SECTION 6.

Covalent Bonding and

Molecular Compounds
Most of the chemicals inside living things and produced by KEY TERMS
living things are molecules. A molecule is a neutral group of
molecule
atoms that are held together by covalent bonds. A molecule molecular compound
formed by polar-covalent bonds is still considered neutral chemical formula
molecular formula
because the sum of the partial charges on either end of the bond energy
bond is zero. electron-dot notation
Lewis structure
A molecular compound is any chemical compound structural formula
whose simplest units are molecules. In other words, a single single bond
multiple bond
molecule of any molecular compound is an individual unit resonance
that is capable of existing on its own. A molecule may
contain two or more atoms of the same element, as in
oxygen. Or, a molecule may consist of two or more atoms
of different elements, as in water and sugar.
The composition of a compound is given by its chemical
formula. A chemical formula indicates the relative number
of each type of atom necessary to form a single unit of a
compound. For compounds that form molecules, the
molecular formula shows the types and number of atoms
necessary to form a single molecule.
The molecular formula for water, H2O, shows that two READING CHECK
hydrogen atoms and one oxygen atom are necessary to form 1. The formula for sucrose,
a molecule of water. A molecule of oxygen, O2, contains two C12H22O11, shows that a
atoms of oxygen and is an example of a diatomic molecule.
sucrose molecule contains
A diatomic molecule contains only two atoms.
carbon atoms,

hydrogen atoms, and

(a) Water molecule,
oxygen atoms.
H2O

(b) Oxygen molecule,

O2

(c) Sucrose molecule,

C12H22O11

Three examples of molecular compounds are shown: (a) water, (b) oxygen,
and (c) sucrose.

ChemiCal Bonding 175

 Covalent bonds form from shared electrons.

In Section 1, you learned that nature favors chemical bonding

because atoms have lower potential energy when they are
bonded than they have alone. Examining the formation of a
hydrogen-hydrogen bond can illustrate the point.
The potential energy of two hydrogen atoms changes as the
strengths of the attractive and repulsive forces between the Both nuclei repel
each other, as do both
atoms change. The electrons in each hydrogen atom repel electron clouds.
each other, as do the protons. This repulsion corresponds to
an increase in potential energy, similar to two boulders being –
pushed up opposite sides of a valley. On the other hand, the + +
proton in one atom is attracted to the electron in the other
–
atom, and vice versa. This corresponds to a decrease in
potential energy, similar to two boulders falling down the sides
The nucleus of one atom
of a valley toward each other. attracts the electron cloud of
the other atom, and vice versa.
The graph below shows the total potential energy of the two
hydrogen atoms versus the distance between the atoms.
Consider four stages shown on the graph.
(a) The two atoms do not influence each other. At this point,
the potential energy is defined as zero.
(b) As the atoms approach each other, the electron-proton
attractions are stronger than the electron-electron
and proton-proton repulsions. The net potential
energy decreases.
(c) When the atoms are 75 pm apart, the strengths of the READING CHECK
attractions and repulsions are balanced. This is the point at 2. Two atoms form a stable
which potential energy is at a minimum and a stable
chemical bond when their potential
hydrogen molecule forms.
energies are
(d) If the atoms got any closer together, the repulsive forces
than their potential energies as
would be stronger than the attractive forces, and would
force them apart again. separate particles.
Potential energy (kJ/mol)

0 +
(d) (a)
(b)

75 pm
The graph shows the changes in
-436 (c)
potential energy of two atoms of
75 hydrogen versus the distance between
Distance between hydrogen nuclei (pm) the two atoms.

176 ChaPTeR 6
 Bond lengths and energy vary from molecule
to molecule.

A stable covalent bond forms when the attractive forces

between two atoms balance the repulsive forces between
two atoms. In a hydrogen-hydrogen bond, the electrons of
each hydrogen atom are shared between the two nuclei. The
molecule’s electrons can be pictured as occupying overlapping
orbitals, moving freely in either orbital.

Electron clouds Region of orbital

The orbitals of two hydrogen atoms
overlap
overlap when the atoms bond. Both
electrons feel the attraction from both
nuclei. As a result, the electron density
between the nuclei increases.

Nuclei

Hydrogen atoms Hydrogen molecule

The bonded atoms can vibrate, but they remain bonded

as long as their potential energy remains close to the
minimum value. Bond length is the average distance between READING CHECK
two bonded atoms. The bond length for a hydrogen-hydrogen 3. Define the following terms in
bond is 75 pm. your own words.

Energy in a closed system is always conserved. Therefore, bond:

when two atoms form a bond and their potential energy
decreases by a certain amount, an equal amount of
energy must be released by the atoms. The graph on
the previous page shows that the hydrogen atoms must release energy:
436 kJ/mol of energy when forming a bond. In other words,
436 kJ of energy are released when a mole of hydrogen
molecules forms.
The same amount of energy that is released when a bond 4. Consider a system consisting of
forms is required to force the atoms apart. Bond energy is the one diatomic molecule. When the
energy required to break a chemical bond and form neutral chemical bond is broken, is energy
put into the system or is energy
isolated atoms. The bond energy for a hydrogen-hydrogen taken out of the system?
bond is 436 kJ/mol. In other words, it takes 436 kJ of energy to
break the bonds in a mole of hydrogen molecules.

ChemiCal Bonding 177

 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

The table above shows the average bond lengths and

bond energies for some common covalent bonds. The actual
bond length and bond energy for a particular bond can vary
depending on the influence of the other atoms in a molecule.

Atoms tend to form bonds to follow the octet rule.

As the diagram at the right shows, the overlapping orbital in a Bonding electron pair in
hydrogen molecule contains two electrons. This is the same overlapping orbitals
electron configuration as in a helium atom, which is a stable
noble gas. Each hydrogen atom in the molecule is said to have ↑ ↑
a noble-gas configuration, since its outermost electron shell H H
1s 1s
(the n = 1 shell) is completely filled by the shared electrons.
Usually, the outermost electron shell of an atom in a noble- ↓ ↓
H H
1s 1s
gas configuration contains 8 electrons, with 2 in the outermost
s sublevel and 6 in the outermost p sublevel. Atoms tend to Hydrogen Hydrogen
atoms molecule
form bonds such that they obtain noble-gas configurations.
Thus, the octet rule states that chemical compounds form so By sharing electrons in overlapping
that each atom, by gaining, losing, or sharing electrons, has an orbitals, each hydrogen atom in a
hydrogen molecule experiences
octet of electrons in its highest-occupied energy level. the stable effect of a stable 1s2
configuration.
Critical Thinking
5. Compare What feature do atoms in a noble gas and atoms
in a molecule have in common?

178 ChaPTeR 6
 (a)(a)
↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ Bonding
Bonding
(a) F F ↑↓ ↑↓ ↑↓ ↑↓ ↑ F F ↑↓ ↑↓ ↑↓ ↑↓ ↑ electron
1s 1s2s 2s 1s 1s2s 2s electron
2p2p 2p2p pair in in
pair
overlapping
overlapping
↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓
F F ↑↓ ↑↓ ↑↓ ↑↓ ↓ F F ↑↓ ↑↓ ↑↓ ↑↓ ↓ orbitals
orbitals
1s 1s2s 2s 1s 1s2s 2s
2p2p 2p2p
Fluorine atoms
Fluorine atoms Fluorine
Fluorinemolecule
molecule
Bonding electron
Bonding pair
electron pair
in in
overlapping orbitals
overlapping orbitals
(b)(b)
↑↑ ↑↑
(b) HH HH
1s 1s 1s 1s
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓
ClCl ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ClCl ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓
1s 1s2s 2s 3s 3s 1s 1s2s 2s 3s 3s
2p2p 3p3p 2p2p 3p3p
Hydrogen and
Hydrogen chlorine
and atoms
chlorine atoms Hydrogen chloride
Hydrogen molecule
chloride molecule

One example of a stable molecule that follows the octet (a) Both atoms in a fluorine
rule is the fluorine molecule shown above. A fluorine atom has molecule experience neon’s stable
seven electrons in its outermost energy level, including six 1​s2​ ​2​s2​ ​2​p6​ ​configuration. (b) Both
atoms in an HCl molecule experience
paired electrons and one unpaired electron in a 2p orbital. stable configurations.
When two fluorine atoms bond, they share the unpaired
electrons. The result is that each atom essentially has an octet
of electrons at the n = 2 level.
Another example is an HCl molecule. The chlorine atom
achieves an octet by sharing an electron with a hydrogen atom.
The chlorine essentially gets an eighth electron to give it an
octet at the n = 3 level. The hydrogen atom receives a second
electron to achieve helium’s stable noble-gas configuration.

Exceptions to the Octet Rule

Most main-group elements tend to form covalent bonds Critical Thinking
according to the octet rule. Hydrogen is one exception, as its 6. Apply A chlorine atom has the
atoms only form bonds with two electrons. Boron is another electron configuration [Ne]3​s2​ ​ 3​p​5​.
Explain how atoms in a molecule of
exception. Boron has three valence electrons, [He]2​s2​ ​ 2​p1​ ​. It chlorine (​Cl​2​) follow the octet rule.
forms bonds by sharing all three of its electrons to form three
electron pairs, such as in the molecule B​F​3​.
Other atoms have more than eight electrons in their
outermost energy level when they combine with highly
electronegative elements such as fluorine, oxygen, and chlorine.
In these cases of expanded valence, bonding involves electrons
in the d orbitals as well as the s and p orbitals. P​F5​ ​ and S​F6​ ​ are
two examples of compounds with expanded valence.

Chemical Bonding 179

 Dots placed around an element’s symbol can
represent valence electrons.

Usually, covalent bonds involve only the electrons in the

outermost energy level of an atom. Electron-dot notation is
useful for keeping track of these valence electrons. Electron-
dot notation is an electron-configuration notation in which
only the valence electrons are shown, as dots placed around a
chemical symbol. The inner-shell electrons are not shown.
Electron-dot notation reflects the number of valence
electrons in the outermost energy level. For example, a fluorine
atom has an electron configuration of [He]2s22p5. Each atom
has seven valence electrons, six paired electrons that fill three
orbitals and one unpaired electron in one orbital. Therefore,
the electron-dot notation for fluorine looks like this.
F

The table below shows the electron-dot notation used in this

book for the eight possible numbers of valence electrons
in an atom.

Number of Electron-dot Example Examples of electron-dot notation

valence electrons notation for atoms of elements with 1 to 8
valence electrons.
1 X Na
2 X Mg
3 X B
4 X C

5 X N

6 X O

7 X F

8 X Ne

PRACTICE

Write the electron-dot notation for the following elements.

A. hydrogen C. silicon
B. nitrogen D. selenium

180 ChaPTeR 6
 Electron-dot notations can represent compounds.

Electron-dot notation can also be used to represent molecules.

A Lewis structure, named after American chemist G. N. Lewis,
is any formula in which
• atomic symbols represent nuclei and inner-shell electrons
• dot-pairs or dashes between two atomic symbols represent
electron pairs in covalent bonds
• dots adjacent to only one atomic symbol represent
unshared electrons
For example, a hydrogen molecule, H2, is represented by
combining the notations of two individual hydrogen atoms.
The pair of dots between the hydrogen symbols represents the
shared electron pair in a hydrogen-hydrogen bond.

HH

For a molecule of fluorine, F2, the Lewis structure also

includes the three unshared pairs of electrons in each fluorine
atom. These pairs that are not shared in bonds are also called
lone pairs.

F F

Another way to write the Lewis structures of hydrogen

molecules and fluorine molecules is to represent the shared
pair of electrons by a long dash, as shown below.

H−H F−F
READING CHECK
Yet another way to write Lewis structures is only to use
7. How is electron-dot notation
dashes to show the shared electrons. A structural formula
related to Lewis structures?
indicates the kind, number, arrangement, and bonds, but not
the unshared electrons of the atoms in a molecule. For
example, F–F and H–Cl are structural formulas.
The sample problem on the next page shows the basic steps
that can be used to draw the structural formula of many
molecules. The single dash between two atomic symbols
represents a single bond. A single bond is a covalent bond in
which one pair of electrons is shared between two atoms.

ChemiCal Bonding 181

 SAMPLE PROBLEM
​ H​3​I.
Draw the Lewis structure of iodomethane, C

SOLVE

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

Iodomethane has one C atom, three H atoms, and one I atom.

STEP 2 Write the electron-dot notation for each type of atom.

C, I, and H atoms have 4, 7, and
C I H
1 valence electron, respectively.

STEP 3 Determine the number of electrons available for bonding.

4 electrons in each C atom → 1 × ​4e​–​ = 4​e–​ ​
1 electron in each H atom → 3 × ​1e​–​ = 3​e–​ ​
7 electrons in each I atom → 1 × ​7e​–​ =​ 7​e–​
e​–
14​

STEP 4 Arrange the atoms to form a skeleton structure for the molecule.
If carbon is present, make it the central atom. Otherwise, the most
electronegative element besides hydrogen is central. Then connect
the atoms with electron-pair bonds.

H
H C I
H

STEP 5 Add unshared pairs of electrons to each nonmetal atom (besides

hydrogen) so that each is surrounded by an octet.

H H
H C I or H-C-I
H H

STEP 6 Count the electrons in the structure to be sure it shows the same
number of available valence electrons as calculated in Step 3.
The four covalent bonds add up to eight electrons, and the six
unpaired electrons make a total of 14 electrons. This matches the
number of available valence electrons.

182 C HA P T E R 6
PRACTICE

E. Draw the Lewis structure of ammonia, ​NH​3​.

One molecule has N atom(s) and H atom(s).

Each N atom has valence electrons.

Each H atom has valence electrons.

There are valence electrons available for bonding.

Use the space at the right to arrange the
N and H atoms, using dots to represent
electron pairs and lone pairs. Make sure
the final result contains the same number
of dots as there are valence electrons
available for bonding.

F. Draw the Lewis structure of phosphorus trifluoride, P

​ F​3​.
One molecule has P atom(s) and F atom(s).

Each P atom has valence electrons.

Each F atom has valence electrons.

There are valence electrons available for bonding.

Use the space at the right to arrange the
P and F atoms, using dots to represent
electron pairs and lone pairs. Make sure
the final result contains the same number
of dots as there are valence electrons
available for bonding.

G. Draw the Lewis structure for hydrogen sulfide, H

​ 2​ ​S.

H. Draw the Lewis structure for silane, Si​H4​ ​.

Chemical Bonding 183

 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 ↑↓ ↑↓ ↓ ↓ ↓
N
1s 2s
in which two pairs of electrons are shared between two atoms. 2p
A double bond is either shown by two side-by-side pairs
↑↓ ↑↓ ↑ ↑ ↑
of dots or by two parallel dashes. For example, in ethane, N
1s 2s
C2H4, two electron pairs are shared at the same time by two 2p
carbon atoms. Nitrogen molecule

H H H H In a molecule of nitrogen, N2,

C C or C=C each nitrogen atom is surrounded
by an octet that includes one
H H H H
unshared pair and six shared
electrons.
A triple covalent bond, or triple bond, is a covalent bond in
which three pairs of electrons are shared between two atoms.
A triple bond is either shown by three side-by-side pairs of
dots or by three parallel dashes. For example, nitrogen
normally exists as a diatomic molecule. The nitrogen atom has
three unpaired electrons in its 2p orbitals. These unpaired
electrons form an octet when two nitrogen atoms bond.

N N or N≡N

Carbon can also form compounds with triple bonds. For

example, ethyne, C2H2, contains a carbon-carbon triple bond.

H C C H or H-C≡C-H

Double bonds and triple bonds are also referred to as

multiple covalent bonds, or multiple bonds. In general,
double bonds are shorter and have greater bond energies TIP If you are making a Lewis
structure of a molecule,
than single bonds. Triple bonds are even stronger and shorter. and it does not seem that there
The table on the top of the next page compares single, double, are enough electrons available to
and triple bonds. form complete octets, this often
indicates that a double or triple
It is important to remember that multiple bonds are bond is present.
possible when writing Lewis structures for molecules that
contain carbon, nitrogen, or oxygen. A hydrogen atom, on the
other hand, can only form single bonds.

Critical Thinking
8. Infer Why can an oxygen atom not form a triple bond?

184 ChaPTeR 6
 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

Resonance structures show hybrid bonds.

Some molecules cannot be represented by a single Lewis

structure. For example, ozone, O3, can be represented by the
two structures below. Each structure indicates that an ozone
molecule includes one single bond and one double bond.

O=O-O or O-O=O

At one time, scientists hypothesized that ozone constantly

switched between each structure. However, experiments have
shown that the two oxygen-oxygen bonds are identical, not
distinct as shown in the diagrams. Therefore, scientists now say READING CHECK
that ozone has a single structure that is the average of the two 9. Why can ozone not be represent-
ed by the structure O=O–O alone?
structures above. The structures are referred to as resonance
structures, or resonance hybrids.
In general, resonance refers to bonding in molecules or
ions that cannot be represented by a single Lewis structure.
To indicate resonance, a double arrow is placed between a
molecule’s resonance structures.

O=O-O  O-O=O

Some compounds are networks of bonded atoms.

All of the covalent molecules discussed so far have been

molecular. However, there are other covalently bonded
compounds that do not contain individual molecules, but are
three-dimensional networks of bonded atoms. These
covalently bonded networks will be discussed in the chapter
“States of Matter.”

ChemiCal Bonding 185

 SAMPLE PROBLEM
Draw the Lewis structure for methanol, C​H2​ ​O.

SOLVE

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

Methanol has one C atom, two H atoms, and one O atom.

STEP 2 Write the electron-dot notation for each type of atom.

C, O, and H atoms have 4, 6, and    
C O H
1 valence electron respectively.

STEP 3 Determine the number of electrons available for bonding.

1 × 4​e–​ ​ + 2 × 1​e–​ ​ + 1 × 6​e–​ ​ = 12​e–​ ​

STEP 4 Arrange the atoms to form a skeleton structure for the molecule .
Then connect the atoms with electron-pair bonds.

H
H C O

STEP 5 Add unshared pairs of electrons to each nonmetal atom

(besides hydrogen) so that each is surrounded by an octet.

H
HCO

STEP 6 Count the electrons in the structure to make sure the structure
shows the sum of the available valence electrons calculated. If
it does not, subtract the extra electrons and change lone pairs
to shared pairs until each atom is surrounded by an octet.
Delete a lone pair from the O atom to get H
H
12 electrons. Move the C lone pair so that
H C O or H-C=O
it is shared with the O atom.

PRACTICE Draw the Lewis structure for each molecule.

I. carbon dioxide, C​O2​ ​ J.  hydrogen cyanide, HCN

186 C HA P T E R 6
 SECTION 6.2 REVIEW
VOCABULARY
1. Define the following.

a. bond length

b. bond energy

REVIEW
2. State the octet rule.

3. How many pairs of electrons are shared in the following types of

covalent bonds?

a. a single bond

b. a double bond

c. a triple bond

4. Draw the Lewis structures for the following molecules.

a. C​H3​ ​Br c. SiC​l4​

b. C
​ 2​ ​HCl d. ​OF​2​   

Critical Thinking
5. APPLYING MODELS Compare the molecules H
​ 2​ ​NN​H2​ ​and HNNH. Which
molecule has the stronger N–N bond?

Chemical Bonding 187