Influence of asymmetric depletion of solvents on the electric double layer of charged objects in binary polar solvent mixture

TL;DR

This paper develops a theoretical model to analyze how asymmetric solvent depletion near charged objects affects the electric double layer in binary polar solvent mixtures, considering solvent size and dipole moment differences.

Contribution

It introduces a general mean-field framework accounting for solvent size and dipole moment differences, predicting asymmetric solvent depletion and changes in permittivity.

Findings

Asymmetric solvent depletion occurs near charged surfaces.

Decreased permittivity of the solvent mixture is predicted.

Solvent dipole moment to volume ratio is key for depletion behavior.

Abstract

For binary solvent mixtures composed of ions and two kinds of polar solvents, electric double layer near a charged object is strongly affected by not only the binary solvent composition but also nature of solvents such as volume and dipole moment of a solvent molecule. Accounting for difference in sizes of solvents and orientational ordering of solvent dipoles, we theoretically obtain general expressions for the spatial distribution functions of solvents and ions, in planar geometry and within the mean-field approach. Although focusing on long-range electrostatic interaction, we neglect short-range interactions such as preferential solvation, our approach predicts an asymmetric depletion of the two solvents from the charged surface and a behavior of decreased permittivity of the binary solvent mixture. Furthermore, we suggest that the key factor for the depletion is the ratio of the solvent dipole moment to the solvent volume. The influence of binary solvent composition, volume of solvent and dipole moment of solvent on the number density of solvents, permittivity and differential capacitance are presented and discussed, respectively. We conclude that accounting for difference in the volume and dipole moment between polar solvents is necessary for new approach to represent more realistic situations such as preferential solvation.