Temperature-dependent kinetic study for ozonolysis of selected tropospheric alkenes

Ozonolysis reactions of alkenes are suggested to play major roles in the chemistry of the troposphere. Rate constants for the gas-phase reactions of O-3 with a series of alkenes were determined using relative rate technique based on GC/FID measurements of alkene decays, Experiments were carried out in air over the temperature range of 278-353 K at an atmospheric pressure of 760 Torr. An excess of 1,3,5-trimethylbenzene was used as a HO radical scavenger in all experiments. Arrhenius parameters were calculated for ozonolysis of 1-butene, 1-pentene, 1-hexene, 1-heptene, 2-methyl-1-butene, isobutene, trans-2-butene, trans-2-pentene, cis-2-pentene, trans-2-hexene, cis-2-hexene, 3-chloropropene, 1,1-dichloroethene, and isoprene from temperature-dependent studies of the rate constants. The rate constants obtained in this study are compared with previous literature data. A good linear correlation between the logarithms of the rate constants and calculated HOMO energies of selected alkenes is observed. However, no clear correlation could have been drawn for chlorinated substituted alkenes. (C) 2002 Wiley Periodicals, Inc.