60 Scopus citations

Abstract

A methodology is presented for the direct determination of phase equilibria in mixtures from Monte Carlo simulation. The Widom test-particle expression is used for the evaluation of the chemical potential. The novel features of the proposed methodology include use of fluctuation theory that allows one to “observe” the approach of the system to a stability limit and introduction of an interchange algorithm to facilitate the calculation of properties for highly nonideal mixtures. The key attributes of simulations for the determination of the chemical potential and the phase diagrams are illustrated with simple Lennard-Jones fluids. It is shown that the interaction energies between unlike molecules are particularly important in determining the tendency of a system to phase-separate or to form an azeotrope. Molecular size differences between components were found to be less important. Finally, by choosing potential parameters that reproduce the critical constants of carbon dioxide and acetone, we obtained a simulated phase diagram that captures all the essential elements of the phase equilibrium behavior of the real mixture.

Original languageEnglish (US)
Pages (from-to)525-535
Number of pages11
JournalIndustrial and Engineering Chemistry Fundamentals
Volume25
Issue number4
DOIs
StatePublished - Jan 1 1986

All Science Journal Classification (ASJC) codes

  • Engineering(all)

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