Chapter 9

Chemical Bonding I:
Basic Concepts

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 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 valencee −
−

1A ns1 1
2A ns 2 2
3A ns 2 np1 3
4A ns 2 np 2 4
5A ns 2 np 3 5
6A ns 2 np 4 6
7A ns 2 np 5 7
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Lewis Dot Symbols for the Representative
Elements & Noble Gases

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 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]

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 Example 9.1
Use Lewis dot symbols to show the formation of
aluminum oxide ( Al 2O3 ) .

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 Electrostatic (Lattice) Energy
Lattice energy (U) is the energy required to completely
separate one mole of a solid ionic compound into gaseous
ions.
E is the Potential energy
Q+ is the charge on the cation
Q+Q−
E=k Q− is the charge on the anion
r r is the distance between the ions
Compound Lattice Energy ( kj / mol )

Lattice energy increases as MgF2 2957 Q : + 2, − 1

Q increases and/or MgO 3938 Q : + 2, − 2
as r decreases. LiF 1036 rF − < rCl−
LiCl 853 rF− < rCl−
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Lattice Energies for Some Metal Halides
and Oxides
Table 9.1 Lattice Energies and Melting Points of Some Alkali Metal and
Alkaline Earth Metal Halides and Oxides
Lattice Energy Melting
Compound
(kJ/mol) Point (°C)
LiF 1017 845
LiCl 828 610
LiBr 787 550
LiL 732 450
NaCl 788 801
NaBr 736 750
Nal 686 662
KCl 699 772
KBr 689 735
Kl 632 680
MgCl2 2527 714
Na2O 2570 Sub*
MgO 3890 2800

* Na 2 O sublimes at 1275°C. © McGraw-Hill Education. 9-7

 The Covalent Bond (1 of 2)

A covalent bond is a chemical bond in which two or

more electrons are shared by two atoms.
Why should two atoms share electrons?

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 The Covalent Bond (2 of 2)
Lewis structure of water

Double bond – two atoms share two pairs of electrons

Triple bond – two atoms share three pairs of electrons

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 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

Bond Lengths Triple bond < Double Bond < Single Bond
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 Polar Covalent Bonds
Polar covalent bond or polar bond is a covalent bond
with greater electron density around one of the two
atoms

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 Electronegativity
Electronegativity is the ability of an atom to attract toward itself
the electrons in a chemical bond.
Electron Affinity − measurable, Cl is highest
X(g ) + e− → X − (g )

Electronegativity − relative, F is
highest

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The Electronegativities of Common
Elements

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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 −

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 Example 9.2

Classify the following bonds as ionic, polar covalent, or

covalent:

(a) the bond in HCl (EN: H=2.1; Cl=3.0) Polar Covalent

(b) the bond in KF (EN: K=0.8; F=4.0) Ionic

(c) the CC bond in H3CCH3 (EN: C=2.5) Pure Covalent

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 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 structure contains too many electrons, form
double and triple bonds on central atom as
needed.
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 Example 9.3
Write the Lewis structure for nitrogen trifluoride ( NF3 )
in which all three F atoms are bonded to the N atom.

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 Example 9.4
Write the Lewis structure for nitric acid (HNO3)

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

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 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.

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

C − 4e − 2single bonds ( 2 × 2 ) =
4
O − 6e − 1double 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 

formalcharge on C =4 − 2 − 1 × 6 =−1
2
formalcharge on O =6 − 2 − 1 × 6 =+1
2
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 Two Possible Skeletal Structures of
Formaldehyde (CH2O),Structure 2
C − 4e − 2single bonds ( 2 × 2 ) =
4
O − 6e − 1double 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 

formalcharge on C = 4 − 0 − 1 × 8 = 0
2
formalcharge on O = 6 − 4 − 1 × 4 = 0
2
CH 2O
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 Example 9.6

Write formal charges for the carbonate ion.

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 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.

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 Example 9.7 (1 of 3)

Draw three resonance structures for the molecule

nitrous oxide, N 2O
(the atomic arrangement is NNO).

Indicate formal charges.

Rank the structures in their relative importance to the

overall properties of the molecule.

© McGraw-Hill Education. 9-25

 Example 9.7 (2 of 3)
Strategy
The skeletal structure for N 2Ois

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 x

© McGraw-Hill Education. 9-26

 Example 9.7 (3 of 3)

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 it has a larger

separation of formal charges. Also, 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 Education. 9-27

 Exceptions to the Octet Rule (1 of 2)
The Incomplete Octet

BeH 2 B − 3e −
3F − 3 × 7e −
24e −

BF3

Βe − 2e − 3 Single bonds (3×2) = 6

9 lone pairs (9×2) = 18
2Η − 2 × 1e −
Total = 24
4e −

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 Exceptions to the Octet Rule (2 of 2)
Odd-Electron Molecules
N − 5e −
NO −
0 − 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

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 Example 9.8 (1 of 3)

Draw the Lewis structure for aluminum triiodide ( AlI3 ) .

AlI3 has a tendency to dimerize or form two units as Al2 I6

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 Example 9.8 (2 of 3)
Strategy
We follow the procedures used in Examples 9.5 and 9.6 to draw the Lewis
structure and calculate formal charges.

Solution
2 1 2 5
The outer-shell electron configurations of Al and I are 3s 3 p and 5s 5 p ,
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.

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 Example 9.8 (3 of 3)

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 Education. 9-32

 Example 9.9 (1 of 3)
Draw the Lewis structure for phosphorus pentafluorid ( PF5 ) ,
in which all five F atoms are bonded to the central P atom.

PF5 is a reactive gaseous compound.

© McGraw-Hill Education. 9-33
 Example 9.9 (2 of 3)
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 Education. 9-34

 Example 9.9 (3 of 3)
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.

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 Example 9.10 (1 of 6)

Draw a Lewis structure for the sulfate ion SO 24−

in which all four O atoms are bonded to the central S atom.

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 Example 9.10 (2 of 6)
Strategy
Note that S 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.

Solutions
The outer-shell electron configurations of S and O
3s 2 3 p 4 and 2 s 2 2 p 4 ,
Step 1: The skeletal structure of SO 42− is

© McGraw-Hill Education. 9-37

 Example 9.10 (3 of 6)
Step 2: Both O and S are Group 6A elements and so have six
valence electrons each. Including the two negative
charges, we must therefore account for a total of 6 +
(4 × 6) + 2, or 32, valence electrons in SO 42−

Step 3: We draw a single covalent bond between all the

bonding atoms:

© McGraw-Hill Education. 9-38

 Example 9.10 (4 of 6)
Next we show formal charges on the S and O atoms:

Note that we can eliminate some of the formal charges for

SO 24− by expanding the S atom’s octet as follows:

© McGraw-Hill Education. 9-39

 Example 9.10 (5 of 6)
The question of which of these two structures is more
important, that is, the one in which the S atom obeys the octet
rule but bears more formal charges or the one in which the S
atom expands its octet, has been the subject of some debate
among chemists. In many cases, only elaborate quantum
mechanical calculations can provide a clearer answer.

At this stage of learning, you should realize that both

representations are valid Lewis structures and you should be
able to draw both types of structures. One helpful rule is that
in trying to minimize formal charges by expanding the central
atom’s octet, only add enough double bonds to make the
formal charge on the central atom zero.

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 Example 9.10 (6 of 6)
Thus, the following structure would give formal charges
on S(−2) and O(0) that are inconsistent with the
electronegativities of these elements and should
therefore not be included to represent the SO 24− ion.

© McGraw-Hill Education. 9-41

 Example 9.11 (1 of 3)

Draw a Lewis structure of the noble gas compound xenon

tetrafluoride ( XeF4 )
in which all F atoms are bonded to the central Xe atom.

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 Example 9.11 (2 of 3)
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 Education. 9-43

 Example 9.11 (3 of 3)
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.
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