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Model for Competitive Adsorption of Organic Cations on Clays

Published online by Cambridge University Press:  02 April 2024

L. Margulies ,
H. Rozen  and
S. Nir
L. Margulies
Affiliation:
Seagram Centre for Soil and Water Sciences, Faculty of Agriculture, The Hebrew University, Rehovot 76-100, Israel
H. Rozen
Affiliation:
Seagram Centre for Soil and Water Sciences, Faculty of Agriculture, The Hebrew University, Rehovot 76-100, Israel
S. Nir
Affiliation:
Seagram Centre for Soil and Water Sciences, Faculty of Agriculture, The Hebrew University, Rehovot 76-100, Israel
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Abstract

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The adsorption on montmorillonite of two monovalent organic cations, methylene blue (MB) and thioflavin T (TFT), was studied in four different situations: (1) separate adsorption of MB or TFT; (2) competitive adsorption of TFT and Cs; (3) competitive adsorption of the two organic cations from their equimolar solutions; and (4) adsorption of TFT on a clay whose cation-exchange capacity (CEC) had been previously saturated with MB. MB and TFT adsorbed to as much as 120% and 140% of the CEC, respectively. Cs did not appear to compete with TFT for the adsorption sites of the clay. TFT molecules adsorbed more strongly than those of MB and displaced them from the clay surface. A model was developed to evaluate the strength of the clay-organic cation interactions. The specific binding of the cations to the negatively charged surface, determined by solving the electrostatic equations, appears to account for adsorption exceeding the CEC and formation of positively charged complexes, which are due to non-coulombic interactions between the organic ligands.

The charge reversal predicted by the model beyond the CEC of the clay was confirmed by microelec-trophoretic experiments. Particles in a sample of montmorillonite loaded with 50 meq TFT/100 g clay moved to the positive electrode, whereas in samples containing the two dyes, MB and TFT, coadsorbed at a total concentration of 100–120 meq/100 g clay, the particles moved to the negative electrode. Binding coefficients describing the formation of neutral and charged complexes of TFT and the clay were larger than those for MB and the clay, thereby explaining the preferential adsorption of TFT observed experimentally. The binding coefficients for the formation of neutral complexes of either MB and TFT and the clay were more than six orders of magnitude larger than those previously reported for inorganic monovalent cations.

Keywords

AdsorptionClay-organicMethylene blueMontmorilloniteOrganic cationThioflavin T
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 3 , June 1988 , pp. 270 - 276
Copyright
Copyright © 1988, The Clay Minerals Society

References

Barrow, N. J., Bowden, J. W., Posner, A. M. and Quirk, J. P., 1980 An objective method for fitting models of ion adsorption on variable charge surfaces Aust. J. Soil Res. 18 37 – 47.CrossRefGoogle Scholar
Bowden, J. W., Posner, A. M. and Quirk, J. P., 1977 Ionic adsorption on variable charge mineral surfaces. Theoretical charge development and titration curves Aust. J. Soil Res. 15 121 – 136.Google Scholar
Chu, C. H. and Johnson, L. J., 1979 Cation-exchange behavior of clays and synthetic aluminosilica gels Clays & Clay Minerals 27 87 – 90.CrossRefGoogle Scholar
Davis, J. A., James, R. O. and Leckie, J. O., 1978 Surface ionization and complexation at the oxide/water interface. 1. Computation of electrical double layer properties in simple electrolytes J. Colloid Interface Sci. 63 480 – 499.CrossRefGoogle Scholar
De, D. K. D. Kanungo, J. L. and Chakravarti, S. K., 1974 Interaction of crystal violet and malachite green with ben-tonite and their desorption by inorganic and surface active quaternary ammonium ions Indian J. Chem. 12 165 – 166.Google Scholar
Eisenberg, M., Gresalfy, T., Riccio, T. and McLaughlin, S., 1979 Adsorption of monovalent cations to bilayer membranes containing negative phospholipids Biochemistry 18 5213 – 5223.CrossRefGoogle ScholarPubMed
Ghosal, D. N. and Mukherjee, S. K., 1972 Studies on the sorption and desorption of crystal violet on and from ben-tonite and kaolinite J. Indian Chem. Soc. 49 569 – 572.Google Scholar
Grauer, Z., Avnir, D. and Yariv, S., 1984 Adsorption characteristics of rhodamine 6G on montmorillonite and La-ponite, elucidated from electronic absorption and emission spectra Can. J. Chem. 62 1889 – 1894.CrossRefGoogle Scholar
Kurland, R. N. C. Nir, S. and Papahadjopoulos, D., 1979 Specificity of Na+ binding to phosphatidylserine vesicles from a “Na NMR relaxation rate study Biochim. Biophys. Acta 551 137 – 147.CrossRefGoogle Scholar
Margulies, L., Cohen, E. and Rozen, H., 1987 Photo-stabilization of bioresmethrin by organic cations on a clay surface Pest. Sci. 18 79 – 87.CrossRefGoogle Scholar
Margulies, L. and Rozen, H., 1986 Adsorption of methyl green on montmorillonite J. Molec. Structure 141 219 – 226.CrossRefGoogle Scholar
Margulies, L., Rozen, H. and Cohen, E., 1985 Energy transfer at the surface of clays and protection of pesticides from photodegradation Nature 315 658 – 659.CrossRefGoogle Scholar
Margulies, L., Rozen, H. and Cohen, E., 1987 Photosta-bilization of a nitromethylene heterocycle on the surface of montmorillonite Clays & Clay Minerals 36 159 – 164.CrossRefGoogle Scholar
McBride, M. B., Pinnavaia, T. J. and Mortland, M. M., 1975 Perturbation of structural Fe3+ in smectites by exchange ions Clays & Clay Minerals 23 103 – 107.CrossRefGoogle Scholar
McBride, M. B., Pinnavaia, T. J. and Mortland, M. M., 1975 Exchange ion positions in smectite: Effects on electron spin resonance of structural iron Clays & Clay Minerals 23 162 – 163.CrossRefGoogle Scholar
Mortland, M. M., 1970 Clay-organic complexes and interactions Adv. Agron. 22 75 – 117.CrossRefGoogle Scholar
Narine, D. R. and Guy, R. D., 1981 Interactions of some large organic cations with bentonite in dilute aqueous systems Clays & Clay Minerals 29 205 – 212.CrossRefGoogle Scholar
Nir, S., 1984 A model for cation adsorption in closed systems: Application to calcium binding to phospholipid vesicles J. Colloid Interface Sci. 102 313 – 321.CrossRefGoogle Scholar
Nir, S., 1986 Specific and non-specific cation adsorption to clays: Solution concentrations and surface potentials Soil Sci. Soc. Amer. J. 50 52 – 57.CrossRefGoogle Scholar
Nir, S., Hirsch, D., Navrot, J. and Banin, A., 1986 Specific adsorption of lithium, sodium, potassium, cesium, and strontium to montmorillonite: Observations and predictions Soil Sci. Soc. Amer. J. 50 40 – 45.CrossRefGoogle Scholar
Nir, S., Newton, C. and Papadhadjopoulos, D., 1978 Binding of cations to phosphatidylserine vesicles Bioelectro-chem. Bioenerg. 5 116 – 133.CrossRefGoogle Scholar
Pham, T. H. and Brindley, G. W., 1970 Methylene blue adsorption by clay minerals. Determination of surface areas and cation exchange capacities (Clay-organic studies XVIII) Clays & Clay Minerals 18 203 – 212.Google Scholar
Shainberg, I. and Kemper, W. D., 1966 Hydration status of adsorbed cations Soil Sci. Soc. Amer. Proc. 30 707 – 713.CrossRefGoogle Scholar
Theng, B. K. G., 1974 The Chemistry of Clay-Organic Reactions .Google Scholar
van Olphen, H. and Fripiat, J. J., 1979 Data Handbook for Clay Materials and Other Non-Metallic Minerals .Google Scholar
Venugopal, J. S. and Nair, M. M., 1974 Preferential dye sorption in clay minerals by acid treatment Indian Mineral. 15 23 – 27.Google Scholar