Ch.

9 Chemical Bonding and

Molecular Structure

Brady & Senese, 5th Ed

Index
9.1. Molecules are three-dimensional with shapes that are
built from five basic arrangements
9.2. Molecular shapes are predicted using the VSEPR model
9.3. Molecular symmetry affects the polarity of molecules
9.4. Valence bond theory explains bonding as an overlap of
orbitals
9.5. Hybrid orbitals are used to explain experimental
molecular geometries
9.6. Hybrid orbitals can be used to explain multiple bonds
9.7. Molecular orbital theory explains bonding as constructive
interference of atomic orbitals
9.8. Molecular orbital theory uses delocalized orbitals to
describe molecules with resonance structure
The Five Basic Electron Arrangements

Electron Shape Electron Pair

Domains Geometry
2 linear

3 trigonal planar

4 tetrahedral

9.1 Molecules are three-dimensional with shapes that are built from five basic 3
arrangements
The Five Basic Electron Arrangements (Cont.)

Electron Domains Shape Electron Pair Geometry

5 trigonal bipyramidal

has equatorial and axial

positions.

6 octahedral

has equatorial and axial

positions

9.1 Molecules are three-dimensional with shapes that are built from five basic 4
arrangements
Learning Check:
Identify The Electron Pair Geometry For Each Center

tetrahedral tetrahedral Trigonal

bipyramidal

9.1 Molecules are three-dimensional with shapes that are built from five basic 5
arrangements
Your Turn!

What is the electron pair geometry for C in CO2?

A. linear
B. planar triangular
C. tetrahedral
D. trigonal bipyramidal
E. octahedral

9.1 Molecules are three-dimensional with shapes that are built from five basic 6
arrangements
Bonding Domains And Non-bonding Domains

• Bonding domains are shared

between nuclei
• Non-bonding domains are not
shared between nuclei-they exert a
greater electrical field
• Repulsion leads non-bonding
domains to occupy larger space
• The basic shapes are distorted by
non-bonding domains to create the
molecular geometry

9.2 Molecular shapes are predicted using the VSEPR model 7

Trigonal Planar Molecular Geometries

Bonding Domains Non-bonding Molecular

Domains Geometry

3 0 trigonal planar

2 1 bent

9.2 Molecular shapes are predicted using the VSEPR model 8

Tetrahedral Molecular geometries

9.2 Molecular shapes are predicted using the VSEPR model 9

Trigonal Bipyramidal

• Equatorial (e)
positions are
substituted first
• This is because
the e,e bond
angles are 120°,
while a,e bond
angles are only
90°

9.2 Molecular shapes are predicted using the VSEPR model 10

Octahedral Geometries

• All bond angles

are 90°
• Axial positions
are substituted
first

9.2 Molecular shapes are predicted using the VSEPR model 11

Learning Check:
Identify the molecular geometry for each center

Trigonal Non-linear,
Linear
pyramidal bent

9.2 Molecular shapes are predicted using the VSEPR model 12

Your Turn!

Which require more space?

A. bond pairs
B. lone pairs
C. both are the same

9.2 Molecular shapes are predicted using the VSEPR model 13

Your Turn!

Which bond angles are closer in a trigonal

bipyramidal structure (a= axial; e=equatorial)?
A. a-a
B. a-e
C. e-e
D. they are all the same

9.2 Molecular shapes are predicted using the VSEPR model 14

Your Turn!

What is the molecular geometry of C in CH4?

A. Linear
B. Square planar
C. Square pyramidal
D. Tetrahedral
E. None of these

9.2 Molecular shapes are predicted using the VSEPR model 15

Polar Molecules Are Asymmetric
• To determine the polarity, draw the structure using
the proper molecular geometry
• Draw the bond dipoles
• If they cancel, the molecule is non-polar
• If the molecule has uneven dipole distribution, it is
polar

9.3 Molecular symmetry affects the polarity of molecules 16

Learning Check:

Polar or non-polar?

polar polar Non-polar

9.3 Molecular symmetry affects the polarity of molecules 17

Your Turn!

CH2ClCH2Cl (freon-150) is likely to be:

A. Polar
B. non-polar
C. cannot tell

9.3 Molecular symmetry affects the polarity of molecules 18

Your Turn!

Benzoyl peroxide (used in common acne

medications) is likely to be:
A. polar
B. non-polar
C. cannot tell

9.3 Molecular symmetry affects the polarity of molecules 19

Valence Bond Theory

• H2 bonds form because atomic valence orbitals

overlap

1s 1s

• HF involves overlaps between the s orbital on H

and the 2p orbital of F

1s 2s 2p
9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 20
VB Theory And H2S

• Assume that the

unpaired e- in S and H
are free to form a
paired bond
• We may assume that
the H-S bond forms
between an s and a p
orbital

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 21

Your turn!

According to VB Theory:
Which type of overlap does not occur in BH3?
A. s-s
B. s-p
C. p-p
D. none of these

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 22

Your turn!

According to VB Theory:
Which orbitals overlap in the formation of NH3?
A. s-s
B. s-p
C. p-p
D. none of these

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 23

Difficulties With VB Theory So Far:

• Most experimental bond angles do not support

those predicted by mere atomic orbital overlap
• For example: C 1s22s22p2 and H 1s1
• Experimental bond angles in methane are 109.5°
and all are the same
• p orbitals are 90° apart, and not all valence e- in C
are in the p orbitals
• How can multiple bonds form?

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 24

Hybridization

• The mixing of atomic orbitals to allow formation

of bonds that have realistic bond angles
• The new shapes that result are called “hybrid
orbitals”
• The number of hybrid orbitals required = the
number of bonding domains + the number of
non-bonding domains on the atom

9.5 Hybrid orbitals are used to explain experimental molecular geometries 25

What Shall We Call These New Orbitals?

• Since we have annexed the spaces previously

defined by atomic orbitals, we name the hybrid as
a combination of the orbitals used to form the new
hybrid
• One atomic orbital is used for every hybrid formed
(orbitals are conserved)

9.5 Hybrid orbitals are used to explain experimental molecular geometries 26

Hybrids From s & p Atomic Orbitals take
VSEPR Geometry
Hybrid Atomic Electron
Orbitals Geometry
Used
sp3 s + px + py Tetrahedral,
+ pz bond angles
109.5˚
sp2 s + px + py Trigonal
planar, bond
angles 120 ˚
sp s + px Linear,
bond angles
180 ˚

9.5 Hybrid orbitals are used to explain experimental molecular geometries 27

Learning Check:

Identify The Hybrid Orbitals In The Following, Based

On Their VSEPR Geometry

9.5 Hybrid orbitals are used to explain experimental molecular geometries 28

Determining hybridization:

1. expand all valence electrons within the valence

energy level. For C, for example this means:
• 2s↑↓ 2p ↑ _ ↑ ___ [He]2s2 2p1
• Becomes:
• 2s↑ 2p ↑ _ ↑ _ ↑ __

9.5 Hybrid orbitals are used to explain experimental molecular geometries 29

Hybridization

• 2. Now analyze the bonding and lone pair needs.

You will need to use one hybrid orbital for every
bonding domain and one for every non-bonding
domain.
• For C in CH4 we see that there are 4 attached
atoms and no lone pairs on C. Thus we will need 4
hybrid orbitals.

H
C
H H
9.5 Hybrid orbitals are used to explain experimental molecular geometries 30
Hybridization (sp3)

• 3. Now analyze the atomic orbital needs. You will need

to use one atomic orbital for every hybrid orbital .
• For C in CH4 we will need 4 hybrid orbitals.
• 2s↑ 2p ↑ _ ↑ ↑_
• Thus, we will need to use all valence level atomic
orbitals available to us.
• (2s↑ 2p ↑ _ ↑ _ ↑)
• S + p + p + p → 4 new equivalent “sp3” orbitals.
H

H
C
H H
9.5 Hybrid orbitals are used to explain experimental molecular geometries 31
Bonding in CH4 H

• The 4 hybrid orbitals are H

evenly distributed around
H H
the C
• The H s-orbitals overlap
the sp3 hybrid orbitals to
form the bonds.

9.5 Hybrid orbitals are used to explain experimental molecular geometries 32

s & p hybrid shapes

9.5 Hybrid orbitals are used to explain experimental molecular geometries 33

Your Turn!

In the compound CH3OH, what is the expected

hybridization on O?
A. sp
B. sp2
C. sp3
D. O does not hybridize

9.5 Hybrid orbitals are used to explain experimental molecular geometries 34

Expanded Octet Hybridization

• Can be predicted from the geometry as well

• In these situations, d orbitals are be needed to
provide room for the extra electrons
• One d orbital is added for each pair of electrons in
excess of the standard octet

9.5 Hybrid orbitals are used to explain experimental molecular geometries 35

Expanded Octet hybridization

9.5 Hybrid orbitals are used to explain experimental molecular geometries 36

 Bonding Types
• Two types of bonds result from
orbital overlap:
• sigma bonds
▪ from head-on overlap
▪ lie along the bond axis
▪ account for the first bond
• pi bonds
▪ from lateral overlap by adjacent p or
d orbitals
▪ pi bonds are perpendicular to bond
axis
▪ account for the second and third
bonds in a multiple bond
9.6 Hybrid orbitals can be used to describe multiple bonds 37
 Hybridization of C in CH2O O
C
H H
1. Expand all valence electrons within the same energy
level. For C, for example this means:
• 2s↑↓ 2p ↑ _ ↑ ___ [He]2s2 2p1
• Becomes:
• 2s↑ 2p ↑ _ ↑ _ ↑ __

9.6 Hybrid orbitals can be used to describe multiple bonds 38

Hybridization of C in CH2O O
C
H H

• 2. Now analyze the bonding and lone pair needs.

You will need to use one hybrid orbital for
every attached atom and one for every lone pair.
▪ For C in CH2O we see that there are 3 attached atoms
and no lone pairs on C. Thus we will need 3 hybrid
orbitals.

9.6 Hybrid orbitals can be used to describe multiple bonds 39

sp2 Hybridization
• 3. Now analyze the atomic orbital needs. You will
need to use one atomic orbital for every hybrid
orbital.
▪ For C in CH2O we will need 3 hybrid orbitals.
▪ 2s↑ 2p ↑ _ ↑ ↑_
▪ Thus, we will need to use 3 valence level atomic
orbitals available to us, and one of the p orbitals will
remain.
▪ (2s↑ 2p ↑ _ ↑ ) _ ↑
▪ s + p + p → 3 new “sp2” orbitals.
▪ We are left with one unhybridized orbital.

9.6 Hybrid orbitals can be used to describe multiple bonds 40

Now analyze the O: O
C
• [He] 2s2 2p2 (2s↑↓ 2p ↑ ↓_ ↑ ) _ ↑ H H
• The O is has one bonding domain and 2 non-
bonding domains, hence it will require three
hybrid orbitals.
• No expansion needed, as one unpaired e- is
available to bond. Use 3 atomic orbitals to make
the new hybrids, sp2. (2s↑↓ 2p ↑ ↓_ ↑ ) _ ↑
• Again we are left with one unhybridized p
orbital

9.6 Hybrid orbitals can be used to describe multiple bonds 41

Pi Bonding

9.6 Hybrid orbitals can be used to describe multiple bonds 42

H−C≡C −H

• Each C has a
triple bond
and a single
bond
• Requires 2
hybrid
orbitals, sp
• unhybridized
p orbitals
used to form
the pi bond
9.6 Hybrid orbitals can be used to describe multiple bonds 43
Your Turn!

Consider a molecule of CH3CO2H:

How many pi bonds are there in the molecule?
A. 1
B. 2
C. 3
D. 4
E. There are none

9.6 Hybrid orbitals can be used to describe multiple bonds 44

Molecular Orbital Theory
• Modification of VB theory that considers that the orbitals
may exhibit interference.
• Waves may interfere constructively or destructively
• Bonding orbitals stabilize, antibonding destabilize.

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 45

orbitals
MO diagrams

• Show atomic energy level diagram for each atom

• Show molecular orbitals (bonding and
antibonding*)
• 1 MO for each Atomic orbital.
• Show electron occupancy of the orbitals.

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 46

orbitals
Filling MO diagrams

1. Electrons fill the lowest-energy orbitals that are

available.
2. No more than two electrons, with spins paired,
can occupy any orbital.
3. Electrons spread out as much as possible, with
spins unpaired, over orbitals that have the same
energy.
4. Bond order = e- in bonding orbital-e- in
nonbonding orbitals.

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 47

orbitals
Diatomic MO diagrams differ by group
• A) I - V B) VI-VIIIA

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 48

orbitals
MO diagrams
Draw the expected MO diagram for:
• O2

• BH

• He2

Which are not likely to exist, and why?

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 49

orbitals
Delocalized Electrons

• Lewis structures use resonance to explain that the

actual molecule appears to have several equivalent
bonds, rather than different possible structures
• MO theory shows the electrons being delocalized
in the structure

9.8 Molecular orbital theory uses delocalized orbitals to describe molecules with 50
resonance structures
CO32- Hybridization

• Carbonate has three equivalent resonance

structures. What are they, and which electrons are
delocalized?

• Draw the hybrid molecule to indicate the

delocalization of these electrons.

9.8 Molecular orbital theory uses delocalized orbitals to describe molecules with 51
resonance structures