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Effect of Cd(II) on the Ripening of Ferrihydrite in Alkaline Media

Published online by Cambridge University Press:  01 January 2024

Mariana Alvarez ,
María Fernanda Horst ,
Elsa E. Sileo  and
Elsa H. Rueda
Mariana Alvarez*
Affiliation:
INQUISUR, Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
María Fernanda Horst
Affiliation:
INQUISUR, Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
Elsa E. Sileo
Affiliation:
INQUIMAE, Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina
Elsa H. Rueda
Affiliation:
INQUISUR, Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
*
*E-mail address of corresponding author: alvarezm@criba.edu.ar
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Abstract

To acquire a better understanding of the influence exerted by the presence of Cd2+ during the process of transforming ferrihydrite to goethite, the morphological and structural changes of several samples obtained by the addition of Cd2+ to a suspension of nascent goethite were explored, and their chemical reactivity in acid media assessed. The samples (series Gi) were obtained by adding, at different times during the synthesis process, Cd2+ ions to ferrihydrite (Fe5HO8.4H2O) formed in alkaline media. The suspensions were aged for 5 days at 70°C, and the amorphous materials were extracted using a HCl solution (series GHCl-i). The X-ray diffraction (XRD) patterns showed that a goethite-like phase was formed, and chemical analyses indicated that the Cd content, xCd, increased with the earlier addition of the Cd2+ ions to the Fe oxyhydroxide suspension. Lattice parameters and cell volume, obtained by the Rietveld simulation of XRD data, indicated an enlargement of the cell parameters of goethite in line with the Cd-for-Fe substitution. In order to determine the influence of oxalate ions on the non-extracted solids, a second set of samples was also prepared that was kept in contact with an ammonium oxalate solution for 4 h (series Gox-i). The dissolution behavior of two series of Cd goethites and of a third series, obtained from coprecipitation of Fe3+ and Cd2+ ions in alkaline media, was observed. Kinetics measurements in 4 M HCl showed that the initial dissolution rate of samples Gox-i decreased with aging time, while the opposite effect was observed for series GHCl-i. Dissolution–time curves were well described by the Kabai equation, and activation energies were calculated using the Arrhenius equation. The results indicate that the presence of Cd during the crystallization process of goethite leads to the formation of a Cd goethite with modified morphology, structural parameters, and chemical reactivity.

Keywords

Acid ReactivityAgingCadmium IncorporationGoethiteHCl ExtractionOxalate Extraction
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 2 , April 2012 , pp. 99 - 107
Copyright
Copyright © Clay Minerals Society 2012

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