Albany Paper - Electrolytic Lead-Refining

A solution of lead-fluosilicate, containing an excess of fluosilicic acid, has been found to work very satisfactorily as an electrolyte for refining lead. It conducts the current well, iseasily handled and stored, non-volatile and stable under electrolysis, may be made to contain a considerable amount of dissolved lead, and is easily prepared from inexpensive materials. It possesses, however, in common with other lead electrolytes, the defect of yielding a deposit of lead lacking in solidity, which grows in crystalline branches toward the anodes, causing short circuits. But if a reducing-action (practically accomplished by the addition of gelatine or glue) be given to the solution, a perfectly solid and dense deposit is obtained, having very nearly the same structure as electrolytically-deposited copper, and a specific gravity of about 11.36—that of cast-lead. Lead-fluosilicate may be crystallized in very soluble, brilliant crystals, resembling those of lead-nitrate and containing four molecules of water of crystallization, with the formula PbSiF,,4H20. This salt dissolves at 150 C. in 28 per cent. of its weight of water, making a sirupy solution of 2.38 sp. gr. Heated to 60° C., it melts in its water of crystallization. A neutral solution of lead-fluosilicate is partially decomposed on heating, with the formation of a basic insoluble salt and free fluosilicic acid, which keeps the rest of the salt in solution. This decomposition ends when the solution contains, perhaps, 2 per cent. of free acid; and the solution may then be evaporated without further decomposition. The solutioi~s desired for refining are not liable to this decomposition, since they contain much more than 2 per cent. of free acid. The electrical conductivity depends mainly on the acidity of the solution. My first experiments were carried out without the addition of gelatine to the fluosilicate solution. The lead-deposit con-