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Photochemical Properties of Hydrofluoroethers CH3OCHF2, CH3OCF3, and...

Orkin, V. L., V. G. Khamaganov, and A. G. Guschin (2014), Photochemical Properties of Hydrofluoroethers CH3OCHF2, CH3OCF3, and CHF2OCH2CF3: Reactivity toward OH, IR Absorption Cross Sections, Atmospheric Lifetimes, and Global Warming Potentials, J. Phys. Chem. A, 118, 10770-10777, doi:10.1021/jp506377w.

Rate constants for the gas phase reactions of OH radicals with three partially fluorinated ethers, CH3OCF3 (kHFE‑143a), CH3OCHF2 (kHFE‑152a), and CHF2OCH2CF3 (kHFE‑245fa2), were measured using a discharge flow−electron paramagnetic resonance technique over the temperature range 298−460 K. The temperature dependences of the rate constants can be represented by the following expressions: kHFE‑143a(T) = (1.10 ± 0.20)×10−12×exp{−(1324 ± 61)/T} cm3molecule−1s−1; kHFE‑152a(T) = (11.6 ± 4.2)×10−12×exp{−(1728 ± 133)/T} cm3molecule−1s−1; and kHFE‑245fa2(T) = (3.04 ± 0.57)×10−12×exp{−(1665 ± 66)/T} cm3molecule−1s−1. The atmospheric lifetimes due to reactions with tropospheric OH were estimated to be 5.2, 1.9, and 5.6 years, respectively. The IR absorption cross sections of these fluorinated ethers were measured between 400 and 2000 cm−1, and their global warming potentials were estimated.

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Upper Atmosphere Research Program (UARP)