Measurements of rate constants for the OH reactions with bromoform (CHBr3), CHBr2Cl, CHBrCl2, and epichlorohydrin (C3H5ClO).
Measurements of rate constants for the OH reactions with bromoform (CHBr3), CHBr2Cl, CHBrCl2, and epichlorohydrin (C3H5ClO).
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测量 OH 与溴仿 (CHBr3)、CHBr2Cl、CHBrCl2 和环氧氯丙烷 (C3H5ClO) 反应的速率常数。
DOI：
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发表时间：
2013
影响因子：
2.9
通讯作者：
M. Kurylo
中科院分区：
文献类型：
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作者：
V. L. Orkin;V. Khamaganov;S. Kozlov;M. Kurylo
用闪光光解共振荧光技术在230-370 K温度范围内测定了OH自由基与溴仿（CHBr_3）和环氧氯丙烷（C_3 H_5ClO）的气相反应速率常数。速率常数的温度依赖性可以由以下表达式表示：KBF（230-370 K）=（9.94 ± 0.76）× 10（-13）exp[-（387 ± 22）/T] cm（3）molecule（-1）s（-1）; kECH（230-370 K）= 1.05 × 10（-14）（T/298）（5.16）exp（+1082/T）cm（3）molecule（-1）s（-1）。在230 ~ 330 K范围内测定了OH与CHCl_2Br和CHClBr_2反应的速率常数。它们可以由以下表达式表示：kDCBM（230-330 K）=（9.4 ± 1.3）× 10（-13）exp[-（513 ± 37）/T] cm（3）molecule（-1）s（-1）; kCDBM（230-330 K）=（9.0 ± 1.9）× 10（-13）exp[-（423 ± 61）/T] cm（3）molecule（-1）s（-1）。由于与对流层OH反应，大气寿命估计分别为57、39、72和96天。由于与OH反应和光解，含溴甲烷的总大气寿命计算为22，50和67天CHBr 3，CHClBr 2，和CHCl 2Br，分别。
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] cm(3) molecule(-1) s(-1) and kECH(230-370 K) = 1.05 × 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: kDCBM(230-330 K) = (9.4 ± 1.3) × 10(-13) exp[-(513 ± 37)/T] cm(3) molecule(-1) s(-1) and kCDBM(230-330 K) = (9.0 ± 1.9) × 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.