Isomerism | 9.

11

4. GEOMETRICAL ISOMERISM
The main criteria for geometrical isomerism is the restriction in rotation:
In alkenes, (C=C) bond is made of σ –and π –bonds. A π –bond is made by the sideways overlap of the un–
hybridised π–orbitals of two C atoms above and below the plane of two C atoms. If one of the atoms is rotated
through 90o, orbitals will no longer overlap and π –bond would break, which requires 25kJ/mol of energy. Hence,
the rotation around (C=C) bond is not free but restricted. Due to this restricted rotation, the relative position of
atoms or groups attached to the C atoms of the double bond gets fixed, which results in the formation of two
distinct forms called geometrical isomers.

On rotation
C C C C
 Overlap is
destroyed
 - bond

Types of geometrical isomerism: There are 3 types of geometrical isomerism on the basis of groups attached to
double bond or the site of restricted rotation. They are mentioned below:

4.1 Cis–Trans Isomers

This kind of isomerism is used when there is at least a common group on both sides of the double bond or the site
of restricted rotation (especially cycloalkane)

CH3 CH3 CH3

H
C C C C
H H H CH3
cis-But-2-ene trans-But-2-ene
(I) (II)
The isomer (I) in which similar groups or atoms lie on the same side of the double bond is called cis–isomer,
whereas the isomer (II) in which the similar atoms or groups lie on the opposite side of the double bond is called
the trans–isomer.
H C COOH H C COOH H3C C COOH H3C C COOH
E.g. (I) (II)
H C COOH HOOC C H HOOC C H
H C COOH
Maleric acid (cis) Fumatic acid (trans) Crotonic acid (cis-isomer) Mesaconic acid (tran-isomer)

Properties of cis–trans isomer

(i) Stability: Cis < Trans
H C CH3 H C CH3
Cis forms is less stable then trans because of the mutual repulsion between
the same group e.g. H C CH3 CH3 C H
Cis form Trans form
(ii) Dipole moment: Asymmetrical trans molecule has zero dipole moment, (more repulsion) (less repulsion)
even if trans molecule is not symmetrical than its dipole moment is less than
that of the cis isomer.
µ (Sym trans)=0
(unsym trans) µ < cis isomer
H C  CH3 H C  CH3
H C  CH3 CH3  C H
Cis form Trans form
=+ve =0
9 .12 | Isomerism

(iii) Polarity: Cis > Trans

(iv) Solubility: Soluble in a polar solvent. Cis > Trans O
(v) Boiling point: Cis >Trans (due to high polarity) H C COOH 100oC H C C
O
(vi) Melting point: Cis < Trans. It is due to better packingHin Ccrystal
COOH due to-Hsymmetry.
2O H C C heat of hydrogenation,
But
heat of combination, density refractive index is higher in cis isomer than trans.
O
(vii) Heating effect: Maleic acid from anhydride at 100oC but fumaric acid forms anhydride at 250oC
Maleic Acid
O O
H C COOH o
100 C H C C H C COOH 240oC H C O
-H2O O O + H2O
H C COOH H C C HOOC C H H C O
O O
Maleic Acid Fumaric Acid
O
H C O
4.2 E–Z Isomerism
H C COOH 240oC
O + H2O
HOOC C H H C O
a 
C=C O
b 
A better system E–Z, is applicable for those type of compounds which cannot be express by cis trans
nomenclature.
E → Entegen (opposite) Z → Zusamann (same)
E–form: When two same priority groups present on the opposite side of the double bonded is known E–form and
when the same priority group present on same side of the double bond is called Z–form.

L.P .b C a H.P L.P .b C a H.P L.P=Low Priority group or atom
H.P .b C a L.P L.P .b C a H.P H.P.= High Priority group or atom
E-Form Z-Form

Priority rule: Chann, ingold & prelong proposed a sequence rule:

Rule 1: When an atom or group of atoms which are directly attached L.P .Br C l H.P L.P .Br C l H.P
to the stereo genic centre have a higher atomic number, they will
have higher priority. For example H.P Cl C F L.P L.P F C Cl H.P
E-Form Z-Form

Rule 2: When the atomic number will be same, then higher atomic L.P D C T H.P L.P D C T H.P
weight or group of atom have higher priority
L.P H C CH3 H.P H.P CH3 C H L.P
Z-Form E-Form

Rule 3: When both atomic number and atomic weight are the L.P Cl3C C CBr3 H.P L.P Cl3C C CBr3 H.P
same, then priority will be decided by the next joining atom.
H.P CH3 C H L.P L.P H C CH3 H.P
E-Form Z-Form

C
Rule 4: If multiple bonded group attach to the double bonded carbon, C O C O C C C C
then they are considered in the following manner.
O C
 Isomerism | 9.13

Some E–Z configuration of following compounds

(2) CH=CH2 (2) (2)

NC CH3 (1)’ H (2) (2)’
C=C
C=CH2 (1) (1) C=C CH3
(1) CH CH3- CH2 C=C
(Z-form) (2)’H (1)’ CH2CH3 (1)’
O
(3Z,5E)
(1) (1)
CN (2)’ CH2 Cl (1)’ H
C=C CH = C
(2)HC C C=C H
CH2 (2) CH CH3
(2)
(1) CH3 CH3
(2Z, 4E)’

4.3 Syn–Anti Isomerism

C=O+H2

Aldoximes
N OH C=N OH
Oxime  Oxime of aldehyde
and oxime of unsymmetrical
ketone also show
Geometrical Isomerism

CH3 C H CH3 C H

N OH HO N
Syn form Anti form

When the –OH group and H atom is on the same side of the double of C and N, then it is the syn form otherwise
anti form

CH3 C CH2 CH3 CH3 CH2 C CH3

N OH N OH
Syn form Anti form

In unsymmetrical Ketoxime, if –OH and the alphabetically alkyl present on the same side of double bond, then it is
syn form and other isomer is anti form.

Geometrical isomerism in AZO compounds:

Ph Ph
N N
N N
Ph Ph
Syn form Anti form cycloalkanes cycloalkanes
H H Cl H

4.4 Geometrical Isomerism in Cyclic Compounds

Cl Cl H Cl
There is a restriction in rotation about the bonds in geometrical
Cisisomerism
form which is also seen
Transin cycloalkanes.
form

cycloalkanes cycloalkanes HOOC COOH H COOH

H H Cl H

Cl Cl H Cl H H HOOC H
Cis form Trans form Cis form Trans form

HOOC COOH H COOH

9 .14 | Isomerism

MASTERJEE CONCEPTS

•• I n E–Z nomenclature, According to CIP rules priority is to be given to atomic numbers but in case they have
same atomic number, i.e., isotopes, then priority is to be given to molecular weights.
••  isconception– it is not necessary that a compound having double bond must have geometrical isomers.
M
In case if the 2 substituents on 1 side are the same, geometrical isomers are not possible.
•• Geometrical isomers are diastereomers
••  isconception– in compounds having cumulative double bonds geometrical isomerism need not
M
be defined. Those having an even number of double bonds can be optically active but doesn’t have
geometrical isomers while those having an odd number of double bonds cannot be chiral (unless chiral
substituents) but can have geometrical isomers.
••  isconception– geometrical isomerism is not only restricted to double bonds but it can be extended to
M
cyclic compounds and spiranes.

Nikhil Khandelwal (JEE 2009, AIR 94)

Illustration 10: Arrange the following ligands in the decreasing order of priority. (JEE MAIN)

(i) −CH( CH3 )2 (ii)

 
Cyclohexyl

Sol: In cyclohexyl, (–CH) is joined to two (CH2) groups and is further joined to another ring C atom. In (i), (–CH) is
joined to two (CH3) groups each having three H atoms.

 
C H
CH2
CH(CH3)2 HC HC H
CH2
2H H C H

H
3H

Illustration 11: Assign E–Z configuration to each of the following: (JEE MAIN)

C C-H Cl Me

a. Me b.
Me
Me
Me Me Me
Me
Sol: If two higher priority groups are on same side we assign it Z–configuration.
If two higher priority groups are on opposite sides we assign it E–configuration.
(i) 
(Z) Priority of HC≡C–>–CMe3 and priority of CH2 = CH–>–CHMe2 . So two higher priority groups on same
side, hence Z–configuration.
(E) Priority of −C H2 C l > Me , and CH3 CH2–>Me. So two higher priority groups on opposite sides, hence
(ii) 
E–configuration.
 Isomerism | 9.15

Illustration 12: Give the decreasing order of net dipole moments of the following (JEE ADVANCED)
Br H Br Br Br H
(I) (II) (III)
Br H H H H Br
Sol: I>II>III
(I) has a smaller angle of separation between two Br atoms than in (II) and (III). Resulting in more net dipole
moment (µ).
Br H

Br H

(II) Has a large angle of separation between two Br atoms; therefore, net ( µ ) is less than (I).
Br H

Br H

In (III), two Br atoms and two H atoms have equal and opposite bond moments; therefore, net µ is zero.
Br H

H Br

Illustration 13: Give the structural and diastereomers of pent–1–ene. (JEE ADVANCED)

Sol: Write the C–skeletons and introduce double bond. The possible structures are: (In Image II double bond is missing)

4 2 4 2 H
5 1 5 1 4
4 1 Me
3
2
1
5 3
3 3 5 2
C-Skeleton Pent-1-ene Me Me Me
H H
(I) H
(E)-Pent-2-ene (Z)-Pent-2-ene

(II) (III)
1
1
4 2 Me 4 Me Me
2 4 1 1
2
3 3 Me Me 4
3
C-Skeloton 3 Me 2 Me
(IV) (V) (VI)
3-Methyl
2-Methyl but-1-ene 2-Methyl but-2-ene
but-1-ene

(II) and (III) are diastereomers (geometrical isomers).

C–2 is 4° C atom and cannot form a double bond to give an alkene.

1
2

3
C-Skeleton
9 .16 | Isomerism

5. OPTICAL ISOMERISM
Compounds which can rotate plane polarised
light, are called optically active compounds and
this phenomenon is called optical activity. Plane
polarised light can obtained by passing ordinary
light through Nicol prism. Solution of an Optical
active compound can rotate plane polarised
Ordinary light
light either left or to the right through the angle Nicol prism Plane polarizes waves
waves vibrating in
α. This property of a substance of rotating plane vibrating in one direction
all direction
polarized light is called optical activity and the
substance passing through it, is said to be
optically active.

The observed rotation of the plane of polarised

light produced by a solution depends upon–
(i) The amounts of the substance in tube.
Plane Rotated Plane polarizes Plane Rotated
(ii) On the strength of the solution examined.
to the right light to the left
(iii) T
 he temperature of the experiment and
the wavelength of the light used.

All these substance are known to exist in three stages.

(i) One rotating the plane of polarised light to the left this forms is named laevorotatory.
(ii) O
 ne rotating the plane of polarized light exactly to the some extent but to the right. This form is named
dextrorotatory.
(iii) A
 n inactive form which does not rotate plane polarized light at all this is mixture of equal amounts of (+) and
(–) forms and hence it is optical inactive. It is named ( ± )–mixture or Racemic mixture. (Latin, Racemic–mixture
of equal compounds)

+
Analyzer
(can be rotated) 0
- Observer
+90

-90
As the arrows indicate, the optically
active substance in solution in the 180 Degree scale
tube is causing the plane of the (Fixed)
polarized light to rotate The plane of polarization
of the emerging lights is
not the same as that of
the entering polarized light
Polarimeter tube

Polarizer (fixed)

The principal working parts of a polar meter and the measurement of optical rotation.
 Isomerism | 9.17

(a)

(b)

-40

( c)

Polarizer Analyzer Observer

 olarizer and analyser are parallel. No optically active substance is present. Polarized light can get through the
P
analyser.
•• Polarizer and analyser are crossed.
•• No optically active substance is present.
•• No polarized light can emerge from the analyser.
•• The substance between polarizer and analyser is optically active.
••  nalyser has been rotated to the left (from observer’s point of view) to permit rotated polarized light through
A
(substance is levorotatory).
•• Clockwise direction is also said to be dextrorotatory, and one that rotates plane–polarized light in a

counterclockwise direction is said to be levorotatory (Latin: dexter, right, and leavus, left).

5.1 Specific Rotation

The number of degrees that the plane of polarization is rotated as the light passes through a solution of an
enantiomer depends on the number of chiral molecules that it encounters. This, of course, depends on the length
of the tube and the concentration of the enantiomer. In order to place measured rotations on a standard basis,
chemicals calculate a quantity called the specific rotation, [α], by the following equation: [α] =α where [α]= The
specific rotation α = The observed rotation c.l

Asymmetric carbon (or) Chiral Carbon: If all the four bonds of carbon are bounded by four different atoms /
groups, it is chiral. Chiral carbon is denoted by star.
a

d C* c

b
Optical isomerism in bromochlorofluoroiodo methane: The structural formula of bromo chloroiodomethane is
Br

F C* Cl

I
The molecule has one chiral carbon as designated by star. So, the molecule is chiral and is non–super imposable
on its mirror image.
According to Van’t Hoff rule, Total number of optical isomers should be = 2n, where n is number of chiral centre(s).
9 .18 | Isomerism

The fischer projections of the two isomers are

Br Br

F l I F

Cl Cl
(I) (II)

These are optically active, which are non–super imposable mirror images of each other and can rotate the plane
of polarized light.
Stereoisomers which are mirror–images of each other can called enantiomers (or) Enantiomorphs. (i) and (ii) are
enantiomers. All the physical and chemical properties of enantiomers are the same except two: They rotate PPL to
the same extent but in opposite directions. One which rotates PPL in clockwise direction is called dextro–rotatory
(dextro is Latin word meaning thereby right) and is designated by d (or) (+). One which rotates PPL in anti–clockwise
direction is called laevo rotatory (means towards left) and designate by  (or) (–).

5.2 Chirality
This term is been used to describe molecules without any elements of symmetry, thus unsymmetrical
molecules are also called chiral molecules and optical activity is attributed to certain chiral centres in them. An
asymmetrical carbon is a chiral center. Chirality is lost when two atoms bonded to an asymmetric carbon become
similar, thus lactic acid is optically active but propionic acid is inactive.

Conditions for optical activity

(i) I t must have an asymmetric C atom or the chiral C atom. C atom which is attached to four different atoms
or groups is called an asymmetric C atom or the chiral centre or stereo genic or stereo centre.

Br Br

Cl C H H C Cl

F F

(ii) It must have a non–superimposable mirror image.

(iii) It should not contain any element of symmetry, i.e.,

● Plane of symmetry or (mirror plane or σ –plane).

● Alternating axis of symmetry.
● Centre of symmetry or centre of inversion.
COOH
(i)  lane of symmetry or mirror plane or σ –plane: It is defined as
P COOH COOH
an imaginary plane which divides the molecule into two equal H OH HO H H OH
HO H H OH H OH
parts such that one part of the molecule is a mirror image of
COOH COOH COOH Plane of
the other part. For example: (+) form of (-) form Meso form symmetry
tartaric acid
(ii) A
 lternating axis of symmetry: A molecule possesses an n–
fold alternating axis (A.A) of symmetry. When rotated through b b b
a d a a
an angle of 360 / n about this axis, followed by the reflection
ο
d
d
a a a
d
d d
in a plane perpendicular to this axis, the molecule is identical
b b b
to the original molecule. For example, 1,2,3,4–tetramethyl (+) form (-) form Meso form
cyclobutane (I) contains four–fold alternating axis of symmetry.
Rotation of (I) through 90ο about axis XY, which passes through the centre of the ring perpendicular to its
plane, gives (II) and reflection of (II) in the plane of the ring gives (I).
 Isomerism | 9.19

This situation arises n times

Me in the molecule:
H (I) has two diagonal planes of symmetry.
O O
Me
Me NH HMe NH Me Me Me H
2 1 O O
1 4
Rotated to 90
o Me NH Me NH
H
H H NH Me Me
H NH Me Me H
o
360 4-fold H
o
90 A,A, of
3 4 O symmetry 2 O 4
(Cis form) 3 H NH H NH
H Me

 
Me H (II) Me
 
Optically active (Trans H
form) O
Does (Contains centre of symmetry)
Y not contain It has 4-fold (Cis form)
O
A, A, of Rotated
any symmetry (Optically inactive) H (Trans form) Me

 
(I) symmetry and two diagonal o
to 90
Optically active
(Optically inactive) Does not contain (Contains centre of symmetry)
Dimethylplane
diketoofpiperzine
symetry
any symmetry (Optically inactive)

Dimethyl diketo piperzine

+ +
A H H A
2 1 +
1 4 +
o A H H A
+ - Rotated to 90 +
H H A A 4 fold AA A H H 2
1
1
4
o
- Rotated to 90


of symmetry


+ +
3 4
It does not have
2 3 H H A A 4 fold AA A H H
- -
A H H

of symmetry


(III)
plane of symmetry
(IV) A 3 4 2 3
-
It does not have
-
(Optically inactive) A H plane of symmetry H A
(III) (IV)
(Optically inactive)
(iii) C
 entre of symmetry (or centre of inversion): It is defined as a point from which lines when drawn on one
side and produced to an equal distance on the other side will meet identical points in the molecule. For
example: (It possesses a centre of symmetry, which is the centre of the ring and is therefore optical inactive)
F ig. – Dimethyl cyclobutane–1.3 – dicarboxylic acid (It possess a centre of Me COOH
symmetry, which is the centre of the ring and is therefore optical inactive. 2
I
It may be noted that only an even–membered ring can possibly possess a H H H H
centre of symmetry. 3 4
+ − + −
A and A are chiral group,e.g., A ⇒ A ⇒ HOOC Me
Me 2,4–Dimethyl cyclobutane–
Me
1,3–dicarboxylic acid
(+) C Et (-) C Et

H H

Stereoisomerism in Tartaric acid: Compounds which contain two asymmetric carbon atoms and are of the type
Cabc–Cabc exist in only three isomeric forms. Two of these are non–superimposable mirror images of each other
and are optically active and the third, a diastereomer of the first two, contains a plane of symmetry, is super
imposable on its mirror image, and is not optically active.
OH CO2H
OH
OH CO2H
CO2H H C OH
HO2C HO2C HO2C

CO2H OH H C Cl
OH
OH CH2H
I(-) tartaric d(-) tartaric Mesotartaric
acid acid acid
The inactive diastereomer is usually described as a meso form. As with other examples of diastereomers, the
properties of meso forms are different from those of the isomeric mirror–image pairs; for example, mesotartaric
acid melts at a lower temperature [140° C] than the d and  isomers [170° C], and is less dense, less soluble in
water, and a weaker acid.
9 .20 | Isomerism

5.3 R–S System (Absolute Configuration)

R → Rectus (Right) S → Sinister (Left)
R → S nomenclature is assigned as follow:
Step I: By the set of sequence rule, we give the priority order of atom or group connected through the chiral
carbon.
Step II: If atom/group of minimum priority is present on the vertical line, then
Movement of eyes in clockwise direction = R
Movement of eyes in anticlockwise =S
Movement of eyes taken from 1 → 2 → 3 through low molecular weight group (if needed)

2b c3
s

1a c3 1a b2
R CW ACW

d4 d4
2b 1a
Step III: If minimum priority group present on the horizontal line, then s

clockwise rotation ⇒ S 2b b4 d4 c3
anticlockwise rotation ⇒ R R ACW ACW

c3 b2

5.4 ENANTIOMERS
Those compounds which are nor superimposable on their mirror image, is called enantiomeric pairs.
Condition → same molecular formu, same structure formul, different configuration.
Some important facts about the fisher projection formulae.
(a) If the fisher projection of stereoisomers is lifted from the plane of paper & turned over, then such an operation
will be result in enantiomers of the original compound.
d d

a b If it is a
turn over
c c


(A) Enantiomer of A
c

a b

dd
i.e. if either vertical or Horizontal line groups are inverted, then enantiomers of the original compound result.

(b) If more than one chiral centre is present molecule have plane of CH3 CH3
symmetry
H Br Br H
H Br Br H

CH3 CH3
(A) Same as A
 Isomerism | 9.21

Properties of enantiomers:
(i) Enantiomers have a chiral molecule
(ii) E
 nantiomers have identical physical properties like b.p.,m.p., refractive index, density etc. They rotate the ppl
in opposite direction but to equal extent.
(iii) 
They have identical chemical properties, However, their reactivity i.e. rate of reaction will be differ if they
combine with other optically active reagents.
•• A
 ll the optically active compounds exist in two or more isomeric forms, which differ from one another in
the relative spatial arrangement of atoms or groups.
•• T
 hese stereoisomers which resemble one another in their chemical reactions and most of the physical
properties but differ only in their behaviour towards plane–polarised light are called optical isomers and
the phenomenon is called optical isomerism.
•• O
 ptical isomers which are non–superimposable mirror images of each other are called enantiomers
and the phenomenon is called enantiomerism. The enantiomers have identical physical and chemical
properties but rotate the plane of polarised light in opposite directions but to the same extent.
•• It may be noted that the necessary and sufficient condition for a molecule to exhibit enantiomerism (and
hence optical activity) is chirality or dissymmetry of molecules, i.e., the molecule and its mirror image
must be non–superimposable. It may or may not contain chiral or asymmetric carbon atoms.
•• U
 sually, the presence of one or more chiral carbon atoms causes COOH COOH
the molecule to show enantiomerism and hence the optical activity *C *C H
H OH HO
but certainly it is not the necessary and sufficient condition. For
example, meso–tartaric acid contains two chiral carbon atoms *C *C
H OH HO H
(marked by asterisks) but does not show enantiomerism and is
actually optically inactive. COOH COOH
Meso-tartaric acid Optically inactive

Plane of Symmetry (contains a plane of symmetry and hence does not show enantiomerism)
This is because it contains a plane of symmetry which divides the molecule into two equal halves so that one half of
the molecule is a mirror image of the other. As a result, meso–tartaric acid and its mirror image are superimposable.
In other words, meso–tartaric acid is an achiral or non–dissymmetric or symmetric molecule and hence it does
not show enantiomerism or optical activity. Thus, the optical inactivity of meso–tartaric acid is due to internal
compensation, i.e., the rotation caused by one half of the molecule is exactly cancelled by an equal and opposite
rotation caused by the other half of the molecule.

5.5 Diastereomers
Those compounds which are neither mirror images nor are superimposable on each other, are called as
diastereoisomers.
Ex: Cis–trans isomer are configurational isomers but they are not mirror images and are thus, they are said to be
diastereomers.

Characterstic of Diastereomers
●● Generally optical active, however geometrical isomers are an exception.
●● Their physical properties are different like mpt, bpt, density, solubilities & values of specific rotation.
●● They can be separated by fractional distillation, fractional crystallization & chromatography etc.
●● They exhibit similar but not identical chemical behaviour.
9 .22 | Isomerism

5.6 Meso Compounds

A meso compound is superimposed on its mirror image. It is optically inactive although H C Cl H C Cli t
contains two or more stereocenters. All meso compounds are achiral due to internal H C Cl Cl C H
compensation.
CH3 CH3
H Br H Br
Br H H Br
CH3 CH3
5.7 Racemic Mixture and Optical Resolution
When equal amounts of two enantiomers are mixed together, it gives an optically inactive form called racemic
mixture or modification. It is denoted by using the prefix ± or dl before the name of compound. For example, if
equal amounts of (+) lactic acid and (–) lactic acid are mixed together, we get the racemic or ( ± ) lactic acid, which
is optically inactive. Evidently, the optical inactivity of a racemic mixture is due to external compensation i.e. the
rotation caused by molecules of one enantiomer is exactly cancelled by an equal and opposite rotation caused
by the same number of molecules of the other enantiomer.
A racemic mixture can also be obtained chemically. The process by which one enantiomer (+or–) of an optically
active compound is converted into a racemic mixture is called racemization. Racemisation can be carried out by
heat, light, or chemical reagents. For example, lactic acid and tartaric acid undergo racemisation in the presence
of a base.

Resolution of a Racemic Mixture

1.  ince a racemic mixture contains equal amounts of two enantiomers, so they can be separated into (+) or
S
(–) enantiomers by a number of methods. The process of separation of a racemic mixture into its (+) and
(–) enantiomers is called resolution. Since, the enantiomers have identical physical and chemical properties
except towards optically active reagents, they cannot be separated by the usual techniques such as fractional
crystallization, fractional distillation, chromatography, etc. Therefore, special methods are used to achieve
their separation. Some of these are listed below:
●● Mechanical method.
●● Biological method using enzymes.
●● C
 hemical methods (by making their diastereomers).
●● C
 hromatographic separation by using special adsorbents.
2.  iastereomeric method: One of the most common methods is to allow a racemic mixture to react with an
D
enantiomer of some other compound. This changes a racemic form into a mixture of diastereomers which
have different solubilitys as well as melting and boiling points. These can be separated from one another by
conventional methods of separation of compounds. The separated diastereoisomer is then broken down to
give pure enantiomers.