Non-Arrhenius behavior in the initial rate of a catalytic-surface reaction: Theory and Monte Carlo simulation

Kristen Ann Fichthorn, Prakash G. Balan

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We have identified the factors contributing to the compensation effect in the initial rate of a bimolecular surface reaction, the kinetics of which are influenced by adsorbate lateral interactions. A simple theory, based on the quasichemical approximation, can predict the temperature ranges over which compensation is the most pronounced in Monte Carlo simulations of the initial rate. Both the simulations and the theory reveal an interesting phenomenon - apparent negative activation energies, which occur when the activation energy for reaction increases with increasing temperature faster than kBT. This phenomenon could contribute to experimentally observed decreases seen in the rate of the CO oxidation reaction on several single-crystal metal surfaces.

Original languageEnglish (US)
Pages (from-to)10028-10037
Number of pages10
JournalThe Journal of Chemical Physics
Volume101
Issue number11
DOIs
StatePublished - Jan 1 1994

Fingerprint

Surface reactions
surface reactions
Activation energy
Adsorbates
Carbon Monoxide
activation energy
simulation
Metals
Single crystals
Oxidation
Temperature
Kinetics
metal surfaces
oxidation
temperature
single crystals
kinetics
approximation
Monte Carlo simulation
Compensation and Redress

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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Non-Arrhenius behavior in the initial rate of a catalytic-surface reaction : Theory and Monte Carlo simulation. / Fichthorn, Kristen Ann; Balan, Prakash G.

In: The Journal of Chemical Physics, Vol. 101, No. 11, 01.01.1994, p. 10028-10037.

Research output: Contribution to journalArticle

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