A Kinetic Study on the Mass Transfer Phenomena in Reversed-Phase Liquid Chromatography

反相液相色谱传质现象的动力学研究

基本信息

批准号：
12640581
负责人：
MIYABE Kanji
金额：
$ 2.24万
依托单位：
Nagoya Institute of Technology (2003)University of Toyama (2000-2002)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2003
项目状态：
已结题

项目摘要

Kinetic studies on the mass transfer phenomena in columns were studied by means of pulse response experiments and the moment analysis under the conditions of reversed-phase liquid chromatography (RPLC). Various stationary phases having different physical and chemical properties were used, that is, porous silica gel particles bonded with alkyl chains of different carbon numbers, porous silica gel particles bonded with C_<18>-ligands of different surface coverages, porous silica gel particles bonded with phenyl group, porous particles made of styrene-divinylbenzene copolymer, and porous particles made of graphitic carbon. Methanol/water mixtures and standard materials of benzene derivatives and phenol derivatives were mainly used as the mobile phases and sample compounds, respectively. The information about the retention equilibrium and mass transfer kinetics were derived from the first absolute moment and the second central moment of the elution peak profiles. Especially, the characteri … More stics and mechanism of surface diffusion were studied in detail. To the best of the author's knowledge, there is so far no systematic study on surface diffusion. Thermodynamic properties of the retention equilibrium and surface diffusion were derived from the results of the pulse response experiments carried out under different temperature conditions. It was tried to systematically analyze the results in this study from various points of view in order to consistently understand the separation mechanism in RPLC.On the basis of the results about surface diffusion, the surface-restricted molecular diffusion model was proposed for surface diffusion as a first approximation. The new model was formulated according to the absolute rate theory. This model is effective for a comprehensive interpretation of the intrinsic characteristics and mechanism of surface diffusion.New moment equations were derived for monolithic columns packed with continuous porous separation media by solving the basic equations of the general rate model of chromatography in the Laplace domain. They correlate the peak moments and some parameters characterizing the retention equilibrium and the mass transfer kinetics in monolithic columns. Some items of new information on the mass transfer kinetics in C_<18>-silica monolithic columns were derived by applying the new moment equations to a set of experimental data. The validity of the new moment equations was confirmed. Less

采用脉冲响应实验和反相液相色谱（RPLC）条件下的矩分析，对柱内传质现象进行了动力学研究，采用了不同物理化学性质的固定相，即多孔固定相。键合有不同碳数的烷基链的硅胶颗粒、键合有不同表面覆盖度的C_<18>-配体的多孔硅胶颗粒、键合有苯基的多孔硅胶颗粒、主要使用苯乙烯-二乙烯基苯共聚物制成的多孔颗粒、石墨碳混合物制成的多孔颗粒以及苯衍生物和苯酚衍生物的标准材料，分别作为流动相和样品化合物。从洗脱峰轮廓的第一绝对矩和第二中心矩推导了传质动力学，特别是对表面扩散的特性和机理进行了详细研究。据作者所知，迄今为止还没有系统地研究从不同温度条件下进行的脉冲响应实验的结果得出的平衡和表面扩散的热力学性质。为了一致地理解RPLC中的分离机理，本研究从不同的角度对结果进行了分析。在表面扩散的结果的基础上，提出了表面扩散的表面限制分子扩散模型作为新的第一近似。模型是根据该模型对于全面解释表面扩散的内在特征和机制是有效的。通过求解色谱中一般速率模型的基本方程，推导了填充连续多孔分离介质的整体柱的新力矩方程。拉普拉斯域将峰矩与表征整体柱中平衡保留和传质动力学的一些参数相关联，并通过应用推导了有关 C_18>-二氧化硅整体柱中传质动力学的一些新信息。新的矩方程的有效性得到了一组实验数据的证实。