期刊
JOURNAL OF RAMAN SPECTROSCOPY
卷 42, 期 3, 页码 496-504出版社
WILEY-BLACKWELL
DOI: 10.1002/jrs.2729
关键词
sulfide; iron; oxidation; solid-state transformation; localized corrosion
类别
资金
- French national radioactive waste management agency (ANDRA)
In this study, Raman spectroscopy was used to precisely understand the mechanisms of oxidation of mackinawite (FeS). Two experimental conditions were considered: (1) oxidation in air at room temperature and (2) oxidation in acidic anoxic solutions at 80 degrees C. In both cases, the oxidation process began by the in situ oxidation of Fe(II) cations inside the crystal structure of mackinawite and led to Fe(III)-containing mackinawite, (Fe1-3xFe2xS)-Fe-II-S-III. The oxidation in air finally led to Fe(III) oxyhydroxides and elemental sulfur alpha-S-8, but greigite (Fe3S4) was observed as an intermediate compound. In anoxic acidic solutions, the product of the oxidation was proved to depend on the Fe/S concentration ratio. For Fe/S = 3/4, greigite was the only product obtained, and this allowed us to determine unambiguously the Raman spectrum of this compound. For Fe/S = 1/2, the reaction led to pyrite FeS2. Copyright (C) 2010 John Wiley & Sons, Ltd.
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