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Hypothesis The phase behavior of amphiphiles is known to depend on their solvent environment. The organic character of ionic liquids suggested the possibility to tune surfactant aggregation, even in the absence of water, by selection of appropriate ionic liquid chemistry. To that end the behavior of the surfactant sodium dodecylsulfate in a chemically similar imidazolium ionic liquid, 1-ethyl-3-methyl imidazolium ethylsulfate, was explored. Experiments The solubility of sodium dodecylsulfate in 1-ethyl-3-methyl imidazolium ethylsulfate was determined, establishing the Krafft temperature. Tensiometry was performed to obtain interfacial properties such as the surface excess and area per molecule. Pulsed-field gradient spin-echo NMR was used to determine the diffusion coefficients of all the major species, including micelles, as a function of surfactant concentration. Importantly, all three methods provided consistent values for the critical micelle concentration. Findings Analysis of tensiometry data suggests, and is confirmed by NMR results, that the ionic liquid ions are incorporated along with surfactants into micelles, revealing a complex micellization behavior. In light of these findings past studies with ternary mixtures of surfactants, ionic liquids, and water may merit additional scrutiny. Given the large number of ionic liquids, this work suggests opportunities to further control micelle formation and properties.

The aggregation and interfacial behavior of mixtures of anionic (sodium dodecylsulfate, SDS) and cationic (dodecylammonium bromide, DTAB) surfactants were investigated. A room-temperature ionic liquid (IL) was explored as a solvent for the SDS/DTAB system and compared to water. The critical micelle concentration (cmc) and composition in mixed micelles were determined for both solvents. Our experiments showed nearly ideal mixing of SDS/DTAB over the entire composition range and suggest that charge screening is prominent in ILs. This behavior is in sharp contrast to the strong electrostatic attraction and a multiphase composition gap in water. Two models by Clint and Rubingh, which describe ideal and nonideal micellar behavior, respectively, are discussed on the basis of our results. According to Rubingh's model, the composition of mixed micelles is gradually changing with the bulk composition in ILs but tends to be a 1:1 ratio in water. The results here are further support of the strong charge screening in ionic liquids.

The dynamical and aggregation behaviors of sodium dodecyl sulfate (SDS) in 1-ethyl-3-methylimidazolium ethylsulfate [EMIM+][EtSO4–] are characterized experimentally and computationally. A retardation of the ionic liquid (IL) and SDS diffusion coefficients with a concentration increase of SDS is observed. In agreement with experiments, aggregation is detected for concentrations higher than the experimental critical micelle concentration (CMC), which is mostly driven by alkyl tail aggregation. Solvent-exposed hydrophobic patches are observed on the micelle's surfaces. The hydrophobic tails of the IL molecules are found to fill those micelle's hydrophobic patches. Also, penetration of the IL is found in the SDS micelles, indicating that the IL acts as a cosurfactant, allowing the formation of "mixed" micelles. A higher level of Na+ counterion dissociation compared to previous studies of SDS micelles in aqueous solutions is also observed. A multilayering effect of alternating IL anions and cations is detected at the surface of the formed aggregates. The observed increase in system ordering with SDS concentration is what hinders the mobility of each chemical species.

Room-temperature ionic liquids (ILs) exhibit a unique set of properties, leading to opportunities for numerous applications. To obtain a better understanding of IL interfaces at a molecular level, we combined charged surfactants with ILs and studied their interfacial behavior. The critical micelle concentration (cmc) of each surfactant–IL pair was determined from both solubility phase diagrams and isotherms. Because the cmc is equivalent to the solubility at the Krafft temperature, a connection between the solubility of the surfactant and the physical properties of the underlying ionic liquid was established. Interfacial energy was found to be the major factor affecting the surfactant aggregation process, although its magnitude depends strongly on the IL structure. The results here give insight into explaining the nature of self-assembly of surfactants at IL interfaces and the interaction between solutes and IL solvents.

Room-temperature ionic liquids (ILs) exhibit a unique set of properties due to their charged character, presenting opportunities for numerous applications. Here, we show that the combination of charged surfactants with ILs leads to rich interfacial behavior due to the interplay between electrostatic and surface forces. Using traditional measures of surface activity and X-ray photoelectron spectroscopy (XPS), we find that sodium alkyl sulfates and alkyl trimethylammonium bromides are, indeed, surface-active at the air-IL interfaces of both [EMIM][EtSO(4)] and [BHEDMA][MeSO(3)]. XPS also reveals that surfactant counterions readily dissociate into the bulk, which when combined with the surfactant surface activity has striking consequences. We find that ion exchange occurs between surfactants and like-charged IL ions, with the greatest exchange for short surfactant alkyl chains. The initial negative surface charge of neat [EMIM][EtSO(4)] can be switched to positive by the addition of alkyl trimethylammonium bromides, with the effect most pronounced at short chain lengths. By contrast, the surface charge of [BHEDMA][MeSO(3)] is largely unaffected by the added surfactants, suggesting a key role for the strength of ion-pairing within the IL. The results here illustrate a simple but effective means of manipulating IL interfacial properties.