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

The multivariate relative rate method was applied to a range of volatile organic compound (VOC) reactions with OH. This previously published method (Shaw et al., 2018) was improved to increase the sensitivity towards more slowly reacting VOCs, broadening the range of compounds which can be examined. A total of 35 room temperature relative rate coefficients were determined, eight of which have not previously been reported. Five of the new reaction rate coefficients were for large alkyl substituted mono-aromatic species recently identified in urban air masses, likely with large ozone production potentials. The new results (with k(OH) (296 K) values in units of 10(-12) cm(3) 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 for smaller VOCs agreed well with available structure-activity relationship (SAR) calculations, the larger alkyl benzenes were found to be less reactive than the SAR prediction, indicating that our understanding of the oxidation chemistry of these compounds is still limited. k(OH) (296 K) rate coefficients (in units of 10(-12) cm(3) molec.(-1) s(-1)) for reactions of three large alkanes with OH were also determined for the first time: 2-methylheptane, 9.1 (+/- 0.3); 2-methylnonane, 11.0 (+/- 0.3); and ethylcyclohexane, 14.4 (+/- 0.3), all in reasonable agreement with SAR predictions. Rate coefficients for the 27 previously studied OH + VOC reactions agreed well with available literature values, lending confidence to the application of this method for the rapid and efficient simultaneous study of gas-phase reaction kinetics.