Kinetics Studies of Bromine Monoxide and Methylperoxy Free Radicals by Flash Photolysis

Author: Sander, Stanley Paul

Year: 1980

Degree: Dissertation (Ph.D.)

Advisor: Seinfeld, John H.

Committee Member: Unknown, Unknown

Option: Environmental Science and Engineering; Chemistry

DOI: 10.7907/9BZ5-X071

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:

[...].

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

[...].

The atmospheric implications of the rate constant measurements are discussed.

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