Optical Isomerism

Isomers are molecules with the same molecular formula, but have different arrangements of
their atoms.

Table of Contents

Stereoisomers are compounds which have the same structural formula but their atoms are
arranged differently in space.

Geometric (E/Z) and optical isomerism are the two different types of stereoisomerism.

The following diagram summarises the different types of isomers possible and how they are
connected.

Optical Isomerism

Optical Isomerism
Optical isomers are molecules that are non-superimposable mirror images of each other and
they are not identical.

Molecules with a chiral carbon show this kind of isomerism. Chiral carbons, also known as
asymmetric carbons, refer to a carbon atom that is bonded to four different functional groups.
 Optical Isomerism
Each carbon in this diagram has four different groups bonded to it.

They have the same structural formula and are arranged so that they are non-superimposable
mirror images of each other. This makes them optical isomers.

Here are some other examples of optical isomers you are likely to come across:

Optical Isomerism
All amino acids, except the simplest, glycine, are optical isomers.
 Optical Isomerism

Identifying Optical Isomers

Enantiomers differ in the way they affect plane polarised monochromatic light.

Plane polarised light is produced by passing light waves through a polariser. This absorbs the
light waves traveling in all directions except one. Light waves in one plane are produced.

Optical Isomerism
Plane polarised light is passed through the sample containing the optical isomer. Depending on
the direction in which the plane of polarisation of plane polarised monochromatic light rotates we
get:

​ (+) enantiomer – Rotates plane polarised light clockwise.

Drawing Optical Isomers

1. Draw the structural formula and identify the chiral carbon. The first step is to find the chiral
carbon, the carbon with four different substituents bonded to it. An asterisk is sometimes used to
identify this carbon atom.
 Optical Isomerism
2. Draw the tetrahedral enantiomer and its mirror image. Do this by using the chiral carbon as
your centre mark.

Optical Isomerism
Worked example: Identify the chiral carbon in the following structure.

Answer Carbon atom 2 on the ring has four different groups and is chiral

Geometrical isomerism:
Geometrical isomers are stereoisomers that have a different arrangement of groups or atoms

around double bonds.

Geometrical Isomerism is also known as Cis-trans isomerism. In the geometrical isomers, if the

methyl groups are present on the same side, then they are called the cis isomer, and if isomers

have groups located on opposite sides, such types of isomers are called the trans isomer. Cis

isomers of compounds are less stable than trans-isomers.

●​ Cis isomers: If the functional groups (substituents) are on the same side of the plane.

●​ Trans isomers: If functional groups are on the opposing sides.

Geometric Isomers are stereoisomers which are the pair of molecules having the same formula

but different functional groups. Geometric Isomerism occurs both in organic molecules and

inorganic coordination complexes.

Let us now define geometrical isomerism for better understanding. Geometric Isomerism is

defined as two or more molecules that contain the same type of atoms and bonds but have

different spatial arrangements of atoms. However, not all pairs of molecules have geometric

isomers.

Geometric Isomers cannot move freely due to rigid structures like carbon-carbon,

carbon-nitrogen, or nitrogen-nitrogen. Rigidity is due to a double bond. Some geometrical

isomerism examples are : stilbene, C14H12, a cyclic compound, rigid due to the ring structure.

Geometrical isomerism is generally seen in alkenes ( >C=C<) and oximes ( >C=NOH).

Necessary conditions for geometrical isomerism:

i) restricted rotation around the C – C double bond.

different. However, it doesn’t matter whether the left side groups are the same or different on the

right side.

The distinction between cis and trans isomer

1. Dipole moment of polar groups have an additive effect in cis isomers and an opposing effect

in trans isomers (tends to cancel each other). Thus, cis isomers have a higher dipole moment

than corresponding trans-isomers.

2. The structure is not symmetrical in cis-isomers and symmetrical in trans isomers; thus, a cis

configuration has a lower melting point and trans isomer (due to higher lattice energy)hence a

higher melting point.

3. Cis isomers are weakly held in the lattice, and trans – isomers are tightly held in the lattice,

thus resulting in a higher melting point of cis type than trans-isomers.

4. Cis – isomers have a lower density in comparison with trans-isomers due to higher lattice

energy.

5. Cis-isomer has a higher boiling point have comparatively low boiling point due to dipole

interaction.

E – Z nomenclature of geometric isomers:

For naming geometrical isomerism, there is a system of nomenclature of geometrical isomerism

developed by Ingold and Prelog called E-Z notation of Geometrical isomerism. According to this

system of nomenclature, priority is assigned to the groups which are attached to double-bonded

carbon atoms. If groups of similar priority lie on the similar side of a double bond, the isomer is
designated as Z ( Zusammen, means together). If groups of similar priority lie on the opposite

side of a double bond, the isomer is designated as E ( Entgegen, means the opposite).

Cis-Trans nomeclature:

Syn-Anti system of Nomenclature:

Physical properties of geometrical isomers:

●​ Cis-2-pentene while trans-2-pentene.

●​ The cis isomer is maleic acid, while the trans isomer is fumaric acid.

●​ Cis-1,2-dichloroethene while trans-1,2-dichloroethene.

●​ Cis is oleic acid, while trans is Elaidic acid.

Given here in below are a few examples of Geometrical isomers:

●​ Pt(NH3)2Cl2: species are arranged around Pt in the order Cl, Cl, NH3.

In another, it is arranged as NH3, Cl, NH3, Cl.

Geometrical isomerism in cyclic systems:

We know that geometrical isomerism can occur when there is a restricted rotation around a

bond. Apart from restrictions around a double bond, there could be other possibilities also such

that there is no possibility of rotation around any of the carbon-carbon bonds. Example

cyclohexane. Suppose we replace two of the hydrogens in the cyclohexane molecule with two

bromine atoms.
In cycloalkane, the tetrahedral shape occurs around each carbon, and bromine can be attached

in two different ways, either both above the ring or one can be above the ring and the other

below.

Cyclic alkanes also show both cis and trans geometrical isomerism. If in cyclic alkanes the

substituents attached to a ring system are on the same side of the ring, then cis isomers form,

and if on the opposite side of the ring, then form trans isomerism occurs. The letters E and Z are

not used in cyclic alkanes.