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


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.


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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.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Environmental Science and Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Seinfeld, John H. (advisor)
  • Watson, Robert T. (co-advisor)
Thesis Committee:
  • Unknown, Unknown
Defense Date:6 December 1979
Record Number:CaltechETD:etd-11032006-131828
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4396
Deposited By: Imported from ETD-db
Deposited On:05 Dec 2006
Last Modified:21 Dec 2019 04:27

Thesis Files

PDF (Sander_sp_1980.pdf) - Final Version
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