20.

Hybridization
Prof Dr Abida Latif
Basic Concepts

+ Chemical Bonding and concept of Hybridization

Structure of atom
+The study of organic chemistry involves the reactions and interactions
of molecules. It is necessary to review he structure of atoms and how they
contribute properties to molecules.
+According to Bohr theory, atom has
• A central positively charged nucleus containing positively charged
particles called protons and neutral particles called neutron both having
unit mass.
• The nucleus is surrounded by negatively charged particles called
electrons.
Structure of atom
• The electrons revolve around the nucleus in fixed orbit or
energy level.
• The electrons are arranged in the orbitals such that the
maximum number of electrons in the various orbitals starting
from the one nearest to nucleus is 2,8,18,32 and so on.
• The outermost orbit of electrons in different atoms except inert
gases is incomplete
Chemical Bonding
 CONTD
• A key point:
• Most of the volume of an atom is occupied by the electrons.
The area occupied by electrons is referred to as the electron
cloud.
Atoms combine --------Molecules
+Why do atoms combine to form a molecule?

+Atoms combine to form molecules because atoms, in general,

cannot exist on their own. Each atom is also unstable and
therefore needs stability. Therefore, atoms combine to
complete their outermost orbital and achieve a stable electronic
configuration.
Atoms combine to form molecules
+When two or more atoms chemically bond together, they form
a molecule. Sometimes the atoms are all from the same
element. For example, when three oxygen atoms bond
together, they form a molecule of ozone (O3).
+Atoms can chemically bond in three basic ways.
+Ionic or electrovalent bond
+Covalent bond
+Coordinate bond
Ionic Bond
+Ionic bonding is the complete transfer
of valence electron(s) between atoms. It is a type of chemical
bond that generates two oppositely charged ions.
+ In ionic bonds, the metal loses electrons to become a
positively charged cation, whereas the nonmetal accepts
those electrons to become a negatively charged anion. Ionic
bonds require an electron donor, often a metal, and an electron
acceptor from nonmetal. They both achieve a more stable
electronic configuration through this exchange.
Ionic bond

In this example, the sodium The magnesium atom is donating both of its
atom is donating its 1 valence valence electrons to chlorine atoms. Each
chlorine atom can only accept 1 electron.
electron to the chlorine atom. Therefore, 2 atoms of chlorine are required to
This creates a sodium cation and accept the 2 electrons donated by the
a chlorine anion. Therefore, net magnesium. It means that the net charge of
charge of the resulting the compound is 0.
compound is 0.
Ionic Bond
+Ionic or electrovalent compounds are non-
volatile.
+ Soluble in water.
+ Possess high Melting Points.
+Their aqueous solutions conduct electric
current.
Covalent Bond/Molecular Bond
+A covalent bond, is a chemical bond that involves the sharing
of electron pairs between atoms. These electron pairs are
known as shared pairs or bonding pairs, and stable balance
of attractive and repulsive forces between atoms, when they
share electrons, is known as covalent bonding.
+If atoms have similar electronegativities (the same affinity for
electrons), covalent bonds are most likely to occur.
Covalent Bond
when two hydrogen atoms
get close enough together,
the attraction is balanced in
both directions and they
share the electrons between
them. A covalent bond is
made and hydrogen gas (H2)
is formed

It is indicated by a line.
Covalent Bond

PCL3: In this example, a phosphorous atom is sharing its three unpaired

electrons with three chlorine atoms. In the end product, all four of these
molecules have 8 valence electrons.
Covalent Bond
+Covalent bonding includes many kinds of interactions,
including σ-bonding, π-bonding, metal-to-metal bonding,
,three-center two-electron bonds and three-center four-
electron bonds.
+Covalent bonding is the sharing of electrons between atoms.
Covalent bonds are commonly found in organic compounds.
Covalent compounds are volatile, generally insoluble in water
but soluble in organic solvents. They possess low melting and
boiling points.
Sigma σ-bonding
+There are two main types of covalent bonds or molecular
orbitals:
+Sigma bonds
+Pi bonds
+Sigma Bond it is formed by the linear or end to end overlap of
[Link] may be obtained by many ways.
+ see next slide
Sigma bond formation
Co-ordinate Bond
+Co-ordinate bond is a type of alternate covalent bond that is
formed by sharing of electron pair from a single atom. Both
shared electrons are donated by the same atom. It is also
called dative bond or dipolar bond.
+The bond is shown by an arrow which points in the direction
where an atom is donating the lone pair to the atom that is
receiving it, see next slide.
Co-ordinate Bond Diagram

[Link] this type of bonding, the atom that shares an electron pair from itself
is termed as the donor.
[Link] other atom which accepts these shared pair of electrons is known
as a receptor or acceptor.
[Link] bond is represented with an arrow →, pointing towards acceptor
from the donor atom.
[Link] sharing of electron pain each atom gets stability.
Formation of ammonium ion

The nitrogen atom in Ammonia donates its electron pair to the empty
orbitals of H+ ion thus nitrogen is donor, H+ is acceptor and a co-ordinate
bond is formed.
Valence of Carbon
+The atomic number of carbon is 6 and its atomic weight is 12.
its electronic configuration is 2,4. the four electrons in the last
orbital and tend to gain four more electrons by forming four
covalent bonds with other atoms,

+This is General Note

Valence of Carbon
Orbital structure of atom
+An atom consists of a nucleus of protons and neutrons,
surrounded by electrons.
+Electrons have such little mass that they exhibit properties
of both particles and waves; there are regions around the
atom where the electron has a high probability of being
found. Such regions are referred to as atomic orbitals.
Orbital Notation

Or Shell number

Or Shell number
Orbital structure of atom
+A quantum number is a value that is used to describe the energy levels
available to atoms and molecules
+Theerefore, electrons in an atom may be identified by Four quantum numbers :
• Principal quantum number (n); energy, distance from nucleus, size of
orbital
• Azimuthal quantum number (ℓ); shape of the orbital
• Spin quantum number (s); spin of electrons about its own axis
+If the electron spins clockwise on its axis, it is described as spin-up;
counterclockwise is spin-down. See next slide.
Spin Quantum Number
Magnetic Quantum Number
+Magnetic quantum number (m); Gives orientation of the orbital in space

+In other words, the value of m describes whether an orbital lies along
the x-, y-, or z-axis on a three-dimensional graph, with the nucleus of
the atom at the origin.
+ For this purposes, it is only important that this quantum number tells
us that for each value of n there may be up to one s-orbital, three p-
orbitals, five d-orbitals, and so on. For example:
+( n= number of Electrons)
+See next slide
Magnetic Quantum Number

The s orbital (l = 0) has one orbital,

since m can only equal 0. That
orbital is spherically symmetrical
about the nucleus.
Magnetic Quantum Number
The p orbital (l = 1) has
three orbitals. These
three orbitals lie along
the x-, y-, and z-axes
Orbital structure of atom
+Electrons occupy concentric shells and subshells around a nucleus. The shells
are given numbers called principle quantum numbers of 1, 2, 3, etc., to identify
the levels. The energy of each shell and distance between the electrons in a
shell and the nucleus increases with increasing principle quantum number.
+Level 1 is the lowest energy level and the electrons in that shell are nearest to
the nucleus.
+Level 2 is higher in energy and the electrons in this level are found further far
from the nucleus than are the electrons in Level 1.
+Shells are composed of subshells. Subshells have designations s, p, d, and f.
Orbital structure of atom

Or
Shell
Orbital structure of atom
+Therefore, four subshells are designated as: s, p, d or f.
+The first s shell has only one subshell designated as 1s,
+the second p shell has two subshells designated as 2s and 2p.
+The third shell has three subshells designated as 3s, 3p, 3d; and
fourth shell has four subshells as 4s, 4p, 4d, 4f.
+The subshells are further divided into smaller units called Orbitals
which are the actual seat of electrons.
+An s subshell is made up of one orbital, a p subshell of three orbitals,
a d subshell of five orbitals and f subshell of seven orbitals, see
coming slide.
Orbital structure of atom

+The outermost shell is known as Valence Shell and the

electrons that occupy this shell are called the Valence
Electrons.
Shapes of Orbitals
+An orbital represents a well defined regions in space in
which electrons can be found.
+They have definite three dimensional shapes.
+In organic chemistry mainly concerned with the s and p
orbitals.
+
+The shapes and orientations of these orbitals are as given
on coming slides :
Shapes and orientation of Orbitals

An s orbital has the shape of

sphere. All the s orbitals has
this shape. In this orbital there
is an equal probability of
finding the electron in any
direction away from the
nucleus. The difference
between 1s and 2s orbital is
that the electron in the 2s
orbital is far away from the
nucleus and has greater
energy.
P orbitals
+A p orbital is dumbbell in shape. There are two lopes
associated with this orbital. They are located on opposite
sides of the nucleus and directed along a particular axis.
+In contrast to s subshell for which there is only one orbital,
but in the p subshell there are three orbitals of equal
energy for electrons to occupy.
+These three p orbitals are directed along the three
coordinate axes as shown in next slide.
Shapes and orientation of p Orbitals
 Hybridization

+By understanding the background

knowledge, now it is very easy to understand
the concept/ topic of Hybridization.
Hybridization
+The phenomenon of mixing up of atomic orbitals of similar
energies and formation of equivalent number of entirely new
orbitals of identical shape and energy is known as "hybridization"
and the new orbitals so formed is called as "hybrid orbitals.
+One of the new Mos (Molecular bonds) formed is more stable (of
lower energy) than the originating AOs. This MO is called a
bonding orbital. The other MO is less stable than the originating
AOs and it is called an antibonding MO.
Key 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 shape of the molecule can be predicted if hybridization of the molecule is
known.
• The bigger lobe of the hybrid orbital always has a positive sign, while the
smaller lobe on the opposite side has a negative sign.
Simply Hybridization
Hybridization tells about:
+ Structure of Molecule
+ Bond of Molecule
+ Bond Angle of Molecule
+ Geometry of Molecule
+ Shape of Molecule
Types of Hybridization
+sp hybridization:
+It 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°.
Examples of sp Hybridization

• All compounds of beryllium like BeF2, BeH2, BeCl2

• All compounds of carbon-containing triple Bond like (Acetylene)

C2H2
General representation of sp
Hybridization
Sp hybridization in BeCl2
+Beryllium chloride, BeCl2
+The electronic configuration of 'Be' in ground state is:
+ 1s2 2s2.
+Since there are no unpaired electrons, it undergoes
excitation by promoting one of its 2s electron into
empty 2p orbital.
+Thus in the excited state, the electronic configuration of
Be is 1s2 2s1 2p1.
Sp hybridization in BeCl2
+In the excited state, the beryllium 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 or give a linear shape.

+
Sp hybridization in BeCl2
+These half filled sp-orbitals form two σ bonds with two 'Cl'
atoms.
+Thus BeCl2 is linear in shape with the bond angle of 180o.
Sp hybridization in BeF2

In BeF2 (Beryllium fluoride) molecule the sp-hybridized orbitals of

Be overlap with the half-filled orbitals of two fluorine atoms to give a
linear shape.
a
Sp hybridization of BeH2
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 orbital. The
new orbitals formed are called sp2 hybrid orbitals.
• It is also called trigonal hybridization.
• A mixture of s and p orbital formed in trigonal symmetry 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 33.33% s character and
66.66% ‘p’ character.
Examples of sp2 Hybridization

• All the compounds of Boron i.e. BF3, BCl3 , BH3(Borane)

• All the compounds of carbon containing a carbon-carbon

double bond e.g. Ethylene (C2H4)
sp2 Hybridization in BCl3
+The electronic configuration of 'B' in ground
state: 1s2 2s2 2p1 with only one unpaired
electron.
+Since the formation of three bonds with chlorine
atoms require three unpaired electrons, there is
promotion of one of 2s electron into the 2p
sublevel by absorbing energy.
+Thus Boron atom gets electronic
configuration: 1s2 2s1 2px1 2py1.
sp2 Hybridization in BCl3
+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 σsp-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.
sp2 Hybridization in BCl3
+Thus the shape of BCl3 is trigonal planar with bond
angles equal to 120o.
+

+
sp2-hybridization in BF3
sp2-hybridization
When three sp2 hybridized orbitals of B overlaps with three
p-orbitals of fluorine, three σ -bonds are formed with bond
angle 120°. The shape of BF3 molecule is thus trigonal
planar.
sp3-hybridization---4 [Link]
+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
regular tetrahedron and make an angle of 109.280 with one another.
• Therefore, the angle between the sp3 hybrid orbitals is 109.280
• Each sp3 hybrid orbital has 25% s character and 75% p character.
• Example of sp3 hybridization: methane (CH4), ethane (C2H6),
sp3-hybridization in Methane
+ During the formation of methane molecule, the carbon atom
undergoes sp3 hybridization, in the excited state by mixing one ‘2s’
and three 2p orbitals to complete four half filled sp3 hybrid orbitals,
which are oriented in tetrahedral symmetry in space around the
carbon atom.
sp3-hybridization of Methane
sp3d-hybridization -----[Link]
+sp3d hybridization involves the mixing of one s, three p orbitals and
one d orbital to form 5 sp3d hybridized orbitals of equal energy.
• 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.
• Example: Hybridization in Phosphorus pentachloride (PCl5)
sp3d-hybridization:
sp3d-hybridization of PCl5
+ The ground state electronic configuration of phosphorus atom is:
1s2 2s22p6 3s23px13py13pz1.
+ The formation of PCl5 molecule requires 5 unpaired electrons. Hence
the phosphorus atom undergoes excitation to promote one electron
from 3s orbital to one of empty 3d orbital.
+ Thus the electronic configuration of 'P' in the excited state is
1s2 2s22p6 3s13px13py13pz1 3d1.
sp3d-hybridization of PCl5
sp3d-hybridization of PCl5
The shape
of
PCl5 molecul
e is trigonal
bipyramidal
with
120o and
90o .
sp3d-hybridization of PCl5
+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.
+Three orbitals are arranged in trigonal planar
symmetry, whereas the remaining two are
arranged perpendicularly above and below this
plane.
+See in the next slide
sp3d2-Hybridization
+The combination of one s, three p and two d-orbitals to
form six hybrid orbitals of equal energy is known as sp3d2-
hybridization.

+Examples : SF6 ( sulfer hexafluoride) molecule.

sp3d2-Hybridization of SF6
+The electronic configuration of 'S' in ground state is
1s2 2s22p6 3s23px23py13pz1.

+ In SF6 molecule, there are six bonds formed by sulfur

atom. Hence there must be 6 unpaired electrons.

+However there are only 2 unpaired electrons in the ground

state of sulfur. Hence it promotes two electrons into two
of the 3d orbitals (one from 3s and one from 3px).
sp3d2-Hybridization of SF6---6.
[Link]
+ Thus the electronic configuration of 'S' in its
2nd excited state is 1s2 2s22p6 3s13px13py13pz13d2.
In the second excited state, sulfur
under goes sp3d2 hybridization by
mixing a 3s, three 3p and two 3d
orbitals. Thus formed six half filled
sp3d2 hybrid orbitals are arranged
in octahedral symmetry. SF6 is
octahedral in shape with bond
angles equal to 90o.
sp3d2-Hybridization of SF6
Hybridization

END
How to determine types of Hybridization
+Before discussing hybridization first understand a small
concept of Steric Number(SN) which will give the idea
about different types of Hybridization.
+SN = No of sigma bonds + lone pair of electron
+How to calculate SN e.g,
+ CH4
SN of CH4

SN = 3 + 1 = 4
SN of Ammonia

(Steric Number of
Ammonia) = 3 + 1 = 4
SN to find type and shape of molecules
+SN Hybridization Geometery
+2 sp Linear
+3 sp2 Trigonal plannar
+4 sp3 Tetrahedral
+5 sp3d Trigonal bi-pyramidal
+6 sp3d2 Square bi-pyramidal
+7 sp3d3 Pentagonal bi-pyramidal
Sp3 by SN is Tetrahedral
Sp3 by SN is Tetrahedral
Conclusion of SN Number
+Now it is conclude that with the help of SN, the type of
hybridization, geometery, shape and approximate angles of
hybrid molecule can be determined.
+Examples:
Methane, amonia, water, sulfor dioxide, sulfur trioxide, XeO4,
XeO3F2, PCl4 (+), PCl6(-) etc.
Trigonal Planar