Statistical mechanics of fluids at a permeable wall

TL;DR

This paper develops a statistical mechanics framework for fluids near permeable walls, analyzing surface effects, adsorption, and tension through cluster expansion and pressure tensor methods, providing new insights into surface thermodynamics.

Contribution

It introduces a unified approach connecting cluster expansion and pressure tensor methods for surface phenomena at permeable boundaries.

Findings

Derived expressions for Henry constants of adsorption and absorption.

Extended Kirkwood-Buff formula for finite potential fields.

Established the equivalence of cluster and pressure tensor approaches.

Abstract

The problem of surface effects at a fluid boundary created by the force field of finite value is investigated. A classical simple fluid with a locally introduced field imitating a permeable solid is considered. The cases of micro- and macroscopically smooth boundary are examined and the analysis of static membranes is performed. Henry constant of adsorption and its connection with Henry constant of absorption, specific surface grand potential (gamma) and the surface number density are determined. High-temperature expansions and low-temperature limit for basic values are obtained. "The surface tension coefficient" decomposes into a value proportional to Henry constant of adsorption depending on the position of the separating surface, and a universal nonlinear surface coefficient. Two approaches to this problem are analyzed: through the surface cluster expansion and through the pressure tensor. Within the first approach, the series in powers of activity is obtained for gamma. This expression is similar to the cluster expansion for pressure but in contrast to this case the integrals of Ursell factors contain the multipliers depending on the potential of particles interaction with the external field. Within the second approach, Kirkwood-Buff formula for gamma is extended for the case of the field of finite value. A complete identity of the approaches of "cluster expansion" and "pressure tensor" is demonstrated, and the near-surface virial expansion which determines the exact equation of state of the "two-dimensional" gas of the near-surface region is constructed. Coincidence of pressure acting on a transverse wall and the tangential component of pressure tensor, both averages over the transition layer as well as the symmetry of the solution with respect to the permutation of sorbent - fluid are demonstrated.