Rate Constants for the Reactions of OH Radicals with CH3OCF2CHF2, CHF2OCH2CF2CHF2, CHF2OCH2CF2CF3, and CF3CH2OCF2CHF2 over the Temperature Range 250−430 K

Abstract

The OH reaction rate constants have been measured for CH3OCF2CHF2, CHF2OCH2CF2CHF2, CHF2OCH2CF2CF3, and CF3CH2OCF2CHF2 over the temperature range 250−430 K. Kinetic measurements have been carried out using the flash photolysis, laser photolysis, and discharge flow methods, combined respectively with the laser-induced fluorescence technique to monitor the OH radical concentrations. The influence of impurities contained in the samples of fluorinated ethers has been investigated by means of sample purification using gas chromatography. No sizable effect of impurities was found on the measured rate constants of these fluorinated ethers, if the purified samples were used in the kinetic measurements. The Arrhenius rate constants have been determined from the respective kinetic data as k(CH3OCF2CHF2) = 2.60 × 10-12 exp[−(1420 ± 170)/T], k(CHF2OCH2CF2CHF2) = 2.49 × 10-12 exp[−(1500 ± 170)/T], k(CHF2OCH2CF2CF3) = 2.14 × 10-12 exp[−(1580 ± 170)/T], and k(CF3CH2OCF2CHF2) = 1.49 × 10-12 exp[−(1520 ± 170)/T] cm3 molec...