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C
H
A
P 1
T
E
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PART A: Chemical Bonding
 Contents
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 Explaining Covalent Bonding  Overlapping of Atomic Orbitals

in Single and Multiple Bonds
 Valence Bond Theory
 Delocalized π Bonding
 Hybridization of Atomic Orbitals

 sp Hybrid Orbitals

 sp2 Hybrid Orbitals

 sp3 Hybrid Orbitals

 sp3d Hybrid Orbitals

 sp3d2 Hybrid Orbitals

Explaining of Covalent Bonding
3

Molecular Formula

Lewis Structure

VSEPR Model
a) Electron-domain geometry
b) Molecular geometry

Valence Bond Theory

 Valence Bond Theory
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VSEPR Model:
 It predicts the geometry/shape of a molecule.
 It does not explain why bonds exist between atoms in a molecule.

VB Theory
 It is a model of covalent bonding.

 It explains the bonding together with the geometry of molecule

(VSEPR model) using atomic orbitals (what is atomic orbital?).

 It shows the ways of atomic orbitals can mix one another to form a
chemical bond.
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 In the Lewis theory, covalent bonding occurs when atoms share electrons.
Such sharing concentrates electron density between the nuclei.

 In the VB theory, the buildup of electron density between two nuclei is

visualized as occurring when valence atomic orbital of one atom overlaps
with that of another atom.

 The overlap of these orbitals allows two electrons of opposite spin to share
the common space between the nuclei, forming a covalent bond.
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The overlap of orbitals in a molecule of hydrogen gas :

Orbital diagram of valence electron

1s 1s
H H

H–H
End to end overlap = sigma () bond
1 σ bond
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The overlap of orbitals in a molecule of hydrogen fluoride:

Orbital diagram of valence electron

1s 2s 2p
H F

H–F

1 σ bond
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The overlap of orbitals in a molecule of oxygen gas:

Orbital diagram
of valence electron
2s 2p 2s 2p
O O

O=O
Side to side overlap = pi (π) bond 1 σ bond
1 π bond
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The overlap of orbitals in a molecule of nitrogen gas:

Orbital diagram
of valence electron
2s 2p 2s 2p
N N

OΞO
1 σ bond
2 π bonds
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Remember:

 The space formed by overlapping of orbitals has a maximum capacity

of two electrons that must have opposite spins.
 Hybridization of Atomic Orbitals
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 The atomic orbitals on an atom mix to form new orbitals called

hybrid orbitals.

 The process of mixing atomic orbitals as atoms approach each other to

form covalent bonds is called hybridization.

 The hybrid orbitals have different shapes than the original atomic
orbitals.

Hybrid orbital
Atomic orbitals Hybridization
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Five Types of Hybrid Orbitals:

 sp (linear)

 sp2 (trigonal planar)

 sp3 (tetrahedral)

 sp3d (trigonal bipyramidal)

 sp3d2 (octahedral) We postulate the type of hybrid orbital

after we observe the molecular geometry
using VSEPR model.
How to predict the hybridization of the central atom of
a molecule?

Count the electron domains (lone pairs + bonding pairs) around the
central atom.

Electron Domains Hybridization Examples

2 sp BeCl2

3 sp2 BF3

4 sp3 CH4, NH3, H2O

5 sp3d PCl5

6 sp3d2 SF6
 sp Hybrid Orbitals
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Lewis structure of BeCl2

Bond diagram of BeCl2

2 electron domains
Central atom (Be): sp

Geometry of BeCl2 It has two bonding pairs. Thus, the

geometry of BeCl2 is a linear.
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Use VB theory to describe the bonding:

2s 2p
Orbital diagram of valance (ground state)
electron for central atom (Be)

(excited state)

hybridization

(hybridized state)

sp
In order to form two covalent bonds with chlorine atoms, beryllium atom must supply two orbitals
which are half-filled. This can be achieved through sp hybridization.

The two chlorine atoms are then covalently bonded to the beryllium atom through the overlap of the p
orbital and with the sp hybrid orbitals.
Atomic orbitals Two sp hybrid orbitals
 sp2 Hybrid Orbitals
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Lewis structure of BF3

Bond diagram of BF3

3 electron domains
Central atom (B): sp2

Geometry of BF3 It has three bonding pairs. Thus, the geometry

of BF3 is a trigonal planar.
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2s 2p
Orbital diagram of valance
electron for central atom (B) (ground state)

(excited state)

hybridization

(hybridized state)
sp2

In order to form three covalent bonds with fluorine atoms, boron atom must supply three orbitals
which are half-filled. This can be achieved through sp2 hybridization.
The three fluorine atoms are then covalently bonded to the boron atom through the overlap of the
p orbital and with the sp2 hybrid orbitals.
 sp3 Hybrid Orbitals
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Lewis structure of CH4

Bond diagram of CH4

4 electron domains
Central atom (C): sp3

Geometry of CH4 It has four bonding pairs. Thus, the geometry of

CH4 is a tetrahedral.
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2s 2p
Orbital diagram of valance (ground state)
electron for central atom (C)

(excited state)

hybridization

(hybridized state)
sp3

In order to form four covalent bonds with hydrogen atoms, carbon atom must supply four orbitals
which are half-filled. This can be achieved through sp3 hybridization.
The four hydrogen atoms are then covalently bonded to the carbon atom through the overlap of the
s orbital and with the sp3 hybrid orbitals.
The sp3 hybrid orbitals in NH3
The sp3 hybrid orbitals in H2O
 sp3d Hybrid Orbitals
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Lewis structure of PCl5

Bond diagram of PCl5

5 electron domains
Central atom (P): sp3d

Geometry of PCl5 It has five bonding pairs. Thus, the

geometry of PCl5 is a trigonal bipyramidal.
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Orbital diagram of valance
electron for central atom (P)

3s 3p 3d
(ground state)

(excited state)

hybridization

(hybridized state)

sp3d
In order to form five covalent bonds with chlorine atoms, phosphorus atom must supply five
orbitals which are half-filled. This can be achieved through sp3d hybridization.
The five chlorine atoms are then covalently bonded to the phosphorus atom through the overlap of
the p orbital and with the sp3d hybrid orbitals.
 sp3d2 Hybrid Orbitals
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Lewis structure of SF6

Bond diagram of SF6

6 electron domains
Central atom (S): sp3d2

Geometry of SF6 It has six bonding pairs. Thus, the geometry

of SF6 is a octahedral.
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Orbital diagram of valance
electron for central atom (S)

3s 3p 3d
(ground state)

(excited state)

hybridization

(hybridized state)

sp3d2
In order to form six covalent bonds with fluorine atoms, sulphur atom must supply six orbitals
which are half-filled. This can be achieved through sp3d2 hybridization.
The six fluorine atoms are then covalently bonded to the sulphur atom through the overlap of the p
orbital and with the sp3d2 hybrid orbitals.
Overlapping of Atomic Orbitals in
Single and Multiple Bonds
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Sigma () bond = end-to-end overlap

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Pi () bond = side-by-side overlap

ONLY p orbitals
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C-C 1  bond

C=C 1  bond
1  bond

C C 1  bond
2  bonds
 The σ bonds in ethane(C2H6)

both C are sp3 hybridized

s-sp3 overlaps to  bonds

sp3-sp3 overlap to form a  bond

All single bonds are
sigma bonds.
 The σ and π bonds in ethylene (C2H4)

overlap in one position - 

p overlap - 

The half-filled unhybridized 2p orbitals of C are close enough to overlap side-to-side (pi bond).
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 The σ and π bonds in acetylene (C2H2)

overlap in one position - 

p overlap - 

The half-filled unhybridized of two 2p orbitals of C are close enough to overlap side-to-side
(pi bond).
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How many sigma and pi bonds are in the acetic acid
(vinegar) molecule CH3COOH?

O
H
 bonds = 6 + 1 = 7
H C C O H
 bond = 1
H
 Describe the types of bonds and orbitals in acetone,
(CH3)2CO.

sp2 sp2
sp3 hybridized
O
O
O sp2
H H
sp3 hybridized H C H sp 2
sp3
C C
H H H H sp3 2
sp2 C sp C sp3 C
C H
sp2 hybridized 3 sp3 H3 C CH3
3
sp H sp 3H
H sp3 sp

bond
bonds
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 Delocalized π Bonding
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Localized electrons:

The sigma and pi electrons are associated totally with the two atoms that
form the bond. These bonding electrons are localized.

Delocalized electrons:

Electrons that are spread over a number of atoms in a molecule rather than
localized between a pair of atoms.
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Remember:

 In many molecules, however, we cannot adequately describe the

bonding as being entirely localized.

 This situation arises particularly in molecules that have two or more

resonance structures involving π bonds.

Benzene Ozone
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Delocalized π bonding in benzene:

Resonance structure of benzene is

 If the resonance structures involve the placement of the double bonds in

different locations, that suggests that the π component of the double bonds is
actually delocalized in a way suggested by the resonance.

 In each of the structures the geometry at C atom is trigonal planar, which implies
sp2 hybridization of the C atom.
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 The sp2 hybrid orbitals are used to construct the six localized C – C σ bonds and
six localized C – H σ bonds that are present in each of the resonance structures.

 The unhybridized 2p orbital on the C atom could be used to make π bonds.

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 These π electrons are delocalized over the six C – C bonds as shown in figure
below.

 As conclusion, there are three delocalized C – C π bonds in each of the

resonance structures.
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Delocalized π bonding in ozone:

Resonance structure of ozone is

' '

 If the resonance structures involve the placement of the double bonds in

different locations, that suggests that the π component of the double bonds is
actually delocalized in a way suggested by the resonance.

 In each of the structures the geometry at O' atom is trigonal planar, which
implies sp2 hybridization of the O' atom.
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 The sp2 hybrid orbitals are used to construct the two localized O – O σ bonds
that are present in each of the resonance structures.

 The unhybridized 2p orbital on the O atom could be used to make π bonds.

 These π electrons are delocalized over the three O – O bonds as shown in figure
below.

 As conclusion, there is a delocalized O – O π bonds in each of the resonance

structures.
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