Ionic association and interactions in aqueous methylsulfate alkyl-imidazolium-based ionic liquids

Several experimental techniques were used to study ionic association and interactions in aqueous [C(1)C(2)Im][MeSO4], 1-ethyl-3-methylimidazolium methylsulfate, and [C(1)C(4)Im][MeSO4], 1-butyl-3-methylimidazolium methylsulfate. Two transport properties, viscosity and electrical conductivity, were determined for these two binary mixtures. For a better assessment of the ionic association and the perturbation of water into the molecular structure of the ionic liquid, diffusion coefficients of ions and water molecules were obtained by NMR spectroscopy while molecular interactions were probed by IR spectroscopy. The comparison of the two ionic liquids shows that for the shorter alkyl chain the viscosity was lower and the electrical conductivity was higher. While the viscosity of the mixture drops already with small additions of water, the electrical conductivity of the solution is only significantly increased for high water concentrations. A maximum is observed for compositions around x(water) = (0.90 to 0.95). The SO3 asymmetric stretching band of the IR spectrum can be used as a probe to observe the evolution of the structure around the anion which was mainly occurring for high concentrations of water. Several experimental techniques show than the main change in the ionic association was only observed for high water contents (water mole fraction > 0.8). (C) 2014 Elsevier Ltd. All rights reserved.