A Gaskinetic Investigation of HOBr Reactions with CI(2P), O(3P) and OH(2II). The Reaction of BrCl with OH(2II)

Abstract

AbstractThe reactions of HOBr with atomic chlorine (1), with oxygen (2) and with hydroxyl radicals (3) have been investigated at 300 K using the discharge flow technique with mass‐spectrometric detection. The rate constants based on HOBr consumption have been determined to be k1 = (8.0±0.4)·10−11 and k2 = (3.1±0.2)·10−11. For the reaction with OH radicals k3<5×10−13 was obtained. All rate constants are given in units cm3 molecule−1 s−1.The reactions of HOBr with Cl and with O are shown to proceed via bromine abstraction with formation of BrCl and BrO, respectively. The predominant channel in the reaction of OH with BrCl was identified to be step (4a) OH+BrCl → HOBr+Cl (4a) Based on the present kinetic investigation the heat of formation for HOBr at T = 300 K was evaluated to be ΔH0f (HOBr) = −(60.22±2) kJ · mol−1.