Lattice ionic compounds

Heterodesmic lattices ionic compounds metallic compounds... 

To date there is no evidence that sodium forms any chloride other than NaCl indeed the electronic theory of valency predicts that Na" and CU, with their noble gas configurations, are likely to be the most stable ionic species. However, since some noble gas atoms can lose electrons to form cations (p. 354) we cannot rely fully on this theory. We therefore need to examine the evidence provided by energetic data. Let us consider the formation of a number of possible ionic compounds and first, the formation of sodium dichloride , NaCl2. The energy diagram for the formation of this hypothetical compound follows the pattern of that for NaCl but an additional endothermic step is added for the second ionisation energy of sodium. The lattice energy is calculated on the assumption that the compound is ionic and that Na is comparable in size with Mg ". The data are summarised below (standard enthalpies in kJ) ... 

The enthalpy of solution is quite small for many simple ionic compounds and can be either positive or negative. It is the difference between two large quantities, the sum of the hydration enthalpies and the lattice energy. 

Prediction of solubility for simple ionic compounds is difficult since we need to know not only values of hydration and lattice enthalpies but also entropy changes on solution before any informed prediction can be given. Even then kinetic factors must be considered. 

The small lithium Li" and beryllium Be ions have high charge-radius ratios and consequently exert particularly strong attractions on other ions and on polar molecules. These attractions result in both high lattice and hydration energies and it is these high energies which account for many of the abnormal properties of the ionic compounds of lithium and beryllium. 

As a result of these effects, anions in general are larger than cations. Compare, for example, the Cl- ion (radius = 0.181 nm) with the Na+ ion (radius = 0.095 nm). This means that in sodium chloride, and indeed in the vast majority of all ionic compounds, most of the space in the crystal lattice is taken up by anions. 

Compare the relative lattice energies of two ionic compounds (Example 2.2). 

When the radius ratio of an ionic compound is less than about 0.4, corresponding to cations that are significantly smaller than the anion, the small tetrahedral holes may be occupied. An example is the zinc-blende structure (which is also called the sphalerite structure), named after a form of the mineral ZnS (Fig. 5.43). This structure is based on an expanded cubic close-packed lattice of the big S2 anions, with the small Zn2+ cations occupying half the tetrahedral holes. Each Zn2+ ion is surrounded by four S2 ions, and each S2" ion is surrounded by four Zn2+ ions so the zinc-blende structure has (4,4)-coordination. 

Many ionic compounds are considered to pack in such as way that the anions form a close-packed lattice in which the metal cations fill holes or interstitial sites left between the anions. These lattices, however, may not necessarily he as tightly packed as the label close-packed implies. The radius of an F ion is approximately 133 pm. The edge distances of the cubic unit cells of LiF, NaF, KF, RbF, and CsF, all of which... 

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. 

C08-0074. Consider three possible ionic compounds formed by barium and oxygen Ba O, Ba O, and Ba O . (a) Which would have the greatest lattice energy (b) Which would require the least energy to form the ions (c) Which compound actually exists, and why ... 

The packing in ionic crystals requires that ions of opposite charges alternate with one another to maximize attractions among ions. A second important feature of ionic crystals is that the cations and anions usually are of different sizes. Usually the cations are smaller than the anions. Consequently, ionic compounds adopt a variety of structures that depend on the charges and sizes of the ions. One way to discuss ionic structures is to identify a crystal lattice for one set of ions, and then describe how the other ions pack within the lattice of the first set. 

The table shows the lattice energy for some ionic compounds. Based on these data, which of these compounds would require the most energy to separate the bonded ions ... 

Recognizing Cause and Effect In a crystal lattice structure, the electrons are held tightly by the ions, which are rigidly held in place by electrostatic attraction. Discuss how this characteristic explains why ionic compounds generally (a) have high melting points and (b) do not conduct electricity in the solid state. 

The structures of ionic compounds comprising complex ions can in many cases be derived from the structures of simple ionic compounds. A spherical ion is substituted by the complex ion and the crystal lattice is distorted in a manner adequate to account for the shape of this ion. 

The strong electrostatic lattice forces in ionic compounds give them high melting points. 

An enormous amount of chemistry is carried out in solutions that consist of ionic compounds that have been dissolved in a solvent. In order to separate the ions from the lattice in which they are held, there must be strong forces of interaction between the ions and the molecules of the solvent. The most common solvent for ionic compounds is water, and that solvent will be assumed for the purposes of this discussion. 

When an ionic compound is dissolved in a solvent, the crystal lattice is broken apart. As the ions separate, they become strongly attached to solvent molecules by ion-dipole forces. The number of water molecules surrounding an ion is known as its hydration number. However, the water molecules clustered around an ion constitute a shell that is referred to as the primary solvation sphere. The water molecules are in motion and are also attracted to the bulk solvent that surrounds the cluster. Because of this, solvent molecules move into and out of the solvation sphere, giving a hydration number that does not always have a fixed value. Therefore, it is customary to speak of the average hydration number for an ion. 

From the standpoint of energy, the processes of separating the crystal lattice and solvating the ions can be related by means of a thermochemical cycle of the Born-Haber type. For an ionic compound MX, the cycle can be shown as follows ... 

The attractions between positive ions (cations) and negative ions (anions) are strong, and ionic compounds have a giant lattice stmcture. 

Conductivity Metals are good conductors of electricity and heat because electrons can move freely throughout the metallic structure. This freedom of movement is not possible in solid ionic compounds, because the valence electrons are held within the individual ionic bonds in the lattice. 

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