Clay minerals exchange

Ion-exchange processes on clay minerals moving from riverwater to seawater (Section 6.2.3) remove about 26% of the river flux of Na+ to the oceans and are significant removal processes for K+ and Mg2+ (Table 6.3). To balance this removal, clay minerals exchange a significant amount of Ca2+ to the oceans, adding an extra 8% to the river flux (Table 6.3). These modern values are,... 

There are several causes of the generally poor correlation between the extractable quantity of a heavy metal and soil pH or availability to plants. Varying amounts of carbonates, organic matter, hydrous oxides of manganese and iron, as well as soil Eh values all affect the amounts of these metals which are extractable. Much better correlations than those obtained would be expected if the heavy metals were located on clay mineral exchange sites or were complexed by organic matter. 

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). 

In ceramics, plasticity is usually evaluated by means of the water of plasticity. Values for the common clay minerals are given in Table 1. Each clay mineral can be expected to show a range of values because particle size, exchangeable ion composition, and crystallinity of the clay mineral also exert an influence. Nonclay mineral components, soluble salts, organic compounds, and texture can also affect the water of plasticity. 

It is believed that clay minerals promote organic reactions via an acid catalysis [2a]. They are often activated by doping with transition metals to enrich the number of Lewis-acid sites by cationic exchange [4]. Alternative radical pathways have also been proposed [5] in agreement with the observation that clay-catalyzed Diels-Alder reactions are accelerated in the presence of radical sources [6], Montmorillonite K-10 doped with Fe(III) efficiently catalyzes the Diels-Alder reaction of cyclopentadiene (1) with methyl vinyl ketone at room temperature [7] (Table 4.1). In water the diastereoselectivity is higher than in organic media in the absence of clay the cycloaddition proceeds at a much slower rate. 

The clay mineral bentonite (sodium montmorillonite) has an excellent ion exchange and adsorption capacity. Films can be applied to electrode surfaces from colloidal clay solutions by simple dip or spin coating that become electroactive after incorporation of electroactive cations or metal particles 136-143)... 

In clay mineral crystals, atoms having different valences commonly will be positioned within the sheets of the structure to create a negative potential at the crystal surface. In that case, a cation is adsorbed on the surface. These adsorbed cations are called exchangeable cations because they may chemically trade places with other cations when the clay crystal is suspended in water. In addition, ions may also be adsorbed on the clay crystal edges and exchange with other ions in the water. 

Reactions with clay minerals can neutralize both low-pH and high-pH solutions. Neutralization of acids occurs when hydrogen ions replace Al, Mg, and Fe. In alkaline solutions, neutralization is more complex and may involve cation exchange, clay dissolution, and reaction of cations with hydroxide ions to form new minerals called zeolites.39... 

Adsorption (including both physical adsorption and ion exchange) by clay minerals and silicates... 

Radenti et al. reported the corrosion rate of a typical potassium chloride fluid of 247 mils/year at 212°F. In contrast, they found by substituting potassium carbonate for potassium chloride, the corrosion rate was reduced to 3 mils/year t10 . Unfortunately, potassium carbonate is not optimum as a drilling fluid additive because it can produce massive amounts of calcium precipitation, may elevate the pH to undesirable levels, and in all cases reduces the calcium ion concentration to such a low level as to promote destabililzing cation exchange with clay minerals. 

Exchangeable ions (EXC), sometimes including ions nonspecifically adsorbed and specifically absorbed on the surface of various soil components, such as carbonate, organic matter, Fe, Mn, Si, and Al oxides, and clay minerals. This part is controlled by adsorption-desorption processes. 

---