Kinetics of the Reactions of Chlorine Atoms with Selected Fluoroacetates at Atmospheric Pressure and 298 K

M. B .BLANCO, I. BEJAN, I. BARNES, P. WIESEN AND M.A.TERUEL

CHEMICAL PHYSICS LETTERS

ELSEVIER SCIENCE BV

Año: 2008 p. 18 - 23

0009-2614

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 FTIR 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) x 10-13, k(Cl +CF3C(O)OCH2CH3) = (1.78 ±0.57) x 10-12, k(Cl +CF2HC(O)OCH3) = (2.03 ± 0.65) x 10-13 and k(Cl + CF3C(O)OCH2CF3) = (1.18 ±0.43) x 10-15. The errors quoted are a combination of the 2ƒÐ 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.