Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

Abstract

Abstract A comprehensive study of several atmospheric degradation routes for two hydrofluoroalcohols, CF 3 (CH 2 ) x =1,2 CH 2 OH, is presented. The gas‐phase kinetics of their reactions with hydroxyl radicals (OH) and chlorine (Cl) atoms are investigated by absolute and relative techniques, respectively. The room‐temperature rate coefficients (± σ , in cm 3 molecule −1 s −1 ) k OH and k Cl , are respectively (9.7±1.1)×10 −13 and (1.60±0.45)×10 −11 for CF 3 CH 2 CH 2 OH, and (2.62±0.32)×10 −12 and (8.71±0.24)×10 −11 for CF 3 (CH 2 ) 2 CH 2 OH. Average lifetimes of CF 3 CH 2 CH 2 OH and CF 3 (CH 2 ) 2 CH 2 OH due to the OH and Cl reactions are estimated to be 12 and 4 days, and greater than 20 and 4 years, respectively. Also, the IR and UV absorption cross sections of CF 3 (CH 2 ) x =1,2 CH 2 OH are determined in the spectral ranges of 500–4000 cm −1 and 200–310 nm. Photolysis of CF 3 (CH 2 ) x =1,2 CH 2 OH in the actinic region (λ ≥290 nm) is negligible compared to their homogeneous removal. Additionally, computational IR spectra are consistent with the experimental ones, thus giving high confidence in the obtained results. The lifetimes of CF 3 (CH 2 ) x =1,2 CH 2 OH and IR spectra reported herein allow the calculation of the direct global warming potential of these hydrofluoroalcohols. The contribution of CF 3 (CH 2 ) x CH 2 OH to radiative forcing of climate change will be negligible.