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)  

Thermodynamic Parameters of Interaction of HCI with Alcohols in Water II. HCl -Glycerol- Water System at 278. 15-318. 15K

作　　者：卓克垒[1] 王键吉[1] 卢锦梭[1] 

机构地区：[1]河南师范大学化学系,新乡453002

出　　处：《化学学报》1996年第2期175-181,共7页Acta Chimica Sinica

基　　金：国家自然科学基金资助的课题

摘　　要：在278.15～318.15K间隔10K)下,测定了无液接电池Pt,H_2(g,P~θ│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_(EN)(g_(EN),S_(EN),h_(EN)和c_(p.EN)).结果表明k_s>0,g_(EN)>0,S_(EN)>0,C_(p.EN)<0.在353K时k_s有最小值0.0076kg·mol^(-1).f_(HCl～GL)的数值比f_(HCl～PG)(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.The emfs of cells without - junctionPt, H2 (g, p ) | HCl (mE) |AgCl-Ag Pt, H2 (g, p ) |HC1 (mE), GL (mN) |AgCl-Aghave been measured at 10 degree intervals from 278.15 to 318.15K, where GL refers toglycerol, mE = 0.005-0.1mol· kg-1, mN = 0.4~1.0mol·kg-1. The emf data were used to calculate salting constant ks for HC1 - GL - H2O system and thermodynamic parameters of interactions, fEN (gEN, hEN, SEN and cp, EN) between HCl and GL in water. It has been shown that ks>0, gEN>0, hEN>0. sEN>0 and CP,EN<0. The minimum in k, is 0.0076 kg mol-1 at 353K. fEN values of HC1 - GL are smaller than that of HC1 - 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.

关 键 词：盐效应 热力学参数 基团加合性 盐酸 丙三醇 

分 类 号：O645.164[理学—物理化学]