Atmospheric Degradation of CF₃OCFCF₂: Kinetics and Mechanism of Its Reaction with OH Radicals and Cl Atoms

Abstract

Smog chamber/FTIR techniques were used to study the OH radical and Cl atom initiated oxidation of CF3OCFCF2 in 700 Torr of air at 296 K. Using relative rate techniques it was determined that k(OH + CF3OCFCF2) = (2.6 ± 0.3) × 10-12 and k(Cl + CF3OCFCF2) = (3.0 ± 0.4) × 10-11 cm3 molecule-1 s-1. Cl atom initiated atmospheric oxidation of CF3OCFCF2 gives COF2 and CF3OC(O)F in molar yields of 100%. OH radical initiated atmospheric oxidation of CF3OCFCF2 in 700 Torr of air at 295 K gives COF2, CF3OC(O)F, and FC(O)C(O)F in molar yields of 90, 53, and 40%. The results are discussed with respect to the atmospheric degradation mechanism of CF3OCFCF2 and other ethers.