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Development of Measurement System for Fast Thermal Reactions in Solutions

溶液中快速热反应测量系统的开发

基本信息

批准号：
11554030
负责人：
INADA Yasuhiro
金额：
$ 4.61万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11554030/
关键词：
Variable Rate Flow Method Fast Thermal Reaction Variable Flow Rate Rapid Mixing Technique Complexation Reaction Copper(II) Ion Zinc(II) Ion Silting-Atop Complex 高速サンプリング機構置換活性 PAF装置高速サンプリング電子移動反応フロー法変速フロー装置パルスYAGレーザー

项目摘要

The purpose of this study was to develop the Variable Rate Flow (VRF) instrument in order to determine the rate constants for the fast thermal reactions with the rate constant of ca. 10^6 s^<-1> (the half-life of ca. 0.5 μs) occurred in solutions. In the VRF instrument, the flow rate of the mixed solution is controlled with the high accuracy and the change in the transmitted light intensity is measured by varying the flow rate.In order to achieve the purpose, we first modified the commercial VRF instrument to introduce the 10-jet mixing chamber and the piston cylinder which is connected with a high-power servo motor controlled automatically. Then we developed the data reduction system to collect the output signals from the encoder of the servo motor to measure the flow velocity and from the photomultiplier detector to measure the transmitted light intensity.By using the newly developed VRF instrument, the kinetic measurements for the fast complexation reactions of Cu(II) and Zn(II) ion … More s were systematically performed in acetonitrile. It has been too difficult to measure directly the complexation reactions for these metal(II) ions because of their lability. Owing to the development of the VRF instrument, it becomes possible to monitor directly and to determine the rate constants. For the Cu(II) ion, the complexation reactions with some porphyrins were measured, and the formation mechanisms of the Sitting-Atop intermediate, which is existed during the dynamic processes of the metalation reaction, have been clarified. An unique trend of the observed rate constants is interpreted in terms of the axially-elongated distorted octahedral solvation structure of the Cu(II) ion and the limited axial-equatorial interconversions of the substituted Cu(II) species. For the Zn(II) ion, the complexation rate constants with some aromatic amine ligands were successfully determined. Especially in the case of the multidentate ligand, such as 2,2'- bipyridine, an unknown pathway for the complexation reaction was suggested kinetically according to the dependency of the rate constant as a function of the widely-variable concentration of the Zn(II) ion. Less

本研究的目的是开发可变速率流动（VRF）仪器，以确定快速热反应的速率常数，速率常数约为。10^6 s^<-1>（ca的半衰期）。0.5μs）发生在溶液中。在VRF仪器中，通过改变混合溶液的流速来测量透射光强的变化，并对商用VRF仪器进行了改进，引入了10喷嘴混合室和活塞缸，活塞缸与大功率伺服电机相连，伺服电机自动控制。利用自行研制的VRF仪器，对Cu（Ⅱ）、Zn（Ⅱ）离子的快速络合反应进行了动力学测量，并对实验结果进行了分析 ...更多信息在乙腈中系统地进行。由于这些金属离子的不稳定性，直接测量它们的络合反应非常困难。由于VRF仪器的发展，直接监测和测定速率常数成为可能。对于Cu（II）离子，测定了其与某些卟啉的络合反应，阐明了金属化反应动力学过程中存在的Sitting-Atop中间体的形成机理。所观察到的速率常数的一个独特的趋势被解释在轴向拉长扭曲的八面体溶剂化结构的Cu（II）离子和有限的轴向赤道相互转换的取代Cu（II）物种。对于锌（II）离子，络合速率常数与一些芳香胺配体被成功地确定。特别是在多齿配体的情况下，如2，2 '-联吡啶，一个未知的途径的络合反应动力学建议根据依赖性的速率常数作为一个函数的广泛可变浓度的Zn（II）离子。少