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. The multivariate relative rate method was applied to arange of volatile organic compound (VOC) reactions with OH. This previouslypublished method (Shaw et al., 2018) was improved to increase thesensitivity towards more slowly reacting VOCs, broadening the range of compoundswhich can be examined. A total of 35 room temperature relative ratecoefficients were determined, eight of which have not previously beenreported. Five of the new reaction rate coefficients were for large alkylsubstituted mono-aromatic species recently identified in urban air masses,likely with large ozone production potentials. The new results (withkOH (296 K) values in units of 10−12 cm3 molec.−1 s−1) were n-butylbenzene, 11 (±4); n-pentylbenzene, 7 (±2); 1,2-diethylbenzene, 14 (±4); 1,3-diethylbenzene, 22 (±4);and 1,4-diethylbenzene, 16 (±4). Interestingly, whilst results forsmaller VOCs agreed well with available structure–activity relationship (SAR)calculations, the larger alkyl benzenes were found to be less reactive thanthe SAR prediction, indicating that our understanding of the oxidationchemistry of these compounds is still limited. kOH (296 K) ratecoefficients (in units of 10−12 cm3 molec.−1 s−1) forreactions of three large alkanes with OH were also determined for the firsttime: 2-methylheptane, 9.1 (±0.3); 2-methylnonane, 11.0 (±0.3);and ethylcyclohexane, 14.4 (±0.3), all in reasonable agreement withSAR predictions. Rate coefficients for the 27 previously studiedOH + VOC reactions agreed well with available literature values, lendingconfidence to the application of this method for the rapid and efficientsimultaneous study of gas-phase reaction kinetics.

Rate coefficients for reactions of OH with aromatic and aliphatic volatile organic compounds determined by the multivariate relative rate technique