Kinetic modeling of the benzyl + HO2 reaction

Document Type

Conference Proceeding

Publication Date

1-1-2007

Abstract

Benzyl is a resonantly stabilized radical that commonly occurs as an intermediate in the combustion of aromatic compounds. The bimolecular reaction of benzyl with HO2 is important in the thermal and oxidative destruction of benzyl, especially at low to moderate temperatures, where unimolecular decomposition of the benzyl radical is slow. We show that the addition of HO2 to the methylene site in benzyl produces a vibrationally excited benzyl hydroperoxide adduct, with over 60 kcal mol-1 of excess energy over the ground state. RRKM simulations are performed on the benzyl + HO2 reaction, using thermochemical and kinetic parameters obtained from ab initio calculations, with variational transition state theory (VTST) for treatment of barrier-less radical + radical reaction kinetics. Our results reveal that the benzyl + HO2 reaction proceeds predominantly to the benzoxyl radical + OH at temperatures over 700 K, with the production of stabilized benzylhydroperoxide molecules dominating at lower temperatures.

Identifier

84946575851 (Scopus)

ISBN

[9781604239454]

Publication Title

Fall Technical Meeting of the Eastern States Section of the Combustion Institute 2007 Chemical and Physical Processes in Combustion

First Page

212

Last Page

217

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