Virial equation of state

The virial equation of state is used to describe the behavior of diluted gases. It is usually written as an expansion of the compressibility factor, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z } , in terms of either the density or the pressure. Such an expansion was first introduced by Kammerlingh Onnes. In the first case:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \frac{p V}{N k_B T } = Z = 1 + \sum_{k=2}^{\infty} B_k(T) \rho^{k-1}} .

where

• Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p } is the pressure

• Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle V } is the volume

• Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N } is the number of molecules

• Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \rho \equiv \frac{N}{V} } is the (number) density

• Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_k\left( T \right) } is called the k-th virial coefficient

Virial coefficients

The second virial coefficient represents the initial departure from ideal-gas behavior

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_{2}(T)= \frac{N_A}{2V} \int .... \int (1-e^{-\Phi/k_BT}) ~d\tau_1 d\tau_2}

where $N_{A}$ is Avogadros number and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle d\tau_1} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle d\tau_2} are volume elements of two different molecules in configuration space.

One can write the third virial coefficient as

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_{3}(T)= - \frac{1}{3V} \int \int \int f_{12} f_{13} f_{23} dr_1 dr_2 dr_3}

where f is the Mayer f-function (see also: Cluster integrals). See also:

• M. S. Wertheim "Fluids of hard convex molecules III. The third virial coefficient", Molecular Physics 89 pp. 1005-1017 (1996)

Convergence

See Ref. 3.

References

1. H. Kammerlingh Onnes "", Communications from the Physical Laboratory Leiden 71 (1901)
2. James A Beattie and Walter H Stockmayer "Equations of state", Reports on Progress in Physics 7 pp. 195-229 (1940)
3. J. L. Lebowitz and O. Penrose "Convergence of Virial Expansions", Journal of Mathematical Physics 5 pp. 841-847 (1964)