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Dissolution of Iron Oxides and Oxyhydroxides in Hydrochloric and Perchloric Acids

Published online by Cambridge University Press:  01 July 2024

P. S. Sidhu ,
R. J. Gilkes ,
R. M. Cornell ,
A. M. Posner  and
J. P. Quirk
P. S. Sidhu*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009, Australia
R. J. Gilkes
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009, Australia
R. M. Cornell*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009, Australia
A. M. Posner
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009, Australia
J. P. Quirk*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009, Australia
*
1Present address: Department of Soils, Punjab Agricultural University, 141004, Ludhiana, India.
2Present address: Chemistry Department, University of Berne, Berne, Switzerland.
3Present address: Waite Agricultural Research Institute, University of Adelaide, Glen Osmond, South Australia, 5064, Australia.
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Abstract

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The dissolution of synthetic magnetite, maghemite, hematite, goethite, lepidocrocite, and akaganeite was faster in HCl than in HClO4. In the presence of H+, the Cl− ion increased the dissolution rate, but the ClO4− ion had no effect, suggesting that the formation of Fe-Cl surface complexes assists dissolution. The effect of temperature on the initial dissolution rate can be described by the Arrhenius equation, with dissolution rates in the order: lepidocrocite > magnetite > akaganeite > maghemite > hematite > goethite. Activation energies and frequency factors for these minerals are 20.0, 19.0, 16.0, 20.3, 20.9, 22.5 kcal/mole and 5.8 × 1011, 1.8 × 1010, 7.4 × 107, 5.1 × 1010, 2.1 × 1010, 3.0 × 1011 g Fe dissolved/m2/hr, respectively. The complete dissolution of magnetite, maghemite, hematite, and goethite is well described by the cube-root law, whereas that of lepidocrocite is not.

Резюме

Резюме

Растворение синтетического магнетита, маггемита, гематита, гетита, лепидокрокита и акаганеита происходило быстрее в НСl, чем в НСlO4. В присутствии Н+, ион Сl− увеличивал скорость реакции, а ион СlO4− не имел никакого эффекта. Это указывает на то, что формирование поверхностных комплексов Fe-Cl содействует растворению. Эффект температуры на начальную скорость реакции может быть описан формулой Аррениуса, при порядке скоростей растворения: лепидокрокит > магнетит > акаганеит > маггемит > гетит. Энергии активации и факторы частот для этих минералов были соответственно: 20,0, 19,0, 16,0, 20,3, 20,9, 22,5 ккал/моль и 5,8 × 1011, 1,8 × 1010, 7,4 × 107, 5,1 × 1010, 2,1 × 1010, 3,0 × 1011 грамма Fe растворенного/м2/час. Полное растворение магнетита, маггемита, гематита и гетита хорошо описывается законом кубического корня, однако растворение лепидокрокита не совпадает с этим законом. [Е.С.]

Resümee

Resümee

Synthetischer Magnetit, Maghemit, Haematit, Goethit, Lepidokrokit, und Akaganeit löste sich in HCl schneller als in HClO4. In Gegenwart von H+ vergrößerte Cl− die Löungsgeschwindigkeit, während ClO4− ohne Einfluß war. Dies deutet darauf hin, daß die Bildung von Fe-Cl-Oberfläichenkomplexen die Auflösung fördert. Der Temperatureffekt auf die anffängliche Lösungsgescbwindigkeiten kann durch die Arrhenius-Gleichung beschrieben werden, wobei sich für die Lösungsgeschwindigkeiten folgende Reihenfolge ergibt: Lepidokrokit > Magnetit > Akaganeit > Maghemit > Haematit > Goethit. Die Aktivierungsenergien bzw. Häufigkeitsfaktoren dieser Minerale sind 20,0, 19,0, 16,0, 20,3, 20,9, 22,5 kcal/Mol bzw 5.8 × 1011, 1,8 × 1010, 7,4 × 107, 5,1 × 1010, 2,1 × 1010, 3,0 × 1011 g Fe gelöst/m2/hr. Die vollständige Auflösung von Magnetit, Maghemit, Haematit, und Goethit wird durch das Kubikwurzelgesetz beschrieben, während es für die von Lepidokrokit nicht gilt. [U.W.]

Résumé

Résumé

La dissolution de magnétite, maghémite, hématite, goethite, lépidocrocite, et d'akaganéite synthétiques était plus rapide dans HCl que dans HClO4. En présence d'H+, l'ion Cl− a augmenté l'allure de dissolution, mais l'ion ClO4− n'avait aucun effet, suggérant que la formation de complexes Fe-Cl de surface aide la dissolution. L'effet de la température sur l'allure de dissolution peut être décrite par l’équation d'Arrhenius avec les allures de dissolution dans l'ordre suivant: lépidocrocite > magnétite > akaganéite > maghémite > hématite > goethite. Les énergies d'activation et les facteurs de fréquence pour ces minéraux sont 20,0, 19,0, 16,0, 20,3, 20;9, 22,5, kcal/mole et 5,8 × 1011, 1,8 × 1010, 7,4 × l07, 5,1 × 1010, 2,1 × 1010, 3,0 × 1011 g Fe dissolu/m2/hr, respectivement. La dissolution complète de magnétite, maghémite, hématite, et de goethite est bien décrite par la loi de racine cubique, tandis que celle de la lépidocrocite ne l'est pas. [D.J.]

Keywords

AcidAkaganeiteDissolutionGoethiteHematiteIron oxideLepidocrociteMaghemiteMagnetite
Type
Research Article
Information
Clays and Clay Minerals , Volume 29 , Issue 4 , August 1981 , pp. 269 - 276
Copyright
Copyright © 1981, The Clay Minerals Society

Footnotes

†

Deceased August 1980.

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