物理化学学报 >> 1990, Vol. 6 >> Issue (05): 549-555.doi: 10.3866/PKU.WHXB19900508

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极性有机化合物在电解质水溶液中盐效应的研究(II)应用Pitzer方程关联二(2-乙基已基)磷酸在碱金属氯化物水溶液中的活度系数

陆九芳; 牛淑芳; 李以圭   

  1. 清华大学化工系
  • 收稿日期:1989-07-10 修回日期:1990-02-16 发布日期:1990-10-15
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Salting Effect of Polar Organic Compound in Electrolyte Solutions(II) An Application of Pitzer Equations in D2EGPA-Alkali Chloride-H2O Systems

Lu Jiu-Fang; Niu Shu-Fang; Li Yi-Gui   

  1. Department of Chemistry Engineering, Tsinghua University, Beijing
  • Received:1989-07-10 Revised:1990-02-16 Published:1990-10-15
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摘要： 本文将用放射性磷32标记法测得的二(2-乙基己基)磷酸在碱金属氯化物水溶液(LiCl、NaCl、KCl、RbCl、CsCl和NH_4Cl)中的溶解度数据~[1], 分别用Pitzer(1973年)方程和Pitzer-Li(1983年)方程进行活度系数的关联. 计算结果表明, 由于Pitzer-Li方程考虑了溶质-溶剂间的短程作用能, 所得参数更能反映盐效应的本质, 故优于Pitzer方程. 同时还表明, 上述体系中离子-水之间的作用能远大于离子-有机化合物之间的作用能。

Abstract: In this paper, the Pitzer equation (1973) and Pitzer-Li equation (1983) are used to correlate the activity coefficient data of di (2-ethyl-hexyl) phosphoric acid (D_2EHPA) in aqueous alkali chlorides (LiCl, NaCl, KCl, RbCl, CsCl and NH_4 Cl), which were determined by P~(32) radioisotope tracer technique. The calculated results show that the Pitzer-Li equation is better than the Pitzer equation, since the ion-solvent short range interaction energy and the ion-ion long range interaction energy are considered in the Pitzer-Li equation. The parameters thus regressed can reflect the sequence of the salting effect for alkali cation series and can explain the salting-out phenomenon for D_2EHPA. It also shows that the ion-water interaction energies are much greater than the ion-D_2EHPA interaction energies in th D_2EHPA-MCl-HCl-H_2O systems.