Abstract
The crystalline and osmotic swelling of Na-, Cs-, Mg- and Ca-montmorillonite has been measured in dimethyl sulphoxide and in formamide, N-methyl formamide, dimethyl formamide, N-methyl acetamide and dimethyl acetamide. These liquids have similar dipole moments but their relative permittivities vary appreciably from values less than water to values greater than water.
Na-montmorillonite exhibits osmotic swelling (diffuse double layer development −d(001) ≫ 19 Å) in formamide and N-methyl formamide and Cs gives osmotic swelling behavior in formamide. Cs-montmorillonite in the crystalline swelling region give spacings greater than those found for water with all liquids. Mg- and Ca-montmorillonite did not give spacings greater than 19 Å in any of the liquids studied.
The swelling behavior of montmorillonite is affected by relative permittivity but for liquids with a similar relative permittivity methyl substitution in the molecule may prevent the development of diffuse double layers on the particle surfaces.
Résumé
Le gonflement cristallin et osmotique de montmorillonites Na, Cs, Mg, et Ca, a été mesuré dans le diméthylsulfoxyde, la formamide, la N méthylformamide, la diméthylformamide, la N méthylacétamide et la diméthylacétamide. Ces liquides ont des moments dipolaires voisins, mais leur permittivité relative varie d’une façon appréciable de valeurs inférieures à des valeurs supérieures à celle de l’eau.
La montmorillonite Na montre un gonflement osmotique (développement d’une double couche diffuse — d (001) ≫ 19 Å) dans la formamide et la N méthylformamide, et l’argile Cs a un comportement de gonflement osmotique dans la formamide. La montmorillonite Cs donne, avec tous les liquides, dans la région de gonflement cristallin, des espacements plus grands que ceux qui sont trouvés avec l’eau. Les montmorillonites Mg et Ca ne donnent pas d’espacements supérieurs à 19 Å dans aucun des liquides étudiés.
Le comportement gonflant de la montmorillonite est affecté par la permittivité relative, mais pour les liquides qui ont une permittivité relative semblable, la méthyl substitution dans la molécule peut empêcher le développement de doubles couches diffuses à la surface des particules.
Kurzreferat
Die kristalline und osmotische Quellung von Na-, Cs-, Mg- und Ca-Montmorillonit wurde in Dimethylsulphoxid und in Formamid, N-Methylformamid, Dimethylformamid, N-Methylacetamid und Dimethylacetamid gemessen. Diese Flüssigkeiten haben ähnliche Dipolmomente, aber ihre Dielektrizitätskonstanten variieren erheblich schwischen Werten, die geringer und solchen, die größer sind als die des Wassers.
Na-Montmorillonit zeigt osmotische Quellung (Entwicklung einer diffusen Doppelschicht — d (001) ≫ 19 Å) in Formamid und N-Methylformamid und Cs ergibt osmotisches Quellungsverhalten in Formamid. Cs-Montmorillonit weist im Bereich der kristallinen Quellung mit allen Flüssigkeiten Schichtabstände auf, die größer als die mit Wasser gefundenen sind. Mg- und Ca-Montmorillonit ergaben mit allen untersuchten Flüssigkeiten keine Schichtabstände über 19 Å.
Das Quellungsverhalten von Montmorillonit wurde durch die Dielektrizitätskonstante beeinflußt, jedoch kann für Flüssigkeiten mit ähnlicher Dielektrizitätskonstante Methylsubstitution im Molekül die Ausbildung einer diffusen Doppelschicht an den Teilchenoberflächen verhindern.
Резюме
Измеряют кристаллическое и осмотическое разбухание Na-, Cs- Mg- и Са-монт- мориллонитов в диметилсульфоксиде и в формамиде, в N-метилформамиде, в диметил- формамиде, в N-метилаиетамиде и в диметилацетамиде. Эти жидкости имеют одинаковые дипольные моменты, но их сравнительные диэлектрические проницаемости значительно различаются от числовых значений ниже воды до числовых значений выше воды.
Na-монтмориллонит выявляет осмотическое разбухание в формамиде и N-метилформамиде (развивается диффундирование двойных слоев — d(001) ≫ 19Å), a Cs выявляет поведение осмотического разбухания в формамиде. В области кристаллического разбухания Cs-монтмориллонит образует большие расстояния между атомами во всех этих жидкостях, чем в воде. Mg- и Са-монтмориллониты не дали расстояний более, чем 19А в экспериментальных жидкостях.
Ha поведение разбухания монтмориллонита влияет диэлектрическая проницаемость, но в жидкостях с тождественной диэлектрической проницаемостью замена метила в молекуле может предотвратить развитие диффудированных двойных слоев на поверхностях частиц.
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Olejnik, S., Posner, A.M. & Quirk, J.P. Swelling of Montmorillonite in Polar Organic Liquids. Clays Clay Miner. 22, 361–365 (1974). https://doi.org/10.1346/CCMN.1974.0220407
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DOI: https://doi.org/10.1346/CCMN.1974.0220407