Demulsification of Redox-Active Emulsions by Chemical Oxidation

This article reports the influence of redox reactions on emulsions of n-octane and an aqueous solution of a ferrocene-containing surfactant (FTMA; (11-ferrocenylundecyl)trimethylammonium bromide). Above a certain surfactant concentration, stable O/W emulsions were formed from an aqueous solution of reduced FTMA; in contrast, mixtures of n-octane and an aqueous solution of oxidized FTMA did not form emulsions at any surfactant concentration. Furthermore, adding an oxidant to the stable O/W emulsions of reduced FTMA led to coalescence of the oil (octane) droplets in the emulsions, and subsequently, the oil and water (aqueous FTMA solution) phases fully separated from the emulsions, i.e., demulsification occurred. Equilibrated interfacial tension measurements indicate that oxidation of the ferrocenyl group in FTMA brings about an increase in the interfacial tension between the octane and aqueous surfactant solution phases. From these results, we concluded that the oxidation of reduced FTMA to oxidized FTMA led to the desorption of surfactant molecules adsorbed at the interface of the octane/aqueous surfactant solution, leading to demulsification.