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1,3-二烷基咪唑离子液体-水二元混合物的溶致显色参数和优先溶剂化行为

Solvatochromic Parameters and Preferential Solvation Behavior for Binary Mixtures of 1,3-Dialkylimidazolium Ionic Liquids with Water

  • 摘要: 以1,3-二烷基咪唑离子液体(ILs)-水二元混合物为目标体系,研究25℃溶质-溶剂和溶剂-溶剂之间相互作用对溶致显色探针分子的优先溶剂化影响. 通过测量4-硝基苯胺、4-硝基苯甲醚和理查德染料的紫外-可见光光谱迁移,得到偶极性/可极化性(π*)、氢键酸性(α)、氢键碱性(β)和理查德极性参数(ETN)等溶致显色经验参数. 研究表明,离子液体种类和摩尔分数(xIL)影响离子液体-水混合物的溶剂性质. 所有研究的体系都表现出非理想特性行为. xIL=0.1~0.3,溶致显色参数偏离理想值最大. 对于大多数二元混合物,π*值显示存在协同作用,而ETNαβ值并没有体现出这一效应. 协同作用程度与染料探针和离子液体种类等研究体系特性有关. 利用优先溶剂化模型深入分析和研究混合物中分子之间相互作用. 优先溶剂化染料探针分子的顺序为:离子液体 >离子液体-水 >水.

     

    Abstract: Binary mixtures of 1,3-dialkylimidazolium based ionic liquids (ILs) and water were selected as solvent systems to investigate the solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators at 25℃. Empirical solvatochromic parameters, dipolarity/polarizability (π*), hydrogen-bond donor acidity (α), hydrogen-bond acceptor basicity (β), and Reichardt's polarity parameters (ETN) were measured from the ultraviolet-visible spectral shifts of 4-nitroaniline, 4-nitroanisole, and Reichardt's dye. The solvent properties of the IL-water mixtures were found to be influenced by IL type and IL mole fraction (xIL). All these studied systems showed the non-ideal behavior. The maximum deviation to ideality for the solvatochromic parameters can be obtained in the xIL range from 0.1 to 0.3. For most of the binary mixtures, the π* values showed the synergistic effects instead of the ETN, α and β values. The observed synergy extent was dependent on the studied systems, such as the dye indicator and IL type. A preferential solvation model was utilized to gather information on the molecular interactions in the mixtures. The dye indicator was preferentially solvated on the following trend: IL >IL-water complex >water.

     

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