物理化学学报 >> 1993, Vol. 9 >> Issue (03): 351-356.doi: 10.3866/PKU.WHXB19930313

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电极/溶液界面内层形成熵的统计力学处理

苏文煅; 叶晖   

  1. 厦门大学化学系，厦门 361005
  • 收稿日期:1991-12-02 修回日期:1992-06-16 发布日期:1993-06-15
  • 通讯作者: 苏文煅

The Statistical Mechanics Treatment for the Inner-layer Entropy of Formation of Electrode/Solution Interface

Su Wen-Duan; Ye Hui   

  1. Department of Chemistry, Xiamen University, Xiamen 361005
  • Received:1991-12-02 Revised:1992-06-16 Published:1993-06-15
  • Contact: Su Wen-Duan

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摘要： 根据文[1a]提出的电极/溶液界面偶极取向分布模型, 导出金属/溶液界面内层形成熵ΔS~(m-d)(σ)以及溶剂化层构型熵S_k(σ)的统计力学计算式, 讨论了影响ΔS~(m-d)变化的主要因素, 并给出对汞/甲醇、汞/碳酸亚乙酯和汞/水溶液等三种界面的处理结果.

关键词: 界面形成熵, 汞/溶液界面

Abstract: The inner layer entropy of formation of metal/solution interface (△S~(m-d)) as a function of electrode charge (σ) is derived by using statistical mechanics based on the model of dipole orientation distribution presented in previous paper. the relating curves of △S~(m-d) with σ has been calculated for three different interface systems, namely, the Hg/methanol, Hg/ethylene carbonate and Hg/aqueous solution. According to the present results, the variation in △S~(m-d)(σ) of Hg/methnol interface seems to be chiefly depended on the structure of solvate layer and its dipole orientation distribution. But for the interface of the Hg/ethylene carbonate or the Hg/aqueous, the change of ΔS~(m-d) with σ would be regarded as due to the contribution of surface Hg atoms.

Key words: Interfacial entropy of formation, Mercury/solution interface