Accurate rate expressions for simulations of gas-phase chemical reactions

Patrick D. O'Connor, Lyle Norman Long, James B. Anderson

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Several of the commonly used expressions giving reaction rates for model chemical reactions, though accurate for very high activation energies (i.e. Ea ≫ kBT), are inaccurate for more typical reaction conditions. In this paper we provide the complete and accurate rate expressions for model reactions having cross-sections dependent on translational, line-of-centers translational, and internal energies as well as on combinations thereof. Included are rate expressions for models giving Arrhenius-like temperature dependencies. Tests of several of the models and their corresponding cross-section expressions were made using Bird's direct simulation Monte Carlo method. These were successful in reproducing the experimentally determined rates over the full range of temperatures for the representative reactions: HF + H → H2 + F, CO + OH → CO2 + H, H2 + O → OH + H and H2 + Cl → HCl + H.

Original languageEnglish (US)
Pages (from-to)7664-7673
Number of pages10
JournalJournal of Computational Physics
Volume227
Issue number16
DOIs
StatePublished - Aug 10 2008

Fingerprint

Chemical reactions
chemical reactions
vapor phases
Gases
simulation
birds
cross sections
Birds
internal energy
Reaction rates
Monte Carlo method
reaction kinetics
Monte Carlo methods
Activation energy
activation energy
Temperature
temperature

All Science Journal Classification (ASJC) codes

  • Numerical Analysis
  • Modeling and Simulation
  • Physics and Astronomy (miscellaneous)
  • Physics and Astronomy(all)
  • Computer Science Applications
  • Computational Mathematics
  • Applied Mathematics

Cite this

O'Connor, Patrick D. ; Long, Lyle Norman ; Anderson, James B. / Accurate rate expressions for simulations of gas-phase chemical reactions. In: Journal of Computational Physics. 2008 ; Vol. 227, No. 16. pp. 7664-7673.
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Accurate rate expressions for simulations of gas-phase chemical reactions. / O'Connor, Patrick D.; Long, Lyle Norman; Anderson, James B.

In: Journal of Computational Physics, Vol. 227, No. 16, 10.08.2008, p. 7664-7673.

Research output: Contribution to journalArticle

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