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2-乙氧基-3,3,4,4,5-五氟四氢-2,5-双[1,2,2,2-四氟-1-(三氟甲基)乙基]呋喃的大气化学:氯原子和羟基自由基引发氧化的动力学、机理及产物

Atmospheric chemistry of 2-ethoxy-3,3,4,4,5-pentafluorotetrahydro-2,5-bis[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-furan: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation.

作者信息

Javadi M S, Nielsen O J, Wallington T J, Hurley M D, Owens J G

机构信息

Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark.

出版信息

Environ Sci Technol. 2007 Nov 1;41(21):7389-95. doi: 10.1021/es071175c.

Abstract

Smog chamber/FTIR techniques were used to study the atmospheric chemistry of the title compound which we refer to as RfOC2H5. Rate constants of k(Cl + RfOC2H5) = (2.70 +/- 0.36) x 10(-12), k(OH + RfOC2H5) = (5.93 +/- 0.85) x 10(-14), and k(Cl + RfOCHO) = (1.34 +/- 0.20) x 10(-14) cm3 molecule(-1') s(-1) were measured in 700 Torr of N2, or air, diluent at 294 +/- 1 K. From the value of k(OH + RfOC2H5) the atmospheric lifetime of RfOC2H5 was estimated to be 1 year. Two competing loss mechanisms for RfOCH(O*)CH3 radicals were identified in 700 Torr of N2/O2 diluent at 294 +/- 1 K; decomposition via C-C bond scission giving a formate (RfOCHO), or reaction with 02 giving an acetate (RfOC(O)CH3). In 700 Torr of N2/O2 diluent at 294 +/- 1 K the rate constant ratio k(O2)/k(diss) = (1.26 +/- 0.74) x 10(-19) cm3 molecule(-1). The OH radical initiated atmospheric oxidation of RfOC2H5 gives Rf0CHO and RfOC(O)CH3 as major products. RfOC2H5 has a global warming potential of approximately 55 for a 100 year horizon. The results are discussed with respect to the atmospheric chemistry and environmental impact of RfOC2H5.

摘要

利用烟雾箱/傅里叶变换红外光谱技术研究了我们称为RfOC2H5的标题化合物的大气化学。在700托的氮气或空气稀释剂中,于294±1K下测量了k(Cl + RfOC2H5) = (2.70±0.36)×10(-12)、k(OH + RfOC2H5) = (5.93±0.85)×10(-14)和k(Cl + RfOCHO) = (1.34±0.20)×10(-14) cm3·分子(-1)·s(-1)的速率常数。根据k(OH + RfOC2H5)的值,估计RfOC2H5的大气寿命为1年。在700托的N2/O2稀释剂中,于294±1K下确定了RfOCH(O*)CH3自由基的两种竞争损失机制;通过碳 - 碳键断裂分解生成甲酸盐(RfOCHO),或与O2反应生成乙酸盐(RfOC(O)CH3)。在700托的N2/O2稀释剂中,于294±1K下,速率常数比k(O2)/k(分解) = (1.26±0.74)×10(-19) cm3·分子(-1)。OH自由基引发的RfOC2H5大气氧化反应产生Rf0CHO和RfOC(O)CH3作为主要产物。对于100年的时间跨度,RfOC2H5的全球变暖潜能值约为55。针对RfOC2H5的大气化学和环境影响对结果进行了讨论。

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