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Phase evolution and kinetics of the oxidation of monosulfide solid solution under isothermal conditions
- Source :
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Thermochimica Acta . Mar2005, Vol. 427 Issue 1/2, p13-25. 13p. - Publication Year :
- 2005
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Abstract
- Abstract: In this work, the effects of stoichiometry on phase evolution during the oxidation of mss (monosulfide solid solution) were investigated. A series of mss samples, ranging from Fe7.9S8 to Fe2.37Ni5.53S8 were synthesized from pure components. Samples with grain size 53–90μm were oxidized at 830 and 850K in air in a muffle furnace. The Rietveld quantitative phase analysis method was used to identify and quantify the phase information from powder X-ray diffraction (XRD) profiles. Hematite was observed and accounted for most of the oxidized iron. Nickel in mss was not oxidized to NiO under current isothermal conditions; instead, it was finally transformed to Ni17S18. Hematite, Fe2(SO4)3 and residual mss were identified in the final phases after 24h oxidation of the mss composition Fe7.9S8; hematite and Ni17S18 for compositions Fe6.15Ni1.54S8 and Fe2.37Ni5.53S8; hematite, Ni17S18 and pentlandite for Fe6.4Ni1.6S8. Given a constant iron to nickel atomic ratio of 4:1, the sample with lower metal concentration, Fe6.15Ni1.54S8, showed a faster oxidation rate than its metal richer counterpart, Fe6.4Ni1.6S8. The mean oxidation rates for these two samples are 1.85 × 10-4 and 1.22 × 10-4s-1 respectively for 1.5h heating at 830K. Vyazovkin''s theory of changing activation energy (Ea) with reaction extent (y) was employed in the current kinetic study. The activation energy was determined using a model-free method. The oxidation of Fe6.4Ni1.6S8 exhibited a higher Ea than Fe6.15Ni1.54S8 over the course of reaction. The activation energy increases with y from 67.1 to 103.3kJmol-1 for mss composition Fe6.15Ni1.54S8; 76.1 to 195.0kJmol-1 for Fe6.4Ni1.6S8. Bulk compositions Fe7.9S8, Fe2.37Ni5.53S8 were selected to give a constant metal to sulfur atomic ratio of 7.9:8. Oxidation of Fe2.37Ni5.53S8 achieved equilibrium within 1h, compared to 5h for Fe7.9S8. [Copyright &y& Elsevier]
- Subjects :
- *SULFUR compounds
*OXIDATION
*STOICHIOMETRY
*DYNAMICS
Subjects
Details
- Language :
- English
- ISSN :
- 00406031
- Volume :
- 427
- Issue :
- 1/2
- Database :
- Academic Search Index
- Journal :
- Thermochimica Acta
- Publication Type :
- Academic Journal
- Accession number :
- 16204401
- Full Text :
- https://doi.org/10.1016/j.tca.2004.08.007