Incorporation of Co in the rosasite–malachite carbonate group

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Marco E. Ciriotti
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Incorporation of Co in the rosasite–malachite carbonate group

Messaggio da Marco E. Ciriotti » sab 09 giu, 2018 15:02

Prossima pubblicazione.

▪ Perchiazzi, N., Dragone, R., Demitri, N., Vignola, P., Biagioni, C. (2018): Incorporation of Co in the rosasite–malachite carbonate group of minerals: crystal structure studies of kolwezite and synthetic cobaltoan malachites. European Journal of Mineralogy, 30, (in press).

The crystal structure of kolwezite, (Cu, Co)2(CO3)(OH)2, was refined by Rietveld method from synchrotron X-ray powder data to Rp = 4.56%, wRp = 6.51%. Kolwezite, P21/a, a = 12.201(1), b = 9.354(1), c = 3.1494(3) Å, β = 98.922(7)°, is isostructural with rosasite. Because of the Jahn-Teller effect, the Me1 polyhedron hosting Cu2+ only is strongly distorted towards a (4+2) coordination, while the Me2 octahedron, with major Co, is neatly a more regular one. The Me2+ polyhedra are connected through edge-sharing, forming “ribbons” running along [0 0 1] direction. These ribbons are interconnected by corner sharing to form “corrugated” layers, interlinked by the carbonate groups, giving rise to an infinite framework structure, with notation M − M = M−T. The Rietveld study of synchrotron X-ray powder data of synthetic cobaltoan malachites shows a decrease in unit-cell volume, with an anisotropic contraction of unit-cell parameters, with increasing Co content. The major progressive shortening of apical bonds in Me2 octahedra, with consequent regularization of the Jahn-Teller distorted Cu octahedra, drives a progressive compaction of the malachite structure; it is the main factor accounting for volume contraction in cobaltoan malachites.
Marco E. Ciriotti

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