The kinetics of C-Cl bond cleavage on the Pd(111) surface have been measured using four chlorofluorocarbons (CFCs) containing different numbers of chlorine atoms on the primary carbon: CF3CCl3, CF3CFCl2, CF3CF2Cl, and CF3CHFCl. The desorption energies, DeltaE(des), Of the CFCs were found to increase with increasing number of chlorine atoms in the following order: CF3CF2Cl < CF3CHFCl < CF3CFCl2 < CF3CCl3. The rate constants and apparent barriers to C-Cl cleavage, DeltaE(app), on the Pd(111) surface were measured using CF3CFCl2, CF3CF2Cl, and CF3CHFCl. The trend in DeltaE(app) was found to be opposite that for DeltaE(des): CF3CFCl2 < CF3CHFCl < CF3CF2Cl. For CF3CFCl2 and CF3CHFCl the intrinsic activation energy for C-Cl cleavage on the Pd(111) surface, DeltaE(C-Cl), was determined by adding the desorption energies and the apparent activation energies for dissociative adsorption, DeltaE(C-Cl) = DeltaE(app) + DeltaE(app). In contrast with the other compounds, CF3CCl3 adsorbed on the Pd(111) Surface dechlorinates rather than desorbing during heating, thus allowing direct measurement of DeltaE(C-Cl). Comparison of DeltaE(C-Cl) and DeltaE(des) among the CFCs suggests that the variations in DeltaE(des) have a greater influence on the dechlorination reactivity than the variations in DeltaE(C-Cl). (C) 2004 Elsevier Inc. All rights reserved.