Fugacity of a real gas

This lecture aims to address the following questions:

What is fugacity?
When and why do we use fugacities?
What is a fugacity coefficient?
How are fugacities derived?
What is the Lewis-Randall rule?

Fugacity of a real gas

We have seen that the chemical potential of a component
of an ideal gas mixture varies with the partial pressure
of that component in a logarithmic fashion:
p
i = io + RT ln io
1
p
We would like to similarly express the chemical
potential of a component of a real gas mixture as a
function of its partial pressure.
The difficulty is that we would soon lose the simple
form of equation 1. Each real gas would have its
own equation, and the functionality could take on a
very complex form.
2

Fugacity of a real gas

i = io + RT ln

pi
po

The approach taken has been, for a real gas, to retain the
simple form of equation 1, and to replace the actual
partial pressure pi of the gas by a quantity called the
fugacity (or effective partial pressure) of the gas
concerned. The assigned value of the fugacity of a
particular gas, fi , in a specified state, is arrived at such
that
f
i = io + RT ln io
p
Departures of the gas from ideal gas behaviour will be
reflected in departures of fi from pi.

Fugacity of a real gas

In doing so, the molar Gibbs energy of the real gas would
match that of the ideal gas after scaling.
Note that the Gibbs energy of the ideal
and perfect gases approach each other as
the pressure 0.
Also, attractive forces act to lower the
Gibbs energy of a real gas at intermediate
pressures.
At high pressures, the repulsive forces act
to raise the Gibbs energy of a real gas
relative to the equivalent value expected
for an ideal gas.

Fugacity of a real gas

So- the definition of this new function fugacity has
been developed with an eye on retaining the convenient
form of equation 1 which applies to an ideal gas
mixture.
Also, for real gases, equation 1 becomes more and more
nearly correct, as the pressure is lowered.
Accordingly, the fugacity, fi of a component i of a real
gas mixture (with units of pressure) is defined such that

i = Bi (T ) + RT ln ( fi / p o )
where Bi(T) represents a quantity which depends on T,
but does not depend on pressure.

Fugacity of a real gas

i = Bi (T ) + RT ln ( fi / p o )

Equation 2 introduces two new quantities, Bi and fi.

To complete the definition of fi we specify that
fi
1 as p 0
pi

Fugacity of a real gas

The standard state of a component i of a real gas mixture is
taken as a hypothetical pure gas i at the temperature T of
the mixture, at 1 bar pressure, with properties calculated on
the assumption that it behaves as an ideal gas over the
pressure range 0 to 1 bar.
1

Hypothetical pure ideal

gas i at p = 1 bar

fi / bar
Real gas mixture with
component i at pi = 1 bar

pi / bar

Fugacity of a real gas

1

Hypothetical pure ideal

gas i at p = 1 bar

fi / bar
Real gas mixture with
component i at pi = 1 bar

pi / bar

From equation 2, by setting fi = p = 1 bar, it follows that

and

io = Bi (T )

i = io (T ) + RT ln ( fi / p o )

4
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Fugacity of a real gas

Chemical potential of a component of a real gas
mixture
From equation 4 we had that, for a component of a real gas
mixture
i = io (T ) + RT ln ( fi / p o )
This expression can be contrasted with the corresponding
expression for a component of an ideal gas mixture

i = io (T ) + RT ln ( pi / po )
We see that fugacity plays the role of effective partial
pressure for real gases.
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Fugacity of a real gas

Fugacity coefficient
The deviation of the fugacity fi of i from the partial
pressure pi is expressed by the fugacity coefficient i
(phi i) of gas i.

f i = i pi = i xi p

Like fi , i is a function of T, p, and the composition of

the gas mixture.
We shall now see how numerical values of fi and i can be
obtained for a component of a gas mixture.
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Fugacity of a real gas

Fugacity of a component of a gas mixture
For a component i of a gas mixture, we have, from the
relevant Gibbs equation, for a system at constant
composition

dGi = d i = Vi dp Si dT
At constant T, dT = 0, and

d i = Vi dp

Differentiating equation 4, we have that

d i = RT d ln i o (at const.T )
p

4 = (T ) + RT ln ( f / p )
From equations 6 and 7
i

o
i

7
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Fugacity of a real gas

Fugacity of a component of a gas mixture

Vi dp = RT d ln i o (const.T )
p

V
d ln ( fi p o ) = i dp
(const.T )
RT
Equation 5:
f i = i pi = i xi p

Dividing both sides by p = 1 bar :

(f
ln ( f

p o ) = i xi ( p p o )

p o ) = ln + ln xi + ln ( p p o )

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Fugacity of a real gas

Fugacity of a component of a gas mixture
d ln ( f i p o ) = d ln i + d ln ( p p o )

(const. xi)

= d ln i + ( p o p ) d ( p p o )
= d ln i + (1 p ) dp

Use

d ln x 1
=
dx
x

Equation 8 becomes

V
d ln i + (1 p ) dp = i dp
RT
d ln i = (Vi RT ) dp (1 p ) dp

Integrating this expression from state 1 to state 2:

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Fugacity of a real gas

Fugacity of a component of a gas mixture
p2

d ln = (V
i

RT ) (1 p ) dp

p1

i ,2 p
ln
= (V RT ) (1 p ) dp
i ,1 p i
2

const T

In the limit as p 0, we have that i ,1 1 and

ln i ,2 =

p2

(V

RT ) (1 p ) dp

const T

0
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Fugacity of a real gas

Fugacity of a component of a gas mixture

ln i ,2 =

p2

(V

RT ) (1 p ) dp

const T

To determine the fugacity coefficient of a component of a

gas mixture at temperature T and at a total pressure of p2
and a certain composition we measure the partial molar
volume Vi in the mixture as a function of pressure.
We then plot Vi RT 1 p versus p and measure the area
under the curve from p = 0 to p = p2. Once i,2 is known
then fi,2 can be calculated from equation 5.
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Fugacity of a real gas

Fugacity coefficient of a pure gas
For a pure gas the same equation can be used, with the
partial molar volume replaced by the molar volume.

ln 2 =

p2

(Vm RT ) (1 p )dp
0

const T
9

Expressing this relationship in terms of the compressibility

factor of the gas (from 1st lecture), we have that
Vm
z
=
RT p

Substituting into equation 9 :

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Fugacity of a real gas

Fugacity coefficient of a pure gas

ln 2 =

p2

( z p ) (1 p )dp
0

z 1
=
dp
p
0
Replacing p by pcpr
p2
z 1
ln 2 =
d ( pc pr )
p

p
r
0 c
p2

z 1
=
dpr
p
r
0
p2

10

17

Fugacity of a real gas

Fugacity coefficient of a pure gas

ln 2 =

p2

( z p ) (1 p )dp
0

z 1
=
dp
p

0
Replacing p by pcpr
p2
z 1
ln 2 =
d ( pc pr )
p pr
0 c
p2

z 1
=
dpr
p
r
0

See alternative
derivation in
Atkins

p2

10

18

Fugacity of a real gas

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Fugacity of a real gas

Fugacity coefficient of a pure gas
According to the law of corresponding states, the
compressibility factor, z, is a universal function of pr and
Tr , i.e.,

z = z ( pr , Tr )

From equation 10 it is clear that the fugacity coefficient 2

is also a universal function of pr and Tr .
It follows that universal curves of versus pr at constant
values of Tr can also be plotted (Levine 5th edition,
Figure 10.11). These are, once again, useful
approximations to the behaviour of real gases, based on
20
the Law of corresponding states.

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Fugacity of a real gas

G for a chemical reaction involving real gases
For the chemical reaction
aA(g) + bB(g) cC(g) + dD(g)
G = c C + d D a A b B

f
f
f
f
= c Co + RT ln Co + d Do + RT ln Do a Ao + RT ln Ao b Bo + RT ln Bo
p
p
p
p

f
f
f
f
= ( cCo + d Do a Ao b Bo ) + cRT ln Co + dRT ln Do aRT ln Ao bRT ln Bo
p
p
p
p

c
d
a
b

f
f
f
f
= G o + RT ln Co + RT ln Do RT ln Ao RT ln Bo
p
p
p

p


= G

(f
+ RT ln
(f

po )

(f
p ) (f
c

o a

po )

po )

d
b

G = G o + RT ln Q f

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Fugacity of a real gas

The Lewis-Randall rule for real gases
To roughly estimate fugacities and fugacity coefficients for
components of real gas mixtures use can be made of the
Lewis-Randall rule.
This rule states that the fugacity coefficient of a component
i in a mixture of real gases is roughly equal to the fugacity
coefficient of pure gas i at the temperature T and (total)
pressure p of the mixture.
Ex.:
For air at 1 bar pressure and 0C the fugacity coefficient of O2 can be
estimated by the fugacity coefficient of pure oxygen at 1 bar pressure
and 0C. See Levine pp. 312-3 for some limitations to this rule. 22

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