Instituto de Investigaciones en Fisicoquímica de Córdoba (I.N.F.I.Q.C.), Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Centro de Laser de Ciencias Moleculares, Universidad Nacional de Córdoba, Ciudad Universitaria, Pabellón Argentina, Ala 1, 5000 Córdoba, Argentina.
Chemphyschem. 2010 Dec 17;11(18):4053-9. doi: 10.1002/cphc.201000430.
The relative rate technique has been used to determine the rate constants of the reactions of OH radicals with CF(3)CCl=CCl(2) (k(1)), CF(3)CCl=CClCF(3) (k(2)) and CF(3)CF=CFCF(3) (k(3)). Experiments were carried out at (298±2) K and atmospheric pressure using ultrapure nitrogen as gas bath. The decay rates of the organic species were measured relative to those of ethane, methanol, acetone, chloroethane and 2-butanone. The following rate constants were derived in units of cm(3) molecule(-1) s(-1): k(1)= (10±1)×10(-13), k(2)=(2.1±0.2)×10(-13) and k(3)=(3.7±0.2)×10(-13). This is the first experimental determination of k(1) and k(2). The rate constants obtained are compared with previous literature data to establish reactivity trends and are used to estimate the atmospheric lifetimes of the studied perhaloalkenes. From the calculated lifetimes, using an average global concentration of hydroxyl radicals, the atmospheric loss of these compounds by the OH-initiated oxidation was determined. Also, estimations have been made of the ozone depletion potential (ODP), the radiative forcing efficiency (RE), the halocarbon global warming potential (HGWP) and the global warming potential (GWP) of the perhaloalkenes. The approximate nature of these values is stressed considering that these are short-lived compounds for which these atmospheric parameters may vary according to latitude and season.
相对速率技术已被用于测定 OH 自由基与 CF(3)CCl=CCl(2)（k(1)）、CF(3)CCl=CClCF(3)（k(2)）和 CF(3)CF=CFCF(3)（k(3)）反应的速率常数。实验在（298±2）K 和大气压下进行，使用超纯氮气作为气体浴。有机物种的衰减速率相对于乙烷、甲醇、丙酮、氯乙烷和 2-丁酮进行测量。以下速率常数以单位 cm(3) molecule(-1) s(-1)表示：k(1)= (10±1)×10(-13)，k(2)=(2.1±0.2)×10(-13)和 k(3)=(3.7±0.2)×10(-13)。这是 k(1)和 k(2)的首次实验测定。将获得的速率常数与以前的文献数据进行比较，以确定反应性趋势，并用于估计所研究的全卤代烯烃的大气寿命。根据计算出的寿命，使用平均全球羟基自由基浓度，确定了这些化合物通过 OH 引发氧化的大气损失。此外，还估算了这些全卤代烯烃的臭氧消耗潜势 (ODP)、辐射强迫效率 (RE)、卤碳全球变暖潜势 (HGWP)和全球变暖潜势 (GWP)。考虑到这些是短寿命化合物，这些大气参数可能会根据纬度和季节而变化，因此强调了这些值的近似性质。
