Cation exchange smectite

M. F. Brigatti, T. Manfredini, M. Montorsi, G. Ori, and C. Siligardi, Cation-exchanged smectites Preparation, characterization and modeling. Submitted for publication. 

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). 

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)... 

Fig. 6. Uptake of benzene from water by various smectites exchanged with trimethylphenylammonium (TMPA) ions (cf. Fig. 2). Numbers in brackets refer to the cation exchange capacities of the smectites, (cf. Fig. 4). After Jaynes and Boyd (1991b).

Another type of reaction that responds to WD cycles is the fixation of K and NH4 ions by smectite (3-7). The fixation of K in smectite has been studied extensively by soil scientists because of its effect on the availability of plant nutrients. The reaction also decreases smectite s ability to swell, decreases its cation exchange capacity (CEC), and modifies its BrjSnsted acidity. Therefore, an understanding of this phenomenon is applicable to many fields of study that are concerned with swelling clays, fields such as soil fertility, soil mechanics, waste disposal, clay catalysis, and the geochemistry of ground and surface waters. 

XRD) and chemical extraction procedures, that much of the observed cation exchange capacity (CEC) arises from smectite impurities, the external surface CEC of kaollnite ranging from 0-1 meq/100 g. 

Na -loess clay, where batch experiments were analyzed by X-ray diffraction and infrared and far-infrared measurements. The adsorption isotherm (Fig. 8.36) shows that loess clay is selective for cesium cations. The raw material contained a large amount of quartz, and the clay material was a mixture of kaolinite and an interstrati-fied iUite-smectite mineral as a result, equilibrium Cs" adsorption data are not consistent with a single site Langmuir model. Cesium adsorption on this particular soil clay occurs by cation exchange on sites with various cesium affinities. At low concentration, far-infrared spechoscopy shows the presence of very selective adsorption sites that correspond to internal collapsed layers. At high concentration, Cs MAS-NMR shows that cesium essentially is adsorbed to external sites that are not very selective. 

The smectite group of clay minerals is also poorly crystalline but perhaps better known because of their cation exchange capacity and their occurrence in the bentonite clays. A general formula for montmorillonite, which is one of the dioctahedral smectites is... 

Zeolite surface chemistry resembles that of smectite clays. In contrast to clays, however, natural zeolites can occur as millimeter- or greater-sized particles and are free of shrink-swell behavior. As a result, zeolites exhibit superior hydraulic characteristics and are suitable for use in filtration systems (Breck 1974) and as permeable barriers to dissolved chemical migration. Internal and external surface areas up to 800 m2 g have been measured. Total cation exchange capacities in natural zeolites vary from 250 to 3000 meq kg 1 (Ming and Mumpton 1989). External cation exchange capacities have been determined for a few natural zeolites and typically range from 10 to 50 percent of the total cation exchange capacity (Bowman et al. 1995). 

Teppen, B. J., and Aggarwal, V. (2007).Thermodynamics of organic cation exchange selectivity in smectites. Clays Clay Min. 55,119-130. 

Drame, H. 2005. Cation exchange and pillaring of smectites by aqueous Fe nitrate solutions. Clays Clay Miner. 53 335-347. 

---