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Contents
C 2

H  Explaining Covalent Bonding  Overlapping of Atomic Orbitals

in Single and Multiple Bonds
 VBT
A  Hybridization of Atomic Orbitals
 Delocalized π Electrons

P 1  sp Hybrid Orbital

 sp2 Hybrid Orbital

T
 sp3 Hybrid Orbital

E  sp3d Hybrid Orbital

R  sp3d2 Hybrid Orbital

PART A: Chemical Bonding

Explaining of Covalent Bonding VBT

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Molecular Formula VSEPR Model:

 It predicts the geometry of molecule.
 It doesn’t explain why bonds exist between atoms in a molecule.

Lewis Structure
VSEPR Model
a) Electron-domain geometry
b) Molecular geometry
VBT
 It is another model that used to explain further the covalent
bond.
 It explains the covalent bond using atomic orbitals that
overlapped between the two atoms.

 It shows the way of atomic orbitals can mix one another to form the
covalent bond.
VBT

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The overlapping of atomic orbitals in H2 molecule: The overlapping of atomic orbitals in HF molecule:

Orbital diagram of valence electron Orbital diagram of valence electron

1s 1s 1s 2s 2p
H H F
H

H–F
H–H

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The overlapping of atomic orbitals in O2 molecule: The overlapping of atomic orbitals in N2 molecule:
Orbital diagram
of valence electron Orbital diagram
2s 2p 2s 2p of valence electron
2s 2p 2s 2p
O O
N N

O=O NΞN

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Hybridization of Atomic Orbitals

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Remember:
 Hybridization is the process of mixing of the two or more atomic
 The space (electron domain) that formed by overlapping of atomic orbitals to form a new set of orbital that is called as hybrid orbital.
orbitals between two atoms only has two valence electrons with opposite
spins.  The hybrid orbital formed exhibited different shape of the orbital
than the original atomic orbital.

Hybridization

Atomic orbitals Hybrid orbital

How to determine the type of hybrid orbital of the

central atom for particular molecule?
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Five Types of Hybrid Orbitals: Count the electron domains (lone pairs + bonding pairs) around the central
atom.
 sp (linear)
Electron Domains Hybridization Examples
 sp2 (trigonal planar) 2 sp BeCl2

 sp3 (tetrahedral) 3 sp2 BF3

 sp3d (trigonal bipyramidal) 4 sp3 CH4, NH3, H2O

5 sp3d PCl5
 sp3d2 (octahedral)
We determine the type of hybrid orbital based
on the electron-domain geometry. 6 sp3d2 SF6

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sp Hybrid Orbital
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sp

BeCl2  In order to form two covalent bonds with chlorine atoms, beryllium atom
must supply two single valence electrons. This can be achieved using sp
Electron-domain geometry: Linear hybridization.
Hybridization: sp
 Then, the two chlorine atoms are covalently bonded to the beryllium atom
E through the overlapping between the p orbital (Cl) and the sp hybrid
orbital (Be).

Energy Level Diagram

sp2 Hybrid Orbital

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sp2
 In order to form two covalent bonds with fluorine atoms, boron atom
BF3
must supply three single valence electrons. This can be achieved using
sp2 hybridization.
Electron-domain geometry: Trigonal Planar
E Hybridization: sp2  Then, the three fluorine atoms are covalently bonded to the boron atom
through the overlapping between the p orbital (F) and the sp2 hybrid
orbital (B).

Energy Level Diagram

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sp3 Hybrid Orbital

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sp3
 In order to form four covalent bonds with hydrogen atoms, carbon atom
CH4
must supply four single valence electrons. This can be achieved using
sp3 hybridization.
Electron-domain geometry: Tetrahedral
E
Hybridization: sp3  Then, the four hydrogen atoms are covalently bonded to the carbon atom
through the overlapping between the s orbital (H) and the sp3 hybrid
orbital (C).

Energy Level Diagram

The sp3 hybrid orbitals in NH3 The sp3 hybrid orbitals in H2O
E E

Energy Level Diagram

Energy Level Diagram

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sp3d Hybrid Orbitals

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sp3d
 In order to form five covalent bonds with chlorine atoms, phosphorus
atom must supply five single valence electrons. This can be achieved
PCl5
using sp3d hybridization.

Electron-domain geometry: Trigonal bypiramidal  Then, the five chlorine atoms are covalently bonded to the phosphorus
E
Hybridization: sp3d atom through the overlapping between the p orbital (Cl) and the sp3d
hybrid orbital (P).

Energy Level Diagram

sp3d2 Hybrid Orbitals

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sp3d2
 In order to form six covalent bonds with fluorine atoms, sulphur atom
must supply six single valence electrons. This can be achieved using
SF6 sp3d2 hybridization.

 Then, the six chlorine atoms are covalently bonded to the sulphur atom
E Electron-domain geometry: Octahedral through the overlapping between the p orbital (F) and the sp3d2 hybrid
Hybridization: sp3d2 orbital (S).

Energy Level Diagram

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Overlapping of Atomic Orbitals in

Single and Multiple Bonds
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Sigma () bond = end-to-end overlapping Pi () bond = side-by-side overlapping

ONLY p orbitals

The σ bonds in ethane (C2H6)

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C-C 1  bond
both C are sp3 hybridized
C=C 1  bond s-sp3 overlaps to  bonds

1  bond

C C 1  bond
2  bonds sp3-sp3 overlap to form a  bond
All single bonds are
sigma bonds.

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The σ and π bonds in ethylene (C2H4)

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overlap in one position - 

p overlap - 

The half-filled unhybridized 2p orbitals of C are close enough to overlap side-to-side (pi bond).

The σ and π bonds in acetylene (C2H2)

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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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Delocalized π Electrons
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Remember:
Localized electrons:
 In many molecules, however, we cannot adequately describe the
The sigma or pi electrons are associated totally with the two atoms that bonding as being entirely localized.
form the bonding.
 This situation arises particularly in molecules that have two or more
resonance structures involving π bonds.

Delocalized electrons:

The pi electrons that are spread over a number of atoms in a molecule

rather than localized between a pair of atoms.

Benzene Ozone

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Delocalized π electrons in benzene:  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.
Resonance structure of benzene is

 If the resonance structures involve the placement of the double bonds in  The unhybridized 2p orbital on the C atom could be used to make π bonds.
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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Delocalized π electrons in ozone:

 These π electrons are delocalized over the six C – C bonds as shown in figure
below.
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.
 As conclusion, there are three delocalized C – C π bonds in each of the
resonance structures.
 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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