Abstract
As a contribution to the systematic study of iron oxide thermodynamics, this work reports enthalpies of formation of green rust, a double layered (Fe II, Fe III) hydroxide with the ideal stoichiometry Fe II 1 - x Fe III x ( OH ) 2 [ A m - ] y / m · n H 2 O , with sulfate as the anion in the interlayer. Samples were characterized by X-ray powder diffraction, thermogravimetric analysis, infrared spectroscopy, and Mössbauer spectroscopy. Full chemical analysis was performed. Contents of Fe II, Fe III, water, and sulfate were obtained. We report standard enthalpies of formation for green rust with different Fe II/Fe III ratios. Enthalpies of formation from single cation compounds, namely, Fe(OH) 2, Fe(OH) 3, FeSO 4 and H 2O show reasonable agreement with Gibbs free energies of formation from single cation compounds recalculated from the reported literature values. These values show that green rust has little stabilization over a mechanical mixture of these single cation compounds and there is no thermodynamic preference for any particular Fe II/Fe III ratio.
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