Thermoelectric powers of cells with NaF-AlF3-Al2O3 melts

A thermodynamic description of the Peltier heat at the aluminum and the oxygen electrode in the system NaF-AlF3-Al2O3 is given. The thermoelectric power in melts with molar ratios n(NaF)/In-AlF3 from 3.0 to 1.0, saturated with alumina are measured. Seebeck coefficients for molten fluoride electrolytes saturated with alumina, electrolytes that are relevant for aluminum electrowinning electrolysis cells, are reported. The results allow determinations of Peltier heats of aluminum, oxygen and carbon electrodes in NaF-AlF3 electrolytes saturated with alumina. For molar ratios of n(NaF)/n(AlF3) between 2.6 and 1.2, there is a Peltier heating of the aluminum cathode. This heating is in the same order of magnitude as the electrolyte Joule heat, when the current density is 0.7 A cm(-2). For molar ratio n(NaF)/n(AlF3) equal to 1.0 the Peltier effect at the aluminum electrode approaches zero. From theoretical considerations we expect a drop also for molar ratio 3.0. For the anode we report a Peltier cooling that is larger than the heat produced by the anodic overvoltage, in melts with NaF/AlF3 molar ratio between 2.6 and 1.2 saturated with alumina.