Physicochemical studies on the interfacial and aggregation behavior of immidazolium- and pyrrolinidium-dodecyl sulfate in aqueous medium

Abstract

Salt free surface active ionic liquids (SAILs), 1-butyl-3-methylimidazolium dodecyl sulfate ([bmim]DS) and N-butyl-N-methylpyrrolidinium dodecyl sulfate ([bmp]DS) were synthesised by stoichiometric mixing of ionic liquid (IL) and sodium dodecyl sulfate (SDS). SAILs were characterised by FTIR, 1H NMR, 13C NMR and thermogravimetric analysis and differential thermal analysis (TGA-DTA). Interfacial and aggregation behavior of the SAILs were investigated by surface tension, conductance, UV–visible absorption, emission spectroscopy, dynamic light scattering and isothermal titration calorimetric studies. Results were compared with the precursor surfactant SDS. Critical micelle concentration (CMC) of the surfactants followed the sequence: SDS > [bmp]DS > [bmim]DS. Lower surface excess values of SAILs were due to electrostatic interaction between IL cation and DS-, besides the higher aqueous solubility of DS-, induced by the IL cations. Negative Gibbs free energy of micellization and higher fraction of counter ion binding values further support the proposition. Aggregation number (n) and size (dh) of the micelles were determined by fluorescence quenching and dynamic light scattering studies respectively; both ‘n’ and ‘dh’ values were higher for SAILs than SDS ([bmim]DS > [bmp]DS > SDS). SAIL aggregates, although larger in size with higher aggregation number, were more compact than SDS micelles. Enthalpies of micellization, being exothermic in nature, were higher for SAILs although the micellization processes were entropically controlled. SAILs are considered to have dual advantages of surfactant and IL with substantial decrease in toxicity level.