Because learning changes everything.

Chapter 9

Compounds and
Bonding

© McGraw Hill LLC. All rights reserved. No reproduction or distribution without the prior written consent of McGraw Hill LLC.
 Valence Electrons
Valence electrons are the outer shell electrons of
an atom. The valence electrons are the electrons
that participate in chemical bonding.
Group e⁻ configuration # of valence e⁻
1A ns¹ 1
2A ns² 2
3A ns²np¹ 3
4A ns²np² 4
5A ns²np³ 5
6A ns²np⁴ 6
7A ns²np⁵ 7

© McGraw Hill LLC 2

 Lewis Dot Symbols for the Representative
Elements & Noble Gases

© McGraw Hill LLC 3

 The Ionic Bond
Ionic bond: the electrostatic force that holds ions
together in an ionic compound.

1s 2 2 s1 1s 2 2 s 2 2 p 5 1s 2 1s 2 2 s 2 2 p 6
[He] [Ne]

© McGraw Hill LLC 4

 Example 9.1
Use Lewis dot symbols to show the formation of
aluminum oxide (Al2O3).

The mineral corundum (Al2O3).

© McGraw Hill LLC 5

 Example 9.1
Strategy
We use electroneutrality as our guide in writing formulas for ionic
compounds, that is, the total positive charges on the cations must
be equal to the total negative charges on the anions.

Solution
According to Figure 9.1, the Lewis dot symbols of Al and O are

Because aluminum tends to form the cation (Al3+ ) and oxygen the anion (O2− )
in ionic compounds, the transfer of electrons is from Al to O.
There are three valence electrons in each Al atom; each O
atom needs two electrons to form the (O 2− )
ion, which is isoelectronic with neon.
© McGraw Hill LLC 6
 Example 9.1
Thus, the simplest neutralizing ratio of Al3+ to O 2− is 2 : 3; two Al3+
ions have a total charge of +6, and three O 2−
ions have a total charge of − 6. So the empirical formula of
aluminum oxide is Al2O3, and the reaction is

Check
Make sure that the number of valence electrons (24) is the same
on both sides of the equation. Are the subscripts in A l2O3
reduced to the smallest possible whole numbers?

© McGraw Hill LLC 7

 The Covalent Bond
A covalent bond is a chemical bond in which two or
more electrons are shared by two atoms.
Why should two atoms share electrons?

© McGraw Hill LLC 8

 The Covalent Bond
Lewis structure of water

Double bond – two atoms share two pairs of electrons

Triple bond – two atoms share three pairs of electrons

© McGraw Hill LLC 9

 Lengths of Covalent Bonds
Table 9.2 Average Bond Lengths
of Some Common Single, Double,
and Triple Bonds
Bond Type Bond Length (pm)
C–H 107

C–O 143

C=O 121

C–C 154

C=C 133

CC 120
C–N 143

C=N 138
CN 116

N–O 136
N=O 122

O–H 96

CO 113

N–N 147

Bond Lengths: Triple bond < N=N 124

Double Bond < Single Bond NN

O–O
110

148
O=O 121

© McGraw Hill LLC 10

 Polar Covalent Bonds
Polar covalent bond or polar bond is a covalent bond with greater
electron density around one of the two atoms.

H2 HF

© McGraw Hill LLC 11

 Electronegativity
Electronegativity is the ability of an atom to attract toward itself
the electrons in a chemical bond.

© McGraw Hill LLC 12

 The Electronegativities of Common
Elements

© McGraw Hill LLC 13

 Classification of Bonds by Difference in
Electronegativity

Difference Bond type

0 Covalent
≥2 Ionic
0 < and < 2 Polar covalent

⎯⎯⎯⎯⎯⎯→
Increasing difference in electronegativity

Covalent → Polar Covalent → Ionic

share e − → partial transfer of e − → transfer e −

© McGraw Hill LLC 14

 Example 9.2
Classify the following bonds as ionic, polar covalent,
or covalent:

(a) the bond in HCl

(b) The bond in KF

(c) the CC bond in H3CCH3

© McGraw Hill LLC 15

 Example 9.2
Strategy
We follow the 2.0 rule of electronegativity difference and look up the
values in Figure 9.5.

Solution
(a) The electronegativity difference between H and Cl is 1.0, which is
appreciable but not large enough (by the 2.0 rule) to qualify HCl as an
ionic compound. Therefore, the bond between H and Cl is polar
covalent.
(b) The electronegativity difference between K and F is 3.2, which is
well above the 2.0 mark; therefore, the bond between K and F is ionic.
(c) The two C atoms are identical in every respect—they are bonded to
each other and each is bonded to three other H atoms. Therefore, the
bond between them is purely covalent.

© McGraw Hill LLC 16

 Writing Lewis Structures
1. Draw skeletal structure of compound showing
what atoms are bonded to each other. Put least
electronegative element in the center.
2. Count total number of valence e − . Add 1 for each
negative charge. Subtract 1 for each positive
charge.
3. Complete an octet for all atoms except hydrogen.
4. If an atom in the structure has fewer then eight
electrons, form double and triple bonds on the
central atom as needed.

© McGraw Hill LLC 17

 Example 9.3
Write the Lewis structure for nitrogen trifluoride (NF3)
in which all three F atoms are bonded to the N atom.

NF3 is a colorless, odorless, unreactive gas.

© McGraw Hill LLC 18

 Example 9.3
Solution
We follow the preceding procedure for writing Lewis structures.

Step 1: The N atom is less electronegative than F, so the skeletal

structure of NF3 is

Step 2: The outer-shell electron configurations of N and F are

2 s 2 2 p 3 and 2 s 2 2 p 5 , respectively.
Thus, there are 5 + (3  7),
or 26, valence electrons to account for in NF3.
© McGraw Hill LLC 19
 Example 9.3
Step 3: We draw a single covalent bond between N and each F,
and complete the octets for the F atoms. We place the remaining
two electrons on N:

Because this structure satisfies the octet rule for all the atoms,
step 4 is not required.
Check
Count the valence electrons in NF3 (in bonds and in lone pairs).
The result is 26, the same as the total number of valence electrons
on three F atoms (3 × 7 = 21) and one N atom (5).

© McGraw Hill LLC 20

 Example 9.4
Write the Lewis structure for nitric acid (HNO3) in which the
three O atoms are bonded to the central N atom and the
ionizable H atom is bonded to one of the O atoms.

HNO3 is a strong electrolyte.

© McGraw Hill LLC 21

 Example 9.4
Solution
We follow the procedure already outlined for writing Lewis
structures.

Step 1: The skeletal structure of HNO3 is

Step 2: The outer-shell electron configurations of N, O, and

H are 2 s 2 2 p 3 , 2 s 2 2 p 4 , and 1s1, respectively. Thus, there are
5 + (3  6) + 1, or 24, valence electrons to account for in HNO3.

© McGraw Hill LLC 22

 Example 9.4
Step 3: We draw a single covalent bond between N and
each of the three O atoms and between one O atom
and the H atom. Then we fill in electrons to comply
with the octet rule for the O atoms:

Step 4: We see that this structure satisfies the octet rule for
all the O atoms but not for the N atom. The N atom
has only six electrons. Therefore, we move a lone
pair from one of the end O atoms to form another
bond with N.
© McGraw Hill LLC 23
 Example 9.4
Now the octet rule is also satisfied for the N atom:

Check
Make sure that all the atoms (except H) satisfy the octet rule.
Count the valence electrons in HNO3 (in bonds and in lone
pairs). The result is 24, the same as the total number of valence
electrons on three O atoms (3 × 6 = 18), one N atom (5), and
one H atom (1).

© McGraw Hill LLC 24

 Example 9.5
Write the Lewis structure for the carbonate ion (CO32− ).

© McGraw Hill LLC 25

 Example 9.5
Solution
We follow the preceding procedure for writing Lewis
structures and note that this is an anion with two negative
charges.

Step 1: We can deduce the skeletal structure of the

carbonate ion by recognizing that C is less electronegative
than O. Therefore, it is most likely to occupy a central
position as follows:

© McGraw Hill LLC 26

 Example 9.5
Step 2: The outer-shell electron configurations of C and O
are 2s 2 2 p 2 and 2s 2 2 p 4 , respectively, and the ion itself
has two negative charges. Thus, the total number of
electrons is 4 + (3  6) + 2, or 24.

Step 3: We draw a single covalent bond between C and each O

and comply with the octet rule for the O atoms:

This structure shows all 24 electrons.

© McGraw Hill LLC 27

 Example 9.5
Step 4: Although the octet rule is satisfied for the O atoms, it is
not for the C atom. Therefore, we move a lone pair from
one of the O atoms to form another bond with C. Now the
octet rule is also satisfied for the C atom:

Check
Make sure that all the atoms satisfy the octet rule. Count the
valence electrons in CO32− (in chemical bonds and in lone pairs).
The result is 24, the same as the total number of valence electrons
on three O atoms (3 × 6 = 18), one C atom (4), and two negative
charges (2).
© McGraw Hill LLC 28
 Two Possible Skeletal Structures of
Formaldehyde (CH2O)

An atom’s formal charge is the difference between the

number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
formal charge on atom total number of valence electrons total number of 1  total number of 
= − −  
in a Lewis structure in the free atom nonbonding electrons 2  bonding electrons 

The sum of the formal charges of the atoms in a molecule

or ion must equal the charge on the molecule or ion.

© McGraw Hill LLC 29

 Two Possible Skeletal Structures of
Formaldehyde (CH2O), Structure 1

C − 4e − 2single bond(2  2) = 4
O − 6e − double bond = 4
2H − 2 1e − 2lone pairs(2  2) = 4
12e − Total = 12

formal charge on atom total number of valence electrons total number of 1  total number of 
= − −  
in a Lewis structure in the free atom nonbonding electrons 2  bonding electrons 

formal charge on C = 4 − 2 − 1  6 = −1
2
formal charge on O = 6 − 2 − 1  6 = +1
2
© McGraw Hill LLC 30
 Two Possible Skeletal Structures of
Formaldehyde (CH2O), Structure 2
C − 4e − 2single bond(2  2) = 4
O − 6e − double bond = 4
2H − 2 1e − 2lone pairs(2  2) = 4
12e − Total = 12
formal charge on atom total number of valence electrons total number of 1  total number of 
= − −  
in a Lewis structure in the free atom nonbonding electrons 2  bonding electrons 

formal charge on C = 4 − 0 − 1  8 = 0
2
formal charge on O = 6 − 4 − 1  4 = 0
2
CH2O
© McGraw Hill LLC 31
 Example 9.6
Write formal charges for the carbonate ion.

© McGraw Hill LLC 32

 Example 9.6
Strategy
The Lewis structure for the carbonate ion was developed in
Example 9.5:

The formal charges on the atoms can be calculated using the

given procedure.

Solution
We subtract the number of nonbonding electrons and half of the
bonding electrons from the valence electrons of each atom.
© McGraw Hill LLC 33
 Example 9.6
The C atom: The C atom has four valence electrons and
there are no nonbonding electrons, one double
bond and two single bonds on the atom in the
Lewis structure. Therefore, the formal charge is
4 − 4 = 0.
The O atom in C = O: The O atom has six valence electrons
and there are four nonbonding electrons and a
double bond on the atom. Here the formal
charge is 6 − 4 − 2 = 0.

© McGraw Hill LLC 34

 Example 9.6
The O atom in C − O: This atom has six nonbonding electrons
and one single bond. Therefore, the formal
charge is 6 − 6 −1 = −1.

Thus, the Lewis structure for CO32−

with formal charges is

Check
Note that the sum of the formal charges is −2, the same as the
charge on the carbonate ion.
© McGraw Hill LLC 35
 Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which
there are no formal charges is preferable to one in
which formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar
distributions of formal charges, the most plausible
structure is the one in which negative formal
charges are placed on the more electronegative
atoms.

© McGraw Hill LLC 36

 Example 9.7
Formaldehyde (CH2O), a liquid with a disagreeable odor,
traditionally has been used to preserve laboratory specimens.
Draw the most likely Lewis structure for the compound.

© McGraw Hill LLC 37

 Example 9.7
Strategy
A plausible Lewis structure should satisfy the octet rule for
all the elements, except H, and have the formal charges (if
any) distributed according to electronegativity guidelines.

Solution
The two possible skeletal structures are

© McGraw Hill LLC 38

 Example 9.7
First we draw the Lewis structures for each of these
possibilities

To show the formal charges, we follow the procedure given in

Example 9.6. In (a) the C atom has a formal charge = 4 − 2 −
½(6) = −1. The O atom has a formal charge = 6 − 2 − ½(6) =
+1.

© McGraw Hill LLC 39

 Example 9.7
In (b) the C atom has a formal charge 4 − ½(8) = 0. The O atom has a
formal charge = 6 − 6 = 0.
Although both structures satisfy the octet rule, (b) is the more likely
structure because it carries no formal charges.

Check
In each case make sure that the total number of valence electrons is 12.

© McGraw Hill LLC 40

 Resonance Structures
A resonance structure is one of two or more Lewis
structures for a single molecule that cannot be
represented accurately by only one Lewis structure.

© McGraw Hill LLC 41

 Example 9.8
Draw three resonance structures for the molecule
nitrous oxide, N2O (the atomic arrangement is NNO).

Indicate formal charges.

© McGraw Hill LLC 42

 Example 9.8
Strategy
The skeletal structure for N2O is

We follow the procedure used for drawing Lewis structures

and calculating formal charges in Examples 9.5 and 9.6.

Solution
The three resonance structures are:

© McGraw Hill LLC 43

 Example 9.8
We see that all three structures show formal charges.

Structure (b) is the most important one because the negative charge is
on the more electronegative oxygen atom.

Structure (c) is the least important one because the positive charge is
on the more electronegative oxygen atom.

Check
Make sure there is no change in the positions of the atoms in the
structures. Because N has five valence electrons and O has six valence
electrons, the total number of valence electrons is 5 × 2 + 6 = 16. The
sum of formal charges is zero in each structure.

© McGraw Hill LLC 44

 Exceptions to the Octet Rule
The Incomplete Octet

BeH2 Be − 2e −
2H − 2 1e −
4e −

BF3
B − 3e −
3 Single bonds (3  2) = 6
−
3F − 3  7e 9 lone pairs (9  2) = 18
24e − Total = 24

© McGraw Hill LLC 45

 Exceptions to the Octet Rule
Odd-Electron Molecules

N − 5e −
NO
O − 6e −
11e −
The Expanded Octet (central atom with principal quantum
number n > 2)

S − 6e − 6 Single bonds (6  2) = 12
SF6 6F − 42e − 18 lone pairs (18  2) = 36
48e − Total = 48

© McGraw Hill LLC 46

 Example 9.9
Draw the Lewis structure for aluminum triiodide (AlI3).

© McGraw Hill LLC 47

 Example 9.9
Strategy
We follow the procedures used in Examples 9.5 and 9.6 to draw the Lewis
structure and calculate formal charges.

Solution
The outer-shell electron configurations of Al and I are 3s 2 3 p1 and 5s 2 5 p 5 ,
respectively. The total number of valence electrons is 3 + 3 × 7 or 24. Because
Al is less electronegative than I, it occupies a central position and forms three
bonds with the I atoms:

Note that there are no formal charges on the Al and I atoms.

© McGraw Hill LLC 48

 Example 9.9
Check
Although the octet rule is satisfied for the I atoms, there
are only six valence electrons around the Al atom.

Thus, AlI3 is an example of the incomplete octet.

© McGraw Hill LLC 49

 Example 9.10
Draw the Lewis structure for phosphorus pentafluoride (PF5),
in which all five F atoms are bonded to the central P atom.

PF5 is a reactive gaseous compound.

© McGraw Hill LLC 50
 Example 9.10
Strategy
Note that P is a third-period element. We follow the procedures
given in Examples 9.5 and 9.6 to draw the Lewis structure and
calculate formal charges.

Solution
The outer-shell electron configurations for P and F are
3s 2 3 p 3 and 2 s 2 2 p 5 , respectively, and so the total number of
valence electrons is 5 + (5  7), or 40.

Phosphorus, like sulfur, is a third-period element, and therefore

it can have an expanded octet.

© McGraw Hill LLC 51

 Example 9.10
The Lewis structure of PF5 is

Note that there are no formal charges on the P and F atoms.

Check
Although the octet rule is satisfied for the F atoms, there are 10
valence electrons around the P atom, giving it an expanded octet.

© McGraw Hill LLC 52

 Example 9.12
Draw a Lewis structure of the noble gas compound xenon
tetrafluoride (XeF4) in which all F atoms are bonded to
the central Xe atom.

XeF4

© McGraw Hill LLC 53

 Example 9.12
Strategy
Note that Xe is a fifth-period element. We follow the procedures in
Examples 9.5 and 9.6 for drawing the Lewis structure and calculating
formal charges.

Solution
Step 1: The skeletal structure of XeF4 is

Step 2: The outer-shell electron configurations of Xe and F are

5s 2 5 p 6 and 2 s 2 2 p 5 ,
respectively, and so the total number of valence electrons is 8 + (4  7) or
36.

© McGraw Hill LLC 54

 Example 9.12
Step 3: We draw a single covalent bond between all the bonding atoms.
The octet rule is satisfied for the F atoms, each of which has
three lone pairs. The sum of the lone pair electrons on the four
F atoms (4 × 6) and the four bonding pairs (4 × 2) is 32.
Therefore, the remaining four electrons are shown as two lone
pairs on the Xe atom:

We see that the Xe atom has an expanded octet. There are no

formal charges on the Xe and F atoms.

© McGraw Hill LLC 55

 Because learning changes everything. ®

[Link]

© McGraw Hill LLC. All rights reserved. No reproduction or distribution without the prior written consent of McGraw Hill LLC.