Chapter 11

Theories of Covalent Bonding

11-1
 Theories of Covalent Bonding

11.1 Valence bond (VB) theory and orbital hybridization

11.2 The mode of orbital overlap and types of

covalent bonds

11.3 Molecular orbital (MO) theory and electron delocalization

11-2
 The three models of chemical bonding

Figure 9.2

11-3
Covalent bond
formation in H2

Figure 9.11

11-4
 Key Principles

Structure dictates shape

Shape dictates function

shape = conformation

Molecules can assume more than one

shape (conformation) in solution!

11-5
 The Complementary Shapes of an Enzyme and Its Substrate

11-6
 Valence-shell Electron-Pair Repulsion (VSEPR) Theory

A method to predict the shapes of molecules from their

electronic structures (Lewis structures do not depict
shape)

Basic principle: each group of valence electrons around a central

atom is located as far away as possible from the others in order to
minimize repulsions

Both bonding and non-bonding valence electrons around

the central atom are considered.

AXmEn symbolism: A = central atom, X = surrounding atoms,

E = non-bonding electrons (usually a lone pair)

11-7
 A periodic table of partial ground-state electron configurations

Figure 8.12

11-8
 The steps in determining a molecular shape

molecul Step 1
ar
formula
Lewis Step 2 Count all e- groups
structure around the central atom
A
Note lone pairs
electron- Step 3
and
group
arrangemen double bonds
Count bonding
t bond Step 4 and non-bonding
angles e- groups
separately.
molecula
Figure 10.12
r shape
(AXmEn)

11-9
 Steps to convert a molecular formula into a Lewis
structure
Place the atom with
molecul Step the lowest EN in the
ar 1 center
formula
atom Step Add A-
placeme 2 group
nt numbers
sum of Step Draw single bonds
valence 3 and subtract 2e- for
e- each bond
remainin Step Give
g valence 4 each
e- atom 8e-
Figure 10.1 (2e -
for
Lewis
structure H)

11-10
 Electron-group repulsions and the five basic molecular shapes

Figure 10.5

Ideal bond angles are shown for each shape.

11-11
 The three molecular shapes of the tetrahedral
electron-group arrangement

Examples:
CH4, SiCl4,
SO42-, ClO4-

Examples: Examples:
NH3 H 2O
PF3
OF2
ClO3
H 3O+ SCl2

Figure 10.8
11-12
 The four molecular shapes of the trigonal bipyramidal
electron-group arrangement

Examples:
Examples:
SF4
PF5
XeO2F2
AsF5
IF4+
SOF4
IO2F2-

Examples:
Examples:
XeF2
ClF3
I3-
BrF3
IF2-
Figure 10.10
11-13
 VSEPR
(Valence Shell Electron Pair RepulsionTheory)

Accounts for molecular shapes by assuming that electron

groups tend to minimize their repulsions

Does not show how shapes can be explained from

the interactions of atomic orbitals

11-14
 The Central Themes of Valence
Bond (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.

Three Central 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
(hybridization).
11-15
 Orbital overlap and spin
pairing in three diatomic
molecules

hydrogen, H2

hydrogen fluoride, HF

Figure 11.1

fluorine, F2
11-16
 Linus Pauling

Proposed that valence atomic orbitals in the molecule are

different from those in the isolated atoms

Mixing of certain combinations of atomic orbitals

generates new atomic orbitals

Process of orbital mixing = hybridization; generates

hybrid orbitals

11-17
 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

11-18
 The sp hybrid orbitals in gaseous BeCl2

atomic
orbitals

hybrid
VSEPR
orbitals
predicts a
linear
shape

Figure 11.2

orbital box diagrams

11-19
 The sp hybrid orbitals in gaseous BeCl2 (continued)

orbital box diagrams with orbital contours

Figure 11.2
11-20
 The sp2 hybrid orbitals in BF3

VSEPR predicts
a trigonal planar
shape

Figure 11.3

11-21
 The sp3 hybrid orbitals in CH4

VSEPR
predicts a
tetrahedral
shape
Figure 11.4

11-22
 The sp3 hybrid orbitals in NH3

VSEPR predicts
a trigonal
pyramidal shape

Figure 11.5

11-23
 The sp3 hybrid orbitals in H2O

VSEPR predicts
a bent (V) shape
Figure 11.5

11-24
 The sp3d hybrid orbitals in PCl5

VSEPR predicts
a trigonal bipyramidal
Figure 11.6 shape

11-25
 The sp3d2 hybrid orbitals in SF6

VSEPR predicts an
octahedral shape

Figure 11.7

11-26
11-27
 Conceptual steps from molecular formula to the
hybrid orbitals used in bonding

Step 1 Step 2 Step 3

molecular shape
molecular Lewis hybrid
and e- group
formula structure orbitals
arrangement
Figure Figure Table 11.1
10.1 10.12

Figure 11.8

11-28
 SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

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

atomic orbitals on the central atoms leads to hybrid orbitals in
each of the following molecules.
(a) methanol, CH3OH (b) sulfur tetrafluoride, SF4

PLAN: Use Lewis structures to establish the arrangement of groups

and the 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 has a tetrahedral arrangement
with two non-bonding e- pairs.

11-29
 SAMPLE PROBLEM 11.1 (continued)

2p 2p
sp3 sp3
hybridized C atom hybridized O atom
2s 2s
single C atom single O atom

(b) SF4 has a seesaw shape with four bonding and one non-bonding e- pairs.
F
F S
F 3d 3d
F

distorted 3p
trigonal
bipyramidal sp3d
hybridized
S atom
3s S atom
11-30
 Covalent Bonds Between Carbon Atoms - Single Bonds
 bonds in ethane, CH3-CH3
both carbons are sp3
hybridized s-sp3 overlaps to  bonds

sp3-sp3 overlap to form a  bond

relatively even
distribution of electron
~109.5o density over all  bonds

Figure 11.9 free rotation

11-31
 Covalent Bonds Between Carbon Atoms - Double Bonds
 and  bonds in ethylene, C2H4
overlap in one position - 

p overlap - 

hindered rotation

~120o

electron density
11-32 Figure 11.10
 Covalent Bonds Between Carbon Atoms - Triple Bonds
 and  bonds in acetylene, C2H2

overlap in one position - 

p overlap - 

hindered rotation

180o

Figure 11.11
11-33
 Video: Hybridization

11-34
 SAMPLE PROBLEM 11.2 Describing bonding in molecules with
multiple bonds

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

PLAN: Use the Lewis structure to determine the arrangement of groups and the
shape at each central atom. Postulate the hybrid orbitals, taking note of
multiple bonds and their orbital overlaps.

SOLUTION:
sp2 sp2
sp3 hybridized
O O
O
H sp2
sp hybridized H
3 C H
2
C C H sp sp3
H H H sp3 C
H sp2 C sp
2 3
C sp
sp2 hybridized C 3
H H3 C CH3
sp 3 sp 3 H
sp3 H sp
H sp3
bond
bonds

11-35
 Restricted rotation in -bonded molecules

cis trans
No spontaneous interconversion between
cis and trans forms (isomers) in solution at room temperature!

11-36 Figure 11.12

 Limitations of VB Theory

Inadequately explains magnetic/spectral properties

Inadequately treats electron delocalization

VB theory assumes a localized bonding model

11-37
 Molecular Orbital (MO) Theory
A delocalized bonding model

A quantum-mechanical treatment of molecules

similar to that used for isolated atoms
Invokes the concept of molecular orbitals (MOs)
(extension of atomic orbitals)

Exploits the wave-like properties of matter (electrons)

11-38
 Central themes of molecular
orbital (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).

11-39
 An analogy between light waves and atomic wave
functions

Amplitudes of wave
functions are added

Figure 11.13
Amplitudes of
wave functions are
11-40 subtracted
 Contours and energies of the bonding and antibonding
molecular orbitals in H2

Figure 11.14
11-41
 number of AOs combined = number of MOs produced

Bonding MO: lower in energy than isolated atoms

Antibonding MO: higher in energy than isolated atoms

To form MOs, AOs must have similar energy and orientation

Sigma () and pi () bonds are denoted as before; a star (asterick)
is used to denote antibonding MOs.

11-42
 Molecular orbital diagram for
the H2 molecule

MOs are filled

in the same
sequence
as for AOs

(aufbau and
exclusion
principles, Hund’s
rule)

Figure 11.15

11-43
 The MO bond order

[1/2 (no. of e- in bonding MOs) - (no. of e- in antibonding MOs)]

higher bond order = stronger bond

Has predictive power!

11-44
 MO diagrams for He2+ and He2

*1s *1s
Energy

Energy
1s 1s 1s 1s

1s 1s
AO MO of AO AO MO of AO
of He+ of of He2 of
He He+ He He

He2+ bond order = 1/2 He2 bond order = 0

can exist! cannot exist!
11-45 Figure 11.16
 SAMPLE PROBLEM 11.3 Predicting species stability using MO diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- can exist.
Determine their bond orders and electron configurations.
PLAN: Use H2 as a model and accommodate the number of electrons in
bonding and antibonding orbitals. Calculate the bond order.

SOLUTION: bond order bond order

= 1/2(1-0) = 1/2(2-1)
= 1/2 = 1/2
 H2+ does exist! 
H2- does exist!

1s 1s 1s 1s

AO of H AO of H-
AO of H AO of H+

 

MO of H2+ MO of H2-
configuration is (1s)1 configuration is (1s)2(1s)1
11-46
Figure 11.17

*2s *2s

2s 2s 2s
2s
Energy

Bonding in s-block Be2

Li2 2s homonuclear 2s
diatomic molecules

*1s *1s

1s 1s 1s
1s

1s 1s
11-47 Li2 bond order = 1 Be2 bond order = 0
 Bonding and antibonding MOs for core
electrons cancel = no net contribution to bonding

Only MO diagrams showing MOs created by

combining valence-electron AOs are important.

11-48
 Contours and energies of  and  MOs through
combinations of 2p atomic orbitals

end-to-end
overlap

side-to-side
overlap

Figure 11.18

11-49
 Relative energies

2p < 2p < *2p < *2p

More effective end-to-end interaction

relative to side-to-side in bonding MOs

11-50
 Relative MO energy levels for Period 2 homonuclear
diatomic molecules

without 2s-2p with 2s-2p

mixing mixing

Figure 11.19 MO energy levels MO energy levels

for O2, F2 and Ne2 for B2, C2 and N2
11-51
MO occupancy and
molecular
properties for B2
through Ne2

Figure 11.20
11-52
 The paramagnetic
properties of O2

Explained by
MO diagram

Figure 11.21

11-53
 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 showing the sequence and

occupancy of MOs.
PLAN: Find the number of valence electrons for each species, draw the MO
diagrams, calculate bond orders, and compare the results.
SOLUTION:
N2 has 10 valence electrons, so N2+ has 9.

O2 has 12 valence electrons, so O2+ has 11.

11-54
 SAMPLE PROBLEM 11.4 (continued)

N2 N2+ O2 O2+

2p 2p antibonding

e- lost
bonding e- lost 2p 2p

2p 2p

2p 2p

2s 2s

2s 2s

1/2(8-2) = 3 1/2(7-2) = 2.5 1/2(8-4) = 2 1/2(8-3) = 2.5

(weaker) (weaker)
bond orders
11-55
 Heteronuclear Diatomic
Figure 11.22 Molecules
The MO diagram for HF

Energy

1s
nonbonding MOs

2p
2px 2py
lower in energy
than 1s of H!


AO MO of AO
of H HF of F
11-56
 In polar covalent compounds, bonding MOs
are closer in energy to the AOs of the more
electronegative atom.

11-57
 Figure 11.23
*2s The MO diagram for NO

bond order = 2.5

*2p

2p
Energy

2p 2p

2p possible Lewis

structures
0 0
*2s N O
2s -1 +1
2s
AO of N N O
AO of O
2s

MO of NO
11-58
 The lowest energy -bonding MOs in benzene and ozone

O
O O

resonance hybrid

Figure 11.24
11-59