Effect of Bjerrum pairs on electrostatic properties in an electrolyte solution near charged surfaces: A mean-field approach

TL;DR

This study uses a mean-field approach to explore how ion pairing, finite size effects, and dipole moments influence electrostatic properties in electrolyte solutions near charged surfaces, revealing key phenomena affecting capacitance and permittivity.

Contribution

It introduces a lattice statistical mechanics model that accounts for ion association, finite sizes, and dipole moments, providing new insights into electrostatic behavior near charged interfaces.

Findings

Bjerrum pairs affect permittivity and capacitance.

High dipole moment Bjerrum pairs increase near charged surfaces.

Concentration and dipole differences influence osmotic pressure.

Abstract

In this paper, we investigate the consequences of ion association, coupled with the considerations of finite size effects and orientational ordering of Bjerrum pairs as well as ions and water molecules, on electric double layer near charged surfaces. Based on the lattice statistical mechanics accounting for finite sizes and dipole moments of ions, Bjerrum pairs and solvent molecules, we consider the formation of Bjerrum pairs and derive the mathematical expressions for Bjerrum pair number density as well as cation/anion number density and water molecule number density. We reveal the several significant phenomena. Firstly, it is shown that our approach naturally yields the equilibrium constant for dissociation-association equilibrium between Bjerrum pairs and ions. Secondly, at low surface charge densities, an increase in the bulk concentration of Bjerrum pairs enhances the permittivity and decreases the differential capacitance. Next, for cases where Bjerrum pairs in an alcohol electrolyte solution have a high value of dipole moment, Bjerrum pair number density increases with decreasing distance from the charged surface, and differential capacitance and permittivity is high compared to ones for the cases with lower values of Bjerrum-pair dipole moments. Finally, we show that the difference in concentration and dipole moment of Bjerrum pairs can lead to some variation in osmotic pressure between two similarly charged surfaces.