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On the use temperature parameterized rate coefficients in the estimation of non-equilibrium reaction rates

TitleOn the use temperature parameterized rate coefficients in the estimation of non-equilibrium reaction rates
Publication TypeJournal Article
Year of Publication2006
AuthorsShizgal, BD, Chikhaoui, A
JournalPhysica a-Statistical Mechanics and Its Applications
Volume365
Pagination317-332
Date PublishedJun
Type of ArticleArticle
ISBN Number0378-4371
KeywordsBIMOLECULAR CHEMICAL-REACTION, Boltzmann equation, BOLTZMANN-EQUATION, Chapman-Enskog, CHAPMAN-ENSKOG METHOD, CHEMISTRY, DILUTE GAS, LORENTZ GAS, MULTICOMPONENT SYSTEMS, NITROGEN-ATOMS, nonequilibrium, PERTURBATION, REACTIONS, VELOCITY DISTRIBUTION
Abstract

The present paper considers a detailed analysis of the nonequilibrium effects for a model reactive system with the Chapman-Eskog (CE) solution of the Boltzmann equation as well as an explicit time dependent solution. The elastic cross sections employed are a hard sphere cross section and the Maxwell molecule cross section. Reactive cross sections which model reactions with and without activation energy are used. A detailed comparison is carried out with these solutions of the Boltzmann equation and the approximation introduced by Cukrowski and coworkers [J. Chem. Phys. 97 (1992) 9086; Chem. Phys. 89 (1992) 159; Physica A 188 (1992) 344; Chem. Phys. Lett. A 297 (1998) 402; Physica A 275 (2000) 134; Chem. Phys. Lett. 341 (2001) 585; Acta Phys. Polonica B 334 (2003) 3607.] based on the temperature of the reactive particles. We show that the Cukrowski approximation has limited applicability for the large class of reactive systems studied in this paper. The explicit time dependent solutions of the Boltzmann equation demonstrate that the CE approach is valid only for very slow reactions for which the corrections to the equilibrium rate coefficient are very small. (c) 2005 Elsevier B.V. All rights reserved.

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