Part XI - Papers - Kinetics of Near-Equilibrium Reduction of Wustite

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.