Chemistry : Isomerism ALLEN®

Pre-Medical

Chapter No. 02
ISOMERISM

S.No. Contents Page

01. Structural Isomerism 33
02. Chain Isomerism 33
03. Position Isomerism EN 33
04. Ring-chain Isomerism 35
05. Functional Isomerism 36

06. Metamerism 36
07. Geometrical Isomerism 38
LL
08. Conformational Isomerism 41
09. Exercise-I (Conceptual Questions) 44
10. Exercise-II (Previous Years Questions) 46
11. Exercise-III (Analytical Questions) 47
A

NEET SYLLABUS
Isomerism (Conformational, Geometircal Isomerism)

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OBJECTIVES
After studying this unit, we will be able to :
 recognise and write structures of isomers of alkanes, alkenes, alkynes and aromatic


hydrocarbons ;
EN
understand the concept of molecular and structural formula;
 draw and differentiate between various conformations of ethane;
 understand the concept of restricted rotation;
LL

"Dream is not that which you see while sleeping it is something that;
does not let you sleep."

A.P.J. Abdul Kalam, Wings of Fire : An Autobiography

A

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ISOMERISM
Two or more than two compounds having the same molecular formula but different physical/chemical or
both properties are called isomers and the phenomenon is called isomerism.
ISOMERISM

Structural Isomerism/Constitutional isomerism Stereoisomerism

Chain Position Ring Chain Functional Metamerism Tautomerism

Configurational Conformational

Geometrical Optical

2.1 Structural Isomerism

2.1.1 Chain Isomerism (C.I.)

The compounds which have same molecular formula, same functional group but different arrangement of
carbon chain show chain isomerism.

Ex. CH3–CH2–CH2–CH3 EN CH3–CH–CH3

CH3

Butane (4C) 2–Methyl propane (3C)

Ex. CH3–CH2–CH2–CH2–OH CH3–CH–CH2–OH

CH2
LL

1–Butanol (4C) 2–Methyl–1–propanol (3C)

Ex.
A

Methylcyclobutane Cyclopentane

2.1.2 Position Isomerism (P.I.)

The compounds which have same molecular formula, same functional group, same parent carbon chain but
different position of functional group or multiple bond or substituents, show position isomerism.

Ex. CH2=CH–CH2–CH3 CH3–CH=CH–CH3

But–1–ene But–2–ene

Ex. CH3–CH2–CH2–CH2–OH CH3–CH2–CH–CH3

OH

1–Butanol 2–Butanol
Cl

Ex. Br
Cl
Br

1-Bromo-2-chlorocyclopropane 1-Bromo-1-chlorocyclopropane

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Example of CI and PI :
(i) C5H12 has three structural isomers :
CH3

CH3–CH2–CH2–CH2–CH3 CH3–CH2–CH–CH3 CH3–C–CH3

CH3 CH3

Pentane 2–Methyl butane 2,2–Dimethylpropane

(ii) C6H14 has 5 structural isomers
(a) CH3CH2CH2CH2CH2CH3 (b) CH3–CH2–CH2–CH–CH3
CH3
Hexane 2–Methyl pentane

(c) CH3–CH2–CH–CH2–CH3 (d) CH3–CH–CH–CH3

CH3 CH3 CH3
3–Methyl pentane 2,3–Dimethyl butane

CH3 EN
(e) H3C–C–CH
 2–CH
3     (a–b), (a–c), (a–d), (a–e)  Chain Isomers
CH3 (b–d), (b–e), (c–d), (c–e)
2,2–Dimethyl butane     b–c, d–e Position Isomers

(iii) C3H6Cl2 has 4 isomers : Position of chlorine atom is different in all the structure, so these are
LL
position Isomers.
Cl Cl
a. H3C–CH2–CH–Cl b. H2C–CH2–CH2–Cl 
1,1-Dichloropropane 1,3-Dichloropropane

Cl Cl
A

 c. H3C–C–CH3 d. H2C–CH–CH3
Cl Cl
2,2-Dichloropropane 1,2-Dichloropropane
Ex. How many structural isomers of C7H16 are possible ?
Ans. (9)
1. CH3–CH2–CH2–CH2–CH2–CH2–CH3 Heptane

2. CH3–CH2–CH2–CH2–CH–CH3 2–Methylhexane
CH3
3. CH3–CH2–CH2–CH–CH2–CH3 3–Methylhexane
CH3

CH3
4. CH3–CH2–CH2–C–CH3 2,2–Dimethyl pentane
CH3

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CH3
5. CH3–CH2–C–CH2–CH3 3,3–Dimethylpentane
CH3
CH3
6. CH3–CH–CH–CH2–CH3 2,3–Dimethylpentane
CH3
CH3 CH3
7. CH3–CH–CH2–CH–CH3 2,4–Dimethylpentane

CH2–CH3
8. CH3–CH2–CH–CH2–CH3 3–Ethylpentane

CH3
9.
CH3–CH–C–CH3 2,2,3–Trimethylbutane
(Triptane)
CH3 CH3

2.1.3 Ring chain isomerism (RCI)

EN
Same molecular formula but different mode of linking (open chain & closed chain) of carbon atoms.

CH3–CH=CH2 [open chain]

C3H6
CH2
LL
[closed chain or ring]
CH2 CH2

BEGINNER'S BOX-1
1. Structures CH3–CH2–CH=CH2 and CH3–C=CH2 are :–
A

CH3

(1) Chain isomers (2) Position isomers

(3) Both chain & position isomers (4) Not isomers

2. How many minimum carbons required for Chain isomerism and Position isomerism in alkanes ?

(1) 4, 5 (2) 3, 5 (3) 4, 6 (4) 4, 4

3. How many minimum carbons required for Chain isomerism and Position isomerism in alkenes ?

(1) 4, 5 (2) 3, 4 (3) 4, 4 (4) 5, 5

4. How many minimum carbons required for Chain isomerism and Position isomerism in alkynes ?

(1) 5, 4 (2) 5, 3 (3) 4, 6 (4) 4, 4

GOLDEN KEY POINTS

 Alkenes with cycloalkane and alkynes and alkadienes with cycloalkenes show Ring-chain Isomerism.
 Ring-chain Isomers are also Functional Isomers but priority must be given to Ring-chain Isomers.

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2.1.4 Functional Isomerism
Same molecular formula but different functional groups.
Following compounds show Functional isomerism, as they have same molecular formula and different
functional group.
(i) Alcohol and Ether   CH3—CH2—OH and CH3—O—CH3
(ii) Aldehydes and Ketones  CH3–CH2–C–H and CH3–C–CH3
O O
(iii) Acids and Ester    CH3–C–OH and H–C–O–CH3
O O
(iv) Cyanide and Isocyanide   CH3—CH2—CH2—CN and CH3—CH2—CH2—NC
O
(v) Nitro and Nitrite    CH3–CH2–N and CH3—CH2—O—NO
O

(vi) 1°, 2°, 3° Amines

CH3
(i) CH3—CH2—CH2—NH2 (ii) CH3—NH—CH2—CH3
EN (iii) CH3–N–CH3

(vii) Alcoholic and Phenolic compounds :

OH
CH2OH CH3
and

(viii) Alkyl halides do not show Functional isomerism.

LL

BEGINNER'S BOX-2
1. Which of the following isomerism is not related to structural isomerism :-
(1) Position (2) Functional (3) Geometrical (4) Chain
A

O
2. and CHO exhibit the isomerism :-
(1) Functional (2) Chain (3) Position (4) Tautomerism

3. Which molecular formula does not exhibit position isomerism :-

(1) C5H12 (2) C4H8 (3) C6H14 (4) C5H10

2.1.5 Metamerism
Same molecular formula, same polyvalent Functional group but different alkyl groups attached to polyvalent
Functional group.
Polyvalent Functional group [Which have more than one valency] are :
O
–C
–O–, –S–, –C–, –C–O–, –C–NH–, –NH–, –N–, O, –C–N–
–C
O O O O
O
Ex. CH3—O—CH2—CH2—CH3 ; H3C–CH2–O–CH2–CH3
Ex. CH3—CH2—NH—CH2—CH3 CH3—NH—CH2—CH2—CH3

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Ex. CH3—NH—CH2—CH2—CH2—CH3 H3C–CH2–NH–CH2–CH2–CH3

Ex. CH3–C–CH2–CH2–CH2–CH3 CH3–CH2–C–CH2–CH2–CH3

O O

Examples Based on Structural Isomerism :-

Ex.1 C4H10O Structural isomers 7 [4 alcohol and 3 ethers] total 7 structural isomers are possible.
Alcohol : CH3—CH2—CH2—CH2—OH CH3–CH2–CH–CH3

OH

CH3
CH3–CH–CH2–OH and CH3–C–OH
CH3 CH3

Ethers : CH3—O—CH2—CH2—CH3, C2H5—O—C2H5, CH3–O–CH–CH3

OH

Ex. 2 Aromatic isomers of C7H8O.

CH3
CH3 O–CH3

(a)
CH2–OH

(b)
CH3
OH
EN (c)
OH
(d) (e)
OH

 a, b – Functional isomers  b, c – Position isomers

 c, d – Position isomers  a, d – Functional isomers
LL

 a, e – Functional isomers  a, c – Functional isomers

Note : Alcoholic and phenolic groups are Functional isomers.

BEGINNER'S BOX-3
1. CH3–CH=CH–CH3 and CH2–CH2 are :–
A

CH2–CH2
(1) Ring-chain Isomers (2) Chain Isomers
(3) Functional Isomers (4) Position Isomers
O O
2. CH3–CH2–CH2–C–OH and CH3–CH2–CH–C–H are
OH
(1) Position isomers (2) Functional isomers
(3) Identical (4) Chain isomers
3. CH3—S—CH2—CH3 and CH3—CH2—S—CH3 are –
(1) Ring-chain Isomers (2) Chain Isomers
(3) Functional Isomers (4) Identical
O O O O
4. CH3–C–O–C–C6H5 and C6H5–C–O–C–CH3 are –

(1) Metamers (2) Chain Isomers (3) Identical (4) Position Isomers

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2.2 Stereo Isomerism
Two or more than two compounds having same molecular formula, same structural formula but different
arrangements of atoms or groups in space.
(A) Configurational Isomerism : Stereo isomers which have following characteristics.
(a) Stereo isomer which cannot interconvert at room temperature due to restricted rotation known as
Geometrical isomerism.
(b) Stereo isomers which have different behaviour towards plane polarised light are known as optical
isomers.
(B) Conformational Isomerism
2.2.1 Geometrical isomerism (G. I) :
(i) Alkenes ( >C=C<), oximes (>C=N—) and azo compounds [—N=N—] etc., show G. I. due to restricted
rotation about double bond and (ii) cycloalkanes show G. I. due to restricted rotation about single bond in
ring.
G. I. IN ALKENES :
Reason : Restricted rotation about double bond :
Condition for Geometrical isomerism :

b
C=C
a
b
EN
Only those alkenes show G. I. in which "Each sp2 carbon individually have different atoms or groups"
a a
b
C=C
x
y
Geometrical isomerism Geometrical isomerism
possible possible
p p
LL

a y C
C=C
b y C
q q
Geometrical isomerism Geometrical isomerism
not possible not possible
A

Nomenclature Systems of Geometrical isomers

(a) Cis–Trans System
If same groups are at same side then cis and if same groups are at different side then trans.
a a b a
C=C C=C
b b a b
[Same groups, same side] [Same groups different side]
cis trans
a a z z
Ex. C=C C=C
x y x y
cis cis
Cl Cl
CH3 H C
Ex. C=C
H CH2–CH3 C
Br Br
trans-2–pentene It does not show Geometrical isomers
So no cis–trans
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(b) E – Z System :
E (Entgegen) : When high priority groups are at opposite side.
Z (Zusamman) : When high priority groups are at same side.
LP HP HP HP
C=C C=C
HP LP LP LP
'E' 'Z'
HP – High priority and LP – Low priority
Priority Rules [CIP Sequence Rule] :
Rule I : Priority is proportional to atomic number of atom which is directly attached to sp2 carbon.
Br F
C=C
[HP] I Cl [HP]

'Z'
Rule II : If rule-I is failed then consider the atomic number of next atom and so on.
CH3
CH3 [C.C.C]
CH3 [HP]
[HP] F C
C=C CH3
[LP] CH3H2C C CH3
EN [C.C. H]
H [LP]

'Z'
Rule III :– If multiple bond is present then consider them as :-
C C
C = C  – C – C C  C  – C – C–
LL
C C C C

O N C
C = O  C C  N  C N
O–C N C
O
[O, O, H]
NC C–H
A

H C=C
[HP] N C–OH
H [O, O, O]
O [HP]
'Z'
Rule IV : If isotopes are present then consider atomic weight.
H CH3
C=C
[HP] D CH2–CH3 [HP]
'Z'

BEGINNER'S BOX-4
1. Assign correct E, Z configuration to following molecules :-

CH3 C H CH3
(1) C (2) CH3 C C
Cl CH3 H Cl
N C CBr3
C C
CH3 CH2 CH2Cl C CH2I
(3) C C (4) CH3
CH C COOH
CH3 CH3

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GEOMETRICAL ISOMERS IN OXIMES [>C = N–] :

 Oximes show G. I. due to restricted rotation about double bond.

 Only those oximes show Geometrical isomerism in which sp2 carbon have two different groups.

CH3–CH=O + H2N–OH  CH3–CH=N–OH (oxime)

Ex. Acetaldoximes has two Geometrical isomers –

CH3–C–H CH3–C–H
N–OH HO–N

syn anti

When H and OH are on the same side. When H and OH are on the opposite side

Ph–C–H Ph–C–H
Ex. Benzaldoxime
N–OH HO–N
[Syn.] [Anti]
EN
GEOMETRICAL ISOMERS IN AZO COMPOUNDS : (  N  N )
 

Ph
Ph
N
N
N Ph–N=N–Ph 
N
LL
Ph Ph
(syn) (Anti)

GEOMETRICAL ISOMERS IN CYCLOALKANES : Cycloalkanes show Geometrical isomerism due to

restricted rotation about single bond. Only those cyclo alkanes show Geometrical isomers in which atleast
A

two different carbons have two different groups.

Me Me Me Me cis

H H H H
Two geometrical isomers H
Me trans
H Me

NUMBER OF GEOMETRICAL ISOMERS IN POLYENES :

R1–CH=CH–CH=CH .................................. CH=CH–R2

(a) If R1 R2 then number of Geometrical isomers = 2n

[n = number of double bonds which show G.I.]

Ex. CH3–CH=CH–CH=CH–CH=CH–CH2CH3

As n = 3, number of Geometrical isomers = 23 = 8

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(b) If R1 = R2 then number of Geometrical isomers = 2n – 1 + 2p – 1
n n 1
where p (when n is even) and p (n is odd)
2 2
Ex. CH3–CH=CH–CH=CH–CH=CH–CH3 [n = 3]
2 1
Number of Geometrical isomers = 2 + 2
=4+2=6

BEGINNER'S BOX-5
1. Which of the following shows Geometrical isomerism –
(a) CH3—CH2—CH=N—OH (b) H2C=N—OH
(c) CH3–C–CH3 (d) CH3–C–CH2CH3

N–OH N–OH
(1) a, c (2) c, d (3) a, d (4) b, c
2. Which of the following show Geometrical isomerism –
(1) 1,1–Diphenyl–1–butene (2) 1,1–Diphenyl–2–butene
(3) 2,3–Dimethyl–2–butene (4) 3-Phenyl–1–butene
3. Which of the following show Geometrical isomerism –

H Cl
EN H
H
Me
Me
(a) H H (b) Cl Cl (c) Cl Br (d) Me
Cl Cl H H Cl Br
Me
LL
(1) a, b, d (2) a, c, d (3) a, b, c (4) b, c, d
4. Calculate total number of geometrical isomers in the following compound
CH3–CH=CH–CH=CH–CH=CH–C6H5
(1) 2 (2) 4 (3) 6 (4) 8
A

(B) Conformational Isomerism

The different arrangement of atoms in space that result from the free rotation around single bond, are called
conformations. The phenomenon is called conformational isomerism
H
H H
H H
C 
 C

C H H C
H
H H H H

Confomations of ethane [CH3—CH3] :

H
H H
H H
C C
60

 

C H H C
H
H H H H

(Saw horse projection)

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H
H H H
H

60

 

H H H
H H H H

(Newman projection)

Stability order : Staggered > Eclipsed

Dihedral Angle : Dihedral angle in eclipsed form of ethane is 0°.

Dihedral angle in staggered form of ethane is 60°.
Conformation of Butane
[CH3—CH2—CH2—CH3]
Me Me
Me Me
H Me H H H
Me
60 60 60

 

EN 
 
 
 

H H H H H H
HH H Me H
H H Me

(I) (II) (III) (IV)

I (Fully eclipsed form) : In this form distance between 2 methyl groups is minimum so maximum repulsion or
minimum stable.
LL

IV (Anti or staggered) : In this form distance between 2 methyl groups is maximum so minimum repulsion or
maximum stable.
Stability order : IV > II > III > I

BEGINNER'S BOX-6
A

1. Which of the following shows conformational isomerism.

H H
O
(a) C (b) C
H
H H H H H

O O
O
(c) (d)
H H
H H

H H H H H

(e) C C H (f) C C C

H H H H H H H H

(1) b, c, e, f (2) a, b, c, f (3) b, c, d, e (4) b, d, e, f

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2. Most stable conformation of butane is :-
(1) Partial eclipsed (2) Fully eclipsed
(3) Staggered (4) Gauche
3. What is dihedral angle in staggered form of ethane :-
(1) 30° (2) 45° (3) 75° (4) 60°

EN
LL
A

ANSWER KEY
Que. 1 2 3 4
BEGINNER'S BOX-1
Ans. 1 3 3 1

Que. 1 2 3
BEGINNER'S BOX-2
Ans. 3 1 1

Que. 1 2 3 4
BEGINNER'S BOX-3
Ans. 1 2 4 3

Que. 1 2 3 4
BEGINNER'S BOX-4
Ans. Z E E E

Que. 1 2 3 4
BEGINNER'S BOX-5
Ans. 3 2 1 4

Que. 1 2 3
BEGINNER'S BOX-6
Ans. 4 3 4

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