Adsorption preference reversal phenomenon from multisite-occupancy theory fortwo-dimensional lattices

TL;DR

This paper develops a statistical thermodynamics model for polyatomic mixtures on 2D lattices, revealing how lattice structure influences adsorption preference reversal phenomena.

Contribution

It introduces a generalized lattice-gas model that accounts for multisite occupancy and provides insights into the effects of dimensionality and lattice structure on adsorption behavior.

Findings

Exact thermodynamics for 1D mixtures

Approximate model for 2D systems

Insights into adsorption preference reversal

Abstract

The statistical thermodynamics of polyatomic species mixtures adsorbed on two-dimensional substrates was developed on a generalization in the spirit of the lattice-gas model and the classical Guggenheim-DiMarzio approximation. In this scheme, the coverage and temperature dependence of the Helmholtz free energy and chemical potential are given. The formalism leads to the exact statistical thermodynamics of binary mixtures adsorbed in one dimension, provides a close approximation for two-dimensional systems accounting multisite occupancy and allows to discuss the dimensionality and lattice structure effects on the known phenomenon of adsorption preference reversal.