JEE - MODULE 4 - CHEM - Organic Chemistry

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TABLE OF CONTENTS
GENERAL ORGANIC CHEMISTRY
Theory ............................................................................................................................................... 8
Solved Examples............................................................................................................................... 56
Exercise - 1 : Basic Objective Questions........................................................................................... 62
Exercise - 2 : Previous Year JEE MAIN Questions .......................................................................... 76
Exercise - 3 : Advanced Objective Questions ................................................................................ 81
Exercise - 4 : Previous Year JEE Advanced Questions ................................................................... 92
Answer Key ....................................................................................................................................... 206
HYDROCARBONS
Theory ............................................................................................................................................... 98
Solved Examples............................................................................................................................... 160
Exercise - 1 : Basic Objective Questions........................................................................................... 166
Exercise - 2 : Previous Year JEE MAIN Questions ........................................................................... 179
Exercise - 3 : Advanced Objective Questions ................................................................................ 186
Exercise - 4 : Previous Year JEE Advanced Questions ................................................................... 201
Answer Key ....................................................................................................................................... 208

General Organic Chemistry 7
Teacher’s Note:
We encounter various petroleum products everywhere

But have you ever thought about what their source is?
The answer is Hydrocarbons !!
Hydrocarbons are naturally occurring compounds, and they
form the basis of crude oil, coal, natural gas, and
other fuel sources. Hydrocarbons are highly combustible
and produce a high amount of energy on burning.
"Samajh ayega to mazaa ayega,

Mazaa ayega to samajh ayega".
Vamsi sir is Graduate from IIT Bombay, his passion is to Re-

Imagine Teaching & Learning. he has been a pioneer in
creating a system to produce Top Ranks in JEE and
Olympiads. He has personally taught and mentored AIR 1,6,7
(JEE ADVANCED), and thousands of more students who have
successfully cleared these competitive exams in the last few
years.
01
Chapter 01 9
tissues and skin are formed by proteins, respiration is

1. GENERAL ORGANIC CHEMISTRY
possible due to haemoglobin, the information in our genes
is carried out in the form of DNA/RNA etc.
1.1 Introduction
General Organic Chemistry is the detailed study of the
In 1807, Berzelius proposed the term ‘Organic Chemistry’ basic concepts and factors that govern the progress
for the study of compounds derived from natural sources. and outcome of reactions.
This was based on the theory of vitalism which said that
all living systems possessed a ‘vital force’ which was absent
in non-living systems. Compounds derived from living The making and breaking of bonds usually occurs
natural sources (organic) were thought to be fundamentally in several discrete steps before transforming
different from inorganic compounds.
into products. The detailed sequential description of all the steps
is called the mechanism of the reaction.
2. REPRESENTATION OF COMPOUNDS
2.1 Sigma and Pi Bonds - Comparison

The vital force could be philosophically thought as the
mysterious force God instilled in the living systems.
In 1823, Friedrich Wohler joined Berzelius as his student.
In 1828, Wohler made a discovery which changed the
definition of organic chemistry. Wohler conducted the
following experiment.
O
||

NH 4 CNO   NH 2  C  NH 2
(Ammonium Urea
Cyanate) ( First organic compound
synthesised in laboratory )
Wohler successfully synthesized an organic compound

starting from an inorganic compound. Following this, many
others synthesized organic compounds starting from
inorganic compounds. Thus, the theory of vitalism and the
definition of organic chemistry lost its meaning.
But what was common in all the above compounds 2.2 Structural Formula
synthesized was the presence of carbon. Carbon shows a Several kinds of formulas are used by organic chemists to
special property catenation. Carbon can connect with other represent organic compounds.
carbon atoms to form long chains and rings (self-
2.2.1 Complete Formula
catenation) and can connect with atoms of many other
elements in the periodic table (cross-catenation). Because Complete formulas are lewis structures which shows all
of this reason, carbon can form a wide variety of bond pair of electrons as a dash (–). Lone pair of electrons
compounds. Therefore, the modern definition of organic are shown as a pair of dots.
chemistry is the study of carbon compounds.
Probably, the vital force can be explained by the fact that
most of the life-giving and life-sustaining functions are
performed by carbon compounds, for example, the human
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General Organic chemistry
GENERAL ORGANIC CHEMISTRY 10
2.3 Degrees of Carbon

H H
| | It is defined as the number of carbons attached to carbon
Example:- H  C  C H under observation.
| |
H H
Methyl
2.2.2 Condensed Formula
Condensed formulas are written without showing all the

individual bonds. Each central atom is shown together with 1° (Primary)
the atoms that are bonded to it.
Example:- CH3–CH3
2.2.3 Line-Angle Formula or Border Line Formula 2° (Secondary)
These are also called skeletal structures or a stick figure.

Line-angle formulas are often used for cyclic compounds
and occasionally for non-cyclic ones. Bonds are represented
by lines, and carbon atoms are assumed to be present where
two lines meet or a line begins or ends. Hydrogens are 3° (Tertiary)
generally implicit in these drawings.
Example:- Propane
2.2.4 Tetrahedral Representation

4° (Quaternary)
This is generally the three-dimensional (3-D)
representation of molecules. Dashed Wedge ( ) or solid
wedge ( ) are used to indicate bonds projecting behind
the plane (away from the observer) and out of the plane 2.4 Hybridization
(towards the observer) respectively. Bonds lying in the Hybridisation is a process in which two or more atomic
plane of paper are depicted by using a normal line (—). orbitals of comparable energy of the valence-shell of an
atom (central atom of the molecule or ion) either in its
ground state or in its excited state mix together and give
rise to the formation of new degenerate orbitals which are
called hybrid orbitals.
Table : Hybridization of Common Molecules.
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2.5 Applications of Hybridization Conjugated > Isolated > Cumulated

Important :
1
Stability 
Energy Content of the molecule
2.7 Commonly Occuring Forms of Carbon

The commonly occuring forms of carbon are
2.5.1 Size of Hybrid Orbitals (a) Diamond (b) Graphite (c) Carbides
As % s-character increases, size of hybrid orbital decreases. (d) Fullerenes (e) Charcoal
Therefore 3
Diamond - Each C is sp . Tetrahedral solid.
3 2 2
Size of Hybrid Orbital : sp > sp > sp Graphite - Each C is sp . Layered solid with weak
2.5.2 Electronegativity of Hybrid Orbitals van der Waal’s forces between layers.
As % s-character increases, electronegativity of hybrid Calcium Carbide - Each C is sp.
orbital increases. Therefore 2
Fullerene - Each C is sp .
2 3
EN of Hybrid Orbital : sp > sp > sp
3. BREAKING OF BONDS
2.6 Dienes
In organic chemistry, the bond that is important for the study
Dienes are organic compounds containing two double of reactions is covalent bond. We, therefore, study ways in
bonds. There are three types of dienes : which a covalent bond can be broken.
(a) Isolated (b) Conjugated (c) Cumulated (a) Homolytic Fission (b) Heterolytic Fission
2.6.1 Isolated Diene 3.1 Homolytic Fission or Homolytic Cleavage
3
In this case, double bonds are separated by atleast one sp In this kind of bond breaking, each atom separates with
carbon. one electron, leading to the formation of highly reactive
species known as radicals (or free radicals).
The bond breaking is shown by two half-headed or fish-

2.6.2 Conjugated Diene hook arrows. A half-headed arrow shows the movement
Double bonds are separated by only one single bond (or 4 of one electron.
2
sp carbons in a row). Radicals are neutral and are odd electron species.
3.2 Heterolytic Fission or Heterolytic Cleavage
In this type of covalent bond breaking, the shared pair of
electrons are transferred to the more electronegative part.
Therefore, this fission leads to the formation of a cation
and an anion (ion-pair).
2.6.3 Cumulated Diene
Both sets of double bonds are at the same carbon.
A substituted allene
The bond breaking is shown by a full-headed arrow. A full
An allene is
headed arrow shows the movement of a pair of electrons. In
2.6.4 Stability of Dienes organic chemistry, the movement of electrons is always
The relative stabilities of dienes follows the order shown by curved arrows - half-headed or full-headed arrows.
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4. INDUCTIVE EFFECT Inductive effect may be due to single atom or a group of
When two unlike atoms form covalent bond, the electron- atoms. Relative inductive effects are measured with
pair forming the sigma bond is never shared equally reference to hydrogen. Those which donate electrons to
between the two atoms but is shifted slightly towards the carbon chain are called electron-donating groups (EDG)
more electronegative species. or electron-releasing groups (ERG) and are said to exert
+I effect. Those which withdraw electrons from carbon
chain are called electron-withdrawing groups (EWG)
and are said to exert –I effect.
Important :
1. I.E. of alkyl groups : 3° > 2° > 1° > CH3–
2. In general, greater is the number of carbons in an alkyl group,
greater is its +I effect.
There are broadly three types of groups/atoms that may 3. For problem-solving, we take electronegativity of sp-
3
be attached to carbon as illustrated. Although C is more hybridized carbon to be more than sp hybridized nitrogen.
electronegative than H, the electronegativity difference is 4.4 Applications of Inductive Effect
small and the bond is generally considered as non-polar.
4.4.1 Effect on Acidic/Basic Strength
4.1 Nature of Inductive Effect
EWG increases acidic strength and decreases basic
Inductive effect is a permanent effect and can be directly
strength. ERG decreases acidic strength and increases basic
correlated to its dipole moment.
strength.
It is a weak effect as the shifting of electrons takes place
Example - 1
only through sigma bonds.
Compare the acidic strength :
4.2 Effect of branched carbon chain
An illustration has been marked for operation of inductive (I) (II)
effect which is self-explanatory.
(III)
Solution :
An alkyl group is donating only if no other EWG is present
More the number of , lesser the effect on it. Therefore, groups like –CH2Cl and –CH2F become
4.3 Electron Donating and Electron withdrawing Groups electron withdrawing groups.
Order of Acidic Strength : III > II > I
Series of +I and –I groups in order of their strength
–I Series (EWG)
+I Series (ERG)
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4.4.2 Effect of Distance (a) (CH3)2NH > CH3NH2 > (CH3)3N > NH3
If the ERG/EWG moves away, the inductive effect i.e. 2° > 1° > 3° > NH3 (R = CH3)
diminishes. (b) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
i.e. 2° > 3° > 1° > NH3 (R = C2H5)
Example - 2
5. RESONANCE
Compare the acidic strength of :
Molecules are generally represented by simple lewis
(I)
structures but some molecules can not be represented by
(II) just one Lewis structure. This led to the discovery of
resonance. Resonance refers to the delocalization of
electrons (generally -electrons).
(III) 5.1 Conjugated Systems
5.1.1 Pi alternate Pi
(IV)
Example - 3
Solution :
(I)
(II)
(III)
(IV)
Order of acidic strength : II > III > IV > I

4.4.3 Basicity of Amines
5.1.2 Pi alternate Positive Charge
The order in gaseous or liquid phase is :
Example - 4
3° > 2° > 1° > NH3
To determine the basic strength of amines in aqueous
phase. We have to consider inductive effect, solvation
effect and steric hinderance. The order of basic strength
is therefore experimental in aqueous state as we can’t give
priority to stability provided by any one factor. Two results
are important for aqueous phase :
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5.1.3 Pi alternate Negative Charge Resonance forms can be compared using the following
criteria in the following order :
Example - 5
1. As many octets as possible (a neutral molecule is always
more stable in which its octet is complete).
2. As many  bonds as possible.
3. Negative charge on more electronegative atom is stable.
5.1.4 Pi alternate Odd Electron
4. Charge separation.
Example - 6 (a) Similar charges - Keep them as FAR as possible to
minimize repulsion and instability.
(b) Opposite charges - Keep them as NEAR as possible to
maximize attraction and stability.
5.1.5 Pi alternate Lone Pair Example - 9
This case is similar to ‘pi alternate negative charge’ as Which of the following structures is more stable ?
lone pair and negative charge are treated similarly.
Example - 7
Solution :
II is more stable as all the octets are complete.
Example - 10
Which of the following is more stable in the following
pairs ?
5.1.6 Lone Pair and Positive Charge on Adjacent Atoms
Example - 8 (a)
5.2 Rules for Validity of Lewis Structures

(b)
Rule-1 :
All the lewis structures must conform to lewis octet rule.
Rule-2 : Solution :
Position of atoms in all resonating structures must be the (a) In II, all octets are complete. Therefore, II is more stable.
same. Only the electrons move.
(b) I and II are tied on octets and number of  bonds but
Rule-3 : negative charge is more stable on more electronegative
All the resonating structures must have the same number atom. Hence, II is more stable.
of paired and unpaired electrons, i.e. sum of bond pairs Example - 11
and lone pairs must be constant.
Give the order of stability of following resonating
Rule-4 : structures
All the atoms participating in resonance in a molecule must
(I)
be coplanar. This is required for the effective overlap of
p orbitals and the delocalization of electrons, for eg,
buta-1,3-diene. (II)
5.3 Criteria for Major/Minor Contributors

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(ENZ > ENY)
(III) 6.1.3 Dual Behaviour
Groups such as are both electron-releasing and
(IV) electron-withdrawing as illustrated.
Example - 12
(V) As electron releasing group
Solution :
In (I), there are maximum number of pi bonds. Therefore,
it is most stable. In (II) and (V), the number of pi bonds is As electron withdrawing group
equal but charge separation is greater in (V). Therefore,
(II) is more stable than (V). In (III) and (IV), there is
maximum charge separation but (III) is highly unstable
Which behaviour dominates and which is used in a
due to electrostatic repulsion. Hence, the order of stability
particular context will be discussed later in Electrophilic
is :
Aromatic Substitution later.
I > II > V > IV > III
Resonance Effect does NOT depend upon distance
6. MESOMERIC EFFECT unlike inductive effect.
The permanent polarization, due to a group conjugated 6.2 Applications of Mesomeric Effect
with a  bond or a set of alternate bonds, is transmitted
through the  electrons of the system-resulting in a different 6.2.1 Effect on Acidic Strength of Carboxylic Acids and Phenols
distribution of electrons in the unsaturated chain. The resonating structure of carboxylic acid leads to charge-
This kind of electron redistribution in unsaturated separated structure which is less stable than the carboxylate
compounds conjugated with electron-releasing or electron- ion in which charge is delocalized. Therefore, carboxylic

withdrawing groups (or atoms) is called Mesomeric Effect acid readily loses proton (H ) to form a carboxylate ion.
or Resonance Effect.
This effect is permanent and is indicated by the dipole
moment.
6.1 Electron-Releasing and Electron-Withdrawing Groups

Groups which release or withdraw electrons by resonance
are said to exert M or R effect.
6.1.1 Electron-Releasing Groups (+R or +M effect)
The common thing about all the groups listed is that the
atom connected with the conjugated system has a lone pair Similarly, in phenol, resonance leads to charge separation
to donate. Therefore, a generic representation can be which increases the rate of ionization and forms phenoxide
ion which is stabilized by charge delocalization which
increase acidic strength of phenol.
6.1.2 Electron-Withdrawing Groups (–R or –M effect)
Order of acidic strength
The common thing about all the groups listed is that the atom RSO3H > RCOOH > H2CO3 > PhOH > CH3OH
connected with the conjugated system has a  bond with > H2O > ROH > HCCH > NH3 > CH4
another more electronegative atom which withdraws the
electrons or directly has a positive charge on them. Therefore,
a generic representation can be
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Example - 13
Arrange the following in the order of decreasing acidic
strength :
Solution :
6.2.2 Effect on Reactivity of Carboxylic Acid Derivatives
A typical nucleophilic reaction is represented as :
The order of acidic strength is : II > V > I > III > IV

In the previous example, let’s also discuss the stability of
phenoxide ions corresponding to (II) and (IV).
The stronger is the bond between C and Z, the difficult it

is for a nucleophile to break a bond and therefore, lower
reactivity.
Reactivity order of carboxylic acid derivatives towards

nucleophilic acyl substitution is :
Acyl Chloride > Acid Anhydride > Ester > Amide
6.2.3 Effect of ERG/EWG on Acidic/Basic Strength
EWG increases the acidic strength and decreases the basic
strength.
ERG decreases the acidic strength and increases the acidic
strength.
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Example - 14
Arrange the following in decreasing order of basic strength
Solution :
7. HYPERCONJUGATION
Hyperconjugation is the ability of the  bond electrons of
an  bond to undergo conjugation with the adjacent
 electrons. It is also known as Baker-Nathan Effect, No-
Bond Resonance and - Effect.
7.1 -Carbon and -Hydrogen

We have already discussed the , ,  nomenclature. Let’s
take an example :
Therefore, order of basic strength is : IV > III > I > V > II

Let’s also discuss the stability of anilinium ions corresponding -Carbon is the carbon attached to a functional group such
to (II) and (IV). as . The hydrogen attached to -carbon is called -
hydrogen. For an  bond to be eligible for
3
hyperconjugation,  C must be sp hybridized.
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Example - 15
Mark the number of -C and -H in the given compounds
(a)
(b)
Now, greater the number of -H, greater the number of
(c)
hyperconjugating structures and more is the electron
(d) donation of alkyl group to  bond.
The order of electron-donation of alkyl groups based on
hyperconjugation is :
Solution :
(a) C  4 H  12
Methyl > 1° > 2° > 3°
More is the number of -H, more is the 

bond delocalized. This implies that more will
be the stability of alkene and less will be the
(b) heat of hydrogenation and more is the no-bond resonance
energy.delocalized.
7.3 Applications of Hyperconjugation
7.3.1 Stability of Alkenes

 C = 4,  H = 0
More is the number of -hydrogen, more is the number of

(c) CH 2  CH  C H  CH 2 hyperconjugating structure and therefore more stability and
greater no bond resonance.
2
 C = 1,  H = 1 but since C is sp hybridized, therefore, Example - 16
it won’t participate in hyperconjugation. Therefore, H =
0 that will participate in hyperconjugation. Which alkene is more stable ?
(d)
Solution :
 C = 2,  H = 3
7.2 Mechanism of Electron Donation in Hyperconjugation
I is more stable than II.

7.3.2 Acidic Character of Alkenes
Hyperconjugation weakens the C-H bond in
The hybrid formed by these resonating structures better hyperconjugation hybrid (partial single bond) and therefore
known as hyperconjugating structures is : H can be lost easily.
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Hyperconjugation is a - interaction and acts through a

strong sigma and a weak pi bond.
Therefore, the order of importance is :
Resonance > Hyperconjugation > Inductive
7.3.3 Stability of Carbocations 10. STERIC INHIBITION OF RESONANCE (SIR)
When both the ortho positions of a bulky functional
group are occupied by bulky substituents, all the three
groups are out of plane of the benzene ring.
The positive charge on C is delocalized over H to give

stability to the carbocation. More is the number of H,
more is the stability of carbocations.
Stability of Carbocations Example - 17
Mark the order of basic strength :
8. ELECTROMERIC EFFECT
Electromeric effect is observed only in the presence of a Solution :
reagent and is therefore, a temporary effect. When a reagent In (II) and (III), the lone pair of N is in conjugation with the
approaches a molecule, the multiple bond such as benzene ring and is not available for donation. (II) is less
or is polarized by the complete transfer of  basic than (III) due to –I and –M of –NO2 group. It may
electrons. seem that (I) is least basic due to presence of 2 –NO2 groups
but –NO2 and –N(CH3)2 are all bulky groups. This is a case
of steric inhibition of resonance due to which the lone pair
of N is not in conjugation and is readily available for electron
donation. Hence, the order of basic strength is :
When the multiple bond is between two unlike atoms, the (I) > (III) > (II)
shift of electrons takes place towards more electronegative
atom. Example - 18
Mark the order of bond lengths in the given molecule.
9. COMPARISON OF INDUCTIVE, HYPERCONJUGATION

AND RESONANCE EFFECTS
Inductive Effect is a - interaction and acts through
strong sigma bonds.
Resonance/Mesomeric Effect is a - or -lone pair
interaction and acts through weak pi bonds.
SCAN CODE
Solution :
–I, –NO2 are bulky groups and is case of steric inhibition
of resonance. Therefore, the –NO2 groups ortho to –I are
out of conjugation while the –NO2 group para to –I will
be in conjugation with the benzene ring. Therefore, bonds
‘a’ and ‘b’ will always have single bond character while
‘c’ has double bond character. Therefore :
c<a=b
11. CARBOCATION
11.1 Definition
Carbocation is the intermediate of carbon containing
positive charge. It has six electrons in the valence shell.
11.2 Geometry and Hybridization
 2
Hybridization of C = sp

Geometry of C = Trigonal Planar
11.4 Stability of Carbocations

There are three factors contributing to the stability of
carbocations :
11.3 Classification of Carbocations (a) Inductive Effect
This classification will also be used for carbanions and (b) Hyperconjugation
carbon free radical and will be studied only in this section.
(c) Resonance
Methyl Carbocation Order of stability :
1° Primary Carbocation
2° Secondary Carbocation
3° Tertiary Carbocation
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Example - 19 Rate of formation of carbocation depends on :

Rank the stability of carbocations in each case : (a) The stability of carbocation formed.
(b) The nature of the leaving group. Weaker the base better
the leaving group. This is because weaker leaving group
implies a stable compound and its formation will therefore
be favoured.
(a)
11.5.2 Addition of Proton to a  bond
Solution :
Rate of carbocation formation depends on :
(a) Stability of carbocation formed.
(b) Strength of the electrophile.
11.6 Reactions of Carbocations

There are three important reactions of carbocations :
(a) Capture a Nucleophile
(b) Lose a proton to form a  bond.
(a) (c) Rearrangement
11.6.1 Capture a Nucleophile
11.6.2 Loose a proton to form a  bond
Example - 20
Form the products from the following reaction :
Solution :
Step-1 : Protonation
Order of stability : III > I > II
11.5 Formation of Carbocations
11.5.1 Ionization of Carbon-Leaving Group Bond Step-2 : Formation of Carbocation

In this method :
(a) Bond between carbon and leaving group ionizes.
(b) Leaving group accepts the pair of electrons that were shared
in the covalent bond. SCAN CODE
12. CARBANIONS
12.1 Definition
Carbanion is the intermediate of carbon containing negative
Step-3 : Deprotonation charge. It has eight electrons in the valence shell.
12.2 Geometry and Hybridization

3
Hybridization of : sp
Geometry : Trigonal Pyramidal
Carbanion and ammonia are isoelectronic species having
same structure
When carbocation deprotonation can lead to more than one

product, all products are formed and the most stable product
is the major product.
11.6.3 Carbocation Rearrangement
12.3 Stability
A carbocation can become more stable by rearrangement.
Bonding electrons of carbocation may shift between ERG will increase the electron density at carbon and will
adjacent atoms to form more stable carbocation. There make it unstable. EWG will decrease the electro density
are two kinds of shifts that take place in order to gain at carbon and will make it stable.
stability. Order of Stability :
(a) Hydride Shift (b) Alkyl Shift
Example - 21
In the above example, both hydride and methyl shifts are

possible leading to more stable carbocation but only that
shift is preferred which leads to more stable
carbocation. In this example, hydride shift will take place.
Important : The shift takes place in the form of
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Example - 22 12.4.2 Formation from Carbonyl Compounds

Give the order of stability of : NOTE:
Solution :
As s-character increases, electronegativity of C increases
and therefore negative charge will become more stable.
Therefore, order of stability is :
III > II > I
There are three reasons for the easy formation of carbanion
from carbonyl compounds
(a) Resonance - stabilization of carbanion which is the
conjugate base of carbonyl compound.
(b) Hyperconjugation makes the C-H bond acidic.
(c) –I of increases the acidic strength of C–H bond.
12.4 Formation of Carbanion
There are two methods for the formation of carbanion : 12.5 Reactions of Carbanion
(A) Partial formation via Grignard Reagent The reactions of carbanion are very fast as electropositive
(B) Formation from Carbonyl Compounds carbon carries negative charge.
We will discuss these methods in the subsequent section 12.5.1 Grignard Reagent as a Base
In this reaction it captures acidic hydrogen.

12.4.1 Formation via Grignard Reagent
1. Carbanion is never formed as an intermediate that can be

isolated in the case of Grignard Reagent. It directly
participates in the reaction.
2. Dry ether is used in this formation as it is inert to Grignard
reagent. For the formation of Grignard reagent from aryl In (d), the reaction with terminal alkyne also takes place
halides, we use tetrahedrofuran (THF) as solvent. as sp-hydridized carbon is highly electronegative and
therefore H attached to it is fairly acidic.
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12.5.2 Grignard Reagent as a Nucleophile
Grignard Reagent reacts with carbonyl compounds to form

alcohols. This is a very important method for the synthesis
of alcohols.
Mechanism :
13. CARBON FREE RADICALS

13.1 Definition
Carbon Free Radical is the intermediate of carbon having
an odd electron. It is neutral and has seven electrons in the
valence shell. It is highly reactive as it requires only one
electron to complete its octet and therefore, is short-lived.
is never added along with the first step as Grignard
Reagent will react with to give as in previous 13.2 Geometry and Hybridization
reaction.
12.5.3 Aldol Condensation
This reaction is shown by carbonyl compounds containing
atleast one H in presence of dilute base such as dilute
NaOH.
The hybridization of carbon free radical was proposed after

Mechanism : experimental verification of structure of different radicals.
• 2
It was proposed that when ERG are placed on C , it has sp
3
hybridization and when EWG are placed on C•, it has sp
hybridization.
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13.3 Stability (b)

ERG increase stability while EWG decrease stability.
(I) (b) will take place as it is energetically feasible.
(II) Chain Propagation
(a)
13.4 Formation of Carbon Free Radical

(b)
Carbon Free Radicals are formed by homolytic cleavage of
bonds. They are formed :
(a) at high temperature in the gas phase
(b) in non-polar solvents (III) Chain Termination
(c) by ultraviolet light The various free radicals in the progress of reaction are :
(d) by addition of other radicals Cl•, CH3•. There are ways in which free radicals from
13.5 Reactions of Carbon Free Radical different chains may combine to terminate the reaction.
The most common reactions in which free radical is

involved are :
(a) Halogenation of alkanes.
(b) Addition of HBr in the presence of peroxides to alkenes.
(Anti-Markonikov Rule)
(c) -Halogenation of alkenes. There is a side-product that is formed in this
(d) Wurtz Reaction reaction. Besides these, a number of other side-products such
(e) Decarboxylation reaction as CH2Cl2, CHCl3 and CCl4 have also been observed. These
get formed since carbon free radical is highly reactive. It
13.5.1 Free Radical Halogenation of Alkanes randomly reacts with other species that make it stabler.
The typical reactions of free radical are chain reaction
mechanisms. There are three steps in a chain reaction
mechanism : initiation, propagation and termination.
Mechanism
(I) Chain Initiation
There are two choices :
(a)
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14. NOMENCLACTURE-I
14.1 INTRODUCTION
In 1949, an organization was set up to formulate the rules for naming organic compounds. This
organization is IUPAC - International Union for Pure and Applied Chemistry. Prior to this, the organic
compounds were known by their trivial/common names which generally indicated their source. For
example, formic acid gets its name from formica (Latin, red ants) and acetic acid gets its name from
acetum (Latin, vinegar).
Important : Systematic nomenclature is required in order to have unambigous names for all
compounds.
14.2 CLASSIFICATION OF HYDROCARBONS
Important :
1. Aliphatic Compounds do not have rings and exist as a chain of carbon atoms.
2. Alicyclic Compounds have similar properties as aliphatic compounds except that the carbon
chain exists in the form of ring.
3. Aromatic Compounds are based on the structure of benzene. These compounds are also
called arenes.
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14.3 HOMOLOGOUS SERIES

A homologous series (Greek homos = “the same as”) is a family of compounds in which each member
differs from the next by one methylene (CH2) group. The members of the homologous series are called
homologues. Example :
(a) Alkanes CnH2n + 2 (b) Alkenes CnH2n (c) Alkynes CnH2n – 2
14.4 IUPAC NAME TEMPLATE
This template will be used to give the name for any organic compound.
14.5 NOMENCLATURE OF UNBRANCHED ALKANES
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Meth, Eth, Prop, But, etc. are called compound roots. Compound roots represent the number of carbon
atoms.
14.6 RULES FOR NOMENCLATURE OF SIMPLE HYDROCARBONS
Rule-1 :
Determine the longest carbon chain in the molecule (parent chain). Where a double/triple bond is
present, choose the chain which includes these bonds. If there is a cyclic structure present, the
longest chain starts and stops within the cyclic structure.
EXAMPLE
(I) C C C C C C C C C Longest chain = 8
C C C
(II) C C C C C C C C C Longest chain = 9
C C C
(II) is the correct chain selection.
Rule-2 :
Assign numbers to each carbon of the parent chain. Numbering is done to identify the parent alkane
(compound root) and to locate the positions of the carbon atoms at which branching takes place. The
numbering is done in such a way that the branched atoms get the lowest possible number.
EXAMPLE
9 8 7 6 5 4 3 2 1
(I) C C C C C C C C C 4, 8-INCORRECT
C C C
1 2 3 4 5 6 7 8 9
(II) C C C C C C C C C 2, 6-CORRECT
C C C
If there is a tie for the first branch, then go to the second and so on until a difference is observed.
EXAMPLE
1 2 3 4 5 6
(I) C C C C C C 2, 4, 5-INCORRECT
C C C
6 5 4 3 2 1
(II) C C C C C C 2, 3, 5-CORRECT
C C C
Rule-3 :
Determine the compound root and the unsaturation index. Compound root corresponds to the number of
carbon atoms in parent chain. Add prefix cyclo if the parent chain is cyclic.
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EXAMPLE
C C C C C C C C C
C C C
C C C C [but] [ene]
 Butene
Rule-4 :
Determine the correct name for each branch for example, alkyl groups such as methyl, ethyl, etc.
Attach the name of the branches alphabetically along with their positions to the parent chain as
prefix. Separate numbers from letters with hyphens.
EXAMPLE
1 2 3 4 5 6 7 8 9
C C C C C C C C C
C C C
6-Ethyl-2-methylnonane
If two substituents are in equivalent positions, the lower number is given to the one coming first in
the alphabetical listing.
1 2 3 4 5 6 7 8
EXAMPLE (I) C C C C C C C C CORRECT
C C C
3-Ethyl-6-methyloctane
8 7 6 5 4 3 2 1
(II) C C C C C C C C INCORRECT
C C C
6-Ethyl-3-methyloctane
Rule-5 :
When two or more branches are identical, use prefixes di-, tri-, tetra-, etc. Numbers are separated with
commas and prefixes are ignored while determining alphabetical order.
EXAMPLE
C C
9 8 7 6 5 4 3 2 1 1 2 3 4 5 6 7 8 9
(I) C C C C C C C C C (II) C C C C C C C C C
C C C C C C
INCORRECT
3, 3-Dimethyl-7-ethylnonane INCORRECT
7-Ethyl-3, 3-dimethylnonane CORRECT
This is an incorrect selection as lowest number rule is violated.
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EXERCISE
Give the IUPAC names of :
CH2 CH2CH3
1. CH 3 CH CH3 2. CH3 CH2 C CH2 C CH3
CH3 CH3
3. 4. CH 3 C C CH CH3
CH3
14.7 ALKYL SUBSTITUENTS - COMMON AND SYSTEMATIC NAMES
CH3 – Methyl
CH3CH2 – Ethyl
From three carbon onwards, alkyl substituents can be complicated for which common as well as
systematic names are possible.
Rules for Systematic and Common Names

Rule-1 : For systematic names, the carbon atom of the branch that attaches to the parent chain is
numbered one.
Rule-2 : Substituents which have branching at the first carbon can be classified as secondary (sec-)
or tertiary (tert-) depending upon the number of carbons attached to it. ‘sec-’ and ‘tert– are
italicized and can also be abbreviated as ‘s-’ or ‘t-’ respectively.
Rule-3 : Substituents which have a CH3– group on second last carbon are called iso and which have
two methyl groups on second last carbon are called neo.
Rule-4 : Iso and neo are considered while determining alphabetical order of substituents. ‘sec-’ and
‘tert-’ are not considered.
CH3 CH3
CH CH3 C CH3
CH3
iso neo
Alkyl Substituent Systematic Name Common Name

1. CH2CH2CH3 propyl propyl
2. CH CH3 1-methyl ethyl isopropyl (not s-propyl)

CH3
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15. NOMENCLATURE–II
15.1 ALKYL SUBSTITUENTS – COMMON AND SYSTEMATIC NAMES

EXERCISE
Give IUPAC names for :
(a) (b)
15.1.1 Corollory to Longest Chain Rule
If there happen to be two chains of equal length, then that chain is selected which contains more
number of side chains
EXAMPLE
7
6
5
6 4 2 4 2
5 3
(I) 7 3 1
(II) 1
CORRECT (4 side chains) INCORRECT (3 side chains)
IUPAC Name : 2,3,5-Trimethyl-4-propyloctane
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15.2 FUNCTIONAL GROUPS
A functional group is an atom or a group of atoms which characterizes the chemical reactivity of
a molecule. The longest chain of atoms containing the functional group is numbered in such a way
that the carbon to which functional group is attached is assigned the lowest number. In case of
polyfunctional compounds, one of the functional groups is chosen as the principal functional group
and the compound is named treating other functional groups as substituents.
Class Formula Prefix Suffix
Acid Halide COX Halocarbonyl – carbonyl halide
(C)OX – – oyl halide
Alcohols OH Hydroxy – ol
Aldehydes CHO Formyl – carbaldehyde
(C)HO Oxo – al
Amides CONH2 Carbamoyl – carboxamide
(C)ONH2 – – amide
Amines NH2 Amino – amine
Carboxylates Carboxylato – carboxylate
– – oate
Carboxylic Acid COOH Carboxy– – carboxylic acid
(C)OOH – – oic acid
Ethers OR Alkoxy– –
Esters of COOR Alkoxy carbonyl Alkyl .. carboxylate
Carboxylic Acid (C)OOR – Alkyl ... oate
Ketones Oxo– – one
cyanides (Nitriles) Cyano – carbonitrile

– – nitrile
Salts of Carboxylic – Cation ... carboxylate
Acids – Cation ... oate

Sulphonic Acids Sulfo– – sulfonic acid
Thiols SH Sulfanyl – thiol
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The order of decreasing priority for functional groups is :
, , , , , , , , , , ,
,
Important :
(a) The –R, –C6H5, halogens, nitro and alkoxy groups are always treated as substituents.
(b) If more than one functional group of same type is present, its number is indicated by adding
di-, tri- etc.
(c) When C is marked in parenthesis, the carbon of the functional group is counted as part of the
parent chain and the numbering will always begin from this carbon and its position need not
be marked in the name.
EXERCISE
Write IUPAC names of :
COOH
(a) CH3CH2CH2CH2COOH (b) CH3CH2CH CH3 (c)
COOH
EXERCISE
O
(a) H C CH CH CH3 (b)
(c) CH3 C CH2CH2 CH 3 (d) H C CH2CH2CH2 CH 3
O O
(e) CH 3 C C CH2CH2 OH (f) CH3 C CH CH CH2OH
Br
(g) CH3 C CH2 COOH
EXERCISE
CH2 OH CH2 COOH CH2 COOH CH2 COOH
(a) CH OH (b) CH2 (c) CH COOH (d) CH OH
CH2 OH CH2 COOH CH2 COOH CH2 COOH
Important : Pentane-1, 5-dioic acid is incorrect name. There is no need to give positions of COOH
because if we include their carbons in the parent chain, they will always be present at the end of the
chain.
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EXERCISE
Give IUPAC names of :
O
O O
(a) (b) OH
OH O
15.3 PRIORITY BETWEEN ALKENE AND ALKYNE
When there is a choice between alkene and alkyne, alkene is given lower number.
EXERCISE
(a) (b) (c)
Important : ‘e’ of ‘ene’ is dropped as ‘yne’ sounds like starting from ‘i’ (vowel).
15.3.1 Common Alkenyl/Alkynyl Substituents
Structure Common Name Systematic Name

Vinyl Ethenyl
Allyl Prop-2-enyl
– Ethynyl
15.3.2 Chain selection Rules for Alkene and Alkyne Priority
Rule-1 : Select that chain which contains maximum number of double and triple bonds.
Rule-2 : If two chains are competing for selection as the chain with maximum number of unsaturated
bonds, then the choice goes to
(a) The one with the greatest number of carbon atoms.
(b) The number of carbon atoms being equal, the one containing maximum number of double bonds.
EXERCISE
(a) (b) (c) (d)
15.4 CYCLIC COMPOUNDS
Corollory to Longest Chain Rule

A ring is treated as a substituent only when the number of carbon atoms are less in the ring than in
the chain.
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EXAMPLE
CH3
(a) Cyclopropane (b) Cyclohexane (c) Methylcyclohexane
CH3 CH3 CH3

5 1 3
4 6 6 2 4 2
(d) (i) (ii) 3 (iii)
1
3 1 5 5
CH2CH3 CH2CH3 CH2CH3
2 4 6
EXERCISE
CH3 OH
CH2CH3 CH3 COOH
(a) (b) (c) (d) (e)
Br CH3
Cl
16. NOMENCLATURE–III
16.1 SUBSTITUENTS – ALKOXY, NITRO AND HALOGEN GROUPS
Alkoxy, nitro and halogen groups are always treated as substituents

Alcohol Alkoxy Group Substituent Name
CH3OH Methoxy
CH3CH2OH Ethoxy
CH3CH2CH2OH Propoxy
Isopropoxy
Phenoxy
EXAMPLE
OCH3
2-Methoxypentane
CH3CH2CHCHCH3
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EXAMPLE
O
(a) CH3 CH CH2 C CH3 (b) CH 3 CH CH CH3
OCH CH3 Cl Br
CH3
16.2 CARBOXYLIC ACID DERIVATIVES
Nomenclature of acid halides and amides is very straight forward.

EXAMPLE
O O
(I) CH3 CH2 C Cl (II) H C Cl

Propanoyl chloride Methonoyl chloride
(III) (IV)
Esters nomenclature is done in the following manner :
O O
(I) H C O CH3 (II) CH3 CH2 CH2 C O CH2CH3

Methyl methanoate Ethyl butanoate
(III)
(I) Methyl methanoate

(II) Ethyl butanoate
(III) 2-Methylpropyl-3-chlorobutanoate
Acid Anhydrides
Alkanoic (R1) + alkanoic (R2) anhydride

If R1 = R2, then name is Alkanoic anhydride
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EXAMPLE :
(I) Ethanoic anhydride
(II) Ethanoic Propanoic anhydride
EXERCISE :
(I) (II)
Cyanides/Nitriles
Alkane nitrile (C is counted as part of parent chain)
Alkane carbonitrile (C is not counted as part of parent chain)
EXAMPLE :
(I) Propanenitrile (II) Cyclohexane Carbonitrile
EXERCISE :
(I) (II) (III)
16.3 N-SUBSTITUTED AMINES/AMIDES

The substituents on nitrogen atom is written as N-<substituent name>. Here, ‘N’(italic) indicates the
position of substituent.
EXAMPLE
O
4 3 2 1 4 3 2 1 3 2 1
(I) CH3 CH2 CH CH2 NH Br (II) CH3 CH2 CH CH2 NH Cl (III) H2C CH C NH Cl
Br Br
15.4 NOMENCLATURE OF BENZENE DERIVATIVES
15.4.1 Common Names and IUPAC names of Important Compounds
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16.4.2 Ortho, Meta and Para Positions
With respect to substituent X, we define three positions on the benzene ring as shown in the figure.
Ortho, meta, para positions are used for writing common names of disubstituted benzenes. The positions
are also abbreviated as o-, m-, p-.
EXAMPLE
Br Br Br
Br
(I) (II) (III)

Br
o-Dibromobenzene
m-Dibromobenzene Br
1,2-Dibromobenzene
1,3-Dibromobenzene
p-Dibromobenzene
1,4-Dibromobenzene
EXERCISE
Give the IUPAC and common name (o/m/p wherever possible).
COOH OH Cl Br COOH SO3H
NO2 CH3 Cl Br F
(a) (b) (c) (d) (e) (f)
Cl O2N NO2
Br F
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16.4.3 Benzene as substituent-Phenyl Group
When C6H5– group is treated as substituent, it’s called phenyl group.

Important :
(a) A saturated chain containing benzene ring is named as derivative of the larger structural
unit. (Use corollory for longest chain selection for cyclic compounds).
(b) If the chain is unsaturated, the compound is always named as a derivative of that chain.
EXAMPLE
There is another special group in which C6H5– is present.
16.5 Alpha (), Beta (), Gamma () Nomenclature
Prior to IUPAC, greek symbols were used to indicate positions of the substituents or functional groups.
The carbons attached to the principal functional group are numbered as illustrated.
EXAMPLE
           
(I) C C C COOH (II) C C C OH (III) C C C (IV) C C C C N
O
   ' '
(V) C C C C C C
EXAMPLE
Draw the structure of
(a) -chloroacetic acid (b) , ‘-Dibromoacetone
Solution :
O
  '
(a) CH 2 COOH (b) CH2 C CH2
Cl Br Br
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17. COMMON NAMES IN ORGANIC CHEMISTRY
A. ALKANES
B. ALKENES
C. ALKYNES
D. ALKYL HALIDES
E. ALCOHOL
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F. ALDEHYDE
G. KETONE
H. CARBOXYLIC ACID
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I. ACID DERIVATIVES
J. N–DERIVATIVES
K. AROMATIC COMPOUNDS
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L. HETEROCYCLIC COMPOUNDS
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METHODS OF PURIFICATION
1. Sublimation 2. Crystallization
3. Distillation 4. Differential Extraction
5. Chromatography
Sublimation
1. Some solid substances change from solid to vapour state without passing through liquid state.
2. The purification technique is used to separate sublimable compounds from nonsublimable impurities.
Crystallization
1. It is based on the difference in the solubility of the compound and the impurities in a suitable solvent.
2. The impure compound is dissolved in a solvent in which it is sparingly soluble at room temperature but appreciably soluble
at higher temperature.
3. The solution is concentrated to get a nearly saturated solution. On cooling the solution, pure compound crystallises out
and is removed by filtration.The filtrate (mother liquor) contains impurities and small quantity of the compound.
4. The process of inducing crystallization by adding a crystal of pure substance into its saturated solution is called seeding.
5. Impurities, which impart colour to the solution, are removed by adsorbing over activated charcoal.
6. Repeated crystallisation becomes necessary for the purification of compounds containing impurities of comparable solubility
7. Sugar and benzoic acid are separated by this process.
Simple Distillation
This important method is used to separate
1. volatile liquids from non-volatile impurities
2. liquids having sufficient difference in their boiling points.
Liquids having different boiling points vaporise at different temperatures. The vapours are cooled and the liquids so formed
are collected separately.
Example
Chloroform (b.p. 334 K) and Aniline (b.p. 457 K)
MECHANISM
1. On boiling, the vapours of lower boiling component are formed first. The vapours are condensed by using a condenser
and the liquid is collected in a receiver.
2. The vapours of higher boiling component form later and the liquid can be collected separately.
Fractional Distillation
Fractional distillation is required if the difference in boiling points of two liquids is not much or less than 25ºC. The vapours of such
liquids are formed within the same temperature range and are condensed simultaneously.
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MECHANISM
1. Vapours of a liquid mixture are passed through a fractionating column before condensation.
2. Vapours of the liquid with higher boiling point condense before the vapours of the liquid with lower boiling point.
3. The vapours rising up in the fractionating column become richer in more volatile component.
4. By the time the vapours reach to the top of the fractionating column, these are rich in the more volatile component.
Fractionating columns
1. A fractionating column provides many surfaces for heat exchange between the ascending vapours and the descending
condensed liquid.
2. The vapours thus become richer in low boiling component. The vapours of low boiling component ascend to the top of the
column.
3. On reaching the top, the vapours become pure in low boiling component and pass through the condenser and the pure
liquid is collected in a receiver.
4. After a series of successive distillations, the remaining liquid in the distillation flask gets enriched in high boiling component.
5. Each successive condensation and vaporisation unit in the fractionating column is called a theoretical plate.
Application: Crude oil in petroleum industry.

Types of Fractionating Columns
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Distillation under Reduced Pressure

This method is used to purify liquids having very high boiling points and those, which decompose at or below their boiling
points.
Such liquids are made to boil at a temperature lower than their normal boiling points by reducing the pressure on their surface.
A liquid boils at a temperature at which its vapour pressure is equal to the external pressure. The pressure is reduced with the
help of a water pump or vacuum pump.
Application: Glycerol can be separated from spent-lye in soap industry.
Steam Distillation
1. It is used to separate substances which are steam volatile and are immiscible with water.
2. In steam distillation, steam from a steam generator is passed through a heated flask containing the liquid to be
distilled. The mixture of steam and the volatile organic compound is condensed and collected.
3. In steam distillation, the liquid boils when the sum of vapour pressures due to the organic liquid (p1) and that due to
water (p2) becomes equal to the atmospheric pressure (p), i.e. p =p1 + p2. Since p1 is lower than (p2) , the organic liquid
vaporises at lower temperature than its boiling point.
4. Thus, if one of the substances in the mixture is water and the other, a water insoluble substance, then the mixture will
boil close to but below, 373K.
5. A mixture of water and the substance is obtained which can be separated by using a separating funnel.
Example: Aniline–Water Mixture
Differential Extraction
When an organic compound is present in an aqueous medium, it is separated by shaking it with an organic solvent in which it
is more soluble than in water.
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The organic solvent and the aqueous solution should be immiscible with each other so that they form two distinct layers which
can be separated by separatory funnel. The organic solvent is later removed by distillation or by evaporation to get back the
compound.
If the organic compound is less soluble in the organic solvent, a very large quantity of solvent would be required to extract
even a very small quantity of the compound. Continuous extraction is employed in such cases. In this technique same solvent
is repeatedly used for extraction of the compound.
Differential Extraction Apparatus
Chromatography
Chromatography is used to separate mixtures into their components, purify compounds and also to test the purity of compounds. It
is based on adsorption.
Greek word chroma - colour.
MECHANISM
1. The mixture of substances is applied onto a stationary phase, which may be a solid or a liquid. A pure solvent, a mixture of
solvents, or a gas is allowed to move slowly over the stationary phase.
2. The components of the adsorbent are placed on the top of the adsorbent column packed in a glass tube. An appropriate
eluant, which is a liquid or a mixture of liquids is allowed to flow down the column slowly.
3. Depending upon the degree to which the compounds are adsorbed, complete separation takes place. The most readily
adsorbed substances are retained near the top and others come down to various distances in the column.
Column Chromatography
Different stages represent the progressive separation of the mixture into three bands.
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Thin Layer Chromatography
It involves separation of substances of a mixture over a thin layer of an adsorbent coated on glass plate. A thin layer of an
adsorbent (silica gel or alumina) is spread over a glass plate of suitable size. The plate is known as thin layer chromatography
plate or chromaplate.
MECHANISM
1. The solution of the mixture to be separated is applied as a small spot about 2 cm above one end of the TLC plate. The
glass plate is then placed in a closed jar containing the eluant.
2. As the eluant rises up the plate, the components of the mixture move up along with the eluant to different distances
depending on their degree of adsorption and separation takes place.
3. The relative adsorption of each component of the mixture is expressed in terms of its retardation factor i.e. Rfvalue.
TLC Apparatus
Distance travelled by substance from the baseline (x)

Rf =
Distance travelled by solvent from the baseline (y)
Detection of Movement
The spots of coloured compounds are visible on TLC plate due to their original colour.
Other Detection Techniques

1. Colourless compounds can be detected by putting the plate under ultraviolet light.
2. Place the plate in a covered jar containing a few crystals of iodine. Spots of compounds, which adsorb iodine, will
show up as brown spots.
3. Spraying Agents - Amino acids may be detected by spraying the plate with ninhydrin solution.
Partition Chromatography
It is based on continuous differential partitioning of components of a mixture between stationary and mobile phases.
Paper chromatography is a type of partition chromatography. A special quality paper known as chromatography paper is used.
MECHANISM
1. Chromatography paper contains water trapped in it, which acts as the stationary phase. A strip of chromatography
paper spotted at the base with the solution of the mixture is suspended in a suitable solvent or a mixture of solvents.
This solvent acts as the mobile phase.
2. The solvent rises up the paper by capillary action and flows over the spot. The paper selectively retains different
components according to their differing partition in the two phases. The paper strip so developed is known as
a chromatogram.
Qualitative Analysis
Detection of Carbon and Hydrogen
Carbon and hydrogen are detected by heating the compound with CuO. Carbon present in the compound is oxidised to carbon
dioxide and hydrogen to water.
CO2 is tested with lime-water, which develops turbidity. H2O is tested with anhydrous copper sulphate, which turns
blue.

C  2CuO   2Cu  CO2
SCAN CODE

2H  CuO   Cu  H 2 O
CO2  Ca  OH 2  CaCO3  H3 O
5H 2 O  CuSO 4  CuSO 4 .5H 2 O

White blue
Detection of Other Elements

Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by Lassaigne’s test.
The elements present in the compound are converted from covalent form into the ionic form by fusing the compound with
sodium metal.

Na  C  N   NaCN

2Na  S 
 Na 2 S

Na  X   NaX
(X  Cl, Br or I)
(A) Test for Nitrogen

The sodium fusion extract is boiled with FeSO4 and then acidified with concentrated sulphuric acid. Sodium cyanide first reacts
with FeSO4 and forms sodium hexacyanoferrate(II).
On heating with concentrated sulphuric acid, some iron(II) ions are oxidised to iron(III) ions which react with sodium
hexacyanoferrate(II) to produce iron(III) hexacyanoferrate(II) (ferriferrocyanide) which is Prussian blue in colour.
4
6CN   Fe2   Fe  CN 6 
4 xH2O
3 Fe  CN 6   4Fe3   Fe4  Fe  CN 6  .xH2 O
3
Prussian blue
(B) Test for Sulphur
(1) The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A black precipitate of lead sulphide
indicates the presence of sulphur.

S2  Pb 2   PbS
Black
(2) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour further indicates the presence
of sulphur.
 2 4
S2   Fe  CN 5 NO    Fe  CN 5 NOS
Violet
Nitrogen and Sulphur Together
In this case, sodium thiocyanate is formed. It gives blood red colour and no Prussian blue since there are no free
cyanide ions.
Na  C  N  S  NaSCN
2
Fe3  SCN    Fe SCN  
Blood red
If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to yield cyanide and sulphide. These ions
give their usual tests.
NaSCN  2Na  NaCN  Na 2S

SCAN CODE
(C) Test for Halogens

The sodium fusion extract is acidified with nitric acid and then treated with silver nitrate.
1. A white precipitate, soluble in ammonium hydroxide shows the presence of chlorine.
2. A yellowish precipitate, sparingly soluble in ammonium hydroxide shows the presence of bromine.
3. A yellow precipitate, insoluble in ammonium hydroxide shows the presence of iodine.
X   Ag   AgX
If nitrogen or sulphur is also present in the compound, the sodium fusion extract is first boiled with concentrated nitric acid to
decompose cyanide or sulphide of sodium formed during Lassaigne’s test. These ions would otherwise interfere with silver nitrate
test for halogens.
(D) Test for Phosphorus
The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the compound is oxidised to
phosphate. The solution is boiled with nitric acid and then treated with ammonium molybdate. A yellow colouration or
precipitate indicates the presence of phosphorus.
Qualitative Analysis
Carbon and Hydrogen
A known mass of an organic compound is burnt in the presence of excess of oxygen and CuO. Carbon and hydrogen in the
compound are oxidised to carbon dioxide and water respectively.
1. H2O is absorbed by anhydrous CaCl 2.

2. CO2 is absorbed by KOH solution.
3. The increase in masses of CaCl 2 and KOH gives the amounts of H2O and CO2.
Percentage of C and H
Let the mass of organic compounds = mg

Mass of water = m 1g
mass of CO2 = m 2g
12  m 2  100
Percentage of C =
44  m
SCAN CODE
2  m1 100
Percentage of H =
18  m
Example
On complete combustion, 0.246 g of an organic compound gave 0.198 g of carbon dioxide and 0.1014 g of water. Determine the
percentage composition of carbon and hydrogen in the sample.
% of carbon = 21.95
% of hydrogen = 4.58
Nitrogen - Dumas Method
The nitrogen containing organic compound, when heated with CuO in an atmosphere of CO 2, yields free N2 in addition to
CO2and H2O.
Calculations
Mass of organic compound = m g

Volume of N2 collected = V1 ml
Room temperature = T1 K
p1  V1  273
Volume of N2 at STP V = ml
760  T1
p1= Barometric pressure – Aqueous tension
Calculations
22400 mL N2 at STP weighs 28 g.
28  V
V ml of N2 at STP weighs= g
22400
28  V 100
Percentage of nitrogen = %
22400  m
Kjeldahl’s method
The compound containing nitrogen is heated with conc H2SO4. Nitrogen in the compound gets converted to (NH4)2SO4. It is
done by estimating unreacted conc H2SO4 left after the absorption of NH3 by titrating it with standard alkali solution.
SCAN CODE
Let the mass of organic compound taken = m g

Volume of H2SO4 (1M) taken = V ml
Volume of NaOH (1M) for titration of excess of H2SO4 = V1 ml
Moles of H2SO4 = 2 × Moles of NaOH
Therefore, V1 ml of NaOH = V1/2 ml of H2SO4
Volume of H2SO4 unused = V – V1/2 ml
(V – V1/2) ml of H2SO4 = 2(V- V1/2) ml of NH3 solution
1000 ml of 1M NH3 solution contains 17 g of NH3 or 14 g of N.
2(V – V1/2) ml of NH3 solution of molarity M contains:
14  M  2 (V  V1 / 2)
Percentage of Nitrogen = gN
1000
14  M  2 (V  V1 / 2) 100

1000 m
Carius Method
A known mass of an organic compound is heated with fuming nitric acid in the presence of silver nitrate contained in a hard
glass tube known as Carius tube, in a furnace.
The halogen present forms the corresponding silver halide (AgX). It is filtered, washed, dried and weighed.
SCAN CODE
Mass of organic compound taken = m g
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X
Atomic Mass of X  m1
Mass of halogen in m1 g of AgX = Molecular Mass of AgX g
Atomic Mass of X  m1  100

Percentage of halogen = Molecular Mass of AgX  m %
Sulphur
A known mass of an organic compound is heated in a Carius tube with sodium peroxide or fuming nitric acid. Sulphur present
in the compound is oxidised to sulphuric acid. It is precipitated as barium sulphate by adding excess of barium chloride
solution in water.
Mass of BaSO4 formed = m 1 g
1 mol of BaSO4 (233 g) contains 1 mol sulphur (32 g)
32  m1
m 1 g BaSO4 contains g sulphur
233
32  m1  100
Percentage of Sulphur = %
233  m
Phosphorus
A known mass of an organic compound is heated with fuming nitric acid whereupon phosphorus present in the compound is
oxidised to phosphoric acid. It is precipitated as ammonium phosphomolybdate, (NH4)3PO4.12MoO3, by adding ammonia and
ammonium molybdate. Alternatively, phosphoric acid may be precipitated as Mg(NH4)PO4 by adding magnesia mixture which
on ignition yields Mg2P2O7.

Mass of ammonium phosphomolydate = m1 g
Molar mass of (NH4)3PO4.12MoO3 = 1877 g
31 m1 100
Percentage of P = %
1877  m
If phosphorus is estimated as Mg 2P2O7,
62  m1 100
Percentage of P = %
222  m
SCAN CODE
Oxygen
Percentage of oxygen in an organic compound = 100 – percentage of other elements
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 (I 2O5) when carbon monoxide is oxidised to carbon dioxide producing iodine.
heat
Compound 
 O 2  other gaseous products
1373K
2C  O2  2CO
I2 O5  5CO  I2  5CO2
CHN Elemental Analyzer

The estimation of elements in an organic compound is carried out by using microquantities of substan ces and automatic
experimental techniques. The elements, carbon, hydrogen and nitrogen present in a compound are determined by an apparatus
known as CHN elemental analyser.
SCAN CODE
SOLVED EXAMPLES
Example-1 Ans. (a)
The state of hybridisation of C2, C3, C5 and C6 of the Sol.

hydrocarbon, The molecule in which all the carbon atoms are sp2-
hybridised will be coplanar. Thus, in option (a) i.e.,
is in the following sequence

All carbons are sp2-hybridised
(a) sp, sp3, sp2 and sp3
(b) sp3, sp2, sp2 and sp
Example-3
(c) sp, sp2, sp2 and sp3
The correct order regarding the electronegativity of
(d) sp, sp2, sp3 and sp2
hybrid orbitals of carbon is
Ans. (a)
(a) sp > sp2 < sp3
Sol. If number of  bonds = 2; hybridisation is sp.
(b) sp > sp2 > sp3
If number of  bonds = 3; hybridisation is sp2.
(c) sp < sp2 > sp3
If number of  bonds = 4; hybridisation is sp3.
(d) sp < sp2 < sp3
Ans. (b)
Sol. The correct order regarding the electronegativity of
hybrid orbitals of carbon is sp > sp2 > sp3 because in sp,
sp2 and sp3 hybrid orbitals, s-orbital character is 50%,
33.3% and 25% respectively. Due to higher s-character
electron attracting tendency, i.e. electronegativity
increases.
Example-2 Example–4
In which of the following molecules, all atoms are The IUPAC name of the compound having the formula
coplanar? CH  C – CH = CH2 is
(a) 3-butene-1-yne
(b) 1-butyn-3-ene
(c) but-1-yne-3-ene
(a) (b)
(d) 1-butene-3-yne
Ans. (d)
Sol. In IUPAC nomenclature double bond is given more
preference than triple bond.
(c) (d)
4 3 2 1
CH  C C H  CH 2
1-butene-3-yne
Example – 5
The IUPAC name of the compound
Example-7
(a) 3-keto-2-methylhex-4-enal Which one of the following compounds has the most
acidic nature?
(b) 5-formylhex-2-en-3-one
(a)
(c) 5-methyl-4-oxohex-2-en-5-al
(d) 3-keto-2-methylhex-5-enal
Ans. (a)
(b)
Sol.
“ CHO group gets higher priority over ketone group in

numbering of principle carbon chain. IUPAC name is 3- (c)
keto-2-methylhex-4-enal
Example-6
The IUPAC name of
(d)
Ans. (b)
(a) 3, 4-dimethylpentanoyl chloride
Sol. Key Idea Presence of electron withdrawing substituent
(b) 1-chloro-1-oxo-2, 3-dimethylpentane increases the acidity while electron releasing substituent,
decreases the acidity.
(c) 2-ethyl-3-methylbutanoyl chloride
Phenyl is an electron withdrawing substituent while -CH3
(d) 2, 3-dimethyl pentanoyl chloride
is an electron releasing substituent. Moreover, phenoxide
Ans. (d) ion is more resonance stabilised as compared to
benzyloxide ion, thus releases proton more easily. That’s
Sol. IUPAC name of the given compound is
why phenol is a strong acid among the given compounds
Example-8
remains same while their energy, stability and dihedral
The correct statement regarding a carbonyl compound angle are different.
with a hydrogen atom on its alpha-carbon, is
(a) a carbonyl compound with a hydrogen atom on its
alpha-carbon rapidly equilibrates with its corresponding Example-10
enol and this process is known as aldehyde-ketone Which one of the following pairs represents
equilibration
stereoisomerism?
(b) a carbonyl compound with a hydrogen atom on its
(a) Chain isomerism and rotational isomerism
alpha-carbon rapidly equilibrates with its corresponding
enol and this process is known as carbonylation (b) Structural isomerism ·and geometrical isomerism
(c) a carbonyl compound with a hydrogen atom on its (c) Linkage isomerism and geometrical isomerism
alpha-carbon rapidly equilibrates with its corresponding (d) Optical isomerism and geometrical isomerism
enol and this process is known as Ans. (d)
keto-enol tautomerism Sol. Pair of optical isomerism and geometrical isomerism
(d) a carbonyl compound with a hydrogen atom on its are able to exhibit the phenomenon of stereoisomerism
alpha-carbon never equilibrates with its corresponding because both type of isomers differ only in their
enol orientation in space
Ans. (c)
Sol. In keto-enol tautomerism, a carbonyl compound with Example-11
a hydrogen atom on its alpha-carbon rapidly equilibrates Which of the following compounds will exhibit
with its corresponding enol. cis-trans (geometrical) isomerism?
(a) 2-butene
(b) Butanol
(c) 2-butyne
(d) 2-butenol
Ans. (a)
Example-9
Sol.
With respect to the conformers of ethane, which of
the following statements is true?
(a) Bond angle remains same but bond length changes
(b) Bond angle changes but bond length remain same
(c) Both bond angle and bond length change
(d) Both bond angles and bond length remain same
Ans. (d)
Sol. Isomers which are possible by rotation about single
bonds without cleavage of any bond are called
conformers. In ethane, an infinite number of
conformations are possible. There are two extreme forms,
the staggered conformation, which is the most stable and
the eclipsed conformation which least stable. Among the
conformers of ethane, bond angle and bond length
Example-12 Ans. (a)
If there is no rotation of plane polarised light by a Sol. Only those compounds exhibit optical isomerism, which
have chiral centre and /or absence of symmetrical
compound in a specific solvent, though to be chiral, it elements. (Chiral carbon is the carbon in which all the
may mean that four valencies are satisfied by four different groups.)
(a) the compound is certainly a chiral
(b) the compound is certainly meso
(c) there is no compound in the solvent
(d) the compound may be a racemic mixture
Ans. (b)
Sol. The compounds in which asymmetric carbon atom is
present, are called optically active, they rotate the plane
polarised light but the compounds which do not show
optical activity inspite of the presence of chiral carbon
atoms are called meso-compounds. The absence of
optical activity in these compounds is due to the presence
of plane of symmetry in the molecule
Example-13 Thus, maleic acid does not exhibit optical isomerism.

Two possible stereo-structures of CH3CHOHCOOH, Note:
which are optically active, are called If R = H, the α-amino acid is achiral
(a) diastereomers Example-15
(b) atropisomers How many stereoisomers does this molecule have?
(c) enantiomers CH3CH = CHCH2CHBrCH3
(d) mesomers (a) 4 (b) 6
Ans. (c) (c) 8 (d) 2
Sol. Ans. (a)
Sol.
C* = asymmetric carbon
Both are enantiomers Number of optical isomers = 2n
where, n = number of asymmetric carbon atoms
Example-14 = 21 = 2
Which of the following acid does not exhibit optical Number of geometrical isomers = 2n
isomerism? where, n = number of double bonds = 21 = 2
(a) Maleic acid Hence, total number of stereoisomers = Total optical
(b) α-amino acid isomers + Total geometrical isomers = 2 + 2 = 4.
(c) Lactic acid

(d) Tartaric acid
Example-16
A compound of molecular formula C7H16 shows optical
isomerism, compound will be
(a) 2, 3-dimethyl pentane
(b) 2, 2-dimethyl butane
(c) 2-methyl hexane
(d) None of the above
Ans. (a)
Sol. 2,3-dimethylpentane
Shows the property of optical isomerism due to presence

of an asymmetric C-atom.
Teacher’s Note:



years.
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
1. The suffixes for alcohols, aldehyes and ketones according 7. The IUPAC name of CH3COCH (CH3)2 is
to IUPAC system are respectively :
(a) isopropylmethyl ketone
(a) -alc, -ald, -ket
(b) 2-methyl-3-butanone
(b) -ol, -al, -ket
(c) 4-methylisopropyl ketone
(c) -ol, -al, -one
(d) 3-methyl-2-butanone
(d) -coh, -ald, -one
2. The correct decreasing order of priority for the
functional groups of organic compounds in the IUPAC 8. The correct IUPAC nomenclature for the following alcohol
system of nomenclature is is :
(a) —COOH, —SO3H, —CONH2, — CHO

(b) —SO3H, —COOH, —CONH2, —CHO
(c) —CHO, —COOH, —SO3H, —CONH2
(a) 2-ethyl-2-butanol
(d) —CONH2, —CHO, — SO3H,—COOH
(b) 3-methyl-3-pentanol
3. The IUPAC name of neopentane is
(c) 3-ethyl-3-methyl-3-pentanol
(a) 2-methylbutane
(d) 1, 1-diethylanol
(b) 2, 2-dimethylpropane
9. The IUPAC name of the compound
(c) 2-methylpropane
(d) 2,2-dimethylbutane
4. Underlined carbon is sp3 hybridised in
(a) (b) is :
(a) 3-ethyl-4-methylhex-5-en-2-ol
(c) (d)
(b) 3-ethyl-4-ethylhex-1-en-5-ol
5. Which one of the following does not have sp 2
hybridised carbon ? (c) 3-ethyl-2-hydroxy-4-methylhex-5-ene
(a) Acetone (b) Acetic acid (d) none of the above
(c) Acetonitrile (d) Acetamide
10. The IUPAC name of the compound
6. How many chiral compounds are possible on
(CH3)2 CH – CH = CH – CHOH – CH3 is :
monochlorination of 2-methyl butane ?
(a) 5-methylhex-3-en-2-ol
(a) 2 (b) 4
(b) 2-methylhex-3-en-5-ol
(c) 6 (d) 8
(c) 2-hydroxy-5-methyl-3-hexene
(d) 5-hydroxy-2-methyl-3-hexene
11. Which of the following compounds has incorrect IUPAC
nomenclature ?
15. The IUPAC name of is
(a) 1, 1-diethyl-2, 2-dimethylpentane

(a) (b)
(b) 4, 4-dimethyl-5, 5-diethylpentane
(c) 5, 5-diethyl-4, 4-dimethylpentane
(d) 3-ethyl-4, 4-dimethylheptane
(c) (d)
16. The correct IUPAC name of the following compound :
12. The IUPAC name of the compound is
is (a) 4 – methyl – 3 – ethylhexane

(b) 3 – ethyl – 4 – methylhexane
(a) 3,3-dimethyl-1-hydroxy cyclohexane (c) 3, 4 – ethylmethylhexane
(b) 1,1-dimethyl-3-hydroxy cyclohexane (d) 4 – ethyl – 3 – methylhexane
(c) 3,3-dimethyl-1-cyclohexanol 17. The IUPAC name of CH3C(CH3)2 CH2CH CH2 is :
(d) 1,1-dimethyl-3-cyclohexanol (a) 2,2-dimethyl-4-pentene

13. The IUPAC name of the following compound is : (b) 4,4-dimethyl-1-pentene
(c) 1,1,1-trimethyl-3-butene
(d) 2-chloro-4,4-dimethylhexane
18. The name of according to

(a) 2,5,6-trimethylheptane
(b) 1,3-isopropyl-3-methylpropane IUPAC nomenclature system is :

(c) 2,6,3-trimethylheptane (a) 2,3-dibromo-1,4-dichlorobutene-2
(d) 2,3,6-trimethylheptane (b) 1,4-dichloro-2,3-dibromobutene-2
14. Name of the compound given below is : (c) dichlorobromobutene
(d) dichlorobromobutane
19. The IUPAC name of CH3CH2C(Br) CHCl is :
(a) 4-chloro-3-bromo but-3-ene
(b) 2-bromo-1-chloro butane
(c) 2-bromo-1-chloro but-1-ene

(a) 2,3-diethylheptane (b) 3-methyl-4-ethyloctane
(d) 2-bromo-2-ethyl-3-chloro propene
(c) 5-ethyl-6-methyloctane (d) 4-ethyl-3-methyloctane
20. The IUPAC name of is :
(a) 3-propylpent-1-ene (b) 3-ethylpent-1-ene
(c) 4-ethylhex-1-ene (d) 3-ethylhex-1-ene

21. The IUPAC name of the compound shown below is Among these, chain isomers are
(a) I and II (b) I and III
(c) II and III (d) all of these
25.
(a) 2-bromo-6-chlorocyclohex-1-ene
(b) 6-bromo-2-chlorocyclohexene
(c) 3-bromo-1-chlorocyclohexene
(d) 1-bromo-3-chlorocyclohexene
22. The IUPAC name of CH3  C  CCH  CH3 2 is:
(a) 4-methyl-2-pentyne
(b) 4,4 -dimethyl-2-pentyne
(c) methyl isopropyl acetylene Among these, I is the chain isomer of
(d) 4,4,4-trimethyl-1-butene (a) II only (b) III only

(c) both (d) none of these
23. The IUPAC name of
26.
is :
(a) 2,2-diethyl pentanoic acid
(b) 2,4-dimethyl hexanoic acid
(c) 2-methyl-4-ethyl pentanoic acid
(d) 4-ethyl-2-methyl pentanoic acid
24.
Among these III is the chain isomer of
(a) I only (b) II only
(c) both I and II (d) none of these

31. Isomers are the compounds having the
27.
(a) same molecular formula but different physical and/or
chemical properties.
(b) same structural formula but different molecular formulae
The tautomer of II is (c) same chemical properties and physical properties
(a) I (b) (III) (d) same physical properties but different chemical properties.
(c) both I and III (d) None of these

28.
32.
Among these, positional isomers are
(c) II and III (d) all of these

Which among these are tautomers ?
33. Number of  electrons present in naphthalene is
(a) 4 (b) 6
(c) II and III (d) None of these
(c) 10 (d) 14
29.
34. Which of the following has maximum enol content ?
OH
(a) Acetaldehyde (b)
(c) Acetylacetaldehyde (d)
35. The number of structural isomers for C6H14 is:
(a) 4 (b) 5
(c) 6 (d) 3
Among these functional isomers are
36. Among the following compounds, E/Z isomerism is
possible for
(c) II and III (d) Both (a) and (c) (a) 2-methybut-2-ene
30. The compound C4H10O can show (b) 2-methylbut-1-ene
(a) metamerism (b) positional isomerism (c) 3-methylpent-1-ene
(c) functional isomerism (d) all types
(d) 3-methylpent-2-ene
37. Among the following acids which has the lowest pKa 42. The simplest alkene which is capable of exhibiting
value ? geometrical isomerism has
(a) CH3CH2COOH (b) (CH3)2CH—COOH (a) 3 carbon atoms (b) 5 carbon atoms
(c) HCOOH (d) CH3COOH (c) 6 carbon atoms (d) 4 carbon atoms
43. Which of the following compounds can exhibit geometrical
38. isomerism ?
(a) Hex–1–ene (b) 2–Methylpent–2–ene
(c) 3–Methylpent–1–ene (d) Hex–2–ene
44. Which one of the following compound will show
geometrical isomerism ?
(a) (b)
(c) (d)
45. How many open chain structural isomers of compound with

Which among these are stereo-isomers ? molecular formula C6H12 show geometrical isomerism ?
(a) I and II (b) I and III (a) 2 (b) 3
(c) II and III (d) all of these (c) 4 (d) 5

46. Which of the following can exist as cis and trans isomers ?
39. Which of the following will exhibit geometrical isomerism ?
(a) (b)
(a) 1–Phenylbut–2–ene
(c) (d)
(b) 3–Phenylbut–1–ene 47. Which of the following pair of structures represent
(c) 2–Phenylbut–1–ene geometrical isomers of each other?
(d) 1,1–Diphenylprop–1–ene
(a)
40. Geometrical isomerism will be exhibited by
(a) Pent–1–ene
(b) 3–Methylbut–1–ene (b)

(c) Pent–2–ene
(d) All of these compounds

(c)
41. Which of the following compounds can show geometrical
isomerism ?
(a) Vinyl chloride (b) 1,1–Dichloroethene

(d)
(c) 1,2–Dichloroethene (d) Trichloroethene
48. Which is a pair of geometrial isomers ?
(a)
(b)
(c)
(d)
53. Which one of the following substituents at para-position

(a) I and II (b) I and III is most effective in stabilizing the phenoxide
(c) II and IV (d) III and IV
49. Which one of the following acids does not exhibit optical ions ?
isomerism?
(a) Maleic acid (b) Tartaric acid (a) –OCH3 (b) –CH2OH
(c) Lactic acid (d) -amino acid
(c) –CH3 (d) –COCH3
50. Inductive effect of —CH3 group operates in
54. Inductive effect of Cl atom operates in
(a)
(a) (b)
(b)
(c) (d) all of these (c)
51. In the following benzyl/allyl system

(d) all of these
55.
Which of these groups has –I effect ?

(R is alkyl group)
(a) I (b) II
decreasing order of inductive effect is
(c) III (d) all of these
(a)
56. Inductive effect of a —CH3 group operates
(b)
(c)
(a) (b)
(d)
52. Arrange the carbanions,
    (c) (d) both (b) and (c)

 CH3 3 C, C Cl3 ,  CH3 2 C H,C6 H5 C H 2 in o rd er of
their decreasing stability

57. Which of the following represents the case of 59. Hyperconjugation occurs in
hyperconjugation ?
(a) (a)
(b)
(b)
(c)
(d) All of these
60.
(c)
How many hyperconjugable H-atoms does this molecule has
?
(a) 0 (b) 2
(c) 3 (d) 4
(d) both (b) and (c) 61.
58. Which of the following orbital diagrams represents the
case of hyperconjugation ?
Canonical structures due to hyperconjugation in this

molecule can be written as
(a) (b)
(a)
(b)
(c) both (a) and (b) (d) none of these

(c) both (a) and (b) 62. Hyperconjugation occurs in
(d) none of these (a) CH CH2 (b) CH CH CH3

3 3
(c) CH CH2 CH2 (d) all of these

3
63. In which of the following molecules, all atoms are coplanar? 65.
Which of the following statements is true about this molecule

?
(a) (a) C1—C2 and C3—C4 bonds are of same length
(b) C1—C2 bond is shorter than C3—C4 bond
(c) C1—C2 bond is longer than C3—C4 bond
(d) C1—C2 and C2—C3 bonds are of same length

(b)
66.
(c)
Among these compounds, which one has shortest C—Cl

bond ?
(d) (a) I (b) II
(c) III (d) IV
67. In which of the following molecule the resonance effect is

64. In which of the following molecules, all atoms are not coplanar not present ?
?
(a)
(a)
(b)
(b)
(c)
(c)
(d)
(d)
68. The most unlikely representation of resonance structure
of p–nitrophenoxide ion is :
71.
(a)
(b)
(c)
Among these canonical structures of pyridine, the correct

order of stability is
(d)
(a) ( I = V) > (II = IV) > III
(b) (II = IV) > (I = V) > III
69. Heat of hydrogenation of cyclohexene is –28.6 kcal/mol (c) (I = V) > III > (II = IV)
and that of benzene is –49.8 kcal/mol. Then resonance
energy of benzene will be (d) III > (II = IV) > (I = V)
(a) 46 kcal/mol (b) 39 kcal/mol
72.
(c) 36 kcal/mol (d) 30 kcal/mol
70.
The correct order of stability among these canonical

structures is The most stable canonical structure among these is
(a) I > III > II (b) III > I > II (a) I (b) II
(c) II > III > I (d) II > I > III
(c) III (d) all are equally stable
77. In which of the following molecules, –NO2 group is not

coplanar with phenyl ring ?
73.
(a) (b)
The stability order of these canonical structures is (c) (d)

(a) I > II > III (b) III > I > II
(c) I > III > II (d) II > III > I
74. Which of the following is most stable
78. For the reactions
(I)
(II)
(III)
(IV)
(a) I (b) II
(c) III (d) IV
The correct decreasing order of enthalpies of reaction for
75. Resonance structure of a molecules should have
producing carbocation is
(a) Identical arrangement of atoms
(a) H1o  H o2  H 3o  H o4
(b) Nearly the same energy content
(c) The same number of paired electrons (b) H o4  H1o  H o2  H 3o
(d) All the above
(c) H 3o  H o2  H1o  H o4
76. In the anion, HCOO– the two carbon-oxygen bonds are
found to be of equal length. What is the reason for it ? (d) H o2  H1o  H o4  H 3o
(a) Electronic orbits of carbon atom are hybridised
(b) The bond is weaker than the bond
–
(c) The anion, HCOO has two resonating structures
(d) The anion is obtained by removal of a proton from
the acid molecule
79. Which of the following species is a nucleophile ?

86. The correct order of increasing acid strength of the
compounds
(a) H2O (b) H3O
(A) CH3CO2H (B) MeOCH2CO2H
(c) both (a) and (b) (d) none of these
80. Which of the following species is a nucleophile ?
(C) CF3CO2H (D) is
(a) CH3O (b) CH3OH
(c) both (a) and (b) (d) none of these (a) B < D < A < C (b) D < A < C < B
81. Which of the following species is an electrophile ?
(c) D < A < B < C (d) A < D < C < B
(a) H (b) H 87. The hybridization of carbon atoms in C—C single bond of
(c) both (a) and (b) (d) none of these H—C C — CH CH2 is :
82. Due to the presence of an unpaired electron, free (a) sp3 – sp3 (b) sp2 – sp3
radicals are
(a) cations (b) anions (c) sp3 – sp (d) sp – sp2
(c) chemically inactive (d) chemically reactive 88. Hybridized carbon atom used in the formation of the
83. Rate of the reaction compound CH3 — CH CH — CH2 — CH3 are :
(a) sp and sp3 (b) sp and sp2
(c) only sp (d) sp2 and sp3
89. In the hydrocarbon,
is fastest when Z is
(a) Cl (b) NH2
The state of hybridization of carbons 1,3,5 are in the
(c) OC2H5 (d) OCOCH3’ following sequence :
84. The reaction
(a) sp, sp2, sp3 (b) sp3, sp2, sp
(c) sp2, sp, sp3 (d) sp, sp3, sp2
90. Which of the following statements is true about hybridization
is fastest when X is ?
(a) OCOR (b) OC2H5 (a) Hybrid orbitals frequently undergo linear overlaps
(c) NH2 (d) Cl making sigma bonds.
85. The decreasing order of nucleophilicity among the (b) Hybrid orbitals frequently undergo lateral overlaps
nucleophiles
making -bonds. In other words, there are several compounds
in which -bonds are formed using hybrid orbitals.
(A)
(c) Hybrid orbitals are molecular orbitals.
(B) CH3O– (d) A hybrid orbital bigger in size makes shorter bond.
(C) CN–
91.
(D) C1—C2 bond of this molecule is formed by
(a) sp3–sp2 overlap (b) sp2–sp3 overlap

(a) (C), (B), (A), (D) (b) (B), (C), (A), (D) (c) sp–sp2 overlap (d) sp2–sp2 overlap
(c) (D), (C), (B), (A) (d) (A), (B), (C), (D)
92. In which of the following compounds, C has used sp2 97.

orbital in making C—O bond ?
(a) (b)
(c) (d) Which of the following orders is correct for the stability of
these carbanions ?
93. (a) I > II > III (b) III > II > I

In this molecule (allene)
(a) all three C-atoms are sp2-hybridized
(b) both terminal C-atoms are sp2-hybridized while central

C-atom is sp-hybridized
(c) both terminal C-atoms are sp-hybridized while central 98.

C-atom is sp2-hybridized
(d) none of these

Which of the following orders is correct for the stability of
94. Carbon atoms in the compound (CN)4C2 are these carbanions ?
(a) sp hybridised (a) I > II > III (b) III > II > I
(b) sp2 hybridised (c) III > I > II (d) II > I > III
(c) sp and sp 2 hybridised
(d) sp, sp2 and sp3 hybridised 99.

95. In which bond angle is the highest
(a) sp3 (b) sp 2
these carbanions ?
(c) sp (d) sp 3d
(a) I > II > III (b) III > II > I
96. (c) II > I > III (d) III > I > II
100. Which of the following carbocation is least stable ?

these carbanions ?
(a) I > II > III

(a) (b) CH CH2
(b) III > II > I
(c) II > I > III
(d) I  II  III
(c) CH2 CH CH2 (d)
101. The order of reactivity of the following alcohols towards 104. The order of stability of the following carbocations
conc. HCl is :
 
CH 2  CH  C H 2 ;CH3  CH 2  C H 2 ;
(I)  I  II 
(II) (III)
(a) I > II > III (b) I > III > II
(c) III > II > I (d) III > I > II (a) III > II > I (b) II > III > I
(c) I > II > III (d) III > I > II
102. What is the correct order of stability of the given cations 105.
:
Which of the following orders is correct for no-bond-

resonance energy of these radicals ?
(c) III > I > II (d) II > III > I
106.
Which of the following orders is correct for no-bond-

(a) III > II > IV > I (b) I > II > III > IV
(c) III > I > II > IV (d) IV > II > III > I
103. Which of the following statements is correct about methyl

group ? 107.
(a) It stabilizes both carbocation and free radical equally
(b) it stabilizes a free radical more than a carbocation
(c) it stabilizes a carbocation more than a free radical Which of the following orders is correct for no-bond-
(d) none of these
(c) I > III > II (d) II > I > III
108. The increasing order of stability of the following free 112. The formula of the compound which gives violet color
radicals is in Lassaigne’s test for sulphur with sodium
   
nitroprusside is:
(a)  CH 3  CH   CH 3  C   C6 H 5  CH   C6 H 5  C
2 3 2 3
(a) Na4[Fe(CN)6S]
   
(b)  C6 H 5  C   C 6 H 5  CH   CH 3  C   CH 3  CH (b) Na4[Fe(CN)5NCS]
3 2 3 2
    (c) Na4[Fe(CN)5NOS]
(c)  C6 H 5  CH   C6 H 5  C   CH 3  C   CH 3  CH
2 3 3 2
(d) Na2[Fe(CN)5NOS]
   
(d)  CH 3  CH   CH 3  C   C6 H 5  C   C 6 H 5  CH
2 3 3 2
109. Which one of the following compounds will not be

soluble in sodium bicarbonate ?
(a) 2, 4, 6 – Trinitrophenol
(b) Benzoic acid
(c) o – Nitrophenol
(d) Benzene sulphonic acid
110. The principle involved in paper chromatography is:
(a) adsorption
(b) partition
(c) solubility
(d) volatility
111. For the estimation of nitrogen, 1.4 g of an organic

compound was digested by Kjeldahl method and the
M
evolved ammonia was absorbed in 60 mL of sulphuric
10
M
acid. The unreacted acid required 20 mL of sodium
10
hydroxide for complete neutralization. The percentage of
nitrogen in the compound is
(a) 5% (b) 6%
(c) 10% (d) 3%

EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS
1.
(a) R and E (b) S and E

(c) R and Z (d) S and Z
5. The “N” which does not contribute to the basicity for the
Among these cations, which of the following orders is
compound is : (2016)
correct for their no-bond-resonance energy ? (2015)

(c) I > III > II (d) III > I > II
2. The number of structural isomers for C6H14 is : (2015)

(a) 4 (b) 3
(c) 6 (d) 5 (a) N 7 (b) N 9
3. Match the organic compounds in column-I with the (c) N 1 (d) N 3
Lassaigne’s test results in column-II appropriately : 6. 3-Methyl-pent-2-ene on reaction with HBr in presence of
Column-I Column-II peroxide forms an addition product. The number of
(A) Aniline (i) Red colour with possible stereoisomers for the product is : (2017)
FeCl3 (a) Zero (b) Two
(B) Benezne sulfonic (ii) Violet colour with
(c) Four (d) Six
acid sodium nitroprusside
7. Which of the following molecules is least resonance
(C) Thiourea (iii) Blue colour with
stabilized ? (2017)
hot and acidic
solution of FeSO4
(a) (b)
(2015)
(a) A– (ii); B– (iii); C– (i) (b) A– (iii); B– (i); C– (ii)
(c) A– (iii); B– (ii); C– (i) (d) A– (ii); B– (i); C– (iii)
4. The configuration of the chiral centre and the geometry of (c) (d)
the double bond in the following molecule can be
described by (2016)
8. The number of geometrical isomers in the following 12. In the following structure, the double bonds are marked
compound as I, II, III and IV
CH3—CH=CH—CH=CH—C2H5 is (2017)
(a) 4 (b) 3
(c) 2 (d) 5
9. Which of the following statements is not true about
partition chromatography ? (2017)
Geometrical isomerism is not possible at site (s) :
(a) Mobile phase can be a gas
(2018)
(b) Stationary phase is a finely divided solid adsorbent
(a) III (b) I
(c) Separation depends upon equilibration of solute (c) I and III (d) III and IV
between a mobile and a stationary phase
13. Which of the following compounds will show highest
(d) Paper chromatography is an example of partition dipole moment (2018)
chromatography
10. The IUPAC name of the following compound is :
(2017)
(a) 1, 1-Dimethyl-2-ethylcyclohexane
(b) 2-Ethyl-1, 1-dimethylcyclohexane (a) I (b) II
(c) 1-Ethyl-2, 2-dimethylcyclohexane (c) III (d) IV
(d) 2, 2-Dimethyl-1-ethylcyclohexane 14. Among the following compounds, the increasing order of
their basic strength is : (2019)
11. Which of the following compounds is most reactive to an
aqueous solution of sodium carbonate ? (2018)
(a) (b)
(c) (d)
(a) (I) < (II) < (IV) < (III) (b) (I) < (II) < (III) < (IV)
(c) (II) < (I) < (IV) < (III) (d) (II) < (I) < (III) < (IV)
15. The IUPAC name of the following compound is : 18. The IUPAC name of the following compound is
(2019) (2019)
(a) 3-methyl-4-(3-methylprop-1-enyl)-1-heptyne
(a) 4-methyl-3-ethylhex-4-ene
(b) 3,5-dimethyl-4-propylhept-6-en-1-yne
(b) 3-ethyl-4-methylhex-4-ene
(c) 3-methyl-4-(1-methylprop-2-ynyl)-1-heptyne
(c) 4-ethyl-3-methylhex-2-ene (d) 3,5-dimethyl-4-propylhept-1-en-6-yne
(d) 4, 4-diethyl-3-methylbut-2-ene 19. The correct IUPAC name of the following compound is:
16. Two compounds I and II are eluted by column (2019)
chromatography (adsorption of I > II). Which one of
following is a correct statement ? (2019)
(a) I moves faster and has higher Rf value than II
(b) II moves faster and has higher Rf value than I
(c) I moves slower and has higher Rf value than II
(d) II moves slower and has higher Rf value than I
17. The increasing order of the acidity of the following

(a) 5-chloro-4-methyl-1-nitrobenzene
carboxylic acids is : (2019)
(b) 2-chloro-1-methyl-4-nitrobenzene
(c) 3-chloro-4-methyl-1-nitrobenzene
(d) 2-methyl-5-nitro-1-chlorobenzene
20. The IUPAC name of the following compound is:
(2019)
CH3 OH
| |
H3 C  CH  CH  CH 2  COOH
(a) I<III<II<IV (a) 4,4-Dimethyl-3-hydroxybutanoic acid

(b) IV<II<III<I (b) 2-Methyl-3-hydroxypentan-5-oic acid
(c) 3-Hydroxy-4-methylpentanoic acid
(c) II<IV<III<I
(d) III<II<IV<I (d) 4-Methyl-3-hydroxypentanoic acid
21. What is the IUPAC name of the following compound? (c)
(2019)
(d)
(a) 3-Bromo-1,2-dimethylbut-1-ene
(b) 3-Bromo-3-methyl-1,2-dimethylprop-1-ene
(c) 3-Bromo-3-methylpent-3-ene
(2020)
(d) 4-Bromo-3-methylpent-2-ene
22. The increasing order of nucleophilicity of the following

nucleophiles is: (2019)
(a) (i) < (iv) < (iii) < (iii)
(b) (ii) < (iii) < (iv) < (i)
(c) (iv) < (i) < (iii) < (ii)
(d) (ii) < (iii) < (i) < (iv)
23. Which of the following compounds will show the maximum

(a) 2-nitro-4-hydroxymethyl-5-amino benzaldehyde
‘enol’ content? (2019)
(b) 3-amino -4-hydroxymethyl-5- nitro benzaldehyde
(a) CH3COCH2COOC2H5 (c) 5-amino -4-hydroxymethyl-2- nitro benzaldehyde
(b) CH3COCH2COCH3 (d) 2-amino -2-formyl-5-hydroxymethyl nitrobenzene
(c) CH3COCH3
(2020)
(d) CH3COCH2COCH2
24. Which one of the following compounds possess the most
acidic hydrogen? (2020)
(a)
(a) 5-Bromo-3-methylcyclopentanoic acid

(b) 4-Bromo-2-methylcyclopentane carboxylic acid
(c) 3-Bromo-5-methylcyclopentanoic acid
(b) H3C – C  C – N (d) 3-Bromo-5-methylcyclopentane carboxylic acid
27. The IUPAC name of the following compound is: 31. The correct order of stability for the following alkoxides is
(2020) :
(a) 2,5-dimethyl-5-carboxy-hex-3-enal
(2020)
(b) 2,5-dimethyl-6-carboxy-hex-3-enal
(a) (B) > (A) > (C) (b) (C) > (B) > (A)
(c) 2,5-dimethyl-6-oxo-hex-3-enoic acid
(c) (C) > (A) > (B) (d) (B) > (C) > (A)
(d) 6-formyl-2-methyl-hex-3-enoic acid
Numeric Type Question
28. Glycerol is separated in soap industries by : (2020) 32. In an estimation of bromine by Carius method, 1.6 g of an
(a) Fractional distillation organic compound gave 1.88 g of AgBr. The mass
(b) Differential extraction percentage of bromine in the compound is _____ .

(Atomic mass, Ag = 108, Br = 80 g mol–1) (2020)
(c) Steam distillation
(d) Distillation under reduced pressure

29. The increasing order of basicity for the following
intermediates is (from weak to strong) (2020)
(a) (iii) < (i) < (ii) < (iv) < (v)
(b) (v) < (i) < (iv) < (ii) < (iii)
(c) (v) < (iii) < (ii) < (iv) < (i)
(d) (iii) < (iv) < (ii) < (i) < (v)
30. A flask contains a mixture of isohexane and
3-methylpentane. One of the liquids boils at 63C while the
other boils at 60C. What is the best way to separate the
two liquids and which one will be distilled out first?
(2020)
(a) fractional distillation, isohexane
(b) simple distillation, 3-methylpentane
(c) simple distillation, isohexane
(d) fractional distillation, 3-methylpentane

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

1. All questions marked “S” are single choice questions
2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions
1.(S) Number of which of the following isomers is always 4. (S) CH2=CH–CH=CH–CH=CH–CH3

infinite? How many geometrical isomers of this compound are
(a) Geometrical Isomers possible ?
(b) Optical Isomers (a) 2 (b) 3
(c) Conformational Isomers (c) 4 (d) 8

(d) Structural Isomers 5. (S) CH3–CH2–CH=CH–CH=CH–CH3
2. (S) Which of the following compounds will exhibit confor-
How many geometrical isomers of this compound are
mational isomerism ? possible ?
(a) CH 3  CH 2  CH 3 (a) 2 (b) 3
(b) CH 3  CH 2  CH 2  CH3 (c) 4 (d) 8
CH 3  CH  CH 3
| 6. (S)
(c)
CH 3
(d) All of these

How many geometrical isomers of this cyclodecene are
3. (S) Which of the following alkenes will exhibit geometrical possible ?
isomerism ?
(a) 0 (b) 2
(a) CH3–CH2–CH2–CH = CH2
(b) CH3–CH2–CH = CH–CH3 (c) 3 (d) 4
(c) CH3–CH2–CH = CH–CH2–CH3

(d) both (b) and (c)
7. (S) 10. (S) Which is the major product of the following reaction ?
(a)
These two conformers exist in a state of dynamic

equilibrium. Which one is more stable ?
(a) I (b) II
(b)
(c) Both are equally stable
(d) It is not possible to compare them for stability
8. (S) Arrange following compounds in decreasing order of
basicity.
(c)
(a) IV > I > III > II (b) III > I > IV > II
(c) II > I > III > IV (d) I > II > III > IV
(d)
9. (S)
11. (S) Correct order of basicity of various nitrogen in
III. CH3  NH 3
Which of the following orders is correct for the basic-

strength of these compounds ? (a) 1 > 2 > 3 (b) 2 > 1 > 3
(c) 2 > 3 > 1 (d) 3 > 2 > 1
(c) I > III > II (d) II > I > III

12. (S) Aniline is weaker base than ethyl amine. This is due to 18. (S) CH 3 CH 3  CH 3 C  CH
I II III
(a) – I effect of NH2 in aniline
Which of these groups has +I effect ?
(b) – R effect of NH2 in aniline
(c) + I effect of NH2 in aniline (a) I (b) II
(d) + R effect of NH2 in aniline (c) III (d) all of these
13.(S) Which of the following is strongest acid ? 19. (S) Which of the following alkyl benzenes has maximum
(a) HCOOH (b) CH3COOH electron density?
(c) (d) (a) (b)
14. (S) (I) CH3NH2 (II) (CH3)2NH (III) (CH3)3N

strength of these 1º, 2º and 3º amines in gas phase ?
(c) II > I > III (d) II > III > I
(c) (b)
15. (S) (I) CH3NH2 (II) (CH3)2NH
(III) (CH3)N
strength of these amines in polar solvents (e.g., –H2O) ?
(a) I > II > III (b) III > II > I 20. (S) Consider the following structures

(c) II > I > III (d) II > III > I 
(I) CH 2  C H (II) CH 3  C H 2
16. (S)
 
(III) CH 2  CH  C H 2 (IV) C6 H 5  C H  C6 H 5
The correct sequence of these carbocations in the

decreasing order of their stability is
(a) IV, III, II, I (b) I, II, III, IV
(c) IV, II, III, I (d) I, III, II, IV
Which of the following orders is correct for the basic- 21. (S) Which of the following is the most stabilized
strength of these anilines ? carbocation?
(c) II > I > III (d) I > III > II
 F COOCH 3 COCl (a) (b)
17. (S) I II III
Which of these groups has –I effect ?

(a) I (b) II
(c) III (d) all of these (c) (d)
22. (S) Which carbocation is the most stabilized ?
25. (S)
(a) (b)
Which of the following no-bond-canonical structures

is correct for this radical ?
(c) (d)
23. (S) Which of the following options is the correct order of

relative stabilities of cations as written below (most
(a)
stable first) ?
(I)
(II)
(b)
(III)
(a) I > II > III (b) II > III > I
(c) III > I > II (d) I > III > II
24. (S) What is the decreasing order of stability (most stable

 least stable) of the following carbocations ?
(c)
(d) none of these

26. (S) Which of the following carbocation is most stable ?
(a) (b)
(a) 3 >2 > 1 > 4 > 5 (b) 3 > 2 >5 > 4 >1
(c) 1  4  2  5  3 (d) 3  1  4  2  5
(c) (d)
27. (S) Relative stabilities of the following carbocation will be 31. (S) Arrange the following in decreasing order of stability.
in order :
(a) I > II > III (b) I > III > II

(a) I < II < III < IV (b) IV < III < II < I
(c) IV < II < III < I (d) II < IV < III < I 32. (S) The correct order of stability of the three isomeric carbanions
is:
28.(S) What is the decreasing order of strength of the bases ?
OH  , NH 2 , H – C  C  and CH 3  CH 2
(a) CH 3  CH 2  NH 2  H  C  C   OH 
(b) H  C  C   CH 3  CH 2  NH 2  OH 
(c) OH   NH 2  H  C  C   CH 3  CH 2
(a) I > II < III (b) I > III > II
   
(d) NH  H  C  C  OH  CH 3  CH
2 2
29. (S) 33. (S) The three carbanions follows which order of stability
Which of the following orders is correct for the stability

of these carbanions ?
(a) I > II > III (b) III > II > I (a) I > II > III (b) I > III > II
(c) II > III > I (d) II > I > III (c) II > I > III (d) II > III > I
30. (S) Which of the following is least stable? 34. (S) The correct arrangement of the relative stability of the
three carbocation is :
(a) I (b) II
(c) III (d) None
(c) I > III > II (d) III > I > II
35. (S) Which of the following is most likely to undergo a

favourable hydride shift ?
38. (S)
(a) (b)
Rearrangement in this carbocation will produce
(a)
(c) (d)
(b)
36. (S) (c) both (a) and (b)

(d) none of these
39. (S)
Regarrangement in this carbocation will produce
(a)
Which of the following orders is correct for the stability (b)

of these carbocations ?
(c) both (a) and (b)
(d) none of these
(c) II > III > I (d) III > I > II
40. (S) The total number of contributing structures showing
hyperconjugation (involving C–H bonds) for the
37. (S)
following carbocation is:
(a) 4
(b) 5
(c) 6
Which of the following orders is correct for the stability
of these carbocations ? (d) 7
41. (S) Which of the following is correctly named? (c)
(a)
(d)
(b)
43. (S) Which of the following ring compounds obeys Huckel’s

rule?
(a) C4 H 41
(b) C4 H 41
(c) C4 H 42
(c)
(d) C4 H 4
44. (S) Which statement explains why the element carbon
forms so many compounds with different shape?
(a) Carbon atoms combine readily with oxygen.
(b) Carbon atoms have very high electronegativity.
(c) Carbon readily forms ionic bonds with other carbon
(d) atoms.
(d) Carbon readily forms covalent bonds with other
carbon atoms.
45. (S) The reaction
42. (S) Which of the following is least stable?

(a) represents
(a) nucleophilic substitution
(b) electrophilic addition
(b)
(c) electrophilic substitution
(d) elimination reaction

46. (S) The hybridization of carbon in diamond, graphite and 50. (M) Which of the statements are incorrect about the
following compound ?
acetylene are respectively:
(a) sp3, sp, sp2
(b) sp, sp2, sp3
(c) sp3, sp2, sp
(d) sp2, sp3, sp

(a) All three C—N bonds are of same length
47. (S) The correct acidity order of the following is
(b) C1 — N and C3 — N bonds are of same length but
shorter than C5 — N bond
(c) C1 — N and C5 — N bonds are of same length but
longer than C3 — N bond
(d) C1 — N and C3 — N bonds are of different length but
both are longer than C5 — N bond
51. (M) Which of the following alkenes are more stable than
(a) (III) > (IV) > (II) > (I) (b) (IV) > (III) > (I) > (II)
(c) (III) > (II) > (I) > (IV) (d) (II) > (III) > (IV) > (I)
48. (M) Br has low reactivity in CH 2  CH  Br because :
(a) the C  Br bond has a partial double bond character
(b) of the +M effect of bromine
(c) Br is electronegative

(a) (b)
49. (M) Which of the following have larger C—O bond length
O
||
than C—O bond length of CH 3  C  CH 3 ?
(c) (d)
(a) (b)
(c) (d)
52. (M) Which statements among following are correct ? 57. (A) Assertion : The carbocation CF3 CH2 is less stable
(a) Hydration effect stabilize dimethyl ammonium ion than CF3 .
more than trimethyl ammonium ion
Reason : In case of CF3 CH2, CF3 is strong electron
(b) is more basic than withdrawing, therefore increases +ve charge whereas in
CF3 , lone pair of ‘F’ overlap with vacant p-orbital of

(c) nucleophilicity in DMSO carbon reducing +ve charge by pp - pp bonding or back
bonding.
(d) Phenol is more acidic than CH3OH
(a) A (b) B
53.(A) Assertion : Tropylium cation is more stable than
(c) C (d) D
 CH3 3 C 58. (A) Assertion : The two structures,
Reason : It is stabilized by both resonance effect and CH3 – CH2 – CH2 – C  CH and CH3  CH  C  CH are
inductive effect. |
CH3
(a) A (b) B
chain isomers.
(c) C (d) D
Reason : The chain isomers differ in the chain of carbon
54.(A) Assertion : p-nitrophenol is a stronger acid than atoms.
o-nitrophenol.
(a) A (b) B
Reason : Intramolecular hydrogen bonding make the
(c) C (d) D
o-isomer weaker acid than p-isomer.
59. (A) Assertion : CHCl = CHBr exhibits geometrical isomerism.
(a) A (b) B
Reason : Presence of C = C is the condition for a
(c) C (d) D
compound to exhibit geometrical isomerism.
55.(A) Assertion : p-hydroxybenzoic acid has a lower boiling (a) A (b) B
point than o-hydroxybenzoic acid. (c) C (d) D
Reason : o-hydroxybenzoic acid has intramolecular 60. (A) Assertion : Ethylene is more reactive than ethane.
hydrogen bonding.
Reason : Ethylene possess  bond.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
56. (A) Assertion : The acetate ion is a weaker base than the
61. (A) Assertion : A mixture of o-nitrophenol and p-nitrophenol
ethoxide ion. can be separated by steam distillation.
Reason : In carboxylic acids, the carbonyl group is Reason : p-Nitrophenol is steam volatile while o-
nitrophenol is not steam volatile.
polarized and so the carbon of the carbonyl group bears
(a) A (b) B
a partial +ve charge.
(c) C (d) D
(a) A (b) B
(c) C (d) D
62. (A) Assertion : The C  C distance is longer than C = C 68. (C) Which of the following has highest heat of
distance hydrogenation?
Reason : Both C atoms in alkenes are sp2 hybridized. (a) CH 2 CH 2 (b) But-l-ene
(a) A (b) B (c) Isobutylene (d) Tetramethyl ethylene
(c) C (d) D 69. (C) Which of the following has highest heat of
combustion ?
63. (A) Assertion : Conjugated dienes are more stable than non-
(a) Isobutylene (b) But-l-ene
conjugated dienes.
(c) Tetramethyl ethylene (d) But-2-ene
Reason : 1,4-Pentadiene is a non-conjugated diene.
70. (C) Which of the following is incorrect hyperconjugative
(a) A (b) B structure?
(c) C (d) D
64. (A) Assertion : All carbon atoms in 1,3-butadiene are sp2
hybridized.
Reason : 1,3-Butadiene is a conjugated diene.
(a) A (b) B (a) (b)
(c) C (d) D
65. (A) Assertion : Tertiary carbocations are generally formed
more easily than primary carbocations.
Reason : Hyperconjugation as well as inductive effect
due to additional alkyl groups stabilize tertiary
carbocations.
(a) A (b) B (c) (d)
(c) C (d) D
66. (X) Match the Column I and II (Matrix)
(A) — NO2 (P) –M effect
– Comprehension
(B) — O (Q) +M effect
(C) — O — CH3 (R) +I effect When (C—H) s electrons are in conjugation to pi bond,
this conjugation is known as hyperconjugation : For
(D) C N (S) –I effect
any compound to show hyperconjugation
67. (X) Match the Column I and II (Matrix)
2

(i) Compound should have one sp -hybridised carbon.
(A) CH 3  C H  CH 3 (P) Pyramidal structure 2 3
(ii) a-carbon with respect to sp should be sp

(B) C H 3 (Q) Planar geometry (iii) a-carbon should contain at least one hydrogen atom.
 No. of a-carbon  stability of cation and alkene.

(C) CH 3  C H  CH 3 (R) Electrophile
(D) Singlet carbene (S) Nucleophile

71. (C) Which of the following alkenes is most stabilized?
Comprehension
Hyperconjugation is no bond resonance. It involves s
electrons of C—H bond. Greater the number of C — H (a) (b)
bonds (a-hydrogen atoms w.r.t. double bond) more will
be hyperconjugative structures, more will be stability.
Heats of hydrogenation of alkenes are affected by
hyperconjugative effects. Greater the hyperconjugative (c) (d)
structures, lower will be the heat of hydrogenation.
72. (C) Which of the following cations is hyperconjugation

destabilized?
(a) (b)
(c) (d)
Subjective Type Questions
73. In acidic medium, ................ behaves as the strongest

base. (nitrobenzene, aniline, phenol)
74. Arrange the following in the order of their increasing

basicity. p-toluidine, N, N-dimethyl-p-toluidine, p-
nitroaniline, aniline.
75. Give reasons for the following in one or two sentences.

The central carbon-carbon bond in 1, 3-butadiene is
shorter than that of n-butane.
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS
Single Choice Questions
1. Which of the following, has the most acidic hydrogen ? 6. Which of the following acids has the smallest dissociation
constant ? (2002)
(2000)
(a) CH3CHFCOOH (b) FCH2CH2COOH
(a) 3-hexanone (b) 2, 4-hexanedione
(c) BrCH2CH2COOH (d) CH3CHBrCOOH
(c) 2, 5-hexanedione (d) 2, 3-hexanedione 7. Which of the following represents the given mode of
2. Among the following, the strongest base is (2000) hybridisation sp2 – sp 2 – sp – sp from left to right ?
(2003)
(a) C6 H 5 NH 2 (b) p  NO2 C6 H 4 NH 2
(a) H2C = CH – C  N (b) HC  C – C  CH
(c) m  NO2  C6 H 4 NH 2 (d) C6 H5 CH 2 NH 2 (c) H2C = C = C = CH2 (d)

3. The correct order of basicities of the following compounds 8. Among the following, the molecule with the highest
is (2001) dipole moment is (2003)
(a) CH3Cl (b) CH2Cl2
(c) CH2Cl2 (d) CCl4
9.
(a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4
(c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4

Arrange in order of increasing acidic strength (2004)
4. Which of the following hydrocarbons has the lowest dipole
(a) X > Z > Y (b) Z < X > Y
moment ? (2002)
(c) X > Y > Z (d) Z > X > Y
(a) cis-2-butene (b) 2-butyne 10. Which of the following resonating structures of 1-methoxy-
(c) 1-butyne (d) 1, 3-butadiene is least stable ? (2005)
 
5. Identify the correct order of boiling points of the following (a) C H 2  CH  CH  CH  O CH3
compounds
 
CH3CH2CH2CH2OH (1) CH3CH2CH2CHO (2) (b) CH 2  CH  C H  CH  O  CH 3
CH3CH2CH2COOH (3) (2002)  

(c) CH2  C H  CH  CH  O  CH3
(a) 1 > 2 > 3 (b) 3 > 1 > 2
 
(c) 1 > 3 > 2 (d) 3 > 2 > 1 (d) CH 2  CH  C H  C H  O  CH 3
11. Which of the following is obtained when 4-methylbenzene
sulphonic acid is hydrolysed with excess of sodium
acetate ? (2005) (d)
(a)
14. The correct stability order for the following species is
(2008)
(b)
(c)
(a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV)
(d)
(c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV)
15. Hyperconjugation involves overlap of the following

12. When benzene sulphonic acid and p-nitrophenol are orbitals (2008)
treated with NaHCO3, the gases respectively are (2006)
(a) - (b) -
(a) SO2, NO2 (b) SO2, NO
(c) p-p (d) -
(c) SO2, CO2 (d) CO2, CO2
16. In the following carbocation ; H/CH3 that is most likely to
13. Among the following, the least stable resonance structure migrate to the positively charged carbon is (2009)
is (2007)
(a)
(a) CH3 at C-4 (b) H at C-4
(b) (c) CH3 at C-2 (d) H at C-2
(c)
17. The correct stability order of the following resonance 21. In the Newmann projection for 2,2-dimethylbutane
structure is
(2009)
X and Y can respectively by (2010)
(a) (I) > (II) > (IV) > (III) (b) (I) > (III) > (II) > (IV)
(a) H and H
(c) (II) > (I) > (III) > (IV) (d) (III) > (I) > (IV) > (II)
(b) H and C2H5
18. Among the following compounds, the most acidic is
(c) C2H5 and H
(2011)
(d) CH3 and CH3
(a) p-nitrophenol
22. With respect to graphite and diamond, which of the
(b) p-hydroxybenzoic acid
statements(s) given below is (are) correct ? (2012)
(c) o-hydroxybenzoic acid
(a) Graphite is harder than diamond.
(d) p-toluic acid
(b) Graphite has higher electrical conductivity than
Multiple Choice Questions diamond.
(c) Graphite has higher thermal conductivity than diamond.

19. Amongst the given options, the compounds in which alll
the atoms are in one plane in all the possible conformations (d) Graphite has higher C—C bond order than diamond.
(if any), is (are) (2011)
23. The IUPAC name(s) of the following compound is (are)
(2017)
(a)
(b)
(c) (a) 4-methylchlorobenzene
(d) (b) 4-chlorotoluene
(c) 1-chloro-4-methylbenzene
20. The compound in which C uses its sp3-hybrid orbitals for
bond formation is (2000) (d) 1-methyl-4-chlorobenzene
(a) HCOOH (b) (H2N)2 CO
(c) (CH3)3 COH (d) CH3CHO

Integer Type Questions
24. Among the following, the number of aromatic compound(s)
is ? (2017)
Matrix-Match Type Questions
25. Match the following with their Ka values (2003)
Benzoic acid 4.2 × 10–5
p-nitrobenzoic acid 3.3 × 10–5
p-chlorobenzoic acid 6.4 × 10–5
p-methylbenzoic acid 36.2 × 10–5
p-methoxybenzoic acid 10.2 × 10–5
Subjective Questions
26. Give reasons for the following
is more basic than HC  C . (2000)
27. Draw the resonating structures of .
(2003)
28. Which of the following is more acidic and why ?
(2004)
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HYDROCARBONS 98
HYDROCARBONS
SCAN CODE
Hydrocarbons
Chapter 02 99
HYDROCARBONS
Introduction :
Compounds containing carbon and hydrogen are hydrocarbons. They are of following types :
1. Saturated Hydrocarbons (Alkanes)
2. Unsaturated Hydrocarbons (Alkenes, Alkynes)
3. Aromatic Hydrocarbons
Alkanes -
(i) Branched and unbranched aliphatic saturated hydro carbons are called member of alkane. The structural formula
of alkane have only single bonds or all bonds in alkane is only  bonds.
(ii) Alkanes are less reactive and does not reacts with chemical reagants such as dil. and conc. HCl, dil. & conc.
H2SO4, dil. & conc. HNO3, Caustic soda, acidic & basic K2Cr2O7, KMnO4 etc. Therefore alkanes are also called
as paraffins. (Parum=little, affins = reactivity).
Methods of Preparations :
1. From alkenes and alkynes (Sabatier and Sandrens reaction) or (By hydrogenation of alkenes and alkynes) : Alkanes,
are obtained by the catalytic hydrogenation of alkenes and alkynes.
R—CH CH—R + H2 Catalyst
  R—CH2—CH2—R
Alkene Alkane
R—C C—R + 2H2 
Catalyst
 R—CH2—CH2—R
Alkyne
Catalyst :
(a) Pd/Pt at ordinary temp. and pressure
(b) Ni, 200–300° C (sabatier)
(c) Raney Nickel at room temp.
(d) Methane can not be prepared by this method (From unsaturated hydrocarbon).
eg : H  C  C  H  2H 2 
Ni / P t
 CH 3  CH 3
SCAN CODE
Hydrocarbons
HYDROCARBONS 100
2. From alkyl Halides (By reduction) :
2[ H ]
R—X   R—H + HX
( Nascent Hydrogen )
Catalyst :
(i) Zn + HCl (ii) Zn + CH3 COOH (iii) Zn—Cu couple in C2H5OH
(iv) Red P + HI (v) Al + Hg + ethanol
eg : CH3  Cl 
2[H]
Zn / HCl
CH 4  HCl
Mechanism :
(a) Alkyl halides can also be reduced to alkane by H2/Pd or LiAlH4 or H2/Ni.
(b) Reduction is due to the electron transfer from the metal to the substrate (R- X)
(c) If any alkyl halide is asked, the H-atom of any carbon atom of given alkane is removed by halogen atom.
3. From alkyl halide (By Wurtz reaction):
A solution of alkyl halide in ether on heating with sodium gives alkane.
Dry
R — X  2 Na  X—R   R—R  2 NaX
ether
(a) Two moles of alkyl halide treated with Na in presence of dry ether. If ether is wet then we obtain alcohol.
CH 3 Cl  2Na  Cl  CH 3 
dry ether
 CH 3  CH 3  2NaCl
(b) Methane cannot be prepared by this method. The alkane produced is higher and symmetrical i.e. it contains
double the number of carbon atoms present in the alkyl halide taken.
(c) Two different alkyl halides, on wurtz reaction give all possible alkanes.
(d) The seperation of mixture in to individual members is not easy because their B.P. are near to each other and thus
wurtz reaction is not suitable for the synthesis of alkanes containing odd number of carbon atom.
(e) This reaction generally fails with tertiary alkyl halide.
Mechanism : Two mechanism have been proposed for this reaction.
(a) Ionic Mechanism:
 2Na   2e 
2Na 
2Na   2X  
 2NaX
Example : 2C 2 H 5  I  2Na 
 C 2 H 5  C 2 H 5  2NaI
n  bu tan e
SCAN CODE
Hydrocarbons
HYDROCARBONS 101
(b) Free radical mechanism :
 Na   e
Na  
R   R  R — R Na   X  
 NaX
Product
Free radicals also undergo Disproportionation i.e. one radical gains hydrogen at the expense of the other which loss
hydrogen.
.
H
. . .
CH2 —CH2 + C2H5  C2H6 + C2H4
Ethane Ethylene
This explains the presence of ethylene and ethane in the butane obtained by Wurtz reaction.
4. Corey-House Synthesis :
This method is suitable for the preparation of unsymmetrical alkanes i.e. those of type R—R'
(i) RX + Li  RLi + LiX
(ii) 2RLi + CuX  R2CuLi + LiX
(iii) R2CuLi + R ' X  R—R' + RCu + LiX

(1 or2  )
Note : In Corey-house reaction symmetrical and unsymmetrical alkane both can be formed.
5. From Frankland Reagent: If Zn is used in place of Na, the reaction is named as Frankland reaction.
R—X + 2Zn +RX 
 R2Zn + ZnX2
Frankland reagent
R2Zn + R—X 
 R—R + RZnX
6. From Carboxylic Acid (By decarboxylation) : Saturated monocarboxylic acid salt of sodium or potassium on dry distillation
with soda lime give alkane.

 HCOONa + NaOH (CaO)   H 2 +Na 2 CO 3 
 

 CH 3 COONa + NaOH + CaO  CH 4 + Na 2 CO 3 
(a) The process of elimination of Carbon dioxide from Carboxylic acid is called decarboxylation.
(b) Replacement of -COOH by hydrogen is known as decarboxylation.
The alkane formed always contains one carbon atom less than the original acid.
(c) This reaction is employed for stepping down a homologous series.
SCAN CODE
Hydrocarbons
HYDROCARBONS 102
7. From carboxylic acid (By Kolbe's process) :
Alkanes are formed on electrolysis of concentrated aqueous solution of sodium or potassium salt of saturated monocarboxylic
acids.
R — R  2CO 2  2NaOH  H 2
Electrolysis
2RCOONa + 2H2O      
At Anode At Cathode
Electrolysis of Sodium propionate solution give n-butane, ethylene, ethane and ethyl propionate as follows-
electro.
2 C 2 H 5 — COONa   C 2 H 5 — C 2 H 5  2CO 2  2 NaOH  H 2
Mechanism : C2H5—COONa 

electro.
 C2H5 —COO- + Na+
H2 O
(Ionization)
e
At Anode : C2H5—COO-   C2H5— COO 

. Fragmentation
 C2 H 5 + CO2
C2H5 C O 
O
 
C2 H 5 + C2 H 5 
 C2H5—C2H5
Product
H
.. . .
CH2 —CH2 + C2H5 
 CH3—CH2—H + CH2 CH2
(minor products)
An ester is also formed.
 
C2H5— CO O + C H 5 
 C2H5 —COOC2H5
2
(minor products)
At cathode : Na+ + e-  Na

Na + H2O 
 NaOH + 1
2 H2
(a) Methane can not be prepared by this method.
(b) Electrolysis of an acid salt gives symmetrical alkane, However in case of a mixture of Carboxylic acid salts, all
probable alkanes are formed.
Electrolysis
R'COOK + R"COOK  (R'—R" + R'—R' + R"—R") +2CO2 + H2 +2KOH
(c) Presence of alkyl groups in  - position decrease the yield of alkanes.
(d) True aromatic acids do not undergo Kolbe's electrolytic reaction.
(e) Free radical mechanism has been suggested for Kolbe reaction.
(f) At anode alkane (major) and CO2 gas is formed while at cathode NaOH and H2 gas is formed.
(g) The concentration of NaOH in solution is increased with time so pH of solution is also increased.
8. From Alcohols, Carbonyl Compounds and Carboxlyic Acids
The reduction of either of the above in presence of red P and HI gives corresponding alkane.
SCAN CODE
Hydrocarbons
HYDROCARBONS 103
R—OH +2HI   R—H+H2O+ I2
Re d P
1 50  C
R—CHO + 4HI 

Re d P
1 50  C
 RCH3+H2O + 2I2
R—CO—R+4HI 
Re d P
150  C
 R—CH2—R+H2O + 2I2
RCOOH + 6HI 

Re d P
1 50  C
 R—CH2—R+H2O + 3I2
In the above reaction I2 is formed which acts as reducing agent and may reduce alkane and form alkyl halide. So red
P is added in the reaction to remove I2 formed in the reaction.


R—CH3 + I2  R—CH2—I + HI
2P + 3I2 
 2PI3
9. From Carbonyl Compounds (By Clemmensen's method) :
Carbonyl compounds (Preferably ketones) may also be reduced with Zinc amalgam and concentrated HCl
(Zn—Hg/HCl), this reaction is called Clemmensen reduction.
R—CO—R'+4H 
Zn / Hg
 R—CH —R'+H O
con. HCl 2 2
e.g : CH3  CO  CH3  4H 

Zn / Hg
Conc.HCl
 CH3CH 2 CH3  H 2 O
CH4, CH3—CH3, isobutane and neopentane are not obtained from Ketones because these alkane do not contain CH2
group.
10. From aldehydes and ketones (By Wolf Kishner reaction) :
C O+ NH2NH2 
 C Glycol / KOH
N.NH2   CH2 + N2

Hydrazine Hydrazone
From Grignard Reagent
(a) Formation of alkanes with same number of C atoms : With same number of C-atoms as G.R. react with compound
containing active hydrogen alkanes is obtained.
R  Mg  X  H  O  H 
 R  H  Mg(OH) X
R  Mg  X  R  O  H 
 R  H  Mg(OR) X
R  Mg  X  R  NH  H 
 R  H  Mg(NHR) X
This reaction is used to determine the number of active H-atoms in the compound this is known as Zerewitnoff's method.
(b) Grignard Reagent react with alkyl halide to give higher alkanes :
RMgX + R'—X   R—R' + MgX2
From metal carbide (By hydrolysis) :
Only CH4 can be obtained by the hydrolysis of Be or Al carbides
Al4 C 3  1 2 H 2 O 
  4 Al(OH )3  3 CH 4
Be 2 C  4 H 2 O 
  2 Be(OH )2  CH 4
NOTE : Many reactions will be covered in later chapters
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Hydrocarbons
HYDROCARBONS 104
Preparation of Alkanes
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Hydrocarbons
HYDROCARBONS 105
Physical Properties of Alkanes :
Physical state :
The first four members (C1 to C4) are gases ; the next thirteen members, (C5 to C17) are liquids while the higher members are
waxy solids.
Boiling points :
The boiling points of n-alkanes increase regularly with the increase in the number of carbon atoms.
Among the isomeric alkanes, the branched chain isomers have relatively low boiling points as compared to their corresponding
straight chain isomers. Greater the branching of the chain, lower is the boiling point. This is due to the fact that branching of
the chain makes the molecule more compact and brings it close to a sphere, so the magnitude of vander wall forces decreases.
Melting Point :
It is evident that the increase in melting point is relatively more in moving from an alkane having odd number of carbon atoms
to the higher alkane with even no. of ‘C’ while it is relatively less in moving from an alkane with even number of carbon atoms
to the higher alkane.
Solubility :
In keeping with the popular rule “like dissolves like” hydrocarbons are insoluble in polar solvent like water because they are
predominantly non-polar in nature.
Density :
The densities of alkanes increase with increasing molecular weight but become constant at about
0.8 g cm–3. This means that all alkanes are lighter than water.
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HYDROCARBONS 106
Chemical Reactions of Alkanes :
Alkanes undergo free radical substitution reaction, these reactions include three steps.
(i) chain initiation (ii) chain propagation. (iii) chain termination
Halogenation :
UV Light or temp
R – H + X2          R – X + HX
250  400C
Mechanism :
(i) Chain initiation 

 It is an endothermic step.
UV or temp.
X2  
 2X
250  400C
(ii) Chain propagation 


X  R  H 
 R  HX
R  X  X 
R  X  X
(iii) Chain termination 

 It is always exothermic
 X
X  
 X2
R  R 
R  R
R  X
 
R  X
Reactivity of X2 : F2 > Cl2 > Br2 > I2
Reactivity of H : 3°H > 2°H > 1° H
With F2 alkanes react so vigorously that even in the dark and at room temperature, reactant is diluted with an Inert gas.
Iodination is reversible reaction, since HI formed as a by product and It is a strong reducing agent and reduces alkyl iodide
back to alkane. Hence iodination can be done only in presence of strong oxidising agent like HIO3, HNO3 or HgO.
R – H + I2 R – I + HI
5HI + HIO3  3H2O + 3I2

2HI + HgO  I2 + H2O + Hg
2HI + 2HNO3  I2 + 2H2O + NO2
Formation of alkyl free radical is rate determining step.
Order of stability of Free radical :
When equimolar amount of methane and Cl2 is taken, a mixture of four possible products are formed, but when we take excess
of CH4 then yield of CH3Cl will be high.
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HYDROCARBONS 107
One chlorine molecule cleaves to form two chlorine radicals, by a photon of light. Each chlorine atom starts a chain reaction
and on an average each chain contains 5000 repetitions of the chain propagating cycle so about 10,000 molecules of CH 3Cl
are formed by one photon of light.
In a chain reaction following reagents are involved -
(i) Initiators : They initiate the chain reaction, Initiators are peroxide (R2O2), etc.
•
h
R – O – O – R  R O
or 
•
h
R  C  O  O  C  R  R  C  O
|| || or  ||
O
O O
(ii) Inhibitors : A substance that slows down or stops the reaction is known as inhibitors
For example O2 is a good inhibitor
• • •
R + O2  R  O  O + R  R – O – O – R
All reactive alkyl free radicals are consumed so reaction stops for a period of time.
Relative reactivity of halogen towards methane :
Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (enthalpy change)
Halogenation of higher alkane :

Cl
(a) CH3 – CH2 – CH3   CH 3  CH  CH 3 + CH 3  CH 2  CH 2  Cl
2
light, 25C
|
Cl
55% 45%
Cl2
(b) CH3 – CH2 – CH2 – CH3 
light, 25C
 CH 3  CH 2  CH  CH 3 + CH 3  CH 2  CH 2  CH 2  Cl
|
Cl
72% 28%
CH3
|
Cl2
(c) CH 3  CH  CH 3   CH 3  CH  CH 2  Cl + CH  C  CH 3
light, 25C 3
| | |
CH 3 CH 3 Cl
64% 36%
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Hydrocarbons
HYDROCARBONS 108
Br2
(d) CH3 – CH2 – CH3 
 CH 3  CH 2  CH 2  Br + CH 3  CH  CH 3
heat, 127C
|
Br
3% 97%
CH3
|
Br2
(e) CH 3  CH  CH 3      CH 3  CH  CH 2 Br + CH3  C  Br
heat, 127  C
| | |
CH 3 CH 3 CH3
trace over 99%
Relative amounts of the various isomers differ remarkably depending upon the halogen used. From the above reaction, it is
observed that chlorination gives mixture in which no isomer greatly dominates while, in bromination gives a mixture in which
one isomer dominates greatly (97% – 99%),
Factors affecting the relative yields :

Factors determining the relative yields of the isomeric products.
(i) Probability factor : Depends on the other number of each type of H atom in the molecule.
(ii) Reactivity of hydrogen : The order of reactivity is 3° > 2° > 1°. The relative rate per hydrogen atom is found to be
(iii) Reactivity v/s selectivity principle :

The more reactive is halogen less selective it will be, so the more reactive chlorine free radical is less selective and more
influenced by the probability factor and the less reactive Bromine free radical is more selective and less influenced by the
probability factors.
Sulphonation :
Lower alkanes are not easily sulphonated but hexane & higher members are sulphonated on heating with oleum (conc. H 2SO4
+ SO3) at 400°C
400C
C6H14 + H2SO4  C6H13SO3H + H2O
Isomerisation :
Alkanes undergo isomerisation
Anhyd. AlCl3 / HCl
CH3CH2CH2CH3       CH 3  CH  CH 3
300C
|
CH 3
Isobutane
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HYDROCARBONS 109
CH3
|
AlCl3 / HCl
CH3 – (CH2)3 – CH3    
  CH3  C  CH3
300C
|
CH3
Neopentane
Alkylation :
Higher branched alkanes are formed when isoalkane add to isoalkene in presence of Conc. H2SO4
CH 3
CH3
| |
conc. H2SO4
CH 3  C  H + H2C  C  CH3      CH3  C  CH2  CH  CH3
| | |
| CH3 CH3
CH3
CH 3 Isobutene
Isooc tan e
Isobutane
Aromatisation :
Alkanes containing 6 or more number of C atoms are oxidised (dehydrogenate & cyclised) in presence of oxidising agent at
higher temparature and form benzene or its derivatives.
Cr O  Al O
CH3 – (CH2)4 – CH3 23  
2 3
+ 4H2
600C
High P
Cr O  Al O
CH3 – (CH2)5 – CH3 23  
2 3
600C
High P
Cr O  Al O
CH3(CH2)6CH3 23  
2 3
+
600C
High P
CH3
| Cr O  Al O
CH3  (CH2 ) 4  CH  CH3 23  
2 3
600C
High P
CH3
| Cr O3  Al 2O3
CH3  (CH2 )3  CH  CH2  CH3 2  
600C
High P
Pyrolysis / Cracking :
CH3 – CH2 – CH3 CH3CH3 + CH3CH = CH2 + CH2 = CH2+ CH4 + H2
Higher alkanes are heated in absence of air so these compounds break down into smaller alkanes which are better fuels.
Mixture of products contains all lower alkanes, alkenes & hydrogens.
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Combustion :
Alkane an complete combustion yield CO2 and H2O.
 3n  1 
combustion
CnH2n+2 +  2  O2     nCO2 + (n + 1) H2O ( ΔH combustion = -ve)
  
exothermic reaction
 y combustion y
CxHy +  x   O2     xCO2 + HO
 4  2 2
combustion
C5H12 + 8O2     5CO2 + 6H2O

Points to remember for H of combustion :
Homologues : Higher homologues have higher heat of combustion.
CH4 < C2H6 < C3H8
Isomers : Branched isomer has lower heat of combustion.More branched alkane has more no. of primary
C – H bonds. (therefore it has more bond energy).
> >
Cyclo-alkanes : More strained ring has higher heat of combustion per – CH2 – unit.
> > > (Hcomb. per ‘CH2’ unit)
Octane Number :
It is a scale used to measure the fuel efficiency when the fuel burns during combustion, more branched alkanes have lower
knocking (cracking sound). so are better fuels. On commercial scale iso-octane has been alotted a rating i.e. octane no. of
Isooctane is 100 & n-heptane is - ‘0’
If the octane no. of a fuel is 80, it means that the efficiency of the fuel is equivalent to the efficiency of mixture of 80% isoctane
and 20% n-heptane.
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Chemical Properties of Alkanes
Solved Examples
1. Predict the product in (a), (b) and (c) of the given reaction :
Sol. In all cases product is
Na
2. C2H5Cl   products
Ether
Write all possible product
Sol. CH3 – CH2 – Cl  CH3  CH2  CH2  CH3

major

CH3 – CH2 – Cl CH3  C H2
coupling
   CH3 – CH2 – CH2 – CH3
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Hydrocarbons
HYDROCARBONS 112
disproportion
  CH3 – CH3 + CH2 = CH2
3. Wurtz reaction will not be observed in
(a) (b) (c) CH3  CH  Br (d) none of these

|
CH3
Ans. (b)
Sol. Na + H2 gas

Li CuI Y
4. CH3 – Br  A  B  C
if C is CH3 – CH2 – (CH2)5 – CH3, than what is Y.
Ans. CH3 – (CH2)6 – Br

Li CuI
Sol. CH3 – Br  CH3Li  (CH3)2CuLi 
CH3 – (CH2 )5 – CH2 – X
 CH3 – CH2 – (CH2)5 – CH3
5. Chlorination of CH4 involves following steps :

•
(i) Chain Initiation Cl2  2 C l
• •
(ii) Chain Propagation CH4 + C l  C H3 + HCl
• •
(iii) Chain Termination C H3 + C l  CH3Cl
Which of the following is rate determining ?

(a) Step (i) (b) Step (ii) (c) Step (iii) (d) Step (ii) and (iii) both
Ans. (b)
Sol. Formation of alkyl free radical is Rate determining step.
Alkenes
1. INTRODUCTION
These are acylic unsaturated hydrocarbons with carbon–carbon double bonds.

They form homologous series with general formula CnH2n Alkenes are also called as olefins, a term derived from olefiant gas,
meaning "oil forming".
Alkenes are among the most important industrial compounds and many alkenes are also found in plants and animals.
Ethylene is the largest–volume industrial organic compound, used to make polyethylene and a variety of other industrial and
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HYDROCARBONS 113
consumer chemicals.
Alkenes polymerise to give many important polymers.
2. STRUCTURE AND BONDING
(1) Alkenes are unsaturated hydrocarbons having at least one double bond.
(2) In Ethene C = C bond length is 1.34 Å
(3) Its bond energy is 146 kcal.mol-1
(4) The hybridization of (C = C) alkenic carbon is sp2
(5) The e cloud is present above and below the plane of   bonded skeleton.
(6) Compounds may exist as conjugated polyenes or as cumulated polyenes or as isolated polyenes
1.34A
117.2°
1.10A
(b)
121.2°
(a)
3. STABILITY OFALKENES
Overall relative stabilities of Alkenes

Studies of numerous alkenes reveal, pattern of stabilities that related to the number of alkyl groups attached to the carbon
atoms of the double bond. The greater the number of attached alkyl groups (i.e., the highly substituted the carbon atoms of
the double bond), the greater is the alkene’s stability. This order of stabilities can be given in general terms as follows.
Relative stabilities of alkenes
R H R R
> > C=C > > C=C > >
R H H H
Another way of measuring the stability of an alkene is the determination of its heat of hydrogenation or the heat of combustion.
( H = – ve)
1
H  (– ve sign indicates the exothermic nature of reaction)
stability
Heat of Hydrogenation of Alkenes :
Note :
Heat of
Alkene combustion
kJ / mol
1-Butene 2719
Isobutene 2703
cis-2-Butene 2712
trans-2-Butene 2707
All four butenes may be compared,

since all give the same products on
combustion viz. 4CO2 + 4H2O.
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HYDROCARBONS 114
Methods of preparation :
(I) From alkynes
(a) By Catalytic Hydrogenation of Alkynes in presence of poisoned catalyst (A Syn Addition of Hydrogen takes place
giving cis alkynes)
(i) Lindlar’s catalyst : Metallic palladium deposited on calcium carbonate conditioned with lead acetate and quinoline.
(ii) P-2 catalyst (Ni2B nickel boride)

General Reaction
H2 ,Pd / CaCO 3
(Lindlar 's catalyst )
R–C  C–R       
quinoline
H2 / Ni2B(P2 )
or H / Pd / CaCO
CH3 CH2C  CCH2CH3 (syn
  
2 3
Ex.
addition)
3  Hexyne
(b) Birch Reduction : (Anti Addition of Hydrogen take place giving trans-Alkenes)
It follows free radical path
Na / Li R H
General Reaction R C C R C C
Liq. NH3 H R
Na / NH (  )
Ex. CH3 – CH2 – C  C – CH2 – CH3   3
Note : This process of reduction is not eligible when terminal alkynes are taken.(R–C  CH) because terminal alkynes form sodium
salt with Na metal.
CH3 – C  CH + Na / NH3  CH3 – C  C¯ Na+ + [H+]
(II) From vicinal dihalides
There are two types of dihalides namely gem (or geminal) dihalides in which the two halogen atoms are attached to the same
carbon atom and vicinal dihalides in which the two halogen atoms are attached to the adjacent carbon atoms.
When vicinal dihalides are heated with Zn metal in presence of NaI in acetone or Zn in C2H5OH or Zn in CH3COOH,
corresponding alkynes are formed. This reaction is caused dihalogenation.
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General Reaction
Br
| |
NaI
CC C C
| | or Zn, CH3COOH
Br
NaI
Ex.4 CH3 – CHBr – CHBr – CH3    CH3 – CH = CH – CH3
Acetone
(III) From alkyl halides
When alkyl halide is heated with alc.KOH hydrogen halide is eliminated giving corresponding alkene. This is called as
dehydrohalogenation
CH3
| Heat
Ex. CH3  C  Br + alc. KOH  CH3  C  CH2  KBr  H2O
| |
CH3 CH3
Here  – H is eliminated by base hence called  elimination following Saytzeff rule
i.e. (Highly substituted alkene is major product). It also involves an anti elimination of HX.
Ex. +
(IV) By Dehydration of alcohols

Alcohols when heated in presence of following reagents undergo loss of water molecule and form alkenes. The elimination
is  elimination.
(i) H2SO4 / 160°C (ii) H3PO4 / D

(iii) P2O5 / D (iv) Al2O3 / 350°C undergo loss of water molecule and form alkenes
General Reaction
CH2
CH2OH
Ex. +
(I)
Minor
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HYDROCARBONS 116
(V) By Kolbe's Electrolytic synthesis :
CH2
Electrolysis
+ H2O     
  || + 2CO2 + 2KOH + H2
Current CH2
Note : Many reactions will be covered in Later Chapters
Preparation of Alkenes
Preparation of Alkenes
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HYDROCARBONS 117
Physical Properties of Alkenes / Hydrocarbons :
Chemical Properties :
Alkenes are more reactive than alkane because -
(a) The  electrons of double bond are located much far from the carbon nuclei and are thus less firmly bound
to them.
(b)  bond is weaker than  bond and more easily broken.
The reactivity order for alkenes -
CH2 CH2 > R—CH CH2 > R2C CH2  RCH CHR > R2C CHR > R2C CR2
(Trans < Cis)
The reactivity order of alkenes has been written in terms of heat of hydrogenation of alkene, more is the heat of
hydrogenation (H = –ve), more is the reactivity, the reactivity of alkene is however also related to
(i) Steric hinderence (ii) Hyperconjugation (iii) Heat of Combustion.
Alkenes give the following type of reactions :
(a) Addition reaction (b) Oxidation reaction. (c) Substitution reaction.
(d) Polymerization Reaction. (e) Isomerisation
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HYDROCARBONS 118
Alkene Hea t o f co mbus tio n (kJ/ mo l) Hea t o f hydro g e na tio n (kca l/ mo l)
1 -Butene 2719 3 0 .3
Isobutene 2703 2 7 .2
Cis-2 -butene 2712 2 8 .6
trans-2-butene 2707 2 7 .6
Alkene react undergo electrophilic addition reactions, under and special conditions alkenes are undergo for radical reaction
(A) Addition Reaction :
Alkene react with H2 in presence of Ni/Pd to give alkanes. This reaction is called as catalytic Hydrogenation.
Free radical addition :
Addition of H2 :
Ni,Pt or Pd
R—CH = CH2+H2   R—CH2—CH3+ Heat of Hydrogenation.
Note: (a) Reaction is exothermic
1 1
(b) Stability of alkene  heat of hydrogenation  reactivity of alkene with H
2
(c) The process is used to obtain vegetable (saturated fats) ghee from hydrogenation of oil.
Electrophilic addition reactions :
Because of the presence of >C C< bond in molecules, alkenes generally take part in the addition reactions.
C C
C C + AB 

A B
Alkene Addition product

From mechanism point of view, the addition in alkenes is generally electrophilic in nature which means that attacking
reagent which carries the initial attack is an electrophile (E+). This is quite expected also as there is high electron
density in the double bond. The mechanism proceeds in two steps.
Step I : The  –electron cloud of the double bond causes the polarisation of the attacking molecule (E–Nu) which
cleaves to release the electrophile ( E  ) for the attack. The double bond simultaneously undergoes electromeric effect
and the attack by the electrophile is accomplished in slow step (also called rate determining step) to form a
carbocation intermediate.
C C  (Slow )
Rate determining step (RDS)

Addition product
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HYDROCARBONS 119
Step II : The nucleophile (: Nu – ) released in the slow step combines with the carbocation to give the desired addition
product in the fast step.
Example of electrophilic addition reaction

Addition of Halogen :
It is a electrophilic addition reaction.
X X
R CH CH2 + X2 R CH CH2
(Vicinal halides)
Note: (a) The reaction is quite fast with Cl2, relatively slow with Br2 and is very slow with I2
(b) Addition of F2 is exothermic reaction so it is difficult to control.
(c) The addition of Br2 on alkenes provides a useful test for unsaturation in molecule.The brown colour of the
bromine being rapidly discharged. Thus decolarization of 5% Br2 in CCl4 by a compound suggest unsaturation
in it. Colourless dibromo compound is formed.
(d) I2 reacts slowly with alkenes to form Vicinal di-iodides which are unstable and eliminated I 2 molecule very
readily to give original alkene due to large size of Iodine they overlap.
CH3—CH CH2 + I2  CH3 CH CH2
I I
Unstable
Mechanism : It is interesting to note that product which is mainly formed as a result of addition is trans in nature
whereas the cis isomer is obtained in relatively smaller proportions. Since carbocation intermediate is planar (sp 2
hybridised), both cis and trans addition products must be formed almost in equal proportions. The trans product
can be justified in case a cyclic ion is formed by the initial electrophile attack.
+ –
CH2 = CH2+ Br—Br  
(Slow )
 CH2 CH2
Br
(Halonium ion)
The attack of Br– ion on the cyclic ion takes place from the side opposite to side where bromine atom is present
in order to minimise steric hindrance.
H2C
Br– + (Fast )
Br  Br H2C
H2C
CH2 Br
1,2–Dibromoethane
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aq.NaCl
Ex. CH 2  CH 2 + Br2   Products, what are the products?
Ethylene
Sol.
Similarly
Addition of hydrogen halides :

X
R—CH CH—R + HX 
 R CH2 CH R
X
R—CH CH2 + HX 
 R CH CH3
Note: (i) The order of reactivity of hydrogen halide is : HI > HBr > HCl > HF
(ii) Their addition is an example of electrophilic addition.
(iii) Addition on alkene proceeds via the formation of more stable carbonium ion.
(iv) Addition of HX on unsymmetrical alkenes (R—CH CH2) takes place according to Markownikoff's rule.
MARKOWNIKOFF'S RULE :
(a) First Rule : When molecule of a HX add up on unsymmetrical unsaturated hydrocarbon, the halogen atom
goes to the unsaturated carbon atom bearing lesser number of hydrogen atoms.
CH3 CH CH2 + HX 
 CH3 CH CH2
H
Mechanism : It is electrophilic addition and is illustrated by the action of HCl to propene.
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
Primary carbocation (CH3—CH2— CH 2 ) is formed but only in very small proportion since it is less stable than the
secondary carbocation. Markownikoff's rule can also be stated as :
The electrophilic addition to unsymmetrical alkenes always occurs through the formation of a more stable
carbocation intermediate.
(b) Second Rule : In the addition of HX to vinyl halide and analogous compounds, the halogen attaches itself
to the carbon atom, on which the halogen atom is already present.
CH2  CH3 CH Cl
CH—Cl+HCl 
Cl
Ethylidene chloride
Mechanism :
In vinyl chloride two effects operate simultaneously in opposite direction-

(i) Inductive effect – electron attracting (-I) effect of chlorine.
(ii) Resonance effect – electron pair releasing (+R) effect of chlorine.
The resonance effect is much more than the -I effect of Chlorine at the time of attack.This creates centres of +ve
and –ve charges.
All polar reagents of the general structure Y  Z  (such as H   X  , H   OH  H   SO 3 H  , X  OH  ) add on
unsymmetrical unsaturated compound in accordance with Markownikoff's rules. Such additions are called normal
Markownikoff's rule, where as additions in the opposite manner are reffered to as abnormal or antimarkownikoff's
additions.
ANTI MARKOWNIKOFF'S RULE OR PEROXIDE EFFECT OR KHARASCH RULE :

(i) In the presence of peroxides the addition of HBr on unsaturated unsymmetrical compound takes place against/
opposite to Markownikoff's rule. This is called peroxide effect and is due to the difference in the mechanism
of the addition.
(ii) In the normal Markownikoff's addition the mechanism is ionic.
(iii) In the presence of peroxide the addition of HBr takes place via free radicals.
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HBr
CH3 CH CH3 Markownikoff's addition.
Br
CH3 CH CH2 Isopropyl bromide
HBr
CH3 CH2—CH2—Br Anti Markownikoff's addition
R O O R
n–Propyl bromide
Mechanism :
(i) Chain initiation -
(a) R—O—O—R 
 2RO•
(b) HBr + RO• 

 ROH + Br•
(ii) Chain propagation
. HBr
.
CH3 CH CH2Br  CH3CH2CH2Br + Br
. 2° free radical more stable (major)
CH3 CH CH2 + Br
Br Br
. HBr
.
CH3 CH CH2 CH3CHCH3 + Br
1° free radical less stable
(iii) Chain termination :
R    R 
 R—R
R    Br 
 R—Br

Br  Br 
 Br—Br
Note : HCl and HI do not give antimarkownikoff products in the presence of peroxides.
Reasons are :
(a) The H—Cl bond is stronger than H—Br. So Cl free radical is not formed.
(b) The H-I bond is weaker than H—Br bond. It is broken by the alkoxy free radicals obtained from peroxides,
but the addition of iodine atom on alkene is endothermic as compared to Br atom therefore iodine atoms so
formed combine with each other to yield iodine.
3. Addition of Hypohalous acid (or X2/H2O, or HOX) : It is a electrophilic addition and follows Markownikoff's rule.
In the fast step, there is competition between Cl- ion and H2O molecule to act as nucleophile but H2O is a better
nucleophile.
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Re activity order is HOCl > HOBr > HOI
7. Addition of H2SO4: Alkene react with conc. H2SO4 to produce alkyl hydrogen sulphate. Which gives alcohols on
hydrolyses.This reaction used to seprate alkene from a mixture of alkane and alkene.
OSO3H OH
H2O
CH3 CH CH2+ HOSO3H  CH3 CH CH3  CH3 CH CH3 + H2SO4
Isopropyl alcohol
Note: Ethyl hydrogen sulphate give ethylene when heated 430-440K while ethanol is obtained on boiling it with water.
4. Addition of water (Hydration of alkenes) : Propene and higher alkenes react with water in the presence of acid to
form alcohol. This reaction is known as the hydration reaction . Intermediate in this reaction is carbocation, so
rearrangement will take place.
+
H
(i) CH3 - CH = CH2 + H2O CH3 - CH - CH3
OH
Propane Propan-2-ol
OH
H
CH3 C CH2 + H2O 
(ii)  CH3 C CH3
CH3 CH3
2–Methylpropene 2-Methylpropan-2-ol
Mechanism :

CH3 CH CH2 + H+ 
(Slow)
 CH3 CH CH3
Carbocation (2°)
 .. –H 
.. H   CH3 CH CH3  CH3 CH CH3
(Fast )
CH3 CH CH3 + H O
H ..
O H O H

Propan-2-ol
5. Hydroboration : It obeys markownikoff's rule. Diborane readily reacts with alkenes giving trialkyl boranes. The reaction
is called hydroboration.
+ – +  –
2R CH CH2 + BH2 6
 2(R CH2 CH2) BH2

 R CH CH2

R CH CH2
(R CH2 CH2)3B  2(R CH2 CH2)2 BH
Trialkylborane
BH3 does not exist or stable as monomer so a solvent THF (tetra hydro furane) is used.
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
 H 
Example : 3CH3 CH CH2 + B H THF
  (CH3—CH2—CH2)3B
H
BHR2 also can be taken.
 
Example : CH3 CH CH2 + BHR2  CH3 CH2 CH2 BR2
6. Oxymercuration – demercuration : Mercuric acetate in tetrahydro furan (THF) is treated with an alkene.The addition
product on reduction with sodium Boro hydride in aqueous NaOH solution gives alcohol. It follows the
markownikoff's rule.
CH3—CH  CH3 CH CH3
CH2 
OH
(i) (AcO)2 Hg/H2O (Mercuric acetate) or (CH3COO)2 Hg/H2O
(ii) NaBH4/NaOH
Mechanism :
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Note : Intermediate is cyclic cation so their is no rearrangement.
7. Hydroformylation or Oxo reaction : Alkenes react with Carbon monoxide and hydrogen at
100 – 150°C temperature and high pressure (200 atm) in the presence of Cobalt catalyst to produce an aldehyde.It
does not follows markownikoff's rule.
The net reaction is the addition of a H–atom to one of the Olefinic bond and a formyl (–CHO) group to the other,
thereby forming aldehydes
Co/ 150°C R CH2 CH2 CHO

R CH CH2 + CO + H2 high pressure
R CH CH3
CHO
8. Alkenylation (Addition of alkene) In presence of H2SO4 or H3PO4 at 80°C dimerisation of isobutylene take place gives
two isomer of octene.
CH3 CH3 CH3 CH3 CH3
H SO , 80°C
2CH3 C CH2  CH2
2 4
C CH2 C CH3 + CH3 C CH C CH3
CH3 CH3
Mechanism :
CH3 CH3
CH3 C CH2 + H CH3 C

CH3

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CH3 CH3 CH3 CH3

CH3 C CH2 +  C CH3  CH3 C CH2 C CH3

CH3  CH3
–H
CH3 CH3 CH3 CH3

CH2 C CH2 C CH3 CH3 C CH C CH3
CH3 CH3
(B) OXIDATION REACTION :

Alkenes are easily oxidised by oxidising agents. Oxidising agents attack on double bond and product formed during
oxidation depends on oxidising agents.
e.g. CH 2  CH 2  H 2 O  [O]  CH 2  CH 2

KMnO 4
| |
OH OH
(6) Alkene on combustion gives CO2 and H2O
3n
CnH2n + O 
 nCO2 + nH2O
2 2
3n
One mole of alkene requires moles of O2 for complete combustion.
2
(1) Ozonolysis : (A test for unsaturation in molecule)
(i) The addition of ozone on the double bonds and subsequent a reductive hydrolysis of the ozonide formed
is termed as ozonolysis.
(ii) When ozone is passed through an alkene in an inert solvent, it adds across the double bond to form an
ozonide. Ozonides are explosive compound they are not isolated.
(iii) On warming with Zn and H2O, ozonides cleave at the site of the double bond, the products are carbonyl
compound (aldehyde or ketone) depending on the nature of the alkene.
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Example : Ozonolysis
CH3 C CH CH3   CH3 C O + CH3CHO
CH3 CH3
(iv) Ozonolysis of alkenes helps in locating the position of double bond in an alkene. It can be achieved by
joining together the carbon atoms of the two carbonyl compounds formed as the products of ozonolysis with
double bond.
H H
1 2 3 4
Example : CH3 C O + O C CH3  CH3 CH CH CH3
Ethanal But-2-ene
H H
1 2 3 4
Example : H C O + O C CH2 CH3  CH2 CH CH2 CH3
Methanal Propanal But-1-ene
CH3 CH3 CH3 CH3
Example : CH3 C O + O C CH3  CH3 C C CH3
Propanone 2,3–Dimethyl but–2–ene
It may be noted that reaction with bromine water or Baeyer's reagent detects the presence of double bond
(or unsaturation) in an alkene while ozonolysis helps in locating the position of the double bond. In reduction of
ozonide by LiAlH4 or NaBH4 gives corresponding alcohols.
O
LiAlH4
R' CH CH R"  R'CH2OH + R"CH2OH
O O (Alcohols)
(2) Hydroxylation : Oxidation of carbon-carbon double bond to C C is known as hydroxylation.
OH OH
(a) Oxidation by Baeyer's reagent (A test for unsaturation) : Alkenes on passing through dilute alkaline 1% cold KMnO4
(i.e., Baeyer's reagent) decolourise the pink colour of KMnO4 and gives brown ppt MnO2 and glycol.
OH –
C C + H2O + [O] 
KMnO  C C Glycol
4
OH OH (cis–addition)
R CH R CH O O R CH OH
H2O
+ OsO4  Os 
(b) By OsO4 : R CH R CH O O R CH OH
cis–addition
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O OH
(c) By peracid : > C  HCOOH  H2 O
C < +H C O O H   >C C<   >C C<
O HO H
trans glycol
(3) Epoxidation :
(a) Alkenes reacts with oxygen in the presence of Ag catalyst at 250°–400° C to form epoxide.
O OH
1 H2 O
CH2 CH2  O 2 
Ag
  CH2 CH2
  CH2 CH2 (anti addition)
2
OH
(b) Prilezhaev reaction: When an alkene is treated with perbenzoic acid, an epoxide is formed. Such an
epoxidation is known as Prilezhaev reactions.
RCH CH2 + C6H5COOOH 
 R CH
O + C6H5COOH
CH2
Epoxide
Syn addition Syn addition
Meso compound Racemic mixture
cis alkene trans alkene
Anti addition Anti addition
Racemic mixture Meso compound
Syn addition on alkene  H 2 , O 2 , Baeyer 's reagent, OsO 4 / H 2 O

Anti addition on alkene  X 2 , HOX, RCOOH / H 2 O, Ag 2 O / H 2 O
Example :
CH3 CH3
(i) Br2
H Br Br H
CH3 H Anti addition +
Br H H Br
C
CH3 Racemic mixture CH3
C
CH3 H CH3
D2
cis–alkene Syn addition H D
H D
CH3
Meso compound
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(ii) CH3 CH3

Baeyer's
OH H H OH
CH3 H Reagent +
Syn addition H OH OH H
C
CH3 Racemic mixture CH3
C
H CH3 CH3
RCOOOH/ H2O
trans-alkene Anti addition H OH
H OH
CH3
Meso compound
(4) Oxidation by strong oxidising agent (Oxidative cleavage) : The alkenes themselves are readily oxidised to acid or
ketone by means of acid permanganate or acid dichromate. If HCOOH is formed, it further oxidized to CO2 and H2O.
Keep it in mind that no further oxidation of ketones will takes place.
CH2 CH2+4[O] 
 2HCOOH 
2[O ]
 2CO2 + H2O
CH3CH CH2 
5 [O ]
 CH3COOH+CO2+H2O
4 [O ]
CH3CH CHCH3   2CH3COOH
CH3 CH3
4 [O ] C O + CO2 + H2O
C CH2 
CH3 CH3
(5) Oxidation with retention of Carbon-Carbon bond - (Wacker's process) :

PdCl
CH2 CH2+H2O2 
CuC l
2
 CH3CHO
2
(C) Substitution Reaction (Allylic substitution) :

When alkenes are treated with Cl2 or Br2 at high temp., one of their allylic hydrogen is replaced by halogen atom.
Allylic position is the carbon adjacent to one of the unsaturated carbon atoms.It is free radical substitution.
0
CH3—CH CH2 + Cl2    ClCH2—CH
50 0 C CH2 + HCl
Allyl chloride
(3-Chloro-1-propene)
N-Bromosuccinimide (NBS) is an important reagent used for allylic bromination and benzylic substitution.
O O
CH3 CH CH2 + CH2 C CH2 C
NBr  NH + Br CH2 CH CH2
CH2 C CH2 C
(NBS)
O O
Substitution reaction is not given by ethene.
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CH3 CH2 Br
Example : (i) NBS
 

(ii) NBS
  Br
 
H . Br
CH3 CH3 CH3
3° more stable
(D) Polymerization :
(i) The process of formation of macro molecules by the addition of simple unsaturated molecules is known
as polymerization
(ii) The macro molecule formed is a polymer and simple molecules from which polymer is formed is called
monomer.
(iii) Molecular weight of polymer is simple multiple of monomer.
(iv) Addition polymerization can also be carried out by ionic mechanism by using Ziegler - Natta Catalysts
(R3Al + TiCl4)
(E) Isomerization :
Alkene on heating to 500° to 700 °C or on heating in presence of catalyst [AlCl3 or Al2(SO4)3] undergo isomerisation.
Catalyst
CH3CH2—CH CH2   CH3—CH CH—CH3 + CH3 C CH2
CH3
1–Butene 2–Butene Isobutylene
Laboratory test of alkene :
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Chemical Reactions of Alkenes
: DIENES :
Dienes are the unsaturated hydrocarbons with carbon-carbon double bonds in their molecules. These are represented
by the general formula C n H 2 n 2 which means that they are isomeric with alkynes (functional isomers). However,,
their properties are quite different from those of alkynes. Depending upon the relative positions of the two double
bond, dienes are classified in three types :
Isolated dienes or non conjugated dienes : In an isolated diene, the two double bonds are separated by more than
one single bond. For example,
CH3
1 2 3 4 5
1 2 3 4 5
CH2 CH CH2 CH CH2 CH2 CH CH CH CH2
Penta–1,4–diene 3–Methylpenta–1, 4–diene
Conjugated dienes : In a conjugated diene, the two double bonds are present in the conjugated or alternate position
and are separated by a single bond.
CH3
1 2 3 4
1 2 3 4 5
CH2 CH CH CH2 CH2 C CH CH CH3
Buta-1,3-diene 2-Methylpenta-1,3-diene
Cumulated dienes : In this case, the two double bonds in the molecules are present at adjacent positions. For
example,
1 2 3 1 2 3 4
CH2 C CH2 CH2 C CH CH3
Propa-1,2–diene Buta–1, 2–diene
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ALKYNES
Introduction :
Unsaturated Hydrocarbon characterised by a presence of C  C
Form homologous series with general formula CnH2n-2 and each homologue of alkyne has 4H atoms less than the corresponding
alkane.
Structure and bonding in Alkynes
(a) Alkynes are hydrocarbons that contain carbon-carbon triple bond.
(b) Alkynes are also called acetylenes because they are derivatives of acetylene
(c) In alkyne C  C bond length is 1.20 Å
(d) Its bond energy is 192 kcal mol–1
(e) The hybridization of carbon atoms having triple bond ( C  C ) in alkynes is sp.
(f) Overlapping of these sp hybrid orbitals with each other and with the hydrogen orbitals gives the sigma
bond framework which is linear (180°) structure.
(g) Two p bonds result form overlap of the two remaining unhybridized p orbitals on each carbon atom. These orbitals
overlap at right angles (90°) to each other, forming one p bond with electron density above and below the C-C sigma
bond, and the other with electron density in front and in back of the sigma bond. This result in a cylindrical p electron
cloud around s bonded structure.
1.20Å 1.06Å
180°
H H H–C–C–H
Note : Any type of stereoisomerism does not arise in acetylenic bond due to linearity of C  C bond.
General Methods of Preparation :
1. By dehydrohalogenation
(a) From Gem dihalides : Dehydrohalogenating agents are : NaNH2 (Sodamide) or Alc. KOH or ROH + RONa.
H X X
alc. KOH NaNH
R C CH 
 HX 
R C CH 
2
 R—C CH + NaX + NH3
H X H
(Stable by resonance)
(Vinyl halide)
(a) Due to stability of vinyl halide by resonance there is partial double bond in which elimination does not take place by alc.
KOH so stronger base NaNH2 is used.
(b) Basic strength :  NH 2 is stronger base then RO
(c) Trans elimination takes place in forming of alkynes.
(b) From Vicinal dihalides :
H H H
alc. KOH NaNH 2
R C C H 
 HX  R C C H 
 HX  R—C CH
X X X
Note : (I) Elimination of Vic. dihalides gives also alkadiene (1, 2 and 1, 3
alkadienes) but the major product is alkyne.
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(II) Non terminal gem dihalide gives 2-Alkyne in presence of alc. KOH while gives 1-alkyne in presence of NaNH 2.
H X H Alc. KOH
CH3 C C CH3 (major)
Example : CH3 C C CH
NaNH2
H X H CH3 CH2 C CH (major)
2. Dehalogenation of tetrahalo alkane : By heating 1, 1, 2, 2 - tetra halo alkane with Zn dust.

X X
2 Zn
R C C H  R—C CH + 2ZnX2
X X
3. From Kolbe's electrolysis : By the electrolysis of aqueous solution of sodium or potassium fumarate or maleate, acetylene is
formed at anode.
CH COOK CH
Electrolysis +CO2


CH COOK CH
Mechanism :
CH COOK CH COO—
lonization
  —
+2K+
CH COOK CH COO
at anode (Alkyl and CO2 gas is formed)
.
CH COO— 2 e – CH COO

.
CH COO
—
CH COO
(Oxygen free radical)
O
CH . C O.
. CH
2CO 2
 
CH. C O. . CH
O
at cathode (KOH and H2 gas is formed)
2K+ + 2e—   2K
2K + 2H2O   2KOH + H2
4. Preparation of higher alkynes by Grignard reagent : By this method lower alkyne is converted in to higher alkyne
    C MgBr Br
RI
CH C — H  CH 3 — Mg —Br 
 + CH4  Mg
 + R —C CH
CH I
Br
C MgBr
R—C CH + CH3Mg—Br 
 + CH4 
R'I
 R' —C C—R + Mg
C R I
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5. Preparation of Ethyne or Acetylene:

(a) From Metal carbide [ Laboratory method] : Acetylene is prepared in the laboratory by the action of water on calcium
carbide.
CaC2 + 2H2O 
 CH CH + Ca(OH)2
Ca+2 +  C C  + 2H+ + 2OH– 

 CH CH + Ca(OH)2
(b) Manufacture : Acetylene is manufactured by heating methane or natural gas at 15000C in an electric arc
2CH4 Electric arc CH CH + 3H2
 
(c) Berthelot's process : Acetylene is synthesized by striking an electric arc between carbon electrodes in presence of
hydrogen.
1200  C
2C + H2   CH CH
(d) From haloform [CHI3, CHCl3] : Pure acetylene is obtained when iodoform or chloroform is heated with Silver powder
CHI3 + 6Ag + I3CH 

 CH CH + 6AgI
(e) Partial oxidation of methane : A recent method for manufacturing of acetylene is the controlled partial oxidation of
methane at high temperature.
1500  C
4CH4 + 3O2   2CH CH + 6H2O
Preparation of alkyne
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Physical Properties :
(a) Alkynes are relatively nonopolar (w.r.t. alkyl halides and alcohols) and nearly insoluble in water (but they are more polar
than alkenes and alkanes). They are quite soluble in most organic solvents, (acetone, ether, emthylene chloride, chloroform
and alcohols).
(b) Acetylene, propyne, and butyne are gases at room temperature, just like the corresponding alkanes and alkenes. In fact,
the boiling points of alkynes are nearly the same as those of alkanes and alkenes with same number of carbon atoms.
CHEMICALREACTIONS OFALKYNES
Due to presence of weak p electrons in alkyne, it will go for electrophilic reaction.
In electrophilic substitution reaction, one s bond is broken and a new s- bond between one of the doubly bonded carbon
atoms and the electrophile is formed. Since the bond energies of the s bond broken and the new s bond formed are not much
different therefore electrophilic substitution reaction are not accompnied by large energy changes.
On the other hand in electrophilic addition reactions one weak p-bond (251 KJ mol–1) is broken and two strong s bonds
(2 × 347 = 694 KJ mol–1) are formed. The overall reaction is accompnied by a release of about 694-251 = 443 KJ mol–1 of energy.
In other words electrophilic addition reactions are energetically more favourable than electrophilic substitution reactions
Thus the typical reactions of alkynes are electrophilic addition reaction and not the electrophilic substitution reactions.
Electrophilic Addition to Alkynes :

Many of the reactions of alkynes are similar to the corresponding reactions of alkenes. Like the pi bond of an alkene, the pi
bonds of an alkyne are electron-rich, and they readily undergo addition reaction. The bond energy of the alkyne triple bond
is about 226 kJ (54 kcal) more than the bond energy of an alkene double bond.
Since sigma bonds are generally stronger than pi bonds, the reaction is usually exothermic. Alkynes have two pi bonds, so
upto two molecules can add across the triple bond.
We must consider the possibility of a double addition whenever a reagent adds across the triple bond of an alkyne. Some
conditions may allow the reaction to stop after a single addition, while other conditions give double addition.
 
E Nu E Nu
General Reaction : – C  C –    
Common Reagents :
(i) + X2 (ii) + HOX
(iii) + HX (iv) + H2O/H+
1. CATALYTIC HYDROGENATION
(i) Reduction to Alkenes
(a) By Lindlar's reagent : Hydrogenation of an alkyne can be stopped at the alkene stage by using a “poisioned” (partially
deactivated) catalyst made by treating a good catalyst with a compound that makes the catalyst less effective. Lindlar’s
catalyst is a poisioned Pd catalyst, composed of powdered barium sulfate coated with Pd, poisoned with quinoline.
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HYDROCARBONS 137
Pd / BaSO 4 , quinoline
General Reaction R – C  C – R’ + H2        (syn addtion)
(b) By Birch reduction
Na  NH
General Reaction R – C  C – R’    
3
 (anti addtion)
H2 , Pd / BaSO
CH3 CH2  C  C  CH2CH3     
4
Ex. quinoline
3  Hexyne
(c) By hydroboration reduction
(i) BH3 - THF R R

General Reaction R – C  C – R C=C (syn addtion)
(ii) CH3COOH H H
2. Hydration of Alkynes :
(i) Mercuric ion catalyzed hydration :
Alkynes undergo acid–catalyzed addition of water across the triple bond in the presence of mercuric ion as a catalyst. A
mixture of mercuric sulfate in aqueous sulfuric acid is commonly used as the reagent.
H
|
General Reaction R  C  C  H  H 2 O R CCH
(Markownikoff's rule) || |
O H
ketone
( stable )
O
||
Ex. CH3  C  C  H  H2O CH3  C  CH3
propyne Pr opanone (acetone )
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(ii) Hydroboration Oxidation of Alkynes :

Alkynes react with BH3 or B2H6 + THF to give trivinyl borane which upon subsequent treatment with alkaline H2O2, gives
alcohols corresponding to anti-markovnikov's addition of H2O to alkynes, which on tautomerisation give corresponding
aldehydes or ketone. Terminal alkynes give aldehyde whereas internal alkynes give ketone.
3. ADDITION OF HYDROGEN HALIDES (+ HX)
Markownikoff’s Rule :
When reagent (asymmetrical HX, H2O) adds to asymmetrical alkene eg, propene isobutene etc. the addition occurs
such that the nucleophile attaches itself to the carbon atom of the alkene bearing the least number of hydrogen, or
electrophile adds to the sp2 carbon that is bonded with the greater number of hydrogen.
Alkyne + 2HX  Geminal Dihalides

Hydrogen halides add across the triple bond of an alkyne in much the same way they add across the alkene double
bond. The initial product is a vinyl halide. When a hydrogen halide adds to a terminal alkyne, the product has the
orientation predicted by Markownikoff’s rule. A second molecule of HX can add, usually with the same orientation
as the first.
Br Br
HBr ( dark ) HBr
– –
–
(a) General Reaction R – C  C – H     R – C = C – H   R – C – CH 3
–
H Br
(MK)
(b) Remarks :
(1) Markownikoff’s Addition in both steps.
(2) If two moles of HX are added the final product is Gemdihalide.
(3) Electrophilic addition to terminal alkyne is regioselective.
Cl
|
HCl HCl
Ex. CH3 CH2  C  C  H   CH 3 CH 2  C  CH 3
|
1  Butyne
Cl
2, 2  Dichlorobutane
H CH2CH2CH3 H Br
| |
HBr C C HBr
Ex. H  C  C  CH2 CH 2 CH3   H  C  C  CH2CH2CH3
H Br | |
H Br
4. ADDITON OF HALOGEN (HALOGENATION)

Alkyne + 2X2  Tetrahalide
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Br Br Br
Br2 (1eq.) Br2 (1eq.)
– –
R – C  C – R 
– –
–
(a)   R – C = C – R      R – C – C – R
–
Br Br Br
(Trans-dihalide) (Tetrahalide)
(b) Nature of Addition:- Anti in both step
X (1 eq.) D
2
R – C  C –R   2
(1)Anti ( 2) Syn.
D / Pd / CaCO 3
R – C  C –R 2     
(1) Syn.
[lindlar , catalyst ]
5. ADDITION OF HOX
Alkynes + HOX  ' - dihaloketone + -haloketone

(90% major)
(10% minor)
X
HOX
–
(a) HOX(1 eq.) R – C = CH  

R – C  C – H  

(1 eq.)
–
OH enol
–H2O
R – C – CH2X R – C – CHX2
O O
10% (minor) 90% (major)
[ -Haloketone] [' -Dihaloketone]
(b) Remarks :
Two molecules of HOX can be added, the end product is Dihaloketone.
The intermediate product is an enol which gives a minor product haloketone.
Extention :
KOH –H2 O
R – C – CHX2  
 R – C – CH(OH)2    R – C – CHO
O O O
(major product)
Polymerisation :
(a) Linear polymerisation :
Dimerisation : When two molecules of acetylene passed through a solution of Cu2Cl2 and NH4Cl a vinyl
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acetylene is obtained.
Cu Cl
2HC C—H 
NH 4 Cl  CH2
2 2
CH—C C—H
mono vinyl acetylene
When vinyl acetylene react with HCl then chloroprene is obtained.
HCl
CH2 CH—C C—H  CH2 Polymerisation
CH C CH2   Neoprene (Synthetic rubber)
Cl
2- chloro-1,3-butadiene
[chloroprene]
Trimerisation : 3 molecules of acetylene.
Cu2 Cl2
3CH CH 
NH 4 Cl  CH2 CH—C C—CH CH2
Divinyl acetylene
(b) Cyclic polymerisation : When alkyne is passed through red hot metallic tube, cyclic polymerisation takes place with the
formation of aromatic compound
Re d hot
3CH CH 
iron tube 

Benzene
CH3
Re d hot
3 CH3—C CH 
iron tube 

H3C CH3
Mesitylene
CH3
CH3 CH3
Re d hot
3 CH3—C C—CH3 
iron tube 
 CH3 CH3
CH3
Hexa methyl benzene
Ni(CO )4
3 HC CH 
(C 6 H 5 )3 P

 benzene (90% yield)
(triphenyl–1–phosphene)
CH CH
HC CH
4CH CH Ni(CN)2
 HC CH
CH CH
1,3,5,7–cyclooctatetraene
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Laboratory Test for Alkynes
Laboratory test of terminal alkynes :

When triple bond comes at the end of a carbon chain. The alkyne is called a terminal alkyne.
acetylenic hydrogen
H - C C - CH2CH3
1-Butyne, a terminal alkyne
(i) Decolourization of Br2 in CCl4 solution.

(ii) Decolourisation of 1% alkaline KMnO4 solution.
(iii) 1- alkynes give white ppt. with ammonical AgNO 3 and red ppt with ammonical cuprous chloride
solution.
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Note : (i) and (ii) tests are used for determination of unsaturation (i.e, presence of double or triple bond in any compound)
(iii) Test is used for distinguish between alkenes and 1-alkynes or 1-alkyne and 2-alkyne.
Chemical Properties of Alkynes
Benzene
Benzene is aromatic hydrocarbon. It undergo electrophilic substitution reactions.
Kekule (1865) proposed following structure the basis of the structure of cyclohexane.
So benzene is found to be resonance hybrid of two Kekule structures.
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AROMATICITY(HUCKELRULE)
We have learnt that aromatic compounds are those which resemble benzene in chemical behaviour. These compounds contain
alternate double and single bonds in a cyclic structure. They undergo substitution reactions rather than addition reactions. This
characteristic behaviour is called aromatic character or aromaticity.
Criteria for Aromaticity
The modern theory of aromaticity was advanced by Eric Huckel in 1931. The aromaticity depends upon the electronic structure of
the molecule. A polynuclear compound, heterocyclic rings or cyclic ions may be aromatic if these have a specific electronic
structure.
The main essentials for aromaticity are :
1. Delocalisation, The molecule should contain a cyclic cloud of delocalized n electrons above and below the plane
of the molecule,
2. Planarity. For the delocalisation of p-electrons the ring must be planar to allow cyclic overlap of -orbitals.
Therefore, for a molecule to be aromatic, the ring must be planar.
3. (4n + 2)  electrons. For aromaticity, the -electron cloud must contain a total of (4n + 2) electrons where n is an
integer equal to 0,1, 2, 3........... This is also known as Huckel rule.
In a nutshell for aromaticity, the molecule must be planar, cyclic system having delocalized (4n + 2) electrons.
This is known as Huckel rule.
Thus, according to Huckel rule, the aromatic compounds have delocalised electron cloud of  electrons of 2 or 6
or 10 or 14 electrons.
Propeties of Benzene and Its Homologoues
Physical Properties
(i) Benzene and its homologues containing upto eight carbon atoms are colourless liquids while the higher one are
solids with characteristics smell.
(ii) Aromatic hydrocarbons are immisible with water but are soluble in organic solvents.
(iii) They are inflammable and burn with sooty flame.
(iv) The melting and boiling points of aromatic hydrocarbons increase with increasing molecular mass. This is due
to increase in magnitude of van der Waal's forces of attraction with increase in molecular size. Amongst isomeric
arenes, (i.e., o-, m- and p- xylenes), the p-isomer has the highest melting point because it is most symmetrical.
(v) They are toxic and carcinogenic in nature.
Chemical Properties
Arenes are expected to be quite reactive due to the presence of double bonds. However, benezne is quite stable
and does not undergo common addition reactions undergone by alkenes.
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Preparation of Benzene
Electrophilic Aromatic Substitution Reactions

Aromatic hydrocarbons are generally known as arenes. An aryl group is one derived from an arene by removal of a hydrogen atom
and its symbol is Ar –. Thus, arenes are designated ArH just as alkanes are designated RH.
The most characteristic reactions of benzenoid arenes are the substitution reactions that occur when they react with electrophilic
reagents. These reactions are of the general type shown below.
ArH + E+ 
 Ar – E + H+ or
E
+ +
+ E + H
The electrophiles are either a positive ion (E+) or some other electron-deficient species with a large partial positive charge. For
example, benzene can be brominated when it reacts with bromine in the presence of FeBr3. Bromine and FeBr3 reacts to produce
positive bromonium ions, Br+. These positive bromonium ions act as electrophiles and attack the benzene ring replacing one of the
hydrogen atoms in a reaction that is called an electrophilic aromatic substitution (EAS).
Electrophilic aromatic substitutions allow the direct introduction of a wide variety of groups into an aromatic ring and because of this
they provide synthetic routes to many important compounds. The five electrophilic aromatic substitutions that we shall study in this
package are outlined in fig. All of these reactions involve the attack on the benzene ring by an electron-deficient species – (by an
electrophile). Later we shall learn what the electrophile is in each instance.
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NO2
HONO2
+ H2 O Nitration
H2SO4
X
X2, FeX3 + H2 O Halogenation
(X = Cl, Br)
SO 3H
Sulfonation
SO3
H2SO4
R
RCl, AlCl3 + HCl Friedel-Crafts Alkylation
(R can rearrange)
O
O C
R-C AlCl 3
R
Cl + HCl Friedel-Crafts Acylation
Electrophilic Aromatic Substitution Reactions
5. Mechanism for Electrophilic Aromatic Substitution
and complexes: It might be expected that the first phase of reaction would be interaction between the approaching electrophile
and delocalised  orbitals leading to  complexes (a weakly bonded charge-transfer complex which exists in solution only and is
formed by the association of an electrophilic species (E+) and on electron-donating species) e.g. toluene form a 1:1 complex with HCl
at –78°C, the reaction being readily reversible. DCl also forms  complex with toluene. This complex on decomposition does not form
deuterium substituted toluene. Formation of complex leads to a solution that is a non-conductor of electricity.
When an electrophile reacts with an arene usually in presence of a catalyst, a salt is formed. This salt is composed of an anion and
a complex, resonance stabilized carbenium ion (arenium ion) in which only two of the total  electrons of arene are utilized to form a
 bond between a particular C atom of the ring and the electrophile, known as  complex (also called Wheland intermediate).
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H D H D H D
H + + H
-
+ DCl + AlCl 3 AlCl 4
+
H
H D
 + AlCl 4
-
 complex
Of course one may assume that an aromatic substitution reaction consists of four stpes involving two  and are a complexes as
shown below.
1. Formation of a -complex
+
E
+
+ E
2. Conversion of  complex to a  complex
+
E

E E
+ +
H H
TS (1)
3. Conversion of a  complex into  complex
+
H
E E
+ +

H H
TS (2)
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4. Decomposition of  complex to products
+
H
+
E E + H
However the most widely accepted mechanism for aromatic electrophilic substitution reaction is
the two step mechanism.
i)  complex formation ii) Loss of proton from the  complex
Of the following two steps, step 1, the formation of the arenium ion, is the rate-determining step in electrophilic aromatic substitution.
Step 2, the loss of a proton, occurs rapidly relative to step 1 and has no effect on the overall rate of reaction.
TS I
TS II
Energy
 complex
Substrate
Product
Progress of the reaction
Energy profile of an aromatic electrophilic substitution without formation of complex. The evidence for the two step mechanism are
i) Detection and isolation of  complex: A large number of  complexes as intermediate has been detected, some of them
have also been isolated.
ii) Displacement of an H (or D) atom of C6H6 (or C6D6) by a nitronium ion NO2+ (formed by the action of concentrated
H2SO 4 on concentrated HNO 3) is an aromatic electrophile substitution reaction. If the C – H bond breaking
is the r/d, step, then the reaction will exhibit a primary kinetic isotope effect. By contrast C6H6 and C6D6 are found to
undergo nitration at essentially the same rate, thus C – H bond breaking cannot be involved in the r/d step, that
means  complex formation is the r/d step.
5.1 Nitration of Benzene
Benzene reacts slowly with hot concentrated nitric acid to yield nitrobenzene. The reaction is much faster if it is carried out by heating
benzene with a mixture of concentrated nitric acid and concentrated sulfuric acid.
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Concentrated sulfuric acid increases the rate of the reaction by increasing the concentration of the electrophile –– the nitronium ion
(NO2+).
In step 1 nitric acid acts as a base and accepts a proton from the stronger acid, sulfuric acid. In step 2 the protonated nitric acid
dissociates and produces a nitronium ion. In step 3, the nitronium ion reacts with benzene by attacking the  cloud and forming an
arenium ion.
In step 4, the arenium ion then transfers a proton to some base in the mixture such as HSO4- and becomes nitrobenzene.
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5.2 Halogenation of Benzene
Benzene does not react with bromine or chlorine unless a Lewis acid is present in the mixture, (as a consequence, benzene does not
decolorize a solution of bromine in carbon tetrachloride). When Lewis acids are present, however, benzene reacts readily with
bromine or chlorine, and the reactions give bromobenzene and chlorobenzene in good yields.
The Lewis acids most commonly used to effect chlorination and bromination reactions are FeCl3, FeBr3, and AlCl3 all in the anhydrous
form. Ferric chloride and ferric bromide are usually generated in the reaction mixture by adding iron to it. The iron then reacts with
halogen to produce the ferric halide :
2Fe + 3X2 
 2FeX3
The mechanism for aromatic bromination is as follows :
The function of the Lewis acid can be seen in step 1. The ferric bromide reacts with bromine to produce a positive bromonium ion, Br +
(and FeBr4-). In step 2 this Br+ ion attacks the benzene ring to produce an arenium ion. Then finally in step 3 the arenium ion transfers
a proton to FeBr4-. This results in the formation of bromobenzene and hydrogen bromide –– the products of the reaction. At the same
time this step regenerates the catalyst FeBr3.
The mechanism of the chlorination of benzene in the presence of ferric chloride is analogous to the one for bromination. Ferric
chloride serves the same purpose in aromatic chlorinations as ferric bromide does in aromatic brominations. It assists in the generation
and transfer of a positive halonium ion. The rate of reaction is often of the form, Rate = K [Ar – H] [X2I2] [Lewis acid]
Hypo-halous acids (HO – X) in presence of strong acid also become a very powerful halogenating agent.
HO X H+ H2O X H2O X
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Fluorine reacts so rapidly with benzene that aromatic fluorination requires special conditions and special types of apparatus. Even
then, it is difficult to limit the reaction to monofluorination. Fluorobenzene can be made, however, by an indirect method.
Iodine, on the other hand, is so unreactive that a special technique has to be used to effect direct iodination; the reaction has to be
carried out in the presence of an oxidizing agent such as nitric acid.
I
HNO 3
+ I2  
Kinetic isotope effects have not been observed for chlorination and rarely for bromination, but iodination shows kinetic isotope
effect.
5.3 Sulfonation of Benzene
Benzene reacts with fuming sulfuric acid at room temperature to produce benzenesulfonic acid. Fuming sulfuric acid is sulfuric acid
that contains added sulfur trioxide (SO3). Sulfonation also takes place in concentrated sulfuric acid alone, but more slowly.
O
O
O S H

+ O S 25 C
  O
conc . H2SO 4
O
Suffer trioxide Benzenesulfonic acid
In either reaction the electrophile appears to be sulfur trioxide. In concentrated sulfuric acid, sulfur trioxide is produced in the
following equilibrium in which H2SO4 acts as both an acid and a base.
Step 1: 2H2SO4 SO3 + H3O+ + HSO4-
When sulfur trioxide reacts with benzene the following steps occur.
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All of the steps are equilibria, including step 1 in which sulfur trioxide is formed from sulfuric acid. This means that the overall
reaction is an equilibrium as well. In concentrated sulfuric acid, the overall equilibrium is the sum of steps 1 - 4.
SO3H
+ H2SO4 + H2 O
In fuming sulfuric acid, step 1 is unimportant because the dissolved sulfur trioxide reacts directly.
Because all of the steps are equilibria, the position of equilibrium can be influenced by the conditions we employ. If we want to
sulfonate benzene we use concentrated sulfuric acid (or better fuming sulfuric acid). Under these conditions the position of equilibrium
lies appreciably to the right and we obtain benzenesulfonic acid in good yield.
On the other hand, we may want to remove a sulfonic acid group from a benzene ring. To do this we employ dilute sulfuric acid and
usually pass steam through the mixture. Under these conditions with a high concentration of water the equilibrium lies appreciably
to the left and desulfonation occurs. The equilibrium is shifted even further to the left with volatile aromatic compounds because the
aromatic compound distills with the steam.
We shall see later that sulfonation and desulfonation reactions are often used in synthetic work. We may, for example, introduce a
sulfonic acid group into a benzene ring to influence the course of some further reaction. Later, we may remove the sulfonic acid group
by desulfonation. Like iodination, sulfonation exhibits a kinetic isotopic effect.
5.4 Friedel - Crafts Alkylation
In 1877 a French chemist, Charles Friedel, and his American collaborator James M. Crafts, discovered new methods for the preparation
of alkylbenzenes (ArR) and acylbenzenes (ArCOR). These reactions are now called the Friedel - Crafts alkylation and acylation
reactions. We shall study the Friedel - Crafts alkylation reaction here and then take up the Friedel - Crafts acylation reaction. A general
equation for a Friedel - Crafts alkylation reaction is the following :
R
AlCl3
+ R X   + HX
The mechanism for the reaction (shown in following steps with isopropyl chloride as R –– X) starts with the formation of a
carbocation (step 1). The carbocation then acts as an electrophile (step 2) and attacks the benzene ring to form an arenium ion. The
arenium ion (step 3) then loses a proton to generate isopropylbenzene.
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When R –– X is a primary halide, a simple carbocation probably does not form. Rather, the aluminum chloride forms a complex with
the alkyl halide and this complex acts as the electrophile. The complex is one in which the carbon - halogen bond is nearly broken –
– and one in which the carbon atom has a considerable positive charge.
 
RCH2 —— Cl : AlCl3
Even though this complex is not a simple carbocation, it acts as if it were and it transfers a positive alkyl groups to the aromatic ring.
These complexes are so carbocation like that they also undergo typical carbocation rearrangements.
Friedel - Crafts alkylations are not restricted to the use of alkyl halides and aluminum chloride. Many other pairs of reagents that form
carbocations (or carbocation like species) may be used as well. These possibilities include the use of a mixture of an alkene and an
acid.
CH(CH3)2
0 C
+ CH3CH = CH2 

C

0 C
+ 
C
A mixture of an alcohol and an acid may also be used

60 C
+ OH  
BF3
There are several important limitations of the Friedel - Crafts reaction.
5.5 Friedel - Crafts Acylation
O
||
The R C  group is called an acyl group, and a reaction whereby an acyl group is introduced into a compound is called an acylation
reaction. Two common acyl groups are the acetyl group and the benzoyl group.
O C
CH3C
Acetyl group Benzoyl group
The Friedel - Crafts acylation reaction is an effective means of introducing an acyl group into an aromatic ring. The reaction is often
carried out by treating the aromatic compound with an acyl halide. Unless the aromatic compound is one that is highly reactive, the
reaction requires the addition of at least one equivalent of a Lewis acid (such as AlCl3) as well. The product of the reaction is an aryl
ketone.
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O
O C
AlCl 3
CH3
+ H3C C  
excess benzene
80  C
Cl
acetyl chloride Acetophenon (methyl
phenyl ketone
Acyl chlorides, also called acid chlorides, are easily prepared by treating carboxylic acids with thionyl chloride (SOCl2) or phosphorus
pentachloride (PCl5).
O O

80 C
H3C C + SOCl2   H3C + SO2 + HCl
OH Thionyl chloride Cl
acetic acid acetyl chloride
O O
+ PCl5 + POCl3 + HCl
OH Cl
Phosphorus
benzoic acid pentachloride benzoyl chloride
Friedel - Crafts acylations can also be carried out using carboxylic acid anhydrides. For example :
O O
H3C C C O
AlCl3 CH3
+ O  + H3C
excess benzene
H3C C OH
Acetophenone
O
acetic anhydride
In most Friedel - Crafts acylations the electrophile appears to be an acylium ion formed from an acyl halide in the following way :
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The remaining steps in the Friedel - Crafts acylation of benzene are the following :
O
H
C
R
+ R C +
+
O
Arenium ion
O O
H
C C
R R
-
+ + AlCl 4 + HCl + AlCl 3
R R
O O -
+ AlCl3 AlCl3
+
In the last step aluminum chloride (a Lewis acid) forms a complex with the ketone (a Lewis base). After the reaction is over,
treating the complex with water liberates the ketone.
H3C R
C O AlCl 3 + 3H 2 O C O + Al(OH)3 + 3HCl
H3C H5C6
Several important synthetic applications of the Friedel - Crafts reaction are later in the package.
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(i) Nature of alkyl groups

If the alkyl group is simple CH3- or CH3CH2-, then a complex between alkyl halide and Lewis acid is the electrophile as shown
in second mechanism. But because of the relative stability of s - and t- carbonium ions, the adducts with s- ant t- alkyl
halides ionise and it is now the carbonium ion that is predominantly the active species. e.g.
 Me3C+ + AlCl 4
Me3C-Cl + AlCl3 
(ii) Nature of Lewis acid as catalyst
The order of effectiveness of Lewis acid catalysts has been shown to be
AlCl3 > FeCl3 > BF3 > TiCl3 > ZnCl2 > SnCl4
The action of Me3CCH2Cl/AlCl3 on benzene is found to yield almost completely the rearranged product, PhCMe2CH2Me,
which can be explained on the basis of the initial electrophilic complex being polarized enough to allow the rearrangement of
[Me 3 CCH 2 ]     Cl      AlCl3 to the more stable [Me 2 CCH 2 Me]     Cl      AlCl3 . By contrast
Me3CCH2Cl/FeCl3 on benzene is found to yield almost completely the unrearranged product, Me3CCH2Ph. This is due to the
fact that the complex with the weaker Lewis acid, FeCl3, is not now polarized enough to allow the rearrangement.
(iii) Temperature
Not only nature of the alkyl group, but also temperature determines the nature of electrophile. e.g. n-alkyl group can be
introduced to a fair extent without rearrangement at low temperatures, because ionisation of the adduct is retarded. But at
higher temperatures, carbonium ion is formed which rearranges and the product is rearranged alkyl benzene. Thus n-
propylchloride gives isopropyl benzene.
In the same way, isobutyl chloride gives t-butyl benzene.
Directive influence :
On EAS of substituted benzene, the attacking position of incoming group depends on nature of existing substitutent.
Two types of behaviour are observed :
Ortho and para directing groups
Meta directing group
Ortho and para directing groups:
Increased electron density at ortho and para positions results in incoming group prefering to attack at ortho and para
positions.
For example:
Phenolic (-OH) group increases the electron density in the benzene ring due to its strong +R effect.
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Hydrocarbons
HYDROCARBONS 156
Other examples of ortho and para directing groups are –NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5, X (X = F, Cl, Br, I) etc.
Halogens are o-, p- directing but these are mild activating groups.
Meta directing groups:
Decrease electron density at ortho and para positions as a result incoming group prefer attack at meta position.
For example:
Nitro (-NO2) group reduces the electron density in the benzene ring due to its strong -R and -I effects.
Other examples of meta directing groups are –NO2, –CN, –CHO, –COR, –COOH, –COOR,
–SO3H, etc.
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Hydrocarbons
HYDROCARBONS 157
8. Reactivity: the effect of electron-releasing and electron-withdrawing groups
We have now seen that certain groups activate the benzene ring towards electrophilic substitution, while other groups deactivate
the ring. When we say that a group activates the ring, what we mean, of course, is that the group increases the relative rate of the
reaction. We mean that an aromatic compound with an activating group reacts faster in electrophilic substitutions than benzene.
When we say that a group deactivates the ring, we mean that an aromatic compound with a deactivating group reacts slower than
benzene.
We have also seen that we can account for relative reaction rates by examining the transition state for the rate-determining steps. We
know that any factor that increases the energy of the transition state relative to that of the reactants decreases the relative rate of the
reaction. It does this because it increases the free energy of activation of the reaction. In the same way, any factor that decreases the
energy of the transition state relative to that of the reactants lowers the free energy of activation and increases the relative rate of the
reaction.
The rate-determining step in electrophilic substitutions of substituted benzenes is the step that results in the formation of arenium
ion. We can write the formula for a substituted benzene in a generalized way if we use the letter S to represent any ring substituent
including hydrogen. (If S is hydrogen the compound is benzene itself). We can also write the structure for the arenium ion in the way
shown here. By this formula we mean that S can be in any position – ortho, meta, or para – relative to the electrophile, E. Using these
conventions, then, we are able to write the rate-determing step for electrophilic aromatic substitution in the following general way.
When we examine this step for a large number of reactions, we find that the relative rates of the reactions depend on whether S
withdraws or release electrons. If S is an an electron - releasing group (relative to hydrogen), the reaction occurs faster than the
corresponding reaction of benzene. If S is an electron withdrawing group, the reaction occurs slower than that of benzene.
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Hydrocarbons
HYDROCARBONS 158
S
S
+ Reaction is
+ E + faster
S releases
electrons H H
Arenium ion
is stabilized
S S
+ Reaction is
+ E + slower
S withdraws
electrons H H
Arenium ion is
destabilized
It appears, then, that the substituent (S) must affect stability of the transition state relative to that of the reactants. Electron -
releasing groups apparently make the transition state more stable, while electron withdrawing groups make it less table. That is
entirely reasonable, because the transition state resembles the arenium ion, and the arenium ion is a delocalized carbocation.
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Hydrocarbons
HYDROCARBONS 159
Chemical Reactions of Benzene
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Hydrocarbons
HYDROCARBONS 160
SOLVED EXAMPLES
Example-1 Example-4
Petrol, diesel and kerosene oil are obtained by Arrange the correct sequence for mechanism of
…A… of petroleum. Here, A refers to chlorination of methane


(a) fractional distillation (I) CH 4  Cl 
hv
 C H 3  H  Cl
(b) sublimation

(c) liquefication (II) Cl  Cl 
hv
2Cl
(d) Steam distillation  
(III) C H 3  C H 3  CH 3 – CH 3
Ans. (a)
Sol. Petrol, diesel and kerosene oil are obtained by fractional  
(IV) C l  C l  Cl – Cl
distillation of petroleum under the earth’s crust.
Choose the correct option
(a) II, I, III and IV (b) I, II, III and IV
Example-2
(c) IV, III, II and I (d) II, III, I and IV
Soda-lime is a mixture of
Ans. (a)
(a) NaOH + Ca(OH)2
Sol. Halogenation (chlorination here) of alkane proceeds
(b) NaOH + Mg(OH)2
(c) NaOH + CaO through free radical mechanism as
(d) NaOH + MgO I. Initiation (Homolysis of chlorine molecule)
Ans. (c) Cl  Cl  Cl  Cl
chlorine free rdicals
Sol. Soda lime = NaOH + CaO
II. Propagation
Example-3 
Isomeric pentanes have different value of boiling point CH 4  Cl 
hv
 C H 3  HCl
 
for example, n-pentane has highest boiling point among
C H 3  Cl  Cl  C H3  HCl
its three isomers. This is due to
(a) No branching 
(b) Weak intermolecular force of attraction CH3Cl  Cl  C H 2Cl  HCl

 
(c) Large area of contact
C H 2Cl  Cl  Cl  CH 2Cl 2  C l
Ans. (c) III. Termination
Sol. With increase in number of branched chains the
Cl  Cl  Cl  Cl
molecule attains the shape of a sphere. This result in
 
smaller area of contact and therefore weak H 3 C C H 3  CH 3  CH 3
intermolecular forces between spherical molecules,  
C H 3  C l  CH 3  Cl
which are overcome at relatively lower temperatures.
Hence, correct sequence/order is represented by (a).
HYDROCARBONS 161
Example-5
20kJ/mol due to weak repulsive interactions between
Higher alkanes on heating to higher temperature
adjacent bonds.
decompose into lower alkanes, alkenes etc. this
process is known as
Example-7
(a) pyrolysis
Eclipsed and the staggered conformations can be
(b) cracking
represented by
(c) Both (a) and (b)
(a) Sawhorse
(d) None of these
(b) Newman projection
Ans. (c)
(c) Both (a) and (b)
Sol. Decomposition of higher alkanes into smaller alkanes
(d) None of these
is known as pyrolysis or cracking.
Ans. (c)
Sol. Eclipsed and the staggered conformations can be
represented by Sawhorse and Newman projection.
Pyrolysis of alkenes is believed to be a free radical

reaction.
Preparation of oil gas or petrol gas from kerosene oil
or petrol involves the principle of pyrolysis. For
example, dodecane, a constituent of kerosene oil on
heating to 973 K in the presence of platinum,
palladium or nickel gives a mixture heptane and
pentene.
Pt / Pd / Ni
C12 H 26 
973 K
 C7 H16  C5 H10  Other products
dodecane heptane pentene
Example-8
Example-6 When 2-methyl propane is oxidized in the presence of
Spatial arrangement of atoms which can be con KMnO4, then product formed is
verted into one another by rotation around a C-C (a) 2-methyl propanol
single bond in alkane is termed as conformers. In the
above context one must remember that the rotation (b) 1-methyl propan-2-ol
around the C-C single bond is (c) 2-methyl propan-2-ol
(a) complete free (d) 2, 2 dimethyl ethanol
(b) hindered by an energy barrier of 1-100 Kcal Ans. (c)
(c) hindered by an energy barrier of 1-20 KJ/mol
(d) hindered by an energy barrier of 1-20 Kcal Sol.
 CH 3 3 CH KMnO
 4
Oxidation
  CH 3 3 COH
(2-methypropane) (2-methylpropan-2-ol)
Ans. (c)
Sol. The rotation is hindered by a weak energy barrier of 1-
HYDROCARBONS 162
Example-9
Carbon-carbon double bond in alkene consists of
(a) two sigma bonds
(b) one sigma bond and one pi bond
(c) two pi bonds
(d) None of these
Ans. (b)
Sol. Ethene is a class of alkene consists of one sigma bond
and one pi bond. Example-11
Geometrical isomerism is represented as
(a) YXC – C = XY
(b) Y = XC = CXT
(c) YXC = CXY
Sigma bond is formed by head on overlapping and pi (d) Y = XC = C = XY
bond is formed by sideways overlapping of orbitals. Ans. (c)
Sol.
Example-10
Which of the following has higher dipole moment; cis-
2-butene and trans-2-butene?
(a) cis-2-butene
(b) trans-2-butene
(c) Both have same dipole moment
Ans. (a)
Sol. Cis from of alkene is found to be more polar than the Example-12
trans form. For example, dipole moment of cis-but-2- Ozonolysis of alkenes involves the …A… of ozone
ene is 0.33 Debye, whereas dipole moment of the trans molecule to alkene to form ozonide. Here, A refers to
form is almost zero or it can be said that trans-but-2- (a) breakdown
ene is non-polar. This can be understood by drawing 3 (b) addition
geometries of the two forms as given below from which (c) elimination
it is clear that in the trans-but-2-ene, the two methyl (d) substitution
groups are in opposite directions. Therefore, dipole Ans. (b)
moments of C-CH2 bonds cancel, thus making the trans Sol.
form non-polar.
Zn  H O
CH 3CHO  HCHO 
2
 (propene ozonide)
ethanal methanal
HYDROCARBONS 163
Example-13
Ozonolysis of an organic compound A produces acetone
and propionaldehyde in equimolar mixture. Here, A
refers to.
(a) 2-methyl-1-pentene
(b) 1-penene
(c) 2-pentene
(d) methyl-2-pentene
Ans. (d)
Example-15
Sol.
When propyne reacts with one mole of HBr then product
obtained is
(a) bromoethene
(b) dibromopropane
(c) 2-bromopropene
(d) 1-bromopropene
Formation of acetone confirms that double bond is Ans. (c)
present at second carbon (C-2) atom and formation of Sol.
propionaldehyde confirms that three carbon atoms are Br
|
attached with (C-2) with double bond. Hence, CH 3  C  CH  HBr  CH 2  C H  CH 3
CH 3
|
A  CH 3  C  CH  CH 2  CH 3 Example-16
2-methyl, 2-pentene
The bond angles of alkenes and alkynes with two
Example-14 carbon atoms are
Assertion (A) 1-butene on reaction with HBr in the (a) 120º and 120º respectively
presence of a peroxide, produces 1-bromobutane. (b) 120º and 120º respectively
Reason (R) it involves the formation of a primary (c) 109º and 180º respectively
radical. (d) 109º and 120º respectively
(a) Both A and R are correct; R is the correct explanation Ans. (b)
of A Sol.
(b) Both A and R are correct; R is not the correct
explanation of A
(c) A is correct; R is incorrect
(d) R is correct; A is incorrect
Ans. (a)
Sol.
HYDROCARBONS 164
Example-17 (c) II > III > I (d) III > I > II
By treating calcium carbide with water …A… prepared. Ans. (c)
Sol. As branching increases boiling point decreases, so
Here, A refers to order of boiling point is III > II > I.
(a) ethene
Example-20
(b) ethyne
In the following reaction, the major product is
(c) methyne
(d) None of these
Ans. (b)
CaC2  2 H 2O  Ca  OH  2  C2 H 2 (a)
Sol.  ethyne 
Example-18
Which of the following order is correct regarding acidic
character of hydrocarbons given below?
(I) CH  CH  CH 2  CH 2  CH3  CH3
(II) (b)
HC  CH  CH 3C  CH 2  CH3 C  CCH3
(a) Only I
(b) Only II
(c) Both I and II
(d) None of these
Ans. (c)
(c)
Sol. Both are correct. In (I) 1s character defines correct
trend of acidic strength as Acidicstrength
 %s character In (II) Inductive effect defines acidic
strength and polarity of C-H bond of alkyne. Group
having +I effect increases electron density around C-
H bond hence decrease polarity and acidic strength of (d)
alkyne.
Example-19
Isomers of hexane, based on their branching, can be
divided into three distinct classes as shown in the
figure.
Ans. (d)
Sol.
HYDROCARBONS 165
Example-21 Ans. (c), (d)
Which of the following alkanes will give more than one
Sol. R  COOK H2O
electrolysis
R  R
monochloro product?
R  X 
Na
ether
R  R
(a) Example-23
Structures of σ-complex formed during nitration
of Anisole would be
(b)
(a) (b)
(c)
(d)
(c) (d)
Ans. (a), (b), (d)

Sol. Only in neopentane all H’s are equivalent. Therefore, it
will give only one monochloro derivative. Other alkane Ans. (a), (c)
will give more than one monochloro derivatives. Sol. As MeO – group is ortho-para director the problable
σ-complexes in electrophilic substitution of anisole
are
Example-22
In which of the following cases product will contain
more number of carbon atoms than do present in
reactant molecule?
(a)
(b) RCOOK  OH  

heat
CaO
B
(c) RCOOK  H 2 O 

Electrolysis
C
(d) RX  Na 
dryether
D
HYDROCARBONS 166
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

5. (A) + Cl2 monochloro product
To maximise the yield of monochloro product in the

1. 
Conc.H 2 SO4
 Major product :
 above reaction ?
(a) Cl2 must be added in excess

(a) (b)
(b) Reactant (A) must be added in excess
(c) (d) None of these (c) Reaction must be carried out in dark
(d) Reaction must be carried out with equimolar mixture
2. Alkyl halides react with dialkyl copper reagents to give of Cl2 and A
(a) alkenyl halides (b) alkanes
6. Select the chain propagation steps in the free-radical
(c) alkyl copper halides (d) alkenes chlorination of methane.
3. Which of the following compounds can be best prepared (1)

by Wurtz-reaction ?
(2)
(a) Iso-butane (b) n-butane
(c) n-pentane (d) Iso-pentane (3)
4. Select the structure of the major product formed in the (4)

reaction
(5)
(a) 2, 3, 5 (b) 1, 3, 6
(c) 3, 5 (d) 2, 3, 4
7.
(a) (b)
Br  will abstract which of the hydrogen most readily..

(a) a (b) b
(c) c (d) d
(c) (d)
8. On mixing a certain alkane with chlorine and irradiating it
with ultraviolet light, it forms only one
monochloroalkane. This alkane could be
(a) propane (b) pentane
(c) isopentane (d) neopentane
HYDROCARBONS 167
9. On mixing a certain alkane with chlorine and irradiating it

with ultraviolet light, it forms only one 16. Trans-2-phenyl-1-bromocyclopentane on reaction with
monochloroalkane. This alkane could be
alcoholic KOH produces
(a) neopentane (b) propane
(a) 4-phenylcyclopentene
(c) pentane (d) isopentane
10. Of the five isomeric hexanes, the isomer which can give (b) 2-phenylcyclopentene
two monochlorinated compounds, is
(c) 1-phenylcyclopentene
(a) 2-methylpentane
(b) 2,2-dimethylbutane (d) 3-phenylcyclopentene
(c) 2,3-dimethylbutane 17. Which compound would be the major product when
(d) n-hexane (CH3)2CHCHBrCH2Br is treated with alcoholic KOH ?
11. 2-methyl butane on reacting with bromine in the (a) (CH3)2CHCH2CHOHCH3
presence of sunlight gives mainly
(a) 1-bromo-3-methylbutane (b)
(b) 2-bromo-3-methylbutane
(c) 2-bromo-2methylbutane (c) (CH3)2COCH2CH2CH3
(d) 1-bromo-2methylbutane
(d) (CH3)2C CHCH2OH
12. The major product obtained in the photo catalysed
bromination of 2-methylbutane is: 18. Elimination of bromine from 2-bromobutane results in
the formation of
(a) 1-bromo-2-methylbutane
(a) predominantly 2-butyne
(b) 1-bromo-3-methylbutane
(c) 2-bromo-2-methylbutane (b) predominantly 1-butene
(d) 2-bromo-3-methylbutane (c) predominantly 2-butene
13. (d) equimolar mixture of 1 and 2-butene
19. The treatment of CH3MgX with CH3C  C – H produces
Above reaction is an example of : (a) CH3 – CH = CH2

(a) isomerization (b) polymerization (b) CH3C  C – CH3
(c) cracking (d) de-hydrogenation
14. Which of the following is the major product when 1-
butanol is heated with concentrated H2SO4 ? (c)
(a) 1-butene (b) Cis-2-butene
(d) CH4
(c) Trans-2-butene (d) All of the above
15. The gas liberated by the electrolysis of Dipotassium 20. 2-hexyne gives trans-2-hexene on treatment with
succinate solution is:
(a) Pt/H2 (b) Li/NH3
(a) Ethane (b) Ethyne
(c) Pd/BaSO4 (d) LiAlH4
(c) Propene (d) Ethene
HYDROCARBONS 168
21. Consider the addition of HBr to 3,3-Dimethyl-1-butene

shown below. What is the best mechanistic explanation
for the formation of the observed product ?
(c) (d)
24. Choose the correct major product for the reaction below
(a) Protonation of the alkene followed by a hydride shift

and addition of bromide to the carbocation
(b) Double bond shift in the alkene following by the
protonation and addition of bromide to the carbocation
(c) Addition of bromide to the alkene followed by a
double bond shift and protonation (a)
(d) Protonation of the alkene followed by a methyl shift
and addition of bromide to the carbocation
22. (b)
(c)
Arrange the above in the decreasing order of reactivity

towards HBr : (d)
(a) a > b > c (b) b > a > c

25. Reaction of on molecule of HBr with one molecule of
(c) b > c > a (d) a > c > b 1,3-butadiene at 40ºC gives predominantly
(a) 1-bromo-2-butene under kinetically controlled
conditions
23. (b) 3-bromobutene under thermoynamically controlled
conditions
(c) 1-bromo-2-butene under thermodynamically under
kinetically controlled conitions
(d) 3-bromobutene under kinetically controlled conditions
26. On catalytic reduction with H2/Pt how many alkenes will

(a) (b) give n-butane ?
(a) 1 (b) 2
(c) 3 (d) 4
HYDROCARBONS 169
27. HBr reacts with CH2 = CH – OCH3 under anhydrous 32. Give the major product of the following reaction
3,3-dimethyl-1-butene + HCl Major
conditions at room temperature to give
(a) 2-chloro-3,3-dimethyl butane
(a) CH3CHO and CH3Br
(b) 2-chloro-2,3-dimethyl butane
(b) BrCH2CHO and CH3OH (c) 1,2-dichloro-3,3-dimethylbutane
(d) 1-chloro-3,3-dimethylbutane
(c) BrCH2 – CH2 – OCH3
(d) H3C – CHBr – OCH3

33. Major product :
28. Alkene + H2O Alcohol
Which of the following statements about this reaction is

correct ?
(a) It is Markovnikov addition of water to alkene. (a)
(b) It involves carbonium ion rearrangement, if possible.
(c) both of these
(d) none of these
29. HCl

peroxide
(A) 
EtONa

(Z)(major) (b)
Identify (Z) in the above sequence of reactions :
(a) (b)
(c)
(c) (d)
30.
(d)
Comment on optical activity of the products : 34. In case of addition of HX to an alkene, Markovnikov
originally stated that
(a) Racemic (b) Diastereomer
(a) the H atom adds to the carbon atom of the double
(c) Meso (d) Optically pure enantiomer bond that already has greater number of H atoms and
halide ion adds to the carbon atom of the double bond
31. H3C  CH = CH2 + HCl 
Peroxide
 Product, that has fewer number of H atoms.
the intermediate of reaction is : (b) the H atom adds to the carbon atom of the double
bond that has fewer number of H atoms and halide ion
(a) (b) adds to the carbon atom of the double bond that has
greater number of H atom.
(c) (d)
(c) both of these depending upon situation
(d) none of these
HYDROCARBONS 170
35. (d)
37. Identify the product of the reaction when molecule

undergoes ozonolysis
(a) (b)
(c) (d) none of these (I) (II)
(III) (IV)
(V)
36.
(a) I is only product (b) I and III

(c) I and IV (d) II and IV
38. Which compound will yield 5-keto-2-methyl hexanal upon
treatment with O3 ?
Compound (A) is :
(a) (a) (b)
(b)
(c) (d)
(c)
HYDROCARBONS 171
39. Compound (X)

(d)
42. Which of the following compound does not evolve CO2

gas, when undergo oxidative ozonolysis ?
Find the structure of (X).
(a)
(a) (b)
(c) (d)
(b)
40. Ozonolysis of the following compound will produce;
(c)
is :
(d)
43. In the following sequence of reactions, the alkene affords

the compound ‘B’
O H O
(a) CH 3CH  CHCH3 
3
A 
Zn  B.
2
The compound B is
(b) (a) CH3CH2CHO (b) CH3COCH3
(c) CH3CH2COCH3 (d) CH3CHO
(c) 44. One mole of a symmetrical alkene on ozonolysis gives two

moles of an aldehyde having a molecular mass of 44 u. The
alkene is
(d) (a) propene (b) 1-butene

(c) 2-butene (d) ethene
41. An organic compound C4H6 on ozonolysis give HCHO,
CO2, CH3CHO. Compound will be : 45. Ozonolysis of an organic compound given formaldehyde
as one of the products. This confirms the presence of
(a) (a) two ethylenic double bonds
(b) (b) a vinyl group
(c) (c) an iso-propyl group

(d) an acetylenic triple bond
HYDROCARBONS 172
46. Identify the major product 49. Rank the following compounds with respect to increasing
acidity
(1) 1-butene (2) butane
(3) 1-butyne (4) NH3
(a) 4 < 3 < 1 < 2 (b) 2 < 1 < 4 < 3
(c) 2 < 1 < 3 < 4 (d) 3 < 1 < 2 < 4

(a) (b)
50. Which of the following reacts with Tollen’s reagent giving
white precipitate ?
(a) 2-pentene (b) 2-pentyne
(c) 1-butyne (d) 1-butanol
(c) (d)
51. Which of the following reagents can distinguish propyne
from propene ?
(a) Br2, CCl4 (b) Dilute KMnO4
(c) Conc. H2SO4 (d) AgNO3 in NH4OH
52. Which is the most suitable reagent among the following to

distinguish compound (3) from the others ?
47.
(1) (2)
(3) (4)
P should be (a) Bromine in carbon tetrachloride

(b) Bromine in acetic acid solution
(a) (c) Alk. KMnO4
(d) Ammonical silver nitrate
(b) 53. Which of the following reacts with Tollen’s reagent giving
white precipitate ?
(a) 2-pentene (b) 2-pentyne
(c) 1-butyne (d) 1-butanol
(c)
54. The hydrocarbon which can react with sodium in liquid
ammonia is
(a) CH3CH2CH2C  CCH2CH2CH3

(d)
(b) CH3CH2C  CH
48. The major organic compound formed by the reaction of (c) CH3CH = CHCH3
1,1,1-trichloroethane with silver powder is
(d) CH3CH2C  CCH2CH3
(a) acetylene (b) ethene
(c) 2-butyne (d) 2-butene
HYDROCARBONS 173
55. Predict the product of the reaction 1-butyne with 2 60. Acetylene reacts with hypochlorous acid to form
equivalents of HCl
(a) Cl2CHCHO (b) ClCH2COOH
(c) CH3COCl (d) ClCH2CHO

(a) (b)
61. Acetylene does not react with
(a) Na (b) ammoniacal AgNO3
(c) HCl (d) NaOH

(c) (d)
56. Which alkyne gives 3-ethylhexane on catalytic 62.

hydrogenation ?
(a) (b) Product (C) is
(a) (b)
(c) (d) All of these
(c) (d)
57. On catalytic reduction (H2/Pt) how many alkenes will give
2-methylbutane ? 63. The reagent needed for converting is:
(a) 1 (b) 2
(c) 3 (d) 4
(a) LiAlH4
58. reagent used for the
(b) Cat. Hydrogenation
(c) H2/Lindlar Cat.

reaction :
(d) Li/NH3
(a) LiAlH4 (b) H2/Ni
64. Choose the reagent to carry out the reaction.
(c) NaBH4 (d) H2, Pd — BaSO4
59. Butene-1 may be converted to butane by reaction with
(a) Zn-HCl (b) Sn-HCl

(a) H2 + Lindlar catalyst (b) Li + NH3
(c) Zn-Hg (d) Pd/H2
(c) Conc. H2SO4 (d) H2O + H+
HYDROCARBONS 174
65. How many benzylic hydrogens are present in the 72. Arrange these groups in decreasing order of their electron -
hydrocarbon shown ? donating power in resonance
–OH , –O–CO–CH3 , –NH2 NO2
(I) (II) (III) (IV)

(a) III > I > II > IV (b) II > I > III > IV
(c) III > II > I > IV (d) I > III > II > IV
73. Gammexane can be obtained from benzene with reagent
(a) 3 (b) 5
(a) Br2, sunlight (b) Cl2, sunlight
(c) 4 (d) 6
(c) Cl2, CCl4 (d) COCl2, anhydrous AlCl3
66. The ‘middle oil’ fraction of coal–tar distillation contains
74. The product of following reaction is C6H6 + Cl2
(a) benzene (b) naphthalene
(c) anthracene (d) xylene (a) C6H5Cl (b) ortho C6H4Cl2
67. Catalytic dehydrogenation of n–heptane in the presence of (c) C6H6Cl6 (d) para C6H4Cl2
Cr2O3/Al2O3 at 750 K gives 75. Which of the following will be obtained by the bromination
of ethylbenzene in presence of light ?
(a) iso–heptane (b) 1–heptane
(c) toluene (d) 2,3–dimethyl pentene–1
68. (a) (b)
Product (B) of the reaction is :

(a) Toluene (b) Ethyl-benzene
(c) Benzene (d) Butyne
69. On heating a mixture of sodium benzoate and sodalime, the (c) (d)
following is obtained
(a) toluene (b) phenol
76. Arrange the following in decreasing order of reactivity
(c) benzene (d) benzoic acid
towards EAS (electrophilic aromatic substitution)
70. When sodium benzoate is heated with soda lime, the product
formed is :
(a) phenol (b) chlorobenzene
(c) benzene (d) benzaldehyde
71. In desulfonation of benzene sulfonic acid, on treatment with

steam, electrophile is
(a) a > b > c (b) c > b > a
(a) H (b) SO3
(c) a > c > b (d) c > a > b
(c) H2O (d) none of these
HYDROCARBONS 175
77. Consider the following statements

I : Hyperconjugation helps in increasing electron-density 82.
at ortho and para-sites in case of alkyl groups.
(B), Product (B) in this reaction is
II : Electron-donating groups are activators and ortho and
para-directors because they stabilise the arenium
cations.
(a)
III : Electron-withdrawing groups are activators and are
meta-directors because they stabilise the arenium
cations.
IV : Halogens are activators and ortho and para-directors.
(b)
Select correct statements
(a) I, II (b) I, II, III
(c) II, III, IV (d) I, IV
(c)
78. In electrophilic aromatic substitution reaction, a phenyl
substituent on the aromatic ring is
(a) a deactivator and m–director
(d)
(b) a deactivator and o, p–director
(c) an activator and m–director
(d) an activator and o, p–director HF
83. 
  Suitable
79. In electrophilic aromatic substitution reactions, a –N=O
substituent on the aromatic ring is
(a) a deactivator and m–director product of this reaction is
(b) a deactivator and o, p–director

(c) an activator and m–director
(d) an activator and o, p–director (a) (b)
80. Which of the following is not the activating group ?
(a)
(b)
(c) (d)
(c)
(d) – F
81. Which of the following compounds will not undergo Friedel–

Craft acylation when treated with CH3CH2COCl, AlCl3 ?
(a) Toluene (b) p–Xylene
(c) Chlorobenzene (d) Benzophenone

HYDROCARBONS 176
84.
Compound X, is :
(a) (b)
(a)
(b)
(c) (d) none of these
(c)
(d) all are correct 87. Which of the following compounds will undergo bromination
most rapidly using Br2, FeBr3 ?
85. In the given reaction, what is the product ?
(a) p–methylacetanilide
(b) bromobenzene
(c) acetanilide
(d) benzenesulphonic acid
Product + HCl
88. The major product obtained on the monobromination (with
Br2/FeBr3) of the following compound A is
OCH3
(a) (b)
CH3
(A)
OCH3
OCH3
Br
(c) (d)
(a) (b)
CH3
CH3
Br
OCH3 OCH3
86. Br
(c) (d)
Br CH3 CH3
The compound X is :
HYDROCARBONS 177
89. Consider the following compound
92. Presence of a nitro group in a benzene ring
(a) activates the ring towards electrophilic substitution
(b) renders the ring basic
(c) deactivates the ring towards nucleophilic substitution
The relative reactivity towards halonium ion is such that :

(d) deactivates the ring towards electrophilic substitution
(a) I > II > III (b) II > I > III
93. Which of the following cannot be oxidised to benzoic acid
(c) II > III > I (d) III > I > II
on treatment with KMnO4, ?
90. Which of the following is the major product from
bromination of meta-nitrobenzene sulphonic acid ?
(a)
(b)
(a) (b)
(c)
(c) (d)
(d)
91. The reaction of toluene with Cl2 in presence of FeCl3 gives

94. Which of the following compounds will not undergo Friedel–
predominantly Craft acylation when treated with CH3CH2COCl, AlCl3 ?
(a) Toluene
(a) benzoyl chloride
(b) p–Xylene
(b) benzyl chloride
(c) Chlorobenzene
(c) o - and p - chlorotoluene (d) Benzophenone
(d) m-chlorotoluene
HYDROCARBONS 178
95. Which of the following is the major product from the

sulphonation of -tetralone ?
(a)
(b)
(c)
(d)
HYDROCARBONS 179
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS
1. Which one of the following reaction is a method for the (a) (b) < (a) < (c) < (d)
conversion of ketone into a hydrocarbon? (2015)
(b) (a) < (b) < (c) < (d)
(a) Aldol condensation
(c) (b) < (a) < (d) < (c)
(b) Riemer-Tiemann reaction
(d) (a) < (b) < (d) < (c)
(c) Cannizzaro reaction
6. When 2-butyne is treated with H2/ Lindlar’s catalyst,
(d) Wolf-Kishner reduction compound X is produced as the major product and when
treated with Na/liq. NH3 it produces Y as the major
2. The hottest region of Bunsen flame shown in the figure product. Which of the following statements is correct ?
given below is (2016)
(2018)
(a) X will have higher dipole moment and higher boiling
point than Y.
(b) Y will have higher dipole moment and higher boiling
point than X.
(c) X will have lower dipole moment and lower boiling
point than Y.
(a) region 2 (b) region 3 (d) Y will have higher dipole moment and lower boiling
(c) region 4 (d) region 1 point than X.
3. The hydrocarbon with seven carbon atoms containing 7. 25g of an unknown hydrocarbon upon burning
a neopentyl and a vinyl group is: (2016) produces 88g of CO2 and 9g of H2O. This unknown
hydrocarbon contains: (2019)
(a) 2, 2-dimethyl-4-pentene
(a) 20g of carbon and 5g of hydrogen
(b) Isopropyl-2-butene
(b) 22g of carbon and 3g of hydrogen
(c) 4, 4-dimethylpentene
(c) 24g of carbon and 1g of hydrogen
(d) 2, 2-dimethyl-3-pentene
(d) 8g of carbon and 7g of hydrogen
4. The trans-alkenes are formed by the reduction of alkynes 8. At 300 K and 1 atmospheric pressure, 10 mL of a hydro-
with: (2018) carbon required 55 mL of O2 for complete combustion,
(a) Sn - HCl (b) H2 – Pd/C, BaSO4 and 40 mL of CO2 is formed. The formula of the hydrocar-
bon is: (2019)
(c) NaBH4 (d) Na/liq.NH3
(a) C4H10 (b) C4H6
5. The increasing order of nitration of the following
compounds is : (2018) (c) C4H7Cl (d) C4H8
9. Which of these factors does not govern the stability
of a conformation in acyclic compounds? (2019)
(a) Steric interactions
(b) Torsional strain
(c) Electrostatic forces of interaction
(d) Angle strain
HYDROCARBONS 180
(a)
10. The major product of the following addition reaction
is H3 C  CH  CH 2 
Cl 2 / H 2 O
 (2019)
H 3C  CH  CH 2
| |
(a)
Cl OH
(b)
H3C  CH  CH 2
| |
(b)
OH Cl
(c)
(c)
(d)
11. But 2-ene on reaction with alkaline KMnO4 at elevated

temperature followed by acidification will give:
(2019)
CH3  CH  CH  CH3 (d)

| |
(a) OH OH
(b) one molecule of CH3CHO and one molecule of

CH3COOH
(c) 2 molecules of CH3COOH
(d) 2 molecules of CH3CHO 14. Consider the following reaction:
12. Which one of the following alkenes when treated with
HCl yields majorly an anti Markovnikov product ?
(2019)
(a) CH3O–CH=CH2 (b) Cl–CH=CH2
(c) H2N–CH=CH2 (d) F3C–CH=CH2
13. The major product of the following reactions is:
(2019)
‘A’ is : (2019)
(a) CH  CH (b) CH3 – C  C – CH3
(c) CH3 – C  CH (d) CH2 = CH2
HYDROCARBONS 181
15. The increasing order of the reactivity of the following 19. Which compound (s) out of the following is/are not
compounds towards electrophilic aromatic substitution aromatic? (2019)
reactions is: (2019)
(a) (B), (C) and (D)

(b) (C) and (D)
(c) (B)
(a) II < I < III (b) III < II < I (d) (A) and (C)
(c) III < I < II (d) I < III < II 20. Which of the following compounds is not aromatic ?
16. The increasing order of reactivity of the following (2019)
compounds towards aromatic electrophilic substitution
reaction is: (2019)
(a) (b)
(c) (d)
(a) D < A < C < B (b) B < C < A < D 21. The major product of the following reaction is:
(c) A < B < C < D (d) D < B < A < C

17. The major product of the following reaction is:
CH 3C  CH 
(i) DCl (1 equiv.)
 (2019) (2020)
(ii) DI
(a) CH3CD(I)CHD(Cl) (b) CH3CD(Cl)CHD(I)

(c) CH3CD2CH(Cl)(I) (d) CH3C(I)(Cl) CHD2
18. The correct order for acid strength of compounds
CH  CH, CH3 – C  CH and CH2 = CH2 is as follows :
(2019) (a) (b)
(a) CH  CH > CH2 = CH2 > CH3 – C  CH

(b) CH3 – C  CH > CH  CH > CH2 = CH2
(c) CH3 – C  CH > CH2  CH2 > HC  CH
(d) HC  CH > CH3 – C  CH > CH2 = CH2
(c) (d)
HYDROCARBONS 182
22. Which of the following compounds shows geometrical
isomerism? (2020)
(a) 2-methylpent-2-ene
(b)
(b) 4-methylpent-2-ene
(c) 4-methylpent-1-ene
(d) 2-methylpent-1-ene
23. The increasing order of the boiling point of the
major products A, B and C of the following reactions will
be: (2020)
(c)
(A)
(B) (d)
(C) 26. Which of the following compounds produces an

optically inactive compound on hydrogenation?
(a) B < C < A (b) C < A < B (2020)
(c) A < B < C (d) A < C < B
24. The major product formed in the following reaction is:
(a)
CH 3 CH  CHCH(CH 3 ) 2 
HBr
 (2020)
(a) CH3CH(Br)CH2CH(CH3)2
(b) CH3CH2CH(Br)CH(CH3)2
(c)(CH3)2 CHBr (b)
(d) CH3CH2CH2C(Br) (CH3)2
25. Among the following compounds, geometrical isomerism
is exhibited by: (2020)
(c)
(a)
(d)
HYDROCARBONS 183
27. The major product in the following reaction is :
29. Which of the following has the shortest C–Cl bond?
(2020) (2020)
(a) Cl–CH=CH2 (b) Cl–CH=CH–NO2
(c) Cl–CH=CH–CH3 (d) Cl–CH=CH–OCH3
30. Which of the following reactions will not produce a
racemic product? (2020)
(a)
(a)
(b)
(b)
(c) CH3CH 2CH  CH 2 

HBr
CH3
(c) |
CH 3  C  CH  CH 2 
HCl
(d)
|
H
31. The major products A and B in the following reactions
are:
(2020)
(d)
28. The correct order of heat of combustion for following

alkadienes is: (2020)
(a)
(A)
(b)
(B)
(C) (c)
(a) (A) < (B) < (C)

(b) (A) < (C) < (B)
(d)
(c) (C) < (B) < (A)
(d) (B) < (C) < (A)
HYDROCARBONS 184
32. The major product [B] in the following sequence 34. The major product (Y) in the following reactions is:
of reactions is: (2020) (2020)
(a)
(a)
(b)
(b)
(c)
(c)
(d)
(d)
33. The major product obtained from the following 35. The number of sp2 hybrid orbitals in a molecule of
reaction is: (2020) benzene is : (2020)
(a) 24 (b) 6
(c) 18 (d) 12
36. Consider the following reactions:
(A)
(B)
(a)
(b)
(C)
(c)
(D)
(d)
HYDROCARBONS 185
Which of these reactions are possible ? (2020)
(a) (A) and (B)
(b) (A) and (D)
(c) (B), (C) and (D)
(d) (B) and (D)
37. In the following sequence of reactions the maximum
number of atoms present in molecule ‘C’ in one plane
is _______ .
A 
Red hot
Cu tube
B 
CH3 Cl(1.eq.)
Anhydrous AlCl3
C
(A is a lowest molecular weight alkyne) (2020)

HYDROCARBONS 186
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS
1. All questions marked “S” are single choice questions

2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions
decreases in the order :

1.(S) The compound which has one isopropyl group, is
(a) P > Q > R > S
(a) 2, 2, 3, 3-tetramethyl pentane
(b) S > R > Q > P
(b) 2, 2-dimethyl pentane
(c) 2, 2, 3- trimethyl pentane (c) S > P > Q > R
(d) 2-methyl pentane (d) Q > P > S > R

2. (S) Which of the statements is correct ? 4. (S) Arrange the following alkene in increasing order of
their enthalpy of hydrogenation (–H)
(I) Melting point of alkane increases with increase of C
atoms and with increase in branching.
(II) Boiling point of alkane increases with increase of C
atoms but with decrease in branching.
(III) Cycloalkanes have lower boiling point than normal
alkane with same number of C atoms.
(IV) Alkenes have lower boiling point than same number
of C atoms in alkanes.
(a) (I), (II) (b) (I), (II), (III) (a) III < IV < II < I (b) III < IV < I < II
(c) (III), (IV) (d) (IV) (c) I < II < III < IV (d) I < II < IV < III
3. (S) The bond dissociation energy of the C—H bond for 5. (S) Which of the following is incorrect regarding
the compound combustion of alkanes ?
(a) It is always an exothermic process
(b) It proceeds through a free radical mechanism
(c) It can be controlled to an intermediate stage
(d) 2-methyl butane will liberate less heat than
n-pentane.
HYDROCARBONS 187
6. (S) Choose the major product of reaction
11. (S)
Major product :
(a)
(b)
(a) I (b) II
(c) Both (a) and (b) in same amount
(c) III (d) IV
7. (S) Which of the following would not form upon
12. (S) Arrange the following alkene in increasing order of
electrolysis of aqueous solution of potassium their enthalpy of hydrogenation (–H)
propanoate ?
(a) Butane (b) Ethyl ethanoate
(c) Ethyl propanoate (d) Ethene
8. (S) What will be formed in the following Kolbe’s

electrolysis ?
(a) III < IV < II < I

(a) 2-butene (b) 1-butyne
(b) III < IV < I < II
(c) 2-butyne (d) Both b and c
(c) I < II < III < IV
9. (S) What is the relationship between the two terminal
H 2 C = groups in a cumulene containing three (d) I < II < IV < III
consecutive double bonds (H2C=C=C=CH2) ?
13. (S) Which of the following alkenes is most reactive
(a) They are in the perpendicular plane towards electrophilic addition reaction ?
(b) They are in the same plane (a) H2C = CH2
(c) They are in two planes at 120º (b) CH3 – CH = CH2
(d) They are in two planes at 109º
10. (S) The boiling point of trans-dichloroethene is 48 (c)
degress Celsius. Which number best approximates
the boiling point of cis-dichloroethene ?
(d) H2C = CH – Cl
(a) 36 degrees Celsius (b) 42 degrees Celsius
(c) 48 degrees Celsius (d) 54 degrees Celsius
HYDROCARBONS 188
14. (S) Which molecule will give following dicarboxylic acid 17. (S) Which of the following cannot be used to prepare
upon treatment with acidic solution of KMnO4 ? cumene from benzene ?
(a)
(b) CH3––CH2––CH2––Cl, AlCl3
(c)
(d) CH3––CH2––CH2––OH, BF3
(a) (b)
18. (S)
Which of the following is not the appropriate way of

conversion ?
(a) CH3CH2X, AlCl3
(c) (d)
O
(b) CH3 – C – Cl, AlCl3; Zn–Hg, HCl
15.(S) The number of structural and configurational isomers of a
bromo compound, C5H9Br, formed by the addition of HBr (c) Br2, Fe; C2H5MgCl, ether
to 2-pentyne respectively, are
(d) Br2, Fe; CH3CH2–Br; Na, ether
(a) 1 and 2 (b) 2 and 4
(c) 4 and 2 (d) 2 and 1
3Cl2 Br2 , Fe
16. (S) What is the major product in the reaction ? 19. (S)    
 or light
Zn 

HCl Product
The main product is
(a)
(a) (b)
(b)
(c) (c) (d)
(d)
HYDROCARBONS 189
OH
20. (S) In which of the following the incorrect place for
electrophilic substitution has been indicated ? O2N NO2
(a) SO3H
HNO3
OH
O2N NO2
(b)
NO2
(Picric Acid)
This is because
(c) (a) –SO3H group is a better leaving group than –NO2
group in electrophilic substitution
(b) –NO2 group is a better leaving group than –SO3H
group in electrophilic substitutions
(c) This is a nucleophilic substitution.
(d) both (b) and (c)
(d)
23. (S)
Which of the following is the correct structure of the

21. (S) An electrophile, E attacks the benzene ring to generate organic product of the above reaction ?
the intermediate –complex. Of the following, which –
complex is of lowest energy ?
(a)
(a) (b)
(b)
(c)
(c) (d)
22. (S) The sulfonic acid group is often readily replaced by a

nitro group e.g.,
(d)
HYDROCARBONS 190
24. (S) Which will undergo Friedal-Craft alkylation reaction ?

(d)
CH3 CH2CH3 COOH OH
26. (S) Nitration of benzene is possible by which of the

following reagents ?
NO2
1 2 3 4 (a) Conc. HNO3/Conc. H2SO4
(b) R NO 2/H
(a) 1 and 3 (b) 2 and 4
(c) both (a) and (b)
(c) 1 and 2 (d) 1, 2 and 4
(d) none of these
Br2 /H2O 27. (M) Which of the statements are correct for alkyne with
Conc. H SO
4  (X) 
25. (S) excess  (Y)
2

molecular formula C6H10 ?
: Product (Y) of this reaction is (a) It shows 7 structural isomers.
(b) It shows 4 terminal and 3 internal alkynes.
(a) (c) It shows 3 terminal and 4 internal alkynes.
(d) Only one isomer is chiral.
28. (M) Choose the correct comparisons :
(a)
(b)
(b) >
(c) (c)
(Reactivity towards HBr)
(d)
HYDROCARBONS 191
29. (M) Which of the following reactions are correctly
(a) A is Ph – CH2 – CH2 – CH2 – CH3
represented ?
(a) R – CH = CH2 + HCl (b) B is Ph – CH = CH – CH = CH 2
(c) A is Ph – CH = CH – CH = CH2
(b) R – CH = CH2 + HI R – CH 2 – CH2 – I (d) B is Ph – CH2 – CH2 – CH = CH2
34. (M) :
(c) R – CH = CH2 + HBr R – CH2 – CH2 – Br
(a) A is
(d) R – CH = CH 2 + HI
(b) A is
30. (M) Which of the following will produce a visible change
with 1-butyne and can be used to differentiate it from
2-butyne ?
(c) B is
+
(a) Ag(NH3)2 (b) Cu(NH3)2+
(c) KMnO4/H+ (d) Br2
31. (M) Which of the following reactions are not feasible ? (d) B is
(a)
35. (M) In which of the followings, reactant and product are
correctly matched ?
(b)
(a)
(c)
(d)
32. (M) Which of the following will react with 1-butyne ? (b)
(a) AgNO3 + NH4OH (b) Cu2Cl2 + NH4OH
(c) Na (d) KMnO4/

(c)
33. (M) Predict the products of following reactions :
(d)
HYDROCARBONS 192
36. (M) Which of the following cations are more stable than (D) G NO 2 . Reaction with CH3Cl, AlCl3.
benzyl cation ?
39. (M) Halogens are deactivating yet ortho, para directing
in electrophilic aromatic substitution. Which
statements do not explain this ?
(a) A combination of inductive electron withdrawal
and resonance electron release.
(a) (b) (b) Inductive electron withdrawal with no resonance
effect.
(c) A combination of inductive electron release and
resonance electron withdrawal.
(d) A combination of inductive electron release and
resonance electron release
40. (M) Which of the following are deactivating but ortho,
para directing during el ectrophil ic aromatic
(c) (d)
substitution reaction ?
37. (M) Which of the following is/are deactivating groups

towards electrophilic aromatic substitution ? (a)
(a) – Cl (b) – NO2
(c) – CH2 – CH2Cl (d) Cl
(b)
38. (M) For the following reactions of substituted benzene, mark
the answer using the following guide line
(i) If substitution takes place at ortho/para position
mark 1.
(ii) If substitution takes place at meta, mark 2.
(iii) If reaction takes place at position other than these, (c)
mark 3.
(iv) In case of no reaction, mark 4.
G = substituent
(d)
(A) G CH3 . Reaction with CH3Cl, AlCl3.
(B) G CH3 . Reaction with Cl2, hv..
(C) G NO . Reaction with Cl2, Fe.

HYDROCARBONS 193
In this reaction which ring will be reduced, by

41.(M) Isopropyl benzene can be obtained by :
hydrogenation.
(a) 44. (I) Examine the structural formulas shown below and
find out how many compounds will show oxidation
reaction with acidic KMnO4.
(b)
, ,
(c)
, , ,
(d)
45. (I) Id entify number of subst ituent s those are

deactivating but ortho and para directing.
42. (I) How many mono chlorinated products may be

obtained when the alkane shown below is heated in
the presence of Cl2
43. (I)
HYDROCARBONS 194
46. (I) Each of the compounds shown below has two

aromatic ring, labled as A and Identify number of
compounds in which ring B is more active than ring
A for electrophilic aromatic substitution reaction.
,
, , ,
48. (I) Examine the structural formulas shown below and

find out how many compounds undergo electrophilic
nitration more rapidly than flouro benzene.
, ,
47. (I) Examine the structural formulas shown below and

find out how many compounds can not, give Friedel
Craft reaction.
HYDROCARBONS 195
49. (A) Assertion : Among isomeric alkanes, branching increase 55. (A) Assertion : Addition of HBr in presence of a peroxide
the boiling points. (ROOR) to propene gives 2-bromo propane.
Reason : Branching lowers the intermolecular van der Reason : Reaction involves a bromine free radical.
Waal’s force of attraction.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
56. (A) Assertion : 1-butyne forms white precipitate with
50. (A) Assertion : Addition of HCl to 3-methyl-1-butene ammoniacal silver nitrate solution while 2-butyne
gives 2-chloro-2-methyl butane as the major product. does not.
Reason : Rearrangement of carbocation to more
Reason : 1-butyne has acidic hydrogen.
stable carbocation leads to formation of major
product. (a) A (b) B
(a) A (b) B (c) C (d) D

(c) C (d) D 57. (A) Assertion : Hydrogenation of an alkene is always an
exothermic process.
51. (A) Assertion : A mixture of alkene and alkane can be
separated by passing the mixture through a cold, Reason : Alkane has lower potential energy than an
concentrated sulphuric acid solution. alkene.
Reason : Alkene is absorbed in the solution while (a) A (b) B
alkane passes unreacted. (c) C (d) D
(a) A (b) B
58. (A) Assertion : 2-butyne on controlled hydrogenation
(c) C (d) D
with Pd/CaCO3 in presence of PbO gives cis-2-butene.
52.(A) Assertion: Addition of Br2 to 1-butene gives two optical
isomers. Reason : Hydrogenation occur at the surface of metal
Reason: The product contains one asymmetric carbon. containing adsorbed hydrogen.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
53. (A) Assertion : Alkenes usually undergo electrophilic
addition reaction at carbon-carbon double bond. 59. (A) Assertion : Benzene does not decolourise alkaline
KMnO4.
Reason : Electrophilic addition at double bond
produces carbocation intermediate. Reason : Benzene is stabilized by resonance and -
electrons are delocalized.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
54. (A) Assertion : Propyne is more reactive than propene 60. (A) Assertion : Toluene undergoes nitration much more
towards electrophilic addition of HBr. readily than benzene.
Reason : It is due to electron releasing nature of –CH3
Reason : Propyne has greater electron density group which increases electron density on benzene and
available for electrophile due to two pi-bonds, electrophilic substitution reaction like nitration becomes
faster.
therefore more electrophilic.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
HYDROCARBONS 196
61. (X) 63. (X)
64. (X) Match the following :

Column–I Column–II
62. (X) Column (I) Column (II)
CH2Cl
(a) (P) Dicarboxylic acid will be

(a) (p) Activated towards electrophilic
aromatic substitution
formed when reacts with
hot alkaline KMnO4. OH
(b) (Q) Decolourise Br2/H2O.

(b) (q) Deactivated towards electrophilic
aromatic substitution
N O
(c) (R) Dicarboxylic acid and will (c) (r) Ortho/Para director
be formed when reacts

will O3/H2O2. CH3
(d) (s) Meta-director

(d) (S) Number of allylic
hydrogen is odd.
HYDROCARBONS 197
Passage Q. No. 65 to 67 66. (C) Which of the following cannot be starting material
for this compound
A benzene ring deactivated by strong and moderate
electron withdrawing group that is, any meta directing
group, is not electron rich enough to undergo Friedel-
Crafts reactions.
(a)
(b)
Friedel-Crafts reaction also do not occur with NH 2
group as it react with AlCl3 and produce deactivating
group.
(c)
(d)
X (No reaction) 67. (C) Which of the following sequence of reaction is

correct for the synthesis of product
65. (C) Which of the following compounds undergo Friedel-
Crafts alkylation reaction ?
(a) (b)
(a)
(c) (d) (b)
(c)
(d) All are incorrect

HYDROCARBONS 198
Passage Q.No. 68 to 70 70. (C) Which of the following -complexes generated by the
attack of an electrophile of benzene ring has lowest
Aromatic compounds can easily show electrophilic energy ?
substitution reactions due to the presence of pie electron OCOCH3 NO2
clouds above and below the plane of aromatic ring. This
ring can be easily attached by electrophiles due to high
electro density. The mechanism of these reaction is + +
common in general which can be given as follows : (a) (b)
H E H E
OCH3 OCH3
+ H +
(c) (d)
E H E
H Passage Q.No. 71 to 73
k2 Directing nature of substituted aromatic compound
RX E RX E +H is decided by stability of -complex or arenium ion. If
fast
-complex is stabilise at o-and p-position by attack
of electrophile then the group is o-and p-directing
but if -complex is stabilise at m-position then group
68. (C) In which of the following compounds the rate of will be meta directing
electrophilic substitution (Halogenation) is fastest ?
(a) (b)
NH
s
(c) (d)
NH
N
H
On the basis of above explanation find out correct
69. (C) Which of the following resonance structures is not a answers of following questions.
contributor to the cyclo hexa dienyl cation intermediate
in the halogenation of benzene ?
71. (C) Which of the following is m-directing ?
H X H X
(a) (b)
(a) (b)
X H X
H
(c) (d)
H (c) (d)
HYDROCARBONS 199
72. (C) Which of the following is not o-and p-directing ?
74. (C)
(a)
Find out correct product of reaction.
(b)
(a)
(c)
(b)
(d)
73. (C) Which of the following is o- and p-directing ?
(c)
(a) (b)
(d) No reaction
75. (C) Major product formation take place at which position
in this reaction :
(c) (d)
Passage Q.No. 74 to 76
If aromatic ring is substituted by more than groups (a) 3 (b) 1
then electrophilic aromatic substitution reaction take (c) 6 (d) 4
place according to more activating group. Types of
group which donate electron in aromatic ring known
as activating groups.
HYDROCARBONS 200
76. (C) Find out major product of following reaction : Subjective Type Questions
77. Write down the structure of the stereoisomers formed when

cis-2-butene is reacted with bromine.
78. 1, 3-butadiene with bromine in molar ratio of 1 : 1 generate
predominantly .......... .
(a)
(b)
(c)
(d)
HYDROCARBONS 201
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS
Single Choice Questions 7. Consider the following reaction

1. Which one of the following alkenes will react fastest with
H2 under cataltic hydrogenation condition? (2000)
(a) (b) Identify the structure of the major product X (2002)
(a)
(c) (d)
2. Propyne and propene can be distinguished by (2000)

(b)
(a) conc. H2SO4 (b) Br2in CCl4
(c) dil. KMnO4 (d) AgNO3 in ammonia
3. Hydrogenation of the adjoining compound in the presence
(c)
of poisoned palladium catalyst gives (2001)
(d)
(a) an optically active compound

8. (2003)
(b) an optically inactive compound
(c) a racemic mixture
(d) a diastereomeric mixture
(a) (b)
4. The reaction of propene with HOCl proceeds via the
addition of (2001)
+ +
(a) H in the first step (b) Cl in the first step
– + –
(c) OH in the first step (d) Cl and OH single step
(c) (d)
5. In the presence of peroxide, hydrogen chloride and
hydrogen iodide do not give anti-Markownikoff’s addition
to alkenes because (2001)
(a) both are highly ionic
(b) one is oxidising and the other is reducing 9. 2-phenyl propene on acidic hydration, gives (2004)
(c) one of the steps is endothermic in both the cases (a) 2-phenyl-2-propanol (b) 2-phenyl-1-propanol
(d) all the steps are exothermic in both the cases (c) 3-phenyl-1-propanol (d) 1-phenyl-2-propanol
6. Identify a reagent from the following list which can easily 10. 2-hexyne gives trans-2 hexene on treatment with (2004)
distinguish between 1-butyne and 2-bytyne. (2002)
(a) Li/NH3 (b) Pd/BaSO4
(a) bromine, CCl4 (b) H2, Lindlar catalyst
(c) LiAlH4 (d) Pt/H2
(c) dilute H2SO4, HgSO4 (d) ammoniacal CuCl2 solution
HYDROCARBONS 202
(b) alcoholic KOH followed by NaNH2
11. How many chiral compounds are possible on mono (c) aqueous KOH followed by NaNH2
chlorination of 2 -methyl butane? (2004)
(d) Zn/CH3OH
(a) 2 (b) 4
17. The number of stereoisomers obtained by bromination of
(c) 6 (d) 8 trans-2-butene is (2007)
12. 1-bromo-3-chlorocyclobutane when treated with two (a) 1 (b) 2
equivalents of Na, in the presence of ether which of the
(c) 3 (d) 4
following will be formed? (2005)
18. The synthesis of 3-octyne is achieved by adding a
bromoalkane into a mixture of sodium amide and an alkyne.
The bromoalkane and alkyne respectively are (2010)
(a) (b)
(a) BrCH CH CH CH CH and CH CH C  CH
2 2 2 2 3 3 2
(c) (d) (b) BrCH 2 CH 2 CH 3 and CH 3 CH 2 CH 2 C  CH
13. Cyclohexene is best prepared from cyclohexanol by which (c) BrCH 2 CH 2 CH 2 CH 2 CH 3 and CH 3 C  CH
of the following? (2005)
(d) BrCH 2 CH 2 CH 2 CH 3 and CH 3CH 2 C  CH
(a) conc. H3PO4 (b) conc. HCl/ZnCl2
(c) conc. HCl (d) conc. HBr Multiple Choice Question
14. Identify the product. 19. Hydrogen bonding plays a central role in the following
phenomena (2016)
(2006)
(a) ice floats in water
(a) (b)
(b) higher Lewis basicity of primary amines than tertiary
amines in aqueous solutions
(c) formic acid is more acidic than acetic acid
(c) (d) (d) dimerisation of acetic acid in benzene

Integer Type Question
20. The total number of cyclic isomers possible for a
hydrocarbon with the molecular formula C4H6 is (2010)
15. (isomeric products) C5H11Cl 21. The maximum number of isomers (including stereoisomers)
that are possible on mono-chlorination of the following
compound CH3CH2CH(CH3)CH2CH3, is (2011)
Assertion Reason Type Question
(isomeric products) What are N and (A) Both Assertion and reason are true and reason is the
M? (2006) correct explanation for assertion.
(a) 6, 6 (b) 6, 4 (B) Both Assertion and reason are true but reason is not the
(c) 4, 4 (d) 3, 3 correct explanation for assertion.
16. The reagent(s) for the following conversion, (C) Assertion is true and reason is false
(D) Assertion is false and reason is true
is/are
22. Assertion: 1-butene on reaction with HBr in the presence
(2007) of a peroxide produces 1-bromobutane.
(a) alcoholic KOH Reason: It involves the formation of a primary radical.
(2000)
(a) A (b) B
(c) C (d) D
HYDROCARBONS 203
23. Assertion: Dimethyl sulphide is commonly used for the 26. The structure of the compound Q is (2011)
reduction of an alkene to get the carbonyl compound.
Reason: It reduces the ozonide giving water soluble
dimethyl sulphoxide and excess of it evaporates. (2001)
(a) A (b) B (a)
(c) C (d) D
24. Assertion: Addition of bromine to trans-2 butene yields
meso-2, 3-dibromo butane.
Reason: Bromine addition to an alkene is an electrophilic
(b)
addition. (2001)
(a) A (b) B
(c) C (d) D
Comprehension Based Questions
(c)
An acyclic hydrocarbon P, having molecular formula C6H10,
gave acetone as the only organic product through the
following sequence of reactions, in which Q is an
intermediate organic compound.
(d)
27. The product X is (2011)
(a) (b)
(c) (d)
25. The structure of compound P is (2011)
(a) 28. The correct statement with respect to product Y is

(2014)
(b)
(a) It gives a positive Tollens test and is a functional isomer
of X.
(b) It gives a positive Tollens test and is a geometrical
(c)
isomer of X.
(c) It gives a positive iodoform test and is a functional
isomer of X.
(d) It gives a positive iodoform test and is a geometrical
(d) isomer of X.
Subjective Questions
29. What would be the major product in the following reaction?
(2000)
HYDROCARBONS 204
30. An alkene (A) C16H16 on ozonolysis gives only one
product (B) C8H8O. Compound (B) on reaction with NaOH/ Determine the number of double bonds in Bombykol. Write
I2 yields sodium benzoate. Compound (B) reacts with KOH/ the structures of compound A and Bombykol. How many
NH2NH2 yielding a hydrocarbon (C) C8H10. Write the geometrical isomers are possible for Bombykol? (2002)
structures of compounds (B) and (C). Based on this 34. Monomer A of a polymer on ozonolysis yields two moles
information two isomeric structures and identify the isomer of HCHO and one mole of CH3 COCHO.
which on catalytic hydrogenation (H 2/Pd-C) gives a
(a) Deduce the structure of A.
racemic mixture. (2001)
31. (a) Identify (A), (B), (C), (D) and (E) in the following (b) Write the structure of all “cis” form of polymer of
schemes and write their structures: compound A. (2005)
35. One mole of a hydrocarbon ‘A’ reacts with one mole of
bromine giving a dibromo compound, C5H10Br2. Compound
‘A’ on treatment with cold dilute alkaline potassium
permanganate solution forms a compound, C5H12O2. On

(b) Identify (X), (Y) and (Z) in the following synthetic
ozonolysis ‘A’ gives equimolar quantities of propanone
scheme and write their structures. Explain the formation of
labelled formaldehyde (H2C*O) as one of the products and ethanal. Deduce the structural formula of ‘A’.
when compound (Z) is treated with HBr and subsequently (2011)
ozonolysed. Mark the C* carbon in the entire scheme.
14
BaC*O3 + H2SO4  (X) gas [C* denotes C ]
(2001)
32. Identify X, Y and Z in the following synthetic scheme and
write their structures.
Is the compound Z optically active? Justify your aswer

(2002)
33. A biologically active compound, Bombykol (C16H30O) is
obtained from a natural source. The structure of the
compound is determine by the following reactions.
(a) On hydrogenation, Bombykol gives a compound A,
C16H34O, which reacts with acetic anhydride to give
an ester.
(b) Bombykol also reacts with acetic anhydride to give
another ester, which on oxidative ozonolysis
(O3/H2O2) gives a mixture of butanoic acid, oxalic acid
and 10-acetoxy decanoic acid.
HYDROCARBONS 205
Note:
HYDROCARBONS
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scanning the QR code.
206
Answer Key
CHAPTER -1 GENERAL ORGANIC CHEMISTRY
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS
DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.
1.(c) 2.(b) 3.(b) 4.(b) 5.(c) 1.(c) 2.(d) 3.(c) 4.(c) 5.(b)
6.(a) 7.(d) 8.(a) 9.(a) 10.(a) 6.(c) 7.(c) 8.(a) 9.(b) 10.(b)
11.(d) 12.(c) 13.(d) 14.(d) 15.(d) 11.(c) 12.(b) 13.(a) 14.(c) 15.(c)
16.(b) 17.(b) 18.(a) 19.(c) 20.(d) 16.(b) 17.(d) 18.(d) 19.(b) 20.(c)
21.(c) 22.(a) 23.(b) 24.(d) 25.(a) 21.(d) 22.(d) 23.(b) 24.(d) 25.(c)
26.(c) 27.(c) 28.(d) 29.(d) 30.(d) 26.(b) 27.(c) 28.(d) 29.(c) 30.(a)
31.(a) 32.(d) 33.(c) 34.(c) 35.(b) 31.(b) 32.(50)
36.(d) 37.(c) 38.(c) 39.(a) 40.(c)
41.(c) 42.(d) 43.(d) 44.(b) 45.(c)
46.(c) 47.(c) 48.(c) 49.(a) 50.(d)
51.(a) 52.(c) 53.(d) 54.(d) 55.(d)
56.(d) 57.(b) 58.(a) 59.(d) 60.(d)
61.(a) 62.(d) 63.(a) 64.(c) 65.(b)
66.(a) 67.(b) 68.(c) 69.(c) 70.(b)
71.(a) 72.(c) 73.(b) 74.(d) 75.(d)
76.(c) 77.(c) 78.(b) 79.(a) 80.(c)
81.(a) 82.(d) 83.(a) 84.(d) 85.(a)
86.(c) 87.(d) 88.(d) 89.(d) 90.(a)
91.(c) 92.(c) 93.(b) 94.(c) 95.(c)
96.(a) 97.(b) 98.(d) 99.(b) 100.(b)
101.(d) 102.(a) 103.(c) 104.(d) 105.(a)
106.(c) 107.(c) 108.(a) 109.(c) 110.(b)
111.(c) 112.(c)
ANSWER KEY 207
CHAPTER -1 GENERAL ORGANIC CHEMISTRY
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED
QUESTIONS
DIRECTION TO USE -
Scan the QR code and check detailed solutions. DIRECTION TO USE -
Scan the QR code and check detailed solutions.
1.(c) 2.(d) 3.(d) 4.(c) 5.(c) 1.(b) 2.(d) 3.(b) 4.(b) 5.(b)
6.(b) 7.(a) 8.(d) 9.(c) 10.(b) 6.(c) 7.(a) 8.(a) 9.(a) 10.(c)
11.(c) 12.(d) 13.(a) 14.(b) 15.(c) 11.(c) 12.(d) 13.(a) 14.(d) 15.(b)
16.(d) 17.(d) 18.(a) 19.(a) 20.(a) 16.(d) 17.(b) 18.(c) 19.(b,c) 20.(c,d)
21.(d) 22.(c) 23.(a) 24.(b) 25.(a) 21.(b,d) 22.(b,d) 23.(b,c) 24.(5.00) 25.(Text)
26.(c) 27.(c) 28.(a) 29.(d) 30.(b) 26.(Text) 27.(Text) 28.(Text)
31.(c) 32.(d) 33.(b) 34.(d) 35.(a)

36.(a) 37.(d) 38.(b) 39.(a) 40.(c)
41.(c) 42.(a) 43.(a) 44.(d) 45.(b)
46.(c) 47.(a) 48.(a,b) 49.(a,c)
50.(a,b,c,d) 51.(a,b,c,d) 52.(a,b,d)
53.(c) 54.(a) 55.(d)
56.(b) 57.(a) 58.(a) 59.(c) 60.(a)
61.(c) 62.(d) 63.(b) 64.(b) 65.(a)
66.(Text) 67.(Text) 68.(a) 69.(b) 70.(c)
71.(c) 72.(d) 73.(Text) 74.(Text) 75.(Text)
ANSWER KEY 208
Answer Key
CHAPTER -2 HYDROCARBONS
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

1.(a) 2.(b) 3.(b) 4.(b) 5.(b) 1.(d) 2.(a) 3.(c) 4.(d) 5.(d)
6.(c) 7.(a) 8.(d) 9.(a) 10.(b) 6.(a) 7.(c) 8.(b) 9.(d) 10.(b)
11.(c) 12.(c) 13.(a) 14.(c) 15.(d) 11.(c) 12.(d) 13.(d) 14.(c) 15.(c)
16.(d) 17.(d) 18.(c) 19.(d) 20.(b) 16.(a) 17.(d) 18.(d) 19.(a) 20.(a)
21.(d) 22.(b) 23.(c) 24.(d) 25.(b) 21.(d) 22.(b) 23.(a) 24.(d) 25.(b,c)
26.(c) 27.(d) 28.(c) 29.(b) 30.(a) 26.(d) 27.(b) 28.(a) 29.(b) 30.(d)
31.(c) 32.(b) 33.(c) 34.(a) 35.(b) 31.(d) 32.(b) 33.(a) 34.(d) 35.(c)
36.(b) 37.(c) 38.(b) 39.(a) 40.(a) 36.(d) 37.(13)
41.(b) 42.(d) 43.(d) 44.(c) 45.(b)
46.(c) 47.(b) 48.(c) 49.(b) 50.(c)
51.(d) 52.(d) 53.(c) 54.(b) 55.(c)
56.(d) 57.(c) 58.(b) 59.(d) 60.(a)
61.(d) 62.(b) 63.(d) 64.(a) 65.(b)
66.(b) 67.(c) 68.(c) 69.(c) 70.(c)
71.(a) 72.(a) 73.(b) 74.(c) 75.(d)
76.(a) 77.(a) 78.(d) 79.(b) 80.(d)
81.(d) 82.(b) 83.(b) 84.(b) 85.(b)
86.(c) 87.(a) 88.(b) 89.(b) 90.(b)
91.(c) 92.(d) 93.(d) 94.(d) 95.(c)
ANSWER KEY 209
CHAPTER -2 HYDROCARBONS
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED
QUESTIONS

1.(d) 2.(a) 3.(c) 4.(a) 5.(a) 1.(a) 2.(d) 3.(b) 4.(b) 5.(c)
6.(c) 7.(b) 8.(c) 9.(b) 10.(d) 6.(d) 7.(b) 8.(a) 9.(a) 10.(a)
11.(b) 12.(a) 13.(c) 14.(d) 15.(b) 11.(c) 12.(d) 13.(a) 14.(a) 15.(b)
16.(d) 17.(c) 18.(c) 19.(b) 20.(b) 16.(b) 17.(a) 18.(d) 19.(a,b,d) 20.(0005)
21.(b) 22.(a) 23.(d) 24.(b) 25.(c) 21.(0008) 22.(c) 23.(a) 24.(b)
26.(a) 27.(a,b,d) 28.(a,b,d) 25.(d) 26.(b) 27.(a) 28.(c) 29.(Text)
29.(a,c,d) 30.(a,b) 31.(a,c,d) 30.(Text) 31.(Text) 32.(Text) 33.(Text) 34.(Text)
35.(Text)
32.(a,b,c,d) 33.(a,b) 34.(b,c) 35.(c,d)
36.(a,c,d) 37.(a,b,c,d)
38.(a,b,c,d) 39.(b,c,d) 40.(a,c)
41.(a,b,c) 42.(0001) 43.(0002)
44.(0004) 45.(0005) 46.(0005)
47.(0006) 48.(0006) 49.(d)
50.(a) 51.(a) 52.(a) 53.(b) 54.(d)
55.(d) 56.(a) 57.(a) 58.(b) 59.(a)
60.(a)
61.(Text) 62.(Text) 63.(Text)
64.(Text)65.(c) 66.(c) 67.(c)
68.(d) 69.(c) 70.(d) 71.(c) 72.(c)
73.(b) 74.(a) 75.(b) 76.(c) 77.(Text)
78.(Text)
ANSWER KEY 210
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GENERAL ORGANIC CHEMISTRY

Exercise - 1 : Basic Objective Questions........................................................................................... 62

Exercise - 2 : Previous Year JEE MAIN Questions .......................................................................... 76

Exercise - 3 : Advanced Objective Questions ................................................................................ 81

Exercise - 4 : Previous Year JEE Advanced Questions ................................................................... 92

Answer Key ....................................................................................................................................... 206

Solved Examples............................................................................................................................... 160

Exercise - 1 : Basic Objective Questions........................................................................................... 166

Exercise - 2 : Previous Year JEE MAIN Questions ........................................................................... 179

Exercise - 3 : Advanced Objective Questions ................................................................................ 186

Exercise - 4 : Previous Year JEE Advanced Questions ................................................................... 201

Answer Key ....................................................................................................................................... 208

We encounter various petroleum products everywhere

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Vamsi sir is Graduate from IIT Bombay, his passion is to Re-

GENERAL ORGANIC CHEMISTRY

tissues and skin are formed by proteins, respiration is

2.1 Sigma and Pi Bonds - Comparison

Wohler successfully synthesized an organic compound

2.3 Degrees of Carbon

Condensed formulas are written without showing all the

2.2.3 Line-Angle Formula or Border Line Formula 2° (Secondary)

These are also called skeletal structures or a stick figure.

2.2.4 Tetrahedral Representation

Table : Hybridization of Common Molecules.

2.5 Applications of Hybridization Conjugated > Isolated > Cumulated

2.7 Commonly Occuring Forms of Carbon

The bond breaking is shown by two half-headed or fish-

Order of acidic strength : II > III > IV > I

5.2 Rules for Validity of Lewis Structures

5.3 Criteria for Major/Minor Contributors

6.1 Electron-Releasing and Electron-Withdrawing Groups

6.2.2 Effect on Reactivity of Carboxylic Acid Derivatives

A typical nucleophilic reaction is represented as :

The order of acidic strength is : II > V > I > III > IV

The stronger is the bond between C and Z, the difficult it

Reactivity order of carboxylic acid derivatives towards

7.1 -Carbon and -Hydrogen

Therefore, order of basic strength is : IV > III > I > V > II

Methyl > 1° > 2° > 3°

More is the number of -H, more is the 

7.3 Applications of Hyperconjugation

7.3.1 Stability of Alkenes

7.2 Mechanism of Electron Donation in Hyperconjugation

I is more stable than II.

Hyperconjugation is a - interaction and acts through a

The positive charge on C is delocalized over H to give

9. COMPARISON OF INDUCTIVE, HYPERCONJUGATION

11.4 Stability of Carbocations

Example - 19 Rate of formation of carbocation depends on :

11.6 Reactions of Carbocations

11.6.1 Capture a Nucleophile

11.6.2 Loose a proton to form a  bond

Order of stability : III > I > II

11.5 Formation of Carbocations