Hostname: page-component-cd9895bd7-fscjk Total loading time: 0 Render date: 2024-12-26T01:21:06.982Z Has data issue: false hasContentIssue false
  • English
  • Français

Acidic Properties of Montmorillonite in Selected Solvents

Published online by Cambridge University Press:  02 April 2024

R. H. Loeppert ,
L. W. Zelazny  and
B. G. Volk
R. H. Loeppert
Affiliation:
Department of Soil and Crop Sciences, Texas A&M University, College Station, Texas 77843
L. W. Zelazny
Affiliation:
Department of Agronomy, Virginia Polytechnic and State University, Blacksburg, Virginia 24061
B. G. Volk
Affiliation:
Agronomy Department, University of Missouri, Columbia, Missouri 65211
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.

Montmorillonites saturated with Al3+, H+-Al3+, and K+ were titrated in H2O, acetonitrile (AN), and dimethylformamide (DMF) to investigate the acidic properties of the clay in these solvents and to evaluate the application of nonaqueous titration procedures for studies of the acidic properties of 2:1 swelling clays. Samples were titrated with tetramethylammonium hydroxide using a combination glass electrode for Potentiometric determination. Titers of base required to reach the final Potentiometric endpoints were greater in AN than in DMF and H2O. The larger titers in AN compared to H2O were attributed to pH-dependent sites for which an inflection was not observed in the latter solvent. Titration curves of Al-saturated montmorillonite in AN showed evidence of a salt-induced hydrolysis which was confirmed by titration curves of salt extracts. The hydrolysis reaction was more evident in AN than in H2O and was probably due to a disruption of the H2O structure by AN and a polarization of the H2O of solvation. The hydrolysis reaction was enhanced in the presence of excess salt due to the ion exchange of H+ from the exchange surface. These studies indicate that acidic properties of clays may be drastically altered in organic solvents. The acidic properties may be used to advantage, for example, in the determination of edge-site acidity. In addition, they have implications concerning possible chemical reactions and/or alterations of clay in organic solvents.

Keywords

AcetonitrileAcidic propertiesDimethylformamideHydrolysisMontmorilloniteWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 34 , Issue 1 , February 1986 , pp. 87 - 92
Copyright
Copyright © 1986, The Clay Minerals Society

References

Barnhisel, R., Bertsch, P. M. and Page, A. L., 1982 Aluminum Methods of Soil Analysis, Vol. 9 275–300.CrossRefGoogle Scholar
Barshad, I., 1960 The effect of the total chemical composition and crystal structure of soil minerals on the nature of the exchangeable cations in acidified clays and in natural occurring acid soils 7th Int. Congr. Soil Sci. Trans., Vol. 2, Madison, Wisconsin 435–444.Google Scholar
Coleman, N. T. and Craig, D., 1961 The spontaneous alteration of hydrogen clay Soil Sei. 91 14–18.CrossRefGoogle Scholar
Coleman, N. T., Thomas, G. W., Pearson, R. W. and Adams, F., 1967 Basic chemistry of soil acidity Soil Acidity and Liming 1–41.Google Scholar
Connick, R. E. and Fiat, D. N., 1963 Coordination numbers of beryllium and aluminum ions in aqueous solutions J. Chem. Phys. 39 1349–1351.CrossRefGoogle Scholar
Davis, L. E., Turner, R. and Whittig, L. D., 1962 Some studies of the auto-transformation of H-bentonite to Al-bentonite Soil Sci. Soc. Amer. Proc. 26 441–443.CrossRefGoogle Scholar
Fratiello, A., Lee, R. A., Miller, D. P. and Nishida, W. M., 1967 NMR studies of electrolytes in binary solvent mixtures. II. Aqueous mixtures of acetone, acetonitrile, di-methylformamide, dimethylsulfoxide, dioxane, ethanol, methanol, N-methylformamide, tetramethylfuran, and tet-ramethylurea Mol. Phys. 13 349–359.CrossRefGoogle Scholar
Frenkel, M., 1974 Surface acidity of montmorillonites Clays & Clay Minerals 22 435–441.CrossRefGoogle Scholar
Fripiat, J. J., Vancompernolle, G. and Servais, A., 1960 Etude de l’acidité de surface des silicates et alumino-sili-cates par titration en milieu non-aqueux Bull. Soc. Chim. Fr. 46 250–259.Google Scholar
Fritz, J. S., 1973 Acid-base Titrations in Nonaqueous Solvents .Google 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. Amer. Proc. 33 859–863.CrossRefGoogle Scholar
Huber, W., 1967 Titrations in Nonaqueous Solvents .Google Scholar
Jackson, M. L., 1963 Aluminum bonding in soils: a unifying principle in soil science Soil Sci. Soc. Amer. Proc. 27 1–10.CrossRefGoogle Scholar
Jackson, M. L., 1967 Soil Chemical Analysis .Google Scholar
Kaddah, M.T. and Coleman, N.T., 1967 Salt displacement of acid-treated trioctahedral vermiculites Soil Sci. Soc. Amer. Proc. 13 333–336.CrossRefGoogle Scholar
Kapoor, B. S., 1972 Acid character of nontronite: permanent and pH-dependent charge components of cation exchange capacity Clay Miner. 9 425–433.CrossRefGoogle Scholar
Kissel, D. E., Gentzsch, E. P. and Thomas, G. W., 1971 Hydrolysis of non-exchangeable acidity in soils during salt extractions of exchangeable acidity Soil Sci. 111 293–297.CrossRefGoogle Scholar
Kolthoff, I. M., 1974 Acid-base equilibria in dipolar aprotic solvents Anal. Chem. 46 1992–2003.CrossRefGoogle Scholar
Kucharsky, J. and Safarik, L., 1965 Titrations in Nonaqueous Solvents .Google Scholar
Loeppert, R. H., Zelazny, L. W. and Volk, B. G., 1977 Acidic properties of kaolinite in water and acetonitrile Soil Sei. Soc. Amer. J. 41 1101–1106.CrossRefGoogle Scholar
Loeppert, R. H., Zelazny, L. W. and Volk, B. G., 1979 Titration of pH-dependent sites of kaolinite in water and selected nonaqueous solvents Clays & Clay Minerals 27 57–62.CrossRefGoogle Scholar
Low, P. F., 1955 The role of aluminum in the titration of bentonite Soil Sci. Soc. Amer. Proc. 19 135–139.CrossRefGoogle 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. 44 349–367.CrossRefGoogle Scholar
Mitra, R. P. and Kapoor, B. S., 1969 Acid character of montmorillonite: titration curves in water and some nonaqueous solvents Soil Sci. 108 11–23.CrossRefGoogle Scholar
Mortland, M. M. and Holmes, J. W., 1968 Protonation of compounds at clay mineral surfaces 9th Internat. Congr. Soil Sci., Trans., Adelaide, Australia, Vol. 1 691–699.Google Scholar
Mortland, M. M. and Raman, K. V., 1968 Surface acidity of smectites in relation to hydration, exchangeable cation and structure Clays & Clay Minerals 16 393–398.CrossRefGoogle Scholar
Ragland, J. L. and Coleman, N. T., 1960 The hydrolysis of aluminum salts in clay and soil systems Soil Sci. Soc. Amer. Proc. 24 457–460.CrossRefGoogle Scholar
Rich, C. I., 1970 Conductometric and Potentiometrie titration of exchangeable aluminum Soil Sci. Soc. Amer. Proc. 34 31–38.CrossRefGoogle Scholar
Shainberg, I. and Dawson, J. E., 1967 Titration of H-clay suspension with salt solutions Soil Soc. Amer. Proc. 31 619–626.CrossRefGoogle Scholar
Shirvington, P. J., 1967 The hydrolysis of some acidic metal cations in acetonitrile containing traces of water Aust. J. Chem. 20 447–457.CrossRefGoogle Scholar
Solomon, D. H. and Murray, H. H., 1972 Acid-base interactions and the properties of kaolinite in non-aqueous media Clays & Clay Minerals 20 135–141.CrossRefGoogle Scholar
Supran, D. and Sheppard, N., 1967 A nuclear magnetic resonance study of the solvation of aluminum Perchlorate by water and acetonitrile: separate resonances from differently hydrated aluminum ions Chem. Commun. 832–834.CrossRefGoogle Scholar
Tahoun, S. A. and Mortland, M. M., 1966 Complexes of montmorillonite with primary, secondary and tertiary amides—I. Protonation of amides on the surface of montmorillonite Soil Sci. 102 248–254.CrossRefGoogle Scholar
Volk, V. V., Jackson, M. L. and Bradley, W. F., 1964 Inorganic pH dependent cation exchange charge of soils Clays and Clay Minerals, Proc. 12th Natl. Conf., Atlanta, Georgia, 1963 281–285.CrossRefGoogle Scholar
Wehrli, F. W. and Wehrli, S., 1981 Solution complexes of the aluminum halides in acetonitrile and acetonitrile-water studied by high-field 27Al NMR J. Mag. Reson. 44 197–207.Google Scholar