In a fundamental study of the physical chemistry of steelmaking slag, equilibra bet- ween hydrogen-water vapour gas mixtures and liquid slags contained in solid iron crucibles have been measured for four binary slags, FetO-CaO, FetO-Si02, FetO-TiO2 and FetO-Al203 at 14000C. From the data, the activity of iron oxide and the ratio of ferrous and ferric ions (A = Fe3+/Fe2+) were calculated for the slag composition. The best ionic model is found to be that based on regular solution of cations. The oxygen distribution between slag and metal is quantitatively expressed by this model over a wide range of slag composition.