Mechanism and Rate Constants for the Reactions of Cl Atoms with HOCL, CH_3Ocl and tert-C_4H_9OCl

摘要

Reactions of Cl atoms with HOCl(1), CH_3Ocl(2) and C_4H_9Ocl(3) have been investigated at 300 K using dis- charge flow LIF/MS technique. The mechanism and reaction rate constants were determined by monitoring absolute rates of hypochlorite and Cl atom consumption together with the buil-up of reaction products. Based on the yields of Cl_2 and OH in (1 a), Cl_2 and CH_3O in (2a) and Cl_2 in (3a), as measured by MS/LIF, the reac- tions of Cl atom with the hypochlorites investigated in this work were found to proceed predominantly via the Cl atom abstraction channel with k_1a/k_1 = (0.85 ± 0.06), k_3a/k_3 = (1.01 ± 0.05).