Hostname: page-component-848d4c4894-wg55d Total loading time: 0 Render date: 2024-05-15T06:57:30.881Z Has data issue: false hasContentIssue false
  • English
  • Français

Transformation of Hausmannite into Birnessite in Alkaline Media

Published online by Cambridge University Press:  02 April 2024

R. M. Cornell  and
R. Giovanoli
R. M. Cornell
Affiliation:
ETH Zürich, Laboratory for Inorganic Chemistry, ETH-Zentrum, CH-8092, Zürich, Switzerland
R. Giovanoli
Affiliation:
University of Bern, Laboratory for Electronmicroscopy, Freiestrasse 3, CH-3000 Bern 9, Switzerland
Get access Rights & Permissions [Opens in a new window]

Abstract

The transformation of hausmannite (Mn3O4) into a K-bearing, 7-Å phyllomanganate (K-birnessite) in KOH was followed using X-ray powder diffraction and transmission electron microscopy. The transformation involved dissolution of Mn3O4 followed by reprecipitation of the 7-Å phase. The rate-determining step was the dissolution of Mn3O4. The reaction was accelerated by increasing the pH and/or the temperature of the system.

K-birnessite precipitated initially as thin, irregular plates and films that gradually recrystallized to thicker, more structured plates and laths. A pseudohexagonal unit cell with a0 = 2.87 Å and c0 = 7.09 Å was found for this phase. Synthetic K-birnessite was stable in KOH at 70°C for many months. In neutral to slightly acidic media it converted rapidly to Mn7O13•5H2O, and in more acid media, it dissolved and reprecipitated as γ-MnO2. The replacement of K+ by Na+ was not achieved. Jacobsite and magnetite also underwent a dissolution/reprecipitation transformation in KOH.

Keywords

Alkaline solutionBirnessiteDissolutionHausmanniteManganeseSynthesis
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 3 , June 1988 , pp. 249 - 257
Copyright
Copyright © 1988, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bruyere, V. I. E. and Blesa, M. A., 1985 Acidic and reductive dissolution of magnetite in aqueous sulphuric acid. Site-binding model of experimental results J. Electroanal. Chem. Interfacial Electrochem. 182 141 – 156.CrossRefGoogle Scholar
Buser, W., Graf, P. and Feitknecht, W., 1954 Beitrag zur Kenntnis der Mangan(II)manganite und des γ-MnO2 Helv. Chim. Acta 37 2322 – 2333.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 jacobsite in alkaline media Clays & Clay Minerals 35 11 – 20.CrossRefGoogle Scholar
Cornell, R. M., Posner, A. M. and Quirk, J. P., 1975 The complete dissolution of goethite J. Appl. Chem. Biotechnol. 25 701 – 706.CrossRefGoogle Scholar
Fergusson, J. E., 1982 Inorganic Chemistry and the Earth .Google Scholar
Giovanoli, R., 1976 Vom Hexaquo-Mangan zum Mangan-Sediment. Reaktionssequenzen feinteiliger fester Mangan-oxidhydroxide Chimia 30 102 – 103.Google Scholar
Giovanoli, R., 1980 Layer structured manganese oxide hydroxides. VI. Recrystallization of synthetic buserite and the influence of amorphous silica and ferric hydroxide on its nucleation Chimia 34 308 – 310.Google Scholar
Giovanoli, R. and Hintze, B., 1986 Manganese oxide minerals Transactions XIII Congress Inter. Soc. Soil Sci., 1986, Vol. 5 Hamburg Int. Soc. Soil Science 335 – 345.Google Scholar
Giovanoli, R., Brütsch, R. and Lalou, C.l., 1978 L’Echange des ions de transition par le manganate-10Â et le manganate-7Å La Genèse des Nodules de Manganèse 305 – 315.Google Scholar
Giovanoli, R., Feitknecht, W., Maurer, R. and Häni, H., 1976 Über die Reaktion von Mn3O4 mit Säuren Chimia 30 307 – 309.Google Scholar
Giovanoli, R., Stähli, E. and Feitknecht, W., 1970 Über Oxidhydroxide des vierwerigen Mangans mit Schichtengitter. I. Natriummangan(II,III)manganate(IV) Helv. Chim. Acta 53 209 – 220.CrossRefGoogle Scholar
Golden, D. C., Dixon, J. B. and Chen, C. C., 1986 Ion exchange thermal transformation and oxidizing properties of birnessite Clay & Clay Minerals 34 511 – 520.CrossRefGoogle Scholar
Hem, J. D. and Lind, C. J., 1983 Nonequilibrium models for predicting forms of precipitated manganese oxides Geochim. Cosmochim. Acta 47 2037 – 2046.CrossRefGoogle Scholar
Hixon, A. W. and Crowell, J. H., 1931 Dependence of reaction velocity upon surface agitation Ind. Eng. Chem. 23 923 – 981.CrossRefGoogle Scholar
Holton, D. M., Maskell, W. C., Tye, F. L. and Pearce, L., 1985 The behaviour of γ-MnO2 and reduced forms in concentrated potassium hydroxide solution Power Sources 10 London Paul Press Ltd.Google Scholar
Maeda, Y. and Hirono, S., 1981 Electron microscopic observations on the dendrites of synthetic α-FeOOH particles Japan. J. Appl. Phys. 20 1991 – 1992.CrossRefGoogle Scholar
Strobel, P. and Charenton, J.-C., 1987 On the synthesis of various non-stoichiometric forms of manganese dioxide Rev. Chim. Miner. 24 1 – 22.Google Scholar
Stumm, W. and Giovanoli, R., 1976 On the nature of particulate manganese in simulated lake waters Chimia 30 423 – 4125.Google Scholar
Valverde, N., 1976 Investigations on the rate of dissolution of ternary oxide systems in acidic solutions Ber. Bunsenges. Phys. Chem. 81 380 – 384.CrossRefGoogle Scholar
van Olphen, H., 1977 Clay Colloid Chemistry 2nd New York Wiley.Google Scholar