometimes expressed
ories of heat liberated.
thus
[H2 0]
,
= 68,360 +.
The plus sign means that heat is liberated or that the reaction is
exothermic.
minus sign would mean that the reaction is endo-
g.
by
68,360 calories.
The same
principle holds
when compounds
react.
Thus
ammonia,
written
g.
41,900 calories
we wish
If
is
Thus
bol aq.
we wish
If
to represent the heat set free when a substance dissymbol aq is written after the formula of the
substance
liberated
HC1, aq
= 17,320 means
dissolved in water.
we wish
If
write as follows
and
solution,
we
this
g.
39,300 calories.
THERMOCHEMISTRY
343
stance
And
this
acid
is
= water-vapor
H = liquid water
2
2 0ioo
= ice.
-H
100o
= 9670
cals.
The
is self-evident.
to.
We
shall take
up
first
will,
results
in the other.
He
liber-
344
ated when the substance was burned in ozone, and concluded that
the difference in intrinsic energy of the two modifications of
oxygen
was to be expressed by the following equation
:
=3
+2
17,100
cals.
the intrinsic energies of the two modifications of oxygen. Thus, Berth elot 1 oxidized arsenious to arsenic acid, on the one hand
by oxygen,
on the other by ozone, and concluded from the results that
=3
+2
x 29,600
cals.
The still more recent work of Van der Meulen, in which ozone
was decomposed by platinum black, gave the result
2
O3 = 3
+2
x 36,200
cals.
The
We
'shall see
in
liberated.
set free.
The difference, 2300 calories, is the thermal equivalent of the difference in the intrinsic energy of the two modifications.
were
2 Ibid.
THERMOCHEMISTRY
345
Carbon.
ordinary
and sulphur:
For charcoal.
For retort carbon
For graphite
...
.
.,
.'
Fordiamond
96,980
cals.
96,530
cals.
93,360
cals.
J 93,240 cals.
cals.
\
94,550
Of the different modifications of carbon, charcoal contains the greatest amount of energy, and the crystallized modifications, graphite
and diamond, the least. The same general results obtained with,
other elements appear here in the case of carbon.
fourth non-metallic element which exists in
Phosphorus.
is
phosphorus
heat liberated.
two modifications.
Much work
has been done on the thermochemistry of other inorganic elements, and also an enormous amount on the thermal relations of the metallic elements but for the results obtained, reference
;
must be had
to
with thermochemical
detail
results.
of Neutralization.
When
solutions of acids
tant relation.
Ostwald
suchungen.
Lehrb.
Berthelot
d.
:
Allg. Chem.
II.
Thomsen
Thermochemische Unter*
346
amounts of heat
set free
HEAT or NEUTRALIZATION
The remarkable
fact
....
....
....
.
13,700 cals.
13,700 cals.
13,700 cals.
13,800 cals.
13,760 cals.
13,780 cals.
13,810 cals.
HEAT OF NEUTRALIZATION
'
The heat
....
....
.
13,700 cals.
13,700 cals.
13,800 cals.
13,900 cals.
number
of bases is
also a constant, provided the acid and bases are present in very
dilute solution.
But what is even more surprising, the constant in
this case has the same value as in the preceding case where the
was not
that
was proposed
we could account
of the theory.
Take, as an example, hydrochloric acid and sodium hydroxide.
In a very dilute aqueous solution of hydrochloric acid all the molecules are dissociated into
HC1
= H + Ci.
THERMOCHEMISTRY
347
sodium hydrox-
When
the dilute aqueous solutions of the base and acid are brought
The cation of the base, sodium, and the anion of the acid, chlorine,
remain in solution as ions after the process of neutralization in
The
exactly the same condition as before neutralization took place.
anion of the base-hydroxyl and the cation of the acid-hydrogen
combine and form a molecule of water.
It may be urged that the sodium and chlorine ions combine, since
sodium chloride is formed as the result of the neutralization. The
salt is formed if the solution is evaporated; i.e. if the solution is
concentrated. But it can be shown by several separate and independent methods, that a dilute solution of sodium chloride contains
only ions and no molecules. The sodium and chlorine, then, remain
as ions.
of
always formed
as the result of the process of neutralization; and further, it has
been shown by a half-dozen different methods l that hydrogen and
hydroxyl ions cannot remain in the presence of one another uncombined to any appreciable extent. This is the same as to say that
water is practically undissociated.
Since hydroxyl is the anion of every base, and hydrogen the
This
water.
is
is
The
acid,
forming
process of neutralization of any acid by any base is, theresame as the process of neutralization of any other
by the union of a
514 (1893).
Nernst
348
Thus
ions.
Since
equivalent of hydroxyl
Neutralization of
Weak
ples
is
HEAT OF NEUTRALIZATION
'
13,300-cals.
....
.
13,400 cals.
14,830 cals.
14,000 cals.
14,830
cals.
In these cases the acids are weak and the base is strong; neverthethere are considerable differences between the heats of neutralization and the constant 13,700 calories.
Similar results were obtained when weak bases were neutralized
with a strong acid. If, however, both acid and base are weak, the
heat of neutralization differs still more from the constant 13,700
less,
calories.
A few examples
When
ammonia
is
....
....
....
neutralized
11,900 cals.
11,900 cals.
12,700 cals.
stant 13,700.
If the
Explanation of the Results with Weak Acids and Bases.
is weak, we shall learn that it is only little dissociated
by water, even in dilute solutions. When only a part of the acid or
base is dissociated, the process of neutralization could proceed only
acid or base
had reacted
were
it
fact that as soon as the ions already present begin to react, more
ions would be formed from the undissociated molecules, or, in a word,
When
is
either evolved or
THERMOCHEMISTRY
349
consumed.
dissocia-
of dissociation
if
negative,
is positive, it
adds
itself to
it
Thus, the
heat whjch is liberated when a weak acid acts on a weak base, may
be either greater or less than the constant 13,700 calories
greater
when the heat of dissociation is positive, less when it is negative.
It could be equal to the constant only
of dissociation
is zero.
The
facts, then,
We
the
weak
acids
The theory
the
first
there
is
as ions
little
or
NaCl = Ka
KBr
When
=K
+ Cl
+B~r.
remain in solution as
We
can
now begin
and wide-reaching
sig-
zation of acids
salts
and this
develops, that
and
is
it
350
One important application of the heat of neutralmust be considered here. We have seen that when a very
dilute solution of
any strong
ized
ence of each other, one equivalent of the base is added. If all the
base went to the hydrochloric acid, the heat liberated would be the
same as that set free when the base acted on hydrochloric acid
If all the base went to the sulphuric acid, the heat liberated
would be equal to the heat of neutralization of the sulphuric acid by
the base, under the same conditions. If the base went part to the
hydrochloric acid and part to the sulphuric, the amount of heat set
free would lie between the above two values.
The latter condition is the one which always obtains. The
amount of heat set free falls between the amounts liberated with
alone.
we know
at once the
and
way
in
is
and clearness. In actual practice the mode of procedure is somewhat different, though the principle is the same. One acid is allowed
THERMOCHEMISTRY
351
sodium sulphate.
It is neces-
is
heat evolved
Given
acids.
mined.
Given two bases whose relative strengths are to be deterAn equivalent of each base is neutralized with a given acid,
and the amount of heat measured. Then one equivalent of the acid
added to one equivalent of the two bases in the presence of each
From the relations of
other, and the amount of heat determined.
these three quantities the division of the acid between the two bases
is
is ascertained.
method here
mean
352
quantitative significance, we must deal with definite amounts of substances and in order that the heats of formation of different sub;
stances
may
of substances.
of the
in
many cases directly, by allowing the elements to combine and measuring the heat set free but in many cases this is not possible.
large number of substances cannot be formed directly from the ele-
of formation
these elements, any difference in the amounts of heat set free in the
two cases is the heat of formation of the compound.
of methane.
It
would be impossible
to determine
....
.
Sum =
Heat liberated by burning 16
The
difference
g.
methane
in
oxygen
96,960
cals.
136,720
cals.
233,680 cals.
211,930 cals.
of formation of methane.
THERMOCHEMISTRY
353
Heat of Combustion.
By heat of combustion of a compound is
meant the heat which is evolved when a compound is completely
burned in oxygen. The carbon under these conditions is completely
oxidized to carbon dioxide, the hydrogen to water, the nitrogen to
and the sulphur to sulphur trioxide. The heat of com-
nitric acid,
bustion of organic compounds is a very important quantity to determine, since it is the only means, in many cases, of determining the
heat of formation of the substance. As we have just seen, it is only
necessary to determine the heat of combustion of the elements which
enter into a compound, and the heat of combustion of the compound
itself, and then to subtract the one from the other, in order to arrive
at the heat of formation of the
compound from
its
elements.
the combustion bomb, which has been already described, was devised
and used. In an atmosphere of relatively concentrated oxygen, i.e.
below.
of a
below
HYDROCARBONS
series
354
A constant
The
cally zero,
tion as an
ETHYLENE HYDROCARBONS
to
THERMOCHEMISTRY
ALCOHOLS
355
356
the elements
THERMOCHEMISTRY
357
well-known hexagon of Kekule; the second, the prism formula of Ladenburg. The attempt has been made to decide between these formuThomsen found l that when carbon
las by thermochemical methods.
is united with carbon by double linkage (C =C) the heat of combustion is different from that of carbon united to carbon by single
He worked out, approximately, the heat of comlinkage (C
C).
bustion of carbon under these two conditions, and also the heat of
combustion of six hydrogen atoms. He then determined the heat
of combustion of benzene, and found the value 788 Gals. When the
heat of combustion of the six hydrogen atoms was subtracted from
this quantity, the remainder was found to correspond to the condiIn a word, there
tion of six carbon atoms united by single union.
are nine single unions in benzene, or the prism formula of Ladenburg represents the structure of the benzene molecule.
We
must
We
open one.
Heat of Combustion.
Certain striking
between the heats of combustion of compounds and their
differences in composition have been pointed out.
We must not, however, draw the conclusion that heat of combustion is conditioned
Effect of Constitution on
relations
combustion,
it is
To determine
necessary to
Thermochemische Untersuchungen.
358
HEAT or COMBUSTION
.....
.
.'
395 Cals.
390 Cals.
compounds
HEAT OF COMBUSTION
252 Cals.
210 Cals.
HCOOCH3
acid, CH3 COOH
Methyl formate,
Acetic
When
HEAT OF COMBUSTION
C 6 H6
Dipropargyl, C 6 H6
788.0 Cals.
Benzene,
883.2 Cals.
it is
is,
of
energy.
For the most recent reliable measurements
Stohmann and Kleber Journ. prakt. Chem.
and Langbein:
in
thermochemistry see
Stohmann
Stohmann: Ibid. 48, 447
CHAPTER
VII
ELECTROCHEMISTRY
DEVELOPMENT OF ELECTROCHEMISTRY
The discovery of simple electrical pheEarlier Observations.
nomena preceded, by a long time, the recognition of the relation
between electricity and other manifestations of energy. It was not
1
until about the middle of the eighteenth century that Beccaria showed
that metals like zinc could be obtained from their oxides by means
The observation
of
Van Marum
when heated
it
If this
well as in oxygen, since neither of these gases took part in combusThe fact that no calc was formed in the presence of nitrogen
tion.
was a strong argument against the theory of phlogiston, as a satisfactory and sufficient explanation of the phenomenon of combustion.
Galvani's Discovery.
It was not until the last decade of the
with a scalpel, it was thrown into contraction by an electric discharge in the room. Galvani's investigations in this field brought
out the fact that when both muscle and nerve were connected with
1
359
360
tricity,* and
concluded that
ductors of the second class, i.e. the liquids present in the animal
He concluded that the chief source was at the contact of the
itself.
two metallic
stances
surfaces.
and second
which conduct
classes
placing in the
first
those sub-
which
placed in the hands of the investigator an unlimited supply of elecon systematic investigations
tricity, which made it possible to carry
this time electrochemFrom
hitherto
been
which had
impossible.
one
strides
enormous
important discovery
istry developed by
quickly following another.
The Electrolysis of Water.
The next
was
to determine
whether
it
I, p. 10.
Grens Journ.
1
d.
Phys.
3,
479 (1796).
ELECTROCHEMISTRY
361
1
by Nicholson and Carlisle at the beginning of the nineteenth century.
By means of the current they decomposed water into oxygen and hydrogen, the gases being liberated on the two poles of their couples.
This was an important step, since it showed clearly the transformation of electrical energy into chemical, and made it strongly probable that there is a close relation between the two.
Work
of Davy.
At
this time
Humphry Davy
electric pile,
began
which
his
finally re-
sulted in the separation of the alkali metals from their oxides. The
decomposition of these oxides directly by the current was strong
ies
learn
is
held
Nicholson's Journ.
4,
Gilb.
179 (1800).
Ann.
7,
1,
161 (1808).
Bakerian
362
both kinds of
electricity.
ar-
rangement, and the electrical nature of the atom depends upon which
kind of electricity is present in excess. One kind is usually present
in large excess, giving the atom a decidedly positive or negative
One "pole" is usually much stronger than the other, so
character.
that the atom reacts as if it were " unipolar." Chemical attraction
is
may
The theory
as put forward
If chemical
union
is
due to the
electrical
attraction of
or less
compound must
The theory, however, was soon called upon to meet what was
supposed to be a very serious objection. If chemical union depends
only upon the electrical charges upon the atoms, then, the properties of the compound formed would be a function of the electrical
charges upon the atoms in the compound. It was found to be possible to substitute the three
Gilb.
Ann.
27,
Fysik.
1806.
ELECTROCHEMISTRY
The
363
charge, while the three chlorine atoms each carried a negative charge.
That three positive charges could be replaced in a compound by three
negative charges, without fundamentally changing the nature of
J. J.
positive,
now
electrolyzed hydrogen
gas,
charged
now
one pole and negative to the other. The spectra of the hydrogen
around the two poles was studied and found to be quite different.
The molecule of hydrogen gas is, then, very probably made up of a
positive
We must not,
ion.
hydrogen
some-
is
electropositive element
of
an
are
atoms
replaced by
electronegative element chlohydrogen
rine, without altering the type of the compound.
Thus, for example,
we can
CH by Cl
CH C1 CHC1
CH
S C1,
successively, the compounds
seemed of interest to investigate what
atoms, getting,
and CC14 It
was the nature of the charge
2
2,
3,
364
when
,
Law
is true,
and such
is
the
fact.
of Faraday.
the
different elements
which
current was passed through solutions of, say, copper sulphate, zinc
chloride, and silver nitrate, and the amounts of copper, zinc, and
silver deposited determined by weighing the electrodes before
Expr. Researches,
III, Ser.
ELECTROCHEMISTRY
equivalents of these elements.
The atoms
365
word,
all
which
difference
exists
Elec-
energy
capacity factor
or
quantity
x
x
intensity factor
potential
= electrical energy,
= electrical energy.
compounds.
When
,the
366
of water; yet
directly.
from
Theory of Grotthuss.
for electrolysis
The
was Grotthuss, 1
first
-f
ELECTROCHEMISTRY
The atoms marked
positive represent
hydrogen
367
those marked
negative, oxygen.
passed, each oxygen atom
is combined with a certain definite hydrogen atom, forming water.
When the current is passed, the hydrogen atom nearest the negative
is
becomes electrically
up its positive charge to that pole,
and separates as hydrogen gas. (See Fig. 37.) The oxygen
atom which was originally in combination with this hydrogen is
now free, and combines with the hydrogen of the next molecule of
water.
This sets another oxygen atom free, which combines with
the next hydrogen, and so on until the positive pole is reached,
when the last oxygen atom in the chain not having any hydrogen
pole gives
neutral,
FIG. 37.
stituents.
The
atom, from which it does not part company. The current must first
decompose the water molecules before any electrolysis can take
This theory accounted for the facts known at that time, and
remained as the established theory of electrolysis until after the
middle of the nineteenth century.
place.
it
368
S02
I.
II.
S02
+ HOC H = SOj^" + H
<
<
+ HOC H =
2
The second
ethyl sulphuric acid, by the hydroxyl hydrogen atom from the alcoThe reaction which takes place as represented in I is reversed
hol.
in II, the final result being the removal of a molecule of water from
two molecules of alcohol, and the formation of a molecule of ordinary
ether.
From this Williamson concluded "that in an aggregate of
the molecules of every compound, a constant interchange between
the elements contained in them is taking place."
Williamson 2 concluded his paper with the following very signifi"In recent years chemists have added to the atomic
an
uncertain, and, as I believe, an unsubstantiated hypothesis,
theory
that the atoms are in a condition of rest. I reject this hypothesis
and found my views on the broader basis, the movement of the atoms."
Clausius s did not think it necessary or even
Theory of Clausius.
cant words:
justifiable to
the other hand, he saw that the theory of Grotthuss was not capable
of accounting for facts
light since
it
had been
The
" In order to
separate the once combined
part-molecules, the attractions which they exert upon one another
must be overcome. To accomplish this, a force of definite strength
this point Clausius
is
says
is
Lieb.
8
*
no
de-
ELECTROCHEMISTKY
369
same
effect of the
to one another.
may draw
is
The assumption,
an electrolyte
is
one of
SB
3,
120 (1889).
370
pole,
Such a current,
effect electrolysis of water containing a little acid.
in terms of the theory of Clausius, would simply exert a directing
influence on the part-molecules already present, since it would be
too
factor
capacity factor or amount of heat. The unit for the intensity
of heat energy is the degree, starting from the absolute zero.
have no corresponding unit for the intensity factor of electrical
We
We
can
energy, and may, therefore, choose our unit arbitrarily.
In practice, we usually
start from any constant potential as zero.
The capacity
select the potential of the earth as the zero point.
for electrical energy is the amount present in a given system, for
a definite difference in potential.
comment.
All known substances
Heat and of Electricity.
conduct heat energy. Metals are the best conductors of heat, both
The best conductors of heat energy,
as to quantity and rate.
ELECTROCHEMISTRY
371
The
rai^io
20
tors of electricity is about as 10 to 1.
solids conduct in
general
non-conducting salts when fused
become electrolytes. Gases, according to the recent work of J. J.
1
Thomson, undoubtedly conduct electrolytically.
Substances like the metals, which carry the current without
better than
liquids;
yet,
many
the
first class.
but at the same time they undergo chemical decomposiThese are known as conductors of the second class. So little is
known about the actual mode by which metals conduct the current,
conductors
tion.
that
it is difficult
to say just
to the distinction
upon the quantity of electricity upon the bodies, the distance between the bodies, and the nature of the medium which surrounds
them. If we represent the quantities of electricity by q1 and g2 the
distance between the bodies by d, and the specific inductive capacity
>
in
which
This
verified
medium by
(7,
it
known
as the
it
was he who
first
experimentally.
372
other.
The current always flows from the conductor at higher to
that at lower potential. During the passage of the current, certain
effects are produced in the conductors which obey definite known
most common of these is the heating of the conenergy disappears and heat energy appears.
This fact must have been observed, qualitatively, by every one who
One
laws.
ductor.
of the
Electrical
quantitative
= re
2
.
Law of Ohm.
quantitative relation has also been established
experimentally between the strength of the current, the electromotive force, and the resistance. Let C be the strength of the current,
r _E
~B
which
is
Ohm's law.
the centre.
When
we have
unit
quantity of electricity.
In the electrostatic system, that quantity of electricity is taken
as the unit, which, when placed at a distance of a centimetre from an
equal quantity, the two being separated by air, will exert a force of
a dyne, or will produce an acceleration in a gram-mass, of a centimetre per second. The nature of the medium separating the two
quantities is essential to the definition, since the
depends upon the dielectric constant of the medium.
exerted
force
Phil.
Mag.
ELECTROCHEMISTRY
373
The electromagnetic
The Electromagnetic System of Units.
In
far
the
widest
has
practice the unit of
application.
by
system
is
quantity
The unit
sisting
of mercury, mercurous
solution),
amalgamated
zinc,
- 0.0012
1.4328
The
(f
- 15)
volts.
is
called a coulomb.
The
unit of energy
is
is
called a
joule.
It is
the electrostatic
electromagnetic.
10
real electromagnetic unit of quantity is about 3 x 10 as great
as the electrostatic unit.
But the electromagnetic unit actually in
The
the coulomb
use
unit.
unit of energy
tial is
300
is
volts.
Electrochemical Nomenclature.
We
owe
to
374
position.
is
made,
that
it
careful quantitative study of electrolysis, and determined the relation between the amount of electricity which passed through a solu-
an
tion of
effects.
electrolyte,
He
of
the elements.
Where the ion is elementary, as in the case of a metal, the combining weight is equal to the atomic weight divided by the valency.
Where the ion is complex, as is true especially of many anions, the
combining weight
by
its
is
valency.
second class by the passage of equal quantities of current are, for the
same electrolyte, equal; for different electrolytes are proportional to
the combining weights of the ions.
From
this,
we
Testing the
Law
own experiments
of Faraday.
Faraday
This is analogous
atoms have the
all
2 Brit.
ELECTROCHEMISTRY
375
law of Faraday as the intensity of the current varied. This is supposed to be due to the solvent action of the solution of the copper
A careful
salt on the copper which had already been precipitated.
1
quantitative study of the law of Faraday was made by Buff, using
the silver voltameter.
much
as
from 1
The
Lieb.
Ann.
85, 1 (1853).
3,
120 (1889).
376
That
electricity is
the electrons
has
been made highly probable by the work of J. J. Thomson (see page 40).
Indeed, this conception was in vogue at an earlier date. Helmholtz
was forced to the conclusion that electricity is of an atomic nature,
and Lorentz and Larmor have dealt with the electron. It, however,
remained for Thomson to prove the existence of the electron by
direct experiment, to show its order of magnitude, and to study
of its properties.
It is true that the electrons are the units of negative electricity,
many
In terms of the
electron,
which
is
The
it is
com-
posed of ultimate units, explains the fact that we do not have elements with fractions of valence, just as we do not have compounds
with fractions of atoms. It explains for the first time the real
is purely arbitrary.
Here, as in so many other
convenient to use the gram-molecular weight for
In
univalent, and gram-equivalent weight for polyvalent ions.
case the ion is elementary and univalent, as with silver, the
cases,
it
is
gram-molecular weight
The atomic weight of
is
silver, in
ELECTROCHEMISTRY
377
O.OOlllol
This
is
used.
This
is
also the
when properly
Using
mean
corrected,
Heimrod 1
= 96,580
coulombs.
amount of
electricity
From
Suppose it is
principle of the voltameter is thus very simple.
desired to know the amount of electricity which flows through a
given conductor in a given time.
The current
is
passed through a
solution of
This
silver voltameter.
378
its surface.
The metal
and next
best adapted
to silver
comes
copper.
In addition to the metal voltameters, there is another form which
depends for its utility upon the amount of gas set free when the
current
is
In
this form, which is called the gas voltameter, the gases are collected,
reduced to standard conditions of temperature, pressure, and dry-
gen ions carries 96,530 coulombs. One gram of hydrogen gas has a
volume of 11,188 c.c. Since it is possible to measure a small part of
a cubic centimetre of gas, it is possible to measure a very small quantity of electricity
The phenomenon
of electrolysis
ELECTROCHEMISTRY
379
and exactly an equal amount of copper will pass into solution from
the anode. The total amount of copper in solution will remain constant,
deeper, while in the neighborhood of the cathode it gradually becomes less intense. The solution becomes more concentrated in
copper around the anode and less concentrated around the cathode.
If in this experiment platinum electrodes are employed, copper
at the cathode but since there is no metallic copper
would separate
become constantly
In
less.
would dismore
appear
rapidly around
the cathode.
Hittorf 1
Hittorf s Theory.
either
or
cation
the
solution
of
the
The white
electrolyte
is
passed.
circles
represent
the anions, and the lined circles
the cations. For each anion
of the anion differs greatly from that of the cation, and for the sake
of simplicity let us say that the velocity of the anion is twice that of
the cation. Let the current pass through the solution until three
when
380
the total
number
of
molecules electrolyzed,
we
-|
If,
amount
of the
electrolyte decomposed.
There are, then, three quantities which can be determined experimentally: the change in concentration around the cathode, the
change in concentration around the anode, and the total amount of
the electrolyte decomposed. It is necessary to determine only two
The two
of these, since the third is given by the sum or difference.
which are chosen depend upon the ease and accuracy involved in
making the measurements.
Since the total amount of electrolyte decomposed is proportional
to the amount of current which is passed through the solution, it is
only necessary to measure the latter in order to know the former.
This can be done conveniently by inserting a silver voltameter into
the circuit, and weighing the amount of silver deposited. This is
by
analysis.
The apparatus
ELECTROCHEMISTRY
381
must be so constructed that the effect of diffuto mix the solutions of different concentrawould
tend
which
sion,
tions around the electrodes, is reduced to a minimum.
Several forms of apparatus have been devised for determining
tions are carried out
Nernst
is
the
apparatus
corks
and electrodes
were
by closing
mouth.
and evacuating
The apparatus
is
with the
so constructed as
The
from 40 to 60 c.c. of solution.
C and B are then closed, the
whole apparatus placed in a thermostat and
to hold
openings at
8 Ztsctor.
39, 612.
382
The portion first removed contains the heavier, more concentrated solution around the anode the second, the unaltered middle
layer; and the third, the more dilute solution around the cathode.
ratus.
This method
there
The methods' of Kisticikowsky* and of Bein* are the same in principle as that just described. The burettes are given different forms
in the two cases, and also differ in form from the burette in the
method just described.
The same objection offered to the method
of Loeb and Nernst applies here.
There is no means of completely
the
two
of
the
solution
after the electrolysis is
separating
parts
3
Quite recently Bein has carried out an elaborate investigation on the velocities of ions, which, on the whole,
probably contains some of the best results thus far secured.
brought to an end.
number
large
and
means
forms.
in diameter
and are connected 3 cm. below the stoppers, by a U-tube 1.5 cm. in
diameter. Each arm of the U-tube is 10 cm. long, and at the centre
Into the electrodes, made
it is a stopcock of large bore (1 cm.).
of disks of pure silver, is riveted a short piece of stout platinum
wire, which is then sealed into thick-walled glass tubes of 2 mm.
of
2
Ztschr. phys. Chem. 6, 97 (1890).
Wied. Ann. 48, 29 (1892).
Ztschr. phys. Chem. 27, 1 (1898) ; 28, 439 (1899).
* Amer. Chem.
& Ibid.
Journ. 32, 409 (1904).
31, 427 (1906).
i
ELECTROCHEMISTRY
383
bore.
the electrode
electrodes
through
the
into
stoppers,
is
are
forced
holes
bored
ground-glass
which
close
To
are
attached
outward and
It was found,
especially with alcohol
and acetone solutions,
tending
upward.
The advantages
this
of
FIG. 51.
form of apparatus
It is perfectly
It is easily made and handled.
chamber.
so
that
either
side
can
as
cathode
be
used
symmetrical,
All danger of diffusion is done away with and no membrane is
are
evident.
necessary.
its
The
accurately determined,
quantities of solution.
in both arms can be very accurately levelled, and, finally, the stopcock at the center of the U-tube makes it possible to separate
completely the cathode and anode solutions, and to rinse out the
two
Chem.
384
Causes which
may
It
does not follow that the relative velocities of two ions obtained
The
ment.
1
by Hittorf.
the current.
effect of
He
studied
The
ferent strengths.
copper and
veloci-
The absolute
velocity with
the
directly dependent upon
strength or
is
The second
of
copper
sulphate
to
so
many
parts
of
water.
Ztschr. phys. Chem. 23, 469 (1897).
W. Bein : Ibid. 27, 1 (1898) ; 28, 439
O. Masson: Ibid. 29, 501 (1899); Phil. Trans. 192, A, 331. F.
(1899).
Kohlrausch : Wied. Ann. 66, 785 (1899). A. A. Noyes : Ztschr. phys. Chem.
36, 63 (1901).
Chem.
37,
Ibid. 40, 737 (1902). Noyes and Sammet : Ibid. 42, 49 (1902) ; Journ. Amer.
Chem. Soc. 24, 944 (1903).
Carrara: Gazz. chim. ital. 33, I, 241 (1903).
Denison : Ztschr. phys. Chem. 44, 575 (1903). Tower Journ. Amer. Chem.
:
Pogg. Ann.
ELECTROCHEMISTRY
385
386
and 25
move with the same velocity, which is 0.5. This point was in1
A few of his results for the
vestigated much more fully by Bein.
anions will show that this conclusion is probably true.
to
ELECTROCHEMISTRY
387
so
directions.
many
geo
o
I
40
20
40
80
120
160
500
ATOMIC WEIGHT
FIG. 52.
Ions.
give only the relative velocities with which the ions move. To determine the absolute velocities some other method must be employed.
Two general methods have been employed for determining the absolute
move.
velocities
The one
measures
at
once
is
direct
the
and
absolute
Pt
velocities.
There
is
an
also
indirect
A|
later
388
One end
(Fig. 53).
A piece
A and con-
The hydrogen
t.
They
ions
A into the
vessel
tube
extended is measured.
In making such measurements it is necessary to know the difference in potential at the two ends of the tube, or, as it is called, the
drop in potential along the
A potential
tube.
a volt a centimetre
the unit.
gradient of
is
taken as
the drop
in potential along the tube,
the time during which the
Knowing
have
all
For unit
the swiftest
of
all
ions.
FlG
0.0026,
second.
The
will be
results obtained
compared a
by the
little
indirect
later
small indeed
when
to
ELECTROCHEMISTRY
389
introduced into the longer arm, and then the lighter solution
carefully poured into the shorter arm.
is
The current
is
ammonium
from the
solutions
chloride
is
is
colored,
due
considered hereafter.
law:
The electromotive
force
TT
is
Two
The
reciprocal of
therefore,
is,
monly used
1
Steele
449.
1906,
390
pends upon two things, their nature and their form. To compare
we must use forms which are
comparable. There are two forms which have been used that of a
cube whose edge is 1 cm. long, and that of a cylinder 1 m. in length
the resistances of different substances
and
1 sq.
mm.
in cross-section.
is
is
The specific
When
measured in ohms,
conductivity
is
the resist-
known
it is
as
specific resistance.
which we
will rep-
p = ns.
on the other hand, we represent the specific conductivity of a cylinder of the solution 1 sq. mm. in cross-section and 1 m. in length by
s, this will have -5-5-^-5-5- of the conductivity of the cube above deIf,
scribed.
thus
//,
p = 10,000 ns.
= 1000
= sxlO,OOOxlOOO
= sx!0
The molecular
ELECTROCHEMISTRY
ity
by means
of a continuous current.
391
is
The use
receiver,
The
Fig. 55.
is
in the
method
of Kohlrausch
coils.
is
sketched in
The metre
stick
392
AB
R is
a glass cup which contains the solution whose resistbe measured. The electrodes are cut from thick sheet
platinum, and a piece of platinum wire is welded into the centre of
each plate. This wire is then sealed into a glass tube, which is rilled
current.
ance
is to
with mercury to make electrical contact with a copper wire introduced into the mercury. The telephone is connected between the
rheostat and resistance vessel, and also with the bridge wire by
in the vessel r^
From
would have
rb
= rja
rb
ri==
Since conductivity
c is
_na
=
rb'
by the
which
p.
letter
applies,
we
/*.
= narrb
This expression takes into account all of the factors except the cell
constant k, which depends upon the size of the electrodes which we are
using, and their distance apart. Introducing the constant, we have
na
ELECTROCHEMISTRY
398
solution
At 25 the
is
oO
129.7.
conductivity of this solution, or the value of //,,
is poured into the cell until both electrodes are
This solution
covered.
warmed
to
value of
minimum
in the telephone.
This
is
effected
by electrolyzing
in the
known
noted.
urements.
be
not the case, as in fact it never is, the wire must be calibrated and
The most convenient method of
corresponding corrections applied.
2
The princalibrating a wire is that devised by Strouhal and Barus.
is
For
point^ Boiling-point,
Easton, Pa.).
2
Wied. Ann. 10, 326 (1880).
Co.,
394
air.
The degree of purity attained by this method is best realized
the
by
following comparison of the conductivity of the water with
that of a metal.
cubic millimetre of this water at zero degrees
the
had a
resistance
times.
It is not possible, nor is it at all necessary, to prepare water of this
degree of purity for ordinary conductivity work. In such work comparatively large quantities of water are needed, and methods are
available for obtaining an abundance of water of a high degree of
purity.
water
Traube Physikalisch-chemische Methoden. Jones Freezing-point, Boiland Conductivity Methods. Ostwald Hand- und Hilfsbuch zur Aus-
ing-point,
19, 91 (1897).
ELECTROCHEMISTRY
395
effect of
bath
is filled
in the figure.
Gas enters at A. The
tube
is inserted into one arm of the
regulator,
it
This
nearly touches the mercury.
tube also contains a small hole in the
side.
When the bath becomes warmer
than the regulated temperature, the solution of calcium chloride
expands, drives up the right arm of mercury, and cuts off the gas.
The small hole in the side of
prevents the flame from becoming
2,
565 (1888).
396
When
extinguished.
whose conductivity
it is
desired to measure
is
auto-
placed
Magnitude
Number
of the
Temperature
of Substances.
TABLE
I.
ELECTROCHEMISTRY
397
It w.ill be seen from the above data, taken from the work of Jones
and West, 1 that the temperature coefficients of conductivity are
large, and this must be carefully taken into account in making conductivity measurements.
The Bearing of Hydrates on the Temperature Coefficients of Con-
Jones
ductivity. A Fifth Argument for the Existence of Hydrates.
and West 2 have shown that for temperatures ranging from
to
35,
ture.
electrolytes are slightly less dissociated at the higher temperaThis same fact is established at much higher temperatures by
is
taken
is
and, further, the mass of the ion decreases with rise in temperature.
This does not refer to the charged atom or group of atoms which
we
usually term the ion, but to this charged nucleus plus a larger or
smaller number of molecules of water which are attached to it, and
which
it
it
in its
of the solvent.
That ions are hydrated has been shown beyond question by Jones
and his coworkers. That these hydrates are relatively unstable
compounds has also been demonstrated, the higher the temperature
the less complex the hydrates existing in the solution.
This can be
seen from one example. In a solution of a certain definite concentration, every molecule of
from
it,
its
resistance
Ibid.
Ztschr. phys.
Chem.
This
If this factor
398
We
be remembered
crystallization
little
or
no
crystallize with
lization may be
large
amounts of water.
those in Table II
The water
of crystal-
is
should
conductivity.
ELECTROCHEMISTRY
If we examine the above
The substances in Table I
tables,
we
399
equal.
The substances
and
all
orde.r of
Of the compounds recorded in Table II, the one which, apparently, presents the most pronounced exception to the relation that
temperature
coefficient of conductivity
is,
it crystallizes.
Its
great.
is
At
ficient
factorily
400
of Jones and
by
differ-
is
more
greater the
dilute
the solution.
All three of these conclusions are necessary consequences of the
assumption that the large change in conductivity with change in temperature
is
formed around
of Different Substances.
The
first
pounds can be divided into two large classes. First, those which in
the presence of water conduct the current, undergoing simultaneously decomposition or electrolysis. These are called electrolytes.
Second, those substances which, in the presence of water, do not
conduct the current, and do not undergo any decomposition when an
attempt is made to pass a current through their solutions. These
are called non-electrolytes.
The
power.
high conductivity, as the strong acids, strong bases, and salts and
those with low conductivity, as the organic acids and bases. This
;
the extremes.
Again,
good conductors.
The
we
recognize
marked
strong monobasic
acids,
such as hydrochloric,
Demonstration of the Different Conductivities of Different SubIt can be readily demonstrated that different electrolytes
have very different conductivities. This has been shown by Noyes
stances.
and Blanchard 1
1
in an experiment
which they
state
was devised by
ELECTROCHEMISTRY
401
Whitney.
chloracetic,
which pass glass tubes. These tubes carry copper wires, the wires
terminating in platinum
shown in the
must be
move these glass
disks as
We
figure.
able to
with a 32 candle-power,
The
110-volt
lamp.
other side of each lamp
with one
is connected
wire
from
110-volt,
alternating-current
namo.
FIG. 57.
dy-
the tops of the glass tubes are connected with the other wire from
the dynamo.
Add 100 cc. of pure water to each glass tube. Add 5 cc. of the
of chloracetic acid to
and in the
acetic acid
the electrodes
same concentration
the hydrochloric acid being the most,
the acetic acid the least, dissociated.
This experiment can be used to illustrate another fact. If the
at the
402
all
dissociated.
The study
mo-
The resistance of
lecular conductivity increases with the dilution.
a solution increases with the dilution, which is the same as to say
that the actual conducting power decreases as the dilution increases.
While this is true, the conductivity does not decrease as rapidly
as the dilution increases, hence the molecular conductivity increases
There are so few exceptions known to this
with the dilution.
this point,
however
1.
to 10,000
1.,
may
be carried.
The same general relations hold for the poorer conductors, but
in these cases the constant value of the molecular conductivity is
reached only at dilutions much greater than those named above.
For many of the poorest conductors, the constant value of the molecular conductivity cannot be obtained directly by the conductivity
method. In such cases an indirect method must be applied, as we
shall see later.
The
HYDROCHLORIC ACID
ELECTROCHEMISTRY
application of the conductivity
trolytic dissociation.
These results serve
also
method
to the
403
measurement of
elec-
degrees of
acids, bases,
and
salts.
The value
The value
of
of
is
is
141.0
120.0
21.0
Difference
The value
The value
...
...
121.0
97.5
23.5
Difference
The same
anion.
^ KBr -- ^ KN0
^ NaBr ^ NaN0
3
The
difference
= 141 = 120 -
perimental error.
The value of
is
121
97.5
= 20.0
= 22.5.
The constants above referred to are, then, proportional to the velociand anion respectively. If we represent by c the
+ a.
404
Expressed in words,
gradient,
which
and
it is
is
is
inde
present in
the solution.
This generalization is usually referred to as the law of the independent migration velocities of ions. The law in this form holds, in
general, only for very dilute solutions, since it is only in such solutions that the true values of
^ are
obtainable directly
by experi-
ment.
Ostwald' s Modification of Kohlrausch's Law.
The law
as enun-
can be used with more concentrated as well as with more dilute soluIf, however, the solutions are more concentrated and not completely dissociated, the amount of their dissociation must be taken
tions.
into account.
comes
pv = a
(c
+ a).
As
unity,
rausch.
The
Law
It is obvious
method
of c
/i,^,
is
+ a. We
- by
Knowing
+ a and a-, we
Lehrb.
d.
ELECTROCHEMISTRY
405
rausch l for the chlorine ion. The velocity of this ion was calculated
from several salts and was found to be the same in each case. The
6
velocities are expressed in 10" centimetres per second.
1
the temperature,
is
volt
centimetre
tial gradient
;
per
CONCENTRATION
NORMAL
The poten18.
406
tivity
would
lie
We
any
An
the value of
//^
sodium
ion,
which
anion.
If to this
for the
is
ELECTROCHEMISTRY
for the sodium salt of that acid,
sodium salt plus 275.8.
minus
407
49.2, plus
325
i.e.
^ for the
we wish
If
strictly
The value of
of the base, and the other upon the chlorine anion.
for
the
minus the
base
is the value of
the
free
a
for
chloride,
30
lOG
,
constant for chlorine, plus the constant for hydroxyl. The value of
the constant for chlorine at 25 is 70.2 that of hydroxyl, 170. The
;
is,
N0
base
we must,
therefore,
nitrate of the base.
An
1
empirical method has been worked out by Ostwald for determining the value of /^ for the sodium salt of an acid, from
the value of
By
Volumes:
32
64
128
Differences:
12
10
we obtain
^ at once.
/*
256
6
at
612
1024
the dissociation a
and also the value of
which is equal to ^v divided by /xw
It is genIs Conductivity an Accurate Measure of Dissociation?
erally assumed that the conductivity method is an accurate measure
If there is no dissociation, there is no
of electrolytic dissociation.
.
is a
taken
as
proportional
any
to its conductivity.
In order that this should be true, there must be
no change in the velocity of the ion as the dilution of the solution
conductivity.
maximum.
If dissociation
The
is
dissociation of
at a
maximum, conductivity
solution
is
changes.
much
Lehrb.
d.
Allg.
Chem.
II, 693.
408
move more
slowly.
Conductivity is, therefore, not an accurate
measure of dissociation in concentrated solutions, as is well known.
In dilute solutions there is considerable doubt as to the accuracy
of dissociation as measured by conductivity. The work of Jones and
The
ratio
/*
sociation.
Indeed,
reliable
it
is
electrolytic dissociation.
methods for the same substance at the same dilutions are the same,
A few results will answer this question. In the
or different.
following table the conductivity measurements and freezing-point
1
lowerings were made by Jones and Pearce:
COMPOUNDS
ELECTROCHEMISTRY
COMPOUNDS
409
410
The Dilution
Law
of Ostwald.
we have
seen.
This holds up to a
a
certain
dilution the conBeyond
dilution increases.
Ostwald l found from his own work that the molecular conductivities of all monobasic acids pass through the same series of values.
Thus, if any two acids A and B have the same molecular conductivities at volumes Vi and v2 they will have the same conductivities
Ostwald 2 went much farther, and discovered
at any other volumes.
the mathematical expression connecting dissociation and dilution.
He gave us our first rational dilution law. The law was deduced
,
as follows:
If the laws of gas-pressure hold for dilute solutions, and if the
Arrhenius theory of electrolytic dissociation to account for the exceptions shown by electrolytes is true, then the formula connecting the
degree of dissociation with the volume of gases must apply directly
to the relation between the dilution and the dissociation of electro8
The law of the dissociation of gases must apply also to the
lytes.
into
R log -
PlPll
-2-
? 4-
const.
II, 723.
ELECTROCHEMISTRY
products
411
is
= const.
(1)
Pi
is
position products.
the mass of the dissociated products, and v the volume of the solution
-.
*-=.*-*
(1),
we have
= const.
(2)
Ul
is
Substituting
/*.
(2),
we have
= const
This expression can be simplified by writing a
when we
/*
have
= const.
(1
a)v
number of
Ztschr. phys.
Jahn: Ibid.
solutions of
Chem.
33,
3, 170,
545 (1900).
412
from these
He
the solution, or
number
of litres
The
results for
FORMIC ACID
V
ELECTROCHEMISTRY
AMMONIA
,
413
414
v,
c,
we
= 16,
= 64,
v = 256,
v
= 0.26;
= 0.13;
c = 0.065.
c
glance at these figures will show that a constant would be obtained, if the values of c were multiplied by the square root of v in
each case
:
0.26
x VI6
= 0.13
x V64
= 0.065
x V256.
He
const.
applied this equation to between fifty and sixty strongly dissociated compounds, and the values found for' c always approached
The results for a few substances will be
closely to a constant.
given.
HYDROCHLORIC ACID
ELECTROCHEMISTRY
1
posed.
tioned.
415
He showed
2- =
Q
const.
a) v
(1
that the conductivity method as already pointed out (see page 395)
If the electrolyte
is not a true measure of electrolytic dissociation.
is weak, i.e. not much dissociated, the error in measuring its dis-
by the conductivity method does not have much signifithe results are inserted into the Ostwald equation.
When, however, the electrolyte is strongly dissociated, an appreciable
error in the measurement of its dissociation would produce a large
effect when the results were inserted into the equation expressing
sociation
cance
when
deduction, based upon the law of mass action, as it is, should ultimately be found not to be in accord with the facts.
The Conductivity of Organic Acids and the Determination of Dissociation Constants.
The conductivities of from two to three hundred of the more common organic acids have been measured by
Ostwald,
thousand
this
even
at dilutions ranging
The general
litres.
from a few
litres
fact established
by
to
this
two or three
work is that
whole
1
Ibid. 18,
Van't Hoff: Ztschr. phys. Chem. 18, 300 (1895). Kohlrausch
662 (1895). Bancroft Ibid. 31, 188 (1899).
2
8 Ibid.
Ibid. 3, 170, 241, 369 (1889).
2, 840 (1888).
Bethmann Ztschr.
See Lellmann Ber. d. chem. Gesell. 22, 2101 (1889).
Ann.
D. Berthelot
Ibid. 6, 289 (1890).
phys. Chem. 5, 385 (1890). Bader
:
23, 5 (1891).
Walden
Ztschr. phys.
Chem.
8,
433 (1891)
416
c.
a)v
(1
The value
with
The
all
that
is
has a greater influence than in the meta position, and in the meta
For further details
position a greater influence than in the para.
reference must be had to the tabulated statement which has been pre1
pared by Ostwald.
Basicity of an Acid determined Empirically from its Conductivity.
empirical relation between the rate of increase in the conduc-
An
tivity of the
sodium
dilution of 1024
Hofmann:
77, 5 (1900).
Ztschr. phys.
Chem.
Drucker: Ibid.
Ztschr. phys.
Ibid.
1,
Ibid. 2,
Chem.
105 (1887)
901 (1888).
3,
2,
418 (1889).
902 (1888).
Wegschneider
ELECTROCHEMISTRY
417
68.4
1024
78.8
10.4
difference
= 10x1
fJiV
32
69.2
1024
90.0
20.8
difference
= 10 x
ftV
32
82.1
1024
113.1
31.0
difference
10
x3
= 10
x 4
= 10
x 5
nv
32
80.8
1024
121.2
~4O4
difference
77.7
1024
127.8
50.1
difference
An
elaborate piece of
2,
49 (1888).
2E
418
number
The conductivity
also
of salts of a large
measured by Bredig.
We
have
Migration Velocities of the Complex Organic Anions.
seen from the law of Kohlrausch that the conductivity method can
be used to determine the velocities of ions. The value of
for a
compound
is
the value of
sum
the
we
cations.
Ostwald 1 has arrived at general conclusions from his measurements as to the effect both of composition and constitution of the ion
on its velocity. The effect of increasing complexity is illustrated by
the following example
VELOCITY
HCOO
Anion of acetic acid, CH 3 COO
Anion of propionic acid, CH 8 CH2 COO
Anion
of formic acid,
65.9
43.1
39.0
its
velocity
becomes smaller.
When
as is
VELOCITY
Anion
of acetic acid,
Anion
of monochloracetic acid,
Anion
of dichloracetic acid,
CHCiaCOO
40.1
Anion
of trichloracetic acid,
CC13 COO
37.5
The
CHlcOO
effect of constitution
isomeric ions.
CH 2 ciCOO
42.0
The following
results
....
43.1
Ztschr. phys.
Chem.
2,
848 (1888).
ELECTROCHEMISTRY
f
.....
Anion
of butyric acid,
Anion
of isobutyric acid,
41 9
> CHCOO
of orthonitrobenzoic acid,
Anion
Anion
_ /N0 2
C 6 H4\
34 5
\coo
acid,
C 6 H 4\
of orthoamidobenzoic acid,
_
C 6 H 4<\
of metaamidobenzoic acid,
C 6 H4<T
Anion of paranitrobenzoic
35.4
35 Q
C/HS/
Anion
VELOCITY
\coo
/NH2
34 8
(<>)
.
.35.7
\COO
34 6
\COO
Other relations were pointed out by Ostwald for the organic
anions, but for these his original paper must be consulted.
The velocMigration Velocities of the Complex Organic Cations.
ities of many organic cations were calculated from the conductivities
was determined
by the conductivity
subtracted, and the re-
directly
Ammonium,
NH4
Methylammonium,
must
..........
CH8 NH8
Ethylainmonium, C 2 H 5 NH3
.....
.....
.--
VELOCITY
70.4
67.6
.46.8
Isomeric ions which have analogous constitution have approximately the same velocities.
Propylammonium, CH CH CH 2 NH8
C* W
3
Isopropylammonimn, ^
>CH - NH8
3
\.
~h
......
......
VELOCITY
40.1
40.0
LOG.
tit.
420
The
effect of constitution
may
in
....
36.2
38.2
move the
faster.
VELOCITY
Methyldiethylammonium,
CH
(C 2 H5)2NH
35.8
38.2
The
effect
1
of pressure on the conductivity of solutions was studied
by Fanjung.
The pressure was produced by means of a Cailletet pump.
should
We
expect that whatever the effect of pressure on the amount of dissociation of the compound, it would increase the friction on the ions as
conductivity.
This
is
is
:
increased by pressure.
ELECTROCHEMISTRY
421
solutions,
with
we seem
to be justified in
Measurements
peratures.
of the conductivity of aqueous solutions of a number of
up to 100, have
1
by Schaller.
has also measured a
substances,
been
made
Kraus 2
number of conductivities of
potassium iodide in methyl
far,
in
workers.
In carrying
out
this
Fia. 58.
Ztschr. phys.
Chem.
89 (1904).
8 Ztschr.
phys. Chem. 46, 323 (1903).
*Phys. Rev.
18, 40,
422
held in place by a large steel nut (7. The bomb is lined internallywith sheet platinum about 0.41 mm. thick. The cover is made tight
by a small packing ring of pure gold wire, which fits into a shallow
is
V-shaped groove.
The wall
of the
bomb
The second
elec-
is
num
forcing the ridges of the crystal into the soft gold, and making the
joints tight.
The
object of this
is
twofold.
It serves to
show from the conductivity that the bomb is not completely filled
with the liquid, and it furnishes a means of measuring the volume
of the solution in the bomb.
The bomb must never be filled with
the solution at ordinary temperatures, since it will not withstand
the liquid pressure at the higher temperature
only the vapor pressure.
The specific volume of the solution at the temperature in
question must be determined in order to calculate the equivalent
from the observed conductivity.
The small platinum tube T' serves to exhaust the air from the
bomb.
is
well
platinized.
The
gold,
solution, then,
and quartz
peratures
The above
is
and from
ELECTROCHEMISTRY
423
In the later work the bomb was rotated, thus thoroughly stirring
the solution.
Noyes and
his coworkers
are
nitric,
sulphuric,
the different
Some
substances
dilution
tivity.
AO,
and in the
third, the
424
The
Discussion of Results.
results
of X for
the binary electrolytes become more nearly equal with rise in temperaThis indicates that the specific migration velocities of the
ture.
is
known
rise in temperature,
which
at lower temperatures.
The conductivity
rising temperature.
It should also be noted that the fluidity of water
the same increase with rise in temperature, as the
shows nearly
conductivity
That the
effect of
temperature on dissociation may be clearly seen, the percentage of dissociation of most of the substances investigated at the
different temperatures is given for the dilutions 0.01 and 0.08
rise in
normal.
It will be seen that the dissociation decreases regularly with rise in
This holds for all of the substances except water up
temperature.
to about
The
the strongly dissociated compounds of the same type. If the dissociations are equal at ordinary temperatures, they would be very
nearly equal at the more elevated temperatures.
It will be seen
from the
The
temperature.
The decrease in the dissociation of hydrochloric and nitric acids,
and sodium hydroxide, is about of the same order of magnitude as
that
shown by binary
salts,
ELECTROCHEMISTRY
PERCENTAGE OF DISSOCIATION
SUBSTANCE
425
426
are
They
1
by him as
defined
fol-
"
containing a
common
ion
Given two weak monobasic acids dissolved in water, they are partially dissociated.
first
acid
acid.
From
=c+
M M
'
2 Ibid.
c'.
ELECTROCHEMISTRY
427
The discovery of the nature of isohydric solutions is of considerable importance in physical chemistry.
It comes into play especially
in connection with problems in chemical equilibrium, and the conditions which must be fulfilled in order that equilibrium may exist.
The Condition
tion
etc.,
saltsj
made
difference can be
compound
K CdI
2
clear
K + K + Cdl
much
less
method to
this
well. 8
1
The general
down
Ztschr.phys. Chem.
6,
97 (1890).
Ztschr. phys.
See MacGregor Phil. Mag. 41, 276 (1897)
33, 529 (1900).
Chem. 23, 374 (1897). MacGregor and Archibald: Phil. Mag. (5) 45, 151
:
428
The question
is
it
specific
very important.
They devised a
the molecular conductivities being expressed in reciprocal ohms, to show the order of magnitude of the conductivity
of fused salts.
are
given,
ELECTROCHEMISTRY
429
consulted.
Faraday regarded water as playing no essential part in electrolysis, and naturally drew the conclusion that 'his law also held for fused electrolytes.
He, however,
verified this conclusion experimentally.
Among
this
nearly obtains, that we seem justified in concluding that this generalization holds for fused electrolytes, probably as well as for solu-
tions of electrolytes.
If Faraday's
to find a
with fused
ment
this
silver iodides.
Considerable
4
problem by Lehmann
He showed
that there
in connec-
is
a move-
of the ions,
5
Warburg
cations move during
least the
electrolysis.
These results
all
Ztschr. anorg.
(1904).
8 Ztschr.
phys.
4
5
Chem.
430
Sedate."
Salts.
It is well
known
that fused
high temperature ?
This problem is not a simple one, on account of the difficulties
involved in determining the velocities of the ions at the high temperaThe first attempts in this direction were made by Lorenz, 3
tures.
while Gordon 4 resorted to the measurement of the electromotive force
of certain types of concentration elements, in which the solvent was
a mixture of fused potassium nitrate and sodium nitrate, and the
the latter being used at different
dissolved substance silver nitrate
He concluded from his measurements that the dis50 per cent solution of silver nitrate in the fused
while pure fused silver nitrate is about 58
solvent is 69 per cent
Similar measurements haye been made by
per cent dissociated.
concentrations.
sociation of a
!Davy
507.
(1901).
2
Warburg Wied. Ann. 21, 622 (1884). Foussereau Ann. Chim. Phys. [6],
Barus: Amer. Journ. Set. 37, 339 (1889). Warburg and Teget375
5,
(1885).
ineier: Wied. Ann. 32, 442 (1887); 35, 455 (1888).
Tegetmeier Ibid. 41, 18
(1890). LeChatelier: Compt. rend. 108, 1046 (1889); 109, 264 (1890); 110,
399 (1890).
:
Wesendonc
9,
854 (1902).
ELECTROCHEMISTRY
2
1
Lorenz, Suchy, and others.
The
results
431
In
all
is
complicated
by the
for-
them
in
making any
final
dis-
normally its conductivity increases slowly with increasing temperature above the melting-point, but for a long distance below the
;
melting-point the conductivity decreases very slowly. The conductivity does not decrease rapidly until a temperature as low as
160
is
reached.
DISSOCIATING ACTION OF
Modes
of Ion Formation.
the impression might be gained that ions can be formed from molecules in only one way
the molecules breaking down directly into
Lorenz
2 Ibid.
27,
8
Ztschr. anorg.
152 (1901).
Chem.
Weber
19,
:
cations.
283 (1899)
This
is
one
way
*
Phys. Eev. 24, 77 (1907).
5, 353 (1899).
Wied. Ann. 17, 642 (1882).
" Electrical
Conductivity of Hot Salt Vapors."
See Smithells, Dawson, and Wilson Ztschr. phys. Chem. 32, 302 (1900).
Ztschr. Elektrochem.
in
432
which ions are formed, and the way with which we are most familiar,
since it occurs most frequently.
The following examples illustrate
this
mode
of ion formation
H S0 = H +H + SO*
Ba(OH) = Ba + OH + OH,
K S0 = K +K +8^.
= H +01,
NaOH = Na + OH,
KN0 = K + N0
HC1
\1.
3,
formation.
Cu
+ S0 +
is
Zn
= Zn + S^ + Cu.
the zinc.
zinc
is
This
is
H,C1
+ H, 01 + Zn =
Zn
+ 01 + 01 + H
2.
What
is essentially
is
sub-
ELECTROCHEMISTRY
433
stance passes over into a cation, at the same time that an atom of
another substance passes over into an anion. When gold is dipped
into chlorine water, both the gold and chlorine are in the atomic or
But under these conditions the gold can beand the chlorine can form anions. This we will term
the third method of ion formation.
molecular condition.
come a
cation,
Au +
3.
This
is
Cl
+ Cl + Cl = Au + 01 + 01 + Cl.
water.
The fourth and last method by which ions are formed is where
an atom passes over into an ion, at the same time converting an ion
already present into one with a different quantity of electricity upon
it.
Thus, chlorine brought in contact with ferrous chloride in solution forms an anion, at the
into a ferric ion.
++
Fe
4.
This
is
+++
+ C1 + Cl + Cl = Fe + Cl + Cl + Cl.
istry, oxidation.
shall see that they throw much light on many problems in chemistry,
the meaning of which has hitherto been concealed in darkness.
The Dissociating Power of Different Solvents.
Frequent reference has been made to the power of water to dissociate molecules
into ions.
From
is
We
The same
methods
are available,
at
least theoretically,
for
measuring dissociation in non-aqueous solvents, as have been employed with water. These are, as will be remembered, the freezing1
See Lehrb.
d.
Allg.
Chem.
II, 786.
434
point, boiling-point,
proved
dissociation
know
bered,
To determine
it is
necessary to
know both
//,
and
fji^.
completely dissociated is so great that the conductivity method cannot be applied to it. To determine the value of p,v in such solvents
it is
necessary to
The
dissociating
Inorganic Solvents.
stant of liquid hydrocyanic acid, and found the very large value of
95 at 21
that of water being about 80 at the same temperature.
Centnerszwer 3 showed that liquid hydrocyanic acid has greater dissociating power than any other known solvent.
The dissociating power of water has been measured by a variety
of methods, including the conductivity
1
4
of Kohlrausch, the
Jones Ztschr. phys. Chem. (Jubelband zu Van't Hoff), 31, 114 (1899).
Journ. Phys. Chem. 5, 157 (1901).
*
Ztschr. phys. Chem. 39, 217 (1902).
Wied. Ann. 26, 160 (1885).
:
method
ELECTROCHEMISTRY
435
freezing-point
Nernst,
Noyes.
that water
is
al"
to be a very
strongly dissociating solvent. He studied the conductivity of certain alkaline nitrates in nitric acid with the above result.
of
Bouty
2
8
Ztschr. phys.
Ztschr. phys.
Chem.
Chem.
11, 110,
*
6
436
in liquid iodine
as the solvent, obtaining results that are quite different from those
found by Platnikow 2 in liquid bromine. The electrodes were made
grams of the
salt in
fail-
of a
number
of salts
in this
solvent.
Walden 3 has
erable
power
also
shown that the following solvents have considdown into ions Sulphur dichloride,
to break molecules
sulphuryl chloride,
oxychloride, arsenic
tribromide,
antimony pentachloride,
silicon
tetrachloride,
stannic
We
while phosphorus oxychloride has marked dissociating power. Antimony pentachloride has very little dissociating power, while the
trichloride has considerable power to break molecules down into
ions.
Walden 4 extended
ganic solvents
his investigation also to the following inorArsenic tribromide, dimethyl sulphate, chlorsulphuric
1
Ztschr. phijs.
Ibid. 48,
Chem.
220 (1904).
ELECTROCHEMISTRY
add, and sulphuric
acid.
The tribromide
437
able
power
The other three
slight dissociating power, liquid hydrocyanic acid has greater dispower than even water itself. This is in perfect accord
sociating
with the
employed.
They
by
reaches are, to say the least, surprising. For details reference must
be had to the original paper.
Oddo 5 has also shown that phosphorus oxychloride strongly
7
6
Tolloczko,' as well as Garelli and Bassoni,
with the halides of arsenic and antimony, showing them to
ionizes electrolytes.
worked
have ionizing power. Centnerszwer 8 is authority for placing cyanogen among the solvents that have little or no dissociating power.
Franklin and Farmer 9 have also shown that nitrogen peroxide does
1
6
7
8
Chem.
*
Ibid. 43, 386 (1903).
Ztschr. phys. Chem. 30, 705 (1899).
Atti. E. Accad. dei Lincei, Roma (5) 10, 256.
438
An
and hyriodic
acids,
They found
The following
relations exist
show what
and
dielectric constants,
ASSOCIATION
CONSTANT
FACTOR
Hydrocyanic acid
95
Water
81.12
3.7
Ammonia
16.2
1.0
Sulphur dioxide
13.75
1.0
1.7-1.9
Arsenic trichloride
12.35
Arsenic tribromide
Q-T--^
Nitric acid
13.9
Phosphorus oxychloride
Antimony
33.2
trichloride
Thionyl chloride
Sulphury 1 chloride
Dimethyl sulphate
Chlorsulphuric acid
Sulphuric acid
Sulphur monochloride
1.00
?
9.05
1.08
9.16
0.97
32.0
4.8
0.95-1.05
3.18
1.2-1.3
Cyanogen
2.52
Sulphur trioxide
3.56
Boron
Phosphorus trichloride
Phosphorus tribromide
3.36
1.02
Antimony pentachloride
3.78
1.06
trichloride
Silicon tetrachloride
Tin tetrachloride
The
Hydrogen sulphide
Nitrogen peroxide
values for
searches of
1
3.2
Ramsay and
Shields,
2
ELECTROCHEMISTRY
439
those for the dielectric constants are almost wholly taken from the
work of Turner. 1
Organic Solvents.
large
is
carbons in general.
3
studied
Fitzpatrick
the
and found
in methyl alcohol,
number of salts
was less than in
4
5
Paschow, Vollmer, and
conductivity of a
that,
although
it
water,
solvent.
Carrara. 7
number
same
conditions.
We
14
Kawalki,
and
Schall. 15
of methyl.
Schlamp
propyl alcohol
is less
Carrara
19
5,
503 (1897).
10
19
Gazz. chim.
14
"
ital. 27, 1,
440
Schall
taneo
and Kablukoff. 4
is
that of Cat-
in ether have a
6
6
is
SuUt
$oc Chim
.
(3 ) 19? 32 i (1898).
ELECTROCHEMISTRY
441
Werner
It is, however, to
pyridine and found considerable conductivity.
2
St. v. Laszczynski and St. v. Gorski that we owe most of our knowlFor the determination
edge of the dissociating power of pyridine.
of molecular weights in pyridine we must consult the work of Waiden and Centnerszwer. 3
So few measurements have been made
Other Organic Solvents.
in
other
organic
reference.
brief
compounds belonging
to
classes:
acid
He
dielectric constants,
relations of interest
and importance.
Walden 9 has
1
2
3
list
Ztschr. anorg.
Beibl. Wied.
68,
479 (1907)
50, 192,
442
large
of empirical relations were established.
These investigations of Walden and his coworkers have probably
thrown more light on the dissociating power of organic and inor-
number
ganic solvents in general, than all the other investigations that have
ever been carried out on this problem.
Apparently Abnormal Results obtained in Non-aqueous Solvents.
On
to
2
8
ELECTROCHEMISTRY
POTASSIUM BROMIDE
443
444
allowed that one associated liquid diminishes the association of another associated liquid with which it is mixed.
Since dissociating
power
is
it
follows that
25*
100*
75*
50*
Concentration of Alcohol
FIG. 59.
and
1024.
such a mixture would dissociate less than the pure solvents and
the conductivity in such a mixture would be less than in the pure
;
solvents.
We must
ELECTROCHEMISTRY
445
maximum
of
mixed were measured; and also the viscosities of solutions of calcium nitrate in the pure solvents and in the mixtures. The conductivities in the mixtures of acetone and water show the minimum
already referred to, and this is very closely connected with the
maximum
One
important facts
es-
calcium nitrate, in
mixtures of acetone
show a very
maxi-
pronounced
mum in
conductivity.
This
was shown not to be
due to any marked
(See Fig. 60.)
increase in dissociation
such mix-
in
but
tures,
size
of
to
diminution in
the
the
ionic
it
100*
FIG. 60.
through
the solution.
would move
25*
75*
50*
Percentage of Acetone
The
faster,
446
ATO
40
15
ID-
S'
50*
25*
75*
100*
Percentage of Acetone
FIG. 61.
the
maximum
is
correct.
to the
volumes
There
is
McMaster worked with the same solvents that had been used by
Bingham, and with binary mixtures of these with one another. As
He
electrolytes he used lithium bromide and cobalt chloride.
studied both conductivities and viscosities.
In mixtures of water
with the alcohols and acetone he found again the conductivity minimum, which was closely connected with the viscosity maximum.
The conductivity maximum was found by McMaster
(See Fig. 59.)
in the mixtures of the alcohols with acetone.
This was shown to
be due to the change in the size of the spheres about the ions.
Cobalt chloride in the 75 per cent mixture of acetone with methyl
alcohol,
ELECTROCHEMISTRY
447
It is interesting to note that a zero temperature coefficient of conductivity was found for a solution of cobalt chloride in a 75 per cent
and acetone, and in binary mixtures of these solvents. The minimum was found to be a more general phenomenon than had hitherto
been supposed. The explanation was found for the increase in viscosity
on mixing water and alcohol. These are both strongly associated
The work of Jones and Murray had shown that each diliquids.
minishes the association of the other.
breaks
down
down
size.
Now,
it
is
maximum
why
sum
of
di-
with increase in dilution, and, consequently, the conducfor the different dilutions would approach one another
curves
tivity
as they approach the minima.
Pact and theory are here in perfect
sociation,
accord.
The maxima,
in conductivity were
448
minima
in viscosity.
These minima in viscosity are due, as has
been shown, to an increase in the size of the molecules of the solvent.
This is caused by a combination of one solvent with the other. The
of the
it
Why
pure water.
The explanation l
above-named cations
is
the
movement
of the mole-
elementary cations ?
If we turn to the well-known atomic volume curve (page 29) we
see that potassium, rubidium, and caesium occupy the maxima of
the curve, and have much larger atomic volumes than any other
elements. Even the atomic volume of potassium, which is
smaller than that of rubidium and caesium, is much larger than that
of any other known element except rubidium and caesium.
known
ELECTROCHEMISTRY
If
449
we
tory.
tration
test this relation quantitatively, the result is very satisfacBy comparing the viscosities of solutions of the same concen-
we
chloride.
Mixed
Solvents," by
H.
C. Jones
and
and
5
Shields, that in many liquids the molecules are not the simplest
possible, but are aggregates of these simplest molecules of various
1
2
8
6
Jones-
and Veazey
Ztschr.phys. C7iem/(1907).
320 (1893).
4
Ztschr. phys. CVm., 13, 5.31 (1894).
Compt. rend. 125, 240 (1897).
Ztschr. phys. ChM'12, 433 (1893).
Phil.
Mag.
2G
36,
450
a solvent
is
not polymerized at
all, its
There
is
on the other hand, which have slight ionizing power show very slight
polymerization of their molecules.
Bruhl 2 attempts to go one step farther. He thinks that oxygen
is generally quadrivalent, and that water and other liquids containing oxygen are unsaturated compounds.
down
to
We
have seen
some extent
We have also
into
seen that
any chemical
activity.
*
Ztschr. phys.
Chem.
18,
514 (1895).
ELECTROCHEMISTRY
The
acids
first
ions.
We
we know
know that
bases,
and
salts
conditions
451
is
This is due
entirely in the molecular condition free from ions.
the
of
of
to
trace
water
from the
removing
every
difficulty
chiefly
presence of substances, and wherever water is present we are liable
to
it
results
will
be given.
1
Wanklyn showed
lic
sodium.
ordinary
3
Hughes demonstrated
that dry hydrochloric acid does not decompose carbonates to any appreciable extent.
Marsh 4 has shown that pure sulphuric acid, free from every
Similar results
trace of moisture, has no action on blue litmus.
have been obtained with dry hydrochloric acid.
5
Hughes found that dry hydrogen sulphide does not act on dry
metallic oxides, and does not precipitate a solution of mercuric
chloride in absolute alcohol.
It should be
which
chloride
is
water.
salts
by
by
are,
'
cit.
452
to
air,
which
it
it
was
insufficient.
we can say
that nearly
all, if
not
all
chemical
reactions are due to ions, molecules as such not entering into chemical action.
The molecules which are present gradually dissociate
as the reaction proceeds, and furnish ions which then react.
can now see why inorganic reactions in general proceed to
We
the limit rapidly, while organic reactions take place much more
Inorganic compounds, including the strong acids and
slowly.
bases, and salts, are in general strongly dissociated substances.
The ions are already present and they react very rapidly. Organic
compounds, on the other hand, are weakly dissociated. There are
when
It has long
of the Metals.
1
Journ. Chem. Soc. 65, 611 (1894).
*Lieb.Ann. 299, 1, 267 (1898).
3
*
ELECTROCHEMISTRY
453
ment, they no longer have the properties that they usually possess.
As early as 1790 Kier l observed that when iron is dipped in nitric
acid having a specific gravity of 1.45, it becomes passive, i.e. it is no
longer attacked by dilute nitric acid. Further, it no longer has the
power to precipitate metallic copper from a- solution of a copper salt.
We
number
of the metals.
since the
disturbed.
Thd same fate has befallen the theory that passivity is due to the
formation of a protective layer of gas over the surface of the metal.
The two views of passivity that have acquired the greatest prominence are those of Finkelstein 3 and Hittorf. 4
According to the
This conformer, active iron is bivalent and passive iron trivalent.
clusion was based upon the difference in potential between iron
electrodes and the iron salt in which they were immersed. The
potential difference depends upon whether the iron salt
ferrous or in the ferric condition.
the
is in
Hittorf also points out that in the case of chromium, the passive
condition corresponds to the highest valence, and the active to the
lower valence. He thinks that we have to do with two allotropic
modifications of the elements, one of which
is
active
not.
Amer. Journ. Science, 34, 419 (1887). Houlle408 (1898). Mtiller: Ztschr. phys. Cham. 48, 577
Sackur Ibid. 54, 641 (1906). See Ostwald Ibid. 35, 33 (1909) 35,
(1904).
Ruer Ztschr. Elektrochem. 14,
204 (1900). Brauer: Ibid. 38, 441 (1901).
See Nichols and Franklin
7,
2
8
Ztschr. phys.
Chem.
39, 91 (1901).
454
FIG. 62.
The apparatus
is
is
potential.
By this means differences in potential can be measured
to a few thousandths of a volt.
Ostwald has given the Lippmann
ELECTROCHEMISTRY
The
form
455
microscope, which
is
is
employed
by
On
the box
is,
The
total resistance of
ohms.
number
of normal
ele-
these
FIG. 63.
It
The
is
best
known
of
consists
mercury over
of
which
is
electromotive
force
of
1.4328
volts
- 0.0012
(t
15), t being the temperature at which the
element is used. The objection to this element
is
that
its
temperature coefficient
is
so large.
It consists of
100
456
into
1.0186 volts.
volt element
Upon
prepared as
is covered
Mercury
chloride having the specific gravity 1.409, and into this solution is
dipped a bar of amalgamated zinc. Its electromotive force at ordi-
The measurement of
electromotive force,
is
Fig. 65.
C,
An
ele-
and connected
ONE-VOLT-
ELEMENT
EARTH
FIG. 65,
with the two end plugs of the resistance box just described. There
is a definite fall in potential as the resistance increases from plug to
plug along the box. The element whose electromotive force is to be
measured is placed at E, and connected with the plugs in the box by
means
are
The caps
of metallic caps, which fit tightly over the plugs.
to plug, until the electromotive force to be
measured
is
Jager: Ann. d. Phys. (4) 4, 123 (1901); (4) 5, 1 (1901). Jager and
Lindeck: Ztschr. phys. Chem. 37, 641 (1901). Carhart Phys. Rev. 12, 129
Hulett: Ztschr. phys.
Hulett: Journ. Phys. Chem. 8, 190 (1904).
(1901).
Chem. 49, 483 (1904). Barnes and Lucas: Journ. Phys. Chem. 8, 196 (1904).
1
Ztschr. phys. Chem. 1, 406 (1887).
(1900).
St.
ELECTROCHEMISTRY
457
rent caused by the resistance in the box. This equality is established by means of the Lippmann electrometer.
These two equal
values, being opposite in character, completely compensate each
other, and there is no movement of the mercury in the electrometer.
into
by introducing a standard element
say a one-volt element
the secondary circuit, and moving the caps from plug to plug until
the electrometer shows complete compensation. Knowing the elec-
tromotive force of the standard element, we know the drop in potential produced by a given resistance in the box, since the two are
electrochemical standpoint.
It follows
from the law of the conservation of energy, that whenever one form
of energy appears, an equivalent amount of some other form disThus, when electrical energy appears in the cell, it is
appears.
at the expense of the intrinsic energy of the substances present
in the cell.
It has already been pointed out that the best means
of measuring intrinsic energy, or better, difference in intrinsic
energy, is to transform this into heat and measure the amount
of heat developed,
reaction.
that in the
free during
cell, the intrinsic energy which becomes
the reaction passes over quantitatively into electrical energy. This
was shown first by J. Willard Gibbs, 1 in 1878, and a little later by
simplest form of
2
Helmholtz, not to be true in general. Indeed, it is true only in
very special cases. An element may either take up heat from the
1
Translated into German by Ostwald
Proceed. Conn. Acad.
namische Studien, p. 397. Leipzig, 1892.
2
1882.
ftitzungsber. Ber. Akad., February,
Thermody-
458
surrounding medium, or give out heat, and this must be taken into
The electrical energy produced in the cell is, then, equal
account.
The
TT,
and the
we have
term may be either positive or negative, but is more frei.e. the element gives out heat while it is working.
last
quently negative
now
turn.
method
is
The
of calculating electromotive
based
Nernst.
If
we
to another, the
ft
Pi
*Ztschr.phys. Chem. 4, 128 (1889).
See Lehrb. d. Allg. Chem. II, p. 825.
Ztschr. phys.
Chem.
ELECTROCHEMISTRY
459
weights
J'
Pl
RTln
P2
the work obtained from an ideal solution under the same conditions
that is, a solution of volume v passing isothermally from an osmotic
;
pressure
to an osmotic pressure
p2
We
external
work
far,
how
to calculate the
maximum
when
Knowing
the
electrical' energy,
the
electromotive force?
Electrical energy, like every other manifestation of energy, can be factored into an intensity and a capacity
factor.
The intensity factor of electrical energy is the electromotive
force or potential, and the capacity factor the amount of electricity.
If
we
=. ire
call the
.
If
former
and the
TT,
we know
e,
we
* In
is
natural logarithm.
460
We
have
ve
This is the fundamental equation for calculating the electromotive force of elements, from the osmotic pressures of the electrolytes around the electrodes.
This equation has been very much simplified by Ostwald, by
introducing numerical values wherever it is possible.
R = 2 calories, and 1 calorie = 4.18 x 107 ergs. T, the absolute
temperature, can be taken as 290 C. for the average conditions.
7pm
= 0.0251 volt, since volt X coul = 107 ergs.
The constant
1
-e
= 0.0251 In ?L
Pz
= 0.058 log
P2
1
See Lehrb.
d.
Allg.
Chem.
II, p.
827.
ELECTROCHEMISTRY
where
log. is
461
cases,
we must
We
This pressure
pressure.
'
at the
what
which thus becomes negative. The solution beof the positive ions which it has received.
because
positive,
At the plane of contact of the metal and solution, there is formed
the metal
itself,
comes
much
earlier
2
The positively charged ions in the solurecognized by Helmholtz.
tion and the negatively charged metal attract one another, and a
The solution-tension of the metal
difference in potential arises.
tends to force more ions into solution, while the electrostatic attrac-
Wied. Ann.
7,
337 (1879).
462
is
established
before
is
of the metallic ions in the solution of the salt be p, then any one of
three conditions may exist. The solution-tension may be greater
than the osmotic pressure, less than the osmotic pressure, or just
equal to
it.
We may have
p>p,
P<P,
a)
(2)
P = p.
is
(3)
opposite charges.
" This double
layer has a component of force, which acts at right
angles to the plane of contact of the metal and solution, and tends to
drive back the metallic ions from the electrolytes to the metal.
*
acts in direct opposition to the electrolytic solution-tension."
The
condition of equilibrium
is
reached
when
It
forces just equalize one another and the final result is the existence
of an electromotive force between the metal and the solution, the
;
many ions
into a solution
of its salt as into pure water, because the osmotic pressure of the
metallic ions already in the solution acts against the solution-tension
of the metal.
Let us now take the second case where the solution-tension of the
is less than the osmotic pressure of the metallic ions in the so;
metal
ELECTROCHEMISTRY
463
Metallic ions will separate from the solution upon the metal.
passes over into an atom it gives up its positive
lution.
The
we have again
metal,
it
gives
it
lost
metal
is
motive force exists here, also, between the metal and the solution,
but in the reverse direction from the case first considered.
tablished.
the solution.
is
now we inquire which metals have high, and which low solutiontensions, we shall find that magnesium, zinc, aluminium, cadmium,
iron, cobalt, nickel, and the like are always negative when immersed
in solutions of their own salts.
This means that the solution-tension
If
of the metal is always greater than the osmotic pressure of the metal
ion, in any solution of their salts which can be prepared.
If, on the
is less
When
We
Substances which
to drive the metal over into cations.
can pass over into anions have also a solution-tension, as is pointed
out by Le Blanc. 1 If the chlorine ions in a solution had an osmotic
which tends
Lehrb. Elektrochemie, p. 121. See also Lehfeldt Phil. Mag. (5) 48, 430
Ztschr. phys. Chem. 32, 360 (1900)
Kriiger Ibid. 35, 18 (1901).
(1899)
464
pressure which was greater than the solution -tension of chlorine, the
chlorine ions would pass over into ordinary chlorine.
But Le Blanc
adds that, as far as we know, all substances which can yield negative
ions have a high solution-iension.
Demonstration of the Solution-tension of Metals.
demonstra-
1
by Palmaer.
Mercury
when
is
in contact
N0
cer-
When
N0
the top to the bottom of the solution. The solution will thus become
more concentrated just above the layer of mercury on the bottom of
the vessel.
fine glass
electrode.
tube from which mercury flows is known as a dropin concentration sufficient for the
To produce changes
7,
ELECTROCHEMISTRY
465
Under these
cury salt, and containing mercury at the bottom, since there would
be too much commotion in the solution. The arrangement which
is shown in Fig. 66.
The drop-electrode
into the funnel-shaped vessel 0, which
was used
T dips
is
Palmaer gives data which show that the concentration above had been diminished as much
as fifty per cent,
as forty per cent.
ment was
FlG 66
-
tried.
'
The difference in potential between a metal of solutiontension P, and a solution of one of its salts in which the metal ion
has an osmotic pressure p, can be calculated as follows:
Solution.
When
a substance of solution-tension
osmotic pressure
no work
stance of solution-tension
maximum work
P is
is
done.
to be obtained is the
Now we
have seen that the gas laws apply to the osmotic pressure
and the amount of work can be calculated from a gas in
from
If we deal with a
to gas-pressure p.
passing
gas-pressure
to be
this
we
have
seen
gram-molecular weight,
(p. 447)
of solutions,
RTln-.
p
See Braun: Wied. Ann. 41, 448 (1890).
Meyer: Ibid.
466
We have
work
for
work
amount
gram-molecular quantities,
is
The
an isothermal transformation.
electrical
If
of electricity.
we
it is 7rveQ .
P
the ions are univalent, v
or, if
if
= 1, when we have
= RT,In P
e
Now we
-=
~pnp
0.0251 volt.
Passing
e<>
from natural
The
T = 290,
TT
= 0.058 log -
We
time
it is
it is
inconstant.
these
termed reversible. This applies to elements in which the electrodes are immersed in solutions of their salts. Take as an example
is
When a current is
that the zinc dissolves and copper separates.
passed in the opposite direction, copper dissolves and zinc separates.
But neither process changes the nature
of the
cell.
ELECTROCHEMISTRY
If the electromotive force
is
467
is
passed in
We
Two bars
immersed
in
two zinc
electrical.
of
of the
The
solu-
action of the
such as to make the two solutions become more and more nearly
same concentration. The more dilute solution becomes more
concentrated, and the more concentrated more dilute, until when the
two become equal the element ceases to act. Zinc then passes into
solution in the more dilute solution, and zinc ions separate as metal
on the bar from the more concentrated solution. The electrode in
the more concentrated solution is always positive, since metallic
ions are giving up their positive charges to it and separating as
metal upon it. The electrode in the more dilute solution is negative, because ions are passing from it into the solution, and carrying
In
with them positive charges which come from the electrode.
an element of this kind the current always flows on the outside
from the electrode which is immersed in the more concentrated
solution.
The
is
is
just
what we should
expect.
The
cell.
solu-
The
osmotic pressure of the zinc ions is, of course, greater in the more
concentrated solution. The osmotic pressure, which works directly
against the solution-tension, will cause the ions to separate from the
solution in
which
The electromotive
468
TT
is
P RT,In P = ET,Inp
= MT,In ---ve
Here v
p2
ve
ve
pi
p and p2
l
p2
the osmotic press-
we
The
--a
If
a,
is
s*
The
c-f
is
then,
lyte.
We have
TT
or,
+a
+av
ve
p2
^--'0.0002
According to this formula, the only variables are p and p2) the
osmotic pressures of the cation in the two solutions around the
The electromotive force of such elements should deelectrodes.
pend only upon the relative osmotic pressures of the solutions, and
not upon the absolute osmotic pressures. This has been found to be
true.
The electromotive
kind of zinc
salt used,
same number
ELECTROCHEMISTRY
469
remain unchanged, and again such is the fact. The reason for this
by examining the last equation, since it is only
the osmotic pressure of the cations which comes into play
the
anion having nothing whatever to do with the electromotive force of
will be seen at once
the element.
The electromotive
force of a
number
we
are considering has been measured, and to within the limits which
could reasonably be expected, has been found to agree with that
calculated from the above equation.
To calculate the electromotive
c and a, the relaforce, a number of quantities must be measured,
tive velocities of cation and anion, must be determined; similarly,
p and p
agreement
is
The following
to one
470
In the
we must have
latter case
and
two sides of the
cell.
The
more concen-
The potassium
ions
move with
the element, and form potassium chloride with some of the chlorine
which was there in combination with silver as silver chloride. This
electrolyte.
The electromotive
calculated in a
TT=
As
RT,In P
ET,
ve
ve
p2
In
P =-RT, p
In.
l
pl
ve
p2
metallic
ELECTROCHEMISTRY
471
flow, a
and
If
we
represent the
The change
+a
and
a,
+a
would
be, of
course,
This factor,
+a
+a v
ve
-'
p2
0.0002
T log S
Pz
472
"
culated from the preceding formula, and " ir found is the electromotive force of the combination, as measured by Nernst.
I
SOLUBLE ELECTROLYTE
ELECTROCHEMISTRY
The
Theory of the Liquid Element.
the liquid element we owe to Nernst. 1
473
first satisfactory
What
is
theory of
the source of the
form distribution of ions. The region which is positive must conan excess of cations, and that which is negative an excess of
tain
anions.
found
TJie cause
is to
be
rapidly than chlorine, and will tend to separate from the chlorine.
But the positive ions cannot separate from the negative ions without producing a separation of the two kinds of electricity.
There
velocity.
centrated.
it is
quantitatively.
474
more
dilute solution,
c
move
-\-
current,
and
C
+a
of a gram-equivalent of anions
{*
of cations have
less osmotic pressure.
But
c
+a
+a
of anions have
moved from a
-?-RT
c +a
total gain is the difference
is
P
\n -L
p2
+a
The
of greater to one of
p2
electrical
ire
energy
we have
pi
= c-aRT,In;
c+ a e
p
2
*r
or,
^
c
+a
0.0002
log*!.
*p2
site direction.
member
tromotive force.
It
is,
v_j? 00002
c
+a
ft
*p 2
ELECTROCHEMISTRY
475
Nernst prepared liquid elements and determined their electromotive force. He then calculated the electromotive force from the
above equation, and compared the values found experimentally with
those from calculation.
1234
referred to
was constructed
10
100
100
n
10
n
10'
The potential differences at the ends are equal and opposite, and
The four differences in potential
therefore equalize one another.
which must be taken into account are indicated above. But the
potential differences are dependent upon the relative, not upon the
absolute osmotic pressures. The potentials at 2 and 4 are, thereThis
fore, equal and opposite, and can also be left out of account.
and
3,
method already
p and pl
ions in the
P_ ==
P^
Pi
Pi'
we have
.
This is the expression for calculating the electromotive force in
liquid elements like the above, where the valence of the cation is
the same as that of the anion. If they are different, we will repre-
476
by !>! and vj
become
by v and
v',
0.0002
T log*l.
Pi
means
If different
of calculating the
We may now
analyze more
closely the electromotive force in a concentration element' in the light of what we have learned about the liquid element.
Thus
far
we have
if
the only
sources of .the potential were at the points of contact of the elecAnd indeed this is practically true in the
trodes and the solutions.
cases of the concentration element
which we have
studied.
We have
it
usually small, it may, howassume proportions which must be taken into account.
is
We
We
and
trolytes.
?r",
ELECTROCHEMISTRY
of these
formulas
potentials
are
477
calculated
7r'
= 0.0002 T log-;
Pi
*"
=_ 0.0002 T log
Pa
= 0.0002
c
c
ion
a
a
+ TT")
(TT'
l;
P'2
'-^-log
c + a
PJ_
This must be the same as the equation already deduced (p. 456)
It will be seen to be the case, if we
consider that n = 2, and v for univalent ions equals 1.
for the concentration element.
t
We
we have thus
far
cell
remains unaltered,
the electrical energy produced in the cell must come mainly from
the heat of surrounding objects, which is converted into electrical
energy in the
cell.
There
is
transformed into
electrical,
1
p. 160.
or,
478
We
ele-
from the solution in the metallic form. The zinc electrode is therefore negative, and the copper positive; the current passing on the
outside from the copper to the zinc.
In calculating the electromotive force of the Daniell element, the
solution-tension of both the copper and the zinc must be taken into
In the elements which we have thus far considered, both
account.
electrodes were of the same metal.
The solution-tension of the
metal was, therefore, the same upon both sides of the cell, and being
of equal value and opposite sign, it disappeared from the equation
for the electromotive force of the element.
Whenever the
electrodes
copper sulphate
2e
in
which
Pi
of the
two metals
ELECTROCHEMISTRY
479
Pi
electrical, is
known
as the oxidation
briefly.
1
at a Distance/' Ostwald described such phenomena as the followIf we have a solution of ferrous chloride in contact with a
ing.
an element.
It is not
come
experiment:
Two
beakers are
filled
each vessel, and are connected with each other through a galvanometer. The two beakers are connected by means of a siphon
filled with a solution of potassium chloride, and the ends loosely
stoppered with rolls of filter-paper. When the circuit is closed the
is
passing; and
it
flows in the
liquid from the ferrous chloride to the chlorine. Within the cell
the ferrous ion passes over into the ferric ion, and at the same time
An
sense.
tendency to
See Peters
480
immersed
we have
siphon.
lyte,
Ztschr. phys.
Lehrb.
368 (1901).
Chem.
(1901).
29,
d.
Chem.
Markousky
305 (1902).
Wulf
387 (1892)
29, 305 (1899).
See Heathcote Ztschr. phys. Chem. 37,
Ztschr. anorg.
Wied. Ann. 44, 457 (1891). Bauer
10,
Czepinski
Ibid. 48, 87 (1904).
:
Ibid.
Levi
Bose
(1902).
Gazz. chim. ital 35,
30,
:
Ibid.
1,
38,
391 (1905).
ELECTROCHEMISTRY
481
We
will take
out even a simpler case than the one given above.
first the simplest possible ease, where we have the same gas, say
up
hydrogen, over both electrodes, the hydrogen upon the two sides
being at different pressures.
The action of such an arrangement would be, as Ostwald shows,
to equalize the pressure of the gas on the two sides of the cell.
into solution as ions upon the side where it
under the greater pressure, and ions of hydrogen must separate
as gas upon the other side of the cell.
Upon the side where hydrogen atoms are becoming ions, they take positive electricity from the
electrode,
positive,
The electromotive
= RT In P
,
TT
ve
where
P is the
is
the difference in
p2
RT,In P
'
ve
PJ.
solution-tension of hydrogen,
press-
= O.OOQ2 r
a.
V
Since for the hydrogen molecule, v
TT
p2
= 2,
we have
Ostwald 1 has also calculated the electromotive force for a gasBut as this has been worked out
battery consisting of two gases.
much more fully by Smale, 2 we will turn to his work.
The
P
P
T be
is
^=0.0002 Tlog^.
Pi
Since the solution-tension of oxygen is negative,
7r2
= 0.0002
Tlog^?;
*i
Loc.
cit.
2i
Ztschr. phys.
Chem.
14, 577,
and
16, 662.
482
- 0.0002
0.0002
7T!
Pi
TT
= 0.002
+ 0.0002 T log
Tlog
Pz
Pi
The
theoretical consequences of this equation are very interestof the gases, are independent
2 , the solution-tensions
L and
ing.
electrolyte
and
seven
salts.
The
fact.
ELECTROLYTE USED
this
ELECTROCHEMISTRY
483
and
Electrolytes.
It is
obvious from our studies of the action of the primary cell, that when
a metal is immersed in a solution of one of its salts, there is established
a difference in potential between the metal and the solution. Indeed, we have seen that this is the chief source of the electromotive
The cause
We
made
484
platinum wire, Pt, passed into a glass tube and protruding beyond
This serves as one electrode. The
end, dips into the mercury.
other glass tube, t, passing through the cork, is filled also with the
normal solution of potassium chloride. The glass tube, t1} at the end
of the rubber tube, is inserted into the liquid whose potential
The metal serves
against a given metal it is desired to measure.
its
as
The electromotive
system
ured.
now meas-
Knowing
the
obtained at once.
the liquid in
electrode whose
If
the
potential
it is
desired
to measure, acts
ically
chem-
upon potassium
chloride, a solution of
some indifferent sub-
stance
FIG 67
is
between
Thus,
if
we were measuring
interposed
the
two.
and lead
two
electrolytes
would be very
small.
is
and
ELECTROCHEMISTRY
We
be 1.791 volts.
element
know
which
IT,
of this
expressed thus:
is
,-fIlnf.
2e
p
in
485
is
pressure of the
magnesium
(1)
Pi
We
the osmotic
however, that,
In
^=-0.56
volt.
Pi
we have
1.791=
In
2e
- = 1.231
or,
^+0.56,
volts.
^= 0.029 log-
But,
2<?
0.029
therefore,
log- =1.231
volts.
The
difference in potential
magnesium chloride
tion of
The
solu-
salts
in Ostwald's laboratory.
the results which he obtained
Neumann, working
are taken
from
METAL
486
The question
as to the effect
of the anion on the potential between the metal and the solution
was raised by Neumann. In addition to sulphates and chlorides,
The
acetates.
results,
If,
N0
however,
satisfactorily
explained.
and their solutions at different concenThese include the thallium salts of seventeen organic acids,
A few of his results are
inorganic acids, and the hydroxide.
given below.
SALTS OF THALLIUM
ELECTROCHEMISTRY
We
potential difference,
which we
ir=
will call
0.058
ne
log
*
TT,
is
487
have seen that the
expressed thus
P
,
p'
where ne
The
solution-tensions of
calcu-
lated from
was used.
The value
is
of the osmotic
taken as 22 atmos-
pheres.
.........
..........
.........
........
..........
.......
.........
..........
..........
..........
..........
ATMOSPHERES
Magnesium
10*4
Zinc
1018
Aluminium
3x
Cadmium
Iron
Cobalt
Nickel
Lead
Mercury
Silver
Copper
The Tension
10 18
106
10*
2x10
1x100
Series.
When
KH
10-w
10-"
KH
its
throw
occurs.
Thus, zinc
is
The
(1894).
488
Constancy of Solution-tension.
It
was supposed
which
"
increasing temperature.
So far as we know this holds for a given solvent, but does not
1
apply to different solvents. Jones has found that the solution-tension of metallic silver,
when immersed
in an alcoholic solution of
solved.
that
we would
expect,
dissolves
solvent,
as
we know they
consider
or has a
differently in,
If the substances
every solvent.
when we
do,
so
why
greatly
should
from solvent
not
substances
show
this
same
difference ?
2
Quite recently, Jones and Smith have shown that the solution8
is 10 times its solution-tension in ethyl
Chemical Action at a
has already been made to the paper by Ostwald on " Chemical Action at a Distance." Under that same head
he describes an experiment which must be referred to here. OstDistance.
Reference
wald begins his paper by calling attention to the fact that amalgamated zinc is not dissolved by dilute acids, but if the zinc is
surrounded by a platinum wire, it is dissolved by the acid. It is
not even necessary for the platinum wire to surround the zinc,
for if the wire touches the zinc at any one point, solution will take
place.
solution
He
2,
81 (1894).
ELECTROCHEMISTRY
sulphuric acid be added in order that the zinc
the acid ?
489
may
be dissolved by
If
we
we
hydrogen
number
when hydro-
is
when a
few drops of chromic acid are added to the platinum. Gold dissolves in sodium chloride, if chlorine is brought in contact with the
platinum.
Fill
Experiment to demonstrate Chemical Action at a Distance.
a beaker with a solution of potassium sulphate. Take a piece of
glass tubing about 10 cm. long and 2 cm. wide, and close the lower
end with vegetable parchment. Fit a bar of pure zinc, about 10 cm.
long, tightly into a cork which just closes the top of this glass tube.
Fill the glass tube with some of the same solution of
potassium
the cork closing the top of the
sulphate, and insert the bar of zinc
Around the top of the zinc bar above the cork wrap a
glass tube.
piece of platinum wire of sufficient length to reach nearly to the
bottom of the beaker, when the glass tube is introduced into the
beaker in the manner to be described Jiereafter.
The free end of
the platinum wire should be coiled upon itself a number of times, or
it is better if it is connected with a
piece of platinum foil a few
centimetres square, so as to expose a larger surface.
The glass tube is now immersed in the beaker until the surface
of the solution in the tube is only a centimetre or two above the
surface of solution in the beaker, the free end of the platinum
wire, or the platinum foil, being allowed to rest on the bottom of
the beaker.
490
More than
Free
them
Ions.
When the acid was added to the platinum, the presence of a current
was shown by the throw of the instrument.
The explanation of this phenomenon is perfectly simple, now
that we have the theory of electrolytic dissociation and are familiar
with
When
tension, a certain
is
thus
made
number
negative,
and the
solution,
The
zinc
posidifference in
tive
ions,
that
The
as the zinc.
When
the platinum
is
immersed
ELECTROCHEMISTRY
491
We
is
positive electricity from the hydrogen ions, conducts this over to the
The zinc becomes less negative than before the hydrogen
zinc.
separated as gas.
As Ostwald
acid
the solution of the zinc, but in the ease with which the hydrogen
can escape from the solution. The presence of a metal with small
solution-tension allows this to take place more readily, and this is
the reason that impure zinc dissolves in acids.
The reason why pure zinc does not dissolve in acids
is
because
fore,
is
up
its
492
and escape as gas. The zinc, because of its high solution-tension, and
because the hydrogen cations can so easily escape, then dissolves.
To repeat the essential steps in the explanation of the experiment described above Pure zinc immersed in potassium (or any
acid is added, or in a solution
soluble) sulphate, to which sulphuric
:
of pure sulphuric acid itself, does not dissolve because the zinc has
such a high solution-tension that the hydrogen ions cannot give up
into solution
the platinum
as long, therefore, as there are any hydrogen ions in
the solution to furnish positive electricity to the platinum.
Or, as
we are accustomed to express it, as long as there is any acid in contact with the platinum.
"
:
We
is
place because of galvanic currents between the zinc and the other
The galvanic currents
metals, is not in strict accord with the facts.
are inseparably connected with the process of solution, but they
are not the primary causes of the solution.
They are set up, rather,
of solution, which they must necessarily accompany,
since solution is a question of ion formation and disappearance.
If
it is possible for the
ions
in
to
positive
present
separate
any way
by the process
beaker a solution
An
Ztschr. phys,
Chem.
9,
650 (1892)
p. 467.
ELECTROCHEMISTRY
493
The
free chlorine
ferrous chloride
is
oxidized
The explanation
of
what goes on in
this
experiment
is
com-
The
This electrode
is
thus
left
The current
univalent ion carries one electrical charge, a bivalent ion cartwo such charges, an n valerit ion n such charges. The second
ries
it carries.
With
and
istry,
See Principles of Inorganic Chemistry, and Elements of Inorganic Chemby the author of this work.
494
We
We
have thus raised the valence of an element by inwhich it carries, and we have done it
Much
of these electrodes.
If
solutions of electrolytes, as
cell,
we have
the cathode, the anions the negative charge towards the anode. These
ions give up their charges to the respective electrodes or poles, and
thus become atoms or groups of atoms. These may then separate
cess is
known
sidered a
little later.
When
Products of Electrolysis.
the ions give up their charges
to the electrodes, they may be capable of an independent existence,
or they may not, depending upon their nature.
Many cations, such
as some of the metals, are capable of such an existence, while very
few anions can exist as such, after they give 'up their negative charge.
In the latter case they may decompose into entirely new products, or
may react with some other substance present and give rise to secondary products. We must distinguish, then, between primary and sec-
ELECTROCHEMISTRY
495
does any one suppose that the molecule of a metal in the solid state
The fact that the molecule of many
identical with the atom?
is
metals
is
is
dissolved in
(3)
(4)
products.
If a current is passed through an element containing metal electrodes surrounded by salts of the same metal, the electrodes are not changed, and the solutions around the electrodes are
Polarization.
concentration.
is,
496
made up
therefore,
of
and
pose by Fuchs.
2
by Le Blanc.
The following
modification of this
The electrolyte whose polarization it is desired to study is introduced into the tube T (Fig. 68). Two electrodes connected with the
element E, which furnishes the polarizing current, are introduced as
shown in the figure. To measure the potential at either electrode,
we connect this electrode with a normal electrode. To measure the
potential at b, the arm of the normal electrode n is connected with
the electrolyte in c, and the wire from the normal electrode connected with b through the arrangement for measuring electromotive
The electromotive force of this element is then measured.
force.
FIG. 68.
electrode
The
b.
a can be measured in a
similar manner.
If the polarizing
increases in strength, the
current of polarization will also increase rapidly in strength. After
the electromotive force of the polarizing current has become quite
current
at first very
is
large, the electromotive force of the current of polarization will increase as the former increases, but more and more slowly.
There is,
therefore, no
say
Streintz
Fogg. Ann.
Ztschr. phys.
Jahn: Ibid.
volts.
Chem.
See
299 (1891)
13, 163 (1894).
12, 333 (1893)
Gockel Ibid. 34, 529 (1900). Coehn Ibid. 38,
Tafel: Ibid. 50, 641 (1905).
8,
609 (1901).
3
Wied. Ann. 32,
11(3
(1887).
ELECTROCHEMISTRY
Le Blanc * has measured the electromotive
497
which is required
be
passed through an
may
He found that
a
continuous
effect
so
as
to
decomposition.
electrolyte
for a given substance under given conditions this had a definite value.
This he termed the Decomposition Value of the substance.
force
"
will, therefore,
be given.
ACIDS
=
=
=
Sulphuric acid
Nitric acid
Phosphoric acid
1.67 volts
Malonic acid
1.69 volts
Hydrochloric acid
Triazoic acid
1.70 volts
Oxalic acid
=
=
=
=
1.69 volts
1.31 volts
1.29 volts
0.95 volt
1.66 volts
BASES
= 1.69 volts
= 1.67 volts
Ammonium hydroxide = 1.74 volts
Sodium hydroxide
Potassium hydroxide
SALTS
= 2.25 volts
Strontium nitrate = 2.28 volts
= 2.11 volts
Calcium nitrate
Potassium nitrate = 2.17 volts
= 2.15 volts
Sodium nitrate
Barium
If
nitrate
we examine the
= 1.99
= 2.01
Calcium chloride = 1.89
Potassium chloride = 1.96
= 1.98
Sodium chloride
Barium chloride
volts
Strontium chloride
volts
and
bases,
we
see'
volts
volts
volts
that the
."
by Le Blanc.
1
2 Ibid.
p.
315 (1891).
2K
8,
299 (1891).
498
Primary Decomposition
of
Water
in Electrolysis.
When
solu-
the cathode
been accepted for a long time is as follows Take the case of potassium sulphate; it dissociates into the cation potassium and the
:
anion
SO 4
its
and
liberates
the water
is
act.
ondary
This view'of electrolysis has now been fundamentally changed,
"
"
decomposition values
especially by the work of Le Blanc on the
of electrolytes.
The view which is supported by these facts is that
the decomposition of water is a primary act of electrolysis. Water is
dissociated very- slightly into hydrogen ions and hydroxyl ions,
as is shown by many experiments, but especially by the small
conductivity of the purest water. When a solution of potassium
sulphate
is
anions,
SO 4 anions, form
fits
Why
We
1 See
Arrhenius: Ztschr. phys. Chem. 11, 805 (1893). Le Blanc: Ibid. 12,
333 (1893). Also Outlines of Electrochemistry, Jones
(Elec. Rev. Pub. Co.).
ELECTROCHEMISTRY
499
moves
If in terms of the old theory the cation
say potassium
over to the cathode and gives up its charge, and the metal then acts
As
why
their charge to the cathode when there are hydrogen ions present
which hold their charge less firmly than potassium ?
The objection might be raised in this connection that water is
only slightly dissociated and there are, therefore, only a few hydrogen ions present. These would soon be used up and then the potas-
sium ions would have to give up their charges in terms of the old
This objection has of course no foundation in fact, since
theory.
the water present will continue to dissociate as fast as the hydrogen
ions are used up.
We know from the law of mass action that the
condition which will always obtain is, that the product of the number
of hydrogen ions and the number of hydroxyl ions present will be a
constant.
for the new theory furnished by the " decomposi"
In terms of this
of electrolytes must be considered.
tion values
theory, the electrolysis of the salt of any metal which decomposes
The evidence
water
this is true, then the decomposition values or electromotive force required to affect continuous electrolysis must be the same for the salt
of
such
is
the case
is
different metals
That
terms of the
new theory
of electrolysis the
the cathode, give up their charge and separate. The anion s5 4 moves
to the anode, the hydroxyl ions from the water give up their charge,
500
This is seen to be
other under these conditions.
about 1.75 volts. If the acid yields an anion whose discharging
value is lower than that of hydroxyl. its decomposition value will be
less than the maximum 1.75 volts, and such is the case with the
halogen acids and the organic acids. Bases dissociate into hydroxyl
ions on the
which moves to the anode and gives up its charge, and a cation
which moves to the cathode. The latter does not discharge its positive charge, since it loses its charge with greater difficulty than the
hydrogen cations from the dissociated water already present around
The
the anode.
of a base
must therefore be
It must be the
the same as that of an acid like sulphuric or nitric.
same as the maximum decomposition value of the acid, and such is
liberated
ber of hydroxyl ions around the cathode; and, similarly, the formation of an acid around the anode increases the number of hydrogen
ions around this pole.
Since the product of the number of hydroxyl
and hydrogen ions is a constant, an increase in the number of
hydroxyl ions around the cathode means a decrease in the number of
hydrogen ions around this pole. And for the same reason an increase in the number of hydrogen ions around the anode would
diminish the number of hydroxyl ions around this pole. Both of
these influences would tend to increase the decomposition value of
the compound.
bases,
Metals.
When
a current
is
ELECTROCHEMISTRY
501
electrolytes, all of the ions present take part in conducting the curThe amount of current which will be carried by any kind of
rent.
ions
will
depend upon
their
relative
relative
When
value for any ion, this ion will not lose its charge and separate at
the electrode in any quantity. Every ion has its own decomposition
value, and these values differ very considerably for different ions.
The
effect
an
electromotive force until the element with next higher value sepaTake two metals
and B, and mix solutions of
rates, and so on.
their salts.
its
electromotive force
of B.
When
it
is
increased
to the
decomposition value
from the
will separate
solution.
The possibility of separating metals in general by means of currents of different electromotive force was pointed out by Freuden1
current used is, therefore, very great in effecting electrolytic separation of the metals.
It has,
current density
rations.
a given time
1
2
8
and
if
the density
is
great
it
502
all
CH
2CH~C0 = C
2
H + 2C0
6
2,
The anion
of propionic
2 C 2 H7C0 2 = C 2
H COOH + C H + C0
2
2.
Facts of this kind have already been utilized quite extensively for
An examination of
effecting the synthesis of organic compounds.
the literature * will show that a very large number of organic com-
Thus
The
CH -COOC H
romr
CH < none H =
+ 2 C0 + 2 K.
)C2Hs
CH -COOC H
2
malonic acid.
1
The student is referred in this connection to the admirable
Lob on Electrolysis and Electrosynthesis, translated by Lorenz.
2
*
little
book by
ELECTROCHEMISTRY
Working with
60S
much
in the future.
Cells.
to certain forms of
istry should not be closed without brief reference
of furnishing
as
means
use
into
batteries which have come
general
electrical energy.
Two
of these
cell.
we
We
belong to
shall consider,
electrodes are carbon and zinc, and the electrolyte chromic acid
(potassium bichromate and sulphuric acid). Zinc ions pass into
The ions Cr2 7 probably
solution, consequently this is the anode.
These pass over into
valence.
ions
of
chromium
a
few
high
yield
chromium ions of lower valence, and thus add to the electromotive
The
Mn
We
504
be reconverted again, at
reversible element can be
through
it
will, into
electrical.
Theoretically, any
current
are
current
The chief
is
The quadrivalent
At the anode
removing positive
the ions
S0 4
S0 4
electricity
lead sulphate.
recent
in this
has been
laboratory,
5,
533 (1899);
(1898).
6,
46 (1899).
6,
649 (1900).
ELECTROCHEMISTRY
spit
solution.
505
salt present
in the
salts are
same
mixed
They obtained
The
greater electrical density of the charge upon the smaller ion.
ions with the smallest atomic volumes and therefore greatest
hydrating power, have the smallest migration velocities, as would be
expected.
following relation
and water.
w,
oo
in methyl alcohol
-~
-,
=-
= constant.
in ethyl alcohol
/AGO
3
the
we
viz.,
Chem.
81,
68 (1912).
506
caesium
lower the
The meaning
viscosity of the water in which they are dissolved.
It was found that
of this has already been discussed (p. 448).
rubidium chloride, bromide, iodide, and nitrate also lower the vis-
of Jones, Davis,
2
8
ELECTROCHEMISTRY
The newer work, however,
1
passivity see Heathcote.
concerns us here.
507
is
what
chiefly
The oxide
must therefore be
abandoned.
The theory of Finkelstein, that passivity corresponds to a condition of higher valence than activity, has recently met with strong
Grave 6 calls attention to the fact that when an element
opposition.
exists in different modifications, a definite
amount
make
of energy
is
neces-
To convert a metal
it is
only necessary
it
is
is
no detectable
dif-
it
themselves.
Zeit. anorg.
309 (1907)
8
15,
Zeit. phijs.
Chem.
490 (1909)
Chem.
39, 91 (1902).
* Zeit.
6
6
iZeit.
Mektrochem.
2,
705 (1905).
49 (1906)
13,
508
this
would mean that the metal in the passive state has lower
solu-
"What
is
An
accel-
The hypothesis
of Sackur
to.
The hydrogen
activation hypothesis, which is in direct opposition to the suggestion of Fredenhagen, is based on the assumption that the normal state of a pure metal is passive.
It becomes
(3)
and
others.
and alkaline
solutions.
Abhand. Bunsen.
Ibid.
80,385 (1912).
Ac-
ELECTROCHEMISTRY
509
hydrogen
Eathert.
when
iron
is
is
activated by diffu-
is
While there
it
is
much
seems a
in favor of the
little difficult
to reconcile
passivity,
slight scratches or jars, in causing passive metals to Become active.
Whether a metal absolutely free from hydrogen ions is necessarily
passive
is
hydrogen, since
Ibid. 35,
it
is
dissolved readily
210 (1900).
510
Further investigation
in accord with the facts."
collect.
is
this hypothesis
not
activity is
due to hydrogen
ions.
A convenient
CHAPTER
VIII
PHOTOCHEMISTRY
ACTINOMETRY
Transformation of Radiant Energy into Chemical.
We have daily
as 1727
effects
is
light
have different
He
exposed paper
1839 for obtaining images of objects, and thus was started the
science of photography.
know to-day that the transformation of radiant energy into
chemical depends largely upon the wave-length of the former. Cer-
We
by the
by the
spectrum.
Some
of the
i Eder
Fehling's ffandworterbuch der Chemie, Vol. IV, pp. 124-125 (1886).
Licht / Chemische Wirkungen.
:
511
512
"
Light of every color from the extreme violet to the extreme
and also the invisible ultra-red and ultra-violet rays, can produce
1.
red,
chemical action."
2. "All rays which act chemically on a substance must be
absorbed by it; the chemical action of light is closely connected
with optical absorption."
3. "Every color of the spectrum can have an oxidizing and a
The measurement
Actinometers.
rays
is
effect.
The
light.
hydrogen-chlorine actinometer
adinometers.
The
of hydrogen
*
FIG. 69.
and chlorine,
obtained by electrolyzing
a solution of hydrochloric
acid of specific gravity
on this bulb, when some of the gases combine, forming hydroThe latter is absorbed by the water in i, and the
column of water moves from I along the graduated tube k. By this
means the amount of gases which have combined is readily determined, and from this the intensity of the photochemical action. If
to fall
chloric acid.
the light
eter.
is
To avoid
this
may result in this form of actinomBurnett 4 replaced the hydrogen of the mixture
by carbon monoxide.
1
2
8
PHOTOCHEMISTRY
513
The
the time.
number
which are
effected
by
light,
have been used to measure the intensity of the light. The action of
mercuric chloride on ammonium oxalate takes place in the presence
of light in terms of the following equation
:
HgCl 2 + (NH 4 ) A0 4
= 2 NH C1 + 2 C0 + 2
4
HgCl.
The amount of decomposition can be readily determined by weighing the amount of mercurous chloride formed. The amount of mercurous chloride formed increases more slowly than the intensity of
the light, since the mercuric chloride in the solution is continually
becoming less.- This necessitates the introduction of a correction
used platinum plates in dilute sulphuric acid, and Gouy and Bigol5
employed strips of copper covered with a thin layer of copper
oxide, immersed in a one-tenth per cent solution of sodium chloride,
let
bromide, or iodide.
Ostwald 6
The
it
silver ions give up their charge to the metal and separate upon
as metallic silver, the iodine ions passing into solution.
From
l
Pogg. Ann. 117, 529 (1862) 124, 353 (1865) 132, 404 (1867).
Wiener. Ak. Sitzungsber. [2], 80, Okt. (1879).
;
2
8
Compt. rend.
9,
176 (1851).
*Phil. Mag. [4], 16, 426 (1858).
6
Compt. rend. 106, 1470 (1888).
*Lehrb.
d.
Allg.
Chem.
II, 1043.
514
the pole which has not been exposed to light a corresponding number of silver ions separate, thus rendering this pole negative. This
explanation accords with the fact that in such an actinometer the
current flows on the outside from the pole which has been exposed
to the action of light."
Photochemical Extinction.
decide whether in
They passed
chlorine,
work.
ical
From
it
employed.
2
Against this conclusion of Bunsen and Eoscoe, E. Pringsheim
The light absorbed by pure chlorine is
converted into heat, but when the chlorine is mixed with hydrogen
it is
very probable that the light absorbed
largely in doing chemical work.
Photochemical Induction.
is
used up wholly or
in 1843, that while silver chloride which had not been exposed to light was sensitive only to the short wave-lengths of light,
rel,
[3], 9,
Wiedf
Ann
257 (1843).
32 386 (1887).
,
PHOTOCHEMISTRY
515
silver chloride which had been exposed a short time to light, but
which had not darkened, was sensitive also to the longer wave-lengths.
The former was acted upon only by wave-lengths shorter than the
green, while the latter was sensitive even down into the ultra-red.
Differences of the same kind were observed with other substances.
Similar phenomena were studied quantitatively by Bunsen and
1
Eoscoe, who used the term photochemical induction.
They allowed
to
a
mixture
of hydrogen
from
a
constant
source
through
pass
light
and chlorine, which had been freshly prepared or had stood for a
considerable time in the dark. At first there was little or no action.
After some time a slight action began, and this increased gradually
up to a constant maximum value. The following results taken from
the paper 2 of Bunsen and Eoscoe will make this clear. The first
column gives the time in minutes, the second the amount of hydrochloric acid formed during each minute, as measured by absorption
in water and the movement of the water column in the actinometer.
The source of light was the zenith of a clear sky.
TIME IN MINUTES
TIME IN MINUTES
0.0
0.0
1.7
3
4
5
6
0.9
3.0
1.0
9
10
1.3
11
5.8
2.0
12
6.7
after
2.2
6.2
from nine
maximum
constant value.
maximum
The
first
action of the light, whatever it may be, therefore takes place only
when the molecules of the two gases are in the presence of each
other.
i
2 Ibid.
100,
484 (1857).
516
The
action of light
ties
intensities.
light came.
C 6H 4 Br.CH3
But
if
H CH
number
form
number
of
8
B
.Ber. d.
Monatsh.
8,
101
PHOTOCHEMISTRY
meres, of acetylene into benzene, and
many
517
cited.
done in the
field of
photochemistry.
Bunsen and
E-oscoe 1
showed
equal to the product of the intensity of the light and the time during
it acts.
This is the same as to say that a given photochemical
which
As Rontgen
is
that
states, the
it
The metals, however, differ very considerably in their transparency to this radiation. Some fluorescence was produced when a
screen of aluminium 15 mm. thick was interposed, while a plate
of lead 1.5 mm. thick is practically opaque. Platinum is among the
extent.
(1898).
Scientific
Wiirzb. phys.
Memoirs
"Pressure of Light."
225 (1903).
medicin.
Gesell.
1895.
12,
518
different
degrees of opacity.
This form of radiation produces fluorescence not only in barium
platinocyanide, but also in phosphorescent calcium compounds,
calcite, uranium glass, etc., and also produces chemical action on
photographic dry plates, either directly or by means of the fluores-
it
ionized gases
through which it passed therefore, differs fundamentally from cathode rays. This radiation also differs fundamentally from ultra;
violet
by
light.
this radiation
1
by Stokes.
was produced
Eontgen ray
is
held
He
an irregular manner.
of this theory Stokes shows that he can explain the
Their
are known, in a perfectly satisfactory manner.
By means
which
facts
penetrating power is due to the fact that the pulse is gone before
any harmonious vibration between the ether and the molecules can
be set up.
more
2
by J. J. Thomson is the one now generally accepted.
The Becquerel Bays.
A form of radiation which in some respects resembles the Eontgen rays, but in others seems to differ from
3
in 1896.
it, was discovered by Becquerel
Compounds of uranium
when exposed to light have the property of emitting an invisible
radiation which traverses many substances impervious to light, such
many
1
Manchester Lit. and Phil Soc. 41, Part IV, 1896-1897.
moirs Series, III, 43. " The Wilde Lecture," July 25, 1897.
Phil Mag.
Scientific
Me-
Compt. rend. 122, 420, 501, 559, 589, 762, 1086 123, 855 124, 438, 800
128, 771
129, 912
132, 371 (1896-).
130, 206, 372, 809, 979, 1154
131, 137
Nature, 63, 396 (1901).
;
PHOTOCHEMISTRY
519
This
salts
uranium or of one of
If a piece of
ization
by means of tourmalines.
l
properties analogous to those possessed by light, and led Stokes to
conclude that the Becquerel rays occupy a position intermediate
C.
Loc.
cit.,
pitchblende containing
* Phil.
*
(1903).
520
it
barium.
By
this
gamma
\
2
*
Phil.
6 Itiid.
5, 476 (1903).
A, 270 (1912).
Mag.
86,
PHOTOCHEMISTRY
The alpha
properties.
521
little
the result
light,
The
much
Its
name
is
slight
power to
alpha
effect
of the
beta particles will show that they are essentially cathode rays, but
move with higher velocities than the cathode particles.
The gamma rays have the same general properties as the X-rays.
They have, however, much greater power to penetrate matter than
the X-rays; being able to pass in detectable quantity through a
foot of solid steel.
They always accompany the beta rays, being
probably produced by the beta rays as the X-rays are produced by
which they
They
also
pass.
522
produced.
By determining the
by radium to boil liquid hydrogen.
amount of hydrogen converted into vapor, and knowing the heat
of vaporization of hydrogen, they had all -the data necessary for calculating the amount of heat liberated by radium.
A much better method for measuring the amount of heat liboff
erated by radium,
is
This
consists in allowing the heat that is given off by radium to melt ice,
and then determining the amount of ice melted in a given time.
Knowing
liberated
ice,
we know
by radium.
The
first
this energy ?
How
do these alpha parmust be due to the presence in the radium atom of an enormous quantity of that form of
energy which we call intrinsic, to distinguish it from extrinsic.
leaves unanswered the question,
ticles attain their high
velocity? This
since
it
PHOTOCHEMISTRY
523
The amount
lems.
the question arises whether a part of solar heat may not owe its
This question, which has been asked by Euthorigin to radium.
1
erford, raises the further question, Does radium occur in the sun,
if so, in what quantity ?
We have no means, at present, of
However, while we have no
answering this question directly.
direct evidence of the existence of radium in the sun, we have very
good indirect evidence. Helium exists in the sun in large quantity.
We shall learn that helium is produced from radium. Therefore,
radium probably exists in fairly large quantity in the sun. If so, a
small part of solar heat undoubtedly has its origin in radium.
Eutherford has also pointed out that the calculated age of the
earth probably contains an error introduced by the heat liberated
by radium. In this calculation it is assumed that the earth is a
cooling body, there being no heat produced within it during the
cooling, except that which is liberated in such chemical reactions as
and
the hydration of the rocks, which takes place when the temperature
has become sufficiently low. If there is any appreciable quantity of
radium in the earth, this would be giving off large amounts of heat,
and thus vitiate such calculations as the above. The question is,
Does the earth contain large quantities of radium ? There is indirect evidence that there is considerable radium deep down below
the surface of the earth. The waters from certain springs which
come undoubtedly from considerable depths, contain appreciable
%
quantities of helium, which indicates the presence of radium.
Mag.
5,
591 (1903).
524
through space, the radium coming ultimately from the sun. This
would involve the assumption that the earth also picks up a much
larger quantity of uranium, since these two elements always occur
There is not yet sufficient evidence accumulated to
together.
enable us to pass judgment on this suggestion.
That certain radioactive bodies contain a subThe Emanation.
stance having
Rutherford. 1
first
- 152.
We
know extremely
little as to
allowing
it
to diffuse
We
pound.
Phil.
Mag.
49, 1 (1900).
PHOTOCHEMISTRY
525
its
appearance, the
D3
dium
excluded by Ramsay.
This work, which has been most carefully repeated, has led to no
small amount of sensational literature. It has been stated that the
transmutation of the elements has now been effected, that what the
alchemist sought to do has now been accomplished. This is no
more true to-day than it was a century ago. We have not effected
the transmutation of any elementary substance into anything else.
Radium is an unstable system, which undergoes decomposition
spontaneously, at a rate that cannot even be changed by any means
known to man. It is obvious that this bears no relation to the production of one element from another by artificial means, which is
what is meant by the transmutation of the elements.
The Emanation induces Radioactivity in Objects with which it
The Curies 3 found that when almost any subcomes in Contact.
stance is brought into the presence of a radium salt, and allowed to
remain for a time, it becomes radioactive. This induced or excited
radioactivity was shown by Rutherford to be produced by the emanation.
When the emanation was removed from a radioactive
substance, this substance no longer had the power to excite radioactivity in bodies brought into its presence.
The induced or excited radioactivity was
(1903).
shown
to be due to the
526
off
scheme
series, is
Eadium
emanation
radium
radium
a fty
radium
a
07
radium D
radium E
radium F.
It is not known what is produced
It is
directly from radium. F.
quite possible that it passes through a number of transformations,
and may yield as the final product ordinary lead, which is not radio-
active to
may
its final
decomposition product.
is
If a solution
scarcely less than of epoch-making importance.
of a salt of uranium is treated with a solution of ammonium carbo-
nate, the
monium
active,
1
carbonate.
This residue was found to be strongly radioand the uranium from which it had been separated had
Phil Trans. A,
PHOTOCHEMISTRY
scarcely
any radioactivity at
all.
521
X had
its radioactivity at
laid aside for a time, it was found to regain its radioactivity, and
lost its radioactivity.
at exactly the same rate that uranium
After this uranium had regained its radioactivity, another crop of
uranium
X could
apparently indefinitely.
This shows that uranium
is
itself.
discovery strictly analogous to the above was made by Eutherford and Soddy T in connection with thorium. When ammonia is
The
salt,
the thorium
is precipitated.
If the solution
from which the thorium has been precipitated is evaporated to dryness, a small residue is obtained which is strongly radioactive.
This residue was termed thorium X. Thorium X, like uranium X,
loses its radioactivity on standing, and the rate of its decay has also
been measured.
Thorium from which thorium
has been separated regains its
on
and
standing,
radioactivity
exactly at the same rate that thorium
producing uranium X.
One other
rate at
which uranium
of the temperature
to
The
is entirely
independent
which these substances are subjected. And the
which uranium
X and
thorium
are formed is also indeThis alone would show that these transare not simply chemical reactions, since chemical
reactions have usually a large temperature coefficient, i.e. their ve-
rate at
pendent of
formations
the temperature.
with
rise in
temperature.
see, in
the
528
the
ments.
Origin of Radium.
We
amount
total
other,
this
actinium.
A number of
radioactive elements,
Am. Journ.
Ser.
9, 599 (1905).
Nature, 75, 270 (1907).
3963 (1904); 38, 775 (1905).
Mag.
*
PHOTOCHEMISTRY
529
less
thorium
series,
according to Kamsay,
(1)
Thorium
(2)
Radiothorium
(3)
(4)
inactive
is
Thorium A
Thorium B
(5)
(6)
Thorium
Thorium emanation
(7)
(8)
Helium
Ramsay
The theory which accounts very satisfactorily for many of the phenomena such as we
have been studying, is that proposed by Rutherford and Soddy. 2
The atoms of the radioactive elements are unstable. They
undergo decomposition arid new products arise. These may be unstable and undergo further transformations, giving rise to still other
During these transformations, alpha, beta, or
products, and so on.
gamma particles may be given off. The alpha particles are given
off in the earlier transformations, the beta and gamma rays in the
later
stages
of
These trans-
Another difference between the transformations of the radioand ordinary chemical reactions, which is probably
active elements
i
2M
3,
617 (1906).
Phil.
Mag.
5,
576 (1903).
530
of energy liberated.
in the quantity
quantity of heat incom-
above,
is
parably greater than that set free by the most exothermic chemical
reaction.
are,
what an atom
is.
unstable atom ?
How
Here the
electrons
The
the fact that the atoms with the greatest masses are the most radioactive.
Such atoms obviously contain the largest number of
electrons,
These systems
to manifest the
was begun.
When we
matter
is at
PHOTOCHEMISTRY
531
The lighter atoms are more stable than the heavier ones,
are unstable, undergoing slow transformations into simpler
unstable.
but
all
things.
We
PRODUCTION OF RADIUM
Radium
it
is
He
sufficiently
radium.
number
of months.
532
by Boltwood ionium.
It
closely in its properties the element thorium. Inis so close that it has thus far been found
resemblance
this
deed,
The sequence of decomposition
it from thorium.
free
to
impossible
nium resembles
is
probably uranium
uranium
ionium
radium.
is
all
of the
known
Light
which
is
made
in nature.
crystal is a grating with the distance between
the lines of molecules of molecular dimensions.
When
it,
by
was
reflected
rays.
An
ionization
chamber
is
a flask
filled
When
PHOTOC H EMISTRY
533
1
space of the grating, it was calculated that the x-rays have wavelengths of the order of magnitude of an Angstrom unit being, how;
Phil.
Mag.
CHAPTER IX
CHEMICAL DYNAMICS AND EQUILIBRIUM
HISTORICAL SKETCH
The fact that different forms of matter can
Earlier Views.
combine with one another, giving new products, was recognized as
early as chemical elements and compounds were dealt with. Certain
elements combine with certain other elements giving compounds
many of whose properties differed fundamentally from those of
Some elements combine with the greatest ease,
either element.
evolving a large amount of heat, while others combine with difficulty, or only at elevated temperatures, while others again would
not combine under any known conditions. It was also early observed that one element may have the power of breaking down a
compound containing two or more elements, combining with one
or more elements and setting the remainder free. It was, therefore,
obvious that elements possess very different powers of combination,
and that the compounds formed have very different degrees of
stability.
535
the electric current can not only decompose water, but also many
other chemical compounds, such as salts of the heavy metals. Since
and
electrical attraction.
electrochemical theories of
Davy and
As
the result
we have the
is
these
we
shall
now
turn.
given substance was placed at the top of a table, and other substances arranged in the order of their decreasing affinity for the
substance in question. The substance higher in the table displaced
from their compounds those below it, the ease with which the displacement took place depending upon the relative positions in the
table.
This method of dealing with chemical affinity referred it
entirely to the nature of the substances which were brought together, and made it independent of any external conditions to which
the substances were subjected.
Bergmann went much farther than Geoffroy in that he recognized
that the power of substances to react chemically depended not
536
only upon their nature, but also upon other conditions. Thus, the
state of division had a marked influence on the reactivity of substances,
and
this explained
why
substances react
much
better in
The
We
in the wet.
affinity,
Wenzel to inquire into the effect of different quantities of one substance with respect to the other on the velocity and the amount of
the reaction between the two.
He was led to the conclusion that
chemical action
The Work
of Berthollet.
The
first
communication. 3
Chemical affinities
in this
first
do"
5.
537
which one substance can replace another from its compounds but
and decompositions we must take into account
;
in all combinations
affinities,
The
effect of
number
of experiments,
which he demass
1
scribed in a second communication, showing the effect of
Berthollet studied also the effect of solubility on chemical activIn order that substances may react there must be good contact,
ity.
and such
is
established in solution.
amount
to the total
etc.,
tity of
known
result
OstwaWs
Klassiker, 74, 7.
538
sul-
the most stable compounds known, being decomposed with any considerable velocity only by the most powerful chemical reagents.
Yet
in nature these
is effected
activity.
One other example which was pointed out by Eose should be cited.
sulphate of medium concen-
tration
is
by the formula 3
K S0 H S0
4
crystallization, the neutral salt will separate, showing a further splitting off of sulphuric acid due to the mass action of the water.
Pogg. Ann.
[1], 82,
273 (1812).
539
the two were fused together, and also when the sulphate was boiled
with a solution of the carbonate. The amount of the sulphate
is
added,
it
decomposition of insoluble
salts
by
any
is
by
Pogg. Ann. 94, 481 (1855) 95, 96, 284, 426 (1855).
Ann. Chim. Phys. [3], 51, 328 (1857).
Pogg. Ann. 81, 413 (1850). Ostwaltfs Klassiker, No.
;
29.
540
Wilheliny
that this
is
is
dZ
be
us assume
is
tity of acid.
"
let
which
sugar, which
in
" Let
later
by experiment,
whence, log ZQ
are given, and
logZ= - MST+C.
For T = 0, Z = ZQ,
M"
determine
This work of Wilheliny must be regarded as the foundation of
chemical dynamics. The relation which he established is a general
one, holding for the velocity of all reactions in which only one sub-
to
stance
transformed.
is
the reaction
is
2
any other properties. Lowenthal and Lenssen took up
the latter problem and showed that a very interesting and important
relation exists.
The velocities with which acids will invert cane
acids with
common
relative rates at
which
the halogen
acids and nitric acid having the greatest action, while sulphuric,
phosphoric, and the organic acids invert much slower.
Work
of Berthelot
Pogg. Ann.
8
81,
Gilles.
Berthelot and
418 (1850).
[3], 65,
journm pra
385
66, 5
Jct.
Chem.
68,
225 (1862-1863).
541
by the temperature,
is reversible, i.e.
etc.
first
salt
was formed.
was reached.
ester
With a given
the velocity of ester formation cfoes not vary appreciably with the
x
complexity of the alcohol. Berthelot and Saint Gilles concluded
from their study of the velocity of ester formation, that the amount
of ester formed in every moment is proportional to the product of the
masses of the reacting substances, and inversely proportional to the
volume, which contains essentially the views that we hold to-day.
From the study of the relation between the chemical composition
of the acid and alcohol, and the amount of ester formed, some interA few of their results are given,
esting conclusions were reached.
in which different alcohols and acids were employed.
The reaction
was allowed to proceed until the maximum amount of ester was
formed under the conditions. The results are expressed in percentage of the theoretical amount of ester which would be formed if the
reaction went to the end
:
ESTER FORMED
C 2 H 6 andCH 3 COOH
C 2 H6 O and CH3 .CH 2 .CH2 COOH
C 2 H 6 andC 6 H 6 COOH
CH 4 O andCH3 COOH
CH4 andC 6 H 5 COOH
C 6 H12 and CH COOH
C 6 Hi 2 O and C 6 H 5 COOH
66.9%
69.8%
67.0%
67.5%
64.5%
68.9%
70.0%
542
The result is very surprising in that neither the nature of the acid
nor the base has any marked influence on the amount of ester
formed.
The most interesting question studied by Berthelot and Pean de
Saint Gilles
still
remains.
of alcohol with
and
acetic acid,
representing the
number
amount of
with ethyl
of equivalents
543
When
this
compound
is volatilized, it is
decomposed
to a consider-
The nature
the velocity and amount of the reaction, and the nature of the products had been studied at length.
This is what we would expect,
since the transformations of matter are the most obvious results of
This
1
field
was opened up
in 1854
2
by Julius Thomsen, who sought
Pogg. Ann.
92, 34 (1854).
544
by means of the heat evolved. Thornwork is based upon this fundamental proposition, "We can
now measure in absolute units the magnitude of the force which is
developed in the formation of a compound it is equal to the amount
Alof heat which is evolved in the formation of the compound."
though we know to-day that this proposition leaves out of account
a number of factors, yet it is a very important step in the right
direction.
A
to the
2
began his work in 1867, and during the next fifteen or twenty years,
with the cooperation of his students, improved thermochemical
methods, and made an enormous number of thermochemical deter-
minations.
As the
at the
As
ciple has been subjected.
tains the germ of a great truth.
it
undoubtedly con-
on the synthesis of ether from alcohol and sulphuric acid. This has
already been considered in connection with the origin of the theory
of electrolytic dissociation, but its bearing on chemical equilibrium
is of
epoch-making importance.
Before this time chemical equilibrium was regarded as static.
When equilibrium was reached, the greater forces overcame the
smaller, and the latter were unable to effect any transformation,
Lieb.
Ann.
77, 37 (1851).
545
took place in the opposite direction, but both reactions were going
on simultaneously. If this reciprocal exchange of parts can take
place with atoms or groups which are unlike, so much the more can
take place with similar atoms or groups. Between the molecules
any given compound there is, then, a continual interchange of
parts taking place a given atom, which at any moment forms part
of one molecule, may the next moment form part of an entirely dif"
ferent molecule.
Says Williamson, In a vessel containing hydrochloric acid, we must not regard the hydrogen atoms as fixedly
it
of
combined with the chlorine atoms, but any one hydrogen atom may
take the place of any other hydrogen atom, being now combined
with one chlorine atom and now with another."
This conception of the condition of things when equilibrium is
reached, is fundamentally different from the older or statical view,
which regarded the atoms as fixedly combined in molecules. This
view of equilibrium, where the atoms are continually changing partners, as it were, we will call the dynamical view.
Equilibrium is
then dynamic, not static, the condition which must be fulfilled
being that the same number of transformations must take place in
one sense, in a given time, as take place in the opposite sense. We
shall see that this lies right at the foundation of our present conception of chemical equilibrium in general.
lar in
simi-
cording to Clausius it
molecules are broken
This
is
also distinctively a
is kept constant at
any point, equilibrium will be
but this equilibrium is dynamic, molecules undergoing
decomposition all the while, and other molecules being formed from
the decomposition products. The condition of equilibrium is that
established
same number
2N
&8
(1857).
546
With
study of a generalization
and
The
statics,
Law
we
shall
which underlies
now turn
all
to
a closer
chemical dynamics
of Mass Action.
of
Guldberg,
who was
later
mass on chemical
was
preliminary paper
published in Norwegian
activity.
Their
first
it is
known.
They
is sufficient to
account for
all
the facts
method
for
replaces C from a
the affinity between
A and B is
and C, is not
greater than between
this
since
account
a large
leaves
out
of
assumption
satisfactory,
number of conditions which affect the reaction. The attempt to
measure the magnitude of chemical affinity by the heat evolved
during the reaction was regarded as unsatisfactory, because it depends in part upon the conditions under which the reaction takes
place.
we must study
and where,
"
(6)
1
Investigations on Chemical Affinities. University program for the
semester.
See also OstwaWs Klassiker, No. 104. "Edited by B. Abegg.
first
547
by double substitution into two new substances, A' and B'-, and
and B' can transform themselves into
under the same conditions
A and B. Neither the formation of and B' nor the reformation
of
and B are complete, and at the end of the reaction we have
formation of
A and B
increases proportional to the affinity coeffi-f- B', but it depends also on the
A+B=A
masses of A and B.
" We have learned from our
experiments that, the force is proportional to the product of the active masses of the two substances A and B.
" If we
and B by p and g, and
designate the active masses of
=K
reaction.
A and
and
let
B'.
that the consideration of this ideal reaction, where only the forces
between
and JB, and between
and B' are taken into account,
theory.
" Let the active masses of
coefficient of the reaction
reformation of
By
we can
On
A and B' be p
first force,
and
A' + B' = A + B be
q',
1
and the
affinity
This force
is
in equilib-
consequently,
Kpq =
"
and
K'p'q'.
(1)
if
between the
affinity coefficients
we have found
K*
this ratio
we can
calcu-
substances."
i
g',
K and K'.
548
=
"
By
F we
2
have
(2)
x).
"
By
mined.
"If the two substances A and A' preserve a constant active mass
during the reaction, and both have equal value, formula (2) becomes,
(3)
Q-f?
=,
A and A
(4)
satisfactorily.
Thus originated the law of mass action, which lies at the foundation of chemical dynamics and equilibrium.
Guldberg and Waage point out that these equations hold only
for ideal reactions, which probably seldom exist.
They then consider the other forces which manifest themselves during the reaction.
Thus, side reactions take place, giving rise to other products
(
influences
549
may
into account in
applying the law of mass action to chemical reactions. The remainder of this paper is devoted to a description of experimental
data which bear upon the correctness of this law.
In another important contribution 1 in 1879, Guldberg and Waage
took up the application of their law to more special cases, such as
an ester is formed is really the velocity with which the alcohol and
acid combine to form the ester and water, minus the velocity with
which the ester and water react to reform the alcohol and acid ; in a
word, it is the rate at which the amount of ester accumulates.
If we represent the velocity with which the alcohol and acid
combine by v, this would, in terms of mass action, be equal to cpq,
where p and q are the active masses of the alcohol and acid (v = cpq).
If we represent the velocity with which water and ester react, forming acid and alcohol, by vlt in terms of mass action this would be
equal to Cjpjq^ pj_ and q being the active masses of the ester and
water.
The velocity of the reaction as a whole V, would be the
difference between these
two
F==
This
is
velocities,
v1
= cpq- Cjpflp
dynamics.
1
550
cpq
and
this is the
= c^q^
CHEMICAL DYNAMICS
why
chemical equilibrium.
The cause of all chemical reactions
mental
laivs
named, or
We
intrinsic
forms of
There
energy
intensity
form of energy
known.
This fundamental law applies also to intrinsic energy. Every
substance, elementary or compound, contains a certain amount of
intrinsic energy, at a certain definite potential.
These vary with
every substance.
When two
551
V=
v
V =Cpq
equation for the velocity of a reaction is,
C.g^.,
the actual velocity being the difference between the velocities of the
two opposite reactions. The study of the velocity of reactions is
(7.
A reaction in which
Monomolecular, or First Order Reactions.
one
in
substance
concentration
only
undergoes change
(which is the
same as to say whose active mass changes) is termed a monomolecular
If
reaction.
is the original amount of such a substance
present,
and if x of it is transformed in time , the velocity of transformation
is, from the law of mass action,
dx
dx
is
(7,
In
At the beginning
is
(A
of the
a constant.
Integrating,
= Gt + const.
= 0,
reaction =
In A = const.,
we have
x)
(),
and we have
a;
39,
258 (1901)
41, 62 (1902).
"
"The
552
sugar
is
following equation
it
breaks
down
+ C 6H
]2
C MH a O u + H 2
=C H
6
12
(Glucose)
6,
(Fructose)
cane sugar
can be neglected.
This reaction is unusually simple to study since cane sugar rotates
the plane of polarization to the right, while the products of inversion rotate the plane of polarization to the left.
By measuring the
amount of rotation by means of a polarimeter, we can tell at any
moment how much of the sugar has been inverted without interfering with the reaction. Determining x in this manner, observing t,
it
started,
we
sub-
A =
const., and see whether a constant
x
The following
are a
553
is not exactly proportional to the conacids invert much more rapidly than the
weak. The presence of a neutral salt increases the velocity of inversion produced by the strong acids, and diminishes 2 the velocity
The strong
centration.
of inversion of the
weak
acids.
Since the presence of an acid is necessary to produce any appreciable inversion of cane sugar, and since all acids effect the inversion, we would suspect that the catalyzer in this case was a constituent
common to all acids, and such is the fact. The hydrogen ions are
the catalyzers, and the velocity of inversion is approximately proportional to the concentration of the hydrogen ions present.
This is
the same as to say that the catalytic action of different acids is proportional to their strengths, since the strength of an acid is proportional to the
amount
of
its dissociation.
is
many
We
Notwithstanding
1
these influences,
it
2
8
7, 995.
554
gen
is
ions.
1.
dition than
it
went
in.
known
as a negative catalyzer,
and
new
or catalytic process of
making
sul-
phuric acid.
many
solids act
catalytically
upon
It
known
gases,
causing them
to combine
that
and
1
this led
3
Faraday to conclude that gases thus absorbed by solids
(1901)
Ztschr. phys.
Chem.
d.
chem.
555
have their molecules closer together, and for this reason enter into
chemical reaction.
The
walls of the containing vessel are an important factor in conditioning the velocity of reaction, especially between gases.
Thus,
it
decomposes much
close relation
2
8
Pyrochemische Untersuchungen.
Ztschr. phys. Chem. 20, 303 (1896).
Ztschr. anorg.
;
Chem.
16,
26 (1898).
(184P
39, 24 (1904)
Ber.
d.
556
to the
compound PtO.
think that in
cer-
hydrogen and
existence of intermediate
This applies to both organized ferments, such as yeast, and unorganized ferments which play such a prominent r61e in the living
body. That there is a close relationship between the action of fer-
catalysis,
2
effect.
The
Compt. rend.
1254 (1901)
(1903)
2
8
Lehrbuch, 6, 22 (1848).
Journ. prakt. Chem. I,
(1868).
4
Ztschr. phys.
6
Van de
Stadt
Chem.
:
31,
132, 210,
75, 79 (1858)
258 (1899)
Ztschr. phys.
Chem.
I,
335 (1863)
323 (1901).
329 (1893).
37, 1,
12,
89, 32,
I,
105, 207
is
557
formed. 1
2
Oxygen retards the rate at which hydrochloric acid is formed.
Two suggestions have been made to account for the action of a
methyl acetate
place
is
CH COOCH + H
3
= CH COOH + CH 0.
4
Zengelis
Drucker
Slator
1.
Bodenstein
Vondracek
Ipatiew
Sand Ibid. 51, 641 (1905) Proc. Eoy. Soc. 74, 356 (1905).
Rohland: Ztschr. phys. Chem. 56, 319 (1906).
:
Winther: Ibid.
'
558
increased
ing a measured volume from the solution from time to time, and titrating the acetic acid set free during the reaction.
A large number
showed that - In
t
is
monomolecular,
of such reactions
a constant.
is
x
i.e.
p. 283.)
when examined
shown not to be
By
known
this
as colloidal.
tion
of the decomposition
A.
first order.
559
was a constant.
x
It is
known
that
we
say.
1
Bredig and his pupils have shown that the merest trace of certain
to
diminish greatly the catalytic action of the
substances is sufficient
platinum, and in some cases to destroy it entirely. Thus, a grainmolecular weight of hydrogen sulphide in ten million litres of water
greatly diminishes the action of the colloidal solution of the metal.
And
is
on this subject, that the analogy which they have discovered is only
an analogy. He does not think that there is any identity between
the action of the two classes of substances, which are themselves so
different.
To quote his own words " All these facts point to an
unmistakable analogy between the contact actions in the inorganic
world and the actions of ferments in the organic world. As in the
case of my colloidal catalyzers, we are dealing with reactions in which
:
We
see,
corpuscles, and oxidizing and catalyzing organic substances.
therefore, that the organism develops its enormous surfaces in the
Ztschr.phys. Chem. 37, 1 (1901); 37, 323 (1901); 38, 122 (1901).
Ibid. 37, 323 (1901).
560
is
enzymes.
organic enzymes."
It seems that this
work may prove to be very important as thrownature of enzyme action. The enzymes are
on
the
some
light
ing
while the colloidal solutions of the
substances,
organic
very complex
metals are as simple as any substances known to the chemist. If
the latter effect reactions analogous to the former, by studying the
reactions with the simple elements the problem is certainly very
much simplified. That surface-tension may have much to do with
1
He
catalysis is also in accord with the views of J. J. Thomson.
thinks that this might explain especially the action of the surfaces
of the containing vessels on chemical reactions, changing the physical condition of
The
Aiitocatalysis.
can
effect
from
(1888).
561
This may
be either positive, increasing the velocity of the reaction, or negative, diminishing the velocity of the reaction.
lytically.
autocatatytic.
number
of other
monomo-
lecular reactions have been studied, but nothing essentially new has
should mention the
been brought out in connection with them.
We
work
of Van't Hoff
lowing equation
C 4 H4
=CH
Br2
Br
+ HBr.
CH C1 COOH+H
2
= CH OH COOH + HC1.
.
expression -In
A.
x
The equation developed
Bimolecular, or Second Order Reactions.
above holds where only one substance is undergoing change in cont
centration.
mass of
Where
(1860)
93,
25 (1864)
J. Thiele:
So
31,
562
is a change in concentration of two substances we have a bimolecular reaction, or a reaction of the second order.
Let us represent the active mass of one substance by A, and of
the other substance by J3, and by x the portion transformed in time
there
t,
of
mass action
| =C(A -x)(B-x).
It is
more convenient
to take the
A=B
Integrating,
At
we
-=
the beginning
have, const.
= --
+ const.
Ct
1
t
The constant
is
A(A-x)
tA
Saponification of an Ester.
cally
is
"
"
by sodium hydroxide."
563
This reaction was studied to test the law of mass action first by
1
2
3
4
5
Warder, and later by Eeicher, Van't Hoff, Arrhenius, Ostwald,
and Spohr. 6
Warder determined the amount of ester saponified by deter-
IN
MiNuns
A-x
5
25
65
0.108
120
0.113
Effect- of the
0.113
0.108
of Saponification.
by
ammonium
the
salt
The same
reaction.
Warder
Reicher
by strong bases
Chiminello
"The
Gazz. chim.
410 (1896).
(1886)
2
8
*
19,
1700
564
the
This explains
why
dissociated alkalies, such as potassium and sodium hydroxides, saponify an ester with the greatest velocity. If the base is not completely dissociated, as is always the case except in very dilute solutions,
the amount of the dissociation must be taken into account in order
may be known,
If we represent the
the base being only the dissociated portion.
the
base
this
factor must be
of
dissociation
of
a,
by
percentage
introduced into the above equation for a second order reaction, which
then becomes
We
can
now
see
why
little
quently, when the base forms a salt with the acid of the ester, the
salt does not yield any larger number of the common cations than
were present originally from the dissociating base. There being no
salt of
ammonia
is,
however, very
strongly dissociated.
the ester, forming an
the number of
know
The
increase in the
dissociation of the
number
Facts
present.
perfect accord.
and
theory
are thus
565
qualitatively
in
'
halides and organic acids, and between these halides and salts of the
above acids. A given organic acid may react slowly with ethyliodide in the sense of the following equation
:
Salts of organic
themselves, react
much more
rapidly.
in
terms of
The hydroxyl
K,OH + IC H = C
2
This
is
shown by the
fact that
when
H OH + K,L
5
is
true
when an
acid or salt
is
used
CH CONH + Cl + H +H
2
= NH + 01 + CH C0 H.
4
There are only two substances which undergo change in concenthe amide and the hydrogen ions. The water which is used
tration,
1
566
up
is
that
it
trichloracetic acid
t
is
TIME IK MIHUTM
.........
.........
.........
......
.........
16
60
120
180
240
7
t
A -85
0.0088
0.0088
0.0089
0.0090
0.0090
It is not
and x = 0, we have
We
show how
was employed.
t= TIMK
MINUTES
374
IN
CONSTANT
0.0347
628
0.0348
1359
0.0344
0.0335
II.
II.
669
0.0342
1265
0.0346
342
0.0346
670
0.0347
1103
0.0344
Lieb.
series,
but
we have
same constant
which
verifies the
reaction,
and
567
may have
we would have
at
where A,
jB,
and
D represent the
question.
In such cases
equivalent quantities
Integrating,
much
it is
making
simpler to take
A = B = D.
three substances in
Then,
= 0, x = 0, we have
c = l x(2A-x)
t
all
2A\A-x)
and D are not taken in equivalent quantities, the equabecome very much more complex. 1
The number of third order reactions known is small, and very few
have been studied quantitatively from the standpoint of the law of
mass action. A third order reaction in which three substances un2
dergo change in concentration was studied by Noyes and Wason.
The reaction is between potassium chlorate, ferrous sulphate and sulphuric acid, and is expressed by the following equation
If A) B,
tions
H 0.
2
They
different substances
as
Fuhrmaim
*'
568
The
2 FeCl 3
+ SnCl = 2
2
reaction
is
between
FeCl 2 + SnCl4
ferric chlo-
Although there are only two substances, there are three molecules
involved in the reaction, and we should expect it to be a reaction of
the third order.
Noyes studied the reaction, using the varying quantities of the
two substances, and found fairly satisfactory constants when equivalents were employed, but the values differed very considerably when
non-equivalents were used. This might leave some doubt as to
whether this is a true reaction of the third order but in addition
to the fact that a fairly satisfactory third order constant was generally
;
effect; thus,
two
In the
last reac-
tion studied only two substances took part, and yet we had to deal
with a third order reaction. The difference between this and an
We
acid,
ester
ATT
being involved.
Noyes:
Bodenstein
" Formation of
sulphur trioxide in the presence of platinum."
Bodlander and Koppen Ztschr. Elektrochem. 9, 559 (1903).
:
probably made up
+ Na
CH COOC H Na
CH COONa +
of the following
CH COOC H
CH.COONa
]
^CH.COONa
we might suppose
that
we were
dealing
is
^ CH COOC
An
569
2 2
Ca + 2 C 2 H 5 OH.
to be a bimolecular reaction,
or a
of
much higher
...
jj=C(A-x)(B-x)(D-x)(E-x)
(-*).
belong to the
Some
free
fifth.
from doubt.
place between
more than three molecules, but the study of the velocity of reactions
in terms of the law of mass action has taught us that most of these
reactions are not as complex as they seem, being in reality made up
of a series of simpler reactions.
As an example take the decompo1
570
sition of arsine
known
by
heat.
at these temperatures is
reaction thus
it
fact
to represent the
is,
order reaction.
-In
v
The
As 4 we would have
J&.
is
it is
first
AsH = As + 3 H,
3
and subsequently the arsenic atoms must combine and form As 4 and
the hydrogen atoms form
2
Many reactions of a similar character
are known, the order being much lower than would be indicated by
the usual chemical method of expressing the reaction.
We thus see how the study of the velocity of reactions has thrown
light on the inner mechanism of the reactions themselves, and has
given us a deeper insight into what actually takes place than could
have possibly been obtained by any purely chemical method.
The
Other Methods of Determining the Order of a Reaction.
method of determining the order of a reaction thus far considered,
consists in measuring the velocity of the reaction and inserting the
results into the equations for the constant as obtained from the first,
,
first
order.
duced into the equation for a second order reaction, the reaction in
question belongs to this order, and similarly for a third order
reaction.
It,
" Action of
potassium iodide on potassium ferricyanide. "
Journ. Chem. Soc. 83, 703 (1903).
571
volume
If
we
Consequently,
= ft" Cnn
:
dt
log (Ci
dt )
:
Cn )
is
which make it impossible to apply directly the equations for the first,
second, and third order reaction, and determine the order of the reacVan't Hoff applied this method of variable volume or variable
tion.
concentration in a satisfactory manner.
The experiments were carried out
by Reicher
TlMB IN MlNUTEB
CONCENTRATION
1
96
The value
of the differences
1
dCi
_Ci_
8.88
7.87
dt
-0166-
~ 7 87
w
-
p. 87.
Jbid., p. 89.
572
dilution
Oi
0.00227
3.81
132
3.51
to
first order,
we would expect
whose
integral
is,
is,
Ct=<J>(x).
"If we
ments,
Cfr
<
x have the same value in a series of comparable experihas a constant value, therefore,
let
(x)
= C^ = C3 3
t
or
d d d
:
=iti
tg
1.
t$
" The
and
side reactions."
first order,
amounts of
we
are dealing with a third order reaction, the velocity factors are proportional
to the square of the
concentrations, and the amounts of time inversely as the square of the concentrations.
;
Ztschr. phys.
Chem.
2,
127 (1888).
Lehrb.
d.
Allg.
Chem.
II [2], 236.
573
which
The
veloci-
by a number of influences
and conditions, some of which will be considered.
The influence of temperature on the velocity of reactions is usuties of reactions are considerably affected
The
in temperature over
a considerable range of
an
temperature
example given by Van't
clearly by
Hoff. 2 The following reaction with dibromacetic acid was studied
effect
of
is
rise
shown very
C 4H 4
Br 2
C4H 3
Br
+ HBr.
formed,
is
A number
portional
to the
The study
Ztsr.hr. phys.
*
6
6
Chem.
I,
223.
574
1
of thermodynamics, and the conclusions reached mathematically
of pressure, second
are, that first order reactions are independent
order are proportional to the pressure, while third order are propor-
Rothmund 2 found
cane sugar
is
inverted.
Other 4 first order reactions have been studied at different pressures, with the result that increase in pressure slightly increased the
velocity of the reaction, but, on the whole, experiment shows that
first
As we should
Tammann 5 showed
which a gas
that there
is
is
involved.
a definite press-
ure at which the metals will cease to liberate hydrogen from acids.
the pressure of the hydrogen reached 18 atmospheres, zinc
When
acid
was 0.34.
The equilibrium pressure for the hydrogen was 44 atmospheres
when cadmium acted upon 0.62 normal hydrochloric acid.
The equilibrium pressure for normal hydrochloric acid and manof the acid
ganese
is
52 atmospheres.
for nickel
is
to set
up a
first,
produced, not
simply by the pressure of the gas, but by the counter reaction
acquiring under these conditions the same velocity as the initial
is
reaction.
1
I,
Van't Hoff
235.
2
effect
is,
of pressure
in general, small.
575
Menschutkin 2 shows the magnitude of this influence. He studied a few reactions in a large numA few
ber of solvents, and in each case measured their velocities.
of his results for the action of triethylamine on ethyl iodide, in difused.
(C 2
I
of
The
H N+CHI=
5) 3
(C 2
576
satisfactory explanation of the great differences in the velocities in different solvents has not yet been furnished.
still less.
On
salts diminished the velocity with which ethyl acetate was saponified by bases, sodium salts having a greater influence than potassium,
and barium still greater than sodium. However, results similar to
those first considered were obtained by Arrhenius 4 and Spohr 5 from
a study of the action of neutral salts on the velocity with which cane
The
Under the head with which we are now dealing attention should
be called again to the effect of mere traces of moisture 6 on the velocity
of many reactions.
Dry chlorine is without action on many of the
8
7
Wanklyn has shown, and Baker and
Dixon 9 demonstrated by a number of experiments the comparative
That dry hydrochloric acid does not deinactivity of dry oxygen.
10
compose carbonates was shown by Hughes, who also demonstrated
that
it
benzene.
The presence
1
2
3
*
of moisture
is
Chem. News,
Ibid. 617(1884).
Phil. Mag. 34, 117
10
11
12
it
is
(1892).
73,
422 (1898).
577
moisture
On
conditions,
it is
dissociated
If,
Two
ammonium
chloride, causing
it
ignition temperature
and
ignition pressure.
The study
been made
there
in
is
We
2p
is
Besson
578
That
crease in pressure increases the velocity of the reaction.
with
an
a
reaction
which
at
begins
appreciable
velocity
pressure
is known as the ignition pressure, and at lower pressure the reaction proceeds with still greater velocity.
Thus, a mixture of oxygen with phosphine or with silicon
2
1
Aldehyde is not oxidized by
hydride explodes on expansion.
the
and
under
ignition temperature of a
high pressure,
oxygen
mixture of hydrogen and oxygen is lowered from 620 to 540 by
reducing the pressure from 760 mm. to 360 mm.
Many phenomena
We
might learn how to apply the law of mass action to ideal cases.
In fact, most reactions are much more complex, several reactions
The question arises how would we
occurring simultaneously.
to these more complex cases ?
the
law
of
mass
action
This
apply
becomes a simple matter after we are familiar with the fundamental
principle that every- reaction proceeds as if it alone were present.
This applies to a number of coexisting reactions, and is known as
An
the
first
of ethyl acetate by water in the presence of acids, and for the sake
of simplicity use acetic acid.
Let the amount of acetic acid be
The
would be
set free,
The
iFriedel and Ladenburg: Ann. Chim. Phys. [4], 23, 430 (1871).
Ewan Ztschr.phys. Chem. 16, 340 (1895).
the principle
of.
579
sum
Integrating,
If the acid used as the catalyzer is different from the acid of the
ester, the constants are of course different, and we would have as
the
sum
of the
two
velocities,
f (C'A+Gx)(B-x),
t
whose integral
is,
1
Cases similar to the above were tested by Ostwald and satisfacIf we understand the principle of the
tory constants obtained.
coexistence of reactions, we can proceed to study cases where a
number
Side Reactions.
substances
which were brought together react in more than one way, giving more
than one set of products. In addition to the principal reaction, we
have then one or more side reactions with velocities of their own.
The velocity coefficient which we measure is the sum of the coefficients of the several reactions.
The simplest
case
is
this case
Integrating,
The
"Test
of side reactions"
Wegschneider
Ztschr. phys.
Chem.
580
C
~
=
1
ratio
and
d+ C
K, we can calculate
<7/
and
C2
r,
r.
From
this
^2
The
Integrating,
From
= d (A, - x) - C
?jj
(A2 + x).
(1)
^=C (A-x)(B-x}-~d(C+x)(D +
1
If
C and D at
The equation
who
(2)
x).
the
first
tone,
CH OH CH CH COOH = CH CH CH CO + H 0/
.
It
was
also tested
by
Ktister,
who
Chem.
Ztschr. phys.
"Side reactions."
See Blanchard Ibid. 41, 681 (1902).
Ktister: Ibid. 18, 161 (1895).
:
Bugarky
Ibid. 11,
668 (1893)
12,
223 (1893).
581
The equation
He
lauch. 1
Since
all
is
tion is so great and in the other so small that the latter can be disregarded. Where the counter reaction has an appreciable velocity
it must be taken into account.
We
of another reaction, or we may have the products of a reaction reacting with some of the original substances. In such complex cases it
all the various quantities must be taken into account.
detailed study of such cases would scarcely be profitable in
this connection, since no new principle is brought out or illustrated.
is
obvious that
The
We
is
gation, the velocity of the reaction will depend upon the magnitude
of this surface.
This must be taken into account in dealing with
1
582
We
A heterogeneous
Heterogeneous Reaction of the First Order.
is one in which two substances in different
as the reaction proceeds, while the active mass of the other, or the
surface, remains constant.
Applying the law of mass action to such
a case,
we would have
A the origi-
we have
In
-7^- = CM.
he chose the better crystalline form. The spar was tested not
its crystal planes, but in two other directions, the one paral-
only in
and the other at right angles to the principal axis. Although the
velocity of the reaction between the spar and the acid was different in different directions, it was the same in any given direction.
The result as a whole was that fairly good constants were obtained
indeed, as good as could be expected under the conditions.
An analogous case, as Ostwald 4 points out, is the solution of
solid in liquids, and the
separation of solids from supersaturated
solutions.
Take the first case The velocity with which the solid
lel
Ber.
d. chem. Gesell
9, 1646 (1876)
10, 34 (1877).
3
Ztschr.phys. Chem. 2, 13 (1888).
jfo^.
Lehrb. d. Allg. Chem. II, 127, p. 288.
;
2
*
2 Q9 (1887).
583
dissolves depends upon the magnitude of the surface of contact between the solvent and the solid, and, of course, decreases as the satu-
We
We
supersaturated solution.
If,
**
(1903).
Bruner and Talloczko Ztschr. phys. Chem. 35, 283 (1900) Ztschr. anorg.
Chem. 28, 314 (1901) 35, 23 (1903) 37, 455 (1903).
u Rate of
precipitation."
Gladstone and -Tribe: Proc. Roy. Soc. 19, 498 (1871)
Journ. Chem. Soc.
24, 1123 (1871) Journ. prakt. Chem. (1) 67, 1 (1856)
69, 257 (1856).
See also Haber Ztschr. phys. Chem. 32, 193 (1900) Ztschr. Elektrochem.
:
Hood
Bohr
Drude's Ann.
1,
244
(1900).
(1903).
38,
512 (1894),
584
change in surface,
reactions between
That such reactions take place with a finite velocity is quite certain,
and it seems probable that methods may be devised for measuring
these very great velocities in the future.
reaction between two solutions giving a solid, with a velocity
which can be measured, is the following
Na
S2
+ 2 HC1 = 2 NaCl + H + S0 + S.
2
influences
which
methods of determining
and then some of the
such as tempera-
traces of moisture,
The
principle of the coexistence of reactions was then disand applied to side reactions and counter reactions.
Attention was next turned to heterogeneous reactions of the first
and second orders.
etc.
cussed
With
dynamics we pass to a
15,
533 (1888).
585
CHEMICAL EQUILIBRIUM
the active masses of the original substances become less, and the
active masses of the products of the reaction become greater.
After
a time a condition
maximum
attain a
is
is
known
known,
as the
When ethyl
and
C 2 H5 OH + HOOC
CH = H
3
+ CH COOC H
3
5.
this relation
What
reached
we
586
How
how
We have
reactions in
hol and acid react forming the ester and water, and then the ester
and water react forming the original acid and alcohol. Instead of
C 2H5 OH + HOOC
CH
^CH COOC H + H
3
0,
with the
We
velocities will
condition of equilibrium.
Equilibrium in a chemical reaction
which the
is,
this is the
It is only necessary to
the velocities of the two opposite reactions equal, and we have
at once the condition of equilibrium.
make
We
shall
now study
these conceptions.
Equilibrium in First Order
We
have
Homogeneous Reactions.
seen that the velocity of a homogeneous reaction of the first order is
expressed by the equation,
587
is,
Since the two reactions are exactly the reverse of one another, the
into
1} and the other the
A
=
Xj_
and dx =
dx^
Sub-
The
sum
of the
velocities of the
from which,
When
established, the amounts of the two subwhich are present, are proportional to the velocity
This is true independent
constants C and Ci, of the two reactions.
of the amounts of the substances with which we start so that knowing the velocity constants of the two reactions we can calculate at
stances
the equilibrium
is
A and AI,
once
is
how much
when
equilibrium
established.
fusion,
into
588
homogeneous
In such
Equilibrium in First Order Heterogeneous Reactions.
it will be remembered, the substances are in different states
of aggregation the one a solid and the other a liquid, the one a
liquid and the other a gas, or the one a solid and the other a gas, and
reactions,
Since, as we have seen, the active mass of a solid with rethe other states of aggregation, or of a liquid with respect
to
spect
to a gas is a constant, the active mass of the other substance must
so on.
The transformation
of matter
may
be established.
from one
The
cyanogen being at ordinary temperatures a gas and paracyanogen a solid. At about 500 cyanogen undergoes transformation
into paracyanogen, and above this temperature paracyanogen is
transformed into cyanogen, as Troost and Hautefeuille l have shown.
Equilibrium exists at any given temperature between the two polymeric forms, when the vapor-pressure has reached a certain definite
reaction,
value.
Ponsot
When
Pog g Ann.
f
Foote
[5], 2,
163 (1874).
589
modification
is
book, Etudes sur les Equilibres Chimiques, which is far less known
For details in this connection reference
than, it deserves to be.
must be had
to his work.
Equilibrium in Second
Order
The
Homogeneous Reactions.
thus
where
and
B are
react.
g= a (A For equilibrium
dt
x)
must be equal
to zero, whence,
C(A-x)(B-x) - C^Ai + x) fr + x) = 0,
(A - x) (B - x)
or,
= d (A, + a) (B + x).
t
C
'
'
Ci
1
(A-x)(B-x)
Ann. Chim. Phys.
Moutier
Lieb.
(1862)
23, 14 (1881);
30, 81
(1885).
[3], 65,
Lemoine:
385 (1862)
[3], 66, 6
590
If
we
and
JB,
we should
repre-
by unity.
reaction neither AI nor Bi is present, their active masses would be
zero.
Substituting these values in the above equation, we have
The
reaction
another acid.
Knowing
when each
rately upon the base, and the heat set free when a salt of one of the
acids is treated with the other acid, we have the data necessary for
calculating the amount of the base which goes to each acid in brief,
;
action.
The simplest and most direct method of testing the above equation experimentally was that employed by Ostwald.
When substances react chemically there is almost always a change in volume
produced, and the change in volume
different substances.
is different
by a given
base there results a certain change in volume, which is different from
the change in volume produced when another acid is neutralized
by
acid
is
neutralized
it.
From the above data we could determine at once how the base
divided itself between the two acids how much of the base went
j
591
to each acid
Ostwald used his results to test the above deduction, by calculating the change in specific gravity which should be produced if this
equation is true, and then comparing the values calculated with
those found experimentally.
factorily as could be expected
The two sets of values agree as satiswhen we consider that the change in
volume which
may
be
solid.
We
will take
is
up the simplest
a solid and the
We
The
The
is constant,
velocity of this reaction is
When
and we
is
is
established
we
would have
G(A - x) (B - x) =
d (Ai + x)8,
C1 S_(A-x)(B-x)
C
A!+X
"
If we start with
we would have
unit quantities of
A and B,
at the outset
A t = 0,
G
There are many examples of equilibrium known which belong to
Thus, when two soluble substances are brought together
and a precipitate is formed and only one soluble substance remains
in solution, we have an example of this kind of equilibrium.
The
action of sulphuric acid on barium chloride, giving barium sulphate
and hydrochloric acid, will serve to illustrate this principle.
It is not necessary that the insoluble substance should be formed
this class.
592
may
belong to this
class.
One
COO V
COOH
>Ca + 2HCl:zCaCl +
COO/
COOH
2
When
cs
If
we use
= 0,
CS
A=\ A
and
a?
in the
way
by starting with calcium chloride and oxalic acid, when the equation
first deduced applies to it.
The conclusions from theory have been
verified
by experiment.
Equilibrium in Second Order Heterogeneous Reactions, where
Two Substances are Solid.
If two of the substances which take
in
the
reactions
are solids, their active masses will be
part
reciprocal
1
Journ. prakt. Chem. [2], 22, 251 (1880).
Lang: Ztschr. phys. Chem. 2, 173 (1888).
Ostwald Journ. prakt. Chem. (2) 16, 385
(1877)
:
(1880)
24,
19,
468 (1879)
486 (1881).
Bugarsky
Ztschr. phys.
Chem.
11,
668 (1893)
12,
223 (1893).
28, 259
593
For equilibrium,
from which
G1 S1 = A-x_
OS
A! + x
and the
ward
The
follow-
594
chloride, and it was found that the pressure of the ammonia gas set
free at any given temperature was independent of the amounts of the
The
We
the more
most
exact.
The
when
equilibrium
is estab-
first
and second
orders.
gas.
different-
modifications
substance are
as
phases
of
known
of
that
substance, and we
therefore know most
UOQID
It may ocphases.
cur that the same
substance exists in
VAPO R
-
TEMPERATURE
FIG. 70.
more
than
three
aggregation.
coexist
in
Take a
595
is
water.
Water
depending chiefly upon the temperature, and also upon the pressure.
If we draw the temperature-pressure curves representing the con-
PA
is
above
The curve PB
line of
is
the
equilibrium
PB
above PC.
The
curve PC is the line
of
equilibrium
TEMPERATURE
FIG. 71.
be-
tween the solid phase of water and water-vapor; above this curve
and to the left of PB ice is the stable condition, while below this
curve and PA water-vapor is the stable phase.
596
must be equal to
it.
to the point P.
Since it represents a condition of equilibrium between three phases, it is known as
a Triple Point. The curves PA, PB, and
represent conditions
special
PC
of equilibrium between two' phases, and the areas PAB, PBC, and
represent conditions under which only one phase is stable.
can now state and apply the generalization known as the Phase
PCA
We
Eule,
means that none of the conditions can be varied without destroyis an example of a noning the equilibrium. The triple point
variant system. The number of phases is three and the number
of components one, and we cannot
vary either the temperature or
the pressure without disturbing the equilibrium between the three
phases.
We
we keep on the
597
having two degrees of freedom. This is exemPAB, PBC, and PCA. The number of phases
plified
is one, and the number of components one, and two variables exist.
We can vary both the temperature and the pressure provided that
we keep within the given area, without in any wise destroying the
system
is
divariant,
by the areas
equilibrium.
We have now seen what the phase rule is and what is meant by
a triple point, a non-variant, monovariant, and divariant system. It
is possible to have more than three phases in equilibrium at a point.
if five, a quintuple
If there are four, the point is a quadruple point
had
monovarihave
we
as
And
so
on.
and
non-variant,
just
point,
ant, and diyariant systems, so if the number of components is
;
greater than one we may have systems where there are a still larger
number of degrees of freedom. With these fundamental conceptions clearly in mind, we shall now apply the phase rule to a
of problems in chemical equilibrium.
number
The
have, however, been considered only from one standpoint as illustramust now study more carefully a few
tions of the phase rule.
We
return to the temperature-pressure diagram of water. The following contains in addition to the above-mentioned curves the curve PCj,
and
in the
but we
know
that
we may
below
its
freezing-point
no dust or other solid matter
598
moved.
all
for water.
passes over into the stable condition. This shows that the stability
of the different phases is purely relative.
An
which
is
that
the metastable phase can no longer exist as such, but passes over
into the phase which is stable under the conditions.
we have
At the
two
curve
critical
temperature
PA.
This comparatively simple diagram is, then, a shorthand expression of a large number of experimentally established facts.
have in sulphur a good example of one substance existing in
We
We
liquid phase
slowly.
When the monosulphur melts higher than orthorhombic, at 120.
clinic phase is kept at
it
ordinary temperatures,
passes over gradu1
Ztschr. phys.
Chem.
which
is
599
temperatures.
as we have seen, the orthorhombic passes
Therefore, at low temperatures the orthorhombic is the stable, the monoclinic the metas table phase.
At higher
temperatures, up to 131, the monoclinic is the stable phase, while
the orthorhombic is ths metastable phase.
The temperature at
At higher temperatures,
solid
at
which both
solid phases can coexist without either passing into the other
is known as the transition temperature, and for sulphur this is 95. 6.
In addition to the two solid phases of sulphur we have the
liquid
If
we
diagram of sulphur as we
would have the following form
it
115
120
TEMPERATURE.
FIG. 72.
600
bic sulphur
point
phur, while
phur.
is
repre-
PA
rhombic sulphur
prolong the curve, Pj(7 representing equilibrium between liquid sulphur and its vapor until it meets the prolongation of PB, it will do
see
Pm
If
what kinds
of
clinic,
The point
reprethe three phases orthorhombic, monotherefore, a triple point.
Similarly, P^
is,
n
represents equilibrium between monoclinic, vapor, and liquid
between orthorhombic, monoclinic, and liquid, and
(in the meta;
Pm
We
liquid,
and
then, four
vapor,
triple
and
points,
is
601
non-variant.
curves. PB represents equilibrium between orthorhomand vapor, PPf between monocliiiic and vapor, PjQ between liquid
and vapor, PjPu between monoclinic and liquid, PuP between orthorhombic and monoclinic.
Take the
bic
PA
regions.
is
variant systems.
EPuPB
is
only one
stance
are Variable.
The
reference
volume
to
the
curves
or
pressureisother-
we
start
VOLUME
FIG. 73.
602
At 6 a portion
represents the relations between these two variables.
of the vapor may become liquid if so, further diminution in volume
;
can take place without increasing the pressure. At c all the vapor
has become liquid, and beyond this point enormous pressure is
This is shown by
required to produce small changes in volume.
the dc portion of the isothermal rising nearly parallel to the
The isothermals for higher and higher temperatures
ordinate.
resemble, the one just considered, a greater pressure being required
the higher temperature to liquefy the vapor.
Finally, the
isothermal is reached which passes through the critical point (7, and
at
shown
in
(Fig. 74).
the
sketch
The
position
of the isothermals is seen
at once, also the regions
of pure vapor and of
in
which
both
VOLUME
FIG. 74.
the
learned.
We shall not
Equilibrium between Phases of Two Substances.
take up the large number of conditions of
physical equilibrium
between the substances, such as the solubility of a solid in a liquid,
etc., since these have been referred to in other connections; but
pass at once to the conditions of chemical equilibrium between two
components and three phases.
case which is generally discussed because of its
comparative
between a
containing water of
has been shown that this
salt
and water-vapor. It
depends upon the tension of the water-vapor, and we must
sider a method by which this is measured.
crystallization
first con-
603
first
2
proved and used by the same investigator.
The
tensimeter is
evacuated
and
sealed.
is
to another.
mm.
is
existence of
Ztschr. phys.
Sudden drops
Chem.
1,
10 (1887)
in the vapor-pressure
2
would
604
.of
molecules of water.
We
We
can vary
we
and
pentahydrate, ice, and vapor,
is, therefore, a quadruple point.
we examine
the regions we
the anhydrous salt can
exist in AOT, the monohydrate
If
see that
TEMPERATURE, T
'
DP PE,
FIG. 76.
water in
EPF, and
ice in
Let us turn next to conditions of equilibrium betiveen two compoand four phases. We shall deal with hydrated salts, i.e. those
containing a certain number of molecules of water. We may have a
number of such hydrates formed by the union of one molecule of the
nents
water-vapor
We
still
another phase.
shall study fa
some
formed with
ferric
605
1
chloride, these having been carefully investigated by Roozeboom.
He found that there were four hydrates of this substance containing
and four molecules of water, and their meltingpoints were, respectively, 37, 32.5, 56, and 73.5 at the meltingIf to a
point the liquid and the solid having the same composition.
fused hydrate anhydrous salt is added step by step, a new hydrate
twelve, .seven,
five,
make
its
of water.
- 55,
salt,
TEMPERATURES
FIG. 77.
water and
ered,
and
this is represented
55
ture
= Fe C]
is
H 0,
is
12
Ztschr. phys.
2 Ibid.
8
Chem.
10,
We
If
more
477 (1892).
502 (1892).
Since Roozeboom uses Fe 2 Cl 6
10,
it will be retained.
In connection with these more complex cases, symbols are frequently used
instead of the names of compounds to simplify compa son with the diagrams.
4
606
salt is
added,
and
DN
We
is reached, and
to the transition point
(55), and so on until
the
transition
this is
point between the lowest hydrate and the
represents the solubility of anhyanhydrous salt. The curve
KL
number
libria
vapor
of quadruple points.
The
It has a
between the two hydrates, the saturated solution, and wateri.e. between four phases, and are therefore
quadruple points.
KL
represent solu-
stable
H
HR
regions.
As Roozeboom
DEF, FGH,
etc.)
general phenomenon."
Ztschr. phys.
Chem.
10,
486 (1892).
Ibidi 4j 34 (1889).
607
We
Systems con-
3
by Van der Heide.
The most important applications of the phase rule to systems
containing a number of components have been made in the last few
years by Van't Hoff and his pupils. They have studied the conditions of equilibrium between complex systems, in order to obtain
some light on the problem of the formation of the great salt beds,
and interesting and valuable results have already been obtained. In
It has
Ibid
5,
97 (1890)
9,
641 (1892).
608
and
solids,
Van't Hoff
Cyamelide:^: cyanuric
The transformation point
is
acid.
in temperature.
cyanuric acid by a simple rise
First Method.
Transformation
the
of
Determination
Temperature.
Since transformations in condensed systems are always accompanied
specific
volume of
is
known
as a dilatometer, consisting of a
The substance
glass bulb attached to a fine graduated glass tube.
whose transformation temperature it is desired to determine is introduced into the bulb, and the remainder of the bulb filled with some
liquid (say an oil), which extends into the graduated
tube.
The apparatus is then placed in a bath whose temperature
can be gradually raised. As the liquid in the dilatometer becomes
warmer it expands gradually, the meniscus rising at a regular rate
indifferent
itself
level of
be prevented;
so, also, if
1
p. 141.
609
transformation
Second Method.
temperature heat is
when this thermal change occurs, we can determine the transition
temperature. The substance in question is placed in a tube, into
which a thermometer
is
The substance
introduced.
is
then warmed
or cooled
When
this is
at
The general rule holds that the system formed at the higher
temperature absorbs heat.
TJiird Method.
Another method of determining transformation
1
temperatures is based upon the fact pointed out by Meyerhoffer,
that at this temperature the solution of the original substance is
which it is transformed. The two solutions
+ H 0.
2
The arrangement
(Fig. 78),
which
The
vessels
ZnS0 4 .7H 2 0.
and
The
are
solution in
filled
is
Ztschr. phys.
Chem.
5,
105 (1890).
164 (1889)
34, 179 (1900).
Ibid. 14, 53 (1894).
(1899)
31,
3*
Cohen
30,
623
610
gradually raised to the transformation point, the galvanometer being read every few minutes. As the temperature approaches that of
and less. At the transformation temperatwo sides become the same, and, conse-
little later
FIG. 78.
by a saturated
solid
solution of the
phase of the
same
salt in the
salt.
The electromotive
force of such
an element 2
"
is
a function of the
611
The temperature
solubility of the stable solid phase of the salt.
coefficient of the electromotive force is, therefore, a function of the
temperature coefficient of solubility. It is well known that the latter
changes suddenly at the transformation temperature, and, therefore,
the temperature coefficient of the electromotive force changes sud-
temperature in question.
must be
tem
is
generalization has been reached connecting change in temperature with change in equilibrium, which is very important and
accords with what we should think would take place.
The effect
rise in temperature is to favor the formation of that system which
An increase in temperature, thereabsorbs heat when it is formed.
of
fore,
displaces
which
is
Some interesting relations between temperature and heat evolution in chemical reactions have been discovered.
Bodenstein and v.
Meyer have shown that a much
1
absorbed at 186, the reaction thus becoming less and less endothermic
with rise in temperature. We should, therefore, think that the effect
of rise in temperature
would be
to increase the
amount
of hydriodic
acid formed, and such is the fact up to about 320. With still further
rise in temperature the amount of hydriodic acid formed undergoes
diminution.
This reaction which is endothermic at the lower
Ztschr. phys.
Chem.
13, 56 (1894).
612
peratures.
experimentally.
Troost and Hautefeuille
silicon tetrachloride
the compound Si 2 Cl 9 is
is passed over very highly heated silicon,
substance
this
was determined
of
the
formed. When
vapor-density
the
that
substance
was stable
found
was
it
at different temperatures,
Between 350 and 1000 it was unat all temperatures up to 350.
stable,
maximum
temperatures.
The question
as to
is
exothermic or
endothermic
The action of
Effect of Pressure on Chemical Equilibrium.
pressure on chemical equilibrium is through the resulting change
in volume.
Here also the equilibrium may be displaced in the one
or the other direction, or may be only very slightly displaced.
temperature.
Increase in pressure diminishes the volume, and therefore favors the
formation of that system ivhich occupies the smaller volume. Equi-
librium
4
by Le Chatelier
Brunck: Ibid.
4
Zengelis
Ztschr. phys.
The displacement
of a system produced
613
above principles.
hydrogen acts Upon oxygen, forming water, the resulting
vapor occupies only two-thirds the volume of the original gases. In-
When
than the
initial substances.
When hydrogen and iodine react and form hydriodic acid, there
no change in volume
the resulting gas occupying exactly the
same volume as the original gases.
Increase in pressure should,
therefore, have no effect on this reaction.
The work of Lemoine 1 shows that this is the case. In fact, all
of the above conclusions have been verified experimentally.
is
The amount
of dissociation depends, as
Some
we have
seen,
upon the
or-
Other electrolytes, such as the strong acids and bases, and the salts,
are strongly dissociated even in the most concentrated solutions
which can be prepared.
The degree
614
we mean
ions there
that
when
is
proceeds with
its
own
When
definite velocity.
we have
seen,
Solubility as affected
We
must
with a
first
common
To make
tion ?
KC103 =K
any 'potassium salt represented
by
KA
KA = K + A;
any chlorate represented
by
MC103
MC103 =
The second
thus
M + C10
3.
an ion in
common with
the
first.
615
cealed.
common
ion
We
*
was the first to solve this
from
the
theoretical
question quantitatively
standpoint. He applied
the law of mass action as follows 2 If we start with binary electrolytes which are completely dissociated, the product of the active
masses must be constant, and equal to the square of the solubility
:
termed
common
ond
salt
ion
m (m
-f-
x)
litre,
=m
sec-
2
.
(1)
The
we
ma(ma.
1
Ztschr. phys.
Chem.
4,
-f
xa^
372 (1889).
=m
2
.
(2)
2
/^.
379.
616
This formula simply expresses the fact that the product ot the
masses of the ions is constant.
If we turn our attention to the undissociated portion, we find the
a represents the dissociated portion of
following relations Since
is the undissociated portion
and
the original electrolyte, m (l
#)
since ma is the dissociated portion after the second electrolyte is
0)
=a
1}
(3)
a).
we have
2a
If
= m(l
a2
a2
m=
2 4-\lm
*
<
Nernst tested his equation in a few cases, and found that it held
approximately for the solubility of one substance in the presence of
another.
AMOUNT AoNOg OR
The following
617
the solubility as calculated being several per cent less than the value
found, and the difference increases as the quantity of the second
electrolyte present increases.
clusion
Ostwald
electrolytes.
is
not a
common
f),
m(m + x)a? =
and
m(l
a,
a)
^W,
= m (l
),
eliminating
is
salt in the
6,
259 (1890).
618
From experimental
(m+
x).
presence
soluble in water, and the above and similar relations hold only for
The results for the dissociation of hydrofairly dilute solutions.
chloric acid
and thallous
nitrate, as
method, did not agree with the dissociation of the same substances at
the same dilution as determined by the conductivity method. Noyes
introduced the dissociation values as found by solubility into the
Ostwald equation (dilution law), and obtained a fairly satisfactory
constant for a strongly dissociated electrolyte like thallous nitrate.
It looked, therefore, as if the Ostwald dilution law would hold also
for strongly dissociated electrolytes, when the true values for the
dissociation of such substances were ascertained.
A little later
made
a slight error which, however, affected all of his calculadetermined the dissociation of potassium, sodium, and
ammonium chlorides by means of the solubility method, and when
see,
tions.
He
the values for potassium chloride were introduced into the Ostwald
equation, a very good constant was obtained; while the law does not
hold at
all if
Noyes
chlorides
also
by the
solubility
method.
solution, but in
some
conductivity
Ztschr.phys. Chem.
9,
603 (1892).
619
Noyes was
an accurate measure of the dissociation of strongly dissociated elecIt seemed probable, however, that the conductivity method
was capable of measuring the dissociation of weakly dissociated compounds with a fair degree of accuracy.
Thus the problem stood at this time (1892). There were two
the conmethods available for measuring electrolytic dissociation,
and
these
different
and
the
results.
gave
ductivity
solubility method,
trolytes.
The problem
At the suggestion and under the guidance of Ostwald, Jones l improved the freezing-point method of Beckmann until it could be used
to measure electrolytic dissociation.
He applied it to a number of
acids, bases, and salts at dilutions ranging from 0.1 normal to 0.001
normal, and obtained results for the dissociation of these substances
which agreed very well with those obtained by the conductivity
method.
This
sociation, since
still
all
620
it
was
this fact
many
directions.
Summary
The fundamental
The phase rule was then briefly, disopposite reactions are equal.
and a few of its simpler applications to
cussed,
systems containing
one component, two components, three
components, and four components. Equilibrium was studied where two conditions are
variable, say
temperature and pressure, and also when three conditions are variable,
say temperature, pressure, and volume, and the corresponding diagrams
Some of the applications of the phase rule, not
plotted.
as a
simply
system of classification, but as a direct guide in experimental work,
were considered. This was seen to be the case
especially where the
number
of components is
large, or where the older methods of investigation are insufficient on account of the comparative
complexity of
the
phenomena dealt with. The methods of determining the temperature of transformation were considered, also the effect of temperature and pressure on chemical
equilibrium, and then attention was
directed to a special case of
equilibrium which has proved to yield
extremely important results. This refers to the effect of one salt on
the solubility of another with a common
ion, which has led to an
important method of measuring electrolytic dissociation.
621
CATALYSIS
In connection with catalyzers not being able to start a chemical
reaction, it should be stated also that they cannot affect the final
equilibrium of a reaction which is reversible. The amount of energy
transformed in any reaction depends only on the initial and final
If the catalyzer could change the
states of the reacting substances.
final state, it would change the amount of energy transformed in any
it.
that the
catalytic
with
rise in temperature.
by
The
which cannot be
ture
sels led J. J.
easily
Thompson
changed physical condition of the molecules of the substances entering into the reaction, where they came in contact with the walls of
the vessel.
The molecules
fall in
622
(1)
One
catalyzer
but its surface, which is concatalyzer is not the important feature,
ditioned by its state of division.
The second class assumes the existence of intermediate reac(2)
tions
catalyzers.
The
second
first
is
these sets of
theory of catalysis,
as the inver-
hy
The
others, has
the undissociated, or only partially dissociated molecules of elecThese molecules, when they effect catalysis, may be in the
trolytes.
act of breaking down into ions
or the ions already present may
exert some influence on the undissociated molecules.
Whatever the
;
is
32, 22 (1909)..
3, 30, 1
(1903).
623
ital. 39, 1,
35 (1909).
Zaleski
Marc:
Ber.
d.
Chem.
Zeit. phys.
Paal
Ber.
d.
Zeit.
Chem.
Zeit. phys.
Ipatiew
Taylor
2, 35.
The most
tant in this
field.
Ernest Cohen
75, 1,
Zeit. phys.
Chem.
ALLOTROPY
Space will not permit of any detailed discussion of the work of
Ernst Cohen and his co-workers on the allotropy of the metals.
The work, however, is of such interest that it has seemed desirable
directly
Zeit. phys.
Chem.
33,
624
."
On
129 (1905)
"
"
"
52,
"
CHAPTER X
MEASUREMENTS OP CHEMICAL ACTIVITY
METHODS EMPLOYED AND SOME OF THE RESULTS
OBTAINED
Great Differences in the Activities of Substances.
The student
given metal very readily, others act more slowly, while others
scarcely act at
all.
When we
knew the
we should be in a posiwhen such substances were
We
we have methods
of solving this
by
the velocities will vary from acid to acid, and may be a hundred
times as great for one acid as for another. Take, on the other
2s
625
626
above,
invert cane sugar, or a number of bases saponify an ester, we have
at once the relative activities of the acids, or bases, in question.
This is known as the dynamical method of measuring chemical affinity.
When we
we saw
we can
known
reactions.
Affinity.
(A)
We
we
He
are
now
familiar,
coefficients directly.
627
few of
the results obtained for the inversion coefficients of some of the more
common
unity
.....
.......
.....
.....
.......
.....
......
.......
......
.....
......
.....
.......
......
.......
......
.......
INVERSION COEFFICIENTS
Hydrochloric acid
Nitric acid
1.000
1.000
Ethylsulphuric acid
1.000
Hydrobromic acid.
1.114
Chloric acid
1.035
Benzenesulphonic acid
1.044
Sulphuric acid
0.536
Formic acid
0.0153
Acetic acid
0.0040
Monochloracetic acid
0.0484
Dichloracetic acid
0.271
Trichloracetic acid
0.754
Oxalic acid
Succinic acid
Citric acid
Phosphoric acid
Arsenic acid
0.1857
0.00545
0.0172
0.0621
0.0481
its
velocity
may
this.
The
acid which
is
It acts catalytically.
added
The
active
mass of the
1
This equation was tested experimentally by Ostwald, who used
this reaction to measure the relative activities of acids, and BC was
found to be a constant for this reaction through a long interval of
time.
628
Hydrochloric acid
Nitric acid
1.000
0.915
0.987
Ethylsulphuric acid
Hydrobromic acid
0.983
Chloric acid
0.944
Benzenesulphonic acid
0.991
Sulphuric acid
0.541
Formic acid
0.0131
Acetic acid
Monochloracetic acid
0.00345
Dichloracetic acid
0.2304
Trichloracetic acid
0.6820
Oxalic acid
0.0430
0.1746
Succinicacid
0.00496
Citric acid
0.01635
comparison of the velocity coefficients obtained by the methylacetate method, with the inversion coefficients obtained by the
method involving the inversion of cane sugar, shows a general agree-
CH CONH + H
3
This
in-
= CH COONH
8
4.
is
increased,
and
In the presence of an
CH CONH + H
3
OT
629
nearly the true velocity coefficients for the different acids can be
obtained by studying the decomposition of amides at the very outset of the reaction.
VELOCITY COEFFICIENTS
Hydrochloric acid
Nitric acid
Hydrobromic acid
....
.
0.972
0.547
Sulphuric acid
Formic acid
0.00532
Acetic acid
Monochloracetic acid
Dichloracetic acid
Trichloracetic acid
....
....
....
0.000747
0.0296
0.246
0.670
0.169
Oxalic acid
If
1.000
0.955
Tartaricacid
0.0121
Succinicacid
0.00195
Citric acid
0.00797
Phosph'oric acid
0.0449
we compare the
results obtained
is
decomposed.
acetate
The
of
activities
Reicher. 2
A few
given below
1
3,
340 (1882).
Lieb.
Ann.
630
...
....
Potassium hydroxide
Sodium hydroxide
Ammonium
VELOCITY COEFFICIENTS
hydroxide
2.298
2.307
0.011
Barium hydroxide
2.144
Strontium hydroxide
2.204
The most
ammonia
methods.
We
shall
now
leave the
relative
and pass
Activities.
a simple matter to determine the conditions which exist when equilibrium is established. It is only necessary to determine the amount
of the solid present, or to separate the heterogeneous constituents,
which take
sodium hydroxide, by
from the heat of neutralization of the same amount of the same
base under the same conditions,
by a different acid, say sulphuric
We
Let us
JV3 would
N N
2,
1}
N
NP
and
equal to
-be
3.
631
But
acid,
to act
on the
is
is
as indicated
above.
We
and neutralize
one acid by two bases separately, and then by both bases simultaneously, and from the data thus obtained calculate the relative strengths
of the bases.
and bases can be worked out by thermochemical measurements. In such investigations, however, side reactions may come
into play, and such must of course be taken into account wherever
ities of acids
they appear.
It should be mentioned again in connection with this method,
tha,t thermochemical measurements are difficult to make with even a
fair degree of accuracy, and this method is never used to-day, since,
as
we
When a given
18,
328 (1878).
632
prehend.
is
allowed to act on the salt of another acid, and from the division of
the base between the two acids the relative strengths of the acids
determined.
fusion.
At
first
is liable to
lead to con-
when
acid acts on dry nitrates, practically all of the nitric acid is driven
out.
This might be thought to indicate that sulphuric acid is infinitely strong
Again,
chloride or nitrate of a
heavy metal, the insoluble sulphide is preand in many cases quantitatively. From this it might be
concluded that hydrogen sulphide is a much
stronger acid than
cipitated,
hydrochloric or
nitric.
that,
compound
is
where everything
is
633
utilize, respectively,
the thermal
activity reduces
The problem
itself, then, to
of measuring chemical
dissociation.
of Kohlrausch
and
its
application to the
measurement
same
extent.
nitric,
of the salts of mercury, such as the chloride and cyanide, are scarcely
dissociated at all.
The above statement, nevertheless, applies to
most of the salts, including those of very weak acids, such as car-
634
bonic and
pounds.
Similarly, when
of the substituted
we deal with
we find
that
many
ment
of chemical activity.
bases
-=
applies.
(l-a)v
direct measure of the
strength of the acid
and
base, as
we have
seen.
1
For details in connection with the
strengths of organic acids and bases see
Ostwald Ztschr. phys. Chem. 3,
170, 241, 369 (1889); and Bredig Ibid. 13, 289
:
(1894).
635
sociations at
dilution law,
The
latter
mode
of procedure
is
it is
simpler
since
for measuring
chemical
activity.
If
we
we
it
an element.
"
636
What do we mean by an
do other elements affect acidity at all ?
?
element
acid-forming
Elements other than hydrogen do not affect acidity directly, but
they
may
affect it
we say
that an element
it is
present.
If we examine the strength of acids in the light of these newer
conceptions, we shall find some surprising results even among the
conductivities at the
VOLUMES
same
dilutions,
we
have
with
have
their
637
below
VOLUMES
638
other cases.
of
members
VOLUMES
639
These results show that formic acid is much stronger than any
The acidity of the following
succeeding member of the series.
members does not change very appreciably with increase in the complexity of the molecule there is, perhaps, a slight decrease in the
;
similar
manner
VOLUMES
640
the radical
its
monoxygen
VOLUMES
641
'
VOLUMES
642
643
conception of the tetrahedral carbon atom, these acids are to be represented by the following formulas
:
MALEIO ACID
H - C - COOH
II
H-
C - COOH
FUMARIC ACID
H - C - COOH
II
COOH - C - H
In maleic acid the two hydrogen atoms and, similarly, the two
In fuinaric
carboxyl groups are on the same side of the molecule.
acid,
what
is opposite carboxyl.
It is very interesting to see
influence this difference in configuration would have on the
hydrogen
VOLUMES
644
645
COOH
HC/\CH
HC\/CH
CH
If
or
we
what
VOLUMES
646
it
This
is
VOLUMES
647
We
ent
weak
base
is
strong or
i.e.
When we come
to
ammonium
hydroxide,
we
find a base
which
is
VOLUMES
648
mucous membrane
of the throat
It
base,
The hydroxides
VOLUMES
649
amine, ethylamine,
VOLUMES
etc.
650
The introduction
considerably.
We
radi-
further diminish
VOLUMES
it.
The
effect of constitution
VOLUMES
651
Take
652
(NH3)
strongly dissociated
The
being
by the water.
We
much
INDEX
Abbe-Nollet demonstrated osmotic Anion, effect of the nature of on
potential difference, 486.
freezing-point Archibald and Mclntosh, work in
liquid halogen acids, 438.
method, 234, 235, 435.
Absolute boiling-point of a gas, 92. Arrhenius determines the value of
the coefficient i, 227.
Absorption spectra of gases, 80.
Absorption spectra of solutions, Arrhenius, effect of neutral salts on
the velocity of saponification,
recent work, 320.
576.
Accumulators, 504.
Arrhenius, on additive properties
Acetamide, action of acids on, 565.
and the theory of electrolytic
Acetylene hydrocarbons, thermochemical measurements with,
dissociation, 302.
354.
Arrhenius, on double salts in soluAcid and basic properties, 27.
tion, 427.
pressure, 188.
Acid,
thermochemical
Alcohols,
with, 355.
Alexeew, 180.
Allotropy, 623.
results
strength
Ammonia,
of,
of,
erties,
bers, 4.
to the
Atomic
weights
from
molecular
weights, 8.
435.
Amphoteric
of
relative, 4.
651.
liquid, dissociating
1.
stitution, 127.
specific heats,
10.
electrolytes, 297.
Atomic weights,
isomorphism
Anion, 211.
663
an
INDEX
654
535.
osmotic pressures, 200.
Baeyer, melting-points and composi- Berkeley and Hartley,
method
of
tion, 168.
Baker, dry ammonia does not act on Berthelot and Saint Gilles, bearing
of their work on mass action, 540.
dry hydrochloric acid gas, 452.
Baker showed that certain sub- Berthelot, principle of maximum
stances do not burn in dry
work, 544.
thermochemical work,
oxygen, 451.
Berthelot,
332.
Bancroft, study of oxidizing and reducing elements, 480.
Berthollet, discussion with Proust,
537.
Barmwater, on osmotic pressure, 222.
Barus and Strouhal, method of cali- Berthollet, on the effect of mass, 586.
Berzelius' electrochemical theory,
brating a wire, 393.
361.
Bases, conductivity of organic- and
their dissociation constants, 417. Berzelius'
electrochemical theory,
Thomson overthrows the objecBases, electrolysis of, 500.
Bases organic, strengths of, 648.
tion to, 363.
Basic and acid properties, 27.
Berzelius' method of determining
Basicity conditioned by composicombining numbers, 5.
Berzelius on the catalytic action of
tion, 647.
Basicity conditioned by constituferments, 556.
tion, 651.
Basicity of an acid determined
from
pirically
416.
its
Beckmann,
boiling-point apparatus
263.
Beckmann
boiling-point
method
freezing-point
method
264.
Beckmann
of
Bimolecular, or
actions, 561.
solvents,
445.
229.
INDEX
655
Bunsen
liquids, 99.
ice-calorimeter, 112.
of
col-
dissociation, 268.
Boiling-point of a gas, absolute, 92. Cady and Franklin, velocity of ions
in liquid ammonia, 435.
Boiling-points and composition and
Cailletet liquefied oxygen, 87.
constitution, 102.
certain Caldwell, on double salts in soluof
effect
Boiling-points,
atoms or groups on, 107.
tion, 427.
Boiling-points of liquid mixtures, Calorimeter, water, 325.
Cane sugar, inversion of, 531.
181.
Boiling-points, work since the time Cannizzaro and De Chancourtois,
work of, 20.
of Kopp, 104.
Boltwood, on the origin of radium, Carbon, from the thermochemical
standpoint, 337.
528, 531.
Boltzmann, on the free energy of Carrara, conductivity in methyl
alcohol, 439.
surface, 560.
Bomb, explosion, of Berthelot, 339. Carroll, work in mixed solvents, 444.
Catalysis, 553, 621.
Boyle, exception to the law of, 47.
Catalysis, theories to account for, 554.
Boyle, law of, 47.
Boyle's law for osmotic pressure, 203. Catalytic action of ferments, 556.
Brauner's modification of Mende- Catalytic action of finely divided
leeff's table, 35.
metals, 558.
Bredig and coworkers, catalytic Catalytic action of hydrogenions, 557.
action of finely divided metals, Catalyzers, negative, 556.
Cathode particle, charge carried by,
558, 559.
39.
Bredig and Von Berneck, method of
preparing colloidal suspensions, Cathode particle, mass
283.
Cathode
particle,
Bredig applies the Ostwald dilution
law to weak organic bases, 412.
37.
Bredig determines the conductivity Cation, 211.
of, 38.
relation of
for,
INDEX
656
and some
625.
Chemical
Chemical
affinity, 534.
method
dynamical
affinity,
of measuring, 626.
Chromosphere
stances,
of
subdifferent
of the
demonstration
different, 400.
368.
Clausius,
545.
423.
onductivities
theory
of
solutions,
ciation,
compared with
freezing-
weights, 4.
Conductivity of solutions, method
chemical
of measuring, 390.
Combining
numbers,
methods of determining, 5.
Conductivity of solutions of electroCombining power, chemical proplytes, 389.
erties and atomic weights, 24.
Conductivity, specific, 390.
Combining weights, law of, 3.
Conductivity, temperature coefficients of, 395.
Combustion, heat of, 353.
Composition and constitution, effect Conservation of energy applied to
of on chemical activity, 635.
thermochemistry, 334.
Composition as conditioning acidity Conservation of mass, law of, 1.
635.
Constant ceUs, 466.
INDEX
657
activity, 525.
conductivity
and
De
223.
Corona
De
Vries,
measurement
of relative
De
252.
INDEX
658
Dissociation
450.
Dissociation
Dissociation
and chemical
activity,
534.
of,
549.
trolytes, 613.
refractivity,
117.
Ekaaluminium,
Ekaboron, 33.
33.
Ekasilicium, 33.
Electrical charge, change in color
with change in, 290.
Electrical conductivity of crystals,
164.
Electrical energy, 370.
Electrical method of studying radioactive radiations, 520.
Electrical energy, transformation of
intrinsic energy into, 457.
Electrical units, 372.
Electricity
370.
and
ucts, 68.
Dutoit
vents, 449.
Dynamical method
chemical
of
affinity, 626.
208, 211.
Electrolytic separation of the metals,
500.
Electrolytic solution-tension, 461.
Electromagnetic system of units, 373.
Electromotive force calculated from
osmotic pressure, 458.
measuring Electromotive
of,
456.
force,
measurement
INDEX
Electromotive force of primary
659
454.
lytes, 613.
type, 467.
Emanium,
528.
Emden measured
the lowering
vapor-tension, 257.
Endosmose, 190.
Endothermic reaction, 337.
Energy unchanged in chemical
of
354.
Eutectic alloys, 251.
Evidence
for
hydrate
theory
of
Jones, 239.
re-
when
established, 585.
rotation, 135.
Faraday,
on
gases
absorbed
by
solids, 554.
549.
of,
374.
INDEX
660
Favre and Silbermann, work of, 331. Fused salts, dissociation of, 430.
Fusibility and volatility, 30.
Ferments act catalytically, 556.
Fick's law of diffusion, 274, 275.
359.
Finkelstein, on the passive state, Galvani's discovery,
453.
First law of thermodynamics, 72.
First order reactions, 551.
Fitzpatrick, conductivity in methyl
alcohol, 439.
Gamma rays,
521.
Gas-battery, 480.
Gases, 46.
Gases, absorption spectra of, 80.
and molecular
densities
Gases,
weights of, 57.
Freudenberg, electrolytic
of, 51.
Gay-Lussac's generalization, 6.
Gay-Lussac 's law for osmotic pressure, 203.
zation, 496.
Fused
428, 429.
INDEX
Grotthuss'
366.
theory
of
electrolysis,
661
first
order, 582.
reaction
of
the
of the periodic system, rela- Heterogeneous
second order, 584.
tions within, 26.
Guldberg and Waage, work of, 546. Heterogeneous reactions, 581.
Gutbier, method of preparing col- Hexagonal crystal system, 159.
loidal suspensions, 284.
Heycock and Neville, on solutions
of metals in sodium, 251.
Guthrie, work on cryohydrates, 252.
Groups
and
Kohlrausch,
Heydweiller
Guye, hypothesis of, 133.
method of purifying water, 394.
Guye's method of determining molecular weights of liquids, 318.
Hittorf, on the passive state, 453.
Hittorf's theory, 379.
of the
Hofmann's
modification
Lussac's method, 59.
of
Holohedrism, 160.
Hughes, dry hydrochloric acid does
not decompose carbonates, 451.
Hampson,
Gay-
diffu-
249.
Hartley and Berkeley, method of
measuring osmotic pressure, 217. Hydrates, a
existence
Heat and electricity, conduction of,
fifth
of,
argument
for the
based on tempera-
370.
397.
Heat, dissociation by, 542.
Heat liberated by radium, applica- Hydrates, approximate composition
tion to cosmic problems, 523.
of, 246.
Heat of combustion, 353.
Hydrates, a sixth argument for the
Heat of combustion, effect of conexistence of, 408.
stitution on, 357.
Hydrates, bearing of on the tempera-
Heat
Heat
Heat
of formation, 351.
of fusion, latent, 170.
of neutralization of
Hemihedrism, 160.
Henry's law, 177.
Hess, thermochemical work
330.
INDEX
662
Jones
and
Mackay,
method
of
and
Kohlrausch
method
Heydweiller,
Kopp, work on
boiling-points, 102.
INDEX
663
of gases, 85.
of,
473.
relations
be-
Kiister,
of solids, 312.
Law
optical
activity, 129.
electrolytic separation of
Le Blanc,
235, 435.
Le Blanc, measurements
''de-
of anions,
of
Le Blanc, solution-tension
463.
Le Blanc, source
of
153.
the electrical
refractivity, 117.
INDEX
664
McCoy, on
528.
in
maximum,
406.
Metals in mercury,
solution
and
Methane
actions, 551.
Morgan's
method
of
measuring
surface-tension, 317.
pressure, 319.
INDEX
665
Negative temperature
coefficients of
conductivity, 446.
Nernst and
Tammann,
of
pressure on the action of acids
on metals, 574.
Nernst and Wartemburg, dissociation of water-vapor, 149.
constants
of
dielectric
Nernst,
liquids, 154.
effect
INDEX
666
Wolfgang's classification
of colloidal solutions, 326.
Ota, on double salts in solution, 427.
Ostwald,
Oxidation, 433.
Pfeffer, 191.
by
Osmotic pressure, results of Berke- Palmaer demonstrates the solutiontension of metals, 464.
ley's measurements, 221.
Osmotic pressures, measurement of Paramagnetic bodies, 138.
Passive state of the metals, 452, 506.
Ostwald and Nernst tested the law Pasteur, on optical activity, 128.
of Faraday, 375.
Pebal, vapor-density of ammonium
chloride, 66.
Ostwald, change in volume in neuPeriodic system and the electron
tralization, 301.
classes
actions, 554.
Ostwald,
of
catalytic
re-
theory, 41.
Periodic system of Mendeleeff and
545.
of
osmotic
488.
Phase rule applied to sulphur, 599.
Ostwald, method of determining the Phase rule applied to water, 595.
order of a reaction, 572.
Phase rule of Gibbs, 594.
Ostwald, modification of Kohl- Phosphorus from the thermochemirausch's law, 404.
cal standpoint, 345.
Photochemical action, law of, 517.
Ostwald, one volt element, 456.
Ostwald, on the color of solutions, Photochemical action of newly dis288.
covered forms of radiation, 517.
Ostwald, on the effect of oxygen on Photochemical extinction, 514.
the strength of benzene acids, Photochemical induction, 514.
645.
Photochemistry, 511.
Ostwald, on the inversion of cane Photographic method of studying
sugar by different acids, 626.
radioactive radiations, 520.
Ostwald, on the principle of the Physical properties and atomic
coexistence of reactions, 579.
weights, 27.
Ostwald studied the effect of oxygen Pictet liquefied oxygen, 87.
on acidity, 640.
Poggendorff, method of measuring
Ostwald, thermoregulator, 395.
electromotive force, 456.
Ostwald, volume-chemical method
Polarization and electrolysis, 494.
631.
Polarization, results of the measureOstwald, volume-chemical method
ments of, 496.
of determining chemical equilib- Polarized
light, rotation of the plane
rium, 590.
of, 125.
INDEX
667
Polonium, 528.
Radioactivity of thorium, 519.
Polymers, action of light in the Radioactivity, theory to account
formation of, 516.
for, 529.
Radiothorium, 529.
Polymorphism, 165.
Ponsot, freezing-point method, 234, Radium, discovery of, 519.
235.
Potential between metal and solution, calculation of the difference
in, 465.
Potential differences between metals
and electrolytes, 483.
Potential in a concentration element, sources of, 476.
Potential of ions, discharging, 500.
Poynting, on osmotic pressure, 222.
Precht and Runge, on the atomic
weight of radium, 520.
Radium,
Primary
cells,
electromotive force,
sur-
face-tension, 146.
emanation
that the
produces
heat, 525.
vapor-pres-
sures, 101.
454.
Primary decomposition
of
water in
226.
electrolysis, 498.
Primary products
Radium produces
of
electrolysis,
132.
Refractivity
and
density, 116.
law
of
of
INDEX
668
Regular crystal system, 159.
Rodger
rotation, 138.
position
Schiff,
of
the
electrolytic,
metals, 500.
222.
Shields and Ramsay, work on surRunge and Precht, on the atomic
face-tension, 146.
weight of radium, 520.
Shields, on hydrolytic dissociation,
Rutherford and Barns show that
303.
most of the heat comes from the Silbermann and Favre, work of, 331.
radium emanation, 525.
Silver salts, action of light on cerRutherford and Soddy discover thotain, 516.
rium X, 527.
Smale, work on the gas-battery, 482.
Rutherford and Soddy, theory of Smits, on osmotic pressure, 222.
radioactivity, 529.
Solids, general properties of, 157.
Rutherford discovers the radium Solids in gases, solutions of, 177.
emanation, 524.
Solids in liquids, solutions of, 186.
Rutherford, on the decomposition Solid solutions, properties of, 307,
products of radium, 526.
311.
414.
Riidorff,
Separation
on freezing-point lowering,
INDEX
Solids, molecular weights of, 310.
Solids, solution of liquids in, 306.
Solids, solution of solids in, 306.
Solubility
trolytes, 613.
Solubility, dissociation as
by change
Solubility
616.
in,
617.
experiments
669
of
first
order, 582.
642.
Solutions, 176.
Solutions in solids, 305.
Stieglitz, on the theory of indicators,
293.
Solutions, kinds of, 176.
Solutions of gases in gases, 176.
Stine, law of mass action applied to
Solutions of gases in liquids, 177.
hydration, 250.
Solutions of liquids in gases, 176.
Stokes' equation, 38.
Solutions of liquids in liquids, 178.
Stokes' theory of the Rontgen rays,
Solutions of solids in gases, 177.
518.
Solutions of solids in liquids, 186.
Strengths of acids and bases, thermochemical method of deterSolution-tension, electrolytic, 461.
Solution-tension of metals, calculamining the relative, 350.
tion of the, 486, 488.
Strouhal and Barus, method of caliSolution-tension of metals, demonbrating a wire, 393.
stration of, 464.
St. v. Laszczynski, work in acetone
Solvates in general, 249.
as the solvent, 440.
Solvents, dissociating power of dif- Substitution an electrical act, 432.
Substitution products, organic acids
ferent, 433.
Solvents inorganic, which dissoand their, 638.
ciate, and which do not, 438.
Sulphur and oxygen, effect on
Solvents mixed, conductivity and
acidity, 636.
viscosity in, 443, 504.
Sulphur dioxide, work of Walden on
as a solvent, 436.
Solvents, organic, 439.
Soret, principle of, 204.
Sulphur from the thermochemical
Specific and molecular rotation, 126.
standpoint, 344.
Specific gravity of liquids, methods Sulphuric acid dry, does not act on
of determining, 139,
dry sodium, 452.
Specific heat of gases, 68.
Supersaturated solution, 187.
Surface-tension and composition, reSpecific heat of liquids, 111.
lations between, 143.
Specific heat of solids, 171.
Surface-tension method of determinSpecific heat of water, 112.
Specific heats, atomic weights from,
ing molecular weights of pure
10.
liquids, 145.
Specific heats of a gas, ratio be- Surface-tension, Morgan's method
tween deduced from the kinetic
of measuring, 317.
theory, 76.
Specific heats of gases at constant Tammann and Nernst, effect of
Specific
heats of gases,
ratio
INDEX
670
Temperature
coefficients of
tivity, 395.
Temperature coefficients of
tivity,
conduc- Thomson,
conduc-
397.
Temperature
coefficients of
dissociating
power and
449.
loids
by
ions, 287.
Thorium
Tensimeter, 603.
Tension
liquids, 142.
dielectric
Thwing,
487.
Tetartohedrism, 160.
series,
constants
of
liquids, 154.
free
Thermochemistry
Thermodynamics,
Thermodynamics,
of benzene, 356.
first law of, 72.
612.
Ultramicroscope, 327.
INDEX
671
hols, 439.
546.
an
ester, 563.
Van
sul-
sol-
electro-
synthesis, 502.
vapor-tension, 257.
molecular weights
determined by the lowering of,
261.
67.
Wanklyn showed
Weber, on
specific
heat of
solids,
173.
of, 3.
diffu-
INDEX
672
citraconic
conic acids, 643.
and mesa-
solvent, 441.
property, 138.
of reaction
X-ray, nature
of,
532.
HARRY
C.
JONES
New and
revised edition,
author's
is
book is written.
Elements of Physical Chemistry," by the author,
used in many of our more advanced colleges, as well as
universities
but it frequently occurs that the time at
The
is
in
"
and then only in its merest elements. It is quite possible for a student to use this work
with fair success, even if he is so unfortunate as to have
no knowledge whatever of the calculus especially if the
teacher will take the trouble to elaborate those few sections in which elementary calculus has been used.
;
"
New Tork
Principles of
Inorganic Chemistry
BY HARRY C. JONES
8vo,
Hopkins University
them
to the
phenomena
of in-
may form an
integral part of
the subject, and, at the same time, be intelligible to the
student. The older generalizations are not abandoned
de-
given.
This includes
all
of the
more recent
results prac-
up to the date of publication. Some newly discovcompounds have been described, and certain minor
tically
ered
"The work
- Mining
'Most notable contribution to didactic chemistry produced by an American since the appearance of the Remsen
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New York
BY
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Hopkins University
An
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is
Two
of the chapters.
the
first
feature
is
chapter as a whole.
compelled to review
ments.
the text
when he performs
is
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"An
"A
able of
full
its
many
Journal.
"
Carries out
New
also
excellent features."
new
is
York Times.
"This book
cise and, in the
intended for beginners, and gives a conmain, very clearly written account of the
but the rarer elements. Its chief feature
is
chemistry of all
is that the ionic
theory
New York
The Theory of
Some
Electrolytic Dissociation
of
By
Its
and
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HARRY
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JONES
Hopkins University
An
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The
this
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chemistry
rests,
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chemistry, such
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