Preprints
https://doi.org/10.5194/acp-2021-1031
https://doi.org/10.5194/acp-2021-1031

  03 Jan 2022

03 Jan 2022

Review status: this preprint is currently under review for the journal ACP.

Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction

Mike J. Newland1,a, Camille Mouchel-Vallon1,b, Richard Valorso2, Bernard Aumont2, Luc Vereecken3, Michael E. Jenkin4, and Andrew R. Rickard1,5 Mike J. Newland et al.
  • 1Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, United Kingdom
  • 2Univ Paris Est Creteil and Université de Paris, CNRS, LISA, F-94010 Créteil, France
  • 3Forschungszentrum Jülich GmbH, Institute for Energy and Climate, IEK-8 Troposphere, 52428 Jülich, Germany
  • 4Atmospheric Chemistry Services, Okehampton, Devon, EX20 4QB, United Kingdom
  • 5National Centre for Atmospheric Science, Wolfson Atmospheric Chemistry Laboratories, University of York, United Kingdom
  • anow at: ICARE-CNRS, 1 C Av. de la Recherche Scientifique, 45071 Orléans Cedex 2, France
  • bnow at: Laboratoire d'Aérologie, Université de Toulouse, CNRS, UPS, Toulouse, France

Abstract. Reaction with ozone is an important atmospheric removal process for alkenes. The ozonolysis reaction produces carbonyls, and carbonyl oxides (Criegee intermediates, CI), which can rapidly decompose to yield a range of closed shell and radical products, including OH radicals. Consequently, it is essential to accurately represent the complex chemistry of Criegee intermediates in atmospheric models in order to fully understand the impact of alkene ozonolysis on atmospheric composition. A mechanism construction protocol is presented which is suitable for use in automatic mechanism generation. The protocol defines the critical parameters for describing the chemistry following the initial reaction, namely: the primary carbonyl / CI yields from the primary ozonide fragmentation; the amount of stabilisation of the excited CI (CI*); the unimolecular decomposition pathways, rates and products of the CI; the bimolecular rates and products of atmospherically important reactions of the stabilised CI (SCI). This analysis implicitly predicts the yield of OH from the alkene-ozone reaction. A comprehensive database of experimental OH, SCI and carbonyl yields has been collated using reported values in the literature and used to assess the reliability of the protocol. The protocol provides estimates OH, SCI and carbonyl yields with a root mean square error of 0.13 and 0.12 and 0.14, respectively. Areas where new experimental and theoretical data would improve the protocol and its assessment are identified and discussed.

Mike J. Newland et al.

Status: open (until 14 Feb 2022)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-1031', Anonymous Referee #1, 22 Jan 2022 reply

Mike J. Newland et al.

Mike J. Newland et al.

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Short summary
Alkene ozonolysis produces Criegee intermediates, which can act as oxidants or decompose to give a range of closed shell and radical products, including OH. Therefore it is essential to accurately represent the chemistry of Criegee intermediates in atmospheric models in order to understand their impacts on atmospheric composition. Here we provide a mechanism construction protocol by which the central features of alkene ozonolysis chemistry can be included in an automatic mechanism generator.
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