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

David Laird1 and Chao Shang2
1 USDA, ARS, National Soil Tilth Laboratory, 2150 Pammel Drive, Ames, Iowa 50011
2 Northern Agriculture Research Center, Agriculture Canada P.O. Box 29, Bearverlodge, Alberta, Canada TOH OCO

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 fluoro-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.

Key Words: Cation Exchange Selectivity • Crystalline Swelling • Demixing • Fixation • Ion Exchange Hysteresis • Layer Charge • Smectite

Clays and Clay Minerals; October 1997 v. 45; no. 5; p. 681-689; DOI: 10.1346/CCMN.1997.0450507
© 1997, The Clay Minerals Society
Clay Minerals Society (www.clays.org)