Hostname: page-component-78c5997874-mlc7c Total loading time: 0 Render date: 2024-11-10T06:32:31.708Z Has data issue: false hasContentIssue false
  • English
  • Français

Adsorption of Monovalent Organic Cations on Sepiolite: Experimental Results and Model Calculations

Published online by Cambridge University Press:  28 February 2024

Giora Rytwo ,
Shlomo Nir ,
Leon Margulies ,
Blanca Casal ,
Jesus Merino ,
Eduardo Ruiz-Hitzky  and
Jose Maria Serratosa
Giora Rytwo
Affiliation:
Tel Hai Academic College, Upper Galilee, 12210, Israel The Seagram Center for Soil and Water Sciences, The Faculty of Agriculture, The Hebrew University of Jerusalem, Rehovot 76100, Israel
Shlomo Nir
Affiliation:
The Seagram Center for Soil and Water Sciences, The Faculty of Agriculture, The Hebrew University of Jerusalem, Rehovot 76100, Israel
Leon Margulies
Affiliation:
The Seagram Center for Soil and Water Sciences, The Faculty of Agriculture, The Hebrew University of Jerusalem, Rehovot 76100, Israel
Blanca Casal
Affiliation:
Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid, Spain
Jesus Merino
Affiliation:
Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid, Spain
Eduardo Ruiz-Hitzky
Affiliation:
Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid, Spain
Jose Maria Serratosa
Affiliation:
Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid, Spain
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.

Adsorption of neutral organic molecules and the monovalent organic cations methylene blue (MB) and crystal violet (CV) to sepiolite was determined experimentally and investigated by an adsorption model. The largest amounts of MB and CV adsorbed were about 4-fold of the cation exchange capacity (CEC) of sepiolite. Consequently, it was proposed that most of the above described adsorption was to neutral sites of the clay. The adsorption model considered combines the Gouy-Chapman solution and specific binding in a closed system. The model was extended by allowing cation adsorption to neutral sites of the clay, in addition to adsorption to negatively charged sites and adsorption to neutral complexes formed from 1 cation adsorbed to a negative surface site. The amount of available neutral sites was determined from the adsorption of the neutral molecule Triton-X 100 (TX100). The model could adequately simulate the adsorption of the neutral molecules TX100 and crown ether 15-crown-5 (15C5) as well as the organic cations. Due to aggregation of MB molecules in solution, their adsorption was somewhat less than that of CV at the larger added concentrations. A consideration of the molecular dimensions of TX100, MB and CV suggested that their adsorption was mostly to external sites of the clay and that their entry to the sepiolite channels was largely excluded. This interpretation is supported by infrared spectroscopy (IR) measurements, which show large perturbations of the peak corresponding to vibrations of external Si-OH groups of the clay and confirm complete occupancy of external sites by MB and CV.

Keywords

Adsorption ModelCrystal VioletMethylene BlueSepiolite
Type
Research Article
Information
Clays and Clay Minerals , Volume 46 , Issue 3 , June 1998 , pp. 340 - 348
Copyright
Copyright © 1998, The Clay Minerals Society

Footnotes

†

Deceased.

References

Alvarez, A., 1984 Sepiolite: Properties and uses. Palygorskite-Sepiolite Occurrences, genesis and uses. Devel Sedimentol 37 Amsterdam Elsevier.Google Scholar
Alvarez, A. Santaren, J. Perez-Castells, R. Casal, B. Ruiz-Hitzky, E. Levitz, P. Fripiat, J.J., van Schultz, L.G. Olphen, H. and Mumpton, F.A., 1987 Surfactant adsorption and Theological behavior of surface modified sepiolite Proc Int Clay Conf Bloomington, IN Clay Miner Soc 370–374.Google Scholar
Alrichs, J.L. Serna, J.C. and Serratosa, J.M., 1975 Structural hydrox-yls in sepiolites Clays Clay Miner 23 119–124 10.1346/CCMN.1975.0230207.CrossRefGoogle Scholar
Aznar, A.J. Casal, B. Ruiz-Hitzky, E. Lopez-Arbeloa, I. Lopez-Arbeloa, F. Santaren, J. and Alvarez, A., 1992 Adsorption of methylene blue on sepiolite gels: Spectroscopic and Theological studies Clay Miner 27 101–108 10.1180/claymin.1992.027.1.10.CrossRefGoogle Scholar
Baruch, E. Lichtenberg, D. Barak, P. and Nir, S., 1991 Calcium binding to bile salts Chem Phys Lip 57 17–21 10.1016/0009-3084(91)90045-D.CrossRefGoogle ScholarPubMed
Bergmann, K. and O’Konski, C.T., 1963 A spectroscopic study of methylene blue monomer, dimer, and complexes with montmorillonite J Phys Chem 67 2169–2177 10.1021/j100804a048.CrossRefGoogle Scholar
Brauner, K. and Preisinger, A., 1956 Structure and origin of sepiolite Miner Petr Mitt 6 120–140 10.1007/BF01128033.Google Scholar
Cenens, J. and Schoonheydt, R.A., 1988 Visible spectroscopy of methylene blue on hectorite, laponite B and barasym in aqueous suspension Clays Clay Miner 36 214–224 10.1346/CCMN.1988.0360302.CrossRefGoogle Scholar
Hirsch, D. Nir, S. and Banin, A., 1989 Prediction of cadmium com-plexation in solution and adsorption to montmorillonite Soil Sci Soc Am J 53 716–721 10.2136/sssaj1989.03615995005300030012x.CrossRefGoogle Scholar
Margulies, L. Rozen, H. and Nir, S., 1988 Model for competitive adsorption of organic cations on clays Clays Clay Miner 36 270–276 10.1346/CCMN.1988.0360309.CrossRefGoogle Scholar
Nir, S. Newton, C. and Papadhadjopoulos, D., 1978 Binding of cations to phosphatidylserine vesicles Bioelectrochem Bioenerg 5 116–133 10.1016/0302-4598(87)87012-5.CrossRefGoogle Scholar
Nir, S. Duzgunes, N. and Bentz, J., 1983 Binding of monovalent cations to phosphatidylserine and modulation of Ca2+ and Mg2+ induced vesicle fusion Biochim Biophys Acta 735 160–172 10.1016/0005-2736(83)90271-7.CrossRefGoogle ScholarPubMed
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 10.1016/0021-9797(84)90231-5.CrossRefGoogle Scholar
Nir, S., 1986 Specific and non specific cation adsorption to clays. Solution concentrations and surface potentials Soil Sci Soc Am J 50 52–57 10.2136/sssaj1986.03615995005000010010x.CrossRefGoogle Scholar
Nir, S. Hirsch, D. Navrot, J. and Banin, A., 1986 Specific adsorption of Li, Na, K, Cs, and Sr to montmorillonite Soil Sci Soc Am J 50 40–45 10.2136/sssaj1986.03615995005000010008x.CrossRefGoogle Scholar
Nir, S. Rytwo, G. Yermiyahu, U. and Margulies, L., 1994 A model for cation adsorption to clays and membranes Colloid Polym Sci 272 619–632 10.1007/BF00659277.CrossRefGoogle Scholar
Nir, S. Peled, R. and Lee, K.D., 1994 Analysis of particle uptake by cells: Binding to several receptors, equilibration time, endocytosis Colloids Surfaces A: Physicochem Eng Aspects 89 45–57 10.1016/0927-7757(94)02858-3.CrossRefGoogle Scholar
Ruiz-Hitzky, E., 1974 Contribution a l’etude des reactions de greffage des groupements organiques sur les surfaces minerales Greffage de la sepiolite [Ph.D. thesis] Belgium University of Louvain.Google Scholar
Ruiz-Hitzky, E. and Fripiat, J.J., 1976 Organomineral derivatives obtained by reacting organochlorosilanes with the surfaces of silicates in organic solvents Clays Clay Miner 24 25–30 10.1346/CCMN.1976.0240102.CrossRefGoogle Scholar
Ruiz-Hitzky, E. and Casal, B., 1985 Epoxide rearrangements on mineral and silico-alumina surfaces J Catal 92 291–295 10.1016/0021-9517(85)90263-5.CrossRefGoogle Scholar
Rytwo, G. Serban, C. Nir, S. and Margulies, L., 1991 Use of methylene blue and crystal violet for determination of exchangeable cations in montmorillonite Clays Clay Miner 39 551–555 10.1346/CCMN.1991.0390510.CrossRefGoogle Scholar
Rytwo, G., 1994 Interactions between organic cations and montmorillonite, adsorption and model calculations [Ph.D. thesis] (in Hebrew) Jerusalem Hebrew Univ.Google Scholar
Rytwo, G. Nir, S. and Margulies, L., 1995 Interactions of monovalent organic cations with montmorillonite, adsorption and model calculations Soil Sci Soc Am J 59 554–564 10.2136/sssaj1995.03615995005900020041x.CrossRefGoogle Scholar
Rytwo, G. Nir, S. and Banin, A., 1996 Exchange reactions in the Ca-Mg-Na-montmorillonite system Clays Clay Miner 44 276–285 10.1346/CCMN.1996.0440212.CrossRefGoogle Scholar
Rytwo, G. Nir, S. and Margulies, L., 1996 A model for adsorption of divalent organic cations to montmorillonite J Colloid Interface Sci 181.2 551–560 10.1006/jcis.1996.0412.CrossRefGoogle Scholar
Santaren, J. Sanz, J. and Ruiz-Hitzky, E., 1990 Structural fluorine in sepiolite Clay Miner 38 63–68 10.1346/CCMN.1990.0380109.CrossRefGoogle Scholar
Spencer, W. and Sutter, J.R., 1979 Kinetic study of the monomer-dimer equilibrium of methylene blue in aqueous solution J Phys Chem 83 1573–1576 10.1021/j100475a004.CrossRefGoogle Scholar