Institute of Metals Division - The Graphical Representation of Metallurgical Equilibria (Correction, p 944)

The temperature dependence of the free energies of formation of metallurgically important oxides, sulphides, chlorides, carbonates and sulphates is presented graphically, whereby the task of deriving practical metallurgical information is greatly simplified. The diagrams have been revised according to the latest available thermodynamic data. WHILE it is true that much careful investiga-tional work remains to be done, there are already available in the literature sufficient thermo-dynamic data to enable the metallurgist to predict with reasonable confidence the equilibrium conditions to be expected in most important, and potentially important, metallurgical reactions. In this connection, the careful, critical compilations of K. K. Kelley and his collaborators in numerous U. S. Bureau of Mines Bulletins are particularly valuable. However, the translation of reliable thermo-dynamic data into metallurgical language unfortunately involves lengthy manipulations of the cumbersome formulas which can be set up from heat of formation, entropy, and heat capacity data. Many years ago, Kelley20 predicted that thermo-dynamic calculations would be made in the future "with the aid of free energy, heat content, and entropy tables, rather than by means of the algebraic methods employed at present", and where such tables are available they greatly simplify the task of deriving practical metallurgical information. However, in addition to these tables, there are also available one or two reliable graphical presentations, particularly of free energy data, which may be used in the same way as the tables, but which have the added advantages that interpolation is never necessary, and that the behavior of different metals or compounds may be compared at a glance. Some years ago Professor Robert Lepsoe, Head of the Department of Metallurgy at Norways Institute of Technology (N.T.H.), began a compilation of curves showing the temperature dependence of the heat contents of the elements, and the heat contents and heats and free energies of formation of the common metallurgical compounds. With such a compilation, the thermal and free energy requirements of a reaction may be read from curves in a matter of seconds; and this statement applies not only to the formation of compounds from their elements, and to the reverse dissociation, but to any reaction involving substances whose thermodynamic properties are available. This follows from the fact that heats and free energies of formation are completely additive. For example, the free energy change associated with the chlorination of a metallic oxide at any temperature, T, is given by the free energy of formation of the chloride at temperature T minus that of the oxide also at T; both of these quantities may be read directly from curves of the type suggested above. Since this early, unpublished work of Lepsoe, both Ellingham7 and Richardson and Jeffes46 have