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FTIR Reflectance vs. EPR Studies of Structural Iron in Kaolinites

Published online by Cambridge University Press:  28 February 2024

Thierry Delineau ,
Thierry Allard ,
Jean-Pierre Muller ,
Odile Barres ,
Jacques Yvon  and
Jean-Maurice Cases
Thierry Delineau
Affiliation:
Laboratoire Environnement et Minéralurige, UA 235 CNRS, ENSG-INPL, B.P.40, 54501, Vandoeuvre Cédex, France
Thierry Allard
Affiliation:
Laboratoire de Minéralogie et Cristallographie, Universités Paris VI et VII, 4, Place Jussieu, 75252 Paris Cedex 05, France
Jean-Pierre Muller
Affiliation:
Laboratoire de Minéralogie et Cristallographie, Universités Paris VI et VII, 4, Place Jussieu, 75252 Paris Cedex 05, France O.R.S.T.O.M., Départment T.O.A., UR1G, 213, rue Lafayette, 75480 Paris Cedex 10, France
Odile Barres
Affiliation:
Laboratoire Environnement et Minéralurige, UA 235 CNRS, ENSG-INPL, B.P.40, 54501, Vandoeuvre Cédex, France
Jacques Yvon
Affiliation:
Laboratoire Environnement et Minéralurige, UA 235 CNRS, ENSG-INPL, B.P.40, 54501, Vandoeuvre Cédex, France
Jean-Maurice Cases
Affiliation:
Laboratoire Environnement et Minéralurige, UA 235 CNRS, ENSG-INPL, B.P.40, 54501, Vandoeuvre Cédex, France
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Abstract

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The substitution of Fe3+ in the kaolinite structure is studied by EPR spectrometry and by FTIR spectrometry on a large set of kaolins from different origins (sedimentary and primary ores, soil kaolins). The IR bands at 3598 and 875 cm−1, observed in the literature only in the case of disordered kaolins or in Fe-rich environments (synthetic, lateritic), are revealed by high-resolution IR analysis, whatever the origin and the total Fe content of the samples. The EPR bands corresponding to Fe3+ substituted in sites II of the octahedral sheet increase when the IR absorbance near 3600 cm−1 increases. Two IR absorption bands near 4465 cm−1 and 7025 cm−1 are observed for the first time, both in transmission and diffuse reflectance on all samples. These bands are assigned to the combination of the 3598 and 875 cm−1 bands and to the first harmonic of the band at 3598 cm−1, respectively. The area of the band at 4465 cm−1 in diffuse reflectance is quantitatively correlated to the abundance of Fe3+ located in centers II as measured by ESR. This directly confirms the assignment of the two IR bands at 3598 and 875 cm−1 to OH stretching and deformation vibration bands in octahedral FE3+ environment in the kaolinite structure, respectively. Effects due to the size of particles and to the main kaolins impurities on the near infrared spectra, are also discussed.

Keywords

EPRFeKaoliniteMid and near infraredSubstitution
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 3 , June 1994 , pp. 308 - 320
Copyright
Copyright © 1994, Clay Minerals Society

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