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Structural interpretation of anion exchange in divalent copper hydroxysalt minerals

Published online by Cambridge University Press:  09 July 2018

TS. Stanimirova ,
S. Dencheva  and
G. Kirov
TS. Stanimirova*
Affiliation:
University of Sofia “St. Kliment Ohridski”, Faculty of Geology and Geography, Department of Mineralogy, Petrology and Economic Geology, 1000 Sofia, 15 Tzar Osvoboditel Blvd, Bulgaria
S. Dencheva
Affiliation:
University of Sofia “St. Kliment Ohridski”, Faculty of Geology and Geography, Department of Mineralogy, Petrology and Economic Geology, 1000 Sofia, 15 Tzar Osvoboditel Blvd, Bulgaria
G. Kirov
Affiliation:
University of Sofia “St. Kliment Ohridski”, Faculty of Geology and Geography, Department of Mineralogy, Petrology and Economic Geology, 1000 Sofia, 15 Tzar Osvoboditel Blvd, Bulgaria
*
*E-mail: [email protected]
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Abstract

Minerals with the general formula Cu4(OH)6A2/nn ± pH2O (A = Cl–, NO3–, SO42–) were synthesized and their behaviour following treatment with chloride, nitrate and sulfate solutions was studied by powder XRD and SEM. Two types of transformation were found: (1) an ion-exchange reaction manifested by preservation of both the precursor's morphology and structural type; (2) a dissolution-crystallization mechanism characterized by changes in the structural type and the morphology.

The results were considered by simultaneous application of the binary presentation of the structures, a bond valence approach and the ion-exchange ability. It was found that the structures of minerals with ion-exchange properties are built from similar layered structural unit of edge-shared and corner-shared Jahn-Teller square frameworks and different interstitial complexes of exchangeable ions, water molecules and cation-water groups. On the basis of their structural features the position of the investigated minerals in mineralogical classifications is also discussed.

Keywords

copper hydroxysalt mineralsbinary presentationJahn-Teller effection-exchangepowder XRD
Type
Research Article
Information
Clay Minerals , Volume 48 , Issue 1 , March 2013 , pp. 21 - 36
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2013

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References

Biswick, T., Jones, W.A., Pacula, & Serwicka, E. (2006) Synthesis, characterization and anion exchange properties of copper, magnesium, zinc and nickel hydroxy nitrates. Journal of Solid State Chemistry, 179, 49–55.CrossRefGoogle Scholar
Burns, P.C. & Hawthorne, F.C. (1995) Mixed-ligand Cu2+Φ6 octahedra in minerals: Observed stereochemistry and Hartree-Fock calculations. The Canadian Mineralogist, 33, 1177–1188.Google Scholar
Clark, A.M. (1993) Hey's Mineral Index, Chapman & Hall, London, 852 pp.Google Scholar
Dencheva, S., Stanimirova, Ts. & Kirov, G. (2007), Anionic clays in mineralogy: crystal-chemical classification and nomenclature. Annuaire de L’Universite de Sofia “St. Kliment Ohridski, Faculté de Geologie et Geographie, 100, 177–193 (in Bulgarian).Google Scholar
Eby, R.K. & Hawthorne, F.C. (1993) Structural relations in copper oxysalt minerals. I, Structural heirarchy. Acta Crystallographica, B49, 28–56.Google Scholar
Fleet, M.E. (1975) The crystal structure of paratacamite, Cu2(OH)3Cl. Acta Crystallographica, B31, 183–187.Google Scholar
Gaines, R.V. (1997) Dana's New Mineralogy. John Wiley & Sons, New York, p. 1819.Google Scholar
Gentsch, M. & Weber, K. (1984) Structure of langite, Cu4[(OH)6|SO4].2H2O Acta Crystallographica, C40, 1309–1311.Google Scholar
Hawthorne, F.C. (1985) Refinement of the crystal structure of botallackite. Mineralogical Magazine, 49, 87–89.Google Scholar
Hawthorne, F.C. (1992) The role of OH and H2O in oxide and oxysalt minerals. Zeitschrift fur Kristallographie, 201, 183–206.Google Scholar
Hawthorne, F.C. & Schindler, M. (2000) Topological enumeration of decorated [Cu2+ϕ2]N sheets in hydroxyl-hydrated copper-oxysalt minerals. The Canadian Mineralogist, 38, 751–761.CrossRefGoogle Scholar
Henrist, C., Traina, K., Hubert, C., Toussaint, G., Rulmont, A. & Cloots, R. (2003) Study of the morphology of copper hydroxynitrate nanoplatelets obtained by controlled double jet precipitation and urea hydrolysis. Journal of Crystal Growth, 254, 176–187.CrossRefGoogle Scholar
Laget, V., Hornick, C., Rabu, P. & Drillon, M. (1999) Hybrid organic-inorganic layered compounds prepared by anion exchange reaction: correlation between structure and magnetic properties. Journal of Materials Chemistry, 9, 169–174.CrossRefGoogle Scholar
Kostov, I. (1968) Mineralogy. Oliver & Boyd, Edinburgh & London, 587 pp.Google Scholar
Mellini, M. & Merlino, S. (1978) Ktenasite, another mineral with ∞ 2[(Cu,Zn)2(OH)3O]– octahedral sheets. Zeitschrift fur Kristallographie, 147, 129–140.CrossRefGoogle Scholar
Mellini, M. & Merlino, S. (1979) Posnjakite: ∞ 2[Cu4(OH)6(H2O)O] octahedral sheets in its structure. Zeitschrift fur Kristallographie, 149, 249–257.Google Scholar
Merlino, S., Perchiazzi, N. & Franco, D. (2003) Brochantite, Cu4SO4(OH)6: OD character, polytypism and crystal structures. European Journal of Mineralogy, 15, 267–275.CrossRefGoogle Scholar
Meyn, M., Beneke, K. & Lagaly, G. (1993) Anionexchange reactions of hydroxy double salts. Inorganic Chemistry, 32, 1209–1215.Google Scholar
Momma, K. & Izumi, F. (2011) VESTA 3 for threedimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44, 1272–1276.Google Scholar
Nechiporenko, G.O. (1971) On the synthetic posnjakite. Proceedings of the Russian Mineralogical Society, 100, 754–756.(in Russian).Google Scholar
Newman, S.P. & Jones, W. (1999) Comparative study of some layered hydroxide salts containing exchangeable interlayer anions. Journal of Solid State Chemistry, 148, 26–40.Google Scholar
Parise, J.B. & Hyde, B.G (1986) The structure of atacamite and its relationship to spinel. Acta Crystallographica, C42, 1277–1280.Google Scholar
Pollard, A.M., Thomas, R.G. & Willams, P.A (1989) Synthesis and stabilities of the basic copper (II) chlorides atacamite, paratacamite and botallackite. Mineralogical Magazine, 53, 557–563.Google Scholar
Rajamathi, J.T., Britto, S. & Rajamathi, M. (2005) Synthesis and anion exchange reactions of a layered copper-zinc hydroxy double salt, Cu1.6Zn0.4(OH)3 (OAc).H2O. Journal of Chemical Sciences, 117, 629–633.CrossRefGoogle Scholar
Rajamathi, M., Thomas, G.S. & Kamath, P.V. (2001) The many ways of making anionic clays. Proceedings of the Indian Academy of Sciences (Chemical Sciences), 113, 671–680.Google Scholar
Sarp, H., Černý, R. & Guenee, L. (2001) Rouaite, Cu2(NO3)(OH)3, un nouveau minéral: sa description et sa structure cristalline (Alpes-Maritimes, France). Riviera Scientifique, 85, 3–12.(in French).Google Scholar
Schindler, M. & Hawthorne, F.C. (2001) A bond-valence approach to the structure, chemistry and paragenesis of hydroxy-hydrated oxysalt minerals. I, Theory. The Canadian Mineralogist, 39, 1225–1242.Google Scholar
Schindler, M. & Hawthorne, F.C. (2008) The stereochemistry and chemical composition of interstitial complexes in uranyl-oxysalt minerals. The Canadian Mineralogist, 46, 467–501.Google Scholar
Sharkey, J.B. & Lewin, S.Z. (1971) Conditions governing the formation of atacamite and paratacamite. American Mineralogist, 56, 179–192.Google Scholar
Strandberg, H., Langer, & V. Johansson, L.G. (1995) Structure of Cu2.5(OH)3SO4.2H2O: a novel corrosion product of copper. Acta Chemica Scandinavica, 49, 5–10.CrossRefGoogle Scholar
Strunz, H. (2004) http://webmineral.com/strunz.shtml Google Scholar
Uvarova, Y.A., Sokolova, E., Hawthorne, F.C., Karpenko, V.V., Agakhanov, A.A. & Pautov, L.A. (2005) The crystal chemistry of the “nickelalumite”-group minerals. The Canadian Mineralogist, 43, 1511–1519.CrossRefGoogle Scholar
Woods, T.L. & Garrels, R.M. (1986a) Phase relations of some cupric hydroxy minerals. Economic Geology, 81, 1989–2007.Google Scholar
Woods, T.L. & Garrels, R.M. (1986b) Use of oxidized copper minerals as environmental indicators. Applied Geochemistry, 1, 181–187.Google Scholar
Yamanaka, S., Sako, T., Seki, K. & Hattori, M. (1992) Anion exchange reactions in layered basic copper salts. Solid State Ionics, 53–56, 527–533.Google Scholar
Yoder, C.H., Agee, T.M., Ginion, K.E., Hofmann, A.E., Ewanichak, J.E., Schaeffer, C.D., Carroll, M.J., Schaeffer, R.W. & McCaffrey, P.F. (2007) The relative stabilities of the copper hydroxyl sulphates. Mineralogical Magazine, 71, 571–577.CrossRefGoogle Scholar
Yoder, C.H., Gotlieb, N.R. & Rowand, A.L. (2010a) The relative stability of stoichiometrically related natural and synthetic double salts. American Mineralogist, 95, 47–51.Google Scholar
Yoder, C.H., Bushong, E., Liu, X., Weidner, V., McWilliams, P., Martin, K., Lorgunpai, J., Haller, J. & Schaeffer, R.W. (2010b) The synthesis and solubility of the copper hydroxyl nitrates: gerhardtite, rouaite and likasite. Mineralogical Magazine, 74, 433–440.CrossRefGoogle Scholar