Organic Compound Qualitative Analysis

Classisfication Purification Quantitative Analysis

Methods
Acyclic or Halogens
open chain Carbon and Hydrogen
Cyclic or Sodium Extract is acidified m-Mass of org. Compound
Alicyclic Compounds O Closed chain Distillation with conc. HNO3 and 12 × m 2 × 100 2 × m 1 × 100
%C = %H = M2-mass of co2 produced

—
—
— , treated with silver nitrate.

—
44 × m 18× m M1-mass of H2 produced

—
—

—
Heterocyclie Differential Extraction Nitrogen
Homocyclic Sulphur
Aromatic Compunds Compounds
Compounds Sodium Exract is acidified Dumas method Kieldahl's method m-Mass of org. Compound
with acetic acid and lead acetate 28 × V × 100
N-Normality of acid
%N = 1.4× N × V V-Volume of acid
Crystallisation is added %N =
, o 22400 × m m
Benzenoid Hologen
compounds Nitrogen
NH2
Ring chain isomerism Chromatography Carius method
Non-benzenoid Sodium extract is boiled with iron at.mass of × M 1 × 100 m-Mass of org. Compound
and (II) sulphate, then acidified with %halogen =
compounds molar mass of Ag × m M1-mass of AgX formed
, conc. H2SO4
o But - 1 - ene cyclobutane Sublimation Sulphur

Phosphorous Carius method

Structural Isomerism 32 × m 1 × 100 m-Mass of org. Compound
Position Isomerism Tautomeris m Compound is treated with %S =
OH oxidising agent, then boiled 233 × m M1-mass of BaSo4 formed
OH O OH with HNO3 and ammonium molybdate.
CH3 - C - H CH2 = C - H Phosphorus
Compounds that true
same chemical formula Keto form enol form × m 1 × 100 m-Mass of org. Compound
Propane - 1 - ol %P = 62
but different chemical Propan - 2 - ol Carbon & Hydrogen 222 × m M1-mass of Mg2p2O7 formed
bond arrangement by heating with copper (II) oxide
are called structural
isomers. metamerism Functional Isomersim
O
O Organic Reaction Bond
Fission
O Types
Parts of Iupac methoxy propane ethyoxyethane
propanal
CHO
Organic Chemistry : Homolytic
propanone free radicals are fomed.
Name
Some Basic Addition reaction
Heterolytic
Chain Isomerism
. Prefix Principles and Techniques Substitution reaction Carbocation and carbanion
is formed.
. Root word
Elimination reaction
. Primary suffix
Pentane 2 - methyl butane 2,2 - Dimethyl propane Electronic displacement
. Secondary Suffix
Effect Electrophile Nucleophile
Hyperconfugation Effect
Electron deficient species. Electron rich species
Rules for IUPAC Naming delocalisation of s electrons of C-H
Inductive Effect
Lewi's acid. + lewi's base.
ISOMERISM bond of an alkyl group directly Example-Cl+, Br+, NO2, Example- H2O, NH3 , OH,
Rule 1 : Select the longest possible attached to an atom with CH3, AlCl3, etc. Cl , F , CH3
unshared p-orbital. Partial displacement of sigma
carbon chain. electrons towards more
electronegative atom/Group.
Rule 2 : Numbering of parent chain is done It is a permanent effect
from that side where functional group, Electromeric Effect Attaching Reagent
multiple bond and substituent get Stereo Isomerism
the lowest number. Compounds that have same In the presence of reagent, +I Effect -I Effect
the double or triple bonds get Organic molecule Intermedite Products(s)
chemical formula and sequence broken double or It is a CH3 , C3H5 , etc. -CN , -COOH , etc.
Rule 3 : Lowest sum rule — If first substituent temperory effect.
gets same number from all side then of covalent bonds but differ
chain selected should have lowest sum in spatial arrangement are
of all subtituent numbering.
called stereo isomers Resonance Effect Corbocation Carbanion Free Radical
Rule 4 : Alphabet rule — Naming should be done • Carbon atom having a positive • Carbon atom having a negative • Carbon atom having 7
in alphabitical order if the numbering When a molecule can be represented charge with only six electron charge on it. electron in the valance shell
of all substituent is same. by two or more structures which in its valence shell. • Carbonion carbon is sp3 hybridised. is called carbon free radical.
have same arrangement of atoms • Carbocation carbon is sp2 • Carbon of free radical is Sp2
Rule 5 : It the molecule have more than one but differ in distribution of hybridised. hybridised.
functional group, the functional group electrons is called resonance. - - - -
Geometrical Optical Isomerism + + + +
with highest prriority receives the +R Effect -R effect C > CH > CH2 > CH3 CH3 > CH2 > CH > C C > CH > CH2 > CH3
lowest number. Isomerism halogen, -OH, OR -COOH, -CHO, -CN
 GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

BASIC PRINCIPLES & TECHNIQUES IN

ORGANIC CHEMISTRY (GOC)

Introduction
‘The branch of chemistry dealing with these compounds, which are widely distributed in
nature and play an important role in our daily lives’, is called organic chemistry.

In earlier period of development of chemistry, compounds were classified as follows

1. Organic compounds derived from ‘living matter’ (plants and animals).
2. Inorganic compounds prepared from ‘non-living matter’ (mineral sources).
Berzelius, a Swedish chemist proposed the mistaken notion that a ‘vital force’ present in
living matter was essential for the synthesis of organic compounds. However, the synthesis
of urea an organic compound present in urine, from ammonium cyanate, an inorganic
compound by Frederic Wohler in 1828 effectively destroyed the myth of organic compounds
being associated with a ‘vital force’.

Soon afterwards the pioneering work of Herman Kolbe who synthesized acetic acid and of
Berthelot who synthesized methane showed conclusively that organic compounds are
essentially the compounds formed by carbon with itself and other elements and that they
can be synthesized in a laboratory as easily as inorganic compounds.

CH 3 − CHO ⎯[⎯→
O]
CH 3 − COOH
Acetic acid
Acetaldehyde
(First organic compound synthesized from its elements)

The chemistry of hydrocarbons and their derivatives constitutes organic chemistry.

The number of organic compounds available today is more compare to total inorganic
compounds of all elements except carbon. This is due to unique catenation property of
Carbon.

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Some properties of Carbon

• Catenation: is the property of an element where a large
number of its own atoms join together through covalent
bonds. Due to which it forms single as well as multiple
covalent bonds with other carbon atoms. It is further
supplemented by the fact that it also forms covalent bonds
with atoms of other elements like hydrogen, oxygen,
nitrogen, Sulphur, phosphorus and halogens in a variety of
ways (i.e., single and multiple bonds).
This property gives a scope for the Chemists to synthesize new compounds.
• Tetravalency of carbon atom
The atomic number of carbon is 6 and it has four electrons in its valence shell. In order to
acquire a stable noble gas configuration, it can share its 4 electrons with the electrons of its
atom or electrons of other atoms to form four covalent bonds. The bonds can be sigma(σ) or
pi(π).

2s2 2p2 2s1 2p3

energy

Ground state Excited state

Alkanes → CnH2n+2 Alkenes→CnH2n Alkynes→CnH2n–2

As per Lewis theory, Carbon can easily form tetra-bonds with other carbon atoms & other atoms. C-C,
C=C, C≡C exists in nature but not Carbon-Carbon tetrabonds.
Carbon can form single, double or triple bond (covalent). When a single bond is formed between carbon
atoms (or any atoms), energy is released. Changing the molecule's electron arrangement to make a
double bond releases more energy, but not as much as when the first bond was made. Making a triple
bond again releases energy, but again to a lesser degree. However, when a fourth bond is attempted,
the overcrowded electrons between the atoms resist the change so strongly that it releases little, if
any, energy. This arrangement is therefore unstable, so a quadruple bond will be essentially impossible.
• Hybridization in carbon compounds
Hybridization is defined as intermixing of degenerate orbitals (orbitals at nearly same
energy) to produce entirely equivalent number of new orbitals of same energy, identical
shapes and symmetrically disposed in planes. The orbitals formed are called hybrid
orbitals.

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➢ The orbitals of an isolated atom can undergo hybridization.

➢ Numbers of hybrid orbitals generated are equal to number of contributing atomic orbitals.
➢ The hybrid orbitals orient in the space providing definite geometry to molecule or ion.
➢ Like atomic orbital, a hybrid orbital cannot have more than two electrons of opposite spins.
In diamond carbon is sp3 hybridized and in graphite carbon is sp 2 hybridized.
There are three types of hybridization,
(i) sp3 hybridization (contain saturated organic compounds with only single covalent bonds)
(ii) sp2 hybridization (here organic compounds having carbon atoms linked by double bonds)
(iii) sp hybridization (here organic compounds having carbon atoms linked by a triple bonds).
Type of hybridization sp3 sp2 sp

Number of orbitals used 1s and 3p 1s and 2p 1s and 1p

Number of unused p-orbitals Nil One Two

Bond Four - Three -, One - Two -, Two -

Bond angle 109.5 120 180

Geometry Tetrahedral Trigonal planar Linear

% s-character 25 or 1/4 33.33 or 1/3 50 or 1/2

Prediction of hybridization- It can be done by two methods,

(i) First Method: In this method hybridization can be known by the number of  − bonds
present on that particular atom.
Number of – bond/s 0 1 2
3 2
Type of hybridization sp sp sp
O (ii)
(i) || CH 2 = C = CH 2
CH3 − CH = CH −C − CH 3   
    
sp 2 sp sp
2
2
sp3 sp sp 2 sp 2 sp3

(iii) (iv) HC  C − CH = CH 2
CH 3 − CH = CH − CH 2 − C  N
         
sp3 sp
2
sp 2 sp3 sp sp sp sp sp 2 sp 2

(ii) Second Method (Electron pair method): The hybridized state of an atom of a molecule
or an ion or radical can be predicted by calculating number of orbitals or electron pairs
involved in hybridization (H) which is evaluated as follows.
H = (number of  bonds formed with adjected atom/s + number of lone pairs of electrons
ep = bp + lp;
where, ep = electron pair present in hybrid orbitals,
bp = bond pair present in hybrid orbitals
Number of bp = Number of atoms attached to the central atom of the species (do not include  electron pairs).

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Value of H 2 3 4
Hybridization sp sp2 sp3
Structure linear trigonal planar tetrahedral
Central atom
First atom H
H
C=C
Second atom H H
bp = 3
Third atom
Central atom
1 2
H − C  C− H 2
1
H

bp = 2
3
bp = 3

Number of lp’s can be determined as follows,

(a) If C has  - bonds or positive charge or odd electron, than lp on C will be zero.
(b) If carbon has negative charge, then lp will be equal to one.
Example:
   • 
CH 2 = CH CH  C CH 2 = CH CH 2 = C − CH 3 CH3 − CH − CH3
   | 
bp=1 bp=3
bp = 2 lp = 1
bp = 2
lp = 0 lp = 1
CH 3 lp = 1
ep = 2,sp bp = 3 ep = 4,sp3
ep = 2,sp ep = 3,sp 2 lp = 0
ep = 3,sp 2

Pitfall - It may be noted that, the hybridized state of a heteroatom containing lone
pair electrons or carbanion or free radical bonded in conjugation with multiple bond/s is
sp2. For example, hybridized state of allylic or benzylic carbanions or free radicals or
atoms of aromatic ring is sp2.

Problem 1: How many sigma () and pi () bonds are present in each of the following
molecules? a) CH2 = C = CH2 b) CH3 – CH = CH – C  C – CH3
Solution: Every single bond is a  bond; every double bond contains one −bond and one
−bond while every triple bond consists of one − and two −bonds. Thus
a) C−C : 2, C−H : 4, C−C : 2 b) C−C : 5, C−H : 8, C−C : 3
Problem 2: Predict the shape of each of the following molecules.
a) HC  CH b) CH3Cl c) H2C = O
Solution: sp hybridization can always be correlated to tetrahedral shape, sp2 to trigonal
3

planar and sp to linear. Thus,

a) sp hybridized carbon atoms, linear
b) sp3 hybridized carbon, tetrahedral
c) sp2 hybridized carbon, trigonal planar

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Applications of hybridization
(i) Size of the hybrid orbitals: Since s- orbitals are closer to the nucleus than p-orbitals, it
is reasonable to expect that greater the s-character of an orbital the smaller it is. Thus, the
decreasing order of the size of the three hybrid orbitals is opposite to that of the decreasing
order of s orbital character in the three hybrid orbitals. sp3  sp 2  sp
(ii) Electro negativity of different orbitals
(a) Electro negativity of s-orbital is maximum.
(b) Electro negativity of hybrid orbital  % s-character in hybrid orbitals
Orbital sp sp 2 sp3
% s -character 50 33.33 25
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
s-character in decreasing order and electronegativity in decreasing order
Thus sp-hybrid carbon is always electronegative in character and sp3-hybrid carbon is
electropositive in character. sp 2 -hybrid carbon can behave as electropositive (in carbocation)
as well as electronegative (in carbanion) in character.
 
CH3 − CH 2 CH 2 = CH

sp 2 sp

Electropositive carbon Electronegative carbon

having positive charge

(c) Electro negativities of hybrid & unhybrid orbitals in decreasing order is as follows
2 3
s  sp  sp  sp  p
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
% s-character and electronegativity in decreasing order.
(iii) Bond length in hydrocarbons,% of s orbital character  1

1
C − C bond length C − H bond length
Bond type (C – H) Bond length Bond type (C – C) Bond length
sp − s (alkanes)
3
1.112Å sp − sp (alkanes)
3 3
1.54 Å
sp − s (alkenes)
2
1.103Å sp − sp (alkenes)
2 2
1.34Å
sp − s (alkynes) 1.08Å sp − sp (alkynes) 1.20Å

(iv) Bond strength in hydrocarbons: The shorter is the bond length, the greater is the
compression between atomic nuclei and hence greater is the strength of that bond.
Bond type(C – H) Bond energy (kcal/mole) Bond type (C – C) Bond energy (kcal/mole)
3 3 3
sp -s (in alkanes) 104 sp -sp (in alkanes) 80 – 90
sp2-s (in alkene) 106 sp2-sp2 (in alkenes) 122 – 164

sp-sp (in alkynes) 121 sp-sp (in alkynes) 123 – 199

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Structural representation of Organic Compounds

Structural formula (structure) is the sequence in which different atoms constituting the
molecule are bonded to one ano0ther. Structures of molecules of organic compounds can be
described in various ways. The most common types of representations are:
1) Lewis structure (or electron dot structure) Here dots are used to represent all of the
valence electrons of all the bonded atoms in the molecule:
H H H
H C H H C C H H C C H
H Ethene Ethyne
Writing dot structure is tedious and time–consuming. The other representations are more
convenient and are, therefore, more often used.
2) Dash structural formula The Lewis structure can be simplified by representing a shared
electron pair by a ‘stick’ (dash, −) between the bonded atoms. When there is one dash
between two atoms, the atoms are said to be bonded by a single covalent bond. A double
covalent bond, in which two pairs of electrons are shared, is shown by two dashes between
the atoms. A triple bond is represented by three dashes between the atoms.
The valence electrons that are not included in covalent bonds are called nonbonding
electrons (lone pairs). These are assigned to specific atoms and are represented by dots
drawn next to the symbols for these atoms.
Lone pair of electrons on hetero atoms (e.g. oxygen, nitrogen, sulphur, phosphorus, halogens)
may or may not be shown. Such structural formulae which focus only on the valence
electrons involved in bond formation are called complete structural formulae.

H H H H
| | | |
H − C− C− H H − C = C− H H−C  C −H
| |
H H
Ethane Ethene Ethyne
H H H H
| gg | | gg |
H − C− Cl
gg
g
g or H − C − Cl H − C − O
gg
− H or H − C −O −H
| | | |
H H H H
Methyl chloride Methyl alcohol
chloromethane methanol

3) Condensed structural formula Complete structural formulae can be shortened by leaving

out some or all of the covalent bonds and by denoting the number of identical groups
attached to an atom by a subscript. The resulting description of the molecule is called a
condensed structural formula. Thus,
CH3CH3 H2C = CH2 HC  CH CH3CH2Cl
or or or or
C2H6 C2H4 C2H2 C2H5Cl
Ethane Ethene Ethyne Ethyl Chloride

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CH3CH2CH2OH CH3CH2CH2CH2CO2H
or or
CH3(CH2)2OH CH3(CH2)3CO2H
Methanol Pentanoic acid
Condensed structural formulae are easier to write than dash formulae. In condensed formulae
all of the hydrogen atoms that are attached to a particular carbon are usually written
immediately after the carbon. In fully condensed formulae, all of the atoms that are attached
to the carbon are usually written immediately after that carbon, listing hydrogens first.
For example, the condensed formula for isopropyl alcohol can be written in four different
ways:
CH3 CHCH3 CH3CH ( OH) CH3 CH3 CHOHCH3 or(CH3 )2 CHOH
⏟
|
condensedformulae
OH

4) Bond-line structural formula: For further simplification only lines are used to represent
the structures of organic molecules. Here carbon and hydrogen atoms are not shown. The
lines denoting the carbon – carbon bonds are drawn in a zig – zag fashion. The only atoms
especially written are the hetero atoms (oxygen, nitrogen etc). They are neither carbon nor
hydrogen bonded to carbon. The termini describe methyl (CH3 − ) groups (unless denoted
otherwise by a functional group). The line junctions indicate carbon atoms bonded to
suitable number of hydrogens needed to satisfy the covalency of the carbon atoms: Thus
The bond-line representation is the quickest of all to write because it shows only the carbon
skeleton.
CH3

a) CH3CH2CH2CH(CH3)CH2CH2CH2CH3 ⎯⎯⎯
step 1
⎯→ CH2 CH CH2 CH3

CH3 CH2 CH2 CH2

Step 2

Line junctions denote carbon atoms

Terminals describe methyl groups

Cl

CH CH2

b) CH3CHClCH2CH2CH3 ⎯⎯⎯→
step1
CH3 CH2 CH3
step 2

Cl

CH2 CH2 CH2 CO2H

c) CH3(CH2)6CO2H ⎯⎯⎯→ step1

CH3 CH2 CH2 CH2
Step 2

OH

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Ring or cyclic compounds - An organic compound in which carbon atoms are not bonded in
chain but are bonded in closed structures called rings are known as cyclic compounds. Such a
compound containing one or more rings is represented by drawing the suitable ring (polygon)
without indicating the carbon and hydrogen atoms. The corner of the polygon denotes a
carbon atom and its sides represent a carbon – carbon bond. An atom or a group of atoms
(other than hydrogen) bonded to the carbon is however shown in the structure.
Bond–line formulae of some cyclic compounds are:
CH2
CH2 H2C CH2
H2C CH2

H2C CH2 H2C CH2 H2C CH2

Cyclopropane Cyclobutane Cyclopentane
OH CO2 H
OH CO2 H
CH CH

H2C CH2 H2 C CH2

H2C CH2 H2 C CH2

CH2 CH2
Cyclohexanol Cyclohexane carboxylic acid

Multiple bonds are also indicated in bond-line formulae.

For example:
H3 C CH CH3
C H2 C

CH3
CH2 CH CH 2 OH .

OH
Exp 1: Convert each of the following Lewis structures into complete structural formulae:
O H
a) H C O H b) H C N c) H C Cl
H
Solution: Use the dash to represent the shared electron pair.

H H
gO g
g O | gg |
a)
g
|| || b) H – C  N: or H – C  N c) H − C − Cl
gg or
g
g H − C− Cl
gg
H− C − O − H or H − C− O − H | |
gg H H
Exp2: Convert each of the complete structural formulae into condensed formulae.
H H H H H H H
a) | |
H − O − C− C− N− H
b) | | | | |
H − C− C  C − C − C − C − C − H
| | | | | | | |
H H H H H H H H
H O H H H H H
c) H − C| − C|| − C| − H d) H − C| − C| − C| − C| − N = O
| | | | | | 
H H H H H H O
Solution: Omitting some or all of the dashes and indicating the number of identical groups by
a subscript we get
a) HO(CH2)2NH2 b) CH3C  C(CH2)3CH3 c) H3CCOCH3 d) CH3(CH2)3NO2

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Exp 3: Write the condensed structural formulae for the compound that follows in different
ways.
H H H H

H C C C C H

H H H
H C H

Solution: CH3− CH CH2CH3 or CH3CH ( CH3 ) CH2CH3 or CH3 CH2 CHCH3

| |
CH3 CH3
or ( CH3 )2 CHCH2CH3 or CH3 CH2CH ( CH3 )2

Exp 4: Write the bond–line formula for H3C− CH−CH2− CH2− CH2− OH
|
CH3
Solution: First, outline the carbon skeleton, including the OH group as follows:
H3C CH2 CH2 C C
C
C C OH
CH CH2 OH
C
CH3
Thus, the bond–line formula is .
OH

.
Exp 5: For following condensed formulae write the corresponding bond-line formula.
a) (CH3)2CH(CH2)2CH2OH b) CH3(CH2)4CHICH2CHO
c) (CH3)2CHCH3CH(CH2)3NO2 d) (CN)2CHCH2COCl
Solution: In bond-line formula carbon and hydrogen atoms except those that are part of the
functional groups are not shown. We show only the carbon skeleton. The number of hydrogen
atoms necessary to fulfill the carbon atoms’ valences is assumed to be present, but we do not
write them in. Other atoms (e.g., Cl, O, N) are written in. Each intersection of two or more
lines and the end of a line represent a carbon atom unless some other atom is written in.
CH3

a) (CH3)2 CH (CH2)2CH2OH ⎯⎯⎯→ step1

CH CH2 OH

CH3 CH2 CH2

Step 2

OH

I
b) CH3(CH2)4CHICH2CHO ⎯⎯⎯→
step1
CH2 CH2 CH CHO
CH3 CH2 CH2 CH2

step 2

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. NO 2
c) (CH3)2CHCH3CH(CH2)3NO2 ⎯⎯⎯
step 2
⎯→

.
CH2 Cl
NC
CH C
d) (CN)2CHCH2COCl ⎯⎯⎯→ step1

CN O
step 2

Cl
NC
C

CN O

Exp 6: Draw all possible bond-line formulae for a cyclic compound, C5H10.
Solution: Start with the maximum number of carbon atoms in the ring and move towards the
ring of 3 carbon atoms. Explore all sorts of possibilities on this route:

Three-dimensional representation of organic molecules

None of the formulae that we have described so far conveys any information about how the
atoms of a molecule are arranged in space. Shape or the three-dimensional (3-D) structure
of organic molecules can be described on a paper (two-dimensional) by exploring certain
conventions. For instance, by using solid and dashed wedge formula the 3–D
image of an organic molecule can be perceived on a two-dimensional paper.
In solid-wedge and dashed-wedge description the solid-wedge denotes a bond projecting
out of the plane of the paper towards the viewer. The dashed-wedge depicts the bond
projecting behind the plane of the paper and going away from the viewer. Both the wedges
are drawn in such a way that the broad end of the wedge is near the viewer. The other two
bonds lying in the plane of the paper are shown by using a normal line ( ⎯ ).
Let’s consider the wedge- and dashed-wedge representation of methane (CH4) molecule:
H H

H or H
H H H
H

The two carbon-hydrogen bonds represented by normal lines are in the plane of paper,
whereas the carbon-hydrogen bond represented with a solid wedge is aimed to be in front of
the plane of paper. The hydrogen bonded to carbon by dashed wedge is intended to be
behind the plane of paper. Note that the carbon atom is lying in the plane of paper.
Wedge and dashed-wedge formulae are an important tool for clearly showing three
dimensions.

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Classification of organic compounds

The compounds with C and H are called hydrocarbons. Organic compounds are considered as
the derivatives of hydrocarbons obtained by replacing H-atoms by other atoms or groups.
Based on C - skeleton, organic compounds divided as below,
1. Acyclic compounds - The open chain organic compounds are called acyclic compounds.
The carbon chains may be linear or branched.
The open chain compounds are classified into two groups.
a. Saturated compounds: Open chain compounds in which carbon atoms of parent chain are
bonded with single bonds are called saturated acyclic compounds.
Example:
CH3CH2CH2CH3 O CH3
CH − CH − CH || |
n–Butane 3 3
H − C− H
| CH3 −C− OH
CH3 |
Formaldehyde CH3
Isobutane
tert-Butyl alcohol
b. Unsaturated compounds: The open chain organic compounds in which parent chain contains
one or more carbon-carbon double bonds or triple bonds are called unsaturated acyclic
compounds.
CH3 CH3
CH2 CH2 CH3CH CH2 CH3CH CHCH3 CH3C CHCH3 CH3 CH C CH
ethylene propene 2-butene 2-methyl-2-butene 2-methyl-1-butyne

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2. Cyclic Compounds – Here carbon atoms are linked by covalent bonds to form ring
structures are called cyclic compounds. Depending upon the constituents of ring, these
compounds are further classified into two groups.
A. Carbocyclic compounds (Homocyclic compounds): The cyclic compounds containing only
carbon atoms in their ring are called carbocyclic compounds. They are further divided into
two groups.
➢ Alicyclic compounds: The carbocyclic compounds which resemble with aliphatic
compounds in most of their properties are called alicyclic compounds.
H2
C H2 C CH2
or or
H2 C CH2 H2 C CH2
cyclopropane cyclobutane

H2 H2
C C
H2 C CH2 H2 C CH2
or or
H2 C CH2 H2 C CH2
C
cyclopentane H2 cyclohexane

Aromatic compounds: Benzene is the parent aromatic hydrocarbon. The organic compounds
containing one or more isolated or fused benzene rings and their functionalized derivatives
are called aromatic compounds or benzenoid compound.
CH3
OH CHO

benzene naphthalene diphenyl toluene phenol benzaldehyde

The aromatic compounds which resemble benzene in most of their properties are called non-
benzenoid aromatic compounds.

O
azulene tropolone

➢ Heterocyclic compounds: The cyclic compounds containing one or more heteroatoms

(atom other than C it may be O, N, S, etc.,) in their ring are called heterocyclic
compounds. Depending upon their chemical behaviors, they are further classified into
two groups.
i. Alicyclic heterocyclic compounds: The aliphatic cyclic compounds containing one or more
hetero atoms in their ring are called alicyclic heterocyclic compounds.
O O H2C CH2
or or
CH2 N
H2 C CH2 H2C
O O H
oxirane (ethylene oxide) tetrahydrofuran (THF) pyrrolidine
or epoxide

ii. Aromatic heterocyclic compounds: The aromatic cyclic compounds containing one or
more hetero atoms in their molecules are called aromatic heterocyclic compounds.

O N N S
furan pyrrole pyridine thiophene
H

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Organic Compound

Open chain/Acyclic/Aliphatic Closed chain/Cyclic/Aliphatic

Hydrocarbon Containing
functional Homocyclic/ Heterocyclic
group Carbocyclic [Ring having at least one
[Ring having only hetero Atom][N, O, S]
Saturated C atoms]
Unsaturated
Ex :- Alkane
CnH2n+2
Alicyclic Aromatic
Alicyclic Aromatic
Ex :- CH2–CH2
Alkene Alkyne Alkenyne Containing O
CnH2n CnH2n–2 CnH2n–4 Alternate O
– and = Bond Oxirane
[C=C] [C  C] [C=C–CC] Cyclo Cyclo Furan
CH2–CH2
Propane Butane Ex :-
Cl
CH2–CH2
O NH
Benzene Tetra hydrofuran Pyrrole
Cyclo Cyclo Chloro (THF)
Pentane Hexane benzene CH2–CH2
S
CH2–CH2
Thiophene
Nephthalene NH
Pyrrolidine
N

Anthracene Pyridine

Functional groups: is defined as “an atom or group of atoms present in a molecule which
decides the chemical properties of the organic compounds”.
Double and triple bonds are also considered as functional groups.
The organic compounds are further classified into different classes depending upon the
nature of functional group. Classification of organic compounds based on functional group is
summarized in the table.

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Homologous Series
A series of structurally related organic compounds with same functional group can be
represented by a general formula and differ by -CH2 group is called homologous series.
The individual members of such series are called homologue and this phenomenon is known
as homology.

Characteristics of a homologous series are as follows.

• Each homologues series can be represented by general molecular formula.
Exp - General molecular formula of alkane is CnH2n+2. Molecular formula CnH2nO2
represents alkanoic acids (carboxylic acids) and alkyl-alkanoates (esters).
• All members of a given homologous series (homologues) possess the same functional group.
• The successive members of a homologous series differ by a -CH2- group or by mass units.
• Homologues of a homologous series can be prepared by general methods.
• The physical properties such as boiling point, melting point, density, etc., of the members
of a homologues series show a regular gradation with increase in molecular mass.

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• Chemical properties of the members of a homologous series are similar though the first
homologue may vary considerably from the rest of the homologues.

Nomenclature of Organic Compounds

The nomenclature deals with the naming of millions of organic compounds. The following
systems are employed.
1. Trivial system (common system)
It is the oldest system of naming organic compounds. In the early stages of the development
of organic chemistry, organic compounds were named after the source from which they were
first isolated. Generally, the names chosen had Latin or Greek roots. The following illustrations
justify the statement.

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2. IUPAC System - Saturated hydrocarbons are the parent compounds and other organic
compounds as their derivatives obtained by substituting one or more hydrogen atoms
with functional groups. IUPAC name of any organic compound may consist of three parts.
“prefix-root word-suffix”.
IUPAC system for naming is something that is very similar to addressing a person with his
complete designation.

a. Root word – is assigned to organic molecule based on the number of carbon atoms
present in the main parent chain
No. of C atoms Root word Molecular formula Molecular structure IUPAC name
1 Meth CH4 CH4 Methane
2 Eth C2H6 CH3CH3 Ethane
3 Prop C3H8 CH3CH2CH3 Propane
4 But C4H10 CH3(CH2)2CH3 Butane
5 Pent C5H12 CH3(CH2)3CH3 Pentane
6 Hex C6H14 CH3(CH2)4CH3 Hexane
7 Hept C7H16 CH3(CH2)5CH3 Heptane
8 Oct C8H18 CH3(CH2)6CH3 Octane
9 Non C9H20 CH3(CH2)7CH3 Nonane
10 dec C10H22 CH3(CH2)8CH3 Decane
11 Undec
12 dodec

b. Suffix – is based on the nature of bonds and functional group present in the molecules.
It is of 2 types,
• Primary suffix: A primary suffix is added next to the root word to indicate whether the
parent chain is saturated or unsaturated.

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Type of carbon chain root word primary suffix generic name

Saturated (C-C single bonds) alk ane alkane

Unsaturated [C=C bond] alk ene alkene

Unsaturated [−CC−] alk yne alkyne

Note: A carbon-carbon double bond or triple bond must be included in parent chain even if it
contains less number of carbon atoms.
• Secondary suffix added next to the primary suffix to indicate the presence of a functional
group in organic compounds which determines the class of organic compounds.
Secondary suffix of a few functional groups are given.
Functional group Structure Secondary suffix Class of organic compounds

Hydroxyl –OH - ol Alcohols

Aldehydic O
- al Aldehydes
C H

Ketonic C O - one Ketones

Carboxy O
-oic acid Carboxylic acids
C OH

Ester O
alkylalkanote Esters
C OR

Amino –NH2 - amine Amines

Note - While adding the secondary suffix, the letter ‘e’ of the primary suffix (i.e., ane, ene
and yne) is dropped if the secondary suffix begins with a vowel (a, e, i, o or u). It is retained
if secondary suffix begins with a consonant.
c. Prefix (substituent)
All the groups which are not names in parent chain and functional groups are called as
substituents. Its name placed before the root word.
Exp – Alkyl group, halo atoms, nitro group
Substituents group Prefix
-CH3 Methyl
-C2H5 Ethyl
-NO2 Nitro
-Cl Chloro
-OR Alkoxy
–C–C– Epoxy
O
-NO Nitroso

Alkyl groups – derived from an alkane, by removing a hydrogen atom bonded to carbon.
These groups are named simply by dropping –ane from the name of the corresponding alkane
and replacing it by –yl. R is a general symbol, general formula for an alkyl group is CnH2n+1,
because it contains one less hydrogen atom than the parent alkane, CnH2n+2.

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Alkane Alkyl group Abbreviation

Methane, CH4 Methyl, CH3− Me−
Ethane, CH3CH3 Ethyl, CH3CH2− or C2H5− Et −
n – propyl, CH3CH2CH2−
Propane, CH3CH2CH3 Isopropyl, CH3CHCH3 n-Pr – or Pr – i-Pr−
|
n-Butyl, CH3CH2CH2CH2−
n-Bu– or Bu–
n-Butane, CH3CH2CH2CH3 sec – Butyl, CH3 CH2CHCH3
| s-Bu–

Isobutyl, CH3CHCH2
|
CH3 i-Bu–
Isobutane, CH3CHCH3
| CH3
CH3 |
tert–Butyl, CH3−C−
| t-Bu−
CH3

Among the alkyl groups we encounter the problem of isomerism.

• While only one alkyl group can be derived from methane (the methyl, CH3−)
• Ethane (the ethyl, CH3CH2−)
• Two or more alkyl groups can be derived from higher alkanes.
Exp – (1) From propane (C3H8), two alkyl groups can be derived. Removal of one of the
hydrogens from one of the end carbon atoms gives an alkyl group that is called the propyl
group or n-propyl group.
→ CH3 CH2CH2 − or n − Propyl
−H
CH3 CH2CH3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯
from endcarbon
Propane Propyl
Removal of one of the hydrogens from the middle carbon atom gives an alkyl group that is
called the isopropyl group.
−H
CH3CH2CH3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → CH3CHCH3
Propane frommiddlecarbon |
Isopropyl

Both these alkyl groups contain the propane chain, but differ in the point of attachment of
the group to the rest of the molecule.
(2) There are four butyl groups, two derived from the straight–chain n-butane, and two
derived from the branched–chain isobutane. These are given the designations: n− (normal),
sec– (secondary), iso– and tert– (tertiary) as shown below:
−H
−H
CH3−CH 2CH 2CH 2 − from a terminal CH 3−CHCH 2−
from a terminal carbon |
n-Butyl group
carbon CH 3
Isobutyl group
CH3CHCH3
CH3CH2CH2CH3 |
n-Butane CH3
−H |
−H CH 3−C− CH 3
CH 3CH 2C HCH 3 from the central |
from the | carbon CH 3
non-terminal carbon sec− Butyl group tert-Butyl group

CH3 CH3

CH3 CH2 CH2 CH2 CH3 CH3 CH CH2 CH3 CH3 C CH3
n-pentane iso-pentane CH3
neo-pentane

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An alkyl group is described as,

❖ primary if the carbon at the point of attachment is bonded to only one other carbon,
❖ as secondary if bonded to two other carbons,
❖ tertiary if bonded to three other carbons. Thus, if R is any hydrocarbon radical, the
different kinds of alkyl groups are
RCH2− R2CH− R3C−
Primary Secondary Tertiary

Problem 1: Classify each of the following alkyl groups as primary, secondary or tertiary:
Butyl, Isopropyl, Isobutyl, sec-Butyl and tert-Butyl.
Solution: Primary alkyl group is RCH2 −
CH3CH2CH2CH2− CH3CHCH2−
Butyl |
CH3
Isobutyl
Secondary alkyl group is
CH3CH2
CH3
R CH − CH −
CH − CH3 H3C
R Isopropyl sec - Butyl

R
R C

Tertiary alkyl group is

CH3
(tert-Butyl)
R
|
CH3 −C−
|
CH3

 Prefix n-(normal) is used for those alkanes in which all the carbon atoms form a
continuous chain with no branching.
CH 3 CH 2CH 2CH 3 ; CH 3 CH 2 CH 2 CH 2 CH 3
n − Butane n − Pentane

 Prefix iso is used for those alkanes in which one methyl group is attached to the next-to-
end carbon atom (second last) of the continuous chain.
CH 3 − CHCH 3 CH 3 − CH − CH 2 CH 3 CH 3 − CHCH 2 CH 2 CH 3
| | |
CH 3 CH 3 CH 3
Isobutane Isopentane Isohexane

 Prefix neo is used for those alkanes which have two methyl groups attached to the second
last carbon atom of the continuous chain.
CH 3 CH 3
| |
CH 3 − C − CH 3 CH 3 − C − CH 2 − CH 3
| |
CH 3 CH 3
Neopentane Neohexane

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Rules for naming of open chain Organic compound.

Rule 1 - Longest chain rule (root word rule)
The continuous carbon chain containing maximum carbon atoms including the function group
is selected. It is called the parent chain. For one to four carbon atoms of the parent chain,
special root words are used but for chains of five or more carbon atoms Greek number roots
are employed.
The generic root word for any parent chain is ‘alk’.
Priority order: Functional group > Multiple bond (= or ) > Substituent
Substituents
CH 3
|
Parent chain
CH 3 − CH − CH 2 − CH 2 − C − CH 2 − CH 3
| |
CH 3 CH 3
CH3
| Substituents
CH3 CH2
| |
CH3 − CH − CH − CH3 - substituted pentane
Similarly, the following hydrocarbon will be regarded as a substituted hexane because the
longest continuous carbon chain (parent chain/ root chain) contains six carbon atoms.
CH3 − CH2 − CH2 − CH2 − CH − CH3 Substituted hexane
|
CH3

CH3 ( CH2 )3CHCH3CH2CH3 → CH3 − CH2 − CH2 − CH2 − CH − CH3 Substituted heptane
|
CH2
|
CH3

CH2CH3 CH2CH2CH2CH3
| |
CH3CH2CHCH3 ( CH2 )2 CHC2H5 ( CH2 )3 CH3 → H3C −CH− CH2 − CH2 − CH− CH2CH3
substituted decane

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Note:
• If two different chains of equal length are possible, the chain with maximum number
of side chains or alkyl groups is selected.
• Number used to specify the position of the substituents is called locant.

Rule 2 - Lowest sum rule (rule of locant)

Parent carbon chain is numbered using Arabic numerals 1, 2, 3, 4, 5..... in such a way that
functional group or substituents containing carbon receive least number.
CH3
| 1 2 3 4 5 6 7 3
5
CH3 − CH − CH 2 − CH 3 6 5 4 3 2 1 2 6 4 4 6 2
1 3 4 8
2 CH 3CH 2 CH 2 CH 2 CH CH 3
1 3 5 7 1 
4 3 |
2 1
CH 3
8 

1 2 3 4 5 5 CH 3 1
7 6 5 4 3 |
CH 3CH 2CH 2CH 2− CH−CH 3 CH34 CH 2 2
| | | 9 8 7 6 5 4 3 2 1
2CH 2 6 CH3 − CH − CH − CH3 1 2 3 4 5 6 7 8 9
1 2 3 CH3CHCH 2CH2CH2CHCH 2CH2CH3
|
5 4 3
1CH 3 7 CH3 CH2CH3

 When the parent chain contains two or more substituents, the numbering is done from the
end where the sum of the locants is least.
CH3
6 5 4 3 2 1 (2 + 5 + 5 = 12, wrong)
CH3 C2 CH2 CH2 CH CH3
1 2 3 4 5 6
CH3 CH3 (2 + 2 + 5 = 9, correct)

 Parent chain with one substituent: Prefix the name of the substituent to the root word
of parent chain and indicate its position. The name of the substituent is separated from its
locant by a hyphen (-). Name of the organic compound is written as one word.
1 2 3 4 1 2 3 4 5 6
1 2 3
CH3 CH CH3 CH3 CH CH2 CH3 CH3CH2 CH CH2CH2CH3

CH3 CH3 CH2CH3

2-methylpropane 2-methylbutane 3-ethylhexane
 Naming of different substituents: When two or more different substituents are
present on the parent chain, they are named in alphabetical order along with their
appropriate locants.
1 2 3 4 5 6 7 1 2 3 4 5 6 7 8
CH3 CH CH2 CH CH2CH2CH3 CH3 CH CH2CH2CHCH2CH2CH3
CH3 CH2CH3 Cl CH3
4-ethyl-2-methylheptane 2-chloro-5-methyloctane
 Numbering of different substituents at equivalent positions: If two different alkyl or
halo groups are present at equivalent positions, the numbering of the parent chain is done in
such a way that the substituent which comes first in the alphabetical order gets the lower
number.

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CH2 CH3
6 5 4 3 2 1 correct numbering
CH3 CH2 CH CH CH2CH3
1 2 3 4 5 6
incorrect numbering
CH3

3-ethyl-4-methylhexane (NOT 3-methyl-4-ethylhexane)

Br
1 2 3 4 correct
CH3 CH CH CH3
4 3 2 1 incorrect
Cl
2-bromo-3-chlorobutane (NOT 3 - chloro-2-bromobutane)
 Presence of the same substituent more than once: If the same substituent occurs
more than once, the prefixes di, tri, tetra are prefixed to the name of the substituent. It
may be noted that the position and name of the substituent are separated by a hyphen (-)
whereas the numerals representing the positions of the substituents are separated by
commas.
CH3 CH2CH3 CH3

CH3 CH CH CH3 CH3 CH CH CH C CH3

CH3 CH3 CH3

2, 3-dimethylbutane 4-ethyl-2,2,5-trimethylhexane
 Naming a complex substituent: In case the substituent on the parent chain is complex
(i.e., it has a branched chain), it is named as a substituted alkyl group by numbering the
carbon atom of this group attached to the parent chain as 1. Name of complex substituent is
enclosed in bracket to avoid confusion with the numbers of parent chain.
CH3
1 2
CH3 CH CH3 CH3 CH CH CH3
1 2 3
CH3 CH2 CH2 CH CH2 CH2 CH3 CH3CH2CH2CH2CHCH2CH2CH2CH3
1 2 3 4 5 6 7 1 2 3 4 5 6 7 8 9

4-(1-methylethyl)heptane 5-(1, 2-dimethylpropyl)nonane

If same complex substituent occurs more than once on the parent chain, prefixes bis, tris,
tetrakis, etc., are used before the name of the complex substituent.
The application of IUPAC rules to the structure of a molecule to arrive at IUPAC name
is illustrated as follows.
CH2 CH3
CH3 CH CH CH CH3
5 4 3 2 1
CH3 Br

• Parent chain has 5 carbon atoms, and it has more number of substituents. The root word is
‘pent’.
• Primary suffix is ‘ane’
• Sum of locants is 9, the substituent which comes first in alphabetical order gets the lower
number.
• Prefixes to the rootword are bromo, ethyl and methyl. Hence, IUPAC name is
• “2-bromo-3-ethyl-4-methylpentane”
•

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A few examples are given below:

CH3 Br CH3
CH3 C CH2 CH CH3 CH3 CH CH CH CH2 CH3
1 2 3 4 5 1 2 3 4 5 6
CH3 CH3 CH2 CH3

2,2,4-trimethylpentane 2-bromo-3-ethyl-4-methylhexane
1 2 3 4 5 6 1 2 3 4 5 6 7 8 9
CH3CHCH 2CH2CH2CH3 C H 3C H C H 2C H 2C H 2C H C H 2C H 2C H 3
| |
CH3
CH 3 CH 2CH 3
2−Methylhexane 6–Ethyl–2−methylnonane
CH3
1 2 3 4 5 6 7 1 2 3 4 5 6 7
CH3CH2CHCH2CH2CH2CH3 CH3 CH 2 C CH 2CH2CH2CH3
|
CH3 CH2
CH3
3−Methylheptane 3–Ethyl–3–methylheptane
1 2 3 4 5 6
C H 3C H −C H 2CHCH2C H 3
| |
4–Ethyl–2–methylhexane
CH 3 CH 2
|
CH 3
not
2–Methyl–4−ethylhexane because ethyl comes before methyl alphabetically

1 2 3 CH 3 CH3 CH3
C H 3− C H− C H − CH 3 2 |3 4
| | 1 5 1| 3 4| 5
2

CH 3 4 CH 2
C H 3C H C HCH−CH 3 C H3−C − CH2− C− C H 3
| | | |
| CH3 CH3
5
CH 3
CH 3 CH 3

2, 3 – Dimethylpentane 2, 3, 4 – Trimethylpentane 2, 2, 4, 4 – Tetramethylpentane

CH 3CH 2 CH 3 CH 3
1 2 | 3 |4 5 6 7
8 7 6 5 4 3 2| 1
C H 3C H 2CH − C − C H 2C H 2CH 3 CH 3CHC H 2CH 2− CHCH 2− C − CH 3
| | | |
CH 3 CH 3 CH2CH3 CH 3
3 – Ethyl – 4, 4 – dimethylheptane 4 – Ethyl – 2, 2, 7− trimethyloctane

8 10 7 5 3 1
2 3 4 5 6 7 9
1 6 4 2
8

4,5–Diethyl–3, 6-dimethyldecane 5-Ethyl–2, 2–dimethyloctane

(“di” not considered in alphabetical ordering)
CH3

1 CH CH 3
1 2 3 4 5 6 7 8 9 10
7 6 5 4 3 2 CH3CH2CH2 CH CH CH 2CH2CH2CH2CH3
8
H3C CH CH 2 CH 3
5–(1, 1-Dimethylethyl)−3−ethyl-6-methyloctane 5–sec–Butyl– 4−isopropyldecane
(“di” is being part of substituent name)

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1 2 3 4 5 6 7 8 9
2 CH3CH2CH2CH2 CH CH 2CHCH 2CH3
CH3
1CH
1 2
CH3 CH
1 2 3 4 5 6 7 2
CH3 C CH3
CH3CH2CH2CHCH 2CH2CH3
3 CH
3
4 – Isopropylheptane 5-(2, 2–Dimethylpropyl)nonane
or
4–(1–Methylethyl)heptane
CH2CH3
10 9 8 7 6 5 1 2 3 4
CH3CH2CH2CH2CH2 CH CH 2 CH CH 2CH3

4 CH2

H3C C CH 3
3
CH2 CH 3
2 1
5–(2–Ethylbutyl)–3, 3–dimethyldecane
N.B. Longest chain selected has maximum number of side chains.
Naming of organic compounds containing a functional group
Prefix and suffix names of a few common functional groups and their decreasing order of
priority are given in the table.

Group Prefix name Suffix name Class of organic compounds

−COOH − -oic acid Carboxylic acids

−COOR − alkyl....oate Esters

−COX − -oyl halide Acid halides

−CONH2 carbamoyl -amide Amides

−CHO formyl -al Aldehydes

−CO oxo -one Ketones

−OH hydroxyl -ol Alcohols

−NH2 amino -amine Amines

− -ene Alkenes
C C

−CC− − -yne Alkynes

−X (halogen) halo − Alkyl halides

−NO2 nitro − Nitroalkanes

−OR alkoxy − Ethers

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It may be noted that the groups -R, -OR, -NO2, -X, etc. are considered as substituents
and are indicated as prefixes.
1. Longest chain- The parent chain is the one which has functional group directly attached
to it, even if it violates the longest chain rule.
2. Numbering of parent chain-The numbering should be done in such a way that the carbon
linking to the functional group gets the lowest number even if it violates the lowest sum
rule or locant rule.
When the functional group itself contains carbon atom, then that carbon atom is assigned as
number 1.
3. Naming of compounds with polyfunctional group- If there is more than one functional
group present in a compound, then one of the functional group is chosen as the principal
functional group (secondary suffix) and the remaining functional groups are treated as
(substituents) subordinate functional groups.
The functional group with higher priority in the sequence given below is termed as principal
functional group.

1. Write the correct IUPAC names of the following bond line formula:
Me

O
C
O
(i) (ii) (iii) (iv)
Cl H3CO
O OMe
Me Me OH Me Et

H OH Me Me Me
HO H Me Me
(v) Me (vi) (vi) H H (vii) Me COOH

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 GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

O
Me
N CHO

(ix) O (x) (xi) (xii)

Me Me

O
(xiii) H H (xiv) O
Answers
(i) 2-Methylpropanoyl chloride (ii) Methyl propanoate
(iii) Methyl 2-ethylbutanoate (iv) 5-Ethyl-4, 6-dimethyloct-1-ene
(v) Butane-2,3-diol (vi) 5,6-Diethyl-3-methylundec-4-ene
(vii) 3-Methyl cyclopentam-1-ol (viii) 7-Ethyl-6-methylundec-6-cnoic acid
(ix) Ethyl propanoate (x) N-Ethyl-N-methyl propan-1-amine
(xi) Hex-3-yne (xii) 3-Ethyl-4-methylpentanal
(xiii) 2,3-Dimethyloxirane (xiv) Tetrahydrofuran

2. Write the IUPAC names of the following compounds:

(i) HOH2C –CH = CH – CH2OH (ii) H2C = C –CH2–CH2–OH
CH3

(iii) HC = C–CH2–CH2–CH–CHO (iv) CH3COCOOH

Cl
O
(v) CH2–CH – CHO (vi) CH3–CH – C – CH – OCH3
OH Cl CH3 CH3

–CH–CCl3
(vii) (viii) C H –CH = CH – COOH
6 5

O
(ix) CH3–CH – C – CH – OCH2CH3 (x) CH2–CH–CH2
OCH3 CH3 OH OH OH
O CH3
(xii) –O–C–CH–CH3 (xiii) [(CH3)2CH]3COH

CH3
(xiv) (CH3)3COH (xv) CH3–CH2 – CH – C – CH2Cl
Br Br
NO2
(xvi) CH3CH2CH(CHO)CH2COOH (xvii)
H2N NO2

3. Write correct IUPAC names of the following polyfunctional compounds:

(i) CH2 = CH–CH2Cl (ii) CH3CH CHCH2OH
CH3
CH–C(OCH3)CHO CH3–CH–COOH
CH3
CH3 CH2CHO
(iii) (iv)

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 GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

O O
(v) CH3–C–CH2CH3 (vi) CH3–C–C–OCH2CH3
CH2OH
OO O O
(vii) CH3–C–C–OCH2OCH3 (viii)
H–C–C–OH
O
(ix) CH3CH2N–C–H (x) CH3CH2CHCH2CN
Cl
4. Write IUPAC names of the following compounds:
(i) CH3OCH2CH2CH2OC2H5 (ii) HOCH2CHCHO
NH2
O
(iii) CH3–C–N–CH2CH3 (iv) HC=C–CH=CH–CH3
H
OH
(v) CH3–C–COOH
H
Answers
1. (i) –C = N> –C– > –OH (ii) –SO3H > –COCl > –CHO
(i) –COOR > –CONH2 > –CHO
2. (i) But-2-ene-1, 4-diol (ii) 3-Methyl-but-3-en-l-ol
(iii) 2-Chlorohex-5-yn-l-al (iv) 2-Ketopropanoic acid
(v) 2-Chloro-3-hydroxypropanal (vi) 2-Methoxy-4-methylpentan-3-one
(vii) 1,1,1-Trichloro-2,2-diphenylethane (viii) 3-Phenylprop-2-en-l-oic acid
(ix) 2-Ethoxy-4-methoxypentan-3-one (x) Propane 1,2,3-triol
(xi) 2-Methoxybenezoic acid (xii) Phenyl 2-methylpropanoate
(xiii) 2,4-Dimethyl-3-(1-nethylethyl) pentan-3-ol (xiv) 2-Methylpropan-2-ol
(xv) 2,3-Dibromo-1-chloro-2-methylpentane (xvi) 3-Formylpentanoic acid
(xvii) 2,4-Dinitro benezamine
3. (i) 3-chloroprop-1-ene (ii) butane-1,2,3-triol
(iii) 2-Methoxy-2,3-dimethylbutanal (iv) 3-Formyl-2-methylproanoic acid
(v) 2-Ethyl-3-hydroxy-2-methyl propanal (vi) Ethyl-(2-oxo) propanoate
(vii) 1-Methoxy-2-3,-butanedione (viii) Formylmethanoic acid
(ix) N-Chloro-N-ethyl methanamide (x) 2-Ethyl-butane-1,4-dinitrile
4. (i) 1-Ethoxy-3-methoxypropane (ii) 2-Amino-3-hydroxypropanal
(iii) N-Ethyl ethanamide (iv) Pent-3-en-1-yne
(v) 2-Hydroxypropanoic acid

Nomenclature of substituted benzene compounds

Benzene is a six membered cyclic compound with alternate single and double bonds. It is
represented in any one of the following ways:

or
(i) Naming of monosubstituted benzene
It is derived by adding the name of the substituent with the word benzene.

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Substituent + benzene → substituted benzene

CH3 Br NO2

Example:
methylbenzene bromobenzene nitrobenzene
Special names of some monosubstituted benzene compounds
Molecular formula Structural formula IUPAC name Special name
CH3
C6H5CH3 methylbenzene Toluene

NH2
C6H5NH2 benzenamine Aniline

OH
C6H5OH phenol Phenol

C6H5CHO CHO Benzene Benzaldehyde

Carbaldehyde

C6H5COOH Benzene Benzoic acid

COOH
Carboxylic acid

C6H5OCH3 OCH3 methoxybenzene Anisole

If the functional group is attached to the carbon chain connected to benzene ring, then
benzene ring is considered as substituent and is prefixed before the root word as phenyl.
Example: CH CH CHO CH CH Cl
2 2 2 2

3-phenylpropanal 2-phenylchloroethane
(ii) Naming of disubstituted benzene
(a) If the substituents are same: In such case, the relative position of the substituents
must be indicated by adding the symbols o − (1, 2) ; m − (1, 3) ; p − (1, 4).
X o-ortho : positions 2, 6
1
2
m-meta : positions 3, 5
6
p-para : positions 1, 4
5 3
4
In the trivial system of nomenclature, the terms ortho(o), meta(m) and para(p) are used as
prefixes to indicate the relative positions 1, 2-; 1, 3 and 1, 4-respectively.

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 GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Cl NO2 SO3 H
Cl

Example: NO2
SO3 H
1,2-dichlorobenzene 1,3-dinitrobenzene 1,4-benzenedisulphonic acid
(or) o-dichlorobenzene (or) m-dinitrobenzene (p-benzenedisulphonic acid)
(b) If the two substituents are different, they are named in the alphabetical order.
I Cl

NO2
Br
1-bromo-4-iodobenzene 1-chloro-3-nitrobenzene
(or) p-bromoiodobenzene (or) m-chloronitrobenzene
(c) If there are more than two substituents: The numbering is done in such a way that it
satisfies the lowest sum rule.
Cl 1 COOH
3

CH3 2
1
2 Cl 4 3
Br NO2
1-bromo-3-chloro-2-methylbenzene 4-chloro-3-nitrobenzoic acid

Nomenclature of Bicyclo compounds

(i) Bicyclo compounds contain two fused rings with the help of a bridge. We use the name of
the alkane corresponding to the total number of carbon atoms as the base name. The
carbon atoms common to both the rings are called bridge heads, and each bond or chain
of atoms connecting the bridgehead atoms called a bridge.
(ii) While naming the bi-cycloalkane we write an expression between the word bicyclo and
alkane (in square bracket), that denotes the number of carbon atoms in each bridge. The
numerals are written in descending order and the numbers are separated by a point.
(iii) If substituents are present, we number the bridged ring system beginning at one bridge
head, proceeding first along the longest bridge to the other bridge head, then along the
second next longest bridge back to first bridge head. The shortest bridge is numbered in
the last.
Example:
Bridge head
One carbon bridge
CH2 1
CH2 CH2
(1) Two carbon bridge { CH CH2
CH
}Two carbon bridge 2

3
7
6

5
Bicyclo [2, 2, 1] heptane
It's common name is norborane
2 2
CH 4

Bridge head

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7
(4)
(2) (3) 4 6

1 5
3
2
Biyclo [4.1.0] heptane Bicyclo [2.2.1] hept-2-ene Bicyclo [3.2.2] nonane
1 7 1 2

7
2 (6) CH2 CH CH2
6 3
(5) CH2
5 8 CH3 8CH
3
4
CH2 CH CH2
6 5 4
Bicyclo [2.2.2] octa-2,6-dione 8-Methylbicyclo [3.2.1] octane

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Isomerism
The existence of two or more compounds with the same molecular formula but different
physical and chemical properties is known as isomerism and the molecules themselves called
as isomers.
The term was given by Berzelius. The difference
in properties of the two isomers is due to
difference in the arrangement of atoms within
their molecules.

Isomerism is mainly classified into structural isomerism and stereoisomerism.

1. Structural isomerism
It is due to the differences in structures of the isomers. Structural isomerism is further
classified into 5 types.
(i) Chain isomerism (nuclear isomerism)
Compounds with same molecular formula but differ in the arrangement and number of
carbon atoms within the molecule are called chain isomers and the phenomenon as chain
isomerism.

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DIFFERENCES BETWEEN CHAIN ISOMERS

Chemical properties- Isomers show similar chemical properties because the same
functional group is present.
Physical Properties- such as density and boiling point show trends according to the of
the degree of branching
Boiling Point of straight chain isomers have higher values than branched ones the
greater the degree of branching the lower the boiling point branching decreases the
effectiveness of intermolecular forces less energy has to be put in to separate the
molecules

For example,
(i) Butane (C4H10) has two isomers – normal butane and isobutene. One isomer has a straight
chain and the other has a branched chain.
CH3−CH2−CH2−CH3 CH3−CH−CH3
|
n−butane CH3
isobutane
(ii) cyclohexane and methylcyclopentane are nuclear isomers.
CH3
CH2 |
CH
CH2 CH2
CH2 CH2
CH2 CH2
CH2 CH2 CH2

cyclohexane methylcyclopentane
(iii) C5H12 has three chain isomers.
CH 3
CH 3CH 2CH 2CH 2CH 3 CH 3CH 2 − CH − CH 3 CH 3 − C − CH 3
CH 3 CH 3
n−pentane Isopentane neopentane

(iv) C4H9NH2 also shows two chain isomers.

CH 3
CH 3CH 2CH 2CH 2N H CH 3 C − NH2
2 CH 3

n−butylamine tert.butylamine

Solve 1- How many chain isomers does butane have?

CH3−−CH 2CH 2 = CH 2 CH3−−C = CH 2
CH 3
n − Butylene (1 − Butene ) CH 3
Isobutylene ( 2-Methylpropene ) CH 2 CH 2 CH3 CH−−CH 3

Solve 2 - How many chain isomers does propyl benzene have?

n − Propylbenzene Isopropylbenzene

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(ii) Functional isomerism

Compounds with same molecular formula but differ in functional groups are called functional
isomers and the phenomenon is known as functional isomerism.
For example

• Diethyl ether butyl alcohol both has the molecular formation C4 H6 O, but contains different
functional groups.
C2 H5 − O − C2 H 5 C4 H9 − OH
diethyl ether butyl alcohol
Thus, functional group in diethyl ether is ( −O − ) , while is butyl alcohol it is ( −OH ) .

• Acetone and propionaldehyde both with the molecular formula C3 H 6 O are functional isomers.
CH3 − CO − CH3 CH3 − CH 2 − CHO
acetone acetaldehyde
In acetone the functional group is ( −CO − ) , while in acetaldehyde it is ( −CHO )

• Cyanides are isomeric with isocyanides;

RCN RNC
Alkyl cyanide Alkyl isocyanide

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• Carboxylic acids are isomeric with esters.

CH3CH 2COOH CH3COOCH3
Propanoic acid Methyl ethnoate
• Nitroalkanes are isomeric with alkyl nitrites:
O
R−− N R−−O −−N = O
O Alkyl nitrite
Nitroalkane

• Sometimes a double bond containing compound may be isomeric with a triple bond containing
compound. This also is called as functional isomerism. Thus, butyne is isomeric with butadiene
(molecular formula C 4 H 6 ).
CH3 − CH 2C  CH CH 2 = CH − CH = CH 2
1 – Butyne 1, 3 – Butadiene
• Unsaturated alcohols are isomeric with aldehydes. Thus,
CH 2 = CH − OH CH3CHO
Vinyl alcohol Acetaldehyde
• Unsaturated alcohols containing three or more carbon atoms are isomeric to aldehydes as well
as ketones:
CH 2 = CH − CH 2OH CH3CH 2CHO CH3COCH3
Allyl alcohol Propionaldehyde Acetone
• Aromatic alcohols may be isomeric with phenols
CH 2 OH CH 3
OH

Benzyl alcohol o − Cresol

• Primary, secondary and tertiary amines of same molecular formula are also the functional
isomers.
CH3−− N−−CH3
CH3CH 2CH 2 NH 2 CH3 − NH − C2 H5
n-propylamine (1o) Ethylmethyla min (2o) CH 3
Trimethylamine ( 3)
• Alkenes are isomeric with cycloalkanes:

CH3CH 2CH = CH 2 CH 3
Butene
Cyclobutane
Methycyclopropane
• Such isomers in which one is cyclic and other is open chain are called ring-chain isomers. Alkynes
and alkadienes are isomeric with cycloalkanes.
CH3CH 2C  CH CH 2 = CH −−CH = CH 2
1 − Butyne 1,3 − Butadinene

Cyclobutene

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(iii) Position isomerism

Compounds which have the same structure (arrangement) of carbon chain (carbon
skeleton) but differ in the position of the multiple bond or the functional group are
called position isomers and the phenomenon is known as position isomerism.
Thus the following compounds can exhibit position isomerism:
(a) Alkenes (b) Alkynes (c) Arenes d) Alkyl halides
(e) Aryl halides (f) Alcohols (g) Amines and h) Nitro compounds
a) Alkenes containing four or more carbon atoms can exhibit position isomerism due to the difference in the
position of double bond on the same carbon skeleton, For example:

i) CH3CH2CH = CH2 CH3CH = CHCH3

But-1-ene But-2-ene
ii) CH3CH2CH2CH = CH2 CH3CH2CH = CHCH3
Pent-1-ene Pent-2-ene
iii) CH3CH2CH2CH = CH2 CH3CH2CH2CH = CHCH3
Hex-1-ene Hex-2-ene
CH3CH2CH = CHCH2CH3
Hex-3-ene
b) Alkynes containing four or more carbon atoms can exhibit position isomerism due to the difference in the
position of triple bond on the same carbon skeleton. For example:
i) CH3CH2 C  CH CH3C  CCH3
But-1-yne But-2-yne
ii) CH3CH2CH2C  CH CH3CH2C  CCH3
Pent-1-yne Pent-2-yne
c) Arenes containing eight or more carbon atoms exhibit position isomerism due to the difference in the
position of alkyl groups on the benzene ring. For example:
i)
CH3 CH
3 CH 3

CH3

CH 3

CH 3

o – Xylene m – Xylene p - Xylene

ii)
CH3 CH3 CH3

CH3 CH3

H3 C CH3
CH3
CH3

1, 2, 3 – Trimethyl benzene 1,2,4– Trimethylbenzene 1, 3, 5 – Trimethylbenzene

(hemimellitene) (pseudocumene) (mesitylene)

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d) Alkyl halides containing three or more carbon atoms can exhibit position isomerism due to the difference in
the position of halogen atom on the same carbon skeleton. For example
i) C3H7Cl has two position isomers:
CH3CH2CH2Cl CH3 − CH− CH3
|
1 – Chloropropane Cl
2 – Chloropropane
ii) n – Pentane on monochlorination gives three isomeric chloropentanes:
CH3CH2CH2CHCH3 CH3CH2 CHCH2CH3
CH3CH2CH2CH2CH2Cl | |
Cl Cl
1 – Chloropentane 2 – Chloropentane 3 – Chloropentane
Polyhalogen derivatives containing two or more carbon atoms can also exhibit position isomerism. For example:
CH3CHCl2 1, 1 – Dichloroethane ClCH2CH2Cl 1, 2 – Dichloroethane
e) Aryl halides containing two or more benzene rings can exhibit position isomerism due to the difference in
the position of halogen atom. For example:
Cl
Cl

1 – Chloronaphthalene 2 – Chloronaphthalene
Polyhalogen compounds containing just one benzene ring can also exhibit position isomerism. For example:
Br
Br
Br

Br Br
Br
1, 2 – Dibromobenzene 1, 3 – Dibromobenzene 1, 4 – Dibromobenzene

f) Alcohols containing three or more carbon atoms exhibit position isomerism due to the difference in the
position of functional group ( −OH). For example :
i) The molecular formula C3H8O represents two isomeric alcohols:
CH3CH2CH2OH CH3CHCH3
|
OH
Propan-1-ol Propan-2-ol
ii) Four monohydric alcohols differing in the position of – OH group can be derived from isopentane:
OH
CH3CH− CH2CH2− OH |
| CH3CH− CHCH3
CH3 |
CH3
3 – Methylbutan-1-ol 3 – Methylbutan-2-ol
OH
| HO − CH2− CHCH2CH3
CHCCH |
3 2CH3
| CH3
CH3
2 – Methylbutan-2-ol 2 – Methylbutan-1-ol
g) Primary amines (RNH2) containing three or more carbon atoms can exhibit position isomerism due to the
difference in the position of amino group on the same carbon skeleton. For example:
NH2
|
CH3CH2CH2NH2 CH3 − CH − CH3
1 – Aminopropane 2 – Aminopropane

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h) Nitro compounds (RNO2) containing three or more carbon atoms can exhibit position isomerism due to the
difference in the position of nitro group on the same carbon skeleton. For example:
CH3 CHCH2CH3
|
CH3CH2CH2CH2NO2 NO2
1-Nitrobutane 2-Nitrobutane

(iv) Metamerism
Here two or more different compounds having the same molecular formula but different number and
arrangement of carbon atoms on either side of the functional group is called metamerism. Such
compounds are known as metamers.
Metamerism is never possible in compounds possessing the univalent functional group.
Metamerism is due to the difference in the nature of alkyl groups attached to the same polyvalent
functional group such as −C−, −Ö̤ −, −S̤̈ −, −N̈H−, −N̈ −and − C− O − .
|| |
O
||
O

Metamerism is exhibited by compounds of the same homologous series.

a) Ethers, R–O–R, exhibit metamerism due to difference in the nature of the alkyl groups
attached to the oxygen atom. Thus, the molecular formula, C4H10O, represents the following
metamers:
CH3CH2 − O − CH2CH3 CH3 − O − CH − CH3 CH3 − O − CH2CH2CH3
|
CH3
O
||
b) Ketones, R − C − R , exhibit metamerism due to the difference in the nature of the alkyl groups
attached to the carbonyl group. Thus, the molecular formula, C5H10O, represents the following
metamers:
O O O
|| || ||
CH3 − C − CH2CH2CH3 , CH3 − C − CHCH3 , CH3 − CH2 − C− CH2 − CH3
|
CH3

c) Thioethers, R–S–R, exhibit metamerism due to the difference in the nature of the alkyl groups
attached to the sulphur atom. Thus, the molecular formula, C4H10S, represents the following
metamers:
CH3 − S − CH2CH2CH3 CH3 − CH2 − S − CH2 − CH3 CH3 − S − CH − CH3
|
CH3

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d) Secondary and tertiary amines exhibit metamerism due to the difference in the nature
|
of the alkyl groups attached to the – NH – group and the − N− atom respectively. Thus
the molecular formula, C4H11N, represents the following metamers:
CH3CH2 − NH − CH2CH3 CH3 − NH − CH2CH2CH3 CH3 − NH − CH − CH3
|
CH3
O
||
e) Esters, R − C − O − R , exhibit metamerism due to the difference in the nature of the alkyl
O
||
groups attached to the − C− O − group. Thus, the following esters are metamers:
O O
|| ||
CH3CH2 − C− O − CH3 CH3 − C− O − CH2CH3
Note- If same polyvalent functional group is present in two or more organic compounds, then
instead of chain or position isomerism, treat the phenomenon as metamerism.
(i) Pentan – 2- one and pentan – 3- one are metamers and not position isomers. They can be
included in position isomerism, if metamerism is not mentioned.
(ii) Similarly, pentan – 2- one and 3 – methylbutan-2-one are metamers and not chain isomers.
Metamers may be considered as position isomers. For instance, pentan – 2- one and penta-3-
one may be regarded as position isomers as well as metamers.

(v) Tautomerism
Here a single compound exists in two readily interconvertible structures that differ in
position of hydrogen atom. Tautomer exhibits dynamic equilibrium with each other.
A very common form of tautomerism is that between a carbonyl compound containing an  -
hydrogen and its enol form. This type of isomerism is also known as keto−enol isomerism.
R' R' O OH
H O
R − C − C − R'' R − C = C − R" O H
H CH3 C CH3 CH3 C CH2
H O O−H
keto form enol form
Keto form Enol form
The percentage of enol form increases in the order simple aldehydes and ketones <
−keto esters < −diketones < −diketones having phenyl group < phenols. This
increase in the enol content is due to the fact that the enol form of the above type of
compounds is increasingly stabilized by resonance and hydrogen bonding than the
corresponding keto form.

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(vi) Ring – chain isomerism

The phenomenon of existence of two or more compounds having the same molecular formula
but possessing open chain and closed chain (cyclic structure) is called ring – chain isomerism.
This type of isomerism arises due to different modes of linking of carbon atoms. Thus ring-
chain isomers possess open chain or closed chain structures as illustrated by the following
examples:
i) Two ring-chain isomers are possible corresponding to the molecular formula C3H6:

CH3CH = CH2 and

Propene Cyclopropane
ii) Six pairs of ring-chain isomers are possible for the molecular formula C4H8:
CH3CH2CH = CH2 and
Me
CH3CH2CH = CH2 and

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CH3CH = CHCH3 and

CH 3
CH3CH = CHCH3 and

CH3 − CH = CH2
| and
CH3
CH3 − CH = CH2 CH 3
| and
CH3
iii) The molecular formula C3H4 represents the two ring – chain isomers:

and
CH3 – C  CH
Ring chain isomerism, can be included in functional isomerism, if not considered separately.

Concepts in organic reaction mechanism

The organic reactions involve the breaking of covalent bonds in the reacting molecules and
formation of new bonds to give product molecules
The organic molecule which reacts with attacking reagent is called substrate. In multistep
organic reactions, substrate react with reagent and leads to the formation of one or more
reaction intermediates. The general reaction path involving the formation of one reaction
intermediate is depicted as follows.

Organic molecule + attacking reagent [reaction intermediate] product(s) + byproduct (s)

(substrate)
Substrate + Reagent ⎯⎯→ Intermediate ⎯⎯→ Products
(Transition state)

Fission or Cleavage of covalent bond

The fission of covalent bond can take place in two ways depending on the nature of covalent
bond, nature of attacking reagent and conditions of the reaction.
Like other chemical reactions, organic reactions are also a process of bond breaking and bond
making. A covalent bond between two atoms can be broken in essentially the following ways:
R. .
X
R:X R : X
-

R :X-
1) Homolytic cleavage (Homolytic fission)
“In this type of fission bond breaks symmetrically and each fragment formed gets an odd
electron from the shared bond pair electrons”.
This cleavage results in the formation of
specie(s) with unshared electron called free
radicals. It is also known as free radical cleavage
or non-polar bond fission. The homolytic fission of a sigma () bond is shown as follows.
A – B ⎯⎯→ A• + B•

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Cl Cl
sunlight
2 Cl
.
Cl Cl
sunlight
2 Cl
. free radical
chlorine
chlorine free radical
heat or light
R
. +
.
R X X
heat or light .
alkylRradical +
.
R X halogen radical
X
alkyl radical halogen radical
The free radicals contain unpaired electron (with odd number of electrons), electrically
neutral and paramagnetic.

The conditions favorable for homolytic cleavage are

• The difference in electro negativity between A and B is less or zero.
• Homolysis takes place in gaseous phase or in the presence of non polar
solvents(CCl4, CS4), peroxide, UV light, high temperature (≥5000C),
electricity and free radical.

2) Heterolytic cleavage (Heterolytic fission)

In this type of cleavage, covalent bond breaks asymmetrically & one of the two species
gets both the electrons and other loses resulting in the formation of ions. Heterolytic
cleavage results in formation of electron deficient and electron rich fragments.
It is also known as ionic cleavage or polar bond or ionic fission.
The electron deficient fragment is called electrophile
while electron rich fragment is known as nucleophile.
In case of organic compounds, if positive charge is
present on the carbon then cation is termed as
carbocation. If negative charge is present on the
carbon then anion is termed as carbanion. The
heterolytic fission is shown below
[Electronegativity of A is greater than B]
_
A - B ⎯⎯
→ A : + B+
[Electronegativity of B is greater than A]
_
A - B ⎯⎯
→ A+ + B :

H Br H
+
+
..
Br
electrophile nucleophile

CH3 Br
+
CH3 + Br
..
electrophile nucleophile
Both electrophile and nucelophile contain even number of electrons, influenced by strong
electrical field as they possess positive or negative charge and they are diamagnetic.
• The factor which favors heterolysis is greater difference of electro
negativities between A and B.
• The energy required for heterolysis is always greater than that for
homolysis due to electrostatic forces of attraction between ions.
• Low temperature
• Polar nature of substrate and attacking reagent
• Presence of acid or base catalyst

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Reaction intermediates
Highly reactive, short lived and energetic intermediate formed in multistep organic
reactions by the action of reagent on substrate and readily transformed into product(s)
is called reaction intermediate.
The important reaction intermediates are free radicals, carbocations, carbanions, carbenes,
benzyne and nitrenes.
(i) Carbocations or Carbonium ions
A reaction intermediate formed by heterolytic fission of a covalent bond which contains
one positively charged carbon with three bond pair electrons (sextext of electrons) is
called carbocation.
For example,
CH 3+ ,CH 3 CH 2+ ,(CH 3 CH 2 )2 CH + ,(CH 3 )3 C + et c.
+ –
C X C +X

Formation of carbocations:
(i) (CH3)3CCl ⎯⎯→ (CH3)3C+ + Cl− (Heterolytic fission)
+
(ii) CH3 – OH ⎯⎯→
H
CH3 – OH2+ (Protonation)
_
H 3C Br ⎯⎯⎯
FeBr3
⎯
→ CH 3+ + F eBr 4 (Abstraction of halide ion by Lewis acid)

+
H 3C N (Removal of N2 from diazonium cation)
⎯⎯→ CH 3+ + N 2
N

The carbocations are classified into different groups depending upon the nature of carbon
bearing the positive charge. Alkyl carbocations may be primary (1), secondary (2) or
tertiary (3) carbocations.
+ + + +
CH3 CH3 CH2 CH3 CH CH3 CH3 C CH3
methyl ethyl iso propyl CH3 tertiary butyl
carbocation carbocation carbocation carbocation
(1o ) (1o ) (2o ) (3o )
+
CH2
+ +
CH2 CH CH2 CH CH2
vinyl carbocation allyl carbocation beznyl carbocation
Structure of carbocation: The carbocations are electron deficient and contain six electrons
(three bond pair electrons). In strong electrical field, carbocations move towards cathode.
The carbocations have trigonal planar structure and the positively charged carbon in sp2
hybridized.
Rate of formation of carbocations:
More stable carbocation forms at faster rate as compared to less stable carbocation.
For example,
(i) R – CH2 – Cl ⎯⎯→ R – CH2+ + Cl−
(ii) R3C – Cl ⎯⎯→ R3C+ + Cl−
A tertiary carbocation is more stable, the transition state of tertiary carbocation is lower in
energy than transition state of primary carbocation. As a result, a tertiary carbocation will
form more rapidly than primary carbocation.

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Stability of carbocations:
➢ Electron deficient carbocations are stabilized by electron releasing group. Participation
of empty p-orbital in lateral overlap with completely filled orbital is the major
contributing factor for stability to stability in which positive charge is delocalized.
Alkyl group directly bonded to the positively charged carbon stabilize the carbocations
due to inductive and hyperconjugation effects. The dispersal of the positive charge due to
hyperconjugation stabilize the carbocation. The observed order of carbocation stability is
(C6H5 )3 C+  (C6H5 )2 CH+  C6H5 CH2+  CH2 = CH − CH2+  3  2  1  CH3+
+ + + +
CH3 C CH3 > CH3 CH CH3 > CH3 CH2 > CH3
CH3 o
2o 1
3o
➢ The reaction intermediates are highly reactive, usually order of reactivity of such
intermediates is reverse that of its stability. Therefore, order of reactivity of
+
carbocations follows the sequence: CH3  1  2  3
➢ Electron attractors (−I effect) increases the postive charge on carbon atom and thus
reduces the stability of carbocation, e.g.𝑂2 𝑁 − 𝐶𝐻2 − 𝐶𝐻2+ , 𝐶𝑙 − 𝐶𝐻2 − 𝐶𝐻2+ .]
➢ Carbocation are sp2 hybridized and have trigonal planar structure, so the attacking
species can approach both from top and bottom.
➢ Hybridized state of carbon:
Higher the s-character, lesser the stability. The order of stability is
+
+ + +
CH3 CH2 > CH2 CH < > CH C

➢ Resonance: The greater the delocalization of positive charge of carbocations, higher is

the stability. The stability of benzyl carbocation is comparable with allyl carbocation as
resonance energies is nearly the same
+
CH2
> +

➢ Carbocations, undergo rearrangement forming more stable carbocations.

H
..
H shift +
+

(ii) Carbanions
A reaction intermediate formed by heterolytic fission of a covalent bond which results
negatively charged carbon with eight electrons in its valence shell is called carbanion.
The heterolytic cleavage of a covalent bond as indicated inC the
X following
C – +X reactions gives +

carbanions.
O H O H
–
– + OH –
C X C +X H C C H H C C + H2O
H H

For example, − − −
CH ,CH3 CH ,(CH3 )2 CH ,CH CHO etc.
3 2
−
2
O H O H
Formation of carbanion: OH –
–
H
H C −C base H C C +HO
(i) CH3 – CHO + OH ⎯⎯⎯ → CH2− − CHO + H2O 2

H H
(ii) C2H5O− + CH3 − COOC2H5 ⎯⎯→CH2− − COOC2H5 + C2H5OH

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The carbanions are classified as primary (1), secondary (2) and tertiary (3) depending upon
the nature of carbon bearing negative charge.
.. .. ..
CH3 C CH3 CH2 CH
CH3
o o phenyl carbanion
tertiarybutyl carbanion (3 ) vinyl carbanion (1 )
Structure of carbanion: The carbanions are electron rich with complete octate configuration.
Shape of alkyl carbanion is usually pyramidal like ammonia when carbon atom carrying the
negative charge is sp3 hybridised.
In contrast, carbnions which are stabilised by resonance are planar and carbon atom carrying
negative charge is sp2 hybridised. The vinyl carbanion, phenyl carbanion and cyclopentadiene
carbanion are sp2 hybridised where as acetylide carbanion is sp hybridised.
sp3
sp 2
H 2C C HC C
C
H
H H
H
P yr a m ida l P la n a r Lin ea r
(I) (II) (III)

St a bilit y order III  II  I

Stability of carbanions:
➢ Alkyl group bonded to negatively charged carbon increases the intensity of negative
charge due to +I effect and destabilize the carbanion. The order of stability of alkyl
carbanions is:
.. .. .. >
..
CH3 > CH3 CH2 > CH3 CH CH3 CH3 C CH3
CH3
methyl
carbanion 1° 2° 3°
➢ The order of reactivity of carbanions is reverse that of its stability. Therefore, order
..
of reactivity of carbanions follows the sequence: 3o > 2o > 1o > CH3
➢ Higher the s character greater the stability of carbanion. Order of stability is
.. .. .. ..
HC C > > CH2 CH > CH3 CH2

➢ Resonance: Greater the delocalisation of negative charge by resonance, higher the

stability. The stability of benzyl carbanion is comparable with allyl carbanions.
CH2
..
> CH2 CH2 CH2

(iii) Free radicals

A reaction intermediate formed by the homolytic cleavage of a covalent bond which
contains an unpaired electron is called free radical.
The homolytic cleavage is favored for nonpolar covalent bond. Such cleavage for bond is
initiated by the action of heat, light or a reagent.
For example, CH•3 ,CH 3 CH•2 ,(CH 3 )2 CH• ,CH 2 = CH - CH •2 ,C 6 H 5CH •2 et c.

Cl Cl
light
2 Cl
.
homolysis
chlorine radical

. light .
CH3 H + Cl CH3 + HCl
methane homolysis
reagent
methyl radical

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Depending upon nature of carbon atom carrying the unpaired electron, free radicals are also
classified as primary (1), secondary (2) and tertiary (3) free radicals.
. . .
CH3 CH3 CH2 CH3 CH CH3

methyl radical (1o ) ethyl radical (1o ) iso propyl radical (2o )
.
. . CH2
CH3 C CH3 CH2 CH CH2
CH3
tertiary butyl radical (3o ) allyl radical (1o ) benzyl radical (1o )

Structure of free radical: The free radicals are electron deficient since they contain seven
electrons on carbon atom. They are electrically neutral and paramagnetic. The structure of
alkyl radical is not known with certainty. For alkyl radicals two possible structures have been
proposed. The first is a planar sp2 hybridised radical similar to a carbocation. The second one
is a pyramidal sp3 hybridised radical similar to a carbanion.
• Resonance stabilised free radicals such as allyl radicals and benzyl radicals are planar sp 2
hybridised.
• The bridge head free radicals are pyramidal (sp3-hybridised) because they cannot assume
planar geometry due to angle strain. Further, the free radicals in which carbon is bonded
to highly electronegative atoms are pyramidal.
.
. CF3
.
bridge head radical (sp3-hybridised) trifluoromethyl radical
(sp3-hybridised)
Stability of free radicals: The relative stability of alkyl free radicals is explained on the
basis of hyperconjugation and inductive effects. Greater the number of alkyl groups attached
to the carbon atom carrying unpaired electron, higher the delocalisation and hence more stable
is the alkyl radical. The order of stability of a few alkyl radicals is given below
. . . .
CH3 C CH3 CH3 CH CH3 CH3 CH2 CH3
CH3
t-butyl radical (3o) iso propyl radical (2o) ethyl radical (1o) methyl radical (1o)
The order of stability of free radicals on the basis of resonance inductive effect is as follows:
(C 6 H 5 )3 C• > (C 6 H 5 )2 CH• > C 6 H 5• > CH 2 = CH CH •2 > 3° > 2° >1° > CH •3

Like carbocations and carbanions, free radicals are highly reactive and short-lived
intermediates because of the strong tendency of the carbon atom carrying the unpaired
electron to acquire one more electron from an atom or a group to complete its octate. The
•
reactivity of alkyl radical is reverse the order of stability CH3  1  2  3
The allyl and benzyl radicals are stabilised by resonance. The stability of allyl and benzyl
radicals is comparable.
.
CH2 .
> CH2 CH CH2

The allyl or benzyl radicals are more stable than alkyl radicals.

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The reactions involving free radicals are

(i) catalysed by light, heat etc.
(ii) proceed in vapour phase or in non polar solvents.
(iii) autocatalytic.

(iv) Carbenes
They are neutral and highly reactive species generally obtained by successive elimination of an
electrophile and a nucleophile from the same carbon atom (-elimination). The carbon atom of
carbene has six electrons in valence shell, out of which two constitute unshared electrons and
two bond pair electrons. So they are divalent carbon species containing two unshared electrons
and electrically neutral.
Carbenes exist in two possible forms
(i) Singlet
(ii) Triplet
(i ) Sin glet (ii ) Tr iplet
H
C
H C H
H
sp 2 h ybr idized sp h ybridized
Two elect r on s a r e Two elect r on s a r e in
in sa m e orbit a l t wo differ en t orbit a ls
(spin pa ir ed ) (spin fr ee)

O
. . . . .
H C. H R C. H Cl C
. H R C C. H Cl C. Cl
carbene alkyl carbene chloro carbene acyl carbene dichloro carbene

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Attacking Reagents
The organic reactions proceed by the attack of highly reactive reagents on the substrate molecule.
These reagents are called attacking reagents which may be electron deficient or electron rich. They
are classified into two groups.
Electrophiles
The electron deficient molecules or positively charged ions which are capable of accepting an
electron pair from substrate molecule are called electrophiles.
These species act as Lewis acids and attack the electron rich centre of the organic molecules.

C..
+
+ E C E
substrate electrophile
They are of following types,
(i) Positively charged: The species having a positive charge, e.g.
H+ ,CH3+ ,NO2+ ,H3 O + ,NO + ,Br + ,CH3CO + etc .
(ii) Neutral: The molecules containing electron deficient atom (i.e. Lewis acids) e.g. :CH2, AlCl3,
BF3, ZnCl2, FeCl3, SO3, etc.
(ii) Ambident: Molecules with 2 electrons deficient centers,
e.g. , -unsaturated carbonyl compounds.
It may be noted that all the positively charged species do not act as electrophiles. The positively
charged species which can accept an electron pair can act as electrophiles. The positively charged ions
+ + + 2+
such as H3 O, N H4 , Na, C a , etc. do not act as electrophile as they cannot accept electron pair, since all
the ions have an octet configuration.

Nucleophiles
The molecules or negatively charge ions which are capable of donating an electron pair
to electron deficient centre of the substrate are called nucleophiles.
These species act as Lewis bases & attack on electron deficient centre of organic molecule.
..
C+ + Nu C Nu

substrate nucleophile

The common examples of nucleophiles are given below:

(i) Negatively charged: The species having a negative charge, e.g. Cl−, Br−, OH−, CN−, NO2− etc.
(ii) Neutral: The molecules having an unshared pair of electrons (i.e. Lewis base),
.. .. .. .. ..
e.g. 𝑁𝐻3 , 𝑅 − 𝑁𝐻2 , 𝑅2 − 𝑁𝐻, 𝐻2 𝑂, 𝑅 − 𝑂 − 𝐻 𝑒𝑡𝑐.
.. ..
.. .. .. .. ..
(iii) Ambident: The molecule with two electron rich centres, e.g. − C  N,N
.. = O, O  N− O etc.
Comparison between Nucleophiles and electrophiles
Nucleophiles Electrophiles
• Electron rich, donate electron pair, generally • Electron deficient, accept electron pair, generally
anions. cations
• Act as Lewis bases • Act as Lewis acids
• Attack an region of low electron density of • Attack on region of high electron density of
substrate substrate
..
• They are represented by a general symbol ( Nu ) • They can be represented by a general symbol (E+)

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Electron Displacement Effects in Covalent Bonds

The electron pair displacement in organic molecules takes place under the influence of a
hetero atom/group or by the attacking reagent. The displacement or shift of electron pair in
the organic molecule under the influence of substituent makes the molecule permanently
polar.

(i) Inductive effect (I effect)

The inductive effect is defined as “the permanent displacement of sigma (σ) bond pair of
electrons towards more electronegative atom or group and as a result molecule becomes
permanently polar”.
Larger the displacement of σ bond pair electrons greater the polarity. Consider the carbon
chain in which terminal carbon is bonded to a chlorine atom. Since chlorine is more
electronegative bond pair of electrons are displaced towards chlorine.
𝐂 − 𝐂 − 𝐂 − 𝐂 is non polar
+ + + + −
C  C  C  C X

− − − − +
C  C  C  C Y

+3 +2 +1 −

C C C Cl order of intensity of I effect +3  +2   +

There are two types of Inductive effect,

a. Positive inductive effect (+I effect)
Here substituent (Y) releases electron pair away from itself. In other words,  bond pair
of electrons are displaced away from the substituent towards the C-chain.
When less electronegative atom is attached to carbon atom (i.e. electron donating group),
the inductive effect is called + I effect.

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electron releasing substituent

 +
C Y
− −− − +
+ I effect C3 C2 C1 Z
Electronegativity of Y or Z is less than carbon atom, so the Y or Z group releases electron and
gets a partial positive charge (i.e. +) and induces a partial negative charge (i.e. −) on C1. As we
move along the chain from C1 to C3, the partial negative charge decreases.
The examples of electron donating group are (CH3)3C, (CH3)2CH, CH3CH2, CH3 etc.
The order of electron releasing or releasing ability of substituent is given below.
O
.. .. o
C6 H5 O > C O > (CH3)3C > (CH3)2CH > CH3 CH2 > CH3 > D > H
phenate ion carboxylate ion 3oalkyl 2oalkyl 1oalkyl
+ I power in decreasing order with respect to the reference H

b. Negative inductive effect (−I effect)

Here, the sigma bond pair of electrons are displaced towards electron withdrawing
substituent (X) or away from the carbon chain.
More electronegative atom is attached to carbon atom (i.e. electron withdrawing group), the
inductive effect is called – I effect.
+
The examples of electron withdrawing group 𝑁𝑅3 , 𝑁𝑂2 , 𝐹, 𝐶𝑙, 𝐼, 𝑂𝐻 𝑒𝑡𝑐.
electron withdrawing substituent
+

C X
+ + + −
C3 C2 C1 Z I effect
Order of electron withdrawing ability (−I effect) of a few substituents is given below.
⊕
𝑵𝑯𝟑 > 𝑵𝑶𝟐 > 𝑪𝑵 > 𝑺𝑶𝟑 𝑯 > 𝑪𝑯𝑶 > 𝑪𝑶 > 𝑪𝑶𝑶𝑯 > 𝑪𝑶𝑪𝒍 > 𝑪𝑶𝑶𝑹 > 𝑪𝑶𝑵𝑯𝟐 > 𝑭 > 𝑪𝒍 > 𝑩𝒓 > 𝑰 > 𝑶𝑯 > 𝑶𝑹 > 𝑵𝑯𝟐 > 𝑪𝟔 𝑯𝟓 > 𝑯
–I power of groups in decreasing order with respect to the reference H

Applications of inductive effect:

(i) Magnitude of +ve and -ve charges: can be compared by + I or – I groups present in it.
• Magnitude of +ve charge 
1
 −I power of the group.
+ I power of the group

• Magnitude of −ve charge 

1
 +I power of the group.
− I power of the group

(ii) Reactivity of alkyl halide: + I effect of methyl group enhances – I effect of the halogen
atom by repelling the electron towards tertiary carbon atom.
CH 3 CH 3
H 3C C X  H3C CH X  CH 3 CH 2 X  CH 3 X
CH 3
Tertiary > Secondary > Primary > Methyl
(iii) Relative strength of the acids:
(a) Any group or atom showing +I effect decreases the acid strength as it increases the
negative charge on the carboxylate ion which holds the hydrogen firmly. Alkyl groups have + I
effect. Thus, acidic nature is, HCOOH  CH 3 COOH  C2 H 5 COOH  C3 H7 COOH  C4 H 9 COOH
+I effect increases, so acid strength decreases
Formic acid, having no alkyl group, is the most acidic among these acids.

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(b) The group or atom having – I effect increases the acid strength as it decreases the
negative charge on the carboxylate ion. Greater is the number of such atoms or groups (having
– I effect), greater is the acid strength.
Thus, acidic nature is, CCl3 COOH  CHCl 2 COOH  CH 2 ClCOOH  CH 3 COOH
Trichloro Dichloro Monochloro Acetic acid
acetic acid acetic acid acetic acid

(– Inductive effect increases, so acid strength increases)

(c) Strength of aliphatic carboxylic acids and benzoic acid
R COOH C6 H 5 COOH
 
+ I group − I group

Hence benzoic acid is stronger acid than aliphatic carboxylic acids but exception is formic
acid. Thus, HCOOH > C6 H 5 COOH > RCOOH
Acid strength in decreasing order
As compared to water, phenol is more acidic (–I effect) but methyl alcohol is less acidic (+I
effect).
OH  H − OH > CH 3 OH
Phenol Water Methyl alcohol

(vi) Relative strength of the bases (Basic nature of −𝑵𝑯𝟐 )

The difference in base strength in various amines can be explained on the basis of
inductive effect. The +I effect increases the electron density while –I effect decreases it.
The amines are stronger bases than NH 3 as the alkyl groups increase electron density on
nitrogen due to + I effect while ClNH2 is less basic due to –I effect. “So more is the tendency
to donate electron pair for coordination with proton, the more is basic nature, i.e., more is the
negative charge on nitrogen atom (due to +I effect of alkyl group), the more is basic nature”.
Thus, the basic nature decreases in the order; (C 2 H 5 )2 NH  CH 3 CH 2 NH 2  CH 3 NH 2  NH 3  ClNH2
Diethyl Ethyl Methyl Ammonia Chloro
amine amine amine amine

The order of basicity is as given below;

Alkyl groups (R–) Relative base strength
CH3 R 2 NH > RNH2 > R 3 N > NH3
C2 H5 R 2 NH > RNH2 > NH3 > R 3 N
(CH3 )2 CH RNH2 > NH3 > R 2 NH > R 3 N
(CH3 )3 C NH3 > RNH2 > R 2 NH > R 3 N
(vii) Basicity of alcohols: The decreasing order of base strength in alcohols is due to +I effect
of alkyl groups. (CH 3 )3 COH  (CH 3 )2 CHOH  CH 3 CH 2 OH  CH 3 OH
(3 o ) (2 o ) (1 o )

(viii) Stability of carbonium ion: +I effect tends to decrease the (+ve) charge and –I effect
tends to increases the +ve charge on carbocation.
(CH 3 )3 C   (CH 3 )2 CH   CH 3 CH 2  CH 3

(ix) Stability of carbanion: Stability of carbanion increases with increasing – I effect.

CH 3−  CH 3 CH 2−  (CH 3 )2 CH −  (CH 3 )3 C −

(x). Dipole moment: Inductive effect produces dipole moment in a molecule. As this effect
increases (electronegativity difference increases) the dipole moment also increases.
CH3 − I  CH3 − Br  CH3 − Cl
1.648 D 1.79 D 1.83 D

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(ii) Resonance effect (R−effect) or Mesomeric effect

“The permanent polarity produced in the molecule by the shift of pi() or lone pair
electrons in the conjugate system creating electron deficient and electron rich centres
called resonance effect (R−effect).
The conditions required for M or R effect:
1. Molecule should be unsaturated with conjugated system (presence of alternate single and
double bond or heteroatom containing one or more lone pair electrons linked to multiple
bonded atom) of double bond.
1,3-butadiene, aniline, phenol, nitrobenzene, etc. In such systems,  or lone pair electrons are
delocalised and the molecule develops polarity.
2. Negative charge is in conjugation with double (or multiple) bond.
3. Lone pair of electrons in conjugation with double bond.
The reactivity of compounds is affected by the presence of groups like
NO2 , C  N, O , Cl, NH 2 etc.

The movement of  electrons from one end to the other end of the chain through a conjugated
system of double bond is observed in resonance effect. It is a permanent effect.
Depending upon the direction of shift of electron pair in conjugate system, R−effect is
classified into two types.
a. Positive resonance effect (+R effect / +M effect): In this effect, of electron pair
( or lone pair) moves away from the substituent or towards the conjugate system.
The +R effect in aniline as shown below.

.. ..
Substituents exert only +R effect as follows, −𝐂𝐥, −𝐁𝐫, −𝐈, −𝐍𝐇𝟐 , −𝐍𝐑𝟐 , −𝐎𝐇, −𝐎𝐑, −𝐒𝐇, −𝐎𝐂𝐇𝟑 , −𝐒𝐑
..
The substituent which exerts +R effect are called electron releasing groups.
The resonance effect in which resonance structure violates the octate rule should not be
considered. For example, structure (II) cannot be considered as resonance structure since it
violates the octate rule because oxygen has 10 electrons in the valence shell.
.. + ..
CH2 CH ..OCH3 X CH2 CH ..OCH3
I II
b. Negative resonance effect (−R effect / −M effect): isthe shift of  or lone pair
electrons is towards the substituent attached to the conjugate system. The electron
displacement depicted in nitrobenzene represents −R effect.
.. .. .. .. .. .. .. ..
O + O O + O +
O N O +
O N O +
O N O
N N

+ +

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𝑶
||
Substituents, which exert −R effect are given below. −𝑵𝑶𝟐 , −𝑪 ≡ 𝑵, −𝑪−, −𝑪𝑯𝑶, −𝑪𝑶𝑶𝑯, −𝑺𝑶𝟑𝑯, −𝑪𝑶𝑶𝑹
The substituent which exert −R effect is called electron withdrawn group. Resonance effect
provides explanation to least reactivity of haloalkenes and aryl halides towards nucleophilic
substitution reactions, acidic nature of phenols and carboxylic acids, mechanism of
electrophilic substitution reactions of benzene.
..
Substituents like N O , (phenyl) etc. exert both +R and −R effects.
➢ Resonance
• Delocalization of p-electrons in conjugation is known as resonance.
• When one structure is not sufficient to explain each and every property (chemical &
physical) then, a different structure has been drawn which is known as Resonating
Structure (canonical structure).
• All these structures contribute to the formation of a Real structure, known as
Resonating Hybrid.

or
(Actual Structure)
(resonating structures) (Resonance hybrid)
Condition for showing resonance:
(i) Molecule should be planar, nearly planar or a part of it is planar
(ii) Molecule should possess conjugated system.

Note:
They are not resonating structures rather they are tautomers.
➢ Resonating Structure
• Hypothetical structure existing on paper.
• The energy difference b/w different resonating structure is very small.
• All R.S. contribute towards the formation of resonance hybrid (Their contribution
may be different).
• A single R.S. can't explain each & every property of that particular compound.

Q. Draw the resonating structures:

Sol. (i)

(ii)

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• Resonance hybrid: It is a real structure that explains all the properties of a

compound formed by the contribution of different R.S.
It has got maximum stability as compared to any R.S.
• Resonance Energy: It is the difference b/w theoretical value of H.O.H &
experimental value. Or it can be defined as the difference b/w more stable R.S. &
R. H.
The more resonance energy, the more stable will be the molecule.
Resonance energy is an absolute term.
Note: Cyclohexane is thermodynamically more stable than benzene, even though the
resonance energy of benzene is more.
Contribution of different R. S. towards resonance hybrid:
• Non-polar R.S. contributes more than polar R.S.
Example: (a) CH2 = CH - CH = CH2 (b) CH2-CH = CH - CH2 (c) CH2 - CH = CH - CH2
Order of stability of given R.S. ⇒ a > b = c
• Polar R. S. with complete octet will contribute more as compared with the one with an
incomplete octet
CH3 - CH - OCH3 (Incomplete octet) CH3 - CH = :O - CH3 (Complete octet)
• In polar R. S. the -ve charge should be on more electro - ve atom & +ve charge should
be on more electro +ve atom.
Example:

(a) (more stable)

(b) (less stable)

• Compound with more covalent bonds will contribute more.
• Unlike charges should be closer to each other whereas like charges should be isolated.
• Extended conjugation contributes more than cross conjugation.

Example: < (Cross conjugation < Extended conjugation)

➢ Fries Rule:
• Compounds with more benzenoid structures are more stable.
• As the Resonance energy is greater than those in which lesser no. of benzenoid
structures are present.

• R. E. is <
• If a double bond is participating in resonance then it will acquire a partial single
bond character as a result of which bond length increases & bond strength
decreases.
• If a single bond is involved in resonance then it will acquire partial double bond
character. As a result of which bond length decreases & bond strength increase.

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Q. Find the order of Stability in the following:

(i)

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

(iii)

(iv) (a) (b) CH2 - CH = F

Sol. (i) a = e > b = d > c
(ii) a > b > c > d, c and are in complete
(iii) +CCl3 < +CF3, due to back bonding in +CF 3
(iv) a > b (stability)

Note:
When lone pair, as well as a double bond, is present in some atom then only p bond will be
participating in resonance. Whereas lone pair remains sp 2 hybridized orbital. When an atom
has two or more than two lone pairs then only one lone pair will participate in resonance and
the other one remains in sp2 hybridized orbital.

(iii) Hyperconjugation (No bond resonance)

The phenomenon of hyperconjugation is also known as Baker-Nathan effect as it was proposed
by Baker and Nathan. The hyperconjugation effect is much weaker compared to resonance
effect, yet it is quite useful is explaining relative stability, physical and chemical properties
of organic molecules.
This effect is extension of resonance in which C–H sigma () bond pair electrons are involved
in delocalization. It is a permanent effect in which electron releasing alkyl group bonded
to unsaturated system in which delocalization of electrons takes place through overlap
between C–H sigma () orbital and Pi() bond orbital or vacant p-orbital is known as
hyperconjugation.
The hyperconjugation is a stabilizing interaction. The delocalization of electrons by
hyperconjugation in propene molecule is depicted as in figure

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vacant p orbital overlap (hyperconjugation)

of a carbocation

sp 2 Csp 3-Hs
hybridized sigma bond
carbocation H orbital
..
+
C C H
H

HYPERCONJUGATION

Propene molecule may be regarded as the resonance hybrid of the following hyperconjugative
structures (I – IV).
+
H H H H
.. + .. ..
H C CH CH2 H C CH CH2 H C CH CH2 H C CH CH2
+
H H H H
(I) (II) (III) (IV)
Since there is no bond between carbon and hydrogen atoms in these structures (II –IV),
hyperconjugation is also called no bond resonance. It may be noted that although a free proton
(H+) has been shown in the above structures, it is still bound firmly to the - cloud and hence
is not free to move.
Hyperconjugation effect in carbocations, let us take an example of ethyl carbocation
+
(CH3 − CH 2 ) , in which the positively charged carbon atom has an empty p orbital. One of the C–
H  bond orbital of methyl group align in the plane of empty p orbital and this bond pair
electrons delocalise into the empty p-orbital as shown in figure.
(  conjugation) hyperconjugation
H
sp3 s
 bond
H
+
C C
H H
H empty p-orbital
Orbital diagram showing hyperconjugation in ethylcarbocation
The overlap of completely filled C–H  bond orbital with empty p-orbital of carbocation
causes dispersion of positive charge and stabilize the carbocation. The ethyl carbocation is
resonance hybrid of following contributing structures.
+
H H H H
+ +
H C CH2 H C CH2 H C CH2 H C CH2
+
H H H H
(I) (II) (III) (IV)

In general, larger the number of -hydrogen atoms of alkyl groups attached to a

positively charged carbon atom greater the stability of carbocations.

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Applications of hyperconjugation effect:

1. Stability of alkenes: Larger the number of hyperconjugative structures higher the
delocalization of electron pairs and greater the stability of alkene. Number of
hyperconjugative structures is equal to number of -hydrogen atoms plus one.
More number of methyl groups attached to double bonded carbon atom more would be the
stability of alkene.
CH2 = CH2 < CH3 – CH = CH2 < (CH3)2 C = CH2
No hyperconjugation 3 hyperconjugation 6 hyperconjugation
structures structures structures
This order of stability is because of greater number of hyperconjugative contributing
structures causing larger delocalisation of -electrons solve and hence accounts for higher
stability of alkene.
CH 3 − CH = CH 2  CH 3 − CH 2 − CH = CH 2  CH 3 − CH − CH = CH 2
|
CH 3
Stability in decreasing order
2. Stability of carbonium ions: More, number of hyperconjugation structures of the
carbocation more will be its stability.
tert–butyl > isopropyl > ethyl
9 hyperconjugation 6 hyperconjugative 3 hyperconjugation
structures structures structures
3. Bond lengths: The bond length in a molecule change if there is hyperconjugation. In
•
C3H3 − C2H = C1H2 , the C1−C2 bond length is found to be more than 1.34 A (normal C = C bond
•
length) while the C2−C3 bond distance is less than 1.54 A (normal C – C bond length).
4. Directive influence of the group: +M effect of methyl group in toluene is due to
hyperconjugation.
H
H H H H H H
+ + +
H H H H H

Due to hyperconjugation, there are nine different structures having negative charge at ortho
and para positions. Hence, + M effect of alkyl group attached to benzene ring follows the
order: 𝐦𝐞𝐭𝐡𝐲𝐥 > 𝐞𝐭𝐡𝐲𝐥 > 𝐢𝐬𝐨𝐩𝐫𝐨𝐩𝐲𝐥 > 𝐭𝐞𝐫𝐭 − 𝐛𝐮𝐭𝐲𝐥.
In the same way, the meta directing influence and deactivating effect of –CCl3 group in
benzotrichloride can be explained on the basis of hyperconjugation as follows,
Cl
Cl Cl Cl Cl Cl Cl
- - -
Cl Cl Cl Cl Cl

Due to low electron density at ortho and para positions, the meta position becomes point
of high electron density, hence electrophilic substitution takes place in meta position.

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(iv) Electromeric effect (E effect)

The complete transfer or shift of  electron pair of a multiple bond to one of the bonded
atoms during the attack of positively or negativity attacking agents. As soon as the reagent is
removed, the molecule reverts back to original position.
𝐄 ⊕ −
𝐀=𝐁 → 𝐀 − 𝐁:
Reagent

Temporary polarization of the substrate molecule at the site of multiple bonds, by

complete shift of an  electron pair from one atom to the other under the influence of
attacking reagents.
H H H H
⎯⎯⎯⎯⎯⎯⎯
Reagent added
⎯⎯⎯⎯⎯⎯ →
⎯
+
C C
Re agent removed

H H H H
Depending upon the direction of displacement, E effect is also of two types.
• −E effect: An attacking reagent is said to have −E effect when the direction of 
electron pair transfer of multiple bond is away from the attacking reagent.
CH3 H
.. ..
C O + CN CH3 C O
H
CN
acetaldehyde; (-E effect)
The −E effect operates during nucleophilic addition reaction of aldehydes and ketones.
• +E effect: An attacking reagent is said to have +E effect when the direction of 
electron pair transfer of a multiple bond is towards the attacking reagent.
+ +
CH3CH CH2 + H CH3CHCH3
Propene ; (+E effect) isopropyl carbocation
The +E effect is observed during electrophilic addition reaction of alkenes and alkynes
.. +
CH3 MgI CH3 + MgI

.. ..
HO + H CH2 CHO CH2 CHO + H2O
ethanal ethanal carbanion

.. ..
H2N + H C CH C CH + NH3
amide acetylide ion
Steric Hindrance or Steric Strain
When two atoms are closer to each other than the sum of their van der Waal’s radii
they repel each other due to spatial crowding. Steric hindrance or steric strain refers
to non-bonded repulsive interactions between atoms which arise when the atoms come
too close due to the shape of the molecule. The repulsion arises due to nuclear-nuclear
and electron-electron repulsive forces which start dominating the attractive forces.
Molecules with steric strain are relatively less stable than those having no strain or
less strain.

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For example, in cis-but-2-ene steric hindrance is present because the two methyl
groups are quite close to each other wheras in trans-but-2-ene no steric hindrance is
there because the two methyl groups on the opposite sides.
Steric hindrance NoSteric hindrance

CH3 H
C=C C=C
H H H CH3
cis-But-2-ene trans-But-2-ene
(Sterically hindered (No Steric hindrance,
molecule, less stable) more stable)

Steric factors have great influence on orientation and reactivity of organic molecules
in various reactions.

Types of Organic Reactions

I. Substitution reaction
The reactions in which an atom or a group in a molecule is replaced by another are called
substitution reactions. The incoming group gets attached to the same carbon atom to which
leaving group was attached. The substituting species may be a nucleophile, an electrophile or
a free radical.
A – B + X – Y ⎯⎯⎯→ A – X + B – Y
(i) Nucleophilic substitution (SN) reactions
The substitution reactions which are brought about by the attack of nucleophile (Nu)..
are called nucleophilic substitution reactions.
R// R//
.. ..
[ Nu = attacking reagent; L = leaving group]
Nu + R/ C L Nu C R/ + L
R R
The common examples of S N reactions are as follows.
R−CH2−X + NaOH ⎯⎯⎯→ aqueous
R−CH2−OH + X− (X = Cl, Br, I)
R−CH2−X + KCN ⎯⎯⎯→ R−CH2CN + X−
alcohol

R−CH2OH + SOCl2 ⎯⎯ → R−CH2Cl + HCl + SO2

(ii) Electrophilic substitution (SE) reactions
The substitution reactions which are brought about by the attack of an electrophile are
called electrophilic substitution reactions. The substitution reactions of aromatic
compound such as chlorination, nitration of benzene are representatives of S E reactions.
• Chlorination: Cl2 + FeCl3 → FeCl −4 + Cl+
H + H
+ slow FeCl4 Cl
+ Cl Cl + FeCl3 + HCl
heat

(iii) Free radical substitution

The substitution reactions which are brought about by the attack of free radical are
called free radical substitution reactions. The chlorination of aliphatic hydrocarbons in
presence of diffused sunlight is common example of free radical substitution.

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sunlight
CH4 + Cl2 CH3Cl + HCl

O
h/CCl4
+ N Br + HBr
heat
Br
O
N-bromosuccinamide(NBS)

h
Br
+ Br2 + HBr

II. Addition reaction

“An addition reaction is defined as one in which an unsaturated molecule combines with
reagent (addendum) to give a single saturated or nearly saturated compound”. If one  bond
is broken then two  bonds are formed. A few examples for different types of addition
reactions are given below
A = B + X–Y ⎯⎯→ X–A–B–Y
(i) Electrophilic addition reactions
The addition of common reagents like X 2 (X = Cl, Br or I) , HX, H2O, HOCl, etc to alkenes and
alkynes are common examples of electrophilic addition reaction. The addition of
unsymmetrical molecules like HX, H2O, HOCl, etc. to unsymmetrical alkenes or alkynes takes
place according to Markownikoffs’ rule.
R CH CH2 + HX R CH CH3
X

R CH CH2 + HOCl R CH CH2Cl

OH
(ii) Nucleophilic Addition Reactions
The electron deficient carbonyl group of aldehydes or ketones is easily attacked by
nucleophile which can supply an electron pair. Thus the addition reactions of carbonyl
compounds initiated by nucleophile and known as nucleophilic addition reactions.
R R R
.. .. H CN ..
C O + CN R/ C O R/ C OH + CN
Addition of hydrogen cyanide R/ CN CN

R′=H or alkyl (−CH3, −CH2CH3, etc.) or aryl (C6H5−) or aralkyl (C6H5CH2−)

R + R
R .. + H3O
C O + R// Mg.X R/ C O . MgX R/ C OH

Addition to Grignard reagent R/ R// R//

R/
R
C O + NaHSO3 R/ C OH
SO3Na (white solid)
Addition of sodium bisulphite R/

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III. Elimination reactions

The loss of atoms or group from adjacent carbon atoms (one in the form of a nucleophile and
other in the form of an electrophile) resulting in the formation of an unsaturated compound is
known as elimination reaction.
CH 3 CH 3 H 3C CH 3
H 3C CH 3 ⎯⎯→ + H+ + X−
H X H 3C CH 3

[Note: If these two groups or atoms are removed from adjacent carbon atoms, then it is known
as  elimination reaction.]
R
R
⎯⎯⎯⎯
con c.
H SO
→ + H 2O
H OH 2 4 CH 2
The elimination reactions are two types, -elimination reactions and -elimination reactions
(i) -elimination reactions
This type of reaction involves loss of two atoms or groups from vicinal (adjacent) carbon
atoms resulting in the formation of a  bond. Thus, it is the reverse of addition reactions.
The most familiar example of
-elimination reactions are dehydrohalogenation reactions of alkylhalides, dehalogenation of
dihaloalkanes, dehydration of alcohols, pyrolysis of esters, Hofmann elimination of
quaternary ammonium hydroxide.
Dehydrohalogenation
When alkylhalides are treated with alcoholic potassium hydroxide solution or sodamide the
corresponding alkenes are formed with the elimination of hydrogen halide.
  alcohol
R CH CH R/ + KOH R CH CH R/ + KX + H2O
alkene
H X

-elimination
R   H
C heat H + NaX + NH3
C + NaNH2 R C C
H X alkyne
-elimination
(i) Sodamide (NaNH2) is stronger dehydrohalogenating agent.
(ii) An example of 1,4-elimination (-elimination) is

R CH CH CH CH2 + KOH R CH CH CH CH2 + KX + H2O

H X 1,3-alkadiene
1,4-elimination

Dehalogenation
The dehalogenation involves the removal of halogen molecule (X2) from vicinal dihalide by
heating with zinc dust in alcoholic medium.
ethanol
R CH CH R/ + Zn R CH CH R/ + ZnBr2
Br Br
 -elimination

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Dehydration of alcohols
When alcohols are heated with dehydrating agent like concentrated sulphuric acid, the
corresponding alkenes are formed with the elimination of water (-elimination). The reaction
is called dehydration of alcohols.
 
170o C
CH2 CH2 CH2 CH2 + H2O

H OH
170o C
CH3 CH CH2 CH3 CH CH2 + H2O
H OH

100o C
CH3 CH CH2 CH3 CH CH2 + H2 O

OH H

(ii) -elimination: It involves loss of two atoms from same atom resulting in the formation of
reaction intermediates like carbine
H
H
H C H + alc.KOH C : + KCl + H2O
H
H
IV. Rearrangement reactions
The reactions which proceed by a rearrangement or reshuffling of atoms or groups in the
molecule to produce a structural isomer of the original substance are called rearrangement
reactions.
A B A B

X Y Y X
H H
OH O+ H
H+ +
–H2O Rearrangement –H+
CH3
+

OH
HN NH2

⎯⎯
→

OH
P h en yl h ydroxyla m in e p − a m in oph en ol
(i)
H3C N N
H3C C
(ii) O
O
acetyl nitrene methyl isocyanate

CH3
+ +
H3C CH H3C C
CH3
CH3
CH3
(iii) sec − ca rboca t ion t ert − ca rboca t ion

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Purification and Characteristics of Organic Compounds

The study of organic compounds starts with the characterization of the compound and the
determination of its molecular structure. The procedure generally employed for this purpose
consists of the following steps:
(1) Purification of organic compounds
(2) Qualitative analysis of organic compounds
(3) Quantitative analysis of organic compounds
(4) Determination of molecular mass of organic compounds
(5) Calculation of Empirical formula and Molecular formula of organic compounds

(1) Purification of organic compounds: A large number of methods are available for the
purification of substances. The choice of method, however, depends upon the nature of
substance (whether solid or liquid) and the type of impurities present in it. Following methods
are commonly used for this purpose,
(i) Filtration
The process of filtration is used to separate insoluble
solid component of a mixture from the soluble
components in a given solvent.
Exp- It is used to separate a mixture of Naphthalene
and Urea using a water as solvent. Urea dissolves in
water while Naphthalene remains insoluble. Upon
filtration, naphthalene remains on the filter paper
while urea is recovered from the filtrate by
evaporating water.
Filtration is very slow and takes along time. In
such cases, filtration is carried out under reduced
pressure using a Buchner funnel and water suction pump.

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(ii) Crystallization
The method is based on the difference in
the solubilities of the compound and the
impurities in a suitable solvent. Pure
compound crystallises out from the
solution and highly soluble impurities
remain in the solution. Impure organic
compounds like glucose, urea, cinnamic
acid, etc are purified. Fractional
crystallisation is used for the separation
of a mixture of two compounds which are
soluble in the same solvent but to a
different extent.
Ex: Separation of sugar and salt.

(ii) Sublimation is the process of direct conversion of a solid into the gaseous state on
heating without passing through the intervening liquid state and vice versa on cooling.
Heat
Solid Vapour
Cool

Only those substances whose vapour pressure becomes equal to the atmospheric pressure
much before their respective melting points are capable of undergoing sublimation.
There exists an equilibrium between the solid and its vapours.

Camphor, naphthalene, anthracene, iodine, benzoic acid, salicylic acid, NH4Cl, HgCl2, etc are
purified by sublimation.

(iii) Distillation- Distillation is a method used to separate constituents of a liquid mixture

which differ in their boiling points.
Distillation is a process which involves two steps:
Vapourisation: Liquid is converted into vapours.
Condensation: Vapours are condensed again into liquid.
Depending upon the difference in the boiling points of the constituent liquids, different types
of distillation methods are employed.

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• Simple distillation: Simple distillation is applied only for volatile liquids which boil without
decomposition at atmospheric pressure and contain non-volatile impurities.

This method can also be used for separating liquids having sufficient difference in their boiling
points. For example,
(i) benzene (boiling point 353 K) and aniline (boiling point 475 K)
(ii) chloroform (boiling point 334 K) and aniline (boiling point 457 K)
(iii) ether (boiling point 308 K) and toluene (boiling point 383 K)
Nitrobenzene prepared in the laboratory can also be purified by distillation.
• Fractional distillation: This method is used for the separation of two or more volatile
liquids from a liquid mixture which has boiling points close to each other. Liquids forming a
constant boiling mixture (azeotropic mixture) such as rectified spirit cannot be separated
by this method.

Fractional distillation is used these days in industries, especially, in the distillation of

petroleum, coal tar and crude alcohol. A mixture of methanol (boiling point 338 K) and
propanone (boiling point 330 K) or a mixture of benzene and toluene may be separated by
fractional distillation.

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• Distillation under reduced pressure (Vacuum distillation): The compounds, which

decompose at a temperature below their normal boiling points, cannot be purified by
distillation under ordinary atmospheric pressure.

Glycerin is one such compound which decomposes at its boiling point. The pressure is reduced
by suction pump and the distillation is carried out at lower temperature as glycerine can be
distilled at 453 K (normal boiling point 563 K) under a pressure of 10-12 mm. Cane juice can
also be concentrated by this method. This technique can be used to separate glycerol from
spent lye in soap industry.

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• Steam distillation: This method is used to purify the organic compounds which
❖ Are volatile in steam but are immiscible with water.
❖ Possess high vapour pressure at the boiling point of water.
❖ Contain nonvolatile impurities.

The compound to be purified is distilled with steam and impurities being nonvolatile remains in
mother liquor. For example, o- nitrophenol (volatile) and p-nitrophenol (non volatile) are
separated by this method.

(iv) Differential extraction (or solvent extraction): The process

of separation of an organic compound (solid or liquid) from its
aqueous solution by shaking with a suitable
organic solvent is termed as solvent extraction. This method is
employed for non-volatile compounds. For example, benzoic acid is
extracted from its aqueous solution using benzene as solvent.

(v) Chromatography
Chromatography is the technique of separating the components of mixture in which the
separation is achieved by the differential movement of individual components through a
stationary phase under the influence of a mobile phase.

jar adsorbent coated solvent

front
on glass plate
spot
sample dot
base line y
solvent x
base line
Thin layer chrom atography
chromatogram being developed Developed chromatogram
Dis tance moved by the substance formbaseline ( x )
Rf = Dis tance moved by the solvent from base line ( y)
Depending upon the nature of the stationary phase (either a solid or a liquid tightly bound on
a solid support) and the nature of the mobile phase (either a liquid or a gas), different types
of chromatographic techniques are followed.

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Chromatography

Adsorption Chrom. Partition Chrom.

Column chromatography
Paper Chrom.
High Performance Liquid Chrom. (HPLC)
Ascending Decending Radial
Thin Layer Chrom. (TLC)

Gas-Liquid Chrom. (GLC)

Type of chromatography Stationary phase Mobile phase Application
Column/adsorption Solid Liquid Large scale separation
Thin layer chromatography (TLC Solid Liquid Qualitative analysis
High performance liquid Qualitative analysis and also
Solid Liquid
chromatography (HPLC) for separation
Qualitative analysis and also
Gas liquid chromatography(GLC Liquid Gas
for separation
Qualitative analysis and also
Proper chromatography Liquid Liquid
for separation
The various components on the developed TLC plate are identified through their retardation
factor, i.e., Rf values.
distance moved by the substance from base line
Rf =
distance moved by the solvent from base line
A component with highest value of Rf elute first. A component with greater tendency to adsorb
on solid has lesser the Rf value.

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2. Qualitative Analysis (Detection of Elements)

The qualitative analysis of an organic compound involves the detection of all the elements
present in it. Carbon and hydrogen are generally present in all organic compounds. Other
elements which may be present in organic compounds are oxygen, nitrogen, sulphur, halogens,
phosphorus, etc. These elements are detected by the following tests.

Detection of Carbon and Hydrogen by Copper oxide test

Principle Organic compounds undergo oxidation in the presence of a suitable oxidizing agent. In
this process, carbon is oxidized to CO2 and hydrogen is oxidized to water.

Procedure The compound is intimately mixed with dry cupric oxide. The mixture is strongly
heated in a hard glass test tube fitted with a cork and a delivery tube. The liberated gases
are passed into lime water.

Organic compound + CuO CO2 + H2O +Cu

Carbon Water Copper
dioxide

Passed into
lime water
Ca(OH) 2 Passed into
anhydrous
CuSO4

lime water
turns milky
Copper sulphate
turns blue

Carbon (C) present

in organic compound Hydrogen (H) present
in organic compound
ℎ𝑒𝑎𝑡
[𝐶] + 2𝐶𝑢𝑂 → 𝐶𝑂2 + 2𝐶𝑢
𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
CO 2 + Ca(OH) 2 ⎯⎯
→ CaCO3 + H 2O
lime water (milky)
ℎ𝑒𝑎𝑡
[2𝐻] + 𝐶𝑢𝑂 → 𝐻2 𝑂 + 𝐶𝑢
𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

𝐶𝑢𝑆𝑂4 + 5𝐻2 𝑂 → 𝐶𝑢𝑆𝑂4 . 5𝐻2 𝑂

(𝑤ℎ𝑖𝑡𝑒) (𝑏𝑙𝑢𝑒)

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Detection of Nitrogen, Halogen and Sulphur by Lassaigne’s test

Principle This is the most reliable test for the detection of nitrogen, sulphur, halogens etc. In
this method sodium fusion extract of organic compound is prepared. In this fusion process,
carbon and nitrogen present in the organic compounds get converted into cyanide ion (CN–),
sulphur (S) into sulphide ion S2– and halogens (X) into halide ion (X–). By testing for radicles,
presence of these elements can be find.
Preparation of Sodium fusion extract
A piece of Na metal taken in a fusion tube and heated. Na melts to form shining globule.
Organic compound added to it and heated to red hot. Red hot tube is now dropped into water
taken in a porcelain dish. The contents are heated to concentrate the solution. Solution is then
filtered. The filtrate is called sodium fusion extract.
Test for nitrogen
Ferrous sulphate are added to the sodium fusion extract. The mixture is boiled and cooled. It
is acidified with hydrochloric acid and a few drops of ferric chloride solution are added.
Sodium cyanide in the filtrate reacts with ferrous sulphate to give sodium ferrocyanide. It
further reacts with ferric chloride to give a blue coloured solution of ferric ferrocyanide.
𝑓𝑢𝑠𝑒
[𝐶, 𝑁] + 𝑁𝑎 → 𝑁𝑎𝐶𝑁
𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

𝐹𝑒𝑆𝑂4 + 2𝑁𝑎𝐶𝑁 → 𝐹𝑒(𝐶𝑁)2 + 𝑁𝑎2 𝑆𝑂4

𝐹𝑒(𝐶𝑁)2 + 4𝑁𝑎𝐶𝑁 → 𝑁𝑎4 [𝐹𝑒(𝐶𝑁)6 ]

𝑠𝑜𝑑𝑖𝑢𝑚𝑓𝑒𝑟𝑟𝑜𝑐𝑦𝑎𝑛𝑖𝑑𝑒

3𝑁𝑎4 [𝐹𝑒(𝐶𝑁)6 ] + 4𝐹𝑒𝐶𝑙3 → 𝐹𝑒4 [𝐹𝑒(𝐶𝑁)6 ]3 + 12𝑁𝑎𝐶𝑙

𝑓𝑒𝑟𝑟𝑖𝑓𝑒𝑟𝑟𝑜𝑐𝑦𝑎𝑛𝑖𝑑𝑒(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)

Few drops of NaOH

Organic compound Lassaignes’s extract Na4 Fe(CN)
Fused with sodium (has NaCN) and freshly prepared FeSO 6
4 Sodium ferrocyanide

Excess of HCl
and FeCl 3

𝑭𝒆𝟒 [𝑭𝒆(𝑪𝑵)𝟔 ]𝟑
𝒇𝒆𝒓𝒓𝒊𝒇𝒆𝒓𝒓𝒐𝒄𝒚𝒂𝒏𝒊𝒅𝒆(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)

Note- If organic compound contains N and S, sodium thiocyanate is formed in sodium extract
which gives blood red colouration with FeCl3 due to the formation of ferric thiocyanate.
𝒇𝒖𝒔𝒆
[𝑪, 𝑵, 𝑺] + 𝑵𝒂 → 𝑵𝒂𝑪𝑵𝑺
𝒐𝒓𝒈𝒂𝒏𝒊𝒄𝒄𝒐𝒎𝒑𝒐𝒖𝒏𝒅

𝑵𝒂𝑪𝑵𝑺 + 𝑭𝒆𝑪𝒍𝟑 → 𝑭𝒆(𝑪𝑵𝑺)𝑪𝒍𝟐 + 𝑵𝒂𝑪𝒍

𝒇𝒆𝒓𝒓𝒊𝒄 𝒔𝒖𝒍𝒑𝒉𝒐 𝒄𝒚𝒂𝒏𝒊𝒅𝒆(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)

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Test for Sulphur

Lead acetate test: Second part of the filtrate is treated with excess of acetic acid and
lead acetate solution. A black precipitate of lead sulphide is formed.
𝑓𝑢𝑠𝑒
[𝑆] + 2𝑁𝑎 → 𝑁𝑎2 𝑆
(𝑜𝑓𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑)

𝑁𝑎2 𝑆 + 𝑃𝑏(𝐶𝐻3 𝐶𝑂𝑂)2 → 2𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 + 𝑃𝑏𝑆 ↓

𝑏𝑙𝑎𝑐𝑘𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
Sodium nitroprusside test: To the sodium fusion extract, a few drops of sodium nitroprusside
are added. The appearance of violet or purple colour indicates the presence of sulphur.
𝑁𝑎2 𝑆 + 𝑁𝑎2 [𝐹𝑒(𝐶𝑁)5 𝑁𝑂] → 𝑁𝑎4 [𝐹𝑒(𝐶𝑁)5 𝑁𝑂. 𝑆] or 𝑁𝑎3 [𝐹𝑒(𝑂𝑁𝑆𝑁𝑎)(𝐶𝑁)5 ]
            Sodium nitroprusside 𝑠𝑜𝑑𝑖𝑢𝑚 𝑠𝑢𝑙𝑝ℎ𝑜 𝑛𝑖𝑡𝑟𝑜 𝑝𝑟𝑢𝑠𝑠𝑖𝑑𝑒 Sodium thionitroprusside
(Purple) (Violet)

Organic compound Lassaignes's extract Divide the extract in two parts
Fused with sodium (has Na2S
sodium shulphide)

To one portion add acetic acid To other portion add

(CH3COOH) and lead acetate freshly
[Pb(CH3COO)2] prepared sodium
nitroprusside
Na2[Fe(CN)5(NO)]

Black ppt. of lead sulphide

Violet colouration
(PbS) confirms the presence
of Na4[Fe(CN)5NOS]
of sulphur in organic compound
confirms the presence
of sulphur in organic
compound
Test for Halogens
Silver nitrate test A portion of the stock solution is boiled with dil. HNO3, cooled and silver
nitrate is added.
A white precipitate soluble in ammonium hydroxide shows the presence of chlorine. A pale
yellow precipitate slightly soluble in ammonium hydroxide shows the presence of bromine. A
yellow precipitate insoluble in ammonium hydroxide shows the presence of iodine.
𝐻𝑁𝑂3
𝑁𝑎𝑋 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝑋 ↓
𝑝𝑝𝑡

NaCl + AgNO3 → AgCl ↓ + NaNO3

white ppt

NaBr + AgNO3 → AgBr ↓ + NaNO3

pale yellow ppt

NaI + AgNO3 → AgI ↓ + NaNO3

yellow ppt
Note: During the detection of halogens, the sodium fusion extract is boiled with nitric acid in
order to expel the N and S as HCN and H2S.
When AgNO3 added cyanide gives white ppt, sulphide gives black ppt and interfere with
observation.

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 dil. HNO3
Organic compound Lassaignes extract
and AgNO3
Fused with sodium (has NaX
(has covalent bonds sodium halide)
with carbon and halogens)
White ppt of Pale yellow ppt Yellow ppt of
silver chloride of silver iodide
(AgCl) soluble in silver bromide (Agl)
ammonia confirms (AgBr) sparingly insoluble
the presence of soluble in in ammonia
chlorine in ammonia confirms the
organic compound confirms the presence of
persence of iodine in
bromine in organic
organic compound
compound

Note: Beilstein’s test: Beilstein’s test is used to detect the halogen in an organic compound.
A copper wire is heated in a Bunsen flame till no colour is imparted to the flame. The copper
wire is dipped in the given organic compound and exposed to the non-luminous zone of the
Bunsen flame. A bluish green coloured flame indicates the presence of halogen.

Test for Phosphorus

Organic compound containing phosphrous is fused with sodium peroxide. The phosphorus of
the compound is oxidised to phosphate. The fused mass is extracted with water and filtered.
The filtrate containing sodium phosphate is boiled with nitric acid and then treated with
ammonium molybdate. A yellow solution or precipitate indicates the presence of phosphorus.
Na + P + O → Na3PO4
Na3PO4 + 3HNO3 → H3PO4 + 3NaNO3
H 3PO 4 + 12(NH 4 ) 2 MoO 4 + 2HNO 3 → (NH 4 ) 3 PO 4 12MoO 3 + 21NH 4 NO 3 + 12H 2O
ammonium molyblate ammonium phosp hom olybdate


Phosphorus present in organic compound
Organic compound
With Na2O change to phosphate (Na
3PO4)

(sodium peroxide)
boiled with nitric acid
(HNO3) and added
ammonium molybdate
[(NH4)2MoO4]

Yellow ppt of
ammonium
phosphomolybdate
[(NH4)3PO4.12MoO3]
confirms the presence
of phosphorus in
organic compound

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(3) Quantitative analysis The quantitative analysis deals with the determination of
percentage of various elements. The following methods are employed for the determination
of percentage composition of elements present in the organic compounds.
Estimation of carbon and hydrogen by Liebig’s combustion method
Principle: A known mass of organic compound is oxidized with cupric oxide in C0 2 free
atmosphere. C gets oxidized to C02, H to H2O. Water formed is absorbed in weighed anhydrous
CaCl2 U bulbs and carbon dioxide absorbed in weighed KOH bulbs. Increase in mass of CaCl2
and KOH bulbs are determined. Difference in mass corresponds to the mass of H2O and C02
respectively.
Knowing the increase in mass, the percentage of C and H in the organic compound can be
calculated.
𝒚 𝜟 𝒚
𝑪𝒙 𝑯𝒚 + (𝒙 + ) 𝑶𝟐 → 𝒙𝑪𝑶𝟐 + 𝑯𝟐 𝑶
𝟒 𝟐

Calculations
• Let the mass of organic compound taken = m g
• Mass of water formed = m1 g
(increase in CaCl2 U-tube)
• Mass of carbon dioxide formed = m2 g
(increase in potash tubes)
(a) Percentage of Carbon
We know that 1 mole of carbondioxide (44 g) contains 1 gram atom of carbon (12g).
44 g of CO2 contain C = 12g
12
m2 g of CO2 contains C = × m2 g
44
12𝑚2
Hence Percentage of carbon = × 100
44×𝑚
(b) Percentage of Hydrogen
We know that one mole of water (18g) contains 2gram atom of hydrogen (2g)
H2O = 2H
18g of H2O contain H = 2g
2
m1 g of H2O contains H = × m1 g
18
2𝑚1
Percentage of hydrogen = × 100
18×𝑚

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Estimation of nitrogen by Kjeldahl’s method

Principle: Kjeldahl’s method is based on the quantitative conversion of nitrogen of the

organic compound to ammonium sulphate by sulphuric acid. The reaction product is treated
with an alkali and the ammonia released is determined. From this the amount of nitrogen in
the organic compound is calculated.
𝑐𝑜𝑛𝑐.𝐻2 𝑆𝑂4
[𝐶, 𝐻, 𝑁, 𝑆] → 𝐶𝑂2 + 𝐻2 𝑂 + 𝑆𝑂2 + (𝑁𝐻4 )2 𝑆𝑂4
𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 ℎ𝑒𝑎𝑡
ℎ𝑒𝑎𝑡
(𝑁𝐻4 )2 𝑆𝑂4 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝑆𝑂4 + 2𝐻2 𝑂 + 2𝑁𝐻3
2𝑁𝐻3 + 𝐻2 𝑆𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4
This method is simple, convenient and largely used for the estimation of nitrogen in food
stuffs, drugs, fertilizers and many other organic compounds. However, this method cannot
be employed for the estimation of nitrogen in following types of organic compounds.
• Organic compound containing nitrogen in aromatic ring such as pyridine, quinoline, etc.,
• Organic compounds containing nitro (−NO2) and diazo (− N = N −) groups.

Calculations
Let the mass of organic compound = w g
Volume of standard acid taken = V cm3
Normality of acid = N1
Let vol. of standard alkali used for neutralisation of unused acid = V2 cm3
Normality of standard alkali = N2
𝑁
⏟ 1 𝑉1 =𝑁
⏟2 𝑉2
𝑎𝑙𝑘𝑎𝑙𝑖 𝑎𝑐𝑖𝑑
Let this volume of v cm3
Vol. of acid used for neutralisation of ammonia = (V – v) cm3 of N1 normality
Ammonia liberated = (V – v) cm3 of N1 solution
Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g
(V – v) cm3 of N1 NH3 solution contains
14(V − v)x N1
nitrogen = g
1000
Mass of nitrogen
Percentage of nitrogen = × 100
Mass of organic compound

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14(V − v)xN1 100 1.4(V − v)x N1

= × =
1000 w w
volume of the acid (cm3 ) × normality of the acid × 1.4
Percentage of nitrogen in the compoun =
mass of organic compound in g

Estimation of Nitrogen by Duma’s method

Principle: The organic compound containing nitrogen when heated with excess of copper oxide
in the atmosphere of carbon dioxide, yields nitrogen in addition to carbon dioxide and water.
𝑪 + 𝟐𝑯 + 𝟑𝑪𝒖𝑶 → 𝑪𝑶𝟐 + 𝑯𝟐 𝑶 + 𝟑𝑪𝒖
𝟐𝑵 + 𝟐𝑪𝒖𝑶 → 𝑵𝟐 +oxide of nitrogen
or
𝑦 𝑦 𝑦 𝑧
[𝐶𝑥 𝐻𝑦 𝑁𝑧 ] + (2𝑥 + ) 𝐶𝑢𝑂 → (2𝑥 + ) 𝐶𝑢 + 𝑥𝐶𝑂2 + 𝐻2 𝑂 + 𝑁2
𝑂𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 2 2 2 2
Traces of nitrogen oxides formed during combustion of organic compound are reduced to
nitrogen by passing the gaseous mixture over a heated copper gauze. The percentage of
nitrogen present in a given organic compound is calculated from the volume of nitrogen
collected over potassium hydroxide solution from a known mass of organic compound.

Calculations
Let the mass of organic compound = wg
The volume of nitrogen collected = Vcm3
Atmospheric pressure from barometer) = P mm of Hg
0
Room temperature = t C
0
Aqueous tension at t C = a mm of Hg
Pressure of dry nitrogen = (P – a) mm of Hg
Let us first convert the volume of nitrogen to volume at S.T.P.
Experimental conditions S.T.P. conditions
P1 = (P – a)mmHg P2 = 760 mm
T1 = (273 + t)K T2 = 273
V1 = V cm3 V2 = ?

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𝑃1 𝑉1 𝑃2 𝑉2
Applying gas equation =
𝑇1 𝑇2
= x cm3 (say)
𝑃1 𝑉1 𝑇2 (𝑃−𝑎)𝑥𝑉𝑥273
V2 = =
𝑃2 𝑇1 760(273+𝑡)
Now 22400 cm3 of N2 at S.T.P. weight = 28 g
x cm3 of N2 at S.T.P. will weigh = ×
28
xg
22400
𝑀𝑎𝑠𝑠𝑜𝑓𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 28𝑥𝑥100
Percentage of nitrogen = x 100 =
𝑀𝑎𝑠𝑠𝑜𝑓𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 22400𝑥𝑤
28 𝑉
% of N = × × 100
22400 𝑊
Where, V= volume of 𝑁2 in nitrometer (in ml) at NTP,
1.4×N×𝑉
W= Weight of substance taken; % of 𝑁 =
𝑊

Estimation of Halogen by Carius method

Principle: A known mass of an organic compound is heated with fuming nitric acid and a few
crystals of silver nitrate in a sealed tube called Carius tube. The Carbon, hydrogen or sulphur
present in the compound will be oxidised to CO2, H2O and H2SO4 respectively. Halogen is
precipitated to give silver halide.
[C H X] + [O] ⎯⎯⎯⎯⎯
fuming HNO3
→ CO 2 + H 2O + HX
heat
Organic compound

HX + AgNO3 → AgX + HNO3

Precipitate

• This method does not give satisfactory results in the estimation of iodine as AgI is slightly
soluble in nitric acid and iodide may oxidise to iodine to some extent.
• The results of this method is not very accurate in case of polyhalogenated aromatic
compounds
• Estimation of fluorine can not be carried out as AgF is soluble in water.
Calculations:
Let the mass of organic compound be w g
Mass of silver halide formed = a g
Now, AgX = X
108 + X parts by weight of silver halide contains X parts by weight of halogen (X is its atomic mass)
(108 + X) g of silver halide give halogen = X
𝑋
a g of silver halide will give halogen = (108+𝑋) × ag

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atomic mass of X mass of silver halide in grams

Percentage of halogen =  100
molecular mass of AgX mass of organic compound in grams Xxa 100
= ×
(108+ X) w
Here X is the atomic mass of halogen, e.g. Cl = 35.5 , Br = 80 (79.9 exact), I = 127 (126.9 exact)
35.5 mass of silver chloride in grams
Percentage of chlorine =  100
(108 + 35.5) mass of organic compound in grams
80.0 mass of silver bromide in grams
Percentage of bromine =  100
(108 + 80) mass of organic compound in grams

127 mass of silver iodide in grams

Percentage of iodine =  100
(108 +127) mass of organic compound in grams

Estimation of sulphur by Carius method

Principle: An organic compound is digested with fuming nitric acid in a sealed tube. The sulphur
present in the compound is quantitatively oxidised into sulphuric acid. Sulphuric acid so formed
is precipitated as barium sulphate by adding excess of barium chloride.
The main reactions are : S + H2O + 3O ⎯HNO
⎯⎯3 → H2SO4
H2SO4 + BaCl2 ⎯→ BaSO4
ppt.
Calculations :
Let the mass of organic compound = w g
Mass of BaSO4 formed = ag
BaSO4 137 + 32 + 64 = 32 = 233
233 g of BaSO4 contain sulphur = 32 g
32 x a
ag of BaSO4 will contain sulphur = g
233
𝑀𝑎𝑠𝑠 𝑜𝑓𝑠𝑢𝑙𝑝ℎ𝑢𝑟 32𝑎 100
Percentage of sulphur = × 100 = ×
𝑀𝑎𝑠𝑠𝑜𝑓𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 233 𝑤
32 mass of barium sulphate in grams
Percentage of sulphur =  100
233 mass of organic compounds in grams

Estimation of phosphrous by Carius method

Principle: The phosphorus present in the organic compound is oxidised to orthophosphoric acid
by heating with fuming nitric acid. The phosphoric acid so obtained is precipitated as
MgNH4PO4 which on ignition is converted into Mg2P2O7.
[C, H, P] + [O] ⎯⎯⎯
fuming
→ H3PO4 + H 2O + CO2
Organic compound nitric acid

H 3PO 4 + [NH 4Cl + NH 4OH + MgCl 2 ] → MgNH 4PO 4

magnesia mixture white precipitate

2MgNH 4 PO4 ⎯⎯⎯

ignite
→ Mg P O
2 2 7 + H 2O + 2NH3
magnesium pyrophoshate

62 mass of Mg 2 P2O 7 in grams

Percentage of phosphorus = 222  mass of organic compound in grams 100

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Estimation of oxygen
There is no direct method for the estimation of oxygen present in the organic compound. The
percentage of oxygen in the compound is generally estimated by difference.
Percentage of oxygen = 100 − [sum of percentage of all other elements present in it]
The percentage of oxygen in an organic compound is usually found by difference between the
total percentage composition (100) and the sum of the percentages of all other elements.
However, oxygen can also be estimated directly as follows:
A definite mass of an organic compound is decomposed by heating in a stream of nitrogen gas.
The mixture of gaseous products containing oxygen is passed over red-hot coke when all the
oxygen is converted to carbon monoxide. This mixture is passed through warm Iodine
pentoxide (I2O5) when carbon monoxide is oxidised to carbon dioxide producing iodine.
Compound ⎯⎯ ⎯
heat
→ O2 + other gaseous products
2C + O2 ⎯⎯⎯→ 2CO]  5 … (A)
1373 K

I2O5 + 5CO ⎯⎯ → I2 + 5CO2 ]  2 … (B)

On making the amount of CO produced in equation (A) equal to the amount of CO used in
equation (B) by multiplying the equations (A) and (B) by 5 and 2 respectively; we find that each
mole of oxygen liberated from the compound will produce two moles of carbon dioxide.
Thus 88 g carbon dioxide is obtained if 32 g oxygen is liberated.
Let the mass of organic compound taken be mg
Mass of carbon dioxide produced be m1g
32  m1
 m1g carbon dioxide is obtained from g O2
88
32  m1  100
 Percentage of oxygen = %
88  m
The percentage of oxygen can be derived from the amount of iodine produced also.
Presently, the estimation of elements in an organic compound is carried out by using
microquantities of substances and automatic experimental techniques. The elements, carbon,
hydrogen and nitrogen present in a compound are determined by an apparatus known as CHN
elemental analyser. The analyser requires only a very small amount of the substance (1-3 mg)
and displays the values on a screen within a short time. A detailed discussion of such methods
is beyond the scope of this book.

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Ques 12.1: What are hybridisation states of each carbon atom in the following
compounds?
CH2=C=O, CH 3CH=CH2, (CH3)2CO, CH2=CHCN, C6H6
Ans:

(i)
C–1 is sp2 hybridised.
C–2 is sp hybridised.

(ii)
C–1 is sp3 hybridised.
C–2 is sp2 hybridised.
C–3 is sp2 hybridised.
(iii)

C–1 and C–3 are sp3 hybridised.

C–2 is sp2 hybridised.

(iv)
C–1 is sp2 hybridised.
C–2 is sp2 hybridised.
C–3 is sp hybridised.
(v) C6H6
All the 6 carbon atoms in benzene are sp2 hybridised.

Ques 12.2: Indicate the σ and π bonds in the following molecules:

C6H6, C6H12, CH2Cl2, CH2 = C = CH2, CH3NO2, HCONHCH3
Ans:
(i) C6H6

There are six C–C sigma ( ) bonds, six C–H sigma ( ) bonds, and three C=C pi (
)resonating bonds in the given compound.
(ii) C6H12

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There are six C–C sigma ( ) bonds and twelve C–H sigma ( ) bonds in the given
compound.
(iii) CH2Cl2

There two C–H sigma ( ) bonds and two C–Cl sigma ( ) bonds in the given
compound.
(iv) CH2 = C = CH2

There are two C–C sigma ( ) bonds, four C–H sigma ( ) bonds, and two C=C pi (
) bonds in the given compound.
(v) CH3NO2

There are three C–H sigma ( ) bonds, one C–N sigma ( ) bond, one N–O sigma (
) bond, and one N=O pi ( ) bond in the given compound.
(vi) HCONHCH3

There are two C–N sigma ( ) bonds, four C–H sigma ( ) bonds, one N–H sigma
bond, and one C=O pi ( ) bond in the given compound.

Ques 12.3: Write bond line formulas for: Isopropyl alcohol, 2,3-Dimethyl
butanal, Heptan-4-one.
Ans: The bond line formulae of the given compounds are:
(a) Isopropyl alcohol

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(b) 2, 3–dimethyl butanal

(c) Heptan–4–one

Ques 12.4: Give the IUPAC names of the following compounds:

(a)

(b)

(c)

(d)

(e)
(f) Cl2CHCH2OH
Ans: (a)

1–phenyl propane
(b)

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3–methylpentanenitrile
(c)

2, 5–dimethyl heptane
(d)

3–bromo–3–chloroheptane
(e)

3–chloropropanal
(f) Cl2CHCH2OH
2, 2–dichloroethanol

Ques 12.5: Which of the following represents the correct IUPAC name for the
compounds concerned?
(a) 2,2-Dimethylpentane or 2-Dimethylpentane
(b) 2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane
(c) 2-Chloro-4-methylpentane or 4-Chloro-2-methylpentane
(d) But-3-yn-1-ol or But-4-ol-1-yne
Ans: (a) The prefix di in the IUPAC name indicates that two identical substituent groups
are present in the parent chain. Since two methyl groups are present in the C –2 of the
parent chain of the given compound, the correct IPUAC name of the given compound is 2,
2–dimethylpentane.
(b) Locant number 2, 4, 7 is lower than 2, 5, 7. Hence, the IUPAC name of the given
compound is 2, 4, 7–trimethyloctane.
(c) If the substituents are present in the equivalent position of the parent chai n, then
the lower number is given to the one that comes first in the name according to the
alphabetical order. Hence, the correct IUPAC name of the given compound is 2 –chloro–4–
methylpentane.
(d) Two functional groups – alcoholic and alkyne – are present in the given compound. The
principal functional group is the alcoholic group. Hence, the parent chain will be suffixed
with ol. The alkyne group is present in the C–3 of the parent chain. Hence, the correct
IUPAC name of the given compound is But–3–yn–1–ol.

Ques 12.6: Draw formulas for the first five members of each homologous series
beginning with the following compounds.

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(a) H–COOH
(b) CH3COCH3
(c) H–CH=CH2
Ans: The first five members of each homologous series beginning with the given
compounds are shown as follows:
(a)
H–COOH : Methanoic acid
CH3–COOH : Ethanoic acid
CH3–CH2–COOH : Propanoic acid
CH3–CH2–CH2–COOH : Butanoic acid
CH3–CH2–CH2–CH2–COOH : Pentanoic acid
(b)
CH3COCH3 : Propanone
CH3COCH2CH3 : Butanone
CH3COCH2CH2CH3 : Pentan-2-one
CH3COCH2CH2CH2CH 3 : Hexan-2-one
CH3COCH2CH2CH2CH 2CH3 : Heptan-2-one
(c)
H–CH=CH2 : Ethene
CH3–CH=CH2 : Propene
CH3–CH2–CH=CH2 : 1-Butene
CH3–CH2–CH2–CH=CH2 : 1-Pentene
CH3–CH2–CH2–CH2–CH=CH2 : 1-Hexene

Ques 12.7: Give condensed and bond line structural formulas and identify the
functional group(s) present, if any, for :
(a) 2,2,4-Trimethylpentane
(b) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(c) Hexanedial
Ans: (a) 2, 2, 4–trimethylpentane
Condensed formula:
(CH3)2CHCH2C (CH3)3
Bond line formula:

(b) 2–hydroxy–1, 2, 3–propanetricarboxylic acid

Condensed Formula:
(COOH)CH 2C(OH) (COOH)CH 2(COOH)
Bond line formula:

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The functional groups present in the given compound are carboxylic acid (–COOH) and
alcoholic (–OH) groups.
(c) Hexanedial
Condensed Formula:
(CHO) (CH 2)4 (CHO)
Bond line Formula:

The functional group present in the given compound is aldehyde (–CHO).

Ques 12.8: Identify the functional groups in the following compounds

(a)

(b)

(c)

Ans: The functional groups present in the given compounds are:

(a) Aldehyde (–CHO),
Hydroxyl(–OH),
Methoxy (–OMe),

C=C double bond

(b) Amino (–NH2); primary amine,
Ester (-O-CO-),
Triethylamine (N(C 2 H5)2); tertiary amine
(c) Nitro (–NO2),
C=C double bond

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Ques 12.9: Which of the two: O 2NCH 2CH2O– or CH3CH2O– is expected to be more
stable and why?
Ans: NO2 group is an electron-withdrawing group. Hence, it shows –I effect. By
withdrawing the electrons toward it, the NO 2 group decreases the negative charge on
the compound, thereby stabilising it. On the other hand, ethyl group is an electron -
releasing group. Hence, the ethyl group shows +I effect. This increases the negative
charge on the compound, thereby destabilising it. Hence, O 2NCH2CH2O– is expected to
be more stable than CH 3CH2O–.

Ques 12.10: Explain why alkyl groups act as electron donors when attached to
a π system.
Ans: When an alkyl group is attached to a π system, it acts as an electron-donor group
by the process of hyperconjugation. To understand this concept better, let us take the
example of propene.

In hyperconjugation, the sigma electrons of the C–H bond of an alkyl group are
delocalised. This group is directly attached to an atom of an unsaturated system. The
delocalisation occurs because of a partial overlap of a sp3 –s sigma bond orbital with an
empty p orbital of the π bond of an adjacent carbon atom.
The process of hyperconjugation in propene is shown as follows:

This type of overlap leads to a delocalisation (also known as no-bond resonance) of

the π electrons, making the molecule more stable.

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Ques 12.11: Draw the resonance structures for the following compounds. Show the
electron shift using curved-arrow notation.
(a) C6H5OH
(b) C6H5NO2
(c) CH3CH = CH – CHO
(d) C6H5CHO

(e)

(f)
Ans: (a) The structure of C 6H5OH is:

The resonating structures of phenol are represented as:

(b) The structure of C 6H5NO2 is:

The resonating structures of nitro benzene are represented as:

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(c) CH3CH = CH – CHO

The resonating structures of the given compound are represented as:

(d) The structure of C 6H5CHO is:

The resonating structures of benzaldehyde are represented as:

(e) C6H5CH2⊕
The resonating structures of the given compound are:

(f) CH3 CH = CH CH 2⊕
The resonating structures of the given compound are:

Ques 12.12: What are electrophiles and nucleophiles? Explain with examples.
Ans: An electrophile is a reagent that takes away an electron pair. In other words, an
electron-seeking reagent is called an electrophile (E + ). Electrophiles are electron-
deficient and can receive an electron pair.

Carbocations and neutral molecules having functional groups such as carbonyl

group ( ) are examples of electrophiles.
A nulceophile is a reagent that brings an electron pair. In other words, a nucleus -seeking
reagent is called a nulceophile (Nu:).
Example: OH–, NC–, carbanions (R 3C–), etc.
Neutral molecules such as H 2Ö and ammonia also act as nulceophiles because of the
presence of a lone pair.

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Ques 12.13: Identify the reagents shown in bold in the following equations as
nucleophiles or electrophiles:

Ans: Electrophiles are electron-deficient species and can receive an electron pair. On
the other hand, nucleophiles are electron-rich species and can donate their electrons.

Here, HO – acts as a nucleophile as it is an electron-rich species, i.e., it is a nucleus-

seeking species.

Here, –CN acts as a nucleophile as it is an electron-rich species, i.e., it is a nucleus-

seeking species.

Here, acts as an electrophile as it is an electron-deficient species.

Ques 12.14: Classify the following reactions in one of the reaction type studied in
this unit.
(a) CH3CH2Br + HS– → CH3CH2SH +Br–
(b) (CH 3)2 C = CH2 + HCl → (CH3)2 ClC–CH3
(c) CH3CH2Br + HO– → CH2 = CH2 + H2O Br–
(d) (CH 3)3 C – CH2 OH+ HBr → (CH3)2 CBrCH2CH3 + H2O
Ans:
(a) It is an example of substitution reaction as in this reaction the bromine group in
bromoethane is substituted by the –SH group.
(b) It is an example of addition reaction as in this reaction two reactant molecules
combine to form a single product.
(c) It is an example of elimination reaction as in this reaction hydrogen and bromine are
removed from bromoethane to give ethene.
(d) In this reaction, substitution takes place, followed by a rearrangement of atoms and
groups of atoms.

Ques 12.15: What is the relationship between the members of following pairs of
structures? Are they structural or geometrical isomers or resonance contributors?

(a)

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(b)

(c)

Ans:
(a) Compounds having the same molecular formula but with different structures are
called structural isomers. The given compounds have the same molecular formula but they
differ in the position of the functional group (ketone group).

In structure I, ketone group is at the C-3 of the parent chain (hexane chain) and in
structure II, ketone group is at the C-2 of the parent chain (hexane chain). Hence, the
given pair represents structural isomers.
(b) Compounds having the same molecular formula, the same constitution, and the
sequence of covalent bonds, but with different relative position of their atoms in space
are called geometrical isomers.

In structures I and II, the relative position of Deuterium (D) and hydrogen (H) in space
are different. Hence, the given pairs represent geometrical isomers.
(c) The given structures are canonical structures or contributing structures. They are
hypothetical and individually do not represent any real molecule. Hence, the given pair
represents resonance structures, called resonance isomers.

Ques 12.16: For the following bond cleavages, use curved-arrows to show the
electron flow and classify each as homolysis or heterolysis. Identify reactive
intermediate produced as free radical, carbocation and carbanion.
(a)

(b)

(c)

(d)

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Ans: (a) The bond cleavage using curved-arrows to show the electron flow of the given
reaction can be represented as

It is an example of homolytic cleavage as one of the shared pair in a cova lent bond goes
with the bonded atom. The reaction intermediate formed is a free radical.
(b) The bond cleavage using curved-arrows to show the electron flow of the given
reaction can be represented as

It is an example of heterolytic cleavage as the bond breaks in such a manner that the
shared pair of electrons remains with the carbon of propanone. The reaction
intermediate formed is carbanion.
(c) The bond cleavage using curved-arrows to show the electron flow of the given
reaction can be represented as

It is an example of heterolytic cleavage as the bond breaks in such a manner that the
shared pair of electrons remains with the bromine ion. The reaction intermediate formed
is a carbocation.
(d) The bond cleavage using curved-arrows to show the electron flow of the given
reaction can be represented as

It is a heterolytic cleavage as the bond breaks in such a manner that the shared pair of
electrons remains with one of the fragments. The intermediate formed is a carbocation.

Ques 12.17: Explain the terms Inductive and Electromeric effects. Which electron
displacement effect explains the following correct orders of acidity of the
carboxylic acids?
(a) Cl3CCOOH > Cl2 CHCOOH > ClCH 2COOH
(b) CH3CH2COOH > (CH 3)2CHCOOH > (CH 3)3C.COOH
Ans: \

• Inductiveeffect: The permanent displacement of sigma (σ) electrons along a

saturated chain, whenever an electron withdrawing or electron donating group is
present, is called inductive effect.
Inductive effect could be +I effect or – I effect. When an atom or group
attracts electrons towards itself more strongly than hydrogen, it is said to
possess – I effect. Example:

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When an atom or group attracts electrons towards itself less strongly than
hydrogen, it is said to possess I effect.
Example:
• Electrometric effect
It involves the complete transfer of the shared pair of π electrons to either of
the two atoms linked by multiple bonds in the presence of an attacking agent.

For example,
Electrometric effect could be +E effect or – E effect.
+E effect: When the electrons are transferred towards the attacking reagent.
– E effect: When the electrons are transferred away from the attacking
reagent
(a) Cl3CCOOH > Cl2CHCOOH > ClCH 2COOH
The order of acidity can be explained on the basis of Inductive effect ( – I effect). As
the number of chlorine atoms increases, the – I effect increases. With the increase in –
I effect, the acid strength also increases accordingly.

(b) CH3CH2COOH > (CH 3)2 CHCOOH > (CH 3)3 C.COOH
The order of acidity can be explained on the basis of inductive effect ( I effect). As the
number of alkyl groups increases, the +I effect also increases. With the increase in +I
effect, the acid strength also increases accordingly.

Ques 12.18: Give a brief description of the principles of the following techniques
taking an example in each case.
(a) Crystallisation
(b) Distillation
(c) Chromatography
Ans: (a) Crystallisation
Crystallisation is one of the most commonly used techniques for the purification of s olid
organic compounds.
Principle: It is based on the difference in the solubilites of the compound and the
impurities in a given solvent. The impure compound gets dissolved in the solvent in which
it is sparingly soluble at room temperature, but appreciably soluble at higher

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temperature. The solution is concentrated to obtain a nearly saturated solution. On

cooling the solution, the pure compound crystallises out and is removed by filtration.
For example, pure aspirin is obtained by recrystallising crude aspirin. Approximately 2 –
4 g of crude aspirin is dissolved in about 20 mL of ethyl alcohol. The solution is heated
(if necessary) to ensure complete dissolution. The solution is then left undisturbed until
some crystals start to separate out. The crystals are then filtered and dried.
(b) Distillation
This method is used to separate volatile liquids from non-volatile impurities or a mixture
of those liquids that have a sufficient difference in their boiling points.
Principle: It is based on the fact that liquids having different boiling points vapourise at
different temperatures. The vapours are then cooled and the liquids so formed are
collected separately.
For example, a mixture of chloroform (b.p = 334 K) and aniline (b.p = 457 K) can be
separated by the method of distillation. The mixture is taken in a round bottom flask
fitted with a condenser. It is then heated. Chloroform, being more volatile, vaporizes
first and passes into the condenser. In the condenser, the vapours condense and
chloroform trickles down. In the round bottom flask, aniline is left behind.
(c) Chromatography
It is one of the most useful methods for the separation and purification of organic
compounds.
Principle: It is based on the difference in movement of individual components of a
mixture through the stationary phase under the influence of mobile phase.
For example, a mixture of red and blue ink can be separated by chromatography. A drop
of the mixture is placed on the chromatogram. The component of the ink, which is less
adsorbed on the chromatogram, moves with the mobile phase while the less adsorbed
component remains almost stationary.

Ques 12.19: Describe the method, which can be used to separate two compounds
with different solubilities in a solvent S.
Ans: Fractional crystallisation is the method used for separating two compounds with
different solubilities in a solvent S. The process of fractional crystallisation is carried
out in four steps.
(a) Preparation of the solution: The powdered mixture is taken in a flask and the
solvent is added to it slowly and stirred simultaneously. The solvent is added till the
solute is just dissolved in the solvent. This saturated solution is then heated.
(b) Filtration of the solution: The hot saturated solution is then filtered through a
filter paper in a China dish.
(c) Fractional crystallisation: The solution in the China dish is now allowed to cool. The
less soluble compound crystallises first, while the more soluble compound remains in the
solution. After separating these crystals from the mother liquor, the latter is
concentrated once again. The hot solution is allowed to cool and consequently, the
crystals of the more soluble compound are obtained.

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(d) Isolation and drying: These crystals are separated from the mother liquor by
filtration. Finally, the crystals are dried.

Ques 12.20: What is the difference between distillation, distillation under reduced
pressure and steam distillation ?
Ans: The differences among distillation, distillation under reduced pressure, and steam
distillation are given in the following table.

Distillation under reduced

Distillation Steam distillation
pressure

It is used for the purification It is used to purify

of compounds that are compound, which is s
This method is used to purify
associated with non-volatile immiscible in water.
a liquid that tends to
impurities or those liquids, steam, the compoun
decompose on boiling. Under
which do not decompose on and the steam gets
the conditions of reduced
boiling. In other words, water. After some t
1. pressure, the liquid will boil at
distillation is used to separate of water and liquid s
a low temperature than its
volatile liquids from non-volatile passes through the
boiling point and will,
impurities or a mixture of those condensed mixture o
therefore, not decompose.
liquids that have sufficient liquid is then separa
difference in boiling points. separating funnel.

Glycerol is purified by this

method. It boils with
Mixture of petrol and kerosene decomposition at a A mixture of water
2.
is separated by this method. temperature of 593 K. At a separated by steam
reduced pressure, it boils at
453 K without decomposition.

Ques 12.21: Discuss the chemistry of Lassaigne’s test.

Ans:
Lassaigne’s test
This test is employed to detect the presence of nitrogen, sulphur, halogens, and
phosphorous in an organic compound. These elements are present in the covalent form in
an organic compound. These are converted into the ionic form by fusing the compound
with sodium metal.

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The cyanide, sulphide, and halide of sodium formed are extracted from the fused mass
by boiling it in distilled water. The extract so obtained is called Lassaigne’s extract. This
Lassaigne’s extract is then tested for the presence of nitrogen, sulphur, halogens, and
phosphorous.
(a) Test for nitrogen

Chemistry of the test

In the Lassaigne’s test for nitrogen in an organic compound, the sodium fusion extract is
boiled with iron (II) sulphate and then acidified with sulphuric acid. In the process,
sodium cyanide first reacts with iron (II) sulphate and forms sodium hexacyanoferrate
(II). Then, on heating with sulphuric acid, some iron (II) gets oxidised to form iron (III)
hexacyanoferrate (II), which is Prussian blue in colour. The chemical equations involved
in the reaction can be represented as

(b) Test for sulphur

Chemistry of the test

In the Lassaigne’s test for sulphur in an organic compound, the sodium fusion extract is
acidified with acetic acid and then lead acetate is added to it. The precipitation of lead
sulphide, which is black in colour, indicates the presence of sulphur in the compound.

Chemistry of the test

The sodium fusion extract is treated with sodium nitroprusside. Appearance of violet
colour also indicates the presence of sulphur in the compound.

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If in an organic compound, both nitrogen and sulphur are present, then instead of NaCN,
formation of NaSCN takes place.
Na +C +N +S → NaSCN
This NaSCN (sodium thiocyanate) gives a blood red colour. Prussian colour is not formed
due to the absence of free cyanide ions.

(c) Test for halogens

Chemistry of the test

In the Lassaigne’s test for halogens in an organic compound, the sodium fusion extract is
acidified with nitric acid and then treated with silver nitrate.

If nitrogen and sulphur both are present in the organic compound, then the Lassaigne’s
extract is boiled to expel nitrogen and sulphur, which would otherwise interfere in the
test for halogens.
Ques 12.22: Differentiate between the principle of estimation of nitrogen in an
organic compound by
(i) Dumas method and (ii) Kjeldahl’s method.
Ans: In Dumas method, a known quantity of nitrogen containing organic compound is
heated strongly with excess of copper oxide in an atmosphere of carbon dioxide to
produce free nitrogen in addition to carbon dioxide and water. The chemical equation
involved in the process can be represented as

The traces of nitrogen oxides can also be produced in the reaction, which can be reduced
to dinitrogen by passing the gaseous mixture over a heated copper gauge. The dinitrogen
produced is collected over an aqueous solution of potassium hydroxide. The volume of
nitrogen produced is then measured at room temperature and atmospheric pressure.

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On the other hand, in Kjeldahl’s method, a known quantity of nitrogen containing organic
compound is heated with concentrated sulphuric acid. The nitrogen present in the
compound is quantitatively converted into ammonium sulphate. It is then distilled with
excess of sodium hydroxide. The ammonia evolved during this process is passed into a
known volume of H 2SO4. The chemical equations involved in the process are

The acid that is left unused is estimated by volumetric analysis (titrating it against a
standard alkali) and the amount of ammonia produced can be determined. Thus, the
percentage of nitrogen in the compound can be estimated. This method cannot be applied
to the compounds, in which nitrogen is present in a ring structure, and also not applicable
to compounds containing nitro and azo groups.
Ques 12.23: Discuss the principle of estimation of halogens, sulphur and phosphoru s
present in an organic compound.
Ans: Estimation of halogens
Halogens are estimated by the Carius method. In this method, a known quantity of
organic compound is heated with fuming nitric acid in the presence of silver nitrate,
contained in a hard glass tube called the Carius tube, taken in a furnace. Carbon and
hydrogen that are present in the compound are oxidized to form CO 2 and H2O
respectively and the halogen present in the compound is converted to the form of AgX.
This AgX is then filtered, washed, dried, and weighed.
Let the mass of organic compound be m g.
Mass of AgX formed = m1 g
1 mol of Agx contains 1 mol of X.
Therefore,

Mass of halogen in m 1 g of AgX

Estimation of Sulphur
In this method, a known quantity of organic compound is heated with either fuming nitric
acid or sodium peroxide in a hard glass tube called the Carius tube. Sulphur, present in
the compound, is oxidized to form sulphuric acid. On addition of excess of barium
chloride to it, the precipitation of barium sulphate takes place. This precipitate is then
filtered, washed, dried, and weighed.
Let the mass of organic compound be m g.
Mass of BaSO 4 formed = m1 g
1 mol of BaSO 4 = 233 g BaSO 4 = 32 g of Sulphur

Therefore, m1 g of BaSO 4 contains

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Estimation of phosphorus
In this method, a known quantity of organic compound is heated with fuming nitric acid.
Phosphorus, present in the compound, is oxidized to form phosphoric acid. By adding
ammonia and ammonium molybdate to the solution, phosphorus can be precipi tated as
ammonium phosphomolybdate.
Phosphorus can also be estimated by precipitating it as MgNH 4PO4 by adding magnesia
mixture, which on ignition yields Mg 2P2O7.
Let the mass of organic compound be m g.
Mass of ammonium phosphomolybdate formed = m1 g
Molar mass of ammonium phosphomolybdate = 1877 g

If P is estimated as Mg 2P2O7,

Ques 12.24: Explain the principle of paper chromatography.

Ans: In paper chromatography, chromatography paper is used. This paper contains water
trapped in it, which acts as the stationary phase. On the base of this chromatography
paper, the solution of the mixture is spotted. The paper strip is then suspended in a
suitable solvent, which acts as the mobile phase. This solvent rises up the
chromatography paper by capillary action and in the procedure, it flows over the spot.
The components are selectively retained on the paper (according to their differing
partition in these two phases). The spots of different components travel with the mobile
phase to different heights. The paper so obtained (shown in the given figure) is known as
a chromatogram.

Ques 12.25: Why is nitric acid added to sodium extract before adding silver nitrate
for testing halogens?
Ans: While testing the Lassaigne’s extract for the presence of halogens, it is first
boiled with dilute nitric acid. This is done to decompose NaCN to HCN and Na 2S to H2S
and to expel these gases. That is, if any nitrogen and sulphur are present in the form of

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NaCN and Na2S, then they are removed. The chemical equations involved in the reaction
are represented as

Ques 12.26: Explain the reason for the fusion of an organic compound with metallic
sodium for testing nitrogen, sulphur and halogens.
Ans: Nitrogen, sulphur, and halogens are covalently bonded in organic compounds. For
their detection, they have to be first converted to ionic form. This is done by fusing the
organic compound with sodium metal. This is called “Lassaigne’s test”. The chemical
equations involved in the test are

Carbon, nitrogen, sulphur, and halogen come from organic compounds.

Ques 12.27: Name a suitable technique of separation of the components from a
mixture of calcium sulphate and camphor.
Ans: The process of sublimation is used to separate a mixture of camphor and calcium
sulphate. In this process, the sublimable compound changes from solid to vapour state
without passing through the liquid state. Camphor is a sublimable compound and calcium
sulphate is a non-sublimable solid. Hence, on heating, camphor will sublime while calcium
sulphate will be left behind.
Ques 12.28: Explain, why an organic liquid vaporises at a temperature below its
boiling point in its steam distillation?
Ans: In steam distillation, the organic liquid starts to boil when the sum of vapour
pressure due to the organic liquid (p1) and the vapour pressure due to water (p2) becomes
equal to atmospheric pressure (p), that is, p = p1 + p2
Since p1 < p2, organic liquid will vapourise at a lower temperature than its boiling point.
Ques 12.29: Will CCl 4 give white precipitate of AgCl on heating it with silver
nitrate? Give reason for your answer.
Ans: CCl4 will not give the white precipitate of AgCl on heating it with silver nitrate. This
is because the chlorine atoms are covalently bonded to carbon in CCl 4. To obtain the
precipitate, it should be present in ionic form and for this, it is necessary to prepare the
Lassaigne’s extract of CCl 4.
Ques 12.30: Why is a solution of potassium hydroxide used to absorb carbon dioxide
evolved during the estimation of carbon present in an organic compound?

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Ans: Carbon dioxide is acidic in nature and potassium hydroxide is a strong base. Hence,
carbon dioxide reacts with potassium hydroxide to form potassium carbonate and water
as

Thus, the mass of the U-tube containing KOH increases. This increase in the mass of U-
tube gives the mass of CO 2 produced. From its mass, the percentage of carbon in the
organic compound can be estimated.
Ques 12.31: Why is it necessary to use acetic acid and not sulphuric acid for
acidification of sodium extract for testing sulphur by lead acetate test?
Ans: Although the addition of sulphuric acid will precipitate lead sulphate, the addition
of acetic acid will ensure a complete precipitation of sulphur in the form of lead sulphate
due to common ion effect. Hence, it is necessary to use acetic acid for acidification of
sodium extract for testing sulphur by lead acetate test.
Ques 12.32: An organic compound contains 69% carbon and 4.8% hydrogen, the
remainder being oxygen. Calculate the masses of carbon dioxide and water produced
when 0.20 g of this substance is subjected to complete combustion.
Ans: Percentage of carbon in organic compound = 69 %
That is, 100 g of organic compound contains 69 g of carbon.

∴0.2 g of organic compound will contain

Molecular mass of carbon dioxide, CO 2 = 44 g
That is, 12 g of carbon is contained in 44 g of CO 2.

Therefore, 0.138 g of carbon will be contained in = 0.506 g of CO 2

Thus, 0.506 g of CO 2 will be produced on complete combustion of 0.2 g of organic
compound.
Percentage of hydrogen in organic compound is 4.8.
i.e., 100 g of organic compound contains 4.8 g of hydrogen.

Therefore, 0.2 g of organic compound will contain

It is known that molecular mass of water (H 2O) is 18 g.
Thus, 2 g of hydrogen is contained in 18 g of water.

∴0.0096 g of hydrogen will be contained in of water

Thus, 0.0864 g of water will be produced on complete combustion of 0.2 g of the organic
compound.

Ques 12.33: A sample of 0.50 g of an organic compound was treated according to

Kjeldahl’s method. The ammonia evolved was absorbed in 50 mL of 0.5 M H 2 SO4.
The residual acid required 60 mL of 0.5 M solution of NaOH for neutralisation. Find
the percentage composition of nitrogen in the compound.

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Ans: Given that, total mass of organic compound = 0.50 g

60 mL of 0.5 M solution of NaOH was required by residual acid for neutralisation.

60 mL of 0.5 M NaOH solution H2SO4 = 30 mL of 0.5 M H 2SO4

∴Acid consumed in absorption of evolved ammonia is (50–30) mL = 20 mL
Again, 20 mL of 0.5 MH 2SO4 = 40 mL of 0.5 MNH 3
Also, since 1000 mL of 1 MNH 3 contains 14 g of nitrogen,

∴ 40 mL of 0.5 M NH 3 will contain = 0.28 g of N

Therefore, percentage of nitrogen in 0.50 g of organic compound = 56 %

Ques 12.34: 0.3780 g of an organic chloro compound gave 0.5740 g of silver

chloride in Carius estimation. Calculate the percentage of chlorine present in the
compound.
Ans: Given that,
Mass of organic compound is 0.3780 g.
Mass of AgCl formed = 0.5740 g
1 mol of AgCl contains 1 mol of Cl.
Thus, mass of chlorine in 0.5740 g of AgCl

∴ Percentage of chlorine
Hence, the percentage of chlorine present in the given organic chloro compound
is .

Ques 12.35: In the estimation of sulphur by Carius method, 0.468 g of an organic

sulphur compound afforded 0.668 g of barium sulphate. Find out the percentage of
sulphur in the given compound.
Ans: Total mass of organic compound = 0.468 g [Given]
Mass of barium sulphate formed = 0.668 g [Given]
1 mol of BaSO 4 = 233 g of BaSO 4 = 32 g of sulphur

Thus, 0.668 g of BaSO 4 contains of sulphur = 0.0917 g of sulphur

Therefore, percentage of sulphur = 19.59 %

Hence, the percentage of sulphur in the given compound is 19.59 %.

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Ques 12.36: In the organic compound CH 2=CH–CH2–CH2–C≡CH, the pair of hydridised

orbitals involved in the formation of: C 2 – C3 bond is:
(a) sp – sp2
(b) sp – sp3
(c) sp2 – sp3
(d) sp3– sp3

Ans:
In the given organic compound, the carbon atoms numbered as 1, 2, 3, 4, 5, and 6
are sp, sp, sp3, sp3, sp2, and sp2 hybridized respectively. Thus, the pair of hybridized
orbitals involved in the formation of C 2-C3 bond is sp – sp3.

Ques 12.37: In the Lassaigne’s test for nitrogen in an organic compound, the
Prussian blue colour is obtained due to the formation of:
(a) Na4[Fe(CN)6]
(b) Fe4[Fe(CN)6]3
(c) Fe2[Fe(CN)6]
(d) Fe3[Fe(CN)6]4
Ans: In the Lassaigne’s test for nitrogen in an organic compound, the sodium fusion
extract is boiled with iron (II) sulphate and then acidified with sulphuric acid. In the
process, sodium cyanide first reacts with iron (II) sulphate and forms sodium
hexacyanoferrate (II). Then, on heating with sulphuric acid, some iron (II) gets oxidised
to form iron (III) hexacyanoferrate (II), which is Prussian blue in colour. The chem ical
equations involved in the reaction can be represented as

Hence, the Prussian blue colour is due to the formation of Fe 4[Fe(CN) 6]3.

Ques 12.38: Which of the following carbocation is most stable?

(a)

(b)

(c)

(d)

Ans: is a tertiary carbocation. A tertiary carbocation is the most stable

carbocation due to the electron releasing effect of three methyl groups. An increased +I
effect by three methyl groups stabilizes the positive charge on the carbocation.

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Ques 12.39: The best and latest technique for isolation, purification and separation
of organic compounds is:
(a) Crystallisation
(b) Distillation
(c) Sublimation
(d) Chromatography
Ans: Chromatography is the most useful and the latest technique of separation and
purification of organic compounds. It was first used to separate a mixture of coloured
substances.

Ques 12.40: The reaction:

is classified as :
(a) electrophilic substitution
(b) nucleophilic substitution
(c) elimination
(d) addition

Ans:
It is an example of nucleophilic substitution reaction. The hydroxyl group of KOH (OH –)
with a lone pair of itself acts as a nucleophile and substitutes iodide ion in CH 3CH2I to
form ethanol.

Q.1 Ethyne is a stronger acid than propyne. Explain.

Answer: Terminal alkynes (R−C≡C−H) are weakly acidic in nature because of sp-
hybridised state of the triple bonded carbon atom. Due to substantial s -character (50%),
the triple bonded carbon is electronegative in nature and this enables the release of
H+ ion from ≡C−H bond. However, ethyne is a stronger acid than propyne. This is
attributed to the electron releasing +I effect of the methyl group which tends to
increase the electron density on the triple bonded carbon atom in propyne. The release
of H+ion from propyne is more difficult than from ethyne or it is a weaker acid than
ethyne.

Q.2 Electromeric effect is a temporary effect. Assign reason.

Answer: The electromeric effect is noticed in the organic compounds containing multiple
bond i. e., double bond (> C = C < or > C = O) or triple bond (−C≡N) under the influence of
the attacking reagent. The moment the attacking reagent is removed, pi ( π) electron pair
comes back to its original position forming multiple bond again. Therefore, electromeric
effect is a temporary effect.
Q.3 Alcohols are weaker acids than water. Why?

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Answer: In alcohol (R→−O−H), the alkyl group has +I effect. It increases the electron
density on the oxygen atom. As a result, the release of H + ion from alcohol is more
difficult than from water or alcohol is a weaker acid.
Q.4 Ethylamine is a stronger base than acetamide. Assign reason.
Answer: In acetamide, the carbonyl group is electron withdrawing in nature. It
decreases the electron density on the nitrogen atom of the amino group due to
conjugation. On the other hand, in ethylamine, the ethyl group

has

effect and it increases the electron density on the nitrogen

atom. Therefore, electron releasing tendency is more in ethylamine than in acetamide or
the former is a stronger base.
Q.5 Higher alkyl substituted alkene is formed in greater proportion than the lower
alkyl substituted alkene. Justify.
Answer: In alkyl substituted alkene, the α-hydrogen atoms of the methyl group are
involved in the hyper conjugation with the pi(π) electron pair of the double bond. As a
result, the stability of alkene increases. Greater the number of such groups more will be
the stability of alkene. Thus, the relative order of stability of the following alkenes is:

Q.6 Benzyl carbocation is more stable than ethyl carbocation. Justify.

Answer: In ethyl carbocation, there is only hyper-conjugation of the three α-hydrogen
atoms and as a result, the following contributing structures are feasible.

But benzyl carbocation is more stable due to the presence of resonance and the following
resonating structures are possible:

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Q.7 How will you separate a mixture of benzoic acid and naphthalene?
Answer: Both these solids sublime on heating. Therefore, these cannot be separated by
sublimation. The mixture is heated with water when only benzoic acid will dissolve. Upon
filtration, naphthalene is separated and the solution upon cooling gives crystals of
benzoic acid. Alternatively the mixture is reacted with strong aqueous sodium hydroxide
when benzoic acid is converted to soluble sodium benzoate while napthalene is
unaffected. It can be separated by filtration. The filtrate is then treated with dilute
HCl to regenerate benzoic acid.

Q.8 Give the IUPAC name of the saturated hydrocarbon having the following carbon
skeleton.

Answer: 5-Ethyl-2, 3, 4-trimethyloctane

Q.9 Give the IUPAC name for the amine.

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Answer: N, N, 3-Trimethylpentan-3-amine (Alphabets are given preference over

numerals).
Q.10 Write resonance structures of the given compound.

Answer: The following four resonance structures can be written for the given compound.

Q.11 (a) Write down resonating structure and tautomer

of is more basic than HC≡C−. Explain why.

Answer:

(b) Since, sp-carbon is more electronegative than

sp carbon, therefore, CH≡C is less willing to donate a pair of electrons than H 2C=CH−.
2- −

In other words, H 2C=CH− is more basic than HC≡C−.

Q.12 Which of the following pairs do not constitute resonance structures? (a)

(d) CH3CH=CHCH3andCH3CH2CH=CH2

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Answer: (a) The two structures differ in the position of atoms and hence they are not
resonance structures. In fact, these are functional isomers, i.e., CH 3−NO2 having nitro
(−NO2) group as the functional group and CH 3−ONO having nitrite (O=N−O −) as the

functional group. (b) These two are resonance

structures because they differ in the position of electrons only and not atoms. (c) These
are not resonance structures since they differ in the position of atoms. They are, in

fact, tautomers. (d) These are not resonance

structures since these differ in the position of double bond. In fact, these are position
isomers.

Q.13 Explain the following: (i) exists in keto form but exists in
enol form. (ii) CH 2=CH is a better nucleophile than HC≡C−.
−

Answer: (i)

Enol form (II) is not stabilized

and hence it exists in the keto form (I) Enol form (IV) is stabilized by resonance energy
(150.6kJmol−1) of the benzene ring and hence (III) exists in the enol form (IV) (ii) In
H2C=CH−, the carbon atom carrying the -ve charge is sp 2-hybridized while in HC≡C−, the
carbon atom carrying the -ve charge is sp-hybridized. Since a sp 2-hybridized carbon is
less electronegative than a sp-hybridized carbon, therefore, H 2C=CH−is a better
nucleophile than HC≡C−.
Q.14 When do we use a fluted filter paper or hot water funnel for filtration?
Answer: To avoid crystallization during filtration, fluted filter paper is used when the
volume of the solution to be filtered is small and hot water funnel when the volume is
large.
Q.15 How will you purify a liquid having non-volatile impurities?
Answer: Simple distillation will give us the pure liquid while the non- volatile impurities
will remain in the flask as residue.
Q.16 Suggest a method to purify : (i) Camphor containing traces of common salt. (ii)
Kerosene oil containing water. (iii) A liquid which decomposes at its boiling point.
Answer: (i) Sublimation. Camphor sublimes while common salt remains as residue in the
china dish. (ii) Since the two liquids are immiscible, the technique of solvent extraction

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with a separating funnel is used. The mixture is thoroughly shaken and the separating
funnel is allowed to stand. Kerosene being lighter than water forms the upper layer while
water forms the lower layer. The lower water layer is run off when kerosene oil is
obtained. It is dried over anhydrous CaCl 2 or MgSO4 and then distilled to give pure
kerosene oil. (iii) Distillation under reduced pressure.
Q.17 A mixture contains two components A and B. The solubilities of A and B in
water near their boiling point are 10 grams per 100 mL and 2 g per 100 mL
respectively. How will you separate A and B from this mixture?
Answer: Fractional crystallization. When the saturated hot solution of this mixture is
allowed to cool, the less soluble component B crystallizes out first leaving the more
soluble component A in the mother liquor.
Q.18 Suggest methods for the separation of the following mixtures. (i) A mixture of
liquid A (b.p. 365 K) and liquid B (b.p. 356 K). (ii) A mixture of liquid C (b.p. 353
K) and liquid D (b.p. 413 K).
Answer: (i) Fractional distillation because the boiling points of the two liquids differ by
just 9∘. (ii) Simple distillation since the boiling points of the two liquids are widely apart.
Q.19 How will you purify essential oils?
Answer: Essential oils are volatile and are insoluble in water. Therefore, they are
purified by steam distillation.
Q.20 How will you separate a mixture of o-nitrophenol and p-nitrophenol?
Answer: Steam distillation. o-Nitrophenol being steam volatile distils over along with
water while p-nitrophenol being non-volatile remains in the flask.
Q.21 (a) Write the IUPAC name of

(i) (b) Out

of which will be eluted first in moderately

polar solvent and why?
Answer: (a) (i) Methyl 3-chlorobut-2-en-1-oate (ii) 3-Methylcyclohexyne

(b) has significant dipole moment while being

symmetrical has zero dipole moment. Therefore, di-tert-butyl benzene is non-polar and
hence will not be adsorbed strongly on the adsorbent and hence it will be eluted first in
moderately polar solvent.

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Q.22 A liquid (1.0 g) has three components. Which technique will you employ to
separate them?
Answer: Column chromatography.
Q.23 The R f value of A and B in a mixture determined by TLC in a solvent mixture
are 0.65 and 0.42 respectively. If the mixture is separated by column
chromatography using the same solvent mixture as a mobile phase, which of the two
components, A or B, will elute first? Explain.
Answer: Since the R f value of A is 0.65, therefore, it is less strongly adsorbed as
compared to component B with R f value of 0.42. Therefore, on extraction of the column,
A will elute first.
Q.24 A mixture contains benzoic acid and nitrobenzene. How can this mixture be
separated into its constituents by the technique of extraction using an appropriate
chemical reagent?
Answer: The mixture is shaken with a dilute solution of NaHCO 3 and extracted with
ether or chloroform when nitrobenzene goes into the organic layer. Distillation of the
solvent gives nitrobenzene. The filtrate is acidified with dil. HCl when benzoic acid gets
precipitated. The solution is cooled and benzoic acid is obtained by filtration.
Q.25 Without using column chromatography, how will you separate a mixture of
camphor and benzoic acid?
Answer: Sublimation cannot be used since both camphor and benzoic acid sublime on
heating. Therefore, a chemical method using NaHCO 3 solution is used when benzoic acid
dissolves leaving camphor behind. The filtrate is cooled and then acidified with dil. HCl
to get benzoic acid.
Q.26 Name two compounds which do not contain halogen but give positive Beilstein
test.
Answer: Urea and thiourea give positive Beilstein test due to the formation of volatile
cupric cyanide.
Q.27 Will sodium cyanide give a positive Lassaigne's test for nitrogen?
Answer: Yes. During fusion with Na metal, the N of the organic compound is actually
converted into NaCN which is the primary requirement for Lassaigne's test for nitrogen.
Q.28 How will you test the presence of nitrogen in hydrazine?
Answer: If hydrazine (NH 2NH2)is fused with Na metal, it does not form NaCN since it
does not contain carbon and hence will not give +ve test for nitrogen. In order to test
the presence of N in such compounds, during fusion with Na, some charcoal or preferably
starch (which contains C but not N, S, halogens, etc.) is added. Under these conditions, C
of starch or charcoal combines with N of the compound to form NaCN which will now give
a +ve test for nitrogen.
Q.29 Lassaigne's test is not shown by diazonium salts. Why?
Answer: Diazonium salts usually lose N 2 on heating much before they have a chance to
react with fused sodium metal. Therefore, diazonium salts do not show positive
Lassaigne's test for nitrogen.

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Q.30 Sometimes a red colour is not produced in the Lassaigne's test even if both
nitrogen and sulphur are present in the organic compound. Explain.
Answer: In principle, if the organic compound contains both N and S, sodium thiocyanate
should be formed in Lassaigne's test and this should give blood red colouration

with

3NaCNS+FeCl3→

However, if blood red colouration is not

obtained, it does not necessarily mean that S is absent. This is because in presence of
excess of sodium metal, sodium thiocyanate initially formed, decomposes to form sodium

cyanide and sodium sulphide. 2Na+2NaCNS NaCN+Na2S As a result, blood red

colouration is not obtained.
Q.31 Why is a freshly prepared saturated solution of ferrous sulphate used in the
Lassaigne's test for nitrogen?
Answer: On keeping aq. FeSO 4 solution, it undergoes oxidative-hydrolysis to form basic
ferric sulphate 4FeSO 4+2H2O+O2 4Fe(OH)SO 4 The pale yellow colour of Fe 3+ ions
interferes with the light green colour usually obtained in Lassaigne's test.

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