Influence of Fe(II) on the Formation of the Spinel Iron Oxide in Alkaline Medium
Fe(II) and Fe(III) in various proportions were coprecipitated by NH3 at pH ≈ 11. The Fe(II)/Fe(III) ratio (x) was varied from 0.10 to 0.50. After stabilization by aging at pH ≃ 8 in anaerobic conditions, hydrous precipitates were characterized by electron microscopy, Mössbauer spectroscopy, and kinetics of dissolution in acidic medium. At any x value, all stable products exhibited the structure of (oxidized) magnetite. For x ≤ 0.30, two distinct species were coexisting: the one (“m”) was made up of ca. 4nm-sized particles with a low Fe(II) content (Fe(II)/Fe(III) ≈ 0.07), and the other (“M”) consisted of particles of larger, more or less distributed sizes, and composition Fe(II)/Fe(III) ≈ 0.33; “M” increased relative amount with increasing x. For x ≥ 0.35, “M” was the only constituent and its Fe(II)/Fe(III) ratio was equal to x. “M” is identified with (nonstoichiometric) magnetite, whereas “m” is likely to be an oxyhydroxide. Mechanisms of formation are discussed, and a phase diagram is proposed which schematizes the evolution of the coprecipitation products with x and with time. Addition of Fe(II) after the precipitation of Fe(III), instead of coprecipitation, yielded very similar results.
Key WordsDissolution Ferrihydrite Maghemite Magnetite Mössbauer spectroscopy
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