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Effect of Cobalt on the Formation of Crystalline Iron Oxides from Ferrihydrite in Alkaline Media

Published online by Cambridge University Press:  02 April 2024

R. M. Cornell  and
R. Giovanoli
R. M. Cornell
Affiliation:
ETH-Zentrum Zürich, Laboratory for Inorganic Chemistry, CH-8092 Zürich, Switzerland
R. Giovanoli
Affiliation:
University of Berne, Laboratory for Electron Microscopy, Freiestrasse 3 CH-3000 Berne 9, Switzerland
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Abstract

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At pH 12 Co-ferrihydrite transformed to either Co-goethite or Co-magnetite, the latter compound appearing at Co additions of > 18 mole %. Although Co was readily taken up by the magnetite structure, chemical analysis showed that no more than 7 mole % substitution of Co in goethite was achieved. Hematite formation was not strongly promoted by the presence of Co; with 9 mole % Co in the system, the amount of hematite relative to goethite in the product increased slightly. Co-substituted goethites grew as long, thin crystals. The presence of Co promoted some dendritic twinning of goethite. Cobalt retarded the transformation of ferrihydrite to more crystalline oxides mainly by stabilizing ferrihydrite against dissolution. A comparison of Co with divalent ions previously studied showed that their stabilizing ability decreases in the order Cu > Co > Mn, i.e., they follow the Irving-Williams series for the stability of metal complexes.

Keywords

CobaltCrystal growthFerrihydriteGoethiteSpinelTransmission electron microscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 37 , Issue 1 , February 1989 , pp. 65 - 70
Copyright
Copyright © 1989, The Clay Minerals Society

References

Abeck, W. and Hund, F., 1964 Process for the production of needle-shaped, cobalt-containing 7-ferric oxide crystalline particles U.S. Patent 3 117.Google Scholar
Ardizzone, S., Chittofrati, A. and Formaro, L., 1987 Iron(II) cobalt ferrites: Preparation and interfacial behaviour J. Chem. Soc, Farad. Trans. 783 1159 – 1168.CrossRefGoogle Scholar
Ardizzone, S., Formare, L. and Svieri, E., 1983 Preparation and characterization of magnetite samples having different stoichiometric composition J. Chem. Soc. Farad. Trans. I 79 2449 – 2456.CrossRefGoogle Scholar
Azaroff, L. V., 1960 Introduction to Solids New York McGraw-Hill.Google Scholar
Borggaard, O., 1987 Influence of iron oxides on cobalt adsorption by soils J. Soil Sci. 38 229 – 238.CrossRefGoogle Scholar
Cornell, R. M., 1987 Comparison and classification of the effects of simple ions and molecules upon the transformation of ferrihydrite into more crystalline products: Z Pflanzenernähr. Bodenk. 150 304 – 307.CrossRefGoogle Scholar
Cornell, R. M. and Giovanoli, R., 1985 Effect of solution conditions on the proportion and morphology of goethite formed from ferrihydrite Clays & Clay Minerals 33 424 – 432.CrossRefGoogle Scholar
Cornell, R. M. and Giovanoli, R., 1987 Effect of manganese on the transformation of ferrihydrite into goethite and ja-cobsite in alkaline media Clays & Clay Minerals 35 11 – 20.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.CrossRefGoogle Scholar
Feitknecht, W. and Michaelis, W., 1962 Über die Hydrolyse von Eisen(III)-Perchlorat-Lösungen Helv. Chim. Acta 26 212 – 224.CrossRefGoogle Scholar
Giovanoli, R., 1976 Vom Hexaquo-Mangan zum Mangan Sediment. Reaktionsequenzen feinteiliger fester Manga-noxidhydroxide ChimiaiO 118 – 119.Google Scholar
Halbach, P., Giovanoli, R. and von Borstel, D., 1982 Geo-chemical processes controlling the relationship between Co, Mn and Fe in early diagenetic deep sea nodules Earth Planet. Sci. Lett. 60 226 – 236.CrossRefGoogle Scholar
Irving, H. and Williams, R. J. P., 1953 Stability of transition metal complexes J. Chem. Soc 3192 – 3210.CrossRefGoogle Scholar
Lewis, D. G. and Schwertmann, U., 1979 The influence of Al on iron oxides. Part III. Preparation of Al goethites in M KOH Clay Miner. 14 115 – 126.CrossRefGoogle Scholar
Lim-Nunez, R., Gilkes, R. J., Schulze, L. G., van Ol-phen, H. and Mumpton, F. A., 1987 Acid dissolution of synthetic metal-containing goethite and hematites Proc. Int. Clay Conf., Denver, 1985 Indiana The Clay Minerals Society, Bloomington 197 – 204.Google Scholar
Maeda, Y. and Hirono, S., 1981 Electron microscopic observations of the dendrites of synthetic a-FeOOH particles Jpn. J. Appl. Phys. 20 1991 – 1992.CrossRefGoogle Scholar
Music, S., Gessner, M. and Wolf, R. H. H., 1979 Sorption of small amounts of cobalt on iron(III) oxide Mikrochim. Acta 6 105 – 112.CrossRefGoogle Scholar
Schulze, D. G., 1984 The influence of aluminum on iron oxides. VIII. Unit-cell dimensions of Al-substituted goethites and estimation of Al from them Clays & Clay Minerals 32 36 – 44.CrossRefGoogle Scholar
Schwertmann, U., 1964 Differenzierung der Eisenoxides des Bodens durch Extraktion mit einer Ammonium-oxalat-lösung: Z Pflanzenernähr. Düng. Bodenkd. 105 194 – 202.CrossRefGoogle Scholar
Schwertmann, U. and Fischer, W. R., 1966 Zur Bildung von a-FeOOH und a-Fe2O3 aus amorphem Eisen-(Ill)hydroxid: Z Anorg. Allg. Chem. 346 137 – 146.CrossRefGoogle Scholar
Schwertmann, U., Taylor, R. M., Schlichtling, E. and Schwertmann, U., 1972 The in vitro transformation of soil lepidocrocite to goethite Pseu-dogley and Gley: Genesis and Use of Hydromorphic Soils, Proc. Int. Soc. Soil Sci., Trans., Stuttgart, Germany 45 – 54.Google Scholar
Shannon, R. D. and Prewitt, C. T., 1969 Effective ionic radii in oxides and fluorides Acta Crystallogr. B25 925 – 946.CrossRefGoogle Scholar
Sidhu, P. S., Gilkes, R. J. and Posner, A. M., 1978 The synthesis and some properties of Co, Ni, Zn, Cu, Mn and Cd substituted magnetites J. Inorg. Nucl. Chem. 40 429 – 435.CrossRefGoogle Scholar
Stiers, W. and Schwertmann, U., 1985 Evidence for manganese substitution in synthetic goethites Geochim. Cos-mochim. Acta 49 1909 – 1911.CrossRefGoogle Scholar
Sugimoto, T., 1987 Preparation of monodisperse colloidal particles Adv. Colloid Interface Sci. 28 65 – 108.CrossRefGoogle Scholar
Sugimoto, T. and Matijevic, E., 1979 Formation of uniform spherical particles by crystallization from ferrous hydroxide gels J. Colloid Interface Sci. 74 227 – 243.CrossRefGoogle Scholar
Tamaura, Y., Buduan, P. V. and Katsura, T., 1981 Studies on the oxidation of iron(II) ion during formation of Fe3O4 and 7-FeOOH by air oxidation of Fe(OH)2 suspensions J. Chem. Soc. Dalton 1807 – 1811.CrossRefGoogle Scholar