AN INTERPRETATION O F VAN D E R WAALS' EQUA-

TION FROM T H E STAKDPOINT O F VOLUME

D E T E R M I N E D BY EQUILIBRIUiM O F
PRESSURES

BY TV. V . METCALF

Van der Waals' equation is ( p + a - b) = R T , in

'ti2)(?

which p represents the external pressure; a c 2 , according to

the kinetic interpretation of the equation, represents the pres-
sure which is due to the attraction between the molecules,
and which acts with the external pressure to compress the mass;
t represents the volume; b the correction in the ideal gas equa-
tion necessitated by the volume actually occupied by the mole-
cules; T the absolute temperature; and R a quantity which
is constant for a given mass of a given substance.
In spite of the fact that this equation is not quantita-
tively accurate, the fact that it predicts and interprets quali-
tatively the metastable conditions ; the critical point; the
minimum volume of pc in the case of gases, with the excep-
tional case of hydrogen; and other phenomena; makes it one
of the important generalizations of science. Its most impor-
tant achievement is its qualitative interpretation of the phe-
nomena connected with the boiling points of a liquid at
successively higher pressures until the critical point is
reached, with its continuity between the liquid and the gaseous
states. The equation is one of the third degree in a. Figure I
shows the type of the curves obtained by plotting the equation
for 'L' as a function of T a t successively higher constant pres-
sures; Figure 2 the type obtained by plotting for u as a func-
tion of p a t successively higher constant temperatures.
Each point on these curves represents a condition of equi-
librium between the volume, the temperature, and the external
pressure of a given mass of a given substance. Confining
our attention to Figure I , it is to be noted that the dotted
line bf is not a part of van der Waals' curve. If we substi-
tute b f for bcdej, then the curve abfg represents what happens
when a liquid is heated to its boiling point, then boiled away
at constant temperature, and the resulting T-apor heated
still further. There is a sharp distinction between what hap-
pens along this line b j and what is represented by the curve
bcdej. There are two possible methods by which a given mass
can pass from the liquid to the gaseous condition. One is a
process of evaporation from a surface, and i n ~ o l v e sa dis-
continuous change in volume and in other physical properties.
The other is a process of continuous expansion of the entire
mass, and involves only a single phase and only continuous
changes in properties. The two are wholly independent pro-
cesses, although they may take place simultaneously. Van der

Fig. I
V
]k* Fig. 2
A'

Waals' equation has to do only with the latter,-the con-

tinuous expansion process. The distinction between these
two processes has not always been kept as clearly in mind as
it should have been.
On the curve abcdefg, ab represents the ordinary stable
condition of the liquid; the ordinate of the line bf represents
the boiling temperature; the parts bc and e j represent the so-
called metastable conditions which are realized experimentally
in a superheated liquid and a supercooled vapor; the part
ce represents the unstable condition which has not been studied
experimentally. A comparison of the successive curves of the
figure, plotted for successively higher constant pressures,
shows that as the pressure increases, the maximum and mini-
mum points c and e approach each other horizontally and
 Interpretatioti oj va?z der lT7aals’ Equation, Etc. 707

vertically, and finally, a t a certain definite temperature,

pressure and volume, represented by h, the two points coincide.
Above this critical point ” no unstable condition can inter-
“

xrene between the liquid and the gaseous states.

Van der JTaals’ equation emphasizes the fact of the con-
tinuity of the liquid and the gaseous states, and, according
to the kinetic interpretation of the equation, it makes it clear
that in the liquidas well as in the gaseous state, the volume under
given conditions is the result of an equilibrium between op-
posing pressures, some of which tend to decrease the volume
and others to increase it. The equation may be written
RT
p + a i‘2 = t‘ - [I- ’ in which p represents the external pres-
sure, and a i’? the pressure due to cohesion between
the molecules. This latter pressure the Germans call Binnen-
druck or Kohasionsdruck. In English it is usually called in-
ternal pressure,-an ambiguous term unless distinguished as
positive or negative. I will call it cohesive pressure. In
the case of the more perfect gases it is ordinzrily negligible.
In ordinary liquids however we have reason to believe that
it amounts to some thousands of atmospheres. The external
and the cohesive pressures act together in tending to decrease
the volume. If these were the only pressures tending to
change the x-olume, there could be no volume equilibrium.
There must be another pressure balanced against these two,
which tends to increase the volume. The value of this third
pressure is expressed in the equation by the term RT I’ - b.’
The kinetic theory explains this pressure as due to the total
effect, per unit area, of the blows of the individual molecules.
It is a function of the temperature and of the density.
It is due to the elasticity and to the heat vibrations of the mole-
cules. In the more perfect gases it is comparatively small,-
practically equal to the external pressure. In liquids it is
ordinarily very large,-approximately equal to the cohesive
The term RT, c - b has the dimensions of pressurr, since R has the
dimensions of pv, v - b expresses a volume, and T simply multiplies the term by
a n abstract number without changing its dimensions
708 W . V . Metcalf

pressure. I will call it elastic pressure. The condition of con-

stant volume then, in both states, is expressed by the equation :
External Pressure + Cohesive Pressure =
Elastic Pressure, or p +a ~

‘ir2
=
v
RT
- b.
It is not a new idea to look at these phenomena from
the viewpoint that volume, in the case of liquids as well as of
gases, is determined by an equilibrium of pressures. Harold
Whiting’ in I 884 published a somewhat elaborate mathematical
paper, taking this equation as the starting point of his argu-
ment. Such an equilibrium, in the case of both liquids a n d
gases, is really involved in the kinetic interpretation of van der
Waals’ equation, and it is more or less clearly implied in most
of the thought on the subject1 It has not however been
kept always so clearly in mind as to avoid all confusion of
thought on the subject.
A second point is necessarily involved in the kinetic ex-
planation of van der Waals’ equation. Suppose we have a
given mass of liquid in equilibrium, and we cause a minute
rise in temperature by adding heat. This has no effect on the
external pressure and probably none on the cohesive pres-
sure, but i t increases the kinetic energy of the molecules and
thus increases the elastic pressure. This destroys the equi-
librium by making the force tending to cause expansion greater
than that tending to cause contraction, and an increase in
volume results. As the volume increases, the average dis-
tance between the molecules increases. This does not affect
the external pressure, but both the elastic and cohesive pres-
sures are decreased. If these two pressures decreased by equal
amounts for a given decrease in density,--that is, neglecting
external pressure for the time being, if the density coefficients2
.. .

1 Proc. Am. ilcad., 19,353 (1884). See also Thomas Young, Phil. Trans.
for 1805, p. 43, quoted by hlathews: Jour. Phys. Chem., 17,491 ( 1 9 1 3 ) ;also Lewis:
Proc. Faraday Soc., 7, 94 (1911-12); Bridgman: Proc. Am. Acad., 49, 96 ( 1 9 1 3 ) .
The term “density coefficient” of a pressure means, in this paper,
PI - Pp I dP
or ~ ~ The term rate of change of a pressure with density
PI(D1- DI) P d D ’
dP
means -. The first is the rate of change of the pressure relative to its own
dD
value; the second is its absolute rate of change.
 Interpretation of van der Waals’ Equation, Etc. 709

of the two pressures were equal,-then the equilibrium could

not be restored by expansion and the volume would go on
increasing indefinitely. As a matter of fact the volume in-
creases slightly and then comes t o equilibrium again at the
higher temperature. This must mean that the pressure tend-
ing to cause expansion decreases, as the density decreases,
more rapidly than the pressure tending to cause contraction,
-that is, when the two pressures are equal, that the density
coefficient of the elastic pressure is greater than that of the
cohesive pressure. The equilibrium is thus automatically re-
stored by an increase in volume as soon as the disturbing
cause ceases to act, and the condition is therefore stable. If
the density coefficient of the cohesive pressure were greater
than that of the elastic pressure, then any inequality of pres-
sures would be increased, not decreased, by a change of vol-
ume, and equilibrium could not be restored by expansion or
contraction. No stable equilibrium would be possible in this
case. A necessary condition of stable equilibrium is that the
pressure tending to cause expansion changes with density more
rapidly than that tending to cause contraction.
One further point:-It seems to be true that in the case
of all pure liqhids the coefficient of expansion by heat in-
creases as the temperature rises toward the boiling point.’
There can be but one interpretation, from the standpoint
of pressure equilibrium, for this increase in the coefficient
of expansion. If the density coefficients of the two pres-
sures were the same, external pressure neglected, then a slight
rise in temperature would cause the mass to expand indefinitely,

The only exceptions known to the author are water, which we now be-
lieve to be a mixture of different kinds of molecules rather than a pure liquid,
and several liquids under very high pressure which have been studied by Bridg-
m a n : Proc. Am. Acad., 49, I (1913-14) and Amagat: Ann. chim. phys., 11,
j z o (1877). All of these exceptions are capable of explanation as due to com-
plex phenomena of association and dissociation, although Bridgman suggests
also a second explanation on the basis of the introduction into liquids a t high
pressures of an incipient form energy before the solid condition is reached.
Either explanation would remove these cases from the category of normal pure
liquids.
710 M'. V . Metcalf
as explained above, and the coefficient of expansion would be
infinite. On the other hand, if the density coefficient of the
elastic pressure be very much greater than that of the co-
hesive pressure, then equilibrium is restored by a slight in-
crease in volume and the coefficient of expansion is small.
A small coefficient of expansion, then, means a large difference
between the density coefficients of the two pressures, and
x"c i ' e m . The fact, therefore. that the coefficient of expan-
sion of a liquid increases as the temperature rises must mean
that, while the density coefficient of the elastic pressure on
the right side of the equation is greater than that of the total
pressure on the left, the difference between the two density
coefficients decreases with rise in temperature.
T. W. Richards1 in a recent article calls attention to the
fact that a small coefficient of expansion necessarily involves
a large cohesive pressure. It is of interest to note that the
converse of this, while probably always true, does not follow
necessarily from the nature of the case. We might conceiv-
ably have a large cohesive pressure with a large coefficient of
expansion. If we should have in equilibrium with each other
two pressures whose rates of change with density were the same,
then, however powerful the pressures, a slight force added to
either would permanently destroy the equilibrium, and the
coefficient of expansion would be infinite. The value of the
coefficient of expansion depends ultimately not on the intensity
of the pressures, but on the difference of their density coeffi-
cients. The same kind of statement applies to compressibility.
To sum up, we have three propositions derived as neces-
sary consequences of the kinetic interpretation of van der
Waals' equation: First, volume is determined by an equilib-
rium of opposing pressures. Second, in the case of a stable
liquid the elastic pressure, which tends to increase the volume,
increases with density more rapidly than does the cohesive
pressure which tends to decrease the volume. Third, the
difference between the density coefficients of these two pres-

1 Jour, -4m. Chem. SOC.,36, 2425 (1914)

 lnterpretation o j Llaz der Waals’ Equation,Etc. 7I I

sures decreases as the density of a liquid decreases. The

first of these propositions is not new. Attention has not been
called t o the last two, however, so far as I know, although
they seem to be necessarily implied in the kinetic interpreta-
tion of van der Waals’ equation.
These three propositions furnish a simple interpretation
for the different parts of van der Tiaals’ curve and the phe-
nomena represented by them. Part a b represents the ordinary
stable condition of the liquid, as explained aha\-e. The part
61 represents the metastable condition,-the superheated
liquid. If our propositions represent the real facts, then this is
a true stable condition, so far as the continuous volume change
is concerned. But the liquid is above its boiling point and
therefore there is a strong tendency for evaporation to take
place. I n other words, the conditionis stable in reference to
the continuous volume change, but unstable in reference to
the surface change. If we could exclude the possibility of
evaporation, all portions of this part of the curve might be
realized experimentally. It is the difficulty of preventing
evaporation that makes it difficult to obtain and hold a liquid
in this condition. This difficulty has been partially overcome
in numerous cases, and we are fairly familiar with this meta-
stable condition in the case of many liquids.
The equilibrium conception points also to the real signifi-
cance of the maximum point c on the curve. Continuing to
neglect external pressure, from a to c the condition is stable
because the density coefficient of the elastic pressure is greater
than that of the cohesive pressure, but as we have seen, the
difference between the two coefficients is steadily decreasing.
The point c represents the density a t which the two coeffi-
cients become equal and the equilibrium therefore ceases to he
stable. From c on, the deizsitj, coefjicient &
;() of the cohesive
pressure becomes increasing greater than that of the elastic
pressure. From c to some point, as d,the rate of change 2();
of the cohesive pressure is also increasingly greater than that
of the elastic pressure. But a t the point d this latter change
712 W . V . Metcalj’
reverses, and from d on, the rate of the elastic pressure gains
on that of the cohesive pressure, becoming equal to it again
at e. From a to d the rate of change of the cohesive pressure
gains on that of the elastic pressure, passing it a t c where the
two are momentarily equal. From a to c the rate of change
of the elastic pressure is the greater. From c to e that of the
cohesive pressure is the greater, this difference reaching a
maximum a t d and then decreasing to zero again at e. From
c to e, then, the condition is unstable because the cohesive
pressure changes with density more rapidly than the elastic
pressure, and consequently the equilibrium, if once disturbed,
cannot be restored by the resulting change of volume.’ From
e on, the rate of change of the elastic pressure is greater than
that of the cohesive pressure. The condition is therefore stable
so far as volume is concerned, but from e to J the condition is
that of a vapor below its boiling point, and i t is therefore un-
stable in reference to the surface change. Here again we have
the metastable condition, which simply means a condition of
stability in reference to the continuous volume change, but of
instability in reference to the surface changes of evaporation
and condensation.
Attention was called above to the fact that in the curves
plotted for successively higher constant pressures, the maxi-
mum and minimum points c and c approach each other as the
external pressure increases, and finally come together at h,
the critical point. The reason for this is clear from the stand-
point from which we are viewing the subject. The statement
was made above that the maximum point c represents the
density a t which the density coefficients of the elastic and co-
hesive pressures became equal. This is not strictly true,
1 I t is possible that the passage of a substance through an unstable condi-

tion similar to that from C to E along van der Waals’ curve (Fig. 2) is realized
in nature on the surface of dust particles that prevent the supersaturation of
water vapor. I t is possible that the cause of their action is the condensation
of the vapor onto their surface by adsorption until the vapor reaches the condi-
tion represented by c . After this it would contract spontaneously and practically
adiabatically to a liquid condition. The liquid phase would thus be introduced
and prevent the supersaturation of the remaining vapor.
 Interpretatim OJ van der Waals’ Equation, Etc. 713

however, since we were rejecting for the time being the ex-
ternal pressure. This would be rigidly true only in the absence
of external pressure, an impossible limiting case. The ac-
curate statement is that c, the point a t which the equilib-
rium changes from stable t o unstable, represents the density
a t which the rate of change of the elastic pressure on one
side of the equation equals the rate, not of the cohesive
pressure alone, but of the sum of the cohesive and external
pressures on the other side of the equation. At ordinary
pressures these two statements are nearly equivalent, but as
the external pressure increases it becomes an increasingly
important term on the left side of theequation. Theexternal
pressure does not change with the density. The maximum
point c, therefore, must correspond to a density coefficient
of the cohesive pressure which is somewhat greater than that
of the elastic pressure, in order to make the rate of change
of the total pressure on the left equal to that of the pressure
on the right, and this excess must increase with an increase
in the external pressure. But this increase in the excess of
the density coefficient of the cohesive pressure over that of the
elastic pressure corresponds, as shown above, to a decrease
in density,-that is, to a movement of the point c further to the
right. As the external pressure increases, therefore, the maxi-
mum point c, a t which the equilibrium changes from stable
to unstable, moves toward the right. In an exactly similar
way it can be shown that the minimum point e must move
toward the left with increasing external pressure, and the two
points therefore approach each other horizontally. It is
easy t o show that the vertical distance between them must
also decrease and that they coincide a t a certain definite value
of the external pressure.
The interpretation that this concept gives to the critical
point is of interest. As stated above, there is a certain
maximum possible excess of the rate of change with density
of the cohesive pressure over that of the elastic pressure.
This occurs on the curve of the limiting case of external pres-
sure equal to zero, and is a characteristic of each substance.
7’4 W . V . Jfetcalj

It occurs at the density represented by the point d on the

curve,-approximately that of the critical point, The critical
point is the point a t which, in the equation
External Pressure + Cohesiye Pressure = Elastic Pressure,
the cohesive pressure has become so small a proportion of the
left side of the equation, and therefore of the elastic pressure
on the right, that the maximum possible rate of change of the
cohesive pressure is no longer great enough to make the rate
of change of the total pressure on the left of the equation
greater than that of the pressure on the right Beyond this
point there can be no unstable equilibrium, and the change
from liquid to gaseous state must be a single-phase continuous
process.
In a speech’ made in 1910 in Stockholm, on the occasion
of his receiving the Kobe1 Prize, van der \Iraals made the
following statement in reference to the critical temperature :
“Bei dieser Temperatur sind die koexistierenden Densitaten
gleich gross. Das ist das einzige, was dieser Temperatur eine
Bedeutung gibt, die in allen Beziehungen ihr nicht zukommt.”
If the above treatment of the critical point is correct, there
is a property which characterizes this point which is more
fundamental than the equality of densities, of which the
equality of densities is merely a consequence.
T. W. Richards? has explained the peculiar sensitiveness
to change of volume a t the critical point as due to the fact
t h a t a t this point the \-olume is determined simply by such
an equilibrium of pressures as we are discussing. If our
viewpoint is correct, such an equilibrium exists a t all points
of the curve, as recognized elsewhere by Richards, and the
stability a t any point depends not on the existence of such an
equilibrium, but on the difference between the density coeffi-
cients of the different pressures inL-olved. The sensitiveness
to volume change a t the critical point would be due, not to the
fact that the volume is dependent on an equilibrium a t this
1 Van der IVaals “Die Zustsndsgleichung,” p 14 (1911)
* Jour. Am Chem. S o c , 36, 632 ( 1 9 1 4 ) .
 Iiiterpretatioiz o j x i z der 1T’aals’ Equatio+i,Etc. 715

point, but to the fact that as the substance, in moving along

the curve, passes through the critical point, it is momentarily
in a condition in which the densit>- coefficients on the two
sides of the equation are equal and the coefficient of expansion
is therefore momentarily infinite In both directions along
the curve from the point lz the excess of the density coefficient
on the right side of the equation over that on the left in-
creases ; the coefficient of expansion therefore decreases and
the volume conditions become more stable.
TTe have so far confined our attention to the curves
shown in Fig I . An entirely similar analysis applies t o those
shown in Fig. 2,-the pressure-volume curves plotted a t suc-
cessively higher constant temperatures.
It seems to be true, then, that the equilibrium conception
under discussion furnishes a clear, qualitative interpretation
of all parts of van der TVaals’ cur\-es and the phenomena
connected with them.
It helps also to gixre an insight into other problems,-into
the mechanical explanation of osmotic pressure for example,
and the mechanical explanation of whj- the vapor tension of
a liquid is decreased by dissolving in it a non-volatile substance
without change of temperature. Some hax-e found difficulty
in explaining this latter problem on the basis of the kinetic
theory of solution.’ The vapor tension of a liquid depends
on the rate a t which the molecules escape from its surface.
Cohesion tends t o hinder their escape One might think
therefore that the solute pressure, which acts against co-
hesion, should increase rather than decrease the vapor tension.
A more careful anal!-& however makes the situation clear.
The tendency of the molecules to escape depends on the kinetic
energy of the molecules,-that is, on the temperature,-and also
on the density of the liquid, exactly the factors on which
the elastic pressure depends. n‘hen the solute is introduced,
its gas pressure is added to the previous elastic pressure and
the equilibrium is thus destroyed. The volume therefore
increases until the expansion causes such a decrease in the
See Nernst: “Theoretische Chemie,” 7th Ed., page 248
716

elastic pressure that it, plus the solute pressure, is now equal
to the cohesive pressure plus the external pressure. At this
point the equilibrium is restored. The cohesive pressure
has been decreased,’ due to the decrease in density, but the
decrease in the elastic pressure has exceeded that of the co-
hesive pressure by an amount equal to the solute pressure,
in spite of the fact that the kinetic energy of the molecules has
not changed. We should therefore expect a lowering of the
vapor pressure proportional to the solute pressure,-propor-
tional that is, in dilute solutions, to the concentration. The
equilibrium conception therefore explains the phenomena both
qualitatively and quantitatively. The decrease in vapor ten-
sion, if the thought of this paper is valid, is not contrary to the
kinetic theory, but is what that theory would predict. The
mechanical explanation therefore is as clear as the dynamic.
No mere thermodynamic explanation of a phenomenon is a
complete one. It needs to be supplemented by a clearing up
of the mechanical situation.
If this explanation is the true one, it ought to be possible
to increase the vapor tension of a solution until it equals
that of the pure solvent, by applying to the solution what
Ostwald calls a “Pressung,” equal in amount to the solute
pressure, According to Callender’s* vaporization theory of
osmosis, this is what really does take place at the
semi-permeable membrane when the back pressure becomes
Jager (Drude’s Ann., 41,854 (1913)) argues that because of variation
from Dalton’s law, the solute when added without change of volume adds more
than its normal gas pressure to the elastic pressure of the liquid, b u t t h a t where
flow through a semi-permeable membrane is possible, this flow takes place in
such a way as to automatically restore the equality between the elastic pressure
of the solvent in the solution and that of the pure solvent without, thus leaving
the total elastic pressure of the solution greater than t h a t of the pure solvent
by a n amount just equal to the gas pressure of the solute. If Jager is right,
then the decrease in the cohesive pressure caused by expansion when a solute is
dissolved in a liquid should be just equal to its increase due to variation of the
elastic pressure from Dalton’s law. The two should just balance, leaving t h e
cohesiye pressure of the solvent in the solution the same as t h a t of the pure
solvent.
S a t u r e , 81, 2 3 5 (1909). See also Battelli and Stefanini: Abs. Chem. Soc.,
92, 11, 233 !19o7).
 Interpretation of ‘wzn der Waals’ Equation, Etc. 717

sufficient to stop the flow. Callender assumes that the pores

of the membrane are filled with vapor instead of liquid, and
that the osmotic flow is due to vaporization and condensation
within the pores. If his assumption is correct, his theory
offers a self-consistent and logical explanation of osmosis, in ac-
cordance with the kinetic theory of solution. But ordinarily,
probably always, the membrane is wet by the solvent and
the pores are filled with liquid rather than with vapor. In
this case the kinetic theory offers an equally clear mechanical
explanation of osmosis along the line of LeBlanc’s sug-
gestion.’ In either case, the oft-repeated statement that the
real mechanical cause of osmotic flow is still a mystery is not
true. The kinetic theory offers as clear a qualitative ex-
planation of osmotic pressure as it does of gas pressure, and
the quantitative limitations are analogous in the two cases,
although more complicated in the case of solutions.
Another point should be considered,-the question why
a decrease in density should cause such curious changes in
the relative rates of changes );:( of the two internal pressures
as is described above. As shown, it seems to follow from the
kinetic interpretation of van der Waals’ equation, that when
along any curve the density of the mass is greater than a certain
fixed value the rate of change of the cohesive pressure divided
by that of the elastic pressure increases as densitj- decreases; but
that, a t this particular density of the mass, the process reverses,
and thereafter the value of this fraction decreases as density
decreases. The reason for this is inherent in the nature of the
equation,-in the relative importance in the equation of the
quantities a L~ and b at different densities.
There has been much discussion as to whether the in-
accuracy of van der Waals’ equation is due to the variability
of the quantity “a” or of the quantity “b” or of both. It seems
now to be fairly established that “b” is variable. Van der
Waals’ latest thought2 is that “a” also is variable in all cases.
“Lehrbuch der Elektrochemie,” 3rd Ed., p. 40.
* Van der Waals: LOC.cit., pp.
14-17.
His hypothesis is that as a substance approaches the liquid
from the gaseous state, association always takes place, and
that this causes a decrease in the cohesive pressure and re-
sults in less compression than is called for by the equation.
The theory of the compressibility of the molecule and of the
atom has an interesting bearing on this point In the light
of the evidence presented by Richards and others, and in the
light of our present views a5 to the complexjty of the atom
as well as of the molecule. it seems difficult to doubt that
both the molecule and the atom are compressible and that they
therefore have volume elasticity as well as form elasticity.
Richards believes that as a vapor is cooled the molecules
approach each other until, somewhere in the region of con-
densation, they come into continual contact with each other ;
and that as the liquid is cooled still further the molecules
become more and more compressed. If this is true it intro-
duces a new element into the situation not taken into account
in the kinetic demonstration of van der Waals’ equation,-
namely, the volume elasticity of the molecules and perhaps
also of the atoms. The elastic pressure due to this cause
could not be identical with that due to heat vibrations, since
it would exist in the absence of heat vibrations. Bridgman’
has given us a most interesting discussion of this kind of
elastic pressure. This pressure would be introduced gradually
as the density of the vapor or the gas is increased toward the
boiling point or the critical point. The phenomena produced
would be qualitatively the same as the experimental varia-
tions from van der Waals’ equation. The same lessening
of the full compression called for by the equation would be
produced either by a lessening of the cohesive pressure through
association or by an increase in the elastic pressure due to
molecular compression Van der IVaals’ hypothesis, however,
makes “il” variable in all substances, while the molecular
compression hypothesis leaves it still reasonable to suppose
that in normal liquids “a” is constant and therefore that the
cohesive pressure is a function of the density only, varying
_ _ -
1 Bndgman: L O ~a.t . , 11. 105 and follouing
 Interpetatiow of tiaqq der Waals’ Equation, Etc. jr9

inversely as the square of the volume, as called for by van

der Waals’ equation.
The presentation of the thought of this paper is a purely
qualitative one. In order to give the thought its full value
the density coefficients of the cohesive and the elastic pres-
sures. and their changes with density, would have to be ex-
pressed in terms of the first and second derivatives of the pres-
sures with respect to density, and the relation between these
and compressibility, coefficient of expansion, and other phys-
ical properties would have to be expressed mathematically
and tested experimentall>*. It may prove possible, also, t o
work back by integration to the values of the two internal
pressures, and to determine the laws of their variation. The
question may be raised whether there would be advantage in
substituting a new equation of state, expressed in terms that
can not a t present be measured with any accuracy, in place
of the older one expressed in easily measurable quantities.
The answer is that there is no suggestion of replacing van der
Waals’ equation, but only of supplementing it. The ad-
vantage of the new standpoint is that it is an attempt to deal
directly with the forces themselves, which are the real causes
of the phenomena in question. However the quantitative
side may work out, the fact that the three fundamental prop-
ositions of this paper seem to be necessarily involved in the
kinetic theory would seem to make it legitimate and of value
to use them qualitatively, in order to visualize the phenomena
involved, and in order to check up other thought on the sub-
ject.
Oberlin, 0.