Thermochemistry and kinetic modeling for OH addition to ethylene and propene and subsequent hydroxyethyl radical + O2 reactions in atmospheric chemistry

Document Type

Conference Proceeding

Publication Date

1-1-2009

Abstract

Regeneration of OH radicals has recently been considered as an important process in atmospheric chemistry of unsaturated hydrocarbons. We study the reaction of OH with ethanol and with propene and the subsequent reactions of the beta-hydroxyethyl radicals with O2 using theoretical density functional theory and ab initio methods. Detailed potential energy surfaces for these reactions are presented, with rate parameters calculated for each reaction step from transition state theory. The chemically activated hydroxyethyl + O2 systems are modeled using quantum Rice- Ramsperger-Kassel (QRRK) theory, with master equation analysis for falloff. The reaction system is further modeled under conditions of atmospheric experiments under varied NOx conditions using an elementary reaction mechanism with all reactions reversible. Major products in the β- hydroxyethyl radical + O2 reaction include formaldehyde, vinyl alcohol, and at low temperatures and high pressures the stabilized β-hydroxyethylperoxy radical. Incorporation of detailed kinetic modeling into analysis of atmospheric chemistry reaction systems may lead to better kinetic models for olefin oxidation chemistry the atmospheric.

Identifier

84946592953 (Scopus)

ISBN

[9781615676682]

Publication Title

Fall Meeting of the Eastern States Section of the Combustion Institute 2009

First Page

204

Last Page

211

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