STUDY PACK : 4.

ORGANIC CHEMISTRY

ISOMERISM

COMMONLY ENCOUNTERED GROUPS LISTED IN ORDER

OF INCREASING RANK
First Edition Jan 2006
Second Edition Jun 2009
Third Edition Jun 2011
Fourth Edition Jun 2021 (Revised New Syllabus)

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Imran Razeek I.Chem.C (P1), M.Ed, Ph.D (Reading)

Lecturer in Chemistry cum Chairman

Chembase - School of Chemistry,

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 Isomerism
1. Define the term ‘Isomerism’

Isomers are molecules that have the same molecular formula but different
structures or configuration of atoms.

2. State the classification of Isomers

Structural Isomerism

3. Explain what is meant by term ‘Structural Isomerism’?

Structural isomers are molecules, which has the same molecular formula but
different structures.

4. Explain what is meant by ‘stereo isomerism’?

The isomerism, which arises due to different orientations or configurations of

atoms in space.

5. Write short notes on the different types of structural isomers

I. Chain Isomers:-
The Isomerism has different arrangement of ‘C’ chain

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 II. Positional Isomers:-
The isomers have the same functional group at different positions.

III. Functional group Isomers:-

The isomers have different functional groups.

6. Explain why molecules that have the same molecular formula differ in physical
properties?

Because they exists as structural isomers. Each structural isomer will have
its unique boiling point based on the surface area of the molecule. The
straight chain isomer possess higher boiling & melting point compared to
branched isomers as the surface area of the straight chain isomer is
greater than the branched isomer. Molecules with greater surface area
forms greater number of intermolecular attractions.

7. How do you explain the below observation.

An Organic compound having same molecular formula of C4H10 shows two different
boiling points of -0.5 oC & -11.7 oC

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C4H10 exist as two structural isomers Butane & 2-methyl propane
Butane has a large surface area when compared with 2-methyl propane. Hence
butane will possess more intermolecular attraction than 2-methyl propane. As a
result, butane will exhibit a higher boiling (-0.50C) than 2-methylpropane
(-11.70C)

8. Draw the structural formulae of different isomers of below compounds & name them according
to IUPAC nomenclature. (Include branched cyclic isomers where applicable)

i) C3H6 ii) C4H8 iii) C5H12 iv) C5H10 v) C6H14 vi) C6H12

vii) C2H5OH or C2H6O viii) C3H7OH or C3H8O ix) C3H5OH x) C2H3Br3

xi) C4H8Br2 xii) C3H4Cl4 xiii) C3H6(OH)2 xiv) C2H4(OH)2 xv) C5H8Cl2 xvi) C6H12(OH)2

Answers

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Answers

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Geometric Isomerism

1. Explain how Restricted bond rotation give rise to geometric isomerism

There is free rotation in a C-C single sigma bonds but there is no free rotation
about a C=C. The rotation of C=C double bond involves breaking of a π (pi) bond
this requires more energy than what is available at room temperature.

2. Lack of rotation in the carbon-carbon double bond give rise to two types of geometric
isomers. Name & describe them

cis isomer and trans isomer.

The isomer with the 2 functional group (or 2 similar groups) on the same side of
the molecule is called the cis form (cis means same side in latin). When the
functional groups are on the opposite side of the molecule, it is called as the trans
form. (trans means opposite side in latin)

3. What are the conditions other than the restricted rotation, that must be met to give rise
to geometrical isomerism

Restricted rotation alone does not give rise to geometrical isomerism. At the point
of restricted rotation, each ‘C’ must be bonded to the same functional group. The
below structures do not exhibit geometrical isomerism.

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4. Compare the stability of cis-trans isomers

The trans isomer is more stable than the cis isomer, because cis isomer exhibit
steric hindrance (crowding of the molecule) due to the functional group being
present on the same side. The cis isomer can be transformed in to trans isomer by
heating.

5. Draw & name the geometrical isomers of below compounds

CH3CH=CHCH3

CHBr=CHBr

CHOH=CHOH

CH3CH2CH=C-CH2CH3
Cl

ClCI=CIBr

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 CHOCH=CHCHO

6. Explain why is cis-1,2 di chloroethene is polar while its trans isomer is not?

cis isomer is not symmetrical hence the center of positive charge does not coincide
exactly with its center of negative charge resulting the molecule to be polar. ‘Cl’
attracts electrons more towards itself due to its greater electronegativity. As a
result the center of negative charge will be drawn towards chlorine resulting
polarization as shown above. But the trans isomer is symmetrical where equal
dipoles cancel each other resulting no polarization.

7. Why the below structures are not considered to be isomers?

H Br H H

H–C–C–H & H–C–C–H

Br H Br Br

Because there is free rotation between the C-C single sigma bonds, there is no
bond-restricted rotation.

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E-Z Isomerism

1. Discuss giving examples how the cis-trans naming system breaks down, hence the need
for an E-Z naming system

When there are 3 or 4 different substituents attached across the C=C the
cis – trans system cannot be used.

E.g.

Therefore in such situations the molecules are named as to E-Z naming system.
(‘E’ is for entgegen, German for opposite & ‘Z’ is for zuzumen, German for
together)

2. Explain how a molecule is named according to the E-Z naming system.

The E-Z naming system is based on the relative priorities of the two groups
bonded to each ‘C’ atom across the C=C bond. If the high priority groups are on the
same side of the double bond, the isomer is said to have the z-configuration (zame
zide),if the high, priority groups are opposite side of the double bond, the isomer
has E-configuration.

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 Rules for assigning relative priorities to groups

The relative priorities of the groups depends on the atomic numbers of the atoms
Rule 1
directly bonded to each C on the C=C. The greater the atomic number, higher the
priority.

high (35) high (17) high (35) low (6)

Br Cl Br CH3
C=C C=C
H CH3 H Cl
low (1) low (6) low (1) high (17)

(Z)-1-bromo-2-chloro propene (E)-1-bromo-2-chloro propene

(Note: use the atomic number of Carbon not the formula weight of the –CH3 group,
because the priorities are based on the atomic number of the atoms not the formula
mass of groups.)

If the two substituents, which are directly attached to the ‘C’, are identical atoms,
Rule 2 compare the atoms attached with those two on the basis of their atomic numbers.

Eg:- -CH3 & -CH2CH3 group

The methyl group ‘C’ is attached to 3 ‘H’ where as ethyl group ‘C’ is attached to a ‘C’ & 2
‘H’. The ‘C’ has a greater atomic number than ‘H’, so the ethyl group has more priority
than the methyl group.

Eg:- Priority order of some alkyl groups.

-C(CH3)3 > -CH(CH3)2 > -CH2CH3 > -CH3

-C (C,C,C) > -C (C,C,H) > -C (C,H,H) > -C (H,H,H)

Work outward from the point of attachment, comparing all the atoms attached to the first
Rule 3
atom, before proceeding further along the chain.

-CH(CH3)2 [-C (C,C,H) ] outranks –CH2CH2OH [-C (C,H,H) ]

Rule 4 When considering groups with different atoms attached to the ‘C’ do not add the atomic
numbers, always evaluate substituent atoms one by one & consider the single atom with
the greatest atomic number.

-CH2OH [-C(O,H,H) ] outranks -C(CH3)3 [-C(C,C,C) ]

Because oxygen has a higher atomic number (8) than carbon (6)

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 If an atom is doubly bonded to another atom it is considered to be if it were singly
Rule 5
bonded to two of those atoms.
Eg:- O
II
-C--H is treated as it were -C (O,O,H)
-CH=CH2 is treated as it were -C (C,C,H)
The group -CH=O [-C (O,O,H) ] outranks -CH2OH [-C (O,H,H) ]

3. Draw & name the E & Z isomers of each of the following compounds.

i. CH3CH2CH = CHCH3

ii. CH3CH2C(Cl) = CH(CH2CH3)

iii. BrC(Cl) = CC(CH3)3(CH2OH)

iv. BrC(I) = C(CH2OH) (CH=O)

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 v. CH3CH2C(C4H7) = C(CH2Cl) (CHCH3CH3)

vi. CH3C(C2H5) = C(CH2CH3)(CH2CH2Cl)

vii. H3CC(Br) = C(CH2Br)(C4H7)

viii. CH2OH C (CH3CO) = C (CH2Br) (CH2CH2Cl)

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