Hostname: page-component-78c5997874-m6dg7 Total loading time: 0 Render date: 2024-11-17T17:23:17.230Z Has data issue: false hasContentIssue false
  • English
  • Français

Structural Study of Tetramethylphosphonium-Exchanged Vermiculite

Published online by Cambridge University Press:  28 February 2024

A. Vahedi-Faridi  and
Stephen Guggenheim
A. Vahedi-Faridi
Affiliation:
Department of Earth and Environmental Sciences, University of Illinois at Chicago, 845 W. Taylor Street, Chicago, Illinois 60607
Stephen Guggenheim
Affiliation:
Department of Earth and Environmental Sciences, University of Illinois at Chicago, 845 W. Taylor Street, Chicago, Illinois 60607
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.

Vermiculite from Santa Olalla, Spain, was intercalated with tetramethylphosphonium [P(CH3)4+ = TMP], using a TMP-bromide solution at 70°C for three weeks. The resulting TMP-exchanged vermiculite, which contained a small (<5% of a site) amount of residual interlayer Ca, showed near perfect three-dimensional stacking. Cell parameters are a = 5.3492(8) Å, b = 9.266(2) Å, c = 14.505(6) Å, β = 97.08(2)°, space group is C2/m, and polytype is lM. Single-crystal X-ray refinement (R = 0.052, wR = 0.061) located two crystallographically unique sites for the phosphorus atoms (TMP molecule). The phosphorus atoms are occupied partially [P1 = 0.146(6), P2 = 0.098(5)] and are offset from the central plane of the interlayer by 1.23 Å to form two P-rich planes in the interlayer. Electrostatic interactions between the P cations and basal oxygen atoms essentially balance the negative charge associated with Al for Si substitutions in the tetrahedral sites. In addition, the orientations of the TMP molecules are probably different owing to packing constraints. The H2O site is located in the center of the interlayer, at the center of the silicate ring, and ∼3.09 Å from the Ca, which is also located on the central plane of the interlayer. Other H2O molecules are present in the interlayer, but could not be located by the diffraction experiment because they are randomly positioned in the interlayer. The tetrahedral rotation angle, α, is affected by the intercalation of TMP relative to tetramethylammonium (TMA), thus indicating that 2:1 layers are not simply rigid substrates, and that dynamic interactions occur during reactions involving adsorption and exchange.

Keywords

OrganoclayTetramethylphosphoniumTetramethylphosphonium VermiculiteTMP-VermiculiteVermiculite
Type
Research Article
Information
Clays and Clay Minerals , Volume 47 , Issue 2 , April 1999 , pp. 219 - 225
Copyright
Copyright © 1999, The Clay Minerals Society

References

Barrer, R.M., 1984 Sorption and molecular sieve properties of clays and their importance as catalysts Philosophical Transactions of the Royal Society (London), A 311 333–352 10.1098/rsta.1984.0032.Google Scholar
Barrer, R.M., 1989 Shape-selective sorbents based on clay minerals: A review Clays and Clay Minerals 37 385–395 10.1346/CCMN.1989.0370501.CrossRefGoogle Scholar
Barrer, R.M. and McLeod, D.M., 1955 Activation of mont-morillonite by ion exchange and sorption complexes of tetra-alkyl ammonium montmorillonites Transactions of the Faraday Society 50 1290–1300 10.1039/tf9555101290.CrossRefGoogle Scholar
Barrer, R.M. and Millington, A.D., 1967 Sorption and intra-crystalline porosity in organo-clays Journal of Colloid Interface Science 25 359–372 10.1016/0021-9797(67)90042-2.CrossRefGoogle Scholar
Barrer, R.M. and Perry, G.S., 1961 Sorption of mixtures, and selectivity in alkylammonium montmorillonites Journal of the Chemical Society 842–858.CrossRefGoogle Scholar
Barrer, R.M. and Reay, J.S.S., 1957 Sorption and intercalation by methylammonium montmorillonites Transactions of the Faraday Society 53 1253–1261 10.1039/tf9575301253.CrossRefGoogle Scholar
Brown, I.D., 1977 Predicting bond length in inorganic crystals Acta Crystallographica B33 1305–1310 10.1107/S0567740877005998.CrossRefGoogle Scholar
Cromer, D.T. and Mann, J.B., 1968 X-ray scattering factors computed from numerical Hartree-Fock wave functions Acta Crystallographica A24 321–324 10.1107/S0567739468000550.CrossRefGoogle Scholar
de la Calle, C. Pezerat, H. and Gasperin, M., 1977 Problemes d’ordre—Desordre dans les vermiculites. Structure du minerai calcique hydrate a deux couches Journal de Physique, Colloque, C.7 Suplement au nx 12 38 128–138.Google Scholar
Diamond, S. and Kinter, E.B., 1961 Characterization of montmorillonite saturated with short chain amine cations Clays and Clay Minerals 10 163–173 10.1346/CCMN.1961.0100114.CrossRefGoogle Scholar
Gast, R.G. and Mortland, M.M., 1971 Self-Diffusion of alkylammonium ions in montmorillonite Journal of Colloid Interface Science 37 80–92 10.1016/0021-9797(71)90267-0.CrossRefGoogle Scholar
Kukkadapu, R.K. and Boyd, S.A., 1995 Tetramethylphos-phonium- and tetramethylammonium-smectites as adsorbents of aromatic and chlorinated hydrocarbons: Effect of water on adsorption efficiency Clays and Clay Minerals 43 318–323 10.1346/CCMN.1995.0430306.CrossRefGoogle Scholar
Ladd, M.F.C. and Palmer, R.A., 1977 Structure Determination by X-ray Crystallography New York Plenum 10.1007/978-1-4615-7930-4.CrossRefGoogle Scholar
Lee, J. Mortland, M.M. and Boyd, S.A., 1989 Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite Journal of the Chemical Society, Faraday Transactions I 85 2953–2962 10.1039/f19898502953.CrossRefGoogle Scholar
Lee, J. Mortland, M.M. Chiou, C.T. Kile, D.E. and Boyd, S.A., 1990 Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities Clays and Clay Minerals 38 113–120 10.1346/CCMN.1990.0380201.CrossRefGoogle Scholar
Luque, F.J. Rodas, M. and Doval, M., 1985 Mineralogia y genesis de los yacimientos de vermiculite de Ojen Boletin de la Sociedad Espanola de Mineralogico 8 229–238.Google Scholar
Norrish, K. and Serratosa, J.M., 1973 Factors in the weathering of mica to vermiculite Proceedings of the International Clay Conference, Madrid, 1972 Madrid Division de Ciencias, CSIC. 417–432.Google Scholar
Rowland, R.A. and Weiss, E.J., 1961 Bentonite-methylamine complexes Clays and Clay Minerals 10 460–468 10.1346/CCMN.1961.0100140.CrossRefGoogle Scholar
Sales, K.D., 1987 Atomic scattering factors for mixed atom sites Acta Crystallographica A43 42–44 10.1107/S0108767387099938.CrossRefGoogle Scholar
Siemens, 1990 SHELXTL PLUS 4.0, Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin .Google Scholar
Slade, P.G. Raupach, M. and Radoslovich, E.W., 1985 Interlayer structures of the two layer hydrates of Na-and Ca-vermiculites Clays and Clay Minerals 33 51–61 10.1346/CCMN.1985.0330106.CrossRefGoogle Scholar
Theng, B.K.G. Greenland, D.J. and Quirk, L.P., 1967 Adsorption of alkylammonium cations by montmorillonite Clay Minerals 7 1–17 10.1180/claymin.1967.007.1.01.CrossRefGoogle Scholar
Vahedi-Faridi, A. and Guggenheim, S., 1997 Crystal structure of TMA-exchanged vermiculite Clays and Clay Minerals 45 859–866 10.1346/CCMN.1997.0450610.CrossRefGoogle Scholar