Determination of Calcium Vapour Pressure in the Thermal Production of Calcium Metal

Abstract The production of metallic calcium, by reduction of lime with aluminium, was investigated. Using a modified form of the effusion method, the vapour pressure of calcium above the reaction: 4CaO + 2Al ~ 3Ca + CaO.AI203 was determined and found to vary from 1.0 to 1.3 mm. Hg from 1,150° to l,200°C. From the magnitudes of the various thermodynamic quantities involved, together with a consideration of the known chemical characteristics of the reaction, it was suggested that the reaction proceeded by reduction of lime with aluminium vapour. INTRODUCTION The conventional production of metals by reduction of their ores by carbon (or carbon monoxide) may be represented by the equilibrium: MO+ R [] RO+ M . . . . . . . . . .(1) where MO represents the metal oxide, and R the reducing agent (carbon or carbon monoxide). The free energy change ?F° associated with the reaction is given by -?F° = RTlnKp . . . . . . . . ... . (2) where R is the gas constant, T the absolute temperature, and KP the equilibrium constant. It should be noted that ?F° represents ? the standard free energy gained by the system and hence -?F° is the free energy gained by the surroundings - and that as ?F° increases K must decrease, and conversely. For metals above manganese in the electromotive series, the ?F° associated with reaction would quantity and from it can be seen that this corresponds to a small fraction for K. The equilibrium pressure of the oxide of carbon represented by RO is then too near its concentration in the furnace gases for the reaction to proceed in an internally fired furnace. For the practical reduction of such metals, fuel fired furnaces are inadequate. Electric furnaces may be used to give higher temperatures with lower concentration of carbon oxides and the reaction may still proceed. However, for many metals such as calcium and aluminium the formation of stable carbides or acetylides may prevent production of the metal by this reaction. In this case, either electrolytic methods must be used, orrecourse must be had to reducing agents other than carbon. It is the latter method which is under consideration here.