OH yields in the gas-phase reactions of ozone with alkenes

Hydroxyl radical yields are reported for the gas-phase ozonolyses of a range of alkenes. 1,3,5-Trimethylbenzene was employed as an OH tracer, and the diminution in its concentration was used to calculate OH yields by both a simple analytical kinetic expression and a numerically integrated model. The following OH yields were obtained, relative to alkene consumed: ethene (0.14), propene (0.32), 2-methylpropene (0.60), 2,3-dimethyl-2-butene (0.89), isoprene (0.44), beta-pinene (0.24), and alpha-pinene (0.83). A structure activity relationship (SAR) is presented for the estimation of OH yields based on structural moieties and reaction branching ratios. Reaction stoichiometries (Delta[alkene]/Delta[ozone]) are also reported, along with primary carbonyl yields measured in the presence and absence of excess SO2, both under "OH-free" conditions. Reaction stoichiometries are shown to be correlated with alkene OH yields, and the mechanistic implications of this observation are discussed. The fractional increase in primary carbonyl yield in the presence of excess SOz is shown to be inversely related to the OH yield and is interpreted as a measure of the fraction of the vibrationally excited Criegee intermediate that is stabilized in air at a pressure of I atm.