Kinetic Studies on Metal Complexation Reactions by High-Performance Liquid Chromatography

高效液相色谱法研究金属络合反应的动力学

基本信息

批准号：
06640776
负责人：
SHIBUKAWA Masami
金额：
$ 1.47万
依托单位：
Chiba 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：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

Equilibrium and kinetic studies on the ligand exchange reactions of 5-sulphoquinoline-8-ol (HQS) complexes of various metal ions with inorganic anions were carried out by high-performance liquid chromatography. The retention behavior of the metal complexes in reversed-phase ion-pair liquid chromatography was investigated by using an octadecyl-modified silica or a polystirene-divinylbenzene copolymer as a column packing and tetrabutylammonium ion as an ion pairing agent.1. The aluminum complex gave two or three peaks on the chromatograms whem eluents containing phosphate ion or fluoride ion were used, whereas the other metal complexes exhibited only one peak. In contrast with the results obtained with the phosphate or fluoride ion system, acetate and chloride ion eluent systems gave only one sharp peak for an injection of aluminum. It was elucidated that some of the aluminum peaks corresponded to mixed ligand complexes with HQS and phosphate ion or fluoride ion from the effects of the concentrations of HQS and these inorganic anions in the eluents on the areas of the peaks. The compositions of the mixed ligand complexes and the equilibrium constants of the ligand exchange reactions were also determined.2. The rate constants for the ligand exchange reactions described above were estimated from the relationship between the peak areas and the reaction time.3. The aluminum-HQS complex could completely be separated from the gallium complex by utilizing the ligand exchange reaction with fluoride ion.4. The kinetic studies on the ligand exchange reaction with reaction rates larger than that for the reactions described above has jist been started. It is also scheduled to clarify the mechanism of the, ligand exhange reaction of the aluminum-HQS complex.

采用高效液相色谱法对多种金属离子与无机阴离子的5-磺基喹啉-8-醇(HQS)配合物的配体交换反应进行平衡和动力学研究。以十八烷基改性硅胶或聚苯乙烯-二乙烯基苯共聚物为填料，四丁基铵离子为离子对剂，研究了金属配合物在反相离子对液相色谱中的保留行为。 1．当使用含有磷酸根离子或氟离子的洗脱液时，铝络合物在色谱图中出现两个或三个峰，而其他金属络合物仅显示一个峰。与用磷酸盐或氟离子系统获得的结果相反，乙酸盐和氯离子洗脱液系统对于铝的进样仅给出一个尖峰。从洗脱液中HQS和这些无机阴离子浓度对峰面积的影响，阐明一些铝峰对应于HQS与磷酸根离子或氟离子的混合配体络合物。测定了混合配体配合物的组成和配体交换反应的平衡常数。 2．上述配体交换反应的速率常数是根据峰面积和反应时间之间的关系估计的。 3．利用氟离子的配体交换反应，可以将铝-HQS配合物与镓配合物完全分离。4．反应速率大于上述反应的配体交换反应的动力学研究已经开始。还计划阐明铝-HQS复合物的配体交换反应的机理。