Organic Chemistry

Lecture
Lesson 1 - Covalent bond – sigma and pi
bonds, and hybridization

Week 1 – Oct. 26 – 28; 10:00 AM – 12:00 NN

Learning Goals
• At the end of the lesson, YOU should be able to:
1. Explain hybridization and the characteristics of the different hybrid
orbitals;
2. Correlate the two theories of covalent bonding with the formation
of different orbitals; and
3. Analyze the characteristics of covalent bonds in organic
compounds.
What is Covalent bonding?
• It forms by the sharing (overlapping) of atomic orbitals to form
molecular orbital.
• Types of covalent bonds – sigma (σ) and pi (π)
Remember…
• S orbitals are spherical shaped
Remember…
• p orbitals are dumbbell shaped
Sigma (σ) bonds
• It forms by a head on
overlap of atomic
orbitals which results in
electron density
concentrated between
the nuclei of the bonding
atoms.
Sigma (σ) bonds
• It forms by a head on
overlap of s orbital with
H (1s orbital F (2p orbital HF (overlap
p orbital of hydrogen) of fluorine) creates H—F
• It forms by a head on sigma bond

overlap of two p orbitals.

F (2p orbital F (2p orbital F2 (overlap

of fluorine) of fluorine) creates F--F
sigma bond
Pi (π) bonds
• It is formed by sideways
overlap of atomic orbitals
which results in electron
density above and below
the plane of the nuclei of
the bonding electrons.
Pi (π) bonds
• Unhybridised p orbital
sigma (σ) and pi (π) bonds
Type of bond Sigma (σ) Pi (π)
single 1 0
double 1 1
Triple 1 2

Ethane
Let’s Try This!
Directions: Distinguish the number of σ and π bonds in the given
molecules.
What is hybridization?
• It is the mixing of atomic
orbitals to produce hybrid
orbitals.
• The atomic orbitals of the
same energy level and both full
filled and half-filled orbitals
provided they have equal
energy.
• It forms a new orbitals with
different energies and shapes
than the original orbitals.
sp3 hybridization
• One s orbital mixes with
three p orbitals forming
four equivalent sp3
hybrid orbitals.
• 25% s and 75% p
characters
• Tetrahedral (109.5°)
• CH4, ethane
sp2 hybridization
• One s orbital mixes
with 2 p orbitals
forming three
equivalent sp2 hybrid
orbitals.
• 33.3% s and 66.7% p
characters.
• Trigonal planar (120°)
• BCl3, carbon-carbon
double bond
sp hybridization
• One s orbital mixes
with one p orbital,
forming 2 equivalent
sp hybrid orbitals.
• 50% s and 50% p
characters
• Linear (180°)
• BeCl2, all carbon-
containing triple
bond
Hybridization
Let’s Try This!
Directions: Distinguish the σ and π bonds in the given molecules.
Covalent Bond Characteristics
Bond Polarity
- It is associated
with the atom’s
different
electronegativities
(ability of an atom
to attract electrons
from another
atom).
Covalent Bond Characteristics
Bond Polarity
Nonpolar Covalent bond
- It occurs when electrons are equally shared
between bonded atoms.
- ΔE = 0.5 or less
Covalent Bond Characteristics
Bond Polarity
Polar Covalent bond
- It occurs when electrons are unequally
shared between bonded atoms.
- ΔE = 2.1 to 0.5
Let’s Try this!
Directions: Determine the bond polarity of the given molecules.
1. O-H 3. N-H

2. C-O 4. C-Cl
Covalent Bond Characteristics
Bond Length
- It is the equilibrium distance between the centers of the nuclei of
the two bonded atoms.
Covalent Bond Characteristics
Factors affecting Bond Length
• Size of the atoms: The bond length increases with an increase in the
size of the atom. (HI > HBr > HCl > HF)

Atomic size of
hydrogen
Covalent Bond Characteristics
Factors affecting Bond Length
• The multiplicity of Bond: The bond length decreases with an
increase in bond order.( C-C > C=C > CΞC )
Covalent Bond Characteristics
Factors affecting Bond
Length
• Type of hybridization: A‘s’
orbital is smaller in size,
greater the ‘s’ character,
shorter is the bond length.
(sp3 > sp2 > sp )
Covalent Bond Characteristics
Factors affecting Bond Length
• Bond Polarity: Less polar bond has longer bond length; more
polar bond has a shorter bond length ( C-C > C-N > C-O > C-F)
• Bond length is inversely proportional to the bond polarity
Covalent Bond Characteristics
Bond enthalpy (Bond
energy)
• It is the amount of
energy required to break
one mole of bonds of a
type so as to separate
the molecule into
individual gaseous
atoms.
• It is expressed in kJ/mol
(kJ mol-1)
Covalent Bond Characteristics
Bond enthalpy (Bond
energy)
• Greater is the bond dissociation
enthalpy, the greater is the bond
strength. For diatomic
molecules like H2, Cl2, O2, N2, HCl,
HBr, HI the bond enthalpies are
equal to their dissociation enthalpy.
• Bond energy is directly proportional
to the bond polarity where the more
polar bond has strong bond energy
and less polar bond has weak bond
energy. (C-Cl > C-O > C-N > C-C)
Covalent Bond Characteristics
Bond Angle
• A bond is formed by the overlap of atomic orbitals. The direction of overlap
gives the direction of the bond. The angle between the lines representing
the direction of the bond i.e. the orbitals containing the bonding electrons
is called the bond angle.

Bond Order
• In Lewis representation, the number of bonds present between two atoms
is called the bond order. The greater the bond order, the greater is the
stability of the bond during chemical bonding, and also greater is the bond
enthalpy. The greater the bond order, the shorter is the bond length.
Covalent Bond Characteristics
Resonance in
Chemical Bonding
(pi-electron
delocalization)
Structures (A) and (B) are called resonating
or canonical structures and (C) is the
resonance hybrid. This phenomenon is
called resonance, a situation in which more
than one canonical structure can be written
for a species. The chemical activity of an
atom is determined by the number of
electrons in its valence shell. With the help
of the concept of chemical bonding, one
can define the structure of a compound
and is used in many industries for
manufacturing products in which the true
structure cannot be written at all.