Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction
<p>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 req...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2018-07-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/18/9329/2018/acp-18-9329-2018.pdf |
| Summary: | <p>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 O<sub>2</sub>.</p> |
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| ISSN: | 1680-7316 1680-7324 |