Thermodynamic Properties of Electrolyte Solutions

研究了混合电解液的热力学性质。本文提出的等活性溶剂理论是建立在半格兰特正则系综基础上的，其中溶剂活度是自变量，热力学过剩函数用摩尔比表示。初步评价表明，该理论预测的汽液平衡与含有混合溶质和/或混合溶剂的三元体系的实验结果吻合较好。该理论正在广泛的条件下对各种类型的系统进行测试，并与已建立的理论和关联进行比较。对含有非挥发性电解质的水溶液进行了从25℃到100℃的等压实验。在这些测量中，对单一和混合溶质同时测定溶剂的活度。因此，可以直接将理论与实验进行比较，而不需要在实验点之间进行插补。

The thermodynamic properties of electrolyte mixtures are studied. The isoactive-solvent theory developed in this work is based upon a semi-grant canonical ensemble, for which the solvent activity is the independent variable and the thermodynamic excess functions are expressed in mole ratios. Preliminary evaluations indicate that vapor-liquid equilibria predicted by the theory are in excellent agreement with experiments on ternary systems containing mixed solutes and/or mixed solvents. The theory is being tested for various classes of systems under a wide range of conditions and compared with established theories and correlations. Isopiestic experiments from 25 to 100 C are performed for aqueous solutions containing non-volatile electrolytes. In these measurements, the activity of the solvent is determined simultaneously for single and mixed solutes. Therefore, the theory can be compared directly with experiment without interpolating between experimental points.