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  • Author or Editor: I. Igumenov x
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Abstract  

The temperature dependency of the saturated vapor pressure of Ir(acac)3 has been measured by the method of calibrated volume (MCV), the Knudsen method, the flow transpiration method, and the membrane method. The thermodynamic parameters of phase transition of a crystal to gas were calculated using each of these methods, and the following values of ΔH T 0 (kJ mol−1) and ΔS T 0 (J mol−1K−1), respectively, were obtained: MCV: 101.59, 156.70; Knudsen: 130.54, 224.40; Flow transpiration: 129.34, 212.23; Membrane: 95.45, 149.44 Coprocessing of obtaining data (MCV, flow transportation method and Knudsen method) at temperature ranges 110−200C as also conducted:ΔH T 0 =127.92.1 (kJ mol−1 ); ΔS T 0 =215.25.0 (J mol−1 K−1 ).

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Abstract  

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 ΔH T* and entropy
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta S^{\text{o}}_{T*}$$ \end{document}
of this complexes were determined.
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Abstract

A universal (that is, actual for any reaction) interconnection between enthalpy (Δr H), entropy (Δr S), and Gibbs energy (Δr G) 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.

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Abstract

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 ΔH T and entropy ΔS T o, were determined. The atom-atomic potential calculation of the van der Waals energy (E cryst) of the crystal lattice was performed and the results were compared to the experimental values of the sublimation enthalpy for the complexes under study.

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Journal of Thermal Analysis and Calorimetry
Authors: E. Filatov, S. Sysoev, Ludmila Zelenina, Tamara Chusova, V. Logvinenko, P. Semyannikov, and I. Igumenov

Abstract  

Thermal behaviour of a series of lithium β-diketonates: Li(dpm) (dpm=dipivaloylmethanate (2,2,6,6-tetramethylheptane-3,5- dionate)), Li(pta) (pta=pivaloyltrifluoracetonate (2,2-dimethyl-6,6,6-trifluoro-3,5-hexanedionate)), Li(tfa) (tfa=trifluoracetylacetonate (1,1,1-trifluoro-2,4-pentandionate)), Li(hfa) (hfa=hexafluoracetylacetonate (1,1,1,5,5,5-hexafluoro-2,4-pentandionate)) has been investigated. Gas phase composition of these complexes has been established. Temperature dependences of vapor pressure of lithium compounds were obtained by static and dynamic methods, and thermodynamic parameters were calculated. Dependence of compound volatility on ligand structure is shown. For Li(dpm) detailed investigation has been done by differential scanning calorimetry (DSC).

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Abstract  

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 ΔH T* and entropy ΔS T 0 were determined. The energy of intermolecular interaction in the crystals of complexes was calculated.

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Journal of Thermal Analysis and Calorimetry
Authors: A. Bessonov, N. Morozova, P. Semyannikov, S. Trubin, N. Gelfond, and I. Igumenov

Abstract  

The thermal properties of dimethylgold(III) carboxylates of general formula [(CH3)2Au(OOCR)]2 (R=methyl (1), tert-buthyl (2), trifluoromethyl (3), or phenyl (4)) in solid state have been investigated by the thermogravimetric analysis. The temperature dependences of saturated vapour pressure of complexes have been studied by the Knudsen effusion method with mass spectrometric indication. The thermodynamic parameters Δsub H T 0 and Δsub S T 0 of the sublimation processes have been calculated. Thermal decomposition of the vapour of complexes 1 and 2 has been studied by means of high temperature mass spectrometry in vacuum, and by-products of decomposition have been determined.

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