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Quantum chemical approach to calculating the enthalpies of the formation of alkali metal xanthates

https://doi.org/10.32362/2410-6593-2020-15-2-30-37

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Abstract

Objectives. The aim of this work is to study the possibility of the joint use of quantum chemical methods and correlation analysis to determine the formation enthalpies of metal-containing organic substances using the example of alkali metal xanthates, which are of interest as biologically active substances and effective flotation reagents.

Methods. Semi-empirical methods of quantum chemical calculating (Modified Neglect of Diatomic Overlap, Austin Model 1, Recife model 1 methods) and linear regression analysis were used.

Results. Using the semi-empirical Modified Neglect of Diatomic Overlap, Austin Model 1, and Recife model 1 methods, the enthalpies of formation of 16 potassium and sodium alkyl xanthates were calculated, and the obtained results were compared with experimental data. It was found that the best correlation for potassium and sodium salts of dithiocarbonic acid esters could be observed using the Austin Model 1 method. Using the obtained regression equations, the enthalpies of formation were calculated for 30 xanthates, the organic part of which contained alkyl, cyclic non-aromatic structures, and one or two heteroatoms such as nitrogen, oxygen, and fluorine, and for which there are no experimental data.

Conclusions. As a result of the study, an excellent correlation was established between the experimental and the calculated (by the Austin Model 1 method) values of the enthalpies of formation of potassium and sodium alkyl xanthates. The data obtained can be used to calculate the thermal effect of the xanthogenation reactions of alcohols and to design the production of the corresponding xanthates. 

About the Authors

Yu. V. Popov
Volgograd State Technical University
Russian Federation

Yuriy V. Popov, Dr. of Sci. (Chemistry), Professor, Head of the Department of Organic and Petrochemical Synthesis Technology

28, pr. im. V.I. Lenina, Volgograd, 400005



A. S. Dolgachev
Volzhskii Orgsintez
Russian Federation

Aleksandr S. Dolgachev, Head of the Engineering Center

100, Aleksandrova ul., Volzhskii, Volgograd oblast, 404117



E. V. Shishkin
Volgograd State Technical University
Russian Federation

Evgeniy V. Shishkin, Dr. of Sci. (Chemistry), Associate Professor, Dean of the Chemical Technology Faculty

28, pr. im. V.I. Lenina, Volgograd, 400005



Yu. L. Zotov
Volgograd State Technical University
Russian Federation

Yuriy L. Zotov, Dr. of Sci. (Chemistry), Professor, Department of Organic and Petrochemical Synthesis Technology

28, pr. im. V.I. Lenina, Volgograd, 400005



V. E. Shishkin
Volgograd State Technical University
Russian Federation

Veniamin E. Shishkin, Dr. of Sci. (Chemistry), Professor, Department of Organic and Petrochemical Synthesis Technology

28, pr. im. V.I. Lenina, Volgograd, 400005



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Supplementary files

1. In the present study, the concurrent use of quantum chemical methods and correlation analysis for the determination of formation enthalpies of metal-containing organic substances employing alkali metal xanthates as examples was investigated. An excellent correlation was established between the experimental values of enthalpies for the formation of potassium and sodium alkyl xanthates and those calculated utilizing the Austin Model 1 method. The obtained data can be used to calculate the thermal effects of xanthogenation reactions of alcohols as well as to design the production of the corresponding xanthates.
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2. This is to certify that the paper titled Quantum chemical approach to calculating the enthalpies of the formation of alkali metal xanthates. commissioned to Enago by Yuriy V. Popov, Аleksandr S. Dolgachev, Еvgeniy V. Shishkin, Yuriy L. Zotov, Veniamin E. Shishkin has been edited for English language and spelling by Enago, an editing brand of Crimson Interactive Inc
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In the present study, the concurrent use of quantum chemical methods and correlation analysis for the determination of formation enthalpies of metal-containing organic substances employing alkali metal xanthates as examples was investigated. An excellent correlation was established between the experimental values of enthalpies for the formation of potassium and sodium alkyl xanthates and those calculated utilizing the Austin Model 1 method. The obtained data can be used to calculate the thermal effects of xanthogenation reactions of alcohols as well as to design the production of the corresponding xanthates.

For citation:


Popov Yu.V., Dolgachev A.S., Shishkin E.V., Zotov Yu.L., Shishkin V.E. Quantum chemical approach to calculating the enthalpies of the formation of alkali metal xanthates. Fine Chemical Technologies. 2020;15(2):30-37. https://doi.org/10.32362/2410-6593-2020-15-2-30-37

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