Water on smectites

Water on Smectites. Compared to vermiculites, smectites present a more difficult experimental system because of the lack of stacking order of the layers. For these materials, the traditional technique of X-ray diffraction, either using the Bragg or non-Bragg intensities, is of little use. Spectroscopic techniques, especially nuclear magnetic resonance and infrared, as well as neutron and X-ray scattering have provided detailed information about the position of the water molecules, the dynamics of the water molecule motions, and the coordination about the interlayer cations. 

The important role of the exchangeable cation in determining the structure of adsorbed water on smectites was discussed in the review of experimental studies of the structure of water adsorbed on smectites [32], It was concluded that the spatial arrangement of the adsorbed water molecules indeed derives mainly from the solvation of exchangeable cations. Despite the great... 

SMECTITE GROUP MINERALS. The structuTe of Water adsorbed by smectite group minerals has been studied extensively in both its static (D structure) and dynamic aspects. As with water molecules on vermiculite, the behavior of water on smectite surfaces is conditioned sensitively on the type of exchangeable cation and on the location of isomorphic cation substitutions in the layer structure. In many respects, a discussion of the configuration of water molecules hydrating smectites is parallel to that for vermiculite. 

The spatial extent of adsorbed water on smectite surfaces is a matter of some controversy. Infrared spectroscopy, NMR relaxation, and X-ray and neutron diffraction experiments all point to a thickness of the adsorbed water film of around 1.0 nm. However, certain thermodynamic data, summarized for Na-montmorillonite in Table 2.5, suggest a thickness as great as 10 nm or more." These data are for partial and apparent specific properties of montmorillonite-water systems whose variation with water... 

See, e.g., D.M.C. MacEwan and M. J. Wilson, Interlayer and intercalation compounds of clay minerals, in G. W. Brindley and G. Brown, op cit. That 1 1 electrolytes cannot be dissolved completely in adsorbed water on smectites and illitic micas has been shown by A. M. Posner and J. P. Quirk, The adsorption of water from concentrated electrolyte solutions by montmorillo-nite and illite, Proc. Royal Soc. (London) 278A 35 (1964). 

Kowalska M, Gtiler H, Cocke DL (1994) Interactions of clay minerals with organic pollutants. Sci Total Environ 141 223-240 Kukkadapu RK, Boyd SA (1995) Tetramethylphosphonium-smectite and tetramethylammonium-smectite as adsorbents of aromatic and chlorinated hydrocarbons - effect of water on adsorption efficiency. Clays Clay Miner 43 318-323... 

Laird DA, Barriuso E, Dowdy RH, Koskinen WC (1992) Adsorption of atrazine on smectites. Soil Sci Soc Am J 56 62-67 LeBaron PC, Wang Z, Pinnavaia TJ (1999) Polymer-layered silicate nanocomposites an overview. Appl Clay Sci 15 11-29 Lee J-F, Crum JR, Boyd SA (1989) Enhanced retention of organic contaminants by soil exchanged with organic cations. Environ Sci Technol 23 1365-1372 Lee J-F, Mortland MM, Boyd SA, Chiou CT (1989a) Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite. J Chem Soc Faraday Trans I 8 2953-2962... 

Halloysite-10A represents a structure with few if any interlayer cations, allowing one to investigate the relatively simple case of water interacting with a clay surface. Similarly, ice-like models have been proposed for water adsorbed on smectite and vermie-ulite surfaces (2, 12, 12). These represent cases of charged clay layers with adsorbed exchangeable cations. 

Water on Vermiculite. For low water contents (that is, one or two water layers), the evidence for highly structured water in the interlayer spaces of smectites and vermiculites is most easily seen in X-ray diffraction structure determinations of ordered hydrate structures such as the two-water layer hydrate of Ca-vermiculite (14. 15) and Na-vermiculite (15., 16). 

The view that the clay surface perturbs water molecules at distances well in excess of 10 A has been largely based on measurements of thermodynamic properties of the adsorbed water as a function of the water content of the clay-water mixture. There is an extensive literature on this subject which has been summarized by Low (6.). The properties examined are, among others, the apparent specific heat capacity, the partial specific volume, and the apparent specific expansibility (6.). These measurements were made on samples prepared by mixing predetermined amounts of water and smectite to achieve the desired number of adsorbed water layers. The number of water layers adsorbed on the clay is derived from the amount of water added to the clay and the surface area of the clay. 

Our model for the adsorption of water on silicates was developed for a system with few if any interlayer cations. However, it strongly resembles the model proposed by Mamy (12.) for smectites with monovalent interlayer cations. The presence of divalent interlayer cations, as shown by studies of smectites and vermiculites, should result in a strong structuring of their primary hydration sphere and probably the next nearest neighbor water molecules as well. If the concentration of the divalent cations is low, then the water in interlayer space between the divalent cations will correspond to the present model. On the other hand, if the concentration of divalent cations approaches the number of ditrigonal sites, this model will not be applicable. Such a situation would only be found in concentrated electrolyte solutions. 

Clay minerals with their own surface properties affect the near surface water in different ways. The adsorbed water in the case of kaolinite consists only of water molecules ( pure water), whereas water adsorbed on a smectite-type mineral is an aqueous solution, due to the presence of exchangeable cations on the 2 1 layer sihcate. Sposito (1989) noted the generally accepted description that the spatial extent of adsorbed water on a phyUosilicate surface is about 1.0 nm (two to three layers of water molecules) from the basal plane of the clay mineral. 

Sposito G, Prost R (1982) Structure of water adsorption on smectites. Chem Rev 82 553-573... 

In many layer structures, such as clay minerals, the extent of lattice adjustment on entry of guest molecules is intermediate between the behaviors of zeolites and of clathrates. The layers remain intact, but the distance between them changes substantially (8). For water-free smectite crystals the d(001) distance is 9.4 A. The van der Waals diameter of a water molecule is 2.8 A so that, in batavite, for example, the water layer in the Na form is about 14.8 — 9.4 = 5.4 A thick, corresponding with two monolayers. 

Sposito, G. and Prost, R. (1982) Structure of water adsorbed on smectites, Chemical Reviews 82 Suppl. 6, 553-572... 

The definition of adsorbed water adopted in Sec. 2.3 requires an arrangement of water molecules that differs significantly from that in an appropriate reference aqueous phase. For water on the surfaces of kaolinite group minerals the reference phase is bulk liquid water, whereas for water on vermiculite and smectite surfaces the reference phase is an aqueous solution because of the presence of exchangeable cations on the 2 1 layer silicates. On the ba,si.s of this definition, the consensus developed in Sec. 2.3 is that the spatial extent of adsorbed water on a phyllosilicate... 

Another important chemical property of adsorbed water on vermiculite and smectite surfaces is its Br nsted acidity. This property should refer principally to the acidity of the solvated exchangeable cations, as described by the reaction... 

As the basal spacing increases, the structure expands. Smectites thus expand on absorption of water. On heating between 100-200°C, much of the interlayer H2O is lost, and basal spaeing deereases to about 10 A. When heated above 500°C, basal spacing reduees further to 9.6 A and the structure comes to fully collapsed state. 

The adsorption of neutral molecules on smectites is driven by various chemical interactions hydrogen bonds, ion-dipole interactions, coordination bonds, acid-base reactions, charge transfer, and van der Waals forces. Several polar molecules, such as alcohols, amines, and acids, form intercalation complexes with montmorillonites. The intercalation can be performed from the vapor, liquid, or even solid state. In intercalation from solution, solvent molecules are generally coadsorbed in the interlayer space. Guest molecules may be intercalated in dried clay minerals or may displace the water molecules of hydrated montmorillonite. 

FIGURE 6 Water vapor sorption isotherms on smectites exchanged with Ca, Ba, Cs, and Na ions. (Adapted from Ref. 89.)... 

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