The tie-lines delineating equilibria between CoO-NiO and Co-Ni solid solutions in the ternary Co-Ni-O system at 1373 K have been determined by electron microprobe andedax point count analysis of the oxide phase equilibrated with the alloy. The oxygen potentials corresponding to the tie-line compositions have been measured using a solid oxide galvanic cell with calcia-stabilized zirconia electrolyte and Ni + NiO reference electrode. Activities in the metallic and oxide solid solution have been derived using a new Gibbs-Duhem integration technique. Both phases exhibit small positive deviations from ideality; the values ofG^E/X₁X₂ are 2640 J mol⁻¹ for the metallic phase and 2870 J mol⁻¹ for the oxide solid solution.

The thermodynamic capacity of a species (C_i)in a homogeneous phase is defined as (∂n_i/∂µ_{iP, T, nj}wheren_iis the total number of moles ofi per unit quantity of the system irrespective of the actual system chemistry andµ_iis its chemical potential. Based on this definition, the thermodynamic capacity of oxygen in non-reactive and reactive gas mixtures and in binary and ternary liquid solutions has been computed. For reactive gas mixtures containing stable chemical species which do not undergo significant dissociation such as CO + CO₂, H₂ + H₂O and H₂ + CO₂, the capacity curves show a maximum at equimolar ratio and a minimum at higher oxygen potentials. If one of the chemical species partly dissociates as in the case of H₂S in H₂ + H₂S mixtures or SO₃ in SO₂ + SO₃ mixtures, capacity curves do not exhibit such maxima and minima, especially at high temperatures. It would be difficult to produce stable oxygen fugacities when the capacity has a low value, for example at compositions near the minimum. Oxygen capacities of non-ideal liquid solutions, Cu-O and Cu-O-Sn, and heterogeneous systems formed at saturation with the respective oxides are discussed.

Gibbs energies of formation of CoF₂ and MnF₂ have been measured in the temperature range from 700 to 1100 K using Al₂O₃-dispersed CaF₂ solid electrolyte and Ni+NiF₂ as the reference electrode. The dispersed solid electrolyte has higher conductivity than pure CaF₂ thus permitting accurate measurements at lower temperatures. However, to prevent reaction between Al₂O₃ in the solid electrolyte and NiF₂ (or CoF₂) at the electrode, the dispersed solid electrolyte was coated with pure CaF₂, thus creating a composite structure. The free energies of formation of CoF₂ and MnF₂ are (± 1700) J mol⁻¹; {fx37-1} The third law analysis gives the enthalpy of formation of solid CoF₂ as ΔH° (298·15 K) = −672·69 (± 0·1) kJ mol⁻¹, which compares with a value of −671·5 (± 4) kJ mol⁻¹ given in Janaf tables. For solid MnF₂, ΔH°(298·15 K) = − 854·97 (± 0·13) kJ mol⁻¹, which is significantly different from a value of −803·3 kJ mol⁻¹ given in the compilation by Barinet al.

A methodology for evaluating the reactivity of titanium with mould materials during casting has been developed. Microhardness profiles and analysis of oxygen contamination have provided an index for evaluation of the reactivity of titanium. Microhardness profile delineates two distinct regions, one of which is characterised by a low value of hardness which is invariant with distance. The reaction products are uniformly distributed in the metal in this region. The second is characterised by a sharp decrease in microhardness with distance from the metal-mould interface. It represents a diffusion zone for solutes that dissolve into titanium from the mould. The qualitative profiles for contaminants determined by scanning electron probe microanalyser and secondary ion mass spectroscopy in the as-cast titanium were found to be similar to that of microhardness, implying that microhardness can be considered as an index of the contamination resulting from metal-mould reaction.

The Gibbs’ energies of formation of Pt₅La, Pt₅Ce, Pt₅Pr, Pt₅Tb and Pt₅ Tm intermetallic compounds have been determined in the temperature range 870–1100 K using the solid state cell:$$Ta,M + MF_3 /CaF_2 /Pt_5 M + Pt + MF_3 ,Ta$$.

The reversible emf of the cell is directly related to the Gibbs’ energy of formation of the Pt₅M compound. The results can be summarized by the equations:$$\begin{gathered} \Delta G_f^ \circ \left\langle {Pt_5 La} \right\rangle = - 373,150 + 6 \cdot 60 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Ce} \right\rangle = - 367,070 + 5 \cdot 79 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Pr} \right\rangle = - 370,540 + 4 \cdot 69 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Tb} \right\rangle = - 372,280 + 4 \cdot 11 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Tm} \right\rangle = - 368,230 + 4 \cdot 89 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \end{gathered} $$ relative to the low temperature allotropic form of the lanthanide element and solid platinum as standard states The enthalpies of formation of all the Pt₅M intermetallic compounds obtained in this study are in good agreement with Miedema’s model. The experimental values are more negative than those calculated using the model. The variation of the thermodynamic properties of Pt₅M compounds with atomic number of the lanthanide element is discussed in relation to valence state and molar volume.

The conductivity of MgAl₂O₄ has been measured at 1273, 1473 and 1673 K as a function of the partial pressure of oxygen ranging from 10⁵ to 10⁻¹⁴ Pa. The MgAl₂O₄ pellet, sandwiched between two platinum electrodes, was equilibrated with a flowing stream of either Ar + O₂, CO + CO₂ or Ar + H₂ + H₂O mixture of known composition. The gas mixture established a known oxygen partial pressure. All measurements were made at a frequency of 1 kHz. These measurements indicate pressure independent ionic conductivity in the range 1 to 10⁻¹⁴ Pa at 1273 K, 10⁻¹ to 10⁻¹² Pa at 1473 K and 10⁻¹ to 10⁻⁴ Pa at 1673 K. The activation energy for ionic conduction is 1·48 eV, close to that for self-diffusion of Mg²⁺ ion in MgAl₂O₄ calculated from the theoretical relation of Glyde. Using the model, the energy for cation vacancy formation and activation energy for migration are estimated.

The high temperature ceramic oxide superconductor YBa₂Cu₃O_7-x (1–2–3 compound) is generally synthesized in an oxygen-rich environment. Hence any method for determining its thermodynamic stability should operate at a high oxygen partial pressure. A solid-state cell incorporating CaF₂ as the electrolyte and functioning under pure oxygen at a pressure of 1·01 × 10⁵ Pa has been employed for the determination of the Gibbs’ energy of formation of the 1–2–3 compound. The configuration of the galvanic cell can be represented by: Pt, O₂, YBa₂Cu₃O_7−x, Y₂BaCuO₅, CuO, BaF₂/CaF₂/BaF₂, BaZrO₃, ZrO₂, O₂, Pt. Using the values of the standard Gibbs’ energy of formation of the compounds BaZrO₃ and Y₂BaCuO₅ from the literature, the Gibbs’ energy of formation of the 1–2–3 compound from the constituent binary oxides has been computed at different temperatures. The value ofx at each temperature is determined by the oxygen partial pressure. At 1023 K for O content of 6·5 the Gibbs’ energy of formation of the 1–2–3 compound is −261·7 kJ mol⁻¹.

New galvanic cell designs, incorporating one or two buffer electrodes, are developed to minimize the electrode polarization caused by electrochemical permeability of the electrolyte at high temperature. When a nonpolarizable reference electrode is employed, a cell with three-electrode compartments can be used to measure the chemical potential of oxygen in two-phase fields of ternary systems, associated with one degree of freedom at constant temperature. A buffer electrode is placed between the reference and measuring electrodes. The buffer electrode, maintained at approximately the same oxygen chemical potential as the measuring electrode, absorbs the semipermeability flux of oxygen between reference and measuring electrodes.

When the reference electrode is polarizable, two buffer electrodes are required between the reference and measuring electrodes. The reference and reference-buffer electrodes have the same chemical potential of the active species. Similarly the measuring electrode and its buffer are of approximately the same chemical potential. A significant chemical potential difference exists only between the two buffers, which may become polarized due to coupled transport of ions and electronic defects through the electrolyte. Since the reference and measuring electrodes are insulated, the emf of the solid state cell is unaffected. The use of the buffer electrode designs permit more accurate thermodynamic measurements on metal and ceramic systems at high temperature.

The composition of Pt-Rh alloys that co-exist with Rh₂O₃ in air have been identified by experiment at 1273 K. The isothermal sections of the phase diagram for the ternary system Pt-Rh-O at 973 K and 1273 K have been computed based on experimentally determined phase relations and recent thermodynamic measurements on Pt_1−XRh_X alloys and Rh₂O₃. The composition dependence of the oxygen partial pressure for the oxidation of Pt_1−XRh_X alloys at different temperatures, and temperature for the oxidation of the alloys in air are computed. The diagrams provide quantitative information for optimization of the composition of Pt_1−XRh_X alloys for high temperature application in oxidizing atmospheres.

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 Δ_f(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.

Isothermal stability field diagrams for Ln−O−Cl systems (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) are developed by taking partial pressures of volatile components oxygen and chlorine as variables. Thermodynamic properties of all the oxides and trichlorides (LnCl$_3$) are available in the literature. However, data for oxychlorides (LnOCl) and dichlorides (LnCl$_2$) are limited. Based on systematic trends in stability of these compounds across the lanthanide series, missing data are estimated to construct the diagrams for 13 Ln−O−Cl systems at 1000 K. All the lanthanide elements form stable LnCl$_3$ and LnOCl. Dichlorides of Nd, Sm, Eu, Dy, Tm and Yb are stable. For systems in which dichlorides are unstable (Ln = La, Ce, Pr, Gd, Tb, Ho, Er), the LnOCl is in equilibrium with the metal (Ln) and the stability field of LnOCl is sandwiched between those of oxides and trichlorides. Stability field diagrams of lanthanide systems forming stable LnCl$_2$ are of two kinds: in the first kind (Ln = Nd,Dy) the stability fields of Ln and LnOCl are in contact and the stability field of LnOCl separates the fields of chlorides and oxides. In diagrams of the second kind (Ln = Sm, Eu, Tm, Yb) there is a direct equilibrium between the oxides and dichlorides at low partial pressures of oxygen and chlorine. There is no contact between the stability fields of Ln and LnOCl; the stability field of LnOCl intervenes between the oxide and chloride phases only at higher partial pressures.