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Kaolinite hydroxyls in dimethylsulphoxide-intercalated kaolinites at 77 K – a Raman spectroscopic study

Published online by Cambridge University Press:  09 July 2018

R. L. Frost ,
J. Kristof ,
E. Horvath  and
J. T. Kloprogge
R. L. Frost*
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001, Australia
J. Kristof
Affiliation:
Department of Analytical Chemistry, University of Veszprem, H 8201 Veszprem, PO Box 158
E. Horvath
Affiliation:
Research Group for Analytical Chemistry, Hungarian Academy of Sciences, H8201 Veszprem, PO Box 158, Hungary
J. T. Kloprogge
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001, Australia
*
*E-mail: r.frost@qut.edu.au
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Abstract

Kaolinite hydroxyls in dimethylsulphoxide-intercalated (DMSO-intercalated) kaolinites have been determined using Raman spectroscopy at 298 and 77 K. The inner surface hydroxyl frequencies at 3650, 3670, 3684 and 3693 cm-1 move to higher wavenumbers upon cooling to 77 K and are observed at 3659, 3676, 3692 and 3702 cm-1. The inner hydroxyl frequency is at 3620 cm-1 at 298 K and is at 3615 cm-1 at 77 K. Upon intercalation with DMSO, additional bands are found at 3660, 3536 and 3501 cm-1 for the low-defect kaolinite and at 3664, 3543 and 3509 cm-1 for the high-defect kaolinite at 298 K. The 3660 cm-1 band at 298 K is resolved into two bands at 3658 and 3663 cm-1 at 77 K for the low-defect kaolinite and these bands are assigned to the inner surface hydroxyl groups, hydrogen-bonded to the DMSO molecule. It is proposed that the DMSO molecule exists with two different orientations in the intercalate and these two molecular forms are differentiated by the OH-stretching bands of the inner surface hydroxyl groups. This band for the high-defect kaolinite is found at 3664 cm-1 at 298 K and resolves into two bands at 3664 and 3673 cm-1 at 77 K.

Keywords

dimethylsulphoxide (DMSO)low-defect kaolinitehigh-defect kaoliniteRaman microscopyDRIFT spectrometryintercalationkaolinite
Type
Research Article
Information
Clay Minerals , Volume 35 , Issue 2 , April 2000 , pp. 443 - 454
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2000

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