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Influence of Silica Content on the Surface Charge Characteristics of Allophanic Clays

Published online by Cambridge University Press:  02 April 2024

A. Gonzales-Batista ,
J. M. Hernandez-Moreno ,
E. Fernandez-Caldas  and
A. J. Herbillon
A. Gonzales-Batista
Affiliation:
Catedra de Edafologia, Universidad de La Laguna, Santa Cruz de Teneriffe, Spain
J. M. Hernandez-Moreno
Affiliation:
Catedra de Edafologia, Universidad de La Laguna, Santa Cruz de Teneriffe, Spain
E. Fernandez-Caldas
Affiliation:
Catedra de Edafologia, Universidad de La Laguna, Santa Cruz de Teneriffe, Spain
A. J. Herbillon
Affiliation:
Section de Physico-Chimie Minérale du Musée Royal de l'Afrique Centrale and Université Catholique de Louvain, B-1348, Louvain-la-Neuve, Belgium
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Abstract

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The surface and charge characteristics of 6 allophanic clays originating from a climatosequence of Andisols have been studied by titration, ion retention, surface area, and reactivity measurements. Several properties of these clays, such as the pH of zero charge, the magnitude of the surface area, and the reactivity of structural hydroxyl groups, appear to be governed by their chemical composition, especially by their silica content. A similar relationship between the above properties and silica content also exists for synthetic aluminosilicate gels (often quoted in the literature as possible models of allophanes), despite their different structure to the natural clays. An explanation is that as desilication proceeds, octahedral polymeric units of aluminum progressively individualize in both the synthetic and natural samples. The surface areas of the aUophanic clays, based on the slope of the titration curve at pH 7, are closely related to the amounts of structural hydroxyl that can react with fluoride at about the same pH. The permanent negative charges are always very low, even for silica-rich, allophane-bearing samples. It is therefore suggested that all of these clays should be virtually free of tetrahedral aluminum.

Резюме

Резюме

Характеристики поверхности и заряда шести аллофановых глин, присходящих из климатического ряда Андисоли, исследовались путем титрования, измерений сохранения ионов, площади поверхности и реактивности. Несколько свойств этих глин, как pH нулевого заряда, величина площади поверхности, и реактивность структурных гидроксиловых групп, регулируется химическим составом, особенно содержанием кремнезема. Похожая связь между этими свойствами и содержанием кремнезема наблюдалась также в случае синтетических алюминоси- ликатовых гелей (часто цитированных в литературе как возможные модели аллофанов), несмотря на различиные структуры гелей и натуральных глин. Это объясняется тем, что в меру десих ликации полимерические октаэдрические элементы алюминия придают более индивидуальный х арактер в обоих, натуральных и синтетических, образцах. Площади поверхности аллофановых глин, полученные на основе наклона кривых титрования при pH = 7, тесно связаны с количеством структурных гидроксиловых групп, которые могут реагировать с фторидом при том же самом pH. Постоянные отрицательные заряды всегда очень низкие, даже в случае кремнеземо-богатых аллофановых образцов. В связи с этим предлагается, что все эти глины являются фактически свободны от тетраэдрического алюминия. [Е.С.]

Resümee

Resümee

Die Oberflächen- und Ladungscharakteristika von 6 Allophanartigen Tonen, die von einer klimatischen Abfolge von Andisolen stammten, wurden mittels Titration, lonenretention, Oberflächenbestimmung, und Reaktivitätsmessungen untersucht. Einige Eigenschaften dieser Tone, wie z.B. der pH-Wert bei Null-Ladung, die Größe der Oberfläche und die Reaktivität struktureller OH-Gruppen scheinen durch die chemische Zusammensetzung, vor allem vom SiO2-GehaIt, bestimmt zu werden. Eine ähnliche Beziehung zwischen den oben genannten Eigenschaften und dem SiO2-Gehalt ist auch bei synthetischen Alumosilikat-Gelen vorhanden (die in der Literatur oft als mögliches Modell für Allophane herangezogen werden) trotz ihrer zu natürlichen Tonen verschiedenen Struktur. Eine Erklärungsmöglichkeit ist, daß mit fortschreitender SiO2-Abnahme oktaedrische polymere Einheiten von Aluminium in zunehmendem Maße einzeln auftreten sowohl in den synthetischen als auch in den natürlichen Proben. Die Oberflächen der Allophan-artigen Tone (gewonnen aus der Neigung der Titrationskurve bei pH 7) hängt eng mit den Gehalten an strukturellen Hydroxyl zusammen, das mit Fluorid bei etwa dem gleichen pH reagieren kann. Die permanenten negativen Ladungen sind immer sehr niedrig, selbst für SiO2-reiche AUophan-haltige Proben. Es wird daher angenommen, daß alle diese Tone nahezu frei von tetraedrischem Aluminium sein sollten. [U.W.]

Résumé

Résumé

Les propriétés de surface et de charge de 6 argiles en provenance d'une climatoséquence de sols à caractères andiques ont été étudiées en mettant en oeuvre des techniques telles que titrations potentiométriques, rétentions d'ions, déterminations de la surface spécifique, et tests de réactivité en présence de fluorure. Plusieurs caractéristiques de ces argiles comme la localisation du pH correspondant à une charge nulle, la grandeur de l'aire de surface, et la réactivité des groupements hydroxyliques structuraux sont déterminés par leur composition chimique, tout particulièrement par leur teneur en silice. De ce point de vue, on observe une remarquable analogie entre ces argiles naturelles et les gels aluminosiliciques synthétiques souvent présentés comme modèles d'allophanes dans littérature. Il est suggéré que, tant dans les échantillons naturels que synthétiques, la désilicification en entraînant l'individualisation progressive d'unités polymériques d'aluminium octaédrique est responsable des modifications observées. Pour les échantillons naturels, l'aire de la surface estimée par la pente de la courbe de titration à pH 7 montre une étroite relation avec la quantité d'hydroxyles structuraux réagissant avec fanion fluorure au même pH. La charge négative permanente de ces argiles est toujours très faible, même lorsque leur teneur en silice est élevée. Ceci suggère que leur contenu en Al tétraédrique est négligeable.

Keywords

AllophaneAndisolsDesilicationSoilsSpecific surfaceZero point of charge
Type
Research Article
Information
Clays and Clay Minerals , Volume 30 , Issue 2 , April 1982 , pp. 103 - 110
Copyright
Copyright © 1982, The Clay Minerals Society

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