Isomers and Isomerism

In organic chemistry, we come across

some compounds which have similar
number of atoms but differ in physical
and chemical properties and are
called isomers and the phenomenon
is called isomerism
Isomers have same molecular formula
but differ in arrangement of atoms
within a molecule

Types of isomerism

Mainly isomerism is of two types

1. Structural isomerism
2. Stereoisomerism

1-Structural isomers
Are compounds having same molecular
formula but different structural formula

These are of further 5 types

Chain isomerism
Position isomerism
Functional isomerism
Metamerism
Tautomersim

 Stereoisomers
Are compounds having same
structural formula but different in
arrangement of atoms in space
Stereoisomers are of two types
Geometrical or Cis-Trans isomerism
Optical isomerism

Structural isomerism
Chain Isomerism
Such compounds have the same
molecular formula but differ in the order
in which the carbon atoms are bonded
to each other
Examples are
n-butane and isobutane

2-methylbutane and 2, 2-dimethylpropane

Positional isomers
Positional isomers have same
molecular formula but differ in the
position of a functional group on
the carbon chain. For example

1-bromobutane and 2bromobutane

Functional isomerism
Functional isomers have same
molecular formula but differ in
functional groups. For example
Ethyl alcohol and Dimethyl ether

Metamerism
This type of isomerism is due to
unequal distribution of carbon atoms
on either side of the functional group
Such compounds are members of
homologous series
Example: Diethyl ether and Methyl
propyl ether

Tautomerism
This is a special type of functional
isomerism in which isomers are in
dynamic equilibrium with each other
For example: ethyl acetoacetate is an
equilibrium mixture of 2 forms-93%
keto form and 6% enol form

Geometric isomerism
In alkenes two carbons are linked
through sigma bond (SP2 hybridized
orbitals) and a pi bond due to overlap
of p orbitals
In such compounds these two carbons
along with other 4 substituent remain
in plane and are locked
Because rotation will break the double
bond

 This restriction of rotation is responsible for

geometric isomerism in alkenes

 Consider the case of 2 butene. It exists in two special

arrangements
Cis 2 butene and Trans 2 butene

Such compounds are referred as geometrical isomers

 Cis isomer is one in which two similar

groups are on the same side of a double
bond
Trans isomer is that in which two similar
groups are on the opposite side of the
double bond
Conversion of such isomers into each other
is only possible if heated at high
temperature or absorb light. Energy around
62 Kcal/mole is needed to break pi bond

 Trans isomers are more stable than the

corresponding cis isomer
This is because in trans bulky groups are on
the opposite side, hence less repulsion or
steric hindrance
Geometrical isomers have different
physical and chemical properties. These
can be separated by conventional
techniques like distillation and gas
chromatography etc.

Geometrical isomerism in
cyclic compounds
Geometrical isomerism is possible in cyclic
compounds
There should be restriction of rotation if
two carbons are linked with a cyclic
structure