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Measurements of Rate Constants for the OH Reactions with Bromoform (CHBr3),...

Orkin, V. L., V. G. Khamaganov, S. N. Kozlov, and M. J. Kurylo (2013), Measurements of Rate Constants for the OH Reactions with Bromoform (CHBr3), CHBr2Cl, CHBrCl2, and Epichlorohydrin (C3H5ClO), J. Phys. Chem. A, 117, 3809-3818, doi:10.1021/jp3128753.

Measurements of the rate constants for the gas phase reactions of OH radicals with bromoform (CHBr3) and epichlorohydrin (C3H5ClO) were performed using a flash photolysis resonance-fluorescence technique over the temperature range 230−370 K. The temperature dependences of the rate constants can be represented by the following expressions: kBF(230−370 K) = (9.94 ± 0.76) × 10−13 exp[−(387 ± 22)/T] cm3molecule−1s−1 and kECH(230−370 K) = 1.05 × 10−14(T/298)5.16 exp(+1082/T) cm3molecule−1s−1. Rate constants for the reactions of OH with CHCl2Br and CHClBr2 were measured between 230 and 330 K. They can be represented by the following expressions: kDCBM(230−330 K) = (9.4 ± 1.3) × 10−13 exp[−(513 ± 37)/T] cm3molecule−1s−1 and kCDBM(230−330 K) = (9.0 ± 1.9) × 10−13 exp[−(423 ± 61)/T] cm3molecule−1s−1. The atmospheric lifetimes due to reactions with tropospheric OH were estimated to be 57, 39, 72, and 96 days, respectively. The total atmospheric lifetimes of the Br-containing methanes due to both reaction with OH and photolysis were calculated to be 22, 50, and 67 days for CHBr3, CHClBr2, and CHCl2Br, respectively.

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Upper Atmosphere Research Program (UARP)