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Synthesis and Properties of Poorly Crystalline Hydrated Aluminous Goethites

Published online by Cambridge University Press:  01 July 2024

Martin Venn Fey  and
Joe Boris Dixon
Martin Venn Fey*
Affiliation:
Department of Soil and Crop Sciences, Texas Agricultural Experiment Station, Texas A&M University, College Station, Texas 77843
Joe Boris Dixon
Affiliation:
Department of Soil and Crop Sciences, Texas Agricultural Experiment Station, Texas A&M University, College Station, Texas 77843
*
1Present address: Department of Soil Science and Agrometerology, University of Natal, P.O. Box 375, Pietermaritzburg 3200, Republic of South Africa.
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Abstract

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Al-substituted goethites were prepared by rapid oxidation of mixed FeCl2-AlCl3 solutions at pH 6.8 in the presence of CO2 at 25°C. A combination of Al substitution and adsorption of CO2 reduced crystal size (except for an increase at small additions of Al) and produced unusual thin, porous particles. Product goethites had surface areas up to 283 m2/g and unit-cell expansions induced by hydration. Substitution of Al for Fe reduced the 111 spacing and increased infrared OH-bending vibrational frequencies. Al substitution split the goethite dehydroxylation endotherm during differential thermal analysis into a doublet and increased the temperature of all reactions. Both cold and hot alkali solutions dissolved Al from the goethite structure.

After drying the product in vacuo at 110°C. X-ray powder diffraction data indicated minimal deviation from Vegard's law for the goethite-diaspore solid solution up to about 30 mole % Al substitution. Goethite prepared in the presence of 40 mole % Al had a 111 spacing of 2.403 Å corresponding to 36 mole % structural Al if Vegard's law was obeyed. Rapid oxidation of mixed FeCl2-AlCl3 solutions appears to be conducive to a higher degree of Al substitution in goethite than alkaline aging of hydroxy-Fe(III)-Al coprecipitates.

Резюме

Резюме

Аl-замещенные гетиты были приготовлены путем быстрого окисления смешанных растворов FeCl2-AlCl3 при рН = 6,8 в присутствии СO2 при температуре 25°С. Сочетание замещения А1 и адсорбции СO2 уменьшало разиер кристаллов (исключая их увеличение при малых добавках Аl) и производило необычно тонкие, пористые частицы. Полученные гетиты имели площади поверхности до 283 M2/г и расширение элементарных ячеек, вызванное гидрацией. Замещение алюминия ферритом уменьшило 111 параметр решётки и увеличило инфракрасные ОН-изгибающие колебательные частоты. Замещение Аl расщепило эндотермальные кривые дегидроксилации гетита во время дифференциального термического анализа в дуплет и увеличило температуру всех реакций. Оба, холодный и горячий щелочные растворы вытесняли Аl из структуры гетита. После высушения продукта в вакууме при 110°С, данные по рентгеновской порошковой дифракции показали минимальное отклонение от закона Вегарда для твёрдых растворов гетита-диаспора до около 30 молярных % замещения А1. Гетит, приготовленный в присутствии 40 молярных % Аl, имел 111 расстояние, равное 2,403 Å, что соответствует 36 молярных % структурного А1, если применить закон Вегарда. Быстрое окисление смешанных растворов FeCl2-AlCl3 может скорее привести к замещению А1 в гетите, чем щелочное старение совместных осадков гидрокси-Fe(III)-Al. [Е.С.]

Resümee

Resümee

Al-substituierte Goethite wurden durch schnelle Oxidation von FeCl2-AlCl3-Lösungsgemischen bei pH 6,8 und bei der Anwesenheit von CO2 bei 25°C hergestellt. Eine Kombination von Al-Substitution und CO2-Adsorption reduzierte die Kristallgröße (ausgenommen einer Vergrößerung der Kristalle bei geringer Al-Zugabe) und erzeugte ungewöhnlich dünne, poröse Partikel. Die erzeugten Goethite hatten eine Oberfläche bis zu 283 m2/g und zeigten Vergrößerungen der Einheitszelle aufgrund von Hydratation. Die Substitution von Al für Fe reduzierte den 111-Abstand und vergrößerte die OH-Deformations-schwingungsfrequenzen im Infrarot. Bei der Differentialthermoanalyse wurde die Dehydroxylierungs-Endotherme des Goethit dutch Al-Substitution in ein Dublett aufgespalten und erhöhte die Temperatur aller Reaktionen. Sowohl kalte als auch heiße Alkali-Lösungen lösten Aluminium aus der Goethitstruktur.

Röntgenpulverdiffraktometer-Daten zeigten nach dem Trocknen des Produktes im Vakuum bei 110°C eine minimale Abweichung von Vegard'schen Gesetz für Goethit-Diaspor-Mischkristalle bis zu 30 Mol.−% Al-Substitution. Goethit, der in der Anwesenheit von 40 Mol.−% Al hergestellt wurde, hatte einen 111-Abstand von 2,403 Å, was bei Gültigkeit des Vegard'schen Gesetzes 36 Mol.−% Al in der Struktur entspräche. Die schnelle Oxidation von FeCl2-AlCl3-Lösungsgemischen scheint für eine höhergradige Al-Substitution im Goethit förderlicher zu sein als die Alterung dutch alkalische Lösungen von Hydroxy-Fe(III)-A1-Mischfällungen. [U.W.]

Résumé

Résumé

Des goethites substituées à l'Al ont été préparées par oxidation rapide de solutions mélangées FeCl2-AlCl3 à un pH de 6,8 en présence de CO2 à 25°C. Une combinaison de substitution à Al et d'adsorbtion de CO2 a réduit la taille du cristal (sauf pour un agrandissement lors de l'addition de petites quantités d'Al) et a produit des particules rares, minces, et poreuses. Les goethites produites avaient des aires de surface jusqu’ à 283 m2/g et des expansions de maille induites par hydration. La substitution d'Al à Fe a réduit l'espacement (111) et a accru les fréquences vibrationelles pliant OH de l'infrarouge. La substitution d'Al a divisé I'endotherme de déshydroxylation de la goethite pendant l'analyse thermique différentielle en un doublet e t a accru la température de toutes les réactions. Des solutions chaudes et froides alkalines ont dissolu l'Al de la structure de la goethite.

Après avoir seché le produit in vacuo à 110°C, des données de diffraction poudrée aux rayons-X ont indiqué une déviation minimale de la loi de Vegard pour la solution solide goethite-diaspore jusqu’à près de 30 mole % de substitution d'Al. La goethite préparée en présence de 40 mole % d'Al avait un espacement (111) de 2,403 Å correspondant à 36 mole % d'Al structural si la loi Vegard était suivie. L'oxidation rapide de solutions mélangées FeCl2-AlCl3 semble être plus favorable à un plus haut degré de substitution d'Al dans la goethite que le vieillisement alkalin de coprécipités hydroxy-Fe(III)-Al. [D.J.]

Keywords

AluminumDiasporeGoethiteInfraredSynthesisVegard's lawX-ray powder diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 29 , Issue 2 , April 1981 , pp. 91 - 100
Copyright
Copyright © 1981, The Clay Minerals Society

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