| Abstract: | Absolute rate coefficients for the gas‐phase reactions of trans‐dichloroethene and trichloroethene with O(3P) atoms have been measured at 298 K using a discharge flow tube coupled to a chemiluminescence detection system. The observed rate constant values are (2.2 ± 0.4) × 10?13 and (1.4 ± 0.2) × 10?13 cm3 molecule?1 s?1, respectively. The experiments were carried out under pseudo‐first‐order conditions with O(3P)]o ? alkene]o. These results are compared to those of O atom reactions with other chloroethenes and with different electrophiles, such as OH and NO3. Different factors that affect the rate of addition to the double bond are considered. The rate constants for these reactions do not correlate in a simple manner with the experimental ionization potential, as is the case in the alkene and methyl‐substituted alkene reactions. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 415–421, 2001 |
