期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 117, 期 18, 页码 3809-3818出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp3128753
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资金
- Upper Atmosphere Research Program of the National Aeronautics and Space Administration
- NATO CLG Program [ESP.EAP.CLG.983035, EST.CLG979421]
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: k(BF)(230-370 K) = (9.94 +/- 0.76) x 10(-13) exp[-(387 +/- 22)/T] cm(3) molecule(-1) s(-1) and k(ECH)(230-370 K) = 1.05 x 10(-14)(T/298)(5.16) exp(+1082/T) cm(3) molecule(-1) s(-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: k(DCBM)(230-330 K) = (9.4 +/- 1.3) x 10(-13) exp[-(513 +/- 37)/T] cm(3) molecule(-1) s(-1) and k(CDBM)(230-330 = (9.0 +/- 1.9) x 10(-13) exp[-(423 +/- 61)/T] cm(3) molecule(-1) s(-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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