Kinetic studies on the interfacial reaction in solvent extraction

溶剂萃取中界面反应的动力学研究

• 批准号: 05453066
• 负责人: WATARAI Hitoshi
• 金额: $ 3.65万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453066/
• 关键词: Solvent extraction; Extraction rate; Liquid-liquid interface; Interfacial complexation; Interfacial ion-association; Porphyrins; Pyridyl-azo compounds; High-speed stirring method; 溶液界面; プロトン付加反応; 外部電場効果

Interfacial reactions in chelate extraction, ion-association extarction and synergistic extraction were investigated experimentally :1) Chelate extraction system : The relationship between the extraction rate of Ni(II) with 5-nonylsalicyl aldoxime(P50) and the interfacial concentration of P50 was studied by means of the high-speed stirring apparatus instuled with a photodiode-array spectrophotometer. The rate determining step in the extraction was found to be the formation rate of the 1 : 1 complex at the interface and the rate process was interpreted in terms of the Eigen mechanism. On the other hand, the extraction rate of Ni(II) with 5-Br-PADAP was shown to be much slower than the P50 system, suggesting the rate determining step to be the ring-closure.2) Ion-association extraction system : The extraction of acid with tetraphenylporphyrin(TPP)in toluene and the interfacial ion-association adsorption were studied by means of an optical stirr cell method, a Teflon capillary method and a membrane filter method as well as the high-speed stirring method. Interfacial ion-association adsorption was found also in the systems of water-soluble porphyrin and ionic surfactant paris. The adsorption of ion-pair was affected by an external electric field.3) Synergistic extraction : The extraction of Ni(II) with buthyldithizone was enhanced by the addition of 1,10-phenanthroline. In the course of the extraction, the existance of an interfacial complex was concluded.

实验研究了螯合物萃取、离子缔合萃取和协同萃取中的界面反应：1)螯合物萃取体系：研究了Ni(II)与5-壬基水杨醛肟(P50)的萃取率与P50界面浓度之间的关系。通过装有光电二极管阵列分光光度计的高速搅拌装置。发现萃取中的速率决定步骤是界面处 1:1 复合物的形成速率，并且根据本征机制解释速率过程。另一方面，5-Br-PADAP 对 Ni(II) 的萃取速率比 P50 系统慢得多，表明速率决定步骤是闭环。2) 离子缔合萃取系统：采用光学搅拌池法、聚四氟乙烯毛细管法、膜过滤法等研究了甲苯中四苯基卟啉(TPP)萃取酸及界面离子缔合吸附。高速搅拌法。在水溶性卟啉和离子表面活性剂巴黎体系中也发现了界面离子缔合吸附。离子对的吸附受外部电场的影响。3) 协同萃取：加入1,10-菲咯啉可增强丁基二硫腙对Ni(II)的萃取效果。在萃取过程中，得出了界面复合物存在的结论。

项目成果

H.Watarai: "Simple devices for the measurements of absorption spectra at liguid/liguid interfaces" Anal.Sci.10. 105-107 (1994)

H.Watarai：“用于测量液体/液体界面吸收光谱的简单装置”Anal.Sci.10。

H.Watarai: "Simple devices for the measurements of absorption spectra at liquid-liquid interfaces" Anal.Sci.10. 105-107 (1994)

H.Watarai：“用于测量液-液界面吸收光谱的简单装置”Anal.Sci.10。

H.Watarai: "Total internal reflection fluorescence measurements of ion-association adsorption of water-soluble porphyrins at liquid/liquid interface" Chem.Lett.(in press).

H.Watarai：“液/液界面水溶性卟啉离子缔合吸附的全内反射荧光测量”Chem.Lett.（正在出版）。

H.Watarai: "What's happening at the liquid/liquid interface in solvent extraction ?" Trend in Anal.Chem.12. 313-318 (1993)

H.Watarai：“溶剂萃取中液/液界面发生了什么？”

H.Watarai: "Total internal reflection fluorescence measurements of ion-association adsorption of water-soluble porphyrins at L-L interface" Chem.Lett.(in press).

H.Watarai：“水溶性卟啉在 L-L 界面离子缔合吸附的全内反射荧光测量”Chem.Lett.（正在出版）。