Petrucci’s General Chemistry

P R I N C I P L E S A N D M O D E R N A P P L I C AT I O N S
Twelfth Edition

PETRUCCI HERRING MADURA BISSONNETTE

Chemical Bonding I:
Basic Concepts 10

Chemical Bonding I: CONTENTS

10-1 Lewis Theory: An Overview
Basic Concepts
10-2 Covalent Bonding: An Introduction

10-3 Polar Covalent Bonds and

Electrostatic Potential Maps
10-4 Writing Lewis Structures

10-5 Resonance

10-6 Exceptions to the Octet Rule

10-7 Shapes of Molecules

10-8 Bond Order and Bond Length

10-9 Bond Energies

 10-1 Lewis Theory: An Overview

1. Valence e− play a fundamental

role in chemical bonding.
2. e– transfer leads to
ionic bonds.
3. Sharing of e– leads to a
covalent bond.
4. e– are transferred or shared to
give each atom a noble gas
configuration, the octet.

Gilbert Newton Lewis (1875-1946)

Lewis Symbols and Lewis Structures

A chemical symbol represents the nucleus and the core e−.

Dots around the symbol represent valence e−.

•
• Si •
•

•• •• •• •• ••
•N• • P• • As • • Sb • • Bi •
• • • • •

•• •• ••
• Al • • Se I • Ar
•
••
••
••

• • •• ••
Lewis structure

Lewis Structures for Ionic Compounds

No bond is 100% ionic.

All bonds have some
covalent character.

FIGURE 10-1
Portion of an ionic crystal
10-2 Covalent Bonding: An Introduction

Coordinate Covalent Bonds

(10.5)

(10.6)
 FIGURE 10-2
Formation of the ammonium ion, NH4+

Multiple Covalent Bonds

 FIGURE 10-3
Paramagnetism of Oxygen
10-3 Polar Covalent Bonds and
Electrostatic Potential Maps

FIGURE 10-4
Determination of the electrostatic potential map for ammonia

FIGURE 10-5
The electrostatic potential maps for sodium chloride, hydrogen chloride and chlorine
Electronegativity

(10.10)

(10.11)
 FIGURE 10-6
Electronegativities of the elements

FIGURE 10-7
Percent ionic character of a chemical bond as a function of electronegativity difference
 Electrostatic potential maps demonstrating differences in ionic character.

10-4 Writing Lewis Structures

• All the valence e– of atoms must appear in the structure.

• Usually, all the e– are paired.
• Usually, each atom requires an outer-shell octet of e–.
• H only requires 2 e–.
• Sometimes, multiple bonds may be needed.
• Readily formed by C, N, O, S, and P.
Skeletal Structure
Identify central and terminal atoms.

H H
H C C O H
H H

• Hydrogen atoms are always terminal atoms.

• Central atoms are generally those with the lowest
electronegativity.
• Carbon atoms are always central atoms.
• Generally structures are compact and symmetrical.
Summary scheme for
drawing Lewis Structures

FIGURE 10-8
Summary scheme for drawing Lewis structures

Example 10-7 Writing a Lewis Structure

for a Polyatomic Ion
NO2+

e– = 5+6+6-1=16

+
O—N—O

•• •• +
O—N—O
••
••

•• ••

•• •• + •• •• +
O—N—O O N O
••
••

••
••

•• •• •• ••
 Formal Charge

1
FC = #valence e− −#lone pair e− − #bond pair e−
2

•• •• +
O N O

••
••
•• ••

1 1
FC(O) = 6 −4 – (4) = 0 FC(N) = 5− 0 – (8) = +1
2 2

•• + ••
O=N=O
••
••

Formal Charge of an Alternative Lewis Structure

•• •• •• +
O—N—O O N O
••
••

••
••

•• •• ••

1 1
FC(O≡) = 6−2 – (6) = +1 FC(N) = 5−0 – (8) = +1
2 2
1
FC(O–) = 6−6 – (2) =−1
2

+ + •• -
O N O
••
••

••
 General Rules for Formal Charge

• Sum of FC is the overall charge.

• FC should be as small as possible.
• Negative FC usually on most electronegative elements.
• FC of same sign on adjacent atoms is unlikely.

+ + •• -
O≡N—O

••
••

••

10-5 Resonance

•• ••+ •• - - •• ••+ ••
O O O O O O
••
••

•• •• •• ••

-½ •• ••+ •• -½
O
••
O O
••

Electrostatic potential map of ozone

 10-6 Exceptions to the Octet Rule
Odd-Electron Species

•• ••
N=O

•
••

H
••
H—C—H O—H

•
••
•

Incomplete Octets
•• •• ••
F F
••

F
••
••
••

••
••

- +
B B B
F F + F F F – F

•• •• –
F F
••
••

••
••

•• – •• ••
F B F B F
••

••
••
••

•• •• ••
F F
F
••
••

••
Expanded Valence Shells

•• •• ••
Cl Cl F

••
••
••
••

••
••
Cl F F
Cl
P P S
Cl Cl Cl Cl F F
F

••
••
••

octet expanded valence expanded valence

shell shell
 10-7 The Shapes of Molecules

Bond length
distance between nuclei.

Bond angle
angle between adjacent bonds.

FIGURE 10-10
Geometric shape of a molecule

Valence-Shell Electron Pair Repulsion (VSEPR) Theory

Electron pairs repel each other whether they are in

chemical bonds (bond pairs) or unshared (lone pairs).
Electron pairs assume orientations about an atom to
minimize repulsions.

Electron group geometry – distribution of e− pairs.

Molecular geometry – distribution of nuclei.
 FIGURE 10-11
Balloon analogy to valence-shell electron-pair repulsion

FIGURE 10-12
Molecular shapes based on tetrahedral electron-group geometry of CH4, NH3, and H2O
Possibilities for Electron-Group Distributions

Electron-group geometries
• two electron groups: linear
• three electron groups: trigonal planar
• four electron groups: tetrahedral
• five electron groups: trigonal bipyramidal
• six electron groups: octahedral

FIGURE 10-13
Several electron-group geometries illustrated
 Applying VSEPR Theory
1. Draw a plausible Lewis structure.
2. Determine the number of e– groups and identify them as
bond or lone pairs.
3. Establish the e– group geometry.
4. Determine the molecular geometry.

Structures with Multiple Covalent Bonds

•• •• + •• +
S S S
– –
O O O O O O
 Molecules with More Than One Central Atom

The geometric distribution of terminal atoms around each central

atom must be determined and the results then combined into a single
description of the molecular shape. See Example 10-12.

Molecular Shapes and Dipole Moments

FIGURE 10-15
Polar molecules in an electric field
 FIGURE 10-16
Molecular shapes and dipole Moments

10-8 Bond Order and Bond Length

Bond Order
Single bond, bond order = 1
Double bond, bond order = 2
Triple bond, bond order = 3
Bond Length
The distance between the centers of two
atoms joined by a covalent bond.

the length of the covalent bond between two atoms can be approximated as the
sum of the covalent radii of the two atoms.
Average Bond Order

•• - •• -
O O O
••
••
••

••
••

••

C C C
-
O O - O O -
O O -

(1 + 1 + 2) bonds 4
average bond order = = = 1⅓
(3) structures 3
10-9 Bond Energies

FIGURE 10-17
Some bond energies compared
Calculating an Enthalpy of Reaction from Bond Energies.

ΔHrxn = Σ ΔH(bond breakage) + ΣΔH(bond formation)

≈ Σ BE(reactants) − Σ BE(products)

Predict whether a reaction will be

endothermic or exothermic using bond energies.