Abstract
Bentonite, biotite, illite, kaolin, vermiculite and zeolite were treated with 0.1, 1.0 and 5.0 mol. dm−3 HCl or NaOH. Suspensions of Na homoionic forms of the initial and the treated minerals were back titrated with 0.1 mol. dm−3 NaOH. From back-titration data variable surface charge, QV, vs. pH dependencies and apparent surface dissociation constant distribution functions were estimated. Variable charge vs. pH curves were scaled against cation exchange capacity at pH 7.2 to obtain actual charge, QA, vs. pH plots. In general both treatments led to an increase of QV, while the QA value increased and decreased depending on the mineral and the treatment. Products of 5 mol dm−3 NaOH action on zeolite and of 1 and 5 mol. dm−3 NaOH on kaolin apparently developed a positive surface charge below pH ∼3.7 and below ∼4.3, respectively.
The heterogeneity of charge-generating surface groups was observed in natural minerals. During acid treatment, the number of weakly-acidic surface functional groups increased while the number of groups of stronger acidic character decreased. The opposite was found for alkaline treatment: the number of surface groups of intermediate acidity increased and that of low acidity decreased.
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Baccouche, A., Srasra, E. and El Maaoui, M. (1998) Preparation of Na-P1 and sodalite octahydrate zeolites from interstratified illite-smectite. Applied Clay Science, 13, 255–273.
Breen, C., Madejova, J. and Komadel P. (1995) Correlation of catalytic activity with infra-red, Si mass NMR and acidity data for acid-treated fine fractions of montmorillonites. Clay and Clay Material Sciences, Proceedings Euroclay’95, Leuwen (A. Elsen, P. Grobet, M. Keung, H. Lehman, R. Schoonheydt and H. Toufar, editors), pp. 202–203.
Brown, D. and Rhodes, C.N. (1995) Acid-treated and ion exchanged montmorillonite catalysts: dependence of activity on composition. Clay and Clay Material Sciences, Proceedings Euroclay’95, Leuwen (A. Elsen, P. Grobet, M. Keung, H. Lehman, R. Schoonheydt and H. Toufar, editors), pp. 189–190.
Chi Ma and Eggleton, R.A. (1999) Cation exchange capacity of kaolinite. Clays and Clay Minerals 47, 174–180.
De Wit, J.C.M, Van Riemsdijk, W.H., Nederlof, M.M., Kinniburgh, D.G. and Koopal, L.K. (1990) Analysis of ion binding on humic substances and the determination of intrinsic affinity distributions. Analytica Chimica Acta, 232, 189–207.
Dekany, I., Turi, L., Fonseca, A. and Nagy, J.B. (1999) The structure of acid treated sepiolites: small-angle X-ray scattering and multi MAS-NMR investigations. Applied Clay Science, 14, 141–160.
del Rey-Perez-Caballero, F.J. and Poncelet, G. (2000) Microporous 18 angstrom Al-pillared vermiculites: preparation and characterization. Microporous Mesoporous Materials, 37, 313–327.
Duquette, M. and Hendershot, W. (1993a) Soil surface charge evaluation by back-titration: I. Theory and method development. Soil Science Society of America Journal, 57, 1222–1228.
Duquette, M. and Hendershot, W. (1993b) Soil surface charge evaluation by back-titration: II. Application. Soil Science Society of America Journal, 57, 1228–1234.
Frank, U. and Gebhardt, H. (1991) Transformation and destruction of clay minerals caused by recent strong acidification of selected forest soils of Northern Germany. Proceedings 7th Euroclay Conference, Dresden (M. Storr, K.H. Henning and P. Adolphi, editors), pp. 369–374.
Goates, J.R. and Anderson, K. (1956) Acidic properties of quartz. Soil Science, 81, 277–282.
Huang, C.P. (1981) The surface acidity of hydrous solids. Pp. 183–218 in: Adsorption of Inorganics at Solid-Liquid Interfaces (M.A. Anderson and A. Rubin, editors). Ann Arbor Science, Michigan.
Janek, M. and Lagaly, G. (2001) Proton saturation and rheological properties of smectite dispersions. Applied Clay Science, 19, 121–130.
Jozefaciuk, G. and Bowanko, G. (2002) Effect of acid and alkali treatments on surface areas and adsorption energies of selected clay minerals. Clays and Clay Minerals (in press).
Jozefaciuk, G. and Shin, J.S. (1996a) A modified back-titration method to measure soil titration curves minimizing soil acidity and dilution effects. Korean Journal of Soil Science and Fertilizer, 29, 321–327.
Jozefaciuk, G. and Shin, J.S. (1996b) Distribution of apparent surface dissociation constants of some Korean soils as determined from back titration curves. Korean Journal of Soil Science and Fertilizer, 29, 328–335.
Keren, R. (1986) Reduction of the cation-exchange capacity of montmorillonite by take-up of hydroxy Al polymers. Clays and Clay Minerals, 22, 41–47.
Koopal, L.K., Van Riemsdijk, W.K. and Roffey, M.G. (1987) Surface ionization and complexation models: a comparison of methods for determining model parameters. Journal of Colloid and Interface Science, 118, 117–136.
McBride, M.B. (1997) A critique of diffuse double layer models applied to colloid and surface chemistry. Clays and Clay Minerals, 45, 598–608.
Mrad, I., Ghorbel, A., Tichit, D. and Lambert J.F. (1997) Optimisation of the preparation of an Al-pillared clay: thermal stability and surface acidity. Applied Clay Science, 12, 349–364.
Nederlof, M.M., Venema, P., Van Riemsdijk, W.H. and Koopal, L.K. (1991) Modeling variable charge behaviour of clay minerals. Proceedings 7th Euroclay Conference, Dresden (M. Storr, K.H. Henning and P. Adolphi, editors), pp. 795–800.
Nederlof, M.M., De Wit, J.C., Riemsdijk, W.H. and Koopal, L.K. (1993) Determination of proton affinity distributions for humic substances. Environmental Science and Technology, 27, 846–856.
Parks, G.A. (1965) The isoelectric points of solid oxides, solid hydroxides and aqueous hydroxo complex systems. Chemical Review, 65, 177–198.
Petit, S., Righi, D., Madejova, J. and Decarreau, A. (1999) Interpretation of the infrared \({\rm{NH}}_4^ + \) spectrum of the \({\rm{NH}}_{{4^ - }}^ + \)-clays: application to the evaluation of the layer charge. Clay Minerals, 34, 543–549.
Rampazzo, N. and Blum, W.E.H. (1991) Decrease of layer charge in 2:1 clay minerals through soil acidification. Proceedings 7th Euroclay Conference, Dresden (M. Storr, K.H. Henning and P. Adolphi, editors), pp. 863–864.
Rassineux, F., Griffault, L., Meunier, A., Berger, G., Petit, S., Vieillard, P., Zellagui, R. and Munoz, M. (2001) Expandability-layer stacking relationship during experimental alteration of a Wyoming bentonite in pH 13.5 solutions at 35 and 60°C. Clay Minerals, 36, 197–210.
Righi, D., Velde, B. and Meunier, A. (1995) Clay stability in clay-dominated soil systems. Clay Minerals, 30, 45–54.
Ruiz, R., Blanco, C., Pesquera, C., González, F., Benito, I. and López, J.L. (1997) Zeolitization of a bentonite and its application to the removal of ammonium ion from waste water. Applied Clay Science, 12, 73–83.
Shin-Jyung Kang, Kazuhiko Egashira and Akira Yoshida (1998) Transformation of a low-grade Korean natural zeolite to high cation exchanger by hydrothermal reaction with or without fusion with sodium hydroxide. Applied Clay Science, 13, 117–135.
Sinitsyn, V.A., Aja, S.U., Kulik, D.A. and Wood, S.A. (2000) Acid-base surface chemistry and sorption of some lanthanides on K+-saturated marblehead illite: I. Results of an experimental investigation. Geochimica et Cosmochimica Acta, 64, 185–194.
Srasra, E. and Trabelsi-Ayedi, M. (2000) Textural properties of acid activated glauconite. Applied Clay Science, 17, 71–84.
Šucha, V., Środoń, J., Clauer, N., Elsass, F., Eberl, D.D., Kraus, I. and Madejová, J. (2001) Weathering of smectite and illite-smectite under temperate climatic conditions. Clay Minerals, 36, 403–419.
Sun Kou, M.R., Mendioroz, S. and Munoz, V. (2000) Evaluation of the acidity of pillared montmorillonites by pyridine adsorption. Clays and Clay Minerals, 48, 528–536.
Suraj, G., Iyer, C.S.P. and Lalithambika, M. (1998) Adsorption of cadmium and copper by modified kaolinites. Applied Clay Science, 13, 293–306.
Thomas, G.W. and Hargrove, W.L. (1984) The chemistry of soil acidity. In: Soil Acidity and Liming, 2nd edition, Agronomy Series 3 (F. Adams, editor). American Society of Agronomy.
Van Olphen, H. (1963) An Introduction to Clay Colloid Chemistry, Wiley Interscience Publishers, New York.
Ward, D.B. and Brady, P.V. (1998) Effect of Al and organic acids on the surface chemistry of kaolinite. Clays and Clay Minerals 46, 453–465.
Warren, C.J., Dudas, M.J. and Abboud, S.A. (1992) Effects of acidification on the chemical composition and layer charge of smectite from calcareous till. Geoderma, 40, 731–739.
Yeoh, N.S. and Oades, J.M. (1981) Properties of soils and clays after acid treatment. I Clay minerals. Australian Journal of Soil Research, 19, 147–158.
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Jozefaciuk, G. Effect of acid and alkali treatments on surface-charge properties of selected minerals. Clays Clay Miner. 50, 647–656 (2002). https://doi.org/10.1346/000986002320679378
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DOI: https://doi.org/10.1346/000986002320679378