Construction of subcritical isotherms for model and real gases on the basis of Mayer's cluster expansion

Physical Review. E
M V Ushcats, L A Bulavin

Abstract

Existing rigorous statistical approaches still cannot quantitatively describe condensation phenomena in real fluids and even model systems with some simplified interaction potential. Here, we present a method to evaluate the unlimited subcritical set of Mayer's reducible cluster integrals (the power coefficients of virial expansions) by using the information on several virial coefficients and empirical value of saturation activity. As to the requirements on the initial number of known virial coefficients, the calculations for the Lennard-Jones model indicate that only the second virial coefficient is sufficient to reproduce gas isotherms (including the flat phase-transition region) with high accuracy at low temperatures. This remarkable feature allows the simplification of the method for real fluids with an unknown interaction potential: In particular, the calculated isotherms of several real substances (including water) are in good agreement with experiments. Additionally, the obtained results indicate the existence of some important universality which needs serious future exploration.

References

Jul 13, 2004·Physical Review Letters·Jayant K Singh, David A Kofke
Sep 26, 2012·Physical Review Letters·M V Ushcats
Mar 15, 2013·The Journal of Chemical Physics·M V Ushcats
May 18, 2013·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·M V Ushcats
Feb 14, 2015·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Patrick Huber
Jun 13, 2015·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·M V Ushcats
Aug 4, 2015·The Journal of Chemical Physics·Chao FengDavid A Kofke
Aug 31, 2016·Physical Review. E·M V UshcatsS J Ushcats
Jan 20, 2018·Physical Review. E·M V UshcatsS Yu Ushcats
Nov 2, 2019·Physical Chemistry Chemical Physics : PCCP·Maxim M LazarenkoLeonid A Bulavin
Dec 25, 2019·Physical Review. E·Timur Aslyamov, Iskander Akhatov

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Citations

Nov 21, 2020·Physical Review. E·M V UshcatsL M Markina

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