MODULE-1

ISOMERISM
TOPIC OVERVIEW: -
 ISOMERISM
 Structural Isomers
 Stereoisomers
 Geometrical isomers
 Conformations
ISOMERISM
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https://www.youtube.com/watch?v=BcxsUQyNZ64
Isomers may be defined as two or more compounds having same
molecular formula but different properties due to difference in molecular
structures. The phenomena shown by such compounds is called
Isomerism.

Structural Isomers – The isomers have different molecular structures

due to different arrangement of atoms within their molecules. This kind of
isomerism is called structural isomerism.
1. Chain Isomerism or Nuclear Isomerism – In this type of
isomerism, the isomers have different skeletons of carbon atoms.
E.g.
CH 3 CHCH 2 CH 3
CH 3 CH 2 CH 2 CH 2 CH 3 
Pentane CH 3
(n-pentane) 2-Methylbutane
(iso-pentane)
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2. Position Isomerism – In this type of isomerism the isomers have
different positions of functional group or multiple bonds. For e.g.
CH 3 CH =CHCH 3 C H 3 CH 2 C H ❑=C H 2
And
But-2-ene But-1-ene
CH 3 CH CH 2 CH 3
CH 3 CH 2 CH 2 CH 2 OH 
And OH
Butan-1-ol
Butan-2-ol
(sec-Butyl alcohol)

3. Functional Isomerism – In this type of isomerism, the isomers

have different functional groups and thus, belongs to different
families. E.g.

CH 2 =CH  CH =CH 2 CH ≡C  CH 2  CH 2
And
Buta-1, 3-diene But-1-yne
O O
 
CH 3  C CH 2 CH 3 And CH 3 CH 2 CH 2  C  H
Butan-2-one Butanal
O O
 
CH 3 CH 2  C OH And CH 3  C OCH 3
Propanoic acid Methyl ethanoate

4. Metamerism – In this type of isomerism the isomers differ in

structure due to difference in distribution of carbon atoms about the
functional group. E.g.

CH 3 O CH 2 CH 2 CH 3

CH 3 CH 2 Ο CH 2 CH 3
And 1-Methaoxypropane
Ethoxyethane
CH 3  NH CH 2 CH 2 CH 3
CH 3 CH 2  NH CH 2 CH 3 1-(N-Methyl)
N-Ethylethanamine And propanamine

5. Ring- Chain isomers: - Compounds having the same molecular

formula but possessing open chain and cyclic structures are called
ring chain isomers and the phenomenon is called ring-chain
isomerism. E.g. propene and cyclopropane are ring chain isomers.
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Stereoisomerism – Two isomers having same structural formulae but
different spatial arrangement of atoms is called stereoisomers and the
phenomena is called stereoisomerism. It is of the following types:
(i) Geometrical isomerism
(ii) Optical isomerism
(iii) Conformational isomerism
Geometrical isomerism – The stereoisomerism exhibited by alkenes
due to the difference is the spatial arrangement of groups about the
double bonded carbon atom due to restricted / hindered rotation around
C= C is called geometrical isomerism.
For But-2-ene

 The isomer with similar atoms/ groups on same side of C= C is

called cis-isomer, whereas the one with similar atoms/ groups
on opposite sides of C=C are called trans-isomers.
Conditions Geometrical isomerism
1. Presence of a double bond.
2. The two atoms groups attached to each double bonded c-atom
should be different.

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Important features of Geometrical isomers:
1. They differ in physical properties such as melting point, boiling point,
dipole moment, solubility etc.
2. Cis-isomer is more polar than Trans isomer.

Cis-But-2-ene trans-But-2-ene
( =0.33) ( =0)
Bond-dipoles don’t cancel each Bond-dipoles cancel each other
other
3. Cis-isomer has greater boiling point than trans-isomer, due to greater
polarity and hence stronger inter-particle forces.
4. Trans-isomer has higher melting point than Cis-isomer as its
molecules are more closely pack in solid state, due to symmetry.
5. Trans isomer is more stable than cis-isomer as in cis-isomer there is
stearic hindrance due to proximity of the two similar bulky groups.

Conformations in Alkanes: -
Conformation: These are the different arrangements of atoms in a
molecule which can be obtained due to free rotation about carbon-carbon
single bond.
The weak repulsive interactions between the electron pairs of the bonds
on adjacent C-atom are called Torsional strain.
Representation of conformation
(a) Sawhorse Representation of Ethane:
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 The molecule is viewed along the axis of the model from above and
right.
 The central C-C bond is drawn as a straight line, slightly tilted to
right for the sake of clarity.
 The front carbon is shown as the lower left-hand carbon and the rear
carbon is shown as the upper right-hand carbon.
 The three bonds around each C-atom (C-H is ethane or C-C higher
alkanes) are shown by three lines.

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 (i) Eclipsed (ii) Staggered

(b) Newman Projection Ethane :

Video link: - https://www.youtube.com/watch?v=tEXtJLTmdDI

 The molecule is viewed from the front along the C-C bond axis.
 The two C-atoms forming the -bonds are represented by two
circles; one behind the other so that only the front carbon is
seen.
 The front C-atom is shown by a point whereas the carbon
further from the eye is represented by the circle.
 The C-H bonds of the front C-atom are depicted from the
Centre of the circle while C-H bonds of the back carbon are
drawn from the circumference of the circle at an angle of 120 °
to each other.

(i) Eclipsed (ii) Staggered

The two conformations of ethane:

If one of the C-atoms is kept fixed and the other is rotated about the C-C
bond, infinite no. of arrangements are possible. Out of these infinite
conformations only two extreme conformations are important.
1. Staggered conformation: - The H-atoms of the two C-atoms are
staggered with respect of one another. So, they are at maximum
distance apart and have minimum repulsion between them and the
torsional strain is minimum. Hence it is more stable.
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 2. Eclipsed conformation: - The H-atoms eclipse each other i.e. the
hydrogens of one C-atom are directly behind those of the other. So,
the repulsion in these atoms are maximum (maximum torsional
strain) hence less stable than staggered form.

 When the staggered conformation is rotated through an angle

of 60°, it changes to eclipsed conformation and vice-versa.

 The infinite number of conformers between the eclipsed and

staggered form is called skew/gauge form.

 The difference in the energy contents of the staggered and

eclipsed conformation is 12.5 Kj mol -1. This small barrier to
rotation is also called torsional barrier of the single bond.
This energy difference is not large enough to prevent rotation..
Even at ordinary temperatures, the molecules have thermal or
K.E. to overcome this energy barrier. So, the two
conformations of ethane go on changing from one form to
another and consequently, it is not possible to isolate the
different conformations of ethane.

Conformations of propane:

Staggered Eclipsed

Conceptual questions: -

Q. Which among but-1-ene and but-2-ene will exhibit geometrical

isomerism and why?
Ans: But-2-ene will exhibit geometrical isomerism as the two groups
attached to the double bonded carbon atom are different.

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Q. Cis- But-2-ene has lower melting points than Trans- But-2-ene. Give
reasons.
Ans: In the cis isomer, both the bulky groups are present on the
same side, hence it has a dipole moment, thus, cis-But-2-ene has a
higher dipole moment due to which it is more polar, hence higher
boiling point.

Assignment

MCQ

Q.1. Two isomeric forms of a saturated hydrocarbon

(a) Have the same structure.
(b) Have different compositions of elements.
(c) Have the same molecular formula.
(d) Have a different content of the isotopes of hydrogen.
(e) React vigorously with one another.
Q.2. The name of the alkane isomer of cis-3-hexene is:
(a) 2-methylpentane
(b) 3-methylpentane
(c) n-hexane
(d) 2, 3-dimethylbutane
(e) Cyclohexane

Q.3. Which of the following compounds is a functional group isomer of

C2H5OH, ethanol (ethyl alcohol)?
(a) Ethanal, CH3CHO
(b) Acetic acid, CH3COOH
(c) diethyl ether, (C2H5)2O
(d) Dimethyl ether, (CH3)2O
(e) Propanol, C3H7OH

Q.6 Which of the following does NOT exhibit geometric isomerism? (Hint:
draw them!)
(a) 4-octene
(b) 2-pentene
(c) 3-hexene
(d) 2-hexene
(e) 1-hexene

Short Answer

Q.1 Consider structures I to VII and answer the questions

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 (i) Which of the above compounds form pairs of metamers?
(ii) Identify the pairs of compounds which are functional group
isomers.
(iii) Identify the pairs of compounds that represents position
isomerism.
(iv) Identify the pairs of compounds that represents chain
isomerism.

Q.2 Compounds with same molecular formula but differing in their

structures are said to be structural isomers. What type of structural
isomerism is shown by?

Q.3 Write all possible structural isomers of the compound with molecular
formula C5H12O.
Q.4 Solve example no.13.7, 13.8, 13.9.
Q.5 Solve Exercise question no. 13.3.
Q.6 Draw the cis and Trans isomer of Hex-2-ene.
Q.7 Write two functional group isomers with molecular formula C 3H6O.
Q.8 Draw all position isomers of alcohol with molecular formula C 3H8O
Q.9 Which of the following exhibit zero dipole moment?
(a) Cis – Hex-3-ene (b) trans-Hex-3-ene

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