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Effect of autotransformation on the layer charge of smectites determined by the alkylammonium method

Published online by Cambridge University Press:  09 July 2018

M. Janek ,
P. Komadel  and
G. Lagaly
M. Janek
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovak Republic
P. Komadel
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovak Republic
G. Lagaly
Affiliation:
Institut für anorganische Chemie der Universität Kiel, Olshausenstr. 40, 24098 Kiel, Germany
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Abstract

Hydrogen-forms of <2 µm fractions of six bentonites of various Fe contents were prepared by H+→OH-→H+ ion exchange using resins. Potentiometric titration curves revealed that the number of strong acid sites varied and accounted for 60-95% of the total acidity in the freshly prepared H-forms. The number of strong acid sites decreased and that of the weak acid sites increased on ageing. The process of autotransformation in aqueous dispersion at 90~ was completed within four days. Layer-charge distributions of all samples were inhomogeneous with layer charges from 0.25-0.39 Eq/unit O10(OH)2. Oxalate pretreatment of the samples resulted in changes in the layer-charge distribution due to the removal of readily soluble phases which may have blocked exchange sites. After autotransformation, the alkylammonium exchange method revealed inhomogeneous charge density distributions; the fraction of layers of the highest charge decreased. Comparison of total CEC obtained from potentiometric curves and interlamellar CEC calculated from the mean layer charge confirmed attack of protons from particle edges. However, for several samples the structural attack may also occur from the interlayer space. Autotransformation of the Hsmectites decreased the mean layer charge. Protons probably attack the Mg(O,OH)6 octahedra preferentially during the autotransformation.

Type
Research Article
Information
Clay Minerals , Volume 32 , Issue 4 , December 1997 , pp. 623 - 632
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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References

Aldrich, D.G. & Buchanan, J.R. (1958) Anomalies in techniques for preparing H-bentonites. Soil Sci. Soc. Am. Proc. 22, 281–285.Google Scholar
Bandosz, T.J., Jagiello, J., Putyera, K. & Schwarz, J.A. (1994) Characterization of acidity of pillared clays by proton affinity distribution and DRIFT spectroscopy. J. Chem. Soc. Faraday Trans. 90, 3573–3578.Google Scholar
Banin, A. (1995) Surface acidity of clays. In: Abstracts of Israeli-Spanish Workshop on Organo-clays: Structure, Properties and Uses. Ein Gedi, Israel.Google Scholar
Banin, A. & Ravikovitch, S. (1966) Kinetics of reactions in the conversion of Na- or Ca-saturated clay to H-Al clay. Clays Clay Miner. 14, 193–204.Google Scholar
Barshad, I. (1969) Preparation of H saturated montmorillonites. Soil Sci. 108, 38–42.Google Scholar
Barshad, I. & Foscolos, A.E. (1970) Factors affecting the rate of the interchange reaction of adsorbed H+ on the 2:1 clay minerals. Soil Sci. 110, 52–60.CrossRefGoogle Scholar
Beneke, K. & Lagaly, G. (1982) The brittle mica-like KNiAsO4 and its organic derivates. Clay Miner. 17, 175–183.Google Scholar
Coleman, N.T. & Craig, D. (1961) The spontaneous alteration of hydrogen clay. Soil Sci. 91, 14–18.Google Scholar
Čičel, B. (1991) Mechanism and kinetics of proton attack of smectites. DrSc. thesis, Institute of Inorganic Chemistry, SAS, Bratislava, (in Slovak).Google Scholar
Čičel, B. & Komadel, P. (1994) Structural formulae of layer silicates. Pp. 114–136 in: Quantitative Methods in Soil Mineralogy (Amonette, J.E. & Zelazny, L.W., editors). SSSA Misc. Publ., SSSA, Madison, Wisconsin.Google Scholar
Čičel, B., Komadel, P., Lego, S., Madejová J. & Vlčková, L. (1992) Iron-rich beidellite in the fine fraction of Stebno bentonite. Geol. Carph. Ser. Clays. 43, 121–124.Google Scholar
Davis, L.E., Turner, R. & Whittig, L.D. (1962) Some studies of the autotransformation of H-bentonite to Al-bentonite. Soil Sci. Soc. Am. Proc. 26, 441–443.CrossRefGoogle Scholar
Jagietto, J., Bandosz, T.J., Putyera, K. & Schwarz, J.A. (1995) Determination of proton affinity distributions for chemical systems in aqueous environments using a stable numerical solution of the adsorption integral equation. d. Coll. Interj. Sci. 172, 341–346.Google Scholar
Janek, M. & Komadel, P. (1993) Autotransformation of H-smectites in aqueous solutions. Effect of octahedral iron content. Geol. Carph. Ser. Clays. 44, 59–64.Google Scholar
Kaviratna, H. & Pinnavaia, T.J. (1994) Acid hydrolysis of octahedral Mg2+ sites in 2:1 layered silicates: an assessment of edge attack and gallery access mechanisms. Clays Clay Miner. 42, 717–723.Google Scholar
Kelley, W.P. (1955) Interpretation of chemical analyses of clays. Clays Clay Miner. 1, 92–94.Google Scholar
Komadel, P. & Čičel, B. (1987) Sedimentation volumes of H-montmorillonites. I. The effect of the conditions of preparation. Silikáty, 31, 247–253.Google Scholar
Komadel, P., Bujdhk, J., Madejová, J., Sucha, V. & Elsass, F. (1996a) Effect of non-swelling layers on dissolution of reduced-charge montmorillonite in hydrochloric acid. Clay Miner. 31, 333–345.Google Scholar
Komadel, P., Madejová, J., Janek, M., Gates, W.P., Kirkpatrick, R.J. & Stucki, J.W. (1996b) Dissolution of hectorite in inorganic acids. Clays Clay Miner. 44, 228–236.Google Scholar
Lagaly, G. (1981) Characterization of clays by organic compounds. Clay Miner. 16, 1–21.Google Scholar
Lagaly, G. (1994a) Layer charge determination by alkylammonium ions. Pp. 1–46 in: Layer Charge Characteristics of 2:1 Silicate Clay Minerals (Mermut, A.R., editor), Clay Minerals Society Workshop Lectures 6, Boulder, CO, USA.Google Scholar
Lagaly, G. (1994b) Bentonites: adsorbents of toxic substances. Progr. Coll. Polym. Sci. 95, 61–72.Google Scholar
Lagaly, G. & Beneke, K. (1991) Intercalation and exchange reactions of clay minerals and non-clay layer compounds. Coll. Polym. Sci. 269, 1198–1211.Google Scholar
Lagaly, G. & Weiss, A. (1969) Determination of the layer charge in mica-type layer silicates. Proc. Int. Clay Conf., Tokyo I, 61-80.Google Scholar
Lagaly, G. & Weiss, A. (1971) Neue Methoden zur Charakterisieung und Identifizierung quellungsfähiger Dreischichttonminerale. Z. Pflanzenern. Bodenkunde. 130, 9–24.Google Scholar
Lagaly, G. & Weiss, A. (1975) The layer charge of smectitic layer silicates. Proc. Int. Clay Conf., Mexico, 157-172.Google Scholar
Lagaly, G., Fernandez Gonzales, M. & Weiss, A. (1976) Problems in layer-charge determination of montmorillonites. Clay Miner. 11, 173–187.Google Scholar
Laird, D.A. (1994) Evaluation of structural formulae and alkylammonium method of determining layer charge. Pp. 79–104 in: Layer Charge Characteristics of 2:l Silicate Clay Minerals (Mermut, A.R., editor), Clay Minerals Society Workshop Lectures 6, Boulder, CO, USA.Google Scholar
Laird, D.A., Scott, A.D. & Fenton, T.E. (1987) Interpretation of alkylammonium characterisation of soil clays. Soil Sci. Soc. Am. J. 51, 1659–1663.Google Scholar
Laird, D.A., Scott, A.D. & Fenton, T.E. (1989) Evaluation of the alkylammonium method of determining layer charge. Clays Clay Miner. 37, 41–46.Google Scholar
Low, P.F. (1955) The role of aluminium in the titration of bentonite. Soil Sci. Soc. Am. Proc. 19, 135–139.Google Scholar
Maes, A., Stal, M.S. & Cremers, A. (1979) Layer charge - cation-exchange capacity relationships in montmorillonite. Clays Clay Miner. 27, 387–392.Google Scholar
Malla, P.B. & Lowell, A.D. (1987) Layer charge properties of smectites and vermiculites: tetrahedral vs. octahedral. Soil Sci. Soc. Am. J. 51, 1362–1366.Google Scholar
Mermut, A.R. (1994) Problems associated with layer charge characterisation of 2:1 phyllosilicates. Pp. 105-127 in: Layer Charge Characteristics of 2:1 Silicate Clay Minerals (Mermut, A.R., editor), Clay Minerals Society Workshop Lectures 6, Boulder, CO, USA.Google Scholar
Miller, R.J. (1965) Mechanisms for hydrogen to aluminum transformations in clays. Soil Sci. Soc. Am. Proc. 29, 36–39.Google Scholar
Sawlmey, B.L. & Frink, C.R. (1966) Potentiometric titration of acid montmorillonite. Soil Sci. Soc. Am. Proc. 30, 181–184.Google Scholar
Stul, M.S. & Van Leemput, L. (1982) Particle size distribution, cation exchange capacity and charge density of deferrated montmorillonites. Clay Miner. 17, 253–264.Google Scholar
Thompson, D.W. & Mitchell Ch.J. (1993) The hydrolytic precipitation of iron in aqueous dispersions of mineral particles. Coll. Surf. 73, 103–115.Google Scholar
Thompson, D.W. & Tahir, N.M. (1991) The influence of a smectite clay on the hydrolysis of iron(III). Coll. Surf. 60, 369–398.Google Scholar