STOICHIOMETRIC AND KINETIC STUDY OF ION ASSOCIATION INVOLVING SOLVATOCHROMISM AND ITS USE IN ANALYTICAL CHEMISTRY

本研究人员发现，一些染料离子在水溶液中与其配对离子发生反应，形成离子缔合体并改变最大吸收波长及其吸收强度。发现吸收波长和强度的变化是由“溶剂化变色现象”引起的。通过使用新设计和合成的染料离子，已经详细研究了这种溶剂化显色现象。溶剂化显色是一种新型现象，是由于染料离子与疏水配对离子反应形成离子缔合体时，周围微环境的极性发生变化而发生的。通过利用颜色变化反应，对水溶液中的离子缔合反应进行了化学计量和动力学研究。首先通过分光光度法、毛细管电泳迁移率变化法和光子滴定法测定水溶液中形成的各种疏水性离子缔合物的离子缔合常数。新开发的试剂的离子缔合反应被应用于各种离子物质的分析，例如阳离子、阴离子和非离子表面活性剂以及磷酸盐和硅酸盐以及杂多酸的形成。本研究取得的成果如下： 1．新型离子缔合试剂的合成与开发。开发了两种类型的试剂，在配对离子存在下，最大吸收波长向较短和较长的波长移动。 2．水溶液中离子缔合常数的测定。通过使用溶剂化变色和离子迁移率的变化，并通过分析光度滴定曲线来确定疏水离子​​缔合物的常数。对离子缔合进行了热力学研究，表明离子缔合的熵变非常重要。 3．分析用途。新开发的缔合试剂可用于流动注射分析中离子物质的分光光度测定、柱后显色检测、光度滴定以及毛细管电泳分离和检测。较少的

The present investigator found that some dye ions reacted with their pairing ions in an aqueous solution to form ion associates and to change the maximum absorption wavelengths and its absorption intensity. The change in absorption wavelength and intensity was found to be caused by "solvatochromism". Such solvatochromism has been studied in detail by using newly designed and synthesized dye ions. The solvatochromism, which was found a new-type phenomenon, was occurred on the basis of the change in the polarity of the micro-environment around the dye ions, when they reacted with hydrophobic pairing ions to form ion associates. By utilizing the color change reactions, the ion association reactions in aqueous solutions were studied stoichiometrically and kenetically. Ion association constants of various hydrophobic ion associates formed in aqueous solutions were first determined spectrophotometrically, as well as by a mobility change method using capillary elelctrophoresis and by a photom … More etric titration method. The ion association reactions with newly developed reagents were applied to the analysis of various ionic substances such as cationic, anionic and nonionic surfactants and phosphate and silicate coupled with the formation of heteropoly acids. The results obtained in this research are summarized as follows.1. Sysnthesis and developments of novel ion association reagents. Two types of reagents, which showed the shift of maximum absorption wavelength toward a shorter and a longer wavelengths in the presence of pairing ions, were developed.2. Determination of ion association constants in aqueous solutions. The constants of hydrophobic ion associates were determined by using the solvatochromism and the change in ionic mobility, and by analysing the photmetric titration curves. Thermodynamic study of ion association was carried out, which showed the entropy change involging ion association was very important.3. Analytical uses. The newly developed in association reagents were used for the spectrophotometric determination of ionic substances for flow injection analysis, for the detection in post column coloration, for photometric titration and for the separation and detection in capillary electrophoresis. Less