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Characterization of an alkylammonium-montmorillonite-phenanthrene intercalation complex by carbon-13 nuclear magnetic resonance spectroscopy

  • B. K. G. Theng (a1), R. H. Newman (a2) and J. S. Whitton (a1)

Abstract

Low molecular weight polycyclic aromatic hydrocarbons can intercalate from the solid phase into montmorillonite (Mt) saturated with quaternary alkylammonium ions. However, the interaction and relationship between guest and host organic molecules in the interlayer space of the clay are not well understood. We have intercalated phenanthrene into tetradecyltrimethylammonium (TDTMA)-montmorillonite by a solid-solid reaction. The basal spacing of the original TDTMA-Mt complex is close to 1.8 nm, indicating the presence in the interlayer space of a double layer of TDTMA ions with the alkyl (polymethylene) chains lying parallel to the silicate layers, and the carbon zig-zags adopting an all-trans conformation. After intercalation of phenanthrene the basal spacing increases to about 3.4 nm, indicating a change in orientation of the alkyl chains with respect to the silicate layers. 13C-NMR spectroscopy shows that adding phenanthrene to TDTMA-Mt leads to a displacement by -3 ppm of the -(CH2)n- signal for TDTMA. This signal and that for interlayer phenantbrene are also broadened relative to the respective pure compounds. These observations, together with measurements of nuclear spin relaxation time constants, strongly suggest that in the complex with phenanthrene the polymethylene chains of TDTMA extend away from the silicate layers, and no longer assume a rigid all-trans carbon zig-zag conformation. Rather, the TDTMA chains become relatively disordered and intimately mixed with phenanthrene.

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Alla, M. & Lippmaa, E. (1976) High resolution broad line 13C NMR and relaxation in solid norbornadiene. Chem. Phys. Lett. 3'7, 260264.
Blakemore, L.C., Searle, P.L. & Daly, B.K. (1987) Methods for chemical analysis of soils. NZ Soil Bureau Scientific” Report 80.
Byers, W., Meyers, M.B. & Mooney, D.E. (1994) Analysis of soil from a disused gasworks. Water Air Soil Pollut. 73, 1-9.
Canet, D., Brondeau L, Boubel, J.C. & Retournard, A. (1987) A one-dimensional selective version of the INADEQUATE experiment for determining carboncarbon connectivities. Analysis of multi-pulse experiments by a vectorial representation. Magn. Reson. Chem. 25, 798803.
Chen, C.S., Rat, P.S.C. & Lee, L.S. (1996) Evaluation of extraction and detection methods for determining polynuclear aromatic hydrocarbons from coal tar contaminated soils. Chemosphere, 32, 1123–1132.
Cheung, T.T.P. & Gerstein, B.C. (1981) 1H nuclear magnetic resonance studies of domain structures in polymers. J. Appl. Phys. 52, 55175528.
Durant, N.D., Wilson, L.P. & Bouwer, E.J. (1995) Microcosm studies of subsurface PAH-degrading bacteria from a former manufactured gas plant. J. Contam. Hydrol. 17, 213237.
Earl, W.L. & VanderHart, D.L. (1979) Observations in solid polyethylenes by carbon-13 nuclear magnetic resonance with magic-angle spinning. Macromolecules, 12, 762–767.
Grosser, R.J., Warshawsky, D. & Vestal, J.R. (1995) Mineralization of polycyclic and N-heteroeyclic aromatic compounds in hydrocarbon-contaminated soils. Environ. Toxicol. Chem. 14, 375382.
Hong, S.B., Cho, H.M. & Davis, M.E. (1993) Distribution and motion of guest molecules in zeolites. J. Phys. Chem. 97, 16221628.
Iwasaki, T. & Onodera, Y. (1995) Sorption behaviour of caesium ions in smectites. Proc. lOth Int. Clay Conf, Adelaide, 67-73.
Jaynes, W.F. & Boyd, S.A. (1990) Trimethylphenylammonium smectite as an effective adsorbent of water-soluble aromatic hydrocarbons. J. Air Waste Manage. 40, 16491653.
Jaynes, W.F. & Boyd, S.A. (1991) Clay mineral type and organic compound sorption by hexadecyltrimethylammonium- exchanged clays. Soil Sci. Soc. Am. J. 55, 4348.
Johnson, L.F. & Jankowski, W.C. (1972) Carbon-13 NMR Spectra: a Collection of Assigned, Coded and Indexed Spectra. Wiley-Interscience, New York.
Lagaly, G. (1993) Reaktionen der Tonminerale. Pp. 89–167 in: Tonminerale und Tone (Jasmund, K. & Lagaly, G., editors). Steinkopff Verlag, Darmstadt.
Lechert, H. & Basler, W.D. (1989) Molecular motion in zeolite sorbents, studied by various NMR methods. J. Phys. Chem. Solids, 50, 497521.
Ogawa, M., Shirai, H., Kuroda, K. & Kato, C. (1992) Solid-state intercalation of naphthalene and anthracene into alkylammonium-montmorillonites. Clays Clay Miner. 40, 485490.
Ogawa, M., Wada, T. & Kuroda, K. (1995) Intercalation of pyrene into alkylammonium-exchanged swelling layered silicates: the effects of the arrangements of the interlayer alkylammonium ions on the states of adsorbates. Langmuir, 11, 45984600.
Pfeifer, H. (1976) Surface phenomena investigated by nuclear magnetic resonance. Physics Reports, 26, 293338.
Qiang, Xu, Eguchi, T., Nakayama, H. & Nakamura, N. (1996) Proton magnetic resonance of CnH2n+2 (n = 1–4) adsorbed in mordenite. Dynamic behaviour and host-guest interaction. J. Chem. Soc. Faraday Trans. 92, 10391042.
Schwerk, U., Michel, D. & Pruski, M. (1996) Local magnetic field distribution in a polycrystalline sample exposed to a strong magnetic field. J. Magn. Reson. Series A, 119, 157164.
Smith, J.A., Iaffe, P.R. & Chiou, C.T. (1990) Effect often quaternary ammonium cations on tetrachloromethane sorption to clay from water. Environ. Sci. Technol. 24, 11671172.
Stothers, J.B. (1972) Carbon-13 NMR Spectroscopy. Academic Press, New York.
Tekely, P., Canet, D. & Delpuech, J.-J. (1989) Observation of 1H nuclei in heterogeneous solids via cross-polarization 13C.N.M.R. Molec. Phys. 67, 8196.
Theng, B.K.G. (1974) The Chemistry of Clay-Organic Reactions. Adam Hilger, London and Wiley, New York.
van Olphen, H. (1977) An Introduction to Clay Colloid Chemistry, 2nd Edition. Wiley-Interscience, New York.
Whitton, J.S. & Churchman, G.J. (1987) Standard methods for mineral analysis of soil survey samples for characterisation and classification in NZ Soil Bureau. NZ Soil Bureau Scientific Report 79.
Zumbulyadis, N. (1983) Selective carbon excitation and the detection of spatial heterogeneity in crosspolarization magic-angle-spinning NMR. J. Magn. Reson. 53, 486494.

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