具有不同电离趋势的熔体的双亚晶格模型

A TWO-SUBLATTICE MODEL FOR MOLTEN SOLUTIONS WITH DIFFERENT TENDENCY FOR IONIZATION

  • 摘要: 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。

     

    Abstract: Different models accounting for the introduction of an excess of cations or anions in an ionic melt are considered.A new model whchi describes the variation in the thermodynamic properties in a melt as itgrabually changes its composition from purely metallic state to complete ionization is developed.The model is based upon Temkin's expression for the configurational entropy of mixing.Neutral species and hypothetic cal vacancies with an induced charge are introduced on the anion subla-ttice.The induced charge is equal to the average valency of the species occupying the cation sublattice.When the tendency of ionization is weak the model approaches the substitutional model.For binary systems the new model is formally identical to the associate solution model if the associates are defind in such a way that they contain one atom of the electronegative element.For higher-order systems the new model works with a lower number of composition variables and parameters than the associate solution model.

     

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