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Influence of Fe(II) on the Formation of the Spinel Iron Oxide in Alkaline Medium

Published online by Cambridge University Press:  28 February 2024

J. P. Jolivet ,
P. Belleville ,
E. Tronc  and
J. Livage
J. P. Jolivet
Affiliation:
Chimie de la Matière Condensée (CNRS URA 1466), Université Pierre et Marie Curie, Paris 05, France
P. Belleville
Affiliation:
Chimie de la Matière Condensée (CNRS URA 1466), Université Pierre et Marie Curie, Paris 05, France
E. Tronc
Affiliation:
Chimie de la Matière Condensée (CNRS URA 1466), Université Pierre et Marie Curie, Paris 05, France
J. Livage
Affiliation:
Chimie de la Matière Condensée (CNRS URA 1466), Université Pierre et Marie Curie, Paris 05, France
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Abstract

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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.

Keywords

DissolutionFerrihydriteMaghemiteMagnetiteMössbauer spectroscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 40 , Issue 5 , October 1992 , pp. 531 - 539
Copyright
Copyright © 1992, The Clay Minerals Society

References

Chukhrov, F. V., Zvyagin, B. B., Gorshkov, A. I., Yermilova, L. P. and Balashova, V. V., 1973 Ferrihydrite Intl. Geol. Rev. 16 1131 – 1143 10.1080/00206817409471766.CrossRefGoogle Scholar
Coey, J M D and Khalafalla, D., 1972 Superparamagnetic γ-Fe2O3 Phys. Stat. Sol. 11 229 – 241 10.1002/pssa.2210110125.CrossRefGoogle Scholar
Cornell, R. M., 1988 The influence of some divalent cations on the transformation of ferrihydrite to more crystalline products Clay Miner. 23 329 – 332 10.1180/claymin.1988.023.3.10.CrossRefGoogle Scholar
Cornell, R. M. and Giovanoli, R., 1987 Effect of manganese on the transformation of ferrihydrite into goethite and jacobsite in alkaline media Clays & Clay Minerals 35 11 – 20 10.1346/CCMN.1987.0350102.CrossRefGoogle Scholar
Cornell, R. M. and Giovanoli, R., 1988 The influence of copper on the transformation of ferrihydrite (5Fe2O3 9H2O) into crystalline products in alkaline media Polyhedron 7 385 – 391 10.1016/S0277-5387(00)80487-8.CrossRefGoogle Scholar
Daniels, J. M. and Rosencwaig, A., 1969 Mössbauer spectroscopy of stoichiometric and nonstoichiometric magnetite J. Phys. Chem. Solids 30 1561 – 1571 10.1016/0022-3697(69)90217-0.CrossRefGoogle Scholar
De Bakker, P M A De Grave, E., Vandenberghe, R. E. and Bowen, L. H., 1990 Mössbauer study of small-particle maghemite Hyperf. Interac. 54 493 – 498 10.1007/BF02396078.CrossRefGoogle Scholar
Eggleton, R. A. and Fitzpatrick, R. W., 1988 Newdataand a revised structural model for ferrihydrite Clays & Clay Minerals 36 111 – 124 10.1346/CCMN.1988.0360203.CrossRefGoogle Scholar
Fischer, W. R., Schlichting, E. and Schwertmann, U., 1973 Die Wirkung von zweiwertigem Eisen auf Lösung und Umwandlung von Eisen(III)-hydroxiden Pseudogley and Gley 37 – 44.Google Scholar
Haneda, K. and Morrish, A. H., 1977 On the hyperfine field of γ-Fe2O3 small particles Phys. Lett. 64A 259 – 262 10.1016/0375-9601(77)90736-8.CrossRefGoogle Scholar
Henry, M., Jolivet, J. P. and Livage, J., 1992 Aqueous chemistry of metal cations: Hydrolysis, condensation, and complexation Structure and Bonding 77 154 – 206.Google Scholar
Jolivet, J. P. and Tronc, E., 1988 Interfacial electron transfer in colloidal spinel iron oxide. Conversion Fe3O4→γ-Fe2O3 in aqueous medium J. Colloid Interface Sci. 125 688 – 701 10.1016/0021-9797(88)90036-7.CrossRefGoogle Scholar
Jolivet, J. P. Massart, R. and Fruchart, J. M., 1983 Synthèse et étude physicochimique de colloïdes magnétiques non surfactés en milieu aqueux Nouv. J. Chim. 7 325 – 331.Google Scholar
Mann, S., Sparks, N H C Couling, S. B., Larcombe, M. C. and Frankel, R. B., 1989 Crystallochemical characterization of magnetic spinels prepared from aqueous solution J. Chem. Soc, Faraday Trans. 1 85 3033 – 3044 10.1039/f19898503033.CrossRefGoogle Scholar
Misawa, T., Hashimoto, K. and Shimodaira, S., 1974 The mechanism of formation of iron oxides and oxyhydroxides in aqueous solutions at room temperature Corrosion Sci. 14 131 – 149 10.1016/S0010-938X(74)80051-X.CrossRefGoogle Scholar
Morup, S., Dumesic, J. A. and Topsøe, H., 1980 Magnetic microcrystals Applications of Mössbauer Spectroscopy 2 1 – 53.Google Scholar
Morup, S., Topsae, H. and Lipka, J., 1976 Modified theory for Mössbauer spectra of superparamagnetic particles: Application to Fe3O4 J. Physique 37 287 – 290.Google Scholar
Murad, E., Bowen, L. H., Long, G. J. and Quin, T. G., 1988 The influence of crystallinity on magnetic ordering in natural ferrihydrites Clay Miner. 23 161 – 173 10.1180/claymin.1988.023.2.04.CrossRefGoogle Scholar
Murad, E. and Johnston, J. H., 1987 Iron oxides and oxyhydroxides Mössbauer Spectroscopy Applied to Inorganic Chemistry 2 507 – 582.Google Scholar
Murad, E. and Schwertmann, U., 1980 The Mössbauer spectrum of ferrihydrite and its relation to those of other iron oxides Amer. Mineral. 65 1044 – 1049.Google Scholar
Ramdani, A., Steinmetz, J., Gleitzer, C., Coey, J M D and Friedt, J. M., 1987 Perturbation de l’échange électronique rapide par les lacunes cationiques dans Fe3-xO4 (x < 0.09) J. Phys. Chem. Solids 48 217 – 228 10.1016/0022-3697(87)90016-3.CrossRefGoogle Scholar
Sawatzky, G. A., Van der Woude, F. and Morrish, A. H., 1969 Recoilless-fraction ratios for Fe57 in octahedral and tetrahedral sites of a spinel and a garnet Phys. Rev. 183 383 – 386 10.1103/PhysRev.183.383.CrossRefGoogle Scholar
Tamaura, Y., Buduan, P. V. and Katsura, T., 1981 Studies in the oxidation of iron (II) ion during formation of Fe3O4 and α-FeOOH by air oxidation of Fe(OH)2 suspensions J. Chem. Soc. Dalton Trans. 1807 – 1811.CrossRefGoogle Scholar
Tamaura, Y., Ito, K. and Katsura, T., 1983 Transformation of γ-FeOOH to Fe3O4 by adsorption of Fe(II) ion on 7-FeOOH J. Chem. Soc. Dalton Trans. 189 – 194.CrossRefGoogle Scholar
Tronc, E. and Bonnin, D., 1985 Magnetic coupling among spinel iron oxide microparticles by Mössbauer spectroscopy J. Physique Lett. 46 L437 – L443 10.1051/jphyslet:019850046010043700.CrossRefGoogle Scholar
Tronc, E., Belleville, P., Jolivet, J. P. and Livage, J., 1992 Transformation of ferric hydroxide into spinel by Fe(II) adsorption Langmuir 8 313 – 319 10.1021/la00037a057.CrossRefGoogle Scholar