278 CHAPTER 8  Covalent Compounds: Bonding Theories and Molecular Structure

TABLE 8.2 Hybrid Orbitals and Their Geometry

Number of Charge Arrangement of Charge

Clouds Clouds Hybridization
2 Linear sp
3 Trigonal planar sp2
4 Tetrahedral sp3

Atoms with Five and Six Charge Clouds

Main-group atoms with five or six charge clouds, such as the phosphorus in PCl5 and the
sulfur in SF6, were at one time thought to undergo hybridization by combination of five and
six atomic orbitals, respectively. Because a given shell has a total of only four s and p orbitals,
however, the need to use five or six orbitals implies that d orbitals are involved. As we’ll see
in Section 20.11, hybridization involving d orbitals is indeed involved for many compounds
of transition metals. Recent quantum mechanical calculations indicate, however, that main-
group compounds do not use d orbitals in hybridization but instead use a more complex
bonding pattern that is not easily explained by valence bond theory.
A summary of the three common kinds of hybridization for main-group elements and
the geometry that each corresponds to is given in TABLE 8.2 .

8.5 ▶ POLAR COVALENT BONDS AND DIPOLE MOMENTS

REMEMBER…
Polar covalent bonds are those in which
the bonding electrons are shared unequally
between two atoms but are not completely
transferred. Thus, they are intermediate
between nonpolar covalent bonds and ionic
bonds. (Section 7.3)
REMEMBER…
Electronegativity is the ability of an atom
in a molecule to attract the shared electrons
in a covalent bond. Metals on the left of the
periodic table are the least electronegative,
while halogens and other reactive nonmetals
in the upper right of the table are the most
electronegative. (Section 7.3)
REMEMBER…
Molecular polarity is an important characteristic that influences both chemical and physical
properties of molecules. To understand the notion of molecular polarity, it’s first necessary to
develop the ideas of bond dipoles and dipole moments. We saw in Section 7.3 that polar covalent
bonds form between atoms of different electronegativity. In chloromethane 1CH3Cl2, chlorine
is more electronegative than carbon so the chlorine atom attracts the electrons in the C ¬ Cl
bond more strongly than carbon does. The C ¬ Cl bond is therefore polarized so that the chlo-
rine atom is slightly electron-rich 1d -2 and the carbon atom is slightly electron-poor 1d +2.
Because the polar C ¬ Cl bond in chloromethane has a positive end and a negative end—we
describe it as being a bond dipole, and we often represent the dipole using an arrow with a cross
at one end 1\2 to indicate the direction of electron displacement. The point of the arrow repre-
sents the negative end of the dipole 1d -2, and the crossed end (which looks like a plus sign) rep-
resents the positive end 1d +2. The C ¬ H bond in chloromethane also has a small bond dipole
because carbon is slightly more electronegative than H. In theory, a bond dipole can be drawn
with the arrow pointing towards the partially negative carbon atom, but in practice the C ¬ H
bonds are considered to be nearly nonpolar. Due to the small difference in electronegativity be-
tween carbon and hydrogen, bond dipoles are not typically drawn for C ¬ H bonds.
Just as individual bonds in molecules are often polar, molecules as a whole are also of-
ten polar because of the net sum of individual bond polarities and lone-pair contributions.
The overall molecular polarity of CH3Cl is clearly visible in an electrostatic potential map,
which shows the electron-rich chlorine atom as red and the electron-poor remainder of the
molecule as blue-green. The resultant molecular dipole can be looked at in the following way:
Assume that there is a center of mass of all positive charges (nuclei) and all negative charges
(electrons) in a molecule. If these two centers don’t coincide, the molecule has net polarity.

An electrostatic potential map uses color to

portray the calculated electron distribution in
a molecule. Electron-rich regions are red, and δ−
electron-poor regions are blue. (Section 7.3) Cl
+
Cδ or
H H H H
H H
Chloromethane, CH3Cl
Chlorine is at the negative
end of the bond dipole.
Cl
Carbon is at the positive
C end of the bond dipole.
Net
 8.5  Polar Covalent Bonds and Dipole Moments 279

The measure of net molecular polarity is a quantity called the dipole moment (μ), (Greek
TABLE 8.3 Dipole Moments of
mu), which is defined as the magnitude of the charge Q at either end of the molecular dipole Some Common Compounds
times the distance r between the charges: m = Q * r. Dipole moments are expressed in de-
byes (D), where 1 D = 3.336 * 10-30 coulomb meters 1C # m2 in SI units. To calibrate your Compound Dipole Moment (D)
thinking, the charge on an electron is 1.60 * 10-19 C. Thus, if a proton and an electron were NaCl a
9.0
separated by 100 pm (a bit less than the length of a typical covalent bond), then the dipole
moment would be 1.60 * 10-29 C # m, or 4.80 D:
CH3Cl 1.90
H2O 1.85
m = Q * r NH3 1.47
-19 -12 1D HCl 1.11
m = 11.60 * 10 C21100 * 10 m2a b = 4.80 D
3.336 * 10-30C # m CO2 0
It’s relatively easy to measure dipole moments experimentally, and values for some com- CCl4 0
mon substances are given in TABLE 8.3 . Once the dipole moment is known, it’s then pos- a
Measured in the gas phase.
sible to get an idea of the amount of charge separation in a molecule. In chloromethane, for
example, the experimentally measured dipole moment is m = 1.90 D. If we assume that
the contributions of the nonpolar C ¬ H bonds are small, then most of the chloromethane
dipole moment is due to the C ¬ Cl bond. Since the C ¬ Cl bond distance is 179 pm, we can
calculate that the dipole moment of chloromethane would be 1.79 * 4.80 D = 8.59 D if the
C ¬ Cl bond were ionic—that is, if a full negative charge on chlorine were separated from a
full positive charge on carbon by a distance of 179 pm. But because the measured dipole mo-
ment of chloromethane is only 1.90 D, we can conclude that the C ¬ Cl bond is only about
11.90>8.5921100%2 = 22% ionic. Thus, the chlorine atom in chloromethane has an excess of
about 0.2 electron, and the carbon atom has a deficiency of about 0.2 electron.
Perhaps it’s not surprising that by far the largest dipole moment listed in Table 8.3 be-
longs to the ionic compound NaCl, which exists in the gas phase as a pair of Na+ and Cl- ions
held together by a strong ionic bond. The molecular compounds water and ammonia also
have substantial dipole moments because both oxygen and nitrogen are electronegative rela-
tive to hydrogen and because both O and N have lone pairs of electrons that make substantial
contributions to net molecular polarity:

Net

N O
H H H
H Net H

Ammonia (μ = 1.47 D) Water (μ = 1.85 D)

In contrast with water and ammonia, carbon dioxide and tetrachloromethane 1CCl42 have
zero dipole moments. Molecules of both substances contain individual polar covalent bonds,
but because of the symmetry of their structures, the individual bond polarities exactly cancel.

Cl
C
Cl Cl
Cl
O C O
Carbon dioxide (μ = 0) Tetrachloromethane (μ = 0)
280 CHAPTER 8  Covalent Compounds: Bonding Theories and Molecular Structure

▶ FIGURE 8.8
Strategy for predicting molecular polarity.
Draw electron-dot
structure of molecule.
Use VSEPR Model
(Section 8.1)

Predict three-dimensional
shape of molecule.
Use electronegativity
values for elements
(Figure 7.4)
Draw bond dipoles.

Evaluate symmetry of bond dipoles

and lone pairs of electrons.

Polar molecule
Nonpolar molecule
Bond dipoles and lone pairs of
Bond dipoles are arranged
electrons are arranged asymmetrically
symmetrically and cancel.
and result in a net dipole moment.

FIGURE 8.8 outlines the strategy for predicting molecular polarity. The first step is to
draw an electron-dot structure and use the VSEPR model (Section 8.1) to determine three-
dimensional molecular shape. Next draw bond dipoles using electronegativity values (Figure
7.4) and examine symmetry in bond dipoles and lone pairs to determine if a molecule has a
dipole moment.
Worked Examples 8.6 and 8.7 illustrate the process for predicting molecular polarity and
calculating the percent ionic character given the magnitude of a dipole moment.

● Conceptual WORKED EXAMPLE 8.6

Predicting the Presence of a Dipole Moment
Would you expect vinyl chloride 1H2C “ CHCl), the starting material used for preparation of
poly(vinyl chloride) polymer, to have a dipole moment? If so, indicate the direction.

STRATEGY AND SOLUTION The molecule as a whole is planar because the unhybridized carbon
Follow the procedure outlined in Figure 8.8 for determining 2p orbitals in the pi part of the C “ C double bond overlap in a
molecular polarity. sideways manner:
The electron-dot structure for vinyl chloride is:
H H
H H H H
Vinyl chloride C C C C
H Cl
C C
H Cl
H Cl Top view Side view

The VSEPR model described in Section 8.1 is then used to predict Then, assign polarities to the individual bonds according to the
the molecular shape of vinyl chloride. Each carbon has trigonal pla- differences in electronegativity of the bonded atoms, and make a
nar geometry because both carbon atoms have three charge clouds. reasonable guess about the overall polarity that would result by
 8.5  Polar Covalent Bonds and Dipole Moments 281

evaluating symmetry in bond dipoles and summing the individual (a) (b)
contributions. Only the C ¬ Cl bond has a substantial polarity, giv-
ing the molecule a net polarity in the direction of the chlorine atom:

H H
C C
H Cl
(c) (d)

▶ Conceptual PRACTICE 8.11 Tell which of the following com-

pounds is likely to have a dipole moment, and show the direction of
each.
(a) SF6 (b) H2C “ CF2
(c) SO3 (d) BrF3

▶ Conceptual APPLY 8.12 Match the following electrostatic

potential maps with their corresponding molecule: CH3F, CHF3,
CF4, CH2F2.
●

● WORKED EXAMPLE 8.7

Calculating Percent Ionic Character from a Dipole Moment
The dipole moment of HCl is 1.11 D, and the distance between atoms is 127 pm. What is the
percent ionic character of the HCl bond?
STRATEGY
If HCl were 100% ionic, a negative charge 1Cl- 2 would be separated from a positive charge
1H+ 2 by 127 pm. Calculate the expected dipole moment, and compare that calculated value
to the actual value.
SOLUTION
The calculated dipole moment is
m = Q * r
1D
m = 11.60 * 10-19C21127 * 10-12m2 a b = 6.09 D
3.336 * 10-30C # m
The observed dipo le moment of 1.11 D for HCl implies that the H ¬ Cl bond is only about
18% ionic:

1.11 D
* 100% = 18.2%
6.09 D

▶ PRACTICE 8.13 The dipole moment of HF is m = 1.83 D, and the bond length is 92 pm.
Calculate the percent ionic character of the H ¬ F bond. Is HF more ionic or less ionic than
HCl (Worked Example 8.7)?

▶ APPLY 8.14 Without performing any calculations, predict which bond has a greater per-
cent ionic character, H ¬ Br or H ¬ I. Check your prediction using the following data: the
dipole moment of HBr is m = 0.82 D, and the bond length is 142 pm; the dipole moment of
HI is m = 0.38 D, and the bond length is 161 pm.

●
282 CHAPTER 8  Covalent Compounds: Bonding Theories and Molecular Structure

8.6 ▶ INTERMOLECULAR FORCES

Now that we know a bit about molecular polarities, let’s see how they give rise to some of
the forces that occur between molecules, called intermolecular forces. These forces are
different than covalent bonds between atoms within a molecule. For example, in H2O there
are two covalent bonds between hydrogen and oxygen, but there are also attractive forces
between two H2O molecules that we refer to as intermolecular forces. (Strictly speaking, the
term intermolecular refers only to molecular substances, but we’ll use it generally to refer to
interactions among all kinds of particles, including molecules, ions, and atoms.)

Covalent bond
H
O
O H H
Intermolecular
H force

Intermolecular forces influence many important macroscopic properties of matter such as

REMEMBER…
Ionic bonds generally form between the
cation of a metal and the anion of a reactive
nonmetal. (Section 6.7)
solubility, melting point, and boiling point. They also play a key role in stabilizing the shapes
and interactions of biomolecules, as we’ll see at the end of this section. To understand how the
strength of substance’s intermolecular forces influences its melting and boiling point we must
first visualize the difference between a gas, liquid, and solid at the molecular level. FIGURE 8.9
shows that the particles in a gas are free to move around at random and fill the volume of a
container because the attractive forces (intermolecular forces) between particles are weak.
Liquids and solids are distinguished from gases by the presence of substantial attractive forces
between particles. In liquids, these attractive forces are strong enough to hold the particles in
close contact while still allowing them to move freely past one another. In solids, the forces
are so strong that they hold the particles rigidly in place and prevent their movement.
Temperature influences the phase of matter because at higher temperatures particles
have greater kinetic energy and can overcome the intermolecular forces holding them to-
gether. We are familiar with a sample of H2O that exists either as solid ice, liquid water, or
gaseous vapor, depending on its temperature. Nitrogen 1N22 offers another example; nitro-
gen is a gas at higher temperatures but becomes a liquid at low temperature (FIGURE 8.10).
Intermolecular forces as a whole are usually called van der Waals forces after the Dutch
scientist Johannes van der Waals (1837–1923). These forces are of several different types, in-
cluding dipole–dipole forces, London dispersion forces, and hydrogen bonds. In addition, ion–
dipole forces exist between ions and molecules. All these intermolecular forces are electrostatic
in origin and result from the mutual attraction of unlike charges or the mutual repulsion of
like charges. If the particles are ions, then full charges are present and the ion–ion attractions
are so strong (energies on the order of 500–1000 kJ/mol) that they give rise to what we call
ionic bonds. If the particles are neutral, then only partial charges are present, but even so, the
attractive forces can be substantial.

▶ FIGURE 8.9
A molecular comparison of gases,
liquids, and solids.

Figure It Out
Which phase of matter has the strongest
intermolecular forces?
Answer: Solid

In gases, the particles In liquids, the particles In solids, the particles

feel little attraction are held close together are held in an ordered
for one another and by attractive forces arrangement.
are free to move but are free to move
about randomly. around one another.
 8.6  Intermolecular Forces 283

N2 molecules are weakly

attracted to one another
at low temperature by
intermolecular forces,
causing nitrogen to
become liquid.

At higher temperatures,
intermolecular forces are
no longer able to keep
molecules close together,
so nitrogen becomes
a gas.

▲ FIGURE 8.10
Intermolecular forces.

Ion–Dipole Forces
We said in the previous section that a molecule has a net polarity and an overall dipole moment
if the sum of its individual bond dipoles is nonzero. One side of the molecule has a net excess
of electrons and a partial negative charge 1d -), while the other side has a net deficiency of elec-
trons and a partial positive charge 1d +). An ion–dipole force is the result of electrical interac-
tions between an ion and the partial charges on a polar molecule (FIGURE 8.11).
The favored orientation of a polar molecule in the presence of ions is one where the
positive end of the molecular dipole is near an anion and the negative end of the dipole is LOOKING AHEAD…
near a cation. The magnitude of the interaction energy E depends on the charge on the ion
In Section 12.2, we’ll look at the energy
z, the strength of the dipole as measured by its dipole moment m, and the inverse square
changes accompanying the formation
of the distance r from the ion to the dipole: E∝zm>r2. Ion–dipole forces are highly variable of solutions and at how those energy
in strength and are particularly important in aqueous solutions of ionic substances such as changes are affected by different kinds of
NaCl, in which polar water molecules surround the ions. We’ll explore the formation of intermolecular forces.
solutions in more detail in Chapter 12.

◀ FIGURE 8.11
Ion–dipole forces.
δ− δ− δ+ δ+

δ+ δ+ δ− δ−

− +

δ+ δ+ δ− δ−
δ− δ− δ+ δ+

Polar molecules orient toward ions so … the negative end of the dipole
that the positive end of the dipole is is near a cation.
near an anion and …
284 CHAPTER 8  Covalent Compounds: Bonding Theories and Molecular Structure

Dipole–Dipole Forces
Neutral but polar molecules experience dipole–dipole forces as the result of electrical
interactions among dipoles on neighboring molecules. The forces can be either attractive or
repulsive, depending on the orientation of the molecules (FIGURE 8.12), and the net force in
a large collection of molecules is a summation of many individual interactions of both types.
The forces are weaker than ion–dipole forces, with energies on the order of 3–4 kJ/mol.
The strength of a given dipole–dipole interaction depends on the sizes of the dipole mo-
ments involved. The more polar the substance, the greater the strength of its dipole–dipole
interactions. Butane, for instance, is a nonpolar molecule with a molecular weight of 58 and a
boiling point of - 0.5 °C, while acetone has the same molecular weight yet boils 57 °C higher
because it is polar.

H H H H O δ−
H C C H C δ+ H
C C H C C
H H H H H H H H
Butane (C4H10) Acetone (C 3H6O)
Mol. wt. = 58 Mol. wt. = 58
bp = −0.5 °C bp = 56.1 °C

TABLE 8.4 lists several substances with similar molecular weights but different dipole
moments and indicates that there is a rough correlation between dipole moment and boiling
point. The larger the dipole moment, the stronger the intermolecular forces and the greater
the amount of heat that must be added to overcome those forces. Thus, substances with
higher dipole moments generally have higher boiling points.

▶ FIGURE 8.12
Dipole–dipole forces.
δ− δ+

δ+ δ− δ+ δ− δ+ δ−
δ+
δ+ δ− δ+ δ− δ+ δ− δ+ δ−
δ−
δ+ δ− δ+ δ−
δ+

δ− δ− δ+

Polar molecules attract one another when they … they repel one another when they
orient with unlike charges close together, but … orient with like charges together.

TABLE 8.4 Comparison of Molecular Weights, Dipole Moments, and Boiling Points

Substance Mol. Wt. Dipole Moment (D) bp (K)

CH3CH2CH3 44.10 0.08 231
CH3OCH3 46.07 1.30 248
CH3CN 41.05 3.93 355
 8.6  Intermolecular Forces 285

London Dispersion Forces

The causes of intermolecular forces among charged and polar particles are relatively easy to
understand, but it’s less obvious how attractive forces arise among nonpolar molecules or
among the individual atoms of a noble gas. Benzene 1C6H6), for instance, has zero dipole
moment and therefore experiences no dipole–dipole forces. Nevertheless, there must be some
intermolecular forces present among benzene molecules because the substance is a liquid
rather than a gas at room temperature, with a melting point of 5.5 °C and a boiling point
of 80.1 °C.

H C H
Benzene
C C
μ=0
C C mp = 5.5 °C
C bp = 80.1 °C
H H

All atoms and molecules, regardless of structure, experience London dispersion forces,
which result from the motion of electrons. Take even a simple nonpolar molecule like Br2,
for instance. Averaged over time, the distribution of electrons throughout the molecule is
symmetrical, but at any given instant there may be more electrons at one end of the molecule
than at the other, giving the molecule a short-lived dipole moment. This instantaneous dipole
on one molecule can affect the electron distributions in neighboring molecules and induce
temporary dipoles in those neighbors (FIGURE 8.13). As a result, weak attractive forces de-
velop and Br2 is a liquid at room temperature rather than a gas.
Dispersion forces are generally small, with energies in the range 1 - 10 kJ>mol, and
their exact magnitude depends on the ease with which a molecule’s electron cloud can be
distorted by a nearby electric field, a property referred to as polarizability. A smaller mol-
ecule or lighter atom is less polarizable and has smaller dispersion forces because it has only
a few, tightly held electrons. A larger molecule or heavier atom, however, is more polarizable
and has larger dispersion forces because it has many electrons, some of which are less tightly
held and are farther from the nucleus. Among the halogens, for instance, the F2 molecule is
small and less polarizable, while I2 is larger and more polarizable. As a result, F2 has smaller
dispersion forces and is a gas at room temperature, while I2 has larger dispersion forces and
is a solid (TABLE 8.5).
Shape is also important in determining the magnitude of the dispersion forces affecting
a molecule. More spread-out shapes, which maximize molecular surface area, allow greater
contact between molecules and give rise to higher dispersion forces than do more compact
shapes, which minimize molecular contact. Pentane, for example, boils at 309.2 K, whereas
2,2-dimethylpropane boils at 282.6 K. Both substances have the same molecular formula,

◀ FIGURE 8.13
δ− δ+ δ− δ+ London dispersion forces.

Averaged over time, the
electron distribution in a Br2
molecule is symmetrical.
At any given instant, the electron distribution
in a molecule may be unsymmetrical,
resulting in a temporary dipole and inducing
a complementary attractive dipole in
neighboring molecules.
286 CHAPTER 8  Covalent Compounds: Bonding Theories and Molecular Structure

TABLE 8.5 Melting Points and Boiling Points of the Halogens

Halogen mp (K) bp (K)

F2 53.5 85.0
Cl2 171.6 239.1
Br2 265.9 331.9
I2 386.8 457.5

▶ FIGURE 8.14
The effect of molecular shape on London H
dispersion forces.
H C H
H H

H C C C H
H H H H H H H
H C C C C C H H C H

H H H H H H

Pentane (bp = 309.2 K) 2,2-Dimethylpropane (bp = 282.6 K)

Longer, less compact molecules More compact molecules

like pentane feel stronger dispersion like 2,2-dimethylpropane feel
forces and consequently have weaker dispersion forces and
higher boiling points. have lower boiling points.

C5H12, but pentane is longer and somewhat spread out, whereas 2,2-dimethylpropane is more
spherical and compact (FIGURE 8.14).

LOOKING AHEAD…
In Section 23.11, we’ll examine the
molecular composition of DNA and the
role of hydrogen bonding in structure and
replication.
Hydrogen Bonds
In many ways, hydrogen bonds are responsible for life on Earth. They cause water to be a
liquid rather than a gas at ordinary temperatures, and they are the primary intermolecular
force that holds huge biomolecules in the shapes needed to play their essential roles in bio-
chemistry. Deoxyribonucleic acid (DNA), a molecule that stores our genetic code, contains
two enormously long molecular strands that are coiled around each other and held together
by hydrogen bonds.

Hydrogen bond
between chains

A short segment
of DNA