Optical Isomerism

By

Dr. Irshad Ali

(University Professor)
Department of Chemistry
Bihar National College
Patna University, Patna
 OPTICAL ISOMERISM
➢ Plane Polarized Light – Ordinary light ray vibrate in all possible directions
perpendicular to the direction of propagation. When ordinary light is passed
through a nicol prism the vibration of ray are adjected in a single phase only. The
light whose vibration occurs only in one plane is called plane polarized light. The
apparatus which bring polarization in the light is called polarimeter.

Ordinary light Nicol Prism Plane polarized light

➢ Optical Activity – Some substances have the property to rotate plane polarized
light to the left or to the right. These substances are termed as optically active
substance and this property is called Optical activity. The apparatus which
measure the extent of the plane polarized light is called polarimeter.
The substance which rotate the polarized light to the
right is called dextrorotatory or d – form and the substance which rotate the
plane polarized light to the left is called laevorotatory or l – form. d – form is also
indicated by (+) sign and l – form is also indicated by (–) sign.

➢ Optical Isomerism – Compounds having same molecular formula and same

structural formula but differ in behavior of plane polarized light are called optical
isomers and this phenomenon is called optical isomerism.
eg.
COOH COOH
| |
H – C – OH OH – C – H
| |
CH3 CH3
d – lactic acid l – lactic acid
 d – lactic acid and l – lactic acid are optical isomers.
d – lactic acid rotate the plane polarized light to the right
and l – lactic acid rotate the plane polarized to the left.

➢ Asymmetric Carbon or Chiral carbon – A carbon atom which is attached to four

different atoms or groups is called asymmetric carbon atoms or chiral carbon.
COOH
|
H – C* – OH Lactic Acid
|
CH3
Asymmetric carbon atom is shown by star (*). In lactic acid, there is one
asymmetric carbon.

➢ Necessary condition for Optical Isomerism

There are two necessary conditions for optical isomerism.
i. The molecule must have an asymmetric carbon.
ii. The mirror image of the molecule must be non – superimposable.
COOH COOH
| |
H – C – OH OH – C – H
| |
CH3 CH3
Lactic acid has an asymmetric carbon atom and its mirror image is non
superimposable i.e. mirror image represents different optical isomer.
Therefore lactic acid shows the phenomenon of optical isomerism.

➢ Plane of Symmetry – A plane which cut an object into two equal halves is called
plane of symmetry.
 COOH
|
H – C – OH
|
H – C – OH
|
COOH
Tartaric Acid
Tartaric acid has plane of symmetry.
An object lacking a plane of symmetry is called dissymmetry or
chiral dissymmetry.
A dissymmetric object can’t be superimposable on its mirror
image.

➢ Racemic Mixture – An equimolar mixture of ‘d’ and ‘l’ form of the same
compound is called racemic mixture or d l mixture or ± mixture.
Racemic mixture is optically inactive. This is because
rotation caused by one enantiomer is exactly due to the rotation caused by the
another enantiomer. Hence net rotation of the mixture becomes zero. The optical
inactivity of racemic mixture is due to external compensation.

➢ Enantiomers :- Optical isomers which are mirror image of each other are called
Enantiomers.
or
Compounds having same molecular formula, mirror images of each other and are
non superimposable are called enantiomers.

➢ Chirality Centre or Steriogenic Centre – A carbon atom which is attached to four

different atoms or groups is called asymmetric carbon. This asymmetric carbon is
treated as Steriogenic centre or Chirality Centre.

➢ Enantiomer :- Two optical isomer which are non superimposable mirror image of
each other are called Enantiomers.
➢ Enantiomers are always dissymmetry hence optically active. However if one
enantiomer is dextrorotatory then the another enantiomer is laevorotatory .

➢ Mesomer – Symmetric optical isomer is called Mesomer.

eg.
COOH
|
H – C – OH
| Symmetric
H – C – OH
|
COOH
i. Mesomer is only if molecule has two or more similar C*.
ii. Mesomer is optically inactive.
iii. Mesomer has opposite superimposable mirror image.
iv. Mesomer has opposite configuration on two C*.
The compounds which show mesomerism are called
mesocompound.
The cause of optical inactivity of mesomers is internal
compensation.

➢ Diasterioisomer – Two optical isomers which are not mirror image of each other
are called Diasterioisomer.
COOH COOH
| |
H – C – OH OH – C – H
| |
H – C – OH OH – C – H
| |
COOHCH3 COOHCH3
(I) (II)
 COOH COOH
| |
H – C – OH OH – C – H
| |
OH – C – H H – C – OH
| |
COOHCH3 COOCH3
(III) (IV)

(I) and (II) are enantiomers.

(III) and (IV) are enantiomers.
(I) is disteriomer of both (III) and (IV), (II) is also disteriomer of third
and fourth.

i. Disteriomer is possible only if molecule have two or more asymmetric

carbon.
ii. Disteriomers have different physical properties eg. m.p., b.p.

iii. Disteriomers have neither same nor opposite configuration.

➢ Optical Isomerism in Lactic Acid

COOH
|
H – C – OH
|
CH3
Lactic acid contain one asymmetric carbon atom. Three forms of lactic acid are
found out of which two are optically active and remaining one is optically inactive.

➢ Racemic Mixture – An equimolar mixture of ‘d’ and ‘l’ form of a compound is

called a racemic mixture or racemet or ± mixture is optically inactive because the
two enantiomers (d and l) rotate the plane polarized light equally in opposite
 direction and cancel the rotation. This phenomenon is called external
compensation.

➢ Resolution or Resolution of racemic mixture – The process of separation of a

racemic mixture into two ‘d’ and ‘l’ form is called Resolution.
The separation of ‘d’ and ‘l’ form of a racemic
mixture is very difficult because they have identical physical and chemical
properties.
Following methods can be used for the separation of
‘d’ and ‘l’ form.

i. Mechanical Separation – If the ‘d’ and ‘l’ form of a compound exist in well
defined crystalline form the separation can be done by hand picking with
the help of magnifying lens.
eg. – d and l forms of sodium ammonium tartrate can be separated by this
method but this method has very limited applications.
ii. Biochemical Separation – In this method the resolution is done by the use of
microorganism when certain bacteria are added to a solution of a racemic
mixture, they decompose one of the optically active form rapidly than the
other. This process is very slow and only small amount of material can be
separated.
iii. Chemical Seperation – This is the best method of resolution. In this method
the racemic mixture is combine with another optically active compound and
the resulting product differ in properties particularly in solubility in various
solvent. By fractional crystallization from a suitable solvent, they can be
separated.

➢ Racemization – The process of conversion of ‘d’ and ‘l’ form of the compound
into a racemic mixture is called Racemization.
Racemization can occur either by heat, light or by
chemical reagent.
eg. – When solution of d and l tartaric acid in water is heated under pressure, it is
converted into a completely inactive mixture of Racemic tartaric acid.
➢ Optical Isomerism in Lactic Acid
Lactic acid contains only one asymmetric carbon. Three fotms of lactic acid are
found. Among them two are optically active and rest one is optically inactive.
i. d – lactic acid – It is optically active. It rotates the plane polarized light to the
right.
COOH
|
H – C – OH d – lactic acid
|
CH3
ii. l – lactic acid – It is optically active. It rotates the plane polarized light to the
left.
COOH
|
OH – C – H l – lactic acid
|
CH3

iii. dl lactic acid – It is optically inactive. It is the equimolar mixture of ‘d’ and ‘l’
form of lactic acid.

➢ Optical Isomerism in tartaric Acid

COOH
|
H – C* – OH
|
H – C* – OH
|
COOH
Tartaric acid contain two asymmetric carbon. Four forms of tartaric acid are
found. Among them two are optically active and rest two are optically inactive.
 i. d – tartaric acid – It is optically active. It rotates the plane polarized light to
the right.
ii. l – tartaric acid – It is optically active. It rotates the plane polarized light to
the left.
iii. dl tartaric acid – It is optically inactive. It is the equimolar mixture of ‘d’ and
‘l’ form of tartaric acid.
iv. Mesotartaric acid – It is optically inactive. It has a plane of symmetry. It is
optically inactive due to internal compensation.

COOH COOH
| |
H – C – OH HO – C – H
| |
OH – C – H H – C – OH
| |
COOH COOH
(I) d – tartaric acid (II) l – tartaric acid

***********************