26.

1 The van der Waals gas 281

Origin of the a/V
2
m
term
Assume n
moles
moles of gas in volume V . The number of nearest neigh-
bours is proportional to n
moles
/V , and so attractive intermolecular in-
teractions lower the total potential energy by an amount proportional
the number of atoms multiplied by the number of nearest neighbours,
i.e. we can write the energy change as
an
2
moles
V
, (26.3)
where a is a constant. Hence, if you change V , the energy changes by
an amount

an
2
moles
dV
V
2
, (26.4)
but this energy change can be thought of as being due to an eective
pressure p
e
, so that the energy change would be p
e
dV . Hence
p
e
= a
n
2
moles
V
2
=
a
V
2
m
. (26.5)
The pressure p that you measure is the sum of the pressure p
ideal
neglecting intermolecular interactions and p
e
. Therefore
p
ideal
= p p
e
= p +
a
V
2
m
(26.6)
is the pressure which you have to enter into the formula for the ideal
gas,
p
ideal
V
m
= RT, (26.7)
making the correction V
m
V
m
b to take account of the excluded
volume. This yields

p +
a
V
2
m

(V
m
b) = RT, (26.8)
in agreement with eqn 26.10. This equation of state can also be justied
from statistical mechanics as follows: taking the expression for the
partition function of N molecules in a gas, Z
N
= (1/N!)(V/
3
th
)
N
, we
replace the volume V by V n
moles
b, the volume actually available
for molecules to move around in; we also include a Boltzmann factor
e
(an
2
moles
/V )
to give
Z
N
=
1
N!

V n
moles
b

3
th

N
e
an
2
moles
/V
, (26.9)
which after using F = k
B
T ln Z
N
and p = (F/V )
T
yields the
van der Waals equation of state.
282 Real gases
The equation of state for a van der Waals gas is

p +
a
V
2
m

(V
m
b) = RT. (26.10)
In this equation, the constant a parameterizes the strength of the in-
termolecular interactions, while the constant b accounts for the volume
excluded owing to the nite size of molecules. If a and b are both set
to zero, we recover the equation of state for an ideal gas, pV
m
= RT.
Moreover, in the low-density limit (when V
m
b and V
m
(a/p)
1/2
)
we also recover the ideal gas behaviour. However, when the density is
high, and we try to make V
m
approach b, the pressure p shoots up.
1
The
1
To understand this, consider eqn 26.10
at some xed T. When V
m
b, the
term (V
m
b) is very small, and hence
(p+a/V
2
m
) (p+a/b
2
) is very big and
hence p increases.
motivation for the a/V
2
m
term in the van der Waals model is outlined in
the box on page 281.
V
p
b
Fig. 26.2 Isotherms of the van der Waals gas. Isotherms towards to the top right of the graph correspond to higher temperatures.
The dashed line shows the region in which liquid and vapour are in equilibrium (see the end of Section 26.1). The thick line is
the critical isotherm and the dot marks the critical point.
26.1 The van der Waals gas 283
Multiplying eqn 26.10 by V
2
for one mole of van der Waals gas (where
V
m
= V ), we have
pV
3
(pb + RT)V
2
+ aV ab = 0, (26.11)
which is a cubic equation in V . The equation of state of the van der
Waals gas is plotted in Fig. 26.2 for various isotherms. As the temper-
ature is lowered, the isotherms change from being somewhat ideal-gas
like, at the top right of the gure, to exhibiting an S-shape with a min-
imum and a maximum (as expected for a general cubic equation) in
the lower left of the gure. This provides us with a complication: the
isothermal compressibility (eqn 16.71) is
T
=
1
V
(V/p)
T
, and for
the ideal gas this is always positive (and equal to the pressure of the
gas). However, for the van der Waals gas, when the isotherms become
S-shaped, there is a region when the gradient (V/p)
T
is positive and
hence the compressibility
T
will be negative. This is not a stable situ-
ation: a negative compressibility means that when you try to compress
the gas it gets bigger! If a pressure uctuation momentarily increases
the pressure, the volume increases (rather than decreases) and negative
work is done on the gas, providing energy to amplify the pressure uctu-
ation; thus a negative compressibility means that the system is unstable
with respect to uctuations. The problem starts when the isotherms
become S-shaped, and this happens when the temperature is lower than
a certain critical temperature. This temperature is that of the criti-
cal isotherm, which is indicated by the thick solid line in Fig. 26.2.
This does not have a maximum or minimum but shows a point of inec-
tion, known as the critical point, and which is marked by the dot on
Fig. 26.2.
Example 26.1
Find the temperature T
c
, pressure p
c
and volume V
c
at the critical point
of a van der Waals gas, and calculate the ratio p
c
V
c
/RT
c
.
Solution:
The equation of state for one mole of van der Waals gas can be rewritten
with p as the subject as follows:
p =
RT
V b

a
V
2
. (26.12)
The point of inection can be found by using

p
V

T
=
RT
(V b)
2
+
2a
V
3
= 0 (26.13)
and

2
p
V
2

T
=
2RT
(V b)
3

6a
V
4
= 0. (26.14)
284 Real gases
Equation 26.13 implies that
RT =
2a(V b)
2
V
3
, (26.15)
while eqn 26.14 implies that
RT =
3a(V b)
3
V
4
, (26.16)
and equating these last two equations gives
3(V b)
V
= 2, (26.17)
which implies that V = V
c
, where V
c
is the critical volume given by
V
c
= 3b. (26.18)
Substituting this back into eqn 26.14 yields RT = 8a/27b and hence
T = T
c
where T
c
is the critical temperature given by
T
c
=
8a
27Rb
. (26.19)
Substituting our expressions for V
c
and T
c
back into the equation of
state for a van der Waals gas gives the critical pressure p
c
as
p
c
=
a
27b
2
. (26.20)
We then have that
p
c
V
c
RT
c
=
3
8
= 0.375, (26.21)
independent of both a and b. At the critical point,

p
V

T
c
= 0, (26.22)
and hence the isothermal compressibility diverges since

T
=
1
V
(V/p)
T
. (26.23)
We have found that the compressibility
T
is negative when T < T
c
and so the system is then unstable. Let us now examine the isotherms
below the critical temperature. Since the constraints in an experiment
are often those of constant pressure and temperature, it is instructive
to examine the Gibbs function for the van der Waals gas, which we
can obtain as follows. The Helmholtz function F is related to p by
p = (F/V )
T
and so (for 1 mole)
F = f(T) RT ln(V b)
a
V
, (26.24)
26.1 The van der Waals gas 285
p p
c
G
V
V
c
Fig. 26.3 The behaviour of the volume
V and Gibbs function G of a van der
Waals gas as a function of pressure at
T = 0.9T
c
.