Engineering Chemistry 1 – Sem 1

Prof. Sunil Nagare

M.Tech (VJTI) & B.Tech (SPIT)
 Chapter 2 : Aromatic System
Question Bank
1. Explain Aromatic Compounds with characteristics
2. Explain Kekule structure of benzene (resonance)
3. Explain Huckel’s rule
4. Structure & Bonding : Pyrrole
5. Why does Anthracene qualify as an aromatic molecule but Cyclobutadiene
does not?
6. Why Benzene is Aromatic Molecule ?
7. Why Cyclopentadiene is Aromatic Molecule ?
 Aromatic Compound
• Aromatic compounds are chemical compounds that consist of conjugated
planar ring systems accompanied by delocalized pi-electron clouds in place
of individual alternating double and single bonds.
Characteristics :
• A delocalized conjugated pi system, an arrangement of alternating single
and double bonds
• Coplanar structure, with all the atoms in the same plane
• Contributing atoms should be arranged in one or more rings
• A number of π delocalized electrons that is even, but not a multiple of 4.
• 4n + 2 π electrons, where n = 0, 1, 2, 3, 4, 5, and so on. This is Huckel’s rule.
 Huckel’s Rule
Huckel rule:
• The cyclic π molecular orbital
formed by overlap of p orbitals
must contain (4n + 2) p electrons,
where n = integer 0, 1,2,3, … etc.
Explanation:
• According to Huckel rule, a cyclic
and planar compound is aromatic if
it the number of π electrons is
equal to (4n + 2), where n = integer
0, 1, 2, 3,… etc
Huckel’s Rule
 Kekule Structure of Benzene
• August Kekule in 1865 suggested the structure for benzene having a cyclic
planar ring of six carbon atoms with alternate single and double bonds and
hydrogen atom attached to each carbon atom.
 Kekule Structure of Benzene
• The Kekule structure indicates the possibility of two isomeric 1,2-
dibromobenzenes.
• In one of the isomers, the bromine atoms would be attached to the doubly
bonded carbon atoms whereas in the other, they would be attached to
single bonded carbons.
 Kekule Structure of Benzene
Resonance Condition :
• The phenomenon in which two or more structures can be written for a
substance which involves the identical position of atoms is referred to as
resonance.
• The actual structure of the molecule is referred to as resonance hybrid.
• The alternative structures are known as resonating structures.
• To represent the resonance a double headed arrow ( )will be used.
• In case of benzene, the Kekule's structure I and II represent the resonating
structures.
 Kekule Structure of Benzene
Limitations
• According to the prediction made by the Kekule structure, there should be
two different 1,2-bromobenzene, which represent the two different bonds
present in the benzene structure.
• But in actual practice, only one 1,2-bromobenzene has ever been found,
denoting the fact that all the bonds in benzene are equivalent and for
resonance with each other.
• According to Kekule's structure benzene contains three double bonds and
hence the chemical properties of benzene should resemble those of alkene,
but in actuality, it is not so as Benzene is highly stable and forms
substitution compounds easily.
 Structure & Bonding : Pyrrole
• Pyrrole is a heterocyclic aromatic organic compound,
• a five-membered ring with the formula ( C4H4NH ).
• It is a colourless volatile liquid that darkens readily upon exposure to air.
• Substituted derivatives are also called pyrroles.
• Pyrrole has a relatively high boiling point as compared to furan and
thiophene, this is due to the presence of intermolecular hydrogen bonding
in pyrrole
 Structure & Bonding : Pyrrole
• The lone pair on nitrogen is in the
p orbital so it is involved in the 6
pi-electron aromatic system,.
• Hence pyrrole is not very
nucleophilic and is only weakly
basic at nitrogen.
• Because of the lobes are much
bigger at the 2- and 5- positions,
this indicates that the reactions of
pyrrole are most likely to take
place at these positions
 Why does Anthracene qualify as an aromatic
molecule but Cyclobutadiene does not?
Anthracene:
• Anthracene is a tricyclic aromatic hydrocarbon.
• It has a planar structure with six π electrons in each benzene ring and a
total of 14 π electrons (4n + 2 for n = 3).
• Therefore, anthracene satisfies all the conditions for aromaticity and is
considered an aromatic molecule
 Why does Anthracene qualify as an aromatic
molecule but Cyclobutadiene does not?
• Cyclobutadiene has a square planar structure with four
carbon atoms.
• While it is cyclic and has all carbon atoms in the ring
possessing p orbitals, it has only four π electrons.
• According to Huckel's rule, the number of π electrons in an
aromatic system should be 4n + 2. For n = 1, this would be 6.
• Since cyclobutadiene does not fulfill the 4n + 2 rule, it is not
considered aromatic. Moreover, it is highly reactive and
tends to dimerize to form a stable, non-aromatic species.
• In summary, anthracene qualifies as an aromatic molecule
because it meets all the criteria outlined by Huckel's rule,
whereas cyclobutadiene fails to satisfy the rule and is not
considered aromatic.
 Why Benzene is Aromatic Molecule ?
• Benzene is considered an aromatic molecule due to its unique stability
and bonding pattern.
• The key features that make benzene aromatic are:
• Planar Structure: Benzene has a planar, hexagonal structure with all
carbon atoms in the same plane. Each carbon atom is bonded to two
other carbon atoms and one hydrogen atom.
• Equal Carbon-Carbon Bond Lengths: In benzene, all carbon-carbon
bond lengths are identical. This is in contrast to what would be expected
in a structure with alternating single and double bonds, where the
double bonds would be shorter than the single bonds.
 Why Benzene is Aromatic Molecule ?
• Resonance Structure: The concept of resonance is crucial in
explaining the stability of benzene. Benzene can be represented by
multiple resonance structures where double bonds are delocalized or
spread out across the entire ring
• Delocalized Pi Electrons: Benzene has six pi electrons, corresponding
to three double bonds. However, these electrons are not localized
between specific pairs of carbon atoms. Instead, they are delocalized
over the entire ring, providing extra stability to the molecule.
• Stability and Aromaticity: The delocalization of pi electrons results
in a particularly stable molecular system. According to Huckel's Rule, a
molecule is considered aromatic if it has 4n + 2 pi electrons, where n is a
non-negative integer. For benzene, n is equal to 1, and 4n + 2 equals 6 (2
pi electrons for each double bond), confirming its aromaticity.
 Why Cyclopentadiene is Aromatic Molecule ?
• Cyclopentadiene is not considered
aromatic in its basic form. The
molecule has an alternating single
and double bond pattern, which
might suggest aromaticity, but it
lacks the necessary characteristics
for aromaticity. Specifically:
Planarity:
• Cyclopentadiene is not completely
planar. The p-orbitals of the double
bonds are not aligned, preventing
the delocalization of pi electrons
required for aromaticity.
 Why Cyclopentadiene is Aromatic Molecule ?
Equal Bond Lengths:
• The carbon-carbon double bonds in
cyclopentadiene have different bond
lengths, which is unlike the equal bond
lengths found in aromatic compounds
like benzene.
Huckel's Rule:
• According to Huckel's Rule, for a
compound to be aromatic, it should
have 4n + 2 pi electrons.
Cyclopentadiene has six pi electrons
(two for each double bond), which
doesn't satisfy Huckel's Rule.