R. Kaiser, J. Hasenbein, Zhuangjie Li
Jul 1, 2019
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Journal
The journal of physical chemistry. A
Abstract
The kinetics of reactions of 4-methyl-2-pentanone (MIBK) and m-ethyl toluene (MET) with hydroxyl radical has been studied at a total pressure of 1 - 8 Torr and 240 - 340 K using the RR/DF/MS technique. The rate constant for the reaction of MIBK with hydroxyl radical was found to be essentially pressure independent in a range of 1 - 3 Torr. The rate constant for MET reaction with hydroxyl radical increased with pressure at 1 - 5 Torr, and a high pressure limit was reached at 5 Torr. At 298K, rate constants (in cm3 molecule-1 s-1) of kMIBK+OH(298K) = (1.25±0.21) × 10-11 and kMET+OH(298K) = (2.05±0.23) × 10-11 were determined with n-nonane as a reference compound, while kMIBK+OH(298K) = (1.25±0.11) × 10-11 and kMET+OH(298K) = (1.88±0.17) × 10-11 were obtained with 1,4-dioxane as the reference compound, where kMIBK+OH was measured at 1 Torr and at kMET+OH 5 Torr. The rate constant of MIBK reaction with hydroxyl radical was found to be negatively dependent on temperature at 240 - 340 K, with an Arrhenius expression of kMIBK+OH(T) = (2.00±0.07) × 10-12exp[(535±11)/T] cm3 molecule-1 s-1. The rate constant of MET reaction with the hydroxyl radicals was also found to negatively depend on temperature at 240 - 340 K, but with non-linear behavior in the Arrhenius plot.