Phase behaviour of a symmetrical binary fluid mixture

TL;DR

This study explores the complex phase behavior of a symmetrical binary fluid mixture with differing chemical potentials, using theoretical calculations and simulations to identify distinct phase diagram subtypes and their evolution.

Contribution

It introduces a detailed analysis of phase diagram subtypes in binary mixtures with varying chemical potentials, combining integral-equation theory and Monte Carlo simulations.

Findings

Identification of two phase behavior subtypes

Good agreement between theory and simulations

Insights into the evolution between subtypes

Abstract

We have investigated the phase behaviour of a symmetrical binary fluid mixture for the situation where the chemical potentials $\mu_1$ and $\mu_2$ of the two species differ. Attention is focused on the set of interparticle interaction strengths for which, when $\mu_1=\mu_2$, the phase diagram exhibits both a liquid-vapor critical point and a tricritical point. The corresponding phase behaviour for the case $\mu_1\ne\mu_2$ 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.