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Reductive Dissolution Kinetics of Al-Substituted Goethites

Published online by Cambridge University Press:  01 January 2024

Estela Gonzalez ,
María C. Ballesteros  and
Elsa H. Rueda
Estela Gonzalez
Affiliation:
Departamento de Química e Ingeniería Química, Universidad Nacional del Sur, Av. Alem 1253, 8000 - Bahía Blanca, Argentina
María C. Ballesteros
Affiliation:
Departamento de Química e Ingeniería Química, Universidad Nacional del Sur, Av. Alem 1253, 8000 - Bahía Blanca, Argentina
Elsa H. Rueda*
Affiliation:
Departamento de Química e Ingeniería Química, Universidad Nacional del Sur, Av. Alem 1253, 8000 - Bahía Blanca, Argentina
*
*E-mail address of corresponding author: ehrueda@criba.edu.ar
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Abstract

Several Al-substituted goethites were synthesized by hydrolysis of Fe3+ salt solutions. The kinetics of the reductive dissolution of these goethites in dithionite-ethylenediaminetetra acetic acid (D-EDTA) was studied at pH 5.5, at 303, 323 and 333 K. The initial dissolution rate (R) per unit of surface area decreases with Al substitution. In the sample with greater Al content (G″7), the kinetic profiles of the dissolved Fe fraction vs. time gave a small positive intercept. The kinetic profile of R as a function of EDTA initial concentration shows a significant weakening in the presence of Al. The maximum is flatter and wider in Al-substituted goethite than that of pure goethite. In sample G″7, where the Al content is 11.3 mol.% the maximum is obtained when the [D]:[EDTA] initial ratio is ∼4.5 vs. 2 in un-substituted goethite. These results can be attributed to the lesser density of the more active dimeric sites, the presence of more strongly bonded Al-O-Fe with regard to Fe-O and the small value for the ≡ Al-EDTA surface species constant. Activation energy (Ea) increases with Al substitution. Its value is doubled from GO (pure goethite) to G″7 (11.3 mol.% of Al). The frequency factor (A) acts in the opposite sense to Ea, but it is not sufficient to outweigh the effect of Ea.

Keywords

Al SubstitutionDithionite-EDTAIron OxideReductive Dissolution
Type
Research Article
Information
Clays and Clay Minerals , Volume 50 , Issue 4 , August 2002 , pp. 470 - 477
Copyright
Copyright © 2002, The Clay Minerals Society

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