Absolute rate of the reaction of O/3-P/ with hydrogen sulfide over the temperature range 263 to 495 K

The technique of flash photolysis coupled with time resolved detection of O via resonance fluorescence has been used to obtain rate constants for the reaction of O(3-P) with H2S at temperatures from 263 to 495 K and at pressures in the range 10-400 torr. Under conditions where secondary reactions are avoided, the measured rate constants for the primary step obey the Arrhenius equation k = (7.24 plus or minus 1.07) x 10 to the -12th exp(-3300 plus or minus 100/1.987 T) cu cm/molecules/s. Experiments with D2S show that the reaction exhibits a primary isotope effect, in support of a hydrogen abstraction mechanism.