A deeper look 2   The fugacity

At various stages in the development of physical chemistry In this expression, f1 is the fugacity when the pressure is
it is necessary to switch from a consideration of ideal- p1 and f2 is the fugacity when the pressure is p2. That is,
ized systems to real systems. In many cases it is desirable from eqn 3b,
to preserve the form of the expressions that have been
derived for an idealized system. Then deviations from the
p2 f2
idealized behaviour can be expressed most simply. For
∫ p1
Vm d p = RT ln
f1  (4a)

instance, the pressure-dependence of the molar Gibbs

For a perfect gas,
energy of a perfect gas is
 p p2 p2
Gm = G m + RT ln  −○−   ∫ Vperfect ,mdp = RT ln  (4b)
−−
○
(1a)
p  p1 p1

For a real gas, the true pressure, p, is replaced by an effec-

tive pressure, called the fugacity,1 f, to give Step 2  Express the integral in terms of the difference of
molar volumes of real and perfect gases
 f 
Gm = G m + RT ln  −−○  
−−
(1b)
○
The difference between the real and perfect expressions is
p 
The fugacity, a function of the pressure and temperature, p2  f p  f /p
is defined so that this relation is exactly true. A very simi- ∫ p1
(Vm − Vperfect,m )dp = RT  ln 2 − ln 2  = RT ln 2 2
 f1 p1  f1 / p1
lar approach is taken in the discussion of real solutions
where ‘activities’ are effective concentrations, so f/p may
⦵
which can be rearranged into
be regarded as a gas-phase activity.
f 2 / p2 1 p
f1 / p1 RT ∫p m perfect,m
2
Although thermodynamic expressions in terms of ln = (V − V )dp  (5)
1
fugacities derived from this expression are exact, they
are useful only if fugacities can be expressed in terms of
Step 3  Allow one of the pressures to approach zero
actual pressures. To develop this relation the fugacity is
written as When p1 → 0, the gas behaves perfectly and f1 becomes
equal to the pressure, p1. Therefore, f1/p1 → 1 as p1 → 0. On
f = ϕp (2) taking this limit, which means setting f1/p1 = 1 on the left
where ϕ is the dimensionless fugacity coefficient, which in of eqn 5 and p1 = 0 on the right, eqn 5 becomes
general depends on the temperature, the pressure, and the
identity of the gas. For a perfect gas, ϕ = 1 at all tempera- f2 1 p2

tures and pressures.

ln =
p2 RT ∫ 0
(Vm − Vperfect,m )dp (6)

The starting point for establishing the relation between

the fugacity coefficient and the pressure of a gas is the
general relation that, at constant temperature,
dGm = Vmdp
At this stage the subscript 2 may be dropped (so that p2
becomes p, the pressure of interest, and f2 becomes f, the
fugacity at that pressure), and with ϕ = f/p,
(3a)
1 p

and its integral form

ln φ =
RT ∫0
(Vm − Vperfect,m )dp (7)

p2
Gm( p2 )− Gm ( p1 ) = ∫ Vm d p  (3b) For a perfect gas, Vperfect,m = RT/p. For a real gas, Vm =
p1
RTZ/p, where Z is the compression factor of the gas. With
Step 1  Express the molar Gibbs energies in terms of fugacity these two substitutions, eqn 7 becomes
From the definition in eqn 1b,
p Z −1
ln φ = ∫ d p (8)
 −−○ f   −−○ f  0 p
Gm ( p2 )− Gm ( p1 ) = G m + RT ln −−○2  − G m + RT ln −−○1 
 p   p 
Provided it is known how Z varies with pressure up to the
f pressure of interest, this expression can be used to deter-
= RT ln 2
f1 mine the fugacity coefficient and hence, through eqn 2, the
fugacity of the gas at the pressure interest.
1
  The name ‘fugacity’ comes from the Latin for ‘fleetness’ in the sense
of ‘escaping tendency’; fugacity has the same dimensions as pressure.
2 A deeper look 2  The fugacit y

Step 4  Analyse the implications of the equation 3

5 1.5 3.0
For a perfect gas, ϕ = 1 at all pressures and tempera- 2.0
tures. For most gases Z < 1 up to moderate pressures, but

Fugacity coefficient, ϕ = f/p

Z > 1 at higher pressures. If Z < 1 throughout the range 2.5
6
1.5
of integration, then the integrand in eqn 8 is negative 1
and ϕ < 1. This value implies that f < p (the molecules 8 15
tend to stick together) and that the molar Gibbs energy 2
1.2
of the gas is less than that of a perfect gas. At higher pres- 10
20
sures, the range over which Z > 1 may dominate the range 0.5
25
over which Z < 1. The integral is then positive, ϕ > 1, and 1.5
1.1
f > p (the repulsive interactions are dominant and tend to 35
drive the particles apart). Now the molar Gibbs energy of 1.0

the gas is greater than that of the perfect gas at the same 1 0
0 20 40 60 80 100 0 4 8 12 16 20
pressure. Reduced pressure, pr = p/pc Reduced pressure, pr = p/pc
Figure 1, which has been calculated using the full van
der Waals equation of state, shows how the fugacity coef- Figure 1  The fugacity coefficient of a van der Waals gas
ficient depends on the pressure in terms of the reduced plotted using the reduced variables of the gas. The curves are
labelled with the reduced temperature Tr = T/Tc.
variables.