Phase behaviour of a symmetrical binary fluid mixture

Abstract

We have investigated the phase behaviour of a symmetrical binary fluid mixture for the situation where the chemical potentials $μ_1$ and $μ_2$ of the two species differ. Attention is focused on the set of interparticle interaction strengths for which, when $μ_1=μ_2$, the phase diagram exhibits both a liquid-vapor critical point and a tricritical point. The corresponding phase behaviour for the case $μ_1\neμ_2$ is investigated via integral-equation theory calculations within the mean spherical approximation (MSA), and grand canonical Monte Carlo (GCMC) simulations. We find that two possible subtypes of phase behaviour can occur, these being distinguished by the relationship between the critical lines in the full phase diagram in the space of temperature, density, and concentration. We present the detailed form of the phase diagram for both subtypes and compare with the results from GCMC simulations, finding good overall agreement. The scenario via which one subtype evolves into the other, is also studied, revealing interesting features.