高等学校化学学报 ›› 1983, Vol. 4 ›› Issue (2): 218.

• 论文 • 上一篇    下一篇

萃取体系的热力学研究(Ⅰ)——磷-32标记TBP分配法测定TBP-惰性溶剂二元体系的活度系数

高宏成, 彭启秀, 彭立娥, 王文清, 徐光宪   

  1. 北京大学
  • 收稿日期:1981-08-25 出版日期:1983-04-24 发布日期:1983-04-24

THERMODYNAMIC INVESTIGATION OF THE EXTRACTION SYSTEM(Ⅰ) ——DETERMINATION OF THE ACTIVITY COEFFICIENTS OF BINARY SYSTEMS OF TBP-DILUENT BY ~(32)P-LABELED TBP DISTRIBUTION METHOD

Gao Hongcheng, Peng Qixiu, Peng Lie, Wang Wenqing, Hsu Kwang-hsien   

  1. Peking University Beijing
  • Received:1981-08-25 Online:1983-04-24 Published:1983-04-24

摘要: 本文提出用磷-32标记TBP分配法,测定TBP-惰性溶剂(苯、正己烷、四氮化碳、三氯甲烷等)二元体系的活度系数。此法比常用的蒸气压法、溶解度法等操作简便、快速准确和测量浓度范围大、应用体系广。实验测得四种不同溶剂体系中各种浓度TBP的活度系数,并根据实验的结果对溶剂的影响进行了讨论。

Abstract: The activity coefficients of TBPin various diluents have been determined by 32P-labeled TBP distribution method. 33P-labeled TBPhas been preparedby Higgin's method.It was dissolved in various diluents-benzene,hexane,carbon tetrachloride, chloroform and odourless kerosene. The composition of TBPsolutions could be varied with a wide range from 1 to 98 volume%. This method is simpler, more rapid and the range of cnocentration studied is broader than other physico-chemical methods.The radioactivities of aqueous phase equilibrated with 32P-labeled TBPand its solutions were first measured, then the ratios A2 of the radioactivities were calculated therefrom. The thermodynamic equilibrium constant λ0 is equal to the ratio of the activities of TBPbetween the two phases.As the solubility of TBPin water is low, the activity coefficient of TBPin water can be assumed to be equal to unity. Pure TBPis used as the standard state of solute for the determination of f2 which is the activity coefficient of the solute TBP. Let The effect of different solvents on the activity coefficients thus measured has been discussed from the point of view of intermolecular interactions. As an alternate approach we choos ean infinitely dilute solution of TBPas the reference state so that the activity coefficients at infinitely dilute solution were taken to be unity. The standard state of the solute TBPwas obtained by extrapolating the Henry's law line to N2→ and it is a hypothetical state.

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