Free-volume approximations for asymmetric hard-sphere mixtures

doi:10.1088/0953-8984/14/40/320

Free-volume approximations for predicting the phase behaviour of asymmetric hard-sphere mixtures

Henk N W Lekkerkerker et al 2002 J. Phys.: Condens. Matter 14 9317-9322 doi: 10.1088/0953-8984/14/40/320

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Henk N W Lekkerkerker¹ and S Martijn Oversteegen
Van 't Hoff Laboratory for Physical and Colloid Chemistry, Debye Research Institute, Utrecht University, PO Box 80051, 3508 TB Utrecht, The Netherlands
E-mail: h.n.w.lekkerkerker@chem.uu.nl
¹ Author to whom any correspondence should be addressed.

Abstract. Two different levels of the free-volume approximation for the calculation of the phase diagram of a asymmetric hard-sphere mixture are compared to direct simulations of the phase behaviour. The mean-field-level free-volume approach, where only the statistically pre-averaged free volume is accounted for, is already in satisfactory agreement with the simulation results. Taking correlations into account within the free-volume approach improves the agreement with the solid branch of the phase diagram but, remarkably, this version performs somewhat worse for the fluid branch.

Print publication: Issue 40 (14 October 2002)
Received 2 May 2002
Published 27 September 2002

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Free-volume approximations for predicting the phase behaviour of asymmetric hard-sphere mixtures

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