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Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

Frost, Ray L., Reddy, B. Jagannadha, & Keeffe, Eloise C. (2010) Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding. Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy, 77, pp. 388-396.

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Abstract

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.

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ID Code: 33688
Item Type: Journal Article
Keywords: chalcophyllite; chenevixite;Near-infrared and Mid-infrared
DOI: 10.1016/j.saa.2010.05.020
ISSN: 1386-1425
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Structural Chemistry and Spectroscopy (030606)
Divisions: Past > Schools > Chemistry
Past > QUT Faculties & Divisions > Faculty of Science and Technology
Copyright Owner: Copyright 2010 Elsevier
Deposited On: 03 Aug 2010 08:54
Last Modified: 01 Mar 2012 00:17

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