Smectites properties

Intracrystallihe swelling was not discovered until the advent of the X-ray diffraction method of analysis (Hofmann et al. [1933], Hofmann and Bilke [1936]). X-rays are, therefore, very important in the study of smectites. Their role is not limited to the analysis of the structure and the identification of the different types of smectites. Instead, X-ray diffraction is the principal method used in the qualitative and quantitative description of smectite properties. 

Smectites are stmcturaUy similar to pyrophylUte [12269-78-2] or talc [14807-96-6], but differ by substitutions mainly in the octahedral layers. Some substitution may occur for Si in the tetrahedral layer, and by F for OH in the stmcture. Deficit charges in smectite are compensated by cations (usually Na, Ca, K) sorbed between the three-layer (two tetrahedral and one octahedral, hence 2 1) clay mineral sandwiches. These are held relatively loosely, although stoichiometricaUy, and give rise to the significant cation exchange properties of the smectite. Representative analyses of smectite minerals are given in Table 3. The deterrnination of a complete set of optical constants of the smectite group is usually not possible because the individual crystals are too small. Representative optical measurements may, however, be found in the Uterature (42,107). 

Allophane and Imogolite. AUophane is an amorphous clay that is essentially an amorphous soHd solution of sUica, alumina, and water (82). In allophane less than one-half of the aluminum is held in tetrahedral coordinations and the Si02 to AI2O2 ratio typically varies between 1.3 and 2.0, but values as low as 0.83 have been reported. The typical morphology of allophane is cylindrical (37). AUophane may be associated with haUoysite, smectite minerals, or it may occur as a homogeneous mixture with evansite, an amorphous soHd solution of phosphoms, alumina, and water. Its composition, hydration, and properties vary. Chemical analyses of two allophane samples are given in Table 5. 

Cations exchanged into the interlayers of expandable clays (smectites) are comparatively easy to study with NMR methods because the cations become major components of the phase and their concentrations are often several wt %. In addition to Cs Li, Na, K, and Cd have been studied by NMR. We have chosen to investigate Cs because it is a significant component of nuclear waste, because it provides an end-member case as the least electronegative cation, and because it has desirable nuclear properties (100% abundance, relatively high frequency, 65.5 MHz at H = 11.7 T, and small quadrupole moment)... 

Vaccari (1983,1999) has given a state-of-the-art account of the preparation and catalytic properties of cationic and anionic clays. Some examples of industrial importance have also been reported. Clays exhibit many desirable features, such as low cost, wide range of preparation variables, ease of set-up and wOrk-up, high selectivity, and environmental friendliness. Cationic clays are widespread in nature, whereas anionic clays are rarely found in nature, but they can be synthesized cheaply. Cationic clays are prepared from the minerals but industrial anionic clays are generally synthetic. Smectite clays exhibit both Brpnsted and Lewis acid sites on the edges of the crystals. Hammet s acidity function values are as follows Na -montmorillonite (M), -3 to t- 1.5 NH4VM -3 to 1.5 H M -8.2 to -5.6 acid activated clay less than -8.2. Laporte also has a synthetic version of cationic clays, Laponite. The acid... 

The abundant dark brown to black soft minerals in the collected samples are identified as smectite, based on optical properties under a polarizing microscope. 

Chatteijee, A., Iwasaki, T., Ebina, T., and Mizukami, F. 2003. Intermolecular reactivity study to scale adsorption property of para- and meta-substituted nitrobenzene over 2 1 dioctahedral smectite. J. Chem. Phys. 118 10212-10220. 

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. 

The assumption that the water is adsorbed in uniform layers on all the clay surfaces for a wide range of mixtures has been criticized (2, 20). The argument is that the individual clay particles in the clay-water mixture do not expand beyond a certain distance regardless of the quantity of water which is added. The clay layers group themselves into tactoids resulting in two populations of water those molecules which are found between the tactoids and those directly perturbed by the clay layers. If true, this would invalidate the procedure used to calculate the thermodynamic properties of the adsorbed water. However, other workers have reported complete delamination of certain smectites (21., 22). It is not clear under what conditions tactoids will form, or not, and this uncertainty is underlined in (21) (see remarks by Nadeau and Fripiat, pages 146-147). 

The validity of the assumption that the various thermodynamic properties of the smectite remain invariant, regardless of the state of hydration, has been addressed in detail by Sposito and Prost (1). They point out that one would, for example, expect hydrolysis of the clay to occur at high water contents, and also, it is likely that the exchangeable cations will change their spatial relationship with the clay layers. Thus, the derived thermodynamic properties of the adsorbed water would not represent correct values. 

It is believed that CuO O) " - orients in vermiculite interlayers (2 water layers thick) as shown in Figure 18B (6). Yet, the smectites with more vermiculite-like properties (high tetrahedral charge, high total charge) showed no evidence of this orientation, even in cases where two layers of water were situated between the plates. It is necessary to conclude that Cud O) " or Cu(H20)5 + ions are found in the two-layer hydrates of the smectites, with the orientation shown in Figure 18C. 

---