CIESC Journal

• 化工学报 • 上一篇    下一篇

液体混合的通用Gibbs自由能模型

俞春芳,刘国杰   

  1. 华东理工大学化学系!上海200237,华东理工大学化学系!上海200237
  • 出版日期:2000-04-25 发布日期:2000-04-25

GENERALIZED GIBBS FREE ENERGY MODEL FOR MIXING OF LIQUIDS

Yu Chunfang and Liu Guojie(Department of Chemistry, East China University of Science and Tehnology, Shanghai 200237)   

  • Online:2000-04-25 Published:2000-04-25

摘要: 鉴于活度系数与内压密切相关 ,修正了熟知的vanLaar理论 ,用Frank关系式替代了原理论推导中的vanderWaals流体内压 ,从而导得一个十分类似于Wohl方程的过量函数式 ,vanLaar方程、溶解度参数方程、Margules方程和Scatchard -Hamer方程等都是它的特例 .通过对过量熵贡献的修正 ,建立了一个活度系数方程 .它已被证明具有通用性 ,即不仅适用于各种小分子液体混合物 ,而且亦适用于各种高分子溶液 ,有比局部组成型方程更广的适用范围 .此外 ,由该Gibbs自由能模型还得到了溶解度参数一个新的定义 ,它比Hildebrand定义的溶解度参数更加广义 .

Abstract: The close relationship between activity coefficient and internal pressure is noticed. The van Laars theory is modified by substituting the internal pressure of van der waals fluid with Franks relation. An excess Gibbs free energy equation which is very similar to Wohls equation is derived and the famous van Laar equation, solubility parameter equation, Margules equation and Scatchard-Hamer equation etc. are all its special examples. The corresponding activity coefficient equation is established by further taking account of the contribution of excess entropy. It was proved that this equation is general, namely it is applicable not only to various small molecular liquid mixtures, but also to various polymer solutions, and has more extensive applicability than local-composition activity coefficient equations. In addition, a new definition of solubility parameter, which is more generalized than that proposed by Hildebrand, is obtained from this Gibbs free energy model.

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