物理化学学报 >> 1993, Vol. 9 >> Issue (06): 776-787.doi: 10.3866/PKU.WHXB19930611

研究论文 上一篇    下一篇

TBP体系活度系数的测定和微扰理论的研究

丛威; 陆九芳; 李以圭   

  1. 清华大学化学工程系,北京 100084
  • 收稿日期:1992-04-13 修回日期:1992-10-04 发布日期:1993-12-15
  • 通讯作者: 丛威

Determination of Activity Coefficients of TBP-Contaning Systems and Study on Perturbation Theory

Cong Wei; Lu Jiu-Fang; Li Yi-Gui   

  1. Department of Chemical Engineering, Tsinghua Universtiy, Beijing 100084
  • Received:1992-04-13 Revised:1992-10-04 Published:1993-12-15
  • Contact: Cong Wei

摘要: 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.

关键词: TBP, 稀释剂, 水, 活度系数, 微扰理论

Abstract: In this paper, the authors modify the technique for determining the activity coefficients by the method of head-space gas chromatography and improve the accuracy of the measurement. The activity 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 with saturated 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 and CHCl_3.
A simple activity coefficient model is derived on the basis of Pierott's theory with modified hard-sphere residual chemical potential and radial distribution function. Every kinds of forces between molecules are considered. The model is used to calculate the activity coefficients of TBP and diluents systems, From the molecular parameters regressed from two-component systems, the activity coefficients of three-component systems are calculated.

Key words: TBP, Diluent, Water, Activity coefficient, Perturbation theory