Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction
<p>Organic peroxy radicals (<span class="inline-formula">RO<sub>2</sub></span>), 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 a...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2019-06-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/19/7691/2019/acp-19-7691-2019.pdf |
| Summary: | <p>Organic peroxy radicals (<span class="inline-formula">RO<sub>2</sub></span>), 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 <span class="inline-formula">RO<sub>2</sub></span> radical, the relative rates of which depend
on both the structure of <span class="inline-formula">RO<sub>2</sub></span> and the ambient conditions. Published
kinetics and branching ratio data are reviewed for the bimolecular reactions
of <span class="inline-formula">RO<sub>2</sub></span> with NO, <span class="inline-formula">NO<sub>2</sub></span>, <span class="inline-formula">NO<sub>3</sub></span>, OH and <span class="inline-formula">HO<sub>2</sub></span>; and for their
self-reactions and cross-reactions with other <span class="inline-formula">RO<sub>2</sub></span> 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 <span class="inline-formula">RO<sub>2</sub></span> 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 <span class="inline-formula">RO<sub>2</sub></span> radical chemistry in the next
generation of explicit detailed chemical mechanisms.</p> |
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| ISSN: | 1680-7316 1680-7324 |