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Dissolution of Iron Oxides and Oxyhydroxides in Hydrochloric and Perchloric Acids

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Clays and Clay Minerals

Abstract

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

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

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

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.]

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Author notes

  1. P. S. Sidhu

    Present address: Department of Soils, Punjab Agricultural University, Ludhiana, 141004, India

  2. R. M. Cornell

    Present address: Chemistry Department, University of Berne, Berne, Switzerland

  3. J. P. Quirk

    Present address: Waite Agricultural Research Institute, University of Adelaide, Glen Osmond, South Australia, 5064, Australia

Authors and Affiliations

  1. Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009, Australia

    P. S. Sidhu, R. J. Gilkes, R. M. Cornell, A. M. Posner & J. P. Quirk

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  1. P. S. Sidhu
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  2. R. J. Gilkes
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  3. R. M. Cornell
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  4. A. M. Posner
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  5. J. P. Quirk
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Deceased August 1980.

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Sidhu, P.S., Gilkes, R.J., Cornell, R.M. et al. Dissolution of Iron Oxides and Oxyhydroxides in Hydrochloric and Perchloric Acids. Clays Clay Miner. 29, 269–276 (1981). https://doi.org/10.1346/CCMN.1981.0290404

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  • DOI: https://doi.org/10.1346/CCMN.1981.0290404

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