Van der Waals equation approximates real gas behavior

3.
4 Van der Waals Equation of State

3.4.1 Approximating the Partition Function
Rather than perform an exact calculation in powers of a small parameter
(the density), we shall adopt a different approach by making an
approximation to the partition function, which should be reasonably
valid at all densities.
The approximation is based on the single-particle partition function.
Shall obtain an equation of state approximating behaviour of real gases.

Originally proposed by van der Waals in his Ph. D. Thesis in 1873.
4211 Statistical Mechanics 1 Week 3

In the absence of interactions the single-particle partition function is
V
z= 3.
Λ
Recall: factor V comes from integration over the position coordinates.
► How to treat inter-particle interactions – in an approximate way?
Interaction U(r) comprises:

i ) a strong repulsive core at short separations
ii) a weak attractive tail at large separations.
The key is to treat these two parts separately/differently:

i) The repulsive core effectively excludes regions of space from the
integration over position coordinates. This may be accounted for by
replacing V by V − Vex where Vex is the volume excluded by the hard
core.
ii) The attractive long tail is accounted for by including a factor in the
expression for z of the form
− E kT
e
where 〈E〉 is some average of the attractive part of the potential.
► Thus we arrive at the approximation

V − Vex − E kT
z= e .
Λ 3

We have approximated the interaction by a mean field assumed to apply
to individual particles.
This allows us to keep the simplifying feature of the free-particle

calculation where the many-particle partition function factorizes into a
product of single-particle partition functions.
Accordingly, this is referred to as a mean field calculation.

3.4.2 Van der Waals Equation
The equation of state is found by differentiating the free energy
expression:
∂ ln Z ∂ ln z
p = kT = NkT
∂V T , N ∂V T .
Now the logarithm of z is
ln z = ln (V − Vex ) − 3ln Λ − E kT
so that
∂ ln z NkT d E
p = NkT = −N
∂V T V − Vex dV
since we allow the average interaction energy to depend on volume
(density). This equation may be rearranged as
d E NkT
p+N =
dV V − Vex

or
⎛ d E ⎞
⎜ p+N ⎟ (V − Vex ) = NkT .
⎝ dV ⎠
This is similar to the ideal gas equation except that the pressure is
increased and the volume decreased from the ideal gas values. These are
characteristic parameters. They account, respectively, for the attractive
long tail and the repulsive hard core in the interaction. Conventionally
we express the parameters as aN2/V2 and Nb, so that the equation of
state is
⎛ N2 ⎞
⎜ p + a 2 ⎟ (V − Nb ) = NkT
⎝ V ⎠
and this is known as the van der Waals equation of state.

3.4.3 Microscopic ‘estimation’ of Parameters
In mean field, the repulsive and the attractive parts of the inter-particle
interaction were treated separately.
How are the two parameters of the van der Waals equation related to the
parameters of the Lennard-Jones inter-particle interaction?
i) The repulsion is strong. We accounted for this by saying that there is

zero probability of two particles being closer than σ. Then that region of
co-ordinate space is excluded; form of the potential in the excluded
region (U(r) very large) does not enter the discussion.
Interaction → boundary condition. Thus the excluded volume will be

2
Vex = Nπσ 3 ,
3
the total hard core volume.

ii) The attractive part of the potential is weak. Here there is very little
correlation between the positions of the particles; we therefore treat
their distribution as approximately uniform. The mean interaction for a
single pair of particles 〈E1〉 is then
∞
1
E1 = ∫ 4π r 2U ( r ) dr
Vσ
1
∞ ⎧
⎪ ⎛ σ ⎞
12
⎛ σ ⎞
6
⎫⎪ 32πσ 3
= ∫ 4π r 2 4ε ⎨⎜ ⎟ − ⎜ ⎟ ⎬ dr = − ε.
Vσ ⎪⎩⎝ r ⎠ ⎝r⎠ ⎪
⎭
9V
Now there are N(N – 1)/2 pairs, each interacting through U(r), so
neglecting the 1, the total mean energy per particle is
E = E1 N 2
16πσ 3 N
=− ε.
9 V

In the van der Waals equation it is the derivative of this quantity we
require. Thus we find
2
d E 16 3 ⎛ N ⎞
N = πσ ⎜ ⎟ ε
dV 9 ⎝V ⎠ .
These results give the correct assumed N and V dependence of the

parameters used in the previous section. So finally we identify the van
der Waals parameters a and b as
16 3 2 3
a = πσ ε , b = πσ .
9 3

3.4.4 Virial Expansion
It is a straightforward matter to expand the van der Waals equation as a
virial series. We express p/kT as
p N aN 2
= −
kT V − Nb kTV 2
−1 2
⎛ N ⎞⎛ N⎞ a ⎛N⎞
= ⎜ ⎟⎜1 − b ⎟ − ⎜ ⎟ .
⎝ V ⎠⎝ V ⎠ kT ⎝ V ⎠
and this may be expanded in powers of N/V to give
2 3 4
p ⎛N⎞ ⎛N⎞ ⎛ a ⎞ ⎛N⎞ 2 ⎛N⎞ 3
= ⎜ ⎟+⎜ ⎟ ⎜b − ⎟ + ⎜ ⎟ b + ⎜ ⎟ b +K .
kT ⎝ V ⎠ ⎝ V ⎠ ⎝ kT ⎠ ⎝V ⎠ ⎝V ⎠
Thus we immediately identify the second virial coefficient as

a
B2 (T ) = b −
VW
kT .

This has the form as sketched for the square well potential. For this
model we can find the Boyle temperature and the inversion temperature:
a
TB = ,
bk
2a
Ti = .
bk
So we conclude that for the van der Waals gas the inversion temperature
is double the Boyle temperature.
Incidentally, we observe that the third and all higher virial coefficients,
within the van der Waals model, are constants independent of
temperature.

3.5 Other Phenomenological Equations of State
3.5.1 The Dieterici equation
The Dieterici equation of state is one of a number of purely

phenomenological equations crafted to give reasonable agreement with
the behaviour of real gases. The Dieterici equation may be written as
Na
−
p (V − Nb ) = NkTe kTV
.
As with the van der Waals equation, this equation has two parameters, a
and b, that parameterise the deviation from ideal gas behaviour. The
interest in the Dieterici equation is that it gives a reasonable
description of fluids in the vicinity of the critical point.

3.5.2 Virial expansion – for Dieterici equation
In order to obtain the virial expansion we express the Dieterici equation
as
Na
p N −
= e kTV .
kT V − Nb
And from this we may expand to give the series in N/V
2 3
p N ⎛N⎞ ⎛ a ⎞ ⎛N⎞ ⎛ 2 a2 ab ⎞
= +⎜ ⎟ ⎜ b − ⎟+⎜ ⎟ ⎜b − 2 2 − ⎟ +K
kT V ⎝ V ⎠ ⎝ kT ⎠ ⎝ V ⎠ ⎝ 2k T kT ⎠
This gives the second virial coefficient to be
a
B2 = b −
D
kT .
This is the same as that for the van der Waals gas, and the parameters a
and b may thus be identified with those of the van der Waals model. As
a consequence, we conclude that both the van der Waals gas and the

Dieterici gas have the same values for the Boyle temperature and the
inversion temperature.
The third virial coefficient is given by

2
a ab
B3D (T ) = b2 − 2 2 − ;
2k T kT
we see that this depends on temperature, unlike that for the van der
Waals equation, which is temperature-independent.

3.5.3 The Berthelot equation
As with the Dieterici equation, the Berthelot equation is another of
phenomenological origin. The equation is given by
⎛ αN2 ⎞
2 ⎟(
⎜ p+ V − Nb ) = NkT
⎝ kTV ⎠ .
The parameters of the Berthelot equation are given by α and b. We
observe this equation is very similar to the van der Waals equation;
there is a slight difference in the pressure-correction term that accounts
for the long distance attraction of the intermolecular potential.
Since the Berthelot and van der waals equation are related by
a = α kT it follows that the Berthelot second virial coefficient is given
α
B =b−
B
( ) .
2 2
by kT

3.5.4 The Redlich-Kwong equation
Equation proposed by Redlich and Kwong. [Chem. Rev. 44, 234
(1949)] This is another two-parameter equation.
NkT N 2a
p= −
(V − Nb ) V (V + Nb )( kT )1 2 .
It is instructive to compare this with the van der Waals equation, written
in a similar form
NkT N 2a
p= − 2
(V − Nb ) V
and the Berthelot equation
NkT N 2α
p= − 2
V − Nb V kT
- so the R-K equation has a more complicated ‘pressure correction’
term, that includes some temperature dependence.

Expansion of the pressure in powers of the density gives the virial
expansion:
p N ⎛ a ⎞⎛ N ⎞ ⎛ 2 ab ⎞ ⎛ N ⎞
2 3
= + ⎜b − ⎟
32 ⎜ ⎟ + ⎜b + ⎟
52 ⎜ ⎟ +K
kT V ⎜⎝ ( kT ) ⎟⎠ ⎝ V ⎠ ⎜⎝ ( kT ) ⎟⎠ ⎝ V ⎠
and so we identify the second virial coefficient to be
a
B2RK = b −
( kT ) .
32

**3.6 Hard Sphere Gas (not covered this year)
Chaikin and Lubensky: “Although this seems like an immense
trivialisation of the problem, there is a good deal of unusual and
unexpected physics to be found in hard-sphere models.”
P. M. Chaikin and T. C. Lubensky, Principles of Condensed Matter

Physics, Cambridge University Press, (1995)
U(r)
U (r ) = ∞ r <σ
σ =0 r >σ
0
r

There is no analytic solution to the problem. So…….
Three possible approaches:
1 Mean field
2 Virial expansion
3 Molecular dynamics
Task is to solve for the equation of state and, more generally, all
thermodynamic properties.

3.6.1 Mean field treatment
→ Clausius equation of state: p(V – Vex) = NkT .
Correct in the 1-d case

3.6.2 Hard Sphere Equation of State
The equation of state of a hard-sphere fluid has a very special form.

Start from Helmholtz free energy F:
F = −kT ln Z .
Recall that for an interacting gas Z may be written as

Z = ZidQN
where Zid is the partition function for an ideal (non-interacting) gas
N
1 ⎛V ⎞
Z id = ⎜ ⎟
N ! ⎝ Λ3 ⎠
and QN is the configuration integral
− ∑U kT
1
QN = N ∫ e i< j d 3 N q .
V

Equation of state – find the pressure, by differentiating the free energy
∂F
p=−
∂V T , N
∂ ln Z
= kT
∂V T ,N
⎛ ∂ ln Z id ∂ ln QN ⎞
= kT ⎜⎜ + ⎟⎟ .
⎝ ∂V T ,N ∂V T ,N ⎠
Note: QN is independent of temperature. This must be so, since there

is no energy scale for the problem; the interaction energy is either zero
or it is infinite. Thus the ratio E/kT will be temperature-independent.

The pressure of the hard-sphere gas is then given by:
⎛N ⎞
p = kT ⎜ + g ( N V ) ⎟
⎝V ⎠.
The function g(N/V) is found by differentiating lnQ with respect to V.
We know it is a function of N and V and in the thermodynamic limit the
argument must be intensive. Thus the functional form and we have the
low-density ideal gas limiting value g(0) = 0.
The important conclusion we draw from these arguments, and in

particular from the equation above is that for a hard sphere gas the
combination p/kT is a function of the density N/V. This function must
depend also on the only parameter of the interaction: the hard core
diameter σ.

3.6.3 Virial Expansion
The virial expansion is written as
2 3
p N ⎛N⎞ ⎛N⎞
= + B2 ⎜ ⎟ + B3 ⎜ ⎟ + K
kT V ⎝V ⎠ ⎝V ⎠ ,
where the virial coefficients Bm are, in the general case, functions of
temperature. However, as argued above, for the hard sphere gas the
virial coefficients are temperature-independent.
The virial expansion may be regarded as a low-density approximation to

the equation of state – true when only a finite number of coefficients is
available. If, however, all the coefficients were known, then provided
the series were convergent, the sum would give p/kT for all values of the
density N/V: the complete equation of state.

Now although we are likely to know the values for but a finite number
of the virial coefficients, there may be ways of guessing / inferring /
estimating the higher-order coefficients. We shall examine two ways of
doing this.

3.6.4 Virial Coefficients
The second virial coefficient for the hard sphere gas has been
calculated; we found
2 3
B2 = πσ
3
where σ is the hard core diameter.
General term of the virial expansion is Bm(N/V)m, which must have the
dimensions of N/V. Thus Bm will have the dimensions of (volume)m–1.
Now the only variable that the hard sphere virial coefficients depend on
is σ. Thus it is clear that
Bm = const × σ 3( m −1)
where the constants are dimensionless numbers – which must be
determined.

It is increasingly difficult to calculate the higher-order virial
coefficients; those up to sixth order were evaluated by Rhee and Hoover
in 1964, and terms up to tenth order were found by Clisby and McCoy
in 2006. These are listed in the table below, in terms of the single
parameter b:
2 3
b = B2 = πσ .
3
B2/b = 1
B3/b2 = 0.625
B4/b3 = 0.2869495 Rhee & Hoover
B5/b4 = 0.110252 1964
B6/b5 = 0.03888198
B7/b6 = 0.01302354
B8/b7 = 0.0041832 Clisby & McCoy
B9/b8 = 0.0013094 2006
B10/b9 = 0.0004035

3.6.5 Carnahan and Starling procedure
Remarkable procedure: They inferred a general (approximate)
expression for the nth virial coefficient, enabling them to sum the virial
expansion and thus deduce an (approximate) equation of state. The
virial expansion is written as
2 3
pV ⎛N⎞ ⎛N⎞ ⎛N⎞
= 1 + B2 ⎜ ⎟ + B3 ⎜ ⎟ + B4 ⎜ ⎟ + K
NkT ⎝V ⎠ ⎝V ⎠ ⎝V ⎠
This is written out for the known values of the virial coefficients:
2 3
pV N ⎛ N⎞ ⎛ N⎞
= 1 + b + 0.625 ⎜ b ⎟ + 0.2869495 ⎜ b ⎟ +
NkT V ⎝ V ⎠ ⎝ V ⎠
4 5 6
⎛ N⎞ ⎛ N⎞ ⎛ N⎞
+0.110252 ⎜ b ⎟ + 0.03888198 ⎜ b ⎟ + 0.01302354 ⎜ b ⎟ +
⎝ V ⎠ ⎝ V ⎠ ⎝ V ⎠
7 8 9
⎛ N⎞ ⎛ N⎞ ⎛ N⎞
+0.0041832 ⎜ b ⎟ + 0.0013094 ⎜ b ⎟ + 0.0004035 ⎜ b ⎟ + K .
⎝ V ⎠ ⎝ V⎠ ⎝ V⎠

In terms of the dimensionless density variable y = Nb/4V this becomes
pV
= 1 + 4 y + 10 y 2 + 18.364768 y 3 + 28.224512 y 4 + 39.81514752 y 5 +
NkT
+53.34441984 y 6 + 68.5375488 y 7 + 85.8128384 y 8 + 105.775104 y 9 +K
Only terms up to y5 were known to Carnahan and Starling.
Round coefficients to whole numbers: 4, 10, 18, 28, 40.
Then the coefficient of yn is n(n + 3) – assume it works in general.
Check this with the newly-known virial coefficients; Carnahan and

Starling’s formula gives 54, 70, 88, 108;
actual rounded integers are 53, 69, 86, 106. Agreement is quite good.

From this assumption, the general expression for the nth virial
coefficient is
Bn =
( n − 1)( n + 2 ) n−1
b .
n −1
4
These are tabulated below, together with the true values.
C+S value
B2/b = 1 1
B3/b2 = 0.625 0.625
B4/b3 = 0.2869495 0.28125
B5/b4 = 0.110252 0.109375
B6/b5 = 0.03888198 0.0390625
B7/b6 = 0.01302354 0.0131836
B8/b7 = 0.0041832 0.00427246
B9/b8 = 0.0013094 0.00134277
B10/b9 = 0.0004035 0.000411987

We can now sum the infinite virial series, with the general Bn; we obtain
pV 4 y + 2 y2
= 1+
( ) .
3
NkT 1 − y
In terms of the number density N/V this gives the equation of state as
p N ⎪ b V + 8 (V ) ⎪
⎧ N b2 N 2 ⎫
= ⎨1 + ⎬
kT V ⎪⎩ (1 − 4 V ) ⎪⎭ .
b N 3
Incidentally, the universal function g(n) in the equation of state is then

given by
bn + (bn) 2 8
g ( n) = n
( ) .
3
1 − bn 4

Conventionally the equation of state is expressed and plotted in terms of
the ‘packing fraction’ V0/V, where V0 is the volume occupied by the
hard spheres V0 = Nπσ3/4 so that
V0 πσ 3 N 3b N
= =
V 4 V 8 V.
Then we obtain
p N⎪ 3V 9 V ⎪
= ⎨1 +
( )
⎧ 8 V0 + 8 V0 2 ⎫
3 ⎬
kT V ⎪
⎩ (
1− 3 V)
2 V0
⎪
⎭
.
This is plotted in the figure below. For comparison we have also shown
some data points obtained by molecular dynamics simulations.

15 Carnhan + Starling
pV
NkT - molecular dynamics
10
ideal gas
1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 V/V0
At higher densities the data points from molecular dynamics simulations

fall consistently below the curve of Carnahan and Starling. This
indicates the shortcoming of their method. Inspired as the C+S
procedure is, it is not quite correct. And the discrepancy is expected to
become greater at the higher densities. Perhaps the problem is to be
expected – after all, even the lower order virial coefficients have been
approximated, when the coefficients of the powers of y were truncated
to integers.

A more systematic way at arriving at an equation of state is the Padé
method.
3.6.6 Padé approximants

The equation of state of the hard sphere gas takes the form
pV
= f (V0 V )
NkT
where f is a universal function of its argument. So if the function is
determined then the hard sphere equation of state is known.
The virial series gives f as a power series in its argument. And in reality
one can only know a finite number of these terms. The Carnahan and
Starling procedure takes the known terms, ‘guesses’ the (infinite
number of) higher-order terms and then sums the series. The figure
above indicates that the result is good, but it could be better.

For the Carnahan and Starling equation of state the function f may be
written as
1 + 23 x + 209 x 2 − 278 x3
f ( x) =
1 − 2 x + 43 x 2 − 278 x3 .
In this form we observe that f (x) is the quotient of two polynomials.
And this leads us naturally to the Padé method.
One knows f (x) to a finite number of terms. In the Padé method the
function f (x) is approximated by the quotient of two polynomials
P ( x)
f ( x) ≈ Fn ,m ( x) = n
Qm ( x) .
Here Pn(x) and Qm(x) are polynomials of degrees n and m respectively.

Pn ( x) = p0 + p1 x + p2 x 2 + K + pn x n ,
Qm ( x) = q0 + q1 x + q2 x 2 + K + qm x m .
Without loss of generality we may (indeed it is convenient to) restrict
q0 = 1.
The terms of Pn(x) and Qm(x) may be determined so long as f (x) is

known to at least n + m terms. In other words if f (x) is known to n + m
terms, then Fn,m(x) agrees with the known terms of the series for f(x);
moreover the quotient generates a series of higher order terms as well.
The hope is that this series will be a good approximation to the true (but
unknown) f(x).
Power series of f (x) Qm(x) – Pn(x) begins with the term xm + n + 1.
Different m, n subject to m + n = N. – See Reichl for (some) details.

Thus Ree and Hoover (1964) – (i.e. before Clisby and McCoy’s extra
virial coeffs) constructed
pV
= 1+
2.66667 + 0.451605 V0
V + 0.328609 ( ) V0 2
V ( )
V0 3
V
NkT 1 − 1.49731 V + 0.578226 V

V0 V0 2
( )
15
3, 2 Padé
pV
NkT
10
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 V/V0
which is seriously better than the Carnhan + Starling expression.

3.6.7 Phase transition
15
pV
NkT
10
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 V/V0
We note that a random assembly of spheres will pack to V0/V = 0.638

so this is the greatest density possible for the fluid. However a close-
packed lattice (fcc or hcp) will pack more densely, to 0.7405. Thus there
should be a phase transition to a solid phase.…..

3d hard spheres 2d hard discs
The lack of an attractive part of the inter-particle interaction means that

there will be no gas-liquid transition; attraction is needed to have a self-
bound fluid phase coexisting with a dispersed gas phase.

Van der Waals equation approximates real gas behavior

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3.

4 Van der Waals Equation of State

The approximation is based on the single-particle partition function.

Shall obtain an equation of state approximating behaviour of real gases.

4211 Statistical Mechanics 1 Week 3

► How to treat inter-particle interactions – in an approximate way?

Interaction U(r) comprises:

The key is to treat these two parts separately/differently:

4211 Statistical Mechanics 2 Week 3

► Thus we arrive at the approximation

4211 Statistical Mechanics 3 Week 3

This allows us to keep the simplifying feature of the free-particle

Accordingly, this is referred to as a mean field calculation.

4211 Statistical Mechanics 4 Week 3

4211 Statistical Mechanics 5 Week 3

4211 Statistical Mechanics 6 Week 3

i) The repulsion is strong. We accounted for this by saying that there is

Interaction → boundary condition. Thus the excluded volume will be

4211 Statistical Mechanics 7 Week 3

4211 Statistical Mechanics 8 Week 3

These results give the correct assumed N and V dependence of the

4211 Statistical Mechanics 9 Week 3

Thus we immediately identify the second virial coefficient as

4211 Statistical Mechanics 10 Week 3

4211 Statistical Mechanics 11 Week 3

The Dieterici equation of state is one of a number of purely

4211 Statistical Mechanics 12 Week 3

4211 Statistical Mechanics 13 Week 3

The third virial coefficient is given by

4211 Statistical Mechanics 14 Week 3

4211 Statistical Mechanics 15 Week 3

4211 Statistical Mechanics 16 Week 3

4211 Statistical Mechanics 17 Week 3

P. M. Chaikin and T. C. Lubensky, Principles of Condensed Matter

4211 Statistical Mechanics 18 Week 3

Three possible approaches:

4211 Statistical Mechanics 19 Week 3

→ Clausius equation of state: p(V – Vex) = NkT .

Correct in the 1-d case

4211 Statistical Mechanics 20 Week 3

The equation of state of a hard-sphere fluid has a very special form.

Recall that for an interacting gas Z may be written as

4211 Statistical Mechanics 21 Week 3

Note: QN is independent of temperature. This must be so, since there

4211 Statistical Mechanics 22 Week 3

The important conclusion we draw from these arguments, and in

4211 Statistical Mechanics 23 Week 3

The virial expansion may be regarded as a low-density approximation to

4211 Statistical Mechanics 24 Week 3

4211 Statistical Mechanics 25 Week 3

4211 Statistical Mechanics 26 Week 3

4211 Statistical Mechanics 27 Week 3

4211 Statistical Mechanics 28 Week 3

Only terms up to y5 were known to Carnahan and Starling.

Round coefficients to whole numbers: 4, 10, 18, 28, 40.

Then the coefficient of yn is n(n + 3) – assume it works in general.

Check this with the newly-known virial coefficients; Carnahan and

4211 Statistical Mechanics 29 Week 3

4211 Statistical Mechanics 30 Week 3

Incidentally, the universal function g(n) in the equation of state is then

4211 Statistical Mechanics 31 Week 3

4211 Statistical Mechanics 32 Week 3