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.

实验研究了螯合萃取、离子缔合萃取和协同萃取中的界面反应：1)螯合萃取体系：利用光电二极管阵列分光光度计高速搅拌装置，研究了5-壬基水杨基醛肟（P50）对Ni（II）的提取率与界面浓度的关系。发现萃取速率的决定步骤是界面处1:1配合物的形成速率，并根据本征机理解释了萃取速率过程。另一方面，5-Br-PADAP体系对Ni（II）的萃取速率比P50体系慢得多，表明速率决定步骤是闭合环。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和膜过滤法以及高速搅拌法，研究了四苯基卟啉（TPP）在甲苯中对酸的萃取及其界面离子缔合吸附。在水溶性卟啉和离子表面活性剂paris体系中也发现了界面离子结合吸附。离子对的吸附受外加电场的影响。3)协同萃取：1,10-菲罗啉的加入增强了丁基双硫腙对Ni（II）的萃取作用。在萃取过程中，确定了一种界面配合物的存在。

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: "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: "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: "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）。