STEREOISOMERISM

KEY CONCEPTS
STEREOISOMERISM
• Stereoisomers have the same molecular formula and the same structure but they differ in configuration, i.e. in
the arrangement of their atoms in space.

GEOMETRICAL ISOMERISM :
In this type of isomerism the compounds possessing same molecular formula differ in their properties due to the
difference in their geometry.

H–C–COOH H–C–COOH
|| ||
H–C–COOH HOOC–C–H

Maleic acid Fumaric acid

 CONDITIONS FOR GEOMETRICAL ISOMERISM

1. There should be a double bond ring in the molecule.
2. The two atoms or groups attached to each doubly bonds carbon atom should be different. If one of
the two doubly bonded carbon atoms carries two identical groups then the molecule does not
exhabit geometrical isomerism.
 Examples :
2 1 2 1
• Alkenes CH3  CH  CH  CH3 C 6H5  CH  CH  COOH
In these cases both substitx Vuents on carbon-1 and carbon-2 are different hence they will show
geometrical isomerism.
• Cycloalkanes
Geometrical isomerism is possible in cyclic compounds also. There can be no rotation possible
above C — C single bonds. In such compounds thus for rotation breakage in the bonds is required
resulting to breakage in the ring, e.g.
1, 2-dimethyl cyclopropane exists in two isomeric forms written below :
H CH3

CH3 H
CH3 CH3

H H
trans form cis form

1, 2-dimethyl cyclopropane

A requirement for geometrical isomerism in cyclic compounds : There must be at least 2 other groups
besides hydorgen on the ring and these must be on different ring C-atom. for example no geometrical
isomers are possible for 1, 1-dimethyl cyclopropane.

CH3

CH3
1, 1-dimethyl cyclopropane (No isomers possible)
• Oximes and Azo compounds
The oximes are formed by the reaction of carbonyl compounds (>C=O compounds i.e., aldehydes and
ketones) with NH2OH (hydroxyl amine) as :
>C = O + H2 N—OH  >C=N—OH + H2O
oxime
R H
If –C– = aldehyde then oxime = aldoxime = C = N—OH or C = N—OH
H H
O
R
If –C– = ketone then oxime = ketoxime = C = N—OH
R
O

(a) IN ALDOXIMES :

The first member of aldoximes does not show any geometrical isomer.

(b) IN KETOXIMES :

This compound is syn for ethyl group and anti for methyl group or this can be called anti compound.
Similarly,

This compound is anti for ethyl group and syn for methyl group or this can be called syn compound.

(c) IN AZO COMPOUNDS i.e.,

C6H5
N N
N=N and
C6H5 C6H5 C6H5
anti form syn form

 E, Z SYSTEM FOR GEOMETRICAL ISOMERS :

The stereochemistry of highly substituted alkenes cannot be defined as cis or trans. For this purpose a new
notation known as E-Z notation is used. Following a set of rules (Cahn-Ingold-Prelog rules) the substituents
on a double bond are assigned priorities. The double bond is assigned the configuration E (From entgegen,
the German word for opposite) if the two groups of higher priority are on the opposite sides of the double
bond.
On the other hand the double bond is assigned the configuration Z (from zusammen, the German word
for together) If the two groups of higher priority are on the same side of the double bond.

Cahn-Ingold-Prelog Rules
1. The higher the atomic number of the atom bonded directly to the stereocentre, the higher is the priority of
the substituent. Among isotopes, the one with higher mass number gets the higher priority.

2. If two identical atoms are attached to the stereocentre, the relative priorityof the two groups is decided by
a similar comparison of the next atoms in the group moving away from the stereocentre.
 3. A double is counted as two single bonds for both the atoms involved. Thus

Priority Order :- –I, –Br, –Cl, –SO3H , –SH, –F, –OCOR, –OR, –OH, –NO2, –NR2, –NHCOR, NHR, –
CO2R,
–CO2H, –CONH2, COR, –CHO, –CH2OH,–CN, –CR3, –C6H5, –CHR2 , CH3 , D, H
Some examples are being given below :

1. H3C OCH3 2. Higher priority

Higher priority CH3 H
C
C C

H C2H5 C
Higher priority Br
C2H5 Higher priority

The groups of higher priorities are on same side. The groups of higher priorities are on opposite sides.
Hence it is (Z) - 2-Methoxypent-2-ene Hence it is (E) - 3-Bromopent-2-ene

3.

4.

OPTICAL ISOMERISM
 The stereoisomerism which arises due to non-susperimposability of mirror image structure is called
enantiomerism or optical isomerism. The mirror image isomers are called enantiomers.

Dissymmetry or chirality is the necessary and sufficient conditions for the enantiomerism. A carbon
atom bonded to four different atom/groups in a molecule is called chirality. A molecule is said to be
dissymmetric or chiral if it is not superimposable on its mirror image. On the other hand, a molecule
which is superimopsable on its mirror image is called non-dissymmetric or a chiral. Non dissymmetric
molecules do not show enantiomerism.
• Generally, the compounds containing an asymmetric carbon in their molecules are dissymmetric and hence
show enantiomerism. But there are example where in spite of the presence of asymmetric carbons the
compound does not show enantiomerism because its molecules are non-dissymmetric. For example,
meso-tartaric acid.
Mirror

meso-Tartaric acid
Superimposable : does not show enantiomerism

• There are compounds which do not contain any asymmetric carbon atom but still show enantiomerism and
optical activity because their molecules are dissymmetric. For example, substituted allenes and substituted
biphenyls.

Non-superimposable : shows enantiomerism DISSYMMETRIC MOLECULE (Shows enantiomerism)

 Representation of Enantiomers
1. Perspective Formula : In this method a normal line means bonds lying in the plane of paper and broken
line means bonds going behind the plane of paper. A solid wedge represents bond projected out towards
viewers.

(Enantiomers of 2-butanol)

2. Projection Formula : Here the molecule is imagined to be held in such a way that two of the bonds
coming towards the viewer are in the horizontal plane and are represented by solid wedges. The other
two bonds going behind the plane of paper are in vertical plane which are represented by broken lines.
The formula of enantiomers of 2-butanol are

3. Fischer Projection Formulae : Envil Fischer devised a most simple and convenient method to represent
the three dimensional arrangement of groups bonded to chirality centre. He used the point of intersection
of two perpendicular lines to represent the chirality centre. Horizontal lines represent the bonds projected
out of the plane of the paper towards viewer. Vertical lines on the other hand, represent the bonds
 projected back from the plane of the paper away from the viewer.

E.g.

 Characteristics of Enantiomers
Some of the important characteristics of enantiomers are as given below :
1. Enantiomers have chiral structures.
2. Enantiomers have identical physical properties such as melting point, boiling point, density, refractive index
etc.
3. Enantiomers are optically active substances. They rotate the plane of polarized light in opposite
directions but to the equal extent.

(+)-2-Methyl-1-butanol (–)-2-Methyl-1-butanol
Specific rotation : + 5.90º – 5.90º
Relative density : 0.8193 0.8193
Boiling point : 128.9ºC 128.9ºC
Refractive index : 1.4107 1.4107

4. Enantiomers have identical chemical properties. This means that they form same products as a result
of chemical combination. However, their reactivity, i.e. rates of reaction with other optically active substances
are different.

 Stereoisomers with more than one chirality centres

We have already studied that organic compounds having one chirality centre always possess chiral
structures and they exhibit enantiomerism. However, organic molecules having more than one chirality
centres may have chiral as well as a chiral structures. The number of possible stereoisomers also increases
with the increase in the number of chirality centres, in the molecule. In general, a compound having n
chiral carbon atoms can have 2n stereoisomers. In this section we shall study some aspects of organic
compounds having two chirality centre.

 Diastereomers
The stereoisomers which are non superimposable and do not bear mirror-image relationship are called
diastereomers. Let us understand it by taking the example of 3-chloro-2-butanol. The molecule has
two chirality centre. Thus, the number of possible stereoisomers are 22, i.e. 4. The four possible
stereoisomers are shown below by Fischer projection formulae.
 Erythro enantiomers Threo enantiomers

• Stereoisomers I and II are non-superimposable mirror images. Hence, they are called enantiomers.

• Stereoisomers III and IV are also non-susperimposable mirror images. They are also enantiomers.

• I and II also represent enantiomers in which similar groups (H atoms) are present on same side of carbon
chain such enantiomers are called erythro enantiomers.

• In III and IV similar groups (H atoms) are present on opposite side of carbon chain. Such enantiomers are
called threo enantiomers.

• Stereoisomers I and III are neither identical nor mirror images. Such stereoisomers are called diastereomers.

• In the similar way I and IV; II and III; II and IV also represent diastereoisomeric pairs.
Thus, diastereomers are configurational isomers which are not enantiomers (It may be noted that
cis-trans geometrical isomers which are configurational isomers but not enantiomers can also be called
diastereomers).

Characteristics of Diastereomers
(i) The diastereomers have different physical properties such as melting points, boiling points, densities,
solubilities and values of specific rotation.
(ii) They can be separated from one another by physical means like fractional distillation, fractional
crystallization, chromatography, etc.
(iii) They are generaly optically active. However, geometrical isomers are exceptions.
(iv) They exhibit similar but not identical chemical behavior.

 Meso compounds
According to 2n rule each compound having two chirality centres should have (22 = 4) four stereoisomers.
However, there are some compounds with two chiral carbons which have only three stereoisomers. For
example, tartaric acid molecule has two chirality centres but it has only three stereoisomers. For example,
tartaric acid molecule has two chirality centres but it has only three stereoisomers as shown below :

Pair of enantiomers Optically inactive

• Structure I and II are nonidentical mirror images and thus represent pair of enantiomers.

• Structure III is achiral inspite of the presence of two chirality centres. This is because of the presence of
plane of symmetry in the molecule. If we draw the mirror image of structure III we shall find that it is
superimposable on its mirror image (IV).

(Identical Mirror Images)

• Structure III or IV which are identical are called meso compounds (From Greek : meso means middle).
 Thus, the compounds containing two or more chirality centres but possessing a chiral molecular structure
because of having plane of symmetry, are called meso compound.

MESO compound
(Plane of symmetry is represented by dotted line ..............)

• Meso compounds are optically inactive

Meso compounds do not rotate the plane of polarized light in any direction i.e. they are optically inactive.
This is because of achiral nature of their molecules. Because of the present of plane of symmetry the
optical rotation caused by half of the molecule is compensated by the rotation caused by the other half.
This cancellation of rotation within the molecule is referred to as internal compensation. In short, the
meso compounds are optically inactive due to internal compensation.
It may be noted that if a compound with two chirality centres has the same four groups bonded to each of
the chiral carbon, than one of its stereoisomer will be a meso compound.

Pair of enantiomers Meso Compound

 RACEMIC MIXTURE
An equimolecular mixture of a pair of enantiomers is called racemic mixture or racemic modification.
A racemic mixture is optically inactive. This is because of the fact that in equimolecular mixture of enantiomeric
pair, that rotation caused by the molecules of one enantiomer is cancelled by the rotation caused the
molecule of other enantiomer. This type of compensation of optical rotation in a racemic mixture is referred
to as external compensation. Thus, racemic mixture becomes optically inactive because of
external compensation.
Representation of a racemic mixture. The racemic mixture of a particular sample is indicated by using
the prefix (dl) or (±). For example, racemic mixture of lactic acid is represented as (±) lactic acid.

 Calculation of d-, -forms and meso forms

For molecules having For molecules having

no plane of symmetry plane of symmetry

No. of a symmetric carbon n when n is odd When is even

atoms = n (even or odd)
No. of d- and -forms 2n 2n – 1 2n – 1 – 2(n –1)/2
No. of meso forms 0 2(n/2) – 1 2(n – 1)/2
 Total no. of stereoisomers 2n 2n – 1 + 2(n/2) – 1 2n – 1

 Absolute Configuration (R, S configuration)

The actual three dimensional arrangement of groups in a molecule containing asymmetric carbon is termed
absolute configuration.
System which indicates the absolute configurastion was given by three chemists R.S. Cahn, C.K. Ingold
and V. Prelog. This system is known as (R) and (S) system or the Cahn–Ingold system. The letter (R)
comes from the latin rectus (means right) while (S) comes from the latin sinister (means left).
It is batter system because in manycases configuration to a compound cannot be assigned by D, L
method.

(R) (S) nomenclature is assigned as follows :

1. Each group attached to stereocentre is assigned a priority on the basis of atomic number. The group with
the directly attached atom with highest atomic number out of the four groups gets top priority while the
group with the atom of least atomic number gets the least priority.

2. If out of the four attached atoms in consideration, two are isotopic (like H and D), then priority goes to
higher atomic mass i.e. D.

3. If out of the four attached atoms in consideration, two or more are same, then priority is decided on the
basis of the atom attached next to it in its group.

4. While deciding the priority, if the atom in consideration is attached is further to an atom through a double
bond then it is treated as if it is attached to two such atoms.

CH
/
• In this way, the phenyl group i.e., is treated as if it is is treated as if it is  C  C
\
CH

Thus, out of – CH2CH3 and – CH = CH2, the – CH = CH2 gets priority.

5. After assigning priorties, the lest priority group is written at remotest valency (going away), while the top
priority group is written at the top directed valency (towards viewer). Remaining two groups now have two
possibilities, giving two configuration. Thus, in the above compound (i.e. Bromochlorofluoriodo methane) we
have

Note that priority order is : I > Br > Cl > F

• Now the order from top priority to the one of second priority and then to the one of third priority is determined.
If this gives a clockwise direction then it is termed R configuration and if the anticlockwise direction is
obtained then it is assigned S configuration. Eg. :
 R–configuration S–configuration R–configuration S–configuration
(clockwise from top priority) (clockwise from top priority) (clockwise from top priority) (clockwise from top
priority)

6. If we have to assign the configuration to a given structure and in that the lowest priority group is not on the
remotest valency, then we have to first bring this lowest priority group at the valency by exchange rule. One
mutual interchanging of the groups lead to reverse configuration and therefore to retain the given configuration
the double exchange is to be performed.

Thus, the give structure hs R configuration. Note that the top priority group is not to be necessarily on top
valency. We have to simply start the direction form top priority group.

Important : Note that the designation of a compound as R or S has nothing to do with the sign of rotation.
the Cahn-Ingold rule can be applied to any three dimensional representation of a chiral compound to determine
whether it is R or S only. For example in above case (i.e. lactic acid), R configuration is laevo rotatory is
designated as R-(–)-lactic acid. Now the other configuration of it will have opposite sign of rotation i.e. S-
(+)- lactic acid.

7. For the compounds containing more than one asymmetric carbon, again the same rules apply. Configuration
to each asymmetric carbon is assigned separately. Thus, to assign configuration to first asymmetric
carbon in (+)-tartaric acid, we have

CONFORMATIONS
• The different spatial arrangements of atoms which arise due to rotation around carbon-carbon single bond are
called conformations.

Conformation of Ethane
• Out of infinite number of possible conformations of ethane, the two extreme conformations are staggered
conformation and eclipsed conformation. The infinite intermediate conformations are known as skew
conformations.

• The Sawhorse projection formula of the two extreme conformations of ethane are shown in figure.
 (a) Staggered form (b) Eclipsed form

Staggered and Eclipsed conformations of ethane

• The Newman’s projection formula for staggered and eclipsed conformations of ethane are shown in figure.

I Staggered form Skew II Eclipsed

Newman’s projection formulae of conformations of ethane

Relative Stabilities of the Conformations of Ethane

The conformations of ethane do not have same stability. The staggered conformations is relatively more
stable than the other conformations. It is because the repulsive interactions between the H-atom attached to the
two carbon atoms are minimum due to the maximum distance between them. On the other hand, the eclipsed
conformation is associated with maximum energy because the repulsive interactions between
H-atomson adjacent carbon atoms are maximum due to minimum distance between them. The difference in the
energy content of staggered and eclipsed conformations is 12.5 KJ mol–1.
The variation of energy with rotation about the C–C bond in ethane has been shown in figure below :
Potential Energy

12.5

Rotation

Changes in energy during rotation about C–C bond in ethane

The difference in the energy of various conformers constitutes an energy barrier to rotation. The energy required
to rotate the ethane molecule about carbon-carbon single bond is called torsional energy. But this energy
barrier is not large enough to prevent the rotation. Even at ordinary temperature the molecules possess
sufficient thermal and kinetic energy to overcome the energy barrier through molecular collisions. Thus,
conformations keep on changing form one form to another very rapidly and cannot be isolated as separate
conformers.

• Torsional energy :-
The energy required to rotate the ethane molecule about ‘C–C’ bond is called torsional energy
Conformations of Butane
Butane molecule can be represented as derivative of ethane as given below :
Considering the rotation around single bond between C-2 and C-3 we get many conformations. Some of them
have been given as Newman Projections in figure.

60º 60º

I. Staggered (Anti) II. Eclipsed III. Staggered (Gauche)

60º

60º 60º

VI. Eclipsed V. Staggered (Gauche) IV. Fully Eclipsed

Conformations of Butane

Staggered conformations (I), in which methyl groups are as far apart as possible, is most stable due to minimum
repulsion between methyl groups. This conformations is also called anti conformations. This on rotation through
60º gives eclipsed conformations (II), in which methyl group on one carbon is overlapped by the hydrogen atom
on the other carbon.

Further rotation through 60º gives another staggered conformation (III). The conformation is also called gauche
conformation. Gauche conformation on further rotation through 60° gives fully elipsed conformation (IV).
(IV) in which methyl groups on two carbons are just opposite each other. In this conformations steric strain is
maximum hence this conformations is most unstable. Further rotation through 60º gives again gauche
conformations (V) which is mirror image of gauche conformation (III). Conformation (V), on rotation through 60º
gives conformation (VI) which is again eclipsed conformation.

The energy profile diagram for the conformation of butane is given below along with the difference of energy
between various conformation of butane.
 PART - I : SUBJECTIVE QUESTIONS

1. Calculate the number of aromatic 1°-amine isomers possible of toluidine

2. Calculate the number of aromatic isomeric amides possible of acetanilide

3. Calculate the number of isomeric ethers possible of

4. How many pair(s) of geometrical isomers are possible with C5H10 (only in open chain structure)
5. Total number of compounds with molecular formula C5H10 which can show geometrical isomerism are
(only cyclic) ?

6. How many enantiomers are possible on monochlorination of isopentane.

7. Find out the total number of cyclic isomers of C5H10 which are optically active ?

8. Calculate the total number of open chain isomeric compounds of molecular formula C4H8O which can
show geometrical isomerism.

9. How many stereoisomers exist for

(a) 3-methylcyclopentanol (ii) 1, 3-Cyclohexanediol ?

10. Total stereoisomers of a given compound are ?

(a) (ii)

11. Mark each chiral centre in the following molecules with an asterisk. How many stereoisomers are possible
for each molecule ?

(a) (b) (c) (d)

(e) (f) (g)

12. (a) Label the four chiral ceners in amoxicillin, which belongs to the family of semisynthetic penicillins.

(b) Mavacor is used clinically to lower serum cholesterol levels. How many chirality centers does Mevacor
have ?

13. Among the following how many compounds are chiral ?

(a) (b) (c) (d)

(e) (f) (g) (h)

14. Are the following structures chiral as drawn ? When placed in a solution at 298 K, which structure will show
an optical rotation ? Explain.

(a) (b) (c)

(d) (e) (f)

15. Which of the following compounds are chiral ? Which, if any, are meso ?

(a) (b) (c) (d)

16. Among of the following how many are meso compouds ?

(i) (ii) (iii)

(iv) (v) (vi)

(vii) (viii) (ix)

17. Among the following compounds how many has a stereoisomer that is a meso compound ?
(a) (i) 2, 3-dimethylbutane (ii) 2-bromo-2-methylpentane (iii) 1-bromo-2-methylcyclohexane
(b) (i) 3, 4-dimethylhexane (ii) 3,4-diethylhexane
(c) (i) 1,3-dimethylcyclohexane (ii) 1,4-dimethylcyclohexane (iii) 1,2-dimethylcyclohexane

18. How many compounds among the following have a stereoisomer that is achiral ?
(a) (i) 2,3-dichlorobutane (ii) 2,3-dichloropentane (iii) 2,3-dichloro-2,3-dimethylbutane
(b) (i) 1,2-dimethylcycobutane (ii) 1,3-dibromocyclobutane (iii) 1,3-dichlorocyclopentane
(iv) 1,2-dimethylcyclopentane
(c) 2,4-dibromopentane (ii) 2,3-dibromopentane (iii) 1,4-dimethylcyclohexane
19. Are the formulas with in each set identical, enantiomers or diastereomers ?

(a) (b)

(c)

20. Following are four Newman projection formula for tartaric acid.

(1) (2) (3) (4)

(a) Which represent the same compound ? (b) Which represent enantiomers ?
(c) Which represent a meso compound ? (d) Which are diastereomers ?
21. Following are stereorepresentations for the three, stereoisomers of 2, 3-butanediol. The carbons are
numbered beginning from the left, as show in (1).

(1) (2) (3)

(a) Assign an R or S configuration to each chiral centre (b) Which are enantiomers ?
(c) Which is the mesto compound ? (d) Which are diastereomers ?
22. Find out the total number of major product (including stereoisomers) are obtained in each of the following
reactions.
(i) (a) 1-butene + HCl  x (ii) 1-butene + HBr + peroxide  y
Find the value of (x + y) ?

peroxide
(ii) (a) + HBr  x (b) + HBr   y

Find the value of (x + y) ?

H
(iii) (a) CH3CH2CH2CH = CH2 + HCl  x (b) + H2O 
 y

(c) + HBr  z

Find the value of (x + y + z) ?

23. Find out the total number of major products (inculding stereoisomers) are obtained in each of the following
reactions.
(i) (a) cis-3-heptene + Br2  x (b) trans-3-heptene + Br2  y
(c) trans-3-hexene + Br2  z
Find the value of (x + y + z) ?

Br2 H2
(ii) (a)  x (b) 
 y
CH Cl2 2 Pt

Find the value of (x + y) ?

24. Find out the total number of major products (inculding stereoisomers) are obtained in each of the following
reactions.

H2 H2
(i) (a) 
 x (b) 
 y
Pt Pt

Pt
(c) + H2  z

Find the value of (x + y + z) ?

H2 Br2
(ii) (a) 
 x (b)  y
Pt CH2Cl2

Find the value of (x + y) ?

PART - II : OBJECTIVE QUESTIONS

1.

Number of chiral centers are :

(A) 1 (B) 2 (C) 3 (D) 4
2. In the given following compound find out the pair of enantiomers and diastereomers.

(A) 2, 2 (B) 2, 4 (C) 4, 4 (D) 4, 2

3. The molecule(s) that exist as meso structure(s)

(A) only M (B) both K and L (C) only L (D) only K

4. Which the following, a pair of resolvable configurational enantiomers is given by

(A) cis-1, 2-dimethylcyclohexane (B) cis-1,3-dimethylcyclohexame
(C) cis-1,4-dimethylcyclohexane (D) trans-1,3-dimethylcyclohexane

5. Write two of the following compounds are identical ?

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

(A) I & II (B) II & IV (C) III & IV (D) I & III

6. Which two of the following compounds are diastereomers ?

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

(A) I & II (B) II & IV (C) III & IV (D) I & III

7. Which of the following is properly classified as a meso compound ?

(A) (B) (C) (D)

8. Which two of the following compounds represents a pair of enantiomers ?

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

(A) I & II (B) II & III (C) III & IV (D) II & IV
9. Which of the following compounds is (S)–4–chloro–1–methylcyclohexene ?

(A) (B) (C) (D)

10. Which of the following compounds has two stereogenic centers (asymmetric carbons) ?

(A) (B) (C) (D)

11. The drawing on the right shows that trans-1,3-dichlorocyclohexane is chiral. Efforts to resolve this compounds
fail. Why ?

(A) the cis and trans isomers rapidly interconvert

(B) the compound is acutally a meso structure
(C) the chair conformers rapidly interconvert producing a recemic mixture.
(D) method for resolving alkyl chlorides are not availabl.

12. How many stereoisomers of (CH3)2CHCH=CHCH2CH(OH)CH2Br are possible ?

(A) 2 (B) 3 (C) 4 (D) 5

13. What kind of reagent would be needed to resolve a recemic amine, such as 2-aminobutane ?
(A) the pure optically active amine to serve as a reagent for crystallization
(B) an achiral carboxylic acid to give a recemic mixture of amine salts.
(C) an enantiomerically pure chiral carboxylic acid to give a diastereomeric mixture of amine salts.
(D) a recemic chiral carboxylic acid to give a complete mixture for isomeric amine salts.

14. What common symmetry elements if any are found in the stable chiar conformer of trans-1,2-
dichlorocyclohexane ?
(A) a single mirror plane and a C2 rotational axis
(B) a single mirror plane and a C3 rotational axis
(C) two orthogonal mirror planes and a C2 rotational axis
(D) a single C2 rotational axis but no mirror plane.

15. Which of the following structures represents a chiral compound ?

(A) (B)

(C) (D)
16. Examine the compound givrn below. How many stereoisomers having this compound constitution are possible
?

(A) 2 (B) 4 (C) 6 (D) 8

17. How many stereoisomers are possible for the following.

(A) 4 (B) 8 (C) 16 (D) 32

18. Which of the following heptanols are chiral-1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol.
(A) All are chiral (B) 2-heptanol and 3-heptanol
(C) 2-heptanol, 3-heptanol & 4-heptanol (D) 3-heptanol and 4-heptanol

19. How many stereoisomers are possible for the following compound ?

(A) 2 (B) 4 (C) 6 (D) 8

20. Which of the following will exhibit geometrical isomerism ?

(A) 1-phenyl-2-butene (B) 3-phenyl-1-butene (C) 3-phenyl-1-butene (D) 1,1-diphenyl-1-propene

21. Optical rotation produced by is 36° then that product by is

(A) –36° (B) 0° (C) +36° (D) unpredictable

22.

Relation between given pair is

(A) Enatiomer (B) Diastereomer (C) Identical (D) Structural isomer

23. Following eclipsed form of propene is repreated after rotation of

(A) 45° (B) 90° (C) 120° (D) 180°

24. are

(A) chain isomers (B) positional isomers (C) both (D) none

25. Dextrorotatory -pinene has a specific rotation []D20  51.3 . A sample -pinene containing both the

enantiomers was found to have a specific rotation value []D20  30.8 . The percentage of the (+) and
(–) enantiomers present in the sample are, respectively.
(A) 70% and 30% (B) 80% and 20% (C) 20% and 80% (D) 60% and 40%

26. (+)-mandelic acid has a specific rotation of 158°. What would be the observed specific rotation of a mixture
of 25% (–)-mandelic acid and 75% (+)-mandelic acid ?
(A) +118.5° (B) –118.5° (C) –79° (D) +79°

27. Number of structural isomers of compoud having molecular formula C4H7Cl.

(A) 4 (B) 8 (C) 12 (D) 16

28. Stereoisomers differ from each other in what respect ?

(A) Composition (B) Constitution (C) Configuration (D) Seric hindrance

29. Which of the following sugar has the configuration (2S, 3R, 4R) ?

(A) (B) (C) (D)

30. Which of the following statements must be true for two pure chiral isomers ?
(A) they must be enantiomers (B) they must be diastereomers
(C) they must be stereoisomers (D) they must be optically active
31. Which of the following statements is true for a pair of diastereomers ?
(A) they will have identical physical properties
(B) they will have specific rotations of opposite sign
(C) they will have identical chemical properties (e.g reactivity)
(D) they will have different physical properties

32. How many stereoisomer are possible for this natural occuring compound.

(A) 8 (B) 16 (C) 64 (D) 128

33. An optically pure compound X gave an []D25  20.0 . A mixture of X and its enantiomer Y gave

[]D25  10 . The ratio of X to Y in the mixture is

(A) 2 : 1 (B) 1 : 3 (C) 3 : 1 (D) 1 : 2

34. Molecular formula C3H6Br2 can have (including stereoisomers) :

(A) Two gem dibromide (B) One vic dibromide
(C) Two tertiary dibromo alkane (D) Two secondary dibromo alkane

35. The number of isomers of C5H10 is

(A) 10 (B) 11 (C) 12 (D) 13

36. Meso-tartaric acid and d-tartaric acid are

(A) positional isomers (B) enantiomers (C) diastereomers (D) racemic mixture
37. The number of isomers of C3H5Br3 is (including stereoisomers)
(A) 4 (B) 5 (C) 6 (D) 7

38. The number of optically active compounds in the isomers of C4H9Br is

(A) 1 (B) 2 (C) 3 (D) 4

39.

The compound with the above configuration is called:

(A) (2S, 3S)-2-chloro-3-pentanol (B) (2S, 3R)-2-chloro-3-pentanol
(C) (2R, 3R)-2-chloro-3-pentanol (D) (2R, 3S)-2-chloro-3-pentanol

40. The prefered conformation of trans-1,2-dibromocyclohexane is :

(A) diaxial (B) diequatorial (C) axial / equatorial (D) neither A, B nor C
41. How many stereoisomers of the following molecule are possible?
HOOC.CH=C=CH.COOH
(A) two optical isomers (B) two geometrical isomers
(C) two optical and two geometrical isomers (D) None

42. The structures shown here are related as being:

(I) (II)
(A) confermers (B) enantiomers
(C) geometrical isomers (D) diastereoisomers

43. Which of the following cannot be written in an isomeric form ?

(A) CH3–CH(OH)–CH2–CH3 (B) CH3–CHO
(C) CH2=CH–Cl (D) Cl–CH2CH2–Cl

44.

Which of the above formulae represent identical compounds?

(A) I and II (B) I and IV (C) II and IV (D) III and IV

45.

Which of the above compounds are enantiomers?

(A) II and III (B) III and IV (C) III and V (D) I and V
46.

The above compounds differ in

(A) configuration (B) conformation (C) structure (D) chirality

47. Which species exhibits a plane of symmetry?

(A) (B) (C) (D)

48. Number of possible 3D-isomers (Stereoisomer) of glucose are

(A) 10 (B) 14 (C) 16 (D) 20

49. The compounds C2H5OC2H5 and CH3OCH2CH2CH3 are

(A) chain isomers (B) geometrical isomers
(C) metamers (D) conformational isomers

50. Which of the following, compounds displays geometrical isomerism ?

(A) CH2 = CHBr (B) CH2=CBr2 (C) ClCH = CHBr (D) Br2C=CCl2

51. Match List-I with List-II and select the correct answer from the codes given below the lists :
List-I List-II

(P) and (1) Enantiomer

(Q) and (2) Position isomers

(R) and (3) Metamers

(S) and (4) Tautomers

(P) (Q) (R) (S) (P) (Q) (R) (S)

(A) 3 2 4 1 (B) 3 2 1 4
(C) 1 2 3 4 (D) 2 3 4 1
52. The number of optically active isomers observed in 2,3-dichlorobutane is:
(A) 0 (B) 2 (C) 3 (D) 4
53. How many total isomers are possible by replacing one hydrogens atoms of propane with chlorine
(A) 2 (B) 3 (C) 4 (D) 5

54. On chlorination of propane number of products of the formula C3H6Cl2 is

(A) 3 (B) 4 (C) 5 (D) 6
55. The two compounds given below are

(A) enantiomers (B) identical

(C) optically inactive (D) diastereomers

56. Which of the following will not show optical isomersim.

(A) Cl–CH=C=C=CH–Cl (B) C–CH=C=C=C=CH–Cl

(C) (D)

57. Given compound shows which type of isomerism

O O
S—O and S—O
O O
(A) Chain isomerism (B) Positional isomerism
(C) Metamerism (D) Functional group isomerism

O O
58. Cl C—O and C—O Cl
H CH3
C=C C=C
H CH3 H H
Shows which type of isomerism
(A) Functional group isomerism (B) Geometrical isomerism
(C) Metamerism (D) Position isomerism

59. Which conformer of cyclohexane is chiral

(A) Chair (B) Boat (C) Twisted boat (D) None of these

60. Which of following pair is diastereomers :

(A) (B)

(C) (D)
61. Sum of stereoisomer in given compound (a) and (b) are

a + b = ?
(A) 3 (B) 4 (C) 5 (D) 6

62.

equilibrium constant for above reaction is :

(A) K = 1 (B) K > 1 (C) K < 1 (D) K = 0

63.

Incorrect statement about this compound is :

(A) It shows geometrical isomerism (B) It posses centre of symmetry
(C) It process plane of symmetry (D) It shows optical isomerism

64. Minimum C atoms required for a compound to show geometrical isomerism :

(A) 2 (B) 3 (C) 4 (D) None of these

65.

Which of the following statement is correct ?

(A) I & II are conformational isomers while II & III are functional isomers
(B) I & II are functional isomers while II & III are conformational isomers
(C) I & II are functional isomers while I & III are conformational isomers
(D) None of the above

66. How many planes are present in nepthalene

(A) 1 (B) 2 (C) 3 (D) 6

67. Total number of optically active alkyne possible from molecular formula C3FCBrI
(A) 2 (B) 4 (C) 6 (D) 8

68. Total number of geometrical isomer of given compound will be

(A) 2 (B) 4 (C) 6 (D) 8

69.

Number of geometrical isomer of given compound will be

(A) 2 (B) 3 (C) 4 (D) 5

70. The number of steoisomers obtained by bromination of cis-2-butene is

(A) 1 (B) 2 (C) 3 (D) 4
71. The number of steoisomers obtained by reaction of cis-2-butene with bromine in the presence of water is
(A) 1 (B) 2 (C) 3 (D) 4

72. The number of steoisomers obtained by bromination of trans-2-butene is

(A) 1 (B) 2 (C) 3 (D) 4

73. The number of steoisomers obtained by bromination of 1-butene is

(A) 1 (B) 2 (C) 3 (D) 4

74. Isobutene + Br2  number of possible products

s
(A) 1 (B) 2 (C) 3 (D) 4

75. Statement-1 : This compound will show geometrical isomerism

Statement-2 : Terminal carbon groups are perpendicular to each other

(A) Statement-1 is true, Statement-2 is true, Statement-2 is correct explanation for statement-1
(B) Statement-1 is true, Statement-2 is true, Statement-2 is NOT a correct explanation for statement-1
(C) Statement-1 is true, Statement-2 is false.
(D) Statement-1 is false, Statement-2 is true.

76. Which of the following compounds is optically active ?

(A) 1-Bromobutane (B) 2-Bromobutane
(C) 1-Bromo-2-methylpropane (D) 2-Bromo-2-methylpropane

77. Which of the following operations on the Fischer formula does not change its absolute

configuration ?
(A) Exchanging groups across the horizontal bond
(B) Exchanging groups across the vertical bond
(C) Exchanging groups across the horizontal bond and also across the vertical bond
(D) Exchanging a vertical and horizontal group

78. Which of the following combinations amongst the four Fischer projections represents the same absolute
configurations ?

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

(A) (II) and (III) (B) (I) and (IV) (C) (II) and (IV) (D) (III) and (IV)

79.* In which of the following molecule show chirality.

(A) I is trans & chiral (B) II is trans & chiral (C) I is cis & chiral (D) II is trans & achiral
80.* Total number of stereoisomer is odd number for

(A) (B) (C) (D)

81.* Which of the following compounds is optically active ?

(A) (B)

(C) (D)

82.* C4H6O2 does represent.

(A) A diketone (B) A compound with two aldehyde
(C) An alkenoic acid (D) An alkanoic acid
83.* Which of the following statements is/are not correct ?
(A) Metamerism belongs to the category of structural isomerism
(B) Tautomeric structures are the resonating structures of a molecule
(C) Keto form is always more stable than the enol form
(D) Geometrical isomerism is shown only by alkenes

84.* Which of the following statements is/are correct ?

(A) A meso compound has chiral centres but exhibits no optical activity
(B) A meso compound has no chiral centres and thus are optically inactive.
(C) A meso compound has molecules which are superimposable on their mirror images even though they
contain chiral centres
(D) A meso compound is optically inactive because the rotation caused by any molecule is cancelled by an
equal and opposite rotation caused by another molecule that is the mirror image of the first.

85.* Which of the following statements is/are not correct for D-(+) glyceraldehyde ?
(A) The symbol D indicates the dextorotatory natural of the compound
(B) The sign (+) indicates the dextrorotatory nature of the compound
(C) The symbol D indicates that hydrogen atom lies left to the chiral centre in the Fischer projection diagram
(D) The symbol D indicates that hydrogen atom lies right to the chiral centre in the Fischer projection
diagram.

86.* Which of the following statements for a meso compound is/are correct ?
(A) The meso compound has either a plane or a point of symmetry
(B) The meso compound has at least one pair of similar stereocenters
(C) The meso compound is achiral
(D) The meso compound is formed when equal amounts of two enantiomers are mixed

87.* Which of the following compounds are optically active ?

(A) CH3.CHOH.CH2.CH3 (B) H2C=CH.CH2.CH=CH2

(C) (D)
88.* Which of the following will show optical isomerism as well as geometrical isomerism.

(A) (B) (C) (D)

89.* Which of the following are correct representation of L-amino acids

(A) (B) (C) (D)

90.* Which of the following are D-sugars :

(A) (B) (C) (D)

91.* The Fischer projection of the molecule as represented in the wedge edge.

(A) (B) (C) (D)

92.* Given compound shows which type of isomerism

and

(A) Chain isomerism (B) Positional isomerism

(C) Constitutional isomerism (D) None

99.* Which of the following having plane of symmetry.

(A) (B) (C) (D)

MATCH THE FOLLOWING
1. Match the Column
Column-I Column-II

(A) (P) Total number of stereoisomers is odd

for the structure

(B) (Q) Total number of stereoisomers is

even for the structure

(C) (R) Odd number of chiral centre

(D) (S) Even number of chiral centre centres.

2. Match the Column

Column-I Column-II

(A) (P) show optical isomerism

(B) (Q) show geometrical isomerism

(C) (R) Resolvable

(D) (s) non-resolvable

3. Match the Column
Column-I Column-II

(A) (P) Position isomers

(B) (Q) Enantiomers

(C) (R) Diastereomers

(D) (S) Identical

4. Match the Column

Column-I Column-II

(A) (P) Total number of stereoisomers are odd

(B) (Q) Total number of stereocenter are even

or have centre of symmetry

(C) (R) Compounds having plane of symmetry

or axis of symmetry

(D) (S) Compounds have zero dipole in given

form
5. Match the Column
Column-I Column-II

(A) (P) Structural isomer

(B) (Q) Identical

(C) (R) Enantiomers

(D) (S) Diastereomers

COMPREHENSION
Comprehension # 1
If a molecule contains one carbon atom carrying four different groups it will not have a plane of symmetry
and must therefore be chiral. A carbon atom carrying four different groups is a stereogenic or chiral centre.
A structure with a plane of symmetry is achiral and superimposable on its mirror image and cannot exist as
two enantiomer. A structure without a plane of symmetry is chiral and not superimposable on its mirror
image and can exist as two enantiomer.

6.

Number of enantiomers pairs are

(A) 2 (B) 4 (C) 8 (D) 10

7.

Relation between (a) & (b) is

(A) Enantiomer (B) Diastereomer (C) Identical (D) Structural isomer

8. Compound has both center of symmetry and P.O.S.

(A) (B) (C) (D)

FILL IN THE BLANKS
9. Determine if the following pairs are identical, isomers, enantiomers or diasteromers.

(i) ___________________

(ii) ___________________

(iii) ___________________

10. Determine if the following pairs are identical, isomers, enantiomers, or diastereomers.

(i) ___________________

(ii) ___________________

(iii) ___________________

11. Classify each of the following pairs of structures as :

I. Identical E. Enantiomers D.Diastereomers

(a)

(b)

(c)
12. Classify each of the following pairs of structures as :
I. Identical E. Enantiomers D.Diastereomers

(a) (b)

(c) (d)

(e)

13. State the relationship between each of the following five (5) pairs of structures (identical , enantiomers,
diasteromers, structural isomers, different compounds that are not isomeric).

(a) ___________________

(b) ___________________

(c) ___________________

(d) ___________________

(e) ___________________
14. State the relationship between each of the following five (5) pairs of structures (identical , enantiomers,
diasteromers, structural isomers, different compounds that are not isomeric).

(a) ___________________

(b) ___________________

(c) ___________________

(d) ___________________

(e) ___________________

15. Select chiral molecule out of the following list of compounds.

(i) (ii) (iii)

(iv) (v)
16. Discuss the optical activity of the following two compounds and also label them as polar and non polar.

(i) (B)

17. Match the column :

Column A Encircle the words Column B Encircle the words that

that describe the best describes the
molecule in relationship between the
column A molecule of columns A & B

(a) chiral, achiral, (a) enantiomers, diastereomers,

meso, none of these identical, none of these

(b) chiral, achiral, (b) enatiomers, diastereomers,

meso, none of these identical, none of these

(c) chiral, achiral, (c) enatiomers, diastereomers,

meso, none of these identical, none of these

(d) chiral, achiral, (d) enatiomers, diastereomers,

meso, none of these identical, none of these

18. A cyclobutandicarboxylic acid exist in two stereo-isomeric forms in which one is polar but non-resolvable
while other is non-polar but resolvable into enantiomers. Deduce structures of all these compounds.

19. How many isomers are possible for nitrophenol ?

20. A compound with molecular formula C4H10O, can show metamerism, functional isomerism and positional
isomerism. Justify the statement with the help of structures.

21. Calculate the total number of stereoisomers in the following compounds.

(i) (ii) (iii)

22. In what stereoisomeric forms would you expect the following compounds to exist ?

(a) EtCH(CO2H)Me (b) MeCH(CO2Et)CO2H (c)

(d) (e) (f) Et(Me)C=C=C(Me)Et

(g) (h) (i)

(j) (k)

23. With reasons, state whether each of the following compounds I to VII is chiral

(i) (ii) (iii)

(iv) (v) (vi)

24. Considering rotation about the C–3–C–4 bond of 2-methylhexane :

(a) Draw the Newman porjection of the most stable conformer
(b) Draw the Newman projection of the least stable conformer.

25. Determine whether each of the following compounds is a cis isomer or a trans isomer.

(a) (b) (c)

(d) (e) (f)

26. An object that has no element of symetry of called what ?

(A) tetrahedral (B) achiral (C) symmetric (D) asymmetric

27. Draw all the possible stereoisomers of 3-pentene-2-ol.

 EXERCISE # 1
PART - I
1. 4 2. 9 3. 5 4. 1 5. 1 6. 2 7. 2

8. 2 9. (a) 4 (b) 3 10. (a) 16 (b) 4

11. (a) 4 (b) 4 (c) 2 (d) 8 (e) 4 (f) 4 (g) 4

12. (a) 4 (b) 8 13. 3 14. 2 15. chiral  a, b ; meso  c

16. 5 17. (a) 0 (b) 1 (c) 2 18. (a) 2 (b) 4 (c) 2

19. (a) enantiomers (b) enantiomer (c) diastereomers

20. (a) 3 & 4 (b) 1 & 3 (c) 2 (d) 1 & 2, 2 & 3, 2 & 3
21. (a) 2R 3R, 2R 3S, 2S 3S (b) 1 & 3 (c) 2 (d) 1 & 2 ; 2 & 3

22. (i) 3 (ii) 3 (iii) 5 23. (i) 5 (ii) 4

24. (i) 5 (ii) 3

PART - II
1. (B) 2. (B) 3. (B) 4. (D) 5. (B) 6. (D) 7. (A)

8. (C) 9. (A) 10. (D) 11. (C) 12. (C) 13. (C) 14. (D)

15. (D) 16. (D) 17. (C) 18. (B) 19. (D) 20. (A) 21. (B)

22. (C) 23. (C) 24. (A) 25. (B) 26. (D) 27. (C) 28. (C)

29. (C) 30. (D) 31. (D) 32. (C) 33. (C) 34. (A) 35. (D)

36. (C) 37. (C) 38. (B) 39. (A) 40. (B) 41. (A) 42. (D)

43. (C) 44. (B) 45. (C) 46. (C) 47. (D) 48. (C) 49. (C)

50. (C) 51. (A) 52. (B) 53. (A) 54. (C) 55. (A) 56. (B)

57. (C) 58. (C) 59. (C) 60. (B) 61. (C) 62. (B) 63. (B)

64. (D) 65. (D) 66. (C) 67. (D) 68. (B) 69. (C) 70. (B)
71. (B) 72. (A) 73. (B) 74. (A) 75. (D) 76. (B) 77. (C)

78. (C) 79.* (AD) 80.* (ABC) 81.* (BC) 82.* (ABC) 83.* (BCD) 84.* (AC)

85.* (AD) 86.* (ABC) 87.* (ACD) 88.* (ACD) 89.* (ACD) 90.* (ACD) 91.* (AC)
92.* (BC) 99.* (ABCD)
EXERCISE # 2
1. (A)  Q, S ; (B)  Q, S ; (C)  P, S ; (D)  Q, R

2. (A)  P, R ; (B)  S ; (C)  P, R ; (D)  P, Q, S 3. (A)  R ; (B)  P ; (C)  S ; (D)  S

4. (A)  P, Q, R ; (B)  Q, R, S ; (C)  Q, R, S ; (D)  P, Q, R

5. (A)  P ; (B)  R ; (C)  Q ; (D)  R 6. (B) 7. (B) 8. (D)

9. (i) Diasteromers (ii) Enantiomers (iii) Identical

10. (i) Identical (ii) Diasteromers (iii) Diasteromers

11. (a) E (b) D (c) I

12. (a) E (b) I (c) D (d) I (e) E

13. (a) Diasteromers (b) Diasteromers (c) Different compound (d) Structure isomers
(e) Enantiomers

14. (a) Diasteromers (b) Not isomer (c) Enantiomers (d) Structural isomers
(e) Identical
15. (i) achiral (ii) achiral (iii) chiral (iv) chiral
(v) achiral

16. Compound I is optically inactive since it contain a plane of symmetry. Compound II is enantiomeric since it
does not contain plane of symmetry, hence chiral. Also compound I is polar while II is non polar.

17. (A) Column (a) chiral (b) chiral (c) meso (d) chiral
(B) Column (a) enantiomers (b) enantiomers (c) diastereomers (d) diastereomers

18. The compound must be 1,2-cyclobutan-dicarboxylic acid since all other constitutional isomers are non-
resovable.

19. 3

20. (i) Et–O–Et, (ii) CH3–O–CH2–CH2–CH3, (iii) CH3–CH2–CH2–CH2–OH. (iv)

I & II metamers, I & III functional isomers, III & IV position isomers.

21. (I) 4, (II) 3, (III) 4

22. Optical : a, b, c, d, f, g, i, k ; Geometrical isomer : c, g, j ; None : e, h

23. achiral : I, III ; chiral : II, IV, V, VI

24. (a) (b)

25. (a) cis (b) cis (c) cis (d) trans (e) trans (f) trans

26. (D)

27. Total 4
 EXERCISE - 3 : PREVIOUS YEAR JEE MAINS QUESTIONS
1. The optically inactive compound from the following is chromatography.
(2015) (d) Stationary phase is a finally divided solid absorbent.
(a) 2-chloropropanal (b) 2-chloropentane Ans. (a)
(c) 2-chlorobutane (d) 2-chloro-2-methylbutane Sol. Mobite phase is liquid
Ans. (d)
Cl 5. The configuration of the chiral centre and the geometry of
Sol. the double bond in the following molecule can be described
| by Online 2016 SET (1)
CH 3  C  CH 2  CH 3
|
CH 3

2. The number of structural isomers for C6H14 is :

Online 2015 SET (1)
(a) 4 (b) 3
(c) 6 (d) 5
Ans. (d)
Sol. (a) R and E (b) S and E
(c) R and Z (d) S and Z
Ans. (c)
Sol. Geometry of double bond
F

HOOC 1
C OH Me
1
C C 'Z'
3. Match the organic compounds in column-I with the
Lassaigne’s test results in column-II appropriately : 2 H 2
Column-I Column-II Me
(A) Aniline (i) Red colour with
FeCl3
(B) Benezne sulfonic (ii) Violet colour with
acid sodium nitroprusside
(C) Thiourea (iii) Blue colour with
hot and acidic
solution of FeSO4
Online 2015 SET (1)
(a) A– (ii); B– (iii); C– (i) (b) A– (iii); B– (i); C– (ii)
(c) A– (iii); B– (ii); C– (i) (d) A– (ii); B– (i); C– (iii)
Ans. (c)
Sol. Aniline  blue colour with hot and acidic solution of FeSO4.
Benzene Sulphonic acid  violet colour with sodium
6. The “N” which does not contribute to the basicity for the
nitroprusside
compound is : Online 2016 SET (2)
Thiourea  Red colour with FeCl3

4. Which of the following statements is not true about

partition chromatography ? (2016)
(a) Mobile phase can be a gas.
(b) Separation depends upon equilibration of solute
between a mobile and a stationary phase.
(c) Paper chromatography is an example of partition

(a) N 7 (b) N 9
 (c) N 1 (d) N 3
Ans. (b)
6 7
Sol. 5
1 N
N
8
Involve in resonance
Online 2017 SET (1)
2 4
N N 9 (a) 1, 1-Dimethyl-2-ethylcyclohexane
3 H (b) 2-Ethyl-1, 1-dimethylcyclohexane
(c) 1-Ethyl-2, 2-dimethylcyclohexane
7. Which of the following compounds will be suitable for (d) 2, 2-Dimethyl-1-ethylcyclohexane
Kjeldahl's method for nitrogen estimation ? (2017) Ans. (b)

(a) (b) Sol.

11. Which of the following compounds is most reactive to an

aqueous solution of sodium carbonate ?
(c) (d) Online 2017 SET (2)

Ans. (d) (a) (b)

Sol. Kjedohl’s method suitable for estimation of nitrogen in
aniline but it is not used for pyridine nitro and azo
compounds.
8. The number of geometrical isomers in the following
compound
(c) (d)
CH3—CH=CH—CH=CH—C2H5 is
Online 2017 SET (1)
(a) 4 (b) 3 Ans. (c)
(c) 2 (d) 5
Ans. (a)
Sol.

Sol. Compound (C) is most reactive towards aqueous solution

of sodium carbonate because it is most acid among given
let of compounds. The main cantre of the acidity is that
the anion formed after the removal of proton from
compound is aronoatic

9. Which of the following statements is not true about

partition chromatography ?
Online 2017 SET (1) 12. In the following structure, the double bonds are marked
(a) Mobile phase can be a gas as I, II, III and IV
(b) Stationary phase is a finely divided solid adsorbent
(c) Separation depends upon equilibration of solute
between a mobile and a stationary phase
(d) Paper chromatography is an example of partition
chromatography
Ans. (a)
Sol. Mobile phase is in liquid form.
10. The IUPAC name of the following compound is :
 (a) (I) < (II) < (IV) < (III) (b) (I) < (II) < (III) < (IV)
Geometrical isomerism is not possible at site (s) :
(c) (II) < (I) < (IV) < (III) (d) (II) < (I) < (III) < (IV)
Online 2017 SET (2)
Ans. (c)
(a) III (b) I
(c) I and III (d) III and IV
Ans. (b)
II Sol.
Sol.

III

IV

Not possible
geometrical isomerism

because on one side of double bond there are similar

groups.

13. Which of the following compounds will show highest

dipole moment Online 2017 SET (2)

(III) > (IV) > (I), (II)

15. The IUPAC name of the following compound is :
Online 2018 SET (1)

(a) I (b) II
(c) III (d) IV
Ans. (d)
(a) 4-methyl-3-ethylhex-4-ene
Sol. + - (b) 3-ethyl-4-methylhex-4-ene
O O (c) 4-ethyl-3-methylhex-2-ene
(d) 4, 4-diethyl-3-methylbut-2-ene
Ans. (c)
Aromatic
14. Among the following compounds, the increasing order of
their basic strength is : Online 2017 SET (2)
Sol. Ans. (c)
Sol. (C2H5)2 NH > C2H5NH2 > NH3
20 amine 10 amine ammonia
This order due to electron donating gronp  es basic
strength.
19. Which of these factors does not govem the stability of a
conformation in acyclic compounds ?
(2019-04-10/Shift-2)
(A) Torsional strain (B) Angle strain
16. Two compounds I and II are eluted by column (C) Steric interactions (D) Electrostatic forces of
chromatography (adsorption of I > II). Which one of interaction
following is a correct statement ? Ans. (b)
Online 2018 SET (2) Sol. Angle strain govern stability in cyclic compound.
(1) I moves faster and has higher Rf value than II 20. In the following skew conformation of ethane, H'–C–C–H"
(2) II moves faster and has higher Rf value than I dihedral angle is : (2019-04-12/Shift-2)
(3) I moves slower and has higher Rf value than II
(4) II moves slower and has higher Rf value than I
Ans. (b)
Sol. Two compounds (i) and (ii) are eluted by column
chromatography (adsorption of I > II). So (II) moves faster
and has higher Rf value than (I).
17. The increasing order of the acidity of the following
carboxylic acids is : Online 2019 SET (1)

(A) 58 (B) 120

(C) 149 (D) 151
Ans. (c)
Sol. Dihedral angle is then angle between bond pairs present
on adjacent atoms.

(a) I<III<II <IV (b) IV <II< III<I

(c) II<IV <III<I (d) III<II <IV <I
Ans. (d)
Sol.
COOH COOH COOH COOH

H ' C  C  H '
Hence angle between
NO2 OH Cl H ' C  C  H"
–I × –I –I (120  29)  149
–R × +R +R
(I<R) (I<R) (I>R) 21. Among the following compounds, geometrical
(I) (II) (III) (IV) isomerism is exhibited by :
So (I) > (IV) > (II) > (III)
(2020-09-05/Shift-2)
18. In the following compounds, the decreasing order of basic
strength will be : Online 2019 SET (3)
(a) C2H5NH2 > NH3 > (C2H5)2 NH
(b) NH3 > C2H5NH2 > (C2H5)2 NH
(c) (C2H5)2 NH > C2H5NH2 > NH3
(d) (C2H5)2 NH > NH3 > C2H5NH2
 (a) (b)

(c) (d)

Ans : (a & b)
Sol :
 EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION
Objective Questions (Only one correct option) Ans. (d)

1. Which of the following compounds will exhibit geometrical

isomerism ? (2000) Sol.
(a) 1–phenyl–2–butene (b) 3–phenyl–1–butene
(c) 2–phenyl–1–butene (d) 1, 1–diphenyl–1–propene Has a chiral carbon, optically active.
Ans. (a)
5.

Sol.

C2 is rotated clockwise 120° about C2––C3 bond. The

2. Identify the pairs of enantiomers and diastereomers from resulting conformer is (2004)
the following (2000) (a) partially eclipsed (b) eclipsed
(c) gauche (d) staggered
Ans. (c)

Sol.

Sol. I and III are mirror images of one another as well as they
are non-superimposable while II is a meso form.

6. obs   i x i
3. The number of isomers for the compound with molecular where i is the dipole moment of stable conformer and xi is
formula C2BrCFI is (2001) the mole fraction of that conformer.
(a) 3 (b) 4
(a) Write stable conformer for Z – CH2 – CH2 – Z in
(c) 5 (d) 6
Newman’s projection.
Ans. (d)
If solution = 1.0D and mole fraction of anti form = 0.82,
F Cl F I
+ Geometrical isomers find gauche
Sol. C=C C=C
(b) Write most stable meso conformer of (CHDY)2
Br I Br Cl
If (i) Y = CH3 about C2–C3 rotation and
F Br F I
(ii) Y = OH about Cl-C2 rotation. (2005)
C=C + C=C Geometrical isomers
Cl I Cl Br
F Br F I
C=C + C=C Geometrical isomers
Cl I Cl Br Sol.

4. Which of the following compounds exhibits, stereoisomerism ?

(2002)
(a) 2–Methyl But–1–ene Mole fraction of anti form = 0.82
(b) 3–Methyl But–1–yne Mole fraction of gauche form = 0.18
(c) 3–Methyl Butanoic Acid
(d) 2–Methyl Butanoic Acid obs =1D
 Sol. Molecules that are non-superimposable on its mirror image
 1 =  anti  0.82  +  gauche  0.18 
are optically active and known as chiral molecule. However,
 anti = 0
for chirality of molecule, presence of chiral centre is not
 1=gauche  0.18 essential, e.g.

1
 gauche = =5.55D
0.18

Molecule is chiral but does not possesses any chiral

carbon.
9. The number of isomers of C6H14 is ( 2007)
(a) 4 (b) 5
Structure (ii) is more stable than its anti conformer because (c) 6 (d) 7
Ans. (b)

of intramolecular H - bonding.
Sol.
7. The number of stereoisomers obtained by bromination of
trans-2-butene is (2007)
(a) 1 (b) 2
(c) 3 (d) 4
Ans. (a)

Sol.

10. The correct statement(s) about the compound given below

is (are) (2008)

(a) the compound is optically active

(b) the compound possesses centre of symmetry
(c) the compound possesses plane of symmetry
(d) the compound possesses axis of symmetry
8. Statement–1 : Molecules that are non-superimposable Ans. (a,d)
on their mirror images are chiral. (2007) Sol. The compound is optically active as well as it possesses a
Statement–2 : All chiral molecules have chiral centres. two-fold axis of symmetry.
(a) Statement–1 is True, Statement–2 is True; Statement–2
is a correct explanation for Statement–1. 11. The correct statement(s) concerning the structures E, F
(b) Statement–1 is True, Statement–2 is True; Statement–2 is and G is (are) (2009)
not a correct explanation for Statement–1.
(c) Statement–1 is True, Statement–2 is False.
(d) Statement–1 is False, Statement–2 is True.
Ans. (c)
 (a) E, F and G are resonance structures
(b) E, F and E, G are tautomers
(c) F and G are geometrical isomers
(d) F and G are diastereomers
Ans. (b,c,d)
Sol. E, F and G are not resonance structures because movememt
of hydrogen between E and F are involved.
E, F and E, G are tautomers in which E is keto form and
both F and G are enol form of the same E.
F and G are geometrical isomers.

12. Give the total number of cyclic structural as well as stereo

isomers possible for a compound with the molecular
formula C5H10. (2009) Sol.

Sol.

Total six isomers. In both cis and trans forms, there are two
enantiomers each.

14. The correct order of acidity for the following compounds

is (2013)

 Total seven isomers

13. The correct statement (s) about the compound
H3C(HO) HC–CH=CH–CH(OH)CH3 (X) is (are)
(2009)
(a) The total number of stereoisomers possible for X is 6. (a) I > II > III > IV (b) III > I > II > IV
(b) The total number of diastereomers possible for X is 3. (c) III > IV > II > I (d) I > III > IV > II
(c) If the stereochemistry about the double bond in X is Ans. (a)
trans, the number of enantiomers possible for X is 4. Sol. Duo to ortho effect in (i) it is more acidic than others Acidic
(d) If the stereochemistry about the double bond in X is
cis, the number of enantiomers possible for X is 2. 1
strength  – I, – M, +
Ans. (a,d) M
COOH COOH
COOH
HO OH OH

OH
orthro less ortno
effect effect –I
(I) (II) (III)
 COOH

18. Newman projections P, Q, R and S are shown below :

OH
–I and +R
(I) > (II) > (III) > (IV)

15. The IUPAC name(s) of the following compound is (are)

(2017)

Which one of the following options represents

(a) 4-chlorotoluene identical molecules ? (2020/Shift-1)
(b) 4-methylchlorobenzene (a) P and Q (b) Q and S
(c) 1-chloro-4-methylbenzene (c) Q and R (d) R and S
(d) 1-methyl-4-chlorobenzene Ans : (c)
Ans. (a,c)
Sol :

Sol. CH 3 Cl

4–chlorotoluene/ 1–chloro –4–methylbenzene

16. (a) Draw Newman’s projection for the less stable staggered
form of butane.
(b) Relatively less stability of the staggered form is due to
(i) Torsional strain
(ii) van der Waals’ strain
(iii) Combination of the above two

Sol.

The less stability of above mentioned comformer is due to

van der Waals’ repulsion between the adjacent methyl
groups.

17. Total number of isomers considering both structural

and stereoisomers, of cyclic ethers with the molecular
formula C4H8O is__________ (2019/Shift-2)
Ans : 10.00
Sol :
 (2020/Shift-1)
(a) P  2, Q  3, R  2, S  2

(b) P  3, Q  1, R  1, S  2

(c) P  2, Q  1, R  1, S  3

(d) P  2, Q  3, R  3, S  1

Ans : (c)

Sol :

Q and R is same.
19. The Fischer projection of D-erythrose is shown below.

D-Erythrose and its isomers are listed and P, Q, R, and

S in Column-I. Choose the correct relationship of P, Q,
R and S with D-erythrose from Column-II.
 (c) –NO2 is –I group (electron withdrawing
group). It increases acid strength.
(d) Acid strength order : IV > V > I > II > III
21. Consider the following four compounds I, II, III, and IV.
20. With respect to the compounds I-V, choose the
correct statement(s).

Choose the correct statement(s). (2020/Shift-2)

(a) The order of basicity is II > I > III > IV.
(b) The magnitude of pK b difference between I and II
(a) The acidity of compound I is due to delocalization
is more than that between III and IV.
in the conjugate base.
(c) Resonance effect is more in III than in IV.
(b) The conjugate base of compound IV is aromatic.
(d) Steric effect makes compound IV more basic than
(c) Compound II becomes more acidic, when it has a –
III.
NO2 substituent.
Ans : (c,d)
(d) The acidity of compounds follows the order
Sol :
I > IV > V > II > III. (2020/Shift-1)
Ans : (a,b,c)
Sol :

pKb different between I and II is 0.53 and that of III

and IV is 4.6.
So option (B) is incorrect
Correct Statement (C), (D)
The most basic compound in the given option is (II)
and least basic compound is (III)
In 2,4,6-trinitro aniline (III) due to strong –R effect
of  NO 2 groups, the .p. of  NH 2 is more
involved with benzene ring hence it has least basic
strength.
Whereas (IV) N,N-Dimethyl 2,4,6-trinitro aniline, due
to steric inhibition to resonance (SIR) effect; the lone
pair of nitrogen is not in the plane of benzene, hence
make it (.p.) more free to protonate.