Extractive Metallurgy Division - Thermodynamics of Iron-Silicate Slags: Slags Saturated with Gamma Iron

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,