Effect of the cation on the interactions between alkyl methyl imidazolium chloride ionic liquids and water

A systematic study of the interactions between water and alkyl methyl imidazolium chloride ionic liquids at 298.2 K, based on activity coefficients estimated from water activity measurements in the entire solubility range, is presented. The results show that the activity coefficients of water in the studied ILs are controlled by the hydrophilicity of the cation and the cation-anion interaction. To achieve a deeper understanding on the interactions between water and the ILs, COSMO-RS and FTIR spectroscopy were also applied. COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies, suggesting the formation of complexes between three molecules of water and one IL molecule. On the basis of quantum-chemical calculations, it is found that cation-anion interaction plays an important role upon the ability of the IL anion to interact with water. The changes in the peak positions/band areas of OH vibrational modes of water as a function of IL concentration were investigated, and the impact of the cation on the hydrogen-bonding network of water is identified and discussed.

Volumetric interactions of a series of α-amino acids in aqueous magnesium chloride solutions at 278.15, 288.15, 298.15, and 308.15 K

In this work, the partial molar volumes of glycine, l-alanine, l-valine, l-serine, and l-threonine in aqueous solutions of magnesium chloride at 0.0, 0.1, 0.3, 0.7, and 1.0 molal are addressed between 278.15 and 308.15 K. Volumes of transfer were obtained, following the rank serine > glycine a parts per thousand threonine > alanine > valine. Differently, the hydration numbers follow the sequence serine > valine > alanine > threonine > glycine, and dehydration of the amino acids is observed, rising the temperature or salt molality. The data suggest that interactions are mainly pairwise, between the ions and charged/hydrophilic groups of the amino acids. Within the Friedman and Krishnan formalism, a group-contribution scheme has been successfully applied to the pairwise volumetric interaction coefficient. Finally, the dehydration effect of MgCl2 on glycine, alanine, and serine has been predicted applying empirical correlations developed before, showing satisfactory results.