Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range

Chao Yan, Stefani Kocevska, Lev Krasnoperov

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33 Scopus citations

Abstract

Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O(1D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10-11(T/298 K)â 81 cm3 molecule-1 s-1 (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.

Original languageEnglish (US)
Pages (from-to)6111-6121
Number of pages11
JournalJournal of Physical Chemistry A
Volume120
Issue number31
DOIs
StatePublished - Aug 11 2016

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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