Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

Michael E. Jenkin; Richard  Valorso; Bernard Aumont; Andrew Robert Rickard

doi:10.5194/acp-19-7691-2019

Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

Michael E. Jenkin, Richard Valorso, Bernard Aumont, Andrew Robert Rickard

Chemistry

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

Abstract

Organic peroxy radicals (RO2), formed from the
degradation of hydrocarbons and other volatile organic compounds
(VOCs), play a key role in tropospheric oxidation
mechanisms. Several competing reactions may be available
for a given RO2 radical, the relative rates of which depend
on both the structure of RO2 and the ambient conditions.
Published kinetics and branching ratio data are reviewed
for the bimolecular reactions of RO2 with NO, NO2, NO3,
OH and HO2; and for their self-reactions and cross-reactions
with other RO2 radicals. This information is used to define
generic rate coefficients and structure–activity relationship
(SAR) methods that can be applied to the bimolecular reactions
of a series of important classes of hydrocarbon and oxygenated
RO2 radicals. Information for selected unimolecular
isomerization reactions (i.e. H-atom shift and ring-closure reactions)
is also summarized and discussed. The methods presented
here are intended to guide the representation of RO2
radical chemistry in the next generation of explicit detailed
chemical mechanisms.

Original language	English
Pages (from-to)	7691-7717
Journal	Atmospheric Chemistry and Physics
Volume	19
DOIs	https://doi.org/10.5194/acp-19-7691-2019
Publication status	Published - 7 Jun 2019

Bibliographical note

Keywords

peroxy radical chemistry
atmospheric chemistry
structure activity relationships
gas kinetics
automatic chemical mechanism development

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10.5194/acp-19-7691-2019

ACPJenkin19
© Author(s) 2019.
Final published version, 1.79 MBLicence: CC BY

Mechanisms for Atmospheric chemistry: GeneratioN, Interpretation and FidelitY (MAGNIFY)
Rickard, A. R. & Evans, M. J.
NATURAL ENVIRONMENT RESEARCH COUNCIL
1/08/15 → 31/01/19
Project: Research project (funded) › Research

Cite this

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title = "Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction",

abstract = "Organic peroxy radicals (RO2), formed from thedegradation of hydrocarbons and other volatile organic compounds(VOCs), play a key role in tropospheric oxidationmechanisms. Several competing reactions may be availablefor a given RO2 radical, the relative rates of which dependon both the structure of RO2 and the ambient conditions.Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3,OH and HO2; and for their self-reactions and cross-reactionswith other RO2 radicals. This information is used to definegeneric rate coefficients and structure–activity relationship(SAR) methods that can be applied to the bimolecular reactionsof a series of important classes of hydrocarbon and oxygenatedRO2 radicals. Information for selected unimolecularisomerization reactions (i.e. H-atom shift and ring-closure reactions)is also summarized and discussed. The methods presentedhere are intended to guide the representation of RO2radical chemistry in the next generation of explicit detailedchemical mechanisms.",

keywords = "peroxy radical chemistry, atmospheric chemistry, structure activity relationships, gas kinetics, automatic chemical mechanism development",

author = "Jenkin, {Michael E.} and Richard Valorso and Bernard Aumont and Rickard, {Andrew Robert}",

note = "{\textcopyright} Author(s) 2019.",

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doi = "10.5194/acp-19-7691-2019",

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TY - JOUR

T1 - Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

AU - Jenkin, Michael E.

AU - Valorso, Richard

AU - Aumont, Bernard

AU - Rickard, Andrew Robert

N1 - © Author(s) 2019.

PY - 2019/6/7

Y1 - 2019/6/7

N2 - Organic peroxy radicals (RO2), formed from thedegradation of hydrocarbons and other volatile organic compounds(VOCs), play a key role in tropospheric oxidationmechanisms. Several competing reactions may be availablefor a given RO2 radical, the relative rates of which dependon both the structure of RO2 and the ambient conditions.Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3,OH and HO2; and for their self-reactions and cross-reactionswith other RO2 radicals. This information is used to definegeneric rate coefficients and structure–activity relationship(SAR) methods that can be applied to the bimolecular reactionsof a series of important classes of hydrocarbon and oxygenatedRO2 radicals. Information for selected unimolecularisomerization reactions (i.e. H-atom shift and ring-closure reactions)is also summarized and discussed. The methods presentedhere are intended to guide the representation of RO2radical chemistry in the next generation of explicit detailedchemical mechanisms.

AB - Organic peroxy radicals (RO2), formed from thedegradation of hydrocarbons and other volatile organic compounds(VOCs), play a key role in tropospheric oxidationmechanisms. Several competing reactions may be availablefor a given RO2 radical, the relative rates of which dependon both the structure of RO2 and the ambient conditions.Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3,OH and HO2; and for their self-reactions and cross-reactionswith other RO2 radicals. This information is used to definegeneric rate coefficients and structure–activity relationship(SAR) methods that can be applied to the bimolecular reactionsof a series of important classes of hydrocarbon and oxygenatedRO2 radicals. Information for selected unimolecularisomerization reactions (i.e. H-atom shift and ring-closure reactions)is also summarized and discussed. The methods presentedhere are intended to guide the representation of RO2radical chemistry in the next generation of explicit detailedchemical mechanisms.

KW - peroxy radical chemistry

KW - atmospheric chemistry

KW - structure activity relationships

KW - gas kinetics

KW - automatic chemical mechanism development

U2 - 10.5194/acp-19-7691-2019

DO - 10.5194/acp-19-7691-2019

M3 - Article

SN - 1680-7316

VL - 19

SP - 7691

EP - 7717

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

ER -

Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

Abstract

Bibliographical note

Keywords

Access to Document

Projects

Mechanisms for Atmospheric chemistry: GeneratioN, Interpretation and FidelitY (MAGNIFY)

Cite this