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Thermal expansion of alunite up to dehydroxylation and collapse of the crystal structure

Published online by Cambridge University Press:  05 July 2018

M. Zema ,
A. M. Callegari ,
S. C. Tarantino ,
E. Gasparini  and
P. Ghigna
M. Zema*
Affiliation:
Dipartimento di Scienze della Terra e dell’Ambiente, Universitá di Pavia, via Ferrata 1, I-27100 Pavia, Italy
A. M. Callegari
Affiliation:
Dipartimento di Scienze della Terra e dell’Ambiente, Universitá di Pavia, via Ferrata 1, I-27100 Pavia, Italy Sistema Museale di Ateneo, Universitá di Pavia, Corso Strada Nuova 65, I-27100 Pavia, Italy
S. C. Tarantino
Affiliation:
Dipartimento di Scienze della Terra e dell’Ambiente, Universitá di Pavia, via Ferrata 1, I-27100 Pavia, Italy
E. Gasparini
Affiliation:
Dipartimento di Scienze della Terra e dell’Ambiente, Universitá di Pavia, via Ferrata 1, I-27100 Pavia, Italy
P. Ghigna
Affiliation:
Dipartimento di Chimica, Universitá di Pavia, Viale Taramelli 16, I-27100 Pavia, Italy
*
E-mail: michele.zema@unipv.it
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Abstract

The high-temperature (HT) behaviour of a sample of natural alunite was investigated by means of in situ HT single-crystal X-ray diffraction from room temperature up to the dehydroxylation temperature and consequent collapse of the crystal structure. In the temperature range 25–500°C, alunite expands anisotropically, with most of the contribution to volume dilatation being produced by expansion in the c direction. The thermal expansion coefficients determined over the temperature range investigated are: αa = 0.61(2) × 10–5 K–1 (R2 = 0.988), αc = 4.20(7) × 10–5 K–1 (R2 = 0.996), αc/αa = 6.89, αV = 5.45(7) × 10–5 K–1 (R2 = 0.998). At ∼275–300°C, a minor discontinuity in the variation of unit-cell parameters with temperature is observed and interpreted on the basis of loss of H3O+ that partially substitutes for K+ at the monovalent A site in the alunite structure. Increasing temperature causes the Al(O,OH)6 sheets, which remain almost unaltered along the basal plane, to move further apart, and this results in an expansion of the coordination polyhedron around the intercalated potassium cation. Sulfate tetrahedra act as nearly rigid units, they contract a little in the lower temperature range to accommodate the elongation of the Al octahedra.

Keywords

alunitethermal expansionsingle-crystal X-ray diffraction
Type
Research Article
Information
Mineralogical Magazine , Volume 76 , Issue 3 , June 2012 , pp. 613 - 623
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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