Ni+Pd+Ga and Ni+Pd+in liquid alloys: Enthalpies of formation

In order to fill the evident gap in the thermodynamic data of nickel-palladium-gallium and nickel-palladium-indium ternary alloys, the enthalpies of formation of these systems in the liquid state have been determined. This was achieved by means of a very high temperature calorimeter (T<1800 K), using the direct drop method, and based on analogous measurements of the respective binary alloys previously published. Complete automation of the calorimeter led to a good precision even at the highest temperatures. The enthalpies of formation of the ternary liquid alloys were measured between 1400 and 1600 K on the whole composition range. As in the limiting binary systems, enthalpies of formation are negative and non temperature dependent at any composition.

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Zusammenfassung Um die Lücke hinsichtlich thermodynamischer Daten von Nickel-Palladium-Gallium und Nickel-Palladium-Indium Legierungen zu füllen, wurden die Bildungsenthalpien dieser ternÄren Systeme im flüssigen Zustand bestimmt. Dies erfolgte mittels eines Kalorimeters für sehr hohe Temperaturen (T<1800 K), unter Verwendung der direkten Einwurfmethode auf der Basis früher veröffentlichter Messungen an den entsprechenden binÄren Systemen. Die Bildungsenthalpien der flüssigen ternÄren Legierungen wurden zwischen 1400 und 1600 K über den gesamten Zusammensetzungsbereich bestimmt. VollstÄndige Automation des Kalorimeters bewirkte hohe PrÄzision selbst bei den höchsten Temperaturen. Wie in den begrenzenden binÄren Systemen sind die Bildungsenthalpien negativ und bei allen Zusammensetzungen nicht temperaturabhÄngig.

     

Enthalpies of Phase Transitions and Heat Capacity of TbCl3 and Compounds Formed in TbCl3–MCl Systems (M=K, Rb, Cs)

The molar enthalpies of the solid–solid and solid–liquid phase transitions were determined by differential scanning calorimetry for pure TbCl₃ and KTb₂Cl₇, RbTb₂Cl₇, CsTb₂Cl₇, K₃TbCl₆, Rb₃TbCl₆ and Cs₃TbCl₆ compounds. Both types of compounds, i.e. M₃TbCl₆ and MTb₂Cl₇ (M=K, Rb, Cs) melt congruently and show additionally a solid–solid phase transition with a corresponding enthalpy Δ_trs H ⁰ of 6.1, 7.6 and 7.0 kJ mol^–1 for potassium, rubidium and caesium M₃TbCl₆ compounds andΔ_trs H ⁰ of 17.1 (rubidium) and of 12.1 and 10.9 kJ mol^–1 (caesium) for MTb₂Cl₇ compounds, respectively. The enthalpies of fusion were measured for all the above compounds with the exception of Rb₃TbCl₆ and Cs₃TbCl₆. The heat capacities of the solid and liquid compounds have been determined by differential scanning calorimetry (DSC) in the temperature range 300–1100 K. The experimental heat capacity strongly increases in the vicinity of a phase transition, but varies smoothly in the temperature ranges excluding these transformations. C _p data were fitted by an equation, which provided a satisfactory representation up to the temperatures of C _p discontinuity. The measured heat capacities were checked for consistency by calculating the enthalpy of formation of the liquid phase, which had been previously measured. The results obtained agreed satisfactorily with these experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Solubility of Lanthanide Chlorides ( Ln Cl3) in Alkali Metal Chlorides ( M Cl): Thermodynamics and Electrical Conductivity of the M 3 Ln Cl6 Compounds

Summary.  Several compounds may exist in LnCl₃–MCl mixtures. Those corresponding to the M ₂ LnCl₅ and MLn ₂Cl₇ stoichiometries are formed in a few systems only, with diverse stability strongly dependent on both the corresponding lanthanide and alkali metal. On the other hand, M ₃ LnCl₆ that occur in most systems have a far larger stability range and melt congruently. These latter compounds were investigated in the present work by differential scanning calorimetry and electrical conductivity measurements. The thermodynamic and transport properties were correlated to structural features and related to the mechanism of compound formation. Corresponding author. E-mail: Marcelle.Gaune-Escard@polytech.univ-mrs.fr Received October 2, 2002; accepted November 6, 2002 Published online April 24, 2003 RID="a" ID="a" This paper is dedicated to Professor H. Gamsj?ger on the occasion of his birthday     

Electrochemical synthesis of rare-earth metal (Eu,Nd) borides in molten salts

Rare-earth metal borides are widely used in different fields of modern techniques. Electrochemical synthesis at moderate temperatures (973–1023 K) is a cost-effective alternative to direct reaction techniques. The present work reports the mechanism and kinetics of boron and europium, boron and neodymium joint electrodischarge in chloride-fluoride molten systems. The optimum regimes of europium and neodymium borides electrodeposition are worked out on the base of voltammetric experiments. Europium compound is synthesized as a single-phase EuB₆ product, while neodymium compounds is co-deposited as NdB₄ and NdB₆. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 8, pp. 978–984. The article was translated by the authors.     

Phases of the K2TaF7–TaF5 binary system

The phase equilibria in the K₂TaF₇–TaF₅ binary system were determined up to x _TaF5 = 0.5 by means of differential scanning calorimetry. XRD diffraction analysis of solidified mixtures was performed. Besides the K₂TaF₇ and KTaF₆ phases, the presence of a third phase was observed, as well. It was suggested that the last phase melts incongruently. Correspondence: B. Kubikova, Institute of Inorganic Chemistry SAS, Dúbravská cesta 9, Bratislava, 845 36, Slovakia.     

Calorimetric investigations of the MBr−NdBr3 melts (M=Li,Na, K,Cs)

Present work is a part of thermodynamic research program on the MX?LnX₃ system (M=alkali metal,X=Cl, Br andLn=lanthanide). Molar enthalpies of mixing in the LiBr?NdBr₃, NaBr?NdBr₃ and KBr?NdBr₃ liquid binary systems have been determined at temperature 1063 K by direct calorimetry in the whole range of composition. Investigated systems are generally characterized by negative enthalpies of mixing with minimum atX _NdBr3≈0.3–0.4. These enthalpies decrease with decrease of ionic radii of alkali metals. Molar enthalpies of solid-solid and solid-liquid phase transitions of K₃NdBr₆ and Cs₃NdBr₆ have been also determined by differential scanning calorimetry (DSC). K₃NdBr₆ is formed at 689 K from KBr and K₂NdBr₅ with enthalpy of 44.0 kJ·mol^?1 whereas Cs₃NdBr₆ is stable at ambient temperature and undergoes phase transition in the solid state at 731 K with enthalpy of 8.8 kJ·mol^?1. Enthalpies of melting have been also determined.     

Phase diagram and electrical conductivity of TbBr3-NaBr binary system

Several experimental techniques were used to characterise the physicochemical properties of the TbBr₃-NaBr system. The phase diagram determined by DSC, exhibits an eutectic and a Na₃TbBr₆ stoichiometric compound that decomposes peritectically (759 K) shortly after a solid-solid phase transition (745 K). The eutectic composition, x(TbBr₃)=39.5 mol%, was obtained from the Tamman method. This mixture melts at 699 K. With the corresponding enthalpy of about 16.1 kJ mol^-1. Diffuse reflectance spectra of the pure components and their solid mixtures (after homogenisation in the liquid state) confirmed the existence of new phase exhibiting its own spectral characteristics, which may be possibly related to the formation of Na₃TbBr₆ in this system. Additionally, the electrical conductivity of TbBr₃-NaBr liquid mixtures was measured down to temperatures below solidification over the whole composition range. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase diagram and electrical conductivity of the CeBr3–CsBr binary system

Journal of Thermal Analysis and Calorimetry - Phase equilibrium in the CeBr3–CsBr binary system was established from differential scanning calorimetry (DSC). This system includes three...     

Reinvestigation of phase equilibria in TbCl<Subscript>3</Subscript>–LiCl binary system

The phase equilibria in the terbium(III) chloride–lithium chloride pseudobinary system were established by means of differential scanning calorimetry. It was established that the pure terbium(III) chloride undergoes solid–solid phase transition at 790 K and melts at 859 K. The TbCl₃–LiCl pseudobinary system is characterized by the existence of two compounds. First one, namely Li₃TbCl₆, forms at 553 K and melts incongruently at 727 K. Second compound, LiTbCl₄, decomposes in the solid state at 609 K. The composition of Li₃TbCl₆–TbCl₃ eutectic corresponding to terbium(III) chloride mole fraction x = 0.521 (T = 665 K) was found from Tammann plot, which predict, through application of the lever rule, the variation of the enthalpy associated with eutectic melting as a function of composition. The obtained results have been compared with the literature data concerning for the TbCl₃–LiCl pseudobinary system. The phase diagram of the TbCl₃–LiCl pseudobinary system was also optimized by CALPHAD method.     

Phase diagram and electrical conductivity of the DyBr<Subscript>3</Subscript>–RbBr binary system

Phase equilibrium in the DyBr₃–RbBr binary system was established from differential scanning calorimetry measurements. This system exhibits three compounds, namely Rb₃DyBr₆, Rb₂DyBr₅, and RbDy₂Br₇, and two eutectics located at DyBr₃ molar fraction x = 0.116 (T = 886 K) and x = 0.458 (T = 702 K), respectively. Rb₃DyBr₆ undergoes a solid–solid phase transition at 726 K and melts congruently at 1,059 K. Rb₂DyBr₅ and RbDy₂Br₇ melt incongruently at 737 and 748 K, respectively. The electrical conductivity of DyBr₃–RbBr liquid mixtures was measured over the whole composition range. Results obtained are discussed in term of possible complex formation.