Dielectric Properties of Aqueous Electrolyte Solutions Confined in Silica Nanopore: Molecular Simulation vs. Continuum-Based Models

Abstract

Dielectric behavior of electrolyte aqueous solutions with various concentrations in a cylindrical nanopore of MCM 41 silica has been investigated. The effect of confinement is investigated by using isothermal-isosurface-isobaric statistical ensemble, which has proved to be an effective alternative to the Grand Canonical Monte Carlo (GCMC) simulation method. Several single-salt solutions have been considered (e.g., NaCl, NaI, BaCl2, MgCl2) in order to investigate the effect of ion polarizability, ion size, and ion charge. The effect of salt concentration has also been addressed by considering NaCl solutions at different concentrations (i.e., 0.1 mol/L, 0.5 mol/L, and 1 mol/L). The motivation in performing this integrated set of simulations is to provide deep insight into the dielectric exclusion in NF theory that plays a significant role in separation processes. It was shown that the dielectric constant increased when ions were added to water inside the nanopore (with respect to the dielectric constant of confined pure water) unlike what was obtained in the bulk phase and this phenomenon was even more pronounced for electrolytes with divalent ions (MgCl2 and BaCl2). Therefore, our simulations indicate opposite effects of ions on the dielectric constant of free (bulk) and nanoconfined aqueous solutions.