Abstract
Pure iron and an Fe-41 weight percent (w/o) Ni alloy were reacted at temperatures in the range 793 to 1073 K with hydrogen-hydrogen sulfidenitrogen atmospheres corresponding to equilibrium p(S2) levels from 6.5:E-5 to 0.65 Pa. The kinetics of iron sulfidation were intermediate in form to linear and parabolic rate laws. The instantaneous parabolic rate constant was found to increase with extent of reaction until a constant value was reached. For fixed equilibrium sulfur pressures, the instantaneous rate increases with hydrogen sulfide partial pressure; for fixed hydrogen sulfide partial pressure, the instantaneous rate decreases as the equilibrium sulfur pressure is increased. It is demonstrated that hydrogen sulfide is the reactant species. A Langmuir-Hinshelwood kinetic model based on the slow dissociation of adsorbed hydrogen sulfide accounts satisfactorily for the unusual gas-phase compositional effects, and also for the rate at which the reacting system approaches the steady state. Similar effects were found for the Fe-Ni alloy, where nickel sulfide whisker formation results from localized catalysis of the hydrogen sulfide dissociation reaction.
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