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化学学报
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化学学报 ›› 1996, Vol. 54 ›› Issue (2): 175-181. 上一篇    下一篇

研究论文

水溶液中盐酸-醇相互作用的热力学参数Ⅱ: 盐酸-丙三醇-水体系(278.15～318.15K)

卓克垒;王键吉;卢锦梭   

  1. 河南师范大学化学系
  • 发布日期:1996-02-15

Thermodynamic parameters of interaction of HCl with alcohols in waterⅡ: HCl-glycerol-water system at 278.15～318.15K

ZHUO KELEI;WANG JIANJI;LU JINSUO   

  • Published:1996-02-15

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534

被引次数

2

在278.15～318.15K(间隔10K)下, 测定了无液接电池Pt,H~2(g,p)│HCl(m~E)│AgCl-AgPt,H~2(g,p)│HCl(m~E),GL(m~N)│AgCl-Ag的电动势, 其中GL为丙三醇, m~E=0.005～0.1mol·kg^-^1,m~N=0.4～1.0mol·kg^-^1。实验数据用来计算HCl-GL-H~2O体系的盐效应常数k~s及HCl-GL在水中的相互作用的热力学参数f~E~N(g~E~N,s~E~N,h~E~N和C~p~,~E~N)。结果k~s＞0,g~E~N＞0, s~E~N＞0, C~p~,~E~N＜0。在353K时k~s有最小值0.0076kg·mol^-^1。f~H~C~l~-~G~L的数值比f~H~C~l~-~P~G(PG是1,2-丙二醇)小。应用结构相互作用模型和基团加合性原理分析讨论了这些参数的符号及其随温度变化的规律。

关键词: 盐酸, 电动势, 甘油, 盐效应, 热力学参数, 对相互作用, 基团加合性, 结构相互作用

The emfs of cells without-junction Pt,H~2(g,p)│HCl(m~E)│AgCl-Ag Pt,H~2(g,p)│HCl(m~E),GL(m~N)│AgCl-Ag have been measured at 10 degree intervals from 278.15 to 318.15K, where GL refers to glycerol, m~E=0.005～0.1mol·kg^-^1, m~N=0.4～1.0mol·kg^-^1. The emf data were used to calculate salting constant k~s for HCl-GL-H~2O system and thermodynamic parameters of interactions, f~EN (g~EN, h~EN, s~EN and C~p~,~E~N) between HCl and GL in water. It has been showed that k~s＞0, g~E~N＞0, h~E~N＞0, s~E~N＞0 and C~p~,~E~N＜0. The minimum in k~s is 0.0076kg·mol^-^1 at 353K. f~E~N values of HCl-GL are smaller than that of HCl-PG (1,2-propanediol). The signs of the pair parameters and the temperature dependence of them have been interpreted by the model of structural interaction and the group-additivity principle.

Key words: HYDROCHLORIC ACID, ELECTROMOTIVE FORCES, GLYCEROL, SALT EFFECT, THERMODYNOMICS PARAMETER

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