Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

Annu Rev Phys Chem. 2017 May 5:68:183-207. doi: 10.1146/annurev-physchem-052516-050739.

Abstract

The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

Keywords: aerosols; atmospheric chemistry; chemical kinetics; hydrocarbon oxidation; ozonolysis; particulates.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.