High-Accuracy Measurements of OH Reaction Rate Constants and IR Absorption...

Orkin, V. L., L. E. Martynova, and A. N. Ilichev (2010), High-Accuracy Measurements of OH Reaction Rate Constants and IR Absorption Spectra: CH2=CF-CF3 and trans-CHF=CH-CF3, J. Phys. Chem. A, 114, 5967-5979, doi:10.1021/jp9092817.

Rate constants for the gas phase reactions of OH radicals with two isomers of tetrafluoropropene, CH2=CF-CF3 (k1) and trans-CHF=CH-CF3 (k2), were measured using a flash photolysis resonance-fluorescence technique over the temperature range 220 to 370 K. The Arrhenius plots were found to exhibit a noticeable curvature.
The temperature dependences of the rate constants are very weak and can be represented by the following expressions over the indicated temperature intervals:

k1(220-298 K) = 1.145 × 10-12 × exp{-13⁄T} cm3 molecule-1 s-1

k1(298-370 K) = 4.06 × 10-13 × (T⁄298)^1.17 × exp{+296⁄T} cm3 molecule-1 s-1

k2(220-370 K) = 1.115 × 10-13 × (T⁄298)^2.03 × exp{+552⁄T} cm3 molecule-1 s-1

The overall accuracy of the rate constant measurements is estimated to be ca. 2% to 2.5% at the 95% confidence level. The uncertainty of the measured reaction rate constants is discussed in detail. The atmospheric lifetimes due to reactions with tropospheric OH were estimated to be 12 and 19 days respectively under the assumption of a well mixed atmosphere. IR absorption cross-sections were measured for both compounds and their global warming potentials were estimated.

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Upper Atmosphere Research Program (UARP)