Kinetic study on reactions of 1- and 2-methylvinoxy radicals with O2

Tatsuo Oguchi*, Akira Miyoshi, Mitsuo Koshi, Hiroyuki Matsui, Nobuaki Washida

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

The reactions of 1- and 2-methylvinoxy radicals with O2 have been studied by laser-induced fluorescence coupled with pulsed laser photolysis of precursor molecules at room temperature (298 ± 5 K). The rate constants for both reactions showed typical falloff pressure dependence in the investigated pressure range (8-330 Torr, He buffer), which suggests the dominance of recombination processes to form peroxy radicals. From the Rice - Ramsperger - Kassel - Morcus fit to the experimental data, the limiting high-pressure rate constants were derived to be k (1-methylvinoxy + O2) = 9.8 × 10-13 and k∞ (2-methylvinoxy + O2) = 1.3 × 10-12 cm3 molecule-1 s-1, which are 5-7 times larger than that for the reaction of a nonsubstituted vinoxy radical. The influence of the methyl substituent effect and the resonance stabilization on the rate constants is discussed.

Original languageEnglish
Pages (from-to)378-382
Number of pages5
JournalJournal of Physical Chemistry A
Volume105
Issue number2
DOIs
StatePublished - 18 Jan 2001

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