Hostname: page-component-586b7cd67f-vdxz6 Total loading time: 0 Render date: 2024-11-23T02:27:32.316Z Has data issue: false hasContentIssue false

Origin and Position of Exchange Sites in Kaolinite: An ESR Study

Published online by Cambridge University Press:  01 July 2024

Murray B. McBride*
Affiliation:
Department of Land Resource Science, University of Guelph, Guelph, Ontario, Canada
*
*Present address: Department of Agronomy, Cornell University, Ithaca, NY 14853, USA.
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.

Electron spin resonance (ESR) spectroscopy is used to investigate the nature of exchange sites on kaolinite. ESR spectra of exchangeable Cu2+ and Mn2+ on kaolinite indicate that divalent exchange ions are about 11–12Å apart on kaolinite surfaces and that planar Cu (H2O)42+ ions are oriented parallel to the surfaces. Solution-like spectra for exchangeable Cu2+ and Mn2+ are observed at high relative humidities, suggesting a high degree of mobility of exchange cations on kaolinite surfaces. The evidence seems to eliminate edge sites as being active in cation exchange at least in the acidic range of pH. Similar conclusions are derived from ESR studies of Cu2+-saturated talc and pyrophyllite. It is proposed that most exchange sites arise from ionic substitutions or mineral impurities in phyllosilicates.

Type
Research Article
Copyright
Copyright © 1976 The Clay Minerals Society

References

Berkheiser, V. and Mortland, M. M. (1975) Variability in exchange ion position in smectite: dependence on inter-layer solvent: Clays & Clay Minerals 23, 404410.CrossRefGoogle Scholar
Bundy, W. M., Johns, W. D. and Murray, H. H. (1965) Interrelationships of physical and chemical properties of kaolinites: Clay Miner. Soc., 2nd meeting, p. 34.Google Scholar
Clementz, D. M., Mortland, M. M. and Pinnavaia, T. J. (1974) Properties of reduced charge montmorillonites: Hydrated Cu (II) ions as a spectroscopic probe: Clays & Clay Minerals 22, 4957.CrossRefGoogle Scholar
Clementz, D. M., Pinnavaia, T. J. and Mortland, M. M. (1973) Stereochemistry of hydrated copper (II) ions on the interlamellar surfaces of layer silicates. An electron spin resonance study: J. phys. Chem. 77, 196200.CrossRefGoogle Scholar
Grim, R. E. (1968) Clay Mineralogy, 2nd edition, p. 193: McGraw-Hill, New York.Google Scholar
Jones, J. P. E., Angel, B. R. and Hall, P. L. (1974) Electron spin resonance studies of doped synthetic kaolinite—II: Clay Minerals 10, 257269.CrossRefGoogle Scholar
McBride, M. B. and Mortland, M. M. (1974) Copper (II) interactions with montmorillonite: evidence from physical methods: Soil Sci. Soc. Am. Proc. 38, 408415.CrossRefGoogle Scholar
McBride, M. B., Pinnavaia, T. J. and Mortland, M. M. (1975) Electron spin relaxation and the mobility of manganese (II) exchange ions in smectites: Am. Miner. 60, 6672.Google Scholar
Nicula, A., Stamires, D. and Turkevich, J. (1965) Paramagnetic resonance absorption of copper ions in porous crystals: J. Chem. Phys. 42, 36843692.CrossRefGoogle Scholar
Sumner, M. E. (1963) Effect of iron oxides on positive and negative charges in clays and soils: Clay Minerals 5, 218224.CrossRefGoogle Scholar
Van der Marel, H. W. (1958) Quantitative analysis of kaolinite: J. Int. Etud. Argiles 1, 119.Google Scholar
Van Olphen, H. (1966) An Introduction to Clay Colloid Chemistry, pp. 7172: Interscience Publishers, New York.Google Scholar
Weaver, C. E. and Pollard, L. D. (1973) The Chemistry of Clay Minerals, pp. 131144: Elsevier Publishing Co., New York.Google Scholar