Ionic compounds halides

Numerous ionic compounds with halogens are known but a noble gas configuration can also be achieved by the formation of a covalent bond, for example in halogen molecules, X2, and hydrogen halides, HX. When the fluorine atom acquires one additional electron the second quantum level is completed, and further gain of electrons is not energetically possible under normal circumstances, i.e... 

Beryllium Halides. The properties of the fluoride differ sharply from those of the chloride, bromide, and iodide. BeryUium fluoride is essentiaUy an ionic compound, whereas the other three haUdes are largely covalent. The fluoroberyUate anion is very stable. 

In the absence of die polyether, potassium fluoride is insoluble in benzene and unreactive toward alkyl halides. Similar enhancement of solubility and reactivity of other salts is observed in the presence of crown ethers The solubility and reactivity enhancement result because the ionic compound is dissociated to a tightly complexed cation and a naked anion. Figure 4.13 shows the tight coordination that can be achieved with a typical crown ether. The complexed cation, because it is surrounded by the nonpolar crown ether, has high solubility in the nonpolar media. To maintain electroneutrality, the anion is also transported into the solvent. The cation is shielded from interaction with the anion as a... 

The oxide (p. 1209), chalcogenides (p. 1210) and halides (p. 1211) have already been described. Of them, the only ionic compound is HgF2 but other compounds in which there is appreciable charge separation are the hydrated salts of strong oxoacids, e.g. the nitrate, perchlorate, and sulfate. In aqueous solution such salts are extensively hydrolysed (HgO is only very weakly basic) and they require acidification to prevent the formation of polynuclear hydroxo-bridged species or the precipitation of basic salts such as Hg(OH)(N03) which contains infinite zigzag chains ... 

Because the fluoride ion is so small, the lattice enthalpies of its ionic compounds tend to be high (see Table 6.6). As a result, fluorides are less soluble than other halides. This difference in solubility is one of the reasons why the oceans are salty with chlorides rather than fluorides, even though fluorine is more abundant than chlorine in the Earth s crust. Chlorides are more readily dissolved and washed out to sea. There are some exceptions to this trend in solubilities, including AgF, which is soluble the other silver halides are insoluble. The exception arises because the covalent character of the silver halides increases from AgCl to Agl as the anion becomes larger and more polarizable. Silver fluoride, which contains the small and almost unpolarizable fluoride ion, is freely soluble in water because it is predominantly ionic. 

Although naturally occurring compounds of transition metals are restricted in scope, a wide variety of compounds can be synthesized in the laboratory. Representative compounds appear in Table 20-2. These compounds fall into three general categories There are many binary halides and oxides in a range of oxidation numbers. Ionic compounds containing transition metal cations and polyatomic oxoanions also are common these include nitrates, carbonates, sulfates, phosphates, and perchlorates. Finally, there are numerous ionic compounds in which the transition metal is part of an oxoanion. 

Ionic compounds such as halides, carboxylates or polyoxoanions, dissolved in (generally aqueous) solution can generate electrostatic stabilization. The adsorption of these compounds and their related counter ions on the metallic surface will generate an electrical double-layer around the particles (Fig. 1). The result is a coulombic repulsion between the particles. If the electric potential associated with the double layer is high enough, then the electrostatic repulsion will prevent particle aggregation [27,30]. 

The properties of HF reflect the strong hydrogen bonding that persists even in the vapor state. As a result of its high polarity and dielectric constant, liquid HF dissolves many ionic compounds. Some of the chemistry of HF as a nonaqueous solvent has been presented in Chapter 10. Properties of the hydrogen halides are summarized in Table 15.9. 

The sodium chloride structure is adopted by a large number of compounds, from the ionic alkali halides NaCl and KC1, to covalent sulfides such as PbS, or metallic oxides such as titanium oxide, TiO. Slip and dislocation structures in these materials will vary according to the type chemical bonding that prevails. Thus, slip on 100 may be preferred when ionic character is suppressed, as it is in the more metallic materials. 

Ion exclusion chromatography, of ascorbic acid, 25 760 Ion hopping, 14 469 Ionic aggregates, 14 463—466 Ionically conducting polymers, 13 540 Ionic carbides, 4 647 Ionic compounds, rubidium, 21 822 Ionic conduction, ceramics, 5 587-589 Ionic crystals, 19 185. See also Silver halide crystals... 

For example, consider a solution that contains three halide ions Cl , Br , and l. Since these halides all come from the same group on the periodic table, they share many properties. When they are the anions in slightly soluble ionic compounds, however, they have different solubilities. (See Table 9.4.) Therefore, chemists can use fractional precipitation to separate them from solution. 

In practice, this hard-core model is too simple to predict reliably the ground-state structure of ionic compounds such as the alkali halides that are located in the upper left-hand corner of the AB structure map in Fig. 1.9. Nevertheless, it provides a simple introduction to the importance of the radius ratio in determining structural stability. 

It has been shown in Chapter VI that the stability of most complexes formed by two halides, oxides or hydrides follows the rules for complex formation of two ionic compounds. The formation of the complex ions BFt and NH " was described as an addition of the ions F and H+ to the molecules BF3 and NH3, caused by the attraction of the highly-charged ions B3+ and N3-. However, this complex formation can be given quite a different interpretation, and it can be argued that F ions combine with BF3 because, in this process, the octet of the B atom is completed... 

This brings us to a class of compounds too often overlooked in the discussion of simple ionic compounds the transition metal halides. In general, these compounds (except fluorides) crystallize in structures that are hard to reconcile with the structures of simple ionic compounds seen previously (Figs. 4.1-4.3). For example, consider the cadmium iodide structure (Fig. 7.8). It is true that the cadmium atoms occupy octahedral holes in a hexagonal closest packed structure of iodine atoms, but in a definite layered structure that can be described accurately only in terms of covalent bonding and infinite layer molecules. 

The Shannon-Prewitt ionic radii (r+ + r ) are based on the most ionic compounds, the fluorides and oxides for the radii of the metal cations, and the alkali hahdes for the radii of the anions of the remaining halides. The shortening of silver halide bond lengths is attributahle to polarization and covalency. 

The tetraalkylammonium halides formed by complete alkylation of amines are ionic compounds that resemble alkali-metal salts. When silver oxide is used to precipitate the halide ion, tetraalkylammonium halides are converted to tetraalkylammonium hydroxides, which are strongly basic substances similar to sodium or potassium hydroxide ... 

Halides of metals tend to be ionic unless the metal has an oxidation number greater than +2. For example, sodium chloride and copper(II) chloride are ionic compounds and have high melting points, but TiCl4 and FeCl3 sublime as molecules. 

The above characterizations primarily concern the interactions between molecular solutes and ILs. However, ILs are also good solvents for ionic compounds, and have been studied extensively as media for transition metal catalysis [4, 38, 219] and for the extraction of heavy metals [23]. ILs are capable of solvating even simple salts, such as NaCl, to some degree [219], and in fact the removal of halide impurities resulting from synthesis can be a considerable challenge [68]. However, ionic complexes are generally far more soluble than simple salts [220], and we focus our attention on these systems as they have received greater study and are more relevant to the processes noted above. 

A majority of halides and oxides have the structures expected for largely ionic compounds, with the metal in octahedral... 

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