The theory of the lime-roasting processes is not yet well established. It is recognized that the explanation offered by Huntington and Heberlein in their original patent specification is erroneous. There is no good evidence in their process, or any other, of the formation of the higher oxide of lime, which they suggest.
At the present time there are two views. In one, formulated most explicitly by Professor Borchers, there is formed in this process a plumbate of calcium, which is an active oxidizing agent. A formation of this substance was also described by Carmichael in his original patent, but he considered it to be the final product, not the active oxidizing agent.
In the other view, the lime, or limestone, serves merely as a diluent of the charge, enabling the air to obtain access to the particles of galena, without liquefaction of the latter. The oxidation of the lead sulphide is therefore effected chiefly by the air, and the process is analogous to what takes place in the bessemer converter or in the Germot process of smelting, or perhaps more closely to what might happen in an ordinary roasting furnace, provided with a porous hearth, through which the air supply would be introduced. Roasting furnaces of that design have been proposed, and in fact such a construction is now being tested for blende roasting in Kansas.
Up to the present time, the evidence is surely too incomplete to enable a definite conclusion to be reached. Some facts may, however, be stated.
There is clearly reaction to a certain extent between lead sulphide and lead sulphate, as in the reverberatory smelting furnace, because prills of metallic lead are to be observed in the lime-roasted charge.
There is a formation of sulphuric acid in the lime-roasting, upon the oxidizing effect of which Savelsberg lays considerable stress, since its action is to be observed on the iron work in which it condenses.
Calcium sulphate, which is present in all of the processes, being specifically added in the Carmichael-Bradford, evidently plays an important chemical part, because not only is the sulphur trioxide expelled from the artificial gypsum, but also it is to a certain extent expelled from the natural gypsum, which is added in the Carmichael-Bradford process; in other words, more sulphur is given off by the charge than is contained by the metallic sulphides alone.
Further evidence that lime does indeed play a chemical part in the reaction is presented by the phenomena of lime-roasting in clay dishes in the assay muffle, wherein the air is certainly not blown through the charge, which is simply exposed to superficial oxidation as in ordinary roasting.
The desulphurized charge dropped from the pot is certainly at much below the temperature of fusion, even in the interior, but we have no evidence of the precise temperature condition during the process itself.
Pyrite and even zinc blende in the ore are completely oxidized. This, at least, indicates intense atmospheric action.