Part VII – July 1969 – Communications - Nonisothermal Electromotive Force of Galvanic Cells with Zirconia-Lime or Thoria-Lime Electrolyte

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.'