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Mechanisms of oxidation of Ni(II)-Fe(II) hydroxides in chloride-containing aqueous media: role of the pyroaurite-type Ni-Fe hydroxychlorides

Published online by Cambridge University Press:  09 July 2018

Ph. Refait  and
J.-M. R. Genin
Ph. Refait
Affiliation:
Laboratoire de Chimie Physique pour l'Environnement, UMR 9992 CNRS-Université Henri Poincaré, Equipe sur la Réactivité des Espèces du Fer, and Département de Science des Matériaux, ESSTIN, 405, rue de Vandoeuvre, F 54600 Villers-les-Nancy, France
J.-M. R. Genin
Affiliation:
Laboratoire de Chimie Physique pour l'Environnement, UMR 9992 CNRS-Université Henri Poincaré, Equipe sur la Réactivité des Espèces du Fer, and Département de Science des Matériaux, ESSTIN, 405, rue de Vandoeuvre, F 54600 Villers-les-Nancy, France
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Abstract

Ni-Fe pyroaurite-type hydroxychlorides were prepared by aerial oxidation of Ni(II)-Fe(II) hydroxides precipitated in aqueous solution with various P = Fe/Ni ratios. When P≥ 1/3, Ni(II)-Fe(II)-Fe(III) hydroxychlorides characterized by a specific Fe(IIl)/[Fe(II)+Ni(II)] ratio of 1/3, corresponding to the idealized formula of NiII3-xFeIIxFeIII(OH)8Cl.nH2O (with 0 ≤ x ≤ 3), were obtained at the end of the first stage of oxidation, In a second reaction stage, these hydroxychlorides oxidize with deprotonation of hydroxyl ions into O2- ions, i.e. the remaining FeII(OH)2 groups are transformed into FeIIIOOH groups. Along with the Ni(II)-Fe(III) hydroxychloride which contains a part of the FeIIIOOH groups a second phase is obtained. It is an amorphous Fe(III) or Ni(II)-Fe(III) oxyhydroxide when 1/3<P≤3/2, and a ferric oxyhydroxide identified as γ-FeOOH (lepidocrocite) when P>3/2. On the other side of the domain, when P<1/3, the Fe(III)/[Fe(II)+Ni(II)] ratio cannot reach the specific value of 1/3; this gives rise to a pyroaurite-type Ni(II)-Fe(III) hydroxychloride with a lower chloride content, that is with an average composition of NiII3+yFeIII1-y(OH)8Cl1-y.nH2O where y = {[4/(1+P)] - 3}, down to minimum Fe(III) and Cl contents corresponding to y = 1/3 (P = 1/5). The in situ mechanisms of oxidation of Ni(II)-Fe(II) hydroxides into Ni(H)-Fe(II)-Fe(III) hydroxychlorides are discussed.

Type
Research Article
Information
Clay Minerals , Volume 32 , Issue 4 , December 1997 , pp. 597 - 613
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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