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

Huang Jingyi, Weihua Zhu, Qiwei Yang, G. Qian, Huabin Xing
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引用次数: 10

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 ( ð *), 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 ð * 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.
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氯咪唑离子液体与分子溶剂二元混合物的溶剂致变色参数
咪唑基氯离子液体(ILs)在生物质溶解和萃取等重要应用中表现出了显著的性能,但其大粘度是一个不可忽视的问题。在氯离子中加入分子共溶剂可有效降低粘度;然而,对伴随而来的热力学极性变化的认识却很少。因此,在这项工作中,我们报道了三个Kamlet-Taft溶剂变色参数,包括双极性/极化率(ð *),氢键酸度(α)和氢键碱度(β),用于几种咪唑基氯离子偶极质子溶剂(水和甲醇)或偶极非质子溶剂(二甲亚砜,N, N -二甲基甲酰胺和乙腈)的二元混合物。结果表明,这些参数会因溶剂-溶剂和溶剂-溶剂的相互作用而受到IL结构和助溶剂类型的影响。烷基阳离子链结构对IL水溶液随IL浓度的变化有较大影响,但对其他混合物影响不大。此外,在偶极非质子共溶剂中,探针对β和α有明显的优先溶剂化作用,而偶极质子共溶剂与IL之间的氢键相互作用使得优先溶剂化作用得到缓解,β和α随IL摩尔分数的线性变化更明显。而且对于通过提供具有理想物理化学性质的IL+共溶剂混合物来改善IL基应用的热力学性能也具有指导意义。
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