Permanent structural charge

Application of the electric double layer theory to soil minerals at a quantitative level is difficult because soil mineral surfaces at the microscopic scale are not well defined, that is, they are neither perfectly spherical nor flat, as the double layer requires. However, application of the double layer theory at a qualitative level is appropriate because it explains much of the behavior of soil minerals in solution, for example, dispersion, flocculation, soil permeability, and cation and/or anion adsorption. When equilibrium between the counterions at the surface (near the charged surface) and the equilibrium solution is met, the average concentration of the counterions at any 

R = universal gas constant (8.314 Jmol-1 °K) p = charge density at any point T = absolute temperature K = Boltzman constant (1.38 x 10 23 J °K I) 

When y is negative, n+ n, whereas when is positive, n n+. The surface charge density p and the electrical point / at any point are related by Poisson s equation  

The component k is the inverse of the thickness of the double layer, which extends from the solid surface to the point where the local potential is that of the bulk solution, and is given by (Stumm and Morgan, 1970) 

Equation 3.7 points out that the variation in the electric field strength (-dy/dx) is related to the second power of the inverse of the thickness of the double layer times /, while Equation 3.8 shows that / decays exponentially with respect to distance (jc) from the surface (Fig. 3.23). A plot of ln( // (/0) versus x produces a straight line with slope k, which is the inverse of the double layer thickness. The assumption ij/0 25 mV is not applicable to all soil minerals or all soils. Commonly, clay minerals possess more than 25 mV in surface electrical potential, depending on ionic strength. The purpose of the assumption was to demonstrate the generally expected behavior of charged surfaces. 

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Since cations are adsorbed electrostatically not only due to the permanent structural charge, a0, (caused by isomorphic substitution) but also due to the proton charge, oh, (the charge established because of binding or dissociating protons -see Chapter 3.2) the ion exchange capacity is pH-dependent (it increases with pH). Furthermore, the experimentally determined capacity may include inner-spherically bound cations. 

The overall charge of a sorbent would then be the sum of any permanent structural charges and any charges resulting from surface reactions with the aqueous solution (Krauskopf and Bird, 1995), 140. 

Oq = permanent structural charge (usually for a mineral) caused by isomorphic substitutions (or the formation of solid solutions) in minerals significant charge is produced primarily in the 2 1 phyl-losilicates. 

The surface charge characterization of clay minerals, when permanent charges from isomorphic substitutions of ions in a clay crystal lattice are present besides the variable edge charges, is more complicated than that of metal oxides. In this case, the intrinsic surface charge density, Cin, can be defined as the sum of the net permanent structural charge density, oq, and the net proton surface charge density, ffo.H, i-C-, [2,... 

Clay minerals have a permanent negative charge due to isomorphous substitutions or vacancies in their structure. This charge can vary from zero to >200cmol kg" (centimoles/kg) and must be balanced by cations (counter-ions) at or near the mineral surface (Table 5.1), which greatly affect the interfacial properties. Low counter-ion charge, low electrolyte concentration, or high dielectric constant of the solvent lead to an increase in interparticle electrostatic repulsion forces, which in turn stabilize colloidal suspensions. An opposite situation supports interparticle... 

The net permanent structural surface charge density, denoted gq and measured in coulombs per square meter (C/m2), is created by isomorphic substitutions in minerals [4]. These substitutions in clay minerals produce significant surface charge only in the 2 1 layer types. In these minerals, Co < 0 invariably because of structural cation substitutions. The relation between gq and the layer charge jc is [3]... 

Kaolinite is a 1 1 (T-O) phyllosilicate. The fundamental unit of its structure is an extended sheet of two constituents a silica-type layer of composition (Si4O10)4- and a gibbsite-type layer of composition (0H)6A14(0H)204 (see schematic representation in Fig. 10). Ideally, kaolinite crystals are not permanently charged. However, due to isomorphic substitution of Si by Al at the siloxane surface, kaolinite platelets carry a small, permanently negative charge (Van Olphen, 1977). Lim et al. (1980) and Talibudeen (1984) postulate that the permanent charge of kaolins is caused by contamination with small amounts of 2 1 phyllosilicates rather than a consequence of isomorphic substitution. 

The most important physical characteristic of an electrifled interface is its surface charge density. The concept of surface charge density was introduced in Sec. 1.5 in the discussion of the surface density of intrinsic, permanent structural, and net proton charge. These three surface charge densities are related by the equation... 

Most commonly used layered silicate is montmorillonite clay, which is composed of micron-sized particles. The particles are constructed of platelets with thickness of lnm and width of 100-200 nm. Platelets have permanent negative charge and they are held together by charge balancing cations such as Na" or Ca [2-i] ions. The significant disruption of individual silicate layers in polymer matrix with nanoscopic dimensions (exfoHated structure) leads to improvements of the nanocomposite properties. However, in many cases, the isolated silicate layers are not completely dispersed throughout the polymer matrix, instead, the clay particles in polymer matrix maintain the hierarchical architecture, and an interlayer expansion occurs (intercalated structure). 

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