Kinetic description of site ensembles on catalytic surfaces.

ABSTRACT: We demonstrate that the Langmuir-Hinshelwood formalism is an incomplete kinetic description and, in particular, that the Hinshelwood assumption (i.e., that adsorbates are randomly distributed on the surface) is inappropriate even in catalytic reactions as simple as A + A → A2 The Hinshelwood assumption results in miscounting of site pairs (e.g., A*-A*) and, consequently, in erroneous rates, reaction orders, and identification of rate-determining steps. The clustering and isolation of surface species unnoticed by the Langmuir-Hinshelwood model is rigorously accounted for by derivation of higher-order rate terms containing statistical factors specific to each site ensemble. Ensemble-specific statistical rate terms arise irrespective of and couple with lateral adsorbate interactions, are dist

SUBMITTER: Razdan NK 

PROVIDER: S-EPMC7923573 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature