Papers - Equilibria of Liquid Iron and Slags of the System Ca0-Mg0-Fe0-SiO2 (T.P. 1316, with discussion)

The relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steel-making processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the -subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of labora- tory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermo-dynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component svstem seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest