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Studies on Ternary Heteropoly Acids in Analytical Chemistry

三元杂多酸在分析化学中的研究

基本信息

批准号：
60470037
负责人：
IKEDA Shigero
金额：
$ 3.58万
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：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470037/
关键词：
Ternary heteropoly acid Group 4A element Group 5A element 溶媒パラメーター

项目摘要

An inorganic heteropoly anion produced through the reaction of an isopoly molybdate anion with a phosphate one was found to have very specific character acting as an analytical reagent for heavy elements and alkali elements. Each of group 4A elements such as Ti( <IV> ), Zr( <IV> ), Hf( <IV> ), Th( <IV> ) and Ce( <IV> ) and group 5A elements such as V( <V> ), Nb( <V> ) and Ta( <V> ), in the periodic table, could be substituted for one of the molybdenum elements so as to form a ternary heteropoly anion. The nuclear magnetic resonance spectrum of each ternary heteropoly anion shows a specific chemical shift for each substituted heavy element in its resonance peak position. This fact is quite useful for simultaneous quantitative analysis of the group 4A and group 5A elements in the aqueous medium.The solute-solvent interaction was investigated to find out the empirical parameters for the extraction of each ternary heteropoly anion in organic solvents. These parameters were applied to the selective separation of 12-molybdosilicate and 12-molybdophosphate and also to that of the binary heteropoly anion and the ternary one.The local structure around the molybdenum atom in the binary heteropoly anion and the ternary one and that around the vanadium atom in the 11-molybdo-vanado-phosphate vanado-phosphate ternary heteropoly anion were examined by extended X-ray absorption fine structure analysis.

由钼酸盐异聚阴离子与磷酸盐异聚阴离子反应产生的无机杂多离子具有非常特殊的性质，可作为重元素和碱元素的分析试剂。元素周期表中4A族元素Ti（<IV>）、Zr（<IV>）、Hf（<IV>）、Th（<IV>）、Ce（<IV>）和5A族元素V（<V>）、Nb（<V>）、Ta（<V>）均可取代其中一种钼元素，形成三元杂多离子。各三元杂多阴离子的核磁共振谱显示出各取代重元素在其共振峰位置的特定化学位移。这一事实对于同时定量分析水介质中4A族和5A族元素非常有用。研究了溶剂-溶质相互作用，确定了在有机溶剂中萃取各三元杂多离子的经验参数。这些参数适用于12-钼酸盐和12-钼磷酸的选择性分离，也适用于二元杂多离子和三元阴离子的选择性分离。采用扩展x射线吸收精细结构分析方法研究了二元杂多阴离子中钼原子周围的局部结构和11-钼-钒-磷酸钒-磷酸三元杂多阴离子中钒原子周围的局部结构。