Hostname: page-component-848d4c4894-8bljj Total loading time: 0 Render date: 2024-07-02T08:33:39.831Z Has data issue: false hasContentIssue false
  • English
  • Français

Effects of Exchanged Cation and Layer Charge on the Sorption of Water and Egme Vapors on Montmorillonite Clays

Published online by Cambridge University Press:  28 February 2024

Cary T. Chiou  and
David W. Rutherford
Cary T. Chiou
Affiliation:
U.S. Geological Survey, Box 25046, MS 408, Denver Federal Center, Denver, Colorado 80225
David W. Rutherford
Affiliation:
U.S. Geological Survey, Box 25046, MS 408, Denver Federal Center, Denver, Colorado 80225
Get access Rights & Permissions [Opens in a new window]

Abstract

The effects of exchanged cation and layer charge on the sorption of water and ethylene glycol monoethyl ether (EGME) vapors on montmorillonite have been studied on SAz-1 and SWy-1 source clays, each exchanged respectively with Ca, Na, K, Cs and tetramethylammonium (TMA) cations. The corresponding lattice expansions were also determined, and the corresponding N2 adsorption data were provided for comparison. For clays exchanged with cations of low hydrating powers (such as K, Cs and TMA), water shows a notably lower uptake than does N2 at low relative pressures (P/P0). By contrast, EGME shows higher uptakes than N2 on all exchanged clays at all P/P0. The anomaly for water is attributed to its relatively low attraction for siloxane surfaces of montmorillonite because of its high cohesive energy density. In addition to solvating cations and expanding interlayers, water and EGME vapors condense into small clay pores and interlayer voids created by interlayer expansion. The initial (dry) interlayer separation varies more significantly with cation type than with layer charge; the water-saturated interlayer separation varies more with cation type than the EGME-saturated interlayer separation. Because of the differences in surface adsorption and interlayer expansion for water and EGME, no general correspondence is found between the isotherms of water and EGME on exchanged clays, nor is a simple relation observed between the overall uptake of either vapor and the cation solvating power. The excess interlayer capacities of water and of EGME that result from lattice expansion of the exchanged clays are estimated by correcting for amounts of vapor adsorption on planar clay surfaces and of vapor condensation into intrinsic clay pores. The resulting data follow more closely the relative solvating powers of the exchanged cations.

Keywords

Cation SolvationEGME IsothermsExcess Interlayer UptakeExchanged CationInterlayer SpacingsLayer ChargeLayer SeparationMicroporosityMontmorilloniteSurface AdsorptionWater Isotherms
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 6 , December 1997 , pp. 867 - 880
Copyright
Copyright © 1997, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Carter, D.L. Heilman, M.D. and Gonzalez, C.L., 1965 Ethylene glycol monoethyl ether for determining surface area of silicate minerals Soil Sci 100 356–360 10.1097/00010694-196511000-00011.CrossRefGoogle Scholar
Chen, N.Y., 1976 Hydrophobic properties of zeolites J Phys Chem 80 60–64 10.1021/j100542a013.CrossRefGoogle Scholar
Chiou, C.T. Rutherford, D.W. and Manes, M., 1993 Sorption of N2 and EGME vapors on some soils, clays, and mineral oxides and determination of sample surface areas by use of sorption data Environ Sci Technol 27 1587–1594 10.1021/es00045a014.CrossRefGoogle Scholar
de Boer, J.H. Lippens, B.C. Linsen, B.G. Broekhoff, J.C.P. van den Heuvel, A. and Osinga Th, J., 1966 The t-curve of multilayer N2-adsorption J Colloid Interface Sci 21 405–414 10.1016/0095-8522(66)90006-7.CrossRefGoogle Scholar
Doner, H.E. and Mortland, M.M., 1969 Benzene complexes with Cu-montmorillonite Science 166 1406–1407 10.1126/science.166.3911.1406.CrossRefGoogle Scholar
Fu, M.H. Zhang, Z.Z. and Low, P.E., 1990 Changes in the properties of a montmorillonite-water system during the adsorption and desorption of water hysteresis Clays Clay Miner 38 485–492 10.1346/CCMN.1990.0380504.CrossRefGoogle Scholar
Hendricks, S.B. Nelson, R.A. and Alexander, L.T., 1940 Hydration mechanism of the clay montmorillonite with various cations J Am Chem Soc 62 1457–1464 10.1021/ja01863a037.CrossRefGoogle Scholar
Keren, R. and Shainberg, I., 1975 Water vapor isotherms and heat of immersion of Na/Ca-montmorillonite systems—I: homoionic clay Clays Clay Miner 23 193–200 10.1346/CCMN.1975.0230305.CrossRefGoogle Scholar
Kittrick, J.A., 1969 Interlayer forces in montmorillonite and vermiculite Soil Sci Soc Am Proc 33 217–222 10.2136/sssaj1969.03615995003300020017x.CrossRefGoogle Scholar
McNeal, B.L., 1964 Effect of exchangeable cations on glycol retention by clay minerals Soil Sci 97 96–102 10.1097/00010694-196402000-00005.CrossRefGoogle Scholar
Mooney, R.W. Keenan, A.G. and Wood, L.A., 1952 Adsorption of water vapor by montmorillonite. I. Heat of desorption and application of BET theory J Am Chem Soc 74 1367–1371 10.1021/ja01126a001.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 10.1021/ja01126a002.CrossRefGoogle Scholar
Mortland, M.M. and Halloran, L.J., 1976 Polymerization of aromatic molecules on smectite Soil Sci Soc Am J 40 367–370 10.2136/sssaj1976.03615995004000030019x.CrossRefGoogle Scholar
Parker, J.C. and Sparks, D.L., 1986 Hydrostatics of water in porous media Soil physical chemistry Boca Raton, FL CRC Pr. 209–296.Google Scholar
Pinnavaia, T.J. Hall, P.L. Cady, S.S. and Mortland, M.M., 1974 Aromatic radical cation formation on the intracrystal surfaces of transition metal layer lattice silicates J Phys Chem 78 994–999 10.1021/j100603a010.CrossRefGoogle Scholar
Quirk, J.P., 1955 Significance of surface areas calculated from water vapor sorption isotherms by use of the B.E.T. equation Soil Sci 80 423–430 10.1097/00010694-195512000-00001.CrossRefGoogle Scholar
Rutherford, D.W. Chiou, C.T. and Eberl, D.D., 1997 Effects of exchanged cation on the microporosity of montmorillonite Clays Clay Miner 45 534–543 10.1346/CCMN.1997.0450405.CrossRefGoogle Scholar
Skipper, N.T. Refson, K. and McConnell, J.D.C., 1989 Computer calculation of water-clay interactions using atomic pair potentials Clay Miner 24 411–425 10.1180/claymin.1989.024.2.16.CrossRefGoogle Scholar
van Olphen, H. and Fripiat, J.J., 1979 Data handbook for clay minerals and other nonmetallic minerals New York Pergamon Pr..Google Scholar
Wohleber, D.A. and Manes, M., 1971 Application of the Polanyi adsorption potential theory to adsorption from solution on activated carbon. II. Adsorption of partially miscible liquids from water solution J Phys Chem 75 61–64 10.1021/j100693a014.CrossRefGoogle Scholar