Modelling of surface reactions and diffusion mediated by bulk diffusion

Abstract

We develop a continuum framework applicable to solid-state hydrogen storage, cell biology and other scenarios where the diffusion of a single constituent within a bulk region is coupled via adsorption/desorption to reactions and diffusion on the boundary of the region. We formulate content balances for all relevant constituents and develop thermodynamically consistent constitutive equations. The latter encompass two classes of kinetics for adsorption/desorption and chemical reactions—fast and Marcelin–De Donder, and the second class includes mass action kinetics as a special case. We apply the framework to derive a system consisting of the standard diffusion equation in bulk and FitzHugh–Nagumo type surface reaction–diffusion system of equations on the boundary. We also study the linear stability of a homogeneous steady state in a spherical region and establish sufficient conditions for the occurrence of instabilities driven by surface diffusion. These findings are verified through numerical simulations which reveal that instabilities driven by diffusion lead to the emergence of steady-state spatial patterns from random initial conditions and that bulk diffusion can suppress spatial patterns, in which case temporal oscillations can ensue. We include an extension of our framework that accounts for mechanochemical coupling when the bulk region is occupied by a deformable solid.

This article is part of the theme issue ‘Foundational issues, analysis and geometry in continuum mechanics’.