Chemical Bonding III -

Valence Bond Theory

MUST, CHEMISTRY SECTION -2025

 Objectives
• By the end of this lecture, you should be able to:
1. Determine the hybridization of atomic orbitals.
2. Show the process of hybridization by drawing orbital
diagrams.

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 Problems with Lewis Theory
• Lewis theory does not explain why some single
bonds are stronger than others.
• It does not explain why some single bonds are
longer than others.
• It does not explain how the bond angles in
molecules come to be.
• It often does not predict the correct magnetic
behavior of molecules
 e.g. O2 is paramagnetic, though the Lewis structure
predicts it is diamagnetic

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 Valence Bond Theory (VBT)
It explains :
• The number of bonds that an atom forms in
relation to the configuration of valence electrons.
• The molecular geometries of molecules in terms
of overlapping of atomic orbitals in the valence
shell.
• Why some single bonds are longer than others,
and why some are stronger than others.
• The composition and properties of multiple bonds
, i.e. double and triple bonds.

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 Valence Bond Theory (VBT)
The VB theory says that:
• A covalent bond forms when the orbitals of two
atoms overlap and a pair of electrons occupy the
overlap region.
• The space formed by the overlapping orbitals can
accommodate a maximum of two electrons and
these electrons must have opposite (paired) spins.
• The greater the orbital overlap, the stronger the
bond. Extent of orbital overlap depends on orbital
shape and direction.

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 VB Theory – Orbital overlap
• The diagram below shows the formation of a
hydrogen to hydrogen bond.
• Notice that each atom is coming with a single
unpaired electron in the s-orbital, and these
orbitals are overlapping to form a single bond.

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 VB Theory – Orbital overlap
• In the case of hydrogen fluoride, HF, the single
bond arises from overlap of the s-orbital in
hydrogen, and a 2px-orbital in fluorine:

Hydrogen fluoride, HF.

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 VB Theory – Orbital overlap
• In the case of the fluorine molecule, F2, the single
bond arises from the head-to-head overlap of the
2px-orbital in one F atom, and a 2px-orbital in the
other atom:

Fluorine, F2.
• The single bonds H2, HF, and F2 results from
overlap of different orbitals, hence have different
bond lengths and strength. Explore more on this!
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How do we explain the bond angles in
molecular geometry?

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 VB Theory and Molecular Geometry
• Let us consider the bonding in methane, CH4:
• The Carbon atom has 4 valence electrons, of
which 2 are unpaired.
• Hydrogen has a single electron:

• Looking at the orbital diagram of C, how many

bonds would you expect it form with hydrogen?
What would be the bond angles?
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 VB Theory and Molecular Geometry
• …we expect C to form a maximum of two single bonds with
H using the p-orbitals with unpaired electrons.
• …we expect the bond angle to be 90°. Why? The 3 p-
orbitals in a shell are at right angles to each other. See the
diagram below.

• Does C bond in this

This diagram is manner in reality?
showing 2 of the  No, C can form 4 single
3 p-orbitals (2px bonds with H, with bond
and 2py). angles of 109.5°.
• How do we explain
this discrepancy?
 Read the next slide.

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 VB Theory and Molecular Geometry
• VB theory says that the valence atomic orbitals of
carbon hybridize before bonding with hydrogen.
• Hybridization is mixing of valence atomic orbitals
to form a set of new hybrid orbitals:
 one hybridization of C is to mix all the 2s and 2p orbitals
to get four hybrid orbitals that point at the corners of a
tetrahedron
Bonding in methane
where carbon uses 4
hybrid orbitals that are
109.5° apart, hence
explaining origin of
the 4 bonds and
tetrahedral geometry

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 VB Theory and Orbital Hybridization
• The orbitals that form when bonding occurs are
different from the atomic orbitals in the isolated
atoms.
 If no change occurred, we could not account for the molecular
shapes that are observed.
• Atomic orbitals “mix” or hybridize when bonding
occurs to form hybrid orbitals.
• The spatial orientation of these hybrid orbitals
correspond with observed molecular shapes.

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 Features of Hybrid Orbitals
• The number of hybrid orbitals formed equals the
number of atomic orbitals mixed.
• The hybrid orbitals are degenerate (are at the
same level in energy).
• The type of hybrid orbitals formed varies with the
types of atomic orbitals mixed i.e.,
 sp hybrid orbitals = a single s-orbital + a single p-orbital;
 sp2 hybrid orbitals = a single s-orbital + two p-orbitals
 Sp3 hybrid orbitals = a single s-orbital + three p-orbitals
• Same type of atom can have different types of
hybridization depending on molecule.
 C undergoes sp, sp2, sp3 hybridization.
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 What’s next
• Next we will start looking at examples of sp, sp2,
and sp3 hybridization.
• We will look at:
 sp hybridization of Be in BeCl2;
 sp2 hybridization of B in BF3;
 sp3 hybridization of C in CH4;
 sp3 hybridization of N in NH3;
 sp3 hybridization of O in H2O;
 sp2 hybridization of C;
 sp hybridization of C.
• In all these examples you should be able to draw
the orbital diagrams to show the process of
hybridization.
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 sp hybridization of Be
• An isolated Be atom has two valence electrons that are in
the 2s orbital.
• Be undergoes sp hybridization in order to form 2 bonds:
 In the isolated Be atom, an electron is promoted from the 2s, to one of the
2p orbitals.
 Then, the 2s orbital combines with the 2p orbital (one with a unpaired
electron) to form two sp hybrid orbitals.
 Two of the 2p orbitals remains unhybridized. See the orbital diagrams
below:

You
should Be uses
be able these sp
to draw hybrid
this orbitals to
form two
single bonds.
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 sp2 hybridization of B
• An isolated B atom has 3 valence electrons, 2 in the 2s
orbital & 1 in the 2p orbital.
• B undergoes sp2 hybridization in order to form 3 single
bonds:
 An electron is promoted from the 2s orbital to one of the empty 2p orbitals.
 The 2s orbital combines with two 2p orbitals to form three sp2 hybrid
orbitals.
 The empty 2p orbital remains unhybridized.

B uses these
sp2 orbitals to
form three
single bonds.

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 sp3 hybridization of C (as in CH4)
• An isolated C atom has 4 valence electrons, 2 in the 2s
orbital & 2 in the 2p orbital.
• C undergoes sp3 hybridization in order to form 4 single
bonds:
 An electron is promoted from the 2s orbital to the empty 2p orbital.
 The 2s orbital combines with all the 2p orbitals to form four sp3 hybrid
orbitals as shown below:

These sp3
orbitals are
used to form
four single
bonds.

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 sp3 hybridization of N in NH3
• An isolated N atom has 5 valence electrons, 2 in the 2s
orbital & 3 in the 2p orbital.
• N undergoes sp3 hybridization in order to form 3 single
bonds:
 The 2s orbital combines with all the 2p orbitals to form four sp3 hybrid
orbitals.
 The lone pair is also in a hybrid sp3 orbital.

Three of these
sp3 orbitals are
used to form
three single
bonds.

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 sp3 hybridization of O in H2O
• An isolated O atom has 6 valence electrons, 2 in the 2s
orbital & 4 in the 2p orbital.
• O undergoes sp3 hybridization in order to be able to form 2
single bonds:
 The 2s orbital combines with all the 2p orbitals to form four sp3 hybrid
orbitals.
 The two lone pairs are also in a hybrid sp3 orbitals.

Two of these
sp3 orbitals are
used to form
two single
bonds.

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 Reflection:






What is the hybridization of C in ethylene
(C2H4)?




- There is a C to C double bond in ethylene

- Hence, we need to understand the composition of the
double bond to be able to answer this question.

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 Types of covalent Bonds
• A sigma () bond results when the interacting
atomic orbitals point along the axis connecting the
two bonding nuclei
 either standard atomic orbitals or hybrids
 s–to–s, p–to–p, hybrid–to–hybrid, s–to–hybrid, etc.
• A pi () bond results when the bonding atomic
orbitals are parallel to each other and perpendicular
to the axis connecting the two bonding nuclei
 between unhybridized parallel p orbitals
• The interaction between parallel orbitals is not as
strong as between orbitals that point at each other;
therefore  bonds are stronger than  bonds
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 Types of covalent Bonds

• A single bond consists of a single sigma bond.

• A double bond consists of a sigma bond and a pi bond.
• A triple bond consists of one sigma bond and two pi bonds.

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 Hybridization of C in C2H4
C C

H • In C2H4, each C atom forms 1 double

bond to another C and 2 single bonds to
H atoms.
• Double bond = 1 sigma and 1 pi bond
• 2 single bonds = 2 sigma bonds
• Therefore, each C atom forms a total of
3 sigma bonds (from 3 hybrid orbitals),
and 1 pi bond (from 1 unhybridized p-
orbital). C is sp2 hybridized in C2H4:
 Promote an electron from 2s to empty 2p
 Mix 2s orbital with two of the 2p orbitals to
get 3 hybrid orbitals.

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 Practice Question 1

• What is the hybridization of the carbon atoms in

acetylene (C2H2)?

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 Practice Question 1 - Solution
• Each carbon atom forms 2 sigma bonds and 2 pi bonds.
• Each carbon atom uses 2 hybrid orbitals for the sigma
bonds, and 2 unhybridized p-orbitals for the pi bonds.
• It is sp hybridization that can give us this.

Unhybridized C atom sp hybridized C atom

2 pi bonds
   
2p 2p
2 sigma
   bonds
2s 2sp
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 Practice Question 2

• Determine the hybridization of the phosphorous

atom in PCl5.

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 Practice Question 2 - Solution
• P forms 5 sigma bonds.
• We need 5 hybrid orbitals on P to get 5 sigma bonds.
• The hybridization is sp3d as shown below. Remember, the

valence shell in P has empty d-orbitals that are used.

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The End

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