Lincoln, Azariah Thomas 1918 Textbookofphysic00lincrich

TEXTBOOK OF
PHYSICAL CHEMISTRY
BY
AZARIAH
T.
LINCOLN, PH.D.
PROFESSOR OF PHYSICAL CHEMISTRY RENSSELAER POLYTECHNIC INSTITUTE
D. C.
HEATH
CO.,
PUBLISHERS
CHICAGO
BOSTON
NEW YORK
Copyright, 1918, by
D.
C.
Heath
&
Co.
PREFACE
intended primarily for the use of classes In the subject of Physical Chemistry. beginning to in mind text I of the have endeavored keep preparation that the presentation is to students who meet the subject
is
THIS textbook
the
matter for the first time, and that they are to acquire a broad foundation for their subsequent work. As some time intervenes between the elementary courses in which the fundamental ideas of chemistry are presented and the time at which the work in Physical Chemistry is given, it is found that a short review of these fundamental concepts is necessary in order to have the student properly oriented as to the relationship of his elementary work and that which is usually incorporated in a course in Physical Chemistry.
That
this is absolutely necessary is the experience of
most
can be attained more quickly by briefly restating this fundamental matter in a form in which it can subsequently be utilized. Hence, there is given a resume* of some of the information which the student is assumed to have in order to place him in a position to correlate the new material with that which he already posteachers,
result
sesses.
and the
The order ment of the

are
first
of topics usually follows the logical developsubject matter in that the experimental data presented with the statement of the laws, then the
explanation of the facts
by the formulation of the theory. limitations are then emphasized by presentation of experimental data which appear to be abnormal, with the subsequent modification of the theory to explain these, and
The
in
some cases to show that the

iii
facts are not in accord with
IV
PREFACE The historical setting is illustrated names of the men who have been
the present theories. by recording after the
influential in developing the science of chemistry, the date at which each man was actively engaged in the work with
which
of the
his
name
is
associated.
This chronological sequence
in chemistry is of vital importance in aiding the student to acquire a true perspective of the
main advances
subject.
The subject matter has been presented by employing only the more elementary mathematics, arithmetic and algeand in but few has use been made of higher cases bra,
mathematics.
practically
all
if
Where the
desired,
it
of this matter has
way
that,
has been employed, been incorporated in such can be omitted without disturbing
calculus
the order of the presentation of the subject. In the presentation it is recognized that only by many numerical examples can the principles be properly illustrated and
emphasized. Therefore, there is incorporated in the Appendix a large number of problems, the data for which are
tabulated in such a
way
that the answers appear as one of
the parts of the tabulation. By not expressing the conditions of the problem in words, much space is saved and the instructor
desires.
may
clothe the data in whatever form he
The
character resolves
selection of the subject matter for a textbook of this itself into the process of exclusion, and
the guiding factors in making the selections have been the general information for the student, the fundamental character of the material, and the technical importance of the
facts as well as of the theoretical considerations.
Special
emphasis has been placed upon the equilibrium reactions in gases with technical uses as illustrated by means of problems. The conception of phases has been introduced early
in the discussion, and their relation and utilization in explanation of many operations has been emphasized, particu-
PREFACE
larly in the formulation of the Phase Rule, with illustrations of its industrial importance and applications. The theories
of solutions
have been presented so that the student
may
become
familiar with their experimental basis, the assumpIt is necessary that tions involved, and their limitations.
students beginning the study of theoretical chemistry should acquire a working knowledge of the prevailing theories in
order to
to them.
make
the voluminous literature more accessible
In order to accomplish this result the discussion has been extended to a consideration of concentrated soluis
and nonaqueous solutions. The colloid state of matter receiving such marked attention from the industrial as well as from the theoretical point of view, that it is betions
coming of great importance. Hence, colloid chemistry has been presented in considerable detail. There have been presented a large number of tables of experimental data, most of which have been taken from LanWith dolt, Bornstein, and Roth's Tabellen, edition of 1912.
this material directly before the student, the discussion of
the principles and facts presented may be more fully carried on, and in this way the subject can be much better presented
to the student
and he
will
be in a better position to see the
Then these data may be significance of the conclusions. utilized as a valuable source of material from which prob-
may be formulated. Free use has been made of the available literature in obtaining the material for this text, and the author desires to express his indebtedness for the same, and particularly to the following, to which the student is referred for further
details
:
lems
Text Books of Physical Chemistry, edited by Sir William Ramsay, which include A System of Physical Chemistry by W. C. McC. Lewis, The Phase Rule and its Applications by Alexander Findlay, Stoichiometry
by Sidney Young, Stereochemistry by Alfred W. Stewart, Metallography by Cecil H. Desch. Monographs on Inorganic and Physical Chemistry,
VI
edited
PREFACE
;
by Alexander Findlay particularly The Chemistry of the RadioElements by Frederick Soddy, and Osmotic Pressure by Alexander Findlay. Text Book of Inorganic Chemistry, edited by J. Newton Friend Vol. I,
;
An
Introduction to
H. F. V. Little
Modern Inorganic Chemistry by J. Newton Friend, and W. E. S. Turner; Vol. IV, Aluminium and its ConRare Earth Metals by H. F. V.
Little.
;
geners, Including the
Organic Chemistry for Advanced Students
by Julius B. Cohen
Vol. II,
Handbook of Colloid Chemistry by Wolfgang Ostwald, translated by Martin H. Fischer.
On the Physical Aspect of Colloidal Solutions by E. F. Burton, University of Toronto Studies No. 36. An Introduction to the Physics and Chemistry of Colloids by Emil
Hatschek. The Chemistry of Colloids by by H. J. H. Fenton.
W. W.
Taylor.
Outlines of Chemistry
For valuable suggestions and assistance, the author wishes to express his appreciation to Dr. M. A. Hunter for reading the manuscript; to Dr. A. M. Greene for his kindly criticism on the chapter on Thermodynamic Considerations; to Mr. T. H. Learning for his most valuable assistance,
But particularly in collecting and verifying the data. especially to Mr. G. B. Banks the author wishes to express his sincere gratitude and deep obligation for his untiring
and painstaking criticisms and for his efforts to prevent errors which would otherwise have appeared. Corrections and suggestions from others will be appreciated.
A. T. LINCOLN.
TROY, N.Y. May, 1918.
CONTENTS
CHAPTER
I.
INTRODUCTION
..'.",,
=
PAGE
I
II.
III.
IV.
V.
VI.
LAWS OF COMBINATION AND CHEMICAL UNITS. THE GAS LAW ^.. ^ DETERMINATION OF MOLECULAR AND SYMBOL WEIGHTS t ..* ATOMIC AND MOLECULAR THEORIES DEVIATIONS FROM THE GAS LAW AND DISSOCIATION
.
;
6
18
\,
..-
29
36
OF GASES
VII.
VIII.
46 64
82
IX.
X.
XI.
XII.
XIII.
THE PERIODIC SYSTEM THE KINETIC THEORY OF GASES SPECIFIC HEAT OF GASES VAN DER WAALS' EQUATION THE PHYSICAL PROPERTIES OF LIQUIDS
.
90
,
%
.
97
in
122
REFRACTION OF LIGHT
OPTICAL ROTATION
133
I
XIV.
SOLUTIONS
46
XV.
XVI.
XVII.
XVIII.
SOLUTION OF LIQUIDS IN LIQUIDS SOLUTION OF LIQUIDS IN LIQUIDS
157
1
II
68
PHASE RULE
SOLUTION OF SOLIDS IN LIQUIDS SOLUTION OF SOLIDS IN LIQUIDS
SOLUTION OF SOLIDS IN LIQUIDS SOLUTION OF SOLIDS IN LIQUIDS
APPLICATION OF THE PHASE RULE
I
183 195
XIX.
II
'III
.
XX.
XXI. XXII.
XXIII.
204 216
229
248 255 265
273 282
IV
OSMOTIC PRESSURE
XXIV.
XXV. XXVI,
LOWERING OF VAPOR PRESSURE FREEZING POINTS AND BOILING POINTS OF SOLUTIONS THERMODYNAMIC CONSIDERATIONS
vii
.... ....
Vlll
CONTENTS
PAGE
CHAPTER
XXVII. XXVIII.
ELECTRICAL CONDUCTANCE
301
321
ELECTROLYTIC DISSOCIATION
XXIX.
EQUILIBRIUM BETWEEN THE DISSOCIATED AND UNDISSOCIATED PARTS OF AN ELECTROLYTE IN
SOLUTION
,-.,.
336
358
XXX. CONCENTRATED
XXXI.
XXXII. XXXIII.
HYDRATION
HYDROLYSIS
SOLUTIONS
368 386
395
XXXIV.
NONAQUEOUS SOLUTIONS THERMOCHEMISTRY

COLLOID CHEMISTRY
410
XXXV.
XXXVI.
RATE OF CHEMICAL REACTIONS

APPENDIX
INDEX
....
433 475
507
541
PHYSICAL CHEMISTRY
CHAPTER
I
INTRODUCTION
Units of Measure.
The work
in chemistry
and physics
consists chiefly in making measurements in order to ascertain the quantity of the materials present or the forces acting between these substances. Shortly after the intro-
duction of the balance into the chemical laboratory there began a yigorous campaign to determine the weights of substances as well as of the relative quantities of the constituents of which these were composed and in what ratio various
It was not only necessary to have a unit of weight but also a unit to represent these combining relations, just as it was necessary to have a unit of length
substances combined.
to obtain the dimensions of substances or their distances

apart.
forces,
When an effort was made to measure the various some convenient standard of reference had to be
which these forces could be repremeasurement is some convenient quanthat particular thing which is to be applied as a diin terms of
employed
sented.
tity of
unit for
visor in order to ascertain
how many
times this arbitrarily
selected quantity
to be
measured.
contained in the quantity of the thing Or in other words, a unit is any quantity
is
to which another quantity of the same kind can be compared for the purposes of measurement and for expressing the
magnitude of the same.

is
represented
by
the
The measure of this unit quantity number i. The fundamental units
CHEMISTRY
are selected arbitrarily, and the derived units are defined in terms of the fundamental units.
The method
of
measurement
is
quantity to be measured with our unit.
the comparison of the This may be ac-
complished (i) by applying the unit directly to the quantity to be measured, as that of a foot rule to a floor to find its dimensions, a graduated vessel to the liquid to be measured
;
or (2) by the effect the particular quantity to be measured has as compared to the effect that unit quantity has, as in determining the strength of an alkali by titrating it against a standard acid which has been expressed in terms of our
unit alkali, or any of our quantitative methods for determining the quantity of a particular substance present, as by determining the refractivity of a liquid, the electrical
conductance,
etc.
The knowledge of the phenomena occurring about us has been obtained by accurate measurements, and the fundamental units in which these have been expressed are the The scientific unit of time, units of time, space, and mass.
the second, is the 86,4ooth part of a mean solar day, which is the average interval (or period) that elapses between successive transits of the sun across the meridian at
any place
during the whole year. Owing to the fact that the speed of the rotation of the earth is decreasing, resulting in the corresponding increase in the length of the second, it has been suggested that the
time of vibration of the atom of some element be selected as our unit of time, as this seems to be invariable and unalterable.
Our conception of position is that of relative positions only, and the location of one object is expressed in relation to some other object. The change of the position of a body
with respect to another is termed motion, i.e. motion is the change of position. The change of position in unit time is the speed, while the rate of change of position in a specified
INTRODUCTION
direction
If this velocity is not constant is the velocity. successive intervals of time, the amount of change during in the velocity during the interval of unit time is designated
the acceleration,
V2
i.e.
~ Vl
= a, where
/,
the change of velocity

giving an acceleration
has been from

represented Matter.
vi
to v2 in the time
by
a.
Being familiar with handling various subsuch as iron, sodium chloride, water, etc., we are stances,
able to distinguish them by certain individual characteristics that we call properties. These properties are always constant and persistent and are not detachable from the
The embodiment of these properties is that somewhich is familiarly known as matter. thing Closely associated with these properties are manifestations of what we designate energy, and in our experiences we have not been able to separate energy from matter. Yet it is through
body.
these manifestations that
we know
of the existence of that
which we designate matter. The quantity of matter is measured by means of the balThis ance, and its measure is expressed in terms of weight. measure is the attraction of the earth for the particular
quantity of the material substance or matter.
Since the
attraction of the earth varies with the distance from the
center of the earth, a body would not have the same weight on all parts of the earth's surface. The quantity of matter
does not change, and the mass, as it is termed, remains constant. Hence in stating the quantity of a substance, it is
not sufficient to speak of its having a certain weight, but the term mass is used to definitely express the quantity of the
substance.
Masses
are
compared
units of
by
comparing
their
weights. Units of Mass.
The
mass are founded on the
kilogram, which is the metric standard of mass and is defined as the mass of a piece of platinum-iridium deposited at the
PHYSICAL CHEMISTRY
International Bureau of Weights and Measures near Paris. known as the International Proto" " kilogramme des Archives type Kilogram, is equal to the
This standard of mass,
made by Borda, which was intended
to have the
same mass
as a cubic decimeter of distilled water at the temperature of 4 C. and 760 mm. Hg pressure, which weighs i kilogram
and equals actually 1.000027 cu. dm. The English standard of mass is the pound and is the weight
of a piece of platinum weighed in vacuo at the temperature of o C., and which is deposited with the Board of Trade. Force is that which changes or tends to change Force.
the velocity of a body. It may be measured by the gravitation method, the ordinary spring balance method, or the dynamic method; the first of which is the one generally
used by chemists. The unit of force is that force which In the C.G.S. produces in unit mass unit acceleration. defined as that and is is the of force dyne system the unit of unit mass a on force which acting produces an body The second. second centimeter of one acceleration per per mass is when a called is unit force expressed in poundal Force in seconds. time and in may be feet, pounds, length
defined
eration.
by F
Ma, where
is
mass and a
is
the accel-
The units of force, the dyne and poundal, are absolute units, but the so-called gravitational the designated units are more commonly employed, wherein use is made of the force of the attraction of the earth for the body. The
Weight.
unit of force then becomes the attraction of the earth for one gram or one pound. the unit of mass
The
attraction of
the earth
2
.
acceleration of 98 1 cm./sec.
on one gram causes an The force of one dyne produces

1
an acceleration
of one
sec.
^when 2
it
acts
on one gram.
Hence
the weight of one

1
gram
is
equivalent to 981 dynes.
This has different values at different places.
INTRODUCTION
Pressure.
Pressure
is
a distributed force.
The
inten-
is used exsity of pressure, i.e. the pressure per unit area, in and in science chemistry, particularly, when the tensively
;
term pressure
is
used the intensity of pressure
is
meant.
The mass of a substance in Density and Specific Gravity. unit volume is termed the density of that substance. Density
is
represented
by
p.
Then by
is
definition p
The
specific gravity of
a substance
the ratio of the mass of a
given volume of a substance to the mass of an equal volume The specific of another substance taken as a standard.
gravity
is
represented
by s.
is
Then
=
&
where g is the mass
of the substance, and g, the standard substance.
the mass of an equal volume of It is not always customary to com-
pare the substance at the same temperature. Hence if water at its greatest density (4 C.) is selected as the standard
and the other substance compared with

.0
it
if
at this temperais
ture, this is usually expressed -^
while
the substance
at
some other temperature, as 20, the comparison with water

Q
at 4
would be indicated as follows

signifies
^-, and
4
the expression
that both the substance and the standard are to
be compared at 15.
p is the density of standard.
We
should also have

p, is
=
P
in
which
any substance, and
the density of the
CHAPTER
II
LAWS OF COMBINATION AND CHEMICAL UNITS

THE uniform occurrence of
natural
phenomena
is
observed
to take place and the conditions best suited for their reproduction are ascertained by experimentation. The facts
gathered by observation and experimentation are
classified,
and certain particular groups of related facts are then expressed in a generalization which is the so-called law. Or, " as Mellor expresses it, The laws of chemical and physical phenomena are collocations of those circumstances which have been found by experiment and observation to accompany all chemical and physical changes included in the statement of the law." We have as some of the fundamental generalizations of science the following The Law of the Conservation of Energy the Law of the Conservation of Matter; Newton's Law of Gravitation; Boyle's Law;
:
;
thus see that a Law of Science is a general statement of what has been found to be true by experiment and observation and of what will probably be true in the future.
etc.
We
THE LAW OF DEFINITE PROPORTIONS
When magnesium
oxide,
is
burned,
it is
changed to the white
and we have on the one hand metallic magnesium and on the other hand the white oxide, there being no The amount of the magnesium oxide that can gradation. be formed depends upon the quantities of magnesium and oxygen available, and there is a constant relation between the amounts of substances taken and the amount of sub6

stance formed.
In general this may be stated that when changes to substance B the ratio of the masses It was not possible to formulate any such law is constant. It was then until the balance was introduced by Lavoisier.
substance
of zinc oxide.
demonstrated that 100 parts of zinc always yield 124.5 parts By using different amounts of potassium chloride, varying from 44 to 80 grams, the result of seven
experiments showed that 100 parts of potassium chloride

yield 135.645 parts of potassium nitrate.
If
react
two chemically homogeneous substances, A and B, upon each other and yield a third substance, C, then
:
the following relations hold
Mass A = ~ TT7 Mass B

This
T. ,
AX
: '
(constant)
Mass A = T , Ki -^ Mass C
^ -^ Mass C
Mass
Kz.
be demonstrated by adding, drop by drop, a solution of potassium bromide to a solution of silver nitrate. It has also been shown that these relations hold under what-
may
ever conditions the substances react/
For example, the
amount of silver chloride formed from a constant given weight of silver is always the same, whatever the method be by means of which it is prepared, as is shown by the following
:
1.
2.
3. 4.
Ag yielded Ag yielded Precipitating AgNO 3 with HC1 aq g. Ag yielded Precipitating AgNO 3 with NaCl aq 100 g. Ag yielded
g.
Burning Ag in Cl gas Dissolving Ag in KC1
100
132.842
g.
100 100
g.
132.847
132.848 132.842
g. g. g.
AgCl. AgCl. AgCl. AgCl.
A large number of experiments were made to determine whether the mass formed was equal to the sum of the masses taking part in the reaction. In seven experiments with the formation of silver iodide from silver and iodine, in which quantities of silver varying from 27 to 136 grams were used, the weights of the silver iodide formed did not differ from the sum of the weights of the silver and the iodine taken by more than one part in 20,000 in anyâse. From this it is seen that there is a definite relation between the substances
PHYSICAL CHEMISTRY
used and the products formed. This may be expressed in the following form The ratio of the mass formed to the con:
stituents is constant
and
also the ratio of the constituents to the
This is termed the Law of Definite or Constant Proportions. While this has been fully demonstrated to the satisfaction
mass formed
is constant.
of
most
investigators, there are
some who
still
question
whether the mass of a substance always remains constant during its passage through chemical changes. Very recently Landolt 1 published the result of his investigation on the question as to whether chemical changes alter the mass of a Of 14 reactions of various types only particular substance. two gave systematically a change in weight larger than the errors of observation. Each of the experiments, in which 250 to 310 grams were used, has corresponding differences in Out of 70 exweights, varying from 0.068 mg. to o.n mg. periments 6 1 showed losses in weight. Babcock, from his
work upon the effect of molecular changes upon weight, states 2

that his experiments indicate that the weight of a body
is
an
inverse function of its energy. While the difference between the weight of the ice and the water resulting from it is always
small, the ice
was always found to be heavier than the water.
THE LAW OF MULTIPLE PROPORTIONS

The mass
of a
system
is
not altered by chemical changes
that occur in the system, or, as expressed above, the mass of a composite substance is equal to the sum of the masses of its component elements. By the term element we underall efforts
stand those particular substances which have so far resisted of the analyst to decompose them into simpler or
constituents. 3
more elementary
1
2
3
We have
already seen that
Landolt, Jour, de chem. phys. 6, 625-27 (1908). In a private communication to the author.
The
ments that require peculiar and
rare earth elements constitute a group of closely related elespecial methods in order to separate
these elements combine in constant ratios to form chemically homogeneous substances. Such chemically homogeneous substances, whose percentage composition by mass is invariable, are termed chemical compounds.
burning portions of 10 grams of lead in oxygen the quantities of lead oxide were formed: 10.77, 10.775, 10.78, and 10.75 grams, and Berzelius found as an average of his determinations 10.78 grams of the oxide of
By
following
lead produced from 10 grams of lead. Taking 10.78 as the value, and expressing the amount of lead oxide produced
from 100 grams of
lead,
we would obtain
107.8
grams
of the
yellow oxide of lead. It has also been found that 100 grams of lead unite with 11.7 grams of oxygen to form minium
(red oxide of lead) and that 100 grams of lead unite with 15.6 grams of oxygen to form brown oxide (peroxide) of lead. These different quantities of oxygen combining with the same
polonium, actinium,
and distinguish them. Certain elements, which include uranium, radium, etc., are designated radioactive elements and are
characterized by giving rise to emanations. The theory of the disintegration of these radioactive elements assumes that the emanations give rise, in some cases, to active deposits which are transformed into another element, and this in turn is transformed into a non- radioactive and stable
In some radioactive changes, the particles emitted are of helium, as is illustrated in the growth of helium from actinium. Resulting from these emanations there is a group of elements of different atomic weights but which are chemically identical. Such a group of elements is termed isotopes and the elements are called isotopic. The following members of the actinium series are given by Soddy *
element.
ex.
charged atoms
1.
2. 3.
Radioactinium, thorium, radiothorium, ionium, uranium-X. Actinium and mesothorium-2.
4.
5.
6.
7.
Actinium-X, radium, mesothorium-i, thorium-X. Actinium emanation and emanations of radium and thorium. Actinium-B, lead, radium-B, thorium-B, radium-D. Actinium-C, bismuth, radium-C, thorium-C, radium-E. Actinium-D, thallium, and thorium-D.
* Soddy, The Chemistry of the Radio-Elements (1914), and the Text-book of Inorganic Chemistry, Edited by J. Newton Friend, Vol. IV by H. F. V. Little, are sources of additional information and extensive references to the literature.
10
PHYSICAL CHEMISTRY
:
amount
15.6,
of lead (100 grams) are in the ratio of 7.8 11.7 : is the more simple ratio of 2 hence a con3 4 stant quantity of lead combines with different quantities of oxygen in the simple integral ratio 2:3:4. Similarly it has
which
been found that 100 grams of nitrogen unite with the following quantities of oxygen to form distinct chemical individuals 57.1; 114.3; I 7 I -4> 228.6; 285.7 grams, which
:
reduces to the following simple ratio 1:2:3:4:5. In the case of hydrogen and oxygen the quantities of oxygen found
:
in combination with the
the ratio of 1:2.
same quantity of hydrogen are in Hence from the above the following
:
general statement may be made When an element combines with another element or group of elements to form different compounds, the masses of the first
element that combine with a given mass of the other element or group of elements are in some simple ratio to one another.
THE LAW OF RECIPROCAL PROPORTIONS

In the above examples of ratios between the elements lead and oxygen, we expressed the amount of oxygen that combined with 100 parts by weight of lead. We could have expressed the ratio by stating the amount of lead that combined with i, or 10, or 100 parts of oxygen. The same is true in the case of oxygen and nitrogen; either element might have been selected as the unit of comparison, in any convenient quantity. Further, if the ratio of the two elements, nitrogen and oxygen, is established, and also the ratio of hydrogen and oxygen, the ratio of hydrogen and nitro-
gen can readily be ascertained by calculation. Again, if the ratio of hydrogen and chlorine be determined and the other two ratios, nitrogen to oxygen and oxygen to hydrogen, then the cross-relation between chlorine and nitrogen can be calculated. This relation can be illustrated in the case of chlorine, iodine, and silver. Let us compare the ratios of the amounts of these elements that combine with

equal amounts of
II
In silver chloride silver, say 75.26 parts. 24.74 per cent chlorine and 75.26 per cent silver; in silver iodide we have 54.04 per cent iodine and 45.96 per cent silver in chlorine iodide we have 2 1.84 per cent chlorine
we have
and 78.16 per cent iodine. Then from the proportion

Iodine
:
Silver
Iodine
Silver
we have From which

x
the
54-04
45.96 26
::
x: 75.26.
54
"
'
I 45.96
88.49
amount
silver.
amount
of iodine that would combine with 75.26 parts of Since 24.74 parts of chlorine combine with this same of silver, 88.49 parts of iodine would be equivalent
to 24.74 parts of chlorine.

lent to
One part
of iodine will be equiva-
= 0.279 part of chlorine. In the direct comQ 88.49 bination of chlorine and iodine we have the ratio of 21.84
'
parts of chlorine
78.16 parts of iodine, or
0.279
70.10
part of chlorine, uniting with one part of iodine, which is the same ratio as above. By a similar method these crossrelations can be calculated
it is
between
all
of the elements,
and
this relation that is
known
as the
Proportions, or the as follows

:
Law of Equivalents.
Law of Reciprocal It may be expressed
When
other, or
different elements are
combined successively with any
with a group of others, the masses of the former that are combined with a given mass of the latter are to one
another in the same ratio in which these different elements combine with any other element or group of elements. From our consideration of the previous laws, and our information concerning chemical compounds, it is evident
that
we have
to distinguish between equal quantities of the
12
constituents of a
PHYSICAL CHEMISTRY
of the constituents.
compound and equal chemical quantities In the compounds cited above, silver
and and
chloride, for instance, contains 75.26 per cent of silver 24.74 per cent of chlorine, i.e. these quantities of silver
chlorine are equal chemically. In the chemical sense, then, the equal quantities of matter are the weights or masses
which unite with each other chemically.
The amounts
of
the different substances that unite chemically are chemically equivalent and depend entirely upon the specific nature of the substances.
UNITS OF CHEMISTRY
employ symbols to represent the elements and a combination of symbols in the form of a formula to represent the composition of a compound. For example, water is composed of hydrogen and oxygen, and hydrogen peroxide is composed of hydrogen and oxygen. We use H to represent the element hydrogen and O to represent the element oxygen then the combination HO represents both water and hydro;
We
gen peroxide, but not their composition. By analysis we know that water contains 88.85 per cent of oxygen and 11.15 per cent of hydrogen, and hydrogen peroxide 5.91 per cent In water the of hydrogen and 94.09 per cent of oxygen. Then the amount which combines ratio is 11.15:88.85. with 94.09 parts of oxygen in the hydrogen peroxide would be 11.15:88.85: :#:94.09. Solving for x we have 11.82 The quantities of hydrogen combining with the parts.
same quantity
of oxygen, 94.09 parts, are 11.82 parts

:
and
That is, there are 5.91 parts, which are in the ratio of 2 i. two different quantities of hydrogen combining with the same quantity of oxygen to form these two different chemThe hydroical substances, water and hydrogen peroxide. or has two equivalents. We could combining weights gen use this weight of oxygen as our unit quantity and represent
it
by the symbol
for oxygen, O, or
we could
select
any

other quantity arbitrarily.
13
The quantity that has been
selected arbitrarily is 16, and so we shall arbitrarily select as our symbol weight of oxygen, 16 grams. Then the equivalent weights of hydrogen would be 2 in the compound water
and i in the compound hydrogen peroxide. Then the formulae for these substances could be written respectively 2 O and HO, if we let the symbol represent the smaller
hydrogen combining with the 16 grams of oxygen, thus avoiding a fractional part of the symbol weight were we to select the larger value H = 2. From 34 grams of hydrogen peroxide we can obtain 16 grams of oxygen and 18 grams of water at the same time. This 1 8 grams of water on decomposition will yield 16 grams of oxygen and 2 grams of hydrogen that is, the oxygen of hydrogen peroxide can be separated into two equal quantities, but the oxygen in the water cannot be thus separated, for we obtain free hydrogen and free oxygen. From this we assume that the oxygen in water is in the simplest amount possible and is the quantity represented by our symbol
of
;
amount
weight of oxygen, O, while in the peroxide there

.
is
twice this
quantity, or O 2 In the decomposition of hydrogen peroxide we find that all of the hydrogen present remains with one part of the
oxygen and is the same as that in the water. Now if we treat water with sodium, we obtain free hydrogen and a compound, sodium hydroxide, which upon analysis gives all of the oxygen of the sodium, oxygen, and hydrogen, water appearing in this compound and the hydrogen of the water separating into two equal parts, one part appearing free and the other in combination with the oxygen and sodium. The formula for water must show that the hydrogen can be divided therefore, the formula becomes H 2 O. vSimilarly, the formula for hydrogen peroxide must show
;
that
it
contains the
and
also that the
same amount of hydrogen as in water oxygen contained can be divided hence

;
14
PHYSICAL CHEMISTRY
the formula for hydrogen peroxide becomes instead of 2 O2 the chemical which we saw HO, represents composition as well.
,
A chemical formula is a combination of symbols wherein each symbol represents that equivalent quantity of the element which we cannot further divide by chemical transformations. These chemical formulae are the result of experiment and are designated the empirical formulae. If our method is good, only integral multiples of the chemical units represented by symbols enter into and go out of combinaweight of oxygen is defined as 16 grams of the and oxygen, symbol weight of hydrogen is then i. The sum of the symbol weights is designated the formula weight. This is usually called the molecular weight. For example, two symbol the formula we derived for the water is H 2 weights of H = 2 and one of O = 16 and the sum 18 is the
tion.
;
The symbol
formula weight for water. The symbol weight of other elements may be determined in a similar manner. Carbon when burned in air forms two
oxides which are
compounds
of
oxygen and carbon;
by
analysis one contains 12 grams of carbon and the other 6 grams of carbon in combination with 16 grams of oxygen.
So the formulae would be
C O and CO
2
or
CO
and
CO
re-
spectively, depending upon whether we select 12 or 6 as the equivalent weight of C. Since carbon has two combining
weights, it is necessary for us to have more data in order to decide which we shall select as the symbol weight. Either of the formulae would represent the chemical composition
and would be designated an empirical formula. In the case of nitrogen, we have five different compounds of nitrogen and oxygen. Expressed in terms of the quantities of nitrogen in combination with 16 grams of oxygen, we have 28, 14, 9^, 7, 5! grams of nitrogen respectively, i.e. we have five different combining weights of nitrogen, and the question arises, which of these equivalent weights shall be selected
as the symbol weight of nitrogen ?

The answer
of the
15
volume
to this question is obtained by a consideration relations of gaseous compounds and of the
elements entering into the reactions. These volume relations are summed up by Gay Lussac's Law of Combination by
When reacting gaseous Volume, which is stated as follows elements combine, the volumes of the different gases under the same conditions of pressure and temperature are in simple
:
ratio to one another
and
to the resulting
products.
Taking the volume of 16 grams of oxygen as the unit volume under specified conditions of temperature and
pressure, we find experimentally under these same conditions of temperature and pressure the following volume relations
between the reacting substances and the resulting

:
product
Hydrogen 2 grams
16
Oxygen grams
18
Water grams
2.
16
Nitrogen
14 grams
-j-
PHYSICAL CHEMISTRY
Hydrogen 3 grams
Ammonia
17
grams
vol.
i
+
we observe
2
3 vols.
2 vols.
In No.
arbitrarily selected
gen represents
uct,
1
that since 16 grams of oxygen is the symbol weight and the quantity of hydrosymbol weights of hydrogen the prod-
We
is represented by the formula 2 O. notice that the formula weight of water occupies twice
grams of water,
symbol weights
the volume of the one symbol weight of oxygen, while two of hydrogen occupy the same volume as the
formula weight of water or twice the volume of one symbol weight of oxygen. From an examination of the weights of these various compounds used and produced in these five examples, it will be noticed that the volume occupied by the formula weight of water (2 vols.) is the same as that occupied by the formula weights of the other compounds hydro:
chloric acid, nitric oxide, nitrogen peroxide, nitrous oxide,
and ammonia.
That
is,
the
formula weight of every gaseous
We compound considered above occupies the same volume. can generalize and state that the formula weight of all gaseous compounds occupies the same volume under the same conditions of temperature and pressure. This may be the same as the empirical formula, which is taken as the simplest formula, or it may be some integral multiple of the
empirical formula.
at o
Experimentally, it has been found that 16 grams of oxygen C. and under 760 mm. mercury pressure occupies 11.2
Under these conditions of temperature and pressure the volume occupied by the formula the of gaseous compounds. This volume is termed weight
liters.
22.4 liters is therefore
the formula volume.

of a compound is, then, a combination of that represents the percentage composition of the symbols
The formula
17
compound and such that the formula weight in grams of the compound in the gaseous state occupies 22.4 liters of space
under standard conditions. A formula is, therefore, purely an arbitrary affair, subject to definition. It follows then that we can have a formula of an element thus O 2 is a combination of two symbol weights of oxygen representing 32 grams of oxygen and occupying 22.4 liters under standard conditions of temperature and pressure. Similarly the formula of hydrogen is H 2 of chlorine C^, of nitrogen N 2 Rewriting the above reactions, employing formulae for the reacting substances and products, we have
;
.
1.
H + O
2
=2H O
2
2 vols.
2.
+ +
+
Vol.
2 vols.
C1 2
I
+ H =2
2
I
HC1
vol.
vol.
=
=
2 VOls.
3.
NO + O
I
=2
NO
2
2 VOls.
4.
VOl.
2 VOls.
H
i
+NO
2
=
=
HO+ N
I
vol.
vol.
vol.
vol.
These chemical equations represent the chemical reaction
and the quantities by weight
of the reacting substances. the formulas appearing in the equation are the same as the number of volumes of the compounds in the
The
coefficients of
gaseous state.
Experimentally,
we have developed
that equal volumes of
substances in the gaseous state contain the
same number of
formula weights of the compounds.
Avogadro's Law.) We have also established the following rule for checking the symbol weight of an element Determine the weights in grams of the designated element in 2 2 .4 liters, under standard
(This
:
is
The conditions, of the gaseous compounds of that element. greatest common divisor of all these numbers is the symbol
weight of the element.
CHAPTER
III
THE GAS LAW

the mass of
THROUGH whatever chemical change a substance passes, The same may be said it remains the same.
concerning physical transformations as well. If a definite mass of a gas is selected under a specific temperature and If, however, this pressure, it will occupy a definite volume.
mass be subjected to different pressures and temperatures, the volume which it occupies may vary greatly, and hence the volume which this constant mass occupies that is, the depends upon the pressure and temperature values for the pressure, p, the temperature, /, and the volume,
definite
;
V, are so related to one another that simultaneous values of any two determine the functional relation. This may be = f (p,t). This equation is expressed mathematically, V
known
In the functional relation as the Equation of State. the volume which a given mass occupies depends upon the temperature and pressure. The pressure, p, and the temperature, /, are spoken of as the independent variables, and the volume, V, as the dependent variable, because its value depends upon the values arbitrarily selected for p and /.
By
keeping one of these independent variables constant
it is
possible to determine what relation exists between the dependent variable and the other independent variable.
i. Assume a constant mass of gas. The volume which it occupies depends upon p and Then F is a dependent variable. If we assume t and the mass constant, V depends on
/.
p,
18
THE GAS LAW

Let volume at pressure p be
19
V and the volume at pressure pi

if
beVi.
Now by
500'
experiment we find that
1000
cc. of
if
mm.
is
sure
pressure, then the volume will be 500 cc. increased to 1000 mm. That is,
gas is at the pres-
1000
cc.
500
cc.
1000
mm.
500
mm.
or
V:Vn
If
2.
:pnp.
the temperature is constant, the volumes are inversely proportional to the pressures. This is Boyle's Law.
assume pressure and mass constant and vary the Gay Lussac found experimentally that if 100 cc. of gas at o C. were heated, the volume was 136.65 cc. at 100 C. or an increase of 36.65 cc. for a change of 100 C., or 0.3665 cc. for i. The change for i cc. is y^ of this, or 0.003665 cc. That is, for every increase of one degree centigrade the volume is increased this proportional amount,
temperature.
or
i
Now
cc. increases
0.003665
cc.
1/273.
Any volume
of degrees of
of gas at o
per degree C. But 0.003665 = C. will increase for any
number
change of temperature
273
times the
original volume.
Let Fo
= volume of mass of gas at / V = volume of mass of gas at

pressure. Vo = increase in
at pressure po. t, and at the
same
Then V volume = change in temperature. and t to But a gas increases 1/273 of the original volume per degree; then 1/273 times Vo = increase in volume per degree.
t
toX
increase for change of temperature
to
on
273
the centigrade scale. But the increase in volume
is
Vo,
hence
V-
V,
= ^
XF
which becomes
V~
ô
Vo
= ^-273
273
20
PHYSICAL CHEMISTRY
We are expressing our temperature as temperature differences on the arbitrarily selected centigrade scale.
- = - could be simplified matheô 273 matically if we were to take / = 273 and substitute in the above equation. The zero of the centigrade scale then would become 273 centigrade divisions above the zero point on our
The equation
+
t.
new temperature
scale. This new point is known as the Absolute Zero and is found to be practically the same as the Absolute Zero on the thermodynamic scale. The readings
on the centigrade
scale, or
scale equal
273
-f-
on the Absolute
T =
TQ
Now
Vo
: :
having assigned these values,
the equation becomes

tain
--To
-,
from which we ob-
=
Vo
TQ
or
Vo
To which states that the volumes
of gas under constant pressure are directly to the Absolute temperatures. This is Charles' proportional or Gay Lussac's Law.
of a given
mass
These two laws can be combined into one expression by assuming a constant mass of the gas and then (i) with the temperature constant, change the pressure and then (2) with
: ;
the pressure constant, change the temperature. Assuming the mass constant and the temperature constant, then let V = the volume of the gas at pressure po and tem-
perature TQ.
Vi
the volume of the gas at pressure pi and tem-
perature
TV
to Boyle's
Then according
Law
Vi
:
:
Vo
Solving for Vi,
pi
po.
we have
pi
THE GAS LAW
21
ing the pressure constant, pi
change the temperature on this new volume keep= p%; we have according to Charles' or Gay Lussac 's Law
:
Now
Vi
Ti
or
ViT2 =
-
Ti.
Substituting the value of Vi
=
pi
we have
** = y2 Ti.
pi
Now
i
eliminate intermediate values

.
and remember To =
.
and pi = p2
We have
~\7 >>
T*
=VT
2
Rearranging,
we
have
-To
-/2
is an expression and Boyle.
which
for the
combined laws
of
Gay Lussac
new ones
Now
it is
possible to change these last values to

similarly the
and obtain
same
relation.
^=
Tz
13
^,
or in
general the initial volume multiplied by its corresponding pressure divided by its corresponding temperature, is equal to any other volume times its corresponding pressure divided
by
its
corresponding temperature.
-4p =
To
/
*,
which
is
con-
stant,
or
constant
Vp = KT.
(A)
ANOTHER DEVELOPMENT OF THE GAS LAW EQUATION

gas, the
has been shown experimentally that if we take a definite mass of volume it occupies will be dependent on its temperature and That is, keeping the mass constant, pressure.
It
V =
f(p,
t] t)
or
it
p = f(V,
may
also,
be stated that
/
and
f(V, p).
Gay Lussac showed by experiment that when the volume is constant, the change in pressure is directly proportional to the change in tern-
22
PHYSICAL CHEMISTRY
perature. Assuming this to be true for the entire range of temperature and pressure the functional relation p = f(V, t) is expressed by the
equation
p
where k
po
k(t
t )
(i)
may
It will
be a function of the volume. be recalled that y
ax
is the ordinary equation of a straight line, in which a represents the tangent of the angle which the line makes with the x axie and b represents the intercept on the y axis. Any given point (x y') on this line
f
,
must
satisfy the equation which gives y'
ax'
b.
Eliminating b
we
get
y'
a(x
x').
(2)
This is the equation of a straight line through the point (#', y') making an angle, whose tangent is a, with the x axis. Equation (i) is the same form as equation (2). Therefore the equation
p-po =
k(t
-to)
(to,
represents a straight line through a given point with the temperature axis whose tangent is k.
,
po)
making an angle
Since we may arbitrarily select (/ po), let us assume it to be the This is the zero melting point of ice under atmospheric pressure. on the ordinary centigrade scale. That is, t = o and p = the pressure of one atmosphere. Substituting to = o in equation (i) we get
P
In Fig.
i
po
kt.
(3)
let
the melting point of ice
(to,
po),
and some distance above the temperature

;> t
axis,
on the pressure axis be represented by A.
Now we know by
the temperature
is
experiment that, when

is
raised, the pressure Therefore, any other point representing a greater pressure will be to the right and above the point A, as
increased.
point
(pi,ti).
Then the
straight line
FIG.
i.
through these two points will be the locus of equation (3). The value of po is taken as one atmos-
AB
phere above absolute zero pressure, as we selected the melting point at the pressure of one atmosphere, but the value of to was assumed
THE GAS LAW
23
without reference to any absolute zero of temperature. Therefore, where the locus cuts the temperature axis is represented the absolute zero of pressure, and it is of some advantage to us, to take the origin
If we do this, all values of presof the coordinants at this point 0. sures remain the same, but the value of each temperature will be increased by the distance between this point O and the point A', the origin of our old system of axes, i.e. the distance OA ', which we will
designate
axis
TV
then
So
if
we
refer the
temperatures to our new coordinate

or
by
T,
T =
To
= T- T
we
get
Substituting this value in equation (3)
p-p
Equation
(4)
= k(T-
To).
(4)
may
p
be written
Po
- kT =
- kT
(4')
Since the locus of this equation passes through the origin, the coordinates (0, O) of the origin must satisfy it.
Substituting,
we have
o
ko
po
kTQ
or po
kT =
it
o.
Substituting this value back in equation (4') = o or
then becomes p
kT
(5)
P = kT.
a simple form of the equation (4) representing the same locus. Now, equation (4) was developed directly from Gay Lussac's generalization, which, as he showed experimentally, is true for any gas assuming the mass and volume constant. Therefore, equation (5) is true
This
is
for
any
gas.
Solving this equation for k,
we have
(50
*-f
t
Now Boyle's generalization is, that keeping the mass and temperature constant, the pressures are inversely proportional to the volume or as we saw, V: V\\:p\:p which becomes Vp = V\pi or keeping the
;
mass and temperature constant the product

is
of the
volume and pressure

is
a constant,
i.e.
pV =
K\, or
p =
ip
,
the pressure
inversely pro-
portional to the volume.
'
'
.
*'
24
PHYSICAL CHEMISTRY
Applying this generalization to

that
(5')
we have k
T
-.
=-y and remembering

is
T is
is
constant
we then have k =
This means that k

;
con-
stant only
when the mass and volume

increased, k
is
are constant
but that when the

jp
volume
decreased.
(5),
Substituting this value of k in equation
we have p =
or
(6)
pV =
KiT.
DISCUSSION OF THE CONSTANT OF THE GAS

Equation (A)
is
LAW
developed from Boyle's and Gay Lussac's This is true, generalization, assuming a constant mass. in the of case a true is a hypowhich however, only gas, wherein the internal thetically perfect gas, energy is deon the temperature only. Oxygen, hydrogen, air, pendent
and nitrogen so nearly conform to
perfect gases that for
practical purposes they may and obeying the laws of perfect gases.
be considered as ideally perfect
The equation
means that
K=
^
shall
(i)
if the volume of a given mass of gas is changed, the pressure or the temperature, or both temperature and pressure, must change so that the pressure multiplied by the
volume divided by the absolute temperature

the same.
always be
By experiment we find that keeping the pressure and temperature constant, the volumes of different masses of the
same gas are directly proportional to the masses, i.e. V: Vi: :M: Mi, where V is the volume of mass M, and V\ is the volume of mass Mi. So, different masses of the same
know
gas have different values of K. Also, by experiment, we that equal masses of different gases have different
volumes under the same conditions of temperature and
THE GAS LAW
25
In general, then, we must use different values of pressure. for equal masses of the different gases.
The value of K for unit mass by r. Let us denote the volume

then equation
Since
(i)
of unit
of a given gas is denoted mass of a gas by v,
becomes
pv
rT.
(2)
has different values for different gases, the gas
must be
specified
when using equation
(2),
and
r is called
the specific gas constant. It follows, then, that
K for any mass M K = Mr.
is
equal to
Mr
or
(3)
the masses of the different gases so as to give the same volumes at the same temperature and pressure,
If
we choose
has the same value for every gas, according to equation (i). By experiment we find that the molecular weight of every chemical compound in the gaseous state occupies the same
volume at a
If
definite pressure and temperature. the molecular weight of a gas is chosen, the value of If is the molecular weight, then is denoted by R.
from equation
(3)
R = mr
becomes
(4)
and equation
(i)
PV = RT.
Since the value of
(5)
all gases,
is
the same for
is
called
the Universal Gas Constant.
The molecular weight of a compound in grams is called the gram-molecular weight, or mole. If any number of moles, n, are used, the more general form of the equation is
pV = nRT.
Since n
(6)
-,'
where g
is
the weight in grams,
we may sub-
stitute in equation (6)
and obtain
(7)
26
PHYSICAL CHEMISTRY
Solving equation (5)
pV = RT
for R,
we have
-?-
But we saw that
for the
same mass
of gas
under different
conditions of pressure and temperature

therefore,
we have Ki =
To
And by
definition
is
we have p = the pressure of one atmos-
equivalent to 760 mm. of mercury, i.e. to the pressure of a column of mercury of one sq. cm. crosssection and 76 cm. high, or to the weight of 76 cubic centiphere, which
meters of mercury. Now, since one cubic centimeter of mercury weighs 13.6 grams, 76 cc. will weigh 76 X 13.6, or 1033-6 grams. The pressure of one atmosphere is therefore equivalent to 1033.6 grams per unit area of one square centimeter.
The temperature To = 273

Vo
is
,
tigrade scale, while
absolute on the cendenned as the volume of one
gram-molecule of oxygen, O 2 i.e. 32 grams of oxygen. Since the weight of one liter of oxygen is 1.429 grams, this
volume
of
oxygen
liters,
will
be
is
32
,
or 22.4
liters.
Therefore,
1.429
Vo = 22.4 volume.
which
designated
the gram-molecular
Substituting these values in our equation
R = ^-=-* we
,
To
have
of
It is
R=
R=s
22 4
'
= 0.08204
22400
liter-atmosphere
.
per degree,
273
1033-6
2 73
= 84?78o gram
centimeters
p er
degree.
in the
customary in Thermodynamics to express the terms Gas Law Equation in the English system and the
Fahrenheit temperature scale. If we have a mass of gas at the temperature of melting ice, 32 F., and at atmospheric pressure, then
THE GAS LAW

PQ
27 per
atmosphere
per square
14.6967
Ib.
square
inch
2116.32
Ib.
foot.
To
= 491.6 absolute on the Fahrenheit scale. v = volume of unit weight of the gas (i pound). B = characteristic gas constant and is the symbol used in
when
the English system of units
(2)
is
place of r
employed.
Then equation
becomes
pv
= BT.
(B)
If p is
From equation
of unit
(4)
we obtain
R = mB.
v
the mass
volume
of the gas,
we have
=
we
Substituting for v and obtain

P
P their values in equation (B),
=RT
Solving for R,
we
get
R = *% pT
If
(C)
m and p are known for any gas, R can be calculated. For oxygen p = 0.089222 Ib. per cubic foot at atmospheric pressure and 32 F. and m = 32. Substituting in above equation, we have
R=
The
'
'v 0.089222 X
I544
ft -- lb -
per degree
491.6
universal gas constant
R is
then equal to 1544
ft.-lb.
per degree.
From
stant
is
this value of R, the characteristic or specific con-
B of any gas may be determined if its molecular weight
known.
For carbon dioxide we have
It is often
B=
I ^
44
35.09.
44
convenient to express the density and the
volume
of unit weight of a gas in terms of the molecular
28
PHYSICAL CHEMISTRY
weight
ture
when
referred to standard conditions of tempera-
and
pressure.
From R =
~, we
lb.
have p
=
Rl
,
hence substituting the
pi numerical values
p = 2116.3
T=
491.6 F.,
P er sq.ft., we have
R=
i544ft.-lb. per degree,
and
=
degree.
2116.3
Xm
491-6
1544
=0-002788
rb.
per cubic foot per
And
for the
normal
specific
-
volume we have
X 4T
p
pm
2116.3
= ^^5
cubic feet per pound
CHAPTER
IV
DETERMINATION OF MOLECULAR AND SYMBOL WEIGHTS
THE method employed

weights at present
is
for the determination of
symbol
virtually that of Cannizzaro, wherein the weight of the gram-molecular volume is obtained for a large number of gaseous compounds containing that element,
and the greatest common
divisor of these quantities of the
element occurring in the gram-molecular volume is selected as the symbol weight of the element and is also termed the atomic weight. We selected arbitrarily as the unit volume of combina-
volume occupied by one gram-molecule of oxygen, 32 grams of oxygen under the standard conditions of temperature and pressure. For the standard conditions we have defined the standard pressure as the pressure of one atmosphere at sea-level and latitude 45, or 760 mm. of mercury, and the temperature as the zero on the Centigrade The unit for volume measurements scale or 273 absolute. is the cubic centimeter, one thousand of which are designated
tion the
i.e.
a liter. The weight of one cubic centimeter of oxygen under standard conditions of temperature and pressure has been determined very accurately and is found to be 0.001429
One liter weighs 1.429 grams. The volume occupied by one gram molecule of oxygen, i.e. 32 grams, is
gram.
32
-r-
1.429
22.4 liters under the standard conditions of

liters
temperature and
molecule,
i.e.
Hence, we designate 22.4 pressure. as the gram-molecular volume, as it is the volume of one
29
gram
the volume which the molecular weight of a
30
PHYSICAL CHEMISTRY
gas expressed in grams would occupy under standard conditions.
Density Relations.
generally for gases.
We have seen that pV = nR T holds

Let us assume that
g, it
does for those

of a gaseous
some other measured at the same and gas pressure temperature, and the same volume as the occupying standard, m a the weight
of
of a gram-molecular volume, 22.4 liters of the standard, the weight of a gram-molecular volume, 22.4 liters of the other gas. From the definition of the number of formula
with which we are dealing, and let body we select as our standard, g
grams
= grams
weights of any gas
we have n a =
nig
for the standard,
and
n =
tion
-&-
for
the other gas.
Substituting, the
Gas Law Equa-
becomes
d)
and
Solving,
pV =
RT.
.
(2)
m m RT m g = m,. But since 5 = Solving this for m, we have m 6* we have m = sm
RT m
g
>
&
t.
is
Since air obeys the Generalized Gas Law very closely, it considered for this reason a very good standard. The
weight of air has been determined very accurately, and it has been found that one liter of air at o C. and 760 mm. pressure at sea-level in the latitude of 45 weighs 1.293 grams. If one liter under standard conditions weighs 1.293 grams, then 22.4 liters, the gram-molecular volume, weighs If we now substitute this value for m, in the 28.96 grams.
equation above, we have molecular weight of a gas
m =
is
28.96.
That
is,
the
equal to its specific gravity
DETERMINATION OF MOLECULAR WEIGHT

expressed in terms of air multiplied
31
is
by
28.96,
which
the
weight of 22.4 liters of our standard (air). So, to determine the molecular weight of a gaseous substance we need only determine its specific gravity with respect to air, and mulThis is nothing more than finding the tiply this by 28.96. weight of the gas that would occupy one gram-molecular volume under standard conditions. It is not even necessary to determine the specific gravity with respect to air, but any other gas may be used as a
standard.
specific gravity
In that case, however, we have to multiply the with reference to that particular gas as a
standard, by an entirely different factor. For instance, if we use hydrogen as our standard, the weight of the gram-
molecular volume, 22.4 liters of hydrogen, is 2.016 grams, = SH X 2.016. If we and the equation would then become = s X 32, i.e. the use oxygen as the standard, we have
m m
specific gravity of the gas
with reference to oxygen multi-
plied
lar
by
From
equal to the molecular weight of the gas. what has preceded, in order to determine the molecu32
is
weight of a gaseous body, all we need to do is to determine the specific gravity, and from this to calculate the amount by weight that will occupy the gram-molecular volume, 22.4 liters, under the standard conditions of temperature and pressure. This number we call the formula
weight, or molecular weight.
The two
chief
methods
for the determination of
vapor
densities are the
Dumas method and
the Victor
Meyer
method. Only a brief description of the principles of these methods will be given. The technique of the operations may be found in the laboratory manuals on physico-chemical methods. Dumas' Method. A weighed glass bulb of about 200 cc. capacity, into which some of the substance has been introduced, is immersed in a water-bath, the temperature of which is kept about 30 above the boiling-point of the sub-
32
stance.
PHYSICAL CHEMISTRY
When
the end of the bulb

of the bath is
is all in the form of vapor, at which time the temperature sealed, and also the barometric pressure. recorded,
the substance
is
The bulb
weight of substance found.
then removed, cooled, and weighed, and the By filling with water at known the and weighing, weight of the water is found by temperature difference. The volume which this weight occupies is found
is
from tables of densities of water at
different temperatures. the volume, temperature, and weight of the Then, knowing barometric reading, the density and and the substance,
specific gravity
but
little
can readily be calculated. used at present.
This method
is
The
Victor
Meyer Method.
The Victor Meyer method
consists in measuring the increase in volume of a quantity of air, caused by introducing into it a weighed quantity of
the substance whose density is to be determined, and vaporizThe vaporized substance displaces an equal volume ing it.
and this displaced volume of air is collected and measured, and at the same time its temperature and the barometric pressure are observed and recorded. This then gives the weight of the substance taken, and the volume, temperature, and pressure, from which the density, specific gravity, and the molecular weight can readily be
of air,
calculated.
Molecular Formulae and Formula Weight. Having just how the molecular weight of a gaseous substance can be obtained, we can ascertain the formula which expresses not only the relative quantities of the component elements, but also the weight of the substance which occupies a grammolecular volume. Such formulae we designate as molecuseen
and they are now employed to represent the quantity of the substance designated by the molecular weight, whether it exists in the gaseous, liquid, or solid
lar formulae,
condition.
Suppose benzene
is
tain 92.25 per cent of carbon
and
found by analysis to con7.75 per cent of hydrogen.

Then
33
many
in every 100 g. of the substance we should have as Q2 2 C or 7.69, and of symbol weights of carbon as
,
hydrogen as -^~r, or
weight of carbon there
7.69.
is
That
is,
for
every symbol
;
same number
is
of
one of hydrogen there are the of the two elements. Assymbol weights
suming the simplest number present, the empirical formula CH. The specific gravity of benzene with respect to
is
oxygen
2.47 at 100
C.
The molecular weight
is,
there-
fore, 2.47 79.04, which is nearly six times the sum 32 of the symbol weights of carbon and hydrogen as represented by the empirical formula. The molecular formula is therefore CeHe, and the molecular weight is 78.06. The symbol (or atomic) weight of an Symbol Weight. element may be deduced from the molecular weights of its gaseous elements in the following manner In order to ascer:
symbol weight of compounds are selected
tain the
hydrogen a large number of gaseous which contain hydrogen, and the
molecular weight of these substances is ascertained from In Table I are density and specific gravity determinations.
given the names of the substances, in the second column the molecular weights, i.e. the grams of the substance that occupy
22.4 liters under standard conditions of temperature and pressure, while in the third column is given the number of grams of hydrogen found by analysis in the amount of the
substance represented by the molecular weight given in the second column. In the last column is the greatest common
divisor of the weights of
hydrogen in column three, times
multiplied to give the amount of these various hydrogen gram-molecules of the gases. Now in the case of hydrogen, the greatest common divisor
the factor
by which
it is
in
of the quantities of this element appearing in the grammolecules of these various substances is i g. hence we take
;
the symbol weight of hydrogen to be
i.
Proceeding in a
34
PHYSICAL CHEMISTRY
similar manner, we can compile tables for other elements such as given for nitrogen.
TABLE
HYDROGEN

not be the true one
;
35
however, those so obtained have a
high degree of probability.
however, there are but very few volatile compounds containing the element, which are available for vapor denThere are a sity determinations, the method may fail.
If,
number of other methods, however, for obtaining the molecular weight of substances, and these values may be used in our tabulations just as well as those obtained
through the vapor density relations.
Some
of the
more recently discovered elements, the gases
argon, helium, xenon, etc., are supposed to be elementary, and to contain only one symbol weight in their gram-molecular weight. As they form no compounds, we cannot use
the
method
If,
just
weights.
suggested for determining the symbol however, we remember that the molecular
weight is the weight of the substance that occupies 22.4 1. under standard conditions of temperature and pressure, we can find the molecular weight by ascertaining the number of grams of the gas that are contained in a gram-molecular
volume.
We have just seen that by our volumetric method we may determine which of several quantities is the correct one for the symbol weight of an element but in order to determine these values with a high degree of accuracy, it is necessary to employ quantitative gravimetric methods. By the above methods it is possible to determine which of a number of values is the correct one for both the symbol weight of elements and also the molecular weight of the compounds.
;
The
International
Committee on Atomic Weights publishes
periodically a table of values, which it designates the Atomic Weights, based upon the unit of oxygen taken as 16 and
representing relative weights.
CHAPTER V
ATOMIC AND MOLECULAR THEORIES
are
FROM observed experimental scientific facts, conjectures made as to how other substances react and these are
employed as the starting point for additional experimentation and investigation. This is regarded as a working hypothesis. While a hypothesis is a tentative speculative conjecture of the causes for the observed facts, it is an assumption which goes beyond these observed facts and is to be used as a basis for their arrangement and classification as well as that of all other facts of the same class.
it
a hypothesis explains all of the known facts, then " ranks as a theory. A theory is defined as a systematic entertained as generalization seriously exclusively or emiof for a series or group phenomena." As nently accounting
When
soon as a number of facts are collected which the theory does not accord with or explain, the theory becomes untenable, and a new one has to be formulated which will harmonize with the known facts. We have hypotheses and
some
theories undergoing frequent changes, as they always contain unproved assumptions. How our path of progress is blazed out and marked is indicated by the following quotations from two noted pioneer
investigators. Tyndall states
"
:
We
agination,
and by
this
are gifted with the power of impower we can enlighten the darkness
of the senses.
which surrounds the world

ditioned
Bounded and con-
by cooperant
reason,
36
imagination becomes the
37
mightiest instrument of the physical discoverer. ... By his observations and reflections in the domain of fact the
scientific
philosopher
is
led irresistibly into the
domain
of
depending on the establishment of absolute harmony between both domains." " The world little knows how many of Faraday wrote the thoughts and theories which have passed through the mind of an investigator have been crushed in silence and
theory, his final repose
:
secrecy by his own severe criticism and adverse examination that is, in the most successful instances not a tenth of
;
the suggestions, the hopes, the wishes, and the preliminary conclusions are realized."
THE ATOMIC THEORY

not continuous, but composed of minute, atoms is a very ancient idea. This idea was purely speculative and not founded on observation or experiment. Democritus (460 B.C.) attributed the difference in substances to the atoms of which they are constituted, and these atoms he considered to be different in
is
That matter
indivisible particles or
Lucretius (50 A.D.) forsize, shape, position, and motion. mulated the ideas of the atomic constitution of matter in practically the form in which it is familiarly expressed to-day.
following are his conclusions In a solid the atoms are squeezed closely together in a liquid the atoms are similar and less closely packed while
:
The
1
.
in a gas there are but freedom of motion.
few atoms and they have considerable
2. Atoms are imperishable, of a finite number of different shapes, each shape being infinite in number. 3. The atoms are always in motion and move through
space at a greater speed than sunlight. 4. The properties of substances depend upon the manner in which the atoms combine. During the seventeenth century the atomic conception of
38
PHYSICAL CHEMISTRY
the composition of matter was very popular and was employed by Bacon, Boyle, Hooke, and others. Newton showed that Boyle's law of gases must necessarily follow
from
this assumption.
The two Irish chemists, Bryan Higgins (1737-1820) and his nephew and pupil, William Higgins (1765-1825), were among the first to seek quantitative relation between the atoms and to attempt to determine the number of atoms which combined to produce a new compound. They concluded that combinations took place most readily between the single ultimate particles of two substances, and William Higgins emphasized the law of multiple proportions, and also the greater stability of the products formed by the union
same as those formuby Dalton, as early as 1803. The Daltonian Atomic Theory was based on facts obtained by experiment and was Dal ton's method of explaining these weight relations that he had obtained. Dal ton's Atomic Theory is stated as follows 1. Atoms are the smallest ultimate particles attainable and therefore cannot be subdivided by any known chemical
lated later
:
of these single particles (atoms). These views are substantially the
means.
2. An elementary substance is composed of an enormous number of these particles, called atoms, which are of the same kind and equal in weight. 3. Atoms of different elements have different properties,
such as weight, affinity, etc. 4. Chemical compounds are formed by the union of the atoms of different elements in the simplest numerical proportions.
In 1808, Dalton in his statement of the atomic theory emphasized how important it is to be able to arrive at a
knowledge of the relative weights of these ultimate particles which combine to form compounds, and that these relative
39
weights serve as a guide in obtaining the composition of other substances. These relative weights he collected in 1803 in what was termed a Table of Atomic Weights. Dal ton considered atoms, the ultimate particles of com-
pounds, as the ultimate particles of elementary substances. He assumed for example that one atom of hydrogen unites
with one atom of oxygen to produce one atom of water. In the development of these atomic weight relations many discrepancies arose which were difficult to reconcile. Gay Lussac presented his Law of Combining Proportions by
Volume (about 1 801-08), which
is,
that the weights of equal
volumes of gaseous substances are proportional to their combining weights or, as Dal ton called them, atomic
weights.
It has been shown that definite quantities by weight of certain substances called elements unite to form new sub-
stances termed
strated that
compounds it has further been demonwhen one element combines with another in
;
two or more
different ratios forming different substances, the quantities of the first element combining with a unit quantity of the second are in simple, integral ratios. It has
further been
shown by Gay Lussac, and has subsequently been confirmed, that when reacting gaseous elements combine, the volumes of the different gases under the same conand temperature are in simple ratios to one another and to the resulting gaseous product. The
ditions of pressure
following facts will serve as examples
I.
i.
The combination
sulting
of one volume of chlorine, bromine, or iodine with one volume of hydrogen to form two volumes of the re-
compound.
2.
The combination
iodine to form
3.
of one volume of chlorine with one volume of two volumes of the resulting compound. The substitution of chlorine, bromine, iodine, fluorine, and
cyanogen
volumes.
in
many
organic compounds are reactions of equal
40
II.
i.
PHYSICAL CHEMISTRY
The combination of one volume of oxygen, or one volume of the vapor of sulphur or selenium, with two volumes of hydrogen to produce two volumes of the resulting product. The combination of one volume of oxygen with two volumes of
chlorine.
3.
2.
The combination
nitrogen.
of
one volume of oxygen with two volumes of
III.
i.
of
2.
of one volume of nitrogen with three volumes hydrogen to form two volumes of the resulting product. The combination of one volume of nitrogen with three volumes
The combination
of chlorine.
combines with chlorine,
a definite volume of hydrogen has been shown experimentally that this volume of chlorine is the same, under the same
illustrated above,
if
As
it
the hydrogen with which
conditions of temperature and pressure, as that occupied by it combined. We have seen that the
law of combination by weight holds true and that it is absoThere must, therefore, be some weight relalutely exact. tion existing between these volume relations, since they combine with one another in such simple integral ratios.
If
we take the quantity
of
oxygen that
is
equivalent to the
arbitrarily selected amount of our arbitrarily selected Unit of Reference, and the same volume of hydrogen under the
same conditions
of temperature
and pressure, we
shall find
that the oxygen weighs 15.88 times as much as the hydrogen. If we take 16 g. of oxygen, the same volume of hydrogen will weigh i .008 g. This same volume of chlorine weighs 35.45 g.
and the same volume of nitrogen weighs 14.0 g., it being understood that the volumes are under the standard condiIt will be recalled that tions of temperature and pressure.
numbers are the same as those representing the symbol weights of the elements hydrogen, chlorine, and nitrogen.
these
If we take the quantities of gaseous elements equivalent to these weights, called by Dalton atomic weights, the volumes which these occupy under the same conditions of
temperature and pressure
will
be the same.
Dalton con-
41
eluded that in equal volumes of different gases at the same temperature and pressure there were not the same number of
ultimate particles.
Gay Lussac showed
that the combining
weights (or
some multiple)
of different substances were pro-
In 1811 Avogadro accepted portional to their densities. this law of Gay Lussac and concluded that the number of " " in equal volumes of all gases is the same integral molecules
for the
that
if
we were
same temperature and pressure. Avogadro insisted to assume the molecules of elementary gases
identical with the atoms, the volumetric relations could not be explained, as it would'necessitate the subdivision of some
of the atoms.
It
was
this particular feature
which met
with such marked opposition from Dalton and his contemporaries and at that time prevented the acceptance of Avoof
Hence the existence of small particles and the atoms, as advocated by Avogadro, received little notice and the revival of the idea by Ampere in 1814 did not succeed in having it
gadro 's hypothesis.
two
different orders, the molecules
accepted. For the next forty or fifty years a rather chaotic condition prevailed, and very little progress was made in the develop-
system of atomic weights. In 1860 a conference of chemists met at Karlsruhe for the purpose of discussing the subject and eliminating the confusion arising from the use of the four systems of atomic weights then in use. These methods were that of (i) Dalton, based on weight relations and chemical analysis (2) Berzelius, based partly on chemiof a
:
;
ment
on physical principle (the Law of Isomorphism) and partly on the Law of Combining Proportions by Volume, all of which did not differentiate between atom and molecule and (3) Gmelin's weight method (4) Gerhardt and Laurent's method, in which a realization of Avogadro's hypothesis was manifest, and had a farreaching effect. The work of Cannizzaro, in 1858, revolutionized the atomic weight methods by making Avogadro's
cal analysis, partly
; ;
42
PHYSICAL CHEMISTRY
hypothesis the basis of his system ,and thus established our modern system of atomic weights. This work was brought to the attention of those chemists while in session at
Karlsruhe.
It was by affirming the universal applicability of Avogadro's supposition that Cannizzaro stated that results are obtained which are in keeping with certain formulated laws
of chemistry and physics. Avogadro's method of determination of molecular weights, which had been practically
abandoned, was revived by Cannizzaro, who changed the

unit to which vapor densities were referred and restated it as " Instead of taking for your unit the weight of an follows
:
entire molecule of hydrogen, take rather the half of this weight, that is to say, the quantity of hydrogen contained
a molecule of hydrochloric acid." using the hypothesis of Avogadro, Cannizzaro examined the relative weights of compounds, the composition of which he determined, and described his method in the fol"If the body is a compound, it is lowing exact terms analyzed and the constant weight-relations of its constituents the molecular weight is then divided into are determined
in
By
parts proportional to the relative weights of the compounds, and the result is the quantities of the elements contained in
the molecule of the compound, referred to the same unit (namely, the semi-molecule of hydrogen) as is used for the
all molecular weights." Cannizzaro 's law of atoms has made it possible to express the composition of molecules in terms of their constituent
expression of
atoms, for
all
gaseous and gasifiable compounds, and was

as follows
:
stated by him
By comparing the different quantities of one and the same element which are contained, either in the molecules of the
free elements, or in the molecules of its
:
compounds, the fol" in relief The law stands out different weights of one lowing and the same element contained in the various molecules are

always whole multiples of one quantity, which
the atom, because
it
43
is
justly called
invariably enters the
compounds without
division."
The atom of an element, Cannizzaro said, " is expressed by that quantity of it which invariably enters as a whole
into equal volumes of the simpler substance and its compounds this quantity may be either the whole quantity contained in a volume of the free element or a fraction thereof." " However, In order to determine the atomic weights of any
;
it is essential to know the molecular weights, and the compositions, of all or most of its compounds." We then have described by Cannizzaro a clear picture of the interrelations of all the fundamental conceptions of
element
Dalton and Avogadro, which were at their time practically in this way there was developed a complete " placed the atomic weights of the metallic theory which elements on their present consistent bases." Cannizzaro thus advanced the theory of atomic equivalency, which em" the unchangeability of the proportions between phasized the atomic weights of the bodies which usually replace one another, whatever be the nature and number of the other constituents of the compounds." This is a law which limits
discarded
;
of possible compounds and all cases of double exchange. to applies
the
number
more
especially
THE MOLECULAR THEORY

This
is
the
method
for the determination of the
combin-
ing or atomic weights which is employed at the present time, and which is illustrated in the following consideration
:
For chemical reasons, chemists have accepted Avogadro's hypothesis, which leads to the molecular structure of matter.
This hypothesis,
known
as the Molecular
Theory
of the
conceives matter as discontinuous and

particles called molecules.
made up
of Matter, of minute
The molecules
all
same sub-
Stance are assumed to be alike in
respects.
The mole-
44
PHYSICAL CHEMISTRY
cules are considered to be practically independent, with " that minute space between them, and may be defined as
moves about as a whole so that has any, do not part company during the and the molecular weight is excursions the molecule makes the weight of this ultimate particle referred to the weight of the molecule of a standard substance." As a working hypothesis this assumption of Avogadro has been very fruitful, as the following illustration indicates.
portion of a substance which
its parts, if it
;
i.
Hydrogen and
chlorine unite to produce hydrochloric
acid.
have determined experimentally volumes of hydrogen and chlorine react to proEqual duce two volumes of hydrochloric acid.
Facts.
i
. :
We
Hydrogen
Chlorine
Hydrochloric acid
vol.
vol.
2 vols.
2. By analysis it has been shown that hydrochloric acid consists of hydrogen and chlorine in the ratio of one symbol
weight of hydrogen to one symbol weight of chlorine. Assumptions. In unit volume let us assume that there are n 1.
molecules.
2. According to Avogadro's assumption equal volumes contain an equal number of molecules. Since there are two volumes of hydrochloric acid, accord-
ing to Avogadro's hypothesis this volume must contain twice as many molecules of hydrochloric acid as there are molecules
hydrogen in the one volume of hydrogen. That is, one volume of hydrogen contains n molecules of hydrogen, and two volumes of hydrochloric acid contain 2 n molecules of
of
hydrochloric acid.

It follows that the
2
45
in
number of atomic weights of hydrogen n molecules of hydrochloric acid must be the same as in the n molecules of hydrogen.
If we assume, for simplicity, that each molecule of hydrochloric acid contains one atom of hydrogen, then 2 n mole-
cules of hydrochloric acid will contain 2 n atoms of hydrogen ; but these 2 n atoms of hydrogen must have been furnished
by the n molecules of hydrogen. Therefore, one molecule of hydrogen must contain at least two atoms of hydrogen, and the formula is written H 2 which represents the molecule
,
of hydrogen. Similarly the molecule of chlorine shown to contain two atoms, and its formula is C1 2
it
may
.
be
By pursuing a course of reasoning analogous to the above, may be shown that the molecules of some other gaseous elements consist of at least two atoms. By grouping the
symbols of the elements we obtain the formula of the element which represents the molecular weight and indicates the number of atoms of each element present in the molecule.
CHAPTER
DEVIATIONS
VI
FROM THE GAS LAW AND DISSOCIATION

OF GASES
IT has already been stated that only for ideally perfect gases does the Gas Law Equation hold, but in the case of O2 2 2 and air the deviations are so small for moderate
,
N H
,
ranges of pressure and temperature that they conform to the laws very closely and therefore may be considered for
all practical purposes as perfect gases. Although these deviations are small, they are real, and there must be certain causes which produce these deviations from the theoretical
laws.
Deviation from Boyle's Law. If gases are subjected to does not conform the in volume very high pressures, change
too
FIG.
2.
to Boyle's Law Vo V p po, or Vo = constant. Or, expressed graphically, curve as represented in Fig. 2.
:
: :
: :
po
Vp, or
Vp
the
we would have
But the experimental
results of
Amagat on
the effects
of high pressure show that the value of p V is not a con-. stant for different pressures, and this is illustrated by the
data given in Table
II.
46
DEVIATIONS FROM THE GAS LAW
47
TABLE
p
II
Value of
pV at
o C.
48
PHYSICAL CHEMISTRY
Fig. 3 it
is
From
apparent that with increase of pressure
the value of
pV first decreases, reaches a minimum, and then
increases, except in the case of hydrogen, where we have only the portion of the curve representing an increase in the " value of pV, which led Regnault to call hydrogen a more than perfect gas," because the volume was not decreased as much as it should be according to Boyle's Law. That portion of the curve of all gases which represents the high pressure shows that the gases are not compressed as much as they should be according to Boyle's Law.
Confirmation of these results
is
found in the work of Wit-
kowski, Kamerlingh Onnes and Brook,
Ramsay and Young,
Barus, and others. The change of the value of p V with the change
in
p at various temperatures has been obtained by these workers,
and
this is illustrated in Fig. 4.
It appears, then, that there
must
be a particular temperature for each gas at which the depression

in the isothermal just disappears,
so that
it is
horizontal through a
considerable
range of pressures. At this temperature a gas follows Boyle's Law exactly, up to a fairly
high pressure, and behaves to this extent like an ideal or perfect gas. This is also true for a short distance at and near the minimum value for pV, while at the high pressures the isotherms approxi-
100 ZOO Pressure In- Atmosphere
mate nearly parallel straight lines. In the case of very low pressures, there is not so marked a variation, and the conformity to Boyle's Law is more marked. Experimentation along this line has
FlG. 4.
Low
Pressures.
49
been carried out by Mendeleeff, Amagat, Ramsay and The Barly, Battelli, Rayleigh, Regnault, Leduc, and others.
conclusion from their work
is
that in the equation ^

is
b,
where
is
the larger volume and p
the smaller pressure,
the value of b approaches and finally reaches unity as the In the case of hydrogen the value rises, and pressure falls.
for other gases
it falls.
For the range
of pressures, of 75 to
150 mm. the differences from unity are quite negligible in the cases of hydrogen, air, and probably nitrogen. There is
a slight difference in the case of oxygen, but this difference disappears at still lower pressures. For N2O the value of b
high between 75 and 150 mm. the values of b obtained by Rayleigh
is fairly
:
The
following are
b
............ ............ ........... Argon NO ...........

H
2
Air
....... .....
0.99997 0.99997
1.00024 1.00021
1.00066
O2
While the deviations from Boyle's Law are apparent, they are so small at low pressures that they are difficult to detect, even by very accurate experiments, yet they prove that these
gases do not follow Boyle's Law absolutely. Deviation from Charles' or Gay Lussac's Law.
efficient of
The
co-
expansion of gases varies with a change of temand This is emphasized in the case of perature pressure. in Table taken from Amagat's data. ethylene III, The pressure remaining constant, the horizontal lines in Table III show a variation of the coefficient of expansion with the change of temperature. There is no regularity in the
is less
change, but, in general, at higher temperatures the variation than at lower temperatures. The vertical columns
increased pressure.
show a marked decrease in the coefficient of expansion with The minimum value of the coefficient
PHYSICAL CHEMISTRY
of expansion corresponds closely with the for pV.
minimum
values
TABLE
PRESSURE
III
COEFFICIENTS OF EXPANSION OF ETHYLENE
METERS OF MERCURY
Law
of pressure
they therefore all had the same coefficient of increase = (3. (|3) at constant volume, i.e. a
TABLE IV
GAS
52
PHYSICAL CHEMISTRY
such as hydrogen, nitrogen, air, oxygen, but the variations are very pronounced in the case of those which are readily liquefiable, such as sulphur dioxide, carbon dioxide, ethylene, etc. Various efforts have been made to explain these variations from The Gas Law, which we have seen show that at low pressures some gases are too compressible, while under high pressure they are not comdifficult to liquefy,
etc.,
Among the most fruitful of the explapressible enough. nations offered is the one of van der Waals. There is another type of variation from The Gas Law in the case of certain other gases which give abnormal values for the den-
with increased temperature. This variation is explained upon the supposition that the gas molecules are dissociated with the formation of new chemical individuals.
sity
VARIATIONS FROM THE GAS LAW AS EXPLAINED UPON THE BASIS OF DISSOCIATION OF THE GAS
Attention has been called to the fact that a number of
substances do not conform to the Gas Law Equation and that the vapor density determinations give abnormal values It was recognized by the earfor the molecular weights.
lier
workers that the results must be due to abnormal
molecular conditions and that Avogadro's hypothesis did not hold for these cases, such as ammonium chloride, phos-
phorus pentachloride, nitrogen dioxide, etc. Almost simultaneously Cannizzaro (1857), Kopp (1858), and Kekule* (1858) advanced the idea that these abnormal values were due to the decomposition of the substance. This decomposition was termed dissociation by St. Claire Deville (1857). This assumption of the dissociation of the gaseous molecules to account for the low density was not readily accepted, and it devolved upon the champions of the idea to prove that dissociation did take place. The following four typical examples were employed to
prove the dissociation of these substances
:

1
.
53
Deville found on raising the temperature of PC15 that at high temperatures the colorless gas became decidedly green. This may be explained by the following equation PC15 = PCla
:
-f C1 2
2.
the green color being due to the chlorine gas present.
On
heating
NO
2
4,
which
it
is
colorless, it
brown, and on cooling
decolorizes again.
becomes dark Salet showed
(1868) that the color varied with the vapor density. high pressures approximately normal densities for
Under
N O4 are
2
obtained, while at high temperatures and low pressures, values approximating that of 2 are obtained, and hence
NO
we conclude
3.
that the brown color
is
due to
NO
2.
Pebael heated
ammonium
chloride which
had been
incorporated in an asbestos plug. During the heating a current of air was passed through the tube. By means of
litmus paper he proved that an excess of hydrochloric acid was present in one end of the tube, while at the other end
ammonia was
and by a
4.
in excess.
Thau used
chloride.
slight modification of the
nitrogen instead of air, method confirmed the
dissociation of
ammonium
In the case of chloral hydrate, Toost proved that the
low density was due to dissociation by distilling chloral hydrate (melting point 57 C.), and collecting its vapor in chloroform. Chloral dissolves but the water does not hence he concluded that the chloral hydrate was dissociated
;
according to the equation
CC1 3
CH(OH) 2 = CC1 3 CHO
+ H O.
2
of these data soon resulted in the general that dissociation was the cause of the abnormal acceptance values of the densities.
The presentation
One
of the
common
applications of dissociation
is
made
use of in cleaning the soldering iron by rubbing it against solid ammonium chloride, the liberated hydrochloric acid Commercial hydrochloric acting as the cleaning agent. acid is now used extensively for that purpose.
54
PHYSICAL CHEMISTRY
Degree
of Dissociation.
a.
Let
n = number / = number
then an
degree of dissociation or per cent dissociation of molecules

of parts into
which each molecule
is
disso-
ciated
= number of molecules dissociated an = number of molecules undissociated anf = number of parts resulting from dissociated molecules n an + anf = total number of parts or molecules after dissociation. Let i denote the ratio of the number of molecules after dissociation to the number of molecules before dissociation,
n
Then
That
Let
is
n-c n+anf
i
OT
+a
(/
i)a or
a = -*-=-^
(2)
an
Since
= = Pi V = Vi = n = anf =
p
density before dissociation
density after dissociation
volume before dissociation volume after dissociation
number number
of molecules before dissociation of molecules after dissociation.
=
mass
and*-
From Avogadro's Hypothesis

Substituting
~ = n an ~ an = n
pi
+ anf
+ anf =
-
we have
a we have
n
P
!-+/
(3)
5i
and solving
If 5 is
for
a =
Pl
Pi(f-
the specific gravity before dissociation and

5,
the
sp s
specific gravity after dissociation, then from page and pi = Sip s Substituting in formula (3) we have
.
Sp s r'
Sip s
or
Si
s lPs (f-i)
55
_p
If
* =
have
^,we
r
That
cent.
If
Pi
is,
^^
/
is
if pi
k.
the degree of dissociation
complete, or 100 per
a substance dissociates into

-, 2
is,
2 parts, its
that
is,
of original density.
If into 3 parts, pi
vapor density =3
p,
that
and no
\ of its original density. dissociation takes place.
But
then a
EXAMPLE. At 90 C. the specific gravity of nitrogen peroxide (N 2O 4 ) is 24.8 (H = i). Calculate degree of dissociation.
''
a =
=
J/"-*)
2^8 7/i)
'
'
8547
''
8547 per cent dissociated.
EXAMPLE. When 5 g. of are completely vaporized at 200

under a pressure of 740
tion.
ammonium carbamate
C., it occupies
NH CO NH
4
mm.
2
mercury.
a volume of 7.66 liters Calculate the degree of dissocia-
NH + CO
3
m
--
78, molecular weight of
ammonium carbamate
gram-molecules
-5-
78
(i
+ 2 a) m
total
number
of molecules
pV = nRT:
24. 700
pV = --(1 w x 7-66 = -^
78
(i
.+ 2 a)tfr
/>
74? atmosphere 760
+ 2 a) X
r
0.082
473.
Solving, find
a = 0.999
99-9 per cent dissociation.
56
PHYSICAL CHEMISTRY
On complete dissociation, we have in the case of nitrogen peroxide a simple gas, while in the case of ammonium carbamate we have a gaseous mixture consisting of ammonia
and carbon
pressure
dioxide.
Depending upon the temperature and
have, in all intermediate states, partial dissociation. We see that certain gaseous substances which give abnormal values for their densities, upon the basis that they
are dissociated, confirm Avogadro's hypothesis, and that the state of an ideal gas is realized when there is complete dissociation, as in the case of the undissociated gases we have
we
previously considered.
The Law
of
Mass
Action.
In the type of reactions
we
have been discussing, at ordinary temperatures and pressures the substances nitrogen dioxide and ammonium carbamate are distinct chemical individuals, the one a gas and the other
a
solid.
If
tion of
tions
new chemical individuals as above. As the temperature
they are heated, they dissociate, with the formaillustrated in the equais
increased
more and
more, the original substance is dissociated, while at any specified temperature the products of dissociation are in
equilibrium with the undissociated substance.
The
state of
equilibrium represent by equations, such as N 2 O 4 ^ 2 NO 2 which means that the reaction may proceed in either direction and is designated a reversible reaction but for in directions conditions it does both any specified proceed at the same rate, and consequently an equilibrium is thus
we
maintained.
The law governing the
this statical condition of the reaction is
state of equilibrium or known as the Law

;
Mass Action and can be developed thermodynamically but this particular theoretical consideration of the subject will have to be deferred, and we will illustrate the of the law by applying it to a few specific meaning
of
cases.
Suppose we have two substances, A and B, reacting to form their resulting product, AB. Then A -f B = AB,
57
we may have the reverse, AB = A one equation we have AB ^ A + B.

or
B, or writing as
more general
statement would be where more substances react, forming The reaction is represented a homogeneous system.
thus,
A + A + A - ^ AS + AJ + A
1
'
...
which indicates that only one molecule of each substance

takes part in the reaction. That this reaction takes place depends, according to the kinetic theory of gases, upon the collision of the molecules, and it is obvious that the nearer they are together the more numerous such collisions and the
greater the relative Hence the reaction
number
(i.e.
collisions)
of molecules per unit space. is proportional to the
concentration.
Then the velocity of the reaction is proportional to the products of the concentrations. = velocity from left to right, and ci, c2 represent Let i.e. the the concentrations of the substances A\, 2
number
equation
of gram-molecules
is
per
liter.
Then the
reaction
V=
KciC2
where
is
a constant for the
given temperature. If the reaction proceeds in the direction from right to left, = f c\c2 in which the terms have we shall have
analogous meaning to those in the first cases. As the values of V and cannot be measured alone, the course of the reaction can only be given by the difference of the two values. The total reaction velocity is made up of
the difference between the two partial reacting velocities for the change actually observed for any amount of time is
;
equal to the reaction in one direction minus the change in the opposite direction during this same time. When the
condition of equilibrium has been reached, we are not to conclude that no further change takes place but should
;
assume that the change, in the sense of the reaction equation from left to right, is compensated by a change from right to
58
left,
PHYSICAL CHEMISTRY
and therefore that the
i.e.
total
change to be observed
zero,
the system stands in equilibrium.
Then we
have for equilibrium
VA
o,
'"
or
V =
.'.Kcic2
K'CI'CZ '.
more general statement would be to remove the restriction that only one molecule takes place in the reaction and that there is only one molecule of each molecular species
form
produced. In that case the formula takes the following for the Generalized Mass Law Equation
:
gl
*. g.*.
'
,.....
c3
'
ci'
n *'
c2
n3 '
n3 '
= IC
k a Qon
which
to
is
dissociation
termed the equilibrium constant; but where applied phenomena it is termed the dissociation
constant.
Now
applying this Mass
Law Equation
case of dissociation, when a compound the two parts A and B, we have ^
AB
to the simplest dissociated into
(1)
Kci
cz
cz.
If
A B, the reacting substance

A
2,
AB
is
made up
of like parts, then
we have
A
(2)
which becomes
Kci
cz
.
C2
c2
That
which is obtained from the above when is, where the substance dissociates into two
,
like constituents.
Let
c,
the concentration
= g/no FV
'
of
vol.
\ /
Substitut-
ing this value for the concentration in equations (i)
and
(2)
we have
VJ
59
Now
since n%
n$,
we have
which becomes
HI
That
is,
increasing the
volume produces a
relative increase of
dissociation.
Many times it is difficult to determine
the concentration of
the components. We can avoid the necessity of doing so by introducing the pressure factor and measuring that instead
of determining tjie
concentration.
The
final
form of the
(3)
Gas Law Equation was
pV = nRT
which becomes
n But
since
'
V
c
RT
=
-*
= c, we have
RT
to the pres-
sures.
The concentrations are directly proportional The equation then becomes

c
Idp.
(4)
for
Now, since concentration is proportional to the pressure, c\ we may substitute K\p in the equations above, and we
for equation (2)
have
or
Kc\
(c2
)
the following
z
K(KlPl = (K p,Y
Now
since
represents a
new
constant,
we may
ex-
press this
by some
single letter, as k,
hence we have k
= &->
60
PHYSICAL CHEMISTRY
This gives us the pressures due to the individual constituents of the gas mixture, and these are designated the partial
pressures.
pressures,
lar species
The
i.e.
total
pressure
is is
the
P=
pi
+
'
pz.
This
sum of the partial Dalton's Law. From
a consideration of The Gas
Law we have, for several molecuoccupying the same volume at the same tempera-
ture, the relation
^=
p2
nz
Mixtures of Gases. We should expect that the most simple relations would be found to exist in the case of mixtures of different gases. Such is the case where there is no
chemical action between the gaseous particles. Each gas remains unchanged and conducts itself as though the other one was not present. The pressure exerted upon the walls
of the containing vessel, the capacity of absorbing and reflecting light, the specific heat, etc., in fact all of the properties of the gases experience no change when the gases are
mixed.
These particular relations should hold only in the case of ideal gases and as all the gases only approximately follow The Gas Law, we should expect to find some slight
;
deviations
when the gases are mixed. Dissociation of Gases. Let us consider the following cases
:
(i)
PC1 5 ^
PC1 3
+
.
C1 2
and
(2)
HI ^
H +
2
I2 .
Applying the mass law, we have

Kci
c2
c3
Kci 2
c2
c3
Expressing concentrations in terms of number of molecules in unit volume,

7^wi_
we have
tt2
nj
.V.
=^ x^ V V
2
'
^
V*
Multiplying through by V,
and by
V
.
2
,
Kn, =
25-
Km
n,
n3
6l
In the case of PC1 5 the dissociation is proportional to the volume, while in HI as there is no value of V in the equation, the dissociation is independent of the volume.
Introducing the pressures instead of the concentrations
we have
Kipi
= p2
pi.
KipS =
p2
p.
We
m-fold,
can decrease the volume by increasing the pressure when we shall have
which become
Kipi
In the
first
p2
mp
z.
Kipi
p2
p3
case
we have
it is
while in the other case
the dissociation forced back, not affected by the increase of
pressure, as the factor disappears. Hence, in all cases where the number of reacting substances, i.e. the number of molecules on both sides of the equation, are equal, the change in the volume has no effect on the degree of dissociation.
Dissociation of
Ammonium
Carbamate.
Carbamic acid
in
may
be considered as carbonic acid,
CÔH, X)H
which one
of the hydroxyl groups
(OH) has been replaced by the amido
group
(NH
2 ),
C^-OH
\NH
The ammonium
3,
salt is
formed by
8 -f-
the direct addition of
NH as in the NH C1, when we have (NH CO

4
3) 2 2.
reaction
NH
HC1
On
heating
ammonium
carbamate,
2
we have
2.
(NH
3) 2
C0
NH + C0
3
Now
applying the mass law,
we have
62
PHYSICAL CHEMISTRY
Since the carbamate
is
solid, its
concentration will re-
main
that
is so small practically in comparison to the pressures of the dissociated products
constant, and the vapor pressure

will
.
it
can be neglected, when we
have
Ki =
C2
ct
Substituting pressures for the concentrations,
we have
K
But the
i.e.
= p
z 2
pz.
P=
cules of
for pz
+ NH as
3
total pressure is the sum of the partial pressures, ps, and since there are twice as many molep2
of
CO
2,
=
/>
p3
3
Substituting this value
we have
P=
p3
+
(f
p 3 or
p 3 or p 3
P.
Now substituting
these values of p%
and p 3 we have
^2=
It is
P)
-iP
or
^P^
force
evident that the addition of
ammonia should
back the dissociation more than the addition of carbon

dioxide.
In the case
-f
of
ammonium
chloride,
NH C1
4
HC1, Neuberg found the density of NH 4 C1 in the vapor form to be 1.13, while the calculated value is 1.85. In an excess of 34.6 cc. of HC1 the density was 1.5, while in an
excess of 60 cc. of
NH
forced back
dissociation.
NH 3 it was by the addition of

:
1.68.
The
dissociation
either of the
was components of
Ammonium hydrogen sulphide dissociates

following equation
according to the
NH HS ^ NH + H S.
4
(solid)
Applying the mass law and using pressures, we have
Kpi = p 2
But
is
p3
since
NH HS
4
is solid,
the concentration of
its
NH HS
4
practically constant,
and
vapor pressure
is
so small

that
it
63
can be
left
any
since
appreciable error.
out of consideration without introducing We then have 2 = p 2 p s and
P=
and
NH
we have
ps and the number of dissociated products, p 2 S, are equal, p2 = p 3 Substituting p 2 for p 3 = 2 p2 or p 2 = -J P. Introducing these values in
2
.
the original equation
we have
or
(^
P)
2
.
|P*.
Isambert presents the following experimental data in confirmation of the dissociation constant
:
CHAPTER
VII
THE PERIODIC SYSTEM

DALTON presented a number
"
of
tables illustrating the
relative weight of the ultimate particles of gaseous and other bodies," but it was not until 1803 that he published
his first table of
atomic weights, and this was not printed
This table was on the basis of hydrogen equal until 1805. to one. The other table of atomic weights that was used
lius,
during the early part of the last century was that of Berzewhich was on the basis of oxygen equal to 100. With
these relative weights of the elements available, numerous efforts were made to find relations existing between the ele-
ments themselves as well as between their atomic weights and the various properties of the elements.
Prout's Hypothesis.
press
Among
the
first
attempts to ex-
some relationship was that of W. Prout, in 1815, who aimed to show that the atomic weights of the elements were
exact multiples of that of hydrogen, that is, that the elements were aggregates of the fundamental element hydrogen.
the atomic weight of hydrogen be taken as unity, which was done in the atomic weight table of Dalton, the
So,
if
atomic weights of the other elements should be expressed by whole numbers. This hypothesis of Prout had many supporters,
the idea, but
among whom was Thomas Thomson, who accepted among those who opposed it was Berzelius, who
renounced it. In the efforts to substantiate their respective positions a vigorous campaign was inaugurated, which re64
THE PERIODIC SYSTEM

suited in the early establishment of accurate values for the
atomic weights. It was found that the value given by Berzelius for carbon was wrong, and Dumas and his pupil Stas redetermined it and found the value for carbon to be exactly 12. This fact aided in making Dumas a strong advocate of Prout 's hypothesis and also led to the extensive accurate atomic weight determinations of Stas. It was found that about 24 out of the 70 elements had atomic weights that did not vary from a whole number by more than one unit in the first decimal place. (Of the elements listed in the Periodic Table, page 72, about half have values within one tenth of
an
integer.)
V are given the comparative values of the atomic weights that Prout used, and the values for 191 5, one hundred years later.
In Table
TABLE
(After Harkins)
66
PHYSICAL CHEMISTRY
gave values, such as that of chlorine (35.5), which were hard to reconcile, and Marignac, who favored Prout's hypothesis, suggested that a unit one half that of hydrogen be selected.
Then others suggested further subdivisions to account for the other irregularities, with the result that this brought Prout's hypothesis into disfavor for a time at least. In
1901 Strut t concluded from the theory of probabilities that the instances of the atomic weight approximating to or
being a whole number were more numerous than chance would allow and hence were not accidental, but indicated
fact of nature. Prout's assumption, that elements are simply condensations of hydrogen, contains " the fundamental idea of the primal element or mother " substance of which all the elements are composed and
all
some fundamental
" " " earth," fire," variously termed protyle," hydrogen, and now the modern scientists embody this idea in the electron theory. That this idea is one of the live
has been
questions, as it was one hundred years ago, is evidenced by the extensive investigations at present along this line. 1 Doebereiner's Triads. Doebereiner (1817) arranged similar elements in chemically groups of three in the order
of their of the middle one
symbol weights and showed that the symbol weight was the mean of the other two. There is
a constant difference in the symbol weights of succeeding members of the triads similar to the difference between homologous series in organic chemistry. It was not until 1851, when Dumas again took Up this idea of triads, that any interest was manifested but subsequent to this time many chemists began to investigate these relations between the 1 A large number of articles have recently been added to the already
;
extensive literature.
Among
these recent contributions reference will
be given to a few, such as that of Sir William Ramsay, Proc. Roy. Soc., A 92, 451 (1916) Parson, Smithsonian Publication, 2371 (1915) R. A. Millikan's recent book, The Electron (1917); G. N. Lewis, Jour. Am. Chem. Soc., 35, 1448 (1914), 38, 762 (1916) and Harkins, Ibid., 39,
;
; ;
856 (1917)-
THE PERIODIC SYSTEM

properties of the elements
67
and the
relation of their
symbol
weights.
Table VI, in which are given some of the more important triads, emphasizes the constant differences between the symbol weights.
TABLE VI
ELEMENTS
68
PHYSICAL CHEMISTRY
THE PERIODIC SYSTEM
69
Gladstone (1853) arranged the elements in the order of increasing symbol weights, but the values were so inaccurate that no relations were really apparent. Cannizzaro's more accurate values enabled Chancourtois a few years later (1862) to point out important and remarkable relations between the physical and chemical properties and the symHe arranged the elements in a spiral around a bol weights. which he divided into 16 vertical sections. The cylinder, elements in any vertical section were found to have analogous chemical and physical properties. This arrangement is
known
as the Telluric Screw.
of Octaves. Newlands (1864-66) arthe in the elements increasing order of their symbol ranged and announced his Law of Octaves as follows " If weights
:
Newlands' Law
the elements are arranged in the order of their equivalents with a few slight transpositions, it will be observed that ele-
ments belonging to the same group usually appear on the same horizontal line members of the analogous elements generally differ either by seven or some multiple of seven. In other words, members of the same group stand to each other in the same relation as the extremities of one or more
;
octaves in music."
Mendele'eff (1869) and Lother Meyer and (1869) independently practically simultaneously formulated periodic systems which were very similar to that put
forth
The Periodic Law.
by Newlands, but they were not familiar with it. Their generalization, commonly known as the Periodic Law, is expressed by the statement that the properties of the elements are periodic functions of The Atomic Volume Curve.
their
symbol weights.
tion to the physical properties weights as periodic functions of the specific gravities of the elements. He pointed out that the periodicity is more
closely manifest in the so-called atomic volumes, which he defined as equal to the symbol weight divided by the specific
Meyer paid special attenand expressed the symbol
70
PHYSICAL CHEMISTRY
-symbol weight ~- = atomic volume.
specific gravity
gravity,
i.e.
He
plotted
these values of the atomic volumes against the symbol weights and obtained an atomic volume curve such as is
represented in Fig. 5. The whole curve is
made up of a The summits (i.e. the crests) cupied by the alkali metals
waves.
:
series of periods
or
of the
waves are oc-
Cs =
135,
Rb =
85,
39,
Na =
23,
and Li =
16
Differences 47.5
46.5
16
We
have two
short periods,
other between
one between The remainder of the curve

is
one between Li and Na and the Na and K. Then follow two long periods, and Rb and the other between Rb and Cs.
is partly of a different form and evidently incomplete, and there is no reason to suspect
another alkali of higher symbol weight than Cs. By a consideration of the troughs of the curve, differences between the long and short periods may be indicated. The
elements of
minimum atomic volume
are
Pt
191,
Rh =
102,
Co =
43
59,
Al
27,
B =
16
Differences 89
32
These differences between the symbol weights of the elements at the trough of the curves are about 16 and some
multiple of 16, and the same is true for the metals that occupy the crests or peaks of the curve. The elements with
the smallest atomic volume do not form a group, as do those with the highest atomic volumes, but belong to two widely
which do not show any chemical analogy. Other elements fall into (i) two short periods, beginning with Li and with Na (2) two complete long series, beginning and with Rb (3) a third long series, beginning with with
different groups,
;
Cs followed regularly by Ba, La, and Cr and interrupted by

regularly
the intrusion of closely related rare elements, followed again by metals from Ta to Bi, and lastly by a small
THE PERIODIC SYSTEM
71
and
We thus have five portion of a fourth long series. six minimum sections of the curve.
maximum
The descending portion of the curve, representing the increase in symbol weight and decrease in atomic volume, is The composed of the so-called base-f.orm.mg elements.
ascending portions are occupied by the acid-forming elements, while the minima portions represent the elements Al, Mn, Ru, Pd, etc., which are not decidedly acid-forming or base-
forming.
The position of elements on the curve is closely connected with the physical as well as the chemical properties. Elements chemically similar occupy corresponding positions on
we
At the maximum positions similar portions of the curve. find the light elements at the minimum positions the
;
The Periodic Table presented by Mendelêff illustrates the periodicity of chemical properties much better than the curve that we have just been considering. The following modern Periodic Table given in Table VII
is
heavy elements. The Periodic Table.
same as the one presented by Mendele'eff, the that except symbol weights are more accurately known and the new group of the rare elements in Group III and
practically the
Group
is
added.
DISCUSSION OF THE PERIODIC TABLE

Arrangement.
All the elements are arranged in suc-
cession in the order of their increasing symbol weights. Starting with Li next above H, we find that the one above
fluorine,
Na, has properties very similar to
Li.
If
Na
be
placed in the same vertical column with Li and we then arrange the other elements in the increasing order of their
atomic weights, the elements which fall in the same vertical column resemble each other very closely chemically. The
set of seven elements starting the second set in properties.
with Li agree very closely with The first of the next set, K,
72
PHYSICAL CHEMISTRY
HH
s
*!
SN
Offi
q
(J
-!
C M
s&
.a.3
^
offi
.>
55
zs
ON
1
S
a
1
8
-d
eres
ries
^
I
2
11
THE PERIODIC SYSTEM
73
falls into the group with Li and Na, and the remainder have a striking analogy to the corresponding element of the other sets. After manganese we have one of the weakest points in the Periodic Law, but here also certain regularities are again manifest by the subsequent elements. The elements on the left are eleChemical Properties.
ments present in the strongest
alkalies, while those
on the
extreme right are the elements present in the acids and are the so-called acid-forming elements. Between, we have the gradation between acid properties and basic properties. Valency. Valency with respect to oxygen increases from unity for elements in the first column until it reaches seven, when the valency of one recurs and the other valencies are repeated. Valency with respect to H decreases from left to
right.
or
The first 14 elements (not counting Group H) arranged in the horizontal rows constitute what is designated two short periods, for the eighth of these, Na,
Periods.
;
has chemical properties analogous to the first Li the ninth, Mg, analogous to the second, Be, the tenth, Al, analogous to the third, B, and so on to the seventh, F, which has chemical properties analogous to the i4th element, Cl. In the next elements we have to pass over 14 before we find one with properties similar to the i4th, K, which is the 28th
element, Rb. That is, we have passed over a long period, and find the elements arranged in a long period, which is followed again by another long period of 14 elements. There
two short periods and five long periods. The last long periods are not completely filled out, and there are a number of vacant places. When the Periodic Tables were first preare
many of the elements known at present were unknown, and there were a larger number of vacant places in the table than at present. Notable among these were the spaces now occupied by gallium, scandium, and germanium. Mendeleeff predicted the chemical and physical properties
pared
74
PHYSICAL CHEMISTRY
that the elements occupying these places should have. A short time afterward the above-named elements were discovered, and they were found to have the properties MendeThis fulfillment of prophleeff predicted they should have.
ecy brought the attention of the

deleeff's classification
it.
scientific
world to Menof
and resulted in the rapid adoption
was soon demonstrated that in such a system as this we had not only a means of prediction but also the only way by which the elements could be grouped together as a whole for the purpose of representing conveniently and conThis was of great advantage. cisely their interrelations.
It
in the atmosphere, the Argon Group, fall into a column to the left of the strongly basic elements, Group I, and constitute the Zero Group, because they are inert and are said to have a valency of zero. There are many other physical Physical Properties. properties of the elements and of their compounds which manifest a periodic function of the symbol weights, and among these may be listed a few of the principal ones.
vertical
1
.
The elements
(a)
Malleability. Light malleable metals
occupy the points of

;
maximum
and contiguous portions of descending curves Li, Be, Na, Mg, Al K, Ca Rb, Sr Cs, Ba. (b) The heavy malleable metals are found in the lowest points of the atomic volume curve and adjacent sections of the ascending curves Fe, Co, Ni, Cu, Zn Rb, Pd, Ag, Cd,
;
; ;
In, Sn, Pt,

(c)
Au, Hg,
Tl, Pb.
Less malleable metals are found just before the lowest points on the descending curves Zr, Nb, Ti, V, Cr,
;
Mn
Mo, Ru
(d)
Os, Non-metallic and semi-metallic elements are found in

;
Ta,
W,
Ir.
each section on the ascending branches of the curves preceding the

2.
maximum.
is
Hardness of elements atomic volume.
inversely proportional to their
THE PERIODIC SYSTEM

3.
75
Melting point data are shown diagrammatically in Fig. 5 and illustrate the periodic function of this property with increasing atomic weight. (a) All gaseous elements, and all elements that fuse below a red heat are found on the ascending portions and at the maximum points of the atomic volume curve. (6) All infusible and difficultly fusible elements occur at the points of the minima and descending portions of the
The periodicity corresponds to that shown by atomic volume and malleability. For those elements that are easily fusible the atomic volume is larger than that of the element with next smaller symbol weight. There are,
curve.
however, some considerable variations the melting point decreases with increase in symbol weight only in the following (i) Alkalies, Li, Na, K, Rb, and Cs, (2) Alkaline earths, Mg, Ca, Sr, Ba, and in Cu, Cd, and Hg. The compounds of the elements also exhibit relations in their melting points. This has been worked out by Carnelley. with fusibility. 4. Volatility is intimately associated Easily fusible volatile metals ar.e found on the ascending Elements on ascendportions of the atomic volume curve. ing portions of the curve are gaseous and easily volatile, but many elements of high atomic weight which occupy a similar position, however, require a strong red heat or even a white heat for volatilization. 5. Fizeau has shown that the volatile elements occurring on the ascending curve possess almost without exception a larger coefficient of expansion by heat between o and 100 than the difficultly fusible elements occupying the minimum. Carnelley states that the coefficient of expansion of an ele: :
ment
6.
increases as the melting point decreases.
The refraction of light by the elements and their compounds is also essentially related to the symbol weight.
7.
Conductivity for heat and for electricity of the

their ductility
ele-
ments are dependent upon
and
malleability,
76
PHYSICAL CHEMISTRY
and hence are periodic functions of the atomic weights, the periodicity of which coincides with that of the atomic
volume.
Magnetic and dimagnetic properties of the elements appear to be closely connected with their symbol weights and atomic volumes. Those elements the atomic volumes Obserof which approach the minima are usually magnetic. vations differ so that it is difficult to tell whether there is a periodic relation between the magnetic and dimagnetic However, from maxima to properties and atomic weights. the elements are minima, entirely magnetic, and at minimum
8.
the magnetism exhibits

of the iron group.
its
From
the
This is true greatest intensity. minimum to maximum, follow
dimagnetic elements only. The magnetic susceptibility is a periodic function of the atomic weight, as is illustrated in
Fig.
9.
5-
Electropotential series according to electropositive

in malleability
is
the arrangement of elements
and electronegative character.
These properties exhibit variations similar to those exhibited
and
brittleness.
The electrochemical character of the elements becomes more positive as the symbol weight increases. Cu is replaced by silver. A strongly electronegative element Cl will The electropositive character bedisplace a weaker one I. comes less marked with increase of symbol weight in the groups Cu, Ag, Au Zn, Cd, Hg. In the two short periods the elements become regularly less electropositive and more
;
electronegative as the symbol weight increases, but in the long periods the change is less regular. The elements in the
groups on the left-hand side and those on the right-hand
of the table are electropositive side are electronegative.

:
Some of the other periodic properties are the following The crystalline forms of various compounds of the elements,
heats of chemical combination, ionic mobilities, distribution of the element in the earth, spectra of the elements, refrac-
THE PERIODIC SYSTEM

tive indices, ultra-violet
77
vibration frequencies, solubility,
electrode potentials, etc. Advantages of the Periodic

i
.
Law and
Classification.
only known satisfactory method of classifying the elements so as to exhibit the relationship of the physical and chemical properties of the elements and of their
It affords the
compounds. 2 The symbol weights of the elements may be determined by means of the periodic system when their equivalent weights are known. Many of the symbol weights used when
.
Mendeleeff presented his periodic table did not allow placing the elements in the position which corresponds to their properties, so he assumed that there had been an error made
in the determination of the equivalent weight or that the For example, the symincorrect multiple had been selected.
bol weight for uranium was thought to be 60 changed to 120, and finally to 240 (238.5).
3.
this
was
The
prediction of
unknown
elements, a statement of
As an their properties and general chemical characteristics. illustration, in the following table, properties of the prophesied elements are compared with those of the elements
subsequently discovered.
PROPHESIED ELEMENTS
ELEMENTS DISCOVERED
Ek-aluminium
Symbol weight, 68
Specific gravity, 6.0
Gallium Discovered by Lecoq de Boisbaudran in 1875
Symbol weight, 69.5

Eka-boron
Scandium
Discovered by Nilson in 1879
3.5
3
Symbol weight, 44
Eb 2 O sp. gr. Sulphate, Eb 2 (SO 4 )

Oxide,
,
Symbol weight, 43.8

isomor-
Double
sulphate not phous with alum
Sc2 O 3 sp. gr. 3.86 Sc2 (SO 4 ) 3 Sc 2 (SO 4 ) 3 3 2 SO 4

,
- slender
prisms
PHYSICAL CHEMISTRY
PROPHESIED ELEMENTS
ELEMENTS DISCOVERED
Eka-silicon
Germanium
Discovered by Winkler in 1887
Symbol weight, 72
Symbol weight, 72
Oxide,
EsO 2
sp. gr. 4.7
Chloride, EsCLj,, liquid, boiling
point slightly under 100, sp.

gr. 1.9
Oxide, GeO2, sp. gr. 4.7 Chloride, GeCU, liquid, boiling point 86, sp. gr. 1.887
Ethide,
Es(C 2 H6 ) 4
liquid, boil-
Ethide,
point
less
Ge(C 2 H 6 ) 4
1
liquid, boiling
gr.
ing point 160, sp. gr. 0.96

Fluoride,
60,
sp.
slightly
than that of water.
EsF 4 not gaseous

,
Fluoride,
solid
GeF 4
H O,
2
white
mass
Imperfections of the Periodic Law and Classification. seen that by this system not only all of the known elements can be classified, but also the unknown ones as
We have
well.
It is not surprising then that from such a universal proposition there should be some variations and irregularities, and so we do find in this classification a few weak points.
first presented there was a arrangement in the case of the following elements, but according to the present accepted values for their symbol weights that has disappeared, as is shown in Table VIII.
When
the Periodic Table was

in the
marked discrepancy
TABLE VIII
ELEMENT
THE PERIODIC SYSTEM
79
sphere of activity, and hence because of insufficient and inaccurate data concerning certain elements erroneous conclusions hare been drawn. However, there still remain a
few remarkable exceptions to the Periodic Law. lowing are some of the most pronounced ones
:
The
fol-
1. In Group I and in Group VII, the elements have a valency of one, and since the valency of hydrogen is unity, it could be placed in either. Owing to the fact that it has a low boiling-point and that its formula weight is represented
it is in2 (as many other gaseous elements) as diatomic, cluded in Group VII by many chemists. Solid hydrogen does not resemble the alkali metals in physical properties, and it
,
is
typically non-metallic. Chemically, however, hydrogen acts very similarly to the alkalies, forming stable compounds with non-metallic elements, such as the halogens. Owing
to this
2.
it is placed in Group I. The symbol weight of argon, 39.88, is larger than that of potassium, 39.15, and so these two elements should change places. With argon between potassium and calcium we should have a decided discontinuity in the properties, and
furthermore, this would bring potassium into Group 0, and the properties of potassium are decidedly unlike those of the other members of this group.
The same holds for tellurium and iodine they should 3 be interchanged according to their symbol weights, but according to their chemical properties iodine must be placed
.
in
iron, cobalt, and nickel, but from the symbol weights nickel and cobalt should exchange Since cobalt and iron form two series of salts, and places.
4.
Group VII. In Group VIII we have
in the properties is represented iron and nickel.

5.
nickel forms only the nickelous salts, the gradual variation by placing cobalt between
The
three groups of triads in
in that the triads are arranged in horizontal lines
Group VIII are peculiar and con-
8o
nect the
PHYSICAL CHEMISTRY
members of the three long series. They destroy somewhat the symmetry of the whole system. 6. Between lanthanum, 139, and tantalum, 181, there are a large number of blank spaces, but it is not possible to fit the
elements into these places, as the symmetry Since these elements are trivaof the system is destroyed. are grouped together in Group III. lent, they
fifteen rare earth
Graphic Representations of the Periodic Table. Many graphic representations of the periodic arrangement of the
FIG. 6.
Electro-Positive Elements, above plane of paper, black letters on white ground. Electro-Negative Elements, below plane of paper, white letters on black ground. Intermediate Elements, in plane of paper, black letters on sectioned ground.
elements have been devised, and these
may
be
classified as
plane diagrams and as space forms. They are designed to bring out more distinctly the relation of the properties of the elements and the atomic weights, but while some of them well express the relations to certain properties, others do
Many not, but represent another group of properties better. of the later designs of the space forms are valuable aids in
the study of the periodic functions of the atomic weights.
THE PERIODIC SYSTEM
81
Only one of the best of these will be presented here in Fig. 6, which is the space form according to Soddy, wherein the figure
8 design
1
is
employed.
For other graphic designs the following references may be consulted, where full description of them may be found (i) Crooks, Chem. News, 78, 25 (1898), employs a figure 8 form (2) Emerson, Am. Chem. Jour., 45, 1 60 (1911), places the elements on a helix; (3) Harkins and Hall, Jour. Am. Chem. Soc., 38, 169 (1916), give illustrations of a number of models, many of which are their own designs.
: ;
CHAPTER
VIII
THE KINETIC THEORY OF GASES

IN our preceding considerations we found it desirable to adopt Avogadro's Theory of the structure of a gas, wherein it is assumed that a gas is made up of molecules in motion, which in turn are aggregates of one or more atoms which may be alike or of different kinds. Bernoulli published in 1738 the fundamental notions of the Kinetic Theory of Gases, in which he pointed out that the pressure of a gas is due to the impact of the molecules on the walls of the containing vessel. The mathematical theory, however, was developed much later by Clausius, and it is due largely to
his efforts
and those of Maxwell that the theory as now accepted has been promulgated and developed. The fundamental assumptions upon which the Kinetic Theory is based may be stated as follows
:
1.
Gases are made up of molecules of very small dimen-
sions.
2.
The space that the molecules occupy

of the gas itself.
is
is
small
when
compared to the volume

3.
The
distance of the molecules apart
very large as
compared to their size, i.e. they are so far apart that they have no marked influence on one another. 4. The molecules are in rapid motion in all directions, and are assumed to be perfectly elastic. Deduction of The Gas Law from the Kinetic Theory of The total pressure exerted by a gas on the walls Gases. of the containing vessel is due to the impacts of the gas
82

molecules, which are
walls.
83
moving
in all directions, against the
Let be the mass of a given gas inclosed in a box, Fig. 7, whose parallel sides are all rectangles, the inside dimensions If m repof which are b, c, and d. resents the mass of one molecule,
M=
m
n, the
number of molecules.
We
F IG
assume that these n molecules of the gas are moving about in all direcLet us assume that there is tions.
is
but a single molecule of the gas in the box, and that it moving with any velocity. The force that this molecule The exerts on the different sides is found as follows velocity of the molecule, u, may be resolved into three components perpendicular to the faces of the box. Let x
:
represent the
component perpendicular to the face
be
y represent the component perpendicular to the face cd\
component perpendicular to the face exerted by the face, be, upon the molecule may be found by the formula F = ma, where F represents the force, m the mass of the molecule, and a
z represent the
bd.
and
Then the
force
represents the acceleration of the molecule in the direction

of the force.
But acceleration a =
t
where
v2 reprevi,
sents the velocity after impact with the face,
and
the
.
velocity before impact.
= m ^~ v ^ Substituting, we have F
The molecule
strikes the face be with the velocity x normal to the face, then rebounds from the face with a velocity x. That is, vi = x and vz = of x. The effect of the force
impact upon one face is distributed over the period of time that it takes the molecule to travel the distance 2d, when
another similar impact occurs.
This time,
/,
is
equal to
84
PHYSICAL CHEMISTRY
vi, v%,
Substituting these values, for

tion, gives
and
2
.
/,
in the
above equa-
= m\
*
xx]
2
-, d-
or
mx
d
JNow, since the torce
TVT
upon the face by the molecule is equal to that exerted by the molecule upon the face, but in opposite direction, we may write the force exerted by one molecule upon
exerted
the face
be,
as
F = ^-. The
Ct
force exerted
by the molecule
n
2 Wt^C
upon the two parallel faces,
be,
then,
is
r~-
In the same
way
the force exerted by the molecule upon the two parallel

2 is
faces cd,
m^
,
and
similarly
upon the two
faces bd
2
is
mz
c
is
Let us assume that this force exerted by the one molecule the mean force of all of the molecules then if there are n
;
molecules the total force or pressure upon the two parallel

faces be will be
2
nmx
d
2
Similarly on the two parallel faces
cd the pressure will be

I-,-, M1 bd, it will
If
i
nm/y
,
and on the two
parallel faces
be
nmz
c
designate the force on unit area by p, which is the intensity of pressure, then the pressure p on each face will be the same. The area of the two faces be is 2 be, and the x 2nm% hence the total force is pressure p will be
we
oca
Similarly, for the pressures on the other faces

2
we have
cdb
2
nmx'
bdc
'

Adding these three equations, we have
2
85
bed
Simplifying and writing the mean square velocity for the sum of the squares of the three components, u2 = #2 + y2 + z 2
,
we have $p =
bed
but the product,

is
bed,
of the three
dimensions of the box

for bed, the equation
the volume, hence, substituting
becomes
Deduction of Boyle's Law. We may define heat as the or due to the position velocity of the molecules of a energy substance. JHeat, due to the velocity of the molecules, we
term Thermal Kinetic Energy. A measure of this Thermal Kinetic Energy is Temperature, then T = f(mu z ) For any constant temperature, u is a constant, and the mass, nm, of the gas, is also constant therefore, the righthand member of the equation, J nmu 2 is a constant. The equation may then be written pV = a constant. This is Boyle's Law, which we have deduced from the Kinetic
.
Theory
of Gases.
of Charles' or
is
Deduction
Gay Lussac's Law.
If
we
as-
sume that T
a linear function of
mu
2
,
i.e.
T =
3
k(mu?),
t
then substituting in
pV =
mnu we
2
get
pV
- n
but
T 3/2
is
a constant, hence
pV = T X
a constant or
^r= 1
constant.
Thus, from the Kinetic Theory of Gases we have derived The Gas Law. From this equation we also have the conclusion that at constant pressure the volume of a constant mass of gas is directly proportional to the absolute temperature or, if the volume is constant, the pressure is
;
directly proportional to the absolute temperature,
i.e.
the
86
coefficient of
PHYSICAL CHEMISTRY
expansion of a gas
is
a constant, which
is
Charles'
Law.
Deduction of Avogadro's Hypothesis. Let us now apply the equation just obtained in the deduction of Boyle's Law to two different gases which are under the same conditions
of temperature
and pressure and which occupy the same
volume.
spectively
This equation for the two gases becomes re-
pV =
=
J miHiUj
and
pV =
m^nû^
\ m\n\u? J m^n^-. (i) has been shown experimentally that when two gases are under the same conditions of temperature and pressure they
It
Hence
are in physical equilibrium
and may be mixed without change
in temperature. conclude from this that the kinetic energy of the two molecular species remains unchanged, and
further, that at the same temperature the kinetic energy of a molecule of one gas must be equal to the kinetic energy
We
of a molecule of
any other
2
,
gas.
Since the kinetic energy of
a molecule
is
^ mu
then
, v
Dividing equation
or
(i)
by equation
(2)
we have f n\
f HZ
the equal volumes of all gases at the same temand pressure contain the same number of moleperature
That
is,
cules.
This is Avogadro's Hypothesis. Molecular Velocity. Solving equation
pV =
=
w
J
.
nmu2
for
u,
we have
u*
nm
or u
=V
or
nm
(3 )
of
This equation then gives us the velocity of the molecules any gas, providing we know its volume and pressure and
the quantity of gas present.
87
o Centigrade
Let us calculate the velocity of the hydrogen molecule at when under one atmosphere pressure.
mX
= mass
of gas.
One gram-molecular weight of a gas at o and i atmosphere It will require 2.016 grams of pressure occupies 22.4 liters. hydrogen to occupy this volume under the conditions
specified.
Hence, substituting these values in the above
equation,
we have
u
^
/3
1033
980.6 2.OIO
22400
Solving for u we obtain u = 183,700 cm. per second, or 1.837 kilometers per second, as the velocity of the hydrogen molecule under the conditions of our problem. The molecules of a gas moving in Diffusion of Gases.
an inclosed space bombard the walls. Now, if there is an opening in one side, the molecule will meet with no resistance and will continue in its path on through the opening and thus pass out. It will pass through with the original speed
it
possessed inside the vessel, and this speed of diffusion originated directly from the speed of the molecular motion, and we conclude that the mean speed of the issuing mole-
must therefore be proportional to the mean speed of the molecules within the vessel. Since this speed is proporcules
on the gas, the rate of outflow will be dependent somewhat on the resistance the gas meets in If the gas flows through a very small aperflowing out. ture in a thin membrane into a vacuum, then the resistance is reduced practically to the minimum. If we have two gases under the same conditions of prestional to the pressure
sure
and temperature, from the equation u = \/

P
ui'.uzi
:
we
have
Vp
V/^.
That
is,
the molecular velocities are
inversely proportional to the square roots of the densities of

the gases.
88
PHYSICAL CHEMISTRY
This relationship may be deduced not only from the Kinetic Theory of Gases, but it has also been developed from flow of liquids through orifices, which fact is presented as an
argument in favor
of the kinetic theory.
Bernoulli
pre-
sented a theory of the process of effusion by an extension to gases of Torricelli's Law, which states that the velocity with
which a liquid issues through an
orifice is proportional to or the head of the liquid. the square root of the pressure,
This law
is
expressed as follows
which gives us
the same relation as
u =
%P
deduced from the Kinetic
Theory, which states that the pressure varies as the square
through membranes and porous media as well as through cracks has been the subject of
of the molecular velocity. The diffusion of gases
Graham (1833) investigation since the time of Priestley. recognized the similarity of diffusion and the passage of a
gas as a whole through fine openings, which process he termed effusion in distinction from the passage of a gas
through capillary tubes, which he designated transpiration. The latter process did not conform to the law of diffusion, while the process of effusion did conform to the diffusion law. Graham's Effusion Law is stated as follows The times required for equal volumes of different gases to flow through
:
an aperture
densities.
is
This law
proportional to the square roots of their is true for the flow of all liquids through
as a
a small
orifice
and was employed by Bunsen
method
It has for the determination of the specific gravity of gases. also been extended to the determination of molecular weights.
If ui u* Vp2 Vpi, and we assume the same volume of the two gases under the same conditions of temperature and PI P2, since the molecular weights pressure, then m\ m^
:
:
If we ratios as the densities of the gases. refer the densities to that of some standard, such as air,
are in the
same
89
we have the specific gravities Si and 52. Substituting, we Vs2 Vsi. Since the times of efflux of equal have ui Uz volumes are inversely proportionaljto the velocity of effuThat is, the times reVsi Vs2 sion, then we have t\ t%
: : : : : : : :
.
quired for the efusion of equal volumes of different gases under the same conditions of temperature and pressure are directly
proportional
the gases.
to the
specific
The molecular weights are proportional substituting, we have gravities

;
square roots of the specific gravities of to the
Table
IX
recalculated
contains some of Graham's data arranged by O. E. Meyer.
and
TABLE IX
GAS
CHAPTER IX
SPECIFIC
HEAT OF GASES
THE amount of heat required to raise the temperature of a substance one degree is known as the heat capacity of the body and will be designated by q. If the amount of heat absorbed by a body when its temperature is raised from ti to AJ is H units of heat, then the mean heat capacity (qM )
would be qM
=-~
1?
specific heat capacity, C, usually called the specific of a substance is the amount of heat required to raise heat, one gram of the substance one degree. The unit of heat,
The
the calorie,
raise
is defined as the amount of heat required to one gram of water one degree Centigrade. The amount of heat required to raise the temperature of one gram of water one degree is different at different temperatures. Therefore it is necessary to define very accurately the tem-
perature used.
Table illustrates the variation of the specific heat of water with the temperature as given by Callendar at 20 C.
as the unit.
The
unit employed
is
the calorie at 20
C., while the
calorie at o
would be 1.0094 calories at 20, and the mean calorie between o-ioo is equal to 1.0016 calories at 20 and the value at 15 is equal to i.oon calories at 20. The atomic heatoi an element is the specific heat multiplied
by the atomic weight, that
times atomic weight = the atomic heat. Similarly, the molecular heat is the specific heat of the substance multiplied by the molecular weight.
is,
90
SPECIFIC
HEAT OF GASES HEAT OF WATER
TABLE
TEMPERATURE
SPECIFIC
PHYSICAL CHEMISTRY
But 0.08204 liter atmosphere. R constant of the Gas Law the atmosphere per degree Therefore the difference between the molecular Equation. heat at constant pressure, mCp and at constant volume,
equal
to
0.08204
liter
is
mC is R, that is, mCp = mC + R. R may be calculated in calories as

v, v
follows
calorie
42 ,690 gram-centimeters
is
expressed in gram-centimeters
1033.6X22400 = 84?8o and 84780

273
1.986
calories
or
42690
2 calories.
v and heats, p of in are Table XI. gases given
,
approximately
The molecular
mC
mC
some
of the
more
common
TABLE XI
The
values for
mCp
were determined experimentally and
mC
by
difference.
GAS
SPECIFIC
HEAT OF GASES
93
overcoming the mutual attraction of the molecules. In the case of ideally perfect gases the molecules are out of the sphere of action of one another, and consequently the effect
of this last consideration is very small
tically negligible.
If
and therefore prac-
the law
pV=RT
holds for the gas, the specific heat of
the gas must be independent of the pressure and also of the
volume. The whole work done during a change of volume If the volume changes from Vi to v2 under will be external. constant pressure p, the external work will be p(v2 Vi). Now, as we have seen, the specific heat at constant pressure exceeds that at constant volume by the thermal equivalent
of the
work required to overcome the resistance offered to the expansion of the gas. = R, substituting for R its value, In equation v p
mC
mC
2
,
we have
273
mCp
mC =
v
273
From the consideration of the Kinetic Theory of Gases we found that pV = J mnu 2 and for the kinetic energy
,
K = % (mn)u
2
.
Equating these, we have

or
pV = %K,
which enables us to express the molecular energy in a form which can be readily determined. The pressure and kinetic energy of a gas are in an invariable ratio which is independent of the temperature. Substituting this value for in the equation above, we have
pV
mCp - mC =
v
273X3
All of the energy, E, possessed by the substance is the heat required to warm it from absolute zero to the given
94
PHYSICAL CHEMISTRY
temperature at constant volume. This is increased by the heat required to warm the gas from o to i, that is, by But this heat at constant volume is the specific 2^-5- of E.
heat at constant volume, that
dividing the above equation
is,
mC =
9
E.
Then
273
by
this,
we have
mCp
mC
In case the total energy is the kinetic energy, then and the equation becomes
= E
which
is
the
maximum
value of the ratio of the specific heat
at constant pressure to the specific heat at constant volume. This value has been obtained experimentally in the case
of
monatomic gases, mercury vapor, argon, and helium. In the case of diatomic or polyatomic gases, an appreciable portion of the heat applied to raise the temperature is utilized
mutual attraction
of the molecules or in
It is possible to raise the
in overcoming the
intermolecular work.
ture of
of
tempera-
some substances to such an extent that this portion the energy increases the speed of the atoms within the
molecule whereby they are separated from their combination with the others, and the freed atoms thus become like independent molecules, the atomic energy going to increase the
total molecular energy. This would lead us to the conclusion that the kinetic energy of the atoms would be decreased
and the molecular energy increased, hence K < E. It is apparent that in the case where the amplitude of vibration of the atoms of the molecules has not been increased sufficiently to cause them to pass beyond the influence of the other atoms within the molecule, just before dissociation takes place, that we will have the maximum of heat energy
SPECIFIC
HEAT OF GASES
95
being utilized in the atomic energy. The more atoms there are in the molecule, the greater will be the amount used in this way and consequently the greater the decrease in the
kinetic energy
and the
less
the value of the ratio
molecular heat at constant pressure mCP molecular heat at constant volume mC v
Hence it follows that by determining y for a given gas or vapor, it would be possible to determine the complexity of the molecules.
may
There are a number of methods by which the value of y be obtained, and it is not always necessary actually to determine both of the specific heats. Laplace showed that the velocity of sound in a gas is
expressed as follows
:
=\
1
P of
where
v is the velocity,
is
the ratio of the two specific heats, p the pressure, and p the
density.
The method
is
Kundt and Warburg, which
is
a means of finding experimentally the usually employed, value of v. The apparatus consists of a " Kundt 's dust tube," and as employed by Ramsay in the determination of the specific heat of helium consisted of a long tube of narrow
bore, closed at one end, through which is sealed a glass rod extending for an equal distance inside and outside of the
tube.
Some lycopodium powder is distributed along the tube and dry air is introduced. The glass rod is set in vibration by rubbing it with a cloth wet with alcohol. By movthe on the rubber other which closes the ing clamp tubing end of the tube, the length can be adjusted till it resounds to the proper note. The interference of the waves deposits
the lycopodium in piles at the nodes. The distance between these nodes represents one half the wave length and
can be readily measured. Air is then removed by evacuation, and the tube is refilled with the gas under investigation
and the wave length determined.
96
PHYSICAL CHEMISTRY
Let X represent the wave length of a sound of frequency n
in
any
specified gas
let
p = the pressure and

:
p its density,
then from Laplace's formula we have for any two gases under the same pressure and temperature
and
pi
%
pz
vz
pi yz
Since
weights,
the
densities
we may
are proportional write the equation
to the molecular
yz
mi
which becomes
Vz
yz
mi
;
Taking air as the standard gas, y\ = 1.408 the value of y any other gas is then obtained by comparing the wave lengths of the same sound in the gas and in air, providing The the molecular weight or density of the gas is known.
for
velocity is equal to the wave length times the number of If x is the distance vibrations (pitch) in a unit of time.
between the nodes or ridges of dust, then X = 2 x and the Then we would have vi = 2 nx\, and vz velocity is 2 nx. = 2 nxzj which, substituted in the above equation, gives
Substituting the value for air, y\ the value for y2 can be obtained
=
if
1.408
and m\ =
28.9,
the other values are
known
xz and known. being

;
x\
being obtained experimentally and mz
CHAPTER X
VAN DER WAALS' EQUATION
saw that the Laws of Boyle, Gay Lussac, and Avoare gadro only strictly applicable to perfect gases. Under low pressure the deviation is small, but it is greater when considered that the kigases are highly compressed.
WE
We
netic energy of rectilinear motion of the molecules is directly proportional to the absolute temperature under all conditions,
and
so certain modifications in the Kinetic
Theory
were suggested by van der Waals to explain the observed

variations.
ment
In the Kinetic Theory the pressure due to the bombardof the walls of the vessel by the molecules of the gas is
calculated on the assumption (i) that the actual volume occupied by the molecules is inappreciable compared with
the total volume of the gas, and (2) that the molecules exert no appreciable attraction for each other. It is found that when the gas is greatly rarefied, this assumption is admissible, but when the molecules are brought close together by compression of the gas, it is not hence the Gas Law Equation must be modified to take these facts into consideration. Many attempts have been made to correct the Gas Law Equation for this purpose, the most successful being that of van der Waals (1879). According to the Kinetic Theory the total volume occupied by the molecules is small in comparison to the total volume of the gas. Van der Waals corrected for the volume actually
;
occupied by the molecules thus

97
98
Let b
v
PHYSICAL CHEMISTRY
= volume occupied by molecules of gas = volume of the gas

6)
then
(v
=
is
cules are free to
pressure this
the actual or free space in which the molemove, and when the gas is subjected to the part which decreases in volume.
In 1854 Joule and
Thomson showed experimentally
that
strongly compressed gases are cooled by expansion. Then, on expansion, work is done against the molecular force, and
that the molecules have attracted one another. Hence a certain cohesion is ascribed to the gases, which is more noticeable the greater their density. Under high pressure gases contract more than they should according to Boyle's Law, and this is explained on the supposition that in compression the molecules are drawn more closely together by their attractive force, and this tends to aid the external pressure in making the volume smaller. Therefore this
factor should be added to the external pressure. This force must be proportional to the number of molecules attract-
we conclude
ing each other, that
is, to the density of the gas, since the of a given gas is proportional to the number of density
molecules per unit volume. Van der Waals concluded that the attraction is proportional to the square of the density
or inversely to the square of the volume,
and gave
as the
-^-
expression for this correction. Substituting these two values in the
Gas Law Equation we
have
+ -rk\(V-b)-RT
which is known as van der Waals' Equation of Condition. This equation gives the behavior of the so-called permanent gases, of the easily condensed gases, and it is also claimed that it can be applied to the liquid state as well, although Tait has pointed out that it does not hold for any real liquid.

It is
99
apparent that when the volume
is
large, the correct-
ing factors,
and
b,
have no appreciable influence and the
= RT. When the pressure is very equation is really pV to be negligible, and its influence factor b ceases the great,
increases
more rapidly than -^
The product p V reaches a
minimum, and afterwards
much
increases, and eventually becomes than at low greater pressures. For ethylene, which is readily liquefiable, Baynes calculated the values of p V from the following formula
:
V-
0.0024)
0.0037 (272.5
pV = 1000 for p = i atmosphere at 20 C. The observed values in Table XII are from Amagat's results.
where
TABLE XII
p
100
If
PHYSICAL CHEMISTRY
V remains
constant, then
takes the form

(p
QC = RT
=
where
C and C
is,
are constants and k

is
That
ture
the p
a linear function of the absolute tempera-
when the volume of the mass remains constant. The constants a and b in van der Waals' equation may be calculated from experimental data or from a number of iso;
therms the pressure and temperature at a series of constant volumes may be read off and the values of the constants k C calculated for each volume. and C in the formula p = kT Clausius (1880) claimed that van der Waals' equation did not represent the facts with sufficient exactness and developed an equation himself which allowed for the variation of molecular attraction with change in temperature.
The Clausius
equation,
p =
-RO
a
B(v
r
-\-
contains
B)
four constants, R, c, a, B, which necessitate four experiments on p and V at different temperatures to establish, and it is
claimed to give greater range and better agreement than van der Waals' equation which contains only three constants.
APPLICATION OF VAN DER WAALS' EQUATION
The
of his
following quotation is Andrews' description (1863) experiments on the behavior of carbon dioxide
to changes of pressure and of temperature carbonic acid by pressure alone and
:
when subjected
"
On partially liquefying
gradually raising at the same time the temperature to 88 F.
VAN DER WAALS;
EQ(JATIQ$)
'-'',
;^
\\
SOI
the surface of demarcation between the liquid and gas became fainter, lost its curvature, and at last disappeared. The space was then occupied by a homogeneous fluid, which exhibited, when the pressure was suddenly diminished or
moving or
the temperature slightly lowered, a peculiar appearance of At flickering striae throughout its entire mass.
temperatures above 88 F. no apparent liquefaction of carbonic acid, or separation into two distinct forms of matter,
could be effected even
pheres was applied.
when a pressure of 300 or 400 atmosNitrous oxide gave analogous results. "
Andrews plotted the results of his experiments, and the curves in Fig. 8 represent them. The p-V curve of constant temperature, isothermal curve,
obey Boyle's Law, should be a rectangular hyperbola, and the curve for CC>2 at
for gases that
48.1
approximates this closely.
At
35.5
the curve has a decided flexure,
while at 32.5 this is more marked, and at 31.1 still more marked, when
flexure. This curve runs for a short distance parallel to the F-axis and represents the
critical
we have a double
temperature of
CO
2.
The
in-
volume diminishes regularly with
crease in pressure at this temperature until a pressure of 73 atmos-
pheres is reached, when the volume decreases very rapidly, about one
half of it disappearing. required to produce this
FIG. 8.
steady increase in pressure is and by the time 77 atmospheres are reached we have a homogeneous mass which responds to a regular change in volume with inchange,
creased pressure. At 21.5 we have the volume gradually decreasing with increased pressure until about 60 atmospheres
are reached,
when
there
is
a sudden break in the curve which
CHEMISTRY
runs parallel to the V axis, showing a marked decrease in volume without change in temperature. This is similar to
the curve at 13.1, which becomes horizontal at 49 atmospheres pressure, showing a change of about f the volume a perfect gas should occupy at this temperature.
work insisted on the idea vapor into the liquid form on increasing the pressure, and Thomson, in an effort to explain the shape of the isotherms just above the critical temperature, prescribed an hypothesis in confirmation of this idea
Andrews from
his experimental
of the continuous passage of
as illustrated
by
Fig.
8.
represents the isotherm above the critical temperature and pressure, where van der Waals' equation assumes a
vice versa.
FGH
continuous passage from the liquid to the vapor state or The line ABC, which is a broken line, represents the ordinary isotherm of a substance passing from the
The part refers to the liquid to the gaseous state. the vapor pressure is equal to the external liquid state, at
AB
pressure,
and the substance begins

liquid.
is
vapor and
The
while this change
to separate into saturated horizontal portion BC shows that taking place the pressure remains con-
stant and represents the isotherm of the mixture. The portion represents non-saturated vapor, and the isotherm
CD
approximates more nearly that of a perfect gas. James Thomson suggested that A A' and CD are portions of the same continuous curve and are connected by some ideal branch, such as AMBNC, along which the substance might pass continuously from liquid to gaseous condition below the critical temperature, as it does above that temperature, without separation into two distinct states simultaneously existing in contact with each other. Along we have the condition of superheated liquids, and along C N, supersaturated vapors. So the abnormal conditions of both liquid and vapor are represented by Thomson's curve
AM
AMB NC, as conditions of unstable equilibrium.
The vapor

at
103
is supersaturated, it condenses when equilibrium is destroyed, and if the temperature be kept constant, a decrease of pressure to the point n will take place. Similarly
we have a superheated liquid which on disturbing the equilibrium assumes a condition of stable equilibrium with explosive violence and assumes the condition represented by
at
Between
when the substance is partly liquid and partly vapor. N and we have the volume and pressure in-
creasing simultaneously, a condition difficult to realize in a homogeneous mass. It is apparent that the pressure curve cuts the Thomson hypothetical curve at three points, A, B,
and
C, which would correspond to three different values for the volume for the one value of the pressure. As the pres-
sure increases
it is
apparent that the Thomson curve de-
creases in length, the difference between the three values of the volumes becomes less and as we approach the critical
;
point these values likewise approach this value of the critical volume as their simultaneous and limiting value.
i. Methyl Realization of Parts of Curve Experimentally. formate (31.9 B. Pt.) was heated to 80 and the whole of the vapor condensed. Pressure was lowered below 800 mm. without boiling taking place at 80 the vapor pressure is 3500 mm., so that the pressure was reduced to less than one
;
fourth of the vapor pressure
in other words,
it
was more
above its boiling point under 800 mm. and 80 C. Boiling finally took place with explosive violence. 2. Worthington showed that when a sealed tube, nearly full of pure liquid free from air, is gently warmed until the liquid fills the tube completely, a bubble of vapor will not form on cooling until a very large negative pressure is reached.
than 45
The tubes
3.
collapsed in
some
cases.
Aitken showed that temperature of dust-free vapors could be lowered many degrees below the condensing point
before liquefaction takes place. It is therefore proved that part of the continuous isother-
104
PHYSICAL CHEMISTRY
and from C towards (Fig. 8) from A to may to increase in volbe realized experimentally. From ume is attended with rise of pressure, and if it could be brought about, would take place with explosive rapidity.
mal
CALCULATION OF CRITICAL CONSTANTS FROM VAN DER WAALS'. EQUATION
The Gas Law Equation

the volume
b,
pV = RT, when
corrected for
actually occupied
by the molecules and the
us van der mutual attraction of the molecules, -^, gives
Waals' equation
(i)
which,
when rearranged
in
the order of the decreasing
powers of V, gives
p J
Under normal conditions of temperature, when p = i, and T = 273, equation (i) becomes
(i
V=
i,
a) (i
a)
6)
273
(3)
Solving for R,
we have
R _ d +
d -
b)
273
Substituting this value of
R in equation
2
(2),
we have
Q
(
+ a v _a =
p
p
273
stant, with three roots,
a cubic equation with respect to V, if p is conone or all of which may be real. We saw that there is one temperature at which the three values
is
This
of
V for one value of

Temperature.
ical
p become equal and that is at the CritBut at this temperature the pressure is
105
designated the critical pressure and the volume the critical volume. Let us designate these critical values for V, p,
If the three e respectively as follows p n and Te become the critical roots are equal, they volume e and the
and
cubic equation becomes
e)
o,
which, on expanding,
becomes
which
Equating
is
equivalent to our equation (4). 1 the coefficients of equations (4) and (5), where the critical volume, and remembering that the correis
sponding values for then have

3 V.
T and p
are their critical values,
we
(6)
=
=
+ (l+a)
^-
b)
273ft
3^
(7)
From these three equations we can calculate the critical values in terms of a and b, the constants of van der Waals*
equation.
Dividing
(8)
by
(7),
we have
<*
3V.1
3
P.
^=b
Wells states the Theorem of "[Indeterminate Coefficients as follows A Bx Cxz Dx*+ ... is always equal to the series A Bx C'x2 D 'x3 where x has any value which makes both series convergent, the coefficients of like powers of x in the two series will be equal; that is, A = A', B = B', C = C', D = D', etc.
1
:
If
the series
+
.
'
'
From this we have the following rule If two equations represent the same locus and one term of one equation is exactly the same as one
:
term of the other, then the

equal.
coefficients of like
powers of the variable are
106
PHYSICAL CHEMISTRY
Then
V =
e
3 b (critical
volume).
(9)
Substituting this value in (7),
we have
Solving for pe
pe =
(critical pressure).
(10)
Substituting these values of
and pe
in equation (6)
we
have
If we desire to retain the value of the gas constant R in the equation, instead of expressing the initial standard con-
ditions as
P
TO
and defining them
as po
V =
and
(4)
To
273,
we
could have kept this as R, and equation
would take the form
RI] V*+a V -ri =0

P )
P
(12)
and equation
(6)
would become
3 f.
&+
calculated
(9)
(13)
From which T can be

e
of
and p c from equations we have

c
by substituting values and (10) respectively, and
107
RT
27
a a
Conversely,
a, b,
we may
(9),
express the values of the constants
and
/?
in terms of the critical values.
From
equation
Solving for
6,
we have
b
=-7 o
(i5)
From
equation (10),
*---^ 27 6
Solving for
a,
we have
a
2 27 6
(16)
Substituting the value of b from (15),
we have
(, 7 )
'-^t'-sV-'PSolving equation (14) for R,
we have
and substituting the value we have
of a
from
(17)
and
from
(15),
R-
Vfp.
108
PHYSICAL CHEMISTRY
simplifies to
which
THE REDUCED EQUATION OF STATE

If
we
substitute in
critical
values of
van der Waals' equation the values of the pressure, volume, and temperature, we
have
This
tion
may
O
be simplified
;
if
we
divide each side of the equafactor of the left
by
-^-*"
dividing the
e
first
member
by pe and the second by

O
- we have
,
X-
(22)
It is apparent that the values of the pressure, volume, and temperature are expressed as factors of the critical values, hence if we substitute for these fractions
we have
(3
i)
6.
Therefore, expressing V, p, and T respectively in fractions of the critical volume, pressure, and temperature, the equation of condition assumes the same form for all substances, or
two liquids be taken under the conditions and temperature pressure which are the same fractions
if
of
of

their respective critical values, such conditions are as corresponding conditions; the law is called the
109
known
Law
of
Corresponding States, and the equation

tion of State.
is
the Reduced Equa-
This equation
is
independent of the substance and of the
physical state of the substance, as there are no arbitrary constants, provided that molecular association or dissociation does not take place.
Young
investigated this relation-
ship and showed that the value for the reduced pressures is the same for all substances and is 0.08846. The substances at their boiling point are under corresponding states, and the
value of the ratio of the boiling temperature to the critical temperature is about 0.75. If the substance is under cor-
responding pressure and temperature, the volume is also a corresponding volume. This is emphasized by the data
given in Table XIII.
TABLE XIII
REDUCED VALUES
IN
CORRESPONDING STATES
(COMPILED FROM YOUNG'S STOICHIOMETRY)

Ratio of Pressure to Critical Pressure
SUBSTANCE
0.08846
*'.
10
PHYSICAL CHEMISTRY
proportional to their absolute critical temperatures, their
vapor pressures
critical presof a liquid at a given sures, a to the vapor presand under pressure equal temperature as a to their critical and both sure) volumes, vapor, liquid
will
be proportional to their
and
their orthobaric (the
volume
volumes."
CHAPTER XI
THE PHYSICAL PROPERTIES OF LIQUIDS
MOLECULAR VOLUME
KOPP
volume
(1858)
of
showed that
it is
possible to calculate the
one gram-molecule of a liquid organic substance at its boiling point from its composition. Molecular volume equals the specific volume times the
molecular weight
A,
j
;
that
7
is,
Molecular volume
= Molecular
=
p
weight
density
or
mol.
vol.
selected their boiling points as his condition for comparing substances. The question arises, was he justified
Kopp
in selecting this particular condition,
boiling
and if so, then the must temperatures represent corresponding states

If
and consequently corresponding temperatures.
the boil-
ing points are reduced temperatures, his selection of the boiling temperatures has been justified. Guldberg .(1890) and Guye (1890) both showed that the boiling temperature at atmospheric pressure is about two
scale.
thirds of the critical temperature expressed on the absolute have just seen that the work of Young presented
We
in
Table XIII confirms this and that the boiling temperature of liquids is a reduced temperature and that the substances at their boiling points are at corresponding states.
in
112
PHYSICAL CHEMISTRY
the molecular volume of a
Kopp determined
:
liquids at their boiling points clusions

1.
number of and drew the following conthe same difference of
Among homologous compounds,
molecular volume corresponds to the same difference of composition.

2.
Isomeric liquids have the same molecular volume.
replacing two atoms of hydrogen by one atom of oxygen the molecular volume is unchanged. 4. An atom of carbon can replace two atoms of hydrogen without change of volume. The first conclusion stated above is illustrated in Table XIV, where m = molecular weight, v the specific volume,
3.
By
where p
the
density.
The molecular volume
m
TABLE XIV

In his later more accurate investigations
value for
Kopp found
the
CH
in
two homologous
series as
given in Table
XV.
TABLE
XV
*;,
114
PHYSICAL CHEMISTRY
This fact led
the calculated volumes.

ferent values to the
Kopp
to assign dif-
same element, depending upon the influence of the nature of the atom and its linking or archiHence there was a tectural relation to the other atoms. constitutive relation which had to be taken into consideration which demonstrated that this property is not strictly additive.
that for oxygen singly linked, as in the hydroxyl group (OH), the value of the atomic volume is 7.8, while for doubly linked oxygen, in the carbonyl group (CO)
it is 12.2.
Kopp found
On
this basis, the calculated values for forty-five
different
compounds did not vary more than four per

:
cent.
Kopp C O (OH) O (CO)

.
gives the following values for the elements
n.o
7.8 12.2 5-5
Cl
22.8
.
Br
I
..
".
... V.
,
.
27.8
.'".;'
. .
37.5 22.6
Sulphur and nitrogen show variations similar to oxygen; they have different values in some different types of com-
pounds
in
28,
CN,
it
ammonia, N = 2.3, in the cyanogen group, and in the nitro group, NO2 it = 33, which,
,
shows great variations in the value of the nitrogen. Schroeder, as well as Kopp, suggested that the atomic volume of different elements is the same or some multiple of the same number, which unit is called a stere, the value Later Buff (1865) of which was between 6.7 and 7.4. showed that unsaturated elements gave higher values than saturated ones that is, a correction had to be made for the double bond, which was estimated at about fojir units.
;
But
in the case of the paraffins aaid their corresponding

of ring
defines this value of the double bond
The formation
compounds
is practically nil. results in the decrease
in the molecular volume.
XVI
for the
paraffins,
By comparing the values in Table homologous series of paraffins with the cyclowhich differ by 2 H, Willtstatter (1907) showed the
effect of the ring structure.

TABLE XVI
PARAFFIN
115
Il6
PHYSICAL CHEMISTRY.
designated the surface tension, and hence the unit surface tension, y, of a liquid is the force acting at right angles
to a line one centimeter in length along the surface of the The molecules on the surface must have more enliquid.
ergy than those on the interior, and this increase in energy expressed in ergs per square centimeter of surface is numerically equal to the surface tension expressed in dynes per
linear centimeter.
The
to
surface tension
may
which the liquid

Let h
r
will rise in
be determined from the height a capillary tube.
= = =
height in centimeters that the liquid rises, radius of the capillary tube, surface tension, expressed in dynes per centimeter.
of contact of the surface of the liquid with the
The length
inner surface of the tube, multiplied by the tension per centimeter, gives the total force acting, i.e. = 2 wry; but
this is equivalent to supporting
h, and density we have
p,
against the force of gravity.

7rr
2
a column of liquid of height Therefore

2irry
gph
Solving for y
we then have
=
which
is
expressed in absolute units.
The
and
surface tension decreases with the rise in temperature, vanishes at the critical point.
Ramsay and
Shields (1893)
employed the surface tension
of liquids for the determination of molecular weights of pure substances in the liquid state, which was an extension of
the earlier work of Eotvos (1886). In the gas equation pV = RT,
volume energy
of the gas,
and
it
pV may be termed the was shown by Eotvos that
a similar equation expresses the relation, within certain

limits,
117
between the surface energy of the liquid and the temperature, which is
yV* =
in
k(t Q -t)
t
which y
/
yV% =
ular
= surface tension, Q = temperature at which = o, temperature of observation, and V = molecvolume which is equivalent to mv. If mv = volume
one of the faces is (mu)*, and volumes contain the same number of
of a cube, then the area of
since the molecular
an equal number
molecules, the molecular surface (w) or V* would have of molecules distributed on it.
Experimentally the temperature,
was found
to cointo
cide practically with the critical temperature, i.e. it is apparent that r If we define r = tc t, then
te .
is
the
temperature measured downward from the ature. We may then write our equation
critical
temper-
yV* =
and as V* = surface
(s)
kr
over which a definite number of
molecules are distributed, substituting

y
5
we have
kr.
Ramsay and Shields, from carefully determined surface tension measurements over the whole range of temperatures up to the critical temperature, showed that this equation
holds
only
approximately.
By
plotting the values of y
5 against
temperatures
represented r = o and y
(t)
we have
Fig.
9.
;
the curve
in
5
At
tc
t,
but at lower
temperatures, T increases and the values of y 5 are represented by
ABC, a
portion,
AB, being curved
and the remainder, BC, being a straight line. Hence at temperatures represented by A A' the equation does not
Il8
PHYSICAL CHEMISTRY
it
hold, but beyond a certain distance from the critical point does hold.
Ramsay and Shields suggested that a correction for this be introduced and that we begin to count from a point A'. Making this correction for the distance d represented by
A', the equation
becomes
y
.
k(r-d).
The value
of
is
This formula
may
usually 6. be rewritten thus
y(mv)%
k(r-d).
ments
In order to obtain the value of the constant k, measureof the surface tension will have to be made at two
temperatures.
Then
for simultaneous values
we have
yi(mvi)%
= kfad) and
y2 (
Solving for k
we have
and solving
Substituting the values obtained by Ramsay and Shields for k, the following results were obtained
:
Ether
.".'..
Methyl formate Ethyl acetate
Carbon tetrachloride Benzene Chlorbenzene
............ ..... ..... Average ...........

x
....... .......... ....' ...... ........
2.1716
2.0419
2.2256
2.1052
2.1043
2.0770 2.1209
Hence, using the molecular weight, m, of the substance

in the gaseous state, they conclude that the constant k is 2.12 (C.G.S. units) for normal liquids whose molecular aggre-
gate
is
the same in the liquid as in the gaseous state.
That

is,
19
holds for non-associated liquids. It follows that if a liquid gives a value of the constant 2.12, or more, it is nonit
;
hence we have a associated, and if less, it is associated of determining the degree of association by determining the relation of the found value of k and the value 2.12
method
for
normal liquids. x = the number of molecules in the associated molecule, m% = number of times the mass of the associated molecule is greater than that of the unassociated molecule. Our equation would then be
If
y (mxv)*
2.i2(r
d)
(l)
but from the data we would obtain
y(mv)\
Dividing
(i)
= k^r-d).
(2)
by
(2)
we have
)
(3)
in
which x
is
number
of gaseous molecules
termed the association factor and represents the combined to form the liquid
practical details
molecule.
Morgan has worked out the

of
by means
which the proportionality of the surface tension of a liquid to the weight of a falling drop of it can be determined. This relationship is known as Tale's Law. Morgan substituted the weight of the drop, falling from a fine capillary
tube, for the surface tension of the drop
and obtained the
following equation
w(mv)%
where k
benzene.
is
= k(rd)
^liquid
established
by using the non-associated
Walden makes use

he defines as a 2
^
P
of the term' specific cohesion (a 2 )

,
which
where y
is
the surface tension and
120
p,
PHYSICAL CHEMISTRY
the density. If the surface tension is measured at the boiling point of the liquid, Walden finds a relation existing between the latent heat of vaporization and the specific
is
cohesion, which
expressed thus
a?
-= constant, where L 9 is
the latent heat of vaporization at the boiling point. The average value of this constant is given as 17.9. Trouton showed that the latent heat of vaporization, L,, multiplied by the molecular weight, m, was proportional to the boiling 'point of the liquid measured on the absolute scale;
i.e.
constant.
This
is
known
as Trouton's Law, which
emphasizes that the boiling points of liquids are ing states, and hence we are justified in using peratures as comparable temperatures, and as points are approximately the same fraction of
values, they are reduced temperatures. sized this, too, when he obtained for a large
correspondthese tem-
the boiling
the critical
Walden emphanumber of liquids
20.7 as the value of the constant for the equation repre-
senting Trouton's Law.
As
and
solving for
=
=
constant
=17.9
(i)
20.6
(2)
m we have
_
20.6
T_
1.16
17.90?
a2
from which the molecular weight can be calculated. Using this formula Walden has calculated the molecular weight of a large number of substances and found the usual
formula to represent the substance in the liquid state, such
SnCl 4 SiCl 4 CC1 4 PC1 3 CSs, etc. extended his formula and showed that it is applicable to the melting point of substances and that this temperature
as
,
, ,
He

is
21
also
parable temperature.
a reduced temperature and consequently a comThe formula takes the form
m
From this fused salts appear to be highly associated, for he obtained for sodium chloride (NaCl)io, for sodium bromide
(NaBr)g, and for sodium iodide (Nal)6.2, as the respective formulae representing the molecules in the solid state.
NOTE.
See Appendix for further discussion of the relative surface
tension and association factors.
CHAPTER
XII
REFRACTION OF LIGHT
THE
refraction of light furnishes, for transparent liquids,
a set of physical constants which may be conveniently and accurately measured. When a ray of light passes from one
medium
incident ray)
into another, the direction of the entering ray (the changes at the surface separating the two
media, and will pass into the other
medium
as the refracted
The angle this refracted ray makes with the normal ray. to the surface of separation is called the angle of refraction,
and the angle the incident ray makes with the normal to the surface is termed the angle of incidence. The refracted ray lies in the plane of incidence and on the opposite side of
the normal to the incident ray. Let the surface of separation of the two media be reprein Fig. 10, the incident ray by bo, the resented by
AB
fracted ray
the surface
of
by oc and the normal to by aod, while i is the angle incidence, and r is the angle of re-
fraction.
Then
cd
sin
= -^ and
bo
bo
sin r
d
co
j0r
*A = ri,
sin r
Si n ce
and
co are
is
,
radii of the circle.
This ratio, which

is
termed the relative index of refraction,
designated by
and we have
n~
sin i sin r
That
is,
the sine of the angle of refraction bears a constant
REFRACTION OF LIGHT
ratio to the sine of the angle of incidence. Law. The numerical value of this ratio
123
This
is
Snell's
depends on the
nature of the two media and on the character of the incident

ray.
According to the wave theory of
light, this ratio of
the
sines of the angles of incidence and of refraction is the same as the ratio of the velocities with which the light wave traverses the
two media.
The
absolute index
of refraction is
the value for light passing from a vacuum and would be but this correction is slightly higher than the value for air
;
rarely
made.
we have
In the determination of the index of refraction of liquids, the passage of a ray of light through the liquid into
the glass prism and then into the air, that is, we have the passage
of the ray through the glass prism. In the Pulfrich refractometer, which
is
one of the principal ones in use,
the entering ray of light is adjusted so as to pass horizontally between

the liquid and the prism, and the angle of incidence then becomes
90.
If
a ray of light be allowed to enter the prism as
is
indicated in Fig. n, it will be refracted as it passes into the glass from the liquid and again as it passes from the
glass into the air, where it is observed desire telescope of the instrument.
We
the index of refraction

is
between the
air
by means of the an expression for and the liquid as it
customary to define the ratio when the ray passes from air into the denser medium. For these three media we
would have the following relations

liuid
; '
,r N
=
by
air , '
then
.-,
N=
n\
air
glass
glass
n.
liquid
which we
shall designate
124
PHYSICAL CHEMISTRY
have
Now we
and
glass
sin r
glass
sin r'
and remembering the angle

i
of incidence
is
90, then we have

f x
sin
.
90
sin
(2)
Since sin 90
i,
this
becomes
sin r'
But
sin r'
cos r
(i)
Vi
sin 2
r.
(4)
Transposing
we have
sin r
= ^P~^
(5)
Substituting in (4)
Substituting this value in
(3),
i
we have
N
Substituting in
n =
N
,
we have
n = VjV 2
sin 2
2
i.
Therefore the index of refraction, n

9
= VN
sin 2
i.
is usually furnished with the instrument, and tables The value of are provided for obtaining the value of n for any observed value of the
angle
*".
It is necessary to use
monochromatic
light, as light of
different
wave
lengths
is
quently gives different tomary to use sodium light, the

elements
is
differently refracted indices of refraction.
and conseIt
is
cus-
D line, but the light of other

:
also used, such as that of lithium, strontium, or
the three rays of the hydrogen spectrum the blue line H/s, and the violet line y
the red line
Ha
REFRACTION OF LIGHT
125
METHODS OF EXPRESSING REFRACTIVE POWER

of refraction varies with the temperature and with the pressure, in general, with all conditions that in-
The index
fluence the density, and hence efforts have been made to find an expression which will be independent of these various
1
physical factors and which is dependent only upon the chemical nature of the substance. Gladstone and Dale developed
the empirical formula r

specific refractive
n
,
and named
refractivity.
this
r,
the
index or specific
Lorentz of Leyden proposed (1880) a formula deduced from the electromagnetic theory of light,
r
*r
Lorenz of Copenhagen simultaneously derived the same formula deduced from the undulatory theory of light. This formula is independent of temperature, pressure, and change Table XVII represents the specific refractivity of of; state.
water at different temperatures as calculated from both The n2 formula, as it is termed, apparently gives formulae.
more constant values
TABLE XVII
126
PHYSICAL CHEMISTRY
such great differences between the value of the vapor and liquid as by the Gladstone-Dale formula.
TABLE XVIII
SUBSTANCE
REFRACTION OF LIGHT
and which
is
I2 7
unaffected
by change
of temperature."
Lan-
dolt (1864), from extensive data, confirmed the refractive values for the elements carbon, hydrogen, and oxygen, and
showed that the constitution had an
effect
on the
refractivity.
Bruhl (1891) extended the work of the previous investigators and tabulated the following values for the refractivity constants.
commoner elements are given in and the hydrogen lines, H a Hp, H y and also the dispersive power for H/s H a and H y H a These are the recalculated values of Eisenlohr and are pracrefractivities of the
The
,
Table
XIX
for the
line,
tically the
same as the
original values of
Bruhl and Conrady.
TABLE
ELEMENT
XIX
128
PHYSICAL CHEMISTRY
TABLE
XX
(After Cohen)
REFRACTION OF LIGHT TABLE

SUBSTANCE
I2 9
XXI
Cont.
130
PHYSICAL CHEMISTRY
effect of simple ring
formation gives very small values, than the variations due to experimental greater from a error. Tschugaeff large amount of data found a = value of about D 0.67, while Oesterling found nearly the same value (MD = 0.71). These values were used to
The
not
much
establish the cyclic structure of various compounds. Upon the basis that benzene has three double bonds, the
value for the molecular refractivity may be calculated as follows, from the atomic refractivities given in Table XIX,
for the red
line,
Ha
6 atoms 6 H atoms 6 3 double bonds 3 6
X X X
2.41
1.09
i
.68
= = =
14.46
6.54
5.04
Sum
of
atomic refractivities
26.04
Experimentally at 20, n = 1.4967, p = 0.8799, and the molecular weight is 78. 2 Substituting in the n formula we have
i.4o67
I.4967
2
2
i -
78
r-*
25.93
0.8799
which
is
a close agreement.
Similarly,
some
of the other simple
benzene derivatives
give the following values according to Cohen.
REFRACTION OF LIGHT
The
close
131
following complex
:
compounds do not show such a
agreement
132
PHYSICAL CHEMISTRY
index, and hence the index of refraction varies with the The difference between the spekind of light employed. cific refractivities for light of greatly different wave lengths
is
called the specific dispersive power or dispersivity. This is obtained by using either of the -formulae and subtracting
the specific refractivities.

2
The molecular
dispersivity
is
the molecular weight (m)
times the specific dispersivity.
The
dispersivity values
have been determined in a man-
ner similar to the method for obtaining the refractivity constants for the elements and the different linkages. Bruhl
concludes that dispersivity
property and
ing
is
much more
relations
is preeminently a constitutive valuable as an aid in establish-
structural
than the refractivity.
Eykman
has shown that dispersivity affords a valuable indication of the position of the double bond. Auwers and Ellinger have
shown that
dispersivity
is
increased
by the double bond
in
the side chain as compared with it in the nucleus. In Table XIX is given the atomic dispersive power of a number of ele-
ments using the hydrogen lines and in Table XXI is given the molecular dispersive power of a few isomeric compounds.
CHAPTER
XIII
OPTICAL ROTATION
ORDINARY
light consists of
transverse vibrations which
take place in all directions at right angles to the direction of the ray. If a ray of light is allowed to pass through a piece
of tourmaline (an
aluminium boron
silicate)
cut parallel to
the crystallographic axis, a part of the light will pass through. If another similar piece of tourmaline is placed with its
axis parallel to the first, the ray of light will pass through If this second piece be rotated in a this second piece also.
plane perpendicular to the ray of light, the intensity of the light will gradually diminish with the rotation, and
are at right angles the light which passes through the first tourmaline plate will not pass through the second when in this position. Transverse vibrations in only one plane pass through the first plate of tourmaline, and the light which comes through is said to be plane
polarized.
If a ray of light be allowed to pass through a piece of Iceland spar normal to one of the faces, it will be broken up into two rays which are differently refracted. This phe-
when the axes
nomenon is termed double refraction, and the two rays are designated the ordinary ray, which follows the laws of refraction, and the extraordinary ray, which does not follow these
These two rays are polarized at right angles to each Hence Iceland spar can be used for the purpose of obtaining plane polarized light, but in order to do this it is
laws.
other.
133
134
PHYSICAL CHEMISTRY
necessary to intercept one of the rays, and thus permit only one to pass through. This may be done by taking a long crystal of Iceland spar, grinding the ends so as to change the
angle about three degrees, thus making the angle (Fig. 12) > 68, and then cutting it in two along the line
DAB
DB
perpendicular to the a right angle.
new
ADB
thus making the angle These cut surfaces are then polished
face
AD,
and cemented
in their original position
by Canada balsam. The ray of light entering
at
is
doubly refracted,
the ordinary ray following the law of refraction is

refracted
surface of
which has an index of refraction of 1.55, than that of the Iceland spar, 1.48, for the ordinary ray. If it strikes the Canada balsam at an angle greater than the The critical angle, it will be totally reflected at the surface. extraordinary ray, RE, is refracted less than the ordinary
ray.
Its
and meets the Canada balsam, which is greater
index of refraction in the
medium
is
greater
than that of the Canada balsam, consequently it can never be reflected at that surface and so will pass through the prism as indicated by REE'. At the point of entrance, R, and also at the surface where the two pieces are cemented together, the extraordinary ray is refracted, but
amount is so small that on a diagram of this size, can hardly be represented in any other way than by a This straight line through both sections of the prism. prism is known as a Nicols prism, and since it produces plane The plane in which polarized light it is known as a polarizer. the plane of polarization is located can be ascertained by means of a second Nicols prism when it is used in this
the
it
;
manner it Method
is
designated an analyzer.
of
of rotation can be
The amount Measuring Optical Rotation. bethe substance measured by placing
OPTICAL ROTATION
135
tween two Nicols prisms, one a polarizer to produce the polarized light, and one an analyzer to determine the amount the plane of polarization has been rotated. This is measured by having a scale divided into degrees and fractions
thereof attached to the analyzer so as to determine the angle through which the analyzer has to turn in order to
permit the light to pass through. Such an instrument is The light which comes through would called a polarimeter. either a bright field or total darkness in either case produce
;
would be difficult to read accurately. In order to obtain a field which can be read easily a number of devices have been designed and are now employed, such as the bi-quartz disk, the quartz wedge compensator, and the Lippich halfshadow apparatus consisting of small Nicols.
it
The angle of optical rotation is proportional to the thickness of the liquid through which the light passes. The
divided by the specific rotation is the angle of rotation, Since length, I, of the column of liquid times its density, p. the rotation varies with the temperature, it is customary
,
mination
to state the temperature of the solution at which the deteris made as well as the kind of light used. The equation for the specific rotation is
'
in which
represents the temperature

this case.
and D, the
spec-
trum
g,
line,
sodium in
For solutions when the concentration is expressed in grams, in definite volume, v, we have
[a]
=
D
or,
for concentration
in
per cent, p,
136
PHYSICAL CHEMISTRY
rotation of liquids would be expressed
The molecular
m[
or
it is
i'
a
/
J>
7-p
sometimes written
and owing to the
large value of the rotation to divide the result by 100.
it is
customary
It was early recognized by Biot that many Asymmetry. substances in aqueous solutions had the power of rotating the plane of polarized light, while an explanation was offered through the classic researches of Pasteur. One peculiarity
of
compounds and
is
their solutions
which manifest optical
activity metric atoms of either carbon, nitrogen, sulphur, selenium, In fact, there is no authentic case in which tin, silicon, etc.
that the compounds contain one or more asym-
an active compound has been found that does not contain an asymmetric atom. That is, a carbon atom is said to be asymmetric when all four of the valences are satisfied by groups which are different chemically or structurally. For example, amyl alcohol, which is optically active, may be
represented by the formula designated active. If, however, the group be replaced by hydrogen, we obtain the formula
OH
CH
C HB
2
H
CH OH
2
CH
CsHg
H
CH
ACTIVE
INACTIVE
atom
designated inactive, and the groups attached to the carbon are not all different, as they are in the formula marked active. In the substitution, however, it is necessary to
fore the substance will
destroy the asymmetric character of the carbon atom bebecome inactive. In the case of
OPTICAL ROTATION
137
malic acid (monohydroxysuccinic acid) and of tartaric acid, there are four different groups attached to the asymmetric
carbon atoms as the following formulas indicate
H
I
H
I
OH C COOH
OH C COOH
I
H C COOH
OH C COOH
i
MALIC ACID
i
TARTARIC Acir
These active compounds have isomers which have analogous properties, and while they are both optically active, and the rotation is of the same magnitude, it is in opposite directions for the two compounds, one rotating the plane of
left.
polarized light to the right, and the other rotating it to the Those that rotate the plane of polarized light to the
right are termed dextro-rotatory, and those that rotate the plane of polarized light to the left are termed Icevorotatory.
In 1867, Kekule proposed that the carbon be conceived as located at the center of a regular tetrahedron and that the four affinities be represented by lines drawn to the four
For convenience of writing, the symbol for caromitted and the elements or groups in combination with the carbon are indicated at the vertices, as shown in the following figures. In order to explain isomerism, Le Bel and van't Hoff simultaneously (1874) and independently made use of the idea of the tetrahedron carbon atom and grouped the elements or groups in combination with the carbon atom around the base of the tetrahedron in one direction to represent one isomer and in the opposite direction
vertices.
bon
is
to represent the other isomer. This is illustrated in Fig. in I where we have the 13, symbols acd arranged from II to while in are right left, arranged from left to right. they
The
rotation would be represented as
or laevorotatory
138
in I
PHYSICAL CHEMISTRY
and
II,
and
These two figures, 1 or dextro-rotatory in II. are the mirrored images of each other, and while
alike,
they are
they cannot be superposed that is, they are right-handed and left-handed. It
;
is
known
isomeric
that solutions of two compounds can be mixed
in equal quantities so as to produce an inactive mixture, and such mixFIG. 13.
tures are termed racemic mixtures.
There
of isomeric active
are,
however, certain forms
compounds which are inactive, and this property is explained upon the assumption that by an internal compensation the compound is rendered inactive. Such inactive
compounds are designated the meso form. Here we have an illustration of a compound containing an asymmetric carbon atom without rendering the compound optically active. In the case of tartaric acid we have the example of a compound existing in these three forms, and in Fig. 14 is illustrated the structural arrangements by means of which
they are explained.
COOH
COOH
COOH
H C OH
OH C H
H C OH
HO C H
I
H C OH
I
CQOH
COOH
MESOTARTARIC ACID
L^VOTARTARIC ACID
FIG. 14.
DEXTROTARTARIC ACID
OPTICAL ROTATION
139
The meso form manifests no rotation, the laevotartaric acid rotates the plane of polarized light to the left, and the dextrotartaric acid rotates the plane of polarized light to the right. In addition, we have the racemic acid, which is a mixture of
equimolecular parts of /- and of d-tartaric acids. Many substances are optically active, and the specific
rotation of these
is
listed in tables of physical constants.
of this property is one of the principal methods employed in identifying, testing the purity, as well as making
The use
quantitative determinations of such substances as sugars

essential
etc.
;
oils,
including
lemon, wintergreen, peppermint,

;
the alkaloids, nicotine, brucine, strychnine, etc. turIn the case pentine, camphor, and a long list of others. of sugars, this method is generally employed, as the rotation
is
proportional to the concentration
in
which
c equals concentration in 100 cc. of solution.

c,
Then
[a]/
and
is
since a tube of constant length,

is
in decimeters,
expressed employed, and the specific rotation of

/,
cane sugar
substituting
fc,
constant,
[a]
=
/
(66.5,
c,
= one
/
decimeter)
we have a
kc,
66.5-
but 66.5
is
a constant,
then a
the rotation
tration.
In Table
XXIII
rotation, [a]2, at 20 spectrum, for the carbohydrates

foods.
is proportional to the concenare given the values of the specific for sodium light, the D-line of the
commonly occurring
in
These values are the ones usually employed in analytical work and are sufficiently exact for that purpose. Effect of Temperature. We have seen that the temperature affects the specific rotation, and the formula contains a term designating the temperature at which the determination is made. The rotation may increase or decrease
with the change of temperature. Methyl tartrate is practically inactive at o C., while below this temperature it is
140
laevorotatory,
taric acid pass
i.e.
PHYSICAL CHEMISTRY
negative.
value for the specific rotation with change of temperature, while some of those with large negative rotation change but little with a large
through a
Many maximum
of the esters
of
tar-
change in temperature.
tation
is
For most sugars the

for
all
specific ro-
temperatures. In the rotation decreases with the general, however, specific

practically
constant
temperature, as is shown by laevulose and arabinose, particularly while xylose increases and dextrose remains practically constant for
temperature changes up to 100.
It is
necessary to determine the temperature accurately in all sugar analysis and to make the necessary corrections.
Browne has compiled formulae by which such corrections can be made and these are given in Table XXIII.
TABLE XXIII
OPTICAL ROTATION
141
active substances
The rotation of optically Effect of Varying the Solvent. is very different in solution from the rota-
tion of the pure substance, and the nature of the solvent has a marked effect upon the magnitude of this rotation. Table XXIV shows the change in the specific rotation of
ethyl tartrate and of nicotine when dissolved in different solvents, the specific rotation of the pure substances being
respectively
+7.8 and
161.5.
TABLE
XXIV
(Thorp's Dictionary)
SOLVENT
142
PHYSICAL CHEMISTRY
in the specific rotation is very pronounced in the case of the reducing sugars, certain oxy-salts, and lactones. Dextrose gives a value of 105.2 for freshly prepared solutions, which
This phenomenon Landolt and others on the explained by assumption of different molecular arrangements of active forms in the freshly prepared solutions which gradually break down into molecules of lower rotation. This change to a constant rotation can be produced by allowing the solution to stand for sevfinally gives the constant value of 52.5.
is
eral hours,
by
boiling the solution, or
by the addition
of a
small quantity of alkali or acid.
Electromagnetic Rotatory Power. Optical activity is due to the inner structure, and not many substances possess this property. Electromagnetic rotatory power is possessed all substances. This property was discovered by Faraby in He 1846. day placed glass between poles of a magnet and found that the plane of polarized light was turned. This
phenomenon lasts only while the current is passing. The electromagnetic rotatory power is a function
of the
temperature, depends upon the strength of the magnetic field, and, as in the case of optically active substances, is dependent upon the density of the solution and length of
the observing tube. If polarized light which passes through a solution in the electric field is reflected back through it, the plane will be turned back to its original position while in case of an optically active compound, if the ray be sent back through it, the amount of rotation will be doubled. The formula for the magnetic rotation is similar to that
;
for the specific rotation of optically active substances. The of the rotathe ratio rotation specific magnetic is, however,
tion of the given substance to the rotation of water which
Perkin used as the standard,

refers to water.
i.e.
lp
-r-
-^- =
,
where
is
pn
The
molecular magnetic rotation
the
OPTICAL ROTATION
specific rotation multiplied by the molecular weight of the substance divided by the molecular weight of water, i.e.
uiQpQm
lp<i>o 1
_ mo ecu ar
i i
magnetic rotation.
as well as a constitutive property.
The molecular magnetic rotatory power is an additive The value for CH2 is
CH,
SERIES
obtained from homologous series such as the following:

Paraffins
1.051
Alcohols
Aldehydes Fatty acids

Esters
1.057 1.022 1.021 1.023
Alkyl chlorides Alkyl bromides Alkyl iodides
Phenyl esters
I.OI5 1.031 1.031 1-053
individual values vary as in the case of alkyl iodide they range from 1.005 to 1.066. Perkin takes as the mean If there are a number of carbon atoms 2 =1.023. value,
;
The
CH
in the molecules of a particular group of compounds, then by deducting n times the value of CH 2 from the total magnetic
rotation, a value
(5)
.
is
obtained which
is
called the series constant

:
In
the fatty acid series
we have
ACID
144
large
PHYSICAL CHEMISTRY
out,
number of series of organic compounds has been worked and in Table XXV a few of these are given.
TABLE
SERIES
XXV
CHAPTER XIV
SOLUTIONS
IT
is
a familiar fact that the physical form in which matter
dependent on temperature and pressure. Water forms which can be changed one into the other by slight variations in the temperature without changing the pressure. This is true of a very large number of substances but in many cases, these changes in form can be much more easily accomplished by changing the pressure also, whereas some substances which exist ordinarily in the gaseous form cannot be changed to the other forms unless there is a change in the pressure as well as in the temperature. Theoretically matter exists in all three forms, and to these forms of matter solid, liquid, and gaseous we are to apply the term phase, a concept which was creâted by Willard Gibbs and which he defined as follows: " We may call such bodies as differ in composition or state different phases of the matter considered, regarding all bodies which differ only in quantity and form as different examples of the same phase." This is analogous to our conception
exists is exists in three physical
;
of
form of matter, physical modification, or state. By the term phase we understand a mass that is chemically and physically homogeneous. Any mass of matter under consideration which may exist in one or more phases is termed
a system.
a system results from the system is independent of the time. For in heterogeneous (non-homogeneous) systems, such as a salt in contact with a solvent, or two gases that
of
The homogeneity
being in a state of equilibrium which
145
'
146
PHYSICAL CHEMISTRY
have just been brought into contact, the concentration is different at different places, and the mixtures are of different
composition in different parts of the systems. The systems not being in equilibrium will change simultaneously into homogeneous systems, and equilibrium will result. This would also take place if different parts of the same system
were at different pressures or different temperatures. Hence, our considerations are limited to the state of equilibrium of
bodies or systems of bodies and consequently to homogeneous systems. The existence of water in contact with water vapor might be considered contradictory to the idea
of physical homogeneity, yet
when the system
is
of
uniform
temperature and pressure, equilibrium exists, although we have it consisting of more than one homogeneous body, for the water is itself homogeneous and the water vapor too. In such systems we must have the same temperature and the same pressure throughout, for otherwise there would not be equilibrium and consequently a change would occur in the volume energy of the bodies that constitute the system. Such a system is said to be a one-component system
because
it
consists of only one chemical individual, species,
or compound.
Now
this
system
liquid
water and water vapor
consists of
two phases, the
and the vapor.

;
It is
not necessary
that a phase consist of only one body, for it may be distributed among a large number or, in other words, a very large number of bodies of one particular chemical individuality may constitute a phase, as the vast number of globules of butter fat in milk all constitute one phase. Or, a large
number
of different chemical individuals
may
constitute one
phase, as the casein and milk sugar in the water solution This last case constitute the second liquid phase in milk.
is
an example of a multiple component system. This then would give a two -phase system for milk. If to distilled water sodium chloride is added, we obtain a solution which
SOLUTIONS
is
147
physically as well as chemically homogeneous and thereIf we continue to add salt, we fore constitutes one phase. no more salt will go into soluwhich reach a point beyond
tion
and the
solid
added
will
eventually in equilibrium with the solution. one solid phase but an additional phase
;
;,
remain undissolved and be We now have if we were to
decrease the temperature of the system sufficiently, there would appear solid water (ice) as a second solid phase, and
the vapor above the solution a fourphase system. It is possible to make our selection such that the solid substance used is capable of existing in two solid modifications, and with the appropriate solvent we could
we should have with
then have
five
phases
two
solid phases of the dissolved
substance, the solid phase of the solvent, the liquid phase If we (solution), and the vapor phase of the pure solvent.
select
two non-miscible substances, we should then have

;
two
is
the vapor phase, and, if the temperature very low, possibly a solid phase. So by the judicious selection of substances we can make any complexity of phases
liquid phases
we
desire.
As in the case of physical homogeneity, Components. so also with chemical homogeneity, it is necessary that the system be in a state of equilibrium, otherwise there may be a gradual transformation of one of the chemical individuals into the other, or vice versa, and it is not with the process of change that we have to do, but with the state of equilibrium to which the subsequent considerations apply. The
determination of the number of components that constitute a system is not always an easy matter, hence it is necessary
that the idea of components be clearly in mind. In the water system consisting of the three phases, solid, liquid,
an analysis of all the phases would show that and vapor, they are composed of oxygen and hydrogen and that the proportion is the same in all three phases, and further, that this proportion is that in which oxygen and hydrogen com-
148
PHYSICAL CHEMISTRY
bine to form water.
The system
is
said to consist of one
and consequently is desigThe same is true of sulphur a nated one-component system. of them would show the but all be four there would phases, case of water, howIn the same composition by analysis. raised was if the very high, it would be ever, temperature found that the water was decomposed into its constituents, hydrogen and oxygen, arid that they existed as the elemental substances in equilibrium with water vapor. Here we should have a somewhat different state, as they would then
chemical individual or substance
;
be considered as components, because they take part in the Hence, a change in the conditions of the equilibrium. a change in the number of comnecessitate system may therefore We distinguish the components of a ponents.
phase or system as the constituents of independently variable concentration, and they may be either elements or compounds.
Therefore
we
define the
" individuals components or
of
any reacting system as the separate chemical substances undecomposed in the reactions concerned, which are necessary to construct the system. The ponents or) individuals to be chosen
necessary to construct the system."
number
is
of such (com-
the smallest
number
,
(Richards.)
This may be illustrated by the system CaCO 3 CaO + CO2 wherein only two of the three constituents, CaO and CO 2 " are undecomposed in the reaction concerned." Conse,
quently the system
is
a two-component system.
The composition of Glauber salt is Na2 SO 4 ioH 2 O, that of its solution Na2 SO 4 and H 2 O, and that of the vapor of the
solution
H O,
2
is 2 0, so that, varying the ratios of Na 2 SO 4 and the constituents of the solution, we can produce all of
the three phases, therefore this is a two-component system. Similarly other hydrates can be obtained by variation of two
components.
This
4
is
2
also true for double salts,

2
such as
2
K SO MgSO
2
H O (Schonite), K SO CuSO 6H O, etc.,

4
where the components are the undecomposed single
salts
SOLUTIONS
149
and water, therefore a three-component system, such as they are, is sufficient to form all modifications that can exist.
The tests employed by the orSeparation of Phases. and purity of substances for the identification chemist ganic
by means of phase transformations with a record of the accompanying heat change. If he desires to determine the
are
purity of a beautiful crystalline product, he determines
its
so-called melting point. nothing more at a at what temperconstant pressure than determining in On ature the solid and liquid phases are equilibrium.
This
.consists
in
the other hand, if the substance is a liquid, he determines at constant pressure the temperature at which the liquid
and vapor phases are

point.
If
either
is
in equilibrium, that is, the boiling constant, the substance has the same
composition in both phases, and he is working with a onecomponent system and concludes that the substance is pure.
(This is true except in some special cases that will be considered in detail subsequently.) Not only in the preparation
and
identification of substances
do we make use of the
phase conceptions, but in the preparation and purification of the same. Our gravimetric methods are based on the separation of the pure solid phase which is one of the components of our In fractional crystallization multiple component system. we have the separation of a solid phase, while in the process
of fractional distillation
we make use
of the
vapor phase for
the separation of 'components. So in a large majority of our chemical manipulations we have to do with the separation
of phases.
liquid, or
difficult
When these phases are alike, both solid, both both vapors, the operation becomes much more
is
and particularly
this true in the separation of
vapor phases.
In the separation of these latter
we have
not as yet made very rapid progress. When the components are increased, the complexity of some of the systems is very much increased, for there are
150
PHYSICAL CHEMISTRY
a great many possibilities in multiple component systems. These compounds may be so selected that they form a phase which conforms to the laws of Definite and Multiple ProThen the phase is known as a chemical compound. portions. If, however, the components do not conform to this law, the phase is called a solution. A solution may better be defined as a phase in which the relative quantities of the components can vary continuously within certain limits, or as a phase of continuously varying concentrations. There is, however, no stipulation as to the particular phase of which a solution may be formed, therefore it is possible that a solution may be of any of the three phases solid,
vapor, or liquid. In the case of solutions that are in the form of liquids, one of the components is called the solvent and the other the dissolved substance or solute.
We
are familiar with
many
gas).
examples
of solutions wherein the solvent is liquid

is
and the
dissolved substance
solid,
a liquid, or a vapor (or
Where
solids act as the solvent
and the
so-called solid soluis
tions result,
we have a conception which
perhaps not
quite so well known but which is very common. Examples of solid solutions include such double salts as potassium
and ammonium alum, ammonium and ferric chlorides, potassium and thallium chlorates, etc. the occlusion of gases by metals, such as hydrogen by palladium and the absorption of oxygen and carbon dioxide by glass at a temperature
; ;
of 200
into platinum
under 200 atmospheres pressure. Copper diffuses and into zinc. For the same reason hot crucibles should not be handled with brass tongs. platinum Another very interesting case is the passage of sodium through sodium glass without any visible change. If electrodes of lithium amalgam are used, the sodium is replaced by lithium and the glass becomes opaque and crumbly, owing to the fact that there was a contraction. It has, however, been found impossible to electrolyze a sodium glass
SOLUTIONS
151
between electrodes of potassium amalgam. Many other examples of solid solutions will be met in the course of our work.
GAS AS SOLVENT
When hydrogen is introduced into a vessel containing oxygen at ordinary temperature, after a short time the two gases will be mixed thoroughly. It is immaterial what relative quantities of the two are brought together, there will be produced a homogeneous mixture of the two. This is true of any other gases that do not react chemically. So it may be stated that gases are miscible in all proportions. Here we have a simple intermingling of the gases, and as a
we should expect the properties of the mixtures to be the summation of those of the individual constituents, and in fact this is the case, each individual gas conducting
result
itself
of the gas mixture is the
as though the other were not present. The pressure sum of the individual pressures.
The
specific heat, the
power
all
when they are mixed. Dewar has shown that a vessel containing air is more highly colored by iodine than when the iodine is introduced
into one
of a
the solubility, in fact gases remain the same
of absorbing and refracting light, of the physical properties of the
from which the
air
was removed.
This
is
also true
of gases, thus showing that the gas present exerts a solvent action on the iodine and more of it is therefore present.
number
solved
by
CO
Villard (1895) nas shown that iodine is dis.as the spectra of the vapor do not show
,
the least characteristic of gaseous iodine. That iodine and bromine are soluble in CS 2 above its critical temperature,
and that KI
is soluble in alcohol vapor, have been fully demonstrated by Pictet, Wood, Hannay, and Hogarth, and others. While the question of a gas acting as a solvent has been quite fully demonstrated in cases where the solute is a gas, liquid, or solid, the subject does not present any-
thing of importance in our present consideration further
152
PHYSICAL CHEMISTRY
than the fact that a gas may be considered as a solvent, thus illustrating our second group of solvents.
LIQUID AS SOLVENT
Gas as Solute. When a gas is brought into contact with any selected liquid, the gas is absorbed by it but the quantity absorbed varies greatly with the liquid employed, with the gas used, as well as with the temperature and
;
In the case of oxygen, hydrogen, nitrogen, and other gases, the quantity of the gas dissolved is very many small whatever the liquid employed. In any case when the
pressure.
maximum amount
has been absorbed under the prevailing results a state of affairs such that the same there conditions, number of molecules of the gas pass into the liquid and pass from the liquid into the gaseous space above, in unit
time. The system consisting of the gas said to be in a state of equilibrium.
and the
liquid
is
It was shown by Henry (1803) that the mass of any gas that dissolves in a selected solvent is in direct ratio to the
pressure of the gas. For example, at three atmospheres pressure three times as much can be dissolved by a liquid at a conis dissolved at one atmosphere pressure. This law of Henry may be expressed in a number of ways. If we designate the Statement of Henry's Law. i. mass of the gas in unit volume of the liquid as the concentration of the gas in the liquid, C and represent the concentration of the gas in the space above the liquid by Cv then
stant temperature as
t,
the ratio of these two concentrations remains constant for

all
values of the pressure,

2.
i.e.
C9
=k.
absorbed
is
The
total quantity of a gas
always pro-
portional to the pressure on the gas. As we usually express the quantity as the mass (i.e. the weight) then the mass of
the gas per unit volume, i.e. the concentration (Ci) then have C = k'p. portional to the pressure.
is
pro-
We
SOLUTIONS
3.
it
153
If
follows
the quantity be expressed in terms of volume, then from Boyle's Law that twice the mass occupies
the same volume under twice the pressure, and as Henry 's" Law states that the quantity of gas absorbed is proportional to the pressure, it follows that the same volume of gas
is
dissolved in a specified quantity of a liquid at
all
pressures.
Confirmation of Henry's Law. Henry's Law has been subsequently confirmed by a number of workers, particu-
by Bunsen and by Khanikof and Luginin, the results whose experiments on the solubility of CO 2 in water are given in Table XXVI.
larly
of
TABLE
p
XXVI
154
over at 126.
PHYSICAL CHEMISTRY
These gaseous substances which are so very
readily soluble in water do not follow Henry's Law. Coefficient of Absorption is defined as the number of cubic
centimeters of the gas absorbed by one cubic centimeter of the liquid at o C. and 760 mm. pressure. This coefficient
for the so-called
permanent gases
is
from
o.o i to 0.05, while in the case of those gases
very small and varies which are
Law the coefficient is much larger. of The solubility gases decreases with an increase of temperature, as is illustrated in Table XXVII.
exceptions to Henry's
TABLE XXVII
GAS
COEFFICIENT OF ABSORPTION
SOLUTIONS
155
containing vessel, the specific heat, etc., experience no change. Hence, if we have a mixture of gases in contact with a liquid,
each individual gaseous species exerts its own individual pressure, and according to Henry's Law the amount of this particular gas absorbed should be proportional to this
In fact, it has been shown by Dalton (1807) that the solubility of a gas is unaffected by the presence of other gases and that the amount of each absorbed is propressure.
This is known as portional to its own partial pressure. the Absorption Law of Dalton. By the partial pressure of a gas we mean the pressure exerted by that particular gas.
For example, if we have a mixture of two gases, oxygen and nitrogen, the total pressure, p, which would be required to keep them at a certain volume would be the pressure of one atmosphere. Now the oxygen in this volume would exert its
own
the
and the nitrogen its own pressure, pNt would equal the total atmospheric pressure exerted upon the mixture, i.e. p = po + py, which is the expression for Dalton 's Law that the total pressure
sum
pressure, po, of which
equal to the sum of the partial pressures of the individual species of a gaseous mixture. Water exposed to air becomes saturated at the given
is
sure
temperature and pressure. Let us assume that the presis 760 mm. This is the total pressure, and since the
oxygen constitutes 20.9 and the nitrogen 79.1 per cent by volume of the air, then the partial pressure of the oxygen
will
be be
20 9 of 760 100.0
'
mm.,
or 158.84
mm., and that of nitrogen

18 the solubility
will
'
9>I
100.0
of
of 760
mm., or 601.16 mm. At
1^8.84. -*
0.0324 and of nitrogen is 0.01605 under 760 mm. * , 601.16 v -X 0.03242 = 0.006776; 0.01605 = 0.01269. 760 760 0.006776 0.01269 34-8 65.2 per cent of oxygen and of
oxygen
is
,,
nitrogen respectively.
CHAPTER XV
SOLUTION OF LIQUIDS IN LIQUIDS
SOLUBILITY
I
WHEN
portions.
liquids
sulate liquids.
mix in all proportions they are termed conWater and alcohol are miscible in all proare
They
termed a pair of consulate
liquids.
Mercury and water do not mix in any proportion, neither do kerosene and water. These are non-miscible liquids. Intermediate between these two types of pairs of liquids we have a very large number of liquids which manifest a partial
solubility of the
one in the other.
These pairs of liquids
are termed partially miscible liquids. If we add ether to water, there is formed a solution of ether
becomes more and more concentrated as ether is added. Finally a concentration is reached in which a second liquid layer appears. We have saturated the water with ether we have two liquid layers that are non-miscible. If we were to add water to ether, the same result would be the formation of two non-miscible layers. If obtained, we continue to add ether in the first case, the relative volumes of the two layers would change, the lighter one increasing in volume and the lower one decreasing until finally it would disappear, when we should have water dissolved in If we were to add water to ether, we should have ether. practically the same result, the water dissolving, two liquid layers formed, the volume of the layers changing until one
in water,
and
this
(the lighter in this
case) disappeared with

156
the formation

of a
157
homogeneous solution
of ether in water.
15.
This
may
AB
EUur
be represented graphically by Fig.

If
A =
100 per cent of water and
B =
will represent all possible concentrations of
100 per cent ether, then water and ether.

Ethly
Let the concentration of the liquid layers be represented by the vertical axis A C. If we start out with pure water, at A and
,
add ether, the concentration of the solutions would be represented by the line AE. At
the concentration represented by
liquid layer
E the second
would appear. The two liquid layers would have the concentrations represented by E and E' respectively, E' being
the concentration of the upper layer. Now as more ether is added, the concentraFIG. 15.
tion of the two liquid layers when in equilibrium would remain constant, as represented by the lines E'F' and EF. By the continued addition of ether a point, F, would finally be reached at which the lower layer would disappear, and we should have a homogeneous solution of water
which would be represented by F'. As continued, solutions of water in ether would be 1 formed, which are represented by the line F'D. EF and E'F represent the two non-miscible liquid layers, and since these are in equilibin ether, the concentration of
the addition of ether
is
to ether
rium, they represent saturated solutions EF saturated with respect and the lighter layer E'F' saturated with respect to water.
;
Hence it is apparent that the two non-miscible liquids formed from the partially miscible liquids are saturated
solutions,
and these saturated solutions are themselves non-
miscible liquids, so we may consider the pair of saturated solutions formed from partially miscible liquids in the
class of non-miscible liquids.
The determination
of
the mutual
solubilities
of
this
system at different temperatures would give us the different concentration in the two layers. So a study of the behavior of a pair of partially miscible liquids resolves itself into the determination of the solubility at different temperatures.
Alexejeff (1886) took a definite weight of water
PHYSICAL CHEMISTRY
and
of aniline, put
them into a tube,
sealed
it,
and determined
the temperature at which the mixture became clear. He did this for a number of concentrations and obtained the
following data:
TEMPERATURE
159
Most
partially miscible liquids
become consulate at high
temperatures, but there are a number of interesting exceptions to this. A mixture of di- or trimethyl amine and water separates into two liquid layers when the temperature
is
lowered, the mutual solubility increases, and if the temperature be lowered sufficiently the liquids become consu-
late. This decrease in solubility with rise of temperature has been observed in many other cases, such as butyl alcohol in water, and also paraldehyde in water. In Fig. 17 we have minimum solubility, while with de-
crease in temperature the solubility increases
and
finally
reaches a temperature below which the liquids are consulate. Many ketones and lactones show a peculiar characteristic
have a minimum solubility at an intermediate temperature, and the solubility increases with either an increase or a decrease of temperature. In Fig. 18 we have
in that they
ISO"
100%
JVator
100*
Triethylamine
100 *
100*
Methylethylketone
Water
FIG. 17.
FIG.
i 8.
represented the temperature of

either
minimum
solubility,
and
above or below
this
temperature the solubility in-
creases.
It is conceivable that the solubility curve may be a closed curve as these figures represent the three different portions of a closed curve. Recently Hudson found this to be real-
ized in the case of nicotine
and water. Figure 19 represents the effect of temperature on the solubility of nicotine in water.
i6o
PHYSICAL CHEMISTRY
By heating mixtures of non-miscible liquids, we saw that above a certain temperature for all concentrations they become consulate. If, however, we keep the temperature constant, we can accomplish practically the same result by adding a liquid which is consulate with both the components. So if we have three liquid components A, B, and C, and if Cis consulate with A and B, then the mutual solubility of A and B is increased, and by addition of a sufficient quantity of C one liquid It is conlayer can be produced.
150"
ceivable, however,
JOO* Water
1009
Nicotine
that
if
is
consulate with A, but only partially miscible with B, the addition of
FlG I9
would increase the
solubility of B.
By
but might decrease the solubility of the proper selection of the three com:
C A
to a mixture of
and
ponents we could obtain combinations which would result in the formation of these three classes of reactions
1.
The
three components form only one pair of partially
miscible liquids. 2. The three components form

cible liquids.
3.
two
pairs of partially mis-
The
three components form three pairs of partially
miscible liquids.
In representing the relation of Triangular Diagram. the mutual solubility to the change in temperature we used the horizontal axis to represent the concentration and the
To represent vertical axis to represent the temperature. the concentration of three liquid components use is made
of the triangular diagram, and since this is on a plane surface it represents the concentration at one temperature.
There are two methods of representing the concentration by means of a triangular diagram, and we shall use the method of Roozeboom, and only refer to that of Gibbs indirectly.
161
Construct an equilateral triangle, A CB, Fig. 20. We saw that a line such as AB would represent all possible concentrations of A and B. Similarly let BC represent all possible concentrations of B and C, and AC represent all possible concentrations of A and C. The concentration of any mixture of A B, and C will be represented by some point within the triangle. Assume the ends of the lines, i.e. the corners of the
,
100%
100%
70
60
30
40
50 60
40
30
70
zo
10
o*
100
1
80
90
FIG. 20.
triangle, to represent 100 per cent respectively of A, B, and C; then divide the sides into 10 equal parts and draw lines parallel to the sides of the triangle. Then from the intersection of these lines the composi-
tion of a mixture represented by any point, such as O, can be readily ascertained. Counting the composition of A on the lines parallel to
for B,
the side opposite A, we have 4, i.e. 40 per cent; counting similarly we find i.o or 10 per cent, and since O is on 5th line from the side opposite C, then the concentration of C is 50 per cent, and that of our mixture is A =40 per cent, B = 10 per cent, and C = 50
per cent.
162
PHYSICAL CHEMISTRY
Ether and alcohol are miscible in all proportions (and also water and alcohol), but water and ether are only partially So if a mixture of ether and water be taken in miscible. known proportions of about equal quantities and shaken with a little alcohol and allowed to come to equilibrium, two
FIG. "2i.
liquid layers will
be formed. By repeating this with sucof alcohol a concentration will eventually be cessive additions but one liquid layer is formed. If the at which reached point of concentration be established where just one drop of the alcohol will cause the disappearance of one of the two
Similarly sucliquid layers, we have a point of saturation. cessive points of saturation could be established synthetically for all concentrations of ether
and water.
Then by
163
plotting these results on a triangular diagram, we would have a curve similar to x y z y\ %i in Fig. 21.
Let then the sides of the ether, A alcohol represent water, triangle will represent all possible mixtures of the three pairs of liquids, taken two at a time. Since ether is partially soluble in water, x repre;
sents the saturated solution of ether in water, similarly Xi represents a saturated solution of water in ether. The line would represent solutions of ether in water and Exi solutions of water in ether.
Wx
The
x y
series of saturated solutions of water, ether,
and alcohol at con-
stant temperature
z yi
XL
If
be represented schematically by the isotherm one starts with the liquid phase designated by x and
may
varies the three components, the line xyz would represent one series of saturated solutions. From Xi the same point z would be reached, and
the curve Xiyiz would represent the composition of the other series of So by starting with the concentration designated by either x or Xi and varying the composition, the same concentration
saturated solutions.
of saturation as represented by the point z would be reached, two solution phases become identical. Hence the isotherm
where the x y z yi x\
represents the series of saturated solutions of the three components which are in equilibrium at a definite constant temperature. Above and outside of this isotherm is the field of unsaturated solutions,
and the portion of the figure included by the curve represents the field of mixtures which separate into two liquid phases, the composition of which is given by some two points on the isotherm. Since the
isotherm represents the composition of these saturated solutions in or E will cause clouding. equilibrium, the addition of the component
which of the conx was due to the saturation of would not cause by E, so any further addition of clouding of this solution, but as we follow up the isotherm there must come a point at which the addition of will cause clouding. Such a point, y, is where the line drawn through is tangent to the
it
Now let us inquire whether

is
makes any
difference
of
stituents
added.
We
saw that the location
WH
curve.
The same
is
true for the addition of the
EK through E being
perimentally that indicated by H,
if
tangent to the curve at
to a mixture of
A and E
be gradually added, clouding will eventually take be place and the mixture separate into two liquid phases but if added to a mixture of E and A containing less of E than indicated by H, no clouding will result. The same reasoning may be applied to the addition of E to solutions of and A containing more or less of than indi;
component E, the line It has been shown exyi. containing more of E than
cated by K, clouding occurring in the
first
case
and not
in the second.
1 64
PHYSICAL CHEMISTRY
It is therefore apparent that the isotherm is divided into four parts which correspond to the following four distinct sets of equilibria 1. The solutions represented by the line xy are saturated with does not produce a precipitate. respect to E, and an excess of 2. The solutions represented by the line yz are saturated with respect or E produces a precipitate of E. to and an excess of 3. The solutions represented by the line zy\ are saturated with or E produces a precipitate of W. respect to W, and an excess of 4. The solutions represented by the line yix\ are saturated with respect to W, and an excess of E does not produce a precipitate. Above the solubility curve we have the area of unsaturated solutions, while within the curve all possible mixtures of water and ether and alcohol which will separate into two liquid layers may be represented. Any point, such as d, represents the proportions of water, ether, and alcohol which when shaken together and allowed to come to equilibrium would separate into liquid layers the composition of the lower heavier liquid layer would be represented by some point, as m, on the solubility curve and the upper liquid layer by n on the other side of the solubility curve. The straight line passing through the point d and connecting
:
If any other mixture, repthese two points is designated the tie line. resented by a point k on this line, was to be prepared and allowed to come to equilibrium, the composition of the two layers would also be
represented by the same two points m and n on the solubility curve. That is, if we were to take a number of mixtures represented by points on this tie line and allow them to come to equilibrium, the upper layers on analysis would all be found to have the same composition represented by n, while the lower layers would all have the composition represented by the point m on the solubility curve.
Another case similar to the water-ether-alcohol system
is
that of silver, lead, and zinc. Molten lead and silver are miscible in all proportions, silver and zinc are also consuThis late, but lead and zinc are only partially miscible.
system has been worked out by Wright, who obtained the data given in Table XXVIII. The values given in the horizontal rows represent com-
and lower layers in equilibrium at the These would compare to such particular temperature. in Fig. 2 1 which are designated conjugate points as n and The points, and the liquids are termed conjugate liquids.
position of upper

composition of the upper layer is much richer in silver than the lower layer. So by this means silver can be separated from lead and the upper layer rich in silver can be
is
TABLE XXVIII
UPPER LAYER PERCENTAGE AMOUNT or
1 66
PHYSICAL CHEMISTRY
is
the concentration Cz in the other liquid,

>5
a constant,
i.e.
-r C\
is
k.
That
is,
the ratio of distribution between two liquids

is
a constant.
This
known
it is
as Nernst's Distribution Law. as
This law has
its application,
we have
seen, to metal-
lurgical processes,
and
constant the more
apparent that the greater the of the dissolved substance (Ag, for ex-
ample) can be removed from the liquid by adding zinc. As the solubility of silver is greater in aluminium than in zinc, the substitution of aluminium for zinc would give a larger value for the constant, and consequently a greater quantity of silver would be found in the upper layer, and therefore a So the practice consists in greater percentage extraction. a considerable of aluminium to increase the adding quantity
efficiency of the desilverization of the lead.
The ordinary shaking out proShaking Out Process. in the organic laboratory is nothing more employed than the application of this principle. If a compound is prepared in an aqueous solution and this solution shaken with ether, in which the substance is more soluble, and the ether is then removed by means of a separatory funnel and
cess
evaporated, the separated material is obtained in the free state. The greater the distribution ratio the more efficient
the extraction, and it is better to extract with successive small quantities of the solvent than to use the total quantity at
one time, as the following consideration will show. Let us assume that we have' 12 grams of a substance dissolved in 100 cc. of water and that it is twice as soluble in benzene as it is in water. If we add an equal volume of benzene to the 100 cc. of water, then the substance dissolved will distribute itself between the benzene and water
in the ratio of 2:1,
and
f of 12,
or 8 grams, or 66 f per
cent, will be contained in the benzene, and ^ of 12, or 4 grams, or 33^ per cent, will remain in the water. Hence,
by extracting with equal
quantities of the benzene, 66 f

per cent of the substance could be extracted.
167
Now
as-
sume that we divide the benzene into two portions of 50 cc. each and extract the 100 cc. of aqueous solution with them
Since the substance is twice as soluble in successively. benzene as in water, 50 cc. of benzene will dissolve as much
and so after shaking water with 50 cc. of benzene the substance would be equally divided between the two solvents or in the ratio of i i, and one half of the substance would be extracted,
of the substance as the 100 cc. of water,
100
cc. of
i.e.
it
50 per cent. By extracting again with 50 cc. of benzene is apparent that 50 per cent of the remainder would be
extracted, or 25 per cent of the original quantity. Hence, by extraction with 100 cc. of benzene, using successively 50
cc.
portions, the total

is
amount
of the dissolved substance
removed
75 per cent as against 66 f per cent when it was all used at once. It is better, therefore, to extract several times with small quantities of the liquid than to extract once
with a volume equal to the aggregate of the volumes used.
CHAPTER XVI
VAPOR PRESSURE
boils at a lower temperature on a high mountain does in a valley. This is commonly explained by saying that the pressure exerted by the atmosphere on the surface of the water is less at the higher altitude, or that the
WATER
it
than
liquid water passes into the
vapor phase at a lower tem-
perature when the pressure is diminished. This fact is made use of in organic chemistry when we carry on the operation known as distillation under diminished pressure. At these respective temperatures under their corresponding pressures there exists a state of equilibrium between the vapor and the liquid, and the liquid will all pass over into the vapor phase without change in temperature, if heat be
continuously supplied. If at these various temperatures of equilibrium the corresponding pressures be determined and
represented diagrammatically so that the ordinates represent the pressures and the abscissae the temperatures, and if the points are connected by a curve, we should have the
temperatures and pressures. as the Vaporization Curve and represents all possible temperatures and pressures at which the It can thereliquid and vapor are in stable equilibrium.
values
for
all
intermediate
Such a curve
is
known
fore be designated the vapor exerts
an Equilibrium Curve. The pressure that under these conditions of equilibrium is
designated the Vapor Pressure of the substance. Methods of determining vapor pressures of substances
are usually classified as the static
1 68
method and the Ramsay

and Young or dynamic method.
substance
is
169
By
the
static
method the
placed in a Torricellian vacuum above a column of mercury, is heated, and the pressure determined by change in height of the column of mercury.
By
the
Ramsay and Young method

is
constant and the temperature that pressure is established.
the pressure is kept varied until equilibrium at
We shall consider the vapor pressure determinations of two substances, benzene and water, and represent them diagrammatically. When the pressures are represented as ordinates and the temperatures as abscissae, the diagram is known as a p-t diagram, that is, a pressure-temperature
diagram.
The following values for benzene have been found by Ramsay and Young, and subsequently confirmed by Fischer
TABLE
t
XXIX
VAPOR PRESSURE OF BENZENE
170
PHYSICAL CHEMISTRY
the pressure axis represents the pressures and temperatures at which benzene will exist as a liquid.
In a like manner
of
we
give values for the vapor pressure
water
TABLE
t
XXX
VAPOR PRESSURE OP WATER
171
The mass
vapor phase
of the phase or phases does not influence the

will disappear.
if we increase the pressure, the The pressure is independent of
equilibrium of the system, for
the relative or absolute volumes of the vapor and liquid If the pressure and temperature are maintained conphases.
stant, it does not
matter whether we have 500 or 50 cc. of the
liquid present, the equilibrium will be preserved and we could remove most of the liquid without disturbing the equilibrium.
It Limits of the Vapor Pressure Curve. it and to what temperature pressure inquire
is is
natural to
possible to
subject a two-phase liquid- vapor one-component system, such as water or benzene, and still obtain a condition of equilibrium between the two phases. The vapor pressure curve is a boundary curve and separates the area of the
if
diagram into the areas of pure liquid and pure vapor hence, we follow this curve to a sufficiently high temperature with its corresponding pressure, we reach the point at which there is no distinction between the liquid and the vapor phases, and the system ceases to be heterogeneous and is a homogeneous single phase. This would occur at the at which there is no distinction between the temperature
;
vapor and
at the critical temperature, and the called the critical pressure. Hence, corresponding pressure, the vapor pressure curve must end at the critical point, and
liquid, that
is,
above
this
temperature there
is
no pressure great enough

In the case of water the
to produce the liquid phase.
vapor pressure curve would terminate at a temperature of 633 absolute, and a pressure of 195.5 atmospheres, which
are called respectively the critical temperature pressure of water. For benzene the critical
561.5
It is
and
critical
values are
absolute and 47.89 atmospheres pressure. a familiar fact that if the temperature of a liquid, as water, is lowered, there occurs a time when the substance
ceases to exist in the liquid phase and a new phase appears the solid phase. Hence, it follows that there must be a
172
PHYSICAL CHEMISTRY
lower limit to the vapor pressure curve for liquid water, that is, to the vaporization curve. It is also a familiar
fact that
when
This is due to the fact that the water on exposure to the cold becomes ice and later disappears in the form of vapor. That is, the solid water (ice) passes directly from the solid to the vapor phase without passing through the intermediate liquid phase. This happens in the case of a large number of substances, for example, if mercuric chloride is heated at ordinary atmospheric pressure, it liquefies, and if the heat be increased, the liquid
passes into the vapor phase. diminished to 200 or 300 mm.
If,
they freeze, thus becoming found to be soft and dry.
clothes are placed on the line in winter, stiff and hard. Later they are all
and heat
however, the pressure is applied, it is found
that the solid passes over into the vapor phase without This paspassing through the intermediate liquid phase. sage of a substance from the solid to the vapor phase without passing through the intermediate liquid phase is desig-
nated sublimation.
The solid like the liquid has a certain the vapor phase, and as this can be to into pass tendency measured as a pressure, we speak of the vapor pressure of This tendency to sublime can be measured in a solids.
manner somewhat analogous
to the determination of the
liquids,
vapor pressure of
and
it
;
may
be
represented on thep-t diagram the curve representing the vapor pressure of a solid
is
an equilibrium curve and represents the equilibrium between the solid (ice) and vapor, and is called the Sublimation
Curve.
In
pressures are given in Table XXIX. Representing these data on the p-t diagram, Fig. 24, we have CD, which terminates at the melting point of benzene, that is,
FiG^J
the case of benzene the vapor
where the sublimation curve intersects the vaporization curve.

In the case of water we have the following values for the vapor pressure of ice
:
TABLE
/
XXXI
VAPOR PRESSURE OF ICE
PHYSICAL CHEMISTRY
If the vapor pressures of all mixtures of A and B are intermediate between the vapor pressures of A and B, then the curve AB represents the vapor pressures of all mixtures,
and the
total pressure is the sum of the partial pressures of the vapor of the two components. The addition of a second component to a solvent may affect the vapor pressure in
one of three ways

(2) it
it.
may
lower the vapor pressure, raise the vapor pressure, or (3) it may not affect
:
(i) it
may
and
In the pressure-concentration diagram, Fig. 27, let C represent the vapor pressures of two miscible liquids,
then as we add D to C the vapor pressure of C is raised. If we take D as the solvent and add C, the vapor pressure will be raised, and if we plot these results we obtain a curve represented by COD which indicates a maximum vapor
pressure for
some mixture
of these
two miscible
liquids.
C
100%
D
100%
FIG. 27.
FIG. 28.
In the pressure-concentration diagram, Fig. 28, let E and represent the vapor pressures of two miscible liquids. Let us assume that the addition of the second ^component diminishes the vapor pressure of the solvent then by adding F
;
the vapor pressure will be decreased, and similarly by adding E to F the vapor pressure of the mixture will be less
to
than that of F. By plotting such results we obtain the curve EMF, which represents a minimum vapor pressure while in the first case, where the vapor pressures of the mixtures were intermediate between the vapor pressures of the
;
175
two components, we have neither maximum nor minimum

pressures.
sure which
have already seen that the vapor pressure is the presis necessary to balance the tendency of the solvent to pass into the vapor phase, and at a given temperature this tendency is much less than it was before the solute was
added.
It will
We
be necessary to raise the temperature con-
siderably to form the amount of vapor sufficient to produce the pressure equivalent to the pressure of the vapor of the pure solvent. Therefore, the liquid with the lower vapor
pressure at a given temperature is the liquid with the higher boiling point. Representing the pairs of liquids A
on a temperature-concentration we would have the boiling point of A higher than that of B, and since the vapor pressure of mixtures of the two liquids is intermediate between that of the liquids
diagram, Fig. 29,
themselves, the boiling point of their solutions
and
m%
FlG 2g
is
intermediate
between the boiling points of the pure liquids, as is shown by the line A B, which represents the boiling points of all
mixtures of
and B. the same amount of vapor from solutions of two miscible liquids which can have a minimum vapor pressure, requires a larger expenditure of energy in the form of heat than to produce the same pressure from the pure solvent. So if we take different mixtures of two miscible manifest minimum vapor pressures and dewhich liquids termine the boiling points and plot them on a temperature-
To produce
concentration diagram, as in Fig. 30, we obtain the curve EMF, which shows that as we add the component F to
the solvent the boiling point is raised, and the rise is greater the greater the concentration within certain limits. The same is true if we use F as the solvent, and as we add
i 76
PHYSICAL CHEMISTRY
the boiling point of the solutions increases with the increased concentration of E. We obtain the curve
EMF
E
which shows a
maximum
boiling point for mixtures of
100*
100*
/>
FIG. 30.
FIG. 31.
and F.
curve.
Pairs of miscible liquids which have a
minimum
vapor pressure curve also have a

Similarly
it
maximum
boiling point
two miscible
curve (Fig.
be shown, as represented in Fig. 3 1 that liquids which have a maximum vapor pressure 27) have a minimum boiling point curve, COD.
may
COMPOSITION OF THE VAPOR PHASE
The vapor phase under constant pressure and temperature will be in equilibrium with the liquid phase, and we have just seen that the pressure of the vapor phase is due
to the vapor pressures of the individual components of the vapor, i.e. p = pi -\- pz, which is Dal ton's Law. The con-
sures,
centrations in a gas are proportional to the partial presand hence we could determine the concentration of
the components in the vapor phase if we knew the partial The determination of the partial pressures is pressures.
and satisfactory methods have not been devised. But we can determine the concentration by distilling over fractions, collecting, and analyzing them. Let us consider a pair of liquids whose mixtures have
difficult,
boiling points intermediate
between the boiling points
of

the two components.
177
two components and

mixtures.
A and B represent the the boiling points of the AyB represent Let us consider* a mixture represented by the
In Fig. 32
let
'
point p, the composition of which is, say, 80 per cent A and If we heat this mixture and continue to 20. per cent B.
raise" its
temperature until we intersect the boiling point at z, the liquid will boil at this temperature, / and the vapor which passes off will be richer in B than in A.
curve
AB
of the. liquid in the flask will rise and pass line the zA, and the concentration of the liquid in the along flask will approach the composition
The temperature
of pure
A.
The
distillate
passes off at z is the liquid from which

tilfed,
richer in
it
which than was dis-
and may be represented by

x.
is
some point as
If
the vapor of
*
IT
this composition then heated to

it
condensed and
boiling point, to boil at the
will
boil,
its
will
be found
t
temperature
richer in
y.
This
is
and the vapor
will
be
represented by the concentration y, The vapor w, if coni.e. some concentration such as w. densed, would be found to have a boiling point /, and the
than
vapor of
in B,
ficient
this
would be
redistillation
we
times we approach B and thus comfrom A. From the liquid remaining in the flask we obtain A and from the distillates pure B, and therefore can completely separate them by this means, which is termed fractional distillation. Any point on the curve
of
it
and it is number
richer in B. By this, process of are obtaining distillates successively richer apparent that if this be continued a suf-
pletely separate
BwxA represents the composition of the vapor phase, i.e. of the distillates, at the boiling point of the mixture from
which
it
was obtained.
This curve
is
called the
Vapor
Composition Curve.
178
PHYSICAL CHEMISTRY
In Fig. 33, where we have a maxiiattm boiling point, the vapor composition curve is represented by the dotted curve
CcOdD.
If
we take any mixture
richer in
than the
maximum
boiling mixture, and fractionate it, the distillate be will richer in D than in C, and the composition of the liquid in the flask becomes richer in C. For mixtures richer in
C than the maximum boiling mixture, the vapor will be richer in C and the composition of the
c
liquid remaining in the flask becomes richer in D. For any mixture the
concentration of the liquid in the flask tends to become of the concentration as represented by the concentration 0, at which the boiling 1 1*1 r point is the highest or any mixtures
j j
j
j
100*.
of the vapor
we
of C and D, and the composition the same as that of the distilling liquid, i.e. have a constant boiling liquid, and all of. the liquid
'
FlG 33
'
is
passes over without change in temperature. This phenomenon is the same as in the case of pure substances. The boiling point is used as a means of deter-
mining whether a substance

is
constant,
we conclude
If the boiling point is pure. that the substance is a pure one
and that the composition

the same.
vapor and of the liquid are be applied to this boiling mixture, the conclusion would be that it is a pure chemical compound. For a long time such mixtures were considered as chemical compounds. In the case of pure substances
of the
If this criterion
the composition of the liquid and vapor phases is the same, irrespective of the pressure at which the boiling point is determined. If, however, these constant boiling mixtures
of pairs of miscible liquids be determined at different pressures, vapors of different composition will be obtained.
This proves that they are not chemical mixtures.
compounds but

In Fig. 34,
179
EeMfF is the vapor composition curve of the from the mixtures of pairs of liquids with a jniaimum boiling point. The distillates of mixtures whose boilare richer in F than the ing points are represented by mixtures from which they were obtained, and as these distillates are continuously fractionated by distillation the comdistillates
EM
liquids
position of the distillate approaches whose boiling points are
M.
<
Similarly, for the
the composition represented by of the distillates obtained by fractional distillation approaches the final value. That is, the
tillates
MF
M as
dis-
of all mixtures
upon
frac-
tionation give as final values
the
'" *
-jr
composition represented by M, which is that mixture with the lowest

boiling point.
FlG> 34
'
At
this
temperature the mixture of this
at constant temperature and the vapor and liquid have the same composition. What was stated with respect to the point of the maximum boiling liquids
composition
distills
of the minimum boiling liquids the applies to the point composition varies with the pressure and therefore they are
;
not pure chemical compounds. Mixtures of the type illustrated in Fig. 32 are not very common. In the case of methyl alcohol-water and acetonewater mixtures, approximate separation by fractional dis-
can be obtained. Mixtures of the type illustrated in Fig. 33 are represented by a number of solutions of acids in water where
tillation
maximum boiling Table XXXII.
points
are
obtained as illustrated in
Mixtures of the type illustrated in Fig. 34 are common, and a few of the more common pairs of miscible liquids that have a maximum vapor pressure and a minimum boiling point
are given in Table
XXXIII.
180
PHYSICAL CHEMISTRY
TABLE XXXII

FRACTIONAL DISTILLATION WITH STEAM
181
In the case of a one-component system of a liquid and

vapor, the vapor pressure of the pure liquid at the boiling
sure.
point under atmospheric pressure is equal to 760 mm. presThat is, the vapor exerts a pressure of this amount
of
In the case against the tendency of the liquid to vaporize. two non-miscible or partially miscible liquids, the vapor
pressure of these at the boiling point of the mixture will be the sum of the partial vapor pressures of the two liquids. This will be equal to the external or atmospheric pressure, if If carbon bisulphide boiling under atmospheric pressure.
50 C. the vapor pressure at this temperature is balanced by the atmospheric pressure, and if we have water mixed with it at this temperature the vapor pressure of the water is appreciable, as p = p cs, PH&, hence the vapor
boils at
CSz does not have to equal the atmospheric the combined pressures of the carbon bisulphide as pressure, and of the water are equal to the external pressure. It is,
pressure of
therefore, apparent that the aggregate pressures of the two vapors will equal the atmospheric pressure at a temperature
below 50, the boiling point of the lower boiling liquid. That is, the mixture will boil at a temperature below that of
the lower boiling liquid.
in the
The
quantities of the substances
vapor
phase will, of course,
depend upon the vapor

This
pressure of the substances at that temperature. be illustrated by a specific case.

boils at 99
may
In the distillation of nitrobenzene by steam the mixture C. at a pressure of 760 mm. At this temperature the vapor pressure of water is 733 mm. and that of the nitrobenzene would be the difference 760 733 or 27 mm. Since 22.4 liters, the gram-molecular volume, would contain
1 8 grams of water vapor under the standard conditions, an equal volume under 760 mm. pressure and at o would contain 123 grams of nitrobenzene. Since the volumes
182
are
PHYSICAL CHEMISTRY
indirectly proportional to the pressures have, as the weights are proportional to the
18
we would
gr.
gr.
760
mm.
733
mm.
pressures, (the vapor pressure of
water at 99
C.).
This gives -
733
grams
of
water
*
760
which would pass over.
In a like manner
we
find
760
grams
of nitrobenzene in the distillate.
These give us the

:
733 or 367 1466 or i 4 as the 760 relative weights of the distillates. As the water is much than the the of water is much volume lighter nitrobenzene,
ratio of
I23
2?
l8
760
larger relatively to that of the nitrobenzene that passes over. If the molecular weight of the substance being distilled
with steam is not known, it can be readily calculated by measuring the volume of the liquids distilled over, and from
from
their specific gravities the weight could be determined and this ratio the value of in place of the molecular
weight of nitrobenzene
vapor could be calculated.
CHAPTER XVII
PHASE RULE
SINCE we know that the existence of water in the vapor, phase depends upon the conditions of tem-
liquid, or solid
perature and pressure, the limiting value for any particular
phase is a question merely of the relation of these factors. In a consideration of the subject of phases and of the problems of equilibrium from this point of view, we practically take
into consideration the heat
and volume energy and leave out of consideration the force of gravity, electrical strains and stresses, distortion of the solid mass, capillary tension, etc., and thus confine ourselves to those systems wherein there exists only uniform temperature, pressure, and chemical
potential.
In a system that contains only one phase, unless we have both the pressure and temperature designated, the conBoth of these factors are needed centration is not known. to establish the system. We know that both of these independent variables can be changed within certain limits and the system still be maintained as a one-phase system. Then the question arises What are the limits to which these independent variables can be varied and yet retain the system as a one-phase system ? That is, What are the boundaries of any of these different possible one-phase systems such as
:
water, and what will happen to the system when these limits are exceeded? If the pressure and temperature are varied
in the proper direction, a
vapor can be made to condense into
a liquid,
the greater the pressure the more of the vapor will and the greater the liquid phase will become. The disappear
183
1 84
PHYSICAL CHEMISTRY
concentration of the system has increased and we have a two-phase system. If, on the other hand, the pressure is diminished and the temperature increased sufficiently, it
may break up and become disintegrated by the decomposition

of the components. So that the boundary limits in all directions are not accessible and hence not easily established
experimentally.
By
water
decreasing the temperature of the two-phase system of

liquid
a new phase appears. This is we have the system more (ice). for none of the variables can now be it as were, securely fixed, the without changed causing disappearance of some of the if the phases ice, temperature is increased, or liquid, if the temperature is decreased. Every phase of a system has its boundaries or limitations on all sides, that is, its sphere of existence. These boundaries are represented by the in-
and vapor
the solid
When
this occurs
dependent variables
centrations.
amount
the temperature, pressure, and consee then that every system has a certain of freedom in the variation of its variables in so far
We
as the identity of the system is not destroyed, and we have also seen that this sphere of freedom is not necessarily
bounded on
existence
all
"
is
This "sphere of sides by other phases. spoken of as the number of degrees of freedom
"
of the system and is defined as the number of the variable factors temperature, pressure, and concentration of the
components
the conditions of the system
which must be arbitrarily fixed in order that " may be perfectly defined. Findlay's Phase Rule, p. 16. A gas would have two degrees of freedom because, in order to determine its concentration, we should have to define both the pressure and temperature. A system, liquid-vapor, has one degree of freedom, while a system, solid-liquid-vapor, has no degree of freedom, because a change of any of the variables would cause one of the phases to disappear and the equilibrium to be disturbed.
PHASE RULE
185
In speaking of the amount of variance or variation of the system, we say that the system is non variant (invariant), monovariant, divariant, multivariant, etc., when the number
etc.
of degrees of freedom is respectively zero, one, two, three, This relation between the number of degrees of freedom,
number of independent variables, and the number of components of the system has been expressed by Gibbs in his celebrated Phase Rule, which defines the system completely. The number of This Phase Rule may be stated as follows degrees of freedom of a system is equal to the number of components plus two, minus the number of phases. This may be
the
:
expressed by the following equation
JV +
in
- P= F
components,
which
is
the
number
of
the
number
of
phases, and F the number of degrees of freedom, or the variance of the system.
The concept of phases has been of great importance in aiding the classification and correlation of a large number of isolated facts, in the interpretation of new phenomena, and
in guiding us in the discovery of new In this respect the Phase relations.
classification of interrelated
phenomena and
is
their
Rule as a system of
to chemistry in
phenomena
is
It to inorganic chemistry. is really a basis of classification of the phenomena of chemistry rather than a separate division of the subject.
general
what the
periodic law
Ostwald goes even farther and states that it is possible from the principles of chemical dynamics (the theory of the progress of chemical reaction and the theory of chemical equilibrium) to deduce all of the stoichiometrical laws, the
-
laws of constant proportion, the laws of multiple proportions, and the law of combining weights. Through this conception
by Gibbs and amplified by himself and Franz Wald, Ostwald proceeds to deduce these laws in his Faraday Lecture (Jour. Chem. Soc., 85, 506 (1904)).
of the phase introduced
86
PHYSICAL CHEMISTRY
SYSTEM OF WATER
diagram, Fig. 35, represents the whole range of temperatures and pressures of the system water, and this
p-t
The
area
is
divided into three areas representing the ranges of
temperature and pressure at which water can exist as vapor,

as liquid,
of
and as
phase,
solid.
Each
1
one
2
hence,
of these three systems consists according to the Phase Rule
N+
P=
F,
we have
of
2;
i.e.
two degrees
freedom or a Divariant System. The three divariant systems then are: 1. The area DCB-t-axi$ representing
the vapor phase, 2. The area ECB representing the
liquid phase,
The area DCE-p-axis representing 3 the solid phase. It is apparent, as in the case of the liquid phase, that at a point such as G, if the temperature be kept constant, there
0"
.
FIG. 35.
number of pressures to which the liquid can be without subjected introducing a new phase or causing the to liquid phase disappear. Likewise, if the pressure at G be kept constant, there are a large number of temperatures
are a large
at which the liquid phase persists, i.e. the liquid phase is capable of existing at various temperatures at the same
This is true of any other phase each pressure has pressure. a number of temperatures and each temperature a number of pressures at which the phase exists. The boundary between the vapor area and the liquid area is represented by the curve CB, which is the Vaporization Curve and represents the equilibrium between the liquid and
;
vapor phases. Since we have two phases in equilibrium, 2 2 = 1, according to the Phase Rule we should have 1 or a Monovariant System. The same is true of the equilibrium
curve between vapor and
solid,
represented by the Sublima-
PHASE RULE
tion Curve,
187
liquid
three
DC, and the equilibrium between the solid and represented by the Fusion Curve, EC. Hence we have monovariant systems represented by the following
:
curves
1.
CB, representing equilibrium between the
liquid
and
vapor phases,
2.
CD, representing equilibrium between the vapor and

CE, representing equilibrium between the
liquid
solid phases,
3.
and
solid phases.
The
intersect for water at a point
three curves representing the monovariant systems known as the triple point.
This point represents the only temperature and pressure at can which the three phases solid, liquid, and vapor exist in equilibrium for water this is at 4.6 mm. pressure and
;
0.0075. According to the Phase Rule, since we have three phases present we should have 1-1-23 = 0; i.e. the system is a Nonvariant System. We have just denned the boundaries of the various phases
at
when
in equilibrium, but it is natural to inquire if any particular phase can exist under any other conditions than It is known that if those represented by the diagram.
vapor
is
perature
cooled very carefully, it can be obtained at a temmuch below that at which it should condense and
become a liquid. In the diagram, Fig. 35, let F represent some temperature and pressure of the vapor. By cooling
the vapor very carefully it may be made to follow the conditions represented by the line FG, and at G, in the liquid That is, the vapor is area, the vapor phase still exists.
capable of existing under other conditions than that represented by the area designated vapor, but under such
conditions the system
;
is said to be in a state of labile equilibrium and if a minute trace of the liquid phase be introduced, some of the vapor will become liquid and assume a condition of stable equilibrium with the vapor represented by a point
88
PHYSICAL CHEMISTRY
on the equilibrium curve CB. If we continue to cool the monovariant system, liquid-vapor, it is possible to continue the curve CB into the solid area to A without the appearance of the solid phase. That is, we have undercooled the liquid below its freezing point. If, however, a portion
,
is introduced, the liquid phase will disappear and the system will become a system composed of solid and vapor in equilibrium. We have not been able to obtain the solid phase under such conditions that a liquid or vapor exists, but a liquid can be heated above the temperature at which it is in equilibrium with the vapor phase and be represented in the vapor phase area. It is claimed that water has been heated to about 200 C. and still remained in the
of the solid phase
liquid phase.
C we have the three phases in equithe system, solid-liquid-vapor, be heated, the solid phase will disappear first and the equilibrium between and if heat be continually liquid- vapor will be produced
At the
triple point
If
librium.
added, the system will take the direction represented by the curve CB. If the system be cooled, the liquid water will disappear and the equilibrium will be described by the
curve CD, which represents the equilibrium between ice and vapor. The triple point C for water is not exactly o C., as the
melting point is defined as o under a pressure of 760 mm. This ice is under its own vapor pressure, which is nearly 4.6
mm.,
From Table practically one atmosphere less. which gives the fusion pressure of ice for pressure as high as about 2000 atmospheres, it is found that an increase of one atmosphere lowers the melting point of ice it would require 134 atmospheres to change the 0.0075,
or
XXXIV,
*"
melting point
C.
PHASE RULE
189
TABLE
XXXIV
FUSION PRESSURE OF ICE
TEMP.
190
PHYSICAL CHEMISTRY
;
dimorphous
phous.
for three, trimorphous
for four, tetrarhor-
The term polymorphism is frequently applied to both compounds and elements, but does not include the
allotropy of
amorphous substances, such
as ozone, or of
liquid sulphur. Types of Polymorphism
or Allotropy. The different allotropic modifications of substances have different and distinct physical properties crystalline form, melting
:
point, rate of expansion,

electricity, color, etc.
conductivity of both heat and
The transformation of a substance from one phase into another takes place at constant temperature for a given This is illustrated by the change of liquid water pressure.
into ice, where
we have
the two phases coexisting in equilibrium pressures the reverse change may occur.
the appearance of a new phase and or at very high The conditions

;
of temperature and pressure under which the change of one phase into another occurs or where a new phase appears
and
coexists in equilibrium with the others
is
termed the
transition point.
the transition
pressure,
The temperature at which this occurs is temperature, and the pressure, the transition
which, however, may vary over wide ranges without appreciably affecting the temperature of equilibrium, and as a result is many times neglected, particularly in the case of such transitions as that of a iron into
/3
iron.
The
transition point
is
also called
the inversion
point.
The three following types of polymorphic or allotropic substances exist

:
Enantiotropic substances are those whose polymorphic forms may be directly transformed one into the other, and
I.
the transition point the forms.
lies
below the melting point of each of

well-marked examples of
inorganic substances.
In Table
XXXV are listed a few
enantiotropic polymerization
among
PHASE RULE
191
TABLE
SUBSTANCES
XXXV
I Q2
PHYSICAL CHEMISTRY
irreversible
being reversibly transformable and polymorphism of this kind is termed monotropy. It is known that two of the III. Dynamic Allotropy.
liquid forms of sulphur, S\ definite proportions, which
and S M can exist together in depend on the temperature.

,
The various is termed dynamic allotropy. polymorphic forms cannot exist together except at the transition point, but those manifesting dynamic allotropy can do so, and this is explained on the basis of the existence
This phenomenon
solid
of molecules of different complexity. Smith and his colaborers have shown that the
,
two
liquid
phases of sulphur, SA and S M have different solubilities in a number of different solvents diphenylmethane, di:
phenyl, /?-naphthol and triphenylmethane in these solvents with an absorption of heat as

;
S A dissolves
shown by the
tion of heat as
ascending curve of solubility, while S^ dissolves with evolushown by the descending curve of solubility.
Many
substances that manifest polymorphism have labile
modifications that exist at temperatures far below the transition point or inversion temperature as in the case of calcite
aragonite, the two solid modifications of calcium carbonate. On heating, aragonite changes to calcite, but at ordinary temperatures the two forms exist in apparent
stable equilibrium. In the case of carbon the three modifications exist together under ordinary conditions of tem-
and
perature and pressure, which is possibly due to the high The same is probably true in the inversion temperature. case of titanic acid and many others.
ONE COMPONENT SYSTEM
SULPHUR
The p-t diagram for sulphur is represented in Fig. 36. Sulphur exists in two solid crystalline forms, the rhombic, stable below 95.5, and the monoclinic, the stable form, between 95.5 and 120.
PHASE RULE
This figure will probably be more readily understood
is
193
if it
redrawn, first drawing the p-t diagram for rhombic sulphur and then drawing the p-t diagram for monoclinic sulphur superposed upon this with the
melting point of monoclinic sulphur (120) located upon the vapor pressure curve for rhombic sulphur. Applying the phase rule to the
various systems represented
by the
Vapor
areas, lines, and points as we did in the case of the p-t diagram for
water we would have

I.
Fields
or
areas.
have one phase. Phase Rule,
Here we Then from the
IlA 120*151* Sulphur
FIG. 36.
P 2 = F, substituting, we have i i Therefore the areas represent divariant systems. There are four of these
2.
1.
2.
3. 4.
II.
1
Area under line EFCB sulphur vapor Area to the right of BCGH liquid sulphur Area to left of EFGH rhombic sulphur Area of the triangle GFC monoclinic sulphur Curves. According to the Phase Rule we have,
2
1,
therefore monovariant systems:
3. 4.
5.
6.
Curve Curve Curve Curve Curve Curve
EF FC CB
CG
rhombic-vapor
monoclinic -vapor
liquid-vapor
monoclinic-liquid
GH
FG
rhombic-liquid rhombic-monoclinic
III.
At the
intersection of
three phases in equilibrium,
Rule we have These are called

1
.
13 + 2=0;
triple points.
some of these curves we have and according to the Phase

therefore nonvariant systems.
Point Point
F C
rhombic-monoclinic-vapor
monoclinic-liquid-vapor
IQ4
3
.
PHYSICAL CHEMISTRY
Point
rhombic-liquid-monoclinic
4.
Point
labile equilibrium
rhombic-monoclinic-vapor is a condition of and is not readily realized.

of
The
intersection
the
two sublimation curves
at
represents the transition point 95.5 at which rhombic and monoclinic sulphur are in equilibrium. Below this temperature rhombic sulphur has the lower vapor pressure and is the
stable form, while above this temperature monoclinic sulphur is the stable form.
CHAPTER
XVIII
I
SOLUTION OF SOLIDS IN LIQUIDS
THE
solubility of
solid in
a liquid depends upon the
nature of the solvent as well as upon the solute. The solubility is also usually greatly affected by the temperature,
but the pressure does not have such a marked effect. In Figs. 37 and 38 we have represented the change in the solubility of solids in water with changes in temperature. These are termed temperature-concentration diagrams.
ments of the same family,
Generally speaking, the analogous compounds of the eleif arranged in the order of their
FIG. 37-
FIG. 38.
be found to be in the increasing or the deof their atomic weights. order creasing Cs, Rb, K, Na, Li, with decreasing order of atomic weights,
solubility, will
have increasing
solubility of their chlorides
and
nitrates.
This does not hold absolutely. These solubility curves are equilibrium curves and represent the equilibrium between the solid salt and the solution, which is saturated with respect to the solid phase
separating.
saturated solution is then a solution, at a specified temperature, in equilibrium with the solid phase.
196
If
PHYSICAL CHEMISTRY
curves, as in Fig. 37,
we have two
A B must
represent the
solubility of
one chemical individual and BC that of another. That is, along the line A B a different solid phase separates than along the line BC. Below the curve A B we have un-
saturated solutions, and on the curve, saturated, and above, supersaturated solutions. In all solubility work we must
consider
since
what
solid is in equilibrium
with the solution, and
many
salts separate
with water of crystallization,
we
may have the same solubility at different temperatures. It must be remembered that a solution is saturated with respect to a particular substance only when it is in equilibrium with that particular substance at the specified temperature.
The solubility of organic substances, likewise, depends upon the solvent and the solute, that is, upon the chemical
character of both.
In water, almost all substances containing the hydroxyl group (OH) dissolve more or less In the case of organic acids, the readily, e.g. the alcohols.
solubility of the
members
of a
homologous
(e.g.
series decreases
as the carbon content increases
The solubility of butyric). series is small. Benzene, C 6 6 is insoluble in water phenol, C 6 6OH, is soluble to the extent of about two per cent in
formic, acetic, propionic, the higher members of the

;
water
tions
while dihydric phenols,

3
and trihydric phenols,

with water.
C H 4 (OH) are very soluble, C 6H (OH) are miscible in all propor6

2
,
3,
Following the analogy, practically
all
alcohols are soluble in alcohol

all
and
all
acids in acetic acid,

effort
hydrocarbons in benzene,
etc.
An
has been
made
by Carnelly and Thomson (Jour. Chem. Soc. 53, 782 (1888)) to formulate some rules for the solubility of substances, and
they
i.
the following general statements any series of isomeric organic compounds the order of solubility is the same as the order of fusibility the most fusible is the most soluble. Taking all solvents
:
make
That
for
into account, 1755 out of 1778 cases hold.

2.
197
is
In any series of isomeric acids not only
the order
of solubility of the acids themselves the same as the order of fusibility, but the same order of solubility extends to all
the salts of the second acids, so that the salts of the more soluble and more fusible acids are also more easily soluble
than the corresponding salts of the less fusible and less Five exceptions out of 143 cases were found. soluble acids. 3. For any series of isomeric compounds the order of solubility is the same no matter what may be the nature of the solvent. No exception to this was found out of 666
cases.
4. The ratio of the solubilities of the two isomerides in any given solvent is very nearly constant, and is therefore
independent of the nature of the solvent. In the pitch of the solubility Pitch of Solubility Curve. curve one has some criterion as to the true heat of solution of the particular substance. By inspecting a solubility curve
the sign of the heat effect involved in the solution of the substance can be ascertained. If the substance dissolves
with an absorption of heat, it will dissolve in greater quanMost inorganic salts tity as the temperature is increased.
dissolve in water with absorption of heat, and their soluExbility increases with an increase in the temperature.
amples are NH 4NO 3 and NH 4CNS. A number of salts dissolve with the evolution of heat, and their solubility decreases with increase in temperature; examples are most anhydrous sulphates, calcium isobutyrate, etc. We have a large number of salts, intermediate between these two classes, which dissolve with practically no heat effect, and the solubility of which is nearly constant for wide ranges of temperature. Common salt, NaCl, is an example of this
class.
must not fail to distinguish between the heat of solution usually determined in thermo-chemistry and the true heat of solution, or perhaps it had better be called the
We
198
heat
PHYSICAL CHEMISTRY
By of precipitation, which has the opposite sign. heat of solution or heat of precipitation we mean the heat effect when the solute is added to an almost saturated solution.
the heat effect

of
The heat of solution in the thermo-chemical sense is when the solute is dissolved in a large amount water and is very much more easily measured than the
of precipitation. Calcium isobutyrate below 80 dissolves in a large quantity of water with evolution of heat, in a little water with absorption of heat. Cupric
heat
chloride dissolves in a large amount of water with evolution of heat, and this heat effect decreases as the quantity of water used is decreased. In nearly saturated solutions
the heat of solution changes sign and

of heat.
It follows
we have an absorption
then that there must be some quantity of water
in
definite quantity of the salt will dissolve without either evolution or absorption of heat. This has been veri-
which a
fied experimentally in the case of the
hydrates of FeCla.
of precipitation of NaCl is very nearly zero, and consequently the change in the solubility of this salt with
The heat
the increase in temperature is very slight. So one can tell very readily the sign of the heat effect from the soluif
they are continuous curves. But a curve has a break in it at some point, a discontinuity, we know that some change has taken place, probably in the phases in contact with the solution. Hence any such sharp discontinuity will lead us to suspect that there is a change in the phase relations. As we have a number of such
bility curves, providing
cases
coming under the head
of hydrates
we
shall defer their
treatment.
THEOREM OF LE CHATELIER
We have seen that the results of the determinations of the effect of pressure on the fusion point of ice show that the temperatures at which the solid and liquid are in equilib-
199
rium are below the triple point. Ice has a lower density than liquid water, showing that the most dense phase of water is liquid water, hence when the system is subjected
to pressure it will tend to compensate for this external pressure by readjusting itself so as to occupy a smaller volume, and if we have ice present this increased pressure will result
in liquefying the ice,
volume.
If,
and the system will occupy a smaller however, the temperature at which the solid
and
liquid are in equilibrium is above the temperature of the triple point, the substance has a greater density in the solid than in the liquid state, and increased pressure will
is
tend to cause the system to pass into the solid state which the most dense. For substances in general, the solid is
the most dense phase.
Water
is
one of the few exceptions
to this general rule. In the case of benzene the
most dense phase is the solid. Hence an increase in the pressure will cause the freezing point to rise, and the fusion curve will slant away from the
If benzene is subjected to pressure axis toward the right. mm. the pressure, melting point will be raised 0.143. 3742.7 This fact, that by means of an increase in pressure the
most dense phase of the substance tends to form, represents one of the most fundamental laws. This law has its counterpart in the Law of Motion, that action and reaction are equal and in the opposite direction. This is known in chemistry as the Theorem of Le Chatelier and may be ex" pressed as follows Any change in the factors of equilibrium from outside is followed by an inverse change inside the system " i.e. there is a change in the factors of equilib:
rium tending to restore equilibrium. Hence by increasing the external pressure on a system there would be an increase of that component or phase occupying the least volume or if heat is added, we have an increase of that component or phase which involves an absorption
;
of heat.
Hence a system
in equilibrium tends to return
200
to
PHYSICAL CHEMISTRY
equilibrium
Ammonium
chloride
by eliminating the disturbing element. dissolves with expansion, and the
about one per cent by increasing 160 atmospheres. Copper sulphate dissolves with contraction, and the solubility increases 3.2 per
solubility is diminished
the pressure to
cent on increasing the pressure to 60 atmospheres. Sodium sulphate with 10 molecules of water of crystallization dissolves with absorption of heat, hence the solubility increases with an increase in temperature. All of these facts are in
accord with the Theorem of Le Chatelier. If a system is in equilibrium at a specified temperature and heat be applied, there will be a tendency to compensate
for this heat
added to the system by a readjustment within
the system either through a physical adjustment, such as increase of the volume if the pressure remains constant, or by an increase of pressure in order to maintain the volume
constant.
Or
if
this addition of
heat results in the com-
pensating change through a chemical reaction, such as the formation of ozone from oxygen, or in the preparation of
nitric oxide,
carbon bisulphide, acetylene, etc., or the dissociation of calcium carbonate, we shall have either an absorption of heat or an evolution of heat, depending upon
the particular type of reaction that is taking place under our In most cases of dissociation the inspecified conditions.
is associated with an absorption of that it is an For as heat is endothermic reaction. heat, is, the reaction and applied being accompanied by proceeds, an absorption of heat, the heat from the outside of the
crease in dissociation
system has to be applied to maintain the system at a constant temperature, so that a rise in temperature favors the formation of the products of the reaction. Ozone is prepared according to the equation 3 O 2 = 2 O 3 and the reIt is an is accompanied by an absorption of heat. endothermic reaction, and therefore the percentage of ozone formed increases with the rise in temperature. If
,
action

the reaction evolves heat
it is
2OI
said to be exothermic
and
takes place best with a decrease in temperature. The inversion temperature at which the rhombohedral
form of NH 4 NO 3 can be transformed into the /?-rhombic form can be changed from 85.45 under a pressure of one
atmosphere to 82.29 mospheres.
by increasing the pressure
to 250 at-
The following geological application of the Theorem of Le Chatelier worked out by Van Hise is a marked confirmametamorphic changes of the minerals, silicates by means of hydration, and carbonation, desilicification, which are accompanied of a liberation heat, decrease in the density, and an inby This region is known as the Zone crease in the volume. of Katamorphism, and in it the average specific gravity of
such as the alteration of the
the minerals is 2.948. In the inner zone of metamorphism, a few thousand feet from the surface of the earth, where there is an increased pressure due to the overlying rocks, there is also a much higher temperature than in the outer zone of metamorphism. This inner region is known as the Zone of Anamorphism, and we have the alteration of the minerals due to dehydration, decarbonation, and silicification, which are accompanied by an absorption of heat and condensation of volume, which are the typical changes.
tion of this principle. there takes place the
In the outer zone of the earth's crust
The average specific gravity of the minerals in Anamorphism is 3.488, which is about 18 per
the Zone of
cent higher
than that of the minerals in the Zone of Katamorphism. This is a fair approximation and shows that a given mass of material occupies a much larger volume in the Zone of Katamorphism than in the Zone of Anamorphism. A few special examples will serve to illustrate this. The change of hematite into limonite may be represented by the equation 2 Fe2 0s + 3 H 2 O = 2 Fe 2 O 3 3 H 2 O. This reaction takes place in the Zone of Katamorphism and is one of
202
PHYSICAL CHEMISTRY
hydration. The specific gravity of hematite is 5.225 and of limonite 3.80, which change represents an increase in volume of 60.7 per cent. One of the most common and best
known
Fe2 O 3
If
alterations
is
hematite into
:
siderite.
This
may
k
be
represented as follows
2H 2 S
+ CO =
2
FeSa
FeCO 3
+ 2HO+
2
cal.
the products of alteration are pyrite (isometric, sp.gr. 5.025) and siderite (sp.gr. 3.855), the increase in volume is
;
76 per cent but if marcasite (orthorhombic, sp.gr. 4.875) is formed instead of pyrite, the increase in volume of marcasite and siderite over the -hematite is 78.7 per cent. The most marked case known in which minerals are concerned
is
the alteration of magnetite into siderite.

4
Fe 3
+ CO + 2 CO = 3 FeCO
2
The equation the alteration represents
which gives a change of
specific gravity from 5.74 for magnetite to 2.83 for siderite, which represents the enormous increase in volume of 101 per cent. These changes all take
place with the liberation of heat, expansion of volume, and

decrease in symmetry.
typical example of deep-seated reactions under great pressure and high temperature, the change of calcite into
As a
one that is well known, CaCO 3 + SiO2 = k cal. Here we have a change in specific from 2.713 for calcite and 2.655 f r SiO 2 to 2 -&5 for gravity which wollastonite, represents a decrease in volume of 31.5 cent the silica is solid and the carbon dioxide per provided in all other deep-seated reactions, an We as have, escapes. of heat and condensation of volume as the typical absorption
wollastonite
is
2
CaSiO 3
+ CO
changes in the Zone of Anamorphism.
The same
of
the alteration of
principles are clearly illustrated in the case of silicates, which are brought up by means
some erogenic movement

it.
to the surface of the earth or
near to
silicates by hydration, carbonation, and desilicification is attended with the concomitant liberation of heat, a decrease in the specific grav-
This alteration of the

ity,
203
alteration of
and a marked increase
in the volume.
The
garnets into different combinations of the following minerals is well known: serpentine, talc, chlorite, epidote, zoisite,
magnesite, and gibbsite.

following equation, which is typical of these transformations, will suffice to illustrate the marked change
The
which amounts in
per cent
:
this case to
an increase in volume
of 76
+
pyrope
sp.gr. 3.725
15
H O + 3 C0
2
H Mg Si
2
3
12
+ 3 MgC0 +
3
A1(OH) 3
gibbsite
sp.gr. 2.35
cal.
talc
sp.gr. 2.75
magnesite
sp.gr. 3.06
CHAPTER XIX
II
THE SOLVENT AND SOLUTE CRYSTALLIZE TOGETHER MIXTURE OF THE PURE COMPONENTS
AS A
IN the two component systems in which we have a liquid solvent, and a solid solute, we assume that the vapor pressure
of the solid
is
so small that
it is negligible,
so that in the
systems we
volatile
and
I.
are to consider one of the components is nonone volatile. There are three general types of
:
such systems
solvent and solute may crystallize together Type as a mixture of the pure components. Type II. The solvent and solute crystallize in accordance
The
with the Laws of Definite and Multiple Proportions.
Type III.
The
solvent
in accordance with the
and solute crystallize together not Laws of Definite and Multiple Pro-
portions, but as solid solute dissolved in a solid solvent in varying proportions, within certain limits.
TYPE
SYSTEM WATER AND SODIUM CHLORIDE
At the intersection of the vapor pressure and sublimation curves for pure water, the solid, liquid, and vapor phases are in equilibrium, and we designate this the fusion point of
ice,
or the transition point.
As these phases are
in equilib-
rium under the pressure of the vapor of the system, it is a pressure of 4.6 mm. and at the temperature + 0.0075 C. The freezing point of liquids is the temperature at which the
204

solid
205
liquid phases are in equilibrium under atmospheric in the case of water would be under nearly which pressure, one atmosphere pressure more than at the transition temperAs an increase in pressure of one atmosphere lowers ature.
and
the melting point of ice 0.0076,

point, freezing point,
it is
and
transition point
apparent that the fusion may be considered
thep-t diagram, Fig. 39, represent the one-component systems by the following dotted lines. A B is the vapor pressure curve
let
the same.
On
us
AC is the sublimation curve
AD is the fusion curve

A is the triple point and represents the melting point of ice and the freezing point of water.
If
pIG
39<
a second component, solid salt, NaCl, be added to water, the vapor pressure of the solution produced is lower than the vapor pressure of the pure solvent water, and the amount of the lowering of the vapor pressure is proportional to the concentration. By adding successive amounts of NaCl the vapor pressures of the solutions would be represented by vapor pressure curves parallel to AB, but successively lower until we would reach a concentration
representing the maximum amounts of salt that are soluble at the different temperatures, when we would have saturated solutions, the vapor pressures of which we represent by CF.
This represents the
maximum
lowering of the vapor pressure
of the pure water. If these vapor pressure curves are prountil intersect the freezing point curve, we have jected they
the point A, the intersection of the vapor pressure curve
and the sublimation curve, passing down successively to the

point C, its lowest limit. Similarly, the curve AD, the fusion curve, would pass over the space to the left of its original position and take up as its final position, CE. A,
the freezing point of pure water, has been lowered from the
206
PHYSICAL CHEMISTRY
tc ,
temperature o to the temperature
and the distance along
the temperature axis represents the the freezing point.
maximum
lowering of
The degree of variance of this two-component system may be obtained by applying the Phase Rule as follows I. Areas. (N P 2 = F), 2 2 2 = 2.'. Divariant
:
systems
1
.
2.
Salt-vapor below GCF and above Solution- vapor between BACF.

Solution-ice between
Ice-salt
/-axis.
3. 4.
between
:
II.
Curves.
DACE. ECG and -axis. (N - P + 2 = F), 2 -
+2
.'.
Mono-
variant systems
1.
CF
Solution-vapor-salt.
Solution-ice-salt.
2.
CE
CG
3.
-4.
Ice-salt-vapor.
CA
Solution-ice-vapor.
III.
Point C.
(N - P
F),
+2
/.
Non-
variant system. At point C the four phases, solution-salt ice-vapor, are in This is known as a Quadruple Point. equilibrium.
If a body in the liquid state be allowed to cool without change of state, and measurement of the temperature be made at different times, and these results plotted on a a temperature-time axis, the curve has a regular form logarithmic curve when the cooling takes place for constant temperature surroundings. But if a change of state occurs, there is a decided change in the shape of the curve. In all cases observed the passage of a liquid to a solid is accompanied by the evolution of heat. This heat liberated compensates for loss of heat by radiation and maintains the
temperature constant, the solid separating and the process continuing until the whole of the liquid has changed to the
solid state,
when the temperature changes become
regular
again.
207
In Fig. 40 we have an illustration of the continuous cooling curve without change of state, while Fig. 41 illustrates the These show cooling curves of a number of pure substances.
a marked break at the temperature of the melting point of
Time
Time
FIG. 40.
FIG. 41.
above and below this the temperature falls at but this point the temperature remains conregularly, stant until all of the substance has solidified.
the substance
;
The cooling curves for two component systems, such as solutions of sodium chloride in water, differ from that of a
pure substance. For when solidification begins, either of the two components may separate, depending upon the concentration of the solution. At the point of solidification we have a marked break in the cooling curve, the separation of the pure component, which results in a change
in the concentration of the solution
with a lowering of the freezing point. Hence, on a t-time diagram for a

solution of the concentration of ten
per cent of sodium chloride, we should have the regular cooling of the solution,
Time
FIG. 42.
as represented by ab in Fig. 42, until at the point 6, the solid water (ice) begins to separate, and we have a change in the slope of the cooling curve. This
separation of the ice continues until the point c is reached, when the remainder of the solution solidifies completely.
208
PHYSICAL CHEMISTRY
cd,
During the time indicated by

constant.
the temperature remains

is
On
further cooling a regular cooling curve
obtained, as represented by de. By this method the cooling curves of solutions over the
whole range of concentrations desired may be obtained. The temperature, b, at which these a a solutions begin to solidify has thus been determined. So if
these values of the freezing points are plotted on a temper-
ature-concentration
diagram
against their respective concentrations and the points

FIG. 43-
connected, we obtain the
line,
curve represented by a dotted the freezing or solidification curve. If on this diagram the cooling curves be superposed so that the freezing points,
are placed on the freezing curve at the point corresponding to their proper concentration, we have the diagram repre6,
sented by Fig. 43. The first curve at the
left is the cooling curve for pure water, and we have the usual curve for a pure substance, with the break occurring at b when it begins to freeze, and the temperature remaining constant until the liquid has all
disappeared
as
(be),
when
shown by the
section
ce.
the cooling again becomes regular, It will be noticed that the cool-
ing curve for a solution containing 23 per cent of sodium chloride is exactly like this and is analogous to the cooling curve of a pure substance as shown in Fig. 41. That is, at
the temperature designated / the solidification begins, and the temperature remains constant until the whole mass has
solidified.
This
takes
the
time indicated
by
cd.
This
freezing point is different from the freezing point of any of these solutions in so far as the solidification takes place at constant temperature, and the composition of the solid

phase separating
is
209
the same as that of the solution from
This temperature is the lowest temseparates. at which perature any solution of these two components can It is also the lowest melting point of any mixture of exist.
it
which
the
two
components.
;
This
temperature
is
called
the
the solid which separates the eutectic and the point C, Fig. 44, is called the eutectic point. When water is one of the components, this point is also termed the
eutectic temperature
cryohydric point, the mixture the cryohydrate, perature the cryohydric temperature.
and the tem-
For
solid
all
solutions in
is less
chloride
which the concentration of the sodium than that represented by the point C, the
is
phase separating
pure water, while for
all
concentrachloride.
tions greater than C, the solid phase is pure
sodium
The curve ACB,
Fig. 44, represents the temperatures at
which solutions of sodium chloride begin to solidify, that is, where the solid phase appears. This is an equilibrium curve, and since it is not a continuous curve, but composed of two
branches, it must represent two different conditions of equilibrium, that is, along the curve pure
AC
water
is
librium
the solid phase in equiwith the solution, and
along the curve CB pure NaCl the solid phase in equilibrium with the solution. The curve A C
is
**
is
termed the Freezing Curve and
""freight fcrcem
the curve
the Solubility Curve, both of which are also Solidification or Fusion Curves.
CB
FlG 44
The
Eutectic Point
of
may
also
(of
two fusion curves

.
be defined as the intersection a freezing curve and a solubility

for the solidification of these difis
curve)
That the time required

ferent solutions
is
not the same,
shown by the
different
lengths of the horizontal sections cd, of the t-time curves.
210
PHYSICAL CHEMISTRY
This indicates that there are different quantities of the and consequently the times required for solidification will be different, and we have, therefore, an indication of the relative quantities of the eutectic separated
eutectic formed,
upon solidification of the The area above the

concentration
solutions of different concentrations.
curve,
Fig.
ACB, on
44,
the temperatureof
diagram,
sodium chloride in water;

solid ice separates;
represents solutions along the equilibrium curve
AC
along the equilibrium curve
CB
solid
NaCl, while at the intersection of these two curves at C a mixture of ice and salt separates, consisting of 22.43 P er cent of sodium chloride. Connecting the points designated
by
C,
we
obtain the line
DCE parallel to the
concentration
This represents the lowest limit of solidification of all mixtures of the two components. In the area between this line and the freezing curve, AC, we have solution and ice, and in the area between CB and CE there exist solution
axis.
salt, while below DCE we have solid only existing, which consists of the two crystalline species, ice and salt. The mutual solubility of AgCl and KC1 is represented on the tem-
and
perature-concentration diagram, Fig.
The melting point of KC1 is 790. As AgCl is added, the freezing point is lowered, and we obtain AC
45.
Tw)%
as the equilibrium curve, along which
KC1
and
as
is
the solid phase separating,

Similarly,
AC is a fusion curve.
the melting point of which is 451, represented by B, the freezing point is lowered, and the curve CB represents the freezing points of solutions of KC1 in
KC1 is added to molten AgCl,
The solid phase separating is AgCl, and this- is in equilibrium with the solution along the fusion curve CB. At the intersection C of the two fusion curves, both KC1 and AgCl
AgCl.
separate in the proportion of 70 per cent of
AgCl and 30
211
per cent of KC1. The mixture of this concentration has the lowest fusion point of all mixtures of these two compounds and
is
therefore the eutectic, and the eutectic temperature is 306. The fusion curves of the alloys of lead and antimony,
eutectic, are represented on the temperature-concentration diagram in Fig. 46. If a melt of the composition represented by
is reached separate when the curve and the composition of the liquid will become richer in Sb. On further cool-
which show the existence of a
m be selected and cooled, pure Pb will AC
'!* rT>
ing, the fusion
curve will follow the line
AC
until sufficient
centration to that indicated
mass same
will
is
solidify
Pb has been removed to bring the conby C, the eutectic, when the without change of temperature. The
by
true of mixtures containing more Sb than indicated the concentration C. When these molten mixtures are
cooled, the pure metal
is
reached,
when
Sb separates until the concentration the mass solidifies like a pure substance
of these
without change of temperature. It is evident that no alloy two metals has a melting point lower than 246, the eutectic temperature, which is represented by the horizontal line
DCE
also represents the temperature at
through the eutectic point C. This line which any alloy of Pb-Sb
would begin to melt.
The concentration-temperature diagram is divided into the following fields of concentration by the fusion curves and the eutectic horizontal
:
i.
I
Above the
In area In area
fusion curve
ACB
Pb
is is
2.
ACD,
crystallized
the liquid or melt. in equilibrium with the

in equilibrium with
liquid.
3.
BCE,
field
crystallized
Sb
is
the liquid. 4. In the
below
DCE
two
the homogeneous crystalline
mass, composed
of the
crystalline solids
Pb and
Sb,
'
212
exists.
PHYSICAL CHEMISTRY
This
field
may
be divided into two areas by a
line
These have parallel to the temperature axis through C. differences in structure, recognized microscopically. Hence,
the eutectic
is
regarded as an individual structural element
in all metallurgical investigations. In many cases the fusion curves
eutectic point such as
we have
do not show a marked been considering, but we just have a fusion curve that shows that the fusion point of certain mixtures lies much below the melting point of
the lower melting substance, i.e. they manifest a minimum freezing point.
'<*>*
we, e
h%
100%
K C03
2
NnC03
The temperature-concentration diagram for mixtures of K^COs and work in analytical Na2 CO 3 employed r J J
is
FIG. 47.
given in Fig. 47.
mixture of
and
lar proportions
Na2 CO
in about molecu-
has the lowest fusion point, about 700, and employed in fusions in preference to the pure components, as the reaction with the refractory substances can be carried on at a much lower temperature.
this is
In the preparation of explosive mixtures use

this
is
made
of
It is desirable to introprinciple in filling shells. duce the material and handle it in liquid condition. Different
same
explosives are mixed so as to produce a mixture that has a low melting point, thus preventing obnoxious fumes, loss of In material, and reducing the hazard to the minimum. Table 1 VI are given a few explosives with their melting points and also the melting point of their mixture.
XXX
is a very common Using water as one of the components, the eutectic (cryohydric) point for a great many substances has been determined, and in Table XXXVII is given a list of some of these, with the eutectic (cryohydric) temperature
The
existence of eutectic mixtures
phenomenon.
and the composition
of the eutectic (cryohydrate)
213
TABLE
SUBSTANCE
XXXVI
214
2.
PHYSICAL CHEMISTRY
on heating, the ice will melt, the and as more heat is added the ice will all disappear and we have the monovariant system salt-solutionsalt in excess,
salt will dissolve,
With
vapor.
not in equilibrium above the cryohydric they are mixed above this temperature the ice will melt, and depending upon the relative quantities of salt and ice, we shall get one of the two monovariant systems,
Ice
salt are
If
and
temperature.
represented
by
CE or
CF.
heat
is absorbed, and when a salt dissolves When be either absorbed, evolved, or neither absorbed nor may
ice melts
heat
evolved.
This can be readily ascertained from the slope So that in using a mixture for freezthe ing purposes, object being to remove heat from the substance we desire to cool, it is evident that the removal of heat is going to be accomplished by (a) the melting of the ice
of the solubility curve.
and
If
(6)
the solution of the
salt.
the salt absorbs heat, then the two factors (a) and (6) are going to work together but if the salt evolves heat, they
;
will
is
oppose each other and if the heat of solution of the salt zero, the whole cooling effect is due solely to the melting
;
of the ice.
ice are used.
Such
is
the case
when common
salt,
NaCl, and
salt-ice-vapor above the cryohydric not in temperature, equilibrium and so will tend to pass into a state of stable equilibrium. The temperature will fall until (i) one or both of the solids disappear or (2) until the cryohydric temperature is reached. This is the lowest temperature attainable at atmospheric pressure with a given freezing mixture, for we then have equilibrium between the solids at and below this temperature. The temperature reached in the laboratory is not always the cryohydric temperature, for the solution that is being continually formed has to be cooled with the rest of the system. There results a
If
it is
we have a system
temperature at which the heat absorbed by the solution
215
being formed, in unit time, is just sufficient to keep the mass of solution present at a constant temperature. Attaining
temperature, then, depends on (i) the initial temperature, (2) the rate of radiation, (3) quantities of salt and ice used, and (4) the thoroughness of the mixture,
the
since the speed of reaction
is
minimum
the solids.
When
the ice is in large pieces, less
proportional to the surfaces of heat will be
absorbed in unit time. Therefore, the equilibrium will be reached at a higher temperature than if the pieces are small. In order to obtain a low temperature by means of a freezing mixture the following precautions should be observed 1. Select a mixture with a low cryohydric temperature. 2. Select a mixture such that the heat absorbed per gram
:
formed is as great as possible. This is realized if the solubility increases rapidly with the temperature. (NaCl is not ideal, as heat absorbed is nearly zero, hence the heat
of solution
absorbed
3.
is
due practically to the melting of the

in proportion indicated
ice.)
Take substances
by the cryohy-
drate.
4.
5.
Remove
Use
solution as fast as formed.
fine material to increase
producing
maximum
speed of reaction, thus absorption in unit time.
CHAPTER XX
SOLVENT AND SOLUTE CRYSTALLIZE IN ACCORDANCE WITH THE LAWS OF DEFINITE AND MULTIPLE PROPORTIONS
TYPE
II
substances on crystallizing from aqueous solutions to contain a considerable amount of the solvent, found are is which always in a definite ratio to the solute or some The solute is said to crystallize with this ratio. of multiple Na2 SO4 10 H2 O, of water crystallization, e.g. CuSC>4 5 H 2 O act in a similar manner, etc. solvents than water Other of and we may have alcohol crystallization, benzene, acetone, The compounds containing water of crystallization etc. are known as hydrates and have been very extensively studied, while those in which other liquids appear as the solvent have also been studied. It is possible for us to take up the consideration of only a few of the hydrates. Sodium Sulphate and Water. From the solubility determinations of sodium sulphate in water, the data of which
;
MANY
are represented diagrammatically on the concentration-temperature diagram, Fig. 48, it is apparent that the curves represent the equilibrium between different solid phases and
the solution.
The abscissas are the per cent of sodium sulphate, the ordinates the temperature, and the system is supposed to be
under
its
own
pressure.
Starting with water at zero degrees, the freezing points of the solutions of increasing concentration are represented
216
217
curve.
by the curve At
A B,
B,
familiarly
known
the
cryohydric
as the freezing-point the hydrate point,
Na2 SO 4 ioH 2 O begins to crystallize out, and we have the 1.2 inversion point at and a concentration of about 40 grams per 100 grams of water. The curve represents
BC
.the solubility curve for the decahydrate and is rium curve between the solid and the solution.
an
equilib-
On
heating
a decrease in the solubility, as is represented by the curve CD, which is an equilibrium curve between the anhydrous solid and the solution. The intersection of these two
there
is
solubility curves at C indicates another transition point, and we have
the two solid phases in equilibrium with the solution and vapor. The
temperature of this transition point

32.5 (Richards, 32.379 hydrogen thermometer, 32.482 mercury thermometer) at a concentration of 49.8
is
grams.
Hence, above this tempera-
ture the solid anhydrous salt is in equilibrium with the solution, and below, the hydrated salt with ten molecules
of water of crystallization.
The curve
BCD
is
then not
a continuous curve, but the
solubility curve shows a break or discontinuity in direction, which is characteristic of the sulphates and indicates that entirely different phases are
in equilibrium along the respective curves. The curve has not been realized very far beyond the inversion tem-
BC
perature C.
There is one other hydrate known, the heptahydrate, which can be very readily obtained in the presence of alcohol, but which also separates out of a solution of sodium sulphate which has been saturated at about 34 and allowed to The comcool below 17, having it protected very carefully. position of these crystals which separate is Na 2 SO 4 7 H 2 O.
The
solubility curve for this solid is represented
by EB',
"
2l8
PHYSICAL CHEMISTRY
its
and
25
intersection with
DC
continued in the vicinity of
represents a labile nonvariant system unstable with respect to Na2 SO 4 ioH 2 O.
and
of course
We
had
is
stated that the solubility curve of the decahydrate been carried out a little ways beyond the transition
point.
Above
greater than is saturated with the decahydrate would be supersaturated with respect to the anhydrous salt. Likewise, if we have a concentration and the temperature of a solu-
this point the solubility of the decahydrate that of the anhydrous salt, and so a solution
which
tion as represented by the point N, and this be cooled in a closed vessel, the changing state of the system will be repAt N' the solid phase resented by the vertical line TV N'
.
decahydrate should appear. If, however, the solution be cooled carefully, it may be possible to get the temperature much below that indicated by N' and prolong the line con-
The solution contains very much more salt than a saturated solution contains and is said to be supersaturated, for if the solid phase of Na2 SO 4 10 H 2 O be brought in contact with the solution, the amount of the salt in excess of that contained in a saturated solution at that temperature will be separated out. Hence, our definition of a saturated solution must contain the statement as to the temperature of the solution and the solid phase with which It might be stated, however, that any it is in equilibrium. substance which is isomorphous with the solid phase will also
siderably.
produce the precipitation. This phenomenon of supersaturation is not confined to aqueous solutions, but it may be stated in general that those
out with water of crystallization form solutions much more readily than those that supersaturated the in anhydrous form. This is by no means uniseparate
salts that separate
versal, for
state
many substances which separate in the anhydrous form supersaturated solutions very readily. This is true for silver nitrate and sodium chlorate in aqueous solu-

tions, while in the case of organic solvents this is
219
very com-
mon. most
It is
generally held that those salts that separate

salts that
with water of crystallization form large crystals and form

easily
on crystals already present, while

solutions
form
supersaturated
with difficulty crystallize spon-
taneously in very small crystals.
Pressure-Temperature Diagram of Sodium Sulphate and The curves A B, AC, and AM, Fig. 49, represent Water. the system for pure water. We saw that upon adding a solid solute to water the vapor pressure of the system was
If Na 2 SO 4 is added to water, p the resulting solution will have a lower vapor pressure than the pure solvent
lowered.
under the same

perature.
conditions
shall
:
of
temthe
We
then
have
following systems
Curve CD, mono variant system

<IG
'
Hydrate-solution-vapor.
,
49
'
Curve CA monovariant system Ice-solution-vapor. Curve C K, monovariant system Hydrate-solution-ice. Curve CH, monovariant system Hydrate-ice-vapor. Point C, cryohydric point, non variant system Hy-
by C, the system is heated and the volume kept constant, the ice will disappear
If
first
drate-ice-solution-vapor. under the conditions represented
shall have the system solution-hydratewhich will increase in temperature with increased vapor, pressure, and the curve CD will represent the equilibrium of
and we
the system. At the point the solid anhydrous phase apand there results the non variant system anhydrous pears, This represents the point salt-hydrate-solution-vapor.
inversion point
and
is
the intersection of four curves
DE,
DF, DC, and

30.8
mm.
at the temperature 32.5 and a pressure of mercury, representing the four possible mono:
DG
variant systems
220
PHYSICAL CHEMISTRY
Anhydrous
salt-solution-vapor.
salt-solution.
DE
DF DC DG
Hydrate-anhydrous
Hydrate-solution-vapor.
Anhydrous
salt-solution-vapor.
is below pressure curve for anhydrous salt that for the hydrate DC, but the stable system below 32.5, D, is the hydrate-solution-vapor, and the labile system is
The vapor
DG
salt -solution- vapor. But this is the reverse of what we considered under the sulphur system, where we saw that the stable system was that one which had the lower vapor "pressure. The more stable system is the one with the lesser concentration and therefore greater vapor This is a general condition, as there are two pressure.
anhydrous
forces acting (i) the tendency of the vapor to distill from the higher to the lower pressure and (2) the tendency of the
:
solute to precipitate
from the more concentrated
solutions.
The
latter is
equilibrium. the less stable form

of the
the stronger, but either would bring about This condition depends upon the fact that
is
the more soluble, and as the lowering vapor pressure is proportional to the concentration, the result is a much lower vapor pressure for the labile solutions (Bancroft's Phase Rule). Solubility Curves of Hydrates
Which Do Not Have
following diagrams, Figs. 50, illustrate the and 52, types of solubility curves obtained 51, for salts that crystallize with water of crystallization.
Definite Melting Point.
The
10%
30%
50%
Nal
80*
CulNOjj),
FIG. 50.
FIG. 51.
FIG. 52.
221
of individual
Each
solubility curve is
made up
of a
number
curves, each of which represents the equilibrium between some specific hydrate and solution, and there will be as
many
ments.
different solid phases separating as there are segHence, in determining the solubility of a substance
it is necessary to know the composition of the solid phase in equilibrium with the solution as well as the temperature at which this equilibrium is established. To establish thor-
oughly the point of equilibrium it is best to approach it from both a higher and a lower temperature, or by establishing the rate at which it is attained. A saturated solution is a solution in equilibrium with the solid phase (i.e. with the pure In these cases the pure solute) at a specified temperature.
solutes are the hydrates
Solubility
Curves
of Hydrates,
and the anhydrous salt. Some of Which May Have
a Definite Melting Point.
and substances, some

Figs.
53,
54,
The following solubility curves, represent the equilibrium curves of of the hydrates of which melt without
55,
change of temperature and form a liquid of the same composition as that of the crystalline solid hydrate. It will be noticed that the curves starting from the left
of the figure represent first the lowering of the freezing point of water as the concentration of the solute is increased.
This is usually designated a freezing-point curve, and it is a cooling curve for the solvent which separates along this curve, as solutions of concentrations up to that represented
B are cooled. It also represents the temperatures at which mixtures of these concentrations, when in the solid state, will have to be heated before they begin to melt; they may also be termed fusion curves. We reach a miniby
mum
is
it is
compounds can
value for the temperature at which the mixture of the exist in the liquid state. This temperature
the eutectic temperature, or when water is the solvent, termed the cryohydric temperature. The curve is termed the This is solubility curve.
BCD
222
PHYSICAL CHEMISTRY
for all along this curve the
an equilibrium curve,
is
same
solid
in equilibrium with the solutions of phase (a hydrate) various concentrations. The temperature at which this
hydrate is in equilibrium with the saturated solution increases with increased concentration until a maximum value, C, is reached, when the solid hydrate is of the same concentration as that of the solution
from
In other words, separates. if we had a solution of this specific concentration and cooled it, at the
which
it
mum value
solidify
Weight
7.
temperature represented by this maxithe whole solution would

ture, or
without change in temperaif we had a solid hydrate of
FlG S3
this concentration, it
would melt at
temperature without change in temperature, i.e. it has a constant melting point, and the These are characsolution has a constant freezing point. teristics of pure chemical compounds, and therefore we conclude that such points as C represent definite chemical compounds, which in these cases are termed hydrates. The remainder of the curve CD shows a decrease in the
this
temperature at which this solid hydrate is in equilibrium with solutions of increasing concentration. This decrease
continues until the point is reached, where our solubility curve is intersected by another so-called solubility curve,
DBF, along which another solid phase of a different hydrate separates and is in equilibrium with a series of still more concentrated solutions. It will be noticed that this
portion of the curve is practically a repetition of what we have just explained the point E represents the maximum temperature at which this solid hydrate is in equilibrium with the solution and is the melting point of the hydrate, and melting points of this character are termed congruent
:
melting points.
223
The
retroflex
portion of the curve
EF,
similar to
CD,
is
B, the freezing-point curve, for in all of really similar to these cases we have a case of the lowering of the freezing point of the solute by the addition of a second component. This second component in all cases is the anhydrous salt, but the solvent in the first case is pure water, the freezing
point of which is A in the second case the solve at is the hydrate of the composition represented by C, the freezing point of which is the temperature corresponding to C\
;
while the solvent in the third case
is
the hydrate of the com-
position E, the freezing point corresponding to the temIt is then apparent that these curves, which perature E.
we term
solubility curves (portions of them at least), are readily recognized as freezing-point curves or fusion curves. It is also apparent that if these values were plotted with
the two components interchanged, the portions of the curves we have been designating solubility curves become the portions recognized as the freezing-point curves and the freezing-point curves become the solubility curves. are, therefore, justified in using the terms fusion curves, solu-
We
bility curves, and freezing-point curves as synonymous, and subsequently we shall do so. It is evident that the intersection of a fusion and a solubility curve is the eutectic
or cryohydric point, or this point could be defined as the point of intersection of two fusion curves.
If
at
any temperatures between

it will
C and D
a horizontal line
be drawn,
points,
which are two solubilities of the hydrate of the composition represented by C. In the weaker solution we have a hydrate separating which is richer in the solute component than the
in two intersect the solubility curve indicates that for the same temperatures there
BCD
solution, while in the other case the concentration of the solution is richer than the hydrate in the solute component.
The hydrate can
exist in equilibrium with two solutions of very different concentrations at the same temperature.
224
PHYSICAL CHEMISTRY
of
In the diagram, Fig. 54, representing the solubility curve FeCl 3 in water, let us draw the line representing a
XY
temperature of about 31.2. If a solution of ferric chloride is evaporated at this constant temperature, the concentration will increase until
the solubility curve
BC
is
intersected,
when FeCl 3
12
HO
2
will crystallize out.
This crystallization will continue until all the solution will have disappeared. Liquefaction occurs again where CD is intersected and at the concentration on DF above
solidification
again occurs.
On
further
407o
t
%
;
80%
Fe4ci
evaporation liquefaction again occurs and at the intersection of FG it again solidifies Hence we have sucan(j remains solid.
cessively solution
;
solidification to dode-
cahydrate
liquefaction
;
solidification
to
heptahydrate
liquefaction solidification to pentahydrate. In the case of the system 2 O-SO 3 , Fig. 55, we have a marked example of the formation of H 2 0+2S03=H 2 S 2 7 H 2 O+SO 3 =H 2 SO4 hydrates. Here we have five as rep2H 2O+SO 3 =I1 2 SO4 +H 2O
resented
points C, E,
exhibits a
is
by the congruent melting H, J, and L.
This type of solubility curve, which congruent melting point,
common
when
in aqueous solutions, and other substances are employed
as the solvent, as mixtures of organic substances and in alloys, we find

it
a very common type of solubility This fact in the latter cases FIG. 55is used as a basis for the establishment of the existence of chemical compounds. The dehydration of Vapor Pressure of Hydrates. the dissociation of is to analogous crystalline hydrates
fflP
curve.

other substances such as
sociation
225
dis-
ammonium
3
chloride,
which on
Cu(NO
3) 2
gives 6 2
NH C1 ^ NH + HC1. Similarly we have H ^ Cu(NO 3 H O + 3 H O but as we

4 3) 2 2
2
;
have a two-component system, salt-water, in three phases, we have a mono variant system, and at each specified temperature there will be a certain definite corresponding vapor pressure which is independent of the masses of the phases
present.
Hydrated salts give off their water of crystallization as vapor in vacua. This is also true when the substance is heated at other pressures, and for a definite temperature there is a certain pressure of the vapor which is independent of the water given off as vapor. This law has been very
thoroughly established, and the vapor pressures of many hydrated salts have been measured. The vapor pressure in
number of hydrates is given in Table XXXVIII, which shows the variation of the pressure with the temperature.
millimeters of mercury of a
TABLE XXXVIII
SALT
226
PHYSICAL CHEMISTRY
for saturated solutions in equilibrium with the penta-
CE
hydrate.
Os dissociation curve for CuS0 4 5 H 2 O CuSO 4 -3 H 2 O+ 2 H 2 O 03 dissociation curve for CuSO 4 3 H 2 O CuSO 4 H 2 O+2 H 2 O Oi dissociation curve for CuSO 4 H 2 O CuSO 4 + H 2 O If at some arbitrarily selected
;
; ;
temperature, as indicated at
k,
water vapor be admitted to the anhydrous CuSO 4 the vapor pres,
sure will increase.
By
the contin-
uous addition of water vapor the vapor pressure will continue to increase,
FIG. 56.
and at various pressures we
should have the vapor in equilibrium with the different hydrates
represented by the intersection of the vertical line from k intersecting the vapor pressure curves at the points j, i, h, g, and / respectively, when we should obtain an
infinitely dilute solution the
be practically that of
intersection
/.
vapor pressure of which would pure water, represented by the
Pareau measured the values of the vapor pressure of hydrates of CuSO 4 by withdrawing the vapor gradually
and
thus formed.
establishing points of equilibrium of the lower hydrates The data in Table were obtained by
XXXIX
him
at 50.
TABLE
XXXIX
PRESSURE
CuSO 4
4 5
HO
2

For compositions between CuSO 4
5
227
-
H O and CuS0
2
;
HO
2
the pressure remains practically constant at 47 mm. it then drops to 30 mm., at which pressure it stays until there remains only one molecule of water of crystallization, when
the pressure
salt is
salt. falls
to 4.4
mm.,
at which
it
remains until the
completely dehydrated and we have the anhydrous
This may be represented on a pressure-concentration diagram at 50, as is shown in Fig. 57. The vapor pressure of pure water at 50 is represented by /, and as the CuSO 4 is added the vapor pressure changes as represented by the line /g, when a
saturated solution
is
reached, as
56.
shown
the
by curve
CE
in Fig.
Now
vapor pressure remains constant until sufficient anhydrous salt has been added
to convert the
CuSO 4
HO
2
all
into
ESQ.
<IG>
CuSO 4
H O,
2
and then the vapor

S7
'
pressure drops suddenly to 47 mm. If we were to start with the anhydrous salt
CuSO 4 and add water vapor, the vapor pressure would increase until we reach point j, Fig. 57, when the monohydrate will be formed, and we shall have the monovariant system CuS04CuSO 4 H2 O-vapor at constant temperature and constant
pressure (4.4 mm.).
will
By continued addition of vapor there be a continued formation of the monohydrate from the anhydrous CuSO 4 until it has all disappeared, when we have a divariant system represented by line ji with increase of
pressure until i is reached, which represents the formation of the trihydrate, when we have a new monovariant system
CuS0 4
H O-CuSO
2
H O-vapor.
2
The
pressure
on
this
system will remain constant (30 mm.) until there has been added enough vapor, to convert all of the CuSO 4 H 2 O into CuSO 4 3 H 2 O. As soon as this occurs we have a divariant system, the pressure on which changes as represented by
228
ih until
PHYSICAL CHEMISTRY
h
is
reached, and
5
we have
4
the
system
sure (47
CuSO 4
mm.)
5
H O-CuSO
2
H O-vapor,
2
new mono variant when the presthe trihydrate

di variant
will
remain constant until
all of
has disappeared,
CuSO 4
when we have a new H 2 O-vapor. The pentahydrate,
like the other
system hy-
drates, can exist with water
and the area sOCE represents the area

variant system
this
vapor at different pressures, in which this di-
may
is
temperature
exist. So that if the vapor pressure at increased, at g the vapor will begin to
we shall have introduced the new phase The curve CE then represents the equilibrium between CuSO 4 5 H 2 O-solution-vapor and is the vapor prescondense, and
solution.
sure curve of saturated solutions.
Data such as represented for copper sulphate and its hydrates enable us to determine the relation between the vapor pressure of water in the atmosphere under ordinary
conditions and that of the hydrates. So that a particular hydrate, such as the pentahydrate CuSO 4 5 2 O, with a vapor pressure represented by curve O$, Fig. 56, begins to lose
water of crystallization if it is brought into an atmosphere which the vapor pressure is less than the amount represented by 05 it will take on water if the vapor pressure in the atmosphere is greater than the pressure represented by 05. This process of crystalline hydrates losing water of
in
;
crystallization
efflorescence,
and the process
under atmospheric conditions is designated of taking on water is designated
This principle is made use of in the processes deliquescence. of desiccation, and the particular substances employed,
H 2 SO4 CaCl2 etc., have low vapor pressures and become hydrated by the absorption of the water from the
such as
, ,
substance to be dried.
CHAPTER XXI
IV
SOLVENT AND SOLUTE CRYSTALLIZE TO FORM SOLID SOLUTIONS OR MIXED CRYSTALS
TYPE
III
IN the examples of the freezing point of mixtures we have assumed that the solid phases that separated were the pure substances along their respective solubility curves, and at did we have the two the eutectic point only one point
This is, however, only a special of binary mixtures the solid phase separating along the fusion curve consists of a mixture of the two components in proportions varying within certain limits.
solids separating together.
case, for in a large
number
This, as
we
recall, is
solid phases that separate
our definition of a solution, and these were termed solid solutions by
They are generally termed mixed crystals or mixtures. isomorpkous It will be recalled that the addition of a solute lowers the
van't Hoff.
freezing point of the solvent, and the greater the concentration the greater the lowering until we reach the maximum solubility in saturated solutions, when we have the eutectic
temperature reached. Let BC, Fig. 58, be the vapor pressure curve and BD the sublimation curve for the pure solvent water. On addition of a solute the vapor pressure is lowered, and as the concentration is increased the vapor pressure curve takes the succes229
230
PHYSICAL CHEMISTRY
sive positions indicated by the dotted lines. These, continued until they intersect the curve BD, give the triple point for
responding
the successive solutions, with the corlowering of the freezing
temperature.
Our
case
solid
FIG
is
explicit
assumption
in
this
that the vapor pressure of the phase as represented by the

i.e.
separates is pure curve. Now, if the solute
is that of the pure that solid phase that the solvent, and is its sublimation solvent,
sublimation curve
BD
and solvent separate
together,
the vapor pressure of this solid phase will be different from that of the pure solvent as represented by the freezing
curves.
may represent this in Fig. 59, where the vapor pressure of the solid phase separating varies with the increase of solute, and we have also the vapor
pressure curves of these various solid
solutions
We
represented by a, b, c. of these vapor pressures are higher than they would be were the It solid that separates pure solvent.
The values
evident that the freezing point (represented by the intersection of a, a'

is
b,
FIG. 59.
f
;
c, c') is
raised,
and
it
may
be higher than that of the
thus have mixtures separating which have pure solvent. the of properties of ordinary liquid solutions, although many
We
they are in the solid
state.
These are called
solid solutions
or mixed crystals, and are also termed isomorphous mixtures. and A/", which are If, however, a solution of two metals,
miscible at
somewhat
cool, we have a different cooling curve, as illustrated in Fig. 60. The part of the cooling curve, AB, is regular, but at the temperature tB the solid separating out is a mixture
all
temperatures, be allowed to

of
23 I
than the mother liquor. The and N, richer in temperature at which more crystals can be separated from it becomes lower and lower, and this may be represented by BC. When the temperature /cis reached, the whole mass
then solidifies, and the cooling curve represents the regular cooling of the
solid mass.
CD
Curves of Binary Alloys. which was described on page 207, cooling curves be obtained for alloys of different percentage composition and these results plotted on a
Fusibility
If,
in the manner
have a means rium diagram

for
all
temperature-concentration diagram, we of obtaining the fusibility curves or equilibfor all possible mixtures of these two metals
ranges of temperature.
fusibility curves so constructed.
Figure 61 illustrates the Let and represent
and N, respectively the melting points of the two metals then the horizontal axis, represents all
possible mixtures of
M the metals M and N.
The curve X represents the points of initial solidification and is designated the liquidus curve. Now
by connecting the points
MBB -N
MCC -N,
X
an equilibrium curve which all temperatures at which all represents FIG. 61. mixtures of the two metals and N completely solidify, and this is designated the solidus curve. Cooling Curves. By means of the thermoelectric pyrometer, temperature measurements can be readily made and data obtained for determining the heating and cooling curves from which the thermal critical points are determined. In order to emphasize the existence of such critical points and then determine their location more accurately the data are
get
we
plotted in a
number
of different ways.
23 2
PHYSICAL CHEMISTRY
i. The time-temperature curve. In this method the coordinates are the time / in seconds and the temperature
6.
The
perature,
ordinates are the successive rises (or falls) of temand the abscissas the corresponding time in seconds
when the temperature readings

beginning of the observations.
Temperature-Time
850*
made counting from the The data for a cooling curve

are
D/ftenence
/nverserate
curve
curve
ct/rre
Derweef-d/fferentia/ curve.
830'-
8tO L Fio.
62.
TYPES OF Cooling Curves
Desch.
showing two critical points are represented by by curve A in Fig. 62.
this
method
2. Inverse-rate curve. If the temperatures are plotted against the actual interval of time required for each successive change of i C. in temperature, we have what is known as
the inverse-rate curve, such as
C in
Fig. 62.
represents
the change in time required for a change in temperature and gives us the time required for cooling through i. Plotting
these values against the temperatures
0,
we have
as the
coordinates
and
The
fact that the slight retardation in rate of cooling
might be overlooked, owing to the small jogs in the curves, suggested to Osmond the desirability of emphasizing these
thermal points by using the inverse-rate curves, the breaks
in
which are approximately proportional to the amount of
233
heat evolved on cooling or absorbed on heating. To still further overcome the irregularities and effects of the furnace
and other surrounding

bodies, the cooling of
influences, use is
made
of neutral
sample to be tested.
neutral
of temperature
which is compared with that of the Robert Austen introduced the use of a
body and two thermocouples, so that the difference between it and the sample to be tested
metals.
could be determined, as well as the actual temperature of the The temperature of the two would be the same if
the heat capacities and emissivities were identical, and they would be different, only at the critical points, where
is evolved on cooling or absorbed on heating. There always be a little lagging in one of the substances, for they will not have the same heat capacities, but the critical points will be represented by abrupt differences between the
heat
will
temperatures of the two bodies.

3. Difference curves. By employing a neutral body that shows no thermal inversion points, and plotting the difference in temperature between the neutral body and the one under examination against the temperatures, we then have as the coordinates the temperature and Such a difference {
.
curve
is
nated
in Fig. 62, while the curve desigrepresented by represents the temperature-time cooling curve for a
neutral body. 4. Derived differential curve.
curve
If the slope of the difference plotted against the temperature, we have as the coordinates the temperature 0, and the rate of cooling for
is
each degree of temperature
A
is
This
is
the method
employed by Rosenhain and
represented
by curve
in
This method gives the most pronounced indication Fig. 62. of the thermal critical points, as is readily seen from a
comparison of these different curves, and thus eliminates more completely the irregularities which are due primarily
to the differences of the heat capacities
and
emissivities of
234
PHYSICAL CHEMISTRY
the neutral body and the sample under examination resulting
from
their different rates of cooling
and heating.
Figure 63 represents a typical fusion curve of binary alloys whose metals form solid solutions. For, if at some concentration, such as 50 per cent of A and 50 per cent of B, we
_
100 /&
i0
have the liquid at the temperature

t
and
if
represented by the point P, we cool the melted mass
we
at
reach the liquidus curve AlB the point / temperature t

t.
Solidification begins and the crystals that separate must have the
composition represented by
on
FIG 6
^ e so ^dus curve, which is obtained by drawing a horizontal line

t]
through
This
is
until it intersects the solidus curve at
s.
This
must represent the composition
Now
as the
designated a mass continues to cool from
of the crystals that separate. solid solution.

tt
to
t lt
the solid
crystals that separate at I' continue to grow and become richer and richer in the metal A, while the remaining mother
liquid likewise
fusible.
becomes richer in A and therefore more The varying composition of the liquid is represented
A, and at any temperature by the part of the curve //' the composition of the crystals is designated by 5 on the solidus curve, and at the still lower temperature t v by s',
This means that the crystals that separate out on cooling change in composition from s, through 5' to A represented by the solidus curve. This means that the crysetc.
tals first
formed increase in size by addition of crystals of but as the temperature falls diffusion takes place, and the crystals become homogeneous. At the temperature tw the solidification is complete, and the composition of the last drop of molten liquid to solidify has the composition of nearly pure A.
different composition,
235
Diffusion takes place readily in the case of liquid solutions,
but to produce homogeneous crystals with solid solutions the solidification and subsequent cooling must be very slow, otherwise the solid solutions will be heterogeneous, that is, the different layers on the crystals may be of different composition, the proportion of the more fusible metal increasing from the inside to the outside. By heating the alloy a long time at a temperature below the melting point, diffusion
takes place and destroys the heterogeneous structure of the solid solution. This is designated the annealing process.
This will become clearer if we give a specific example. In Fig. 64 we have the temperature-concentration diagram of the fusibility curves for gold and platinum, which are AlB is the typical of such isomorphous pairs of solids. liquidus curve and AsB the solidus curve, and in the area between the two the alloys are partially liquid and partially solid. In Fig. 65 for Cu and Ni series, this area is much
1007,
FIG. 64.
FIG. 65.
smaller than in the Au-Pt series.
If
a Cu-Ni alloy
is
rapidly
cooled, it will be much more nearly homogeneous than an alloy of Au-Pt when cooled under the same conditions.
There is less difference in the composition of the liquid and the solid which separates, and consequently incompleteness of equilibrium has a less influence in the case of Cu-Ni than in the case of Au-Pt. It is conceivable that the liquidus and
solidus curves
may be so close together that it would be practi-
*.
236
PHYSICAL CHEMISTRY
cally impossible to distinguish them, and then the solid and liquid phases in equilibrium would be identical in composition. The type of freezing curve depends upon the mutual action
of the pairs of liquids selected.
In the cases just considered
we have systems
the components of which form no chemical compounds, and the crystals that separate are miscible in all Now it is conceivable proportions, forming solid solutions.
that the restriction that no chemical
compound formed by
the action of the constituents can be removed, and also that the crystals separating may be nonmiscible or insoluble.
It is
upon the
I.
then possible to classify these various binary systems basis of the freezing-point curves as follows The freezing-point curve represents a complete series of
:
mixed
i.
crystals
or solid solutions which are miscible in all
proportions.
The
metals
freezing points of all possible mixtures of the two in Fig. 66 are intermediate between the and
freezing point of
B
and that
of B.
The curve AlB
represents the freezing
points of the molten masses and AsB the solidus curve which represents the
composition
of
the
solid
solutions
which separate when these mixtures These solid solusolidify completely.

FIG. 66.
tions vary in concentration as indi-
cated by the horizontal axis.

2.
The
the freezing point point. is raised until a certain concentration, C, is reached, when
the
freezing-point curve shows a That is, by the addition of to
maximum
freezing
maximum
value
is
obtained.
Likewise
when
is
added to liquid
the freezing point of the solution is higher than that of the pure solvent B. As the concentration of A
increases, the freezing point of the solution increases until a concentration is reached which gives the solution of the
maximum
freezing point, designated
by C
in Fig. 67.
Now

if
237
a solution of B in A be allowed to cool, at the freezing the crystals which separate will be richer in B t.j than the solution from which they separate, as s, and similarly for other solutions, we have a
point
series of points representing the concentrations of the solid solutions separating, and these are represented by
At the point the composition of the solid which separates is the same as that of the
the solidus curve AsC.
solutions,
solidifies.
that
is,
the
whole mass
FIG. 67.
Similarly the curve Cl'B represents the liquidus curve for solutions rich in B, and the corresponding solidus curve is represented by Cs'B.
The liquidus and solidus curves coincide at this point, C, and we have an equilibrium when the molten mass solidifies
without change of temperature, as in the case of a pure substance, and the structure of an alloy of the composition
by C will be completely homogeneous. examples of this case are known among alloys, but the system d- and /-carvoxim shows this type of freezing-point
represented
No
curve.
3.
The
freezing-point curve shows a
minimum
freezing
The curve AlC, Fig. 68, reppoint. resents the liquidus curve of alloys rich
in A,
and AsC
its
corresponding solidus
curve, which shows that the composition of the solid solutions that separate
richer in A than that of the solutions from which they separate. Likewise the curve Cl'B represents the liquidus FIG. 68. curve of the alloys rich in B and Cs'B its corresponding solidus curve, which shows that the composition of the solid solutions which separate is richer in B than that of the solutions from which they separated. At
is
;
PHYSICAL CHEMISTRY
C the crystals and the liquid from which they the same composition, and the alloy is cryshave separate tallized at constant temperature and must be homogeneous. Binary systems of alloys which belong to this type of curves are Mn-Cu and Mn-Ni. It is conceivable that one or more minimum or maximum points may occur in the same system, and that even a combination of these three types might be present, thus giving Such combinarise to a very complicated cooling curve.
the point
tions are represented in Fig. 69. to raises
In
I the
addition of
B
a
the melting point, and the addition of A to B lowers the
melting point, while at

considerable
of
there
is
range over which the liquidus and solidus curves are the same, and we have
concentration
a marked horizontal inflection of the It is possible to overlook such curve. 10 * a in plotting the expericondition FIG 09 mental determinations of the cooling curve, but the halting of the crystallization interval would be much more pronounced than at other portions of the curve where no such intervals of crystallization take place. The
systems Br-I and
curves.
III
Mg-Cd are examples of this type of fusion There are no known examples of the curves II and
in Fig. 69.
shown
By a consideration similar to that employed in connection with fractional distillation it can be readily shown that Type I, i represents the only pairs of binary mixtures that can be
completely separated by fractional crystallization. II. Freezing-point curves which do not represent a continuous
series of
mixed
crystals or solid solutions
and which are not
miscible in all proportions.

i.
The
meet at a
freezing-point curves of a binary system which transition point form two series of solid solutions.
239
This type of freezing-point curves is represented by the system Hg-Cd, Fig. 70. The two liquidus curves for this system are A B and BC.
Hg separates along the solidus the solid solution richer in Cd separates along the solidus curve EC, and at the point of intersection, B,
solid solution richer in
The
curve
AD, and
two liquidus curves we have the two solid solutions in

of the
equilibrium. At this temperature, 1 88 C., the two solid solutions separating
have the com-
position represented by atomic per cent of Cd)

(65.2
(62.7
"*
and E atomic per cent Cd) and
with the liquid of the composition atomic per cent Cd). B is a transition point, where we have the transition of one series of crystals into the other taking place at constant temperature, as
are in equilibrium
represented by
(51
represented by the horizontal line BDE. Along the liquidus curve BC we have crystals of one solid solution (b) separating,
and along
AB
crystals of another solid solution (a).

:
So we
may divide our diagram into the following areas the alloys of Hg-Cd Above the freezing-point curve are liquid. All alloys of which A B is the liquidus solidify with the separation of crystals of the solid solution a, and the
ABC
and the solidus area inclosed between the liquidus curve curve contains crystals of this solid solution and the liquid,
AB
AD
and at temperatures below that represented by the curve we have only solid solution a.
solidus
All alloys with a Cd concentration greater than represented consist of crystals of the solid solution b, and those by between concentrations designated by consist of a and
mixture of crystals of two solid solutions, a and b, and the solid alloy is a mixture of a and b, as represented by the area
240
PHYSICAL CHEMISTRY
marked FDEG. That is, we have a solution of the one in the other, and as the solubility is dependent upon the temperature, the curves DF and EG represent their mutual
solubility, decreasing
with decrease of temperature.
This
is
the area where
we have the crystals a and
b existing together.
It is analogous to the system aniline and water, Fig. 16, wherein the area inclosed within the equilibrium curve represents the area of mixtures which separate into two liquid
layers, the compositions of which are represented by points on the two limbs of the equilibrium curve.
some
If
mixture of a composition intermediate between that represented by the lines fF and gG be cooled sufficiently low,
say to about
40, they will eventually separate into the two
types of solid crystals a and 6, but if the composition is than indicated by fF, only a crystals will appear, richer in
Hg
and
will
If,
if
richer in
b.
Cd than
indicated
by gG, the
crystals
be
however, a solution of the composition as represented

it will
by
m be solidified,
consist wholly of the solid solution

;
whose
crystals are a only but if this be cooled, the curve will be intersected and the solid solution will separate into
FD
two nonmiscible isomorphous mixtures which are represented by n and o respectively. The curves DnF and EoG represent the change in concentration of the two sets of mixed crystals which are in equilibrium at different temperatures. That of the mixed is, we have a change in the composition is again our which a in with change temperature, crystals annealing process, and in the production of alloys this is of
very great importance, as the physical properties depend upon the type of mixed crystals present.
The
MnSiO3
freezing-point curves of liquid solutions of MgSiO 3 and have in this case are represented in Fig. 71.
We
the melting point of all mixtures of MgSiO 3 and intermediate between that of the two components.
MnSiO 3
one part of the freezing-point curve
AB
Along one set of solid
241
solutions separate, and along CB another set of solid solutions separate, and at their point of intersection, B, we have a marked discontinuity represented. For this pair of binary
mixtures this
The
at 1328 and is known as the transition point. composition of the two solid
is
solutions
that
separate
at
the
transition point
is
designated by
and E.
2.
show
tals
curves freezing-point and the a eutectic point crys-
The
separated are partially miscible

FIG. 71.
(Roozeboom's Type 5). The binary system Cu-Ag

illustration,
is
an
of this type of fusion curve, which out has been worked Along the liquidus very carefully. solution solid the of a, which is a curve CB the crystals Fig.
72,
solution of
Cu
in
Ag, separate.
solid solution varies, as indicated
The composition by the curve CE.
of this
Like-
wise along the liquidus curve separates, and at the intersection
AB
the solid solution b
curves the concentration of the

rate
is
B of the two liquidus two solutions which sepadesignated by D and E. These represent saturated solutions which are in equilibrium at the point B. This is designated a eutectic point and indicates a marked arrest during which the temperature remains constant while the mass The eutectic is then comsolidifies.
FIG. 72.
posed of a saturated solid solution of Cu in Ag, represented by E, and of a saturated solid solution of Ag in
Cu, represented by D. Just as any two partially miscible liquids have different solubilities at different temperatures, so these partially miscible solid solutions have a solubility curve analogous to that of liquids such as aniline and water.
242
PHYSICAL CHEMISTRY
then consider the curves DF and EG portions of the solubility curves of these partially miscible solid solutions. Figure 73 represents the freezing-point curves for Li2 SiO 3 AC and' CB are the freezing-point curves, and MgSiO 3
We may
and
is
the eutectic point.
If any liquid solution of these two substances be selected at a temperature and concentration represented by P, and if this be cooled to the temperature at which we meet the freezing curve CB at D, the solution will freeze, and the
100*
solid solid
phase
will
USiO,
MfiSiO,
FIG. 73.
in this
as the separate case is a particular

;
mixture of Li 2 SiOs and MgSiO 3 its be represented by some such point may as E, richer in Mg than the solution from which it
,
concentration
was separated, and the liquid will become richer in the other component. We can obtain the composition of the
other solids separating, which we represent by the curve BEG, while similarly AF represents the solids separating and CB, representing the freezing along the curve AC.
AC
points of liquid solutions, are designated the liquidus curves, and and BG, representing the melting points of the solid
AF
solutions, are
termed the solidus curves.

solid
At the eutectic point C the

separating
solid
is
phase
eutectic consisting of
two
solutions of the concentrations
The area represented by F and G. between the liquidus and solidus curves
represents both liquid and solid. In the case of Zn-Al alloys,
74,
it
Fig.
be noted that the saturated solutions of Zn contain but a small quantity of Al, whereas solutions of Al contain a very much larger quantity of Zn. The eutectic C is composed of these two
will

solid solutions,
243
D and E, and the concentration D of the solid
solution of Al-Zn
III.
is nearly over to the pure zinc concentration. The components of the binary system form chemical compounds and the freezing-point curves show one or more chemical compounds. It is conceivable that a conglomerate consisting of mixed crystals may not only melt at constant temperature, as in the case of eutectic mixtures, but also that they may be in such a proportion as to conform to the laws of definite and multiple proportions, when we should have a pure chemical compound separating, which would also be characterized by the liquid solution solidifying completely without change of temperature. In Fig. 75 we have represented the
freezing-point curves for solutions of
K SO
2
and
Along
AB
4.
MgSO 4 above 700 C. the solid phases separating
are solid solutions,
MgSO
eutectic
and along ED pure and D we have two points at 747 and 884 re-
At
spectively.
The curve BCD represents the solubility or freezing-point curve of the chemical compound
known
927.
of composition C, which is 2 MgSO 4 and 2 SO 4 as the mineral Langbeinite, with a melting point of Along the curve CB the solid phase which crystal-
lizes is this
mineral,
and the
liquid
until the concentration

solidifies into
is
becomes richer in K2 SO 4 reached, when the whole mass
the conglomerate, the solid solution

,
and
K SO
2
4 MgSO 4 without change of temperature. Along CD, the solid phase which separates is 2 SO 2 MgSO 4 the liquid
solution becomes richer in
MgSO 4
until the concentration of
the eutectic is reached, when it will solidify without change of temperature at 884, and the mixed crystals will be a con2 2 SO 4 4 and pure glomerate of the mineral 4
MgSO
MgSO
The complete concentration-temperature diagram for Mg-Sn is given in Fig. 76, in which the curve ABCDE
244
represents
PHYSICAL CHEMISTRY
the fusion
curve.
It
is
composed
of
three
along each of which there is a separate definite crystalline variety in equilibrium with the
branches,
AB, BCD, and DE,
the pure a (Mg) is in equilibrium while along the fusion curve /3 (Sn) along DE, no shows which BCD, discontinuity at C and is to be conliquid.
Along curve
the pure
AB
sidered a single continuous fusion curve, the chemical compound SnMg2 separates out along the whole range of temperatures.
That is, in melts richer than about 70 per cent Sn and those richer in Mg than about 30 per cent Mg to about 60 per cent, we have for temperatures above the eutectic
two
different concentrations at
temperature B, about 565, this chemical compound existing

in equilibrium with melts of

the same temperature.
245
The point C is a maximum temperature and corresponds to the melting point of the pure chemical compound SnMg2 At points B and we have two marked breaks in the fusion curve and these represent
.
the two eutectic points

eutectic horizontals,
known for aBc and c'De,
this alloy.
The two
are at different tem-
peratures,
and
their
components, which are represented by
the ends of the
lines,
separates into pure

,
are nonmiscible. The eutectic B magnesium and the pure chemical com-
pound SnMg2 and the eutectic D separates into pure SnMg2 and pure Sn. The method of obtaining a cooling curve is represented by Fig. 77, in which we have represented on a temperatureconcentration diagram the temperature-time cooling curves
FIG. 77-
246
for
PHYSICAL CHEMISTRY
a number of alloys of different concentrations, represented by the numbers on the fusion curve in Fig. 76. We have the pure metal Mg, the cooling curve of which is represented the molten metal cools regularly until the temby mA perature represented by A is reached, when its temperature
;
is
arrested for the time Fs, during which the metal solidifies completely, and then the cooling proceeds regularly as represented by sn. A melt containing approximately 90 per
cent
is
is cooled, and we have the curve when the point F reached, the melt begins to solidify with the separation of pure Mg, and the solidification continues until the tempera;
mF
ture of the eutectic
B is reached, when we have another arrest
in the rate of cooling, as designated by s, at which the temperature remains constant until the remaining liquid has
completely solidified. In a similar manner the temperaturetime curves illustrating the rates of cooling are deter-
mined for alloys representing the whole range of concentration, and the points F, representing the initial freezing, are
all connected, giving us the heavy line representing the freezfor the alloys composed of ing-point or fusion curve Mg-Sn. The horizontal portions designated by 5 represent the eutectic temperature, or the lowest temperature at which
ABODE
these constituents can exist in the liquid state. It will be noticed that the time required for the solidification of these different alloys is not the same, and this is shown by the different lengths of the horizontal sections represented
is more of the eutectic and consequently more time is required for its solidification, and the temperature therefore remains constant for a greater length of time. We therefore have an indication
by
s.
This indicates that there
present,
of the relative quantities of the constituents present with the eutectic alloy.
Methods have been employed to represent graphically the per cent of the eutectic present in any particular solidified melt. This is shown by the dotted portion of the diagram in

Fig. 76.
247
Draw
the line
Bb
of a length representing 100 per
all solidifies to eutectic, then quantity of the eutectic that can be produced from the melt, since all of the melt goes over into the eutectic without change of temperature. At a, which
cent,
and
since at
the melt
this is the
maximum
Mg, there would be no eutectic, hence the would be zero per cent the same is true for c, quantity which represents all pure SnMg2 and no eutectic. Connecting these points with b we have the percentage of the
represents pure
;
eutectic in the solidified melt of
such as
i, 2, 3, 5, 6, etc.,
the base line aBc.
any specified concentration, represented by the distances from If the distance from this line to b were
divided into 100 parts, the percentage of the eutectic alloy in the solidified melt could be readily ascertained. The
same is true for the eutectic and the per cent it is of any melts above approximately 70 per cent Sn, the structural composition of the solidified melt being represented by the curve c'de drawn upon the base c'De. Many times, these are drawn with the base line the same as that of the concentration axis, and a convenient distance on the vertical
axis taken as 100 per cent for the eutectic D. These different solidified melts have their characteristic microscopic appear-
and the different mixed crystals are readily distinguished and the different components thus recognized.
ance,
CHAPTER XXII
APPLICATIONS OF THE PHASE RULE
THE number and nature of the phases possible to any system when in equilibrium depend on the composition and the temperature, and it is due largely to the application of the Phase Rule to the study of alloys that such marked progress has been made in the last few years. So we shall confine our
consideration of the application of this rule to the study of
alloys primarily.
COPPER-ZINC ALLOYS
In Fig. 78 we have reproduced Shepard's freezing-point curve for alloys of copper and zinc. This cooling liquidus curve consists of six branches,
thus showing the existence of six
solid solutions; but there are no chemical compounds
different
of copper and zinc such as we found in the case of magnesium and tin. There is a distinct solid solution in equilibrium with each
FIG. 78.
of the six branches of the freezingpoint curve.
Along the section of the liquidus curve designated AB homogeneous a crystals separate, the composition of which is represented by the solidus curve A b, thus showing that the left-hand portion of the diagram from the Cu axis over to the line bbi, which represents about 65 per cent of copper, consists of a crystals. The area between the solidus curve
248
249
and the liquidus curve AB represents a crystals with the mother liquor. The area BbbiBi is occupied by a and ft
Ab
crystals, the latter being stable along the freezing curve BC, and the area cBB\c\ gives the limits of the solid solution, the
composition of which varies greatly with the change in temperature. At the lower temperature the ft crystals break down along the line BBi with the formation of the homo-
geneous a crystals, while along the line cc\ they break down with the formation of 7 crystals. The existence of a and 7 ft and 7 crystals in the same ingot has not been discovered
;
exist in the area Ccc\C\, while
is
in equilibrium along the
portion of the liquidus curve designated CD, and the area CCidid is the field of pure 7 crystals, d crystals form from the melt along DE, while at lower temperatures these break
The crystals or e and 7 crystals. into e crystals is so marked that it can be accurately observed to 29 per cent of copper. The exact
down, forming
5
and
e-5
transformation of
is
and
not definitely known, but it lies between 20 Below dêê^ the alloy consists of the mixed crystals of 7 and e. The e crystals separate out
position of des
3
1
per cent of copper.
along the liquidus EF, and these solid solutions vary in concentration from 13 to 20 per cent of copper. Alloys of copper
and
zinc containing
solid consist of the
from 2.5 to 14 per cent of copper when mixed crystals c and 77, the 77 crystals
being stable along that part of the cooling curve designated FG. Below concentrations less than 2.5 per cent of copper, the solid alloy consists of homogeneous solid solutions of 77.
Muntz's metal, which contains 60 per cent copper, is composed at ordinary temperatures of the a and ft crystals, but if quenched above 750 it will consist of homogeneous ft crystals, which make the brass ductile at temperatures above
750 so that it may be rolled hot. ft crystals are less ductile at lower temperatures than the a crystals. Quenched from
temperatures above 750, Muntz's metal is harder and stronger but less ductile than the annealed alloy.
250
PHYSICAL CHEMISTRY
These different mixed crystals are readily recognized under the microscope, and by means of micro-photographs the heat treatment of brass has been carefully studied.
IRON-CARBON ALLOYS
Among the binary alloys, that of iron and carbon is perhaps the most important. The complexity of the system is much increased by the fact that iron exists in three allotropic modiSteel
Cast Iron
lOO /.
.Per cent
Carbon
Metastajble or Cementite-Austentite Carbon-Iron
Diagram (Howe)
FIG. 79.
fications
Howe's carbon-iron equiliba, /3, and y forms. rium diagram is given in Fig. 79. The melting point of pure iron is 1530. The three allotropic modifications of
:

iron
251
all crystallize in the regular system, and as there are decided energy and volume changes at their points of transformation, there are evidences of discontinuity in the cooling curve of pure iron, and consequently proof of the different
The 7-iron is the stable form above passes on cooling into 0-iron with the evolution of heat and a considerable expansion of volume. 7-iron
physical modifications.
920, where
it
has a marked solvent power for carbon, and AB, the liquidus curve, represents the freezing points of solutions of carbon in iron, while AE, the solidus curve (melting point curve), " represents the temperature at which the alloys have just completed their freezing process, that is, have just become
" " of incipient fusion on heating The method (Rosenhain). of determining the solidus was to take small pieces of steel of known composition, heat these, and suddenly cool them
completely solid
or conversely
it
represents the temperature
from successively higher temperatures; afterwards, each specimen was examined by means of the microscope. It is easy, as the photographs show, to determine what is the particular point at which you have reached a temperature where there was a small quantity of liquid metal present
at the
moment
of quenching."
Thermal Points of Pure Iron. When pure iron is cooled from a high temperature (1000 or above), the cooling proceeds slowly and regularly, then it is arrested for a
Critical
considerable time while the temperature remains constant, and in some instances the temperature of the cooling sample of iron actually rises the metal becomes hotter, it recalesces ;
;
hence the name recalescence is given to this particular critical thermal point. This recalescence or glow of the steel may be readily seen if the experiment is conducted in a darkened room. Eschernoff designated such critical points by A, and to distinguish those obtained on cooling from those on heating, it has been agreed to designate the former by Ar (from the French refroidissement, meaning cooling) and the
252
latter
PHYSICAL CHEMISTRY
critical points
by Ac (from the French chauffage, heating). These Ar and Ac do not occur at exactly the same and for steel are as much as 25 to 50 apart. temperature,
critical point on cooling behind the crition heating is the physical phenomenon known as The hysteresis and is due to the delayed transformation. at which the transformations actuequilibrium temperature ally occur, designated by Ar and Ac, is distinguished from the equilibrium temperature Ae, at which they are due to
This lagging of the

cal point
occur.
If
a molten steel of low carbon content
(less
than about
0.4 per cent carbon), represented by the linej, be cooled, it will begin to freeze with the formation of crystals of the solid
solution termed austenite, the composition of which

in carbon than the solution
is
poorer
from which they separated, and
these crystals are represented in composition by the solidus curve Aj"E, while Aj'B is the liquidus curve. On further cooling there is no change in the austenite until about 805 is reached, when the transformation into /3-iron occurs, which
consists in the separation of pure /3-iron.
The concentration
,
of the austenite remaining is represented by the curve Ar$ (GO) until the temperature 780 is reached at j iv when aferrite appears,
more
of
of this is
and as the temperature is further lowered separated from the austenite, the composition
.
is represented by the curve Ar3 2 (OS). On reaching the temperature 725 at the point j v the composition of the residual austenite is represented by 5, which is pearlite
which
of a carbon content of 0.9 per cent. to a eu tec tic point, but we do not
This point
is
analogous
have the lowest point at which the particular mixture is a liquid, but it is the lowest transformation point for austenite, which is a solid solution. We have a eutectoid substance which consists of a mixture So below a temperature of 725 of a-ferrite and pearlite. and up to a carbon content of 0.9 per cent the solid steel when slowly cooled consists of pure a-ferrite and pearlite.
253
On
represented
cooling a mixture containing 4.3 per cent of carbon, by the line w, the molten mass of cast iron re-
mains liquid until the temperature 1135 is reached at the eutectic point E with the formation of the eutectic LedeThis eutectic is a conglomerate consisting of a mixburite.
ture of a
honeycomb
structure of eutectic cementite
filled
in with the darker masses of eutectic austenite.

is
Cementite
rated with carbon.
the carbide of iron, Fe 3 C, while the austenite is iron satuOn further cooling the chemical com-
pound cementite does not change, but the austenite changes over into pearlite and cementite at 725, as represented by
In an analogous manner the various concentrations such
as are represented by h, k, m, and p could be discussed, but this would lead us too far and the student can work the
changes out as an exercise.
APPLICATIONS TO ANALYTICAL CHEMISTRY

In the analysis of multiple component systems the properties of the individual constituents are often so nearly alike that the usual methods of analysis fail. So that in order to
determine the quantities of the constituents it is necessary to do this by some method wherein the separation of the components of the system is not necessary. This method
dependent on the relationship established under conditions of equilibrium and by means of equilibrium
of procedure is
diagrams obtained experimentally. In the case of the determination of alcohol in alcoholic beverages we have one of the principal applications of this method. It is known that if to a solution of alcohol in water certain salts, such as 2 CO 3 NaF, etc., be added, the single solution into The equibreaks two liquid liquid phases. librium is established between the two saturated solutions, and this equilibrium can be obtained at the point at which
254
PHYSICAL CHEMISTRY
the components are in equilibrium just before the separation

into
two
liquid layers occurs.
This equilibrium is dependent on the reduction of the degrees of freedom of the system by the introduction of the
second liquid layer in this case, or the solid phase in others. For at a given temperature a definite solution of alcohol and water will dissolve a definite quantity of the salt (K2 CO 3 ) and if we know the amount of salt, we then know the amount
,
of alcohol in the alcohol- water mixture
This will become more
apparent after the following consideration of the special cases. By a method similar to that described for obtaining the equilibrium curve for the system water-alcohol-ether, page 163, the equilibrium curve for the system water-alcohol-salt may be constructed on a triangular diagram. These data
may
be expressed on a rectangular diagram by calculating the amounts of the alcohol and of salt (K2 CO 3 ) in a constant
quantity of water and plotting the results. It is evident then that if the amount of salt is known, the percentage composition of alcohol and of water can be calculated. The actual determination is made in the following manner
:
If
we employ
the system water-acetone-K2 CO 3
the actual
experimental data are obtained by the general method just described. Weigh out 100 grams of the solution of acetone
and water to be analyzed. Add K2 CO 3 as a solid, or in the form of a solution of known strength, until the solution breaks into two liquid layers. Determine the amount of K2 CO 3 added. Render the solution homogeneous by the addition of water, then titrate back and forth with acetone and water until the correct end point is ascertained. Weigh again and determine the amounts of the solvents added. Now from these weights and the amount of the carbonate added compute the grams of K 2 CO 3 in 100 grams of the solvent (water). Referring to the acetone-K2 CO 3 curve the amount of acetone can be obtained and from this the percentage composition of the mixture.
CHAPTER XXIII
OSMOTIC PRESSURE
placing in pure water a bladder filled with alcohol (1748) observed that the bladder became greatly distended, but it was not until many years later that this phenomenon was rediscovered and explanations offered.
Nollet
BY
Dutrochet (1822-) observed that there were two currents connected with the passage of liquids through membranes during such phenomena as that just described (i) the
:
principal current inward through the membrane, which he termed the endosmotic current, and (2) the secondary one
outward, the exosmotic current while the phenomena were called respectively endosmosis and exosmosis. Later the term osmosis was applied to the phenomenon as a whole and is the one now employed.
;
Graham
(1854)
employed septa
of different kinds
and
demonstrated that, depending upon the character of the membranes employed and of the solute present, both the
and the solute would pass through the membrane while in the case of certain solutes they would not pass
solvent
;
through.
He utilized
this
for the separation of substances into
method, which he termed dialysis, two general classes
those which passed through the membrane, crystalloids, and those which did not pass through, colloids. Therefore it is
necessary to distinguish between dialysis, wherein the solute passes through the membrane, and osmosis, where only the
solvent passes through the membrane. In this latter case the membrane is said to be semipermeable, being pervious
to only one of the constituents of the solution, that solvent.
255
is,
to the
256
PHYSICAL CHEMISTRY
It was recognized in the process of osmosis that some of the solute also appeared on the side of the septum opposite where the solution was placed, and many explanations have
been offered to account not only for
this small trace of the
solute passing through, but also for the membrane being pervious to the solvent particularly. The conception of the
sieve construction of the
membrane supposes
it
to be com-
posed of
numerous small openings
of such size that only sub-
stances with molecules of small dimensions can pass through, while those substances with large molecules are prevented
The passage of small quantities of some as such sugar, through animal or vegetable memsolutes, branes was explained by assuming the openings to be of such size that in the passage of the solvent the inflowing current would pass along the walls of the openings, while through the central channel the outflowing current would be located. When the thickness of the solvent layer was such as to remove the particles of the solute a distance from the walls of the opening in the membrane greater than that represented by their molecular dimensions, they would slip through and
from going through.
thus pass out into the pure solvent. Lhermite (1854) showed, however, that if a layer of chloroform be placed on top of water in a large test tube, and then ether placed on top of the chloroform and the vessel closed
of a stopper and allowed to stand for a day or two, The ether passes there would be only two liquid layers. through the chloroform and appears in the water layer.
by means
That
is,
soluble in water
the ether dissolves in the chloroform, but being more it is extracted by the water, and most of it
appears in this layer. The ether is distributed between the chloroform and the water layers and the chloroform is the
semipermeable septum. Flusin (1898-1900)
showed that by using vulcanized
caoutchouc as the semipermeable membrane and employing numerous liquids in pairs of all possible combinations,
OSMOTIC PRESSURE
257
the main current was from the liquid which is the more readily absorbed (imbibed) by the rubber, through the membrane into the liquid less readily absorbed. The combination of liquids included carbon bisulphide, chloroform, toluene, benzene, xylene, benzyl chloride, turpentine, nitrobenzene, ether, methyl alcohol, ethyl alcohol, and acetic acid. By using as the membrane hog's bladder and having ethyl alcohol on one side, he placed on the other side water, methyl
alcohol, amyl alcohol, amyl acetate, chloroform, benzene, and many others, and in each case found the direction of the main current always toward the ethyl alcohol. Raoult, by employing a rubber septum, found the current to be from ether through the membrane to methyl alcohol, and by using hog's bladder as septum the main current was reversed.
Kahlenberg (1906) by employing a rubber septum has collected a large amount of data confirmatory of the solvent action of the semipermeable membrane and concludes
"
that whether osmosis will take place in a given case or not depends upon the specific nature of the septum and the
and if osmosis does occur, these factors liquids that bathe it also determine the direction of the main current and the
;
magnitude
The motive power in of the pressure developed. osmotic processes lies in the specific attractions or affinities between the liquids used, and also those between the latter
and the septum employed." The mechanism of osmosis
Chapter XXXV on
will
be further discussed in
Colloid Chemistry.
membrane over the end of a with a solution of cane sugar, and placing the bulb of the tube in pure water, the solvent will
By
fastening a parchment
thistle tube, filling this
pass into the solution, which becomes diluted. The passage of the water into the solution will continue until the hydrostatic pressure of the dilute solution in the tube is such that it prevents any more of the water from going through the
membrane
into the solution,
i.e.
the tendency of the water
258
to pass in
is
PHYSICAL CHEMISTRY
balanced by this hydrostatic pressure, and the a state of equilibrium. The pressure thus developed can be measured, and it is the pressure measured by such a device that is termed the osmotic pressure of the
osmotic
cell is in
This pressure is also conceived to be due to the of the membrane by the molecules of the solute present in the solution, and, as will be shown later, is
solution.
bombardment
considered analogous to the pressure of gaseous molecules on the walls of the containing vessel.
In addition to the numerous Precipitation Membranes. materials that have been given as examples of semipermeable
membranes, such as platinum, palladium, red-hot

table
iron, vege-
animal membranes (bladder), parchment paper, caoutchouc, zeolites, etc., there is another class termed precipitation membranes, which are colloidal gelatinous precipitates such as ferric hydroxide, calcium phosphate, gelatine, tannates, etc. but the one most
membranes (begonia
leaf),
successfully
employed
is
copper ferrocyanide, discovered by
Traube.
It
was
this
botanist, used in his classic experiments.
type of membrane that Pfeffer (1877), the In order to obtain
a strong membrane firmly attached, he precipitated the membrane in the interstices of a porous unglazed porcelain cup. He prepared these cells by soaking them first in water, then
in a three per cent copper sulphate solution, then filling the cell with a three per cent solution of potassium ferrocyanide
and immersing
tion.
this in the three per cent
copper sulphate solucell,
The
solutions diffuse into the walls of the
where
they meet with the formation of the gelatinous precipitate of copper ferrocyanide.
2
CuSO 4
+ K FeCN
4
= Cu FeCN 6
2
+ 2 K SO
2
4.
After standing some time the

off.
cell is
removed and the excess

and that the
of salts carefully washed tate be deposited in the interstices of the wall,
It is essential that the precipi-
OSMOTIC PRESSURE
deposit be thin, adherent, and absolutely continuous. conditions are very difficult to obtain.
to the dissolved substances.
259
These
These membranes are pervious to the solvent water but not Pfeffer found that when these cells containing salt solutions were immersed in pure water,
that water entered through the semipermeable wall and The tendency of the water to dilute diluted the solution.
the solution was measured height to which the liquid
by the
would
rise in
pressure exerted or the a tube against the
atmospheric pressure and the force of gravity. Pfeffer found that these pressures against the walls of the
membrane were enormous
amounting to
meas-
many
atmospheres.
Pfeffer used for
The simple device
uring these pressures is illustrated in Fig. 80. It consisted of an unglazed porcelain cell, C, in the interstices of which the copper
ferrocyanide
this
cell
membrane was precipitated. To was attached a manometer, M, by means of which the pressures could be
determined.
Table
XL
contains
Pfeffer's
FlG 8o
-
'
data and illustrates the effect of concentration on this pressure, which is termed osmotic pressure.
TABLE
PER CENT CONCENTRATION,
c
XL
260
PHYSICAL CHEMISTRY
pressure,
is
The
which
mercury,
directly
expressed in centimeters of proportional to the concentration,

is
The
effect of
is
solutions
illustrated
temperature on the osmotic pressure of sugar by the data in Table XLI.
TABLE XLI
TEMP.
SUGAR AS SOLUTE
OSMOTIC PRESSURE
which,
261
when n
i,
becomes
V=
kT.
(2 )
Van't Hoff recognized this as similar to the Gas Law Equation pV = RT and inquired if k were the same as R. This was readily ascertained by calculating the value of k from Pfeffer's data as follows A one per cent sugar (C^HÔu) solution at 13.8 C. gave an osmotic pressure of 52.2 cm. of mercury.
:
Since
solving for k
p Q V = nkT
we have
= p V
nT
Substituting in this equation the following .values p Q = a 52.2 cm. of mercury, or 710 grams per square centimeter one per cent solution contains 10 grams per liter (assuming
: ;
the density
342,
=
*
i)
we have
^%
since the molecular weight of sugar gram-molecules in i liter, or 1000 cc.

-ST2
and
is
n =
and
V=
13.8
1000
cc.
T =
we have
T
273
+
X
'
or 286.8
_ =
710
looo
286.8
710
10
X looo X X 286.8
342
or
84600 gram-centimeters per degree.
But R, the gas constant, equals 84,700 gram-centimeters per degree, and van't Hoff concluded, since these values were = R, and that we can apply experimentally the same, that k
the Gas
Law Equation to solutions in which the osmotic presis
sure of a dilute solution

pressure of an equivalent
mass
the same value as the gaseous of solute would be at the same
temperature, and occupying the volume of the solution. This application of The Gas Law to solutions is one of the great contributions of van't Hoff to the development of
chemistry.
262
PHYSICAL CHEMISTRY
OSMOTIC PRESSURE OF SOLUTIONS
Confirmatory data have been published by numerous workers, including Ladenburg, Adie, Tammann, Ponsot, and particularly Naccari (1897), whose results are among the few marked duplications of Pfeffer's work. A four per cent glucose solution at o C. should give an osmotic pressure of 37.6 cm., and Naccari found the following values.: 37.0, For a four per cent mannite solution the calcu37.8, 37.8. lated value is 38.3 cm. at o, and Naccari found 37.3, 37.6, 37-9, 37-5, 37-5, 36.3, 3^-4, which is an excellent agreement. More recently, however, we have the excellent work of Morse and his collaborators (1908-13). This shows a marked confirmation of van't Hoff's generalization, as Table XLII
illustrates.
TABLE XLII
same temperature, the volume
Ratio of observed osmotic pressure to calculated gas pressure at the of the gas being that of the solvent in the pure state.
OSMOTIC PRESSURE
of a gas
263
would exert if its volume were reduced, at the same temperature, to the volume of the solvent in the pure state." Lord Berkeley and E. G. J. Hartley (1906), instead of measuring the pressure developed in an osmotic cell by the
passage of the solvent into the cell, as is usually done, separated the solution from the solvent by a semipermeable membrane and then subjected the solution to a gradually
increasing pressure until the solvent which first flowed into the solution reversed its direction and flowed out. The
pressure, which was just sufficient to produce this reversal of the current and to prevent the solvent from flowing into
the solution, was taken as the equivalent of the osmotic pressure of the solution.
By this new dynamic method Lord Berkeley and Hartley determined the osmotic pressure by measuring the rate of flow of the solvent into the solution. By assuming that this rate of flow is the same as that which would occur if the solvent were caused to pass through the semipermeable membrane under a mechanical pressure equal to the osmotic
pressure of the solution, they find that if only the initial rate of flow is considered, the values for the osmotic pressure,
in the case of dilute solutions, agree well with those obtained by the direct measurement. In concentrated solutions the
discrepancy
is
greater than
by the other method, yet
it
may
of
have wide application.
De
Vries, the botanist,

cells.
worked on the osmotic pressure

if
plant placed in a in a weak solution the cell will while strong sugar shrink, solution it will swell up. of a cell into the introduction By
He found
that
a plant
cell is
other solutions the same results were obtained.
The
cell
permeable to water substances.

wall
is
and impervious to the dissolved
De Vries determined the strength of various solutions that caused the plant cell wall to be just separated from the protoplasm. This process of the separation is designated plas-
'
.
264
PHYSICAL CHEMISTRY
Those solumolysis, and the cell is said to be plasmolyzed. tions of the strength just sufficient to produce plasmolysis are
equal in osmotic action. Solutions, such as these, which have the same osmotic pressure, contain equimolecular quantities of the dissolved substances and are called isotonic solutions.
results are designated as normal but another class of compounds gave values for the plasmolysis that were abnormal, and the osmotic pressure values for these solutions were
;
These
likewise abnormal.
The binary substances
(uni-univalent)
such as
NaCl, KBr, KQjHsC^, etc., gave practically twice the osmotic action they should have from the gram3,
KNO
molecular content of the solution.

diacid bases
Salts (uni-bivalent) of
and of dibasic acids gave values approximately three times what they should have. Hamburger obtained, with red blood corpuscles, results which were in accord with the other animal and vegetable organisms employed as semipermeable membranes. Hence in dilute solutions of different substances we find
that the osmotic pressure conforms to all the gas laws, being proportional to the concentration, that is, inversely proportional to the
volume (Boyle's Law) the coefficient of variation of the pressure with the temperature is the same for all substances (Gay Lussac's Law) equimolecular solutions
;
;
have the same osmotic pressure, or conversely, solutions that have the same osmotic pressure contain the same number of moles in a given volume (Avogadro's Law). The absolute value of the osmotic pressure is the same as the gaseous pressure of the dissolved substance would be if we could allow it to remain at the same temperature and occupy the volume of the solution but remove the solvent. The laws of gases we have seen hold only for ideal gases
;
shall see that the application of these to solutions holds only for ideal solutions, but in the case of dilute solu-
so too
we
tions the variations are not so
pronounced as in more con-
centrated solutions.
CHAPTER XXIV
LOWERING OF VAPOR PRESSURE
IN the discussion of one and two component systems it be recalled that the vapor pressures of these systems were In Fig. 8 1 we may represent the represented on pt diagrams. the vertical axis and the f on vapor pressure axis. Then the horizontal on temperature the vapor pressure of the system water may
will
be represented by the following curves
_ CA
.
= CD =
the vaporization curve. the sublimation curve.

.,,
the fusion curve.
FIG. 81.
(a nonvolatile solute) is added, the the solvent is lowered, and for a specified of vapor pressure concentration the vapor pressure of the solution would be
As a second component
represented by the curve EF. At a specified temperature, t, the vapor pressure of the solvent has been lowered by the
p to pi. That is, at the temperathe vapor pressure of the solvent pi is equal to Bt, and the vapor pressure of the solution at the same temperature t is Ht, then the vapor pressure has been lowered p pi
addition of the solute from
ture
t
or
BH. At any
is
vapor pressure
other temperature, t\, the lowering of the or p2 The ratio of the lowering to ps.
the original vapor pressure of the pure solvent is

T
IS"
*-
^=
.
T2TT
-=
Bt
ratio
and
jj
tj
3 -
j^-
But von Babo showed that the
of the lowering of the vapor pressure of the solvent to the vapor pressure of the pure solvent is not a function of the
temperature, hence
265
266
PHYSICAL CHEMISTRY
IK ^p z
p3
therefore
have seen that the amount of lowering of the vapor pressure of the solvent is proportional to the concentration. This is known as Wullner's Law, which is expressed as follows The ratio of the change in the vapor pressure of the solvent
:
We
to the vapor pressure of the solvent

centration,
i.e.
is
proportional to the con-
If
we
of moles of the solvent
express the concentration in terms of the and of the solute, we have
number
P
in
Pi
N
N the num-
n_
which n
the number of moles of the solute and
This is known as Raoult's Law. ether as a solvent, Raoult showed that the ratio Employing of the vapor pressures of solvent and solution is independent of the temperature, which is a confirmation of von Babo's Law. This is evident from Table XLIII.
ber of moles of the solvent.
TABLE XLIII
(After Jones)
16.482
GRAMS OIL OF TURPENTINE
IN too
267
Raoult selected a number of substances with a low vapor pressure, such as oil of turpentine, aniline, nitrobenzene, ethyl salicylate, etc., the boiling points of which ranged between 160 and 222, and dissolved these in ether, which has a high vapor pressure as compared with the solutes. In Table XLIV are given the solutes, the molecular weights, n, the
number of moles
in the
of the solutes,
^
P
ft the ratio of the change

,
vapor pressure of the solvent, caused by addition of the solute, to the vapor pressure of the solvent, i.e. the fractional lowering of the vapor pressure, and in the next
column,
np
lowering of the
are employed.
the fractional lowering produced

ether.
by one
mole when dissolved in 100 moles of

vapor pressure
is
the molar
when 100 grams
of the solvent
TABLE XLIV
SOLUTES
268
0.0098, which
is
PHYSICAL CHEMISTRY
practically o.oi, that
is,
one mole of any sub-
stance dissolved in 100 moles of the solvent (ether) lowers the vapor pressure of the solvent one one-hundredth of its value.
And
since
N=
=
100 and 2
^=
np
o.oi,
we have on
is,
substi-
tution o.oi
k
100
or
k.
That
the constant of
Raoult's
Law is
law becomes
~ ? f = -^l
unity for ether, and so the expression for the
in general.
From
the data pre-
sented in Table
XLV the mean value of the constant for a large

which
is
number
of solvents is 0.0105,
virtually one one-
hundredth.
Therefore, one mole of a nonvolatile substance
TABLE
XLV
(After Jones)
SOLVENTS

For concentrated
the right-hand
tion
is
269
solutions, in the equation
^=
p
-^- ,
member may become

number
this
when
the solu-
so concentrated that the

is
number
moles
of moles (n) of the

(
solute
equal to the
of
N)
of the solvent.
Then ^
P
"=
and
o,
may
is
be written
O
P
P
which becomes
^=
P
which
an impossibility,
for the
vapor pressure of a concentrated solution will always have some numerical value. Raoult therefore changed the for-
mula
the
to read
*-
&=
p
N+n
which expresses the ratio of
present,
number of moles of the solute to the total number of moles and this holds for concentrated solutions. If we obtain the relative lowering of the vapor pressure of
when we have a
P
specified weight,
g,
of the solute dis-
solved in a constant quantity of the solvent, then P

is
~
gP
P1
the relative lowering for one
gram of solute, and

That is,
^ ~ Pv m
gP
is
the lowering for one mole of the solute.
^~P m
1'
&
is
Values of
the fractional molecular lowering of the vapor pressure. for 100 grams of the solvent are given in Table
XLV.
The lowering of the vapor pressure can be utilized as a means for the determination of the molecular weight of substances.
By
definition
-,
in
which g
is
the grams of the solute
and
m the molecular weight,
270
PHYSICAL CHEMISTRY
and
N = M .in which 5
and
is
the grams of the solvent
M
n
is its
molecular weight.
is
Substituting in the modified Raoult formula, which
Pi =
N+n
JL
we have
p L
pi *-*
-r;
M +1 m
This equation may be used for calculating the molecular weight of the solute, or if this is known, 'the vapor pressure, pi, of the solution can be ascertained providing the other
terms of the equation are known.
RELATION OF THE LOWERING OF THE VAPOR PRESSURE TO OSMOTIC PRESSURE
The vapor pressure of a solution is intimately related to the osmotic pressure of the solution. Suppose that an aqueous solution of a nonvolatile solute and the pure water
be placed in separate vessels under a bell jar and the air exhausted until the liquids are virtually under the pressure Since the vapor pressure of the vapor of the pure solvent. of the solution is less than that of the pure solvent, distillation will take place from the pure solvent to the solution, where condensation will occur with an increase in the volume
of the solution
and a resulting decrease
in the
volume
of the
keeping the solution stirred, the dilution will continue until the liquids are in equilibrium with the vapor directly above and in contact with them.
solvent.
By
If we have two isotonic solutions, A and B, separated by a semipermeable membrane and contained in an inclosed vessel, and if the saturated vapor above the solutions be not
271
the same, there will be a passage of the vapor from the one solution, A, to the other, B, resulting in the dilution of B
and a corresponding concentration of A. This change in concentration would cause the passage of the solvent through the semipermeable membrane from B to A, which would result in the production of
a condition for a perpetual motion.
It therefore follows that in the case of isotonic solutions the
vapor pressures are equal. By a simple proof Arrhenius has shown the relation between the vapor pressure and osmotic pressure without the use of
thermodynamics
In Fig. 82
is
illustrated
an osmotic pressure
cell in
which
has
the solution within the cell has
come to
rest at the height h,

air
and
all is
inclosed under the bell jar
from which the
been removed, leaving the system under the pressure of the vapor of the pure solvent.
At equilibrium the solvent does not pass by

distillation either into the solution or
out of
it. But the vapor pressure, p, of the solvent is greater than the vapor pressure, pi,
of the solution
of
by the weight of the column vapor represented by the difference between the height h of the two surfaces.
Therefore, the vapor pressure of the solution must be less than the vapor pressure of the pure solvent by the amount equivalent to the weight of the column
of
if
FIG. 82.
vapor of unit area of the height
h.
That
is,
p = = pi h = P =
vapor vapor
pressure of solvent pressure of solution
height of the osmotic column density of the vapor of solvent
then
pi
hp.
(i)
pressure of the solution is equivalent to the of the column of the solution per unit area of the height weight
The osmotic
272
h.
PHYSICAL CHEMISTRY
Hence the change in the vapor pressure is to the osmotic pressure as the weight of any volume of vapor is to the weight of the same volume of the liquid, which gives
in which pi
-,
is
the density of the solution.
Now,
since p
substituting in the
Gas Law Equation,
pV = nRT, we
which g
is
have
= ^Kl
Similarly, since pi
-f-,
in
the
weight of the solution and V its volume, substituting in = nRT, we van't Hoff's equation for osmotic pressure,
pV
have
pi
-. nRT
Then
PI
=
p
pi
g
Substituting this value
in equation (2)
we have p
an
^
g
As
is
the weight
of the solvent (of
infinitely dilute solution)
and
the
molecular weight as determined from the vapor density (no assumption is made concerning its molecular weight in the
liquid state)
=
,
g
of the solute.
the reciprocal of the
number
of moles
The equation then
takes the form
which
is
Raoulfs Law.
>:*-?
CHAPTER XXV
FREEZING POINTS AND BOILING POINTS OF SOLUTIONS
IT will be recalled that the freezing point is the temperature at which the three phases solid, liquid, and vapor in Fig. 83. On are in equilibrium, and is represented by
the pt diagram, A B is the vapor pressure curve of pure water, and
'
AC
is
the sublimation curve.
The
^
intersection,
A,
is
the triple point
and represents the temperature and pressure at which the three phases are in ice, liquid, and vapor equilibrium. The pressure is, however, the
substance and
vapor pressure of the pure is, as we have previ-
FIG. 83.
ously seen, 4.6mm., while the temperature is not o C., since the freezing point is designated as the temperature of equilib-
rium under atmospheric pressure. The freezing point is then not quite the same as the triple point A, but at 760 mm. pressure differs from it slightly, the freezing point being 0.0075 lower than the transition point. As the change for one atmosphere pressure is small, for a few millimeters difference in pressure the differences are negligible, and no serious error is introduced in practice-if we consider the two points identical,
remembering, however, that to obtain the true transition point correction for the pressure must be made. For the solution, the vapor pressure is lower than the
vapor pressure of the pure solvent, and at some specified concentration we shall assume that the line CE represents
the vapor pressure of the solution.
273
The
intersection, C, of
ff
274
PHYSICAL CHEMISTRY
the vapor pressure curve, CE, of the solution, and the sublimation curve, AC, represents the equilibrium between ice, solution, and vapor, and is the freezing point of the solution. The freezing point then has been lowered from the temperato the temperature k, i-e- the lowering of the freezing time the vapor pressure has /2, and at the same point is /i been lowered from pi, that of the pure solvent, to p%, the vapor
ture
/i,
pz pressure of the solution, or pi It is therefore apparent that the lowering of the freezing point bears an intimate relation to the lowering of the vapor
.
pressure of solutions, and there must be a way of expressing this lowering of the freezing point in terms of the lowering of the vapor pressure of the solvent.
should be remembered that we are assuming that the solid phase separating from the solution is pure solvent, otherwise we might get a rise of the freezing point, as in the case
It
where
solid solutions or
isomorphous mixtures are separated
In the case of the separation of eutectic mixtures the out. simple relation will not hold.
early as 1788 Blagden showed that the freezing points of aqueous solutions of a given substance are lower than that
As
of the pure substance, and that this lowering of the freezing point is proportional to the concentration. But it was not
work of Rudorff (1861) and of Coppet (1871) that was given to the freezing point of solutions. It was, however, the work of Raoult, published in 1882, that presented the fundamental facts. He showed that the lowuntil the
attention
ering of the freezing point

tion,
is
proportional to the concentra-
and that the lowering
for various solutes is
of the freezing point of solutions nearly the same when one mole of the
solutes is dissolved in the
same amount
of the solvent.
He
found that
not only for water but also for a large number of organic solvents as well. This is illustrated in Table XLVI, which contains some of Raoult 's extensive data.
this is true
The molecular lowering
represents the lowering of the freez-
FREEZING POINTS AND BOILING POINTS
275
ing point produced by one mole of solute dissolved in 100 grams of the solvent.
TABLE XLVI
Solvent
:
Water
SOLUTE
276
PHYSICAL CHEMISTRY
Solvent
Acetic Acid
SOLUTE
277
and as shown from the values given in the above table, it is independent of their nature. We have previously seen that some substances in the liquid state have molecules which are
aggregates of the molecules of the substance when it is in the gaseous state, i.e. they are said to be associated. These
abnormal values of the molecular lowering can be accounted for by assuming that there is a decrease in the number of molecules of the solute due to association, while in the case of some solutes in water the increase in the number of molecules of the solute is due to the dissociation of the solute
molecules.
MOLECULAR WEIGHT DETERMINATIONS

Let Freezing Point Method. g = the number of grams of solute
= 5 = A =
the molecular weight in grams of solute the weight in grams of the solvent the lowering of the freezing point produced
by
grams
of solute in
5 grams
of solvent.
Then
-
lowering of freezing point produced by one

solute in
gram
of
5 grams
of solvent.
-= lowering
o
of freezing point
produced by one gram of
solute in one
gram
of the solvent.
- = lowering
8
of freezing point produced
by one mole
i.e.
of
solute in one
is
gram
of the solvent,
the
mo-
lecular lowering.
is
100 g
the molecular lowering for 100 grams of the solvent.

for a specified solvent the molecular lowering
But we saw that
constant, hence
we have
100 g
278
PHYSICAL CHEMISTRY
solving for
And
m we have
in
which Kpg is the molecular lowering when one mole is dissolved in 100 grams of solvent; then 100 F would be the molecular lowering when one mole is dissolved in one gram
of solvent.
From this equation we have a method for calculating the molecular weight of a substance from the freezing point lowering, for it is only necessary to determine A, the lowering
produced when g grams of solute are dissolved in
the solvent, and the constant p is known for the solvent. We have seen that Raoult determined the value for p ex-
5 grams
of
Subsequently a very large amount of work has been done in order to obtain this value with a high degree of accuracy. Nernst and Abegg discussed the theory of the
perimentally.
freezing point determinations, the common form of apparatus
and Beckmann has devised employed in these determina-
tions. We define the freezing point as the temperature at which the liquid and solid solvent are in equilibrium at atmospheric pressure. In Beckmann's apparatus, Fig. 84, we have an inner vessel, in which a thermometer and a stirrer are placed, containing an isolated mass of liquid to be frozen. This is surrounded by another tube forming an air jacket, which in turn is surrounded by the freezing mixture. In this determination it is assumed that when the liquid freezes a small quantity of ice is formed, and this is in equilibrium with the liquid at a fixed temperature, which is taken as the true freezing point of the liquid. But as Nernst and Abegg have shown, this isolated mass of liquid and ice is at a higher temperature than the surrounding freezing mixture and will therefore radiate heat, which would result in the establishment of some intermediate equilibrium temperature below the true freezing
279
point of the liquid under investigation. Then, too, the rate of stirring will affect the equilibrium temperature as
well as the
amount
of ice
which separates at the time of
Hence it is freezing the solution. evident that unless this equilibrium

temperature does not coincide with
the freezing point, the reading of the thermometer will not record the true
freezing point of the liquid.
Recent investigators have aimed to produce conditions such as to eliminate as many of these sources
of error as possible, with the result that the values of p for a large
number
rately
of solvents are fairly accuknown. For water the ac-
That p is 18.6. cepted value of is, one mole of the solute when dissolved in 100 grams of the solvent
will lower the freezing point of water 18.6; if one mole is disFlG. 84. solved in one liter (1000 grams) the constant becomes 1.86, i.e. the freezing point is lowered 1.86. If one mole could be dissolved in one gram of solvent, the freezing point would be lowered 1860, i.e. the Various authors use these freezing point constant is 1860. different values for F and hence more or less confusion may arise. In Table XLVI we saw that in one of the columns
"
freezing point
are given abnormal values for the molecular lowering of the an explanation of these will be taken up sub;
sequently.
Boiling Point Method. By referring to Fig. 83 it will be observed that if pz represents the vapor pressure of the pure
solvent
and
for
and is one atmosphere, then the boiling point is ts a solution of such concentration that its vapor pres,
280
sure curve
is
PHYSICAL CHEMISTRY
represented
24 .
represented by
The
boiling point would be of the solvent has been boiling point raised by the addi-
by CE, the
tion of
the solute
to
/4,
from
is,
/3
that
the rise of the

is /4
boiling point
/3 ,
while the pressure has remained

constant.
That the
the
rise of
boiling point of solutions is prothe to portional
concentration
was
emphasized
by
and has Raoult been confirmed subsequently. Raoult devised a method by means of which
these small changes
can
be
measured
accurately; in Fig. 85 is represented the general form of the apparatus. As

in the freezing point method sointheboil-
ing point constant

FIG. 85.
method a
quantity
is
of
the
solvent
employed, S, in which g
grams of the solute are dissolved,
and a
rise of
the boiling point of
degrees
is
obtained.
formula similar to that obtained by the freezing point method
281
may
be obtained, from which the molecular weight of the
solute
is
may
be calculated, that
is,
m = -^^
^,
in
is
which
KB
the molecular rise
when one mole
of the solute
dissolved
in 100
grams
of the solvent.
An
additional discussion of these
two methods and the
significance of the constants will
be presented in the following
chapter.
CHAPTER XXVI
THERMODYNAMIC CONSIDERATIONS
1798 Count Rumford's experiments on the boring cannon convinced him that heat is nothing more than energy of motion. Heat had been termed caloric, an igneous fluid, and this new view received but slight attention until the determination of a numerical relation between the quantity of work and quantity of heat made by Robert Mayer (1842) and by James Prescott Joule (1843) were published. Various experiments in this field have been performed, such
of
ABOUT
by the friction of liquids, by the of gases, heating effect of electric currents and compression the agreement between the results is as close as the errors of
as the heat effects produced
;
experimentation justify. These lead to the formulation of the Principle of Equivalence, familiarly known as the First Law of Thermodynamics or the Mayer-Joule Principle
:
heat is transformed into work, or conversely when work is transformed into heat, the quantity of heat gained or
11
When
proportional to the quantity of work lost or gained." " old fundamental notion that a body or system con" necessitates obtaining a clear conception tains so much heat
lost is
The
and energy. mass of a gas under specified conditions given of pressure and temperature, it will occupy a certain volume. If this gas be brought into contact with a body at a higher temperature and the pressure remain constant, the volume will increase, which, under suitable conditions, would result
of the terms heat, work,
If
we have a
The system receives heat energy from an external source and in turn does mechanical work. The relation between the heat energy imparted and the
in doing mechanical work.
282
283
mechanical energy obtained is represented in the statement that the total energy gained by a body is equal to the energy
supplied to
i.e.
it
in the
form
of heat,
and
in
any other form
of
the energy supplied in the form of heat can be energy, obtained in the form of work, and energy supplied as work is
withdrawn as heat.
servation of Energy.
These are statements of the law of Con-
It is only under perfect conditions that one form of energy can be completely transformed into another, and the reverse transformation accomplished. Such a process is termed
reversible.
maximum
processes are actually irreversible. quantity of heat that can be converted into
All
The work
by any machine depends upon the Principle of CarnotClausius and is known as the Second Law of Thermodynamics or the Law of Degradation of Energy. "Heat
cannot pass from a colder
to
a warmer body without some

"
// is imposcompensating transformation taking place," or sible by means of a self-acting machine unaided by any external agency to convey heat from one body to another at higher
"No change in a system of bodies that can take place of itself can increase the available energy of the
temperature," or
system."
Mechanical energy as well as can be energy completely transformed into heat but heat energy, energy cannot be completely converted into mechanical energy. It is not the actual amount of energy a system possesses, but the amount that can be utilized in any special transformation desired, that is of importance; that is, it is the
Availability of Energy.
electrical
utilized in
part of the energy present that is available and that can be any particular transformation.
Let dU represent the increase of the intrinsic energy of a system when the work, dW, is done by the addition of the
quantity of heat, dQ.
Then,
dQ = dU
dW.
284
This
is
PHYSICAL CHEMISTRY
the quantity of heat absorbed by the system, which In increases its intrinsic energy and does external work.
this equation Q,
U, and
is
of energy.
If
mechanical units,
the left-hand side.
are measured in the same units in measured in heat units and U and must be used on Joule's equivalent, /,
We
consider
dQ
it
positive
when
the sys;
dW is tem absorbs heat, is the is done work dU when by positive system, positive when the intrinsic energy is increased during the transnegative when
gives out heat
formation.
Since it is impossible to obtain work Carnot's Cycle. heat of a the from system unless there is another system at a lower temperature, Carnot showed that it is possible to
obtain work continuously from the two systems at different temperatures by employing a third intermediate system and causing it to undergo a series of cyclic transformations
known
as Carnot's Cycle.
Suppose we have two systems, 5, a source, and R, a refrigerator, at the constant temperatures /i and /2, respecIf they are placed in contact, heat will tively, with /i > /2. flow from 5 to R and no work will be done but if they are kept separated and a third system, M, used to convey the energy, work can be obtained.
;
at the temperature h is brought by some 1. The system convenient mechanical means, without gain or loss of heat, to the temperature /i (for a gaseous system, by compresThis is called adiabatic action. sion). 2. It is now placed in contact with the system 5 and receives from it a certain quantity of heat, Qi, while its tem-
The system perature remains constant and equal to t\. This is called isothermal also expands and does work.
action, as there is
no change
of temperature.
3. The temperature is now allowed to fall to h without the medium receiving or parting with heat (by expansion of
a gas).
Adiabatic action.
4.
285
refrig-
The system
is
brought in contact with the
erator
this
R and is allowed to return to the initial state.

Q
2,
During
change a certain quantity of heat,

Isothermal action.
is
given up to the
refrigerator.
This
may
be represented diagrammatically by the p-V
diagram, Fig. 86. 1. At the volume and pressure designated by A at the temperature /2 by adiabatic compression the volume will
,
change as indicated by the
line
AB without
BC we
:/**ftW
Voknw
gain or loss of heat. 2. Along the isothermal line
have the change of volume indicated,

while the quantity of heat, Qi, is being absorbed by the system at the constant
FlG 86
temperature t\. 3. During the fall in temperature the adiabatic line CD represents the change in volume through expansion while cooling to the temperature ^. at temperature k represents the 4. The isothermal change during which the quantity of heat Q2 has been given
DA
to the refrigerator. This is known as the Carnot Cycle, and the work done in the cycle is represented by the area A BCD. The difference Qi 02 is the heat transformed into work. This Then we should have the same process could be reversed.
up
area,
A BCD.
this perfectly reversible process, the Carnot Cycle, work can be derived indefinitely from a single source and refrigerator maintained at given constant temperatures, but since this cannot be exactly obtained on account of resist-
By
ance, friction, velocity, etc., the resulting cycle in practice is irreversible, and consequently the maximum work cannot
be obtained.
Efficiency is defined as the ratio between what is obtained to that which might be obtained. The quantity of heat Q\
286
is
PHYSICAL CHEMISTRY
the
is
amount that
that
Q2 is the amount supplied, but Qi it is the of or transformed, Q\ that is actually part

is
;
available
then the ratio
^ ~ ^2
l
is
called the efficiency, or
the availability of Q\ for transformation into work. If reversible cycles are operated between the same source
and
refrigerator,
:
seen as follows
they have the same Let
efficiency.
This
is
If the more efficient cycle be used as an engine moving directly to drive the less efficient cycle in a reverse direction,
the numerators which represent the work would be equal, and hence Qu> > Q\ a This means that the cycle b returns more heat to the source than cycle a takes from the source or, heat flows from a point of low temperature to a point of high temperature. This is impossible, and hence cycle a cannot be more efficient than b. In the same way b cannot be more efficient than a. The efficiencies, therefore, are If a were a non-reversible cycle, the above proof equal. would show that it could not have a higher efficiency than that of 6, but we could not prove that it was less. In other words, no cycle can be more efficient than a reversible cycle when acting between the same source and refrigerator.
.
;
The reversible cycle therefore has the maximum efficiency. The absolute temperature is sometimes defined by the
statement that the absolute temperatures of two bodies are proportional to the quantities of heat given up by one body
to the
medium and
rejected
by the medium
to the other in
the Carnot cyclic transformation in which the bodies play the part of source and refrigerator. Using this concept,
we have
T,- T
Or
TV
would be the value
of the efficiency of the of the heat energy available for
2,
287
The portion
Carnot Cycle. work between

be
1
the two temperature limits, TI and
T would
~
-
which
is
of heat absorbed
designated the availability. So if Qi is the quantity by a system at the temperature 7\, then
1/
7-
T\
^F 1
")
1
(
the quantity available for useful work, and
[
\TJ
Q\
is
the
quantity unavailable, or the waste
or the Available
Work =
Oi'fr-
The following is van't HofPs Applications to Solutions. of the of The Gas Law to dilute solutions, application proof
and
is virtually his own presentation By means of a reversible cyclic process carried out at a constant temperature, T, one mole of the dissolved sub:
i
stance
to
is
to be
solution in
it
again.
B, Fig. 87, a semipermeable membrane impervious to the solvent. Remove the pure solvent
to the outside through the walls ab and cd, which are impervious to the dissolved
removed from an aqueous the form of a gas and restored By raising the pistons A and remove the solute through oc,
Gas
Soiu&an
Solvent
substance, so as to stant concentration.
maintain
con-
FIG. 87.
By the two pistons, A and B, the is to be maintained between the gas pressure equilibrium and the osmotic pressure. At the temperature TI and pressure pi one mole of the solute will occupy a volume V\
as a gas.
The absorption
of the gaseous solute
is
such that
the gas
mole which
in equilibrium with a solution that contains one of the solute in volume VQ, the osmotic pressure of
is
is'-p^.
288
PHYSICAL CHEMISTRY
action desired includes the following steps
:
The
I.
both pistons be moved upward, one mole of the soltite may be removed reversibly and at constant pressure from the solution, and the amount of work done by it on A
If
is
piVi.
By The Gas Law

piV,.
is
= RT,
(i)
An amount of work performed by against the constant osmotic pressure, which will be expressed with a negative
signas
'-.:'
II.
-PO VO
work
By
First let
Foo,
a second process restore the solute to the solution. the gas expand isothermally to an infinite volume,
and
in so doing perform
This infinitely diluted gas

tact with the
may now
be brought into con-
volume VQ of solvent, and under these circumstances the solvent would not absorb any of the gas
because the gas pressure is zero. III. Now let the piston be lowered so that the solute
is
brought into solution, as the pressure

of
rises.
The expenditure
work
is
-J Jo
rv "pdV.
Here, however, p has not the value given by pV = RT, but a smaller value, because a part of the vapor has gone This part is exactly one into solution, as the pressure rises. mole when the pressure has increased to pi, and consequently if Henry's Law be true, when the pressure is p, the quantity of gas absorbed amounts to p/pi moles the undissolved part remaining is therefore (i p/pi) moles and p may be calculated from
:
pV=(i -p/pj RTi = RT
-pV
so that
"
289
RTi
Y + Vi'
is
Consequently the work done
since
V^
is infinitely
great, in
comparison to FI, the expresT/
sion becomes
-RTtlog.**.
Since the total
(4)
at constant temperature
Fig.
work done in a reversible cyclic process must be zero because the cycle of 83 would have no area,
(i)
(2)
(3)
(4)
and
or
V =
=
and
see that for equal values of V\
But
since T\
is
piVi
constant
we
VQ we must have
= p
any dissolved body which con-
From
this
we
see that for
forms to Henry's Law, for the same temperature and concentration the gas pressure and the osmotic pressure of its solution must be equal. Assuming that a gas dissolving according to Henry's Law has the same molecular character in the solution and in the gas, we may consequently draw all the conclusions as to the osmotic pressure of dissolved bodies that have been
drawn as to gas pressure or vapor pressure, i.e. we may apply Avogadro's Law to solutions, making use of the osmotic pressure instead of the gas pressure. It follows that The Gas Law can be applied to solutions.
2QO
PHYSICAL CHEMISTRY
to the
Relation between Lowering of Vapor Pressure due Solute and the Osmotic Pressure
use of the fundamental conceptions of thermovan't Hoff showed by the following isothermal dynamics reversible cyclic process the relation between the osmotic
By making
pressure and the lowering of the vapor pressure of the solvent due to the presence of a nonvolatile solute.
a solution containing a nonvapor pressure of the solution being pi and that of the solvent p. Then, as shown above, p > pi.
volatile solute, the
Let us assume that
we have
Let po be the osmotic pressure of the solution. The following order in the cyclic process is taken I. By means of a semipermeable membrane as a piston, remove through the piston osmotically and reversibly the amount of the solvent containing one gram-molecule of the
:
,-,
solute,
is
i.e.
^
g
grams.
Then VQ =
gP
The work done
P
II.
V
is
where
is
the volume in which one mole of the

pressure.
solute
dissolved
and p the osmotic
restore reversibly this quantity of solvent by distilling it, expanding iso thermally to pressure pi, condensing, and returning this solvent to the solution.
of
Now
At the temperature T and pressure p we gain a quantity work done by the reversible evaporation.
expanding this vapor (which is considered to be a gas) at the temperature T to the pressure pi, an additional quantity of work is gained. For one mole of the vapor of the solvent the work gained would be
By
pi
and for the mass containing one gram-molecule it would be
of the solute,
yS RT ^t_, gM pi
291
Finally, the vapor is to be condensed in contact with the solution at pi and T, in which process the work gained by evaporation is used up. The heats required for evapora-
tion
and obtained from condensation are assumed equal.
Since this cyclic process has been carried out at constant temperature, the net work is zero as before, and the osmotic
work spent must equal the work
of expansion gained,
Substituting for
VQ
.
its
value above,
r>-ri
we
obtain
mS = mS F Pn TT
gp
Pi
P *-
Mg
P
from which we get
RT
In dilute solutions p
which
is
the relation sought.
V =
nRT
Vo.
where
n = number
JL2-
of molecules dissolved in
volume
From this, since

\
RT
>i
substituting
we have
y.o
OZ S
P = Mn_. P Vo
This is an accurate form of Raoult's Law. If the difference between p and pi is small one may substitute in place
1
and obtain
p
p
pi
~~
M PQ
p
RT
Vo
_M n
P
Since
P
=
is
V"( moie),
the volume of one mole of the solvent
and
the volume of the solution which
when very dilute
292
PHYSICAL CHEMISTRY
becomes the volume of the solvent, hence Vo/ ^(moie) = A/", the number of moles of the solvent. This is the reciprocal of what we have in the formula, hence we have
=
p
This
is
~N*
the form of Raoult's
Law
previously used.
Relation between the Osmotic Pressure and the Lowering of the Freezing Point of the Solvent due to a Non-volatile
Solute
The following cyclic process showing the relationship between the osmotic pressure of solutions and the lowering
of the freezing point of the pure solvent when the nonvolatile solute is present cannot be carried out at constant
temperature and hence involves the Second
Law
of
Thermo-
dynamics. Let us assume that we have a large mass of a very dilute solution such that when the amount of the solvent that contains one mole of the solute is removed the concentraSince tion of the solution remains practically constant.
is
is very dilute, the change in the freezing point very small and when the volume of solvent containing one mole has been removed, the volume change is very small. Let us suppose that we have this solution so inclosed that by means of a frictionless semipermeable piston we can remove the desired quantity of solvent, at the temperature
the solution
Allow this to of the freezing point, T, of the pure solvent. freeze; cool the whole system to the freezing point of the
Bring the ice in contact with the solution and allow it to melt and become part of the solution. Finally warm the whole system up to its original temperature, then we shall be back to the initial state, having comsolution
A/.
pleted the cyclic transformation.

stages in this reversible process
:
We
have the following
I.
293
At the temperature of the freezing point, 7", of the pure we have done work in removing osmotically by means of the semipermeable piston the quantity of the There have solvent containing one mole of the solute.
solvent
been removed
g
is
grams
of the solvent at this temperature.
external work done against the osmotic pressure po P O VQ mechanical units or ApQ V calories, where VQ is the volume of solvent removed and A is the conversion factor.
II.
The
Now
allow these -
grams of the solvent to freeze
isothermally and in doing so there will be liberated

calories of heat at the temperature T, where L F heat of fusion of one gram of the solid solvent.
III.
is
LF
g the latent
Now
cool adiabatically the solution

is
and
also the -
grams of the solvent which T - AT.

IV.
now
ice,
to the temperature
AT") we place the to melt and to be-
At
this lower
ice in contact
temperature (T with the solution, allow
it
come a part
of the solution again.

is
In melting, the heat
absorbed at this lower temperature

V.
Lr
calories.
Now
is
raise the
batically to the original temperature
temperature of the whole system adiaT, during which no
heat
given out or absorbed. is a reversible cyclic process, and the sum of the work terms is zero. The work in III is equal and opposite in direction to that in V, and therefore they may be neg-
This
lected.
We
shall
then have
T/
Po v
or
Sm o~ L * 8 +
T
,
j ,Sm = L *
8
'
-
V ^ y PO o
= ^'
-L ^f
2Q4
r-
PHYSICAL CHEMISTRY
is
But Lf
g
the heat absorbed by the system at the higher

TI.
temperature,
heat,
Let us designate this by Q\ and the

the lower temperature,
LF
', given up at 8
by
Qz.
we
will
designate
On
P
substitution
we have
ft.
V =
1
Qx
But from the equation ^
~
Qi
~
?
,page 286, we
should have on substitution, since TI
T2 = AT
or
T7
T SmAT V = L F
~.
Sub-
We assumed that The Gas Law for ideal gases holds in the case of infinitely dilute solutions. Hence for the osmotic pressure at the freezing point T\ of the pure solvent we will
have upon the basis of this assumption p V = RT\. we have^ stituting in the above the value of P V
,
rC/i
DT
Sm -Lp
g
AT
TI
Solving for the slight temperature difference
AT
which
we
will designate as A,
we have
LfSm
which gives us
mA
g
'
LPS
the gram-molecular lowering, since it is the lowering of the freezing point of a solution of one mole of the solute con-
tained in
5 grams
of the solvent.
It is
customary to take
ioo grams of the solvent, then
tion gives
295
5 =
100,
which on substitu-
mA
g
ioo
We have previously seen

R,
is
i
(page 26) that the gas constant,
equal to 84,780 gram-centimeters per degree.

i
calorie is 4.186 Joules, and calorie
Joule is
-^- gram-centimeters.
981
=
=
I0
or 42,670 gram-centimeters.
Then
or
^
42670
981
1.987 calories per degree as the value of R,
R =
2 calories
per degree approximately.
Substituting, the equation takes the
form
,.
g
as the expression for
T2 ioo L
2
the gram-molecular lowering of the the freezing point of the pure solvent on the absolute scale. expressed
freezing point when T is
The
left-hand
member
is
the form of the expression
used by
g Raoult, which he stated
was equal to a constant
Kf ^
.
= K, is the empirical
formula obtained by him and
g
It subsequently confirmed by numerous experimenters. states that the lowering of the freezing point, when one mole of various solutes is dissolved in the same arbitrarily
selected quantity (ioo grams) of a solvent,
is
a constant
Hence it is evident that the right-hand member quantity. of equation (i) must also represent this same constant. Therefore, knowing T, which is the temperature of the freezing point of the pure solvent, and L p which is the latent
,
heat of fusion of the pure solvent, the value of
IOO
can be
296
PHYSICAL CHEMISTRY
is
readily ascertained, which
the value of the gram-molecu-
lar lowering of the solvent.
There
is
no term in
this ex-
pression which relates to the dissolved substance, hence the character of the solute should not affect the value, and we
are justified in drawing the conclusion that the gram-molecular lowering of the freezing point is a constant and inde-
pendent of the solute,

molecular lowering.
i.e.
100
LF
KP
= ^
g
gram-
We have then two experimental methods by means of which the value of this constant, F can be determined the as Raoult (i) lowering produced did, by determining by the freezing point method, (2) as van't Hoff did, by calF from the latent heat of fusion of culating the value of the solvent. The agreement between the two methods is very close, as the values in Table XLVII show, wherein
the quantity of the solvent, 5, employed
is
100 grams.
TABLE XLVII
SUBSTANCE AS SOLVENT
297
from the value of Kp the latent heat was and found to be 13, and Pettersson 's subsequent determination was 12.94. So it is evident that the freezing
for ethyl bromide,
Pettersson subsequently determined 22.1 calories per gram. the latent heat and found it to be 22.3 calories. Similarly
calculated
of fusion
point constant can be employed to calculate the latent heat by van't Kofi's formula.
The equation
takes the form
for the lowering of the freezing point then
mA
which A is the lowering when g grams of the solute are dissolved in 100 grams of the solvent,
in
or
~
which A
is
mA _
100
KF
~~s~
in
solved in
5 grams
the lowering when g grams of solute are disof the solvent.
Solving for m,
we have
as the general Freezing Point Equation. Relation
between
the
of the Boiling
Osmotic Pressure and the Elevation Point of the Solvent due to a Non-volatile
Solute
By evaporation at the boiling point of the solution, T -f A T,

remove from a large mass of a very dilute solution a quantity of the solvent that would contain one mole of the solute
without materially changing the concentration of the solution; cool the vapor separated and the solution to the temperature of the boiling point of the pure solvent, T; condense the vapor and introduce it osmotically into the
298
PHYSICAL CHEMISTRY
solution again; raise the temperature of the solution to the boiling point of the solution. By such a cyclic process similar to that employed in the case of the lowering of the
freezing point relationship, we derive an expression for the elevation of the boiling point analogous to that obtained for
the lowering of the freezing point,
i.e.
wA
g
in
100
T2 Lv
which the terms have the same significance as in the molecular lowering of the freezing point equation, except that T refers to the boiling point of the pure solvent at atmospheric pressure on the absolute scale, L r is the latent heat
of vaporization of
one gram of the pure solvent at the temThis is the rise of the boiling point. have and a we elevation is constant gram-molecular quantity
perature T, and A
IOO
which can be calculated from the boiling point and latent

heat of the pure solvent. As in the case of the lowering of the freezing point we may obtain
SA
the general Boiling Point Equation, in which A is the rise of the boiling point when g grams of the solute are dissolved
in
S grams
of the solvent.
Similarly the constant for the boiling point can be obtained by each of these two. methods and the experimental values
agree well with those calculated by the use of van't Hoff's formula, as is seen from the values given in Table XLVIII, wherein the quantity of the solvent, 5, employed is 100
grams.
TABLE XLVIII
299
300
PHYSICAL CHEMISTRY
the value of
boiling
the latent heat of fusion of the pure solvent. Similarly B is designated the gram-molecular rise of the
point and can be obtained experimentally from boiling point determinations or calculated from the latent heat of vaporization of the pure solvent.
In Table XLV are given the values for the freezing point constant and in Table XLVI the boiling point constant of a
number
of the
most common solvents used
in
making molecof solvent are
ular weight determinations
when 100 grams
employed.
CHAPTER XXVII
tricity
VOLTA recognized two different types of conductors of elecand upon this basis divided them into Conductors of the First Class and Conductors of the Second Class. Conductors of the First Class include those substances in which
the passage of the electric current is not accompanied by a simultaneous motion of matter itself. The metals belong to
this class as well as
some other good conductors, such as
To the Second Class certain metallic sulphides and oxides. belong those conductors in which the passage of the electric current is accompanied by the corresponding motion of the
matter composing them. These comprise solutions that conduct the electric current. This is the classification that
also recognized to-day. Many theories have been proposed in order to explain the mechanism by which the electric current passes through a
is
Among
trical.
conductor as well as the various phenomena observed. the first efforts was Davy's Electrochemical Theory,
is
wherein he assumed that chemical affinity
essentially elec-
That is, that the atoms possess electrical charges, and when atoms possessing electrical charges of different sign come near one another there results a decomposition and a
recombination depending upon the relative strength of the charges of the same sign, the stronger uniting with the atoms
having the charge of opposite sign, thus producing a new compound. He also supposed that a large number of atoms of small charges of the same sign might unite and form a unit
301
302
PHYSICAL CHEMISTRY
with a greater charge than that of some single atom. This theory of Davy was not very generally accepted. Berzelius, from his work on the decomposition of numerous solutions by means of an electric current obtained from a Voltaic Pile, concluded that the compounds in solution were electrically decomposed into two parts, a basic oxide and an anhydride. Copper sulphate, CuSO 4 for example, he consid,
ered as electrically decomposed into the basic oxide, CuO, and the anhydride, SOs, which were respectively positively and negatively electrified. In order to explain such reactions Berzelius
tion with another

tive
assumed that each atom when in juxtaposiatom possesses two poles, one electroposi-
and the other electronegative. When in contact, one of these poles is much stronger than the other, and the atom " reacts as though it were unipolar." Hence, the chemical an of element upon the amount of the elecdepends affinity
trical charge of its atoms positively charged atoms reacting with negatively charged atoms, and the electricities of opposite signs neutralizing each other, resulting in the forma-
tion of a
tive,
compound
electrically positive or electrically nega-
depending upon which is in excess. This may result from the direct union of the elements, and two such compounds may in turn combine, forming a still $iore complex substance. The formation of the so-called double compounds SO 3 is the union of negatively charged S is thus explained.
with three negatively charged oxygen atoms, resulting in the formation of the strongly negative residue SOs. The union of two negatively charged atoms is accounted for by assuming that every atom possesses two charges, positive and negative, and that in each case the negative charge predominates.
The negative charge
of the
oxygen neutralizes the positive
charge of the sulphur, giving a negatively charged compound, SOs. This theory of Berzelius, known as the Dualistic Theory, met with general acceptance and had a very pronounced
influence
303
Particularly in quantitative anallines Berzelius was a pioneer, in which ysis and mineralogy, Dualistic the of the has he left Theory in the methods imprint
upon chemistry.
adopted in writing the formulae of minerals and in reporting

the analysis of substances. The mineralogists employ this idea in writing the formulae of minerals for example, the formula
;
for
feldspar,
K Al Si Oi
2
2
6,
is
written
A1 2 O 3
6 SiO 2
The chemist reports his analysis, not as the percentage of the particular element, but as the oxide thus, calcium
;
is
reported as CaO, phosphorus as P2 6 sulphur as SO 3 etc. In this way the imprint of the Dualistic concep,
tion of Berzelius
is
very marked even to-day, although

effort to get
many are making an

analytical data.
away from
it,
e.g.
the
agricultural chemists in their methods of reporting their
Many objections
time
all
to Berzelius' Dualistic
Theory
arose,
among them were two which he could not
explain. acids were supposed to contain oxygen, but with the discovery of the halogen acids and their salts there was
and At that
presented a large group of compounds that could not be conceived as being composed of a basic oxide and an anhydride,
and consequently presented a most
serious obstacle to the
general application of the theory. Liebig called attention, to the replacement in organic compounds of the positively charged by the negatively charged Cl, such as the forma-
from tion of the chloracetic acids, 2 C1COOH, CC1 3 These acids all have properties similar to those 3 COOH.
CH
COOH
CH
of acetic acid.
Recently
gas
tive
is
J. J.
Thomson has shown
that
when hydrogen
electrolyzed, positive appears at one pole and negaat the other, from which he concluded that the hydro-
gen molecule is probably made up of a positive and a negative part molecule and that hydrogen is not always positive. He called attention to the fact that we have negative chlorine replaced by positive hydrogen without altering the type
304
of the
PHYSICAL CHEMISTRY
compound.
For example; from
3,
.
CH
C1,
CH
C1 2
CHC1 and CC14
CH 4 we may obtain From CHC1 3 vapor, as

,
well as from a study of the spectra of the vapor of methyl-
ene chloride, ethylene chloride, and even CC1 4 Thomson " concluded that it would appear that the chlorine atoms,
in the chlorine derivatives of
electricity of the
same
sign as the hydrogen
methane, are charged with atoms they
displace."
Faraday, after having convinced himself that there is only one kind of positive and one kind of negative electricity, showed experimentally that the chemical or magnetic effects
circuit are proportional to the amount or quantity of electricity passing through the circuit. By arranging a number of solutions so that he could pass the same quantity of electricity through them, he demonstrated " that the quantities of the substances separating at the elec-
produced in any
trodes in the
same time are in
the proportion of their equivalent
weights ," or as Helmholtz states

tricity
to other
is
"
it,
the
same quantity of
elec-
passing through an electrolyte either
sets free or transfers
known
conditions always the same number of valencies" This as Faraday's Law, and the constant 96,540 cou-
.will
lombs, onefaraday, means that 96,540 coulombs of electricity deposit one gram-equivalent of a metal or do other
chemical work equivalent to this. Faraday (1839) called those parts which migrate through the solution under the electrical stress and conduct the
electricity, ions.
He
also
emphasized the fact that
it is
not
easy to
same
ions are, as frequently they are not the as that which separates out on the electrodes. In the
tell
what the
case of the decomposition of solutions of sodium hydroxide and sodium sulphate, there appear at the electrodes in both
hydrogen and oxygen; but the parts which migrate through the solution of NaOH are undoubtedly not hydrogen and oxygen ions, but are supposed to be Na and OH ions. In
cases,
the case of
Na SO 4
2
solution, Daniells said
if
the ions are
305
Na and SC^, the sodium reacts with the water, liberating hydrogen at one electrode, while the SO 4 reacts with water at the other electrode, forming sulphuric acid and liberating oxygen. The ions which migrate toward the cathode are designated cations, and those which migrate toward the anode are the anions. This process of migration occurs only in conductors of the Second Class, and substances which yield solutions that conduct electricity in this way Faraday termed electrolytes, and the process of decomposing the substances (electrolytes)
by the
electric current
he called
It was,
electrolysis.
however, previous to this time that Nicholson and decomposed water by means of the electric current, and many attempts were made to explain the process by means of which this occurred. In 1805 Grotthus presented the first complete theory for this phenomenon of the conduction of a current through the solution and also for
Carlisle (1800)
tific
His theory satisfied the scienworld and was universally accepted until recent times. According to the theory one electrode is positively charged
the decomposition of water.
and the other electrode is negatively charged by the electric current, and these charges are communicated to the molecules of water, which become polarized and oriented so that
the positive part of the molecules, the hydrogen atom, all face in one
direction
part, the oxygen atom, in the opposite direction. This is illustrated in Fig. 88. The
and the negative
f>
~^
c~+
-o f>
"*
c>
î
CE2D CET3CZD G
CUD CZD CUD

FIG. 88.
current enters the solution through the anode, and the positively charged
parts of the molecules are all in the direction of the negative electrode or cathode, by which they are attracted and
arrange themselves as represented. If the charges on the electrodes
(i.e.
the Electromotive
Force) are large enough, the extreme hydrogen and oxygen
306
PHYSICAL CHEMISTRY
atoms nearest the electrodes are liberated and go to neutralcharge on the electrodes where the hydrogen and oxygen appear as gases the condition is represented by
ize the electrical
;
This leaves the other parts of the molecules free. These immediately combine with the free parts from the adjacent molecules, and this decomposition and recombination pass on throughout the liquid between the electrodes. These new molecules become oriented as shown in III, when In making these the process just described is repeated.
II in the figure.
transfers of parts of the molecules
some would have
to
move
over a considerable distance.

molecules.
This theory of Grotthus calls for a decomposition of the To accomplish the decomposition of the moleThen a recomcules would require a good deal of energy. bination would take place, but before this takes place some time would elapse, during which the particles would be free. The question arose as to what would inaugurate the second decomposition, and the third, and, in fact, where would the
energy come from for the nth decomposition. The question was asked whether it was the molecules of water or the molecules of the dissolved substance that were decomposed and conducted the electric current. This was a point of controversy for a long time, opinion was divided, and such
:
" water evasive expressions as the following were used which by the addition of sulphuric acid has become a good conductor."
In order to electrolyze a solution the electromotive force has to reach a certain value a value below which no detakes and the composition place affinity of the atoms would not be overcome. Experimentally it has been found that
the electric current can be
tive force is very small. nitrate is placed between
made
to pass
when the electromo-
For example, if a solution of silver two silver electrodes, the decomposition of the silver nitrate with the deposition of silver on one electrode and the dissolution of silver from the other can be
shown
307
to take place. We have merely the transfer of silver from one electrode to another, and this holds for all differences of potential however small. It was Clausius, about fifty years later, who first pointed out this contradiction, and he stated that any theory which requires the decomposition of the substance must be aban-
Using Faraday's definition of terms, Clausius concluded that the individual ions are not bound together, but must exist uncombined and free to move in the solution.
doned.
Employing the conception of the Kinetic Theory of Gases, which was being emphasized by the scientific world at the time, Clausius assumed that a few part molecules or ions are free in so far as they are in independent motion or vibration, but are kept close together by their chemical affinity. This affinity is overcome by the rapid vibrations, and the molecules get into such positions that it is more convenient for one part of the molecule to unite with the other part of another molecule than to recombine with its original partner. He imagined a continual exchange taking place between the parts of the molecules. So when an electric current passes, this simply guides the exchanges, which become much more frequent under the electrical stress. If we consider a cross
more
section at right angles to the direction of the current, positive ions would move in the direction of the cathode
than toward the anode, and more negative ions would move As a result there would be a in the direction of the anode. certain number of positive ions going in one direction and negative ions in the opposite direction. This motion of the
two parts
of the molecules in the solution causes the con-
duction of the electricity. Hence, according to Clausius' Theory, the current does not cause a decomposition of the molecules but guides those part molecules which are mo" mentarily free. Clausius in his conclusion declares every assumption is inadmissible which required the natural condition of a solution of an electrolyte to be one of equilib-
308
PHYSICAL CHEMISTRY
rium in which every positive ion is firmly combined with its negative ion, and which, at the same time, requires the action of a definite force in order to change this condition of equilibrium into another differing from it only in that some of the positive ions have combined with other negative ions than those with which they were formerly combined. Every such assumption is in contradiction to Ohm's Law." As we shall see subsequently, this theory of Clausius, which was very generally accepted, is the basis of the present theory as presented by Arrhenius but before we take up a consideration of this it is necessary to present some of the experimental work of Hittorf on the migration of ions, and on the electrical conductance of solutions by Kohlrausch, which led to the theory of free ions as shown by Arrhenius and by Planck.
;
In the electrolysis of a solution of the substances appear at the two equivalent quantities If a solution of HBr be electrolyzed, for one gram electrodes.
of
will
Transference Number.
hydrogen separating on the cathode, 80 grams of bromine appear at the anode and if a solution of HC1 be employed and electrolyzed until one gram of hydrogen is ob;
tained, the equivalent of chlorine, 35.5 grams, is liberated at the anode. In order for these quantities to appear at the electrodes, it is necessary that they come from different parts
said, the parts of the elecand conduct the current. the solution trolyte migrate through A current of one faraday flowing through a solution liberates one gram-equivalent of hydrogen (1.008 grams) and at the
of the solution,
and as Faraday
same time there is liberated at the anode one gram-equivaHence both of these quantities lent of some other substance. of material must have migrated through the solution to their respective electrodes and consequently have transported their
respective shares of the quantity of electricity that passed through the solution. It was thought that equal quantities
of electricity
moved through
the solution in opposite direc-
309
This is not necessary, for it is conceivable that in tions. order to cause a definite quantity of electricity to pass through a given cross section of the solution we could imagine all of
the electricity to be transported by the ions moving toward the anode, or that it could be divided in any ratio we might
the ions migrating toward their respective elecat the same speed, they would carry the same of the current, but if one traveled twice as fast, quantities the proportions of the current transported by each would
choose.
If
trodes
moved
be
i.
Let us assume that we have a solution of HC1 and that the vessel, Fig. 89, containing it is divided into three compartments, A, B, and C, each of which contains 10 gram-equivaLet us electrolyze until lents of hydrogen and of chlorine.
there
has been separated one gram of

35.5
hydrogen and
grams of chlorine. Then there should be left in compart-
ment C, 9 gram-equivalents of hydrogen, and in A 9 gram-equivalents of chlorine. FlG 8g But some chlorine ions have migrated over to A, and some of the hydrogen ions have wandered The question arises, how much of these have into C. If we assume that ^ gram-equivalent of hydrogen ? migrated has wandered from A to B and from B to C, then there has been removed from C % gram-equivalent of hydrogen more
than there migrated into C, hence there is a change in concentration of the hydrogen contents of C as well as of A while there migrated into B just the same quantity that migrated Let us assume out, and the concentration remains constant.
,
it
that the hydrogen ions move five times as fast as the chlorine, then f of the transportation of the electricity should be done
In this case, A chlorine. should have lost f gram-equivalent of chlorine, or there should remain 9^ gram-equivalents. As one gram-equivalent of
by the hydrogen and ^ by the
hydrogen was deposited from
C and
f was transferred from
PHYSICAL CHEMISTRY
to
and from
gram-equivalents.
The
to C, there must be remaining in C, gf loss in C, the cathode chamber, is
f gram-equivalent.
gram-equivalent, and the loss from the anode chamber The ratio of these losses,
is
Cathode chamber loss ^ gram-equivalent Anode chamber loss f gram-equivalent

is
-J-,
or the ratio of the rates of migration of the anion and of

i.e.
the cation,
Rate Rate
of migration of anion of migration of cation
_ "~
i_
Loss at the cathode Loss at the anode

l
Hittorf carried out (1853-57) a
ar Se
number
of experi-
ments in which he determined the ratio of the losses in concentration of the solution about the electrodes after electrolysis and from these determined the ratios of the rates of migration of the ions. He found that it was not necessary to electrolyze until one gram-equivalent had been separated, but passed the current a sufficient length of time to get a marked change in concentration in
the electrode chambers. The type of apparatus frequently employed is illustrated in After electrolyzing a solution of silFig. 90.
ver nitrate,
of
cell
it
was found that 1.2591 grams

deposited in the electrolytic
Ag had been
A
FIG. 90.
;
and the same amount in the coulometer. unit volume of the solution contained
before electrolysis the equivalent of 17.4624
grams AgCl and after electrolysis 16.7694 grams AgCl, which represents a loss equal to 0.5893 gram of silver. If no silver had come into the cathode liquid, then there should have been a loss in concentration the same as the amount of silver deposited, 1.2591 grams, but there was a change in concentration of only 0.5893 gram, hence
311
the
the difference, 1.25910.5893, or 0.6698 gram, represents amount of silver that migrated into this part of the
If as
solution.
much
silver
had migrated as was
precipi-
the current would have been transported by the tated, and its share in transporting the current would have silver, been 100 per cent or unity, and the 3 would not have
all of
NO
But only 0.6698 gram migrated, so the share of the current that deposited 1.2591 grams of silver must have
assisted.
been
9-
0.532; or 53. 2 per cent of the electricity was
1.2591
= 53.2 by the silver, and the difference, 100 the was NOs. Or, representing 46.8 per cent, transported by this on the basis of unity, the part carried by the silver is 0.532 and that by the NO 3 is 0.468.
transported
In general, then,
if
n c = transference number n a = transference number

then n c
of the cation
of the anion
na =
i.
It
was seen above that
the change in concentration at the cathode the total change the current would produce
j
the change in concentration at the anode the total change the current would produce
Dividing the second by the
first
we have
_ ~~ n^ f
the change in concentration at the anode

the change in concentration at the cathode
na
speed of the ions

trates.
is proportional to the the solution varies with the temthrough the as Table XLIX illusand with concentration, perature
The
transference
number which
312
PHYSICAL CHEMISTRY
TABLE
XLIX
TRANSFERENCE NUMBERS OF THE CATIONS

by Noyes and Falk
So-called Best Values Compiled
313
The limiting value of the transport numbers with an increase in temperature seems to be 0.5, which indicates that the current is transported by the cation and anion
equally. anions.
This applies to
all
combinations of cations and
In the case of a number of electrolytes the transport numand vary greatly with the concentration as well as with the temperature. Hittorf found for aqueous
bers are abnormal
cadmium iodide values greater than unity for more concentrated than normal; for 3 -normal the value for cadmium is 1.3, and for 0.03 -normal the value is 0.6 1 These abnormal values are explained primarily upon
solutions of
solutions
the basis of the formation of complexes in solution with or without the combination of the solute with the solvent. It
is
further assumed in the determination of the transference

there
is
number that
this is
no movement
of the water with the
electric current,
and
in the case of concentrated solutions
no longer the case. By the introduction of a substance will remain stationary and will not take part in the conduction of the current, methods have been devised in
which
order to determine the
different ions.
amount
of water transferred with the
current and consequently the
amount
associated with the
Kohlrausch's Law. By employing the principles that Wheatstone used in measuring the resistance of conductors of the first class, Kohlrausch devised a method for measuring the con-
ductance of solutions.
paratus,
illustrated
The apFig.
91, consists of a wire, AB, provided with a scale so that the sections
in
a and b can be measured
the
known
resistance R, and the electrolytic cell, C, into which the solution, the resistance of which is to be measured, can be placed (the Arrhenius
"
314
PHYSICAL CHEMISTRY
;
a battery, type of cell is illustrated in detail in Fig. 92) B, and induction coil, /, or some means of producing an alternating current. T represents the telephone by means of which the adjustment of the contact point can be correctly made. By introducing a
known
is
resistance into
and moving the point
k along the wire until the
minimum sound
obtained, the resistances in the four parts or arms of the apparatus will be in the ratio,
R R =
:
b.
Solving,
we have
R =
c
^-^
a
which gives the resistance of the solution in the electrolytic cell. The conductance is
the reciprocal
FIG. 92.
of
the
resistance,
then
the
conductance, c
=
RC
Electrical resistance
in reciprocal
ohms
is expressed in ohms and conductance or mhos. The unit of conductance is the
ohm, the mho. The specific conductance, *, is the conductance of a cube of the solution having sides i cm. The conductance of the solution containing one gramlong.
reciprocal
equivalent of the solute when placed between two electrodes i cm. apart and of such size as to contain the specified volume
is designated the equivalent conductance and represented by A. Then A = *V, in which V is the volume in cubic centimeters which contains one gram-equiv-
of the solution
is
alent.
It is customary to employ a subscript to designate the volume of the solution that contains one gram-equivalent of the solute, i.e. A F which is the equivalent conductance at
,
volume V, and A w
lution.
is
The molecular conductance n

i
the equivalent conductance at infinite diis the conductance of a
mole of the solute placed between two cm. apart and of sufficient size to include the volume of the solution, ^ = *cV. In many texts and journals it is customary to use X to represent the equivalent conductance.
solution containing one
electrodes
It is
315
more convenient
so that the electrodes are not exactly
to prepare the electrolytic cells i cm. apart, are not
i sq. cm. in area, and do not inclose a volume of one cubic centimeter of solution. Consequently, it exactly is necessary to employ some factor, K, such that the value of the conductance of the solution, as obtained by this cell,
exactly
will give the specific conductance, that is, multiplied by the conductance of a cube of the liquid one centimeter on a
side.
We
times
since c
K
=
then have, the conductance of the solution c equals the specific conductance, i.e. cK = K, and
-^-,
we have
of
f-,
or solving,
is
we obtain
Rh
.
The value
K, which
termed the
Cell Constant,
may
the
be readily determined experimentally by employing in a specified solution, the specific conductance of which is known, determining the value of R, a, and b by the Kohlrausch method, substituting, and solving for K. Then
cell
knowing
tion
K for the particular cell, the equivalent conductance

K
of other solutions
A =
V which
can be readily determined from the relaon substitution of the value of K becomes
KaV A A=
^T-
Kohlrausch (1873-80) by the above method made the measurements of the conductance of a very large number of solutions of different strength. By dissolving one grammolecule and making it up to one liter we have a molar solution, and if the quantity representing one gram-equivalent be dissolved, we have a gram-equivalent solution. In
the case of KC1, NaCl, NaOH, etc., these two kinds of solutions are the same but with BaCl 2 etc., one half a 2 SO 4
;
mole
required for a gram-equivalent solution, and hence these are one half the strength of molar solutions. In Table L is compiled the equivalent conductance A of aqueous
is
solutions at 18
salts.
C. of
many of
of the
the
common
acids, bases,
and
The headings
columns are self-explanatory.
hH
O HH
00
f^
î~
'""'
ONCOOO
i-i
O ON 1^* iO\O tÔO O ^00 lOOcd ^cOt> O O lOOoOO

i-c
rt- (S
ONOO tî-<
MD~
^f
iO
l~>.
ON t>.vO vO t>GO vO vO
!>
W "
10^
>-i
r>
"-
iO
i-<
ON ON(N
<N
^ lOOO iO lOvD ON:
rj-oo
^X
NO rO fO ONOO
ÔO
00 fÔO 00 ONOO
"^"i
~
O
VO
HH
ONOO 00
"*
ON
O
ON
HI
vO Ô
(M
ON ^*vO ro
M~)
O
"-1
*^
r^
HH
^
Tf-
O lOvO
HH
rCNO ON "- oJ ONOO ON ON O ONOO
O\OO vO ON
GO
10
v> vO 00
MVOC4oOfO*-ivO>-i ON vO ONCOiOCSNO'o\
10 ONOO
ONO
<v
if)
i-
lONO ONOO
O
i-.
ON o '* vO
O
PQ
oo OO rOOO
rr>>-iOOO
vo MOONO
NOON
O
t-i
vO
MOONHH
ro
O d
OONtÔooiOcO
rHO ONVO
NO 00 00
HH
t^-Ô
O>-iOOONrl-i-irJ-rOC<
10
tGO
00 10
OOONiOOvOvOrtHH HH
fOvO
10
O '~~
ON
'
t^
-ii-
voq^-HH 00
ONOO
t>-
lOvO
hi
HH
O '~N M
>O >O X
iO
"oio^qo-oo
10 to M vo 10 10 (S O ON
O M d
ONOO qvoo
oo* oo*
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10
ON
o
UIV
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r>.oo ON
i-*
1
.
317
the data in this table it will be observed that the of all these solutions increases with conductance equivalent the dilution, and it is found that the difference of the conductance for the first dilutions is very marked, while for high
dilutions the differences are small,
From
showing that the values
for the equivalent conductances are reaching a limiting maximum value. That is, at infinite dilution, which is ap-
proximately 1000 liters and above, the value for A becomes constant. This is shown in the following numbers for NaCl,
the difference being with increased dilution
3.69;
is
:
6.69
4.29
1.77; 0.94; 0.79; 0.64; 0.28. This shows that the value for the equivalent conductance
3.91;
2.33;
1.83;
approaching a limiting value.

2.
The
is
illustrated
additive property of the equivalent conductance by the values given in Table LI, which are
obtained from Table
L for dilution
TABLE LI
of 10,000 liters,
which we
may
take as A w
ELECTROLYTE
318
PHYSICAL CHEMISTRY
the same value for the sulphates. In the case of the acetates the agreement is not so marked. From a consideration of the data he obtained, Kohlrausch found that the equivalent conductance at infinite dilution
could be represented by the sum of the equivalent conductances of the cations and of the anions. That is, the migra-
and
tions of the ions in solution are independent of each other, their combined effect results in the conductance of the
solution.
Hence we have the formulation
of
Kohlrausch 's
is
Dilution
Law
of the
independent migration of the ions in the

-f
expression
A^ = A c
which, stated in words,
the
equivalent conductance of a solution at
infinite dilution is
i.e. the equivthe plus equivalent
the
sum
of the equivalent ionic conductances,
alent ionic conductance of the cations,

ionic
3.
Ac
conductance of the anions,
The
ratio of the current carried
by the cations
to the
termed the transference or transport number of the cation, and similarly we have the transference number of the anion. These transference numbers are dependent
total current is
on the
velocities of the ions,
and we have the
relation
=
na
the
in which
uc
is
Va
the velocity of the cation and v a
is
velocity of the anion.

is
As the
total equivalent
conductance
the
sum
of the equivalent ionic conductances, it follows
that the relation
^=A
va
holds,
and therefore
^=^
na
Aa
na
Add-
ing unity to both sides of the equation
we
Aq
,
obtain
+ =
i
^+ A
a
i,
which becomes
+ Ha =
na
AC
+
Aa
and remembersub,
ing that
stitution
nc
na
na =
.
i,
and A c
A =
A^-,
we have on
= *
Aa
we may
Solving for
A we have A = n a A x and
.
similarly
also obtain
A c = nc Aw
319
illus-
We may now
tration.
is
/u,
apply this to a
specific
problem as an
The equivalent conductance A^ at infinite dilution of NaCl 109 mhos, and this for NaCl is also the molar conductance, The transport number, n a for the anion, the chlorine M ion, is 0.615. Substituting these values in the equation we have A = 0.615 X 109, or A = 67, the equivalent ionic conductance of chlorine. The equivalent ionic conductance of
.
the sodium ion

tion above,
or substituting in the equa(10.615) 109, and A c =42. It is apparent that if the transference number of one ion is known, then the ionic conductance of it and of the one with which it is associated may be readily calculated. Above we have determined the equivalent ionic conductance for Na and Cl. Now if we determine experimentally the equivalent conductance, A w for NaNOs, we have from Kohlrausch's
is
109
67
A c = WcA^,
is
= 42, A =
c
Law, A^
= ANa
we can
solve for
ANOS and since we know A^ and ANa ANO3 the equivalent ionic conductance of
>
NOs. By the proper combinations it is possible to determine the ionic conductance for any of the ions. These values of the
equivalent conductances of the separate ions at 18 C. have been accurately determined, and the values compiled by
Noyes and Falk are given
in Table LII.
From the values
of the equivalent
conductances of the ions

holds,
it is
and assuming that Kohlrausch's Dilution Law
then possible to calculate the equivalent conductance at infinite dilution, A^, for any electrolyte. This gives us, then, the equivalent or the molecular conductance at infinite dilution, and Ostwald has proposed that the conductance at any moderate dilution could be represented byA = a(A c A a) where a is the fractional part the equivalent conductance at
any
dilution
is
of the equivalent
tion.
Since
A^ = A c
conductance at infinite diluthen A = aA w or solving for a

,
we have a =
A OQ
3 20
PHYSICAL CHEMISTRY
TABLE LII
EQUIVALENT IONIC CONDUCTANCES OF THE SEPARATE IONS

Jour.
(Noyes and Falk

VALUES AT 18 C.
Am. Chem.
Soc., 34,
479 (1912))
CHAPTER XXVIII
FROM
the equivalent conductance of solutions compiled
in Table L, it will be seen that the only substances listed are acids, salts, and bases. It has also been found that the
only aqueous solutions that conduct the electric current are

solutions of these three classes of substances, which are termed It has also been shown that it was these same electrolytes.
abnormal values
three classes of substances which in aqueous solutions gave for (i) the osmotic pressure, (2) the lower-
ing of the vapor pressure, (3) the lowering of the freezing If 342 grams of point, and (4) the rise of the boiling point. cane sugar are dissolved in water and made up to one liter
we have a molar
will
A molar solution of grape sugar solution. contain 180 grams. The osmotic pressures of these two solutions are the same, the vapor pressures are the same, the freezing points are the same, and the boiling points are
That is, one gram-molecule of any substance, such as these, will produce the same lowering of the vapor pressure of the solvent, whatever the difference in the formula weights may be. It is the same number of moles of
the same.
the different solutes that causes the same change of the boiling points, the same lowering of the freezing points and
of the of the
vapor pressures, when dissolved in the same amounts same solvent. If we have the same number of moles
all
of different solutes dissolved in the
the osmotic pressures of
same quantity of solvent, the solutions will be the same.
321
322
PHYSICAL CHEMISTRY
Those properties such as the osmotic pressure, the lowering vapor pressure, the rise of the boiling point, etc., which depend upon the number of moles or parts in solution, are designated Colligative Properties. The relative magnitudes of the values are proportional to the number of moles of
of the
solute.
It was shown in the discussion of osmotic pressure measurements that a large number of substances gave abnormal values for the osmotic pressure and that van't Hoff proposed to introduce a correcting factor i in the formula to take care of these. The formula then took the form p V = iR T, in which i is the number of times larger the osmotic pressure found is than it should be on the basis of the formula weight of the solute. The value of i is then the value of the ratio of the number of moles present to the number which corresponds to the formula weight this is on the basis that the osmotic pressure is a colligative property. Similarly we have seen that the vapor pressures of solutions of salts, acids, and bases are much lower than they should be. In Table XLVIII the last columns show that the rise of the
;
some solutions is two and in some cases three times what the changes should be. From these values we may obtain the ratio of the number of moles necessary to produce this pressure to the number of molecules represented by the
boiling point of
formula weight, i.e. the value i of van't Kofi's formula, or as sometimes called, van't HofT's coefficient. If g grams of
the solute produces a lowering of A degrees when dissolved in 100 grams of the solvent, the formula weight, m, will produce
a lowering of
g
degrees,
and as the gram-molecular lower-
wA
ing
is 1 8.
6,
it
follows that
= / lo.O
bases,
Arrhenius recognized that the aqueous solutions of acids, and salts also conduct the electric current. He formu-
lated
323
in
the
Electrolytic
Dissociation
Theory
order
to
account for the extra number of moles present in these aqueous solutions which apparently produce these abnormal values of the osmotic pressure, the lowering of the vapor
pressure, the lowering of the freezing point, and the elevation of the boiling point. saw that Clausius in his explanation of the passage of electricity assumed that there were a
We
few ions in solution resulting from the bombardment and collision of the polarized molecules. Arrhenius went confarther and assumed that a large part of the solute siderably existed in the ionic form and that through the mere act of
solution the solute
is
dissociated.
is separated into its ions, that is, the solute Arrhenius assumed that the solute exists in
solution in
two ways, part

part being the inactive
of it as active
and part
the
ions,
active
the
part
dissociated,
inactive, existing as
and
part
being
the
part remaining
undissociated.
On
have
dissolving
sodium chloride in water we would then
NaCl
inactive
^ Na
^
Q-
active
the inactive sodium chloride being in equilibrium with the active part, which is the part ionized and existing as Na and
Cl ions. The relative quantities of the active and inactive parts of the molecule depend upon the dilution. As water is added, the amount of dissociation increases, while if the
concentration of the salt
creases,
is
and the dissociation decreases.
increased, the inactive part inTo these dissociated
or active parts in solution Arrhenius gave the term ions, retaining the term introduced by Faraday to represent that which conducted the electric current. He further showed
that one gram-equivalent of the ions which migrated to the cathode carried 96,540 coulombs or onefaraday of electricity,
and the ions which migrated toward the anode carried a charge of 96,540 coulombs of electricity but of the opposite
324
sign.
PHYSICAL CHEMISTRY
It was recognized that the dissociated parts, the ions, are not like the metallic sodium and the elemental chlorine,
but that they are decidely different, and this difference is due to the difference of their energy content, for when the
ions reach the electrodes in the processes of electrolysis they give up their electrical charge and become the elemental substances.
The
ionic
form
differs
from the elemental form

;
in
that the ions carry charges of electricity the cations positive charges and the anions negative charges. The sodium ion is
represented thus,
Na+
the symbol for sodium with a small
plus sign indicating that the electrical charge is positive and that on each gram-equivalent of ions there is a positive charge of 96,540 coulombs. The chlorine ion is -expressed Cl~,
the negative sign indicating a negative charge of 96,540
coulombs of
ionic
electricity
of chlorine ions.
The
residing difference
on one gram-equivalent between the atomic and
form
is
then merely a difference in their energy
content.
The dissociation of acids results in the formation of hydro+ Cl~ gen ions and the ion of the acid part or radical thus H
:
H + H + SO
-
H + NO - CH COO- H +
3
;
From the dis-
sociation of bases
we have
the basic ion and the hydroxyl

4
;
ions
thus,
Na+
OH~
NH + OHwe have
Ba++
OH-
OH-
while in the case of salts
the part that takes the of the in acid part of the comacids and the place hydrogen ~ + ClSr+ 3 NOr Na + C2 3 O2 pound thus,
;
N0
is
the same as the separation which takes place in chemical reactions. In fact, some go so far as to state that all reactions are ionic, hence, the reactetc.
The
dissociation into ions
ing parts and the parts which go from one compound to another are those which in aqueous solutions are recognized
as the ions.
It
was shown by Kohlrausch and confirmed subsequently

is
that the conductance
the
sum
of the ionic conductances,
and hence the maximum equivalent conductance must be
attained
325
when the
electrolyte
is
completely dissociated.
Ostwald showed that the conductance at any other dilution

could be represented by
A =
o:(A c
or
Ac
Aa
= a,
or
A OO
=a
which
is
the ratio of the conductance at the given
dilution to the conductance at infinite dilution,
is
called
the Degree of Dissociation. We saw when we were studying the dissociation of gases that a relation between the degree
of dissociation
a and
.
was expressed
as follows
(/
i)a or
a =
/
J
The
factor
i is
the ratio of the total
number
number.
in
of parts present after dissociation to the original
The
original
number
of parts is defined
by-^
n,
which g is the weight in grams, m is the formula weight, and n is the number of gram-molecules or moles. The value for a. can be obtained from the electrical conductivity methods van't HofT showed that the value for i could be obtained from osmotic pressure data. We have seen that the freezing point, boiling point, and vapor pressure methods all give abnormal values for the molecular weight of the solute, and from these the value of i can be calculated. Then from the above relation between i and a the value for i can be calculated, providing a is known and /, the number of parts into which the dis;
solved electrolyte
is
dissociated.
Arrhenius did
this, tak-
ing the best data available at that time (1887), and found that the values for i' calculated by the two methods agreed
fairly well.
He
concluded that the value for

point,
could be
ascertained from any of the five methods;

pressure,
viz.
osmotic
boiling
freezing
point,
vapor pressure,
and electrical conductivity. Hence it follows that all of them carl be used for the determination of <*, the degree of
dissociation.
TABLE LIII
DEGREE OF DISSOCIATION
327
In Table LIII are given data compiled by Noyes and Falk which are supposed to be the best available, and from these it is apparent that Arrhenius was justified in his conclusion
that the degree of dissociation
is
practically the
same when
determined fromT the lowering of the freezing point and from the electrical conductance of the solution, although the former is determined at o C. and the latter at 18 C. From the data available Arrhenius pointed out many discrepancies and called special attention to the sulphates. For the sulphates of the alkalies the values for the degree of dissociation vary several per cent, while in the case of CuSO 4 ZnSO 4 CdSO 4
, , ,
the variation according to the data in this table is very marked, amounting in some cases to 10 or 1 2 per cent. In the case of MgSO4, at the dilution of 5 liters, according to the
etc.,
freezing point method, the value of

electrical
is 22.3,
while by the
2
conductance 40.3 was found.

for the degree of dissociation of
The value
solutions in
liters.
K SO
is
89.9 in
which one gram-equivalent is contained in 100 Taking this value as 90 per cent, what will be the
value of i?
The
electrolyte dissociates according to this
2 SO 4 ^ equilibrium equation, sociates into three parts, and/ then
K+ K+
=
SO4 ~ ~,
3.
i.e. it
disis
The
relation
(/
i
i)a.
we have
Substituting these values for / and a, = 2.80, that is, (3 1)0.9. Solving, i
there are 2.8 times as
many
parts in the solution after
it is
90 per cent dissociated as before dissociation. In case of complete dissociation a is one, or the degree of dissociation 100 per cent. Then substituting in the formula, we have = 3, the number of times the total * = i 1)1, and i (3 number of parts is of the original number of molecules. This
is
if
apparent from an inspection of the equilibrium equation we have one mole of and it dissociates into 2 SO 4 + and one SO ~ 4 ~, there are three times as many parts
;
(ions in this case) as there of molecules.
were of the original number
328
PHYSICAL CHEMISTRY
examination of the values of the equivalent conductXLVI 1 1 shows that the values for the acids HC1, HNO 3 and H 2 SO 4 are very high as compared with the values of the other electrolytes the values for the bases, KOH and NaOH, are next in size while the values for the Since the speeds salts of the alkalies are next in magnitude.
ances given in Table
, ;
An
and ions are the most rapid, we expect solutions containing them to be the best conductors. Such is the case, and in general acids are the best conductors, bases next, and It will be obsalts of the alkalies are all good conductors.
of the
OH
served, however, in the case of acetic acid, that the value of the equivalent conductance is only about one tenth that of the other acids, yet each solution contains the same gram-
equivalent of hydrogen. Similarly, solutions of are very poor conductors, the value of AIQO being against 203 for NaOH and 228 for KOH, yet there
NH OH
4
7.1
is
as
the
same quantity of
is
OH by weight in the solutions.

by the
ions,
How,
the difference in the conductance accounted for?

is
then, Since
is
the current
there
carried
we assume
that there
not the quantity of

is
ions in a solution of acetic acid that
in the
HC1
4
solution of
NH OH
solution, nor are there the that there are in the
OH ions in the
solution.
NaOH
Since these ions

lytes,
come from the
dissociation of the electro-
we conclude they
are very slightly dissociated.
In
ways the strength of the different acids can be determined, and they all give values showing that acetic acid is a weak acid as compared to HC1. It is concluded that those acids that are highly dissociated and yield a large number of hydrogen ions are strong acids and the slightly dissociated acids are weak acids. The same holds true for bases NH 4OH is therefore a weak base. Upon the basis of this we
different
;
may
formulate the following definitions An acid is a substance which in an aqueous solution yields hydrogen ions. A base is a substance which in an aqueous solution yields
:
hydroxyl ions.
Electrolytes in general
may be
classified into
329
strong electrolytes or those which in aqueous solutions are highly dissociated, and weak electrolytes or those which are
The salts of the alkalies and of the more than 80 per cent dissociated in dilutions greater than 100 liters and the sulphates of the heavy metals are only about 50 to 60 per cent dissociated, and the weak electrolytes, such as the weak acids and bases, are
but slightly dissociated.
alkaline earths are
than 25 per cent dissociated. arises, how can the equivalent conductance be obtained in the case of weak electrolytes ? Suppose the equivalent conductance at infinite dilution, A^, of acetic Acetic acid is so acid, CH 3 COOH, is to be obtained. slightly dissociated that the value at infinite dilution cannot be determined experimentally. The value for H + can be obtained from the completely dissociated HC1 providing the + equivalent ionic conductance of Cl is known. Then in a similar way by taking a solution of an alkali acetate- such as CH 3 COONa, the maximum value, A^, can be obtained experimentally since it is a strong electrolyte. From Kohlrausch's Law we have A^ = A c + A a From Table L we find the value of the equivalent ionic conductance of Cl~ at 1 8 C. is 65.5, and if A^ for HC1 is 377, then we have
less
The question
~ 65.5 = 311.5 as the value of the equivalent ionic 377 conductance of H + Similarly for CH 3 COONa we have
.
Na+ is 43.4 then the value for the acetate-ion is 76.8 43.4 = The value of A^ for acetic acid is then 311.5 +33.4 = 33.4. 344.9, but the value at the dilution 100 liter is AIM = 14-3,
76.8,
;
A^ =
and the equivalent
ionic conductance of
and the degree
of dissociation is
^
A,
I4 '^
=4.1 percent.
344-9
There are a number of interesting properties of solutions which are attributed to the properties of the ions, and many of these have been put forth as confirmatory evidence in
favor of the theory of electrolytic dissociation. The theory has been applied to explain many phenomena and particularly
/*
330
PHYSICAL CHEMISTRY
in qualitative analysis.
We
shall present
a few of the more

of the elec-
general and commonly accepted applications
trolytic dissociation theory in order to emphasize the method of using it to explain the properties of solutions and chemical
reactions.
i.
Effect of temperature
is
on the conductance
is
shown
in
given the equivalent ionic conductances For example, the value for at 18 of the separate ions. it is 74.8 mhos, thus showing a marked is 64.5, while at 25
Table L, in which
increase in the ionic conductances with the temperature. The equivalent conductances of the electrolytes then increase
with the increase in the temperature, and tables have been compiled showing the temperature coefficient of the conductance of a large number of electrolytes. The transport
numbers
also
vary with the temperature, as

is
is
shown in Table
proportional to the speed of the ions, the equivalent conductance is proportional to the number of these which are transporting the current. It fol-
XLIX.
As the conductance
lows then that in order to determine the effect of temperature upon the degree of dissociation a number of factors will have
to be taken into consideration.
resulting
In addition to the number

will
from the dissociation their speed
be influenced
viscosity of the solution, that is, to the friction which the ions encounter in their passage through the solution, which
by the
The thermal change accomvaries with the temperature. panying the ionization is termed the heat of ionization, and Arrhenius calculated this from the rate of change of conductit
ance with the temperature. The heat of ionization, while may be either positive or negative, is usually positive, which means that the ionization is accompanied with evolution of heat, and according to Le Chatelier's theorem the
The ionization should decrease with a rise in temperature. heat of ionization may be determined from the constant of
the heat of neutralization and from the law of thermal neutrality, reference to
which
will
be
made
subsequently, but
it
would lead us too
ionization.
far to develop the
331
for calculating the influence of temperature
thermodynamic formula on the degree of
2. Basicity of organic acids has been shown by Ostwald to bear a definite relation to the equivalent conductance of the
sodium salts of the acid at 32 and 1024 liters dilution. For monobasic acids this difference is 10 units, and as the basicity increases the differences are found to be multiples of 10.
That
Al024
is,
Aa2
10
the basicity of the organic acid.
In
Table LIV from data according to Ostwald is given the difference in the equivalent conductance of the sodium salts
of a of organic acids, and in the last as from the above formula. calculated basicity
number
column the
TABLE LIV
SODIUM SALT
332
PHYSICAL CHEMISTRY
before the formulation of the electrolytic theory many observers attributed the properties of the solution to the inde-
pendent characteristic properties of the constituents of the

solute.
calls attention to the following relations which additive properties of solutions of electrolytes. the emphasize When ionization is complete, the properties of the solution
Whetham
of the ions
should be the additive result of the individual properties and of the solvent, and when dissociation is not
complete, there should appear an additive factor due to the undissociated solute. The specific gravities of salt solutions
were calculated by Valson from experimentally determined moduli of the elements. By the specific volume relations Groshaus showed that the molecular volume of the solute is, in dilute solutions, the sum of two constant factors, one for
the acid and the other for the base.
That the
densities
and
thermal expansions of solutions are also additive has been confirmed by Bender. The volume change accompanying the
neutralization of acids
by bases
also illustrates the additive
properties as shown by Ostwald and by Nicol. The additive character of colored solutions
is
readily
seen from an examination of the absorption spectra of a series of such solutions containing a common ion, the absorption
spectra due to this ion being unaffected by the other parts of the solute in solution. In aqueous solutions anhydrous
salt itself is blue.
cobalt chloride forms solutions red in color while the pure The color of the cobalt ion is then red.
In alcoholic solutions, in which the dissociation as obtained
from the conductance

the solution is blue
is
practically negligible, the color of
Upon
the color of the undissociated compound. addition of water to this solution the red color gradu-
Copper ions are blue, hence all aqueous solually appears. tions of copper salts should be blue. If, however, we add
to an ammoniacal copper sulphate solution, we have the solution completely decolorized with the formation of
KCN
3
333
K Cu(CN)4 and the complete disappearance of copper ions. and forms yellow K CrO4 dissociates into 2 K + CrO
2
4
aqueous solutions hence the CrO4 ion is yellow as solutions of salts of the alkalies are colorless, their ions are colorless.
; ;
If the chromate is reduced by 2 S, we obtain a greenish solution with the formation in the presence of 2 SO4 of Cr 2 (864)3, Since the which dissociates as follows: 2 Cr + + 4 3 SO4
"
864 ions are colorless, the green color of the solution uted to the green color of the Cr ions.
Similarly manganese,
is
attrib-
when
salts,
it
functions as a base with the

2,
formation of manganous
MnCl
MnSC>4,
etc.,
produces
very pale pink or nearly colorless solutions, while KMnC>4 solutions are highly colored, due to the presence of the MnO^ In its salts manganese has a valency of two, while in ions.
the permanganate compounds its valency is seven, and it is Hence, the change from a fulfilling the function of an acid. cation to an anion consists in increasing the valency of the
manganese from two to seven. The same is true for chromium as illustrated above as in the cation it has the valency of three, and in the anion its valency is six. In both cases we have the change from cation to anion accompanied by an increase in valency, which process we call oxidation and the
;
reverse process reduction. So, too, for iron in ferrous chloride

2 Cl~.
is
we have FeCl 2 Fe ++ The solution is practically colorless, but when this oxidized we have a yellow solution, FeCl 3 Fe +++ 3 Cl~,
the difference being that in one case the colorless ion of iron carries two charges, and the colored iron ion carries three
charges of electricity. Hence, the process of oxidation is due to the increase in the valency of the iron obtained by adding an additional faraday of electricity to the gram-equivalent of the iron ions.
oxidation and reduction
That the
ciation
rise
our processes of be may explained upon this basis. in temperature decreases the degree of dissoIt is evident that
may
be illustrated in the case of colored solutions.
334
PHYSICAL CHEMISTRY
blue,
Copper chloride solutions are

chloride
is
yellow.
When
this latter is
and anhydrous copper added to aqueous
tions,
solutions of copper chloride to produce concentrated soluwe have the combination of the blue and yellow pro-
ducing a solution with a decided green color. If water is now added, the solution becomes blue, and on heating the green color can be restored, thus showing the reduction in dissociation on heating the same as on increasing the concentration of the solution.
Other properties of solutions, such as viscosity, surface tenoptical rotatory power, etc., illustrate the additive properties of the solutions which are attributed to the additive
sion,
properties of the dissociated parts.

4.
Substitution.
We
have seen the
effect of the substitu-
tion of a group such as 3 upon the various properties of the compound, such as boiling point, refraction, etc. The effect of the first substitution is greatest and diminishes
CH
with the successive substitutions. In the case of the electrical conductance of aqueous solutions of these substitution products we likewise find a marked effect resulting from these This will be considered more in detail under substitutions.
the discussion of the dissociation constant, page 340. 5. The mutual reaction of two electrolytes resulting in the
so-called process of double decomposition is explained upon In the equithe basis of the electrolytic dissociation theory. + + +
Cl- ^ AgCl librium equation Ag 3 an as ionic we see that there has been reaction, expressed a disappearance of the Ag and Cl ions, resulting in the forma-
NCV + H
+H
NO
tion of AgCl,
which we
recall is insoluble
and
is
precipitated.
We say that the chlorine and silver ions
cannot exist in soluIn tion at the same time and are consequently precipitated. the reaction representing the neutralization of a base by an
acid,
we have Na+ OH~ + H+ Cl- ^ Na+ Here we have the disappearance of the H + and
2
Cl-
OH
H2 O. with the
formation of
H O, which is soluble, while the Na + and Cl" re-
main
salt
335
in solution as before the reaction, but we say we have a formed, and this is dissociated, thus giving us practically the Na and Cl ions as they originally existed. We have the undissociated water produced by this process of neutralization, and for all cases we have approximately the same
gram-molecule of water proIn other words, neutralization consists in the forma+ and OH~. In like tion of water from the union of the manner, the chemical reactions representing double decomof heat evolved for each
amount
duced.
The application of the theory positions may be explained. to Qualitative Analysis is evident and serves as a basis for the
Some authors state that all presentation of this subject. chemical reactions are ionic, and that it is only between the
ions that reactions occur, whether these be in aqueous or nonaqueous solutions and even in cases where no solvent medium
is
employed.
These relations
will
be considered somewhat
more
in detail in a few specific cases subsequently.
CHAPTER XXIX
EQUILIBRIUM BETWEEN THE DISSOCIATED AND UNDISSOCIATED PARTS OF AN ELECTROLYTE IN SOLUTION
ARRHENIUS assumed that the electrolyte exists in solution as the active and the inactive parts, and that the active part consists of the ions or constitutes the parts into which the
electrolyte
is dissociated. As we have just seen, it is to these parts, the ions, that the chemical reactions are all attributed.
Since there
two
is an equilibrium always existing between these parts, Ostwald, as well as van't Hoff, showed that the
Mass Law is applicable to this equilibrium between the undissociated part of the electrolyte and the ions into which it is dissociated. Applying the Mass Action Law to the equation
NaCl
Na+
Cl~
wehave
but the concentration of the sodium and chlorine ions
is the same, as there are the same number of positive ions produced as there are negative ions when the NaCl is dissociated, hence + [Na ] = [Cl~] and the equation may be written
V
Since
we
a = the part or concentration
represent the degree of dissociation by a, then of the dissociated

parts the part or concentration of the undissociated
part.
and
Substituting these respectively for
[Na
+
]
and [NaCl] the
equation becomes
336
EQUILIBRIUM OF AN ELECTROLYTE IN SOLUTION

k
337
^r
a2
.
which becomes
k(i
- a)V =
=
This
is
known
as Ostwald's Dilution
Law, and
may be written
V(i-a)'
The degree
trical
of dissociation is usually obtained

i.e.
by the
elec-
value for a
conductance method, we have
a =
2-,
and substituting
this
=
171
or
A,
-A )A
V
from which the value of k, the dissociation constant, can be readily determined by measuring the electrical conductance, A r at the volume, V, and knowing A^ This Law of Dilution has been verified in the case of over two hundred forty organic acids, and Ostwald's data given in Table LV illus.
trate the satisfactory agreement for the values of k over a wide range of concentration.
TABLE LV
338
PHYSICAL CHEMISTRY
In Table LV V is the volume in liters of solution in which one gram-equivalent of the acid is contained A the equivathe third lent conductance for the given volume at 25 C.
;
;
column, 100 times a, the per cent dissociation, and in the last column, k, the dissociation constant. Bredig found upon investigation 50 bases conforming fairly well to the Dilution Law of Ostwald as the data in Table LVI The molecular conductance is expressed in reillustrate. One ohm equals i .063 Siemens units. units. Siemens ciprocal
/u.
TABLE LVI

Ostwald's equation
is
339
may
be written *-*r
\1A>\
k,
in which
[i]
the concentration of each of the ions and
tration of the un-ionized part.
[u] is the concenVan't Hoff proposed the
empirical equation
=
(i
a3
a)
2
or k
=
(i
1- 5
a)
^V
which then becomes k
yL-
which gives us a simple relation
between the concentration of the ionized parts and the undissociated part. For Ostwald's formula the exponential value is 2, that of van't Hoff 1.5, and Bancroft proposed that the general character n be employed, which gives the equation
k
=
-J^L
He found
that for strong electrolytes this value
ranges from 1.43 to 1.56, while for the weak electrolytes it is practically two. In Table LVII are given the values of k for 4 C1 at 18 C. as determined by all three of these equa-
NH
tions.
TABLE LVII
340
PHYSICAL CHEMISTRY
Both the Rudolph! and van't Hoff equations give equally constant values for k, particularly for the more dilute solutions (from V = 10 to V = i ooo liters), while the Ostwald equation
gives values for k which decrease regularly and rapidly. Several attempts have been made to obtain a physical
significance for van't Kofi's equation, such as the equations of Kohlrausch, of Kendall, and of Partington particularly,
whose equation gives a constant that passes through a maxi-
mum and holds only fairly well for strong electrolytes.

Dissociation or lonization Constant.
trolytes,
It
is,
however, still a question whether the Law of Mass Action can be applied to the electrolytic dissociation of strong electrolytes.
The
strong elec-
which include practically all of the ordinary inorganic acids, bases, and salts, with a few exceptions, are highly dissociated, and the values of the dissociation constant,
as
we saw in the case of
NH C1, are not of the same magnitude

4
for the different dilutions.

trolytes,
But
in the case of the
weak
elec-
which include a few inorganic acids, bases, and salts, and most of the organic acids and bases, we have a class of substances slightly dissociated to which the Law of Mass Action appears to be applicable or sufficiently so that the degree of dissociation can be calculated and also the dissociaIt is to be remembered that the value of a, tion constant. which as we have seen can be ascertained in a variety of ways, Then too the value of the conductance is usually very small. at infinite dilution, A^, is not easy to determine, and slight variations in this value may affect the value of a greatly,
since
=a, and then the value

00
of the dissociation constant
becomes somewhat uncertain. There have been compiled in Landolt-Bornstein's Tdbellen the dissociation constants of a large number of acids and bases, both inorganic and organic, and in Table LVIII we have selected a few of these in order to show the order of the
constant at 25
C.
341
TABLE LVIII
SUBSTANCE
342
PHYSICAL CHEMISTRY
of dissociation of
is
The degree
small,
weak
acids
is
comparatively
and a
therefore very small as
compared to unity.
(i
Hence
is
in the equation k
=
(i
a)
the expression
(i),
a)
not materially different from unity
and the equation
then becomes k
or a
= kV, and
a = V&F.
The
de-
gree of dissociation of two acids can then be readily compared by expressing the ratio of these two factors or the square
root of the value of the dissociation constant, thus

Oi2
=
Since
and
for the
of.
same volume we have

<**
= \^.
AjjV
^2
proportional to their degree of dissoreadily ascertain from the dissociation constants the relative strength of the acids (and the bases as
is
the strength
acids
ciation,
we can
well) since the dissociation constant is also
a measure of the
concentration of the hydrogen ions. For example, from Table LVI we find the dissociation constant for acetic acid
is 1.8
io~ 5
and
for the trichlor acetic acid is 3.0
lo" 1
we then have
9fl
/v
= \ r'^ X
o *3.0
*
-?
io
/o.
oooo 1 8
r\
/_
N/ IO" T f\~ 1
V '
0-3
^16666.66
i
I2Q.I
The
substitution of chlorine for the hydrogen of the methyl group increases the strength of the acid enormously. The
same
i o~
5
is
true in the case of the bases
amine.
The
and
ammonia and diethyldissociation constants are respectively 1.8 i. 2 6 io~ 3 The ratio becomes
01
>'v
...
/o. oooo 1
*
r\ r\r\
/__
^r/^ ^7O
=
8-37
T i f\ O.OOI26
which shows that the strength of the base is increased several times by substituting two ethyl groups in place of the hydrogen of ammonia.
343
Arrhenius showed that two acids Isohydric Solutions. have same concentration of hydrogen ions can be the which
mixed in any proportions without changing their degrees He termed these solutions which have the of dissociation. of hydrogen ions, isokydric solutions, concentration same and went further and stated, " what has just been said about
isohydric solutions of acids can be applied without change to other isohydric solutions which have a common ion." Ar-
rhenius based this
^Jiat all electrolytes follow the dilution law, but this statement is too sweeping and must be revised if what we have seen above is true. He
upon the assumption
found that in the cases of mixtures of hydrochloric acid and of acetic acid the specific conductance of the mixture was
practically the same as the sum of the specific conductances of the two solutions and complied with the mixture
law which
may
be expressed as follows
V,
v.+
vj
V.
>v a
+v
In this equation Km is the specific conductance of the mixture, K O is the specific conductance of one solution at volume
and Kb at volume
a,
is
b.
the specific conductance of the other solution It is further assumed that the two solutions
are sufficiently dilute so that the final volume is the sum of the original volumes, that is, Va Vh This is the case
in concentrations of
above 10,000
liters.
The degree
is
of
dissociation of
weak
electrolytes at these dilutions is very
small, while that of the strong electrolytes cent.
over 80 per
:
The
following presentation follows Bancroft very closely In the case of mixtures of solutions of acetic acid and of
potassium acetate we have
CHsCOOH ^ CH COO3
H+
K+
and
CH COOK 5* CH COO3 3
344
PHYSICAL CHEMISTRY
Assuming the Law of Mass Action to hold if one formula weight of acetic acid is used, then there will be formed x formula weights of CH 3 COO~ and we have
7
X_ = X
'
V
We
have a
V'
different dissociation constant k2 for potassium
acetate than for acetic acid, as they are very differently dissociated, and we cannot therefore start with equivalent quantities in equaf volumes in order to obtain the same con-
common anion of acetic acid, CH 3 COO~, but with some concentration such as C formula weights. The Mass Law Equation for potassium acetate then takes the ~* = form fe2 Substituting for the right-hand
centration of the
s~+
.
member
of this equation its equal in the
acetic acid
we have k2
we have
^-^
= ki
'*
above equation,
.
for
x'
Solving for C,
r _ ^1 +
fe
fei)*
Now
acid
let
us add the volume
nV
i)x
of the
solution to the acetic acid solution.

i
We
'
potassium acetate have for the acetic
-x
(n
_x
and
for the potassium acetate
^ n(C
as
x)
(n
-j-
i)x
nx
when the volume
total
volume becomes
nV of potassium acetate is added the V + nV or (n + i)F, and the mass

becomes (n
of the anion of acetic acid
i)x,
and that
of the
+ is hydrogen ion remains the same, while the mass of the nx. i) and n, the equations simplify to By canceling (n
345
'
which are the original equations of equilibrium, thus showing that the degree of dissociation of each of the electrolytes
remains unchanged.
For solutions of acetic acid and of zinc acetate we have CH 3 COOH ^ CH 3 COO- H + and (CH 3 COO) 2 Zn ^ 2 CH 3 COO~ Zn ++ from which we have respectively
,
From
this the value of
becomes
r _ o
(ki -
Now
add volume, n V,
of zinc acetate solution to the acetic
acid solution.
We obtain for the acetic acid
and
for the zinc acetate

r
Kz
n(C
:
1/2 x)
.
2 _ f(nj-i)x\ f(n + i)*V
1/2 nx _J
(n
\(n
i)V)
and n the two equations reduce to the original equilibrium equations, thus showing no change in the degree of dissociation when the isohydric solutions are mixed
By
canceling (n
-\-
i)
in
any volume. For solutions of zinc acetate and of zinc sulphate we have
(CH 3 COO) 2 Zn ^ 2 CH 3 COO- Zn ++ Zn++ SO 4~ and ZnSO 4 for which we have, assuming x formula weights the Mass Law Equations
of zinc ions,
x\ 2
"v'v'
346
PHYSICAL CHEMISTRY
add the volume, nV,
n(i
l
Now
of the zinc acetate solution,
when we obtain
,
for the zinc acetate
(n
+ *)V
~
*)
-x) _(
n2x
(n
i)*
\(n+i)Vj
(n+i)V
.
and
for the zinc sulphate
k 2 (C
Simplifying,
= n+
(
*)*
(n-r-i)F
(n
-f-
i)V
(n
+
V
i)V
we have
k
d-*) _ _*_(L*\* ~V~ ~n+i(v)

fe2
and
from which
it
^*=.|
n
same equilibrium equation
appears that for the zinc sulphate we have the as before mixing, but in the case
of the zinc acetate the factor
does not cancel out.

i
There will therefore be increased dissociation of zinc acetate, and as a secondary phenomenon a decrease in the dissociation of zinc sulphate.
These
are,
however, not binary electrolytes which Arrhe-
nius was considering in his generalizations. and zinc sulphate are similar to zinc acetate
Sodium sulphate and zinc sulphate,
and sodium sulphate and sodium oxalate are analogous to In the case of sodium sulphate zinc acetate and zinc chloride. and sodium oxalate there would, however, be no change in dissociation, but for sodium sulphate and potassium sulphate or zinc chloride and zinc acetate both salts tend to dissociate and a general expression has been worked out for all of these cases.
Bancroft further applies van't Hoff 's equation to the case of isohydric solutions, and for hydrochloric acid and potassium chloride shows that the degree of dissociation of each of the
The recent experimental electrolytes should be decreased. work on the mixtures of salt solutions, including acids, shows
347
a decided change in the degree of dissociation of these, and since solutions are considered isohydric on the basis of their
conductance, it emphasizes Arrhenius' definition of isohydric solutions that the ion concentration is independent of the conThe concentration centration of the undissociated substances.
of the undissociated part is very great relatively to the concentration of the ions in the case of the weak electrolytes.
We know that in many cases the concentration of the ions does

not remain constant, and particularly is this true when salt solutions containing a common ion are mixed, such as potassium cyanide and silver cyanide. Even when the solutions
containing different ions are mixed
we have marked change
in the conductance, demonstrating the increased dissociation of many acids caused by the presence of other electrolytes,
producing ions not
common
to the acid.
Mutual Effect
electrolytes
of Ions.
The
effect of
mixing solutions of
two
acids.
may be illustrated in the case of the addition of Let HAi and HA2 be the two acids, and their disand &2
c2
c\
sociation constants ki
be mixed when
and
Let these acids respectively. represents the concentration of the
two acids
in the mixture,
and a\ and
a^ their degree of disso-
ciation respectively.
Then
in the mixture
we have
a\Ci
the concentration of the
ions
=
==
+
for each acid
the concentration of the Ai~ ions ~ the concentration of the A2 ions
According to Ostwald's Dilution

ki(i
Law we have
ai)Ci
k z (i
This gives the relation
az )c2
which becomes
'
348
PHYSICAL CHEMISTRY
since, in the case of
Now
weak
it
electrolytes, the degrees of
dissociation are very small,
follows that -
kz
at)
is
approxi-
(i
mately unity, and the expression becomes
=
a2
The
ratio of the dissociation constants
is
equal to the ratio
and we have seen that the acids with the greater dissociation constants are the more highly dissociated acids and therefore the stronger. Let us consider the case of a weak acid, such as acetic, and
of the degrees of dissociation,
a strong acid, such as hydrochloric. For acetic acid we have in the mixture of the two
and
for hydrochloric acid
These
may
then be written in the following form

ki
=
i
i
(aid
2 c2 )
and
k2
=
i
a2
(aid
+ac
2
2 ).
But
in the case of acetic acid the degree of dissociation is so cti) is so nearly unity (i) that slight that the value of (i
no great error
will be made by this substitution and our then takes the form equation
In the case of dilute solutions of hydrochloric acid the dis= i. We then is practically complete, hence 2 have ki = ai z ci As a \ is very small, much less than a\cz.
sociation
unity, the value of the first term may be neglected in comparison to the second, and we then have ki = ctiCz, from which
we have
a\
That
is,
the degree of dissociation of the
349
weak
acid in the mixture
is
inversely proportional to the con-
centration of the strong acid. Hence by adding large quantities of hydrochloric acid to an acetic acid solution, the
dissociation of the acetic acid will be forced
back and
may
become
The
practically undissociated. forcing back of the dissociation
in analytical chemistry, as When ber of cases. 4
may
is
of great importance be illustrated in a large numis

2,
NH OH is added to a solution of MgCl
a precipitate of
reaction,
Mg(OH) 2
4
produced according to the ionic
+ 2 NH + OH- ^ Mg(OH) + 2 NH + CK Now NH OH is a weak base and therefore produces few OH ions, according to the ionic equilibrium equation NH OH + OH~ for which we would have the Mass Law ^ NH
Mg++
2
Cl4
Equation
k
[NH OH] =
4
mixed with a strong electrolyte containing the common NH 4 ion, such as any ammonium salt, the concentration of the ions furnished by this would be very much in excess of that furnished by the NH 4 OH. According to the equilibrium equation above we readily see that with the
increase of the concentration of the
Now when
NHiCl
the value for
becomes very small the degree of dissociation of the 4 and can be decreased to such an extent that the number required for the formation of Mg(OH) 2 is not sufficient to proi.e. it will all duce enough of the Mg(OH) 2 to precipitate
;
NH OH
remain in solution. So in the preparation of the so-called magnesium mixture enough ammonium salts are added to
prevent the ionization of the
NH OH to the extent necessary

4
to produce enough Mg(OH) 2 so that it will exceed its soluSince the hydroxides of Fe, Al, and Zn are but bility. slightly soluble, it is more difficult to prevent their precipitation in this
manner.
350
Ionic Product.
PHYSICAL CHEMISTRY
If
the dissociation of the precipitating reagent can be forced back to such an extent that the ions it produces are practically negligible, then to precipitate a substance and prevent it from going into solution again would require the presence of a large number of either of the ions
For example, resulting from the solution of that substance. of HC1 be solution concentrated if to a solution of BaCl2 a
added, the concentration of the chlorine ion can be increased For to such an extent that the BaCl 2 will be precipitated. of the that an excess it recommended is this reason precipitating reagent be added. In order to prevent the precipitate from redissolving, the precipitating reagent containing an ion in common with
the saturated solution

tate
is
is
washed and thus separated from the excess

ion, the
present in excess, but as the precipiof the
pure water will dissolve the precipitate. It is therefore necessary to wash the precipitate with wash water which contains an ion common with that produced
in saturated solutions of the precipitate.
is
common
Magnesium amammonia with washed monium phosphate water, ammonium phosphomolybdate with a solution of NH4 NO 3 PbS0 4 with wash water cpntaining H 2 SO 4 etc. Electrolytes
,
,
chosen for this purpose should be readily volatile if the precipitate is to be weighed. In saturated solutions the concentration of the undissociated solute in solution is in equilibrium with the solid The solute, and this concentration is a constant quantity.
solute in solution
is
dissociated
is
and there
exists, as
we have
seen, a condition which
represented
by
,
the equilibrium re_
lation
AgC1
solid
AgC1 _> Ag+

undissociated
and
for a saturated solution the concentration of the undisis
sociated solute
a constant.
It is evident that the silver ion
and the chlorine ion are found in equivalent quantities and
in
351
definite concentrations, and according to the Law of Mass Action we have the products of the concentration of the ions
and as
proportional to the concentration of the undissociated part, + this latter is constant we then have [Ag ] [Cl~] =
a constant, which is usually designated by L and is called the Solubility Product or the Ionic Product. This equation is then Lo
"
[Ag+J
[Cl-].
Lewis says, Again, as already pointed out, the saturated solution of a body such as AgCl is very dilute, and since it is a salt, the small quantity which is dissolved suffers almost
complete dissociation in solution. Hence the concentration of the undissociated molecules must be small compared even
with the ions.
That
is,
CQ
is
negligible
compared to the con-
centration [Ag+] or [Cl~]. Hence in such a case, say when AgCl is dissolved in water alone, the concentration of Ag+ or Cl~ in gram ions per liter gives a number identical with the
solubility of the entire salt.
But [Ag+]
[Cl~]
LO.
Hence
Now the solubility is identical with the V solubility product. take the case of AgCl in presence of some KC1. The solubility
least represented ion,
simply becomes identical with the concentration of the + ion. An estimation of the i.e. the Ag
is
Ag+
ion in solution
therefore the experimental
way
of ar-
riving at the solubility of AgCl in aqueous KC1 solution. can evidently calculate this quantity if we know what value
We
Lo has (say by estimating the Ag+ or Cl~ in absence of KC1) and remembering that Lo is constant whether KC1 is present
or not.
By the addition of KC1 in a given amount we know the quantity of Cl~ present (the Cl~ originally present from the AgCl itself being usually negligible compared to the
quantity added), and the solubility of the AgCl in presence of KC1, or the Ag+ concentration is simply
'
'
[C1
352
PHYSICAL CHEMISTRY
The numerical value of the ionic product may be calculated

the solubility of the salt and its degree of dissociation are known. At 25 the solubility of BaSO 4 is 0.0023 gram per The BaSO4 is assumed to liter, or practically o.o 4 i mole.
if
be completely dissociated,
o.o 4 i
0.041
o.ogi,
which
is
then Lo = [Ba ++ [SO 4 ~] = the ionic product of BaSO 4

]
and as determined by Hulett

of
is
0.94
io~ 10
The amount
BaSO4
liter.
2
per
remaining in solution would be very small, 23 mg. In the determination of sulphur in sulphates by the
BaQ
excess of
method the SO 4 ions left would be reduced by a slight BaCl 2 so that there would be but a small fraction of
a milligram per liter remaining. We have again emphasized the necessity for adding a small excess of the precipitating
reagent. The ionic product of Agl is much smaller than that of AgCl, so that on the addition of a solution of KI to a saturated solu-
AgCl in equilibrium with an excess of the solid AgCl the concentration of the Ag + would be decreased. This will
tion of
result in a final state of equilibrium according to the following
equation
AgCl ^
solid
AgCl
undisspciated
(negligible)
^ Ag+
4- Cl-
K+
I-
Agl
(negligible)
Agl
solid
undissociated
solution
When equilibrium is established, the concentration of the ions

must be such that
iodide, that
is,
their products are the ionic products (solubility products) of the silver chloride and of the silver
[Ag+] [Ag+]
[C1-,
[I-]
= LAgQ =
is
But the concentration

therefore
of the
Ag+
the same in both cases,
by
division
we have
[Cl-]_LAg ci
353
This means that at equilibrium the concentration of the Cl must be greater than the concentration of the I~ in the ratio of their ionic products. The ionic product of AgCl is 1.56 X io~ 10 and of Agl is 0.94 X io~ 16 then
,
[I-]
0.94
icr 16
which means that the concentration of the I~ must become about one millionth of that of the chlorine ions, hence virtually all of the AgCl can be transformed into Agl and practically all of the silver precipitated from the solution. In Table LIX there are compiled the values of the Ionic Product or Solubility Product of a few of the more common
compounds.
TABLE LIX
SUBSTANCE
IONIC PRODUCT
354
PHYSICAL CHEMISTRY
whether the conditions under which they react are such that both are under the most favorable conditions. If many acids or salts of these acids are treated with H 2 SO4 and heated,
sulphuric acid will take their place, according to the reaction 2 HC1, which is the usual 2 NaCl = Na2 SO 4 2 SO 4
method for the preparation of HC1. From such reactions one would say that H 2 SO 4 is the stronger acid. If a number
of acids or their salts are heated, they would pass off in the order of their volatility, and phosphoric acid would be among
the ones to remain, therefore phosphoric acid would be conIn the glazing of potsidered stronger than HC1 or HNOs. tery NaCl is introduced on to the hot pottery, which is covered
with SiO 2 where we have a replacement of the chlorine with the formation of sodium silicate. By analogous reasoning we should conclude that silicic acid is stronger than hydroThe difficulty with methods of this kind is that chloric acid. under the conditions the two acids have not equal chances
,
is
to compete for the base, as one of the acids readily removed from the scene of action.
is
volatile
and
terms have been applied to what we call strength of such as affinity, activity, and avidity. Many methods have been devised for determining the strength or avidity " " one by the of acids, such as the method of turning out other, but we have seen that this is not a really satisfactory
Many
acids,
method.
hydrogen
Since the degree of dissociation determines the number of ions, and this is readily ascertained from the
method, we then have a satisfactory and convenient method for ascertaining the relative strength of acids from their conductance. From the values of the dissociation constants given in Table LVIII the relative strength of these weak acids can be readily obtained. Suppose we have two weak acids, HAi and HA 2 which form salts with the strong base BOH. Let us assume that we have one mole each of the two acids and of the base. Then
electrical conductivity
,
355
ments of the two
there will not be enough of the base to supply the requireacids, and so it will be distributed between
fraction of a mole
the acids in proportion to their dissociation. Let x be the which reacts with the acid HAi, then (i x)
.
moles of the base react with the acid HA2 shall then have the equilibrium equation
Accordingly
we
BAi
+ HA
2 :
BA +
2
HAi.
From which
the concentrations are
x moles of the salt BAi and (i 00} moles of HAi (i x) moles of the salt BA 2 and x moles of HA2
.
Now
assuming that Ostwald's Dilution
Law
[x]
holds,
we have
for the
two acids
k
.-
[H
+
]
[Ar]
[H+]
[i
[HA!]
x]
and
[HA,]
[x]
The above equations then become, dividing the one by the

ther
'
*i
k,
=
[i
[H+]
[x]
[x]
[i
MI
[i-*] 2
'
-*]
[H+]
-*]
since the distribution of the base between the two acids in the ratio of their degrees of dissociation, and when one mole of the base meets with one mole each of the two acids we
is
But
have
[i
or
x]*
I [i
_!*]_ = J*T \ tl X\ -x]
Hence, the distribution ratio is obtained by determining the dissociation constant of each acid and the ratio of the strength
of the acids is equal to the square root of the ratio of the dis-
sociation constants.
Thomsen's Thermochemical method for the determination of the relative strength of acids, of their avidity, as he termed
356
it,
PHYSICAL CHEMISTRY
and determining the heat

heat of neutralization of
actual heat absorbed
consisted in treating a salt of an acid, Na2SO4, with HC1, effect. Having determined the
NaOH by H2 SO4 and by HC1, and the when Na2 SO4 reacts with HC1, it would
be an easy matter to calculate the proportion of the sodium sulphate converted into sodium chloride. From this the relative amounts of the sodium distributed between the two
acids can be readily ascertained.
By employing
this
method Thomsen determined the
rela-
tive strengths of a number of acids upon the basis of HC1 as under the heading 100 and his values are given in Table
LX
Avidity.
TABLE
LX RELATIVE STRENGTH OF ACIDS AS DETERMINED BY A NUMBER OF THE COMMON METHODS, ASSUMING HCL = 100
(After Walker)
357
changes Ostwald calculated the relative strength of some of the more common acids and found the same general order
to prevail as by the other methods. The values as determined by the rate of inversion of cane sugar and by the catalysis of an acetate are in agreement with the other methods. These two methods will be referred to subse-
quently. The order
is
the same
by
all
methods.
Practically the same methods may be employed for determining the relative strength of bases. The values in Table LXI illustrate about the average relative strength of the
common
as 100.
bases and their order, assuming lithium hydroxide
TABLE LXI
(After Walker)
BASES
AVIDITY
Lithium hydroxide Sodium hydroxide Potassium hydroxide Thallium hydroxide
100
. . .
Tetraethylammonium hydroxide Triethylammonium hydroxide Diethylammonium hydroxide
98 98 89 75
14 16
12 2
Ethylammonium hydroxide
Ammonium
hydroxide
The hydroxides
dissociated
and are the strong
of the alkalies are practically completely bases, the hydroxides of the
droxide
alkaline earths are also strong bases, while is a very weak base.
ammonium
hy-
CHAPTER XXX
CONCENTRATED SOLUTIONS
IN the presentation of the relations of the vapor pressure to osmotic pressure it was emphasized that The Gas Law could be applied to solutions, but that these solutions had to be of
the type known as ideal or perfect solutions, and this is analogous to the statement that The Gas Law holds only for Perfect Gases. We saw that certain modifications of The Gas
Law were made
in attempting to use
it
;
in connection with
most gases under the usual conditions so, too, in the application of The Gas Law to solutions other than the perfect solutions certain modifications must be made in order to take into consideration the numerous assumptions postulated in connection with the applications of The Gas Law.
In the formulation of his Modern Theory of Solutions van't Hoff fully realized the limitations of his conceptions of solutions and showed the necessity of limiting its application, and in his presentation stipulated the explicit assumptions made in applying the Laws of Gases to solutions and these may be
;
summarized as follows 1 There is no reaction between the solvent and the solute. 2. The solvent and the solute are neither associated nor
:
.
dissociated.
The compressibility of the solution is negligible. 4. The Heat of Dilution of the solution is zero. We know from experience, in many solutions at least, that there is a marked reaction between the solvent and solute
3.
and that the heat of dilution is zero in but few cases. Further, we have just been considering a number of methods by means
358
of
359
which the dissociation of the solute can be determined, and we have also presented methods for determining the It will therefore be necesassociation constant of liquids. detailed consideration of these for us to take a more up sary HofFs formula will and see in van't what ways assumptions be affected by dropping each and all of these assumptions. As van der Waals' equation was one Weight Normality. of the modifications of the Gas Law Equation to account for the variations from the law that occurred in concentrated gases, there are likewise numerous equations which attempt to represent the quantitative relations between the osmotic pressure and the concentration of the solution by correcting for the mutual attraction of the solute molecules and also for the attraction between the solvent and solute. The main idea is to get an expression which would incorporate the volume of the solvent and not the volume of the solution that contained the molar concentration of the solute. It was
through the work of Earl of Berkeley and E. G. J. Hartley and of Morse that the best agreement between theory and experimental data was obtained by expressing the concentration in terms of weight normality instead of volume normality, as was done by van't Hoff, and is usually employed in practically all lines of experimental work.
methods of expressing the concenbecome more apparent by a specific example. Suppose we have a 40 per cent cane sugar solution. What is the normal volume concentration of this solution and what is the normal weight concentration? The specific
difference these
will
What
tration
makes
gravity of a 40 per cent sugar solution at 20 C. is 1.17648 then one liter of this solution would weigh 1176.48 grams, and it would contain 470.59 grams or 1.376 moles of sugar and
;
705.89 grams of water. That is, there are 1.376 moles of sugar contained in one liter of a 40 per cent sugar solution. Now
by weight normal we mean the number

in 1000
of moles contained
grams
of water.
Since there are 470.59 grams of
360
PHYSICAL CHEMISTRY
sugar contained in 705.89 grams of water, then we have Solving for x, we have 470.59 705.89 :: x: 1000 grams. 666.7, therefore there are 666.7 grams, or 1.9493 moles, of sugar in i ooo grams of water. From this then we see that a 40
:
per cent sugar solution expressed as a normal volume solution would have a concentration of 1.376 moles dissolved in one
liter of
the solution, and expressed as a normal weight concentration of 1.949 moles dissolved in one liter of solvent. So it is apparent that there is a very decided difference
whether our concentration is expressed as a normal volume As stated above, or as a normal weight concentration. Morse found better agreement between the experimental results and theoretical values by employing normal weight, that is, a volume of 1000 grams of the solvent. Thermodynamic Equations for Concentrated Solutions. For solutions a complete thermodynamic equation would be very complicated, as it would have to take into consideration a large number of assumptions concerning the two components, the solvent and the solute. The expression would have to include among other assumptions the molecular
state of the solvent
and
of the solute, their
volume change
when mixed, the heat
of dilution, compressibility, etc.
By
simplifying the conditions there has been obtained a general equation for ideal or perfect solutions by assuming that these
is
two components do not interact with each other, that there no heat of dilution, that the resulting volume on dilution is the sum of the original volume plus that of the solvent, and that the properties are intermediate between the properties of the
pure components.
Previously
we saw
that log p/pi

fl
=
P
the molecular volume Vm we have log e p/pi
^ Rl VP =-
and
since
=
P
we
get
p =
RT
-
K1
from which
log e p/pi
From
Raoult's
Law we have
-.;.;.
361
pi
_ n
p
which gives us
T
N
N
-Pl = JL
p
and
if
we
define the ratio of the
number
of molecules of the
solute to the total
number
of molecules
by
x,
then %
x.
Substituting and transposing

stituting this value of
i
we obtain
&
P
=* i
Sublog e
we have p =
log (i
RT
[
*
n the equation pn = (i x)],
Vm\
Pi/
log,
which on expanding
m x) into a series, the equation then takes the form
RT
This equation, into which a factor for the compressibility been introduced, is the one given by Findlay and takes the following form
:
of the solutions has
RT
r
in
which p
is
the osmotic pressure and defined as the addi-
tional pressure that must be put upon the solution to prevent the inflow of the solvent through a perfectly semipermeable
membrane,
Vm
is
the molecular volume of the solvent under
standard pressure, x
the solute to the
coefficient of
is the ratio of the number of moles of number of moles of the solvent, and a is the But since the compressibility compressibility.
of solutions is very slight except for enormous pressures, it is assumed for moderate pressures that the compressibility fac-
362
PHYSICAL CHEMISTRY
tor is negligible, and no appreciable error is introduced by omitting this factor entirely. So employing the equation without the compressibility
factor
we have
For concentrated solutions Raoult used N + n as the total number of molecules in the system and then x would be and substituting in the above equation this value. N+n we have n RT n f
,
.
In the case of infinitely dilute solutions, however,
N+n
becomes
and the value of
this fraction
becomes very
small and the terms involving the higher powers of the The equation then simplifies to fraction are negligible.
Po
_RT ~
Vn
pQ V
N
it-
n_
Now
self
since
VmN represents
^,
the volume, V, of the solution
we have p =
or
= nRT, which
Law
is
the usual
form of van't Hoff 's equation or the Gas

Another Form of the Equation.
.
Equation.
L
By
employing a method of ex-
pansion
for the
term log
Pi
in the equation
pn =
IT) /T-i
Vm
:
log
-,
pi
different
from the one employed above, we obtain the following
From Raoult 's formula

obtained
:
l(P 5 (p
+ pJ
~ frV +
...1
P p
+ pi
2N + n
1
- -5
N+
the following relation
may
be
Substituting this value in the above
equation we have
See Wells' College Algebra.
363
?= RT
.
This equation may preferably be employed for the calculation of the osmotic pressure from the experimental data. Exact values are obtained by employing the first term of this expression, while with the
other formula two and sometimes three terms are required for the same degree of exactness. It will
be recalled that Morse employed normal weight
concentrations in expressing his osmotic pressure results. So in the equation

_
'
RT
T
I
Vm N + nL
'*~2(N + n)^3\N +
if
V,
"1
n)~ "J
in 1000
2 93
;
the values for a solution containing n moles of sugar dissolved grams of water at 20 C. would be T = 273 -+- 20 =
:
V
is
which
-i-
8
;
=
%
being the volume of 1000 grams of water at 20, 1001.8 cc. N, the number of moles of water, is 1000 the molecular volume Vm is 1001.8 divided by 55.5
; ;
55.5
R =
81.6 cc. atmos., as
employed by
Morse on the
basis that
instead of the usual value
82.04 cc. atmospheres. Substituting these values,
we have
n
(
,
81.6
293 1001.8
55-5
n
2(55.5
55-5+ n\
from which the osmotic pressure
may
be calculated.
This
gives us the osmotic pressure of solutions by means of which Morse's observed values are checked fairly closely, as shown
in the third
column of Table LX. assume that the solvent takes the form equation
Now let us
is
associated, then the
364
PHYSICAL CHEMISTRY
RT
where a
is
the association factor for the solvent.

is
The num-
ber of moles of the solvent then
According to van Laar the association factor,

at 20
a, for
water
C.
is 1.65,
and the number

is
of associated molecules in
iooo grams of water
*"1*
1.65
33.7,
and the molecular

'
vol-
ume
which is m of the 33-7 formula. Substituting these values in the equation above and calculating for the osmotic pressure, we obtain 23.5 atof the associated molecule is
,
I001
mospheres as against the value 23.64 without correction for the association of the solvent. These values are practically
the same, showing that up to this concentration the association of the solvent can be neglected. Even making the calculations upon the basis of normal
weight relations instead of normal volume relations, and correcting for the association of the solvent, there still remains
some considerable discrepancy between the experimental values of the osmotic pressure and the values calculated in the manner just indicated. Now let us make the addiassumption that the solvent and the solute do react with the formation of hydrates of the solute. In the process
tional
of hydration there is then removed from the solvent that amount of the solvent which is in combination with the solute
molecules, and this quantity will disappear in so far as its action as a solvent is concerned. Hence the number of molecules of solvent will be decreased
by
this
amount.
Then
the equation becomes
RT
Vm
N-
(3n
nl
2(N - pn
n)
in
365
which we have introduced the correction /3 for the number combining with each molecule of the solute, and (3n is then the number of moles of solvent that have disappeared from the scene of action as solvent. The molecular volume of the solvent then should be the 18 (3n) grams of water at the specified volume of (1000
of molecules of the solvent
temperature, divided by
(N
(3n),
the
number
of molecules
of solvent actually serving as solvent. The values as calculated according to this assumption with /3 = 5 are given in
the fifth column of Table LXII.
TABLE LXII
(Findlay's Osmotic Pressure, page 41)
366
PHYSICAL CHEMISTRY
In this case the value of

the volume (1000
moles.
Vm
the molecular volume, would be
18 0n)
grams of water divided by
^-@H
a
Upon
the basis of these two formulae and on the as-
sumption that sugar forms a pentahydrate, values for the osmotic pressure have been calculated from Morse's data and are incorporated in Table LXII, the columns being fully
explained by their headings. In the last column there are added the calculated values
on the assumption of association of the solvent, that the molecule of sugar has six molecules of water of hydration, .and the usual value (82.04) of R is employed. With these assumptions the calculated values approximate very closely
to the observed experimental values of Morse. From these values it is seen that by introducing into the equation for ideal solutions factors for the association of the
and the hydration of the sugar, we obtain values for the osmotic pressure nearer those actually obtained experimentally than the values given in the third column, where
solvent
these assumptions were not made. Further, the hydration correction is much more pronounced in the more concen-
trated solutions than the association factor correction.
The
same
is
noticed
if
the data of Earl of Berkeley and Hartley
are employed and a hexahydrate of sugar be assumed. Heat of Dilution. More than ten years ago Bancroft called attention to the relation of the Heat of Dilution and
bearing on the van't Hoff-Raoult Formula, and referred Ewan's discussion (1894) of this problem and the formula he worked out showing the relation of the heat of dilution to the osmotic pressure, which had been practically neglected. Bancroft formulates a relation and proceeds to show how the
its
to
osmotic pressure varies with the heat of dilution, that the abnormal molecular weights for sodium in mercury, sulphuric
acid in water, resorcinol in alcohol, cupric chloride in water, and alcohol in benzene are due wholly or in part to the heat
of dilution,
367
but the abnormal weights for sodium chloride in water are not due to the heat of dilution. In the case of sodium in mercury the apparent molecular weight was found to be 16.5, and, correcting for the heat of dilution, 22.7 was obtained. The apparent molecular weight of sulphuric acid varies from 57.7 in a 5.6 per cent solution to 11.7 in a 68.5 per cent solution, and when the correction for the heat of
applied we get molecular weights that are approximately constant but somewhat in excess (115) of the true molecular weight (98), and increasing at first and then redilution
is
maining practically constant with the increase of concenIn the case of sodium chloride the apparent molectration. ular weight is about 29, or one half of the formula weight
at infinite dilutions, while the change of the heat of dilution with the concentration is zero, hence these abnormal values
for
sodium chloride are real and are not to be explained on the
basis of the heat of dilution.
CHAPTER XXXI
HYDRATION
WE have seen that by assuming the hydration of the solute and thus removing a part of the solvent from the sphere of action as solvent, the solution becomes more concentrated, and the osmotic pressure calculated on this basis conforms more nearly to the values determined experimentally. Jones and his students ascribed the deviation in the freezing point determinations to the formation of hydrates and assumed
of
that they existed only in concentrated solutions. In the case many of the other properties of solutions which are colligative, there is a marked difference in the values determined
experimentally and calculated upon the basis of the Arrhenius Electrolytic Dissociation Theory. There is now a tendency to explain these abnormal results upon the assumption of the union of the solvent
and the
solute,
i.e.
on the
assumption of the existence of hydrates in solution. This is bringing us back to the fundamental conceptions of the old Hydrate Theory of Solutions which was strongly advocated
In the Mendele"eff (1886) and by Pickering (1890). foundation of the old Hydrate Theory, the points of discontinuity in the plotted observed data wherein the graphic method was employed were taken as evidence of the existence
by
of hydrates.
Pickering justified this method and fully apin its application, as is shown from difficulties the preciated the following quotation
:
application of the graphic method requires a great amount of close attention to experimental and other conditions, and it is to be feared that hurried use of it by those who have not taken the trouble to master the necessary details, or to acquire the requisite
"
The
care
and a
368
HYDRATION
369
amount of skill, may bring it into undeserved disrepute. From the study of any one, or any few, particular breaks I concluded nothing from a study of a whole series of density results I only concluded that it was advisable to make other series at other temperatures; from a study of the series at four different temperatures I concluded only that I had strong presumptive evidence of the existence of changes, but that confirmatory evidence from the study of independent properties was necessary before such changes could be regarded as established, and it was only after obtaining such evidence from the study of three or four properties that I ventured to call the evidence proof, and then that many of these changes were only with oft-repeated caution, " admittedly of a very doubtful nature.'
;
'
'
'
The points of discontinuity were observed in the case of density curves, the determination of capillarity, viscosity, etc. This group of physical properties of solutions conforms to the so-called
Law
of Mixtures
and
is
additive with
Where there is a variation from respect to the constituents. the law it is customary to assume that the molecular property of the solvent remains unchanged and to ascribe all deviations to changes in the physical property of the solute,
which in many cases has led to absurd conclusions. To get around these, complexes between the solvent and solute have been assumed, and the literature contains references to a large number of such cases which have been determined from the discontinuity in property-curves of the following
physical properties of solutions
:
heat capacity,
density,
viscosity, refr activity, conductivity, compressibility, surface It tension, coefficient of expansion, and heat of solution.
would, however, lead us too far to consider in detail the evidence presented by these experimental methods, but many
experimenters attribute the irregularities in the property curves to the presence of hydrates and use these properties
for proving the presence of hydrates in solution. In Fig. 55 we have from the so-called solubility curve for
S0
in
H O,
2
a confirmation of the " breaks " of Mendeleff
and of Pickering.
We now recognize definite hydrates among
370
PHYSICAL CHEMISTRY
" " breaks between which it is possible to account for all 10 and go per cent H 2 SO 4 by assuming three known hydrates and one unknown hydrate instead of the three known and We have the following six unknown hydrates of Pickering.
well-defined hydrates
1.
:
very stable but does not reveal itself in the density curve, but the capillarchange abrupt by any both reveal it. This is known as curves and the viscosity ity acid and is not usually considered as a hydrate. pyro-sulphuric 2. SOs Ho>O, a monohydrate, is familiarly known as sul-1/2
2
2 SO 4 phuric acid and contains 100 per cent 2 O, the dihydrate of SO 3 is scarcely a matter 2 SO 4 3.
.
SO 3
H O is
H
2
of controversy.
4.
5.
H SO H SO
2 2
4 4
H O has been obtained in the crystalline form. H O, the pentahydrate, may be responsible
2 2
for breaks at 59 per cent. The electrical conductance of solutions of sulphuric acid gives a curve that indicates most clearly the presence of three
hydrates.
trioxide of sulphur are both exbut a mixture of two parts of SO 3 to four parts of H 2 O is one of the best conductors known, the specific resistance being 0.7388 ohm at 18 C. The curve is smoothly
cellent insulators,
Water and the
rounded, and according to Kohlrausch's rule that mixtures give higher conductance than the pure substances, there is no reason for attributing this maximum to the formation of it would agree fairly well with the formula hydrates
SO 3
H O.
2
The mixture, on changing the ratio,
decreases
in conductance until at the concentration 81.44 per cent SOs the value is 0.0080 ohm, which is about one per cent of the
maximum
This minimum is very clearly defined, as value. the conductance increases 100 per cent when the solution is mixed with 0.17 per cent of 2 O or with 0.23 per cent of 2 O. Kohlrausch has shown that this minimum is reached when
the
ally
SO 3 and
i
:
H O are in the ratio of 0.9975

2
i,
and
therefore this
minimum
which is virtube attributed to can

:
i,
HYDRATION
the hydrate
371
SO 8
an
insulator.
The hemi-hydrate
H O, which is a chemical compound and is 2 SO H O has even a

2 3 2
lower conductance (0.0008) than the monohydrate, and soluThe minimum tions of SO 3 in this give zero conductance.
value at 69 per cent SOs corresponds to the dihydrate SO 3 2 2 O, the conductance at 18 being 0.098 ohm, and this minimum is 300 times less sensitive than in the case
of the
It will lytic
monohydrate. be recalled that the Arrhenius Theory of ElectroDissociation was advanced to account for the abnormal
values that are obtained
by the lowering of the freezing point, the elevation of the boiling point, the osmotic pressure, and the lowering of the vapor pressure. The degree of electroby
these various
lytic dissociation
methods and
could be determined with equal accuracy also by the electrical conduc-
These properties of solutions are Colligative, that is, they depend upon the number of parts in the solution, and, the solutes are said to be ionized in order to account for these
tivity.
additional parts in solution. What is the cause of this ionization ?
One of the questions that has been asked frequently is, Why is it that these substances which liberate so much heat when they are formed
become dissociated so easily when they are dissolved? In other words, what is the motive of the electrolytic dissociation? In the formation of KC1 from its elements there is a liberation of 105,600 calories, which means an absorption of this same amount of heat when the compound is again
decomposed, but the heat of electrolytic dissociation
as 250 calories.
"
is
given
Bonsfield says
This extraordinary discrepancy between the two values appears
to indicate that the process of ionization cannot consist merely of the separation of the molecule into its constituent atoms even though
may be endowed with electrical charges, and we are driven to assume that the essentially endothermic process of dissociation must be balanced by some powerful exothermic action, associative rather than dissociative."
they
372
PHYSICAL CHEMISTRY
Fitzgerald in his classic Helmholtz Memorial Lecture delivered in 1892 says

"
:
heat absorbed when ions are dissociated has been proposed to explain this by various suggestions which do little more than re-state the facts in some other form and call for new properties of ions especially invented to suit the circumstances. The suggestion mentioned is that the presence of a
Why is
there then so
?
little
by going
into solution
It
of high specific inductive capacity, like water, very much diminishes the force of the attraction between the electrons by providing, what comes to the same thing, induced electrons in the water moleThis is an excellent cules to help in drawing those in the salt apart. suggestion but is it not really the same thing, under another guise,
body
as stating that it is by chemical combination with water that the salt has conferred upon it the property of exchanging partners ? What are these electric charges supposed to be induced on water but electrons
thereon
and what
is
the attraction of the electrons

for chemical
among
the mole-
cules but another
name
combination
All of this hangs
together, but it lends no support at all to the dynamically impossible theory that the ions are free. What it suggests is that this so-called freedom is due to there being complete bondage with the solvent."
At the time Arrhenius published the relative values of i and a calculated from the electrical conductance, the freezing point, and the boiling point determinations, he recognized
great discrepancies in the cases of the sulphates in general, which he sought to explain by assuming polymerization of
the undissociated molecules. Since the data employed by Arrhenius were obtained, more accurate data have been colThe lected, showing that these abnormal values are real.
freezing point determinations by Loomis, Abegg, Jones, Roth, Raoult, Ewan, Kahlenberg, Biltz, as well as boiling point
determinations by the same experimenters, and particularly the data by Smits, show that these methods give values for
the degree of electrolytic dissociation which are in many cases entirely different from the values obtained by the conductivity
method.
A few specific cases will suffice to illustrate the
general trend of these irregularities. The data given in Table LXIII are taken from that compiled in Landolt and Born-
HYDRATION
stein's Tabellen
373
with the exception of that for
KBr and some
of the data for
NaCl by the boiling
point method, which were
obtained from- the original source. The degree of dissociation from the electrical conductance method are taken partially from Jones' work, and the other values were calculated from
data given in Landolt and
TABLE LXIII
FREEZING POINT OF SOLUTIONS
GRAM ANHYDROUS
SALT IN 100 GR. H-iO
374
PHYSICAL CHEMISTRY
the data obtained
freezing point method the practically constant for all concentrations, showing, however, a slight decrease in the degree of dissociation with the increased concentration up to about
From
by the
molecular weight of
NaCl
is
molar concentrations.
At the lower
dilutions the degree
from the conductance agrees very well with that obtained from the freezing point data, but at the higher concentrations there begins to appear a marked divergence. For MgSO 4 the degree of dissociation decreases very rapidly with the concentration and becomes only a few per cent at approximately normal concentration. The conductance gives at these higher concentrations a degree of dissociation of about 40 per cent. Practically the same holds for ZnSO 4 at molar concentration the degree of dissociaof dissociation as calculated
,
tion is practically zero according to the freezing point determinations and 26 per cent by the electrical conductivity method.
TABLE LXIV
BOILING POINT DETERMINATIONS
GRAM ANHYDROUS
SALT IN
100 GR.
HzO
HYD RATION
TABLE LXIV
Cont.
95.3
375
MgCb, Molecular Weight

3-371
376
PHYSICAL CHEMISTRY
the same
is
KBr
true, for concentrations 2.8 to 4.3
molar the
degree of dissociation ranges from 99.5 per cent to 114.9, while according to the conductivity method the values for
the same concentrations are 69 and 63.2 per cent respectively. For MgCl2 the molecular weight decreases with increased concentration, giving a dissociation increasing with concentration, being at approximately 2 molar concentration 146 per cent as against about 31 per cent as determined by For BaCl 2 the molecular weight decreases as the conJones. centration is increased, showing a dissociation ranging from 53 per cent for approximately 0.15 molar solution to 103 per cent, while for the same concentrations the degree of dissociation by the electrical conductivity method is 7 2 per cent and 45 per cent respectively. For CuSO4 the molecular weights are all above that represented by the formula weight except at the very highest concentration which is nearly 5 molar. There would be no dissociation at the lower concentration, but at the higher concentrations the molecular weight found is lower than the theoretical value. The same is also found for the non-electrolyte sugar, the molecular weight
decreases with increased concentration.
tions the molecular weight
is
In the dilute soluabout normal, while at about 8
molar concentration the value is 214. By the vapor pressure measurements at o Dieterici found that the molecular lowering for CaCl 2 diminished rapidly with the increase of dilution, and at about o.i concentration increased with the dilution. The freezing point determinations of Loomis and of Ponsot show a minimum for the mo-
lecular lowering of the freezing point at nearly the same concentration. Jones and Chambers' results confirm this.
For 3 PO 4 2 SO 4 NaCl, CaCl2 cane sugar, dextrose, and urea in concentrations o.i to i.o N, Dieterici found that the molecular lowering of the vapor pressure diminishes as the dilution increases, which is opposite to that required by the
, ,
,
electrolytic dissociation theory as stated.
Dieterici therefore
HYDRATION
refrains
377
from even attempting to make any further comparison between the degree of dissociation as calculated from the vapor pressure measurements on the one hand and the conductivity on the other. From vapor pressure determinations
molecular weight of
Lincoln and Klein found practically the same values for the 3 as that found by other workers
KNO
by the freezing point and boiling point methods. For NaNO 3 however, the value for the molecular weight was practically
,
the same, 48.13-48.91, over the whole range of concentraThis is approximately one half the theoretical value, tion.
85.1, and the degree of dissociation would be the same for the whole range of concentration. For the most concentrated solutions of LiNOs the molecular weight was found to be
17.58,
and
for the
most
dilute, 36.09, as
compared to the
formula weight, 69.07. molecular weight, 34.5,
In the most dilute solutions the
is practically one half the theoretical of dissociation virtually of 100 per cent, a value, giving degree while for the most concentrated solutions employed the value 17.35 found is about one fourth the molecular weight and would correspond to a dissociation of about 200 per cent. By the freezing point method Biltz found the same general results, i.e., in the more highly concentrated solutions the
LiNO 3
is the more highly dissociated. Various explanations have been put forth to account for these numerous irregularities such as illustrated above, and
one marked similarity in them. They all aim to anomalous results upon the assumption of some these explain combination between the solvent and the dissolved substance.
there
is
Arrhenius was
among
the
first
to suggest that ionization
depends not on the physical properties of the solvent but upon the chemical equilibrium between' the solute and the As early as 1872 Coppet, from his freezing point solvent. measurements, ascribed his results to the formation of hydrates, and calculated the composition of many of them.
Jones ascribes the deviation in the freezing point determina-
378
PHYSICAL CHEMISTRY
tions to the formation of hydrates, but assumes that they
He assumes that the exist only in concentrated solutions. degree of hydration can be calculated upon the normal
volume
plan, notwithstanding that this
method involves
the acceptance of the Ionic Hypothesis and the application throughout of the factor 18.6 in calculating the lowering
of the freezing point. Jones also leaves out of account the effect of hydration on the ionic mobility, the polymerization
effects, and practically all others, and concentrates the whole variation to the formation of hydrates resulting in the removal of part of the water from its function as a solvent. " The fact that a part of the water is combined with the dissolved substance and is not acting as solvent, must be taken
into account in dealing with all solutions and especially concentrated ones. This accounts in large part for the abnormal " " conclude that behavior of concentrated solu tions.
We
both molecules and ions have the power to combine with water in aqueous solutions and form hydrates." In many " combined " amounts to a large percentage cases the solvent of the water present and in a few cases to between 100 per
cent and 114 per cent.
Biltz, although he pointed out that Nernst had shown that the formation of hydrates is directly contrary to the Law of Mass Action, and consequently untenable, recognizes that
their formation
may be
of strong electrolytes.
the cause of the abnormal properties He argued that CsN0 3 to be slightly
hydrated, if at all, lowers the freezing point in accordance with the Ostwald Dilution Law and is to be regarded as be-
having normally. The electrical conductance of such solutions is not that to be expected from the freezing point determinations, and it therefore follows that conductivity cannot be taken as a true measure of the state of dissociation even
in the case of salts that are not hydrated. Taking the cases the dilution law to of NaCl and KC1, which do not conform
as regards freezing point,
and assuming that they are
dis-
HYDRATION
sociated to about the
379
same extent
as
CsN0
3,
Biltz calculated
NaCl can be associated with 19 to 20 molecules of water and KC1 with 15 to 24 molecules, according to the concentrathat
tion. Biltz, as well as Jones, finds indications that the complexity of the hydrates decreases with rise of temperature. The abnormal boiling point values are explained upon the
basis of the formation of hydrates.
Smits determined the vapor pressure at o of NaCl, H 2 SO 4 and sugar. For sugar he finds an average molecular 3 hydration of 5.7 as compared to 6.0 obtained by the freezing
,
KNO
point method, hence we would conclude that sugar exists in solution as a hexahydrate. Compare this with the assumed
hydration, page 365. Abegg has stated very clearly the application of the hydrate theory to the equilibrium between the solvent and solute,
and his researches show that what is ordinarily termed normal

or simple ionization may be to a very large extent a complex ionization in which the solvent molecules play an essential
part.
He assumes that the molecules possess a power of spontaneous ionization which is independent of the association of the ions with the solvent. Armstrong says that apart from the fact that the Electrolytic Dissociation Theory is irrational and inapplicable to compounds in general, there are experimental facts ob-
tained
by several different lines that militate against it. Sucrose and esters are hydrolyzed in the presence of acids and also of enzymes, and in both cases the degree of acidity varies with the acid or with the enzyme. Since the selective
action of the enzymes can be explained on the basis of combination with the hydrolyte, there is no reason why this ex-
planation should not be extended to the acids. Further, it found that the acidity of an acid as a hydrolyzing agent
is is
frequently increased by the addition of its neutral salts, and as non-electrolytes also sometimes act in the same way there
is
no reason to account
for the activity of the electrolytes
by
380
PHYSICAL CHEMISTRY
is inapplicable to non-electrolytes. Since alcohol, equally with hydrochloric acid, causes the precipitation of chlorides from solution, the explanation which
an explanation which
can be applied to alcohol, namely, hydration formation, should also be applicable to hydrochloric acid. In 1886 Armstrong attributed the increased molecular
conductivity of dilute solutions to the gradual resolution of the more or less polymerized molecules of the salt into simpler
molecules or monads which, when combined with the solvent, " constituted a composite electrolyte." Recently he adds " that the electrolytically effective monads must be thought
of as hydrated in
some particular manner, perhaps
as hydrox-
ylated and that the association of the solvent with the negative radical of the solute was the determining factor in electrolysis."
He
considers that the positive radical
of the
solute has
no tendency to associate with the solvent and that
the power of ionization does not involve the resolution of the molecules into separate ions. Werner in his New Ideas on Inorganic Chemistry presents a re'sume' of his work on the ammonia substitution products and the reactions in the formation of analogous compounds, which
he develops into his theory of Bases and Acids and the Theory In this he presents, in opposition to the above idea, the suggestion that the ionization is due to the
of Hydrolysis, etc.
association of molecules of water or ammonia with the metal, the negative radicals being regarded as inert. Many metallic salts form hydrates with six molecules of water such as the
following:
[Ni(OH 2 ) 6 ]Cl 2
,
[Co(OH 2 ) 6 ]Cl 2
,
[Zn(OH 2 ) 6 ](NO 3 ) 2
,
[Mg(OH 2 ) 6 ]Br2 [Ca(OH 2 ) 6 ]Cl2 [Sr(OH 2 ) 6 ]Br2 [Fe(OH2 ) 6 ]Cl 3 Many of these hydrates contain the maximum number of water molecules known to the salt, and their con.
stitution is analogous to the hexamine metallic salts which have been extensively studied. Werner assumes, therefore,
that the hexahydrates are salt-like compounds in which the positive radical consists of complexes containing
HYDRATION
381
the metal and six molecules of water, which are linked directly to the metallic atom and in a separate sphere from the
acid residues.
greenish blue hexahydrate CrCl 3 6 H 2 O a blue-violet solution, and all three of the dissolves, giving
The
chlorine
trical
atoms are present as ions, as is shown by the elecconductivity and freezing point determinations and by
.
treatment with silver nitrate. It is therefore represented by the formula [Cr(OH 2 ) 6 ]Cl 3 On losing two molecules of water this is transformed into a green hydrate, CrCl 3 4 H 2 O. This hydrate in solution shows that only part of its chlorine is in the ionogen condition as only two thirds of the chlorine
can be precipitated by
l
AgNO
3.
The formula would then be

is
still
2-H2 O.
There
another hexahydrate
which contains only one chlorine with ionogen properties,
and the formula assigned to
it
is
Cr/Q H
Cl
H O.
2
These extra molecules of water are not linked to the dissociated chlorine ions, and from evidence presented he concludes
that they belong in some way to the chromium complex, and the following expression illustrates the relations between these
three isomeric hexahydrates
:
[Cr
(OH 2 ) 6 ]C1 3
chloride
Cr
|
^wT
1
I
12
|
Cr Cl
[<
chromium
H 0~| H O Cl
2 2
(OH 2 ) 4 J
Green hydrate of
chloride
Blue hydrate of
chromium
Bierrum's chloride
Werner further shows that acids
as well as bases are formed through the combination of the solvent and solute, so in general he expresses the view that the ionization is preceded by a combination with the solvent. It is primarily the metallic
t
or positive part of the solute that is hydrated. It would lead us too far to consider the experimental data
that led
Tammann
to consider that salt solutions resemble

;
the pure solvent under increased external pressure
Traube
382
PHYSICAL CHEMISTRY
is
to state that each ion

of water
;
in combination with a single molecule
most
Vaillant from density determinations to conclude ions to be anhydrous, but OH", F~, S~~, and CO 3 to
be monohydrated Philip to deduce from solubility of hydrogen and oxygen in salt solutions the agreement of the degree of hydration with the values obtained by the acceleration of the inversion of cane sugar by acids as influenced by salts as measured by Caldwell and from the freezing
;
how
and to show point determinations by Bonsfield and Lowry the Phase Rule could be applied to the determination
;
of hydrates in solution.
Kohlrausch's observation led him to consider the ions water coated and that the combined water altered the size of the ions, and he concluded that the effect of the change
for the
and of size of the ions might adequately account change in the migration velocity observed with the change in the dilution, i.e. that there is a change in the degree of hydration of the ion with the change in the concentration of the solution. From Table XLIX of Transference numbers it appears that the heavier atoms yield the more mobile ions, and for this reason it is concluded that the ions are hydrated. Lithium ion is the most highly hydrated and the caesium ion
of velocity
the least hydrated of the metals of the alkalies. When a current is passed through the solution of an electrolyte the transfer of the current should be accompanied by
the transfer of water
if
an easy matter to detect
the ions are hydrated, and it should be this. Various attempts have been
made
to determine this transfer of water by electrolyzing a solution containing a small quantity of a non-electrolyte that could be used as a reference substance. This reference
substance not being affected by the current will remain distributed, after the electrolysis, just as before, and any
change resulting from the transference of the water from the anode chamber will be recognized by an increase in the
concentration of the non-electrolyte at the anode and a cor-
HYDRATION
responding decrease at the cathode. place when the electrolyte is absent,
383
As no change takes assumed that the water is transported by the migrating ions and that this is the amount of water that is in combination with the respecNernst and his pupils have tried this method with tive ions. Washburn found that the cations are indifferent success.
it is
hydrated as follows: H(H 2 O) 3 K(H 2 O)i. 8 Na(H 2 O) 2 .o, Ganard and Oppermann have found by asLi(H2 O) 4 7 suming the hydrogen ion to be anhydrous the following values SO 4 (H 2 0) 9 C1(H 2 O) B of hydration for some of the anions
.
Br(H2 O) 4
NO
(H 2 O) 2
5.
Newberry
states:
"
Previous de-
terminations of the hydration of ions by observations of the change of concentration of the non-electrolyte present have given incorrect values due the transport of the non-electrolyte
by the ion present and
also
by the action
of electric en-
concludes from a study of metal over voltage that H, OH, Fe, Ni, and Co ions are hydrated in + 4 aqueous solution while Cu, Ag, Zn, Cd, Hg Tl, Pb, Sn, SO4 ions are not hydrated. 3 Na, K, Cl,
dosmosis."
He
NH
NO
Constitution of Water.
sions that water
We have seen on several occawas considered a highly associated liquid,

of the associated molecules has
and the exact composition
been the subject of extensive research. As early as 1891, Rontgen put forth the idea that water is a binary mixture of " " " " water molecules and of ice molecules of greater complexity but smaller density, so that when the liquid is heated these complexes are decomposed, and a contraction is produced which is sufficient between o and 4 to counteract the ordinary thermal expansion of the liquid. Tammann made use of the composite character of liquid water to account for the abnormal character of his data obtained on the compressibility of the liquid, and also regarded water as a binary mixture. Sutherland, within the last few years, from his extensive researches, concludes that water vapor in the condi1
Jour. Chem. Soc.
in, 470
(1917).
384
PHYSICAL CHEMISTRY
is hydrol (H 2 O), ice is trihydrol liquid water is a mixture of the trihydrol and dihydrol (H 2 O) 2 in proportions which vary with the temperaIt is to this comture, pressure, and the presence of solutes.
tion of a nearly perfect gas
(H2O)a,
and
plex character of water that

ties of
many
of the exceptional proper-
water and of aqueous solutions are attributed. Bonsfield and Lowry, from a study of the density of aqueous
solutions of caustic soda, sugar, chloral, acetic acid, silver
sodium chloride, potassium chloride, lithium chloride, and calcium chloride, conclude that water is really a ternary mixture consisting of the trihydrol, dihydrol, and monohynitrate,
drol.
On
cooling liquid water there

ice molecules,
is
a formation of the
more polymerized
and heating causes their dissociation, yielding the monohydrol or steam molecules. Each of these changes is accompanied by an increase of volume superimposed upon the expansion or contraction reHence the sulting from the mere temperature change.
density of solutions
of hydrates.
It is
is
presented as evidence of the formation
argued that the influence of the solute cannot be accounted for unless some abnormal value is assigned to the density of water in combination with the solute. Hydrate formation is stated to be always accompanied by a contraction of volume, hence, the density of this water must be greater than that of the water in the ordinary state. In F. Clark W. attributed to of water 1875 crystallization a molecular volume of 14 cc., and this is practically the same as that deduced by Thorp and Watts from the metallic sulThese values give a density of phates, which was 14.5 cc. for the Sutherwater of crystallization. approximately 1.24
land gives 1.089 as the density of dihydrol, and Bonsfield calculates the density of water of hydration of KC1 as i i which
.
value gives a degree of hydration of this salt practically the same as the value found by Philip from the solubility of hydrogen gas in KC1 solutions and that of Caldwell from the
influence of
KC1
in accelerating the inversion of cane sugar
HYDRATION
by acids.
water.
385
Hence they conclude that the density of combined water approximates that of the denser constituent of liquid
his extensive experimentation on vapor pressurface sure, tension, molecular weight determinations, and association coefficients, concludes that the data obtained
Guye, from
appear to form new evidence in favor of the chemical concep-
phenomenon of association or polymerization in the liquid phase of water or other associated liquids. And further, the coefficient of association of Dutoit and Majoin
is
tion of the
in agreement with the results according to which liquid water at o is mostly t'rihydrol, (H 2 O) 3 and at the boiling point dihydrol, (H 2 O) 2 Walden from his researches on the anomalous behavior of water when dissolved in solvents of high dielectric constants concludes that a chemical interpretation of these results must be attempted and that there is formed, owing to the chemical nature of the solvent and solute, a molecular combination of a salt character which is then the conductor of the electric current and an electrolyte.
,
.
From
the foregoing
we see
that there
is
a tendency for the
modern workers
lation of
to get back to the earlier conception of a reaction between the solvent and the solute, and that the formu-
any theory
of solutions should take this into con-
sideration.
CHAPTER XXXII
HYDROLYSIS
WE
is
are familiar with the fact that a solution of

;
Na C0
2
denned as a normal salt, i.e. one in which all of the hydrogen of the acid had been replaced by sodium. We further define a substance which in aqueous solutions yields hydroxyl ions a base, and conalkaline in reaction
but
Na CO
2
is
3 versely, since there are hydroxyl ions in a solution of Na2 it is therefore a base. As there is no in Na2 3 the nec,
CO
OH
CO
essary hydroxyl ions
must come from the water

,
carbonate
2
is
dissolved.
2
in which the So the reaction between the solvent,
water, and the
Na+ CO ~
3
Na CO 3
2
the solute,
is
represented thus
(H
OH-)
NaOH
(Na
OH')
+ H CO
2
3.
As
is
hydroxyl ions.
highly dissociated, this then is the source of the A solution of ferric chloride is acid in reis
action, and similarly this reaction: Fe +++ 3 Cl~

-
accounted for by the following
+3
(H
OH~) ^
Fe(OH) 3
3 (H acid
highly dissociated as it is a strong and yields hydrogen ions. It is to the presence of these that the acid character is attributed.
Cl~).
is
The HC1
Dissociation of Water. We have seen that pure water is one of the best of insulators consequently, its electrical conductance is very slight. This conductance must be due to the presence of hydrogen and hydroxyl ions, but since their ionic conductances are the greatest of any ions there must be but a few of them to account for the slight conductance of pure water. Kohlrausch found, for the purest water that he could prepare, a conductance at 18 of 0.040 X io~ 6
;
.
386
HYDROLYSIS
387
.
6 From the con0.054 X io~ ductance the concentrations of the hydrogen and of the
The conductance
at 25
C.
is
hydroxyl ions have been calculated, and it is found to be about i.o X io~ 7 normal. Or applying the Mass Law to the dissociation of water we have
HO
2
H + OH
[H
+
]
.
fc[H 2 0]
[OH-].
Solving for
k,
the dissociation constant,
we have
fc
_[H+] -[OH-]. [H0]
but since the concentration of the undissociated water, [H 2 O], is very large as compared to the dissociated part, it may be considered as practically constant and the equa] [OH-]. Substituting the above + and OH~ we have value of the concentrations of
tion written
Kw
= [H +
Kw
as the
of water.
[i.o
io- 7 ]
[i.o
io- 7 ]
i.o
io~ 14
Ionic Product or so-called
Dissociation Constant
Dissocia-
In Table
LVIIIwe have compiled the

and
bases,
and the value for water is very small as compared with most of these. There are a number of other methods by which the dissociation of water has been determined, and among these may be mentioned the Catalysis of Esters, Catalytic Muta-Rotation of Glucose, Hydrolysis of Salts, and the Electromotive Force Method. These methods, some of which will be contion Constant of a few acids
sidered subsequently, give results that ably with the above.

tion to a
compare very favor-
The change in temperature affects the degree of dissociamarked extent, as the data in Table LXV obtained
:
by Heydweiller shows
388
PHYSICAL CHEMISTRY
TABLE
LXV
WATER
DISSOCIATION CONSTANT FOR

tC.
HYDROLYSIS
389
tained from the completely dissociated salt is the same as that from the completely dissociated HC1, hence our equation may be written
Kk=
in
..
[CJfrNH,C.H.OOH]
[C6 H 6
[H+l
NH C H 0-]
2
which
h is
termed the Hydrolytic Constant.

is
The
dissociation constant of water
Kw
= [H +
[OH~],
from which the concentration of the hydrogen ions

rjr+1
is
=
[OH-]
is
The
dissociation constant for the base

,
[C6 H 6
NH C H + [OH[C H NH C2H OOH]

2
2 3
]
+ Substituting the value of the hydrogen ion, [H ], in the above
equation
we have
[C 6
H NH C2H3O +
6
2
[OH-]
but the terms in brackets are

\
we have
~K
in which
K K
Therefore, substituting,
h is
Kb
of the salt.
the Hydrolytic Constant

;
Kw
by
is
the Ionic Product of the water
is
the
Dissociation Constant of the base.

Similarly
selecting a salt such as
it
7V-
drolysis gives
an alkaline reaction,
KCN, which on hymay be readily shown
that the hydrolytic constant

If
the two products of hydrolysis both weak electrolytes, as in the case of aniline acetate, C 6 B NH3CH 3 COO, the hydrolytic constant may be worked out in a similar
we have
manner.
3QO
PHYSICAL CHEMISTRY
ionic reaction
3
The
5
is
as follows
C6 H NH + CHaCOO- + HOH $ C H NH
6 5
OH + CHaCOOH.
Applying the Mass

[C 6
Law Equation we have

[HOH]
H NH +
5
3
[CHaCOO-]
=
and
since this
is
[C6 H 6
NH OH]
3
[CHaCOOH]
a dilute solution the concentration of the
water [HOK]
constant and the products of the hydrolytic dissociation are assumed to be un-ionized, the equation beis
comes
[C 6 H 6 [C 6 H 6
NH OH] NH +
3
3]
[CHaCOOH] [CH 3 COO-]

is
The
dissociation constant for the acid
[CH 3 COO-] [H + [CH 3 COOH]

therefore,
[H
+
]
_ " [CH COOH]

3
r
CH
COO-]
of the base
and similarly from the dissociation constant have [OH-] = [C 6 H 5 NH 3 OH]
we
[C6
H NH +
5
3
Now
have
substituting these values in the equation above
we
[H+]
[OH-]
K.-K,
but the numerator is the dissociation constant of water, hence substituting we have
"
Kw
HYDROLYSIS
which
is
391
the kydrolytic constant for the cases where both prodof Hydrolysis.
ucts of the hydrolysis are
Degree
anilid
weak electrolytes. The Mass Law Equation
for acet-
hydrochloride gives us the hydrolytic dissociation constant according to the equation
[C6H5NH2C2H300H]
[H
+
]
is the degree of hydrolysis, then as we have preseen in the case of electrolytic dissociation, the conviously centrations of the ions when there is one mole of the salt
Now if x
dissolved in v liters of water are

1
~
v
mole
mole
of
CeHsNHkQjHaO-
ions unhydrolyzed
of
H + ions
C6 H
5
mole
of
NH C2H3OOH undissociated base.

2
Substituting these values in the equation,
we have
x2
Kh =
TS
x
V
i
x
V
t which gives x
.
7, = Kh
-,
(i
x )v
Similarly in the case of aniline acetate
we have from
= [C 6
[C6
H NH OH] H NH +
5
3
[CH 3 COOH1 [CH 3 COO-]
the expression for the hydrolytic dissociation the equation
x
V
=
i
- *vi v
x\
)
)(
392
PHYSICAL CHEMISTRY
which becomes
as the hydrolytic constant for the cases where the two products It is evident, since the of hydrolysis are weak electrolytes. not appear in this does solution term for the volume of the
equation, that in cases of this type the hydrolytic dissociation is independent of the volume.
of x, the degree of hydrolysis, can be obtained experimentally from the speed of inversion of cane sugar or
The value
Then from
the hydrolysis of esters, which will be discussed subsequently. this value the hydrolytic constant can be calculated from the equations given above. The value of oo is determined from the electrical conduct-
is
ance of the solutions on the assumption that the conductivity an additive property, and hence the conductance of the solution is the sum of the individual conductances of the ions
For example, in the case of acetaniline hydrochlopresent. ride we have
A =
(i
x)A. v
+ #A H
ci,
in
which the total conductance, A, is the sum of the conductances of the un-hydrolyzed salt plus the conductance of the hydrochloric acid. Solving for x, we have
x
- Av = A
AHCI
Av
As the HC1 is completely dissociated, the value of AHCL becomes its value A^ and the value A v is the value of the conductance of the salt at the specified volume, assuming no
,
This value is obtained by forcing back the when hydrolysis by the addition of a large excess of the salt, A v becomes the conductance of the solution A. In Table LXVI will be found the values for the degree of h of a number hydrolysis and the Hydrolytic Constant
hydrolysis.
of
compounds.
HYDROLYSIS
393
TABLE LXVI
SUBSTANCE
394
PHYSICAL CHEMISTRY
TABLE LXVI
Cont.
SUBSTANCE
CHAPTER XXXIII
NON AQUEOUS SOLUTIONS
IN our study of solutions we have been considering primarily aqueous solutions, and the numerous theories we have been studying have been developed from these. The question arises, Are these theories applicable to solutions wherein
any substance may be taken as the solvent, or are they only applicable to the solutions in which water is the solvent? We have just considered in detail the Electrolytic Theory of Dissociation as developed to explain certain abnormal
values obtained in aqueous solutions wherein the solute was assumed to be independent of the solvent and was dissociated
by
it.
lected that are
now
Then we saw that many facts have been colbeing explained upon the basis of a com-
bination of the solvent and the solute as well as a combination of the dissociated parts of the solute with the solvent. Particularly in concentrated solutions have these assumptions
of hydration
been made to account for the abnormal values
presented by the data collected and interpreted in the light of the theory of dilute solutions.
The question arises, determination of the

solutions,
Can we employ
various
these methods to the
properties of nonaqueous and can the data collected by them be interpreted in a similar manner ? For example, do nonaqueous solvents yield solutions that conduct the electric current, and does the
conductance represent the degree of dissociation of the

solute
all
?
solvents
different
an electrolyte dissociated to the same extent by do the ions have the same ionic conductance in if they do not, why not, or in other solvents,
Is
;
395
3Q6
PHYSICAL CHEMISTRY
words, to what is the ionization of the solute due ? We know that some solvents yield conducting solutions, while others do not. Then is the degree of dissociation as determined by
the conductivity comparable to that determined by the other methods that are employed in aqueous solutions, such as freezing point, boiling point, osmotic pressure, and vapor
pressure ? It is therefore evident that the detailed consideration of nonaqueous solutions requires an extensive study of
we have been considering, as applied to solutions of solvents other than water. During the last
the methods and theories
few years
amount
tions.
many investigators have collected an enormous of data and have attempted to correlate these in the
developed on the basis of aqueous solu-
light of the theories
One
To what
of the principal questions that has been discussed is, is the ionizing power of a solvent due? Various
explanations have been presented, and we shall take up a consideration of these in our presentation. Among these
may
be mentioned the relation between the ionization power
and its dielectric constant, its association facthe electrical conductance of its solutions, the viscosity, tor, the combination of the solvent and solute, as well as the lowof the solvent
ering of the freezing point, the rise of the boiling point,
and
the osmotic pressure of the solutions.
Determinations of the electriconductances of solutions of many solvents, both organic and inorganic, have been made. These show that, as in the case of water, the conductance of the pure solvent is very
cal
Electrical Conductance.
small, while the solutions have a very appreciable conductance. In most cases the conductance is less than in aqueous
but in a few cases they conduct much better. Such inorganic solvents as NH 3 SO 2 and HCN yield solusolutions,
, ,
tions that conduct very well, in many cases as well as water solutions, while the solutions of various solutes in PC1 3 AsCl 3
, ,
etc.,
have a relatively small conductance.
A consideration of
NONAQUEOUS SOLUTIONS
397
the various groups of organic solvents shows, in a general way, that liquid hydrocarbon solutions, as well as their halogen The alcohols substitution products, are nonconductors.
yield solutions that conduct very well, but the conductance decreases with the increase of the carbon content as well as
with the complexity of the alcohol. The aldehydes yield conducting solutions, and many of the solutions of ketones are excellent conductors, while the esters yield conducting solutions which are however not very good conductors. Many of the organic compounds containing nitrogen, such as
the organic bases, amines, and nitriles, yield solutions that the nitriles in particular yield solutions that are conduct
;
excellent conductors.
The conductance of alcoholic solutions, particularly methyl and ethyl alcohols, has been studied extensively, and in general limiting values of the conductance have been found.
From
these values, then, as in the case of aqueous solutions, the degree of dissociation of the solute has been calculated. In Table LXVII are given Carrara's values for A^ for a number
of solutes in
methyl alcohol solutions. Some of these may be readily compared with the values in aqueous solution Table L. These values of A^ are expressed in the reciprocal Siemens unit.
TABLE LXVII
A^
IN
METHYL ALCOHOL
398
PHYSICAL CHEMISTRY
Since the value of A^ depends on the ionic conductances, Carrara has calculated these values for a number of the ions, and these are given in Table LXVIII. To compare these values with the values given for aqueous solutions in Table LII, they will have to be converted to mhos.
TABLE LXVIII
EQUIVALENT IONIC
CONDUCTANCE
IN
METHYL ALCOHOL
sequently the conductance
is
399
greater.
In such solvents as
hydrocyanic acid, ammonia, pyridine, and some nitriles, the conductance of solutions of certain electrolytes is much The equivalent congreater than their aqueous solutions. ductance increases with the dilution, but there are a few marked exceptions. In pyridine and benzaldehyde solutions the equivalent conductance of ferric chloride decreases with the dilution. This was also found to be the case in solutions of
HC1
in ether
and
solutions of sulphuric acid
also in isoamyl alcohol, as well as in and in acetic acid the molecular

;
Dutoit conductance decreased with the increased dilution. and Friderich found the conductance of CdI 2 to be practically constant with the change of dilution in acetophenone solutions, and in methly propyl ketone and methyl ethyl ketone the equivalent conductance decreases with the dilution. This is also true of stannous chloride in acetone. Euler found the molecular conductance of both Nal and NaBr in benzonitrile to decrease with the dilution and this is also true of
solutions of silver nitrate in piperidine. Dielectric Constant. It will be recalled that the electrostatic action of
two
electrically
charged bodies varies with
the nature of the

stance which
sulator, is
is
medium
in
which they are placed.
sub-
a very poor conductor, or is, as we say, an inalso called a dielectric. Upon ionization of a solute
in a
rated
nonconducting solvent, the charged ions will be sepaby this medium, and Faraday emphasized that its nature must be taken into consideration. This is always constant for a given medium and is termed the specific inductive capacity and is familiarly known as the Dielectric Constant.
Thomson, and subsequently Nernst, emphasized the relation between the dissociative or ionizing power of a solvent and its dielectric constant. They showed that the
greater the dielectric constant the greater the ionizing power of the solvent, and this is known as the Thomson-Nernst
Rule.
400
PHYSICAL CHEMISTRY
TABLE LXIX
SOLVENT
In Table
401
LXIX will
be found the dielectric constants for a
of types of solvents. It has been found that large in general the Thomson-Nernst rule does hold, and those solvents with the highest dielectric constants yield the best
number
conducting solutions. The conductance of the solution is, however, not commensurate with the dielectric constant, as is shown by an examination of the columns containing the
data of the conductances of a number of solutes in various

solvents.
Some
of the
most conspicuous exceptions to the
rule are given in the Table. In addition to these it may be mentioned that the value for LiCl in water of A^ at 1 8 is 95,
and that at dilution of 3000 liters in propyl alcohol is 1 28.9 in fact, most of the values for propyl alcohol solutions (D.C. 2 1 .6)
;
are greater than those for solutions in water (D.C. 81). The values of A for acetonitrile (D.C. 38.8) solutions approximate
closely those of of A for Nal,
,
NH
many of the solutes in water. The value 4 I, N(C 2 H 5 )4l and of S(C H 5 )I in acetone
2
(D.C. 2 1 .5) according to Carrara, is greater in dilute solutions than the assigned values of A^ in aqueous solutions. In the case of hydrocyanic acid solutions the dielectric constant (95)
indicates that
we should have excellent conducting solutions, but as a matter of fact they are comparatively poor conductors as compared with aqueous solutions. Orthonitrophenol forms solutions that conduct poorly as compared with solutions of the same solute in ammonia. In general, however, ammonia solutions are better conducting solutions than the corresponding aqueous solutions
Nitrobenzene (D.C. 36.5) yields poor the conductivity of which is not at all conducting solutions, commensurate with the magnitude of its dielectric constant. The increase in the conductance with the increased tem.
perature holds generally, as in the case of aqueous solutions,
but there are a few marked exceptions.

of of
The conductance
same over the range in acetone the temand from o.2to37.2C., temperature
CdI 2
in acetonitrile is practically the
perature coefficient
is
virtually zero.
402
PHYSICAL CHEMISTRY
Dutoit and Friderich from the
Association Constant.
result of their extensive researches
on nonaqueous solutions
concluded that only in associated liquids are the electrolytes dissociated, and the more highly the solvent is associated the
its
greater is its ionizing power and consequently the better do solutions conduct the electric current. In Table LXIX are
given the association constants of a number of solvents, and while in general the solvents that yield the best conducting solutions are polymerized, the reverse is not true, for many solvents that are not supposed to consist of associated molecules do yield solutions that conduct the electric current. For example, water, the alcohols, the nitriles, and the ketones are the most highly associated liquids, and they are the
solvents that yield the best conducting solutions. The aldehydes, nitrobenzene, benzonitrile, and the esters are not polymerized liquids, but they yield solutions that conduct the elec-
and many of them are fairly good conductors. Crompton emphasized the connection between the specific inductive capacity and the degree of association of the solvents, and Abegg also pointed out this parallelism, but he also observes that nitrobenzene, ethyl nitrite, and benzotric current,
have rather high dielectric constants yet their " association factors are unity. It is Crompton states almost impossible to doubt that association plays an all-important part in determining the value of the specific inductive
nitrile all
; :
capacity of a liquid and that if there is any connection between the specific inductive capacity and the power of forming electrolytes, it may be looked for rather in the fact that electrolytes are solutions of approximately monomolecular
an associated solvent rather than in there being any peculiar dissociative power attached to the solvent." Numerous freezing point and Colligative Properties. boiling point determinations of nonaqueous solutions have been recorded, but the data on vapor pressure and osmotic pressure measurements are rather meager.
salts in
' '
403
The degree of dissociation as calculated from boiling point determinations shows closer agreement with the values by the
conductivity method in methyl alcohol solutions than in the In Table are given case of other alcoholic solutions. the comparative values of the degree oT dissociation as calcu-
LXX
lated from the boiling point determinations of Woelfer the conductivity measurements of Vollmer.
and
TABLE
LXX
404
salts of the
PHYSICAL CHEMISTRY
heavy metals
in pyridine.
The average
;
of the
,
values for
AgNO
and
216.68, theory, for Pb(NO 3 )2, 352.07, theory requires 330.35.

,
for Hg(CN) 2 165.4, theory, 169.55 for HgI 2 308.0, theory, 452.88; 251.76;
3
is
In most
cases he found values slightly under the theoretical. From these data it is apparent that there is not that agreement between the degree of dissociation as calculated from
the boiling point or the cryoscopic determinations and from the conductivity measurements in nonaqueous solutions as has been found to hold in aqueous solutions, and this has
been confirmed by numerous investigators. We have already seen how well Ostwald's Dilution Law. this Dilution Law of Ostwald holds in the case of aqueous solutions, and many attempts have been made to apply it to
nonaqueous
solutions.
Most
investigators, including Voll-
mer, Woelfer, Cattaneo, and others, have found that Ostwald's Dilution Law does not hold for methyl and ethyl alcoholic solutions. Cohen, who has considered this subject
at considerable length, comes to the
same conclusion.
The
Table LXXI show that the formulae of of Ostwald do not hold when applied to and Rudolphi The following data for a solution of alcoholic solutions. potassium acetate are taken from Cohen's results.
data
given in
TABLE LXXI
V
NONAQUECUS SOLUTIONS
405
the calculation of these constants, and we have seen that the data for this are very meager, and not sufficiently exact,
in
most cases, to justify its use in this connection, and particularly is this true in those cases where the conductance decreases with the dilution.
Mixtures
of Solvents.
Within recent years the problem
of the conductance of electrolytes in mixtures of two different solvents has been the subject of numerous investigations. It is beyond our purpose to discuss this work in detail, but a
few illustrations of the data collected will indicate some of the

peculiarities of these solutions.
In Table
LXXII
are given the molecular conductances of

;
certain salts in aqueous solutions, A in methyl alcoholic soluand in 50 per cent solutions of methyl alcohol and tions,
These values are taken from the work of êlinsky and Kraprivin, and expressed in the reciprocal Siemens unit.
water, C.
TABLE LXXII
406
PHYSICAL CHEMISTRY
values are found in solutions of other salts in mix-
maximum
tures of solvents, as illustrated in the case of lithium nitrate in mixtures of acetone and methyl alcohol and of silver nitrate
in mixtures of ethyl alcohol and acetone, particularly at the higher dilutions. There seems to be some parallelism between these maximum values and the minimum viscosity of
the mixtures.
Carrara has shown that the electrolytic dissociation of water in methyl alcohol is greater than in aqueous solutions,
while the reverse
is
the case in ethyl alcohol.
It is also of
interest to note that
KOH and NaOH in methyl alcohol show the same conductance as CH OK and CH ONa.
3
Additional Theories.
From
a consideration of the opti-
cal properties of solvents, Bruhl comes to the conclusion that oxygen, is generally tetravalent. He attributes the polymerization of the molecules of water and of other oxygenated
liquids, their
high specific inductive capacity, as well as the
power exerted upon the dissolved substance, to It is true that a great their being unsaturated compounds. many oxygenated solvents do yield solutions that conduct but it has been pointed out by Dutoit and electricity; Friderich that the ethers and the ether salts are not polymerized solvents, and that they yield solutions that do not conduct, or the conductance of which is very slight, as in the
dissociative
case of ferric chloride solutions in phenyl-methyl ether. Ethyl carbonate does not yield solutions that conduct. The
same is true bon content

slight.
for chloral solutions, and the esters of high caryield solutions the conductance of which is very In the case of the substitution of chlorine for the
ethoxy group in ethyl carbonate, the number of spare valences is undoubtedly reduced, yet this product, ethyl chlorcarbonate, yields solutions that conduct well. In compounds containing nitrogen, Bruhl holds that the conductance of their solutions is due to the extra valences of
the nitrogen.
He
predicts that hydrazine will prove to yield
407
solutions that conduct, but phenylhydrazine does not yield solutions of the salts tested that conduct electricity; how-
He ever, it still remains to be seen what hydrazine will do. states that, in general, the dissociative power in the case
compounds will vary with the nitrogen content, without being proportional to it, however just as he claims that it varies with the oxygen content of oxygen compounds. He further predicts that the anhydrous hydrocyanic acid,
of nitrogen
;
diazo compounds, and even unsaturated compounds of the elements other than oxygen, namely, PC1 3 AsCl 3 mercaptans, and sulphur ethers, will possess dissociation power. Attention has been called to the fact that when the CN group
, ,
is
substituted for hydrogen in ethyl acetate, the equivalent conductance is materially increased. Hydrocyanic acid and nitriles do yield solutions that conduct very well. Contrary to Bruhl's prediction, PC1 3 does not yield solutions that
but in the case of AsCl 3 his prediction is confirmed. solutions of cuprous chloride in methyl sulphide conduct very poorly. From the evidence we have at present it seems that the theory that the dissociative power of solvents is due to the unsaturated valences, that is, that the only solvents that yield solutions that conduct electricity are unsaturated compounds, is not substantiated by the facts
conduct
;
Werner found that
in
many
is
cases.
Therefore the theory as promulgated by
Bruhl
untenable.
It is quite noticeable that a large number of the investigators of the properties of nonaqueous solutions express the thought that there is manifested considerable influence be-
This factor of the influence of the solvent upon the dissolved substance and in the is one that is no doubt of very great importance development of the electrolytic dissociation theory (which is based upon the behavior of aqueous solutions) the action of the solvent upon the dissolved substance has been entirely
tween the dissolved substance and the solvent.
neglected.
408
PHYSICAL CHEMISTRY
Fitzpatrick concludes from his investigation on the conductivity of alcoholic solutions that the action of the solvent upon
the dissolved substance
is
a chemical one.
He
conceives the
dissolved salt as decomposing and forming molecular groups in the solvent. Owing to the large excess of the solvent there
will
be a continual decomposition and recombination of these molecular groups. He cautions one against regarding the solvent as a medium in which the salt particles are suspended or as a dissociating agent. Wildermann, on the other hand,
one the electrolytic recognizes two kinds of dissociation dissociation of the dissolved substance, and the other, the
ones.
dissociation of the larger molecular aggregates into smaller For example, in a solution of KC1 in water the follow:
+ 2 C1, 2 C1 2 KC1, ing aggregates are assumed to exist + and Cl~. He further maintains that solutions KC1~ 2
, ,
of all substances,
whatever the solvent or concentration,
undergo electrolytic dissociation. Cattaneo was impressed with the fact that the molecular
conductivity
is
greatly influenced
by the nature of the solvent

sol-
employed.
He was not able, however, to point out any direct

between the various properties of the
solutions
yield
relation existing
vents .which
that
conduct.
Konovaloff,
sol-
from
his
work on the amines, concludes that only those
vents that react chemically with the dissolved substance It is true that there are many yield solutions that conduct.
solvents of this nature which do react with the dissolved substance,
and yet which do not
'yield solutions that
electricity.
Picric acid reacts with benzene,
ing solution does not conduct electricity. combination of the dissolved substance with the solvent
conduct but the resultHence chemical
may
take place and yet the solutions need not necessarily conduct. Werner has isolated and analyzed a large number of products of pyridine and piperidine, among those of other organic solvents, with salts of the
heavy metals.
From
the boiling
point determinations, the molecular weights of these salts
seem to be very
solvent.
tallize
409
This
is
slightly influenced by their union with the analogous to the fact that salts which crys-
from an aqueous solution with water
of crystallization
yield the same molecular weights whether dissolved in the anhydrous form or with their water of crystallization.
Carrara thinks that the union of solvent and dissolved substance accounts for the slight conductivity in certain cases. The low values for A in the case of acetone solutions of HC1
and LiCl he attributes to this fact. It has been pointed out by Ciamician that the
power
of a solvent
dissociative
structure.
That
is,
depends principally upon its chemical compounds of the same chemical type,
for example, of the

well.
HOH
type, yield solutions that conduct
This is true in the case of alcoholic solutions, which are not the only class of compounds that possess dissociative power, as has already been pointed out. In general, however, if one member of a particular type of compounds (e.g. nitriles) yields solutions that conduct, it has been found that and if a member other members also possess this property
;
of
some other type
(e.g.
hydrocarbons),
is
found not to yield

possess dis-
solutions that conduct, other sociative power.
members do not
The data
relation
collected are as yet insufficient to
show what the
between solvent and dissolved substance must be in order to yield solutions that conduct electricity. Enough facts have been presented, however, to make it apparent that any theory that aims to explain the electrical conductivity
of solutions in general fluence of the solvent
must take
into consideration the in-
upon the dissolved substance. This is interest for closely connected with it with subject replete is the true cause of the solubility of substances.
;
CHAPTER XXXIV
THERMOCHEMISTRY
IN the consideration of the various chemical reactions no account is usually taken of the energy changes accompanying them. But it is fully recognized now that the thermal change which results from the reaction may so modify the temperature of the system that the best results are not obtainable and
it is necessary to control the temperature very is only over a small range of temperature, relaas it carefully, In a few that the particular reaction takes place best. tively,
consequently
special industrial applications only is the energy manifest in the thermal changes considered of sufficient importance to
be
utilized.
In the combustion of
fuel,
which
is
a chemical
reaction consisting of the union of oxygen and the constituents of the fuel, the reaction is carried on for the sole purpose of
obtaining the energy in the form of heat. The study of the heat energy changes associated with and accompanying
chemical reactions and changes constitute what

Thermochemistry.
is
termed
amount of thermochemical data has been obbut most of this was collected some time ago when the tained, field of chemical reactions was confined to a comparatively small range of temperature being only a few hundred
large
degrees above ordinary room temperature. By the use of such appliances as the electric furnace the temperature range for chemical reactions has been so extended that entirely new conditions have been provided which have resulted in the production of entirely new types of chemical reactions. The
410
THERMOCHEMISTRY
41 1
thermal energy changes accompanying these reactions are entirely different from those of the analogous reactions under ordinary conditions, and the thermochemical data available for these are not applicable to the new conditions, nor are the
data for these new reactions under the new conditions availRichards 1 states that the available thermochemical able. " data enable us to figure out easily the energy of a chemical
reaction beginning and ending at ordinary temperatures, when the heats of formation of all the substances concerned
They give us no exact information at all about the energy of the chemical reaction at temare contained in the tables.
peratures other than the ordinary room temperature. larger part of metallurgical reactions are carried on at tem.
. .
up to 3000 C. in But, for any temperature above the ordinary, the thermochemical data are not exact, and the energy involved in the reaction is different from what it is beginning
electric furnaces.
peratures above the ordinary, running
and ending
at
room temperature."
Units of Thermochemistry. The amount of heat is measured in a number of different units. Those employed in technical work differ from those used in scientific investiThe unit most extensively used is the i5-calorie. gations. which is the amount of heat required to raise one gram of
On page C., the mean temperature being 15 C. 91 we saw that the specific heat of water is different at different temperatures, and so the value of the calorie varies with the temperature taken.
water
i
The
Bureau
"
of
Standards
employs
the
20-calorie.
In view of the greater convenience of 20 Affirming that, as a working temperature, smaller rate of variation in the
heat capacity of water at this temperature, and the fact that calorimetric observations are commonly made at
temperatures near this, it appears desirable to follow what seems to be a growing tendency among experimenters and
1
J.
W.
Richards, /.
/.
E.
C., 9,
1056 (1916).
f
412
PHYSICAL CHEMISTRY
this
adopt the 20 as the basis for expressing the results of
investigation." " Although the calorie has been adopted as the primary unit
of heat, the extreme precision with which electrical measurements can be made has led to the use of the joule expressed in electrical units, as a calorimetric unit. Such use involves
to the calorie,
the acceptance of a specific value for the ratio / of the joule when results are to be expressed in calories.
of such secondary units
is
The adoption
hardly justifiable
.
. .
unless greater comparative accuracy can be obtained thereby. Investigation seems to show that this is not true
;
therefore, the calorie should be adopted for work of this kind and the incidental value of J (one 20 cal = 4.181
. . .
joules) will serve as
an excellent check on the other measure:
ments.
."
The
following heat units are employed

(cal.)
is
The Gram Calorie
The
15
calorie
at the
mean temperature
calorie
is
the heat required to raise one of 15 C. or 60 F.

of
gram gram
of
water
The 20
the heat required to raise one
of water
one
degree at the
mean temperature
20.
The mean calorie is one one-hundredth of the heat required to raise one gram of water from o to 100 C. This is practically the same
as the 15
calorie.
;
The Kilogram Calorie
i.e. the (Cal.) is 1000 times the gram calorie heat required to raise one kilogram of water one degree. The Ostwald Calorie (K) is the heat required to raise one gram of water from o to 1 00 C. and is also termed the average calorie. This is practically 100 times the value of the 15 calorie. The Pound Calorie (pound cal. or Calb.) is the heat required to raise the temperature of one pound of water i C. The British Thermal Unit (b. t. u.) is the amount of heat required to raise the temperature of one pound of water i F., from 60 to 61 F. The Evaporation Unit is the amount of heat required to convert one
pound of water at 212 F. into steam at the same temperature, at normal atmospheric pressure.
1
Bull. Vol.
u,
220 (1915).
THERMOCHEMISTRY
The
relation
413
between the various heat units

:
may
be ex-
pressed as follows
b.
t.
u.
Evaporation Unit
15
cal.
= =
252 967
cal.
b. t. u.
20 cal. watt hour
=4.186 =4.181
joules (or 4.2)

joules (Beau. Stan.)
0.86 Cal.
as the
The specific heat capacity, C, is defined Specific Heats. amount of heat required to raise one gram of the sub-
stance one degree. This amount will of course depend upon the temperature of the substance as well as upon its physical
state, for the capacity for
heat of a body varies with these
factors.
necessary to designate both. The atomic heat of an element is the specific heat multiplied by the atomic weight. Dulong and Petit stated (1819)
it is
Hence
that this value
is
a constant quantity,
i.e.
the capacity of
atoms
for heat is practically the This is Dulong and Petit 's Law.
and 7 upon the accurate determinations

varies between 6
same for all solid elements. The value of the constant with an average of 6.4. It was chiefly
of
Regnault of the
specific
heats of the metals at ranges of temperatures from 10 to 100 that this generalization was based and consequently there
were
many marked exceptions. The most pronounced exceptions are carbon, silicon, and boron. By using the specific heats of these elements at higher temperatures, the atomic heat approaches more nearly that of the constant 6.4.
The
.
following values
Al
5.4
show the most marked variations

B
2.8
Element Atomic heat
Be
3.7
C
1.8
Si
P
5.9
S
5.7
4.5
The
variation from the constant becomes less
marked
if
the specific heat at higher temperatures is employed. The values given in Table LXXIII illustrate the change of the
specific
heat with the temperature.
414
PHYSICAL CHEMISTRY
TABLE LXXIII
ALUMINIUM
THERMOCHEMISTRY
415
the specific heat of an element, its atomic weight may be In the formulation of this law Dulong and Petit calculated. the accepted value of the atomic weight of a number changed
For example, two thirds of the twice the value bismuth was selected and of cobalt the value times half one one and selected new values These silver. of the value found subsequently to be the true ones.
of the elements.
value for
original of lead
;
one half were all
a marked difference in the specific heat of a substance, depending upon the physical state in which it exists. This is illustrated in the case of water by the following data
There
is
PHASE
41 6
PHYSICAL CHEMISTRY
the
In the case of alloys, the specific heat is almost exactly sum of the specific heats of the constituents, and this
applies to mixtures in general, as well as to compounds. The specific heat of water varies with the temperature,
and this is shown by the values given in Table X. For most liquids the specific heat increases with an increase in the temperature, but mercury is an exception. The specific
heat of twenty-seven esters of the aliphatic series can be represented by a linear equation, but other series do not
The specific heat of gases has give as good an agreement. been considered in Chapter IX. Heats of Reactions. The heat capacity of a substance varies with its state of aggregation hence, it is necessary to designate the phase in which the material under discussion exists. So, in writing equations representing thermochemical
;
reactions, different
different phases
liquid,
;
the following
methods are employed to distinguish the is the usual form solid [HÔ],
:
and vapor or gas (H 2 O). In ascertaining the thermal change accompanying a chemical reaction it is not only necessary to know the phase in which the reacting substances exist, but also whether there is a change from one
2
H O,
phase to another, whether the substances reacting are in solution,
and
if
so
what the solvent
is,
and
also the concentration
of the solution.
The eat of Reaction is defined as the number of calories of heat absorbed or evolved by the reaction of stoichiometrical quantities of the substances that are represented
by the
chemical
equation.
When
the
formation of a substance,
it is
represents the termed the heat of formation;

reaction
is
when
the combustion of a substance
represented,
it is
termed the heat of combustion ; when the process of neutralization is represented, it is termed the heat of neutralization. Similarly we have the heat of solution, heqt of dilution, heat of precipitation, heat of ionization; and when there is a change of state involved, we have heat of fusion and heat of vaporization.
THERMOCHEMISTRY
The
is
417
reaction representing the formation of ferrous oxide expressed by the equation

[Fe]
(O)
[FeO]
65,700
cal.
which shows that during the formation of one mole of ferrous In the oxide there are 65,700 calories of heat liberated.
reaction representing the decomposition of ferrous oxide there would be absorbed this same quantity of heat in order
This illustrates what is to obtain the original conditions. sometimes called the First Law of Thermochemistry, which was first stated by Lavoisier and Laplace in 1780. This may
The amount of heat required to debe expressed as follows a into its elements is equal to the heat evolved compose compound to the elements combine when form the compound. known that It is well many compounds cannot be formed from the elements, and so the heat of formation directly cannot always be obtained by direct means. In 1840 Hess discovered the Law of Constant Heat Summation, which is the fundamental law upon which all thermochemical calculations are based. This law is stated as follows The total heat effect of a chemical change depends only on the initial and final stages of the system and is independent of the intermediate The heat of the reacstages through which the system passes. should the same in be tion, then, employing different methods,
:
irrespective of the number of different processes or reactions involved in the production of the particular substance. This
is
illustrated in the formation of
an aqueous solution
of
am-
monium
chloride.
Adding,
Or,
Mixing,
Adding,
= [NH C1] + 42,100 cal. + C1] aq = NH Clqg 3,900 cal. = NH + + (NH (HC1) aq Clog + 38,200 cal. = (NH + aq NH ag + 8,400 cal. + 17,300 cal. (HC1) + aq = HClog NH ag + HClag = NH Cla<? + 12,300 cal. (NH + (HC1) + aq = NH Clo^ + 38,000 cal.
(NH [NH
8)
(HC1)
3)
3)
8)
418
PHYSICAL CHEMISTRY
difference in the heat of formation of
The small
solution of
an aqueous
ammonium
is
chloride
by
the two methods indicates

is
that
it is
immaterial which method

obtained.
employed, for the same
heat value
The term aq signifies that such a quantity of water has been employed that upon further addition of water the heat Hence HClag signifies a of dilution is practically zero. dilute aqueous solution of HC1 such that the further addition or subtraction of water would produce no appreciable heat
effect.
Heat
of Formation.
The heat
of formation of
methane
is
represented by the following equation,

[C]
+ +
(H 2 ) = (CH 4 )
+
-
22,250
cal.
for ethylene
2
by
2
[C]
(H 2 ) = (C 2 H 4 )
1 1, 2
50
cal.
In the formation of methane there
is
an evolution
of heat.
Reactions of this type are designated exothermic, and the compound is termed an exothermic compound. There is a
loss of
heat,
and
heat from the system itself, that is, an evolution of this is the usual type of thermochemical reactions.
is
is an absorption of heat and termed endothermic, while the compound is designated an endothermic compound. The following are endothermic compounds: Acetylene absorbs 54,750 calories of heat in the formation of one mole [CaC2 absorbs 6,259
In the formation of ethylene there
the reaction
absorbs 25,400 cal. Endothermic compounds are comparatively unstable and readily decomposed, sometimes with violence.
cal.;
(AsHa) absorbs 44,200 cal.;
CS2
Heats
of carbon
of
Combustion.
Since the heats of combustion

of great practical importance
compounds are
and
the values are comparatively easily determined, the values are usually employed in calculating the heats of formation
of
compounds.
THERMOCHEMISTRY
419
Depending upon the allotropic modification of carbon employed, different values are obtained for the heat of formation of carbon dioxide, as the following shows
:
[C]
+ [C] graphite + [C] amorphous + [C] amorphous +

diamond
(O 2 ) (O 2 ) (O 2 )
(O)
= (CO 2 ) = (CO 2
)
= (CO2 ) = (CO)
+ 94,300 cal. + 94,800 cal. + 97,200 cal. + 29,160 cal.
(Richards)
The heat
of formation of carbon
monoxide from the com:
bustion of carbon cannot be determined experimentally, but it can be obtained indirectly as follows
[C]
amorphous (CO)
+ +
(O 2 )
(O)
= (CO2 ) = (CO 2 )
+ +
97,200 68,040
cal.
cal.
If
is
the heat of formation of carbon monoxide, according
Law x -f- 68,040 = 97,200. Solving, we have % = or subtracting the second thermochemical equation 29,160, from the first, we have C (CO) (O) = 29,160 cal., or
to Hess'
[C]
(O)
(CO)
-f 29,160 cal.
Many
lar
of the
importance as
is
compounds containing carbon are of particufuels, and the heat obtained by burning
them
the
utilized as a source of heat in

calorific
many
of the industries.
Then, too, the
value of foods which are oxidized in
body in order to maintain its normal temperature is assuming more and more importance in dietary studies, not only for the human race, but particularly in providing balanced rations for animals.
Calorific
Power
of Fuels.
In the combustion of fuels
water
one of the products, furnace is such that the water

is
and the temperature

is
of the
usually uncondensed. So in the calculation of the calorific power of fuels, in order to
obtain the correct heat balance sheet for the furnace, it is necessary to consider the water as vapor, for the condensa-
420
PHYSICAL CHEMISTRY
tion of the vapor would give a large increase in heat due to the latent heat of condensation, and this would result in a loss
which would appear in the waste gases and thus unduly increase the apparent chimney loss. In the calculation of the calorific power of fuels, as in the combustion of other substances, Dulong and Petit 's method That is, the heat value is obtained by assumis employed. ing the carbon all free to burn, the oxygen present combined with hydrogen in the ratio 2 Hz O%, and the excess of hydrogen free to burn. The calorific value of fuel may be determined directly in a calorimeter or may be calculated from the
'.
The maximum temperature attainable depends upon many factors, among which are the conditions under
analysis.
which the fuel is burned, whether the fuel is cold or hot, and whether the air used is cold or has been preheated. It is not possible to preheat many gaseous fuels because they are decomposed and carbon is deposited. Another important factor is the heat radiation of the furnace, which introduces
in this connection the construction of the various furnaces
and
this is particularly the heat conductance of materials of the of one thermochembecoming important departments istry. Particularly is this true of electric furnaces, in which
;
is supplied, not from a but from an and also sometimes parelectrical fuel, source, the from chemical reactions between the substances tially But an as this extended discussubject requires employed. is to such as The reference sion, given special presentations,
the external source of heat energy
Electric Furnace,
by Stansfield, Chapter III. Methane burns according to the following thermochemical

:
equation
(CH 4 )
22,250
+ +
(2
H =
2)
(C0 2 )
97,200
+ +
(2
H 0)
2
58,060
If the water is assumed to be in the form of vapor, its heat of formation is 2 X 58,060 cal., and the heat of formation of
THERMOCHEMISTRY
42 1
carbon dioxide from amorphous carbon is 97,200 cal., which would give as the total heat liberated in the formation of two formula weights of water and one formula weight of carbon But a part of this will be required dioxide, 213,320 calories. to decompose the methane, and this quantity will be equivalent to the heat of formation of methane, which has been found to be 22,250 cal. Then the difference, 191,070 cal., is the heat of combustion of methane, which may also be obtained by adding the numerical values in the above equation. In the case of the combustion of ethylene we have in a
similar
manner the
(C 2 H 4 )
following equation
(0 2 )
=
2
(C0 2 )
97,200
11,250)
+ 2 (H 0) + 2 X 58,060
2
In the formation of ethylene, since it is an endothermic compound, the summation of these heats of formation would be
(
11,250)
97,200
58,060
312,770
cal.
as the heat of combustion of one formula weight of ethylene, assuming that both the products of combustion are gaseous.
If, however, we assume the water vapor to condense, then heat of formation would be 69,000 cal. and we have
its
11,250)
+2X
97,200
69,000
343,650
cal.
are gaseous carbon dioxide
as the heat of combustion of ethylene when the products and liquid water.
For endothermic compounds as illustrated by ethylene, the heat of combustion is greater than the heat obtainable if the amounts of carbon and hydrogen in the compound were burned in the free state while exothermic compounds give less heat than could be obtained by the direct combustion of free carbon and hydrogen equivalent to the formula
;
weight. The heats of formation as well as the heats of combustion

of a few of the
more common compounds are given
in Table
422
PHYSICAL CHEMISTRY
LXXIV. The products of the reaction are assumed to be gases and the water formed to be uncondensed. Most of the data are from Richard's Metallurgical Calculations.
TABLE
LXXIV
SUBSTANCE
THERMOCHEMISTRY
423
reaction
eluded that van't Hoff's formula for calculating heats of But J. W. is not applicable to this class of reactions.
Richards shows from the following calculations that this conclusion is not justifiable. The heat in the products at 960 is
3
Fe
2
56
X
1.)
(0.218
HO =
4(22.22
(0.34
960 39) 960 + .00015
28,560
cal.
X
is
960
2 )
41,300 69,860
cal.
Heat
in the reacting substances at 960
Fe 3 O 4 = 232
4
(0.1447
1.)
960
4(22.22
(0.303
+ 0.0001878 X 960 X 960 + 0.000027 X 960

2
)
= =
72,384
28,075
100,459
cal.
The heat
of reaction at 960
is
therefore the
summation
of the heats of the reactions beginning and ending at zero 38,560 cal. and these heats of the compounds at 960,
which gives
38,650
is
69,860
100,459
~-
7j76i
calories,
which
in better agreement with the value obtained
by Preuner.
following example illustrates the general methods employed in certain types of thermochemical calculations.
The
natural gas was found
by analysis centage composition by volume:
to have the following per-
CH
(i) if
4,
94.16;
2,
1.42;
C2 H
the
4,
0.30;
0.18.
The
0.27; 62,0.32; following solutions are desired

2,
:
00,0.55;
CO
2,
2.80;
H S,
2
What would be
maximum
flame temperature,
of cold air
;
theoretical
amount
(2) if
burned cold with the burned cold, employ4
ing air preheated to iooo? First find the heat of combustion of one cubic meter of
If the molecular weights of the constituents are expressed in kilograms, then the volume will be 22.4 cubic meters, and the molecular heat of combustion the values
the gas.
expressed in Table LXXIV in kilogram calories (Cal.). The heat of combustion of one cubic meter will be this value di-
424
PHYSICAL CHEMISTRY
vided by 22.4. The values employed are for 22.22 as used by Richards and have not been recalculated. We then have the
following for the heats of combustion
:
8,095.2 Cal. 37-1 Cal.
43.4 Cal. 16.8 Cal.

9.9 Cal. 8,203.1 Cal.
The oxygen needed

the air
quantities of the gases
combustion of these respective can be readily calculated and also necessary to supply it. These values are given in the
for the
:
second column of the following table
TABLE
LXXV
THERMOCHEMISTRY
CUBIC METERS
SP.
42 5
HEATS
= N HO =
2 2
7.266
1.9052
CO
SO 2
= =
0.9558 0.0018
X X X X
1
(0.303
(0.34
(0.37
(0.444
X X X X
/
t
t
t 1
+ + + +
=
0.000027 1 ) 0.00015 f)
0.00027 0.00027
I
2 )
Total heat = mined above.
3.2044
0.00074057
?) 8203 Cal. as deter-
we find t = 1806 the temperature of the flame attained when the gas and air employed are cold. Now if the air is preheated to 1000, we have i m. 3 of air
Solving,
2 or the heat 0.000027 X iooo = in i cubic meter of air at 1000 3 30 Cal., and in 9.14 cubic meters of air at 1000 = 3016 Cal. Therefore,
at 1000
0.303
1000
3.2044
+ 0.00074057
2288
have
air
It
8203 3016 Cal., and solving we as the temperature of the flame providing
t
preheated to 1000 is employed. may be readily shown that if air in excess of the theoretical amount required to burn the gas be employed, the heat obtained by the combustion would be required to raise the
temperature of this mass of material, and as a result the maximunl temperature of the flame would be decreased by an amount depending upon the quantity of air used in excess. The combustion of food, which Calorific Value of Foods.
consists of a
mixed
diet, is
as
it is
in a calorimeter.
not exactly the same in the body About 98 per cent of the carbohythat
is,
drates
and 95 per cent
of the fats are digested
absorbed by the body. In the case of these the products of combustion in the body are the same as in the calorimeter but the products of combustion include urea, creatin, uric acid, etc., which are eliminated in this form from the body, hence the proteins are not completely burned as they are
;
in the calorimeter.
Therefore,
it is
evident that the physio-
logical fuel value is smaller
than the heat of combustion. This is apparent from the values of the heat of combustion and the physiological fuel values of a few foods given in Table LXXVI.
426
PHYSICAL CHEMISTRY
TABLE
FOOD
LXXVI
THERMOCHEMISTRY
Heat
of Solution.
427
When
a solute
is
dissolved in water, a
change in temperature is usually obtained. If the quantity of water is just sufficient to produce a saturated solution of the solute, the heat change, or heat tone as it is sometimes
called the integral heat of solution. The heat of is of the opposite sign and is the heat absorbed or evolved when the solute dissolves in a nearly saturated
termed,
is
precipitation
water be added to a saturated aqueous solution, an additional heat effect then if more solvent be added, the change becomes less with the successive additions of solvent until finally no further thermal change is noticed. So if one mole of the solute be added to an indefinitely large volume of solvent, the heat effect of solution is the maximum When a obtainable, and this is termed the heat of solution. solution of a specified concentration is diluted to an infinitely
solution.
If
there will be
large volume, the heat tone of this reaction represents the difference between the heat of solution and the heat tone of the original solution, and this difference is termed the heat oj'dilution, thatis, the heat effect obtained by diluting the solution to that of a solution of infinite dilution.
TABLE LXXVIII
HCl
428
PHYSICAL CHEMISTRY
The heat effects obtained by diluting a solution with successive quantities of water are also designated heats of dilution with specified quantities of water, as the data in Table
show.
is
LXXV
The
many thermochemical tables the heat of solution as the heat tone obtained when one mole of the subgiven
In
is
stance
dissolved in the specified
amount
of solvent.
heats of solution given are the values for the quantity of water designated in each case and the heats of dilution at these dilutions may be obtained by subtracting the value at any
The values given dilution from that of the preceding one given under heats of dilution were obtained in this manner. The combination of water with Heat of Hydration.
many
substances with the production of hydrates is accompanied by a marked thermal change. If these hydrates are then dissolved in water, the heat of solution is much less than when the anhydrous salt is dissolved. In Table LXXIX the
heat of hydration of a few common hydrates is given. The values which are expressed in kilogram calories (Cal.) represent the heat tone when one mole of the solid salt combines with the quantity of liquid water specified, forming the solid
hydrate.
TABLE
SUBSTANCE
LXXIX
THERMOCHEMISTRY
Since the reaction of
429
many substances takes place in soluthe products of the reaction dissolve, and the total heat of reaction includes the heats of solution and is then extion,
pressed as the heat of formation in dilute solution. When dilute aqueous solutions of salts are mixed, there
practically
is
This
is
no heat effect providing a precipitate is not formed. sometimes referred to as the Law of Thermal Neu-
It is explained upon the basis of trality of Salt Solutions. the complete ionization of the salts in dilute solutions, which
results in the
same
state after mixing as before,
and conse-
quently the chemical reaction which is termed double decomposition (metathesis) takes place with no concomitant heat
change. While in the case of such exceptions as noticed in mercury and cadmium salts, which are only partially dissociated, dilution takes place by mixing the solutions, and additional dissociation and reaction, accompanied by a thermal
effect follow.
When precipitation takes place, there is assumed to be a change in the ionic concentration, and the heat effect produced is that of precipitation. The molecular heat of precipitation should be the same by whatever means the precipitation is accomplished in infinitely dilute solutions, i.e. for very slightly soluble substances such as silver chloride. The neutralization of an acid by a base is accompanied by a large heat effect, and upon the ionic basis the equation
representing the reaction would be
H+C1-
+ Na + OH- =
Na+Cl-
+ H 0.
2
This indicates that the only change is the disappearance of the hydrogen and hydroxyl ions with the formation of water which remains in solution. The process of neutralization then consists of the formation of undissociated water, and the heat of neutralization should be the same per mole of water
formed, irrespective of the acids or bases employed. The data in Table illustrates this for strong acids and bases.
LXXX
f
430
PHYSICAL CHEMISTRY
TABLE
LXXX
HEATS OF NEUTRALIZATION
REACTION
THERMOCHEMISTRY
43 1
of
In the neutralization Heat of lonization or Dissociation. weak acids and bases the heat of neutralization is quite different from the normal value of 13.7 Cal., as is illustrated
by the values given
in Table
LXXX.
In the process of
neutralization, as the weak component is not completely dissociated, there must be a gradual dissociation taking place in
order to furnish the ions of water which combine to form the
Accompanying this process of gradual the concomitant heat change due to the Owdissociation, which is termed the heat of dissociation. ing to the low concentration of the hydrogen and hydroxyl
undissociated water.
dissociation there
is
ions, there is
tion.
an incompleteness
this variation of
is
Hence
of the process of neutralizathe total heat effect from
the value 13.7 Cal.
considered as the heat of dissociation.
That is, H D = H N 13.7, in which H D is the heat of dissociation and H N is the heat of neutralization. For example, in the case of HCN, where a is practically zero, this discrep10.8 Cal., while 13.7 Cal. or ancy amounts to 2.9 Cal. = + 2.7 Cal which values are for HF we have 16.1 13.7 designated the heat of dissociation of HCN and HF respecThat is, the quantity of heat, 13.7 Cal., is involved tively. in the process of neutralization on the formation of one gram mole of the water from its ions; then the reverse
,
operation or dissociation of water into its ions involves the absorption of the same quantity of heat. The heat
effect is
13.7 Cal.
The heat
tion
of ionization
may
of the dissociation constants obtained
be calculated from the change from Ostwald's Dilu-
Law Equation
;
for the
ent temperatures
or direct
same concentrations at two differfrom the change in the electri-
cal conductance with the change in the temperature. The heat of ionization is then defined as the heat evolved during
the dissociation of one
gram mole
of the electrolyte.
The
data in Table
these values
LXXXII
and show
give an idea of the magnitude of that ionization usually takes place
432
PHYSICAL CHEMISTRY
with an evolution of heat and refer to the heat evolved in the ionization of substances already in solution.
TABLE LXXXII
SUBSTANCE
CHAPTER XXXV
COLLOID CHEMISTRY
Diffusion.
is
We
are familiar with the fact that
if
one
introduced into the space occupied by another, the gas two species will intermingle and they will soon thoroughly
The mixture will be uniform, and we say that the one diffused throughout the other. If a bottle of perhas gas fume is opened in a room, the odor will soon be distinguished The perfume has diffused throughout the in all parts of it.
mix.
air in the room. Similarly, if sugar is placed in a beaker of water and allowed to stand, the sugar will subsequently be found in all parts of the water. The same is true of other
soluble substances,
and we
say that the
substance
dif-
fuses throughout the water and will eventually occupy all of the space (volume of liquid) allotted to it as the gas occupies the
We
volume in which it is confined. have seen that when gases are brought into contact
with liquids, the amount absorbe'd depends upon the particuThe lar substances selected and also upon the temperature. the volume is also with changes absorption accompanied by
concomitant heat change. When a dry rope is wet with water, there is a marked decrease in volume accompanied by an evolution of heat. This fact is made use of in tightening the ropes of a sail. The water saturates the soil and rocks in a similar manner we say that oil or rock absorbs the
;
water, and this is an important property, making the supply available for plants. How does the water travel through
soil to the plants ? We know that the oil passes " the wick when the up through lamp is lighted," i.e. only when there is a constant removal of the oil from the end
the rocks and
433
*
434
PHYSICAL CHEMISTRY
through combustion. The oil passes through the fiber of the wick by a process termed imbibition, and the passage of the water through rocks is explained by the same process. We have previously called attention to the passage of gases
through
solids,
such as the passage of hydrogen through the
walls of platinum tubes, of carbon monoxide through red-hot iron and through glass and also of the diffusion of carbon
;
into iron, and copper into platinum, as examples of diffusion of solids into solids.
The diffusion of solids through liquids is the most common and has been extensively studied. If CuSO 4 is placed in the bottom of a tall cylinder filled with water, the liquid becomes colored but very slowly, and it may take many days before the solution becomes uniformly colored. If a few crystals of KMnO 4 are placed on the bottom of another cylinder
with water, the liquid is colored throughout quickly, thus showing the 4 diffuses very much more rapidly than does the CuSO 4 That is, different substances have
filled
KMnQ
.
different rates of diffusion.
Work
of
Graham.
Thomas Graham
extensive study of the diffusion of a large
(1861) made an number of acids,
salts, bases, and organic substances, and determined their rates of diffusion. He found that the rate of diffusion is
directly proportional to the concentration. coefficient x is understood in this case the

of the substance that diffuses
By
the diffusion
number of grams upwards per day when the con-
centration at each horizontal layer differs from that one centimeter above by i gram per cubic centimeter.
In Table
LXXXIV are
given the different rates of diffusion
in water of a few substances.

1 On the assumption of Frick's Law that the quantity of salt which diffuses through a given area is proportional to the difference between the concentrations at two areas infinitely near each other, the diffusion constant or specific diffusion
" equal to an amount of the solution which would diffuse across the unit area under a concentration gradient of unity in unit time if the rate were constant during that time (days)."
rate is
COLLOID CHEMISTRY
435
TABLE
SUBSTANCE
LXXXIV
436
PHYSICAL CHEMISTRY
not possess this property, but gelatinized on separating out, and if they crystallized at all it was only after a very long
time.
that these crystalloids diffuse agar, etc.) or membranes of colloidal substances approximately as rapidly as through pure water,
Dialysis.
Graham showed
through
jellies (gelatine,
while by these the colloids are completely prevented from

diffusing.
distinction
to utilize
loids
This led Graham not only to emphasize a marked between these two classes of substances, but also this property as a means of separation of crystalcolloids,
from
of solutions of colloids.
loids, their
thus giving a method for the preparation " Of all the properties of liquid col-
slow diffusion in water and their arrest by colloidal
septa are the most serviceable in distinguishing

crystalloids."
them from
crystalloid
The method
of
separation
by
diffusing the
through a septum of gelatinous matter, Graham termed Dialysis, while to the whole apparatus, which consisted of a glass vessel over one end of which the septum is drawn, or the septum itself in the form of a tube, he gave the name
Dialyzer.
One
of the best
and most extensively used
dialytic
septa
is
parchment paper.
One
illustration of this
method
for the preparation of col-
loidal solutions will suffice.

silica is
Graham
"
says
solution of
obtained by pouring sodium silicate into dilute HC1, the acid being maintained in excess. But in addition to HC1,
salt
such a solution contains NaCl, a
which causes the
silica
to gelatinize when the solution is heated, and otherwise modifies its properties. Now such soluble silica, placed for
twenty-four hours in a dialyzer of parchment paper, to the usual depth of 10 mm., was found to lose in that time 5 per cent of its silicic acid and 86 per cent of its hydrochloric acid.
After four days on the dialyzer, the liquid ceased to be disAll of the chlorine was gone, with no turbed by AgNO 3
.
further loss of silica."
COLLOID CHEMISTRY
437
The preparation of colloid solutions of metals by Bredig's sparking electrode method consists of bringing the ends of the metal electrodes together under the surface of the liquid and then separating them so as to form an arc. By repeatedly touching the electrodes together and separating them a colloid solution of the metal may be formed. Colloid solu-
may also be obtained by employing reducing agents according to the method used by Carey Lea. In our consideration General Character of Colloids.
tions
thus far
substance that
we have denned a pure chemical compound as a is chemically homogeneous. The method
of ascertaining this is by process of analysis, and in the case of many very complex substances it is not a simple matter
to determine whether the constituents present conform to the Law of Definite Proportions. saw in the considera-
We
tion of simple binary systems that by variation of the components we could obtain fusion curves and solubility curves
which would manifest characteristic properties at certain points, from which we conclude the existence of a definite
chemical compound, the evidence being the change of state without change in temperature, i.e. a constant fusion point, or a constant freezing point. As the methods have become
more
cases)
refined the increased accuracy of the
measurements has
revealed additional chemical

.
So by the use of
compounds (hydrates in many new methods we are able to collect
additional information concerning the relationship existing between the components.
In the discussion of binary systems
we met
a type of solu-
tions designated solid solutions. These conform to our usual definition of solutions, which is, a phase in which the relative quantities of the components can vary continuously within
certain limits, or a phase of continuously varying concentra-
while by phase we understand a mass that is chemiand physically homogeneous. So it is evident that the identification of any particular phase depends upon our
tions
cally
;
438
PHYSICAL CHEMISTRY
ability to determine whether it is physically homogeneous also chemically homogeneous, and this, of course, is dependent upon the degree of refinement of our methods.
and
defines a homogeneous system as one in which mechanically separable parts show the same chemical constitution and the same chemical or physical properties.
all of its
Roozeboom
"
Gases and liquids which have been well mixed possess this
homogeneity of constitution because of the smallness of molecules and the grossness of our means of observation." The attempts to determine whether a system is a solution have led to such definitions of a solution as " a homogeneous
as mingling physical mixtures the complexes of different substances in every part physically and chemically homo;
"
"
" a homogeneous phase." geneous," or, as Ostwald states it, The basis of the conception of solution, then, depends not upon the many properties of solutions that we have been
discussing, but upon the question of the homogeneity or heterogeneity of the system, and consequently upon our conception of and our means of determining homogeneity. From the process of diffusion we have seen how the solute
divided and subdivided and thus distributed throughout the whole of the solution. Here it exists in such a fine state of division that we are unable to distinguish any
becomes
of the individual particles
and the mass
(solution) is said to
be homogeneous.
it
If
we take a
solution of colloidal
A1(OH) 3
appears perfectly clear, and from a casual observation looks like a clear solution of any crystalloid yielding a colorless
solution.
The same
is
true of
many
other colloid solutions,
a microscopic examination of which would not reveal the presence of any of the diffused substance in the solution. If, however, a convergent ray of light were permitted to pass through these solutions, it would be possible to follow the ray through the solution in a manner similar to that when a bright ray of light passes into a darkened room through a
small orifice in the curtain.
The boundary
surfaces of the
COLLOID CHEMISTRY
439
made
particles of dust in the air reflect the light, and they are thus but if the strong ray of light visible to the naked eye
;
passing through the solution is examined by a powerful microscope, very small particles can be readily recognized. These are termed ultramicroscopic particles, and an arrange-
ment such
as this,
making use
of the strong ray of light (the
Tyndall effect) and the microscope, was designed by Siedentopf and Zsigmondy and is known as the Ultramicroscope. By use of this method a solution of sodium chloride would appear optically homogeneous, whereas in colloid
solutions there
would be a lack
ceivable that the particles
may
It is conof homogeneity. be of such a size that they
would be recognizable without the aid of the microscope and the Tyndall method would render them visible. We might imagine the particles to be still larger and of such size that they would remain suspended in the liquid only a relatively
short period.
In this latter case of mere suspension, as
it is
case readily designated as heterogeneous, for the boundaries of the components of the system It is therefore conceivable could be readily recognized.
termed,
we would have a
that
we may have
all
degrees of division of matter and thus
produce a continuous gradation of sizes of particles, from the one extreme of suspended particles through those of microscopic and ultramicroscopic size to the still finer ones, which
at present no means of recognizing, on down to the ultimate molecular particles. " We see that, just as other investigators Zsigmondy says
we have
have
said,
when
solutions are spoken of as

it
homogeneous
dis-
tributions, mixtures, etc.,
cannot be meant that they are If such great homoabsolutely homogeneous mixtures. geneity is demanded of solutions that we can detect no inhomogeneity in them by our most sensitive methods, we would thereby exclude altogether from this classification solutions not only of many colloids, but also of numerous crystalloids, for example, fuchsin, ferric chloride, chromic chloride,
440
PHYSICAL CHEMISTRY
and solutions
in the critical state.
saccharose, raffinose,
We
would thus run a

every time
we
'
risk of reducing the sphere of solutions increase the sensitiveness of our methods of
The danger can be easily avoided if we use investigation. in its usual chemical acceptance, solution the word
'
meaning thereby subdivisions which appear clear in ordinary daylight and which cannot be separated into their constituents by the ordinary mechanical means of separation (nitraWo. Ostwald emphasizes, " that tion and decantation)." it is not the presence of many more or less evident particles which may be recognized either macroscopically or microscopIt is ically that distinguishes a colloid from a true solution. rather the intensity of the unbroken light cone passing through the solution which betrays the state of the liquid. It is safe to say that liquids which show no definite Tyndall light cone or show it only in high concentrations are true (molecularPractically all colloid solutions give a disperse) solutions. effect." positive Tyndall
It is generally accepted at the present time that colloid solutions are regarded as heterogeneous two-phase systems,
and that
their particular distinguishing properties are due principally to their very great specific surface, and thus it is
evident that what
we
are considering
is
really a state of matter

colloid state.
and should refer to this condition as the was fully recognized by Graham, for he
loidal
This
col-
states
;
"
:
The
is, dynamical state of matter the crystalloidal the statical condition. The colloid possesses Energies. being It may be looked upon as the probable primary source of the
in fact, a
To the gradforce appearing in the phenomena of vitality. ual manner in which colloidal changes take place (for they
always demand time as an element), may the characteristic protraction of chemico-organic changes also be referred." Various methods of Classification of Colloid Systems. classification of colloid systems have been used, but the This classification of Zsigmondy is now generally employed.
COLLOID CHEMISTRY
is
441
based upon the progressive subdivision of the given phase. Considering the system to consist of two phases, we have one phase being distributed throughout the other phase. The
solvent or continuous phase is termed the disperse means, while the solute is termed the disperse phase, and the entire
system
is
termed a dispersed system or a dispersoid (which synonymous with colloid).

is
face of the
As the subdivision of the disperse phrase increases, the surmass increases enormously. This is illustrated in Table LXXXVI given by Wo. Ostwald.
TABLE
LXXXVI
INCREASE IN THE SURFACE OF A CUBE WITH PROGRESSIVE DECIMAL SUBDIVISION
442
PHYSICAL CHEMISTRY
instead of using the concept, specific surface, this other expression

is is
also used
frequently employed. The degree of dispersion synonymously with the expression colloidality.
Hence we can use the degree of dispersion as our means and since there is a gradual successive subdivision, the colloidality will become gradually more pronounced as the subdivision of the particles increases. As there are no marked breaks or lines of demarcation, our classification must be made arbitrarily, and the basis of this is the relative sizes of the particles and our means of disThere is, however, a gradual transition tinguishing them.
of classification of dispersoids,
of one class into the other.
The following diagrammatic representation according Wo. Ostwald illustrates the classification of dispersoids
:
to
Molecular and supermolecular dispersoids
(Von Weimarn's solutoids) Size of particles of the disperse phase about i or less
Specific surface
>6
io 7
Colloid Solutions
Size of the particles
of
the dis-
DISPERSOIDS
perse phase between o. i A* and i MA* 5 Specific surface between 6- io and
True or coarse dispersions

(suspensions, emulsions) Size of the particles of the disperse
phase greater than

Specific surface
o.i
/*
<
io 5
The particles larger than about o.i /x in diameter which represents the limit of microscopic visibility and which constitute the is taken as the lower limit of dispersion Colloid solutions and Emulsions. comprise the Suspensions i between o.i and in size. particles By the ultra/x/x
//.
COLLOID CHEMISTRY
443
microscope particles smaller than about 6 /A/A have not been recognized, and the lower limit has, therefore, been placed a little beyond the range of vision of our present instruments.
Their degree of dispersion is between 6 io 5 and 6 io 7 Dis7 persoids with a degree of dispersion greater than 6 io are
.
known
as molecular dispersoids, which comprise
Graham's
following illustrate the sizes of some of Crystalloids. the molecular species: Hydrogen gas, 0.067 to 0.159 /A/A;
The
water vapor, 0.113

chloride, 0.26
/A/A;
carbon dioxide, 0.285

/A/A.
/A/A;
sodium
/A/A; sugar, 0.7 Additional Nomenclature.
Owing
to different
methods
of classification of dispersoids a large number of terms appear in the literature, and it is necessary to become familiar with
Depending upon which phases are taken for the dismeans and for the disperse phase, we have as in true perse " solutions nine different combinations and possible solutions."
them.
I.
II.
Liquid as the disperse means when the disperse phase is a (a) Solid, they are termed suspensions. (b) Liquid, they are termed emulsions. (c) Gas, they are termed foams. Gas as the disperse means we have when the disperse phase is smoke (tobacco smoke) condensing vapors of metals (a) Solid
; ;
(ammonium
(b)
(c)
Liquid
cosmic dust, etc. atmospheric fog, clouds, condensations of steam,

chloride, etc.)
;
etc.
Gas
no example known.
;
III.
Solid as the disperse means we have when the disperse phase is known as solid solutions, mixed crystals, carbon (a) Solid
(b)
(c)
Liquid
particles in iron, etc. occlusion of water, inclusion.
Gas
solutions
of
gases
in
solids,
gaseous inclusions in
minerals.
This classification
definition
is
Colloid chemistry is the chemistry of bubbles, drops, grains, films, and filaments." Graham gave the name sols to those dispersoids which we
:
"
then in harmony with Bancroft's
usually designate colloids, the degree of dispersion of which
444
lies
PHYSICAL CHEMISTRY
.
between 6 io 5 and 6 io 7 If the degree of dispersion decreases below the lower limit of colloids, then the system becomes microscopically heterogeneous and the dispersoid is said to exist in the gel condition. There is, therefore, a loss of uniform distribution of the disperse phase throughout the In the case of colloid silicic acid Graham disperse means.
called this solution a sol;
into a jelly-like
mass he applied the term
after the silicic acid precipitated gel to the precipitate.
Various terms are employed to express this change, which results in a decrease in the degree of dispersion, and the disperse
phase
is
said to coagulate, precipitate, gelatinize,
clot, set, etc.
reverse of this process was designated by Graham peptization, and represents the dispersion of the disperse phase throughout the disperse means. If for any dispersoid the
The
degree of dispersion can be increased and also decreased at will, so as to change the state by reversing the conditions
which brought about the change, it is said to be If this cannot be done, it is irreversible.
reversible.
Depending upon the character of the disperse means we have, when water is the disperse means, hydro sols and hydro gels ; with alcohol, ale o sols and ale o gels. In general, when the disperse means is an organic liquid the dispersoid is termed an organosol or an organogel. And to designate
may
if
the substance in the disperse phase a prefix is employed, i.e., gold is the disperse phase and water the disperse means,
then
we have
The
gold-hydrosol, etc. Colloid State. Hundreds of substances
have been
obtained as colloids, and these comprise elements as well as practically all types of chemical compounds and it has been
;
recently emphasized that the possibility of converting a substance into the colloidal state has no relation whatever to the
chemical character of the substance. The conception that the colloid solutions are a special class of disperse systems
leads to the acceptance of the universality of the colloid state. Just as we say that all substances are soluble, so with
COLLOID CHEMISTRY
445
the proper conditions all substances can be sufficiently dispersed in the proper disperse means to have a degree of dispersion sufficient to produce particles of the size we define as
belonging to the division designated colloid solutions. As there are different degrees of solubility, so there is a marked
difference in the ease with
which various substances assume
the colloid state, for it is a state or condition of matter. The study of the colloid state comprises colloid-chemistry, which is
an important division of physical chemistry and is assuming as prominent a place as electrochemistry, thermochemistry, actino-chemistry, and radio-chemistry. Wo. Ostwald states " that, Colloid-chemistry deals with the relations of the surface energies to other kinds of energy as shown in an especially
way in dispersed heterogeneous systems." number of substances are known to exist both as a colloid and as a crystalloid. Sodium chloride, which is usually a known as crystalloid, can be obtained in the colloid form,
characteristic
while albumen, which

crystallized
is
usually classed as a colloid,
may
be
It is conceivable that the disperse
means and the
disperse
phase could have the same chemical composition. In the case of a number of liquids the Tyndall effect is very marked, which shows the existence of a heterogeneous system, i.e. there is a disperse phase present. This has been noticed
in the case of oils, waxes, different varieties of rubber, molten
These are phosphoric acid, arsenious acids, etc. designated isocolloids ; and if the substance appears in allotropic modifications, the colloid system is termed an allosalts,
Sulphur, phosphorus, and selenium are allocolloids. Posnjak states that styrol, C 8 H 8 polymerizes into (C 8 H 8 ) n and becomes a jelly-like mass or glass-like (metastyrol) " If one depending upon the degree of polymerization. adds to pulverized metastyrol an equal weight of styrol, the former gradually absorbs the latter. In the process the originally opaque powder becomes translucent and
colloid.
, ,
446
PHYSICAL CHEMISTRY
gradually changes into a homogeneous, gelatinous or jellyIf less styrol is added to like, viscid, transparent mass.
the metastyrol, say only about a fourth as much of the former as of the latter, a transparent mass results, which is not viscid, but glossy."
Two
8,1,
allotropic liquid modifications of
sulphur, S\
are
recognized, and the
system
is
and designated an
over a certain range of temperature it is assumed that the dispersion of one form throughout the other
allocolloid, for
conforms to a colloid condition. If the substance exists in a number of different physical forms, then it is possible to have a large number of isocolloids. In the case of water, in addition to the vapor and liquid forms, there have been four or more different modifications of solid
There are some sixteen different colloid which have been investigated and described. types and Emulsoids. In the case of two comSuspensoids in which the ponent systems degree of dispersion is such that the disperse phase exists in the colloid state, the sols are termed suspensoids ; if the disperse phase is liquid, the sols are termed emulsoids. These are synonymous with the two classes of sols termed lyophobic and lyophilic colloids. Since the classifications are based upon the degree of dispersion, it is evident that the lyophobic colloids approach on one side
ice
recognized.
suspensions in liquid-solid systems, while the lyophilic colloids approach emulsions in liquid-liquid systems and on the other hand they both approach very closely to the
;
molecular dispersion or the condition of true solutions. In this connection it is interesting to note that under cervice versa;
the transition of liquids to solids and so, too, in the colloid state it is possible for a to phase pass from a solid to a liquid or a liquid to a solid. Under proper conditions certain emulsoids may be made
tain conditions
we have
to precipitate as a solid. We then have the transition of an emulsoid to a suspensoid and the subsequent enlargement
COLLOID CHEMISTRY
of the particles, so that
447
we may eventually have a suspension
with the
final precipitation, or it
may even
coagulate without
assuming the microscopic dimensions. suspensions to emulsions and vice versa
The
is
transition of
known,
a
little
also familiarly as in concentrated alcoholic solutions of rosin to which
water has been added.
These phenomena have led
many to suggest that in the condensation of molecular dispersion we have the formation of droplets, i.e. the liquid phase, which changes to the solid phase and further, that in
;
all
processes of crystallization or separation of the solid phase the liquid phase is first formed as an intermediate
transitional stage. In some cases this transition stage exists for a very short time, while in other cases it exists for an ap-
preciable time
days, in many cases. That certain molecular Crystallization or Vectoriality. condense and disperse phases eventually separate into
crystalline
masses indicates that there
is
a definite molec-
ular arrangement of the molecules in space. The stage of the condensation process at which these vectorial properties
manifest themselves
is
shown
to be while the phase
is still
liquid, as a number of liquids are known to manifest the vectorial properties which characterize them as crystals.
We
have Lehmann's extensive researches in confirmation
of
the vectorial character of liquids. Von Weimarn even believes vectoriality is manifested by gaseous substances and in
addition has presented evidence which he considers to be direct proof of the vectoriality of the colloid phases. In the case of colloid iodine and certain colloid dyes, L. Pelet and
Wild claim to have observed the fusion of ultramicroscopic W. particles which assumed definite crystalline shapes. Ostwald says, " The precipitation of the insoluble from liquids seems always to occur primarily in the form of droplets, that is, in the state of an under-cooled liquid," and Wo. Ostwald concludes, "It," therefore, seems possible theoretically that a
development of crystals
may
take place in that
448
the
'
PHYSICAL CHEMISTRY
'
crystal embryos are at first liquid and only later become solid as they enlarge because of a progressive coalition of
'
'
molecularly dispersed particles."
The degree of dispersion of colloids can be a changed by variety of methods and to such an extent that the disperse phase may become a mere suspension and eventually separate. Then, too, from suspensions and emulsions the disperse phase can be caused to deposit as a solid or liquid phase, and thus resembles the precipitate obtained from colloid solutions. The separated phase may be a granular precipitate, may be flocculent or gelatinous, or the whole mass may set to jelly. Depending upon the particular form assumed, various terms have been loosely applied to the such as coagulation, precipitaphenomenon of separation
Coagulation.
tion, flocculation, gelatinization, setting, etc.
Among a few of the methods by which this phenomenon may be brought about we have change in temperature
:
change in concentration
;
addition of electrolytes If gelatin is dissolved in water and this solution

to cool,
it will
agitation, including centrifuging and addition of non-electrolytes.

is
allowed
adding more water and jelly. becomes the mass again liquid, and we have the warming, the That redissolved. If, is, process is reversible. gelatin
set to
a firm
On
however, a solution of colloid silicic acid is caused to gelatinize, one way to get this again into the form of a colloid solution is to fuse the precipitate with sodium hydroxide, dissolve the mass in water, decompose with acid, place in a dialyzer,
and remove the salt. Colloids of this class are designated Whether a colloid system is reversible or irreirreversible. versible is determined many times by the treatment to which the system is subjected, and Zsigmondy suggests that this
classification
should be confined to the one factor of desicca-
That is, a reversible colloid tion at ordinary temperature. is one which on addition of the original solvent or disperse
means
to the precipitated disperse phase will cause the forma-
COLLOID CHEMISTRY
tion of the original dispersoid system.
449
According to
this,
colloid metals, hydroxides, and sulphides are while irreversible, among the reversible colloids may be listed,
then, most
molybdic acid,
gum
arabic, dextrin,
and most albumens.
Addition of Electrolytes. In general, it may be stated that electrolytes when added to colloid solutions cause the
coagulation of the disperse phase.
The amount
of the elec-
trolyte required to produce precipitation in the case of irreversible colloids is usually very small, while it is necessary
to
add
large quantities to the reversible colloids, as they are
not so sensitive.
concentration of 24 per cent of ammonium sulphate is required, according to Kauder, before any precipitation of
globulins begins,
precipitation.
and 36 per cent is necessary for complete This method of salting out is employed in
separating many organic colloids, particularly the emulsoids such as albumens, etc. A 35 per cent solution of ammonium
sulphate when added to blood serum separates the globulins, but a concentration of 70-80 per cent is necessary for the preThe kind of salt employed has cipitation of the albumens. a marked effect, and it has been shown that the precipitation
albumen increases for the cations in the order NH 4 K, Na, Li, and for the anions in the order CNS, I, Br, NO 3 Cl, C 2 H 3 O 2 and SO 4 It has been shown by Linder and Picton that minute quantities of electrolytes cause the coagulation of most irreversible inorganic colloids, and this has been confirmed by numerous workers. Benton gives the following classification of colloid solutions and suspensions
of pure
,
.
I.
Anionic, solutions in water in which the particles anode, i.e. are negatively charged
:
move toward
the
1.
The
2. 3.
4.
5.
sulphides of arsenic, antimony, and Solutions of platinum, silver, and gold.
cadmium.
Vanadium
pentoxide. Stannic acid and silicic acid.
Aniline blue, indigo, molybdena blue.
450
6.
7.
PHYSICAL CHEMISTRY
Iodine, sulphur, shellac, rosin.
II.
Starch, mastic, caramel, lecithin. Cationic, solutions in water in which particles cathode, i.e. are positively charged
:
move toward
the
1.
The hydrates
of iron,
chromium, aluminium, copper, zirconium,
cerium, and thorium.

2. 3.
Bredig solutions of bismuth, lead, iron, copper, and mercury. Hoffmann violet, Magdala red, methyl violet, rosaniline hydrochloride, and Bismarck brown.
4.
Albumen, haemoglobin, and agar.
From the fact that the particles of the disperse phase may be either positively or negatively charged Hardy formulated a general statement, which is also known as the LinderThe most active Picton-Hardy Law, expressed as follows
:
precipitants are those ions carrying a charge of opposite sign The to that carried by the particles of the disperse phase. precipitating power also increases greatly with tne valency
of the ion.
The
coagulative power of electrolytes, that
is,
the recipro-
necessary to coagulate a given solution, increases greatly with the valency of the ion. Whetham points out that in order to produce coagulaliter
cal of the concentration in
moles per
minimum electrostatic charge has to be brought into contact with the particle constituting the disperse phase. Through the velocity of these particles the
tion of a sol a certain
number
As of collisions results in the union of the charges. these charges are proportional to the valency of the ions and their number proportional to the conductance of the solution, the coagulative power of the electrolyte, as Linder and Picton showed, depends upon the electrical conductance of the solution. An equal number of electrical charges would be obtained from two trivalent ions, from three divalent ions, and from six monovalent ions. Burton determined the velocity under electrical pressure
of the positively charged copper of a copper colloid solution and the effect on the same when solutions of electrolytes of
COLLOID CHEMISTRY
different concentrations
451
of his results
were added.
Some
are given in Table
LXXXVII.
TABLE LXXXVII
SOLUTION
452
PHYSICAL CHEMISTRY
Cataphoresis and Endosmose.

suspensions, emulsions, and
We have
seen that
when
colloid solutions are subjected to electrical pressure, the disperse phase wanders to one of the
poles,
which shows that these particles possess an

This phenomenon
is
electric
charge.
known
as cataphoresis
and
is
the reverse of endosmose, which denotes the passage of the liquid along the walls of the tube under electrical pressure.
We could imagine the particles of the disperse phase to be so

numerous as to form
of microscopic size.
practically a continuous cellular structure such as in the fine unglazed china where the tubes are
The disperse phase would then be stabe the disperse means, when the considered and might tionary then become the would disperse phase and would liquid move under the electrical pressure to which it would be
subjected. Effect of
well
The effect of the medium may be Medium. shown by a few typical examples. In acid solution alis
bumen
is
positively charged, while in neutral solutions there
practically
no motion under the
electrical pressure
and
if
the solution
Platinum
alkaline, the particles are negatively charged. in chloroform was found by Billitzer to be posiis
The additively charged and in water negatively charged. tion of certain electrolytes to metallic hydrosols even
changes the sign of the charge carried by the particles in
solution.
Benton prepared Bredig solutions of lead, tin, and zinc which all were positively charged, while bromine was negatively charged in the same solvent. In
in alcohol, in
methyl alcohol Bredig solutions of lead, bismuth, iron, copper, tin, and zinc were found to be positively charged, while in ethyl malonate solutions platinum, silver, and gold were
negatively charged. In aqueous solutions of starch, gelatin, agar, and silicic acid the charges on the particles could hardly
be detected, as there was such a
slight
movement
of
them
when subjected
to electrical pressure.
COLLOID CHEMISTRY
Adsorption.
trolytes
it is
453
In the precipitation of colloids by elecfound in many cases that the electrolyte also
appears with the precipitated colloid. By the process of washing, it cannot be removed from the gel. We say that the electrolyte has been adsorbed. When a colloidal solution of arsenious sulphide is coagulated by BaCl2, it is found that there is considerable barium present in the gel, while the
concentration of the chlorine in the solution remains constant.

It
has further been shown that the quantities of
dif-
ferent metals which are adsorbed
are in the
alents.
same ratio to one These adsorbed metallic constituents cannot be removed by washing but can be removed by displacement with other elements and in equivalent quantities. This is, however, a mass action phenomenon, for the process of substitution may be reversed by changing the relative masses Linder and Picton found that of the reacting substances. when calcium chloride was employed, the calcium adsorbed by the gel could be replaced by cobalt and if a salt of cobalt was employed as the coagulant, the cobalt adsorbed by the gel could be replaced by calcium. From such experiments as these it has been concluded that
;
by any particular colloid another as their chemical equiv-
chemical reactions take place and the resulting precipitate is a true chemical compound. In the case of many substances whose degree of. dispersion is less than that of the disperse phase in colloid solutions, wherein we have mere suspension, suspensions such as clay manifest the same phenomenon. While in the case of many precipitates in analytic work we have the electrolyte adsorbed by the precipitate, as in the case of precipitation of BaSO 4 which adsorbs BaCl2 readily, and in the precipitation of zinc and of manganese with the
,
members
of the preceding group, as well as in
numerous other
examples wherein the precipitates are washed free from impurities with difficulty. When two colloids of opposite signs electrically are mixed, the gel resulting will be a mixture
f
454
PHYSICAL CHEMISTRY
of the two, the composition depending
upon the
original
relative concentration of the colloid solutions.

ple,
when a
colloidal solution of ferric
For examhydroxide, which is
electrically positive, is
mixed with a
colloid solution of arse-
nious sulphide, which is electrically negative, the resulting gel is a mixture of the two, and by varying the original concentration of the colloid solutions gels of continuously varying
composition can be obtained, and when the electrical charges are just neutralized complete precipitation takes place. Some investigators, including van Bemmelen, even go so far as to consider many of the gelatinous precipitates, such as
the hydroxides of iron, aluminium, etc., as oxides of the metals which have absorbed water, i.e. they are adsorption compounds. Many other substances which have been considered as true chemical compounds are now held to be ad-
For example, purple of Cassius (formally termed aurous stannous stannate) is considered by Zsigmondy to be an adsorption compound of colloidal gold and
sorption products.
colloidal stannic acid.
From the foregoing we have seen that these adsorption compounds have been considered as true chemical compounds, and it is evident that we may also be dealing with
but the tendency at present is to consider these products as the result of surface-tension phenomena, and they are designated as surface-tension condensation
solid solutions
;
products.
Adsorption by charcoal
is
very pronounced and
is
com-
monly known
of sirups
in its use for the removal of the last traces of
gases in the production of a high vacuum, for the purification and numerous other liquids by the removal of the
coloring matter, as well as for the adsorption of metals from all of which constitute many imtheir aqueous solutions
portant technical processes. In the case of vapors of iodine, the amount adsorbed is proportional to the vapor pressure,
and a
final state of equilibrium results.
COLLOID CHEMISTRY
455
The amount
of solute
adsorbed
is
face of the adsorbent and

i
proportional to the surexpressed by the following

is
equation
adsorbed,
m m the
a c n in
,
which %
is
the weight of the substance

c
weight of the adsorbent,
the volume con-
and - are constants. This n has been confirmed by Walker and Appleyard, who obtained for the adsorption of picric acid from a o.oi N solution in water and in alcohol by charcoal and by silk
centration after adsorption, a
:
^(charcoal) ~
water
alcohol
5-2
7-3
(silk)
For any substance the adsorption is proportional to the specific surface, which is closely related to the amount of chemical change. Since all surface energies and volume energies are interrelated, electrical energy, which is a surface energy, and surface phenomena, such as adsorption, must be
related.
It is assumed that at the boundary surface, solution-solid, in these heterogeneous systems there is a surface concentration
from that within the solution, and that the greater the extension of the solid surface, i.e. of the disperse phase, the From extensive greater becomes the concentration on it.
different
experimental evidence Lagergren has shown, by the application of Le Chatelier's theorem, that depending upon the
change in solubility of the solute with change of pressure we may have either positive or negative adsorption, and from this experimental evidence it is concluded that the surface layer is in a state of high compression, which is due to the action of the cohesive forces. The heat evolved when insoluble powders are wetted would be due then to compression of the adsorbed solvent.
456
PHYSICAL CHEMISTRY
surface of substances does not consist of the
The absolute
external surface only, for all solids are more or less porous and therefore contain numerous capillary tubes which give the
mass a
cellular structure, increase greatly the absolute surface as well as the specific surface, and likewise the adsorbing power of the adsorbent. So this cellular or honeycomb struc-
is
which is attributed by some authors to gels in general, assumed for all very finely divided substances as well. This is manifest particularly in the case of charcoal, which adsorbs metals from aqueous solutions, and in many cases the metal is completely removed, the solution becoming strongly acid while the adsorbed metal cannot be washed out from the charcoal. Not only is this phenomenon assumed to be one of adsorption, but even the formation (precipitation) of metals from metal ions need not be considered primarily a chemical reaction, but is explained upon the basis of the
ture,
also
highly porous character of the substances, such as charcoal. In contact with water, the adsorbent becomes negatively 1 and the water positively charged, and a metal charged ion in attempting to diffuse into the body of the charcoal will pass into the capillary opening and may have its electrical charge neutralized
by the negative charge
of the charcoal
is
and be deposited
as the metal.
This explanation
also given
for the deposition of metals in very fine cracks in glass. The adsorption of dyes by filter paper is explained in a
manner, the fiber is negatively charged while the positive, and a positive sol will neutralize the charge on the paper, will become neutral, and be precipitated on the fiber. Similarly, a negative dye would not be precipitated, thus giving a method of separating and distinguishing them. The same is true of gels which are themselves strongly posisimilar
water
is
Perrin has
shown that
for
many
cases this
is
not true.
Coehn
states that the
substance with the higher dielectric constant is positive against the substance with a lower value for constant. Hence, as water has nearly the highest value known
(81) all other substances
would be electronegative toward water.
Also see Briggs,
Jour. Phys. Chem., 21, 198 (1917).
COLLOID CHEMISTRY
457
is
tive or strongly negative, and their strong adsorptive power attributed to this. The adsorption results in the concomi-
tant decomposition of the adsorbed salts. We will not take up Gibbs' consideration wherein he has
shown thermodynamically that
if
a dissolved substance had
the property of lowering the surface tension of the solution, the substance would exist at a higher concentration in the
lose sight of the fact that while
Nor must we surface layer than in the bulk of the solution. many of these attempted explanations are purely physical, it is possible to apply the Distribution
Law
to
them and show that the phenomenon
is
of
the nature of solution, and giving rise in other cases to the
many
so-called solid solution theory of dyeing. Then, too, in of these purely physical theories we find no factors
of the dyes, a fact which emphasizes the chemical reaction between the dye and
which account for the fastness
the fiber or the mordants employed.
The same
applies to
the enzyme-action where some kind of combination takes place between the enzyme and the substance upon which it
acts,
thus demonstrating their colloidal character and marked power as adsorbents. With the increased dispersion of the disperse phase the absolute surface increases enormously, and since the amount
their of chemical
change in unit time is proportional to the absolute
we should expect the reactions to occur much more slowly when the particles are coarse than when they are very fine. Hydrogen peroxide is decomposed slowly when smooth
surface,
num
employed, but if this is covered with platiis metallic platinum in a very fine state of Since division, the decomposition is very much more rapid. in colloidal systems we have the disperse phase in a very fine state of division, the specific surface would be large and we should expect the colloids to have a very marked influence upon the speed of the chemical reaction. Such is the case, and we have the great increase in the speed of the chemical
platinum
foil is
black, which
458
PHYSICAL CHEMISTRY
reaction through the mere contact of the finely disseminated This phenomenon is designated catalysis, and the colloid.
substance which brings about this enormous change is designated a catalyzer. Bredig and his pupils have shown that not
only are
many inorganic substances in the colloidal state capable of producing catalysis, but the same results may also be accomplished by the organic ferments termed enzymes.
Protective Colloids One would conclude from what has been said concerning the precipitating effects of electrolytes, that in order to have a colloid solution that is stable, it would be necessary, in the preparation of colloid solutions by chemical reaction and the subsequent removal of the electrolyte by dialysis, to remove all traces of the electrolytes. As a general thing this is true, but some authors believe that these minute traces are essential to the formation of a stable colloid solution and that they have a very pronounced stabilizing
effect.
Graham proved
that colloid
silicic
acid solutions are
stable the longer they are dialyzed, but it is known that colloid solutions of ferric hydroxide are less stable if
more
all
of the hydrochloric acid has been removed. Numerous workers have presented a number of facts which show that both effects are produced, and that even some colloids have a
This is true particularly stabilizing effect on other colloids. in the case of suspensoids where the stabilizing agent is an
emulsoid.
This
is
not due primarily to a change in the
viscosity of the disperse means. Hydrosols of metals usually exist in very dilute solutions, but by the addition of albumen,
dextrin, or starch very
much more
concentrated solutions can
be obtained.
will
one milligram of gelatin prevent the precipitation by sodium chloride of a liter of colloidal gold. Blood serum will do the same. Quincke has shown the protective action of gelatin in the system,
It is stated that
mastic-gelatin-water. This is also pronounced in the case of suspensions as well as where the protective action is produced by organic as well as by inorganic colloids. Carey
COLLOID CHEMISTRY
459
Lea's colloid silver, which is produced by reducing silver salts with tartrates, ferrous salts, dextrin, carmin, or such substances, may be protected by either an electrolyte or a colloid, and a colloid silver content of over 90 per cent soluble
in
water can readily be obtained. Certain colloid silver solutions containing protein substances used in medicine contain as high as 75 per cent of silver upon this basis. Zsigmondy
has devised a method for the identification and separation of various proteins, and these have been extended by the
work
of Biltz.
Physical Properties.
The change
in
volume
of colloid
solutions with pressure is but very little different from that of the pure disperse means and also from that of true molec-
ular dispersoids.
Gelatin at 100 is about 10 per cent less compressible than pure water, while a 30 per cent solution of KI according to Gilbant is even less compressible.
We have seen that as the degree of dispersion increases

specific
the
volume (volume weight) increases enormously, and that at the intersurf ace contact there is a marked condensa-
drops 0.3
tion of the disperse means. It has been found that water mm. in diameter have a density 0.5 per cent
greater than water in usual condition.
So
it
follows that the
density of colloid systems must be greater than when they are in a less dispersed condition. Molten and compressed
"that precipitated by oxalic acid, gold has a density of 19.33 while that precipitated by ferrous sulphate is 19.55 19.49
; ;
to 20.71. That is, the greater the degree of dispersion of suspensoids the greater their density. In the case of emulsoids this is just as pronounced. Quincke observed a decrease
in volume of more than 3.5 per cent in the system dried eggThe density of hydrogels is decidedly albumen-water. greater than that of the dry substance for example, a 50 per cent solution of gelatin gave an observed density of 1.242, whereas the calculated value was 1.206.
;
If
the volume of the disperse means, water,
is
calculated
460
PHYSICAL CHEMISTRY
found to be much
less
after this contraction, it will be
with
increasing concentration of the disperse phase, as is shown by the following calculated value of the volume of i cc. of water
after contraction
:
In a 10 per cent solution of gelatin In a 25 per cent solution of gelatin In a 50 per cent solution of gelatin
0.96069
0.93748
0.90201
;
cc. cc. cc.
The same
is
true for the starch-water system
the contrac-
tion increases with the concentration, whether it be referred to the disperse means or to the
disperse phase.
From Fig. 93 it will be seen that for the suspensoids such as As 2 S 3 the density-concentration
is
a linear function, while for
emulsoids such as gelatin there is a decided curve, which is con-
cave toward the concentration

Concentration
FIG. 93.
axis.
As
illustrated
by the
curve for NaCl, we see that it is analogous to that for emulsoids and emphasizes the similarity of the true molecular disperse systems and the properties of emulsoids. The density-concentration gives us a
means
of distinguishing the two.
Colligative Properties of Colloid Solutions.
We have seen
in the case of true solutions, i.e. molecular dispersed systems, that the vapor pressure of the disperse means is greatly modified
by the addition of the second component, the disperse phase. The vapor pressure of the pure solvent is lowered by the addition of the solute. Likewise, there is a marked lowering of the freezing point and a rise of the boiling point produced by the addition of the solute. The amount of change in the vapor pressure, the freezing point, and the boiling
is
point is proportional to the concentration of the solute, and a function of the molar concentration.
COLLOID CHEMISTRY
461
i.e. the disperse phase, is molecularly disIn dilute solutions the changes of these properties conform to the laws of solutions which we have previously
The
solute,
persed.
considered, but we have seen that as the concentration of the disperse phase (solute) is increased and the solutions
become concentrated, abnormal values are obtained for the data, for which explanations are attempted upon various
assumptions, such as association of solute as well as of the solvent, combination of the solvent and solute (hydration), etc.
The measurements of the vapor pressure, the freezing point, and the boiling point of colloid solutions show that these properties of the disperse means are but slightly if at all
affected
by the addition
of disperse phase of the degree of
dispersion
of
we
designate colloid.
colloid solutions
have been
that the vapor pressure, are practically the same as those of the pure disperse means, nor are they changed appreciably by a large increase in the
Data from a large number and these show and freezing point, boiling point
collected,
concentration of the disperse phase. The slight change observed in some cases is attributed to the presence of impurities in the materials used.
Osmotic Pressure.
In the discussion of the
osmotic
pressure of true solutions we have seen that by the use of a colloid septum, such as a precipitated copper ferrocyanide
membrane, we have a semipermeable membrane which permits the passage of the solvent, i.e. of the disperse means. The hydrostatic pressure developed by the use of such a membrane in the osmotic cell we term the osmotic pressure of the dispersoid. It is stated that the disperse means passes
through the membrane, diluting the solution contained in the osmotic cell. It was not stated, however, just how the disthe membrane, whether it was due to the sieve-like character or the selective solvent action of the membrane.
perse
means " passed through
"
462
:
PHYSICAL CHEMISTRY
"
We can get osmotic phenomena in two Bancroft says l distinct ways depending on whether we have a continuous In the case of a continuous film it is film or a porous one.
essential that the solvent shall dissolve in the
membrane and
Since the permeability is not dependent on adsorption, there is no reason why there should be any fundamental difference between the adsorption of a solute
the solute shall not.
which does pass through the membrane and of one which If we have a porous film, we get does not pass through. osmotic phenomena only in case the pore walls adsorb the pure solvent and the diameter of the pores is so small that the adsorbed film of the pure solvent fills the pores full. Under these circumstances the dissolved substance cannot
pass through the pores. On the other hand, if the dissolved substance can pass through the membrane, it must be adsorbed by the latter. There is therefore a fundamental dif-
membrane and one that does not by the membrane and the second
If colloid solutions
ference between a solute which does pass through a porous in that the first is adsorbed
is
not."
osmotic pressure
is
are employed in an osmotic cell, a small developed but the question arises as to
;
whether
this small value
may
For
in the colloid solutions.
it will
not be due to the impurities be remembered that by
the process of dialysis it is exceedingly difficult to remove the electrolytes from them, owing to the marked adsorptive power of the colloid and also because of the stabilizing
all of
power
of certain electrolytes.
Numerous
efforts
have been
made
to determine whether the osmotic pressure developed was really due to the colloid or to the impurities present.
This was accomplished by determining the electrolyte content of the colloid and then introducing the same content into the outer liquid so as to have the concentration of the electrolyte the same within the cell as on the outside, thus elimThen the inating the osmotic effect due to the electrolyte.
1
Jour. Phys. Chem., 21, 450 (1917).
COLLOID CHEMISTRY
463
value obtained would be the experimental value of the osmotic pressure of the colloid itself.
The values obFactors Affecting Osmotic Pressure. tained vary greatly, depending upon the method of prepaThe osration of the dispersoid and its previous treatment.
motic pressure of molecularly disperse systems soon reaches a maximum and remains at that value, whereas the osmotic pressure of colloid systems reaches a maximum and then a
marked decrease takes place. Shaking or stirring the soluIn fact, tion has a marked effect upon the osmotic pressure. the variability is a marked distinction between colloid solutions and molecular dispersoids and is attributed to a change
taking place in the dispersion of the colloid system resulting in different states of aggregation and a change in viscosity.
This is true particularly in emulsoids. In molecular dispersoids Pfeffer showed that the osmotic pressure is proportional to the concentration of the disperse phase and also to the absolute temperature, but in the case
of colloid solutions there is
According to Martin
no such regularity manifest. and Bayliss
the osmotic pressure of albu-
men, haemoglobin, and congo

red varies directly with the absolute temperature. tin solutions Moore
For gelaand Roof
sol
found that the osmotic pressure increased much faster than the absolute temperature. Duclaux vshowed that the osmotic pressure decreased with the increase
of temperature.
fest
Concentration
FIG. 94.
The same marked
irregularities are
mani-
with reference to the relation between the osmotic pressure and the concentration, the value of the ratio of the osmotic pressure to the concentration is not a constant. This is well illustrated in Fig. 94. Congo red gives nearly a
464
PHYSICAL CHEMISTRY
constant value for this ratio, iron hydroxide sol gives a marked increase in the values of the ratio with the increase in concentration, while in the case of haemoglobin we have a decided deThe laws of solutions as developed from a consideracrease.
tion of the molecular dispersoids do not appear to be valid for colloid systems, for the attempt to apply them does not seem to be any more successful than in the case of osmotic pressure,
which apparently demonstrates that we are not justified in applying the laws of molecular dispersoids to the colloid systems. The addition of substances to colloid systems manifests
the same erratic change in the osmotic pressure as we noticed with reference to the change in the concentration of the disIn molecular disperse systems the addition of perse phase. another substance has an additive effect. The osmotic pressure of a highly dispersed congo red sol was found by Bayliss to be 207 mm. By replacing the water about the cell with water saturated with carbon dioxide, the osmotic pressure
was 120
mm. The addition of alkali usually causes an increase in the osmotic pressure in certain cases, but in the case of egg albumen the osmotic pressure
is
always diminished.
disperse
cell
The
motic motic
fer,
means enters the osand there is the increased

in the so-called os-
volume resulting
effect,
or as
some authors
"
pre-
the
"
pseudo-osmotic
pressure.
This
00010
a solid colloid. In Fig. 95 is given the effect of acid and alkali on the pseudo-osmotic pressure of a 1.5 per cent gelatin sol as determined by Lillie, while in Fig. 96 is illusFIG. 95.
Normal
00jo ooeo Concentration
pseudo-osmotic imbibition is not unlike the swelling phenomena in
trated the influence of acid
and alkali on the swelling of gelatin
according to the experiment of
Wo. Ostwald.
The analogy
is
very pronounced.
COLLOID CHEMISTRY
465
sol as af-
The
fected
relation
between the viscosity of albumin

of acid
by the addition
and
of alkali as
shown
in Fig.
97, according to Pauli,
and the change
of the pseudo-osmotic
pressure according to Lillie, is very manifest The increase in internal friction curves.
(viscosity) corresponds to a decrease in the pseudo-osmotic pressure, and this holds completely not only in the case of viscosity
by the
shape, of
and osmosis, but also for gelatinization, and as w e have seen for swelling as well.
r
We
are then dealing with complex phenomena which are most intimately con-
nected with one another. The addition of salts to sols of albumin
0009
'
013
036
and
been found by Lillie to decrease- the osmotic pressure. The magof gelatin has
alkali
formal Concentration
nitude of the decrease
is less in the case of normal salts of the metals than in the case of the alkaline earth metals,
while the salts of the heavy metals produce the most marked decrease in the osmotic pressure. The acid or alkaline char-
aooi
.ooz
.003
Normal
Concentration
Normal Concentration
FIG. 97
b.
FIG. 97 a.
we have just seen, not only affects the pseudo-osmotic pressure but also the viscosity of the
acter of a colloid system, as
colloid system.
The English botanist R. The Brownian Movement. Brown (1827) observed under the microscope that particles
466
if
PHYSICAL CHEMISTRY
these
not too large are always in rapid motion. Picton observed movements in the microscopically visible particles in
colloid metallic sulphide solutions,
to
is
and Zsigmondy shows it be very pronounced under the ultramicroscope. This termed the Brownian movement. The particles recogall
nizable in
dispersoids manifest this

if
movement
if
they are
not too large and
the disperse means, which may be either or does not offer too much resistance. The gaseous, liquid upper limit in size of particles is about o.oi /A/A in diameter.
The movements of these larger particles, which are very small, are spontaneous and continuous and of a trembling or vibratory kind and in a curved path. With increased dispersity the motion is translatory in a zigzag fashion and " Zsigmondy described it as dancing, hopping, and skipping," " as well as translatory and progressive." The viscosity of the disperse phase has a marked effect on
the
accelerates the
Brownian movement. The increase in temperature Brownian movement and also decreases the
This has been investigated extensively by Seddig, who concludes that the movement of the particles, the amplitude A, is dependent on
viscosity of the disperse means.
the temperature
and expressed the
relation
as follows:
A.*VJ,
in
which
17
is
the viscosity
or
A =
2
which states that
the path-length squared is directly proportional to the absolute temperature and inversely proportional to the viscosity of the liquid. Svedberg's law (Arj = k) applied to
this gives
2
rj
= kT
or
Arj
= kT and
since At]
k,
we
have A =
k\ T,
which states that when the viscosity

is
is
con-
stant the path-length
directly proportional to the absolute

in water
temperature.
very
fine
powder when placed
becomes coated
COLLOID CHEMISTRY
467
with the disperse means and soon becomes uniformly distributed throughout the water, thus showing that the
Brownian movement overcomes the action of gravity. Perrin showed that mastic dispersoids under the influence of gravity become stratified. This is general, and he concludes that in the case of the larger particles the downward component in the irregular motion of the particles is aug-
mented and previous uniform
distribution results in the ac-
cumulation of the particles at the bottom. Since electrolytes cause the coagulation of the disperse phase we should expect that the addition of electrolytes to
colloid systems
would have a marked influence on the Brown-
to caoutchouc juice On adding N/io of the gutta-percha particles was decreased to one half of their original rate, while N/io HC1 reduced the
ian
movement.
NaOH
the
movement
motion to only about one ninth of its original value. The original path length was 0.62/1/1, while in the alkaline solution
it
was
0.3
/A/A,
and
in the acid solution it
had decreased
to 0.07 /A/A. Schulze states that the motion of the particles in opalescent liquids is caused to cease by the addition of
in
small quantities of alum, lime, and acids with clumping, but some cases the retardation of the Brownian movement
occur without clumping, particularly in the more highly dispersed systems. Although the Brownian movement will not prevent the stratification of the larger sized particles, it
may
is
considered as one of the chief stabilizing factors of sols. by observing the rate of fall of a cloud of gamboge particles under the influence of gravity was able to deterPerrin
of particles per unit volume.
particles
mine the number

Stoke 's
1
Law
of
moving
By applying 1 through a medium, know-
The velocity of a particle is proportional to the square of its radius and inversely proportional to the viscosity of the medium. Expressed mathematically
it is v
= - Pl
9
~
"Q
gr
2
,
where
>?
v is the velocity, pi the density of the particle, P
the density of the liquid, radius of the particles.
the viscosity, g the gravitational constant and r the
468
PHYSICAL CHEMISTRY
ing the total mass, the viscosity, the density of the particles in the solid form and also in the emulsion, he was able to calculate the diameter of the particles as well as the Avoga-
dro constant, N, which is the number of parts in one gramThe mean value for equivalent of the disperse phase.
.
N
.
With other emulsions Perrin he found to be 70.0 X io 22 has repeated his experiments and obtained the value 68 X io 22 Utilizing the mathematical deductions of Einstein, who assumed that the Brownian movement is due to the impacts of the molecules of the liquid on the particle, the value obtained is 68.6 X io 22 from which he concluded that there is no essential difference between these particles and mole;
cules,
thus
confirming
the
kinetic
theory of Brownian
movement.
Applications of Colloid Chemistry.
colloid chemistry
The phenomena
of
which we have been considering include
adsorption, surface tension, surface concentration, diffusion, etc. These factors control our so-called physical and chemical reactions.
The
the
phenomena
applications of the principles embodying are so broad in scope that they include prac-
tically all of the principal
departments of chemistry.
Since
colloid chemistry deals with all degrees of dispersion in a
system except that designated as molecular dispersion, the
domain of colloid chemistry is practically coextensive with and comprises most of the industrial applications of chemistry. The list of industries which utilize the applications of these principles includes most of the commercial applications of chemistry, among which may be mentioned the wide field of
biological chemistry, agriculture, plastics, ceramic industry,
dyeing, tanning, rubber, sanitation, soap, photography, and It is beyond the scope of our presentation to metallurgy.
consider these in detail, and we shall only refer to the application of the principles of colloid chemistry to the new metallurgical process of ore flotation.
For a comprehensive conapplications of colloid
sideration of the other industrial
COLLOID CHEMISTRY
469
chemistry reference may be had to the current periodical An literature, and to the following recent publications
:
and Applied Colloid Chemistry by translated Wolfgang Ostwald, by M. H. Fischer, and The Colloids Chemistry of by Zsigmondy and Spear. In general, the process of ore flotation Ore Flotation. consists in employing a flotation machine in which are the ore, which is approximately 80 mesh, and water in the ratio of
Introduction
to Theoretical
together with small quantities of oil. Air is forced " " mechanically into this pulp by means of beaters. Then in this froth-flotation process we have the following systems
3 to i,
present
oil)
;
two
solid-liquid systems
;
(ore-water)
liquid-liquid (water-oil)
solid-gas
and (ore(ore-air), and two

.
liquid-gas systems
ous phases have

terfacial tension.
It is
These vari(water-air) and (oil-air) at their surfaces their existing respective
individual surface tensions,
and these are referred to as

is
in-
known
that the surface tension of water
changed
by the addition of various solutes or soluble contaminants, as they are sometimes called. All acids lower the surface
tension,
and the same
is
true of
oils, i.e.
the
oil will
reduce
the interfacial tension between the water-oil phases. We have seen that this change in surface tension is accompanied
by
adsorption, which results in the increased concentration of the contaminating or dissolved substance. We also have seen that the surface film might contain less of the contaminant
than the solution, when we have negative adsorption. That is, we may have a condensation of the disperse phase upon the
interfacial
boundary, while in the case of negative adsorp-
tion the disperse phase would be rejected. So in the case of two non-miscible liquids, liquid-liquid system, we have the
condensation of the disperse phase at the interface. Substances placed in contact with water, and also with many other liquids, assume an electric charge. Most of these
substances in contact with water become negatively charged,
47
PHYSICAL CHEMISTRY
and we have seen that by the addition of electrolytes these charges can be changed and even reversed. These charges are found in particles of varying degrees of dispersion, from
the ultramicroscopic particles to those occurring in coarse
suspensions.
Mineral gangues such as finely ground quartz,
when suspended
in water, are negatively charged, while sulphide minerals such as pyrite are positively charged. Oil drops are negatively charged, and the same is true of air
In colloid systems these bubbles, under certain conditions. contact films are electrically charged, and in the case of the
oil-water contact film the negative charge would tend to attract the positively charged sulphide particles of the ore,
causing this to adhere to the interface of the oil-water system, while the gangue particles would be repelled.
Upon
ores
the basis of this electrical conception the flotation of

:
by means of oil is considered to be an electrostatic process, and this electrical theory of Callow is stated as follows " It is a scientific fact that when the solid particle is suspended
around the particle a contact an electric charge, the amount
in water, the water will form film which generally possesses
and polarity depending upon the nature of the surface of the particle and the electrolyte in which it is suspended.
The presence
fact that the particles possessing placed in an electric field. It has
can be demonstrated by the them will migrate when been demonstrated that flotable particles have charges of one polarity (positive), and that non-notable particles have charges of the opposite
of these charges
that the froth is charged negatively polarity (negative) so attracts the positively charged or flotable minerals
;
and and
It is repels the negatively charged or non-flotable ones. this, it is believed, that causes the flotable minerals, galena,
sphalerite, etc., to adhere to the froth, and the gangue minerals, silica, etc., to remain in the liquid where they can be discharged as tailings."
It is
maintained by some investigators that as the electro-
COLLOID CHEMISTRY
static charges are small
471
compared to the
size of the particles,
they are hardly sufficient to hold together the particles of sulphides and the gas. It is therefore necessary to seek other explanations for the flotation of minerals by the froth process.
They
attribute the
phenomenon
in the froth process to be
due to the
interfacial surface tension
which determines the
character as well as the formation of froths. A froth is de" fined as a multiplicity of bubbles." As pure water will not produce a froth, it is necessary to introduce an impurity which will cause " a variable surface tension." The perma-
nency of a froth
is greatly affected by the viscosity, as the tenacity of the liquid film may be so modified by securing the proper viscosity and variable surface tension that the bubble
can be made more or less resistant to bursting or rupture, which is due primarily to concussion, pressure, evaporation,
and adhesive force. Anderson says l " Solutions

:
is
in which the continuous phase a solution of soap, various products from the saponification of albumens, etc. will froth voluminously even in a very dilute condition frothing never occurring in pure liquids and is a
,
definite proof that the solute or disperse phase lowers the vapor tension of the solvent. froth which shows adsorption at the
interfacial
sistence
and gas, depends for its peron the production of a viscous film at that boundary
boundary
of solution
these viscous films are the direct result of surface adsorption of the disperse phase, i.e. dissolved contaminants, the amount
of
which
is
small
disappearingly so."
The kind
of oil
and
the
factors in the production of a froth as well as in insuring its stability. " The most successful
amount of air are important
frothing oils include the pure oils, cresylic acid and turpentines, and other pyroligneous products from the distillation of wood
the coal tar phenols and their nearby derivatives, and almost all of the so-called essential oils are good frothers." Pure oil makes a brittle froth which dies immediately creosote
. .
.
MsL Chem.
Eng., 15, 82 (1916).
472
PHYSICAL CHEMISTRY
;
makes a stable elastic froth
coal tar products increase the visare but poor frothing agents. An oil mixture of different cosity oils will effect a better separation than a single oil, as in the " case of zinciferous slimes, the best combination consisted of pure oil as a frother, plus wood creosote as a froth and Anderson selector, plus refined tar oil as a froth stiffener."
gives as the " tion: (i)
main and essential requirements for froth flotaThe production of a persistent froth by any
the attachment of the bubbles of air to the sul;
means
(2)
and (3) the mainphides or other material to be floated of a selective action of froth bubbles for the the taining
sulphides or other material to be floated." Bancroft says " cannot get a froth with a pure liquid and air. There must be present a third substance in colloidal
:
We
solution which will tend to form
an emulsion
of air in the
liquid in question, for a froth is essentially a very concentrated emulsion of air in liquid. If the colloidal material is not present, it must be added. It has often been overlooked
that what
The
needed for ore flotation is a froth of air in oil. have proved successful are substances like which things sodium resinate, so called, which produce a froth of air in water in an alkaline solution but one of air in oil in an acid solution, because free rosin forms a colloidal solution in oil but not in water substances which form colloidal solutions in oil and not in water tend to emulsify water in oil."
is
;
. .
.
The tendency
oil
used in the process, and
of the practice is to reduce the quantity of if the amount is sufficiently de-
we have the particle of ore not surrounded by a film but oil, merely wetted partially with the oil, while a part of it is in contact with the water and another part in contact with air. This gives then, in addition to the effect of the oil,
creased
of
the flotation effect of the air as well.

air film
"
It is possible that the
surround the oiled particle of ore completely, In so that the oil does not come in contact with the water. that case we are back to a straight air flotation of oiled par-
may
COLLOID CHEMISTRY
tides.
473
if
This point
it
calls
for further study because,
es-
would have a very important bearing on the tablished, " future development of the subject.
fication of colloid
According to the classiPreparation of Colloid Systems. basis of the degree of disthe upon systems
all methods for preparing can be classified either as (i) condensation or (2) dispersion methods. The condensation methods diminish the dispersivity to
persion of the disperse phase,
colloid solutions
within the limits assigned arbitrarily to colloid systems. The disperse phase which exists in the molecularly disperse condition may be precipitated by double decomposition, hy-
In the case of BaSO 4 we have a case drolysis, or reduction. of double decomposition with the formation of very fine
which have a strong adsorptive power. Aluminium hydroxide is precipitated, and in the presence of the ammonium salts it is converted into a gel but if the ammonium salts are washed out, part of the hydroxide precipitate redissolves with the formation of the aluminium hydroxide sol.
particles
;
This same phenomenon is marked in the case of many precipitates, and the presence of electrolytes is necessary to prevent
them from forming
colloid solutions.
Carey Lea employed,
in the preparation of colloid solutions of silver, ferrous citrate as a reducing agent. Zsigmondy used formaldehyde to pro-
duce his gold sols from alkaline solutions of auric chloride carbon monoxide and phosphorus are also employed in the preparation of gold sols, while Gutbier obtained red and blue gold sols with hydrazine. The hydrolysis of salts is a special case of double decomThis is a reversible reaction and increases with position. the dilution as well as with the rise of the temperature. The
;
preparation of hydrosols of the metallic hydrates of aluminium iron, tin, bismuth, cerium, thorium, and zirconium by hydrolysis and the removal of the free acid by dialysis are typical
examples.
474
PHYSICAL CHEMISTRY
dispersion
methods increase the dispersivity of the disThere are a number of special methods by perse phase. which this may be accomplished. Washing out precipitating reagents from finely divided precipitates causes the parti" run through " the filter paper, thus demonstrating cles to
the necessity of the presence of the electrolyte to prevent the precipitate from "redissolving," that is, from its disBy the addition of a suitable persivity being increased.
peptiser the dispersivity can be increased until a sol is produced, and a typical example of this method is peptisation. Some metallic sulphides are peptised with hydrogen sulphide.
The
Zinc hydroxide and beryllium hydroxide form sols when treated with alkalies. Sols of many metals, such as chro-
mium, manganese, molybdenum, tungsten, titanium, silicon, thorium, platinum, etc., can be obtained by using suitable
peptisers,
which include organic

caustic
alkalies,
chloride,
alkaline
cyanide, and organic bases.
aluminium, potassium The disperse means may be

acids, phenols,
carbonates,
water,
methyl alcohol, ethyl alcohol, or glycerine.
By
mechanical disintegration (grinding) many substances can be so finely divided that they form colloid solutions. The electric dispersion method of Bredig (1898) consists in producing by means of a direct current an electric arc between electrodes of the metal to be dispersed under the surface of the liquid employed as the disperse means. Many hydrosols as well as organosols have been prepared by this method. Svedberg, by using oscillating discharges instead of a direct current, has prepared pure metal sols in water and other
liquids.
CHAPTER XXXVI
IN our discussion so far we have not considered that these
various reactions require any time for their performance, but have rather assumed that the chemical reactions take place
Such is not the case, however, for all reinstantaneously. actions require a definite period of time for the substances taking part in the reaction to produce a system that is in
equilibrium.
While the transformations are themselves
in-
stantaneous, the conversion of all of one set of substances into another set depends upon many factors, one of which is
the quantity of the substances to be transformed, that is, the of the reacting substances. In some cases the whole masses are transformed into new ones almost instantane-
mass
ously, the time of the reaction being a small fraction of a second, while other reactions may require days or even longer
Connected with the compleperiods for their completion. tion of any reaction there are two opposing forces, one the
moving power or the affinity, and the other the resistance to the reaction that comes into play. The latter can be varied
considerably, in fact so much that the speed of a reaction can be decreased materially and made so slow that the reaction while the affinity is definite for a has practically ceased The resistance to a reaction may be of matter. state given caused by the distance between the bodies reacting, by the viscosity of the medium in which the reaction is taking
;
place, etc.
and sulphuric acid may be decreased by subjecting the system to great pressure, greatly
reaction between zinc
475
The
476
PHYSICAL CHEMISTRY
where the evolution of hydrogen may cease entirely. A pressure of eighteen atmospheres stops the reaction, while a higher pressure, when 1.3 normal sulphuric acid is employed, reverses the reaction and causes zinc to be precipitated. Frowein found that the maximum vapor pressure of ZnSO 4 7 H 2 O at 18 C. is 8.406 mm., and a lower pressure produces a reversal of the reaction
:
ZnSO 4
HO+HO
2
2
ZnSO 4
H O.
2
In the case of evaporation we have a condition of equilibrium only when the maximum pressure of the body vaporizing is
equal to the vapor pressure. The rate of evaporation will be proportional to the difference between the two vapor pressures. Noyes and Whitney found practically the same relation for the rate of solution of benzoic acid and of lead
chloride, since the rate of solution proved to be proportional to the difference between the saturated concentration, C, and the concentration actually existing, i.e. the rate of
solution
is
proportional to the difference in concentration
k(C--c).
Affinity.
The idea of the mutual attraction of the elements
has been emphasized from very early times, and the property which causes the element to enter into chemical comIt was Newton who binations is termed chemical affinity.
first
considered that this force was inherent in the element
itself,
and he showed that this chemical attraction decreased with the distance more rapidly than the law of gravitational Various efforts were made to measure attraction required.
the magnitude of this attraction and represent the relative affinities of the various substances. Geoffrey (1718) was the
The elements to compile a table of this character. were arranged in the order of their decreasing attraction, and those above would replace the ones lower down from their compounds. Bergmann (1775) found that the conditions in which a substance existed affected its position in Geoffrey's
first

table.
477
These conditions were not only the state of aggreor gas) of the substance, but also the The value of such temperature and the medium present
gation
(solid, liquid,
a table of
affinities therefore became practically negligible. Wenzel in his discussion (1777) of the subject of affinity shows that the conditions under which the reactions proceded were dependent on the masses of the reacting substances, and he concluded that the chemical reaction is proportional
to the concentration of the reacting substances. Berthollet confirmed this experimentally and in 1801 emphasized that
the masses of the reacting substances must also be taken into consideration, for the effect of the mass may become such as to overcome completely the force of affinity. It
follows then that the activity of substances
must be measured
by the masses which produce a definite reaction, and this " Berthollet stated as follows The chemical activity of a
:
substance depends upon the force of its affinity and upon the mass which is present in a given volume." But this idea of the influence of the mass received a great deal of opposition
and was not accepted. It was not, however, until almost two decades later that Rose (1842) emphasized in a The decomposistriking manner the action of the mass. tion of silicates in the presence of water and carbon dioxide
of the air illustrates the breaking
down of very stable comweak chemical pounds by very reagents when they are in
These reactions canlarge quantities acting for a long time. not be duplicated to any appreciable extent in the laboratory.
Further, in the crystallization of acid sulphates of potassium
from boiling solutions, a portion of the sulphuric acid is split off to combine with the water. On redissolving this crop and
recrystallizing, the neutral salt is obtained, thus
showing the
further splitting off of the sulphuric acid by the mass action of the water. Other investigators now took up this work and
marked
presented a large number of experiments which show the effect of the mass of the reacting substances on the
478
reaction.
PHYSICAL CHEMISTRY
In the study of such reactions as the decomposi-
barium sulphate by boiling in a solution of potassium carbonate, it was recognized that there are really two reversible reactions to be considered, and for a particular condition, a maximum amount of decomposition of barium
tion of
sulphate.
It was not until 1850, when Wilhelmy published his data on the inversion of cane sugar, that we had the first method outlined by which the speed of the chemical reactions can be
measured.
Wilhelmy showed that by placing a sugar solution containing acid in a polarimeter tube and keeping the temperature constant, the progress of the inversion of the
cane sugar could be readily followed by observing the optical
condition at definite intervals of time.
He
studied the redifferent
action carefully at different temperatures with
quantities of sugar, of acids, and with different acids, and concluded that the amounts of sugar inverted in a given time
were proportional to the amounts of acid and of sugar present, and this also varied with the temperature.
Several years later (1862) Berthelot and Gilles studied the formation of esters from alcohols and acids, and these data emphasized the effect of the mass on the speed of these chemical reactions. They concluded that the amount of ester
formed in unit time
proportional to the product of the concentrations (the masses) of the reacting substances and inversely porportional to the volume.
is
It,
however, remained for Guldberg and
Waage
(1867)
to formulate mathematically these ideas of affinity, the effedt of mass, and the speed of the chemical reactions. " the chemical reactions in which the forces must
We study which produce new compounds are held in equilibrium by other forces," and particularly is this true where the reactions do not run to an end but are partial. If by the reaction of two subLaw of Mass Action. two new compounds, C and D, are the A and B, stances,
479
formed, the chemical equilibrium would be represented thus, A B ^ C -f- D. The substances A and B combine to
produce
C and
D, while under the same conditions
C and
and B, and when equilibrium is esreact to produce There is, then, tablished the four substances are present. a force causing the union of A and B with the formation of
C and D, thus resulting in the reaction going from left to This velocity was shown by right at a certain velocity. Guldberg and Waage to be proportional to the product of
the active masses of the two substances, that is, the velocity = k a b, in which a and b are the active masses of A and
Similarly, respectively, and k is the affinity coefficient. in the reverse reaction in the re-formation of the substances
A and B by the reaction of C and D, we have a velocity which is equal to k' c d, in which c and d are the active masses of C and D respectively, and k' is the affinity coeffiAs this is an equilibrium equation, it represents the cient. reaction from right to left proceeding at the same rate as the reaction from left to right, and in unit time there are as many moles of A and B decomposed to form C and D as there are of C and D decomposed to re-form A and B. That is, the velocities of these two reactions are equal, and we then have k a b = k' c d. If the reaction is in a state of equilibrium as just illustrated, then the velocity of the reaction represented by the reaction of the substances A and B must be equal to the
velocity of the reaction of k a b and v' = k' c d.

-
C and
D,
i.e.
v'
and
But where the
velocity in
one
from that in the opposite direction, going to proceed more rapidly in that direction, and as a result the reaction as a whole proceeds in that We speak of the reaction running to an end, i.e. direction.
direction
is
different
the reaction
is
until there is a complete predominance of one of the two is defined as the systems. The velocity of the reaction
difference
between the individual
velocities,
i.e.
V=
v',
480
or
PHYSICAL CHEMISTRY
V=
a
b
k'
d,
which
is
the fundamental ex-
pression for the velocity of reactions.
In the expression
k'
d or
k
=
a
we
recognize the
Mass Law
Equation, and the equilibrium constant

*
= K.
K
The Guld-
berg-Waage expression for the velocity of the reaction when the velocities of the two systems are equal is identical with the above expression, showing the reaction to be proportional to the products of the reacting masses.
means
Lewis by Thermodynamic Deduction of the Law of Mass Action. of an isothermal reversible cycle in which the "Equilibrium Box"
is
of van't Hoff
tion of the
Mass Law Equation
employed gives the following thermodynamic deducfor a homogeneous gaseous system. In
the reaction
+ B ^ C + D let the four gaseous substances be in the

two
reservoirs,
I, II,
with the concentrations

f
,
a, b, c, d,
and
a', b', c
d', respectively.
The
"
p IG
g
-J-
temperature of the two reservoirs is the same, and the substances are in equilibrium. I. Iso thermally and reversibly remove one mole of A from I at its partial pressure p A and the volume will be VA The work done
,
.
by the system is
V CA pdV.
p A VA
taneously the volume changes from
Now change p A to p A reversibly, and simulVA to VA The work done is then

.
Jy y
Now
is
force the
mass
of gas, one molecular

of the
volume VA ',
into II, the
work
p A VA
Then the summation
work done is
Assume The Gas Law, pV = nRT; since T is constant, then pV = a constant. As we have the same mass of gas it follows that pA VA =
CV
pA 'VA
,
'
hence the total work done
is
) JV
pdV, which
in this case
is
equal to } p ,Vdp.
II.
Similarly
and simultaneously with the transfer

I
of
let
one mole
of
be transferred from
to II.
Then

the work per mole of
481
B =J
B
t
VB dp.
to hold,
As the system
hence the
The Gas Law = RTa and pA p A = RTa' work on A = RT log

is
gaseous, assuming
we have
'
and the work on
B = RT log
III. Now in equilibrium box II, assume that the moles of A and added are changed into C and D and no external work is done. IV. Finally transfer one mole of C and one mole of D from II to I the above manner. Then
B
in
work =
c RT log + RT log ^c a
Now let these molecules of C and D

sume no
external
change into
initial
A and B
in I
and
as-
work
is
done.
The
conditions have been
restored and the cycle is complete. Since this was accomplished isothermally and reversibly the summation of the work done is zero.
Hence we have
*riog
log a + log b which becomes
abed
+ RT
log
RTlog
c + RTlog 3
= o
or
log d'
log c
log d
log a'
+ log
b'
log c'
=
c
'
a constant.
'
d
for a
This
is
is
the
Law
of
Mass Action
system following The Gas
Law
and
Guldberg-Waage's expression.
We
v
to form
-
have seen that when two substances A and B react C and D the velocity of the action of A on B is k a b; but it is apparent that this velocity must
change as the reaction proceeds, since the concentrations of A and B, a and b respectively, are changing continuously. Let us assume that x moles of A and of B have been used up in the definite time /, then the concentrations of A and B at the end of this time will be (a x) and (b x) respectively, and we have for the reaction velocity
v (after
time
/)
k(a
x)(b
x).
__-
482
PHYSICAL CHEMISTRY
this
During
time
wise have increased to

v' (after
time
/)
C and of D will like+ x) and (d + x) respectively, and We then state that the =k'(c + x)(d + x).
/
the concentrations of
(c
small
time,
amount
dt,
of
changed, dx, in the small interval of
would be
<^
dt
= k(a-
x)(b
-x) -
k'(c
+ x)(d + x).
is
if the reaction of the resulting products of the reaction so slight, that the speed of the reverse reaction can be neglected entirely, then the reaction velocity equation
But
becomes
Or
only one substance, A undergoing decomposition into products which do not react, then the equation takes
if
there
is
the form -^
dt
k(a
x),
which
is
Wilhelmy's law that the
velocity of the chemical reaction at any moment will be proportional to the amount of the substance, a, actually pres" the amount of ent. Or, as Harcourt and Esson state it, chemical change in a given time is directly proportional to
the quantity of reacting substance present in the system." The differenEquation for Monomolecular Reactions.
dx
tial
equation ^7
k(a
x) is then a
mathematical expres-
sion of the theory of the speed of reaction. Reactions which to an of this are termed monocorrespond equation type
molecular.
The equation
contains the variables
-j.
and x
and the constants k and a. If different sets of corresponding values of these variables be determined experimentally, together with the value of a, and substituted in the equation, the computed values for k should agree. It is of course im-

possible to get instantaneous values of -^,
te
483
and the approximaresults.
tions that can be obtained
do not give satisfactory
another equation, the terms in which can be readily and accurately measured. It is possible to derive another equation involving the same
It is therefore necessary to obtain
constant, k,
by
integrating this differential equation.

00}
The equation -^ = k(a at

dx
may
be written
kdt,
which on integration gives
which becomes
loge (a
x)
/
kt
C.
oc
At the
becomes
initial
conditions
log, (a
o and
fco
o,
the equation
C= -
o)
= -
log. a.
Substituting this value for

solving
in the
above equation and

x) or
we have
kt
=
=
log, log,
log, (a
kt
a a
or
-*
;
It is customary to use the logarithms to the base 10, log, instead of the natural logarithms, log e then the equation
becomes
0.4343 k
log
x
it
It is evident that since this is
a constant
could be ex-
pressed directly in terms of log, and the equation takes the
form
/
484
which
PHYSICAL CHEMISTRY
may
be considered a special case of the general
formula.
Reactions wherein Equation for Bimolecular Reactions. there are two of the reacting substances changing in concentration during the reaction are termed bimolecular reactions.
The
reaction velocity at
at
any moment
x)(b
x),
is
given by the
in
differ-
ential equation
-^ =
k(a
which a and
represent the concentrations of the two substances the concentrations of which are changing. Let x represent the amount of one substance that has changed in time /, then the
same number
have changed during the same time. If we assume that there are the same number of moles of the two substances present at the beginning of the reaction, then a = b and the equation
becomes -^
dt
of moles of the second substance will
k(a
x)
/
2
;
or
rearranging,
dt
k(ax)
o and
Integrating,
we obtain
=
k(a
-f constant.
Evaluating
/
x)
the constant in the usual

substituting,
stituting,
way by putting x =
o and
hz we have
the integration constant
-^-.
ka
S UD -
we have
k(a
-x)
x)
ka
or k
and simplifying
= t
ka(a
If,
a(a
x)
however, the quantities of

is
and
are not equal, then
the equation
^ = k(a-x)(b-x)
'
which
may
be rewritten
*
-<**-( a b\b
x
a
\=
xj
kdt.

Integrating,
485
we obtain
-
-a
If
b\
(log *
a
b
xj
kt
constant.
o and
o, substituting,
1
we have
constant.
log
=a
Introducing this value, the equation becomes

l
a
Solving,
b\
=kt- -^-r log (log^-?-} b a a a xj

b
â
~~t3
a
-
x x
which
simplifies to
Equation
for
Trimolecular
<-^^|5fReactions.
If
*
there
are
three reacting substances and x represents the number of moles of each entering into the reaction in the time t, then
dx
at
= k(a
x)(b
x)(c
x).
The
simplest case
is
where
the three reacting substances are in equivalent proportions.
Then the equation

integration
gives
takes the form -~-= k(a

at
x)
3
,
which on
and by the evaluation

T
of the integration constant

x)
\~~
*
i x(2 a ~
/
Degree
of the Reaction.
The number of different molec-
ular species whose concentration changes during the course of the reaction is used as the basis for designating the order
of the reaction. The reactions are termed monomolecular when only one molecular species changes in concentration bimolecular, when two change trimolecular, when three
; ;
486
PHYSICAL CHEMISTRY
constituents change in concentration, etc. The three equations just derived are very different, and the question arises,
how can they be used

reaction?
times,
/,
to determine the order of a chemical
By substituting in the equations the different at which the concentrations, x, are determined, and knowing the initial concentration, the velocity constant
can be calculated. The formula which gives a constant value would designate the order of the reaction. It is, however, necessary to make but a few determinations, for if the time in which one half of the material available for transformation is known, the relation between the time and the original concentration of the constituent
different types of reactions.
is
very characteristic for the
If
on substituting
this
value in the equation for monomolecular reactions and solving for /, we find that the time is independent of the original
concentration,
i.e.
substituting,
tk
we have
2.
log
As the
This
is
tion, the
original concentration does not appear in the equatime / is independent of the original concentration.
known
as the period of half change.
Similarly, it
is
may
be shown that for bimolecular reactions the time
inversely proportional to the initial concentration, and for trimolecular reactions it is inversely proportional to the In general, the time square of the initial concentration.
required to change one half o'f the substance present undergoing the chemical change is inversely proportional to the
(n i)th power of the initial concentration. the reaction is then readily established.
The order
of
Reactions of different degrees of complexity are known,
and those to the eighth order have been described.

the
When
number
of reacting substances is increased, reactions
between the original constituents and the new constituents become possible as well as the reactions between the new

constituents themselves.
487
of side
There
will result a
number
reactions which will be of different orders, depending on the number of molecular species produced by the original re-
action as well as
by the secondary
side reactions.
Then
there will be reactions which are opposite to the original These may take place at the same time as the reactions.
original reaction, or they may be at a different time, thus giving rise to what is termed consecutive reactions. So the
actual rate of a reaction, which is what the velocity constant, will be dependent
we understand by
upon the
relative
rates of the other reactions, and the value will be the sum of all the intermediate independent changes. Our discussion
will be confined to a few examples of the simple cases free from these auxiliary reactions. Monomolecular Reactions Running One Way. Reactions of the first order are very common, and among these may be mentioned reduction of potassium permanganate reduction of hydrogen peroxide decomposition of diazo compounds decomposition of chlor- and brom-acetates forma;
;
tion of anilids
formation of esters in methyl alcohol catalysis of sulphonic esters the conversion of persulphuric acid into
; ;
"
Caro's
"
acid
;
sis of
starch
decomposition of nickel carbonyl hydrolyhydrolytic action of yeast, and inversion of

;
sugar.
inversion of cane sugar by acids and salts in aqueous solutions is one of the important chemical reactions that
it
The
the conditions for a reaction of the first order, since has been found that the concentration of the hydrolyzing or inverting agents remains constant throughout the reacfulfill
tion.
The equation
12
representing the reaction

2
is
12
C H 2Oii + H O
2
^CH
6
12
+CH O
6
6.
dextrose
levulose
This appears to be a bimolecular reaction, but the amount of the water that enters into the reaction is so small com-
pared with the amount of solvent present that
its
concentra-
488
PHYSICAL CHEMISTRY
This reaction may be tion remains practically constant. carried out experimentally by placing equal volumes of a 20 per cent sugar solution and a fourth normal acid solution into
a number of small flasks which have been freed from alkali by thorough steaming. These flasks are placed in a water
At bath, which is maintained at a constant temperature. convenient intervals of time (about 30 minutes) one flask is removed and the sugar determined by the polarimeter. Having determined the initial concentration (polarimeter
reading) at the time of mixing the acid and sugar solutions and the readings for several hours, the solution is permitted to stand for several days or is heated to obtain the end point
of the reaction, that
The is, the point of complete inversion. value obtained in this manner does not always agree with
the value calculated from the weight of sugar employed. A of experimenters have shown that the specific rotais
number
tion
and
also
dependent on the concentration, time, temperature, upon the acid used. By substituting the data in
the equation k
=/
log
and solving
for k, the values
for the velocity constant or coefficient may be obtained as illustrated in Table LXXXVIII. It is immaterial in what units
a, of the substance changing is expressed. convenient to employ the values as expressed usually of the scale the polarimeter for designating the values of by a and of x. In Table LXXXVIII / represents the time in
the concentration
So
it is
minutes, after the solutions of sugar and acid were mixed, when the polarimeter reading was taken a the reading on the scale x the difference between the initial reading and the
; ;
reading at the given time. In the last column are given the values for k, which indicate a good constant value. From an inspection of the equation it will be seen that
there are no factors that take into account the concentration
of the sugar or of the hydrolyzing agent. Ostwald from his experimental results showed that the concentration did have

an
489
effect on the velocity coefficient. Cohen, however, considered that the molecules in a concentrated sugar solution
path of motion than those in less concensince the speed is proportional to the free path it is proportional to the actual space occupied by the sugar molecules. By applying the proper correction for this, he concluded that the concentration did not affect the
have a shorter
free
trated solutions,
and
velocity constant,
of the sugar.
i.e. it is
independent of the concentration
TABLE LXXXVIII
INVERSION OF CANE SUGAR
a (total change)
/
65.50
4QO
PHYSICAL CHEMISTRY
The strength of an acid is tions that yield hydrogen ions. attributed to the hydrogen ions present due to the dissociation of the acid, that is, the greater the degree of dissociation the greater the hydrogen ion concentration. In the case of
the inversion the greater the concentration of the hydrogen ions the quicker the inversion of the cane sugar. Trevor used the cane inversion of as a of means deter(1892) sugar
mining the concentration of the hydrogen
ions,
i.e.
of the
degree of dissociation of the acids. This method has been employed extensively for establishing the relative strength of acids and in Table LVIII, page 356, is given in one column the
relative values referred to hydrochloric acid taken as i.ooo. These values give an excellent idea of the variability of the
inversion coefficients of the various acids.
be remembered that certain organic salts undergo hydrolytic dissociation with the formation of hydrogen ions. Trevor employed the inversion of cane sugar as a method for the determination of the degree of dissociation of a number of the sodium salts of organic acids, and W. A. Smith also determined the hydrolytic dissociation of organic salts by this method and compared the values with those obtained by the electrical conductivity method. Long published the results of his experiments on the inversion of .cane sugar by inorganic salts. His results, given in Table LXXXIX, will
It will
illustrate
value, k,
the type of reactions and the constancy of the obtained for the velocity constant.
in the solutions
The data show that
employed the normal
solution inverted the sugar but little more rapidly than the From the data obtained he calculated half normal solution.
the degree of hydrolytic dissociation of these salts. The addition of normal binary salts with a common ion
to
an acid has a marked
effect
upon the
velocity of inversion
For example, potassium chloride added to of cane sugar. a solution of cane sugar containing hydrochloric acid greatly
increases the velocity of inversion, while the addition of a
49 1
salt to a weak organic acid with a common ion greatly decreases the velocity. Arrhenius says, " The catalytic activity of hydrogen ions is greatly stimulated by the presence of other ions."
TABLE
LXXXIX
0.5
INVERSION OF CANE SUGAR BY
FeSO 4
NORMAL
HO
2
49 2
PHYSICAL CHEMISTRY
and a
salt of the corresponding organic acid. This be illustrated by the following chemical equation
:
may
ethyl acetate
H OH + CH COONa NaOH^C sodium sodium

2
5
hydroxide
ethyl alcohol
acetate
In order to determine the velocity of this reaction equal volumes of ester and the base of the same molecular concentration are mixed in a flask and placed in a constant temperature bath.
At convenient intervals of
time,
/,
a definite quan-
tity of this mixture is pipetted into a definite excess quantity of standard acid. The excess is determined by titration, and
the alkali at this time can be calculated

a, is
and
if
the original
concentration, known, the velocity can be calculated by means of the bimolecular reaction equation
a (a
'
x)
since the
two substances changing simultaneously were taken
in equal molecular quantities.
This equation contains no term designating the nature of the ester or of the saponifying agent, and the question has been raised whether they do affect the velocity of saponification and also whether an excess of either would have any influence.
Reicher attempted to answer this and obtained data which show that different bases give different values for the constant. This is illustrated by the following data
for
methyl acetate, using bases of the same concentration

BASE
493
The strong bases all give practically the same value for the constant coefficient, while the saponification by ammonium
hydroxide takes a
much
longer time.
That the alcohol radical has a marked influence is shown from the following data, which give the constant for the saponification of these various acetates by solutions of sodium hydroxide of the same concentration
:
ESTER
494
PHYSICAL CHEMISTRY
determination of the degree of electrolytic dissociation, that The rate of is, the concentration of the hydroxyl ions.
saponification can be followed by the conductivity method, and the values of the velocity constant as found by different
investigators agree well. Saponification of esters
by weak
bases, such as
ammonium
hydroxide, methylamine, ethylamine, etc., proceeds slowly and gives a small velocity constant which varies with the
time.
1.76
salts
:
Ammonium
i. 21
:
i. 01
hydroxide gives, for example, the values 0.845 0.501. Ostwald showed that neutral
:
have a marked
by weak bases
to this cause.
It
upon the rate of saponification particularly, and attributed their variations

effect
has also been shown that saponification can be produced
by substances that on hydrolysis yield alkaline solutions, and since the rate is proportional to the concentration of the
ions, this method may be employed as a means See of determining the degree of hydrolytic dissociation.
hydrogen
Table LXVI, page 393. Other Molecular Reactions. There are numerous reactions of a higher order than those in which only two molecIn many of these there are secondary ular species take part. reactions which are not only reverse reactions which prevent the major reaction from going to completion, but also side reactions which result from the inter-reactions with the products of the reaction. These side reactions may be simultaneous with the main reaction or they may be consecutive. When a number of substances are present, they may react so that there is a series of consecutive reactions. The
most pronounced example of consecutive reactions probably is the formation of radium emanations. This is true not
only in the case of homogeneous reactions but we may also have reactions of different orders in the case of heterogene-
ous chemical changes wherein the reacting substances are in different states of aggregation. For a discussion of these

the student
is
495
referred to special texts
on advanced Physical
Chemistry. Iron Factors which Influence the Velocity of Reactions. at the with to air combines oxygen ordinary exposed slowly
temperature. If a piece of iron picture wire is heated and introduced into oxygen, the iron burns very rapidly with an evolution of much heat and light. The reaction is of such
velocity at this higher temperature that the heat developed is greater than can be conducted or radiated away, so that
the heat in turn accelerates the reaction.
Similarly, for
many
other substances there
is
no reaction between them, or the
On inreaction proceeds slowly at the lower temperatures. creasing the temperature the speed of the reaction increases
until a temperature is reached at
which the heat generated exceeds that conducted or radiated away, and the mass becomes incandescent, breaks into a flame, or ignites. With
gases
it is
we designate this the flash point, with the temperature of explosion. This minimum temperature at which combustion or explosion takes place is designated the ignition temperature, or the kindling temliquids such as oils
perature.
When phosphorus is placed in air, the reaction with the oxygen is slow but when the temperature is raised above 60 There is some reaction taking C., the phosphorus ignites. place below the ignition temperature, but it is slow, and in most cases the reaction is so slow that it cannot be observed.
;
The reaction velocity at the ignition temperature is so great that the heat evolved is sufficient to maintain this temperature
and even increase
it
the speed of the reaction.

perature
with the accompanying increase in In many cases a small rise in tem-
may
of the reaction.
fast at 55
then give an enormous increase in the velocity Cane sugar is inverted about five times as
as at 25. According to Berthollet an ester may be formed about twenty-two thousand times as fast at 200 as at 7. Many empirical formulations of the change of the
496
PHYSICAL CHEMISTRY
velocity of a reaction with the temperature have been made. The relation seems to be, that the velocity is nearly proportional to the square root of the absolute temperature.
influence of pressure on the velocity of reaction is practically negligible in the case of reactions of the first order, but for reactions of the second order the effect is nearly a
The
The velocity of decomposilinear function of the pressure. tion of hydriodic acid is, according to Bodenstein, practically proportional to the pressure to
jected.
The
reaction between metals
which the gas is suband acids with the
hydrogen ceases above a certain pressure, to and Tammann. Nernst according The nature of the medium in which a chemical reaction takes
liberation of
place has a
marked effect on the velocity of the reaction. Menshutkin gives the data in Table XC for the velocity con-
stant in a
number
of solvents for the reaction of ethyliodide
on triethylamine,
CH
2
5I
(C 2 H 5 ) 3 N
(C 2 H 5 ) 4 NI
TABLE
SOLVENT
XC
497
for the solvents is given in the last column of the table. The velocity constants do not appear to bear any relation to the
dielectric constant of the solvent or to the viscosity changes.
From
but
solvents alone do not

it is
the evidence available the physical properties of the seem to determine the reaction velocity,
to be noted that those solvents with high dissociapower are the ones in which the reaction of dissolved substances is the most pronounced. In the reaction of hydrogen and oxygen, as in the case of the ignition of other gases, there is a definite rate at which the flame travels throughout the mass of gas. The ignition is started at one point and owing to the intense heat developed, due to the chemical reaction of the gases, there is an increase
tive
in pressure.
The time required to develop the maximum pressure is then a measure of the explosiveness and is the time of explosion. The explosion is considered complete when
maximum
pressure
is
reached.
Bunsen found that
for
pressure was attained in -ôVo of a second and the high temperature lasted for at The temperature obtained by calculeast ^3- of a sceond.
oxygen and hydrogen
maximum
lation necessary to produce this pressure was 2500. making corrections for steam condensed the value found
But was
3897, but on further corrections for heat evolved by the combustion, which was assumed complete before maximum pressure was reached, constant specific heat of steam at constant volume, etc., assuming ideal conditions, the value of 9000 was found. But these ideal conditions are unattainable,
and the maximum temperature ranges between 2500 and 3900, which, however, does not account for all of the
heat evolved.
As the ignition of the mixture takes place from particle to particle, the heat due to the reaction causes an expansion, which in turn causes the projection of the ignited into the unignited particles and increases the rate of
ignition.
The formation
of these gases is so violent that their quick
498
PHYSICAL CHEMISTRY
expansion produces another blow on the surrounding mass, which causes complete explosion of the entire mass. The rise of pressure is exceedingly rapid and produces not only a forward wave of detonation but also a sudden backward wave of compression which hastens this residual combustion.
explosive, or detonating wave set up is comparable to a sound wave passing through a gaseous mixture. It results, " an abrupt change in chemical condition however, from which is propagated in the explosive wave and which generates an enormous force as it passes through successive layers Berthelot considers that the main velocity of the media."
The
of translation of the molecules of the products of combustion, retaining kinetic energy corresponding to the heat developed
in the reaction, may be regarded as the limiting maximum rate of propagation of the explosive wave. Berthollet and
Vieille found the rate of propagation of the explosive wave in pure electrolytic gas to be 2810 meters per second, and
Dixon's value, 2819 meters per second, confirmed this. The inversion of cane sugar is much more Catalysis. rapid in the presence of acids than in pure aqueous solution,
and we have seen that the rate

the concentration of the acid,
of inversion
is
proportional to
i.e.
to the concentration of the
hydrogen ions. The hydrogen does not enter into the products of the reaction, but its presence greatly accelerates the Berzelius introduced the term progress of the reaction. " A catalytic agent catalytic agent and defined it as follows
:
is
a substance which, merely by its presence and not through its affinity, has the power to render active, affinities which
at ordinary temperature." The agent which causes the catalytic action or catalysis is called a catalyzer or a Ostwald defines a catalytic agent as a substance catalyst.
are latent
which
self
affects the velocity of a chemical reaction appearing in the final product.
without
it-
A catalyzer cannot start a reaction, but it merely modifies the velocity of the reaction. It does not change the equilib-
499
rium point, as it affects the velocity of the inverse reactions to the same degree. There is no change in the concentration
of the catalyst, for if in the inversion of cane sugar by means of acid, the concentration of the acid be ascertained at differ-
ent stages of the reaction, the values will all be the same. An infinitely large quantity of the reacting substances can be
transformed by a very small quantity of the catalyzing agent.

Titoff says that the rate of oxidation of a solution of
sodium
sulphite is noticeably increased by even dipping a strip of clean copper into the solution for a few seconds. The re-
duction of mercuric chloride by oxalic acid is greatly increased by the addition of potassium permanganate to a concentration of o.ooooo i
gram
in ten cubic centimeters.
The
nature and the quantity of the catalyst does not affect the finaf state of an equilibrium. There are a large number of
catalytic agents and reactions, " state that there is probably
and Ostwald goes so far as to no kind of chemical reaction which cannot be influenced catalytically, and there is no substance, element, or compound which cannot act as a catalyzer." Although there have been several efforts to
classify catalytic reactions, we shall not present any of these, but shall consider a few of the marked examples of catalysis
and mention a few technical applications

tions.
of catalytic reac-
On placing a platinum wire heated to redness in various mixtures of gases and vapors combination results. This
was shown by Humphry Davy (1817), and this fact was utilized by Hempel for the analysis of mixtures of gases. By
passing a mixture of oxygen with hydrogen, carbon monoxide, methane, and nitrogen over spongy platinum at 177, only the hydrogen and the carbon monoxide are oxidized. Phillips
in 1831 patented the method for manufacturing sulphuric acid by the process of oxidizing SOz with the use of platinum wire or platinum sponge. But owing to the fact that certain
impurities destroyed the catalytic action of the platinum
the.
500
PHYSICAL CHEMISTRY
process was abandoned.
number
of substances such as
etc.,
hydrogen sulphide, ammonia, ethylene,
have been found
to destroy or inhibit the activity of the platinum. The more highly dispersed the catalyst is, the greater its
chemical activity.
For example, platinum black
is
more
active than sheet platinum, i.e. there is more surface exposed. " the layer of carbon dioxide Mitscherlich concludes that which condenses on the walls of wood charcoal is about
0.00005 cm thick," and that at least one third of the carbon dioxide so condensed is in the liquid state. That perfectly
-
dry gases do not unite has been demonstrated by a number Dixon (1880) demonstrated that the reacof investigators. tion takes place only in the presence of moisture and showed
that at 100 sulphur dioxide and oxygen will not unite in the presence of water vapor, but that a particle of liquid water This condensation theory of combusproduces oxidation.
tion proposed by Faraday has been supported by many others and particularly by Dixon, who attributes to water vapor " the r61e of an oxygen carrier." This was stated by Mrs. Fulhame in 1794, nearly a century before, as follows " Water is essential for the oxidation, and it is always decomposed in carbon monoxide unites with the oxygen the process;
: .
.
hydrogen of the latter seizes the oxygen of the air." Dixon showed that when the vapors such as hydrogen sulphide, ammonia, formic acid, ethylene, etc., were mixed with oxygen and carbon monoxide the explosion would take place, while if carbon dioxide, nitrogen monoxide, and carbon bisulphide were employed no explosion resulted. Hence, not only steam but all substances which will form steam under the conditions of the experiment will cause the reaction
to take place.
of the water, while the
A minute portion of the solid phase of the solute introduced

into a supersaturated solution of this particular solute may the blow by a trigger causes cause the mass to crystallize
;
the materials in the detonator to react
and
similarly the
501
addition of small amounts of material or small amounts of
energy in various forms such as heat, light, etc., may result in chemical changes which produce enormous quantities of energy in other forms. These results are not at all commensurate with the initial inaugurating effect and are independ-
ent of
it.
Phenomena
is
of this type
must be
it is
clearly different
from what
termed
catalysis,
but
not an easy matter
to distinguish the differences.
There are a large number of reacwhich we term catalytic for which no very satisfactory explanation had been presented, and the method of the reac" " tion has been explained by stating that it was catalytic, " which of course does not explain." Efforts have been made
Catalytic Processes.
tions
to show how the catalyst actually takes part in the reaction, and the " combination hypothesis " as employed by Dixon
is
This is analogous to the explanation of extensively used. the electrolytic decomposition of water. We use, however, either an acid or an alkaline solution and obtain hydrogen and
oxygen, the constituents of water. In the catalytic action of dilute acids Kastle and other workers state that the hydrogen
ions react first to
form addition products, and these subsequently are decomposed into the final products. In the
and
Crafts' reaction
Friedel
anhydrous aluminium chloride
is
used as the catalytic agent. The reaction is explained usually by assuming the formation of additive intermediate compounds, which then react to reform the catalytic agent alu-
minium
chloride
chloride.
is
The
reaction between benzene

:
and ethyl
explained as follows
2 6
and
A1 2 C1 5
A1 C1 6 + C H 6 = C H + C H C1 =
6
5
A1 2 C1 5 A1 2 C1 6
C H + HC1 +CH CH
6
5
5.
intermediate
The aluminium chloride reacts with the benzene, and this compound then reacts with the ethyl chloride
is
with the reformation of aluminium chloride. The manufacture of chlorine by the Deacon Process
f
502
PHYSICAL CHEMISTRY
usually explained chemically by assuming the formation of intermediate products. Thus,
CuSO 4
4
+
2
HC1 = CuCl2
2
CuCl 2 =
CuCl
+ H SO + C1
2 2
CuCl
+O =
2
2(CuCl 2
2
CuO)
2
CuCl 2
+ CuO
HC1 =
CuCl 2
+HO
The copper acting as a carrier of the chlorine, we have the formation of cupric chloride, its decomposition into cuprous
chloride with liberation of chlorine, and then its subsequent regeneration in the presence of hydrochloric acid. The ex" " contact agent which planation that the copper salt is a
is
aids in attaining the equilibrium also offered.
HC1
+ O $ H O + 2 CU
2
2
Metallic Catalysts.
Platinum in a very
fine state is
em-
ployed in
many catalytic processes, and it has been found that
numerous other metals as well as their oxides can be employed

in a large number of reactions in order to increase the velocity of the reaction to such an extent that it can be carried on
under normal conditions (which include lower temperature) with the insurance of a large yield of the desired product
and the
financial success of the process.
In addition to platinum
may
be mentioned finely divided
indium, palladium, osmium, copper, iron, nickel, cobalt, vanadium, ruthenium, and the oxides of the same colloidal suspensions of metals have proved excellent catalyzers. Cerium
;
was used
to
pose.
make ammonia, but
as catalyst for combining hydrogen and nitrogen iron is extensively used for that pur-
Electrolytic cerium, mixed with about two per cent of potassium nitrate when employed as a catalytic agent for the combination of hydrogen and nitrogen, gave about three times
the yield of the untreated cerium. Substances of this type are designated promoters. In general, the compounds of the
metals of the alkali and the alkaline earths are promoters of catalytic action, as well as the oxides of the rare earth metals

tantalum and niobium, as well as
silica,
503
while the metal-
loids, sulphur, selenium, tellurium, arsenic, phosphorus, and easily fusible and easily reducible metals such as zinc, lead,
and tin, usually act as contact poisons. There are two of these used in extensive industrial processes which will be considered in some detail. They are
platinum in the contact process for the manufacture of sulphuric acid and nickel in the hydrogenation of oils. The Hydrogenation of Oils. The addition of hydrogen to oleic acid (CigH^C^) with the formation of stearic acid (Ci8 H 36 O 2 ) has been one of the problems of the chemist for Oleic acid is a liquid and stearic acid is a solid at ordiyears. nary temperatures. This fact, in addition to the great
abundance
of oleic acid,
made
it
desirable to utilize oleic

late as 1897
acid as a source of hard fats.

states that while the lower
Lewkowitsch as
members
of the oleic acid series
can be converted into saturated acids, " oleic acid itself has resisted all attempts at hydrogenation." It was not until about ten years later (1907) that Bedford and Williams published the first description of a method of exposing oil to the action of hydrogen by forming the oil in a spray or film in an atmosphere of hydrogen in contact with a catalyzer of nickel. They converted linseed oil into a hard fat melting at 53, oleic acid into stearic acid with a melting point of 69,
and the solidifying point of paraffin wax was raised 3. While this is still the general method employed in the hydrogenation of oils, many detailed mechanical devices have been
introduced.
Various catalyzers have been tried, but the one used

principally is metallic nickel, and numerous patents have been issued on methods for the preparation of the catalytic agent.
An
effective nickel catalyzer
may
be prepared by either
ig-
niting nickel nitrate to obtain the oxide, or by precipitating the nickel hydroxide from a sulphate solution by an alkali.
This oxide or hydroxide
is
then reduced by hydrogen at a
504
PHYSICAL CHEMISTRY
temperature between 250 and 500 or until water is no longer formed. The lower the temperature at which the reduca good working tion takes place, the more sensitive it is
;
range
cient
is
between 300 and 350.

active surface
is
when the
catalyzer is more effiincreased by employing a
The
So there are employed a large number of carriers and extenders, such as pumice stone, kieselguhr, charcoal, and sawdust. The catalyzer should be protected from the air to prevent oxidation. It is claimed by various investithat a short is gators period required for the nickel catalyzer to become acclimated, as it were, before reaching its maximum efficiency or activity, after which there is then a period
carrier.
of decline.
The most active period is generally very long, and

is
the period of decline
usually attributed to the action of
For treating liquids, superficially treated or coated poisons. carriers are most desirable, while for the hydrogenation of
gases or vapors porous impregnated catalyzers are better.
The Mechanism of Hydrogenation. The methods by which the various catalytic metals transfer the hydrogen during the process of addition or hydrogenation of numerous bodies, as well as the reduction by hydrogen of other bodies, has led to many attempted explanations. The prevalent ones are the adsorption method and the hydride formation.
Whether the hydrogen
there
is
is
difference of opinion, as Firth
adsorbed, absorbed, or occluded, shows that adsorption
of hydrogen by wood charcoal takes place in a few minutes, while hours are required for an equilibrium to be realized by That many metals dissolve hydrogen has been absorption.
demonstrated by many workers, and in Table XCI are given the volumes of hydrogen under normal conditions that are adsorbed by one volume of the metal.
is
of hydrogen by palladium and by platinum very pronounced, and the same is true for cobalt, nickel, and iron. The solubility increases with a rise in temperature,
The adsorption
and the metals copper,
iron,
and nickel
in the liquid
505
state manifest a very marked increase in solubility with inOn solidifying at 1084, copper crease in temperature. gives up twice its volume of hydrogen, iron at 1510 about
seven times
volume.
volume, and nickel at 1450 about 12 times its " " They all spit when allowed to freeze in an atits
mosphere
of hydrogen.
TABLE XCI
ADSORPTION OF HYDROGEN
(Abegg and Auerbach) Anorganischen Chemie

METAL
PHYSICAL CHEMISTRY
in
which
KP
is
the equilibrium pressure constant.
The values
of this constant with increase in temperature are given (by
Bodenstein) as follows
Degree C.
APPENDIX
To
tions,
supply the data for numerous problems such as are
required for use with large classes necessitates
and
in
most
type are given.
To
many duplicaof problems but few of the same multiply these as usually stated requires
lists
considerable space,
and as
this has not
been done there
is
demand
for
more
illustrative material.
We have endeavored
to provide this material in the tables compiled in this Appendix, which affords material for the problems illustrating
the fundamental principles given in the text. The principal formulae have been collected under the
different headings, and as supplementary to the subject matter of the text are used to indicate the method of solution
of the problems, instead of giving type solutions. Instead of expressing in words the conditions of a problem, the data have been arranged in tabular form, and the instruc-
tor can clothe the data in the form he
may
desire.
This
method
is
of presentation has several advantages, one of

is
which
compactness, and another
as one of the terms in the table.
that the answers appear For instance, in the Gas
Law Equation pV = nRT, there are five terms, any one of which may be assumed unknown with the others known the value of the one unknown is the answer to the specified problem formulated in any appropriate terms. Another illustration will suffice to represent the general
;
plan of the arrangement and the method of employing the data tabulated. Take the first problem in Table XX, C, 53 4 which as stated in the usual manner would read
:
507
508
PHYSICAL CHEMISTRY
specific
is
5 per cent solution of HC1 the equivalent conductance at infinite dilution A^ is 376, calculate the degree of dissociation. Also calculate the freezing point of the solution. Calculate
The
1
conductance of a
If
at
0.3948 mho.
the vapor pressure. As tabulated there are the following terms the specific conductance *, the per cent composition, the density p, the value of A,*,, all of which may be considered the known data
:
from which the degree of dissociation a, the freezing point, and the vapor pressure may be calculated, and may be termed the answers.
1.
To
calculate the degree of dissociation a,
A F must
first
be obtained from
is
and
but
and the per cent composition.

readily calculated.
2.
V is obtained from Now knowing A F and

and the
A^, a
With the data
given, the freezing point
vapor pressure of the solution may be calculated. Now, considering these answers as part of the given data, other problems which illustrate the principles involved equally as well as the above problems may be formulated, and the answers appear in the table. A few of these may be
outlined.
3.
calculate the degree of dissociation point of the solution.
Given the vapor pressure and the concentration, and the freezing
4. Given the freezing point and the concentration, calculate the degree of dissociation and the vapor pressure of the solution.
5.
Select the proper data
and calculate the concen-
tration of the solution from the freezing point, the vapor pressure, and the electrical conductance of the solution.
6.
Calculate
the
specific
conductance,
given
the
concentration of the solution.
From
the data tabulated in these ten problems,
we not
in the
only have thirty problems on the basis that the values
APPENDIX
last three
509
we could have all
columns are the answers, but as indicated above, together over one hundred problems. The same holds for the other tables. We have a great variety offered, with the answers in one of the columns.
TABLE
Percentage Composition and Formula
The formula
of a
compound
is
a combination of symbols
that represents the percentage composition of the and such that the formula weight in grams of the
in the gaseous
compound compound
state occupies
If
22.4 liters of space under
standard conditions.
the
compound cannot be obtained
in the gaseous state, then other facts are used, such as the effect of the compound upon a solvent in lowering the vapor
pressure, lowering the freezing point, raising the boiling point. In general, the formula of a compound is obtained by the
following rule
Use
the simplest combination of symbols that represents the
percentage composition of the
compound and
agrees with the
known facts.
510
PHYSICAL CHEMISTRY
TABLE
II
The Gas Law Equation

expresses the relationship of the mass, pressure, temperature, and volume of a gas may be utilized in solving problems involving these variables.
The Gas Law Equation pV = nRT which
For a given gas we then have
pV = nRT,
or pv
rT, in which
R = mr and
(a)
Or
if
any three
of the values
g,
V, T, and p are known,
the other
may
be calculated.
(b) For a constant mass of gaseous substances which would occupy a volume of V, at the temperature /, and pressure p, either V 2 t 2 or p z may be readily obtained if the other two are known.
, ,
The data for problems given in the following tables are arranged so that the values describing the conditions under which the gas exists are designated by the same subnumbers. In Table II problems might read 1. What will be the volume of at 20 C. grams of and under a pressure of 750 mm. ? -2. At what temperature will grams of occupy liters under a pressure of 750 a volume of mm./
:
j. Under what pressure will liters at temperature volume of

4.
gt ?
of
occupy a
How many
mm.
?
grams of
liters
will
a volume of
750
at 20
be required to occupy C. under a pressure of

desig-
Or these same problems, assuming that the condition nated by the subscript i are known,
APPENDIX
1.
511
raised so that
it
To what
If
t2
must the gas be
will
occupy a volume
2.
the gas
is
at the pressure p 2 ? heated to a temperature

2
t2 ,
what
vol-
ume
j.
will it
To
its
the pressure is p 2 ? occupy, what pressure must the gas be subjected so

2 , if
volume will be V 2 at t 2 ? Or the values indicated by the subscript 2 may be assumed to be the known values and in the manner just indicated the values marked by the subscript i calculated.
that
SUBSTANCE
PHYSICAL CHEMISTRY
TABLE IV
The
Specific
Gas Constant
Given the weight
culate the specific gas constant,
of one liter of the following gases, calr, and express the same in
liter-atmospheres per degree
and
in gram-centimeters per
degree
APPENDIX
TABLE VI
Molecular Weight and Formula
513
Calculate the molecular weight or obtain the formula.
These
may
all
be solved from
pV = nRT and
g n =
SUBSTANCE
'
PHYSICAL CHEMISTRY
Dissociation of
PC1 5 under Atmospheric Pressure
APPENDIX
TABLE IX
Dissociation of
515
NH HS
4
4 HS to be a solid and the part vaporized to Assuming be completely dissociated

:
NH
1.
From
the mass
V and
calculate the partial pressures.
Now by introducing a given mass of one of the products

compute the
partial pressures
of dissociation
and the per-
4 HS which remains dissociated. centage of the original Calculate the specific gravity with respect to air of each 3 of the mixtures.
.
NH
PHYSICAL CHEMISTRY
k,
=
2(1
respectively.
The
2
equilibrium equation for

2
a)
the dissociation of
NO
2
is
NO
;:
N0
or \
ki
NO
2
^
a2
NO
a
2.
Show
k2
that
-
the
dissociation
constant
is
=
i
A.
and
a
a)
2
(i
respectively, in
which one
is
the square root
of the other.
From
the following data for hydriodic acid calculate the
degree of dissociation a, or the equilibrium constant kz at the different temperatures, assuming that the value of a is known
:
APPENDIX
suiting gases of 0.32.
3
?
517
is
K at this temperature
2
2
2
in the
neighborhood
CO + H = CO + H O +
C+
67750
cal.
Under equilibrium conditions Let x volume CO 2 then % = volume H 2 O x = volume H 2 0.5 = volume CO -5 3 x
.*.
x X
= = =
total final
x
I
Pcot
HJO
0.5
volume
x
0.5
I
(0.5
~ 2 *) = - 3*
x X
Pco
0-22
Solving,
2
x x
X #
= =
0.069
= =
6.9 per cent
gas lost in reaction

0.862
8 per cent
=13.8 per
cent
CO
2
x
I
0.060
2
0.862
8 per cent
HO
=
2
I.
^
0.862
50 per cent
the principles illustrated in the solution of the above, problem apply these to a mixture of 1000 cubic feet each of carbon monoxide and hydrogen, assuming that no hydrocarbons are formed and that there is a net loss of 13.8
From
what is the number of cubic per cent due to the reaction feet of the gaseous constituents and the number of pounds of
;
carbon formed
stituents
What
?
is
permanent gas and how many cubic

remain
the percentage composition of the feet of the original con-
518
II.
PHYSICAL CHEMISTRY
If
i
liter of
carbon dioxide
is
passed over carbon heated
at 600, calculate the composition of the resulting mixture C = 2 CO. assuming the reaction to be CO 2
K
Let
I
(CO)' -
_
'
2 x
= volume = volume
=
i
of of
CO CO
Ans. Final volume

2
+x
If
final
volume
CO = percentage CO = percentage CO =
volume
2
1.156 0.312 26.99 73.01
liter liter
III.
liter of
CO
forms
CO
and carbon at 750,

2 (CO) '
v
calcu-
late the percentage composition of the resulting
mixture and
the degree of dissociation.

Ans. Percentage dissociation Percentage CO2
KP =
= =
0.27 22.7
CO
3.94
Percentage
CO =
77.3
IV.
Ethylene dissociates into acetylene and hydrogen.
The
values for the equilibrium constant
KP =
C* 2 TT *
TT
-
at
2 .H.4
the temperatures 600, 750, and 900 C. are 0.00018, 0.0093, and 0.0178 respectively. Calculate the volume of acetylene
and the
Ans.
total gas
volume at the
different temperatures.
600
750
900
Volume
of acetylene
. .
...
.
Total volume
0.01342 1.01342
2
0.09602 1.09602
0.1323 1.1323
V.
If 0.5 liter of
NO and 0.5 liter of O
are allowed to
come
to equilibrium at 2195 of the mixture.
C., find the percentage composition
KP =
Ans.
P NO =
0.0242
Degree of dissociation a
0.0119
NO =
O =
2
N =
2
1.19 per cent 20.4 per cent 77.4 per cent
APPENDIX
VI.
519
of mixtures of
:
The percentage composition

3
N H
2,
2,
and
NH
is
given in the following table
520
PHYSICAL CHEMISTRY
IX. The following are the values of
KP =
from
Bodenstein's measurements for the reaction
SO 3
,
^ SO
TEMP.
+\O
2.
.
for the values of
KP
Calculate the degree of dissociation,
APPENDIX
521
TABLE XII
Surface Tension and Association Factors
1.
By employing
the equation y
the value for any
one term
The
2.
may be calculated, providing the others are known. values of these terms are given in Table XIII, from
y.
which calculate
(where
r
The constant
of
the equation
6)
is
tt
t,
d) y(mV)% = k\(r in order to calculate required
the association factor x (from the equation x
and
k\j
tained
which has a value of 2.12 for normal liquids, is obby solving two simultaneous equations for different
temperatures.
for
ki,
of different temperatures,
In the table are given the data at a number from which calculate the value then calculate the association factor.
is y = kw, in which w is the weight of a drop and k is a constant for a given tip of the capillary tube from which the liquid drops. In calculating the association factor from the falling drop data, the same general formula as was used above is employed but instead of 2 1 2 the constant for normal liquids, the constant kw obtained from the following relation, must be employed, y w 2.12 k w
Tate's
Law
of the liquid
Solving,
we have kv
2 12
'
w
.
Calculate the association fac-
tor, using the
weight of the drop.
The capillary constant or the specific cohesion is represented by a2 and by definition we have a2 = rh. From the = 9 r ap = &LB. we then have, since =
3
. ,
equation y
981, y
and when a2
is
expressed in millimeters
we have y =
ap
,
0.204*
522
or a2
PHYSICAL CHEMISTRY
=
p
4_2.
Calculate the values for a 2 from the data

table.
in the
accompanying
TABLE XIII
Relation of Latent Heat of Vaporization and Trouton's Law
a?,
and
SUBSTANCE
APPENDIX
by the constant, the
result
is
523
a value that approximates very
closely to that given for the association factor in the last
SUBSTANCE
524
PHYSICAL CHEMISTRY
temperature on the Absolute scale at which the heat of The boiling point under vaporization was determined.
The 760 mm. pressure is usually given in the formula. value of the constant can be calculated if the other values are given, or assuming all values known but one, this may
be calculated.
TABLE XIV
Construction of Temperature-Concentration Diagrams
From
liquidus
the data for each of the following systems, plot the and solidus curves on a temperature-concentration
diagram, and draw the horizontals at the transition points and Indicate the solid phase separating along each liquidus curve, and the components of the systems
at the eutectic points.
in equilibrium in the various areas into
which the curves
divide the diagram.
APPENDIX
525
PHYSICAL CHEMISTRY
APPENDIX
The molecular
hydrogen
line
527
line or for the refractivity for either the be calculated. may By calculating both of
these values the molecular dispersion
may
be obtained.
528
PHYSICAL CHEMISTRY
TABLE XVI
Calculation of Osmotic Pressure
Calculate the osmotic pressure from the data given in the Or, assuming the osmotic pressure known, following table. calculate the apparent molecular weight, A and then the
degree of dissociation, a. For additional problems see tables of data, page 534.
SOLVENT
APPENDIX
529
TABLE XVII
Osmotic
Pressure,
Comparison of Normal Weight Normal Volume Concentrations

in the following table
and
lation
Check the values for p from density tables Landolt and Borns tern's
by interpoof sugar solutions such as given in Then express the conTabellen.
and
centration in moles per liter (molal volume concentration) in moles per 1000 grams of solvent (molal weight concen.
Calculate the osmotic pressure, using each of these tration) values for the concentration and ascertaining which set of results conforms more nearly to the observed values.
530
PHYSICAL CHEMISTRY
TABLE XVIII
Vapor Pressure Calculations
In order to determine the molecular weight from the lowering of the vapor pressure Raoult's modified formula for the
vapor pressure
is
used
Solving
Since
m mA
-?-
solve for
i.
Since
a =
^,
solve for a.
The following data are for aqueous solutions wherein 100 grams of the solvent were employed in each case. The vapor
pressure of water at o
C.
is
4.62.
SOLUTE
APPENDIX
531
532
PHYSICAL CHEMISTRY
calculate the degree of dissociation. Assuming the formula weight, m, calculate the apparent molecular lowering, A For additional problems see or the apparent molecular rise.
tables of data, page 534.
SOLUTE
APPENDIX
.
533
534
PHYSICAL CHEMISTRY
TABLE B
EQUIVALENT CONDUCT-
ANCE
APPENDIX
535
depending upon the assumptions made. Two of the simple cases may be illustrated by a consideration of uni-univalent
or bi-bivalent
1.
and
PbSO 4
]
.
Action [Pb++ ]
[Pb
++
^ [Pb
of uni-bivalent salts as PbSO 4 and PbCl 2 ++ then from the Law of Mass
]
+ [SO ~
4
.
[SO 4 ~] = L
But the concentration
of the
= L (NH
the concentration of the [SO 4~] = VZo or [Pb ++ ] 2 Now assume that a definite concentration, c, of
is
)2
SO 4
added to a
4
.
solution of
PbSO
]
What
Pb+ + present ? = LQ but [Pb ++

;
We
=
[SO 4~]
or
[SO 4
-+
[Pb ] [SO 4 [S0 4~~] in concentration, hence

c]
2
specified quantity of the saturated will be the concentration of the ++ would then have
c]
=L
or [SO 4-] 2
c[SO 4-]
= L
[S0 4 -]
c[S0 4-]
Lo
o.
Solving this quadratic equation for [SO 4~~] gives the ionic concentration from which the solubility of PbSO 4 is readily
obtained.
and then [Pb ] [I~] [Pb ] [2 I-] But there are twice as many [I~] as [Pb ++ ], hence
2.
:
PbI 2
++
++
[2
Pb++ ].
Then [Pb ++
and
4
[2
Pb++
2
]
= L
or 4 [Pb ++ ] 3
= L = [I~] = L or
2
.
[Pb++l
of the
[I-]
17,
from which the
solubility
individual ions.
PbI 2 can be calculated or the concentration of the Now if an electrolyte with a common ion is added to a saturated solution a cubical equation is obtained. Show the form of this expression and how it
be employed in determining the solubility of the diffiIt must be remembered in solving the cultly soluble salt. cubical equation that since the root is a very small decimal the terms involving the second and the third powers are practically negligible with respect to the first power, hence a very close approximation may be obtained by employing the term involving the first or the second power and solving. This method of approximation was utilized to obtain the
values in the last column.
may
536
PHYSICAL CHEMISTRY
the data presented in the table, calculate the Ionic This is obtained by expressing the concentration of the ions in terms of gram-ions per liter and the solu-
From
Product.
obtained from these values would be expressed in gram-molecules or moles per liter. To 100 cc. of a saturated solution of the substance listed
bility
column add 100 cc. of the designated solution an electrolyte containing a common ion. This substance is assumed to be completely dissociated, and the solution of the original substance is to remain saturated. Calculate the concentration of the original substance and express the same in moles per liter.
in the first
of
APPENDIX
537
TABLE XXII
Ionic Product, Solubility and Specific Conductance
the data in the following table and the equivalent conductances ionic given in Table L, page 320, calculate the in moles per liter. Assume the conductance of solubility the water to be i.2Xio~ 6
ionic product.
specific
From
mhos
in all cases.
solubility
Calculate the
calculate the
Or assuming the
conductance of the solution.
SUBSTANCE
PHYSICAL CHEMISTRY
in
Table LVI calculate the hydrolytic constant for the substances in the following table and then calculate the per cent of hydrolysis at the specified temperature.
SUBSTANCE
APPENDIX
TABLE
539
XXVI
Table of Atomic Weights
The values given in this Table of Atomic Weights are the ones that have been used in the problems.
Aluminium Antimony Argon
INDEX
Absolute zero, 51 Absorption coefficient, definition of, 155 table of, 155
Acceleration, definition of, 3 Acid, definition of, 328
relative strength of, 383 Additive properties, 331 Adiabatic, definition of, 284 Adsorption, 453
Bimolecular reactions, 484, 491 Binary Systems Cu-Ag, 241 Cu-Zn, 248 Hg-Cd, 239 Iron Carbon, 250 KCl-AgCl, 210 212 2 CO 3 -Na 2 CO 2
K K SO -MgSO
2
4,
243
,
Li2 SiO 3 -MgSiO 3 242
dyes, 456 Adsorption compounds, 454 Affinity, 475, 476 Allocolloids, 445 Allotropes, 189 Allotropy, 189 types of, 190 Association constant, 402
by by
charcoal, 454
Mg-Sn, 244
MgSiO 3 -MnSiO 3
Pb-Sb, 211
241
Birotation, 142 Boiling point constants, table of, 299 curves, types of, 175, 176, 178,
Association factor, termining, 119 Asymmetry, 136 Atomic heat, 413

definition of, 90
method
of de-
179 equation, 298 of concentrated solutions, 374

of solutions, 273
Boyle's Law, 19
deduction
of,
from the Kinetic
Theory
of Gases, 85
Atomic theory,
Dalton's statement of, 38 Lucretius' statement of, 37
deviation from, 46 Brownian movement, 465

Calorie, definition of, 412 Calorific power
Atomic volume, 113 Atomic volume curve, 69
of foods, 425 Avidity, 355 of fuels, 419 Avogadro's Hypothesis, 17, 41 deduction of, from the Kinetic Cannizzaro's Theory of Atomic Theory of Gases, 86 Equivalency, 43 Carnot's Cycle, 284 Base, definition of, 328 application of, to solutions, 287 relative strength of, 353 Catalysis, 458, 498 Basicity of organic acids, 331 Catalysts, 498
542
Catalysts, metallic, 502 Catalytic agent, 498 processes, 501 Catalyzer, 458 Cataphoresis, 452 Cell constant, 315 Charles' or Gay Lussac's
INDEX
Copper sulphate- water system, 226
Corresponding states, law of, 109
Critical constants,
in
calculation of,
104
Critical pressure, definition of, 171
Law, 20
Critical
solubility,
temperature,
deduction
of,
from the Kinetic
159
Critical temperature, definition of,
Theory
of Gases, 83
of,
Chemical affinity, 476 Chemical compound, definition

9,
171
Critical thermal points, 251
151
of,
Chemical formula, definition

Clausius' equation, 100 Clausius' theory, 307
14
Cryohydrate, 209 Cryohydric point, 209 temperature, 209 Crystalloids, 255, 435
Dalton's absorption law, 155 Dalton's Law, 60
Coagulation, 448
by
electrolytes,
449
322,
Colligative
properties,
371,
402
Colloidality, 442
Deacon
process, 501
Colloid chemistry, 443, 445 applications of, 468 Colloids, 255, 435 general character of, 437 Colloid solutions, colligative propof, 461 physical properties of, 459 Colloid state, 440, 444 "Colloid systems, preparation
Degree of reaction, 485 Deliquescence, 228

Density, definition
of, 5 relations of gases, 30
erties of, 460 osmotic pressure
of,
473
by condensation, 473 by dispersion, 473, 474

Components,
definition of, 148
Concentrated solutions, 358 Conductance, effect of temperature on, 330 Conductors, electrical classes of, 301 Conjugate points, 165 Consolute liquids, 157 Constant boiling mixture, 178 Contact poisons, 503
Cooling
types
curves,
of,
Deviation from Charles' Law, 49 Dialysis, 255, 436 Dielectric constant, 399 table of, 400 Diffusion, 433 Diffusion of gases, 87 Dilution Law, Bancroft's, 331 Ostwald's, 337 Rudolphi's, 338 van't Hoff's, 339 Disperse means, 441 phase, 441 system, 441 Dispersion, degree of, 441 Dispersivity, 132 Dispersoids, 441 classification of, 442 Dissociation constant, 58, 337, 340 degree of, 54 of gases, 52, 60
of water, 387 Distribution Law, Nernst's, 166 Doebereiner's triads, 66
construction
of,
207, 245
231-233
INDEX
Dualistic theory, 302 Dulong and Petit 's Law, 413 Dumas' method, 31 Dynamic allotropy, definition of,
543
Exothermic reactions, 418 Explosion, time of, 497

Faraday, a, 308, 323 Faraday's Law, 304
Ferric chloride-water system, 224 Flash point, 495 Force, definition of, 4 unit of, 4 Formula volume, 16
192
Dyne,
definition of,
Efflorescence, 228
Effusion, Graham's Law of, 88 Electrical conductance, 301
Electrochemical
theory,
Davy's,
Formula weight,
301
Electrolysis, definition of, 305 Electrolytes, classification of,
328
14, 32 Fractional crystallization, 238 Fractional distillation, 177 with steam, 181
definition of, 305
Electrolytic dissociation, 321
degree
of,
325
table of, 326 theory, 323
Electromagnetic
142
rotatory
power,
Freezing curve, 209 Freezing mixtures, properties, 214 Freezing point constant, 299 equation, 297 'gram-molecular lowering of, 294 of concentrated solutions, 373
of solutions, 273 table of, 296
Element, definition of, 8 Emulsoids, 446 Enantiotropic substances, 190

table of, 191
Freezing point curves, intermediate, 236
Type
I,
Endosmose, 452
Endosmosis, 255
maximum, 236 minimum, 237 Type II, show transition

238
point,
Endothermic reactions, 418

Energy, availability of, 283 Enzymes, 458 Equation of state, 18
the reduced, 108
show eutectic point, 241 show chemical compound, 243 Friedel and Craft's reaction, 501
Froth, production of a, 471 Fusibility curves of binary alloys,
Equilibrium constant, 58
labile,
187
electrolyte
in
231
solution,
of
an
Fusion point, 204

Gas, as solvent, 152 as solute, 153
337 Equivalent conductance, 314

of inorganic salts, table of, 316 method of calculation, 329 Equivalent ionic conductances,
Gas Law,
the, 18
table of, 320
Eutectic, 209 point, 209 table of, 213
constant of, 24 deduction of, from the Kinetic Theory of Gases, 82
Gas law equation, application

to osmotic pressure, 261
of,
temperature, 209 Exosmosis, 255
development
Gel, 444
of,
21
544
Gladstone- Dale formula, 125 Graham's Effusion Law, 88
INDEX
Ionization constant, table
Isocolloids,
of,
341
445
Gram-molecular volume, 26, 29 Gram-molecular weight, 25 Gravitational units, 4 Grotthus' Theory, 305
Isohydric solutions, 343

definition of, 347 Isomorphous mixtures, 229 Isothermal, definition of, 284 Isotonic solutions, 264
Heat capacity, definition of, 90 Heat of combustion, 416, 418

dilution, 416, 418, 427 relation to osmotic
Isotropes, 9
366
dissociation, 431
formation, 416, 418

fusion,
Kindling temperature, 495 pressure, Kinetic Theory of Gases, 82 deduction of the Gas Law from, 82 Kohlrausch's Law, 313, 318
418
hydration, 428 ionization, 416, 431

neutralization, 416, 429 precipitation, 198, 416,
Law,
definition of, 6
15,
Law of combination by volume,

39
427,
definition proportions, 6, 8
429
reaction, 416
solution, 416, 427
mass action, 56, 478 thermodynamic deduction 480

mixtures, 369 octaves, 69
of,
vaporization, 416 Henry's Law, statement of, 153 exceptions to, 154 Hess' Law of Constant Heat Summation, 417 Hydrate theory of solutions, 368 Hydration of ions, 380, 383 Hydrogenation of oils, 503 mechanism of, 504 Hydrolysis, degree of, 391 table of, 393 Hydrolytic constant, 389
Ignition temperature, 495 Index of refraction, 123 Inversion of cane sugar,
Linder-Picton-Hardy Law, 450

Liquids, physical properties of,
in
Liquidus curve, 234 Lorentz-Lorenz formula, 125 Lyophilic colloids, 446 Lyophobic colloids, 446
Mass
action,
law
of,
478
Mass, units
Mass Law
Matter, 3
3 equation, 58
of,
Maximum
by
acids,
489
by
salts,
490
Ionic product, 350

definition of, 351 of water, 387
point of mix1 80 Melting point, congruent, 222 Meso form, 138 Minimum boiling point of mixtures, table of, 1 80
boiling
tures, table of,
crystals, 229 Mole, definition of, 25 Molecular conductance, 315 Molecular formulae, 32, 33 Molecular heat, 415
Mixed
table of, 353

Ions, 323 definition of, 304
neutral effect
of,
347
definition of,
90
INDEX
Molecular theory, the, 43 velocity, 86
volume,
Oxidation and
tions of, 333
545
reduction,
defini-
in
Parke's process, 165 Partially miscible liquids, 157 Peptization, 444 Perfect solutions, 358 Periodic Law, the, 69 Periodic Systems, the, 64
of, 77 imperfections of 78 Periodic table, the, 68 discussion of, 71
,
weight, determination of, 29 by freezing point method, 277 by boiling point method, 279 Monomolecular reactions, 482, 487 Monotropic substances, 191 Monotropy, definition of, 192
Motion, definition of, 2 Multiple proportions, law

Muta-rotation, 141
Nicols prism, 134
advantages
of, 8,
10
Nonaqueous
solutions,
of,
electrical
Pfeffer's
of,
graphic representation of, 80 osmotic cell, description
conductance
theories of, 406
396
259
of,
Phase, definition
146
Nonmiscible
liquids, 157
Phase
freedom,
rule, applications of, 248,
253
Number
degrees of definition of, 184

of
definition of, 185
Optical rotation, 133

effect of
temperature on^ 139
of concentration, 140 of solvent, 141
Phases, conception of, 185 separation of, 150 Plasmolysis, 263 Polarimeter, 135 Polarized light, 133
measurement
of,
134
molecular, 135 specific, 135
Polymorphism, definition of, 189 Poundal, definition of, 4 Precipitation membranes, 258
Pressure, definition of, 5
Ore
flotation,
469
of,
Promoters, 502
Osmosis, definition
255
nature
of,
mechanism of, 256 Osmotic phenomena, 462 Osmotic pressure, 255

application
of
Protective colloids, 458 Prout's hypothesis, 64
Pseudo-osmotic pressure, 464
Quadruple point, 206
the Gas Law Racemic mixtures, 138 Equation to, 261 Raoult's Law, 266 factors affecting, 463 of colloid solutions, 461 Reciprocal Proportions, Law of, 10, ii of concentrated solutions, 365 Reduced temperatures, in, 120 of solutions, 262 relation of, to concentration, 258 Refraction, double, 133 of light, 122 to boiling point, 299 Refractive power, methods of exto freezing point, 292
to temperature, 260 to vapor pressure, 290, 291
pressing, 125 Refractivity, specific, 125 molecular, 126
Ostwald's Dilution Law, 337
546
Refractivities, table of, 127 of isomeric substances, 128
INDEX
Specific heats of gases, 90
Cont.
Refractometers, kinds
of,
131
of water, table of, 91 ratio of, 95

of,
Saponification of esters, 492
Saturated solutions, definition 195 Shaking out process, 166

Snell's
Specific surface, 441 Speed, definition of, 2

Stere, 114
Stoke 's law of moving particles, 467 Sublimation curve, 172 Law, 123 definition of, 172 Sodium chloride- water system, 204 Sodium sulphate- water system, 216 Sulphur, system of, 193
temperature concentration dia- Sulphur trioxide- water system, 224 Sulphuric acid, contact process, 505 gram, 2 17 pressure temperature diagram, Surface tension of liquids, 115 Ramsay and Shield's work on, 1 16 219 Suspensoids, 446 Sol, 443 Solid solutions, 229 Symbol weight, 14 determination of, 29, 33 definition of, 151 or atomic weight, 34 Solidification curve, 209
Solidus curve, 234 Solubility curve, 195, 219 of hydrates, 220, 221
of
System, definition of, 146 Systems, divariant, 186 mono variant, 186
SO 3 369
,
non variant, 187

on a
tri-
of water-ether-alcohol
angular diagram, 163

pitch of, 197 types of, 1 60 Solubility product, 351
Solubility, relation of, to chemical
Tate's Law, 119
Temperature of explosion, 495 Theorem of Le Chatelier, 199

geological application of, 201
Theory, conception
,
of, 36,
37
character, 196 Solute, definition of, 151 Solution, definition of, 151
Solutions, 146, 440 of solids and liquids, 229
Thermal neutrality of salt solutions,

law of 429 Thermochemistry, 410 first law of, 417 Thermodynamic deduction of law
of
types
of,
204
mass
action, 480
for con-
Solvent, definition of, 151

Specific conductance,
Thermodynamic equations
Thermodynamics
first
,
314
centrated solutions, 360
Specific gas constant, 25 Specific gravity, definition of, 5
law of, 282 second law of, 283 Specific heats, at constant volume, Thomson's hypothetic curve, 102 9i Tie line, 164 at constant pressure, 91 Torricelli's Law, 88 difference of, 93 Transference numbers, 308 methods of determining, 95 table of, 312 of compounds, 415 Transition point, definition of, 190 of elements, 413
INDEX
Triangular diagram, 161 Trimolecular reactions, 485
Triple point, definition
of,
547
Cont.
Vapor pressure
187
of concentrated solutions, of hydrates, 224 of ice, table of, 173 of water, table of, 170
376
Tyndall
Trouton's Law, 120 effect, 439
relation to osmotic pressure, 270
Ultramicroscope, the, 439 Unit, definition of, I Units, fundamental, 2

derived, 2
gravitational, 4 of chemistry, 12
of force, 4 of mass, 3
Vectoriality, 447 Velocity, definition of, 3 Velocity of reactions, factors which

influence, 495
Victor Meyer's method of vapor density determinations, 32 Volume normality, 359
Universal gas constant, 25 numerical values of, 26
Van der Waals'

application
equation, 97
of,
100
Water, as catalyst, 500 constitution of, 383 dissociation of, 386 ionic product of, 387 system of, 186
Water-aniline system, 159 Water-ether system, 185 Weight, normality, 359 definition of, 4 Working hypothesis, 36
Wiillner's
Vapor composition curve, 177 Vapor pressure curve, 169

limits of, 171
types
of, 173,
174
definition
of,
Vapor
1
pressure,
of, of,
68
Law, 266
lowering lowering
265
in
relation
to
os-
motic pressure, 290
Zone Zone
of
of
anamorphism, 201 katamorphism, 201
UNIVERSITY OF CALIFORNIA LIBRARY
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on the
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1947
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TEXTBOOK OF

PROFESSOR OF PHYSICAL CHEMISTRY RENSSELAER POLYTECHNIC INSTITUTE

this is absolutely necessary is the experience of

The order ment of the

explanation of the facts

some cases to show that the

facts are not in accord with

the present theories. by recording after the

This chronological sequence

of this matter has

that the answers appear as one of

clothe the data in whatever form he

have been presented so that the student

the voluminous literature more accessible

be in a better position to see the

geners, Including the

Organic Chemistry for Advanced Students

Handbook of Colloid Chemistry by Wolfgang Ostwald, translated by Martin H. Fischer.

SOLUTION OF LIQUIDS IN LIQUIDS SOLUTION OF LIQUIDS IN LIQUIDS

EQUILIBRIUM BETWEEN THE DISSOCIATED AND UNDISSOCIATED PARTS OF AN ELECTROLYTE IN

NONAQUEOUS SOLUTIONS THERMOCHEMISTRY

RATE OF CHEMICAL REACTIONS

to obtain the dimensions of substances or their distances

visor in order to ascertain

times this arbitrarily

magnitude of the same.

The measure of this unit quantity number i. The fundamental units

quantity to be measured with our unit.

the comparison of the This may be ac-

the change of velocity

has been from

of the existence of that

weights. Units of Mass.

mass are founded on the

This standard of mass,

made by Borda, which was intended

on one gram causes an The force of one dyne produces

the weight of one

equivalent to 981 dynes.

This has different values at different places.

used the intensity of pressure

the ratio of the mass of a

where g is the mass

of the substance, and g, the standard substance.

the mass of an equal volume of It is not always customary to com-

and the other substance compared with

ture, this is usually expressed -^

some other temperature, as 20, the comparison with water

would be indicated as follows

that both the substance and the standard are to

should also have

any substance, and

the density of the

LAWS OF COMBINATION AND CHEMICAL UNITS

gathered by observation and experimentation are

THE LAW OF DEFINITE PROPORTIONS

changed to the white

LAWS OF COMBINATION AND CHEMICAL UNITS

experiments showed that 100 parts of potassium chloride

the following relations hold