Kaolinite exchangeable cations

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. 

Rearrangement reactions catalyzed by the clay surface were observed for par-athion (an organophosphate pesticide) when it was adsorbed on montmorillonite or kaolinite in the absence of a liquid phase. The rate of rearrangement reactions increased with the polarization of the hydration water of the exchangeable cation (Mingelgrin and Saltzman 1977). Table 14.1 summarizes a series of reactions catalyzed by clay surfaces, as reported in the literature. 

The identity of the exchangable cations is seldom determined although Hinckley (1961) showed that in the Georgia kaolinites exchangable Ca was two to five times as abundant as K. Na and Mg were not determined. Hydrogen is presumably the most abundant exchangable cation at the time of formation. 

Dehydrated halloysites have C.E.C. in the range of 6—10 mequiv./lOO g (Van der Marel, 1958 Garrett and Walker, 1959). Garrett and Walker have shown that the exchangable cations are located on the external surfaces of the crystals and not in the interlayer position of halloysite. Until it is possible to obtain accurate chemical analyses of the kaolinite minerals, it will be difficult to determine their exchange capacity and the source of the charge. 

The most powerful methods for the study of adsorption mechanism of nitroaromatic compounds on clay minerals have become in situ spectroscopic investigations. Handerlein et al. [152, 153] and Weissmahr et al. [154-156] have investigated the adsorption of NACs particularly on illites, montmorillonites and homoionic kaolinites. The substituted nitrobenzenes on the surface of smectites were investigated by Boyd et al. [157, 158], The main focus in the experimental study of adsorption of NACs on the surface of clay minerals is the influence of the type of clay mineral, the effect of exchangeable cation of the mineral, the effect of the structure and the kind of substituents of NAC compound on the position and orientation of NACs to the surface of mineral, the character of interaction between NACs and the surface of mineral, the adsorption energy. 

Clay minerals are hydrous aluminum phyllosilicates made of sheets or layers composed of tetrahedra and octahedra. This mineral type includes the following groups kaolinite, smectite, illite, and chlorite. In the case of smectite, each layer comprises two sublayers of tetrahedra with an inserted octahedral layer, where, between layers, an interlayer space where the exchangeable cations are located is formed [131-133], In Figure 2.24... 

There are inconsistencies in the model for the calculation of activity products for the "clays. Exchangeable cations are disregarded for the low exchange capacity kaolinite, halloysite, chlorite, and moderate capacity illite. For certain expansible layer silicates and two zeolites, the logjo of the activity of selected cations is added into the sum of the activity products. 

Mineralogical phases formed at different temperatures for each coal sample are summarized in Table III. The major mineral phases detected by XRD in LTA samples are quartz, pyrite, bassanite, kaolinite and plagioclase. The processes responsible for subsequent mineral transformations include oxidation, vaporization, sulfur fixation, dehydration and solid-state Interactions. The temperatures at which specific transformations occur are assigned on the basis of previous experimental work by Mitchell and Gluskoter (4) and published chemical data in the Handbook of Chemistry and Physics ( ). In addition to mineral-mineral interactions it is believed that reactions between minerals and exchangeable cations occur (2) ... 

Aluminosilicates such as montmorillonite, kaolinite, illite, and vermiculite are solids that have structures readily accessible to counter ions. The excess negative charge resulting from isomorphic substitution of Al for Si is primarily distributed over the three adjacent surface O atoms of the layer, where it is electrically balanced by mobile, exchangeable cations- Thermodynamically, ion exchange can be interpreted in terms of the interlayer electrostatic interaction between surface charges and hydrated cations in accordance with the classical Eisenman theory (Eisenman, 1983). A comprehensive description has recently been given by Maes and Cremers (1986). 

At higher Si(OH)4 activities, Fig. 7.5 shows that kaolinite is unstable and is transformed to montmorillonite. Assuming that Ca2+ is the only exchangeable cation in the system, the equation for the equilibrium between kaolinite and montmorillonite... 

Chemical Properties. An important chemical property of clays, which directly affects fines migration is the cation exchange capacity (CEC) (6-9). CEC is a measure of the capacity of a clay to exchange cations. It is usually reported in units of milliequivalents per 100 g of clay (meq/100 g). The CEC depends on the concentration of exchangeable cations in the diffuse Gouy-Chapman layer (see later). This concentration depends on the total particle charge, which may vary with pH. Unless stated otherwise, the reported values of CEC are measured at neutral pH. CEC values (meq/lOOg) of common clay minerals are as follows smectites, 80-150 vermiculites, 120-200 illites, 10-40 kaolinite, 1-10 and chlorite, <10 (10). 

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... 

With a change in the composition of exchange cations, the microstructure of kaolinite sediments is practically unchanged (Fig. 4). 

Many mineralogic reactions involve exchange of cations or anions. Hence, geochemists commonly need to determine equilibrium lines in terms of activity ratios. Consider, for example, the reaction at 25 °C between the clay kaolinite [Al2Si205(0H)4] and the mica muscovite. The RXN commands... 

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