Abstract
The kinetics of the decay reaction of the ClO(X2Π) radical have been investigated by time-resolved electronic absorption spectrophotometry in a discharge-flow system. Ar and Ar + SF6 mixtures were used as carrier gases at 294 K; over the concentration range 45.31 × 10–8[Ar]2.53 × 10–8 g atom cm–3 the decay reaction of ClO radicals was second order. Insignificant effects of third bodies (M = Ar, SF6) were observed. Decay of ClO occurred predominantly under these conditions via reaction (2), [graphic omitted] with k2= 10(11.89 ± 0.04) exp [(–1150±50)/T] cm3 mol–1 s–1 in the temperature range 273 to 710 K. The low activation energy for reaction (2) and the large range of T–1 of these measurements closely define the frequency factor for reaction (2). The data were combined with earlier measurements of k–2 by Johnston, Morris and Van den Bogaerde to give an accurate value for the dissociation energy of the ClOO radical, D°298(Cl—OO)=(29±3) kJ mol–1.
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