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Modeling of H+ and Cu2+ Adsorption on Calcium-Montmorillonite

Published online by Cambridge University Press:  28 February 2024

Markus Stadler  and
Paul W. Schindler
Markus Stadler*
Affiliation:
Institute for Inorganic Chemistry, University of Berne, Freiestrasse-3, CH-3012-Berne, Switzerland
Paul W. Schindler
Affiliation:
Institute for Inorganic Chemistry, University of Berne, Freiestrasse-3, CH-3012-Berne, Switzerland
*
1Author to whom correspondence should be addressed.
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Abstract

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The interaction of H+- and Cu2+-ions with Ca-montmorillonite was investigated in 0.1 mol/dm3 solutions of Ca(CIO4)2 at 298.2 K by Potentiometrie titrations using both glass electrodes (for H+) and ion specific electrodes (for Cu2+ ). The experimental data were interpreted on the basis of the surface complexation model. The calculations were performed with the least-squares program FITEQL (Westall, 1982) using the constant capacitance approximation. The best fit was obtained with a set of equilibria of the general form

pH++qCu2++≡SOH⇔(H+)p(Cu2+)q(≡SOH)(p+2q)+βp,q(int)s=[HpCuq(≡SOH)(p+2q)][H+]p[Cu2+]q[≡SOH]
and the constants log β1,0(int)S = 8.16 (± 0.04), log β-1,0(int)S = −8.71 (± 0.08), log β0,1(int)S = 5.87 (± 0.06), log β−1,1(int)S = −0.57 (± 0.12), log β−2,1(int)S = −6.76 (± 0.02). An appropriate modeling of the H+ adsorption data requires the introduction of a second surface group ≡ TOH with the acidity constant
≡TOH−H+⇔≡TO−logβ−1,0(int)S=−5.77(±0.07).
 In addition, the ion exchange equilibria Ca2+ − Cu2+ and Ca2+ − H+ had to be taken into account. Arguments are presented to identify the groups ≡ SOH and ≡ TOH as surface aluminol groups =Al(OH)(H2O) and surface silanol groups ≡ Si-OH, respectively.

Keywords

AdsorptionCopperModelingMontmorillonite
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 3 , June 1993 , pp. 288 - 296
Copyright
Copyright © 1993, The Clay Minerals Society

References

Baes, C. F. and Mesmer, R. E., 1976 The Hydrolysis of Cations New York Wiley Interscience 189.Google Scholar
Banin, A., 1969 Ion exchange isotherms of montmorillonite and structural factors affecting them Isr. J. Chem. 6 27 – 36 10.1002/ijch.196800005.CrossRefGoogle Scholar
Benson, L. V., 1982 A tabulation and evaluation of ion exchange data on smectites Environ. Geol. 4 23 – 29 10.1007/BF02380496.CrossRefGoogle Scholar
Davis, C. W., 1962 Ion association London Butterworths.Google Scholar
Davis, J. A., Kent, D. B., Hochella, M. F. Jr. and White, A. F., 1990 Surface complexation modeling in aqueous geochemistry Mineral-water Interface Geochemistry Washington, D.C. Reviews in Mineralogy 23, Mineralological Society of America 177 – 260 10.1515/9781501509131-009.CrossRefGoogle Scholar
El-Sayed, M. H., Burau, R. G. and Babcock, K. L., 1970 Thermodynamics of copper(II)-calcium exchange on Bentonite clay Soil Sci. Soc. Am. J. 34 397 – 400 10.2136/sssaj1970.03615995003400030016x.CrossRefGoogle Scholar
Eltantawy, I. M. and Arnold, P. W., 1973 Reappraisal of the ethylene glycol mono-ethyl ether (EGME) method for surface area estimations of clays J. Soil Sci. 24 232 – 238 10.1111/j.1365-2389.1973.tb00759.x.CrossRefGoogle Scholar
Fletcher, P. and Sposito, G., 1989 The chemical modeling of clay/electrolyte interactions for montmorillonite Clay Miner. 24 375 – 391 10.1180/claymin.1989.024.2.14.CrossRefGoogle Scholar
Gaines, G. L. and Thomas, H. C., 1953 Adsorption studies on clay minerals. II. A formulation of the thermodynamics of exchange adsorption J. Chem. Phys. 21 714 – 718 10.1063/1.1698996.CrossRefGoogle Scholar
Hiemstra, T., Van Riemsdijk, W. H. and Bolt, G. H., 1989 Multisite proton adsorption modeling at the solid/solution interface of (Hydr)oxides: A new approach J. Colloid Interface Sci. 133 91 – 104 10.1016/0021-9797(89)90284-1.CrossRefGoogle Scholar
James, R. O., and Parks, G. A., (1982) Characterization of aqueous colloids by their electrical double-layer and intrinsic surface chemical properties: Surface and Colloid Science, Vol. 12, Matijevic, E., ed., Plenum Publishing Corporation, New York.Google Scholar
King, E. J., 1965 Acid-Base Eauilibria Oxford Pergamon Press 117 – 128.Google Scholar
Martell, A. E. and Smith, R. M., 1976 Critical Stability Constants, Vol. 4: Inorganic Complexes New York and London Plenum Press.Google Scholar
Pulfer, K., 1981 Kinetik und Mechanismus der Auflösung von γ-Al(OH)3 (Bayerit) in HNO3-HF-Lösungen Switzerland University of Berne.Google Scholar
Pulfer, K., 1984 Kinetics and mechanism of dissolution of Bayerite γ 101 2 554 – 564.Google Scholar
Schindler, P. W. and Gamsjäger, H., 1972 Acid-base reactions of the TiO2 (anatase)-water interface and the point of zero charge of TiO2 suspensions Kolloid Z. und Z. Polymere 250 759 – 765 10.1007/BF01498568.CrossRefGoogle Scholar
Schindler, P. W., Stumm, W. and Stumm, W., 1987 The surface chemistry of oxides, hydroxides and oxide minerals Aquatic surface chemistry New York Wiley Interscience 83 – 110.Google Scholar
Schindler, P. W., Liechti, P. and Westall, J. C., 1987 Adsorption of copper, cadmium and lead from aqueous solution to the kaolinite/water interface Netherlands J. of Agricultural Science 35 219 – 230.CrossRefGoogle Scholar
Schindler, P. W., and Sposito, G., (1991) Surface complexation at (hydr)oxide surfaces: in Interactions at the Soil Colloid-Soil Solution Interface, G. H. Bolt, M. F. DeBoodt, M. H. B. Hayes, and M. B. McBride, eds. NATO ASI Series; Series E; Applied Sciences Vol. 190; Kluwer Academic Publishers Dordrecht, Boston, London.CrossRefGoogle Scholar
Shaviv, A. and Mattigod, S. V., 1985 Cation exchnge equilibria in soils expressed as cation-ligand complex formation Soil Sci. Soc. Am. J. 49 569 10.2136/sssaj1985.03615995004900030007x.CrossRefGoogle Scholar
Sposito, G., 1981 Thermodynamics of Soil Solutions .Google Scholar
Sposito, G., Holtzclaw, K. M., Charlet, L., Jouany, C. and Page, L., 1983 Sodium-Calcium and Sodium-magnesium exchange on Wyoming Bentonite in Perchlorate and chloride background ionic media Soil Sci. Soc. Am. J. 47 51 – 56 10.2136/sssaj1983.03615995004700010010x.CrossRefGoogle Scholar
Sposito, G., 1984 The Surface Chemistry of Soils Oxford Oxford University Press.Google Scholar
Westall, J. C. and Stumm, W., 1987 Adsorption mechanisms in aquatic surface chemistry Aquatic Surface Chemistry New York Wiley Interscience 3 – 32.Google Scholar
Westall, J. C., 1982 A program for the determination of chemical equilibrium constants from experimental data Corvallis User’s Guide vs. 1.2., Oregon State University.Google Scholar