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The Chemical Form of Vanadium (IV) in Kaolinite

Published online by Cambridge University Press:  28 February 2024

A. U. Gehring ,
I. V. Fry ,
J. Luster  and
Garrison Sposito
A. U. Gehring
Affiliation:
Department of Soil Science, University of California Berkeley, California 94720
I. V. Fry
Affiliation:
Department of Plant Biology, University of California Berkeley, California 94720
J. Luster
Affiliation:
Department of Soil Science, University of California Berkeley, California 94720
Garrison Sposito
Affiliation:
Department of Soil Science, University of California Berkeley, California 94720
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Abstract

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A combined application of electron paramagnetic resonance (EPR) and Fourier-transform infrared (FTIR) spectroscopies with thermal methods was used to determine the chemical form of V(IV) in a Georgia kaolinite (KGa-I). Precise values of the EPR spectroscopic g-values and hyperfine coupling constants were obtained for an untreated sample (g∥ = 1.940, A∦ = 18.71 mT; g⊥ = 1.966, A⊥ = 7.63 mT). Heating the sample to 1000°C in steps while monitoring phase changes with EPR and FTIR spectra led to the following structural interpretations: 1) Vanadium (IV) occurs almost entirely as an isomorphically substituted species in the octahedral sheet of KGa-1 kaolinite; 2) during the dehydroxylation of kaolinite at about 500°C and the subsequent formation of metakaolinite, V(IV)-substituted octahedral sites are readily converted into truncated octahedra exhibiting fourfold coordination; and 3) in these highly distorted four-coordinated sites, V(IV) is metastable, being completely oxidized at about 800°C.

Keywords

Electron paramagnetic resonanceIsomorphic substitutionKaoliniteVanadium
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 6 , December 1993 , pp. 662 - 667
Copyright
Copyright © 1993, The Clay Minerals Society

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