Sorptive redistribution of volatile organic compounds in a mixed gas–liquid crystal–macrocycle–adsorbent system under reversed gas chromatography conditions

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Abstract

4-[(S)-2-Methyl-3-hydroxypropoxy]-4'-formylazobenzene, 4-(3-hydroxypropoxy)-4'-formylazobenzene, and µ-oxo dimer of iron 2,8,12,18-tetramethyl-3,7,13,17-tetra-n-amylporphyrin were synthesized using known methods. A mixture with a specified concentration of the synthesized compounds was prepared and used to impregnate a wide-pore adsorbent Chromaton N-AW. The degree of impregnation was 10%. The prepared adsorbent was used as the stationary phase for reversed gas-mesophase chromatography. Using the reversed gas chromatography method, the sorptive redistribution of a series of volatile organic compounds—methyl- and dimethylpyridine isomers, weakly polar xylenes, and enantiomers—was studied from the gas phase on the prepared adsorbent. During the experiment, specific retained volumes of sorbates, characterizing the sorptive activity of the prepared stationary phase, were calculated. Activity coefficients of sorbate distribution in the liquid layer of the liquid crystal were obtained for structural isomers. To confirm the data on sorptive activity, thermodynamic parameters of the dissolution of specific isomers were found. Conclusions were made regarding the influence of enthalpy and entropy factors on the retention capacity of the sorbates. The influence of structure, isomerism, intermolecular interactions, and the addition of a macrocycle on the sorptive characteristics of sorbates is discussed. Analytical sorption features were evaluated, and maximum values of separation factors for structural and optical isomers, as well as for compounds with different structures but close boiling points, were calculated. It was experimentally established that the prepared adsorbent exhibits sufficiently high capability for separating structurally similar isomers with close boiling points and moderate capability for enantiomer separation. Special attention was given to the maximum separation factor for 3,4- and 3,5-lutidines, which was higher than that of previously developed stationary phases of similar structure. The application of the prepared adsorbent in an integrated chemical analysis system is justified.

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About the authors

G. V. Kuvshinov

Ivanovo State University of Chemistry and Technology

Author for correspondence.
Email: gmkuvv@gmail.com
Russian Federation, Ivanovo

L. O. Monakhov

Ivanovo State University of Chemistry and Technology

Email: gmkuvv@gmail.com
Russian Federation, Ivanovo

A. A. Kuzmina

Ivanovo State University of Chemistry and Technology

Email: gmkuvv@gmail.com
Russian Federation, Ivanovo

A. S. Semeykin

Ivanovo State University of Chemistry and Technology

Email: gmkuvv@gmail.com
Russian Federation, Ivanovo

O. I. Koifman

Ivanovo State University of Chemistry and Technology; Research Institute of Macroheterocyclic Compounds

Email: gmkuvv@gmail.com
Russian Federation, Ivanovo; Ivanovo

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2. Рис. 1. Зависимость логарифма удельного удерживаемого объема от обратной температуры колонки. (а) – для 3,4- и 3,5-лутидинов, (б) – для (2S,3S)-(+)- и (2R,3R)-(-)-2,3-бутандиолов).

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3. Рис. 2. Хроматограмма разделения 3,4- и 3,5-лутидинов.

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4. Рис. 3. Хроматограмма разделения (2S,3S)-(+)- и (2R,3R)-(-)-2,3-бутандиолов.

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5. Схема 1. Структурные формулы (а) 4-[(S)-2-метил-3-гидроксипропилокси]-4-формилазобензол, (б) 4-(3-гидро ксипропилокси)-4-формилазобензол, (в) µ-оксодимер железа 2,8,12,18-тетраметил-3,7,13,17-тетра-н-амилпорфина.

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