Phase behaviour in ionic solutions: restricted primitive model of ionic liquid in explicit neutral solvent

TL;DR

This study investigates the phase behavior of ionic solutions modeled as a restricted primitive model mixed with neutral hard spheres, using various approximations to analyze fluid-fluid coexistence and critical phenomena.

Contribution

It introduces a comprehensive theoretical framework for phase behavior in ionic solutions with explicit solvent, comparing multiple regularizations and approximations against simulation data.

Findings

All approximations predict a fluid-fluid coexistence with an upper critical point.

Increasing pressure shifts the coexistence region to higher densities and solvent concentrations.

AMSA with the Olaussen-Stell association constant best matches simulation results.

Abstract

We study fluid-fluid equilibrium in the simplest model of ionic solutions where the solvent is explicitly included, i.e., a binary mixture consisting of a restricted primitive model (RPM) and neutral hard-spheres (RPM-HS mixture). First, using the collective variable method we find free energy, pressure and partial chemical potentials in the random phase approximation (RPA) for a rather general model that takes into consideration solvent-solvent and solvent-ion interactions beyond the hard core. In the special case of a RPM-HS mixture, we consider two regularizations of the Coulomb potential inside the hard core, i.e., the Weeks-Chandler-Andersen (WCA) regularization leading to the WCA approximation and the optimized regularization giving the optimized RPA (ORPA) or the mean spherical approximation (MSA). Furthermore, we calculate the phase coexistence using the associative mean spherical approximation (AMSA). In general, the three approximations produce qualitatively similar phase diagrams of the RPM-HS mixture, i.e., a fluid-fluid coexistence envelope with an upper critical solution point, a shift of the coexistence region towards higher total number densities and higher solvent concentrations with increasing pressure, and a small increase of the critical temperature with an increase of pressure. As for a pure RPM, the AMSA leads to the best agreement with the available simulation data when the association constant proposed by Olaussen and Stell is used. We also discuss the peculiarities of the phase diagrams in the WCA approximation.