title: Ionizing power and nucleophilicity in water in oil AOT-based microemulsions.
abstract: A study was carried out on the solvolysis of substituted phenyl chloroformates in AOT/isooctane/water microemulsions. (AOT is the sodium salt of bis(2-ethyhexyl)sulfosuccinate.) The results obtained have been interpreted by taking into account the distribution of the chloroformates between the continuous medium and the interface of the microemulsions, where the reactions take place. The values obtained for the rate constant in the interface, k(i), decreases as the water content of the microemulsions increases, as a consequence of the decrease in its nucleophilic capacity. This behavior is consistent with a rate-determining step of water addition to the carbonyl group. The values of k(i) allow us to obtain the slopes of the Hammett correlations at the interface of the microemulsions, rho = 2.25, whose values are greater than those obtained in an aqueous medium, rho = 0.82. This increase in the Hammett slope is similar to that observed in ethanol/water mixtures and is a consequence of a variation in the structure of the transition state of the reaction where there is a smaller extension of the expulsion of the leaving group. The values of the rate constants at the interface of the microemulsions have allowed us, by means of the Grunwald-Winstein equation, to obtain the solvent ionizing power and the nucleophilicity of the solvent. The values obtained for Y(Cl) increase together with the water content of the microemulsion, whereas the values of N(T) decrease. These variations are a consequence of the interaction between the AOT headgroups and the interfacial water, where the water molecules act like electronic acceptors. The intensity of this interaction is greater if the system has a small water content, which explains the variation of Y(Cl) and N(T).
authors.affiliation: Departamento de Química Física, Facultad de Química, Universidad de Santiago, 15782 Santiago, Spain. qflgr3cn@usc.es
authors.forename: Luis
authors.initials: L
authors.lastname: García-Río
authors.forename: Pablo
authors.initials: P
authors.lastname: Hervella
authors.forename: José Ramón
authors.initials: JR
authors.lastname: Leis
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D002723:Chlorobenzoates / Q000737:chemistry*; D004655:Emulsions; D006860:Hydrogen Bonding; D008956:Models, Chemical; D015394:Molecular Structure; D009795:Octanes / Q000737:chemistry; D012995:Solubility; D013386:Succinates / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D002723:Chlorobenzoates; D004655:Emulsions; D009795:Octanes; D013386:Succinates; C511925:bis(2-ethylhexyl)sulfosuccinate; D014867:Water; C032544:phenyl chloroformate; C045798:2,2,4-trimethylpentane