Estimation of rate coefficients for the reactions of O3 with unsaturated organic compounds for use in automated mechanism construction

Michael E. Jenkin; Richard Valorso; Bernard Aumont; Mike J. Newland; Andrew R. Rickard

doi:10.5194/acp-20-12921-2020

Estimation of rate coefficients for the reactions of O₃with unsaturated organic compounds for use in automated mechanism construction

Michael E. Jenkin^*, Richard Valorso, Bernard Aumont, Mike J. Newland, Andrew R. Rickard

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Reaction with ozone (O₃) is an important removal process for unsaturated volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of ₃with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models. Updated and extended structure-activity relationship (SAR) methods are presented for the reactions of O₃with mono- and polyunsaturated organic compounds. The methods are optimized using a preferred set of data including reactions of O₃with 221 unsaturated compounds. For conjugated dialkene structures, site-specific rates are defined, and for isolated polyalkenes rates are defined for each double bond to determine the branching ratios for primary ozonide formation. The information can therefore guide the representation of the O₃reactions in the next generation of explicit detailed chemical mechanisms.

Original language	English
Pages (from-to)	12921-12937
Number of pages	17
Journal	Atmospheric Chemistry and Physics
Volume	20
Issue number	21
DOIs	https://doi.org/10.5194/acp-20-12921-2020
Publication status	Published - 5 Nov 2020

Bibliographical note

Keywords

Atmospheric chemistry
kinetics
Ozonolysis
chemical mechanisms

Access to Document

10.5194/acp-20-12921-2020

acp-20-12921-2020
© Author(s) 2020.
Final published version, 1.42 MBLicence: CC BY

Cite this

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title = "Estimation of rate coefficients for the reactions of O3 with unsaturated organic compounds for use in automated mechanism construction",

abstract = "Reaction with ozone (O3) is an important removal process for unsaturated volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of 3with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models. Updated and extended structure-activity relationship (SAR) methods are presented for the reactions of O3 with mono- and polyunsaturated organic compounds. The methods are optimized using a preferred set of data including reactions of O3 with 221 unsaturated compounds. For conjugated dialkene structures, site-specific rates are defined, and for isolated polyalkenes rates are defined for each double bond to determine the branching ratios for primary ozonide formation. The information can therefore guide the representation of the O3 reactions in the next generation of explicit detailed chemical mechanisms.",

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T1 - Estimation of rate coefficients for the reactions of O3 with unsaturated organic compounds for use in automated mechanism construction

AU - Jenkin, Michael E.

AU - Valorso, Richard

AU - Aumont, Bernard

AU - J. Newland, Mike

AU - Rickard, Andrew R.

N1 - © Author(s) 2020

PY - 2020/11/5

Y1 - 2020/11/5

N2 - Reaction with ozone (O3) is an important removal process for unsaturated volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of 3with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models. Updated and extended structure-activity relationship (SAR) methods are presented for the reactions of O3 with mono- and polyunsaturated organic compounds. The methods are optimized using a preferred set of data including reactions of O3 with 221 unsaturated compounds. For conjugated dialkene structures, site-specific rates are defined, and for isolated polyalkenes rates are defined for each double bond to determine the branching ratios for primary ozonide formation. The information can therefore guide the representation of the O3 reactions in the next generation of explicit detailed chemical mechanisms.

AB - Reaction with ozone (O3) is an important removal process for unsaturated volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of 3with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models. Updated and extended structure-activity relationship (SAR) methods are presented for the reactions of O3 with mono- and polyunsaturated organic compounds. The methods are optimized using a preferred set of data including reactions of O3 with 221 unsaturated compounds. For conjugated dialkene structures, site-specific rates are defined, and for isolated polyalkenes rates are defined for each double bond to determine the branching ratios for primary ozonide formation. The information can therefore guide the representation of the O3 reactions in the next generation of explicit detailed chemical mechanisms.

KW - Atmospheric chemistry

KW - kinetics

KW - Ozonolysis

KW - chemical mechanisms

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Estimation of rate coefficients for the reactions of O3 with unsaturated organic compounds for use in automated mechanism construction