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本文考察了解释在离子熔体中引入过量阳离子和阴离子的各种不同模型,并提出了一个描述熔体中当成分逐渐从纯金属状态变化到完全电离状态时,热力学性质变化的新模型。该模型以描述混合物位形熵的Temkin表达式为基础,中性物质和假想的带有诱发电荷的空位被引进了阴离子亚晶格中。诱发电荷的大小等于占据着阳离子亚晶格的物质的平均价。当电离趋势弱时,新模型近似于替位模型,如果缔合体的概念是它们含有一个原子的电负性元素的话,那么新模型形式上和缔合溶液模型相同。对于多元体系,新模型比缔合溶液模型含有较少的成分变量和参数。 本文的大部分内容曾在1984年8月20～24日在丹麦召开的欧洲熔盐化学会议上宣读。
This paper examines the different models that explain the incorporation of excess cations and anions into ionized melts and proposes a new model that describes the changes in the thermodynamic properties of the melt as it gradually changes from a purely metallic state to a fully ionized state. The model is based on the Temkin expression that describes the entropy of the mixture’s configuration, and the neutral species and the hypothetical vacancy with evoked charge are introduced into the anionic sublattice. The magnitude of the induced charge is equal to the average value of the species that occupy the cationic sublattice. The new model approximates the surrogate model when the ionization trend is weak, and the new model is formally the same as the associative solution model if the concept of associations is that they contain one atom of electronegative elements. For multivariate systems, the new model contains fewer constituent variables and parameters than the associated solution model. Much of this work was presented at the European Molten Salt Chemistry Conference, Denmark, August 20-24, 1984.