Rate constants for the reaction of NO and HO2 with peroxy radicals formed from the reaction of OH, Cl or NO3 with alkenes, dienes and α,β-unsaturated carbonyls
King, M.D. and Thompson, Katherine C. (2003) Rate constants for the reaction of NO and HO2 with peroxy radicals formed from the reaction of OH, Cl or NO3 with alkenes, dienes and α,β-unsaturated carbonyls. Atmospheric Environment 37 (32), pp. 4517-4527. ISSN 1352-2310.
Rate constants for the gas-phase reaction of NO and HO2 radicals with 33 peroxy radicals are presented. The peroxy radicals are derived from the addition of either OH, Cl, or NO3 radicals, followed by addition of O2, to a series of alkenes: tetrachloroethene, ethene, 2,3-dimethyl but-2-ene, butadiene, 2,3,4,5-tetramethyl hexa-2,4-diene, 1,1,2,3,4,4-hexachlorobutadiene, but-1-ene-3-one (methyl vinyl ketone) and 2,3-dimethylpen-2-ene-4-one. The rate constants were predicted using a correlation between the singly occupied molecular orbital (SOMO) energy of the peroxy radical and the logarithm of the rate constant for reaction with NO or HO2. A discussion of the accuracy of the method and the trends in the reactivity of the titled peroxy radicals is given. Peroxy radicals derived from halogenated alkenes have larger values of rate constants for reaction with NO relative to reaction with HO2, indicating that they are more likely to react with NO, rather than HO2, in the atmosphere. The reverse is true for peroxy radicals derived from alkylated alkenes.
|Keyword(s) / Subject(s):||HOMO energy, SOMO energy, Halogenated alkenes, Alkylated alkenes, Troposphere oxidation, Peroxy radical|
|School:||Birkbeck Schools and Departments > School of Science > Biological Sciences|
|Research Centre:||Structural Molecular Biology, Institute of (ISMB)|
|Date Deposited:||05 Oct 2005|
|Last Modified:||06 Dec 2016 10:38|
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