Criegee Intermediates: Production, Detection and Reactivity

Rabi Chhantyal Pun*, M. A. H. Khan*, Craig A. Taatjes, Carl J. Percival, Andrew J Orr-Ewing, Dudley E Shallcross

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

Abstract

In the context of tropospheric chemistry, Criegee intermediates denote carbonyl oxides with biradical / zwitterionic character (R1R2COO) that form during the ozonolysis of alkenes. First discovered almost 70 years ago, stabilized versions of Criegee intermediates formed via collisional removal of excess energy have interesting kinetic and mechanistic properties. The direct production and detection of these intermediates were not reported in the literature until 2008. However, recent advances in their generation through the ultraviolet irradiation of the corresponding diiodoalkanes in excess O2 and detection by various spectroscopic techniques (photoionization, ultraviolet, infrared, microwave and mass spectrometry) have shown that these species can react rapidly with closed shell molecules, in many cases at or exceeding the classical gas-kinetic limit, via multiple reaction pathways. These reactions can be complex, and laboratory measurements of products and the temperature and pressure dependence of the reaction kinetics have also revealed unusual behaviour. The potential role of these intermediates in atmospheric chemistry is significant, altering models of the oxidising capacity of the Earth's atmosphere and the rate of generation of secondary organic aerosol.
Original languageEnglish
Pages (from-to)385-424
Number of pages41
JournalInternational Reviews in Physical Chemistry
Volume39
Issue number3
DOIs
Publication statusPublished - 31 Jul 2020

Keywords

  • Criegee Intermediates
  • Reaction Mechanisms
  • Atmospheric Chemistry

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