Hostname: page-component-78c5997874-ndw9j Total loading time: 0 Render date: 2024-11-20T01:20:09.330Z Has data issue: false hasContentIssue false
  • English
  • Français

Effect of Negative Surface-Charge Densities of Smectite Clays on the Adsorption Isotherms of Racemic and Enantiomeric Tris(2,2′-Bipyridyl)Ruthenium(II) Chloride

Published online by Cambridge University Press:  02 April 2024

Gilles Villemure
Gilles Villemure*
Affiliation:
Centre de Recherche en Photobiophysique, Université du Québec à Trois-Rivières, 3351, boul. des Forges, C.P. 500, Trois-Rivières, Quebec G9A 5H7, Canada
*
1Present address: Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton, New Brunswick E3B 6E2, Canada.
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 level of adsorption of enantiomeric tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) by seven different smectite samples was found to be controlled by the total surface area of the clay. The level corresponded to one monolayer. The adsorption of the racemic mixture was lower for all samples, being limited to saturation of the clay's cation-exchange capacity. The addition of NaCl increased the adsorption of the racemic Ru(bpy)32+ to the same level as the enantiomers. The dependence on the clay's surface charge density, expected on the basis of the limited face-to-face aggregation model, was not found. The sharp decrease in adsorption of the enantiomers by low charge-density clays and the corresponding sharp increase in adsorption of the racemate by high charge density clays were not observed. These results do not necessarily invalidate the model. The range of negative charges examined may not have been wide enough. Also, charge distribution in smectite is generally not uniform.

Keywords

AdsorptionEnantiomorphsRacemic pairsSmectiteSurface chargeTris(2,2′-bipyridyl)ruthenium(II)
Type
Research Article
Information
Clays and Clay Minerals , Volume 38 , Issue 6 , December 1990 , pp. 623 - 630
Copyright
Copyright © 1990, The Clay Minerals Society

References

Cairns-Smith, A. G., 1982 Genetic Takeover and the Mineral Origins of Life Cambridge Cambridge University Press 34 – 45.Google Scholar
Dwyer, F. P. and Gyarfas, E. C., 1949 The chemistry of ruthenium. Part VII. The oxidation of D and L tris, 2,2′dipyridyl ruthenium (II) iodide J. Royal Soc. N.S. Wales 83 173 – 175.Google Scholar
Fitch, A., Lavy-Feder, A., Lee, S. A. and Kirsh, M. T., 1988 Montmorillonite face surface associated Cr(bpy)3 2+ monitored electrochemically J. Phys. Chem. 92 6665 – 6670.CrossRefGoogle Scholar
Jackson, M. L., Wittig, L. D. and Pennington, R. P., 1949 Segregation procedure for the mineralogical analysis of soils Soil Sci. Soc. Amer. Proc. 14 77 – 81.CrossRefGoogle Scholar
Jaynes, W. F. and Bigham, J. M., 1986 Multiple cation-exchange capacity measurements on standard clays using a commercial mechanical extractor Clays & Clay Minerals 34 93 – 95.CrossRefGoogle Scholar
Jaynes, W. F. and Bigham, J. M., 1987 Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites Clays & Clay Minerals 35 440 – 448.CrossRefGoogle Scholar
Joshi, V. and Ghosh, P. K., 1987 Luminescence spectroscopy as a probe of binding state differences between enantiomeric and racemic poly(pyridyl)-ruthenium(II) chelates intercalated in smectite clays J. Chem. Soc. Chem. Commun. 789 – 791.CrossRefGoogle Scholar
Joshi, V. and Ghosh, P. K., 1989 Spectral evidence of spontaneous racemic and “pseudoracemic” interactions between optically active poly(pyridyl)metal chelates adsorbed on smectite clays J. Amer. Chem. Soc. 111 5604 – 5612.CrossRefGoogle Scholar
Kalyanasundaram, K., 1982 Photophysics, photochemistry and solar energy conversion with tris (bipyridyl) ruthe-nium(II) and its analogues Coord. Chem. Rev. 46 159 – 244.CrossRefGoogle Scholar
Lagaly, G., 1981 Characterization of clays by organic compounds Clay Miner 16 1 – 21.CrossRefGoogle Scholar
Mehra, O. P., Jackson, M. L. and Swineford, A., 1958 Iron oxide removal from soils and clays by a dithionite-citrate system buffered with sodium bicarbonate Clays & Clay Minerals, Proc. 7th Natl. Conf., Washington, D.C., 1958 New York Pergamon Press 317 – 327.Google Scholar
Nadeau, P. H., 1987 Clay particle engineering: A potential new technology with diverse applications Appl. Clay Sci. 2 83 – 93.CrossRefGoogle Scholar
Ponnamperuma, C., Shimoyam, A. and Friebele, E., 1982 Clay and the origin of life Origins of Life 12 9 – 40.CrossRefGoogle ScholarPubMed
Schoonheydt, R. A., De Pauw, P., Vliers, D. and De Schrijver, F. C., 1984 Luminescence of tris-(2,2′-bipyridine)ruthenium(II) in aqueous clay mineral suspensions J. Phys. Chem. 88 5113 – 5118.CrossRefGoogle Scholar
Thomas, J. K., 1988 Photophysical and photochemical processes on clay surfaces Acc. Chem. Res. 21 275 – 280.CrossRefGoogle Scholar
Traynor, M. F., Mortland, M. M. and Pinnavaia, T. J., 1978 Ion exchange and intersalation reactions of hectorite with trisbipyridyl metal complexes Clays & Clay Minerals 26 318 – 326.CrossRefGoogle Scholar
van Olphen, H., 1977 An Introduction to Clay Colloid Chemistry 2nd ed. New York Wiley Interscience 254 – 259.Google Scholar
Villemure, G. and Bard, A. J., 1990 Clay modified electrodes: 10. Studies of clay-adsorbed Ru(bpy)3 2+ enantiomers by UV-visible spectroscopy and cyclic voltametry J. Electroanal. Chem. .CrossRefGoogle Scholar
Vliers, D. P. and Schoonheydt, R. A., 1985 Synthesis and luminescence of ruthenium tris-(2,2’-bipyridine)-zirconium phosphates J. Chem. Soc. Faraday Trans. 1 81 2009 – 2019.CrossRefGoogle Scholar
Yamagishi, A., 1985 Racemic adsorption, antiracemization, and induction of optical activity of metal chelates in the presence of colloidal clay Inorg. Chem. 24 1689 – 1695.CrossRefGoogle Scholar
Yamagishi, A., 1987 Optical resolution and asymmetric syntheses by use of adsorption on clay minerals J. Coord. Chem. 16 131 – 211.CrossRefGoogle Scholar
Zhang, X. and Bard, A. J., 1989 In-trough cyclic voltametric studies of Langmuir-Blodgett monolayers of surfactant derivatives of Ru(bpy)3 2+ at an indium-tin oxide electrode J. Amer. Chem. Soc. 111 8098 – 8105.CrossRefGoogle Scholar