具有不同電離趨勢的熔體的雙亞晶格模型
doi: 10.13374/j.issn1001-053x.1985.02.007
A TWO-SUBLATTICE MODEL FOR MOLTEN SOLUTIONS WITH DIFFERENT TENDENCY FOR IONIZATION
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摘要: 本文考察了解釋在離子熔體中引入過量陽離子和陰離子的各種不同模型,并提出了一個描述熔體中當成分逐漸從純金屬狀態變化到完全電離狀態時,熱力學性質變化的新模型。該模型以描述混合物位形熵的Temkin表達式為基礎,中性物質和假想的帶有誘發電荷的空位被引進了陰離子亞晶格中。誘發電荷的大小等于占據著陽離子亞晶格的物質的平均價。當電離趨勢弱時,新模型近似于替位模型,如果締合體的概念是它們含有一個原子的電負性元素的話,那么新模型形式上和締合溶液模型相同。對于多元體系,新模型比締合溶液模型含有較少的成分變量和參數。
本文的大部分內容曾在1984年8月20~24日在丹麥召開的歐洲熔鹽化學會議上宣讀。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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