RI 8704 Electrochemical Determination of Thermodynamic Properties of Manganomanganic Oxide and Manganese Sesquioxide

The Bureau of Mines investigated thermodynamic properties of Mn304 (manganomanganic oxide) and Mn203 (manganese sesquioxide). The standard Gibbs energies of formation (?Gf°) of Mn304 and Mn203 from their lower oxides were determined with high-temperature galvanic cells using stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, MnO, Mn304//Zr0 2//02(g, 0.0112 atm), Pt, with the overall cell reaction 6Mn0(c) + 02(g, 0.0112 atm) = 2Mn304(c), where- 02 refers to indicated partial pressure of oxygen at the reference electrode. Similar measurements were obtained for the cell Pt, Mn304, Mn203//ZrO2//02(g, 0.0115 atm), Pt, with the overall cell reaction 4Mn304(c) + 02(g, 0.0115 atm) = 6Mn203(c). Equilibrium oxygen pressures for the Mn0-Mn304-02 and Mn304-Mn203-02 systems were measured and may be expressed for the respective systems as [23,400 109 P02 T + 11.91 (764.9 - 1,208.6 K) and log p02 = - 11,957 + 9.66 T (968.6 - 1,208.2 K),] where pressure (p02) is in atmospheres and temperature (T) is in kelvins. Standard thermodynamic properties of Mn304 and Mn203 were derived from these measurements and auxiliary thermodynamic data from the literature.