Oxidation of magnetite in aerated aqueous media

摘要

Metastable equilibria involving phases less stable than hematite can be significantly more oxidizing than the calculated equilibrium between well-crystallized hematite and magnetite. In this report, generalized solubility and stability relationships between magnetite and Fe(sub 2)O(sub 3).xH(sub 2)O phases are derived to describe the metastable equilibria. Experiments with synthetic magnetite powders in aerated aqueous solutions show that crystalline hematite is formed within days at temperatures above 100 C in pure water or solutions containing anions (e.g., Cl(sup -), SO(sub 4(sup 2))(sup -), HCO(sub 3)(sup -) that do not form very strong surface complexes with iron oxides. In the presence of dissolved phosphate or silica, however, the dissolution-precipitation route to hematite is strongly inhibited, and maghemite is a persistent metastable product. Thus, phosphate or silica are expected to delay the approach to magnetite-hematite equilibrium in aerated groundwaters conditioned by magnetite. These findings are presented in the context of nuclear fuel waste disposal. (author). 63 refs., 1 tab., 11 figs. (Atomindex citation 27:000133)