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CHM 211: BASIC
INORGANIC CHEMISTRY I
Prof. (Mrs.) C.A. AKINREMI
Module 3&4: CHEMICAL BONDING
AND BONDING THEORIES
Course Content:
Module Topics
1 Wave mechanical treatment of atomic structure.
2 Periodicity and periodic table.
3 Chemical bonding.
4 Bonding theories; valence bond theory, molecular bond
theories.
5 Inorganic stereochemistry.
6 Chemistry of group IIIA (Boron group), VA (Nitrogen
group), Noble gas.
7 Introduction to 1st row transition metal chemistry
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Chemical bonding
• refers to the formation of a chemical
bond between two or more atoms,
molecules or ions to give rise to a
chemical compound.
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Lewis Structure
• Lewis proposed that a covalent bond is
formed when two neighboring atoms share
one or more electron pair.
• Octet Rule
states that. “Each atom shares electrons
with neighboring atoms to achieve a total
of eight valence electrons (an octet)”.
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Example:
• Chlorine:
Cl Cl Cl Cl
•CCl4
Cl
C 4 Cl Cl C Cl
Cl
•N2:
N + N N N
Exceptions
•Hydrogen(1), Beryllium(2,2) and B(2,3)
Be + 2 [ F ] F Be F
F
B + 3[ F ] F B F
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• For molecules with odd numbers of
electrons
Example;
NO=11 electrons,
ClO2=19 electrons
• Compounds with more than four covalent
bonds must break the octet rule
Eg PF3 obeys octet rule but PF5 doesnot.
[P=2,8,5].
Valence shell electron pair repulsion
theory (VSEPR)
This theory provides a method for predicting the shape of
molecules, based on the electron pair electrostatic
repulsion.
Sidgwick-Powell theory suggests that for molecules and ions
that contain single bonds, the approximate shape can be
predicted from the number of electron pairs in the outer or
valence shell of the central atom.
It was assumed that electron pairs will arrange themselves
so as to be far apart as possible because of their mutual
repulsion.
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Valence shell electron pair repulsion
theory (VSEPR)
1. The shape of the molecule is determined by repulsions
between all the electron pairs present in the valence shell.
2. A lone pair of electrons takes up more space round the
central atom than a bond pair, since the lone pair is
attracted by one nucleus while a bonded pair is shared
between two nuclei. Therefore, repulsion is in this order,
two lone pair>between a lone pair and bond pair> two
bond pairs.
3. The magnitude of repulsions between bond pairs of
electrons depends on the electronegativity difference
between the central atom and other atoms
4. Double bonds cause more repulsion than single bonds,
and triple bonds than double bonds
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Valence Theory.
• This theory was proposed by Linus Pauling
• This theory considers the interaction of separate
atoms as they are brought together to form a
molecule.
• It is a way of expressing the lewis theory in terms of
wave concepts.
• In VB theory, a bond between atoms A and B is
formed when two atomic orbitals, one from each
atom, merge with one another (the technical term is
overlap), and the electrons they contain pair up (so
that their spins are ↓↑).
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• The merging of orbitals gives rise to
constructive interference—i.e., an
enhancement of amplitude—between the
wavefunctions in the areas where they
overlap, which results in the internuclear
region.
• There is an increased probability of finding
the electrons in the internuclear region (so
echoing Lewis' conception of the bond)
and, by implication, a lowering of the
energy of the molecule.
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In summary
• A single bond in a Lewis structure
corresponds to a σ bond of VB theory.
• A double bond corresponds to a σ bond
plus a π bond, and a triple bond
corresponds to a σ bond plus two π
bonds.
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H2
• Here, the VB wavefunction is formed by
spin pairing of the electrons in the two
contributing atomic orbitals. This electron
distribution is called a σ bond. This has a
cylindrical symmetry around the
internuclear axis, and the electrons in it
have zero orbital angular momentum about
that axis. 15
H2O
1s 2s 2p
2px 2py 2pz
Electronic structure of
oxygen atom-ground state
Oxygen atom having
gained 2 electrons from H
atom in H2O molecule
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N2
1s 2s 2p
2px 2py 2pz
Electronic structure of
nitrogen atom-ground
state
Nitrogen atom having
gained 3 electrons from
Natom in N2 molecule
π bond
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Promotion is the excitation of an electron to an orbital of
higher energy in the course of the bond formation.
Promotion of electrons may occur if the outcome is to
achieve more or stronger bonds and a lower overall energy
1s 2s 2p
2px 2py 2pz
Electronic structure of
carbon atom-ground state
1s 2s 2p
Electronic structure of
carbon atom-excited state
Carbon atom having
gained 4 electrons from H
atoms in CH4 molecule
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Hybridization is the mixing of atomic orbitals on the same
atom or when atomic orbitals on the same atom interfere,
giving rise to hybrid orbitals. For effective mixing, the
energy of the orbitals must be the same.
1s 2s 2p
2px 2py 2pz
Electronic structure of
boron atom-ground state
1s 2s 2p
Electronic structure of
boron atom-excited state
Boron atom having gained
3 electrons from F atoms
in BF3 molecule
s p2
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Molecular Orbital theory
• This considers the ways in which electrons
are influenced by the presence of two or
more nuclei, the electrons in bonded
atoms being said to occupy molecular
orbitals.
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Molecular Orbital theory
Example: H2 molecule
If 2 hydrogen atoms are first considered to be
widely separated, then each electron is
influenced by its own nucleus, each electron
occupying a 1s atomic orbitals.
• As each atom come close to one another, they
also come under the influence of two H nuclei
and form a chemical bond.
• Under these conditions, the separate atomic
orbitals can be said to merge and form
molecular orbitals.
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Molecular Orbital theory Example: H2
molecule
The number of possible molecular orbitals is
equal to the number of the separate atomic
orbitals in the separated atom.
• Hydrogen molecule has two atomic orbitals,
hence two possible molecular orbitals.
• The 2 molecular orbitals are obtained by adding
and subtracting the two atomic orbitals. This is
called Linear combination of atomic orbitals
abbreviated as LCAO method. The two possible
molecular orbitals are represented by
bonding A.1s B .1s antibonding A.1s B.1s
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where A and B are the 2 H atoms
A bonding molecular orbital
• is obtained by adding together the
separate atomic orbitals and this results in
the build-up of negative charge between
the two nuclei.
+ + . + .
. .
Bonding molecular orbitals(σ1s)
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An antibonding molecular orbital
• is obtained by subtracting two atomic
orbitals and this leads to a draining away
of negative charge between the two nuclei.
+ -
. . + . . -
Antibonding molecular orbitals(σ*1s)
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A bonding molecular orbitals is of lower energy than two
separate atomic orbitals, while, antibonding molecular orbitals
has a higher energy than the two separate atomic orbitals.
+ . . -
The σ*1s unoccupied
Increasing energy
+ +
. .
2 separate H 1s atomic orbitals
each singly occupied +
. .
The bonding molecular orbital
occupied by 2 electrons of
opposite spin σ1s
Hence for the hydrogen molecule, both electrons occupy the bonding molecular
orbital, a chemical bond being established because this bonding molecular orbital
is of lower energy than two singly atomic orbital of the H atoms
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Conditions for atomic orbitals to give
molecular orbitals.
• The atomic orbital must overlap to an appreciable extent
otherwisw there will be no significant build up of charge
between the nuclei and therefore no chemical bond will be
established.
• In the region of overlap, the wave functions to the
separate atomic orbitals must be of the same sign,
otherwise there will be no build up of charge between the
two nuclei.
• The energies of the separate atomic orbitals must be of
comparable magnitude.
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Application of Molecular orbital
Theory For s atomic orbitals
• He diatomic molecule
The lower energy of
Increasing Energy
the bonding molecular
σ*1s2
orbital is effectively
+. .-
cancelled out by the higher
energy of antibonding
molecular orbital so no
He .+. chemical bond is
He
1s2 established, hence no He2
1s2
σ1s2 molecule is formed.
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• He diatomic ion
He2+ contains 3
electrons and 2 are in
a bonding molecular
σ*1s1
orbital while the third
Increasing Energy
+. .- occupy the
antibonding molecular
orbital. There is some
overall bonding and
this specie can exist. It
He .+. can be obtained by
He
subjecting He gas at a
1s2
1s1 low pressure to a high
σ1s2
energy discharge.
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Application of Molecular orbital Theory
For p atomic orbitals
P atomic orbitals can overlap in two distinct
ways:
• Two 2px can overlap along x-axis and give
rise to σ bonding and antibonding
molecular orbital.
• Two 2px can also overlap laterally and
again give rise to π bonding and
antibonding molecular orbital.
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Example-
σ *2Px
π*2Py2 π*2Pz2
2Px 2Py 2Pz 2Pz 2Py 2Px
π2Py2
π2Pz2
σ2Px2
σ*2S2
2S 2S
σ2S2
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1s 2 s 2 p 2 p 2y *2 p 2y
F2 * *
2
1s 2 2
2s2 2
x 2 pz2 2 pz2
NH3= 1s 1s 2s 2s 2p =10
MO for * *
2 2 2 2 2
x
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