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 .
The close relationship between activity coefficient and internal pressure is noticed. The van Laar's theory is modified by substituting the internal pressure of van der waals fluid with Frank's relation. An excess Gibbs free energy equation which is very similar to Wohl's 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.
出处
《化工学报》
EI
CAS
CSCD
北大核心
2000年第2期181-186,共6页
CIESC Journal
基金
国家自然科学基金!资助项目 (No 2 93762 36
2 96760 1 1 )
关键词
Gibbs自由能
活度系数
溶解度
液体混合
模型
internal pressure, excess Gibbs free energy, activity coefficient, solubility parameter, excess enthalpy
