Hostname: page-component-78c5997874-xbtfd Total loading time: 0 Render date: 2024-11-19T22:44:30.809Z Has data issue: false hasContentIssue false
  • English
  • Français

The synthesis of copper/zinc solid solutions of hydroxyl carbonates, sulphates, nitrates, chlorides and bromides

Published online by Cambridge University Press:  05 July 2018

C. H. Yoder ,
R. W. Schaeffer ,
P. McWilliams ,
A. Rowand ,
X. Liu  and
J. Shambeda
C. H. Yoder*
Affiliation:
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604, USA
R. W. Schaeffer
Affiliation:
Department of Chemistry, Messiah College, Grantham, PA 17055, USA
P. McWilliams
Affiliation:
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604, USA
A. Rowand
Affiliation:
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604, USA
X. Liu
Affiliation:
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604, USA
J. Shambeda
Affiliation:
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604, USA
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

The relative stabilities of the copper/zinc solid solutions of hydroxyl sulphates, carbonates, nitrates, chlorides and bromides were studied by attempting their preparation using a variety of methods. All of the naturally occurring solid solutions except rosasite were obtained as single phases. Rosasite crystallized in a mixture with malachite and calcium carbonate during a room temperature preparation from calcium carbonate, copper nitrate and zinc nitrate. The solid solution with the antlerite stoichiometry [endmember Cu3SO4(OH)4] as well as the nitrates were not produced by the methods employed. All of the natural polymorphs of Cu2(OH)3Cl were obtained and a new method for the preparation of botallackite is reported. Botallackite was found to be stable in solution for over a year, contrary to previous reports. A bromine-bearing analogue of botallackite was prepared. Compounds were characterized by X-ray diffractometry, which was used to determine the unit-cell parameters, and by atomic absorption spectroscopy. The relative instability of solid solutions with certain stoichiometries is discussed in terms of the Jahn-Teller effect and relative solubilities.

Keywords

Cu/Zn ratiossolid solutionhydroxyl carbonates and sulphatessynthesis
Type
Research Article
Information
Mineralogical Magazine , Volume 75 , Issue 5 , October 2011 , pp. 2573 - 2582
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Adib, D. and Ottemann, J. (1972) Ein neues Mineral, (Cu,Zn)2(OH)3Cl, aus der Kali-Kafi Mine, Provinz Anarak, Zentral Iran. Neues Jahrbuch für Mineralogie, Monatshefte, 335–338. [abstracted with comments, in American Mineralogist (1973), 58, 560-561.Google Scholar
Bems, B., Schur, M., Dassenoy, A., Junkes, H., Herein, D. and Schlögl, R. (2003) Relations between synthesis and microstructural properties of copper/ zinc hydroxycarbonates. Chemistry; a European Journal, 9, 2039-2052.CrossRefGoogle ScholarPubMed
Bevins, R.E., Turgoose, S. and Williams, P.A. (1982) Namuwite, (Zn,Cu)4SO4(OH)6.4H2O, a new mineral from Wales. Mineralogical Magazine, 46, 51-54.CrossRefGoogle Scholar
Braithwaite, R.S.W., Mereiter, K., Paar, W.H. and Clark, A.M. (2004) Herbertsmithite, Cu3Zn(OH)6Cl2, a new species, and the definition of paratacamite. Mineralogical Magazine, 68, 527-539.CrossRefGoogle Scholar
Bulko, J.B., Herman, R.G., Klier, K. and Simmons, G.W. (1979) Optical properties and electronic interactions of microcrystalline copper/zinc oxide (Cu/ZnO) catalysts. Journal of Physical Chemistry, 83, 3118-3122.CrossRefGoogle Scholar
Cocco, G. and Mazzi, F. (1959) La struttura della brochantite. Periodico di Mineralogia – Roma, 28, 121-149.Google Scholar
Fang, D., Liu, Z., Meng, S., Ligang, W., Xu, L. and Wang, H. (2005) Influence of aging time on the properties of precursors of CuO/ZnO catalysts for methanol synthesis. Journal of Natural Gas Chemistry, 14, 107-114.Google Scholar
Fleet, M.E. (1975) The crystal structure of paratacamite, Cu2(OH)3Cl. Acta Crystallographica, B31, 187-.Google Scholar
Fujita, S., Satriyo, A.M., Shen, G.C. and Takezawa, N. (1995) Mechanism of the formation of precursors for the Cu/ZnO methanol synthesis catalysts by a coprecipitationme thod. Catalysis Letters, 34, 85-92.CrossRefGoogle Scholar
Gilbert, J. (1977) Les sulphates basiques mixtes de cuivre et de zinc. Bulletin des Sociétés Chimiques Belges, 86, 1-9.CrossRefGoogle Scholar
Grice, J.D., Szymanski, J.T. and Jambor, J.L. (1996) The crystal structure of clinoatacamite, a new polymorph of Cu2(OH)3Cl. The Canadian Mineralogist, 34, 73-78.Google Scholar
Groat, L.A. (1996) The crystal structure of namuwite, a mineral with Zninte trahedral and octahedral coordination, and its relationship to the synthetic basic zinc sulphates. American Mineralogist, 81, 238-243.CrossRefGoogle Scholar
Harding, M.M., Kariuki, B.M., Cernik, R. and Cressey, G. (1994) The structure of aurichalcite, (Cu,Zn)5(OH)6(CO3)2, determined from a microcrystal. Acta Crystallographica, B50, 67-.Google Scholar
Hawthorne, F.C. (1985) Refinement of the crystal structure of botallackite. Mineralogical Magazine, 49, 87-89.CrossRefGoogle Scholar
Hawthorne, F.C., Groat, L.A. and Eby, R.K. (1989) Antlerite, Cu3SO4(OH)4, a heteropolyhedral wallpaper structure. The Canadian Mineralogist, 27, 205-20.Google Scholar
Herman, R.G., Bogdan, C.E., Kumler, P.L. and Nuszkowski, D.M. (1993) Preparationan d characterizationof hydroxycarbonate precursors that yield successful alcohol synthesis catalysts. Materials Chemistry and Physics, 35, 233-239.CrossRefGoogle Scholar
Holland, T.J.B. and Redfern, S.A.T. (1997) Unit cell refinement from powder diffraction data: the use of regressiondiagn ostics. Mineralogical Magazine, 61, 65-77.CrossRefGoogle Scholar
Jambor, J.L., Dutrizac, J.E., Roberts, A.C., Grice, J.D. and Szymanski, J.T. (1996) Clinoatacamite, a new polymorph of Cu2(OH)3Cl, and its relationship to paratacamite and “anarakite”. The Canadian Mineralogist, 34, 61-72.Google Scholar
Nowacki, W. and Scheidegger R. (1952) Die Kristallstructurbestimmung des monoklinen, basischenKupf ernitrates Cu4(NO3)2(OH)6 II. Helvetica Chimica Acta, 35, 375-390.CrossRefGoogle Scholar
Oswald, H.R., Iitaka, Y., Locchi, S. and Ludi, A. (1961) Die Kristallstruckturen von Cu2(OH)3Br und Cu2(OH)3 . Helvetica Chimica Acta, 44, 2103-2109.CrossRefGoogle Scholar
Parise, J.B. and Hyde, B.G. (1986) The structure of atacamite and its relationship to spinel. Acta Crystallographica, C42, 1280-.Google Scholar
Pollard, A.M., Thomas, R.G. and Williams, P.A. (1989) Synthesis and stabilities of the basic copper (II) chlorides atacamite, paratacamite, and botallackite. Mineralogical Magazine, 53, 557-563.CrossRefGoogle Scholar
Ramirez Garcia, A., Gutierrez Rexach, P., Cano-Ruiz, J. and Garcia Martinez, O. (1974) Hydroxy salts XVII copper and zinc mixed hydroxysulphates. Anales de Quimica, 70, 687-695.Google Scholar
Reddy, J., Frost, R.L. and Locke, A. (2008) Synthesis and spectroscopic characterisation of aurichalcite (ZnCu2+)5(CO3)2(OH)6; implications for Cu–ZnO catalyst precursors. Transition Materials Chemistry, 33, 331-339.CrossRefGoogle Scholar
Susse, P. (1967) Verfeinerung der kristallstruktur des malachits, Cu2(OH)2CO3 . Acta Crystallographica, 22, 146-151.CrossRefGoogle Scholar
Wells, A.F. (1949) The crystal structure of atacamite and the crystal chemistry of cupric compounds. Acta Crystallographica, 2, 175-180.CrossRefGoogle Scholar
Xue, M., Chitrakar, R., Sakane, K., Ooi, K., Kobayashi, S., Ohnishi, M. and Doi, A. (2004) Synthesis of ktenasite, a double hydroxide of zinc and copper, and its intercalation reaction. Journal of Solid State Chemistry, 177, 1624-1630.CrossRefGoogle Scholar
Yoder, C.H. and Rowand, J.P. (2006) Application of the simple salt lattice energy approximation to the solubility of minerals. American Mineralogist, 91, 747-752.CrossRefGoogle Scholar
Yoder, C.H., Agee, T.M., Ginion, K.E., Hofmann, A.E., Ewanichak, J.E., Schaeffer, C.D., Jr, Carroll, M.J., Schaeffer, R.W. and McCaffrey, P.F. (2007) The relative stabilities of the copper hydroxyl sulphates. Mineralogical Magazine, 71, 571-577.CrossRefGoogle Scholar