Rate Constants for the Reactions of OH Radicals with Fluorinated Ethenes: Kinetic Measurements and Correlation between Structure and Reactivity.

The rate constants for the reaction of OH radicals with four fluorinated ethenes (CF═CHF, ( E)-CHF═CHF, CF═CH, and CHF═CH) have been measured over the temperature range of 250-430 K. Kinetic measurements have been carried out using flash photolysis and laser photolysis methods combined with a laser-induced fluorescence technique. The Arrhenius expressions for the rate constant have been determined as k(CF═CHF) = (3.12 ± 0.11) × 10 exp[(270 ± 10)/ T], k(( E)-CHF═CHF) = (3.75 ± 0.08) × 10 exp[(230 ± 10)/ T], k(CF═CH) = (1.15 ± 0.07) × 10 exp[(230 ± 20)/ T], and k(CHF═CH) = (1.16 ± 0.09) × 10 exp[(390 ± 20)/ T] cm molecule s. Infrared absorption spectra of the fluorinated ethenes have been measured at room temperature. The atmospheric lifetimes and global warming potentials of the fluorinated ethenes have been estimated. The correlation between the reactivity and the structure of the halogenated ethenes has been investigated by considering the structure containing the atoms attached to the carbons on both sides of the double bond. The calculated rate constants of 14 halogenated ethenes showed agreement with the measured rate constants within a factor of 2, except for that of one compound.