Structural and thermodynamic properties of the restricted primitive model electrolyte in a mixture with uncharged hard spheres: a grand canonical Monte Carlo simulation and integral equation study

Abstract

A restricted primitive model electrolyte in a mixture with uncharged hard spheres was studied at room temperature using grand canonical Monte Carlo computer simulation and Ornstein–Zernike integral equation theory in the hypernetted chain approximation (HNC). The mean spherical approximation results are also presented for a few cases. We obtained the pair distribution functions of species of the system, the dependencies of the total fluid density and the ionic fraction on the chemical potentials, the excess internal energy and the heat capacity at constant volume for a wide range of chemical potentials of the species from the simulations and HNC theory. In the majority of cases, good agreement between the theoretical predictions and simulation data is obtained. The composition of the mixture is determined by the chemical potentials of both species. The pair distribution functions have a Debye-like shape at low densities for various values of the ion fraction. By increasing the chemical potential of the uncharged component, weak trends for structuring of the solution are observed with the formation of ion-hard sphere-ion complexes. At high densities, a tendency for in-phase oscillations of ion–ion functions is observed similar to the pure electrolyte in the restricted primitive model. We analysed the chemical potential–density and the chemical potential–ion fraction projections of the equation of state in detail. Also, the heat capacity at constant volume has been calculated for the first time. The model and the results are useful for the development of the theory of inhomogeneous fluid mixtures.

Keywords:

• electrolyte solutions
• mixtures
• grand canonical MC
• integral equations

Acknowledgements

M.L. and B.H.-L. acknowledge support from the Slovenian Research Agency (ARRS) through program P1-0201. We are grateful to Professor Vojko Vlachy for careful reading of the manuscript and useful comments. The authors are grateful to David Vazquez at the Institute of Chemistry, UNAM, for technical support.