物理化学学报 >> 1987, Vol. 3 >> Issue (02): 170-177.doi: 10.3866/PKU.WHXB19870211

研究论文 上一篇    下一篇

混合溶剂中多组分电解质溶液热力学性质的研究
Ⅱ. HCl+NaCl+2-propanol+H2O体系15~45 ℃

吕殿祯; 门殿元; 杨家振; 梁春余; 吕仁刚; 潘玄   

  1. 辽宁大学化学系
  • 收稿日期:1985-11-08 修回日期:1986-05-13 发布日期:1987-04-15
  • 通讯作者: 吕殿祯

STUDY ON THERMODYNAMIC PROPERTIES OF MIXED ELECTROLYTES IN MIXED SOLVENTS
Ⅱ. System of HCl+NaCl+2-propanol+H20 from 15 to 45 ℃

Lu Dianzhen; Men Dianyuan; Yiang Jiazhen; Liang Chunyu; Lu Rengang; Pan Xuan   

  1. Department of Chemist; Liaoning University; Shenyang
  • Received:1985-11-08 Revised:1986-05-13 Published:1987-04-15
  • Contact: Lu Dianzhen

摘要: 本文在恒定异丙醇摩尔分数x=0.05的条件下, 应用电动势法测定无液体接界电池(A)和电池(B)的电动势:
Pt, H_2(latm)|HCl(m), 2-propanol(x), H_2O(1-x)|Agcl-Ag (A)

Pt, H_2(latm)|HCl(m_A), NaCl(m_B), 2-propanol(x), H_2O(1-x)|AgCl-Ag (B)
根据电池(A)电动势确定混合溶剂中的Ag-AgCl电极的标准电极电势, 讨论了HCl的迁移性质; 利用电池(B)电动势确定HCl在该体系中的活度系数γ_A, 在恒定总离子强度下, HCl的活度系数遵守Harned规则。在溶液组成恒定时, logγ_A是温度倒数1/T的线性函数, 讨论了混合物中HCl的相对偏摩尔焓, 计算了HCl的一级、二级和总介质效应。

Abstract: This paper reports our study on thermodynamic properties of HCl+NaCl+ 2-propanol+H_2O system by means of emf measurements of the cells without liquid junction,
Pt, H_2(1atm)|HCl(m), 2-propanol(x), H_2O(1-x)|AgCl-Ag (A)
Pt, H_2(1atm)|HCl(m_A), NaCl(m_B), 2-propanol(x), H_2O(1-x)|AgCl-Ag (B)
at constant total ionic strenths I=0.5, 1.0, 2.0 and 3.0 mol kg~(-1), from 5 to 45 ℃, where m_A and m_B are the molalities of HCl and NaCl, respectively, x is the mo- lar fraction of 2-propanol in the mixed solvent, which is 0.05 during all measurements.
The standard electrode potential of Ag-AgCl in mixed solvent have been determined from equation (1) and using emf data of the cell (A) in table 1. The transfer properties of HCl have been calculated and listed in table 2. Using emf of cell (B), the activity coefficients of HCl, γ_A, in the system have determined according to equation (16).
The results show that HCl obeyes Harned Rule up to I=3.0 mol kg~(-1) over a range 15—45 ℃ (Fig.1). Under the condition of constant components of mixture, the logarithm of HCl activity coefficients, logγ_A are a linear function for reciprocal of temperatures equation (17). The primary, secondary and total medium effect of HCl have been calculated and discused (see table 5).