Iron and Steel Division - Silicon-Oxygen Equilibrium in Liquid Iron-A Revision

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram