Kinetics of the reactions of chlorine atoms with selected fluoroacetates at atmospheric pressure and 298 K

The kinetics of the reactions of chlorine atoms with four fluoroacetates (FACETs) have been studied by the relative kinetic method at 298 ± 2 K and atmospheric pressure (760 ± 10 Torr) in a 1080 l quartz-glass photoreactor using in situ FT-IR spectroscopy for the detection of the organics. The following rate constants (in units of cm3 molecule−1 s−1) were derived: k(Cl + CF3C(O)OCH3) = (0.90 ± 0.30) × 10−13, k(Cl + CF3C(O)OCH2CH3) = (1.78 ± 0.57) × 10−12, k(Cl + CF2HC(O)OCH3) = (2.03 ± 0.65) × 10−13 and k(Cl + CF3C(O)OCH2CF3) = (1.18 ± 0.43) × 10−15. The errors quoted are a combination of the 2σ statistical errors and a 20% error in the reference reactions. Reactivity trends with respect to the degree and position of halogen substitution in the acetate are discussed together with possible atmospheric implications of the reactions.