Atmospheric chemistry of 4:2 fluorotelomer alcohol (CF3(CF2)3CH2CH2OH):: Products and mechanism of Cl atom initiated oxidation
Atmospheric chemistry of 4:2 fluorotelomer alcohol (CF3(CF2)3CH2CH2OH):: Products and mechanism of Cl atom initiated oxidation
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DOI：
10.1021/jp0493576
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发表时间：
2004-07-01
影响因子：
2.9
通讯作者：
Mabury, SA
中科院分区：
文献类型：
--
作者：
Hurley, MD;Ball, JC;Mabury, SA
采用烟雾室/FTIR 技术研究了在 296 K、700 Torr N-2/O-2 稀释剂中 Cl 原子引发的 4:2 含氟调聚物醇 (CF3(CF2)(3)CH2CH2OH) 氧化的产物和机理。CF3(CF2)(3)CH2CHO 是唯一的初级氧化产物。 CF3(CF2)(3)CHO、CF3(CF2)(3)CH2COOH和CF3(CF2)(3)CH2C(O)OOH是二次氧化产物。进一步照射导致形成CF3(CF2)(3)COOH、COF2和CF3OH。 CF3(CF2)(3)CHO、CF3(CF2)(3)CH2COOH和CF3(CF2)(3)CH2C(O)OOH由CF3(CF2)(3)CH2CHO氧化形成，产率分别为46%、27%和小于或等于27%。使用相对速率技术，确定 k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) 分子(-1) s(-1) 的值。由4:2含氟调聚物醇得到的全氟化酸CF3(CF2)(3)COOH的产率随着稀释气体氧气浓度的增加而增加。对于本文使用的实验条件并采用> 98%消耗的4:2含氟调聚物醇，在用10、140、400和700托O-2进行的实验中，CF3(CF2)(3)COOH的摩尔产率分别<0.011、0.031、0.042和0.056。这些结果表明，含氟调聚物醇的大气氧化可能是在偏远地区观察到的全氟化羧酸的重要来源。
Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46%, 27%, and less than or equal to 27%, respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration. For the experimental conditions used herein and employing > 98% consumption of 4:2 fluorotelomer alcohol, the molar yields of CF3(CF2)(3)COOH were < 0.011, 0.031, 0.042, and 0.056 in experiments conducted with 10, 140, 400, and 700 Torr O-2, respectively. These results suggest that the atmospheric oxidation of fluorotelomer alcohols may be a significant source of the perfluorinated carboxylic acids that are observed in remote areas.