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Influence of Inorganic and Organic Ligands on the Formation of Aluminum Hydroxides and Oxyhydroxides

Published online by Cambridge University Press:  02 April 2024

A. Violante  and
P. M. Huang
A. Violante*
Affiliation:
Department of Soil Science, University of Saskatchewan, Saskatoon, Saskatchewan S7N 0W0, Canada
P. M. Huang
Affiliation:
Department of Soil Science, University of Saskatchewan, Saskatoon, Saskatchewan S7N 0W0, Canada
*
1Institute of Agricultural Chemistry, University of Naples, Portici, Italy.
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Abstract

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Hydroxide and oxyhydroxide products of aluminum were formed at room temperature at an initial Al concentration of 2 × 10-3 M, pH 8.2, and at varying concentrations of organic and inorganic ligands commonly found in nature. The effectiveness of the ligands in promoting the formation of noncrystalline products over crystalline Al(OH)3 polymorphs was found to be in the following order: phthalate ≅ succinate < glutamate < aspartate < oxalate < silicate ≅ fluoride < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. The lowest ligand/Al molar ratio at which the production of Al hydroxides or oxyhydroxides was inhibited ranged from 0.02 to 15. Above critical ligand/Al ratios, crystalline products were inhibited and ligands coprecipitated with noncrystalline products which remained unchanged for at least 5 months. Polydentate and large ligands generally were more inhibitive than those with fewer functional groups or of smaller size.

The perturbing ligands promoted and stabilized the formation of pseudoboehmite over crystalline Al(OH)3 polymorphs in the following sequence: chloride < sulfate < phthalate ≅ succinate < glutamate < silicate < aspartate < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. The optimal range of the ligand/Al molar ratios for the formation of pseudoboehmite varied, for example, from 0.005–0.015 for tartrate to 600–1000 for chloride. Pseudoboehmite was not formed in the presence of fluoride.

Резюме

Резюме

Гидроокисные и оксигидроокисные продукты алюминия формировались при комнатной температуре, начальной концентрации Al равной 2 × 10-3 М, pH равным 8,2 и различных концентрациях органических и неорганических лигандов, обычно находящихся в природе. Эффективность лигандов в способствовании образованию некристаллических продуктов предпочтительно полиморфом А1(ОН)3 находилась в следующем порядке: фталат ≅ сукцинат < глутамат < аспартат < оксалат < силикат ≅ фторид < фосфат < салицилат ≅ малат < таннат < цитрат < тартрат. Наиболее низкая величина молярного отнощения лиганд/Аl, при которой задерживалось образование гидроокисей или оксигидроокисей Al, находилась в диапазоне от 0,02 до 15. Выше критических величин отношений лиганд/Аl, кристаллические продукты не образовывались, а лиганды осаждались вместе с некристаллическими продуктами, которые оставались неизмененными в течение не менее, чем 5 месяцев. Полидентат и большие лиганды имели большую способность задерживания, чем лиганды, содержащие меньшее количества функциональных групп или лиганды меньших размеров. Возмущающие лиганды способствовали и стабилизировали формирование скорее псевдобемита, чем кристаллических полиморфов Аl(ОН)3 в следующем порядке: хлорид < сульфат < фталат ≅ сукцинат < глутамат < силикат < аспартат < фасфат < салицилат ≅ малат < таннат < цитрат < тартрат.

Оптимальный диапазон величин молярных отнощений лиганд/Аl для образования псевдобемита изменялся, например, от 0,005–0,015 для тартрата до 600–1000 для хлорида. Псевдобемит не образовывался в присутствии фторида. [E.G.]

Resümee

Resümee

Hydroxid- und Oxyhydroxid-Verbindungen von Aluminium wurden bei Raumtemperatur und mit einer ursprünglichen Al-Konzentration von 2 × 10-3 m, bei pH 8,2 und mit verschiedenen Konzentrationen von organischen und anorganischen Liganden, die in der Natur üblich sind, gebildet. Die Wirksamkeit der Liganden bei der Förderung der Bildung von nichtkristallinen Produkten gegenüber kristallinen polymorphen A1(OH)3-Modifikationen geht in folgender Reihenfolge: Phtalat ≅ Succinat < Glutamat < Asparat < Oxalat < Silikat ≅ Fluorid < Phosphat < Salicylat ≅ Malat < Tannat < Citrat < Tartrat. Das niedrigste Ligand/Al-Molverhältnis, bei dem die Entstehung von Al-Hydroxiden oder -Oxyhydroxiden verhindert wurde, liegt bei 0,02–15. Oberhalb der kritischen Ligand/Al-Verhältnisse wurde die Bildung kristalliner Verbindungen verhindert und die Liganden fielen mit nichtkristallinen Produkten zusammen aus, die über mindestens 5 Monate unverändert blieben. Polydentat und große Liganden wirkten sich im allgemeinen mehr verhindernd aus als solche, mit weniger funktionellen Gruppen oder mit geringer Größe.

Die störenden Liganden förderten und stabilisierten die Bildung von Pseudoboehmit gegenüber kristallinen polymorphen Al(OH)3-Modifikationen in der folgenden Reihenfolge: Chlorid < Sulfat < Phtalat ≅ Succinat < Glutamat < Silikat < Asperat < Phosphat < Salicylat ≅ Malat < Tannat < Citrat < Tartrat. Der optimale Bereich der Ligand/Al-Molverhältnisse für die Bildung von Pseudoboehmit variierte, z.B. von 0,005–0,015 für Tartrat bis 600–1000 für Chlorid. Pseudoboehmit wurde in Gegenwart von Fluorit nicht gebildet. [U.W.]

Résumé

Résumé

Des produits d'aluminium hydroxide et oxyhydroxide ont été formés à une concentration initiale d'Al de 2 × 10-3 M, au pH 8,2 et à des concentrations variées de ligands organiques et inorganiques trouvés communément dans la nature. On a trouvé que l'efficacité des ligands à promouvoir la formation de produits non-cristallins plutôt que des polymorphes Al(OH)3 cristallins était dans l'ordre suivant: phthalate ≅ succinate < glutamate < aspartate < oxalate < silicate ≅ fluoride < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. La proportion molaire ligand/Al la plus basse à laquelle la production d'hydroxides Al ou d'hydroxides Al a été inhibée s’étendait de 0,02 à 15. Au dessus des proportions ligand/Al critiques, les produits cristallins étaient inhibés et les ligands ont coprécipite avec des produits non-cristallins qui sont restés inchangés pendant au moins 5 mois. Les ligands polydentates ou larges étaient généralement plus inhibants que ceux avec moins de groupes fonctionnels ou de plus petite taille.

Les ligands perturbants ont promu et stabilisé la formation de pseudoboéhmite relativement aux polymorphes cristallins Al(OH)3 selon la séquence suivante: chloride < sulphate < phthalate ≅ succinate < glutamate < silicate < aspartate < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. L’étendue optimale des proportions molaires ligand/Al pour la formation de pseudoboéhmite a varié, par exemple, de 0,005–0,015 pour la tartrate à 600–1000 pour la chloride. La pseudoboéhmite n'a pas été formée en la présence de fluoride. [D.J.]

Keywords

Aluminum hydroxideBoehmiteLigandPrecipitationPseudoboehmiteX-ray powder diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 33 , Issue 3 , June 1985 , pp. 181 - 192
Copyright
Copyright © 1985, The Clay Minerals Society

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