Effect of ions on confined near-critical binary aqueous mixture

TL;DR

This paper investigates how ions influence the behavior of near-critical binary aqueous mixtures confined between charged surfaces, revealing modifications in charge profiles and effective interactions, especially near the critical point, with results aligning with recent experimental data.

Contribution

It extends Landau-Ginzburg theory to include electrostatic effects in near-critical mixtures with ions, providing analytical insights into charge profiles and surface interactions.

Findings

Charge density profiles are modified by ion solubility preferences.

Electrostatic interactions can produce attractive potentials between surfaces.

Theoretical results agree quantitatively with recent experiments.

Abstract

Near-critical binary mixtures containing ions and confined between two charged and selective surfaces are studied within a Landau-Ginzburg theory extended to include electrostatic interactions. Charge density profiles and the effective interactions between the confining surfaces are calculated in the case of chemical preference of ions for one of the solvent components. Close to the consolute point of the binary solvent, the preferential solubility of ions leads to the modification of the charge density profiles in respect to the ones obtained from the Debye-H\"uckel theory. As a result, the electrostatic contribution to the effective potential between the charged surface can exhibit an attractive well. Our calculations are based on the approximation scheme valid if the bulk correlation length of a solvent is much larger than the Debye screening length; in this critical regime the effect of charge on the concentration profiles of the solvent is subdominant. Such conditions are met in the recent measurements of the effective forces acting between a substrate and a spherical colloidal particle immersed in the near-critical water-lutidine mixture [Nature V. 451, 172 (2008)]. Our analytical results are in a quantitative agreement with the experimental ones.