Kinetic studies of diatomic free radicals using mass spectrometry. Part 2.—Rapid bimolecular reactions involving the ClO X2Πradical

Abstract

The kinetics of rapid bimolecular reactions involving ClO, X²Π, v= 0, radicals at 298 K have been studied mass spectrometrically using molecular beam sampling from a discharge-flow system. The following rate constants (298 K, cm³ molecule^–1 s^–1) are reported: [graphic omitted] ClO radicals were found to be unreactive towards a range of singlet ground state molecules, up to 670K. The reactions (1) and (2) are important rate-determining steps in the proposed ClO_x cycle for depletion of ozone in the stratosphere. The implications for this ClO_x cycle of recent measurements of rate constants involving Cl, ClO and OClO, are discussed.