Abstract
A reversible silver - silver chloride reference electrode for use in melts at high temperatures has been developed. It was found that the solution of silver chloride in an equimolar mixture of KCI-NaC1 melt is ideal for the range of concentrations studied, i.e. 1.0X10-3 to 6.0X10-2 mole fraction of AgCl. The electromotive force of the voltaic cell Co I CoCl2 (x2 ) AgCI (xi) I Ag, I KCI-NaCI (1/1 mole) II KCI-NaCI (1/1 mole) I in which the half-cell to the right contains the above-mentioned reference electrode, was measured as a function of CoC12 concentration. The applicability of the Nernst equation to this system vas established. Deviation from ideality was observed in the case of the solution of CoCl 2 in the melt solvent, and this was attributed to the formation of a complex. The dissociation constant of this complex was calculated as 4.50 X10-2 at 710° C. The effect of temperature on the electromotive force of this cell was also measured, and the heat of the cell reaction in the presence of solvent (Co + 2AgCI --> CoCl2 2Ag) was calculated from the data as 22.8±1.3 kcal. The thermodynamic significance of the standard electrode potential of the Co-Ag voltaic cell, derived experimentally as 0.324 volt, is discussed briefly
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