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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

✍ Scribed by Ole J. Nielsen; Howard W. Sidebottom; Michael Donlon; Jack Treacy

Publisher: Elsevier Science
Year: 1991
Tongue: English
Weight: 652 KB
Volume: 178
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(91)87051-c

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✦ Synopsis

Rate constants for the reactions of OH radicals and Cl atoms with CH30N02. C,H,ONO,, n-C3H,0N02, n-C4H90N02, and n-C5H,,0NOZ have been determined at 298 f 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute-rate technique of 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 -ONO* group substantially decreases the rate constant for H-atom abstraction by OH radicals from groups bonded to the -ONO* group and also decreases that for groups in the p position. Similar results were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends.

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