Surface barriers and symmetry of adsorption and desorption processes

Abstract

Adsorption and desorption of hydrocarbons in a realistic model (2496 atoms) of ZSM-5 zeolite (MFI), including an external surface and a reservoir for molecules, have been studied using classical molecular dynamics, with special focus on surface barriers. Different degrees of surface blocking have been modeled according to experimental observations. Using previous molecular dynamics results, from the analysis of adsorption and desorption path lengths, we demonstrate that surface barriers are symmetric, i.e. with equal paths for desorption and adsorption, in agreement with the principle of microscopic reversibility and in contradiction with a model proposed recently. A new thermodynamic analysis confirms the symmetry of adsorption/desorption paths.