Technical Papers and Discussions - Technical Notes - Note on the Distribution of Sulphur between Molten Iron and Slag (Metals Tech., October 1948, T.N. 7)

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations