Yu. G. Safina

Thermochemistry of dithiophosphoric acid derivatives

Thermal effects of reactions involving dithiophosphoric acids were analyzed and formation enthalpies of a series of dithiophosphates are determined. Analysis of the resulting experimental data was carried out on the basis of the additive scheme. Group contributions into the vaporization and formation enthalpies were determined, and thermochemical characteristics of the compounds were calculated.

The thermochemical characteristics of vaporization and formation of organic three-coordinate arsenic derivatives

The experimental data on the enthalpies of vaporization and formation of more than 30 three-coordinate arsenic derivatives of various structures were collected and analyzed. The group contributions of arsenic-containing fragments to the enthalpies of vaporization and formation were calculated. This opens up the possibility of calculating the fundamental thermochemical characteristics of a wide range of As(III) derivatives by the additive scheme.

Enthalpies of specific interaction of heteroatom derivatives of three-coordinate phosphorus with chloroform

The nature of hydrogen bonds formed by chloroform with three-coordinate phosphorus derivatives containing sulfur, silicon, and chlorine atoms and their carbon analogs was revealed by analysis of the experimental enthalpies of specific interactions. The main donor centers in the examined compounds were found to be oxygen atoms and π-electron systems of aromatic rings. Sulfur atoms give rise to weaker complexes as compared to oxygen. Phosphorus, chlorine, and silicon atoms are not involved directly in specific interactions with the solvent.

Electronic effects on the enthalpy of specific interaction of three-coordinate phosphorus compounds and acetals with chloroform

The effect of electronic factors in five- and six-membered cyclic three-coordinate phosphorus compounds and acetals on the enthalpy of their specific interaction with chloroform was estimated.

Thermochemical characteristics of phosphorous acid derivatives

Enthalpies of formation enthalpies of a series of phosphorous acid derivatives were estimated from the heat effects of their reactions. The collected thermochemical data was used to analyze, on the basis of the additive scheme, the experimental enthalpies of formation and vaporization of four-coordinate phosphorus derivatives.

Applicability Limits of Calculation Methods for Estimating the Enthalpy of Vaporization of Organophosphorus Compounds

Quantitative relationships used today for calculating the enthalpies of vaporization of organophosphorus compounds are analyzed. The parameters of equations used in these calculations largely depend on specific structural features and are common for closely related compounds only. With various P(III) derivatives as examples, narrow ranges are distinguished in which the enthalpies of vaporization can be estimated from the boiling points using common relationships. The group contributions of phosphorus-containing fragments for calculations by the additive scheme are determined.