Kinetic and Equilibrium Studies of Ion Association Reaction Between Ternary Heteropolyacids and Cat Ionic Dyes

1. 金属离子IV_A和V_A与磷酸盐、砷酸盐和硅酸盐杂多酸反应生成三元杂多酸。这种三元杂多酸能与阳离子染料反应形成有色离子缔合物。有色离子缔合物可用于磷酸盐、砷酸盐和硅酸盐的灵敏和选择性测定：它们存在于水相中，漂浮在有机相和水相之间的界面上，并被提取到有机相中。本研究探讨了离子缔合反应的机理。用停流分光光度法研究了三苯甲烷染料在水介质和两相平衡中的特性和行为。在三苯基甲烷染料中，水分子在中心碳原子上的加成是一个速率决定步骤，-OH在中心碳原子上的消去也是一个速率决定步骤。考察了影响杂多酸生成速率的各种因素，发现醇类和丙酮等有机溶剂、季铵离子和质子化三苯甲烷染料对杂多酸的生成有促进作用。研究了杂多酸与阳离子染料的离子缔合反应。钼（VI）可与孔雀石绿（MG^+）在水相中形成离子缔合。钼钒酸盐与HMG^<2+>形成离子缔合物形成黄色缔合物。三元杂多酸如钒钼磷酸酯和锆钼磷酸酯与阳离子染料形成离子缔合，以及钼磷酸盐和硅酸钼与阳离子染料形成离子缔合。这些离子结合物可用于分光光度法测定磷酸盐、硅酸盐和钒酸盐。根据阳离子染料与阳离子染料形成离子缔合反应，建立了测定磷、硅、钒的灵敏、选择性方法。用分光光度法测定了亚ppt水平下的硅酮浓度。少

1. Metal ions such as IV_A and V_A ions react with heteropolyacids of phosphate, arsenate and silicate to form ternary heteropolyacids. Such ternary heteropolyacids can react with cationic dyes to form colored ion associates. The colored ion associates can be used for the sensitive and selective determination of phosphate, arsenate and silicate : they are present in an aqueous phase, and floated on the interface between an organic and an aqueous phase and are extracted into an organic phase. In this research, the mechanism of the ion association reactions are investigated.2. The characteristics and behavior of triphenylmethane dyes in an aqueous medium and in two-phase equilibrium has been examined spectrophotometrically by a stopped-flow method. The addition of water molecule to the centered carbon atom of the triphenylmethane dyes was found to be a rate-determining step, and also the elimination of -OH from the centered carbon atom was found to be a rate-determining step.3. Various f … More actors affecting the formation rate of heteropolyacids was examined : organic solvent such as alcohols and acetone, quaternary ammonium ions and protonated triphenylmethane dyes was found to accelerate the formation reaction of heteropolyacids.4. Ion association reaction of heteropolyacids with cationic dyes was examined. Molybdenum (VI) can form an ion associate with malachite green (MG^+) in an aqueous phase. Molybdovanadete forms an ion associate with HMG^<2+> to form a yellow associate. The ternary heteropolyacids such as vanadomolybdophosphate and zirconomolybdophosphate form ion associate with cationic dyes, as well as molybdophosphate and molydbdosilicate do. These ion associates can be used for the spectrophotometric determination of phosphate, silicate and vanadate.5. The sensitive and selective methods for the determination of phosphorus, silicone and vanadium were developed on the basis of the formation of ion associate with cationic dyes. Silicone at concentrations of sub-ppt levels has been determined by spectrophotometry. Less