Iron and Steel Division - The Manganese Equilibrium Under Simple Oxide Slags

IN the basic open hearth process the reaction of manganese in the bath with iron oxide in the slag attains a condition very closely approximating true equilibrium, and the distribution of manganese between slag and metal during the refining period is determined by the factors which control this equilibrium condition. For this reason a number of investigators have studied this reaction both in the laboratory and under various conditions of furnace operation. The principle reaction and its equilibrium constant are: FeO (in slag) + Mn = MnO (in slag) + Fe (liq.) [1] (MnO) .= (FeO),[%Mn] The symbols in parentheses represent activities of the two oxides in the slag which, in the simple slags consisting almost wholly of the two oxides, may be assumed equal to the respective mol fractions. The symbol (FeO)r is used to denote the total iron oxide computed as FeO; or it is the sum of the mol fraction of FeO plus twice that of Fe2O3. Early attempts to obtain laboratory data on this reaction suffered from failure to appreciate the great speed of the reaction. When slag and metal are cooled slowly together, the equilibrium shifts with temperature and the final compositions correspond to equilibrium at the freezing point rather than at bath temperature. The early work of Oberhoffer and Schenck¹ and of Tammann and Oelsen² apparently suffered from this source of error. In most of the other published laboratory investigationsa. '.' this error was not present but other uncertainties have existed, notably dependence upon optical temperature measurements and exposure to atmospheric oxidation.