Atmospheric chemistry of 4:2 fluorotelomer alcohol (CF3(CF2)3CH2CH2OH):: Products and mechanism of Cl atom initiated oxidation

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.