Determination of gibbs energy of formation of cuspidine (3CaO · 2SiO<Subscript>2</Subscript> · CaF<Subscript>2</Subscript>) from the electromotive force method using CaF<Subscript>2</Subscript> as the solid electrolyte

The standard Gibbs energy change for the following reaction has been directly determined by electromotive force (EMF) measurement using CaF₂ as the solid electrolyte in the temperature range from 1313 to 1329 K.

Electrochemical determination of gibbs energy of formation of NiTiO3 (ilmenite)

Gibbs energy of formation of NiTiO₃ (ilmenite) relative to its component oxides, NiO (rock salt) and TiO₂ (rutile), has been measured employing the solid-state electrochemical cell,

Thermodynamics of the system NaF-AlF3: Part VII. Non-stoichiometric solid cryolite

Earlier data are recalculated to give the boundaries of the homogeneous field of solid cryolite. The equilibrium constant

Equilibrium of calcium vapor with liquid iron and the interaction of third elements

The dissolution equilibrium of calcium vapor in liquid iron was carried out at 1873 K in a two-temperature zone furnace using a vapor-liquid equilibration method. A sealed Mo reaction chamber and a self-made CaO crucible were used in this study. The thermodynamic parameters obtained are as follows. For reaction Ca (g)=[Ca],

Phase equilibria in the titanium-oxygen system

Data in the literature on the Magneli oxides of titanium have been critically evaluated and equations have been developed from these data for the standard-state Gibbs energy of formation of the following oxides: Ti₄O₇, Ti₅O₉, Ti₆O₁₁, Ti₈O₁₅, and Ti₉O₁₇. Examination of those data yielded the following:

Determination of standard gibbs energies of formation of Fe2Mo3O12, Fe2Mo3O8, Fe2MoO4, and FeMoO4 of the Fe-Mo-O ternary system and μ phase of the Fe-Mo binary system by electromotive force measurement using a Y2O3-stabilized ZrO2 solid electrolyte

The standard Gibbs energies of formation of Fe₂Mo₃O₁₂, Fe₂Mo₃O₈, FeMoO₄, and Fe₂MoO₄ of the Fe-Mo-O ternary system and the μ phase of the Fe-Mo binary system have been determined by measuring electromotive forces of galvanic cells having an Y₂O₃-stabilized ZrO₂ solid electrolyte. The results are as follows: $$\begin{gathered} \Delta _f G^\circ (FeMoO_4 )/kJ \cdot mol^{ - 1} = - 1053.5 + 0.2983(T/K) \pm 0.4 \hfill \\ Temperature range: 1112 to 1339 K \hfill \\ \Delta _f G^\circ (Fe_2 Mo_3 O_8 )/kJ \cdot mol^{ - 1} = - 2347 + 0.6814(T/K) \pm 1 \hfill \\ Temperature range: 1112 to 1339 K \hfill \\ \Delta _f G^\circ (Fe_2 Mo_3 O_{12} )/kJ \cdot mol^{ - 1} = - 2993 + 0.9105(T/K) \pm 2 \hfill \\ Temperature range: 1040 to 1145 K \hfill \\ \Delta _f G^\circ (Fe_{0.58} Mo_{0.42} )/kJ \cdot mol^{ - 1} = - 18.7 + 0.0117(T/K) \pm 0.1 \hfill \\ Temperature range: 1162 to 1223 K \hfill \\ \Delta _f G^\circ (Fe_2 MoO_4 )/kJ \cdot mol^{ - 1} = - 1174 + 0.342(T/K) \pm 1 \hfill \\ Temperature range: 1243 to 1466 K \hfill \\ \end{gathered} $$ where the standard pressure is 1 bar (100 kPa).     

Enthalpy of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys

The partial (Δ and the integral (ΔH) enthalpies of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys have been determined by high-temperature isoperibolic calorimetry at 1565 ± 5 K. The heat capacity (C _p) of liquid Ni₂₆Zr₇₄ has been measured by adiabatic calorimetry (C _p=53.5±2.2 J mol⁻¹ K⁻¹ at 1261±15 K). The integral enthalpy of mixing changes with composition from a small positive (Cu-Ni, ΔH (x _Ni=0.50, T=1473 to 1750 K)=2.9 kJ mol⁻¹) to a moderate negative (Cu-Zr; ΔH(x _Zr=0.46, T=1485 K)=−16.2 kJ mol⁻¹) and a high negative value (Ni-Zr; ΔH(x _Zr=0.37, T=1565 K)=−45.8 kJ mol⁻¹). Regression analysis of new data, together with the literature data for liquid Ni-Zr alloys, results in the following relationships in kJ mol⁻¹ (standard states: Cu (1), Ni (1), and Zr (1)):for Ni-Zr (1281≤T≤2270 K),

Determination of standard gibbs energies of formation of Cr2N and CrN

The standard Gibbs energies of formation of Cr₂N and CrN have been measured by an equilibration technique and by using thermogravimetry and differential thermal analysis (TG-DTA) at temperatures ranging from 1232 to 1523 K. The results are expressed as follows:

Thermodynamic investigations of Cr<Subscript>3</Subscript>C<Subscript>2</Subscript> and reassessment of the Cr-C system

The Gibbs energies of formation for Cr₃C₂, , have been obtained from electromotive force (EMF) measurements, in the temperature range 950 to 1150 K, using the following galvanic cells with CaF₂ single crystals as the electrolyte:

Thermodynamic study of MnO-SiO2-Al2O3 slag system: Liquidus lines and activities of MnO at 1823 K

The liquid MnO-SiO₂-Al₂O₃ system was studied at 1823 K by equilibrating MnO-SiO₂-Al₂O₃ melts of different compositions with Pt-Mn alloys and an oxygen-bearing gas phase. Liquid compositions for cristobalite saturation were determined at 1823 K. A new liquidus for the cristobalite primary field is proposed. The activity of Mn in the Pt-Mn alloy at 1823 K can be represented by the following equation:

The rate of antimony elimination from molten copper by the use of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> slag

The rate of Sb elimination from molten copper by the use of Na₂CO₃ slag was measured at 1523 K. The results obtained under the present experimental conditions show that Sb in molten copper is eliminated in a tri-valent or a penta-valent form, depending on the oxygen concentration at the slag-metal interface, and its elimination rate increases with increasing initial oxygen concentration in molten copper. The overall elimination rate of Sb is affected by the stirring condition of the molten copper, which indicates a rate control by mass transfer in that phase. The mass-transfer coefficients of Sb and oxygen in molten copper at 1523 K without external stirring were determined, respectively, to be

Thermodynamic study of the effect of calcium on removal of phosphorus from silicon by acid leaching treatment

The interaction between calcium and phosphorus in molten silicon was investigated for predicting the removal of phosphorus from silicon by an acid leaching treatment with calcium addition. In the present study, two immiscible liquids of silicon and lead were equilibrated, and the interaction parameter between calcium and phosphorus and the self-interaction parameter of phosphorus in molten silicon at 1723 K were determined.

Kinetics of formation and dissociation of Na2SiF6

Spontaneous fluoride emissions from high-temperature processes can result in an increased atmospheric fluorine content and environmental contamination. Slags containing SiO₂, Na₂O, and CaF₂ tend to be unstable at high temperatures, and gaseous species such as NaF and SiF₄ evolve simultaneously. Furthermore, a reaction between NaF and SiF₄ can occur to produce Na₂SiF₆ (sodium hexafluorosilicate), the behavior and properties of which are not well established. In a previous study, the diffusivity of NaF in argon, nitrogen, and helium was measured. In this study, the rate of NaF vaporization in a SiF₄-Ar atmosphere was investigated and the rates of formation and dissociation of Na₂SiF₆ were measured. Kinetic analyses were carried out and the rate constants of the formation and dissociation of Na₂SiF₆ were obtained. The rate equation for Na₂SiF₆ formation was expressed as follows:

Determination of standard gibbs energies of formation of MgO,SrO, and BaO

The standard Gibbs energy of formation of MgO was determined from the measurement of the ΔG° for the reaction ; by equilibrating Mg and Nb with a magnesia crucible and is expressed as follows: Mg(l)+ l/2O₂(g) = MgO(s) ΔG° = −657,000(±5000) + 141(±13)T [J/mol] (973 to 1323 K) The standard Gibbs energies of formation of SrO and BaO were determined by equilibrating silver and MO(M: Sr, and Ba) in a graphite crucible on the basis of the reactionM(in Ag) + CO (g) = MO (s) + C (s), yielding the following results:

Thermodynamic properties of aluminum, magnesium, and calcium in molten silicon

The thermodynamic properties of aluminum, magnesium, and calcium in molten silicon were investigated using a chemical equilibration technique at 1723 to 1848 K, 1698 to 1798 K, and 1723 to 1823 K, respectively. The activity coefficient of aluminum in molten silicon was determined by equilibrating molten silicon-aluminum alloys with solid Al₂O₃ and Al₆Si₂O₁₃, that of magnesium was determined by equilibrating molten silicon-magnesium alloys and MgO-SiO₂-Al₂O₃ melts doubly saturated with MgSiO₃ and SiO₂, and that of calcium was determined by equilibrating molten silicon-calcium alloys with SiO₂-saturated CaO-SiO₂ melts. The activity coefficients at infinite dilution relative to the pure liquid state were determined as follows:

The oxidation of zinc vapor in CO-CO2-N2 gas mixtures

The kinetics of oxidation of zinc vapor in the Zn-CO-CO₂-N₂ system was investigated for zinc partial pressures of 0.01 to 0.09 atm, carbon monoxide partial pressures up to 0.5 atm, and carbon dioxide partial pressures up to 0.6 atm at 730 °C to 900 °C. The experimental apparatus consisted of a flow reactor and a multitemperature zone furnace. Known gas compositions were generated and the rate of oxidation of zinc vapor was determined from the mass of zinc oxide deposited under controlled conditions. The rate of oxidation of zinc was found to be a function of temperature and of the partial pressures of zinc, carbon monoxide, and carbon dioxide. It was autocatalytic with respect to carbon monoxide and independent of the total mass of zinc oxide deposited. The reactions occurring in parallel for this mechanism are

Kinetic modeling of titania reduction by a methane-hydrogen-argon gas mixture

This article describes kinetic modeling of titania reduction and carburization by methane-containing gas, based on experimental data reported previously by Zhang and Ostrovski. A sequence of titania reduction to titanium oxycarbide,

Thermodynamic properties and phase equilibria for Pt-Rh alloys

The activity of rhodium in solid Pt-Rh alloys is measured in the temperature range from 900 to 1300 K using the solid-state cell