John E. McMurry • Robert C.

Fay

General Chemistry: Atoms First

Chapter 5
Covalent Bonds and Molecular Structure

Lecture Notes
Alan D. Earhart
Southeast Community College • Lincoln, NE

Copyright © 2010 Pearson Prentice Hall, Inc.

 Molecules and the Covalent
Bond
Covalent Bond: A bond that results from the sharing
of electrons between atoms.

Molecule: The unit of matter (atoms) held together

by covalent bonds.

Chapter 5/2
Molecules and the Covalent
Bond

Chapter 5/3
Molecules and the Covalent
Bond
Strengths of Covalent Bonds
A Comparison of Ionic and
Covalent Bonds

Chapter 5/6
 Polar Covalent Bonds:
Electronegativity
Electronegativity: The ability of an atom in a molecule
to attract the shared electrons in a covalent bond.

Chapter 5/7
Polar Covalent Bonds:
Electronegativity

Chapter 5/8
Polar Covalent Bonds:
Electronegativity

Chapter 5/9
Polar Covalent Bonds:
Electronegativity

Chapter 5/10
Polar Covalent Bonds:
Electronegativity

Chapter 5/11
Naming Molecular Compounds

Because nonmetals often combine

with one another in different
proportions to form different
compounds, numerical prefixes
are usually included in the names
of binary molecular compounds.

Chapter 5/12
 Naming Molecular Compounds

N2O4

The first element listed The second element listed

is more cationlike and is more anionlike and takes
takes the name of the the name of the element
element. with an “ide” modification
to the ending.

The prefix is added to the front of each to indicate

the number of each atom.

dinitrogen tetraoxide

Chapter 5/13
 Electron-Dot Structures

Electron-Dot Structures (Lewis Structures): A

representation of an atom’s valence electrons by using
dots and indicates by the placement of dots how the
valence electrons are distributed in the molecule.

Chapter 5/14
Electron-Dot Structures

Chapter 5/15
stop1
Electron-Dot Structures

Chapter 5/16
Electron-Dot Structures

Chapter 5/17
 Electron-Dot Structures of
Polyatomic Molecules
Step 1: Valence Electrons
• Count the total number of valence electrons for
all atoms in the molecule.
• Add one additional electron for each negative
charge in an anion or subtract one for each
positive charge in a cation.

Chapter 5/18
 Electron-Dot Structures of
Polyatomic Molecules
Step 2: Connect Atoms
• Draw lines to represent bonds between atoms.
• For hydrogen and second row atoms, use the
number of bonds listed below.
• For third row and greater atoms, they may have
more bonds than predicted by the octet rule.
• The least electronegative atom is usually the
central atom.

Chapter 5/19
 Electron-Dot Structures of
Polyatomic Molecules
Step 3: Assign Electrons to the Terminal Atoms
• Subtract the number of electrons used for
bonding in the previous step from the total
number determined in step 1.
• Complete each terminal atom’s octet (except
for hydrogen).

Step 4: Assign Electrons to the Central Atom

• If unassigned electrons remain after step 3,
place them on the central atom.

Chapter 5/20
 Electron-Dot Structures of
Polyatomic Molecules
Step 5: Multiple Bonds
• If no unassigned electrons remain after step 3
but the central atom does not yet have an octet,
use one or more lone pairs of electrons from a
neighboring atom to form a multiple bond
(either a double or a triple).

Chapter 5/21
 Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for H2O.
Step 1:
2x(1 valence e- for each H) + 1x(6 valence e- for each O)
= 8 total valence electrons

H H

Step 2: O H Step 4: O H

bonding pair of electrons

lone pair of electrons

Chapter 5/22
 Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for CCl4.
Step 1:
1x(4 valence e- for each C) + 4x(7 valence e- for each Cl)
= 32 valence electrons

Cl Cl
Step 2: Cl C Cl Step 3: Cl C Cl

Cl Cl

Chapter 5/23
 Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for H3O1+.
Step 1:
3x(1 valence e- for each H) + 1x(6 valence e- for each O)
- 1 (for the + charge on O) = 8 total valence electrons

1+
Step 2:
H H

H O H Step 4: H O H

Chapter 5/24
 Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for CH2O.
Step 1:
1x(4 valence e- for each C) + 2x(1 valence e- for each H)
+ 1x(6 valence e- for each O) = 12 valence electrons

O O

Step 2: H C H Step 5: H C H

O O

Step 3: H C H H C H
Chapter 5/25
 Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for SF6.
Step 1:
1x(6 valence e- for each S) + 6x(7 valence e- for each F)
= 48 valence electrons

F
F F
F F
F
Step 3: S
Step 2: S
F F
F F F
F
Chapter 5/26
 Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for ICl3.

Step 1: 7 + 3(7) = 28 valence electrons

Cl Cl
Cl Cl Cl Cl
Step 2: I Step 4: I

Cl
Cl Cl
Step 3:
I
Chapter 5/27
 Electron-Dot Structures and
Resonance
Draw an electron-dot structure for O3.

Step 1: 3(6) = 18 valence electrons

Step 2: O O O Step 4: O O O

Step 3: O O O Step 5: O O O

Chapter 5/28
Electron-Dot Structures and
Resonance
Move a lone pair from this oxygen?

Step 4: O O O

Or, move a lone pair from this oxygen?

O O O O O O

Resonance
Chapter 5/29
 Formal Charges

# of # of # of
Formal 1
= valence e- - bonding - nonbonding
Charge in free atom 2 e- e-

Calculate the formal charge on each atom in O3.

O O O

1 1 1
6 - 2 (4) - 4 = 0 6 - 2 (6) - 2 = +1 6 - 2 (2) - 6 = -1

Chapter 5/30
Molecular Shapes: The VSEPR
Model
VSEPR: Valence-Shell Electron-Pair Repulsion model

Electrons in bonds and in lone pairs can be thought of

as “charge clouds” that repel one another and stay as
far apart as possible, this causing molecules to
assume specific shapes.

Working from an electron-dot structure, count the

number of “charge clouds,” and then determine the
molecular shape.

Chapter 5/31
Molecular Shapes: The VSEPR
Model
Two Charge Clouds

Chapter 5/32
Molecular Shapes: The VSEPR
Model
Three Charge Clouds

Chapter 5/33
Molecular Shapes: The VSEPR
Model
Four Charge Clouds

Chapter 5/34
Molecular Shapes: The VSEPR
Model
Four
Charge
Clouds

Chapter 5/35
Molecular Shapes: The VSEPR
Model
Five Charge Clouds

Chapter 5/36
Molecular Shapes: The VSEPR
Model
Five Charge Clouds

Chapter 5/37
Molecular Shapes: The VSEPR
Model
Five Charge Clouds

Chapter 5/38
Molecular Shapes: The VSEPR
Model
Five Charge Clouds

Chapter 5/39
Molecular Shapes: The VSEPR
Model
Five Charge Clouds
Molecular Shapes: The VSEPR
Model
Six Charge Clouds

Chapter 5/41
Molecular Shapes: The VSEPR
Model
Six Charge Clouds

Chapter 5/42
Molecular Shapes: The VSEPR
Model
Six Charge Clouds

Chapter 5/43
Molecular Shapes: The VSEPR
Model
Six Charge Clouds

Chapter 5/44
Chapter 5/45
Chapter 5/46
 Valence Bond Theory

Valence Bond Theory: A quantum mechanical model

which shows how electron pairs are shared in a
covalent bond.

sigma () bonds

Chapter 5/47
 Valence Bond Theory

Valence Bond Theory: A quantum mechanical model

which shows how electron pairs are shared in a
covalent bond.

• Covalent bonds are formed by overlap of atomic

orbitals, each of which contains one electron of
opposite spin.
• Each of the bonded atoms maintains its own
atomic orbitals, but the electron pair in the
overlapping orbitals is shared by both atoms.
• The greater the amount of overlap, the stronger
the bond.

Chapter 5/48
Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?
4 valence electrons
2 unpaired electrons

Chapter 5/49
Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?
4 valence electrons
4 unpaired electrons

Chapter 5/50
 Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?

4 nonequivalent orbitals

Chapter 5/51
 Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?

4 nonequivalent orbitals 4 equivalent orbitals

Chapter 5/52
Hybridization and sp3 Hybrid
Orbitals
Hybridization and sp3 Hybrid
Orbitals
Other Kinds of Hybrid Orbitals
Other Kinds of Hybrid Orbitals

Chapter 5/56
Other Kinds of Hybrid Orbitals
Other Kinds of Hybrid Orbitals

Chapter 5/58
Other Kinds of Hybrid Orbitals

Chapter 5/59
Molecular Orbital Theory: The
Hydrogen Molecule
Atomic Orbital: A wave function whose square gives
the probability of finding an electron within a given
region of space in an atom.

Molecular Orbital: A wave function whose square

gives the probability of finding an electron within a
given region of space in a molecule.

Chapter 5/60
Molecular Orbital Theory: The
Hydrogen Molecule
 bonding orbital
lower in energy

* antibonding orbital
higher in energy
(# Bonding e- - # Antibonding e-)
Bond Order =
2
Chapter 5/61
Molecular Orbital Theory: The
Hydrogen Molecule

2-0
Bond Order = =1
2
Chapter 5/62
 Molecular Orbital Theory: The
Hydrogen Molecule

2-1 1 2-2
Bond Order: = =0
2 2 2
Chapter 5/63
 Molecular Orbital Theory:
Other Diatomic Molecules
O2 O O

Diamagnetic: All electrons are spin-paired. It is

weekly repelled by magnetic fields.

Paramagnetic: There is at least one unpaired

electron. It is weakly attracted by magnetic fields.

Oxygen, O2, is predicted to be diamagnetic by

electron-dot structures and valence bond theory.

However, it is known to be paramagnetic.

Chapter 5/64
Molecular Orbital Theory:
Other Diatomic Molecules
Molecular Orbital Theory:
Other Diatomic Molecules

Chapter 5/67
Molecular Orbital Theory:
Other Diatomic Molecules

Chapter 5/68