Ionic Solids

You learned in Chapter 8 "Ionic versus Covalent Bonding" that an ionic solidA solid that consists of positively and negatively charged ions held together by electrostatic forces. consists of positively and negatively charged ions held together by electrostatic forces. (For more information about ionic solids, see Chapter 8 "Ionic versus Covalent Bonding", Section 8.2 "Ionic Bonding".) The strength of the attractive forces depends on the charge and size of the ions that compose the lattice and determines many of the physical properties of the crystal.

The lattice energy, the energy required to separate 1 mol of a crystalline ionic solid into its component ions in the gas phase, is directly proportional to the product of the ionic charges and inversely proportional to the sum of the radii of the ions. For example, NaF and CaO both crystallize in the face-centered cubic (fcc) sodium chloride structure, and the sizes of their component ions are about the same: Na⁺ (102 pm) versus Ca²⁺ (100 pm), and F⁻ (133 pm) versus O²⁻ (140 pm). Because of the higher charge on the ions in CaO, however, the lattice energy of CaO is almost four times greater than that of NaF (3401 kJ/mol versus 923 kJ/mol). The forces that hold Ca and O together in CaO are much stronger than those that hold Na and F together in NaF, so the heat of fusion of CaO is almost twice that of NaF (59 kJ/mol versus 33.4 kJ/mol), and the melting point of CaO is 2927°C versus 996°C for NaF. In both cases, however, the values are large; that is, simple ionic compounds have high melting points and are relatively hard (and brittle) solids.

Molecular Solids

Molecular solidsA solid that consists of molecules held together by relatively weak forces, such as dipole-dipole interactions, hydrogen bonds, and London dispersion forces. consist of atoms or molecules held to each other by dipole–dipole interactions, London dispersion forces, or hydrogen bonds, or any combination of these, which were discussed in Chapter 11 "Liquids". The arrangement of the molecules in solid benzene is as follows:

The structure of solid benzene. In solid benzene, the molecules are not arranged with their planes parallel to one another but at 90° angles.

Because the intermolecular interactions in a molecular solid are relatively weak compared with ionic and covalent bonds, molecular solids tend to be soft, low melting, and easily vaporized (ΔH_fus and ΔH_vap are low). For similar substances, the strength of the London dispersion forces increases smoothly with increasing molecular mass. For example, the melting points of benzene (C₆H₆), naphthalene (C₁₀H₈), and anthracene (C₁₄H₁₀), with one, two, and three fused aromatic rings, are 5.5°C, 80.2°C, and 215°C, respectively. The enthalpies of fusion also increase smoothly within the series: benzene (9.95 kJ/mol) < naphthalene (19.1 kJ/mol) < anthracene (28.8 kJ/mol). If the molecules have shapes that cannot pack together efficiently in the crystal, however, then the melting points and the enthalpies of fusion tend to be unexpectedly low because the molecules are unable to arrange themselves to optimize intermolecular interactions. Thus toluene (C₆H₅CH₃) and m-xylene [m-C₆H₄(CH₃)₂] have melting points of −95°C and −48°C, respectively, which are significantly lower than the melting point of the lighter but more symmetrical analog, benzene.

Self-healing rubber is an example of a molecular solid with the potential for significant commercial applications. The material can stretch, but when snapped into pieces it can bond back together again through reestablishment of its hydrogen-bonding network without showing any sign of weakness. Among other applications, it is being studied for its use in adhesives and bicycle tires that will self-heal.

Toluene and m-xylene. The methyl groups attached to the phenyl ring in toluene and m-xylene prevent the rings from packing together as in solid benzene.

Covalent Solids

Covalent solidsA solid that consists of two- or three-dimensional networks of atoms held together by covalent bonds. are formed by networks or chains of atoms or molecules held together by covalent bonds. A perfect single crystal of a covalent solid is therefore a single giant molecule. For example, the structure of diamond, shown in part (a) in Figure 12.19 "The Structures of Diamond and Graphite", consists of sp³ hybridized carbon atoms, each bonded to four other carbon atoms in a tetrahedral array to create a giant network. The carbon atoms form six-membered rings.

Figure 12.19 The Structures of Diamond and Graphite

(a) Diamond consists of sp³ hybridized carbon atoms, each bonded to four other carbon atoms. The tetrahedral array forms a giant network in which carbon atoms form six-membered rings. (b) These side (left) and top (right) views of the graphite structure show the layers of fused six-membered rings and the arrangement of atoms in alternate layers of graphite. The rings in alternate layers are staggered, such that every other carbon atom in one layer lies directly under (and above) the center of a six-membered ring in an adjacent layer.

The unit cell of diamond can be described as an fcc array of carbon atoms with four additional carbon atoms inserted into four of the tetrahedral holes. It thus has the zinc blende structure described in Section 12.3 "Structures of Simple Binary Compounds", except that in zinc blende the atoms that compose the fcc array are sulfur and the atoms in the tetrahedral holes are zinc. Elemental silicon has the same structure, as does silicon carbide (SiC), which has alternating C and Si atoms. The structure of crystalline quartz (SiO₂), shown in Section 12.1 "Crystalline and Amorphous Solids", can be viewed as being derived from the structure of silicon by inserting an oxygen atom between each pair of silicon atoms.

All compounds with the diamond and related structures are hard, high-melting-point solids that are not easily deformed. Instead, they tend to shatter when subjected to large stresses, and they usually do not conduct electricity very well. In fact, diamond (melting point = 3500°C at 63.5 atm) is one of the hardest substances known, and silicon carbide (melting point = 2986°C) is used commercially as an abrasive in sandpaper and grinding wheels. It is difficult to deform or melt these and related compounds because strong covalent (C–C or Si–Si) or polar covalent (Si–C or Si–O) bonds must be broken, which requires a large input of energy.

Other covalent solids have very different structures. For example, graphite, the other common allotrope of carbon, has the structure shown in part (b) in Figure 12.19 "The Structures of Diamond and Graphite". It contains planar networks of six-membered rings of sp² hybridized carbon atoms in which each carbon is bonded to three others. This leaves a single electron in an unhybridized 2p_z orbital that can be used to form C=C double bonds, resulting in a ring with alternating double and single bonds. Because of its resonance structures, the bonding in graphite is best viewed as consisting of a network of C–C single bonds with one-third of a π bond holding the carbons together, similar to the bonding in benzene.

To completely describe the bonding in graphite, we need a molecular orbital approach similar to the one used for benzene in Chapter 9 "Molecular Geometry and Covalent Bonding Models". In fact, the C–C distance in graphite (141.5 pm) is slightly longer than the distance in benzene (139.5 pm), consistent with a net carbon–carbon bond order of 1.33. In graphite, the two-dimensional planes of carbon atoms are stacked to form a three-dimensional solid; only London dispersion forces hold the layers together. As a result, graphite exhibits properties typical of both covalent and molecular solids. Due to strong covalent bonding within the layers, graphite has a very high melting point, as expected for a covalent solid (it actually sublimes at about 3915°C). It is also very soft; the layers can easily slide past one another because of the weak interlayer interactions. Consequently, graphite is used as a lubricant and as the “lead” in pencils; the friction between graphite and a piece of paper is sufficient to leave a thin layer of carbon on the paper. Graphite is unusual among covalent solids in that its electrical conductivity is very high parallel to the planes of carbon atoms because of delocalized C–C π bonding. Finally, graphite is black because it contains an immense number of alternating double bonds, which results in a very small energy difference between the individual molecular orbitals. Thus light of virtually all wavelengths is absorbed. Diamond, on the other hand, is colorless when pure because it has no delocalized electrons.

Table 12.5 "A Comparison of Intermolecular (Δ" compares the strengths of the intermolecular and intramolecular interactions for three covalent solids, showing the comparative weakness of the interlayer interactions.

Metallic Solids

Metals are characterized by their ability to reflect light, called lusterThe ability to reflect light. Metals, for instance, have a shiny surface that reflects light (metals are lustrous), whereas nonmetals do not., their high electrical and thermal conductivity, their high heat capacity, and their malleability and ductility. Every lattice point in a pure metallic element is occupied by an atom of the same metal. The packing efficiency in metallic crystals tends to be high, so the resulting metallic solidsA solid that consists of metal atoms held together by metallic bonds. are dense, with each atom having as many as 12 nearest neighbors.

Bonding in metallic solids is quite different from the bonding in the other kinds of solids we have discussed. Because all the atoms are the same, there can be no ionic bonding, yet metals always contain too few electrons or valence orbitals to form covalent bonds with each of their neighbors. Instead, the valence electrons are delocalized throughout the crystal, providing a strong cohesive force that holds the metal atoms together.

The strength of metallic bonds varies dramatically. For example, cesium melts at 28.4°C, and mercury is a liquid at room temperature, whereas tungsten melts at 3680°C. Metallic bonds tend to be weakest for elements that have nearly empty (as in Cs) or nearly full (Hg) valence subshells, and strongest for elements with approximately half-filled valence shells (as in W). As a result, the melting points of the metals increase to a maximum around group 6 and then decrease again from left to right across the d block. Other properties related to the strength of metallic bonds, such as enthalpies of fusion, boiling points, and hardness, have similar periodic trends.

A somewhat oversimplified way to describe the bonding in a metallic crystal is to depict the crystal as consisting of positively charged nuclei in an electron seaValence electrons that are delocalized throughout a metallic solid. (Figure 12.20 "The Electron-Sea Model of Bonding in Metals"). In this model, the valence electrons are not tightly bound to any one atom but are distributed uniformly throughout the structure. Very little energy is needed to remove electrons from a solid metal because they are not bound to a single nucleus. When an electrical potential is applied, the electrons can migrate through the solid toward the positive electrode, thus producing high electrical conductivity. The ease with which metals can be deformed under pressure is attributed to the ability of the metal ions to change positions within the electron sea without breaking any specific bonds. The transfer of energy through the solid by successive collisions between the metal ions also explains the high thermal conductivity of metals. This model does not, however, explain many of the other properties of metals, such as their metallic luster and the observed trends in bond strength as reflected in melting points or enthalpies of fusion. A more complete description of metallic bonding is presented in Section 12.6 "Bonding in Metals and Semiconductors".

Figure 12.20 The Electron-Sea Model of Bonding in Metals

Fixed, positively charged metal nuclei from group 1 (a) or group 2 (b) are surrounded by a “sea” of mobile valence electrons. Because a group 2 metal has twice the number of valence electrons as a group 1 metal, it should have a higher melting point.