TBP体系活度系数的测定和微扰理论的研究

DETERMINATION OF ACTIVITY COEFFICIENTS OF TBP-CONTANING SYSTEMS AND STUDY ON PERTURBATION THEORY

在前人工作的基础上,改进了液上空间气相色谱测活度系数的方法,实验测定了TBP.稀释剂和水形成的多个二元系、三元系和四元系的活度系数和密度.选用的稀释剂有n-C_6H_(14)、n-C_7H_(16)、n-C_8H_(18)、C_6H_6、cy-C_6H_(12)、CCl_4和CHCl_3.在Pierotti 理论的基础上,采用新的硬球作用表达式和径向分布函数,并计及分子间的排斥能、色散能、取向能和诱导能,建立了简单的活度系数模型,并用于TBP 和稀释剂体系的计算.从二元系回归得到的分子参数较好地预测了三元系的活度系数.

In this paper,the authors modify the technique for determining the activity coefficients by themethod of head-space gas chromatography and improve the accuracy of the measurement.Theactivity coefficients of volatile components and densities of the solutions are measured for diluent-diluent,TBP-diluent and TBP-diluent-diluent systems and those TBP-containing systems withsaturated water.The diluents used are n-C_6G_(14),n-C_7H_(16),n-C_8H_(18),C_6H_6,cy-C_6H_(12),CCl_4 andCHCl_3.A simple activity coefficient model is derived on the basis of Pierotti's theory with modifiedhard-sphere residual chemical potential and radial distribution function.Every kinds of forcesbetween molecules are considered.The model is used to calculate the activity coefficients of TBPand diluents systems,From the molecular parameters regressed from two-component systems,theactivity coefficients of three-component systems are calculated.