Synthesis and Thermodynamic Functions of Ruthenium Dichalcogenides in a Wide Temperature Range

Thermodynamic properties of polycrystalline powders of ruthenium dichalcogenides have been studied using calorimetric isobaric heat capacity measurements in a wide temperature range. The adiabatic and differential scanning calorimetry data for ruthenium disulfide and ruthenium diselenide have been used to determine standard thermodynamic functions (heat capacity, entropy, enthalpy increment, and reduced Gibbs energy) of these compounds in the range 10–965 K. At 298.15 K, the functions of RuS₂ are as follows: \(C_{p}^{^\circ }\) = 60.82 ± 0.12 J/(K mol), S° = 56.05 ± 0.11 J/(K mol), Н°(298.15 K) − Н°(0) = 9.75 ± 0.02 kJ/mol, and Ф° = 23.34 ± 0.05 J/(K mol). For RuSe₂, we have obtained \(C_{p}^{^\circ }\) = 69.96 ± 0.14 J/(K mol), S° = 80.62 ± 0.16 J/(K mol), Н°(298.15 K) − Н°(0) = 13.05 ± 0.03 kJ/mol, and Ф° = 36.85 ± 0.08 J/(K mol). The data obtained above 298 K have been used to determine empirical coefficients of the Maier–Kelley and Khodakovsky equations. The absolute entropies obtained in this study for the ruthenium dichalcogenides, in combination with literature data, have made it possible to evaluate the Gibbs energy of formation of RuS₂(cr) and RuSe₂(cr) at 298.15 K.