The reactions of the plithalimide N-oxyl (PINO) radical with several hydrocarbons having different C-H bond dissociation energies (BDEs) were investigated in HCAc at 25 degreesC. The slope of the Evans-Polanyi plot is 0.38, which indicates that the reactions are mildly exothermic or almost thermoneutral. This finding is supported by the O-H BDE of N-hydroxyphthalimide (NHPI), 375 +/- 10 kJ mol(-1), obtained by means of a thermodynamic cycle. The observed kinetic isotope effects (KIEs) are related to the reaction free-energy changes, which can be explained by a Marcus-type equation. The comparison of the PINO radical reactions with analogous hydrogen atom abstraction reactions of the dibromide radical implies that HBr2.reactions are more exothermic than the PINO radical reactions. This factor is put forth to explain the different KIEs.