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The Effect of Surface Modification by an Organosilane on the Electrochemical Properties of Kaolinite

Published online by Cambridge University Press:  28 February 2024

Belinda Braggs ,
Daniel Fornasiero ,
John Ralston  and
Roger St. Smart
Belinda Braggs
Affiliation:
School of Chemical Technology, University of South Australia, The Levels, S.A. 5095, Australia
Daniel Fornasiero
Affiliation:
School of Chemical Technology, University of South Australia, The Levels, S.A. 5095, Australia
John Ralston
Affiliation:
School of Chemical Technology, University of South Australia, The Levels, S.A. 5095, Australia
Roger St. Smart
Affiliation:
School of Chemical Technology, University of South Australia, The Levels, S.A. 5095, Australia
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Abstract

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The electrochemical properties of kaolinite before and after modification with chlorodimethyl-octadecylsilane have been studied by electrophoretic mobility, surface charge titration, and extrapolated yield stress measurements as a function of pH and ionic strength. A heteropolar model of kaolinite, which views the particles as having a pH-independent permanent negative charge on the basal planes and a pH-dependent charge on the edges, has been used to model the data. The zeta potential and surface charge titration experimental data have been used simultaneously to calculate acid and ion complexation equilibrium constants using a surface complex model of the oxide-solution interface. The experimental data were modeled following subtraction of the basal plane constant negative charge, describing only the edge electrical double layer properties. Extrapolated yield stress measurements along with the electrochemical data were used to determine the edge isoelectric points for both the unmodified and modified kaolinite and were found to occur at pH values of 5.25 and 6.75, respectively. Acidity and ion complexation constants were calculated for both sets of data before and after surface modification. The acidity constants, pKa1 = 5.0 and pKa2 = 6.0, calculated for unmodified kaolinite, correlate closely with acidity constants determined by oxide studies for acidic sites on alumina and silica, respectively, and were, therefore, assigned to pH-dependent specific chemical surface hydroxyl groups on the edges of kaolinite. The parameters calculated for the modified kaolinite indicate that the silane has reacted with these pH-dependent hydroxyl groups causing both a change in their acidity and a concomitant decrease in their ionization capacity. Infrared data show that the long chain hydrocarbon silane is held by strong bonding to the kaolinite surface as it remains attached after washing with cyclohexane, heating, and dispersion in an aqueous environment.

Keywords

Acidity constantsElectrophoresisKaoliniteModelingSilaneSurface chargeSurface modification
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 2 , April 1994 , pp. 123 - 136
Copyright
Copyright © 1994, Clay Minerals Society

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