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On the kinetics of ion exchange in phlogopite — An in situ AFM study

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Clays and Clay Minerals

Abstract

The kinetics of cation exchange in phlogopite have been studied in situ by hydrothermal atomic force microscopy (HAFM). The exchange of interlayer K by octylammonium ions caused an increase in the interlayer distance and the formation of reaction fronts which can be locally resolved by AFM. The observed reaction fronts revealed substantial variations in their propagation rates — even within single interlayers. This observed variability in interlayer reactivity could mainly be attributed to chemical and structural inhomogeneities of the samples. A quantitative evaluation of the front propagation at representative sites yielded a diffusion coefficient of the K+ exchange by octylammonium of 1.2±0.6 × 10−11 cm2/s assuming negligible transport normal to the layers. The reverse reaction, i.e. the exchange of organic ions by K+, resulted in a retreat of the reaction fronts and a general restoration of the original morphological state. However, indications of structural alterations and areas with trapped octylammonium ions were found.

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References

  • Aldushin, K., Jordan, G. and Schmahl, W.W. (2006) Basal plane reactivity of phyllosilicates studied in situ by hydrothermal atomic force microscopy (HAFM). Geochimica et Cosmochimica Acta, 70, 4380–4391.

    Article  Google Scholar 

  • Barshad, I. and Kishk, F.M. (1968) Oxidation of ferrous iron in vermiculite and biotite alters fixation and replaceability of potassium. Science, 162, 1401–1402.

    Article  Google Scholar 

  • Bassett, W.A. (1960) Role of hydroxyl orientation in mica alteration. Geological Society of America Bulletin, 71, 449–455.

    Article  Google Scholar 

  • Ferrow, E.A., Kalinowski, B.E., Veblen, D.R. and Schweda, P. (1999) Alteration products of experimentally weathered biotite studied by high-resolution TEM and Mössbauer spectroscopy. European Journal of Mineralogy, 11, 999–1010.

    Article  Google Scholar 

  • Ghabru, S.K., Mermut, A.R. and St. Arnaud, R.J. (1989) Layer-charge and cation-exchange characteristics of vermiculite (weathered biotite) isolated from a Gray Luvisol in northeastern Saskatchewan. Clays and Clay Minerals, 37, 164–172.

    Article  Google Scholar 

  • Higgins, S.R., Eggleston, C.M., Knauss, K.G. and Boro, C.O. (1998) A hydrothermal atomic force microscope for imaging in aqueous solution up to 150°C Review of Scientific Instruments, 69, 2994–2998.

    Article  Google Scholar 

  • Jordan, G., Higgins, S.R., Eggleston, C.M., Knauss, K.G. and Schmahl, W.W. (2001) Dissolution kinetics of magnesite in acidic aqueous solution, a hydrothermal atomic force microscopy (HAFM) study: Step orientation and kink dynamics. Geochimica et Cosmochimica Acta, 65, 4257–4266.

    Article  Google Scholar 

  • Kodama, H. and Ross, G.J. (1973) Structural changes accompanying potassium exchange in a clay-size muscovite. Pp. 481–492 in: Proceedings of the International Clay Conference, Madrid 1972, (J.M. Serratosa, editor). Div. Ciencias C.S.I.C., Madrid.

  • Lagaly, G. (1981) Characterization of clays by organic compounds. Clay Minerals, 16, 1–21.

    Article  Google Scholar 

  • Lagaly, G. (1991) Erkennung und Identifizierung von Tonmineralen mit organischen Stoffen. Pp. 86–130 in: Identifizierung und Charakterisierung von Tonmineralen (H. Tributh und G. Lagaly, Hrsg.). Berichte der Deutschen Ton- und Tonmineralgruppe, DTTG, Gießen, Germany.

    Google Scholar 

  • Lagaly, G. and Weiss, A. (1969) Determination of the layer charge in mica-type layer silicates. In: Proceedings of the International Clay Conference, Tokyo, 1969, Vol. 1 (L. Heller, editor). Israel University Press, Jerusalem.

  • Laird, D.A., Scott, A.D. and Fenton, T.E. (1987) Interpretation of alkylammonium characterization of soil clays. Soil Science Society of America Journal, 51, 1659–1663.

    Article  Google Scholar 

  • Mackintosh, E.E., Lewis, D.G. and Greenland, D.J. (1971) Dodecylammonium-mica complexes — I. Factors affecting the exchange reactions. Clays and Clay Minerals, 19, 209–218.

    Article  Google Scholar 

  • Marcks, C., Wachsmuth, H. and von Reichenbach, H.G. (1989) Preparation of vermiculites for HRTEM. Clay Minerals, 24, 23–32.

    Article  Google Scholar 

  • Mermut, A.R. and Lagaly, G. (2001) Baseline studies of the Clay Minerals Society source clays: Layer-charge determination and characteristics of those minerals containing 2:1 layers. Clays and Clay Minerals, 49, 393–397.

    Article  Google Scholar 

  • Newman, A.C.D. (1970) The synergetic effect of hydrogen ions on the cation exchange of potassium in micas. Clay Minerals, 8, 361–373.

    Article  Google Scholar 

  • Rausell-Colom, J.A., Sweatman, T.R., Wells, C.B. and Norrish, K. (1964) Studies in the artificial weathering of mica. Pp. 40–72 in: Experimental Pedology (E.G. Hallsworth and D.V. Crawford, editors), Butterworth, London.

    Google Scholar 

  • Ruehlicke, G. and Kohler, E.E. (1981) A simplified procedure for determining layer charge by the n-alkylammonium method. Clay Minerals, 16, 305–307.

    Article  Google Scholar 

  • Vali, H., Hesse, R. and Kodama, H. (1992) Arrangement of n-alkylammonium ions in phlogopite and vermiculite: an XRD and TEM study. Clays and Clay Minerals, 40, 240–245.

    Article  Google Scholar 

  • Walker, G.F. (1959) Diffusion of exchangeable cations in vermiculite. Nature, 184, 1392–1393.

    Article  Google Scholar 

  • Walker, G.F. (1967) Interactions of n-alkylammonium ions with mica-type layer lattices. Clay Minerals, 7, 129–143.

    Article  Google Scholar 

  • Weiss, A. (1963) Mica-type layer silicates with alkylammonium ions. Clay Minerals, 10, 191–224.

    Article  Google Scholar 

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Correspondence to Guntram Jordan.

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Aldushin, K., Jordan, G., Aldushina, E. et al. On the kinetics of ion exchange in phlogopite — An in situ AFM study. Clays Clay Miner. 55, 339–347 (2007). https://doi.org/10.1346/CCMN.2007.0550401

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  • DOI: https://doi.org/10.1346/CCMN.2007.0550401

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