THERMODYNAMIC FUNCTIONS OF FORMATION OF LITHIUM TITANATES

By the method of electromotive forces measuring concentration chains: Pt│Li2O│ ZrO2+10 wt% Y2O3, lithium glass. (Li2O)x(TiO2)1-x│Pt in the temperature range T=1000–1200K and concentrations 0.35÷0.95 mol fraction TiO2, the thermodynamic functions of the formation of the compounds Li4TiO4, Li2TiO3, Li4Ti5O12 and phases based on Li2TiO3:Li1.92Ti1.04O3.04, Li2.12Ti0.94O2.92 were determined. With the exception of the compound Li2TiO3, the thermodynamic functions of the formation of lithium titanates are deter¬mined for the first time. The thermodynamic functions of formation are calculated for the 1200 K and for the standard state at 298 K. The thermodynamic functions of the formation of lithium titanates are determined from simple substances and from binary compounds Li2O and TiO2. In particular, for the free energy, enthalpy of formation and standard entropy we obtained: ∆G_298^0(Li4TiO4)=–2149 kJ∙mol-1; ∆G_298^0(Li2TiO3)=–1565; ∆G_298^0(Li4Ti5O12)=–5923; ∆H_298^0(Li4TiO4)=–2286 kJ∙mol-1; ∆H_298^0(Li2TiO3)=–1662; ∆H_298^0(Li4Ti5O12)=–6287; S_298^0(Li4TiO4)=119.1 J∙mol-1∙K-1; S_298^0(Li2TiO3)=84; S_298^0(Li4Ti5O12)=315.7

Thermodynamic properties of the GdTe3 compound

The alloys of the Gd-Te system in the range of compositions > 75 at% Te were studied by the methods of X-ray diffraction (XRD) and electromotive forces (EMF). From the EMF measurements of the concentration cells relative to the GdTe electrode in the 300-450 K temperature range, the partial thermodynamic functions of GdTe in alloys were determined. By combining these data with the corresponding functions of Gd in GdTe, the partial molar functions of gadolinium in GdTe3+Te alloys, and standard thermodynamic functions of formation and standard entropy of the GdTe3 compound were calculated. The obtained results were compared with the literature data.

Thermodynamic study of the thallium-thulium tellurides by EMF method

In this study the phase equilibria in the Tl2Te–Tl2Te3–TlTmTe2compositions area of the Tl–Tm–Te ternary system were studied by powder X-ray diffraction (PXRD) analysis. Based on PXRD data, the solid-phase equi-libria diagram was plotted. The thermodynamic functions of the Tl9TmTe6and TlTmTe2ternary compounds were calculated by the electromotive forces method. The electrochemical cells of the following type (−) TmТе (s.) | glycerol + KCl + TmCl3 | (Tm in alloys of Tl–Tm–Te system) (s.) (+) were assembled and their EMF were measured in the 300-450 Ktemperature range. Based on obtained EMF data for the Tl2Te3–TlTe–TlTmTe2and TlTe–TlTmTe2–Tl9TmTe6three-phase regions, the relative partial thermodynamic functions of TmTe in alloys were calculated. The combination of these functions with the partial molar functions of thulium in TmTe allowed calculating the corresponding partial functions of thulium in the above phase regions. The potential-forming reactions responsible for the indicated partial molar values were obtained based on con-structed solid-phase equilibria diagram. Using indicated potential-forming reactions, for the first time, the standard thermodynamic functions of formation and standard entropies of the Tl9TmTe6and TlTmTe2 compounds were calculated.

Thermodynamic study of a synthetic analog of the famatinite mineral - Cu3SbS4

Fundamental thermodynamic properties of the synthetic analog of the famatinite mineral - Cu3SbS4 were studied on the basis of electromotive force (EMF) measurements. The EMF of the concentration chains relative to the Cu electrode with a solid electrolyte was measured for the alloys from the Cu3SbS4 + Sb2S3 + S phase region at 300-380K temperature interval. Based on measurement data, the relative partial thermodynamic functions of copper in alloys, the standard thermodynamic functions of formation, as well as, the standard entropy of the Cu3SbS4 ternary compound were calculated for the first time.

Thermodynamıc Propertıes of the BiTe and Bi8Te9 Compounds

Two-phase alloys Bi8Te9+Bi4Te5 and BiTe+Bi8Te9 were studied by the electromotive forces method (EMF) in the temperature range 300-450 K. From the EMF data, the relative partial molar functions of bismuth in the alloys were calculated. The potential-forming reactions responsible for these partial functions were compiled, the values of the standard thermodynamic functions of formation, and the standard entropies of Bi8Te9 and BiTe compounds were calculated. A comparative analysis of the data for BiTe with the literature data was carried out; for Bi8Te9, the thermodynamic functions were obtained for the first time.

Electrochemical and thermodynamic properties of U4+ and U3+ on Mo electrode in LiCl-KCl eutectic

In this study, UCl4 was prepared by the reaction of HCl gas with UO2 in the LiCl-KCl eutectic. Then, the electrochemical behavior of U4+ and U3+ on a Mo cathode was investigated by various electrochemical techniques. The reduction process of U4+ was regarded as two steps: U4++e=U3+; U3++3e=U. Diffusion coefficients of U4+ and U3+, the apparent standard potential of U4+/U3+, U3+/U as well as U4+/U in the LiCl-KCl molten salt on the Mo electrode was determined by numerous electrochemical methods. The thermodynamic functions of formation of Gibbs free energy of UCl4 and UCl3 are calculated as well.

Spectral studies on the interaction of iodine with thiazoles

The electron donor–acceptor molecular complexes between thiazole and some of its derivatives and iodine in several solvents have been investigated spectrophotometrically at different temperatures. Spectral characteristics, equilibrium constants, K, extinction coefficients, ε, and thermodynamic functions of formation, ΔH0, ΔG0, and ΔS0 have been determined. It was found that the data fit satisfactorily the 1:1 stoichiometric equilibrium: D + I2 = DI2 "outer complex". The EDA complexes obtained are of "n–σ*" type in which the nitrogen atom of thiazole is the donor center. Moreover, the effect of solvents on the K values is discussed in terms of the solute–solute and solute–solvent competing equilibria.