System Cu-Rh-O: Phase diagram and thermodynamic properties of ternary oxides CuRhO2 and CuRh204

An isothermal section of the phase diagram for the system Cu-Rh-O at 1273 K has been established by equilibration of samples representing eighteen different compositions, and phase identification after quenching by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive analysis of X-rays (EDX). In addition to the binary oxides Cu2O, CuO, and Rh2O3, two ternary oxides CuRhO2 and CuRh2O4 were identified. Both the ternary oxides were in equilibrium with metallic Rh. There was no evidence of the oxide Cu2Rh2O5 reported in the literature. Solid alloys were found to be in equilibrium with Cu2O. Based on the phase relations, two solid-state cells were designed to measure the Gibbs energies of formation of the two ternary oxides. Yttria-stabilized zirconia was used as the solid electrolyte, and an equimolar mixture of Rh+Rh2O3 as the reference electrode. The reference electrode was selected to generate a small electromotive force (emf), and thus minimize polarization of the three-phase electrode. When the driving force for oxygen transport through the solid electrolyte is small, electrochemical flux of oxygen from the high oxygen potential electrode to the low potential electrode is negligible. The measurements were conducted in the temperature range from 900 to 1300 K. The thermodynamic data can be represented by the following equations: {fx741-1} where Δf(ox) G o is the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides. Based on the thermodynamic information, chemical potential diagrams for the system Cu-Rh-O were developed.

Solid-state cells with buffer electrodes for accurate thermodynamic measurements: system Nd-Ir-O

A new design for the solid-state cell incorporating a buffer electrode for high-temperature thermodynamic measurements is presented. The function of the buffer electrode, placed between the reference and working electrodes, is to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevents polarization of the measuring electrode and ensures accurate data. The application of this novel design and its advantages are demonstrated by measurement of the standard Gibbs energies of formation of Nd6Ir2O13 (low-temperature form) and Nd2Ir2O7 in the temperature range from 975 to 1450 K. Yttria-stabilized zirconia is used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system NdIrO were investigated at 1350 K. The two ternary oxides, Nd6Ir2O13 and Nd2Ir2O7, compositions of which fall on the join Nd2O3IrO2, were found to coexist with pure metal Ir. Therefore, two working electrodes were prepared consisting of mixtures of Ir+Nd2O3+Nd6Ir2O13 and Ir+Nd6Ir2O13+ Nd2Ir2O7. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. The standard Gibbs energies of formation (ΔG°f (ox)) of the compounds from their component binary oxides Nd2O3 and IrO2, obtained from the emf of the cells, can be represented by the equations:View the MathML source View the MathML source Based on the thermodynamic information, chemical potential diagrams for the system NdIrO are developed.

Solute-solute and solute-solvent interactions in transition metal alloys: Pt-Ti system

An isothermal section of the phase diagram for (silver + rhodium + oxygen) at T = 1173 K has been established by equilibration of samples representing twelve different compositions, and phase identification after quenching by optical and scanning electron microscopy (s.e.m.), X-ray diffraction (x.r.d.), and energy dispersive analysis of X-rays (e.d.x.), Only one ternary oxide, AgRhO2, was found to be stable and a three phase region involving Ag, AgRhO2 and Rh2O3 was identified. The thermodynamic properties of AgRhO2 were measured using a galvanic cell in the temperature range 980 K to 1320 K. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa was used as the reference electrode. The Gibbs free energy of formation of the ternary oxide from the elements, ΔfGo (AgRhO2), can be represented by two linear equations that join at the melting temperature of silver. In the temperature range 980 K to 1235 K, ΔfGo(AgRhO2)/(J . mol-1) = -249080 + 179.08 T/K (±120). Above the melting temperature of silver, in the temperature range 1235 K to 1320 K, ΔfGo(AgRhO2)/(J . mol-1) = -260400 + 188.24 T/K (±95). The thermodynamic properties of AgRhO2 at T = 298.15 K were evaluated from the high temperature data. The chemical potential diagram for (silver + rhodium + oxygen) at T = 1200 K was also computed on the basis of the results of this study.

Refinement of thermodynamic properties of ReO2

The standard Gibbs energy of formation of ReO2 in the temperature range from 900 to 1200 K has been determined with high precision using a novel apparatus incorporating a buffer electrode between reference and working electrodes. The role of the buffer electrode was to absorb the electrochemical flux of oxygen through the solid electrolyte from the electrode with higher oxygen chemical potential to the electrode with lower oxygen potential. It prevented the polarization of the measuring electrode and ensured accurate data. The Re+ReO2 working electrode was placed in a closed stabilized-zirconia crucible to prevent continuous vaporization of Re2O7 at high temperatures. The standard Gibbs energy of the formation of ReO2 can be represented by the equation View the MathML source Accurate values of low and high temperature heat capacity of ReO2 are available in the literature. The thermal data are coupled with the standard Gibbs energy of formation, obtained in this study, to evaluate the standard enthalpy of formation of ReO2 at 298.15 K by the ‘third law’ method. The value of standard enthalpy of formation at 298.15 K is: View the MathML source(ReO2)/kJ mol−1=−445.1 (±0.2). The uncertainty estimate includes both random (2σ) and systematic errors.

Phase relations in the system Cu-Eu-O and thermodynamic properties of CuEu2O4 and CuEuO2

Phase relations in the system Cu-Eu-O have been determined by equilibrating samples of different average composition at 1200 K and by phase analysis after quenching using optical microscopy (OM), x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray (EDX). The equilibration experiments were conducted in evacuated ampoules and under flowing inert gas and pure oxygen. The Cu-Eu alloys were found to be in equilibrium with EuO. The higher oxides of europium, Eu3O4 and Eu2O3, coexist with metallic copper. Two ternary oxides CuEu2O4 and CuEuO2 were found to be stable. The ternary oxide CuEuO2, with copper in the monovalent state, can coexist with Cu, Cu2O, Eu2O3 and CuEu2O4 in different phase fields. The compound CuEu2O4 can be in equilibrium with Cu2O, CuO, CuEuO2, Eu2O3, and O2 gas under different conditions at 1200 K. Thermodynamic properties of the ternary oxides were determined using three solid-state cells based on yttria-stabilized zirconia as the electrolyte in the temperature range from 875 to 1250 K. The cells essentially measure the oxygen chemical potential in the three-phase fields: Cu+Eu2O3+CuEuO2, Cu2O+CuEuO2+CuEu2O4, and Eu2O3+CuEuO2+CuEu2O4. The thermodynamic properties of the ternary oxides can be represented by the equations: $\begin{gathered} {\raise0.5ex\hbox{$Couldn't find \end for begin{gathered} Thermogravimetric analysis (TGA) studies in Ar+O2 mixtures confirmed the results from emf measurements. An oxygen potential diagram for the system Cu-Eu-O at 1200 K was evaluated from the results of this study and information available in the literature on the binary phases.

Internal displacement reactions in multicomponent oxides: Part I. Line compounds with narrow homogeneity range

Structure and phase transition of LaO1−xF1+2x, prepared by solid-state reaction of La2O3 and LaF3, was investigated by X-ray powder diffraction and differential scanning calorimetry for both positive and negative values of the nonstoichiometric parameter x. The electrical conductivity was investigated as a function of temperature and oxygen partial pressure using AC impedance spectroscopy. Fluoride ion was identified as the migrating species in LaOF by coulometric titration and transport number determined by Tubandt technique and EMF measurements. Activation energy for conduction in LaOF was 58.5 (±0.8) kJ/mol. Conductivity increased with increasing fluorine concentration in the oxyfluoride phase, suggesting that interstitial fluoride ions are more mobile than vacancies. Although the values of ionic conductivity of cubic LaOF are lower, the oxygen partial pressure range for predominantly ionic conduction is larger than that for the commonly used stabilized-zirconia electrolytes. Thermodynamic analysis shows that the oxyfluoride is stable in atmospheres containing diatomic oxygen. However, the oxyfluoride phase can degrade with time at high temperatures in atmospheres containing water vapor, because of the higher stability of HF compared with H2O.

Activity of TiO2 in the System ZrO2-TiO2 and Gibbs Energy of Formation of ZrTiO4

The activity of Ti02 in single and two··phase regions of ihe system ZrOrTi02 has heen measured lIsing solid state cells based on yttria··doped tho ria (YDT) as the solid electrolyte at 1373 K. The cells used can be represented as: Pt, Tio.07PtO.Y3 + Zrj.,Tix0 2 / YDT / Ti02 + Tio.07Pto.93, Pt Pt, Tio.07Pto.93 + ZrJ.xTix02 + ZrTi04 / YDT / Ti02+ Tio.07PtO.93, Pt In each cell the composition of Pt-Ti alloy was identical at hoth electrodes. The emf of the cell is therefore directly related to the activity of Ti02 in oxide phase or oxide phase mixture: aTiO~ :;: cxp (-4FE/RT). The activity coefficient of Ti02 in th~ zirconia-rich solid solution with monoclinic structure (CUl2 2" XTi02 2" 0) can be expressed as:In the zirconia-rich solid solution with tetragonal structure (0.085 2" X ri02 2" 0.03), the activity coefficient is given by:In YTi02 (± 0.012) = 2.354 (1-XTiO? )2 +0.064 The standard Gibbs energy of formation of ZrTi04 is -5650 (± 200) J/mol at 1373 K .

Thermodynamic activities in the Pb(Zr1−XTiX)O3 solid solution at 1373K

Although Pb(Zr1−XTiX)O3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1−XTiX)O3 solid solution with cubic perovskite structure and (Zr1−YTiY)O2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs–Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1−YTiY)O2 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model:View the MathML sourcewhere ΔGE,M is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution.

Gibbs energy of formation of CaCu3Ti4O12 and phase relations in the system CaO-CUO/CU2O-TiO2

he standard Gibbs energy of formation of CaCu3Ti4O12 (CCTO) from CaTiO3, CuO and TiO2 has been determined as a function of temperature from 925 to 1350 K using a solid-state electrochemical cell with yttria-stabilized zirconia as the solid electrolyte. Combining this result with information in the literature on CaTiO3, the standard Gibbs energy of formation of CCTO from its component binary oxides, CaO, CuO and TiO2, has been obtained: View the MathML source (CaCu3Ti4O12)/J mol−1 (±600) = −125231 + 6.57 (T/K). The oxygen chemical potential corresponding to the reduction of CCTO to CaTiO3, TiO2 and Cu2O has been calculated from the electrochemical measurements as a function of temperature and compared on an Ellingham diagram with those for the reduction of CuO to Cu2O and Cu2O to Cu. The oxygen partial pressures corresponding to the reduction reactions at any chosen temperature can be read using the nomograms provided on either side of the diagram. The effect of the oxygen partial pressure on phase relations in the pseudo-ternary system CaO–CuO/Cu2O–TiO2 at 1273 K has been evaluated. The phase diagrams allow identification of secondary phases that may form during the synthesis of the CCTO under equilibrium conditions. The secondary phases may have a significant effect on the extrinsic component of the colossal dielectric response of CCTO.

Phase Equilibria in the System Al2O3-CaO-CoO and Gibbs Energy of Formation of Ca3CoAl4O10

An isothermal section of the system Al2O3-CaO-CoO at 1500 K has been established by equilibrating 22 samples of different compositions at high temperature and phase identification by optical and scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy after quenching to room temperature. Only one quaternary oxide, Ca3CoAl4O10, was identified inside the ternary triangle. Based on the phase relations, a solid-state electrochemical cell was designed to measure the Gibbs energy of formation of Ca3CoAl4O10 in the temperature range from 1150 to 1500 K. Calcia-stabilized zirconia was used as the solid electrolyte and a mixture of Co + CoO as the reference electrode. The cell can be represented as: ( - )\textPt,\textCaAl 2 \textO 4 + \textCa 1 2 \textAl 1 4 \textO 3 3 + \textCa 3 \textCoAl 4 \textO 10 + \textCo//(CaO)ZrO 2 \text// \textCoO + \textCo,\text Pt ( + ). (−)PtCaAl2O4+Ca12Al14O33+Ca3CoAl4O10+Co//(CaO)ZrO2//CoO+Co Pt (+) From the emf of the cell, the standard Gibbs energy change for the Ca3CoAl4O10 formation reaction, CoO + 3/5CaAl2O4 + 1/5Ca12Al14O33 → Ca3CoAl4O10, is obtained as a function of temperature: \Updelta Gr\texto Unknown control sequence '\Updelta'/J mol−1 (±50) = −2673 + 0.289 (T/K). The standard Gibbs energy of formation of Ca3CoAl4O10 from its component binary oxides, Al2O3, CaO, and CoO is derived as a function of temperature. The standard entropy and enthalpy of formation of Ca3CoAl4O10 at 298.15 K are evaluated. Chemical potential diagrams for the system Al2O3-CaO-CoO at 1500 K are presented based on the results of this study and auxiliary information from the literature.

La-Doped Ba2In2O5 Electrolyte: Pechini Synthesis, Microstructure, Electrical Conductivity, and Application for CO Gas Sensing

Dense (Ba1―xLax)2In2O5+x (BLIO) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were fabricated using powders obtained by the Pechini method. The formation of BLIO powders was investigated by using X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The calcination temperature and time were optimized. The sintered (Ba1―xLax)2In2O5+x electrolytes showed a relative density greater than ∼97%, and the major phase of three electrolyte compositions was indexed as a cubic perovskite. The electrical conductivity of BLIO ceramics at elevated temperatures in air was measured by ac-impedance spectroscopy. The activation energies for conduction in BLIO were 102 kJ mol―1 between 473 and 666 K and 118 kJ mol―1 between 769 and 873 K, which are comparable to that for 8 mol % yttria-stabilized cubic zirconia. Mixed-potential gas sensors utilizing BLIO-based electrolytes exhibited good sensitivity to different CO concentrations from ∼100 to ∼500 ppm and excellent selectivity to methane at around 873 K.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

System Ho-Rh-O: Phase Equilibria, Chemical Potentials and Gibbs Energy of Formation of HoRhO3

The thermodynamic properties of the HoRhO3 were determined in the temperature range from 900 to 1300 K by using a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of orthorhombic perovskite HoRhO3, from Ho2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure, can be expressed by the equation; Delta G(f)degrees((ox)) (+/- 78)/(J/mol) = -50535 + 3.85(T/K) Using the thermodynamic data of HoRhO3 and auxiliary data for binary oxides from the literature, the phase relations in the Ho-Rh-O system were computed at 1273 K. Thermodynamic data for intermetallic phases in the binary Ho-Rh were estimated from experimental enthalpy of formation for three compositions from the literature and Miedema's model, consistent with the phase diagram. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1273 K, and temperature-composition diagrams at constant oxygen partial pressures were computed for the system Ho-Rh-O. The decomposition temperature of HoRhO3 is 1717(+/- 2) K in pure O-2 and 1610(+/- 2) K in air at a total pressure p(o) = 0.1 MPa.

Electrochemical determination of thermodynamic properties of DyRhO3 and phase relations in the system Dy-Rh-O

Thermodynamic properties of Dysprosium rhodite (DyRhO3) are measured in the temperature range from 900 to 1,300 K using a solid-state electrochemical cell incorporating yttria-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of DyRhO3 with O-type perovskite structure from its components binary oxides, Dysprosia with C-rare earth structure and beta-Rh2O3 with orthorhombic structure, can be represented by the equation: Delta G(f(OX))(O) (+/- 182)/J mol(-1) = -52710+3.821(T/K). By using the thermodynamic data for DyRhO3 from experiment and auxiliary data for other phases from the literature, the phase relations in the system Dy-Rh-O are computed. Thermodynamic data for intermetallic phases in the binary system Dy-Rh, required for constructing the chemical potential diagrams, are evaluated using calorimetric data available in the literature for three intermetallics and Miedema's model, consistent with the phase diagram. The results are presented in the form of Gibbs triangle, oxygen potential-composition diagram, and three-dimensional chemical potential diagram at 1,273 K. Temperature-composition diagrams at constant oxygen partial pressures are also developed. The decomposition temperature of DyRhO3 is 1,732 (+/- 2.5) K in pure oxygen and 1,624 (+/- 2.5) K and in air at standard pressure.

System Gd-Rh-O: Thermodynamics and phase relations

Thermodynamic properties of GdRhO3 are investigated in the temperature range from 900 to 1300 K by employing a solid-state electrochemical cell, incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of GdRhO3 from component binary oxide Gd2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure can be expressed as; Delta G(f(ox))(o)(+/- 60)/J mol(-1) = -56603 + 3.78(T/K) Based on the thermodynamic information on GdRhO3 from experiment and auxiliary data for binary oxides from the literature and estimated properties of Gd-Rh alloys, phase relations are computed for the system Gd-Rh-O at 1273 K. Gibbs free energies for intermetallic phases in the binary Gd-Rh are evaluated using calorimetric data available in the literature for two compositions and Miedema's model, consistent with the binary phase diagram. Isothermal section of the ternary phase diagram, oxygen potential-composition diagram and a 3-D chemical potential diagram for the system Gd-Rh-O at 1273 K are developed. Phase relations in the ternary Gd-Rh-O are also computed as a function of temperature at constant oxygen partial pressures. The ternary oxide, GdRhO3 decomposes to Gd2O3 with B-rare earth structure, metallic Rh and O-2 at 1759(+/- 2) K in pure O-2 and 1649(+/- 2) K in air at a total pressure P-0 -0.1 MPa. (c) 2012 Elsevier B.V. All rights reserved.