Hostname: page-component-586b7cd67f-gb8f7 Total loading time: 0 Render date: 2024-11-23T05:05:05.319Z Has data issue: false hasContentIssue false
  • English
  • Français

Protonation of Organic Bases in Clay—Water Systems

Published online by Cambridge University Press:  01 July 2024

Samuel W. Karickhoff  and
George W. Bailey
Samuel W. Karickhoff
Affiliation:
Environmental Research Laboratory, U.S. Environmental Protection Agency, Athens, Georgia 30601, U.S.A.
George W. Bailey
Affiliation:
Environmental Research Laboratory, U.S. Environmental Protection Agency, Athens, Georgia 30601, U.S.A.
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.

The extent of protonation of organic bases in clay—water systems depends upon the adsorptive properties of the organo-clay species involved, and upon the structure and degree of hydration of the clay system. Organic molecules that can disperse cationic charge over two or more condensed aromatic rings give rise to greater surface-induced protonation than do single-ring organic molecules with similar solution pKa. Protonation in clay suspensions is frequently far in excess of that predicted on the basis of electrolytic suspension pH and solution pKa of the organic base. For a given organic base, protonation in a clay film exceeds that in the suspended clay system. Protonation in an organo-clay film increases as the film moisture content decreases. The extent of protonation in organo—clay systems varies with cationic species, cationic saturation, and clay type.

Type
Research Article
Information
Clays and Clay Minerals , Volume 24 , Issue 4 , August 1976 , pp. 170 - 176
Copyright
Copyright © 1976 The Clay Minerals Society

Footnotes

*

Reference to trade names is for information only and does not constitute endorsement by the U.S. Environmental Protection Agency.

References

Albert, A. (1968) Heterocyclic Chemistry: Athlone Press, London, pp. 125–133.Google Scholar
Armstrong, D. E. and Chesters, G. (1968) Adsorption catalyzed chemical hydrolysis of atrazine: Environ. Sci. Technol. 2(9), 683–689.CrossRefGoogle Scholar
Bailey, G. W., Brown, D. S. and Karickhoff, S. W. (1973) Competitive hydration of quinazoline at the montmorillonite–water interface: Science 182, 819–821.CrossRefGoogle ScholarPubMed
Bailey, G. W. and Karickhoff, S. W. (1973) An ultraviolet spectroscopic method for monitoring surface acidity of clay minerals under varying water content: Clays & Clay Minerals 21, 471–477.CrossRefGoogle Scholar
Bailey, G. W. and White, J. L. (1965) Herbicides: A compilation of their physical, chemical, and biological properties: Residue Reviews 10, 97–122.Google ScholarPubMed
Bailey, G. W. and White, J. L. (1970) Factors influencing the adsorption-desorption and movement of pesticides in soil: Residue Reviews 32, 29–92.Google Scholar
Bailey, G. W., White, J. L. and Rothberg, T. (1968) Adsorption of organic herbicides by montmorillonite: Role of pH and chemical character of adsorbate: Soil Sci. Soc. Am. Proc. 32, 222–234.CrossRefGoogle Scholar
Benesi, H. A. (1956) Acidity of catalyst surfaces—I: Acid strength from colors of adsorbed indicators: J. Am. Chem. Soc. 78, 5490–5494.CrossRefGoogle Scholar
Conley, R. F. and Althoff, A. C. (1971) Surface acidity in kaolinites: J. Coll. Interface Sci. 37(1), 186–195.CrossRefGoogle Scholar
Frenkel, M. (1974) Surface acidity of montmorillonites: Clays & Clay Minerals 22, 435–441.CrossRefGoogle Scholar
Harter, R. D. and Ahlrichs, J. L. (1967) Determination of clay surface acidity by i.r. spectroscopy: Soil Sci. Soc. Am. Proc. 31, 30–33.CrossRefGoogle Scholar
Harter, R. D. and Ahlrichs, J. L. (1969) Effect of acidity on reactions of organic acids and amines with montmorillonite clay surface: Soil Sci. Soc. Am. Proc. 33, 859–863.CrossRefGoogle Scholar
Kerr, G. T., Zimmerman, R. H., Tox, H. A. and Wells, F. H. (1955) Degradation of hectorite by hydrogen ion: Clays & Clay Minerals 4, 322–329.Google Scholar
Mortland, M. M. (1970) Clay–organic complexes and interactions: Advan. Agron. 22, 75–117.CrossRefGoogle Scholar
Mortland, M. M. and Raman, K. V. (1968) Surface acidity of smectites in relation to hydration, exchangeable cation and structure: Clays & Clay Mineral 16, 393–398.CrossRefGoogle Scholar
Paver, H. and Marshall, C. E. (1934) The role of aluminum in the reactions of the clays: J. Soc. Chem. Ind. 53, 750–760.Google Scholar
Perrin, D. D. (1965) Dissociation Constants of Organic Bases in Aqueous Solution 473 pp. Butterworths, London.Google Scholar
Touillaux, R., Salvadore, P., Vandermeersche, C. and Fripiat, J. J. (1968) Study of water layers adsorbed on Na– and Ca–montmorillonite by the pulsed nuclear magnetic resonance technique: Israel J. Chem. 6, 337–348.CrossRefGoogle Scholar
Tullock, R. J. (1970) Surface acidity measurements of a bentonite clay with benzoic acid: M.S. Thesis, Dept. of Agronomy, Purdue University, Lafayette, Ind.Google Scholar
Weed, S. B. and Weber, J. B. (1974) Pesticide–organic matter interactions: In Pesticides in Soil and Water (Edited by Guenzi, W. D.) pp. 39–66. Soil Sci. Soc. Am. Inc., Madison, Wisconsin.Google Scholar
Young, J. F. (1967) Humidity control in the laboratory using salt solutions—A review: J. appl. Chem. 17, 241–245.CrossRefGoogle Scholar