Influence of Anions and Micelle and Submicellar Aggregates on the Alkaline Hydrolysis of Malachite Green: Tensiometric, Spectrophotometric, and Kinetic Investigations

The influence of mono- and bivalent anions and micelle/submicellar clusters of different ionic and nonionic surfactants on the hydrolysis of malachite green (MG(+)) was studied in the presence of low alkali concentrations. Large polarizable I- ion and bivalent SO42- ion show specific interaction toward MG(+) with the formation of dye-anion ion-pair resulting in a retardation of the reaction rate. Tensiometric studies for anionic surfactants sodium dodecyl sulfate (SDS) and dioctyl sodium sulfosuccinate (AOT) in the presence of dye indicate the formation of ion-pair micelles which subsequently break down to form normal micelles. A change of the absorbance value accompanied by a red shift in the electronic spectra with increase in surfactant concentration also evidenced the formation of ion-pair. The observed rate inhibition by the anionic surfactants and the interaction behavior/nature of binding between the dye and surfactant in the premicellar region have been analyzed in terms of different kinetic models. The Piszkiewicz cooperativity index (n) suggests 1:1 association between the anionic surfactant monomer and MG(+) in the submicellar cluster. A catalyzing effect for the cationic surfactant, cetyltrimethylammonium bromide (CTAB), was noticed in the post-CMC region leading toward a limiting reaction rate, and the Menger-Portonoy pseudophase model was employed to explain the behavior with evaluation of the binding parameter. The nonionic surfactant poly(oxyethylene) (20) sorbitan monolaurate (Tween 20) exerts inhibition effect on the hydrolysis reaction which may be explained qualitatively by the dearth of HO- ions in the vicinity of the micelle-bound dye and quantitatively in light of the pseudophase model. Different equilibrium constants and binding constant parameters suggest appreciable binding between the dye and surfactant monomer/micelles owing to electrostatic/hydrophobic interactions.