摘要
在恒定溶液总离子强度I=1.00mol·kg^(-1), 改变异丙醇在混合溶剂中的摩尔分数x=0.025、0.075和0.100条件下,测定了无液接界电池(A)和电池(B)的电动势。 Pt,H_2(1.013×10~5Pa)|HCl(m),i-PrOH(x),H_2O(1-x)|AgCl-Ag (A) Pt,H_2(1.013×10~5Pa)|HCl(m_A),NaCl(m_B),i-PrOH(x),H_2O(1-x)|AgCl-Ag(B) 根据电池(A)的电动势,确定混合溶剂中Ag-AgCl电极的标准电极电势,讨论了HCl的迁移性质。利用电池(B)的电动势,确定HCl活度系数γ_A。结果表明,在恒定I为1.00mol·kg^(-1)时,HCl的活度系数仍然服从Harned规则。在恒定溶液组成时,lgγ_A对热力学温度的倒数1/T作图,具有良好直线关系。进一步讨论了混合物中HCl的相对偏摩尔焓和HCl的溶剂化数及介质效应。
The termodynamic properties of HCl--NaCl--i-PrOH--H_2O system was studied by
means of emf measurements of the cells without liquid junction.
Pt, H_2(1.013×10~5Pa)|HCl(m), i-PrOH(x), H_2O(1-x)|AgCl-Ag (A)
Pt, H_2(1.013×10~5Pa)|HCl(m_A), NaCl(m_B), i-PrOH(x), H_2O (1-x)|AgCl-Ag (B)
at the molar fraction of i-PrOH x=0. 025, 0. 075 and 0. 100 in the mixed solvent, from 5
to 45℃ for cell (B) at constant total ionic strength I=1.00 mol. kg^(-1). The standard
electrode potential of Ag-AgCl in the mixed solvent have been determined from cell
(A). The activity coefficients of HCl, γ_A in the system have been determined from cell
(B). The results show that HCl still obeyes Harned Rule, logarithm of HCl activity
coefficient, lg γ_A is a linear function for reciprocal of the absolute temperatures at
constant components of mixture. Relative molar enthalpies of HCl, L_A are linear
function to the ionic strength fraction of NaCl at constant total ionic strength and
temperature. Finally, the primary, secondary and total medium effect of HCl have been
calculated and discussed.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1989年第1期6-13,共8页
Acta Chimica Sinica
基金
中国科学院科学基金
