Theories of Covalent Bonding

Theories of Covalent Bonding

11.1 Valence Bond (VB) Theory and Orbital Hybridization

11.2 The Mode of Orbital Overlap and the Types of

Covalent Bonds

11.3 Molecular Orbital (MO)Theory and Electron Delocalization

The Central Themes of VB Theory

Basic Principle
A covalent bond forms when the orbitals of two atoms overlap
and are occupied by a pair of electrons that have the highest
probability of being located between the nuclei.
Themes
A set of overlapping orbitals has a maximum of two electrons
that must have opposite spins.
The greater the orbital overlap, the stronger (more stable) the
bond.
The valence atomic orbitals in a molecule are different from
those in isolated atoms.

Orbital overlap and

spin pairing in three
diatomic molecules

Hydrogen, H2

Hydrogen fluoride, HF

Fluorine, F2

Hybrid Orbitals
Key Points
The number of hybrid orbitals obtained equals the number of
atomic orbitals mixed.
The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed.
Types of Hybrid Orbitals
sp

sp2

sp3

sp3d

sp3d2

The sp hybrid orbitals in gaseous BeCl2

atomic
orbitals
hybrid
orbitals

orbital box diagrams

The sp hybrid orbitals in gaseous BeCl2(continued)

orbital box diagrams with orbital

contours

The sp2 hybrid orbitals in BF3

The sp3 hybrid orbitals in CH4

The sp3 hybrid orbitals in NH3

The sp3 hybrid orbitals in H2O

The sp3d hybrid orbitals in PCl5

The sp3d2 hybrid orbitals in SF6

The conceptual steps from molecular formula to the hybrid orbitals

used in bonding.

Step 1
Molecular
formula

Step 2
Lewis
structure

Figure 10.1

Step 3
Molecular shape
and e- group
arrangement

Figure 10.12

Table 11.1

Hybrid
orbitals

SAMPLE PROBLEM 11.1

PROBLEM:

Postulating Hybrid Orbitals in a Molecule

Use partial orbital diagrams to describe mixing of atomic

orbitals on the central atoms leads to hybrid orbitals in each of
the following:
(a) Methanol, CH3OH

PLAN:

(b) Sulfur tetrafluoride, SF4

Use the Lewis structures to ascertain the arrangement of groups

and shape of each molecule. Postulate the hybrid orbitals. Use
partial orbital box diagrams to indicate the hybrid for the central
atoms.

SOLUTION:

(a) CH3OH

H
C O
H
H H

The groups around C are

arranged as a tetrahedron.
O also has a tetrahedral
arrangement with 2 nonbonding
e- pairs.

SAMPLE PROBLEM 11.1

Postulating Hybrid Orbitals in a Molecule

continued

2p
2s

2p

sp3
single C atom

hybridized
C atom

2s

sp3
hybridized
O atom

single O atom

(b) SF4 has a seesaw shape with 4 bonding and 1 nonbonding e- pairs.
F
F S
F
F

3d

3d

3p
sp3d
3s

S atom

hybridized
S atom

The bonds in ethane.

both C are sp3
hybridized

s-sp3 overlaps to
bonds

sp3-sp3 overlap to form a

bond

relatively even
distribution of
electron density over
all bonds

The and bonds in ethylene (C2H4)

overlap in one position
p overlap -

electron
density

The and bonds in acetylene (C2H2)

overlap in one position

p overlap -

SAMPLE PROBLEM 11.2

PROBLEM:
PLAN:

Describing the Bonding in Molecules with

Multiple Bonds

Describe the types of bonds and orbitals in acetone, (CH3)2CO.

Use the Lewis structures to ascertain the arrangement of groups and

shape at each central atom. Postulate the hybrid orbitals taking note of
the multiple bonds and their orbital overlaps.
sp2

SOLUTION:

sp2

sp3 hybridized

sp hybridized H
3

sp

C
C
H H H H
sp2 hybridized

sp3

H sp
C

sp H

2
sp2 C sp

sp3
H sp3

sp3

sp3
H
3
sp 3 H
sp

bonds

C
H3 C

CH3
bond

Restricted rotation of -bonded molecules

CIS
TRANS

The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a
collection of nuclei surrounded by delocalized molecular orbitals.
Atomic wave functions are summed to obtain molecular wave
functions.
If wave functions reinforce each other, a bonding MO is formed
(region of high electron density exists between the nuclei).
If wave functions cancel each other, an antibonding MO is formed
(a node of zero electron density occurs between the nuclei).

An analogy between light waves and atomic wave functions.

Amplitudes of wave
functions added

Amplitudes of wave
functions
subtracted.

Contours and energies of the bonding and antibonding

molecular orbitals (MOs) in H2.

The MO diagram for H2

MO diagram for He2+ and He2

*1s
1s

1s

Energy

Energy

*1s

1s

1s

1s
AO of
He

MO of
He+

1s
AO of
He+

He2+ bond order = 1/2

AO of
He

MO of
He2

AO of
He

He2 bond order = 0

SAMPLE PROBLEM 11.3

PROBLEM:
PLAN:

Predicting Species Stability Using MO Diagrams

Use MO diagrams to predict whether H2+ and H2- exist.

Determine their bond orders and electron configurations.

Use H2 as a model and accommodate the number of electrons in

bonding and antibonding orbitals. Find the bond order.

SOLUTION:

1s

bond order
= 1/2(1-0)
= 1/2
H does exist

1s
AO of H

AO of H

MO of H2+

+
2

configuration is (1s)1

1s

bond order
= 1/2(2-1)
= 1/2
H2- does exist
1s
AO of H-

AO of H

MO of H2-

configuration is
(1s)2(2s)1

*2s

*2s
2s

Energy

2s
Li2

2s

Bonding in s-block
homonuclear
diatomic
molecules.

2s

1s

1s

1s

Li2 bond order = 1

1s

Be2

*1s

*1s

1s

2s

2s

Be2 bond order = 0

1s

Contours and energies of s and p MOs through

combinations of 2p atomic orbitals

Relative MO energy levels for Period 2 homonuclear

diatomic molecules.
without 2s-2p
mixing

with 2s-2p
mixing

MO energy levels
for O2, F2, and Ne2

MO energy levels
for B2, C2, and N2

MO occupancy and
molecular
properties for B2
through Ne2

The paramagnetic
properties of O2

SAMPLE PROBLEM 11.4

PROBLEM:

Using MO Theory to Explain Bond Properties

As the following data show, removing an electron from N2 forms

an ion with a weaker, longer bond than in the parent molecules,
whereas the ion formed from O2 has a stronger, shorter bond:
N2

N2+

O2

O2+

Bond energy (kJ/mol)

945

841

498

623

Bond length (pm)

110

112

121

112

Explain these facts with diagrams that show the sequence and occupancy of MOs.
PLAN:

Find the number of valence electrons for each species, draw the MO
diagrams, calculate bond orders, and then compare the results.

SOLUTION:
N2 has 10 valence electrons, so N2+ has 9.
O2 has 12 valence electrons, so O2+ has 11.

SAMPLE PROBLEM 11.4

Using MO Theory to Explain Bond Properties

continued
N2

bonding e- lost

1/2(8-2)=3

N2+

O2

O2+

2p

2p

2p

2p

2p

2p

2p

2p

2s

2s

2s

2s
1/2(7-2)=2.5

bond
orders

1/2(8-4)=2

antibonding
e- lost

1/2(8-3)=2.5

The lowest energy -bonding MOs in benzene and ozone.

The MO diagram for HF

Energy

1s

2px 2py

AO
of H

MO of
HF

2p

AO
of F

The MO diagram for NO

*s

Energy

*p
2p

2p

possible Lewis
structures

p
*s
2s

2s

AO of N

AO of O
s
MO of NO

-1

+1

The steps in converting a molecular formula into a Lewis structure.

Molecular
formula

Step 1

Atom
placement

Place atom
with lowest
EN in center
Step 2
Sum of
valence e-

Add A-group
numbers
Step 3
Remaining
valence e-

Draw single bonds.

Subtract 2e- for each bond.
Step 4
Lewis
structure

Give each
atom 8e(2e- for H)

The steps in determining a molecular shape.

Molecular
formula

Step 1
Lewis
structure

See Figure
10.1
Step 2

Electron-group
arrangement

Count all e- groups around central

atom (A)
Step 3
Bond
angles

Note lone pairs and double

bonds
Count bonding and
Step 4
nonbonding egroups separately.
Molecular
shape
(AXmEn)