Net Material PDF

CSIR-NET
Chemical Sciences (CH)

SAMPLE
Eduncle.com For Counselling

MPA 44, 2nd Floor, Rangbari Main Road, Contact Us : 9829489592
Mahaveer Nagar 2nd, Kota Email : info@eduncle.com
Rajasthan, 324005 Visit Us : www.eduncle.com
Organic Chemistry-I
1. IUPAC NOMENCLATURE OF ORGANIC COMPOUNDS
The simplest organic compounds containing carbon and hydrogen only are called hydrocarbons
and when combined with a hetero atom are called hydrocarbon derivatives. The properties of an organic
compound chiefly depend upon the presence of functional group which contains a hetero atom (O, N,
S, X, etc). Each homologous series containing a specific functional group show similar properties.
Organic compounds are named by the rules quoted by IUPAC (International Union of Pure and Applied
Chemistry).
Naming of Organic Compounds
The International Union of Pure and Applied Chemistry (IUPAC) system of naming is primarily
based on :
1. Word root
2. Suffix (primary and secondary)
3. Prefix (primary and secondary)
Word Root
The number of carbon atoms present in the longest chain of the compound is the basis of word root.
Table : Word Root for Different Carbon Chains
Length of Chain Word Root Length of Chain Word Root
C1 Meth C10 Dec
C2 Eth C11 Undec
C3 Pr op C12 Dodec
C4 But C13 Tridec
C5 Pent C20 Eicos
C6 Hex C21 Heneicos
C7 Hept C22 Doicos
C8 Oct C30 Triacont
C9 Non C31 Hentriacont
Suffix
Primary suffix indicates the unsaturation in carbon chain. e.g.,
Unsaturation Primary Suffix
C–C ane
C=C ene
CC yne
If the parent chain contains two or more double bonds then the numerical prefixes like di, tri, tetra
etc., are added before the primary suffix. e.g.,
For two = bonds : diene
For three = bonds : triene
For two  bonds : diyne
For three  bonds : triyne
Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 1

Chemical Sciences - CH (Organic Chemistry-I)
The secondary suffix indicates the functional group present in the organic compound. e.g.,
Functional Group Secondary Guffix
Alcohol (–OH) ol
Aldehyde (–CHO al
Prefix : In case of cyclic compounds, the primary prefix, cyclo is added before the word root of
the parent chain of the compound. e.g.,
Cyclopropane
The secondary prefixes indicate the substitution of groups (other than functional group) in place
of hydrogen atoms in the compound. e.g.,
Atom/Group Name
–F Fluoro
–Cl Chloro
–OCH3 Methoxy
Some suffix and prefix for functional groups are given in Table.
Table : Suffix and Prefix for Functional Groups

General Rules for IUPAC Nomenclature of Organic Compounds

Nomenclature of Saturated Hydrocarbons (Alkanes)
1. Selection of the longest carbon chain which is called parent chain.
2. Number of the carbon atoms in the parent chain as 1, 2, 3... etc., starting from the end
which gives smaller number to the carbon atoms carrying the substituent.
When two or more substituents attached to the parent chain, then the end of the parent
chain which gives lowest set of the locants is preferred for numbering.
3. If two or more substituents are present on the parent chain, they are named in the
alphabetical order. If more than one locants of similar types are present at the same or
different position di, tri, tetra etc., are prefixed before the locants.
6-ethyl-2, 4-dimethyl nonane

(not 2, 4-dimethyl-6-ethylnonane)
4-ethyl-2, 3, 6, 6, 8-pentamethyl-5-propylnonane
(not 6-ethyl-2, 4, 4, 7, 8-pentamethyl-5-propylnonane)
4. When two different alkyl locants are equidistant from the two ends of main chain, they are
numbered in alphabetical order as
3-ethyl-7-methylnonane (not 3-methyl-7-ethylnonane)

4-ethyl-7-propyldecane (not 7-ethyl-4-propyldecane)

Note : When the same complex substituents occur more than once, it is indicated by multiplying
prefix bis, tris, tetrakis etc.
5, 5-bis (1, 1-dimethylpropyl) 2-methyldecane

Nomenclature of Unsaturated Hydrocarbons (Alkenes and Alkyne)
1. The longest chain determined must have multiple bond.
2. The suffix ‘ane’ of the corresponding alkane is replaced by ‘ene’ and ‘yne’ for double and
triple bonds respectively.
3. If a compound contains two or more double bonds or triple bonds, the letter ‘a’ should be
added to word root.
2, 4-heptadiene
1, 3, 5-octatriene
2, 4, 6-octatriyne
4. The numbering of atoms in parent chain is done in such a way that the carbon atom
containing the = bond or  bond gets the lowest number..
5. Unsaturated unbranched acyclic hydrocarbons, having both double and triple bonds are
named by replacing ending “ane” from the name of the corresponding saturated
hydrocarbons by “enyne”, “adienyne”, “atrienyne” “enediyne” etc. Numbers as low as

possible are given to double and triple bonds even though at this time gives “yne” a lower
number than “ene”.
1, 3-hexadien-5-yne 3-penten-1-yne
6. When there is a choice in numbering between double and triple bond (this occur when
double and triple bonds are equidistant from the two terminal), the double bonds are given
lowest number (ene comes before yne in alphabetical order).
1-penten-4-yne
7. All the rules for naming the substituent are same as that of alkane.
Nomenclature of Compounds Containing Functional Group
1. Select the longest continuous chain containing the carbon atom having the functional
group.
2. The numbering of atoms in the parent chain is done in such a way that the carbon atom
bearing the functional group gets the lowest number.
2, 2-dimethylpropan-1-ol 2, 4,4-trimethylpentan-1-ol
Note : The functional group should get the lowest number even if it violates the lowest
set rule or lowest sum rule.
3. The functional groups such as –CHO, –COOH, –CONH2, –CN etc., always start the
numbering of the parent chain.
4. All the rules for naming the substituents are same as that of alkane.
5. If a compound contains several functional groups, the senior most functional group will be
considered as a principal functional group (suffix) while all other groups should be treated
as prefix. The order for preference of principal functional group is :
Sulphonic acid > carboxylic acids > acid anhydrides > esters > acid chlorides > amides > nitriles
> aldehydes > ketones > alcohols > amines > ethers.
All the remaining groups such as halo, nitro, nitroso and alkoxy are always treated as substituent
groups.
Some examples of compounds containing more than one type of functional groups.
5-oxohexanoic acid
6-oxohexanoic acid 3-formyl-6-oxononanoic acid

Nomenclature of Alicyclic Compounds

1. The name of the alicyclic compound is obtained by adding the prefix cyclo to the name
of the corresponding straight chain hydrocarbon (alkane, alkene or alkyne).
2. If only one substituent is present, it is not necessary to designate its position. If two or
more substituents are present in the ring, their positions are indicated by arabic numerals
(1, 2, 3, 4...) while numbering the ring the substituent which comes first in alphabetical
order is given the lowest number and the ring is numbered in the direction that gives the
next substituent the lowest number possible. When three or more substituents are present,
we begin from the substituent which leads to the lowest set of locants.
1-ethyl-3-methylcyclohexane
(not 1-ethyl-5-methyl cyclohexane)
4-chloro-2-ethyl-1-methylcyclohexane
(not 1-chloro-3-ethyl-4-methylcyclohexane)
3. When a single ring system is attached to a single chain with a greater number of carbon
atoms, or when more then one ring system is attached to a single chain, then they are
named as cycloalkylalkane.
1-cyclobutylpentane 1, 3-dicyclohexylpropane
4-cyclopropyl-3-methyloctane5-cyclobutyl-1-pentyne or 5-cyclobutylpent-1-yne

Nomenclature of Bicyclic Compounds

Cycloalkanes consisting of two rings only and having two or more atoms in common are named
by taking the prefix bicyclo followed by the name of the alkane. In between bicyclo and alkane, number
of carbon atoms representing the bridge (except bridge head positions) are written within bracket. The
carbon atoms common to both the ring are called bridgeheads and each bond or chain of atoms
connecting the bridgehead atoms is called a bridge.
If substituents are present, we number the bridged ring system beginning at one bridgehead,
proceeding first along the longest bridge to the other bridgehead, then along the next longest bridge back
to the first bridgehead. The shortest bridge is numbered last.
Nomenclature of Spiro Compounds

Two rings with one common atom–spiro ring system.
The ring system in spiro compounds is indicated by the word “spiro” (instead of “cyclo”), followed
by brackets indicating how many atoms are contained in each path around the rings, ending with the
alkane name describing how many carbons are in the ring systems including the spiro carbon. Numbering
follows the smaller path first, passing through the spiro carbon and around the second ring.

Substituents and functional groups are indicated in the usual ways. Spiro ring systems are always
numbered smaller before larger, and numbered in such a way so as to give the highest priority functional
group the lower position number.
IUPAC Nomenclature of Aromatic Compounds

Substituted aromatic hydrocarbons
Following names for the substituted monocyclic aromatic hydrocarbons are retained.
Other monocyclic substituted hydrocarbons are named as derivatives of benzene or one of the
compounds listed above. However, if the substituent introduced into such a compound is identical with
already present in that compound, then the substituted compound is named as derivatives of benzene
as :
The positions of substituents are indicated by numbers except o-(ortho), m-(meta), p-(para) may
be used in place of 1, 2-, 1, 3- and 1, 4-respectively, when only two substituents are present. The lowest
possible number given to the substituent coming first in alphabetical order.
Benzene Derivatives
The nomenclature of substituted benzene ring compounds is less systematic than that of the
alkanes, alkenes and alkynes. A few mono-substituted compounds are named by using a group name
as a prefix to “benzene”, as shown by the combined names listed below. A majority of these compounds,
however, are referred to by singular names that are unique.
Note : Two commonly encountered substituent groups that incorporate a benzene ring are
phenyl and benzyl.
When more than one substituent is present on a benzene ring, the relative locations of the
substituents must be designated by numbering the ring carbons or by some other notation. In the case
of disubstituted benzenes, the prefixes ortho, meta and para are commonly used to indicate a 1, 2- or
1, 3- or 1, 4- relationship respectively.
Finally, if there are three or more substituent groups, the ring is numbered in such a way as to
assign the substituents the lowest possible numbers. The substituents are listed alphabetically in the
final name. If the substitution is symmetrical numbering corresponding to the alphabetical order.
When large and complex groups are attached to the benzene ring it is common practice to name
the molecule as an alkane, alkene, etc., and benzene as side chain derivative written as phenyl (C6H5,
–, Ph).

Regioisomers
The type of isomerism which is produced as a result of the different outcomes of chemical
reactions in which there are different orientations or sites to choose from. For example, when addition
reactions between unsymmetrical reagents and unsymmetrical double or triple bonds occur, two outcomes
are possible. As part of the original observations of this chemistry, wherein one of the atoms added was
a hydrogen and the other was some distinctive, non-hydrogen atom, the placement of this distinctive
atom was said to occur at one region or other of the molecule, hence, the formation of regioisomers.
Based on the mechanism of the chemical reaction, the selectivity for one of these regioisomers forming
faster than the other can be predicted. With the addition of simple mineral acids, for example, the product
derived from a faster protonation giving a more stable intermediate is referred to as the Markownikoff's
regioselectivity.
Regioselectivity in the formation of regioisomers is also observed in electrophilic aromatic
substitution reactions. In the case of monosubstituted benzene derivative, there are three possible
regioisomeric products that form at different rates, based on the mechanism of the reaction.
One of the most fundamental reactions in organic chemistry is the addition of HX to an
unsymmetrical alkene. In those cases, two different ‘regioisomers’ could be formed. The reaction is
according to Markownikoff's rule.
The addition of HCI to propene is shown below
In fact, the only product that is formed in the reaction of propene with HCI is 2-chloropropane.
None of the regioisomer 1-chloropropane is formed. As such, we call this a “regiospecific” reaction, since
only one of several possible regioisomers was formed.
Note : The structural isomers, functional isomers and positional isomers are also called
regioisomers. Tautomers are the subcategory of functional isomers.
IUPAC name of some position isomers is as :
R, S Nomenclature for Stereoisomers

The different stereoisomers of a molecule can be expressed in terms of R and S configuration.
This method was proposed by Cahn, Ingold and Prelog. This method has been accepted by IUPAC. The
method involves the following steps :
Step I : Identify the centre of chirality in the molecule.
Step II : The four atoms or groups of atoms joined to the asymmetric carbon atom are assigned
as sequence of the priority by the sequence rules. These are also called Cahn, Ingold, Prelog (CIP) rules.
These rules are as follows :

1. The four substituents are listed in order of decreasing atomic number of the atom directly
attached to the chiral carbon atom. e.g.,
If two atoms are isotopes of the same element, the atom of higher mass number has the
higher priority.
2. If the relative priority of two groups is not decided by rule I (on the basis of the atomic
number of the atoms that are directly attached to the asymmetric carbon atom), then the
next atoms are considered for priority assignment.
3. Where there is a double bond or triple bond, both atoms are considered to be duplicated
or triplicated.

4. All atoms except hydrogen are formally given a valence of four. If the actual valence is less
than four as in case of nitrogen, oxygen, etc. phantom atoms are used [designated by a
subscript (o)]. These phantom atoms are assigned zero atomic number and ranked the
lowest in priority sequence.
According to the above sequence rule of R–S notation, a list of common atoms and groups in
the increasing order of priority is as :
I > Br > Cl > SO2R > SO R > SR > SH > F > OCOR > OR > OH > NO2 > NO > NHCOR >
NR2 > NHR > NH2 > CX3 (X = halogen) > COOX > CO2R > CONH2 > COR > CHO > CR2OH > CHOHR
> CH2OH > CCR > C6H5 > CHC > CRCR2 > CR3CHR2 > CH2R > CH3 > D > H > Phantom atoms.
Step III : After assigning the priorities to the four groups or atoms attached to the asymmetric
C-atom, the molecule is visualized to be in a position where the atom or group of atoms of lowest priority
is directed away from us. Then we trace the path from atom/group in the decreasing order of priorities.
R is given to the isomer if sequence is left to right i.e., clockwise (R stands for rectus, a Latin
word for right).
S is given to the isomer if sequence is right to left i.e., anticlockwise (S stand for sinister, a Latin
word for left).
Note : When the molecule contains more than one chiral centre, configuration of each centre is
determined separately following same the sequence rule.
Let us consider some examples.
(i) Butan-2-ol :
Priority order : OH, CH2CH3, CH3, H
(ii) 1-aminoethanol
Priority order : OH, NH2, CH3, H

(iii) 3-bromobutan-2-ol
Designation of Configuration of C-2 and C-3 :
Hence, the molecule may be represented as (2R, 3S).

E-Z System of Nomenclature for Geometrical Isomers
When there are three or four different groups attached to the carbon atoms of a double bond, it
becomes difficult to assign cis and trans designation to isomers. To overcome this problem, Cahn-
Ingold-Prelog developed the E-Z system which is based on the assignment of priorities to atoms or
groups attached to each carbon of the double bond. According to priority sequence rule by Cahn-Ingold
-Prelog the priority of the substituents is determined for each carbon atom. (These rules are same as
given earlier for R, S nomenclature system).
If the two higher priority groups are on the same side of the double bond, the isomer is called
Z (German Zusammen meaning together) and if the two higher priority groups are on the opposite side
of the double bond, the isomer is called E (German, Entgegen meaning opposite).
(Priority : Cl > F and I > Br)
(Priority : CH3 > H and Cl > CH2CH3)

Some other examples of E and Z nomenclature are as

2. PRINCIPLE OF STEREOCHEMISTRY
 The branch of chemistry which deals with three dimensional structures of molecules and
their effect on physical and chemical properties is known as stereochemistry.
Isomerism : Greek Word isos = equal
meros = part.
 Compounds having same molecular formula (M.f) but differ in their properties are known
as isomers and this phenomenon is known as isomerism.
Isomerism
Structural isomerism Stereo isomerism
1. Chain isomerism
Conformational Configurational
2. Ring chain isomerism isomerism isomerism
3. Position isomerism
4. functional isomerism
5. Metamerism Optical Geometrical
isomerism isomerism
6. Tautomerism
Stereoisomerism :
 Compounds having same constitution but different spatial arrangements of their atoms
are known as stereoisomers and the isomerism exhibited them is called stereoisomerism.
There are two types of stereoisomer.
Stereoisomer
Conformational Configurational
 These are inconvertable  these are non inconvertable
 for interconversion, the energy  High amount of energy required
required for interconversion is for interconversion that is not
very low that is available at room available at room temperature.
temperature
 these can't be separated  these can be separated
 these are also called rotamers or  these are also called rigid
conformers or flexible molecules molecules
Conformational Isomers :
 Special orientations of a molecule which differ only in the dihedral angle and easily
interconvertable through mechanical process without making or breaking of bonds.
Mechanical processes involve rotation around single bonds or twisting of bonds.
 Isomers developed due to such orientations are termed as conformational isomers.

Representation of Conformational Isomers :

(i) Newmann Projection Formula
(ii) Sawhorse projection Formula
(i) Newmann Projection :
 It is front view representation.
 It is 2-D representation.
1 2
eg. H3 C CH3 (ethane)
suppose C-1 is front carbon and C-2 is rear carbon
1 2
2 3 1 3
front carbon rear carbon

H H
H
H H
60°
H
H H H H H
H
Staggered Eclipsed
conformation conformation
( = 60°) ( = 0°)
(ii) Sawhorse Representation :
 It is a side view representation.
 It is a 3-D representation.
60°
(Eclipsed) (Staggered)
Conformations of Acyclic System
(1) Conformations of Ethane :
CH3 — CH3
0°
H H
H
H 60° H
60° rotation
H
H H H H H
H
Staggered Eclipsed
Q = 60°, 180°, 300° Q = 0°, 120°, 240°, 360°
 All intermediate conformations (0° <  < 60°) are known as skew form.

Eclipsed
2.9kcal
PE
Staggered
0° 60° 120° 180° 240° 300° 360°

Dihedral angle
PE = Eclipsed > skew > Staggered

Stability = Staggered > skew > Eclipsed
 The staggered form is most stable due to -
(i) the carbon - hydrogen bonds are as far away from each other as possible.
(ii) there is no torsional strain.
(iii) Hyperconjugation

Interaction between  and *
PE decreases
stability increases.
*
*

* ABMO
 The eclipsed form is least stable (unstable) due to

(i) maximum repulsion between H.
(ii) maximum torsional strain (repulsion between bond pairs).
Atomic repulsion
H H
H
Repulsion between bondpairs

H
H (Torsional strain)

(2) Conformation of Propane :

1 2
CH3 CH2CH3
H H
CH3
H CH3
60°
H
rotation
H H H H H
H
(Eclipsed) (Staggered)
Eclipsed
E 3.4kcal
Staggered

(3) Conformations of n-Butane :
1 2 3 4
CH3 CH2 CH2 CH3
Rotation between C2 and C3
CH3 CH3 CH3

CH 3 H
H CH3
60° 60°
H H
rotation rotation
H H H H H H CH3 H
H
 = 0°  = 60°  = 120°
fully eclipsed Gauche Eclipsed
  
rotation 60°
CH3 CH3 CH3

H
CH3 H H H
60° 60°
CH3
rotation rotation
H H H H H H H
H CH3
 = 300°  = 240°  = 180°
Gauche Eclipsed fully staggered (Anti)
VI V IV

Energy Profile Diagram :
I III V VII = I
4.5
3.8 kcal
PE II
VI
0.9
IV
0° 60° 120° 180° 240° 300° 360°

Dihedral angle
Thus, the relative stabilities are :
Anti > Gauche > Eclipsed > Fully eclipsed
IV II and VI III and IV I
 Molecule with carbon-carbon single bonds have many interconvertible conformers.
 Conformers can’t be separated because they rapidly interconvert so these are not
stereoisomers.
 On increasing temperature staggered form will convert into higher energy eclipsed form.
So percentage composition of eclipsed form increases with increase in temperature.
Q. Draw the most stable conformation of following compounds.
1 2 3 4 5
(1) CH3 CH2 CH2 CH2 CH3
CH3
H H
(C2 — C3 bond)
H H
C2H5
1 2 3 4 5 6
(2) CH3 CH2 CH2 CH2 CH2 CH3
C2H5
H H
(C3 — C4 bond)
H H
C2H5
1 2 3 4 5
(3) CH3 CH2  CHCH2 CH3
|
CH3

CH3
H CH3
(C2 — C3 bond)
H H
C2H5
1 2 3 4 5 6
(4) CH3 CH2 CH2 C(CH3 )2 CHCH3
C2H5
H H
(C3 — C4 bond)
H3 C CH3
C2H5
(5) In the following case Gauche is more stable than the Anti form due to strong electrostatic
force of attraction (H-bonding, dipole - dipole interactions etc).
CH2 CH2
| |
X Y (Gauche > Anti)
– OH – OH
– NH2 – NH2
– NH2 – OH
– OH –F
– COOH – COOH (low pH)
–F –F
O
||
– NH3 – C – OR
But in this case :
CH2 CH2
| |
X Y (Anti > Gauche)
–R –R
+ +
– NH3 – NH3
– –
– COO – COO
– Cl/Br/I – Cl/Br/I
 This is due to steric repulsion of bulky groups.

Examples :
H
O
CH2 — CH2
| | H O
OH OH H
(Gauche)
(I)
H H
H
F
CH2 — CH2
| | H F
F F
(Gauche)
(II)
H H
H
Cl
CH2 — CH2
| | H H
Cl Cl
(Anti)
(III)
H H
Cl
+
CH3
CH2 — CH2 –
| | H Cl
CH3 Cl
(Gauche)
(IV)
H H
H
OH
CO COO
CH2 — CH2 OH
| | H CO H H
COOH COOH
(V) H H H H
H COO
Law pH High pH
(Gauche) (Anti)
+
NH2 NH3
CH2 — CH2
H NH2 H H
| |
NH2 NH2
(VI) H H H H
+
H NH3
(High pH) (Low pH)
(Gauche) (Anti)
H  = 60°, 180°
H
H
H CH3 H
H
CH3 CH3  = 60°, 180°
H
CH3 CH3 CH3
CH 3
(6)
• ••  = 60°, 180°
•
H
• O H
•
H
••

(7) CH3CH2 NH2
H •• CH3
here is no repulsion
N (Gauche) between lone pair
and CH3 group
H H
H
CH3
CH3 — CH — CH — CH3
| | H OH
OH OH
H
(8)
H O
CH3
 
(9) Hydrazine (NH2 NH2 )
•• •• less stable
H H H due to pyramidal
••
inversion eclipsed
N N form is obtained
which is less stable
H H H •• H
H
(Gauche)
obs = anti × a + gauche × g
 = fraction
But a = 0
 obs   gauche   g

Q.
CH2 — CH2
| |
G G
net = 1.0 D
anti = 0.82
gauche = ?
net = anti × a + gauche × g
1 = anti × 0·82 + gauche × 0.18
1
gauche = = 5.55 D
0.18
Gibb’s free energy and relative population of conformers.
Eclipsed Staggered
x%
Q. At equilibrium
[P] = 80%
[R] = 20%
Find out keq.
80
Sol. keq = = 4
20
Q. keq = 5 , [P] = ?
[R] = ?
x
Sol. 5 = or x = 83.33 = [P]
100  x
[R] = 100 – 83.33 = 14.67%
Q. G for the following reaction is – 12.55 kJ mol–1. Find out the keq at 298 k.
Sol. G = –2.303 RT log keq
–12.55 × 103 = –2.303 × 8.314 × 298 log keq
12.55  1000
log keq =
2.303  8.314  298
= 2.2
keq = Antilog 2.2
= 158
Conformational analysis of propene, But-1-ene, Acetaldehyde, Propanaldehyde, ,-unsaturated
ketones and 1,3-diene :

(1) Acetaldehyde :
O
H ||
H—C—C—H
H
H
O O
60°
rotation
H H
Eclipsed Bisect form
(E) (B)
PE = B > E
Stability = E > B
(2) Propene :
CH2
H ||
H—C—C—H
H
H
CH2 CH2
H H
60°
rotation
H H
H H
H
Eclipsed Bisect
PE = B > E
Stability = E > B
(3) Propanaldehyde :
CH3CH2CHO
H3C H
O O O O
H CH 3 H H
60° 60° 60°
H H H CH3
H H H H
H CH 3
E1 B1 E2 B2
PE = B1 > B2 > E2 > E1

Stability = E1 > E2 > B2 > B1

(4) But-1-ene :
CH3CH2CH = CH2
H3 C H
CH2 CH2 CH2 O
H CH 3 H H
60° 60° 60°
H H H CH3
H H H CH3
H H
E1 B1 E2 B2
PE = B2 > B1 > E1 > E2
Stability = E2 > E1 > B1 > B2
(5) 1,3-Butadiene :
H H
H H
H H
H H H
(Steric H
H repulsion
more) H
Cissoid Transsoid
5% 95%
H3 C O H3 C O
H H
H H
(Steric
(6) repulsion H H
less) Cissoid Transsoid
(More stable)
Conformation in Cycloalkanes
 Compounds with three and four membered rings are less stable as compare to compounds
with five and six membered ring.
 The instability of these small ring compounds can be explained by Baeyer strain theory.
 According to Baeyer strain theory when an open chain compound having the normal BA
109·5° (tetrahedral) is converted into a cyclic compound. There is deviation from the
normal tetrahedral angle leading to the development of a strain in the molecule. This strain
is called as angle strain or Baeyer strain.
 According to Baeyer cycloalkanes are planar and angle strain in various cycloalkanes can
be expressed in term of angle of deviation (distortion) d, i.e., deviation from 109·5° for one
bond.
1 2(n  2) 
d 109.5   90 
2 n 
1
d
2
109.5   
where; n = no. of edges (C – C bonds)
 = inner bond angle.
Angle strain  d
1
Stability 
d
 for cyclopropane :
inner angle () = 60°
d = ½ (109.5 – 60) = 24.75°
60°
24.75°
deviation
. 5°
1 09
60°
24.75°
deviation
60° 90° 108° 120°
Cyclopropane Cyclobutane Cyclopentane Cyclohexane

 = 60°  = 90°  = 108°  = 120°
d = 24.75° d = 9.75° d = 0.75° d = –5.25°
 According to Baeyer strain theory most stable cycloalkane should be cyclopentane due to
least angle strain but it is not practically true.
 The stability of cycloalkanes is :
 This can be explained by Heat of combustion

and H combustion  no. of C-atoms
1

Stability
 So cyclohexane is most stable cycloalkane, So we take its angle strain = 0.
 Cyclopentane and cycloheptane are equally stable.
 Cyclic compounds twist and bent in order to achieve a final structure which minimises the
following types of strain.
1. Angle strain - deviation from tetrahedral bond angle (109.5°).
2. Torsional strain - repulsion between bond pairs.
3. Steric strain (Vander Waals strain) - repulsion between atoms or group.
Conformations of Cyclohexane
 Six membered cyclohexane are most stable because they can exist in a conformation that
is almost completely free of strain, this is called chair conformation.
 Cyclohexane have as no. of conformers out of which most important conformations for
cyclohexane are :
(1) Chair form
(2) Boat form
(3) Half chair form
(4) twist boat form
(1) Chair Form :

 There are two types of H in chair conformation of cyclohexane
a a 6-H Axial   to the molecular plane
e
e e
a
e e
e a
6-H equatorial  II to the molecular plane
a a
 It is staggered conformation.
 Bond angle is 111.4° which is very close to 109.5. So it is most stable conformation of
cyclohexane.
 Angle Strain = 0
Torsional Strain = 0
(2) Boat Form :
Flagpole hydrogens
H H
H H H
H
H H
H
H
H H
 It is eclipsed conformation.
 In the boat conformation there is steric repulsion between flagpole hydrogens pointing
towards each other. This causes steric strain (Vander - Waals Strain). Hence, the total
stain in the boat form is larger than that in the chair form.
 Angle strain = 0
Torsional strain = high
(3) Half Chair :
(Twist boat)
 Angle strain as well as torsional strain are very high for half chair conformation.
 It is least stable conformation of cyclohexane.
(4) Twist Boat Form :
Angle Strain = O
Torsional Strain = O
 It is stable than Boat form.
 It is Chiral Conformation ( and i absent).
 It is Dissymmetric (C2 – Present).

Newman projection of chair and Boat form :
Ha H HF
e Ha Ha H
He He HF H
H H
H H
He He
He Ha H H
Ha Ha
H H
(Chair form) (Boat form)
Flipping of Ring
 At room temperature cyclohexane rapidly interconverts (flip) to mirror image chair form
Ha
He Flipping
Ha
He
 for flipping low amount of energy required that is available at room temperature.
 On flipping all the equatorial hydrogens become axial and all the axial hydrogens become
equatorial.
 During flipping following conformers are obtained.
Chair Half Chair Twist Boat

I II III
Half Chair Twist Boat True Boat

VI V IV
Inverted Chair
VII

Energy Profile
Half-Chair Half-Chair
IV
II VI
III V
PE
Twist Twist
Boat Boat VII
Chair Inverted
I Chair
Flipping
Potential Energy
Half Chair > True Boat > Twist Boat > Chair
Stability
Chair > Twist Boat > True Boat > Half Chair
Evidences in Favour of Flipping
 At room temperature cyclohexane rapidly flips. This is so rapid that all hydrogens on
cyclohexane can be considered equivalent. So it gives only one 1H NMR signal.
 Ring flipping is slowed down below –80°C, therefore, axial and equatorial hydrogens can
be differentiated and give two ‘H NMR signals.
1,3-diaxial Interactions
 When one hydrogen in cyclohexane is replaced by a larger atom or group, Crowding
occurs.
 The most severer crowding is among atoms held by the three axial bonds on the same
side of molecule the resulting repulsive interaction is called 1,3-diaxial interaction. This
causes steric (Van – der – waal’s) strain in the molecule.
In Monosubstituted Cyclohexane
H G
+G
–H
H G
H
Keq > 1
H
G
(Preffered
Conformation) H
Q. If G = –H, –CH3, – CH – CH3 , – (CCH3)3 and the value of keq for these groups are k1, k2, k3 and
|
CH3
k4 respectively then find out the decreasing order of keq.
Sol. k4 > k3 > k2 > k1
 That means bulky group has the tendency to occupy equatorial position rather than axial
position in order to minimize 1,3-diaxial interactions.
 As well as the size of group increases, the population of conformer having group at
equatorial position is increased.
 When group is t Butyl, then
100%
It is called locking or freezing of flipping
some other examples are -
O C O
Trans Decaline
In Disubstituted Cyclohexane
+ 2G
C6H10G2
– 2H
1,1 1,2 1,3 1,4
G G G G G
G
G
G
gives geometrical isomerism

(i) 1,2-disubstituted Cyclohexane :
CH3 CH3
CH3
CH3 CH3
a,e or a,a e,e
e,a Trans CH3 Trans
(cis) (most stable)
Stability  e,e > ae > aa

(diaxial interations)
(ii) 1,3-disubstituted Cyclohexane :
CH 3 CH3 CH3
CH3 CH3 CH3
a, a e, e a,e or
(cis) (cis) e,a
Trans
Stability  e,e > ae > aa
(iii) 1,4-disubstituted Cyclohexane :
CH3 CH3
CH3 CH3 CH3
ae or
ea CH3 aa ee
(cis) (Trans) (Trans)
Stability  ee > ae > aa
Q. Arrange the following in decreasing order of stability.
Me Me
Me
Me
Et Et
I II III IV
Et Et
Sol. IV > I > III > II
Q. Draw the stable conformer of following compounds.
Me OH
Me Me
(i) (ii)
Me
tBu tBu
Et
Cl
(iii) (iv)
CH3
CH3 Cl Cl
Sol. To draw stable conformer of cyclohexane, first of all the most bulky group is arranged at equatorial
position and then remaining groups are arranged according to their relative stereochemistry with
respect to the bulky group.
Me
Me
Me OH
(i) (ii)
Me
Cl Cl
CH3 C2H 5
(iii) (iv)
CH3
Cl

Conformations of Sugars
CH 2OH H
O OH O
CH
2
H H HO H
H
• *
OH H H
OH OH OH H
HO
H OH H OH
-D(+) glucopyranose
(Less Stable)
CH 2OH H
O OH O
CH
2
H OH HO H
H
*
OH H H
OH H OH OH
HO
H OH H H
-D(+) glucopyranose
(More Stable)
(all groups are equiatorial)
Conformations of Fused Rings (Decalin)

 Decalin exists in two diastereioisomeric forms; (cis and trans)
 In both the diastereoisomers of decalin, the two cyclohexane rings are joined together in
the chair conformation.
(i) Cis-Decalin :
H(e)
H(a)
(a) H
H(e)
 In cis decalin, the ring fusion involves ae bonds, hence it is flexible and exists in two forms
which are interconvertible as a result of conformational flipping at room temperature.
 In cis decalin C2-axis of symmetry is present while plane and centre of symmetry is
absent so it is Dissymmetric molecule hence it is chiral.
 Because of rapid interconversion, cis-decalin exist as a nonresolvable enantiomeric pair
and is, therefore optically inactive.
(ii) Trans-Decalin :
H
H
H
H
 Since, trans-decalin involves two aa or ee bonds for the ring fusion, it is rigid molecule
and can’t undergo conformational flipping.
 In trans-decalin plane as well as C2-axis of symmetry are present so it is symmetric
molecule hence it is achiral and optical inactive.
 It is non resolvable.
Exceptions of Conformation
(i) Cyclohexane-1,3-diol :
H—O H—O OH
OH
HO OH HO
OH
(aa) (ee) (a,e)
In these cases aa form is stable :
OH G
G = Cl, OR, F, NH 2
This is due to intramolecular
H-bonding.
(ii) Cyclohexane 1,4-diol :
It exists in the boat conformation due to intramolecular H-bonding.
H
|
O H-O
H H
Preffered Conformation
Boat form
(iii) 1,2-dihalocyclohexane :
X
X
X X
X
X X
aa X e,e a,e
(trans) (trans) (cis)
=0  0
(most stable) (lest stable)
 As well as size of halogens increases (F < Cl < Br < I) repulsion between halogens
increases in ee form hence, stability of aa form increases.
F Cl Br I
F Cl Br I
Stability
(iv) -halocyclic Ketone :
H Br
O
Br Br H
O O
• Maximum Polar • Less Polar
• Dipolar interaction • Dipolar interaction
maximum minimum
(Preffered)
• Major in more polar
solvent
• It is the preffered conformation
for favoraskii rearrangement.
(Twist Boat)
most preffered
(v)
Both t butyls at pseudo equatorial
R R
O S
(vi) H H
O S
 In this case alkyl group preferred axial position because lone pair on O and S have a small
steric repulsion than the C — H bonds in the corresponding cyclohexane.
Q. In Cis-and trans-2-methyl-5 t-butyl;-1,3-dioxane each can exist as two conformers as given below.
O
O
CH3
O
O
Cis-P Cis-Q
CH3 CH3
O
O
H3C O
O
Trans-R Trans-S
The preferred conformations for the cis and trans compound will be
(a) P,R (b) Q,S
(c) P,S (d) Q,R
Sol. (b) In heterocyclic rings the steric repulsion for axial substituents are reduced due to the
replacement of methylene groups of cyclohexane by oxygen or nitrogen.
OH
Q. Draw the most stable conformation of
O
Sol.
H
—
O
H O
(Intramolecular H-bonding)
Configurational Isomers
(i) Geometrical isomerism.
(ii) Optical isomerism.
(i) Geometrical Isomerism :
 The isomerism which arises due to different arrangement of atoms or group of atoms
around a system in which free rotation is restricted.
 Geometrical isomers are non inter convertible at room temperature.
(i) Restricted Rotation :
Restricted rotation
Due to double bonds Due to cyclic structure Due to steric hinderance


OH
eg  eg 
(i) Oxims C N (i) Monocyclic ,
(ii) Azocompounds (ii) Bicyclic

—N N—
(these two groups
(iii) Alkenes - (iii) Bridge must be different)
C C Compounds
(iv) Polyspiro compounds
Isolated Conjugated Cumulated
odd number of odd number of

double bond rings

(ii) The site about which rotation is restricted must have different atoms or group of atoms.
a a a c a OH
C C C C C N
b b b d b
a  b; c  d a  b; c  d ab
a b
C N
•• ••
Example :
•• •• Ph H
N N N N
(1) (2)
H H
•• ••
H OH CH3 OH
C N (Aldoxims) C N
(3) (4)
CH3 C2H5
CH3 H H Cl
C C C C
(5) (6)
C2 H5 H Cl H
(7) (8) *
* *
D
(9) * * * (10) *
H
Cl
(11) Cl Cl (12)
Cl
Monocyclic System :
H
CH3
Br
Cl Cl C2 H5
H I
D I
H
Bicyclic System :
H H H
H H H
Bridge Compounds :
Cl Cl
Cl Cl
(iii) Planarity : molecule must be planar or substituents must be in the same plane.
eg. (i) Cumulenes having odd no. of double bonds
Cl Cl Cl Cl
C C C C C — C — C — C
H H H H
sp2 sp sp sp2
In In
Plane Plane
(ii) Spiranes : Since the replacement of a double bond in allene by a ring does not
alter the basic geometry of the molecule.
Cl Cl
eg.
H H
(iii) Hemispiranes :
Cl Cl
H H
Note :
(i) Cumulenes, spiranes or hemispiranes having even no. of double bond or rings or both
gives optical isomerism.
Cl Cl
C C C Optical active
H H
Cl Cl
Optical active
H H
Cl Cl
Optical active
H H
(ii) Cycloalkenes (up to 7 C) does not gives geometrical isomerism due to angle strain their
trans isomer does not exist.
H
(Cis)
H
H H H H
H
(Cyclooctene)
H H
(Cis) H
(Trans)
H
H
H
H
(Cis) (Trans)
Q. Which of the followings will give geometrical isomerism.

Cl
(1) (2)
Cl
(3) (4)
Br
(5) (6)
Cl Br Br
F
Br F
(7) (8)
Me Me
Cl
H
(9) (10) HO — N
CH3
F O

I Br
(11)
Cl F
free rotation due to
aromaticity
Notations for Geometrical Isomers
(i) Cis-Trans Configuration.
(ii) E–Z Configuration.
(iii) Syn–Anti Configuration.
(i) Cis-Trans Configuration :
a a a a a b a c
C C C C C C C C
b b b c b a b a
Same groups Same groups

same side opposite side
 
Cis Trans
Examples :
H H H CH3
C C C C T T
CH3 CH3 CH3 H T = Trans

Cis Trans C = Cis
T CH3
C
C Cis
C CH3
CH3 H H H Cl
C C C C
CH3 Trans Cl Cis Cl Cl Trans H
(ii) E-Z Configuration : Based on CIP (Cohn-Ingold-Prelog) rule

CIP-Rules :
 CIP rules are applied in succession.
 Priority of atoms or groups of atoms attached to each carbon of restricted site is determined
by using sequence rules which are follows.

Rule-I : Higher atomic no. will get higher priority
1 I F 2 2 CH3 NH2 1
C C C C
2 Br Cl 1 1 Cl CH3 2
I > Br Cl > F Cl > C N>C
Rule-II : Heavy isotopes will get higher priority.
35
2 Cl H 2
C C
1 37
Cl D 1
Rule-III : If the relative priority of two groups cannot be decided by rule mentioned above then
look for next higher priority atom.
2 H CH2 CH3 (C,C) 2
C C
1 CH3 CH(CH3)2 (C,C,C) 1
(C, H)
2 H CH2 CD3 1 (C, D)
C C
1 D CH2 CH2 CH3 2 (C, C,)
Rule-IV : When there is a double bond or triple bond both atoms are considered to be duplicated
or triplicated.
A C
C A C A C A C A
A C A C
H H C H
C O C O CH CH2 C C C
O C H H
2 H2NOC CHO 2
C C
1 ClOC COOH 1
Rule-V :
cis > Trans
R > S
RR or SS > RS or SR
RR > SS > RS > SR
Z> E
Rule-VI : lone pair gets lowest priority
2 H3 C OH 1
C N
1 Et •• 2
Rule-VII : Ring System
(i) O & O I > II
I II
C C C C
| | | |
O O C C
| | | |
C C O O
| | | |
C C C C
| |
C C
| |
C C
O
(ii) & O I > II
O C C C
| | | |
C C O O
| | | |
C O C C
| | | |
C C C C
(iii) & II > I
C | C—C C C—C
| C | |
C | C C—C
| C | |
|

O
(iv) & O I > II
O
O O
(v) & II > I
(vi) & I > II
Q. Assign E-Z configuration in following compounds.

H CH3 ClH 2C CH3
C C C C
(i) (ii)
D C2H5 H3C C2H5
Z E
O2 N CCl3 CH3 COOH
C C C C
(iii) (iv)
F OC2H 5 H CH3
E E
S
O +
P O
C C
C C
(v) HN (vi) P P
E
E
S
(iii) Syn-Anti :
Azo Compounds Oximes
CH3 •• CH3 ••
N N
|| || Aldoximes Ketomes
N N H3C H H5C2 CH3
CH3 •• •• CH3
C C
Syn Anti || ||
N N
•• OH •• OH
Syn Anti
If H and OH OH and higher
sameside Priority carbon
opposite side
H3C H H3C C2H5
C C
|| ||
N N
HO •• •• OH
(Anti) Syn

Preparation of Oximes :
OH
–H2O
O + H2 N – OH N
(Oxime)
 The carbon attached to nitrogen should bear different groups to show geometrical isomerism.
Aldoximes :
R •• R OH
–H 2O
R—C O + NH2 — OH C N + C N
|
H H OH H ••
Syn Anti
Syn  OH and H on same side
Anti  OH and H on opposite side
 Except Formaldehyde all aldehydes gives geometrical isomerism.
H H OH
C O + NH 2OH C N
H H
Ketoximes :
R1 R1 •• R2 ••
–H2O
C O + H2N – OH C N + C N
R2 R2 R1
OH OH
There may be two names of one ketoxime
Me OH Me ••
C N C N
Et •• Et OH
Syn-Methylethyl ketoxime Anti-Ethylmethyl ketoxime
Anti-Ethylmethyl ketoxime Syn-Methylethyl ketoxime
 All unsymmetrical ketones form geometrical isomeric oxime on reaction with NH2OH
Q. Which of the following carbonyl compounds will form geometrically isomeric oxime on reaction
with NH2OH ?
(i) HCHO
(ii) PhCHO
(iii) O
O
Me
(iv)
— C — CH3
(v) ||
O
(vi) O
(vii) HCOD
(viii) CH3COCH3
(ix) C2H5COCH3
 Hydrazones and Imines also gives geometrical isomerism
NH2 H H
R1 R1 R1 +
N N N
R2 R2 R2
R1  R2 R1  R2 H
 Minimum Carbon atoms required to show geometrical isomerism = 0.
E.g. : Diazocompounds which have zero carbon atoms
HN = NH
 Minimum carbon atoms required to slow GI in alkenes = 4
E.g. :
CH3 CH 3
C C
H H
Q. Draw all the isomers of C2FClBrI .
Sol.
F Cl F Br
C C C C
 Br  Cl
F  F Cl (Total 6 isomers)
C C C C
Br Cl Br 
F Br F 
C C C C
Cl  Cl Br
Number of Geometrical Isomers
Total GI
for unsymmetric for symmetrical

molecule molecule
n n–1 p–1
2 2 +2
n = stereogenic area
(Where GI is observed)
n
P (when n  even)
2
n 1
 (when n  odd)
2
Examples :
n=1 2n–1 + 2p–1
Sym 1–1 1–1
2 +2
1+1=2
Cl Cl n=1 GI = 2
Sym
2–1 1–1
n=2 GI = 2 +2 =2+1=3
Sym
n 1
CH2 CH — CH CH — CH3 n=1 2 =2 =2
Unsym GI = 2
3–1 2–1 2 1
Cl Cl n=3 GI = 2 +2 =2 +2 =6
Sym
CH2 CH — CH CH — CH CH CH CH — CH3
2
n=2 GI = 2 = 4
Unsym
2–1 1–1
n=2 GI = 2 +2
Sym
=2+1=3
Cl Cl
1–1 1–1
n=1 GI = 2 +2
Sym
=1+1=2
2
n=2 GI = 2 = 4
Cl Unsym
Cl
Cl — CH CH — CH CH Cl
3
n=3 GI = 2 = 8
Unsym
2
n=2 GI = 2 = 4
Unsym
NH 2
n=2 GI = 2 = 4
Unsym
CH CH — CH3 GI = 4
CH 3 — CH 2 C
CH CH — CH3
Sol.
Z E Z E
Z E
X X E
Z E Z
NH
HN C GI = 4
NH
HN C GI = 4
NH
NH
O C n = 2 Sym.
GI = 3
NH
C C CH 2 No GI
C C C CH2 No GI
CH C C CH — CH 3 n = 2 Sym.
2n = 22 = 4
Cl
C n=1 GI = 2
H Sym
No. of GI in Cycloalkanes
No GI
GI = 2 (cis and trans)
a a
a a a
GI = 2
+
a a a a a a
a
GI = 2
a a
a a a a
GI = 3
+ +
b a b a b a b a
b b b
GI = 4
+
a c a c a c
b b
a c a c
8 GI
Physical Properties of GI
(i) Solubility and Stability : Trans is more stable than cis due to repulsion between groups so
it is less soluble in H2O.
H3C CH3 H CH3

C C C C
H H CH3 H
more repulsion less repulsion
less stable more stable
H F F F
C C C C Stability
F H H H
Trans Cis
Exception :
vacant
d-orbitals
•• •
• Cl Cl Cl H
C C C C Stability
H H H Cl
Cis Trans

(ii) Dipole Moment :

Case-I :
EWG EWG EWG H

C C C C Cis > Trans
H H H EWG
 0 =0
E.g. :
Cl3C CCl3 Cl3C H

C C C C
H H H CCl3
 0 =0
Cl Cl Cl H
C C C C
H H H Cl
Cl Br Cl H
C C C C
H H H Br
Case-II :
ERG H ERG ERG

C C C C Cis > Trans
H ERG H H
=0  0
E.g.
CH3 CH 3 CH3 H
C C C C
H H H CH3
Case-III :
ERG H ERG EWG

C C C C Trans > Cis
H EWG H H
Case-IV :
1
Polarity 
Bond angle

E.g.
Cl Cl Cl
Cl
Cl
Cl
=0
CH3 CH3 CH3
CH3
CH3
CH3
Exception :
CH3 CH3 CH3
NO2
NO2
NO2
(iii) Boiling Point :
BP  Polarity
 Molecular weight
 Surface area
 VF of attraction
 H-bonding
BP  BPCis  BPTrans
(iv) Melting Point :

MP  Packing efficiency
1

Voids
 Symmetry
MP  MPTrans  MPCis
(v) Heat of Combustion and Heat of Hydrogenation :
HCis  HTrans
Optical Isomerism
Any substances which are capable of rotating the plane of polarized light are called optical
isomers and the phenomenon is called optical isomerism.
Optical isomers are two types :
1. Enantiomers
2. Diastereomers
Optical Isomers
Enantiomers Diastereomers
Enantiomers are mirror Diastereomers are not mirror

images of each other images of each others.
These cannot be super- These have atleast two chiral
imposed upon their mirror centres having same configuration
image. at one chiral centre but there is a
oppose configuration at another
chiral centre.
Enantiomers are also called
enantiomorphs.
Optical antipodes
Ex.(i) (Enantiomers)
Mirror-image isomers.
COOH COOH
C C OH
HO
H CH3 HC H
Mirror 3
(2R)-lacticacid (2S)-lacticacid
I II
I and II are non-super impossible mirror images isomers.
Ex.(ii) (Diastereomers)
COOH COOH
HO * H HO * H
H * OH HO * H
COOH COOH
(2S, 3S)-Tartaric Acid (2R, 3S)-Tartaric Acid
Threo isomer Erythro isomer
(Similar groups lies (Similar groups lies
on oppose side) on same side)
Cis-trans isomers, Anomers, Epimers are Diastereomers.

Relationship between the Molecules
Molecule with the same
molecular formula
Superimposable
Yes No
Homomers isomers
(identical) Same Constitutation
Yes No
Stereoisomers Constitutional
Non Superimposable Isomers
Yes No
Enantiomers Diastereomers
Optical Activity : The rotation of plane polarized light is known as optical activity and substances
possessing this properties are called optical active. The optical activity is observed and measured by an
instrument called polarimeter.
Plane Polarized Light (PPL) : In ordinary light vibration occurs in all the planes perpendicular
to the direction in which light travel. When ordinary light passed through Nicol prism. Then vibration takes
place in only one direction.
It is called plane polarized light (PPL)
Ordinary Light Plane-Polarized Light

 Eye
Light
Source
Ordinary Polarizer PPL Sample Tube Analyzer

Light (Nicolprism) (Chiral Compound)
Figure : Polarimeter
Solid line : before rotation
Broken line : after rotation
 the angle of rotation
Angle of Rotation and Specific Rotation
Optically active compounds rotate the plane of the polarized light through an angle of .
The angle , measured in degree (°) is called the angle of rotation ()
A compound that rotate the plane of polarized light is said to be optically active.
Optically active compound can exist in four forms :
1. Dextrorotatory (d) or () form : If the rotation of the plane is to the right (clockwise) then
the substance is called dextrorotatory (Latin : Dexter = right).
2. Laevorotatory () or (–) form : If the rotation of the plane is to the left (Anticlockwise)
then the substance is called laevorotatory. (Latin : laevus = left)
3. Mesoform : Optical isomers which have atleast two chiral centre but posses plane of
symmetry is called Mesoform.
It is optically inactive due to internal compensation i.e. the rotation caused by the upper
half of the molecule is neutralized by the lower half of the molecule.
Examples :
COOH
H OH H H H H
Plane of
Symmetry
H OH
COOH
OH OH OH OH

4. Racemic Mixture (dl) or (±) : Equimolar mixture of Pairs of enantiomers is called racemic
mixture. It is optically inactive due to external compensation i.e. the rotation caused by the
d form is neutralized by the  from.
Angle of rotation depends upon :
1. The nature of substrate
2. Concentration of the sample (c)
3. Length of tube ()
4. Wavelength of the light
5. Temperature (t)
The common polarimeter use the sodium D-line or Mercury green line. Now new modern spectra-
polarimeter use photocells because they give more accurate value.
Specific Rotation : Specific rotation is the observe angle of rotation if 1-dm (10 cm) long tube
is used and concentration of sample is 1g/ml.

  SP D 
t
c
observed angle of rotation ()
Specific rotation = length (dm)  g / ml
If pure sample of optically active substance is used then

 SP D    d
t
here d represents density of a pure sample

That means specific rotation is independent on
1. Length of tube ()
2. Concentration of the sample (c)
Enantiomeric Excess : Some times we deals with a mixture that is neither optical pure enantiomer
nor a racemic mixture. One enantiomer is present in excess of the other.
The enantiomeric excess (ee) also called the optical purity, tells how much more there is of one
enantiomer.
Enantiomeric excess (ee) = % of one enantiomer – % of the other enantiomer
Ex.1 If a mixture contain 75% of one enantiomer and 25% of the other. Then the enantiomeric excess
is ?
Sol. ee = 75% – 25% = 50%
There is a 50% excess of one enantiomer over the racemic mixture.
Ex.2 If the enantiomeric excess is 75% then how much of each enantiomer is present?
Sol. 75% ee means that the solution contains an excess of 75% of an enantiomer and 25% of the
racemic mixture of both enantiomers.
Because racemic mixture contains an equal amount of both enantiomers, it has 12.5 % of each
enantiomer.
Total amount of one enantiomer = 75 + 12.5 = 87.5%
Total amount of other enantiomer = 12.5%
100  ee
% major enantiomer 
2
100  ee
% minor enantiomer 
2
The enantiomeric excess can also be calculated as :
[]mixture
ee   100%
[]pure enantiomer
[] = specific rotation
(moles of major enantiomer)  (moles of min or enantiomer)

ee   100
moles of both enantiomer
Conditions for Optical Activity : A compound is said to be optical active if it is non- superimposable
on its mirror image due to asymmetry.
Chirality is the necessary and sufficient condition for a molecule to be optically active.
1. All Asymmetric and dissymmetric molecules are chiral and optical active.
An Asymmetric molecule has no element of symmetry.
Elements of Symmetry Asymmetric Dissymetric Symetric

1. Centre of Symmetry (i) Absent Absent i-Present
or
2. Plane of Symmetry () Absent Absent -Present
or
3. Axis of Symmetry (Cn) Absent Present Both Present
Chiral Achiral
Optically Active Optically Inactive

Elements of Symmetry
1. Plane of Symmetry : The plane which cuts through the middle of a molecule in such a way
that one half of the molecule is a mirror image of the other half.
Example
OH CN OH
CN
Plane of Symmetry run through
Me Me Me Me central carbon, OH and CN
COOH COOH COOH

COOH
Plane of Symmetry run through
H H central carbon, and both COOH
H H
H OH
No plane of Symmetry because

COH CH3 both are non-identical atom
2

2. Centre of Symmetry (i) : A point in the molecule through if a line is drawn in one direction,
then extended to equal distance in opposite direction. It meets another similar group or atom.
Cl Br
H H
H H
Br Cl
3. Axis of Symmetry (Cn) : An imaginary axis through which the object is rotated by an angle,
leave the orientation of the object indistinguishable from its original orientation.
180º 180º
 = 180º
n=2
H Cl H Cl
Cl H Identical Cl H
Structures
Ex. Which of the following molecules are chiral ?
H H H H Cl
H H Cl OH H
H OH H H H
(1) (2) (3)
OH H Cl OH Cl
H
H H HO H
Cl H
(4) (5) (6)
OH OH H OH
Cl
Ans. (1)
180º
H H Cl
H OH Cl OH H
H H H
OH H
Cl OH Cl
(1) (2) (3)
 = Absent
 = Present  Present
i = Absent
Cn = Present Symmetric Symmetric
Achiral Achiral
Dissymmetric molecule
optically inactive optically inactive
chiral optically active

180º
H
HO H
H H
Cl H
H OH
OH OH
i Present Cl
(4)  = Present (5)  Present (6)
 = Present
Symmetric C2 Present Symmetric
Achiral Symmetric Achiral
optically inactive Achiral optically inactive
optically inactive
2. Compounds with Asymmetric Carbon Atom

A carbon atom is asymmetric if four different groups or atoms are attached to it
b c* b Chiral carbon atom

(Asymmetric Carbon atom)
c
Example :
COOH CH3 CH 3
* * *
HO H C2H5 Cl C2H5 H
CH 3 Br OH
Lactic Acid 2-Bromo-2-Chlorobutane 2-Butanol
CH2OH
C O
H H
HO C* H COOH
*
H C* OH (CHOH)4 C* C* NHCH3
H C* OH COOH Br
OH CH3
4-Chiral Centre 1-Chiral Centre
2-Chiral Centre
CH2OH
3-Chiral Centre

3. Optical Activity Even in The Absence of Chiral Carbon Atom

A. Optical Activity Due to a Chiral Axis :
1. Allene :
a b
c c (a  b)
b a
If no’s of double bonds If no’s of double bonds

are even are odd
a b a a
c c c c c c c
b a b b
Perpendiculars In In In
to plane Plane Plane Plane
The groups at the end of allenes The groups at the end of allenes
are perpendicular to each other are in same plane
Here Axis of symmetry Present Here Plane of symmetry Present

C2
 = Present
i = Absent
c=c=c C2 = Absent
Symmetric,
Achiral optical Inactive
Here, C= 2 Present
Gives geometrical
i = Absent
isomerism
 = Absent
Dissymmetric molecule a a
Chiral c c c c
optically active b cis b
a a a a
c c c c c c a b
c c c c
b b b b
b Trans a
Thus Allenes of type abc = c = cab and abc = c = ccd are chiral, when it has even no's of double
bond.
Cl Me H COOH
C C C C C C
H CMe3 HOOC H
1-chloro-3, 4, 4-trimethyl- (R)–(–)–gutinic acid

1-2-pentadiene

2. Sprains :
A
A
AB
B B
Since the replacement of a double bond in allene by a ring does not alter the basic geometry of
the molecule thus the conditions for Chirality in sprains are quite analogous to those in allenes.
here, C2 = Present
i = Absent
 = Absent
Dissymmetric molecule
Chiral
Optically active.
A A A A A
A
C C C
B B B B B
Allene B
Example :
H H
H H
H2 N NH2 HOOC COOH

Diaminospiro-heptane Spiro-heptanedi carboxilic acid
3. Hemisprains :
A A
(A  B)
B
B
Asymmetric
Chiral
Optically active
Example :
Me H2N NH2
H
C
COOH H
H H
4. Biphenyls : Biphenyls show enantiomerism when the following two conditions are satisfied.
(i) Neither of the rings should possess plane of symmetry ()
A B A A
A B B B
Both rings have plane Chiral Axis
of symmetry Chiral
achiral optically inactive optically active

(ii) The ortho-substituents should be larger in size so that the two rings must not be coplanar,
they should be orthogonal to each other
Here A and B = COOH, NO2, I, Br etc.
Example :
H COOH
SO3H COOH NO2 COOH
HO OH
H NO2 OH OH
SO3H COOH OH OH
5. Bridged Biphenyls :
a b
here a=b
or
ab
(CH2)n
non planar
optically active
Example :
EtOOC COOEt
HOOC CH3 CH2

Me Me CH2
CH2 CH2 - CH2
6. Bipyrroles :
X X
N N
Y Y
7. Binepthols :
OH
OH

8. Compounds having Chiral Centres other than Carbon :

Example :
CH 3 CH3 CH 3 C 6H 5
Si Ge Sn N X
C2 H 5 H C 2H 5 H C2H5 I CH3 C 2H 5
C 3H 7 C3 H7 C 3H 7 CH2C6H5
X X = N, P, As, Sb
R1
R3
R2
Here pyramidal inversion takes place at room temperature.
X X
R1 R3 R1
R3
R2 R2
R2
R1 R3
Due to pyramidal inversion both forms are interconvertable therefore they always exist as racemic
mixture it is chiral but optically inactive.
B. Optical Activity Due to Chiral Plane
1. Ansa Compounds :
(CH 2)n
2. Para Cyclophanes :
(CH2)n (CH2)n
3. Trans Cyclooctane :

Calculation of Optical Isomers

Optical isomer can be calculated by using following flow-chart
Calculate the total no’s of

chiral centre (n)
Chiral molecule Achiral molecule

( = Absent ( = Present or
i = Absent) i = Present or
both present)
1. Total enantiomers
(Total optically active
n n = even n = odd
forms) (E) = 2
E  2(n1) E  2(n1)  2
(n–1)/2
2. Total optically inactive
forms (meso forms) n
– –1
m=0 m  22 m2
(n–1)/2
3. Total stereo isomers

T=E+m T=E+m T=E+m
n n (n 1)
2+0=2 E 2 E
P  P =—
2
4. Total pair of enantiomers 2 2
E 2n R=m+P R=m+P
p 
2 2
5. Total racemic mixture

or
Total racemic modification
2n
R mp 
2
Example :
2–1
COOH E=2 =2 COOH E=2 CHO E = 16
m  2(2/2–1) = 1 m=2 m=0
(CHOH)2 (CHOH)3 (CHOH)4
T=2+1=3 T=4 T = 16
COOH
(1) COOH 2
P  1 (2) (3) CHOH
2
-Present 2 -Present P=1 -Absent P= 8

Achiral Achiral Chiral
n = 2 (even) R=1+1=2 n = 3 (odd) R=3 n=4 R=8
Q. Calculate the value of total optically active isomers ?
CH2OH
CHO
Br C O
Cl Cl Br Cl (CHOH)2
(1) (2) (3) (4) (CHOH)3
CN
CH2OH
CH2OH
Ans. (1) 8, (2) 2, (3) 4, (4) 8

Br
*
* *
(1) CN
n=3
TOA = 2n = 23 = 8
Cl Cl Br Cl
(2) *
n=1
TOA = 21 = 2
CHO
| n=2
*CHOH
n 2
| TOA = 2 = 2 = 4
(3) *CHOH
|
CH2OH
CH 2OH
|
C=O
|
*CHOH n=3
|
*CHOH n
TOA = 2 = 2 = 8
3
(4) |
*CHOH
|
CH 2OH
Configuration : The arrangements of atoms that characterizes a particular stereoisomer is
called its configuration.
(A) Representation of a Configuration
1. Wedge-Dash Representation :
Chiral Centre 4
Lies on plane of paper
3 represent principal axis
dash 2
1 wedge
Lies away
from the Lies toward
viewer the viewer
2. Fischer Projection Formula :
4 4
Principal chain
(away from the viewer)
1 3 or 1 3
Towards the viewer
Chiral Centre
2 2

Characteristics
1. Fischer projection formula is always eclipsed conformation.
2. One inter change or odd number interchange of ligands at one chiral centre, gives
enantiomers
Two interchange or even number interchange of ligands at one chiral centre, gives identical
configuration.
1 2 2
st nd
I Changes II Changes
4 2 4 1 3 1
3 3 4
I II III
Ist and IInd = Enantiomers
IInd and IIIrd = Enantiomers
Ist and IIIrd = Identical
3. When fischer projection formula is rotated 180º on the plane of paper then it gives identical
configurations.
1 3
180º
4 2 2 4
on the plane
of paper
3 1
4. When fischer projection formula is rotated 180º out of the plane of paper, then it gives
enantiomers.
1 1
180º
4 2 2 4
out of the plane
of paper
3 3
5. When fischer projection formula is rotated 90º on the plane of paper then it gives
enantiomers.
1 4
90º
4 2 3 1
on the plane
of paper
3 2
6.
1 Constant 1
4 2 3 4
3 2
(identical)

Inter Conversion of Wedge-Dash and Fischer Projection Formula

The group which is below the plane of the paper (dash) is kept at the bottom and remaining three
groups are attached in the same sequence (i.e., clockwise or anticlockwise) as they appear in the flying
Wedge formula.
COOH COOH OH OH
H OH H Ph COOH
OH
(1) H (2)
CH3 Ph COOH H
CH3
(R) (R) R
NH2 H Ph NH3
NH3
Me COOH
Ph CH3
(3) H (4)
Me NH2 CH3
COOH OH OH
Assignment of Configuration
1. D/L System (Relative Configuration)
2. R/S Configuration (Absolute Configuration)
1. D/L System (Relative Configuration) : In relative configuration we deals only with the
configuration of one chiral Centre.
This method is used to assign the configuration of sugars and amino acids.
In the case of sugars the reference substances is glyceraldehyde.
CHO CHO
H OH HO H
CH2OH CH2OH
(OH group (OH group
right side) left side)
D(+)-glyceraldehyde L(–)-glyceraldehyde
While in the case of amino acids the reference substances is alanine.
COOH COOH
H NH2 NH 2 H
CH 3 CH3
D(+)-Alanine L(–)-Alanine
Rules for Determining Relative Configuration
Rule 1 : First the main chain determined and its atoms are numbered.
Example :
5
CH2OH 5
CH3
4 4
HO H H OH
3 3
HO H H NH2
2 2
HO H H2 N OH
1
1
CHO COOH
I II
Rule 2 : Numbering should move from up to down. If it moves from down to up then we
rotate the projection formula about 180º on the plane of paper.
5 1 5 1
CH2OH CHO CH 3 COOH
4 2 4 2
HO H H OH H OH HO NH2
3 180º 3 3 180º 3
HO H H OH H NH 2 H2N H
2 4 2 4
HO H H OH H2N OH HO H
1 5 1 5
CHO CH2OH COOH CH3
I II
Rule 3 : In the case of sugars; we will see the highest numbered chiral centres while in the case
of Amino Acids, we will see the configuration of lowest no. of chiral centres
1 1
CHO COOH
2 2
H OH H NH2
3 3
H OH H2N H
4 4
H * OH HO H
5
CH2OH CH3
D-form D-form
Examples :
CHO
H OH CH2OH COOH
HO H
H CHO
H OH H 3C
H OH OH NH 2
[D] H
CH2OH
[D]
[D]
H
H COOH
H
HO CH2OH
HOH2C H2 N
HO H
H OH NH2
OH
CHO H CHO
[L] OH CH3 H
[L] [D]
2. R/S Configuration : To assign an enantiomer as R or S, first assign a priority (1, 2, 3 or 4)

to each group
Priorities are assigned to groups by a series of rules known as the Cohn-Ingold-Prelog (CIP)
sequence rule, named after the three chemists who developed them.

Rule 1 : The atom of highest atomic number gets the highest priority.
4 2
H Cl
3 F Br 1 4 H SO3H 3
Cl I
2 1
Rule 2 : If two atoms are isotopes of the same element, the atom of higher mass numbered has
the highest priority.
4 1
37
H Cl
35
2 H3 C D 3 4 H Cl 2
I CH3
1 3
Rule 3 : When first atom is same then the next sets of atoms are examined.
The process is continued.
3 (C H H H)
CH 3 H H
1 Cl CH 2CH 3 2 (C C H H ) C C H
H H H
4
Rule 4 : Groups containing double or triple bond are assigned as.
C O equals C O
O C Consider this oxygen

bonded to 2 C’s
Consider this
carbon bonded to 2 O’s
N C
C N equals C N
N C Consider this nitrogen

bonded to 3 C’s
Consider this
carbon bonded to 3 N’s
C
equals
HC CH
C
C

Example :
1
OH
Consider this carbon
4H C CH2OH 3 bonded to 1 oxygen
COOH ( C O H
2
O
Consider this carbon
bonded to 3 O’s
Assignment of R or S to a Chiral Centre
(A) R/S configuration in Wedge-Dash formula :
Example :
COOH COOH
CH3 CH3
C2H5 H5C2
H H
Enantiomer-A Enantiomer-B
Step 1 : Assign a sequence of priorities 1 to 4 to the four atoms or group of atoms bonded to
the chiral centre.
COOH > C2H5 > CH3 > H
1 2 3 4
Step 2 : We visualize the molecule oriented so that the ligand/atoms of lowest priority is directed
away from the viewer (on the dash)
1 1
COOH COOH
3 H3C rotate 4H
C 2 H5 2
H C2H5 CH3 3
4 2
Lowest Priority Lowest Priority

towards the away from
viewer the viewer
Enantiomer-A
1 1
COOH COOH
CH 3 3 rotate H 4
2 H5C2 3 H3C
H C2H5
4 2
Lowest Priority
Lowest Priority away from
towards the viewer the viewer

Step 3 : Trace a circle from priority group 1  2  3. If the arrow point of the circle goes in the
clockwise direction, the configuration is specified R (Latin : Ractus = right).
If Anticlockwise the configuration is specified S (Latin : Sinister = left).
1 1
COOH COOH
H H
CH3 3 CH3 C2 H5
C2 H5 3
2 2
Anticlockwise Clockwise
S-isomer R-isomer
Simple method for Assignment of R or S
4
4
4
Answer Answer even change

as such reverse
Examples :
1 4 1
OH H 1 Cl 4
H4 OH H
Ph COOH me COOH me NH2

3 3 3
2 2 2
Lowest Priority Lowest Priority Lowest Priority
away from the away from the towards the viewer
viewer viewer Answer reverse
Answer as such Answer as such S-Configuration
R-Configuration R-Configuration
H 4 CF3 2
1 Cl C
Even 1 Cl C
Change
C2H5 3 H
4
CF 3 C2H5
2 3
R-Configuration
R and S Configuration in Fischer Projection
Example :
Cl H
H CH3 Br CH3
Br Cl
1-bromo-1-chloro-ethane
Step 1 : Assign a sequence of priority 1 to 4 and trace a circle from priority group 1234.
2 4
Cl H
4H CH3 3 1 Br CH3 3
Br Cl
1 2
Step 2 : Case-I if the group of lowest priority is on the horizontal line then clockwise sequence
gives S and Anticlockwise sequence R configuration.
2 4
Cl H
4H CH3 3 1 Br CH3 3
Br Cl
1 2
Lowest Priority left side Lowest Priority is
clockwise above the plane
[S]-Configuration Anticlockwise
[S]-Configuration
Step 3 : Case-II If the group of lowest priority is above or below the plane then clockwise
sequence gives R and anticlockwise sequence S configuration.
4
H
1 Br CH3 3
Cl
2
S-Configuration
Examples :
3 3 4 1
CHOH
2 COOMe CH3 NH2
R R R R
4H Cl 2 1 HO H 4 1 Cl NH2 2 4H COOH 3
Br CH 2Br C2H5 COOEt

1 2 3 2
[R] [R] [R] [R]
Nomenclature of Compounds with a Chiral Axis
When the sequence rule is to be applied to axial chirality for the specification of absolute
configuration, an additional rule is needed which states that the two near groups precede to the two far
groups. By doing this the R or S designation of a chiral axis becomes independent of the way the axis
is viewed. Thus, when one views structure II from the X end, and if a > b and c > d, the sequence of
priority shown in I is obtained which is equivalent to I' and I''. According to usual procedure, when I'' is
viewed from the side remote from 4, a clockwise sequence 1  2  3 is obtained which shows that
the arrangement II is (R)-configuration.
X
(a)
1
(b) (a) 2
(d)
(d) 4
(c) (b)
(c) 3
Y
I
1
1
3 2 4
4 3 2
I'' I'
(R)-configuration
However, if II is viewed from Y end then pair (c) and (d) will represent 1 and 2, and pair (a) and
(b) will be 3 and 4 to give I’’ which is equivalent to I’. After two interchanges I’ becomes equivalent to
I’’, which still gives a clockwise sequence 1  2  3, and shows (R)-configuration of II.
3
4 3
3 2
2 1 4 1 3
2 2 4
1 4
1 two interchanges II' II''
II
For the R, S nomenclature of chiral biphenyls, firstly the four ortho substituents are examined;
if the ortho substituents in each of the upper and lower rings are different then these are selected for
the nomenclature purpose.
X
Cl (b) 2
(a) 1
2
HO2C NO2
CO2H 3 1
O2N
(b) 4 4
Br (a) 3
Y NO2 = a
CO 2H = b (priority a > b)
III
(S)-configuration
Thus, molecule III showing the sequence 1  2  3 anticlockwise is of (S)-configuration. In the

case of IV, since, ortho substituents in the upper ring are identical (viz, Cl), the groups H and CH3 are
selected for the nomenclature purpose and IV is assigned (S)-configuration.
H Me (d) 4
(c) 3
4 2
Cl Cl
CO2H 1 3 3 1
O2N (b) 2 2 4
two interchanges
(a) 1
Y NO2 = a, CO2H = b
IV Me = c and H = d
(S)-configuration
The R or S specification of absolute configuration of other classes of compounds with chiral axis
is done in a way similar to that of biphenyls. In allenes the chiral axis passes through the cumulative
double bonds, thus the allene V is assigned (S)-configuration. Similarly, the spirane VI and
alkylidenecycloalkane VII have been assigned (R)-configuration.
(a) 1
Me3C Me (b) 2
C 1 2
||
C 4 2 3 1
||
C (c) 3 3 4
H Cl
V (d) 4
(S)-configuration
X HOOC Me
H2N H C
H2N H
CH 3 H
Y
VI VII
(R)-configuration (R)-configuration
Some other examples are :
(CH 2)n
(a) CH2 3’ CH2

1
2 O O
1 2
3
3 Br
clockwise
VIII (R)-

mirror
(CH2)10 CH2 CH2 CH2 CH2

HOOC
resolvable
CH2 CH2
2 1
CH2 2 CH2
1
3 3
CO2H HO2C
paracyclophare (R)-
(S)- the carboxyphenyl ring
cannot rotate to give
the enantiomer
CH2 H CH2 CH2 CH2

CH2 H
CH2 C CH2 CH CH2
C C
CH2 C CH2 CH H CH2 CH 2
CH2 H CH2 CH2 CH2
cyclohexene cis-cyclooctene trans-cyclo-octene
(a) CH2 — CH2 — CH2 H H
CH2
H CH2
(a)
C— C
H H
H CH2 (R)-(–) (S)-(+)
trans-cyclooctene enantiomers
mirror
M-(minus, left-handed) P-(phus, right-handed)

helical configuration
Q. Assign R or S configuration to the following compounds :
OH H H OH
(a) (b)
Ph COOH Me COOH
H COOH NH2
(c) (d)
Me NH2 Me COOH
Sol. (a) R, (b) R, (c) S, (d) S

Q. Assign R or S configuration to the following compounds :
CH3
H
Cl — C C
(a) (b) H CH2CH2CH3
CF3 CH3
CH 2CH3
O
OH
CH 3 H C
(c) (d) CH2CH3
H
CH3 H3C
Sol. (a) R, (b) S, (c) S, (d) R
Q. Assign the absolute configuration R or S to the following compounds :
O2N COOH Ph
H
(a) O2N COOH (b) C— C — C
H Ph
HOOC H
H2N Me
(c) Me NH 2 (d)
Me H
HN C— O
H2 N H | |
O—C NH
C
(e) (f)
HN C— O
H |
NH2
O—C NH
Me
Cl Cl
(g) O2N COOH
Sol. (a) R, (b) R, (c) S, (d) R, (e) R, (f) S, (g) S

Q. Assign the absolute configuration R or S to each chiral centre in the following compounds
H Me
H CH3
b a b a
(a) c OH (b) c H
H H
O
H
OH Me
b a
a
(c) c H (d) b
O
H H
OH H
Me OH
1 b a
8a
(e) 4a (f) c H
H H
H H
b a
(g) c OH
H
Sol. (a) a, S; b, R; c, S
(b) a, S; b, R; c, R
(c) a, S; b, R; c, R
(d) a, S; b, S
(e) 1, S; 4a, R; 8a, S
(f) a, R; b, R; c, R
(g) a, S; b, R; c, R
Resolution
The Separation of a racemic modification into its constituent enantiomers is known as resolution.
Enantiomers have identical, physical and chemical properties so these cannot be separated by
normal physical method.
Separation of Pair of Enantiomer by using Chemical Method (Via Diastereomers)
This is the best method of resolution. In this method a racemic modification is converted into a
mixture of diastereomers by using a pure enantiomer of another compound.

Racemic Optically Pure Compound (R’ or S’)

modification R/S
R’
Mixture of diastereomers
RR'+SR'
The diastereomers have different physical
properties, so can be separated by
any physical method
Fractional Crystallisation
RR' SR'
Hydrolysis Hydrolysis
R + R’ S + R'
Properties of Enantiomers
Enantiomers have identical physical and chemical properties except :
1. Odour
Ex. (+) – Limonene has smell of oranges and
(–) – Limonene has smell of lemons
2. Optical rotation (equal magnitude but opposite direction)
3. Physical activity
Ex. (–) – Nicotine is poisonous than (+) – Nicotine;
(+) – histidine is sweet whereas (–) – histidine is tasteless.
4. Reactivity towards optically active compound because it causes them to behaves as
Diastereomers.
R S
+ R’ + R’
RR’ SR’
Diastereomers
Diastereomers have different (optically active) physical properties
Diastereomers react with O.A (optically active) as well as optically inactive (OI) compounds with
different rate.
Stereochemistry of Chemical Reactions
(A) Stereochemistry of Addition Reactions
Recall that an addition reaction is a reaction in which a general species X — Y adds to each end
of a bond. The cases we’ve studied so far involve addition to double bonds:

An addition reaction can occur in either of two stereochemically different ways, called synaddition
and anti-addition.
The stereochemistry of addition to a double bond is discussed with reference to the plane that
contains the double bond and its four attached groups. The sides of this plane are called faces. The side
of the plane nearest the observer is the top face, and the other side is the bottom face.
In a syn-addition, two groups add to a double bond from the same face:
Syn-Addition :
In an anti-addition, two groups add to a double bond from opposite faces:

Anti-addition:
(B) Stereochemistry of Substitution Reactions

In a substitution reaction, one group is replaced by another. In the following substitution reaction,
for example, the Br is replaced by OH:
   
H3 C — Br    OH 
 H3 C — OH  Br  
   
The oxidation step of hydroboration–oxidation is also a substitution reaction in which the boron
is replaced by an OH group.
–
OH + 3HO – OH + (CH3CH2)3B  3CH3CH2–OH + –B(OH)4
A substitution reaction can occur in two stereochemically different ways, called retention of
configuration and inversion of configuration. When a group X’ replaces another group X with retention
of configuration, then X and X’ have the same relative stereochemical positions. Thus, in the following
example, if X is cis to Y, then X’ is also cis to Y.
Substitution with retention of configuration:
Substitution with retention also implies that if X and X’ have the same relative priorities in the R,S
system, then the carbon that undergoes substitution will have the same configuration in the reactant and
the product. Thus, if this carbon has (for example) the R configuration in the starting material, it has the
same, or R, configuration in the product.
When substitution occurs with inversion of configuration, then X and X’ have different relative
stereochemical positions. Thus, if X is cis to Y in the starting material, X’ is trans to Y in the product:
Substitution with inversion of configuration:
Substitution with inversion also implies that if X and X’ have the same relative priorities in the R,S
system, then the carbon that undergoes substitution must have opposite configurations in the reactant
and the product. Thus, if this carbon has (for example) the R configuration in the starting material, it has
the opposite, or S, configuration in the product.
As with addition, it is also possible that a reaction might occur so that both retention and inversion
can occur at comparable rates in a substitution reaction. In such a case, stereoisomeric products
corresponding to both pathways will be formed. Examples of substitution reactions with inversion, retention,
and mixed stereochemistry are all well known.
As analysis of the stereochemistry of substitution requires that the carbon that undergoes
substitution must be a stereocenter in both the reactants and the products. For example, in the following
situation, the stereochemistry of substitution cannot be determined.
Because the carbon that undergoes substitution is not a stereocenter, the same product is
obtained from both the retention and inversion modes of substitution.
A reaction in which particular stereoisomers of the product are formed in significant excess over
others is said to be a stereoselective reaction. Thus, an addition that occurs only with anti
stereochemistry, is a stereoselective reaction because only one pair of enantiomers is formed to the
exclusion of a diastereomeric pair.
A substitution that occurs only with inversion, is also a stereoselective reaction because one
diastereomer of the product is formed to the exclusion of the other.
(C) Stereochemistry of Bromine Addition
The addition of bromine to alkenes is in many cases a highly stereoselective reaction.
When cis-2-butene reacts with Br2, the product is 2,3-dibromobutane.

You should now realize that three stereoisomers of this product are possible: a pair of enantiomers
and the meso compound. The meso compound and the enantiomeric pair should be formed in different
amounts. If the enantiomers are formed, they should be formed as the racemate because the starting
materials are achiral.
When bromine addition to cis-2-butene is carried out in the laboratory, the only product is the
racemate. Bromine addition to trans-2-butene, in contrast, gives exclusively the meso compound. To
summarize these results:
Experimental Facts :
This information indicates that addition reactions of bromine to both cis- and trans-2-butene are
highly stereoselective. Are these additions syn or anti? Because the alkene is not cyclic , the answer is
not obvious. Study Problem illustrates how to analyze the result systematically to get the answer.
Study Problem
According to the experimental results, is the addition of bromine to cis-2-butene a syn-or an anti
addition?
Solution. To answer this question, you should imagine both syn- and anti-additions to cis-2-
butene and see what results would be obtained for each. Comparison of these results with the experimental
facts then shows us which alternative is correct.
If bromine addition were syn, the Br2 could add to either face of the double bond. (In the following
structures, we are viewing the alkene edge-on.
meso-2,3-dibromobutane

This analysis shows that syn-addition from either direction gives the meso diastereomer. Because
the experimental facts show that cis-2-butene does not give the meso isomer, the two bromine atoms
cannot be adding from the same face of the molecule. Therefore syn-addition does not occur.
Because bromine addition is not a syn-addition, presumably it is an anti-addition. Let’s verify this.
Consider the anti-addition of the two bromines to cis-2-butene. This addition, too, can occur in two
equally probable ways.
(±)-2,3-dibromobutane
This analysis shows that each mode of addition gives the enantiomer of the other; that is, the two
modes of anti-addition operating at the same time should give the racemate. Because the experimental
facts show that bromine addition to cis-2-butene indeed gives the racemate, this reaction is an anti-
addition.
It is very important that you analyze the addition of bromine to trans-2-butene in a similar manner
to show that this addition, too, is an anti-addition.
Thus, formation of a bromonium ion followed by backside substitution of bromide is a mechanism

that accounts for the observed anti-addition of Br2 to alkenes.
The reaction, then, would not be stereoselective. Because this result is not observed, a carbocation
mechanism is not in accord with the data. This mechanism also is not in accord with the absence of
rearrangements in bromine addition. The bromonium-ion mechanism, however, accounts for the results
in a direct and simple way. The credibility of this mechanism has been enhanced by the direct observation
of bromonium ions under special conditions. In 1985, the structure of a bromonium ion was determined
by X-ray crystallography.
(D) Stereochemistry of Hydroboration–Oxidation

Because hydroboration–oxidation involves two distinct reactions, its stereochemical outcome is
a consequence of the stereochemistry of both reactions.
Hydroboration is a stereospecific syn-addition.
The syn-addition of borane, along with the absence of rearrangements, is the major evidence for
a concerted mechanism of the reaction.
Occurrence of an anti-addition by the same concerted mechanism would be virtually impossible,

because it would require an abnormally long B—H bond to bridge opposite faces of the alkene  bond.
The oxidation of organoboranes is a stereospecific substitution reaction that occurs with retention
of stereochemical configuration.
hydroboration–oxidation of an alkene brings about the net syn-addition of the elements of H—OH
to the double bond.

(E) Stereochemistry of Other Addition Reactions

Catalytic Hydrogenation : Catalytic hydrogenation of most alkenes is a stereospecific syn-
addition.
Oxymercuration–Reduction : Oxymercuration of alkenes is typically a stereospecific anti-addition.
Q. Label the following pairs of compounds as homoners, constitutional isomers, enantiomers or

diastereomers.
Me Me
H Cl Cl Cl
N and N and
(a) Ph H H Ph (b)
CH2Ph CH2Ph Cl H H H
H H Br
and and Br
(c) Cl Cl Cl Cl (d) Br
Cl Cl Br
Cl Br Br
Cl O O
and
(e) and (f) Br
Me Me Br
OH
(g) OH and
Sol. (a) enantiomers, (b) diastereomers, (c) homomers, (d) homomers, (e) homomers, (f) diastereomers,
(g) constitutional isomers
Solved Problems
Prob. Show interconversions between various projection formulae, taking suitable examples.
Sol. Example-I
COOH COOH COOH COOH
R
H
* HO Me HO Me H * OH
HO Me R
H
Flying-wedge Perspective H Me
Fischer (eclipsed) Fischer (eclipsed)
H
COOH
COOH COOH
HOOC
HOOC H H H
H Me H
HO Me
OH
H H H OH
Zig-zag OH Newman (eclipsed)
OH
Tetrahedral Sawhorse (eclipsed)
H
Tetrahedral
Example-II
H H
1 OH
COOH OH
rotation by HOOC
COOH 180° COOH
2 HO
H OH H
3 H OH
HO H Sawhorse (staggered)
COOH
4COOH Sawhorse (eclipsed)
COOH COOH
IV HO H H
(2R,3R)-Tartaric acid OH HO H H OH
(active isomer)
Threo– rotation by
Fisher projection (eclipsed) HOOC 180° HO H H OH
COOH
COOH COOH
Newman (eclipsed) Newman (staggered)
Newman (staggered)
1
COOH
2
H OH
(2R,3R)=Tartaric acid
3 (active isomer)
HO H
Threo-
4
COOH Fisher projection (eclipsed)
COOH IV
H OH HOOC HOOC
H
HO H OH
HO OH
COOH HO
H
Perspective COOH COOH
Flying-wedge Zig-zag
Prob. Optically pure (R)-enantiomer of 1-phenylethanol is separately treated with (i) p-TsCl followed by
EtOK and (ii) K followed by EtOTs. Identify the products with their stereochemical relationship.
Sol. Case-I :
Me Me Me
p-TsCl EtOK
OH * * H
OTs
Ph Ph Sn 2
Ph
H H OEt
(inversion) (A)
(R)-1-Phenylethanol Tosylatederivative (R) (S)-1-Ethoxy-1-phenylethane
During tosylation there occurs no change in the configuration of the chiral centre, but the change
occurs in the second step involving a SN2 displacement reaction resulting the product (A) with
inverted configuration.
Case-II :
Me Me Me
K *
OH * O– OEt
Ph Ph SN 2
Ph
H H H
(R)- (B)
(R)-1-phenylethanol (alkoxide as nucleophile) (R)-1-ethoxy-1-phenyl-
ethane
There is no change in configuration of the chiral centre of the product.
Prob. 1,2-Diphenyl-1-propanol may be prepared by either of the two ways:
(i) LiAlH4 reduction of PhCH(Me)COPh.
(ii) Reaction of PhCH(Me)CHO with PhMgBr.
Which method would you choose to prepare the threo-isomer? Give reason in favour of your
answer.
Sol. The second method would be effective in preparing the threo-isomer of 1,2-diphenyl-1-propanol
as may be rationalized from the following reaction sequence. The nucleophilic attack at the
carbonyl carbon obeys Cram's rule and accordingly the products will be erytho- as major one
from both the (R)- & (S)-isomers of PhCH(Me)COPh and threo-from both the (R)- & (S)-isomers
of PhCH(Me)CHO.
O
Me H HO H
Me H
1. LiAlH4
+
2. H3O
Ph Ph
Ph Ph
R-isomer
(preferred conformation) (R,R)-erythro-isomer
O H OH
H Me H Me
1. LiAlH4
+
2. H3O
Ph
Ph Ph
Ph (S,S)-erythro-isomer
S-isomer
(preferred conformation)
O
Me H HO Ph
Me H
1. LiAlH4
2. H3O+
Ph Ph
H H
R-isomer (S,R)-threo-isomer
O Ph OH
Me H Me
H
1. LiAlH4
+
2. H3O
Ph
Ph H
H (R,S)-threo-isomer
S-isomer
Prob. What do you mean to say 'anomeric effect' ?
Sol. Let us consider the axial and equatorial isomers of 2-methoxy tetrahydropyran :
O O
H OMe
OMe H
(axial-isomer) (equatorial-isomer)
From the first sight it is apparent that the equatorial-isomer having anomeric substituent at
equatorial position should be more stable than the axial-isomer; but in practice the reverse is the
observed phenomenon. This is usually observed when the anomeric substituents are electronegative
having non-bonding electron-pair(s). Such preference of electronegative substituents for the axial
position at the anomeric carbon is known as anomeric effect. Electronic repulsion between non-
bonding electrons on the ring oxygen atom and those on the equatorially oriented methoxyl
oxygen is greater in magnitude than that developed in the axial isomer as they are farther apart
in the latter geometry.
O O Equatorial-isomer
Axial-isomer (electronic repulsion
H O
(electronic repulsion is more)
1 (stability order) 1 CH3
is less)
O H
CH3
Due to such anomeric effect a-anomer of methyl D-glucopyranoside is more stable than the -
anomer.
H CH
6
H 6
2OH CH2OH
4 H 4
H
HO 5
-O HO 5 -O
HO 3 H HO 3 O
2
1 (stability order) 2
CH3
Methyl H H OH
1
H H OH
-D-Glucopyranoside O H
(electronic repulsion CH Methyl -D(+)-Glucopyranoside
is less)
3
(electronic repulsion is more)
Q. State whether the marked hydrogens HA, HB in the following compounds are homotopic, enantiotopic
or diastereotopic. Give reasons in favour of your answer.
Et Et
Et
HA OH Br Br HA
HO HB H
H
Et HA HB HB
(I) (II) (III)
Ans. The best way of ascertaining the topicity of a pair of identical ligands in a molecule is to carry
out substitutions of the concerned ligands, one at a time, by a non-identical ligands. If those
manipulations give same compounds, then the ligands in questions are homotopic. If enantiomers
are formed, then the ligands are enantiotopic and if a pair of diastereoisomers is formed, ligands
are diastereotopic.
On the basis of this argument, HA and HB in (I) are homotopic. HA and HB in (II) are enantiotopic
and HA and HB in (II) are diastereotropic. These can be shown by the following substitutions.
Et Et Et
Replacement of
HA OH HA and HB X OH ; H OH
HO HB by X in turn HO HO
H X
Et Et Et
(I)
A pair of homomers
(HA and HB
(Identical)
are homotopic)
Et Et Et
Br Br Replacement of Br Br Br Br
H HA and HB H H
by X in turn ;
HA HB X H H X
(II) A pair of enantiomers
(HA and HB
are enantiotopic)
Et Et Et
Replacement of
HA HA and HB H X
H by X in turn H H
HB (III) X H
A pair of diastereoisomers
(HA and HB
are diastereotopic)
Q. Find out the absolute configuration of the asterisked chiral centre of each of the following
compounds. Give explanation in each case.
CH(n-C5H11)2
CH2OCH2CH3
(a)
*
(b) (n-C6H13)2CH C*
CH2CH2OCH2CH3
O H

HO HH
OH CH 3
C C N — CH CH — N
H3C * CH3 || C *C C
(c) C (d) N — NH N — NH
H CH3 H
CH3
H OH
CH 3 Cl
H OH
Cl C* H * OH
(e) (f) HO H
CH 3O H OCH3 H OH
CH3
Ph Me Me
OH H
| C—C
CH3CH2CH2—C—* CHDCH3 C— C
(g) (h) H *
C
| Ph
H HO H
16 +
OH NH3
(i) — C *C
CH3— C — CH3
(j) H2 N * COO
18
OH COOH
Ans. (a) Ligand complementation is required when there is a cyclic component to a ligand. In the
present case, cyclic oxide ring (THF derivative) can be written in the disconnection form
as shown here, where the chiral centre itself serves as a duplicated atom at the end of
the expanded chains. Duplicated atom is written within the parentheses. Phantom atoms
are inserted for tetra ligandation of the phantom atoms.
2
CH2OCH2CH3 4
CH2OCH2CH3 H2 C
* 3
CH2CH2OCH2CH3 H2C C* 3 2
CH2CH2OCH2CH3
O
000 (C) CH2—O CH2—O—CH2CH2 (C)000 1
4 1
After opening the ring, CIP rules may be applied to find out the absolute configuration. In
Fischer projection the compound is as just shown. Therefore, the absolute configuration
of the asterisked carbon atom is 'S'.
(b) The compound can be written in the following disconnected form.
3 3
CH(n-C5H11)2 CH (n-C 5H 11)2
2 (CH2)5—(C)000 1 2
(n-C6H13)2 HC C* (n-C6H13)2HC C CH
1
(CH2)5—(C)000
H H 4
4
Applying CIP rules, the disconnected compound can be written in the Fischer form, as
shown. Therefore, the absolute configuration of the chiral centre is S.
(c) In the compound, asterisked chiral centre is attached to two enantiomorphic groups.
According to CIP rules, the enantiomorphic group having R-configuration has priority over
the group having S-configuration.
S
HO HH OH HO HH R OH CH(OH)CH3 2 2
S
C C C C 3
H3 C *
C
CH3 H3 C *
C
CH 3 H 3C * H 4 3 4
H CH3 H CH3 R 1
CH(OH)CH3
1
Therefore, the absolute configuration of the asterisked chiral centre of R. Lowest priority
group (4) is on a horizontal bond.
N N
(d) In this example, the cyclic groups, and are interconvertible by
N N N N
tautomeric change. H H
N N




N N HN N
H
Both of these groups can be expanded as shown.
(C) (N) (C) (C)
N N N N
;
* * *
C NH
C N C N *
C NH
N (C) N (N) N N
H H (N)
|
(C)
N N
*
Therefore, the tautomeric form C *
NH gets priority over the form C N
N N
H
The absolute configuration of the chiral centre is (R).
3
CH3 3
N N
2 C 1
2 1
N N N NH
H 4
H4
(R)
(e) In this case, we move along the prior branches following –CH(OCH3)CH2– and find the
first difference in the cyclohexane ring having Cl atom marked. That is why the left-hand
ring has priority. It is to be noted that the Cl+ being on the junior branch, that is, less prior
branch, does not in this case affect the result although it is closer to the branch point.
3
CH3 Cl 3
Cl 1 2
C*
4
H3CO H OCH3
1 4 2
Configuration of the asterisked chiral centre is S
(f)
1
CH3
2
H OH
3
H OH
H 4
* OH
5
HO H
6
H OH
CH3
In this compound, chiral centres C-2, C-3, C-5, and C-6 have the configurational
descriptors, S, S, S, and R respectively. Therefore, the compound can be written as
shown in the figure. According to CIP rules (1966), (S, S) gets priority over (S, R).
Therefore, the priority order of the ligands is in the Fischer projection, and the absolute
configuration of the asterisked chiral centre is R.
b
S, S
d a
H OH
*
S, R
c
 = Chiral centre
at C-4
(g) In this compound, the priority order of the substituents attached to the chiral centre is –
OH> –CH2CH2CH3 > –CHDCH3 > –H. When isotopic atom is present in the group but not
directly attached to the chiral centre then atomic number method (Rule 1) should be first
tried out to determine the priorities of the groups. That is why, –CH2CH2CH3 gets priority
over –CHDCH3.
1
OH 1
CH3CH2CH2 C* CHDCH 3 2 3
2 3
H 4
4 (S)
The absolute configuration of the compound is S.

(h) According to CIP rules (1966), between the two diastereomeric groups, one having Z
configuration gets priority over the group having E configuration.
3
Ph Me Me H
E Z
C—C 4 1
C— C
3 * 2
H C Me 2
HO H (R)
1 4
Therefore, the configuration of the asterisked chiral centre is S.

–18
(i) In the compound, the priorities of groups attached to the chiral centre are OH > –CC–
CH3> – C6H4 –CH3. Therefore, the compound can be written as

2
16
OH
2
CH3 C C C* CH3 3 4
3 18
OH 4 1
1
The absolute configuration in R. The lowest priority group (4) is on a horizontal bond.
(j)
+
NH3

–
H2 N COO
COOH

In the compound, the priority order is – NH3 –NH2 > –COOH > –COO–
This is because of the fact that according to CIP rules, H atom gets priority over lone pair
of electrons (..). The charged atoms have no effect on the determination of priorities.
Therefore, the compound can be written as
+
NH3 1

H2N COO
– 2 4
COOH 3
The configuration of the chiral centre is, therefore, R.
Q. What would be the be absolute configurations of atrolactic acid from the following sequence of
reactions.
O
 M
+
Ph C C CH 3MgX H3O
O L ? ?
(a) C
S
O
O
 S
+
Ph C C CH 3MgX H3O
O L ? ?
(b) C
M
O
O
 M
C C PhMgX H3O+
CH3 O L ? ?
(c) C
S
O
O
S

C C PhMgX H3O+
CH3 O ? ?
(d) C L
M
O
Ans. The respective compounds in each case are shown.

(a)
O O
M
Ph C * CH3MgX M
C Ph C *
C
C O L workup O
C L
S HO CH3 S
O
H 3O+
COOH
OH
Ph CH 3
(R)-Atrolactic acid
(b)
O O
M
* CH3MgX S
Ph C C Ph C *
C O C
L C O L
S HO CH3 M
O
H 3O+
COOH
CH3
Ph OH
(S)-Atrolactic acid
(c)
O O
M
* PhMgX M
CH 3 C C CH 3 C *
C O C
L working C O L
S HO Ph S
O
+
H 3O
COOH
OH
H3 C Ph
(S)-Atrolactic acid
(d)
O O
S S
C * PhMgX *
CH 3 C CH 3 C C
C O L working O
C L
M Ph OH M
O
+
H 3O
COOH
Ph
H3 C OH
(R)-Atrolactic acid
Q. Identify the pro-R and pro-S hydrogen atoms (marked) in each of the following molecules.
1
COOH
2
H OH
a 3
H H OH
a 4 b
OH H H
(a) (b) H
5
OH
H3C H
b
H
6
OH
7
COOH
CH3
CH3 Br
a
H H
(c) Ph (d) CH3
Br H
a
b b
H H OH
b a a
H H H H
OH
H C CH3 CH3
(e) C—
—C C— —C (f) H
H3C H3C CH3 H Hb
1
CH3
2
H OH
H Cl a H
3
OH
H b 4 a
Hb H H
(g) (h) H
5
OH
H 6
Cl H OH
7
CH3
Ans. (a) In the compound, Ha is pro-S and Hb is pro-R.
(b) In the compound, C-2 and C-3 have R-configurations and C-5 and C-6 have S-configuration.
Therefore, the compound can be represented by the Fischer projection,
R, R
Ha Hb
S, S
According to CIP rules, (R, R) gets priority over (s, s). Therefore, Ha in the compound is
pro-S and Hb is pro-R.
(c) In this compound, Ha is pro-S and Hb is pro-R.
(d) In this molecule, Hb is pro-R and Ha is Pro-S.
(e) In this case, diastereoisomeric E and Z groups are attached to the carbon centre bearing
Ha and Hb. The molecule can be represented as
b
H H
a
b a
H C H H
E CH 3
Z C
C—C C—C
H3C H3C CH3 H E Z
According to CIP rules, Z-gets preference over E. Therefore Ha is pro-S and Hb is pro-R.
(f) In this cyclohexane derivative, Ha is pro-R and Hb is pro-S.

(g) In this molecule, the carbon atoms bearing –Ch(Cl)-groups are enantiomorphic having R
and S configurations. According to CIP rules, the enantiomorphic group with R-configuration
gets priority over the enantiomorphic group having S-configuration. Therefore, in this
compound Ha is pro-S and Hb is pro-R.
H Cl
a
R H
Hb
Cl
S
H
(h) In this structure, C-2 and C-3 have S and R configuration respectively. Again, C-5 and C-
6 have S and R configuration respectively. Therefore, the compound can be represented as
1
CH3 2
S
2 S
H OH 3
3 R R
H OH
Hb 4
Ha H
b
H
a
5 S
H OH 5
6 R S
H OH
7 6
CH3 R
According to CIP rules, like configuration (R, R) or (S, S) gets preference over either (R,
S) or (S, R). However, in this case, standard sub rules (5) may be used where R
precedes over S. According to this rule, Ha in (h) represents pro-r hydrogen and Hb
represents pro-s hydrogen C-4 is a pro-pseudoasym-metric centre.
Q. Find out the absolute configurations of the chiral centres of compounds formed from the following
reactions.
(a) Br2 is added to Re-Re and Si-Si faces of fumaric acid.
(b) Acetaldehyde is treated with PhMgBr where nucleophilic attack occurs on the Si-face.
(c) R-3-hydroxybutanal is treated with CH3MgBr where nucleophilic attack on the aldehydic
carbonyl takes place from the Re-face.
(d) Z-isomer of 2,3-dibromobut-2-ene is catalytically hydrogenated where hydrogenation takes
place from the Re-Si face looking from the top.
Ans. (a) Fumaric acid is trans-butenedioic acid. It can be represented as follows, one having Re-
Re face and the other having Si-Si face looking from the top.
H COOH HOOC H
C C
C C
HOOC H H COOH
Re-Re face Si-Si face
Br2 addition is electrophilic trans-addition. One bromine becomes attached from the top
and the other from the bottom. In case of trans-addition to a symmetrical trans-alkene,
meso-compound is always formed. Therefore, both Re-Re and Si-Si faces give the some
meso-2,3-dibromobutanedioic acid. That is Re-Re and Si-Si faces are homotopic in this
particular case.

H COOH CH3 HOOC H

C C
Br2 H Br Br2
C H Br
C
HOOC H H COOH
Re-Re face CH3
(2S, 3R)-2,3-Dibromobutane Si-Si face
(b) The Si-face of acetaldehyde, as observed from the top, is
CH3
C—O
H
The nucleophilic addition to the Si-face of acetaldehyde with PhMgBr is given here.
Ph
–
H 3C Ph H3C Ph
H3C
C H2O C
C O + PhMgBr H OH
H OMgBr
H Si-face (R)-configuration
The secondary alcohol formed has R configuration.

(c) R-3-Hydroxypropanal in flying wedge projection is shown and that reacts with CH3MgBr
from the Re-face.
–
CH3
H H OH
CH3MgBr H3C 
H3C —O C
C—
C H2O C CH3
OH H OH
H
Re-face meso-compound
The carbonyl face of the compound represents a diaste-reotopic face. The absolute
configuration of the newly formed chiral centre (asterisked) is R.
(d) The compound on catalytic hydrogenation gives meso-2,3-dibromobutane. Catalytic
hydrogenation is a cis-addition reaction.
Re
H3C Br
C
C
H3C Br
Si
2,3-Dibromobut-2-ene (Z-isomer)
+H2
Ni or Pt
1 1
H CH3 CH3
2
H
2
Br Br H
H3C Br or
3
H H 3
Br Br H
4 4
CH3 CH3
H3C Br
(2S, 3R)-2,3- or (2R, 3S)-2,3-
Dibromobutane Dibromobutane

Chemical Sciences (MSP)
CSIR-UGC (NET) Chemical Sciences

Model Solved Paper
Duration : 180 minutes Maximum Marks : 200
Read the following instructions carefully.
The question paper is divided in three parts :
Part ‘A’ : This part contains twenty (20) objective type questions. The candidates shall be required
to answer any 15 questions. Each question shall be of two marks. The total marks
allocated to this section shall be 30 out of 200.
Part ‘B’ : This part contains forty (40) objective type questions. The candidate shall be required to
answer any 35 questions. Each question shall be of two marks.The total marks allocated
to this section shall be 70 out of 200.
Part ‘C’ : This part contains sixty (60) objective type questions. A candidate shall be required to
answer any 25 questions. Each question shall be of four marks. The total marks allocated
to this section shall be 100 out of 200.
» There will be negative marking for all PART @ 25% marks for each wrong answer.

PART - ‘A’
1. Select the right option which can be placed at the sign of interrogation ?
4 8 20
9 3 15
6 6 ?
(A) 24 (B) 16
(C) 20 (D) 18
2. If GIVE is coded as 5137 and BAT is coded as 924, how is GATE coded?
(A) 5427 (B) 5724
(C) 5247 (D) 2547
3. Starting from his house, Sachin walks a distance of 8m towards north, then he turns left and
walks 6m, then walks 3m towards south and finally travels 6m towards west. To reach his office.
What is the distance between his house and office ?
(A) 10m (B) 13m
(C) 12m (D) 16m
4. Problem Figures
Answer Figures
(A) (B)
(C) (D)
5. EFG2, EFGH2, EFGHI2, _____ ,EFGHIJK2.

(A) EFGH3 (B) EFGHI3
(C) E3FGHI (D) EFGHIJ2
6. The largest triangle is inscribed in a semi-circle of radius 4 cm. Find the area inside the semi
circle which is not occupied by the triangle.
(A) 8( – 2) sq cm (B) 7( – 1) sq cm
2
(C) 8( – 1) sq cm (D) 6( – 2) sq cm

4
7. If tan = and 0 <  < 90°, then find the value of sin  + cos  ?
3
3 7
(A) (B)
5 25
7 7
(C) (D)
5 10
8. Two dice are thrown together .What is the probability that the sum of the number on the two faces
is divided by 4 or 6 ?
(A) 7/18 (B) 14/35
(C) 8/18 (D) 7/35
9. Length of train is 130 meters and speed of train is 45 km/hour. This train can pass a bridge in
30 seconds, then find the length of the bridge.
(A) 230 meters (B) 235 meters
(C) 240 meters (D) 245 meters
10. Jayesh is as much younger to Anil as he is older to Prashant. If the sum of the ages of Anil and
Prashant is 48 years, what is the age of Jayesh?
(A) 20 (B) 24
(C) 30 (D) cannot be determined
11. A grocer has a sale of Rs.6435, Rs.6927, Rs.6855, Rs.7230 and Rs.6562 for 5 consecutive
months. How much sale must he have in the sixth month so that he gets an average sale of
Rs.6500?
(A) Rs.4991 (B) Rs.5991
(C) Rs.6001 (D) Rs.6991
12. In a mixture 60 liters, the ratio of milk and water 2 : 1. If the this ratio is to be 1 : 2, then the
quantity of water to be further added is
(A) 20 liters (B) 30 liters
(C) 50 liters (D) 60 liters
13. Which of the following numbers will completely divide (325 + 326 + 327 + 328)?
(A) 11 (B) 16
(C) 25 (D) 30
14. Six sides of the block are coloured Green, Blue, Red, Yellow, Orange, White in the following
manner :
White Orange
Yellow
Blue
Green Red
When Blue is on top, which colour will be at the bottom ?

(A) Orange (B) Red
(C) White (D) Yellow
Direction (15) : Study the graph and answer the question.
Firm’s position
60
Income
Income of Exp.
50
(in lacs)
40
30
Expenditure
20
10
1970 1975 1980 1985 1990

15. Which conclusion is not true ?
(A) Profit of the firm was minimum in 1980 and maximum in 1985
(B) Rate of increase in income is less than that of increase in expenditure upto 1980
(C) There is a direct relation between income and expenditure after 1980
(D) All of the above
16. A play ground is rectangular in shape. In order to make this ground fit for games, Rs 1000 was
spent at the rate of 25 paise per m². The width of the field is 50 m. If the length of the ground
is increased by 20 m, the cost of making it suitable for game at the same rate in rupee will be?
(A) 1,250 (B) 1,000
(C) 1,500 (D) 2,250
17. Find the number of triangles in the below figure?
(A) 10 (B) 12
(C) 18 (D) 13
18. Which will replace the question mark?
(A) 80 (B) 10
(C) 88 (D) 84
19. Sum of three Natural numbers a, b and c is 10. How many ordered triplets (a, b, c) exist?
(A) 45 (B) 36
(C) 54 (D) 28
20. Teepu sells onions in the streets of Chandni Chowk. Due to recent shortfall in the supply of
onions, he doubles his selling price despite the cost price remains same for him due to a fixed
price contract. He realizes that his profit have tripled. Find the original profit percent.
(A) 100/6% (B) 100%
(C) 120% (D) 105%
PART - ‘B’
21. The structure of SbPh5 and PPh5 respectively are

(A) Trigonal bipyramidal, square pyramidal
(B) Square pyramidal, trigonal bipyramidal
(C) Trigonal bipyramidal, trigonal bipyramidal
(D) Square pyramidal square pyramidal
22. Lewis acidity of BCl3, BPh3, BMe3, with respect to pyridine follows the order.
(A) BCl3 > BPh3 > BMe3 (B) BMe3 > BPh3 > BCl3
(C) BPh3 > BMe3 > BCl3 (D) BCl3 > BMe3 > BPh3
23. Which one of the following reactions is not expected to occur on HSAB principle
(A) NaF + HCl  NaCl + HF (B) CaCl2 + 2F–  CaF2 + 2Cl–
(C) HgCl2 + 2F–  HgF2 + 2Cl– (D) MgO + H2O  Mg(OH)2
24. The correct statement about C60 is

(A) C60 is soluble in benzene
(B) C60 does not react with tert-butyllithium
(C) C60 is made up of 10 five-membered and 15 six-membered rings.
(D) Two adjacent five-membered rings share a common edge.
25. For the complex ion [Cu(NH3)6]2+, the coordination geometry will be
(A) octahedral (B) Tetragonally distorted octahedral
(C) Trigonal prismatic (D) Trigonal antiprismatic
26. Coordinated water molecules of a Cd(II) complex can be successively replaced by Br– finally to
result in [CdBr4]2–. In this process, the fourth equilibrium constant is observed to be higher than
the third one, because
(A) equilibrium constant for the last step is always the highest.
(B) three molecules of H2O are released during the fourth step.
(C) the aqua-Cd(II) species is octahedral.
(D) an anion(Be–) replaces a neutral (H2O) molecule from the coordination sphere.

27. The correct order of the rate of exchange of water molecules between the coordination sphere
and the bulk is
(A) Cr3+ < Al3+ < Cr2+ < Ni2+ (B) Cr3+ < Al3+ < Ni2+ < Cr2+
(C) Cr3+ < Ni2+ < Cr2+ < Al3+ (D) Cr3+ < Cr2+ < Al3+ < Ni2+
28. Considers the reactions.

A. [Cr(H2O)6]2+ + [CoCl (NH3)5]2+  [Co(NH3)5(H2O)]2+ + [CrCl(H2O)5]2+
B. [Fe(CN)6]4– + [Mo(CN)8]3–  [Fe(CN)6]3– + [Mo(CN)8]4–
Which one of the following is the correct statement?
(i) Both involve an inner sphere mechanism
(ii) Both involve an outer sphere mechanism
(iii) Reaction A follows inner sphere and reaction B follows outer sphere mechanism
(iv) Reaction A follows outer sphere and reaction B follows inner sphere mechanism
(A) i (B) ii
(C) iv (D) iii
29. Ligand field stabilization energies are smaller for lanthanides compared to transition metals in the
same oxidation state because
(A) Size of lanthanide ions are larger.
(B) f orbitals interact less effectively with ligands.
(C) Size of lanthanide ions are smaller.
(D) Lanthanides favour oxygen donor ligands.
30. The red colour of oxyhaemoglobin is mainly due to the

(A) d-d transition
(B) Metal to ligand charge transfer transition
(C) Ligand to metal charge transfer transition
(D) Intraligand   * transition
31. The ortho form of molecular hydrogen contains

(A) Nuclear spins which are opposed to each other
(B) Nuclear spins which are aligned to each other
(C) Nuclei with one proton and one neutron
(D) Nuclei with one proton and two neutrons
32. Solubility product constants (Ksp) of salts of types MX, MX2 and M3X at temperature ‘T’ are 4.0 ×
10–8, 3.2 × 10–14 and 2.7 × 10–15, respectively, solubilities (mol dm–3) of the salts at temperature
‘T’ are in the order :
(A) MX > MX2 > M3X (B) M3X > MX2 > MX
(C) MX < M3X < MX2 (D) MX2 > M3X > MX
33. The order of carbonyl stretching frequency in the IR spectra of ketone, amide and anhydride is
(A) Anhydride > Amide > Ketone (B) Ketone > Amide > Anhydride
(C) Amide > Anhydride > Ketone (D) Anhydride > Ketone > Amide

34. The compound that is NOT aromatic is
+ –
(A) (B)
– –
(C) (D)
–
35. The gauche interaction values for Me/Me, Me/Br and Br/Br are 3·3, 0·8 and 3·0 kJ/mol, respectively.
Among the following, the most stable conformation of 2,3-dibromobutane is
Br Br
Me Br H Me
(A) (B)
Me H Me H
H Br
Br Br
H Br Br Me
(C) (D)
Me H Me H
Me H
36. The major products X and Y formed in the following reactions are
Mel
x
25ºC
N NaH, Mel
H y
(A) x= y=
N + N –
N N l
H
Me Me
(B) x= y=
–
+
N N N N
H
Me Me
(C) Me
Me
x= y=
N N N N
H H
(D) x= y=
–
+
N N N N
H Me H
Me
37. The expected product of the reaction is :

S 
 H2 O /H/ 

(i) BuLi
78 C
 (A)   (B)   (P)
(ii) EtBr
EtO
O
Et S
(A) Et (B)
S OEt
O
Et O
(C) (D) Et
OH CHO
38. In the given reaction

OH
COOH
HNO3/H 2SO4
[X]
[X] is :
(A) 2-hydroxy-3-nitrobenzoic acid (B) 2-hydroxy-5-nitrobenzoic acid
(C) 2, 4, 6-trinitrophenol (D) 2-hydroxy-4-nitrobenzoic acid
39. The compound (C) in the given reaction

–
KCN/C2H5OH/HOH KOBr3 (i)C2H5OH/OH
CHO (A) (B) +
(C)
O (ii) H
is :
OH
OH O |
| ||
C
(A) CH — C (B) O O
|
O O COOH
O O O
|| || ||
(C) CH2 — C (D) C—C
O O O O
40. The reagent for the following conversion is :
(A) KMnO4/NalO4, 
  
(B) O3 / CH3  S  CH3 ; Ag2O;C2H5OH / H;C2H5 O/ C2H5OH : H2O / H 
(C) O3/CH3 — S — CH3 ; Ag2O, 
(D) All of these

41. The correct combination of reagents required to effect the following conversion is:
I
N N
O O
(A) I2, HNO3 (B) s-BuLi, –78ºC followed by KI
(C) NaOEt followed by ICH2CH2I (D) s-BuLi, –78ºC followed by ICH2CH2I
42. Among the following dienes, the one that undergoes a degenerate cope rearrangement is
H
(A) (B)
H
(C) (D)
43. The major product formed in the following reactions is

N2
O O
1.h, aq.THF

2. 
O
N O
(A) N (B)
O
O
O
(C) (D)
OH
44. Match List-I with List-II and select the correct answer using the codes given below the lists :
List - I List - II
(a) (+) and ( ) glucose (1) Mutarotation
(b) -D and -D glucose (2) Enantiomers
(c)  form, open chain form and (3) Anomers
-form
(d) R and S-notation (4) Configurational relationship
Codes :
a b c d
(A) 2 3 4 1
(B) 2 3 1 4
(C) 3 2 4 1
(D) 3 2 1 4
45. Polymerisation using Ziegler-Natta catalysis is advantageous over free radical polymerisation
because :
(A) It can lead to living polymers via anionic polymerisation
(B) It allows one to make polymers of specific tacticity
(C) It gives highly branched polymer with a high degree of crystallinity
(D) It permits step-reaction polymerisation resulting in a highly cross-linked polymer
46. The number of signals that appear in the broad band decoupled 13C NMR spectrum of phenanthrene
and anthracene, respectively are
(A) Ten and four (B) Ten and ten
(C) Seven and four (D) Seven and seven
 – 2
– 
E
47. +
 + 2
Shown above is the energy level diagram far the -orbitals of benzene, calculated on the basis
of huckel molecular orbital theory. According to this theory delocalisation energy of benzene of the
six electrons of the ground state benzene is given by
(A) 4 (B) 3
(C) 2 (D) 1
48. Consider the following :

 H   G   T 
1.    Cp 2.   V 3.     JT
 p p  p T  p H
Which of the above is/are the thermodynamic relation?
(A) 1 only (B) 1 and 3
(C) 2 and 3 (D) 1 and 2
49. The number of microstates that are possible, when two particle are distributed in four states such
that resulting wave functions are anti-symmetric with respect to exchange of the particle is -
(A) 16 (B) 12
(C) 8 (D) 6
50. The initial rate r0 of a certain reaction depends on the initial concentration of species A, B and
C as shown in the table. (Concentration in mM and r0 in mM s–1)
[A]0 [B]0 [C]0 r0
I 1.00 1.00 100 1.0
II 1.00 2.00 100 2.0
III 2.00 2.00 100 4.0
IV 1.00 1.00 400 0.25
What is the orders of the reaction?
(A) 2 (B) 4
(C) 3 (D) 1

51. A first order decomposition reaction complete its 50% in 20 minutes. In what does it complete
its 87.5%?
(A) 35 minutes (B) 40 minutes
(C) 50 minutes (D) 60 minutes
52. Calculate molar conductivity for NH4OH given that molar conductivity for Ba(OH)2, BaCl2 and
NH4Cl are 523.28, 280.0 and 129.8 S cm3 mol–1 respectively.
(A) 200.44 S cm2 mol–1 (B) 147.22 S cm2 mol–1
(C) 251.44 S cm2 mol–1 (D) 300.22 S cm2 mol–1
53. A dilute solution of KCl was placed between two Pt electrode 10.0 cm apart. Across which a
potential difference of 6.0 volt was applied. How far would K+ ions move in 2 hour at 25°C? Ionic
conductivity of K+ at infinite dilution is 73.52 S cm2 eq–1. at 25°C.
(A) 2.125 cm (B) 3.292 cm
(C) 1.511 m (D) 2.512 cm
54. If the bond length of heteronuclear diatomic molecule is greater in the upper vibrational state, the
gap between the successive absorption lines of P-branch.
(A) Increases non linearly (B) Decreases non linearly
(C) Increases linearly (D) Decreases linearly
55. Among the following, the CORRECT statement is

(A) The number of irreducible representations is equal to classes of symmetry options.
(B) The number of irreducible representations is equal to the order of the symmetry point
group.
(C) The irreducible representations contained in any point group are always of the dimension.
(D) A symmetry point group may not contain a totally symmetric irreducible representation.
56. A compound AxBy has a cubic structure with A atoms occupying all corners of the cube as well
as all the face centre positions. The B atoms occupy four tetrahedral voids. The values of x and
y, respectively, are
(A) 4,4 (B) 4, 8
(C) 8,4 (D) 4,2
x
57. Graph between log and log P is straight line inclined at an angle  = 45°. When pressure of
m
0.5 atm and log k = 0.699, the amount of solute adsorbed per g of adsorbent will be
(A) 1 g/g adsorbent (B) 2.5 g/g adsorbent
(C) 1.5 g/g adsorbent (D) 0.25 g/g adsorbent
58. If the dissociation constant of NH4OH is 1.8 × 10–5 the concentration of OH– ions in moles per
litre of a 0.1 molar NH4OH solution is
(A) 1.80 × 10–6 (B) 1.34 × 10–3
(C) 4.20 × 10–3 (D) 1.80 × 10–4

59. The pressure of a moist gas at 27°C is 2 atm. The volume of the container is doubled at the
same temperature. The new pressure of the moist gas (Given vapour pressure of water at 27°C
= 0.4 atm)
(A) 1 atm (B) 0.9 atm
(C) 1.2 atm (D) 1.1 atm
60. At 80°C, the vapour pressure of pure liquid ‘A’ is 280 mm Hg and that of pure liquid ‘B’ is 1000
mm Hg. If a mixture solution of ‘A’ and ‘B’ boils at 80°C and 1 atm pressure, the amount of ‘A’
in the mixture is (1 atm = 760 mm Hg)
(A) 52 mol per cent (B) 34 mol per cent
(C) 48 mol per cent (D) 50 mol per cent
PART - ‘C’
61. The first ionisation energy of Na, NO, Xe and O2 follows the order Na < NO < Xe  O2. O2 reacts
with the powerful oxidising agent, PtF6 to yield O2+[PtF6]–. If PtF6 is allowed to react with other
mentioned species then the products is
(A) Na+[PtF6]– (B) NO+[PtF6]–
(C) Xe+[PtF6]– (D) Na+[PtF6]–, NO+[PtF6]–, Xe+[PtF6]–
62. [XeO6]4– is octahedral whereas XeF6 is a disordered one, because

(A) fluorine is more electronegative than oxygen
(B) Xe-F bond has more ionic character
(C) XeF6 is neutral whereas [XeO6]4– is anionic.
(D) Xe has a lone-pair in XeF6
63. According to polyhedral electron count rule, the structure of Rh6(CO)16 is :

(A) closo (B) nido
(C) arachno (D) hypho
64. Which of the following given below is a closo-carborane?

(A) CB4H55  (B) CB4H56 
(C) CB4H5 (D) CB4H52
65. In a homogeneous catalytic reaction, 1.0 M of a substrate and 1.0 M of a catalyst yields 1.0 mM
of a product in 10 seconds. The turnover frequency (TOF) of the reaction (s–1) is
(A) 10–2 (B) 102
(C) 10–3 (D) 103
66. The Bronsted acidity of boron hydrides follows the order

(A) B2H6 > B4H10 > B5H9 > B10H14 (B) B2H6 = B4H10 > B5H9 = B10H14
(C) B10H14 > B5H9 > B4H10 > B2H6 (D) B5H9 = B4H10 > B2H6 > B10H14

67. The reaction of [Cp2TaMe2] (Cp = C5H5) with NaOMe yields.

(A) [Cp2Ta(OMe)2] (B) [Cp2Ta(Me)OMe]
(C) [Cp2Ta(Me) = CH2] (D) [Cp2Ta(OMe) = CH2]
68. Which one of the following has larger number of isomers?

(R = alkyl group, en = ethylenediamine)
(A) [Ru(NH3)4Cl2]+ (B) [Co(NH3)5Cl]2+
(C) [Ir(PR3)2H(CO)]2+ (D) [Co(en)2Cl2]+
CO
69. The correct name of (CO)3 Fe — CO — Fe(CO)3 is :
CO
(A) Hexacarbonyl iron(III) -tricarbonyl ferrate(0)
(B) Tricarbonyl iron(0) -tricarbonyl iron(0) tricarbonyl
(C) Tri--carbonyl bis (tricarbonyl) iron(0)
(D) None of these
70. Three bands in the electronic spectrum of [Cr(NH3)6]3+ are due to the following transitions.
(a) 4
A2g  4Tig (b) 4
A2g  4T2g
(c) 4
A2g  2Eg
Identify the correct statement about them.
(A) Intensity of (A) is lowest.
(B) Intensity of (C) is lowest.
(C) Intensities of (A), (B) and (C) are similar.
(D) Intensities of (B) and (C) are similar.
71. Considering the quadrupolar nature of M-M bond in [Re2Cl8]2–, the M-M bond order of
[Re2Cl4(PMe2Ph)4]+ and [Re2Cl4(PMe2Ph)4] respectively are
(A) 3.0 and 3.0 (B) 3.0 and 3.5
(C) 3.5 and 3.5 (D) 3.5 and 3.0
72. The pair of compounds having the same hybridization for the central atom is
(A) XeF4 and [SiF6]2– (B) [NiCl4]2– and [PtCl4]2–
(C) Ni(CO)4 and XeO2F2 (D) [Co(NH3)6]3+ and [Co(H2O)6]3+
73. The set of ions expected to show Jahn-Teller distortion in their complexes is
(A) Cu2+, Ti3+, Fe3+ (LS) (B) Ti3+, Cu2+, Fe3+ (HS)
(C) Cu+, Ni2+, Fe3+ (HS) (D) Fe3+ (LS), Cu+, Mn2+ (HS)
74. In the reaction shown below X and Y respectively are
Mn2  CO 10 

Na
 X  
CH3 COCl
  Y
(A) [Mn(CO)4]–, [CH3C(O) Mn(CO)5] (B) [Mn(CO)4]2–, [CH3C(O) Mn(CO)5]

(C) [Mn(CO)5]–, [ClMn(CO)5] (D) [Mn(CO)4]2–, [ClMn(CO)5]–

75. The separation of trivalent lanthanide ions, Lu3+, Yb3+, Dy3+, Eu3+ can be effectively done by a
cation exchange resin using ammonia o-hydroxy isobutyrate as the eluent. Which of the following
order is correct in which the ions will be separated is?
(A) Eu3+, Dy3+, Yb3+, Lu3+ (B) Lu3+, Yb3+, Dy3+, Eu3+
(C) Dy3+, Yb3+, Eu3+, Lu3+ (D) Yb3+, Dy3+, Lu3+, Eu3+
76. When a reduced cytochrome transfers from its Fe(II) to the bound O2,
(A) The bond order of O2 is reduced by one and vO decreases.
2
(B) A metal bond superoxide is formed and vO increases.
2
(C) A metal bond superoxide is formed and vO decreases.
2
(D) The bond order of O2 is reduced by one and vO increases.
2
77. Treatment of the pentapeptide Gly-Arg-Ala-, in separate experiments, with the enzymes Trypsin,
Chyemotrypsin and Carboxypeptidase A respectively, gives :
(A) Gly-Arg+Phe-Ala-Ala; Gly-Arg-Phe+Ala-Ala; Gly-Arg-Phe-Ala+Ala
(B) Gly-Arg–Phe-Ala-Ala; Gly-Arg-Phe+Ala-Ala; Gly-Arg-Phe-Ala+Ala
(C) Gly-Arg+Phe-Ala-Ala; Gly-Arg-Phe+Ala+Ala; Gly-Arg-Phe+Ala-Ala
(D) Gly-Arg+Phe-Ala-Ala; Gly-Arg-Phe+Ala-Ala; Gly+Arg-Phe-Ala+Ala
78. A thin sample of gold was irradiated in a thermal neutrons flux of 1012 neutrons cm2 s–2 for 25.6
hr. In the reaction the nuclide 198Au is product with a half-life of 64 hr. If the thermal neutron
absorption cross section is 98 barns, what is the specific activity of the sample ?
(A) 1.96 Ci/g (B) 2.59 Ci/g
(C) 6.42 Ci/g (D) 0.895 Ci/g
79. The approximate mass of uranium that must undergo fission to produce the same energy as 105
kg of coal is (Assume that heat of combustion of coal = 8000 cal g–1 and one fission of uranium
releases 200 MeV)
(A) 235 g (B) 39 g
(C) 32 g (D) 35 g
1
80. If CIF3 were to be stereochemically rigid, its 19F NMR spectrum (1 for 19F = ) would be (assume
2
that CI is not NMR active)
(A) a doublet and a triplet (B) a singlet
(C) a doublet and a singlet (D) two singlets
81. An aqueous solution of an optically pure compound of concentration 100 mg in 1ml of water and
measured in quartz tube of 5 cm lengths was found to be –3º. The specific rotation.
(A) – 30º (B) – 60º
(C) – 6º (D) + 6º

82. The products A & B formed in the following reaction sequence are
SeO2 aq. NaCN, MnO2

 
 A  B
Dioxane Reflux i  Pr OH, Me2NH
CHO O N
(A) A: B:
CHO O O
(B) A: B:
A: B: O
(C) CHO
O
A: B: N
(D) CHO
O
83. The number of aldol reaction(s) that occurs in the given transformation is :
(A) 4 (B) 3
(C) 2 (D) 1
84. In the given reactions, identify the correct combination of their major products P and Q.
[LDA = LiN(i-Pr)2]
(A) (B)
(C) (D)

85.
(A) (B)
(C) (D)
86.
(A) (B)
(C) (D)
87. The major product of the following reaction is :
(A) (B)
(C) (D)

88. The major product in the following reaction will be :
(A) (B)
(C) (D)
89. The structure of major product, Z and the overall yield for its formation from the ketone, X, in the
following reaction sequence are :
(A) (B)
(C) (D)
90. The most appropriate set of reactions for carrying out the following conversion is :
(A) (i) peracid; (ii) H+; (iii) Zn/dil.HCl

(B) (i) Alkaline KMnO4; (ii) NaIO4; (iii) N2H4/KOH
(C) (i) Alkaline KMnO4; (ii) H+; (iii) Zn/dil.HCl
(D) (i) O3/Me2S; (ii) NaOEt; (iii) N2H4/KOH

91. Which of the following sequence of reagents suitable for the following conversion.
O
O
(A) (CH3)2NH/HCHO/; CH3I, AgOH, ; NH2NH2/alc KOH/; OsO4/NaIO4

(B) (CH3–CH2)2NH/HCHO/; CH3I, AgOH, ; Zn-Hg/conc HCI; KMnO4/NaIO4
(C) Ph2NH/HCHO/; CH3CH2I, AgOH, ; Zn/Hg/HCl; Ozonolysis
(D) All of these
92. The product of the given reaction is :
DDQ
?
CH3
CH3
(A) (B)
CH3
CH3
(C) (D)
93. The final product (P) in the given reaction sequence is?
OMe
+
H3O/ HS—(CH2)3 — SH/BF3 (i) BuLi HgCl2/MeOH/KOH 
O (A) (B) (C) (D) (P)
Br
(ii)
OMe Br
O O
(A) (B)
O O
(C) (D)

94. Produce (P) in the given sequence is :
(i) O
NaNH2 (i) NaNO2/HCI Mg/ether Al 2O 3
(A) (B) (C) +
(D) (E)
 (ii) Cu2Br 2 
N (ii) H3O
HCN
DIBAL
(P) (F)
–80°C
(A) (B)
N CONH2 N CHO
(C) (D)
N CHO N NH2
95. In the reaction :
13
where * = C labelled carbon
the major products, X & Y are respectively :
(A) (B)
(C) (D)
96. The major product in the following reaction is :
(A) (B)
(C) (D)

97.
(A) (B)
(C) (D)
98. In the given reaction, the product (P) is/are
NH 2
CH3
COOMe
(P)
N Cl
CH3 COOMe
Only
CO — NH N NH
(A) Only (B)
N Me
COOMe
Only
N CH2
(C) Mixture of (A) and (B) (D)
NH2
99. The mass spectrum of a dihalo compound shows peaks with relative intensities of 1 : 2 : 1
corresponding to M, M + 2 and M + 4 (M is the mass of the molecular ion), respectively. The
compound is —
Br Br
Cl
(A) (B)
Me Br Me
Me Cl
Cl Me
(C) (D)
Cl F

100. Calculate max values for the following compounds according to the existing emperical rules.
Cl O
Ome
(A) 366 nm (B) 361 nm
(C) 348 nm (D) 378 nm
2 nx
101. The set of eigen function
a
sin
a
 0  x  a,n  1,2,3....
(A) Orthogonal (B) Normalized
(C) Both orthogonal and Normalized (D) Unnormalized
102. Calculate the degeneracies of a particle of mass m in a three-dimensional cubical box of width
a having energies equal to 14 in units of (h2/8ma2).
(A) 2 (B) 5
(C) 7 (D) 6
103. First order perturbation correction n(1) to energy level n of a simple harmonic oscillator due to
the anharmonicity perturbation x3 is given by
(A) n(1) =  (B) n(1) = 2
(C) n(1) = –1 (D) n(1) = 0
104. For an adiabatic process what is the relation between temperature and pressure?
1 1
T2  P2  T2  P2  1
(A)   (B)  
T1  P1  T1  P1 
1 
T2  P2   T2  P2  1
(C)   (D)  
T1  P1  T1  P1 
105. Calculate the final volume of one mole of an ideal gas initially at 0°C and 1 atm pressure if it
absorbs 1000 cal of heat during a reversible isothermal expansion.
(A) 141·25 dm3 (B) 100.3 dm3
(C) 6.27 dm3 (D) 73.28 dm3
106. The isomerisation of cis to trans-but-2ene, C4H8, follows a Lindemann mechanism. At high pressure,
the pseudo first-order rate constant for the isomerisation is 2 × 10–5 s–1 at 500°C. Given that, at
this temperature, collisional activation occurs with an efficiency that is 1011 times slower than that
of collisional deactivation, determine the rate constant for the final step of the mechanism.
(A) 5 × 105 s–1 (B) 2 × 10–5 s–1
(C) 2 × 10–16 s–1 (D) 5 × 10–7 s–1

107. At 100°C, the gaseous reaction A  2B + C is found to be of first order. Starting with pure A, if
at the end of 10 min, the total pressure of the system is 308 mm and after a long time it is 360
mm, the partial pressure of A at the end of 10 min will be?
(A) 94 mm (B) 43 mm
(C) 26 mm (D) 176 mm
108. For the half cell Cl–1/Pt(Cl2), the value of (E – E°) :

(A) increases as [Cl–] increases
(B) decreases as [Cl–] increases
(C) remains constant as [Cl–] increases
(D) cannot be predicted
109. Standard electrode potential data are useful for understanding the suitability of an oxidant in a
redox titration. Some half cell reactions and their standard potentials are given below :
1. MnO4 (aq.)  8H (aq.)  5e  Mn2+ (aq.) + 4H2O() ; E° = 1.51 V
2. Cr2O72 (aq.)  14H (aq.)  6e  2Cr3+ (aq.) + 7H2O() ; E° = 1.38 V
3. Fe3+ (aq.) + e–  Fe2+ (aq.) ; E° = 0.77 V
4. Cl2(g) + 2e–  2CI– (aq.) ; E° = 1.40 V
Identify the only incorrect statement regarding the quantitative estimation of aqueous Fe(NO3)2.
(A) Cr2O72 can be used in aqueous HCl
(B) MnO4 can be used in aqueous HCl
(C) Cr2O72 can be used in aqueous H2SO4
(D) MnO4 can be used in aqueous H2SO4
110. The C = O bond length is 120 pm in CO2. The moment of inertia of CO2 would be close to
(masses of C and O are 1·9 × 10–27 kg and 2·5 × 10–27 kg) respectively.
(A) 1·8 × 10–47 kg m2 (B) 3·6 × 10–47 kg m2
(C) 5.4 × 10–47 kg m2 (D) 7·2 × 10–47 kg m2
111. The correct pair of 1H and 31

P NMR spectral patterns for C(H)(F)(PCl2)2 is :
(A) (B)
1 31 1 31
H P H P
(C) (D)
1 31 1 31
H P H P

112. The molecule that has an S6 symmetry element is

(A) B2H6 (B) CH4
(C) PH5 (D) SF6
113. For the Daniel cell involving the cell reaction

Zn(s) + Cu2+ (aq)  Zn2+ (aq) + Cu(s),
the standard free energies of formation of Zn(s), Cu(s), Cu2+ (aq) and Zn2+ (aq) are 0, 0, 64·4 kJ
mol–1 and –154·0 kJ mol–1, respectively. Calculate the standard EMF of the cell.
(A) – 1.13 V (B) 2.16 V
(C) 1.13 V (D) – 2.16 V
114. A sample of an oxide ore of nickel has formula Ni0.98 O1.00.The percentage of nickel as Ni2+ ions
is nearly
(A) 2 (B) 96
(C) 4 (D) 98
115. Calculate the rate of absorption of nitrogen, N2, molecules on a tungsten (320) surface for a
pressure of 0.10 kPa and temperature of 298 K, given that the sticking probability is 0.74.
(A) 7.37 × 1024 s–1 m–2 (B) 2.13 × 1024 s–1 m–2
(C) 2.88 × 1024 s–1 m–2 (D) 1.28 × 1024 s–1 m–2
116. N2O4 (g) 

 2NO2 (g)


At Equilibrium the partial pressure of both the gases are 2 atm each at 27°C in a closed container.
If the volume of the container is doubled at the same temperature what will be the final equilibrium
pressure of the container.
(A) 0.16 atm (B) 1.16 atm
(C) 2.16 atm (D) 1.48 atm
117. Equal numbers of molecules with M1 = 10,000 and M2 = 100,000, are mixed. Calculate the
number-average molar mass ( MN ).
(A) 25,000 (B) 55,000
(C) 98,818 (D) 62,000
118. 3.2g S is heated if occupy a volume of 780 ml at 450°C and 723 mm pressure. Formula of
sulphur is
(A) S2 (B) S
(C) S4 (D) S8
119. When 15 g of naphthoic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 Kg mol–1), a
depression in freezing point of 2K is observed. The Van’t Hoff factor (i) is
(A) 0.5 (B) 1
(C) 0.75 (D) 3

120. [CoCl4]2– is a blue coloured complex. Controlled-treatment of this complex with water generates
two isomeric light pink colour complexes of composition [Co(H2O)4Cl2].
Identify the correct point groups for [CoCl4]2– and two isomeric complexes [Co(H2O)4Cl2].
(A) D2h and (C2v and C2h) (B) Td and (C2v and D4h)
(C) D4h and (C2v and D4h) (D) Td and (C2v and C4v)
ANSWER KEY
1 2 3 4 5 6 7 8 9 10
D C B A D A C A D B
11 12 13 14 15 16 17 18 19 20
A D D D C A C D B B
21 22 23 24 25 26 27 28 29 30
B B C A B B B D B D
31 32 33 34 35 36 37 38 39 40
B D D B B B D C B D
41 42 43 44 45 46 47 48 49 50
D A B B B C C C D D
51 52 53 54 55 56 57 58 59 60
D C B A A A B B C B
61 62 63 64 65 66 67 68 69 70
D D A C B C C D C B
71 72 73 74 75 76 77 78 79 80
D D A A B C A A B A
81 82 83 84 85 86 87 88 89 90
B D B C B A C D B D
91 92 93 94 95 96 97 98 99 100
A B B B B D C C A D
101 102 103 104 105 106 107 108 109 110
C D D C A C C A B D
111 112 113 114 115 116 117 118 119 120
C D C B B C B D C B

SOLUTIONS
PART - ‘A’
1. (D) 20 = 8 × 2 + 4, 15 = 3 × 2 + 9
 ? = 6 × 2 + 6 = 18
2. (C) The alphabets are showed as show :
G I V E B A T
5 1 3 7 9 2 4
So, G is coded as 5,
A as 2,
T as 4 and
E as 7.
Thus, the code for GATE is 5247.
3. (B)
6m B
6m 3m
F X
D
8m
A
Office will be in NORTH WEST from his house.
Let A be the Sachin's house and E his office.
The distance between A and F
= (AX)2  (XF)2 (Pythagoras theorem)
AF  (AX)2  (XF)2
AF  (5)2  (12)2 ( AB = 8m and XB = 3m, So, AX = 5)
AF  169  13m
4. (A) The elements are moved half step anticlockwise and a new element is added alternately
in the front and back of the trail.
5. (D) In this series, the letters remain the same: EFG. After EFG in next number is add next
alphabet in itself, like EFG, EFGH, EFGHI, EFGHIJ, EFGHIJK
6. (A) According to the formula,
4 cm
8 cm
1
Area of the triangle = × 8 × 4 = 16 sq cm
2
r 2 16
Area of semi-circle =  = 8
2 2
 Required answer = 8 – 16
= 8( – 2) sq cm
QR 4
7. (C) tan   
PQ 3 R
 PR  (4)2  (3)2  5
QR 3
 sin   
PR 5
PQ 3 
and cos   
PR 5 P Q
4 3 7
 sin   cos    
5 5 5
8. (A) Clearly n(S) = 6 × 6 = 36
Let E be the event that the sum of the numbers on the two faces is divided by 4 or 6.
Then
E = {(1,3), (1,5), (2,2), (2,4), (2,6), (3,1), (3,3), (3,5), (4,2), (4,4), (5,1), (5,3), (6,2), (6,6)}
n(E) = 14.
Hence p(e) = n(e)/n(s) = 14/36 = 7/18
9. (D) Let the length of bridge is x.
First convert speed into m/sec
 5  25
Speed = 45 km/hr.   45    m/sec
 18  2
Time = 30 seconds
Total distance = 130 + x
Dis tan ce
Time =
speed
130  x 25
 
30 2
 2(130+x) = 750
 x = 245 meters
So length of the bridge is 245 meters.
10. (B) Anil - Jayesh = Jayesh - Prashant or Anil + Prashant = 2 Jayesh.
So 2 × Jayesh = 48 or
Jayesh = 24.

11. (A) Total sale for 5 months

= Rs.(6435 + 6927 + 6855 + 7230 + 6562) = Rs.34009.
Required sale
= Rs. [(6500 × 6) – 34009]
= Rs.(39000 – 34009)
= Rs.4991.
12. (D) Quantity of Milk = 60 × (2/3) = 40 liters
Quantity of water = 60 – 40 = 20 liters
As per question we need to add water to get quantity 1:2.
Let quantity of water to be added further be x litres.
 40 
Then, milk : water =  
 20  x 
 40/(20 + x) = 1/2
 20 + x = 80
 x = 60 liters
25
13. (D) (3 + 326 + 327 + 328) = 325 × (1 + 3 + 32 + 33) = 325 × 40
= 324 × 3 × 4 × 10
= (324 × 4 × 30), which is divisible by 30.
14. (D) The coloured sides of the block which are clearly understood to be the opposites are:
White – Orange, Blue – Yellow and Green – Red. So, when blue is on the top, yellow will
be at the bottom.
15. (C) Expenditure is highly fluctuating so relationship is not direct.
16. (A) Area of rectangular field
1000
 4000 m2
1
4
4000
 Length   80m
50
New length of field = 100 m
Area = 100 × 50 = 5000 m2
 1
 Required cost =  5000    Rs 1250
 4
17. (C)
Total number of triangles = 14 + 2(combination of triangles[(10,9),(1,3),(2,4),(11,12)]) = 18

18. (D) (7 + 4) × 8 = 88
(5 + 6) × 11 = 121
Similarly,
(9 + 3) × 7 = 84
19. (B) a + b + c = 10. Now, let us place ten sticks in a row
| | | | | | | | | |
This question now becomes the equivalent of placing two '+' symbols somewhere between
these sticks. For instance,
| | | | + | | | | | + |
This would be the equivalent of 4 + 5 + 1. or, a = 4, b = 5, c = 1.
There are 9 slots between the sticks, out of which one has to select 2 for placing the '+'s.
The number of ways of doing this would be 9C2. Bear in mind that this kind of calculation
counts ordered triplets. (4, 5, 1) and (1, 4, 5) will both be counted as distinct possibilities.
We can also do a + b + c = n where a, b, c have to be whole numbers (instead of natural
numbers as in this question) with a small change to the above approach. Give it some
thought.
The question is "Sum of three Natural numbers a, b and c is 10. How many ordered
triplets (a, b, c) exist?"
Hence the answer is "9C2 = 36."
20. (B) Let the C.P. be x and S.P. be y.
 Given,
3(y – x) = 2y – x
 3y – 3x = 2y – x
 y = 2x
Original profit = Rs y – x
= Rs 2x – x (Since, y = 2x)
= Rs x
 Original profit % = x/x × 100
= 100 %
The question is "Find the original profit percent."
The original profit percent is 100%.
PART - ‘B’
21. (B) The structure of SbPh5 and PPh5 are square pyramidal, trigonal bipyramidal respectively.
( Hint - Due to larger size of Sb, the structure of SbPh5 rearrange from trigonal bipyramidal
to square pyramidal shape.)
22. (B) Lewis acidity of BCl3, BPh3 and BMe3 with respect to pyridine follows the order, BMe3 >
BPh3 > BCl3. Among BCl3, BMe3 & BPh3; BCl3 is weak lewis acidic due 2p(B) - 3p(Cl) 
back bonding. Among BMe3 and BPh3 ; BMe3 is strong Lewis acid with respect to pyridine
due to steric factor in BPh3.
23. (C) Hg2+ – SA, Cl– – SB, F– – HB
HgF2 (SA + HB) is not stable, so reaction is not expected.
24. (A) Being organic in nature C60 is soluble in non-polar solvent such as benzene and react with
tert-butyllithium. C60 is made up of 12 five-membered and 20 six-membered ring & adjacent
five & six membered rings share a common edge.
25. (B) For the complex ion [Cu(NH3)6]2+, the coordination geometry will be tetragonally distorted
octahedral.
Jahn teller distortion [d9 system of Cu(II)] shows dynamic Jahn teller distortion.
2 
26. (B) Cd H2O 6  
k1
 Cd Br H2O 5   H2O
Br 

Cd Br H2O 5  
k2
 Cd Br2 H2O 4   H2O
Br 

 C d  B r2  H 2 O  4     C dB r3  H 2 O 3  H 2 O
 k 
3
Br

CdBr3 H2O 3   CdBr4 
k4 2

Br 
 3H2O
Fourth equilibrium constant is observed higher than the third one because three molecules
of H2O are released during the fourth step (k4 >> k3)
27. (B) The rates of water exchange in high-spin hexaaqua ions follows the sequences.
V2+ < Ni2+ < Co2+ < Fe2+ < Mn2+ < Zn2+ < Cr2+ < Cu2+
A series is based on loss or gain of CFSE. A loss of CFSE means an increase in the
activation energy for the reaction and hence a decrease in its rate & vice a versa.
28. (D) Inner sphere Mechanism : Inner sphere electron transfer occurs between complexes
via a bridging ligand. At least one of the complex needs to be labile to allow the bridge to
form.
Ex. [Cr(H2O)6]2+ + [CoCl (NH3)5]2+  [Co(NH3)5(H2O)]2+ + [CrCl(H2O)5]2+
Cr2+ (HS), Co3+ (LS)
t2g6 (labile) t2g3eg1 (Inert)
(Bridging ligand Present)
Outer sphere Mechanism - Occurs between complexes that do not undergo substitution
no new bonds are formed or broken.
Ex. [Fe(CN)6]4– + [Mo(CN)8]3–  [Fe(CN)6]3– + [Mo(CN)8]4–
29. (B) Ligand field stabilization energies are smaller for lanthanides compared to transition metals
in the same oxidation state because f orbitals interact less effectively with ligands. Since
the 4f electrons are well shielded and not affect by the environment of the ion.
30. (D) The red colour of oxyhaemoglobin is mainly due to the intraligand * transition.
The wavelength of light absorbed by hemoglobin exactly corresponds to the difference in
energy between the highest occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) of the heme -system and is what gives hemoglobin its colour,
Changes in this colour, therefore are the direct result of changes in the energies of the
molecular orbitals of the hemoglobin -system.
31. (B) A molecule of dihydrogen contains two atoms, in which the nuclei of both the atoms are
spinning. Depending upon the direction of the spin of the nuclei, the hydrogens are of two
types.
Ortho Hydrogen : Spins of both the nuclei are in the same direction.
Para Hydrogen : Spins of both the nuclei are in the opposite direction.
ortho para
hydrogen hydrogen

32. (D) We know that

Ksp = S2 (S = solubility)
S1 = solubility of MX
S2 = solubility of MX2
S3 = solubility of M3X
 
M  X
MX(s) 


S1 S1
Ksp = S12 = 4 × 10–8

or S1 = 2 × 10–4 (M)
2 
 M  2X
MX2 (s) 


S2 2S1
Ksp = (S2) (2S2)2

= 4S23
= 32 × 10–15
or S2 = 2 × 10–5(M)
M3X(s) 3M+ + X3–
3S3 S3
3
Ksp = (3S3) (S3)
= 27S34 = 27 × 10–16
S3 = 10–4 (M)
33. (D) The order of carbonyl stretching frequency in the IR spectra of ketone, amide and anhydride
is anhydride > Ketone > Amide .
The general order of carbonyl stretching frequency in the IR- spectra :
acid chlorides > anhydrides > ester > Aldehydes > ketones > carboxylic acids > Amides.
+
34. (B) (A) Planar, Cyclic, Conjugated System, 6 electrons (follow huckel rule)
Aromatic in nature
(B) Planar, Cyclic, Conjugated System, 8 electrons

Antiaromatic in nature
(C) Planar, Cyclic, Conjugated System, 6 electrons (follow huckel rule)

Aromatic in nature
–
Planar, Cyclic, Conjugated System, 10 electrons (follow huckel rule)
(D) Aromatic in nature
–

35. (B) The most stable conformation of 2,3-dibromobutane is (b) in which Me/Br are gauche to
each other because gauche interaction values for Me/Br is only 0·8 kJ/mol, Which is least
among all.
Br
H Me
H Me
Br
Both bulky groups are away from each other.
36. (B) Lone pair of nitrogen is localized & basic and a reasonably good nucleophile. In second
reaction NaH (base) abstract an acidic proton to form Na-Salt of Indole & Nucleophilic
substitution reactions on indole nitrogen.
Mel
  –
.. 25º C + N
N N
.N. H H
Me—l Me
NaH  Me Me

 
N N N
N N– N
H H –
Na+ Me—l Me
37. (D)
H
S S S



Base
 
EtBr
   Et
SN2 S
EtO EtO EtO OEt
H


H2 O / H
 Et O  Product
OH
thioaldehyde on hydrolysis converts into aldehyde.
38. (C) —OH is o/p director and —COOH is electrophilic group as leaving group.
+
••O—H
•
O—H OH
• O
|| + NO 2
C—O—H NO2 NO2
C—O—H
||
O +
NO 2
OH
O 2N NO2
NO2

39. (B)
O KOBr
|| (Oxidation)
KCN/HOH
CHO C — CHOH
O C2H5OH O O
Benzoin
condensation
OH – O O
| OH || ||
C C—C
O | O Benzilic acid O O
COOH rearrangement
40. (D)
KMnO 4 COOH 
(A) O
NaIO 4 COOH
1,6-dibasicacid
+
(i) O 3 COOH C2H5OH/H COOEt
(B)
(ii) CH3—S—CH 3 COOH COOEt
(iii) Ag 2O –
C2H5OH C2H5O
+
H/ 
Product O
COOEt
(i) O 3 CHO Ag2O COOH

(C)
(ii) CH3—S—CH 3 CHO COOH

O
41. (D) The correct combination of reagents :

s - BuLi, –78ºC followed by ICH2CH2I
Li l
Sec .BuLi l – CH 2 – CH 2– l
N  
78º C N N
O
O O

42. (A) Compound (a) will undergo a degenerate cope rearrangement :
H 3 H
12

 
1 3,3
H 2 3 H
A rearrangement in which product and reactant are identical is called a degenerate cope
rearrangement.
43. (B) It is a rearrangement of carbene formed by loss of N2 from diazoketone to give ketene
which cannot be isolated but is hydrolysed under aqueous condition & undergo subsequent
decarboxylation.
O
N2 OH
C O CO O
O O O •• O
1. h, aq.THF H2 O
, –CO2
O
44. (B) 2 3 1 4
45. (B) Ziegler-Natta polymerization is a method of vinyl polymerization. It’s important because it
allows one to make polymers of specific tacticity.
Ziegler-Natta catalysis is especially useful, because it can make polymers that can’t be
made any other way, such as linear, unbranched poyethylene and isotactic polypropylene
Free radical vinyl polymerisation can only give branched polyethylene, and propylene won’t
polymerize at all by free radical polymerisation. So it is a pretty important polymerisation
reaction.
46. (C)
e
f d
f g b d b
e g c c c
a a
b
a a a
d b c c
c a b d b
7 Signals 4 Signals
47. (C) The delocalisation energy of benzene is the total -electrons energy minus the energy of
the molecule if it were bonded with three ethylenic type double bonds. Since we have six
-electrons and since the lowest energy are E1, E2 and E3 we get delocalisation energy
= 2( + 2) + 4( + ) – 3(2 + 2)
= 2
This delocalisation energy is an additional stabilization of the molecule due to the
delocalisation of the -electrons over the whole ring.
 H 
48. (C) Cp   
 T p
and dG = V dp – S dT
At constant temperature
 G 
(dG)T = Vdp    V
 p T
 T  1  H 
and, J.T      
 p H Cp  p T
N!
49. (D) Microstate 
r ! N  r  !
Given N = 4 , r = 2
4!
Microstate  6
2!2!
50. (D) Comparing column II and III
[B]0 and [C]0 constant, doubling [A]0, doubles r0
 Order of reaction w.r.t. A = 1
Comparing column I and II
[A]0 and [C]0 constant, doubling [B]0, doubles r0
 Order of reaction w.r.t. B = 1
Comparing column I and IV
[A]0 and [B]0 constant, quadrupling (i.e., four time) [C]0, r0 becomes one fourth
 Order of reaction w.r.t. C = –1
Comment : Choose the set of readings in which concentration of one reactant varies and
that of rest is constant.
Rate = k[A]0x [B]0y [C]0z order = x + y + z
= k[A]10 [B]10 [C]01 = 1 + 1 – 1 = 1

51. (D) For first order reaction
1 a ln 2
k  ln 
t a  x t1/ 2
a – x = 100 – 87.5 = 12.5
1 100 ln 1 ln 2
ln  or ln8 
t 12.5 20 t 20
1 3 ln 2 3 1
or ln 2  or   t = 60 minutes
t 20 t 20
Alternatively 100 

20 min
50 
20 min
25 
20 min
12.5
Initial Amount left on completion of 87.5%
(100 – 87.5 = 12.5)
There are three half-lives required to complete its 87.5%
Time Required
= 3 × t½
= 3 × 20 = 60 minutes

52. (C) The molar conductivity of a weak electrolyte at infinite dilution ( mo ) can be determined by
using the kohlrausch’s equation i.e.,
mo  v  o  v  o

where, v+ and v– are the number of cation and anions respectively.
 Ba(OH)
o
2
 Ba
o
2   2
o
OH
 523.28 ...(1)
 BaCl
o
2
  Ba
o
2   2   280.00
o
Cl
...(2)
NH
o
4 Cl
 NH
o
     129.80
o
Cl ...(3)
4
Multiply Equation (3) by two and subtract from Equation (2).
Ba
o
2   2
o
NH
 280  2  129.8 ...(4)
4
 Ba
o
2   2
o
NH
 20.40 ...(5)
4
Now subtract Eq. (5) from Eq. (1)
2NH
o
  2 2
o
OH
 502.88
4
502.88
 NH
o
  
o
OH
 NH
o
4 OH

4
2
= 251.44 S cm2 mol–1
53. (B) Given, Ko   73.52
Ionic mobility,
Ko  73.25
uKo   
F 96500
= 7.619 × 10–4 cm2 sec–1 volt–1
Potential gradient applied
6.0
= = 0.6 volt cm–1
10
Speed of K+ = ionic mobility × potential gradient
= 7.619 × 10–4 × 0.6 cm sec–1
= 45.714 × 10–5 cm sec–1
 Distance traveled by K+ in 2 hour
= 45.714 × 2 × 60 × 60 × 10–5
= 3.292 cm
54. (A) If the bond length of heteronuclear diatomic molecule is greater in the upper vibrational
state, the gap between the successive absorption lines of P-Branch increases non- linearly
& that of R-branch decreases non-linearly.
55. (A) The CORRECT statement is the number of irreducible representations is equal to classes
of symmetry operations according to assumptions of the great orthogonality theorem.

56. (A) A Corners (8) + Face Centre (6)

1 1
8 1 6 3
8 2
 1 + 3 = 4(x)
B  Tetrahedral voids (each body diagonal contains two tetrahedral voids)
Total tetrahedral voids
= 2 × 4 = 8
Contribution = 1 per tetrahedral void
hence B = 8 × 1 = 8(y)
Put here only 4 out of 8 tetrahedral voids are present
hence B will be 4 (y)
A : B
4 : 4
57. (B) As per freundlich adsorption equation
x
 kP1/ n
m
Taking log both sides of equation, we get
x 1
log    logk  logP
m n 1
Slope 
since log k = 0.699 n
x
Hence, k = 5 log
m
1 intercept = log k
slope = = tan 45° = 1
n
or n = 1 log P
x
thus,  kP1/ n
m
= 5 × 0.5
= 2.5 g/g adsorbent
58. (B) [OH]  k b C
 1.8  10 5  0.1
 1.8  10 6
= 1.34 × 10–3
59. (C) Pmoist = Pdry + PHo2O

2 atm = Pdry + 0.4 atm
 Pdry = 1.6 atm
Final pressure of dry gas = Pdry = 0.8 atm
(volume is doubled hence pressure of dry gas will be half)
PHo2O = 0.4 atm (Does not change with volume only changes with temperature)
o
Pmoist (final) = Pdry + PH2O = (0.8 atm + 0.4 atm) = 1.2 atm

60. (B) At 1 atmospheric pressure the boiling point of mixture is 80°C

At boiling point the vapour pressure of mixture, PT = 1
atmosphere = 760 mm Hg.
Using the relation,
PT  PAo X A  PBo XB , we get
 PAo  280mmHg,
PBo  1000mm Hg
XA + XB = 1 or XB = 1 – XA
PT = 280 XA + 1000(1 – XA)
or 760 = 280 XA + 1000 – 1000XA
or 720XA = 240
240 1
or XA   or 34 mol. per cent
720 3
PART - ‘C’
61. (D) First ionisation energy of O2 is highest in given series. Since lose its electron with PtF6.
So other Na, NO and Xe also lose their electron with PtF6.
62. (D)
O
O O 4–
Xe
O O
O
4–
[XeO6]
V MC A
n
2
V = no. of valence electrons
M = Monovalent atoms
C = Charge on Cation
A = Charge on Anion
8  0  0  4 12
n  6 sp3d2, octahedral
2 2
F
F F
Xe distorted octahedral
F F

XeF6.
8600
n 7
2
sp3d3, distored octahedral due to one lone pair.
63. (A) Rh6(CO)16
TEC  6 × 9 + 16 × 2 = 86 (TEC = total electron count)
Polyhedral electron count (PEC) = 86 – 6 × 12 = 14
PEC 14
 = 7 = 6 + 1  (n + 1)  closo.
2 2
64. (C) CB4H5

(C = BH)
(BH) B4H5–1
B5H6–1
B5H511 (closo-borane).
product 1 10 3 1
65. (B) TOF =   6  = 100
catalyst time 10 10
66. (C) The correct order of bronsted acidity of boron hydrides follows the order
B10H14 > B5H9 > B4H10 > B2H6
acidity of boron hydride depends on the size of borane greater the size higher will be the
acidity. This is because the negative charge, formed upon deprotonation, can be better
delocalized over a larger anion with many boron atoms than over a small one.
67. (C)
–
CH3 CH2
NaOMe –I
Cp2 — Ta Cp2 — Ta Cp2MeTa = CH2
Shrock’s carbene
CH3 CH3
 
Correct option is (C).
68. (D) All the given compounds exhibit geometrical (cis and trans) isomers but only cis isomer
of [Co(en)2Cl2]+ possess optical isomers ( d and l) due to the presence of symmetrical
bidentate, (ethylenediamine).
69. (C) Bridging ligands () helps in attaching two metals through them. Bis tells that there are
two (tricarbonyl iron(0)).
70. (B) [Cr(NH3)6]3+ that is Cr3+ ion & it is d3 system
+3 3
Cr = d
2 1 0 –1 –2
3
Thus, L = 3, S   The term symbol is 2S+1
L = 4F
2
The free- ion term for F is T1g × T2g + A2g.
Splitting pattern of Cr3+ ion in [Cr(NH3)6]3+

2 2 2 Set of e.g. orbitals

dx – y dz
d3
Set of t 2g orbitals
dxy dyz dxz
The ground state spectroscopic term is 4A2g & according to orgel diagram. It has three
types of transition: -
4
A2g  4T2g ; 4A2g  4T1g & 4A2g  4T1g (P)
All the above three transitions are spin allowed but transition 4A2g  2Eg is spin forbidden
transition (according to a spin selection rule). Therefore intensity of this transition is lowest
among three.
71. (D) [Re2Cl4(PMe2Ph)4]+
Step (1) : Let the oxidation state of ‘Re’ atom is x
2x – 4 = +1  2x = 5
Re+2 = 4d5 Re3+ = 4d4
Step (2) : Therefore, number of d electron on Re+2 and Re+3 ions
= 5 + 4 = 9
Step (3) : Electronic configuration in cluster ion is
2 4 2 *1
1
B.O = (8 – 1) = 3.5
2
Similarly, [Re2Cl4(PMe2Ph)4]
Step (1)  2x – 4 = 0  2x = +4  x = +2
Re+2 = 4d5 Re+2 = 4d5
Step (2) = 5 + 5 = 10
1
Step (3) = 3 4 2 +2; (8 – 2) = 3
2
72. (D) [Co(NH3)6]3+ and [Co(H2O)6]3+ both are low spin complexes. They involve inner 3d orbital
in hybridization. Hence, they have same hybridization i.e., d2sp3
73. (A) The Jahn-Teller effect is a geometric distortion of a non-linear molecular system that
reduces its symmetry and energy Jahn-Teller distortion shown by complexes having
unsymmetrically filled energy levels. Thus, Cu(II), Fe(III) LS, Ti(III) will show J.T. distortion.
74. (A)
O
Cl
Mn2 (CO) 1 0 2[Mn(CO) 5 ]– (CO) 5 Mn(O)CCH 3
Carbonylate ion
nucleophillic in
nature
75. (B) Lanthanides, as the atomic number increases, size of lanthanide ions(III) decreases. O-
hydroxylsobutayrate ion forms a stable complex with smaller ion. The correct order of
trivalent lanthanide ion is separation by
Lu3+ > Yb3+ > Dy3+ > Eu3+
76. (C) When a reduced cytochrome transfers and electron from its Fe(II) to the O2, a metal
bound superoxide is formed and vO decreases. Because bond order of O2 is 2 and O2–
2
is 1.5.
77. (A) (i) Enzyme trypsin cuts the peptide chain from c-terminal side of Arg, Cys
(ii) Chyemotrypsin cuts peptide chain from c-terminal side of Phe, Trp, Tyr
(iii) Carboxypeptidase cuts peptide chain from c-terminal side.
Correct option is (A).
78. (A) Specific activity is given by :
 0.693
t 
A = N   1  e t1/ 2 
 
 
here A = Specific activity

 = thermal neutrons flux
 = Cross section
Suppose 1 g of the gold was irradiated, then
1
N = × 6.023 × 1023 atoms
198
 = 1012 neutrons cm–2 s–1
 = 98 barns = 98 × 10–24 cm2
t1/2 = 64 hr and t = 25.6 hr
Substituting these values, we get
6.023  1023  0.693

25.6 
A = × 1012 × 98 × 10–24  1  e 64

198  
= 1.96 curie/g
79. (B) Mass of coal = 105 kg = 108 g
Heat of combustion of coal = 8000 cal g–1
Total heat produced on combustion of 108 g coal
= 8000 × 108 = 8 × 1011 cal
= 8 × 4.184 × 1011 J = 33.5 × 1011 J
Energy released per fission = 200 MeV
= 200 × 106 × 1.6 × 10–19 J
= 3.2 × 10–11 J
Number of U-235 atoms needed to produce this amount of energy
33.5  1011
=  1023 atoms
3.2  1011
 Mass of 1023 atoms of U-235
235  1023
= = 39 g
6.02  1023

80. (A)
a
F
b
C F
F
a
two Fa splits into a doublet with one Fb
one Fb splits into a triplet with two Fb
 1 
Fa  (2NI + 1)   2  1  1 = 2 (doublet)
 2 
 1 
Fb   2  2   1 = 3 (triplet)
 2 
81. (B) The specific rotation is – 60º
Given : Optical rotation – 3º
Concentration – 100 mg in 1 ml = 0·01 g cm-3.
Path length = 5 cm
Optical Rotation
Specific rotation = Concentration  Path length
 3º
   CL   0·01 5  60º
82. (D) In first step SeO2 selectively oxidizes the less substituted allylic end of an alkene that is
E- methyl group into the aldehyde. In next step aldehyde which reacts with cyanide to give
the cyanohydrin. Oxidation of the cyanohydrin with manganese dioxide gives the acyl
nitrile, which then reacts with the amine to give a amide by a loss of CN– ion
SeO2 aq. NaCN

Dioxane CN
Reflux CHO
OH
MnO2
1–PrOH,Me2 NH
N CN
O O
83. (B) Since there are 3 -hydrogens in acetaldehyde it undergoes crossed aldol reactions with
3 moles of formaldehyde i.e., three aldol reactions.

84. (C) Above reactions are directed aldol reactions which involve preformed enolate of the carbonyl
compound using strong base like LDA. The lithium enolate is treated with another carbonyl
compound to achieve desired crossed aldol addition.
The lithium enolate can be either cis (Z) or trans (E). Cis enolate usually gives syn addition
product and trans enolate gives anti addition product.
However with cyclic systems, trans enolates are formed due to ring constraints. Hence
anti addition product is formed as major product.

85. (B) Initially, iodine attacks the double bond from opposite side of carboxyl group, which gives
an iodolactone with trans configuration.
In the next step, iodine is substituted by allyl group in a radical mechanism using
tributylstannane. This reaction is initiated by AIBN, a free initiator. This reaction is called
Keck allylation.
Chain Initiation
(2, 2’-azo bisisobutyronitrile)
Chain Propagation

86. (A) This is an example for Robinson annulation reaction which involves, initial Michael addition
followed by intramolecular aldol condensation to produce a new ring.
87. (C) It is Robinson annulation: Michael addition followed by intra molecular aldol condensation.
Initial abstraction of proton occurs preferentially from benzylic carbon since the carbanion
generated will be more stable.
In the final step, intra molecular aldol condensation, the removal of water molecule occurs
such that the double bond formed will be in conjugation with the keto group.
88. (D) It is Baeyer villiger oxidation involving migration of 3° bridge head carbon since it has more
migratory aptitude over phenyl ring.

89. (B) The oxime, Y formed in the initial step is subjected to Beckmann rearrangement to furnish
an amide. Even though there are two amides possible, the one that is obtained from E-
oxime is predominantly formed due to steric reasons. Since the migration of tertiary group
is more faster and populates the reactions mixture with more E-oxime under equilibration
conditions.
The yield of Z is 70% of Y, which in turn is formed in 90% yield from X. Hence the overall
yield is 70% of 90% of X.
90 70
i.e., 100 ×  = 63%
100 100
90. (D)
OH
peracid H
+
H
+
(A) O
(Epoxidation)
O
Pinacole
rearrangement OH Zn/dil HCl
(B)
OH
Alk KMnO 4 H
+
Zn
(C) dil HCl
O
Pinacole
cis-hydroxylation OH rearrangement
(D)
91. (A)
O O
CH3
(CH3)2NH/HCHO CH2 — N (i) CH3I
CH3
Mannich reaction (ii) AgOH
O O CH 3
+ –
CH2 CH2 CH 2 — N — CH 3 OH
NH2NH2 
alc. KOH/ CH 3
OsO4 NaIO4
Product
92. (B) Benzylic and allylic hydrogen is abstracted by DDQ.
H 3C CH 3 CN CN H3 C CH3 H3C CH3
H H H
O O
H
H +
Cl Cl DDQ
CH3 CH3
H3C CH3
CH3 H 1,2-Shift +
+
CH3
93. (B)
OMe OMe OMe OMe O
+ +
H + + H2O OH H2O/H H HS—(CH2)3—SH
O O—H
OH OH H BF 3
OMe OMe OMe OMe O

(A)
O O
S S S S
 HgCl 2/MeOH (i) BuLi H
|3, 3| Br H
(ii)
S S S S
O O Br
(P) (D)
(C) (B)
94. (B)
NaNH2 (i) NaNO2/HCI Mg/ether

 (ii) Cu2Br2
N N NH2 N Br N MgBr
(A) (B) (C)
+
(i) O (ii) H2O/H
DIBAL HCN Al 2O3

CHO –80°C CN  OH
N N N N
(P) (F) (L) (D)
95. (B) It is Claisen rearrangement involving [3, 3]-sigmatropic rearrangement of phenyl allyl either
to give both ortho and para substituted phenols as shown below. The para product is
formed after two consecutive [3, 3]-sigmatropic rearrangements.
96. (D) It is an anion assisted [3, 3] oxy-cope rearrangement. The OH group is deprotonated by
strong base, KH to furnish an oxy anion, which assists the oxy cope rearrangement.
The stereo relation between two hydrogens is cis. It can be justified by following
stereochemical perspective of transition state.

97. (C)
98. (C)
O O
|| ||
C — OMe C — NH
••
H2N
N Cl N Cl
CH3
Me
– –
O O O
|| | |
C — OMe C — OMe C — OMe
+
•• NH
N Cl Cl H 2N Cl
N N
Me
Me
COOMe
N NH
Me
99. (A)
Br
Me Br
In the mass spectrum of this compound the intensity of bromide is 1 : 2 : 1 because
bromide has two isotope i.e. 79Br and 81Br.
Correct option is (A)
100. (D) Parent Value for , -unsaturated carbonyl 215 nm
One -substituent 12 nm
One -substituent 18 nm
Two extended conjugation 2 × 30 = 60 nm
Homoannular diene component 39 nm
One exocyclic double bond 5 nm
-methoxy group 17 nm
-chloro 12 nm
__________________________________________________
Total (max calculated) 378 nm
2  nx 
101. (C)  x  sin  
a  a 
For orthogonal function
i j d  1
a 2  nx  2  nx 
 x   sin  . sin   dx
0 a  a  a  a 
2 a  nx 
    sin2   dx
 
a 0
 a 
   2nx   
  1  cos   
2 a  2   dx 
     
a 0  2  
   
 
 2  1  a  2  1 a  2nx 
      dx       cos   dx
 a  2  0
 a  2  0
 a 
 2  1  a
      x 0  0
 a  2 
1
= a
a
= 1
This function is orthonormal i.e., both orthogonal and normalized.
102. (D) n2x  n2y  n2z  14
Here, six combinations, as shown, give energy = 14(h2/8ma2).

Hence, g = 6. The energy level is thus six-fold degenerate
nx ny nz
1 2 3
1 3 2
2 1 3
3 1 2
2 3 1
3 2 1
 1/ 4 x2 1/ 4 x 2 1/ 2 
  
     e 2r x 3   e 2 dx    r  x3 ex
2
103. (D)
 
   
x  n = even,
n
  0
xn  n = odd,  = 0
n(1) = 0
Correct option is (D).


104. (C) For an adiabatic process P V = constant
pV = RT (For ideal gas)

 RT 
P   constant
 P 
or P1–T = constant
or P11 T1  P21 T2
1 1
T2  P1   P  
or    2 
T1  P2   P1 
105. (A) The gas is under the conditions of S.T.P. so that V1 = 22·4 dm3. V2 is to be determined.
Since the expansion is reversible and isothermal, U = 0 so that
q = – w = 1000 cal = 1000 × 4·184 J
w = – nRT In (V2/V1)
Since
 nRT In V2/V1 = – w = 1000 × 4·184 J
(1 mol) (8·314 J K–1 mol–1) (273 K) In (V2/22·4 dm3) = 1000 × 4·1804 J
V2 = 141·25 dm3
106. (C) At high pressure, the rate law for a reaction that follows the Lindemann mechanism is
given by
k ak b
kr 
k a
so that the rate constant of the final step of the mechanism is
k a
kb   kr
ka
If collisional activation is 10–11 times slower than collisional deactivation, it follows that
ka
= 10–111
k a
k a
so that kb = k × kr = 10–111 × 2 × 10–5 s–1
a
= 2 × 10–16 s–1
107. (C) After long time whole of A would change into B and C. On decomposition one mole of A
360
changes into three moles of B and C. Therefore, Initial pressure of A = = 120 mm.
3
Suppose after 10 minutes pressure of A falls x mm. In that case pressure of B and C
would be 2x and x mm respectively.
Total pressure = (120 – x) + 2x + x = (120 + 2x) mm
120 + 2x = 308 mm
2x = 308 – 120 mm
308  120
x  94mm
2
Pressure of A after 10 minutes,
= (120 – 94) mm
= 26 mm.

108. (A) Cl–/Pt(Cl2)
1
Cl–  Cl2  e
2
0.0591 1
E  E  log 
n [Cl ]
0.0591 1
 E  E   log 
n [Cl ]
0.0591
 E  E   log[Cl ]
n
[Cl ] , E  E increases
Correct option is (A)
109. (B) MnO4 will oxidize Cl– ion
According to the equation,
2MnO4  16H  10Cl  2Mn2  8H2O  5Cl2

The cell corresponding to this reaction is as follows :
Pt,Cl2 (1 atm)Cl MnO 4 , Mn2 , H2 | Pt
E°Cell = 1.51 – 1.40 = 0.11 V

E°Cell = being +ve, G° = will be –ve hence spontaneous
MnO4 will not only oxidize Fe2+ ion but also Cl– ion simultaneously..
110. (D) For a triatomic linear rotor like
mAR  mCR ' 

2
OCS = I = mAR + mCR 2 '2


m
But for a centrosymmetric triatomic linear rotor like CO2 :

mA = mC & R = R’.
Above equation becomes :
I = 2mAR2 = 2 × 2·5 × 10–27 × (120 × 10–12 m)2
= 7·2 × 10–47 kgm2
111. (C) The correct pair 1H and 31
P NMR
C(H)(F)(PCI2)2
H PCI2
C
F PCI2
1
H NMR  (2NIP + 1) (2NIP + 1)
 1  1 
  2  1  1  2  2   1
 2  2 

  2 3
 
Doublet Triplet
1 1
1 2 1 1 2 1
(Two triplets)
P NMR  (2NIF + 1) (2NIH + 1)
31
 1  1 
  2   1  1  2  1  1
 2  2 
 2 2
 
Doublet Doublet
1 1
1 1 1 1
(Two doublets)
112. (D) The molecule that has an S6 symmetry element is SF6. Here S6 is improper axis of
rotation. Condition for the improper axis (Sn):- There must be either rotation followed by
reflection or reflection followed by rotation occurs that is Sn = Cn. n or n. Cn this type
of rotation only when Cn  n.
113. (C) We know that
G° = G°f (Products) – G°f (Reactants)
= (–154·0 + 0) – (0 + 64·4 kJ) = –218·4 kJ
From Eq. 1, G° = – nFE°
G 218·4kJ mol1 218400 V C mol1
E° = –  1

nF 2  96485 C mol 2  96485 C mol1
= 1·13 V (J = V C)
114. (B) Let number of nickel ions = 98
 Number of oxide ions = 100
Total negative charge on O2– ions
= 2 × 100 = 200
Let number of Ni3+ ions = x
 Number of Ni2+ ions = 98 – x
x × 3 + (98 – x) × 2 = 200
3x – 2x = 200 – 196
x= 4
Number of Ni2+ ions = 98 – x
= 98 – 4 = 94
Percentage of nickel as Ni2+
94
  100  95.91%
98
115. (B) The sticking probability for adsorption is defined as
Rate of adsorption of particles by the surface

s
Rate of collision of particles with the surface
The rate of collision of the gas molecules with the metal surface may be calculated using
collision theory. The flux is
p
ZW 
(2mkT)1/ 2
here P = Pressure = 0.10 kPa
= 100 Pa
m = mass of N2
k = boltzmann constant
= 1.381 × 10–23 Jk–1
T = temperature
so, that because the mass of a nitrogen molecules is
m = 2 × 14.01 × 1.661 × 10–27 kg
= 4.56 × 10–26 kg
the rate of collision per unit area is
p
ZW =
(2mkT)1/ 2
100
 26
(2  3.14  4.65  10 kg  1.381 1023 JK 1  298 K)1/ 2
= 2.88 × 1024 s–1 m–2
The rate of adsorption is therefore,
s × ZW = 0.74 × 2.88 × 1024 s–1 m–2
= 2.13 × 1024 s–1 m–2
(s = sticking probability)
116. (C)
N2O4 (g) 
 2NO2 (g)


2atm 2atm
2
P NO2
Kp = P = 2 atm.
N2O 4
The moment when volume is doubled the pressure becomes exactly half.
N2O4 (g) 
 2NO2 (g)


1atm 1atm
Final : (1–x) atm (1 + 2x) atm
Total pressure = (1 – x) + (1 + 2x) = 2 + x
P2NO2
Kp = P
N2O 4
(1  2x)2
2
(1  x)
or x = 0.16
PT = (2 + x) = (2 + 0.16) = 2.16 atm.

117. (B) Let n1 = n2 = 10 (say). Then

n1M1  n2M2 10  10,000  10  100,000
MN  
n1  n2 10  10
105  106 105 (1  10) 11

    10 4  55,000
20 20 2
w
118. (D) PV  RT
M
Given w = 3.2g
723
P atm
760
780
V lit.
1000
723 780 3.2
   0.0821 683
760 1000 M
M = 256
256
 atomicity = = 8
32
119. (C) Molecular weight of naphthoic acid
C11H8O2 = 172 gmol–1
The theoretical value of depression in freezing point = kf × molality
w /M
= Kf   1000
W
Given w = weight of napthoic acid = 15 g
M = molecular weight of napthoic acid = 172 g mol–1
W = weight of benzene = 50 g
15 /172
 1.72   1000
50
= 3 K
Van’t Hoff factor,
Observed value of colligative property 3
i   0.75 .
Theoretical value of colligative property 4
120. (B) [CoCl4]2–  sp3  tetrahedral geometry  point group  Td
[Co(H2O)4Cl2]  two isomers
Cl Cl
H2 O OH2 H2 O Cl
Co Co
H2 O OH2 H2 O OH2
Cl OH2
Trans Cis
D4h C2v

Net Material PDF

Uploaded by

Copyright:

Available Formats

Net Material PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Net Material PDF

Uploaded by

Copyright:

Available Formats

CSIR-NET

Chemical Sciences (CH)

Eduncle.com For Counselling

1. IUPAC NOMENCLATURE OF ORGANIC COMPOUNDS

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 1

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 2

General Rules for IUPAC Nomenclature of Organic Compounds

6-ethyl-2, 4-dimethyl nonane

3-ethyl-7-methylnonane (not 3-methyl-7-ethylnonane)

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 3

4-ethyl-7-propyldecane (not 7-ethyl-4-propyldecane)

5, 5-bis (1, 1-dimethylpropyl) 2-methyldecane

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 4

6-oxohexanoic acid 3-formyl-6-oxononanoic acid

Nomenclature of Alicyclic Compounds

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 6

Nomenclature of Bicyclic Compounds

Nomenclature of Spiro Compounds

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 7

IUPAC Nomenclature of Aromatic Compounds

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 9

R, S Nomenclature for Stereoisomers

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 10

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 11

Priority order : OH, CH2CH3, CH3, H

Priority order : OH, NH2, CH3, H

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 12

Designation of Configuration of C-2 and C-3 :

Hence, the molecule may be represented as (2R, 3S).

(Priority : Cl > F and I > Br)

(Priority : CH3 > H and Cl > CH2CH3)

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 13

Structural isomerism Stereo isomerism

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 14

Representation of Conformational Isomers :

front carbon rear carbon

0° 60° 120° 180° 240° 300° 360°

PE = Eclipsed > skew > Staggered

 The eclipsed form is least stable (unstable) due to

Repulsion between bondpairs

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 16

(2) Conformation of Propane :

CH3 CH3 CH3

CH3 CH3 CH3

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 17

Energy Profile Diagram :

0° 60° 120° 180° 240° 300° 360°

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 18

But in this case :

 This is due to steric repulsion of bulky groups.

CH3 CH3  = 60°, 180°

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 21

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 22

PE = B1 > B2 > E2 > E1

Contact Us : Website : www.eduncle.com | Email : info@eduncle.com | Call Us : 9829489592 23

60° 90° 108° 120°

Cyclopropane Cyclobutane Cyclopentane Cyclohexane

 This can be explained by Heat of combustion

(1) Chair Form :