RI 3340 Progress Reports - Metallurgical Division - 18. Studies in the Metallurgy of Copper

"In matte smelting of copper it has been established that the sulphpr present will combine with copper as long as the latter is present, and that thereafter it will combine with iron. The Cu-Fe ratio in the matte is determined by the Cu-S ratio, presumably owing to the much greater affinity of copper for sulphur or, expressed thermodynamically, the greater stability of copper sulphide in contact with silicate slag. Now, the work of Fournet and of Schütz, which is quoted in many elementary metallurgical texts, indicates that manganese ranks ahead of copper in its affinity for sulphur. Hence, we might expect that manganese could be concentrated from its admixture with iron. Compounds by matte smelting, and Rotts / has patented such a process. This greater affinity of manganese or sulphur is used to advantage in iron metallurgy, also, in which it is well-known that sulphur will combine with manganese and separate from metallic iron as manganese sulphide. Manganese sulphide,however, is quite soluble in silicate slags. 5/ The loss of manganese in slag in any attempted matte smelting is therefore great.If this solubility of manganese sulphide is slag is a physical one and the reaction MnO + FeS MnS + FeOIs substantially complete, then it might be expected that the addition of copper sulphide, which is almost entirety insoluble in slag, would serve to extract the manganese sulphide with the formation of a manganese-copper matte on the other hand, if an equilibrium exists in the above reaction, a copper sulphide layer would displace that equilibrium in one direction or the other, according to whether iron sulphide or manganese sulphide were more soluble in the matter layer."