First Evidence of Simultaneous Different Kinetic Behaviors at the Interface and the Continuous Medium of w/o Microemulsions

Luis García-Rio, Juan C. Mejuto, and Moisés Pérez-Lorenzo
J. Phys. Chem. B, 2006, 110, 812–819


A study was carried out on the butylaminolysis reaction of 4-nitrophenyl caprate in AOT/chlorobenzene/water microemulsions, with the observed rate constant, kobs, showing both first- and second-order dependence on butylamine concentration. The first-order term in [BuNH2] is due to the reaction occurring at the interface of the microemulsion while the second-order term is due to the reaction in the continuous medium. The different kinetic behavior is accounted for by the mechanism by which the reaction proceeds:  at the interface of the microemulsion, the rate-determining step is the formation of the addition intermediate, T±, whereas in the continuous medium the slow step is the base-catalyzed decomposition of this intermediate. The application of the pseudophase formalism allows the observed kinetic behavior to be explained and to obtain the rate constants at the interface, = 0.13 M-1 s-1, and in the continuous medium, KT = 2.46 × 10-2 M-2 s-1. These values indicate that the reaction rate decreases approximately 23 times upon going from the aqueous medium to the interface of the microemulsion, whereas the rate constant in the continuous medium is consistent with that obtained in pure chlorobenzene, KT = 2.09 × 10-2 M-2 s-1.