Theoretical calculation of the parameters of the three-parameter chromatographic phase characterization method I. Dispersion forces parameter – generalized charge
Abstract
In this work we studied the flavonoid composition of tangerine skins using 10 kinds of tangerines from the selectivity of separation in gas chromatography is determined by the nature of the stationary phase. The authors previously proposed a model of intermolecular interactions and a theoretical method of three-parameter characterisation of stationary phases in liquid chromatography based on it. They were applied to quantify the ability of molecules to participate in dispersion and dipole-dipole interactions and hydrogen bonds. The method proved to be efficient to describe the properties of stationary phases based on hydrocarbons, polyethylene glycol, polysiloxanes, and ionic liquids. The properties of stationary phases and analyte molecules are described by two selectivity characteristics: polarity and hydrophilicity, which can be calculated as a direct problem using the structural formula of the substance, or as an inverse problem using experimental data in the form of the Kovacs retention indices or Rohrschneider and McReynolds constants. No contradictions have been found between the characteristics calculated by the two methods. Using the proposed method, the relationship between the molecular weight of the polymer molecule and the values of selectivity characteristics was revealed. We proposed a selectivity map as a convenient and illustrative way to classify the stationary phases. Backed by the principle of similarity of properties, it can be used to determine the most selective stationary phase for a given analyte, without any experiments.
The aim of this work was to determine the generalised charge as the first and key parameter of the three-parameter characterisation method. The main tool was the theory of generalised charges developed earlier in the laboratory of sorption methods of GEOKHI RAS. This theory, derived from fundamental principles, describes van der Waals interactions in the form of a Lennard-Jones potential, using the characteristics of molecules determined from their molecular structure. Previously, it successfully described nonpolar chromatographic systems. In the present study, we defined generalised charges, showed their relation to physical and experimental values, and provided calculation formulas for isolated molecules and for liquid phases. We presented the results of a detailed calculation of the generalised charges of substances of different classes, including gas chromatographic stationary phases.
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