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The van-der-Waals equation of state takes into account the repulsive and attractive interactions explicitly:

a
(p + ) (Vm − b) = RT .
Vm2
(p+aVm2)(Vm−b)=RT.

Compared with the ideal gas law, the molar volume is reduced by a constant known as the excluded volume,
bb, which is interpreted as the volume blocked by the gas atoms or molecules themselves to account for the
fact that several atoms cannot occupy the same space and that the atoms make fast random movements about
their position as a consequence of their thermal energy. At the same time, the pressure is increased by
theinternal pressure, Va 2 aVm2. The rationale for this is that the long-range attractive forces are balanced for
m
all gas atoms except for those near the walls of the container since these atoms are lacking gas atoms on one
side (facing the wall). As a result, they are pulled into the container, and the effective pressure (force acting
on the wall) is reduced accordingly, i.e. the correction term is added to the measured pressure, pp. The
correction scales with Vm−2 Vm−2 because the force acting on the affected gas atoms and the number of atoms
both depend on the number density (∝ Vm−1 ∝Vm−1), combining to the inverse-square relationship.

The van-der-Waals equation is only one parameterisation of the attractive and repulsive interactions.
There are other equations of state that address these interactions differently, but they all have two
parameters for the two types of interaction. All of them are approximations. Compared to the virial
equation, they all have the advantage of describing a simple model based on physical understanding but
the disadvantage of greater deviations from observed behaviour for any particular gas.

Because of the absence of interatomic

interactions, all isotherms of an ideal
gas are hyperbolae:

RT
p(Vm ) =
Vm
p(Vm)=RTVm

In a real gas, supercritical isotherms look

fairly similar, except that they have a
shallower slope due to the exclusion volume.
This deviation is strongest at high pressure
and low molar volume. As we have seen
when discussing phase diagrams, subcritical
isotherms of real gases are very different as
they cut through thephase transition region
between liquid and gas. The apex of the two-
phase region is thecritical point, located on the critical isotherm at Tc Tc.

An isothermal quasi-static compression process will follow a sub-critical isotherm such as the blue line in
the diagram from right to left. As the boundary of the two-phase region is reached, the pressure remains
constant (horizontal line in the pV diagram) during further compression as gas is transformed into liquid.
At the end of the two-phase region, as no gas is left, the pressure rises sharply with further compression
due to the much smaller compressibility of the condensed phase.

If the compression is carried out more quickly, i.e. deviating from quasi-static conditions, it is possible to
continue following the isotherm around the edge of the two-phase region up to the local maximum shown
in the diagram. The gas is known asoversaturated vapour in this metastable regime. Similarly, when
expanding the liquid phase under non-quasistatic conditions, it is possible to continue on the subcritical
isotherm to its local minimum, the metastable retarded boiling regime. Within these metastable
areas, spontaneous phase change can always occur if a sudden disturbance or the presence of a surface
enables the nucleation of the second phase. It is important to note that these metastable conditions are
deviations from thermodynamic equilibrium, a concept which assumes all changes to be quasi-static.
The instable region of the isotherm between its local minimum and its local maximum is totally

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inaccessible since it would mean that an increase in pressure would result in an expansion of the medium,
which is clearly unphysical.

We can use the van-der-Waals equation

a
(p + ) (Vm − b) = RT
Vm2
(p+aVm2)(Vm−b)=RT

to estimate the critical parameters of a real gas considering that the critical point is apoint of inflection of the
critical isotherm. By re-writing the van-der-Waals equation in terms of pressure as a function of (molar)
volume,
RT a
p(Vm ) = − 2 ,
Vm − b Vm
p(Vm)=RTVm−b−aVm2,

we can take the first and second derivative of the critical isotherm and find the inflection point by forcing
them both to zero. (The first derivative must be zero for minima, maxima and inflections, i.e. the slope at all
these points is horizontal. The second derivative determines whether the direction of the slope changes or, in
the case of an inflection point, stays the same on either side.) Therefore,

dp ∣ RTc 2a !
∣ =− + = 0
dVm ∣T=Tc (Vm,c − b) 2 3
Vm,c
dpdVm|T=Tc=−RTc(Vm,c−b)2+2aVm,c3=!0

and

d2p ∣ 2RTc 6a !
∣ = − = 0 .
2
dVm ∣T=Tc (Vm,c − b) 3 4
Vm,c
d2pdVm2|T=Tc=2RTc(Vm,c−b)3−6aVm,c4=!0.

This produces two simultaneous equations:

3
RTcVm,c = 2a(Vm,c − b) 2
{ 4
} ,
2RTcVm,c = 6a(Vm,c − b) 3
{RTcVm,c3=2a(Vm,c−b)22RTcVm,c4=6a(Vm,c−b)3},

which can be divided by one another, conveniently removing the higher powers:

2Vm,c = 3(Vm,c − b) .
2Vm,c=3(Vm,c−b).

This is solved for the critical molar volume:

Vm,c = 3b
Vm,c=3b

By substituting that back into one of the two simultaneous equations, we get

RTc(3b) 3 = 2a(3b − b) 2
RTc(3b)3=2a(3b−b)2

and solve for the critical temperature:

8ab2 8a
Tc = = .
27Rb 3 27Rb
Tc=8ab227Rb3=8a27Rb.

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Both Tc Tc and Vm,c Vm,c can be substituted back into the van-der-Waals equation, giving a solution for
the critical pressure:
RTc a R8a a 4a a a
pc = − 2 = − 2 = − 2 = .
Vm,c − b Vm,c 27Rb(3b − b) 9b 27b2 9b 27b2
pc=RTcVm,c−b−aVm,c2=R8a27Rb(3b−b)−a9b2=4a27b2−a9b2=a27b2.

Now that all critical variables are expressed in terms of the van-der-Waals parameters, internal pressure
coefficient a a and excluded volume bb, it is possible to normalise all state variables anywhere in the
pV TpVT cube to these critical values and introduce a set ofreduced variables:

p T Vm
pr = , Tr = , Vm,r = .
pc Tc Vm,c
pr=ppc,Tr=TTc,Vm,r=VmVm,c.

As long as a real gas is adequately described by the van-der-Waals model, the theorem of corresponding
states maintains that the behaviour of any real gas should be the same in terms of these reduced variables.
For example, the critical compression factor can be reduced to a simple number valid for all van-der-Waals
gases:
pc Vm,c 3
Zc = = .
k B Tc 8
Zc=pcVm,ckBTc=38.

It may be useful to compare the van-der-Waals and virial equations to backfill the virial equation with a
model of the physical effects causing the behaviour it describes. To do this, we need to bring the van-der-
Waals equation into the shape of the virial equation, a series of powers of V1m 1Vm:

RT a RT a
p= − = − .
Vm − b Vm 2 b
Vm (1 − V ) Vm2
m
p=RTVm−b−aVm2=RTVm(1−bVm)−aVm2.

The bracket can be expanded into a series according to

1
= 1 + x + x2 + … (for x < 1) :
1−x
11−x=1+x+x2+…(forx<1):

RT b b2 a
p= (1 + + + …) − .
Vm Vm Vm2 Vm2
p=RTVm(1+bVm+b2Vm2+…)−aVm2.

Bring one Vm Vm over to the left to match the left-hand side of the virial equation:
a
b b2 a b − RT b2
pVm = RT (1 + + + …) − = RT (1 + + + …)
Vm Vm2 Vm Vm Vm2
pVm=RT(1+bVm+b2Vm2+…)−aVm=RT(1+b−aRTVm+b2Vm2+…)

By comparison with the virial equation,

B C
pVm = RT (1 + + 2 + …) ,
Vm Vm
pVm=RT(1+BVm+CVm2+…),

it is clear that we can express the virial coefficients in terms of the van-der-Waals parameters:
a
B = b− and C = b2 .
RT

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B=b−aRTandC=b2.

The Boyle temperature is the temperature at which a real gas behaves almost like an ideal gas for an extended
range of pressures by virtue of the fact that the second virial coefficient is zero:
a !
B = b− = 0 .
RTBoyle
B=b−aRTBoyle=!0.

By solving this for the temperature, we can see that any van-der-Waals gas will behave like an ideal gas at
one specific multiple of its critical temperature:
a 27Tc
TBoyle = = .
bR 8

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