CHAPTER 6

Chemical
Bonding
BIG IDEA
Atoms form chemical bonds
by sharing or transferring
electrons.

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SECTION 1 ONLINE LABS

Introduction to Chemical  Conductivity as an Indicator of

Bonding Bond Type

 Chemical Bonds
SECTION 2  Types of Bonding in Solids
Covalent Bonding and GO ONLINE

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SECTION 3
Ionic Bonding and Ionic Chemical Bonding
Compounds

SECTION 4
Metallic Bonding

SECTION 5
Molecular Geometry
 Section 1

Introduction to Main Idea

Atoms form compounds by

Chemical ­Bonding
gaining, losing, or sharing
electrons.

Key Terms
chemical bond nonpolar-covalent bond
ionic bonding polar
covalent bonding polar-covalent bond

Atoms seldom exist as independent particles in nature. The oxygen you breathe,
the water you drink, and nearly all other substances consist of combinations of
atoms that are held together by chemical bonds. A chemical bond is a mutual
electrical attraction between the nuclei and valence electrons of different atoms
that binds the atoms together.
Why are most atoms chemically bonded to each other? As independent
particles, most atoms are at relatively high potential energy. Nature, however, favors
arrangements in which potential energy is minimized. Most atoms are less stable
existing by themselves than when they are combined. By bonding with each other,
atoms decrease in potential energy, creating more stable arrangements of matter.

Main Idea
Atoms form compounds by gaining, losing,
or sharing electrons.
When atoms bond, their valence electrons are redistributed in ways
that make the atoms more stable. The way in which the electrons are
redistributed determines the type of bonding. As discussed in the chapter
“The Periodic Law,” main­-­group metals tend to lose electrons to form
positive ions, or cations, and nonmetals tend to gain electrons to form
negative ions, or anions. Chemical bonding that results from the electrical
attraction between cations and anions is called ionic bonding. In purely
ionic bonding, atoms completely give up electrons to other atoms, as
illustrated in Figure 1.1 on the next page. In contrast to atoms joined by
ionic bonding, atoms joined by covalent bonding share electrons.
Covalent bonding results from the sharing of electron pairs between two
atoms (see Figure 1.1). In a purely covalent bond, the shared electrons are
“owned” equally by the two bonded ­atoms.

Ionic or Covalent? go online

Bonding between atoms of different elements is rarely purely ionic or
purely covalent. It usually falls somewhere between these two extremes, Chemistry
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depending on how strongly the atoms of each element attract electrons.
Recall that electronegativity is a measure of an atom’s ability to attract Types of Bonds
electrons. The degree to which bonding between atoms of two elements
is ionic or covalent can be estimated by calculating the difference in
the elements’ electronegativities (see Figure 1.2 on the next page).

Chemical Bonding 171

 Figure 1.1
IONIC BONDING Anion B
Ionic Bonding and Covalent Cation A
Bonding In ionic bonding, atoms Many atoms
Electrons transferred –
transfer electrons. The resulting positive from atoms A to + +
– – –
and negative ions combine due to mutual atoms B
+ + +
electrical attraction. In covalent bonding,
+ – +
atoms share electron p­ airs to form – –
Atoms A Atoms B
independent molecules. +

COVALENT BONDING

+
Electron pair shared
Atom C Atom D between atom C and
Atom C Atom D
atom D
Two atoms

For example, the electronegativity difference between fluorine, F, and

cesium, Cs, is 4.0 - 0.7 = 3.3. So, according to Figure 1.2, cesium­-­fluorine
bonding is ionic. Fluorine atoms, which are highly electronegative, gain
valence electrons, causing the atoms to become anions. Cesium atoms,
Figure 1.2 which are less electronegative, lose valence electrons, causing the atoms
to become cations.
Bonding and
Electronegativity Differences Bonding between atoms with an electronegativity difference of 1.7 or
in electronegativities reflect the less has an ionic character of 50% or less. These compounds are typically
character of bonding between classified as covalent. Bonding between two atoms of the same element is
elements. The electronegativity of completely covalent. Hydrogen, for example, exists in nature not as
the less­-electronegative element is isolated atoms but as pairs of atoms held together by covalent bonds. The
subtracted from that of the more­-­ hydrogen-hydrogen bond is a nonpolar­-­covalent bond, a covalent bond in
electronegative element. The greater which the bonding electrons are shared equally by the bonded atoms, resulting
the electronegativity difference, the in a balanced distribution of electrical charge. Bonds having 0% to 5% ionic
more ionic ­is the bonding. character, corresponding to electronegativity differences of roughly 0 to
0.3, are generally considered nonpolar­-­covalent bonds. In bonds with
3.3 100% significantly different electronegativities, the electrons are more strongly
attracted by the more-electronegative atom. Such bonds are polar, meaning
that they have an uneven distribution of charge. Covalent bonds having 5% to
Difference in electronegativities

Ionic 50% ionic character, corresponding to electronegativity differences of 0.3

Percentage ionic character

to 1.7, are classified as polar. A polar­-­covalent bond is a covalent bond in

which the bonded atoms have an unequal attraction for the shared e
­ lectrons.
1.7 50% Nonpolar- and polar­-c­ ovalent bonds are compared in Figure 1.3, which
illustrates the electron density distribution in hydrogen-hydrogen and
hydrogen-chlorine bonds. The electronegativity difference between
Polar-covalent chlorine and hydrogen is 3.0 - 2.1 = 0.9, indicating a polar­-c­ ovalent
bond. The electrons in this bond are closer to the more-electronegative
chlorine atom than to the hydrogen atom. Thus, the chlorine end of the
0.3 5%
bond has a partial negative charge, indicated by the symbol δ-. The
Nonpolar-covalent
0 0% hydrogen end of the bond then has an equal partial positive charge, δ+.

172 Chapter 6
 Figure 1.3

Electron Density Comparison of the electron density in Chlorine

Hydrogen nuclei Hydrogen nucleus
(a) a nonpolar hydrogen-hydrogen bond and (b) a polar hydrogen- nucleus
chlorine bond. Because chlorine is more electronegative than
hydrogen, the electron density in the hydrogen-chlorine bond is
greater around the chlorine ­atom.
δ+ δ-
critical thinking
Explain Why is the density of the electron cloud greater around
the chlorine atom in the polar hydrogen-chlorine bond?
(a) Nonpolar-covalent bond (b) Polar-covalent bond

Classifying Bonds
Sample Problem A Use electronegativity differences and Figure 1.2 to classify bonding
between nitrogen, N, and the following elements: carbon, C; sodium, Na; and oxygen, O.
In each pair, which atom will be more ­negative?

Solve From the Periodic Table of Electronegativities in the chapter “The Periodic
Law,” we know that the electronegativity of nitrogen is 3.0. The electronegativi-
ties of carbon, sodium, and oxygen are 2.5, 0.9, and 3.5, respectively. In each
pair, the atom with the larger e­ lectronegativity will be the more-negative atom.
Bonding between Electronegativity More­-­negative
sulfur and difference Bond type atom
carbon 3.0 - 2.5 = 0.5 polar-covalent nitrogen
sodium 3.0 - 0.9 = ­2.1 ionic nitrogen
oxygen 3.5 - 3.0 = 0.5 polar-­covalent oxygen

Answers in Appendix E

Use electronegativity differences and Figure 1.2 to classify bonding between oxygen, O, and the following
elements: potassium, K; phosphorus, P; and fluorine, F. Indicate the more­-­negative atom in each ­pair.

Section 1 Formative ASSESSMENT

Reviewing Main Ideas Critical Thinking
1. What is the main distinction between ionic and 5. INTERPRETING CONCEPTS Compare the
covalent ­bonding? following two pairs of atoms: Cu and F; I and F.
2. How is electronegativity used in determining a. Which pair would have a bond with a greater
the ionic or covalent character of the bonding percent ionic character?
between two elements? b. In which pair would F have the greater
negative charge?
3. What type of bonding would be expected be-
tween the following ­atoms? 6. INFERRING RELATIONSHIPS The isolated
a. Li and ­F K atom is larger than the isolated Br atom.
b. Cu and ­S a. What type of bond is expected between K
c. I and ­F and Br?
b. Which ion in the compound KBr is larger?
4. List the three pairs of atoms referred to in the
previous question in order of increasing ionic
character of the bonding between ­them.

Chemical Bonding 173

 SECTION 2
Main Ideas
Covalent Bonding
and Molecular
Covalent bonds form from
shared electrons.

Bond lengths and energy vary

from molecule to molecule.

Atoms tend to form bonds to

follow the octet rule.
Compounds
Key Terms
Dots placed around an molecule Lewis structure
element’s symbol can represent molecular compound structural formula
valence electrons. chemical formula single bond
molecular formula multiple bond
Electron-dot notations can bond energy resonance
represent compounds. electron-dot notation

Some atoms can share multiple

Many chemical compounds, including most of the chemicals that are in living things
pairs of electrons.
and are produced by living things, are composed of molecules. A molecule is a
Resonance structures show neutral group of atoms that are held together by covalent bonds. A single molecule
of a chemical compound is an individual unit capable of existing on its own. It may
hybrid bonds.
consist of two or more atoms of the same element, as in oxygen, or two or more
Some compounds are networks different atoms, as in water or sugar (see Figure 2.1). A chemical compound whose
simplest units are molecules is called a molecular compound.
of bonded atoms.
The composition of a compound is given by its chemical formula. A
chemical formula indicates the relative numbers of atoms of each kind in a
chemical compound by using atomic symbols and numerical subscripts. The
chemical formula of a molecular compound is referred to as a molecular formula.
A molecular formula shows the types and numbers of atoms combined in a
single molecule of a molecular compound. The molecular formula for water, for
example, is H2O. A single water molecule consists of one oxygen atom joined by
separate covalent bonds to two hydrogen atoms. A molecule of oxygen, O2, is an
example of a diatomic molecule. A diatomic molecule contains only two atoms.

FIGURE 2.1

Covalently Bonded Molecules The models for (a) water,

(b) oxygen, and (c) sucrose, or table sugar, represent a few examples
of the many molecular compounds in and around us. Atoms within
molecules may form one or more covalent bonds.

(a) Water molecule,

H2O

(b) Oxygen molecule,

O2

(c) Sucrose molecule,

C12H22O11

174 Chapter 6
FIGURE 2.2

Potential Energy Changes during the

0
Formation of a Hydrogen-Hydrogen +

Potential energy (kJ/mol)

Bond (a) The separated hydrogen atoms do not (d) (a)
affect each other. (b) Potential energy decreases as (b)
the atoms are drawn together by attractive forces.
75 pm
(c) Potential energy is at a minimum when attractive
forces are balanced by repulsive forces. (d) Potential
-436 (c)
energy increases when repulsion between like charges
outweighs attraction between opposite charges.
75
Distance between hydrogen nuclei (pm)

MAIN IDEA
Covalent bonds form from shared electrons.
As you read in Section 1, nature favors chemical bonding because most
atoms have lower potential energy when they are bonded to other atoms
than they have when they are independent particles. In the case of
covalent-bond formation, this idea is illustrated by a simple example, the
formation of a hydrogen-hydrogen bond.
Picture two isolated hydrogen atoms separated by a distance large FIGURE 2.3
enough to prevent them from influencing each other. At this distance,
the overall potential energy of the atoms is arbitrarily set at zero, as shown Attractive and Repulsive
in part (a) of Figure 2.2. Forces The arrows indicate
Now consider what happens if the hydrogen atoms approach each the attractive and repulsive forces
between the electrons (shown as
other. Each atom has a nucleus containing a single positively charged
electron clouds) and nuclei of two
proton. The nucleus of each atom is surrounded by a negatively charged
hydrogen atoms. Attraction between
electron in a spherical 1s orbital. As the atoms near each other, their
particles corresponds to a decrease
charged particles begin to interact. As shown in Figure 2.3, the approach-
in potential energy of the atoms, while
ing nuclei and electrons are attracted to each other, which corresponds to
repulsion corresponds to an increase.
a decrease in the total potential energy of the atoms. At the same time, the
two nuclei repel each other, and the two electrons repel each other, which CRITICAL THINKING
results in an increase in potential energy. Explain How do covalently bonded
The relative strength of attraction and repulsion between the charged compounds stay together if both
particles depends on the distance separating the atoms. When the atoms the nuclei and the electrons of the
atoms involved repel each other?
first “sense” each other, the electron-proton attraction is stronger than the
electron-electron and proton-proton repulsions. Thus, the atoms are Both nuclei repel
drawn to each other, and their potential energy is lowered, as shown in each other, as do both
part (b) of Figure 2.2. electron clouds.

The attractive force continues to dominate, and the total potential

energy continues to decrease until, eventually, a distance is reached at –
which the repulsion between the like charges equals the attraction of the + +
opposite charges. This is shown in part (c) of Figure 2.2. At this point, –
which is represented by the bottom of the valley in the curve, potential
energy is at a minimum, and a stable hydrogen molecule forms. A closer
The nucleus of one atom
approach of the atoms, shown in part (d) of Figure 2.2, results in a sharp attracts the electron cloud of
rise in potential energy as repulsion becomes increasingly greater the other atom, and vice versa.
than attraction.

Chemical Bonding 175

why it matters

Waste to
Energy
N
o one likes garbage piling up. It’s unsightly, smelly, electricity. There are four steps in the process, each carried
and unhealthful. You might think the garbage problem out by a different type of bacteria:
is solved once it’s hauled away—out of sight, out of
1. Hydrolysis breaks down long-chain organic molecules by
mind. But what happens to this waste after the garbage
adding a water molecule to –COOC– bonds.
truck takes it away? In many places, it is simply dumped into
a landfill and then covered with soil. The problem with this 2. The products of the first step are broken down further by
method is that trash contains toxic materials that eventually a fermentation process similar to the souring of milk.
leach down into the groundwater and pollute the water table, 3. The next stage converts stage 2 products into hydrogen,
making the water unfit for drinking or irrigation. acetic acid, and carbon dioxide.

One solution to waste disposal is to incinerate, or burn, the 4. Finally, these molecules are converted to carbon dioxide
combustible materials in the waste to produce thermal and methane. The overall process can be summarized by
energy, which can be transformed into electrical energy. the equation for the anaerobic digestion of glucose:
Combustible materials in waste include hydrocarbons, C6H12O6 → 3CO2 + 3CH4
carbohydrates, and cellulose. These materials have the An added bonus to this process: the bacteria do all this work
general formulas CnH(2n + 2), Cn(H2O)m, and (C6H10O5)n, for free!
respectively. When each of these compounds burns, the
products are water, carbon dioxide, and thermal energy. One
problem with incineration is that carbon dioxide is a Questions
greenhouse gas that usually escapes into the atmosphere. 1. T his equation for the combustion of methane is
Waste also contains toxic materials that can cause health unbalanced:
problems. Technological advances have helped reduce this
CH4 + O2 → CO2 + H2O
problem. The incineration plant in the photo is equipped with
devices that remove the pollutants dioxin and gaseous Balance the equation and explain why burning methane
oxides of nitrogen. to produce another greenhouse gas helps reduce global

(bck) ©Hans Blossey/imageBROKER/age fotostock; (t) ©Mikalai/YAY Micro/age fotostock

climate change.
Another waste-to-energy process is anaerobic digestion.
Anaerobic means “in the absence of oxygen.” Bacteria digest 2. Often, toxins and other pollutants are buried to get rid of
the waste, producing carbon dioxide and methane. Waste left them. Use evidence to explain if you think this approach
unattended in a landfill undergoes this process spontaneously. is a viable long-term solution. Develop a model to help
The problem with this method of waste disposal is that both explain the rationale behind your argument.
carbon dioxide and methane are greenhouse gases, and, in
fact, methane adds to the greenhouse effect much more
than carbon dioxide does.
One solution is to encourage anaerobic digestion in a
closed container and use the methane to fuel production of

176
 MAIN IDEA
Bond lengths and energy vary from molecule
to molecule.
In Figure 2.2, the bottom of the valley in the curve represents the balance
between attraction and repulsion in a stable covalent bond. At this point,
the electrons of each hydrogen atom of the hydrogen molecule are shared
between the nuclei. As shown in Figure 2.4, the molecule’s electrons can
be pictured as occupying overlapping orbitals, moving about freely in
either orbital.
The bonded atoms vibrate a bit, but as long as their potential energy
remains close to the minimum, they are covalently bonded to each other.
The distance between two bonded atoms at their minimum potential
energy, that is, the average distance between two bonded atoms, is the
bond length. The bond length of a hydrogen-hydrogen bond is 75 pm.
In forming a covalent bond, the hydrogen atoms release energy as CHECK FOR UNDERSTANDING
they change from isolated individual atoms to parts of a molecule. The Apply Does electronegativity play
amount of energy released equals the difference between the potential a role in the formation of covalent
energy at the zero level (separated atoms) and that at the bottom of the bonds? Explain.
valley (bonded atoms) in Figure 2.2. The same amount of energy must be
added to separate the bonded atoms. Bond energy is the energy required to
break a chemical bond and form neutral isolated atoms. Scientists usually
report bond energies in kilojoules per mole (kJ/mol), which indicates the
energy required to break one mole of bonds in isolated molecules. For
example, 436 kJ of energy is needed to break the hydrogen-hydrogen
bonds in one mole of hydrogen molecules and form two moles of
separated hydrogen atoms.
The energy relationships described here for the formation of a
hydrogen-hydrogen bond apply generally to all covalent bonds. However,
bond lengths and bond energies vary with the types of atoms that have
combined. Even the energy of a bond between the same two types of
atoms varies somewhat, depending on what other bonds the atoms have
formed. These facts should be considered when examining the data in
Figure 2.5 on the next page. The first three columns in the table list bonds,
bond lengths, and bond energies of atoms in specific diatomic molecules.
The last three columns give average values of specified bonds in many
different compounds.

FIGURE 2.4
Region of orbital
Overlapping Orbitals The orbitals Electron clouds overlap
of the hydrogen atoms in a hydrogen
molecule overlap, allowing each electron
to feel the attraction of both nuclei. The
result is an increase in electron density
between the nuclei.

Nuclei

Hydrogen atoms Hydrogen molecule

Chemical Bonding 177

FIGURE 2.5

BOND LENGTHS AND BOND ENERGIES FOR SELECTED COVALENT BONDS

Average bond Average bond Average bond Average bond
Bond length (pm) energy (kJ/mol) Bond length (pm) energy (kJ/mol)

H-H 75 436 C-C 154 346

F-F 142 159 C-N 147 305
Cl-Cl 199 243 C-O 143 358
Br-Br 229 193 C-H 109 418
I-I 266 151 C-Cl 177 327
H-F 92 569 C-Br 194 285
H-Cl 127 432 N-N 145 163
H-Br 141 366 N-H 101 386
H-I 161 299 O-H 96 459

All individual hydrogen atoms contain a single, unpaired electron in a

1s atomic orbital. When two hydrogen atoms form a molecule, they share
electrons in a covalent bond. As Figure 2.6 shows, sharing electrons allows
each atom to have the stable electron configuration of helium, 1s2. This
tendency for atoms to achieve noble-gas configurations by bonding
covalently extends beyond the simple case of a hydrogen molecule.

FIGURE 2.6

Bond Length and Stability Bonding electron pair in overlapping orbitals

By sharing electrons in overlapping
orbitals, each hydrogen atom in a
hydrogen molecule experiences the ↑ ↑
H H 1s
effect of a stable 1s2 configuration. 1s

↓ ↓
H H
1s 1s
Hydrogen Hydrogen
atoms molecule

MAIN IDEA
Atoms tend to form bonds to follow the octet rule.
Unlike other atoms, the noble-gas atoms exist independently in nature.
They possess a minimum of energy existing on their own because of the
special stability of their electron configurations. This stability results from
the fact that, with the exception of helium and its two electrons in a
completely filled outer shell, the noble-gas atoms’ outer s and p orbitals
are completely filled by a total of eight electrons. Other main-group
atoms can effectively fill their outermost s and p orbitals with electrons by
sharing electrons through covalent bonding.

178 Chapter 6
 Such bond formation follows the octet rule: Chemical compounds
tend to form so that each atom, by gaining, losing, or sharing electrons,
has an octet of electrons in its highest occupied energy level.
Let’s examine how the bonding in a fluorine molecule illustrates the
octet rule. An independent fluorine atom has seven electrons in its highest
energy level ([He]2s22p5). Like hydrogen atoms, fluorine atoms bond
covalently with each other to form diatomic molecules, F2. When two
fluorine atoms bond, each atom shares one of its valence electrons with its
partner. The shared electron pair effectively fills each atom’s outermost
energy level with an octet of electrons, as illustrated in Figure 2.7a.
Figure 2.7b shows another example of the octet rule, in which the chlorine
atom in a molecule of hydrogen chloride, HCl, achieves an outermost
octet by sharing an electron pair with an atom of hydrogen.

FIGURE 2.7

Octet Rule (a)

(a) By sharing valence electrons in ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ Bonding
F F 1s 2s electron
overlapping orbitals, each atom in a 1s 2s
2p 2p pair in
fluorine molecule feels the effect of overlapping
neon’s stable configuration, [He]2s22p6. ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ orbitals
(b) In a hydrogen chloride molecule, F 1s 2s
F
1s 2s
the hydrogen atom effectively fills its 2p 2p
1s orbital with two electrons, while the Fluorine atoms Fluorine molecule
chlorine atom experiences the stability of
an outermost octet of electrons. Bonding electron pair
in overlapping orbitals

(b)
↑ ↑
H H
1s 1s
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓
Cl Cl
1s 2s 3s 1s 2s 3s
2p 3p 2p 3p
Hydrogen and chlorine atoms Hydrogen chloride molecule

Exceptions to the Octet Rule

Most main-group elements tend to form covalent bonds according to the
octet rule. However, there are exceptions. As you have seen, hydrogen
forms bonds in which it is surrounded by only two electrons. Boron, B,
has just three valence electrons ([He]2s22p1). Because electron pairs are
shared in covalent bonds, boron tends to form bonds in which it is
surrounded by six electrons. In boron trifluoride, BF3, for example, the
boron atom is surrounded by its own three valence electrons plus one
from each of the three fluorine atoms bonded to it. Other elements can be
surrounded by more than eight electrons when they combine with the
highly electronegative elements fluorine, oxygen, and chlorine. In these
cases of expanded valence, bonding involves electrons in d orbitals as well
as in s and p orbitals. Examples of compounds that have an expanded
valence include PCl5 and SF6, as shown in Figure 5.4 (in Section 5).

Chemical Bonding 179

FIGURE 2.8 MAIN IDEA

Writing Electron-Dot Notations To write an Dots placed around an element’s symbol

element’s electron-dot notation, determine the element’s can represent valence electrons.
number of valence electrons. Then place a corresponding
number of dots around the element’s symbol, as shown. Covalent-bond formation usually involves only the
electrons in an atom’s outermost energy levels, or the
Number of Electron-dot
valence electrons notation Example
atom’s valence electrons. To keep track of these electrons,
it is helpful to use electron-dot notation. Electron-dot
1 X Na notation is an electron-configuration notation in which only
the valence electrons of an atom of a particular element are
2 X Mg shown, indicated by dots placed around the element’s
3 X B symbol. The inner-shell electrons are not shown. For
example, the electron-dot notation for a fluorine atom
4 X C (electron configuration [He]2s22p5) may be written
as follows.
5 X N
..
6 X O : F. :

7 X F In general, a main-group element’s number of valence

electrons can be determined by adding the superscripts
8 X Ne of the element’s noble-gas notation. In this book, the
electron-dot notations for elements with 1–8 valence
electrons are written as shown in Figure 2.8.

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Sample Problem B a. Write the electron-dot notation for hydrogen.

b. Write the electron-dot notation for nitrogen.
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SOLVE a. A hydrogen atom has only one occupied energy level, the n = 1 level,
which contains a single electron. Therefore, the electron-dot notation for
hydrogen is written as follows.
H.

b. The group notation for nitrogen’s family of elements is ns2np3, which

indicates that nitrogen has five valence electrons. Therefore, the
electron-dot notation for nitrogen is written as follows.
.
.N. :

MAIN IDEA
Electron-dot notations can represent compounds.
Electron-dot notations are also useful for representing molecules. For
example, a hydrogen molecule, H2, is represented by combining the
notations of two individual hydrogen atoms, as follows.
H:H

180 Chapter 6
The pair of dots represents the shared electron pair of the hydrogen-hydrogen
covalent bond. For a molecule of fluorine, F2, the electron-dot notations of
two fluorine atoms are combined.
.. ..
:.F. :.F. :

Here, too, the pair of dots between the two symbols represents the shared
pair of a covalent bond. In addition, each fluorine atom is surrounded by
three pairs of electrons that are not shared in bonds. An unshared pair,
also called a lone pair, is a pair of electrons that is not involved in bonding
and that belongs exclusively to one atom.
The pair of dots representing a shared pair of electrons in a covalent
bond is often replaced by a long dash. According to this convention,
hydrogen and fluorine molecules are represented as follows.
.. ..
H-H :.F. -.F. :

These representations are all Lewis structures, formulas in which atomic

symbols represent nuclei and inner-shell electrons, dot-pairs or dashes
between two atomic symbols represent electron pairs in covalent bonds, and
dots adjacent to only one atomic symbol represent unshared electrons. It is
common to write Lewis structures that show only the electrons that are
shared, using dashes to represent the bonds. A structural formula indicates
the kind, number, arrangement, and bonds but not the unshared pairs of the
atoms in a molecule. For example, F-F and H-Cl are structural formulas.
The Lewis structures (and therefore the structural formulas) for many
molecules can be drawn if one knows the composition of the molecule
and which atoms are bonded to each other. The following sample prob-
lem illustrates the basic steps for writing Lewis structures. The molecule
described in this problem contains bonds with single, shared electron
pairs. A single covalent bond, or a single bond, is a covalent bond in which one
pair of electrons is shared between two atoms.

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Sample Problem C Draw the Lewis structure of iodomethane, CH3I.

SOLVE 1. Determine the type and number of atoms in the molecule.

The formula shows one carbon atom, one iodine atom, and
three hydrogen atoms.
2. Write the electron-dot notation for each type of atom in the
molecule.
Carbon is from Group 14 and has four valence electrons.
Iodine is from Group 17 and has seven valence electrons.
Hydrogen has one valence electron.
. ..
.C. : I : H .
. .

Continued
Chemical Bonding 181
 Lewis Structures (continued)

3. Determine the total number of valence electrons available in the atoms to

be combined.
C 1 × 4e- = 4e-
I 1 × 7e- = 7e-
3H 3 × 1e- = 3e-
14e-
4. Arrange the atoms to form a skeleton structure for the molecule. If carbon is
present, it is the central atom. Otherwise, the least-electronegative atom is
central (except for hydrogen, which is never central). Then connect the atoms
by electron-pair bonds.
H
..
H: C
.. :I
H
5. Add unshared pairs of electrons to each nonmetal atom (except hydrogen)
such that each is surrounded by eight electrons.
H
H
.. ..  ..
H: C
. . : .I. :
or H- C -.I. :
H 
H
6. Count the electrons in the structure to be sure that the number of valence
electrons used equals the number available. Be sure the central atom and other
atoms besides hydrogen have an octet. There are eight electrons in the four
covalent bonds and six electrons in the three unshared pairs, giving the
correct total of 14 valence electrons.

1. Draw the Lewis structure for ammonia, NH3.

2. Draw the Lewis structure for hydrogen sulfide, H2S.
3. Draw the Lewis structure for silane, SiH4.
4. Draw the Lewis structure for phosphorus trifluoride, PF3.

MAIN IDEA
Some atoms can share multiple pairs of electrons.
Atoms of some elements, especially carbon, nitrogen, and oxygen, can
share more than one electron pair. A double covalent bond, or simply a
double bond, is a covalent bond in which two pairs of electrons are shared
between two atoms. A double bond is shown either by two side-by-side
pairs of dots or by two parallel dashes. All four electrons in a double bond
“belong” to both atoms. In ethene, C2H4, for example, two electron pairs
are simultaneously shared by two carbon atoms.

H H H H
C::C or C=C
H H H H

182 Chapter 6
 A triple covalent bond, or simply a triple bond, is a covalent bond in
FIGURE 2.9
which three pairs of electrons are shared between two atoms. For example,
elemental nitrogen, N2, like hydrogen and the halogens, normally exists as Forming Triple Bonds In a
diatomic molecules. In this case, however, each nitrogen atom, which has molecule of nitrogen, N2, each nitrogen
five valence electrons, acquires three electrons to complete an octet by atom is surrounded by six shared electrons
sharing three pairs of electrons with its partner. This is illustrated in the plus one unshared pair of electrons. Thus,
Lewis structure and the formula structure for N2, as shown below. each nitrogen atom follows the octet rule
in forming a triple covalent bond.
:N:::N: or :N≡N: ↑↓ ↑↓ ↓ ↓ ↓
N
1s 2s
Figure 2.9 represents nitrogen’s triple bond through orbital notation. Like 2p
the single bonds in hydrogen and halogen molecules, the triple bond in
nitrogen molecules is nonpolar. ↑↓ ↑↓ ↑ ↑ ↑
N 1s 2s
Carbon forms a number of compounds containing triple bonds. For 2p
example, the compound ethyne, C2H2, contains a carbon-carbon triple
Nitrogen molecule
bond.

H:C:::C:H or H-C≡C-H

Double and triple bonds are referred to as multiple bonds, or multiple covalent
bonds. Double bonds in general have greater bond energies and are
shorter than single bonds. Triple bonds are even stronger and shorter.
Figure 2.10 compares average bond lengths and bond energies for some
single, double, and triple bonds.
In writing Lewis structures for molecules that contain carbon, nitrogen, CHECK FOR UNDERSTANDING
or oxygen, one must remember that multiple bonds between pairs of these Explain Although silicon is in the
atoms are possible. (A hydrogen atom, on the other hand, has only one same periodic group and shares many
electron and therefore always forms a single covalent bond.) The need properties with carbon, it has a
for a multiple bond becomes obvious if there are not enough valence significantly greater bond length.
electrons to complete octets by adding unshared pairs. Sample Problem D Explain why this would make carbon
on the next page shows how to deal with this situation. a better building block than silicon
for living organisms.

FIGURE 2.10

BOND LENGTHS AND BOND ENERGIES FOR SINGLE AND MULTIPLE COVALENT BONDS

Average bond Average bond Average bond Average bond

Bond length (pm) energy (kJ/mol) Bond length (pm) energy (kJ/mol)

C-C 154 346 C-O 143 358

C=C 134 612 C=O 120 732

C≡C 120 835 C≡O 113 1072

C-N 147 305 N-N 145 163

C=N 132 615 N=N 125 418

C≡N 116 887 N≡N 110 945

Chemical Bonding 183

 Lewis Structures

Sample Problem D Draw the Lewis structure for methanal, CH2O, which is also known
as formaldehyde.

SOLVE 1. Determine the number of atoms of each element present in the molecule.
The formula shows one carbon atom, two hydrogen atoms, and one
oxygen atom.
2. Write the electron-dot notation for each type of atom.
Carbon is from Group 14 and has four valence electrons. Oxygen, which is in
Group 16, has six valence electrons. Hydrogen has only one electron.
. . .
.C
. . : O. : H
3. Determine the total number of valence electrons available in the atoms to
be combined.
C 1 × 4e- = 4e-
O 1 × 6e- = 6e-
2H 2 × 1e- = 2e-
12e-
4. Arrange the atoms to form a skeleton structure for the molecule, and connect the
atoms by electron-pair bonds.
H
..
H :C : O
5. Add unshared pairs of electrons to each nonmetal atom (except hydrogen) such
that each is surrounded by eight electrons.
H
.. ..
HC: . . :O
.. :
6a. Count the electrons in the Lewis structure to be sure that the number of valence
electrons used equals the number available.
The structure above has six electrons in covalent bonds and eight electrons in
four lone pairs, for a total of 14 electrons. The structure has two valence
electrons too many.
6b. If too many electrons have been used, subtract one or more lone pairs until the
total number of valence electrons is correct. Then move one or more lone
electron pairs to existing bonds between non-hydrogen atoms until the outer
shells of all atoms are completely filled.
Subtract the lone pair of electrons from the carbon atom. Then move one lone
pair of electrons from the oxygen to the bond between carbon and oxygen to
form a double bond. There are eight electrons in covalent bonds and four
electrons in lone pairs, for a total of 12 valence electrons.

H
H.. ..  ..
H C : :O
: .. or H -C =O
..

1. Draw the Lewis structure for carbon dioxide, CO2.

2. Draw the Lewis structure for hydrogen cyanide, which contains one hydrogen atom, one
carbon atom, and one nitrogen atom.

184 Chapter 6
 MAIN IDEA
Resonance structures show hybrid bonds.
Some molecules and ions cannot be represented adequately by a single
Lewis structure. One such molecule is ozone, O3, which can be repre-
sented by either of the following Lewis structures.
.. .. .. .. .. ..
. . =O -O
O .. : or :O
. . -O =O
..
Notice that each structure indicates that the ozone molecule has two
types of O-O bonds, one single and one double. Chemists once specu-
lated that ozone split its time existing as one of these two structures,
constantly alternating, or “resonating,” from one to the other.
Experiments, however, revealed that the oxygen-oxygen bonds in ozone
are identical. Therefore, scientists now say that ozone has a single struc-
ture that is the average of these two structures. Together the structures are
referred to as resonance structures or resonance hybrids. Resonance
refers to bonding in molecules or ions that cannot be correctly represented by a
single Lewis structure. To indicate resonance, a double-headed arrow is
placed between a molecule’s resonance structures.
.. .. .. .. .. ..
. . =O -O
O . . : ←→ :O
. . -O =O
..

MAIN IDEA
Some compounds are networks of bonded atoms.
The covalent compounds that you have read about so far consist of many
identical molecules held together by forces acting between the molecules.
(You will read more about these intermolecular forces in Section 5.) There
are many covalently bonded compounds that do not contain individual
molecules but instead can be pictured as continuous, three-dimensional
networks of bonded atoms. You will read more about covalently bonded
networks in the chapter “Chemical Formulas and Chemical Compounds.”

SECTION 2 FORMATIVE ASSESSMENT

Reviewing Main Ideas 4. Draw the Lewis valence electron dot structures
to show the arrangement of electrons in the
1. Define the following: following atoms and molecules:
a. bond length a. C
b. bond energy b. Al
2. State the octet rule. c. C2HCl
3. How many pairs of electrons are shared in the d. SiCl4
following types of covalent bonds? e. OF2
a. a single bond
b. a double bond Critical Thinking
c. a triple bond 5. APPLYING MODELS Compare the molecules
H2NNH2 and HNNH. Which molecule has the
stronger N—N bond?

Chemical Bonding 185

 SECTION 3
Main Ideas
Ionic Bonding and
Ionic Compounds
Ionic bonds form from
attractions between positive
and negative ions.

Differences in attraction strength Key Terms

give ionic and molecular ionic compound lattice energy
compounds different properties. formula unit polyatomic ion

Multiple atoms can bond

Most of the rocks and minerals that make up Earth’s crust consist of positive and
covalently to form a single ion.
negative ions held together by ionic bonding. A familiar example of an ionically
bonded compound is sodium chloride, or common table salt, which is found in
nature as rock salt. A sodium ion, Na+, has a charge of 1+. A chloride ion, Cl-,
has a charge of 1-. There is an electrical force of attraction between oppositely
charged ions. In sodium chloride, these ions combine in a one-to-one ratio—
Na+Cl-—so that each positive charge is balanced by a negative charge. The
chemical formula for sodium chloride is usually written simply as NaCl.
An ionic compound is composed of positive and negative ions that are
combined so that the numbers of positive and negative charges are equal. Most
ionic compounds exist as crystalline solids (see Figure 3.1). A crystal of any ionic
compound is a three-dimensional network of positive and negative ions mutually
attracted to one another. As a result, in contrast to a molecular compound, an ionic
compound is not composed of independent, neutral units that can be isolated
FIGURE 3.1 and examined. The chemical formula of an ionic compound merely represents the
simplest ratio of the compound’s combined ions that gives electrical neutrality.
Ionic Compounds Sodium The chemical formula of an ionic compound shows the ratio of the ions present
chloride (common table salt) is an in a sample of any size. A formula unit is the simplest collection of atoms from
ionic compound. which an ionic compound’s formula can be written. For example, one formula unit
of sodium chloride, NaCl, is one sodium cation plus one chloride anion. (In the
CRITICAL THINKING
naming of a monatomic anion, the ending of the element’s name becomes -ide.)
Explain How is the structure of
The ratio of ions in a formula unit depends on the charges of the ions combined.
sodium chloride typical of ionic
For example, to achieve electrical neutrality in the ionic compound calcium fluoride,
compounds? two fluoride anions, F-, each with a charge of 1-, must balance the 2+ charge of
each calcium cation, Ca2+. Therefore, the formula of calcium fluoride is CaF2.

MAIN IDEA
Ionic bonds form from attractions between positive
and negative ions.
Electron-dot notation can be used to demonstrate the changes that take
place in ionic bonding. Ionic compounds do not ordinarily form by the
combination of isolated ions, but consider for a moment a sodium
atom and a chlorine atom approaching each other. The two atoms are
©Charles Falco/Photo Researchers, Inc

neutral and have one and seven valence electrons, respectively.

. ..
Na .:
:Cl
Sodium atom Chlorine atom
We have already seen that atoms of sodium and the other alkali metals
readily lose one electron to form cations. And we have seen that atoms of
chlorine and the other halogens readily gain one electron to form anions.

186 Chapter 6
 The combination of sodium and chlorine atoms to produce one formula FIGURE 3.2
unit of sodium chloride can thus be represented as follows.
Ions and Electrical Forces The
. .. .. -
Na + :Cl  Na+ ions in an ionic compound lower their
.: + .. :
: Cl
potential energy by forming an orderly,
Sodium atom Chlorine atom Sodium cation Chloride anion
three-dimensional array in which the
positive and negative charges are
The transfer of an electron from the sodium atom to the chlorine atom
balanced. The electrical forces of attraction
transforms each atom into an ion with a noble-gas configuration. In the
between oppositely charged ions extend
combination of calcium with fluorine, two fluorine atoms are needed to
over long distances, causing a large
accept the two valence electrons given up by one calcium atom. decrease in potential energy.
.. .. .. ..
. Ca . + :F. : + :F. :  Ca2+ - :.F. : - : .F. :-
Calcium atom Fluorine atoms Calcium cation Fluoride anions
- +
-
Characteristics of Ionic Bonding -
+ +
Recall that nature favors arrangements in which potential energy is -
+ - -
minimized. In an ionic crystal, ions minimize their potential energy by + +
+ - +
combining in an orderly arrangement known as a crystal lattice (see
- - -
Figure 3.2). The attractive forces at work within an ionic crystal include + -
+ + +
those between oppositely charged ions and those between the nuclei and -
electrons of adjacent ions. The repulsive forces include those between -
-
like-charged ions and those between electrons of adjacent ions. The +
distances between ions and their arrangement in a crystal represent a
balance among all these forces. Sodium chloride’s crystal structure is
shown in Figure 3.3 below.

FIGURE 3.3

Crystal Structure of NaCl Two models of the crystal

structure of sodium chloride are shown.

Cl-
Na+

Na+

Cl-

(a) To illustrate the ions’ actual (b) In an expanded view, the

arrangement, the sodium distances between ions have
and chloride ions are shown been exaggerated in order to
with their electron clouds clarify the positioning of the
just touching. ions in the structure.

Chemical Bonding 187

FIGURE 3.4

Crystal Structure of NaCl The

figure shows the ions that most closely +
Na
surround a chloride anion and a sodium
cation within the crystal structure of NaCl.

(a) (b)
Six Na+ ions surround _ Six Cl- ions surround each Na+
Cl
each Cl- ion. ion (which cannot be seen, but
whose location is indicated by
the dashed outline).

Figure 3.4 shows the crystal structure of sodium chloride in greater

detail. Within the arrangement, each sodium cation is surrounded by six
chloride anions. At the same time, each chloride anion is surrounded by
six sodium cations. Attraction between the adjacent, oppositely charged
ions is much stronger than repulsion by other ions of the same charge,
which are farther away.
The three-dimensional arrangements of ions and the strengths of
attraction between them vary with the sizes and charges of the ions
and the numbers of ions of different charges. For example, in calcium
fluoride, there are two anions for each cation. Each calcium cation is
surrounded by eight fluoride anions. At the same time, each fluoride ion
is surrounded by four calcium cations, as shown in Figure 3.5.
To compare bond strengths in ionic compounds, chemists compare
the amounts of energy released when separated ions in a gas come
together to form a crystalline solid. Lattice energy is the energy released
when one mole of an ionic crystalline compound is formed from gaseous ions.
Lattice energy values for a few common ionic compounds are shown in
Figure 3.6 (on the next page). The negative energy values indicate that
energy is released when the crystals are formed.

FIGURE 3.5 Calcium ion, Ca2+

Crystal Structure of CaF2 In the

crystal structure of calcium fluoride, CaF2,
each calcium cation is surrounded by eight
fluoride anions, and each fluoride ion is
surrounded by four calcium cations. This is
the closest possible packing of the ions in
which the positive and negative charges
are balanced.

Fluoride ion, F-

188 Chapter 6
 MAIN IDEA FIGURE 3.6
Differences in attraction strength give ionic and LATTICE ENERGIES OF
molecular compounds different properties. SOME COMMON IONIC
COMPOUNDS
The force that holds ions together in ionic compounds is a very strong
overall attraction between positive and negative charges. In a molecular Lattice energy
compound, the covalent bonds of the atoms making up each molecule Compound (kJ/mol)
are also strong. But the forces of attraction between molecules are much
weaker than the forces among formula units in ionic bonding. This NaCl -787.5
difference in the strength of attraction between the basic units of molecu-
lar and ionic compounds gives rise to different properties in the two types NaBr -751.4
of compounds.
The melting point, boiling point, and hardness of a compound CaF2 -2634.7
depend on how strongly its basic units are attracted to each other.
Because the forces of attraction between individual molecules are not LiCl -861.3
very strong, many molecular compounds melt at low temperatures. In
fact, many molecular compounds are already completely gaseous at LiF -1032
room temperature. In contrast, the ions in ionic compounds are held
together by strong attractive forces, so ionic compounds generally have
MgO -3760
higher melting and boiling points than do molecular compounds.
Ionic compounds are hard but brittle. Why? In an ionic crystal, even a
KCl -715
slight shift of one row of ions relative to another causes a large buildup of
repulsive forces, as shown in Figure 3.7. These forces make it difficult for
one layer to move relative to another, causing ionic compounds to be
hard. If one layer is moved, however, the repulsive forces make the layers
part completely, causing ionic compounds to be brittle.
In the solid state, the ions cannot move, so the compounds are not
electrical conductors. In the molten state, ionic compounds are electrical
conductors because the ions can move freely to carry electrical current.
Many ionic compounds can dissolve in water. When they dissolve, their
ions separate from each other and become surrounded by water mol-
ecules. These ions are free to move through the solution, so such solutions
are electrical conductors. Other ionic compounds do not dissolve in
water, however, because the attractions between the water molecules and
the ions cannot overcome the attractions between the ions.

FIGURE 3.7 (a) + (b) + Strong repulsion

Ionic Properties (a) The attraction – + – + +

between positive and negative ions in a
crystalline ionic compound causes layers + – + + – –
of ions to resist motion.
(b) When struck with sufficient force, – + – – + +
the layers shift so that ions of the same
charge approach each other, causing – + – –
repulsion. As a result, the crystal shatters Attraction
along the planes. –
Attraction
Force
dislocates crystal plane
(a) (b)

Chemical Bonding 189

 MAIN IDEA
Multiple atoms can bond covalently
to form a single ion.
Certain atoms bond covalently with each other to form a group of atoms
that has both molecular and ionic characteristics. A charged group of
covalently bonded atoms is known as a polyatomic ion. Polyatomic ions
combine with ions of opposite charge to form ionic compounds. The
charge of a polyatomic ion results from an excess of electrons (negative
charge) or a shortage of electrons (positive charge). For example, an
ammonium ion, a common positively charged polyatomic ion, contains
one nitrogen atom and four hydrogen atoms and has a single positive
charge. Its formula is NH + +
4 , sometimes written as [NH4] to show that the
group of atoms as a whole has a charge of 1+. The seven protons in the
nitrogen atom plus the four protons in the four hydrogen atoms give the
ammonium ion a total positive charge of 11+. An independent nitrogen
CHECK FOR UNDERSTANDING atom has seven electrons, and four independent hydrogen atoms have a
Why is it necessary to add or subtract total of four electrons. When these atoms combine to form an ammo-
electrons from the total number of nium ion, one of their electrons is lost, giving the polyatomic ion a total
valence electrons for polyatomic ions? negative charge of 10-.
Lewis structures for the ammonium ion and some common negative
polyatomic ions—the nitrate, sulfate, and phosphate ions—are shown
below. To find the Lewis structure for a polyatomic ion, follow the steps of
Sample Problem D, with the following exception. If the ion is negatively
charged, add to the total number of valence electrons a number of
electrons corresponding to the ion’s negative charge. If the ion is posi-
tively charged, subtract from the total number of valence electrons a
number of electrons corresponding to the ion’s positive charge.

 +  .. -  .. 2-  .. 3-
H :O
.. : .. .. :O .. : .. .. :O.. : ..
 ..
H: N
. . :H  . . ::O
N
:.. :

..   
. . : .S. : O
:O .. : :O .. :O
.. : P
:O

.. :
 H  O  
:O
.. :   .. : 
Ammonium ion Nitrate ion Sulfate ion Phosphate ion

SECTION 3 FORMATIVE ASSESSMENT

Reviewing Main Ideas 4. Compound B has lower melting and boiling
points than compound A. At the same tempera-
1. Give two examples of an ionic compound. ture, compound B vaporizes faster than com-
2. Use electron-dot notation to demonstrate the pound A. If one of these compounds is ionic and
formation of ionic compounds involving the the other is molecular, which would you expect
following: to be molecular? ionic? Explain your reasoning.
a. Li and Cl
b. Ca and I Critical Thinking
3. Distinguish between ionic and molecular 5. ANALYZING DATA The melting points for
compounds in terms of the basic units that the compounds Li2S, Rb2S, and K2S are 900°C,
make up each. 530°C, and 840°C, respectively. List these three
compounds in order of increasing lattice energy.

190 Chapter 6
 SECTION 4

Metallic Bonding Main Idea

Metal electrons move freely in
Key Terms empty, overlapping orbitals.
metallic bonding
malleability
ductility

Chemical bonding is different in metals than it is in ionic, molecular, or covalent-

network compounds. This difference is reflected in the unique properties of metals.
They are excellent electrical conductors in the solid state—much better conductors
than even molten ionic compounds. This property is due to the highly mobile
valence electrons of the atoms that make up a metal. Such mobility is not possible
in molecular compounds, in which valence electrons are localized in electron-pair
bonds between neutral atoms. Nor is it possible in solid ionic compounds, in which
electrons are bound to individual ions that are held in place in crystal structures.

MAIN IDEA
Metal electrons move freely in empty,
overlapping orbitals.
The highest energy levels of most metal atoms are occupied by very few
electrons. In s-block metals, for example, one or two valence electrons
occupy the outermost orbital, and all three outermost p orbitals, which
can hold a total of six electrons, are vacant. In addition to completely
vacant outer p orbitals, d-block metals also possess many vacant
d orbitals in the energy level just below their highest energy level.
Within a metal, the vacant orbitals in the atoms’ outer energy levels FIGURE 4.1
overlap. This overlapping of orbitals allows the outer electrons of the
atoms to roam freely throughout the entire metal. The electrons are Crystal Structure of Solid
delocalized, which means that they do not belong to any one atom but Sodium The model shows a
move freely about the metal’s network of empty atomic orbitals. These portion of the crystal structure of solid
mobile electrons form a sea of electrons around the metal atoms, which sodium. The atoms are arranged so
are packed together in a crystal lattice (see Figure 4.1). The chemical that each sodium atom is surrounded
bonding that results from the attraction between metal atoms and the
by eight other sodium atoms. The
atoms are relatively fixed in position,
surrounding sea of electrons is called metallic bonding.
while the electrons are free to move
throughout the crystal, forming an
Metallic Properties electron sea.
The freedom of electrons to move in a network of metal atoms accounts
for the high electrical and thermal conductivity characteristic of all
metals. In addition, metals are both strong absorbers and reflectors of
light. Because they contain many orbitals separated by extremely small
energy differences, metals can absorb a wide range of light frequencies.
This absorption of light results in the excitation of the metal atoms’
electrons to higher energy levels. However, in metals the electrons
immediately fall back down to lower levels, emitting energy in the form
of light at a frequency similar to the absorbed frequency. This re-radiated
(or reflected) light is responsible for the metallic appearance or luster
of metal surfaces.

Chemical Bonding 191

FIGURE 4.2 Most metals are also easy to form into desired shapes. Two important
properties related to this characteristic are malleability and ductility (see
Shaping Metals Unlike ionic Figure 4.2). Malleability is the ability of a substance to be hammered or beaten
crystalline compounds, most metals into thin sheets. Ductility is the ability of a substance to be drawn, pulled, or
are malleable. This property allows extruded through a small opening to produce a wire. The malleability and
iron, for example, to be shaped into
ductility of metals are possible because metallic bonding is the same in
useful tools.
all directions throughout the solid. When struck, one plane of atoms in a
metal can slide past another without encountering resistance or breaking
bonds. By contrast, recall from Section 3 that shifting the layers of an
ionic crystal causes the bonds to break and the crystal to shatter.

Metallic Bond Strength

Metallic bond strength varies with the nuclear charge of the metal atoms
and the number of electrons in the metal’s electron sea. Both of these
factors are reflected in a metal’s enthalpy of vaporization. The amount of
energy as heat required to vaporize the metal is a measure of the strength
of the bonds that hold the metal together. The enthalpy of vaporization is
defined as the amount of energy absorbed as heat when a specified
amount of a substance vaporizes at constant pressure. Some enthalpies
of vaporization for metals are given in Figure 4.3.

FIGURE 4.3
ENTHALPIES OF VAPORIZATION OF SOME METALS
(kJ/mol)
Period Element

Li Be
Second
147 297

Na Mg Al
Third
97 128 294

K Ca Sc
Fourth
77 155 333

Rb Sr Y
Fifth
76 137 365

Cs Ba La
Sixth
64 140 402

SECTION 4 FORMATIVE ASSESSMENT

Reviewing Main Ideas 3. Explain why most metals are malleable and
ductile but ionic crystals are not.
1. Describe the electron-sea model of metallic
bonding.
Critical Thinking
2. What is the relationship between metallic bond
4. ORGANIZING IDEAS Explain why metals are
strength and enthalpy of vaporization?
©Photri

good electrical conductors.

192 Chapter 6
 Section 5

Molecular Geometry Main Ideas

Negative particles repel and
Key Terms move away from each other.
VSEPR theory hybrid orbitals hydrogen bonding
hybridization dipole London dispersion forces Multiple orbitals can combine to
form hybrid orbitals.
The properties of molecules depend not only on the bonding of atoms but also
Weak forces exist between
on molecular geometry—the three­-­dimensional arrangement of a molecule’s
atoms in space. The polarity of each bond, along with the geometry of the molecules.
molecule, determines molecular polarity, or the uneven distribution of molecular
charge. As you will read, molecular polarity strongly influences the forces that
act between molecules in liquids and ­solids.
A chemical formula reveals little information about a molecule’s geometry.
After performing many tests designed to reveal the shapes of various molecules,
chemists developed two different, equally successful theories to explain certain
aspects of their findings. One theory accounts for molecular-bond angles. The
other is used to describe the orbitals that contain the valence electrons of a
molecule’s atoms.

Main Idea
Negative particles repel and move away from
each other.
As shown in Figure 5.1, diatomic molecules, like those of hydrogen, H2,
and hydrogen chloride, HCl, must be linear because they consist of only
two ­atoms. To predict the geometries of more­-­complicated molecules,
one must consider the locations of all electron pairs surrounding the Figure 5.1
bonded atoms. This is the basis of VSEPR ­theory.
Linear Molecules Ball­-­and­-­
The abbreviation VSEPR stands for “valence­-­shell, electron­-­pair
stick models illustrate the linearity
repulsion,” referring to the repulsion between pairs of valence electrons of diatomic molecules.
of the atoms in a molecule. VSEPR theory states that repulsion between the
sets of valence­-­level electrons surrounding an atom causes these sets to be
oriented as far apart as possible. How does the assumption that electrons in
molecules repel each other account for molecular shapes? For now, let us
(a)—Hydrogen,
(a) Hydrogen, H2 H2
consider only molecules with no unshared valence electron pairs on the
central atom. (a) A hydrogen molecule is
represented by two identical balls
Let’s examine the simple molecule BeF2. The beryllium atom forms a (the hydrogen atoms)
(a)—Hydrogen, H2joined by a
covalent bond with each fluorine atom and does not follow the octet rule. solid bar (the covalent bond).
It is surrounded by only the two electron pairs that it shares with the
fluorine ­atoms. (b)—Hydrogen chloride, HCl
.. ..
. . ​  : Be: ​ F
: ​ F . . ​  :
According to VSEPR theory, the shared pairs will be as far away from MC99PEC06000018A
(b)—Hydrogen chloride,
(b) Hydrogen chloride, HCl HCl
each other as possible. As shown in Figure 5.2a on the next page, the (b) A hydrogen chloride molecule
distance between electron pairs is maximized if the bonds to fluorine are is composed of dissimilar atoms,
on opposite sides of the beryllium atom, 180° apart. Thus, all three atoms MC99PEC06000018A
but it is still l­inear.
lie on a straight l­ ine. The molecule is linear.

Chemical Bonding 193

 Figure 5.2 If we represent the central atom in a molecule by the
letter A and the atoms bonded to the central atom by the
Molecular Geometry Ball­-­and­-­stick models show the letter B, then according to VSEPR theory, BeF2 is an
shapes of molecules according to ­VSEPR theory. example of an AB2 molecule, which is linear. Can you
180˚ determine what an AB3 molecule looks like? The three
A—B bonds stay farthest apart by pointing to the corners
of an equilateral triangle, giving 120° angles between the
bonds. This trigonal­-­planar geometry is shown in
AB2 Figure 5.2b for the AB3 molecule boron trifluoride, BF3.
(a) Beryllium fluoride, BeF2
The central atoms in AB4 molecules follow the octet
rule by sharing four electron pairs with B atoms, for a total
of eight shared electrons. The distance between electron
120˚ pairs is maximized if each A­—B bond points to one of four
corners of a tetrahedron. This geometry is shown in
Figure 5.2c for the AB4 molecule methane, CH4. The same
AB3 figure shows that in a tetrahedral molecule, each of the
(b) Boron trifluoride, BF3 bond angles formed by the A atom and any two of the
B atoms is equal to ­109.5°.
The shapes of various molecules are summarized in the
table on the next spread (Figure 5.4). B can represent a single
109.5˚
type of atom, a group of identical atoms, or a group of
different atoms in the same molecule. The shape of the
molecule will still be based on the forms given in the table.
However, different sizes of B groups distort the bond angles,
AB4 making some bond angles larger or smaller than those given
(c) Methane, CH4 in the ­table.

go online

VSEPR Theory and Molecular Geometry Learn It! Video

HMHScience.com
Sample Problem E Use VSEPR theory to predict the molecular
geometry of boron trichloride, BCl3. Solve It! Cards
HMHScience.com

Solve First write the Lewis structure for BCl3. Boron is

in Group 13 and has three valence ­electrons.
.  
. ​  B ​.
Chlorine is in Group 17, so each chlorine . . atom has seven valence ­electrons.
: Cl​  . ​:
The total number of available valence electrons is therefore 24e- (3e- from
boron and 21e- from chlorine). The following Lewis structure uses all 24e-.
..
:​   ​:
​  . . Cl
   . . . .  ​
: ​ Cl
  . .  ​: ​ Cl
 ​ : ​  B . . ​  :
This molecule is an exception to the octet rule because in this case B forms only
three bonds. Boron trichloride is an AB3 type of molecule. Therefore, according
to VSEPR theory, it should have trigonal­-p ­ lanar ­geometry.

Answers in Appendix E

1. Use VSEPR theory to predict the molecular geometry of the following m

­ olecules:
a. HI   b. CBr4   c. CH2Cl2

194 Chapter 6
 VSEPR Theory and Unshared Electron Pairs
Ammonia, NH3, and water, H2O, are examples of molecules in which the
central atom has both shared and unshared electron pairs (see Figure 5.4
on the next page for their Lewis structures). How does VSEPR theory
account for the geometries of these ­molecules?
The Lewis structure of ammonia shows that in addition to the three
electron pairs it shares with the three hydrogen atoms, the central nitrogen
atom has one unshared pair of ­electrons.
..
H:​ N  ​  :H
​  . .  ​
  
H
VSEPR theory postulates that the lone pair occupies space around the
nitrogen atom just as the bonding pairs do. Thus, as in an AB4 molecule,
the electron pairs maximize their separation by assuming the four
corners of a tetrahedron. Lone pairs do occupy space, but our description
of the observed shape of a molecule refers to the positions of atoms only.
Consequently, as shown in Figure 5.3a, the molecular geometry of an
ammonia molecule is that of a pyramid with a triangular base. The
general VSEPR formula for molecules such as ammonia is AB3E, where
E represents the unshared electron p­ air.
A water molecule has two unshared electron pairs. It is an AB2E2
molecule. Here, the oxygen atom is at the center of a tetrahedron, with
two corners occupied by hydrogen atoms and two by the unshared pairs
(Figure 5.3b). Again, VSEPR theory states that the lone pairs occupy space
around the central atom but that the actual shape of the molecule is
determined by the positions of the atoms only. In the case of water, this
results in a “bent,” or angular, molecule. In Figure 5.3b, the bond angles in
ammonia and water are somewhat less than the 109.5° bond angles of a
perfectly tetrahedral molecule, because the unshared electron pairs repel
electrons more strongly than do bonding electron pairs.

Figure 5.3

Molecular Shape The locations of bonds and unshared critical thinking

electrons are shown for molecules of (a) ammonia and (b) water. Explain Why would unshared electrons affect the geometry
Although unshared electrons occupy space around the central atoms, of a molecule?
the shapes of the molecules depend only on the position of the
molecules’ atoms, as clearly shown by the ball­-a­ nd­-­stick ­models.

107˚ 105˚

N O

H
H H

H H

(a) Ammonia, NH3 (b) Water, H 2 O

Chemical Bonding 195

MC99PEC06000020aA
 Figure 5.4 also includes an example of an AB2E-type molecule. This
type of molecule results when a central atom forms two bonds and
retains one unshared electron ­pair.
Finally, in VSEPR theory, double and triple bonds are treated in the
same way as single bonds. And polyatomic ions are treated similarly to
molecules. (Remember to consider all of the electron pairs present in any
ion or molecule.) Thus, Lewis structures and Figure 5.4 can be used
together to predict the shapes of polyatomic ions as well as molecules
with double or triple bonds.

Figure 5.4

VSEPR Theory and Molecular Geometry

Atoms Lone
bonded to pairs of Type of Formula
Molecular shape central a
­ tom electrons molecule example Lewis structure
.. ..
Linear 2 0 AB2 BeF2 : ​  .F. ​ - Be -​ .F. :​
.. ..
: ​.F.​  ​F.​  :
.
     
Trigonal- ​
      B  ​
3 0 AB3 BF3
planar �
: ​ .F.​  :
F  Be F
. ​ ​
​  . ​
Bent or F  Be
N F
2 1 AB2E ONF N
Angular ​  .​  .    O
 ​ ​ F. .
O    . . N ​ .F. :​
FO H FF
B�
Tetrahedral 4 0 AB4 CH4 H
F C –​ ​   ​​– H
F F
B�
H F
H
..
​ H​  C ​ N​ H​ ​
H
Trigonal- |
pyramidal
3 1 AB3E NH3 H H C H
​   ​HH
90 H
N

Bent or ​  .​ .      
​H H. ​. H​ ​
N
O
120 2 2 AB2E2 H2O
Angular HH H
O HH
90 H H
90 O
90
90
9090 H Cl H
90 Cl
Trigonal- 120
120
90 5 0 AB5 PCl5 Cl P
Cl Cl
bipyramidal 120
120120 Cl
90
90 Cl Cl
P
12090
Cl Cl
90 9090
90 F F F
90 120
90
90
90
90 F FS
90 F F FF
Octahedral 6 0 AB6 SF6 S
90 F F F
90

196 Chapter 6
 VSEPR Theory and Molecular Geometry

Sample Problem F
a. Use VSEPR theory to predict the shape of a molecule of hydrogen bromide, HBr.
b. Use VSEPR theory to predict the shape of a phosphite ion, ​PO –3​ ​.

Solve a. The Lewis structure of hydrogen bromide shows a single hydrogen-

bromine bond and no unshared electron pairs. To simplify the molecule’s
Lewis structure, we represent the covalent bonds with lines instead of ­dots.
..
H — Br ​  . . ​ :
This is an AB2 molecule, which is ­linear.
b. The Lewis structure of a phosphite shows three oxygen atoms and an
unshared pair of electrons surrounding a central phosphorus atom. Again,
lines are used to represent the covalent ­bonds.
. . .. ..
:​ O . . ​:
. . ​  — ​ P ​ —  ​ O
:​ O
. . ​:
The phosphite ion is an AB3E type. It has trigonal­-­pyramidal geometry, with
the three oxygen atoms at the base of the pyramid and the phosphorus
atom at the ­top.

Answers in Appendix E

1. Use VSEPR theory to predict the molecular geometries of the molecules whose Lewis
structures are given b
­ elow.
.. ..
      :​ Br ​: :​ Cl ​:
.. .. .. ..
a. :​ Br
. . ​— C — ​ Br
. . :​    b. :​ Cl
. . ​— B — Cl
​ . . :​
        :​ Br. . :​

Main Idea
Multiple orbitals can combine to form hybrid orbitals.
VSEPR theory is useful for explaining the shapes of molecules. However,
it does not reveal the relationship between a molecule’s geometry and the
orbitals occupied by its bonding electrons. To explain how the orbitals
become rearranged when an atom forms covalent bonds, a different
model is used. This model is called hybridization, which is the mixing of two
or more atomic orbitals of similar energies on the same atom to produce new
hybrid atomic orbitals of equal energies. Methane, CH4, provides a good
example of how hybridization is used to explain the geometry of molecu-
lar orbitals. The orbital notation for a carbon atom shows that it has four
valence electrons, two in the 2s orbital and two in the 2p ­orbitals.
↑↓ _ ↑↓ _ ↑ ↑
C   ​ _ ​   ​ ​ _ ​ ​ _ ​ ​
 ​ ​   ​ ​    
1s 2s ​      ​
2p

Chemical Bonding 197

 Figure 5.5 ↑ ↑
2p Hybridization ↑ ↑ ↑ ↑
Hybridization of Carbon The sp 3

Energy
hybridization of carbon’s outer orbitals ↑↓ sp 3
combines one s and three p orbitals to 2s
form four sp 3 hybrid orbitals. Whenever ↑↓ ↑↓
hybridization occurs, the resulting hybrid 1s 1s
orbitals are at an energy level between the Carbon’s orbitals Carbon’s orbitals after
levels of the orbitals that have ­combined. before hybridization sp3 hybridization

We know from experiments that a methane molecule has tetrahedral

geometry. How does carbon form four equivalent, tetrahedrally arranged
covalent bonds by orbital overlap with four other ­atoms?
Two of carbon’s valence electrons occupy the 2s orbital, and two
occupy the 2p orbitals. Recall that the 2s orbital and the 2p orbitals have
different shapes. To achieve four equivalent bonds, carbon’s 2s and three
2p orbitals hybridize to form four new, identical orbitals called sp3
orbitals. The superscript 3 indicates that three p orbitals were included in
the hybridization; the superscript 1 on the s is understood. The sp3
orbitals all have the same energy, which is greater than that of the 2s
orbital but less than that of the 2p orbitals, as shown in Figure 5.5.
Hybrid orbitals are orbitals of equal energy produced by the combination of
two or more orbitals on the same atom. The number of hybrid orbitals
produced equals the number of orbitals that have ­combined. Bonding
with carbon sp3 orbitals is shown in Figure 5.6a for a molecule of methane.
Hybridization also explains the bonding and geometry of many
molecules formed by Group 15 and 16 elements. The sp3 hybridization of
a nitrogen atom ([He]2s22p3) yields four hybrid orbitals—one orbital
containing a pair of electrons and three orbitals that each contain an
unpaired electron. Each unpaired electron is capable of forming a single
bond, as shown for ammonia in Figure 5.6b. Similarly, two of the four sp3
hybrid orbitals of an oxygen atom ([He]2s22p4) are occupied by two
electron pairs, and two are occupied by unpaired electrons. Each un-
paired electron can form a single bond, as shown for water in Figure 5.6c.

Figure 5.6

Hybrid Orbitals Bonds formed by the overlap of the 1s orbitals of (c) oxygen. For the sake of clarity, only the hybrid orbitals of the central
hydrogen atoms and the sp 3 orbitals of (a) carbon, (b) nitrogen, and atoms are ­shown.

C N O
H H H
H H

H H H

(a) Methane, CH 4 (b) Ammonia, NH 3 (c) Water, H2 O

198 Chapter 6
 Figure 5.7

Geometry of Hybrid Orbitals

Atomic Type of Number o ­ f
orbitals hybridization hybrid orbitals Geometry

s, p sp 2
180
180
180
Linear
Linear
s, p, p sp2 3 Linear

120
Trigonal-planar
120
Trigonal-planar
120
Trigonal-planar
s, p, p, p sp3 4 109.5
109.5
109.5

Tetrahedral
Tetrahedral
MC99PEC06000022A
Tetrahedral
MC99PEC06000022A
MC99PEC06000022A

The linear geometry of molecules such as beryllium fluoride, BeF2,

is made possible by hybridization involving the s orbital and one available
empty p orbital to yield sp hybrid orbitals. The trigonal-planar geometry of
molecules such as boron fluoride, BF3, is made possible by hybridization
involving the s orbital, one singly occupied p orbital, and one empty
p orbital to yield sp2 hybrid orbitals (see Figure 5.7).

Main Idea
Weak forces exist between molecules.
As a liquid is heated, the kinetic energy of its particles increases. At the
boiling point, the energy is sufficient to overcome the force of attraction
between the liquid’s particles. The particles pull away from each other
and enter the gas phase. Boiling point is therefore a good measure of the
force of attraction between particles of a liquid. The higher the boiling
point, the stronger the forces between p ­ articles.
The forces of attraction between molecules are known as intermolecular
forces. Intermolecular forces vary in strength but are generally weaker than
bonds that join atoms in molecules, ions in ionic compounds, or metal
atoms in solid metals. Compare the boiling points of the metals and ionic
compounds in Figure 5.8 (on the next page) with those of the molecular
substances listed. Note that the values for ionic compounds and metals are
much higher than those for molecular ­substances.

Chemical Bonding 199

 Figure 5.8

Boiling Points and Bonding Types

Bonding type Substance bp (1 atm, °C)

Nonpolar-covalent H2 −253
(molecular) O2 −183
Cl2 −34
Br2 59
CH4 −164
CCl4 77
C6H6 80

Polar-covalent PH3 −88

(molecular) NH3 −33
H2S −61
H2O 100
HF 20
HCl −85
ICl 97

Ionic NaCl 1413

MgF2 2239

Metallic Cu 2567
Fe 2750
W 5660
Computational
Chemist
Computational chemistry is the Molecular Polarity and Dipole-Dipole Forces
study of molecules, their properties, The strongest intermolecular forces exist between polar molecules.
and the interactions between them, Polar molecules act as tiny dipoles because of their uneven charge
using mathematical equations that distribution. A dipole is created by equal but opposite charges that are
are based on the laws of quantum
separated by a short distance. The direction of a dipole is from the dipole’s
mechanics and which describe the
positive pole to its negative pole. A dipole is represented by an arrow with
motion of the electrons. Today, widely-
a head pointing toward the negative pole and a crossed tail situated at
available software packages exist
the positive pole. The dipole created by a hydrogen chloride molecule,
that allow chemists to solve these
which has its negative end at the more electronegative chlorine atom, is
equations for molecules under study.
Computational chemists combine
indicated as f­ ollows.
their expertise in mathematics, their -
↦
computer skills, and their love of H-Cl
chemistry. Computational chemistry
The negative region in one polar molecule attracts the positive region
has been used in industry to aid in
the discovery of new pharmaceutical
in adjacent molecules, and so on throughout a liquid or solid. The forces
drugs and new catalysts. Computa­ of attraction between polar molecules are known as dipole­-­dipole forces.
tional chemists are employed in all These forces are short­-­range forces, acting only between nearby mol-
areas of chemistry and work closely ecules. The effect of dipole­-d
­ ipole forces is reflected, for example, by the
with experimental chemists. significant difference between the boiling points of iodine chloride, I—Cl,
and bromine, Br—Br. The boiling point of polar iodine chloride is 97 °C,
whereas that of nonpolar bromine is only 59 °C. The dipole­-­dipole forces
responsible for the relatively high boiling point of ICl are illustrated
schematically in Figure 5.9 (on the next page).

200 Chapter 6
 Figure 5.9

Dipole-Dipole Forces Ball-and-stick δ+ δ- δ+ δ– Key:

models illustrate the dipole-dipole forces
between molecules of iodine chloride, ICl.
In each molecule, the highly electronegative
chlorine atom has a partial negative charge,
leaving each iodine atom with a partial
positive charge. Consequent­ly, the negative Cl
and positive ends of neighboring molecules
Dipole-dipole
attract each other.
δ- δ+ δ+ forces
δ–

The polarity of diatomic molecules such as ICl is determined by just

one bond. For molecules containing more than two atoms, molecular
polarity depends on both the polarity and the orientation of each bond.
A molecule of water, for example, has two hydrogen­-o ­ xygen bonds in which
the more­-­electronegative oxygen atom is the negative pole of each bond.
Because the molecule is bent, the polarities of these two bonds combine
to make the molecule highly polar, as shown in Figure 5.10. An ammonia
molecule is also highly polar because the dipoles of the three nitrogen­-­
hydrogen bonds are additive, combining to create a net molecular dipole.
In some molecules, individual bond dipoles cancel one another, causing
the resulting molecular polarity to be zero. Carbon dioxide and carbon
tetrachloride are molecules of this type.
A polar molecule can induce a dipole in a nonpolar molecule by
temporarily attracting its electrons. The result is a short­-­range intermo-
lecular force that is somewhat weaker than the dipole-dipole force. The
force of an induced dipole accounts for the slight solubility of nonpolar
O2 in water. The positive pole of a water molecule attracts the outer

Figure 5.10 δ-
δ–
Bond Polarities (a) The bond
polarities in a water or an ammonia
molecule are additive, causing the δ+
molecule as a whole to be ­polar.
δ+
(b) In molecules of carbon tetrachloride
and carbon dioxide, the bond polarities (a)—Water, H2O Ammonia, NH 3
extend equally and symmetrically in
different directions, canceling each
other’s effect and causing each
molecule as a whole to be ­nonpolar.
MC99PEC06000024aA
critical thinking
Explain What explanation can you
give for the fact that the boiling point
of H20 is significantly higher than the
boiling point of either H2 (g) or O2 (g)
alone? (b) Carbon tetrachloride, CCl 4 Carbon dioxide, CO 2
(no molecular dipole) (no molecular dipole)

Chemical Bonding 201

 Figure 5.11

Dipole-Induced Dipole Interaction The positive pole of a of an oxygen molecule. The negative pole induced in the oxygen
water molecule causes a temporary change in the electron distribution molecule is then attracted to the positive pole of the water molecule.

δ+ δ+

δ- δ+

δ– δ-

δ+ δ+

Water, H 2 O Oxygen, O 2
electrons of an adjacent oxygen molecule. The oxygen molecule, then,
has an induced negative pole on the side toward the water molecule and
an induced positive pole on the opposite side. The result is an attraction
MC99PEC06000026A to the water ­molecule, as shown in Figure 5.11.

Hydrogen Bonding
Some hydrogen-containing compounds, such as hydrogen fluoride
(HF), water (H2O), and ammonia (NH3), have unusually high boiling
points. This is explained by the presence of a particularly strong type
of dipole-dipole force. In compounds containing H—F, H—O, or H—N
bonds, the large electronegativity differences between hydrogen atoms
and fluorine, oxygen, or nitrogen atoms make the bonds connecting
them highly polar. This gives the hydrogen atom a positive charge that
is almost half as large as that of a proton. Moreover, the small size of
the hydrogen atom allows the atom to come very close to an unshared
pair of electrons on an adjacent molecule. The intermolecular force in
which a hydrogen atom that is bonded to a highly electronegative atom is
attracted to an unshared pair of electrons of an electronegative atom in a
nearby molecule is known as hydrogen bonding.
Figure 5.12
Hydrogen bonds are usually represented by
Hydrogen Bonding Space-filling models illustrate hydrogen dotted lines connecting the hydrogen­-­bonded
bonding between water molecules. The dotted lines indicate the hydrogen to the unshared electron pair of the
attraction between electronegative oxygen atoms and electropositive electronegative atom to which it is attracted, as
hydrogen atoms of neighboring ­molecules. illustrated for water in Figure 5.12. The effect of
hydrogen bonding can be seen by comparing the
boiling points in Figure 5.8. Look at phosphine, PH3,
compared with hydrogen­-­bonded ammonia, NH3.
©Serge Krouglikoff/Digital Vision/Getty Images

How does hydrogen sulfide, H2S, compare with

hydrogen­-­bonded water, H2O?
In living organisms, hydrogen bonds play an
extremely important role: that of stabilizing the
structure of deoxyribonucleic acid (DNA).
Hydrogen bonds are individually very weak, but the
sum of millions of these bonds forms a very strong
force holding two DNA strands together.

202 Chapter 6
Figure 5.13

Temporary Dipoles When an instantaneous, temporary dipole

develops in a helium atom, it induces a dipole in a neighboring ­atom.

– – –
+2 +2
– – +2 +2
– – Weak –
attractive
force
Momentary dipole Dipole induced in
in one helium atom neighboring atom

London Dispersion Forces

Even noble­-­gas atoms and molecules that are nonpolar experience a
weak intermolecular attraction. In any atom or molecule—polar or
nonpolar—the electrons are in continuous motion. As a result, at any
instant, the electron distribution may be slightly uneven. The momen-
tary, uneven charge creates a positive pole in one part of the atom or
molecule and a negative pole in another. This temporary dipole can then
induce a dipole in an adjacent atom or molecule. The two are held
together for an instant by the weak attraction between the temporary
dipoles, as illustrated in Figure 5.13. The intermolecular attractions resulting
from the constant motion of electrons and the creation of instantaneous
dipoles are called London dispersion forces, after Fritz London, who first
proposed their existence in 1
­ 930.
London forces act between all atoms and molecules. But they are the
only intermolecular forces acting among noble­-­gas atoms and nonpolar
molecules. This fact is reflected in the low boiling points of the noble
gases and nonpolar molecular compounds listed in Figure 5.8. Because
London forces are dependent on the motion of electrons, their strength
increases with the number of electrons in the interacting atoms or
molecules. In other words, London forces increase with increasing atomic
or molar mass. This trend can be seen by comparing the boiling points of
the gases helium, He, and argon, Ar; hydrogen, H2, and oxygen, O2; and
chlorine, Cl2, and bromine, Br2.

Section 5 Formative ASSESSMENT

Reviewing Main Ideas 4. Explain what is meant by sp3 ­hybridization.

1. What two theories can be used to predict 5. What type of intermolecular force contributes to
molecular ­geometry? the high boiling point of water? E
­ xplain.

2. Draw the Lewis structure and predict the mo­

Critical Thinking
lecular geometry of the following m
­ olecules:
a. SO2 b. CI4 c. BCl3 6. inferring relationships What
experimental property directly correlates
3. What factors affect the geometry of a ­molecule? with the strength of the intermolecular forces?
Briefly explain your answer.

Chemical Bonding 203

Math Tutor Drawing Lewis Structures

Drawing Lewis dot structures can help you understand how structures for covalently bonded atoms are written, the dots
valence electrons participate in bonding. Dots are placed may be placed as needed to show the electrons shared in each
around the symbol of an element to represent the element’s bond. Most atoms bond in a way that gives them a stable octet
valence electrons. For example, carbon has four valence . of s and p electrons in the highest energy level. So whenever
electrons, and its Lewis dot structure is usually written as . C. .. possible, dots should be arranged in a way that represents a
An atom of fluorine has seven valence electrons. Fluorine’s stable octet around each atom.
..
Lewis dot structure can be written as : F. :. When Lewis

Problem-Solving TIPS
• Hydrogen is an exception to the octet rule, because hydrogen has only one electron and becomes stable
with two electrons.
• Some elements, such as boron, can bond without achieving an octet, because they have three or fewer
electrons to share.

Sample Problem

Draw the Lewis dot structure for a molecule of sulfur dichloride, SCl2.

First, write the electron-dot notation for each. . atom. .. .

: Cl
.: : Cl
.: : S. :

Next, determine the total number of valence electrons in the atoms.

S 1 × 6e- = 6e-

2Cl 2 × 7e- = 14e-

Total e- = 20e-

Arrange the atoms to form a skeleton structure for the molecule, and place electron pairs between atoms
to represent covalent bonds. You can predict the arrangement of atoms by figuring out how many covalent
bonds each atom must form in order to achieve a stable octet. Each chlorine atom, which has 7 valence
electrons, must form a single covalent bond. Sulfur, which has 6 valence electrons, must form two covalent
bonds. The only possible structure is Cl-S-Cl.

Finally, insert dots representing the remaining electrons (16 in this case), in order to give each
atom an octet. .. .. ..
: Cl
. . : .S. : Cl
.. :

1. Draw the electron-dot notations for a silicon atom and a strontium atom.
2. Draw Lewis structures for hydrogen sulfide, H2S, and formic acid, HCO2H.

204 Chapter 6
 BIG IDEA Atoms form chemical bonds by

CHAPTER 6 Summary sharing or transferring electrons.

SECTION 1 Introduction to Chemical Bonding KEY TERMS

• Most atoms are chemically bonded to other atoms. The three chemical bond nonpolar-covalent
major types of chemical bonding are ionic, covalent, and ionic bonding bond
metallic. polar
covalent bonding
• In general, atoms of metals bond ionically with atoms of non- polar-covalent bond
metals, atoms of metals bond metallically with each other, and
atoms of nonmetals bond covalently with each other.

SECTION 2 Covalent Bonding and Molecular KEY TERMS

Compounds
• Atoms in molecules are joined by covalent bonds. In a covalent molecule Lewis structure
bond, two atoms share one or more pairs of electrons. molecular compound structural formula
• The octet rule states that many chemical compounds tend to chemical formula single bond
form bonds so that each atom shares or has eight electrons in
molecular formula multiple bond
its highest occupied energy level.
bond energy resonance
• Bonding within many molecules and ions can be indicated by a
Lewis structure. Molecules or ions that cannot be correctly electron-dot notation
represented by a single Lewis structure are represented by
resonance structures.

SECTION 3 Ionic Bonding and Ionic KEY TERMS

Compounds
• An ionic compound is a three-dimensional network of positive ionic compound
and negative ions mutually attracted to one another. formula unit
• Ionic compounds tend to be harder and more brittle and have lattice energy
higher boiling points than materials containing only covalently
polyatomic ion
bonded atoms.

SECTION 4 Metallic Bonding KEY TERMS

• The “electron sea” formed in metallic bonding gives metals their metallic bonding
properties of high electrical and thermal conductivity, malleabil- malleability
ity, ductility, and luster.
ductility

SECTION 5 Molecular Geometry KEY TERMS

• VSEPR theory is used to predict the shapes of molecules based VSEPR theory
on the fact that electron pairs strongly repel each other. hybridization
• Hybridization theory is used to predict the shapes of molecules, hybrid orbitals
based on the fact that orbitals within an atom can mix to form
dipole
orbitals of equal energy.
hydrogen bonding
• Intermolecular forces include dipole-dipole forces and London
dispersion forces. Hydrogen bonding is a special case of London dispersion
forces
dipole-dipole forces.

Chapter Summary 205

 Review
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CHAPTER 6 Interactive Review

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SECTION 1 SECTION 2

Introduction to Chemical Covalent Bonding and

Bonding Molecular Compounds
REVIEWING MAIN IDEAS REVIEWING MAIN IDEAS
1. What is a chemical bond? 10. What is a molecule?

2. Identify and define the three major types of chemical 11. a. What determines bond length?
bonding. b. In general, how are bond energies and bond
lengths related?
3. What is the relationship between electronegativity
and the ionic character of a chemical bond? 12. Describe the general location of the electrons in a
covalent bond.
4. a. What is the meaning of the term polar as applied
to chemical bonding? 13. As applied to covalent bonding, what is meant by an
b. Distinguish between polar-covalent and unshared or lone pair of electrons?
nonpolar-covalent bonds.
14. Describe the octet rule in terms of noble-gas configu-
5. In general, what determines whether atoms will form rations and potential energy.
chemical bonds?
15. Determine the number of valence electrons in an
atom of each of the following elements:
PRACTICE PROBLEMS a. H
6. Determine the electronegativity difference, the b. F
probable bond type, and the more-electronegative c. Mg
atom with respect to bonds formed between the d. O
following pairs of atoms. (Hint: See Sample e. Al
Problem A.) f. N
a. H and I g. C
b. S and O
16. In a Lewis structure, which atom is usually the
c. K and Br
central atom?
d. Si and Cl
e. K and Cl 17. Distinguish between single, double, and triple
f. Se and S covalent bonds by defining each and providing an
g. C and H illustration of each type.

7. List the bonding pairs described in item 6 in order of 18. For Lewis structures, how is the need for multiple
increasing covalent character. bonds generally determined?

8. Use orbital notation to illustrate the bonding in each

of the following molecules:
PRACTICE PROBLEMS
a. chlorine, Cl2 19. Use Lewis valence electron dot structures to express
b. oxygen, O2 the arrangement of valence electrons present in one
c. hydrogen fluoride, HF atom of each of the following elements. (Hint: See
Sample Problem B.)
9. The lattice energy of sodium chloride, NaCl, is
a. Li e. C
-787.5 kJ/mol. The lattice energy of potassium
b. Ca f. P
chloride, KCl, is -715 kJ/mol. In which compound is
c. Cl g. Al
the bonding between ions stronger? Why?
d. O h. S

206 Chapter 6
 CHAPTER REVIEW

20. Use electron-dot structures to demonstrate the 28. a. In general, how do ionic and molecular
formation of ionic compounds involving the compounds compare in terms of melting points,
following elements: boiling points, and ease of vaporization?
a. Na and S b. What accounts for the observed differences in the
b. Ca and O properties of ionic and molecular compounds?
c. Al and S c. Cite three physical properties of ionic compounds.

21. Draw Lewis structures for each of the following 29. a. What is a polyatomic ion?
molecules. (Hint: See Sample Problem D.) b. Give two examples of polyatomic ions.
a. contains one C and four F atoms c. In what form do such ions often occur in nature?
b. contains two H and one Se atom
c. contains one N and three I atoms SECTION 4
d. contains one Si and four Br atoms
e. contains one C, one Cl, and three H atoms Metallic Bonding
22. Determine the type of hybrid orbitals formed by the REVIEWING MAIN IDEAS
boron atom in a molecule of boron fluoride, BF3.
30. a. How do the properties of metals differ from those
23. Draw Lewis structures for each of the following of both ionic and molecular compounds?
molecules. Show resonance structures, if they exist. b. What specific property of metals accounts for their
a. O2 unusual electrical conductivity?
b. N2
31. What properties of metals contribute to their
c. CO
tendency to form metallic bonds?
d. SO2
32. a. What is metallic bonding?
24. Draw Lewis structures for each of the following
b. How can the strength of metallic bonding be
polyatomic ions. Show resonance structures, if they
measured?
exist.
a. OH-
b. H3C2O - SECTION 5
2
c. BrO -
3 Molecular Geometry
SECTION 3 REVIEWING MAIN IDEAS

Ionic Bonding and Ionic 33. a. How is the VSEPR theory used to classify
molecules?
Compounds b. What molecular geometry would be expected for
F2 and HF?
REVIEWING MAIN IDEAS
34. According to the VSEPR theory, what molecular
25. a. What is an ionic compound? geometries are associated with the following types
b. In what form do most ionic compounds occur? of molecules?
26. a. What is a formula unit? a. AB2
b. What are the components of one formula unit b. AB3
of CaF2? c. AB4
d. AB5
27. a. What is lattice energy? e. AB6
b. In general, what is the relationship between lattice
energy and the strength of ionic bonding? 35. Describe the role of each of the following in
predicting molecular geometries:
a. unshared electron pairs
b. double bonds

Chapter Review 207

CHAPTER REVIEW

36. a. What are hybrid orbitals? 47. On the basis of individual bond polarity and
b. What determines the number of hybrid orbitals orientation, determine whether each of the
produced by the hybridization of an atom? following molecules would be polar or nonpolar:
a. H2O
37. a. What are intermolecular forces? b. I2
b. In general, how do these forces compare in c. CF4
strength with those in ionic and metallic bonding? d. NH3
c. What types of molecules have the strongest e. CO2
intermolecular forces?
48. Draw a Lewis structure for each of the following
38. What is the relationship between electronegativity molecules, and then use the VSEPR theory to predict
and the polarity of a chemical bond? the molecular geometry of each:
39. a. What are dipole-dipole forces? a. SCl2
b. What determines the polarity of a molecule? b. PI3
c. Cl2O
40. a. What is meant by an induced dipole? d. NH2Cl
b. What is a consequence of this type of intermolecu- e. SiCl3Br
lar force? f. ONCl
41. a. What is hydrogen bonding? 49. Draw a Lewis structure for each of the following
b. What accounts for its extraordinary strength? polyatomic ions, and then use VSEPR theory to
determine the geometry of each:
42. What are London dispersion forces?
a. NO -3
b. NH +4
PRACTICE PROBLEMS c. SO 2-
4
43. According to the VSEPR theory, what molecular d. ClO -2
geometries are associated with the following types of

Mixed Review
molecules?
a. AB3E
b. AB2E2 REVIEWING MAIN IDEAS
c. AB2E
50. Arrange the following pairs from strongest to weakest
44. Use hybridization to explain the bonding in attraction:
methane, CH4. a. polar molecule and polar molecule
45. For each of the following polar molecules, indicate b. nonpolar molecule and nonpolar molecule
the direction of the resulting dipole: c. polar molecule and ion
a. H-F d. ion and ion
b. H-Cl 51. Determine the geometry of the following molecules:
c. H-Br a. CCl4
d. H-I b. BeCl2
46. Determine whether each of the following bonds c. PH3
would be polar or nonpolar: 52. What types of atoms tend to form the following types
a. H-H of bonding?
b. H-O a. ionic
c. H-F b. covalent
d. Br-Br c. metallic
e. H-Cl
f. H-N

208 Chapter 6
 CHAPTER REVIEW

53. What happens to the energy level and stability of two 66. Draw a Lewis structure for each of the following
bonded atoms when they are separated and become polyatomic ions and determine their geometries:
individual atoms? a. NO -
2
b. NO -
3
54. Draw the three resonance structures for sulfur c. NH +
4
trioxide, SO3.
67. Why do most atoms tend to bond to other atoms?
55. a. How do ionic and covalent bonding differ?
b. How does an ionic compound differ from a
molecular compound? CRITICAL THINKING
c. How does an ionic compound differ from a metal?
68. Inferring Relationships The length of a bond varies
56. Write the electron-dot notation for each of the depending on the type of bond formed. Predict and
following elements: compare the lengths of the carbon-carbon bonds in
a. He the following molecules. Explain your answer. (Hint:
b. Cl See Figure 2.10)
c. O
H H H H
d. P    
e. B
H- C - C -H H- C = C -H H-C≡C-H
57. Write the structural formula for methanol, CH3OH.  
H H
58. How many K+ and S2- ions would be in one formula
C2H6 C2H4 C2H2
unit of the ionic compound formed by these ions?
69. Why does F generally form covalent bonds with great
59. Explain metallic bonding in terms of the sparsely
polarity?
populated outermost orbitals of metal atoms.
70. Explain what is wrong with the following Lewis
60. Explain the role of molecular geometry in
structures, and then correct each one.
determining molecular polarity.
..
a. H-H-.S.:
61. How does the energy level of a hybrid orbital
compare with the energy levels of the orbitals :O:
from which it was formed?  ..
b. H- C =O . . -H
62. Aluminum’s enthalpy of vaporization is 284 kJ/mol.
..
Beryllium’s enthalpy of vaporization is 224 kJ/mol. :Cl :
In which element is the bonding stronger between 
c.
atoms? N
63. Determine the electronegativity difference, the .. ..
probable bonding type, and the more-electronegative
: Cl
.. .. :
Cl
atom for each of the following pairs of atoms: 71. Ionic compounds tend to have higher boiling points
a. Zn and O than covalent substances do. Both ammonia, NH3, and
b. Br and I methane, CH4, are covalent compounds, yet the boiling
c. S and Cl point of ammonia is 130 °C higher than that of meth-
ane. What might account for this large difference?
64. Draw the Lewis structure for each of the following
molecules:
a. PCl3 USING THE HANDBOOK
b. CCl2F2
c. CH3NH2 72. Figure 4.1 shows a model for a body-centered cubic
crystal. Review the Properties tables for all of the
65. Draw the Lewis structure for BeCl2. (Hint: Beryllium metals in the Elements Handbook (Appendix A). What
atoms do not follow the octet rule.) metals exist in body-centered cubic structures?

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CHAPTER REVIEW

73. Group 14 of the Elements Handbook (Appendix A) 77. Searching for the perfect artificial sweetener—great
contains a discussion of semiconductors and the taste with no Calories—has been the focus of chemi-
band theory of metals. How does this model explain cal research for some time. Molecules such as
the electrical conductivity of metals? sucralose, aspartame, and saccharine owe their
sweetness to their size and shape. One theory holds
that any sweetener must have three sites that fit into
RESEARCH AND WRITING the proper taste buds on the tongue. This theory is
appropriately known as the triangle theory. Research
74. Prepare a report on the work of Linus Pauling. artificial sweeteners to develop a model to show how
a. Discuss his work on the nature of the chemical the triangle theory operates.
bond.
b. Linus Pauling was an advocate of the use of
vitamin C as a preventative for colds. Evaluate ALTERNATIVE ASSESSMENT
Pauling’s claims. Determine if there is any scien-
tific evidence that indicates whether vitamin C 78. Devise a set of criteria that will allow you to classify
helps prevent colds. the following substances as ionic or non-ionic:
CaCO3, Cu, H2O, NaBr, and C (graphite). Show your
75. Covalently bonded solids, such as silicon, an element criteria to your instructor.
used in computer components, are harder than pure
metals. Research theories that explain the hardness of 79. Performance Assessment Identify 10 common
covalently bonded solids and their usefulness in the substances in and around your home, and indicate
computer industry. Present your findings to the class. whether you would expect these substances to
contain ionic, covalent, or metallic bonds.
76. Natural rubber consists of long chains of carbon and
hydrogen atoms covalently bonded together. When
Charles Goodyear accidentally dropped a mixture of
sulfur and rubber on a hot stove, the energy from the
stove joined these chains together to make vulca-
nized rubber (named for Vulcan, the Roman god of
fire). The carbon-hydrogen chains in vulcanized
rubber are held together by two sulfur atoms that
form covalent bonds between the chains. These
covalent bonds are commonly called disulfide
bridges. Explore other molecules that have such
disulfide bridges. Present your findings to the class.

210 Chapter 6
 TEST PREP

Standards-Based Assessment
Record your answers on a separate piece of paper. 5 The Lewis structure of HCN contains
MULTIPLE CHOICE A one double bond and one single bond.
1 Between which two atoms are ionic bonds most B one triple bond and one single bond.
likely to form? (Draw electron-dot structures to help C two single bonds.
you decide.) D two double bonds.
A K and F
6 Which of the following molecules contains a double
B O and O
bond?
C C and H
D N and O A COCl2
B C2H6
2 Which of the following is a possible electron C CF4
configuration ending for an element with the Lewis D SF2
dot structure pictured below?
7 Which of the following represents the correct Lewis
A 4s23d104p3
dot structure for sodium chloride?
B 2s22p1 ..
A Na + : Cl
.. :
X ..
B [Na]- + : Cl .. :
C 3s23p6 .. -
C Na+ + [: Cl . . :]
D 5s24d3
.. +
D [Na]- + : Cl .. :
3 Which of the following correctly illustrates the Lewis
structure for a covalent compound?
GRIDDED RESPONSE
H
8 The first step in constructing a Lewis dot structure
A H C H
for a molecule is to determine how many valence
H
electrons are in all of the atoms contained in the
B C molecule. How many total valence electrons are
H
C H C H contained in the atoms of a molecule of butane,
C4H10?
H
D H C H
H

4 Lewis structures use dots to depict valence elec-

trons. For the following elements, what pattern in
the corresponding Lewis dot structures can you
identify?
lead (Pb) antimony (Sb) sulfur (S) chlorine (Cl)
A The dot structure for each contains the same
number of outer electrons.
B The number of outer electrons increases by 2 for
each element.
C The number of outer electrons increases by 1 for
each element.
D The number of outer electrons corresponds to
11 12 1
Test Tip
the total number of electrons in each element. 2
9
10
3
When several questions refer to the same
8 4 graph, table, drawing, or passage, answer
7 6 5
the questions you are sure of first.

Standards-Based Assessment 211