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 Heike Kamerlingh Onnes in 1901 . 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 T} is the temperature
• 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 k_B} is the Boltzmann constant
• 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
• $B_{k}\left(T\right)$ is called the k-th virial coefficient

Virial coefficients

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

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 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_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

$B_{3}(T)=-{\frac {1}{3V}}\int \int \int f_{12}f_{13}f_{23}dr_{1}dr_{2}dr_{3}$

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

For a commentary on the convergence of the virial equation of state see and section 3 of

References

Related reading

• James A Beattie and Walter H Stockmayer "Equations of state", Reports on Progress in Physics 7 pp. 195-229 (1940)
• Edward Allen Mason and Thomas Harley Spurling "The virial equation of state", Pergamon Press (1969) ISBN 0080132928