Abstract
AbstractReactions of Cl atoms with HOCl (1), CH3OCl (2) and C4H9OCl (3) have been investigated at 300 K using discharge flow LIF/MS technique. The mechanism and reaction rate constants were determined by monitoring absolute rates of hypochlorite and CI atom consumption together with the build‐up of reaction products. Based on the yields of CI2 and OH in (1a), Cl2 and CH3O in (2a) and Cl2 in (3a), as measured by MS/LIF, the reactions of Cl atom with the hypochlorites investigated in this work were found to proceed predominantly via the Cl atom abstraction channel with k1a/k1 = (0.96±0.05), k2a/k2 = (0.85 ± 0.06), k3a/k3 = (1.01 ±0.05). The reaction rate constants were determined to be k1 = (2.28±0.09)·10−12, k2 = (6.0±0.2)·10−11, and k3 = (4.26±0.2)·10−11, all in units cm3·molecule−1·s−1. A reevaluation of the heat of formation of HOCl yielded ΔH0f (298 K) = −75.1 kJ·mol−1.
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