Methyl-Perfluoroheptene-Ethers (CH3OC7F13): Measured OH Radical Reaction Rate...

Jubb, A. M., T. Gierczak, M. Baasandorj, R. L. Waterland, and J. Burkholder (2014), Methyl-Perfluoroheptene-Ethers (CH3OC7F13): Measured OH Radical Reaction Rate Coefficients for Several Isomers and Enantiomers and Their Atmospheric Lifetimes and Global Warming Potentials, Environ. Sci. Technol., 48, 4954-4962, doi:10.1021/es500888v.

Mixtures of methyl-perfluoroheptene-ethers (CH3OC7F13, MPHEs) are currently in use as replacements for perfluorinated alkanes (PFCs) and poly-ether heat transfer fluids, which are persistent greenhouse gases with lifetimes >1000 years. At present, the atmospheric processing and environmental impact from the use of MPHEs is unknown. In this work, rate coefficients at 296 K for the gas-phase reaction of the OH radical with six key isomers (including stereoisomers and enantiomers) of MPHEs used commercially were measured using a relative rate method. Rate coefficients for the six MPHE isomers ranged from ∼0.1 to 2.9 × 10−12 cm3 molecule−1 s−1 with a strong stereoisomer and −OCH3 group position dependence; the (E)-stereoisomers with the −OCH3 group in an α- position relative to the double bond had the greatest reactivity. Rate coefficients measured for the d3-MPHE isomer analogues showed decreased reactivity consistent with a minor contribution of H atom abstraction from the −OCH3 group to the overall reactivity. Estimated atmospheric lifetimes for the MPHE isomers range from days to months. Atmospheric lifetimes, radiative efficiencies, and global warming potentials for these short-lived MPHE isomers were estimated based on the measured OH rate coefficients along with measured and theoretically calculated MPHE infrared absorption spectra. Our results highlight the importance of quantifying the atmospheric impact of individual components in an isomeric mixture.

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Upper Atmosphere Research Program (UARP)