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

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.

Keywords

• alkali metal xanthates
• semi-empirical quantum chemical calculation methods
• correlation analysis
• formation enthalpy