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Catalytic Effect on the Proton Transfer Reaction

对质子转移反应的催化作用

基本信息

批准号：
02640350
负责人：
NISHIKAWA Sadakatsu
金额：
$ 1.41万
依托单位：
Saga 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-02640350/
关键词：
Proton transfer reaction Catalysis Ultrasonic Absorption Relaxation phenomenon Polymer effect アミン水溶液

项目摘要

The pro ton t iansf er react i on i n aqueous soIution is the diffusion controlled process and the ultrasonic relaxation in dilute aqueous solutions of various amine has been attributed to a perturbation of the equilibrium associated with such reaction. In the solution in which propylamine and polyvinyl alcohol (PVA), the rate constants for the proton transfer reaction have been determined. The concentration dependence of PVA on the rate constants and the dependence ofthe degree of the polymerization have been studied. It has been found that the rate constants depend on both of the concentration and the degree of the polymerization. That is, the diffusion controlled rate constant shows a maximum when the degree of polymerization for PVA is kept constant. When the concentration of PVA is constant, the rate constant also show a maximum when the degree of polymerization increases. These results indicate that the solution characteristics of PVA depend on both of the degree of polymerizatio … More n and the concentration. PVA has the hydroxyl groups as the hydrophilic ability. Polypropylene glYcol (PPG) has the ether oxygens and the solubility into water is quite high. In order to examine the effect of these two polymers on the proton transfer reaction of the amine, it is considered hopefully that the catalytic effects on the reaction may be further clarified. PPG polymer, the degree of which is 13, has been added at various concentrations to the propyl amine solution. The rate constants have been determined and it has found that the diffusion controlled rate constant at low concentration of PPG is almost the same as that without the polymer. In the concentrated aqueous solution of PPG, the ultrasonic relaxational absorption is observed. The addition of the amine into the polymer solution, the ultrasonic absorption spectra are so complicate that it was difficult to distinguish two relaxation processes. However, the precise determinations of the absorption coefficients in PPG solution have made to divide the two relaxation parameters. Following these analysis of the absorption spectra, the rate constants for the proton transfer reaction have been determined. As the results, the obtained rate constant for the diffusion controlled reaction has been half of that without PPG. This may be because the mobility of the reactants has been prevented by the existences of the PPG polymers in the aqueous solutions.The kinetic study for triple ion formation has also made in the solvents with very low dielectric constants. The process associated with the large aggregate formation, casein micelle formation, has been also investigated. Furthermore, the solute-solvent interaction kinetic has performed in the aqueous solution of some alcohols in our series of the dynamic studies in solutions. Less

水溶液中的质子转移反应是扩散控制过程，各种胺稀溶液中的超声弛豫归因于与该反应有关的平衡扰动。在丙胺和聚乙烯醇（PVA）的溶液中，测定了质子转移反应的速率常数。研究了聚乙烯醇浓度对反应速率常数的依赖性和聚合度对反应速率常数的依赖性。结果表明，聚合反应的速率常数与聚合物的浓度和聚合度有关。也就是说，当PVA的聚合度保持恒定时，扩散控制速率常数显示最大值。当PVA浓度一定时，随着聚合度的增加，反应速率常数也出现最大值。这些结果表明，PVA的溶液特性取决于聚合度和粘度， ...更多信息 n和浓度。PVA具有羟基作为亲水性基团。聚丙二醇（PPG）具有醚氧，在水中的溶解度很高。为了考察这两种聚合物对胺的质子转移反应的影响，人们认为有希望进一步阐明这两种聚合物对该反应的催化作用。将度为13的PPG聚合物以各种浓度加入到丙胺溶液中。速率常数已被确定，它已经发现，在低浓度的PPG的扩散控制的速率常数几乎是相同的，没有聚合物。在PPG浓水溶液中，观察到超声弛豫吸收。在聚合物溶液中加入胺后，其超声吸收光谱非常复杂，很难区分两个弛豫过程。然而，PPG溶液中吸收系数的精确测定使得两个弛豫参数分开。在这些吸收光谱的分析之后，已经确定了质子转移反应的速率常数。作为结果，所获得的扩散控制反应的速率常数是没有PPG的速率常数的一半。这可能是因为PPG聚合物的存在阻碍了反应物在水溶液中的流动性。在介电常数很低的溶剂中也进行了三重离子形成的动力学研究。与大聚集体的形成，酪蛋白胶束的形成，相关的过程也进行了研究。此外，在我们的系列溶液动力学研究中，还对某些醇的水溶液进行了溶质-溶剂相互作用动力学研究。少