Temperature dependence of the rate constant for the HO/sub 2/ + CH/sub 3/O/sub 2/ gas-phase reaction

Journal Article · Thu Jun 30 04:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100324a030· OSTI ID:6477682

Dagut, P; Wallington, T J; Kurylo, M J

The temperature dependence of the reaction between hydroperoxy and methylperoxy radicals was measured in a flash photolysis ultraviolet absorption apparatus over the temperature range 228-380 K: HO/sub 2/ + CH/sub 3/O/sub 2/ ..-->.. CH/sub 3/O/sub 2/H + O/sub 2/ (1). The data, represented by the Arrhenius expression k/sub 1/ = (3.0 +/- 1.2) x 10/sup -13/ exp((720 +/- 100)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, are compared to earlier results and discussed in terms of the reaction mechanism. Due to overlapping absorptions of the two radicals and deviations of the complex reaction system from both pseudo-first-order and pseudo-second-order behavior, the rate constants were determined from a detailed modeling of the radical decay curves. A sensitivity analysis of the rate constant determination procedure to the assumed radical absorption cross sections and correlated changes in the rate constants for the HO/sub 2/ and CH/sub 3/O/sub 2/ self-reactions was performed, and the results are reported. The present results were also used to assess the effects of secondary chemistry in the authors measurements of the temperature dependence of the rate constant of the CH/sub 3/O/sub 2/ + CH/sub 3/O/sub 2/ reaction, and the revised Arrhenius parameters are presented.

• Research Organization: National Bureau of Standards, Gaithersburg, MD (USA)
• OSTI ID: 6477682
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:13; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EQUATIONS
EXPERIMENTAL DATA
FLUIDS
GASES
HYDROPEROXY RADICALS
INFORMATION
KINETICS
NUMERICAL DATA
PEROXY RADICALS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
TEMPERATURE DEPENDENCE