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叔铵类(R_3N)萃取剂萃取金属离子需在酸性介质中进行,与无机酸先形成铵盐(属阴离子表面活性剂类),然后与金属配阴离子进行阴离子交换反应。而将R_3N制成无机酸盐,作为表面活性剂以微乳液为模型对其进行热力学函数与结构研究尚未见报道。 本文制备了TOA·HCl、N235·HCl、N235·HNO_3与N235·HClO_44种叔铵无机酸盐,测定了叔铵盐的界面化学性质。以w/o型微乳液的球形颗粒结构为模型,用稀释法测定了叔铵盐(TOA·HCl,N235·HCl,N235·HNO_3,N235·HClO_4)-烷烃-醇-水四元均相透明体系的结构参数;并用不同醇时,醇由油相(o)转移至界面层(i)的标准自由能变(?)结果表明其结构“颗粒”半径小于0.5nm,表面活性剂叔铵盐的平均聚集数小于0.05,应属醇的反向胶团。 1 实验 1.1 试剂 三正辛胺(TOA,德国);N235(R_3N,R=C_5—C_(10),大连油脂化学厂)。叔铵盐TOA·HCl分别用干法(D)与湿法(W)制备。向TOA中通入干燥HCl气体至饱和,再加入分析量的TOA中和过量的HCl,制得TOA·HCl(D).TOA与过量10mol/L盐酸振荡平衡,再加入分析量的TOA中和过量酸制得TOA·HCl(W),样品均为淡黄色蜡状固体,N235·HCl、N235·HNO_3、N235·HClO_4均用湿法制备。其它试剂均为A.R.级,未进一步处理,水为二次蒸馏水。
The extraction of metal ions by tertiary ammonium (R_3N) extractant needs to be carried out in acidic medium, forming ammonium salt (an anionic surfactant) with inorganic acid, followed by anion exchange reaction with metal anions. The R_3N made of inorganic acid salt, as a surfactant to microemulsion as a model of its thermodynamic function and structure of the study has not been reported. In this paper, TOA · HCl, N235 · HCl, N235 · HNO3 and N235 · HClO44 kinds of tertiary ammonium inorganic acid salt were prepared, and the interfacial chemical properties of the tertiary ammonium salt were measured. The spherical particles structure of w / o microemulsion was taken as the model to determine the four components of tertiary ammonium salt (TOA · HCl, N235 · HCl, N235 · HNO3, N235 · HClO4) -alkane-alcohol- The standard free energy change (?) Of the alcohol transferred from the oil phase (o) to the interfacial layer (i) with different alcohols showed that the “particle” radius of the structure was less than 0.5 nm, and the surface area of the surfactant tertiary ammonium salt The average aggregation number is less than 0.05, should belong to alcohol reverse micelles. 1 Experiment 1.1 Reagents Tri-n-octylamine (TOA, Germany); N235 (R_3N, R = C_5-C_ (10), Dalian Oil Chemical Factory). The tertiary ammonium salt TOA.HCl was prepared by dry (D) and wet (W) respectively. TOA · HCl was added to the TOA to saturation, then TOA · HCl (D) was prepared by neutralizing the excess amount of HCl in the analytical volume, TOA · HCl was equilibrated with an excess of 10 mol / L hydrochloric acid, and the analytical volume was added to neutralize TOA Excess acid was used to make TOA · HCl (W). The samples were all yellowish waxy solid. Both N235 · HCl, N235 · HNO3 and N235 · HClO4 were prepared by wet method. Other reagents are A.R. grade, without further treatment, the water is double distilled water.