Efficient Coupling of Reaction Pathways of Criegee Intermediates and Free Radicals in the Heterogeneous Ozonolysis of Alkenes.

In the gas phase, ozonolysis of olefins is known to be a significant source of free radicals. However, for heterogeneous and condensed phase ozone reactions, the importance of reaction pathways that couple Criegee intermediates (CI) with hydroxyl (OH), alkoxy, and peroxy free radicals remains uncertain. Here we report experimental evidence for substantial free radical oxidation during the heterogeneous reaction of O with -9-tricosene (Tri) aerosol. A kinetic model with three coupled submechanisms that include O, CI, and free radical reactions is used to explain how the observed Tri reactivity and its product distributions depend upon [O], [OH], and the presence of CI scavengers. During multiphase ozonolysis, the kinetic model predicts that only ∼30% of the alkene is actually consumed by O, while the remaining ∼70% is consumed by free radicals that cycle through pathways involving CI. These results reveal the importance of free radical oxidation during heterogeneous ozonolysis, which has been previously difficult to isolate due to the complex coupling of CI and OH reaction pathways.