BIROn - Birkbeck Institutional Research Online

    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.

    [img]
    Preview
    Text
    thompson2.pdf

    Download (546kB) | Preview

    Abstract

    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.

    Metadata

    Item Type: Article
    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)
    Depositing User: Administrator
    Date Deposited: 05 Oct 2005
    Last Modified: 06 Dec 2016 10:38
    URI: http://eprints.bbk.ac.uk/id/eprint/236

    Statistics

    Downloads
    Activity Overview
    354Downloads
    514Hits

    Additional statistics are available via IRStats2.

    Archive Staff Only (login required)

    Edit/View Item Edit/View Item