Skip to main content
Log in

Adsorption of 1-n-Alkyl Pyridinium Bromides by Montmorillonite

  • Symposium on Clay—Organic Complexes
  • Published:
Clays and Clay Minerals

Abstract

Adsorption isotherms of 1-n-alkyl pyridinium bromides on Na-montmorillomte, and in addition of cetyl pyridinium bromide on Ca-montmorillonite, have been determined. For up to eight carbon atoms in the alkyl chain adsorption has a limit close to the exchange capacity of the clay. With larger ions adsorption occurs beyond this and is accompanied by adsorption of the bromide ion. Adsorption of the cetyl pyridinium ion beyond the exchange capacity is greater on Na- than on Ca-montmorillonite. Replacement of the cation initially present is incomplete. X-ray diffraction analysis shows that the adsorbed ions normally lie flat on the clay surface, but cetyl pyridinium ions may stand up in a plane at right angles to the surface. Interlamellar separations somewhat less than the minimum molecular thicknesses, found for the methyl and ethyl pyridinium ions, are attributed to a combination of (1) “keying” of the alkyl groups into the clay surface, and (2) the effect of the attractive forces between the clay and the pyridinium ring. It is concluded that adsorption is due to ionic and dispersion forces between the pyridinium ions and the clay. For the cetyl compound the dispersion forces are larger than ionic forces. The exchangeable cation initially present influences the adsorption by its effect on the exchange reaction and probably also by its influence on the domain structure of the clay and hence the accessibility of external surfaces of the crystallites.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Addison, C. G. and Furmidge, C. G. L. (1956) Critical concentrations of some alkyl pyri-dinium iodides in water and in xylene evaluated from solubility measurements: J. Chem. Soc., pp. 3229–3230.

    Google Scholar 

  • Aylmore, L. A. G. and Quirk, J. P. (1959) Swelling of clay-water systems: Nature, v. 183, pp. 1752–1753.

    Article  Google Scholar 

  • Barrer, R. M. and Ibbitson, D. (1944) Occlusion of hydrocarbons by chabazite and analcite: Tram. Faraday Soc., v. 40, pp. 195–206.

    Article  Google Scholar 

  • Bradley, W. F. (1945) Molecular associations between montmorillonite and some poly-functional organic liquids: J. Amer. Chem. Soc., v. 67, pp. 975–981.

    Article  Google Scholar 

  • Chakravarti, S. K. (1956) Sedimentation volume and zeta potential of pure clay minerals and their mixtures as influenced by quaternary ammonium compounds: Sci. and Cult., v. 22, pp. 170–172.

    Google Scholar 

  • Chakravarti, S. K. (1957) Adsorption of higher alkyl quaternary ammonium and pyridinium compounds by clay minerals: J. Indian Soc. Soil Sci., v. 5, pp. 85–90.

    Google Scholar 

  • Clare, K. E. (1947) Effect of cetyl pyridinium bromide on the water absorption and swelling of soil: Nature, v. 160, pp. 828–829.

    Article  Google Scholar 

  • Cowan, C. T. and White, D. (1958) The mechanism of exchange reactions occurring between sodium montmorillonite and various n-primary aliphatic amine salts: Trans. Faraday Soc., v. 54, pp. 691–697.

    Article  Google Scholar 

  • Franzen, P. (1955) X-ray analysis of an adsorption complex of montmorillonite with cetyl-trimethyl ammonium bromide (lissolamine): Clay Min. Bull., v. 2, pp. 223–225.

    Article  Google Scholar 

  • Glaeser, Rachel (1951) Sur la retention des molecules organiques par la montmorillonite: C. R. Acad. Sci. (Paris), v. 232, pp. 1496–1498.

    Google Scholar 

  • Greene-Kelly, R. (1953) Studies of the sorption of polar molecules by layer lattice silicates: Ph. D. Thesis, University of London.

    Google Scholar 

  • Greene-Kelly, R. (1955a) Sorption of aromatic organic compounds by montmorillonite, 1. Orientation studies: Trans. Faraday Soc., v. 51, pp. 412–424.

    Article  Google Scholar 

  • Greene-Kelly, R. (1955b) Sorption of aromatic organic compounds by montmorillonite, 2. Packing studies with pyridine: Trans. Faraday Soc., v. 51, pp. 425–430.

    Article  Google Scholar 

  • Greenland, D. J. (1956) The adsorption of sugars by montmorillonite, I. X-ray studies: J. Soil Sci., v. 7, pp. 319–328.

    Article  Google Scholar 

  • Grim, R. E. (1953) Clay Mineralogy: McGraw-Hill Book Co., Inc., New York, 384 pp.

    Book  Google Scholar 

  • Grim, R. E., Allaway, W. H. and Cuthbert, P. L. (1947) Reaction of different clay minerals with organic cations: J. Amer. Ceram. Soc., v. 30, pp. 137–142.

    Article  Google Scholar 

  • Grossey, F. X. and Woolsey, L. J. (1955) Effect of fatty quaternary ammonium salts on physical properties of certain soils: Ind. Eng. Chem., v. 47, pp. 2253–2258.

    Article  Google Scholar 

  • Hendricks, S. B. (1941) Base-exchange of the clay mineral montmorillonite for organic cations and its dependence upon adsorption due to van der Waals forces: J. Phys. Chem., v. 45, pp. 65–81.

    Article  Google Scholar 

  • Jordan, J. W. (1949a) Organophilic bentonites, I. Swelling in organic liquids: J. Phys. Chem., v. 53, pp. 294–306.

    Article  Google Scholar 

  • Jordan, J. W. (1949b) Alteration of the properties of bentonite by reaction with amines: Min. Mag., v. 28, pp. 598–605.

    Google Scholar 

  • Knight, G. A. and Shaw, B. D. (1937) Long-chain alkylpyridines and their derivatives. New-examples of liquid crystals: J. Chem. Soc., pp. 682–683.

    Google Scholar 

  • Kurilenko, O. D. and Mikhalyuk, R. V. (1959) Adsorption of aliphatic amines on bentonite from aqueous solutions: Kolloidny Zh., v. 21, pp. 195–199.

    Google Scholar 

  • MacEwan, D.M. C. (1948) Complexes of clays with organic compounds. I. Complex formation between montmorillonite and halloysite and certain organic liquids: Trans. Faraday Soc., v. 44, pp. 349–367.

    Article  Google Scholar 

  • McAtee, J. L. (1958) Random interstratification in organophilic bentonites: in Clays and Clay Minerals, Natl. Acad. Sci.—Natl. Res. Council, pub. 566, pp. 308–317.

    Google Scholar 

  • Mukherjee, H. (1954) Adsorption of cetyl trimethyl ammonium bromide and krilium by bentonite: J. Indian Soc Soil. Sci., v. 2, pp. 99–103.

    Google Scholar 

  • Sieskind, O. and Wey, R. (1958) Influence du pH sur l’adsorption d’amines aliphatiques normales par la montmorillonite-H: C. E. Acad. Sci. (Paris), v. 247, pp. 74–76.

    Google Scholar 

  • Weiss, A. (1958a) Die innerkristalline Quellung als allgemeines Modell für Quellungsvorgänge: Chem. Ber., v. 91, pp. 487–502.

    Article  Google Scholar 

  • Weiss, A. (1958b) Der Kationenaustausch bei den Mineralen der Glimmer-, Vermikulit-und Montmorillonitgruppe: Z. anorg. Chem., v. 297, pp. 257–286.

    Article  Google Scholar 

  • Williams, B. G. (1959) Some physico-chemical aspects of the stability of natural soil aggregates: Honours Thesis, University of Adelaide.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Greenland, D.J., Quirk, J.P. Adsorption of 1-n-Alkyl Pyridinium Bromides by Montmorillonite. Clays Clay Miner. 9, 484–499 (1960). https://doi.org/10.1346/CCMN.1960.0090136

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.1960.0090136

Navigation