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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
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Abstract

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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

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