Chapter 11

Theories of Covalent Bonding

11-1 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 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

11-2
 The Central Themes of VB Theory

Basic Principle

A covalent bond forms when the orbitals of two atoms overlap

and the overlap region, which is between the nuclei, is
occupied by a pair of electrons.

The two wave functions are in phase so the amplitude increases

between the nuclei.

11-3
 The Central Themes of VB Theory

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.
There is a hybridization of atomic orbitals to form molecular
orbitals.

11-4
 Figure 11.1 Orbital overlap and spin pairing in three
diatomic molecules.

11-5
 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

11-6
 Figure 11.2 The sp hybrid orbitals in gaseous BeCl2.

11-7
Figure 11.2
The sp hybrid orbitals in gaseous BeCl2.
(continued)

11-8
 Figure 11.3 The sp2 hybrid orbitals in BF3.

11-9
 Figure 11.4 The sp3 hybrid orbitals in CH4.

11-10
 Figure 11.5 The sp3 hybrid orbitals in NH3.

11-11
 Figure 11.6 The sp3d hybrid orbitals in PCl5.

11-12
 Figure 11.7 The sp3d2 hybrid orbitals in SF6.

11-13
11-14
Figure 11.8
The conceptual steps from molecular formula to the hybrid orbitals
used in bonding.

11-15
 SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

PROBLEM: Use partial orbital diagrams to describe how mixing of the

atomic orbitals of the central atom leads to hybrid orbitals in
each of the following:
(a) Methanol, CH3OH (b) Sulfur tetrafluoride, SF4

PLAN: 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 The groups around C are

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

11-16
 SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

continued

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

11-17
 Figure 11.9 The  bonds in ethane(C2H6).
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

11-18
 Figure 11.10 The  and  bonds in ethylene (C2H4).

11-19
 Figure 11.11 The  and  bonds in acetylene (C2H2).

11-20
 Figure 11.12 Electron density and bond order.

11-21
 SAMPLE PROBLEM 11.2 Describing the Types of Bonds in Molecules

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

PLAN: 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.

SOLUTION:

11-22
 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).

11-23
Figure 11.13 An analogy between light waves and atomic wave functions.

11-24
 Figure 11.14 Contours and energies of the bonding and antibonding
molecular orbitals (MOs) in H2.

The bonding MO is lower in energy and the antibonding MO is higher in

energy than the AOs that combined to form them.

11-25
 Figure 11.15 The MO diagram for H2.
Filling molecular orbitals with electrons follows the
same concept as filling atomic orbitals.

11-26
 Figure 11.16 MO diagram for He2+ and He2.

11-27
SAMPLE PROBLEM 11.3 Predicting Stability of Species Using MO Diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- exist. For any
species that exists, write the electron configuration.
PLAN: Use H2 as a model and accommodate the number of electrons in
bonding and antibonding orbitals. Find the bond order.
bond order bond order
SOLUTION: 1 1
= 2 (1 – 0) = 2 (2 - 1)

1 H2+ does exist

1
=2 =2
H2- does exist

configuration is
(1s)2(2s)1

11-28
 Figure 11.17 Bonding in s-block homonuclear diatomic molecules.

11-29
 Figure 11.18 Contours and energies of σ and π MOs through
combinations of 2p atomic orbitals.

11-30
 Figure 11.19 Relative MO energy levels for Period 2 homonuclear
diatomic molecules.

11-31
 Figure 11.20

MO occupancy
and molecular
properties for B2
through Ne2.

11-32
 Figure 11.21

The paramagnetic
properties of O2.

11-33
 SAMPLE PROBLEM 11.4 Using MO Theory to Explain Bond Properties

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

an ion with a weaker, longer bond than in the parent molecule,
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.

11-34
 SAMPLE PROBLEM 11.4 Using MO Theory to Explain Bond Properties

continued

11-35