BENZENE & ITS

HOMOLOGUES
By Syeda Kiran Ijaz

Benzene & its Homologues

• Constitute the most important class of aromatics.

• Discovered by Michael Faraday.

• Hofmann isolated benzene from coal tar.

 • Molecular weight: 78 a.m.u

• Molecular formula: C6H6

• Special features:

1. Resonance
2. Substitution reactions

from the Greek

phainein, meaning to
shine.

• Molecular structure:
Aromaticity
lost
 Hydrogenation
of banzene

Nomenclature of benzene
iupac system • Rule 2: Special names

• Rule 1: the homologues of benzene having single alkyl group

are named as alkyl benzene. Initially were common names.

Ethyl benzene methyl

benzene
 • Rule 3: benzene with two substituent • Rule 4 : Priority order of different functional groups:

-COOH, -C-N , -CHO , -CRO , -OH , -NH2 , -OR , -R

• Rule 5 : multiple substituents • Rule 6: Alphabetical order

 Structure of benzene
• Planar
• Old Concept: KEKULE’S STRUCTURE FOR BENZENE
• Cyclic structure
• After the discovery of benzene, its structure remained a serious
problem for chemists for about forty year . • Hexagonal , sp2 hybridized, forming trigonal planar geometry
• Presence of alternate single & double bonds i-e conjugated
system
• Kekule was the first chemist to solve this problem in 1865.
• All C-C bond length : 1.39 Å

• According to kekule;

3. Addition of three hydrogen molecules to benzene, proved the

presence of double bonds.
Kekule’s Arguments
1. Addition of mono substituent to banzene gives one product. H
H
H H
Banzene cyclohexane H H
H
Banzene

4. Addition of three molecules of chlorine to benzene, proved the

presence of double bonds.
2. Addition of di substituents to benzene gives three products.
Drawbacks of kekule’s structure: 2. According to kekule , benzene is of regular structure i-e all C-C
bond lengths are same . But due to presence of alternate double
and single bonds , structure shall not remain regular i-eC C
Kekule structure fails to explain :
bond length is shorter than C-C.
• Kekule failed to explain Why all C-C bond length are equal.
1. Banzene practically undergoes substitution reaction readily
and are reluctant to addition reaction. But according to kekule,
s structure of benzene , it has three double bonds and C-C bond length = 1.39Å
molecules with double bonds undergo addition reactions. C-H bond length = 1.09 Å
C-C & C-H bond angle = 120

X-rays Studies Of Benzene

3. Less heat of formation (while it has three double bonds and
Structure
each double bond releases 120KJ/mol ,for 3 double bonds it • X-rays studies confirmed the hexagonal structure of benzene.
would be 360 KJ/mol, but it gives 208 KJ/mol practically).

• C-C bond lengths are 1.397 Å 09

Å
1.
4. Kekule failed to explain why benzene is Less reactive. • C-H bond lengths are 1.09 Å
• All the angles are 120°
Alkane= 1.54
Alkene= 1.34
Alkyne= 1.2
Banzene= 1.397
Modern Concept
Sigma and Pi framework of banzene
Molecular Orbital Theory
In one molecule of
benzene there are 6
carbon -carbon (sp2-
sp2) sigma bonds, 6
carbon - hydrogen(
sp2 - s )sigma bonds,
resulting a total of
12 sigma bonds and
3 carbon - carbon (p-
p) π- bonds.

As a result of
6 delocalization ,
6 strong pi bond is
formed giving
more stable
molecule. Due
to higher
stability pi
bonds of
molecule resist
breaking. That is
why benzene
lack reactivity
towards
addition rxns.
 Resonance , Resonance Energy &
Stability of Benzene
• Resonance: The phenomena in which two or more structures
can be written for a substance which involve identical position
of atoms is called as resonance.
• Resonance hybrid: The actual structure of the molecule .
• Resonance structures: Various possible alternative structures.
• Resonance structures are not actual structures, they only are
theoretical / hypothetical.
• Resonance hybrid is more stable.
• Resonance structures is directly proportional to stability.

Resonance Energy Of Benzene

Definition: Decrease in energy due to resonance is called as
resonance energy.
• When the structures are interconverted there is decrease in
energy.
OR;
Difference in heat of hydrogenation calculated & observed is
resonance energy.
Formula:
Resonance energy = △H(cal)−△H(obs)
• Resonance energy is directly proportional to stability.
• Resonance energy of benzene is 152KJ/mol.
 Evidence For Benzene Stability: Graphical Representation
• 3 Experiments Benzene stability is due to
delocalization of pi electrons,
magnitude of this stability
can be estimated by
measuring the changes in
heat of hydrogenation
associated with reactions.

theoratical

2. Decarboxylation of aromatic acid:

Preparation Of Benzene In this reaction sodium salt of carboxylic acid (sodium benzoate)
is heated with soda lime to produce benzene and sodium
A. Small scale preparation of Benzene carbonate.

1. From phenol
Phenol is reduced to benzene by passing its vapours over heated
zinc dust.
There is removal of oxygen atom.

Sodium benozate Benzene Sodium carbonate

Phenol benzene
C6H6O C6H6
3. From acetylene: 4. From benzene sulphonic acid:
Acetylene (ethyne) on passing through red hot iron tube at 500C Benzene can be prepared from sulphonic acid through their
undergoes cyclic polymerization. Three molecules of acetylene hydrolysis.
polymerizes to give benzene.
Benzene sulphonic acid is treated with super heated steam in the
presence of acid giving benzene.

3 molecules of benzen
acetylene e