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

研究人员发现，一些染料离子在水溶液中与其配对离子反应形成离子缔合物，从而改变其最大吸收波长和吸收强度。吸收波长和吸收强度的变化是由“溶致变色”引起的。用新设计和合成的染料离子对这种溶致变色性进行了详细的研究。溶致变色是由于染料离子与疏水配对离子反应形成离子缔合物时，其周围微环境的极性发生变化而产生的一种新的变色现象。利用变色反应，对水溶液中的离子缔合反应进行了化学计量学和动力学研究。首次用分光光度法、毛细管电泳法和光电…法测定了在水溶液中形成的各种疏水离子缔合物的离子缔合常数。更多的是电滴定法。用新开发的试剂进行离子缔合反应，分析了各种离子物质，如阳离子、阴离子和非离子表面活性剂，以及与杂多酸形成耦合的磷酸盐和硅酸盐。本研究取得的研究成果概括如下：1.新型离子缔合试剂的合成与发展。在配对离子存在的情况下，两种试剂的最大吸收波长分别向短波长和长波长移动。水溶液中离子缔合常数的测定。利用溶致变色性和离子迁移率的变化，并通过分析光度滴定曲线，确定了疏水离子缔合物的常数。对离子缔合的热力学进行了研究，结果表明，离子缔合过程中的熵变是非常重要的。分析用途。新开发的缔合试剂用于流动注射分析中离子物质的光度测定，柱后显色中的检测，光度滴定和毛细管电泳中的分离检测。较少

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