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+/-1 quartz-glass photoreactor using in situ FT-IR spectroscopy for the detection of the organics. The following rate constants (in units of cm(3) 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 + MC(O)OCH2CF3) = 0.18+/-0.43) x 10(-15). The errors quoted are a combination of the 2 sigma 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. (C) 2008 Elsevier B.V. All rights reserved.