混合溶剂中多组分电解质溶液热力学性质的研究I: 5-45℃下氯化氢-氯化钠-1,2-丙二醇-水体系

在恒定1,2-丙二醇摩尔分数X为0.05的混合溶剂中,在5-45℃温度范围内测定无液接电池Pt,H2(1 atm)HCl(ma),1,2-C3H5(OH)2(X),H2O(1-X)|AgCl-Ag(A)和Pt,H2(1 atm)|HCl(ma),NaCl(mb),1,2-C3H5(OH)2(X),H2O(1-X)|AgCl-Ag (B)的电动势.利用电池A的电动势确定混合溶剂中Ag-AgCl电极的标准电极电势,利用电池B的电动势确定了HCl在混合溶剂的多组分电解质溶液中的活度系数γA.指出了在恒定总离子强度下HCl仍然服从Harned规则,在溶液组成恒定时,logγA是温度T的线性函数.HCl的相对偏摩尔焓遵守类似的Harned规则,计算了HCl的一级、二级和总介质效应.

Thermodynamic properties of multicomponent electrolyte solutions in mixed solvents I: The system HCl - NaCl - 1,2-C3H5(OH)2 - H2O at 5-45`C

Emf. measurements for the cells (A) Pt, H2(1 atm)|HCl(mA), 1,2-C3H5(OH)2(X), H2O(1-X)|AgCl-Ag and (B) Pt, H2(1 atm)|HCl(mA), NaCl(mB), 1,2-C3H5(OH)2(X), H2O(1-X)|AgCl-Ag were made at 5-45?for ionic strengths 0.1-3.0 and X = 0.05. The standard potential of the AgCl-Ag electrode in the mixed solvents is obtained from the cell (A). Activity coefficients gA of HCl in the HCl-NaCl-1,2-C3H5(oH)2-H2O system were obtained from the cell (B). The results show that HCl obeys the Harned rule and that log gA is a linear function of temperature The primary, secondary, and total medium effects were calculated The results indicate that related partial molar enthalpies of HCl obey a similar Harned rule.