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Showing papers by "Mary K. Gilles published in 1999"



Journal ArticleDOI
TL;DR: In this paper, the rate coefficient for the reaction OH + ClO → products (1) was measured under pseudo-first-order conditions in OH, and the value of k1 between 234 and 356 K was given by k1(T) = (8.9 ± 2.7) × 10-12 exp[(295 ± 95)/T] cm3 molecule-1 s-1, where uncertainties are 95% confidence limits and include estimated systematic uncertainties.
Abstract: The rate coefficient for the reaction OH + ClO → products (1) was measured under pseudo-first-order conditions in OH. A discharge flow system was used to produce ClO, and its concentration was measured by UV/visible absorption. OH was produced by pulsed laser photolysis of O3 (or ClO) at 248 nm in the presence of H2O and was monitored by laser-induced fluorescence. The value of k1 between 234 and 356 K is given by k1(T) = (8.9 ± 2.7) × 10-12 exp[(295 ± 95)/T] cm3 molecule-1 s-1, where uncertainties are 95% confidence limits and include estimated systematic uncertainties. Our value is compared with those from previous investigations.

25 citations


Journal ArticleDOI
TL;DR: In this article, the role of closed-ring intermediates in chemistry, in general, and focuses on recent experimental and theoretical works that provide compelling evidence for a five-membered ring intermediate in the gas phase.
Abstract: This review considers the role of closed-ring intermediates in chemistry, in general, and focuses on recent experimental and theoretical works that provide compelling evidence for a fivemembered ring intermediate in the gas phase. The reactions of oxygen atoms with ethyl iodide and larger alkyl iodides produce HOI and a corresponding ethylenic compound via attack of the oxygen atom at the iodine and closure of the five-membered ring between the oxygen and a hydrogen on the beta-carbon. Detailed results are gathered from infrared chemiluminescence and molecular beam scattering, as well as new kinetics and product yield experiments. The theoretical calculations fully support and characterize the novel reaction mechanism.