Micellar rate enhancement studies in mixed sodium fluorocarbon/hydrocarbon surfactant solutions

Abstract

Stopped-flow kinetic studies were conducted in mixed micellar solutions of fluorocarbon and hydrocarbon anionic surfactants to determine the prevalent micellar form. The probe reaction was the Niaq2+/pyridine-2-azo-p-dimethylaniline (PADA) complexation, which is many times accelerated in the presence of anionic micelles. Binding constants for Niaq2+ and PADA partitioning between bulk solution and micelles were determined through the murexide technique and solubility measurements respectively and the molar reaction volume was obtained from the Robinson equation. The three binary surfactant systems investigated had sodium perfluoroheptanoate as the fluorocarbon surfactant while the hydrocarbon surfactants were sodium decylsulfate, sodium nonanesulfonate, and sodium octanesulfonate. The kinetic results were consistent with unimicellar composition in all three systems which was not the behaviour previously found with the sodium octane sulfonate/sodium perfluoroctanoate system. The difference was attributed to closer similarity in the surfactant pair hydrophobicities as revealed through their critical micelle concentrations. Another finding was that mixed micelles synergistically can lead to a much greater solubilization of PADA than is possible through either of the pure surfactants.