Thermodynamics and phase equilibria involving the spinel solid solution FexMg1-xCr2O4

Activities of FeCr2O4 in the spinel solid solutions Fe X Mg1−X Cr2O4 (0<X<1) in equilibrium with pure iron and Cr2O3 have been measured in the temperature range 1050 to 1350 K by employing a bielectrolyte solid-state galvanic cell of the type Pt, Fe + Fe X Mg1−X Cr2O4 + Cr2O3//(Y2O3) ThO2/(CaO) ZrO2//Fe + FeCr2O4 + Cr2O3, Pt Activities of both the components exhibit small negative deviation from the ideal behavior, characterized by the regular solution parameter Ω s =−2260 (±200) J/mol. The lattice parameter of the spinel solid solutions quenched from 1200 K was found to obey Vegard’s law. The phase relations in the FeO-MgO-Cr2O3 system have been deduced from the results obtained in this study together with other relevant thermodynamic data from the literature. The tie-lines between the solid solutions with rock salt and spinel structures represent the influence of intercrystalline ion exchange. The tie-lines are skewed toward the FeCr2O4 corner, primarily because of the higher stability of FeCr2O4 compared to MgCr2O4, with respect to their component binary oxides. The oxygen partial pressure corresponding to the two three-phase regions, Fe + Fe X Mg1−X Cr2O4 + Cr2O3 and Fe + Fe Y Mg1−Y O + Fe X Mg1−X Cr2O4, have been evaluated as a function of composition at 1200 K

Oxidation of alkaline earth sulfides to sulfates: Thermodynamic aspects

The emf of the galvanic cell, Pt, Ni + NiO/(CaO) ZrO2/MS + MSO4, Ir, Pt, where M is calcium, strontium, or barium, has been measured in the temperature range 850 to 1100 K. From these measurements the Gibbs’ energy changes for the oxidation of sulfides of alkaline earth metals to their respective sulfates have been calculated. The results are compared with available thermodynamic data in the literature. The agreement varies from ±2 kJ for the strontium system to ±20 kJ in the case of barium. Trends in the stabilities of alkaline earth sulfates are discussed in relation to the properties of the cationic species involved

Thermodynamic study of Fe2O3 Fe2(SO4)3 equilibrium using an oxyanionic electrolyte (Na2SO4 I)

The emf of the cell, Pt, Ar + O2 + SO2 + SO3/Na2SO4-I/Fe2O2 + Fe2(SO4)3, Pt, has been measured in the temperature range 800 to 1000 K, using a gas mixture of known input composition as the reference electrode. The equilibrium composition of the reference gas at the measuring temperatures was computed using the thermodynamic data on the gaseous species reported in the literature. A mixture of ferric oxide and sulfate was kept in a closed system to ensure establishment of equilibrium partial pressure at the electrode. The cell was designed to avoid physical contact between Fe2(SO4)3 and Na2SO4 electrolyte. Uncertainties arising from the formation of sulfate solid solution were thus eliminated. The Gibbs’ energy of formation of ferric sulfate calculated from the emf is discussed in comparison with data reported in the literature. There is no evidence for the formation of oxysulfates in the Fe-S-0 system. Based on the results obtained in the present study for Fe2(SO4)3 and literature data for other phases, chemical potential diagrams have been constructed for the Fe-S-O system at 900 and 1100 K

Determination of the thermodynamic properties of \{xMgO + (1 - x)MnO\} (s, sln) from a solid-electrolyte galvanic cell in the temperature range 1163 to 1318 K

The thermodynamic activities of MgO in the NaCl-type solid solutions which can exist in \{xMgO + (1 − x)MnO\} have been determined in the temperature range 1163 to 1318 K from a solid-state galvanic cell incorporating $MgF_2$ as the solid electrolyte. The activities of MnO have been calculated by a graphical Gibbs-Duhem integration method. The activities of both the components exhibit positive deviations from ideality over the entire composition range. The excess molar enthalpies are found to be positive. Further, \{xMgO + (1 - x)MnO\} does not conform to regular-solution behaviour. The origin of the excess thermodynamic properties is discussed in relation to the cationic size disparity and the crystal-field effects

Phase relations and activities in the Co Ni O system at 1373 K

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/X 1 X 2 are 2640 J mol−1 for the metallic phase and 2870 J mol−1 for the oxide solid solution

Chemical potentials of oxygen for fayalite-quartz-lron and fayalite-quartz-magnetite equilibria

The oxygen potentials corresponding to fayalite-quartz-iron (FQI) and fayalite-quartz-magnetite (FQM) equilibria have been determined using solid-state galvanic cells: Pt,Fe + Fe2SiO4 + SiO2/(Y2O3)ZrO2/Fe + \r"FeO,\l"Pt and Pt, Fe3O4 + Fe2SiO4 + SiO2/(Y2O3)ZrO2/Ni + NiO, Pt in the temperature ranges 900 to 1400 K and 1080 to 1340 K, respectively. The cells are written such that the right-hand electrodes are positive. Silica used in this study had the quartz structure. The emf of both cells was found to be reversible and to vary linearly with temperature. From the emf, Gibbs energy changes were deduced for the reactions: 0.106Fe (s) + 2Fe0.947O (r.s.) + SiO2 (qz) → Fe2SiO4 (ol) δG‡= -39,140+ 15.59T(± 150) J mol-1 and 3Fe2SiO4 (ol) + O2 (g) → 2Fe3O4 (sp) + 3SiO2 (qz) δG‡ = -471,750 + 160.06 T±} 1100) J mol-1 The “third-law≓ analysis of fayalite-quartz-wustite and fayalite-quartz-magnetite equilibria gives value for δH‡298 as -35.22 (±0.1) and -528.10 (±0.1) kJ mol-1, respectively, independent of temperature. The Gibbs energy of formation of the spinel form of Fe2SiO4 is derived by com-bining the present results on FQI equilibrium with the high-pressure data on olivine to spinel transformation of Fe2SiO4

Oxygen potentials, Gibbs' energies and phase relations in the Cu-Cr-o system

Thermodynamic properties of ternary compounds, cuprous and cupric chromites ($CuCro_2$ , $CuCr_2$ $o_4$ ), and oxygen potentials corresponding to three three-phase regions in the $Cu-Cr-o$ system have been measured in the temperature range 900 to 1350 K using a solid state galvanic cell incorporating calcia-stabilized zirconia. Cuprous chromite was found to be nearly stoichiometric. The compositions of non-stoichiometric cupric chromite saturated with $Cuo$ and $Cr_2o_3$ have been determined using electron microprobe and energy dispersive X-ray analysis. The results of this study resolve discrepancies in Gibbs" energies of cuprous and cupric chromites reported in the literature. A ternary phase diagram for the $Cu-Cr-o$ system at 1150 K and phase relations in air for the $Cu_2o$ - $Cuo$ - $Cr_2o_3$ system as a function of temperature have been derived based on the new thermodynamic data. The phase diagram given in the literature is found to be inaccurate

Spinel-Corundum Phase Equilibria in the Systems Mn-Cr-Al-O and Co-Cr-Al-O at 1373 K

The tie lines delineating ion-exchange equilibria between MCr2O4-MAl2O4 spinel solid solution, where M is either Mn or Co, and Cr2O3-Al2O3 solid solution with the corundum structure were determined at 1373 K by electron microprobe and E0AX point count analysis of the oxide phases equilibrated with metallic Co and Au-5% Mn. The component activities in the spinel solid solutions are derived from the tie lines and the thernodynamic data for Cr2O3-Al2O3 soiid solutions available hi the literature. The Gibbs free energies of mixing calculated from the experimental data are discussed in relation to the values derived from the cation distribution a.odel based on the site preference energies and assuming random mixing on both tetrahedral and octahedral sites. Positive deviations from ideality observed in this study suggest a miscibility gap for both series of spinel solid solutions at low temperatures in the absence of oxidation

Phase equilibria in the Co Ni F system and activities in (CoxNi1 x)F2 solid solutions at 1373 K

The tie-lines delineating equilibria between CoF2-NiF2 and Co-Ni solid solutions in the ternary Co-Ni-F system at 1373 K have been determined by electron microprobe and EDAX point count analysis of the equilibrated phases. Activities in the fluoride solid solution have been derived from the knowledge of activitycomposition relation in the metallic solid solution and tie-line data,using a modified form of the Gibbs-Duhem integration. The fluorine potentials corresponding to the tie-line compositions have been calculated.The excess Gibbs' energy of mixing for the fluoride solid solution derived from the present data can be represented by the expressio