Module 1

1.7 Define, with examples, structural isomerism

1.8 Explain stereoisomerism
1.9 Determine the possible isomers from given molecular formula

Molecules which have the same molecular formula, but differ in the arrangement of their atoms,
are called isomers.
The isomerism that exist are:

 Structural isomerism
 Geometrical isomerism
 Optical isomerism

Structural isomerism

Structural isomerism is where compounds have the same molecular formula, but the structural
formula is different. Hence structural isomers are compounds that have the same molecular
formula but different structural formula

Types of Structural Isomerism

There are:
 Chain isomerism: isomers differ in the arrangement of the carbon skeleton
 Positional isomerism: isomers differ in the position of the functional group
 Functional isomerism: isomers differ in the functional group present

Chain isomers are molecules with the same molecular formula but different arrangement of
carbon atoms. Chain isomers show isomerism by branching chains. All organic compounds
can show chain isomerism. Only organic compounds with four or more carbon atoms can
show chain isomerism

Isomers with the length of the chain with three isomers is not possible because there
rearrangement of the skeleton is not possible.
  For Example

When drawing chain isomers remember that the straight chain is also one of the isomers

For example

Organic compound with four carbon atoms has two isomers:

Organic compounds with more than four carbon can form more branched chain compounds.

For example:

Organic compounds with five carbon atoms

Give the fully displayed structure and name of the chain isomers of the following:

1. C4H8

2. C4H9OH

3. C4H9COOH

Positional Isomerism
Positional isomers are molecules with the same molecular formula but have the functional
group on different positions in the molecule.
Alkanes do not show positional isomerism because they do not have any true functional group
Alkenes show positional isomerism by a change in the position of the double bond.
Only alkenes with four or more carbons will show positional isomers.

For Example (with less than four carbons)

 C3H6

For example:(with 4 carbons and more)

Draw the fully displayed structural formula and give the name of the following:
 C4H6

Alcohols show positional isomerism by change in position of their hydroxyl (-OH) group.
Alcohols with three or more carbons in the chain can show positional isomerism.

For Example
Draw the positional isomers of C3H7OH

A Halogenoalkane is an organic compound with an alkane carbon skeleton that has one (1) or
more of its hydrogen atom(s) replaced by a halogen atom(s). Halogenoalkanes with three or
more carbons show positional isomerism.

For example: draw the positional isomers of C3H7Cl

Draw the fully displayed or condensed structure for the positional isomers of the following:
a) C5H10
b) C4H9OH
c) C4H9Br
d) C5H10Cl2

Functional Group Isomerism

Functional group isomers are molecules that have the same molecular formula but different
functional groups

For Example
Cycloalkanes and alkenes are functional group isomers. Cycloalkanes are alkanes with a ring
rather than a straight chain arrangement. Cycloalkanes also have the general formula C nH2n (just
like alkenes)
For Example
The functional group isomers of C6H12

For example: Draw the functional group isomers for: C2H6O

Distinguishing between Isomers

Isomers tend to differ in their boiling points. Molecules with no branching tend to have higher
boiling points than isomers with branching. This is because the former have a higher surface
area, so they pack together better and so the van der Waal forces are stronger.

For example: Isomers of C5H12

Isomer Structure Boiling point /oC

Pentane CH3CH2CH2CH2CH3 36

Methylbutane CH3CH2CH2CH3 28
CH3

For example
Identify the type of structural isomerism that will be shown by the following. Draw the fully
displayed or condensed structural formula of each and name them.
a) C3H8O
b) C4H8Cl2
c) C5H12
Stereoisomerism

This is where two or more compounds have the same molecular formula and the same
functional groups but differ in the arrangement of groups in space. That excludes any different
arrangements which are simply due to the molecule rotating as a whole, or rotating about
particular bonds.

Where the atoms making up the various isomers are joined up in a different order, this is known
as structural isomerism.

There are two types:

 Cis-trans (geometrical isomerism)
 Optical isomerism

Geometrical Isomerism

These are isomers with different spatial orientation around the double bond. Hence
geometrical isomerism can only be observed in alkenes that have two different groups
attached to the double bonded carbons. It is caused by the restriction of movement about the
carbon-carbon double bond

The double bond consists of two types of bond:

 Sigma bond (s bond)
 pi bond (p bond)

An atom consists of what is called atomic orbitals. The atomic orbitals are described as being
regions of space in an atom that an electron can be found. There are different atomic orbitals
each holding a different number of electrons and having a different shape.
S-orbitals: holds two electrons and circular in shape

P- orbitals: 3 p orbitals each holding electron and each has a dumb bell shape. In the formation of
the double bond, first there is the overlap of s orbitals or p orbitals in between the nuclei of the
two atoms
Secondly p-orbitals overlap above and below the plane of the nuclei (internuclear axis). Since
these orbitals overlap in different places, it is not possible to rotate a pi- bond about its axis
without breaking the bond,hence the restricted rotation about the double bond.

For geometrical isomerism to be possible, there should be two different groups on both sides of
the double bonded carbons

For example:

Geometrical isomers can be described as

 Cis: where the the similar groups are on the same side of the molecule
 Trans: when the similar groups are on different sides of the molecule

For example: but-2-ene

The cis and trans isomers are distinct compounds and are not easily interconvertible (by
breaking the double bond). Cis and trans isomers normally have similar chemical properties but
often their physical properties are different

Questions
 Do you expect 1,2 dibromoethene to show geometrical isomerism.
 If possible show and name its possible isomers

 Would

show geometric isomerism? Give reasons for your answer. Draw the fully displayed structural
formula for the isomers and name them.
Optical Isomerism
Light consist of vibrating electric and magnetic fields (electromagnetic radiation). A ray of light
travel in waves

The ray of light vibrate in many directions at right angles to the direction of the travelling ray.

Certain materials have the ability to remove from normal light all waves except those vibrating
in a single plane. When this happens the light is said to be plane polarized. A well known
polariser is polaroid, which is used in the lenses of some sun glasses.

Certain substances have the ability to rotate the plane of polarized light. If a polarized light is
shone through a certain solution, the plane in which the polarized light vibrates will be rotated
clockwise or anticlockwise. These substances are said to be optically active
Hence optical isomerism can be described as when a substance can rotate the plane polarized
light in a clockwise or anticlockwise direction. Hence optical isomers rotate the plane of
polarized light in clockwise or anticlockwise direction to the same degree.

Optical Isomers

Optical isomers do not differ in the type of group they contain, but in the arrangement of the
groups in space

For example:

Optical isomers are non-identical mirror images of one another. This is because they are
asymmetric molecules
 Symmetry describes the ability of molecules made up of similar groups or atoms to
face each other around an axis
 Asymmetric describes molecules that fail to correspond to one another in shape, size
or arrangement around an axis.
Hence they are not superimposable. For example the right hand and the left hand cannot be
placed over each other and the fingers match. Because of asymmetry of optical isomers they are
described as chiral molecules.

The atom at the center of the different groups is described as being the chiral center or the
asymmetric carbon atom
The asymmetric carbon atom is indicated by *

The optical isomers are also called enantiomers. Optical isomerism is when molecules which
are non-identical mirror images are able to rotate polarized light in anticlockwise or clockwise
direction (plane). Optical isomers are molecules which are non-identical mirror images that
rotate polarized light in an anticlockwise or clockwise direction.
Optical isomers:
 Are asymmetric molecules which means they are not superimposable
 Because of their asymmetry are described as chiral molecules
 Most times have a carbon at the center and surrounded by four different groups
 Are also called enantiomers