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OH reaction rate coefficients, infrared spectra, and climate metrics for (E)-...

Burkholder, J., J. Burkholder, C. Sciences, and V. C. Papadimitriou (2023), OH reaction rate coefficients, infrared spectra, and climate metrics for (E)- and (Z)- 2-perfluoroheptene (2-C7F14) and, Int. J. Chem. Kinetics, doi:10.1002/kin.21643.

In this work, perfluoroheptene 2- and 3-C7 F14 stereoisomer specific gas-phase OH reaction rate coefficients, k, were measured at 296 K in ∼600 Torr (He bath gas) using a relative rate (RR) method. Gas-chromatography (GC) with electron capture detection (ECD) was used for the separation and detection of the stereoisomers. Rate coefficients for (E)-2-C7 F14 , (Z)-2-C7 F14 , (E)-3-C7 F14 , and (Z)3-C7 F14 were measured to be (in units of 10−13 cm3 molecule−1 s−1 ) (3.60 ± 0.51), (2.22 ± 0.21), (3.43 ± 0.47), and (1.48 ± 0.19), respectively, where the uncertainties include estimated systematic errors. Rate coefficients for the (E)- stereoisomers were found to be systematically greater than the (Z)- stereoisomers by a factor of 1.6 and 2.3 for 2-C7 F14 and 3-C7 F14, respectively. Atmospheric lifetimes with respect to OH radical reaction for (E)-2-C7 F14 , (Z)-2-C7 F14 , (E)-3-C7 F14 , (Z)-3C7 F14 were estimated to be ∼33, ∼56, ∼36, and ∼86 days, respectively, for an average OH radical concentration of 1 × 106 molecule cm−3 . Quantitative infrared absorption spectra were measured as part of this work. Complimentary theoretically calculated infrared absorption spectra using density functional theory (DFT) are included in this work. The theoretical spectra were used to evaluate stereoisomer climate metrics. Radiative efficiencies (adjusted) and global warming potentials (GWPs, 100-year time-horizon), were estimated to be 0.12, 0.19, 0.12, and 0.23 W m−2 ppb−1 and 1.9, 5.1, 2.1, 9.3 for (E)-2-C7 F14 , (Z)-2-C7 F14 , (E)-3-C7 F14 , (Z)-3-C7 F14, respectively. Atmospheric degradation mechanisms are discussed.

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Atmospheric Composition