Kinetics studies of bromine monoxide and methylperoxy free radicals by flash photolysis

Citation

Sander, Stanley Paul (1980) Kinetics studies of bromine monoxide and methylperoxy free radicals by flash photolysis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/9BZ5-X071. https://resolver.caltech.edu/CaltechETD:etd-11032006-131828

Abstract

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A flash photolysis-ultraviolet absorption system was constructed to study the kinetics of gas-phase free radical reactions over a wide range of pressure and temperature. Because of their atmospheric importance, the reactions of methylperoxy (CH302) and bromine monoxide (BrO) radicals with themselves, and with NO and NO2 were investigated:

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The rate constants for reactions 1 - 6 were determined by measuring the first-order or second-order decay rates of BrO and CH3O2 radicals by ultraviolet absorption spectrophotometry. The rate constants for reactions 3 and 6 were found to vary significantly with pressure, indicating the formation of a stable adduct. The pressure dependence of the rate constants was discussed in terms of the Troe theory of unimolecular reactions. Measurements of the branching ratio of reaction 4 were used to develop a detailed reaction mechanism for the disproportionation of BrO radicals. Upper limits were also obtained for the rate constants for the reactions

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The atmospheric implications of the rate constant measurements are discussed.

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