THERMODYNAMICS OF ELECTROLYTES .5. EFFECTS OF HIGHER-ORDER ELECTROSTATIC TERMS
THERMODYNAMICS OF ELECTROLYTES .5. EFFECTS OF HIGHER-ORDER ELECTROSTATIC TERMS
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DOI：
10.1007/bf00646562
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发表时间：
1975-01-01
影响因子：
1.2
通讯作者：
PITZER, KS
中科院分区：
文献类型：
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作者：
PITZER, KS
本文研究了高阶静电项（超出Debye-Hückel近似）对混合电解质和纯电解质热力学性质的贡献。结果发现，这些影响是重要的情况下，不对称混合，特别是当一个离子有三个单位或更多的电荷。由于同号离子的相互排斥使它们相距足够远，短程力的影响很小，因此可以通过纯静电函数进行适当的校正。这个函数的评估，并给出了几个方便的近似。应用于混合1-2和1-3型离子的系统。高阶限制法律存在对称的混合物和纯，不对称的溶质，但这些影响并没有被发现是显着的关系，现有的活动或摩擦系数的数据。
The contribution of higher-order electrostatic terms (beyond the Debye-Hückel approximation) to the thermodynamic properties of mixed and pure electrolytes is investigated. It is found that these effects are important for cases of unsymmetrical mixing, especially when one ion has a charge of three units or more. The appropriate correction can be made by a purely electrostatic function since the mutual repulsion of ions of the same sign keeps them far enough apart that short-range forces have little effect. This function is evaluated, and several convenient approximations are also given. Application is made to systems mixing ions of the type 1–2 and 1–3. Higher-order limiting laws exist for symmetrical mixtures and for pure, unsymmetrical solutes, but these effects were not found to be significant in relationship to existing activity or osmotic-coefficient data.