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Rate constants for the gas-phase reactions of hydroxyl radicals and chlorine atoms with aliphatic alcohols and ethers have been determined at 298 f 2 K and at a total pressure of 1 atmosphere. The OH radical rate data were obtained using both the absolute technique of pulse radiolysis combined with kinetic UV spectroscopy and a conventional photolytic relative rate method. The C1 atom rate constants were measured using only the relative rate method.

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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.