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Orientation of Trimethylphenylammonium (TMPA) on Wyoming Montmorillonite: Implications for Sorption of Aromatic Compounds

Published online by Cambridge University Press:  28 February 2024

Jeffrey J. Stevens  and
Sharon J. Anderson
Jeffrey J. Stevens
Affiliation:
Department of Crop and Soil Sciences, Michigan State University, East Lansing, Michigan 48824-1325
Sharon J. Anderson
Affiliation:
Department of Crop and Soil Sciences, Michigan State University, East Lansing, Michigan 48824-1325
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Abstract

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The orientation of TMPA cations on montmorillonite affects the adsorbate-accessible siloxane surface area and determines whether the TMPA phenyl ring can interact with other aromatic adsorbates by π-π interactions. The purpose of this study was to determine the orientation of TMPA ions in the interlayer of normal-charge and reduced-charge Wyoming montmorillonite. The orientation of TMPA's phenyl group was investigated using infrared dichroism of selected aromatic ring vibrations. X-ray diffraction (XRD) and MacEwan Fourier transforms were used to determine interlayer spacings and to ascertain whether reduced-charge Wyoming montmorillonite is a randomly interstratified mixture of layers with two different d-spacings. For normal-charge montmorillonite, the infrared results showed that the C-N bond axis is neither perpendicular nor parallel to the surface, yet X-ray data suggested that the TMPA phenyl ring is perpendicular or nearly perpendicular to the siloxane surface. In this orientation, the average adsorbate-accessible space between adjacent TMPA ions is 24 Å2, or about 1/3 of the total surface. When the phenyl ring of TMPA is perpendicular to the clay surface, aromatic compounds should be able to interact with TMPA's aromatic ring by π-π interactions, while polar compounds such as water can interact with positively charged nitrogen atom. The reduced-charge montmorillonite used in this study is a randomly interstratified mixture of about 25% collapsed layers with no adsorbed cations and 75% expanded layers that are propped open by TMPA's methyl groups, not by the aromatic ring. The adsorbate-accessible surface area on expanded layers of reduced-charge montmorillonite is 1.5 to 2 times that on normal-charge TMPA-clay, depending on the orientation of TMPA's aromatic ring.

Keywords

AdsorbateInfrared dichroismMontmorilloniteTrimethylphenylammonium (TMPA)
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 1 , February 1996 , pp. 132 - 141
Copyright
Copyright © 1996, The Clay Minerals Society

References

Barrer, R.M. and Perry, G.S.. 1961. Sorption of mixtures, and selectivity in alkylammonium montmorillonites. Part II. Tetramethylammonium montmorillonite. J Chem Soc 850–858.Google Scholar
Barrer, R.M. and Reay, J.S.S.. 1957. Sorption and intercalation by methylammonium montmorillonites. Trans Faraday Soc 53: 1253–1261.CrossRefGoogle Scholar
Boyd, S.A., Jaynes, W.F. and Ross, B.S.. 1991. Immobilization of organic contaminants by organo-clays: Application to soil restoration and hazardous waste containment. In: Baker, R.S., editor. Organic substances and sediments in water, Vol. 1. Boca Raton, FL: CRC Press, p 181–372.Google Scholar
Brindley, G.W. and Ertem, G.. 1971. Preparation and solvation properties of some variable charge montmorillonites. Clays & Clay Miner 19: 399–404.CrossRefGoogle Scholar
Clementz, D.M. and Mortland, M.M.. 1974. Properties of reduced charge montmorillonites: Tetra-alkylammonium ion exchange forms. Clays & Clay Miner 22: 223–229.CrossRefGoogle Scholar
Clementz, D.M., Mortland, M.M. and Pinnavaia, T.J.. 1974. Properties of reduced charge montmorillonites: Hydrated Cu(II) ions as a spectroscopic probe. Clays & Clay Miner 22: 49–57.CrossRefGoogle Scholar
Cope, A.C., Ciganer, E., Fleckenstein, L.J. and Meisinger, M.A.P.. 1960. Tertiary amines from methiodides and lithium aluminum hydride. J Am Chem Soc 82: 4651–4655.CrossRefGoogle Scholar
Farmer, V.C. and Mortland, M.M.. 1966. An infrared study of the coordination of pyridine and water to exchangeable cations in montmorillonite and saponite. J Chem Soc 344–351.CrossRefGoogle Scholar
Gast, R.G.. 1977. Surface and colloid chemistry. In: Dixon, J.B., Weed, S.B., editors. Minerals in Soil Environments. Madison, WI: American Society of Agronomy. p 27–73.Google Scholar
Greene-Kelly, R.. 1953. The identification of montmorillonoids in clays. J Soil Sci 4: 233–237.CrossRefGoogle Scholar
Greene-Kelly, R.. 1955. Sorption of aromatic organic compounds by montmorillonite. Pt. 1. Orientation studies. Trans Faraday Soc 51: 412–424.CrossRefGoogle Scholar
Jaynes, W.J. and Bigham, J.M.. 1987. Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites. Clays & Clay Miner 35: 440–448.CrossRefGoogle Scholar
Jaynes, W.J. and Boyd, S.A.. 1991. Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water. Clays & Clay Miner 39: 428–436.CrossRefGoogle Scholar
MacEwan, D.M.C.. 1956. Fourier transform methods for studying scattering from lamellar systems I. A direct method for analysing interstratified mixtures. Kolloid Z 149: 96–108.CrossRefGoogle Scholar
Moore, D.M. and Reynolds, R.C.. 1989. X-ray Diffraction and the Identification and Analysis of Clay Minerals. New York: Oxford University Press. 332p.Google Scholar
Pauling, L.. 1960. The Nature of the Chemical Bond. 3rd ed. Ithaca, New York: Cornell University Press. 644p.Google Scholar
Reynolds, R.C.. 1980. Interstratified Clay Minerals. In: Brindley, G.W., Brown, G., editors. Crystal Structures of Clay Minerals and their X-ray Identification. London: Mineralogical Society. p 249–304.CrossRefGoogle Scholar
Serratosa, J.M.. 1966. Infrared analysis of the orientation of pyridine molecules in clay minerals. Clays & Clay Miner 14: 385–391.CrossRefGoogle Scholar
Serratosa, J.M.. 1968. Infrared study of benzonitrile (C6H5-CN)-montmorillonite complexes. Am Mineral 53: 1244–1251.Google Scholar