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Static and Dynamic Structure of Water in Hydrated Kaolinites. I. The Static Structure

Published online by Cambridge University Press:  02 April 2024

P. M. Costanzo ,
R. F. Giese Jr.  and
M. Lipsicas
P. M. Costanzo
Affiliation:
Department of Geological Sciences, State University of New York at Buffalo, 4240 Ridge Lea Road, Amherst, New York 14226
R. F. Giese Jr.
Affiliation:
Department of Geological Sciences, State University of New York at Buffalo, 4240 Ridge Lea Road, Amherst, New York 14226
M. Lipsicas
Affiliation:
Schlumberger-Doll Research, P.O. Box 307, Ridgefield, Connecticut 06877
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Abstract

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Four hydrates with d(001) = 8.4, 8.6, and 10 Å (two types) were synthesized by intercalating kaolinite with dimethylsulfoxide and treating the intercalated clay with fluoride ions. X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, and kinetics of dehydration experiments have led to the identification of two types of interlayer water. One type of water (hole water) is situated in the ditrigonal holes of the silica tetrahedral surface; the second type (associated water) forms a discontinuous layer of mobile water. The 8.4-Å and 8.6-Å hydrates have only hole water, whereas the two synthetic 10-Å hydrates and halloysite(10Å) contain both hole and associated water. The hole water is probably hydrogen bonded to the basal oxygens of the silica tetrahedra or, in the 8-Å hydrates when fluorine exchanges for inner-surface hydroxyls, the water molecules may reorient and form stronger hydrogen bonds to the fluorine. Associated water forms water-water hydrogen bonds approximately equal in strength to liquid water but is less strongly bonded to the clay surfaces than hole water. At room temperature the hole and associated water in the 10-Å hydrates do not form an ice-like structure.

Резюме

Резюме

Четыре гидрата с d(001) = 8,4, 8,6, и 10 Å (два типы) синтезировались путем прослаиваниа каолинита диметилсулфоокисью и обработкой прослойки фтористыми ионами. Два типа межслойной воды идентифицировались при помощи ренигеновской порошковой дифракции, инфракрасной спек¬троскопии, дифференциальной развертывающей калориметрии, термо-гравиметрического анализа и экспериментов по кинетике дегидратации. Один тип воды (пустотная вода) находится в дитригональ-ных местах кремниевой тетраэдрической поверхности; второй тип (ассоциированная вода) образо¬вывает неравномерный слой подвижной воды. 8,4 Å и 8,6 Å гидраты имеют только пустотную воду, тогда как два синтетических 10 Å гидрата и галлуазит (10 Å) содержат оба типа, пустотную и ассоциированную воду. Пустотная вода является, вероятно, связанной водородной связью с основ¬ными атомами кислорода тетраэдров окиси кремния или, молекулы воды могут изменять ориен¬тацию и образовывать более сильную водородную связь с фтором в 8 Å гидратах, если фтор обме¬нивает гидроксиловые группы внутренних поверхностей. Ассоциированная вода образовывает водородные связи вода-вода с прочностью приблизительно такой, как вода в жидком состоянии, но она легче связана с глинистой поверхностью, чем пустотная вода. В комнатной температуре ни пустотная ни ассоциированная вода не формируют структуры типа льда в 10 Å гидратах. [Е.О.]

Resümee

Resümee

Vier Hydrate mit d(001) = 8,4,8,6, und 10 Å (zwei Arten) wurden synthetisiert, indem Kaolinit mit Dimethylsulfoxid wechselgelagert und der wechselgelagerte Ton mit Fluoridionen behandelt wurde. Röntgenpulverdiffraktometrie, Infrarotspektroskopie, Differentialrasterkalorimetrie, und Thermogravi-metrie sowie die Kinetik von Dehydratationsexperimenten haben zur Bestimmung von zwei Arten von Zwischenschichtwasser geführt. Eine Art Wasser (sog. Hohlraumwasser) befindet sich in den ditrigonalen Hohlräumen der Siliziumtetraederoberfläche; die zweite Art (sog. assoziiertes Wasser) bildet eine diskontinuierliche Lage von mobilem Wasser. Die 8,4 Å- und 8,6 Å-Hydrate haben nur sog. Hohlraumwasser, während die zwei synthetischen 10 Å-Hydrate und Halloysit(10 Å) sowohl Hohlraumals auch assoziiertes Wasser enthalten. Das Hohlraumwasser ist wahrscheinlich durch Wasserstoffbrücken an die Basissauerstoffe der Si04-Tetraeder gebunden oder—in den 8 Å-Hydraten, wenn das Fluorid anstelle des Hydroxyls der inneren Oberfläche tritt—die Wassermoleküle können auch reorientiert sein und festere Wasserstoffbindungen zu den Fluoridionen bilden. Das assoziierte Wasser bildet Wasser-Wasser Wasserstoffbindungen, die etwa gleich fest sind wie im flüssigen Wasser, aber weniger fest an die Tonoberfläche gebunden sind als das Hohlraumwasser. Bei Raumtemperatur bilden das Hohlraum- und das assoziierte Wasser in den 10 Å-Hydraten keine Eis-ähnliche Struktur. [U.W.]

Résumé

Résumé

Quatre hydrates avec d(001) = 8,4,8,6, et 10 Å (deux types) ont été synthétisés en intercalant la kaolinite avec la diméthylsulfoxide et en traitant l'argile intercalé avec des ions fluorides. La diffraction des rayons-X, la spectroscopie infrarouge, la calorimetrie différentielle balayante, l'analyse gravimétrique thermale, et des expériences de kinétique de déshydration ont mené à l'identification de deux types d'eau intercouche. Un type d'eau (eau de trou) est situé dans les trous ditrigonaux de la surface tétraèdrale de la silice; le second type (eau associée) forme une couche discontinue d'eau mobile. Les hydrates de 8,4 Å et de 8,6 Å ont seulement de l'eau de trou, alors que les deux hydrates synthétiques de 10 Å et l'halloysite(lOÅ) contiennent à la fois l'eau de trou et associée. L'eau de trou est probablement liée par l'hydrogène aux oxygènes de base des tétraèdres de la silice ou, dans les hydrates de 8-Å lorsque la fluorine est échangée pour les hydroxyles de la surface intérieure, les molécules d'eau peuvent se réorienter et former des liens hydrogènes plus forts avec la fluorine. L'eau associée forme des liens hydrogènes eau-eau à peu près aussi forts que l'eau liquide, mais est moins fort liée aux surfaces argiles que l'eau de trou. A température ambiante, l'eau de trou et associée dans les hydrates de 10 À ne forme pas une structure semblable à de la glace. [D.J.]

Keywords

DimethylsulfoxideHalloysiteHydroxylInfrared spectroscopyKaoliniteWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 32 , Issue 5 , October 1984 , pp. 419 - 428
Copyright
Copyright © 1984, The Clay Minerals Society

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