Abstract
The electrochemical reduction of molten on platinum or nickel electrodes produces insoluble that passivates the cathode at high current densities. The presence of small amounts of silver ions prevents this passivation by undergoing reduction to silver metal in the form of dendritic deposits that increase the effective area of the electrode. The deposited silver is unstable in molten and reacts with the melt to regenerate silver ions. Corrosion studies of silver coupons gave a weight loss rate of 280 μg h−1cm−2 in molten at 350°C, but of only 5 μg h−1cm−2 in at 375°C. The presence of water in the melt increases the corrosion rate of silver. Additions of , , , or to molten significantly decreases the corrosion rate. The addition of oxide ions to a containing melt produces a dark precipitate of in or , but not in . The decomposition reaction of into its elements is kinetically slow in molten nitrates with a rate similar to that observed in air.
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