Catalytic Effect on the Proton Transfer Reaction

质子在水溶液中的传递反应是扩散控制过程，各种胺在稀水溶液中的超声弛豫归因于与此反应有关的平衡扰动。在丙胺-聚乙烯醇(PVA)溶液中，测定了质子转移反应的速率常数。研究了PVA的浓度对速率常数的依赖关系和聚合度的依赖关系。结果表明，反应速率常数与浓度和聚合度有关。也就是说，当PVA的聚合度保持不变时，扩散控制速率常数出现最大值。在PVA浓度不变的情况下，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，聚乙烯醇的溶液性质与…的聚合度有关N越多，浓度越高。PVA具有以羟基为亲水基团的亲水性。聚丙二醇(PPG)含有醚氧基，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，人们认为这两种聚合物对反应的催化作用可能会进一步得到澄清。在丙胺溶液中加入不同浓度的PPG聚合物，其度数为13。测定了PPG的扩散速率常数，发现低浓度PPG的扩散控制速率常数与未加聚合物时的扩散控制速率常数基本相同。在PPG的浓水溶液中，观察到了超声弛豫吸收。在聚合物溶液中加入胺后，超声吸收光谱非常复杂，很难区分两个松弛过程。然而，对PPG溶液吸收系数的精确测定使得这两个松弛参数被分开。通过对吸收光谱的分析，确定了质子转移反应的速率常数。结果表明，扩散控制反应的速率常数是不加PPG时的一半。这可能是因为在水溶液中PPG聚合物的存在阻碍了反应物的迁移率。在介电常数很低的溶剂中也进行了三离子形成的动力学研究。还研究了与大聚集体形成相关的过程--酪蛋白胶束的形成。此外，在我们的一系列溶液动力学研究中，我们还研究了一些醇的水溶液中的溶质-溶剂相互作用动力学。较少

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