36 • Chapter 2 / Atomic Structure and Interatomic Bonding

Figure 2.12 Schematic representation of covalent

bonding in a molecule of hydrogen (H2). H H H H
+

bond is directional—that is, it is between specific atoms and may exist only in the direc-
tion between one atom and another that participates in the electron sharing.
Many nonmetallic elemental molecules (e.g., Cl2, F2), as well as molecules con-
taining dissimilar atoms, such as CH4, H2O, HNO3, and HF, are covalently bonded.8
Furthermore, this type of bonding is found in elemental solids such as diamond (carbon),
silicon, and germanium and other solid compounds composed of elements that are
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located on the right side of the periodic table, such as gallium arsenide (GaAs), indium
Bonding antimonide (InSb), and silicon carbide (SiC).
What Is Covalent
Covalent bonds may be very strong, as in diamond, which is very hard and has a
Bonding?
very high melting temperature, >3550°C (6400°F), or they may be very weak, as with
bismuth, which melts at about 270°C (518°F). Bonding energies and melting tempera-
tures for a few covalently bonded materials are presented in Table 2.3. Inasmuch as
electrons participating in covalent bonds are tightly bound to the bonding atoms, most
covalently bonded materials are electrical insulators, or, in some cases, semiconductors.
Mechanical behaviors of these materials vary widely: some are relatively strong, others
are weak; some fail in a brittle manner, whereas others experience significant amounts
of deformation before failure. It is difficult to predict the mechanical properties of
covalently bonded materials on the basis of their bonding characteristics.

Bond Hybridization in Carbon

Often associated with the covalent bonding of carbon (as well other nonmetallic sub-
stances) is the phenomenon of hybridization—the mixing (or combining) of two or more
atomic orbitals with the result that more orbital overlap during bonding results. For
example, consider the electron configuration of carbon: 1s22s22p2. Under some circum-
stances, one of the 2s orbitals is promoted to the empty 2p orbital (Figure 2.13a), which
gives rise to a 1s22s12p3 configuration (Figure 2.13b). Furthermore, the 2s and 2p orbitals
can mix to produce four sp3 orbitals that are equivalent to one another, have parallel
spins, and are capable of covalently bonding with other atoms. This orbital mixing is
termed hybridization, which leads to the electron configuration shown in Figure 2.13c;
here, each sp3 orbital contains one electron, and, therefore, is half-filled.
Bonding hybrid orbitals are directional in nature—that is, each extends to and over-
laps the orbital of an adjacent bonding atom. Furthermore, for carbon, each of its four
sp3 hybrid orbitals is directed symmetrically from a carbon atom to the vertex of a
tetrahedron—a configuration represented schematically in Figure 2.14; the angle between
each set of adjacent bonds is 109.5°.9 The bonding of sp3 hybrid orbitals to the 1s orbitals
of four hydrogen atoms, as in a molecule of methane (CH4), is presented in Figure 2.15.
For diamond, its carbon atoms are bonded to one another with sp3 covalent
hybrids—each atom is bonded to four other carbon atoms. The crystal structure for
diamond is shown in Figure 12.16. Diamond’s carbon–carbon bonds are extremely
strong, which accounts for its high melting temperature and ultrahigh hardness (it is
the hardest of all materials). Many polymeric materials are composed of long chains of
carbon atoms that are also bonded together using sp3 tetrahedral bonds; these chains
form a zigzag structure (Figure 14.1b) because of this 109.5° interbonding angle.

8
For these substances, the intramolecular bonds (bonds between atoms in a molecule) are covalent. As noted in the
next section, other types of bonds can operate between molecules, which are termed intermolecular.
9
Bonding of this type (to four other atoms) is sometimes termed tetrahedral bonding.
 2.6 Primary Interatomic Bonds • 37

2p
2s
Energy
(a)
1s

promotion
of electron

2p
2s sp3
Energy
(b) H
1s
1s
sp3
109.5°
3
sp3 sp
sp3
C
hybridization sp3
sp3 H C
1s
H
2sp3 1s
3
sp3
H sp
Energy
(c) 1s
1s
Figure 2.14 Schematic Region of overlap
diagram showing four sp3
hybrid orbitals that point to Figure 2.15 Schematic
Figure 2.13 Schematic diagram the corners of a tetrahedron; diagram that shows bonding of
that shows the formation of sp3 hybrid carbon sp3 hybrid orbitals to the
the angle between orbitals
orbitals in carbon. (a) Promotion of
is 109.5°. 1s orbitals of four hydrogen atoms
a 2s electron to a 2p state; (b) this (From J. E. Brady and F. in a molecule of methane (CH4).
promoted electron in a 2p state; Senese, Chemistry: Matter (From J. E. Brady and F. Senese,
(c) four 2sp3 orbitals that form by and Its Changes, 4th edition, Chemistry: Matter and Its Changes,
mixing the single 2s orbital with the 2004. Reprinted with permission 4th edition, 2004. Reprinted with
three 2p orbitals. of John Wiley & Sons, Inc.) permission of John Wiley & Sons, Inc.)

Other types of hybrid bonds are possible for carbon, as well as other substances.
One of these is sp2, in which an s orbital and two p orbitals are hybridized. To achieve
this configuration, one 2s orbital mixes with two of the three 2p orbitals—the third p
orbital remains unhybridized; this is shown in Figure 2.16. Here, 2pz denotes the unhy-
bridized p orbital.10 Three sp2 hybrids belong to each carbon atom, which lie in the same
plane such that the angle between adjacent orbitals is 120° (Figure 2.17); lines drawn
from one orbital to another form a triangle. Furthermore, the unhybridized 2pz orbital
is oriented perpendicular to the plane containing the sp2 hybrids.
These sp2 bonds are found in graphite, another form of carbon, which has a
structure and properties distinctly different from those of diamond (as discussed in
Section 12.4). Graphite is composed of parallel layers of interconnecting hexagons.
Hexagons form from planar sp2 triangles that bond to one another in the manner
presented in Figure 2.18—a carbon atom is located at each vertex. In-plane sp2 bonds
are strong; by way of contrast, weak interplanar bonding results from van der Waals
forces that involve electrons originating from the unhybridized 2pz orbitals. The struc-
ture of graphite is shown in Figure 12.17.

10
This 2pz orbital has the shape and orientation of the pz shown in Figure 2.5c. In addition, the two p orbitals found
in the sp2 hybrid correspond to the px and py orbitals of this same figure. Furthermore, px, py, and pz are the three
orbitals of the sp3 hybrid.