Faculty of Pharmaceutical

Engineering
CHEM-111
LECTURE 5_WS24

Hybridization of
Atomic Orbitals
Marwa Saeed Hany, PhD
[email protected]

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 LECTURE 5- learning Outcomes

 Introduce the valence bond theory

 Define the term hybridization

 Identify the different types of hybrid orbitals

 Define the different geometries of various types of hybrid orbitals

 Apply different types of orbital hybridization

 Determine the effect of multiple bonds

 Identify the formation of sigma and pi bonds

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 Valence Bond (VB) Theory
Considering the formation of a H2 molecule from two H atoms:

• According to the Lewis Theory concerned with Valence Electrons:

The H-H bond is formed in terms of the pairing of the two electrons on the H atoms

• According to the Valence Bond Theory concerned with Valence Orbitals:

The covalent H-H bond is formed by the overlap of the two 1s orbitals in the H atoms
Overlap means that the two orbitals share a common region in space
As two H atoms approach each other:

• Their 1s orbitals begin to interact and each electron

begins to feel the attraction of the other proton

• Gradually, the electron density builds up in the region

between the two nuclei (red color)

• A stable H2 molecule is formed when the inter-nuclear

distance is 74 pm
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 Hybridization of Atomic Orbitals
Valence Orbitals :
• Orbitals associated with the highest principal quantum level that contain electrons on a given atom

• Bonding involves only the valence orbitals

Example:

1. Carbon Atom 1s22s22p2

The valence orbitals of a carbon atom are the 2s and 2p orbitals

C has 2 single electrons only in two of the p orbital

Accordingly, you might expect carbon to be able only to form two bonds using these 2 single electrons

This is NOT true, C is known to bind to 4 H atoms and forms CH4 (methane) NOT CH2
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 Hybridization of Atomic Orbitals
Bonding in Methane (CH4)
How can C form four bonds although it has 2 single electrons not 4 ?

An electron from the 2s is excited (promoted) to the empty p orbital

leading to 4 unpaired electrons in 4 orbitals ready to overlap with the
4H atoms (1s)

• There is only a small energy gap between the 2s and 2p orbitals, and so it pays the carbon to provide a small
amount of energy to promote an electron from the 2s to the empty 2p to give 4 unpaired electrons
• The carbon atom is now said to be in an excited state
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 Hybridization of Atomic Orbitals
Bonding in Methane (CH4)
Since bonding involves only the valence orbitals, can we say :

A Carbon atom uses its 2s and 2p orbitals to form the 4 C-H bonds with four 1s orbitals of 4 H atoms ?

This is NOT true because Methane is known to have four identical C-H bonds

Using the 2p and 2s atomic orbitals will lead to two different types of
C-H bonds:

(a) Three C-H bonds resulting from the overlap of a 2p orbital of

carbon and a 1s orbital of hydrogen
So, HYBRIDIZATION must come after
(b) One C-H bond resulting from the overlap of a 2s orbital of carbon
PROMOTION
and a 1s orbital of hydrogen

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 Hybridization of Atomic Orbitals
Bonding in Methane (CH4):

• The carbon atom has four equivalent atomic orbitals, obtained by MIXING the carbon 2s and 2p orbitals

• This mixing of the native atomic orbitals to form special orbitals for bonding is called HYBRIDIZATION

• The four new orbitals are called sp3 orbitals because they are formed from mixing one 2s and three 2p

orbitals

• The four sp3 hybrid orbitals are identical in shape, each one having a large lobe and a small lobe

• The four orbitals are oriented in space in a tetrahedral arrangement

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 Hybridizatio
n
Hybridization : Mixing of atomic orbitals of different shape, size and energy to form new equivalent hybrid
orbitals of same shape, size and energy

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 Sp3 Hybridization
CH4 has a tetrahedral shape,
Bonding in Methane (CH 4):
each hybrid orbital point to
one corner of the tetrahedron
and all the HCH angles are
109.5°

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 Sp3 Hybridization
Bonding in Methane (CH4):

• In order to form 4 bonds, C must promote an electron

• 4 orbitals are mixed to form 4 hybrid orbitals ready to form 4 bonds

1s + 3p = 4 sp3
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 Types of Hybridization

Number of the hybrid

orbitals formed =
Number of orbitals
participating in
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hybridization
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 How to Determine the Type of Hybridization
1. Count the number of effective electron pairs around the atom OR: Count
attached atoms and lone pairs
• Effective electron pairs can Lone pair
be Single All count
bond as
Double one
bond
2. Deduce the type of hybridization of each atom based
on the number of
Triple bond
effective electron pairs ( you must draw correct Lewis structure)
No. of Type of No. of Effective Type of
Effective Hybridization Electron Hybridization
Electron Pairs Pairs
2 sp 5 dsp3
3 sp2 6 d2sp3
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4 sp3 Dr. Marwa Saeed Hany_ Lec 5
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 Hybridization & Geometry

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 Molecular Geometry

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 Types of Hybridization- TRY IT YOURSELF

SP3

SP2

SP
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 Types of Hybridization- EXAMPLES
Water H2O Sp3 hybridization

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 Types of Hybridization- EXAMPLES
Water H2O Sp3 hybridization

The other two hybrid orbitals Repulsion between the

accommodates the lone pair lone pair electrons and
on oxygen bonding electron pairs
decreases the HOH
bond angles from 109.5°
to 104.5 °

Two of the four hybrid

orbitals of oxygen form
covalent O-H bonds

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 Effect of Lone Pairs on Bond Angles

The electron cloud of an

unshared pair is expected to
spread out over a larger volume
than that of a bonding pair

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 Effect of Lone Pairs on Bond Angles
 Non bonding pairs show greater repulsions
 This tends to force bonding pairs closer to one another
 Thus decrease bond angles in a molecule

Repulsion between:
Lone-pair vs lone-pair > lone-pair vs bonding
>
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bonding-pair vs bonding-pair
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 Types of Hybridization- EXAMPLES
Boron triflouride BF3 Sp2 hybridization
B needs 3 unpaired electrons in 3 hybrid orbitals

Ground state electron configuration, can form only

one bond

Now, 3 sp2 hybrid orbitals with 3 unpaired

electrons can form 3 bonds

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Unhybridized p orbital
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 Types of Hybridization- EXAMPLES
BF3 Sp2 hybridization

Three hybrid orbitals are directed

towards the 3 corners of a trigonal
planar shape

One Unhybridized empty p orbital

is
also available

All the FBF angles are 120°

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 Types of Hybridization- EXAMPLES
Beryllium Fluoride BeF2 Sp hybridization

 Beryllium atom has the configuration 1s2, 2s2

 Since there are NO unpaired electrons in the

valence 2s orbital, it cannot form any covalent
bonds

 Thus, an electron is shifted from 2s-orbital to

2p-orbital followed by hybridization between
one s and one p to give 2 sp hybrid orbitals
carrying 2 single electrons ready to form 2
bonds

 BeF2 molecule is linear with bond angle=

180o
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 Types of Hybridization- EXAMPLES
Sp3d Hybridization
EXAMPLE:

PCl5

A set of five effective pairs around a

given atom always requires a triangular
bipyramid arrangement, which in turn
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hybridizati
requires sp d Dr. Marwa Saeed Hany_ Lec 5
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 Types of Hybridization- EXAMPLES
Sp3d Hybridization
EXAMPLE:

SF4

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 Types of Hybridization- EXAMPLES
EXAMPLE: Sp3d2 Hybridization
SF6

Six electron pairs around an

atom are always arranged
octahedrally and require
d2sp3 hybridization of the
atom

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 Types of Hybridization- EXAMPLES
EXAMPLE: Sp3d2 Hybridization
XeF4

Home assignment:
To be discussed next
lecture:
Full explanation of
formation of XeF4 using
What about F hybridization in XeF4: excitation and hybridization
principles
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 Hybridization- In presence of Double & Triple Bonds
Ethene carbon C2H4 Sp2 hybridization

The arrangement of the hybrid orbitals is This remaining p orbital is oriented

trian12/13/202
4 g u l a r planar arrangement
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 Hybridization- In presence of Double & Triple Bonds

Ethene molecule C2H4 Sp2 hybridization

Sigma () bonds are

formed from Orbitals
whose lobes point
towards each other
(head to head)
Pi (𝝅) bonds result
from parallel (side to
side) orbitals overlap

A double bond is
formed from:
• Hybrid orbitals form only sigma bonds, accommodate lone pairs 1 sigma + 1 pi
• Un-hybridized orbitals overlap to form pi bonds bonds
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 Hybridization- In presence of Double & Triple Bonds
In Ethene Molecule
• Two sp2 -hybridized carbon atoms form a sigma () bond by overlap of their sp2 orbitals (C-C)

• Each carbon forms sigma () bonds with 2 hydrogens through overlap between C sp2 orbital
and H 1s orbital (C-H)

• Sideways overlap of unhybridized p orbitals leads to a pi (𝝅) bond (C=C)

• sigma () bonds are stronger than pi bonds where electron density is concentrated between
the n12/13/202
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Saeedbelow
Hany_ Lec the plane of the nuclei as in pi
 Hybridization- In presence of Double & Triple Bonds
Nitrogen N2 Sp hybridization

form 2 pi bonds

Triple bond is
1 sigma and
2 pi bonds

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 Hybridization- In presence of Double & Triple Bonds
Carbon dioxide CO2 Sp hybridization
Number of effective electron pairs around C is 2 so hybridization of C is sp
Number of effective electron pairs around O is 3 so hybridization of O is sp2
Carbon Atom Oxygen Atom

Promotion

Hybridization

Form 212/13/202
4 s i g m a
11 /2 1 /2 021
Form 2 pi bonds
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 Hybridization- In presence of Double & Triple Bonds
Two sp2 hybrid orbitals of O
accommodate the lone pairs
on oxygen, the 3rd form sigma
bond with C

BUT/ Where are the pi bonds

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 Hybridization- In presence of Double & Triple Bonds
Complete picture of Carbon dioxide
2 un-hybridized p orbitals on the sp hybridized C are used to form the two pi bonds with the
unhybridized 2p orbitals of the 2 O atoms on both sides

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 Types of Hybridization- NOW TRY IT YOURSELF
Select the statement that correctly describes the hybridization of P in PF5

a) Phosphorus is sp2 hybridized

b) Phosphorus is sp3d2 hybridized

c) Phosphorus is sp3d hybridized

d) Phosphorus is sp3 hybridized

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 Types of Hybridization- NOW TRY IT YOURSELF
How many sigma bonds and pi bonds are there in each of the following molecules?

10 σ bonds
3 π bonds

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 Types of Hybridization- NOW TRY IT YOURSELF
What is the hybridization of the oxygen atom and the carbon atoms 1, 2, and 4,
respectively?

sp3 sp3 sp sp2

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 Types of Hybridization- NOW TRY IT YOURSELF
9- Which of the following hybridization patterns best describes the carbon atom in NCO-?

a) sp2
b) sp3d
c) sp3
d) sp
e) sp3d2

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 References

R.Chang, Chemistry, 12th edn., Chapter 10

Zumdahl, Chemistry, 10th edn., chapter 9

Zumdahl, Chemistry, study guide, 10th edn., chapter 9

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