Extractive Metallurgy Division - Thermodynamics of Suboxide Vaporization

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At