Gas‐phase kinetics of the reactions of O( 3 P) atoms with ( Z )‐CHClCHCl, CCl 2 CH 2 , CCl 2 CCl 2 and ( E / Z )‐CFClCHCl at 298 K

The kinetics of the gas‐phase reactions of O( 3 P) atoms with ( Z )‐CHClCHCl, CCl 2 CH 2 , CCl 2 CCl 2 and ( E / Z )‐CFClCHCl were studied at 298 K using a discharge flow tube system. The overall rate constants based on the measured afterglow reactions were (2.0 ± 0.2) × 10 −13 , (11.3 ± 0.9) × 10 −13 , (1.9 ± 0.3) × 10 −13 , and (1.4 ± 0.3) × 10 −14 , respectively, all in units of cm 3 molecule −1  sec −1 . The experiments were carried out under pseudo‐first‐order conditions with [O( 3 P)] 0  ≪ [chloroethene]. Halogen substitution in the alkenes is discussed in terms of reactivity with O( 3 P) and its relation to the ionization potential and the reactivity with OH radicals. Copyright © 2006 John Wiley & Sons, Ltd.