Iron and Steel Division - Attainment of Equilibrium in Gas-Metal Reactions (Discussion page 1550)

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-