Abstract We present a novel approach for the calculation of the Krichevskii parameter A K r of solutes in dilute mixtures according to a universal thermodynamic expression that links the solute-solvent intermolecular asymmetry, as described by the Henry's law constant of the solute species in a pure solvent, to the desired A K r . The derived expression obeys two key thermodynamic constraints, i.e., corresponding to the behavior of either an ideal gas solute or a solute behaving as a solvent species representing a special case of Lewis-Randall ideal solution. Then, we provide a comparison between the thermodynamically consistent A K r values generated by this approach and those reported in the literature, from diverse experimental sources, and for a variety of aqueous solutes. Finally, we discuss how the A K r = 0 line divides the P − T plane of the pure solvent into two regions characterized by unambiguous solute-solvent intermolecular asymmetries, and provide additional microscopic as well as macroscopic interpretations for A K r .

中文翻译：

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关于稀溶液中溶质的 Krichevskii 参数，其大小、溶质-溶剂分子间不对称性以及溶液热力学的精确描述之间存在形式联系

摘要 我们提出了一种计算稀混合物中溶质的 Krichevskii 参数 AK r 的新方法，该方法根据通用热力学表达式将溶质 - 溶剂分子间不对称性联系起来，如纯溶剂中溶质物质的亨利定律常数所述。 , 到所需的 AK r 。导出的表达式服从两个关键的热力学约束，即，对应于理想气体溶质的行为或表现为代表路易斯-兰德尔理想溶液特例的溶剂种类的溶质的行为。然后，我们提供了由这种方法产生的热力学一致 AK r 值与文献中报道的值之间的比较，这些值来自不同的实验来源，并且适用于各种水性溶质。最后，