Modifying properties of aqueous cetyltrimethylammonium bromide with external additives: ionic liquid 1-hexyl-3-methylimidazolium bromide versus cosurfactant n-hexyltrimethylammonium bromide.

Understanding the effect of external additives on the properties of aqueous surfactant solutions is of utmost importance due to widespread applications of surfactant-based systems. Role of ionic liquids (ILs) in this regard may turn out to be crucial as these substances are known to possess unusual properties. To unambiguously understand and establish the role of ILs in modifying properties of aqueous surfactant systems, changes in the physicochemical properties of aqueous cetyltrimethylammonium bromide (CTAB) upon addition of an IL 1-hexyl-3-methylimidazolium bromide ([hmim][Br]) are compared with those when a cosurfactant n-hexyltrimethylammonium bromide (HeTAB) is added to aqueous CTAB. Important physicochemical properties, such as critical micelle concentration (cmc), aggregation number (N(agg)), solution conductance and microfluidity, and average aggregate size and polydispersity, are observed to change as either [hmim][Br] or HeTAB is added to aqueous CTAB; the experimental outcomes clearly imply the changes in most of the physicochemical properties to be significantly more dramatic in case of IL [hmim][Br] addition. The fact that, between the two, only IL [hmim][Br] may show cosolvent-type behavior at high concentrations is evoked to explain the differences in the behavior of the two additives. It is demonstrated that both [hmim][Br] and HeTAB show electrolytic as well as cosurfactant-type behavior within aqueous CTAB when present at low concentrations, with the changes in physicochemical properties being very similar. At high concentrations, although HeTAB still acts as a cosurfactant forming mixed micelles with CTAB, IL [hmim][Br] behaves partly as a cosolvent toward altering the physicochemical properties of aqueous CTAB. The unique role of IL in changing properties of aqueous surfactant systems is demonstrated.