Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: the collective variables-based approach

TL;DR

This paper develops a collective variables-based theory to analyze the vapor-liquid phase behavior of size- and charge-asymmetric ionic fluids confined in disordered porous matrices, revealing how confinement and asymmetry influence phase diagrams.

Contribution

It introduces a new theoretical approach extending scaled particle theory to study asymmetric ionic fluids in disordered matrices, including explicit third-order ion correlations.

Findings

Phase coexistence narrows with decreasing porosity.

Critical temperature and density decrease with porosity reduction.

Increased ion size asymmetry accelerates phase transition disappearance.

Abstract

We develop a theory based on the method of collective variables to study the vapor-liquid equilibrium of asymmetric ionic fluids confined in a disordered porous matrix. The approach allows us to formulate the perturbation theory using an extension of the scaled particle theory for a description of a reference system presented as a two-component hard-sphere fluid confined in a hard-sphere matrix. Treating an ionic fluid as a size- and charge-asymmetric primitive model (PM) we derive an explicit expression for the relevant chemical potential of a confined ionic system which takes into account the third-order correlations between ions. Using this expression, the phase diagrams for a size-asymmetric PM are calculated for different matrix porosities as well as for different sizes of matrix and fluid particles. It is observed that general trends of the coexistence curves with the matrix porosity are similar to those of simple fluids under disordered confinement, i.e., the coexistence region gets narrower with a decrease of porosity, and simultaneously the reduced critical temperature $T_{c}^{*}$ and the critical density $\rho_{i,c}^{*}$ become lower. At the same time, our results suggest that an increase in size asymmetry of oppositely charged ions considerably affects the vapor-liquid diagrams leading to a faster decrease of $T_{c}^{*}$ and $\rho_{i,c}^{*}$ and even to a disappearance of the phase transition, especially for the case of small matrix particles.