Sulfidation of iron at high temperatures and diffusion kinetics in ferrous sulfide

Abstract

The kinetics and mechanism of iron sulfidation have been studied as a function of temperature (950–1200 K) and sulfur pressure (10⁻³-0.065 atm). It has been stated that a compact Fe_1−yS scale on iron grows according to the parabolic rate law as a result of outward lattice diffusion of metal ions through cation vacancies. The activation energy of sulfidation increases with sulfur pressure and the 1/n exponent increases with temperature. This nontypical dependence of iron sulfidation kinetics on temperature and pressure results from the analogous effect of both these parameters on defect concentration in ferrous sulfide. The chemical diffusion coefficients,^∼D_FeS, and diffusion coefficients of defects, D_d, in ferrous sulfide have been calculated on the basis of parabolic rate contacts of iron sulfidation and deviations from stoichiometry in ferrous sulfide. It has been shown that^∼D_FeS is practically independent of cation vacancy concentration whereas the diffusion coefficient of defects depends strongly on that parameter. A comparison of self-diffusion coefficients of iron in Fe_1−yS calculated from the kinetics of iron sulfidation to those obtained from radioisotopic studies indicates that within the range studied of temperatures and sulfur vapor pressures the outward diffusion of iron across the scale occurs preferentially along the c axis of columnar ferrous sulfide crystals.