Ionic liquids comprising bis(fluorosulfonyl)imide (FSI) anion have been recognized to be well suited for technological applications as solvent and electrolyte media. In this work, we thoroughly investigated the thermodynamic and transport behavior of binary aqueous systems of two hydrophobic FSI-based ionic liquids, namely [EMIM][FSI] and [BMPYR][FSI]. Systematic measurements of phase equilibria, density, viscosity, and electric conductivity were conducted, our aim being to provide truly reliable information that would substantially upgrade that existing in the literature. Employing DSC measurements on the neat ILs and dynamic measurements of freezing or cloud point temperatures as well as static solubility measurements for aqueous ILs, phase diagrams for both these systems over a 100 K window were established. Rather large solubilities of water in these ILs allow for measurements of various other properties in the homogeneous IL-rich region. Extensive data thus obtained on water activity in this region were correlated for each system simultaneously with the mutual liquid-liquid solubilities, using an extended SSF (Sum of Symmetrical Functions) equation. This global excess Gibbs energy model not only accurately captures all the VLE, LLE, and SLE data we determined experimentally, but also discloses an enthalpy-driven system energetics with hydrophobic hydration effects that are more pronounced in the case of [BMPYR][FSI]. The measurements of density, viscosity, and conductivity covering the systems from the neat ILs to those almost saturated with water gave positive excess volumes and negative viscosity deviations that rise and diminish, respectively, as T increases. The conductivity increases monotonously with increasing water content and temperature. Accurate functional representations were also established for the volumetric, viscosity, and conductivity data, capturing simultaneously their composition and temperature dependence. The linkage between conductivity and viscosity was further analyzed by means of the fractional Walden rule which provided excellent fits for both isopleths and isotherms and indicated comparatively weaker coupling for the [BMPYR][FSI] system and the direction of the isothermal composition changes. Finally, comparing the FSI ILs with their TFSI analogs, the former were found to be clearly less hydrophobic.

包含双（氟磺酰基）酰亚胺 (FSI) 阴离子的离子液体已被认为非常适合作为溶剂和电解质介质的技术应用。在这项工作中，我们彻底研究了两种基于疏水性 FSI 的离子液体（即 [EMIM][FSI] 和 [BMPYR][FSI]）的二元水性体系的热力学和传输行为。进行了相平衡、密度、粘度和电导率的系统测量，我们的目标是提供真正可靠的信息，大大提升文献中现有的信息。采用纯离子液体的 DSC 测量和凝固点或浊点温度的动态测量以及水性离子液体的静态溶解度测量，建立了这两个系统在 100 K 窗口上的相图。这些 IL 中相当大的水溶解度允许测量同质富含 IL 区域的各种其他特性。使用扩展的 SSF（对称函数总和）方程，由此获得的关于该区域水活度的大量数据与每个系统同时与相互的液-液溶解度相关联。这种全局过量吉布斯能量模型不仅准确地捕获了我们通过实验确定的所有 VLE、LLE 和 SLE 数据，而且还揭示了一种具有疏水水合效应的焓驱动系统能量学，在 [BMPYR] [FSI] 的情况下更为明显. 密度、粘度和电导率的测量覆盖了从纯 IL 到几乎被水饱和的系统，分别给出了正的过量体积和负的粘度偏差，分别上升和下降，T增加。电导率随着含水量和温度的增加而单调增加。还为体积、粘度和电导率数据建立了准确的函数表示，同时捕获了它们的组成和温度依赖性。通过分数瓦尔登规则进一步分析了电导率和粘度之间的联系，该规则为等温线和等温线提供了极好的拟合，并表明 [BMPYR][FSI] 系统和等温成分变化方向的耦合相对较弱。最后，将 FSI ILs 与其 TFSI 类似物进行比较，发现前者疏水性明显较低。