Specific Intermolecular Interactions of Sulfur, Oxygen, and Nitrogenated Organic Compounds

Abstract

The vaporization enthalpies of the sulfide compounds of carbon and carbon dioxide are often measured at temperatures that differ from the standard temperature by 10–14 K, which causes certain errors in the obtained energy characteristics. Nevertheless, they are of special interest in the thermodynamic analysis of specific interactions of the various oxygen- and sulfur-containing compounds. The inherent similarity of the C=O and C=S groups in the compounds’ molecular structure, along with significant differences in the donor–acceptor properties of oxygen and sulfur atoms, allow their influence on the energies of the specific interactions formed to be traced. The difference of 1.5 kJ mol⁻¹ between the vaporization enthalpies of carbon dioxide and carbonyl sulfide points to the unequal influence of the oxygen and sulfur atoms on the stabilization of a specific interaction. In turn, the difference of 11.8 kJ mol⁻¹between the vaporization enthalpies of carbon dioxide and carbon disulfide indicates the formation of more stable specific interactions by the sulfur atoms. The deficit of electron acceptors in the carbon atoms in the formation of specific interactions provides the sulfur atoms with the participation of one free electron pair.