Statistico-Thermodynamical Studies on Fundamental Reactions concerning Steel-Making. VI : On the Configuration of Fe-O Molten Slag and its Interation with Gaseous Oxygen

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The iron and oxygen atom-ratio of Fe-O melts is continuously variable by the change of oxygen pressure in the gaseous phase. It is very reasonable that we suppose Fe-O melts are constructed by ionic components Fe^<++>, Fe^<+++> and O^<-->, thanks to the previous results on Fe-O solid-solution phases (ref. previous Reports II and IV) and the electro-conductivity of melts. We assume the following configurational model for Fe-O molten system : (1) Oxygen ions O^<--> are arranged on the face-centered cubic lattice (nearly close-packed), because they are very large compared with iron ions. (2) Fe^<++> ions are distributed on the tetrahedral and octahedral interstitial lattice points of the oxygen-ion lattice. (3) If any tetrahedral lattice point is occupied by a iron ion, its nearest octahedral lattice points are vacant, and it is the same for the nearest neighbors of octahedral iron ions. (4) Positive holes are randomly distributed on Fe^<++> ions, and thus Fe^<+++> ions are formed. Using the above model the partition function of the Fe-O molten slag was formulated by the statistical thermodynamic method, and the equilibrium relation between the slag composition and the pressure of oxygen in gas phase was calculated. These theoretical results are in good agreement with the measured values of Darken and Gurry (1946) in the wide range of pressure, 10^<-10> to 1 atm of O_2, and temperature 1400°to 1600℃.
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