Phase coexistence in polydisperse multi-Yukawa hard-sphere fluid: high temperature approximation

• Published in: The Journal of chemical physics Vol. 125; no. 3; p. 34501
• Main Authors: Kalyuzhnyi, Yu V, Hlushak, S P
• Format: Journal Article
• Language: English
• Published: United States 21.07.2006
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.2212419

High temperature approximation (HTA) is used to describe the phase behavior of polydisperse multi-Yukawa hard-sphere fluid mixtures. It is demonstrated that in the frames of the HTA the model belongs to the class of "truncatable free energy models," i.e., the models with thermodynamical properties (Helmholtz free energy, chemical potential, and pressure) defined by the finite number of generalized moments. Using this property we were able to calculate the complete phase diagram (i.e., cloud and shadow curves as well as binodals) and size distribution functions of the coexisting phases of several different models of polydisperse fluids. In particular, we consider polydisperse one-Yukawa hard-sphere mixture with factorizable Yukawa coefficients and polydisperse Lennard-Jones (LJ) mixture with interaction energy parameter and/or size polydispersity. To validate the accuracy of the HTA we compare theoretical results with previously published results of more advanced mean spherical approximation (MSA) for the one-Yukawa model and with the Monte Carlo (MC) computer simulation results of [Wilding et al. J. Chem. Phys. 121, 6887 (2004); Phys. Rev. Lett. 95, 155701 (2005)] for the LJ model. We find that overall predictions of the HTA are in reasonable agreement with predictions of the MSA and MC, with the accuracy range from semiquantitative (for the phase diagram) to quantitative (for the size distribution functions).