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An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

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Rate constants for the reaction of OH radicals and Cl atoms with CH3ONO2, C2H5ONO2, n-C3H7ONO2, n-C4H9ONO2, and n-C5H11ONO2 have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute-rate technique or pulse radiolysis combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways. The data show that the -ONO2 group substantially decreases the rate constant for H-atom abstraction by OH radicals from groups bonded to the -ONO2 group and also decreases that for groups in the β position. Similar resuls were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends.

OriginalsprogEngelsk
TidsskriftChemical Physics Letters
Vol/bind178
Udgave nummer2-3
Sider (fra-til)163-170
Antal sider8
ISSN0009-2614
DOI
StatusUdgivet - 22 mar. 1991

ID: 228197648