Theoretical calculation of the parameters of the three-parameter chromatographic phase characterization method II. Hydrogen bond parameter and hydrophilicity characteristic
Abstract
. 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 characterization of stationary phases in liquid chromatography based on it. These were applied to quantify the ability of molecules to participate in dispersion and dipole-dipole interactions and hydrogen bonds. The method has proved to be effective in describing the properties of stationary phases of various classes. The properties of stationary phases and sorbate molecules are described by two selectivity characteristics: polarity and hydrophilicity, which can be calculated from the direct problem using the structural formula of the substance and from the inverse problem using the experimental data in the form of Kovacs retention indices or Rorschneider-McReynolds constants. The chosen model was internally consistent, and both calculation methods were equal. A convenient and illustrative way to classify stationary phases using the three-parameter characteristic method was the selectivity map, which, combined with the principle of similarity of properties, was used to choose the most selective stationary phase for a given sorbate. This choice did not require experimentation.
The proposed work reveals the definitions of the parameters of the probability of hydrogen bonding and hydrophilicity. This is the second part of a series of articles dedicated to determining the parameters of the chosen method. The main tool used to describe intermolecular interactions was the theory of generalised charges developed earlier in the laboratory of sorption methods of IGAC RAS. Using this theory, the key characteristics of the proposed method were determined – generalized charges and the probability of formation of a hydrogen bond. For the first time, the hydrogen bond energy was theoretically estimated as the product of the minimum possible energy of the electronic bond between the donor hydride and the acceptor atom, explained by the properties of the corresponding hydrides, by the probability of its occurrence, which depended on the structure of the interacting molecules. The paper provides definitions and expressions for the hydrogen bond energy, as well as the probability of its formation (the H-bond parameter) and hydrophilicity. We presented the results of a detailed calculation of the hydrogen bond parameters of substances of different classes, including gas chromatographic stationary phases.
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