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Rate coefficients, k, for the gas-phase reaction of the OH radical with ( E)-CF 3 CH═CHCF 3 (( E)-1,1,1,4,4,4-hexafluoro-2-butene, HFO-1336mzz(E)) were measured over a range of temperatures (211-374 K) and bath gas pressures (20-300 Torr; He, N 2 ) using a pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) technique. k 1 ( T) was independent of pressure over this range of conditions with k 1 (296 K) = (1.31 ± 0.15) × 10 -13 cm 3 molecule -1 s -1 and k 1 ( T) = (6.94 ± 0.80) × 10 -13 exp[-(496 ± 10)/ T] cm 3 molecule -1 s -1 , where the uncertainties are 2σ, and the pre-exponential term includes estimated systematic error. Rate coefficients for the OD reaction were also determined over a range of temperatures (262-374 K) at 100 Torr (He). The OD rate coefficients were ∼15% greater than the OH values and showed similar temperature dependent behavior with k 2 ( T) = (7.52 ± 0.44) × 10 -13 exp[-(476 ± 20)/ T] and k 2 (296 K) = (1.53 ± 0.15) × 10 -13 cm 3 molecule -1 s -1 . The rate coefficients for reaction 1 were also measured using a relative rate technique between 296 and 375 K with k 1 (296 K) measured to be (1.22 ± 0.1) × 10 -13 cm 3 molecule -1 s -1 , in agreement with the PLP-LIF results. In addition, the 296 K rate coefficient for the O 3 + ( E)-CF 3 CH═CHCF 3 reaction was determined to be &lt;5.2 × 10 -22 cm 3 molecule -1 s -1 . A theoretical computational analysis is presented to interpret the observed positive temperature dependence for the addition reaction and the significant decrease in OH reactivity compared to the ( Z)-CF 3 CH═CHCF 3 stereoisomer reaction. The estimated atmospheric lifetime of ( E)-CF 3 CH═CHCF 3 , due to loss by reaction with OH, is estimated to be ∼90 days, while the actual lifetime will depend on the location and season of its emission. Infrared absorption spectra of ( E)-CF 3 CH═CHCF 3 were measured and used to estimate the 100 year time horizon global warming potentials (GWP) of 32 (atmospherically well-mixed) and 14 (lifetime-adjusted).

Rate Coefficient Measurements and Theoretical Analysis of the OH + (E)-CF3CH═CHCF3 Reaction

Rate Coefficient Measurements and Theoretical Analysis of the OH + (E)-CF₃CH═CHCF₃ Reaction