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The I.R. Spectra of Interlamellar Kaolinite-Amide Complexes—I. The Complexes of Formamide, N-Methylformamide and Dimethylformamide

Published online by Cambridge University Press:  01 July 2024

S. Olejnik ,
A. M. Posner  and
J. P. Quirk
S. Olejnik*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009
A. M. Posner
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009
J. P. Quirk
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia, 6009
*
*Present address: University of Oxford, Physical Chemistry Laboratory, South Parks Road, OX13QZ, England.
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Abstract

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The i.r. spectra of interlamellar kaolinite complexes with formamide, N-methylformamide and dimethylformamide have been examined. The spectra show that the amides hydrogen-bond, through the C=O group of the amide to the inner surface kaolinite hydroxyls and decrease the intensity of the kaolinite ν(OH) bands. Hydrogen-bonded kaolinite hydroxyl bands appear at lower frequencies and these have been correlated to the original kaolinite ν (OH) bands. Other kaolinite bands in the complexes show smaller perturbations of the kaolinite vibrations. Each amide hydrogen-bonds to different groups of hydroxyls. Formamide hydrogen-bonds to the 3690 and 3664 cm−1 hydroxyls, N-methylformamide to the 3690 and 3648 cm−1 hydroxyls. The interpretation for the dimethylformamide complex is less clear. The ν(NH) frequencies of formamide and N-methylformamide in the complexes are intermediate between that in dilute non-polar solution and in the liquid. This could arise from either or both a degree of intermolecular association of the amide when between the kaolinite lamellae, or to weak N—H … O hydrogen bonds to the tetrahedral oxygen sheet of the lamellae.

Résumé

Résumé

Les spectres i.r. des complexes interlamellaires de la kaolinite avec la formamide, la N-méthylformamide et la diméthylformamide ont été étudiés. Les spectres montrent que les amides sont liés par une liaison hydrogène qui s’établit entre le groupe C=0 de l’amide et les hydroxyles de la surface interne de la kaolinite, ce qui entraîne une diminution de l’intensité des bandes ν(OH) de la kaolinite. Les bandes des hydroxyles pontés de la kaolinite apparaissent à des fréquences plus basses, qui ont été reliées aux bandes ν(OH) de la kaolinite originelle. Dans les complexes, d’autres bandes de la kaolinite montrent de petites perturbations des vibrations de la kaolinite. Chaque amide établit des liaisons hydrogène avec différents groupes d’hydroxyles. La formamide établit une liaison hydrogène avec les hydroxyles à 3690 et 3664 cm−1, et la N-méthylformamide avec les hydroxyles à 3690 et 3648 cm−1. L’interprétation du complexe avec la diméthylformamide est moins évidente. Les fréquences ν(NH) de la formamide et de la N-méthylformamide dans les complexes, sont intermédiaires entre celles d’une solution diluée en milieu non polaire et celles du liquide. Ceci pourrait provenir soit, ou à la fois d’une certain degré d’association intermoléculaire de l’amide lorsqu’elle est entre les feuillets de kaolinite, soit de liaisons hydrogène faibles N—H…O s’établissant avec la couche des atomes d’oxygène tétraédriques du feuillet.

Kurzreferat

Kurzreferat

Die Ultrarotspektren interlamellarer Kaolinitkomplexe mit Formamid, N-Methylformamid und Dimethylformamid wurden untersucht. Die Spektren zeigen, dass die Amide eine Wasserstoffbrücke über die C=0 Gruppe des Amids zu den Hydroxylgruppen an der inneren Oberfläche des Kaolinits bilden und die Intensität der Kaolinit ν(OH) Banden vermindern. Wasserstoffbrücken-Kaolinit Hydroxybanden erscheinen bei niedrigeren Frequenzen, und diese sind mit den ursprünglichen Kaolinit ν(OH) Banden in Beziehung gebracht worden. Andere Kaolinitbanden in den Komplexen zeigen geringere Störungen der Kaolinitschwingungen. Jedes Amid bildet eine Wasserstoffbrücke zu verschiedenen Gruppen von Hydroxylen, und zwar bildet Formamid Wasserstoff brücken zu den 3690 und 3664 cm−1 Hydroxylen, und N-Methylformamid zu den 3690 und 3648 cm−1 Hydroxylen. Die Ausdeutung ist weniger klar für den Dimethyjformamidkomplex. Die ν(NH) Frequenzen des Formamids und des N-Methylformamids in den Komplexen nehmen eine Zwischenstellung ein zwischen den Werten in verdünnter, nichtpolarer Lösung und in der Flüssigkeit. Das kann seine Ursache in einer oder beider der folgenden Erscheinungen haben: nämlich ein bestimmtes Mass intermolekularer Assoziation des Amids wenn es sich zwischen den Kaolinitlamellen befindet, oder aber schwache N—H … O Wasserstoffbrücken zum tetraedrischen Sauerstoffblatt der Lamellen.

Резюме

Резюме

Изучены инфракрасные спектры межслоевых комплексов каолинита с формамидом, N-метилформамидом и диметилформамидом. Спектры показали, что амиды за счет своих групп С=O образуют водородные связи с внутренними гидроксильными поверхностями каолинитовых слоев и уменьшают интенсивность каолинитовых полос ОН. Полосы водородных связей, образованных гидроксилами каолинита, наблюдаются при более низких частотах; они могут быть сопоставлены с полосами ОН исходного каолинита. Другие каолинитовые полосы в комплексах обнаруживают лишь незначительные изменения каолинитовых вибраций. Каждая амидная группа связана водородной связью с различными группами ОН. Формамид образует водородную связь, отвечающую гидроксилам, которые дают полосы при 3690 и 3664 см−1, N-метилформамид — при 3690 и 3648 см−1. Интерпретация ИК-спектров комплексов с диметилформамидом менее ясна. Частота колебаний групп NH формамида и N-метилформамида в комплексах является промежуточной между частотой колебания в разбавленном неполярном растворе и в жидкости. Это может быть обусловлено либо степенью межмолекулярного взаимодействия амидов между слоями каолинита, либо слабыми водородными связями типа N—H…O с тетраэдрическими кислородными поверхностями каолинитовых слоев, либо двумя этими причинами.

Type
Research Article
Information
Clays and Clay Minerals , Volume 19 , Issue 2 , June 1971 , pp. 83 - 94
Copyright
Copyright © 1971, The Clay Minerals Society

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