Atmospheric Chemistry of CH3O(CF2CF2O)nCH3(n= 1-3): Kinetics and Mechanism of Oxidation Initiated by Cl Atoms and OH Radicals, IR Spectra, and Global Warming Potentials

Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH 3 O(CF 2 CF 2 O) n CH 3 (n = 1-3) in 720 ′ 20 Torr of air at 296 ′ 3 K. Relative rate techniques were used to measure k(Cl + CH 3 O(CF 2 CF 2 O) n CH 3 ) = (3.7 ′ 0.7) x 10 - 1 3 and k(OH + CH 3 O(CF 2 CF 2 O) n -CH 3 ) = (2.9 ′ 0.5) × 10 - 1 4 cm 3 molecule - 1 s - 1 leading to an estimated atmospheric lifetime of 2 years for CH 3 O(CF 2 CF 2 O) n CH 3 . The Cl initiated oxidation of CH 3 O(CF 2 CF 2 O) n CH 3 in air diluent gives CH 3 O(CF 2 CF 2 O) n C(O)H in a yield which is indistinguishable from 100%. Further oxidation leads to the diformate, H(O)CO(CF 2 CF 2 O) n C(O)H. A rate constant of k(Cl + CH 3 O(CF 2 CF 2 O) n CHO) = (1.81 ′ 0.36) × 10 - 1 3 cm 3 molecule - 1 s - 1 was determined. Quantitative infrared spectra for CH 3 O(CF 2 CF 2 O) n CH 3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH 3 OCF 2 CF 2 OCH 3 , CH 3 O(CF 2 CF 2 O) 2 CH 3 , and CH 3 C(CF 2 CF 2 O) 3 -CH 3 , respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs).