National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan.
Environ Sci Pollut Res Int. 2018 May;25(15):15204-15215. doi: 10.1007/s11356-018-1700-4. Epub 2018 Mar 20.
The rate constants of OH radicals with CFCF=CCl, CFCH=CF, CFCF=CH, CFCH=CH, and (CF)C=CH have been measured over the temperature range 250-430 K. Kinetic measurements have been carried out using flash photolysis and laser photolysis methods combined respectively with laser-induced fluorescence technique. The Arrhenius rate parameters have been determined as k(CFCF=CCl) = (6.50 ± 0.22) × 10∙exp[(200 ± 10)/T], k(CFCH=CF) = (4.85 ± 0.14) × 10∙exp[(120 ± 10)/T], k(CFCF=CH) = (1.54 ± 0.03) × 10∙exp[- (100 ± 10)/T], k(CFCH=CH) = (1.06 ± 0.02) × 10∙exp[(80 ± 10)/T], and k((CF)C=CH) = (8.75 ± 0.23) × 10∙exp[- (20 ± 10)/T] cm molecule s. Infrared absorption spectra of the halogenated alkenes have been measured at room temperature. The atmospheric lifetime, global warming potential, ozone depleting potential, and photochemical ozone creation potential have been estimated. The change in the reactivity of halogenated alkenes by the substitution has been examined by considering the structure containing the atoms or atomic groups attached to the carbons on both sides of the double bond.
OH 自由基与 CFCF=CCl、CFCH=CF、CFCF=CH、CFCH=CH 和 (CF)C=CH 的速率常数已在 250-430 K 的温度范围内进行了测量。动力学测量分别使用闪光光解和激光光解方法结合激光诱导荧光技术进行。已确定 Arrhenius 速率参数为 k(CFCF=CCl) = (6.50 ± 0.22) × 10∙exp[(200 ± 10)/T]、k(CFCH=CF) = (4.85 ± 0.14) × 10∙exp[(120 ± 10)/T]、k(CFCF=CH) = (1.54 ± 0.03) × 10∙exp[- (100 ± 10)/T]、k(CFCH=CH) = (1.06 ± 0.02) × 10∙exp[(80 ± 10)/T] 和 k((CF)C=CH) = (8.75 ± 0.23) × 10∙exp[- (20 ± 10)/T] cm 分子 s。在室温下测量了卤代烯烃的红外吸收光谱。估计了大气寿命、全球变暖潜能值、消耗臭氧潜能值和光化学臭氧生成潜能值。通过考虑与双键两侧碳原子相连的原子或原子团，考察了卤代烯烃取代后反应性的变化。
