Authors:N. Morozova, K. Zherikova, P. Semyannikov, S. Trubin, and I. Igumenov
Complexes of ruthenium(III) with the following beta-diketones: 2,4-pentanedione (Ru(acac)3), 1,1,1-trifluoro-2,4-pentanedione (Ru(tfac)3), 2,2,6,6-tetramethyl-3,5-heptanedione (Ru(thd)3), 2,2,6,6–tetramethyl-4-fluoro-3,5-heptanedione (Ru(tfhd)3) and 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (Ru(ptac)3) were synthesized and identified by means of mass spectrometry. By effusion Knudsen method with mass spectrometric registration
of gas phase composition the temperature dependencies of saturated vapor pressure were measured for ruthenium(III) compounds
and the thermodynamic characteristics of vaporization processes enthalpy ΔHT* and entropy
Authors:V. I. Belevantsev, K. V. Zherikova, N. B. Morozova, V. I. Malkova, and I. K. Igumenov
A universal (that is, actual for any reaction) interconnection between enthalpy (ΔrH), entropy (ΔrS), and Gibbs energy (ΔrG) was applied to the analysis of the formation of saturated vapor of individual condensed (liquid and solid) substances. This allowed us to specify the conceptual and metrological sense of thermodynamic parameters available for estimation within the framework of tensimetric investigations. Proposals for the procedures of experimental data processing were made. The informativity of the approach was illustrated by the example showing the results of processing two arrays of primary data obtained using the static and the flow methods for crystal hafnium(IV) dipivaloylmethanate.
Authors:G. I. Zharkova, S. V. Sysoev, P. A. Stabnikov, V. A. Logvinenko, and I. K. Igumenov
Volatile palladium(II) β-iminoketonates of the general formula Pd(R–C(NH)–CH–CO–R1),where R and R1 are CH3, CF3, C(CH3)3 in various combinations, were synthesized and identified. Thermal properties of the resulting palladium(II) complexes in the solid phase were studied by thermogravimetric analysis under an argon atmosphere. The temperature dependence of the saturated vapor pressure was measured for the compounds by the flow method and thermodynamic characteristics of vaporization processes, enthalpy ΔHT and entropy ΔSTo, were determined. The atom-atomic potential calculation of the van der Waals energy (Ecryst) of the crystal lattice was performed and the results were compared to the experimental values of the sublimation enthalpy for the complexes under study.
Authors:N. Morozova, P. Semyannikov, S. Trubin, P. Stabnikov, A. Bessonov, K. Zherikova, and I. Igumenov
Volatile compounds of iridium(I): (acetylacetonato)(1,5-cyclooctadiene)iridium(I) Ir(acac)(cod), (methylcyclopentadienyl)
(1,5-cyclooctadiene)iridium(I) Ir(Cp’)(cod), (pentamethylcyclopentadienyl)(dicarbonyl) iridium(I) Ir(Cp*)(CO)2 and (acetylacetonato)(dicarbonyl)iridium(I) Ir(acac)(CO)2 were synthesized and identified by means of element analysis, NMR-spectroscopy, mass spectrometry.
Thermal properties in solid phase for synthesized iridium(I) complexes were studied by means of thermogravimetric analysis
in inert atmosphere (He). By effusion Knudsen method with mass spectrometric registration of gas phase composition the temperature
dependencies of saturated vapor pressure were measured for iridium(I) compounds and the thermodynamic characteristics of vaporization
processes enthalpy ΔHT* and entropy ΔST0 were determined. The energy of intermolecular interaction in the crystals of complexes was calculated.
Authors:V. A. Logvinenko, N. E. Fedotova, I. K. Igumenov, and G. V. Gavrilova
Thermal dissociation processes ofβ-diketonate adducts with the composition ML2 · 2B (L = acetylacetone and its substituted derivatives;M = Ni, Co;B = H2O, BuNH2CH3OH, Py, NH3) were investigated. Kinetics of dissociation were studied in a flow reactor. For dehydration processes a compensation relationship is observed (lgA=E+b), demonstrating analogous mechanisms.
Authors:A. F. Bykov, N. B. Morozova, I. K. Igumenov, and S. V. Sysoev
By means of a tensimetric flow method and a static method with a silica-membrane zero gauge, the dependence of vapour pressure on temperature was obtained for tris(2,4-pentanedionato)ruthenium(III), Ru(aa)3, and tris(1,1,1-trifluoropentane-2,4-dionato)ruthenium(III), Ru(tfa)3. The thermodynamic characteristics of vaporization and sublimation of these complexes were determined. The processes of thermal decomposition of the vapour of the compounds in vacuum, hydrogen and oxygen were investigated by using mass spectrometry in the temperature range 170–550‡C for Ru(aa)3 and 150–620‡C for Ru(tfa)3. The threshold temperatures of the stability of the vapour of the complexes and the rate constants of the thermolysis processes were determined. The main gaseous products of the thermal decomposition and the dependences of their composition on the presence of hydrogen and oxygen were established.