Solvatochromic Parameters of the Binary Mixtures of Imidazolium Chloride Ionic Liquid Plus Molecular Solvent

Abstract

Imidazolium-based chloride ionic liquids (ILs) have exhibited remarkable performance in several important applications such as biomass dissolution and extraction, but their large viscosity is a non-negligible problem. Adding molecular co-solvents into chloride ILs is effective in reducing viscosity; nevertheless, understanding of the accompanied change of thermodynamic polarity is quite few. Therefore, in this work we reported three Kamlet-Taft solvatochromic parameters, including dipolarity/polarizability π*), hydrogen-bond acidity (α) and hydrogen-bond basicity (β), for the binary mixtures of several imidazolium-based chloride ILs plus either dipolar protic solvents (water and methanol) or dipolar aprotic solvents (dimethyl sulfoxide, N,N-dimethylformamide and acetonitrile). The results demonstrated that those parameters could be altered by the structure of IL and type of co-solvent owing to the solute-solvent and solvent-solvent interactions. The structure of alkyl chain of cation had considerable impact on the π* variation of IL aqueous solution against IL concentration but hardly affected other mixtures. Moreover, remarkable preferential solvation of probes was observed for β and α in the mixtures of IL and dipolar aprotic co-solvents, whereas the hydrogen-bond interactions between IL and dipolar protic co-solvent enabled the preferential solvation to be alleviated and resulted in more linear variation of β and α against the molar fraction of IL. The results not only contribute to a better understanding of the effect of co-solvent on imidazolium-based chloride ILs, but also are instructive for improving the thermodynamic performance of IL-based applications via providing IL+co-solvent mixtures with desirable physicochemical properties.