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Organic Chemistry :
Some Basic Principles
and Techniques
This Chapter '’Organic Chemistry : Some Basic Principles and
Techniques’' is taken from our Book:

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AL
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U
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ISBN : 9789386320780
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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
s-character and hence, it is closer to its nucleus and forms shorter

property of carbon results in the formation of a large number of
compounds of carbon. These compounds are covalent in nature
and are studied under a branch of chemistry called organic
chemistry. Carbon atoms present in organic compounds are either
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and stronger bonds than sp3 hybrid orbital.
The bond angles and geometry associated with the three types of
hybridization are summarized below :

Hybridisation sp
3
AL
sp2 sp
N
Angle 109º28' 120º 180º
Geometry Tetrahedral Trigonal Linear
R

Example Alkane, Cycloalkane Alkenes and other compounds Alkynes and all other
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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,
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Bond Four- Three-s Two-s

One- Two-
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s% 25 33.3 50
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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(sp2) – C(sp2) > C(sp3) – C(sp3) (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
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(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

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Open chain Closed chain
or
Acyclic
AL or
Cyclic
or or
N
Aliphatic compounds Ring compounds
R

Unsaturated Homocyclic Heterocyclic

Saturated
U

e.g. Benzene e.g. pyrrole

e.g. Alkanes e.g. Alkenes & Alkynes
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Alicyclic Aromatic
U

Saturated Unsaturated Benzenoids Nonbenzenoids

e.g. cyclopropane e.g. cyclopropene
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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
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(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

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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
indicated by appropriate numbers. If different alkyl groups
AL 2¢ CH - CH3
|
1¢ CH - CH3
are present they are listed in alphabetical order. For example 1 2 3 4 5| 6 7 8 9
N
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
R

CH3 C2 H5 Nomenclature of Cyclic Compounds

3–Ethyl–2 methylpentane and not as
A saturated monocyclic compound is named by prefixing ‘cyclo’
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2 - Methyl- 3- ethylpentane
(d) If two or more identical substituent groups are present, then to the corresponding straight chain alkane. If side chains are given,
then rules given above are applied.
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numbers are separated by commas. The names of identical

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.
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For example : 12
3 1 - methyl - 3 - propylcyclo - hexane
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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
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(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

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butan –2–one

Class of Functional group Functional Functional

compounds
Alkanes
structure
–
AL
group prefix
–
group suffix
-ane
Alkenes >C=C< – -ene
N
Alkynes – C º C– – -yne
Arenes – – -
R

Halides –X halo -
(X = F, Cl, Br, I)
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Alcohols –OH hydroxy -ol

Aldehydes –CHO formyl, -al
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or oxo
Ketones >C=O oxo -one
Nitriles -CN º cyano nitrile
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Ethers R-O-R alkoxy -

Carboxylic –COOH carboxy -oic acid
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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
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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)

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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 : AL CH3

OMe
CH3
N
CH3 1
CH3 1 1 Cl
1 CH3 2 2 - Chloro - 4 - methyl anisole
R

2 3
3 CH3 4 4
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1,2-Dimethylbenzene 1,3-Dimethylbenzene CH3 CH3

(o-Xylene) (m-xylene) 1,4-Dimethylbenzene
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(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
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ISOMERISM
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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.
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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

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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
CH3 – CH2 – CH2 – CH2OH CH3 - CH - CH 2 OH
AL functional group.
Members belong to the same homologous series.
| Ex.
N
CH3 (a) Diethyl ether and methyl propyl ether
n-Butyl alcohol Isobutyl alcohol CH3CH2OCH2CH3 CH3OCH2CH2CH3
R

These two butyl alcohols are chain isomers. Diethyl ether Methyl propyl ether
(b) Diethyl amine and methyl propyl amine
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(ii) Position isomerism : It is shown by the compounds in which

there is difference in the position of attachment of functional CH3CH2 – NH – CH2CH3 CH3CH2CH2 – NH – CH3
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group, multiple bond or substituent along the same chain
length of carbon atoms.
Examples : CH3 – CH2 – CH2Cl & CH3 – CH – CH3
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Diethyl amine Methyl propyl amine
(v) Tautomerism :Tautomerism is a special type of functional
group isomerism which arises due to the migration of H-atom
as proton from a polyvalent atom to other polyvalent atom

|
Cl with reshuffling of p bond.
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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)
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(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

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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. AL 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
N
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
R

right) or direction (+) – form. A

B Y
(c) An inactive form which does not rotate the plane of polarized
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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.
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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
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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:
ED

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
of the covalent bond (i.e., shared pair) are taken away by one
of the bonded atoms, the mode of bond cleavage is called
heterolytic fission or heterolysis.
Heterolytic fission + –
A : B ¾¾¾¾¾¾¾ ® A +:B
(when B is more electronegative than A)
It results in formation of cations and anions
Favourable conditions : (a) Low temperature (b) Polar solvent (c)
Presence of acid or base catalyst (d) Polar nature of the substrate
and attacking reagent.
Nucleophiles and Electrophiles
A reagent that brings an electron pair is called a nucleophile i.e.
nucleus seeking and the reaction is called nucleophilic.
They are of two types :
(a) Charged Nucleophiles :
9
+
e.g. - N R 3 > – NO2 > – CN > – COOH > –F
> – Cl > – Br > – I > – O && H > – O
&& R > –C H > – H
6 5
(b) +I Effect : Those atoms or group of atoms which attract the
shared electron pair (bond pair) less strongly than hydrogen
atom are said to have +I (electron repelling) effect. Such
groups when attached with a carbon chain displace the shared
s electrons towards the chain and make it electron rich.
(CH3)3C – > (CH3)2CH – > CH3 – CH2 – > CH3 –
(ii) Resonance effect : It is defined as the polarity produced in a
molecule by the interaction of two p - bonds or between a p -
bond and lone pair of e–1 s present on an adjacent atom. It is
also called mesomeric effect. It is a permanent effect.
Two types of resonance effects:
(a) Positive resonance effect (+ R effect)
In this effect, transfer of electrons is away from an atom group

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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.
(b) Neutral Nucleophiles : Central atom has electron pair.
AL O
H
O
+
H

&& , R — NH &&
&& , R – NHR && , H O
, R 3N && &&
NH 3 2 2 :,R– O . . – H,
N
A reagent that takes away an electron pair is called an electrophile
(E+) i.e., electron seeking and the reaction is called electrophilic
R

Phenol
Electrophiles may be neutral or positively charged.
(a) Neutral electrophiles : Central atom has deficiency of
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H
electrons. ex. BF3, BCl3, AlCl3, BeCl2, FeCl3, SO3, etc.. +
O
+
O
H H
O
(b) Charged electrophiles :
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All the positive ions behave like electrophiles.

+
Cl+, Br+, I+, NO2+, NO+, H+, H3O+, N H 4 , R+,
+
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R — C = O , etc.
Examples : halogen, – OH, – OR, – OCOR, – NH2, – NHR,
Electrophiles are generated by heterolysis of a covalent bond. – NR2, – NHR, – NR2, – NHCOR
ED

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.
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Effects of hyperconjugation :
Examples : –COOH, – CHO, C = O, – CN, – NO2 (1) Stability of alkenes :
(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)

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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 : ALgreater is the hyperconjugation interaction and stabilisation
of the cation.
CH3 CH CH2 H CH3 CH CH3 The relative stability of carbocations follows the order:
N
Propene Isopropyl carbocation CH3
| + + +
R

(b) – E effect
CH3 — C + > ( CH3 ) 2C H > CH3C H 2 > C H3
In this, p – electrons of multiple bond are transferred to that |
U

atom to which attacking reagent does not get attached CH3

For example :
INTERMEDIATES
O–
JO

H – H
O CN C Free Radicals
H H CN
| |
U

Homolytic fission
Formaldehyde Anion
Anion -C - X ¾¾¾¾¾¾¾¾ ® – C• + X•
Oxygen being more electronegative pulls p electrons of | |
ED

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
 11
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

.IN
| 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
An organic species containing negatively charged carbon atom is
called carbanion.
AL D
C + 2CuO ¾¾® 2 Cu + CO 2
D
2H + CuO ¾¾® Cu + H 2O
N
Stability of carbanion is due to following reasons
(i) Inductive effect CO 2 + Ca( OH ) 2 ¾¾
® CaCO 3 ¯ + H 2 O
R

(ii) Resonance
(iii) s-character in Hybridisation
5H 2 O + CuSO 4 ¾¾
® CuSO4 .5H2 O
U

1
Stability of Carbanion µ –I , µ white blue
+I
JO

– –. 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
– – – –
compounds are converted to ionic form by fusing with Na-metal.
U

(ii) CH 3 > CH3 CH2 > (CH3)2 CH > (CH3)3 C

The reactions involved are:
Note : Carbanions are nucleophiles.
ED

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.
 12
(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 = 760 ´ T (Let it be V mL)
2Na + S ¾¾ ® Na2S ; 1
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

.IN
(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).
(d) Test for P : Phosphorus is detected by fusing the organic
ALH2SO4.
D
compound with an oxidising agent like Na2O2 .P in the N (from compound) + conc. H2SO4 ¾¾ ® (NH4)2SO4
N
D
compound is oxidised to PO34- which is then extracted with (NH4)2SO4 + 2 NaOH ¾¾ ® Na2SO4 + 2H2O + 2NH3
R

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
U

presence of phosphorus. a standard alkali solution.

2 NaOH + H2SO4 ¾¾ ® Na2SO4 + 2H2O.
JO

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
U

14 ´ M ´ 2 ç V - 1 ÷
H3PO 4 +12 ( NH 4 ) 2 MoO4 + 21HNO3 ¾¾
® è 2 ø 100
% of N = ´
ED

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
 13
(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

.IN
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
AL 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)
N
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
R

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
U

mass of CO2 produced = W1 g

of (NH4)3PO4. 12MoO3 is then filtered, washed, dried and
32 ´ W1
weighed.
JO

\ m1 g of CO2 is obtained from g O2

D
88
C + 2 O (from HNO3) ¾¾ ® CO2
32 ´ W1 ´ 100
2H + O (from HNO3) ¾¾
® H2O
D \ % of O2 = 88 ´ W
%
U
ED
 CONCEPT MAP

ED
U
JO
U
R
N
AL
.IN
14
 15

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

.IN
(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 :
CH 2 - CH - CH 2 is 12.
AL
(a) 8 (b) 6 (c) 4
The geometrical isomerism is shown by
(d) 2

| | | CH2
CH2
N
CN CN CN
(a) 1, 2, 3-trinitropropane (a) (b)
R

(b) 1, 2, 3-tricyanopropane
(c) 3-cyanopentane-1, 5-dinitrile CHCl
CCl2
U

(d) 1, 2, 3-pentanetrinitrile
5. The IUPAC name of the compound (c) (d)
JO

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
U

(c) 2, 5-dioxyhexane |
(d) ethoxypropane oxymethane CH3 - C - CH 2 - CH = CH - CH3 is
|
ED

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
 16
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

.IN
(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
(c) R3CNO2
(b) (CH3)3CNO
(d) RCH2NO2
AL(c) only II and IV are chiral compounds
(d) all four are chiral compounds
31. Which of the following is optically inactive?
24. Lassaigne’s test for the detection of nitrogen fails in
H H
N
(a) NH 2 CONHNH 2 .HCl (b) NH 2 NH 2 .HCl
H 3C Cl Cl CH3
(c) NH 2 CONH 2 (d) C 6 H 5 NHNH 2 .HCl (a) (b)
R

Cl CH3 H3C Cl
25. A compound of molecular formula of C7H16 shows optical H H
U

isomerism, compound will be H

(a) 2, 3-Dimethylpentane (b) 2,2-Dimethylpentane H 3C Cl
(c) H C (d) none of these.
JO

(c) 2, 4 - Dimethylpentane (d) None of these 3 Cl

.. .. H
26. CH2 – C – CH 3 and CH2 = C – CH3 are
|| | 32. C8H16 that can form cis-trans geometrical isomers and also
O :O
. .: has a chiral centre, is
U

(a) resonating structures (b) tautomers

(c) geometrical isomers (d) optical isomers H
ED

(a) (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) H
and
HO 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
 17
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 and (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

.IN
(x) (y) H3C CH2Cl CH CH
C (d) C C 2 3
AL 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
N
39. An aromatic compound of formula C7H7Cl has in all ..... 50. Keto-enol tautomerism is observed in :
isomers :
R

(a) 5 (d) 2 (c) 4 (d) 3 O O

40. How many optically active stereoisomers are possible for || ||
H 5 C 6 - C - CH 2 - C - C 6 H 5
U

(a)
lactic acid ?
(a) 1 (b) 2 (c) 4 (d) 3
O
JO

41. The correct IUPAC name for ||

(b) H 5 C 6 - C - CH 3
U

O
||
(c) H 5C 6 - C - H
ED

(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
 18
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?

.IN
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
(c) (A) and (C) are enantiomers
AL +Cl2

(d) (A) and (B) are enantiomers Anh. AlCl3 CH3

59. Which compound on nitration will give highest amount of (c) +CH3Cl
N
m-substituted product ?
R

CH3 CH2–Cl CH2Cl CH2NO2

(d) + AgNO2
U

(a) (b) 67. Which of the following undergoes nucleophilic substitution

exclusively by SN1 mechanism?
JO

Cl (a) Ethyl chloride (b) Isopropyl chloride

Cl
CH C Cl (c) Chlorobenzene (d) Benzyl chloride
Cl Cl 68. Styrene can be purified by
U

(a) Simple distillation (b) Fractional distilation

(c) (d)
(c) Steam distillation (d) Vacuum distillation
ED

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
 19
71. Which one of the following does not have sp2hybridized 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

.IN
(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 –
(a) Br– (b) : OH– AL exhibited by :
(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 :
N
(a) CCl 3COOH (b) CH 3 COOH OH OH OH OH
R

(c) CF3 COOH (d) CBr3 COOH

77. The prussian blue colour obtained in the Lassaigne’s test
U

for nitrogen is due to the formation of NO2

(a) Iron (II) hexacyanoferrate (III) CH3 NO2
JO

(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
U

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
ED

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
(a) %N = (b) %N = 1.4VW (a) B > D > A > C (b) B > D > C > A
N V (c) A > B > C > D (d) B > C > D > A
VNW 1.4 VN 93. The decreasing order of nucleophilicity among the
(c) %N = (d) %N =
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
 20
(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

.IN
2
(c) sp, sp , sp 3 (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
AL 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
N
(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
R

the following represents its R-configuration? (c) sp, sp2, sp3 and sp2 (d) sp, sp3, sp2 and sp3
107. Which of the following compounds will exhibit cis-trans
U

C2 H 5 C2 H5
| | (geometrical) isomerism?
(a) H - C - CH3 (b) Cl - C - CH3 (a) Butanol (b) 2-Butyne
JO

| | (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
U

| | acidic character will be :

(c) H - C - Cl (d) H3C - C - Cl (a) III > II > IV > I (b) II > III > I > IV
ED

| | (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
(b) 3-Ethyl-4-ethenyl heptane
(c) 3-Ethyl-4-propyl hex-1-ene
(d) 3-(1-ethylpropyl) hex-1-ene
112. The IUPAC name of the following compound is
Cl CH2CH3
C C
CH3
(a) trans-2-chloro-3-iodo-2-pentene
(b) cis-3-iodo-4-chloro-3-pentene
(c) trans-3-iodo-4-chloro-3-pentene
(d) cis-2-chloro-3-iodo-2-pentene
113. The IUPAC name of
(a) 3-ethyl-4, 4-dimethylheptane
(b) 1, 1-diethyl-2,2-dimethylpentane
(c) 4, 4-dimethyl-5,5-diethylpentane
21
117. The alkene that exhibits geometrical isomerism is :
(a) 2- methyl propene (b) 2-butene
(c) 2- methyl -2- butene (d) propene
118. The number of stereoisomers possible for a compound of
the molecular formula
CH3 – CH = CH – CH(OH) – Me is:
(b) 2 (c) 4 (d) 6 (d) 3
119. Out of the following, the alkene that exhibits optical isomerism is
I (a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
(c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
120. The IUPAC name of the following compound is OH
(a) 4-Bromo-3-cyanophenol
(b) 2-Bromo-5-hydroxybenzonitrile
is (c) 2- Cyano-4-hydroxybromobenzene CN
(d) 6-Bromo-3-hydroxybenzonitrile Br
121. Hyperconjugation involves overlap of the following orbitals
(a) s-s (b) s - p (c) p- p (d) p-p

.IN
(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
(c) renders the ring basic
(d) deactivates the ring towards nucleophilic substitution.
AL (c) only sp 3 (d) sp2 and sp3
123. Which one of the following conformations of cyclohexane
115. The correct decreasing order of priority for the functional is chiral?
N
groups of organic compounds in the IUPAC system of
(a) Boat (b) Twist boat (c) Rigid (d) Chair.
nomenclature is
R

(a) – COOH, – SO3H, – CONH2, – CHO 124. Directing influence of the methyl group can be explained on
(b) – SO3H, – COOH,– CONH2, – CHO the basis of
U

(c) – CHO, – COOH, – SO3H, – CONH2 (a) inductive effect (b) electromeric effect
(d) – CONH2, – CHO, – SO3H, – COOH (c) resonance effect (d) no-bond resonance
JO

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
U
ED
 22

Hints & Solutions

EXERCISE - 1 1°
CH 3
1. (c) No. of asymmetric carbon = 2 |
1° ° 2° 1°
No. of enantiomers = 22 = 4. 11. (d) CH 3 -4 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
stable due to less crowding.

.IN
that is CH2O. So, percentage of carbon in both of them
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
| |
CN CN CN5
|
AL 1° 2° | | 1°
H3C - H 2 C - CH - C - CH 3
3° | 4°
CH3
N
IUPAC name is 3-cyanopentane-1,5-dinitrile
1°
1 2 3 16. (a)
R

5. (a) CH 3 - O - CH 2 - CH 2 - CH 2 - O - CH 2 CH 3
17. (c) 2
3-ethoxy-1-methoxypropane 1
U

3
7
S 4 6
JO

1 5
CH3
Bicyclo [4, 1, 0] heptane
6. (b) H 2
Cl 18. (d)
U

Cl 3
H H
|
19. (c) H3C - CH 2 - C*- CH 3
ED

C2H5
|
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
 23
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 *

.IN
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.
CH3 CH3
AL nitrophenol due to presence of intramolecular hydrogen
bonding. Since p-nitrophenol is less volatile in steam
than o-nitrophenol hence they can be separated by
N
H OH HO H
and steam distillation.
HO H H OH
36. (c) IR spectroscopy is used for the purification of
R

CH3 CH3 cyclohexanone from a mixture of benzoic acid, isoamyl

U

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.
JO

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
U

agricultural products. | |
29. (a) Clockwise rotation.
CH3 - C* - C* - C 2 H5
ED

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
 24
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

.IN
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 AL 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
N
cis trans
molecules.
43. (d) The parent hydrocarbon of C3H3 Cl 3 is C3 H6 , i.e.
H H
R

3
CH3 2 CH = 1CH 2 . Three chlorine atoms can be C=C CH3
H C=C *
present in following ways.
U

H CH(Cl)CH3
(i) Cl3CCH = CH 2 * marked carbon atom is chiral.
JO

Cl 49. (d) (i) C2H5OC2H5

| diethyl ether
(ii) Cl 2 CHC = CH 2 (ii) CH3OCH2 CH2 CH3
U

methyl propyl ether

(iii) Cl2 CHCH = CH 2 Cl
(iii) CH3 - O - CH - CH3
ED

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
 25
51. (b) Among the given compounds naphthelene is volatile 62. (a).
but benzoic acid is non-volatile (it forms a dimer). So, O
the best method for their separation is sublimation,
which is applicable to compounds which can be (a) CH = CH – OH CH2 – CH
converted directly into the vapour phase from its solid enol form keto form
state on heating and back to the solid state on cooling.
Hence it is the most appropriate method. (b) O O cannot tautomerise
52. (c) The free rotation across C – C gives rise to many spatial
arrangements. These ar rangements are called
conformers and property is called conformation. (c) O OH O, OH
53. (a) Maximum number optical isomers of a compound having
O keto form O OH OH
n assymetric carbon atoms is 2n. enol form
54. (c) Chiral molecules are those molecules which have atleast
one asymmetric carbon atom (a carbon atom attached
(d) O OH , OH
to 4 different groups). This is true in case of
3-methylpentanoic acid.
O O enol form OH
H keto form
|
63. (d) Benzoic acid, camphor and naphthalene sublime on

.IN
C2 H5 – C - CH2 COOH
| heating hence, they are purified by sublimation method.
CH3 64. (d) Due to + I-effect of the CH3 group, toluene has much
55. (d) Kjeldahl’s method depends upon the fact that most of higher electron density in the ring than benzene,
the organic compounds containing nitrogen are
quantitatively decomposed to give (NH4)2SO4 when
AL nitrobenzene and benzoic acid as they show – I-effect
and hence is most reactive towards nitration.
heated strongly with conc. H2SO4. In this method 65. (c) Compound given in option (c) is the only compound
N
CuSO4 acts as catalytic agent. which do not have any chiral carbon atom. Thus, it is
56. (a) Given structures are representing cis-trans isomerism achiral i.e. do not show optical activity.
R

(geometrical) hence differ only in configuration. 66. (b) In the presence of UV rays or energy, by boiling chlorine,
57. (a) free radical is generated which attack the methyl carbon
U

58. (d) A and B are enantiomers. atom of the toluene.

59. (d) –CH3 group has electron donating inductive effect
CH3 CH2
JO

which decreases with replacement of each hydrogen D

atom by chlorine atom. Hence highest amount of m– +H
substituted product will be obtained on nitration of benzyl free
radical
Cl
U

Cl 2 ¾¾® 2Cl•
hn
C Cl
Cl •CH CH2Cl
ED

2 •
+ Cl

60. (b) In diphenylmethane monochlorination at following 67. (d) SN1 reactions involve the formation of carbocation,
positions will produce structured isomers 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
CH2 m ech a n ism . Th us decr ea si n g or der of S N 1
mechanisms follows order Benzyl > allyl > tertiary
alkyl halide> secondary alkyl halide > primary alkyl
1 halides
2 3 4
Å
Cl CH2 CH2 CH2Cl CH2
– Cl
(1) Cl (2)
Cl
(Benzyl cation)
CH2 CH
Obtained from SN1 path. This molecule is resonance
Cl (3) (4) stabilised.
61. (c) Nitroethane (C2H5NO2) can exhibit tautomerism among 68. (d) Styrene can be purified by vacuum distillation.
the given kinds of isomerism due to the presence of a- 69. (a) Among the three given hybrid orbitals, sp hybrid orbital
hydrogen which is labile and form nitrolic acid. is most electronegative. Contribution of s in sp hybrid
O OH orbital is maximum so this orbital is closer to nucleus.
H3 C – CH2 – N H3 C – CH = N Naturally it will have greater tendency to pull electron
O O
 26
towards it. Hence it becomes more electronegative and 80. (d) Due to + M effect of the – OH group in phenol, electron
sp3 becomes least electronegative. density in the ortho and para positions of the phenol
70. (b) It is a coupling reaction of diazonium salt. nucleus increases hence phenol will undergo
In it the aromatic ring undergoing attack by diazonium electrophilic substitution easily than benzene. The other
ion must contain a powerful electron releasing group, three compounds have electron withdrawing groups,
generally –OH, –NR2, –NHR or –NH2. Substitution hence they will undergo electrophilic substitution with
usually secures para- to the activating group. a difficulty than benzene.
It has been established experimentally that coupling is 81. (d)
electrophilic aromatic substitutions. H
s
O O 82. (d) H s C s s
CºN
sp 3 || sp 3 sp3 || s 2p
71. (a) H3 C - C - CH 3 ; CH3 - C - OH ;
sp 2 sp 2 H
Acetone Acetic acid Therefore, the number of s and p bonds in acetonitrile
are 5 and 2 respectively.
O 83. (c) An asymmetric carbon atom is that in which all different
sp3 sp sp3 || groups are attached with carbon. Option (c) is correct.
C H3 - C º N ; CH3 - C - NH2 84. (b) Electrophiles are electron deficient or positively charged
sp 2
species.

.IN
Acetonitrile Acetamide
85. (b)
72. (c) Cl–
is the best leaving group among the given option. 86. (b) Methyl carbanion is sp3 hybridised, with three bond
73. (b) The order of stability of free radicals pairs and one lone pair same is the case with NH3.
• • •
(C6 H 5 ) 3 C > (C 6 H 5 ) 2 CH > (CH 3 ) 3 C > (CH 3 ) 2 C H
The stabilisation of first two is due to resonance and
• AL
87. (d) —NO2 group is electron attractive group, so it is able
to deactivate the benzene ring.
Cl
last two is due to inductive effect.
N
74. (d) Steam distillation is used for the purification of volatile NO2
compounds.
R

75. (c) The strength of nucleophile depends upon the nature

of alkyl group R on which nucleophile has to attack NO2
U

and also on the nature of solvent. The order of strength hence withdrawl of electrons from ortho and para
of nucleophiles follows the order : position cause easy removal of –Cl atom due to
JO

CN– > I– > C6H5O– > OH– > Br– > Cl– development of +ve charge on o- and p positions.
76. (c) CF3COOH has highest acidity due to –I effect of F. 88. (d) Optical inactivity due to internal compensation is
77. (b) The chemistry of the Lassaigne’s test of nitrogen is exhibited by meso-tartaric acid. Option (d) is correct.
U

89. (a) Electron withdrawing group (–NO2) increases acidity

D
Na + C + N ¾¾® NaCN while electron releasing group (–CH3, –H) decreases
ED

From organic
compound acidity. Also effect will be more if functional group
present at para position then ortho and then meta.
2NaCN + FeSO 4 ¾¾
® Fe(CN) 2 + Na 2SO 4 90. (d) Absolute alcohol cannot be obtained by simple
Fe(CN)2 + 4NaCN ¾¾
® Na 4[Fe(CN) 6 ] fractional distillation because a Constant boiling
Sod. ferrocyanide azeotropic mixture is formed. It is impossible to get pure
ethanol by distiling any mixture of ethanol and water
3Na 4 [Fe(CN)6 ] + 4Fe3+ ¾¾
® Fe 4[Fe(CN) 6 ]3 + 12Na +
(Ferric ferrocyanide)
containing less than 95.6% of ethanol. This particular
(Prussian blue) mixture of ethanol and water boils as if it were a pure
78. (c) Isoelectronic species has same number of electrons. liquid. It has a constant boiling point, and the vapour
No. of electrons in different species composition is exactly the same as the liquid.
+ 91. (c) Simple distillation is suitable for liquids which boil
NH3 = 7 + 3 = 10; CH 2 = 6 + 2 - 1 = 7 without decomposition at atmospheric pressure. In case
- - of liquids which decompose before their boiling point
CH 2 = 6 + 2 + 1 = 9; CH 3 = 6 + 3 + 1 = 10 is reached, vaccum distillation is used. Glycerine
+ decomposes at its boiling point (298°C) but can be
CH3 = 6 + 3 - 1 = 8 distilled unchanged at 12 mm pressure at 180°C.
O 92. (d) In aromatic acids presence of electron withdrawing
|| substituent e.g. –NO2 disperses the negative charge
79. (a) In present case, -C - OH is the only group whose of the anion and stablises it and hence increases the
key atom (atom attached to benzene carbon) is having acidity of the parent benzoic acid.
a multiple bond (one of the characteristics of m-directing Further o-isomer will have higher acidity than
groups). corresponding m and p isomers. Since nitro group at
 27
p-position have more pronounced electron Therefore, the correct order of reactivity towards
withdrawing than –NO2 group at m-position hence the electrophile is
correct order is the one given above. C6H5OH > C6H5CH3 > C6H6 > C6H5Cl
COOH COOH 102. (c) Out of the given compounds the most reactive towards
OH
<
NO2 electrophilic attack is . Phenol forms phenoxide
COOH COOH
ion which is stable due to resonance i.e. the correct
NO2 answer is option (c).
< < 103. (a) In the molecule
CH3 CH = CH CH 2 CH- CH 3,
NO2 |
93. (b) The stronger the base the more is the nucleophilic Br
character and vice versa. the number of stereoisomers is given by sum of
Basic character geometrical isomers (because of presence of C = C)
and optical isomers (because of presence of chiral
CH 3O - > CN - > CH3 COO - > H 3C -
–
SO3 carbon atom).

94. (a) 1,2-dihydroxybutane has longest carbon atom chain of
4 atoms and OH groups attached on it at first and
second carbon atoms. So the choice (a) is correct.
95. (b) – I group destablises carbocation and since inductive
effect decreases with increasing length of carbon chain.
AL
104. (d) The stability of carbanions is affected due to resonance,
Therefore (b) is the correct option.
N
96. (b) Being immiscible liquids, they form different layers
hence can be separated with the help of separating
R
.IN
Number of geometrical isomers = 2 (one C = C is
present).
Number of optical isomers = 2 (one chiral carbon atom).
Total number of stereoisomers = 2 + 2 = 4
inductive effect and s - character of orbitals. Greater
the number of groups having + I group (alkyl group)
lesser stable would be the carbanion.

funnel. Further stability of carbanion decreases with decrease

97. (c) Simple distillation can be applied for the separation in s-character. Benzene carbanions are stablized due to
U

and purification of a mixture of two or more liquids resonance, hence the correct order is
provided their boiling points differ at least by 30 K. In
JO

such cases, the low boiling (more volatile) liquid of the R - C = C > R 2C = CH> > R C – CH
3 2
mixture will distil over first. The temperature of the
distillation flask is then raised when high boiling (less The correct order of stability of given carbanion is in
volatile) liquid of the mixture will distil, it is collected in the order I > III > II > IV.
U

a separate flask. 105. (b) C – 1 is sp hybridized (C º C)

98. (c) Pentanoic acid and 2-methyl butanoic acid are chain C – 3 is sp3 hybridized (C– C)
ED

isomers. C – 5 is sp2 hybridized (C = C)

CH3CH2CH2CH2COOH ¾¾ ® Thus the correct sequence is sp, sp3, sp2.
CH3
| CH3 CH3
H3C - CH 2 - HC - COOH sp 3 | sp 2 sp 3 | sp
106. (d) CH3 C CH = CH CH — C º C H
2 7 6| 5 4 3 2 1
C2H5 CH3
3 107. (d) Alkenes with double bonds cannot undergo free
99. (b) Cl — C — CH3 rotation and can have different geometrical shapes with
1 two different groups on each end of the double bond.
H 4 CH3 CH3 CH3 H
C=C C=C
R-configuration H CH3
H H
100. (a) Nucleophilicity increases down the periodic table.
cis-But-2-ene trans-But-2-ene
I - > Br - > Cl - > F- OH
101. (c) Electrophiles have high affinity for electrons. They
attack at the site where electron-density is highest. ON2 NO2
108. (a) > CH3COOH >
Electron donating groups increases the electron
density. The electron donating tendency decreases in
the order : NO2
–OH > –CH3 > –H > –Cl (III) (II)
 28
OH OH O O
|| ||
–COOH > –SO3H > – C - NH 2 > - C - H
> 116. (a) CH3
|
(IV) (I) 1 2 3
H3C- - CH3
C
Explanation : Presence of three — NO 2 groups in |
o–, p– positions to phenolic groups (in III) makes CH3
phenol strongly acidic because its corresponding Neopentane
or 2, 2- Dimethylpropane
conjugate base is highly stabilised due to resonance.
117. (b) H3C CH3 H3C
Conjugate base of CH3COOH, II (i.e. CH3 COO - ) is H
C=C C=C
resonance hybrid of two equivalent structures. The
conjugate base of phenol, IV is stabilized due to H H H CH3
resonance (note that here all resonating structures are *
118. (b) CH 3 – CH = CH – CHCH 3
not equivalent). The conjugate base of cyclohexanol, I |
does not exhibit resonance, hence not formed. OH
109. (a) Tertiary alkyl halide is most reactive towards exhibits both geometrical as well as optical isomerism.
cis - R cis - S
nucleophilic substitution because the corresponding trans - R trans - S
carbocation (3°) is most stable. Aryl halide is least

.IN
119. (c) For a compound to show optical isomerism, presence
reactive due to partial double bond character of the C – of chiral carbon atom is a necessary condition.
Cl bond. H
Presence of — NO 2 groups in ortho and para positions |
increases the reactivity of the – Cl towards
nucleophiles.
AL H 2 C = CH — C* — CH 2 - CH3
|
(CH3)3 – C – X > (CH3)2 – CH2 – X > CH3
N
III IV 3- methyl-1-pentene
X 120. (b) – CN has highest priority. Further the sum of locants is
7 in (b) and 9 in (d).
R

X
NO2 121. (b) Alkyl groups with at least one hydrogen atom on the
a-carbon atom, attached to an unsaturated carbon
U

>
atom, are able to release electrons in the following way.
NO2
JO

II I
or I < II < IV < III
110. (d) Cl– is the weakest base and hence better leaving group
111. (a) The given compound is
U

2 1 Note that the delocalisation involves s and p bond

CH = CH2 orbitals (or p orbitals in case of free radicals) ; thus
ED

it is also known as s – p conjugation. This type of

CH3 — CH2 — CH2 — CH — CH — CH2 — CH3 electron release due to the presence of the system
3 4
H—C—C = C is known as hyperconjugation
CH2 – CH3
5 6 sp 2 sp sp 2
4 ethyl- 3-propyl hex – 1 – ene 122. (b) Allene (C3H4) is H 2 C = C = CH 2
4 5
112. (a) Cl CH2CH3 123. (b) Chiral conformation will not have plane of symmetry.
C=C Since twist boat does not have plane of symmetry it is
2 3
CH3 I chiral.
1
Correct IUPAC name of above compound is 124. (d) Methyl group can’t produce electromeric and
trans-2-chloro-3-iodo-2-pentene resonance effects. Inductive effect affects all the three
CH3 positions of the ring in decreasing order of ortho >
7 6 5 4| 3 2 1 meta > para. It shows hyperconjugation (no-bond
113. (a) CH3 - CH 2 - CH 2 - C - CH - CH 2 - CH3 resonance) which explains beautifully the o, p-directing
| |
CH3 CH 2 influence of the -CH 3 group.
| 125. (d) Taking any two halogens, the possible structural
CH3 isomers for the alkene can be three.
3-ethyl -4,4- dimethyl heptane
114. (a) Nitro group is electron withdrawing group, so it F C = C Br F Cl F Cl
I
C = C C=C
deactivates the ring towards electrophilic substitution. Cl Br I I Br
115. (a) The correct order of priority for the given functional Each of the three alkene can exist as E and Z isomer,
group is making total number of isomers as six.