物理化学学报 >> 1985, Vol. 1 >> Issue (04): 365-369.doi: 10.3866/PKU.WHXB19850411

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四元体系HCl-MClm-M′Cln-H2O中盐酸的活度系数
Ⅱ. HCl-KCl-BaCl2-H2O体系

季明; 游效曾; 傅献彩   

  1. 南京大学化学系
  • 收稿日期:1985-01-30 修回日期:1985-04-24 发布日期:1985-08-15

ACTIVITY COEFFICIENT OF HCI IN QUATERNARY SYSTEM
Ⅱ. HCl-KCl-BaCl2-H2O

Ji Ming; You Xiaozeng; Fu Xiancai   

  1. Department of Chemistry, Nanjing University, Nanjing
  • Received:1985-01-30 Revised:1985-04-24 Published:1985-08-15

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摘要： 从可逆电池H_2|HCl(I_1), KCl(I_2), BaCl_2(I_3)|AgCl-Ag的电位测定求得了在25 ℃时四元体系HCl-KCl-BaCl_2-H_2O中盐酸的活度系数γ_1。结果表明, 在恒定的总离子强度I及I_3条件下, 盐酸的的活度系数的对数亦随I_2线性地变化,但其数值比Harned在三元体系中所得到的对应数值略大一些, 和简单的1-1价硷金属卤化物四元体系中行为略为不同, 可能应表示为:
logγ_1=logγ_(1(0))-a_(12)I_2-a_(13)I_3-K_(23)I_2I_3
其中K_(23)为电解质2和3的作用系数。对我们所研究的体系, K的数值较小。初步的实验结果表明, 我们所推广的计算混介电解质活度系数的Glueckauf公式可以近似地应用于实际体系。
应用热力学的交叉方程式于四元体系可以导出和前人在三元体系中所得到的一些相同的公式, 从这些式子有可能从实验的a_(12)、a_(13)数值求出a_(21)、a_(31)等数值。

Abstract: Activity coefficient ν_1 of HCl in quaternary system of HCl-KCl-BaCl_2-H_2O was investigated by means of a reversible cell.
H_2|HCl(I_1), KCl(I_2), BaCl_2(I_3)|AgCl-Ag
It has been shown by the experiments that logγ_1 varied linearly with I_2 at the constant total ionic strength I and I_3, but its value is only a little different from that of logγ_1 calculated from the data by Harned for the corresponding ternary system. The logγ_1 of HCl in quaternary system may be expressed by
logγ_1=logγ_(1(0))-α_(12)I_2...