Virial equation of state: Difference between revisions
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where ''f'' is the [[Mayer f-function]] (see also: [[Cluster integrals]]). | where ''f'' is the [[Mayer f-function]] (see also: [[Cluster integrals]]). | ||
See also | See also <ref>[http://dx.doi.org/10.1080/002689796173453 M. S. Wertheim "Fluids of hard convex molecules III. The third virial coefficient", Molecular Physics '''89''' pp. 1005-1017 (1996)]</ref> | ||
==Convergence== | ==Convergence== | ||
For a commentary on the convergence of the virial equation of state see <ref>[http://dx.doi.org/10.1063/1.1704186 J. L. Lebowitz and O. Penrose "Convergence of Virial Expansions", Journal of Mathematical Physics '''5''' pp. 841-847 (1964)]</ref> and section 3 of <ref>[http://dx.doi.org/10.1088/0953-8984/20/28/283102 A. J. Masters "Virial expansions", Journal of Physics: Condensed Matter '''20''' 283102 (2008)]</ref> | For a commentary on the convergence of the virial equation of state see <ref>[http://dx.doi.org/10.1063/1.1704186 J. L. Lebowitz and O. Penrose "Convergence of Virial Expansions", Journal of Mathematical Physics '''5''' pp. 841-847 (1964)]</ref> and section 3 of <ref>[http://dx.doi.org/10.1088/0953-8984/20/28/283102 A. J. Masters "Virial expansions", Journal of Physics: Condensed Matter '''20''' 283102 (2008)]</ref>. | ||
==Quantum virial coefficients== | |||
Using the [[path integral formulation]] one can also calculate the virial coefficients of quantum systems <ref>[http://dx.doi.org/10.1063/1.3573564 Giovanni Garberoglio and Allan H. Harvey "Path-integral calculation of the third virial coefficient of quantum gases at low temperatures", Journal of Chemical Physics 134, 134106 (2011)]</ref>. | |||
==References== | ==References== | ||
<references/> | <references/> | ||
Revision as of 10:32, 8 April 2011
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 in 1885 by Thiesen [1] and extensively studied by Heike Kamerlingh Onnes [2] [3], and mathematically by Ursell [4]. One has
- 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
- 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 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
- 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 [5]
Convergence
For a commentary on the convergence of the virial equation of state see [6] and section 3 of [7].
Quantum virial coefficients
Using the path integral formulation one can also calculate the virial coefficients of quantum systems [8].
References
- ↑ M. Thiesen "Untersuchungen über die Zustandsgleichung", Annalen der Physik 24 pp. 467-492 (1885)
- ↑ H. Kammerlingh Onnes "Expression of the equation of state of gases and liquids by means of series", Communications from the Physical Laboratory of the University of Leiden 71 pp. 3-25 (1901)
- ↑ H. Kammerlingh Onnes "Expression of the equation of state of gases and liquids by means of series", Proceedings of the Koninklijke Nederlandse Akademie van Wetenschappen 4 pp. 125-147 (1902)
- ↑ H. D. Ursell "The evaluation of Gibbs' phase-integral for imperfect gases", Mathematical Proceedings of the Cambridge Philosophical Society 23 pp. 685-697 (1927)
- ↑ M. S. Wertheim "Fluids of hard convex molecules III. The third virial coefficient", Molecular Physics 89 pp. 1005-1017 (1996)
- ↑ J. L. Lebowitz and O. Penrose "Convergence of Virial Expansions", Journal of Mathematical Physics 5 pp. 841-847 (1964)
- ↑ A. J. Masters "Virial expansions", Journal of Physics: Condensed Matter 20 283102 (2008)
- ↑ Giovanni Garberoglio and Allan H. Harvey "Path-integral calculation of the third virial coefficient of quantum gases at low temperatures", Journal of Chemical Physics 134, 134106 (2011)
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