Virial coefficient

Virial coefficients Bi appear as coefficients in the virial with the potential operators and the kinetic energies in
expansion of the pressure of a many-particle system in numerator and denominator cancel mutually. The trace
powers of the density, providing systematic corrections to (tr) becomes an integral over the configuration space. It
the ideal gas law. They are characteristic of the interac- follows that classical virial coefficients depend on the in-
tion potential between the particles and in general depend teractions between the particles only and are given as in-
on the temperature. The second virial coefficient B2 de- tegrals over the particle coordinates.
pends only on the pair interaction between the particles,
The derivation of higher than B3 virial coefficients be-
the third ( B3 ) depends on 2- and non-additive 3-body comes quickly a complex combinatorial problem. Mak-
interactions, and so on. ing the classical approximation and neglecting non-
additive interactions (if present), the combinatorics can
be handled graphically as first shown by Joseph E. Mayer
1 Derivation and Maria Goeppert-Mayer.[2]
They introduced what is now known as the Mayer func-
The first step in obtaining a closed expression for virial tion:
coefficients is a cluster expansion[1] of the grand canonical
partition function
[ ]
u(|⃗r1 − ⃗r2 |)
∑ f (1, 2) = exp − −1
kB T
Ξ= λn Qn = e(pV )/(kB T )
n and wrote the cluster expansion in terms of these func-
Here p is the pressure, V is the volume of the vessel con- tions. Here u(|⃗r1 − ⃗r2 |) is the interaction potential be-
taining the particles, kB is Boltzmann’s constant, T is the tween particle 1 and 2 (which are assumed to be identical
absolute temperature, λ = exp[µ/(kB T )] is the fugacity, particles).
with µ the chemical potential. The quantity Qn is the
canonical partition function of a subsystem of n particles:
2 Definition in terms of graphs
Qn = tr[e−H(1,2,...,n)/(kB T ) ].
The virial coefficients Bi are related to the irreducible
Here H(1, 2, . . . , n) is the Hamiltonian (energy opera- Mayer cluster integrals βi through
tor) 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 i
Bi+1 = − βi
includes pair interactions and possibly 3-body and higher- i+1
body interactions. The grand partition function Ξ can be
The latter are concisely defined in terms of graphs.
expanded in a sum of contributions from one-body, two-
body, etc. clusters. The virial expansion is obtained from
this expansion by observing that ln Ξ equals pV /(kB T )
. In this manner one derives βi = The sum of all connected, irreducible graphs with one white and i blac

( ) The rule for turning these graphs into integrals is as fol-

1 Q2 lows:
B2 = V − 2
2 Q1
[ ( ) 1 ( 6Q )] 1. Take a graph and label its white vertex by k = 0 and
2 2Q2 2Q2 3
B3 = V −1 − −1 the remaining black vertices with k = 1, .., i .
Q21 Q21 3 Q31
These are quantum-statistical expressions containing ki- 2. Associate a labelled coordinate k to each of the ver-
netic energies. Note that the one-particle partition func- tices, representing the continuous degrees of free-
tion Q1 contains only a kinetic energy term. In the clas- dom associated with that particle. The coordinate 0
sical limit ℏ = 0 the kinetic energy operators commute is reserved for the white vertex

1
2 5 FURTHER READING

3. With each bond linking two vertices associate the • http://scitation.aip.org/content/aip/journal/jcp/50/

Mayer f-function corresponding to the interparticle 11/10.1063/1.1670994
potential
• Reid, C. R., Prausnitz, J. M., Poling B. E., Properties
4. Integrate over all coordinates assigned to the black of gases and liquids, IV edition, Mc Graw-Hill, 1987
vertices
5. Multiply the end result with the symmetry number
of the graph, defined as the inverse of the number of
permutations of the black labelled vertices that leave
the graph topologically invariant.

The first two cluster integrals are

The expression of the second virial coefficient is thus:

∫ ( )
B2 = −2π r2 e−u(r)/(kB T ) − 1 dr,

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

). This classical expression for the second virial coeffi-
cient was first derived by Leonard Ornstein in his 1908
Leiden University Ph.D. thesis.

3 See also
• Boyle temperature - temperature at which the sec-
ond virial coefficient B2 vanishes
• Excess virial coefficient
• Compressibility factor

4 References
[1] Hill, T. L. (1960). Introduction to Statistical Thermody-
namics. Addison-Wesley.

[2] Mayer, J. E.; Goeppert-Mayer, M. (1940). Statistical Me-

chanics. New York: Wiley.

5 Further reading
• Dymond, J. H.; Smith, E. B. (1980). The Virial
Coefficients of Pure Gases and Mixtures: a Crit-
ical Compilation. Oxford: Clarendon. ISBN
0198553617.
• Hansen, J. P.; McDonald, I. R. (1986). The The-
ory of Simple Liquids (2nd ed.). London: Academic
Press. ISBN 012323851X.
• http://scitation.aip.org/content/aip/journal/jcp/50/
10/10.1063/1.1670902
 3

6 Text and image sources, contributors, and licenses

6.1 Text
• Virial coefficient Source: https://en.wikipedia.org/wiki/Virial_coefficient?oldid=723989165 Contributors: Michael Hardy, Charles
Matthews, MathMartin, Bender235, Bela Mulder, Gene Nygaard, SmackBot, Kazkaskazkasako, Wiki me, Joriskuipers, Thijs!bot,
P.wormer, ClueBot, Addbot, Yobot, PianoDan, FrescoBot, Marie Poise, Dcconsta, Faizan, Imtimtimt and Anonymous: 17

6.2 Images
• File:Graph_Cluster_integral_1.PNG Source: https://upload.wikimedia.org/wikipedia/en/9/91/Graph_Cluster_integral_1.PNG License:
Cc-by-sa-3.0 Contributors: ? Original artist: ?
• File:Graph_Cluster_integral_2.PNG Source: https://upload.wikimedia.org/wikipedia/en/c/c3/Graph_Cluster_integral_2.PNG License:
Cc-by-sa-3.0 Contributors: ? Original artist: ?

6.3 Content license

• Creative Commons Attribution-Share Alike 3.0