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Titration of pH-Dependent Sites of Kaolinite in Water and Selected Nonaqueous Solvents

Published online by Cambridge University Press:  01 July 2024

R. H. Loeppert Jr. ,
L. W. Zelazny  and
B. G. Volk
R. H. Loeppert Jr.*
Affiliation:
Soil Science Department, University of Florida, Gainesville, Florida 32611
L. W. Zelazny*
Affiliation:
Soil Science Department, University of Florida, Gainesville, Florida 32611
B. G. Volk
Affiliation:
Soil Science Department, University of Florida, Gainesville, Florida 32611
*
1Present address: Department of Crop and Soil Sciences, Michigan State University, East Lansing, Mich. 48824, U.S.A.
2Present address: Department of Agronomy, Virginia Polytechnic Institute and State University, Blacksburg, Va. 24061, U.S.A.
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Abstract

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K-saturated kaolinite was titrated in 13 different solvents with tetrabutylammonium hydroxide using a combination electrode for potentiometric determination. The titer of base required to reach the final potentiometric endpoint was dependent on the solvent and increased according to the following solvent order in both the presence and absence of excess neutral salt: methanol ⩽ water < ethanol ⩽ 1-propanol < 1-butanol < 2-propanol < DMF < t-butanol < DMSO < pyridine ⩽ acetonitrile ⩽ methylethyl ketone < acetone. With the protic solvents, titratable acidity increased according to decreasing dielectric constant of the solvent and increasing size and/or branching of the aliphatic constituent. The largest titratable acidities were obtained in the dipolar aprotic solvents with negligible basic character (e.g., acetonitrile, acetone, methylethyl ketone). These results are discussed in terms of solvent properties, solvation characteristics of ions in the solvents, and acid-base behavior of crystalline edge sites.

Резюме

Резюме

Каолинит, насыщенный К, был титрован в тринадцати различных растворителях с гидроокисью тетрабутиламмония с использованием комбинированного электрода для потенциометрического определения. Титр основания, необходимый для достижения окон-чательной потенциометрической границы, зависел от растворителя и возрастал соглас-но следующему порядку растворителей в присутствии и отсутствии избыточной нейтра-ной соли: метанол≤вода<этанол≤1-пропанол<1-бутанол<2-пропанол<Т-бутанол<диметил-сульфоксид<пиридин≤ацетонитрит≤метилэтилкетон<ацетон. С протонными растворами ти-трационная кислотность возрастала в соответствии с уменьшением диэлектрической постоянной растворителя и возрастанием размера и/или разветвлением алифатического компонента. Наибольшие титрационные кислотности были получены в дипольных апро-тонных растворителях с незначительным основным характером.(т.е. ацетонитрил, аце-тон, метилэтилкетон). Эти результаты обсуждаются в отношении свойств растворителей, характеристик сольватации ионов, кислотно-основного поведения некоторых частей кристаллических граней.

Kurzreferat

Kurzreferat

Ein mit Kalium gesättigtes Kaolinit wurde in dreizehn verschiedenen Lösungsmitteln mit Tetrabutylammoniumhydroxyd titriert, indem eine Kombinationselektrode für potentiometrische Bestimmungen benutzt wurde. Die Menge von Alkali, die nötig war, um den potentiometrischen Endpunkt zu erreichen, war vom Lösungsmittel abhängig und nahm in der folgenden Lösungsmittelreihenfolge zu, sowohl in Anwesenheit wie auch in Abwesenheit eines Überschusses an neutralen Salzen: Methanol≤ Wasser< Äthanol≤ 1-Propanol< 1-Butanol< 2-Propanol< DMF< t-Butanol< DMSO< Pyridin≤ Acetonitril≤ Methyläthylketoní Aceton. Mit den protischen Lösungsmitteln nimmt die titrierbare Azidität mit abnehmender Dielektrizitätskonstante des Lösungsmittels und mit zunehmender Länge und/oder Verzweigung des aliphatischen Anteils zu. Die höchsten titrierbaren Aziditäten wurden in den dipolaren, aprotischen Lösungsmitteln mit unbedeutendem basischen Charakter (z.B. Acetonitril, Aceton, Methyläthylketon) erhalten. Diese Resultate werden hinsichtlich der Eigenschaften der Lösungsmittel, Solvatationscharakteristiken der Ionen in den Lösungsmitteln und Säure-Basen Benehmen der kristallinen Randstellen diskutiert.

Résumé

Résumé

Une kaolinite saturée de K a été titrée dans treize solvants différents avec de l'hydroxide de tétrabutylammonium utilisant une électrode de combinaison pour la détermination potentiométrique. Le titre basique nécessaire pour parvenir au point potentiométrique final dépendait du solvant, et augmentait, à la fois en la présence et l'absence d'un excès de sel neutre, dans l'ordre de solvants suivant: méthanol ≤ eau < éthanol ≤ 1-propanol < l-butanol < 2-propanol < DMF < t-butanol < DMSO < pyridine ≤ acétonitrile ≤ méthyléthyl cetone < acétone. Pour les solvants protiques, l'acidité titrable augmentait selon la constante diélectrique décroissante du solvant, et selon la taille et/ou le branchement croissant du constituant aliphatique. Les plus grandes acidités titrables étaient obtenues dans les solvants dipolaires aprotiques à caractère basique négligible (c.à.d. acétonitrile, acétone, méthyléthyl cetone). Ces résultats sont discutés selon les proprétés des solvants, les caractéristiques de dissolution des ions dans les solutions, et le comportement vis à vis des acides et des bases des sites de bords de cristaux.

Keywords

AcidityKaoliniteSolventsTitration
Type
Research Article
Information
Clays and Clay Minerals , Volume 27 , Issue 1 , February 1979 , pp. 57 - 62
Copyright
Copyright © 1979, The Clay Minerals Society

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