Determination of general and specific ionic interactions in solution
Determination of general and specific ionic interactions in solution
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溶液中一般和特定离子相互作用的测定
DOI：
10.1039/df9572400025
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发表时间：
1957
期刊：
影响因子：
--
通讯作者：
M. Eigen
中科院分区：
文献类型：
--
作者：
M. Eigen
从静态热力学数据中确定“一般”和“特殊”离子相互作用通常带有一定的随意性。用动力学方法记录系统的弛豫谱，可以分离出不同种类的离子相互作用。介绍了该方法在2∶2电解质水溶液中的一些应用。结果与最近的统计和热力学研究结果进行了比较。热力学在混凝土体系中的应用不依赖于对其微观结构的特殊假设。然而，对热力学数据的任何物理解释都需要系统的统计图像，并依赖于我们对分子相互作用力的知识，而分子相互作用力通常只能在可观察的量中简单地表达出来。对于电解质溶液，我们对结构和相互作用效应的认识大多是从热力学数据（如活度系数等）的分析中推断出来的。然而，电解质理论的现状只允许在有限的情况下明确区分不同的相互作用效应：
The determination of “general” and “specific” ionic interactions from static thermodynamic data involves in general a certain amount of arbitrariness. By using a dynamical method to record the relaxation spectrum of the system it is possible to separate the different kinds of ionic interaction. Some applications of the method to 2: 2-electrolytes in aqueous solution are described. The results are compared with those of recent statistical and thermodynamic studies.The application of thermodynamics to a concrete system is independent of special assumptions about its microscopic structure. Any physical interpretation of thermodynamic data, however, requires a statistical picture of the system and depends on our knowledge of the molecular interaction forces which generally express themselves only summarily in the observable quantities. With respect to electrolyte solutions most of our knowledge about the structure and interaction effects has been deduced from analyses of thermodynamic data such as activity coefficients, etc. However, the present state of electrolyte theory allows an unequivocal distinction between different interaction effects only in limiting cases: