Oyaro Nathan, Sellevåg Stig R, Nielsen Claus J
Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway.
J Phys Chem A. 2005 Jan 20;109(2):337-46. doi: 10.1021/jp047860c.
The kinetics of the OH radical and Cl atom reactions with nine fluorinated ethers have been studied by the relative rate method at 298 K and 1013 hPa using gas chromatography-mass spectroscopy (GC-MS) detection: k(OH + CH3CH2OCF3) = (1.55 +/- 0.25) x 10(-13), k(OH + CF3CH2OCH3) = (5.7 +/- 0.8) x 10(-13),k(OH + CF3CH2OCHF2) = (9.1 +/- 1.1) x 10(-15), k(OH + CF3CHFOCHF2) = (6.5 +/- 0.8) x 10(-15), k(OH + CHF2CHFOCF3) = (6.8 +/- 1.1) x 10(-15), k(OH + CF3CHFOCF3) < 1 x 10(-15), k(OH + CF3CHFCF2OCHF2) = (1.69 +/- 0.26) x 10(-14), k(OH + CF3CHFCF2OCH2CH3) = (1.47 +/- 0.13) x 10(-13), k(OH + CF3CF2CF2OCHFCF3) < 1 x 10(-15), k(Cl + CH3CH2OCF3) = (2.2 +/- 0.8) x 10(-12), k(Cl + CF3CH2OCH3) = (1.8 +/- 0.9) x 10(-11), k(Cl + CF3CH2OCHF2) = (1.5 +/- 0.4) x 10(-14), k(Cl + CF3CHFOCHF2) = (1.1 +/- 1.9) x 10(-15), k(Cl + CHF2CHFOCF3) = (1.2 +/- 2.0) x 10(-15), k(Cl + CF3CHFOCF3) < 3 x 10(-15), k(Cl + CF3CHFCF2OCHF2) < 6 x 10(-16), k(Cl + CF3CHFCF2OCH2CH3) = (3.1 +/- 1.1) x 10(-12), and k(Cl + CF3CF2CF2OCHFCF3) < 3 x 10(-15) cm3 molecule(-1) s(-1). The error limits include three standard deviations (3 sigma) from the statistical data analyses, as well as the errors in the rate coefficients of the reference compounds that are used. Infrared absorption cross sections and estimates of the trophospheric lifetimes and the global warming potentials of the fluorinated ethers are presented. The atmospheric degradation of the compounds is discussed.
在298 K和1013 hPa条件下，采用气相色谱 - 质谱联用（GC - MS）检测的相对速率法，研究了羟基自由基（OH）和氯原子与九种含氟醚的反应动力学：k(OH + CH3CH2OCF3) = (1.55 ± 0.25) × 10(-13)，k(OH + CF3CH2OCH3) = (5.7 ± 0.8) × 10(-13)，k(OH + CF3CH2OCHF2) = (9.1 ± 1.1) × 10(-15)，k(OH + CF3CHFOCHF2) = (6.5 ± 0.8) × 10(-15)，k(OH + CHF2CHFOCF3) = (6.8 ± 1.1) × 10(-15)，k(OH + CF3CHFOCF3) < 1 × 10(-15)，k(OH + CF3CHFCF2OCHF2) = (1.69 ± 0.26) × 10(-14)，k(OH + CF3CHFCF2OCH2CH3) = (1.47 ± 0.13) × 10(-13)，k(OH + CF3CF2CF2OCHFCF3) < 1 × 10(-15)，k(Cl + CH3CH2OCF3) = (2.2 ± 0.8) × 10(-12)，k(Cl + CF3CH2OCH3) = (1.8 ± 0.9) × 10(-11)，k(Cl + CF3CH2OCHF2) = (1.5 ± 0.4) × 10(-14)，k(Cl + CF3CHFOCHF2) = (1.1 ± 1.9) × 10(-15)，k(Cl + CHF2CHFOCF3) = (1.2 ± 2.0) × 10(-15)，k(Cl + CF3CHFOCF3) < 3 × 10(-15)，k(Cl + CF3CHFCF2OCHF2) < 6 × 10(-16)，k(Cl + CF3CHFCF2OCH2CH3) = (3.1 ± 1.1) × 10(-12)，以及k(Cl + CF3CF2CF2OCHFCF3) < 3 × 10(-15) cm3·分子(-1)·s(-1)。误差限包括统计数据分析中的三个标准偏差（3σ），以及所用参考化合物速率系数的误差。给出了含氟醚的红外吸收截面、对流层寿命估计值和全球变暖潜势。并讨论了这些化合物的大气降解情况。
