Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction

Reaction with the hydroxyl (OH) radical is the dominant removal process for volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for the reactions of OH with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models, and are required more ge...

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Bibliographic Details
Published in:Atmospheric chemistry and physics 2018-07, Vol.18 (13), p.9329-9349
Main Authors: Jenkin, Michael E, Valorso, Richard, Aumont, Bernard, Rickard, Andrew R, Wallington, Timothy J
Format: Article
Language:English
Subjects:
Aliphatic compounds
Aliphatic hydrocarbons
Alkanes
Aromatic compounds
Aromatic hydrocarbons
Atmospheric and Oceanic Physics
Atmospheric models
Chemical attack
Chemical properties
Chemical reactions
Chemical Sciences
Coefficients
Environmental aspects
Hydrocarbons
Hydroxides
Methods
Observations
or physical chemistry
Organic chemistry
Organic compounds
Oxidation
Physics
Ratios
Removal
Representations
SAR (radar)
Theoretical and
VOCs
Volatile organic compounds
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Summary:Reaction with the hydroxyl (OH) radical is the dominant removal process for volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for the reactions of OH with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models, and are required more generally for impact assessments involving estimation of atmospheric lifetimes or oxidation rates for VOCs. A structure–activity relationship (SAR) method is presented for the reactions of OH with aromatic organic compounds, with the reactions of aliphatic organic compounds considered in the preceding companion paper. The SAR is optimized using a preferred set of data including reactions of OH with 67 monocyclic aromatic hydrocarbons and oxygenated organic compounds. In each case, the rate coefficient is defined in terms of a summation of partial rate coefficients for H abstraction or OH addition at each relevant site in the given organic compound, so that the attack distribution is defined. The SAR can therefore guide the representation of the OH reactions in the next generation of explicit detailed chemical mechanisms. Rules governing the representation of the reactions of the product radicals under tropospheric conditions are also summarized, specifically the rapid reaction sequences initiated by their reactions with O2.
ISSN:1680-7324
1680-7316
1680-7324
DOI:10.5194/acp-18-9329-2018