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 almost-equal-to 11. The Fe(II)/Fe(III)ratio (x) was varied from 0.10 to 0.50. After stabilization by aging at pH congruent-to 8 in anaerobic conditions, hydrous precipitates were characterized by electron microscopy, Mossbauer spectroscopy, and kinetics of dissolution in acidic medium. At any x value, all stable products exhibited the structure of (oxidized) magnetite. For x less-than-or-equal-to 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 greater-than-or-equal-to 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.