Tuning of Cloud Point by the Nature of Surfactant Headgroup: Influence of Counterion and Additives

Work was performed to distinguish the role of sulfonate (–SO₃ ^?) and sulfate (–OSO₃ ^?) with respect to the micellization and clouding phenomenon in ionic surfactant solutions. The clouding phenomenon is a recent addition to the conventional one observed with nonionic surfactants. Three ionic surfactants sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSo)] are chosen and the effects of added tetra-n-pentylammonium bromide (TPeAB) and benzyl tributylammonium bromide (BTAC) have been studied on micellization and clouding behaviors in aqueous solution. Based on critical micelle concentration (CMC) and cloud point (CP) measurements, the following order has been observed: SDBS < SDS < SDSo. Though both SDBS and SDSo contain sulfonate groups, they are found at the two ends of the ordering. Therefore, the role of the phenyl ring is also having importance in clouding phenomena. For a typical surfactant, TPeAB was found to be more effective than BTAC. Based on the CP studies, two compositions of SDSo + TPeAB/BTAC were chosen and the effects of different additives (carbohydrate, amino acid, and l-ascorbic acid) on the CP were investigated. Additive may either decrease or increase CP, depending on the structure of the counterion or additive. The present work shows a few novelties: (1) headgroup/counterion dependence of CP and (2) hydrophobicity of counterion/surfactant has an important bearing on the phenomenon. The data can be utilised in improving cloud point extraction methodologies (CPEMs).