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 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.