Isomorphous substitution cations

One of the most important parameters that defines the structure and stability of inorganic crystals is their stoichiometry - the quantitative relationship between the anions and the cations [134]. Oxygen and fluorine ions, O2 and F, have very similar ionic radii of 1.36 and 1.33 A, respectively. The steric similarity enables isomorphic substitution of oxygen and fluorine ions in the anionic sub-lattice as well as the combination of complex fluoride, oxyfluoride and some oxide compounds in the same system. On the other hand, tantalum or niobium, which are the central atoms in the fluoride and oxyfluoride complexes, have identical ionic radii equal to 0.66 A. Several other cations of transition metals are also sterically similar or even identical to tantalum and niobium, which allows for certain isomorphic substitutions in the cation sublattice. 

The isomorphic substituted aluminum atom within the zeolite framework has a negative charge that is compensated by a counterion. When the counterion is a proton, a Bronsted acid site is created. Moreover, framework oxygen atoms can give rise to weak Lewis base activity. Noble metal ions can be introduced by ion exchanging the cations after synthesis. Incorporation of metals like Ti, V, Fe, and Cr in the framework can provide the zeolite with activity for redox reactions. 

We have described above the evolution of the magnetic properties of the [Cp2M (dmit)]AsFg salts upon isomorphous Mo/W substitution. Another possibility offered by this attractive series is the isomorphous substitution of the counter ion, that is PFg- vs AsF6 vs Sbl- fi. Electrocrystallization experiments conducted with [Cp2Mo(dmit)] and the three different electrolytes afforded an isomorphous series, with a smooth evolution of the unit cell parameters with the anion size [32], This cell expansion with the anion size leads to decreased intermolecular interactions between the [Cp2Mo(dmit)]+ radical cation, as clearly seen in Table 2 from the decreased Curie-Weiss temperatures and Neel temperatures (associated with the transition they all exhibit to an AF ground state). 

Another characteristic of 2 1 clays is isomorphous substitution, where iso means same and morphous means shape. During the formation of clay, cations other than aluminum and silicon become incorporated into the structure. In order for this to work and still ensure a stable clay, the cation must be about the same size as either aluminum or silicon, hence the term isomorphous. There are a limited number of cations that satisfy this requirement. For silicon, aluminum as Al3+ and iron as Fe3+ will tit without causing too much distortion of the clay structure. For aluminum, iron as Fe3+, magnesium as Mg2+, zinc as Zn2+, and iron as Fe2+ will fit without causing too much structural distortion (see Figure 3.4). 

The Smectite Clays. The smectite-type clays are distinctive in that they expand and cause significant destruction to synthetic (human-made) structures. In this type of 2 1 clay, isomorphous substitution occurs in the aluminum sheet. If there is substitution of lower-oxidation-state metal such as magnesium, there will be an unsatisfied pair of bonding electrons in the interior of the crystal and there will be no noticeable change in the surface. Because the charge is in the interior of the crystal, its attraction for cations is diminished by distance. Thus, smectite crystals are not held together strongly by cations and are able to incorporate more water and ions between sheets when the environment is wet and less when it is dry. 

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. 

In surface precipitation cations (or anions) which adsorb to the surface of a mineral may form at high surface coverage a precipitate of the cation (anion) with the constituent ions of the mineral. Fig. 6.9 shows schematically the surface precipitation of a cation M2+ to hydrous ferric oxide. This model, suggested by Farley et al. (1985), allows for a continuum between surface complex formation and bulk solution precipitation of the sorbing ion, i.e., as the cation is complexed at the surface, a new hydroxide surface is formed. In the model cations at the solid (oxide) water interface are treated as surface species, while those not in contact with the solution phase are treated as solid species forming a solid solution (see Appendix 6.2). The formation of a solid solution implies isomorphic substitution. At low sorbate cation concentrations, surface complexation is the dominant mechanism. As the sorbate concentration increases, the surface complex concentration and the mole fraction of the surface precipitate both increase until the surface sites become saturated. Surface precipitation then becomes the dominant "sorption" (= metal ion incorporation) mechanism. As bulk solution precipitation is approached, the mol fraction of the surface precipitate becomes large. 

The surfaces of colloidal particles are often charged and these changes can arise from a number of sources. Chemically bound ionogenic species may be found on the surface of particles such as rubber or paint latex particles. Charged species may be physically adsorbed if ionic surface active materials, for example, have been added. A charged surface may occur on a crystal lattice. An example is the isomorphous substitution of lower valency cations such as aluminium for silicon in the lattice structure of clays. A further example is the adsorption of lattice ions... 

The calcium ion is of such a size that it may enter 6-fold coordination to produce the rhombohedral carbonate, calcite, or it may enter 9-fold coordination to form the orthorhombic carbonate, aragonite. Cations larger than Ca2+, e.g., Sr2+, Ba2+, Pb2+, and Ra2 only form orthorhombic carbonates (at earth surface conditions) which are not, of course, isomorphous with calcite. Therefore these cations are incapable of isomorphous substitution in calcite, but may participate in isodimorphous or "forced isomorphous" substitution (21). Isodimorphous substitution occurs when an ion "adapts" to a crystal structure different from its own by occupying the lattice site of the appropriate major ion in that structure. For example, Sr2+ may substitute for Ca2 in the rhombohedral lattice of calcite even though SrC03, strontianite, forms an orthorhombic lattice. Note that the coordination of Sr2 to the carbonate groups in each of these structures is quite different. Very limited miscibility normally characterizes such substitution. 

After delivery to the ocean, clay minerals react with seawater. The processes that alter the chemical composition of the terrigenous clay minerals during the first few months of exposure are termed halmyrolysis. These include (1) cation exchange, (2) fixation of ions into inaccessible sites, and (3) some isomorphic substitutions. Another important transfiarmation is flocculation of very small (colloidal-size) clay particles into larger ones. 

Isomorphic substitution The replacement of some of the aluminum and silicon in aluminosilicate minerals by cations of similar ionic charge and radius. This usually occurs as a result of chemical weathering. 

The particular combinations of ions and molecules that will form precipitates in a given solution can be predicted from equilibrium thermodynamics. However, this often gives a misleading picture because there are kinetic limitations or there is inhibition, particularly in soil solutions. There may also be isomorphous substitution of one cation for another in the precipitate, resulting in a solid solution with a different solubility to the pure compound. 

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 existence of these isostructural compounds suggests that solid solutions could be formed between two end members via isomorphous substitution for Fe " by other cations. The likelihood of substitution depends on the similarity of the ionic radii and the valency of the cations (Goldschmidt, 1937). m " is the most suitable cationic species and a radius about 18% higher or lower than that of high-spin Fe " in sixfold coordination can be tolerated. Isomorphous replacement of Fe in Fe oxides by a number of cations has been observed in nature and, more frequently, in the laboratory. As far as is known, however, almost all these solid solutions have broad miscibility gaps, possibly induced by development of structural strain as substitution rises. 

Macedo et al. [227] studied HY zeolites dealuminated by steaming, and found that the strength of intermediate sites decreased with increasing dealumination for Si/Al ratios varying from 8 to greater than 100. For comparison, isomorphously substituted HY, which is free of extra-framework cationic species, possesses more acid sites than conventionally dealuminated solids with a similar framework Si/Al ratio [227], This is because some of the extra-framework aluminum species act as charge-compensating cations and therefore decrease the number of potential acid sites. 

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