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-unsaturat

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• 作者：King ; Martin D. ; Thompson ; Katherine C.
• 关键词：HOMO energy ; SOMO energy ; Halogenated alkenes ; Alkylated alkenes ; Troposphere oxidation ; Peroxy radical
• 刊名：Atmospheric Environment
• 出版年：2003
• 出版时间：October, 2003
• 年：2003
• 卷：37
• 期：32
• 页码：4517-4527
• 全文大小：196 K

文摘

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.