International Journal of Chemical Kinetics p. 767 - 777 (2012)
Update date:2022-08-24
Topics:
Rissanen, Matti P.
Eskola, Arkke J.
Timonen, Raimo S.
The gas-phase kinetics of CHBr2 + NO2 and CH 3CHBr + NO2 reactions have been studied in direct time resolved measurements using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals were generated by pulsed laser photolysis of bromoform and 1,1-dibromoethane at 248 nm. The subsequent decays of the radical concentrations were monitored as a function of [NO2] under pseudo-first-order conditions. The rate coefficients of both reactions are independent of bath gas (He) pressure and display negative temperature dependence under the conditions of 2-6 Torr pressure (He) and 250-480 K. The obtained bimolecular rate coefficients are k(CHBr2 + NO2) = (9.8 ± 0.4) × 10-12 (T/300 K) -1.65 ± 0.18 cm3 s-1 (288-483 K) and k(CH3CHBr + NO2) = (2.27 ± 0.06) × 10 -11 (T/300 K)-1.28 ± 0.11 cm3 s -1 (250-483 K), with the uncertainties given as one standard error. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are ±25%. The reaction products identified were CBr 2O for the CHBr2 + NO2 reaction and CHBrO and CH3CHO with minor amounts of CH3 for the CH 3CHBr + NO2 reaction, respectively. 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 767-777, 2012 Copyright
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