Atmospheric chemistry of CH2BrCl, CHBrCl2, CHBr2Cl, CF3CHBrCl, and CBr2Cl2

被引:70
作者
Bilde, M
Wallington, TJ
Ferronato, C
Orlando, JJ [1 ]
Tyndall, GS
Estupiñan, E
Haberkorn, S
机构
[1] Natl Ctr Atmospher Res, Div Atmospher Chem, Boulder, CO 80303 USA
[2] Riso Natl Lab, Plant Biol & Biogeochem Dept, DK-4000 Roskilde, Denmark
[3] Ford Motor Co, Food Res Lab, Dearborn, MI 48121 USA
[4] Univ Grenoble 1, IUTI, Dept Chim, F-3800 Grenoble, France
关键词
D O I
10.1021/jp9733375
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Relative-rate methods were used to measure the following rate constants at 296 K in 700 Torr of N-2, O-2, or air diluent (all cm(3) molecule(-1) s(-1)): K(OH + CHBrCl2) = (1.2 +/- 0.3) x 10(-13), k(OH + CH2BrCl) = (1.2 +/- 0.3) x 10(-13), k(Cl + CHBr2Cl) = (2.2 +/- 0.6) x 10(-13), k(Cl + CBr2Cl2) = (1.8 +/- 0.4) x 10(-13), k(CI + CBrCl3) = (7.1 +/- 0.9) x 10(-14), and k(Cl + CF3CHBrCl) = (2.0 +/- 0.3) x 10(-14). Over the temperature range 217-296 k(Cl + CHBrCl2) = (2.6 +/- 0.4) x 10(-12) exp(-852 +/- 76/T) and k(Cl + CH2BrCl) = (1.2 +/- 0.2) x 10(-11) exp(-1000 +/- 82/T) cm(3) molecule(-1) s(-1) were found. The UV absorption spectra of CHBrCl2, CF3CHBrCl, and CHBr2Cl were measured at temperatures between 223 and 298 K over the range 210-320 nm, The products of Cl-atom-initiated oxidation of CHBrCl2, CBr2Cl2 CHBr2Cl, and CF3CHBrCl were determined using FTIR smog-chamber techniques. Reaction of Cl atoms with CHBrCl2, CHBr2Cl, and CF3CHBrCl proceeds via hydrogen abstraction. Reaction of Cl atoms with CHBr2Cl2 and CBrCl3 occurs via bromine abstraction. Product studies of the Cl-initiated oxidation of CHBrCl2 and CBr2Cl2 conducted with, and without, added NO showed strong evidence for the production of chemically activated alkoxy radicals in the reaction of CBrCl2O2 radicals with NO. These results are discussed with respect to the atmospheric chemistry of CH2BrCl, CHBrCl2, CHBr2Cl, CBr2Cl2, CF3CHBrCl, and other brominated organic compounds.
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页码:1976 / 1986
页数:11
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