or all the ferric oxide is used up. If the ferric oxide first disappears, the equilibrium corresponds with a point on the dotted line in the middle area of Fig. 121, which represents equilibria between FeO + C as solid phases, and a mixture of carbon monoxide and dioxide as gas phase. If the temperature is higher than 685°, at which temperature the curve for C—CO—CO2 cuts that for Fe—FeO—CO—CO2; then, when all the ferric oxide has disappeared, the concentration of CO2 is still too great for the coexistence of FeO and C. Consequently, there occurs the reaction C + CO2 = 2CO, and the composition of the gas phase alters until a point on the upper curve is reached. A further increase in the concentration of CO is opposed by the reaction FeO + CO = Fe + CO2, and the pressure remains constant until all the ferrous oxide is reduced and only iron and carbon remain in equilibrium with gas. If the quantities of the substances have been rightly chosen, we ultimately reach a point on the dotted curve in the upper part of Fig. 121.
Fig. 121 shows us, also, what are the conditions under which the reduction of ferric to ferrous oxide by carbon can occur. Let us suppose, for example, that we start with a mixture of carbon monoxide and dioxide at about 600° (the lowest point on the dotted line), and maintain the total pressure constant and equal to one atmosphere. If the temperature is increased, the concentration of the carbon dioxide will diminish, owing to the reaction C + CO2 = 2CO, but the ferric oxide will undergo no change until the temperature reaches 647°, the point of intersection of the dotted curve with the curve for FeO and Fe3O4. At this point further increase in the concentration of carbon monoxide is opposed by the reduction of ferric oxide in accordance with the equation Fe3O4 + CO = 3FeO + CO2. The pressure, therefore, remains constant until all the ferric oxide has disappeared. If the temperature is still further raised, we again obtain a univariant system, FeO + C, in equilibrium with gas (univariant because the total pressure is constant); and if the temperature is raised the composition of the gas must undergo change. This is effected by the reaction C + CO2 = 2CO. When the
temperature rises to 685°, at which the dotted curve cuts the curve for Fe—FeO, further change is prevented by the reaction FeO + CO = Fe + CO2. When all the ferrous oxide is used up, we obtain the system Fe + C in equilibrium with gas. If the temperature is now raised, the composition of the gas undergoes change, as shown by the dotted line. The two temperatures, 647° and 685°, give, evidently, the limits within which ferric or ferrous oxide can be reduced directly by carbon.
It is further evident that at any temperature to the right of the dotted line, carbon is unstable in presence of iron or its oxides; while at temperatures lower than those represented by the dotted line, it is stable. In the blast furnace, therefore, separation of carbon can occur only at lower temperatures, and the carbon must disappear on raising the temperature.
Finally, it may be remarked that the equilibrium curves show that ferrous oxide is most easily reduced at 680°, since the concentration of the carbon monoxide required at this temperature is a minimum. On the other hand, ferric oxide is reduced with greatest difficulty at 490°, since at this temperature the requisite concentration of carbon monoxide is a maximum.
Other equilibria between solid and gas phases are: Equilibrium between iron, ferric oxide, water vapour, and hydrogen,[[380]] and the equilibria between carbon, carbon monoxide, carbon dioxide, water vapour, and hydrogen,[[381]] which is of importance for the manufacture of water gas.
CHAPTER XVIII
SYSTEMS OF FOUR COMPONENTS