Hostname: page-component-848d4c4894-m9kch Total loading time: 0 Render date: 2024-06-04T14:09:07.926Z Has data issue: false hasContentIssue false
  • English
  • Français

Relationship Between Cation Exchange Selectivity and Crystalline Swelling in Expanding 2:1 Phyllosilicates

Published online by Cambridge University Press:  28 February 2024

David A. Laird  and
Chao Shang
David A. Laird
Affiliation:
USDA, ARS, National Soil Tilth Laboratory, 2150 Pammel Drive, Ames, Iowa 50011
Chao Shang
Affiliation:
Northern Agriculture Research Center, Agriculture Canada P.O. Box 29, Bearverlodge, Alberta, Canada TOH OCO
Get access Rights & Permissions [Opens in a new window]

Abstract

A theoretical model describing the interaction between crystalline swelling and cation exchange selectivity is proposed for expanding 2:1 phyllosilicates. The model is based on the assumption that changes in basal spacing of a clay are phase changes, and that each phase of a clay has a different selectivity constant for a particular cation exchange reaction. Energy barriers stabilize the various phases over a limited range of interlayer ionic composition. These energy barriers cause hysteresis in crystalline swelling, which in turn causes hysteresis in cation exchange. Results are presented for an experiment involving Ba-Mg exchange on a synthetic fiuoro-hectorite. The results demonstrate key aspects of the proposed model, including a correlation between measured selectivity coefficients and basal spacings (R2 = 0.85), an abrupt change in basal spacing that corresponds with an abrupt change in selectivity and corresponding hysteresis in crystalline swelling and cation exchange selectivity. The results also demonstrate increased selectivity for the preferred cation (Ba) at high solution mole fraction of the preferred cation. This trend is opposite of that observed for heterogeneous natural smectites but consistent with predictions of the model for a homogeneous smectite.

Keywords

Cation Exchange SelectivityCrystalline SwellingDemixingFixationIon Exchange HysteresisLayer ChargeSmectite
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 5 , October 1997 , pp. 681 - 689
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

Bain, D.C. Smith, B.F.L. and Wilson, M.J., 1987 Chemical analysis Determinative methods in clay mineralogy NY Chapman and Hall 247–248.Google Scholar
Banin, A., 1968 Ion exchange isotherms of montmorillonite and structure factors affecting them Isr J Chem 6 27–36 10.1002/ijch.196800005.CrossRefGoogle Scholar
Barak, P., 1989 Double layer theory prediction of Al-Ca exchange on clay and soil J Colloid Interface Sci 133 479–490 10.1016/S0021-9797(89)80059-1.CrossRefGoogle Scholar
Eberl, D.D., 1980 Alkali cation selectivity and fixation by clay minerals Clays Clay Miner 28 161–172 10.1346/CCMN.1980.0280301.CrossRefGoogle Scholar
Eisenman, G., 1962 Cation selectivity glass electrodes and their mode of operation Biophys J 2 259–323 10.1016/S0006-3495(62)86959-8.CrossRefGoogle ScholarPubMed
Eriksson, E., 1952 Cation exchange equilibria on clay minerals Soil Sci 74 103–113 10.1097/00010694-195208000-00001.CrossRefGoogle Scholar
Fink, D.H. Nakayama, F.S. and McNeal, B.L., 1971 Demixing of exchangeable cations in free-swelling bentonite clay Soil Sci Soc Am Proc 35 552–555 10.2136/sssaj1971.03615995003500040023x.CrossRefGoogle Scholar
Gaines, G.L. and Thomas, H.C., 1953 Adsorption studies on clay minerals. II. A formulation of the thermodynamics of exchange adsorption J Chem Phys 21 714–718 10.1063/1.1698996.CrossRefGoogle Scholar
Gast, R.G., 1972 Alkali metal cation exchange on Chambers montmorillonite Soil Sci Soc Am Proc 36 14–19 10.2136/sssaj1972.03615995003600010003x.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
Laird, D.A., 1987 Layer charge and crystalline swelling of expanding 2:1 phyllosilicates [Ph.D. dissertation] Ames, IA Iowa State Univ.Google Scholar
Laird, D.A., 1996 Model for crystalline swelling of 2:1 phyllosilicates Clays Clay Miner 44 553–559 10.1346/CCMN.1996.0440415.CrossRefGoogle Scholar
Laird, D.A. Shang, C. and Thompson, M.L., 1995 Hysteresis in crystalline swelling of smectites J Colloid Interface Sci 171 240–245 10.1006/jcis.1995.1173.CrossRefGoogle Scholar
Laudelout, H. van Bladel, R. Bolt, G.H. and Page, A.L., 1968 Thermodynamics of heterovalent cation exchange reactions in a montmorillonite clay Trans Faraday Soc 64 1477–1488 10.1039/tf9686401477.CrossRefGoogle Scholar
Maes, A. and Cremers, A., 1977 Charge density effects in ion exchange: I. Heterovalent exchange equilibria J Chem Soc, Faraday Trans I 73 1807–1814 10.1039/f19777301807.CrossRefGoogle Scholar
McBride, M.B., 1976 Exchange and hydration properties of Cu2+ on mixed Na+-Cu2+ smectites Soil Sci Soc Am J 41 1073–1077 10.2136/sssaj1977.03615995004100060011x.CrossRefGoogle Scholar
McBride, M.B., 1979 An interpretation of cation selectivity variations in M+-M+ exchange on clays Clays Clay Miner 27 417–422 10.1346/CCMN.1979.0270604.CrossRefGoogle Scholar
McBride, M.B., 1980 Interpretation of the variability of selectivity coefficients for exchange between ions of unequal charge on smectites Clays Clay Miner 28 255–261 10.1346/CCMN.1980.0280402.CrossRefGoogle Scholar
Neal, C. and Cooper, D.M., 1983 Extended version of Gouy-Chapman electrostatic theory as applied to exchange behavior of clay in natural waters Clays Clay Miner 31 367–376 10.1346/CCMN.1983.0310506.CrossRefGoogle Scholar
Newman, A.D.C., 1970 Cation exchange properties of micas: II Hysteresis and irreversibility during potassium exchange. Clay Miner 8 267–272.Google Scholar
Nir, S., 1986 Specific and nonspecific cation adsorption to clays: Solution concentrations and surface potentials Soil Sci Soc Am J 50 52–57 10.2136/sssaj1986.03615995005000010010x.CrossRefGoogle Scholar
Norrish, K., 1954 The swelling of montmorillonite Dis Faraday Soc 18 120–134 10.1039/df9541800120.CrossRefGoogle Scholar
Parker, J.C. and Sparks, D.L., 1986 Hydrostatics of water in porus media Soil physical chemistry Boca Raton, FL CRC Pr 209–296.Google Scholar
Peigneur, P. Maes, A. and Cremers, A., 1975 Heterogeneity of charge density distribution in montmorillonite as inferred from cobalt adsorption Clays Clay Miner 23 71–78 10.1346/CCMN.1975.0230110.CrossRefGoogle Scholar
Posner, A.M. and Quirk, J.P., 1964 The adsorption of water from concentrated electrolyte solutions by montmorillonite and illite Proc Royal Soc A 278 35–56.Google Scholar
Saehr, D. Le Dreed, R. Wey, R., Van Olphen, H. and Venidle, F., 1982 Thermodynamic study of cation-exchange in vermiculite with K+ ions Proc Int Clay Conf Amsterdam Elsevier 133–139.Google Scholar
Sawhney, B.L. and Heller, L., 1969 Cesium uptake by layer silicates: Effect on interlayer collapse and cation exchange capacity Proc Int Clay Conf Jerusalem Israel Univ Pr 605–611.Google Scholar
Shainberg, I. Alperovitch, N.I. and Keren, R., 1987 Charge density and Na-K-Ca exchange on smectites Clays Clay Miner 35 68–73 10.1346/CCMN.1987.0350109.CrossRefGoogle Scholar
Shainberg, I. and Otoh, H., 1968 Size and shape of montmorillonite particles saturated with Na/Ca ions (inferred from viscosity and optical measurements) Isr J Chem 6 251–259 10.1002/ijch.196800035.CrossRefGoogle Scholar
Shang, C. Laird, D.A. and Thompson, M.L., 1995 Transmission X-ray diffraction technique for measuring crystalline swelling of smectites in electrolyte solutions Clays Clay Miner 43 128–130 10.1346/CCMN.1995.0430115.CrossRefGoogle Scholar
van Bladel, R. and Laudelout, H., 1967 Apparent irreversibility of ion-exchange reactions in clay suspensions Soil Sci 104 134–137 10.1097/00010694-196708000-00010.CrossRefGoogle Scholar
Vanselow, A.R., 1932 Equilibria of the base-exchange reactions of bentonites, permutites, soil colloids, and zeolites Soil Sci 33 95–113 10.1097/00010694-193202000-00002.CrossRefGoogle Scholar
Verburg, K. and Baveye, P., 1994 Hysteresis in the binary exchange of cations on 2:1 clay minerals: A critical review Clays Clay Miner 42 207–220 10.1346/CCMN.1994.0420211.CrossRefGoogle Scholar
Verburg, K. Baveye, P., Churchman, G.J. Fitzpatrick, R.W. and Eggleton, R.A., 1995 Influence of quasi-crystal formation and intercrystalline swelling on cation exchange hysteresis in smectites Clays: Controlling the environment Melbourne, Australia CSIRO Publ 173–177.Google Scholar
Verburg, K. and Baveye, P., 1995 Effects of cation exchange hysteresis on a mixing procedure used in the study of clay suspensions Clays Clay Miner 43 637–640 10.1346/CCMN.1995.0430514.CrossRefGoogle Scholar
Verburg, K. Baveye, P. and McBride, M.B., 1995 Cation exchange hysteresis and the dynamics of the formation and breakdown of montmorillonite quasi-crystals Soil Sci Soc Am J 59 1268–1273 10.2136/sssaj1995.03615995005900050009x.CrossRefGoogle Scholar