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Kinetic Studies on the Reactions of Hydroxyl Radicals with Diethers and Hydroxyethers

Rate constants for the reactions of OH radicals with a series of diethers and hydroxyethers have been determined at 298 ± 2 K. Rate measurements were made using a pulsed laser photolysis resonance fluorescence technique at total pressures of ∼100 Torr and a conventional photolytic relative rate meth...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 1997-08, Vol.101 (32), p.5770-5775
Main Authors: Porter, Edward, Wenger, John, Treacy, Jack, Sidebottom, Howard, Mellouki, Abdelwahid, Téton, Sophie, LeBras, Georges
Format: Article
Language:English
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Summary:Rate constants for the reactions of OH radicals with a series of diethers and hydroxyethers have been determined at 298 ± 2 K. Rate measurements were made using a pulsed laser photolysis resonance fluorescence technique at total pressures of ∼100 Torr and a conventional photolytic relative rate method at atmospheric pressure. The temperature dependencies of the rate constants for four diethers were also studied over the temperature range 230−372 K using pulsed laser photolysis resonance fluorescence. The rate data for reaction of OH with the diethers show significant deviations from simple structure−activity relationships. Evidence is presented that suggests that these deviations may be a consequence of stabilization of the reaction transition states by hydrogen bonding.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp971254i