Hostname: page-component-586b7cd67f-rcrh6 Total loading time: 0 Render date: 2024-11-23T03:59:58.738Z Has data issue: false hasContentIssue false
  • English
  • Français

Solubility and Thermodynamic Properties of Carbonate-Bearing Hydrotalcite—Pyroaurite Solid Solutions with A 3:1 Mg/(Al+Fe) Mole Ratio

Published online by Cambridge University Press:  01 January 2024

K. B. Rozov ,
U. Berner ,
D. A. Kulik  and
L. W. Diamond
K. B. Rozov*
Affiliation:
Waste Management Laboratory, Paul Scherrer Institute, 5210 Villigen, Switzerland Rock-Water Interaction Group, Institute of Geological Sciences, University of Bern, Baltzerstrasse 3, 3012 Bern, Switzerland
U. Berner
Affiliation:
Waste Management Laboratory, Paul Scherrer Institute, 5210 Villigen, Switzerland
D. A. Kulik
Affiliation:
Waste Management Laboratory, Paul Scherrer Institute, 5210 Villigen, Switzerland
L. W. Diamond
Affiliation:
Rock-Water Interaction Group, Institute of Geological Sciences, University of Bern, Baltzerstrasse 3, 3012 Bern, Switzerland
*
* E-mail address of corresponding author: k.rozov@fz-juelich.de
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The naturally occurring layered double hydroxides (LDH, or anionic clays) are of particular interest in environmental geochemistry because of their ability to retain hazardous cations and especially anions. However, incorporation of these minerals into predictive models of water-rock interaction in contaminant environments, including radioactive-waste repositories, is hampered by a lack of thermodynamic and stability data. To fill part of this gap the present authors have derived properties of one of the complex multicomponent solid solutions within the LDH family: the hydrotalcite-pyroaurite series, Mg3(Al1−xFex)(OH)8(CO3)0.5·2.5H2O.

Members of the hydrotalcite-pyroaurite series with fixed MgII/(AlIII+FeIII) = 3 and various FeIII/(FeIII+AlIII) ratios were synthesized by co-precipitation and dissolved in long-term experiments at 23±2°C and pH = 11.40±0.03. The chemical compositions of co-existing solid and aqueous phases were determined by inductively coupled plasma-optical emission spectroscopy, thermogravimetric analysis, and liquid scintillation counting of 55Fe tracers; X-ray diffraction and Raman were used to characterize the solids. Based on good evidence for reversible equilibrium in the experiments, the thermodynamic properties of the solid solution were examined using total-scale Lippmann solubility products, ΣΠT. No significant difference was observed between values of SPT from co-precipitation and from dissolution experiments throughout the whole range of Fe/Al ratios. A simple ideal solid-solution model with similar end-member ΣΠT values (a regular model with 0 < WG < 2 kJ mol −1 sufficient to describe the full range of intermediate mineral compositions. In turn, this yielded the first estimate of the standard Gibbs free energy of the pyroaurite end member, G298,Pyro = −3882.60±2.00 kJ/mol, consistent with G298,Htlco = −4339.85 kJ/mol of the hydrotalcite end member, and with the whole range of solubilities of the mixed phases. The molar volumes of the solid-solution at standard conditions were derived from X-ray data. Finally, Helgeson’s method was used to extend the estimates of standard molar entropy and heat capacity of the end members over the pressure-temperature range 0−70°C and 1–100 bar.

Keywords

Aqueous SolubilityHydrotalciteLDHMolar VolumePyroauriteSolid SolutionsThermodynamic Modeling
Type
Article
Information
Clays and Clay Minerals , Volume 59 , Issue 3 , June 2011 , pp. 215 - 232
Copyright
Copyright © The Clay Minerals Society 2011

References

Allada, R.K. Navrotsky, A. and Boerio-Goates, J., 2005 Thermochemistry of hydrotalcite-like phases in the MgOAl2O3-CoO2-H2O system: A determination of enthalpy, entropy and free energy American Mineralogist 90 329–335 10.2138/am.2005.1737.CrossRefGoogle Scholar
Allmann, R., 1968 Crystal structure of pyroaurite Acta Crystallographica. Section B. Structural Crystallography and Crystal Chemistry B24 972 10.1107/S0567740868003511.CrossRefGoogle Scholar
Bish, D.L. and Howard, S.A., 1988 Quantitative phaseanalysis using the Rietveld method Journal of Applied Crystallography 21 86–91 10.1107/S0021889887009415.CrossRefGoogle Scholar
Brindley, G.W. and Kikkawa, S., 1979 A crystal-chemical study of Mg, Al and Ni, Al hydroxy-perchlorates and hydroxy-carbonates American Mineralogists 64 836–843.Google Scholar
Brindley, G.W. and Kikkawa, S., 1980 Thermal-behavior of hydrotalcite and of anion-exchanged forms of hydrotalcite Clays and Clay Minerals 28 87–91 10.1346/CCMN.1980.0280202.CrossRefGoogle Scholar
Carrado, K.A. Kostapapas, A. and Suib, S.L., 1988 Layered double hydroxides (LDHs) Solid State Ionics 26 77–86 10.1016/0167-2738(88)90018-5.CrossRefGoogle Scholar
Cavani, F. Trifiro, F. and Vaccari, A., 1991 Hydrotalcitetype anionic clays: Preparation, properties and applications Catalysis Today 11 173–301 10.1016/0920-5861(91)80068-K.CrossRefGoogle Scholar
Chibwe, K. and Jones, W., 1989 Intercalation of organic and inorganic anions into layered double hydroxides Journal of the Chemical Society - Chemical Communications 926–927.CrossRefGoogle Scholar
Chisem, I.C. and Jones, W., 1994 Ion-exchange properties of lithium aluminum layered double hydroxides Journal of Materials Chemistry 4 1737–1744 10.1039/jm9940401737.CrossRefGoogle Scholar
Danton, A.R., 1991 Vegard’s law Physical Review 43 3161–3164 10.1103/PhysRevA.43.3161.CrossRefGoogle Scholar
De Roy, A. Forano, C. El Malki, M. and Besse, J.-P., 1992 Anionic clays: Trends in Pillaring Chemistry New York Van Nostrand Reinhold.Google Scholar
Drits, V.A. Bookin, A.S. and Rives, V., 2001 Crystal structure and X-ray identification of layered double hydroxides Layered Double Hydroxides. Present and Future New York Nova Science Publishers 41–100.Google Scholar
Drits, V.A. Sokolova, T.N. Sokolova, G.V. and Cherkashin, V.I., 1987 New members of the hydrotalcite-manasseite group Clays and Clay Minerals 35 401–417 10.1346/CCMN.1987.0350601.CrossRefGoogle Scholar
Frost, R.L. and Reddy, B.J., 2006 Thermo-Raman spectroscopic study of the natural layered double hydroxide manasseite Spectrochimica Acta. Part A. Molecular and Biomolecular Spectroscopy 65 553–559 10.1016/j.saa.2005.12.007.CrossRefGoogle ScholarPubMed
Gutmann, N. and Müller, B., 1996 Insertion of the dinuclear dihydroxo-bridged Cr(IV) aquo complex into the layered double hydroxides of hydrotalcite-type Journal of Solid State Chemistry 122 214–220 10.1006/jssc.1996.0104.CrossRefGoogle Scholar
Helgeson, H.C. Delany, J.M. Nesbitt, H.W. and Bird, D.K., 1978 Summary and critique of the thermodynamic properties of rock-forming minerals American Journal of Science 278A 1–229.Google Scholar
Hummel, W., 2002 Nagra/PSI Chemical Thermodynamic Database 01/01 Parkland, Florida, USA Universal-Publishers.Google Scholar
Johnson, C.A. and Glasser, F.P., 2003 Hydrotalcite-like minerals (M2Al(OH)6(CO3)0.5·nH2O, where M = Mg, Zn, Co, Ni) in the environment: Synthesis, characterization and thermodynamic stability Clays and Clay Minerals 51 1–8 10.1346/CCMN.2003.510101.CrossRefGoogle Scholar
Khan, A.I. and O’Hare, D., 2002 Intercalation chemistry of layered double hydroxides: Recent developments and applications Journal of Materials Chemistry 12 3191–3198 10.1039/B204076J.CrossRefGoogle Scholar
Kovanda, F. Koulousek, D. Cilova, Z. and Hulinski, V., 2005 Crystallization of synthetic hydrotalcite under hydrothermal conditions Applied Clay Science 28 101–109 10.1016/j.clay.2004.01.009.CrossRefGoogle Scholar
Lippmann, F., 1980 Phase diagrams depicting aqueous solubility of binary mineral systems Neues Jahrbuch für Mineralogie Abhandlungen 139 1–25.Google Scholar
Majzlan, J. Grevel, K.D. and Navrotsky, A., 2003a Thermodynamics of Fe oxides: Part II. Enthalpies of formation and relative stability of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe2O3) American Mineralogist 88 855–859 10.2138/am-2003-5-614.CrossRefGoogle Scholar
Majzlan, J. Lang, B.E. Stevens, R. Navrotsky, A. Woodfield, B.F. and Boerio-Goates, J., 2003b Thermodynamics of Fe oxides: Part I. Entropy at standard temperature and pressure and heat capacity of goethite (aα-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe2O3) American Mineralogist 88 846–854 10.2138/am-2003-5-613.CrossRefGoogle Scholar
Miyata, S., 1975 The syntheses of hydrotalcite-like compounds and their structures and physico-chemical properties Clays and Clay Minerals 23 369–375 10.1346/CCMN.1975.0230508.CrossRefGoogle Scholar
Miyata, S., 1980 Physicochemical properties of synthetic hydrotalcites in relation to composition Clays and Clay Minerals 28 50–56 10.1346/CCMN.1980.0280107.CrossRefGoogle Scholar
Miyata, S., 1983 Anion-exchange properties of hydrotalcitelike compounds Clays and Clay Minerals 31 305–311 10.1346/CCMN.1983.0310409.CrossRefGoogle Scholar
Parkhurst, D.L. and Appelo, C.A.J., 1999 User’s guide to PHREEQC 99–4259.Google Scholar
Prikhod’ko, R.V. Sychev, M.V. Astrelin, I.M. Erdmann, K. Mangel, A. and van Santen, R.A., 2001 Synthesis and structural transformations of hydrotalcite-like materials Mg-Al and Zn-Al Russian Journal of Applied Chemistry 74 1621–1626 10.1023/A:1014832530184.CrossRefGoogle Scholar
Rozov, K. Berner, U. Taviot-Gueho, C. Leroux, F. Renaudin, G. Kulik, D. and Diamond, L.W., 2010 Synthesis and characterization of the LDH hydrotalcitepyroaurite solid solution series Cement and Concrete Research 40 1248–1254 10.1016/j.cemconres.2009.08.031.CrossRefGoogle Scholar
Trave, A. Selloni, A. Goursot, A. Tichit, D. and Weber, J., 2002 First principles study of the structure and chemistry of Mg-based hydrotalcite-like anionic clays Journal of Physical Chemistry 106 12291–12296 10.1021/jp026339k.CrossRefGoogle Scholar
Vagvolgyi, V. Palmer, S.J. Kristof, J. Frost, R.L. and Horvath, E., 2008 Mechanism for hydrotalcite decomposition: A controlled rate thermal analysis study Journal of Colloid and Interface Science 318 302–308 10.1016/j.jcis.2007.10.033.CrossRefGoogle ScholarPubMed
Vidal, O. and Dubacq, B., 2009 Thermodynamic modelling of clay dehydration, stability and compositional evolution with temperature, pressure and H2O activity Geochimica et Cosmochimica Acta 73 6544–6564 10.1016/j.gca.2009.07.035.CrossRefGoogle Scholar