My-Lecturer Chemical-Bonds CE PME

Class Lecturer
Chemical Bonds
Chem- 101 & 175
Chem 101 and 175: General Chemistry
Lectures 1-6 : Chemical Bonds
Yunus Ahmed, PhD

Associate Professor
Department of Chemistry, CUET
Email: [email protected]
H/P : 01833512231
Class Lecturer
Lecture Objectives Chem- 101
Chem- 175
By the end of lectures, you should be able to

• Know what is chemical Bond and how it is formed
Learning Outcomes
• Know the different types of chemical bonds like ionic

bond, covalent bond, co-ordinate bond, metallic
bond and hydrogen bond.
• Know the formation mechanisms of some chemical
bonds.
• Characteristics of different bonds and their
compounds
• Different theories for forming chemical bonds like
Valence bond theory, molecular orbital theory,
hybridization and Valence Shell Electron Pair
Repulsion Theory (VSEPR Theory)
Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 2
Class Lecturer
Elements, Atoms, Molecules & Compounds Chem- 101
Chem- 175
• Elements → Substances that can’t be broken down any further.

• Atom → The smallest unit of an element.
• Molecule →A molecule is formed when two or more atoms bond
together chemically.
Molecules can consist of the same type of atoms or different types.
• Compound → A compound is a type of molecule that contains
two or more different types of atoms bonded together.
Examples of molecules: Carbon dioxide (CO2) and methane (CH4) ,

molecular hydrogen (H2), molecular oxygen (O2) and molecular
nitrogen (N2).
Examples of compounds: Only molecules containing two or more
elements, such as carbon dioxide (CO2) and methane (CH4).
Q: Explain why all compounds are molecules but not all
molecules are compounds.
Class Lecturer
What is a chemical bond? Chem- 101

Chem- 175
A chemical bond is an attraction between atoms that

allows the formation of chemical substances that
contain two or more atoms. The bond is caused by
the electromagnetic force attraction between
opposite charges, either between electrons and
nuclei, or as the result of a dipole attraction.
In simple words, the attraction between two atoms

or ions that holds them together is known as
chemical bond.

Class Lecturer
How and why a chemical bond is formed? Chem- 101

Chem- 175
A chemical bond may be formed either by sharing of

electrons or by transfer of electrons between atoms i.e., by
reorganization of electrons between atoms.
A chemical bond is formed by an atom to get more

stability. Every atom tries to get more stability by
lowering its potential energy. This can be achieved by
making a bond.
The potential energy decreases when two atoms attract

each other. Hence energy is liberated during the formation
of a chemical bond i.e., it is an exothermic process.

Class Lecturer
1. IONIC BOND Chem- 101
Chem- 175
The electrostatic force of attraction between two

oppositely charged ions is called ionic bond.
An ionic bond is formed due to transfer of electrons from
one atom to another.
An ionic bond is formed between two atoms when their
electronegativity difference is greater than 1.7 on
Pauling's scale.
In general, an ionic bond is formed between a metal atom
and a nonmetal atom.
E.g., NaCl, NaF, LiF, MgCl2 etc.,

Class Lecturer
Formation of an Ionic Bond and its Compound Chem- 101
Chem- 175
1. Formation of positive ions

Each sodium atom (Na) loses its single valence electron
to form a positively charged sodium ion (Na+).
Na Na+ + e
2. Formation of negative ions
Each chlorine atom gains an electron from a sodium atom
to form a negatively charged chloride ion.
Cl + e Cl -
3. Formation of ionic bonds
Positive sodium ions and negative chloride ions are
attracted to one another by electrostatic attraction to
form sodium chloride.
Na+ + Cl - NaCl
Class Lecturer
Formation of an Ionic Bond and its Compound Chem- 101
Chem- 175
IONIC BOND FORMATION - ELECTRON TRANSFER

BETWEEN METALS & NONMETALS
= a valence electron
+9 F
2e
7e
8e
F-
1e
8e ISOELECTONIC
8e WITH Ne
2e
+19
K
F
ISOELECTRONIC
WITH Ar K K+
Class Lecturer
Characteristics of ionic compounds Chem- 101

Chem- 175
1. The ionic compounds contain oppositely charged ions which are strongly attracted
to each other. Hence these are hard substances existing as crystalline solids at room
temperature. Their melting and boiling points are very high due to strong
electrostatic forces of attractions between the ions.
2. The ionic bond is direction less and the electrostatic forces of attraction are present
in all directions around an ion. Hence there is no isolated discrete molecule in the
ionic crystal. Entire crystal is considered as the giant molecule.
3. The ionic compounds do not exhibit isomerism due to non directional nature of
ionic bond.
4. In the solid state, the ions cannot move freely and hence they do not conduct
electricity. However in the fused state or in aqueous solutions, the ionic
compounds show electrical conductivity due to presence of freely moving ions.
5. Ionic compounds are polar in nature and hence they are soluble in polar solvents
like water. However these are not soluble in non polar solvents like benzene,
carbon tetrachloride etc.
6. The reactions between ionic compounds in aqueous solutions occur very fast due
to presence of separated ions. e.g. A white precipitate of AgCl is formed instantly
when aqueous solution of NaCl and AgNO3 are mixed.
Class Lecturer
2. Covalent Bond Chem- 101
Chem- 175
The chemical bond formed between two atoms due to the sharing of electron
pair(s) is called covalent bond.
It is formed between two atoms for which the electronegativity difference is less
than 1.7 on Pauling's scale.
Usually two nonmetal atoms form a covalent bond. E.g. H2, HCl, H2O.
The shared pair of electrons, also known as bond pair, is either formed due to
equal contribution of electrons by each atom participating in the bond
formation; or contributed by only one atom. In the later case, the bond is also
known as co-ordinate covalent bond or dative bond.
Conditions for formation of covalent bond
1. The combining atoms should be short by 1, 2 or 3 electrons in the valence
shell in comparison to stable noble gas configuration.
2. Electronegativity difference between the two atoms should be zero or very
small.
3. The approach of the atoms towards one another should be accompanied by
decrease of energy.
Class Lecturer
Types of covalent Bond Chem- 101
Chem- 175
Single Covalent Bonds

When only one pair of electrons is shared, the result is a single
covalent bond.
The figure shows two hydrogen atoms forming a hydrogen molecule with a
single covalent bond, resulting in an electron configuration like helium.
• Also called Sigma Bond – represented by σ – forms when valence

atomic orbitals overlap and share localized electrons.
• Sigma bonds are single covalent bonds.
• Sigma bonds occur when the pair of shared electrons is in an area
centered between the two atoms.

Class Lecturer
Chem- 175
Multiple Covalent Bonds

Double bonds form when two pairs of electrons are shared
between two atoms.
Triple bonds form when three pairs of electrons are shared

between two atoms.
A multiple covalent bond consists

of one sigma bond and at least
one pi bond
• The pi bond is formed when
parallel orbitals overlap and
share electrons.
Class Lecturer
Chem- 175
Polar vs. Non-Polar Covalent Bonds

Polar molecules unequally share Non-polar molecules have
electrons between atoms, so have a electrons equally shared
slight positive charge at one end and between their atoms.
a slight negative charge at the other.

Class Lecturer
Polar, Non-Polar and Ionic Bonds Chem- 101
Chem- 175
Polar molecules unequally share

Non-polar molecules
electrons between atoms, so have a
have electrons equally
slight positive charge at one end and
shared between their
a slight negative charge at the other.
atoms.

Class Lecturer
Characteristics of Covalent compounds Chem- 101
Chem- 175
1. These exist as gases or liquids under the normal

conditions of temperature and pressure. Some covalent
compounds exist as soft solids.
2. these compounds have relatively low melting and boiling
points except, Diamond, Carborandum (SiC), Silica (SiO2),
AlN etc. have giant three dimensional network structures
and have exceptionally high melting points
3. In general covalent substances are bad conductor of
electricity. Polar covalent compounds like HCl in solution
conduct electricity. Graphite can conduct electricity in solid
state since electrons can pass from one layer to the other.
4. These compounds are generally insoluble in polar solvent
like water but soluble in non-polar solvents like
benzene etc. some covalent compounds like alcohol,
dissolve in water due to hydrogen bonding.
Class Lecturer
Characteristics of Covalent compounds Chem- 101
Chem- 175
5. The covalent bond is rigid and directional. These compounds, thus

show isomerism (structural and space).
6. Covalent substances show molecular reactions. The reaction
rates are usually low.
7. The number of electrons contributed by an atom of the element
for sharing with other atoms is called covalency of the element.
Covalency = 8 – [Number of the group to which element belongs].
The variable covalency of an element is equal to the total number
of unpaired electrons in s, p and d-orbitals of its valency shell.
8. The element such as P, S, Cl, Br, I have vacant d-orbitals in their
valency shell. These elements show variable covalency by
increasing the number of unpaired electrons under excited
conditions. The electrons from paired orbitals get excited to
vacant d-orbitals of the same shell.
Class Lecturer
3. COORDINATE COVALENT BOND Chem- 101
Chem- 175
This is a special type of covalent bond where the shared pair of

electrons are contributed by one species only but shared by both.
The atom which contributes the electrons is called the donor
(Lewis base) while the other which only shares the electron pair is
known as acceptor (Lewis acid).
This bond is usually represented by an arrow (→) pointing from
donor to the acceptor atom.
BF3 molecule, boron is short of two electrons. So to complete its
octet, it shares the lone pair of nitrogen in ammonia forming a
dative bond.
Examples: CO, N2O, N2O3, N2O4, N2O5, HNO3, NO–3, SO2, SO3,
H2SO4, SO2–4, SO2–2, H3PO4, H4P2O7, H3PO3, Al2Cl6 (Anhydrous),
O3, SO2Cl2, SOCl2, HIO3, HClO4, CH3NC, N2H+5, CH3NO2, NH+4,
[Cu(NH3)4]2+ etc.

Class Lecturer
FORMATION OF COORDINATE COVALENT BOND Chem- 101
Chem- 175
H + H +
LONE e- PAIR
HYDROGEN
N H
. .
H
ION WITH
NO ELECTRONS . .
. .
. .
H
AMMONIUM
AMMONIA
ION3 IS
NH
FORMED NH4+

Class Lecturer
Characteristics of Coordinate Covalent compounds Chem- 101
Chem- 175
1. Their melting and boiling points are higher than purely

covalent compounds and lower than purely ionic compounds.
2. These are sparingly soluble in polar solvent like water but
readily soluble in non-polar solvents.
3. Like covalent compounds, these are also bad conductors of
electricity. Their solutions or fused masses do not allow the
passage to electricity.
4. The bond is rigid and directional.

Class Lecturer
Intramolecular and intermolecular forces Chem- 101

Chem- 175
Intramolecular forces or intra. interaction, are the forces that arise within a
molecule. It is the force responsible for holding the atoms together in a molecule.
The conductivity and solubility of substances in the presence of solvents and the
physical properties of metals depend on the intramolecular forces.
Intermolecular forces or inter. interactions, are the electrostatic forces of

attraction between molecules in a compound. The intermolecular forces tend to
attract the molecules together, bring them closer, and make the compound stable.
Intermolecular forces are important because they affect the compound’s physical
properties and characteristics like melting point, boiling point, vapor pressure,
viscosity, solubility, and enthalpy.
Intramolecular forces are the forces
that hold atoms together within a
molecule.
Intermolecular forces are forces
that exist between molecules.
Class Lecturer
Intramolecular forces Chem- 101
Chem- 175
1. Ionic Bond: It is due to the attraction between ions. Ions are

formed when an atom loses or gains electrons. The ionic bond is
formed between a metal and nonmetal, where the metal loses
electrons, and the nonmetal gains them.
Examples: Sodium chloride (NaCl), potassium iodide (KI), and

magnesium oxide (MgO)
2. Covalent Bond: It is due to sharing of electrons between two
atoms. Atoms share their outermost or valence electrons to fulfill
the octet rule and form bonds. Such a type of bonding occurs
between two nonmetals. The covalent bond is the strongest of all
intramolecular forces and the most common form of chemical
bond in living organisms.
Class Lecturer
Intramolecular forces Chem- 101
Chem- 175
Examples: Water (H2O), carbon dioxide (CO2), and ammonia (NH3)

3. Metallic Bond: It is a force that holds
atoms together in a metal. The outermost
electron shells (orbitals) of each metal
atom overlap with many neighboring
atoms. As a result, the valence electrons
move freely from one atom to another,
which results in an attraction between the
cloud of electrons and the positively
charged nuclei.
Examples: Sodium (Na), Potassium (K), and Gold (Au)
Class Lecturer
Metallic bond Chem- 101
Chem- 175
Atoms of metals are tightly packed together in a giant lattice similar to

the lattice in ionic compounds.
metal sea of free

atoms
ions electrons
The outer electrons separate from their atoms and become

delocalized, creating a ‘sea of electrons’. The atoms become
positive ions and are attracted to these electrons.
This attraction is called metallic bonding and is the reason why
the positive metal ions do not repel each other.
Class Lecturer
Properties of Metals Chem- 101
Chem- 175
1. Lustre –due to mobile electrons within the lattice being able to

reflect light causing the metal to shine
2. Conduction of heat – electrons are able to gain kinetic energy in
hotter areas of the metal and are able to quickly transfer it to
other parts of the metal lattice because of their freedom of
movement. Heat causes the electrons to move faster and the
‘bumping’ of these electrons with each other and the protons
transfers the heat.
3. Conduction of electricity – When an electric field is applied to a
metal, one end of the metal becomes positive and the other
becomes negative. All the electrons experience a force toward the
positive end. The movement of electrons is an electric current.

Class Lecturer
Properties of Metals Chem- 101
Chem- 175
4. Density – most metals have relatively high densities because

metallic lattices are close-packed.
5. Malleability and ductility – metals are malleable and ductile,
rather than brittle, as a result of the non-directional nature of
metallic bonds. The attractive forces exerted by the positive metal
ions for the mobile electrons occur in all directions. The nature of
the metal does not change when the metal becomes thinner.
6. Melting point and hardness – The generally high melting points
and hardness of metals indicate that metallic bonding is quite
strong. Melting points and hardness increase with an increase in
the number of outer shell electrons, since there is a greater
attractive force between the cations and the electrons.
Class Lecturer
Intermolecular forces Chem- 101
Chem- 175
Hydrogen bonding: This is a special kind of dipole-dipole interaction

that occurs specifically between a hydrogen atom bonded to an
electronegative atom. The hydrogen bond is the strongest
intermolecular force.
Essential requirements for formation of hydrogen bond:
A hydrogen atom must be directly bonded to a highly
electronegative atom (e.g. F, O, N, Cl, Br and I)
An unbonded pair of electrons (lone pair electrons) is presented on
the electronegative atom
Examples: Water (H2O),
hydrogen chloride (HCl),
ammonia (NH3), methanol
(CH3OH), ethanol
(C2H5OH), and hydrogen
bromide (HBr)
Class Lecturer
Chem- 101
Chem- 175
Explain why the order of boiling point is H 2O>HF>NH3

The boiling point of H2O is higher than NH3 and HF. Because
▪ H2O can form 2 hydrogen bond per molecule
▪ NH3 and HF can form only 1 hydrogen bond per molecule
➢Comparing N and F, F is more electronegative, the intermolecular hydrogen bond
formed between HF molecules is stronger than NH3
➢HF has a higher boiling point than NH3
➢More energy is needed to break the hydrogen bonds in NH3, H2O and HF
No. of H atoms No. of lone pair No. of hydrogen

available for hydrogen electrons bonds can form
bond formation available per molecule
NH3 3 1 1
H2O 2 2 2
HF 1 3 1

Class Lecturer
THEORIES OF CHEMICAL BONDING Chem- 101
Chem- 175
Electronic theory of chemical bonding: According to this theory proposed

independently by Kossel & Lewis, a chemical bond between atoms is formed in
order to get nearest inert gas configuration. This can be achieved by either losing
or gaining or sharing electrons.
Valence bond theory (VBT theory): The valence bond theory was proposed by
Heitler and London to explain the formation of covalent bond quantitatively using
quantum mechanics. Later on, Linus Pauling improved this theory by introducing
the concept of hybridization.
Valence Shell Electron Pair Repulsion Theory (VSEPR Theory): Sidgwick and
Powell in 1940, proposed a simple theory based on the repulsive interactions of the
electron pairs in the valence shell of the atoms. This theory provides a simple
procedure to predict the shapes of covalent molecules. It was further developed and
redefined by Nyholm and Gillespie (1957).
Molecular orbital theory (MO theory): This theory, developed by Robert S.
Mullikan, incorporates the wave like characteristics of electrons in describing
bonding behavior. According to this theory, the atomic orbitals of bonding atoms
combine with each other by giving rise to molecular orbitals.

Class Lecturer
KOSSELL'S ELECTRONIC THEORY Chem- 101
Chem- 175
The formation of bond was explained by Kossell as follows:

1. The atoms of inert gases are stable due to octet configuration
(ns2np6) in their outer shell. Hence atoms must possess eight
electrons in their outer shell to get more stability. This is referred
to as octet rule.
2. However, Helium is also highly stable due to 1s2 configuration.
3. Every atom tries to get nearest inert gas configuration either by
losing or gaining electrons to form bond.
4. Only the electrons in the outer shell participate in bond formation.
These electrons are also called as valence electrons. The electrons
in the inner shell are called as core electrons and do not
participate in the bond formation.
Class Lecturer
KOSSELL'S ELECTRONIC THEORY Chem- 101
Chem- 175
AlF3 (Aluminium Fluoride) :

The Al atom loses 3 electrons and each F atom gains 1 electron to get
their nearest inert gas: Neon's configuration, [He] 2s22p6.
Thus formed Al3+ and three F- ions combine together to give AlF3.
The electrovalency of Al is 3 and that of F is 1.

Note: The bond between Al (e.n = 1.5) and F (e.n = 4.0) is ionic since
the electronegativity difference between them is 2.5.
Class Lecturer
VALENCE BOND THEORY (VBT) & HYBRIDIZATION Chem- 101
Chem- 175
The main postulates of this theory are as follows:

1. A covalent bond is formed by the overlapping of two half-filled
valence atomic orbitals of two different atoms.
2. The electrons in the overlapping orbitals get paired and
confined between the nuclei of two atoms.
3. The electron density between two bonded atoms increases due
to overlapping. This gives stability to the molecule.
4. The greater the extent of overlapping, the stronger the bond
formed.
5. The direction of the covalent bond is along the region of
overlapping of the atomic orbitals i.e., covalent bond is
directional.

Class Lecturer
Chem- 175
There are two types of covalent bonds based on the pattern of

overlapping as follows:
(i) σ-bond: The covalent bond formed due to overlapping of atomic
orbital along the inter nucleus axis is called σ-bond. It is a stronger
bond and cylindrically symmetrical.
Depending on the types of orbitals overlapping, the σ-bond is divided
into following types:
σs-s bond:
σp-p bond:
σs-p bond:

Class Lecturer
Chem- 175
(ii) π-bond: The covalent bond formed by sidewise overlapping of

atomic orbitals is called π- bond. In this bond, the electron density is
present above and below the inter nuclear axis. It is relatively a
weaker bond since the electrons are not strongly attracted by the
nuclei of bonding atoms.

Class Lecturer
BONDING IN MOLECULES BY VBT Theory Chem- 101
Chem- 175
O2 molecule:
• The electronic configuration of O in the ground state is [He] 2s22px22py12pz1.
• The half-filled 2py orbitals of two oxygen atoms overlap along the inter-nuclear
axis and form σp-p bond.
• The remaining half-filled 2pz orbitals overlap laterally to form a πp-p bond.
• Thus a double bond (one σp-p and one πp-p) is formed between two oxygen atoms.
N2 molecule:
• The ground state electronic configuration of N is [He] 2s2 2px1 2py1 2pz1.
• A σp-p bond is formed between two nitrogen atoms due to
the overlapping of half-filled 2px atomic orbitals along the
inter-nuclear axis.
• The remaining half-filled 2py and 2pz orbitals form two πp-p
bonds due to lateral overlapping. Thus a triple bond (one
and two) is formed between two nitrogen atoms.
Class Lecturer
HYBRIDIZATION Chem- 101
Chem- 175
The intermixing of two or more pure atomic orbitals of an atom

with the almost same energy to give the same number of identical
and degenerate new types of orbitals is known as hybridization.
The new orbitals formed are also known as hybrid orbitals.

Class Lecturer
HYBRIDIZATION Chem- 101
Chem- 175
Silent features of hybridization:

1. The number of hybrid orbitals is equal to the number of atomic orbitals
that get hybridized.
2. The hybridized orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than pure
atomic orbitals.
4. These hybrid orbitals are directed in space in some preferred direction to
have minimum repulsion between electron pairs and thus a stable
arrangement. Therefore, the type of hybridization indicates the geometry
of the molecules.
Important conditions for hybridization
1. The orbitals present in the valence shell of the atom are hybridized.
2. The orbitals undergoing hybridization should have almost equal energy.
3. The promotion of electrons is not an essential condition prior to
hybridization.
4. It is not necessary that only half-filled orbitals participate in
hybridization. In some cases, even filled orbitals of valence shells take
part in hybridization.
Class Lecturer
sp HYBRIDIZATION Chem- 101
Chem- 175
Intermixing of one 's' and one 'p'

orbitals of almost equal
energy to give two identical
and degenerate hybrid
orbitals is called 'sp'
hybridization.
These sp-hybrid orbitals are arranged linearly by making 180o of

angle. They possess 50% 's' and 50% 'p' character.
ILLUSTRATIONS OF SP HYBRIDIZATION
1. Beryllium Chloride (BeCl2):
• The electronic configuration of 'Be' in the ground state is 1s2 2s2. Since
there are no unpaired electrons, it undergoes excitation by promoting
one of its 2s electrons into an empty 2p orbital.

Class Lecturer
sp HYBRIDIZATION Chem- 101
Chem- 175
• In the excited state, the electronic configuration of Be is 1s2 2s1 2p1.

• In the excited state, the Be atom undergoes ‘sp’ hybridization by mixing a 2s and
one 2p orbitals. Thus two half-filled 'sp' hybrid orbitals are formed, which are
arranged linearly.
• These half-filled sp-orbitals form two σ bonds with two Cl atoms.
• BeCl2 is linear in shape with a bond angle of 180o.
2. Acetylene (C2H2)
overlap in one position - 
180o
p overlap - 
Class Lecturer
sp2 HYBRIDIZATION Chem- 101
Chem- 175
• Intermixing of one 's' and two 'p' orbitals of almost equal energy
to give three identical and degenerate hybrid orbitals is known as
sp2 hybridization.
• The three sp2 hybrid orbitals are oriented in trigonal planar
symmetry at angles of 120o to each other.
• The sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p'
character.

Class Lecturer
Chem- 175
ILLUSTRATIONS OF sp2 HYBRIDIZATION

1. Boron trichloride (BF3):
• The electronic configuration of 'B' in the ground state is 1s2 2s2 2p1 with only
one unpaired electron
• In the excited state, Boron undergoes sp2 hybridization by using a 2s and two 2p
orbitals to give three half-filled sp2 hybrid orbitals which are oriented in
trigonal planar symmetry.
• Boron forms three σsp2-p bonds with three chlorine atoms by using its half filled
sp2 hybrid orbitals. Each chlorine atom uses it's half-filled p-orbital for the σ-
bond formation.
• The shape of BF3 is trigonal planar with bond angles equal to 120o.

Class Lecturer
Chem- 175
2. Ethylene (C2H4)
overlap in one position - 
~120o
p overlap - 

Class Lecturer
Chem- 175
• In sp3 hybridization, one 's' and three 'p' orbitals of almost equal
energy intermix to give four identical and degenerate hybrid
orbitals.
• These four sp3 hybrid orbitals are oriented in tetrahedral
symmetry with 109o28' angle with each other.
• The sp3 hybrid orbitals have 25% ‘s’ character and 75% 'p'
character.

Class Lecturer
Chem- 175
ILLUSTRATIONS OF sp3 HYBRIDIZATION

1. Methane (CH4)
• The carbon atom undergoes sp3 hybridization in the excited state by
mixing one ‘2s’ and three 2p orbitals to furnish four half-filled
sp3 hybrid orbitals, which are oriented in tetrahedral symmetry in space
around the carbon atom.
• Each of these sp3 hybrid orbitals forms a σsp3-s bond with one hydrogen
atom. Thus carbon forms four σsp3-s bonds with four hydrogen atoms.
• Methane molecule is tetrahedral in shape with 109o28' bond angle.

Class Lecturer
Chem- 175
both carbons are sp3 hybridized

s-sp3 overlaps to  bonds
2. Ethane (C2H6)
~109.5o
sp3-sp3 overlap to form a  bond
3. Ammonia (NH3)
3. Water (H2O)

Class Lecturer
sp3d HYBRIDIZATION Chem- 101
Chem- 175
• In sp3d hybridization, one 's', three 'p' and one 'd' orbitals of
almost equal energy intermix to give five identical and degenerate
hybrid orbitals, which are arranged in trigonal bipyramidal
symmetry.
• Among them, three are arranged in trigonal plane and the
remaining two orbitals are present above and below the trigonal
plane at right angles.
• The sp3d hybrid orbitals have 20% 's', 60% 'p' and 20% 'd'
characters.

Class Lecturer
sp3d HYBRIDIZATION Chem- 101
Chem- 175
ILLUSTRATIONS OF sp3d HYBRIDIZATION

1. Phosphorus pentachloride(PCl5)
• The ground state electronic configuration of P is: 1s2 2s22p6 3s23px13py13pz1.
• The configuration of 'P' in the excited state is 1s2 2s22p6 3s13px13py13pz1 3d1.
• In the excited state, intermixing of a 3s, three 3p and one 3d orbitals to give five
half-filled sp3d hybrid orbitals, which are arranged in trigonal bipyramidal
symmetry.
• By using these half-filled sp3d orbitals, phosphorous forms five σsp3d-p bonds with
chlorine atoms. Each chlorine atom makes use of half filled 3pz orbital for the
bond formation.
• * The shape of PCl5 molecule is trigonal bipyramidal with 120o and 90o of ∠Cl - P
- Cl bond angles.

Class Lecturer
Sp3d2 and Sp3d3 HYBRIDIZATION Chem- 101
Chem- 175
1. Sulfur hexaflouride (SF6)
1) Iodine heptafluoride (IF7):

Class Lecturer
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY Chem- 101
Chem- 175
The main postulates of VSEPR theory are as follows:

1. The electron pairs in the valence shell around the central atom of a molecule
repel each other and tend to orient in space so as to minimize the repulsions and
maximize the distance between them.
2. There are two types of valence shell electron pairs viz., i) Bond pairs and ii) Lone
pairs
The order of repulsion between different types of electron pairs is as
follows: Lone pair - Lone pair > Lone Pair - Bond pair > Bond pair - Bond pair
3. In VSEPR theory, the multiple bonds are treated as if they were single bonds. The
electron pairs in multiple bonds are treated collectively as a single super pair.
The repulsion caused by bonds increases with increase in the number of
bonded pairs between two atoms i.e., a triple bond causes more repulsion than
a double bond which in turn causes more repulsion than a single bond.
4. The shape of a molecule can be predicted from the number and type of valence
shell electron pairs around the central atom.
When the valence shell of central atom contains only bond pairs, the molecule
assumes symmetrical geometry due to even repulsions between them.
However the symmetry is distorted when there are also lone pairs along with bond pairs due to uneven repulsion forces.
Class Lecturer
Chem- 175
5. Primary & Secondary effects on bond angle and shape:
a) The bond angle decreases due to the

presence of lone pairs, which cause more
repulsion on the bond pairs and as a result
the bond pairs tend to come closer.
b) The repulsion between electron pairs increases with increase in

electronegativity of central atom and hence the bond angle
increases. The bond pairs are closer and thus by shortening the
distance between them, which in turn increases the repulsion. Hence
the bonds tend to move away from each other.

Class Lecturer
Chem- 175
However the bond angle decreases when the electronegativities of

ligand atoms are more than that of central atom. There is
increase in the distance between bond pairs since they are now
closer to ligand atoms. Due to this, they tend to move closer
resulting in the decrease in bond angle.
c) The bond angle decreases with increase in the size of central atom.

Class Lecturer
Chem- 175

However the bond angle increases with increase in the size of
ligand atoms, which surround the central atom.
d) The bond angles are also changed when multiple bonds are
present. It is due to uneven repulsions.
6. When there are two or more resonance structures, the VSEPR

theory is applicable to any of such contributing structure.

Class Lecturer
APPLICATIONS & ILLUSTRATIONS OF VSEPR THEORY Chem- 101
Chem- 175
1) Methane (CH4):
* The Lewis structure of methane molecule is:
There are 4 bond pairs around

the central carbon atom in its
valence shell. Hence it has
tetrahedral shape with 109o28'
of bond angles.

Class Lecturer
Chem- 175
2) Ammonia (NH3):
* The Lewis structure of ammonia indicates there are three
bond pairs and one lone pair around the central nitrogen
atom.
* Since the steric number is 4, its

structure is based on tetrahedral
geometry. However, its shape is
pyramidal with a lone pair on nitrogen
atom.
* The bond angle is decreased from
109o28' to 107o48' due to repulsion
caused by lone pair on the bond pairs.
Class Lecturer
Chem- 175
3) Water (H2O):
* It is evident from the Lewis structure of water molecule,
there are two bond pairs and two lone pairs in the valence
shell of oxygen. Hence its structure is based on tetrahedral
geometry. However its shape is angular with two lone pairs
on oxygen.
* The bond angle is decreased to

104o28' due to repulsions caused by
lone pairs on bond pairs. It can be
noted that the bond angle decreases
with increase in the number of lone
pairs on the central atom.
Class Lecturer
Chem- 175
A method to predict the shapes of molecules from their

electronic structures (Lewis structures do not depict
shape)
Basic principle: each group of valence electrons around a central

atom is located as far away as possible from the others in order to
minimize repulsions
Both bonding and non-bonding valence electrons around

the central atom are considered.
AXmEn symbolism: A = central atom, X = surrounding atoms,

E = non-bonding electrons (usually a lone pair)

Class Lecturer
THE SHAPE OF MOLECULE (AXE Method) Chem- 101
Chem- 175
RELATION BETWEEN NUMBER & TYPE OF VALENCE ELECTRON

PAIRS WITH THE SHAPE OF MOLECULE (AXE Method)
To determine the shape and geometry of a molecule.

AXN/AXE is a simple formula to
represent the number of atoms bonded
to the central atom in a molecule and
the number of lone pairs present on it.
AXN/ AXE notation for the HNO3 molecule

• A in the AXN formula represents the central atom. In HNO3, nitrogen (N) acts
as the central atom, so A= N.
• X denotes the electron domains bonded to the central atom. 2 O-atoms and 1
OH group is directly bonded to the central N atom in HNO3; thus, X=3.
• N stands for the lone pairs present on the central atom. As per the Lewis dot
structure of HNO3, there is no lone pair present on central nitrogen; thus, N=0.
So, the AXN generic formula for HNO3 is AX3.
Class Lecturer
Steric number Chem- 101
Chem- 175
Is equal to the number of sigma bonds surrounding the atom plus the
number of lone pairs on the atoms.
St. number Hybridization
2 sp
3 sp2
4 sp3
5 sp3d
6 sp3d2
Class Lecturer
THE SHAPE OF MOLECULE Chem- 101
Chem- 175
Electron-group repulsions and the five basic

molecular shapes
Linear Trigonal Tetrahedral
Trigonal bipyramidal Octahedral
Ideal bond angles are shown for each shape.

Class Lecturer
Chem- 175
The single molecular shape of the linear

electron-group arrangement
Examples:
CS2, HCN, BeF2

Class Lecturer
Chem- 175
The two molecular shapes of the trigonal planar

Class
Examples: Shape
SO2, O3, PbCl2, SnBr2

Examples:
SO3, BF3, NO3-, CO32-

Class Lecturer
Chem- 175
The three molecular shapes of the tetrahedral

Examples:
CH4, SiCl4,
SO42-, ClO4-
Examples: Examples:
NH3 H2O
PF3
OF2
ClO3
SCl2
H3O+
Class Lecturer
Chem- 175
The four molecular shapes of the trigonal bipyramidal

Examples:
Examples:
SF4
PF5
XeO2F2
AsF5
IF4+
SOF4
IO2F2-
Examples:
Examples:
XeF2
ClF3
BrF3 I3-
IF2-

Class Lecturer
Chem- 175
The three molecular shapes of the octahedral

Examples:
SF6
IOF5
Examples: Examples:
BrF5 XeF4
TeF5- ICl4-
XeOF4

Class Lecturer
THE SHAPE OF MOLECULE (AXE Method) Chem- 101
Chem- 175

Class Lecturer
Chem- 175

Class Lecturer
Chem- 175

Class Lecturer
Chem- 175

Class Lecturer
Chem- 175
St. number Hybridization
2 sp
3 sp2
4 sp3
5 sp3d
6 sp3d2
Class Lecturer
Chem- 175
STEPS INVOLVED IN PREDICTING THE SHAPES OF

MOLECULES USING VSEPR THEORY
1. The first step in determination of shape of a molecule is to write
the Lewis dot structure of the molecule.
2. Then find out the number of bond pairs and lone pairs in the
valence shell of central atom.
3. While counting the number of bond pairs, treat multiple bonds
as if they were single bonds. Thus electron pairs in multiple
bonds are to be treated collectively as a single super pair.
4. Use the previous showing table to predict the shape of molecule
based on steric number and the number of bond pairs and
lone pairs.

Class Lecturer
WEAKNESSES OF VSEPR THEOREY Chem- 101
Chem- 175
1. Does not work well for transition metals. in general, according to

text, ‘whereas the VSEPR model may be applicable to p-block
species, it is not appropriate to apply [VSEPR] to d-electron
configurations of transition metal compounds.
2. Sometimes it’s necessary to take account of ligand size. For
example, the bond angles in PH3 are 93.4° and in PF3 97.8°.
Based on electronegativity, we would expect the bond angles in PF3
to be smaller rather than larger.
3. “Under certain circumstances, metal complexes with a formal d0
electronic configuration may exhibit structures that violate the
traditional structure models, such as the VSEPR concept or
simple ionic pictures. Some examples of such behavior, such as the
bent gas-phase structures of some alkaline earth dihalides, or the
trigonal prismatic coordination of some early transition metal
chalcogenides or pnictides, have been known for a long time.
Class Lecturer
Chem- 175
Steps to convert a molecular formula into a Lewis

structure
Place the atom with the
molecular Step 1 lowest EN in the center
formula
atom Step 2 Add A-group

placement numbers
sum of Step 3 Draw single bonds and

valence e- subtract 2e- for each bond
remaining Step 4 Give each

valence e- atom 8e-
(2e- for H)
Lewis
structure

Class Lecturer
Chem- 175
The steps in determining a molecular shape
Molecular Step 1
formula
Lewis Step 2 Count all e- groups around the

structure central atom A
Note lone pairs and

Electron-group Step 3
arrangement double bonds
Count bonding and
Bond Step 4 non-bonding e-
angles groups separately.
Molecular
shape
(AXmEn)
Class Lecturer
Molecular Orbital (MO) Theory Chem- 101
Chem- 175
A delocalized bonding model
A quantum-mechanical treatment of molecules similar to

that used for isolated atoms
Invokes the concept of molecular orbitals (MOs)

(extension of atomic orbitals)
Exploits the wave-like properties of matter (electrons)
A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.
Atomic wave functions are summed to obtain

molecular wave functions.

Class Lecturer
Chem- 175
Principles of Molecular Orbital Theory

Total number of molecular orbitals is equal to the total number of
1
atomic orbitals from combining atoms.
Bonding molecular orbitals: have less energy than the

constituent atomic orbitals before bonding.
2
Antibonding molecular orbitals: have more energy than the
constituent atomic orbitals before bonding.
Following both the Pauli exclusion & Hund's rule, electrons fill
3
in orbitals of increasing energy.
Molecular orbitals are best formed when composed of atomic

4
orbitals of like energies.

Class Lecturer
Chem- 175
number of AOs combined = number of MOs produced
Bonding MO: lower in energy than isolated atoms
Antibonding MO: higher in energy than isolated atoms
To form MOs, AOs must have similar energy and orientation
Sigma (s) and pi (p) bonds are denoted as before; a star

(asterick) is used to denote antibonding MOs.

Class Lecturer
Chem- 175
Atomic wave functions are summed to obtain

molecular wave functions.
If wave functions reinforce each

other, a bonding MO is formed
(region of high electron density
exists between the nuclei).
Amplitudes of wave
functions are added
If wave functions cancel each other,

an antibonding MO is formed (a
node of zero electron density occurs
between the nuclei).
Amplitudes of wave
functions are subtracted
Class Lecturer
Chem- 175
Contours and energies of the bonding and antibonding

molecular orbitals in H2

Class Lecturer
Chem- 175
Molecular orbital diagram for the H2 molecule
MOs are filled

in the same sequence
as for AOs
(Aufbau and Pauli exclusion
principles, Hund’s rule)
The MO bond order = [1/2 ( e- in bonding MOs) - (e- in antibonding MOs)]
higher bond order = stronger bond Has predictive power!

Class Lecturer
Chem- 175
Molecular Orbital (MO) Theory

*2s *2s
2s 2s 2s
2s
Energy
2s 2s
Bonding in s-block Be2
Li2
homonuclear
diatomic molecules
*1s *1s
1s 1s 1s 1s
1s 1s
Li2 bond order = 1 Be2 bond order = 0
Class Lecturer
Chem- 175
MO diagrams for He2+ and He2
*1s *1s
Energy
Energy
1s 1s 1s 1s
1s 1s
AO of MO of AO of AO of MO of AO of
He He+ He+ He He2 He
He2+ bond order = 1/2 He2 bond order = 0
can exist! cannot exist!

Class Lecturer
Chem- 175
Molecular Orbital (MO) Theory

Contours and energies of  and  MOs through
combinations of 2p atomic orbitals
end-to-end
overlap
side-to-side
overlap
Relative energies 2p < 2p < *2p < *2p More effective end-to-end interaction
relative to side-to-side in bonding MOs
Class Lecturer
Chem- 175
Relative MO energy levels for Period 2 homonuclear

diatomic molecules
without 2s-2p with 2s-2p

mixing mixing
MO energy levels MO energy levels

for O2, F2 and Ne2 for B2, C2 and N2
Class Lecturer
Chem- 175
Heteronuclear Diatomic

Molecules
The MO diagram for HF

Energy
1s
nonbonding MOs
2p
2px 2py
lower in energy
than 1s of H!

AO MO of AO
of H HF of F
Class Lecturer
Chem- 175
The MO diagram for NO

*2s
bond order = 2.5
*2p
Energy
2p 2p 2p
2p possible Lewis

structures
*2s
2s 2s
AO of N AO of O
2s
MO of NO
Class Lecturer
Linear Combination of Atomic Orbitals (LCAO) Chem- 101
Chem- 175
Rules for linear combination

1. Atomic orbitals must be roughly of the same energy.
2. The orbital must overlap one another as much as possible-
atoms must be close enough for effective overlap.
3. In order to produce bonding and antibonding MOs, either the
symmetry of two atomic orbital must remain unchanged when
rotated about the internuclear line or both atomic orbitals must
change symmetry in identical manner.
Rules for the use of MOs

* When two AOs mix, two MOs will be produced
* Each orbital can have a total of two electrons (Pauli principle)
* Lowest energy orbitals are filled first (Aufbau principle)
* Unpaired electrons have parallel spin (Hund’s rule)
Bond order = ½ (bonding electrons – antibonding electrons)
Class Lecturer
Chem- 175
The wave function for the molecular orbitals can be approximated

by taking linear combinations of atomic orbitals.
A B
A B
AB = N(cA A + cBB) c – extent to which each AO
contributes to the MO
2AB = (cA2 A2 + 2cAcB A B + cB2 B 2)
density between atoms

Probability density
Overlap integral
electron density on original atoms
Class Lecturer
Chem- 175
+. +. . +.
g bonding
cA = cB = 1
g = N [A + B]
Constructive interference
all cross-sections perpendicular to the
internuclear axis are circles.
Amplitudes of wave
functions are added

Class Lecturer
Chem- 175
Constructive interference
The accumulation of electron density between the nuclei put

the electron in a position where it interacts strongly with
both nuclei.
Nuclei are shielded from each other
The energy of the molecule is lower

Bonding

Class Lecturer
Chem- 175
node
+
. -. +. .-
cA = +1, cB = -1 u antibonding
u = N [A - B]
Destructive interference
The resulting pattern contains a node
where the electron density is zero.
A-B
Amplitudes of wave
functions subtracted.
Class Lecturer
Linear combination of atomic orbitals (LCAO) Chem- 101
Chem- 175
Destructive interference
The electron is excluded from internuclear region →

destabilizing
Antibonding

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Class Lecturer

Chem 101 and 175: General Chemistry

Lectures 1-6 : Chemical Bonds

Yunus Ahmed, PhD

By the end of lectures, you should be able to

• Know the different types of chemical bonds like ionic

• Elements → Substances that can’t be broken down any further.

Examples of molecules: Carbon dioxide (CO2) and methane (CH4) ,

What is a chemical bond? Chem- 101

A chemical bond is an attraction between atoms that

In simple words, the attraction between two atoms

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 4

How and why a chemical bond is formed? Chem- 101

A chemical bond may be formed either by sharing of

A chemical bond is formed by an atom to get more

The potential energy decreases when two atoms attract

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 5

The electrostatic force of attraction between two

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 6

1. Formation of positive ions

IONIC BOND FORMATION - ELECTRON TRANSFER

Characteristics of ionic compounds Chem- 101

Single Covalent Bonds

• Also called Sigma Bond – represented by σ – forms when valence

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 11

Multiple Covalent Bonds

Triple bonds form when three pairs of electrons are shared

A multiple covalent bond consists

Polar vs. Non-Polar Covalent Bonds

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 13

Polar molecules unequally share

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 14

1. These exist as gases or liquids under the normal

5. The covalent bond is rigid and directional. These compounds, thus

This is a special type of covalent bond where the shared pair of

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 17

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 18

1. Their melting and boiling points are higher than purely

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 19

Intramolecular and intermolecular forces Chem- 101

Intermolecular forces or inter. interactions, are the electrostatic forces of

1. Ionic Bond: It is due to the attraction between ions. Ions are

Examples: Sodium chloride (NaCl), potassium iodide (KI), and

Examples: Water (H2O), carbon dioxide (CO2), and ammonia (NH3)

Atoms of metals are tightly packed together in a giant lattice similar to

metal sea of free

The outer electrons separate from their atoms and become

1. Lustre –due to mobile electrons within the lattice being able to

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 24

4. Density – most metals have relatively high densities because

Hydrogen bonding: This is a special kind of dipole-dipole interaction

Explain why the order of boiling point is H 2O>HF>NH3

No. of H atoms No. of lone pair No. of hydrogen

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 27

Electronic theory of chemical bonding: According to this theory proposed

Prepared by Dr. Yunus. Ahmed, Department of Chemistry, CUET Chemical Bond_Slide : 28

The formation of bond was explained by Kossell as follows:

AlF3 (Aluminium Fluoride) :

The electrovalency of Al is 3 and that of F is 1.

The main postulates of this theory are as follows: