Die Untersuchung der (CuO, PdO)-Mischkristallbildung und ihre Beteiligung an den Gleichgewichten des Systems Cu—Pd—O

Schmahl, N. G.; Minzl, E.

doi:10.1524/zpch.1965.47.3_4.142

Cited by 23 publications

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“…The activities of MgO were calculated by a Gibbs-Duhem integration. The activity-composition relations obtained by Navrotsky [2] agree well with those determined by Schmahl and Minzl [1] for the rock salt phase and the two-phase region containing the rock salt phase and guggenite. No direct measurements of activity of MgO have been reported before.…”

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Thermodynamic activities at 1273 K in the system cupric oxide-magnesium oxide using a solid-state galvanic cell

Raghavan

1987

J Mater Sci Lett

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Schmahl and Minzl [1] examined the phase relationships in the system CuO-MgO by the X-ray method. The phase relations at 1273K are characterized by two terminal solid solutions, the MgO-rich rock salt phase and the CuO-rich tenorite phase which are separated by three regions, i.e. the region in which the rock salt phase and a compound of CuO and MgO, the guggenite phase, coexist; the single-phase guggenite region over a varying composition range and a two-phase region in which the guggenite and the tenorite coexist. The activity-composition relations for CuO and hence the phase-boundary limits were determined at 1273 K by directly measuring the oxygen pressures in equilibrium with the phases in the presence of Cu20. Navrotsky [2] determined the activities of CuO at 1273 K by measuring the oxygen pressures for the equilibrium-phase assemblages. The activities of MgO were calculated by a Gibbs-Duhem integration. The activity-composition relations obtained by Navrotsky [2] agree well with those determined by Schmahl and Minzl [1] for the rock salt phase and the two-phase region containing the rock salt phase and guggenite. No direct measurements of activity of MgO have been reported before.In the present work, a solid-state galvanic cell with MgF2 as the solid electrolyte was used to measure MgO activities at 1273 K in the equilibrium phases of the CuO-MgO system. The suitability and reliability of this technique to measure MgO activities in solid solutions containing MgO are well documented [3][4][5][6].Magnesium fluoride, for making the solid electrolyte pellets and electrodes, was prepared according to the method of Taylor and Schmalzried [3]. The electrolyte was prepared by pressing the powder in a cylindrical die. The green pellet was then sintered in an atmosphere of CO2-free dry oxygen gas at 1323 K for 4 h. Samples of the desired composition were weighed from dried reagent-grade CuO and MgO and ground under acetone. The equilibrium phases were prepared by sintering the oxide-mixture pellets at 1273 K in a stream of CO2-free dry oxygen gas. The product was ground and sintered again at 1273K for 30 to 72h. The formation of true equilibrium phases was confirmed by the X-ray method using CuK~ radiation. The apparatus used in the present investigations was similar to that described earlier [7]. The performance of the polycrystalline MgF 2 as the solid electrolyte was checked by operating the cell:

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confidence: 85%

“…Schmahl and Minzl [1] examined the phase relationships in the system CuO-MgO by the X-ray method. The phase relations at 1273K are characterized by two terminal solid solutions, the MgO-rich rock salt phase and the CuO-rich tenorite phase which are separated by three regions, i.e.…”

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confidence: 99%

Thermodynamic activities at 1273 K in the system cupric oxide-magnesium oxide using a solid-state galvanic cell

Raghavan

1987

J Mater Sci Lett

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Thermodynamics and Defect Chemistry of Some Oxide Solid Solutions Part II: Pair Interactions

Driessens

1968

Ber Bunsenges Phys Chem

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This paper is concerned with solid solutions of two isostructural ionic oxides. Relations are derived between activities and composition on the assumptions that interactions between nearest and next‐nearest neighbours are involved, and that the distribution of the cations present in any sublattice is random.Proof is given that such solutions will be regular if they show no substitutional disorder. A comparison is made with some experimental data given in the literature. The available data show that binary systems of halides, silicates, oxides with rock‐salt structure and oxides with spinel structure are indeed regular, if there is no substitutional disorder. The energy of interactions between next‐nearest neighbours could be evaluated and varied from – 3 to +4 kcal/mol. The nature of these interactions is discussed. It is shown that the „interaction”︁ energy originates from Coulomb energy, crystal‐field stabilization and deviations from stoichiometry with respect to the oxygen content and that further the chemical binding between next‐nearest neighbours is negligibly small except in solid solutions of Fe3O4 and inverse ferrites with other spinels.

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Zellen mit festen Oxidelektrolyten auf der Basis von Zirkonoxid und Thoriumoxid

Fischer¹,

Janke²

1975

Metallurgische Elektrochemie

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Die Untersuchung der (CuO, PdO)-Mischkristallbildung und ihre Beteiligung an den Gleichgewichten des Systems Cu—Pd—O

Cited by 23 publications

References 0 publications

Thermodynamic activities at 1273 K in the system cupric oxide-magnesium oxide using a solid-state galvanic cell

Thermodynamic activities at 1273 K in the system cupric oxide-magnesium oxide using a solid-state galvanic cell

Thermodynamics and Defect Chemistry of Some Oxide Solid Solutions Part II: Pair Interactions

Zellen mit festen Oxidelektrolyten auf der Basis von Zirkonoxid und Thoriumoxid

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