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1,2-Dichlorohexafluoro-cyclobutane (1,2-c‑C4F6Cl2, R‑316c) a Potent Ozone...

Papadimitriou, V. C., M. R. McGillen, S. C. Smith, A. M. Jubb, R. W. Portmann, B. D. Hall, E. L. Fleming, C. H. Jackman, and J. Burkholder (2013), 1,2-Dichlorohexafluoro-cyclobutane (1,2-c‑C4F6Cl2, R‑316c) a Potent Ozone Depleting Substance and Greenhouse Gas: Atmospheric Loss Processes, Lifetimes, and Ozone Depletion and Global Warming Potentials for the (E) and (Z) Stereoisomers, J. Phys. Chem. A, 117, 11049-11065, doi:10.1021/jp407823k.

The atmospheric processing of (E)- and (Z)-1,2-dichlorohexafluorocyclobutane (1,2-c-C4F6Cl2, R-316c) was examined in this work as the ozone depleting (ODP) and global warming (GWP) potentials of this proposed replacement compound are presently unknown. The predominant atmospheric loss processes and infrared absorption spectra of the R-316c isomers were measured to provide a basis to evaluate their atmospheric lifetimes and, thus, ODPs and GWPs. UV absorption spectra were measured between 184.95 to 230 nm at temperatures between 214 and 296 K and a parametrization for use in atmospheric modeling is presented. The Cl atom quantum yield in the 193 nm photolysis of R316c was measured to be 1.90 ± 0.27. Hexafluorocyclobutene (c-C4F6) was determined to be a photolysis co-product with molar yields of 0.7 and 1.0 (±10%) for (E)- and (Z)-R-316c, respectively. The 296 K total rate coefficient for the O(1D) + R-316c reaction, i.e., O(1D) loss, was measured to be (1.56 ± 0.11) × 10−10 cm3 molecule−1 s−1 and the reactive rate coefficient, i.e., R-316c loss, was measured to be (1.36 ± 0.20) × 10−10 cm3 molecule−1 s−1 corresponding to a ∼88% reactive yield. Rate coefficient upper-limits for the OH and O3 reaction with R-316c were determined to be <2.3 × 10−17 and <2.0 × 10−22 cm3 molecule−1 s−1, respectively, at 296 K. The quoted uncertainty limits are 2σ and include estimated systematic errors. Local and global annually averaged lifetimes for the (E)- and (Z)-R-316c isomers were calculated using a 2-D atmospheric model to be 74.6 ± 3 and 114.1 ± 10 years, respectively, where the estimated uncertainties are due solely to the uncertainty in the UV absorption spectra. Stratospheric photolysis is the predominant atmospheric loss process for both isomers with the O(1D) reaction making a minor, ∼2% for the (E) isomer and 7% for the (Z) isomer, contribution to the total atmospheric loss. Ozone depletion potentials for (E)- and (Z)-R-316c were calculated using the 2-D model to be 0.46 and 0.54, respectively. Infrared absorption spectra for (E)- and (Z)-R-316c were measured at 296 K and used to estimate their radiative efficiencies (REs) and GWPs; 100-year time-horizon GWPs of 4160 and 5400 were obtained for (E)- and (Z)-R-316c, respectively. Both isomers of R-316c are shown in this work to be long-lived ozone depleting substances and potent greenhouse gases.

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Upper Atmosphere Research Program (UARP)