Direct Photometric Measurement of Interfacial Reaction in Solvent Extraction Systems

溶剂萃取系统中界面反应的直接光度测量

• 批准号: 02640433
• 负责人: WATARAI Hitoshi
• 金额: $ 1.34万
• 依托单位: Akita University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640433/
• 关键词: Solvent extraction; Interfacial reaction; Chelate extraction kinetics; Synergistic extraction kinetics; Microemulsion; Porphyrins; Interfacial potential; Liquid membrane

The interfacial reaction in solvent extraction systems was investigated by means of the high-speed stirring method and direct photometric measurement of the interface. The followings were elucidated in the present study ;1. The rate-controlling step of the extraction of CU (II) and NI (II) with 2'-hydroxy-5'-nonylbenzophenone oxime was the formation of 1 : 1 complex between the anion of the extractant and the metal ions which occurred at interface. The solvent effect of heptane and chloroform was also discussed.2. The synergistic extraction rate of NI (II) with dithizone and 1, 10-phenanthroline (phen) was measured by using a photodiode-array detector. Under the conditions of higher concentration for phen than that for dithizone, an intermediate complex was formed at the interface.3. The direct measurements of interfacial spectra were made for the next three systems ;(1) The dissociation constants of beta-diketones were determined in anionic, cationic and nonionic o/w microemulsions. The medium effect for the dissociation constants was explained in terms of the electrostatic effect of the surface charge on the adsorption of beta-diketonates.(2) The optical cell for the measurement of absorption spectra of the dispersed systems by stirring was made and the interfacial protonation of tetraphenylporphine (TPP) at toluene/ sulfuric acid system was investigated. Experimental results showed the formation of diprotonated TPP and its aggregate at the interface.(3) Interfacial spectra of liquid membrane was observed by using Teflon filter or Teflon sheet as the supporting material. The interfacial protonations of TPP and a Rhodamine B derivative were measured by this method. This approach is now applied for the measurements of an interfacial kinetics and an electric field effect on interfacial reaction.

采用高速搅拌法和界面直接光度法研究了溶剂萃取体系中的界面反应。1.2‘-羟基-5’-壬基二苯甲酮肟萃取铜(II)和镍(II)的速率控制步骤是萃取剂的阴离子与界面金属离子形成1：1络合物。并讨论了正庚烷和氯仿的溶剂效应。用光电二极管阵列检测器测定了双硫腙与邻菲咯啉(Phen)对镍(II)的协同萃取率。在邻菲咯啉浓度高于双硫腙浓度的条件下，界面处形成了中间络合物。(1)测定了β-二酮在阴离子、阳离子和非离子O/W型微乳液中的离解常数。用表面电荷对β-二酮类化合物吸附的静电效应解释了离解常数的介质效应。(2)制作了搅拌法测量分散体系吸收光谱的光学元件，研究了四苯基卟啉(TPP)在甲苯/硫酸体系中的界面质子化反应。实验结果表明，在界面处形成了双质子化的TPP及其聚集体。(3)以聚四氟乙烯滤膜或聚四氟乙烯薄片为支撑材料，观察到液膜的界面光谱。用该方法测定了TPP和一种罗丹明B衍生物的界面质子化。这种方法现在被应用于界面动力学和电场对界面反应的影响的测量。

项目成果

H.Watarai M.Endoh: "Interfacial Kinetics in the Extraction of Copper(II)and Nickel(II)with 2'ーHydroxyー5'ーnonylbenzophenone Oxime" Analytical Sciences. 7. 137-140 (1991)

H.Watarai M.Endoh：“用 2－羟基－5－壬基二苯甲酮肟萃取铜 (II) 和镍 (II) 的界面动力学”《分析科学》7. 137-140 (1991)。

H.Watarai: "Role of interface in the Kinetics of synergic extraction of nickel(II)ーdithizoneー1,10ーPhenanthroline complex" Proceedings of International Solvent Extraction conference'90.

H.Watarai：“界面在镍(II)－双硫腙－1,10－菲咯啉络合物协同萃取动力学中的作用”国际溶剂萃取会议论文集90。

H. Watarai: "Tautomerization and dissociation equilibria of β-diketones in microemulsions" Bull.Chem.Soc.Jpn.,. 65. 170-174 (1992)

H. Watarai：“微乳液中 β-二酮的互变异构和解离平衡”Bull.Chem.Soc.Jpn., 65. 170-174 (1992)

H. Watarai and M. Endoh: ""Interfacial kinetics in the extraction of copper (II) and nickel (II) with 2'-hydroxy-5'-nonylbenzophenone oxime"" Anal. Sci.7(2). 137-140 (1991)

H. Watarai 和 M. Endoh：“用 2-羟基-5-壬基二苯甲酮肟萃取铜 (II) 和镍 (II) 的界面动力学”Anal。

H. Watarai, M. Takano and N. Suzuki: ""Tautomerization and dissociation equilibria of beta-diketones in microemulsions"" Bull. Chem. Soc. Jpn.65(1). 170-174 (1992)

H. Watarai、M. Takano 和 N. Suzuki：“微乳液中 β-二酮的互变异构和解离平衡”Bull。