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Virial coecient

Virial coecients Bi appear as coecients in the virial

expansion of the pressure of a many-particle system in
powers of the density, providing systematic corrections to
the ideal gas law. They are characteristic of the interaction potential between the particles and in general depend
on the temperature. The second virial coecient B2 depends only on the pair interaction between the particles,
the third ( B3 ) depends on 2- and non-additive 3-body
interactions, and so on.

with the potential operators and the kinetic energies in

numerator and denominator cancel mutually. The trace
(tr) becomes an integral over the conguration space. It
follows that classical virial coecients depend on the interactions between the particles only and are given as integrals over the particle coordinates.
The derivation of higher than B3 virial coecients becomes quickly a complex combinatorial problem. Making the classical approximation and neglecting nonadditive interactions (if present), the combinatorics can
be handled graphically as rst shown by Joseph E. Mayer
and Maria Goeppert-Mayer.

Derivation

They introduced what is now known as the Mayer funcThe rst step in obtaining a closed expression for virial tion:
coecients is a cluster expansion of the grand canonical
partition function
[
]
u(|r1 r2 |)
f
(1,
2)
=
exp

kB T
=
n Qn = e(pV )/(kB T )
n
and wrote the cluster expansion in terms of these funcHere p is the pressure, V is the volume of the vessel con- tions. Here u(|r1 r2 |) is the interaction potential betaining the particles, kB is Boltzmanns constant, T is the tween particle 1 and 2 (which are assumed to be identical
absolute temperature, = exp[/(kB T )] is the fugacity, particles).
with the chemical potential. The quantity Qn is the
canonical partition function of a subsystem of n particles:

2 Denition in terms of graphs

Qn = tr[eH(1,2,...,n)/(kB T ) ].

The virial coecients Bi are related to the irreducible

Mayer cluster integrals i through

Here H(1, 2, . . . , n) is the Hamiltonian (energy operator) of a subsystem of n particles. The Hamiltonian is a
sum of the kinetic energies of the particles and the total n
-particle potential energy (interaction energy). The latter
includes pair interactions and possibly 3-body and higherbody interactions. The grand partition function can be
expanded in a sum of contributions from one-body, twobody, etc. clusters. The virial expansion is obtained from
this expansion by observing that ln equals pV /(kB T )
. In this manner one derives

Bi+1 =

i
i
i+1

The latter are concisely dened in terms of graphs.

i = The sum of all connected, irreducible graphs with one white and i blac
The rule for turning these graphs into integrals is as follows:

)
1 Q2
2
B2 = V
2 Q1
[
(
) 1 ( 6Q
)]
3
2 2Q2 2Q2
B3 = V
1
1
Q21 Q21
3 Q31
(

1. Take a graph and label its white vertex by k = 0 and

the remaining black vertices with k = 1, .., i .
2. Associate a labelled coordinate k to each of the vertices, representing the continuous degrees of freedom associated with that particle. The coordinate 0
is reserved for the white vertex

These are quantum-statistical expressions containing kinetic energies. Note that the one-particle partition function Q1 contains only a kinetic energy term. In the classical limit = 0 the kinetic energy operators commute
1

3. With each bond linking two vertices associate the
Mayer f-function corresponding to the interparticle
potential
4. Integrate over all coordinates assigned to the black
vertices
5. Multiply the end result with the symmetry number
of the graph, dened as the inverse of the number of
permutations of the black labelled vertices that leave
the graph topologically invariant.

The expression of the second virial coecient is thus:

B2 = 2

)
eu(|r1 |)/(kB T ) 1 r2 dr1 ,

where particle 2 was assumed to dene the origin ( r2 = 0

). This classical expression for the second virial coecient was rst derived by Leonard Ornstein in his 1908
Leiden University Ph.D. thesis.

Boyle temperature - temperature at which the second virial coecient B2 vanishes
Excess virial coecient
Compressibility factor

References

 Hill, T. L. (1960). Introduction to Statistical Thermodynamics. Addison-Wesley.

 Mayer, J. E.; Goeppert-Mayer, M. (1940). Statistical Mechanics. New York: Wiley.

Dymond, J. H.; Smith, E. B. (1980). The Virial
Coecients of Pure Gases and Mixtures: a Critical Compilation. Oxford: Clarendon. ISBN
0198553617.
Hansen, J. P.; McDonald, I. R. (1986). The Theory of Simple Liquids (2nd ed.). London: Academic
Press. ISBN 012323851X.
http://scitation.aip.org/content/aip/journal/jcp/50/
10/10.1063/1.1670902

http://scitation.aip.org/content/aip/journal/jcp/50/
11/10.1063/1.1670994
Reid, C. R., Prausnitz, J. M., Poling B. E., Properties
of gases and liquids, IV edition, Mc Graw-Hill, 1987

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