RALPHK.

BIRDWHISTELL
University of West Florida
Pensamla,FL32504

textbook forum
Fugacity-More

Than a Fake Pressure

Maarten C. A. Donkersloot
Department of Chemical Technology, Eindhoven University of Technology, Eindhoven, The Netherlands
Often, fugacitv is introduced as nothing more than a replacement-for
in thermodynamic formulas. A
quick search through some textbooks gave the following
some effective pressure ( l , 2 )
a n effective or thermodynamic pressure (3)
a kind of fictitiouspressure ( 4 )
a sort of idealized pressure (5)
s "corrected pressure" (6)

Using a Maxwell equation

that can be integrated at wnstant temperature to yield

Correspondingly, the standard treatment goes more or less

alone the followine lines. mostlv with a less ex~licitnotation'than that use2 here.'For ideal gases we hake
we get
for the chemical potential, as an explicit function of pressure. Thus, for real gases we must have

where the fugacity f replaces the pressure p and contains

all deviations fmm ideality.
Since it has been experimentally veriiied that all gases
at low pressures behave like ideal gases, we must get

Defining a fugacity coefficient x@, T ) by

1

~~X(P.T)=B(TII,+~WJP'+..

we arrive at
At very low pressures f @, T)+p. Thus, the pressure-independent term ha@o,
T ) can be recognized as the standard
chemical potential of the ideal gas. At low pressures, this
standard chemical potential of the ideal gas becomes identical to that of the real gas for the same pressure and temperature.
The last statement is especially difficult for sceptical students to understand if they have little experience in the
logic of thermodynamics. Thus, the concept off and the
meaning of ha remain a mystery. Even bright students are
at a loss when asked to discuss the temperature dependence off@, 0 and
T).Yet it is almost trivial to introduce the fugacity of a real gas with reference to its
proper meaning as defined below.
Afunction ofp and Tthat contains complete information on the
pressure dependence of the chemical potential of the gas.

In some situations, the fugacity is more convenient to

apply. Also, the term pid@., T ) can be defined independently in such a way that its temperature dependence can
be easily worked out. In the remainder of this paper, I will
outline such an introduction.
Defining the Pressure-Dependent Term
To begin, I choose the experimentally verified virial expansion as a generally valid statement.
290

Journal of Chemical Education

Remember,
lim,,ox@,T)=l
is automatically true because the ideality of a real gas at
low pressures was implied already in the above virial expansion.
A shorter version of this equation withp. as a standard
pressure would be

where the fugacity f @, T ) has been defmed as x@, T ) .p.

From this treatment it is clear that pis@,, 2') is the chemical potential of the real gas at p, and T, explicitly corrected for the extent of nonideality of this gas atp, and T,
as measured by the nrial coefficients. In other words, to
calculate kd(latm, 298.15 K) for a real gas, one needs to
use standard tables to get certain values for that gas: p(1
atm, 298.15 K), and the virial coefficients B(298.15 K),
C(298.15 K), and so forth.
2').,
The problem of the temperature dependence of kid@
can be reduced to the standard problems of the tempera-

ture dependence of p@.,

T)and B(T), C(T), etc. The tem-

Conclusion

Nowhere have I been tempted to intmduce fugaeity as a

fake pressure. From the explicit equations, the equivalence Offugacit~
and chemical potential, in terms of d e ~ e n dence on pressure, should be obvious to any student.

Literature Cited

3. Adamsan,A. W.ATerltmkafPhysiml CkMshy,kdsd.;kademicRess;NeuYarh,

1919:p216.
4.Denbigh. K The Pnnd&s ofChmmM Equitibrium, 4U1 ed.; Cambridge University
Ress. 1986;p 122.
,,,,
,phy,Ml chbhy, 3rd rdddi
-a,
1962;p94.
8. Pmu-tz,. M.; Lkhtenthde, R N.; de & w e d , E.G M o k x h r Titmmcfynmics
O ~ F I Y ~ - P ~ E ~znd
Y .~d.;I RentiecHaU,
~ M ~ .
1986;p 19.

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Volume 69 Number 4 April 1992

291