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Thermal behaviour of alum-(K) KAl(SO4)2·12H2O from in situ laboratory high-temperature powder X-ray diffraction data: thermal expansion and modelling of the sulfate orientational disorder

Published online by Cambridge University Press:  02 January 2018

Paolo Ballirano
Paolo Ballirano*
Affiliation:
Dipartimento di Scienze della Terra, Sapienza Universita` degli Studi di Roma, Piazzale Aldo Moro 5, I-00185, Rome, Italy
*
* E-mail: paolo.ballirano@uniroma1.it
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Abstract

The present work analyses the thermal behaviour of alum-(K), KAl(SO4)2·12H2O, by in situ laboratory high-temperature powder X-ray diffraction data from 303 K to melting, which starts at 355 K and is completed, due to kinetics, at 359 K. The calculated a0 linear thermal expansion coefficient is of 14.68(11) × 10–6 K–1 within the investigated thermal range. The k disorder parameter, describing the extension of the orientational disorder of the sulfate group, has been found to decrease from ∼0.70 to ∼0.65 just before melting. It has been demonstrated that the occurrence of the disorder implies the coexistence of K+ ions in both six- and seven-fold coordination. This is necessary for assigning a reasonable bond-valence sum of 0.81 valence units (vu) to the 'average' K+ ion a instead of 0.66 vu, which is obtained in the case of six-fold coordination alone. We can describe the temperature dependence of k from 93–355 K by means of the empirical equation k = 0.798(12) + 2.5(11) × 10–4 T – 1.9(2) × 10–6T2, which includes reference low-temperature data. Bond-valence analysis has shown that, on cooling, an increase of the k disorder parameter and shortening of the K–O2 bond distance act together to maintain constancy in the bond-valence sum at the K site, stabilizing the structure. Therefore, the need for keeping the 'average' K+ ion at a reasonable bond-valence sum appears to be the driving force for the ordering process involving the sulfate group.

Keywords

alum-(K)powder X-ray diffractionRietveld methodthermal behavioursulfate disorder
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 1 , February 2015 , pp. 157 - 170
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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