首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Atmospheric Chemistry of 4:2 Fluorotelomer Alcohol (CF_3(CF_2)_3CH_2CH_2OH): Products and Mechanism of Cl Atom Initiated Oxidation
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Atmospheric Chemistry of 4:2 Fluorotelomer Alcohol (CF_3(CF_2)_3CH_2CH_2OH): Products and Mechanism of Cl Atom Initiated Oxidation

机译:4:2氟调聚物醇(CF_3(CF_2)_3CH_2CH_2OH)的大气化学:Cl原子引发氧化的产物和机理

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摘要

Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF_3(CF_2)_3CH_2CH_2OH) in 700 Torr of N_2/O_2 diluent at 296 K. CF_3(CF_2)_3CH2_CHO is the sole primary oxidation product. CF_3(CF_2)_3CHO, CF_3(CF_2)_3CH_2COOH, and CF_3(CF_2)_3CH_2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF_3(CF_2)_3COOH, COF_2, and CF_3OH. CF_3(CF_2)_3CHO, CF_3(CF_2)_3CH_2COOH, and CF_3(CF_2)_3CH_2C(O)OOH are formed from CF_3(CF_2)_3CH_2CHO oxidation in yields of 46%, 27%, and ≤27%, respectively. Using relative rate techniques, a value of k(Cl + CF_3(CF_2)_3CH_2CHO) = (1.84 ± 0.30) * 10~(-11) cm~3 molecule-1 s~(-1) was determined. The yield of the perfluorinated acid, CF_3(CF_2)_3COOH, 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 CF_3(CF_2)_3COOH 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.
机译:使用烟雾室/ FTIR技术研究了在296 K的700托N_2 / O_2稀释剂中,Cl原子引发4:2氟代端粒醇(CF_3(CF_2)_3CH_2CH_2OH)的Cl原子氧化反应的产物和机理。CF_3(CF_2)_3CH2_CHO为唯一的一次氧化产物。 CF_3(CF_2)_3CHO,CF_3(CF_2)_3CH_2COOH和CF_3(CF_2)_3CH_2C(O)OOH是二次氧化产物。进一步照射导致形成CF_3(CF_2)_3COOH,COF_2和CF_3OH。 CF_3(CF_2)_3CHO,CF_3(CF_2)_3CH_2COOH和CF_3(CF_2)_3CH_2C(O)OOH由CF_3(CF_2)_3CH_2CHO氧化形成,产率分别为46%,27%和≤27%。使用相对速率技术,确定k(Cl + CF_3(CF_2)_3CH_2CHO)=(1.84±0.30)* 10〜(-11)cm〜3分子-1 s〜(-1)的值。 4:2氟调聚物醇的全氟化酸CF_3(CF_2)_3COOH的产率随稀释气体氧浓度的增加而增加。对于本文使用的实验条件并使用消耗量> 98%的4:2氟调聚物醇,在10、140、400和700进行的实验中,CF_3(CF_2)_3COOH的摩尔产率分别为<0.011、0.031、0.042和0.056分别为O + 2 Torr。这些结果表明,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。

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