title: Change in the acid hydrolysis mechanism of esters enforced by strongly acid microemulsions.
abstract: A kinetic study was carried out on the acid hydrolysis of 4-nitrophenylacetate and 4-nitrophenyllaurate in water/HOT/isooctane microemulsions. The substitution of Na+ in the sodium salt of bis(2-ethylhexyl)sulfosuccinate by H+ has permitted us to obtain a functionalized surfactant (HOT) and, consequently, strongly acid microemulsions. The use of HOT-based microemulsions allows us to reach concentrations of H+ in the aqueous core corresponding to a Hammett acidity function of H0 = -2. The rate constant at the interface and the distribution constants of the carboxylic esters throughout the different microenvironments of the microemulsion have been quantified by application of the pseudophase formalism. The results obtained show that the hydrolysis rate constant at the interface increases as the water content of the system decreases. The correlation of the rate constants at the interface of the microemulsion with the Hammett acidity function, H0 (on the basis of the Bunnett-Olsen criterion), has allowed us to confirm that the hydrolysis process takes place via an A2 mechanism for high water contents and through an A1 mechanism for values of W <or= 15 (W = [H2O]/[HOT]).
authors.affiliation: Departamento de Química Física, Facultad de Química, Universidad de Santiago de Compostela, 15782 Santiago, Spain.
authors.forename: E
authors.initials: E
authors.lastname: Fernández
authors.forename: L
authors.initials: L
authors.lastname: García-Río
authors.forename: P
authors.initials: P
authors.lastname: Rodríguez-Dafonte