Articles | Volume 18, issue 13
Research article
04 Jul 2018
Research article |  | 04 Jul 2018

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

Michael E. Jenkin, Richard Valorso, Bernard Aumont, Andrew R. Rickard, and Timothy J. Wallington

Abstract. 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.

Short summary
Organic compounds are emitted in large quantities from natural and human-influenced sources. Removal from the atmosphere occurs mainly by reaction with hydroxyl (OH) radicals, and initiates reaction sequences forming pollutants such as ozone and organic particles. Due to their very large number, it is impossible to measure the removal rate for all compounds, and most have to be estimated. An updated and extended estimation method is reported for use in atmospheric models and impact assessments.
Final-revised paper