Hostname: page-component-586b7cd67f-t7czq Total loading time: 0 Render date: 2024-11-23T06:55:34.374Z Has data issue: false hasContentIssue false
  • English
  • Français

An FTIR Study of Water Sorption on TMA- and TMPA-Montmorillonites

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
Sharon J. Anderson
Affiliation:
Department of Crop and Soil Sciences, Michigan State University, East Lansing, Michigan 48824
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.

Water inhibits sorption of uncharged organic compounds on montmorillonites saturated with small alkylammonium cations such as tetramethylammonium (TMA) and trimethylphenylammonium (TMPA). As a first step toward understanding the mechanism by which water inhibits arene sorption on TMA- and TMPA-montmorillonites, infrared spectroscopy and water sorption isotherm experiments were conducted to determine whether water preferentially hydrates adsorbed TMA and TMPA cations rather than the siloxane surface. Infrared spectra of normal-charge and reduced-charge TMA- and TMPA-montmorillonites were obtained at partial water vapor pressures from 0.075 to 0.92 to determine if water vapor hydrates the adsorbed cations. Water adsorbed at partial pressures from 0 to about 0.2 caused the wave-number position of the HOH deformation vibration of adsorbed water to shift 4 to 10 cm-1 to higher wavenumber and the methyl deformation vibrations of adsorbed TMA and TMPA cations to shift 1 to 2 cm-1 to higher wavenumber, providing evidence that water interacts directly with adsorbed TMA and TMPA ions. There were no shifts in the ring stretching or C-H out-of-plane vibrations of TMPA, which indicates that water interacts with the methyl groups of TMPA, not with TMPA's aromatic ring. Water vapor sorption isotherms showed that normal-charge montmorillonites adsorb more water than do reduced-charge montmorillonites, consistent with the higher concentration of adsorbed cations on normal-charge clay. More water was adsorbed by TMA-montmorillonite than by TMPA-montmorillonite, consistent with the higher hydration energy of TMA. Thus, both the infrared and sorption isotherm results show that water preferentially hydrates adsorbed TMA and TMPA, not the siloxane surface of montmorillonite.

Keywords

FTIRTMA-montmorillonitesTMPA-montmorillonitesWater Sorption
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 1 , February 1996 , pp. 142 - 150
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. Tetra-methylammonium montmorillonite. J Chem Soc 850–858.CrossRefGoogle Scholar
Barrer, R.M. and Reay, J.S.S.. 1957. Sorption and intercalation by methylammonium montmorillonites. J Chem Soc Faraday Trans 53: 1253–1261.CrossRefGoogle Scholar
Bottger, G.L. and Geddes, A.L.. 1965. The infrared spectra of the crystalline tetramethylammonium halides. Spectrochim Acta 21: 1701–1708.CrossRefGoogle Scholar
Brindley, G.W. and Ertem, G.. 1971. Prepation 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 montmorillonite: Tetra-alkylammonium ion exchange forms. Clays & Clay Miner 22: 223–229.CrossRefGoogle Scholar
Cotton, F.A. and Wilkinson, G.. 1966. Advanced Inorganic Chemistry. 2nd ed. New York: Interscience Publishers. 1145p.Google Scholar
Farmer, V.C. and Russell, J.D.. 1971. Interlayer complexes in layer silicates—The structure of water in lamellar ionic solutions. Trans Faraday Soc 67: 2737–2749.CrossRefGoogle Scholar
Fripiat, J.J., Pennequin, M., Poncelet, G. and Cloos, P.. 1969. Influence of the van der Waals force on the infrared spectra of short aliphatic alkylammonium cations held on montmorillonite. Clay Miner 8: 119–134.CrossRefGoogle Scholar
Gast, R.G. and Mortland, M.M.. 1971. Self-diffusion of alkylammonium ions in montmorillonite. J Colloid Interface Sci 37: 80–92.CrossRefGoogle Scholar
Greene-Kelly, R.. 1953. The identification of montmorillon-oids in clays. J Soil Sci 4: 233–237.CrossRefGoogle Scholar
Griffiths, P.R. and De Haseth, J.A.. 1986. Fourier Transform Infrared Spectrometry. New York: Wiley-Interscience. p 234–237.Google 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
Johnston, C.T., Sposito, G. and Erickson, G.. 1992. Vibrational probe studies of water interactions with montmorillonite. Clays & Clay Miner 40: 722–730.CrossRefGoogle Scholar
Lee, J.F., Mortland, M.M., Chiou, C.T., Kile, D.E. and Boyd, S.A.. 1990. Adsorption of benzene, toluene, and xylene by two tetra-methylammonium-smectites having different charge densities. Clays & Clay Miner 38: 113–120.CrossRefGoogle Scholar
McBain, J.W. and Bakr, A.M.. 1926. A new sorption balance. J Am Chem Soc 48: 690–695.CrossRefGoogle Scholar
Mooney, R.W., Keenan, A.G. and Wood, L.A.. 1952. Adsorption of water vapor by montmorillonite. II. Effect of exchangeable ions and lattice swelling as measured by X-ray diffraction. J Am Chem Soc 74: 1371–1374.CrossRefGoogle Scholar
Poinsignon, C., Cases, J.M. and Fripiat, J.J.. 1978. Electrical polarization of water molecules adsorbed by smectites. An infrared study. J Phys Chem 82: 1855–1860.CrossRefGoogle Scholar
Russell, J.D. and Farmer, V.C.. 1964. Infrared spectroscopic study of the dehydration of montmorillonite and saponite. Clay Min Bull 5: 443–464.CrossRefGoogle Scholar
Sposito, G. and Prost, R.. 1982. Structure of water adsorbed on smectites. Chem Rev 82: 553–573.CrossRefGoogle Scholar
Stevens, J.J. and Anderson, S.J.. 1996b. Orientation of trimethyl-phenylammonium (TMPA) on Wyoming montmorillonite: Implications for arene sorption. Clays & Clay Miner 44: 132–141.CrossRefGoogle Scholar
Stevens, J.J., Anderson, S.J. and Boyd, S.A.. 1996a. FTIR study of competitive water-arene sorption on TMA- and TMPA-montmorillonites. Clays & Clay Miner 44: 88–95.CrossRefGoogle Scholar
Suquet, H., Prost, R. and Pezerat, H.. 1977. Étude par spectroscopie infrarouge de l'eau adsorbée par la saponite-calcium. Clay Miner 12: 113–126.CrossRefGoogle Scholar
Weast, R.C.. 1986. CRC Handbook of Chemistry and Physics 67th ed. Boca Raton, Florida: CRC Press, Inc. E-42.Google Scholar