KINETIC-STUDIES ON THE REACTIONS OF HYDROXYL RADICALS WITH DIETHERS AND HYDROXYETHERS

Rare constants for the reactions of OH radicals with a series of dieth ers and hydroxyethers have been determined at 298 +/- 2 K. Rate measur ements were made using a pulsed laser photolysis resonance fluorescenc e technique at total pressures of similar to 100 Torr and a convention al photolytic relative rate method at atmospheric pressure. The temper ature dependencies of the rate constants for four diethers were also s tudied over the temperature range 230-372 K using pulsed laser photoly sis resonance fluorescence. The rate data for reaction of OH with the diethers show significant deviations from simple structure-activity re lationships. Evidence is presented that suggests that these deviations may be a consequence of stabilization of the reaction transition stat es by hydrogen bonding.