Organic Chemistry :

12 Some Basic Principles and

Techniques
TETRAVALENCY AND SHAPES OF ORGANIC sp, sp2 or sp3 hybridised.
MOLECULES Hybridisation influences the bond length and bond strength in
The tetravalence, formation of covalent bond and catenation organic compounds. The sp hybrid orbital contains more
property of carbon results in the formation of a large number of s-character and hence, it is closer to its nucleus and forms shorter
compounds of carbon. These compounds are covalent in nature and stronger bonds than sp3 hybrid orbital.
and are studied under a branch of chemistry called organic The bond angles and geometry associated with the three types of
chemistry. Carbon atoms present in organic compounds are either hybridization are summarized below :

3
Hybridisation sp sp2 sp

Angle 109º28' 120º 180º

Geometry Tetrahedral Trigonal Linear
Example Alkane, Cycloalkane Alkenes and other compounds Alkynes and all other
and in saturated part containing C=C, C=O, compounds containing
of all organic molecules C=N and C=S double bonds C C and C N triple bonds,

Bond Four- Three-s Two-s

One- Two-

s% 25 33.3 50

p% 75 66.7 50
Electronegativity 2.48 2.75 3.25

C(sp) – H > C(sp2)–H > C(sp3)–H For example few compounds are represented in all three
121 kcal mol –1 106 kcal mol –1 98.6 kcal mol–1 formulas below :
Ex:
C(sp) – C(sp) > C(sp ) – C(sp ) > C(sp3) – C(sp3)
2 2
(a) Butane (C4H10)
200 kcal mol–1 142 kcal mol–1 80-85 kcal mol–1 H H H H CH3CH2CH2CH3
Note : (i) Greater is the s - character of the hybrid orbitals, greater
Condensed
is the electronegativity. Thus, a C - atom having an sp hybrid H C C C C H
orbital with 50% s - character is more electronegative than sp2
(33% s-character) or sp3 (25% s-character) hybrid orbitals. H H H H Bond line
(ii) Since a bigger orbital forms a longer bond, therefore, C–C
single bond length decreases in the order: Complete
(b) 2 - Bromobutane
C(sp3) – C(sp3) > C (sp2) – C(sp2) > C(sp) – C(sp)
H H H H CH3CHBrCH2CH3
1.54 Å 1.34Å 1.20 Å
Condensed
STRUCTURAL REPRESENTATIONS OF ORGANIC H C C C C H
COMPOUNDS
H Br H H
(i) Complete, Condensed and Bond - line
Structural Formulas : Complete Br
Bond - line
 (c) 1- Bromocyclopentane (ii) 3D Representation
H
| By using solid ( ) and dashed ( ) wedge formula, 3-D
C CH2 image of a molecule can be shown from 2D picture. The dashed
H – C – H | H – C – Br line depicts the bond projecting out of the plane of paper and
H CH2 CHBr away from the observer while solid-wedge depicts the bond
projecting out of the plane of paper and towards the observer.
H–C C–H The bonds lying in plane of paper are depicted by using a
| | CH2 CH2
normal line (–).
H H Condensed
Ex: Ethane
Complete
Bonds away Bonds in the
Br from observer C C plane of paper
Bonds toward
observer
Bond line
CLASSIFICATION OF ORGANIC COMPOUNDS
Organic Compounds

Open chain Closed chain

or or
Acyclic Cyclic
or or
Aliphatic compounds Ring compounds

Unsaturated Homocyclic Heterocyclic

Saturated e.g. Benzene e.g. pyrrole
e.g. Alkanes e.g. Alkenes & Alkynes

Alicyclic Aromatic

Saturated Unsaturated Benzenoids Nonbenzenoids

e.g. cyclopropane e.g. cyclopropene

NOMENCLATURE OF ORGANIC COMPOUNDS

CH3 CH2 CH CH2 CH CH3
Nomenclature of Alkanes
CH3 CH CH3
(i) Straight chain hydrocarbons:
CH3
The names of such compounds are based on their chain
structure, and end with suffix ‘-ane’ and carry a prefix 2 side chains (wrong)
indicating the number of C - atoms present in the chain. The CH3 CH2 - CH - CH2 - CH - CH3
alkanes differ from each other by no. of – CH2 groups in the l l
CH3 - CH CH3
chain. l
Some names are: CH3
Methane CH4 Butane C4H10 3-side chains (correct)
Ethane C2H6 Pentane C5H12 1 2 3 4 5 6 7 8 9
Propane C3H8 Hexane C6H14 CH3 — CH — CH2 — CH2CH2CH — CH2CH2 CH3 P Correct
(ii) Branched chain hydrocarbons: The rules for naming are: CH3 CH2CH3
(a) The longest C - chain in the molecule is identified. Out
1 2 3 4 5 6
of all the possible chains. If there are the possibilities of CH3 — CH CH2CH2CH2CH CH2CH2CH3 Incorrect
more than one longest chain the chain which possesses
more than one side chain is selected. CH3 CH2CH3
7 8
(b) The numbering is done in such a way that branched carbon (2) If side chains are different numbering is given in
atoms get the lowest possible numbers. alphabetical preference order.
1 2 3 4 5 6 7 8 9 Ex.
C—C—C—C—C—C—C—C— C Correct P 7 6 5 4
H3C - CH2 - CH - CH2 - CH - CH2 - CH3 (Wrong)
3 2 1

C C—C l l
E H2C CH3 M
9 8 7 6 5 4 3 2 1 l
C—C—C—C—C—C— C—C— C Incorrect H3C
1 2 3 4 5 6 7
C C—C CH3 CH2 CH CH2 CH CH2 CH3 (Right)
In case, the parent chain has two or more substituents, numbering CH2 CH3 M
must be done in such a way that the sum of the locants on the E
parent chain is the lowest possible. Thus in following structures CH3
A and B numbering may be done in two ways : in one (A), the sum (f) Naming the complex substituent : In case the substituent
of locants is 9 while in other (B), it is 12, hence the former is correct
on the parent chain is complex (i.e., it has itself branched chain)
while the latter is wrong.
then it is named as a substituted alkyl group and its carbon chain
C C C C C C is numbered from the carbon atom attached to the main chain. The
| | | | | |
C- C- C - C- C - C C- C - C- C - C- C name of this complex substituent is written in bracket to avoid
1 2 3 4 5 6 6 5 4 3 2 1 confusion with the numbers of the main chain. e.g.,
Sum of locants : 2 + 3 + 4 = 9 (A) Sum of locants : 3 + 4 + 5 = 12 (B)
(correct) (incorrect) 3¢ CH3
(c) The names of alkyl groups attached as a branch are prefixed |
to the name of parent alkane and position of substituents is 2¢ CH - CH3
|
indicated by appropriate numbers. If different alkyl groups 1¢ CH - CH3
are present they are listed in alphabetical order. For example 1 2 3 4 5| 6 7 8 9
CH3 - CH - CH - CH 2 - CH3 CH3 - CH 2 - CH 2 - CH 2 - CH - CH 2 - CH 2 - CH 2 - CH3
| | 5- (1¢, 2¢ - dimethylpropyl) - nonane
CH3 C2H5 Nomenclature of Cyclic Compounds
3–Ethyl–2 methylpentane and not as
2 - Methyl -3- ethylpentane A saturated monocyclic compound is named by prefixing ‘cyclo’
(d) If two or more identical substituent groups are present, then to the corresponding straight chain alkane. If side chains are given,
numbers are separated by commas. The names of identical then rules given above are applied.
substituents are indicated with prefixes such as di, tri, tetra, For example : Cyclobutane
penta, hexa, etc. While writing names of substituents spelling
of these prefixes are not considered.
For example : 12
3 1 - methyl - 3 - propylcyclo - hexane
CH3
6 5 4| 3 2 1
CH3 - CH 2 - CH - CH 2 - CH - CH3 Nomenclature of Organic Compounds Containing
| | Functional Groups
C2 H 5 CH3
4 - Ethyl - 2, 4 - Dimethylhexane
(i) Numbering is given from the end from which functional group
is closest.
CH3 C2H 5 (ii) If the functional group is situated at same carbon from both
1 2 3| 4| 5 6 7 sides, follow the rules of saturated hydrocarbons.
CH 3 - CH 2 - C - CH - CH 2 - CH 2 - CH3 1 2 3 4 5
| Ex. C C C C C ( Wrong )
CH3
4 - Ethyl -3, 3- dimethylheptane C OH
5 4 3 2 1
(e) If side chains are at same carbon from both sides, C C C C C (Right)
following rules are adopted :
C OH
(1) For same side chains numbering may be given from any 7 6 5 4 3 2 1
end. C C C C C C C (Wrong)
1 2 3 4 5 C OH C
C- C- C- C- C
| | ( Right ) C
C C 1 2 3 4 5 6 7

5 4 3 2 1
C C C C C C C (Right)
C - C - C - C - C (Right) C OHC
| |
C C C
(iii) If the organic compound contains two or more functional (iv) — R, — C6H5, halogens (F, Cl, Br, I), –NO2, – OR etc. are
groups, one of the group is selected as principal functional always prefix substituents.
group containing longest possible chain of carbon atom (v) If more than one functional group of same type is present,
and all the remaining functional groups are treated as their number is indicated by adding di -, tri, etc. before the
substituents. class suffix.
Order of preferance used while selecting the principal Examples :
functional group (a) CH3CH2COCH2COCH3
Carboxylic acids > Sulphonic acids > anhydrides > esters Hexane - 2, 4 - dione
> acid chlorides > acid amides > nitriles > aldehydes > (b) CH º C - CH = CH - CH = CH 2
cyanides > isocyanides > ketones > alcohols > phenols > Hexa - 1, 3 - dien - 5 - yne
thiols > amines > ethers > alkenes > alkynes. See the following table for IUPAC names of certain organic
For example : compounds
CH3 – CH – CH2 – CH – CH3 CH3
| | |
NH2 OH CH3 – C – COCH3
4-Aminopentan–2–ol |
OH
–hydroxy –3–methyl
butan –2–one

Class of Functional group Functional Functional

compounds structure group prefix group suffix
Alkanes – – -ane
Alkenes >C=C< – -ene
Alkynes – C º C– – -yne
Arenes – – -
Halides –X halo -
(X = F, Cl, Br, I)
Alcohols –OH hydroxy -ol
Aldehydes –CHO formyl, -al
or oxo
Ketones >C=O oxo -one
Nitriles - CN º cyano nitrile
Ethers R-O-R alkoxy -
Carboxylic –COOH carboxy -oic acid
acids
Carboxylate – -oate
- COO-
ions
Esters –COOR alkoxycarbonyl -oate
Acyl halides –COX halocarbonyl -oyl halide
(X = F, Cl, Br, I)
Amines - NH2 , > NH, N - amino -amine
Amides - CONH,2 carbamoyl -amide
- CONHR,
- CONR 2
Nitro - NO2 nitro -
compounds
Sulphonic - SO3 H sulpho sulphonic acid
acids
Thio alcohol — SH Mercapto – – thiol

Anhydride — CO — – oic anhydride

O
— CO
Isocyanide —N C Carbylamine – iso nitrile
 O O O O (iii) For tri - or higher substituted benzene derivatives, the
compounds are named by identifying substituent positions
Note : C H, C OH, C Cl, C NH2 & – C º N on the ring by following lowest locant rule. In some cases,
are the groups of which carbons are also included in the common name of benzene derivatives is taken as base
longest chain. If these are alone in a compounds they comes compound. Substituent of base compound is assigned no. 1
on first carbon, if double, comes on first and last positions. and then the direction of numbering is chosen such that the
Nomenclature of Aromatic Compounds next substituent gets the lowest number. The substituents
(i) The substituent is placed as prefix to the word benzene. should be numbered according to alphabetical order.
Examples : ex:
Cl
CH3 OMe NH2 1 - Chloro - 2, 4 - dinitrobenzene

ON2 NO2

Methyl benzene Methoxy benzene Amino benzene NO2

(Toluene) (Anisole) (Aniline)
2 - Chloro - 1 - methyl - 4 - nitrobenzene
(ii) If benzene ring is disubstituted, position of substituents is
defined by numbering the C-atoms of ring such that
substituents are located at lowest numbers possible. Cl
Example : CH3

OMe
CH3 CH3 1
CH3 1 1 Cl
1 CH3 2 2 - Chloro - 4 - methyl anisole
2 3
3 CH3 4 4
1,2-Dimethylbenzene 1,3-Dimethylbenzene CH3 CH3
(o-Xylene) (m-xylene) 1,4-Dimethylbenzene
(p-xylene) (iv) When benzene ring is attached to an alkane with a functional
group, it is considered as substituent instead of parent and
its name as a substituent is phenyl

ISOMERISM
The phenomenon of existence of two or more compounds possessing same molecular formula but different properties is called
isomerism and the compounds are called isomers. The following chart shows different types of isomerism.
Types of Isomerism

Structural isomerism Stereoisomerism

Conformational Configurational
Chain Position Functional Metamerism
Tautomerism isomerism Isomerism
isomerism isomerism isomerism

Geometrical Optical
Structural Isomerism: It arises when compounds have same molecular formula but different structures. It arises because of the
difference in the sequence of covalently bonded atoms in the molecule without reference to space.
Types of Structural Isomerism (a) Molecular formula : C2H6O
(i) Chain isomerism : Two or more compounds with same CH3 – CH2 – OH and CH3 – O – CH3 : Functional isomers.
molecular formula but different carbon skeletons are called Ethyl alcohol Dimethyl ether
chain isomers and the phenomena is known as chain (Alcohol) (Ether)
isomerism.
(b) Molecular formula : C3H6O
Examples :
Pentane : C5H12 O O
|| ||
CH3CH2CH2CH2CH3 CH3CHCH 2CH3 CH3 – CH2 – C – H and CH3 – C – CH3 Functional isomers
|
CH3 Propanal Propanone
(Aldehyde) (Ketone)
n-Pentane Isopentane (c) Molecular formula : C3H6O2
CH3
| O
CH3 - C - CH3 ||
| CH3 – CH2 – COOH and CH3 – C – O – CH3
CH3 :Functional isomers
Neopentane Propanoic acid Methyl acetate
n-Pentane, isopentane and neopentane possess the chain of (Acid) (Ester)
five, four and three carbons, respectively. Hence they are (iv) Metamerism :This type of isomerism is due to unequal
chain isomers. distribution of substituents on either side of the polyvalent
Butyl alcohol : C4H9OH functional group.
CH3 – CH2 – CH2 – CH2OH CH3 - CH - CH 2 OH Members belong to the same homologous series.
| Ex.
CH3 (a) Diethyl ether and methyl propyl ether
n-Butyl alcohol Isobutyl alcohol CH3CH2OCH2CH3 CH3OCH2CH2CH3
These two butyl alcohols are chain isomers. Diethyl ether Methyl propyl ether
(ii) Position isomerism : It is shown by the compounds in which (b) Diethyl amine and methyl propyl amine
there is difference in the position of attachment of functional CH3CH2 – NH – CH2CH3 CH3CH2CH2 – NH – CH3
group, multiple bond or substituent along the same chain Diethyl amine Methyl propyl amine
length of carbon atoms. (v) Tautomerism :Tautomerism is a special type of functional
group isomerism which arises due to the migration of H-atom
Examples : CH3 – CH2 – CH2Cl & CH3 – CH – CH3
as proton from a polyvalent atom to other polyvalent atom
|
Cl with reshuffling of p bond.
Keto-Enol Tautomerism :
1-Chloropropane 2-Chloropropane
When the tautomers exist in the two forms keto & enol then, such
Molecular formula : C4H8
CH3 – CH2 – CH = CH2 and CH3 – CH = CH – CH3 : type of tautomerism is called keto-enol tautomerism.
1-Butene 2-Butene Keto means the compound has a keto group > C = O, and the enol
Note : In the disubstituted benzene derivatives also position form has both double bond and OH (hydroxy) group joined to the
isomerism exists because of the relative position occupied same carbon.
by the substituents on the benzene ring. Thus, H O OH
Chlorotoulene, C6H4(CH3)Cl exists in three isomeric forms - | || |
ortho, meta and para. –C–C– Û –C=C–
| |
CH3 CH3 CH3
Keto form Enol form
Cl
O H
P |
(a) CH3 - C - H Û CH 2 = C – OH
Cl
Cl Acetaldehyde Vinyl alcohol
o-Chlorotoluene m-Chlorotoluene p-Chlorotoluene O H OH
(iii) Functional group isomerism : When two or more compounds || | |
have same molecular formula but different functional groups. (b) CH3 – C – CH – COCH3 Û CH3 – C = CH – COCH3
Such compounds are called functional group isomers
(Keto) (Enol)
 (i) Geometrical isomerism : Arises due to different geometries
of compounds, i.e., different arrangement of atoms or groups
around doubly bonded C - atoms.
Two types:

Stereoisomerism
Two or more compounds which
have the same molecular formula Cis-isomer Trans-isomer
and the same connectivity of atoms
but different three dimensional Two identical atoms or Two identical atoms or
arrangement of their constituent groups lie on same side groups lie on opposite
atoms or groups are said to be of double bond i.e. side of double bond, i,e.
stereoisomers and the phenomenon
is termed as stereoisomerism. X X Y
X
C=C C=C
Y Y X X
If the two atoms or groups linked to same doubly linked carbon are similar
as in the molecule aaC = Cab, the compound does not show geometrical
isomerism.
(ii) Optical isomerism : It is shown by compounds which rotates the
plane of polarised light either towards right i.e clockwise or towards left,
i.e., anti - clockwise.
Optical activity : It is the ability of a substance to rotate the plane
of polarisation of plane polarised light. C2H5 C2H5 C2H5
(a) One rotating the plane of polarised light to the left. This form
Y H Y H
is named as laevorotatory. (Latin, laevous = left) or H
direction (–) form X
Y Y
(b) One rotating the plane of polarized light exactly to the same
extent but to the right is named dextrorotatory (Latin Dexter – CH3 CH3 CH3
right) or direction (+) – form. A
B Y
(c) An inactive form which does not rotate the plane of polarized
light at all. This is a mixture of equal amounts of (+) and (–) – A+ B
forms and hence it is optically inactive. It is named (±) - mixture if only (A) is obtained, process is called retention of configuration.
If only (B) is obtained, process is called inversion of configuration.
or Racemic mixture. (Latin, Racemic - mixture of equal If 50:50 mixture of above two is obtained then the process is called
compounds) Asymmetric carbon atom : A carbon atom racemisation and the product is optically inactive.
attached to four different atoms and groups is called
asymmetric carbon atom. e.g. CH3*CHOHCOOH. REACTION MECHANISM
Chirality : If the mirror image of the molecule is different from the A general reaction is depicted as:
molecule it is said to be a chiral molecule. In such case if one Attacking [Intermediate] Product (s)
configuration of the molecule is placed above its mirror image reagent
configuration, the similar atoms and groups do not fall over each By product(s)
other and the configurations are said to be nonsuperimposable. A sequential account of each step, describing details of electron
Chirality is the necessary condition for a compound to be optically movement, energetics during bond cleavage and bond formation,
active. and the rates of transformation of reactants into products is
Enantiomers : Pairs of nonsuperimposable mirror images are called referred to as reaction mechanism.
enantiomers. Enantiomers are non superimposable mirror Fission of a Covalent Bond
image isomers. They have identical physical properties (bpt, mpt, A covalent bond can be cleaved in two ways:
density etc.) except for their rotation of plane polarised light. They (i) Homolytic cleavage : On bond breaking, one of the electrons
are much more difficult to separate. In nature very often only one of shared pair in covalent bond goes with each of the bonded
enantiomer is produced. Living organisms are one of the best atoms.
sources of optically active compounds (plants, enzymes, animals, Homolytic fission
A+ B
A B ¾¾¾¾¾¾¾ ®
cells etc.). Free radicals
Diastereo Isomers : Stereo isomers which are not mirror images of It results in the formation of free radicals which contain an
each other are called diastereo isomers. They have different odd or unpaired electron. Such reactions are called free radical
physical properties (mpt, bpt, solubility) and are often easy to or homopolar or non-polar reactions.
separate by distillation, recrystallisation, chromatography etc.). Favourable conditions :
Racemiemixture : A mixture containing equal amounts of two (a) High temperature (b) Light of suitable wavelength
enantiomers will have zero optical rotation and is called racemic (c) Non polar solvent (d) Presence of peroxide or oxygen
mixture (e) Ability of substrate and attacking reagent to produce free-
radicals.
(ii) Heterolytic cleavage : When a covalent bond joining two +
atoms A and B breaks in such a way that both the electrons e.g. - N R 3 > – NO2 > – CN > – COOH > –F
of the covalent bond (i.e., shared pair) are taken away by one
of the bonded atoms, the mode of bond cleavage is called > – Cl > – Br > – I > – O && H > – O
&& R > –C H > – H
6 5
heterolytic fission or heterolysis. (b) +I Effect : Those atoms or group of atoms which attract the
shared electron pair (bond pair) less strongly than hydrogen
Heterolytic fission + –
A : B ¾¾¾¾¾¾¾ ® A +:B atom are said to have +I (electron repelling) effect. Such
(when B is more electronegative than A) groups when attached with a carbon chain displace the shared
It results in formation of cations and anions s electrons towards the chain and make it electron rich.
Favourable conditions : (a) Low temperature (b) Polar solvent (c) (CH3)3C – > (CH3)2CH – > CH3 – CH2 – > CH3 –
Presence of acid or base catalyst (d) Polar nature of the substrate (ii) Resonance effect : It is defined as the polarity produced in a
and attacking reagent. molecule by the interaction of two p - bonds or between a p -
Nucleophiles and Electrophiles bond and lone pair of e–1 s present on an adjacent atom. It is
A reagent that brings an electron pair is called a nucleophile i.e. also called mesomeric effect. It is a permanent effect.
nucleus seeking and the reaction is called nucleophilic. Two types of resonance effects:
They are of two types : (a) Positive resonance effect (+ R effect)
(a) Charged Nucleophiles : In this effect, transfer of electrons is away from an atom group
All the negative ions qualify as nucleophiles. attached to the conjugated system. This effect results into
F–, Cl–, Br–, I–, OH–, CN–, RCOO– increase in electron density at certain positions in molecule.
– – Example : Phenol
RO–, R–, R—C º C–, NH 2 , SH , etc.
H H
(b) Neutral Nucleophiles : Central atom has electron pair. O O
+

&& , R — NH &&
&& , R – NHR && , H O
, R 3N && &&
NH 3 2 2 :,R– O . . – H,
A reagent that takes away an electron pair is called an electrophile
(E+) i.e., electron seeking and the reaction is called electrophilic
Phenol
Electrophiles may be neutral or positively charged.
(a) Neutral electrophiles : Central atom has deficiency of
H
electrons. ex. BF3, BCl3, AlCl3, BeCl2, FeCl3, SO3, etc.. +
O
+
O
H H
O
(b) Charged electrophiles :
All the positive ions behave like electrophiles.
+
Cl+, Br+, I+, NO2+, NO+, H+, H3O+, N H 4 , R+,
+
R — C = O , etc.
Examples : halogen, – OH, – OR, – OCOR, – NH2, – NHR,
Electrophiles are generated by heterolysis of a covalent bond. – NR2, – NHR, – NR2, – NHCOR
Transition metal cations are electrophiles Decreasing order of activating (+R) groups
For example : Fe3+, Fe2+, Ag+, Hg2+, Cd2+, etc. –O– , –NH2 , –NHR , –NR2 , –OH , –OR , –NHCOR , –R ,
Electron Displacement –Ar , –X (Till –OH they are very strong activating groups)
The electron displacement in an organic molecule may take place (b) Negative resonance effect (– R effect)
either in ground state under the influence of an atom or a group or In this effect, transfer of electrons occurs towards atom or
in presence of an appropriate attacking reagent.
group attached to the conjugated system.
Electron displacement due to influence of an atom or group present
in molecule cause permanent polarisation of the bond. Example: Example : Nitrobenzene
– –
Inductive effect and resonance effect. O O O
O
Temporary electron displacement effects are seen in a molecule N N
when a reagent approaches attack it.
Example: electromeric or polarisability effect.
(i) Inductive Effect : The polarisation of s - bond caused by
polarisation of adjacent s - bond is called inductive effect. It – –
O O O O
is a permanent effect. The effect decreases as the number of
N N
intervening bonds increases and becomes very small after
three C - atoms. Inductive effect (I–effect) is of two types.
(a) –I effect : Atoms or group of atoms which attract the bonded O
electrons more strongly than hydrogen atom, are said to have N O
–I effect and are termed as electron attracting (–I groups).
Such groups when linked with a carbon chain make it electron
poor.
 Effects of hyperconjugation :
– (1) Stability of alkenes :
Examples : –COOH, – CHO, C = O, – CN, NO2
(a) Alkylated alkenes are more stable than others.

R - C = C - R > R 2C = CHR.
The very strong deactivating (–R) groups are | |
–NO2 , –CF3 , –NR3+ R R
Conditions for Resonance : [Tetraalkyl ethylene]
(1) The atomic arrangement is the same in all the canonical forms.
(2) Same number of paired or unpaired electrons must be present RCH = CHR > R2C = CH2 > R – CH = CH2 > CH2 = CH2
in each canonical form. Least stable
(3) The canonical forms must possess same or nearly same (b) Greater the number of a C – H bonds in an alkene, greater
energy. will be the number of hyperconjugated structures, hence
(4) The molecule must have a planar structure. greater will be the stability.
(iii) Electromeric effect (E - Effect) : It is defined as the complete (2) Bond lengths : Hyperconjugation in a molecule results in a
transfer of a shared pair of p - electrons to one of the atoms change in bond lengths.
(more electronegative) joined by a multiple bond on demand (3) Stability of alkyl free radicals :
of an attacking reagent. It is a temporary effect. t–alkyl > sec. alkyl > primary alkyl > CH3 (methyl radical)
Two types of electromeric effect: Greater the number of hyperconjugative structures of an alkyl
(a) + E effect radical, higher is the stability.
In this, p – electrons of multiple bond are transferred to that (4) Stability of alkyl carbonium ions : Greater the number of
atom to which reagent gets attached. alkyl groups attached to positively charged carbon atom,
For example : greater is the hyperconjugation interaction and stabilisation
of the cation.
CH3 CH CH2 H CH3 CH CH3 The relative stability of carbocations follows the order:
Propene Isopropyl carbocation CH3
(b) – E effect | + + +
CH3 — C + > ( CH3 ) 2C H > CH3C H 2 > C H3
In this, p – electrons of multiple bond are transferred to that |
atom to which attacking reagent does not get attached CH3
For example :
INTERMEDIATES
H O–
– H
O CN C Free Radicals
H H CN
| |
Homolytic fission
Formaldehyde Anion
Anion -C - X ¾¾¾¾¾¾¾¾ ® – C• + X•
Oxygen being more electronegative pulls p electrons of | |
multiple bond toward itself. Carbonyl C aquires positive If EN of C – ~ EN of X
charge thus got attacked by nucleophile. It is an atom or group of atoms possessing an odd or unpaired
(iv) Hyperconjugation : It involves delocalisation of s – electrons electron. It is electrically neutral and shows paramagnetism.
of C – H bond of an alkyl group directly attached to an atom Stability of free radicals is due to following reasons :
of unsaturated system or to an atom with an unshared p - (i) Resonance (ii) Hyperconjugation
orbital. It is a permanent effect. Hyperconjugation is also
Order of stability of free radicals :
called no -bond resonance.
t-butyl > isopropyl > ethyl > methyl
In propylene, there are three H—C sigma bonds in Stability on the basis of resonance :
conjugation with the p bond. So, only three resonating forms
Stability µ Number of resonating structures
can be written.
The order is :
H (f)3C· > (f)2CH· > f CH2· > CH2 = CH – CH2·
H+ [where f = C6H5]
H РC РCH = CH2 ¨ H РC = CH РCH2
|
Carbonium ion or Carbocation – C
H H
Propylene contains |
3H – C hyperconjugated bond
| |
Heterolytic fission
H H - C - X ¾¾¾¾¾¾¾¾ ® - CÅ + : X Q
| |
¨ H+ C = CH РCH2 ¨ H РC = CH РCH2

H
H+ If EN of X > EN of C
Organic species containing positively charged carbon atom is PURIFICATION OF ORGANIC COMPOUNDS
known as carbonium ion. The positively charged carbon atom A large number of methods are available for the purification of
contains six electrons in its valence shell. substances. The choice of method, however depends upon the
Stability of carbonium ions : nature of substance (whether solid or liquid) and the types of
1 impurities present in it. Following are some of the important
Stability of carbocation µ +I µ
–I methods which are commonly employed for the purification of
Å organic compounds:
> CH > NO – CH
Å Å
e.g. (i) CH3– CH 2 3 2 2 (1) Filtration, (2) Crystallization, (3) Fractional crystallization, (4)
Å Å Å Sublimation, (5) Distillation, (6) Fractional Distillation, (7)
(ii) (C6H5)3 C > (C6H5)2 CH > C6H5 CH 2 Distillation under reduced pressure, (8) Steam Distillation, (9)
Å Å Differential extraction, (10) Chromatography
> CH2 = CH – CH 2 > 3º > 2º > 1º > CH 3 QUALITATIVE AND QUANTITATIVE ANALYSIS
Stability µ No. of resonating structures
Qualitative Analysis
é | ù The elements present in organic compounds are C and H. In
Carbanion ê -C : - ú :
Q
ê | ú addition to these, they may also contain O, N, S, halogens and P.
ë û Detection of C and H: They are detected by heating the compound
| with copper (II) oxide. C is oxidised to CO2 and H to H2O. CO2
| Heterolytic fission
-C - X ¾¾¾¾¾¾¾¾ ® - C :Q + XÅ turns white lime water milky, while water formed turn white
| | anhydrous CuSO4 to blue hydrated CuSO4.
If EN of C > EN of X D
An organic species containing negatively charged carbon atom is C + 2CuO ¾¾® 2 Cu + CO 2
called carbanion. D
2H + CuO ¾¾® Cu + H 2O
Stability of carbanion is due to following reasons
(i) Inductive effect CO 2 + Ca( OH ) 2 ¾¾
® CaCO 3 ¯ + H 2 O
(ii) Resonance
(iii) s-character in Hybridisation
5H 2 O + CuSO 4 ¾¾
® CuSO4 .5H2 O
1
Stability of Carbanion µ –I , µ white blue
+I
.–. Detection of other elements
.–. .–.
Ex. (i) CH3– CH2 < CH3 < NO2 – CH2 Preparation of Lassaigne’s extract : N, S halogens and P are
detected by Lassaigne’s test. The elements present in organic
– – – –
(ii) CH 3 > CH3 CH2 > (CH3)2 CH > (CH3)3 C compounds are converted to ionic form by fusing with Na-metal.
The reactions involved are:
Note : Carbanions are nucleophiles.
D
TYPES OF ORGANIC REACTIONS Na + C + N ¾¾® NaCN

(i) Substitution or Displacement Reactions D

2Na + S ¾¾® Na 2S
Substitution or displacement reactions are those reactions in which
D
an atom or group of atoms attached to a carbon atom in a substrate Na + X ¾¾® NaX ( X = Cl, Br, I)
molecule is replaced by another atom or group of atoms. They are extracted from fused mass by boiling with distilled water.
(ii) Addition Reactions The extract is known as sodium fusion extract (Lassaigne’s extract).
Addition reactions are those in which the attacking reagent adds (a) Test for N : The extract is boiled with FeSO4 and then acidified
with conc. H2SO4. Prussian blue colour confirms presence
up to the substrate molecule. Such reactions are given by those
of nitrogen.
compounds which possess double or triple bonds.
4-
(iii) Elimination Reactions 6 CN - + Fe2 + ¾¾
® éë Fe ( CN )6 ùû
The reverse of addition reactions are termed as elimination
4- xH 2O
reactions. In these reactions generally atoms or groups from two 3 éë Fe ( CN )6 ùû + 4Fe3+ ¾¾¾¾ ® Fe 4 éë Fe ( CN )6 ùû . xH 2O
adjacent carbon atoms in the substrate molecule are removed and 3
multiple bond is formed. But if sulphur is also present along with nitrogen one gets
blood red colouration due to formation of ferric thiocyanate.
(iv) Rearrangement Reactions
Na + C + S + N ¾¾ ® NaSCN
The reactions which involve the migration of an atom or group
from one site to another within the molecule (nothing is added Fe3+ + 2NaSCN ¾¾ ® Fe(SCN)3 + 3Na+
from outside and nothing is eliminated) resulting in a new molecular Blood red
structure are known as rearrangement reactions.
(b) Test for S: (ii) Nitrogen
(i) To extract, add CH3COOH and lead acetate. A black ppt (a) Duma,s method: The N-containing organic compound, when
of PbS confirms S. heated with CuO in an atmosphere of CO2, yields free N2 in
addition to CO2 and H2O.
S2- + Pb2+ ¾¾ ® PbS ¯
Let mass of organic compound = Wg
black Volume of nitrogen collected = V1 mL
(ii) Take small portion of Lassaigne's extract and add few Room temp = T1 K
drops of sodium nitroprusside solution, a violet
colouration is obtained which fades away on standing. P1V1 ´ 273
Volume of N2 at STP = (Let it be V mL)
2Na + S ¾¾ ® Na2S ; 760 ´ T1
Na2S + Na2[Fe(CN)5NO] ¾¾ ® Na4[Fe(CN)5NOS] P1 = Atm. pressure - Aqueous tension
violet color 22400 mL N2 at STP weighs 28 g.
(c) Test for halogens : The extract is acidified with HNO3 and 28 ´ V
then treated with AgNO3. A white ppt, soluble in NH4OH VmL N2 at STP weighs = g
22400
indicates the presence of Cl. A yellowish ppt, sparingly
soluble in NH4OH indicates the presence of Br. A yellow ppt, 28 ´ V ´ 100
insoluble in NH4OH indicates the presence of I % of N2 = 22400 ´ W

(b) Kjeldhal’s method: The compound is heated with conc

X - + Ag + ¾¾
® AgX ( X = Cl, Br, I )
H2SO4 when nitrogen gets converted to (NH4)2SO4. The
If N or S is also present, then extract is first boiled with conc. mixture is then heated with excess of NaOH. The liberated
HNO3 to decompose CN– and S2 – (they would otherwise NH3 gas is absorbed in an excess of standard solution of
interfere with AgNO3 test for halogens). H2SO4.
(d) Test for P : Phosphorus is detected by fusing the organic
D
compound with an oxidising agent like Na2O2 .P in the N (from compound) + conc. H2SO4 ¾¾ ® (NH4)2SO4
D
compound is oxidised to PO34- which is then extracted with (NH4)2SO4 + 2 NaOH ¾¾ ® Na2SO4 + 2H2O + 2NH3
water. The solution is boiled with HNO3 and then treated 2 NH3 + H2SO4 ¾¾ ® (NH 4)2SO4
with ammonium molybdate. A yellow coloured ppt indicates The volume of the acid left unused is found by titration against
presence of phosphorus. a standard alkali solution.
2 NaOH + H2SO4 ¾¾ ® Na2SO4 + 2H2O.
Na 3PO4 + 3HNO3 ¾¾
® H3PO 4 + 3 NaNO3 The difference between initial amount of acid taken and that
left after reaction gives the amount of acid reacted with NH3.
5Na2O2 +2 P ¾¾
® 2 Na3PO4 + 2 Na2O
æ V ö
14 ´ M ´ 2 ç V - 1 ÷
H3PO 4 +12 ( NH 4 ) 2 MoO4 + 21HNO3 ¾¾
® è 2 ø 100
% of N = ´
1000 W
( NH 4 )3PO 4 .12 MoO3 + 21 NH 4 NO3 + 12H 2 O Where M ® molarity
Ammonium V ® volume of H2SO4 taken
phosphomolybdate V1 ® volume of NaOH used for titration of excess of H2SO4
Quantitative Analysis W ® mass of organic compound
The percentage composition of elements present in an organic æ v ö
compound is determined in following ways: 2 ç v - 1 ÷ ® volume of NH solution
è 2 ø 3
(i) Carbon and Hydrogen
A known mass of an organic compound is burnt in presence (iii) Halogens
of excess of O2 and CuO, when C and H are oxidised to CO2 Carius method: A known mass of organic compound is heated
and H2O. Let mass of organic compound be ‘W’ g, mass of with fuming HNO3 in presence of AgNO3. C and H in the
H2O and CO2 produced be W1 and W2 g. Then, compound are oxidised to CO2 and H2O. The halogen present
12 ´ W2 ´ 100 forms Ag X which is filtered, washed, dried and weighed.
Percentage of C = Let mass of organic compound = Wg
44 ´ W
mass of AgX formed = W1 g
y D y z 1 mol of AgX contains 1 mol of X
Cx HyNz + (2x + 2 ) CuO ¾¾ ® x CO2 + H2O + N2
2 2
atomic mass of X ´ W1g
æ yö mass of X in W1 g of Ag = molecular mass of AgX
+ çè 2x + ÷ø Cu
2
2 ´ W1 ´ 100 at. mass of X ´ W1 ´ 100
Percentage of H= % of X = molecular mass if AgX ´ W
18 ´ W
(iv) Sulphur D
A known mass of organic compound is heated with sodium 2P + 5O (from HNO3) ¾¾ ® P2O5
peroxide or fuming HNO3. S in the compound is oxidised to D
P2O5 + 3H2O ¾¾ ® 2H3PO4
H2SO4. It is precipitated as BaSO4 by adding excess BaCl2
solution in water. Phosphoric acid
D H3PO4 + 12 (NH4)2MoO4 + 21HNO3 ¾¾ D
C + 2O (from HNO3) ¾¾ ® CO2 ®
(NH4)3PO4.12MoO3 + 21 NH4NO3 + 12H2O
D
2H + O (from HNO3) ¾¾ ® H2O Let mass of organic compound = Wg
D mass of ammonium phosphomolybdate = W1 g
S + H 2 O +3O (from HNO3 ) ¾¾
® H 2SO 4 Molar mass of (NH4)3PO4. 12 MoO3 = 1877 g
H2SO4 + BaCl2 ¾¾ ® BaSO4 + 2HCl 31 ´ W1 ´ 100
% of P = %
(white ppt) 1877 ´ W
The ppt is filtered, washed, dried and weighed. If P is estimated as Mg2P2O7.
The % of S is calculated from mass of BaSO4.
Let mass of organic compound taken = Wg 62 ´ W1 ´ 100
% of P = %
mass of BaSO4 formed = W1 g 222 ´ W
1 mol of BaSO4 = 233 g BaSO4 = 32 g S (vi) Oxygen
32 ´ W1 % of O2 = 100 – (sum of % of all other elements)
W1 g BaSO4 contains gS
233 D
Compound ¾¾¾¾ ® O2 + other gaseous products.
N gas 2
32 ´ W1 ´ 100
% of S = 233 ´ W 1373 K
2C + O2 ¾¾¾¾ ® 2 CO ] ´ 5 ... (A)
(v). Phosphorus
A known mass of an organic compound is heated with fuming I2O5 + 5CO ¾¾ ® I2 + 5 CO2 ] ´ 2 ... (B)
HNO3 Carbon and hydrogen are oxidised to CO2 and H2O On solving (A) and (B), we find that each mole of O2 liberated
respectively while P in compound is oxidised to H3PO4. It is produces 2 moles of CO2.
precipitated as ammonium phosphomolybdate, (NH4)3PO4. Let mass of organic compound = Wg
12 MoO3 by adding ammonium molybdate. The precipitate mass of CO2 produced = W1 g
of (NH4)3PO4. 12MoO3 is then filtered, washed, dried and
32 ´ W1
weighed. \ m1 g of CO2 is obtained from g O2
D
88
C + 2 O (from HNO3) ¾¾ ® CO2
32 ´ W1 ´ 100
D
2H + O (from HNO3) ¾¾ ® H2O \ % of O2 = 88 ´ W
%
CONCEPT MAP
1. The number of en antiomers of th e compound 8. The IUPAC name of the compound shown below is :
(a) 3-bromo-1-chlorocyclohexene Cl
CH 3 CHBr CHBr COOH is :
(b) 1-bromo-3-chlorocyclohexene
(a) 2 (b) 3
(c) 2-bromo-6-chlorocyclohex-1-ene
(c) 4 (d) 6
(d) 6-bromo-2-chlorocyclohexene Br
2. The IUPAC name of CH 3 - C º C - CH(CH 3 ) 2 is: 9. In Lassaigne test a violet colour obtained indicates the
(a) 4-methyl-2-pentyne presence of
(b) 4, 4-dimethyl-2-butyne (a) sulphur (b) halogen
(c) methyl isopropyl acetylene (c) nitrogen (d) None of these
(d) 2-methyl-4-pentyne 10. IUPAC name of the compound is :
3. Which pairs have same percentage of carbon? O
(a) CH 3COOH and C 6 H12O 6 ||
H - C - CH 2 - CH 2 - OCH 3
(b) CH 3COOH and C12 H 22O11 (a) 2 – methoxypropanal (b) methoxypropanal
(c) CH 3COOH and C 2 H 5OH (c) 3 – methoxypropanal (d) 2 – formyl methoxyethane
11. The number of secondary hydrogens in 2, 2-dimethylbutane
(d) C 6 H12O 6 and C12 H 22O11 is :
4. The IUPAC name of the compound : (a) 8 (b) 6 (c) 4 (d) 2
CH 2 - CH - CH 2 is 12. The geometrical isomerism is shown by
| | | CH2
CN CN CN CH2
(a) 1, 2, 3-trinitropropane (a) (b)
(b) 1, 2, 3-tricyanopropane
(c) 3-cyanopentane-1, 5-dinitrile CHCl
(d) 1, 2, 3-pentanetrinitrile CCl2
5. The IUPAC name of the compound (c) (d)
CH 3OCH 2 CH 2 CH 2 OCH 2 CH 3 is :
13. The IUPAC name for
(a) 3-ethoxy-1-methoxypropane
(b) 1-ethoxy-3-methoxypropane C1
(c) 2, 5-dioxyhexane |
(d) ethoxypropane oxymethane CH3 - C - CH 2 - CH = CH - CH3 is
6. The absolute configuration of the following : |
H
CH3 (a) 5–chlorohex–2–ene
H Cl (b) 2–chlorohex–5–ene
is (c) 1–chloro–1–methylpent–3–ene
Cl H
(d) 5–chloro–5–methylpent–2–ene
C2H5 14. Among the following the most stable compound is :
(a) 2S, 3R (b) 2S, 3S (a) cis-1, 2-cyclohexanediol
(c) 2R, 3S (d) 2R, 3R (b) trans-1, 2-cyclohexanediol
7. Which of the following compounds has wrong IUPAC name? (c) cis-1,3-cyclohexanediol
(a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl butanoate (d) trans-1, 3-cyclohexanediol
CH3 - CH - CH 2 - CHO ® 3-methyl-butanal 15. Which of the following compounds contains 1°, 2°, 3° as
(b)
| well as 4° carbon atoms ?
CH3 (a) Neopentane (b) 2-methyl pentane
(c) 2,3-dimethyl butane (d) 2,2,3-trimethyl pentane
(c) CH3 - CH - CH - CH3 ® 2-methyl-3-butanol 16. Correct configuration of the following is
| |
OH CH3 CH3
O H OH
||
(d) CH3 - CH - C - CH 2 - CH3 CH3 OH
|
CH3
H
® 2-methyl-3- pentanone (a) 1S, 2S (b) 1S, 2R (c) 1R, 2R (d) 1R, 2S
17. The correct name for the following hydrocarbon is 29. The chirality of the compound
(a) Tricyclo [4.1.0] heptane Br
(b) Bicyclo [5.2.1] heptane
(c) Bicyclo [4.1.0] heptane C
(d) Bicyclo [4.1.0] hextane H is
18. The Beilstein test for organic compounds is used to detect H3C Cl
(a) nitrogen(b) sulphur (c) carbon (d) halogens (a) R (b) S (c) E (d) Z
19. Which of the following is an optically active compound ? 30. Among the following four structures I to IV,
(a) 1-Butanol (b) 1-Propanol
(c) 2-Chlorobutane (d) 4-Hydroxyheptane CH3 O CH3
| || |
20. An important chemical method to resolve a racemic mixture C 2 H 5 - CH - C3 H 7 , CH 3 - C - CH - C 2 H 5,
makes use of the formation of ( II )
(a) a meso compound (b) enantiomers ( I)
(c) diasteromers (d) racemates
H CH3
21. Lassaigne’s test is used in qualitative analysis to detect | Å |
(a) nitrogen (b) sulphur H- C , C2H 5 - CH- C 2H5
(c) chlorine (d) All of these |
22. The process of separation of a racemic modification into d H ( IV)
( III)
and l -enantiomers is called
(a) Resolution (b) Dehydration it is true that
(c) Revolution (d) Dehydrohalogenation (a) only I and II are chiral compounds
23. Tautomerism will be exhibited by (b) only III is a chiral compound
(a) (CH3)2NH (b) (CH3)3CNO (c) only II and IV are chiral compounds
(c) R3CNO2 (d) RCH2NO2 (d) all four are chiral compounds
24. Lassaigne’s test for the detection of nitrogen fails in 31. Which of the following is optically inactive?
H H
(a) NH 2 CONHNH 2 .HCl (b) NH 2 NH 2 .HCl
H 3C Cl Cl CH3
(c) NH 2CONH 2 (d) C 6 H 5 NHNH 2 .HCl (a) Cl CH3 (b) H C Cl
3
25. A compound of molecular formula of C7H16 shows optical H H
isomerism, compound will be H
(a) 2, 3-Dimethylpentane (b) 2,2-Dimethylpentane H 3C Cl
(c) 2, 4 - Dimethylpentane (d) None of these (c) H C Cl (d) none of these.
3
.. .. H
26. CH2 – C – CH3 and CH2 = C – CH3 are 32. C8H16 that can form cis-trans geometrical isomers and also
|| |
O :O
. .: has a chiral centre, is
(a) resonating structures (b) tautomers
(c) geometrical isomers (d) optical isomers (a) H (b) H
27. Which of the following pairs of compounds are enantiomers?
CH3 CH3 (c) Both of these (d) None of these
(a)
HO H HO H 33. Which of the following will have a mesoisomer also?
and
H OH HO H (a) 2, 3- Dichloropentane (b) 2, 3-Dichlorobutane
CH3 CH3 (c) 2-Chlorobutane (d) 2-Hydroxypropanoic acid
CH3 CH3 34. Amongst the following compounds, the optically active
H OH HO H alkane having lowest molecular mass is
(b) and
HO H H HO H
CH3 CH3 |
(a) CH 3 - C -
CH3 CH3 |
H OH HO H C2H 5
(c) and
HO H HO H
CH3 CH3 CH3
|
CH3 CH3 (b) CH3 - CH 2 - CH - CH3
H OH H OH (c) CH 3 - CH 2 - CH 2 - CH 3
(d) and
HO H H OH
CH3 CH3 (d) CH 3 - CH 2 - C º CH
28. Kjeldahl’s method is used in the estimation of 35. The most suitable method for separation of a 1 : 1 mixture of ortho
(a) nitrogen (b) halogens and para nitrophenols is
(c) sulphur (d) oxygen (a) sublimation (b) chromatography
(c) crystallization (d) steam distillation
36. Which one of the following is a technique most suitable for 46. Geometrical isomerism is possible in case of :
purification of cyclohexanone from a mixture containing (a) pentene-2 (b) propane
benzoic acid, isoamyl alcohol, cyclohexane an d (c) pentane (d) ethene
cyclohexanone? 47. The number of isomers of the compound with molecular
(a) Crystallization (b) Sublimation formula C2H2Br2 is
(c) IR spectroscopy (d) Gas chromatography (a) 4 (b) 3 (c) 5 (d) 2
37. Which of the following is optically active ? 48. One among the following will show optical activity?
H H
H H
(a) C C CH3
(a) CH 3 C C C2 H5 (b) CH3 — CHOH — CH3 H C C
CH(Cl)CH3
H
OH OH
Br CH3 H
(b) C C CH(CH3)2
H C C
(c) CH3 C C COOH (d) CH3 CH2 C= O CH3 H

O Br OH H3C CHCl2
38. The correct stability order of following species is – (c) C C CH3
H C C
H3C CH3
(x) (y) H3C CH2Cl CH CH
C (d) C C 2 3
H C C
(z) (w) H CH2Cl2
(a) x > y > w > z (b) y > x > w > z 49. The number of ether isomers possible for C4H10O are :
(c) x > w > z > y (d) z > x > y > w (a) 2 (b) 5 (c) 4 (d) 3
39. An aromatic compound of formula C7H7Cl has in all ..... 50. Keto-enol tautomerism is observed in :
isomers :
(a) 5 (d) 2 (c) 4 (d) 3 O O
40. How many optically active stereoisomers are possible for || ||
(a) H 5 C 6 - C - CH 2 - C - C 6 H 5
lactic acid ?
(a) 1 (b) 2 (c) 4 (d) 3
O
41. The correct IUPAC name for ||
(b) H 5 C 6 - C - CH 3

O
||
(c) H 5C 6 - C - H
(a) 5-methyl -4-(1'-2'-demethylpropyl) heptane (d) Both (a) and (b)
(b) 3-methyl-4-(1',2'-dimethylpropyl) heptane 51. The best method for the separation of naphthalene and
(c) 2,3,5-trimethyl-4-propylheptane benzoic acid from their mixture is:
(d) 4-propyl-2,3,5-trimethylpeptane (a) distillation (b) sublimation
42. Geometrical isomerism is possible in : (c) chromatography (d) crystallisation
(a) CH 3CH(CH 3 )CH 2 CH 2 CH 3 52. Isomerism due to rotation around C–C single bond is :
(a) Enantiomerism (b) Position isomerism
(b) CH 3CH = CHCH 3
(c) Conformation (d) Diastereoisomerism
(c) CH 3 CH = CH 2 53. If a compound has n asymmetric carbon atoms, then maximum
(d) ClH 2 C - CH 2 Cl number of optical isomers are given by the formula
n
43. How many acyclic structural isomers are possible for the æ 1ö
(a) 2n (b) ç ÷ (c) 2n (d) 2 n
compound with molecular formula C3H3Cl3 ? è 2ø
(a) 3 (b) 2 (c) 5 (d) 6 54. Which is a chiral molecule?
44. The number of optical enantiomorphs of tartaric acid is/are: (a) 2, 2-dimethylbutanoic acid
(a) 1 (b) 4 (c) 3 (d) 2 (b) 4-methylpentanoic acid
45. Which of the cations in more stable ? (c) 3-methylpentanoic acid
H (d) 3,3-dimethylbutanoic acid
H 55. In Kjeldahl’s method, CuSO4 acts as
| | +
(a) R '- C + - OR (b) R '- C = OR (a) oxidising agent (b) reducing agent
(c) hydrolysing agent (d) catalytic agent
(c) both equal (d) both are unstable
56. The following compounds differ in 63. Which of the substance is purified by sublimation?
H Cl H Cl (a) Benzoic acid (b) Camphor
C=C C=C (c) Naphthalene (d) All of these
H Cl Cl H 64. The most reactive compound for electrophilic nitration is
(a) configuration (b) conformation (a) Benzene (b) Nitrobenzene
(c) structure (d) chirality (c) Benzoic acid (d) Toluene.
57. A mixture of methyl alcohol and acetone can be separated 65. Which of the following molecules is achiral?
by NH2
(a) distillation H O
(b) fractional distillation
(a) CH2CH3 (b) H
(c) steam distillation
(d) distillation under reduced pressure H OH
58. The correct statement about the compounds (A), (B) and CH3
(C) is : OH
Cl SH
Cl SH
COOCH 3 COOH COOH (c) (d)
H OH H OH H OH
66. Which one of the following is a free-radical substitution
H OH H OH HO H
reaction?
COOH COOCH 3 COOCH 3
(C) (a) CH 3CHO + HCN ¾
¾® CH 3CH ( OH ) CN
(A) (B)
(a) (A) and (B) are identical CH3 CH2Cl
(b) Boiling
(b) (A) and (B) are diastereomers +Cl2
(c) (A) and (C) are enantiomers
(d) (A) and (B) are enantiomers Anh. AlCl3 CH3
59. Which compound on nitration will give highest amount of (c) +CH3Cl
m-substituted product ?
CH3 CH2–Cl CH2Cl CH2NO2
(d) + AgNO2
(a) (b) 67. Which of the following undergoes nucleophilic substitution
exclusively by SN1 mechanism?
Cl (a) Ethyl chloride (b) Isopropyl chloride
Cl
CH C Cl (c) Chlorobenzene (d) Benzyl chloride
Cl Cl 68. Styrene can be purified by
(a) Simple distillation (b) Fractional distilation
(c) (d)
(c) Steam distillation (d) Vacuum distillation
69. The correct order regarding the electronegativity of hybrid
60. The molecular formula of diphenyl methane, orbitals of carbon is
CH2 , is C13H12. (a) sp > sp2 > sp3 (b) sp < sp2 > sp3
2
(c) sp < sp < sp 3 (d) sp > sp2 < sp3
How many structural isomers are possible when one of the 70. The example of an electrophilic substitution reaction is :
hydrogens is replaced by a chlorine atom? NH2 N(C2H 5)2
(a) 6 (b) 4 (c) 8 (d) 7 (a) +C2H5B r®
61. Nitroethane can exhibit one of the following kind of
isomerism:
(a) metamerism (b) optical activity (b) OH + X– N2+ SO3– Na+
(c) tautomerism (d) position isomerism
+ –
62. Tautomerism is exhibited by – ® Na O N=N SO3- Na +

O HBr
(1) CH = CH – OH (2) O (c) H 2 C = CH – CH 3 ¾¾¾¾®
Peroxide
Br – CH 2 – CH 2 – CH3
(3) O (4) O O
||
NuH
(d) H 2C = CH - C - CH3 ¾¾¾ ®
O O
O
(a) (1), (3) and (4) (b) (2), (3), and (4) ||
(c) All of these (d) None of these NuCH2 CH 2 - C - CH3
71. Which one of the following does not have sp2 hybridized 84. Which of the following pairs represent electrophiles?
carbon ? (a) AlCl3, H2O (b) SO3, NO2+
(a) Acetonitrile (b) Acetic acid (c) BF3, H2O (d) NH3, SO3
(c) Acetone (d) Acetamide 85. Chromatography is a valuable method for the separation,
72. Rate of the reaction isolation, purification and identification of the constituents
O O – of a mixture and it is based on general principle of
R – C + Nu R – C + Z is fastest when Z is (a) phase rule (b) phase distribution
Z Nu (c) interphase separation (d) phase operation
(a) OC2H5 (b) NH2 (c) C l (d) OCOCH3 86. The shape of methyl carbanion is similar to that of –
73. The increasing order of stability of the following free radicals (a) BF3 (b) NH3
is (c) methyl free radical (d) methyl carbocation
• • •
(a) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H
• 87. The replacement of chlorine of chlorobenzene to give phenol
• • • • requires drastic conditions, but the chlorine of
(b) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3C 2,4-dinitrochlorobenzene is readily replaced since,
• • • •
(c) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3 C (a) nitro groups make the aromatic ring electron rich at
• • • • ortho/para positions
(d) (C6H5)3C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H
(b) nitro groups withdraw electrons from the meta position
74. Steam distillation is used for the purification of :
of the aromatic ring
(a) covalent compounds
(c) nitro groups donate electrons at meta position
(b) electrovalent compounds
(d) nitro groups withdraw electrons from ortho/para
(c) co-ordinate compounds
positions of the aromatic ring
(d) volatile compounds
88. The optical inactivity due to internal compensation can be
75. Which of the following is strongest nucleophile –
exhibited by :
(a) Br– (b) : OH–
(a) dextro-tartaric acid (b) laevo-tartaric acid
(c) : CN - (d) C2 H 5O : (c) racemic-tartaric acid (d) meso-tartaric acid
76. Strongest acid among the following is : 89. Consider the following phenols :
(a) CCl 3COOH (b) CH 3COOH OH OH OH OH

(c) CF3 COOH (d) CBr3 COOH

77. The prussian blue colour obtained in the Lassaigne’s test
for nitrogen is due to the formation of NO2
(a) Iron (II) hexacyanoferrate (III) CH3 NO2
(b) Iron (III) hexacyanoferrate (II) I II III IV
(c) Iron (III) hexacyanoferrate (III) The decreasing order of acidity of the above phenols is
(d) Iron (II) hexacyanoferrate (II) (a) III > IV > II > I (b) II > I > IV > III
78. Which one of the following species is isoelectronic with (c) I > IV > II > III (d) III > IV > I > II
ammonia ? 90. Absolute alcohol cannot be obtained by simple fractional
distillation because
(a) CH -2 (b) +CH2 (c) –CH3 (d) +CH3 (a) Pure C2H5OH is unstable
79. A meta-directing functional group is : (b) C2H5OH form hydrogen bonds with water
(a) — COOH (b) OH (c) Boiling point of C2H5OH is very close to that of water
(c) — CH3 (d) — Br (d) Constant boiling azeotropic mixture is formed with water
80. The following compound will undergo electrophilic 91. Impure glycerine can be purified by
substitution more readily than benzene : (a) Steam distillation (b) Simple distillation
(a) Nitrobenzene (b) Benzoic acid (c) Vacuum distillation (d) Extraction with a solvent
(c) Benzaldehyde (d) Phenol 92. Consider the acidity of the carboxylic acids :
81. In Kjeldahl’s method for the estimation of nitrogen, the (A) PhCOOH (B) o-NO2C6H4COOH
foumula used is (C) p-NO2C6H4COOH (D) m-NO2C6H4COOH
Which of the following order is correct ?
1.4VW 1.4VW
(a) %N = (b) %N = (a) B > D > A > C (b) B > D > C > A
N V (c) A > B > C > D (d) B > C > D > A
1.4 VN
(c) %N = VNW (d) %N = 93. The decreasing order of nucleophilicity among the
1.8 W nucleophiles
82. The number of s and p bonds in a molecule of acetonitrile
are respectively (A) CH 3C - O - (B) CH 3 O -
(a) 2, 5 (b) 3, 4 (c) 4, 3 (d) 5, 2 ||
O
83. An asymmetric carbon atom is that in which : (C) CN -
(a) three similar and one dissimilar groups O
(b) two similar and two dissimilar groups ||
(c) all the different groups (D) H C
3 S – O – is
(d) none of the above ||
O
 (a) (C), (B), (A), (D) (b) (B), (C), (A), (D) 103. How many stereoisomers does this molecule have ?
(c) (D), (C), (B), (A) (d) (A), (B), (C), (D) CH3CH = CHCH 2CHBrCH 3
94. 1,2-Dihydroxybutane has the formula
(a) 4 (b) 6 (c) 8 (d) 2
(a) C(OH) – C(OH) – C – C (b) C – C(OH)2 – C – C
104. The stability of carbanions in the following :
(c) (OH)C – C – C – C(OH) (d) C – C(OH) – C(OH) – C
95. Which of the following represents the correct order of
stability of the given carbocations ? (I) RC = C (II)
+ |+ + + |+ +
(a) F3C > F3C - C > CH3 (b) H3C > F3C - C > F3C (III) R 2C = CH (IV) R 3C - CH 2
| | is in the order of :
(a) (I) > (II) > (III) > (IV) (b) (II) > (III) > (IV) > (I)
|+ + + |+ + + (c) (IV) > (II) > (III) > (I) (d) (I) > (III) > (II) > (IV)
(c) F3C - C > F3C > H3C (d) F3C - C > H3C > F3C 105. In the hydrocarbon
| |
CH3 – CH = CH – CH2 – C º CH
96. A bottle containing two immiscible liquids is given to you.
6 5 4 3 2 1
They may be separated by using a
The state of hybrization of carbons 1, 3 and 5 are in the
(a) Fractionating column (b) Separating funnel
following sequence :
(c) Vacuum distillation (d) Steam distillation
(a) sp2, sp, sp3 (b) sp, sp3, sp2
97. Distillation is used to separate liquids which differ in the b.p 2 3
(c) sp, sp , sp (d) sp3, sp2, sp
by
106. The state of hybridization of C2, C3, C5 and C6 of the
(a) 5°C (b) 10°C
hydrocarbon,
(c) 30 – 80°C (d) 100°C
CH3 CH3
98. Example of chain isomerism are : | |
(a) Ortho and meta toluic acids CH3 C CH = CH CH C º CH
(b) Methyl acetate and ethyl formate 7 6| 5 4 3 2 1
(c) Pentanoic acid and 2-methyl butanoic acid CH3
(d) 2-pentanone and 3-pentanone is in the following sequence:
99. CH3 – CHCl – CH2 – CH3 has a chiral centre. which one of (a) sp3, sp2, sp2 and sp (b) sp, sp2, sp2 and sp3
the following represents its R-configuration? 2 3
(c) sp, sp , sp and sp 2 (d) sp, sp3, sp2 and sp3
C2 H 5 C2 H5 107. Which of the following compounds will exhibit cis-trans
| | (geometrical) isomerism?
(a) H - C - CH3 (b) Cl - C - CH3 (a) Butanol (b) 2-Butyne
| | (c) 2-Butenol (d) 2-Butene
Cl H 108. Cyclohexanol (I), acetic acid (II), 2, 4, 6-trinitrophenol (III)
CH3 C2 H 5 and phenol (IV) are given. In these the order of decreasing
| | acidic character will be :
(c) H - C - Cl (d) H3C - C - Cl (a) III > II > IV > I (b) II > III > I > IV
| | (c) II > III > IV > I (d) III > IV > II > I
C2 H5 H 109. The correct order of increasing reactivity of C – X bond
100. For (i) I– , (ii) Cl– , (iii) Br – , the increasing order of towards nucleophile in the following compounds is:
nucleophilicity would be X X
(a) Cl– < Br– < I– (b) I– < Cl– < Br– NO2
(c) Br– < Cl– < I– (d) I– < Br– < Cl– (CH3)3 C – X, (CH3)2CH – X
101. The order of decreasing reactivity towards an electrophilic
reagent, for the following would be
(i) benzene (ii) toluene NO2
(iii) chlorobenzene (iv) phenol (I) (II) (III) (IV)
(a) (ii) > (iv) > (i) > (iii) (b) (iv) > (iii) > (ii) > (i) (a) I < II < IV < III (b) II < III < I < IV
(c) (iv) > (ii) > (i) > (iii) (d) (i) > (ii) > (iii) > (iv) (c) IV < III < I < II (d) III < II < I < IV
102. Which one of the following is most reactive towards 110. Among the given compounds, the most susceptible to
electrophilic attack ? nucleophilic attack at the carbonyl group is:
CH2OH (a) CH 3COOCH3 (b) CH 3CONH 2
(b) CH 3 COOCOCH 3 (d) CH3COCl
(a) (b)
111. The correct IUPAC name of the compound

Cl
OH is
(c) (d)
 (a) 4-Ethyl-3-propyl hex-1-ene 117. The alkene that exhibits geometrical isomerism is :
(b) 3-Ethyl-4-ethenyl heptane (a) 2- methyl propene (b) 2-butene
(c) 3-Ethyl-4-propyl hex-1-ene (c) 2- methyl -2- butene (d) propene
(d) 3-(1-ethylpropyl) hex-1-ene 118. The number of stereoisomers possible for a compound of
112. The IUPAC name of the following compound is the molecular formula
Cl CH2CH3 CH3 – CH = CH – CH(OH) – Me is:
(b) 2 (c) 4 (d) 6 (d) 3
C C
119. Out of the following, the alkene that exhibits optical isomerism is
CH3 I (a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
(a) trans-2-chloro-3-iodo-2-pentene (c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
(b) cis-3-iodo-4-chloro-3-pentene 120. The IUPAC name of the following compound is OH
(c) trans-3-iodo-4-chloro-3-pentene (a) 4-Bromo-3-cyanophenol
(d) cis-2-chloro-3-iodo-2-pentene
(b) 2-Bromo-5-hydroxybenzonitrile
113. The IUPAC name of is (c) 2- Cyano-4-hydroxybromobenzene CN
(d) 6-Bromo-3-hydroxybenzonitrile Br
(a) 3-ethyl-4, 4-dimethylheptane 121. Hyperconjugation involves overlap of the following orbitals
(b) 1, 1-diethyl-2,2-dimethylpentane
(c) 4, 4-dimethyl-5,5-diethylpentane (a) s-s (b) s - p (c) p- p (d) p-p
(d) 5, 5-diethyl-4,4-dimethylpentane. 122. In allene (C3H4), the type(s) of hybridisation of the carbon
114. Presence of a nitro group in a benzene ring atoms is (are) :
(a) deactivates the ring towards electrophilic substitution (a) sp and sp3 (b) sp and sp2
(b) activates the ring towards electrophilic substitution 3
(c) renders the ring basic (c) only sp (d) sp2 and sp3
(d) deactivates the ring towards nucleophilic substitution. 123. Which one of the following conformations of cyclohexane
115. The correct decreasing order of priority for the functional is chiral?
groups of organic compounds in the IUPAC system of
(a) Boat (b) Twist boat (c) Rigid (d) Chair.
nomenclature is
(a) – COOH, – SO3H, – CONH2, – CHO 124. Directing influence of the methyl group can be explained on
(b) – SO3H, – COOH,– CONH2, – CHO the basis of
(c) – CHO, – COOH, – SO3H, – CONH2 (a) inductive effect (b) electromeric effect
(d) – CONH2, – CHO, – SO3H, – COOH (c) resonance effect (d) no-bond resonance
116. The IUPAC name of neopentane is 125. The number of isomers of the compound C 2 BrFCl is
(a) 2, 2 dimethylpropane (b) 2 methylpropane
(a) 3 (b) 4 (c) 5 (d) 6
(c) 2, 2 dimethylbutane (d) 2- methylbutane

1. Which of the following is true? (a) 3-pentanone, cyclopentanone, n-pentanal

(a) A cis isomer has lower b.p. than the trans (b) n-pentanal, 3-pentanone, cyclopentanone
(b) A cis isomer has lower m.p. than the tans (c) n-pentanal, cyclopentanone, 3-pentanone
(c) All isomers of nitrophenols are equal soluble in water (d) cyclopentanone, 3-pentanone, n-pentanal
(d) All the three are correct 6. The reaction :
2. Which is weakest base : CH3 (CH2 )5 (CH2)5CH3
H H
(a) C6H5 – CH2 – NH2 (b) C6H5 – CH2 – NH – CH3 OH
(c) O2N – CH2 – NH2 (d) CH3 – NH – CHO C – Br HO – C
3. Which of the following is maximum stable H3C CH3
(a) Conjugated alkadiene (CH2 = CH – CH = CH2) is described as
(b) Isolated alkadiene (CH2 = CH – CH2 – CH = CH2)
(c) Cumulated alkadiene (CH2 = C = CH2) (a) S (b) S (c) S (d) S
E2 N1 N0 N2
(d) All are equal 7. Which of the following is not correct?
4. Which is true regarding the relative basic character of the Order of basicity Order of nucleophilicity
following two pairs?
(a) NH3 > NH2OH (b) –CCl3 > –CF3
(a) F - > Cl - > Br - Br - > Cl - > F -
(c) Both are true (d) Nither is true (b) H - O - O - > OH - H - O - O - > OH -
5. Decreasing order of reactivity towards nucleophilic addition
to carbonyl group among cyclopentanone, 3-pentanone and (c) - CH 3 > NH -2 > OH - - CH 3 > NH 2- > OH -
n-pentanal is (d) H2O > H2S H2O < H2S
8. Among the following compounds (I - III), the ease of their 17. Which of the following is the strongest base ?
reaction with electrophiles is,
OCH3 NO2 (a) (b) NHCH3

(c) NH2 (d) CH2NH2

I II III
18. Which type of isomerism is possible in the compound
(a) II > III > I (b) III > II > I
(c) II > I > III (d) I > II > III
COOH
9. Which one of the following compounds is resistant to ?
nucleophilic attack by hydroxyl ions ? (a) Geometrical (b) Optical
(a) Methyl acetate (b) Acetonitrile (c) Both (d) None
(c) Diethyl ether (d) Acetamide 19. Which pair of isomerism is not possible together?
10. Which one of the following orders is correct regarding the (a) Ring-chain and functional
–I effect of the substituents ? (b) Geometrical and optical
(a) —NR2 <—OR >—F (b) —NR2 > —OR >—F (c) Metamerism and functional
(c) —NR2 <—OR <—F (d) —NR2 >—OR <—F (d) Metamerism and chain
11. Which of the following is false regarding a good contributor 20. CH 3 Br + Nu - ¾¾® CH 3 - Nu + Br -
of a resonance hybrid?
(a) It must have as many bonds as possible The decreasing order of the rate of the above reaction with
(b) It must have as many octets as possible nucleophiles (Nu–) A to D is
(c) Negative charge, if any, should be on electronegative [Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–]
atom (a) A > B > C > D (b) B > D > C > A
(d) None of the three (c) D > C > A > B (d) D > C > B > A
12. Correct order of stability is : 21. Lassaigne’s test is used to detect
(a) cis -2- butene > 1-butene > trans -2-butene (a) nitrogen and halogens (b) sodium and halogens
(b) trans-2-butene > cis-2-butene > 1-butene (c) halogens and sulphur (d) All of these
(c) 1-butene > cis-2-butene > trans-2- butene 22. The reason for the loss of optical activity of lactic acid when
(d) cis-2-butene > trans-2-butene > 1-butene OH group is changed by H is that :
13. The correct order of reactivity towards the electrophilic (a) Chiral centre of the molecule is destroyed
substitution of the compounds aniline (I), benzene (II) and (b) Molecule acquires asymmetry
nitrobenzene (III) is (c) Due to change in configuration
(a) I > II > III (b) III > II > I (d) Structural change occurs
(c) II > III > I (d) I < II > III 23. Which of the following does not exhibit cis-trans isomerism?
14. Which of the following is least reactive in a nucleophilic (a) C 6 H 5CH = NOH (b) C 6 H 5 N = NC 6 H 5
substitution reaction. (c) (d) None of the three
(a) (CH 3 )3 C - Cl (b) CH 2 = CHCl 24. C – H bond energy is about 101 kcal/mol for methane, ethane
(c) CH 3CH 2Cl (d) CH 2 = CHCH 2 Cl and other alkanes but is only 77 kcal/mol for C – H bond of
CH3 in toluene. This is because :
15. Which of the following is true regarding hyperconjugation,
(a) of inductive effect due to – CH3 in toluene
also known as no-bond resonance?
(b) of the presence of benzene ring in toluene.
(i) Like inductive effect it involves donation of electrons
(c) of resonance among the structures of benzyl radical in
through s bonds
toluene
(ii) Hyperconjugation involves overlapping of filled
(d) of aromaticity of toluene
orbitals with the empty p orbital of the carbocation
(iii) Like resonance, it involves displacement of p or lone 25. In Carius method 0.099 g organic compound gave 0.287 g
pair of electrons to the carbon bearing positive charge AgCl. The percentage of chlorine in the compound will be
(iv) It involves delocalisation of s and p- electrons (a) 28.6 (b) 71.7 (c) 35.4 (d) 64.2
(a) (ii) and (iv) (b) (ii) 26. Select the appropriate relation with respect to acidity of X, Y,
(c) (iii) (d) none Z for the given compound, with increasing order.
16. In the anion HCOO– the two carbon-oxygen bonds are found + +
to be of equal length. what is the reason for it ? H3N NH3
Z X
(a) The C = O bond is weaker than the C — O bond
(b) The anion HCOO– has two resonating structures COOH
(c) The anion is obtained by removal of a proton from the Y
acid molecule (a) Z > X > Y (b) Y > Z > X
(d) Electronic orbitals of carbon atom are hybridised (c) Z < X > Y (d) X > Y > Z
 27. The shape of transition state is – COOH (ii)
R
–
Nu + H C X [Transition state]
R
R
NO2
–––––® Nu C H + X–
OH
R (iii)
(a) Triangular planar (b) Square pyramidal HO
(c) Trigonal bipyramidal (d) Tetrahedral (i)
28. Arrange the following alcohols in order of their decreasing
(iv)
tendency to form carbocation.
(a) (ii) > (i) > (iii) > (iv) (b) (ii) > (iii) > (i) > (iv)
(c) (i) > (ii) > (iii) > (iv) (d) (ii) > (iv) > (i) > (iii)
OH 33. Which of the following is most stable?
+
F OH F +
CH 3 (a) (b)
O O
I II
OH H3C CH 3 +
H2C +
C 6 H 5 CH 2 OH
(c) (d)
CH 3 OH O O
II III IV
34. Sodium nitroprusside, when added to an alkaline solution of
(a) I > II > III > IV (b) IV > III > I > II (c) sulphide ions, produces purple colour ion due to the
IV > III > II > I (d) II > I > IV > III formation of
29. Which molecule will be most reactive for SN1 reaction – (a) Na[Fe(H2O)5 NOS] (b) Na2[Fe(H2O)5 NOS]
Cl (c) Na3[Fe(CN)5NOS] (d) Na4[Fe(CN)5NOS]
CH3 CH3 35. Base strength of :
(a) (b) Br – , (B)
(A) H 3CCH 2
H 2C = CH and (C) H - C º C
CH3 is in the order of :
CH3 (a) (B) > (A) > (C) (b) (C) > (B) > (A)
(c) (A) > (C) > (B) (d) (A) > (B) > (C)
Cl CH3 36. Which one of the following is most reactive towards
(c)
CH3 (d) I electrophilic reagent ?
CH3 CH3
CH3
(a) (b)
30. Diazo compounds, sometimes do not respond Lassaigne’s
test for nitrogen because OCH3 OH
(a) these are quite stable compounds and do not CH3 CH3
decompose to elemental nitrogen
(b) these contain very little carbon (c) (d)
(c) these form organometallic compounds with sodium NHCOCH3 CH2OH
(d) their nitrogen contents is removed, during heating, in 37. Which one is a nucleophilic substitution reaction among
the form of nitrogen gas the following ?
(a) CH3 – CH = CH2 + H2O CH3 – CH – CH3
31. — X + Nu ¾¾
® — Nu + X , OH
(b) RCHO + R¢ MgX R – CH – R¢
the reaction is not possible because –
(a) Nu faces steric hinderance on attacking the leaving OH
CH3
group
(b) electrons are delocalised in the benzene ring (c) CH3 – CH2–CH–CH2Br + NH3
(c) reaction is thermodynamically controlled CH3
(d) C – X bond possesses a double bond character
CH 3–CH2–CH–CH2NH2
32. Which of the following represent the decreasing order of Ka
(d) CH3CHO + HCN ¾¾
® CH3CH (OH) CN
values?
38. Which of the following compounds undergoes nucleophilic (c) (CH3 )3 C > (CH3 )2 CH > C6 H5 CH 2 > C Cl3
substitution reaction most easily ? (d) C6 H5 CH 2 > C Cl3 > (CH3 )3 C > (CH3 ) 2 CH
Cl 43. The correct order of increasing basicity of the given
Cl conjugate bases (R = CH3) is
(a) (b) (a) RCOO < HC º C < R < NH 2
NO2 (b) R < HC º C < RCOO < NH 2
CH3 (c) RCOO < NH 2 < HC º C < R
Cl (d) RCOO < HC º C < NH 2 < R
Cl 44. Among the following, the least stable resonance structure
(c) (d) is
Å O
(a) Å
OCH3 N
39. Which of the following molecules is expected to rotate the
plane of plane-polarised light? O
COOH
O
Å
(a) H2N (b)
H Å N
H O
CHO
O
(b) HO H (c) Å
Å N
CH2OH O
(c)
O
Å
SH
H2N NH2 (d)
Å N

(d) H H O
Ph Ph 45. The number of stereoisomers obtained by bromination of
40. The absolute configuration of
trans-2-butene is
HO2C CO2H (a) 1 (b) 2 (c) 3 (d) 4
46. The correct stability order for the following species is
OH
HO H H
+ + +
(a) S, S (b) R, R (b) R, S (c) S, R O O +
41. The electrophile, E Å attacks the benzene ring to generate (I) (II) (III) (IV)

the intermediate s-complex. Of the following, which s- (a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV)
complex is lowest energy? (c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV)
NO2 47. In the following carbocation, H/CH3 that is most likely to
H migrate to the positively charged carbon is
+ + E
(a) (b)
H H
H E 1 2 + 4 5
NO2 NO2 H3C — C —3C — C — CH3
H
(c) + E (d) + H HO H CH3
E
42. Arrange the carbanions, (a) CH3 at C-4 (b) H at C-4
(CH3 )3 C , C Cl3 , (CH3 ) 2 CH , C6 H5 CH 2 (c) CH3 at C-2 (d) H at C-2
in order of their decreasing stability :
(a) (CH3 ) 2 C H > C Cl3 > C6 H5 C H2 > (CH3 )3 C
(b) C Cl3 > C6 H5 CH 2 > (CH 3 )2 CH > (CH3 )3 C
 DIRECTIONS for Qs. 48 to 50 : These are Assertion-Reason 48. Statement-1 : Aniline is better nucleophile than anilium ion.
type questions. Each of these question contains two statements: Statement-2 : Anilium ion have +ve charge.
Statement-1 (Assertion) and Statement-2 (Reason). Answer 49. Statement-1 : Trans-2-butene on reaction with Br2 gives
these questions from the following four options. meso-2, 3-dibromobutane.
(a) Statement-1 is true, Statement-2 is true, Statement-2 is a Statement-2 : The reaction involves syn-addition of bromine.
correct explanation for Statement-1 50. Statement-1 : Different number of electron pairs are present
(b) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT in resonance structures.
a correct explanation for Statement-1 Statement-2 : Resonance structures differ in the location of
(c) Statement-1 is True, Statement-2 is False electrons around the constituent atoms.
(d) Statement-1 is False, Statement-2 is True

Exemplar Questions These are generally insoluble in water at room temperature

1. Which of the following is the correct IUPAC name? but are miscible with water vapour in vapour phase. A suitable
(a) 3-ethyl-4, 4-dimethylheptane method for the extraction of these oils from the flowers is
(b) 4, 4-dimethyl-3-ethylheptane (a) distillation
(c) 5-ethyl-4, 4-dimethylheptane (b) crystallisation
(d) 4, 4-bis(methyl)-3-ethylheptane (c) distillation under reduced pressure
O O (d) steam distillation
|| || 7. During hearing of a court case, the judge suspected that
2. The IUPAC name for CH3 - C - CH 2 - CH 2 - C - OH is some changes in the documents had been carried out. He
(a) 1-hydroxypentane-1, 4-dione asked the forensic department to check the ink used at two
(b) 1, 4-dioxopentanol different places. According to you which technique can give
(c) 1-carboxybutan-3-one the best results?
(d) 4-oxopentanoic acid (a) Column chromatography
3. The IUPAC name for (b) Solvent extraction
Cl (c) Distillation
(d) Thin layer chromatography
NO2 8. The principle involved in paper chromatography is
(a) adsorption (b) partition
(c) solubility (d) volatility
9. What is the correct order of decreasing stability of the
CH3 following cations?
(a) 1-chloro-2-nitro-4-methylbenzene Å Å
(b) 1-chloro-4-methyl-2-nitrobenzene I. CH3 - C H - CH3 II. CH3 - C H - OCH3
(c) 2-chloro-1-nitro-5-methylbenzene Å
(d) m-nitro-p-chlorotoluene III. CH3 - C H - CH 2 - OCH3
4. Electronegativity of carbon atoms depends upon their state (a) II > I > III (b) II > III > I
of hybridisation. In which of the following compounds, the (c) III > I > II (d) I > II > III
carbon marked with asterisk is most electronegative?
(a) CH3 – CH2 – *CH2 – CH3 10. Correct IUPAC name for H3C – CH – CH – CH3 is ......... .
| |
(b) CH3 – *CH = CH – CH3
C2H5 C2H5
(c) CH3 – CH2 – C º *CH
(d) CH3 – CH2 – CH = *CH2 (a) 2-ethyl-3-methylpentane
5. In which of the following functional groups, isomerism is (b) 3, 4-dimethylhexane
not possible? (c) 2-sec-butylbutane
(a) Alcohols (b) Aldehydes (d) 2, 3-dimethylbutane
(c) Alkyl halides (d) Cyanides 11. In which of the following compounds the carbon marked
6. The fragrance of flowers is due to the presence of some with asterisk is expected to have greatest positive charge?
steam volatile organic compounds called essential oils. (a) *CH3 — CH2 — Cl (b) *CH3 — CH2 — Mg+Cl–
(c) *CH3 — CH2 — Br (d) *CH3 — CH2 — CH3
12. Ionic species are stabilised by the dispersal of charge. Which 17. Some meta-directing substituents in aromatic substitution
of the following carboxylate ion is the most stable? are given. Which one is most deactivating? [2013]
O O (a) –SO3H (b) –COOH
|| || (c) –NO2 (d) –C º N
(a) CH3 - C - O - (b) Cl - CH 2 - C - O -
18. Which of the following compounds will not undergo Friedal-
O O Craft’s reaction easily : [2013]
||
-
F ||
(a) Xylene (b) Nitrobenzene
(c) F - CH 2 - C - O (d) CH - C - O-
F (c) Toluene (d) Cumene
13. Electrophilic addition reactions proceed in two steps. The 19. The structure of isobutyl group in an organic compound is :
first step involves the addition of an electrophile. Name the
(a) CH3 - CH - CH 2 - CH3 [2013]
type of intermediate formed in the first step of the following ½
addition reaction. H3C – HC = CH2 + H+ ----® ? (b) CH3 - CH 2 - CH2 - CH 2 -
(a) 2° carbanion (b) 1° carbocation CH3
(c) 2° carbocation (d) 1° carbanion |
14. Covalent bond can undergo fission in two different ways. (c) CH3 - C-
|
The correct representation involving a heterolytic fission of CH3
CH3 – Br is CH 3
(a) Å (d) CH - CH 2 -
CH 3 - Br ¾ ¾
® CH 3 + Br
CH 3
r
(b) ® CH 3 + Br s
CH 3 - Br ¾ ¾ 20. Arrange the following in increasing order of stability
[NEET Kar. 2013]
r
(c) ® CH 3 + Br s
CH 3 - Br ¾ ¾ Å Å
(A) (CH3 )2 C - CH2CH3 (B) (CH3 )3 - C
(d) r s
CH3 - Br ¾ ¾ ® CH 3 + Br Å Å
15. The addition of HCl to an alkene proceeds in two steps. The (C) (CH3 )2 - CH (D) CH3 - CH 2
Å
first step is the attack of H+ ion to C—
—C portion (E) CH 3
which can be shown as (a) E < D < C < B < A (b) E < D < C < A < B
(c) D < E < C < A < B (d) A < E < D < C < B
(a) + —C 21. Given
H C—
Br Br H
H Br
(b) H
+
C—
—C CH3 H

(c) + —C H CH3 and CH3

H C— CH3
Br
(d) All of these are possible
NEET/AIPMT (2013-2017) Questions I II
16. Structure of the compound whose IUPAC name is 3-ethyl-2- I and II are [NEET Kar. 2013]
hydroxy-4-methylhex-3-en-5-ynoic acid is : [2013] (a) A pair of optical isomers
OH (b) Identical
(c) A pair of conformers
COOH (d) A pair of geometrical isomers
(a)
22. Homolytic fission of the following alkanes forms free radicals
OH
CH3 – CH3, CH3 – CH2 – CH3, (CH3)2 CH – CH3, CH3 – CH2
– CH (CH3)2. Increasing order of stability of the radicals is
COOH [NEET Kar. 2013]
(b) g g
(a) (CH3)3 C < (CH3)2 C – CH2CH3 <
g g
CH3 – C H – CH3 < CH3 – C H2
g g g
COOH (b) (CH3)2 C – CH2CH3 < CH3 – C H – CH3 < CH3 – C H2
(c) g
< (CH3)3 C
OH g g
OH (c) CH3 – C H2 < CH3 – C H – CH3 <
g g
(CH3)2 C – CH2 – CH3 < (CH3)3 C
g g g
(d) COOH (d) CH3 – C H2 < CH3 – C H – CH3 < (CH3)3 C < (CH3)2
g
C – CH2CH3
23. What is the hybridisation state of benzyl carbonium 30. Consider the following compounds [2015]
+ CH3 Ph
ion —CH2? [NEET Kar. 2013]
CH3—C—CH— Ph—C—PH
(a) sp3 (b) sp2 CH3
(c) spd 2 (d) sp2 d CH3
24. Nitrogen detection in an organic compound is carried out (I) (II) (III)
by Lassaigne’s test. The blue colour formed corresponds to Hyperconjugation occurs in :
which of the following formulae? [NEET Kar. 2013] (a) II only (b) III only
(a) Fe3[Fe(CN)6]3 (b) Fe3[Fe(CN)6]2
(c) I and III (d) I only
(c) Fe4[Fe(CN)6]3 (d) Fe4[Fe(CN)6]2
31. Which of the following is the most correct electron
25. Which of the following compounds will undergo racemisation
displacement for a nucleophilic reaction to take place?
when solution of KOH hydrolyses? [2014]
[2015]
CH2Cl
H H2
(i) (a) H3C—C = C – C – Cl
H
(ii) CH3CH2CH2Cl H H2
(b) H 3C—C = C – C – Cl
CH3 H
| H H2
(iii) H3C - C H - CH2Cl (c) H 3C—C = C – C – Cl
H
CH3 H H2
(d) H 3C—C = C – C – Cl
C H
(iv) H Cl 32. In Duma's method for estimation of nitrogen, 0.25 g of an
C2H3 organic compound gave 40 mL of nitrogen collected at 300
(a) (i) and (ii) (b) (ii) and (iv) K temperature and 725 mm pressure. If the aqueous tension
(c) (iii) and (iv) (d) (i) and (iv) at 300 K is 25 mm, the percentage of nitrogen in the compound
26. In the Kjeldahl’s method for estimation of nitrogen present is : [2015]
in a soil sample, ammonia evolved from 0.75 g of sample (a) 18.20 (b) 16.76
neutralized 10 mL of 1 M H2SO4. The percentage of nitrogen
(c) 15.76 (d) 17.36
in the soil is : [2014]
(a) 37.33 (b) 45.33 33. The pair of electron in the given carbanion, CH3C º C- , is
(c) 35.33 (d) 43.33
present in which of the following orbitals ? [2016]
27. Two possible stereo-structures of CH3CHOH.COOH, which
(a) 2p (b) sp3
are optically active, are called. [2015 RS]
(c) sp2 (d) sp
(a) Diastereomers (b) Atropisomers
34. Which of the following biphenyls is optically active ?
(c) Enantiomers (d) Mesomers
[2016]
28. Which of the following statements is not correct for a
(a) O2N
nucleophile? [2015 RS]
(a) Nucleophile is a Lewis acid
(b) Ammonia is a nucleophile
I
(c) Nucleophiles attack low e– density sites Br Br
(d) Nucleophiles are not electron seeking.
29. Given (b)
CH3 CH3 CH I I
3
I
CH3 CH3
(c)
CH3
O O O I
(I) (II) (III) CH3
Which of the given compounds can exhibit tautomerism?
(a) I and III (b) II and III [2015] (d)
(c) I, II and III (d) I and II CH3
35. The correct statement regarding the comparison of 37. The IUPAC name of the compound [2017]
staggered and eclipsed conformation of ethane, is [2016] O O
|| ||
(a) The staggered conformation of ethane is less stable H–C
than eclipsed conformation, because staggered
conformation has torsional strain is :-

(b) The eclipsed conformation of ethane is more stable

than staggered conformation, because eclipsed (a) 5-formylhex-2-en-3-one
conformation has no torsional strain (b) 5-methyl-4-oxohex-2-en-5-al
(c) The eclipsed conformation of ethane is more stable (c) 3-keto-2-methylhex-5-enal
than staggered conformation even though the eclipsed (d) 3-keto-2-methylhex-4-enal
conformation has torsional strain 38. The correct statement regarding electrophile is:- [2017]
(a) Electrophile is a negatively charged species and can
(d) The staggered conformation of ethane is more stable form a bond by accepting a pair of electrons from another
than eclipsed conformation, because staggered electrophile
conformation has no torsional strain. (b) Electrophiles are generally neutral species and can form
36. The most suitable method of separation of 1 : 1 mixture of a bond by accepting a pair of electrons from a
ortho and para-nitrophenols is : [2017] nucleophile
(a) Chromatography (c) Electrophile can be either neutral or positively charged
species and can form a bond by accepting a pair of
(b) Crystallisation electrons from a nucleophile
(c) Steam distillation (d) Electrophile is a negatively charged species and can
(d) Sublimation form a bond by accepting a pair of electrons from a
nucleophile
 Hints & Solutions
EXERCISE - 1 1°
CH 3
1. (c) No. of asymmetric carbon = 2 |
1° 4° 2° 1°
No. of enantiomers = 22 = 4. 11. (d) CH 3 - C - CH 2 - CH 3
|
CH 3
CH3 1°
1 2 3 4| 5
2. (a) Thus number of secondary hydrogens is two.
CH3 - C º C - C - CH3
| 12. (d) Geometrical isomerism is obseved when different groups
H are attached to each of the doubly bonded carbon atom.
13. (a) The IUPAC name of th e given compound is
4 -methyl-2-pentyne 5-chlorohex-2-ene.
3. (a) is the answer. 14. (d) Among 1, 2- and 1, 3- configurations, 1, 3- is more stable
Molecular formula of CH3COOH = C2H4O2 due to less repulsion.
Both the compounds given have same empirical formula Further among cis and trans isomers, trans is more
that is CH2O. So, percentage of carbon in both of them stable due to less crowding.
will be same. 15. (d) 2, 2,3-trimethyl pentane
4. (c) 2 3 4 1° 1°
CH 2 - CH - CH 2 CH3 CH3
| | | 1° 2° | | 1°
1 H3C - H 2 C - CH - C - CH 3
CN CN CN5 3° | 4°
IUPAC name is 3-cyanopentane-1,5-dinitrile CH3
1°
1 2 3 16. (a)
5. (a) CH 3 - O - CH 2 - CH 2 - CH 2 - O - CH 2 CH 3
17. (c) 2
3-ethoxy-1-methoxypropane 3 1
7
S 4 6
1 5
CH3
Bicyclo [4, 1, 0] heptane
6. (b) H 2
Cl 18. (d)
Cl 3
H H
|
C2H5 19. (c) H3C - CH 2 - C*- CH 3
|
S Cl
The compound containing a chiral carbon atom i.e., (a
So compound is (2S, 3S) carbon atom which is attached to four different atoms
7. (c) The correct name is 3 - methylbutan - 2 - ol is known as a chiral carbon atom) is optically active. As
2-chlorobutane contains a chiral C* atom hence it is
Cl optically active.
1
6 2 20. (c) Diastereomers since they have different melting points,
8. (a) boiling points, solubilities etc.
5 3 Br 21. (d) Nitrogen, sulphur and halogens are tested in an organic
4
compound by Lassaigne's test. The organic compound
3-bromo-1chlorocyclohexene is fused with sodium metal as to convert these elements
9. (a) Violet colour in Lassaigne's test indicates the presence into ionisable inorganic substances,
of sulpur. Na + C + N ¾¾ ® NaCN
Na 2S + Na 2 [Fe(NO)(CN)5 ] ¾¾ ® 2Na + S ¾¾ ® Na 2S
sodium nitroprusside
Na4[Fe(CN)5NOS] 2Na + X 2 ¾¾
® 2NaX
violet coloured complex The cyanide, sulphide or halide ions can be confirmed
in aqueous solution by usual test.
O
||
22. (a) Resolution.
10. (c) H - C - CH 2 - CH2 - OCH3 23. (d) Tautomerism is exhibited by the oscillation of hydrogen
1 2 3 atom between two polyvalent atoms present in the
3-methoxypropanal
molecule. As (d) has a-hydrogen atom therefore it
 shows tautomerism whereas other structures do not. From the above structure, it is evident than structure
O OH (a) will show cis-trans isomerism and it also has a chiral
R CH2 N R CH N carbon. On the other hand, structure (b) although
Nitro form O Acinitro form O shows cis-trans isomerism, it has no chiral carbon.
24. (b) Hydrazine (NH2NH2) does not contain carbon and 33. (b) The compound has two similar assymmetric
hence on fusion with Na metal, it cannot form NaCN; C-atoms. It has plane of symmetry and exist in Meso
consequently hydrazine does not show Lassaigne’s form.
test for nitrogen.
25. (a) A compound is said to exhibit optical isomerism if it
atleast contains one chiral carbon atom, which is an
atom bonded to 4 different atoms or groups. plane of symmetry
CH3
|
(CH 3 ) 2 CH - C* - CH 2 CH 3
| Meso - 2, 3 dichlorobutane
H
– 34. (a) Only 2- cylcopropyl butane has a chiral centre.
26. (a) CH2 — C — CH3 CH2 = C — CH3 H
O O *
CH3 – C – chiral centre
–
I II C2H5
both are resonating structures.
27. (b) Compound which are mirror image of each other and 35. (d) The boiling point of o-nitrophenol is less than para-
are non superimposable are termed as enantiomers. nitrophenol due to presence of intramolecular hydrogen
CH3 CH3 bonding. Since p-nitrophenol is less volatile in steam
H OH HO
than o-nitrophenol hence they can be separated by
H
and steam distillation.
HO H H OH
36. (c) IR spectroscopy is used for the purification of
CH3 CH3 cyclohexanone from a mixture of benzoic acid, isoamyl
These are enantiomers alcohol, cyclohexane and cyclohexanone.because in this
28. (a) Kjeldahl's method is suitable for estimating nitrogen in method, each functional group appear at a certain peak.
those compounds in which nitrogen is linked to carbon So, cyclohexane can be identified by carbonyl peak.
and hydrogen. The method is not used in case of nitro, 37. (a) Optically active compound has asymmetric carbon
azo and azoxy compound. This method is basically used atom
for estimating nitrogen in food fertilizers and
H H
agricultural products. | |
29. (a) Clockwise rotation.
CH3 - C - C* - C 2 H5
*
1 Br | |
H 4 OH OH
C It has two asymmetric carbon (marked as *) atoms and
H3C Cl 2
3 is optically active.
Hence configuration is R. 38. (c) x is a conjugated diene system, w is an isolated diene
If the eye travel in a clockwise direction, the system, z is a cumulated diene system, y is antiaromatic
configuration is R as the order of priority is system.
Br > Cl > CH3 > H 39. (c) C7 H7 Cl has 4 isomers
30. (a) Carbon atom is connected with four different groups in
chiral structure. CH3 CH3
31. (c) It has centre of symmetry, so optically inactive. | |
Cl
32. (a) Redrawing the given structures we get,
|

H CH3 Cl
|

H H
| | | | o-Chlorotoluene m-Chlorotoluene
CH3 – C = C - CH 3 CH3 - C - C = C
| | | CH3 CH 2 Cl
*
H3C - C - H H H C-C-H | |
| 3
|
H - C-H CH3
|
CH3
|
benzyl chloride
Cl
(a) (b) p-Chlorotoluene
40. (b) No. of optical isomers = 2x (where x = No. of asymmetric 46. (a) Geometrical isomerism is shown by compounds having
atoms) C = C and the two groups attached to each of carbon
CH3 atom are different
HC3 2 5
H – *C – OH C=C
COOH H H
2-pentene
Lactic acid 47. (b) The parent hydrocarbon is C2H4 or CH2=CH2, so,
\ No. of optical isomers of lactic acid = (2)1 = 2 C2H2Br2 can be obtained by replacing two H by two Br
41. (c) In case two or more chains are of equal length, then the for which there are three possibilities.
chain with greater number of side chains is selected as Br H
the principal chain. C=C or
Br H
1, 1-dibromoethene
6 2
7 5 4 3 Br Br Br H
1
C=C or C=C
H H H Br
2, 3, 5-Trimethyl-4-propylheptane trans
cis
42. (b) Geometrical isomerism is shown by compounds which 1, 2-dibromoethene
have C = C and two groups attached to same C atoms 48. (a) Optical activity is the result of chirality (which comes
are different. Choice (b) fulfills both conditions. from the presence of chiral carbon in molecule) or the
H H H CH3 non–superimposibility of certain molecules on their
and mirror images. So, the compound given in option (a)
C=C C=C
which contains a chiral carbon atom(*) is the only chiral
H3C CH3 H3C H molecule and hence is optically active among the given
cis trans
molecules.
43. (d) The parent hydrocarbon of C3H3 Cl 3 is C3 H6 , i.e.
H H
3
CH3 2 CH = 1CH 2 . Three chlorine atoms can be C=C CH3
H C=C *
present in following ways.
H CH(Cl)CH3
(i) Cl3CCH = CH 2 * marked carbon atom is chiral.
Cl 49. (d) (i) C2H5OC2H5
| diethyl ether
(ii) Cl 2 CHC = CH 2 (ii) CH3OCH2 CH2 CH3
methyl propyl ether
(iii) Cl2 CHCH = CH 2 Cl
(iii) CH3 - O - CH - CH3
Cl |
| CH3
(iv) ClCH 2C = CHCl
methyl isopropyl ether
(v) ClCH 2CH = CCl2 50. (d) Keto-enol tautomerism is shown by carbonyl
compounds having a-hydrogen atom.
Cl
| O O
(vi) CH3 C = CCl 2 || a ||
(a) ˆˆ†
H5 C6 - C - C H 2 - C - C6 H5 ‡ˆˆ
44. (d) COOH keto form
|*
HO - C - H O OH
| || |
H - C* - OH H 5 C6 - C - C = C - C 6 H 5
| |
COOH H
Tartaric acid enol form
Tartaric acid is an example of a symmetrical molecule, O
|| a OH
having two asymmetric carbon atoms. In such cases |
(b) H 5C 6 - C - C H 3 ˆˆ† C H - C = CH
Number of optical enantiomorphs (d and l isomers) Keto form ‡ˆˆ 6 5 2
= 2(n – 1) = 21 = 2 enol form
45. (b) Although (b) has positive ch arge on O (an O
electronegative element), it is more stable because here ||
(c) C6 H5 - C - H
every atom has octet of electrons.
no a- H atom
51. (b) Among the given compounds naphthelene is volatile 61. (c) Nitroethane(C2H5NO2) can exhibit tautomerism among
but benzoic acid is non-volatile (it forms a dimer). So, the given kinds of isomerism due to the presence of a-
the best method for their separation is sublimation, hydrogen which is labile and form nitrolic acid.
which is applicable to compounds which can be O OH
converted directly into the vapour phase from its solid H3 C – CH2 – N H3 C – CH = N
O O
state on heating and back to the solid state on cooling.
62. (a).
Hence it is the most appropriate method.
52. (c) The free rotation across C – C gives rise to many spatial O
arrangements. These ar rangements are called (a) CH = CH – OH CH2 – CH
conformers and property is called conformation.
enol form keto form
53. (a) Maximum number optical isomers of a compound having
n assymetric carbon atoms is 2n.
54. (c) Chiral molecules are those molecules which have atleast (b) O O cannot tautomerise
one asymmetric carbon atom (a carbon atom attached
to 4 different groups). This is true in case of
3-methylpentanoic acid. (c) O OH O, OH

O keto form O OH OH
H enol form
|
C2 H5 – C - CH2 COOH
| (d) O OH , OH
CH3

55. (d) Kjeldahl’s method depends upon the fact that most of O O enol form OH
keto form
the organic compounds containing nitrogen are
63. (d) Benzoic acid, camphor and naphthalene sublime on
quantitatively decomposed to give (NH4)2SO4 when
heating hence, they are purified by sublimation method.
heated strongly with conc. H2SO4. In this method
64. (d) Due to + I-effect of the CH3 group, toluene has much
CuSO4 acts as catalytic agent.
higher electron density in the ring than benzene,
56. (a) Given structures are representing cis-trans isomerism
nitrobenzene and benzoic acid as they show – I-effect
(geometrical) hence differ only in configuration.
and hence is most reactive towards nitration.
57. (a) 65. (c) Compound given in option (c) is the only compound
58. (d) A and B are enantiomers. which do not have any chiral carbon atom. Thus, it is
59. (d) –CH3 group has electron donating inductive effect achiral i.e. do not show optical activity.
which decreases with replacement of each hydrogen 66. (b) In the presence of UV rays or energy, by boiling chlorine,
atom by chlorine atom. Hence highest amount of m– free radical is generated which attack the methyl carbon
substituted product will be obtained on nitration of atom of the toluene.
Cl CH3 CH2
C Cl D
+H
Cl
benzyl free
radical

Cl 2 ¾¾® 2Cl•
hn
60. (b) In diphenylmethane monochlorination at following •CH CH2Cl
positions will produce structured isomers 2 •
+ Cl

67. (d) SN1 reactions involve the formation of carbocation,

CH2 more is stability of carbocation, higher will be the
p roba bi l i ty of a l kyl ha l i de t o u n der g o S N 1
1 m ech a n ism . Th us decr ea si n g or der of S N 1
4 mechanisms follows order Benzyl > allyl > tertiary
2 3 alkyl halide> secondary alkyl halide > primary alkyl
halides
Cl CH2 CH2
Å
(1) Cl (2) CH2Cl CH2
– Cl
Cl
CH2 CH
(Benzyl cation)
Cl (3) (4)
Obtained from SN1 path. This molecule is resonance
stabilised.
68. (d) Styrene can be purified by vacuum distillation. O
69. (a) Among the three given hybrid orbitals, sp hybrid orbital ||
is most electronegative. Contribution of s in sp hybrid 79. (a) In present case, -C - OH is the only group whose
orbital is maximum so this orbital is closer to nucleus. key atom (atom attached to benzene carbon) is having
Naturally it will have greater tendency to pull electron a multiple bond (one of the characteristics of m-directing
towards it. Hence it becomes more electronegative and groups).
sp3 becomes least electronegative. 80. (d) Due to + M effect of the – OH group in phenol, electron
70. (b) It is a coupling reaction of diazonium salt. density in the ortho and para positions of the phenol
In it the aromatic ring undergoing attack by diazonium nucleus increases hence phenol will undergo
ion must contain a powerful electron releasing group, electrophilic substitution easily than benzene. The other
generally –OH, –NR2, –NHR or –NH2. Substitution three compounds have electron withdrawing groups,
usually secures para- to the activating group. hence they will undergo electrophilic substitution with
It has been established experimentally that coupling is a difficulty than benzene.
electrophilic aromatic substitutions. 81. (d)
H
O O s
sp 3 sp 3 sp3 ||
71.
||
(a) H3 C - C - CH 3 ; CH3 - C - OH ; 82. (d) H s C s s
CºN
s 2p
sp 2 sp 2
Acetone Acetic acid H
Therefore, the number of s and p bonds in acetonitrile
O are 5 and 2 respectively.
sp3 sp sp3 || 83. (c) An asymmetric carbon atom is that in which all different
C H3 - C º N ; CH3 - C - NH2 groups are attached with carbon. Option (c) is correct.
sp 2
Acetonitrile Acetamide
84. (b) Electrophiles are electron deficient or positively charged
species.
72. (c) Cl– is the best leaving group among the given option. 85. (b)
73. (b) The order of stability of free radicals 86. (b) Methyl carbanion is sp3 hybridised, with three bond
• • • •
(C6 H 5 ) 3 C > (C 6 H 5 ) 2 CH > (CH 3 ) 3 C > (CH 3 ) 2 C H pairs and one lone pair same is the case with NH3.
87. (d) —NO2 group is electron attractive group, so it is able
The stabilisation of first two is due to resonance and
to deactivate the benzene ring.
last two is due to inductive effect.
Cl
74. (d) Steam distillation is used for the purification of volatile
compounds. NO2
75. (c) The strength of nucleophile depends upon the nature
of alkyl group R on which nucleophile has to attack
and also on the nature of solvent. The order of strength NO2
of nucleophiles follows the order : hence withdrawl of electrons from ortho and para
CN– > I– > C6H5O– > OH– > Br– > Cl– position cause easy removal of –Cl atom due to
76. (c) CF3COOH has highest acidity due to –I effect of F. development of +ve charge on o- and p positions.
77. (b) The chemistry of the Lassaigne’s test of nitrogen is 88. (d) Optical inactivity due to internal compensation is
exhibited by meso-tartaric acid. Option (d) is correct.
D
Na + C + N ¾¾® NaCN 89. (a) Electron withdrawing group (–NO2) increases acidity
From organic
compound while electron releasing group (–CH3, –H) decreases
acidity. Also effect will be more if functional group
2NaCN + FeSO 4 ¾¾
® Fe(CN) 2 + Na 2SO 4 present at para position then ortho and then meta.
Fe(CN) 2 + 4NaCN ¾¾
® Na 4[Fe(CN) 6 ] 90. (d) Absolute alcohol cannot be obtained by simple
Sod. ferrocyanide fractional distillation because a Constant boiling
azeotropic mixture is formed. It is impossible to get pure
3Na 4 [Fe(CN)6 ] + 4Fe3+ ¾¾
® Fe 4[Fe(CN) 6 ]3 + 12Na +
(Ferric ferrocyanide)
ethanol by distiling any mixture of ethanol and water
(Prussian blue) containing less than 95.6% of ethanol. This particular
78. (c) Isoelectronic species has same number of electrons. mixture of ethanol and water boils as if it were a pure
No. of electrons in different species liquid. It has a constant boiling point, and the vapour
+ composition is exactly the same as the liquid.
NH3 = 7 + 3 = 10; CH 2 = 6 + 2 - 1 = 7 91. (c) Simple distillation is suitable for liquids which boil
- - without decomposition at atmospheric pressure. In case
CH 2 = 6 + 2 + 1 = 9; CH 3 = 6 + 3 + 1 = 10 of liquids which decompose before their boiling point
+ is reached, vaccum distillation is used. Glycerine
CH3 = 6 + 3 - 1 = 8 decomposes at its boiling point (298°C) but can be
distilled unchanged at 12 mm pressure at 180°C.
92. (d) In aromatic acids presence of electron withdrawing 100. (a) Nucleophilicity increases down the periodic table.
substituent e.g. –NO2 disperses the negative charge
of the anion and stablises it and hence increases the I - > Br - > Cl - > F-
acidity of the parent benzoic acid. 101. (c) Electrophiles have high affinity for electrons. They
Further o-isomer will have higher acidity than attack at the site where electron-density is highest.
corresponding m and p isomers. Since nitro group at Electron donating groups increases the electron
p-position have more pronounced electron density. The electron donating tendency decreases in
withdrawing than –NO2 group at m-position hence the the order :
correct order is the one given above. –OH > –CH3 > –H > –Cl
COOH COOH Therefore, the correct order of reactivity towards
electrophile is
< C6H5OH > C6H5CH3 > C6H6 > C6H5Cl
NO2 102. (c) Out of the given compounds the most reactive towards

COOH COOH OH

NO2
< < electrophilic attack is . Phenol forms phenoxide

NO2 ion which is stable due to resonance i.e. the correct

93. (b) The stronger the base the more is the nucleophilic answer is option (c).
character and vice versa. 103. (a) In the molecule
Basic character
CH3 CH = CH CH 2 CH- CH 3,
- -
CH 3O > CN > CH3 COO > H 3C - - –
SO3 |
Br
94. (a) 1,2-dihydroxybutane has longest carbon atom chain of the number of stereoisomers is given by sum of
4 atoms and OH groups attached on it at first and
geometrical isomers (because of presence of C = C)
second carbon atoms. So the choice (a) is correct.
and optical isomers (because of presence of chiral
95. (b) – I group destablises carbocation and since inductive
effect decreases with increasing length of carbon chain. carbon atom).
Therefore (b) is the correct option. Number of geometrical isomers = 2 (one C = C is
96. (b) Being immiscible liquids, they form different layers present).
hence can be separated with the help of separating Number of optical isomers = 2 (one chiral carbon atom).
funnel. Total number of stereoisomers = 2 + 2 = 4
97. (c) Simple distillation can be applied for the separation 104. (d) The stability of carbanions is affected due to resonance,
and purification of a mixture of two or more liquids inductive effect and s - character of orbitals. Greater
provided their boiling points differ at least by 30 K. In the number of groups having + I group (alkyl group)
such cases, the low boiling (more volatile) liquid of the lesser stable would be the carbanion.
mixture will distil over first. The temperature of the Further stability of carbanion decreases with decrease
distillation flask is then raised when high boiling (less in s-character. Benzene carbanions are stablized due to
volatile) liquid of the mixture will distil, it is collected in resonance, hence the correct order is
a separate flask.
98. (c) Pentanoic acid and 2-methyl butanoic acid are chain
isomers. R - C = C > R 2C = CH> > R C – CH
3 2
CH3CH2CH2CH2COOH ¾¾ ®
The correct order of stability of given carbanion is in
CH3 the order I > III > II > IV.
|
H3C - CH 2 - HC - COOH 105. (b) C – 1 is sp hybridized (C º C)
C – 3 is sp3 hybridized (C– C)
2 C – 5 is sp2 hybridized (C = C)
C2H5 Thus the correct sequence is sp, sp3, sp2.
3
99. (b) Cl — C — CH3 CH3 CH3
1 sp 3 | sp 2 sp 3 | sp
106. (d) CH3 C CH = CH CH — C º C H
7 6| 5 4 3 2 1
H 4
CH3
R-configuration
107. (d) Alkenes with double bonds cannot undergo free 4 5
rotation and can have different geometrical shapes with 112. (a) Cl CH2CH3
two different groups on each end of the double bond. C=C
2 3
CH3 CH3 CH3 H CH3 I
1
C=C C=C Correct IUPAC name of above compound is
H H H CH3
trans-2-chloro-3-iodo-2-pentene
cis-But-2-ene trans-But-2-ene
CH3
OH 7 6 5 4| 3 2 1
ON2 113. (a) CH3 - CH 2 - CH 2 - C - CH - CH 2 - CH3
NO2 | |
108. (a) > CH3COOH >
CH3 CH 2
|
NO2 CH3
(III) (II) 3-ethyl -4,4- dimethyl heptane
OH OH 114. (a) Nitro group is electron withdrawing group, so it
deactivates the ring towards electrophilic substitution.
> 115. (a) The correct order of priority for the given functional
group is
(IV) (I) O O
|| ||
Explanation : Presence of three — NO 2 groups in –COOH > –SO3H > – C - NH 2 > - C - H
o–, p– positions to phenolic groups (in III) makes 116. (a) CH3
phenol strongly acidic because its corresponding 1 2
|
3
conjugate base is highly stabilised due to resonance. H3C- C - CH3
|
Conjugate base of CH3COOH, II (i.e. CH3 COO - ) is CH3
resonance hybrid of two equivalent structures. The Neopentane
or 2, 2- Dimethylpropane
conjugate base of phenol, IV is stabilized due to
resonance (note that here all resonating structures are 117. (b) H3C CH3 H3C H
not equivalent). The conjugate base of cyclohexanol, I C=C C=C
does not exhibit resonance, hence not formed. H H H CH3
109. (a) Tertiary alkyl halide is most reactive towards *
nucleophilic substitution because the corresponding 118. (b) CH 3 – CH = CH – CHCH 3
|
carbocation (3°) is most stable. Aryl halide is least OH
reactive due to partial double bond character of the C – exhibits both geometrical as well as optical isomerism.
Cl bond. cis - R cis - S
Presence of — NO 2 groups in ortho and para positions trans - R trans - S
increases the reactivity of the – Cl towards 119. (c) For a compound to show optical isomerism, presence
nucleophiles. of chiral carbon atom is a necessary condition.
H
(CH3)3 – C – X > (CH3)2 – CH2 – X > |
III IV
X H 2 C < CH — C* — CH 2 , CH3
|
X CH3
NO2
3- methyl-1-pentene
> 120. (b) – CN has highest priority. Further the sum of locants is
7 in (b) and 9 in (d).
NO2
II I 121. (b) Alkyl groups with at least one hydrogen atom on the
or I < II < IV < III a-carbon atom, attached to an unsaturated carbon
110. (d) Cl– is the weakest base and hence better leaving group atom, are able to release electrons in the following way.
111. (a) The given compound is
2 1
CH = CH2
CH3 — CH2 — CH2 — CH — CH — CH2 — CH3 Note that the delocalisation involves s and p bond
3 4 orbitals (or p orbitals in case of free radicals) ; thus
CH2 – CH3 it is also known as s – p conjugation. This type of
5 6 electron release due to the presence of the system
4 ethyl- 3-propyl hex – 1 – ene H—C—C = C is known as hyperconjugation
 In this reaction Walden Inversion takes place so it is an
sp 2 sp sp 2
122. (b) Allene (C3H4) is H 2 C = C = CH 2 exampleof SN 2-reaction.
7. (b) Peroxide ion is more nucleophilic but less basic than
123. (b) Chiral conformation will not have plane of symmetry.
OH–.
Since twist boat does not have plane of symmetry it is
8. (d) –OCH3 activates the benzene ring. –NO2 deactivates
chiral.
the ring. Hence the reaction of the given compounds
124. (d) Methyl group can’t produce electromeric and
with electrophiles is in the order, I > II > III.
resonance effects. Inductive effect affects all the three
9. (c) The compound is diethyl ether (CH3CH2)2O which is
positions of the ring in decreasing order of ortho >
resistant to nucleophilic attack by hydroxyl ion due to
meta > para. It shows hyperconjugation (no-bond
absence of double or triple bond, whereas all other
resonance) which explains beautifully the o, p-directing
compounds given are unsaturated
influence of the -CH 3 group.
O
125. (d) Taking any two halogens, the possible structural ||
isomers for the alkene can be three. C 2 H 5 OC2 H 5 CH3 - C - OCH3
Diethyl ether Methylacetate
F Br F Cl F Cl
C=C I C=C C=C O
Cl Br I I Br ||
Each of the three alkene can exist as E and Z isomer, CH3 - C º N CH3 - C - NH 2
making total number of isomers as six. Acetonitrile acetamide
10. (c) The atom or group which has more power to attract
EXERCISE - 2 electrons in comparision to hydrogen is said to have
1. (b) A cis-isomer has higher b.p. due to polar (or more polar) -I effect. Thus higher the electronegativity of atom
nature but lower m.p. due to asymmetry than the trans- stronger will be the -I effect. As electronegativity of N,
isomer. Among three isomeric nitrophenols, o-isomer O and F follow the order N < O < F hence based upon
forms intramolecular bonding so H-bonding with water electronegative character order of-I effect is
will be restricted. – NR2 < – OR < – F.
2. (d) Due to resonance of lone pair. 11. (d) All statements are ture.
3. (a) Due to resonance conjugated alkadiene is maximum 12. (b) Stability of an alkene depends upon the heat of
stable. Isolated is more stable than cumulated alkadiene. hydrogenation of an alkene. The heat of hydration is
4. (a) NH2OH is less basic than NH3 because of –I effect of the standard enthalpy change in hydrogenation of on
OH. However –CF3 is more basic than –CCl3 because in alkene. The lower the heat of hydrogenation of an
:–CCl3 the unshared electron pair of C in the p orbital alkene higher will be stability.
undergoes extented p–dp bonding into an empty d AO Order of stabilityHeat of hydrogenation
of the three chlorines, hence it is less available for (kJ/mol)
protonation. trans-2-butene – 115.5
cis-2-butene – 119.6 and
.. . .- . . -. . .. 1-butene – 126.8 respectively.
: .C.l - C - C
..l:¬¾® : C
.. l = C -C l : ¬¾® etc.
|
..
| 13. (a) Amino group is activating while nitro group is
:Cl
. .: :Cl
. .: deactivating. Hence, correct order is
aniline > benzene > nitrobenzene.
Since F lies in the 2nd period, it has no d orbital, hence
I > II > III
such dispersal of electrons of C is not possible.
Remember resonance stabilization is generally more NH2 NO2
important than the inductive effect.
5. (c) More is the electron - deficiency on the carbonyl
carbon, greater will be the reactivity of the carbonyl I II III
compounds towards nucleophilic addition. –NO2 is an electron attracting group hence decrease
O the electron density on ring, whereas –NH2 group is
electron releasing group hence increases electron
CH3CH 2CH 2CH 2CHO > > CH3CH2COCH2CH3 density on ring. Benzene is also electron rich due to
delocalization of electrons.
6. (d) When (–) 2-bromooctane is allowed to react with
sodium hydroxide under conditions, where second 14. (b) H 2 C = CHCl is capable of showing resonance which
order kinetics are followed, (+) 2 octanol is obtained. develops a partial double bond character on C–Cl bond,
thereby making it less reactive toward nucleophilic
C6H13 H C6H13 C6H13 substitution.
–
OH – .. _
H C Br HO -----C -----Br HO C H + Br
H 2 C = CH - Cl
.. : H 2 C - CH = Cl+
CH3 CH3 CH3
(–) 2-Bromooctane Transition state (+2) 2–octanol
 .. H
H + 25. (b) % of chlorine = 35.5 ´ Mass of AgCl ´ 100
15. (a) C C 143.5 Mass of substance

..
H H

..
35.5 0.287
H = ´ ´100 = 71.71%
Carbocation Alkyl group 143.5 0.099
+
Hyperconjugation in CH2CH3 Å
H 26. (b) Carboxylic acids are stronger acids than - NH 3
H
because the corresponding conjugate base (–COO–) is
H2C – CH = CH 2 H2C – CH2 more stable than –NH2. Hence Y is the strongest acid.
Since – COOH has – I effect which decreases with
Hyperconjugation in propene Hyperconjugation
in free radical distance, therefore, effect is more pronounced in Z than
16. (b) HCOO – exists in following resonating structures in X. As a result, Z is more acidic than X. Hence the true
O O option is Y > Z > X.
|| | 27. (c) Shape of transition state is as follows:
,
H , C, O « H , C < O
Hence in it both the carbon oxygen bonds are found R
equal. Nu C X
17. (d) Lone pair of electrons present on the nitrogen of benzyl
amine is not involved in resonance. H R
COOH
4 2 Trigonal bipyramidal
18. (b) 5 . Here C 2 is chiral, hence optical CH 3
3 1 + +
isomerism is possible. However, the doubly bonded C4 28. (c) C 6 H5 C H 2 > CH >
has two similar (–CH3) groups, hence geometrical CH 3
isomerism is not possible.
19. (c) Metamerism shown among compounds of the same 23°
functional group. Benzyl
+ +
20. (c) The stronger the acid, the weaker the conjugate base > F - CH 2 -- C H
F - CH 2 - CH 2 - C H
formed. | |
The acid character follows the order : CH 3 CH 3
CH3COOH > C6H5OH > H2O > CH3OH 2° (more stable)
The basic character will follow the order F is more away from +ve charge
CH3COO– < C6H5O– < –OH < CH3O– 29. (d) Order of stability of carbocation 3° > 2° > 1° and I is the
Hence, decreasing order of rate of given reactions with best leaving group among halogens.
Nu– is 30. (d) Since diazo compounds may lose nitrogen in the form
D > C >A> B of nitrogen gas, they sometimes do not respond
21. (d) Lassaigne’s test for nitrogen.
22. (a) CH3* CH (OH)COOH
-OH
¾¾¾® CH 3CH(H )COOH 31. (d) Lone pair present at X can enter in the ring. This gives
Lactic acid +H
No chiral carbon rise to double bond character in C – X bond attached
Chiral carbon is present
(optically active)
(optically inactive ) to the ring .
32. (a) In given structures –
After releasing H+ from (ii) group it forms a more stable
23. (d) resonating structure of carboxylate ion. In case of (i)
the anion formed after release of H+ is more stable due
to present of e– withdrawing NO2 in benzene ring. In
(iii) phenoxide ion formed after release of H+ is more
stable in comparison to Acetylide ion of group (iv)
which is formed after releasing of (iv) H+ ion so acidic
structure of Ka is
(ii) > (i) > (iii) > (iv)
33. (b)
34. (d) Na 2 [Fe(CN)5 NO] + S2 - ® Na 4 [Fe(CN)5 NOS]
Sodium thio-nitroprusside
(violet)

24. (c) Because of partial double bond character (due to 35. (d) The amount of s-character in various hybrid orbitals is
resonance), C – H bond energy is less for toluene. as follows.
sp = 50%, sp2 = 33% and sp3 = 25%
 Therefore s character of the C – H bond in acetylene G releases electrons, intensifies –ve charge,
(sp) is greater than that of the C – H bond in alkene (sp2 destabi l izes car bani on, retards SN reaction
hybridized) which in turn has greater s character of the (deactivation)
C – H bond than in alkanes. Thus owing to a high s NO2 is activating group and CH3 and OCH3 are
character of the C – H bond in alkynes, the electrons deactiving group.
constituting this bond are more strongly held by the Hence, the correct order of nucleophilic substitution
carbon nucleus with the result the hydrogen present reactions
on such a carbon atom can be easily removed as proton.
Cl Cl Cl
The acidic nature of three types of C – H bonds follows
the following order Cl
-C º C - H > - C = C - H > - C - C - H
> > >
Further, as we know that conjugate base of a strong
acid is a weak base, hence the correct order of basicity
is NO2 CH3 OCH3
- - -
H - C º C < CH2 = CH < CH 2 - CH3 39. (b) The organic compounds which have chiral carbon atom
36. (b) Due to + M effect of – OH group and hyperconjugation (a carbon atom attached to four different group or atoms
of – CH3 group. and do not have plane of symmetry rotate plane
37. (c) Because of high electronegativities of the halogen atom, polarised light.
the carbon halogen (C – X) is highly polarised covalent CHO
bond. Thus, the carbon atom of the C – X bond becomes |
HO - C*- H (C* is asymmetric carbon)
a good site for attack by nucleophiles (electron rich |
species). Nucleophilic substitution reactions are the CH 2 OH
most common reactions of alkyl halides. 40. (b) The absolute configuration is (R, R)
38. (a) In SN Ar reactions, a carbanion is formed as an intermediate, (using priority rules to get the absolute configuration)
so any substituent that increases the stability of carbanion So the correct answer is (b)
and hence the transition state leading to its formation will 41. (b) In option (b) the complex formed is with benzene
enhance the SNAr reactions. To compare the rates of whereas in other cases it is formed with nitrobenzene
substitution in chlorobenzene, chlorobenzene having with –NO2 group in different position (o-, m-, p-). The
electron-withdrawing group, and chlorobenzene having complex formed with nitrobenzene in any position of
electron-releasing group, we compare the structures –NO2 group is less stable than the complex formed
carbanion I (from chlorobenzene), II (from chlorobenzene with benzene so the correct answer is (b). The most
containing electron-withdrawing group) and III (from stable complex has lowest energy.
chlorobenzene containing electron-releasing group). Cl
– – – –
Z Cl Z Cl 42. (b) C Cl > C6H5CH2 > (CH3)2 CH > (CH3)3C
Cl
–ve charge –M effect +I effect of CH 3 group
– – highly dispersed delocalises intensifies the –ve charge
due to – I effect –ve charge

43. (d) The correct order of basicity is

G
RCOO - < CH º C - < NH 2 - < R -
I II
44. (a) Due to similar charges on adjacent atoms, the structure
G withdraws electrons, neutralises (disperses) –ve (a) is least stable.
charge of the ring, stabilises carbanion, facilitates 45. (a) Anti addition of Br2 on trans alkene provides meso
SN reaction (activation effect) compound.
CH3
Z Cl H 3C H
CCl4 H Br
C= C + Br2 ¾¾ ¾®
– H CH 3 H Br
CH3
Therefore, no. of stereoisomers = 1
G
46. (d) The correct stability order is
III I > III > II > IV
 Note : Carboxylic acid (—COOH) has more priority
+ + than ketone ( C= O).
O O 3. (b) Cl
I III 1 NO2
+ M effect, 6 hyper-
conjugative H’s, + M, 3 hyperconjugative 2
2 CH 3 groups . H’s, one CH 3 group
3
(+ I effect) 4

CH3
+
+ 1-chloro-4-methyl-2-nitrobenzene
II IV For tri or higher substituted benzene derivatives, the
5 hyperconjugative 5 hyperconjugative H’s compounds are named by identifying substituent
H’s 2 R groups one R group positions on the ring by following the lowest locant
rule.
47. (d) Migrating tendency of hydride is greater than that of 4. (c) Electronegativity of carbon atom depends on its state
alkyl group. Further migration of hydride from C–2 gives of hybridisation. More the s-character more will be the
more stable carbocation (stabilized by +R effect of OH electronegativity.
group and +I and hyperconjugative effects of methyl sp3 < sp2 < sp
group). s-character : 25% 33% 50%
Thus, sp-carbon (CH3 – CH2 – C º *CH) has the highest
H H
electronegativity.
1 2 3+ 4 5
1, 2 hydride
H3C – C — C– C – CH3 ¾¾¾¾¾ ® 5. (c) Two or more compounds having the same molecular
shift
formula but different functional groups are called
OH H CH3 functional isomers. Functional isomer of alcohol is ether,
aldehyde is ketone and cyanide is isocyanide. But alkyl
H H halides do not show functional isomerism.
+
6. (d) Essential oils are insoluble in water and have high
H3C – C — C– C – CH3
vapour pressure at 373K but are miscible with water
..OH H CH3 vapour in vapour phase, it means these are steam
..

volatile. Thus, steam distillation technique is a suitable

More stable carbocation method for the extraction of essential oils.
48. (a) It is fact that aniline is better nucleophile than anilium 7. (d) Thin layer chromatography (TLC) involves separation
ion. Anilium ion contain +ve charge, which reduces the of substances of a mixture over a thin layer of an
adsorbent coated on a glass plate.
tendency to donate lone pair of electron C6 H5 NH3+ .
A thin layer of an adsorbent is spread over a glass
Anilium ion
plate and glass plate is placed in an eluant. As eluant
Therefore , both assertion and reason are true. rises, components of the mixture move up along with
49. (c) The assertion that trans-2 butene reacts with Br 2 to the eluant to different distances depending on their
product meso-2, 3-dibromobutane is correct but it does degree of adsorption and separation takes place.
not involve syn-addition of Br 2. Therefore, TLC technique will give the best results in
50. (d) Resonance structures contain the same number of identifying the different types of ink used at different
unpaired electrons. However, they differ in the way of places in the documents.
distribution of electrons. 8. (b) Partition chromatography is based on continuous
EXERCISE - 3 differential partitioning of components of a mixture
between stationary and mobile phases. Paper
Exemplar Questions chromatography is a type of partition chromatography.
CH3 9. (a) Stability of the given cations can be understood by
7 6 5 4| 3 2 1
the following structures:
1. (a) CH3 – CH2 – CH2 – C – CH – CH2 – CH3 + + ..
| | CH3 CH CH3 ; CH3 - C H - O. . - CH3 ;
(I) (II)
CH3C2H5 + I – effect of the two Strong + R – effect of – OCH3
3-ethyl-4, 4-dimethyl heptane methyl groups stabilises group stabilises the carbocation
the carbocation
O O +
2. (d) 5 || 3 2 1 || CH 3 - C H - CH 2 ®- OCH 3
CH3 -4C - CH 2 - CH 2 - C - OH (III)
4-oxopentanoic acid - I effect of -OCH 3 group
destabilises the carbocation
 Hence, the correct order of decreasing stability of 15. (b) Addition of HCl to an alkene takes place in two steps as
carbocation will be : II > I > III follows:
10. (b) 4 3
Step I : p-bonds creates an electron cloud, electrophile
H3C — CH — CH — CH3 (H+) from H — Cl attacks the electron cloud and a
| | carbocation is formed.
5 CH 2 CH2
2
| | +
C—
+
C—C
H —C
6 CH3 1 CH3

—
3, 4-dimethylhexane H
(carbocation)
11. (a) Electronegativity of Cl, Br, C and Mg follows the order
Step II : The chloride ion attacks the carbocation
Cl > Br > C > Mg, thus chlorine has the greatest –I-
formed.
effect and disperse the positive charge on ‘C’ atom
most effectively.
Å –
Hence, * CH3 — CH2 — Cl has the greatest positive C—C + Cl C—C
charge. | | |
H Cl H
12. (d) In all the given ionic species, the negative charge is
dispersed which stabilises them. Here, the negative NEET/AIPMT (2013-2017) Questions
charge is dispersed by two factors, i.e., +R-effect of
OH
the carboxylate ion (conjugation) and – I-effect of the
halogens. 3 2
1
H3C COOH
As it can be clearly seen in the given structures, that 16. (a) 4
6
+R-effect is common in all the four species, therefore, 5 CH 3
overall dispersal of negative charge depends upon the
IUPAC name of th e structure is 3-eth yl-2-
number of halogen atoms and their electronegativity. hydroxy-4-methylhex-3-en-5-ynoic acid
Since, Fluorine has the highest electronegativity and 17. (c) Decreasing order of deactivating effect of the given
two F-atoms are present in option (d), thus, dispersal m-directing group is
of negative charge will be maximum in it, thus it is most NO2 > – CN > – SO3H > – COOH
stable. –NO2 group is most deactivating group due to
O O
–
strong – E, – I and – M effects.
F || F 18. (b) –NO2 is a powerful electron withdrawing group. Its
—

–
CH C—O CH C—
—O º presence on ring makes the ring less active.
F F CH 3
F O 19. (d) CH - CH 2 - (isobutyl group)
CH C –
CH 3
F O
20. (b) Greater the number of e– donating alkyl groups
Note : In structure (a), methyl group increases the (+I effect), greater will be the stability of carbocations.
density on C-atom.
21. (c) Conformers are form of stereoisomers in which isomers
13. (c) When an electrophile attacks CH3 – CH = CH2, there can be interconverted by rotation about single bonds.
are two possibilities of an intermediate formed: I and II are staggered and eclipsed conformers
+ Å respectively.
CH3 – CH = CH2 + H ® CH3 – C H – CH3 22. (c) Stability depends on number of hyperconjugative
(2°carbocation) structure.
+ Å
CH3 – CH = CH2 + H CH 3 - CH 2 - CH 2 23. (b) In the carbonium ion the carbon atom carrying the
(1° carbocation) positive charge is sp2 hybridized.
As 2° carbocation is more stable than 1° carbocation 24. (c) The prussian ferric ferrocyanide blue colour is of Fe4
thus first addition is more feasible. [Fe(CN)6]3
Note : Stability of carbocations is the basis of 26. (N) Out of the given four compounds only (iv) compound
Markownikoff's rule. is chiral and hence only this compound will undergo
racemisation. Therefore none of the given option is
14. (b) Arrow denotes the direction of movement of electrons.
correct.
Å
CH 3 - Br ¾ ¾
® CH 3 + Br 26. (a) 10 ml, 1 M H2SO4 = 20 ml, 1 M NH3
Q wt of N in one mole NH3 = 14
Since, Br is more electronegative than carbon, hence
heterolytic fission occurs in such a way that CH3 gets \ 20 × 10– 3 mol NH3 ¾®
a positive charge and Br gets a negative charge. 20 × 10– 3 × 14 nitrogen
 \ 0.75 g of sample contains 273 ´ 700 ´ 40
= = 33.52 mL
14 ´ 20 ´ 10 -3 300 ´ 760
= ´ 100 = 37.33% Percentage of nitrogen
0.75
27. (c) H 28× volume of N 2 at STP ×100
= 22400 × wt. of organic substance
C COOH 28 ´ 33.52 ´ 100
CH3 = = 16.76%
OH 22400 ´ 0.25
Four different Substituent, only one chiral centre. 33. (d) CH3—C º C
Hence only enantiomers are possible. No.of s bp - 1 ù
28. (a) Nucleophile is a species that provide electron while lp -1 û
2 & hybridisation is sp
species which are deficient of electrons termed as lewis
acid, hence nucleophiles are usually lewis bases. Br Br
29. (c) All of these compounds show tautomerism
H3C CH3 H3 C CH3
34. (b) is optically active

H I I
O OH due to absence of plane of symmetry and center of
CH3 CH3 symmetry.
CH3 CH3 35. (d) In staggered conformation any two hydrogen atoms
on adjacent carbon atoms are as far apart as possible
H
there by minimising repulsion between the electron
O
O OH
OH
H clouds of s-bonds of two non-bonded H-atomic
H
(torsional strain)
H HH
CH3 CH3
H H
CH3 CH3
O OH
30. (b) Only structure (III) has hyperconjugation with free H
radical. H H H H
H
So, hyperconjugation is possible in III only. H
– Staggered form Eclipsed form
31. (b) p bond is transferred after leaving Cl
Å No torsional strain
CH3 – CH=CH.CH2 —Cl CH3 – CH=CH—CH2 36. (c) Steam distillation is the most suitable method of
Å separation of 1 : 1 mixture of ortho and para nitrophenols
CH 3—CH—CH=CH 2 as there is intramolecular hydrogen bonding in o-
32. (b) Wt. of organic substance = 0.25 g nitrophenol.
V1 = 40 mL, T1 = 300 K O
O
P1 = 725 – 25 = 700 mm of Hg C 2
P2 = 760 mm of Hg (at STP) 37. (d) H 3 4
1
T2 = 273 K 5
6
3-keto-2-methylhex-4-enal
P1V1 P2 V2 Aldehydes get higher priority over ketone and alkene
=
T1 T2 in numbering of principal carbon chain.
V2 (Volume of nitrogen at STP) 38. (c)