We can picture to ourselves how in the first period the savage smith, step by step, bettered his control over his fire, at once his source of heat and his deoxidizing agent.
The fuel has, in addition to its duties of deoxidizing and carburizing the iron and yielding the heat needed for melting both the iron and slag, the further task of desulphurizing the iron, probably by the reaction FeS+CaO+C=Fe+CaS+CO.
In the former case there is no later chance to remove sulphur, a minute quantity of which does great harm by leading to the formation of cementite instead of graphite and ferrite, and thus making the cast-iron castings too hard to be cut to exact shape with steel tools; in the latter case the converting or purifying processes, which are essentially oxidizing ones, though they remove the other impurities, carbon, silicon, phosphorus and manganese, are not well adapted to desulphurizing, which needs rather deoxidizing conditions, so as to cause the formation of calcium sulphide, than oxidizing ones.
After the ascending column of gases has done its work of heating and deoxidizing the ore,.
(4) This same strong deoxidizing action leads to the practically complete deoxidation and hence extraction of the iron.
But the strong deoxidizing conditions needed in the blast-furnace to remove sulphur tend strongly to deoxidize silica and thus to make the pig iron rich in silicon.
Next comes the deoxidizing and desulphurizing stage, of which the first step is to throw some strongly deoxidizing substance, such as coke or ferro-silicon, upon the molten metal, in order to remove thus the chief part of the oxygen which it has taken up during the oxidation of the phosphorus in the preceding stage.
It is by forming calcium sulphide that sulphur is removed in the manufacture of pig iron in the iron blast furnace, in the crucible of which, as in the electric furnaces, the conditions are strongly deoxidizing But in the Bessemer and open-hearth processes this means of removing sulphur cannot be used, because in each of them there is always enough oxygen in the atmosphere to re-oxidize any calcium as fast as it is deoxidized.
The reason for this is that in it the slag, by means of which all the purification must needs be done, is not heated effectively; that hence it is not readily made thoroughly liquid; that hence the removal of the phosphoric slag made in the early dephosphorizing stage of the process is liable to be incomplete; and that hence, finally, the phosphorus of any of this slag which is left in the furnace becomes deoxidized during the second or deoxidizing stage, and is thereby returned to befoul the underlying steel.
As we have seen, the removal of sulphur can be made complete only by deoxidizing calcium, and this cannot be done if much oxygen is present.
But this ancient furnace does its fourfold work of deoxidizing, melting, removing the gangue and desulphurizing, so very economically that it is not likely to be driven out in other places until the exhaustion of our coal-fields shall have gone so far as to increase the cost of coke greatly.
These additions seem to act in part by deoxidizing the minute quantity of iron oxide and carbonic oxide present, in part by increasing the solvent power of the metal for gas, so that even after freezing it can retain in solution the gas which it had dissolved when molten.
5 of a gramme of pure iron wire in a flask, in hydrochloric acid, oxidizing it with a little potassium chlorate, boiling off all traces of chlorine, deoxidizing by one of the methods described above, and titrating with the solution.