Modified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity

Title Modified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity
Publication Type Journal Article
Authors
Keywords
Abstract
Mechanistic modeling provides vital insights into catalytic reactions. To analyze complex reaction networks with parallel pathways, we leverage the graph theory approach of the Energy Span Model (ESM) to develop a modified energy span analysis (MESA). A new method of cycle plots is proposed to perform reaction pathways analysis visually. We demonstrate this method on two published models: one describing carbon monoxide oxidation and the other simulating ethylene conversion to propanal via hydroformylation or ethane via hydrogenation. Fundamental insights explain kinetic observables, such as a reactant’s negative reaction order. General principles are revealed, such as rate-determining surface species being outside the primary reaction flux cycle and pathway selectivity being a purely kinetic property when reaction conditions are not near equilibrium. Finally, we demonstrate MESA’s consistency with published microkinetic modeling results, highlighting this technique’s extension of the ESM to heterogeneous catalysts using collision theory to describe adsorption steps and concentration effects.
Year of Publication
2022
Journal
Industrial & Engineering Chemistry Research
Volume
62
Number of Pages
2191-2201
Date Published
apr
URL
DOI
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