CHAPTER TWO

Chemical bonding and Molecular structure

 Outlines
Introduction to Quantum Mechanics and

Classical mechanics

Shapes of Atomic orbitals

Chemical Bonding

Molecular Structure or shape of molecular

compounds

Bonding in organic Molecules

 Classical mechanics
• Classical mechanics (newton's mechanics) and maxwell's
equations (electromagnetics theory) can explain macroscopic
phenomena such as motion of billiard balls or rockets
predicts a precise trajectory for particles, with precisely
specified locations and moment at each instant, and
allows the translational, rotational, and vibrational modes of
motion to be excited to any energy simply by controlling the
forces that are applied.
• However, Classical mechanics does not extend to individual
atoms
• Careful experiments shows that classical mechanics fails when
applied to the transfers of very small energies and to objects
of very small mass.
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 Quantum mechanics
is used to explain microscopic phenomena such as photon-
atom scattering and flow of the electrons in a semiconductor.
• In newtonian mechanics, the laws are written in terms of
particle trajectories.
• It state of newtonian physics which state that A particle is an
indivisible mass point object that has a variety of properties
that can be measured, which we call observables.
• Quantum particles can act as both particles and waves in nature
(wave-particle duality).
• Quantization of energy is the property of "microscopic"
particles

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 Electromagnetic Radiation
• There are many kinds of waves, such as water waves, sound
waves, and light waves.
• Electromagnetic radiations are the forms of radiant energy
that travel as waves through space.
• Electromagnetic radiation is the emission and transmission of
energy in the form of electromagnetic waves.
• In 1873 James Clerk Maxwell proposed that visible light
consists of electromagnetic waves.
• According to Maxwell’s theory, an electromagnetic wave has
an electric field component and a magnetic field component.
• These two components have the same wavelength,
frequency, and hence the same speed, but they travel in
mutually perpendicular planes
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The electric field and magnetic field components of an
electromagnetic wave. These two components have the
same wavelength, frequency, and amplitude, but they
vibrate in two mutually perpendicular planes
6
 The Wave Nature of Light
• The significance of Maxwell’s theory is that it provides a
mathematical description of the general behavior of light.
• In particular, his model accurately describes how energy in
the form of radiation can be propagated through space as
vibrating electric and magnetic fields.
• Electromagnetic radiations can be characterized by their
wavelength, frequency and velocity which are interrelated
quantities.
1. Frequency (𝑣, Greek 𝑚𝑢) is the number of cycles the wave
undergoes per second and is expressed in units of 1/second
[𝑠 −1 ; also called hertz (Hz]
• It is expressed as [cycles per second].

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2. Wavelength [ , Greek lambda]: is the distance between
any point on a wave and the corresponding point on the
next crest (or trough) of the wave, that is, the distance the
wave travels during one cycle.
• Wavelength is expressed in meters and often, for very short
wavelengths, in nanometers (nm, 10−9 m), picometers (pm,
10−12 m), or the non-SI unit angstroms (A° , 10−10 m).

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3. Speed (Velocity [c]): of the wave is the distance traveled per
unit time (in units of meters per second),
• It is the product of its frequency (cycles per second) and its
wavelength (meters per cycle)

• In a vacuum, all types of electromagnetic radiation travel at

3.00X 108 m/s which is a physical constant called the speed of
light (c)

• Wavelength () and Frequency (v) have a reciprocal

relationship to each other:
• radiation with a high frequency has a short wavelength, and
vice versa.
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4. Amplitude: Another characteristic of a wave is its amplitude, the
height of the crest (or depth of the trough) of each wave
• The amplitude of an electromagnetic wave is a measure of the
strength of its electric and magnetic fields.
• Thus, amplitude is related to the intensity of the radiation, which
we perceive as brightness in the case of visible light.
• Light of a particular color-fire-engine red, for instance-has a
specific frequency and wavelength, but it can be dimmer (lower
amplitude) or brighter (higher amplitude).

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Example: The wavelength of the green light from a traffic
signal is centered at 522 nm. What is the frequency of this
radiation?
Solution: = 522 nm = 522× 10−9 m C= 3.0× 108 m/s

Rearranging Equation

Substituting in the wavelength and the speed of light

= 3.0×108 m/s 14 /s or 5.75× 1014 Hz

𝑣= = 5.75× 10
522×10−9m

Practice Exercise: What is the wavelength (in meters) of an

electromagnetic wave whose frequency is 3.64 × 107 Hz?
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 The Electromagnetic Spectrum
• Visible light represents a small portion of the continuum of
radiant energy known as the electromagnetic spectrum
• All the waves in the spectrum travel at the same speed
through a vacuum but differ in frequency and, therefore,
wavelength
• Some regions of the spectrum are utilized by particular
devices; for example, the long-wavelength, low-frequency
radiation is used by microwave ovens and radios.
• Note that each region meets the next. For instance, the
infrared (IR) region meets the microwave region on one end
and the ultra violet region on the other
• We perceive different wavelengths (or frequencies) of visible
light as different colors, from red ( ≈ 750 nm) to violet
(≈400 nm). By: Efa Kebeda 12
The electromagnetic spectrum extends from the very short
wavelengths (very high frequencies) of gamma rays through
the very long wavelengths (very low frequencies) of radio
waves
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 Planck’s Quantum Theory
• Classical physics assumed that atoms and molecules could emit (or
absorb) any arbitrary amount of radiant energy
• Planck’s quantum theory explains the emission and absorption of
radiation.
• Postulates of Planck’s quantum theory are as follows :
i. Matter radiates energy or absorbs energy in discrete quantities,
discontinuously in the form of small packets or bundles.
ii. The smallest bundle or packet of energy is known as quantum. In
the case of light, a quantum of light is known as a photon.
iii. The energy of the quantum absorbed or emitted is directly
proportional to the frequency of the radiation. So, the energy of
the radiation is expressed in terms of frequency
• Planck gave the name quantum to the smallest quantity of energy
that can be emitted (or absorbed) in the form of electromagnetic
radiation.
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• He proposed certain quantities of energy as:
𝐸 = 𝑛ℎ𝑣
• Where 𝐸 is the energy of the radiation ℎ is called Planck’s
constant, 𝑣 is the frequency of radiation and 𝑛 is a positive
integer (1, 2, 3, and so on) called a quantum number
• The value of Planck’s constant is = 6.626 × 10−34 J.s.
• According to quantum theory, energy is always emitted in
multiples of ℎ𝑣; for example, ℎ𝑣, 2ℎ𝑣, 3ℎ𝑣
𝑣
• Because 𝑐 = , the equation can also be expressed as


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• If an atom can emit only certain quantities of energy, it follows
that the atom itself can have only certain quantities of energy.
• Thus, the energy of an atom is quantized: it exists only in certain
fixed quantities, rather than being continuous
• Each change in the atom's energy results from the gain or loss of
one or more "packets," definite amounts, of energy.
• Each energy packet is called a quantum ("fixed quantity"; plural,
quanta), and its energy is equal to ℎ𝑣.
• Thus, an atom changes its energy state by emitting (or
absorbing) one or more quanta, and the energy of the emitted
(or absorbed) radiation is equal to the difference in the atom 's
energy state

• when an atom in a given energy state changes to an adjacent

state, that is, when ∆n = 1:
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Example: Calculate the energy (in joules) of a photon with a
wavelength of 5.00 × 104 nm
𝑐
Solution: 𝐸 = ℎ𝑣, by substituting the equation of 𝑣 =

ℎ= 6.626 × 10−34 J.s, 𝑐= 3 × 108 m/s
𝑐
then 𝐸 = ℎ ,

= 5.00 × 104 nm = 5.00 × 10−5 m

3 108m/s
Thus, 𝐸 = 6.626 × 10−34 J.s ×
×
−5 = 3.98× 10−21 J
5.00 ×10 m

Practice problem 1: The wavelength of the radiation is 1.20 cm.

What is the energy of one photon of this microwave radiation?
2: The energy of a photon is 5.87× 10−20 J. What is its
wavelength (in nanometers)?
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 de Broglie relation
• Louis de Broglie a French physicist, in 1924 gave his theory in which
he said just like light electrons have properties of waves and
particles.
• This nature was called as dual behavior
• He proposed that all moving objects have wave properties.
Thus
 For light characteristics:
 For particles: E = mc2 (Einstein)
 Therefore, which can be written as

 After all the observation de Broglie obtained a relation between

momentum of matter and wavelength.

particle wave duality of matter!

• This relation is known as de Broglie wavelength.

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Example: Calculate the wavelength associated with a 6.0 × 10−2
-kg tennis ball traveling at the speed of 68 m/s.
Solution:

ℎ = 6.626 × 10−34 J. s
𝑚= 6.0 × 10−2 kg
𝑣= 68 m/s
6.626×10−34 J.s
= = 1.6 × 10−34 𝑚
6.0 ×10−2 kg×68 m/s
(1 𝐽 = 1 𝑘𝑔 𝑚2 /𝑠 2 )
Practice Question: Calculate the wavelength (in nanometers) of
a H atom (mass 1.674 × 10−27 𝑘𝑔) moving at 7.00 × 102 𝑐𝑚/𝑠.

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Probable Location of the Electron
• The electron's Particle-wave occupies the three-
dimensional space near the nucleus and experiences a
continuous, but varying, influence from the nuclear
charge
• Schrödinger applied: idea of an electron behaving as a
wave to the problem of electrons in atoms.
• Although we cannot precisely define an electron’s orbit,
we can obtain the probability of finding an electron at a
given point around the nucleus.
• Erwin Schrodinger defined this probability in a
mathematical expression called a wave function, denoted
(psi).
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 ᴪ Does not describe the exact location of the electron.
 ᴪ 2 are proportional to the probability of finding an electron
at a given point.
• In conclusion, the position of an electron moving with a
definite velocity cannot be determined exactly.
• It is however possible to predict or state the probability of an
electron is being at a given time
• The region in space around the nucleus where there is a
maximum probability of finding an electron is called the
atomic orbital.
• Atomic orbitals are of different kinds and each orbital has a
definite energy, shape and volume.

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 Heisenberg uncertainty principle
• In the classical view of the world, a moving particle has a
definite location at any instant
• In 1927, the German physicist Werner Heisenberg postulated
the uncertainty principle
• Which states that it is impossible to know simultaneously both
the momentum (mass times velocity) and the position of a
particle with certainty
• For a particle with constant mass 𝑚, the principle is expressed
mathematically as

• where ∆𝑥 is the uncertainty in position and ∆𝑢 is the

uncertainty in speed.
• The more accurately we know the position of the particle
(smaller ∆𝑥), the less accurately we know its speed (larger ∆𝑢),
and vice versa.
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 Emission Spectrum of the Hydrogen Atom
• In 1913, discoveries, a theoretical explanation of the emission
spectrum of the hydrogen atom was presented by the Danish
physicist Niels Bohr.
• Bohr postulated that the electron is allowed to occupy only certain
orbits of specific energies.
• In other words, the energies of the electron are quantized.
• Bohr attributed the emission of radiation by an energized hydrogen
atom to the electron dropping from a higher-energy orbit to a lower
one and giving up a quantum of energy (a photon) in the form of
light
• Bohr showed that the energies that an electron in hydrogen atom
can occupy are given by

• where RH, the Rydberg constant, has the value 2.18 × 10−18 𝐽.
• The number n is an integer called the principal quantum number; it
23
has the values n 1, 2, 3, . . . .
• During emission, the electron drops to a lower energy state
characterized by the principal quantum number 𝑛𝑓 (the
subscripts i and f denote the initial and final states,
respectively).
• The difference between the energies of the initial and final
states is

• Therefore,

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• If we combine this Equation with Planck's expression for the
change in an atom's energy we obtain the Rydberg equation

• Therefore,

The negative sign indicates that this is energy associated with an

emission process.
To calculate the wavelength, we will omit the minus sign for because
the wavelength of the photon must be positive.

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Example: What is the wavelength of a photon (in nanometers)
emitted during a transition from the 𝑛𝑖 =5 state to the 𝑛𝑓 =2
state in the hydrogen atom?
Solution:

18 1 1
2.18 × 10 𝐽 ( 2 − 2 ) =−4.58 × 10−19 𝐽
5 2

• To calculate the wavelength, we will omit the minus sign for

because the wavelength of the photon must be positive.
ℎ𝑐 (3.00 ×108 m/s)(6.626 × 10−34 J.s)
= 4.58×10−19 𝐽
∆𝐸
=4.34 × 10−7 𝑚 = 434nm

Practice problem: What is the wavelength (in nanometers) of a

photon emitted during a transition from 𝑛𝑖 =6 to 𝑛𝑓 =4 state in the H
atom?
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 Shapes of Atomic orbitals:
What are Atomic Orbitals
• The 3-dimensional space around the nucleus of an atom
where the possibility of finding an electron is the highest is
called an atomic orbital.
• Solving of wave equations corresponding to different
electrons in an atom shows that the atomic orbitals are
mainly of four types namely s-orbitals, p-orbitals, d-orbitals
and f-orbitals.
• S-orbital
• The shape of the s orbital is spherical with the nucleus in the
centre.
• Therefore, s orbitals can be said to be spherically
symmetrical.
• Due to their symmetry, they have the probability of finding an
electron at equal distances from the nucleus.
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• The size of the s orbital is found to increase with increase in
the value of principal quantum number (n). Hence,
4s>3s >2s>1s.
• The s-orbital corresponding to the k-shell has the lowest
energy. 2s orbital is associated with more energy and so on.

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• p-orbitals
• All p-orbitals have dumb bell shape with contain two sections
called lobes that lie on either side of the plane which passes
through the nucleus of the atom.
• The three p orbitals are identical in terms of shape, size and
energy. However, they differ in their orientation of lobes.
• Since the lobes lie along one out of the three axes, namely, x,
y and z, the three orbitals are designated as 2px, 2py and 2pz.
It can thus be said that there are 3 p orbitals with mutually
perpendicular axes.
• As in s orbitals, the energy and size of p orbitals increases with
an increase in the quantum number i.e. 4p > 3p >2p.

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• These orbitals have three-fold degeneracy corresponding to
the quantum numbers ml = +1, 0, -1.

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 d-Orbitals
• d-orbitals have double dumb bell shape
• The magnetic orbital quantum number for d orbitals is
denoted as (-2, -1, 0, 1, 2). Thus, there exist five d orbitals.
• The d orbitals are given the designations dxy, dyz, dxz, dx2-y2 and
dz2.
• The shapes of the first four d orbitals are similar to one
another while being different from the dz2 orbital.
• The energy of all five d orbitals is the same.

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 f-orbitals
• f-orbital have complex shapes.
• The f orbitals have seven f-orbitals, f-orbitals have seven- fold
degeneracy corresponding to the quantum numbers with
quantum numbers ml (-3, -2, -1, 0, 1, 2 3).

32
 Quantum numbers
• Each electron in an atom is described by four different
quantum numbers.
Those are:
Principal Quantum Number (𝑛)
Angular Momentum Quantum Number (𝑙)
Magnetic Quantum Number (𝑚𝑙)
Spin Quantum Number (𝑚𝑠)
• The first three (𝑛, 𝑙, 𝑚𝑙) specify the particular orbital of
interest, and the fourth ( 𝑚𝑠 ) specifies how many
electrons can occupy that orbital.

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 1. Principal Quantum Number (n): n = 1, 2, 3, …, 8 .
• Specifies the energy of an electron to a large extent and the
average distance of the electron from the nucleus (size of the
orbital).
• All orbitals that have the same value of n are said to be in the
same shell (level).
• For a hydrogen atom with n=1, the electron is in its ground
state; if the electron is in the n=2 orbital, it is in an excited
state.
• The principal quantum number therefore indirectly describes
the energy of an orbital.
• The total number of orbitals for a given n value is 𝑛2 .
• For First energy shell, k-shell n=12
• For second energy shell L-shell n = 28
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 2. Angular Momentum (Secondary, Azimunthal)
Quantum Number (l): l = 0, ..., n-1
• Specifies the shape of an orbital with a particular principal
quantum number.
• The secondary quantum number divides the shells into smaller
groups of orbitals called subshells (sublevels).

• The subshell with n=2 and l=1 is the 2p subshell; if n=3 and
l=0, it is the 3s subshell, and so on.
• The value of l also has a slight effect on the energy of the
subshell;
• the energy of the subshell increases with l (s < p < d < f).

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 3. Magnetic Quantum Number (ml): ml = -l, ..., 0, ..., +l.
• Specifies the orientation in space of an orbital of a given energy (n)
and shape (l).
• Within a subshell, the value of 𝑚𝑙 depends on the value of the
angular momentum quantum number.
• For a certain value of 𝑙, there are (2𝑙 + 1) integral values of 𝑚𝑙 as
follows: −𝑙 𝑡𝑜 + 𝑙.
• For example:
• If l = 0 s-orbital m𝑙 can have only one value
i.e., m𝑙 =0 only one orientation
• If l = 1 p-orbital m𝑙 can have (2𝑙 + 1) no. of values
i.e., (2×1+1)=3 values, they are
m𝑙 =-1,0,+1  p-orbital has 3-fold degeneracy
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• 4. Spin Quantum Number (𝑚𝑠): 𝑚𝑠 = +½ or -½.
• Specifies the orientation of the spin axis of an electron.
• The spin may be in the clock wise or anti clockwise direction.
Accordingly, spin quantum number may have two values + ½
and -½.
• These are symbolically represented as up and down.

Quantum mechanics may be used to determine the

arrangement of electrons within three specific principles.
These are:
Aufbau principle
Hund’s rule and the
Pauli exclusion principle.

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• Aufbau principle: electrons enter orbitals of lowest
energy first.
• Each atomic orbital sublevels can hold specific electrons
for s holds up to 2, p holds up to 6, d holds up to 10
16
Eg. 𝑆 32 : 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝4
Hund’s rule: when electrons occupy orbitals of the same
energy, electrons will enter empty orbitals first.

by Efa Kebeda 38
• Pauli exclusion principle: an atomic orbital can describe
at most two electrons
 no two electrons in the same atom can have identical
values for all four of their quantum numbers.
 What this means is that no more than two electrons can
occupy the same orbital, and that two electrons in the
same orbital must have opposite spins

39
Main shell Principal Azimuthal Name of Magnetic q. no. [m] No. of Total no.
quantum q.no [l] of
the sub (2l+1) no. of values orbitals in
number No. of electrons
[n] sublevels level sub levels in each
shell [2n2]
K 1 0 1s 0 1 2
L 2 0 2s 0 1 2+
1 2p -1,0,+1 3 6=8
M 3 0 3s 0 1 2+
1 3p -1,0,+1 3 6+
2 3d -2,-1,0,+1,+2 5 10=18
N 4 0 4s 0 1 2+
1 4p -1,0,+1 3 6+
2 4d -2,-1,0,+1,+2 5 10+
3 4f -3,-2,-1,0,+1,+2,+3 7 14=32

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Example 1: List the values of 𝑛, 𝑙, 𝑎𝑛𝑑 𝑚𝑙 for orbitals in the 4d
subshell.
solution: In 4d orbitals the shell, the principal quantum
number, so in this case 𝑛 = 4. and the subshell (𝑙) with d
orbitals, 𝑙 =2.
The values of 𝑚𝑙 can vary from −𝑙 to 𝑙. Therefore, 𝑚𝑙 can be
− 2, −1, 0, 1, or 2.
2: What is the total number of orbitals associated with the
principal quantum number n =3?
total number of orbitals = 𝑛2 32 = 𝟗 𝐨𝐫𝐛𝐢𝐭𝐚𝐥𝐬

Practice problem: Give the values of the quantum numbers

associated with the orbitals in the 3p subshell

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 Chemical bonding refers to the attractive forces that hold atoms
together in compounds.
 The attractive force which holds various constituents (atoms,
ions, molecules) together in different chemical species is called a
chemical bond.

 Chemical bond is the mutual electrical attraction between the

nucleus and valance electrons of different atoms to form the
chemical compounds or molecules

A chemical bond is the net result

of attractive and repulsive
electrostatic forces.
 Why atoms are combined?
 Atoms combine to become more stable
 The most stable elements in the periodic table are the noble gases
(Group VIII A) elements.
 Atoms of all elements tend to acquire the noble gas configuration
which is of maximum stability and hence of sharing of electrons
amongst themselves or by the process of transference of electrons
from one atom to another.
 Atoms may attain a stable electronic configuration in three different
ways: by losing electrons, by gaining electrons, or by sharing
electrons.
 Types of Chemical Bonding
• Elements may be divided into:

1. Electropositive elements, whose atoms give up one or more

electrons fairly readily.

2. Electronegative elements. which will accept electrons.

3. Elements which have little tendency to lose or gain electrons.

• Three different types of bond may be formed, depending on

the electropositive or electronegative character of the atoms
involved.

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 Electropositive element
+ Ionic bond
Electronegative element
Electronegative element
+ Covalent bond
Electronegative element
Electropositive element
+ Metallic bond
Electropositive element
 Ionic bonding involves the complete transfer of one or more
electrons from one atom to another. Covalent bonding involves the
sharing of a pair of electrons between two atoms, and in metallic
bonding the valency electrons are free to move throughout the
whole crystal.
 Ionic Bond
• Ionic bonds are formed when electropositive elements react with
electronegative elements.
• When an atom with a high EN is placed near an atom with a high EP, the
first atom may “steal” an electron from the second atom.
• The atom that gives up the electron becomes a positively charged cation,
and the atom that gains the electron becomes a negatively charged anion.
• An ionic bond is the “electrostatic” attraction formed between the
oppositely charged cation and anion.
• Thus, this electron transfer typically occurs between a metal (low IE) and
a non-metal (high EN)
• Thus Ionic compounds are the Compounds between metals and nonmetals
are ionic.
46
11/8/2024 by Efa Kebeda 47
• An ionic bond is formed by the complete transference of one
or more electrons from the outer energy shell of one atom to
the outer energy shell of the other atom. In this way, both
the atoms acquire the electronic configuration of the nearest

noble gases.
• Na is 1s2 2s2 2p6 3s1 Cl 1s2 2s2 2p6 3s2 3p5
• Factors that affect the formation of ionic bond
• Some of the major factors influencing the formation of ionic bond
are as follows:
a. Ionization energy: ionization energy is the energy required to
remove electrons from gaseous atoms to form ions.
• The lower the ionization energy, the easier the metal can lose the
electron. Hence ionic bonds can form easily.
• This is the reason that metals have lower ionization energy and
form the ionic bond easily.
• The ionization energy decrease as we move down the group. So the
elements present at the bottom can form an ionic bond very easily.
A + IE → A+ + e–
(Li > Na > K >Rb >Cs)
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b. Electron affinity: it defined as the amount of energy released
when an electron is added to an isolated gaseous atom of an
element
• The atom which is accepting the electron and becoming a negative
ion should have high electron affinity.
B + e– → B + EA
• The elements of group VIA and VIIA have high electron affinity
and thus can form ionic bonds easily.
• When we move across the period, electron affinity increases, and
the tendency to form ionic bonds also increases.
(F > 0 > N > C)
• Thus, low ionization energy of a metal atom and high electron
affinity of a non-metal atom facilitate the formation of an ionic
bond between them. by Efa Kebeda 50
c. Lattice energy: The amount of energy released when one mole of
the ionic compound is formed by the combination of anions and
cations is called lattice energy.
A+ + B– AB + Lattice energy
• The greater the lattice energy, the greater will be the strength of the
ionic bond.
• The lattice energy depends upon two factors:
a. Size of ion
• The smaller the size of the cation and anion, the greater will be the
force of attraction between them.
b. Charge on ions
• The greater the charge on the anion and cation, the greater will be the
force of attraction between them. The strength of the ionic bond will
also be greater.
d. Electronegativity
• The difference in electronegativity between the metal and non metal
should be high enough to form an ionic compound. For example, the
electronegativity of Sodium and chlorine in sodium chloride is:
Na = 0.9 and Cl = 3.0.
• Here the difference is large enough to make an ionic compound.
• Large differences of electro negativities between the electro positive
element (metal) and electro negative element (non-metal)

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 Properties of Ionic compounds
 Ionic bond has a very characteristic properties which can
differentiate them from the covalent bond.

• High MP & BP • The ions are in a

• Hard, not easily very strong
crushed CRYSTAL
LATTICE pattern.
• Conduct electricity
when melted or
dissolved because
ions are freed up to
move.
1. Appearance at room temperature

• An ionic bond is formed by electrostatic attraction between

oppositely charged ions.

• There is a strong force of attraction due to which these ions cannot

move from their position. Therefore, ionic compounds are solid at
room temperature.

2. Melting points

• Due to the strong force of attraction between anions and cations,

they cannot easily move.

• Therefore, the melting points of ionic compounds are high.

11/8/2024 by Efa Kebeda 54

3. Hard and brittle
• The crystals of ionic compounds are hard and brittle due to the
strong force of attraction.
• The crystals are made up of layers of cations and anions. These
layers are in parallel arrangement thus ions of opposite charges lie
in front of each other.
• When an external force is applied, or knocked out of line the anions
repel the anions and the cations repel the cations and the compound
breaks apart.

11/8/2024 by Efa Kebeda 55

4. Solubility in water

• When an ionic compound is placed in water, polar water molecules

detach the positive and negative ions.

• These ions get surrounded by the water molecules and are thus
soluble in water.

11/8/2024 by Efa Kebeda 56

5. Conductivity
• Ionic compounds can only conduct electricity when they are
dissolved in water or are molten as there are ions free to move.
• Ionic compounds can not conduct electricity as a solid, as the ions
are not free to move.

Physical properties
 Ionic bonds are polar in nature.
 Ionic bond is stronger than covalent bond.
 Compounds with ionic bonds are mostly solid at room
temperature.
 Solid compounds with ionic bonds form lattice structure.
 It has high melting point and boiling point.
  Ionic compounds can conduct electricity only when it is melted
or in aqueous solution.

 These are soluble in water and other polar solvent.

 They are not soluble in any non polar solvent.

Chemical properties

 Ionic compounds are not reactive in its solid state.

 Ionic compounds show ionic reactions in aqueous solution.

 It is very reactive to other ionic compounds in aqueous solution.

11/8/2024 by Efa Kebeda 58

 Covalent Bond
• A covalent bond is formed by the common sharing of an
electron pair between two atoms each of which contribute
one electron to the electron pair.

The shared electrons contribute towards the stability of both the atoms.

 It is the net attractive force between the shared electrons and

the nuclei that holds the atoms together
• Covalent bond is the force of attraction between the pair of
electrons and the two positive nuclei of the atoms

• A covalent bond is the electrostatic force of attraction between

the positively charged nuclei of both atoms and their shared
pair(s) of electrons.

11/8/2024 by Efa Kebeda 60

 Types of Covalent bonds
Single Covalent Bonds
• Each covalently bonded atom equally attracts one pair of shared
electrons.
• Consider the formation of a hydrogen molecule,

• Each covalently bonded atom equally attracts one pair of shared

electrons.
• Thus, two electrons shared by two hydrogen nuclei belong to each
atom simultaneously.
• Both hydrogen atoms have the noble gas configuration of
helium (1𝑠 2 ).
• The hydrogen molecule is more stable than individual hydrogen
atoms.
• When a single pair of electrons is shared, a single covalent bond
forms.
• The shared electron pair, often referred to as the
bonding pair, is represented by either a pair of dots or a line in the
Lewis structure for the molecule.
• The sigma bond Single covalent bonds also are called sigma bonds,
symbolized by the Greek letter sigma (σ).
• A sigma bond occurs when the electron pair is shared in an area
centered between the two atoms.
• When two atoms share electrons, the valence atomic orbital of one
atom overlaps or merges with the valence atomic orbital of the other
atom.
• A sigma bond results if the atomic orbitals overlap end to end,
concentrating the electrons in a bonding orbital between the two
atoms.

by Efa Kebeda 62
Multiple Covalent Bonds

• In many molecules, atoms attain a noble-gas configuration by

sharing more than one pair of electrons between two atoms,
forming a multiple covalent bond.

• The number of valence electrons of an element is associated with

the number of shared electron pairs needed to complete the octet.

• Double and triple covalent bonds are examples of multiple bonds.

• A double covalent bond occurs when two pairs of electrons are

shared.

• The atoms in an oxygen molecule (𝑂2 ) share two electron pairs,

forming a double bond. by Efa Kebeda 63
• A triple covalent bond is formed when three pairs of electrons are
shared between two atoms.

• Nitrogen (𝑁2 ) shares three electron pairs, producing a triple bond.

• The pi bond A pi bond, denoted by the Greek symbol pi (𝜋), is

formed when parallel orbitals overlap to share electrons

• The shared electron pair of a pi bond occupies the space above and
below the line that represents where the two atoms are joined
together.

• Multiple bond consists of one sigma bond and at least one pi bond.
 Polarity of covalent bonds
• The polarity of a bond is the function of the difference in
electronegativity between two bonded atoms
• Not every polar bond results in a polar molecule
• Molecular polarities result from the sum of bond polarities
Two types of covalent bonds occur in molecules:
• Nonpolar covalent bonds; bonding electrons are shared equally
– Non-polar covalent bonds form between atoms of the same type.
Eg: H2, Cl2,
• Polar covalent bonds; bonding electrons are shared unequally
– One atom pulls the electrons closer to itself.
– The atom that pulls the electrons more gets a slightly negative
charge.
– The other atom gets a slightly positive charge.
• Eg Water molecule
11/8/2024 by Efa Kebeda 65
A nonpolar covalent bond between nonmetal atoms
• consists of an equal (or almost equal) sharing of electrons
• has a zero (or close to zero) electronegativity difference (0.0 to
0.4)

A polar covalent bond between nonmetal atoms

• consists of an unequal sharing of electrons
• has an electronegativity difference of 0.5 to 1.7
• The polarity of a covalent bond is measured using its dipole
moment.
Large dipole moment = more polar
Small dipole moment = more nonpolar
• The distribution of electron density in a bond can be depicted
using:
Partial charges
Direction of dipole moment
 Partial charges:
Place the partial negative charge for the more electronegative
element and partial positive charge for the less electronegative
element

11/8/2024 by Efa Kebeda 67

 Direction of dipole
• The positive end of the arrow from the less electronegative
element and the arrow in the direction of the more
electronegative element

Polar vs. Non-Polar Molecules

• Polar molecules: The Electron density is distributed
asymmetrically throughout the molecule
• Contain a “negative” end and a “positive” end
• A molecule is a polar molecule if it contains exactly 1 polar
covalent bond.

11/8/2024 by Efa Kebeda 68

• Nonpolar molecules: Electron density is distributed
symmetrically within the molecule
• A molecule will be nonpolar if:
It contains only nonpolar covalent bonds or
If two more polar covalent bonds are arranged
symmetrically within the molecule.

11/8/2024 by Efa Kebeda 69

 Properties of Covalent Compounds
1. Most covalent compounds have relatively low melting points and
boiling points.
• Covalent bonds create molecules that can separate from each other
when a lower amount of energy is added to them.
• Therefore, molecular compounds usually have low melting and
boiling points.

2. Covalent compounds tend to be soft and relatively flexible.

 This is largely because covalent bonds are relatively flexible and
easy to break.
 The covalent bonds in molecular compounds cause these
compounds to take form as gases, liquids, and soft solids.
by Efa Kebeda 70
3. Covalent compounds tend to be more flammable than ionic
compounds.

 Many flammable substances contain hydrogen and carbon atoms

which can undergo combustion, a reaction that releases energy
when the compound reacts with oxygen to produce carbon dioxide
and water.

4. When dissolved in water, covalent compounds don't conduct

electricity.

 Molecular compounds dissolve into molecules rather than

dissociate into ions, so they typically do not conduct electricity very
well when dissolved in water.
by Efa Kebeda 71
5. Many covalent compounds don't dissolve well in water.

• many covalent compounds are polar molecules that do dissolve well

in a polar solvent, such as water.

 there's a saying that, "Like dissolves like". This means that

compounds tend to dissolve in other compounds that have similar
polarities

 Since water is a polar solvent and most covalent compounds are

fairly nonpolar, many covalent compounds don't dissolve in water.
 3.Metallic Bonding
• Metallic bonding is the electrostatic force of attraction between the
positive metal ions and the delocalized electrons
• The positive ions are formed when the outer electrons become
detached from the atom , leaving a positive ion behind.
• The electrons that leave the atom, join in the sea of delocalized
electrons.
• The metal ions are arranged in a giant lattice.
• The valence electrons of metal atoms can drift freely from one part
of the metal to another- this is sometimes called a “sea of
electrons”

11/8/2024 by Efa Kebeda 73

• Metallic bonds consist of the attraction between these free
floating electrons and the positively charged metal ions
(cations).

• This attraction is the “bond” that holds metals together.

 The three main factors that affect the strength of metallic
bonding are:
i. Number of protons/ Strength of nuclear attraction
– The more protons the stronger the bond
ii. Number of delocalised electrons per atom (the outer shell
electrons are delocalised)
– The more delocalised electrons the stronger the bond
iii. Size of ion.
The smaller the ion, the stronger the bond.
 Properties Metallic Bonding
a. Electrical Conductivity
• Electrical conductivity is a measure of the ability of a
substance to allow a charge to move through it.
• Since the movement of electrons is not restricted in the
electron sea, any electric current passed through it.

• When a potential difference is introduced to the metal, the

delocalized electrons start moving towards the positive
charge. This is the reason why metals are generally good
conductors of electric current.
11/8/2024 by Efa Kebeda 75
b. Thermal Conductivity
• The thermal conductivity of a material is a measure of its
ability to conduct/transfer heat.
• The greater the mobility of the electrons, the quicker the
transfer of kinetic energy.
• Due to metallic bonds, the delocalized electrons are highly
mobile, and they transfer the heat through the metallic
substance by colliding with other electrons.
c. Malleability and Ductility
• In the case of metals, the sea of electrons in the metallic
bond enables the deformation of the lattice.
• Therefore, when metals are beaten with a hammer, the rigid
lattice is deformed and not fractured.
• This is why metals can be beaten into thin sheets. Since
these lattices do not fracture easily, metals are said to be
highly ductile. by Efa Kebeda 76
d. Metallic Luster
• Metallic luster is a property of a metal that describes the
amount of light that reflects off the metal.
• When light is incident on a metallic surface, the energy of the
photon is absorbed by the sea of electrons that constitute the
metallic bond
• The absorption of energy excites the electrons, increasing
their energy levels.
e. High Melting and Boiling Points
• As a result of powerful metallic bonding, the attractive force
between the metal atoms is quite strong.
• In order to overcome this force of attraction, a great deal of
energy is required.
• This is the reason why metals tend to have high melting and
boiling points.
11/8/2024 by Efa Kebeda 77
 1.7

2.00 1.7
 Theories of Covalent Bonding
• Bonding theories are able to explain the observed shapes,
polarities, magnetic and spectroscopic properties of molecules by
using quantum mechanics – atomic and molecular orbitals.
• The two models of chemical bonding that address these factors are
valence bond theory and molecular orbital theory.
• Valence bond theory (VBT) and molecular orbital theory (MOT)
share many assumptions, but also differ in many ways.
• The two theories are similar in that both assume that:
 bonds occur due the sharing of electrons between atoms;
 the attraction of bonding electrons to the nuclei of the bonded
atoms leads to lower energy, and therefore the formation of a
bond; and
 two types of bonds can form (sigma and pi).

11/8/2024 by Efa Kebeda 79

• The two theories differ in:
– how they describe the location of the electrons in bonding
orbitals,
– how they explain the energy of electrons, and
– how they explain the presence of unpaired electrons in
molecules.
• Molecular orbital theory is the more accurate and more
broadly useful of the two theories While valence bond theory
is easier to use.

11/8/2024 by Efa Kebeda 80

 Valence Bond (VB) Theory
• Valence bond (VB) theory is a chemical bonding theory that
explains the chemical bonding between two atoms.
• According to valence bond theory, bonding is caused by the
overlap of half-filled atomic orbitals.
• The two atoms share each other's unpaired electron to form
a filled orbital to form a hybrid orbital and bond together.
• These atomic orbitals overlap, so electrons have the highest
probability of being within the bond region.
• The basic principle of VB theory:
i. A covalent bonds results from the overlap of valence
atomic orbitals on neighboring atoms occupied by unpaired
electrons and the formation of an electron pair which has
highest probability to be between the nuclei
ii. The two electrons in the pair must have opposite spins –
(Pauli exclusion principle)
11/8/2024 by Efa Kebeda 81
iii. The overlapping orbitals are oriented in a way that provides
maximum overlap between them
iv. valence electrons are either involved in bonding between
two atoms (shared bonding pairs) or reside on a single atom
(nonbonding lone pairs).
v. The greater the orbital overlap, the stronger the bond.

The covalent bond in H2 Hydrogen fluoride, HF.

11/8/2024 by Efa Kebeda 82
 Hybridization
• Hybridization is defined as the mixing of two atomic orbitals
to give rise to a new type of hybridized orbitals
• This intermixing usually results in the formation of hybrid
orbitals having entirely different energies, shapes, etc.
• During the process of hybridization, the atomic orbitals of
comparable energies are mixed together
• The new orbitals thus formed are known as hybrid
orbitals.

11/8/2024 By: Efa Kebeda 83

Features of Hybridization
• Atomic orbitals with equal energies undergo hybridization.
• The number of hybrid orbitals formed is equal to the number
of atomic orbitals mixing.
• It is not necessary that all the half-filled orbitals must
participate in hybridization. Even completely filled orbitals
with slightly different energies can also participate.
• Hybridization happens only during the bond formation and
not in an isolated gaseous atom.
• The concept of hybridization is not applied to isolated atoms.
It is a theoretical model used only to explain covalent
bonding

11/8/2024 By: Efa Kebeda 84

• The shape of the molecule can be predicted if the
hybridization of the molecule is known.
• Hybridization is the mixing of at least two nonequivalent
atomic orbitals, for example, s and p orbitals.
• Hybrid orbitals and pure atomic orbitals have very different
shapes.
• Covalent bonds in polyatomic molecules and ions are formed
by the overlap of hybrid orbitals, or of hybrid orbitals with un-
hybridized ones.
• electrons in a molecule are assumed to occupy hybrid orbitals
of the individual atoms.

11/8/2024 By: Efa Kebeda 85

 Types of Hybridization
• Based on the types of orbitals involved in mixing, the
hybridization can be classified as sp3, sp2, sp, sp3d,
sp3d2, sp3d3.
1. sp Hybridization
• sp hybridization is observed when one s and one p orbital in
the same main shell of an atom mix to form two new
equivalent orbitals.
• The new orbitals formed are called sp hybridized orbitals. It
forms linear molecules with an angle of 180°
• Each sp hybridized orbital has an equal amount of s and p
character – 50% s and 50% p character.

11/8/2024 By: Efa Kebeda 86

• Beryllium difluoride, 𝐵𝑒𝐹2 , has a linear geometry with an F–
Be–F angle of 180º.

• Each of the two fluorine atoms has a 2p orbital with one

unpaired electron and each 2p atomic orbital overlaps a
beryllium sp hybrid orbital forming two Be–F sigma bonds
Sigma bonding in BeF2

11/8/2024 87
2. sp2 Hybridization
• sp2 hybridization is observed when one s and two p orbitals of
the same shell of an atom mix to form 3 equivalent orbitals.
• The new orbitals formed are called sp2 hybrid orbitals.
• sp2 hybridization is also called trigonal hybridization.
• All the three hybrid orbitals remain in one plane and make an
angle of 120° with one another.
• Each of the hybrid orbitals formed has a 33.33% ‘s’ character
and 66.66% ‘p’ character.

11/8/2024 By: Efa Kebeda 88

Boron trifluoride, BF3, has a trigonal planar geometry with 120º F–B–F bond angles.
The electron configuration of boron and the F–B–F bond angles suggest that boron
hybridizes when it forms covalent bonds with fluorine

• Boron forms three equal-energy hybrid orbitals by combining its

three lowest energy valence orbitals, the 2s and two 2p orbitals
• Each of the three fluorine atoms has a 2p orbital with one
unpaired electron and each 2patomic orbital overlaps a boron sp2
hybrid orbital, forming three B–F sigma bonds
11/8/2024 By: Efa Kebeda 89
3. sp3 Hybridization
• When one ‘s’ orbital and 3 ‘p’ orbitals belonging to the same
shell of an atom mix together to form four new equivalent
orbital, the type of hybridization is called a tetrahedral
hybridization or sp3. The new orbitals formed are
called sp3 hybrid orbitals.
• These are directed towards the four corners of a
regular tetrahedron and make an angle of 109° with one
another.
• The angle between the sp3 hybrid orbitals is 109.50
• Each sp3 hybrid orbital has 25% s character and 75% p
character.

11/8/2024 By: Efa Kebeda 90

• In methane, one 2s and three 2p orbitals “mix,” or
hybridize, forming four equal-energy hybrid
orbitals

11/8/2024 By: Efa Kebeda 91

92
4. sp3d Hybridization
• sp3d hybridization involves the mixing of 1s orbital, 3p orbitals
and 1d orbital to form 5 sp3d hybridized orbitals of equal
energy. They have trigonal bipyramidal geometry.
• The mixture of s, p and d orbital forms trigonal bipyramidal
symmetry.
• Three hybrid orbitals lie in the horizontal plane inclined at an
angle of 120° to each other known as the equatorial orbitals.
• The remaining two orbitals lie in the vertical plane at 90
degrees plane of the equatorial orbitals known as axial
orbitals.

11/8/2024 By: Efa Kebeda 93

• In PF5 for example, phosphorus has five structural pairs
and therefore forms five hybrid orbitals

11/8/2024 By: Efa Kebeda 94

5. sp3d2 Hybridization
• sp3d2 hybridization has 1s, 3p and 2d orbitals, that undergo
intermixing to form 6 identical sp3d2 hybrid orbitals.
• These 6 orbitals are directed towards the corners of an
octahedron.
• They are inclined at an angle of 90 degrees to one another.
• In SF6 Each sulfur hybrid orbital is labeled an
sp3d2 hybrid orbital

11/8/2024 By: Efa Kebeda 95

• To assign a suitable state of hybridization to the central atom
in a molecule we must have follow the steps below:
a) Draw the Lewis structure of the molecule.
b) Predict the overall arrangement of the electron pairs
(both bonding pairs and lone pairs)
c) Deduce the hybridization of the central atom by matching
the arrangement of the electron pairs with those of the
hybrid orbitals
Molecular shape and
Molecular Lewis Hybrid
electron group
formula structure orbitals
arrangement

11/8/2024 By: Efa Kebeda 96

• Example: Determine the hybridization state of the central atom in
𝐵𝑒𝐻2 molecules:
The steps for determining the hybridization of the central atom in a
molecule are:
determine the electron pair arrangement
draw Lewis structure surrounding the central atom

determine the hybridization state of the central

atom

The Lewis structure of 𝐵𝑒𝐻2 is

There are two bonding pairs around Be; therefore, the electron pair
arrangement is linear.
We conclude that Be uses sp hybrid orbitals in bonding with H,
because sp orbitals have a linear arrangement
11/8/2024 By: Efa Kebeda 97
 Valence Shell Electron Pair Repulsion (VSEPR)
Theory
• The valence shell is the outermost electron-occupied shell of
an atom; it holds the electrons that are usually involved in
bonding.
• The geometry the molecule ultimately assumes (as defined by
the positions of all the atoms) minimizes the repulsion
between electrons in different bonding pairs
• This approach to the study of molecular geometry is called the
Valence-shell electron-pair repulsion (VSEPR) model,
• It accounts for the geometric arrangements of electron pairs
around a central atom in terms of the electrostatic repulsion
between electron pairs.

11/8/2024 By: Efa Kebeda 99

 General rules govern the use of the VSEPR model:
1. As far as electron-pair repulsion is concerned, double bonds
and triple bonds can be treated like single bonds.
2. If a molecule has two or more resonance structures, we can
apply the VSEPR model to any one of them.
• To predict the geometry of molecules (and ions) in a
systematic way, it is convenient to divide molecules into two
categories, according to:
– Molecules in which the central atom has no lone pairs
– Molecules in which the central atom has one or more lone
pairs
• The shape of the molecule depends on the number of
electron pairs (both bond pairs and lone pairs) present in the
valence shell of the central atom.
11/8/2024 By: Efa Kebeda 100
 Molecules in Which the Central Atom Has No Lone Pairs
• For simplicity consider molecules that contain atoms of A and
B, of which A is the central atom.
• These molecules have the general formula ABx, where x is an
integer 2, 3, . . . .
• (If x=1, we have the diatomic molecule AB, which is linear by
definition.)
• In the vast majority of cases, x is between 2 and 6.
• As a result of mutual repulsion, the electron pairs stay as far
from one another as possible.
• Molecules in which the central atom has no lone pairs have
the geometry of molecules with the formulas 𝐴𝐵2 , 𝐴𝐵3 , 𝐴𝐵4 ,
𝐴𝐵5 , and 𝐴𝐵6 .

11/8/2024 By: Efa Kebeda 101

Arrangement of Electron Pairs About a Central Atom (A) in a Molecule and Geometry
of Some Simple Molecules and Ions in Which the Central Atom Has No Lone Pairs

102
Molecules in Which the Central Atom Has One or More Lone
Pairs:
• In such molecules there are three types of repulsive forces—
those between bonding pairs, those between lone pairs, and
those between a bonding pair and a lone pair.
• A lone pair of electrons takes up more space around the
central atom than a bond pair, since the lone pair is attracted
to one nucleus while the bond pair is shared by two nuclei.
• In general, the repulsive forces decrease in the following
order:

11/8/2024 By: Efa Kebeda 103

• The presence of lone pairs at the central atom causes
distortion in molecular shapes and decrease in bond angles.
• We designate molecules with lone pairs as ABxEy, where A is
the central atom, B is a surrounding atom, and E is a lone pair
on A.
• Both x and y are integers; x 2, 3, . . . , and y 1, 2, . . . .
• Thus, the values of x and y indicate the number of
surrounding atoms and number of lone pairs on the
central atom, respectively.

11/8/2024 By: Efa Kebeda 104

• Geometry of Simple Molecules and Ions in Which the Central Atom
Has One or More Lone Pairs

11/8/2024 By: Efa Kebeda 105

11/8/2024 106
Guidelines for Applying the VSEPR Model
• Consider some of the following rules for applying the VSEPR
model to all types of molecules:
i. Write the Lewis structure of the molecule, considering only
the electron pairs around the central atom
ii. Count the number of electron pairs around the central atom
(bonding pairs and lone pairs). Treat double and triple
bonds as though they were single bonds
iii. Predict the geometry of the molecule
iv. In predicting bond angles, note that a lone pair repels
another lone pair or a bonding pair more strongly than a
bonding pair repels another bonding pair.

11/8/2024 By: Efa Kebeda 107

Example: Use the VSEPR model to predict the geometry of the
following molecules and ions: (a) 𝐴𝑠𝐻3 ,
– The sequence of steps in determining molecular geometry is as
follows:

The Lewis structure of 𝐴𝑠𝐻3 is

There are four electron pairs around the central atom; (3-bond
pair and 1-lone pair)
The class for this molecule is: AB3 E
the electron pair arrangement is tetrahedral
the geometry of a molecule is trigonal pyramidal

11/8/2024 By: Efa Kebeda 108

(b) 𝑂𝐹2
The Lewis structure of 𝑂𝐹2 is:
• There are four electron pairs around the central atom (2-bons pair
and 2-lone pair);
• The class of the molecules is 𝑨𝑩𝟐 𝑬𝟐
• therefore, the electron pair arrangement is tetrahedral
• the geometry of a molecule is Bent

Practice Exercise Use the VSEPR model to predict the geometry

of (a) 𝑆𝑖𝐵𝑟4 (b) 𝐶𝑆2 , and (c) 𝑁𝑂3 −

11/8/2024 By: Efa Kebeda 109

 Molecular orbital theory
• Valence bond theory (VBT) and molecular orbital theory (MOT)
share many assumptions, but also differ in many ways.
• The two theories are similar in that both assume that:
 bonds occur due the sharing of electrons between atoms;
 the attraction of bonding electrons to the nuclei of the bonded
atoms leads to lower energy, and therefore the formation of a
bond; and
 two types of bonds can form (sigma and pi).
• The two theories differ in:
– how they describe the location of the electrons in bonding
orbitals,
– how they explain the energy of electrons, and
– how they explain the presence of unpaired electrons in
molecules.
• Molecular orbital theory is the more accurate and more broadly
useful of the two theories While valence bond theory is easier to
use.
11/8/2024 By: Efa Kebeda 110
• A that predict physical and chemical properties of the
molecule such as shape, bond energy, bond length bond
angles, bond order and magnetic properties is the Molecular
orbital theory is one such successful theory.
• Molecular orbital theory describes covalent bonds in terms of
molecular orbitals, which result from interaction of the
atomic orbitals of the bonding atoms and are associated with
the entire molecule.
• According to MO theory the overlap of Atomic orbitals leads
to the formation of two molecular orbitals: one bonding
molecular orbital and one anti-bonding molecular orbital.
• A bonding molecular orbital has lower energy and greater
stability than the atomic orbitals from which it was formed.
• An anti-bonding molecular orbital has higher energy and
lower stability than the atomic orbitals from which it was
formed. 111
 Key Ideas of the MO Model
1. When two atoms approach each other, their atomic orbitals
lose their identity and mutually overlap to form new orbitals
called molecular orbitals.
2. All valence electrons in a molecule exist in a set of molecular
orbitals of a given energy.
3. Valence orbitals of each atom are not acting independently,
but rather interact as a whole to form a set of molecular
orbitals.
4. Each pair of atomic orbitals interacts to form a set of
bonding and antibonding molecular orbitals. (thus MOT is
polycentric).
5. Energy for bonding molecular orbitals is lower than their
atomic orbitals.
6. Antibonding molecular orbitals have higher energy that their
atomic orbitals.
By: Efa Kebeda 112
7. When number of atomic orbitals overlaps to form molecular
orbitals, an equal number of molecular orbitals are formed.
• two s orbitals overlap, they form two new orbitals:
– one at lower energy than the original s orbitals and
– one at higher energy than the original s orbitals”

8. Electrons go into the lowest energy orbital available to form

lowest potential energy for the molecule.
9. The maximum number of electrons in each molecular orbital is
two. (Pauli exclusion principle)
10. One electron goes into orbitals of equal energy, with parallel
spin before they begin to pair up. (Hund's Rule.)
11/8/2024 By: Efa Kebeda 113
• The energy of molecular orbital depends upon the following
two factors.
– (i) The nature of atomic orbitals.
– (ii) The extent of overlap between atomic orbitals
• The sequence of the energies of molecular orbitals for a
homonuclear diatomic molecule [up to Nitrogen Atomic
number 14] is as follows:
•

The sequence of the energies of MO's for molecule atomic

number greater than 14 is given as follows:

11/8/2024 114
11/8/2024 115
 Application of MOT
1. Electron density in Bonding and antibonding Molecular
orbitals; bonding electrons stabilizes Molecule while
antibonding electron destabilizes Bonding.
2. Bond order: As bond order increases, stabilization of the
molecule increases with increase in bond order and
decrease in bond length.
BO= ½[(number of bonding electrons) – (number of
antibonding electrons)]
3. Magnetic properties: Diamagnetic (all electrons are paired;
Paramagnetic (atleast one electron is unpaired).

11/8/2024 By: Efa Kebeda 116

 Bond Order
• The number of covalent bonds formed by the overlapping of atomic
orbitals and the relative stability of the molecular thus formed can
be known by a quantity known as Bond order.
• Bond order may be defined as one half of the difference between
the number of electrons in bonding molecular orbitals and number
of electrons in anti-bonding molecular orbitals.
Significance of Bond Order
• Bond order is useful in getting the following information about a
molecule.
1. Stability of the molecule
 If the Bond order is positive, then the molecule is stable i.e.,
• B.O =+ve only when nb > na
• where nb  Number of electrons in BMO
na  Number of electrons in ABMO
• This is because the number of electrons stabilizing the molecule is
greater than those which destabilize the molecule.
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 B.O = 0; if only when nb = na
• If the Bond Order = O, then the molecule is does not exixt.
2. Bond Length
• Bond order is also useful in predicting the bond length. Bond
order is inversely proportional to bond length. Hence higher
the bond order, shorter is the bond length.
3. Status of the Bond
• The intergral bond orders 1, 2 and 3 correspond to the single,
double and triple bonds
4. Magnetic Behaviour of the Molecule
• If a molecule contains no unpaired electrons then it is
diamagnetic molecules containing one or more unpaired
electrons possesses fractional bond order then it is
paramagnetic.
5. Dissociation Energy of the Molecule
• The dissociation energy of a molecule is proportional to its
bond order. Higher the value of bond order, greater is the
dissociation energy of the molecule 118
• Molecular Orbital Theory of Hydrogen molecule.
• Each of the H atoms has 1𝑠1 atomic orbital
• The interaction between the H1s AOs on forming 𝐻2 may be
represented by the MO diagram shown

The ground state electronic configuration of

𝐻2 may be written as using the
notation; σ(1𝑠 2 ) σ* (1𝑠 0 ).

Bond order = ½[(number of bonding

electrons) – ( number of antibonding
electrons)]
= ½[2 – 0] = 1
i.e. Hydrogen molecule contain one σ-bond.
H2 molecule is diamagnetic - All electrons
are paired.

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Practice Q1: 𝑁2 has greater dissociation energy than 𝑁2 +,
whereas 𝑂2 has lower dissociation energy than 𝑂2 +, . Explain.
Q2: For each of the following species
i. write the molecular orbital diagram
ii. determine the bond order
iii. indicate whether the species is paramagnetic or diamagnetic

Q3: Which of the following species has a longer bond length:

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